尖晶石型LiMn_2O_4的制备与性能研究
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摘要
本文概述了锂离子电池的工作原理、发展现状和正极材料的研究进展。研究了LiMn_2O_4的制备方法及其工艺条件。针对LiMn_2O_4正极材料在充放电循环过程中发生Jahn-Teller畸变、Mn在电解液中溶解和表面形成钝化膜这三个导致容量衰减和循环性能劣化的关键问题,分别采用Fe、Al、Cu阳离子的一元掺杂和多元掺杂两种措施,对尖晶石结构的LiMn_2O_4正极材料进行了改性研究。
采用溶胶.凝胶法制备了LiMn_2O_4和Li_(1.08)Mn_2O_4样品,通过X射线衍射分析和循环性能的分析,比较两者的优劣。结果发现,经过50次循环后Li_(1.08)Mn_2O_4的比容量保持率为80.3%,而LiMn_2O_4的比容量仅为原来的78.10%。可见尖晶石的富锂方案,可以较好地改善尖晶石的循环性能,但同时初始放电容量略有减小。将富锂和掺杂的工艺结合起来,即“富锂+掺杂”方案,用这种方法合成的Li_(1+x)M_yMn_(2+y)O_4,可以抑制容量的衰减。
采用溶胶-凝胶法制备了Li_(1.08)Fe_xMn_(2-x)O_4、Li_(1.08)Al_xMn_(2-x)O_4、Li_(1.08)Cu_xMn_(2-x)O_4、Li_(1.08)Cu_(0.025)M_(0.025)Mn_(1.95)O_4和Li_(1.08)Cu_(0.025)Fe_(0.025)Al_(0.025)Mn_(1.925)O_4尖晶石化合物,并通过X射线衍射分析、扫描电子显微镜、恒电流充放电、电化学阻抗和循环伏安等测试考察了阳离子的一元掺杂和多元掺杂对LiMn_2O_4样品的结构、形貌和电化学性能的影响。结果显示,样品均具有单一尖晶石结构。随着掺杂量的增加,材料的初始放电比容量降低,但却提高了尖晶石结构的稳定性和循环性能。循环伏安测试结果发现,Fe~(3+)、Al~(3+)、Cu~(2+)掺杂改性后的正极材料氧化还原电势差变小,表明其电化学可逆性得到提高。结合各单元素掺杂的优点,又进行了二元及多元掺杂。其中综合性能最好的是LiFe_(0.025)Cu_(0.025)Mn_(1.95)O_4,首次放电比容量为101.89 mAh·g~(-1),经过50次循环后的放电比容量为97.10 mAh·g~(-1),容量保持率高达95.3%。
The principle and development of lithium ion batteries and the survey of cathode materials have been described in this paper. The preparation methods and technical conditions of LiMn_2O_4 were studied. During charge-discharge progress some existing problems of LiMn_2O_4 have been introduced with emphasis, such as the Jahn-Teller distortion, Mn dissolution to electrolyte and the formation of passivating films on the surface, which are the three main factors resulting in fading capacity and poor cyclability. In order to solve these problems, we used two methods such as single ion doping and multiple doping with Fe、Al、Cu cations,and research the modified of spinel LiMn_2O_4 cathode material.
The LiMn_2O_4 and Li_(1.08)Mn_2O_4 samples were prepared by the sol-gel method. The X-ray diffraction and cyclability analysis were used to contrast the two samples. It was found that after 50th charge-discharge cycle, the discharge specific capacity retention of Li_(1.08)Mn_2O_4 was 80.3%,but that of LiMn_2O_4 only turned to 78.10% compared with the original one.So it can be seen clearly that the scheme of lithium-rich improved the cyclability properties of spinel, but the first discharge specific capacity retention slight decreased simultaneously. We combine the scheme of lithium-rich with doping technology, which is named "lithium-rich+ doping" scheme.Li_(1+x)Mn_(2-y)M_yO_4,which was synthesized by the aboved scheme, can restrain the loss of the capacity.
The spinel compound LiFe_xMn_(2-x)O_4,LiAl_xMn_(2-x)O_4,LiCu_xMn_(2-x)O_4, LiCu_(0.025)M_(0.025)Mn_(1.95)O_4 and LiCu_(0.025)Fe_(0.025)Al_(0.025)Mn_(1.925)O_4 were prepared by the sol-gel method. The influences of the single cation doping and multiple doping of cations on the structure, morphology and electrochemical performance of LiMn_2O_4 was investigated by X-ray diffraction (XRD), scanning electric microscopy (SEM), charge-discharge at constant current, AC impedance (EIS), cyclic voltammety (CV) as well as various electrochemical analysis methods. The results show that all the samples formed pure spinel structure. As the doping content increased, the first discharge specific capacity of samples were reduces, but the structural stability and cycle performances were improved. The result of cyclic voltammety (CV) indicated that the electrochemical reversibility was improved, for the redox potential difference of the cathode materials was smaller after doping Fe~(3+),Al~(3+),Cu~(2+) ions. Together with the advantages of single ion doping, two and multiple doping was carried out in this thesis. The property of LiFe_(0.025)Cu_(0.025)Mn_(1.95)O_4 cathode material is the best. The first discharge specific capacity is 101.89 mAh·g~(-1), and the discharge specific capacity is 97.10 mAh·g~(-1) after 50th cycle. The discharge specific capacity retention reaches 95.3%.
采用溶胶.凝胶法制备了LiMn_2O_4和Li_(1.08)Mn_2O_4样品,通过X射线衍射分析和循环性能的分析,比较两者的优劣。结果发现,经过50次循环后Li_(1.08)Mn_2O_4的比容量保持率为80.3%,而LiMn_2O_4的比容量仅为原来的78.10%。可见尖晶石的富锂方案,可以较好地改善尖晶石的循环性能,但同时初始放电容量略有减小。将富锂和掺杂的工艺结合起来,即“富锂+掺杂”方案,用这种方法合成的Li_(1+x)M_yMn_(2+y)O_4,可以抑制容量的衰减。
采用溶胶-凝胶法制备了Li_(1.08)Fe_xMn_(2-x)O_4、Li_(1.08)Al_xMn_(2-x)O_4、Li_(1.08)Cu_xMn_(2-x)O_4、Li_(1.08)Cu_(0.025)M_(0.025)Mn_(1.95)O_4和Li_(1.08)Cu_(0.025)Fe_(0.025)Al_(0.025)Mn_(1.925)O_4尖晶石化合物,并通过X射线衍射分析、扫描电子显微镜、恒电流充放电、电化学阻抗和循环伏安等测试考察了阳离子的一元掺杂和多元掺杂对LiMn_2O_4样品的结构、形貌和电化学性能的影响。结果显示,样品均具有单一尖晶石结构。随着掺杂量的增加,材料的初始放电比容量降低,但却提高了尖晶石结构的稳定性和循环性能。循环伏安测试结果发现,Fe~(3+)、Al~(3+)、Cu~(2+)掺杂改性后的正极材料氧化还原电势差变小,表明其电化学可逆性得到提高。结合各单元素掺杂的优点,又进行了二元及多元掺杂。其中综合性能最好的是LiFe_(0.025)Cu_(0.025)Mn_(1.95)O_4,首次放电比容量为101.89 mAh·g~(-1),经过50次循环后的放电比容量为97.10 mAh·g~(-1),容量保持率高达95.3%。
The principle and development of lithium ion batteries and the survey of cathode materials have been described in this paper. The preparation methods and technical conditions of LiMn_2O_4 were studied. During charge-discharge progress some existing problems of LiMn_2O_4 have been introduced with emphasis, such as the Jahn-Teller distortion, Mn dissolution to electrolyte and the formation of passivating films on the surface, which are the three main factors resulting in fading capacity and poor cyclability. In order to solve these problems, we used two methods such as single ion doping and multiple doping with Fe、Al、Cu cations,and research the modified of spinel LiMn_2O_4 cathode material.
The LiMn_2O_4 and Li_(1.08)Mn_2O_4 samples were prepared by the sol-gel method. The X-ray diffraction and cyclability analysis were used to contrast the two samples. It was found that after 50th charge-discharge cycle, the discharge specific capacity retention of Li_(1.08)Mn_2O_4 was 80.3%,but that of LiMn_2O_4 only turned to 78.10% compared with the original one.So it can be seen clearly that the scheme of lithium-rich improved the cyclability properties of spinel, but the first discharge specific capacity retention slight decreased simultaneously. We combine the scheme of lithium-rich with doping technology, which is named "lithium-rich+ doping" scheme.Li_(1+x)Mn_(2-y)M_yO_4,which was synthesized by the aboved scheme, can restrain the loss of the capacity.
The spinel compound LiFe_xMn_(2-x)O_4,LiAl_xMn_(2-x)O_4,LiCu_xMn_(2-x)O_4, LiCu_(0.025)M_(0.025)Mn_(1.95)O_4 and LiCu_(0.025)Fe_(0.025)Al_(0.025)Mn_(1.925)O_4 were prepared by the sol-gel method. The influences of the single cation doping and multiple doping of cations on the structure, morphology and electrochemical performance of LiMn_2O_4 was investigated by X-ray diffraction (XRD), scanning electric microscopy (SEM), charge-discharge at constant current, AC impedance (EIS), cyclic voltammety (CV) as well as various electrochemical analysis methods. The results show that all the samples formed pure spinel structure. As the doping content increased, the first discharge specific capacity of samples were reduces, but the structural stability and cycle performances were improved. The result of cyclic voltammety (CV) indicated that the electrochemical reversibility was improved, for the redox potential difference of the cathode materials was smaller after doping Fe~(3+),Al~(3+),Cu~(2+) ions. Together with the advantages of single ion doping, two and multiple doping was carried out in this thesis. The property of LiFe_(0.025)Cu_(0.025)Mn_(1.95)O_4 cathode material is the best. The first discharge specific capacity is 101.89 mAh·g~(-1), and the discharge specific capacity is 97.10 mAh·g~(-1) after 50th cycle. The discharge specific capacity retention reaches 95.3%.
引文
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