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Fu-Hua Sun, [Hezhang Li](https://orcid.org/0000-0002-6356-321X), Jun Tan, Lingmei Zhao, Xinyu Wang, Haihua Hu, Chao Wang, [Takao Mori](https://orcid.org/0000-0003-2682-1846)

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Review of current ZT &gt; 1 thermoelectric sulfidesilable at ScienceDirectJournal of Materiomics 10 (2024) 218e233Contents lists avaJournal of Materiomicsjournal homepage: www.journals .elsevier .com/journal-of-mater iomics/Review paperReview of current ZT > 1 thermoelectric sulfidesFu-Hua Sun a, f, 1, Hezhang Li b, c, *, 1, Jun Tan a, Lingmei Zhao a, Xinyu Wang a, Haihua Hu d,Chao Wang c, Takao Mori b, e, **a School of Materials Science and Engineering, Hubei Normal University, Huangshi, 435002, Chinab International Center for Materials Nanoarchitechtonics (WPI-MANA), National Institute for Materials Science (NIMS), Namiki 1-1, Tsukuba, 305-0047,Japanc Department of Precision Instrument, Tsinghua University, Beijing, 100084, Chinad State Key Laboratory of New Ceramics and Fine Processing, School of Materials Science and Engineering, Tsinghua University, Beijing, 100084, Chinae Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba, 305-8671, Japanf Foshan Xianhu Laboratory of the Advanced Energy Science and Technology Guangdong Laboratory, Foshan, 528225, Chinaa r t i c l e i n f oArticle history:Received 25 April 2023Received in revised form26 May 2023Accepted 28 May 2023Available online 20 June 2023Keywords:Synthetic technologyFigure merit of ZTSulfidesThermoelectric* Corresponding author. International Center for M0047, Japan.** Corresponding author. International Center for M0047, Japan.E-mail addresses: lihezhangshishui@163.com (H. L1 These authors contributed equally.https://doi.org/10.1016/j.jmat.2023.05.0112352-8478/© 2023 The Authors. Published by Elseviecreativecommons.org/licenses/by-nc-nd/4.0/).a b s t r a c tThermoelectrics has played a fascinating role in the developments of direct energy conversion tech-nologies. Over the past decade, sulfur-based thermoelectric materials have been significantly advanced inoptimizing electrical and thermal transport due to their similarities in chemical and structural propertieswith tellurides and selenides. This review provides research progress on metal sulfides, particularlyfocuses on materials exhibiting high thermoelectric figure of merit (ZT > 1.0). It highlights the potentialcompounds, e.g. CueS, SneS, PbeS based, and polysulfides. Great strategies of superionic conducting,band configuration tuning, high-entropy alloying, and anomalous harmonic scattering are try todemonstrate the performance-improved mechanisms for thermoelectric sulfides. In addition, somecommon synthesis recipes are briefly introduced, and thereby making potential candidates as excellentalternatives for producing thermoelectric power generators in the mid temperature. Key outcomes alongwith how to further improve the thermoelectric performance and promote its scale-up applications arealso outlined at the end.© 2023 The Authors. Published by Elsevier B.V. on behalf of The Chinese Ceramic Society. This is an openaccess article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).Contents1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2192. Structural merits for sulfide thermoelectrics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2202.1. Superionic conduction of thermoelectric sulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2202.2. Band configuration tuning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2212.3. Anomalous harmonic phonon scattering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2223. High performance thermoelectric binary sulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2223.1. Copper sulfide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2223.2. Lead sulfide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2243.3. Tin sulfide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2244. New polysulfides and thermoelectric enhancement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2264.1. Tetrahedrite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2264.2. Colusite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2264.3. Other metal based sulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226aterials Nanoarchitechtonics (WPI-MANA), National Institute for Materials Science (NIMS), Namiki 1-1, Tsukuba, 305-aterials Nanoarchitechtonics (WPI-MANA), National Institute for Materials Science (NIMS), Namiki 1-1, Tsukuba, 305-i), MORI.Takao@nims.go.jp (T. Mori).r B.V. on behalf of The Chinese Ceramic Society. This is an open access article under the CC BY-NC-ND license (http://http://creativecommons.org/licenses/by-nc-nd/4.0/mailto:lihezhangshishui@163.commailto:MORI.Takao@nims.go.jphttp://crossmark.crossref.org/dialog/?doi=10.1016/j.jmat.2023.05.011&domain=pdfwww.sciencedirect.com/science/journal/23528478www.journals.elsevier.com/journal-of-materiomics/https://doi.org/10.1016/j.jmat.2023.05.011http://creativecommons.org/licenses/by-nc-nd/4.0/http://creativecommons.org/licenses/by-nc-nd/4.0/https://doi.org/10.1016/j.jmat.2023.05.011https://doi.org/10.1016/j.jmat.2023.05.011F.-H. Sun, H. Li, J. Tan et al. Journal of Materiomics 10 (2024) 218e2335. Synthesis recipes of thermoelectric sulfides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2276. Conclusion and outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228Declaration of competing interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2291. IntroductionThermoelectric (TE) technology, namely the capacity of directlyconverting energy fromheat to electricity and vice versa, provides agreat potential in the fields of harvesting waste heat and solid statecooling [1e5]. It possesses great merits, e.g. durability, modula-bility, emission-free, long lifetime, and low maintenance [6e8].Despite notable progress [9,10], the implementation of TE practicalapplication is still limited by its low conversion efficiency, which isdetermined by the dimensionless figure of merit ZT¼ S2sT/k, whereS is the Seebeck coefficient, s is the electrical conductivity, k is thethermal conductivity, and T is the absolute temperature, respec-tively. k can bemainly divided into two parts: lattice (kL) and carrier(ke) contributions.Enhancing ZT requires a trade-off between the inversely relatedelectrical (a and s) and thermal transport (k), making it difficult toimprove any individuals without degrading the others. ZT > 1 hasserved as a historical standard for niche application for a given TEmaterial [11]. Generally, the dominating factors for achieving highZT target either to increase power factor (PF ¼ S2s) or to decrease k.For example, band structure engineering [12] near the Fermi level(EF) has been proved to be one of the effective way to improve PFdue to the optimized charge carrier transport behaviors. Of course,k is also related to the carrier concentration (n). Therefore, thesearch for good TE materials is all about finding a material with thesuitable electronic and atomic structures. It is well described by aquality factor B [13]. B is a function of the number of band valley Nvand the inertial effective mass m*I . Increased Nv means largernumber of conduction pathways for charged carriers to participatein electrical performance. Decreasing m*I (¼ m*B is band effectivemass for an isotropic structure) through maximizing electronicmobility (mft=m*I , where t is the scattering relaxation time), re-ceives a strengthen electronic scattering. Therefore, large Nvdirectly leads to a real enhancement of B and thereby ZT. Greatstrategies, e.g., nanostructure engineering [14e17], entropy engi-neering [18], rattling atoms [19], hierarchical architectures [20],defect engineering [21,22], and exploring novel compounds [23]have beenwell performed to reduce kL. These technologies instructimportant findings of various state-of-the-art TE materials andachieving high ZT, including Mg3Bi2 (ZT ¼ 1.2) [24], (Sn,Cd)Te0.88Se0.12 (ZT ¼ 0.9) [25], (Pb,Sb,Ge)Se (ZT ¼ 1.54) [26], (Bi,Sb)2Te3(ZT ¼ 1.86) [27], Cu2(S,Te) (ZT ¼ 2.1) [28], (Na,Eu,Pb)Te (ZT ¼ 2.2)[29], (Pb,Sr)Te (ZT ¼ 2.5) [30], GeTe (ZT ¼ 2.7) [31] and SnSe crystal(ZT ¼ 2.8 [32] and even over 3.0 [33]).Despite high ZT being achieved in aforementioned TE materials,most of them contain rare-earth and toxic elements and/or tech-nical challenges, which probably hinders large-scale practical ap-plications. Therefore, developing alternative materials composed ofeco-friendly and low-cost elements with acceptable performance isvery essential [34,35]. Noted that sulfur abundance on land hugelyexceeds that of tellurium, enabling metal sulfides to becomeattractive candidates for TE community. Compared with tellurides,high phonon vibrational frequency derived from light sulfur atom219leads to low intrinsic kL. From another perspective, in order to findeffective strategies to achieve high ZT in TE sulfides, optimizing PFhas become the core issue. For example, it attempts to reduce thebandgap (Eg) between anion- and cation-derived orbitals. Theoptimized electronic structure provides more efficient orbitaloverlap and the broadened bands, thereby reducing m*I andincreasing m. That is why the partial substitution of sulfur by sele-nium is successful in fine-tuning electrical transport properties insulfides, and thereby reaching high ZT.As represented in Fig. 1, the majority of high-performance TEsulfides are p-type semiconductors. n-type counterparts are veryrare, and corresponding ZT-enhancement remains a challenge. Itgenerally occurs in lead-based sulfides or compounds with com-plex crystal structures and/or multiple phases existence. Althoughthe rocksalt-structured PbS, regardless of p- and n-type derivatives,achieves high ZT (reach and even exceed 1.0), increasing attentionson environmental impact of lead has been concerned. It promptsmuch investigation of the base-metal sulfides. As expected, tinchalcogenides derived from a single crystalline SnS, ZT > 1.5 [36],have recently motivated a wider investigation in TE community. Inaddition, several high-performance p-type polysulfides with earth-abundant elements were reported at moderate temperatures,ZT > 1.0, e.g., tetrahedrites [37,38], colusites [39], chalcopyrites[40e42] and homo-structure sulfides [43]. For binary sulfides, p-type copper sulfides and their derivatives exhibit the exceptional TEproperties, a peak ZT ~2.3 was achieved [44], which originated fromthe high mobility of Cu-cation. That is, the cation sub-latticeprobably enters the liquid-like state, and induces phonon-liquid-electron-crystal (PLEC) type phases [45]. Noted that cation migra-tion may promote compositional changes and even format sec-ondary phases during preparation or processing, lead to introducean instability into the matrix and cause cracking and loss of TEproperties. Therefore, great efforts of introducing additional cationsor finding alternative structures have been motivated in order toovercome the ionic diffusion and further block the migration path.Taking an overall view, volatilization in sulfur-based TE materialsmay also result in materials degradation and performance deteri-oration at increasing temperature. In favorable case, these faults(interfaces, boundaries or defects) can enhance phonon scatteringand thereby reduce kL, which improves ZT value.This review intends to prospect themerits of metal sulfides fromthe superionic conductivity, band configuration tuning, andanomalous harmonic phonon scattering, and high-entropy alloyingaspects. It discusses some of themost promising binary sulfides andpolysulfides, and underlies their TE properties-improved mecha-nisms. Considering great progress in the implementation of TEtechnology, huge efforts on capturing TE sulfides should be fol-lowed by studies highly reliable devices. Therefore, several fabri-cation technologies of TE sulfides are outlined. The futureperspective and outlook about the material performance-enhancement and scale-up application are also given at the end.Fig. 1. Collections of peak ZT along with years and optimal temperature regions in both (a) p- and (b) n-type thermoelectric sulfides. All related references to ZT > 1 are listed insubsequent tables, while ZT < 1 contains Cu-M1-S (M1 ¼ Sn [46e50], Sb [51,52], Fe [53e59], Zn [60], Co [61], Bi [62]), colusites [37,63e71], M2-S (M2 ¼ Ag [72], Sn [73],Bi [74], Ti[75], Mo [76]), M3-BieS (M3 ¼ Pb [77,78], Mn [43], Fe [43], Te [79]), and other alloys [80].F.-H. Sun, H. Li, J. Tan et al. Journal of Materiomics 10 (2024) 218e2332. Structural merits for sulfide thermoelectricsThe strong linkage of metal sulfides to thermoelectricity origi-nates from the work of M. Telkes [81] in 1950, who studied the TEproperties (primarily electrical conductivity and Seebeck coeffi-cient) of several sulfides in mineral forms. Although the lightersulfur atom presents great challenges in achieving high perfor-mance which is typically attained in good materials with heavyatoms, the unique chemical and crystal structures can be exploitedto synthesize materials with exceptionally high PF and low k. Andthereby it has received great attention in the TE landscape.2.1. Superionic conduction of thermoelectric sulfidesCopper sulfides, particularly digenite Cu2-xS (0 � x � 1), aresimply composed of two elements, but numerous intermediatephases have been found [82], varying from Cu-rich Cu2S to Cu-poorCuS. According to the CueS phase diagram (Fig. 2a), Cu2-xS un-dergoes three phase transitions with increasing temperature, frommonoclinic structure (g phase) at room temperature (RT) to hex-agonal (b phase) at T ~ 376 K, and then to cubic (a phase) at hightemperature (HT). Zhang et al. [83] clearly reported thetemperature-dependent crystal structures of Cu2-xS through HT X-ray diffraction (XRD). It is well indicated that, as shown in Fig. 2b,the hot-pressed Cu1.8S pellet displayed a complex phase transitionfrom the combination of Cu1.96S (tetragonal structure) and Cu2S(monoclinic) to a mixture of hexagonal Cu2S and rhombohedralCu1.8S at T ~ 400 K, and then to cubic Cu2S at temperature around820 K.In low temperature (LT), monovalent Cu vacancies act as p-typedopants in Cu2-xS. Cu vacancies can reduce the antibonding char-acter, lower the energy position of the valence band maximum(VBM), and thereby enlarge the band gap (Eg) [85]. In typical cubicstructure (HT, a phase), S atoms form ordered and rigid sublattice,functioning as the framework, while Cu atoms are disordered andsplit into tetrahedra sites. Cu ions occupy each tetrahedronrandomly [86]. The dCu bands comprising the VBM are degenerateat G point, and the sCu bands, which can be considered to be thelowest CB, lie slightly below it at G point [87]. Therefore, Cu va-cancies mainly shift down EF and do not change the general shapeof the band in Cu2-xS compound. That is, the shapes of the VB areimmune to the Cu vacancies (LT and a phases) and Cu disorder (aphase). And thereby n can be safely tuned by the Cu vacancy con-tent, which will be probably promote the diffusion of Cu ions,220resulting in the liquid-like behavior and subsequent superionicconduction (SIC). Indeed, as previous report [88], the a phase is aclassic superionic phase having freelymobile Cu ions, while b phaseis a solid-liquid hybrid phase with Cu in a liquid-like substructure.SIC has played a fascinating role in the development of TE ma-terials. Based on thermodynamic study, the normal-to-SIC phasetransition indicates that the entropy change per atom is similar tothat half of the crystal state, namely the Cu sublattice is quasi-molten [89]. In SIC state (mainly a phase), the liquid-like sub-lattice is expect to hinder the heat transport by transverse modephonons or lattice vibrations, and thereby the volumetric specificheat (Cv) is lower than that of the Dulong-Petit limit [90] (3NkB, Nand kB are the total number of atoms and Boltzmann constant,respectively). At the same time, the fixed sublattice provides acrystalline pathway for electronic transport. Regardless of coppersulfides, another SICs with good TE values have also been explored,e.g., AgeS alloys [91], AgeCu based sulfides [92], AgBi3S5 [93], andCuTi2S4 [70]. As for an inorganic semiconductor, a-Ag2S receivedlarge attention due to its unusual ductility and respectable TEproperty. Fig. 2c describes the electronic band structures of a-Ag2Susing a PBE (Perdew, Burke, and Ernzerh) exchange-correlationfunctional [84]. a-Ag2S is a direct bandgap semiconductor of Eg~1.1 eV, and Fermi level is mainly formed by 4dAg and 3pS orbitals.The energy barrier between AgI at tetrahedral site and AgII of theoctahedral site is very small, presenting easily diffuse, especially atHT. In addition, the anti-bonding AgeS states appear below EFresult in a structural phase transition, tending to SIC. These featuresof metal sulfides make a reduced kL while preserving high s, whichleads to a significant TE enhancement.Beyond the SIC structures, TE properties are also significantlyoptimized and improved by entropy engineering [94] becausematerial's entropy is a gene-like performance indicator. Increasingentropy works as an effective guide to improve microscopicconfiguration that may enhance the crystal structure symmetry,especially for matrix materials having low symmetry structures,e.g. Cu2-xS-based substituted multicomponent compounds (LTphases). From the viewpoint of thermoelectrics, more elements arealways recommended due to multi-scale phonon scattering theory.In addition, the element distributions should be uniform, and nosecondary phases can be found in order to maintain high electricalproperties. When the configurational entropy is high enough, allmulticomponent materials tend to possess a high symmetrystructure. This is well confirmed by a symmetry transition of high-entropy Cu2S1/3Se1/3Te1/3 [95], increasing from the monoclinicFig. 2. (a) CueS phase diagram presents a series of copper-based sulfides in a narrow sulfur ratio of 30%e50%(in mole). (b) The XRD patterns of Cu2-xS crystals at temperatureincreased from RT to 823 K and then decreased to 323 K. Reprinted from Ref. [83], Copyright (2021), with permission from Elsevier Ltd. (c) Band structure and total/partial-DOS of a-Ag2S in the first-Brillouin zone, and the COHP data of AgeS bonding. EF is referenced at the top of the VB. Reprinted figure with permission from Ref. [84], Copyright (2013) by theRoyal Society of Chemistry.F.-H. Sun, H. Li, J. Tan et al. Journal of Materiomics 10 (2024) 218e233structure to hexagonal at RT when the configurational entropy isabove 0.6 kB f.u.�1. High symmetry crystal structures generally havea high band convergence or overlapped bands near the EF due to thehigh symmetry inducingmore equivalent positions in both real andreciprocal space. This can significantly increase the electronicdensity-of-states (DOS) and effective mass (m*), and therebyenhance S. Competitive TE performance was obtained inCu5Sn1.2MgGeZnS9 [96], in which the additional Sn plays animportant role in tuning n and improving S.2.2. Band configuration tuningTrying to tune the band parameters [97] inmetal sulfides has ledto a fruitful strategy to analyze their complex band structures. It canbe engineered either by modifying the relative energy of the elec-tronic bands through alloying or by introducing impurity energylevels that are resonant with the host band through resonantdoping.Lead sulfide (PbS) is a typical member of lead chalcogenides,known as a promising high-performance TE material. Its valenceband is easily regulated, and thereby the band alignment wasachieved with suitable M(4)S (M(4) ¼ Cd, Zn, Ca, Sr and etc.) [98].Simultaneously, carrier scattering is largely suppressed by reducingcarrier transport barriers. As shown in Fig. 3a, a high energy barrierwas caused by the large energy difference (energy offset DE) be-tween the conduction bands (CBs) of PbS and M4S. For p-type case,the degree of hole scattering scales with the size of the valence221band offsets, and decreases with increasing temperature due tothermal band broadening. DE exceeds the magnitude of thermalenergy kBT at HT. It is very useful to facilitate carrier transmissionacross the interface and further modify the carrier mobility in p-type PbS. The intrinsic band structure is a direct band gap in L pointwith valence band (VB) contributed from S 3p and CB from Pb 6p inPbS. However, alloying (like Sn atom) and incorporating withdopant (like PbTe compound) [99] can sharpen the CB shape andnarrow the band gap in n-type PbS, as well as make the CB positionfine alignment, as displayed in Fig. 3b. These help to obtain highelectron mobility (mH) and relatively high effective mass (m*).Furthermore, element doping can introduce a gap state betweenthe CB and VB or an extra CB (Ga/In doping [100]), which inducesFermi level pinning effect. For example, the Ga-doped PbS sets up ahybrid state, Ga 4s and S 3s-3p states, and the Fermi level lies withinits gap states. GaeIn codoping also adds a In 5s state with a smallelectron energy difference of 0.03 eV at L and G points.Tin sulfide (SnS) is a rising star in the TE community due to itsfascinating electronic and acoustic transport features. SnS is amultiple band structure, and its large m* mainly comes from theincreased energy degeneracy (Nv). It is an effectiveway to shape themultiple band structures through alloying specific elements [36].As shown in Fig. 3c, Se-doped SnS, the energy offsets have droppeddramatically over the sharpened VBs. It is also found that the VBstake on the temperature-dependent evolution behavior after Sealloying, including two-band divergence, convergence, andcrossing with increasing temperature. The structure evolution of VBFig. 3. (a) DFT band alignments of the CB and VB energy levels for PbS, CdS, ZnS, CaS, and SrS. Adapted by permission from Ref. [98], Copyright (2012) by the American ChemicalSociety. (b) Designed strategy to synergistically optimize carrier and phonon transport property in PbS with Sn/In/Ga alloying and PbTe incorporation. Reprinted figure withpermission from Refs. [89,90], Copyright by the American Chemical Society. (c) Schematic diagram of electronic band structures for Se-doped SnS, and corresponding dynamic VBsevolution. Adapted by permission from Ref. [36], Copyright (2019) by the Authors, some rights reserved.F.-H. Sun, H. Li, J. Tan et al. Journal of Materiomics 10 (2024) 218e233promotes the electrical transport property, which can be wellevaluated through the weighted mobility mw (mw z mH(md*/me)3/2),herein the md* and me are the density of states effective mass andthe electron mass, respectively.2.3. Anomalous harmonic phonon scatteringThe CuS4 tetrahedron is considered to be the building block orprototype for a variety of ternary and higher-ordered copper-basedsulfides. The simple vertex linking of CuS4 tetrahedra gives rise to azinc blende network, in which ordered cations probably induceformation of supercells. CuM(5)S2 (M(5) ¼ Fe, Al, Ga, In, Tl and etc.)with a chalcopyrite structure adapts a vertex-linked feature. Thereis ordering of Cu (I) and M(5) (III) cations over 4-coordinate sites.Meantime, replacement of one half of M(5) cations produces astannite structure exemplified by Cu2ABS4, tetrahedrons amongCuS4, AS4 and BS4 linking through their vertices. The antifluorite-type structure of Cu5M(5)S4 also generates a network of vertex-linked CuS4, in which a statistical distribution of Cu cations andvacancies separates over the eight available tetrahedral sites.Complex structures are also observed in copper-containingminerals, e.g., colusites, tetrahedrites, famatinites. Colusite can bevertex-linked by CuS4 and BS4 tetrahedra, while the tetrahedrite isoften considered as a complex defective derivative of zinc blende-like network. Each Cu12d atom forms a tetrahedron with four S24gatoms (as shown in Fig. 4a), and Cu12e atom is linked with one S2aand two S24g atoms, forming a basic unit of CuS3 trigonal plane. Sbatom is coordinated with three S24g atoms as an SbS3 trigonalpyramid. The interplay between electronic transport and crystalstructure has been well provided by Long et al. [101] It is revealedthat the Jahn-Teller driven electronic instability results in a markedreduction in the density of states at Fermi level (DOS patterns inFig. 4b). The formation of molecular-like CueS cluster suppressesthe carrier transport, and thereby the electronic conduction iscompelled by variable-range-hopping mechanism among clusters.Lai et al. [102] further calculated the vibration DOS (VDOS in Fig. 4c)222of all atoms at 300 K and 600 K. Both low- and high-energy modeswere observed in the temperature dependent lattice parameters.The low-lying modes revealed quasilocalized sites and significantlyweakened bonding (i.e. Cu12e) due to their low frequency and en-ergy. The calculated atomic displacement parameter (ADP)value ~ 0.143 2 Å2 for tetrahedrite is much larger than Lindemannparameter, leading to a part-crystalline and part-liquid structure.This structural features displays some similarities with those ofcage-based TE materials, such as skutterudites and clathrates.3. High performance thermoelectric binary sulfidesA common electronic structural feature for above-mentionedsulfides resides in a hybridized VB derived from metal (d) and S(3p) orbitals. A high degeneracy of VB results in relatively high Sand thereby PF. The appreciable SIC (particularly, copper and silverion) in many of the complex structures may manifest itself either inrelatively large ADPs or strong delocalization of cation-ions, leadingto the sublattice atoms keeping a liquid-like state, which purposes agreat effect on phonon transport.3.1. Copper sulfideAlthough stoichiometric copper sulfide (Cu2S) is an intrinsicsemiconductor, Cu deficiency easily leads to a p-type behavior. Thecarrier (hole, hþ) concentration dramatically increases withincreasing Cu vacancies, leading to an enhanced s and reduced S.However, the kL values are nearly independent with Cu-deficiencycontents. As summarized in Table 1, a series of Cu2-xS-based ma-terials exhibits superior TE properties with high ZT (�1), which is abenchmark suggesting potential of materials suitable for applica-tions at intermediate temperatures. Among them, a few peak ZTvalues, for example Cu2-xS-3%Pb [83], can reach or even exceed2.0 at HT.It is found that Cu2-x(Se,Te,S) can form a solid solution incomposition ranges from half Se/Te and half S [25,102] or evenFig. 4. (a) Crystallographic units of Cu12Sb4S13 compound. (b) Electronic band structure and partial density of states for tetragonal Cu12Sb4S13. Reprinted figure with permission fromRef. [101], Copyright 2020 by the WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. (c) Vibration density of states of isotropic motion for all atoms and anisotropic motion for Cu12eatoms in Cu12Sb4S13 at both 300 K and 600 K, respectively. Reprinted figure with permission from Ref. [102], Copyright 2015 by the WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.Table 1State-of-the-art thermoelectric properties of Cu2-xS-based materials.Material T (K) ZTmaxa) S (mV/K) s (104 S/m) nHa)(1020 cm�3)mHa)(cm�2$V�1$s�1)k (W$m�1$K�1) kL (W$m�1$K�1) Synthesis methoda) Ref.Cu1.94Se0.5S0.5 1000 2.30 225 2.50 7.900 2.20 0.58 0.21 SSR þ SPS [44]0.31Cu2S-0.69Cu1.96S 932 2.10 220 2.31 9.300 2.40 0.48 0.14 WC [103]Cu2S0.52Te0.48 1 000 2.10 220 1.80 18.000 0.37 SSR þ SPS [28]Cu2-xS-3%Pb 880 2.03 198 2.90 0.49 0.19 HP [83]Cu1.98S1/3Se1/3Te1/3 1 000 1.90 248 1.80 11.200 0.60 0.30 SSR þ SPS [104]Cu1.97S 973 1.90 245 1.20 0.36 MS [105]Cu2SI0.1 973 1.80 220 1.85 0.50 RFIHP [106]Cu1.97S 1 000 1.70 302 0.91 7.300 0.69 0.48 SSR þ SPS [90]Cu1.9Mn0.1S 700 1.63 275 3.90 0.007 1.25 0.61 SSR þ MA þ SPS [107]Cu1.8S-5%(in mass)CoSb3 773 1.60 192 2.15 0.47 SSR þ SPS [108]Cu1.95S 800 1.56 321 1.40 2.300 6.11 0.66 0.46 FVIR [109]Cu2-xS-0.75%Graphene 873 1.56 163 4.50 13.000 1.25 0.64 0.10 MA þ SPS [110]Cu1.9Fe0.0325S 1 000 1.50 262 1.48 1.100 2.20 0.62 0.41 SSR þ SPS [111]Cu2-xS 710 1.41 248 1.70 0.600 0.62 0.33 HP [112]Cu1.8Se3%In2S3 773 1.40 112 8.70 4.400 0.65 0.33 MA þ SPS [113]Cu1.94S 773 1.23 205 1.90 3.200 4.10 0.45 0.24 MA þ SPS [114]Cu2Se2%In2S3 850 1.23 198 2.65 2.400 5.80 0.98 0.47 SPS [115]Cu1.8Se1%WSe 773 1.22 110 8.00 7.800 19.50 0.68 MA þ SPS [116]Cu1.8Sb0.02Sn0.03S 773 1.20 173 3.10 5.100 2.70 0.60 MA þ SPS [117]Cu1.95SeNaOH 833 1.10 212 2.20 80.000 0.71 0.41 WC þ SPS [118]Cu1.8Na0.05S 773 1.10 112 7.53 59.500 26.90 0.76 MA þ SPS [119]Cu2S 873 1.07 275 0.80 1.100 0.47 0.37 CP [120]Cu2S 873 1.07 270 1.07 2.300 1.40 0.47 0.36 MA þ SPS [121]Cu2-xS-0.25%C 773 1.04 191 1.70 1.300 5.80 0.47 0.22 WC þ SPS [122]Cu1.96S 773 1.01 230 1.60 0.68 HTS þ MA þ SPS [123]Cu1.8Se1%Ru 773 1.00 120 9.00 4.500 14.50 1.05 MA þ SPS [124]Cu2-xS 800 1.00 152 4.10 2.300 8.28 0.75 0.19 WC þ SPS [125]90%Cu2Se10%Cu5FeS4 900 1.00 205 1.75 0.76 SSR þ HP [126]a) ZTmax is the peak ZT at each optimal temperatures, nH (ne) and mH (me) are hole (electron) concentration andmobility, SSR is solid state reaction, SPS is spark plasm sintering,HP is hot pressing, MS is melt solidification, RFIHP is radio frequency-introduced hot pressing, MA is mechanical alloying, FVIR is flash vacuum-induced reaction, WC is wetchemical method, CP is cold pressing, HTS is hydrothermal synthesis, respectively.F.-H. Sun, H. Li, J. Tan et al. Journal of Materiomics 10 (2024) 218e233down to one third of Se/Te/S [104] using Cu2S, Cu2Se, and Cu2Tenanocrystalline specimen. These solids are solved as hexagonalstructures with space group R 3 m. Actually, these compounds arequasi-single crystals consist of a variety of 10e30 nmmosaic grains(Fig. 5a), possessing a unique hierarchical microstructurecomposed of mesoscale polymorphs, nanoscale domains andmodulations. Due to the absence of boundary or interface223scattering, as presented in Fig. 5b, mosaic crystals have dramaticeffects on the charge carrier and phonon transport behaviors.Combined with a low sound speed originating from the intrinsicliquid-like Cu ions at HT, an ultralow k is achieved (almost0.4 W$m�1$K�1, as shown in Fig. 5c). Furthermore, high PF values(PFmax ¼ 13.2 mW$cm�1$K�2) are observed due to a high weightedmobility, which is similar to that of copper selenides [127]. AllFig. 5. (a) Phase mapping and grain size distribution in Cu2(Se,S) compound. (b) Structural characteristics of a single crystal, a usual polycrystal, and a mosaic crystal. Reprintedfigure with permission from Ref. [28], Copyright 2015 by the WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. (c) Seebeck coefficient S as a function of Hall carrier concentration at1 000 K, and temperature dependence of PF, k, and ZT for CueSeeS compounds. Reprinted from Ref. [44], Copyright (2017), with permission from Elsevier Ltd.F.-H. Sun, H. Li, J. Tan et al. Journal of Materiomics 10 (2024) 218e233favorable factors lead to an improved quality factor (B) and then TEproperties in Cu2-x(Se,Te,S) compounds. Finally, a peak ZT value of2.3 was received, which is the highest values in bulk polycrystallinesulfides.Many studies focus on suppressing the phase transitions and Cusegregation for Cu2-xS compounds through alloying Cu sites withlight atoms [107,117], introducing nano-inclusions, encapsulatingthin carbon-shell Cu2-xS@C [122] or Cu2-xS@graphene [110],informing in-situ nanophases induced from In2S3 [115] or WSe[116], and dispersing nanoparticles of Cu2-xS-Ru [124], Cu2Se-Cu5FeS4 [126] or Cu2-xS-NaOH [118]. These composites show anevident improvement of both PF and ZT values due to simulta-neously optimized n and reduced phase transition temperature.Along with the structure stabilization, sulfur volatilization andcopper segregation, high TE performance together with large PFand ZTave [120] values in Cu2-xS will be beneficial to its practicalapplications in TE devices.3.2. Lead sulfideThe quest to achieve high TE performance, low-cost and earth-abundant PbS remains an open opportunity to explore. Its propertycan be enhanced by tailoring the chemical bonding and modifyingnanostructures. As compared to PbSe and PbTe, PbS has higherdeformation potential at similar doping level due to the strongerelectron-phonon coupling. The approaches of elaborately opti-mizing m* and nH to improve the electrical transport are wellvalidated in PbS systems. Meanwhile, nH optimization can effec-tively balance S and s, and thereby produce a high average PF(PFave). Recently, as presented in Table 2, many efforts have beenmade to improve TE properties with ZT over 1.0 for n- and p-typePbS-based materials at optimal temperatures. nH and kL have beenwell optimized by doping and nanostructuring, such as Na, K, Ag,Cu, Te doping or codoping, and/or Cd/Sr/CaS, Cu2S nanostructuringetc. in p-type compounds. Zhao et al. [98,128,129] have investigatedthe effect of endotaxially nanostructured ZnS, CaS, CdS, and SrS onthe TE properties of Na-doped p-type PbS in detail. Fig. 6a is a high-resolution transmission electron microscopy (HRTEM) image of thePb0.975Na0.025Se3%CdS sample. The nanograin shows random dis-tribution of irregularly sized precipitates. The average precipitate224size is about 4 nm. It is confirmed that these nanostructures arelattice-matched, isostructural to PbS with endotaxially orientation.Furthermore, the elastic strain maps present pervasive stain fielddistribution in and around the precipitates. The line scanningprofile shows a maximum 6% difference in lattice parameter at thephase interface. By means of a closely coupled phonon-blocking/electron-transmitting approach through embedding endotaxiallynanostructured second phases in PbS system, as shown in Fig. 6b,ZT values are obviously improved in the entire temperature ranges.A record high ZT of ~1.3 in Pb0.975Na0.025Se3%CdS has been realizedat 923 K (see Table 3).Compared with p-type PbS, n-type materials face huge chal-lenges in improving PF due to a single CB transmission, indicatingthat improvement through the well-known approaches (forexample band convergence) is hardly possible. Hence, TE proper-ties of n-type PbS-based alloys can be only enhanced from theperspectives of improving s and lowering k. Engineering certainelectronic states [89,90] is the common strategies to enhance s, anddesigning novel nanostructures [132,139] and/or multiple defects[146,134] can effectively suppress kL. Sometime, the secondaryphase inclusions trigger a valence disproportionation [135] of metalcations, preserving high mH. Finally, an extraordinary ZT of 1.7 in n-type part was realized both Pb0.93Sb0.05S0.5Se0.5 [132] and PbS-4.4%Ag [133].3.3. Tin sulfideSn-based sulfides came into the sight of TE researchers due toboth high s originating from the high in-plane carrier mobility andultralow k deriving from the strong lattice anharmonicity. Li et al.[151] successfully synthesized pristine SnS bulk using a simpleMA þ SPS method in 2014, and firstly reported a relatively high ZTof 0.16 at HT. They also revealed that the microstructure and TEproperties were independent of the stoichiometric ratio and sin-tering temperature because of the decomposition of redundant Scontent in powder. Adjusting Na-doping content via wet chemical(WC) synthesis [152] leads to a state-of-the-art PF of3.62 mW$cm�1$K�2 for the polycrystalline at 873 K, and therebyraises ZT value up to 0.52. Recently, it is found that heterovalent ormonovalent cation doping (such as Naþ [149] and Agþ [148]) in SnTable 2State-of-the-art thermoelectric properties based on PdS materials.Material T (K) ZTmax ZTave.b) S (mV/K) s (104 S/m) nH (1019 cm�3) mH (cm�2$V�1$s�1) k (W$m�1$K�1) kL (W$m�1$K�1) Preparation Ref.p typePb0.975Na0.025Se3%CdS 923 1.30 296 1.47 4.75 130 0.78 0.62 SSR þ SPS [98]Pb0.975Na0.025Se3%SrS 923 1.22 221 1.70 4.55 93 0.77 0.65 SSR þ SPS [128]Pb0.99Cu0.01Se1%Cu 773 1.20 0.79 263 2.20 2.10 470 0.85 0.65 SSR þ SPS [130]Pb0.98Na0.02Se2%Cu2S 823 1.20 304 1.66 2.10 164 0.89 0.72 SSR þ SPS [129]Pb0.975Na0.025Se3%CaS 923 1.12 220 1.71 4.81 97 0.76 0.72 SSR þ SPS [128]Pb0.81Ag0.16K0.03Te0.33S0.67 620 ~1.00 182 0.98 1.00 0.41 WC þ RFIHP [131]n typePb0.93Sb0.05S0.5Se0.5 900 1.70 �181 4.05 3.80 138 0.81 0.30 SSR þ SPS [132]PbS-4.4%Ag 850 1.70 �220 4.90 3.00 90 0.79 WC þ RFIHP [133]Pb0.9Ge0.1S 900 1.45 �315 1.16 1.48 168 0.63 0.54 SSR þ SPS [134]Pb0.985Sb0.015S-14%GeS 923 1.32 0.76 �276 1.62 3.00 121 1.31 0.61 SSR þ SPS [135]Pb0.94Sn0.06Se8%PbTe 923 1.30 0.72 �247 2.40 6.18 147 0.97 0.62 SSR þ SPS [99]Pb0.95Sb0.02Cu0.03Se3%Cu 923 1.23 0.62 �189 1.60 2.11 28 0.88 0.59 SSR þ SPS [136]Pb0.955Cu0.045S 773 1.22 0.76 �275 2.05 2.52 123 0.96 0.63 WC þ SPS [137]PbSe3%SrSe1%PbCl2 930 1.20 0.78 �226 2.40 7.70 117 0.77 0.65 SSR þ SPS [138]PbSe5%Cu 750 1.10 0.72 �248 2.10 2.10 153 1.12 0.70 WC þ SPS [139]Pb0.99Ga0.01(S,Se,Te) 723 1.10 0.73 �254 1.97 2.35 398 1.01 0.66 WC þ SPS [140]Pb0.995In0.005Se3%Cu 723 1.10 0.80 �226 2.60 8.40 110 1.23 0.76 SSR þ SPS [141]PbSe3%CaSe1%PbCl2 930 1.10 0.80 �234 1.65 6.30 101 0.72 0.61 SSR þ SPS [138]PbSe1%B2S3e1%PbCl2 923 1.10 �221 2.52 1.12 0.64 SSR þ SPS [142]PbS Nanocrystal 838 1.06 �187 3.98 1.73 40 1.13 0.56 WC þ SPS [143]PbCl0.015S0.985 800 1.04 �230 2.04 0.82 0.55 WC þ MS [144]Pb0.995In0.005Se5%Ni 823 ~1.00 0.66 �213 3.04 7.50 264 1.41 0.85 SSR þ SPS [145]PbS-0.067%PbCl2-1.5%Sb 823 ~1.00 0.62 �223 2.56 4.50 1.13 0.74 PAS [146]Pb0.9865Ga0.0125In0.001S 923 ~1.00 0.74 �275 2.10 0.98 0.76 SSR þ SPS [100]Pb0.98Sb0.02(S,Se,Te) 923 ~1.00 �219 2.60 1.21 0.80 SSR þ SPS [147]b) ZTave is the average ZT in temperature ranges and PAS is plasma activated sintering respectively.Table 3State-of-the-art thermoelectric properties of p-type SnS-based materials.Material T (K) ZTmax ZTave. S (mV/K) s (104 S/m) nH (1019 cm�3) mH (cm�2$V�1$s�1) k (W$m�1$K�1) kL (W$m�1$K�1) Preparationc) Ref.SnS0.91Se0.09 Crystal 873 1.60 1.25 376 0.83 2.80 310 0.69 0.51 SSR [36]Sn0.99Ag0.005S 877 1.10 365 0.29 0.43 3.78 0.34 0.31 MA þ SPS [148]Sn0.98Na0.02S Crystal 870 1.10 0.54 353 0.58 2.30 102 0.63 0.52 BM [149]2%hole-dopedSnS Crystal873 1.01 380 0.55 3.70 98 0.76 0.75 SSR [150]c) BM is Bridgman method.Fig. 6. (a) High resolution TEM image and stain maps of Na-doped PbS compound added by 3.0% SrS. Reprinted figure with permission from Ref. [128], Copyright 2012 by theAmerican Chemical Society. (b) Temperature dependence of TE properties for Pb0.975Na0.025S sample with 3.0% metal sulfides (CdS, ZnS, CaS and SrS). Adapted from Ref. [98],Copyright 2012 by the American Chemical Society.F.-H. Sun, H. Li, J. Tan et al. Journal of Materiomics 10 (2024) 218e233225F.-H. Sun, H. Li, J. Tan et al. Journal of Materiomics 10 (2024) 218e233sites can obviously elevate n. ZT values are strikingly promoted,exceeding 1.0 in Na-doped SnS crystals [150] and even reaching 1.6after further Se alloying [36]. The TE performance in SnS crystals issuperior to the polycrystalline materials.4. New polysulfides and thermoelectric enhancementMetal polysulfides also present a hybridized electronic bandstructure (particularly VB), usually deriving from M 3d and S 3porbitals. High VB degeneracy leads to a relatively high PF. Comparedwith binary sulfides, polysulfides possess more complex structures,indicating a relatively larger ADPs. This may lead to the cation ionsublattice attaining a liquid-like state, with a huge impact on the k.4.1. TetrahedriteTetrahedrite materials (based on Cu12Sb4S13) represent twoholes per formula unit, accounting for p-type metallic behavior attemperature above 85 K. They have great advantage in comparisonto other state-of-the-art TE sulfides, composing of light, non-toxicelements of Cu and S. It is natural earth-abundant minerals,possibly lowering production cost. As for TE study, Suekuni et al.[153] firstly synthesized tetrahedrite sample and investigated its TEperformance. A high ZT ¼ 0.15 was received at near RT due to thedecreased k as Ni doping. Relatively, S displays a small value. Sub-sequently, considerable efforts have been directed towardimproving PF through partial substitution at Cu and/or Sb sites.General formulas of Cu12-xM6xSb4S13 (0 � x � 2) andCu12Sb4-yM7yS13 (0 � y � 1) have been prepared for a wide range ofsubstituents.M6 stands for the transition-series elements of Fe [154],Co [155,156], Ni [157], Zn [158], Mn [159], Cr [160] and Cd [161], thegroup of IVA elements Sn [162] and Pb [163], and the third periodelementsMg [164] and Al [165].M7 is generally Ge [166], Sn [167], Bi[168], As [169], and Te [170] elements. Table 4 presents the maximalTE properties at optimal temperature. Substitution of copper and/orantimony results in an addition of electrons based on the top of VB,altering the band degeneracy in vicinity of the EF and further raisingbandgap (Eg). Double substitution of copper [171,172] or sulfur [173]sitesappears tobeparticularlyeffective inenhancingTEperformance,with ZT values closing to or even exceeding 1.0 at their optimaltemperatures. Sometimes, introduction of Se atoms [174e176] in Ssites can balance the electrical and thermal transport properties.Briefly, the aimof elemental doping is to reducen so that PFmax iswelloptimized and thereby receives a relatively high ZT value.Introducing nanostructures into TE tetrahedrites is an effectiveapproach for decreasing kL due to the strong low/middle-frequencyphonon scattering. Compositional fluctuations on the endotaxialnanointerfaces between nanoregions and matrix can probablydecrease the thermal transport and maintain a relatively high PF.Table 4State-of-the-art thermoelectric properties of p-type tetrahedrites.Material T (K) ZTmax S (mV/K) s (104 S/m) k (WCu11.5Ni0.5Sb4S13-0.7%BiI3 723 1.15 154 5.60 0.83Cu11.5Ni0.5Sb4S13-0.3%Nb2O5 723 1.15 172 5.40 1.20Cu11MnSb4S13 575 1.13 142 2.60 0.26Cu13.5Sb4S12Se 723 1.10 177 3.90 0.81Cu11.5Zn0.5Sb4S13 723 1.09 247 0.78 0.31Cu10.5NiZn0.5Sb4S13 723 1.03 210 1.96 0.51Cu11.7Gd0.3Sb4S13 749 ~1.00 153 6.45 1.28Cu11.5Ni0.5Sb4S13e1%Fe2O3 700 ~1.00 168 3.90 0.79Cu12Sb3.65Sn0.35S13 673 ~1.00 182 3.85 0.87Cu12Sb3.96Ge0.04S13-0.5%ZnO 750 ~1.00 152 5.28 0.93Cu11.5Co0.5Sb4S13 673 ~1.00 166 6.62 1.19Cu11.5Co0.5Sb4S13 673 ~1.00 166 5.88 1.21226Li's research group [38] has demonstrated a new strategy to pre-pare porous tetrahedrite-based TE materials with excellent elec-trical and thermal properties. They also have found thatintroducing a small amount of metallic oxide nanoparticles (NPs)into matrix achieves a significantly reduced k, <1.1 W$m�1$K�1over the entire temperatures, and thereby obtained a highest ZT~1.2 at 723 K [177] (as shown in Fig. 7). These NPs include Nb2O5[177], Fe2O3 [179], BiI3 [38], ZnO [180], and etc.4.2. ColusiteRecently, colusite-related TE materials with sphalerite-derivative structure are of interest for TE community because oftheir complex cationic distribution, rich crystal structure, numeruschemical active site and potential energy conversion application.Colusite family is represented by a generic formula ofCu26T2M(8)6S32 (T ¼ V, Nb, Ta, Fe, Ti, Cr, Mo and W, M(8) ¼ Sb, Geand Sn) [54,181]. Its structure exhibits a complex cation distributionand a fascinating interplay between the corner sharing CueStetrahedral network and T sites. Band structure calculation[182,183] reveals that the Fermi level penetrates into the VBmanifold. The electronic states near the top of VB derive from S 3pand Cu 3d orbitals, whereas the minimum of CB is composed of Tand S orbitals. A large number of atoms in a cell lower the groupvelocity of the optical modes and thereby reduce the heat transportefficiency by acoustic modes. It is benefit for low k. Indeed, Suekuniet al. [69] first reported an extremely low kL value of0.6 W$m�1$K�1 at 350e663 K, maintaining a relatively high PF of6.1 mW$cm�1$K�2 at 663 K. The combination of low kL and rela-tively high PF promotes ZT closing to or even exceeding 1.0 ataround 700 K in colusite-based Cu26V2Sn6S32 [67], Cu26Nb2Ge6S32[68], Cu26Ta2Sn5.5S32 [68], and [Cu26Cr2Ge6]1.024S32 [184].4.3. Other metal based sulfidesIn natural minerals, two ecofriendly elements (copper and sul-fur) often appear, usually combining with other elements such asSb, Sn, In, Ti, Bi, of Pb and transitionmetal elements of Mn, Fe, or Co.Most of these minerals (sulfides) do not suffer from Cu liquid-likeelectromigration behavior, and are considered as promisingapplication-driven TE materials at mid-temperatures. However,they exhibit complex phases in synthesized compounds or undergophase transitions in experimental processes, leading to a relativelylow PF. These structural merits motivated great efforts to usechemical manipulation to improve TE properties of bornite [185],thiospinel [66], pavonite [186], famatinite [51], paracostibite [187],and other sphalerite-derived sulfides [188e190], in which bothcarrier concentration and vacancy levels were well modified.Incorporation with dehydrated attapulgite nanorods, p-type Co-$m�1$K�1) kL (W$m�1$K�1) Preparation Ref.0.13 MA þ SPS [38]0.36 MA þ SPS [177]SSR þ SPS [159]0.22 SSR þ Annealing þ SPS [174]0.18 WC þ SPS [178]0.39 SSR þ MA þ CP þ Annealing þ HP [171]0.46 CP þ Annealing þ HP [161]0.31 MA þ SPS [179]0.45 CP þ Annealing þ MA þ SPS [167]0.25 SSR þ Annealing þ HP [166]0.48 SSR þ Annealing þ HP [155]0.49 SSR þ CP þ Anealing þ HP [156]Fig. 7. (a) Schematic illustration presents the formation of BiI3/Cu12Sb4S13 porous composites. Reprinted figure with permission from Ref. [38], Copyright 2021 by the WILEY-VCHVerlag GmbH & Co. KGaA, Weinheim. (b) Temperature dependence of TE properties for a series of Cu12Sb4S13-xNb2O5 nanocomposites. Adapted from Ref. [177], Copyright 2018 bythe Elsevier Ltd.F.-H. Sun, H. Li, J. Tan et al. Journal of Materiomics 10 (2024) 218e233doped Cu2Sn0.8Co0.2S3 [41] exhibited an enhanced S, high PF~9.4 mW$cm�1$K�2, and ultralow kL of 0.27 W$m�1$K�1. Finally, ahigh ZT of ~1.0 has been achieved at 773 K. Through Br dopant-induced phase transition [43], a quasi homo-composition andhetero-structure nanocomposite based on n-type Bi2SeS2 provideda coherent interface and synergistically tuned electrical and ther-mal transport properties (ZTmax ¼ 1.12@773 K). Using Cu and I asthe dual carrier providers [191] suppresses the phonon transportand promotes electrical performance, and also results in an excel-lent ZT of 1.04.5. Synthesis recipes of thermoelectric sulfidesIn this short section, we review some production processes of TEsulfides. Typically, they have been synthesized by one of thefollowing methods [192]: MA, multi-step SSR, FVIR, and bottom upmethod combined sintering process.MA is a relatively rapid method, which has attracted great in-terests for many years in TE field. It is one of the most effectivepowder processing technique. Usually, the start chemicals withhigh purity are mixed according to nominal composition in a dryinert atmosphere, charged to an alloy jar containing balls, and seton a ball milling machine at high speed for a specific duration. TheMA-derived powders are subsequently sintered by SPS or HP. Thenthe consolidated compounds with relatively high density are ob-tained. MA process gives a high-energy impact on particles227involved cold-welding, fracturing and re-welding, leading tofurther pulverization. Therefore, it occupies an important role in TEmaterials, particularly in producing fine-grained composites [193],nanostructure-derived hetero-alloys [110], in-situ nano-defect ar-chitecture compounds [194], and etc. Due to the high-energymilling effect, vacancy engineering provides a huge possibility intuning carrier concentration, effective mass and mobility, forexample Ag-doped polycrystalline SnS [148]. It obtains a high PF of4.25 mW$cm�1$K�2. Incorporating heterogeneous Cu4SnS4 phase[117], hole concentration was well optimized, and a reduced kL wasachieved in Cu12Sb4S13. Substantially, receiving an enhanced TEperformance (ZT¼ 1.2@773 K). MA is greatly effective to strengthenphonon scattering and thereby significantly reduce k. g-Fe2O3-dispersed tetrahedrite [179] achieves an ultralow k,~0.9 W$m�1$K�1 over the entire temperature range, and henceleads to a high ZT up to 1.0, which increases by ~33%.SSR technique is a conventional method for producing TE ma-terials. In laboratory, typically evacuated ampoules are used tosynthesize TE ingots on a gram scale. It deserves several pre-treatments including cleaning quartz tube, coating wall whenvolatile elements are involved, and baking probable organic resi-dues. As followed by grounding the ingots into a fine powder, cold/hot pressed or SPS, and then annealed, the mixed start chemicalsare melted in a furnace and subsequent cooling. Preparing TE ma-terials, some post-treatments, like regulating cooling rate, are alsosignificant in order to control the morphologies and/or crystal sizemailto:1.12@773mailto:1.2@773F.-H. Sun, H. Li, J. Tan et al. Journal of Materiomics 10 (2024) 218e233of as-synthesized ingots. It has been widely studied by variousresearch groups, optimizing the conditions of melting, annealingand pressing procedures and investigating the promotional effectson tuning electrical and thermal transport performance. Forexample, Cu2Se and Cu2S can form a solid solution [44] using SSRmethod at HT to order to ensure compositional homogeneity. Itpossesses a unique hierarchical microstructures composed ofmesoscale polymorphs, nanoscale domains and modulations. Allthese favorable factors lead to a much enhanced PF and yield aremarkably ZT value of 2.3. Jiang et al. [132] introduces zigzagnanoprecipitates with a uniformwidth of ~1.0 nm into n-type PbS-based TE material, which leads to an ultralow kL of 0.4 W$m�1$K�1.Similarly, carefully controlling the composition and reaction con-dition, high-quality p-type SnS crystals [36] were prepared, andshow a boosted PF of 53 mW$cm�1$K�2 at RT, which achieves thehighest ZT of 1.6@876 K.FVIR represents a non-equilibrium synthesis technique with theadvantages of rapid processing, good scalability, and energy sav-ings. Tang's research group [195,196] systematically studied the keyparameters governing the FVIR processing, and reported a widerange of FVIR-synthesized TE materials. Typically, high-puritymetal powders were used as raw materials, mixed and cold-pressed into a pellet, and then sealed in a quartz tube. The FVIRprocess is initiated by point heating a small part of the sample.Once the ignition starts, the combustion wave passes through theremaining sample because the liberated heat of fusion in one sec-tion is sufficient to maintain the reaction in the neighboring region.The propagation of the combustion wave is fast, typically on thetimescale of seconds. As FVIR-induced product is ground intopowder, and then sintered again. Finally, robust TE bulks are ob-tained. the FVIRmethod could be used for the ultra-fast synthesis ofmetal sulfides, in which the composition could be controlled pre-cisely. Combining FVIR with subsequent SPS process, BiAgSeS [197]multicomponent material was prepared. The non-equilibrium FVIRprocess provides an effective step to promote crystal grain growthand shape regular nano- and atomic-scale strain field regions at thegrain boundaries. Then, the extreme low kL was obtained,<0.7 W$m�1$K�1 in the whole temperature ranges, receiving highZT of 0.5 at 773 K. High purity Cu1.95S bulks with tunable compo-sitions were prepared using FVIR method, and achieved a high ZT of1.56 at 800 K [109].Abovementioned processes are top down approaches to prepareTE materials, which have the feature of being somewhat energy-consuming. In order to precisely control the particle size, crystaldistribution and morphology, bottom up method provides a low-cost route towards TE materials. The primary advantages lie in itsversatility in designing various nanostructures, which is favorablefor phonon scattering. Wet chemical synthesis provides a widevariety of nanoscaled architectures with high quality of phase pu-rity, crystallinity, and density. For instance, PbS quantum dots (QDs)[198], the size varies from 0.5 to 5.5 nm, were successfully syn-thesized by an aqueous solution method. Eg can be changed bytuning synthesis parameters in order to improve TE properties. Asynergized soft template-oriented attachment strategy was used tofabricate ZnS quantum wires (QWs) [199], and a typical width wasonly 0.8 nm. The monodisperse plasmonic and nonplasmonic I-IV-VI nanocrystals (NCs) [200] were synthesized and preciselycontrolled using a solvothermal method. Manipulating the chem-ical properties of cation precursors, the Eg of NCs decreased linearlyfrom 2.1 to 1.2 eV MoS2/MoO3 hierarchical structures can be easilysynthesized by hydrothermal method [201], and represented a highs due to the zero-barrier charge injection at MoS2/MoO3 interface.Finally, a maximum ZT of 1.18 at 600 K was achieved. Core-shell-structured Cu5FeS4 icosahedral NPs [202] with high-density twinboundaries were synthesized by using a colloidal solution method.228Orthorhombic and cubic Cu5FeS4 comprise the core and shellstructures, respectively, exhibiting a promising ZT of ~0.62 at 710 K.TiS2/C60 nanosheets [203] were fabricated by a solid-state reactionwith a fine-grinding process, in which a competitive ZT of ~0.3 canbe achieved at 400 K, mainly derived from the improvement of PFand reduction of kL. It is worth mentioning that liquid-based syn-thesis towards high quality TE nanomaterials still remains a chal-lenge because of its low yield in most cases. Scale productionrequires automated processes with high NP contents in solution,low-cost and nontoxic precursors, solvents and surfactants, as wellas the recycling side-products. Moreover, the final products usuallycontain some undesired impurity phases from pollution of organicsolvents.6. Conclusion and outlookIn this review, we give an overview of research progress onhigh-performance TE sulfides. The significant improvements andestablished records of ZT have been achieved in both n- and p-typeTE alloys by carefully carrier concentration regulation, band struc-ture manipulation, and phonon scattering. We discuss how thesestrategies have been validated on eco-friendly metal sulfides,including CueS or Cu-based, SnS, MoS2 and BieS based binarysulfides and polysulfides, and lead based sulfides to improve theirTE performance. In addition, materials fabrication methods andprocess technologies have been discussed in order to discovery newphysical mechanisms, and thereby further facilitate the emergenceof high-performance sulfides. Despite of colossal research progresson some potential candidates, there is still a long way to go beforegetting ready for commercialization.For nanostructure-modified sulfides, the homogeneous phasedispersion is required. To avoid the solubility, especially low-dimensional inclusions, the constituent phases should be chemi-cal, environmental, and thermal stability during the fabrication andoperation processes. It will be also highly valuable for developmentof advanced, practical and high-performance TE technologies tounderstand fundamental mechanisms of electrical and thermaltransport properties in nanostructured sulfides. Furthermore, it isdesirable to understand the hetero-interfaces of promising sulfidesat atomic scale using some advanced spectroscopic techniques,combined with insights rendered by an interatomic potentialapproach of first principles calculations or even machine learning.We note that there is considerable progress on ZT improvementof inorganic and hybrid organic-inorganic TE materials over thepast decade. However, the development of corresponding TE gen-erators (TEGs) and modules, especially at mid to high temperature(600e1 100 K), has proceeded very slowly. To date, the number ofcommercially available TEGs is very small and affects only very fewniche applications. These TEGs still use bismuth and lead telluridealloys. Taking Cu2-xS as an example, p-type parts present highlypromising TE properties with ZT¼ 2.3 at 1000 K due to high PF andintrinsically low kL. However, these materials show poor compati-bility with other state-of-the-art n-type TE parts, which are difficultto prepare segmented modules in mid temperature ranges.Furthermore, the key technical challenges of TE Cu2-xS alloys,relating to the mechanical stability and the long-term chemicalstability, must bemaintained for at least ten years (especially on thehot generator side). This extreme environment sets maybe destroyits TEG modules. Strategies, employing electrically conductive bution-blocking all-scale structural architectures, show that Cu ionelectromigration can be effectively hindered, potentially allowingstable devices. The gap between laboratory research and devicefabrication must be narrowed by reliable materials properties andwell-matched electrodes and barrier materials. Good mechanicalproperties have rarely been addressed yet, including Vickersmailto:1.6@876F.-H. Sun, H. Li, J. Tan et al. Journal of Materiomics 10 (2024) 218e233hardness, fracture toughness, thermal expansion coefficient, andetc. Moving forward to realize widespread commercial interest,fabricating both p-type and n-type counterparts for given materialneeds to be taken into account. Although some binary sulfides(such as PbS and SnS) have already been researched widely, the restare yet to be explored more.Therefore, any breakthrough in any of the aforementioned as-pects will undoubtedly be an important step forward to improve TEperformance and thereby making reliable TEGs. Currently, thefabrication of commercial p-type modules is fully automated ateach step and is capable of mass production. The potentials focus onBi2Te3-based alloys and TE cooling (TEC) applications. Therefore,the development of stable metallized TEG legs at high temperatureduring operation is a problem, especially for TE sulfides, and mustbe mitigated or suppressed by developing effective strategies.Recent attentions, raising the toughness and fracture strength ofhigh-ZT sulfides, reducing thermal expansion coefficients across theinterfaces between TEmaterials and contact layers, developing newmetal electrodes matched metal sulfides, will define the lifetime ofTEGs, which will have to be of the crucial tasks for practicalapplication. We are optimistic that future research focusing ondesigning better and novel TE sulfides with enhanced performanceand achieving meaningful advances in broad-based TE moduledevelopment.Declaration of competing interestThe authors declare that they have no known competingfinancial interests or personal relationships that could haveappeared to influence the work reported in this paper.AcknowledgementsThis work was supported by the National Natural ScienceFoundation of China, China (No. 52202232), the JST Mirai Program,Japan (No. JPMJMI19A1), the Natural Science Foundation of HubeiProvince, China (No. 2022CFB937), the Guangdong Basic andApplied Basic Research Foundation, China (No. 2020A1515110251),and the CAS Key Laboratory of Cryogenics, TIPC, China (No.CRYO202204).References[1] Yan Q, Kanatzidis MG. High-performance thermoelectrics and challenges forpractical devices. Nat Mater 2022;21(5):503e13.[2] Freer R, Powell AV. Realising the potential of thermoelectric technology: aroadmap. J Mater Chem C 2020;8(2):441e63.[3] Mao J, Chen G, Ren Z. Thermoelectric cooling materials. Nat Mater2021;20(4):454e61.[4] Hendricks T, Caillat T, Mori T. Keynote review of latest advances in ther-moelectric generation materials, devices, and technologies. Energies2022;15(19):7307.[5] Chen W-Y, Shi X-L, Zou J, Chen Z-G. Thermoelectric coolers for on-chipthermal management: materials, design, and optimization. Mater Sci Eng R2022;151:100700.[6] Hu B, Shi X-L, Zou J, Chen Z-G. Thermoelectrics for medical applications:progress, challenges, and perspectives. Chem Eng J 2022;437:135268.[7] He J, Tritt TM. Advances in thermoelectric materials research: looking backand moving forward. Science 2017;357(6358):eaak9997.[8] Gayner C, Kar KK. Recent advances in thermoelectric materials. Prog MaterSci 2016;83:330e82.[9] Wei JT, Yang LL, Ma Z, Song PS, Zhang ML, Ma J, et al. Review of current high-ZT thermoelectric materials. J Mater Sci 2020;55(27):12642e704.[10] Pei J, Cai B, Zhuang HL, Li JF. Bi2Te3-based applied thermoelectric materials:research advances and new challenges. Natl Sci Rev 2020;7(12):1856e8.[11] Rowe DM. Thermoelectrics, an environmentally-friendly source of electricalpower. Renew Energy 1999;16(1e4):1251e6.[12] Pei Y, Shi X, LaLonde A, Wang H, Chen L, Snyder GJ. Convergence of electronic229bands for high performance bulk thermoelectrics. Nature 2011;473(7345):66e9.[13] Pei YZ, LaLonde AD, Wang H, Snyder GJ. Low effective mass leading to highthermoelectric performance. Energy Environ Sci 2012;5(7):7963e9.[14] Li JH, Tan Q, Li JF, Liu DW, Li F, Li ZY, et al. BiSbTe-based nanocomposites withhigh ZT: the effect of SiC nanodispersion on thermoelectric properties. AdvFunct Mater 2013;23(35):4317e23.[15] Li JF, Liu WS, Zhao LD, Zhou M. High-performance nanostructured thermo-electric materials. NPG Asia Mater 2010;2(4):152e8.[16] Khan AU, Kobayashi K, Tang D-M, Yamauchi Y, Hasegawa K, Mitome M, et al.Nano-micro-porous skutterudites with 100% enhancement in ZT for highperformance thermoelectricity. Nano Energy 2017;31:152e9.[17] Zheng Z-H, Shi X-L, Ao D-W, Liu W-D, Li M, Kou L-Z, et al. Harvesting wasteheat with flexible Bi2Te3 thermoelectric thin film. Nat Sustain 2023;6(2):180e91.[18] Yang B, Zhang Y, Pan H, Si W, Zhang Q, Shen Z, et al. High-entropy enhancedcapacitive energy storage. Nat Mater 2022;21(9):1074e80.[19] Zhao W, Wei P, Zhang Q, Peng H, Zhu W, Tang D, et al. Multi-localizationtransport behaviour in bulk thermoelectric materials. Nat Commun 2015;6:6197.[20] Zhao LD, Hao S, Lo SH, Wu CI, Zhou X, Lee Y, et al. High thermoelectricperformance via hierarchical compositionally alloyed nanostructures. J AmChem Soc 2013;135(19):7364e70.[21] Pomrehn GS, Zevalkink A, Zeier WG, van de Walle A, Snyder GJ. Defect-controlled electronic properties in AZn2Sb2 Zintl phases. Angew Chem, Int Ed2014;53(13):3422e6.[22] Liu Z, Sato N, Gao W, Yubuta K, Kawamoto N, Mitome M, et al. Demon-stration of ultrahigh thermoelectric efficiency of ~7.3% in Mg3Sb2/MgAgSbmodule for low-temperature energy harvesting. Joule 2021;5(5):1196e208.[23] Hu L, Fang YW, Qin F, Cao X, Zhao X, Luo Y, et al. High thermoelectric per-formance enabled by convergence of nested conduction bands in Pb7Bi4Se13with low thermal conductivity. Nat Commun 2021;12(1):4793.[24] Liu Z, Gao W, Oshima H, Nagase K, Lee C-H, Mori T. Maximizing the per-formance of n-type Mg3Bi2 based materials for room-temperature powergeneration and thermoelectric cooling. Nat Commun 2022;13(1):1120.[25] Zhang Y, Li J, Hu WW, Yang XR, Tang XF, Tan GJ. Boosting thermoelectricperformance of SnTe by selective alloying and band tuning. Mater TodayEnergy 2022;25:100958.[26] Luo ZZ, Hao SQ, Zhang XM, Hua X, Cai ST, Tan GJ, et al. Soft phonon modesfrom off-center Ge atoms lead to ultralow thermal conductivity and superiorthermoelectric performance in n-type PbSe-GeSe. Energy Environ Sci2018;11(11):3220e30.[27] Kim SI, Lee KH, Mun HA, Kim HS, Hwang SW, Roh JW, et al. Thermoelectrics.Dense dislocation arrays embedded in grain boundaries for high-performance bulk thermoelectrics. Science 2015;348(6230):109e14.[28] He Y, Lu P, Shi X, Xu F, Zhang T, Snyder GJ, et al. Ultrahigh thermoelectricperformance in mosaic crystals. Adv Mater 2015;27(24):3639e44.[29] Chen Z, Jian Z, Li W, Chang Y, Ge B, Hanus R, et al. Lattice dislocationsenhancing thermoelectric PbTe in addition to band convergence. Adv Mater2017;29(23):1606768.[30] Tan G, Shi F, Hao S, Zhao LD, Chi H, Zhang X, et al. Non-equilibrium pro-cessing leads to record high thermoelectric figure of merit in PbTe-SrTe. NatCommun 2016;7:12167.[31] Jiang B, Wang W, Liu S, Wang Y, Wang C, Chen Y, et al. High figure-of-meritand power generation in high-entropy GeTe-based thermoelectrics. Science2022;377(6602):208e13.[32] Chang C, Wu M, He D, Pei Y, Wu CF, Wu X, et al. 3D charge and 2D phonontransports leading to high out-of-plane ZT in n-type SnSe crystals. Science2018;360(6390):778e83.[33] Su L, Wang D, Wang S, Qin B, Wang Y, Qin Y, et al. High thermoelectricperformance realized through manipulating layered phonon-electrondecoupling. Science 2022;375(6587):1385e9.[34] Liu X, Shi X-L, Zhang L, Liu W-D, Yang Y, Chen Z-G. One-step post-treatmentboosts thermoelectric properties of PEDOT:PSS flexible thin films. J Mater SciTechnol 2023;132:81e9.[35] Shi X-L, Liu W-D, Li M, Sun Q, Xu S-D, Du D, et al. A solvothermal syntheticenvironmental design for high-performance SnSe-based thermoelectricmaterials. Adv Energy Mater 2022;12(20):2200670.[36] He W, Wang D, Wu H, Xiao Y, Zhang Y, He D, et al. High thermoelectricperformance in low-cost SnS0.91Se0.09 crystals. Science 2019;365(6460):1418e24.[37] Chetty R, Bali A, Mallik RC. Tetrahedrites as thermoelectric materials: anoverview. J Mater Chem C 2015;3(48):12364e78.[38] Hu H, Zhuang HL, Jiang Y, Shi J, Li JW, Cai B, et al. Thermoelectric Cu12Sb4S13-Based synthetic minerals with a sublimation-derived porous network. AdvMater 2021;33(43):e2103633.[39] Hagiwara T, Suekuni K, Lemoine P, Supka AR, Chetty R, Guilmeau E, et al. Keyrole of d0 and d10 cations for the design of semiconducting colusites: largethermoelectric ZT in Cu26Ti2Sb6S32 compounds. Chem Mater 2021;33(9):3449e56.[40] Shi YX, Sturm C, Kleinke H. Chalcogenides as thermoelectric materials. J Solidhttp://refhub.elsevier.com/S2352-8478(23)00108-9/sref1http://refhub.elsevier.com/S2352-8478(23)00108-9/sref1http://refhub.elsevier.com/S2352-8478(23)00108-9/sref1http://refhub.elsevier.com/S2352-8478(23)00108-9/sref2http://refhub.elsevier.com/S2352-8478(23)00108-9/sref2http://refhub.elsevier.com/S2352-8478(23)00108-9/sref2http://refhub.elsevier.com/S2352-8478(23)00108-9/sref3http://refhub.elsevier.com/S2352-8478(23)00108-9/sref3http://refhub.elsevier.com/S2352-8478(23)00108-9/sref3http://refhub.elsevier.com/S2352-8478(23)00108-9/sref4http://refhub.elsevier.com/S2352-8478(23)00108-9/sref4http://refhub.elsevier.com/S2352-8478(23)00108-9/sref4http://refhub.elsevier.com/S2352-8478(23)00108-9/sref5http://refhub.elsevier.com/S2352-8478(23)00108-9/sref5http://refhub.elsevier.com/S2352-8478(23)00108-9/sref5http://refhub.elsevier.com/S2352-8478(23)00108-9/sref6http://refhub.elsevier.com/S2352-8478(23)00108-9/sref6http://refhub.elsevier.com/S2352-8478(23)00108-9/sref7http://refhub.elsevier.com/S2352-8478(23)00108-9/sref7http://refhub.elsevier.com/S2352-8478(23)00108-9/sref8http://refhub.elsevier.com/S2352-8478(23)00108-9/sref8http://refhub.elsevier.com/S2352-8478(23)00108-9/sref8http://refhub.elsevier.com/S2352-8478(23)00108-9/sref9http://refhub.elsevier.com/S2352-8478(23)00108-9/sref9http://refhub.elsevier.com/S2352-8478(23)00108-9/sref9http://refhub.elsevier.com/S2352-8478(23)00108-9/sref10http://refhub.elsevier.com/S2352-8478(23)00108-9/sref10http://refhub.elsevier.com/S2352-8478(23)00108-9/sref10http://refhub.elsevier.com/S2352-8478(23)00108-9/sref10http://refhub.elsevier.com/S2352-8478(23)00108-9/sref10http://refhub.elsevier.com/S2352-8478(23)00108-9/sref11http://refhub.elsevier.com/S2352-8478(23)00108-9/sref11http://refhub.elsevier.com/S2352-8478(23)00108-9/sref11http://refhub.elsevier.com/S2352-8478(23)00108-9/sref11http://refhub.elsevier.com/S2352-8478(23)00108-9/sref12http://refhub.elsevier.com/S2352-8478(23)00108-9/sref12http://refhub.elsevier.com/S2352-8478(23)00108-9/sref12http://refhub.elsevier.com/S2352-8478(23)00108-9/sref12http://refhub.elsevier.com/S2352-8478(23)00108-9/sref13http://refhub.elsevier.com/S2352-8478(23)00108-9/sref13http://refhub.elsevier.com/S2352-8478(23)00108-9/sref13http://refhub.elsevier.com/S2352-8478(23)00108-9/sref14http://refhub.elsevier.com/S2352-8478(23)00108-9/sref14http://refhub.elsevier.com/S2352-8478(23)00108-9/sref14http://refhub.elsevier.com/S2352-8478(23)00108-9/sref14http://refhub.elsevier.com/S2352-8478(23)00108-9/sref15http://refhub.elsevier.com/S2352-8478(23)00108-9/sref15http://refhub.elsevier.com/S2352-8478(23)00108-9/sref15http://refhub.elsevier.com/S2352-8478(23)00108-9/sref16http://refhub.elsevier.com/S2352-8478(23)00108-9/sref16http://refhub.elsevier.com/S2352-8478(23)00108-9/sref16http://refhub.elsevier.com/S2352-8478(23)00108-9/sref16http://refhub.elsevier.com/S2352-8478(23)00108-9/sref17http://refhub.elsevier.com/S2352-8478(23)00108-9/sref17http://refhub.elsevier.com/S2352-8478(23)00108-9/sref17http://refhub.elsevier.com/S2352-8478(23)00108-9/sref17http://refhub.elsevier.com/S2352-8478(23)00108-9/sref17http://refhub.elsevier.com/S2352-8478(23)00108-9/sref17http://refhub.elsevier.com/S2352-8478(23)00108-9/sref18http://refhub.elsevier.com/S2352-8478(23)00108-9/sref18http://refhub.elsevier.com/S2352-8478(23)00108-9/sref18http://refhub.elsevier.com/S2352-8478(23)00108-9/sref19http://refhub.elsevier.com/S2352-8478(23)00108-9/sref19http://refhub.elsevier.com/S2352-8478(23)00108-9/sref19http://refhub.elsevier.com/S2352-8478(23)00108-9/sref20http://refhub.elsevier.com/S2352-8478(23)00108-9/sref20http://refhub.elsevier.com/S2352-8478(23)00108-9/sref20http://refhub.elsevier.com/S2352-8478(23)00108-9/sref20http://refhub.elsevier.com/S2352-8478(23)00108-9/sref21http://refhub.elsevier.com/S2352-8478(23)00108-9/sref21http://refhub.elsevier.com/S2352-8478(23)00108-9/sref21http://refhub.elsevier.com/S2352-8478(23)00108-9/sref21http://refhub.elsevier.com/S2352-8478(23)00108-9/sref21http://refhub.elsevier.com/S2352-8478(23)00108-9/sref21http://refhub.elsevier.com/S2352-8478(23)00108-9/sref22http://refhub.elsevier.com/S2352-8478(23)00108-9/sref22http://refhub.elsevier.com/S2352-8478(23)00108-9/sref22http://refhub.elsevier.com/S2352-8478(23)00108-9/sref22http://refhub.elsevier.com/S2352-8478(23)00108-9/sref22http://refhub.elsevier.com/S2352-8478(23)00108-9/sref22http://refhub.elsevier.com/S2352-8478(23)00108-9/sref23http://refhub.elsevier.com/S2352-8478(23)00108-9/sref23http://refhub.elsevier.com/S2352-8478(23)00108-9/sref23http://refhub.elsevier.com/S2352-8478(23)00108-9/sref23http://refhub.elsevier.com/S2352-8478(23)00108-9/sref23http://refhub.elsevier.com/S2352-8478(23)00108-9/sref24http://refhub.elsevier.com/S2352-8478(23)00108-9/sref24http://refhub.elsevier.com/S2352-8478(23)00108-9/sref24http://refhub.elsevier.com/S2352-8478(23)00108-9/sref24http://refhub.elsevier.com/S2352-8478(23)00108-9/sref24http://refhub.elsevier.com/S2352-8478(23)00108-9/sref25http://refhub.elsevier.com/S2352-8478(23)00108-9/sref25http://refhub.elsevier.com/S2352-8478(23)00108-9/sref25http://refhub.elsevier.com/S2352-8478(23)00108-9/sref26http://refhub.elsevier.com/S2352-8478(23)00108-9/sref26http://refhub.elsevier.com/S2352-8478(23)00108-9/sref26http://refhub.elsevier.com/S2352-8478(23)00108-9/sref26http://refhub.elsevier.com/S2352-8478(23)00108-9/sref26http://refhub.elsevier.com/S2352-8478(23)00108-9/sref27http://refhub.elsevier.com/S2352-8478(23)00108-9/sref27http://refhub.elsevier.com/S2352-8478(23)00108-9/sref27http://refhub.elsevier.com/S2352-8478(23)00108-9/sref27http://refhub.elsevier.com/S2352-8478(23)00108-9/sref28http://refhub.elsevier.com/S2352-8478(23)00108-9/sref28http://refhub.elsevier.com/S2352-8478(23)00108-9/sref28http://refhub.elsevier.com/S2352-8478(23)00108-9/sref29http://refhub.elsevier.com/S2352-8478(23)00108-9/sref29http://refhub.elsevier.com/S2352-8478(23)00108-9/sref29http://refhub.elsevier.com/S2352-8478(23)00108-9/sref30http://refhub.elsevier.com/S2352-8478(23)00108-9/sref30http://refhub.elsevier.com/S2352-8478(23)00108-9/sref30http://refhub.elsevier.com/S2352-8478(23)00108-9/sref31http://refhub.elsevier.com/S2352-8478(23)00108-9/sref31http://refhub.elsevier.com/S2352-8478(23)00108-9/sref31http://refhub.elsevier.com/S2352-8478(23)00108-9/sref31http://refhub.elsevier.com/S2352-8478(23)00108-9/sref32http://refhub.elsevier.com/S2352-8478(23)00108-9/sref32http://refhub.elsevier.com/S2352-8478(23)00108-9/sref32http://refhub.elsevier.com/S2352-8478(23)00108-9/sref32http://refhub.elsevier.com/S2352-8478(23)00108-9/sref33http://refhub.elsevier.com/S2352-8478(23)00108-9/sref33http://refhub.elsevier.com/S2352-8478(23)00108-9/sref33http://refhub.elsevier.com/S2352-8478(23)00108-9/sref33http://refhub.elsevier.com/S2352-8478(23)00108-9/sref34http://refhub.elsevier.com/S2352-8478(23)00108-9/sref34http://refhub.elsevier.com/S2352-8478(23)00108-9/sref34http://refhub.elsevier.com/S2352-8478(23)00108-9/sref34http://refhub.elsevier.com/S2352-8478(23)00108-9/sref35http://refhub.elsevier.com/S2352-8478(23)00108-9/sref35http://refhub.elsevier.com/S2352-8478(23)00108-9/sref35http://refhub.elsevier.com/S2352-8478(23)00108-9/sref36http://refhub.elsevier.com/S2352-8478(23)00108-9/sref36http://refhub.elsevier.com/S2352-8478(23)00108-9/sref36http://refhub.elsevier.com/S2352-8478(23)00108-9/sref36http://refhub.elsevier.com/S2352-8478(23)00108-9/sref36http://refhub.elsevier.com/S2352-8478(23)00108-9/sref36http://refhub.elsevier.com/S2352-8478(23)00108-9/sref37http://refhub.elsevier.com/S2352-8478(23)00108-9/sref37http://refhub.elsevier.com/S2352-8478(23)00108-9/sref37http://refhub.elsevier.com/S2352-8478(23)00108-9/sref38http://refhub.elsevier.com/S2352-8478(23)00108-9/sref38http://refhub.elsevier.com/S2352-8478(23)00108-9/sref38http://refhub.elsevier.com/S2352-8478(23)00108-9/sref38http://refhub.elsevier.com/S2352-8478(23)00108-9/sref38http://refhub.elsevier.com/S2352-8478(23)00108-9/sref38http://refhub.elsevier.com/S2352-8478(23)00108-9/sref39http://refhub.elsevier.com/S2352-8478(23)00108-9/sref39http://refhub.elsevier.com/S2352-8478(23)00108-9/sref39http://refhub.elsevier.com/S2352-8478(23)00108-9/sref39http://refhub.elsevier.com/S2352-8478(23)00108-9/sref39http://refhub.elsevier.com/S2352-8478(23)00108-9/sref39http://refhub.elsevier.com/S2352-8478(23)00108-9/sref39http://refhub.elsevier.com/S2352-8478(23)00108-9/sref39http://refhub.elsevier.com/S2352-8478(23)00108-9/sref39http://refhub.elsevier.com/S2352-8478(23)00108-9/sref39http://refhub.elsevier.com/S2352-8478(23)00108-9/sref39http://refhub.elsevier.com/S2352-8478(23)00108-9/sref40F.-H. Sun, H. Li, J. Tan et al. Journal of Materiomics 10 (2024) 218e233State Chem 2019;270:273e9.[41] Ang R, Khan AU, Tsujii N, Takai K, Nakamura R, Mori T. Thermoelectricitygeneration and electron-magnon scattering in a natural chalcopyrite mineralfrom a deep-sea hydrothermal vent. Angew Chem, Int Ed 2015;54(44):12909e13.[42] Tsujii N, Mori T. High Thermoelectric power factor in a carrier-doped mag-netic semiconductor CuFeS2. APEX 2013;6(4):043001.[43] Jabar B, Li F, Zheng Z, Mansoor A, Zhu Y, Liang C, et al. Homo-compositionand hetero-structure nanocomposite Pnma Bi2SeS2-Pnnm Bi2SeS2 with highthermoelectric performance. Nat Commun 2021;12(1):7192.[44] Zhao KP, Qiu PF, Song QF, Blichfeld AB, Eikeland E, Ren DD, et al. Ultrahighthermoelectric performance in Cu2-ySe0.5S0.5 liquid-like materials. MaterToday Phys 2017;1:14e23.[45] Liu H, Shi X, Xu F, Zhang L, Zhang W, Chen L, et al. Copper ion liquid-likethermoelectrics. Nat Mater 2012;11(5):422e5.[46] Zhao YQ, Gu Y, Zong PA, Pan L, Zhang LJ, Koumoto K, et al. High thermo-electric performance of Co-doped Cu2SnS3-attapulgite nano-compositesachieved by synergetic manipulation of electrical and thermal transportproperties. J Alloys Compd 2021;887:161338.[47] Guelou G, Kumar VP, Carnevali V, Lebedev OI, Raveau B, Couder C, et al. Long-range cationic order collapse triggered by S/Cl mixed-anion occupancy yieldsenhanced thermoelectric properties in Cu5Sn2S7. Chem Mater 2021;33(23):9425e38.[48] Deng TT, Xing T, Brod MK, Sheng Y, Qiu PF, Veremchuk I, et al. Discovery ofhigh-performance thermoelectric copper chalcogenide using modifieddiffusion-couple high-throughput synthesis and automated histogramanalysis technique. Energy Environ Sci 2020;13(9):3041e53.[49] Yang YB, Ying PZ, Wang JZ, Liu XL, Du ZL, Chao YM, et al. Enhancing thethermoelectric performance of Cu3SnS4-based solid solutions through co-ordination of the Seebeck coefficient and carrier concentration. J Mater Chem2017;5(35):18808e15.[50] Cui J, He T, Han Z, Liu X, Du Z. Improved thermoelectric performance of solidsolution Cu4Sn7.5S16 through isoelectronic substitution of Se for S. Sci Rep2018;8(1):8202.[51] Shen M, Lu S, Zhang Z, Liu H, Shen W, Fang C, et al. Bi and Sn co-dopingenhanced thermoelectric properties of Cu3SbS4 materials with excellentthermal stability. ACS Appl Mater Interfaces 2020;12(7):8271e9.[52] Zhang JJ, Wang LJ, Liu M, Wang J, Sun K, Yang Y, et al. Preparation andthermoelectric performance of tetrahedrite-like cubic Cu3SbS3 compound.J Mater Sci Mater Electron 2021;32(8):10789e802.[53] Wang H, Zheng S, Wu H, Xiong X, Xiong Q, Wang H, et al. Realizing enhancedthermoelectric performance and hardness in icosahedral Cu5FeS4-xSex withhigh-density twin boundaries. Small 2022;18(2):e2104592.[54] Zhang RZ, Chen K, Du B, Reece MJ. Screening for Cu-S based thermoelectricmaterials using crystal structure features. J Mater Chem 2017;5(10):5013e9.[55] Liang D, Ma R, Jiao S, Pang G, Feng S. A facile synthetic approach for copperiron sulfide nanocrystals with enhanced thermoelectric performance.Nanoscale 2012;4(20):6265e8.[56] Qiu XX, Qiu PF, Deng TT, Huang H, Du XL, Shi X, et al. Thermoelectricproperties of nano-grained mooihoekite Cu9Fe9S16. Z Anorg Allg Chem2020;646(14):1116e21.[57] Barbier T, Berthebaud D, Fresard R, Lebedev OI, Guilmeau E, Eyert V, et al.Structural and thermoelectric properties of n-type isocubanite CuFe2S3. InorgChem Front 2017;4(3):424e32.[58] Burnett JD, Gourdon O, Ranmohotti KGS, Takas NJ, Djieutedjeu H,Poudeu PFP, et al. Structure-property relationships along the Fe-substitutedCuInS2 series: tuning of thermoelectric and magnetic properties. MaterChem Phys 2014;147(1e2):17e27.[59] Ge B, Shi Z, Zhou C, Hu J, Liu G, Xia H, et al. Enhanced thermoelectric per-formance of n-type eco-friendly material Cu1-xAgxFeS2 (x ¼ 0-0.14) viabandgap tuning. J Alloys Compd 2019;809:151717.[60] Sharma SD, Bayikadi K, Raman S, Neeleshwar S. Synergistic optimization ofthermoelectric performance in earth-abundant Cu2ZnSnS4 by inclusion ofgraphene nanosheets. Nanotechnology 2020;31(36):365402.[61] Lang YD, Pan L, Chen CC, Wang YF. Thermoelectric properties of thiospinel-type CuCo2S4. J Electron Mater 2019;48(7):4179e87.[62] Ahn JY, Hwang JY, Ryu BK, Oh MW, Lee KH, Kim SW. Importance of crystalchemistry with interstitial site determining thermoelectric transport prop-erties in pavonite homologue Cu-Bi-S compounds. Cryst Eng Commun2016;18(8):1453e61.[63] Paradis-Fortin L, Guelou G, Kumar VP, Lemoine P, Prestipino C, Merdrignac-Conanec O, et al. Structure, microstructure and thermoelectric properties ofgermanite-type Cu22Fe8Ge4S32 compounds. J Alloys Compd 2020;831:154767.[64] Bourges C, Al Orabi RAR, Miyazaki Y. Off-stoichiometry effect on thermo-electric properties of the new p-type sulfides compounds Cu2CoGeS4. J AlloysCompd 2020;826:154240.[65] Pavan Kumar V, Supka AR, Lemoine P, Lebedev OI, Raveau B, Suekuni K, et al.High power factors of thermoelectric colusites Cu26T2Ge6S32 (T ¼ Cr, Mo, W):230toward functionalization of the conductive “Cu-S” network. Adv EnergyMater 2018;9(6):1803249.[66] Hashikuni K, Suekuni K, Watanabe K, Bouyrie Y, Ohta M, Ohtaki M, et al.Carrier concentration tuning in thermoelectric thiospinel Cu2CoTi3S8 byoxidative extraction of copper. J Solid State Chem 2018;259:5e10.[67] Bourges C, Bouyrie Y, Supka AR, Al Orabi RAR, Lemoine P, Lebedev OI, et al.High-Performance thermoelectric bulk colusite by process controlled struc-tural disordering. J Am Chem Soc 2018;140(6):2186e95.[68] Bouyrie Y, Ohta M, Suekuni K, Kikuchi Y, Jood P, Yamamoto A, et al.Enhancement in the thermoelectric performance of colusites Cu26A2E6S32(A ¼ Nb, Ta; E ¼ Sn, Ge) using E-site non-stoichiometry. J Mater Chem C2017;5(17):4174e84.[69] Suekuni K, Kim FS, Nishiate H, Ohta M, Tanaka HI, Takabatake T. High-per-formance thermoelectric minerals: colusites Cu26V2M6S32 (M ¼ Ge, Sn). ApplPhys Lett 2014;105(13):132107.[70] Bourges C, Kumar VP, Nagai H, Miyazaki Y, Raveau B, Guilmeau E. Role ofcobalt for titanium substitution on the thermoelectric properties of thethiospinel CuTi2S4. J Alloys Compd 2019;781:1169e74.[71] Mangelis P, Vaqueiro P, Jumas JC, da Silva I, Smith RI, Powell AV. The effect ofelectron and hole doping on the thermoelectric properties of shandite-typeCo3Sn2S2. J Solid State Chem 2017;251:204e10.[72] Wang HT, Ma HQ, Duan B, Geng HY, Zhou L, Li JL, et al. High-Pressure rapidpreparation of high-performance binary silver sulfide thermoelectric mate-rials. ACS Appl Energy Mater 2021;4(2):1610e8.[73] HeWK, Hong T, Wang DY, Gao X, Zhao LD. Low carrier concentration leads tohigh in-plane thermoelectric performance in n-type SnS crystals. Sci ChinaMater 2021;64(12):3051e8.[74] Guo J, Yang JM, Ge ZH, Jiang BB, Qiu Y, Zhu YK, et al. Realizing high ther-moelectric performance in earth-abundant Bi2S3 bulk materials via halogenacid modulation. Adv Funct Mater 2021;31(37):2102838.[75] Gu Y, Song K, Hu X, Chen C, Pan L, Lu C, et al. Realization of an ultrahighpower factor and enhanced thermoelectric performance in TiS2 via micro-structural texture engineering. ACS Appl Mater Interfaces 2020;12(37):41687e95.[76] Gautam AK, Faraz M, Khare N. Enhanced thermoelectric properties of MoS2with the incorporation of reduced graphene oxide (RGO). J Alloys Compd2020;838:155673.[77] Cai FG, Dong R, Sun W, Lei XB, Yu B, Chen J, et al. PbmBi2S3þm homologousseries with low thermal conductivity prepared by the solution-basedmethod as promising thermoelectric materials. Chem Mater 2021;33(15):6003e11.[78] Ohta M, Chung DY, Kunii M, Kanatzidis MG. Low lattice thermal conductivityin Pb5Bi6Se14, Pb3Bi2S6, and PbBi2S4: promising thermoelectric materials inthe cannizzarite, lillianite, and galenobismuthite homologous series. J MaterChem 2014;2(47):20048e58.[79] Joo SJ, Ryu B, Son JH, Lee JE, Min BK, Kim BS. Highly anisotropic thermo-electric transport properties responsible for enhanced thermoelectric per-formance in the hot-deformed tetradymite Bi2Te2S. J Alloys Compd2019;783:448e54.[80] You YH, Su XL, Liu W, Yan YG, Fu JF, Cheng X, et al. Structure and thermo-electric property of Te doped paracostibite CoSb1-xTexS compounds. J SolidState Chem 2018;262:1e7.[81] Telkes M. Thermoelectric power and electrical resistivity of minerals. AmMineral 1950;35(7e8):536.[82] Dennler G, Chmielowski R, Jacob S, Capet F, Roussel P, Zastrow S, et al. Arebinary copper sulfides/selenides really new and promising thermoelectricmaterials? Adv Energy Mater 2014;4(9):1301581.[83] Zhang Y, Xing C, Liu Y, Spadaro MC, Wang X, Li M, et al. Doping-mediatedstabilization of copper vacancies to promote thermoelectric properties ofCu2-xS. Nano Energy 2021;85:105991.[84] Nam HN, Yamada R, Okumura H, Nguyen TQ, Suzuki K, Shinya H, et al.Intrinsic defect formation and the effect of transition metal doping ontransport properties in a ductile thermoelectric material alpha-Ag2S: a first-principles study. Phys Chem Chem Phys 2021;23(16):9773e84.[85] Sun Y, Xi L, Yang J, Wu L, Shi X, Chen L, et al. The “electron crystal” behaviorin copper chalcogenides Cu2X (X ¼ Se, S). J Mater Chem 2017;5(10):5098e105.[86] Voneshen DJ, Walker HC, Refson K, Goff JP. Hopping time scales and thephonon-liquid electron-crystal picture in thermoelectric copper selenide.Phys Rev Lett 2017;118(14):145901.[87] Lukashev P, Lambrecht WRL, Kotani T, Schilfgaarde VM. Electronic andcrystal structure of Cu2-xS: full-potential electronic structure calculations.Phy Rev B 2007;76(19):195202.[88] Wang L-W. High chalcocite Cu2S: a solid-liquid hybrid phase. Phys Rev Lett2012;108(8):085703.[89] Boyce JB, Huberman BA. Superionic conductors: transitions, structures, dy-namics. Phys Rep 1979;51(4):189e265.[90] He Y, Day T, Zhang T, Liu H, Shi X, Chen L, et al. High thermoelectric per-formance in non-toxic earth-abundant copper sulfide. Adv Materhttp://refhub.elsevier.com/S2352-8478(23)00108-9/sref40http://refhub.elsevier.com/S2352-8478(23)00108-9/sref40http://refhub.elsevier.com/S2352-8478(23)00108-9/sref41http://refhub.elsevier.com/S2352-8478(23)00108-9/sref41http://refhub.elsevier.com/S2352-8478(23)00108-9/sref41http://refhub.elsevier.com/S2352-8478(23)00108-9/sref41http://refhub.elsevier.com/S2352-8478(23)00108-9/sref41http://refhub.elsevier.com/S2352-8478(23)00108-9/sref42http://refhub.elsevier.com/S2352-8478(23)00108-9/sref42http://refhub.elsevier.com/S2352-8478(23)00108-9/sref42http://refhub.elsevier.com/S2352-8478(23)00108-9/sref43http://refhub.elsevier.com/S2352-8478(23)00108-9/sref43http://refhub.elsevier.com/S2352-8478(23)00108-9/sref43http://refhub.elsevier.com/S2352-8478(23)00108-9/sref43http://refhub.elsevier.com/S2352-8478(23)00108-9/sref43http://refhub.elsevier.com/S2352-8478(23)00108-9/sref43http://refhub.elsevier.com/S2352-8478(23)00108-9/sref43http://refhub.elsevier.com/S2352-8478(23)00108-9/sref44http://refhub.elsevier.com/S2352-8478(23)00108-9/sref44http://refhub.elsevier.com/S2352-8478(23)00108-9/sref44http://refhub.elsevier.com/S2352-8478(23)00108-9/sref44http://refhub.elsevier.com/S2352-8478(23)00108-9/sref44http://refhub.elsevier.com/S2352-8478(23)00108-9/sref44http://refhub.elsevier.com/S2352-8478(23)00108-9/sref44http://refhub.elsevier.com/S2352-8478(23)00108-9/sref45http://refhub.elsevier.com/S2352-8478(23)00108-9/sref45http://refhub.elsevier.com/S2352-8478(23)00108-9/sref45http://refhub.elsevier.com/S2352-8478(23)00108-9/sref46http://refhub.elsevier.com/S2352-8478(23)00108-9/sref46http://refhub.elsevier.com/S2352-8478(23)00108-9/sref46http://refhub.elsevier.com/S2352-8478(23)00108-9/sref46http://refhub.elsevier.com/S2352-8478(23)00108-9/sref46http://refhub.elsevier.com/S2352-8478(23)00108-9/sref46http://refhub.elsevier.com/S2352-8478(23)00108-9/sref47http://refhub.elsevier.com/S2352-8478(23)00108-9/sref47http://refhub.elsevier.com/S2352-8478(23)00108-9/sref47http://refhub.elsevier.com/S2352-8478(23)00108-9/sref47http://refhub.elsevier.com/S2352-8478(23)00108-9/sref47http://refhub.elsevier.com/S2352-8478(23)00108-9/sref47http://refhub.elsevier.com/S2352-8478(23)00108-9/sref47http://refhub.elsevier.com/S2352-8478(23)00108-9/sref47http://refhub.elsevier.com/S2352-8478(23)00108-9/sref48http://refhub.elsevier.com/S2352-8478(23)00108-9/sref48http://refhub.elsevier.com/S2352-8478(23)00108-9/sref48http://refhub.elsevier.com/S2352-8478(23)00108-9/sref48http://refhub.elsevier.com/S2352-8478(23)00108-9/sref48http://refhub.elsevier.com/S2352-8478(23)00108-9/sref49http://refhub.elsevier.com/S2352-8478(23)00108-9/sref49http://refhub.elsevier.com/S2352-8478(23)00108-9/sref49http://refhub.elsevier.com/S2352-8478(23)00108-9/sref49http://refhub.elsevier.com/S2352-8478(23)00108-9/sref49http://refhub.elsevier.com/S2352-8478(23)00108-9/sref49http://refhub.elsevier.com/S2352-8478(23)00108-9/sref49http://refhub.elsevier.com/S2352-8478(23)00108-9/sref50http://refhub.elsevier.com/S2352-8478(23)00108-9/sref50http://refhub.elsevier.com/S2352-8478(23)00108-9/sref50http://refhub.elsevier.com/S2352-8478(23)00108-9/sref50http://refhub.elsevier.com/S2352-8478(23)00108-9/sref50http://refhub.elsevier.com/S2352-8478(23)00108-9/sref50http://refhub.elsevier.com/S2352-8478(23)00108-9/sref51http://refhub.elsevier.com/S2352-8478(23)00108-9/sref51http://refhub.elsevier.com/S2352-8478(23)00108-9/sref51http://refhub.elsevier.com/S2352-8478(23)00108-9/sref51http://refhub.elsevier.com/S2352-8478(23)00108-9/sref51http://refhub.elsevier.com/S2352-8478(23)00108-9/sref51http://refhub.elsevier.com/S2352-8478(23)00108-9/sref52http://refhub.elsevier.com/S2352-8478(23)00108-9/sref52http://refhub.elsevier.com/S2352-8478(23)00108-9/sref52http://refhub.elsevier.com/S2352-8478(23)00108-9/sref52http://refhub.elsevier.com/S2352-8478(23)00108-9/sref52http://refhub.elsevier.com/S2352-8478(23)00108-9/sref52http://refhub.elsevier.com/S2352-8478(23)00108-9/sref53http://refhub.elsevier.com/S2352-8478(23)00108-9/sref53http://refhub.elsevier.com/S2352-8478(23)00108-9/sref53http://refhub.elsevier.com/S2352-8478(23)00108-9/sref53http://refhub.elsevier.com/S2352-8478(23)00108-9/sref53http://refhub.elsevier.com/S2352-8478(23)00108-9/sref53http://refhub.elsevier.com/S2352-8478(23)00108-9/sref54http://refhub.elsevier.com/S2352-8478(23)00108-9/sref54http://refhub.elsevier.com/S2352-8478(23)00108-9/sref54http://refhub.elsevier.com/S2352-8478(23)00108-9/sref55http://refhub.elsevier.com/S2352-8478(23)00108-9/sref55http://refhub.elsevier.com/S2352-8478(23)00108-9/sref55http://refhub.elsevier.com/S2352-8478(23)00108-9/sref55http://refhub.elsevier.com/S2352-8478(23)00108-9/sref56http://refhub.elsevier.com/S2352-8478(23)00108-9/sref56http://refhub.elsevier.com/S2352-8478(23)00108-9/sref56http://refhub.elsevier.com/S2352-8478(23)00108-9/sref56http://refhub.elsevier.com/S2352-8478(23)00108-9/sref56http://refhub.elsevier.com/S2352-8478(23)00108-9/sref56http://refhub.elsevier.com/S2352-8478(23)0010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78(23)00108-9/sref86http://refhub.elsevier.com/S2352-8478(23)00108-9/sref86http://refhub.elsevier.com/S2352-8478(23)00108-9/sref86http://refhub.elsevier.com/S2352-8478(23)00108-9/sref86http://refhub.elsevier.com/S2352-8478(23)00108-9/sref87http://refhub.elsevier.com/S2352-8478(23)00108-9/sref87http://refhub.elsevier.com/S2352-8478(23)00108-9/sref87http://refhub.elsevier.com/S2352-8478(23)00108-9/sref89http://refhub.elsevier.com/S2352-8478(23)00108-9/sref89http://refhub.elsevier.com/S2352-8478(23)00108-9/sref89http://refhub.elsevier.com/S2352-8478(23)00108-9/sref90http://refhub.elsevier.com/S2352-8478(23)00108-9/sref90F.-H. Sun, H. Li, J. Tan et al. Journal of Materiomics 10 (2024) 218e2332014;26(23):3974e8.[91] Shi X, Chen H, Hao F, Liu R, Wang T, Qiu P, et al. Room-temperature ductileinorganic semiconductor. Nat Mater 2018;17(5):421e6.[92] Guin SN, Sanyal D, Biswas K. The effect of order-disorder phase transitionsand band gap evolution on the thermoelectric properties of AgCuS nano-crystals. Chem Sci 2016;7(1):534e43.[93] Kim JH, Chung DY, Bilc D, Loo S, Short J, Mahanti SD, et al. Crystal growth,thermoelectric properties, and electronic structure of AgBi3S5 and AgSbxBi3-xS5 (x ¼ 0.3). Chem Mater 2005;17(14):3606e14.[94] Jiang B, Yu Y, Cui J, Liu X, Xie L, Liao J, et al. High-entropy-stabilized chal-cogenides with high thermoelectric performance. Science 2021;371(6531):830e4.[95] Liu R, Chen H, Zhao K, Qin Y, Jiang B, Zhang T, et al. Entropy as a gene-likeperformance indicator promoting thermoelectric materials. Adv Mater2017;29(38):1702712.[96] Zhang R-Z, Gucci F, Zhu H, Chen K, Reece MJ. Data-driven design of eco-friendly thermoelectric high-entropy sulfides. Inorg Chem 2018;57(20):13027e33.[97] Pei Y, Wang H, Snyder GJ. Band engineering of thermoelectric materials. AdvMater 2012;24(46):6125e35.[98] Zhao L-D, He J, Hao S, Wu C-I, Hogan TP, Wolverton C, et al. Raising thethermoelectric performance of p-type PbS with endotaxial nanostructuringand valence-band offset engineering using CdS and ZnS. J Am Chem Soc2012;134(39):16327e36.[99] Xiao Y, Wang D, Zhang Y, Chen C, Zhang S, Wang K, et al. Band sharpeningand band alignment enable high quality factor to enhance thermoelectricperformance in n-type PbS. J Am Chem Soc 2020;142(8):4051e60.[100] Luo Z-Z, Hao S, Cai S, Bailey TP, Tan G, Luo Y, et al. Enhancement of ther-moelectric performance for n-type PbS through synergy of gap state andFermi level pinning. J Am Chem Soc 2019;141(15):6403e12.[101] Long SO, Powell AV, Hull S, Orlandi F, Tang CC, Supka AR, et al. Jahn-Tellerdriven electronic instability in thermoelectric tetrahedrite. Adv Funct Mater2020;30(12):1909409.[102] Lai W, Wang YX, Morelli DT, Lu X. From bonding asymmetry to anharmonicrattling in Cu12Sb4S13 tetrahedrites: when lone-pair electrons are not solonely. Adv Funct Mater 2015;25(24):3648e57.[103] Li X, Lou Y, Jin K, Fu L, Xu P, Shi Z, et al. Realizing ZT > 2 in environment-friendly monoclinic Cu2S-tetragonal Cu1.96S nano-phase junctions for ther-moelectrics. Angew Chem, Int Ed 2022;61(45):e202212885.[104] Zhao K, Zhu C, Qiu P, Blichfeld AB, Eikeland E, Ren D, et al. High thermo-electric performance and low thermal conductivity in Cu2-yS1/3Se1/3Te1/3liquid-like materials with nanoscale mosaic structures. Nano Energy2017;42:43e50.[105] Zhao LL, Wang XL, Fei FY, Wang JY, Cheng ZX, Dou SX, et al. High thermo-electric and mechanical performance in highly dense Cu2-xS bulks preparedby a melt-solidification technique. J Mater Chem 2015;3(18):9432e7.[106] Zhao S, Chen H, Zhao X, Luo J, Tang Z, Zeng G, et al. Excessive iodine additionleads to room-temperature superionic Cu2S with enhanced thermoelectricproperties and improved thermal stability. Mater Today Phys 2020;15:100271.[107] Nkemeni DS, Yang Z, Lou S, Li G, Zhou S. Achievement of extra-high ther-moelectric performance in doped copper sulfide. J Alloys Compd 2021;878:160128.[108] Zhang Y-X, Lou Q, Ge Z-H, Gu S-W, Yang J-X, Guo J, et al. Excellent ther-moelectric properties and stability realized in copper sulfides based com-posites via complex nanostructuring. Acta Mater 2022;233:117972.[109] Yu Y, Yang D, Li J, Zhang M, Luo H, Liang Q, et al. A flash vacuum-inducedreaction in preparing high performance thermoelectric Cu2S. Adv FunctMater 2022;32(2):2107284.[110] Tang H, Sun F-H, Dong J-F, Asfandiyar, Zhuang H-L, Pan Y, et al. Graphenenetwork in copper sulfide leading to enhanced thermoelectric propertiesand thermal stability. Nano Energy 2018;49:267e73.[111] Mao T, Qiu P, Hu P, Du X, Zhao K, Wei T-R, et al. Decoupling thermoelectricperformance and stability in liquid-like thermoelectric materials. Adv Sci2020;7(1):1901598.[112] Li M, Liu Y, Zhang Y, Han X, Zhang T, Zuo Y, et al. Effect of the annealingatmosphere on crystal phase and thermoelectric properties of copper sulfide.ACS Nano 2021;15(3):4967e78.[113] Ge ZH, Chong X, Feng D, Zhang YX, Qiu Y, Xie L, et al. Achieving an excellentthermoelectric performance in nanostructured copper sulfide bulk via a fastdoping strategy. Mater Today Phys 2019;8:71e7.[114] Zheng L-J, Zhang B-P, Li HZ, Pei J, Yu J-B. CuxS superionic compounds:electronic structure and thermoelectric performance enhancement. J AlloysCompd 2017;722:17e24.[115] Meng QL, Kong S, Huang ZW, Zhu YH, Liu HC, Lu XW, et al. Simultaneousenhancement in the power factor and thermoelectric performance of coppersulfide by In2S3 doping. J Mater Chem 2016;4(32):12624e9.[116] Qin P, Ge Z-H, Chen Y-X, Chong X, Feng J, He J. Achieving high thermoelectric231performance of Cu1.8S composites with WSe2 nanoparticles. Nanotechnology2018;29(34):345402.[117] Tang H, Zhuang H-L, Cai B, Asfandiyar, Dong J, Sun F-H, et al. Enhancing thethermoelectric performance of Cu1.8S by Sb/Sn co-doping and incorporatingmultiscale defects to scatter heat-carrying phonons. J Mater Chem C2019;7(14):4026e31.[118] Liu W-D, Shi X-L, Gao H, Moshwan R, Xu S-D, Wang Y, et al. Kinetic conditiondriven phase and vacancy enhancing thermoelectric performance of low-cost and eco-friendly Cu2-xS. J Mater Chem C 2019;7(18):5366e73.[119] Ge Z-H, Liu X, Feng D, Lin J, He J. High-performance thermoelectricity innanostructured earth-abundant copper sulfides bulk materials. Adv EnergyMater 2016;6(16):1600607.[120] Luo H, Yang D, Yu Y, Liang Q, Peng H, Xia F, et al. The high-pressure pro-cessed Cu2S: phase intergrowth with strained lamella leading to animproved thermoelectric performance. Adv Electron Mater 2022;8(2):2100835.[121] Yang D, Su X, Yan Y, He J, Uher C, Tang X. Mechanochemical synthesis of highthermoelectric performance bulk Cu2X (X ¼ S, Se) materials. Apl Mater2016;4(11):116110.[122] Chen X, Zhang H, Zhao Y, Liu W-D, Dai W, Wu T, et al. Carbon-encapsulatedcopper sulfide leading to enhanced thermoelectric properties. ACS ApplMater Interfaces 2019;11(25):22457e63.[123] Tang Y-Q, Zhang K, Ge Z-H, Feng J. Facile synthesis and thermoelectricproperties of Cu1.96S compounds. J Solid State Chem 2018;265:140e7.[124] Zhang Y-X, Zhu Y-K, Feng J, Ge Z-H. Precious metal nanoparticles dispersingtoward highly enhanced mechanical and thermoelectric properties of coppersulfides. J Alloys Compd 2022:892162035.[125] Chen X-Q, Fan S-J, Han C, Wu T, Wang L-J, Jiang W, et al. Multiscale archi-tectures boosting thermoelectric performance of copper sulfide compound.Rare Met 2021;40(8):2017e25.[126] Mikula A, Nieroda P, Mars K, Dabrowa J, Kolezynski A. Structural, thermo-electric and stability studies of Fe-doped copper sulfide. Solid State Ionics2020;350:115322.[127] Liu HL, Shi X, Xu FF, Zhang LL, Zhang WQ, Chen LD, et al. Copper ion liquid-like thermoelectrics. Nat Mater 2012;11(5):422e5.[128] Zhao L-D, He J, Wu C-I, Hogan TP, Zhou X, Uher C, et al. Thermoelectrics withearth abundant elements: high performance p-type PbS nanostructured withSrS and CaS. J Am Chem Soc 2012;134(18):7902e12.[129] Qin Y, Xiao Y, Wang D, Qin B, Huang Z, Zhao L-D. An approach of enhancingthermoelectric performance for p-type PbS: decreasing electronic thermalconductivity. J Alloys Compd 2020;820:153453.[130] Qin Y, Hong T, Qin B, Wang D, He W, Gao X, et al. Contrasting Cu roles lead tohigh ranged thermoelectric performance of PbS. Adv Funct Mater2021;31(34):2102185.[131] Ibanez M, Genc A, Hasler R, Liu Y, Dobrozhan O, Nazarenko O, et al. Tuningtransport properties in thermoelectric nanocomposites through inorganicligands and heterostructured building blocks. ACS Nano 2019;13(6):6572e80.[132] Jiang B, Liu X, Wang Q, Cui J, Jia B, Zhu Y, et al. Realizing high-efficiencypower generation in low-cost PbS-based thermoelectric materials. EnergyEnviron Sci 2020;13(2):579e91.[133] Ibanez M, Luo Z, Genc A, Piveteau L, Ortega S, Cadavid D, et al. High-per-formance thermoelectric nanocomposites from nanocrystal building blocks.Nat Commun 2016;7:10766.[134] Rathore E, Juneja R, Sarkar D, Roychowdhury S, Kofu M, Nakajima K, et al.Enhanced covalency and nanostructured-phonon scattering lead to highthermoelectric performance in n-type PbS. Mater Today Energy 2022;24:100953.[135] Luo Z-Z, Cai S, Hao S, Bailey TP, Xie H, Slade TJ, et al. Valence dispropor-tionation of GeS in the PbS matrix forms Pb5Ge5S12 inclusions with con-duction band alignment leading to high n-type thermoelectric performance.J Am Chem Soc 2022;144(16):7402e13.[136] Zhao M, Chang C, Xiao Y, Gu R, He J, Zhao L-D. Investigations on distinctthermoelectric transport behaviors of Cu in n-type PbS. J Alloys Compd2019;781:820e30.[137] Li M, Liu Y, Zhang Y, Chang C, Zhang T, Yang D, et al. Room temperatureaqueous-based synthesis of copper-doped lead sulfide nanoparticles forthermoelectric application. Chem Eng J 2022;433:133837.[138] Hou Z, Qiu Y, Ren D, Huang Z, Zhao L-D. Enhancing thermoelectric transportproperties of n-type PbS through introducing CaS/SrS. J Solid State Chem2019;280:130e8.[139] Li M, Liu Y, Zhang Y, Han X, Xiao K, Nabahat M, et al. PbS-Pb-CuxS compositesfor thermoelectric application. ACS Appl Mater Interfaces 2021;13(43):51373e82.[140] Cheng R, Wang D, Bai H, Wu J, Liu W, Zhao L-D, et al. Bridging the miscibilitygap towards higher thermoelectric performance of PbS. Acta Mater2021;220:117337.[141] Hou Z, Wang D, Hong T, Qin Y, Peng S, Wang G, et al. Boosting thermoelectrichttp://refhub.elsevier.com/S2352-8478(23)00108-9/sref90http://refhub.elsevier.com/S2352-8478(23)00108-9/sref90http://refhub.elsevier.com/S2352-8478(23)00108-9/sref91http://refhub.elsevier.com/S2352-8478(23)00108-9/sref91http://refhub.elsevier.com/S2352-8478(23)00108-9/sref91http://refhub.elsevier.com/S2352-8478(23)00108-9/sref92http://refhub.elsevier.com/S2352-8478(23)00108-9/sref92http://refhub.elsevier.com/S2352-8478(23)00108-9/sref92http://refhub.elsevier.com/S2352-8478(23)00108-9/sref92http://refhub.elsevier.com/S2352-8478(23)00108-9/sref93http://refhub.elsevier.com/S2352-8478(23)00108-9/sref93http://refhub.elsevier.com/S2352-8478(23)00108-9/sref93http://refhub.elsevier.com/S2352-8478(23)00108-9/sref93http://refhub.elsevier.com/S2352-8478(23)00108-9/sref93http://refhub.elsevier.com/S2352-8478(23)00108-9/sref93http://refhub.elsevier.com/S2352-8478(23)00108-9/sref93http://refhub.elsevier.com/S2352-8478(23)00108-9/sref93http://refhub.elsevier.com/S2352-8478(23)00108-9/sref93http://refhub.elsevier.com/S2352-8478(23)00108-9/sref93http://refhub.elsevier.com/S2352-8478(23)00108-9/sref94http://refhub.elsevier.com/S2352-8478(23)00108-9/sref94http://refhub.elsevier.com/S2352-8478(23)00108-9/sref94http://refhub.elsevier.com/S2352-8478(23)00108-9/sref94http://refhub.elsevier.com/S2352-8478(23)00108-9/sref95http://refhub.elsevier.com/S2352-8478(23)00108-9/sref95http://refhub.elsevier.com/S2352-8478(23)00108-9/sref95http://refhub.elsevier.com/S2352-8478(23)00108-9/sref96http://refhub.elsevier.com/S2352-8478(23)00108-9/sref96http://refhub.elsevier.com/S2352-8478(23)00108-9/sref96http://refhub.elsevier.com/S2352-8478(23)00108-9/sref96http://refhub.elsevier.com/S2352-8478(23)00108-9/sref97http://refhub.elsevier.com/S2352-8478(23)00108-9/sref97http://refhub.elsevier.com/S2352-8478(23)00108-9/sref97http://refhub.elsevier.com/S2352-8478(23)00108-9/sref98http://refhub.elsevier.com/S2352-8478(23)00108-9/sref98http://refhub.elsevier.com/S2352-8478(23)00108-9/sref98http://refhub.elsevier.com/S2352-8478(23)00108-9/sref98http://refhub.elsevier.com/S2352-8478(23)00108-9/sref98http://refhub.elsevier.com/S2352-8478(23)00108-9/sref99http://refhub.elsevier.com/S2352-8478(23)00108-9/sref99http://refhub.elsevier.com/S2352-8478(23)00108-9/sref99http://refhub.elsevier.com/S2352-8478(23)00108-9/sref99http://refhub.elsevier.com/S2352-8478(23)00108-9/sref100http://refhub.elsevier.com/S2352-8478(23)00108-9/sref100http://refhub.elsevier.com/S2352-8478(23)00108-9/sref100http://refhub.elsevier.com/S2352-8478(23)00108-9/sref100http://refhub.elsevier.com/S2352-8478(23)00108-9/sref101http://refhub.elsevier.com/S2352-8478(23)00108-9/sref101http://refhub.elsevier.com/S2352-8478(23)00108-9/sref101http://refhub.elsevier.com/S2352-8478(23)00108-9/sref102http://refhub.elsevier.com/S2352-8478(23)00108-9/sref102http://refhub.elsevier.com/S2352-8478(23)00108-9/sref102http://refhub.elsevier.com/S2352-8478(23)00108-9/sref102http://refhub.elsevier.com/S2352-8478(23)00108-9/sref102http://refhub.elsevier.com/S2352-8478(23)00108-9/sref102http://refhub.elsevier.com/S2352-8478(23)00108-9/sref102http://refhub.elsevier.com/S2352-8478(23)00108-9/sref115http://refhub.elsevier.com/S2352-8478(23)00108-9/sref115http://refhub.elsevier.com/S2352-8478(23)00108-9/sref115http://refhub.elsevier.com/S2352-8478(23)00108-9/sref115http://refhub.elsevier.com/S2352-8478(23)00108-9/sref115http://refhub.elsevier.com/S2352-8478(23)00108-9/sref103http://refhub.elsevier.com/S2352-8478(23)00108-9/sref103http://refhub.elsevier.com/S2352-8478(23)00108-9/sref103http://refhub.elsevier.com/S2352-8478(23)00108-9/sref103http://refhub.elsevier.com/S2352-8478(23)00108-9/sref103http://refhub.elsevier.com/S2352-8478(23)00108-9/sref103http://refhub.elsevier.com/S2352-8478(23)00108-9/sref103http://refhub.elsevier.com/S2352-8478(23)00108-9/sref103http://refhub.elsevier.com/S2352-8478(23)00108-9/sref116http://refhub.elsevier.com/S2352-8478(23)00108-9/sref116http://refhub.elsevier.com/S2352-8478(23)00108-9/sref116http://refhub.elsevier.com/S2352-8478(23)00108-9/sref116http://refhub.elsevier.com/S2352-8478(23)00108-9/sref116http://refhub.elsevier.com/S2352-8478(23)00108-9/sref117http://refhub.elsevier.com/S2352-8478(23)00108-9/sref117http://refhub.elsevier.com/S2352-8478(23)00108-9/sref117http://refhub.elsevier.com/S2352-8478(23)00108-9/sref117http://refhub.elsevier.com/S2352-8478(23)00108-9/sref117http://refhub.elsevier.com/S2352-8478(23)00108-9/sref105http://refhub.elsevier.com/S2352-8478(23)00108-9/sref105http://refhub.elsevier.com/S2352-8478(23)00108-9/sref105http://refhub.elsevier.com/S2352-8478(23)00108-9/sref118http://refhub.elsevier.com/S2352-8478(23)00108-9/sref118http://refhub.elsevier.com/S2352-8478(23)00108-9/sref118http://refhub.elsevier.com/S2352-8478(23)00108-9/sref119http://refhub.elsevier.com/S2352-8478(23)00108-9/sref119http://refhub.elsevier.com/S2352-8478(23)00108-9/sref119http://refhub.elsevier.com/S2352-8478(23)00108-9/sref119http://refhub.elsevier.com/S2352-8478(23)001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Sun, H. Li, J. Tan et al. Journal of Materiomics 10 (2024) 218e233performance of n-type PbS through synergistically integrating in resonantlevel and Cu dynamic doping. J Phys Chem Solid 2021;148:109640.[142] Zhao L-D, Lo S-H, He J, Li H, Biswas K, Androulakis J, et al. High performancethermoelectrics from earth-abundant materials: enhanced figure of merit inPbS by second phase nanostructures. J Am Chem Soc 2011;133(50):20476e87.[143] Xu B, Feng T, Li Z, Pantelides ST, Wu Y. Constructing highly porous ther-moelectric monoliths with high-performance and improved portability fromsolution-synthesized shape-controlled nanocrystals. Nano Lett 2018;18(6):4034e9.[144] Du X, Wang Y, Shi R, Mao Z, Yuan Z. Effects of anion and cation doping on thethermoelectric properties of n-type PbS. J Eur Ceram Soc 2018;38(10):3512e7.[145] Hou Z, Hong T, Wang D, Gao X, Qiu Y, Zhao L-D. Contrasting thermoelectrictransport properties of n-type PbS induced by adding Ni and Zn. ACS ApplEnergy Mater 2021;4(6):6284e9.[146] Yang J, Zhang X, Liu G, Zhao L, Liu J, Shi Z, et al. Multiscale structure and bandconfiguration tuning to achieve high thermoelectric properties in n-type PbSbulks. Nano Energy 2020;74:104826.[147] Zhao M, Chang C, Xiao Y, Zhao L-D. High performance of n-type (PbS)1-x-y(PbSe)x(PbTe)y thermoelectric materials. J Alloys Compd 2018;744:769e77.[148] Asfandiyar, Cai B, Zhao L-D, Li J-F. High thermoelectric figure of merit ZT > 1in SnS polycrystals. J Materiomics 2020;6(1):77e85.[149] Wu H, Lu X, Wang G, Peng K, Chi H, Zhang B, et al. Sodium-doped tin sulfidesingle crystal: anontoxic earth-abundant material with high thermoelectricperformance. Adv Energy Mater 2018;8(20):1800087.[150] He W, Wang D, Dong J-F, Qiu Y, Fu L, Feng Y, et al. Remarkable electron andphonon band structures lead to a high thermoelectric performance ZT > 1 inearth-abundant and eco-friendly SnS crystals. J Mater Chem 2018;6(21):10048e56.[151] Tan Q, Li J-F. Thermoelectric properties of Sn-S bulk materials prepared bymechanical alloying and spark plasma sintering. J Electron Mater2014;43(6):2435e9.[152] Tang H, Dong J-F, Sun F-H, Asfandiyar, Shang P, Li J-F. Adjusting Na dopingvia wet-chemical synthesis to enhance thermoelectric properties of poly-crystalline SnS. Sci China Mater 2019;62(7):1005e12.[153] Suekuni K, Tsuruta K, Ariga T, Koyano M. Thermoelectric properties ofmineral tetrahedrites Cu10Tr2Sb4S13 with low thermal conductivity. APEX2012;5(5):051201.[154] Weller DP, Kunkel GE, Ochs AM, Morelli DT, Anderson ME. Observation of n-type behavior in Fe-doped tetrahedrite at low temperature. Mater TodayPhys 2018;7:1e6.[155] Tippireddy S, Chetty R, Naik MH, Jain M, Chattopadhyay K, Mallik RC. Elec-tronic and thermoelectric properties of transition metal substituted tetra-hedrites. J Phys Chem C 2018;122(16):8735e49.[156] Chetty R, Bali A, Naik MH, Rogl G, Rogl P, Jain M, et al. Thermoelectricproperties of Co substituted synthetic tetrahedrite. Acta Mater 2015;100:266e74.[157] Suekuni K, Tsuruta K, Kunii M, Nishiate H, Nishibori E, Maki S, et al. High-performance thermoelectric mineral Cu12-xNixSb4S13 tetrahedrite. J ApplPhys 2013;113(4):043712.[158] Harish S, Sivaprahasam D, Battabyal M, Gopalan R. Phase stability andthermoelectric properties of Cu10.5Zn1.5Sb4S13 tetrahedrite. J Alloys Compd2016;667:323e8.[159] Heo J, Laurita G, Muir S, Subramanian MA, Keszler DA. Enhanced thermo-electric performance of synthetic tetrahedrites. Chem Mater 2014;26(6):2047e51.[160] Kumar DSP, Tippireddy S, Ramakrishnan A, Chen K-H, Malar P, Mallik RC.Thermoelectric and electronic properties of chromium substituted tetrahe-drite. Semicond Sci Technol 2019;34(3):035017.[161] Zhu C, Chen Q, Ming H, Qin X, Yang Y, Zhang J, et al. Improved thermoelectricperformance of Cu12Sb4S13 through Gd-substitution induced enhancementof electronic density of states and phonon scattering. ACS Appl Mater In-terfaces 2021;13(21):25092e101.[162] Goto Y, Sakai Y, Kamihara Y, Matoba M. Effect of Sn-substitution on ther-moelectric properties of copper-based sulfide, famatinite Cu3SbS4. J Phys SocJpn 2015;84(4):044706.[163] Huang LL, Wang YS, Zhu C, Xu R, Li JM, Zhang JH, et al. Preparation andenhanced thermoelectric performance of Pb-doped tetrahedrite Cu12-xPbxSb4S13. J Alloys Compd 2018;769:478e83.[164] Levinsky P, Candolfi C, Dauscher A, Lenoir B, Hejtmanek J. Thermoelectricproperties of magnesium-doped tetrahedrite Cu12-xMgxSb4S13. J ElectronMater 2019;48(4):1926e31.[165] Tippireddy S, Ghosh S, Biswas R, Dasgupta T, Rogl G, Rogl P, et al. Thermo-electric properties of Al substituted tetrahedrite. J Appl Phys 2020;127(3):035105.[166] Huang L, Kong Y, Zhang J, Xu R, Zhu C, Wu J, et al. Achieving a high232thermoelectric performance of tetrahedrites by adjusting the eelectronicdensity of states and enhancing phonon scattering. ACS Appl Mater In-terfaces 2019;11(26):23361e71.[167] Tippireddy S, Kumar DSP, Karati A, Ramakrishnan A, Sarkar S, Peter SC, et al.Effect of Sn substitution on the thermoelectric properties of synthetictetrahedrite. ACS Appl Mater Interfaces 2019;11(24):21686e96.[168] Kumar DSP, Chetty R, Femi OE, Chattopadhyay K, Malar P, Mallik RC. Ther-moelectric properties of Bi doped tetrahedrite. J Electron Mater 2017;46(5):2616e22.[169] Levinsky P, Candolfi C, Dauscher A, Tobola J, Hejtmanek J, Lenoir B. Ther-moelectric properties of the tetrahedrite-tennantite solid solutions Cu12Sb4-xAsxS13 and Cu10Co2Sb4-yAsyS13 (0 < x ¼ y < 4). Phys Chem Chem Phys2019;21(8):4547e55.[170] Bouyrie Y, Candolfi C, Ohorodniichuk V, Malaman B, Dauscher A, Tobola J,et al. Crystal structure, electronic band structure and high-temperaturethermoelectric properties of Te-substituted tetrahedrites Cu12Sb4-xTexS13(0.5 < x < 2.0). J Mater Chem C 2015;3(40):10476e87.[171] Lu X, Morelli DT, Xia Y, Ozolins V. Increasing the thermoelectric figure ofmerit of tetrahedrites by Co-doping with nickel and zinc. Chem Mater2015;27(2):408e13.[172] Weller DP, Morelli DT. Rapid synthesis of zinc and nickel co-doped tetra-hedrite thermoelectrics by reactive spark plasma sintering and mechanicalalloying. J Alloys Compd 2017;710:794e9.[173] Rout U, Tippireddy S, Werbach K, Pambannan P, Rogl G, Rogl P, et al.Simultaneous optimization of power factor and thermal conductivity via Teand Se double substitution in Cu12Sb4S13 tetrahedrite. Scripta Mater2020;188:151e6.[174] Yan Y, Wu H, Wang G, Lu X, Zhou X. High thermoelectric performancebalanced by electrical and thermal transport in tetrahedrites Cu12þxSb4S12Se.Energy Storage Mater 2018;13:127e33.[175] Lu X, Yao W, Wang GW, Zhou XY, Morelli D, Zhang YS, et al. Band structureengineering in highly degenerate tetrahedrites through isovalent doping.J Mater Chem 2016;4(43):17096e103.[176] Lu X, Morelli DT, Wang YX, Lai W, Xia Y, Ozolins V. Phase stability, crystalstructure, and thermoelectric properties of Cu12Sb4S13-xSex solid solutions.Chem Mater 2016;28(6):1781e6.[177] Sun F-H, Dong J, Tang H, Shang P-P, Zhuang H-L, Hu H, et al. Enhancedperformance of thermoelectric nanocomposites based on Cu12Sb4S13 tetra-hedrite. Nano Energy 2019;57:835e41.[178] Weller DP, Stevens DL, Kunkel GE, Ochs AM, Holder CF, Morelli DT, et al.Thermoelectric performance of tetrahedrite synthesized by a modified pol-yol process. Chem Mater 2017;29(4):1656e64.[179] Hu HH, Sun FH, Dong JF, Zhuang HL, Cai BW, Pei J, et al. Nanostructure en-gineering and performance enhancement in Fe2O3-dispersed Cu12Sb4S13thermoelectric composites with earth-abundant elements. ACS Appl MaterInterfaces 2020;12(15):17864e72.[180] Sun F-H, Dong J, Tang H, Zhuang H-L, Li J-F. ZnO-nanoparticle-dispersedCu11.5Ni0.5Sb4S13-d tetrahedrite composites with enhanced thermoelectricperformance. J Electron Mater 2019;48(4):1840e5.[181] Kumar VP, Guelou G, Lemoine P, Raveau B, Supka AR, Al Orabi RAR, et al.Copper-rich thermoelectric dulfides: size-mismatch effect and chemicaldisorder in the TS4Cu6 complexes of Cu26T2Ge6S32 (T ¼ Cr, Mo, W) colusites.Angew Chem, Int Ed 2019;58(43):15455e63.[182] Kumar VP, Mitra S, Guelou G, Supka AR, Lemoine P, Raveau B, et al. Transportproperties and electronic density-of-states of Zn-doped colusiteCu26Cr2Ge6S32. Appl Phys Lett 2020;117(17):173902.[183] Kim FS, Suekuni K, Nishiate H, Ohta M, Tanaka HI, Takabatake T. Tuning thecharge carrier density in the thermoelectric colusite. J Appl Phys2016;119(17):175105.[184] Guelou G, Kumar VP, Bourhim A, Lemoine P, Raveau B, Supka A, et al.Toppling the transport properties with cationic overstoichiometry in ther-moelectric colusite: Cu26Cr2Ge6(1þdelta)S32. ACS Appl Energy Mater2020;3(5):4180e5.[185] Guo L, Zhang B, Zhu H, Wu H, Yan Y, Gong X, et al. Manipulating the phasetransformation temperature to achieve cubic Cu5FeS4-xSex and enhancedthermoelectric performance. J Mater Chem C 2020;8(48):17222e8.[186] Hwang J-Y, Ahn JY, Lee KH, Kim SW. Structural optimization for thermo-electric properties in Cu-Bi-S pavonite compounds. J Alloys Compd2017;704:282e8.[187] You Y, Su X, Liu W, Yan Y, Fu J, Cheng X, et al. Structure and thermoelectricproperty of Te doped paracostibite CoSb1-xTexS compounds. J Solid StateChem 2018;262:1e7.[188] Gu Y, Ai W, Zhao Y, Pan L, Lu C, Zong P, et al. Remarkable thermoelectricproperty enhancement in Cu2SnS3-CuCo2S4 nanocomposites via 3D modu-lation doping. J Mater Chem 2021;9(31):16928e35.[189] Saxena M, Tarachand, Bera AK, Okram GS. Impact of non-stoichiometry inthe thermoelectric performance of polyol method prepared Cu1þxIn1-xS2 (x ¼http://refhub.elsevier.com/S2352-8478(23)00108-9/sref142http://refhub.elsevier.com/S2352-8478(23)00108-9/sref142http://refhub.elsevier.com/S2352-8478(23)00108-9/sref143http://refhub.elsevier.com/S2352-8478(23)00108-9/sref143http://refhub.elsevier.com/S2352-8478(23)00108-9/sref143http://refhub.elsevier.com/S2352-8478(23)00108-9/sref143http://refhub.elsevier.com/S2352-8478(23)00108-9/sref143http://refhub.elsevier.com/S2352-8478(23)00108-9/sref144http://refhub.elsevier.com/S2352-8478(23)00108-9/sref144http://refhub.elsevier.com/S2352-8478(23)00108-9/sref144http://refhub.elsevier.com/S2352-8478(23)00108-9/sref144http://refhub.elsevier.com/S2352-8478(23)00108-9/sref144http://refhub.elsevier.com/S2352-8478(23)00108-9/sref145http://refhub.elsevier.com/S2352-8478(23)00108-9/sref145http://refhub.elsevier.com/S2352-8478(23)00108-9/sref145http://refhub.elsevier.com/S2352-8478(23)00108-9/sref145http://refhub.elsevier.com/S2352-8478(23)00108-9/sref146http://refhub.elsevier.com/S2352-8478(23)00108-9/sref146http://refhub.elsevier.com/S2352-8478(23)00108-9/sref146http://refhub.elsevier.com/S2352-8478(23)00108-9/sref146http://refhub.elsevier.com/S2352-8478(23)00108-9/sref132http://refhub.elsevier.com/S2352-8478(23)00108-9/sref132http://refhub.elsevier.com/S2352-8478(23)00108-9/sref132http://refhub.elsevier.com/S2352-8478(23)00108-9/sref147http://refhub.elsevier.com/S2352-8478(23)00108-9/sref147http://refhub.elsevier.com/S2352-8478(23)00108-9/sref147http://refhub.elsevier.com/S2352-8478(23)00108-9/sref147http://refhub.elsevier.com/S2352-8478(23)00108-9/sref147http://refhub.elsevier.com/S2352-8478(23)00108-9/sref147http://refhub.elsevier.com/S2352-8478(23)00108-9/sref151http://refhub.elsevier.com/S2352-8478(23)00108-9/sref151http://refhub.elsevier.com/S2352-8478(23)00108-9/sref151http://refhub.elsevier.com/S2352-8478(23)00108-9/sref150http://refhub.elsevier.com/S2352-8478(23)00108-9/sref150http://refhub.elsevier.com/S2352-8478(23)00108-9/sref150http://refhub.elsevier.com/S2352-8478(23)00108-9/sref152http://refhub.elsevier.com/S2352-8478(23)00108-9/sref152http://refhub.elsevier.com/S2352-8478(23)00108-9/sref152http://refhub.elsevier.com/S2352-8478(23)00108-9/sref152http://refhub.elsevier.com/S2352-8478(23)00108-9/sref152http://refhub.elsevier.com/S2352-8478(23)00108-9/sref148http://refhub.elsevier.com/S2352-8478(23)00108-9/sref148http://refhub.elsevier.com/S2352-8478(23)00108-9/sref148http://refhub.elsevier.com/S2352-8478(23)00108-9/sref148http://refhub.elsevier.com/S2352-8478(23)00108-9/sref149http://refhub.elsevier.com/S2352-8478(23)00108-9/sref149http://refhub.elsevier.com/S2352-8478(23)00108-9/sref149http://refhub.elsevier.com/S2352-8478(23)00108-9/sref149http://refhub.elsevier.com/S2352-8478(23)00108-9/sref153http://refhub.elsevier.com/S2352-8478(23)00108-9/sref153http://refhub.elsevier.com/S2352-8478(23)00108-9/sref153http://refhub.elsevier.com/S2352-8478(23)00108-9/sref153http://refhub.elsevier.com/S2352-8478(23)00108-9/sref153http://refhub.elsevier.com/S2352-8478(23)00108-9/sref153http://refhub.elsevier.com/S2352-8478(23)00108-9/sref153http://refhub.elsevier.com/S2352-8478(23)00108-9/sref154http://refhub.elsevier.com/S2352-8478(23)00108-9/sref154http://refhub.elsevier.com/S2352-8478(23)00108-9/sref154http://refhub.elsevier.com/S2352-8478(23)00108-9/sref154http://refhub.elsevier.com/S2352-8478(23)00108-9/sref155http://refhub.elsevier.com/S2352-8478(23)00108-9/sref155http://refhub.elsevier.com/S2352-8478(23)00108-9/sref155http://refhub.elsevier.com/S2352-8478(23)00108-9/sref155http://refhub.elsevier.com/S2352-8478(23)00108-9/sref156http://refhub.elsevier.com/S2352-8478(23)00108-9/sref156http://refhub.elsevier.com/S2352-8478(23)00108-9/sref156http://refhub.elsevier.com/S2352-8478(23)00108-9/sref156http://refhub.elsevier.com/S2352-8478(23)00108-9/sref157http://refhub.elsevier.com/S2352-8478(23)00108-9/sref157http://refhub.elsevier.com/S2352-8478(23)00108-9/sref157http://refhub.elsevier.com/S2352-8478(23)00108-9/sref157http://refhub.elsevier.com/S2352-8478(23)00108-9/sref157http://refhub.elsevier.com/S2352-8478(23)00108-9/sref157http://refhub.elsevier.com/S2352-8478(23)00108-9/sref157http://refhub.elsevier.com/S2352-8478(23)00108-9/sref158http://refhub.elsevier.com/S2352-8478(23)00108-9/sref158http://refhub.elsevier.com/S2352-8478(23)00108-9/sref158http://refhub.elsevier.com/S2352-8478(23)00108-9/sref158http://refhub.elsevier.com/S2352-8478(23)00108-9/sref158http://refhub.elsevier.com/S2352-8478(23)00108-9/sref158http://refhub.elsevier.com/S2352-8478(23)00108-9/sref158http://refhub.elsevier.com/S2352-8478(23)00108-9/sref158http://refhub.elsevier.com/S2352-8478(23)00108-9/sref159http://refhub.elsevier.com/S2352-8478(23)00108-9/sref159http://refhub.elsevier.com/S2352-8478(23)00108-9/sref159http://refhub.elsevier.com/S2352-8478(23)00108-9/sref159http://refhub.elsevier.com/S2352-8478(23)00108-9/sref160http://refhub.elsevier.com/S2352-8478(23)00108-9/sref160http://refhub.elsevier.com/S2352-8478(23)00108-9/sref160http://refhub.e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9/sref187http://refhub.elsevier.com/S2352-8478(23)00108-9/sref187http://refhub.elsevier.com/S2352-8478(23)00108-9/sref187http://refhub.elsevier.com/S2352-8478(23)00108-9/sref188http://refhub.elsevier.com/S2352-8478(23)00108-9/sref188http://refhub.elsevier.com/S2352-8478(23)00108-9/sref188http://refhub.elsevier.com/S2352-8478(23)00108-9/sref188http://refhub.elsevier.com/S2352-8478(23)00108-9/sref188http://refhub.elsevier.com/S2352-8478(23)00108-9/sref188http://refhub.elsevier.com/S2352-8478(23)00108-9/sref188http://refhub.elsevier.com/S2352-8478(23)00108-9/sref188http://refhub.elsevier.com/S2352-8478(23)00108-9/sref189http://refhub.elsevier.com/S2352-8478(23)00108-9/sref189http://refhub.elsevier.com/S2352-8478(23)00108-9/sref189http://refhub.elsevier.com/S2352-8478(23)00108-9/sref189http://refhub.elsevier.com/S2352-8478(23)00108-9/sref189http://refhub.elsevier.com/S2352-8478(23)00108-9/sref189F.-H. Sun, H. Li, J. Tan et al. Journal of Materiomics 10 (2024) 218e233-0.3,-0.2,-0.1, 0, 0.1, 0.2) nanowires. J Alloys Compd 2021;881:160517.[190] Labegorre J-B, Virfeu A, Bourhim A, Willeman H, Barbier T, Appert F, et al.XBi4S7 (X ¼ Mn, Fe): new cost-efficient layered n-type thermoelectric sul-fides with ultralow thermal conductivity. Adv Funct Mater 2019;29(48):1904112.[191] Li F, Ruan M, Jabar B, Liang C, Chen Y, Ao D, et al. High thermoelectricproperties achieved in environmentally friendly sulfide compound Bi2SeS2by nanoenginnering. Nano Energy 2021;88:106273.[192] Li J, Pan Y, Wu C, Sun F, Wei T. Processing of advanced thermoelectric ma-terials. Sci China Technol Sci 2017;60(9):1347e64.[193] Li Z-Y, Li J-F. Fine-grained and nanostructured AgPbmSbTemþ2 alloys withhigh thermoelectric figure of merit at medium temperature. Adv EnergyMater 2014;4(2):201300937.[194] Jiang Y, Dong J, Zhuang H-L, Yu J, Su B, Li H, et al. Evolution of defectstructures leading to high ZT in GeTe-based thermoelectric materials. NatCommun 2022;13(1):6087.[195] Su X, Fu F, Yan Y, Zheng G, Liang T, Zhang Q, et al. Self-propagating high-temperature synthesis for compound thermoelectrics and new criterionfor combustion processing. Nat Commun 2014;5:4908.[196] Su X, Wei P, Li H, Liu W, Yan Y, Li P, et al. Multi-scale microstructuralthermoelectric materials: transport behavior, non-equilibrium preparation,and applications. Adv Mater 2017;29(20):1602013.[197] Yang D, Luo T, Su X, Wu J, Tang X. Unveiling the intrinsic low thermalconductivity of BiAgSeS through entropy engineering in SHS kinetic process.J Inorg Mater 2021;36(9):991e8.[198] Das P, Claverie JP. Synthesis of single-core and multiple-core core-shellnanoparticles by RAFT emulsion polymerization: lead sulfide-copolymernanocomposites. J Polym Sci, Polym Chem Ed 2012;50(14):2802e8.[199] Li D, Hao S, Xing G, Li Y, Li X, Fan L, et al. Solution grown single-unit-cellquantum wires affording self-powered solar-blind UV photodetectors withultrahigh selectivity and sensitivity. J Am Chem Soc 2019;141(8):3480e8.[200] Wang XL, Swihart MT. Controlling the size, shape, phase, band gap, andlocalized surface plasmon resonance of Cu2-xS and CuxInyS nanocrystals.Chem Mater 2015;27(5):1786e91.[201] Abinaya R, Harish S, Ponnusamy S, Shimomura M, Navaneethan M,Archana J. Enhanced thermoelectric figure-of-merit of MoS2/a-MoO3 nano-sheets via tuning of sulphur vacancies. Chem Eng J 2021;416:128484.[202] Zhang A, Zhang B, Lu W, Xie D, Ou H, Han X, et al. Twin engineering inwolution-wynthesized nonstoichiometric Cu5FeS4 icosahedral nanoparticlesfor enhanced thermoelectric performance. Adv Funct Mater 2018;28(10):1705117.[203] Wang L, Zhang Z, Geng L, Yuan T, Liu Y, Guo J, et al. Solution-printablefullerene/TiS2 organic/inorganic hybrids for high-performance flexible n-type thermoelectrics. Energy Environ Sci 2018;11(5):1307e17.233Fu-Hua Sun is currently an associate professor of Schoolof Materials Science and Engineering at Hubei NormalUniversity, China. He received his Ph.D. degree fromTsinghua University in 2019. He worked as a postdoctoralresearch fellow at Wuhan University of Technology(2020e2022). His current research focuses on the syn-thesis of nano-bulk sulfur-based materials and their appli-cations in thermoelectric.Hezhang Li received his Ph.D. degree from Tohoku Uni-versity, Japan in 2022 and then worked in National Insti-tute for Materials Science (NIMS), Japan as a postdocresearcher from April 2022 to February 2023. He is now apostdoctoral researcher at Tsinghua University, China. Hisresearch focuses on the calculation of electronic structure,crystal structure analysis and the transport properties ofHeusler alloys and other thermoelectric materials.Takao Mori is a professor at NIMS & University of Tsu-kuba, Tsukuba, Japan. Prof. Mori's present research fieldsfocus on Thermoelectrics, Magnetism, Solid State Physics,Inorganic Materials Science, and Material Synthesis. He isparticularly interested in inorganic compounds with“network” structures; atomic clusters, cages, and nets.One particular focus is to develop thermoelectric mate-rials viable for the first wide scale applications. From 2010Prof. Mori has been a Visiting Professor at HiroshimaUniversity, and Adj. Prof. at Univ. of Tsukuba. Prof. Mori isalso Lab Director of the NIMS Open Innovation Center(NOIC), Thermal Energy Conversion Lab, which is a mul-ticompany and institute open innovation endeavor car-rying out challenging research on thermoelectrics.http://refhub.elsevier.com/S2352-8478(23)00108-9/sref189http://refhub.elsevier.com/S2352-8478(23)00108-9/sref190http://refhub.elsevier.com/S2352-8478(23)00108-9/sref190http://refhub.elsevier.com/S2352-8478(23)00108-9/sref190http://refhub.elsevier.com/S2352-8478(23)00108-9/sref190http://refhub.elsevier.com/S2352-8478(23)00108-9/sref190http://refhub.elsevier.com/S2352-8478(23)00108-9/sref190http://refhub.elsevier.com/S2352-8478(23)00108-9/sref190http://refhub.elsevier.com/S2352-8478(23)00108-9/sref191http://refhub.elsevier.com/S2352-8478(23)00108-9/sref191http://refhub.elsevier.com/S2352-8478(23)00108-9/sref191http://refhub.elsevier.com/S2352-8478(23)00108-9/sref191http://refhub.elsevier.com/S2352-8478(23)00108-9/sref192http://refhub.elsevier.com/S2352-8478(23)00108-9/sref192http://refhub.elsevier.com/S2352-8478(23)00108-9/sref192http://refhub.elsevier.com/S2352-8478(23)00108-9/sref193http://refhub.elsevier.com/S2352-8478(23)00108-9/sref193http://refhub.elsevier.com/S2352-8478(23)00108-9/sref193http://refhub.elsevier.com/S2352-8478(23)00108-9/sref193http://refhub.elsevier.com/S2352-8478(23)00108-9/sref193http://refhub.elsevier.com/S2352-8478(23)00108-9/sref193http://refhub.elsevier.com/S2352-8478(23)00108-9/sref194http://refhub.elsevier.com/S2352-8478(23)00108-9/sref194http://refhub.elsevier.com/S2352-8478(23)00108-9/sref194http://refhub.elsevier.com/S2352-8478(23)00108-9/sref195http://refhub.elsevier.com/S2352-8478(23)00108-9/sref195http://refhub.elsevier.com/S2352-8478(23)00108-9/sref195http://refhub.elsevier.com/S2352-8478(23)00108-9/sref196http://refhub.elsevier.com/S2352-8478(23)00108-9/sref196http://refhub.elsevier.com/S2352-8478(23)00108-9/sref196http://refhub.elsevier.com/S2352-8478(23)00108-9/sref197http://refhub.elsevier.com/S2352-8478(23)00108-9/sref197http://refhub.elsevier.com/S2352-8478(23)00108-9/sref197http://refhub.elsevier.com/S2352-8478(23)00108-9/sref197http://refhub.elsevier.com/S2352-8478(23)00108-9/sref198http://refhub.elsevier.com/S2352-8478(23)00108-9/sref198http://refhub.elsevier.com/S2352-8478(23)00108-9/sref198http://refhub.elsevier.com/S2352-8478(23)00108-9/sref198http://refhub.elsevier.com/S2352-8478(23)00108-9/sref199http://refhub.elsevier.com/S2352-8478(23)00108-9/sref199http://refhub.elsevier.com/S2352-8478(23)00108-9/sref199http://refhub.elsevier.com/S2352-8478(23)00108-9/sref199http://refhub.elsevier.com/S2352-8478(23)00108-9/sref200http://refhub.elsevier.com/S2352-8478(23)00108-9/sref200http://refhub.elsevier.com/S2352-8478(23)00108-9/sref200http://refhub.elsevier.com/S2352-8478(23)00108-9/sref200http://refhub.elsevier.com/S2352-8478(23)00108-9/sref200http://refhub.elsevier.com/S2352-8478(23)00108-9/sref200http://refhub.elsevier.com/S2352-8478(23)00108-9/sref200http://refhub.elsevier.com/S2352-8478(23)00108-9/sref201http://refhub.elsevier.com/S2352-8478(23)00108-9/sref201http://refhub.elsevier.com/S2352-8478(23)00108-9/sref201http://refhub.elsevier.com/S2352-8478(23)00108-9/sref201http://refhub.elsevier.com/S2352-8478(23)00108-9/sref201http://refhub.elsevier.com/S2352-8478(23)00108-9/sref202http://refhub.elsevier.com/S2352-8478(23)00108-9/sref202http://refhub.elsevier.com/S2352-8478(23)00108-9/sref202http://refhub.elsevier.com/S2352-8478(23)00108-9/sref202http://refhub.elsevier.com/S2352-8478(23)00108-9/sref202http://refhub.elsevier.com/S2352-8478(23)00108-9/sref202http://refhub.elsevier.com/S2352-8478(23)00108-9/sref203http://refhub.elsevier.com/S2352-8478(23)00108-9/sref203http://refhub.elsevier.com/S2352-8478(23)00108-9/sref203http://refhub.elsevier.com/S2352-8478(23)00108-9/sref203http://refhub.elsevier.com/S2352-8478(23)00108-9/sref203 Review of current ZT ﹥ 1 thermoelectric sulfides 1. Introduction 2. Structural merits for sulfide thermoelectrics 2.1. Superionic conduction of thermoelectric sulfides 2.2. Band configuration tuning 2.3. Anomalous harmonic phonon scattering 3. High performance thermoelectric binary sulfides 3.1. Copper sulfide 3.2. Lead sulfide 3.3. Tin sulfide 4. New polysulfides and thermoelectric enhancement 4.1. Tetrahedrite 4.2. Colusite 4.3. Other metal based sulfides 5. Synthesis recipes of thermoelectric sulfides 6. Conclusion and outlook Declaration of competing interest Acknowledgements References