Journal Home > Volume 10 , issue 3

CoCO3 with high theoretical capacity has been considered as a candidate anode for the next generation of lithium-ion batteries (LIBs). However, the electrochemical performance of CoCO3 itself, especially the cyclic stability at high current density, hinders its application. Herein, pure phase CoCO3 particles with different particle and pore sizes were prepared by adjusting the solvents (diethylene glycol, ethylene glycol, and deionized water). Among them, CoCO3 synthesized with diethylene glycol (DG-CC) as the solvent shows the best electrochemical performance owing to the smaller particle size and abundant mesoporous structure to maintain robust structural stability. A high specific capacity of 690.7 mAh/g after 1000 cycles was achieved, and an excellent capacity retention was presented. The capacity was contributed by diverse electrochemical reactions and the impedance of DG-CC under different cycles was further compared. Those results provide an important reference for the structural design and stable cycle performance of pure CoCO3.


menu
Abstract
Full text
Outline
Electronic supplementary material
About this article

Solvents adjusted pure phase CoCO3 as anodes for high cycle stability

Show Author's information Liming LIUa,bXiaoxiao HUANGa,b( )Zengyan WEIa,bXiaoming DUANa,bBo ZHONGcLong XIAcTao ZHANGcHuatao WANGcDechang JIAa,bYu ZHOUa,bRui ZHANGd( )
Department of Materials Science, School of Material Science and Engineering, Harbin Institute of Technology, Harbin 150001, China
Key Laboratory of Advanced Structural Functional Integration Materials & Green Manufacturing Technology, Harbin Institute of Technology, Harbin 150001, China
School of Materials Science and Engineering, Harbin Institute of Technology at Weihai, Weihai 264009, China
College of Materials Science and Engineering, Hunan University, Changsha 410082, China

Abstract

CoCO3 with high theoretical capacity has been considered as a candidate anode for the next generation of lithium-ion batteries (LIBs). However, the electrochemical performance of CoCO3 itself, especially the cyclic stability at high current density, hinders its application. Herein, pure phase CoCO3 particles with different particle and pore sizes were prepared by adjusting the solvents (diethylene glycol, ethylene glycol, and deionized water). Among them, CoCO3 synthesized with diethylene glycol (DG-CC) as the solvent shows the best electrochemical performance owing to the smaller particle size and abundant mesoporous structure to maintain robust structural stability. A high specific capacity of 690.7 mAh/g after 1000 cycles was achieved, and an excellent capacity retention was presented. The capacity was contributed by diverse electrochemical reactions and the impedance of DG-CC under different cycles was further compared. Those results provide an important reference for the structural design and stable cycle performance of pure CoCO3.

Keywords:

lithium ion battery (LIB), cobalt carbonate, solvothermal method, morphological control, solvent, pure phase
Received: 11 September 2020 Revised: 24 December 2020 Accepted: 29 December 2020 Published: 15 April 2021 Issue date: June 2021
References(36)
[1]
Li M, Lu J, Chen ZW, et al. 30 years of lithium-ion batteries. Adv Mater 2018, 30:1800561.
[2]
Zeng XQ, Li M, Abd EI-Hady D, et al. Commercialization of lithium battery technologies for electric vehicles. Adv Energy Mater 2019, 9: 1900161.
[3]
Winter M, Barnett B, Xu K. Before Li ion batteries. Chem Rev 2018, 118: 11433-11456.
[4]
Zhang SS. Identifying rate limitation and a guide to design of fast-charging Li-ion battery. InfoMat 2020, 2: 942-949.
[5]
Ely DR, García RE. Heterogeneous nucleation and growth of lithium electrodeposits on negative electrodes. J Electrochem Soc 2013, 160: A662-A668.
[6]
Poizot P, Laruelle S, Grugeon S, et al. Nano-sized transition-metal oxides as negative-electrode materials for lithium-ion batteries. Nature 2000, 407: 496-499.
[7]
Chu YT, Guo LY, Xi BJ, et al. Embedding MnO@Mn3O4 nanoparticles in an N-doped-carbon framework derived from Mn-organic clusters for efficient lithium storage. Adv Mater 2018, 30: 1704244.
[8]
Zhang R, Huang XX, Wang D, et al. Single-phase mixed transition metal carbonate encapsulated by graphene: Facile synthesis and improved lithium storage properties. Adv Funct Mater 2018, 28: 1705817.
[9]
Zhao SQ, Wang ZW, He YJ, et al. A robust route to Co2(OH)2CO3 ultrathin nanosheets with superior lithium storage capability templated by aspartic acid-functionalized graphene oxide. Adv Energy Mater 2019, 9: 1901093.
[10]
Mei J, Liao T, Kou LZ, et al. Two-dimensional metal oxide nanomaterials for next-generation rechargeable batteries. Adv Mater 2017, 29: 1700176.
[11]
Reddy MV, Subba Rao GV, Chowdari BVR. Metal oxides and oxysalts as anode materials for Li ion batteries. Chem Rev 2013, 113: 5364-5457.
[12]
Li JF, Li M, Guo C, et al. Recent progress and challenges of micro-/nanostructured transition metal carbonate anodes for lithium ion batteries. Eur J Inorg Chem 2018, 41: 4508-4521.
[13]
Aragón MJ, Pérez-Vicente C, Tirado JL. Submicronic particles of manganese carbonate prepared in reverse micelles: A new electrode material for lithium-ion batteries. Electrochem Commun 2007, 9: 1744-1748.
[14]
Wang LB, Tang WJ, Jing Y, et al. Do transition metal carbonates have greater lithium storage capability than oxides? A case study of monodisperse CoCO3 and CoO microspindles. ACS Appl Mater Interfaces 2014, 6: 12346-12352.
[15]
Ding ZJ, Qin XY, You CH, et al. Different solid electrolyte interface and anode performance of CoCO3 microspheres due to graphene modification and LiCoO2||CoCO3@rGO full cell study. Electrochimica Acta 2018, 270: 192-204.
[16]
Zhao ZW, Wang ZL, Denis DK, et al. Intrinsic lithium storage mechanisms and superior electrochemical behaviors of monodispersed hierarchical CoCO3 sub-microspheroids as a competitive anode towards Li-ion batteries. Electrochimica Acta 2019, 307: 20-29.
[17]
Ding ZJ, Yao B, Feng JK, et al. Enhanced rate performance and cycling stability of a CoCO3-polypyrrole composite for lithium ion battery anodes. J Mater Chem A 2013, 1: 11200-11209.
[18]
Shao LY, Ma R, Wu KQ, et al. Metal carbonates as anode materials for lithium ion batteries. J Alloys Compd 2013, 581: 602-609.
[19]
Huang GY, Xu SM, Yang Y, et al. Micro-spherical CoCO3 anode for lithium-ion batteries. Mater Lett 2014, 131: 236-239.
[20]
Li HY, Tseng CM, Yang CH, et al. Eco-efficient synthesis of highly porous CoCO3 anodes from supercritical CO2 for Li+ and Na+ storage. ChemSusChem 2017, 10: 2464-2472.
[21]
Shi SJ, Zhang M, Liu YY, et al. Efficient construction of a CoCO3/graphene composite anode material for lithium-ion batteries by stirring solvothermal reaction. Ceram Int 2018, 44: 3718-3725.
[22]
Zeng TB, Zhang CH. Facile-synthesized amorphous CoCO3 for high-capacity lithium-ion battery anode. Ionics 2019, 25: 4149-4159.
[23]
Su LW, Zhou Z, Qin X, et al. CoCO3 submicrocube/ graphene composites with high lithium storage capability. Nano Energy 2013, 2: 276-282.
[24]
Lu ZP, Wang H, Zhou T, et al. CoCO3 micrometer particles stabilized by carbon nanofibers networks as composite electrode for enhanced rate and cyclic performance of lithium-ion batteries. Electrochimica Acta 2018, 270: 22-29.
[25]
Zhao SQ, Wei SS, Liu R, et al. Cobalt carbonate dumbbells for high-capacity lithium storage: A slight doping of ascorbic acid and an enhancement in electrochemical performances. J Power Sources 2015, 284: 154-161.
[26]
Yin JJ, Ding ZJ, Lei DN, et al. Zn-substituted CoCO3 embedded in carbon nanotubes network as high performance anode for lithium-ion batteries. J Alloys Compd 2017, 712: 605-612.
[27]
Jin Y, Zhu B, Lu ZD, et al. Challenges and recent progress in the development of Si anodes for lithium-ion battery. Adv Energy Mater 2017, 7: 1700715.
[28]
Zhao Y, Wang LP, Sougrati MT, et al. A review on design strategies for carbon based metal oxides and sulfides nanocomposites for high performance Li and Na ion battery anodes. Adv Energy Mater 2017, 7: 1601424.
[29]
Wang ST, Yang Y, Dong YH, et al. Recent progress in Ti-based nanocomposite anodes for lithium ion batteries. J Adv Ceram 2019, 8: 1-18.
[30]
Zhou LM, Zhang K, Hu Z, et al. Recent developments on and prospects for electrode materials with hierarchical structures for lithium-ion batteries. Adv Energy Mater 2018, 8: 1701415.
[31]
Du HM, Jiao LF, Wang QH, et al. Morphology control of CoCO3 crystals and their conversion to mesoporous Co3O4 for alkaline rechargeable batteries application. CrystEngComm 2013, 15: 6101-6109.
[32]
Zhong YR, Su LW, Yang M, et al. Rambutan-like FeCO3 hollow microspheres: Facile preparation and superior lithium storage performances. ACS Appl Mater Interfaces 2013, 5: 11212-11217.
[33]
Cao ZX, Ding YM, Zhang J, et al. Submicron peanut-like MnCO3 as an anode material for lithium ion batteries. RSC Adv 2015, 5: 56299-56303.
[34]
Wang YY, Zhao ZW, Liu Y, et al. Precipitant-free solvothermal construction of spindle-like CoCO3/reduced graphene oxide hybrid anode toward high-performance lithium-ion batteries. Rare Met 2020, 39: 1082-1091.
[35]
Laruelle S, Grugeon S, Poizot P, et al. On the origin of the extra electrochemical capacity displayed by MO/Li cells at low potential. J Electrochem Soc 2002, 149: A627-A634.
[36]
Zhang R, Wang D, Qin LC, et al. MnCO3/Mn3O4/reduced graphene oxide ternary anode materials for lithium-ion batteries: Facile green synthesis and enhanced electrochemical performance. J Mater Chem A 2017, 5: 17001-17011.
File
40145_2020_453_MOESM1_ESM.pdf (1,013.5 KB)
Publication history
Copyright
Acknowledgements
Rights and permissions

Publication history

Received: 11 September 2020
Revised: 24 December 2020
Accepted: 29 December 2020
Published: 15 April 2021
Issue date: June 2021

Copyright

© The Author(s) 2020

Acknowledgements

This work was supported by the National Natural Science Foundation of China (NSFC) (Nos. 51772060, 51372052, 51672059, 51621091, and 51902102), Natural Science Foundation of Hunan Province (No. 2020JJ5042), and Postdoctoral Science Foundation of China (No. 2020M672478).

Rights and permissions

This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made.

The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder.

To view a copy of this licence, visit http://creativecommons. org/licenses/by/4.0/.

Reprints and Permission requests may be sought directly from editorial office.

Return