多金属共掺杂制备Na0.67Mn0.67Ni0.33-xCoxO2钠离子电池正极材料及电化学性能优化机理研究

doi:10.3901/JME.2020.10.117

机械工程学报 ›› 2020, Vol. 56 ›› Issue (10): 117-126.doi: 10.3901/JME.2020.10.117

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多金属共掺杂制备Na_0.67Mn_0.67Ni_0.33-xCo_xO₂钠离子电池正极材料及电化学性能优化机理研究

张远朋, 赵方晖, 张国举, 杨洁, 段连峰

长春工业大学材料科学与工程学院长春 130012

收稿日期:2019-11-12 修回日期:2020-02-20 出版日期:2020-05-20 发布日期:2020-06-11
通讯作者: 段连峰(通信作者),男,1981年出生,教授,博士研究生导师。主要研究方向为新能源材料与器件。E-mail:duanlf2011@sina.cn
作者简介:张远朋,男,1992年出生,硕士研究生。主要研究方向为钠离子电池正极材料。E-mail:1254872292@qq.com;赵方晖,女,1994年出生,硕士研究生。主要研究方向为钠离子电池正极材料。E-mail:354498523@qq.com;张国举,男,1995年出生,硕士研究生。主要研究方向为钠离子电池负极锡基合金的制备及电化学性能。E-mail:1486512008@qq.com;杨洁,女,1995年出生,硕士研究生。主要研究方向为柔性锂硫电池。E-mail:1561103091@qq.com
基金资助:
国家自然科学基金资助项目（61774022）。

Preparation of Na_0.67Mn_0.67Ni_0.33-_xCo_xO₂ as Cathode Material for Sodium Ion Battery by Multi-metal Substitution and Electrochemical Performance

ZHANG Yuanpeng, ZHAO Fanghui, ZHANG Guoju, YANG Jie, DUAN Lianfeng

Department of Materials Science and Engineering, Changchun University of Technology, Changchun 130012

Received:2019-11-12 Revised:2020-02-20 Online:2020-05-20 Published:2020-06-11

摘要/Abstract

摘要： 利用简单的水热结合煅烧法制备Na_0.91MnO₂，并以此为前驱体材料，在相同条件下进行Ni掺杂制备Na_0.67Mn_0.67Ni_0.33O₂纳米颗粒有效地提高了比容量。进一步地，又对Na_0.67Mn_0.67Ni_0.33O₂进行Co掺杂制得Na_0.67Mn_0.67Ni_0.33-xCo_xO₂，发现得到的电极材料具有更高的循环稳定性。通过微观结构及成分分析所合成的样品成分均一、形貌均匀，粒径大约300 nm。其中Ni、Co共掺杂的Na_0.67Mn_0.67Ni_0.33-xCo_xO₂在电流密度0.1C时，首次充、放电比容量均为160 mA·h·g^-1以上，经过200次循环的放电比容量保持在120 mA·h·g^-1。电流密度1C时可逆容量可达到90 mA·h·g^-1。研究表明，通过Ni的掺杂提高了纳米颗粒的比容量，Co掺杂可提高电极材料的钠离子扩散系数，减小电荷转移阻抗，双掺杂可有效提高电极材料的比容量、倍率与循环性能。

关键词: 锰酸钠, 多金属掺杂, 钠离子电池, 正极材料, 钠离子扩散

Abstract: The nanoparticles of Na_0.67Mn_0.67Ni_0.33O₂ and Co-Na_0.67Mn_0.67Ni_0.33O₂ are prepared by co-doping multi-metal Ni and Co with Na_0.91MnO₂ though the simple hydrothermal combined calcination method, and their electrochemical properties are optimized as cathode electrode materials for sodium ion batteries. The prepared particles with the size about 300 nm have been the uniform composition and uniform morphology. As the cathode for sodium ion batteries, the initial charge and discharge capacity of Na_0.67Mn_0.67Ni_0.33-xCo_xO₂ are above 160 mA·h·g^-1at 0.1C, and the capacity remained at 120 mA·h·g^-1 after 200 cycles. It shows that the Ni and Co ions are located in the transition metal sites could improve the specific capacity of nanoparticles (Ni) and increase the sodium ion diffusion of electrode materials (Co). The synergetic effects of Co and Ni substitution could effectively improve the specific capacity, rate and cycle performance of the cathode for sodium ion batteries.

Key words: sodim manganate, multi-metal substitution, sodium ion battery, cathode material, sodium ion diffusion

中图分类号:

TM911

张远朋, 赵方晖, 张国举, 杨洁, 段连峰. 多金属共掺杂制备Na_0.67Mn_0.67Ni_0.33-xCo_xO₂钠离子电池正极材料及电化学性能优化机理研究[J]. 机械工程学报, 2020, 56(10): 117-126.

ZHANG Yuanpeng, ZHAO Fanghui, ZHANG Guoju, YANG Jie, DUAN Lianfeng. Preparation of Na_0.67Mn_0.67Ni_0.33-_xCo_xO₂ as Cathode Material for Sodium Ion Battery by Multi-metal Substitution and Electrochemical Performance[J]. Journal of Mechanical Engineering, 2020, 56(10): 117-126.

参考文献

[1] DENG Y P,WU Z G,LIANG R,et al. Layer-based heterostructured cathodes for lithium-ion and sodium-ion batteries[J]. Advanced Functional Materials,2019,29(19):1808522.
[2] SHAN X Y,GUO Z X,ZHANG X,et al. Mesoporous TiO₂ nanofiber as highly efficient sulfur host for advanced Lithium-sulfur batteries[J]. Chin. J. Mech. Eng.,2019,32:60-65.
[3] LI Y,LU Y,ZHAO C,et al. Recent advances of electrode materials for low-cost sodium-ion batteries towards practical application for grid energy storage[J]. Energy Storage Materials,2017,7:130-151.
[4] XIANG X,ZANG K,CHEN J. Recent advances and prospects of cathode materials for sodium-ion batteries[J]. Adv. Mater.,2015,27(36):5343-5364.
[5] HAN M H,GONZALO E,SINGH G,et al. A comprehensive review of sodium layered oxides:Powerful cathodes for Na-ion batteries[J]. Energy & Environmental Science,2015,8(1):81-102.
[6] 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.
[7] SHAN X Y,GUO Z X,ZHANG X,et al. Mesoporous TiO₂ nanofber as highly efficient sulfur host for advanced lithium-sulfur batteries[J]. Chin. J. Mech. Eng.,2019,32:60-66.
[8] 赵新兵,谢健. 新型锂离子电池正极材料LiFePO₄的研究进展[J]. 机械工程学报,2007,43(1):69-76. ZHAO Xinbing,XIE Jian. Recent development of LiFePO₄ cathode materials for lithium-ion batteries[J]. Journal of Mechanical Engineering,2007,43(1):69-76.
[9] HARIHARAN K. Physicochemical properties of Na_xCoO₂ as a cathode for solid state sodium battery[J]. Solid State Ionics,2011,192(1):360-363.
[10] BIANCHINI M,WANG J,CLEMENT R,et al. A first-principles and experimental investigation of nickel solubility into the P2 Na_xCoO₂ sodium-ion cathode[J]. Advanced Energy Materials,2018,8(26):1801446.
[11] MA X,CHEN H,CEDER G. Electrochemical properties of monoclinic NaMnO₂[J]. Journal of The Electroche-mical Society,2011,158(12):A1307-A1312.
[12] CABLLERO A,HERNAN L,MORALES J,et al. Synthesis and characterization of high-temperature hexagonal P2-Na_0.6MnO₂ and its electrochemical behaviour as cathode in sodium cells[J]. Journal of Materials Chemistry,2002,12(4):1142-1147.
[13] KOMABA S,TAKEI C,NAKAYAMA T,et al. Electrochemical intercalation activity of layered NaCrO₂ vs. LiCrO₂[J]. Electrochemistry Communications,2010,12(3):355-358.
[14] HAMANI D,ATI M,TARASCON J-M,et al. Na_xVO₂ as possible electrode for Na-ion batteries[J]. Electro-chemistry Communications,2011,13(9):938-941.
[15] LU Z,DAHN J R. In situ x-ray diffraction study of P2-Na_2/3N_1/3Mn_2/3O₂[J]. Journal of the Electrochemical Society,2001,148(11):A1225-A1229.
[16] KIM D,LEE E,SLATER M,et al. Layered Na[Ni_1/3Fe_1/3Mn_1/3]O₂ cathodes for Na-ion battery applica-tion[J]. Electrochemistry Communications,2012,18:66-69.
[17] KOMABA S,YABUUCHI N,NAKAYAMA T,et al. Study on the reversible electrode reaction of Na_1-xNi_0.5Mn_0.5O₂ for a rechargeable sodium-ion battery[J]. Inorg. Chem.,2012,51(11):6211-6220.
[18] SATHIYA M,HEMALATHA K,RAMESHA K,et al. Synthesis,structure,and electrochemical properties of the layered sodium insertion cathode material:NaNi_1/3Mn_1/3Co_1/3O₂[J]. Chemistry of Materials,2012,24(10):1846-1853.
[19] YABUUCHI N,KAJIYAMA M,IWATATE J,et al. P2-type Na_x[Fe_1/2Mn_1/2]O₂ made from earth-abundant elements for rechargeable Na batteries[J]. Nature Materials,2012,11(6):512-517.
[20] WANG J,QIU B,HE X,et al. Low-cost orthorhombic Na_x[FeTi]O₄ (x=1 and 4/3) compounds as anodematerials for sodium-ion batteries[J]. Chemistry of Materials,2015,27(12):4374-4379.
[21] WANG Y,ZHAO F,QIAN Y,et al. High-performance P2-Na_0.70Mn_0.80Co_0.15Zr_0.05O₂ cathode for sodium-ion batteries[J]. ACS Applied Materials & Interfaces,2018,10(49):42380-42386.
[22] YUE J L,ZHOU Y N,YU X,et al. O₃-type layered transition metal oxide Na(NiCoFeTi)_1/4O₂ as a high rate and long cycle life cathode material for sodium ion batteries[J]. Journal of Materials Chemistry A,2015,3(46):23261-23267.
[23] WANG P F,YOU Y,YIN Y X,et al. Suppressing the P2-O2 phase transition of Na_0.67Mn_0.67Ni_0.33O₂ by magnesium substitution for improved sodium-ion batteries[J]. Ange-wandte Chemie International Edition,2016,55(26):7445-7449.
[24] WANG P F,YAO H R,LIU X Y,et al. Ti-substituted NaNi_0.5Mn_0.5-xTi_xO₂ cathodes with reversible O3-P3 phase transition for high-performance sodium-ion batteries[J]. Advanced Materials,2017,29(19):1700210.
[25] HAN M H,GONZALO E,SHARMA N,et al. High-performance P2-phase Na_2/3Mn_0.8Fe_0.1Ti_0.1O₂ cathode material for ambient-temperature sodium-ion batteries[J]. Chemistry of Materials,2015,28(1):106-116.
[26] Pang W L,Zhang X H,Guo J Z,et al. P2-type Na_2/3Mn_1-xAl_xO₂ cathode material for sodium-ion batteries:Al-doped enhanced electrochemical properties and studies on the electrode kinetics[J]. Journal of Power Sources,2017,356:80-88.
[27] YU T Y,Hwang J Y,Bae I T,et al. High-performance Ti-doped O3-type Na[Ti_x(Ni_0.6Co_0.2Mn_0.2)_1-x]O₂ cathodes for practical sodium-ion batteries[J]. Journal of Power Sources,2019,422:1-8.
[28] WANG X,LIU G,IWAO T,et al. Role of ligand-to-metal charge transfer in O3-type NaFeO₂-NaNiO₂ solid solution for enhanced electrochemical properties[J]. The Journal of Physical Chemistry C,2014,118(6):2970-2976.
[29] NAYAK P K,GRINBLAT J,LEV M,et al. Electrochemical and structural characterization of carbon coated Li_1.2Mn_0.56Ni_0.16Co_0.08O₂ and Li_1.2Mn_0.6Ni_0.2O₂ as cathode materials for Li-ion batteries[J]. Electrochimica Acta,2014,137:546-556.
[30] LI Z Y,ZHANG J,GAO R,et al. Unveiling the role of Co in improving the high-rate capability and cycling performance of layered Na_0.7Mn_0.7Ni_0.3-xCo_xO₂ cathode materials for sodium-ion batteries[J]. ACS Applied Materials & Interfaces,2016,8(24):15439-15448.
[31] XIAO Y,ZHU Y F,YAO H R,et al. A stable layered oxide cathode material for high-performance sodium-ion battery[J]. Advanced Energy Materials,2019,9(19):1803978.
[32] LI J,WANG J,HE X,et al. P2-Type Na_0.67Mn_0.8-Cu_0.1Mg_0.1O₂ as a new cathode material for sodium-ion batteries:Insights of the synergetic effects of multi-metal substitution and electrolyte optimization[J]. Journal of Power Sources,2019,416:184-192.
[33] KALIYAPPAN K,XAIO W,SHAM T-K,et al. High tap density Co and Ni containing P2-Na_0.66MnO₂ Buckyballs:A promising high voltage cathode for stable sodium-ion batteries[J]. Advanced Functional Materials,2018,28(32):1801898.
[34] LIU W,CHEN T,LI J,et al. Investigation on the effect of Cu substitution on structure and Na-ion kinetics of layered P2-Na_0.44Mn_0.6Ni_0.4O₂ cathode material[J]. Solid State Ionics,2019,329:149-154.
[35] TAPIA-RUIZ N,DOSE W M,SHARMA N,et al. High voltage structural evolution and enhanced Na-ion diffusion in P2-Na_2/3Ni_1/3-xMg_xMn_2/3O₂(0≤ x ≤ 0.2) cathodes from diffraction,electrochemical and ab initio studies[J]. Energy & Environmental Science,2018,11(6):1470-1479.
[36] ZHANG X H,PANG W L,WAN F,et al. P2-Na_2/3Ni_1/3Mn_5/9Al_1/9O₂ microparticles as superior cathode material for sodium-ion batteries:Enhanced properties and mechanism via graphene connection[J]. ACS Applied Materials & Interfaces,2016,8(32):20650-20659.
[37] BI K,ZHAO S X,HUANG C,et al. Improving low-temperature performance of spinel LiNi_0.5Mn_1.5O₄ electrode and LiNi_0.5Mn_1.5O₄/Li₄Ti₅O₁₂ full-cell by coating solid-state electrolyte Li-Al-Ti-P-O[J]. Journal of Power Sources,2018,389:240-248.
[38] DENG Y F,ZHAO S X,XU Y H,et al. Effect of temperature of Li₂O-Al₂O₃-TiO₂-P₂O₅ solid-state electrolyte coating process on the performance of LiNi_0.5Mn_1.5O₄ cathode materials[J]. Journal of Power Sources,2015,296:261-267.
[39] HUANG 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.
[40] QIAO R,DAI K,MAO J,et al. Revealing and suppressing surface Mn(II) formation of Na_0.44MnO₂ electrodes for Na-ion batteries[J]. Nano Energy,2015,16:186-195.
[41] CAO Y,XIAO L,WANG W,et al. Reversible sodium ion insertion in single crystalline manganese oxide nanowires with long cycle life[J]. Adv. Mater.,2011,23(28):3155-3160.
[42] BUCHER N,HARTUNG S,NAGASUBRAMANIAN A,et al. Layered Na_xMnO_2+z in sodium ion batteries influence of morphology on cycle performance[J]. ACS Applied Materials & Interfaces,2014,6(11):8059-8065.
[43] 谢永纯,王成,蒋芳,等. 钠锰比对Na_xMnO₂的性能和钠离子脱嵌过程的影响[J]. 电化学,2018,24(4):375-384. XIE Yongchun,WANG Cheng,JIANG Fang,et al. Influences of Na-Mn ratio on electrochemical performances and intercalation-deintercalation processes of sodium ion in Na_xMnO₂[J]. Journal of Electrochemical,2018,24(4):375-384.

多金属共掺杂制备Na_0.67Mn_0.67Ni_0.33-xCo_xO₂钠离子电池正极材料及电化学性能优化机理研究

Preparation of Na_0.67Mn_0.67Ni_0.33-_xCo_xO₂ as Cathode Material for Sodium Ion Battery by Multi-metal Substitution and Electrochemical Performance

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[3]	赵新兵;谢健. 新型锂离子电池正极材料LiFePO4的研究进展[J]. , 2007, 43(1): 69-76.