Effect of Zn Content on Lithium Storage Properties of Rock Salt Type High Entropy Oxides

doi:10.11901/1005.3093.2023.567

Chinese Journal of Materials Research

2024, Vol. 38

Issue (7): 508-518 DOI: 10.11901/1005.3093.2023.567

ARTICLES

Current Issue | Archive | Adv Search

Effect of Zn Content on Lithium Storage Properties of Rock Salt Type High Entropy Oxides

CHEN Shijie¹, BAO Mengfan¹, LIN Na¹, YANG Haiqin¹, MAO Aiqin¹^,²(

)

^1.Advanced Ceramics Research Center, School of Materials Science and Engineering, Anhui University of Technology, Ma'anshan 243032, China
^2.Key Laboratory of Green Fabrication and Surface Technology of Advanced Metal Materials, Ministry of Education, Ma'anshan 243032, China

Cite this article:

CHEN Shijie, BAO Mengfan, LIN Na, YANG Haiqin, MAO Aiqin. Effect of Zn Content on Lithium Storage Properties of Rock Salt Type High Entropy Oxides. Chinese Journal of Materials Research, 2024, 38(7): 508-518.

Download:

HTML

PDF(11106KB)
Export: BibTeX | EndNote (RIS)

Abstract

Rock salt-type high entropy oxide (Co_0.2Cu_0.2Mg_0.2Ni_0.2Zn_0.2)O as anode material for lithium-ion battery has attracted widespread attention due to its unique synergistic effect of multiple elements. Zn and part of Co elements provide the main source of electrode capacities, while MgO stabilizes the crystal structure, Ni, Cu, and the reduced residual Co may form a 3-dimensional network to enhance the conductivities of the oxide. In this study, a series of rock salt-type high entropy oxides (Co_0.22Cu_0.22Mg_0.22Ni_0.22Zn_0.12)O,(Co_0.2Cu_0.2Mg_0.2Ni_0.2Zn_0.2)O and (Co_0.18Cu_0.18Mg_0.18Ni_0.18Zn_0.28)O with different Zn contents were prepared by solution combustion method, while the effect of Zn ion concentration on the electrochemical performance of rock salt-type HEOs was also assessed. The results suggest that with the increasing Zn content, the electrochemical performance of the electrode material was enhanced. Although the (Co_0.2Cu_0.2Mg_0.2Ni_0.2Zn_0.2)O electrode exhibits a higher lattice distortion and oxygen vacancy concentration, resulting in a slightly higher intrinsic conductivity and lithium ion diffusion coefficient, however, the (Co_0.18Cu_0.18Mg_0.18Ni_0.18Zn_0.28)O electrode showed the most excellent electrochemical performance with the highest initial discharge specific capacity (777.06 mAh·g^-1) and cycling stability (capacity retention rate nearly 100% after 150 cycles) at 200 mA·g^-1, as well as excellent rate performance (specific capacity of 140.2 mAh·g^-1 at 3000 mA·g^-1), and it even shows the best cycling stability after 150 cycles at a high current density of 1000 mAh·g^-1 (specific capacity of 198.1 mAh·g^-1). The excellent electrochemical performance of the (Co_0.18Cu_0.18Mg_0.18-Ni_0.18Zn_0.28)O electrode may be attributed to the complete conversion of Zn element during the redox reaction. The higher Zn content is beneficial to increase capacities, while the appropriate oxygen vacancy concentration and lattice distortion may provide more channels for Li ion migration, thus resulting in higher cycle stability of the electrode.

Key words: inorganic non-metallic materials lithium-ion battery different Zn contents rocksalt type high-entropy oxide lattice distortion synergistic effect

Received: 22 November 2023

ZTFLH:

TM912

Fund: Director's Fund of Key Laboratory of Green Fabrication and Surface Technology of Advance Metal Materials, Ministry of Education(GFST2022ZR08);University Natural Science Research Project of Anhui Province(2023AH051104)

Corresponding Authors: MAO Aiqin, Tel: 13855599146, E-mail: maoaiqinmaq@163.com

	Service

	E-mail this article
	Add to citation manager
	E-mail Alert
	RSS
	（）
	Articles by authors
	CHEN Shijie
	BAO Mengfan
	LIN Na
	YANG Haiqin
	MAO Aiqin

URL:

https://www.cjmr.org/EN/10.11901/1005.3093.2023.567 OR https://www.cjmr.org/EN/Y2024/V38/I7/508

Fig.1 XRD patterns of the samples and their magnifications

Fig.2 SEM (a, b) and EDS mapping pictures (c) of Zn0.28 sample and N₂ adsorption/desorption isotherms and the BJH pore size distribution curves of three samples (d)

Table 1 BET specific surface area (S_BET), BJH adsorption cumulative pore volume (V_BJH), average pore diameter (D_aver) and the most probable pore diameter (D_most)

Fig.3 XPS survey spectra of the samples (a), High resolution XPS spectra of Co、Cu、Ni、O (b~e) and electrical conductivity (f)

Table 2 Valence distribution and average valence of Co and Cu elements calculated according to XPS analysis

Fig.4 CV plots at 0.1 mV·s^-1 sweep rate (a~c) and charge/discharge profiles (d~f) of Zn0.12、Zn0.2 and Zn0.28 electrodes; cycling performance and coulomb efficiency at a specific current of 200 mA·g^-1 (g), rate performance (h) and long cycle performance at 1000 mA·g^-1 (i)

Fig.5 SEM images of as-synthesized electrodes before and after 150 cycles at 200 mA·g^-1 (a, d) Zn0.12, (b, e) Zn 0.2, (c, f) Zn0.28

Fig.6 CV curves under various scan rates of Zn0.28 electrode (a), lg(i_p) vs. lg(v) curves (b), capacitance (blue area) and diffusion contribution (red area) at a scan rate of 1 mV·s^-1 (c), and capacitive contribution ratio at different scan rates (d); GITT curves (e) and lithium-ion diffusion coefficients calculated from GITT curves of electrodes during the charge/discharge process (f)

Fig.7 In-situ EIS during the first (a, b) and third (c, d) cycles of Zn0.28 electrode. EIS measurements of the three electrodes before cycling (e) and corresponding plots of Z' against ω^-1/2 in the low-frequency region (i); EIS spectra together with the equivalent circuit before cycling, after 3 and 150 cycles: Zn0.12 (f), Zn 0.2 (g), Zn0.28 (h) and the corresponding plots of Z′ against ω^-1/2 in the low-frequency region (j~l)

Samples	R_s / Ω			R_ct / Ω			D $L i +$ / 10^-21 cm²·s^-1
Samples	Pristine	3rd	100th	Pristine	3rd	100th	Pristine	3rd	100th
Zn0.12	4.4	5.2	6.1	338.0	26.8	31.8	14.9	2.1	14.8
Zn0.2	8.3	6.0	8.6	248.0	42.0	14.9	10.4	2.5	20.4
Zn0.28	5.6	4.3	6.4	283.7	8.1	26.9	17.3	2.5	10.8

Table 3 Parameters of equivalent circuit diagrams and calculated lithium ion diffusion coefficient of as-prepared electrodes at pristine state, after 3 cycles and 100 cycles

[1]	Liu Y Y, Zhu Y Y, Cui Y. Challenges and opportunities towards fast-charging battery materials [J]. Nat. Energy, 2019, 4: 540 doi: 10.1038/s41560-019-0405-3
[2]	Lim S, Kim J H, Yamada Y, et al. Improvement of rate capability by graphite foam anode for Li secondary batteries [J]. J. Power Sources, 2017, 355: 164
[3]	Xiang H M, Xing Y, Dai F Z, et al. High-entropy ceramics: Present status, challenges, and a look forward [J]. J. Adv. Ceram., 2021, 10: 385
[4]	Xiang H Z, Quan F, Li W C, et al. Research progress in preparation and application of high-entropy oxides [J]. Chin. J. Process Eng., 2020, (3): 245
	项厚政, 权峰, 李文超等. 高熵氧化物的制备及应用研究进展 [J]. 过程工程学报, 2020, (3): 245 doi: 10.12034/j.issn.1009-606X.219228
[5]	Rost C M, Sachet E, Borman T, et al. Entropy-stabilized oxides [J]. Nat. Commun., 2015, 6: 8485 doi: 10.1038/ncomms9485 pmid: 26415623
[6]	Sarkar A, Djenadic R, Usharani N J, et al. Nanocrystalline multicomponent entropy stabilised transition metal oxides [J]. J. Eur. Ceram. Soc., 2017, 37: 747
[7]	Sarkar A, Velasco L, Wang D, et al. High entropy oxides for reversible energy storage [J]. Nat. Commun., 2018, 9: 3400 doi: 10.1038/s41467-018-05774-5 pmid: 30143625
[8]	Qiu N, Chen H, Yang Z M, et al. A high entropy oxide (Mg_0.2Co_0.2Ni_0.2Cu_0.2Zn_0.2O) with superior lithium storage performance [J]. J. Alloys Compd., 2019, 777: 767
[9]	Wang S Y, Chen T Y, Kuo C H, et al. Operando synchrotron transmission X-ray microscopy study on (Mg, Co, Ni, Cu, Zn)O high-entropy oxide anodes for lithium-ion batteries [J]. Mater. Chem. Phys., 2021, 274: 125105
[10]	Chen H, Qiu N, Wu B Z, et al. Tunable pseudocapacitive contribution by dimension control in nanocrystalline-constructed (Mg_0.2Co_0.2Ni_0.2Cu_0.2Zn_0.2)O solid solutions to achieve superior lithium-storage properties [J]. RSC Adv., 2019, 9: 28908
[11]	Guo H C, Shen J X, Wang T L, et al. Design and fabrication of high-entropy oxide anchored on graphene for boosting kinetic performance and energy storage [J]. Ceram. Int., 2022, 48: 3344
[12]	Triolo C, Xu W, Petrovičovà B, et al. Evaluation of entropy‐stabilized (Mg_0.2Co_0.2Ni_0.2Cu_0.2Zn_0.2)O oxides produced via solvothermal method or electrospinning as anodes in lithium‐ion batteries [J]. Adv. Funct. Mater., 2022, 32: 2202892
[13]	Wang K, Hua W B, Huang X H, et al. Synergy of cations in high entropy oxide lithium ion battery anode [J]. Nat. Commun., 2023, 14: 1487 doi: 10.1038/s41467-023-37034-6 pmid: 36932071
[14]	Berardan D, Meena A K, Franger S, et al. Controlled Jahn-Teller distortion in (MgCoNiCuZn)O-based high entropy oxides [J]. J. Alloys Compd., 2017, 704: 693
[15]	Quan F, Xiang H Z, Yang L, et al. Research progress in preparation and application of high-entropy-alloy powders [J]. Chin. J. Process Eng., 2019, 19: 447
	权峰, 项厚政, 杨磊等. 高熵合金粉体制备及应用研究进展 [J]. 过程工程学报, 2019, 19: 447
[16]	Thiel T C, Fowlie J, Autieri C, et al. Coupling lattice instabilities across the interface in ultrathin oxide heterostructures [J]. ACS Materials Lett., 2020, 2: 389
[17]	Li Y F, Xu Y S, Yin Y R, et al. Entropy engineering design of high-performing lithiated oxide cathodes for proton-conducting solid oxide fuel cells [J]. J. Adv. Ceram. 2023, 12: 2017
[18]	Mao A Q, Xiang H Z, Zhang Z G, et al. Solution combustion synthesis and magnetic property of rock-salt (Co_0.2Cu_0.2Mg_0.2Ni_0.2Zn_0.2)O high-entropy oxide nanocrystalline powder [J]. J. Magn. Magn. Mater., 2019, 484: 245
[19]	Zhu K X, Gao H Y, Hu G X, et al. Scalable synthesis of hierarchical hollow Li₄Ti₅O₁₂ microspheres assembled by zigzag-like nanosheets for high rate lithium-ion batteries [J]. J. Power Sources, 2017, 340: 263
[20]	Zou F, Hu X, Li Z, et al. MOF-derived porous ZnO/ZnFe₂O₄/C octahedra with hollow interiors for high-rate lithium-ion batteries [J]. Adv. Mater., 2014, 26: 6622
[21]	Noh H B, Lee K S, Chandra P, et al. Application of a Cu-Co alloy dendrite on glucose and hydrogen peroxide sensors [J]. Electrochimica Acta, 2012, 61: 36
[22]	Wang D, Jiang S D, Duan C Q, et al. Spinel-structured high entropy oxide (FeCoNiCrMn)₃O₄ as anode towards superior lithium storage performance [J]. J. Alloys Compd., 2020, 844: 156158
[23]	Usharani N J, Shringi R, Sanghavi H, et al. Role of size, alio-/multi-valency and non-stoichiometry in the synthesis of phase-pure high entropy oxide (Co, Cu, Mg, Na, Ni, Zn)O [J]. Dalton Trans., 2020, 49: 7123
[24]	Guo M, Liu Y F, Zhang F N, et al. Inactive Al³⁺-doped La(CoCrFe-MnNiAl _x )_1/(5+ _x₎O₃ high-entropy perovskite oxides as high performance supercapacitor electrodes [J]. J. Adv. Ceram., 2022, 11: 742
[25]	Li S, Peng Z J, Fu X L. Zn_0.5Co_0.5Mn_0.5Fe_0.5Al_0.5Mg_0.5O₄ high-entropy oxide with high capacity and ultra-long life for Li-ion battery anodes [J]. J. Adv. Ceram., 2023, 12: 59
[26]	Phakatkar A H, Saray M T, Rasul M G, et al. Ultrafast synthesis of high entropy oxide nanoparticles by flame spray pyrolysis [J]. Langmuir, 2021, 37: 9059
[27]	Xu Y S, Xu X, Bi L. A high-entropy spinel ceramic oxide as the cathode for proton-conducting solid oxide fuel cells [J]. J. Adv. Ceram., 2022, 11: 794
[28]	Li L, Meng T, Wang J, et al. Oxygen vacancies boosting lithium-ion diffusion kinetics of lithium germanate for high-performance lithium storage [J]. ACS Appl. Mater. Interfaces 2021, 13: 24804
[29]	Xiao B, Wu G, Wang T D, et al. High-entropy oxides as advanced anode materials for long-life lithium-ion batteries [J]. Nano Energy, 2022, 95
[30]	Tang Z K, Xue Y F, Teobaldi G, et al. The oxygen vacancy in Li-ion battery cathode materials [J]. Nanoscale Horizons, 2020, 5: 1453
[31]	Qian K C, Yan Y, Xi S B, et al. Elucidating the strain-vacancy-activity relationship on structurally deformed Co@CoO nanosheets for aqueous phase reforming of formaldehyde [J]. Small, 2021, 17: 2102970
[32]	Luo X F, Patra J, Chuang W T, et al. Charge-discharge mechanism of high-entropy Co-free spinel oxide toward Li⁺ storage examined using operando quick-scanning X-ray absorption spectroscopy [J]. Adv. Sci., 2022, 9: 2201219
[33]	Liu X F, Xing Y Y, Xu K, et al. Kinetically accelerated lithium storage in high-entropy (LiMgCoNiCuZn)O enabled by oxygen vacancies [J]. Small, 2022, 18: 2200524
[34]	Qiu N, Chen H, Yang Z M, et al. A high entropy oxide (Mg_0.2Co_0.2Ni_0.2Cu_0.2Zn_0.2)O with superior lithium storage performance [J]. J. Alloys Compd., 2019, 777: 767
[35]	Jia Y G, Shao X, Cheng J, et al. Preparation and lithium storage performance of pseudocapacitance-controlled chalcogenide high-entropy oxide La(Co_0.2Cr_0.2Fe_0.2Mn_0.2Ni_0.2)O₃ anode materials [J]. Chem. J. Chin. Univ., 2022, 43: 157
	贾洋刚, 邵霞, 程婕等. 赝电容控制型钙钛矿高熵氧化物La(Co_0.2Cr_0.2Fe_0.2Mn_0.2Ni_0.2)O₃材料的制备及储锂性能 [J]. 高等学校化学学报, 2022, 43: 157
[36]	Li Q, Li H S, Xia Q T, et al. Extra storage capacity in transition metal oxide lithium-ion batteries revealed by in situ magnetometry [J]. Nat. Mater., 2021, 20: 76
[37]	Sun Z, Zhao Y J, Sun C, et al. High entropy spinel-structure oxide for electrochemical application [J]. Chem. Eng. J., 2022, 431: 133448
[38]	Yan S, Luo S, Yang L, et al. Novel P2-type layered medium-entropy ceramics oxide as cathode material for sodium-ion batteries [J]. J. Adv. Ceram., 2021, 11: 158
[39]	Tian K H, Duan C Q, Ma Q, et al. High-entropy chemistry stabilizing spinel oxide (CoNiZnXMnLi)₃O₄ (X = Fe, Cr) for high-performance anode of Li-ion batteries [J]. Rare Metals, 2021, 41: 1265
[40]	Shen L F, Lv H F, Chen S Q, et al. Peapod-like Li₃VO₄/N-doped carbon nanowires with pseudocapacitive properties as advanced materials for high-energy lithium-ion capacitors [J]. Adv. Mater., 2017, 29: 1700142
[41]	Jia Y G, Chen S J, Shao X, et al. Preparation and High-performance Lithium-ion Storage of Cobalt-free Perovskite High-entropy Oxide Anode Materials [J]. Acta Chim. Sin., 2023, 81: 486
	贾洋刚, 陈诗洁, 邵霞等. 高性能无钴化钙钛矿型高熵氧化物负极材料的制备及储锂性能研究 [J]. 化学学报 2023, 81: 486 doi: 10.6023/A23020046
[42]	Wang P P, Jia Y G, Shao X, et al. Preparation and lithium storage performance of K⁺-doped spinel (Co_0.2Cr_0.2Fe_0.2Mn_0.2Ni_0.2)₃O₄ high-entropy oxide anode materials [J]. CIESC Journal, 2022, 73: 5625
	王朋朋, 贾洋刚, 邵霞等. K⁺掺杂尖晶石型(Co_0.2Cr_0.2Fe_0.2Mn_0.2-Ni_0.2)₃O₄高熵氧化物负极材料制备与储锂性能研究 [J]. 化工学报, 2022, 73: 5625 doi: 10.11949/0438-1157.20221116
[43]	Wang X L, Liu J, Hu Y F, et al. Oxygen vacancy-expedited ion diffusivity in transition-metal oxides for high-performance lithium-ion batteries [J]. Sci. China Mater., 2022, 65: 1421
[44]	Jia Y G, Chen S J, Shao X, et al. Synergetic effect of lattice distortion and oxygen vacancies on high-rate lithium-ion storage in high-entropy perovskite oxide [J]. J. Adv. Ceram., 2023, 12: 1214
[45]	Xiao B, Wu G, Wang T, et al. Enhanced Li-ion diffusion and cycling stability of Ni-free high-entropy spinel oxide anodes with high-concentration oxygen vacancies [J]. ACS Appl. Mater. Interfaces, 2023, 15: 2792

[1]	YUAN Xinzhong, WANG Cunjing, YAO Peng, LI Qiong, MA Zhihua, LI Pengfa. Preparation of N and O Co-doped Carbon Materials by Salt Sealing Method for Electrode of Supercapacitors[J]. 材料研究学报, 2024, 38(7): 529-536.
[2]	WU Qianfang, HE Qun, CHANG Bing, QUAN Yuxin, HU Jingwen, LI Saisai, CAO Yingnan. Preparation and Neutron Shielding Properties of Fiberglass Based Thermal Insulating Porous Ceramics[J]. 材料研究学报, 2024, 38(6): 471-480.
[3]	WANG Jun, WANG Xuanli, LIU Shuang, SONG Rui, SONG Xiwen. Effect of Mn Doping on Microstructure and Thermal Conductivity of (Y_0.4Er_0.6)₃Al₅O₁₂ Ceramics Material for Thermal Barrier Coating[J]. 材料研究学报, 2024, 38(6): 463-470.
[4]	GUO Zhinan, ZHAO Qiang, LI Shuying, WANG Junli, XU Lin, SHANG Jianpeng, GUO Yong. Preparation and Degradation Performance of Composite Photocatalyst of Two-Dimensional Layered ZnNiAl-LDH/ Cuprous Oxide Particles[J]. 材料研究学报, 2024, 38(6): 423-429.
[5]	WANG Wei, CHANG Wenjuan, LV Fanfan, XIE Zelei, YU Chengcheng. Preparation and Tribological Properties of Fluorinated Boron Nitride Nanosheets Water-based Additive[J]. 材料研究学报, 2024, 38(6): 410-422.
[6]	TAN Yiling, LI Shichun, SUN Jie. Preparation of Metal-organic Framework Porous Glass a_gSALEM-2[J]. 材料研究学报, 2024, 38(5): 373-378.
[7]	XU Hui, ZHANG Peiyuan, XU Nana, LIU Tao, ZHANG Xiaoshan, WANG Bing, WANG Yingde. Mechanical Property and Thermal Insulation Performance of SiO₂/ZrO₂ Nanofiber Membranes with High Thermal Stability[J]. 材料研究学报, 2024, 38(5): 365-372.
[8]	WANG Yan, ZHANG Hao, CHANG Na, WANG Haitao. Preparation of Acid-alkali Modified Coal Fly Ash Adsorbent and Its Removal Performance on Dyes[J]. 材料研究学报, 2024, 38(5): 379-389.
[9]	LI Jing, XU Yingchao, FAN Haoshuang, LU Yi, LI Li, ZHANG Xianyu. Preparation and Luminescence Properties of a Novel Double Perovskite Ca₂GdSbO₆:Sm³⁺ Reddish-orange Phosphor[J]. 材料研究学报, 2024, 38(4): 288-296.
[10]	LIU Rui, ZHANG Dingdong, ZHANG Hui, REN Wencai, DU Jinhong. Effects of the Thickness of the Hole Transport Layer on the Performance of Graphene-based Organic Light-emitting Diodes[J]. 材料研究学报, 2024, 38(3): 168-176.
[11]	ZHOU Lichen. Preparation of Fluorine Modified Titanium Dioxide Catalyst and Its Photocatalytic Degradation for Oilfield Wastewater[J]. 材料研究学报, 2024, 38(2): 141-150.
[12]	LI Bosen, LIAO Zhongxin, GAO Daqiang. Effect of BNZ Component on Structure and Property of KNN Based Lead-free Piezoelectric Ceramics[J]. 材料研究学报, 2024, 38(1): 51-60.
[13]	SHAO Hongmei, CUI Yong, XU Wendi, ZHANG Wei, SHEN Xiaoyi, ZHAI Yuchun. Template-free Hydrothermal Preparation and Adsorption Capacity of Hollow Spherical AlOOH[J]. 材料研究学报, 2023, 37(9): 675-684.
[14]	SONG Lifang, YAN Jiahao, ZHANG Diankang, XUE Cheng, XIA Huiyun, NIU Yanhui. Carbon Dioxide Adsorption Capacity of Alkali-metal Cation Dopped MIL125[J]. 材料研究学报, 2023, 37(9): 649-654.
[15]	REN Fuyan, OUYANG Erming. Photocatalytic Degradation of Tetracycline Hydrochloride by g-C₃N₄ Modified Bi₂O₃[J]. 材料研究学报, 2023, 37(8): 633-640.

No Suggested Reading articles found!

Viewed

Full text

Abstract

Cited

Shared

Discussed