Battery Energy
·
2025
·
IF 9.9
Jun Ma,Ruilin He,Yidong Jiang,Ludan Zhang,Hongli Xu,Hongbo Zeng,Chaoyang Wang,Xiaoxiong Xu,Yonghong Deng,Jun Wang,Shang-Sen Chi
Solid-state electrolyte (SSE) is a potential way to solve the safety problems of lithium metal batteries (LMBs), and Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 (LLZTO) is one of the most extensive research SSEs due to its good air stability and wide electrochemical window. However, the residual alkali on LLZTO surface limits its application with polyvinylidene difluoride (PVDF)-contained binders, and the uncontrollable lithium dendrites growing between the grain boundaries of LLZTO particles would lead to rapid capacity fading and potential short circuit risk. Herein, by in situ coating Li 3 PO 4 (LPO) on LLZTO particles (LLZTO@LPO) evenly, the residual alkali on the LLZTO surface is neutralized and the pH value is reduced to 8.84. The modified LLZTO can be mixed with PVDF solution and shows good fluidity without a cross-linking reaction, making the subsequent ceramic coating on the separator feasible. The LLZTO@LPO coating polyethylene (PE) separator can achieve 1400 h (115% increase) stable cycling under 1 mA cm −2 current density in the Li∥Li symmetrical cell and 80% capacity retention after 260 cycles (NCM622-Li coin cell with 3 mAh cm −2 loading). Furthermore, the LLZTO SSE pellets were prepared with the LLZTO@LPO and assembled in coin cell. The critical current density (CCD) result increases from 0.7 to 1.6 mA cm −2 owing to that the LPO coating effectively inhibits the lithium dendrites formation through LLZTO grain boundaries. This work provides a strategy for fabricating the coating layer on LLZTO to improve the stability of LMBs.
研究领域:
材料科学
·
电化学
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DOI
高影响因子
Energies
·
2022
·Vol. 15
·期 9
·3206
·
IF 3.252
Li Huang,Jian Gao,Zhijie Bi,Ning Zhao,Jipeng Wu,Qiu Fang,Xuefeng Wang,Yong Wan,Xiangxin Guo
The cubic garnet Li7La3Zr2O12(c-LLZO) is one of the most promising solid electrolytes due to its high ionic conductivity and large electrochemical window. However, the critical issue of Li2CO3formation on the c-LLZO surface when exposed to air is problematic, which is detrimental to the ionic conductivity and storage. Herein, comparative studies were carried out on the air stability of Al-doped Li7La3Zr2O12(Al-LLZO), Al-Ta-doped Li7La3Zr2O12(Al-LLZTO), and Al-Nb-doped Li7La3Zr2O12(Al-LLZNO). It was found that Al-LLZTO and Al-LLZNO are less reactive with air than Al-LLZO. The morphology of Li2CO3on Al-LLZTO micro-sized powders after air exposure was island-like with ~1.5 μm in thickness. The interfacial resistance of Li/Al-LLZTO was also a factor of ~3 smaller than that of Li/Al-LLZO, leading to the improved cycle stability of Li/Al-LLZTO/Li symmetric cells. The first-principles calculations based on density functional theory (DFT) verified that the decomposition energy of Al-LLZTO was larger than that of Al-LLZO, inhibiting the reaction product of Li2O and, thus, the next step product of Li2CO3following the reactions of Li2O + H2O → LiOH and LiOH + CO2→ Li2CO3.
研究领域:
材料科学
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电化学
·
计算化学
✓ 已验证
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2025
·
IF 8.2
Pengfei Pang,Yi Liu,Hu Wang,Mingjie Liao,Hongdou Wei,Jiangchao Chen,Shenfeng Long,Wenping Liu,Kunpeng Jiang,Guisheng Zhu,Huarui Xu,Yunyun Zhao
The cubic phase Li7La3Zr2O12 (c-LLZO) has garnered significant attention as a crucial solid-state electrolyte material for high-energy-density Li metal batteries due to its exceptional chemical stability and safety characteristics. Ga-doped LLZO (Ga-LLZO) has emerged as one of the leading systems owing to its superior ionic conductivity; however, the interfacial instability between Ga-LLZO and Li metal and its underlying mechanisms remain inadequately understood. This study systematically modulated the Ga content in Li6.4GaxLa3Zr2–(0.6–3x)Ta0.6–3xO12 (GaxTa0.6–3x). The aim was to investigate the ionic conductivity enhancement mechanism in Ga-LLZTO and analyze the failure behavior of its interface with Li metal during a high-temperature coating. Ultimately, this work seeks to determine the optimal Ga content for achieving a stable Li metal interface. The results reveal that the improvement in room-temperature ionic conductivity of Ga-LLZTO is attributed to Coulombic repulsion between Ga3+ and Li+. This enhancement effect is only effective below 45 °C. At elevated temperatures, Li+ possesses a sufficient intrinsic driving force for migration within the electrolyte lattice, while Ga3+ occupation of Li sites conversely impedes carrier mobility. Furthermore, the reaction between Ga-LLZTO and Li metal leads to the formation of the Li–Ga alloy and LiGaO2 phases. When the highly electronically conductive alloy phase forms at the electrolyte/Li metal interface, it promotes uniform electron distribution, reduces polarization voltage, and improves interfacial contact. Conversely, accumulation of Li–Ga alloy phases within the electrolyte bulk induces electrolyte failure. The results demonstrate a critical Ga doping threshold at x = 0.10. Within this threshold range, the critical current density (CCD) exhibits a negative correlation with Ga doping content. The Li||Ga0.10Ta0.30||Li symmetric cell demonstrates stable cycling for 537 h at a current density of 0.1 mA cm–2. The formation of detrimental Li2GaO2, Li5GaO4, and Li–Ga alloy phases within the electrolyte bulk induces soft short circuits, resulting in cell failure through a mechanism distinct from conventional Li dendrite penetration. The LiFePO4||Ga0.10Ta0.30||Li full cell achieves a discharge capacity of 144.1 mAh g–1 after 100 cycles with a capacity retention of 92.8%. In conclusion, this work clarifies the regulation mechanism of Ga-LLZTO stability and reveals the dual role of Li–Ga alloys. These findings provide a theoretical foundation for the rational application of Ga-doped garnet-type solid electrolytes.
研究领域:
材料科学
·
电化学
·
储能技术
·
固态电池
·
陶瓷材料
✓ 已验证
产品关联
DOI
PubMed
高影响因子
International Journal of Minerals Metallurgy and Materials
·
2026
·Vol. 33
·期 5
·1574-1584
·
IF 8.8
Liu Ting,Xu Hao,Liu Shuai,Cai Shixia,Wang Weimin,Song Kaikai,Hu Lina,Sui Kunyan
Lithium metal batteries have been widely used in energy storage applications owing to their high theoretical energy density. However, the unstable solid electrolyte interphase (SEI) in the batteries lead to the formation of lithium dendrites and “dead lithium”, thus affecting the safety and cycle life of the battery. To address this issue, an artificial SEI was prepared using a polymer coating strategy. The introduction of succinonitrile (SN) accelerates ion transport by promoting the dissociation of lithium salts. The solid electrolyte Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 (LLZTO) enhances the mechanical strength of artificial SEIs and promotes ion conduction. Furthermore, the competitive coordination between LLZTO and SN inhibits lithium anode corrosion, forming SEI rich in LiF and Li 3 N. Therefore, the lithium metal anode modified with an artificial SEI can be stably plated/stripped for more than 10000 h. The LiFePO 4 full cell assembled with the modified anode exhibited a discharge specific capacity of 133 mAh·g −1 and a capacity retention of 97% after 1000 cycles at 2 C (1 C = 170 mA·g −1 ). Notably, the anode modified with the artificial SEI exhibited excellent electrochemical performance even at low temperatures.
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DOI
高影响因子
ACS Applied Materials & Interfaces
·
2026
·
IF 7.8
Meng Meng,Renli Fu,Keke Ma,Jingnan Yang,Yi Ding,Ran Lu,Xiang Li,Xuhai Liu
Poly(vinyl alcohol) (PVA)-ionic liquid-Li6.75La3Zr1.75Ta0.25O12 (LLZTO) composite electrolyte (PIL) has drawn extensive research attention for lithium-ion batteries due to its high ionic conductivity. However, LLZTO tends to aggregate in PVA solution, which significantly impairs the lithium-ion transport rate within PIL. Herein, we coated the surface of LLZTO with a cylindrical cyclodextrin-LiTFSI (abbreviated as C-T) complex and systematically investigated the effects of the C-T coating and LLZTO content on the electrochemical performance of the PIL@C-T composite electrolyte. Specifically, when the LLZTO content is 60 wt %, the ionic conductivity of PIL@C-T can reach 4 × 10–3 S/cm. Based on lithium-ion transport mechanism analysis, we can conclude that the C-T coating can enhance the compatibility between LLZTO and the PVA matrix while constructing fast lithium-ion transport channels between LLZTO ceramic particles. Furthermore, the LiFePO4 | PIL@C-T | Li cell delivers a discharge capacity of 162 mAh/g, and its Coulombic efficiency can be maintained at approximately 100% after 200 cycles. This work provides a new strategy to develop high-performance composite electrolytes, which hold great potential for applications in advanced lithium-ion batteries.
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2025
·
IF 6.3
Qian Liu,Jinghua Yin,Jialong Shen,Zhen Chen,Minghua Chen
With the rapid development of solid state battery technology, composite electrolytes, as a key material for enhancing battery performance, face poor interfacial compatibility issues between inorganic fillers and the polymer matrix , which becomes a bottleneck restricting the improvement of electrochemical properties of the electrolyte. To address the issues of low ionic transport efficiency and the growth of lithium dendrites , which are triggered by the poor interfacial compatibility, this paper introduces the silane coupling agent (3-chloropropyl) trimethoxysilane (CTMS) into the PEO-LLZTO composite solid electrolytes to bridge the inorganic filler and polymer matrix through an in-situ coupling reaction, thereby enhancing the performance of the composite electrolyte. Its ionic conductivity is 1.84 × 10 −3 S/cm at 60°C, and the stability to lithium anode is improved, with a polarization voltage of only 0.017 V and ultra-long lithium symmetrical battery constant current cycle exceeding 1670 h. The assembled full battery exhibited excellent rate performance and cycle stability at 60°C under 0.2 C, its specific capacity remains 138.52 mAh/g after 135 cycles. The mechanism of CTMS enhancing electrolyte properties was investigated by density functional theory (DFT). The adsorption energy , differential charge density, and ELF are calculated to analyze the interaction between the electrolyte components. DFT calculation results suggest that O-Si-O bonds are readily formed at the LLZTO/PEO interface upon the addition of CTMS. More importantly, CTMS modifies the charge distribution of the space charge layer at this interface, effectively facilitating the migration of lithium ions , thereby optimizing the ionic transport properties at the interface. Both experimental and DFT results indicate that CTMS forms a strong chemical bond between the inorganic and polymer segments , which creates a rapid transport channel for lithium ions and reduces the migration of the lithium salt anion group, thereby improving the electrochemical performance of the electrolyte.
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF SOLID STATE ELECTROCHEMISTRY
·
2023
·Vol. 27
·期 10
·2671-2679
·
IF 2.5
Gu Yuanchun,Liu Huaqian
Significant ultraviolet (UV) technology was used to create a new composite polymer electrolyte (CPE) membrane composed of poly (vinylidene fluoride-hexafluoropropylene) (PVDF-HFP), benzophenone (Bp), and varying amounts of highly ion-conducting Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO) particles. In lithium metal batteries, the CPE membranes demonstrated improved mechanical properties as well as superior electrochemical performances. CPE-15wt% LLZTO typically demonstrated the highest ionic conductivity (σ = 3.7 × 10 −3 S/cm) at room temperature, a high Li-transference (t + = 0.79), and a wider electrochemical stability window (ESW) above 5 V, as well as good mechanical strength (8.2 MPa). More importantly, the CPE-15wt% LLZTO membrane inhibits Li dendrite expansion in Li symmetric cells and exhibits long-term cyclic stability with a current density of 3 mA/cm 2 over 1150 h for Li/CPE-15wt% LLZTO/Li. The current study demonstrates that a UV-irradiated CPE membrane can be a promising electrolyte for next-generation lithium-metallic batteries.
研究领域:
材料科学
·
能源存储技术
✓ 已验证
DOI
高影响因子
JOURNAL OF POWER SOURCES
·
2014
·
IF 5.211
Kai Liu,Jiang-Tao Ma,Chang-An Wang
Garnet type electrolyte “Li 6.5 La 3 Ta 0.5 Zr 1.5 O 12 ” (LLZTO) was prepared by conventional solid-state reaction in alumina crucibles and excess lithium salt (from 0% to 50 mol%) was added into the starting materials to investigate the effects of excess lithium salt on the property of LLZTO. SEM, XRD and AC impedance were used to determine the microstructure, phase formation and Li-ion conductivity. Cubic garnet with a minor second phase LiAlO 2 in the grain boundary was obtained for the pellets with excess lithium salt. As the amount of excess lithium salt increased, more Al element diffused from alumina crucibles to LLZTO pellets and reacted with excess lithium salt to form liquid Li 2 O–Al 2 O 3 phase in the grain boundary, which accelerated the pellets' densification and reduced lithium loss at a high temperature. Ionic conductivity of LLZTO pellets increased with the amount of excess lithium salt added and leveled off at ∼4 × 10 −4 S cm −1 when lithium salt exceeded 30 mol%. The performance of Li-air batteries with hybrid electrolytes, using homemade LLZTO thin pellets as solid electrolytes , was investigated. The LLZTO thin pellet with more excess lithium salt in starting material had a higher density and resulted in better cell performance.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2025
·
IF 9.7
Da Yang,Yaning Liu,Tianqi Yang,Ruyi Fang,Zhen Xiao,Wenkui Zhang,Xinping He,Yongping Gan,Jun Zhang,Xinhui Xia,Hui Huang,Yang Xia
Non-flammable butanedinitrile (SN) is recognized as a highly prospective plasticizer for significantly reducing the operating temperature of polyethylene oxide (PEO)-based solid polymer electrolytes. However, the instability of the lithium anode interface severely hinders the practical application of PEO/SN-based solid polymer electrolytes in room-temperature solid-state lithium metal batteries. In this work, we propose fast-ion conductive Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO) nanoparticles as corrosion inhibitors to constructure a multifunctional buffer layer on the surface of PEO/SN-based solid electrolyte (PSE@LLZTO) to stabilize the interface structure of Li anode via a facile spin-coating transfer technique. This LLZTO modified buffer layer with rigid inorganic LLZTO phase and soft organic PEO-LiTFSI phase, not only significantly homogenizes lithium deposition, but also effectively improves the resistance to dendrite formation. Impressively, the LLZTO phase is able to adsorb free SN molecules, preventing them from continuously corroding the Li anode, thereby significantly reinforcing the interface stability. Meanwhile, these rigid LLZTO ceramic particles effectively inhibit lithium dendrite growth. Consequently, the Li symmetric cell demonstrates consistent performance for 1600 h at room temperature, and the LiFePO 4 |PSE@LLZTO|Li cells exhibit a high reversible specific capacity of 146 mA h g −1 with a remarkable capacity retention of 98.4 % after 200 cycles under 0.5C at room temperature. This study offers a feasible approach for the practical utilization of PEO/SN-based solid electrolyte systems in long lifespan 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
PubMed
高影响因子
Materials
·
2024
·Vol. 17
·期 13
·3094
·
IF 3.1
Chengjun Lin,Yaoyi Huang,Dingrong Deng,Haiji Xiong,Bin Lu,Jianchun Weng,Xiaohong Fan,Guifang Li,Ye Zeng,Yi Li,Qihui Wu
Replacing the flammable liquid electrolytes with solid ones has been considered to be the most effective way to improve the safety of the lithium batteries. However, the solid electrolytes often suffer from low ionic conductivity and poor rate capability due to their relatively stable molecular/atomic architectures. In this study, we report a composite solid electrolyte, in which polyethylene oxide (PEO) is the matrix and Li6.4La3Zr1.45Ta0.5Mo0.05O12(LLZTMO) and Li6.4La3Zr1.4Ta0.6O12(LLZTO) are the fillers. Ta/Mo co-doping can further promote the ion transport capacity in the electrolyte. The synthesized composite electrolytes exhibit high thermal stability (up to 413 °C) and good ionic conductivity (LLZTMO–PEO 2.00 × 10−4S·cm−1, LLZTO–PEO 1.53 × 10−4S·cm−1) at 35 °C. Compared with a pure PEO electrolyte, whose ionic conductivity is in the range of 10−7~10−6S·cm−1, the ionic conductivity of composite solid electrolytes is greatly improved. The full cell assembled with LiFePO4as the positive electrode exhibits excellent rate performance and good cycling stability, indicating that prepared solid electrolytes have great potential applications in lithium batteries.
研究领域:
材料科学
·
能源存储技术
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF POWER SOURCES
·
2024
·
IF 8.1
Nan Zhang,Hongpeng Zheng,Guoyao Li,Cheng Ouyang,Yu Yang,Hong Zhu,Rongzi Zhang,Haidong Sun,Chenglan Zhang,Hezhou Liu,Huanan Duan
Lithium metal is an important strategic resource with diverse industrial applications such as glass, ceramics, and alloys. With the increasing demand for lithium, lithium extraction from brines has become the focus of attention. However, due to the similarity of the radii of Li + and Mg 2+ , conventional lithium extraction methods are inefficient for lithium extraction from brines with a high Mg/Li ratio. Herein we propose a direct electrolytic extraction of lithium (DEEL) system based on a sandwich-structured LLZTO (Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 ) electrolyte with excellent water stability. The lanthanum zirconate (La 2 Zr 2 O 7 ) on the surface of this sandwich-structured LLZTO can achieve high stability to water and air while still maintaining high ionic conductivity (7.5 × 10 −4 S cm −1 ) and low lithium interface resistance (40 Ω cm 2 ). This sandwich-structured LLZTO has been successfully demonstrated to stably extract lithium from simulated and natural brines. The current density for lithium extraction can reach 0.5 mA cm −2 , corresponding to a lithium extraction rate of 126 μg cm −2 h −1 ; the electrochemical extraction devices can stably work for 48 h; the current efficiency can reach 97.71 %. The extracted lithium metal exhibits a purity of 99.475 wt%. This work provides a highly efficient approach for extracting lithium from brines by electrolysis.
研究领域:
材料科学
·
电化学
·
资源工程
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF POWER SOURCES
·
2025
·
IF 7.9
Yaqin Ji,Haoran Du,Kang Wang,Jian Ma,Wenjuan Yang,Xulai Yang,Zhenzhen Liu,Xin Liang,Huaxia Deng,Hongfa Xiang
Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO) is one of the most widely used solid electrolytes for solid-state lithium-ion batteries (SSLIBs). However, this ceramics-type solid electrolyte suffers from poor interfacial contact and impure surface phase, causing large interfacial resistance and hindering Li + transport. In this study, a binary polymer solution acting as a self-purification and surface-coordination agent, consisting of polyacrylonitrile (PAN) and poly (vinylidene fluoride-co-chlorotrifluoroethylene) (PC), are mixed with LLZTO to form a Li + -transport-enhanced solid-state composite electrolyte. PC effectively eliminates the Li 2 CO 3 impurity to form in-situ LiF coating on LLZTO particles. Simultaneously, the –CN groups in PAN establish coordination bonds with LLZTO, creating fast Li + transport channels at the polymer/ceramic interphase. In addition, the introduced flexible polymer phase enhances the interfacial contact between electrodes and electrolyte. The optimized polymer/LLZTO interphase enables the as-prepared solid-state composite electrolyte to deliver excellent electrochemical performances. The assembled quasi-solid-state Li||LiFePO 4 cells stably work at 0.5 C (1 C = 170 mA g −1 ) for >300 cycles at 60 °C and >600 cycles at room temperature, respectively. The Li||Li cell also shows a cycling life of >2000 h at 0.1 mA cm −2 and 0.1 mAh cm −2 . This strategy effectively improves Li + migration on the polymer/LLZTO interphase, providing a new approach for next-generation SSLIBs.
研究领域:
材料科学
·
电化学
✓ 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）