Journal of Energy Chemistry
·
2023
·
IF 13.1
Xiaoye Liu,Xiangkun Kong,Wenyi Xiang,Yining Jiang,Bingqinq Xiong,Weiwei Ping,Changrong Xia,Daoming Huan,Chengwei Wang
Garnet-type Li 7 La 3 Zr 2 O 12 (LLZO) has high ionic conductivity and good compatibility with lithium metal. High-temperature processing has been proven an effective method to decrease the interface resistance of cathode|LLZO. However, its application is still hindered by the interlayer co-diffusion with the cathode and high sintering temperature (>1200 °C). In this work, a new garnet-type composite solid-state electrolyte (SSE) Li 6.54 La 2.96 Ba 0.04 Zr 1.5 Nb 0.5 O 12 -LiCoO 2 (LLBZNO-LCO) is firstly proposed to improve the chemical stability and electrochemical properties of garnet with high-temperature processing. Small doses of LCO (3%) can significantly decrease the LCO|SSE interface resistance from 121.2 to 10.1 Ω cm 2 , while the sintering temperature of garnet-type LLBZNO decreases from 1230 to 1000 °C. The all-solid-state battery based on the sintered LLBZNO-LCO SSE exhibits excellent cycling stability. Our approach achieves an enhanced LCO|SSE interface and an improved sintering activity of garnet SSE, which provides a new strategy for optimizing the comprehensive performance of garnet SSE.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
Journal of Energy Storage
·
2023
·
IF 9.4
Hongying Hou,Baoxiang Huang,Xiaohua Yu,Jian Lan,Sen Ming,Ju Rong,Xianxi Liu,Fangshu Chen
Organic/inorganic composite solid electrolyte has been a hot topic due to combining the merits of both components. Herein, a series of organic/inorganic composite solid electrolytes were prepared by casting method, in which polyvinylidene fluoride (PVDF) was modified with amphoteric sulfonate betaine (SB) and combined with the different contents (0 %, 10 %, 20 % and 30 %) of Li 7 La 3 Zr 2 O 12 (LLZO) and 20 % bis(trifluoromethane) sulphonyl (LiTFSI). The resultant samples were marked as 0%LLZO/SB-PVDF/LiTFSI, 10%LLZO/SB-PVDF/LiTFSI, 20%LLZO/SB-PVDF/LiTFSI and 30%LLZO/SB-PVDF/LiTFSI, respectively. As expected, composite solid electrolyte exhibited the desirable overall performances. Especially, 20%LLZO/SB-PVDF/LiTFSI membrane exhibited high ionic conductivity (1.73 × 10 −4 S/cm), wide electrochemical window (5.22 V), high Li + transference number (t Li + = 0.67) and high mechanical property, probably due to the synergistic effect of LLZO and amphoteric SB modification. Specifically, the amphoteric SB promoted the dissociation of LiTFSI and endowed PVDF matrix with the ionic conductivity, while LLZO facilitated high ionic conductivity, t Li + and mechanical property. Resultantly, Li//LiFePO 4 cell with 20%LLZO/SB-PVDF/LiTFSI membrane delivered 129.5 mAh/g at 1.0C for 200 cycles and 94.0 % capacity retention, demonstrating high application feasibility in the solid-state lithium ion battery . Furthermore, density functional theory (DFT) calculations showed that the binding energy of the amphoteric SB-Li + (C 11 H 21 NO 5 S-Li + ) system was 80.93 kcal/mol, higher than 75.55 kcal/mol of the LiTFSI system, indicating that the amphoteric SB could indeed promote the dissociation of LiTFSI.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
Functional Materials Letters
·
2025
·
IF 1.1
Jie Zhao,Ming Guan,Can Cui,Saifang Huang
To enhance the room-temperature lithium-ion conductivity and interfacial stability of Li 7 La 3 Zr 2 O 1 2 (LLZO) solid-state electrolytes, a co-doping strategy with Ga 3 + and Nb 5 + was employed. By systematically optimizing the sintering protocol — including heating rate, temperature, and dwell time — highly dense and phase-pure cubic-phase LLZO ceramics were successfully synthesized. The co-doping approach effectively stabilized the cubic garnet structure and regulated the lattice framework to facilitate Li + transport pathways. Under optimized conditions, compared to undoped LLZO (0.31 mS cm − 1 , 0.362 eV), the co-doped ceramic exhibited significantly enhanced total ionic conductivity (0.81 mS cm − 1 ) and reduced activation energy (0.207 eV), confirming the superior transport performance enabled by the co-doping strategy. Furthermore, the electrolyte showed good wettability and interfacial compatibility with metallic lithium, enabling stable cycling performance in symmetric Li∥Ga/Nb-LLZO∥Li cells over short durations. These results confirm the practical potential of the co-doped LLZO electrolyte in all-solid-state lithium batteries. This study provides a viable pathway for the material design and processing of high-performance LLZO-based solid electrolytes.
研究领域:
材料科学
·
固体离子学
·
储能技术
·
陶瓷工艺
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2018
·
IF 8.097
Yao Lu,Xiaoyi Meng,José A. Alonso,María T. Fernández-Díaz,Chunwen Sun
Solid-state lithium batteries (SSLBs) are promising technologies with great potential in improving safety and energy density, compared with the traditional liquid based lithium ion batteries. However, the bottleneck of SSLBs lies in the issues of poor interface contact and low electrolyte conductivity. In this work, the crystal structure of garnet-type Li6.25Ga0.25La3Zr2O12 (LGLZO) was engineered more rigidly with subdued atoms displacement by fluorine doping and thus smoother and faster lithium ion diffusion paths are formed. The ionic conductivity of garnet-type electrolyte is significantly increased from 5.43 × 10–4 S/cm to 1.28 × 10–3 S/cm at 25 °C and the activation energy is reduced from 0.33 to 0.28 eV. The solid-state symmetric cell consisting of F doped Li6.25Ga0.25La3Zr2O12 electrolyte and lithium metal has lower resistance and displays stable lithium plating/stripping for over 650 h with smaller overpotentials than those on LGLZO electrolyte. Moreover, the all solid-state lithium battery with F-LGLZO electrolyte and LiFePO4 composite electrode exhibits an improved rate capability, which can still keep 132.9 mAh/g at 1 C. Fluorine substitution in garnet-type electrolyte opens new avenues to design new solid-state electrolytes for practical applications of SSLBs.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
PubMed
高影响因子
JOURNAL OF POWER SOURCES
·
2024
·
IF 8.1
Yu Han,Yonghui Chen,Xueting Pei,Maolin Zhang,Dongyan Zhang,Zhimin Li,Guozhong Cao,Yuan Wang
The development of Li 7 La 3 Zr 2 O 12 solid state electrolyte is retarded by its low ionic conductivity and surface passivation. A few studies suggest those two hurdles can be solved together. Capitalizing on similar physical and chemical properties of Hf 4+ and Zr 4+ , Hf 4+ doped Li 7 La 3 Zr 2- x Hf x O 12 ( x = 0.3, 0.4, 0.5, and 0.6) is prepared and the influence of Hf 4+ on the structure and electrochemical performance of LLZO is investigated systematically. LLZO with Hf 4+ doping is transformed into cubic phase, and also reduces the secondary reaction between H 2 O, CO 2 and LLZO, while increasing the ionic conductivity of the electrolyte to 2.01 × 10 −4 S cm −1 . The electrochemical window between the LLZHO and lithium metal reaches 4.7 V, which is 0.8 V higher than that of LLZO. The specific capacity of the 1st discharge of the all-solid-state batteries assembled with the LiFePO 4 cathode at 0.1C reaches 110.00 mAh·g −1 . The coulombic efficiency reaches 99.18 % after 100 cycles, and the cycle retention rate is 65.82 %.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
SOLID STATE IONICS
·
2025
·
IF 3.3
Shihao Fu,Pingmei Li,Shiyu Yu,Yang Hu,Yibo Liu,Daming Chen,Yaqing Wei,Yuanxun Li,Yong Chen
The garnet-type Li 7 La 3 Zr 2 O 12 (LLZO) has garnered significant attention due to its superior thermal stability and broad electrochemical window. However, LLZO exhibits instability at room temperature and readily transforms from a cubic phase ( c -LLZO) to a tetragonal phase ( t -LLZO), resulting in issues such as low ionic conductivity. Herein, the effect of Ga doping on LLZO is investigated. Combined with SEM, activation energy, ionic conductivity and XRD refinement, the results demonstrate that Li 7-3x Ga x La 3 Zr 2 O 12 exhibits better properties when x = 0.25. Solid-state nuclear magnetic resonance (SSNMR) showed that Ga0.25-LLZO was favorable for promoting Li + transport. Moreover, Li| [email protected] |Li symmetric cells exhibit lower interfacial specific impedance (IASR) and higher critical current density (CCD) than both Li|Ag@Ga0-LLZO|Li and Li| [email protected] |Li and was stabilized at 0.15 mA/cm 2 for 1300 h of stable cycling. In addition, the all-solid-state battery Li| [email protected] |LFP was cycled at 0.2C for 100 cycles with 82 % capacity retention, demonstrating its promising application in lithium batteries.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
Membranes
·
2023
·Vol. 13
·期 2
·216
·
IF 4.2
Shishuo Liang,Dong Yang,Jianhua Hu,Shusen Kang,Xue Zhang,Yanchen Fan
With the rapid development of energy storage and electric vehicles, thiophosphate-based all-solid-state batteries (ASSBs) are considered the most promising power source. In order to commercialize ASSBs, the interfacial problem between high-voltage cathode active materials and thiophosphate-based solid-state electrolytes needs to be solved in a simple, effective way. Surface coatings are considered the most promising approach to solving the interfacial problem because surface coatings could prevent direct physical contact between cathode active materials and thiophosphate-based solid-state electrolytes. In this work, Li7La3Zr2O12(LLZO) and LiNbO3(LNO) coatings for LiCoO2(LCO) were fabricated by in-situ interfacial growth of two high-Li+conductive oxide electrolytes on the LCO surface and tested for thiophosphate-based ASSBs. The coatings were obtained from a two-step traditional sol–gel coatings process, the inner coatings were LNO, and the surface coatings were LLZO. Electrochemical evaluations confirmed that the two-layer coatings are beneficial for ASSBs. ASSBs containing LLZO-co-LNO coatings LiCoO2(LLZO&LNO@LCO) significantly improved long-term cycling performance and discharge capacity compared with those assembled from uncoated LCO. LLZO&LNO@LCO||Li6PS5Cl (LPSC)||Li-In delivered discharge capacities of 138.8 mAh/g, 101.8 mAh/g, 60.2 mAh/g, and 40.2 mAh/g at 0.05 C, 0.1 C, 0.2 C, and 0.5 C under room temperature, respectively, and better capacity retentions of 98% after 300 cycles at 0.05 C. The results highlighted promising low-cost and scalable cathode material coatings for ASSBs.Keywords:solid-state batteries;LiCoO2;sulfide solid-state electrolyte;LiNbO3-coating;LLZO-coating
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
PubMed
高影响因子
ACS Applied Materials & Interfaces
·
2021
·
IF 9.229
Jiaming Xu,Chao Ma,Chengyue Chang,Xiaofeng Lei,Yinwei Fu,Jian Wang,Xizheng Liu,Yi Ding
Hybrid solid/gel electrolytes (SGEs) have generated much research attentions because of their capability to suppress Li dendrite growth and improve battery safety. However, the interfacial compatibility of the electrode/electrolyte or polymer/inorganic ceramics within hybrid electrolytes remains challenging for practical applications. Herein, an SGE is fabricated by confining ceramic particles (Li7La3Zr2O12; LLZO) into in situ formed tetraethylene glycol dimethyl ether (G4)-based gel electrolytes within assembled cells. A hierarchical layered structure is formed when LLZO settles near the Li anode within the liquid electrolyte during the gradual gelatinization process. Good interfacial compatibility is obtained from good contact with the liquid G4 component. The LLZO layer also serves as an ionic sieve to redistribute the Li deposition. This SGE endows stable Li stripping/plating cycling over 800 h at 0.5 mA/cm2 (60 °C). Moreover, Li-metal batteries with an SGE coupled with LiFePO4 and an air cathode both exhibit superior cycling performance. This work presents a promising strategy for hierarchically layered SGEs for high-performance Li-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
PubMed
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2024
·
IF 9.4
Zhiqi Lu,Ji Li,Jiaqi An,Xiaoyue Zeng,Jinle Lan,Yunhua Yu,Xiaoping Yang
The active cyano-group in polyacrylonitrile has severe passivation of lithium anode under larger current density, which restricts the wide application of polyacrylonitrile(PAN) in lithium metal batteries . Herein, in order to address the excessive passivation of lithium metal by PAN, inspired by the pre-oxidation of carbon fibers, PAN was pre-oxidized at 230 °C, which transformed part of the cyano group into a more chemically stable cyclized structure. The electrochemical and mechanical properties of the composite solid electrolyte were effectively improved by introducing the fast ionic conductor Li 6.25 La 3 Zr 2 Al 0.25 O 12 into PAN by electrospinning. The oxidized PAN-based composite solid electrolyte presents high ionic conductivity (3.05 × 10 −3 S·cm −1 ) and high lithium transference number of 0.79 at 25 °C, further contributing to a high electrochemical window (5.3 V). The solid-state batteries assembled by Li||10 wt%-LLZAO@230-oxy-PAN||NCM523 behave superb electrochemical performance , delivering a high initial discharge capacity of 157 mAh g −1 at 0.2 C. After 100 cycles, the capacity retention was 93.3 %, indicating the electrolyte displays great electrochemical stability. This work provides new insights into the structural design of polymer-based high-voltage batteries.
✓ 已验证
DOI
高影响因子
Journal of Materials Chemistry A
·
2023
·Vol. 11
·期 44
·23932-23939
·
IF 11.9
Ying Zhou,Ying Tian,Wen Wang,Yu Zhou
The poor interface between Li/LLZO leads to the easy penetration of lithium metal into the garnet-type electrolyte, which limits its application. A hybrid quasi-solid electrolyte (HQSE) composed of porous LLZO and liquid electrolyte (LE) can effectively solve the interface problem. In practice, the implementation of HQSE-based batteries typically necessitates the use of porous LLZO scaffolds that possess sufficient mechanical strength. Herein, a novel method was developed to prepare porous LLZO scaffolds by combining gel casting and in situ reaction sintering. The enhanced mass transfer effect of the Li2O liquid phase on the surface of LLZO particles in the early stages, as well as the LiGaO2 liquid phase at the grain boundaries in the later stages, would result in the rapid densification of porous LLZO. By controlling the sintering temperature, the degree of densification can be controlled, thereby achieving a balance between porosity and mechanical strength in the porous LLZO scaffolds. When the solid phase content is 27.5 vol%, the porous LLZO scaffold obtained by heating at 1050 °C for 2 h exhibits a porosity of 32.7% and a flexural strength of up to 46.5 MP. In addition, the HQSE exhibits a high room-temperature ionic conductivity of up to 2.06 × 10−3 S cm−1. The symmetric cells delivered high cycling stability of over 800 h for lithium plating and stripping at a current density of 0.5 mA cm−2 with a small polarization voltage of about 0.05 V. This method offers a new route toward constructing a range of 3D scaffolds with SSEs for quasi-solid-state battery applications.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2018
·
IF 8.097
Xiao Huang,Yang Lu,Jun Jin,Sui Gu,Tongping Xiu,Zhen Song,Michael E. Badding,Zhaoyin Wen
Li-garnet Li7La3Zr2O12 (LLZO) is a promising candidate of solid electrolytes for high-safety solid-state Li+ ion batteries. However, because of its high reactivity to water, the preparation of LLZO powders and ceramics is not easy for large-scale amounts. Herein, a method applying water-based solvent is proposed to demonstrate a possible solution. Ta-doped LLZO, that is, Li6.4La3Zr1.4Ta0.6O12 (LLZTO), and its LLZTO/MgO composite ceramics are made by attrition milling, followed by a spray-drying process using water-based slurries. The impacts of parameters of the method on the structure and properties of green and sintered pellets are studied. A relative density of ∼95%, a Li-ion conductivity of ∼3.5 × 10–4 S/cm, and uniform grain size LLZTO/MgO garnet composite ceramics are obtained with an attrition-milled LLZTO/MgO slurry that contains 40 wt % solids and 2 wt % polyvinyl alcohol binder. Li–sulfur batteries based on these ceramics are fabricated and work under 25 °C for 20 cycles with a Coulombic efficiency of 100%. This research demonstrates a promising mass production method for the preparation of Li-garnet ceramics.
研究领域:
材料科学
·
能源技术
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF APPLIED POLYMER SCIENCE
·
2026
·
IF 3.1
Haihua Wang,Haonan Wang,Kewei Shu,Chaoxian Chen,Qing Liu,Rui Cao,Jiaheng Li,Xing Yang,Zhuyu Li
Owing to its high lithium-ion conductivity, the cubic garnet-phase material Li 7 La 3 Zr 2 O 12 (LLZO) is a widely adopted key component in the fabrication of composite solid-state electrolytes (CSSEs). Nevertheless, the advancement of all-solid-state lithium batteries (ASSLBs) is still hindered by two major challenges: the high intrinsic crystallinity of poly(ethylene oxide) (PEO) and poor interfacial stability. Herein, cubic garnet Li 6.3 La 2.7 Ba 0.3 ZrNbO 12 (LLBZNO) featuring Ba and Nb co-doping was first prepared by a conventional solid-state method. Following this, the material was dispersed within a PEO matrix to construct composite solid-state electrolytes. Adding LLBZNO served to decrease PEO's crystallinity while enhancing its mechanical flexibility and bolstering its interfacial compatibility with lithium metal. The optimized membrane demonstrated superior properties, including a high Li + transference number of 0.75 (at 60°C) and an extended electrochemical stability window of up to 5.1 V (vs. Li/Li + ) under the present testing conditions. It also showed an excellent ability to suppress dendrites, facilitating stable cycling at 0.1 mA cm −2 for 1500 h without short-circuiting. Furthermore, the LFP/LLBZNO–PEO/Li battery delivered a high discharge capacity of 101.6 mA h g −1 after 300 cycles at 1°C with nearly 99% coulombic efficiency. These findings highlight that LLBZNO-PEO composite solid electrolytes possess superior ionic transport, electrochemical stability, and mechanical robustness, providing a viable pathway toward the advancement of next-generation high-performance ASSLBs.
✓ 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）