Journal of Energy Chemistry
·
2023
·
IF 13.1
Haochang Zhang,Zhaozhe Yu,Hannan Chen,Yongjian Zhou,Xiao Huang,Bingbing Tian
All-solid-state Li batteries (ASSLBs) with solid-state electrolytes (SSEs) are exciting candidates for next-generation energy storage and receive considerable attention owing to their reliability. Halide SSEs are promising candidates due to their excellent stability against 4 V-class layered cathodes. Compared with Li 3 InCl 6 or Li 3 ScCl 6 , the low ionic conductivity of Li 2 ZrCl 6 (LZC) is a challenge despite its low raw-material cost. Herein, we report a family of Li-Richened chloride, Li 2+2 x Zr 1– x M x Cl 6 , which can be used in high-performance ASSLBs owing to its high ionic conductivity (up to 0.62 mS cm −1 ). The theoretical (ab initio molecular dynamics simulations) and experimental results prove that the strategy of aliovalent substitution with divalent metals to obtain Li-Richened LZC is effective in improving Li + conductivity in SSEs. By combining Li 2.1 Zr 0.95 Mg 0.05 Cl 6 (Mg5-LZC) with a Li–In anode and a LiCoO 2 cathode, a room-temperature ASSLBs with excellent long-term cycling stability (88% capacity retention at 0.3C for 100 cycles) and high-rate capability (121 mA h g −1 at 1C) is reported. This exploratory work sheds light on improving the Li + conductivity of low-cost LZC-family SSEs for constructing high performance ASSLBs.
研究领域:
材料科学
·
电化学
·
能量存储
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DOI
高影响因子
Nano Energy
·
2026
·
IF 16.7
Xuan Yang,Zhaowen Chen,Jingjing Wang,Xuexia Song,Zihao Yang,Yuhui Xu,Boli Tong,Ningjing Hou,Guiqiang Cao,Wei Xiao,Wenbin Li,Jiujun Zhang,Xifei Li
The lattice expansion/softening can significantly increase ionic conductivity. • endow electrolytes with excellent anti-reduction stability. • The low reduction potential of Li 2 ZrCl 4.8 I 1.2 matches well with ASS Li-S batteries. In this study, I - doping was performed to address the limited ionic conductivity of Li 2 ZrCl 6 arising from the excessively narrow Li + transport channels. Owing to its large ionic radius (2.20 Å) and high polarizability, I - incorporation simultaneously expands and softens the lattice of Li 2 ZrCl 6 by enlarging interplanar spacing and weakening anion-cation interactions, thereby broadening Li + migration channels and reducing Li + migration barriers across all crystallographic directions. Furthermore, the introduction of I - disrupts the symmetry of [ZrX 6 ] (X = Cl, I) octahedra and induces the lattice distortion in Li 2 ZrCl 6 , destroying long-range order of structure with an increase in amorphous content. Nevertheless, excessive lattice distortion and overly large interplanar spacing induced by high iodide content block Li + transport pathways, thereby disrupting migration continuity and impeding Li + migration. Therefore, the ionic conductivity of Li 2 ZrCl 6-x I x (0 < x ≤ 1.5) exhibits a volcano-type dependence on the content of I - . At room temperature, Li 2 ZrCl 4.8 I 1.2 with the lowest migration energy barrier (0.286 eV) shows the highest ionic conductivity of 2.18 mS cm −1 which is more than five times that of Li 2 ZrCl 6 . In addition, the enhanced covalent-bond tendency between Zr 4+ and I - in the structure suppresses the reduction of Li 2 ZrCl 4.8 I 1.2 , decreasing its reduction potential down to 1.67 V (vs. Li/Li⁺). Meanwhile, the Li/ Li 2 ZrCl 4.8 I 1.2 /Li battery achieves stable cycling performance over 1200 h at 0.5 mA cm −2 under overpotential of 0.27 V, demonstrating the excellent anti-reduction stability of the solid-state electrolyte. Download: Download high-res image (292KB) Download: Download full-size image The lattice engineering strategy of introducing iodine ions with a large ionic radius (2.20 Å) and high polarizability simultaneously enhances the ionic conductivity (up to 2.18 mS cm - ¹ at room temperature) and anti-reduction stability of Li 2 ZrCl 6 .
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DOI
高影响因子
Journal of Energy Storage
·
2024
·
IF 8.9
Jinyin Cheng,Haochang Zhang,Zhixin Wang,Yaqing Zhou,Kangzhe Yu,Yan Cheng,Zhaozhe Yu,Xiao Huang,Bingbing Tian
Emerging halide superionic conductors with remarkable oxidative stability and deformability , making them a potential game-changer for high-performance all-solid-state Li batteries (ASSLBs). The recently reported Li 2 ZrCl 6 (LZC) with low cost possess great potential. However, its ionic conductivity at 25 °C is below 1 mS cm −1 . Herein, we developed a Li-richened strategy to LZC by doping O 2− at Cl − site via a mechanochemical method to form oxychloride electrolytes Li 2+ x ZrCl 6− x O x (0 ≤ x ≤ 1.8), resulting in high ionic conductivity up to 1.46 mS cm −1 at room temperature (RT). The experimental results and theoretical calculations (ab initio molecular dynamics simulations) demonstrate that the Li 2 O doping leading to a Li-richened LZC lattice effectively enhances the Li + conductivity in solid-state electrolytes (SSEs). Significantly, an increasing O 2− substitution in the Li 2+ x ZrCl 6− x O x microcrystalline framework induces a progressive structural evolution from triangular to monoclinic phases, accompanied by a redistribution of Li + . Furthermore, the ASSLBs formed by Li 3.4 ZrCl 4.6 O 1.4 (LZCO) with Li-In anode and bare LiCoO 2 cathode shows excellent long-term cycling stability (94 % capacity retention for 600 cycles at 1 C) and high-rate performance (105.7 mAh g −1 at 2 C). This exploratory study provides a promising strategy to facilitate the application of low-cost LZC-based SSEs for high-performance ASSLBs.
研究领域:
材料科学
·
能源存储技术
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产品关联
DOI
高影响因子
CHINESE CHEMICAL LETTERS
·
2021
·Vol. 33
·期 10
·4635-4639
·
IF 6.779
Shuai Chen,Chuang Yu,Shaoqing Chen,Linfeng Peng,Cong Liao,Chaochao Wei,Zhongkai Wu,Shijie Cheng,Jia Xie
Solid-state batteries with high energy density and safety are promising next-generation battery systems. However, lithium oxide and lithium sulfide electrolytes suffer low ionic conductivity and poor electrochemical stability, respectively. Lithium halide solid electrolyte shows high conductivity and good compatibility with the pristine high-voltage cathode but limited applications due to the high price of rare metal. Zr-based lithium halides with low cost and high stability possess great potential. Herein, a small amount of In 3+ is introduced in Li 2 ZrCl 6 to synthesize Li 2.25 Zr 0.75 In 0.25 Cl 6 electrolytes with a high room temperature Li-ion conductivity of 1.08 mS/cm. Solid-state batteries using Li 2.25 Zr 0.75 In 0.25 Cl 6 /Li 5.5 PS 4.5 Cl 1.5 bilayer solid electrolytes combined with Li-In anode and pristine LiNi 0.7 Mn 0.2 Co 0.1 O 2 cathode deliver high initial discharge capacities under different cut-off voltages. This work provides an effective strategy for enhancing the conductivity of Li 2 ZrCl 6 electrolytes, promoting their applications in solid-state batteries.
研究领域:
材料科学
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电化学
·
固体离子学
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能源存储
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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 ALLOYS AND COMPOUNDS
·
2025
·
IF 6.3
Fu-Jie Zhao,Lei Xian,Bo Li,Ling-Bin Kong
Li 2 ZrCl 6 has emerged as a promising candidate material due to its notable cost-effectiveness compared to other complex halide superionic conductors. However, its relatively low ionic conductivity at room temperature remains a significant obstacle in practical applications. Doping serves as a prevalent strategy to enhance ion transport capabilities by modulating the lattice structure. In this work, Li 2-x Zr 1-x Nb x Cl 6 electrolyte is synthesized by doping Nb 5+ into Li 2 ZrCl 6 . Nb 5+ doping enhances Li + transport dynamics through a dual mechanism involving vacancies and structural modifications. The ionic conductivity of the modified Li 1.85 Zr 0.85 Nb 0.15 Cl 6 reaches 0.70 mS·cm −1 at room temperature, more than doubling that of Li 2 ZrCl 6 . Furthermore, the electrochemical performance of an all-solid-state battery utilizing Li 1.85 Zr 0.85 Nb 0.15 Cl 6 electrolyte paired with NCM811 cathode is evaluated. The results demonstrate that Nb 5+ doping significantly enhances the specific discharge capacity and cycle stability of Li 2 ZrCl 6 . These findings provide valuable insights into enhancing the ionic conductivity of zirconium-based solid electrolyte systems through the doping of high-valence ions.
研究领域:
材料科学
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储能技术
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固体离子学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
Energies
·
2026
·Vol. 19
·期 12
·2790
·
IF 3.9
Jin Liang,Xiaojin Liu,Weiye Ma,Zhiyi Pan,Zhiqiang Liu,Yuxin Liang,Wence Xu,Shengli Zhu,Zhonghui Gao
N-doped Li2ZrCl6−3xNxchloride solid electrolytes were synthesized via a mechanochemical method, and the effects of N incorporation on crystal structure, Li local environment, and Li+transport were systematically investigated. X-ray diffraction suggested that the main Li2ZrCl6-related diffraction features were largely retained, while N introduction induced partial structural evolution towardC2/m-related features. 7Li MAS NMR revealed that N incorporation sharpened Li resonance peaks. Among the series, Li2ZrCl5.7N0.1exhibited the highest room-temperature ionic conductivity of 1.15 mS cm−1, with the lowest activation energy of 0.237 eV, demonstrating a reduced Li+migration barrier. All-solid-state batteries incorporating Li2ZrCl5.7N0.1showed stable rate capability and long-term cycling, retaining 85.9% capacity after 500 cycles at 1C and 77.4% after 3000 cycles at 3C. These results suggest that appropriate N modification can tune the Li2ZrCl6-based structure and Li local environment, thereby improving Li+transport in all-solid-state lithium batteries. This work provides a feasible strategy for improving chloride-based solid electrolytes for next-generation energy storage.
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DOI
高影响因子
Energy Storage Materials
·
2024
·
IF 18.9
Kang-Ning Gao,Fan Bai,Zhuang Sun,Tao Zhang
Halide solid electrolytes , known for their stability to 4 V-class cathodes and deformability, emerge as promising candidates for high-performance all-solid-state batteries. Unfortunately, their synthesis often involves expensive elements, limiting mass production and cost-effectiveness. In this study, aliovalent-substituted Li 2 ZrCl 6 with Al 3+ is fabricated by one-step ball milling , exhibiting lower cost, higher ionic conductivity and a wider electrochemical window. The cost is reduced by approximately 13.4 % through a 25 % aliovalent substitution. Li + conductivity of Li 2+x Zr 1-x Al x Cl 6 increases from 0.12 mS/cm ( x = 0) to a peak of 1.13 mS/cm ( x = 0.25) at 25 °C, and activation energy (Ea) reduces from 0.43 eV to 0.29 eV, which is attributed to the extension of Li + migration pathways along intra- and inter- ab-plane around Al sites as revealed by AIMD and BVSE calculations. Both experimental result and calculation indicate that the substitution of Al 3+ improves the oxidation potential from 4.1 V in Li 2 ZrCl 6 to 4.3 V in Li 2.25 Zr 0.75 Al 0.25 Cl 6 . Furthermore, the excellent electrochemical performance of all-solid-state batteries is demonstrated using Al 3+ -substituted Li 2 ZrCl 6 and commercial LiNi 0.8 Co 0.1 Mn 0.1 O 2 . The unravelled multifaceted effects of Al 3+ aliovalent substitution in Li 2 ZrCl 6 solid electrolyte endow it highly advantageous for future applications in halide-based all-solid-state lithium batteries.
研究领域:
材料科学
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电化学
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储能技术
·
固态化学
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电池技术
✓ 已验证
DOI
高影响因子
Energy Material Advances
·
2023
·
IF 12.9
Shuai Chen,Chuang Yu,Chaochao Wei,Ziling Jiang,Ziqi Zhang,Linfeng Peng,Shijie Cheng,Jia Xie
Lithium halide electrolytes show great potential in constructing high-energy-density solid-state batteries with high-voltage cathode materials due to their high electrochemical stability and wide voltage windows. However, the high cost and low conductivity of some compositions inhibit their applications. Moreover, the effect of electronic additives in the cathode mixture on the stability and capacity is unclear. Here, the Y 3+ doping strategy is applied to enhance the conductivity of low-cost Li 2 ZrCl 6 electrolytes. By tailoring the Y 3+ dopant in the structure, the optimal Li 2.5 Zr 0.5 Y 0.5 Cl 6 with high conductivity up to 1.19 × 10 −3 S cm −1 is obtained. Li 2.5 Zr 0.5 Y 0.5 Cl 6 @CNT/Li 2.5 Zr 0.5 Y 0.5 Cl 6 /Li 5.5 PS 4.5 Cl 1.5 /In-Li solid-state batteries with different carbon nanotube (CNT) contents in the cathode are fabricated. The stability and electrochemical performances of the cathode mixture as a function of CNT content are studied. The cathode mixture containing 2% (wt.) CNT exhibits the highest stability and almost no discharge capacity, while the cathode mixture consisting of Li 2.5 Zr 0.5 Y 0.5 Cl 6 and 10% (wt.) CNT delivers a high initial discharge capacity of 199.0 mAh g −1 and reversible capacities in the following 100 cycles. Multiple characterizations are combined to unravel the working mechanism and confirm that the electrochemical reaction involves the 2-step reaction of Y 3+ /Y 0 , Zr 4+ /Zr 0 , and Cl − /Cl x − in the Li 2.5 Zr 0.5 Y 0.5 Cl 6 electrolyte. This work provides insight into designing a lithium halide electrolyte-based cathode mixture with a high ionic/electronic conductive framework and good interfacial stability for solid-state batteries.
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DOI
高影响因子
Nanoscale
·
2025
·Vol. 17
·期 26
·15856-15865
·
IF 5.1
Pengfei Du,Peng Zhang,Zhenyang Shen,Yongmei Zhou,Ying Liu,Qingtao Wang
All-solid-state lithium batteries (ASSLBs) are garnering increasing attention as a state-of-the-art energy storage technology. Halide solid electrolytes have emerged as a focal point of research in recent years, owing to their straightforward preparation methods and high ionic conductivity at room temperature. In this study, Bi-doped Li2ZrCl6 was synthesized using a high-energy ball milling method. The Bi3+ ion effectively replaces some of the Zr4+ ions. Due to its lower valence state and larger ionic radius, the concentration of Li+ in the electrolyte increases, and the lattice volume increases, which facilitates Li+ migration. Consequently, the ionic conductivity of modified Li2.15Zr0.85Bi0.15Cl6 at room temperature is 4.9 × 10−4 S cm−1, more than double that of Li2ZrCl6. This enhancement was further validated through cyclic voltammetry and wet air stability tests, which confirmed that Bi3+ doping not only significantly improves the electrochemical high-pressure oxidation stability of Li2ZrCl6 but also enhances its stability in humid air. Additionally, charge/discharge tests on ASSLB using Li2.15Zr0.85Bi0.15Cl6 as the electrolyte demonstrated that Bi doping enhances the electrochemical performance of Li2ZrCl6, leading to improvements in discharge specific capacity and cycle life.
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产品关联
DOI
PubMed
高影响因子
Journal of Materials Chemistry A
·
2024
·
IF 10.7
Deli Xu,Jianshu He,Yuanyuan He,Sheng Wang,Guoxian Wu,Minghua Li,Hao Cheng,Kangzhe Yu,Xiao Huang,Bingbing Tian
All-solid-state Li batteries (ASSLBs) have drawn attention as strong contenders for future energy storage owing to their extreme safety. When paired with uncoated 4 V-class layered positive materials, halide solid-state electrolytes (SSEs) exhibit excellent stability and compatibility, strong Li+ conductivity, and softness, making them highly potential SSE materials. Despite its cost-effective precursors, Li2ZrCl6 is plagued by its inherently poor ionic conductivity. Herein, we report a non-crystalline halide SSE, Li2.2ZrCl5.8S0.2, which possesses a superior Li+ conductivity (0.86 mS cm−1) and can be applied in high-performance ASSLBs. By integrating the Li2.2ZrCl5.8S0.2 SSE with a LiIn negative material and an uncoated LiCoO2 positive material, we acquire ordinary-temperature ASSLBs exhibiting excellent cycle-life (93.4% capacity retention under 1C for 100 cycles) and high-rate capacity (exceeding 80 mA h g−1 at 2C). The work proposes a non-crystalline strategy to improve Li+ conductivity in Li2ZrCl6-family SSEs for ASSLSBs.
研究领域:
材料科学
·
能源存储技术
✓ 已验证
DOI
高影响因子
JOURNAL OF ELECTRONIC MATERIALS
·
2024
·Vol. 54
·期 2
·1021-1028
·
IF 2.2
Yao Zhujun,Jia Qixiang,Xiang Jiayuan,Tu Fangfang,Shi Juntao,Zhang Yuhong,Huang Jianhao,Jiang Yuanyuan,Gong Wei,Yang Donghui
Halides not only possess high ionic conductivity but also exhibit excellent electrochemical stability against high-voltage cathodes, making them promising candidates for solid-state electrolytes in all-solid-state lithium metal batteries (ASSLMBs). Compared with rare-earth halide electrolytes, Li 2 ZrCl 6 electrolytes are less costly. However, they face challenges relating to relatively lower ionic conductivity. Herein, Li 2+ x Zr 1− x La x Cl 6 is synthesized through La 3+ doping in Li 2 ZrCl 6 . The introduction of La 3+ increases the concentration of lithium ions in the crystal and expands the lattice volume, leading to ionic conductivity as high as 8.22 × 10 −4 S cm −1 . When Li 2.1 Zr 0.9 La 0.1 Cl 6 is applied in ASSLMBs (with a LiNi 0.8 Mn 0.1 Co 0.1 O 2 cathode and a Li-In anode), it exhibits superior electrochemical performance, with high initial capacity of 132.5 mA h g −1 , and after 100 cycles at 0.5 C, the battery still maintains a capacity of 72.4 mA h g −1 and high coulombic efficiency of 99.7%. Graphical
研究领域:
材料科学
·
电化学
·
储能技术
·
固体离子学
✓ 已验证
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2022
·
IF 10.383
Xuming Luo,Yu Zhong,Xiuli Wang,Xinhui Xia,Changdong Gu,Jiangping Tu
Superionic halides have returned to the spotlight of solid electrolytes because of their satisfactory ionic conductivity, soft texture, and stability toward high-voltage electrode materials. Among them, Li2ZrCl6 has aroused interests since abundant Zr element can reduce the cost of large-scale synthesis. However, the related research is very limited, including the detailed parameters during synthesis and the possible strategies for enhancing ionic conductivity. In this work, we have systematically investigated the effects of synthesis parameters on the structure and ionic conductivity of Li2ZrCl6 during the ball-milling annealing process. It is found that mild heat treatment (100 °C) can largely enhance the ionic conductivity of ball-milled electrolytes by 2–3 times, which has not been previously reported. Such enhancement is mainly attributed to the network-like micromorphology composed of nanorods, nanowires, or nanoballs, which is beneficial for lithium ion migration. Finally, the modified Li2ZrCl6 (4.46 × 10–4 S cm–1 @ RT) is also proved to be applicable in LiNi0.8Mn0.1Co0.1O2/ Li2ZrCl6/ Li6PS5Cl/Li-In all-solid-state lithium metal batteries (ASSLMBs). It presents high initial charge capacity of 176.4 mAh g–1 and satisfactory cycle stability since a discharge capacity of 90.8 mAh g–1 is maintained after 40 cycles at 0.1 C. The Li2ZrCl6 electrolytes synthesized via the mechanochemical method is promising to be applied in the high-voltage ASSLMBs, and its ionic conductivity can be enhanced by the strategies provided in our work.
研究领域:
材料科学
·
电化学
·
储能
·
固体离子学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）