Surface Treatment on Structure and Property of LiNi0.8Co0.15Al0.05O2 by Silane Coupling Agent

doi:10.15541/jim20170461

Abstract

Abstract:

Silane coupling agent was used to treat surface of cathode material LiNi_0.8Co_0.15Al_0.05O₂ (NCA) for lithium ion battery by a simple thermal decomposition method. Structures and properties of the materials were characterized by XRD combined with Rietveld refinement, SEM, TEM, DSC, EIS and galvanostatic charge/discharge test. The results show that amorphous SiO₂ obtained by decomposition of silane coupling agent is uniformly coated on the surface of NCA whose crystal structure remain unaffected while its comprehensive properties are significantly improved especially at high temperature. In the environment of 60℃ at 0.2C and 1C rate , the discharge capacities of the coated NCA (a-NCA) are 176.4 mAh·g^-1 and 158.9 mAh·g^-1 respectively, whereas counterparts of the pristine NCA are slightly lower and reduced to 174.2 mAh·g^-1and 153.8 mAh·g^-1, respectively. The capacity retention of a-NCA is 91.4% while that of NCA is 86.5% after 50 charge/discharge cycles. Moreover, thermal stability of a-NCA is greatly improved compared with the uncoated material under test condition of 60℃ in that the coating inhibits the side reaction between NCA surface and electrolyte which successfully restrains the surface film resistance and restricts variation of the crystal structure of material in process of cycling.

Key words: LiNi_0.8Co_0.15Al_0.05O₂, silane coupling agent, coating, electrochemical performance, thermal stability

CLC Number:

TQ152

FAN Guang-Xin, LIU Ze-Ping, WEN Yin, LIU Bao-Zhong. Surface Treatment on Structure and Property of LiNi_0.8Co_0.15Al_0.05O₂ by Silane Coupling Agent[J]. Journal of Inorganic Materials, 2018, 33(7): 749-755.

Figures/Tables 15

Fig. 1 (a) TG-DTA curves of the KH550 silane coupling agent in air and (b) XRD pattern for thermal decomposition product of the silane coupling agent after heating at 450℃ for 5 h

Fig. 2 (a) XRD patterns for NCA and a-NCA, and (b) their enlarged XRD patterns.

Fig. 3 XRD Rietveld refinement of a-NCA

Table 1 Structural parameters of NCA and a-NCA

Sample	a/nm	c/nm	c/a	FWHM/(°)
Sample	a/nm	c/nm	c/a	(003)	(104)
NCA	0.2869	1.4193	4.948	0.130	0.225
a-NCA	0.2869	1.4200	4.949	0.131	0.228

Fig. 4 SEM images of NCA(a, b) and a-NCA (c, d)

Fig. 5 EDS mapping of a-NCA

Fig. 6 TEM image of a-NCA

Fig. 7 (a) Initial charge-discharge curves and (b) the corresponding differential capacity (dQ/dV) of NCA and a-NCA

Table 2 Electrochemical performances of NCA and a-NCA

Sample	0.1C/(mAh·g^-1)	0.2C/(mAh·g^-1)	1C/(mAh·g^-1)	Difference values of (Ni²⁺/Ni⁴⁺)/V	Capacity retention
NCA-RT	171.5	164.7	146.0	0.11	94.7%
a-NCA-RT	164.6	153.8	140.2	0.10	96.0%
NCA-HT	184.9	174.2	153.8	0.05	86.5%
a-NCA-HT	183.2	176.4	158.9	0.01	91.4%

Fig. 8 Rate capacity and cyclic ability of NCA and a-NCA

Fig. 9 EIS plots of NCA and a-NCA at (a) room temperature and (b) high temperature with inset in (b) showing the corresponding equivalent circuit diagram

Table 3 Electrochemical AC impedance values of NCA and a-NCA

Sample	Condition	R_s/Ω	R_f/Ω	R_ct/Ω	W_o/(×10^-3, Ω)
NCA	Original	8.6	136.4	211.9	2.0
	RT-50th	7.5	8.3	126.1	2.8
	HT-50th	7.9	55.7	114.2	7.5
a-NCA	Original	6.5	106.0	156.6	3.1
	RT-50th	4.5	7.4	92.1	4.9
	HT-50th	6.2	21.4	75.5	8.6

Fig. 10 DSC curves of NCA and a-NCA

Fig. 11 XRD patterns of (003) peak in original and the 50th cycle sample for NCA and a-NCA at room temperature (a) and high temperature (b)

Table 4 Structural parameters of NCA and a-NCA before and after cycling at room temperature and high temperature

	Condition	a/nm	Δa/a	c/nm	V/(×10^-3, nm³)
NCA	Original	0.2869		1.4193	0.1011
	RT-50th	0.2858	0.39%	1.4246	0.1007
	HT-50th	0.2841	0.96%	1.4299	0.995
a-NCA	Original	0.2869		1.4199	0.1012
	RT-50th	0.2862	0.26%	1.4224	0.1008
	HT-50th	0.2857	0.43%	1.4242	0.1001

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Surface Treatment on Structure and Property of LiNi_0.8Co_0.15Al_0.05O₂ by Silane Coupling Agent

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