Materials Chemistry Frontiers
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2021
·Vol. 5
·期 16
·6171-6181
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IF 6.482
Liewu Li,Qi Yuan,Shenghua Ye,Yonghuan Fu,Xiangzhong Ren,Qianling Zhang,Jianhong Liu
The layered LiCoO2 cathode plays a key role in high-energy-density lithium-ion batteries (LIBs), delivering a capacity of ∼185 mA h g−1 at a high cut-off voltage of 4.5 V (vs. Li/Li+). However, its practical applications in high-voltage LIBs are limited by a severe side reaction and an irreversible structure transition during cycling. Herein, we report a facile surface coating technique to prepare the Li4SiO4-coated LiCoO2 composite (LiCoO2@Li4SiO4) to confront the issue of instability and increase the capacity of the LiCoO2 cathode at 4.5 V. Notably, the LiCoO2@Li4SiO4 electrode exhibits an exceptionally high initial discharge capacity (180.7 mA h g−1 at 0.1 C), a significantly enhanced rate capability (147.2 mA h g−1 at 5 C), and long-term cycling stability (capacity retention of 82.2% after 500 cycles at 2 C). The experimental results demonstrate that the Li4SiO4 coating could effectively reinforce the structural stability of the LiCoO2@Li4SiO4 electrode during cycling. Furthermore, the density functional theory calculation results further confirm that the Li4SiO4 coating facilitates the rapid Li+ diffusion at the LiCoO2@Li4SiO4 electrode. This work provides a potential strategy for interface engineering of the 4.5 V LiCoO2 cathode for high-energy-density LIBs.
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
产品关联
DOI
高影响因子
Advanced Materials Interfaces
·
2021
·Vol. 8
·期 15
·2100624
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IF 6.147
Zhen Sun,Yanqing Lai,Na lv,Yaqi Hu,Bingqin Li,Shenghao Jing,Liangxing Jiang,Ming Jia,Jie Li,Shiyou Chen,Fangyang Liu
Solid-state batteries exhibit promising prospects due to their potential in terms of safety and energy density. Sulfide solid electrolytes have received much attention due to their high ionic conductivity (about 10 −2 S cm −1 ). However, high side reactions between solid sulfide electrolytes and oxide cathodes, such as LiCoO 2 , have hampered the development of all-solid-state sulfide batteries. Here, first-principles calculations and experiments are combined to demonstrate a novel protective layer to cope with the Li 6 PS 5 Cl electrolyte and LiCoO 2 cathode interface problem. By uniformly coating LiCoO 2 with a layer of Li 2 WO 4 , the interfacial resistance (the 100th cycle) between the sulfide electrolyte and LiCoO 2 is reduced to about 68 Ω cm 2 , which is nearly 15 times lower than the premodified 1061 Ω cm 2 . The 2 wt% Li 2 WO 4 -coated LiCoO 2 (2%LWO-LCO)/Li 6 PS 5 Cl/Li-In all-solid-state battery exhibits satisfactory capacity and excellent cycling stability at room temperature (93% capacity retention after 100 cycles). Furthermore, the ab initio molecular dynamics based on the Perdew, Burke, and Ernzerhof density functional theory calculations show that Li 2 WO 4 can effectively prevent the diffusion of Co and O from LiCoO 2 into the Li 6 PS 5 Cl solid electrolyte. It is shown that molecular dynamics help predict the interfacial reactions in all-solid-state sulfide batteries.
研究领域:
材料科学
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电化学
✓ 已验证
产品关联
DOI
高影响因子
Nanoscale
·
2021
·Vol. 13
·期 16
·7822-7830
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IF 7.79
Yuwan Dong,Panzhe Su,Guanjie He,Huiling Zhao,Ying Bai
With high theoretical capacity and tap density, LiCoO2 (LCO) cathode has been extensively utilized in lithium-ion batteries (LIBs) for energy storage devices. However, the bottleneck of structural and interfacial instabilities upon cycling severely restricts its practical application at high cut-off voltage. From another perspective, the compatibility between the electrode and electrolyte is highly valued in the development of all-solid-state batteries. Herein, we construct a compatible interface between Li7La3Zr2O12 (LLZO) and LCO through a facile surface modification strategy, which significantly improves the cycling stability of LCO at a high cut-off voltage of 4.5 V. Characterization results demonstrate that the LCO@1.0 LLZO sample delivers a desirable capacity retention of 76.8% even after 1000 cycles at 3.0–4.5 V with the current density of 1 C (1 C = 274 mA g−1). Further investigation indicates that the LLZO modification layer could protect the LCO electrode through effectively alleviating the side reactions, which not only facilitates the Li+ transportation at the interface but also mitigates the bulk structure degradation. Moreover, it is also established that a small amount of La and Zr ions could gradiently migrate into the surface lattice of LCO to generate a thin layer of the surface solid solution Li–Co–La–Zr–O. Thus formed pinning region between surface modified LLZO and LCO cathode could contribute both to their mechanical compatibility and Li+ kinetics behavior upon repeated cycling. This work not only provides a strategy in broadening the operation potential and extracting higher capacity of LCO but also sheds light on constructing compatible interfaces in LIBs, especially for all-solid-state energy storage and conversion devices.
研究领域:
材料科学
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能源存储与转换
✓ 已验证
DOI
PubMed
高影响因子
RSC Advances
·
2020
·Vol. 10
·期 41
·24533-24541
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IF 3.119
Huiling Chen,Yuehua Wen,Yue Wang,Songtong Zhang,Pengcheng Zhao,Hai Ming,Gaoping Cao,Jingyi Qiu
For high-voltage cycling of lithium-ion batteries, a gel polymer Li-ion conductor layer, P(VDF-HFP)/LiTFSI (PHL) with high electrochemical stability has been coated on the surfaces of as-formed LiCoO2 (LCO) cathodes by a solution-casting technique at low temperature. An LCO cathode coated with around 3 μm thickness of the PHL ultrathin membrane, retains 88.4% of its original capacity (184.3 mA h g−1) after 200 cycles in the 3.0–4.6 V range with a standard carbonate electrolyte, while the non-coated one retains only 80.4% of its original capacity (171.5 mA h g−1). The reason for the better electrochemical behaviors and high-voltage cycling is related to the distinctive characteristics of the PHL coating layer that is compact, has highly-continuous surface coverage and penetrates the bulk of LCO, forming an integrated electrode. The PHL coating layer plays the role of an ion-conductive protection barrier to inhibit side reactions between the charged LCO surface and electrolyte, reduces the dissolution of cobalt ions and maintains the structural stability of LCO. Further, the PHL coated LCO cathode is well preserved, compared to the uncoated one which is severely cracked after 200 cycles at a charging cut-off voltage of 4.6 V.
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
DOI
高影响因子
ACS Applied Materials & Interfaces
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2024
·
IF 8.3
Yuwei Zhao,Wei Zeng,Shengqi Su,Jingzhe Wu,Jiangnan Ke,Yonggang Sun,Xijie Lin
The commercial application of high-voltage LiCoO2 (LCO) faces significant challenges due to rapid capacity decay, primarily attributed to an unstable interface and structure at deeply delithiated states. Herein, a unique rare earth oxide composite coating comprising La2O3, Y2O3, and LaYO3 has been prepared to stabilize LCO at high voltage. The synergistic effect between these rare earth oxides significantly reinforces the protective capabilities of the coating, effectively enhancing the interfacial/structural stability of LCO. When tested at 4.6 V, the coated LCO exhibits an excellent capacity retention of 94.4% after 300 cycles at 1 C. Even after an ultralong charge/discharge test of 700 cycles at 2 C, the coated LCO retains 85.2% of its initial specific capacity, which significantly outperforms the uncoated LCO (6.3%). Moreover, the coated LCO shows enhanced cycling performance at a high temperature of 45 °C, owing to the outstanding thermal stability of the La–Y–O composite. Additionally, the superior cycling stability of the coated LCO at 4.7 V, compared to the uncoated LCO, demonstrated the promising potential of the La–Y–O composite coating in improving electrochemical performance of LCO at higher cutoff voltages. These findings highlight an efficacious strategy to enhance the interfacial/structural stability of high-voltage LCO using rare earth oxides.
研究领域:
材料科学
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电化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
SOLID STATE IONICS
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2019
·
IF 2.886
Ning Xu,Hebing Zhou,Youhao Liao,Guanjie Li,Mengqing Xu,Weishan Li
The rapid capacity fading of LiCoO 2 cathodes under high temperature limits its further development in high energy density of lithium ion batteries , caused by the unmatched liquid electrolyte that tends to decompose when the working potential exceeds 4.2 V (vs. Li + /Li). Gel polymer membrane blended with PEO (poly(ethylene oxide)) and P(VdF-HFP) (poly(vinylidene fluoride- co -hexafluoropropylene)) is used to enhance the oxidative stability of liquid electrolyte in the polymer matrix . In order to maximize the capacity of LiCoO 2 cathode, proper amount of SN (succinonitrile) that helps to construct a stable CEI (cathode electrolyte interface) film is added into the electrolyte. The SN-contained GPE (gel polymer electrolyte) has the highest oxidative decomposition potential of 5.2 V and the lowest interfacial resistance . At 55 °C, the LiCoO 2 /GPE/Li coin-cell keeps 82% of capacity after 350 cycles in 3.0 V ~ 4.45 V at 1 C rate, compared with that of 9% capacity retention using the polyethylene separator saturated with liquid electrolyte. The enhancement in the cyclic stability under elevated temperature attributes to the dual strategies: the GPE guarantees the better oxidative stability by suppressing the further oxidative decomposition of liquid electrolyte, while the high quality CEI film formed by the SN additive protects the structural integrity of LiCoO 2 cathode.
研究领域:
材料科学
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电化学
✓ 已验证
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
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2025
·
IF 9.7
Qiujun Wang,Nana Bai,Yelun Xin,Xiaomeng Fan,Di Zhang,Zhaojin Li,Qujiang Sun,Huilan Sun,Bo Wang,Guoxu Wang,Li-Zhen Fan
LiCoO 2 (LCO) is a prominent high-voltage cathode material due to its exceptional energy density and impressive theoretical specific capacity of 274 mAh g −1 . However, challenges such as irreversible structural phase transitions, loss of reactive oxygen, and cobalt dissolution can lead to unstable interfaces between the electrolyte and the LCO cathode. In this study, sulfolane (SUL)-based composite polymer electrolytes (CPEs) were synthesized through in-situ polymerization, and the LCO cathode was modified using vinylidene carbonate (VC) and lithium difluoro(oxalato)borate (LiDFOB). The synergistic effects of SUL and VC/LiDFOB facilitated the formation of a more stable cathode-electrolyte interface (CEI) layer. Consequently, the Li/EFHTL-15 %SUL/LCO-VC-LiDFOB cell demonstrated excellent reversible cycling performance, achieving 86.36 % capacity retention after 300 cycles at 0.5C within a voltage range of 2.8–4.4 V at 25 ℃. This work provides a viable approach for enhancing the interface stability of the LCO cathode in CPEs.
研究领域:
材料科学
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电化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ACS Applied Energy Materials
·
2025
·
IF 5.5
Zhengde Wang,Zhengfeng Zhang,Xingkai Zhang,Rupeng Li,Yunxia Wang,Jin Li,Bin Zhang
The LiCoO2 cathode cannot maintain stable battery cycling under high voltage, as the undesired release of lattice O and harmful surface side reactions compromise its structural stability, resulting in battery capacity degradation. Herein, inspired by architectural engineering, we proposed a surface–bulk structure dual-reinforced strategy to tackle the aforementioned challenges by room-temperature Al-induced engineering, which could achieve surface disordering and phosphating and bulk gradient Ni doping of the LiCoO2 cathode. Such a multifunctional structure could delay the detrimental transition, restrain lattice O loss, reduce harmful surface side reactions, and form a phosphate-rich CEI with high ionic conductivity and stability. The as-prepared modified LiCoO2 as the cathode in lithium-ion batteries displayed remarkably enhanced cycle stability than bare LiCoO2 (91.9% vs 45.3% after 100 cycles in 3.0–4.6 V at a current density of 1 C). Even at a 5 C high rate, the modified LiCoO2 cathode also displayed superb battery cycling (92% after 100 cycles at 3.0–4.6 V). This room-temperature Al-induced engineering is universal to other layered cathode materials.
研究领域:
材料科学
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电化学
✓ 已验证
产品关联
DOI
高影响因子
ADVANCED FUNCTIONAL MATERIALS
·
2020
·Vol. 30
·期 22
·1909392
·
IF 16.836
Jiliang Qiu,Xinyu Liu,Rusong Chen,Qinghao Li,Yi Wang,Penghao Chen,Luyu Gan,Sang-Jun Lee,Dennis Nordlund,Yijin Liu,Xiqian Yu,Xuedong Bai,Hong Li,Liquan Chen
Poly(ethylene oxide) (PEO)-based solid electrolytes are expected to be exploited in solid-state batteries with high safety. Its narrow electrochemical window, however, limits the potential for high voltage and high energy density applications. Herein the electrochemical oxidation behavior of PEO and the failure mechanisms of LiCoO 2 -PEO solid-state batteries are studied. It is found that although for pure PEO it starts to oxidize at a voltage of above 3.9 V versus Li/Li + , the decomposition products have appropriate Li + conductivity that unexpectedly form a relatively stable cathode electrolyte interphase (CEI) layer at the PEO and electrode interface. The performance degradation of the LiCoO 2 -PEO battery originates from the strong oxidizing ability of LiCoO 2 after delithiation at high voltages, which accelerates the decomposition of PEO and drives the self-oxygen-release of LiCoO 2 , leading to the unceasing growth of CEI and the destruction of the LiCoO 2 surface. When LiCoO 2 is well coated or a stable cathode LiMn 0.7 Fe 0.3 PO 4 is used, a substantially improved electrochemical performance can be achieved, with 88.6% capacity retention after 50 cycles for Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 coated LiCoO 2 and 90.3% capacity retention after 100 cycles for LiMn 0.7 Fe 0.3 PO 4 . The results suggest that, when paired with stable cathodes, the PEO-based solid polymer electrolytes could be compatible with high voltage operation.
研究领域:
材料科学
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电化学
✓ 已验证
DOI
高影响因子
Materials Today Nano
·
2022
·
IF 13.364
Q. Sun,X. Chen,J. Xie,C. Huang,X. Xu,J. Tu,C. Shen,Y. Jin,K. Zhang,F. Chen,T. Zhu,X. Zhao,J. Cheng
Garnet-type Li 7 La 3 Zr 2 O 12 (LLZO) ceramics has been considered as an ideal solid-state electrolyte for Li metal cells because of its high ionic conductivity and relatively stable interface with Li. However, it is electrochemically incompatible with some high-voltage cathodes, e.g. LiCoO 2 . In this work, a nanoscale Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 (LATP) fast ion conductor was coated on LiCoO 2 (only 1 wt% LATP), bringing obviously enhanced interfacial compatibility with a composite electrolyte composed of Al, Nb-codoped LLZO and polyethylene oxide (PEO). A free-standing, flexible and ultrathin (20 μm) electrolyte membrane was successfully fabricated by a facile and scalable route, even though with a high ceramics content (67 wt%). Quasi-solid-state coin and pouch-type Li cells were assembled with the LATP-coated LiCoO 2 cathode, free-standing composite electrolyte and Li anode, together with soft interface modification by in-situ polymerization. The cells show stable cycling due to combined factors of enhanced electrode/electrolyte compatibility, ultrathin nature of the electrolyte membrane and the in-situ built soft interface. The pouch cells can be cycled for 300 cycles at 0.3 C and 60 °C with 80% retention. The pouch cells can endure abuse tests of bending, cutting and nail penetration. At a practical LiCoO 2 loading of 3 mAh cm −2 , the Li|LiCoO 2 pouch cell still shows stable cycling with 90% retention after 100 cycles at 60 °C (0.2 C charge/0.5 C discharge). This work provides a practical method to fabricate high-performance solid-state Li cells.
研究领域:
材料科学
·
电化学
·
固态电池
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能源材料
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界面工程
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纳米技术
✓ 已验证
DOI
高影响因子
JOURNAL OF ELECTROCERAMICS
·
2024
·
IF 1.7
Wang Yikui,Tao Jianming,Wang Jiangjie,Chen Shaoyang,Yang Yanmin,Lin Yingbin
Serious structural irreversibility and interfacial side reactions pose major challenges for the stable operation of LiCoO 2 cathodes at high voltages. Herein, we report a polymer-based solid electrolyte (SLP) composed succinonitrile, LiTFSI and PVDF as a binder to address these issues. The SLP binder exhibits superior performance compared to traditional PVDF and PVDF binders with LiTFSI, with higher ionic conductivity (8.46 × 10 − 5 S cm − 1 at 30 ℃), lower activation energy of 0.38 eV and excellent adhesion. Even with just 3% SLP binder, LiCoO 2 cathode operating at a cutoff voltage of 4.6 V and loaded with ~ 6.0 mg cm − 2 active material demonstrates improved rate capability at higher compaction densities, delivering a discharge specific capacity of 146.5 mAh g − 1 after 100 cycles at 0.5 C-rate. The SLP binder not only enhances Li + conduction but also facilitates the formation of a stable cathode-electrolyte interphase, thus reducing the Li + diffusion barrier and interface polarization, and enhancing battery’s performance at low temperature. Furthermore, the SPL binder’s high compatibility and elasticity with the electrolyte mitigate irreversible structural changes and volume expansion in LiCoO 2 during cycling, leading to better preservation of the layered structure and lower internal stress for stable cycling under high temperatures. This strategy provides a novel interface protection idea for electroceramic cathode materials and may facilitate commercial development.
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
ACS Nano
·
2024
·
IF 15.8
Yu Ye,Jiazhong Geng,Daxian Zuo,Kangdi Niu,Diancheng Chen,Junhao Lin,Xihan Chen,Haw Jiunn Woo,Yizhou Zhu,Jiayu Wan
All-solid-state batteries (ASSBs) have garnered considerable attention as promising candidates for next-generation energy storage systems due to their potentially simultaneously enhanced safety capacities and improved energy densities. However, the solid future still calls for materials with high ionic conductivity, electrochemical stability, and favorable interfacial compatibility. In this study, we present a series of halide solid-state electrolytes (SSEs) utilizing a doping strategy with highly valent elements, demonstrating an outstanding combination of enhanced ionic conductivity and oxidation stability. Among these, Li2.6In0.8Ta0.2Cl6 emerges as the standout performer, displaying a superionic conductivity of up to 4.47 mS cm–1 at 30 °C, along with a low activation energy barrier of 0.321 eV for Li+ migration. Additionally, it showcases an extensive oxidation onset of up to 5.13 V (vs Li+/Li), enabling high-voltage ASSBs with promising cycling performance. Particularly noteworthy are the ASSBs employing LiCoO2 cathode materials, which exhibit an extended cyclability of over 1400 cycles, with 70% capacity retention under 4.6 V (vs Li+/Li), and a capacity of up to 135 mA h g–1 at a 4 C rate, with the loading of active materials at 7.52 mg cm–2. This study demonstrates a feasible approach to designing desirable SSEs for energy-dense, highly stable ASSBs.
研究领域:
材料科学
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能源存储
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电池技术
·
电化学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）