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

doi:10.15541/jim20210757

Abstract

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

CLC Number:

TQ152

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.

Figures/Tables 18

References 28

[1]	DURMUS Y E, ZHANG H, BAAKES F, et al. Side by side battery technologies with lithium-ion based batteries. Advanced Energy Materials, 2020, 10(24): 2000089. DOI URL
[2]	LI L L, LI S Y, LU Y Y. Suppression of dendritic lithium growth in lithium metal-based batteries. Chemical Communications, 2018, 54(50): 6648-6661. DOI URL
[3]	DING Y L, CANO Z P, YU A P, et al. Automotive Li-ion batteries: current status and future perspectives. Electrochemical Energy Reviews, 2019, 2(1): 1-28.
[4]	MU C H, LOU S A, ALI R, et al. Carbon-decorated LiMn₂O₄ nanorods with enhanced performance for supercapacitors. Journal of Alloys and Compounds, 2019, 805: 624-630.
[5]	ZHU Z X, WANG M M, MENG Y H, et al. A high-rate lithium manganese oxide-hydrogen battery. Nano Letters, 2020, 20(5): 3278-3283.
[6]	LI S Y, ZHU K L, LIU J L, et al. Porous LiMn₂O₄ microspheres with different pore size: preparation and application as cathode materials for lithium ion batteries. Journal of Electrochemical Energy Conversion and Storage, 2019, 16(1): 1-8.
[7]	XIANG M W, ZHOU X Y, ZHANG Z F, et al. LiMn₂O₄ prepared by liquid phase flameless combustion with F-Doped for lithium- ion battery cathode materials. Advanced Materials Research, 2013, 652-654: 825-830.
[8]	JIANG Q Q, LIU D D, ZHANG H, et al. Plasma-assisted sulfur doping of LiMn₂O₄ for high-performance lithium-ion batteries. Journal of Physical Chemistry C, 2015, 119(52): 28776-28782.
[9]	LIU J T, LI G, YU Y, et al. Synthesis and electrochemical performance evaluations of polyhedra spinel LiAl_xMn_2-_xO₄ (x≤0.20) cathode materials prepared by a solution combustion technique. Journal of Alloys and Compounds, 2017, 728: 1315-1328.
[10]	CHANDA P, VIVEK BANSALA, SUKRITIA V S. Investigations of spinel LiZn_xMn_2-_xO₄(x≤0.03) cathode materials for a lithium ion battery application. Materials Science & Engineering B, 2018, 238-239(DEC): 93-99.
[11]	XIONG L L, XU Y L, LEI P, et al. The electrochemical performance of sodium-ion-modified spinel LiMn₂O₄ used for lithium-ion batteries. Journal of Solid State Electrochemistry, 2014, 18(3): 713-719.
[12]	XIONG L L, XU Y L, XIAO X, et al. The effect of K-ion on the electrochemical performance of spinel LiMn₂O₄. Electronic Materials Letters, 2015, 11(1): 138-142.
[13]	CHUDZIK K, ŚWIĘTOSŁAWSKI M, BAKIERSKA M, et al. Electrochemical properties of K and S doped LiMn₂O₄ studied by GITT and EIS. Electrochimica Acta, 2021, 373: 137901.
[14]	CHUDZIK K, ŚWIĘTOSŁAWSKI M, BAKIERSKA M, et al. Surface modification and carbon coating effect on a high-performance K and S doped LiMn₂O₄. Applied Surface Science, 2020, 531:147138.
[15]	BAKIERSKA M, ŚWIĘTOSŁAWSKI M, CHUDZIK K, et al. Enhancing the lithium ion diffusivity in LiMn₂O_4-_yS_y cathode materials through potassium doping. Solid State Ionics, 2018, 317(January): 190-193.
[16]	RODRÍGUEZ R A, PÉREZ-CAPPE E L, LAFFITA Y M, et al. Structural defects in LiMn₂O₄ induced by gamma radiation and its influence on the Jahn-Teller effect. Solid State Ionics, 2018, 324(June): 77-86.
[17]	YU Z M, ZHAO L C. Structure and electrochemical properties of LiMn₂O₄. Transactions of Nonferrous Metals Society of China, 2007, 17(3): 659-664.
[18]	MARCHINI F, CALVO E J, WILLIAMS F J. Effect of the electrode potential on the surface composition and crystal structure of LiMn₂O₄ in aqueous solutions. Electrochimica Acta, 2018, 269: 706-713.
[19]	ZHAO H Y, LI F, BAI X Z, et al. Enhanced cycling stability of LiCu_xMn_1.95-_xSi_0.05O₄ cathode material obtained by solid-state method. Materials, 2018, 11(8): 1-10.
[20]	RAGAVENDRAN K, CHOU H L, LU L, et al. Crystal habits of LiMn₂O₄ and their influence on the electrochemical performance. Materials Science and Engineering B: Solid-State Materials for Advanced Technology, 2011, 176(16): 1257-1263.
[21]	WANG X Y, HAO H, LIU J L, et al. A novel method for preparation of macroposous lithium nickel manganese oxygen as cathode material for lithium ion batteries. Electrochimica Acta, 2011, 56(11): 4065-4069.
[22]	CHEN S, CHEN Z, CAO C B. Mesoporous spinel LiMn₂O₄ cathode material by a soft-templating route. Electrochimica Acta, 2016, 199: 51-58.
[23]	ZHOU S, WANG G X, XIAO Y, et al. Influence of charge status on the stress safety properties of Li(Ni_1/3Co_1/3Mn_1/3)O₂ cells. RSC Advances, 2016, 6(68): 63378-63389.
[24]	SETHURAMAN V A, VAN WINKLE N, ABRAHAM D P, et al. Real-time stress measurements in lithium-ion battery negative- electrodes. Journal of Power Sources, 2012, 206: 334-342.
[25]	FAN G X, WEN Y, LIU B Z, et al. An insight into the influence of crystallite size on the performances of microsized spherical Li(Ni_0.5Co_0.2Mn_0.3)O₂ cathode material composed of aggregated nanosized particles. Journal of Nanoparticle Research, 2018, 20(2): 43. DOI URL
[26]	KIZILTAŞ-YAVUZ N, HERKLOTZ M, HASHEM A M, et al. Synthesis, structural, magnetic and electrochemical properties of LiNi_1/3Mn_1/3Co_1/3O₂ prepared by a Sol-Gel method using table sugar as chelating agent. Electrochimica Acta, 2013, 113: 313-321.
[27]	GREELEY J, WARBURTON R E, CASTRO F C, et al. Oriented LiMn₂O₄ particle fracture from delithiation-driven surface stress. ACS Applied Materials and Interfaces, 2020, 12(43): 49182-49191.
[28]	THACKERAY M M. Exploiting the spinel structure for Li-ion battery applications: a tribute to John B. Goodenough. Advanced Energy Materials, 2021, 11(2): 1-8.

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

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

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

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

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