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Hiroaki Kobayashi, Yu Fukumi, Hiroto Watanabe, Reona Iimura, Naomi Nishimura, [Toshihiko Mandai](https://orcid.org/0000-0002-2403-7794), Yoichi Tominaga, Masanobu Nakayama, Tetsu Ichitsubo, Itaru Honma, Hiroaki Imai

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[Ultraporous, Ultrasmall MgMn<sub>2</sub>O<sub>4</sub> Spinel Cathode for a Room-Temperature Magnesium Rechargeable Battery](https://mdr.nims.go.jp/datasets/715e98a3-3756-44ee-885a-f1159e168e41)

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Ultraporous, Ultrasmall MgMn2O4 Spinel Cathode for a Room-Temperature Magnesium Rechargeable BatteryUltraporous, Ultrasmall MgMn2O4 SpinelCathode for a Room-Temperature MagnesiumRechargeable BatteryHiroaki Kobayashi,* Yu Fukumi, Hiroto Watanabe, Reona Iimura, Naomi Nishimura, Toshihiko Mandai,Yoichi Tominaga, Masanobu Nakayama, Tetsu Ichitsubo, Itaru Honma, and Hiroaki Imai*Cite This: ACS Nano 2023, 17, 3135−3142 Read OnlineACCESS Metrics & More Article Recommendations *sı Supporting InformationABSTRACT: Magnesium rechargeable batteries (MRBs) prom-ise to be the next post lithium-ion batteries that can help meetthe increasing demand for high-energy, cost-effective, high-safety energy storage devices. Early prototype MRBs that usemolybdenum-sulfide cathodes have low terminal voltages,requiring the development of oxide-based cathodes capable ofovercoming the sulfide’s low Mg2+ conductivity. Here, wefabricate an ultraporous (>500 m2 g−1) and ultrasmall (<2.5nm) cubic spinel MgMn2O4 (MMO) by a freeze-dry assistedroom-temperature alcohol reduction process. While the as-fabricated MMO exhibits a discharge capacity of 160 mAh g−1,the removal of its surface hydroxy groups by heat-treatmentactivates it without structural change, improving its dischargecapacity to 270 mAh g−1�the theoretical capacity at room temperature. These results are made possible by the ultraporous,ultrasmall particles that stabilize the metastable cubic spinel phase, promoting both the Mg2+ insertion/deintercalation in theMMO and the reversible transformation between the cubic spinel and cubic rock-salt phases.KEYWORDS: magnesium battery, porous nanoparticles, cathode materials, cubic metastable spinel, freeze-dryingWith the growing number of portable electronics andelectric vehicles, the demand for energy storagedevices, such as lithium-ion batteries (LIBs), isever-increasing.1 To meet this demand for high-energy, cost-effective, and high-safety energy storage devices, new types ofpost-LIBs are always in development. To this end, magnesiumrechargeable batteries (MRBs), have gained much attention:the abundant Mg metal undergoes safe anode reactions with apredicted volumetric capacity much higher than that of theexpensive and reactive Li metal.2−4Previously, a working MRB prototype that uses Mo6S8Chevrel-type cathode, Mg metal anode, and Grignard-typeelectrolyte had been reported by Aurbach et al.5 However, thisprototype showed an operating voltage of ∼1.1 V, a low valueattributed to the transition metal sulfide-type cathodematerials. Because transition-metal-oxide materials, such aslayered,6 tunnel,7 and spinel-type8−10 oxides are predicted tohave higher potentials than sulfides, these materials are theprime candidates for the next MRB cathode material.Among the transition metal oxides, the spinel MgMn2O4(MMO) has a suitably high theoretical energy density.11,12However, its conductivity is low due to the strong interactionsbetween Mg2+ and O2−.13 Our previous density functionaltheory (DFT) studies has indicated that the Mg2+ diffusioncoefficients at 298 K in the cubic MMO (6.4 × 10−15 cm2s−1)14 to be 106 times lower than the Li+ diffusion coefficient inthe similar cubic spinel LiMn2O4 (4.7 × 10−9 cm2 s−1).15 Veryrecently, an extended mixed conduction theory has indicatedthat the Mg2+ diffusion coefficient in MgCr2O4 is comparableto the Li+ diffusion, but its conductivity is still estimated at lowvalue.16 A large polarization due to the low conductivity isexpected to cause unwanted effects such as poor energyefficiency and oxidative electrolyte decomposition (>3.5 V vsMg in glyme-based common electrolytes). Some reportssuggest that the Mg insertion/deintercalation in MMO isaccelerated by water addition into the electrolyte.6,17 However,Received: December 14, 2022Accepted: January 18, 2023Published: January 20, 2023Articlewww.acsnano.org© 2023 The Authors. Published byAmerican Chemical Society3135https://doi.org/10.1021/acsnano.2c12392ACS Nano 2023, 17, 3135−3142Downloaded via NATL INST FOR MATLS SCIENCE (NIMS) on March 10, 2023 at 00:01:50 (UTC).See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.https://pubs.acs.org/action/doSearch?field1=Contrib&text1="Hiroaki+Kobayashi"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Yu+Fukumi"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Hiroto+Watanabe"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Reona+Iimura"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Naomi+Nishimura"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Toshihiko+Mandai"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Yoichi+Tominaga"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Yoichi+Tominaga"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Masanobu+Nakayama"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Tetsu+Ichitsubo"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Itaru+Honma"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Hiroaki+Imai"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/showCitFormats?doi=10.1021/acsnano.2c12392&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsnano.2c12392?ref=pdfhttps://pubs.acs.org/doi/10.1021/acsnano.2c12392?goto=articleMetrics&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsnano.2c12392?goto=recommendations&?ref=pdfhttps://pubs.acs.org/doi/10.1021/acsnano.2c12392?goto=supporting-info&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsnano.2c12392?fig=tgr1&ref=pdfhttps://pubs.acs.org/toc/ancac3/17/3?ref=pdfhttps://pubs.acs.org/toc/ancac3/17/3?ref=pdfhttps://pubs.acs.org/toc/ancac3/17/3?ref=pdfhttps://pubs.acs.org/toc/ancac3/17/3?ref=pdfwww.acsnano.org?ref=pdfhttps://pubs.acs.org?ref=pdfhttps://pubs.acs.org?ref=pdfhttps://doi.org/10.1021/acsnano.2c12392?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-ashttps://www.acsnano.org?ref=pdfhttps://www.acsnano.org?ref=pdfthis approach is not applicable to MRBs due to Mg deposition/dissolution at the anode. Therefore, the successful replacementof magnesium sulfides by MMOs in MRBs depends on the useof electrolytes that is compatible with both the cathode and theanode.Here, we demonstrate high-voltage MRB full cells; wefabricate highly porous nanosized oxides to reduce the Mgconduction path in the MMO cathode material, an approachthat was previously attempted by many groups.12 Recently, ourgroup has developed porous MMO nanoparticles (∼8 nmdiameter) with a specific surface area (SSA) of ∼250 m2 g−1 bya sol−gel process,18 and ultrasmall MMO nanoparticles (<5nm) with a SSA of ∼150 m2 g−1 by alcohol reductionprocess,19 which all showed a first discharge capacity of 230mAh g−1 at room temperature. This discharge value, while highamong MMO cathodes, was still 85% of the theoreticalcapacity (270 mAh g−1). To enhance the cathode performanceand achieve the theoretical capacity, the addition of porosity tothe ultrasmall MMO nanoparticles is a possible strategy. In thiswork, we enhance the cathode performance by increasing theporosity of the MMO. We fabricate ultraporous, ultrasmallMMO cathode nanoparticles and demonstrate a first dischargecapacity of 270 mAh g−1, i.e., the theoretical capacity at roomtemperature.RESULTS AND DISCUSSIONPhase Stability and Migration Energy of Mg Hoppingbetween the Spinel and Rock-Salt Phases. First, weinvestigate the theoretical effects of the Mg2+ insertion reactionon the MMO cathode. Figure 1a shows the DFT-calculatedformation energies for MgxMn2O4 (1 ≤ x ≤ 2) with varyingMg/vacancy configurations, where the total energies of bothextremes of the compositional range (x = 1 and 2) are set to 0.The lowest energy configurations for MgMn2O4 andMg2Mn2O4 (x = 1 and 2) are confirmed to be the spineland the rock-salt structures, respectively, where all Mg ionsoccupy the tetrahedral and the octahedral sites. All theformation energies for MgxMn2O4 (1 ≤ x ≤ 2) cells arepositive, indicating a two-phase transformation reactionbetween the spinel MgMn2O4 (x = 1) and the rock-saltMg2Mn2O4 (x = 2). The calculated reaction potential for thetwo-phase transformation is 1.68 V (vs Mg2+/Mg).The kinetics of two-phase transformation reactions are oftenslow, since these reactions involve both nucleation and growthprocesses that accompany phase-boundary motions. However,Malik et al. have suggested previously20 that the kineticallyfeasible single-phase transformation pass (i.e., solid solutionreaction) for the olivine-type LiFePO4−FePO4 system showsultrafast reaction kinetics21 despite the two-phase coexistencereaction system. The availability of the single-phase trans-formation pass is attributed to small formation energies for theintermediate compositions, corresponding to very smalloverpotential. Note that both MgMn2O4 and Mg2Mn2O4structures consist of the same structure flamework of Mn2O4,where oxide ions form cubic closed packing structure and Mnions located at the octahedral sites. Mg ions occupy tetrahedralsites or octahedral sites in MgMn2O4 or Mg2Mn2O4 structures,and both Mg sites are on the 3-dimensional diffusion path.Hence, a single-phase transformation pass is also available forthe MgMn2O4−Mg2Mn2O4 two phase coexistence system.However, the formation energy profile in Figure 1a, relativelylarge overpotential (>1 V) at the onset of discharge reaction(at the compositional range, 1 ≤ x ≤ 1.25, in MgxMn2O4) isrequired to realize single-phase transformation reaction.Accordingly, the reaction should proceed via the two-phasetransformation pass between the spinel MgMn2O4 and therock-salt Mg2Mn2O4.Previously, we reported that the Mg migration energy for thecubic MMO is 0.67 eV, indicating that Mg2+ diffusion iskinetically possible at a 1C-rate, even at 25 °C, via nanoscaleparticle synthesis.14 The estimated migration energy agree wellwith muon spin relaxation (μSR) studies (∼0.7 eV), andpowder diffraction and solid-state NMR studies (∼0.69 eV).22In addition, former DFT-NEB studies for MgMn2O4 andrelatives shows the comparable migration energies rangingfrom 0.49 eV to ∼0.78 eV).22−26 However, the Mg migrationenergy for the reduced phase, i.e. rock-salt Mg2Mn2O4 isexpected to be much larger. Figure 1b compares the DFT-NEBderived energy profiles of Mg migrations in rock-saltMg2Mn2O4 and spinel MgMn2O4. In rock-salt, the straightpass shows the lowest migration energy compared with thebending passes via both tetrahedral vacancy sites (Figure S1).The migration energy in rock-salt is 2.2 eV, which is aboutthree times larger than that in spinel.14 This route is differentfrom the spinel MgMn2O4; the energy maximum is at themiddle of the migration pass, adjacent to two oxide ions.Hence, the repulsive interactions from the overlap of electronclouds between the hopping Mg and the neighboring oxideions may be the primary reason for the large migration energy.According to the migration energies, the diffusioncoefficients of Mg at 298 K for rock-salt Mg2Mn2O4 areapproximately 10−40 cm2 s−1. In other words, the diffusiondistance at 298 K for rock-salt Mg2Mn2O4 corresponds toFigure 1. (a) DFT-calculated formation energies as a function ofcomposition x in MgxMn2O4 (1 ≤ x ≤ 2) with varying Mg/vacancyarrangement. The hatched line corresponds to the convex hull. (b)Energy profile during Mg2+ ion migration in rock-salt Mg2Mn2O4(red curve) and spinel MgMn2O4 (black curve).14 (c) Correlationbetween the particle diameter of the nanostructured MMO and theMg insertion depth published in our previous work.18 The insetshows the correlation between the SSA and the first dischargecapacity.ACS Nano www.acsnano.org Articlehttps://doi.org/10.1021/acsnano.2c12392ACS Nano 2023, 17, 3135−31423136https://pubs.acs.org/doi/suppl/10.1021/acsnano.2c12392/suppl_file/nn2c12392_si_001.pdfhttps://pubs.acs.org/doi/10.1021/acsnano.2c12392?fig=fig1&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsnano.2c12392?fig=fig1&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsnano.2c12392?fig=fig1&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsnano.2c12392?fig=fig1&ref=pdfwww.acsnano.org?ref=pdfhttps://doi.org/10.1021/acsnano.2c12392?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asapproximately 10−11 nm per hour as dictated by random walktheory. Because the discharge reaction of MMO is determinedto be a two-phase transformation reaction, the partial Mginsertion into the MMO surface at the initial discharge step isexpected to form the MgMn2O4-core/Mg2Mn2O4-shellstructure, preventing further Mg uptake due to the slow Mgdiffusion in the rock-salt Mg2Mn2O4-shell phase. This scenariohad been observed in systems such as the MgCo2O4 electrodematerials.10,27However, our previously developed porous MMO nano-particles18 have a Mg insertion depth of ∼1 nm at room-temperature (Figure 1c). This suggests that at the near surfaceregions (∼1 nm), Mg insertion can proceed faster thantheoretically predicted due to the instabilities at these regions.In other words, ultrasmall MMO nanoparticles with ∼2 nmdiameter should exhibit the full transformation to rock-saltMg2Mn2O4 at discharge. Further, our previous study showsthat nanosized spinel LiMn2O4 undergo fast Li insertionwithout formation of the core−shell structure.28 To enable theMg insertion into the bulk spinel MgMn2O4, downsizing theactive materials to the ultrasmall-scale to prevent the core−shell structure formation is essential. In addition, the dischargecapacity of MMO strongly depends on the SSA (inset ofFigure 1c). The complete discharge is also achievable usingultraporous MMO with SSA of ∼300 m2 g−1. Since theaggregates should inhibit the Mg insertion into cores, epoch-making synthesis of ultraporous and ultrasmall MMOnanoparticles is required.Suppressing Aggregation to Enhance the SpecificSurface Area of Ultrasmall Nanoparticles. First, we studythe particle size of the primary nanoparticle structure bysynthesizing the MMO nanoparticles following our proce-dure.19 The transmission electron microscopy (TEM) image ofthe resulting product in Figure 2a shows MMO particles asdark spots with an average size of 2.1 nm dispersed throughoutthe image. Using the MMO density of 4.67 g cm−3 from the X-ray diffraction (XRD) Rietveld analysis (Figure S2), weestimate the SSA to be 610 m2 g−1, a large value amongoxides in general.Entry 1 in Table 1 indicates that the Brunauer−Emmett−Teller (BET) SSA of our MMO previously prepared in ref 19was only 151 m2 g−1, due to aggregation of the unstableultrasmall particles during the drying process. In this work, wesuppress this aggregation by changing both the reaction solventand the drying process. As we have stated previously,19,29 theMMO formation reaction is water-sensitive; water contami-nation should form a less-reactive Mg2+ aqua complex,producing either the todorokite-type Mg-OMS-1, or Mn3O4.Glyme is a well-known electrolyte that interacts with metalcations to form stable cation-glyme complex. Mixing glymeinto the solution can effectively suppress the formation of Mg2+aqua complex, obtaining MMO. In addition, the glyme mixingto the solution is also effective to increase the SSA of spinels,probably due to surface stabilizing effect to prevent anaggregation of the particles. This has been demonstrated byNakai et al., who succeeded in increasing the SSA of Co−Mnspinel from 338 to 425 m2 g−1 by only changing the reactionsolvent�adding glyme to the alcohol solution.30,31 In thepresent work, the SSA of the MMO prepared using the glyme-alcohol mixture (Entry 2 in Table 1) has been practicallydoubled without any change in XRD patterns (Figure S3).Next, we study the control of the secondary porous particlestructure. As the first and second steps in the Figure S4 schemeillustrate, the MMO suspension is intentionally aggregated andprecipitated by adding a small amount of water as a flocculant.At this stage, the particles are weakly aggregated via theintermediate of water. The third and fourth steps in the FigureS4 scheme involve the strong aggregation by drying. Here, wecompare several drying techniques to control the strongaggregation. We applied the freeze-drying process that iscommonly used to produce ceramics with complex porestructure with several dispersion liquids.32 As Table 1 indicates,while the freeze-dried MMO from the water dispersion (Entry3) show almost similar SSA from the heat-drying method(Entry 2), the freeze-dried MMO from the cyclohexanedispersion (Entry 4) considerably decreased SSA (73 m2 g−1).In contrast, the freeze-dried MMO from the tert-butyl alcohol(tBuOH) dispersion (Entry 5) exhibits the greatest improve-ment with a SSA of 506 m2 g−1. The result in Entry 4 is likelycaused by an accelerated nanoparticle aggregation bydispersion of the hydrophilic MMO into the hydrophobiccyclohexane.We investigate the hierarchical structures obtained using theEntry 5 method. The scanning electron microscopy (SEM)image in Figure 2b shows the resulting porous networks that iscomposed of secondary structures of tens of nanometer inaverage size. Further, the TEM image in Figure 2c shows thatthe secondary particles are the results of aggregated primaryFigure 2. (a) TEM image of MMO particles obtained from thediluted condition. (b) SEM and (c) TEM images of the freeze-dried MMO particles from the tBuOH dispersion. (d) Dischargecurves of MMO cathodes prepared using the three different dryingprocesses.Table 1. BET SSA of MMOs Prepared Using DifferentDrying and Dispersion ProcessesEntry Drying process Dispersion Specific surface area (m2 g−1)1a Heat-drying 151192 Heat-drying 3083 Freeze-drying Water 2934 Freeze-drying Cyclohexane 735 Freeze-drying tBuOH 5066 Spray-drying Water 1147 Spray-drying EtOH 155aWithout addition of glyme.ACS Nano www.acsnano.org Articlehttps://doi.org/10.1021/acsnano.2c12392ACS Nano 2023, 17, 3135−31423137https://pubs.acs.org/doi/suppl/10.1021/acsnano.2c12392/suppl_file/nn2c12392_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acsnano.2c12392/suppl_file/nn2c12392_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acsnano.2c12392/suppl_file/nn2c12392_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acsnano.2c12392/suppl_file/nn2c12392_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acsnano.2c12392/suppl_file/nn2c12392_si_001.pdfhttps://pubs.acs.org/doi/10.1021/acsnano.2c12392?fig=fig2&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsnano.2c12392?fig=fig2&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsnano.2c12392?fig=fig2&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsnano.2c12392?fig=fig2&ref=pdfwww.acsnano.org?ref=pdfhttps://doi.org/10.1021/acsnano.2c12392?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asparticles with an average size of 2.4 nm. According to the pore-size distribution analyzed by using Barrette-Joynere-Halenda(BJH) method (Figure S5), the hierarchical structure hasnanopores of around 4 nm, and macropores. This bimodalporous network�with nano- and micropores�is formed bythe weak aggregation of primary and secondary particles,respectively, keeping the interparticle voids. The stronginteractions between MMO particles via water are reducedby substitution with tBuOH, resulting in the ultraporousstructure.We also applied the spray-drying process, which is oftenused to granulate nanoparticles of ceramics.33 The spray-driedMMO powders show spherical morphology (Figure S6), whichis different from the freeze-dried MMO powders. Thesecondary particle size is dependent on dispersants; 5−20μm in water and 2−5 μm in ethanol (EtOH). The SSA of thestructures obtained by the spray-drying process significantlydecreased to 100−150 m2 g−1 (Entries 6 and 7 in Table 1).After fine-tuning the MMO using the above methods, wetest the overall MRB performances of the MMO cathodesusing the coin-type full cells, composed of Mg anode andMg[B(HFIP)4]2/triglyme (HFIP: hexafluoroisopropyl) elec-trolyte. Figure 2d shows the first discharge curves comparingthe MMO obtained from different drying methods. As theblack and red curves in Figure 2d indicate, the heat- and spray-dried MMO exhibit no discharge plateau, with the dischargecapacities of only 20 and 60 mAh g−1, respectively, probablydue to the strong aggregation of MMO particles. The bluecurve in Figure 2d indicates that the freeze-dried MMOexhibits a 2 V-discharge plateau, suggesting that Mn reductionhas occurred. The discharge capacity, however, is 160 mAhg−1, which is much lower than the theoretical capacity ofMMO (270 mAh g−1) predicted from the large SSA (inset inFigure 1c). Since there is no calcination step in the MMOpreparation, the hydroxy groups on the ultraporous particlessurface should be present. These hydroxy groups may inhibitthe discharge reaction.Surface Functionalization of MMO by Heat Treat-ments. To remove the surface hydroxy groups, we apply heattreatment to the tBuOH-freeze-dried MMO. The thermog-ravimetry (TG) curve of MMO in Figure S7 shows a gradualweight decrease as the temperature is ramped up to 300 °C,followed by a sudden weight loss at 500 °C. According to theXRD in Figure 3a, while no major structural change isobserved during the gradual weight decrease, the MMOundergoes drastic structural change after the sudden weightloss. Because the alcohol reduction process is a room-temperature synthesis, the resulting MMO is a room-temperature metastable phase; XRD Rietveld fitting (FigureS2) and inductively coupled plasma atomic emission spectros-copy (ICP-AES) analyses indicate that the obtained MMO is aMg-site defect nonstoichiometric cubic spinel Mg0.72Mn2O4.The Rietveld analysis also shows the MMO treated at 400 °Cretains its cubic spinel structure (Figure S8a). After the heattreatment at 500 °C, the cubic spinel transform to tetragonalspinel (Mg0.8Mn0.2)Mn2O4 by releasing O2 (Figure S8b).Figure 3b shows Mn K-edge X-ray absorption near edgestructure (XANES) spectra acquired on MMO throughout theheat treatment. The edge energy of MMO before heattreatment was between Mn2O3 and MnO2, indicating themixed valence state of Mn3+ and Mn4+. The existence of Mn4+supports the estimated nonstoichiometric formula. After heattreatment, the edge energy shifted to lower energy; reductionof Mn4+ proceeds by the heat treatment. The trend in theenergy shift is also observed in Mn 2p X-ray photoelectronspectra (XPS) (Figure S9).Figure 3c shows the Raman spectra acquired on MMOthroughout the heat treatment. Spectrum i (before heat-treatment) shows a broad peak with a shoulder and two weakpeaks. Comparing this spectrum to that of the cubicLiMn2O434 and other tetragonal Mn spinels,35 we assignthese signals to the cubic spinel phase. We attribute the broadsignal around 615 cm−1 to the symmetric stretching Mn−Ovibration of MnO6 octahedra with A1g symmetry mode; theFigure 3. Heat-treatment of the freeze-dried MMO particles from tBuOH dispersion. (a) XRD, (b) Mn K-edge XANES, (c) Raman, and (d)FT-IR spectra showing the effects of the heat treatment on MMO. (e) Summary of the FT-IR peak-area ratios (Mn−OH/Mn−O−Mn), SSA,and first discharge capacity. (f) Voltage curves of the MMO after heat treatment at 300 °C.ACS Nano www.acsnano.org Articlehttps://doi.org/10.1021/acsnano.2c12392ACS Nano 2023, 17, 3135−31423138https://pubs.acs.org/doi/suppl/10.1021/acsnano.2c12392/suppl_file/nn2c12392_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acsnano.2c12392/suppl_file/nn2c12392_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acsnano.2c12392/suppl_file/nn2c12392_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acsnano.2c12392/suppl_file/nn2c12392_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acsnano.2c12392/suppl_file/nn2c12392_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acsnano.2c12392/suppl_file/nn2c12392_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acsnano.2c12392/suppl_file/nn2c12392_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acsnano.2c12392/suppl_file/nn2c12392_si_001.pdfhttps://pubs.acs.org/doi/10.1021/acsnano.2c12392?fig=fig3&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsnano.2c12392?fig=fig3&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsnano.2c12392?fig=fig3&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsnano.2c12392?fig=fig3&ref=pdfwww.acsnano.org?ref=pdfhttps://doi.org/10.1021/acsnano.2c12392?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asshoulder at 580 cm−1 to the stretching of symmetry mode F2g;and the weak signals to the F2g and Eg mode. Spectrum iv inFigure 3c shows that after heating at 400 °C, while the F2gsignal has decreased in intensity, the A1g signal has increased inintensity. This result suggests the reduction of Mn4+ by heattreatment. Spectrum v in Figure 3c shows that after heating at500 °C, all Raman signals from the cubic spinel phase are nolonger observable, replaced by a set of signals located at 666,375, and 313 cm−1; we assign these signals to the tetragonalMMO spinel phase35 and attribute them to the vibrations ofA1g, B2g, and A1g symmetry mode, respectively. The combinedresults from the Raman measurements indicate that thethermal phase transition from the cubic to the tetragonalMMO takes place above 500 °C.Figure 3d shows the Fourier-transform infrared (FT-IR)spectra acquired on MMO throughout the heat treatment. Weattribute the signal at 600 cm−1 to the Mn−O−Mn latticevibration and the signal at 3200 cm−1 to the OH stretchingmode both of the surface Mn−OH groups and of adsorbedwater. We attribute the signals at 1600 and 1400 cm−1 to theOH bending modes both of the surface Mn−OH groups andof adsorbed H2O. Spectra ii−v in Figure 3d show that after theheating at 200 °C, the signals related to −OH vibrations aresignificantly decreased.Figure 3e summarizes the correlation between the heattreatment temperatures and the integrated Mn−OH:Mn−O−Mn peak area ratio: the ratio decreases with increasingtemperature. This result indicates that the heat treatmentabove 300 °C removes the surface Mn−OH groups. Figure 3ealso summarizes the correlations between the heat treatmenttemperatures and both the SSAs (isotherms were plotted inFigure S10). and the first discharge capacities of the MMO(voltage curves were plotted in Figure S11). Up to 400 °C,while the SSA decreases gradually from 506 to 300 m2 g−1,indicating the presence of both nanopores and macropores(Figure S12a), the discharge capacity greatly increases to reachthe theoretical capacity of 270 mAh g−1 at 300−400 °C, wherethe surface Mn−OH groups are effectively removed. Electro-chemical impedance spectroscopy (EIS) confirmed thedecrease in charge transfer resistance by eliminating surfacehydroxy groups (Figure S13). Figure 3e also shows that afterthe heat treatment at 500 °C, the SSA is drastically reduced tobelow 100 m2 g−1, indicating the complete disappearance ofnanopores (Figure S12b). Similarly, the discharge capacitiesare also reduced to 56 mAh g−1, due to the major structuralchanges and low SSA.Figure 3f shows the discharge/charge cycles of the MMOtreated at 300 °C. We previously confirmed the electrolytedecomposition at the same cell test condition by XPSanalysis.36 Although the decomposition of electrolyte occurredcompetitively during overcharge, but we performed the cell testwith the voltage range of 0.1−4.0 V to proceed the oxidationreaction. The discharge capacity gradually decreases due to theside reaction of electrolyte decomposition at the charge step;the cathode can be well cycled using the high-voltage stableelectrolyte.Figure 4a shows the calculated Mg2+ insertion depths of theultraporous and ultrasmall MMO treated at 300 and 400 °C.The particle diameters were calculated using the SSA. Thecalculated insertion depths are longer than that of thepreviously reported porous tetragonal MMO nanoparticles.18We attribute this improvement to the specific crystal phase: theultrasmall MMO is a metastable cubic spinel phase. Accordingto previous literature, this phase can be obtained in theultrasmall (<7 nm) particle range.14,19 The Mg2+ insertion intoMMO results in a formation of the cubic rock-salt Mg2Mn2O4during the discharge process. Though the Mg2+ migrationenergy is almost same between the cubic and the tetragonalMMOs, the phase transition from the cubic (spinel) to thecubic (rock-salt) is much faster than that from tetragonal(spinel) to cubic (rock-salt) because of the absence of thelattice distortion change during the Mg insertion. This is thekey point that explains the higher performances of the cubicspinel MMOs compared to the tetragonal MMOs.Figure 4b shows the Raman spectra acquired on the MMOelectrode during first cycle. After the first discharge, the strongbroad peak at 580 cm−1 that indicates the high Mn4+ contentshas decreased, suggesting Mn reduction. Further, the peakposition of the A1g mode has shifted to a higher frequency dueto the Mg insertion. After charging, the peak position of the A1gmode has shifted back to the original position of the samplebefore discharge. After the first discharge/charge, the intensityof the MMO F2g mode has decreased compared to the originalsample before discharge. This is because the voltage applied inthe present system can only induce the electrochemicaloxidation from Mn2+ to Mn3+. Notably, the tetragonal spinelphase is not observed through the discharge/charge processes,suggesting that reversible transition between the cubic spineland the cubic rock-salt has occurred; in the ultrasmall region,the cubic MMO phase is rather stable than tetragonal MMOphase. This observation should play an important role in thesmooth insertion/ejection of Mg2+ ions, resulting in a longerMg2+ insertion depth.CONCLUSIONSWe have fabricated a ultraporous (>500 m2 g−1), ultrasmall(<2.5 nm) cubic spinel MnMn2O4 (MMO) by freeze-dryassisted room-temperature alcohol reduction process. We havedetermined that the resulting MMO nanoparticles havehydroxy groups at surfaces, which can be removed by asubsequent heat-treatment at 300−400 °C without structuralchange. We have tested the hydroxy-free MMO cathode andfound a high discharge capacity of 270 mAh g−1, correspondingto its theoretical capacity. The ultrasmall particles stabilize themetastable cubic spinel phase, enabling both the Mg2+insertion into the MMO core and the reversible transformationbetween cubic spinel and cubic rock-salt MMO phases.METHODSComputational Method. First-principles DFT calculations wereused to investigate both the phase stabilities between the spinelMgMn2O4 and the rock-salt Mg2Mn2O4 structures, and the ion-Figure 4. (a) Estimated Mg insertion depth of the MMO. (b)Raman spectra of the MMO during discharge−charge.ACS Nano www.acsnano.org Articlehttps://doi.org/10.1021/acsnano.2c12392ACS Nano 2023, 17, 3135−31423139https://pubs.acs.org/doi/suppl/10.1021/acsnano.2c12392/suppl_file/nn2c12392_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acsnano.2c12392/suppl_file/nn2c12392_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acsnano.2c12392/suppl_file/nn2c12392_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acsnano.2c12392/suppl_file/nn2c12392_si_001.pdfhttps://pubs.acs.org/doi/suppl/10.1021/acsnano.2c12392/suppl_file/nn2c12392_si_001.pdfhttps://pubs.acs.org/doi/10.1021/acsnano.2c12392?fig=fig4&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsnano.2c12392?fig=fig4&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsnano.2c12392?fig=fig4&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsnano.2c12392?fig=fig4&ref=pdfwww.acsnano.org?ref=pdfhttps://doi.org/10.1021/acsnano.2c12392?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asmigration property of Mg ions in Mg2Mn2O4. For the crystal structureinput of the spinel MgMn2O4, the I41/amd space group suggested byboth refs.14 and,37 where all the Mg and Mn ions are located attetrahedral and octahedral sites, was used. To evaluate the totalenergies for compounds after the topochemical Mg insertions (i.e.,MgxMn2O4 (1 < x ≤ 2)), the ATAT software package38 was used toproduce a total of 513 symmetrically distinct Mg/vacancy arrange-ments. The DFT calculations for the total energies, formationenergies and voltages were performed according to previousreports.9,39 A combination of the projector augmented-wave (PAW)method,40 plane-wave basis set, and a generalized gradientapproximation (GGA)-type exchange-correlation functional devel-oped by Perdew, Burke, and Ernzernhof modified for solid materials(PBEsol)41,42 was used as implemented in the Vienna Ab InitioSimulation Package (VASP).43,44 The on-site Coulomb correction(GGA+U) was used to describe the localized electronic states in theMn 3d orbital (UMn,d = 3.9 eV45). The nudged elastic band (NEB)method46 was applied to evaluate the minimum energy pathways ofthe Mg jump in the rock-salt Mg2Mn2O4. In detail, the model cellconsisted of the superstructure of the 2 × 2 × 2 conventional rock-saltstructure with a single Mg vacancy as migration species (i.e.,Mg15Mn16O32). Unless mentioned otherwise, we refer to the Mgvacancy-containing superstructure as Mg2Mn2O4.Sample Preparation. MgMn2O4 (MMO) was prepared using themodified alcohol reduction process.19,36 (n-Bu)4NMnO4 was preparedaccording to a previous report.47 2 mmol of (n-Bu)4NMnO4 powderwas first slowly added to a 2 mmol MgCl2 solution made in a 25 mLethanol and 25 mL diglyme mixture under vigorous stirring for 1 h.Ten milliliters of water was then injected to the brown colloidalsolution, precipitating the MMO. The precipitate was filtered orcentrifuged, followed by washing with ethanol several times to obtainthe MMO wet cake, which was then dried using three differenttechniques: (i) heat-dried at 120 °C in air overnight; (ii) dispersedinto solvents (water, cyclohexane, or tert-butyl alcohol) followed byfreeze-drying using DC401 (Yamato Scientific Co., Ltd.); and (iii)dispersed into solvents (water or ethanol), followed by spray-dryingunder N2 atmosphere using ADL311S-A (Yamato Scientific Co., Ltd.)connected with solvent recovery unit (GAS 410, Yamato ScientificCo., Ltd.).Materials Characterization. The scanning electron microscopy(SEM) images were obtained using JSM-7100F or JSM-7800F. Thetransmission electron microscopy (TEM) images were obtained usingFEI Tecnai G2. The X-ray diffraction (XRD) patterns were obtainedusing a Bruker D2 PHASER XE-T Edition. The Rietveld refinementwas performed using the RIETAN-FP program.48 The Brunauer−Emmett−Teller (BET) specific surface areas were measured by N2adsorption at 77 K using a BELSORP MAX G (MicrotracBEL) or3Flex-3MP (Micromeritics). Samples were degassed at 100 °C for 12h under vacuum. Elemental analysis was performed using inductivelycoupled plasma atomic emission spectroscopy (ICP-AES, ShimadzuICPE- 9000). Thermogravimetric analysis (TG) was performed usingTG-DTA2000S (Netzsch). Raman and Fourier Transform Infrared(FT-IR) spectra were obtained using InVia Raman Microscope(Renishaw) and FT/IR-4200typeA (JASCO), respectively. X-rayabsorption spectroscopy (XAS) in the transmission method wasperformed at the AichiSR. Spectra were analyzed using Athena.49 X-ray photoelectron spectroscopy (XPS) was conducted using a PHI5000 VersaProbe II.Electrochemical Tests. The samples were mixed with acetyleneblack (AB; Denka Black, FX-35, Denka Co., Ltd.) and polytetrafluoro-ethylene (PTFE; Teflon, 6-J, DuPont-Mitsui Fluorochemicals Co.,Ltd.) at a respective weight ratio of 60:30:10. These mixtures were cutinto 8 mm diameter disks of typically 2.5 mg and pressed onto an Almesh current collector to serve as cathodes. The electrodes were driedat 160 °C under vacuum and introduced into an Ar-filled glovebox.The cathode and the Mg−Al−Zn alloy (AZ-31, Nippon Kinzoku Co.,Ltd.) anode, and 0.3 M Mg[B(HFIP)4]2/triglyme (HFIP: hexa-fluoroisopropyl) electrolyte50 were assembled in a 2032 coin-type cell(Hohsen Corp.) with a glass-fiber separator (GA-100, Toyo RoshiKaisha, Ltd.). The charge/discharge tests were performed at 25 °C inthe constant-current (CC) mode using either a multichannelpotentiostat system (VMP3, Bio-Logic Science Instruments), or abattery test system (HJ-1001SD8, Hokuto Denko Corp.). Electro-chemical impedance spectroscopy (EIS) was performed using anactivated carbon counter electrode instead of the Mg anode.ASSOCIATED CONTENT*sı Supporting InformationThe Supporting Information is available free of charge athttps://pubs.acs.org/doi/10.1021/acsnano.2c12392.Results of the theoretical calculations, XRD Rietveldrefinements, pore distributions, XPS, SEM analysis,electrochemical tests (PDF)AUTHOR INFORMATIONCorresponding AuthorsHiroaki Kobayashi − Institute of Multidisciplinary Researchfor Advanced Materials, Tohoku University, Sendai, Miyagi980-8577, Japan; orcid.org/0000-0001-6705-9515;Email: h.kobayashi@tohoku.ac.jpHiroaki Imai − Department of Applied Chemistry, Faculty ofScience and Technology, Keio University, Yokohama,Kanagawa 223-8522, Japan; orcid.org/0000-0001-6332-9514; Email: hiroaki@applc.keio.ac.jpAuthorsYu Fukumi − Department of Applied Chemistry, Faculty ofScience and Technology, Keio University, Yokohama,Kanagawa 223-8522, JapanHiroto Watanabe − Department of Applied Chemistry,Faculty of Science and Technology, Keio University,Yokohama, Kanagawa 223-8522, JapanReona Iimura − Institute of Multidisciplinary Research forAdvanced Materials, Tohoku University, Sendai, Miyagi 980-8577, JapanNaomi Nishimura − Graduate School of Bio-Applications andSystems Engineering, Tokyo University of Agriculture andTechnology, Koganei, Tokyo 184-8588, JapanToshihiko Mandai − Center for Green Research on Energyand Environmental Materials, National Institute forMaterials Science (NIMS), Tsukuba, Ibaraki 305-0044,Japan; orcid.org/0000-0002-2403-7794Yoichi Tominaga − Graduate School of Bio-Applications andSystems Engineering, Tokyo University of Agriculture andTechnology, Koganei, Tokyo 184-8588, Japan; orcid.org/0000-0001-5098-8537Masanobu Nakayama − Department of Advanced Ceramics,Nagoya Institute of Technology, Nagoya, Aichi 466-8555,Japan; orcid.org/0000-0002-5113-053XTetsu Ichitsubo − Institute for Materials Research, TohokuUniversity, Sendai, Miyagi 980-8577, JapanItaru Honma − Institute of Multidisciplinary Research forAdvanced Materials, Tohoku University, Sendai, Miyagi 980-8577, JapanComplete contact information is available at:https://pubs.acs.org/10.1021/acsnano.2c12392Author ContributionsH.K.: Conceptualization in ultrasmall particle application,writing manuscript -draft, project administration. Y.F.:Investigation in ultraporous particles fabrication and batterytests. H.W.: Analyses in Raman and FT-IR spectroscopies,writing manuscript -draft. R.I.: Validation in ultrasmall andACS Nano www.acsnano.org Articlehttps://doi.org/10.1021/acsnano.2c12392ACS Nano 2023, 17, 3135−31423140https://pubs.acs.org/doi/10.1021/acsnano.2c12392?goto=supporting-infohttps://pubs.acs.org/doi/suppl/10.1021/acsnano.2c12392/suppl_file/nn2c12392_si_001.pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Hiroaki+Kobayashi"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://orcid.org/0000-0001-6705-9515mailto:h.kobayashi@tohoku.ac.jphttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Hiroaki+Imai"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://orcid.org/0000-0001-6332-9514https://orcid.org/0000-0001-6332-9514mailto:hiroaki@applc.keio.ac.jphttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Yu+Fukumi"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Hiroto+Watanabe"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Reona+Iimura"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Naomi+Nishimura"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Toshihiko+Mandai"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://orcid.org/0000-0002-2403-7794https://pubs.acs.org/action/doSearch?field1=Contrib&text1="Yoichi+Tominaga"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://orcid.org/0000-0001-5098-8537https://orcid.org/0000-0001-5098-8537https://pubs.acs.org/action/doSearch?field1=Contrib&text1="Masanobu+Nakayama"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://orcid.org/0000-0002-5113-053Xhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Tetsu+Ichitsubo"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/action/doSearch?field1=Contrib&text1="Itaru+Honma"&field2=AllField&text2=&publication=&accessType=allContent&Earliest=&ref=pdfhttps://pubs.acs.org/doi/10.1021/acsnano.2c12392?ref=pdfwww.acsnano.org?ref=pdfhttps://doi.org/10.1021/acsnano.2c12392?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-asultraporous particles fabrication and battery tests. N.N.:Investigation in spray drying. T.M.: Electrolyte supply. Y.T.:Methodology in spray drying. M.N.: Theoretical calculation.T.I.: Methodology in theoretical model. I.H.: Supervision. H.I.:Conceptualization in ultraporous particle application, super-vision, project administration. All coauthors contributed towriting manuscript - review and editing.NotesThe authors declare no competing financial interest.ACKNOWLEDGMENTSThis work was supported by JST ALCA-SPRING(JPMJAL1301). This work was partially supported by JSPSKAKENHI (JP20H02436). We also thank Patrick Han forEnglish editing.REFERENCES(1) Tarascon, J. M.; Armand, M. Issues and Challenges FacingRechargeable Lithium Batteries. Nature 2001, 414, 359−367.(2) Muldoon, J.; Bucur, C. B.; Gregory, T. Fervent Hype behindMagnesium Batteries: An Open Call to Synthetic Chemists�Electrolytes and Cathodes Needed. Angew. Chem., Int. Ed. 2017, 56,12064−12084.(3) Bucur, C. B.; Gregory, T.; Oliver, A. G.; Muldoon, J. 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