JOURNAL OF THE AMERICAN CERAMIC SOCIETY
·
2022
·Vol. 106
·期 1
·274-284
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IF 4.186
Hongpeng Zheng,Guoyao Li,Hezhou Liu,Yongmin Wu,Huanan Duan
A Ta-doped Li 7 La 3 Zr 2 O 12 (LLZTO) solid electrolyte is a promising candidate for all-solid-state lithium battery due to its high ionic conductivity and stability against lithium metal. In this work, physicochemical properties of both dry- and wet-milled LLZTO particles were investigated. Based on X-ray diffraction, Fourier transform–infrared, thermogravimetric analysis, and scanning electron microscopy results, it was confirmed that highly reactive LLZTO powder prepared in dry milling conditions exhibited faster size reduction, rougher surface morphology, fewer surface impurities, and less agglomerated particles, in contrast to those in wet milling conditions. Sintering these dry-milled powders at 1320°C for 10 min in the air via solid-state reaction produced dense ceramic pellets with a relative density of 97.4%. The room-temperature ionic conductivity for LLZTO pellet via the dry milling was determined to be 6.94 × 10 −4 S cm −1 . Li–sulfur batteries based on the pellets showed an initial discharge capacity of 1301 mA h g −1 and a coulombic efficiency of 99.82% when cycled at room temperature. The effect of the milled powder on the sintered pellets was discussed in terms of boundary mobility, pore mobility, and morphology.
研究领域:
材料科学
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电化学
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DOI
高影响因子
ChemistrySelect
·
2024
·Vol. 9
·期 14
·e202400792
·
IF 1.9
Zexian Xu,Wen Zhu,Wenbo Liu,Ken Chen,Yueyang Wu,Jiawei Zhu,Yufei Yang,Wenfang Li,Kang Li
Graphical This paper presents a straightforward preparation method for LLZTO electrolyte tablets with minimal surface passivation layer content. Through experimentation, the optimal conditions for process parameters including mixed powder content, PVA content, and cold pressing pressure are identified. Under these optimized conditions, the LLZTO electrolyte tablets demonstrate a notable enhancement in quality and a reduction in interface resistance, leading to improved electrochemical performance. The garnet-type Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO) is a widely studied solid-state electrolytes (SSEs) due to its high ionic conductivity and electrochemical stability. However, the conventional preparation process of LLZTO electrolyte tablets has encountered several issues such as powder embedment in the mold gaps and inadequate bonding between powders, leading to fragile electrolyte tablets that are prone to cracking. In this study, the effects of LLZTO electrolyte tablet pressing process parameters, including mixed powder content, polyvinyl alcohol (PVA) content and cold pressing pressure, on the electrochemical properties of button cells were investigated. The results indicated that the produced solid-state electrolyte tablets with high quality, low interfacial resistance and low surface passivation layer (Li 2 CO 3 ) content was obtained by using 0.8 g of mixed powder content, 0.7 g of PVA content and 20Mpa pressure. The interface resistance decreased from 2927.1 Ω to 1069.7 Ω under these conditions. Additionally, the Li symmetric cell treated with adhesive exhibited stable cycling for over 400 hours at 25 °C under a current density of 0.1 mA ⋅ cm −2 .
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
MOLECULES
·
2024
·Vol. 29
·期 18
·4452
·
IF 4.2
Xuehan Wang,Kaiqi Zhang,Huilin Shen,Hao Zhang,Hongyan Yao,Zheng Chen,Zhenhua Jiang
Solid-state electrolytes (SSEs), particularly garnet-type Li6.4La3Zr1.4Ta0.6O12(LLZTO), offer high stability and a wide electrochemical window. However, their grain boundaries limit ionic conductivity, necessitating high-temperature sintering for improved performance. Yet, this process results in brittle electrolytes prone to fracture during manufacturing. To address these difficulties, solvent-free solid-state electrolytes with a polyacrylonitrile (PAN) coating on LLZTO particles are reported in this work. Most notably, the PAN-coated LLZTO (PAN@LLZTO) electrolyte demonstrates self-supporting characteristics, eliminating the need for high-temperature sintering. Importantly, the homogeneous polymeric PAN coating, synthesized via the described method, facilitates efficient Li+transport between LLZTO particles. This electrolyte not only achieves an ionic conductivity of up to 2.11 × 10−3S cm−1but also exhibits excellent interfacial compatibility with lithium. Furthermore, a lithium metal battery incorporating 3% PAN@LLZTO-3%PTFE as the solid-state electrolyte and LiFePO4as the cathode demonstrates a remarkable specific discharge capacity of 169 mAh g−1at 0.1 °C. The strategy of organic polymer-coated LLZTO provides the possibility of a green manufacturing process for preparing room-temperature sinter-free solid-state electrolytes, which shows significant cost-effectiveness.
研究领域:
材料科学
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能源技术
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产品关联
DOI
PubMed
高影响因子
Batteries-Basel
·
2023
·Vol. 9
·期 5
·257
·
IF 4
Xinjie Yu,Pengbo Zhai,Ning Zhao,Xiangxin Guo
Solid polymer electrolytes (SPEs) are seen as the key component in the development of solid-state lithium batteries (SSLBs) by virtue of their good processability and flexibility. However, poor mechanical strength, low room-temperature lithium-ion (Li-ion) conductivity and unsatisfactory interfacial compatibility with electrodes limit their practical application. In this work, a composite electrolyte consisting of polyvinylidene fluoride and polyvinylidene carbonate with a Li6.4La3Zr1.4Ta0.6O12(LLZTO) active filler (PFPC: LLZTO-SPE) is reported to achieve excellent ionic conductivity (4.25 × 10−4S cm−1at 30 °C), a wide electrochemical window (>4.6 V), a high Li-ion transference number (tLi+= 0.49) and good interfacial compatibility with the electrode. Incorporating LLZTO as an active filler not only increases the ionic conductivity of the electrolyte, but also homogenizes Li-ion flux and stabilizes the electrode/electrolyte interface, thereby preventing lithium dendrites from piercing the electrolyte. As a result, Li/Li symmetrical cells using PFPC: LLZTO-SPEs deliver more than 800 h of cyclability at 0.1 mA cm−2and a high critical current density (CCD) of 2.6 mA cm−2. The assembled Li/PFPC: LLZTO/LFP SSLBs achieve 87% capacity retention after 150 cycles at 0.2 C and 89% capacity retention for 100 cycles at 0.5 C. This work inspires new insights into designing high-performance SPEs.Keywords:LLZTO;in-situ polymerization;solid polymer electrolytes;solid-state lithium batteries
研究领域:
材料科学
·
电化学
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DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2020
·
IF 7.489
Qian Zhang,Kun Liu,Kang Liu,Junpeng Li,Chunjie Ma,Liang Zhou,Yaping Du
Improving the safety and performance of lithium ion batteries (LIB) sparked the idea of using a solid electrolyte to construct all-solid-state ones. In this study, a composite solid polymer electrolyte based on Li 6.40 La 3 Zr 1.40 Ta 0.60 O 12 (LLZTO) nanoparticles and a random copolymer , poly(vinyl pyrrolidone- co -poly(oligo(ethylene oxide) methyl ether methacrylate) (PPO), was successfully prepared and investigated in detail. The copolymer PPO is mixed with LiTFSI and LLZTO at different ratios and the Li conductivity and other electrochemical properties were studied. The copolymer matrix shows the highest ionic conductivity , 2.43 × 10 −5 S/cm at 60 °C, at the content of 20 wt% LiTFSI, the highest lithium ion transference number is determined to be 0.33 at room temperature , and the electrochemical stability reaches 4.3 V vs. Li + /Li. Interestingly, when compounded with LLZTO nanoparticles , the ionic conductivity is not improved much. For example, the highest ionic conductivity increases a little to 2.74 × 10 −5 S/cm at 60 °C when 5 wt% LLZTO is added. However, a large increase in electrochemical stability to 5.0 V is obtained for the sample of PPO-20%-10LLZTO. Both PPO and the composite electrolyte show good cycling performance during a plating/stripping experiment at a current density of 0.01 mA/cm 2 . The limited improvement of properties is possibly due to the poor interface contact between PPO and LLZTO nanoparticles . The result may shed light on the complexity of fabricating composite electrolytes using mixtures of polymer and lithium-conducting ceramics.
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
·
2022
·
IF 9.965
Lin Peng,Zhengyi Lu,Lin Zhong,Jiejie Jian,Yi Rong,Ruizhi Yang,Yadong Xu,Chao Jin
Improving conductivity and optimizing interface contact are two primary targets to promote the development of solid-state electrolytes. Herein, maleic acid (MA) is introduced into normal PVDF-LLZTO(Li 6.75 La 3 Zr 1.75 Ta 0.25 O 12 ) based composite polymer-ceramic electrolytes (CPEs). Benefiting the self-polymerization of MA, a core–shell structure is spontaneously formed with LLZTO as core and MA nano-film as shell, the MA shell builds a bridge to link LLZTO and PVDF. In addition, carboxyl groups in MA provide extra channels for Li + transmission. As a proof, the optimized 25MA-75PVDF-LLZTO CPEs demonstrates an enhanced conductivity as high as 1.15 × 10 -3 S cm −1 at 30 °C, an extended electrochemical window up to < 5.0 V, a raised Li + transfer number of 0.596, and an improved compatibility with Li metal anode. The as-prepared Li‖25MA-75PVDF-LLZTO CPEs‖LiFePO 4 full cell delivers an initial specific discharge capacity of 170.5 mAh g −1 at 0.2C, a high rate capability up to 1.0C with 138 mAh g −1 and an excellent long-term cycling stability of over 180cycles without capacity attenuation. The work provides a new strategy to optimize solid state lithium batteries by introducing unsaturated small organic molecules.
研究领域:
材料科学
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电化学
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能源存储
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Nanoscale
·
2023
·Vol. 15
·期 31
·12961-12971
·
IF 6.7
Shuo Wang,Mengke Li,Gaojie Yan,Zhipeng Yang,Yuchao Guo,Xi Sun,Yue Wang,Yi Feng,Huili Ding,Xiaojie Zhang
Lithium–sulfur (Li–S) batteries are severely restricted for practical application due to the polysulfide shuttle effect, Li dendrites and thermal runaway. The use of PEO-based polymer composite electrolytes (PCEs) as an alternative strategy suffers from limited lithium-ion conductivity with deficient long-range transfer route. Herein, Li6.4La3Zr1.4Ta0.6O12 (LLZTO) nanoparticles modified with an in situ-synthesized zwitterionic covalent organic framework layer (denoted as LLZTO@HUT4) were introduced into PEO-based PCEs. Zwitterionic HUT4 modified the lithiophobic LiOH/Li2CO3 layer on the surface of LLZTO nanoparticles, which could notably promote Li+ ion transport for superior electrochemical performance of PCEs. Additionally, the intermediate layer HUT4 located between LLZTO and PEO could further improve the mechanical properties of electrolytes due to the enhanced inorganic/organic interface compatibility and intermolecular interaction. As a result, the obtained LLZTO@HUT4-15%/PEO electrolyte exhibited a competent ionic conductivity of 0.73 mS cm−1 with a Li+ transference number of up to 0.74 at 60 °C. The assembled S@CNT|LLZTO@HUT4-15%/PEO|Li coin cell delivered a considerable initial discharge capacity of 1018 mA h g−1 at 0.2 C, with approximately 92.1% capacity retention after 100 cycles, elucidating an obviously suppressed shuttle effect.
研究领域:
材料科学
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电化学
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能源存储
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Journal of Physical Chemistry C
·
2024
·
IF 3.3
Daoxi Wang,Haiting Shi,Shuaitong Liang,Ruiqi Shao,Shuo Wang,Wenhui Cui,Wei Wang,Zhiwei Xu
Garnet-type lithium–lanthanum–zirconium–oxygen (LLZO) oxide solid-state electrolytes (SSEs) have become one of the most promising SSEs for future deep space exploration because of their excellent energy density and mechanical strength. However, the effects of high-energy irradiation on LLZO-type oxide SSEs in the space domain are still unknown. To this end, the Ta-doped lithium–lanthanum–zirconium–tantalum–oxygen (LLZTO) SSE with high ionic conductivity at room temperature was prepared by a solid-phase reaction method, and the γ-irradiation effects on the cell structure and performance (ionic conductivity, hardness, and elastic modulus) of the LLZTO SSE were investigated in detail. The results show that the γ-irradiated electrolyte did not produce other heterogeneous phases, but the lattice spacing was subsequently reduced, which would be detrimental to the ionic transport in the lattice. In addition, the neutron diffraction data also illustrate that irradiation does not change the cell structure of the LLZTO SSE, but the decrease in Li1 occupancy at the tetrahedral-24d site will have a detrimental causal effect on ion transport. The impedance test at room temperature further demonstrated that after γ-irradiation, the total resistance of LLZTO becomes larger and the ionic conductivity of the corresponding irradiated samples tends to decrease. Fortunately, the ionic conductivity retention of irradiated samples at low temperatures was higher than that of unirradiated samples (48.45 > 29.9%). The test results of nanoindentation indicate that the irradiated samples have high mechanical properties at a low load (2 mN), which can effectively prevent lithium dendrite penetration, and this is supported by the low electronic conductivity of the irradiated samples at room temperature. The first use of γ-irradiation to probe its effect on the cell structure and properties (electrochemical and mechanical) of the LLZTO oxide SSE has important research implications for the development of oxide SSEs for aerospace applications.
研究领域:
材料科学
·
航天工程
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DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Yingxin Zhang,Xiaohui Yu,Xiaoxiao Li,Jianguo Ren,Peng He,Chao Zhang,Cuiqing Teng,Yue-E Miao,Tianxi Liu
Flexible composite solid electrolytes (CSEs) show great potentials in high-energy all-solid-state lithium metal batteries owing to their easy fabrication, good electrochemical properties, and high safety. However, it remains challenging to achieve good interfacial compatibility between the inorganic fillers and polymer matrix, which affects the lithium-ion transport efficiency and electrochemical performances of CSEs. Herein, a dynamic crosslinked network with Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO) nanoparticles as the cross-linking point is proposed for fabrication of a rapidly self-healing flexible CSE, which is signed as SHENE. The amino groups in the 3-aminopropyltriethoxysilane modified LLZTO behave as the bridge sites to react with the copolymer of 2-hydroxyethyl methacrylate- g -4-formylbenzoic acid and poly (ethylene glycol) methoxy acrylate to form imine bonds, which effectively connect the organic/inorganic interface. Compared to the traditional physical contact, the covalent imine bonds can not only enhance the interaction between the two phases, but also improve the dispersion of the ceramic LLZTO nanoparticles. Additionally, the dynamic reversibility of imine bonds allows for enhanced mechanical strength and self-repairing capabilities of SHENE. Therefore, a Li||Li symmetrical cell assembled with SHENE can stably cycle for 5000 h at 0.05 mA cm − 2 and 25 °C. The corresponding Li/SHENE/LiFePO 4 full battery also exhibits good rate performance under various C-rates. Additionally, the Li/SHENE/LFP pouch cell exhibits superior safety under various abuse conditions. Therefore, this work provides new ideas for the uniform dispersion of ceramic nanoparticles in CSEs by the facile design of forming dynamic crosslinked networks.
研究领域:
材料科学
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电化学
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能源存储
✓ 已验证
产品关联
DOI
高影响因子
Journal of Energy Storage
·
2024
·
IF 8.9
Rui-You Jian,Chia-Chen Li
This research investigates challenges associated with gelation in Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO) slurry preparation for solid-state Li-ion batteries. Gelation arises from a cross-linking reaction between the sintering aid , boron oxide (B 2 O 3 ), and the poly(vinyl butyral) (PVB) binder. With increasing B 2 O 3 content, LLZTO slurry viscosity dramatically rises, resulting in unsuitable solid-like behavior for tape casting. The alkaline nature of LLZTO powder intensifies cross-linking, a phenomenon confirmed through boron-11 nuclear magnetic resonance spectroscopy. To mitigate gelation, diol compounds, such as ethylene glycol, are introduced to deactivate B 2 O 3 -PVB cross-linking, with selection guided by support from density functional theory-based simulations.
研究领域:
材料科学
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化学
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固态电池
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电化学
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Energy Materials
·
2021
·
IF 6.024
Rong-Ao Tong,Linhui Chen,Bingbing Fan,Gang Shao,Ruiping Liu,Chang-An Wang
All solid-state lithium metal batteries are viewed as a potential next-generation energy storage technology due to their high energy density and better safety performance. The study on solid-state electrolytes (SSE) is of crucial importance for the development of technology in this field. Here, we develop a solvent-free preparation and matrix modification process for all-solid-state composite electrolytes (CSEs) based on the blended PVDF-HFP/PEO polymer matrix, and systematically study the effects of the solvent-free process on their properties. The results show that the solvent-free PVDF-HFP/PEO/10 wt % LLZTO solid-state electrolytes (1:1 mass ratio blended polymer matrix) combine the electrochemical and mechanical advantages of both polymers, thus-prepared electrolytes perform excellent tensile strength and ductility (over 500% strain for polymer matrix as well as 170% strain and 4.78 MPa strength for CSEs), and the ionic conductivity can reach ∼6.2 × 10–4 S·cm–1 at 80 °C. At the same time, the electrochemical stability and cycle stability of the electrolytes are enhanced due to the optimized process. The discoloration reaction of PVDF-HFP in composite electrolytes is further studied in this work as well. In addition to excellent performance, the simple process based on the solvent-free method also lays the foundation for scale-up production.
研究领域:
材料科学
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电化学
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能源存储技术
✓ 已验证
DOI
高影响因子
IONICS
·
2021
·Vol. 27
·期 10
·4127-4134
·
IF 2.817
Guan Dichang,Huang Yong,He Meimei,Hu Guorong,Peng Zhongdong,Cao Yanbing,Du Ke
All-solid-state Li-ion batteries (ASSLBs) are promising systems to power electronic devices and electric vehicles for their high-energy density and safety. PEO-based composite electrolytes containing lithium salts and various fillers have been regarded as the most attractive solid electrolytes for ASSLBs due to their high interfacial compatibility with electrodes, high mechanical flexibility, and easy fabrication. For PEO/lithium salt/ceramic composite electrolytes, both “ceramic-in-polymer” and “polymer in ceramic” can be applied to solid-state batteries. “Ceramic-in-polymer” can provide high ionic conductivity but narrow electrochemical window; “polymer in ceramic” can provide wide electrochemical window but low ionic conductivity. In order to combine the high conductivity of “ceramic in polymer” with the wide electrochemical window of “polymer in ceramic,” we designed multilayer PEO/ Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO) composite electrolytes with low content of LLZTO (10wt %) in the inside layer and high content of LLZTO (40wt %) in the surface layer (PCEs-40–10-40) by a simple solution casting method. The PCEs-40–10-40 showed high ionic conductivity(4.61 × 10 –4 \({\mathrm{S}\cdot \mathrm{cm}}^{-1}\) ) and a wide electrochemical window(> 5.1 V) at 60 ℃. Compared with monolayer composite electrolytes, solid-state LiFePO 4 |Li batteries with multilayer composite electrolytes showed much better cycling stability (capacity retention of 98.8% after 200 cycles) at 0.5C and 60 ℃. This work shall give practical insights for the applications of PEO-based composite electrolytes.
研究领域:
材料科学
·
电化学
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储能技术
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纳米技术
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高分子科学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）