单晶LiNi_(0.6)Co_(0.2)Mn_(0.199)Zr_(0.001)O_2材料的合成及性能改善研究
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摘要
利用共沉淀反应合成Ni_(0.6)Co_(0.2)Mn_(0.199)Zr_(0.001)(OH)_2前驱体,配锂经900℃高温烧结12 h制得平均粒径为3～5 mm的Li Ni_(0.6)Co_(0.2)Mn_(0.199)Zr_(0.001)O_2单晶材料。经喷雾干燥及450℃高温分解4 h制得Al_2O_3包覆单晶Li Ni0.6Co0.2Mn0.199Zr0.001O2复合材料。利用X射线衍射光谱法(XRD)、扫描电子显微镜法(SEM)、透射电子显微镜法(TEM)、电感耦合等离子体光谱分析法(ICP)对材料进行分析,结果表明:Al2O3以非晶态包覆于颗粒表面且不改变材料的晶体结构与形貌特征;包覆0.25%(质量分数)Al_2O_3材料首次放电比容量为163.4 m Ah/g,0.2 C下循环100次后容量保持率为98.69%,5 C/0.2 C容量保持率为78.6%;包覆Al_2O_3有效降低了电极阻抗,抑制了过渡金属离子溶解,包覆0.25%Al_2O_3的材料阻抗最小,电解液中过渡金属离子含量也最低。综合性能的提升证明Al_2O_3包覆层能抑制活性物质与电解液界面副反应,提高材料的结构稳定性。
Ni_(0.6)Co_(0.2)Mn_(0.199)Zr_(0.001)(OH)_2 and single crystal LiNi_(0.6)Co_(0.2)Mn_(0.199)Zr_(0.001)O_2 material with average diameter of 3-5μm were synthesized by co-precipitation reaction and high temperature sintering(900 ℃-12 h). The single crystal Li Ni0.6 Co0.2 Mn0.199 Zr0.001 O2 material was coated with Al_2O_3 by spray drying and following heat treatment(450 ℃-4 h).The prepared samples were characterized by XRD, SEM, TEM and ICP. The results show that amorphous Al_2O_3 is coated well on the surface of Li Ni0.6 Co0.2 Mn0.199 Zr0.001 O2 and makes no change for the local structure. The sample coated with 0.25% Al_2O_3 can deliver an initial specific capacity of 163.4 m Ah/g(2.8-4.25 V, 0.1 C), the capacity retention is 98.69% after 100 cycles at 0.2 C(2.8-4.5 V), and the capacity ratio of 5 C/0.2 C is 78.6%. Impedance and content of Ni, Co, and Mn in electrolyte of the sample coated with 0.25% Al_2O_3 are lower than other samples. It is confirmed that the Al_2O_3 layer can restrain side reactions at electrode/electrolyte interface, inhibit the dissolution of transition metal ions into the electrolyte, apparently suppress the increase of resistance and enhance structure stability.
Ni_(0.6)Co_(0.2)Mn_(0.199)Zr_(0.001)(OH)_2 and single crystal LiNi_(0.6)Co_(0.2)Mn_(0.199)Zr_(0.001)O_2 material with average diameter of 3-5μm were synthesized by co-precipitation reaction and high temperature sintering(900 ℃-12 h). The single crystal Li Ni0.6 Co0.2 Mn0.199 Zr0.001 O2 material was coated with Al_2O_3 by spray drying and following heat treatment(450 ℃-4 h).The prepared samples were characterized by XRD, SEM, TEM and ICP. The results show that amorphous Al_2O_3 is coated well on the surface of Li Ni0.6 Co0.2 Mn0.199 Zr0.001 O2 and makes no change for the local structure. The sample coated with 0.25% Al_2O_3 can deliver an initial specific capacity of 163.4 m Ah/g(2.8-4.25 V, 0.1 C), the capacity retention is 98.69% after 100 cycles at 0.2 C(2.8-4.5 V), and the capacity ratio of 5 C/0.2 C is 78.6%. Impedance and content of Ni, Co, and Mn in electrolyte of the sample coated with 0.25% Al_2O_3 are lower than other samples. It is confirmed that the Al_2O_3 layer can restrain side reactions at electrode/electrolyte interface, inhibit the dissolution of transition metal ions into the electrolyte, apparently suppress the increase of resistance and enhance structure stability.
引文
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[7] ABE M, IBA H, SUZUKI K, et al. Study on the deterioration mechanism of layered rock-salt electrodes using epitaxial thin films Li(Ni, Co, Mn)O2and their Zr-O surface modified electrodes[J]. Journal of Power Sources, 2017, 345:108-119.
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[9] SHI S J, TU J P, MAI Y J, et al. Structure and electrochemical performance of CaF 2coated LiNi1/3Co1/3Mn1/3O2cathode material for Li-ion batteries[J]. Electrochimica Acta, 2012, 83:105-112.
[10] LI J, LI H Y, STONE W, et al. Synthesis of single crystal LiNi0.5-Mn0.3Co0.2O2for lithium ion batteries[J]. Journal of the Electrochemical Society, 2017, 164(14):A3529-A3537.
[2] JIAO L S, LIU Z B, SUN Z H, et al. An advanced lithium ion battery based on a high quality graphitic graphene anode and a LiNi0.6Co0.2Mn0.2O2cathode[J]. Electrochimica Acta, 2018, 259:48-55.
[3] CHEN Z Q, WANG J, HUANG J X, et al. The high-temperature and high-humidity storage behaviors and electrochemical degradation mechanism of LiNi0.6Co0.2Mn0.2O2cathode material for lithium ion batteries[J]. Journal of Power Sources, 2017, 363:168-176.
[4] YUAN J, WEN J W, ZHANG J B, et al. Influence of calcination atmosphere on structure and electrochemical behavior of LiNi0.6Co0.2-Mn0.2O2cathode material for lithium-ion batteries[J]. Electrochimica Acta, 2017, 230:116-122.
[5] REN D, SHEN Y, YANG Y, et al. Systematic optimization of battery materials:key parameter optimization for the scalable synthesis of uniform, high-energy and high stability LiNi0.6Mn0.2Co0.2O2cathode material for lithium-ion batteries[J]. ACS Applied Materials&Interfaces, 2017, 9(41):35811-35819.
[6] HILDEBRAND S, VOLLMER C, WINTER M, et al. Al2O3, SiO2and TiO2as coatings for safer LiNi0.8Co0.15Al0.05O2cathodes:electrochemical performance and thermal analysis by accelerating rate calorimetry[J]. Journal of the Electrochemical Society, 2017, 164(9):A2190-A2198.
[7] ABE M, IBA H, SUZUKI K, et al. Study on the deterioration mechanism of layered rock-salt electrodes using epitaxial thin films Li(Ni, Co, Mn)O2and their Zr-O surface modified electrodes[J]. Journal of Power Sources, 2017, 345:108-119.
[8] MORETTI A, KIM G T, BRESSER D, et al. Investigation of different binding agents for nanocrystalline anatase TiO2anodes and its application in a novel, green lithium-ion battery[J]. Journal of Power Sources, 2013, 221:419-426.
[9] SHI S J, TU J P, MAI Y J, et al. Structure and electrochemical performance of CaF 2coated LiNi1/3Co1/3Mn1/3O2cathode material for Li-ion batteries[J]. Electrochimica Acta, 2012, 83:105-112.
[10] LI J, LI H Y, STONE W, et al. Synthesis of single crystal LiNi0.5-Mn0.3Co0.2O2for lithium ion batteries[J]. Journal of the Electrochemical Society, 2017, 164(14):A3529-A3537.