Effects of SmPO4 Coatingon Electrochemical Performance of High-voltage LiNi0.5Mn1.5O4 Cathode Materials

doi:10.7503/cjcu20210546

Abstract

Abstract:

Spinel-type LiNi_0.5Mn_1.5O₄ has been widely used in large-scale energy storage equipment， energy conversion equipment and power vehicle， due to its low preparation cost， high discharge platform and long cycle life. However， the electrolyte of LiNi_0.5Mn_1.5O₄ decomposes easily under high voltage（5 V） charging， which leads to a decrease in specific capacity and a decline in cycling performance. To solve the above problems， the LiNi_0.5Mn_1.5O₄ cathode material was successfully coated with a thin layer of SmPO₄via a hydrothermal process. The influence of the coating amount of SmPO₄ on the electrochemical performance of LiNi_0.5Mn_1.5O₄ material was systematically studied. The results indicate that the as-prepared LiNi_0.5Mn_1.5O₄ coated with 0.5%（mass fraction） SmPO₄（LNMO@SP-0.5） exhibits optimal electrochemical performance. In case of 0.2C and 5C， the discharge specific capacity of LNMO@SP-0.5 was 129.2^{and 90.9 mA?h/g， respectively， while Pristine LNMO only had 114.2 and 77.7 mA?h/g. LNMO@SP-0.5 exhibited a capacity retention of 93.4% after 500 cycles at 5C and 25 ℃， whereas the Pristine LNMO exhibited a poor capacity retention of 86.6%. The improvement was due to SmPO₄ coating can effectively alleviate the side reaction between LiNi_0.5Mn_1.5O₄ material and electrolyte， and reduce the polarization degree and charge transfer resistance of the electrode， and increase the diffusion coefficient of Li⁺.}

Key words: Spinel-type LiNi_0.5Mn_1.5O₄, Coathode material, SmPO₄ Coating layer, Hydrothermal method

CLC Number:

O646

TrendMD:

LI Xiaohui, WEI Aijia, MU Jinping, HE Rui, ZHANG Lihui, WANG Jun, LIU Zhenfa. Effects of SmPO₄Coatingon Electrochemical Performance of High-voltage LiNi_0.5Mn_1.5O₄Cathode Materials[J]. Chem. J. Chinese Universities, 2022, 43(2): 20210546.

Figures/Tables 16

Fig.1 XRD patterns of Pristine LNMO(a), LNMO@SP?0.25(b), LNMO@SP?0.5(c), LNMO@SP?1(d) and LNMO@SP?2(e) samples

Fig.2 Raman spectra of Pristine LNMO(a), LNMO@SP?0.25(b), LNMO@SP?0.5(c), LNMO@SP?1(d) and LNMO@SP?2(e) samples

Fig.3 SEM images of Pristine LNMO(A), LNMO@SP?0.25(B), LNMO@SP?0.5(C), LNMO@SP?1(D) and LNMO@SP?2(E) samples

Fig.4 EDS spectrum(A) and the corresponding elements mapping images of Ni(B), Mn(C), O(D), Sm(E) and P(F) of LNMO@SP?2 sample

Fig.5 TEM images of Pristine LNMO(A), LNMO@SP?0.25(B), LNMO@SP?0.5(C), LNMO@SP?1(D) and LNMO@SP?2(E) samples

Fig.6 XPS spectra of Ni2p(A), Mn2p(B), Sm3d(C) and P2d(D) for the LNMO@SP?2 sample

Fig.7 Rate capability curves(A) and initial discharge capacities and coulombic efficiencies(B) of Pristine LNMO, LNMO@SP?0.25, LNMO@SP?0.5, LNMO@SP?1 and LNMO@SP?2 samples

Table 1 Discharge capacity of Pristine LNMO, LNMO@SP-0.25, LNMO@SP-0.5, LNMO@SP-1 and LNMO@SP-2 samples at different rates

Sample	Discharge capacity/（mA·h·g^-1）
Sample	0.2C	0.5C	1C	2C	3C	5C
Pristine LNMO	114.2	107.5	104.6	99.2	93.8	77.7
LNMO@SP?0.25	119.7	118.3	113.8	104.8	95.2	78.2
LNMO@SP?0.5	129.2	122.9	118.8	112.3	104.9	90.9
LNMO@SP?1	127.9	122.0	118.0	111.6	101.0	88.8
LNMO@SP?2	119.3	115.4	110.9	103.2	94.2	79.2

Fig.8 Galvanostatic charge?discharge curves of Pristine LNMO(A), LNMO@SP?0.25(B), LNMO@SP?0.5(C), LNMO@SP?1(D) and LNMO@SP?2(E) samples

Fig.9 Cycling performances of Pristine LNMO, LNMO@SP?0.25, LNMO@SP?0.5, LNMO@SP?1 and LNMO@SP?2 samples at 1C

Table 2 Discharge capacity and capacity retention of Pristine LNMO, LNMO@SP-0.25, LNMO@SP-0.5, LNMO@SP-1 and LNMO@SP-2 samples at 1C

Sample	Discharge capacity/（mA·h·g^-1）		Capacity retention（%）
Sample	1st cycle	200th cycle	Capacity retention（%）
Pristine LNMO	96.4	83.5	86.6
LNMO@SP?0.25	105.9	95.1	89.8
LNMO@SP?0.5	113.2	105.7	93.4
LNMO@SP?1	109.9	99.0	90.1
LNMO@SP?2	106.0	94.5	89.2

Fig.10 SEM images of Pristine LNMO(A1, B1), LNMO@SP?0.25(A2, B2), LNMO@SP?0.5(A3, B3), LNMO@SP?1(A4, B4) and LNMO@SP?2(A5, B5) electrodes before(A1—A5) and after(B1—B5) 200 cycles at 1C

Fig.11 Cyclic voltammetry curves for Pristine LNMO, LNMO@SP?0.25, LNMO@SP?0.5, LNMO@SP?1 and LNMO@SP?2 samples at 0.1 mV/s

Table 3 Potential difference between anode and cathode peaks of Pristine LNMO, LNMO@SP-0.25, LNMO@SP-0.5, LNMO@SP-1 and LNMO@SP-2 samples*

Sample	Φ_pa/V	Φ_pc/V	?V/V
Pristine LNMO	4.821	4.582	0.239
LNMO@SP?0.25	4.830	4.611	0.219
LNMO@SP?0.5	4.834	4.622	0.212
LNMO@SP?1	4.828	4.611	0.217
LNMO@SP?2	4.832	4.608	0.224

Fig.12 EIS spectra(A) and graph(B) of Zre plotted against ω-1/2 at low?frequency region of Pristine LNMO, LNMO@SP?0.25, LNMO@SP?0.5, LNMO@SP?1 and LNMO@SP?2 samplesInset of (A): equivalent circuit diagram. Rs: The solution resistance of the cell; CPE: constant phase element, representing the double layer capacitance of the interface; Zw: Warburg impedance.

Table 4 Alternating current(AC) impedance parameters of Pristine LNMO, LNMO@SP-0.25, LNMO@SP-0.5, LNMO@SP-1 and LNMO@SP-2 samples

Sample	R_s/Ω	R_ct/Ω
Pristine LNMO	1.141	240.6
LNMO@SP?0.25	1.084	188.4
LNMO@SP?0.5	1.005	118.2
LNMO@SP?1	1.070	141.3
LNMO@SP?2	1.075	211.7

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Effects of SmPO₄Coatingon Electrochemical Performance of High-voltage LiNi_0.5Mn_1.5O₄Cathode Materials

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