Electrochemical Studies on the Working Mechanism of Lithium-rich Manganese Based Material Coated by MnO2 †

doi:10.7503/cjcu20180343

Abstract

Abstract:

In order to investigate the characteristic reactions and structural changes of lithium-rich manganese based material coated by MnO₂, the lithium-rich manganese based material was prepared by solid state reaction, and then modified with MnO₂ by chemical precipitation and heat treatment. The electrochemical performances of the obtained materials were characterized by constant current charge-discharge, cyclic voltammetry and electrochemical impedance spectroscopy. The working mechanism of lithium-rich manganese based materials coated by MnO₂ was studied by discussing the changes of the electrochemical reactions before and after the modification. The results show that the coating MnO₂ can work as the container of lithium. During the heat treatment process, lithium and nickel elements of the lithium-rich manganese based material migrate and diffuse into the MnO₂ coating to form a new spinel composite phase, which reversibly participates in the subsequent cyclic reactions and makes its contribution to enhance the battery electrochemical performances.

Key words: MnO₂ coating, Lithium-rich manganese based material, Working mechanism

CLC Number:

O646

TrendMD:

QIU Jiaxin,JIANG Qi,GAO Yike,PENG Junqi,DUAN Zhihong,LU Xiaoying. Electrochemical Studies on the Working Mechanism of Lithium-rich Manganese Based Material Coated by MnO₂ ^†[J]. Chem. J. Chinese Universities, 2018, 39(10): 2238.

Figures/Tables 8

Fig.1 XRD patterns of the obtained samplesa. Pristine; b. 3%coated; c. 5%coated; d. 7%coated.

Fig.2 SEM images of pristine(A) and 5%coated(B)

Fig.3 Electrochemical testing results of samples(A) First charge-discharge curves at 0.1C; (B) capacity differential curves; (C) CV curves of pristine sample; (D) CV curves of 5%coated sample.

Table 1 Data of the first charge-discharge of the samples

Sample	Charge capacity/ (mA·h·g^-1)	Discharge capacity/ (mA·h·g^-1)	Irreversible capacity/ (mA·h·g^-1)	Coulomb efficient(%)
Pristine	328.0	269.3	58.7	82.1
3%coated	319.2	273.3	46.2	85.6
5%coated	309.5	281.5	28.0	90.9
7%coated	301.5	286.9	14.6	95.1

Scheme 1 Working mechanism schematic diagram of lithium-rich manganese material modified by MnO2 coating during the first charge-discharge and subsequent cycles

Fig.4 Rate performances(A), normalized capacity retention at different rates(B), cycle performances(C)and coulomb efficiencies(D) of obtained samples

Fig.5 EIS spectra(A) and Zre-ω-1/2 curves(B) of the samplesThe inset is corresponding equivalent circuit.

Table 2 EIS data of the samples

Sample	R_s/Ω	R_sf/Ω	R_ct/Ω	σ_W	$D L i +$ /(cm²·s^-1)
Pristine	3.59	73.71	218.10	21.57	6.79×10^-17
3%coated	5.11	51.79	135.42	16.24	1.17×10^-16
5%coated	7.97	49.05	100.10	13.67	1.69×10^-16
7%coated	4.57	55.92	148.47	14.17	1.40×10^-16

Table 2 EIS data of the samples

Sample	R_s/Ω	R_sf/Ω	R_ct/Ω	σ_W	$D L i +$ /(cm²·s^-1)
Pristine	3.59	73.71	218.10	21.57	6.79×10^-17
3%coated	5.11	51.79	135.42	16.24	1.17×10^-16
5%coated	7.97	49.05	100.10	13.67	1.69×10^-16
7%coated	4.57	55.92	148.47	14.17	1.40×10^-16

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Electrochemical Studies on the Working Mechanism of Lithium-rich Manganese Based Material Coated by MnO₂ ^†

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