Energy Storage Materials
·
2025
·
IF 20.2
Yongsheng Ji,Dan Yang,Yan Li,Maxim Avdeev,Wang Hay Kan,Mengyi Liao,Zhenyan Zhang,Weichen Du,Xinpeng Pi,Chaofan Liang,Zhou Fang,Xiaoqun Qi,Lan Xue,Renyuan Zhang,Long Qie,Yunhui Huang
The proliferation of lithium-ion batteries results in a substantial accumulation of spent batteries. Traditional pyrometallurgical and hydrometallurgical processes require significant energy inputs, involve the use of hazardous chemicals, and generate large amounts of pollutants, making them inefficient for the economic or environmental recycling of spent batteries. For the spent lithium cobalt oxide (LCO) cathodes, which lose electrochemical activity due to the structural damage, we demonstrated that LiF could serve as both a crack/defect healer to repair the damaged structure and a structural stabilizer to consolidate the electrode/electrolyte interface and the reversibility of phase transitions. The density functional theory calculations revealed the presence of F atoms in the U-LCO crystal leads to a widened energy separation between the Co 3d and O 2p orbitals, such an alteration effectively suppresses the activity of lattice oxygen and stabilizes the structure of U-LCO. The as-upcycled LCO cathode demonstrates significantly improved stability with an impressive capacity retention of 81.6% after 260 cycles, surpassing those of the pristine LCO (62.3%) and normally regenerated LCO (35.6%). Moreover, the recycling process only involves a solid sintering procedure, leading to a reduced carbon footprint by 73.1% and 64.1%, and increased benefits by 62.2% and 47.7%, as compared with the pyro and hydro methods, respectively. The as-proposed upcycling strategy provides a practical and efficient solution for the closed-loop development of LCO batteries.
研究领域:
材料科学
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
Nanomaterials
·
2021
·Vol. 11
·期 12
·3393
·
IF 5.076
Shasha Qu,Wenbin Wu,Yunfan Wu,Yanping Zhuang,Jie Lin,Laisen Wang,Qiulong Wei,Qingshui Xie,Dong-Liang Peng
Lithium cobalt oxide (LCO) is the most widely used cathode materials in electronic devices due to the high working potential and dense tap density, but the performance is limited by the unstable interfaces at high potential. Herein, LiF thin film is sputtered on the surface of LCO electrodes for enhancing the electrochemical performance and reducing the voltage polarization. The polarization components are discussed and quantified by analyzing the relationship between electrochemical polarization and charger transfer resistance, as well as that between concentration polarization and Li-ion diffusion coefficients. In addition, the decreased charge transfer resistance, increased lithium-ion diffusion coefficients, and stabilized crystal structure of LiF-coated LCO are confirmed by various electrochemical tests and in-situ XRD experiments. Compared to that of pristine LCO, the capacity and cycling performance of LiF-coated LCO is improved, and the overpotential is reduced upon cycling. This work provides reference for quantifying the various polarization components, and the strategy of coating LiF film could be applied in developing other analogous cathode materials.Keywords:voltage polarization;lithium cobalt oxide;lithium fluoride;lithium-ion battery
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
PubMed
高影响因子
Journal of Cleaner Production
·
2018
·
IF 5.651
JiaKai Mao,Jia Li,Zhengming Xu
The wider application of lithium ion batteries brings more production of spent ones to be recovered. There is a pyrometallurgical treatment by getting negative and positive materials burning together. The paper provides theoretical analysis and support for the feasibility of the treatment. Positive material graphite's burning and pyrolysis of negative material lithium cobalt oxide can make up as a coupling reaction, decreasing the decomposition temperature of lithium cobalt oxide from 1426 K to 1173 K. From the point view of crystal structure, the stronger attraction of graphite to oxygen than lithium and cobalt make oxygen octahedrons insides lithium cobalt oxide unstable to break down. We definite the phenomenon as the oxygen octahedrons collapsing model. Coupling reaction theory and crystal structure analysis indicate that graphite does promote the pyrolysis of lithium cobalt oxide. The study can guide industrial application to recover lithium ion batteries whose structure is similar to oxygen octahedrons at a comparatively low temperature.
研究领域:
冶金学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
Nature Communications
·
2020
·Vol. 11
·期 1
·1-10
·
IF 12.121
Yang Ya-Nan,Li Ying-Xiang,Li Yi-Qiu,Zhang Tao
Lithium garnets have been widely studied as promising electrolytes that could enable the next-generation all-solid-state lithium batteries. However, upon exposure to atmospheric moisture and carbon dioxide, insulating lithium carbonate forms on the surface and deteriorates the interfaces within electrodes. Here, we report a scalable solid sintering method, defined by lithium donor reaction that allows for complete decarbonation of Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO) and yields an active LiCoO 2 layer for each garnet particle. The obtained LiCoO 2 coated garnets composite is stable against air without any Li 2 CO 3 . Once working in a solid-state lithium battery, the LiCoO 2 -LLZTO@LiCoO 2 composite cathode maintains 81% of the initial capacity after 180 cycles at 0.1 C. Eliminating CO 2 evolution above 4.0 V is confirmed experimentally after transforming Li 2 CO 3 into LiCoO 2 . These results indicate that Li 2 CO 3 is no longer an obstacle, but a trigger of the intimate solid-solid interface. This strategy has been extended to develop a series of LLZTO@active layer materials.
研究领域:
材料科学
·
能源存储
✓ 已验证
DOI
高影响因子
JOURNAL OF POWER SOURCES
·
2019
·
IF 7.467
Bin Wang,Xin-Ye Lin,Yuanyuan Tang,Qiang Wang,Michael K.H. Leung,Xiao-Ying Lu
With the massive consumption of lithium-ion batteries in portable consumer electronics and electric vehicles, proper disposal of spent batteries is of paramount importance for sustainable development. In this study, biodegradable organic methanesulfonic acid (MSA) is investigated for the first time to leach valuable metals from waste LiCoO 2 powders for battery material regeneration. Under the optimal conditions, leaching efficiencies of lithium and cobalt are achieved at nearly ∼100% and ∼100%, respectively. Comparison experiment indicates that MSA can achieve better leaching performance than previously reported organic acids (e.g. citric acid , malonic acid , succinic acid , oxalic acid) under the same conditions. Besides, strong leaching capability of MSA at high solid-to-liquid ratios (e.g. 81.2 g L −1 and 163 g L −1 ) is confirmed with satisfactory leaching efficiencies (ca. 92.4%–100%). Feasibility test of MSA utilization for proper treatment of spent batteries is demonstrated at the optimized conditions. Importantly, regeneration study suggests that the as-obtained leachate can be employed to synthesize Co 3 O 4 anode and LiCoO 2 cathode materials with micro/nanostructures. Excellent cycling performance and rate capability of the regenerated electrode materials are demonstrated in the repeated charge-discharge cycles. Overall, the proposed recycling strategy is of great significance for rational resource utilization of spent lithium-ion batteries.
研究领域:
材料科学
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
CHINESE JOURNAL OF CHEMISTRY
·
2016
·Vol. 35
·期 1
·35-40
·
IF 1.872
Xuan Shao,Tao Zhang,Zhaoyin Wen
Conventional binders in the cathode of Li-O 2 batteries are insulated, and integrate with the catalyst and the conducting carbon-support by physical mixing. This limits the transfer of electrons, degrades the cathode structure due to swelling, and finally leads to capacity fading and is deleterious to cycleability. In this study, we realized, for the first time, a one-step fabricated Co 3 O 4 -PPy cathode characterized by an in-situ formed conductive polymer binder. The functional binder, polypyrrole (PPy), was synthesized through electrical method, which acted as both the binder and supporting material in the Li-O 2 battery. Based on the conductive property of PPy, we obtained the Co 3 O 4 -PPy@Ni electrode via the process of CV electro-deposition. This method results in uniform distribution of Co 3 O 4 nanoparticles and can simplify the preparation process of the air cathodes. The Li-O 2 battery with the Co 3 O 4 -PPy@Ni cathode can discharge/charge for over 30 cycles under the limited specific capacity of 1000 mAh/g. The cycleability and impedance spectra of the Li-O 2 battery with the functional binder of PPy are superior to the battery with conventional binders.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
Science Advances
·
2024
·Vol. 10
·期 33
·
IF 11.7
Ang Gao,Shijie Shen,Tongtong Shang,Yuansheng Shi,Huanhuan Zhang,Weiguang Lin,Shiyu Wang,Ting Lin,Pengxiang Ji,Yichi Wang,Yujie Chen,Botao Yu,Xia Lu,Wenwu Zhong,Qinghua Zhang,Lin Gu
High-voltage phase transition constitutes the major barrier to accessing high energy density in layered cathodes. However, questions remain regarding the origin of phase transition, because the interlayer weak bonding features cannot get an accurate description by experiments. Here, we determined van der Waals (vdW) interaction (vdWi) in LixCoO2 via visualizing its electron density, elucidating the origin of O3─O1 phase transition. The charge around oxygen is distorted by the increasing Co─O covalency. The charge distortion causes the difference of vdW gap between O3 and O1 phases, verified by a gap corrected vdW equation. In a high charging state, excessive covalency breaks the vdW gap balance, driving the O3 phase toward a stable O1 one. This interpretation of vdWi-dominated phase transition can be applied to other layered materials, as shown by a map regarding degree of covalence. Last, we introduce the cationic potential to provide a solution for designing high-voltage layered cathodes.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
Nano-Micro Letters
·
2022
·Vol. 14
·期 1
·1-13
·
IF 23.655
Li Jiawen,Ji Yuchen,Song Haoran,Chen Shiming,Ding Shouxiang,Zhang Bingkai,Yang Luyi,Song Yongli,Pan Feng
The cycle performance of poly(ethylene oxide) (PEO)-based all-solid-state lithium batteries with LiCoO 2 cathode was greatly improved via coating LiCoO 2 with high-voltage stable Li 3 AlF 6 .
At the upper cutoff voltage of 4.2 V, the poor electrochemical performance is mainly originated from the structure collapse of LiCoO 2 at the surface instead of the decomposition of PEO.
When the voltage reaches 4.5 V or even higher potentials, the intensive electrochemical decomposition of PEO-based solid polymer electrolyte accelerated interfacial degradation.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
Energy Storage Materials
·
2025
·
IF 20.2
Kai Zhang,Zeyu Wang,Zhenming Xu,Xing Zhou,Guodong Li,Zhe Mei,Yi Yu,Yonggang Wang,Congxiao Wang,Guannan Zhu,Yong-Ning Zhou,Yongyao Xia
Lithium cobalt oxide (LCO) has received considerable attention due to its high volumetric energy density, particularly at elevated cut-off voltages up to 4.7 V. However, the poor cyclic stability of high-voltage LCO limits its practical application, primarily due to detrimental phase transitions above 4.55 V, oxygen loss upon deep delithiation, and the interfacial side reactions. In this study, we introduce an in-situ formed strain buffer layer on LCO particles by CePO 4 coating to improve its high-voltage performance. The coated CePO 4 layer reacts with LCO particles spontaneously to generate a lattice-matched Li 8 CeO 6 phase, which can facilitate Li + transportation and relieve near-surface intrinsic stress. With less lattice strain, the undesirable phase transition and notorious surface degradation are suppressed significantly. Moreover, strong covalence of Ce 4f and O 2p bonds, and delocalized electrons in Ce-O 6 octahedral configuration help to suppress oxygen redox at 4.6 V. A high capacity retention of 93.3% after 300 cycles at 4.6 V and 88% after 100 cycles at 4.7 V is harvested. This strategy of constructing a strain buffer layer near the particle surface provides a novel insight for stabilizing the high-voltage LCO and paves the way for further modification of other cathode materials.
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
CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Shiyou Wu,Tongxing Lei,Zhiyu Ding,Jun Wei,Junwei Wu
Lithium cobalt oxide (LCO) cathode materials could deliver about 220 mAh/g when operated at 4.6 V. However, high-voltage LCO materials still endure detrimental interfacial side reactions and serious structural degradation, leading to severe performance deterioration. Herein, we have proposed a facile strategy that utilizes good-wettability LiPO 3 and ionically conductive Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 (LATP) to successfully construct a highly stable Li 3 PO 4 layer and a well-matched transition layer (such as Co 2 TiO 4 and LiCoPO 4 ) on the surface of LCO material. The designed multifunctional coating can not only suppress the oxygen release and electrolyte decomposition but also facilitate Li + diffusion kinetics. As a result, the modified LCO exhibits superior cycling stability over 200 cycles at 4.6 V, with excellent capacity retentions of 79.24 % at room temperature and 79.45 % at high temperature of 45 ℃. Besides, the modified LCO realizes a reversible discharge capacity of 178.42 mAh/g at 3C (1C = 200 mA/g) over 300 cycles. This work provides a practical reference for mass-production of high-voltage LCO with long lifespan and high-rate capability.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
JOM
·
2023
·Vol. 75
·期 9
·3632-3642
·
IF 2.6
Fei Zitong,Xing Yusen,Dong Peng,Meng Qi,Zhang Yingjie
The traditional direct regeneration of cathode material of spent lithium-ion batteries is encountering the challenge of high energy consumption. Here, an oxidative hydrothermal solution has been developed for direct regeneration of spent LiCoO 2 materials in low-temperature operation. The regenerated cathode material displays a better structural transformation with single-crystal particle morphology. More Co 2+ in spent LiCoO 2 materials are successfully transformed to Co 3+ in regenerated cathode materials. The initial discharge capacity of regenerated cathode materials reaches 153.46 mAh/g with a capacity retention rate of 95.02% after 200 cycles, which are both significantly higher than that of 39.83% in regenerated materials obtained by the traditional hydrothermal regeneration process. This oxidative hydrothermal solution can provide the electrochemical driving force to accelerate the repair of defects of spent cathode materials and break the limit of kinetics under low-temperature conditions. The low-temperature hydrothermal regeneration process is available to guide efficient and economically reasonable recycling of spent cathode materials.
研究领域:
材料科学
·
能源工程
·
环境科学
✓ 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）