Small
·
2021
·Vol. 18
·期 5
·2104508
·
IF 13.281
Jinzhu Wang,Jipeng Hao,Chaomin Duan,Xinchao Wang,Kai Wang,Cheng Ma
Solid-state fluoride-ion batteries (FIBs) circumvent multiple formidable bottlenecks of lithium-ion batteries, but their overall performance remains inferior due to the absence of appropriate solid electrolytes. Presently the conductivity of most solid electrolytes for FIBs is too low to enable room-temperature cycling, while the few sufficiently conductive ones only allow for very low discharge voltages because of the narrow electrochemical stability window (ESW). Here, high room-temperature conductivity and a decent ESW are simultaneously achieved by designing a solid electrolyte CsPb 0.9 K 0.1 F 2.9 . Its room-temperature conductivity is 1.23 × 10 −3 S cm −1 , comparable to the most conductive system reported so far (PbSnF 4 , 5.44 × 10 −4 –1.6 × 10 −3 S cm −1 ), but the ESW is several times broader. With these appealing characteristics simultaneously achieved in the solid electrolyte, a cell with much higher voltages than other room-temperature-operable solid-state FIBs in literature is successfully constructed, and stably cycled at 25 °C for 4581 h without considerable capacity fade.
研究领域:
材料科学
·
电化学
·
固态离子学
·
能源存储
·
无机功能材料
✓ 已验证
DOI
高影响因子
Journal of Materials Chemistry A
·
2021
·Vol. 9
·期 38
·22064-22071
·
IF 12.732
Wenda Zhang,Jie Feng,Fengqi Lu,Alberto J. Fernández-Carrión,Hui Fu,Xiaojun Kuang
Na-doped melilite-type silicate Sr2MgSi2O7 was reported to display high oxide ion conductivity. In this work, through multiple complementary techniques including X-ray diffraction, scanning electron microscopy, transmission electron microscopy, solid-state 29Si and 23Na nuclear magnetic resonance spectroscopy, and DFT calculations of defect formation energies, we found that it is hard to replace Sr with Na in Sr2MgSi2O7, and the Sr2−xNaxMgSi2O7−0.5x compositions formed mixed crystalline Sr2MgSi2O7 and Na-containing glassy phases. AC impedance spectroscopy measurements indicated that the ionic conduction in Sr2−xNaxMgSi2O7−0.5x could be from Na+ ions in the glassy phase, instead of the oxide ions.
研究领域:
材料科学
·
固体离子导体
·
无机非金属材料
·
能源材料
·
电化学
✓ 已验证
DOI
高影响因子
SOLID STATE IONICS
·
2017
·
IF 2.354
Yan Sun,Wenning Yan,Li An,Bingbin Wu,Kaifu Zhong,Ruizhi Yang
A super solid electrolyte of Ba-substituted Li 10 GeP 2 S 12 is designed and fabricated to achieve high electrochemical stability. Among the Ba-substituted Li 10 GeP 2 S 12 solid electrolytes, the composition of Li 9.4 Ba 0.3 GeP 2 S 12 exhibits the highest ionic conductivity of 7.04 × 10 − 4 S cm − 1 with an activation energy of 28.27 kJ mol − 1 at 25 °C. The electrochemical window of Li 9.4 Ba 0.3 GeP 2 S 12 is between 0 and 6 V (vs. Li), which is higher than the typical 5 V window of Li 10 GeP 2 S 12 . As compared with Li 10 GeP 2 S 12 , Li 9.4 Ba 0.3 GeP 2 S 12 demonstrates a significantly reduced polarization and a better cycle stability though its ionic conductivity is slightly lower than that of the former. The electrochemical stability of Ba-substituted Li 10 GeP 2 S 12 can be attributed to the structural stability resulting from the stable interaction between Ba 2 + and S 2 − in the structure.
研究领域:
材料科学
·
固态离子学
·
电化学
·
能源材料
·
无机固体化学
✓ 已验证
DOI
高影响因子
Journal of Materials Chemistry A
·
2018
·Vol. 6
·期 39
·19231-19240
·
IF 9.931
Minjie Xuan,Weidong Xiao,Hongjie Xu,Yonglong Shen,Zhenzhen Li,Shijie Zhang,Zhuo Wang,Guosheng Shao
The development of a solid electrolyte with superb Li+ conductivity is the key to enabling safe and high-performance all-solid lithium ion batteries which are free of the safety issues associated with flammable organic liquid electrolyte. Systematic experimental work has been carried out as a follow up to our recent theoretical prediction that superb ionic conductivity could be achieved through the tuning of the lattice chemistry in the cubic argyrodite Li6PS5Cl. Remarkable enhancement of the ionic conductivity has been achieved through the combined effect of excess Li and substitution of S with Te. This leads to an alloy, Li6.25PTe0.125S5.125Cl0.75, having the superb Li+ conductivity of 4.5 mS cm−1 at 25 °C, together with a low activation energy of 0.16 eV to safeguard adequate ionic conductivity at low temperature. This current work conclusively affirms the theoretical outcome that the superb ionic conductivity is attributed to weakened bonding, an enlarged unit cell, and a softened lattice, making it easier for the long-distance diffusion of Li+. In addition, this new class of solid electrolyte based on cubic chalcogenide is electrochemically compatible with the Li anode over a large potential window up to 7 V, which is highly desirable for high performance solid lithium ion batteries.
研究领域:
材料科学
·
电化学
·
能源存储
·
固体离子学
·
无机化学
✓ 已验证
DOI
高影响因子
Science China-Materials
·
2021
·Vol. 64
·期 6
·1378-1385
·
IF 8.273
Fu Yuanyuan,Ma Cheng
The interplay between solid electrolytes and electrodes is of vital importance to the performance of all-solid-state Li batteries. Recently, halide superionic conductors have emerged as a new family of high-performance solid electrolytes, but their compatibility with Li metal, i.e., the anode with the highest theoretical capacity, has not been systematically studied. Here, we investigate the interaction between Li metal and two representative halide solid electrolytes: Li 3 YCl 6 and Li 3 YBr 6 . Both materials are found to form interphases with Li, similar to most solid electrolytes. However, the interphases observed here contain electronic conducting components, which are detrimental to their compatibility with Li. By elucidating this phenomenon, the present study provides guiding principles for improving the Li compatibility of halide solid electrolytes.
研究领域:
材料科学
·
电化学
·
固态离子学
·
能源存储
·
电池技术
✓ 已验证
DOI
高影响因子
INORGANIC CHEMISTRY
·
2022
·
IF 5.436
Lijia Zhou,Jinxiao Zhang,Congling Yin,Luhui Meng,Jiachen Li,Yuexiang Li,Franck Fayon,Mathieu Allix,Xiaojun Kuang
A nonstoichiometric La1.5Sr0.5Ga3O7.25 melilite oxide ion conductor features active interstitial oxygen defects in its pentagonal rings with high mobility. In this study, electron localization function calculated by density functional theory indicated that the interstitial oxide ions located in the pentagonal rings of gallate melilites may be removed and replaced by electron anions that are confined within the pentagonal rings, which would therefore convert the melilite interstitial oxide ion conductor into a zero-dimensional (0D) electride. The more active interstitial oxide ions, compared to the framework oxide ions, make the La1.5Sr0.5Ga3O7.25 melilite structure more reducible by CaH2 using topotactic reduction, in contrast to the hardly reducible nature of parent LaSrGa3O7. The topotactic reduction enhances the bulk electronic conduction (σ ∼ 0.003 S/cm at 400 °C) by ∼ 1 order of magnitude for La1.5Sr0.5Ga3O7.25. The oxygen loss in the melilite structure was verified and most likely took place on the active interstitial oxide ions. The identified confinement space for electronic anions in melilite interstitial oxide ion conductors presented here provides a strategy to access inorganic electrides from interstitial oxide ion conductor electrolytes.
研究领域:
材料科学
·
固态化学
·
凝聚态物理
·
离子导体
·
电子材料
✓ 已验证
DOI
高影响因子
DALTON TRANSACTIONS
·
2024
·Vol. 53
·期 46
·18674-18687
·
IF 3.5
Yuan Gou,Xiaohui Li,Xiaoge Wang,Mengjia Zhang,Jinxiao Zhang,Qiang Li,Xianran Xing,Xiaojun Kuang
Solid-state nuclear magnetic resonance (NMR) spectroscopy serves as a powerful technique for probing local structures. However, the interpretation of NMR signals mainly based on empirical knowledge could lead to imprecise local structural determinations. To address this, density functional theory (DFT)-based theoretical NMR calculations, aided by experimental three-dimensional continuous rotation electronic diffraction (3D cRED) technique, were performed for ZnxY1−xBO3−0.5x borate oxide ion conductors. The calculations provided fine local structure identification for the experimental 11B NMR spectra of ZnxY1−xBO3−0.5x, providing rich information on multiple experimental 11B NMR signals towards the complex boron oxide anions associated with bridging oxygen vacancies and the coexistence of the monoclinic (C2/c), hexagonal (P63/m), and trigonal (R32) phases in ZnxY1−xBO3−0.5x. Owing to the advantages of solid-state NMR in identifying closely related phases compared to X-ray/neutron diffraction technique, along with the advanced 3D cRED technique that allows for rapid phase identification and structure determination, we provide a fine local structure identification and a more inclusive insight into the coexistence of multiple phases in borate with the same composition. More importantly, this work provides guidance for phase and property modulation. Phase modulation in ZnxY1−xBO3−0.5x was carried out with thermodynamic and kinetic modulation and eventually realized the tuning of the local structures and the resultant oxide ion conductivity of ZnxY1−xBO3−0.5x. This work provides a theoretical and experimental platform to access the flexible structural assignment of boron oxide anions and therefore offers new guidance and insights into the defect structures and the phase-property modulation of inorganic solid functional materials beyond borate oxide ion conductors.
研究领域:
材料科学
·
固态化学
·
计算化学
·
核磁共振（NMR）
·
能源材料
·
离子导体
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）