镁掺杂氧化锰电极材料用于高性能水系镁离子二次电池

赵越; 王贝; 施敏杰; 安世博; 赵丽萍; 晏超

doi:10.1007/s12613-021-2346-7

Volume 29 Issue 11

Nov. 2022

Turn off MathJax

图(8) / 表(2)

数据统计

计量

文章访问数: 1193
HTML全文浏览量: 461
PDF下载量: 80
被引次数: 0

文章导航 > 矿物冶金与材料学报（英文） > 2022 > 29(11): 1954-1962

Yue Zhao, Bei Wang, Minjie Shi, Shibo An, Liping Zhao, and Chao Yan, Mg-intercalation engineering of MnO₂ electrode for high-performance aqueous magnesium-ion batteries, Int. J. Miner. Metall. Mater., 29(2022), No. 11, pp. 1954-1962. https://doi.org/10.1007/s12613-021-2346-7

Cite this article as:

Yue Zhao, Bei Wang, Minjie Shi, Shibo An, Liping Zhao, and Chao Yan, Mg-intercalation engineering of MnO2 electrode for high-performance aqueous magnesium-ion batteries, Int. J. Miner. Metall. Mater., 29(2022), No. 11, pp. 1954-1962. https://doi.org/10.1007/s12613-021-2346-7

Citation:

PDF( 2805 KB)

引用本文 PDF XML SpringerLink

研究论文

镁掺杂氧化锰电极材料用于高性能水系镁离子二次电池

1)
江苏科技大学材料科学与工程学院，镇江 212003，中国
2)
上海交通大学材料科学与工程学院金属基复合材料国家重点实验室，上海 200240，中国

通讯作者:
施敏杰 E-mail: shiminjie@just.edu.cn

晏超 E-mail: chaoyan@just.edu.cn

文章亮点

(1) 提出了一种新颖的氧化锰电极材料的镁掺杂工程技术。

(2) 理论计算与原位拉曼证实了镁掺杂对于氧化锰的重要作用。

(3) 镁掺杂氧化锰作为电极材料展现出高比容量和循环稳定性。

(4) 实现了软包装型水系镁离子二次电池的高比能与长续航特性。

中文摘要

水系镁离子二次电池在低成本与高安全性储能设备中应用前景广阔。虽然氧化锰被认为是水系镁离子电池中一种有潜力的电极材料，但其电子导电性低和循环性能差的问题极大地阻碍了氧化锰电极材料实际应用。本文提出了一种新颖的氧化锰电极材料的镁掺杂工程技术，同时对构建的镁掺杂氧化锰电极材料的电子结构和电化学性能进行了深入研究。DFT理论计算证明了镁掺杂对调节氧化锰电子结构的重要作用，并且原位拉曼结果也证实了镁掺杂氧化锰在充放电过程中可逆的相变过程。因此，该电极材料展现出高比容量（419.8 mAh·g⁻¹），以及优越的循环性能（1000次循环后容量几乎没有衰减）。基于这种镁掺杂氧化锰电极材料，我们成功组装了一种软包装型水系镁离子二次电池，该储能器件具有优越的电化学储能性能，实现了水系镁离子二次电池的高比能与长续航特性，揭示了其在高性能能源技术领域中的巨大应用潜能。

关键词:

Research Article

Mg-intercalation engineering of MnO₂ electrode for high-performance aqueous magnesium-ion batteries

+ Author Affiliations

Abstract

Abstract

Rechargeable aqueous magnesium-ion batteries (MIBs) show great promise for low-cost, high-safety, and high-performance energy storage applications. Although manganese dioxide (MnO₂) is considered as a potential electrode material for aqueous MIBs, the low electrical conductivity and unsatisfactory cycling performance greatly hinder the practical application of MnO₂ electrode. To overcome these problems, herein, a novel Mg-intercalation engineering approach for MnO₂ electrode to be used in aqueous MIBs is presented, wherein the structural regulation and electrochemical performance of the Mg-intercalation MnO₂ (denoted as MMO) electrode were thoroughly investigated by density functional theory (DFT) calculations and in-situ Raman investigation. The results demonstrate that the Mg intercalation is essential to adjusting the charge/ion state and electronic band gap of MMO electrode, as well as the highly reversible phase transition of the MMO electrode during the charging–discharging process. Because of these remarkable characteristics, the MMO electrode can be capable of delivering a significant specific capacity of ~419.8 mAh·g⁻¹, while exhibiting a good cycling capability over 1000 cycles in 1 M aqueous MgCl₂ electrolyte. On the basis of such MMO electrode, we have successfully developed a soft-packaging aqueous MIB with excellent electrochemical properties, revealing its huge application potential as the efficient energy storage devices.
- manganese oxide;
- aqueous batteries;
- intercalation engineering;
- density functional theory calculations;
- in-situ Raman

FullText(HTML)

Supplements(0)

References(48)

References

[1]	G.J. Liang, F.N. Mo, X.L. Ji, and C.Y. Zhi, Non-metallic charge carriers for aqueous batteries, Nat. Rev. Mater., 6(2021), No. 2, p. 109. doi: 10.1038/s41578-020-00241-4
[2]	M. Ren, C.Y. Zhang, Y.L. Wang, and J.J. Cai, Development of N-doped carbons from zeolite-templating route as potential electrode materials for symmetric supercapacitors, Int. J. Miner. Metall. Mater., 25(2018), No. 12, p. 1482. doi: 10.1007/s12613-018-1703-7
[3]	T. Yang, H.J. Liu, F. Bai, E.H. Wang, J.H. Chen, K.C. Chou, and X.M. Hou, Supercapacitor electrode based on few-layer h-BNNSs/rGO composite for wide-temperature-range operation with robust stable cycling performance, Int. J. Miner. Metall. Mater., 27(2020), No. 2, p. 220. doi: 10.1007/s12613-019-1910-x
[4]	C.P. Han, J.X. Zhu, C.Y. Zhi, and H.F. Li, The rise of aqueous rechargeable batteries with organic electrode materials, J. Mater. Chem. A, 8(2020), No. 31, p. 15479. doi: 10.1039/D0TA03947K
[5]	J. Shin and J.W. Choi, Opportunities and reality of aqueous rechargeable batteries, Adv. Energy Mater., 10(2020), No. 28, art. No. 2001386. doi: 10.1002/aenm.202001386
[6]	G. Liu, Q.G. Chi, Y.Q. Zhang, Q.G. Chen, C.H. Zhang, K. Zhu, and D.X. Cao, Superior high rate capability of MgMn₂O₄/rGO nanocomposites as cathode materials for aqueous rechargeable magnesium ion batteries, Chem. Commun., 54(2018), No. 68, p. 9474. doi: 10.1039/C8CC05366A
[7]	H.Y. Zhang, K. Ye, S.X. Shao, X. Wang, K. Cheng, X. Xiao, G.L. Wang, and D.X. Cao, Octahedral magnesium manganese oxide molecular sieves as the cathode material of aqueous rechargeable magnesium-ion battery, Electrochim. Acta, 229(2017), p. 371. doi: 10.1016/j.electacta.2017.01.110
[8]	Y.Q. Zhang, G. Liu, C.H. Zhang, Q.G. Chi, T.D. Zhang, Y. Feng, K. Zhu, Y. Zhang, Q.G. Chen, and D.X. Cao, Low-cost MgFe_xMn_2−xO₄ cathode materials for high-performance aqueous rechargeable magnesium-ion batteries, Chem. Eng. J., 392(2020), art. No. 123652. doi: 10.1016/j.cej.2019.123652
[9]	F. Wang, X.L. Fan, T. Gao, W. Sun, Z.H. Ma, C.Y. Yang, F.D. Han, K. Xu, and C.S. Wang, High-voltage aqueous magnesium ion batteries, ACS Cent. Sci., 3(2017), No. 10, p. 1121. doi: 10.1021/acscentsci.7b00361
[10]	Y.C. Tang, X.J. Li, H.M. Lv, W.L. Wang, Q. Yang, C.Y. Zhi, and H.F. Li, High-energy aqueous magnesium hybrid full batteries enabled by carrier-hosting potential compensation, Angew. Chem. Int. Ed., 60(2021), No. 10, p. 5443. doi: 10.1002/anie.202013315
[11]	Y.L. Liang, Y. Jing, S. Gheytani, K.Y. Lee, P. Liu, A. Facchetti, and Y. Yao, Universal quinone electrodes for long cycle life aqueous rechargeable batteries, Nat. Mater., 16(2017), No. 8, p. 841. doi: 10.1038/nmat4919
[12]	X. Lei, Y.P. Zheng, F. Zhang, Y. Wang, and Y.B. Tang, Highly stable magnesium-ion-based dual-ion batteries based on insoluble small-molecule organic anode material, Energy Storage Mater., 30(2020), p. 34. doi: 10.1016/j.ensm.2020.04.025
[13]	L. Chen, J.L. Bao, X. Dong, D.G. Truhlar, Y. Wang, C. Wang, and Y. Xia, Aqueous Mg-ion battery based on polyimide anode and Prussian blue cathode, ACS Energy Lett., 2(2017), No. 5, p. 1115. doi: 10.1021/acsenergylett.7b00040
[14]	J.S. Kim, W.S. Chang, R.H. Kim, D.Y. Kim, D.W. Han, K.H. Lee, S.S. Lee, and S.G. Doo, High-capacity nanostructured manganese dioxide cathode for rechargeable magnesium ion batteries, J. Power Sources, 273(2015), p. 210. doi: 10.1016/j.jpowsour.2014.07.162
[15]	H.T. Zhu, Y.F. An, M.J. Shi, Z.Q. Li, N.T. Chen, C. Yang, and P. Xiao, Porous N-doped carbon/MnO₂ nanoneedles for high performance ionic liquid-based supercapacitors, Mater. Lett., 296(2021), art. No. 129837. doi: 10.1016/j.matlet.2021.129837
[16]	K.W. Nam, S. Kim, S. Lee, M. Salama, I. Shterenberg, Y. Gofer, J.S. Kim, E. Yang, C.S. Park, J.S. Kim, S.S. Lee, W.S. Chang, S.G. Doo, Y.N. Jo, Y. Jung, D. Aurbach, and J.W. Choi, The high performance of crystal water containing manganese birnessite cathodes for magnesium batteries, Nano Lett., 15(2015), No. 6, p. 4071. doi: 10.1021/acs.nanolett.5b01109
[17]	H.Y. Zhang, D.X. Cao, and X. Bai, High rate performance of aqueous magnesium-ion batteries based on the δ-MnO₂@carbon molecular sieves composite as the cathode and nanowire VO₂ as the anode, J. Power Sources, 444(2019), art. No. 227299. doi: 10.1016/j.jpowsour.2019.227299
[18]	Z.Z. Liu, W.H. Zhou, J. He, H. Chen, R.X. Zhang, Q. Wang, Y. Wang, Y.G. Yan, and Y.G. Chen, Binder-free MnO₂ as a high rate capability cathode for aqueous magnesium ion battery, J. Alloys Compd., 869(2021), art. No. 159279. doi: 10.1016/j.jallcom.2021.159279
[19]	C.L. Wu, G.Y. Zhao, X.Y. Bao, X. Chen, and K.N. Sun, Hierarchically porous delta-manganese dioxide films prepared by an electrochemically assistant method for Mg ion battery cathodes with high rate performance, J. Alloys Compd., 770(2019), p. 914. doi: 10.1016/j.jallcom.2018.08.123
[20]	Q.H. Zhao, A.Y. Song, S.X. Ding, R.Z. Qin, Y.H. Cui, S.N. Li, and F. Pan, Preintercalation strategy in manganese oxides for electrochemical energy storage: Review and prospects, Adv. Mater., 32(2020), No. 50, art. No. 2002450. doi: 10.1002/adma.202002450
[21]	J.W. Wang, X.L. Sun, H.Y. Zhao, L.L. Xu, J.L. Xia, M. Luo, Y.D. Yang, and Y.P. Du, Superior-performance aqueous zinc ion battery based on structural transformation of MnO₂ by rare earth doping, J. Phys. Chem. C, 123(2019), No. 37, p. 22735. doi: 10.1021/acs.jpcc.9b05535
[22]	M. Asif, M. Rashad, Z. Ali, H.L. Qiu, W. Li, L.J. Pan, and Y.L. Hou, Ni-doped MnO₂/CNT nanoarchitectures as a cathode material for ultra-long life magnesium/lithium hybrid ion batteries, Mater. Today Energy, 10(2018), p. 108. doi: 10.1016/j.mtener.2018.08.010
[23]	F. Kataoka, T. Ishida, K. Nagita, V. Kumbhar, K. Yamabuki, and M. Nakayama, Cobalt-doped layered MnO₂ thin film electrochemically grown on nitrogen-doped carbon cloth for aqueous zinc-ion batteries, ACS Appl. Energy Mater., 3(2020), No. 5, p. 4720. doi: 10.1021/acsaem.0c00357
[24]	C. Wei, X.Y. Fu, L.L. Zhang, J. Liu, P.P. Sun, L. Gao, K.J. Chang, and X.L. Yang, Structural regulated nickel hexacyanoferrate with superior sodium storage performance by K-doping, Chem. Eng. J., 421(2021), art. No. 127760. doi: 10.1016/j.cej.2020.127760
[25]	M.J. Young, A.M. Holder, S.M. George, and C.B. Musgrave, Charge storage in cation incorporated α-MnO₂, Chem. Mater., 27(2015), No. 4, p. 1172. doi: 10.1021/cm503544e
[26]	Z.M. Hu, X. Xiao, C. Chen, T.Q. Li, L. Huang, C.F. Zhang, J. Su, L. Miao, J.J. Jiang, Y.R. Zhang, and J. Zhou, Al-doped α-MnO₂ for high mass-loading pseudocapacitor with excellent cycling stability, Nano Energy, 11(2015), p. 226. doi: 10.1016/j.nanoen.2014.10.015
[27]	H.Z. Zhang, Q.Y. Liu, J. Wang, K.F. Chen, D.F. Xue, J. Liu, and X.H. Lu, Boosting the Zn-ion storage capability of birnessite manganese oxide nanoflorets by La³⁺ intercalation, J. Mater. Chem. A, 7(2019), No. 38, p. 22079. doi: 10.1039/C9TA08418E
[28]	L. Wang, Q.Y. Wu, A. Abraham, P.J. West, L.M. Housel, G. Singh, N. Sadique, C.D. Quilty, D.R. Wu, E.S. Takeuchi, A.C. Marschilok, and K.J. Takeuchi, Silver-containing α-MnO₂ nanorods: Electrochemistry in rechargeable aqueous Zn–MnO₂ batteries, J. Electrochem. Soc., 166(2019), No. 15, p. A3575. doi: 10.1149/2.0101915jes
[29]	F.W. Fenta, B.W. Olbasa, M.C. Tsai, M.A. Weret, T.A. Zegeye, C.J. Huang, W.H. Huang, T.S. Zeleke, N.A. Sahalie, C.W. Pao, S.H. Wu, W.N. Su, H.J. Dai, and B.J. Hwang, Electrochemical transformation reaction of Cu–MnO in aqueous rechargeable zinc-ion batteries for high performance and long cycle life, J. Mater. Chem. A, 8(2020), No. 34, p. 17595. doi: 10.1039/D0TA04175K
[30]	A.M. Hashem, H.M. Abuzeid, N. Narayanan, H. Ehrenberg, and C.M. Julien, Synthesis, structure, magnetic, electrical and electrochemical properties of Al, Cu and Mg doped MnO₂, Mater. Chem. Phys., 130(2011), No. 1-2, p. 33. doi: 10.1016/j.matchemphys.2011.04.074
[31]	H.F. Li, H.Y. Wang, M. Yang, Y.C. Sun, Y.R. Yin, and P.Z. Guo, Mg-inserted δ-MnO₂ nanosheet assembly for enhanced energy storage, Colloids Surf. A, 602(2020), art. No. 125068. doi: 10.1016/j.colsurfa.2020.125068
[32]	Q. Chen, J.L. Jin, Z.K. Kou, C. Liao, Z.A. Liu, L. Zhou, J. Wang, and L.Q. Mai, Zn²⁺ pre-intercalation stabilizes the tunnel structure of MnO₂ nanowires and enables zinc-ion hybrid supercapacitor of battery-level energy density, Small, 16(2020), No. 14, art. No. 2000091. doi: 10.1002/smll.202000091
[33]	L.L. Feng, Z.W. Xuan, H.B. Zhao, Y. Bai, J.M. Guo, C.W. Su, and X.K. Chen, MnO₂ prepared by hydrothermal method and electrochemical performance as anode for lithium-ion battery, Nanoscale Res. Lett., 9(2014), No. 1, art. No. 290. doi: 10.1186/1556-276X-9-290
[34]	X. Liang, C. Hart, Q. Pang, A. Garsuch, T. Weiss, and L.F. Nazar, A highly efficient polysulfide mediator for lithium–sulfur batteries, Nat. Commun., 6(2015), art. No. 5682. doi: 10.1038/ncomms6682
[35]	Y. Xu, J. Wan, L. Huang, M.Y. Ou, C.Y. Fan, P. Wei, J. Peng, Y. Liu, Y.G. Qiu, X.P. Sun, C. Fang, Q. Li, J.T. Han, Y.H. Huang, J.A. Alonso, and Y.S. Zhao, Structure distortion induced monoclinic nickel hexacyanoferrate as high-performance cathode for Na-ion batteries, Adv. Energy Mater., 9(2019), No. 4, art. No. 1803158. doi: 10.1002/aenm.201803158
[36]	C. Ling, J.J. Chen, and F. Mizuno, First-principles study of alkali and alkaline earth ion intercalation in iron hexacyanoferrate: The important role of ionic radius, J. Phys. Chem. C, 117(2013), No. 41, p. 21158. doi: 10.1021/jp4078689
[37]	H.Y. Zhang, D.X. Cao, and X. Bai, Ni-Doped magnesium manganese oxide as a cathode and its application in aqueous magnesium-ion batteries with high rate performance, Inorg. Chem. Front., 7(2020), No. 11, p. 2168. doi: 10.1039/D0QI00067A
[38]	J.F. Yin, A.B. Brady, E.S. Takeuchi, A.C. Marschilok, and K.J. Takeuchi, Magnesium-ion battery-relevant electrochemistry of MgMn₂O₄: Crystallite size effects and the notable role of electrolyte water content, Chem. Commun., 53(2017), No. 26, p. 3665. doi: 10.1039/C7CC00265C
[39]	Z.J. Jia, J.W. Hao, L.J. Liu, Y. Wang, and T. Qi, Vertically aligned α-MnO₂ nanosheets on carbon nanotubes as cathodic materials for aqueous rechargeable magnesium ion battery, Ionics, 24(2018), No. 11, p. 3483. doi: 10.1007/s11581-018-2499-1
[40]	X.H. Wang, T.S. Mathis, K. Li, Z.F. Lin, L. Vlcek, T. Torita, N.C. Osti, C. Hatter, P. Urbankowski, A. Sarycheva, M. Tyagi, E. Mamontov, P. Simon, and Y. Gogotsi, Influences from solvents on charge storage in titanium carbide MXenes, Nat. Energy, 4(2019), No. 3, p. 241. doi: 10.1038/s41560-019-0339-9
[41]	L. Naderi, S. Shahrokhian, and F. Soavi, Fabrication of a 2.8 V high-performance aqueous flexible fiber-shaped asymmetric micro-supercapacitor based on MnO₂/PEDOT: PSS-reduced graphene oxide nanocomposite grown on carbon fiber electrode, J. Mater. Chem. A, 8(2020), No. 37, p. 19588. doi: 10.1039/D0TA06561G
[42]	Z.X. Lu, W.X. Wang, J. Zhou, and Z.C. Bai, FeS₂@TiO₂ nanorods as high-performance anode for sodium ion battery, Chin. J. Chem. Eng., 28(2020), No. 10, p. 2699. doi: 10.1016/j.cjche.2020.07.011
[43]	S. Cheng, L.F. Yang, D.C. Chen, X. Ji, Z.J. Jiang, D. Ding, and M.L. Liu, Phase evolution of an alpha MnO₂-based electrode for pseudo-capacitors probed by in operando Raman spectroscopy, Nano Energy, 9(2014), p. 161. doi: 10.1016/j.nanoen.2014.07.008
[44]	T. Gao, H. Fjellvåg, and P. Norby, A comparison study on Raman scattering properties of α- and β-MnO₂, Anal. Chim. Acta, 648(2009), No. 2, p. 235. doi: 10.1016/j.aca.2009.06.059
[45]	M.J. Shi, B. Wang, C. Chen, J.W. Lang, C. Yan, and X.B. Yan, 3D high-density MXene@MnO₂ microflowers for advanced aqueous zinc-ion batteries, J. Mater. Chem. A, 8(2020), No. 46, p. 24635. doi: 10.1039/D0TA09085A
[46]	Q.N. Zhang, M.D. Levi, Q.Y. Dou, Y.L. Lu, Y.G. Chai, S.L. Lei, H.X. Ji, B. Liu, X.D. Bu, P.J. Ma, and X.B. Yan, The charge storage mechanisms of 2D cation-intercalated manganese oxide in different electrolytes, Adv. Energy Mater., 9(2019), No. 3, art. No. 1802707. doi: 10.1002/aenm.201802707
[47]	D.C. Chen, D. Ding, X.X. Li, G.H. Waller, X.H. Xiong, M.A. El-Sayed, and M.L. Liu, Probing the charge storage mechanism of a pseudocapacitive MnO₂ electrode using in operando Raman spectroscopy, Chem. Mater., 27(2015), No. 19, p. 6608. doi: 10.1021/acs.chemmater.5b03118
[48]	M.J. Shi, B. Wang, Y. Shen, J.T. Jiang, W.H. Zhu, Y.J. Su, M. Narayanasamy, S. Angaiah, C. Yan, and Q. Peng, 3D assembly of MXene-stabilized spinel ZnMn₂O₄ for highly durable aqueous zinc-ion batteries, Chem. Eng. J., 399(2020), art. No. 125627. doi: 10.1016/j.cej.2020.125627