ADVANCED FUNCTIONAL MATERIALS
·
2025
·
IF 19
Lei Gao,Zhigang Zhang,Zheyuan Zhang,Yongrui Luo,Bolong Hong,Longbang Di,Haijin Ni,Jinlong Zhu,Ruqiang Zou,Enyue Zhao,Songbai Han
The halide solid-state electrolyte (SSE) Li 2 ZrCl 6 has emerged as a promising candidate for all-solid-state batteries (ASSBs) due to the abundance of Zr in the Earth's crust and its low cost. However, its relatively low ionic conductivity prevents it from meeting the essential performance threshold (> 1 mS cm −1 ) required for application in ASSBs. In this work, a novel strategy is presented to enhance ionic conductivity by incorporating high-valence Ta 5+ into the Li 2 ZrCl 6 framework, resulting in a series of Li-deficient Li 2– x Ta x Zr 1– x Cl 6 (LTZC, 0 ≤ x ≤ 0.4) SSEs. Remarkably, the LTZC ( x = 0.275) achieves a high ionic conductivity of 1.43 mS cm −1 at 30 °C, surpassing that of Li-rich Li 2 ZrCl 6 -based SSEs (e.g., Li 2+2 x Zr 1– x Mg x Cl 6 ). Neutron powder diffraction reveals a pronounced rearrangement of Li + ions upon Ta 5+ doping, and bond-valence site energy calculations indicate that this rearrangement enhances Li + transport within the lattice. Furthermore, ASSBs incorporating LTZC SSE with LiCoO 2 or LiNi 0.8 Co 0.1 Mn 0.1 O 2 cathode and Li-In anode exhibit excellent cycling performance. This work underscores the effectiveness of structural regulation in developing Li-deficient halide SSEs as a viable strategy for enhancing their electrochemical performance.
研究领域:
材料科学
·
电化学
·
储能
·
固态离子学
✓ 已验证
产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2024
·
IF 7.1
Juntao Shi,Zhujun Yao,Jiayuan Xiang,Chen Cai,Fangfang Tu,Yongqi Zhang,Weilin Yao,Qixiang Jia,Yan Zhou,Shenghui Shen,Yefeng Yang
The combined advantages of good mechanical deformability, high Li+ conductivity, and strong compatibility with 4 V-class cathodes make halide solid-state electrolytes promising candidates for high-energy all-solid-state lithium–metal batteries (ASSLMBs). Among these, the cost-effective Li2ZrCl6 has garnered significant attention due to the non-inclusion of rare-earth metals. However, the conventional one-step ball-milling synthesized Li2ZrCl6 always exhibits an ionic conductivity lower than 5 × 10–4 S cm–1 in most literature. Here, a simple optimized two-step ball-milling strategy is adopted to achieve a high Li+ conductivity of nearly 1 × 10–3 S cm–1 at 30 °C for Li2ZrCl6. Simultaneously, the effects of rotational speed and ball-to-powder mass ratio on the structure and ionic conductivity of Li2ZrCl6 are investigated. The Li+ migration pathways in electrolytes are also studied by bond valence site energy (BVSE) calculations. Moreover, the application potential of the modified Li2ZrCl6 electrolyte in ASSLMBs assembled with the LiCoO2 cathode and the lithium–indium alloy anode has been studied. The ASSLMBs exhibit an initial discharge capacity of 123.4 mA h g–1 at room temperature (0.1 C) and a capacity retention of 71% after 50 cycles. Therefore, this study introduces an effective strategy for synthesizing high-performance halide electrolytes, thus facilitating the practical implementation of halide-based ASSLMBs.
研究领域:
材料科学
·
电化学
·
储能技术
·
固态电池
✓ 已验证
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2026
·
IF 7.8
Chao Wu,Zhen Wang,Jiawu Cui,Qi Ling,Xianwei Wang,Zexun Tang,Chengyong Shu,Kang Yang,Yuping Wu,Wei Tang
Halide solid-state electrolytes (SSEs) have emerged as a compelling research focus for advanced all-solid-state lithium-ion batteries (ASSLBs), driven by their concurrent possession of exceptional oxidation stability and remarkable mechanical deformability. While Li2ZrCl6 (LZC) has attracted significant attention for its cost-effectiveness and material abundance, its practical application remains a major challenge due to lower ionic conductivity. Herein, we reported a series of Cd2+-doped lithium-rich superionic conductors Li2+2xZr1–xCdxCl6 (0 ≤ x ≤ 0.2), which collectively adopted a Li3YCl6-like trigonal structure. The incorporation of Cd2+ ions, which possess a lower charge and larger ionic radius, enhanced carrier concentration and caused anisotropic lattice expansion. Specifically, Li2.1Zr0.95Cd0.05Cl6 (LZC-5Cd) exhibited the highest ionic conductivity (9.8 × 10–4 S cm–1) at 30 °C while simultaneously broadening the electrochemical window to 4.11 V. The ASSLBs configuration featuring the LiCoO2 cathode, LZC-5Cd electrolyte, and Li–In anode demonstrated superior reversible capacity (161.4 mAh g–1 at 0.1 C) within the wide potential range of 2.5–4.3 V and remarkable cycling stability (80.69% capacity retention over 250 cycles at 2 C). In this regard, this work presented a cost-effective structural engineering strategy that simultaneously boosted ionic conductivity and broadened the working potential range to provide a potential model for the large-scale application of halide-based ASSLBs.
✓ 已验证
DOI
PubMed
高影响因子
CHEMISTRY OF MATERIALS
·
2025
·
IF 7
Ruishan Zhang,Shunning Li,Feng Pan,Bingkai Zhang
Li2ZrCl6 (LZC), a halide-based solid-state electrolyte, combines high ionic conductivity with cost-effectiveness, yet its atomic-scale ion transport mechanisms and doping strategies are insufficiently understood. Using first-principles calculations and ab initio molecular dynamics (AIMD) simulations, we first evaluated the intrinsic Li-ion migration behavior in bulk LZC. Potential energy surface analysis based on Li-ion site energies, combined with AIMD calculations, confirms the potential promotional effect of bismuth (Bi) cation doping on bulk ionic conductivity, increasing it to 10.93 mS cm–1 and reducing the activation energy to 241.77 meV. Experimental results also demonstrate that Bi doping significantly enhances the electrical conductivity of LZC. This improvement is attributed to a transition from short- to long-range cooperative Li-ion migration. Additionally, 50% bromine (Br) substitution helped to reduce energy fluctuations caused by cation disorder, leading to a more uniform migration pathway. Statistical analysis across multiple solid-state electrolyte (SSE) systems further showed that shorter nearest-neighbor Li–Li distances are strongly correlated with higher conductivity and lower activation energies. This work highlights the importance of local structure and short-range interactions in halide SSEs and proposes a Bi-doped LZC as a cost-effective, high-performance candidate for next-generation solid-state batteries.
✓ 已验证
产品关联
DOI
高影响因子
Journal of Materiomics
·
2026
·
IF 9.6
Ying Liang,Chuangjie Guo,Ying Qi,Hetian Chen,Haocheng Yuan,Dengfeng Yu,Peipei Ding,Yue Li,Hong Liu,Yaoyu Ren,Xue Zhang,Ce-Wen Nan
The development of chloride-based solid-state electrolytes faces significant challenges in achieving an optimal balance among ionic conductivity, compatibility with Li metal, and cost-effectiveness. Herein, a novel Dy 3+ -doped Li 2 ZrCl 6 (Li 2+ x Zr 1− x Dy x Cl 6 ) halide electrolyte is rationally designed via mechanochemical synthesis. By partially substituting Zr 4+ with larger Dy 3+ ions, the optimized Li 2.25 Zr 0.75 Dy 0.25 Cl 6 exhibits: (1) superior ionic conductivity of 1.54 mS/cm (a 4.4-fold increase over pristine Li 2 ZrCl 6 ) after low-temperature annealing, (2) 3D Li + transport pathways confirmed by DFT calculations, and (3) suppressed reduction of Zr 4+ at the Li metal interface, extending symmetric cell cycling to 500 h (0.2 mA/cm 2 ). Synchrotron XAFS and XPS/TOF-SIMS analyses reveal that Dy 3+ doping broadens Li + migration channels and inhibits elemental Zr formation. The LiCoO 2 -based all-solid-state lithium batteries exhibit superior cycling stability (81.4% capacity retention at 1000 cycles) and outstanding rate performance (82.9 mA·h·g −1 at 3 C). This work presents a paradigm for designing efficient and economical halide solid-state electrolytes.
✓ 已验证
产品关联
DOI
高影响因子
ADVANCED FUNCTIONAL MATERIALS
·
2025
·Vol. 35
·期 22
·2426053
·
IF 19
Qixiang Jia,Zhujun Yao,Jiayuan Xiang,Juntao Shi,Yan Zhou,Jianhao Huang,Hongliang Zhang,Xiaoxiao Zhang,Yefeng Yang,Jiangping Tu
Li 2 ZrCl 6 (LZC) solid electrolyte has been recognized as a promising candidate for all-solid-state batteries (ASSBs), owing to its remarkable compatibility with high-voltage cathodes and the cost advantage among halide electrolytes. However, the ionic conductivity of LZC (≈0.4 mS cm −1 ) requires enhancement. Herein, rare earth metal elements (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Y) have been doped into LZC, resulting in a doubling of the ionic conductivity. Moreover, Ta 5+ is utilized to further modulate the concentration of Li + to enhance the ionic conductivity and reduce the dosage of expensive rare-earth metal. Using the Li-Zr-Dy-Cl component as a case study, 16 types of Dy 3+ and Ta 5+ co-doped electrolytes have been synthesized and the optimal Li 2.1 Zr 0.8 Dy 0.15 Ta 0.05 Cl 6 (LZDTC) exhibits the ionic conductivity of 1.67 mS cm −1 . Three-dimensional Li-ion transport pathways in LZDTC has been revealed. The dual-substitution of Dy and Ta at Zr site changes length of Li-Cl bond and Li occupation, thereby reducing the resistance to Li + migration. ASSBs of Li-In/LGPS-LZDTC/NCM811 demonstrate a capacity of 117 mA h g −1 after 500 cycle at 0.5 C with a 74% retention rate, highlighting the effectiveness of the dual-doping strategy for creating superionic conductors for ASSBs.
研究领域:
材料科学
·
电化学
·
储能技术
·
固体离子学
·
电池技术
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Xuming Luo,Xianneng He,Han Su,Yu Zhong,Xiuli Wang,Jiangping Tu
Several halide electrolytes have come back into the spotlight with their high ionic conductivity, soft texture and compatibility with high-voltage electrodes. However, the instability with lithium metal has hindered their application in all-solid-state lithium-metal batteries (ASSLMBs). Thereby, it is urgent to find an efficient way to tackle this issue. Herein, we have simultaneously enhanced the kinetic stability towards lithium metal and intrinsic stability towards high-voltage cathodes for Li 2 ZrCl 6 electrolytes via effective dual-halogen strategy while the ionic conductivity of electrolyte is not sacrificed due to the effects of morphology modification. Specially, the symmetric Li/Li 2 ZrCl 5.2 F 0.8 /Li cell can cycle stably for over 2000 h (0.1 mA cm - 2 , 0.5 mA h cm - 2 ) and the modified electrolyte Li 2 ZrCl 5.2 F 0.8 also shows higher oxidative stability than the original Li 2 ZrCl 6 . The in-situ formed fluoride interphase (LiF, ZrF x ) can account for the excellent kinetic stability at Li/Li 2 ZrCl 5.2 F 0.8 interface while the improved oxidative stability can be attributed to the higher electronegativity of F element. Finally, the Li 2 ZrCl 5.2 F 0.8 is also proved appliable in the Li/Li 2 ZrCl 5.2 F 0.8 /LiNi 0.8 Co 0.1 Mn 0.1 O 2 battery in the form of stable and satisfied discharge capacity (∼106.9 mAh g - 1 , the 20th - 65th cycle) due to the achievement of kinetic stability at Li/Li 2 ZrCl 5.2 F 0.8 interface in the initial stage (the first ∼ 19 cycles). The clever dual-halogen strategy proposed in this work can effectively enhance the electrochemical stability of electrolytes and foster the application of cost-effective Li 2 ZrCl 6 halides in ASSLMBs.
研究领域:
材料科学
·
电化学
·
电池技术
✓ 已验证
DOI
高影响因子
JOURNAL OF POWER SOURCES
·
2023
·
IF 9.2
Wen Tang,Wei Xia,Fiaz Hussain,Jinlong Zhu,Songbai Han,Wen Yin,Pengcheng Yu,Jiuwei Lei,Denys S. Butenko,Liping Wang,Yusheng Zhao
Halide-type solid electrolytes (SEs) have emerged as a new class of promising Li + conductors due to their high ionic conductivity , good deformability and excellent oxidation stability. Nevertheless, to move a step closer to the application in all-solid-state lithium batteries (ASSLBs), the poor compatibility against metal anode for halide SEs needs to be addressed. Herein, a dual-halogen trigonal SE, Li 2 ZrCl 6- x F x is developed. With the proper incorporation of F, the SE can maintain high ionic conductivity and considerable moisture stability. Moreover, protective-layer-free ASSLBs prepared from the single SE and high-voltage cathode materials LiCoO 2 can be reversibly cycled in the voltage window of 2.52–4.32 V (versus Li + /Li) with a high initial coulombic efficiency of 95.57%, and maintain 76% of the initial capacity after 70 cycles. The good electrochemical performance is originated from the in-situ formed interface protective layer between SE and Li alloy, as demonstrated by X-ray photoelectron spectroscopy and computational characterizations. This work indicates that developing mixed halogen-based SEs is a cost-effective way to improve the stability of halide SEs against alkali metal anode, and could accelerate the application for high-voltage ASSLBs.
研究领域:
材料科学
·
电化学
·
能量存储
✓ 已验证
DOI
高影响因子
CHINESE CHEMICAL LETTERS
·
2023
·
IF 9.1
Haochang Zhang,Zhaozhe Yu,Jinyin Cheng,Hannan Chen,Xiao Huang,Bingbing Tian
Li 2 ZrCl 6 (LZC) solid-state electrolytes (SSEs) have been recognized as a candidate halide SSEs for all-solid-state Li batteries (ASSLBs) with high energy density and safety due to its great compatibility with 4 V-class cathodes and low bill-of-material (BOM) cost. However, despite the benefits, the poor chemical/electrochemical stability of LZC against Li metal causes the deterioration of Li/LZC interface, which has a detrimental inhibition on Li + transport in ASSLBs. Herein, we report a composite SSE combining by LZC and argyrodite buffer layer (Li 6 PS 5 Cl, LPSC) that prevent the unfavorable interaction between LZC and Li metal. The Li/LPSC-LZC-LPSC/Li symmetric cell stably cycles for over 1000 h at 0.3 mA/cm 2 (0.15 mAh/cm 2 ) and has a high critical current density (CCD) value of 2.1 mA/cm 2 at 25 °C. Under high temperature (60 °C) which promotes the reaction between Li and LZC, symmetric cell fabricated with composite SSE also display stable cycling performance over 1200 h at 0.3 mAh/cm 2 . Especially, the Li/NCM ASSLBs fabricated with composite SSE exhibit a high initial coulombic efficiency, as well as superior cycling and rate performance. This simple and efficient strategy will be instrumental in the development of halide-based high-performance ASSLBs.
研究领域:
材料科学
·
电化学
·
能源存储
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）