钾离子掺杂提高锂离子电池正极锰酸锂性能的微观机制

doi:10.15541/jim20210757

无机材料学报 ›› 2022, Vol. 37 ›› Issue (9): 1023-1029.DOI: 10.15541/jim20210757

钾离子掺杂提高锂离子电池正极锰酸锂性能的微观机制

王洋¹^,²(), 范广新¹^,³(), 刘培², 尹金佩¹, 刘宝忠², 朱林剑³, 罗成果³

1.河南理工大学材料科学与工程学院, 焦作 454000
2.河南理工大学化学化工学院, 焦作 454000
3.焦作伴侣纳米材料工程有限公司, 焦作 454000

收稿日期:2021-12-10 修回日期:2022-02-13 出版日期:2022-09-20 网络出版日期:2022-02-21
通讯作者: 范广新, 副教授. E-mail: fangx@hpu.edu.cn
作者简介:王洋(1997-), 男, 硕士研究生. E-mail: wangyang1857@126.com
基金资助:
国家自然科学基金(52071135);国家自然科学基金(51871090);国家自然科学基金(U1804135);国家自然科学基金(51671080);河南省科技创新人才计划(194200510019);河南省教育委员会重点项目(19A150025)

Microscopic Mechanism of K⁺ Doping on Performance of Lithium Manganese Cathode for Li-ion Battery

WANG Yang¹^,²(), FAN Guangxin¹^,³(), LIU Pei², YIN Jinpei¹, LIU Baozhong², ZHU Linjian³, LUO Chengguo³

1. School of Materials Science and Engineering, Henan Polytechnic University, Jiaozuo 454000, China
2. College of Chemistry and Chemical Engineering, Henan Polytechnic University, Jiaozuo 454000, China
3. Jiaozuo Banlv Nano Materials Engineering Co., Ltd, Jiaozuo 454000, China

Received:2021-12-10 Revised:2022-02-13 Published:2022-09-20 Online:2022-02-21
Contact: FAN Guangxin, associate professor. E-mail: fangx@hpu.edu.cn
About author:WANG Yang (1997-), male, Master candidate. E-mail: wangyang1857@126.com
Supported by:
National Natural Science Foundation of China(52071135);National Natural Science Foundation of China(51871090);National Natural Science Foundation of China(U1804135);National Natural Science Foundation of China(51671080);Plan for Scientific Innovation Talent of Henan Province(194200510019);Key Project of Educational Commission of Henan Province(19A150025)

摘要/Abstract

摘要：

改善尖晶石锰酸锂的大倍率性能是目前锂离子电池的重点研究方向之一。本研究用高温固相法合成掺K⁺的尖晶石锰酸锂, 研究K⁺提高锰酸锂倍率性能的微观机制。结果表明, 尽管随着电流密度增大, 电极的放电比容量下降, 但掺K⁺提高材料的大倍率性能效果显著, 如最佳掺K⁺量(物质的量分数)1.0%时, 在10C (1C=150 mA·g^-1)下比容量提高了一倍, 远高于0.5C下的1.9%。原因在于掺K⁺后, 首先, 锰酸锂的晶胞体积扩大, Li-O键变长, Li、Mn阳离子混排程度降低, 载流子(Mn³⁺)量增多; 其次, 电极极化和电荷迁移阻抗降低, 提高了材料的充放电可逆性、导电性及锂离子扩散能力; 再者, [Mn₂]O₄骨架更稳定, 减小了电化学过程中内应力变化, 抑制了晶体结构变化和颗粒破碎; 最后, 钾离子掺杂使制备过程中材料团聚, 从而减小电解液与电极的接触面积, 减轻电解液的侵蚀, 抑制锰的溶解。

关键词: 锂离子电池, 正极材料, 钾离子掺杂, 微观机制, 倍率性能

Abstract:

Improving the high rate performance of lithium manganese spinel is one of the key research directions of Li-ion battery. In this study, spinel Li_1.1-_xK_xMn₂O₄ (0≤x≤0.03) was synthesized by a high-temperature solid-state method. The results indicate that K⁺ doping significantly improved the high rate performance of the cathode, while the discharge specific capacity of the electrode decreased with the current density increasing. With the optimum doping amount of 1.0% (molar fraction) K⁺, the discharge specific capacity of the cathode increased by 102.8% at 10C (1C=150 mA·g^-1), much higher than that (1.9%) at 0.5C. It can be attributed to the following points: K⁺ doping can firstly expand the cell volume and the Li-O bond length, lower the cation mixing of Li/Mn, and increase the content of carriers (Mn³⁺) of the material. Secondly, K⁺ doping can reduce the electrode polarization and charges transfer resistance, which develops the charge-discharge reversibility, electrical conductivity as well as the diffusion capability of the Li ions for the cathode. Thirdly, K⁺ doping can stabilize the framework of [Mn₂]O₄, degrade the change of internal stress during the electrochemical process, which inhibits the modification of the crystal structure and particle fragmentation. In addition, the existence of K⁺ promotes the agglomeration of the material during the preparation process, which reduces the contact area between the electrolyte and cathode in cell, thereby alleviating the erosion of the electrolyte, as well as the Mn dissolution of the cathode.

Key words: lithium-ion battery, cathode material, K⁺ doping, microscopic mechanism, rate performance

中图分类号:

TQ152

王洋, 范广新, 刘培, 尹金佩, 刘宝忠, 朱林剑, 罗成果. 钾离子掺杂提高锂离子电池正极锰酸锂性能的微观机制[J]. 无机材料学报, 2022, 37(9): 1023-1029.

WANG Yang, FAN Guangxin, LIU Pei, YIN Jinpei, LIU Baozhong, ZHU Linjian, LUO Chengguo. Microscopic Mechanism of K⁺ Doping on Performance of Lithium Manganese Cathode for Li-ion Battery[J]. Journal of Inorganic Materials, 2022, 37(9): 1023-1029.

图/表 18

图1 LKMO-n的XRD图谱与元素组成

Fig. 1 XRD patterns and elements composition of as-prepared LKMO-n

表1 LKMO-n的详细晶体结构参数

Table 1 Detailed crystal structural parameters for LKMO-n

Sample	d₍₁₁₁₎/nm	FWHM₍₁₁₁₎/(°)	I_(111)/(311)	a/nm	V/nm³	d_(Li-O)/nm	Mn/Li_8a	R_wp	S
LKMO-0	0.474	0.151	1.529	0.822	0.556	0.187	2.53%	10.23	1.13
LKMO-1	0.476	0.166	1.585	0.824	0.561	0.189	2.29%	10.97	1.13
LKMO-2	0.476	0.177	1.876	0.825	0.563	0.193	2.27%	10.53	1.07
LKMO-3	0.477	0.179	1.678	0.826	0.564	0.191	2.23%	10.91	1.15

图2 LKMO-0(a, c)和LKMO-1(b, d)的SEM照片, LKMO-1的EDS分布图(e) (方框区域)

Fig. 2 SEM images of LKMO-0 (a, c) and LKMO-1 (b, d), EDS mappings for LKMO-1 (e) (rectangular area)

图3 LKMO-1的XPS全谱图(a), LKMO-0(b)和LKMO-1(c)的Mn2p XPS高分辨光谱图

Fig. 3 (a) XPS full spectrum of LKMO-1, and High-resolution Mn2p XPS spectra of LKMO-0 (b) and LKMO-1 (c)

图4 LKMO-n的倍率性能

Fig. 4 Rate performances of LKMO-n

图5 LKMO-0(a)和LKMO-1(b)在不同扫描速率下的CV测试结果和氧化还原反应中ip随v1/2变化的拟合曲线(c)

Fig. 5 CV curves of LKMO-0 (a) and LKMO-1 (b) at different scan rates, and plots of ip versus v1/2 for redox reaction (c)

图6 LKMO-0和LKMO-1的EIS谱图

Fig. 6 EIS spectra of LKMO-0 and LKMO-1

表2 LKMO-0和LKMO-1的EIS拟合结果和Li+扩散系数

Table 2 Fitting results of EIS and diffusion coefficients of Li-ions of LKMO-0 and LKMO-1

Sample	Before charging		After charging/ discharging		D_Li⁺/(cm²·s^-1)
Sample	R_s/Ω	R_ct/Ω	R_s/Ω	R_ct/Ω	D_Li⁺/(cm²·s^-1)
LKMO-0	4.22	193.91	6.43	176.00	1.20×10^-11
LKMO-1	3.59	72.62	7.92	63.25	2.35×10^-11

图7 LKMO-0和LKMO-1在0.2C和10C倍率下循环5周后的XRD图谱

Fig. 7 XRD patterns of LKMO-0 and LKMO-1 after 5 cycles at 0.2C and 10C rate

图8 经30周循环后LKMO-0(a, c, d)和LKMO-1(b, e)的SEM照片

Fig. 8 SEM images of LKMO-0 (a, c, d) and LKMO-1 (b, e) after 30 cycles

表3 LKMO-0和LKMO-1在0.2C和10C循环5周后的晶体结构参数

Table 3 Crystal structural parameters of LKMO-0 and LKMO-1 after 5 cycles at 0.2C and 10C

Sample	Condition	a/nm	d₍₁₁₁₎/nm	2θ₍₁₁₁₎/(°)	FWHM₍₁₁₁₎/(°)	I_(111)/(311)	L/nm	Strain/%	Δ_Strain/%
LKMO-0	0.2C, 5th	0.822	0.474	18.661	0.148	1.385	62.7	0.153	0.139
LKMO-0	10C, 5th	0.813	0.469	18.823	0.155	1.663	68.0	0.292	0.139
LKMO-1	0.2C, 5th	0.824	0.476	18.679	0.171	1.394	51.0	0.338	0.020
LKMO-1	10C, 5th	0.822	0.474	18.679	0.165	1.393	51.5	0.358	0.020

图S1 LKMO-0(a)和LKMO-1(b)在不同倍率下的首次充放电曲线

Fig. S3 First charge/discharge curves of LKMO-0 (a) and LKMO-1 (b) at different rates

图S2 LKMO-0和LKMO-1的Z′随ω-1/2变化的拟合曲线

Fig. S3 Fitting curves of Z′ versus ω-1/2 of LKMO-0 and LKMO-1

图S3 LKMO-0和LKMO-1的B2cos2θ随sin2θ变化的拟合曲线

Fig. S3 Fitting curves of B2cos2θ versus sin2θ for LKMO-0 and LKMO-1

表S1 LKMO-0和LKMO-1的粒度分布和比表面积

Table S1 Particle size distributions and specific surface areas of LKMO-0 and LKMO-1

Sample	Particle size distribution/μm			S_BET/(m²·g^-1)
Sample	d₁₀	d₅₀	d₉₀	S_BET/(m²·g^-1)
LKMO-0	1.49	9.23	26.1	1.60
LKMO-1	1.71	8.27	24.9	1.34

表S2 LKMO-n的倍率性能

Table S3 Rate performances of LKMO-n

Sample	Average specific discharge capacity/ (mAh·g^-1)
Sample	0.2C	0.5C	1C	2C	5C	10C	0.2C
LKMO-0	106.33	97.27	90.39	77.54	48.86	27.90	102.40
LKMO-1	100.11	99.15	97.21	93.37	82.66	56.59	96.83
LKMO-2	106.09	101.47	90.60	72.37	44.12	24.11	103.69
LKMO-3	102.89	100.32	91.89	65.63	37.16	16.98	98.14

表S3 LKMO-0和LKMO-1在不同倍率下的充放电效率

Table S4 Charge-discharge efficiency at different rates for LKMO-0 and LKMO-1

Sample	Charge-discharge efficiency/%
Sample	0.2C	0.5C	1C	2C	5C	10C
LKMO-0	87.88	90.86	90.97	88.81	76.81	56.76
LKMO-1	94.54	98.46	96.65	94.79	85.18	63.53

表S4 LKMO-n的元素含量

Table S2 Elemental contents of LKMO-n

Sample	Molar concentration/(mmol·L^-1)			Molar ratio
Sample	Li	K	Mn	Li/K/Mn
LKMO-0	5.895	-	10.452	1.128/-/2
LKMO-1	5.914	0.055	10.775	1.097/0.010/2
LKMO-2	5.805	0.101	10.668	1.088/0.019/2
LKMO-3	5.716	0.154	10.546	1.084/0.029/2

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钾离子掺杂提高锂离子电池正极锰酸锂性能的微观机制

Microscopic Mechanism of K⁺ Doping on Performance of Lithium Manganese Cathode for Li-ion Battery

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钾离子掺杂提高锂离子电池正极锰酸锂性能的微观机制

Microscopic Mechanism of K+ Doping on Performance of Lithium Manganese Cathode for Li-ion Battery

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Microscopic Mechanism of K⁺ Doping on Performance of Lithium Manganese Cathode for Li-ion Battery