富锂正极材料的合成与表面改性研究
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摘要
本论文研究了富锂正极材料Li1.2Mn0.54Ni0.13Co0.13O2的合成与改性，并系统研究了其改性机理。
通过溶胶凝胶法、共沉淀法、Pechini法、醋酸盐共融法、喷雾干燥法5种方法制备了Li1.2Mn0.54Ni0.13Co0.13O2，利用XRD，ICP，SEM，XPS，恒流充放电等测试手段对制备的样品物相、化学组成、形貌、元素化合价、电化学性能进行了表征。测试结果表明，样品元素组成都接近预期组分，结构都具有R-3m六方层状结构，XRD数据显示，衍射峰在20°-25°之间具有超晶格结构。XPS测试结果表明，制备的样品中Mn、Co、Ni三种过渡金属元素主要化合价分别为+4、+3和+2价。电化学性能测试表明，Pechini制备的材料首周可逆容量，库仑效率，前30周容量保持率均优于其它方法合成的样品。
利用ex-situ XANES (X-ray absorption near edge)初步探究了富锂正极材料的充放电机理。结果显示，充放电过程中Mn近边吸收谱变化规律不明显，Mn元素的价态几乎不变。Ni与Co的近边吸收谱变化规律较明显，Ni与Co的近边吸收谱随着充电过程的进行向高能量方向移动。放电过程中的变化与充电过程中变化相反。初步判断，富锂正极材料中Co3+氧化过程发生在Ni2+之前。
采用原位聚合法将导电聚合物聚吡咯(PPy)包覆在富锂正极材料颗粒表面。XRD分析结果表明，PPy包覆层对富锂正极材料结构没有影响。通过SEM，TEM，TG-DSC表征了PPy在颗粒表面存在的形态与含量。电化学性能测试结果表明，电极材料首周库仑效率从包覆前78.3%提高到包覆后88.9%，前30周容量保持率从包覆前69.3%提高到包覆后86.1%。利用循环伏安测试(CV)，高分辨透射电镜(HRTEM)，红外光谱(FT-IR)，电化学阻抗谱(EIS)等测试手段研究PPy改性机理表明，PPy包覆层有效抑制了富锂正极材料首周的析氧过程，减缓了Mn4+的活化并且降低了材料的电荷转移阻抗，从而有效改善了富锂正极材料的电化学性能。除此之外，通过TEM与FT-IR测试，表明原样品充到高压时不会生成SEI膜，而经过PPy包覆的样品表面会有主要成分为Li2CO3和ROCO2Li的SEI膜生成。
This synthesis and surface modification of a lithium-rich cathode materialLi1.2Mn0.54Ni0.13Co0.13O2were studied in this thesis. The mechanism for itselectrochemical performance improvement by PPy surface coating was alsoinvestigated.
Li1.2Mn0.54Ni0.13Co0.13O2was prepared by various methods, including sol-gel,co-precipitation, Pechini, quaternary eutectic Li-Ni-Mn-Co acetate process and sprydrying methods. The prepared cathode materials were investigated by X-raydiffraction (XRD), inductively coupled plasma-atomic emission spectrometry(ICP-AES), scanning electron microscope (SEM), X-ray photoelectron spectroscopy(XPS), and galvanostatic testing. It was shown that most of the XRD diffractions canbe indexed to the R-3m structure. Traces of a superstructure were observed between20°and25°. The main valence of Mn, Co and Ni were determined to be+4,+3,+2,respectively. It was found that the sample prepared by the Pechini method had betterelectrochemical properties (reversible capacity, initial coulomb efficiency andcapacity retention) than that by the other methods. The mechanism ofcharge-discharge cycling of Li_(1.2)Mn_(0.54)Co_(0.13)Ni_(0.13)O_2was studied by ex-situ X-rayabsorption near edge structure (XANES). The results displayed that the valance stateof Mn hardly changed while that of Ni and Co changed drastically in the initial cycle.It was also found that the oxidation of Co3+to Co4+took place before the Ni2+to Ni4+oxidation.
A composite is prepared by coating Li_(1.2)Mn_(0.54)Co_(0.13)Ni_(0.13)O_2with polypyrrole(PPy). No significant structural differences were observed between the pristinesample and PPy-coated sample. SEM, TEM, and TG-DSC were employed tocharacterize the morphology and content of PPy of the Li_(1.2)Mn_(0.54)Co_(0.13)Ni_(0.13)O_2.Galvanostatic test revealed that the initial coulomb efficiency increases from78.3%(pristine) to88.9%(PPy-coated) while the capacity retention in30cycles increasesfrom69.3%(pristine) to86.1%(PPy-coated). The mechanism of the PPy-coatedmaterial was investigated by CV, HRTEM, FT-IR, EIS, etc.. It was found that the PPy coating improves the initial coulombic efficiency and the cycling stability of thematerial by suppressing the electrolyte decomposition and oxygen vacancyelimination at high potentials. Furthermore, the presence of the solid electrolyteinterphase (SEI) is confirmed on the PPy-coated sample. Li2CO3and ROCO2Li weresupposed to be the main components of the SEI layer on the PPy-coatedLi_(1.2)Mn_(0.54)Co_(0.13)Ni_(0.13)O_2.
通过溶胶凝胶法、共沉淀法、Pechini法、醋酸盐共融法、喷雾干燥法5种方法制备了Li1.2Mn0.54Ni0.13Co0.13O2，利用XRD，ICP，SEM，XPS，恒流充放电等测试手段对制备的样品物相、化学组成、形貌、元素化合价、电化学性能进行了表征。测试结果表明，样品元素组成都接近预期组分，结构都具有R-3m六方层状结构，XRD数据显示，衍射峰在20°-25°之间具有超晶格结构。XPS测试结果表明，制备的样品中Mn、Co、Ni三种过渡金属元素主要化合价分别为+4、+3和+2价。电化学性能测试表明，Pechini制备的材料首周可逆容量，库仑效率，前30周容量保持率均优于其它方法合成的样品。
利用ex-situ XANES (X-ray absorption near edge)初步探究了富锂正极材料的充放电机理。结果显示，充放电过程中Mn近边吸收谱变化规律不明显，Mn元素的价态几乎不变。Ni与Co的近边吸收谱变化规律较明显，Ni与Co的近边吸收谱随着充电过程的进行向高能量方向移动。放电过程中的变化与充电过程中变化相反。初步判断，富锂正极材料中Co3+氧化过程发生在Ni2+之前。
采用原位聚合法将导电聚合物聚吡咯(PPy)包覆在富锂正极材料颗粒表面。XRD分析结果表明，PPy包覆层对富锂正极材料结构没有影响。通过SEM，TEM，TG-DSC表征了PPy在颗粒表面存在的形态与含量。电化学性能测试结果表明，电极材料首周库仑效率从包覆前78.3%提高到包覆后88.9%，前30周容量保持率从包覆前69.3%提高到包覆后86.1%。利用循环伏安测试(CV)，高分辨透射电镜(HRTEM)，红外光谱(FT-IR)，电化学阻抗谱(EIS)等测试手段研究PPy改性机理表明，PPy包覆层有效抑制了富锂正极材料首周的析氧过程，减缓了Mn4+的活化并且降低了材料的电荷转移阻抗，从而有效改善了富锂正极材料的电化学性能。除此之外，通过TEM与FT-IR测试，表明原样品充到高压时不会生成SEI膜，而经过PPy包覆的样品表面会有主要成分为Li2CO3和ROCO2Li的SEI膜生成。
This synthesis and surface modification of a lithium-rich cathode materialLi1.2Mn0.54Ni0.13Co0.13O2were studied in this thesis. The mechanism for itselectrochemical performance improvement by PPy surface coating was alsoinvestigated.
Li1.2Mn0.54Ni0.13Co0.13O2was prepared by various methods, including sol-gel,co-precipitation, Pechini, quaternary eutectic Li-Ni-Mn-Co acetate process and sprydrying methods. The prepared cathode materials were investigated by X-raydiffraction (XRD), inductively coupled plasma-atomic emission spectrometry(ICP-AES), scanning electron microscope (SEM), X-ray photoelectron spectroscopy(XPS), and galvanostatic testing. It was shown that most of the XRD diffractions canbe indexed to the R-3m structure. Traces of a superstructure were observed between20°and25°. The main valence of Mn, Co and Ni were determined to be+4,+3,+2,respectively. It was found that the sample prepared by the Pechini method had betterelectrochemical properties (reversible capacity, initial coulomb efficiency andcapacity retention) than that by the other methods. The mechanism ofcharge-discharge cycling of Li_(1.2)Mn_(0.54)Co_(0.13)Ni_(0.13)O_2was studied by ex-situ X-rayabsorption near edge structure (XANES). The results displayed that the valance stateof Mn hardly changed while that of Ni and Co changed drastically in the initial cycle.It was also found that the oxidation of Co3+to Co4+took place before the Ni2+to Ni4+oxidation.
A composite is prepared by coating Li_(1.2)Mn_(0.54)Co_(0.13)Ni_(0.13)O_2with polypyrrole(PPy). No significant structural differences were observed between the pristinesample and PPy-coated sample. SEM, TEM, and TG-DSC were employed tocharacterize the morphology and content of PPy of the Li_(1.2)Mn_(0.54)Co_(0.13)Ni_(0.13)O_2.Galvanostatic test revealed that the initial coulomb efficiency increases from78.3%(pristine) to88.9%(PPy-coated) while the capacity retention in30cycles increasesfrom69.3%(pristine) to86.1%(PPy-coated). The mechanism of the PPy-coatedmaterial was investigated by CV, HRTEM, FT-IR, EIS, etc.. It was found that the PPy coating improves the initial coulombic efficiency and the cycling stability of thematerial by suppressing the electrolyte decomposition and oxygen vacancyelimination at high potentials. Furthermore, the presence of the solid electrolyteinterphase (SEI) is confirmed on the PPy-coated sample. Li2CO3and ROCO2Li weresupposed to be the main components of the SEI layer on the PPy-coatedLi_(1.2)Mn_(0.54)Co_(0.13)Ni_(0.13)O_2.
引文
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