Microwave-assisted Synthesis and Co, Al Co-modification of Ni-rich LiNi0.8Mn0.2O2 Materials for Li-ion Battery Electrode

doi:10.15541/jim20200522

Abstract

Abstract:

Due to high specific capacity and cost performance, high-nickel cathode materials have received much attention. However, its further application is hindered by poor stability and safety performance during cycling. In this work, Ni-rich LiNi_0.8Mn_0.2O₂ materials were prepared through microwave-assisted co-precipitation followed by high-temperature solid-phase method, which can be further modified by doping different proportions of Co and Al. As a result, LiNi_0.8Mn_0.1Co_0.08Al_0.02O₂ (NMCA-2) exhibits the best electrochemical performance, whose capacity retention rate reaches 91.39% after 100 cycles at 1C in the voltage range between 2.75 and 4.35 V, and still owns a specific discharge capacity of 160.03 mAh∙g^-1 at 5C. Its excellent cyclic retention rate can be attributed to the restrained irreversibility of H2→H3 phase transition during cycling with Co and Al doping, and the lower reaction polarization which contributed to the decline of charge transfer resistance, resulting in good cycle and rate performance of the material. Furthermore, high thermal stability of NMCA-2 improves the safety of the material.

Key words: LiNi_0.8Mn_0.2O₂, Co,Al co-modification, microwave-assisted coprecipitation, cycle performance, rate performance

CLC Number:

TQ174

FU Yukun, ZENG Min, RAO Xianfa, ZHONG Shengwen, ZHANG Huijuan, YAO Wenli. Microwave-assisted Synthesis and Co, Al Co-modification of Ni-rich LiNi_0.8Mn_0.2O₂ Materials for Li-ion Battery Electrode[J]. Journal of Inorganic Materials, 2021, 36(7): 718-724.

Figures/Tables 17

Fig. 1 SEM images of (a, b) NM-82, (c-l) NMCA-n (n=0, 1, 2, 3, 5) (c, d) n=0; (e, f) n=1; (g, h) n=2; (i, j) n=3; (k, l) n=5

Fig. 2 XRD patterns of NM-82 and NMCA-n (n=0, 1, 2, 3, 5)

Fig. 3 (a) Total survey and (b) Ni2p, (c) Co2p, (d) Al2p XPS spectra of NM-82 and NMCA-2

Fig. 4 (a,c) TEM images, (b,d)HR-TEM images and (insets in (b, d)) the corresponding FFT graphs of NM-82 and NMCA-2 (a, c) Magnified images of the square areas in the corresponding insets

Fig. 5 (a-c) Charge/discharge curves and (d-f) corresponding dQ/dV plots of NM-82, NMCA-0 and NMCA-2

Fig. 6 Cycling performance and corresponding capacity retention rate (inset) of different materials

Fig. 7 (a-c) CV curves, (d-f) EIS plots and (insert in (d)) corresponding equivalent electrical circuit of NM-82, NMCA-0 and NMCA-2

Fig. S1 Schematic diagram of microwave assisted coprecipitation

Fig. S2 SEM image and TEM-EDS elemental mappings of NMCA-2

Fig. S3 (a, b) Particle size distributions, (c) nitrogen adsorption-desorption isotherms and (d) pore size distributions of NM-82 and NMCA-2

Fig. S4 Schematic diagram of layered material structure

Fig. S5 Rietveld refinement results of (a) NM-82, (b) NMCA-0 and (c) NMCA-2

Fig. S6 Rate performances of different cathode materials

Fig. S7 DSC curves of NM-82, NMCA-0 and NMCA-2

Table S1 Parameters of Rietveld refinement for NM-82, NMCA-0 and NMCA-2

Sample	a/nm	c/nm	c/a	I₍₀₀₃₎/I₍₁₀₄₎
NM-82	0.2875	1.4232	4.9507	1.3197
NMCA-0	0.2877	1.4229	4.9457	1.3945
NMCA-2	0.2872	1.4243	4.9593	1.5888

Table S2 Specific discharge capacities of materials at different rates/(mAh·g-1)

Sample	0.2C	0.5C	1C	2C	3C	4C	5C	0.2C
NM-82	195.57	183.52	175.03	164.59	157.33	149.26	141.49	185.66
NMCA-0	192.45	182.66	176.69	166.91	160.88	157.05	153.17	183.80
NMCA-1	189.79	182.60	177.43	169.72	165.24	162.25	158.83	187.36
NMCA-2	189.70	183.05	177.84	172.80	169.08	164.76	160.03	189.25
NMCA-3	187.28	180.32	174.85	168.60	162.63	158.61	156.14	187.50
NMCA-5	186.04	178.28	173.83	167.08	163.41	157.97	150.84	181.33

Table S3 EIS fitting data of NM-82, NMCA-0 and NMCA-2

Sample	Cycle number	R_s/Ω	R_sf/Ω	R_ct/Ω
NM-82	5	3.85	20.20	46.65
	50	3.09	49.32	64.95
	100	7.27	94.06	138.40
NMCA-0	5	1.89	29.24	20.19
	50	2.01	58.13	72.25
	100	4.04	82.55	114.90
NMCA-2	5	5.11	31.85	19.80
	50	3.30	51.78	72.70
	100	4.08	67.32	67.88

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Microwave-assisted Synthesis and Co, Al Co-modification of Ni-rich LiNi_0.8Mn_0.2O₂ Materials for Li-ion Battery Electrode

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