SOLID STATE IONICS
·
2020
·
IF 3.107
Ying Tian,Ying Zhou,Yang Liu,Chao Zhao,Wen Wang,Yu Zhou
The development of solid-state batteries requires the optimization of ceramic electrolyte such as garnet type cubic Li 7 La 3 Zr 2 O 12 (LLZO). Exploration of powders formation mechanism and the sintering behavior of ceramics are crucial to acquire high performance LLZO electrolytes. This study adopts quantitative analysis based on X-ray adiabatic principle to investigate the formation mechanism of Li 7 − 3 x Al x La 3 Zr 2 O 12 ( x = 0, 0.1, 0.15, 0.2, 0.25, LALZO) powders synthesized by sol-gel method. The whole calcination procedure could be divided into three stages as follows, La 2 Zr 2 O 7 (LZO) formation (<750 °C), transformation from LZO to LLZO (750 °C–850 °C) and LLZO decomposition (>850 °C). The phase, morphology and conductivity of LALZO ceramics demonstrate abnormal grain growth (AGG) caused by over-sintering leads to random orientation and conductivity deterioration. The optimal sintering condition could not only make grains bound tightly but also avoid AGG. Ceramics consist of LALZO ( x = 0.25) exhibit better total ionic conductivity of 3.08 × 10 −4 S cm −1 (E a = 0.27 eV) with density of 92.5% after sintering at 1100 °C for 15 h. This research provides guidance for quickly acquiring pure LLZO powders and excellent performance ceramics.
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 PHYSICS AND CHEMISTRY OF SOLIDS
·
2023
·
IF 4
Zhiwei Qin,Yuming Xie,Xiangchen Meng,Delai Qian,Cheng Shan,Gang He,Long Wan,Yongxian Huang
Cycling performance and Coulombic efficiency of full cell solid-state lithium batteries (SSLBs) are far from satisfactory since low-performance garnet Li 7 La 3 Zr 2 O 12 causes uneven plating/stripping process and severe Li deposition. Herein, Ta-doped garnet Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 (LLZTO) with high Li-ion conductivity and high density is employed to promote the electrochemical performances of full cell SSLBs. The Li-ion conductivity reaches 6.65 × 10 −4 S cm −1 with a density of 96.2%. High-performance LLZTO facilitates the Li-ion transport and reduces the Li deposition along grain boundaries. Full cell LiFePO 4 /LLZTO/Graphite SSLBs display an excellent cycling stability, where the capacity retention remains 85.7% with a Coulombic efficiency over 99% after 40 cycles at 0.1C. The smooth charge-discharge voltage platforms indicate stable REDOX reactions with uniform Li plating/stripping process. This work combines the advantages of graphite electrode and SSLBs with environmental benignity and economic viability, accelerating future SSLBs large-scale industrial application.
研究领域:
材料科学
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储能
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电化学
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全固态电池
✓ 已验证
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2020
·
IF 8.758
Mengjun Wu,Dan Liu,Deyu Qu,Zhizhong Xie,Junsheng Li,Jiaheng Lei,Haolin Tang
Composite polymer electrolytes (CPEs) are very promising for high-energy lithium-metal batteries as they combine the advantages of polymeric and ceramic electrolytes. The dimensions and morphologies of active ceramic fillers play critical roles in determining the electrochemical and mechanical performances of CPEs. Herein, a coral-like LLZO (Li6.4La3Zr2Al0.2O12) is designed and used as a 3D active nanofiller in a poly(vinylidene difluoride) polymer matrix. Building 3D interconnected frameworks endows the as-made CPE membranes with an enhanced ionic conductivity (1.51 × 10–4 S cm–1) at room temperature and an enlarged tensile strength up to 5.9 MPa. As a consequence, the flexible 3D-architectured CPE enables a steady lithium plating/stripping cycling over 200 h without a short circuit. Moreover, the assembled solid-state Li|LiFePO4 cells using the electrolyte exhibit decent cycling performance (95.2% capacity retention after 200 cycles at 1 C) and excellent rate capability (120 mA h g–1 at 3 C). These results demonstrate the superiority of 3D interconnected garnet frameworks in developing CPEs with excellent electrochemical and mechanical properties.
研究领域:
材料科学
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电化学
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储能技术
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固态电池
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聚合物纳米复合材料
✓ 已验证
DOI
高影响因子
CERAMICS INTERNATIONAL
·
2024
·
IF 5.1
Xiangping Feng,Lei Zhang,Chao Li,Ming Shen,Runguo Zheng,Zhiyuan Wang,Hongyu Sun,Yanguo Liu
Cubic phase Li 7 La 3 Zr 2 O 12 (LLZO) is a promising electrolyte material for all-solid-state rechargeable lithium-ion batteries. The homogeneous densification of the garnet solid electrolyte ceramic material is crucial for enhancing its ionic conductivity performance. Herein, an Al/Ta co-doped strategy is employed to stabilize the cubic phase structure of LLZO and is combined with a two-step sintering method to enhance densification, in order to investigate its effect on microstructure, ionic conductivity, and electrochemical properties . During the formation process, amorphous Li 2 O reacts with doped Al 2 O 3 to create a Li–Al–O liquid phase at the grain boundaries. Combined with two-step sintering to ensure that the desired material transformation is achieved, resulting in a dense microstructure and better mechanical properties. The solid electrolyte Li 6.4 Al 0.1 La 3 Zr 1.7 Ta 0.3 O 12 under two-step sintering (LLZATO-2) is successfully synthesized, delivering an ionic conductivity up to 7.33 × 10 −4 S cm −1 at room temperature and an activation energy of 0.22 eV. This work also highlights the critical role of co-doping combined with two-step sintering in preparing well-performing solid-state electrolytes and all-solid-state lithium-ion 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
Science China-Materials
·
2022
·Vol. 66
·期 2
·522-530
·
IF 8.64
Wu Mengjun,Song Jiangping,Zhu Xinxin,Zhan Hui,Tian Tian,Wang Rui,Lei Jiaheng,Tang Haolin
Composite polymer electrolytes (CPEs) are regarded as promising candidates for high-energy-density all-solid-state lithium metal batteries (ASSLMBs) because they combine the merits of solid polymer electrolytes and inorganic solid electrolytes. However, poor electrode/electrolyte interface compatibility and filler agglomeration limit their practical application. In this study, an in-situ polymerization method was used to create a three-dimensional (3D) hierarchical CPE using 3-(trimethoxysilyl)propyl methacrylate (KH570)-modified Li 6.4 La 3 Zr 2 Al 0.2 O 12 (KH@LLZO) particles. The KH@LLZO-rich (up to 80 wt%) region of the electrolyte provides a rigid barrier to prevent lithium dendrite growth, while the other region of the electrolyte with an appropriate KH@LLZO content (8 wt%) achieving optimal ionic conductivity infiltrates into the entire battery system to allow for smooth Li + transport. The symmetric Li|Li cell exhibits steady lithium plating/stripping cycling over 600 h at 0.3 mA h cm −2 and has a decent critical current density of 0.9 mA cm −2 . This is made possible by the elaborate structure of the electrolytes. Full Li|LiFePO 4 cells have preferable cycling stability (capacity retention of 91.6% after 200 cycles at 0.5 C). Moreover, pouch cells that use the in-situ -formed electrolyte exhibit excellent flexibility and safety. This novel design of 3D hierarchical CPEs using surface-modified LLZO particles paves the way for the development of dendrite-free and high-performance ASSLMBs.
研究领域:
材料科学
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能源存储技术
✓ 已验证
DOI
高影响因子
ADVANCED MATERIALS
·
2023
·Vol. 35
·期 12
·2208951
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IF 29.4
Jie Biao,Bing Han,Yidan Cao,Qidong Li,Guiming Zhong,Jiabin Ma,Likun Chen,Ke Yang,Jinshuo Mi,Yonghong Deng,Ming Liu,Wei Lv,Feiyu Kang,Yan-Bing He
Poor ion and high electron transport at the grain boundaries (GBs) of ceramic electrolytes are the primary reasons for lithium filament infiltration and short-circuiting of all-solid-state lithium metal batteries (ASLMBs). Herein, it is discovered that Li 2 CO 3 at the GBs of Li 7 La 3 Zr 2 O 12 (LLZO) sheets is reduced to highly electron-conductive LiC x during cycling, resulting in lithium penetration of LLZO. The ionic and electronic conductivity of the GBs within LLZO can be simultaneously tuned using sintered Li 3 AlF 6 . The generated LiAlO 2 (LAO) infusion and F-doping at the GBs of LLZO (LAO-LLZOF) significantly reduce the Li 2 CO 3 content and broaden the energy bandgap of LLZO, which decreases the electronic conductivity of LAO-LLZOF. LAO forms a 3D continuous ion transport network at the GB that significantly improves the total ionic conductivity. Lithium penetration within LLZO is suppressed and an all-solid-state LiFePO 4 /LAO-LLZOF/Li battery stably cycled for 5500 cycles at 3 C. This work reveals the chemistry of Li 2 CO 3 at the LLZO GBs during cycling, presents a novel lithium penetration mechanism within garnet electrolytes, and provides an innovative method to simultaneously regulate the ion and electron transport at the GBs in garnet electrodes for advanced ASLMBs.
研究领域:
材料科学
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电化学
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电池技术
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固态电解质
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Journal of the American Chemical Society
·
2025
·
IF 15.6
Zeyu Wang,Xiangchen Hu,Yue Zhang,Xiaoyan Wu,Hongsheng Shi,Wei Liu,Yi Yu
Garnet-type solid electrolyte cubic Li7La3Zr2O12 (c-LLZO) emerges as a promising candidate for establishing reliable and high-performance lithium-ion batteries. Its extreme sensitivity to electron irradiation poses a significant challenge in atomically resolving its structure using conventional transmission electron microscopy (TEM) techniques. We demonstrate that the combination of low-dose four-dimensional scanning TEM (4D-STEM) with multislice ptychographic retrieval methodology manages to achieve a sub-Angstrom resolution and the direct visualization of lithium atoms within c-LLZO. The distribution of lithium in depth direction is also obtained. This work provides atomic-scale insights into the distribution of light elements within irradiation-sensitive dense crystals, paving the way for investigating the microstructure–property relationship.
研究领域:
材料科学
·
物理学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Journal of Materials Chemistry A
·
2023
·Vol. 11
·期 38
·20676-20685
·
IF 11.9
Ziwen Pan,Shiyu Cao,Xinqi Lu,Gang Zhang,Qiang Shen,Chong Mao,Xiaobing Dai,Fei Chen
The interphase structure and Li-ion transport across the interface are essential for high-performance composite solid electrolytes (CPEs). Tailoring the interface between rigid inorganic solid electrolyte fillers and the polymer electrolyte matrix is a promising way. A Li-ion conductive filler such as garnet Li7La3Zr2O12 (LLZO) is proposed for the high performance of CPEs, which suffered from an unavoidable insulating contamination layer and incomplete contact with the polymer matrix. In this study, a wet chemical method was applied for converting the insulation layer on the LLZO surface to LiF with the formation of oxygen vacancies by NH4F solution etching at moderate temperature. The equally dispersed in situ formed LiF in CPEs improves the electrochemical stability. Removal of resistive barriers accompanied by firm contact with the polymer matrix induced by bonding between PEO chains and oxygen vacancies forms a CPE with homogeneous fast Li-ion transport. Owing to these advantageous properties, the ionic conductivity of CPEs with etched LLZO increases from 6.45 × 10−4 S cm−1 to 1.28 × 10−3 S cm−1 at 60 °C, and the electrochemical stable window is extended. An all-solid-state battery with etched powder exhibits extraordinary cycle stability at 2C with an initial discharge capacity of 136 mA h g−1, and capacity retention remains at 90.4% after 300 cycles.
研究领域:
材料科学
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储能技术
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固态电化学
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锂离子电池
✓ 已验证
DOI
高影响因子
CERAMICS INTERNATIONAL
·
2026
·
IF 6
Xin An,Feiyan Yang,Pengyu Liu,Qijun Li,Yang Li,Shaoxiong Han,Jiang You,Yongzhen Wang
Elucidating the atomic-scale ion transport mechanism in solid-state electrolytes is crucial for the development of all-solid-state batteries. As a promising oxide-based solid-state electrolyte, Li 7 La 3 Zr 2 O 12 (LLZO) has been a research hotspot regarding its phase transition and ion transport mechanisms. Due to the limited unit cell volume of LLZO, few existing studies have investigated the influence of high-entropy multi-element doping on the crystal structure and ion migration pathways of LLZO. The development of machine learning potential functions has provided a powerful tool for high-precision and high-efficiency simulations of complex systems. In this study, molecular dynamics simulations guided by a machine learning-based neuroevolution potential were employed to systematically investigate the effect of high-entropy elemental doping on the ionic conductivity of LLZO. The computational results indicate that high-entropy doping with high-valence elements significantly reduces the Li + diffusion energy barrier. Simulation results indicate that LLZrSnHfCeTaO possesses superior ionic conductivity. Relative to undoped c-LLZO, this multi-component system achieves a substantial decrease in the ionic migration barrier (from 0.399 eV to 0.22 eV) and an increase in the DOS bandwidth (from 3.7 eV to 4.79 eV). The prepared high-entropy garnet electrolyte Li 7 La 3 (Zr 0.2 Sn 0.2 Hf 0.2 Ce 0.2 Ta 0.2 ) 2 O 12 exhibits a reduced activation energy from 0.43 eV to 0.35 eV, an order-of-magnitude increase in room-temperature ionic conductivity, and excellent air stability. This work reveals the microscopic mechanism by which high-entropy doping enhances the ionic conductivity of LLZO, providing important insights for the rational design and controllable synthesis of high-performance solid-state electrolytes.
✓ 已验证
产品关联
DOI
高影响因子
Journal of Energy Storage
·
2026
·
IF 10.7
Wenteng Yang,Zhiding Han,Zhi Nie,Yingqiang Wu,Zaowen Zhao,Lei Yu,Junchen Zhou,Guizhen Wang,Xuerong Zheng,Yida Deng
Polyethylene oxide (PEO)-based electrolytes exhibit great compatibility with lithium-metal anodes. However, complex cleavage reactions occur with cathode electrode at high voltages, and constructing artificial interfacial layers has emerged as an effective strategy. In this work, we employed atomic layer deposition (ALD) to build a nanometer-scale amorphous Al₂O₃ interlayer between the LiNi₀.₆Co₀.₂Mn₀.₂O₂ (NCM622) cathode and the PEO/Li 7 La 3 Zr 2 O 12 (LLZO) composite electrolyte, which enhanced the cycling stability of the cells at 4.3 V. With an optimized interfacial thickness, the capacity retention improved from 44.8% to 97.3% after 100 cycles and remained 86.5% after 200 cycles, accompanied by enhanced rate capability. The artificial interlayer suppressed parasitic reactions by blocking direct contact between the active material and polymer electrolyte, thereby alleviating interfacial polarization during cycling.
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF MEMBRANE SCIENCE
·
2022
·
IF 10.53
Wen He,Hui Ding,Xu Chen,Wensheng Yang
Composite solid electrolyte (CSE) membranes for lithium metal batteries attract great attention with excellent safety and suitable flexibility. Herein, we construct a polyethylene oxide-based ultrathin CSE membrane that is enhanced by a 3D fiber network composed of Poly (vinylidene fluoride- co -hexafluoropropylene) fibers and Li 7 La 3 Zr 2 O 12 particles directly fabricated on the cathode. The 3D fiber network facilitates the rapid transport and uniform deposition of Li + , and enhances the mechanical strength of the electrolyte membrane, thereby effectively inhibiting the growth of lithium dendrites . Moreover, the unique preparation method reduces the interfacial impedance, and it can also greatly reduce the electrolyte thickness, which is beneficial to increasing the energy density of the battery. The lithium symmetric battery shows stable cycling over 1500 h under 0.2 mA cm −2 . Li/LiFePO 4 battery with the CSE membrane exhibits a high reversible capacity of 155.8 mAh·g −1 at 0.2 C for 100 cycles and the capacity retention rate is 98.0%. Furthermore, the obtained CSE membrane has a broadened electrochemical window of 4.83 V, and the reversible capacity of the Li/LiNi 0.8 Co 0.1 Mn 0.1 O 2 battery is 160.6 mAh·g −1 at 0.2 C for 100 cycles. These findings showed that the structure proposed here is a viable electrolyte strategy for advanced solid-state lithium metal batteries.
研究领域:
材料科学
·
能源存储
✓ 已验证
产品关联
DOI
高影响因子
CERAMICS INTERNATIONAL
·
2020
·Vol. 46
·期 8
·10917-10924
·
IF 3.83
Li Yang,Qiushi Dai,Lei Liu,Dingsheng Shao,Kaili Luo,Sidra Jamil,Hong Liu,Zhigao Luo,Baobao Chang,Xianyou Wang
Solid electrolytes could address the increasingly urgent safety and energy density concerns of lithium-ion batteries. Among several kinds of solid electrolytes, Ta-doped Li 7 La 3 Zr 2 O 12 (Ta-LLZO) became a research hotspot because of its high Li-ion conductivity and chemical stability against Li-metal and air. However, the preparation of high quality LLZO ceramic electrolyte via conventional air ambient sintering method is still a big challenge due to the serious “Li-loss” and abnormal grain growth phenomenon during the long-time high-temperature sintering process . Herein, a new rapid ultra-high-temperature air ambient sintering method without mother powder (MP) is put forward for the preparation of high quality Ta-LLZO ceramic electrolyte. The rapid sintering strategy can effectively restrain “Li-loss”. Furthermore, it is demonstrated that the none-mother-powder method is superior to traditional mother-powder method. Ta-LLZO ceramics sintered without MP via this rapid sintering method own small grain size, tight grain boundary, dense microstructure and high conductivity. Specifically, the Ta-LLZO ceramic sintered at 1360 °C for 10 min without MP exhibits high conductivity (8.5 × 10 −4 S cm −1 at 25 °C) and high relative density (97%), which equate those made by hot pressing sintering method. Without MP, the sintering process can avoid a lot of material waste and simplify the operation process. Moreover, the rapid sintering process can sharply shorten sintering time and reduce energy consumption. Therefore, this low-cost high-efficient sintering strategy can be effectively used in the large-scale production of high-quality Ta-LLZO ceramic electrolyte.
研究领域:
材料科学
·
固态离子学
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能源材料
·
电化学
·
无机非金属材料
·
电池技术
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）