文献类型：期刊文献

英文题名：Ultrathin dense LiF coverage coupled with a near-surface gradient fluorination lattice enables fast-charging long-life 4.6 V LiCoO2

作者：Bi, Zhihong[1,4];Yi, Zonglin[2];Zhang, Liangzhu[6];Wang, Gongrui[1,5];Zhang, Anping[1,4];Liao, Shihao[1];Zhao, Qinghe[3];Peng, Zhangquan[10];Song, Li[11];Wang, Yi[1,4];Zhao, Zhiwei[10];Wei, Shiqiang[11];Zhao, Wenguang[3];Shi, Xiaoyu[1,5];Li, Mingrun[1];Ta, Na[1];Mi, Jinxing[7];Li, Shunning[3];Das, Pratteek[1,5];Cui, Yi[8,9];Chen, Chengmeng[2];Pan, Feng[3];Wu, Zhong-Shuai[1,5]

机构：[1]Chinese Acad Sci, State Key Lab Catalysis, Dalian Inst Chem Phys, 457 Zhongshan Rd, Dalian 116023, Peoples R China;[2]Inst Coal Chem, Chinese Acad Sci, CAS Key Lab Carbon Mat, Taiyuan 030001, Peoples R China;[3]Peking Univ, Sch Adv Mat, Shenzhen Grad Sch, Shenzhen 518055, Peoples R China;[4]Univ Chinese Acad Sci, 19 A Yuquan Rd, Beijing 100049, Peoples R China;[5]Chinese Acad Sci, Dalian Natl Lab Clean Energy, 457 Zhongshan Rd, Dalian 116023, Peoples R China;[6]East China Univ Sci & Technol, Sch Mat Sci & Engn, Shanghai 200237, Peoples R China;[7]Tsinghua Univ, Sch Environm, State Key Joint Lab Environm Simulat & Pollut Cont, Beijing 100084, Peoples R China;[8]Suzhou Inst Nanotech & Nanob, Chinese Acad Sci, Vacuum Interconnected Nanotech Workstat, Suzhou 215123, Peoples R China;[9]Univ Sci & Technol China, Sch Nano Technol & Nano Bion, Hefei 230026, Peoples R China;[10]Chinese Acad Sci, Lab Adv Spectro Electrochem & Li Ion Batteries, Lab Adv Spectroelectrochem & Li Ion Batteries, Dalian 116023, Peoples R China;[11]Univ Sci & Technol China, CAS Ctr Excellence Nanosci, Natl Synchrotron Radiat Lab, Hefei 230029, Peoples R China

年份：2024

卷号：17

期号：8

起止页码：2765

外文期刊名：ENERGY & ENVIRONMENTAL SCIENCE

收录：;EI(收录号：20241015669369);WOS:【SCI-EXPANDED(收录号:WOS:001177289200001)】；

基金：This work was financially supported by the National Key R&D Program of China (Grant 2022YFA1504100), the National Natural Science Foundation of China (Grant No. 22125903 and 22005298), Dalian National Laboratory for Clean Energy (DNL), CAS, DNL Cooperation Fund, CAS (DNL202016 and DNL202019), the Joint Fund of the Yulin University and the Dalian National Laboratory for Clean Energy (YLU-DNL Fund 2021002 and YLU-DNL Fund 2021009), and the Exploratory Research Project of Yanchang Petroleum International Limited and DICP (yc-hw-2022ky-01). We acknowledge the Hefei Synchrotron Radiation Facility for conducting the SXAS experiment (MCD-A and MCD-B Soochow Beamline for Energy Materials at NSRL) and the Vacuum Interconnected Nanotech Workstation (NANO-X) for conducting the FIB and TOF-SIMS experiments. We thank Prof. Yi Cui, Tong Liu and Rong Huang in the Vacuum Interconnected Nanotech Workstation (NANO-X) (Suzhou Institute of Nanotechnology and Nano-bionics, Chinese Academy of Sciences) for kindly conducting FIB and TOF-SIMS characterization.

语种：英文

外文关键词：Cathodes - Charge transfer - Charging (batteries) - Fluorination - Halogenation - Lithium-ion batteries - Oxygen - Surface structure

摘要：LiCoO2 (LCO) is a leading cathode material of lithium-ion batteries in consumer electronics. However, practical applications of high-voltage fast charging are hampered by unstable interfacial structures and unfavorable phase transitions arising from the superimposed high-flux Li+ diffusion of LCO during deep de-lithiation. Here, we report a universal cathode interface engineering strategy of stabilizing 4.45 V commercial LCO by surface fluorination (F-LCO) towards fast-charging long-life cyclability at a high voltage of 4.6 V. It is experimentally observed that the resulting near-surface structure with a similar to 1 nm ultrathin dense LiF covering layer and a 10-20 nm gradient fluorination lattice, together with a trace amount of phosphates, provides extraordinary stabilization to the surface lattice oxygen. F-LCO achieves a record capacity retention of 92% after 1000 cycles at 3C, far outperforming the commercial LCO (31%) and reported 4.6 V LCOs. Further, it is theoretically revealed that the antibonding orbital electron transfer in Co-F bonding greatly inhibits cobalt migration as the de-lithiation approaches 4.6 V. We unravel that the reconstructed high-energy barrier F-rich interface with enhanced charge transfer capability ultimately prevents high-valent oxygen species (On-, 0 < n < 2) from migrating along vacancies and evolving into oxygen to generate interfacial side reactions. Our pouch-type full cells of graphite||F-LCO offer superior high voltage (4.5 V) cyclability without capacity fading over 1100 cycles at a fast-charging rate of 5C. Therefore, this strategy of cathode interface fluorination provides new insights into the commercial realization of high-voltage fast-charging LCOs.