ACS Applied Energy Materials
·
2021
·
IF 6.024
Shengdong Tao,Jian Li,Lihua Wang,Weiguo Huang,Minchao Zhang,Zhexi Chi,Shuohan Wang,Yongzhi Chen,Lei Shang
Development of an active filler with a large specific surface area, fast ion conductivity phase, special shape, and high electrochemical stability is a critical issue for prominent performance composite solid-state electrolytes (CSEs) in solid-state lithium-ion batteries. Here, we report large specific surface area and coral-like cubic Li7La3Zr2O12 (LLZO) that was synthesized via a metal–organic framework (MOF) at a low calcination temperature (1000 °C). As active fillers, the coral-like cubic LLZO and lithium oxalyldifluroborate (LiODFB) uniformly distributed in a poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) matrix provide an interconnected Li-ion transport channel in CSE, which manifests outstanding properties such as a favorable electrochemical stability window (of 4.85 V vs Li/Li+), high ionic conductivity (1.65 × 10–4 S cm–1, 20 °C), and superior interface compatibility with lithium metal. The assembled LiFePO4/CSE/Li and LiCoO2/CSE/Li cells convey predominate performance and initial specific capacities of 135.0 and 135.9 mA h g–1 at 0.5 C, with capacity retention values of 83.51% after 500 cycles and 93.90% after 200 cycles. The coral-like LLZO with a large specific area reduces polymer crystallinity and provides a large phase interface in CSE through interaction of LLZO with LiODFB and PVDF-HFP. The results suggest that coral-like LLZO prepared by MOFs is a promising filler in CSEs for solid-state lithium-ion batteries.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
SENSORS
·
2016
·Vol. 16
·期 3
·369
·
IF 2.033
Liwei Liu,Zheng Zhou,He Tian,Jixue Li
Bismuth oxide (Bi2O3)-doped yttria-stabilized zirconia (YSZ) were prepared via the solid state reaction method. X-ray diffraction and electron diffraction spectroscopy results indicate that doping with 2 mol% Bi2O3and adding 10 mol% yttria result in a stable zirconia cubic phase. Adding Bi2O3as a dopant increases the density of zirconia to above 96%, while reducing its normal sintering temperature by approximately 250 °C. Moreover, electrical impedance analyses show that adding Bi2O3enhances the conductivity of zirconia, improving its capability as a solid electrolyte for intermediate or even lower temperatures.Keywords:solid electrolyte;ionic conductivity;YSZ;bismuth oxide
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Journal of Materials Chemistry A
·
2024
·
IF 10.7
Minghui Li,Cai Chen,Hongze Luo,Qingshuai Xu,Keyou Yan,Yongcai Qiu,Guangmin Zhou
Li metal anodes are considered among the most ideal candidates for next generation batteries owing to their lowest electrochemical potential and high theoretical capacity. However, the highly reactive Li metal is subject to continuous side reactions with conventional carbonate electrolytes. The resulting unsatisfying solid electrolyte interface (SEI) induces severe Li dendritic growth. Therefore, there is an urgent need to effectively control the components of SEI to solve the electrolyte/anode interface electrochemical instability. Herein, LiDFP and LiNO3 are introduced into the electrolyte to modulate the composition of the SEI. Owing to the lower lowest unoccupied molecular orbital (LUMO) energy levels of LiDFP and LiNO3 relative to those of the solvents, LiDFP and LiNO3 have preferential reducibility and thus generate a stable SEI containing LiF and Li3N, which has swift ion migration kinetics and homogeneous Li deposition behaviors. As a result, our electrolyte modified by additives enables the anode to achieve an excellent coulombic efficiency of 98% and exhibits an ultra-long cycling life of over 700 h in symmetrical cells. Li metal full cells paired with the LFP or NCM811 cathode also have excellent long cycling performance. This work demonstrates that additive-modified electrolytes are a viable and simple strategy for the evolution of Li metal batteries.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2023
·
IF 6.2
Shulin Li,Ruifeng Song,Ruonan Xu,Han Yan,Qiaoquan Lin,Xinlin Yan,Zhenyu Wang,Chuang Yu,Long Zhang
Cl-rich Li-argyrodites are promising solid electrolytes (SEs) used in all-solid-state Li batteries (ASSLBs) owing to the fast ion transport. However, they are unstable in the air and their compatibility to metallic Li still needs to be strengthened. Here, we improve these properties through O doping with a relatively high concentration. The high O solid solution in the argyrodite lattice is verified. The optimized Li 5.7 PS 4.5 O 0.2 Cl 1.3 SE possesses an enhanced room temperature ionic conductivity . In parallel, in the sample with a relatively high oxygen dose, a Cl-O coexistence interface layer is revealed at the Li|SE interface region, associated with the formation of LiCl and Li 3 OCl interphases. The highest amount of Li 3 OCl appears also in the interface of Li 5.7 PS 4.5 O 0.2 Cl 1.3 SE. Along with a more stable PS 4- x O x unit, a proper O doing concentration is beneficial to mitigate the decomposition rate of SEs and to improve the compatibility of SE against Li metal. Moreover, Li 5.7 PS 4.5 O 0.2 Cl 1.3 gains significantly enhanced air stability in contrast to the O-free sample. Consequently, the ASSLBs using both pristine and air-exposed Li 5.7 PS 4.5 O 0.2 Cl 1.3 SE demonstrate decent electrochemical performance. In sharp contrast, the ASSLBs using the O-free argyrodite SE after air exposure cannot work for even one cycle. A high amount of O incorporation in Cl-rich Li-argyrodite SEs is thus a facile and effective route for achieving good overall performance including a high ionic conductivity, Li|SE interface stability, Li dendrite suppression capability, and notably, air stability.
研究领域:
材料科学
·
电化学
·
电池技术
✓ 已验证
DOI
高影响因子
SOLID STATE SCIENCES
·
2024
·
IF 3.4
Fei Ruan,Chonggui Lei,Xi Wu,Jinxiao Bao,Fen Zhou,Jianquan Gao,Guoqi Liu
To further investigate the electrochemical performance of Tm doped CaZrO 3 electrolyte, the CaZr 1 −x Tm x O 3 −α ( x = 0, 0.025, 0.05, 0.075 and 0.1) solid electrolyte specimens were prepared by high temperature solid state method. The phase structure and microstructure of the electrolyte samples were analyzed by Raman spectrum, XRD and SEM. The electrical conductivity of the specimen was measured at the temperature of 673∼1373K in hydrogen-rich and oxygen-rich atmosphere by the two-terminal AC impedance spectroscopy method. The H/D isotope effect of the specimen at different temperature was tested to confirm the dominant conducting carrier in predetermined temperature and atmosphere. It is found that proton is the dominant charge carrier both in oxygen-rich and hydrogen-rich atmosphere at the lower temperature below 1073 K. However, at higher temperature above 1073K, the predominant charge carrier seems to be oxygen ion vacancy in hydrogen-rich, whereas to be electron hole in oxygen-rich atmosphere, based on the analysis of the atmospheric dependence of the electrical conductivity. Moreover, partial conductivities of conducting species, the active doping amount of Tm and the standard Gibbs free energy changes for interstitial proton production by dissolution of water and hydrogen in Tm doped electrolyte were estimated based on crystal defect chemistry theory.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2021
·
IF 5.316
Yanhua Zhang,Yuxin Deng,Xinglong Gao,Chao Lv,Dawei Luo,Xing Xiang
Solid electrolyte Li 7 La 3 Zr 2 O 12 (LLZO) has received widespread attention due to its excellent comprehensive properties. However, in order to realize its industrial application in all-solid-state lithium batteries, an efficient and low-cost preparation method must be developed. Herein, molten salt method is applied and the effect of sintering temperature , washing solvent and mother powder distribution on the microstructure and properties of LLZO are investigated. Results show that pure cubic LLZO can be obtained at 1250–1300 °C, the lithium loss phase La 2 Zr 2 O 7 is generated at higher temperature of 1330 °C. The Li + conductivity of LLZO obtained at 1300 °C with short time of 80 min reach 2.9 × 10 −4 S cm −1 . Secondly, compared with washing with deionized water, the LiO 4 occupation reduced while the LiO 6 occupation increased when washing with LiOH aqueous, representing an exchange of Li + /H + . The Li + conductivity of LLZO washed with LiOH solution (6.53 × 10 −5 S cm −1 ) is 76% lower than that of deionized water washing (2.73 × 10 −4 S cm −1 ) which due to the excessive Li + concentration. Besides, the Li + conductivity of LLZO (2.57 × 10 −5 S cm −1 ) obtained with mother powder of 2.5 g: 2.5 g is close to one order of magnitude lower than that with 4 g: 1 g (2.23 × 10 −4 S cm −1 ) which is due to too much lithium loss through the upper surface. Excessive mother powder on the upper surface is beneficial to obtain cubic phase LLZO. The molten salt method greatly reduces the mixing time (less than 30 min) and sintering time (80 min) of materials which is an effective and low-cost method to achieve mass production.
研究领域:
材料科学
·
能源技术
✓ 已验证
DOI
高影响因子
ACS Applied Energy Materials
·
2022
·
IF 6.959
Yixuan Guo,Jun Cheng,Zhen Zeng,Yuanyuan Li,Hongqiang Zhang,Deping Li,Lijie Ci
Garnet-type Li7La3Zr2O12 (LLZO) has been widely used as a filler in composite solid electrolytes (CSEs) to achieve high-performance solid-state batteries (SSBs). Unfortunately, moisture-sensitive LLZO suffers from surface Li2CO3 passivation when being exposed to an ambient atmosphere. The insulated Li2CO3 layer is thought to reduce the Li+ transportability of CSEs. However, further studies are still needed to find out the underlying mechanism, which helps to guide future filler modification and electrolyte design. Herein, the role of the Li2CO3 layer in CSEs is elucidated from different perspectives. The passivate Li2CO3 layer is verified to prohibit the formation of the high conductive interlayer, change the Li+ transport pathway, and decrease the carrier concentration in CSEs. Also, the Li2CO3 layer would reduce the electropositivity of Li6.4La3Zr1.4Ta0.6O12 (LLZTO) particles, which therefore weakens the anchoring effect toward bis(trifluoromethanesulfonyl)imide (TFSI)−. Accordingly, without Li2CO3, the electrolyte of polyethylene oxide/LiTFSI/IL (ionic liquid) with LLZTO-AT (PLILA) displays 2 times higher ionic conductivity and an improved Li+ transference number of 0.49. Additionally, an excellent cycling performance is presented in Li symmetric cells and full cells with PLLA. This work provides a novel perspective for future research on lithium-ion transport mechanisms and inspires designing better-performance SSBs.
研究领域:
材料科学
·
电化学
·
能源存储
✓ 已验证
DOI
高影响因子
Inorganic Chemistry Frontiers
·
2022
·Vol. 9
·期 11
·2644-2658
·
IF 7.779
Xiaoyan Yang,Xiaoling Zeng,Xing Ming,Li Yang,Alberto J. Fernández-Carrión,Sihao Deng,Lunhua He,Xiaojun Kuang
BiVO4 scheelite is one of the few tetrahedra-based structures able to display vacancy-mediated oxide-ion conduction upon the use of an acceptor-doping strategy, leading to oxide-ion migration. In order to modulate the ionic migration process, it is of utmost importance to understand the different parameters affecting it. Here we review phase formation, oxygen vacancy stabilization, and migration for a wide variety of acceptor metal dopants in scheelite BiVO4. Among them, Ca2+-doped materials present the widest solid-solution range, leading to optimized oxide-ion conductivities at moderately high temperatures (σb: ∼10−3 S cm−1 at 500 °C), mainly as a result of their smaller size mismatch with Bi3+ and lower oxygen vacancy defect energy. The results gathered herein provide a useful guide for designing new oxide-ion conductors and tailoring oxide conductivity through the proper selection of doping agents according to several criteria, such as the oxygen defect formation energy, atom size mismatch, polarizability, and bond-dissociation energy with oxygen.
研究领域:
材料科学
·
无机化学
·
固体离子学
·
能源材料
·
电化学
✓ 已验证
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2022
·
IF 10.383
Hanxiao Zhou,Huimin Shang,Tianhui Li,Wenjing Liu,Zhihao Guo,Yuxuan Guo,Jingjing Gao,Meizhen Qu,Huan Zhang,Gongchang Peng
Lithium anodes have attracted much attention because of their high energy density, but the existence of lithium dendrites tremendously limits their practical application. Herein, it is creatively proposed to employ N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) as an electrolyte additive to stabilize the solid electrolyte interface. BSTFA is reduced on the lithium anode surface prior to other components to form a passivation layer composed of LiF, Li3N, and SiOx, which not only significantly prevents the continuous consumption of the electrolyte and reduces side reactions but also effectively promotes the uniform deposition of lithium ions with fast Li+ transmission, thereby solving the problem of lithium dendrites. Electrochemical results indicate that BSTFA can obviously reduce polarization in a Li||Li battery at a current density of 1 mA cm–2. Besides, an excellent cycling performance (107 mA h g–1) and Coulombic efficiency (99%) can be obtained for a Li||LiNi0.6Co0.2Mn0.2O2 (NCM622) battery with 0.5 wt % BSTFA at 2 C after 200 cycles, even at a high NCM622 loading of 6 mg cm–2.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Energy Storage Materials
·
2024
·
IF 18.9
Pushun Lu,Yujing Wu,Dengxu Wu,Fengmei Song,Tenghuan Ma,Wenlin Yan,Xiang Zhu,Fuliang Guo,Jiaze Lu,Jian Peng,Liquan Chen,Hong Li,Fan Wu
All-solid-state batteries (ASSBs) with potentially improved energy density and safety have been recognized as the next-generation energy storage technology. However, their performances at subzero temperatures are rarely investigated, with rate-limiting process/mechanisms unidentified. Herein , the rate-limiting process/mechanisms for -40℃ ASSBs are accurately identified/analyzed by developing a standard test-analysis flow model. We reveal that the rate-limiting processes of LiCoO 2 (LCO)+sulfide solid electrolyte (SE) composite cathode are the sluggish ion transport across unfavorable interfacial reaction layer and charge transfer at damaged LCO cathode surface. After inserting Li 2 ZrO 3 (LZO) coating layer to suppress interfacial reactions, the rate-limiting process of LCO@LZO+sulfide SE composite cathode turns into the arduous ion transport across the interphase composed of the self-decomposition products of sulfide SE. Interestingly, by replacing sulfide SE with halide SE, LCO+halide SE composite cathode delivers fast charge transfer and the ion conduction through the thick SE separator becomes the rate-limiting process, thus enabling a superior capacity retention rate (41.4 %) at -40℃. Furthermore, the capacity retention of ASSB coupling LCO+halide SE composite cathode with Si anode can be boosted from 28.9 % to 38.6 % at -40℃ by employing superionic conductor with low activation energy. These successful identifications/modulations on rate-limiting process/mechanism and improvements on low-temperature performance demonstrate the significant role of this test-analysis flow in propelling the development of low-temperature ASSBs.
研究领域:
材料科学
·
电化学
·
电池技术
✓ 已验证
产品关联
DOI
高影响因子
ENERGY & FUELS
·
2024
·
IF 5.2
Lihao Zheng,Juntao Shi,Gaoya Ren,Tiantian Tang,Yefeng Yang,Shenghui Shen,Zhujun Yao
Sulfide solid electrolytes have emerged as highly promising candidates for an all-solid-state battery, while phosphorus-free compounds with air stability have not gotten enough attention. In this study, we focus on an air-stable compound, Li4SnS4, whose structure can be adjusted by Bi3+ doping through the combination of a two-step ball milling method and thermal annealing. The successful substitution of Sn4+ by Bi3+ with lower valence and larger ionic radius results in the enhancement of Li+ concentration in electrolytes and lattice volume, benefiting the Li+ migration. Therefore, the modified glass-ceramic Li4.025Sn0.975Bi0.025S4 exhibits an ionic conductivity of 1.35 × 10–4 S cm–1 at room temperature, which is twice as high as that of pure Li4SnS4. Moreover, the soft acid characteristic of Bi3+ can further ensure the air stability of Li4SnS4 based on the hard and soft acid and base theory. The findings revealed from this research provide a potential avenue for improving the performance of air-stable Li4SnS4 solid-state electrolytes for future large-scale applications.
研究领域:
材料科学
·
电化学
·
能源存储
✓ 已验证
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Heshuang Dai,Qianqiu Wang,Xing Xiang,Chaofan Wang,Ban Chen,Zi Wang,Zizhuo Teng,Jingyi Peng,Xiaoxia Guo
In response to the demand for high-performance and safe batteries in the field of energy storage, a novel polyurethane-based solid electrolyte system, B x PU-Li y , has been developed. Crystallinity had been effectively reduced by incorporating 1,1′-binaphthol with a special molecular structure leading enhanced ion migration. Among that, B 5 PU-Li 20 demonstrates good mechanical properties and thermal stability, with an ionic conductivity of 3.28 × 10 -5 S cm −1 at room temperature, increasing to 2.0 × 10 -4 S cm −1 at 40 °C. Additionally, this material exhibits excellent electrochemical performance and battery cycling capabilities, offering a new direction for the development of high-performance battery technology, with potential applications in portable electronic devices, electric vehicles, and large-scale energy storage systems.
研究领域:
材料科学
·
能源存储技术
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）