SOLID STATE IONICS
·
2018
·
IF 2.751
Wenping Zha,Yinghui Xu,Fei Chen,Qiang Shen,Lianmeng Zhang
In this work, Li 7 La 3 Zr 2 O 12 (LLZO)-based membrane electrolyte, which has good flexibility and can be easily mass-produced, is proposed to address the intrinsic defects of ceramic electrolytes . The LLZO-based membrane electrolyte is electrochemically stable in the voltage range of 0–5.2 V vs. Li/Li + due to the good oxidative stability of LLZO. We also develop a simple and low-cost approach to fabricate the all-solid-state lithium battery (ASSLB). Wet coating and hot pressing are applied to form a continuous and homogeneous electrolyte layer on a cathode layer. Thanks to the integrated preparation process, there is no obvious interface between the cathode layer and the electrolyte layer, hence reducing the interface resistance. The Li/LiFePO 4 batteries exhibit desirable cycling performance at 60 °C, which deliver a maximum discharge specific capacity of 151.6 mAh·g −1 at 0.1C and maintain 97.8% of the capacity after 50 cycles.
研究领域:
材料科学
·
电化学
·
能源存储
·
固态离子学
·
先进电池技术
✓ 已验证
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Chaoyan Zhang,Zhen Jiang,Xueying Yang,Jingyi Liu,Jianjun Song,Chuan Shi,Peng Zhang,Jinbao Zhao
Lithium-conducting fillers play crucial roles in enhancing the ionic conductivity of solid polymer electrolytes (SPEs). By providing supplementary rapid Li+ transport channels, they substantially boost the practical viability of solid-state batteries. Nevertheless, the inherent incompatibility between polymers and inorganic fillers invariably leads to phase separation, which exacerbates the transport barrier for lithium through interfaces and impedes the full utilization of these swift channels. Herein, a novel “Rotaxane chemistry” has been employed to engineer stable lithium transport pathways at the Li7La3Zr2O12(LLZO)/PEO interface. This strategy confines PEO chains within molecular semicircles on the surface of modified filler, namely LLZO@Rotaxane, which loosens chain entanglement and breaks tight coordination of (EO)n–Li. This promotes Li spontaneous diffusion to and transport through the nano-confinement space in the interface as well as through the LLZO. Consequently, the proportion of lithium transported by LLZO and interface has surged from 28.4 % to 56.0 %, endowing the PEO-LLZO@Rotaxane with an outstanding ionic conductivity of 1.90 mS cm−1 at 60 °C and Li+ transference number of 0.74. Correspondingly, the batteries fabricated with PEO-LLZO@Rotaxane also manifest excellent cyclic and rate performance. Thus, this work offers novel insights into increasing the ionic conductivity by interface engineering.
研究领域:
材料科学
·
电化学
·
能源化学
·
高分子化学
·
固态电池
✓ 已验证
产品关联
DOI
高影响因子
ACS Energy Letters
·
2022
·
IF 23.991
Furong Sun,Yubo Yang,Shu Zhao,Yongtao Wang,Mingxue Tang,Qingzhen Huang,Yang Ren,Heng Su,Boya Wang,Ning Zhao,Xiangxin Guo,Haijun Yu
Garnet-type solid-state electrolytes Li7La3Zr2O12 (LLZO) for high-energy-density batteries have attracted extensive attention. However, stabilizing the high-conductive cubic phase and improving its ionic conductivity remain challenges of current research. Here, a Ca–W dual-substitution strategy has been designed, and the effect of doping on cubic phase formation and Li+ mobility has been investigated thoroughly. The results indicated that the partial substitution of Ca2+ at the La3+ site and W6+ at the Zr4+ site can effectively stabilize the cubic phase while reducing the endothermic enthalpy during the synthesis. Moreover, Ca–W dual substitution regulates the local Li+ framework by increasing Li+ occupancy at the 96h site, which can significantly lower the Li+ migration barrier and thus improve the ionic conductivity by two orders of magnitude. This work addresses the challenge of stabilizing a highly conductive cubic phase with low-energy consumption and represents a major breakthrough in understanding how to improve the ionic conductivity by regulating local structures.
研究领域:
材料科学
·
固体离子学
·
储能技术
·
电池技术
✓ 已验证
DOI
高影响因子
ADVANCED MATERIALS
·
2024
·Vol. 36
·期 18
·2309019
·
IF 27.4
Zhanhui Jia,Hao Shen,Jiawei Kou,Tianyi Zhang,Zhen Wang,Wei Tang,Marca Doeff,Ching-Yu Chiang,Kai Chen
The application of solid-state electrolytes in Li batteries is hampered by the occurrence of Li-dendrite-caused short circuits. To avoid cell failure, the electrolytes can only be stressed with rather low current densities, severely restricting their performance. As grain size and pore distributions significantly affect dendrite growth in ceramic electrolytes such as Li 7 La 3 Zr 2 O 12 and its variants; here, a “detour and buffer” strategy to bring the superiority of both coarse and fine grains into play, is proposed. To validate the mechanism, a coarse/fine bimodal grain microstructure is obtained by seeding unpulverized large particles in the green body. The rearrangement of coarse grains and fine pores is fine-tuned by changing the ratio of pulverized and unpulverized powders. The optimized bimodal microstructure, obtained when the two powders are equally mixed, allows, without extra interface decoration, cycling for over 2000 h as the current density is increased from 1.0 mA·cm −2 , and gradually, up to 2.0 mA·cm −2 . The “detour and buffer” effects are confirmed from postmortem analysis. The complex grain boundaries formed by fine grains discourage the direct infiltration of Li. Simultaneously, the coarse grains further increase the tortuosity of the Li path. This study sheds light on the microstructure optimization for the polycrystalline solid-state electrolytes.
研究领域:
材料科学
·
储能技术
·
固态电池
·
陶瓷电解质
·
微观结构工程
✓ 已验证
DOI
高影响因子
Open Ceramics
·
2025
·
IF 2.8
Chengjian Li,Frank Kern,Lianmeng Liu,Christopher Parr,Andreas Börger,Chunfeng Liu
Garnet-type Li₇La₃Zr₂O₁₂ (LLZO) is a promising solid electrolyte for all-solid-state batteries due to its high ionic conductivity and excellent thermal stability. However, production of high performance LLZO remains constrained by the reliance on high-purity reagents and complex synthesis routes. This study presents a cost-effective strategy to prepare high-performance Ta- and Nb-doped LLZO using commercially sourced raw materials via conventional solid-state reaction. Two lithium precursors, Li 2 CO 3 and LiOH·H₂O, were systematically compared to evaluate their impacts on formation and performances of LLZO. LiOH-derived powders showed higher phase purity and finer morphology, while Li 2 CO 3 -derived powders offered better processability. While the LLZNO-LOH sample achieved 94.4% relative density and 0.78 × 10⁻ 3 S/cm conductivity, LLZTO-LCO also reached 0.75 × 10⁻ 3 S/cm with a relative density of 94.1%. All sintered samples exhibited phase-pure cubic garnet structures. These findings demonstrate the industrial feasibility of LLZO production, paving the way for its practical deployment in next-generation solid-state batteries.
研究领域:
材料科学
·
电化学
·
固态化学
·
储能技术
·
陶瓷材料
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Electronic Materials
·
2023
·
IF 4.7
Ying Zeng,Xingxing Zhai,Yingsong Yu,Dehua Li,Yi Hu
Most current commercial lithium-ion batteries use organic electrolytes, which have considerable safety issues owing to their toxicity, easy combustion, degradation under high pressure, and corrosiveness. Therefore, safer lithium metal batteries with higher energy density have attracted considerable research attention. Composite solid-state electrolytes combining inorganic ceramics and organic polymers have superior performance; however, challenges such as low ionic conductivity, limited electrochemical windows, and low cycling stability remain to be addressed. Herein, we report a method of graft modification of cotton templates via the metal chelator EDTA (ethylenediaminetetraacetic acid). EDTA adsorbs metal ions from LLZO (Li7La3Zr2O12) precursors to prepare LLZO ceramic fabrics (LLZO CF) with cotton/EDTA as templates. Thus, LLZO ceramic fabric composite solid-state electrolytes (LLZO CF-CSE) with a double-layer cast structure are formed. This LLZO CF-CSE increases the lithium-ion conductivity (3.5 × 10–4 S cm–1 at 50 °C) and widens its electrochemical window (5.2 V). The initial specific capacity of a LiFePO4/Li battery with LLZO CF-CSE reaches 144.5 mAh g–1 at 50 °C, and the capacity remains at 117.6 mAh g–1 after 300 cycles, translating into a capacity retention rate of 99.44% under 1C charge/discharge conditions. Our work presents a method to prepare high-performance, safe, and stable cycling composite solid-state electrolytes.
研究领域:
材料科学
·
电池技术
·
电化学
·
能源存储
✓ 已验证
DOI
高影响因子
Advanced Energy Materials
·
2023
·Vol. 13
·期 16
·2204036
·
IF 27.8
Su Wang,Qifang Sun,Qing Zhang,Chen Li,Chaoran Xu,Yue Ma,Xixi Shi,Hongzhou Zhang,Dawei Song,Lianqi Zhang
The low ionic conductivity and short service life of solid polymer electrolytes (SPEs) limit the application of ambient-temperature polymer lithium metal batteries, which is perhaps a result of the inherent restricted segment movement of the polymer at room temperature. Herein, an ambient-temperature dual-layer solid polymer electrolyte is developed and the related working mechanisms are innovatively investigated. In the strategy, poly(propylene carbonate) (PPC)/succinonitrile (SN) contacts with the cathode while polyethylene oxide (PEO)/Li 7 La 3 Zr 2 O 12 is adopted near the anode. Molecular dynamics simulations demonstrate the formation of solvated sheath-like structure [SN···Li + ], which demonstrates strong interaction with polymers (PPC···[SN···Li + ]/PEO···[SN···Li + ]). Further density functional theory calculations show that these structures, allow rapid transport of Li ions through polymer segments. These results are confirmed with Fourier transform infrared spectroscopy and nuclear magnetic resonance. Therefore, the Li-ion transport mechanism for ambient-temperature SPEs can be reasonably revealed. Remarkably, the binding energy between PPC and SN is stronger than that of PEO, which helps avoid the parasitic reaction between SN and Li. A low overpotential of 55 mV is exhibited for Li/Li symmetrical cells after 1000 h. Notably, a capacity retention of 86.3% is maintained for LiNi 0.6 Co 0.2 Mn 0.2 O 2 /Li cell at 25 °C, implying good application potential in ambient-temperature high voltage lithium metal batteries.
研究领域:
材料科学
·
电化学
·
储能技术
·
高分子物理
·
电池技术
✓ 已验证
DOI
高影响因子
Materials
·
2020
·Vol. 13
·期 3
·560
·
IF 3.057
Yan Ji,Cankai Zhou,Feng Lin,Bingjing Li,Feifan Yang,Huali Zhu,Junfei Duan,Zhaoyong Chen
The garnet Li7La3Zr2O12(LLZO) has been widely investigated because of its high conductivity, wide electrochemical window, and chemical stability with regards to lithium metal. However, the usual preparation process of LLZO requires high-temperature sintering for a long time and a lot of mother powder to compensate for lithium evaporation. In this study submicron Li6.6La3Zr1.6Nb0.4O12(LLZNO) powder―which has a stable cubic phase and high sintering activity―was prepared using the conventional solid-state reaction and the attrition milling process, and Li stoichiometric LLZNO ceramics were obtained by sintering this powder―which is difficult to control under high sintering temperatures and when sintered for a long time―at a relatively low temperature or for a short amount of time. The particle-size distribution, phase structure, microstructure, distribution of elements, total ionic conductivity, relative density, and activation energy of the submicron LLZNO powder and the LLZNO ceramics were tested and analyzed using laser diffraction particle-size analyzer (LD), X-Ray Diffraction (XRD), Scanning Electron Microscope (SEM), Electrochemical Impedance Spectroscopy (EIS), and the Archimedean method. The total ionic conductivity of samples sintered at 1200 °C for 30 min was 5.09 × 10−4S·cm−1, the activation energy was 0.311 eV, and the relative density was 87.3%. When the samples were sintered at 1150 °C for 60 min the total ionic conductivity was 3.49 × 10−4S·cm−1, the activation energy was 0.316 eV, and the relative density was 90.4%. At the same time, quasi-solid-state batteries were assembled with LiMn2O4as the positive electrode and submicron LLZNO powder as the solid-state electrolyte. After 50 cycles, the discharge specific capacity was 105.5 mAh/g and the columbic efficiency was above 95%.Keywords:solid-state electrolyte;submicron powder;garnet;lithium-ion conductivity;solid-state batteries
研究领域:
材料科学
·
电化学
·
能源存储
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Advanced Energy and Sustainability Research
·
2022
·Vol. 3
·期 6
·2100193
·
IF 0
Genxi Yu,Long Pan,Heng Zhang,Yaping Wang,Kai Li,Daming Chen,Jian Chen,Zheng Ming Sun
Composite polymer electrolytes (CPEs) are promising for the realization of solid-state lithium metal batteries (SSLMBs) with high energy density and safety. However, CPEs suffer from insufficient ionic conductivity and low mechanical strength at thin films. Herein this study, a porously nanofibrous Li 7 La 3 Zr 2 O 12 (LLZO)/polyacrylonitrile (PAN) substrate prepared by electrospinning is filled with polyethylene oxide (PEO)/lithium salt (LiTFSI) to form LLZO/PAN/PEO/LiTFSI (LPPL) CPEs. The robust LLZO/PAN nanofibrous membrane mechanically supports the soft PEO/LiTFSI, while the dispersed LLZO together with the PEO/LiTFSI forms a dual Li + conductive pathway. Benefiting from the great synergies between the building blocks, the obtained LPPL CPEs possess a high tensile strength (8.2 MPa) with a thickness of only 20 μm, resulting in a good ionic conductivity. In addition, the LPPL CPEs also exhibit a wide electrochemical window (5.5 V), high thermal stability, and excellent stability with lithium metal. As a result, the LiFePO 4 (LFP)/LPPL/Li SSLMBs show good rate capability and cycling stability (100.5 mA h g −1 @1.0 C after 430 cycles) at 60 °C. In addition, the soft-packaged LFP/LPPL/Li SSLMBs demonstrate high safety under destructive conditions such as bending and cutting. Moreover, the LPPL CPEs are also applicable to the SSLMBs with high-energy LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811) or high-capacity sulfur cathodes.
研究领域:
材料科学
·
电化学
·
能源存储
✓ 已验证
DOI
Materials Today Energy
·
2020
·
IF 5.604
Yirui Lu,Xue Zhang,Chuanjiao Xue,Chengzhou Xin,Ming Li,Ce-wen Nan,Yang Shen
Replacing flammable liquid electrolytes with solid polymer electrolytes is a promising route to improve safety of lithium (Li)-metal batteries. However, developing a suitable high-performance electrolyte with both high ionic conductivity and interface stability against electrodes remains as a challenge. Herein, we design a poly(propylene carbonate) (PPC)/poly(vinylidene fluoride-hexafluoropropylene) [P(VDF-HFP)]–based asymmetric solid electrolyte with a 3D blow-spun Li 7 La 3 Zr 2 O 12 (LLZO) framework. The controllable degradation of PPC facilitates the wettability and stability between the electrolyte and Li metal. The P(VDF-HFP) with good electrochemical stability is used to match with cathode. With the support of the 3D LLZO Li-ion conductor, the electrolyte displays high ionic conductivity (4.9 × 10 −4 S cm −1 at room temperature). The Li||Li symmetric cells assembled with this electrolyte show a long cycling life of more than 2700 h at 100 μA cm −2 . The electrolyte also delivers an excellent cycling performance in solid-state LiFePO 4 ||Li batteries (300 cycles with a capacity retention of 91.3%).
研究领域:
材料科学
·
电化学
·
电池技术
·
固态电解质
✓ 已验证
产品关联
DOI
高影响因子
Journal of Energy Storage
·
2023
·
IF 9.4
Di Zhang,Mengmeng Zhang,Yingsong Yu,Shuting Liang,Yi Hu
Composite electrolyte membranes with 3D nanofiber network structure, which can adjust internal stress to achieve cyclic stability, has been proved to play an important role in the cycle process of lithium metal batteries . However, its application is greatly impeded by the inherent instability interface. Here, we have created an excellent ion transport system through simple interface engineering design. The system weakens the interaction between PEO and Li + via a direct interfacial driving mechanism that establishes the ion bonds (Li-O/Zn-O) between LLZO/ZnO and PEO respectively, thereby achieving stable ion transport. As a result, Li | LPZ-5 CSE | Li battery displays highly stable Li plating/stripping cycling for over 1000 h at 0.1 mA cm −2 . In addition, lithium metal batteries (LMBs) based on LiFePO 4 cathode can stably cycle for 250 cycles with a specific capacity of 151.9 mAh g −1 (50 °C, 0.2 C). This work provides a straightforward and effective strategy that employs the stable ion transfer process at molecular-level to construct a self-supported membrane, which is positive to the development of long-cycle-life LMBs.
研究领域:
材料科学
·
电化学
·
电池技术
·
纳米技术
✓ 已验证
DOI
高影响因子
ACS Applied Energy Materials
·
2022
·
IF 6.959
Zichun Xiao,Ya-Nan Zhou,Xiaowei Wang,Jiawu Cui,Mingyu Yang,Chengyong Shu,Duzhao Han,Jiangqi Zhou,Chengxin Peng,Wei Tang,Yuping Wu
Lithium metal is considered as the ultimate anode for next-generation high energy-density batteries. However, its practical application is still severely hindered by Li dendrite growth as well as infinite volume variation along plating and stripping. Herein, we report a dual-layered, spatially ordered composite skeleton for bottom-up lithium growth by uniformly incorporating Li6.06La3Zr2Al0.2O12 (LLZO) in the upper layer and ZnO in the bottom layer, respectively, in the matrix of carbon fibers (CFs). The well-dispersed ZnO nanoparticles on CFs in the bottom layer function as lithiophilic nucleation sites to homogenize Li nucleation, while LLZO nanoparticles on CFs in the upper layer facilitate Li ion diffusion and distribution for stable lithium growth owing to the high ion conductivity of LLZO. Benefiting from this synergetic effect, the CFs@LLZO//CFs@ZnO composite skeleton can effectively induce Li plating/stripping in a controllable spatially ordered manner, suppressing the volume variation and inhibiting the formation of dendritic lithium. As a result, the symmetric cell using Li|CFs@LLZO//CFs@ZnO||CFs@LLZO//CFs@ZnO|Li presents good cycling stability over 2500 h with a small overpotential of 12 mV at 1 mA cm–2. Notably, under a harsh negative-to-positive N/P ratio of 1, the Li|CFs@LLZO//CFs@ZnO||NCM811 full cell delivers a lifespan of 100 cycles with a capacity fading of only 0.175% per cycle and an average CE of 99.3%.
研究领域:
材料科学
·
电化学
·
能源存储
·
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）