Enhanced Lithium Storage Stability Mechanism of Ultra-high Nickel LiNi0.91Co0.06Al0.03O2@Ca3(PO4)2 Cathode Materials

doi:10.15541/jim20210769

Abstract

Abstract:

Ultra-high nickel material as a new lithium-ion battery cathode has attracted much attention due to its high specific capacity, high voltage and low cost. However, the generated microcracks, mechanical pulverization and irreversible phase transformation during cycling, result in poor cycling stability. Herein, a series of Ca₃(PO₄)₂- coated ultra-high nickel LiNi_0.91Co_0.06Al_0.03O₂ materials with different thicknesses (NCA@nCP) were prepared through a facile wet-chemistry strategy. Among them, NCA@1CP manifested specific discharge capacity of 204.8 mAh/g under 2.7-4.3 V at 1C (1C=200 mA/g), with a capacity retention rate of 91.5% after 100 cycles. Even after 300 cycles at 2C, the specific discharge capacity retained 153.4 mAh/g. Material characterization results further confirm that the coating shell inhibits the Li/Ni mixing, irreversible phase transformation and mechanical pulverization of the NCA@1CP, greatly improving the cycling stability. This work shows that the Ca₃(PO₄)₂ coating strategy has great application potential in improving the lithium storage stability of ultra-high nickel cathode materials.

Key words: lithium-ion battery, ultra-high nickel cathode, Ca₃(PO₄)₂, surface coating

CLC Number:

TQ174

ZHU Hezhen, WANG Xuanpeng, HAN Kang, YANG Chen, WAN Ruizhe, WU Liming, MAI Liqiang. Enhanced Lithium Storage Stability Mechanism of Ultra-high Nickel LiNi_0.91Co_0.06Al_0.03O₂@Ca₃(PO₄)₂ Cathode Materials[J]. Journal of Inorganic Materials, 2022, 37(9): 1030-1036.

Figures/Tables 14

Fig. 1 (a) XRD patterns of NCA and NCA@nCP (n=0.5, 1, 3), and (b) Rietveld refinement results of NCA@1CP Colourful figures are available on website

Fig. 2 (a) SEM image of NCA@1CP, high-resolution TEM images of (b) NCA and (c) NCA@1CP, and (d) EDS elemental mappings of NCA@1CP

Fig. 3 (a) Full survey, (b) Ni2p, (c) Co2p, (d) Al2p, (e) P2p and (f) Ca2p XPS spectra for NCA and NCA@1CP Colourful figures are available on website

Fig. 4 CV curves for (a) NCA and (b) NCA@1CP; (c) Initial charge-discharge curves under 2.7-4.3 V at 0.2C and (d) cycling properties under 2.7-4.3 V at 1C for NCA and NCA@nCP; Cycling properties for NCA and NCA@1CP (e) under 2.7-4.5 V at 1C and (f) under 2.7-4.3 V at 2C Colourful figures are available on website

Fig. 5 Voltage-time variation curves during in-situ XRD for (a) NCA and (c) NCA@1CP; In-situ XRD patterns for (b, e) NCA and (d, f) NCA@1CP; (g) Variation curves of the lattice parameter c during charging for NCA and NCA@1CP

Fig. 6 (a) Cycling properties of full cells both NCA and NCA@1CP as cathode, graphite as anode under 2.7-4.25 V at 1C, and (b) charge-discharge curves of the second cycle for NCA@1CP in full cell

Fig. S1 Rietveld refinement results of (a) NCA, (b) NCA@0.5CP and (c) NCA@3CP

Fig. S2 SEM images of (a, b) NCA, (c, d) NCA@0.5CP and (e, f) NCA@3CP

Fig. S3 EDS elemental mappings of NCA

Fig. S4 CV curves for (a) NCA@0.5CP and (b)NCA@3CP

Fig. S5 (a) Rate performance for NCA, NCA@0.5CP, NCA@1CP and NCA@3CP; Corresponding discharge curves during rate tests of (b) NCA and (c) NCA@1CP

Fig. S6 (a, b) SEM images and (c-f) XRD patterns of NCA and NCA@1CP after 100 cycles under 2.7-4.3 V at 1C

Table S1 I(003)/I(104) values for NCA, NCA@0.5CP, NCA@1CP and NCA@3CP

Sample	NCA	NCA@0.5CP	NCA@1CP	NCA@3CP
I₍₀₀₃₎/I₍₁₀₄₎	1.426	2.120	2.261	1.981

Table S2 Lattice parameters of the NCA, NCA@0.5CP, NCA@1CP and NCA@3CP calculated from XRD Rietveld refinement

Sample	a/nm	c/nm	V/nm³	c/a	R_wp	R_p
NCA	0.287398	1.421071	0.101652	4.944609	7.13	4.18
NCA@0.5CP	0.287296	1.420733	0.101556	4.945188	6.63	4.73
NCA@1CP	0.287286	1.420440	0.101527	4.944341	5.86	4.39
NCA@3CP	0.287305	1.420646	0.101556	4.944731	6.74	4.82

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Enhanced Lithium Storage Stability Mechanism of Ultra-high Nickel LiNi_0.91Co_0.06Al_0.03O₂@Ca₃(PO₄)₂ Cathode Materials

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