矿冶2024,Vol.33Issue(6) :867-873.DOI:10.3969/j.issn.1005-7854.2024.06.009

NaNi1/3Fe1/3Mn1/3O2正极材料的NiO表面改性

NiO surface modification for NaNi1/3Fe1/3Mn1/3O2 cathode material

王俊 宋顺林 王春生 刘亚飞 陈彦彬
矿冶2024,Vol.33Issue(6) :867-873.DOI:10.3969/j.issn.1005-7854.2024.06.009

NaNi1/3Fe1/3Mn1/3O2正极材料的NiO表面改性

NiO surface modification for NaNi1/3Fe1/3Mn1/3O2 cathode material

王俊 1宋顺林 1王春生 2刘亚飞 1陈彦彬1
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作者信息

  • 1. 矿冶科技集团有限公司,北京 100160;北京当升材料科技股份有限公司,北京 100160
  • 2. 鹤壁技师学院,河南 鹤壁 458000
  • 折叠

摘要

提高O3型钠电层状氧化物NaNi1/3Fe1/3Mn1/3O2(NFM)的界面稳定性可改善材料的循环和倍率性能.以NiO作为包覆剂,采用高温固相反应法对NFM进行表面改性.研究发现,NiO包覆具有助熔作用,有利于颗粒的生长和材料结晶性的提高;与未包覆样品相比,NiO包覆样品的比表面积降低约50%,乙醇溶剂测试NaOH含量降低约64%,同时pH值也明显降低.电化学性能测试结果表明NiO包覆样品在2.0~4.0 V的放电比容量为139.4 mA·h·g-1,1 C循环80次后的容量保持率达到94.1%,并且表现出更好的倍率性能和更小的极化,显著优于未包覆样品.该性能提升归因于热处理过程中NiO与正极表面的残钠发生化学反应生成新的镍酸钠界面层,阻止了电解液对材料的侵蚀,抑制正极过渡金属的溶解;圆润光滑的正极颗粒表面、低的比表面积,有助于增强颗粒之间的接触,减少与电解液的副反应;新生成的NaFeO2层具有良好的电化学活性,促进了正极和电解液界面之间的钠离子扩散和电子传导.

Abstract

To improve the interface stability of O3-type layered oxide cathode material NaNi1/3Fe1/3Mn1/3O2(NFM)for enhancing its cycle stability and rate capability,NiO was used as a coating agent,surface modification of NFM was carried out by high-temperature solid-state reaction method.It is found that NiO coating has a melting aid effect,which is beneficial for particle growth and well crystallization.Compared with the uncoated sample,the specific surface area of the NiO-coated sample is reduces by about 50%,the NaOH content tested in the ethanol solvent is decreased by about 64%,and the pH value is also lowered significantly.Electrochemical performance tests show that the NiO-coated sample has a discharge specific capacity of 139.4 mA·h·g-1at 2.0-4.0V,with a 1 C capacity retention of 94.1%after 80 cycles.It also exhibits better rate performance and smaller polarization,significantly better than the uncoated sample.The performance improvement is attributed to the chemical reaction between NiO and residual sodium on the cathode surface during the heat treatment process,which generates a new sodium nickel oxide interfacial layer,preventing the electrolyte from corroding the cathode and suppressing the dissolution of the transition metals.The smooth and round surface of the cathode particles and the low specific surface area help to enhance the contact between particles and reduce side reactions with the electrolyte.Additionally,the newly generated NaFeO2 layer exhibits excellent electrochemical activity,promoting sodium ion diffusion and electron conduction between the cathode and electrolyte interface.

关键词

钠离子电池/层状氧化物正极材料/NiO表面改性/NaNi1/3Fe1/3Mn1/3O2/界面稳定性

Key words

sodium-ion battery/layered oxide cathode material/NiO surface modification/NaNi1/3Fe1/3Mn1/3O2/interface stability

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出版年

2024
矿冶
北京矿冶研究总院

矿冶

CSTPCD
影响因子:0.78
ISSN:1005-7854
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