CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Yu-Wei Zhao,Wei Zeng,Sheng-Qi Su,Si-Dong Zhang,Si-Jie Guo,Jian-Hua Qiu,Yong-Gang Sun,An-Min Cao,Xi-Jie Lin
Surface coating as an effective strategy has been extensively utilized to enhance the surface/interface stability of cathode for lithium-ion batteries. As widely recognized, the electrochemical performance of coated cathode is greatly dependent on the properties of coating layer. Rational design on the structure and composition of coating layer becomes crucial. Here, a unique “island-bridge” shaped Zr-based coating layer has been constructed through a facile synthetic protocol. This coating layer composes of several high-crystalline ZrO 2 nanoparticles and a thin low-crystalline zirconium hydroxide layer that connects these nanoparticles, forming a typical “island-bridge” structure. The successful formation of such a unique coating layer was demonstrated to be related to the usage amount of Zr source and the calcined temperature. The novel “island-bridge” coating has been successfully applied to modify the surface of LiCoO 2 , showing excellent capability on improving the electrochemical performance. The unique “island-bridge” structure coating induces the formation of a triple-phase interface, namely island-cathode-bridge interface. Theoretical calculation suggests that such an island-cathode-bridge triple-phase interface can effectively reduce the Li + diffusion energy, leading to favorable Li + transportation kinetics and suppressed cathode-electrolyte interface evolution. Furthermore, this “island-bridge” layer can well prevent direct contact between LiCoO 2 and electrolyte, enhancing the surface/interface stability, resulting in improved cyclic performance. This work provides new insights into the rational design of surface coating for high-energy density cathodes.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
Advanced Energy Materials
·
2023
·Vol. 13
·期 37
·2302058
·
IF 27.8
Zhenzhen Liu,Huaimeng Li,Miaomiao Han,Liang Fang,Zhen Fu,Haimin Zhang,Guozhong Wang,Yunxia Zhang
Faced with the forthcoming tide of retired lithium-ion batteries (LIBs), it is imperative to explore effective regeneration and upcycling strategies to alleviate the resource shortage, address environmental pollution, and cater to the demand for high-energy-density cathode materials. Herein, a facile, non-constructive, one-stone-for-three-birds solid-phase sintering strategy is proposed to regenerate the degraded LiCoO 2 (D-LCO) cathode and even upgrade its stability at high voltages, in which three birds, i.e., lithium supplement, Li 2 SO 4 coating, and Mn doping into Co sites while N, S doping into Li-O slabs are simultaneously hit with one stone (one-pot solid-phase sintering). Benefiting from these favorable characteristics, the upcycled cathode not only yields high discharge-specific capacity of 188.2 mAh g −1 at 0.2 C, but also delivers superior cycling performance with 92.5% of capacity retention after 100 cycles (86.4% after 300 cycles) at 0.5 C and excellent rate capability at a high cutoff voltage of 4.5 V, superior to a freshly commercial counterpart. This work is expected to provide meaningful guidance for the upcycling of D-LCO into high-energy-density batteries with long-term cycling stability.
研究领域:
材料科学
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能源技术
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF POWER SOURCES
·
2021
·
IF 9.127
Bei Hu,Fushan Geng,Ming Shen,Chong Zhao,Qing Qiu,Yang Lin,Changxin Chen,Wen Wen,Shun Zheng,Xiaoshi Hu,Chao Li,Bingwen Hu
LiCoO 2 , as a domain cathode material of Li-ion batteries, faces a great deal of challenges due to the limited cycling stability at high voltage (>4.35 V vs. Li/Li + ). These issues are tentatively addressed here by a multifunctional self-stabilization modification strategy, involving trace Mg bulk doping, surface gradient Ti doping and BaTiO 3 dot coating in LiCoO 2 . The multifunctional synergy is verified to overcome the detrimental irreversible phase transition and the growth of impedance of LiCoO 2 cycling at 4.6 V. By using soft X-ray absorption spectroscopy (sXAS) and electron paramagnetic resonance (EPR) techniques, we also elucidate that Ti surface gradient doping can reinforce the structure rigidity of the particles while significantly attenuates the irreversible oxygen redox at high voltage. All these strategies promote the prolonged cyclic performance of LiCoO 2 under 4.6 V high-voltage through different mechanism. This elaborate investigation provides an instructive contribution in the advancement of high-voltage LiCoO 2 .
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
International Journal of Applied Ceramic Technology
·
2024
·
IF 1.8
Biao Yang,Bo Yin,Han Chen,Yifeng Zheng
LiCoO 2 has become the most widely used cathode material in lithium-ion batteries because of its high capacity and excellent stability. The high-temperature solid-state method is commonly used for the preparation of LiCoO 2 . However, this method will produce highly penetrating Li 2 O, which causes spall or fracture of the insulating refractory materials in the kiln. In this study, the corrosion resistance of bubble alumina, mullite, and calcium hexaaluminate (CA 6 ) insulating refractories to LiCoO 2 has been thoroughly investigated. Combining the laboratory-scale interfacial reaction experiments with post-experimental life cycle analysis of industrial insulating refractories, the interaction between the insulating refractory materials and LiCoO 2 after calcination at 900°C for 5 h and the corrosion behavior of LiCoO 2 on different insulating refractory materials following heat treatment at 900°C for 5 h every time and repeated seven times are investigated. The corrosion mechanisms are concluded by analyzing the physicochemical composition and macro- and micromorphology of the three insulating refractory materials before and after corrosion. The results can provide a basis for the use of insulating refractories in the development of lithium batteries.
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2021
·
IF 8.198
Yue Zou,Ang Fu,Jing Zhang,Tianpeng Jiao,Yong Yang,Jianming Zheng
To achieve higher energy density, LiCoO2 (LCO) is being developed for high-voltage operation at raised charge cutoff voltages up to 4.6 V vs Li/Li+, which however is beyond the electrochemical stability window of carbonate-based electrolytes. In this work, a novel electrolyte additive 2,4,6-tris(4-fluorophenyl)boroxin (TFPB) is proposed for enhancing the interfacial stability of LCO. Thanks to the TFPB additive, the LCO cathode exhibits substantially improved capacity retention of 84.6% after 200 cycles at 1C at a high charge cutoff of 4.6 V, surpassing the 63.2% attained in the baseline electrolyte. The improved performance could be rationalized by the fact that TFPB additive is preferentially oxidized to build a uniform and protective B–O bond-containing cathode–electrolyte interphase, contributing to the reduced parasitic side reactions, inhibited surface structural transformation, and better-maintained interfacial lithium-ion diffusion kinetics.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
ChemElectroChem
·
2021
·Vol. 8
·期 13
·2534-2544
·
IF 4.59
Lengdan Zhang,Xiaoxi Zuo,Tianming Zhu,Wenping Lei,Dongming Xie,Jiansheng Liu,Xin Xiao,Xinli Chen,Junmin Nan
Graphical The role performed by the tetrafluoroethane beta-sultone (TFBS) additive for improving the electrochemical properties of LiCoO 2 /graphite pouch cells at higher charging cutoff voltage (4.5 V) is raised. The energy density of lithium cobalt oxide (LiCoO 2 )-based cells can be increased by charging at voltages above 4.2 V. However, the poor interface stability of the cathode/electrolyte deriving from the continuous severe decomposition of the electrolyte on the cathode/electrolyte surface and the instability of the structure of the cathode at high-voltage operation limits their wider commercial application. Herein, a new fluoro-functionalized electrolyte additive, tetrafluoroethane beta-sultone (TFBS), is used for promoting the electrochemical performance of LiCoO 2 -based cells. Upon cycling between 3.0 and 4.5 V (vs. Li/Li + ) with 0.5 C (1 C=274.4 mAh/g), it is shown that the capacity retention of the LiCoO 2 /graphite pouch-cell with TFBS-controlled electrolyte reaches 96.8 % (183.9 mAh g −1 ), yet it is 66.5 % (126.3 mAh g −1 ) for the pouch-cell without TFBS in baseline electrolyte at the 100 th cycle. All the results indicate that TFBS can be decomposed prior to the solvents in the electrolyte and can then form low-resistance, high-conductivity interface layers on the surfaces of the cathode-electrolyte and the anode-electrolyte, respectively, thus improving the cycling stability of the cells at a high charging cutoff voltage (4.5 V).
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
ADVANCED FUNCTIONAL MATERIALS
·
2023
·Vol. 33
·期 30
·2300589
·
IF 19
Chao Sun,Bing Zhao,Jing Mao,Ke-Hua Dai,Zhen-yu Wang,Lin-bo Tang,He-zhang Chen,Xia-hui Zhang,Jun-chao Zheng
LiCoO 2 plays a key role in energy storage devices due to its high energy density. And the volumetric energy density of LiCoO 2 cathode can be significantly improved by increasing the charging cut-off voltage to 4.6 V. However, the increase in resistance at the LiCoO 2 interface, and the damage to the LiCoO 2 from the outside to the inside by the HF generated that caused by the decomposition of the organic electrolyte and LiPF 6 under 4.6 V conditions are not conducive to structural stability during cycling. Here, it is shown that the decomposition of electrolyte and LiPF 6 is effectively mitigated by inhibiting the interfacial catalytic activity of LiCoO 2 using an atomically thin layer of MXenes as a interlayer. Density functional theory results suggest that the decomposition energy of LiPF 6 is 1.13 and 3.21 eV at the interface of LiCoO 2 and MXenes, respectively. Time of Flight Secondary Ion Mass Spectrometry results further indicate that the decomposition products of the organic electrolyte and LiPF 6 have a thinner thickness at the interface of MXenes (5 nm) than LiCoO 2 (10 nm). This study provides a new and universal strategy for stabilizing the cathode interface to support the development of high energy density lithium-ion batteries.
研究领域:
材料科学
·
电化学
·
能源存储
✓ 已验证
DOI
高影响因子
WASTE MANAGEMENT
·
2021
·
IF 7.145
Huimeng Yang,Bowen Deng,Xiaoyun Jing,Wei Li,Dihua Wang
Regenerating cathode material from spent lithium-ion batteries (LIBs) permits an effective approach to resolve resource shortage and environmental pollution in the increasing battery industry. Directly renovating the spent cathode materials is a promising way, but it is still challenging to efficiently remove all of the complex impurities (such as binder, carbon black, graphite and current collectors) without destroying the material structure in the electrode. Herein, a facile strategy to directly remove these impurities and simultaneously repair the degraded LiCoO 2 by a target healing method is reported. Specifically, by using an optimized molten salt system of LiOH-KOH (molar ratio of 3:7) where LiNO 3 and O 2 both serve as oxidants, the impurities can be completely removed, while the structure, composition and morphology of degraded LiCoO 2 can be successfully repaired to commercial level based on a two-stage heating process (300 °C for 8 h and 500 °C for 16 h, respectively), resulting in a high recovery rate of approximately 100% for cathode material. More importantly, the regenerated LiCoO 2 exhibits a high reversible capacity, good cycling stability and excellent rate capability, which are comparable with commercial LiCoO 2 . This work demonstrates an efficient approach to recycle and reuse advanced energy materials.
研究领域:
材料科学
·
环境科学
✓ 已验证
DOI
高影响因子
JOURNAL OF ELECTROANALYTICAL CHEMISTRY
·
2020
·
IF 3.807
Yiping Sun,Houcai Dong,Kuan Wu,Xi Chen,Shaofei Wang,Wei Gu,Ziwei Hong,Min Liu,Yanbin Shen,Wei Lu
Surface coating is an efficient strategy to enhance the interfacial stability of the electrode. Graphene quantum dots (GQDs) have advantages of excellent dispersion in water, outstanding electron and ion conductivities and high specific surface area. In this work, GQDs were coated directly on the surface of LiCoO 2 particles (GQDs-LiCoO 2 ) through liquid phase method. Compared to bare LiCoO 2 , the cycling performance, rate capacity and thermo-stability of the GQDs-LiCoO 2 have been significantly improved in the voltage range of 3.04.5 V. GQDs-LiCoO 2 showed a much higher capacity retention than that of bare LiCoO 2 (82.8 % vs 46.1 %) after 100 cycles at 0.5 C. The excellent improvement of the GQDs-LiCoO 2 was mainly attributed to the formation of a uniform, stable, dense and well-conductive protective layer on the surface of LiCoO 2 particles by the surface coating of GQDs. The detailed analysis of the cycled electrodes reveals that the GQDs coating stabilizes the crystal structure of LiCoO 2 and suppresses undesirable interfacial side reactions between the cathode and electrolyte, leading to the improvement of battery performance.
研究领域:
材料科学
·
电化学
·
能源存储
·
锂离子电池
·
界面工程
✓ 已验证
DOI
高影响因子
JOURNAL OF POWER SOURCES
·
2021
·
IF 9.127
Zhaoyu Sun,Hebing Zhou,Xuehuan Luo,Yanxia Che,Weishan Li,Mengqing Xu
A novel electrolyte additive designed as a cathode interface formation enhancer for high voltage lithium-ion battery (LIB) systems is investigated. Lithium 4-benzonitrile trimethyl borate (LBTB) is synthesized by a two-step reaction, and the results show that the cycling performance of Li/LiCoO 2 cell at 4.4 V is significantly improved from 15.08% to 73.21% by adding 2.0 wt% of LBTB to the electrolyte (1.0 M LiPF 6 in EC/DEC/EMC = 3/2/5, wt.%). A combination of electrochemical methods , ex-situ spectroscopy characterization techniques and computational calculations are employed to investigate the mechanisms of action for this additive. Cyclic voltammograms indicate the additive is preferably oxidized on the LiCoO 2 surface prior to the electrolyte oxidation and results in a more stable and robust passivation layer than the electrolyte alone. Computational calculations support the observed sacrificial oxidation of LBTB prior to the electrolyte solvents decomposition. The CEI formed by LBTB decomposition mitigates the dissolution of transition metal and subsequently improves the cycling stability of the LiCoO 2 cathodes at high voltages. Surface characterization techniques reveal the presence of -B-O- products derived from LBTB decomposition on the surface of the LCO cathode.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
Nanoscale Research Letters
·
2020
·Vol. 15
·期 1
·1-10
·
IF 3.578
Song Shipai,Peng Xiang,Huang Kai,Zhang Hao,Wu Fang,Xiang Yong,Zhang Xiaokun
The stability issue of LiCoO 2 cycled at high voltages is one of the burning questions for the development of lithium ion batteries with high energy density and long cycling life. Although it is effective to improve the cycling performance of LiCoO 2 via coating individual LiCoO 2 particles with another metal oxides or fluorides, the rate capacity is generally compromised because the typical coating materials are poor conductors. Herein, amorphous Li 0.33 La 0.56 TiO 3 , one of the most successful solid electrolytes, was directly deposited on the surface of made-up LiCoO 2 electrodes through magnetron sputtering. Not only the inherent conductive network in the made-up LiCoO 2 electrodes was retained, but also the Li + transport in bulk and across the cathode-electrolyte interface was enhanced. In addition, the surface chemical analysis of the cycled LiCoO 2 electrodes suggests that most of the stability issues can be addressed via the deposition of amorphous Li 0.33 La 0.56 TiO 3 . With an optimized deposition time, the LiCoO 2 electrodes modified by Li 0.33 La 0.56 TiO 3 performed a steady reversible capacity of 150 mAh/g at 0.2 C with the cutoff voltage from 2.75 to 4.5 V vs . Li + /Li and an 84.6% capacity gain at 5 C comparing with the pristine one.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
PubMed
高影响因子
Journal of Energy Chemistry
·
2023
·
IF 13.1
Jiangli Feng,Chenhui Wang,Hailin Lei,Songtao Liu,Jing Liu,You Han,Jinli Zhang,Wei Li
Lithium cobalt oxide (LiCoO 2 ) is proverbially employed as cathode materials of lithium-ion batteries attributed to the high theoretical capacity, and currently, it is developing towards higher cut-off voltages in the pursuit of higher energy density. However, it suffers from serious structural degradation and surface side reactions, in particular, at the voltage above 4.60 V, leading to rapid decay of the battery life. Taking into account the desirable oxygen buffering property and the fast ion mobility characteristic of cerium oxide fluoride, in this work, we prepared Ce & F co-modified LiCoO 2 by using the precursors of Ce(NO 3 ) 3 ·6H 2 O and NH 4 F, and evaluated the electrochemical performance under voltages exceeding 4.60 V. The results indicated that the modified samples have multiphase heterostructure of surface CeO 2− x and unique Ce O F solid solution phase. At 3.0–4.60 V and 25 °C, the preferred sample LCO-0.5Ce-0.3F has a high initial discharge specific capacity of 221.9 mA h g −1 at 0.1 C, with the retention of 80.3% and 89.6% after 300 cycles at 1 and 5 C, comparing with the pristine LCO (56.4% and 22.6%). And at 3.0–4.65 V, its retention is 64.0% after 300 cycles at 1 C, versus 8.5% of the pristine LCO. Through structural characterizations and DFT calculations, it suggests that Ce 4+ & F − co-doping suppresses the H3 to H1/3 irreversible phase transition, stabilizes the lattice structure, and reduces the redox activity of the lattice oxygen by modulating the Co 3 d –O 2 p energy band, consequently improving the electrochemical performance of LiCoO 2 at high voltages.
研究领域:
材料科学
·
电化学
·
电池技术
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）