Cation and polyanion co-doping synergy to improve electrochemical performances of Li-rich manganese-based cathode materials

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作者
Li, Chunlei [1 ,2 ,3 ]
Cai, Xingpeng [1 ]
Fu, Xiaolan [1 ]
Zhang, Ningshuang [1 ,2 ,3 ]
Ding, Hao [1 ]
Wang, Peng [1 ]
Zhou, Xinan [1 ]
Song, Linhu [1 ]
Huang, Jin [1 ]
Li, Shiyou [1 ,2 ,3 ]
机构
[1] School of Petrochemical Technology, Lanzhou University of Technology, Lanzhou,730050, China
[2] Key Laboratory of Low Carbon Energy and Chemical Engineering of Gansu Province, Lanzhou,730050, China
[3] Gansu Lithium ion Battery Cathode Material Engineering Research Center, Baiyin,730900, China
关键词
The redox of anions can be realized by the Li-rich manganese-based (LRM) cathode materials at high voltage; which provides a high specific capacity application prospect for lithium-ion batteries. However; the anion redox reaction brings problems such as poor cycling performance and serious voltage decay; which can be improved by the doping method. Herein; Al3+ cation and (BO3)3-/(BO4)5- polyanion are introduced into the LRM cathode materials to achieve double site occupation and charge regulation of the structure. It results in excellent electrochemical properties; especially in terms of cycling stability. The doped sample shows a discharged capacity of 239 mAh g−1 at 0.01 C after 100 cycles and a capacity retention rate of 92.0 % (higher than 77.9 % of the pristine sample). Through the brand newly-developed in-situ electrochemical impedance spectroscopy and X-ray photoelectron spectroscopy analysis; the joint regulation of Al3+ and (BO3)3-/(BO4)5- inhibits the attack of singlet oxygen on the electrolyte and makes the cathode electrolyte interphases (CEI) film more uniform. First-principles calculations show that the introduction of electron holes and the reduction of the covalency between transition metal and O are key factors in the improvement of electrochemical property and structural stability of the modified materials. © 2022;
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