钠锰比对NaxMnO2的性能和钠离子脱嵌过程的影响

doi:10.13208/j.electrochem.180207

电化学（中英文） ›› 2018, Vol. 24 ›› Issue (4): 375-384. doi: 10.13208/j.electrochem.180207

钠锰比对Na_xMnO₂的性能和钠离子脱嵌过程的影响

谢永纯¹，王成¹，蒋芳¹，杨洋¹，苏静^1,3,4，龙云飞¹，文衍宣^1,2,3,4*

1. 广西大学化学化工学院，广西南宁 530004；2. 广西高校新能源材料及相关技术重点实验室，广西南宁 530004；3. 广西新型电池材料工程技术研究中心，广西南宁 530004；4. 广西有色金属及特色材料加工重点实验室，广西南宁 530004

收稿日期:2018-02-07 修回日期:2018-03-26 出版日期:2018-08-28 发布日期:2018-04-25
通讯作者: 文衍宣 E-mail:wenyanxuan@vip.163.com
基金资助:
国家自然科学基金资助项目(No. 51564002)资助

Influences of Na-Mn Ratio on Electrochemical Performances and Intercalation-Deintercalation Processes of Sodium Ion in Na_xMnO₂

XIE Yong-chun¹, WANG Cheng¹, JIANG Fang¹, YANG Yang¹,SU Jing^1,3,4, LONG Yun-fei¹, WEN Yan-xuan^1,2,3,4*

1. School of Chemistry of and Chemical Engineering, Guangxi University, Nanning 530004, China;2. Guangxi Key Laboratory of Processing for Non-ferrous Metallic and Featured Materials, Guangxi University, Nanning 530004, China; 3. Guangxi Novel Battery Materials Research Center of Engineering Technology, Nanning 530004, China; 4. Guangxi Colleges and Universities Key Laboratory of Novel Energy Materials and Related Technology, Nanning 530004, China

Received:2018-02-07 Revised:2018-03-26 Published:2018-08-28 Online:2018-04-25
Contact: WEN Yan-xuan E-mail:wenyanxuan@vip.163.com
Supported by:
The National Natural Science Fund(No. 51564002)

摘要/Abstract

摘要：

采用高温固相法合成了Na_xMnO₂，并用X-射线衍射、X-射线光电子能谱、场发射扫描电镜、循环伏安、电化学阻抗谱和恒流充放电技术研究了钠锰比对材料的形态结构、电化学性能和钠离子脱嵌过程的影响. 结果表明，Na_xMnO₂ 主要由Na_0.7MnO₂ 和Na_0.91MnO₂ 组成，且Na_0.91MnO₂ 的量随着钠锰比的增加而增加. 随着钠锰比的增加，SEI 膜扩散、界面电化学反应和固相扩散的活化能先减少后增大，而材料的放电比容量则先增大后减少. 当钠锰比为0.80 时，合成的材料1C 倍率下首次放电比容量为152.8 mAh·g^-1，50 次循环容量保持率为80.6%，5C 大倍率下放电比容量为88.3 mAh·g^-1，表现出了良好的循环性能和倍率性，相应的SEI 膜扩散、界面电化学反应和固相扩散过程的活化能分别为68.23、40.07 和57.62 KJ·mol^-1.

关键词: 钠离子电池, 正极材料, Na_xMnO₂, 钠离子脱嵌

Abstract: In this work, Na_xMnO₂ was synthesized by a solid-state reaction. The influences of Na:Mn ratio on the structure, morphology and electrochemical performance, and sodium ion intercalation/deintercalation processes were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, field emission scanning electron microscopy, cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic charge-discharge test. The prepared Na_xMnO₂ was mainly composed of Na_0.7MnO₂ and Na_0.91MnO₂, and the content of Na_0.91MnO₂ increased with the increase of Na:Mn ratio. However, the activation energy values of surface membrane diffusion, interfacial electrochemical reaction and Na⁺ diffusion in the bulk material first decreased and then increased with the increase of Na:Mn ratio, while the discharge capability first increasedand then decreased with the increase of Na:Mn ratio. The sample synthesized with the Na:Mn ratio of 0.80 delivered a discharge capacity of 152.8 mAh·g^-1 with a capacity retention of 80.6% after 50 cycles at 1C. Even being charged/discharged at 5C, this sample still provided a discharge capacity of 88.3 mAh·g^-1, showing good cycle-stability and rate performance. The activation energy values of surface membrane diffusion, interfacial electrochemical reaction and solid-phase diffusion were found to be 68.23, 40.07 and 57.62 kJ·mol^-1, respectively.

Key words: sodium-ion battery, cathode, Na_xMnO₂, sodium-ion intercalation/deintercalation

中图分类号:

O646

谢永纯，王成，蒋芳，杨洋，苏静，龙云飞，文衍宣. 钠锰比对Na_xMnO₂的性能和钠离子脱嵌过程的影响[J]. 电化学（中英文）, 2018, 24(4): 375-384.

XIE Yong-chun, WANG Cheng, JIANG Fang, YANG Yang, SU Jing, LONG Yun-fei, WEN Yan-xuan. Influences of Na-Mn Ratio on Electrochemical Performances and Intercalation-Deintercalation Processes of Sodium Ion in Na_xMnO₂[J]. Journal of Electrochemistry, 2018, 24(4): 375-384.

参考文献

[1] Xia Y(夏阳), Fang R Y(方如意), Shi S(施思), et al. Review on synthesis of electrode materials derived from biological templates for lithium-ion batteries[J]. Materials Review(材料导报), 2016, 30(1): 128-135.

[2] Shen W(沈伟), Shen L Y(申兰耀), Zhang Z Y(张振宇), et al. Recent developments in cathode materials for Na-ion batteries[J]. Advanced Materials Industry(新材料产业), 2017(5): 61-64.

[3] Ye F P(叶飞鹏), Wang L(王莉), Lian F(连芳), et al. Advance in Na-ion batteries[J]. Chemical Industry and Engineering Progress(化工进展), 2013, 32(8): 1789-1795.

[4] Liu Y C(刘永畅), Chen C C(陈程成), Zhang N(张宁), et al. Research and application of key materials for sodium-ion batteries[J]. Journal of Electrochemistry(电化学),2016, 22(5): 437-452.

[5] Qian J F(钱江锋), Gao X P(高学平), Yang H X(杨汉西). Electrochemical Na-storage materials and their applications for Na-ion batteries[J]. Journal of Electrochemistry(电化学), 2013, 19(6): 523-529.

[6] Wang L B, Wang C C, Zhang N, et al. High anode performance of in situ formed Cu₂Sb nanoparticles integrated on Cu foil via replacement reaction for sodium-ion batteries [J]. ACS Energy Letters, 2017, 2(1): 256-262.

[7] Wang C C, Wang L B, Li F J, et al. Bulk bismuth as a high-capacity and ultralong cycle-life anode for sodium-ion batteries by coupling with glyme-based electrolytes[J]. Advanced Materials, 2017, 29(35): 1702212.

[8] Kim H, Kim H, Ding Z, et al. Recent progress in electrode materials for sodium-ion batteries [J]. Advanced Energy Materials, 2016, 6(19): 1600943.

[9] Jia X P, Chen M. Review of electrode materials for sodium-ion batteries[J]. Journal of China Academy of Electronics Information Technology, 2012, 7(6): 581-585.

[10] Billaud J, Clement R J, Armstrong A R, et al. α-NaMnO₂:a high-performance cathode for sodium-ion batteries [J].Journal of the American Chemical Society, 2014, 136(49):17243-17248.

[11] Ma X, Chen H, Ceder G. Electrochemical properties of monoclinic NaMnO₂[J]. Journal of The Electrochemical Society, 2011, 158(2): A1307-A1312.

[12] Su D,Wang C, Ahn H J, et al. Single crystalline Na_0.7MnO₂,nanoplates as cathode materials for sodium-ion batteries with enhanced performance[J]. Chemistry-A European Journal, 2013, 19(33): 10884-10889.

[13] SohnDR, LimS J, NamDH, et al. Fabrication of Na_0.7MnO₂/C composite cathode material by simple heat treatment for high-power Na-ion batteries[J]. Electronic Materials Letters, 2018, 14: 30-36.

[14] Molenda J, Stoksa A, Than D. Relation between ionic and electronic defects of Na_0.7MnO₂, bronze and its electrochemical properties[J]. Solid State Ionics, 1987, 24(1):33-38.

[15] Luo C, Langrock A, Fan X L, et al. P2-type transition metal oxides for high performance Na-ion battery cathodes [J].Journal of Materials Chemistry A, 2017, 5(34): 18214-18220 .

[16] Kim H, Dong J K, Seo D H, et al. Ab initio study of the sodium intercalation and intermediate phases in Na_0.44MnO₂ for sodium-ion battery[J]. Chemistry of Materials, 2012, 24(6): 1205-1211.

[17] Zhao L W, Ni J F, Wang H B, et al. Na_0.44MnO₂-CNT electrodes for non-aqueous sodium batteries[J]. RSC Advances,2013, 3(18): 6650-6655.

[18] Liu C, Li J G, Zhao P X, et al. Fast preparation of Na_0.44MnO₂, nanorods via a high NaOH concentration hydrothermal soft chemical reaction and their lithium storage properties[J]. Journal of Nanoparticle Research, 2015,17(3): 142.

[19] Bucher N, Hartung S, Gocheva I, et al. Combustion-synthesized sodium manganese (cobalt) oxides as cathodes for sodium ion batteries[J]. Journal of Solid State Electrochemistry,2013, 17(7): 1923-1929.

[20] Huang J J, Luo J. Composites of sodium manganese oxides with enhanced electrochemical performance for sodium-ion batteries: Tailoring properties via controlling microstructure[J]. Science China-Technological Sciences,2016, 59(7): 1042-1047.

[21] Zhang S Q(张淑琼). Preparation and properties research of non-noble metal oxide for energy storage[D]. Anhui Normal University(安徽师范大学), 2015.

[22] Shen K Y, Miklos L, Wang L, et al. Spray pyrolysis and electrochemical performance of Na_0.44MnO₂ for sodium-ion battery cathodes[J].MRSCommunications, 2017, 7(1): 74-77.

[23] Xiang X, Zhang K, Chen J. Recent advances and prospects of cathode materials for sodium-ion batteries[J]. Advanced Materials, 2015, 46(44): 5343-5364.

[24] Xue M M(薛明明). Structural characterization and properties of monoclinic NaMnO₂[D]. Northeast Normal University(东北师范大学), 2010.

[25] Shaju K M, Subba Rao G V, Chowdari B V R. Spinel phases LiMMnO₂(M=Co, CoAl, CoCr, CrAl) as cathodes for lithium-ion batteries[J]. Solid State Ionics, 2002, 148 (3): 343-350.

[26] Zhuang Q C(庄全超), Xu S D(徐守冬), Qiu X Y(邱祥云), et al. Diagnosis of electrochemical impedance spectroscopy in lithium-ion batteries[J]. Progress in Chemistry(化学进展), 2010, 22(6): 1044-1057.

[27] Hou X(侯旭), Tang ZW(唐子威), Pei B(裴波). Research progress of electrode-electrolyte interfacial filmin lithiumion batteries[J]. Marine Electric & Electronic Technology (船电技术), 2017, 37(7): 64-67.

[28] Yang T Y(杨同勇). Study on synthesis and modification of 5V cathode material LiNi_0.5Mn_1.5O₄ for lithium-ion battery[D]. Harbin Institute of Technology(哈尔滨工业大学), 2011.

钠锰比对Na_xMnO₂的性能和钠离子脱嵌过程的影响

Influences of Na-Mn Ratio on Electrochemical Performances and Intercalation-Deintercalation Processes of Sodium Ion in Na_xMnO₂

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

Metrics

[1]	胡炳文, 李超, 耿福山, 沈明. 金属离子电池中的磁共振：从核磁共振(NMR)到电子顺磁共振(EPR)[J]. 电化学（中英文）, 2022, 28(2): 2108421-.
[2]	骆晨旭, 师晨光, 余志远, 黄令, 孙世刚. 富锂锰基层状正极材料的合成及其首周过充下的结构演化[J]. 电化学（中英文）, 2022, 28(1): 2006131-.
[3]	兰道云, 屈小峰, 唐宇婷, 刘丽英, 刘军. 3.9 V电化学稳定窗口的乙酸盐电解液用于低成本高性能的水系钠离子电池[J]. 电化学（中英文）, 2022, 28(1): 2102231-.
[4]	滕久康, 王庆杰, 张亮, 张红梅, 陈晓涛, 张鹏, 赵金保. 热处理时间对锂电池正极材料Cr₈O₂₁的影响[J]. 电化学（中英文）, 2021, 27(6): 689-697.
[5]	李姝谨, 曹志康, 王文凯, 张晓菡, 向兴德. 硫酸盐功能电解液增强水系钠离子电池NaTi₂(PO₄)₃/C负极材料电化学性能的研究[J]. 电化学（中英文）, 2021, 27(6): 605-613.
[6]	吴凯. Na₃V₂(PO₄)₂O₂F的合成及其在钠离子电池中的应用[J]. 电化学（中英文）, 2021, 27(1): 56-62.
[7]	王存, 张维江, 何腾飞, 雷博, 史尤杰, 郑耀东, 罗伟林, 蒋方明. NCA三元锂离子电池分荷电状态循环的热特性和容量衰退研究[J]. 电化学（中英文）, 2020, 26(6): 777-788.
[8]	段明涛, 蒙延双, 张红帅. Ni₃S₂@碳纳米管复合材料的制备及其储钠性能[J]. 电化学（中英文）, 2020, 26(6): 850-858.
[9]	陈嘉卉, 钟晓斌, 何超, 王晓晓, 许清池, 李剑锋. 中空核壳结构Ni_1.2Co_0.8P@N-C钠离子电池负极材料的制备及拉曼研究[J]. 电化学（中英文）, 2020, 26(3): 328-337.
[10]	王杜丹, 王非, 翟欢欢, 李玉鹏, 杨纳川, 陈康华. 富锂层状正极材料Li₂MnO₃的表面改性及其电化学性能研究[J]. 电化学（中英文）, 2020, 26(2): 289-297.
[11]	王非, 翟欢欢, 王杜丹, 李玉鹏, 陈康华. Sn-Cl共掺杂的锂离子正极材料Li₂MnO₃的结构及电化学性能研究[J]. 电化学（中英文）, 2020, 26(1): 148-155.
[12]	黄云辉. 钴酸锂正极材料与锂离子电池的发展 ——2019年诺贝尔化学奖解读[J]. 电化学（中英文）, 2019, 25(5): 609-613.
[13]	王凡凡, 刘晓斌, 陈龙, 陈程成, 刘永畅, 范丽珍. 室温钠离子电池关键材料研究进展[J]. 电化学（中英文）, 2019, 25(1): 55-76.
[14]	孙梦雷, 张达奇, 冯金奎, 倪江锋. 钒基电极材料研究进展[J]. 电化学（中英文）, 2019, 25(1): 45-54.
[15]	颜冲, 寇华日, 颜波, 刘晓静, 李德军, 李喜飞. Ni/Mn₃O₄/NiMn₂O₄@RGO空心微球负极的制备及其储钠性能[J]. 电化学（中英文）, 2019, 25(1): 112-121.