Nano Research
·
2024
·Vol. 17
·期 6
·5251-5260
·
IF 9.5
Fang Chang,Huang Kangsheng,Zhao Jing,Tian Shiqi,Dou Hui,Zhang Xiaogang
Despite the high energy density of lithium metal batteries (LMBs), their application in rechargeable batteries is still hampered due to insufficient safety. Here, we present a novel flame-retardant solid-state electrolyte based on polyvinylidene fluoridehexafluoropropylene (PVDF-HFP) with nano SiO 2 aerogel as an inert filler but Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO) as an auxiliary component to enhance the ion conductivity. The introduction of SiO 2 aerogels imparts the polymer electrolyte with exceptional thermal stability and flame retardancy. Simultaneously, the interaction between hydroxyl groups of SiO 2 particles and PVDF-HFP creates a strong cross-linking structure, enhancing the mechanical strength and stability of the electrolyte. Furthermore, the presence of SiO 2 aerogel and LLZTO facilitates the dissociation of lithium salts through Lewis acid-base interactions, resulting in a high ionic conductivity of 1.01 × 10 − 3 S·cm − 1 and a wide electrochemical window of ∼ 5.0 V at room temperature for the prepared electrolytes. Remarkably, the assembled Li|Li cell demonstrates the excellent resistance to lithium dendrite and runs stablly for over 1500 h at a current density of 0.25 mA·cm −2 . Thus, we prepare a pouch cell with high safety, which can work normally after short-circuiting under the external folding and cutting.
研究领域:
材料科学
·
电化学
·
高分子科学
·
储能技术
·
纳米技术
✓ 已验证
DOI
高影响因子
Journal of the American Chemical Society
·
2024
·
IF 14.4
Wenbo Zhai,Yue Zhang,Hongsheng Shi,Xiangchen Hu,Ruixin Hao,Wei Liu,Yi Yu
Investigating the growth kinetics of Li metal in solid-state batteries is crucial to both a fundamental understanding and practical application. Here, by directly observing the formation of Li metal from Ta-doped Li6.4La3Zr1.4Ta0.6O12 (LLZTO) in a transmission electron microscope, the growth kinetics is analyzed quantitatively. The growth kinetics of Li deposits shows a cubic-curve characteristic for LLZTO with Li-source-free. Instead, a linear growth process is observed with Li-source supplied. The impact of the illuminating electron dose rate on the growth kinetics is clarified, indicating that even low dose rates (1–3 e–/Å2/s) could affect Li growth, highlighting the significance of controlling dose rates. Furthermore, a new pathway for the formation of Li metal from Li-containing materials utilizing the field-emission effect is reported. This work has implications on the failure mechanism in solid batteries by using limited Li anodes and opens pathways for regulating Li growth in LLZTO at various scenarios, which can also extend to other ionic conductors.
研究领域:
材料科学
·
电池技术
·
电化学
✓ 已验证
DOI
高影响因子
Science Advances
·
2022
·Vol. 8
·期 40
·
IF 14.957
Jing Xu,Yang Jin,Kai Liu,Nawei Lyu,Zili Zhang,Bin Sun,Qianzheng Jin,Hongfei Lu,Huajun Tian,Xin Guo,Devaraj Shanmukaraj,Hui Wu,Meicheng Li,Michel Armand,Guoxiu Wang
Recycling lithium from spent batteries is challenging because of problems with poor purity and contamination. Here, we propose a green and sustainable lithium recovery strategy for spent batteries containing LiFePO4, LiCoO2, and LiNi0.5Co0.2Mn0.3O2 electrodes. Our proposed configuration of “lithium-rich electrode || LLZTO@LiTFSI+P3HT || LiOH” system achieves double-side and roll-to-roll recycling of lithium-containing electrode without destroying its integrity. The LiTFSI+P3HT-modified LLZTO membrane also solves the H+/Li+ exchange problem and realizes a waterproof protection of bare LLZTO in the aqueous working environment. On the basis of these advantages, our system shows high Li selectivity (97%) and excellent Faradaic efficiency (≥97%), achieving high-purity (99%) LiOH along with the production of H2. The Li extraction processes for spent LiFePO4, LiNi0.5Co0.2Mn0.3O2, and LiCoO2 batteries is shown to be economically feasible. Therefore, this study provides a previously unexplored technology with low energy consumption as well as high economic and environmental benefits to realize sustainable lithium recycling from spent batteries.
研究领域:
材料科学
·
环境科学
·
可持续发展
·
电池技术
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF POWER SOURCES
·
2023
·
IF 9.2
Qiujun Wang,Pin Zhang,Weiqi Zhu,Zhaojin Li,Di Zhang,Huan Wang,Huilan Sun,Bo Wang,Shang-Sen Chi
The practical application of solid-state batteries is limited by the relatively low ionic conductivity of solid polymer electrolytes (SPEs) and the high charge transfer resistance resulting from poor interfacial wettability between electrodes and solid electrolytes of inorganic solid electrolytes (ISEs). In this manuscript, a dual-salt dual-network composite electrolyte is prepared by adjusting the content of lithium bis(oxalato)borate (LiBOB) and Li 6.75 La 3 Zr 1.75 Ta 0.25 O 12 (LLZTO), and a composite electrolyte with excellent long cycle and interfacial stability is designed. The as-prepared composite electrolyte that includes 77 wt% gel electrolyte, 20 wt% LLZTO and 3 wt% LiBOB (assigned as PDFL-20LLZTO-3LiBOB) has a high ionic conductivity of 1.69 × 10 −3 S cm −1 and a high lithium-ion migration number of 0.833 at 25 °C. The Li metal battery (LMB) with PDFL-20LLZTO-3LiBOB exhibits excellent cycling stability with 94% capacity retention at 25 °C for 100 cycles. The corresponding symmetrical Li|PDFL-20LLZTO-3LiBOB|Li can cycle for over 1200 h with excellent long-term stability. This impressive electrochemical performance is attributed to the in-situ formation of a dense and uniform solid electrolyte interface (SEI) rich in LiF and B–F at the interface under the dual action of LiBOB and fluoroethylene carbonate (FEC). In addition, the high ionic conductivity and high ionic mobility number are favorable for uniform deposition of Li and stable interfacial compatibility.
研究领域:
材料科学
·
电化学
·
能源存储
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Yixiao Zhang,Xue Ye,Han Fu,Yu Zhong,Xiuli Wang,Changdong Gu,Jiangping Tu
Ether-based polymer electrolyte shows promising potential for application in solid-state lithium batteries owing to its cost-effectiveness, excellent flexibility, and above all, remarkable stability to lithium metal anode. However, it still suffers from challenges related to low ionic conductivity and inferior oxidation resistance. Herein, an ether-based gel composite electrolyte containing Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 (LLZTO) ceramics (LL-GCE) is fabricated via an in-situ polymerization method which can guarantee good interface contact with electrodes. The ceramics not only activate the interaction between polymers and lithium salts, resulting in significantly enhanced ionic conductivity (7.9 × 10 −4 S cm −1 ), but also collaborate with poly(1,3-dioxolane) (PDOL) to construct favorable anion-rich solvation configurations, which effectively restrict the anion migration with Li + transference number significantly increased to 0.83. Furthermore, the regulated solvation structures can passivate the electrode surface with a high content of robust LiF components formed on the electrolyte/electrode interphase. Consequently, the composite electrolyte demonstrates excellent abilities to inhibit Li dendrite growth and match with high-voltage cathodes. For instance, the LiFePO 4 ||Li cell using such electrolyte conveys a capacity of 135.4 mAh/g and the capacity retention is 99.3 % after 250 cycles at 1C. The LiCoO 2 ||Li full cell also shows excellent cycling performance. This work provides an effective strategy to modify ether-based polymer electrolytes and can boost their development in high-performance solid state lithium metal batteries.
研究领域:
材料科学
·
电化学
·
能源存储
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2022
·
IF 10.383
Xiang Ma,Mian Liu,Qingping Wu,Xiang Guan,Fei Wang,Hongmei Liu,Jun Xu
Compared with simplex ceramic or polymer solid electrolytes, composite solid electrolyte (CSE) is more promising for its better interfacial compatibility to electrode and high ionic conductivity simultaneously. Further, the interfacial compatibility within ceramic and polymer is considered to be more and more critical to the overall performance of solid-state batteries. Avoiding the agglomeration of ceramic particles at high loadings can improve the whole intrinsic characteristic and electrochemical performance of CSEs. Herein, we designed a CSE (EO@LLZTO–PEO), which consists of composite particles (EO@LLZTO) as a filler and polyethylene oxide (PEO) as polymer matrix. EO@LLZTO was prepared by chemically grafting polyethylene glycol monomethyl ether methacrylate (MPEG-MAA) on the micro-sized Li6.4La3Zr1.4Ta0.6O12 (LLZTO) particles. By introducing of polymer containing EO segments onto LLZTO, the interfacial compatibility between LLZTO and PEO matrix is highly enhanced, and the intrinsic Li+ complexation capability of MPEG-MAA is improved, even at the high loading of garnet. EO@LLZTO–PEO shows a high ionic conductivity (1.91 mS cm–1), a broad electrochemical window (∼5.2 V vs Li/Li+), and a high lithium ion transference number (0.72). The Li/EO@LLZTO–PEO/Li battery also exhibits a long cycle stability (over 1200 h of cycling). Moreover, all-solid-state batteries with LiFePO4 and LiNi0.8Co0.1Mn0.1O2 (NCM811) cathodes exhibit excellent cycling stability and rate performance. Consequently, enhancing the interfacial compatibility between organic and inorganic electrolytes is identified to be one of the crucial strategies for commercial solid-state lithium batteries.
研究领域:
材料科学
·
电化学
·
储能技术
·
纳米技术
·
高分子化学
✓ 已验证
DOI
高影响因子
ELECTROCHIMICA ACTA
·
2018
·
IF 5.116
Zhaoshuai Zhang,Long Zhang,Chuang Yu,Xinlin Yan,Bo Xu,Li-min Wang
Garnet-type Li 7 La 3 Zr 2 O 12 solid electrolytes were commonly prepared by two steps solid-state reaction method, which undergoes high temperature over 1000 °C and thus inevitable for lithium volatilization and formation of secondary phases. Here, we propose a new intergrain architecture engineering of a solution method, to avoid high temperature sintering for preparing lithium halide (LiX) coated garnet-type solid electrolytes, which contain Al and Ta co-doped Li 7 La 3 Zr 2 O 12 (Li 6.75 La 3 Zr 1.75 Ta 0.25 O 12 , LLZTO) synthesized at 900 °C with cubic structure. Owing to the increased relative density, the improved formability, and the altered ion transport mode from point to face conduction by LiX coating on LLZTO grains, LiX-coated LLZTO samples demonstrate a good Li dendrite suppression ability and a high ionic conductivity that is three orders of magnitude higher than pristine LLZTO. In another way, this result demonstrates the critical role of the grain boundaries on the ion transport for oxide superionic conductors. The present coating method provides a new strategy to prepare brittle solid electrolytes avoiding high temperature sintering.
研究领域:
材料科学
·
电化学
·
固体化学
✓ 已验证
产品关联
DOI
高影响因子
ADVANCED FUNCTIONAL MATERIALS
·
2024
·
IF 18.5
Yaping Wang,Pengcheng Yuan,Xiong Xiong Liu,Shengfa Feng,Mufan Cao,Jianxiang Ding,Jiacheng Liu,Song-Zhu Kure-Chu,Takehiko Hihara,Long Pan,ZhengMing Sun
Composite solid electrolytes (CSEs) integrate the fast ion conductivity of inorganic electrolytes and the excellent interfacial compatibility of polymer electrolytes. Typically, fluoropolymers and garnets are promising individuals to formulate cutting-edge CSEs owing to their unique properties. However, the alkaline garnets can induce the dehydrofluorination of fluoropolymers, deteriorating their CSEs performance. Here, for the first time, NH 4 HCO 3 is proposed as a sacrificial inhibitor to effectively prevent the garnet-induced dehydrofluorination, using Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO) and poly(vinylidene fluoride- co -hexafluoropropylene) (PVH) as symbolic garnets and fluoropolymers, respectively. Various findings demonstrate that NH 4 HCO 3 can buffer the alkalinity of LLZTO, thereby inhibiting the dehydrofluorination of PVH. In addition, NH 4 HCO 3 can completely decompose to volatiles upon drying without compromising the properties of LLZTO and PVH. Additionally, a polymer-in-salt strategy is further introduced by adding high-concentration LiTFSI salt to the above system, resulting in the PVH/LiTFSI/LLZTO (PLL) CSEs. Benefiting from the synergetic coupling of the sacrificial inhibitor and polymer-in-salt strategies, the PLL exhibits an exceptionally high ionic conductivity of 1.2 mS cm −1 at 25 °C and stable voltage of 5.09 V, outperforming other reported CSEs. Consequently, the PLL delivers impressive high-rate cyclability in solid-state lithium-metal batteries with an outstanding capacity retention of 95.4% after 240 cycles at 1 C (25 °C).
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
·
2025
·
IF 13.2
Amin Chen,Na Li,Chenxu Sun,Yanmin Qin,Luyao Qi,Huipei Zhang,Haifeng Bao
Both inorganic solid electrolytes and organic polymer solid electrolytes face limitations in practical applications due to their shortcomings. Inorganic solid electrolytes suffer from high interface impedance and poor mechanical properties, while polymer solid electrolytes struggle with low Li-ion conductivity, thermal stability and electrochemical stability. To overcome the drawbacks of single phase solid electrolytes while utilizing their respective advantages, composite solid electrolytes have emerged as a popular research direction in recent years. Typical composite solid electrolytes feature inorganic filler particles dispersed in a polymer matrix. In this work, we introduce a novel non-flammable composite solid electrolyte with inorganic matrix and inorganic fillers. The composite solid electrolyte was prepared by integrating a 3D Si-Zr-O-C inorganic fiber film with Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO) particles that have high ionic conductivity via a vacuum impregnation process, which is all-inorganic solid state electrolyte. This unique design of established network structure provides fast Li-ion transport channels, enabling high ionic conductivity (2.3 × 10 −4 S cm −1 at room temperature). Furthermore, the Si-Zr-O-C/LLZTO (SLTO) composite electrolyte also exhibits superior flexibility, thermal stability, and electrochemical stability. The SLTO composite solid electrolyte presents a promising electrolyte candidate for next generation lithium ion batteries.
研究领域:
材料科学
·
电化学
·
储能技术
·
纳米技术
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2023
·
IF 6.2
Tao Wang,Xiaoyan Liu,Ling Xie,Yuyu He,Haining Ji,Liping Wang,Xiaobin Niu,Jian Gao
The application of solid-state electrolyte in lithium metal batteries is a promising technology to meet the demands for next-generation high-energy-density storage systems. Poly (ethylene oxide) (PEO)-based solid polymer electrolytes have been widely studied, but their electrochemical window is too narrow to be compatible with high-voltage cathodes and their mechanical properties are poor as well. Combination of organic and inorganic compounds is an effective approach to solve this limitation. In this study, Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO) was surface-modified with a silane coupling agent and compounded with polyacrylonitrile (PAN) to form a 3D nanofiber framework via electrospinning technology, and the PEO-Succinonitrile (SN)-LiTFSI solution was uniformly dispersed in the 3D nanofiber framework to form a continuous Li + transport path. The prepared composite solid electrolytes (CSEs) showed high ionic conductivity (1.58 × 10 −4 S cm −1 at room temperature), a broad electrochemical window (5.1 V, vs. Li/Li + ), and an attractive mechanical strength of 49.4 MPa. In addition, solid-state Li/CSE/NCM811 batteries exhibited high coulombic efficiency and significant stable cycling performance.
研究领域:
材料科学
·
电化学
·
能源存储
·
纳米技术
✓ 已验证
产品关联
DOI
高影响因子
ELECTROCHIMICA ACTA
·
2025
·
IF 5.6
Yaqin Ji,Wenjuan Yang,Jian Ma,Haoran Du,Xulai Yang,Zhenzhen Liu,Sheng Liang,Lingli Liu,Lei Hu,Xin Liang
It is a persistent goal for solid-state electrolytes to enhance their ionic conductivity while maintaining good mechanical strength to potentially inhibit lithium dendrites. In this work, we introduce garnet-type Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO) fillers and polyacrylonitrile (PAN) into thermoplastic polyurethane (TPU) to fabricate a composite solid-state electrolyte. The TPU matrix contains hard segments (−NH−COO−) that provide efficient mechanical support and soft segments (−O−) responsible for good flexibility and elasticity. When blended with PAN, hydrogen bonds form between the functional groups of PAN and TPU, establishing strong intermolecular connections that further enhance the structural/electrochemical stability of the electrolyte. A stable polymer/filler interface can be constructed through the ion-dipole coordination interaction between the metal ions at the LLZTO surface and the −CN groups of PAN. Benefiting from the intricate interactions among the PAN/TPU dual polymers and the LLZTO filler, the composite electrolyte exhibits not only exceptional flexibility (a tensile strain of 208%) and tensile strength (40 MPa), but also a good ionic conductivity of 2.33 × 10 −4 S cm⁻¹ at room temperature, a high oxidation potential of 4.48 V, and an excellent Li + transference number of 0.79. The Li||LiFePO 4 battery employing this composite solid-state electrolyte exhibits remarkable electrochemical stability, delivering an initial discharge capacity of 127.4 mAh g −1 at 0.3C and room temperature, and maintains a capacity retention of 91.9% after 600 cycles. This work provides a new electrolyte modification strategy for next-generation solid-state lithium metal batteries.
研究领域:
材料科学
·
电化学
·
储能技术
·
高分子科学
·
纳米技术
·
电池技术
✓ 已验证
产品关联
DOI
高影响因子
Journal of Materials Chemistry A
·
2024
·Vol. 12
·期 45
·31570-31580
·
IF 10.7
Guoxiang Zheng,Yifan Jin,Michal Sedlačík,Elif Vargun,Yifan Zhang,Ying He,Petr Saha,Qilin Cheng
Solid-state lithium metal batteries (SSLMBs) with high energy density and superior safety have been recognized as next-generation energy storage systems and have attracted a lot of attention. Garnet-type oxide solid-state electrolytes, especially Li6.4La3Zr1.4Ta0.6O12 (LLZTO), with high ionic conductivity, low activation energy and superior stability with Li, are among the most promising solid-state electrolyte materials. However, high interfacial resistance, uneven lithium deposition and lithium dendrite growth between Li/LLZTO interfaces have hindered the industrialization of SSLMBs. In this work, a novel mortise–tenon-like hybrid ionic/electronic conductive interface (Li/LZFC@LLZTO) is constructed, which is composed of LiF, LiCl, and a Li–Zn alloy through an in situ transformation reaction. As expected, the interfacial impedance of Li|LZFC@LLZTO|Li is significantly reduced from 128 Ω cm2 to 2.7 Ω cm2, the critical current density increases from 0.3 mA cm−2 to 2.1 mA cm−2, and a prominent cycling performance of 6600 h at 0.2 mA cm−2 or 900 h at 0.4 mA cm−2 is achieved. Consequently, both the Li|LZFC@LLZTO|LiFePO4 and Li|LZFC@LLZTO|LiNi0.8Co0.1Mn0.1O2 full cells exhibit excellent rate performance. Furthermore, Li|LZFC@LLZTO|LiFePO4 can maintain a high discharge specific capacity close to 140 mA h g−1 at 0.2C after 150 cycles of stable cycling. This work lays the foundation for developing garnet-based SSLMBs with high critical current density, low interfacial impedance and long-term cycling performance.
研究领域:
材料科学
·
储能系统
·
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）