尖晶石型锰酸锂正极材料LiNi0.01Co0.03Mn1.96O4的合成及电化学性能

doi:10.7503/cjcu20190346

摘要/Abstract

摘要：

采用固相燃烧法制备了具有多面体形貌的Ni-Co共掺杂尖晶石型LiNi_0.01Co_0.03Mn_1.96O₄(LNCMO)正极材料. 研究结果表明, LNCMO具有优异的倍率性能和长循环稳定性, 在25 ℃, 1C或5C倍率条件下, 初始放电比容量分别为110.6和102.3 mA·h/g, 循环1000次后容量保持率为75.7%和78.3%; 在10C和20C高倍率下, 循环1000次后, 容量保持率分别为78.8%和54.2%; 即使在高温(55 ℃)和1C倍率下, 循环1000次后容量保持率仍为76.6%. LNCMO具有较大的Li ⁺扩散系数(4.77×10 ^-11 cm ²/s)和较低的表观活化能(23.37 kJ/mol).

关键词: Ni-Co共掺杂, 尖晶石型LiMn₂O₄, 固相燃烧法, 锂离子电池

Abstract:

Ni-Co co-doped LiNi_0.01Co_0.03Mn_1.96O₄(LNCMO) cathode material with a polyhedral morphology was prepared via a solid-state combustion method. Results show that the LNCMO sample has excellent rate performance and long cycling stability, it delivers the initial discharge capacity of 110.6 and 102.3 mA·h/g with capacity retention rate of 75.7% and 78.3% after 1000 cycles at 1C and 5C at 25 ℃, respectively. At high current rate of 10C and 20C, the capacity retention rates of 78.8% and 54.2% are obtained after 1000 cycles, respectively. Even at 1C under high temperature of 55 ℃, the capacity retention rate of 76.6% is also maintained after 1000 cycles. The LNCMO sample shows larger Li ⁺ ion diffusion coefficient(4.77×10 ^-11 cm ²/s) and lower apparent activation energy(23.37 kJ/mol) compared to the Co-doped sample.

Key words: Ni-Co co-doping, Spinel LiMn₂O₄, Solid-state combustion method, Lithium ion battery

中图分类号:

O646
TM912

TrendMD:

段玉珍,朱金玉,郭俊明,向明武,刘晓芳,白红丽,苏长伟. 尖晶石型锰酸锂正极材料LiNi_0.01Co_0.03Mn_1.96O₄的合成及电化学性能. 高等学校化学学报, 2019, 40(12): 2574.

Yuzhen DUAN,Jinyu ZHU,Junming GUO,Mingwu XIANG,Xiaofang LIU,Hongli BAI,Changwei SU. Synthesis and Electrochemical Properties of Spinel Lithium Manganese Cathode Material LiNi_0.01Co_0.03Mn_1.96O₄ ^†. Chem. J. Chinese Universities, 2019, 40(12): 2574.

图/表 15

Fig.1 XRD patterns of samples LCMO and LNCMO

Fig.2 SEM images of samples LCMO(A) and LNCMO(B)

Fig.3 TEM(A), HRTEM and SAED(inset) images(B) of sample LNCMO

Fig.4 Elemental mapping of sample LNCMO (A) Mn; (B) Ni; (C) Co; (D) O.

Fig.5 EDS of sample LNCMO

Fig.6 Survey(A) and Mn2p3/2(B), Co2p3/2(C), Ni2p3/2(D) XPS spectra for sample LNCMO

Fig.7 Initial charge-discharge curves(A) and cycle performance(B) of samples LCMO and LNCMO at 1C and 25 ℃

Fig.8 Cycle performance of LCMO and LNCMO samples at 5C under 25 ℃(A), cycle performance of LNCMO sample at 10C and 20C under 25 ℃(B), rate performance of LCMO and LNCMO samples(C) and high-temperature cycle performance of LCMO and LNCMO samples at 1C under 55 ℃(D)

Fig.9 CV curves associated with LCMO, LNCMO at the first(A) and after 1000 cycles(B) ranging from 3.6 V to 4.5 V(vs. Li/Li+) at a scan rate of 0.15 mV/s

Fig.10 CV curves of LNCMO(A) and LCMO(B) electrodes ranging from 3.6 V to 4.5 V(vs. Li/Li+) at different scan rates and ip-υ1/2 plots of LNCMO(C) and LCMO(D)

Table 1 $D_Li^{+}$ values of redox peak of samples LCMO and LNCMO

Redox peak	10¹¹/(cm²·s^-1)
Redox peak	LCMO	LNCMO
A1	2.87	4.77
A2	2.45	3.55
C1	2.62	4.40
C2	1.22	3.21

Fig.11 Nyquist plots of LCMO(A) and LNCMO(B) electrodes after the first cycle, and after 1000 cycles at 1C and 25 ℃ Inset shows the equivalent circuit.

Fig.12 Nyquist plots of LCMO(A) and LNCMO(B) electrodes under various temperatures and Arrhenius plots of LCMO and LNCMO(C)

Fig.13 XRD patterns about LCMO and LNCMO cathodes after 1000 cycles at 1C

Fig.14 SEM images of LCMO(A) and LNCMO(B) after 1000 cycles at 1C Insets are the corresponding SEM images of the two samples at high magnification.

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尖晶石型锰酸锂正极材料LiNi_0.01Co_0.03Mn_1.96O₄的合成及电化学性能

Synthesis and Electrochemical Properties of Spinel Lithium Manganese Cathode Material LiNi_0.01Co_0.03Mn_1.96O₄ ^†

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