水系镁离子电池正极材料钠锰氧化物的制备及电化学性能

张永泉; 姚安权; 杨柳; 朱凯; 曹殿学

doi:10.7498/aps.70.20202130

摘要

近年来镁离子电池正极材料的研发成为研究热点, 提高电池的高倍率性能和循环稳定性成为主要研究目标. 本文采用水热法制备了纳米线和纳米片共混结构的钠锰氧化物(Na_0.55Mn₂O₄·1.5H₂O)纳米材料, 并用X−射线衍射和扫描电子显微镜进行表征, 通过充放电测试仪和电化学工作站进行变倍率充放电循环和变扫速循环伏安测试. 结果表明水热反应时间对材料的相结构和形貌组成影响显著, 其中水热反应72 h样品(NMO-72)中纳米片和纳米线形成紧密共混, 纳米片有效填充到纳米线交叉空隙中, 提高了材料的振实密度. 并且NMO-72材料具有更高的放电比容量和倍率循环性能. 在50 mA·g^–1电流密度下, NMO-72的放电比容量达到229.1 mAh·g^–1; 在1000 mA·g^–1电流密度下, NMO-72材料的放电比容量稳定在81 mAh·g^–1; 而电流密度再次回到50 mA·g^–1时, 其放电比容量稳定保持在164.7 mAh·g^–1. 同时, 循环伏安测试表明NMO-72材料与其他材料相比, 具有最佳的镁离子扩散动力学性能, 由此NMO-72材料具有更为优异的可逆比容量、高倍率性能和循环稳定性.

关键词:

Abstract

In recent years, the cathode materials of magnesium ion batteries have become a hot point of research, and the improvement of high-rate performance and cycle stability has become the main research goal. In this paper, sodium manganese oxide (Na_0.55Mn₂O₄·1.5H₂O) nanomaterial with a blended structure of nanowires and nanosheets is prepared by the hydrothermal method. The structure and morphology of the material are analyzed by X-ray diffraction and scanning electron microscopy. The variable rate charge-discharge curves and variable scan rate cyclic voltammetry curves are obtained by a battery tester and electrochemical workstation, respectively. The results show that the hydrothermal reaction time has significant effects on phase structure and morphology composition of the material. The nanosheets and nanowires in the sample form a closely blend by 72-h hydrothermal reaction (NMO-72), and the nanosheets effectively fill into the intersecting space of the nanowires. In this way, the tap density of the material is improved. More importantly, NMO-72 has higher discharge specific capacity and rate cycling performance. At a current density of 50 mA·g^–1, the discharge specific capacity of NMO-72 reaches 229.1 mAh·g^–1. At a current density of 1000 mA·g^–1, the discharge specific capacity of the NMO-72 stabilizes at 81 mAh·g^–1. When the current density returns to 50 mA·g^–1 again, the discharge specific capacity remains stable at 164.7 mAh·g^–1. Besides, the cyclic voltammetry test shows that the NMO-72 material has more excellent magnesium ion diffusion kinetic performance than other materials. Therefore, the NMO-72 material has more excellent reversible specific capacity, high rate performance and cycling stability.

Keywords:

作者及机构信息

1.
哈尔滨工程大学材料科学与化学工程学院, 超轻材料与表面技术教育部重点实验室, 哈尔滨　150001, 中国

2.
哈尔滨工程大学智能科学与工程学院, 哈尔滨　150001, 中国

3.
哈尔滨理工大学电气与电子工程学院, 工程电介质及其应用教育部重点实验室, 哈尔滨　150080, 中国

4.
卡尔斯鲁厄理工学院, 应用材料研究所, 艾根施泰因-利奥伯德港　76344, 德国

通信作者: 杨柳, lyang@hrbeu.edu.cn

基金项目: 国家自然科学基金(批准号: 11704089, 51672056)、黑龙江省自然科学基金(批准号: LH2020E093)、黑龙江省普通本科高等学校青年创新人才培养计划(批准号: UNPYSCT-2018216)、中国博士后科学基金(批准号: 2017M611355)、中央高校基本科研业务费(批准号: 3072021CFT0402)和黑龙江省留学回国人员择优资助的课题

Authors and contacts

1.
Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, China

2.
College of Intelligent Systems Science and Engineering, Harbin Engineering University, Harbin 150001, China

3.
Key Laboratory of Engineering Dielectrics and Its Application, Ministry of Education, School of Electrical and Electronic Engineering, Harbin University of Science and Technology, Harbin 150080, China

4.
Institute for Applied Materials (IAM), Karlsruhe Institute of Technology (KIT), Eggenstein-Leopoldshafen 76344, Germany

Corresponding author: Yang Liu, lyang@hrbeu.edu.cn

Funds: Project supported by the National Natural Science Foundation of China (Grant Nos. 11704089, 51672056), the Natural Science Foundation of Heilongjiang Province, China (Grant No. LH2020E093), the University Nursing Program for Young Scholars with Creative Talents in Heilongjiang Province, China (Grant No. UNPYSCT-2018216), the China Postdoctoral Science Foundation (Grant No. 2017M611355), Fundamental Research Funds for the Central Universities (Grant No. 3072021CFT0402), and Merit-based funding for returning overseas students in Heilongjiang Province

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参考文献

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施引文献

图 1 制备样品的XRD曲线

Fig. 1. XRD curves of all samples.

下载: 全尺寸图片幻灯片

图 2 制备样品的SEM照片　(a) NMO-60; (b) NMO-72; (c) NMO-84. 插图为局部放大的SEM照片

Fig. 2. (a) NMO-60, (b) NMO-72 and (c) NMO-84 SEM images of all samples. The insets are the enlarged SEM images.

下载: 全尺寸图片幻灯片

图 3 制备样品的EDS图片

Fig. 3. EDS images of all samples.

下载: 全尺寸图片幻灯片

图 4 制备样品在不同倍率下的充放电循环性能

Fig. 4. Charge-discharge cycling performance of all samples at different rates.

下载: 全尺寸图片幻灯片

图 5 不同倍率下的充放电曲线　(a) NMO-60; (b) NMO-72; (c) NMO-84

Fig. 5. Charge-discharge curves at different rates: (a) NMO-60; (b) NMO-72; (c) NMO-84.

下载: 全尺寸图片幻灯片

图 6 不同扫描速率下的循环伏安曲线　(a) NMO-60; (b) NMO-72

Fig. 6. CV curves of (a) NMO-60 and (b) NMO-72 at various scan rates.

下载: 全尺寸图片幻灯片

map

[1]	Muldoon J, Bucur C B, Gregory T 2014 Chem. Rev. 114 11683 Google Scholar
[2]	Huie M M, Bock D C, Takeuchi E S, Marschilok A C, Takeuchi K J 2015 Coord. Chem. Rev. 287 15 Google Scholar
[3]	刘文龙, 黄可贤, 周学俊, 李驰麟 2020 硅酸盐学报 48 978 Google Scholar Liu W L, Huang K X, Zhou X J, Li C L 2020 J. Chin. Ceram. Soc. 48 978 Google Scholar
[4]	刘凡凡, 王田甜, 范丽珍 2020 硅酸盐学报 48 947 Google Scholar Liu F F, Wang T T, Fan L Z 2020 J. Chin. Ceram. Soc. 48 947 Google Scholar
[5]	苏硕剑, 努丽燕娜, 非路热·吐尔逊, 杨军, 王久林 2015 物理化学学报 31 111 Google Scholar Su S J, Nuli Y N, Feilure T, Yang J, Wang J L 2015 Acta Phys. Chim. Sin. 31 111 Google Scholar
[6]	Song J, Sahadeo E, Noked M, Lee S B 2016 J. Phys. Chem. Lett. 7 1736 Google Scholar
[7]	Xu M, Lei S, Qi J, Dou Q, Liu L, Lu Y, Huang Q, Shi S, Yan X 2018 ACS Nano 12 3733 Google Scholar
[8]	Xu C, Chen Y, Shi S, Li J, Kang F, Su D 2015 Sci. Rep. 5 14120 Google Scholar
[9]	Zhang Y, Liu G, Zhang C, Chi Q, Zhang T, Feng Y, Zhu K, Zhang Y, Chen Q, Cao D 2020 Chem. Eng. J. 392 123652 Google Scholar
[10]	Pan H, Shao Y, Yan P, Cheng Y, Han K S, Nie Z, Wang C, Yang J, Li X, Bhattacharya P, Mueller K T, Liu J 2016 Nat. Energy 1 16039 Google Scholar
[11]	Liang Y, Jing Y, Gheytani S, Lee K Y, Liu P, Facchetti A, Yao Y 2017 Nat. Mater. 16 841 Google Scholar
[12]	Zhang H, Ye K, Zhu K, Cang R, Wang X, Wang G, Cao D 2017 ACS Sustainable Chem. Eng. 5 6727 Google Scholar
[13]	Arthur T S, Zhang R, Ling C, Glans P A, Fan X, Guo J, Mizuno F 2014 ACS Appl. Mater. Interfaces 6 7004 Google Scholar
[14]	Liu G, Chi Q, Zhang Y, Chen Q, Zhang C, Zhu K, Cao D 2018 Chem. Commun. 54 9474 Google Scholar
[15]	Liu M, Jain A, Rong Z, Qu X, Canepa P, Malik R, Ceder G, Persson K A 2016 Energy Environ. Sci. 9 3201 Google Scholar
[16]	Saha P, Jampani P H, Datta M K, Hong D, Gattu B, Patel P, Kadakia K S, Manivannan A, Kumta P N 2017 Nano Res. 10 4415 Google Scholar
[17]	NuLi Y, Yang J, Li Y, Wang J 2010 Chem. Commun. 46 3794 Google Scholar
[18]	李卓, 宁哲, 刘坤, 王一雍, 韩露, 路金林 2017 中国冶金 27 1 Google Scholar Li Z, Ning Z, Liu K, Wang Y Y, Han L, Lu J L 2017 China Metall. 27 1 Google Scholar
[19]	李艳阳, 熊跃, 张建民, 陈卫华 2015 材料导报 29 50 Google Scholar Li Y Y, Xiong Y, Zhang J M, Chen W H 2015 Mater. Rep. 29 50 Google Scholar
[20]	Zhang J, He T, Zhang W, Sheng J Z, Amiinu I S, Kou Z K, Yang J L, Mai L Q, Mu S C 2017 Adv. Energy Mater. 7 1602092 Google Scholar
[21]	杨顺毅, 王先友, 魏建良, 李秀琴, 唐安平 2008 物理化学学报 24 1669 Google Scholar Yang S Y, Wang X Y, Wie J L, Li X Q, Tang A P 2008 Acta Phys. Chim. Sin. 24 1669 Google Scholar
[22]	Xu M W, Niu Y B, Li Y T, Bao S J, Li C M 2014 RSC Adv. 4 30340 Google Scholar
[23]	Lv W J, Huang Z G, Yin Y X, Yao H R, Zhu H L, Guo Y G 2019 ChemNanoMat 5 1253 Google Scholar
[24]	Zheng P, Su J X, Wang Y B, Zhou W, Song J J, Su Q M, Reeves-McLaren N, Guo S W 2020 ChemSusChem 13 1793 Google Scholar
[25]	陆雅翔, 赵成龙, 容晓晖, 陈立泉, 胡勇胜 2018 67 120601 Google Scholar Lu Y X, Zhao C L, Rong X H, Chen L Q, Hu Y S 2018 Acta Phys. Sin. 67 120601 Google Scholar
[26]	Zhang Q N, Levi M D, Dou Q Y, Lu Y L, Chai Y G, Lei S L, Ji H X, Liu B, Bu X D, Ma P J, Yan X B 2019 Adv. Energy Mater. 9 1802707 Google Scholar
[27]	Li J N, Yu J, Amiinu I S, Zhang J, Sheng J Z, Kou Z K, Wang Z, Yu Q, Mai L Q, Mu S C 2017 J. Mater. Chem. A 5 18509 Google Scholar
[28]	Chua R, Cai Y, Kou Z K, Satish R, Ren H, Chan J J, Zhang L P, Morris S A, Bai J M, Srinivasan M 2019 Chem. Eng. J. 370 742 Google Scholar
[29]	Wang X Y, Qin X H, Lu Q Q, Han M M, Omar A, Mikhailova D 2020 Chin. J. Chem. Eng. 28 2214 Google Scholar
[30]	Xiao Y, Zhu Y F, Xiang W, Wu Z G, Li Y C, Lai J, Li S, Wang E, Yang Z G, Xu C L, Zhong B H, Guo X D 2020 Angew. Chem. Int. Ed. 59 1491 Google Scholar
[31]	Okamoto S, Ichitsubo T, Kawaguchi T, Kumagai Y, Oba F, Yagi S, Shimokawa K, Goto N, Doi T, Matsubara E 2015 Angew. Adv. Sci. 2 1500072 Google Scholar

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水系镁离子电池正极材料钠锰氧化物的制备及电化学性能