Inorganic Chemistry Frontiers
·
2025
·
IF 6.4
Zesen Gao,Shijie Yang,Yan Yang,Futing Sun,Tianshuo Zhang,Yunluo Wang,Tianrui Zhou,Lang Tao,Hucheng Song,Haijie Chen
Solid-state Li-CO2 batteries possess unique merits, including high environmental friendliness, extremely high energy density, and wide operational temperature range. In this work, we used the garnet-type Li6.4La3Zr1.4Ta0.6O12 (LLZTO) as the solid electrolyte for Li-CO2 batteries. By a simple solid-state reaction under vacuum, LLZTO was tightly composited with organic materials. Detailed analysis confirms that a three-in-one effect was achieved, resulting in additional Li+ migration pathways, improved mechanical properties of the electrolyte, and more active sites for Li2CO3 decomposition. This contributes to accelerated Li+ transport and fast CO2 reaction kinetics. A solid-state Li-CO2 cell was assembled using a Ru@C cathode and an integrated layer of LLZTO@PVDF interfaced with an artificial molten salt. An exceptionally low charging overpotential (below 3.0 V) was achieved, maintaining a charge potential retention rate of over 99%. This work introduces LLZTO as a promising electrolyte for solid-state Li-CO2 batteries, shedding light on the advancement of next-generation Li-CO2 battery technologies.
研究领域:
材料科学
·
电化学
·
能源存储技术
✓ 已验证
产品关联
DOI
高影响因子
Energy & Environmental Materials
·
2022
·Vol. 7
·期 1
·e12498
·
IF 13.443
Zhengyi Lu,Lin Peng,Yi Rong,Enli Wang,Ruhua Shi,Hongxun Yang,Yadong Xu,Ruizhi Yang,Chao Jin
Poly(ethylene oxide) (PEO) and Li 6.75 La 3 Zr 1.75 Ta 0.25 O 12 (LLZTO)-based composite polymer electrolytes (CPEs) are considered one of the most promising solid electrolyte systems. However, agglomeration of LLZTO within PEO and lack of Li + channels result in poor electrochemical properties. Herein, a functional supramolecular combination (CD-TFSI) consisting of active β-cyclodextrin (CD) supramolecular with self-assembled LiTFSI salt is selected as an interface modifier to coat LLZTO fillers. Benefiting from vast H-bonds formed between β-CD and PEO matrix and/or LLZTO, homogeneous dispersion and tight interface contact are obtained. Moreover, 6 Li NMR spectra confirm a new Li + transmission pathway from PEO matrix to LLZTO ceramic then to PEO matrix in the as-prepared PEO/LLZTO@CD-TFSI CPEs due to the typical cavity structure of β-CD. As a proof, the conductivity is increased from 5.3 × 10 −4 S cm −1 to 8.7 × 10 −4 S cm −1 at 60 °C, the Li + transference number is enhanced from 0.38 to 0.48, and the electrochemical stability window is extended to 5.1 V versus Li/Li + . Li‖LiFePO 4 CR2032 coin full cells and pouch cells prove the practical application of the as-prepared PEO/LLZTO@CD-TFSI CPEs. This work offers a new strategy of interface modifying LLZTO fillers with functional supramolecular combination to optimize PEO/LLZTO CPEs for solid lithium batteries.
研究领域:
材料科学
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电化学
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电池技术
✓ 已验证
DOI
高影响因子
Journal of Energy Chemistry
·
2021
·
IF 9.676
Liansheng Li,Yuanfu Deng,Huanhuan Duan,Yunxian Qian,Guohua Chen
Solid electrolytes with desirable properties such as high ionic conductivity, wide electrochemical stable window, and suitable mechanical strength, and stable electrode–electrolyte interfaces on both cathode and anode side are essential for high-voltage all-solid-state lithium batteries (ASSLBs) to achieve excellent cycle stability. In this work, a novel strategy of using LiF and LiNO 3 as synergistic additives to boost the performance of PEO-PVDF/LLZTO-based composite solid electrolytes (CSEs) is developed, which also promotes the assembled high-voltage ASSLBs with dual-interfaces stability characteristic. Specifically, LiF as an inactive additive can increase the electrochemical stability of the CSE under high cut-off voltage, and improve the high-voltage compatibility between cathode and CSE, thus leading to a stable cathode/CSE interface. LiNO 3 as an active additive can lead to an enhanced ionic conductivity of CSE due to the increased free-mobile Li + and ensure a stable CSE/Li interface by forming stable solid electrolyte interphase (SEI) on Li anode surface. Benefiting from the improved performance of CSE and stable dual-interfaces, the assembled NCM622/9[PEO 15 -LiTFSI]-PVDF-15LLZTO-2LiF-3LiNO 3 /Li cell delivers a high rate capacity of 102.1 mAh g −1 at 1.0 C and a high capacity retention of 77.4% after 200 cycles at 0.5 C, which are much higher than those of the ASSLB assembled with additive-free CSE, with only 60.0 mAh g −1 and 52.0%, respectively. Furthermore, novel cycle test modes of resting for 5 h at different charge states after every 5 cycles are designed to investigate the high-voltage compatibility between cathode and CSE, and the results suggest that LiF additive can actually improve the high-voltage compatibility of cathode and CSE. All the obtained results confirm that the strategy of using synergistic additives in CSE is an effective way to achieve high-voltage ASSLBs with dual-interfaces stability.
研究领域:
材料科学
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电化学
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能源存储
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固态电池
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界面化学
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高分子科学
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无机非金属材料
✓ 已验证
DOI
高影响因子
IONICS
·
2024
·Vol. 30
·期 4
·2007-2017
·
IF 2.4
Li Bangxing,Yi Xianlin,Xie Zhenjun,Wu Fei,Kang Xing,Kang Shuai,Hu Xiaolin
Composite solid electrolyte (CSE), especially the composite room temperature solid electrolyte (CRTSE), is emerging as the promising electrolyte for all-solid-state lithium batteries (ASSLB) due to their ability to combine the desirable properties of ceramic and polymer-based electrolytes and the room temperature operation condition. In this paper, the CRTSE with polyethylene oxide (PEO), bis(fluorosulfonyl)imide (LiTFSI), succinonitrile (SN), LLZTO inorganic fillers, and cross-linked ethoxylated trimethylolpropane triacrylate (ETPTA) was proposed. With the help of lithium dendrite suppression via cross-linked microscopic pore structure, enhancement of the ionic conductivity via LLZTO fillers, and wide electrochemical window via SN, the obtained LCSE showed high ionic conductivity (2.12 × 10 −4 S cm −1 ), high Li + transfer number ( t Li + = 0.55), and stable electrochemical window (5.0 V vs Li/Li + ) at room temperature. The Li symmetrical cell with LCSE can cycle over 500 h stably with current density of 0.1 mA cm −2 and 0.5 mA cm −2 at room temperature. The full solid-state LiFePO 4 cell can successfully work over 200 cycles with capacity retention ratio of about 70% at room temperature.
研究领域:
材料科学
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电化学
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能源存储
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固态离子学
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高分子化学
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无机非金属材料
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电池技术
✓ 已验证
DOI
高影响因子
JOURNAL OF POWER SOURCES
·
2023
·
IF 9.2
Tong Duan,Hongwei Cheng,Qiangchao Sun,Yanbo Liu,Wei Nie,Yuehua Chu,Qian Xu,Xionggang Lu
Composite electrolytes (CEs) have a significant potential for achieving excellent safety and energy density in solid-state lithium metal batteries owing to applicable ionic conductivity, easy fabrication, and good electrochemical properties. However, achieving good interfacial compatibility between inorganic fillers and polymer matrix remains challenging. Herein, we design a Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 filler modified with isopropyl tri(dioctyl pyrophosphate) titanate for poly (vinylidene fluoride-co-hexafluoropropylene) electrolyte (denoted as Ti@LLZTO/PVDF-HFP). We reveal the enhanced mechanism of a modified interface on the electrochemical performance by combining experimental results and theoretical calculations. The reinforced interface can facilitate the uniform dispersion of filler in the polymer matrix as well as dissociate more lithium salt, which enables enhanced ionic conductivity (6.86 × 10 −5 S cm −1 at 30 °C). Besides, the Ti@LLZTO can immobilize the anions in lithium salt via hydrogen bonding interactions and the Ti–O chemical bonding. Consequently, the Li||Ti@LLZTO/PVDF-HFP||Li cell shows great cyclability over 1550 h at 0.1 mA cm −2 , 0.1 mAh cm −2 . Moreover, the Li||Ti@LLZTO/PVDF-HFP||LFP cell achieves superior cycling stability at 0.5 C with a high Coulombic efficiency of 98.8 %. This work provides an insightful understanding of designing good interfacial compatibility for advanced composite electrolytes.
研究领域:
材料科学
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电化学
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电池技术
✓ 已验证
DOI
高影响因子
Journal of Materiomics
·
2023
·
IF 9.4
Xiao Chen,Yinda Li,Yunhao Lu,Jian Xie,Cheng Huang,Xiongwen Xu,Jian Tu,Xinbing Zhao,Tiejun Zhu
LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811) is considered as a promising cathode for high-energy-density solid-sate Li metal battery for its high theoretical capacity. However, the high oxidizability and structural instability during charge limit its practical applications. In this work, 1% (in mass) of nanosized Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 (LATP) was coated on NCM811 to enhance its electrochemical stability with a ceramic/polymer composite electrolyte. A robust, ultrathin (11 μm) composite electrolyte film was prepared by combining poly(vinylidene fluoride) (PVDF) with polyethylene oxide (PEO)-Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 (LLZTO). An in-situ polymerization process was used to enhance the interface between the PVDF/PEO-LLZTO (PPL) composite electrolyte and the LATP-coated NCM811 (LATP-NCM811). Coin-type Li|LATP-NCM811 cell with the PPL electrolyte exhibits stable cycling with an 81% capacity retention after 100 cycles at 0.5 C. Pouch-type cell was also fabricated, which can be stably cycled for 70 cycles at 0.5 C/1.0 C (80% retention), and withstand abuse tests of bending, cutting and nail penetration. This work provides an applicable method to fabricate solid-state Li metal batteries with high performance.
研究领域:
材料科学
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电化学
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能源存储
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电池技术
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2024
·
IF 9.4
Hao Xu,Shuai Liu,Zhiang Li,Fan Ding,Jie Liu,Weimin Wang,Kaikai Song,Ting Liu,Lina Hu
Solid polymer electrolytes (SPEs) have been considered the most promising separators for all-solid-state lithium metal batteries (ASSLMBs) due to their ease of processing and low cost. However, the practical applications of SPEs in ASSLMBs are limited by their low ionic conductivities and mechanical strength. Herein, we developed a three-dimensional (3D) interconnected MXene (Ti 3 C 2 T x ) network and Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO) particles synergistically reinforced polyethylene oxide (PEO)-based SPE, where the association of Li + with ether-oxygen in PEO could be significantly weakened through the Lewis acid-base interactions between the electron-absorbing group (Ti–F, −O–) of Ti 3 C 2 T x and Li + . Besides, the TFSI − in lithium salts could be immobilized by hydrogen bonds from the Ti–OH of Ti 3 C 2 T x . The 3D interconnected Ti 3 C 2 T x network not only alleviated the agglomeration of inorganic fillers (LLZTO), but also improved the mechanical strength of composite solid electrolyte (CSE). Consequently, the assembled Li||CSE||Li symmetric battery showed excellent cycling stability at 35 ℃ (stable cycling over 3000 h at 0.1 mA cm −2 , 0.1 mAh cm −2 ) and −2 ℃ (stable cycling over 2500 h at 0.05 mA cm −2 , 0.05 mAh cm −2 ). Impressively, the LiFePO 4 ||CSE||Li battery showed a high discharge capacity of 145.3 mAh/g at 0.3 C after 300 cycles at 35 ℃. This rational structural design provided a new strategy for the preparation of high-performance solid-state electrolytes for lithium metal batteries.
研究领域:
材料科学
·
电化学
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能源存储
·
纳米技术
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF SOLID STATE ELECTROCHEMISTRY
·
2026
·
IF 3.1
Hao Ruixin,Liang Jinjiang,Gao Tianyi,Yuan Qiong,Shi Hongsheng,Liu Wei,Yu Yi
Garnet-type Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO) is a promising solid electrolyte, but Li dendrite penetration remains a critical challenge. Since pores and grain boundaries are often regarded as preferential sites for Li deposition, the local structure and chemistry of these regions were investigated. Zr enrichment was observed near pores and grain boundaries, and focused ion beam (FIB)-transmission electron microscopy (TEM) analysis identified the grain boundary impurity phase as Li 2 ZrO 3 , indicating that local chemical heterogeneity is closely associated with failure-sensitive regions in LLZTO. To trace the origin of this impurity phase, the precursor was further examined. La 2 O 3 was found to undergo hydration during storage, forming La(OH) 3 and introducing an effective stoichiometric deviation during synthesis, which promotes Li 2 ZrO 3 formation. After pre-annealing purification of La 2 O 3 , the impurity phase was significantly suppressed, while the relative density and critical current density (CCD) of LLZTO were both markedly improved. These results demonstrate that precursor purification is an effective strategy for improving the phase purity, relative density, and current tolerance of LLZTO. Graphical abstract Online Figure: La 2 O 3 precursor purification improves LLZTO relative density and current tolerance. Pre-annealing commercial La 2 O 3 at 900 °C for 10 h reduces hydroxide/oxycarbonate-related impurities, suppresses Li 2 ZrO 3 formation, and yields denser LLZTO ceramics with enhanced CCD.
✓ 已验证
DOI
高影响因子
JOURNAL OF THE EUROPEAN CERAMIC SOCIETY
·
2014
·
IF 2.307
Yaoyu Ren,Hui Deng,Rujun Chen,Yang Shen,Yuanhua Lin,Ce-Wen Nan
Cubic garnet-type Al-contained Li 6.75 La 3 Zr 1.75 Ta 0.25 O 12 (Al-LLZTO) ceramics were prepared by conventional solid-state reaction using either Li 2 CO 3 or LiOH·H 2 O as Li source. The effects of Li source on the lithium ionic conductivity of Al-LLZTO ceramics were systematically investigated by comparing the synthesis processes and characteristics of the mother powders and the microstructures of the sintered pellets made with different Li sources. Different calcination processes of the raw materials mixtures with different Li sources are revealed by thermogravimetry-differential scanning calorimetry investigation. The mother powder derived from LiOH·H 2 O is of higher sintering activity than those made from Li 2 CO 3 at the same calcination temperature. For the LiOH·H 2 O-derived pellets, higher relative density and enhanced lithium-ion conductivity is achieved at a much lower sintering temperature of 1100 °C as compared with Li 2 CO 3 -derived pellets. The highest conductivity obtained at room temperature is 9.28 × 10 −4 S cm −1 , which is the highest value reported to date for the same Ta doping level.
研究领域:
材料科学
·
固态电池
✓ 已验证
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2023
·
IF 9.5
Yifan Zhou,Aosong Gao,Mingqiu Duan,Xiaoqi Zhang,Muzi Yang,Li Gong,Jian Chen,Shuqin Song,Fangyan Xie,Hao Jia,Yi Wang
Garnet-type Li6.4La3Zr1.4Ta0.6O12 (LLZTO) is a highly promising solid-state lithium metal battery electrolyte due to its exceptional ionic conductivity and electrochemical stability. However, when exposed to air, a passivation layer can be spontaneously formed on the garnet-type electrolyte, deteriorating its wettability with metallic lithium (Li) and impeding the lithium ion transfer at the Li–garnet electrolyte interface. The passivation layer is considered a critical issue for garnet-type solid electrolytes. Despite intensive research, the formation mechanism of the passivation film remains poorly understood. The key to elucidating the formation mechanism is to obtain a pristine garnet electrolyte surface and study how the pristine garnet electrolyte interacts with air. In this study, different passivation layer removal pretreatments were performed to expose pristine garnet electrolytes, and their impacts on the samples were systematically studied. The results reveal the overlooked negative impacts of vacuum annealing and acid treatment on LLZTO, which are indicated by the severe loss of Li and O and the formation of additional Li-depleted metal oxides. It was confirmed that argon annealing is the only viable approach to remove the passivation layer without introducing concomitant contaminations to LLZTO. Based on this method, we directly evidenced the formation of LiOH on LLZTO under rarefied air using quasi-in situ X-ray photoelectron spectroscopy. It was confirmed that the loss of Li and O ions, rather than Li+/H+ exchange, drives the formation of LiOH in the passivation layer. These results not only provide a better understanding of the surface and interface chemistry of LLZTO but also reveal a reliable surface treatment for the LLZTO sample.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
INTERNATIONAL JOURNAL OF ENERGY RESEARCH
·
2022
·Vol. 46
·期 6
·7686-7693
·
IF 4.672
Weibo Shi,Jiayao Wang,Xinyi Zhang,Qingli Wang,Wenwen Deng
Summary Organic electrode materials have attracted extensive attention because of their high flexibility and sustainability, but their application was limited by the disadvantage of dissolution in conventional electrolyte. Here, we designed an all solid-state lithium-ion battery (ASSLIB) with 11,11,12,12-tetracyano-9,10-anthraquinonedimethane (TCAQ) as the cathode and lithium metal as the anode. The solid electrolyte consisted of Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO)/polyoxyethylene(PEO) and lithium bis(trifluoromethanesulfonimide) (LiTFSI) salt. The Li||TCAQ ASSLIB delivered a discharge specific capacity of 83 mAh g −1 at a current density of 17 mA g −1 with a capacity retention of 72.2% after 100 cycles. Our research provided a new organic cathode material for high-performance ASSLIBs.
研究领域:
材料科学
·
能源存储
✓ 已验证
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2025
·
IF 6.3
Zhiang Li,Shuai Liu,Hao Xu,Fan Ding,Weimin Wang,Kaikai Song,Ting Liu,Lina Hu
Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO) is widely used in polyethylene oxide (PEO) based solid electrolytes preparation due to its high ionic conductivity, electrochemical stability towards lithium and excellent mechanical properties. However, agglomeration of LLZTO and the inert interfacial layer for Li + transport between LLZTO and PEO limit its application. Herein, we systematically study the effect of different contents of 1-methyl-1-propylpiperidinium bis(trifluoromethylsulfonyl)imide (denoted as PP13-TFSI) ionic liquid on PEO/LLZTO composite solid electrolytes (CSEs). PP13-TFSI, which provides a new pathway for Li + transport and promotes the uniform dispersion of LLZTO. By adjusting the proportion of PP13-TFSI reasonably, the agglomeration of LLZTO is weakened, the crystallinity of PEO is reduced, and the growth of lithium dendrites is also inhibited. Therefore, the CSEs with high ionic conductivity (2.03 × 10 −4 S cm −1 , 30 ℃) enhanced by PP13-TFSI. Li||Li symmetric batteries exhibit stable cycling up to 6000 h at 60 °C, and can cycle stably for up to 3000 h at 28 °C. LiFePO 4 ||Li full batteries exhibit high-capacity retention rate (≈ 90.5 %) after 500 cycles at 1 C. This work not only systematically study the effects of different contents of PP13-TFSI on CSEs, but also provide a simple composite solid electrolyte strategy.
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）