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Keisuke Yoshikawa, Takeshi Kato, Yasuhiro Suzuki, Akihiro Shiota, [Tsuyoshi Ohnishi](https://orcid.org/0000-0002-2333-7752), Koji Amezawa, Aiko Nakao, Takeshi Yajima, [Yasutoshi Iriyama](https://orcid.org/0000-0001-8639-0844)

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[Origin of O<sub>2</sub> Generation in Sulfide‐Based All‐Solid‐State Batteries and its Impact on High Energy Density](https://mdr.nims.go.jp/datasets/088f6940-c0cf-43c5-b411-bf81c4c80bb4)

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Origin of O2 Generation in Sulfide‐Based All‐Solid‐State Batteries and its Impact on High Energy DensityRESEARCH ARTICLEwww.advancedscience.comOrigin of O2 Generation in Sulfide-Based All-Solid-StateBatteries and its Impact on High Energy DensityKeisuke Yoshikawa, Takeshi Kato, Yasuhiro Suzuki, Akihiro Shiota, Tsuyoshi Ohnishi,Koji Amezawa, Aiko Nakao, Takeshi Yajima, and Yasutoshi Iriyama*The cathode surface of sulfide-based all-solid-state batteries (SBs) iscommonly coated with amorphous-LiNbO3 in order to stabilizecharge–discharge reactions. However, high-voltage charging diminishes theadvantages, which is caused by problems with the amorphous-LiNbO3coating layer. This study has investigated the degradation ofamorphous-LiNbO3 coating layer directly during the high-voltage charging ofSBs. O2 generation via Li extraction from the amorphous-LiNbO3 coatinglayer is observed using electrochemical gas analysis and electrochemical X-rayphotoelectron spectroscopy. This O2 leads to the formation of an oxidativesolid electrolyte (SE) around the coating layer and degrades the batteryperformance. On the other hand, elemental substitution (i.e.,amorphous-LiNbxP1-xO3) reduces O2 release, leading to stable high-voltagecharge–discharge reactions of SBs. The results have emphasized that thesuppression of O2 generation is a key factor in improving the energy densityof SBs.K. Yoshikawa, T. Kato, Y. Suzuki, A. Nakao, T. Yajima, Y. IriyamaDepartment of Material Design Innovation EngineeringGraduate School of EngineeringNagoya UniversityFuro-cho, Chikusa-ku, Nagoya, Aichi 464-8603, JapanE-mail: iriyama.yasutoshi@material.nagoya-u.ac.jpA. ShiotaConsortium for Lithium Ion Battery Technology and Evaluation Center(LIBTEC)1-8-31 Midorigaoka, Ikeda, Osaka 563-8577, JapanT. OhnishiCenter for Green Research on Energy and Environmental MaterialsNational Institute for Materials Science (NIMS)1-1 Namiki, Tsukuba, Ibaraki 305-0044, JapanK. AmezawaInstitute of Multidisciplinary Research for Advanced MaterialsTohoku University2-1-1, Katahira, Aoba-Ku, Sendai, Miyagi 980-8577, JapanThe ORCID identification number(s) for the author(s) of this articlecan be found under https://doi.org/10.1002/advs.202402528© 2024 The Author(s). Advanced Science published by Wiley-VCHGmbH. This is an open access article under the terms of the CreativeCommons Attribution License, which permits use, distribution andreproduction in any medium, provided the original work is properly cited.DOI: 10.1002/advs.2024025281. IntroductionSulfide-based all-solid-state batteries (SBs)are expected as advanced power sourcesfor electric vehicles (EVs). This is be-cause sulfide-based solid electrolytes (SEs)are highly Li+ conductive materials[1] andare ductile,[2] which are beneficial for fastcharge–discharge reactions in the SBs ofEVs and large-scale battery manufactur-ing processes. However, SEs have a nar-row potential window[3] and they are highlyreactive with cathode materials, leadingto a resistive interface.[4] To overcomethese problems, a coating layer, commonlyamorphous-LiNbO3 (a-LNbO, ≈10 nm inthickness), is formed on the cathode surfaceand several issues have been examined.[5]A practical method for improving theenergy density of SBs is to increase theircharging voltages. However, high-voltagecharging degrades SBs and several types of degradationscan occur inside SBs, such as deterioration of the cathodestructure,[6] degradation of the coating layer,[3] and oxidationof the SEs around the coating layer.[7] A typical cathode mate-rial, LiNixCoyMn1−x−yO2 (NCM), releases O2 during high-voltagecharging (≈4.55 V), and the layered structure of NCM irre-versibly transforms into a resistive spinel or rock-salt structure.[6]Gas analysis has been used to detect O2 release during the SBcharging process, as well as CO2 (due to the decomposition ofLi2CO3 on the NCM surface) and SO2 (due to side reactionswith SEs).[8] Coating layers protect NCM and reduce O2 releasefrom NCM.[6c,d,8b,d,e] However, coating layers also degrade at high-voltage charging and become alternative degradation sources.[7]In the case of the a-LNbO coating layer, the following decompo-sition schemes have been proposed indirectly based on X-ray ab-sorption fine structure (XAFS) analysis of Nb L3-edge local struc-ture variations at high voltages:[7d]LiNbO3 → Li1−2xNbO3−x + xLi2O (1)Li2O → 0.5O2 + 2Li+ + 2e− (2)In this study, we have investigated the gas generation from SBswith and without coating layers on the NCM. We demonstratethat a larger amount of O2 is generated from the a-LNbO coat-ing layer during high-voltage charging. Additionally, Li extractionfrom the a-LNbO coating layer is confirmed using electrochem-Adv. Sci. 2024, 2402528 2402528 (1 of 7) © 2024 The Author(s). Advanced Science published by Wiley-VCH GmbHhttp://www.advancedscience.commailto:iriyama.yasutoshi@material.nagoya-u.ac.jphttps://doi.org/10.1002/advs.202402528http://creativecommons.org/licenses/by/4.0/http://creativecommons.org/licenses/by/4.0/http://crossmark.crossref.org/dialog/?doi=10.1002%2Fadvs.202402528&domain=pdf&date_stamp=2024-07-08www.advancedsciencenews.com www.advancedscience.comFigure 1. a) Charge–discharge curves of B-SB (upper), Nb-SB (middle) and NbP-SB (lower) from 1st to 3rd cycle (3.00–4.55 V, 60 °C, I = 200 μA cm−2).b) Schematic image of gas analysis system. SBs are sealed in SUS vessel, which are stored at 60 °C and connected to mass spectrometer (MS) andpotentiostat-galvanostat.ical X-ray photoelectron spectroscopy (XPS) analysis. These re-sults directly support the forementioned degradation schemes.Based on these results, we propose that the design of coatinglayers that suppress O2 generation is a key factor in stabiliz-ing the high-voltage charging of SBs. In fact, we will show thatan amorphous-LiNbxP1-xO3 (a-LNbPO) coating layer, which isknown to improve the high-voltage stability of SBs,[9] generatesless O2.2. Results2.1. Gas Analysis Using Practical SBsThe SBs used for gas analysis comprise LiNi0.5Co0.2Mn0.3O2(NCM523) particles as the cathode, Li7−xPS6−xClx (x ≈1, con-ductivity ≈2 × 10−3 S cm−1) as the SE, and In–Li alloy (0.62 Vvs Li/Li+[10]) as the anode (FigureS1, Supporting Information).In this study, three types of SBs with a-LNbO-coated NCM523(Nb-SB), a-LNbPO-coated NCM523 (NbP-SB), or bare NCM523(B-SB) were assembled according to previous reports, where thethickness of each coating layer was 2–10 nm.[7,9] Figure 1a showsthe charge–discharge curves of the SBs at 60 °C. The deliveredcapacities and Coulombic efficiencies were in the order of NbP-SB > Nb-SB > B-SB, confirming that coating layers improve thebattery performance as shown in our previous reports.[7a,9] Also,we have preliminary checked that a-LNbPO coating layer hasimproved charge–discharge reactions of an SB when comparedwith a-LNbO coated one using NCM523-graphite laminate celloperating at 60 °C for 300 cycles between 3.00 and 4.35 V (≈4.4 Vvs Li/Li+) (Figure S2, Supporting Information). The SBs wereAdv. Sci. 2024, 2402528 2402528 (2 of 7) © 2024 The Author(s). Advanced Science published by Wiley-VCH GmbH 21983844, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/advs.202402528 by Nagoya University, Wiley Online Library on [08/07/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons Licensehttp://www.advancedsciencenews.comhttp://www.advancedscience.comwww.advancedsciencenews.com www.advancedscience.comFigure 2. Time-dependent ion currents for m/z = 16 (brown), 18 (light blue), 32 (red), 34 (light green), 44 (black), and 64 (dark green) of a) chargedB-SB b) charged Nb-SB, and c) charged NbP-SB. d) Comparison of the current for m/z = 32 from B-SB (black), Nb-SB (red) and NbP-SB (light green).e) Integral amount of m/z = 16 (brown), 32 (red) at 4.55 V for 3 h from B-SB, Nb-SB and NbP-SB.sealed in a stainless use steel vessel. The vessel was placed inan incubator (60 °C) and was connected to a gas analyzer andpotentiostat–galvanostat. Gas analysis was performed undervacuum with constant voltages applied to the SBs (Figure 1b;Figure S3, Supporting Information).Figure 2a–c summarizes the gas analysis results for the B-SB,Nb-SB, and NbP-SB, respectively, where the voltages of the SBswere increased every 3 h to 3.00, 4.25, 4.55, and 5.00 V (vs Li/Li+).The mass-to-charge ratios of the ions (m/z) (16 (O), 18 (H2O), 32(O2 or S), 34 (H2S), 44 (CO2), and 64 (SO2)) were selected basedon previous reports and gas leaks from air.[8,11] An empty vesselwithout SB guaranteed constant ion currents at any m/z for 12 hin our system (Figure S3b, Supporting Information). At 3.00 and4.25 V, the ion currents of the selected m/z values were nearlyconsistent with those of the empty vessel. At 4.55 V, the ioncurrent from m/z = 16 and 32 increased and decayed with time.At 5.00 V, the ion current increased again only for m/z = 16 and32, with the exception of B-SB. Figure 2d compares the ion cur-rents at m/z = 32 for the SBs. The Nb-SB generated the highestpeak current and the NbP-SB generated the lowest peak currentamong the SBs at 4.55 V. Figure 2e summarizes the integralamount of m/z = 16 and 32 at 4.55 V calculated from the peakarea for 3 h in Figure 2d. Each integral amount for the Nb-SBwas 2.4–2.5 times larger than that for the B-SB, whereas that ofthe NbP-SB was 0.6 times smaller than that of the B-SB. Anotherpossible assignment of m/z = 32 (S) was examined by using Spoisoning of Si/Ti/Pt substrates (Figure S4, Supporting Informa-tion). Although a small amount of S was continuously generatedprobably because of the chemical reaction between the SE andthe leaked H2O, the generated S was not voltage-dependent.Thus, S was detected as part of the baseline current at m/z= 32 inFigure 2a–c. The voltage-dependent peak current at m/z = 32 wasassigned to O2 providing a fragment with m/z = 16 (O). These re-sults demonstrate that O2 is generated not only from NCM523[6](Figure 2a) but also from the a-LNbO coating layer (Figure 2b)during high-voltage charging. Because NCM523 maintains a lay-ered structure even after the charge–discharge cycles at 4.55 V,[7b]O2 is mainly generated from the a-LNbO coating layer. In addi-tion, the a-LNbPO coating layer further reduced the O2 release.These results directly support Equation (2), based on O2 genera-tion. The other m/z ratios (1–100) of the SBs did not exhibit anyvoltage dependence (Figure S5, Supporting Information).Adv. Sci. 2024, 2402528 2402528 (3 of 7) © 2024 The Author(s). Advanced Science published by Wiley-VCH GmbH 21983844, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/advs.202402528 by Nagoya University, Wiley Online Library on [08/07/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons Licensehttp://www.advancedsciencenews.comhttp://www.advancedscience.comwww.advancedsciencenews.com www.advancedscience.com2.2. XPS Analysis Using Model BatteriesThe amount of Li in the a-LNbO coating layer during the charg-ing process was examined using electrochemical XPS to vali-date Equation (1). In this study, oxide-based solid-state batterieswith LiCoO2 (LCO) cathode films and flat-textured Li+-conductivesolid electrolyte sheet (Li1.3Al0.3Ti1.7(PO4)3 (LATP)) were con-structed in order to investigate variations in the element ratioswith voltage around the electrode/coating layer interface. An a-LNbO film (30 nm thick) was formed on the LCO films as a modelcoating layer using pulsed laser deposition (PLD), ensuring noexposure of the sample to air. Preliminary tests confirmed thatthe a-LNbO film functioned effectively as a coating layer in the SB(SI-6). Figure 3a shows a schematic of a model solid-state battery,(Fe2(MoO4)3 (FMO)/LATP/LCO). FMO operates with a potentialplateau at 3.0 V (vs Li/Li+) and works as a reference and counterelectrode on LATP.[12] The cathode side of the model battery wasequipped with a Pt current collector only around the edges of theLCO film (Figure S7, Supporting Information). Figure 3b showsthe charge–discharge curve of the battery, with the voltage con-verted to Li/Li+. During the charge–discharge reactions, the volt-age was held constant for the XPS measurements. Co2p3/2, Li1s,Nb3d, and O1s XPS spectra were measured at the same positionon the a-LNbO film (SI-8). Co2p3/2 was not detected at any volt-ages (Figure S8a, Supporting Information), confirming that Li1swas analyzed only in the a-LNbO film. Figure 3c shows the volt-age dependence of the Li1s peak. The intensity of the Li1s peakdecreased with increasing the voltage. These results directly in-dicate that Li is extracted from the a-LNbO film during charging,supporting Equation (1) based on Li extraction. Figure 3d sum-marizes the variations found in both the Li/Nb and O/Nb atomicratios during the initial charge–discharge reaction. At 3.0 V, theLi/Nb and O/Nb ratios were 0.88 and 3.04, respectively. At 3.5 V,the Li/Nb ratio decreased to 0.48, and the O/Nb ratio to 2.81, sug-gesting that the a-LNbO layer oxidizes with O2 release. Above3.8 V, the Li/Nb ratio further decreased with increasing charg-ing voltages, whereas the O/Nb ratio remained at ≈2.8, indicat-ing that the a-LNbO film oxidized without O2 release. Even afterdischarging to 3.0 V, these ratios did not return to their initial val-ues, thus implying irreversible decomposition of the a-LNbO filmduring the initial charging through Li extraction. Delithiation oc-curred in the same manner inside the a-LNbO film until reach-ing the LCO layer (Figure S8e,f, Supporting Information). Thevalence band maximum (VBM) of the a-LNbO film was 5.8 eV(Figure S9, Supporting Information), which is 3.3 eV lower thanthe work function of Li metal (2.5 eV).[13] Therefore, the oxidativedecomposition of a-LNbO below 3.5 V is reasonably explainedalso by the electronic properties of the a-LNbO film.3. DiscussionThe XPS and gas analyses supported Equations (1) and (2), ex-cept for the phase separation of Li2O and its subsequent decom-position. The amount of Li extracted (ΔLi/Nb = 0.40) at 3.5 V isalmost double that of the removed amount of O (ΔO/Nb = 0.23).In contrast, Li2O is not separately detected in the XPS analyses,and 3.5 V is a sufficient voltage to decompose Li2O.[14] Hence, itis reasonable to expect that O2 is released simultaneously withthe Li extraction at lower voltages.The surface of the a-LNbO film shown in Figure 3a doesnot contact with the SE, but it still decreases the Li/Nb ratiosduring charging. Thus, we expect the Li chemical potential (𝜇Li)inside the coating layer to be almost uniform and closely alignedwith that of LCO, where 𝜇Li in LCO decreases with increasingcharging voltage (ϕ). On the other hand, in SBs, the a-LNbOcoating layer contacts with both NCM523 and SE, and then 𝜇Liin a-LNbO film must be aligned with these materials at eachboundary as shown in Figure 4.[3a] Here, Li-deficient a-LNbO hasto be formed at NCM523 boundary according to XPS analyses,while Li-rich a-LNbO will be formed alternatively at the SEboundary through phase separation or diffusion of both Li+ andO2− toward the SE side.[15] Here, the XPS analyses detect O2generation at 3.5 V, while gas analyses detect O2 generation over4.25 V. The anodic potential window calculated for crystallineLiNbO3 and other lithium niobium oxides lies 3.0–4.0 V,[3] andthen XPS results are consistent with the calculated potential win-dow while the gas analyses results exceed it. Thus, we expect thatO2 is released around the surface of the a-LNbO film once the SEboundary voltage (surface potential) of the a-LNbO film exceedsthe threshold voltage for O2 generation. Anodic decompositionof the SE by electron leakage through a-LNbO is likely because ofthe very narrow potential window of the SE (≈0.3 V).[3a,16] Sucha decomposed SE reacts with the generated O2 and increasesthe amount of oxidative SE (POx etc.) around a-LNbO, which isstrongly related to the capacity retention of the SBs operating athigh voltage.[7] In the case of thicker a-LNbO, electron leakagethrough the a-LNbO is suppressed, and then O2 generation willbe further reduced.[16] Also, if the electronic conductivity of thea-LNbO film does not change even after degradation, thickera-LNbO films can reduce the surface potential and subsequentlyreduce O2 generation at a given charge voltage.[17] In fact,a thicker and more uniform a-LNbO coating layer improvescapacity fading for the long-term cycling performance of SBs.[16]Gas analyses clarified that the amount of O2 release was signifi-cantly reduced by applying a-LNbPO instead of a-LNbO as a coat-ing layer. Electrochemical XPS measurements of the a-LNbPOfilm (30 nm thick, P/Nb≈0.5) were also conducted similarly tothose of the a-LNbO film in order to elucidate the mechanism(Figure S10, Supporting Information). The a-LNbPO film alsoworked as a coating layer in an SB (Figure S6, Supporting In-formation). Figure 3e illustrates the voltage dependence for theLi1s peak from the a-LNbPO film. The intensity of the Li1s peakprogressively decreased during the charging process. Figure 3fsummarizes the variations in both the Li/(Nb + P) and O/(Nb+ P) atomic ratios during the initial charge–discharge reaction.At 3.0 V, the Li/(Nb + P) and O/(Nb + P) ratios were 0.55 and2.73, respectively. At 3.5 V, the Li/(Nb + P) ratio decreased to0.36, whereas the O/(Nb + P) ratio decreased slightly to 2.66.Above 3.8 V, the Li/(Nb + P) ratio decreased gradually with anincreasing charging voltage, whereas the O/(Nb + P) ratio at 3.5–4.3 V remained within the error-bar scale at 3.0 V and slightly in-creased to 2.84 over 4.4 V. Although the chemical shifts of theseelements during the charging reaction are not easy to discuss dueto the zig-zag peak energy shift, the O1s of a-LNbPO appearedunique shoulder peak at a higher binding energy with an increas-ing charging voltage (Figure S10c, Supporting Information). Wepredict that this shoulder peak is assigned to peroxide-like O−formation.[18] Assuming that both Nb and P are pentavalent andAdv. Sci. 2024, 2402528 2402528 (4 of 7) © 2024 The Author(s). Advanced Science published by Wiley-VCH GmbH 21983844, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/advs.202402528 by Nagoya University, Wiley Online Library on [08/07/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons Licensehttp://www.advancedsciencenews.comhttp://www.advancedscience.comwww.advancedsciencenews.com www.advancedscience.comFigure 3. a) Schematic image and b) the initial charge–discharge curve (3.0–4.6 V vs Li/Li+, I = 1.0 μA cm−2, room temperature) of FMO/LATP/LCO/a-LNbO model battery for electrochemical XPS measurements. Voltage dependencies of c) Li1s XPS spectra and d) atomic ratios of Li/Nb (black) andO/Nb (red) on the a-LNbO film estimated by XPS (SI-8). Voltage dependencies of e) Li1s XPS spectra and f) atomic ratios of Li/(Nb + P) (black) andO/(Nb + P) (red) on the a-LNbPO film estimated by XPS (Figure S10, Supporting Information).Adv. Sci. 2024, 2402528 2402528 (5 of 7) © 2024 The Author(s). Advanced Science published by Wiley-VCH GmbH 21983844, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/advs.202402528 by Nagoya University, Wiley Online Library on [08/07/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons Licensehttp://www.advancedsciencenews.comhttp://www.advancedscience.comwww.advancedsciencenews.com www.advancedscience.comFigure 4. Schematic image of potential profiles in an SB with a-LNbO coat-ing layer.that both [NbO6] octahedral and [PO4] tetrahedral units are con-nected only by corner-sharing, the ideal O/(Nb + P) ratio is 3,which is close to the experimental value (2.73). During the charg-ing process, a-LNbPO may oxidize lattice-O2− to O−, and O2 gen-eration may be suppressed probably because most of lattice-Osare strongly bonded to P. Because the O/(Nb + P) ratio increasedslightly above 4.4 V, uncaptured oxygen may be trapped by par-tially breaking the corner-sharing bonding. Of course, furtheranalyses are required to clarify the aforementioned mechanismin detail to confirm microscopic guidelines to develop advancedcoating materials for high-energy density SBs. After dischargedto 3.0 V, these ratios did not return to their initial values. The re-maining O1s shoulder at higher binding energy will be due tothe slow recovery of Li to delithiated a-LNbPO. These results in-dicate that delithiation of the a-LNbPO coating layer also occurs,but the reaction primarily proceeds through oxidation of the a-LNbPO film under the capture of oxygen. Thus, we can concludethat suppressing O2 generation from the coating layer is crucialfor achieving stable and long-life SBs operating at high voltages.4. ConclusionIn summary, the a-LNbO coating layer on the NCM523 electrodedecomposes via O2 release with Li extraction. This O2 leads toan oxidative SE around a-LNbO and degrades the battery perfor-mance. Thus, suppressing O2 release from the coating layer is akey strategy for stabilizing the high-voltage charging of SBs, forwhich a-LNbPO is a suitable candidate.The authors have cited additional references within the Sup-porting Information.[4a,7a,9,12,13,19–31]Supporting InformationSupporting Information is available from the Wiley Online Library or fromthe author.AcknowledgementsThis work was supported by NEDO SOLID-NEXT (JPNP23005) andJSPS KAKENHI “Interface IONICS” JP19H05813&05814. The author (KY)would like to express special thanks to the “Interdisciplinary Frontier Next-Generation Researcher Program of Tokai Higher Education and ResearchSystem” for the financial support.Conflict of InterestThe authors declare no conflict of interest.Data Availability StatementThe data that support the findings of this study are available from the cor-responding author upon reasonable request.Keywordsall-solid-state battery, electrochemistry, energy conversion, interfaces,mass spectrometryReceived: March 11, 2024Revised: June 12, 2024Published online:[1] a) N. Kamaya, K. Homma, Y. Yamakawa, M. Hirayama, R. Kanno, M.Yonemura, T. Kamiyama, Y. Kato, S. Hama, K. Kawamoto, Nat. Mater.2011,10, 682; b) H. J. Deiseroth, S. T. Kong, H. Eckert, J. Vannahme,C. Reiner, T. Zaiss, M. Schlosser, Angew. Chem., Int. Ed. 2008, 47,755; c) Y. Kato, S. Hori, T. Saito, K. Suzuki, M. Hirayama, A. Mitsui,M. Yonemura, H. Iba, R. Kanno, Nat. Energy 2016, 1, 16030.[2] a) Y. Yang, Q. Wu, Y. Cui, Y. 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