富锂镍锰铬三元正极材料的制备与改性研究

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本文以Li[Li1/3Mn2/3]O2-Li Cr O2-Li Ni1/2Mn1/2O2组成的体系为研究对象,采用溶胶凝胶法合成了五种三元富锂Li-Ni-Mn-Cr-O正极材料,研究了Cr与Mn+Ni的摩尔比(设Cr/Mn+Ni为x,x=0.44,0.38,0.29,0.21,0.15以下简称A~E)和水洗对材料的结构和电化学性能的影响,选择出较优的材料。然后对较优的材料进行条件优化,详细考察了反应温度、溶剂种类、柠檬酸与过渡金属比、煅烧温度和煅烧时间对材料电化学性能的影响,最后对材料进行了掺杂和包覆研究。通过XRD进行材料结构表征,SEM进行材料表面形貌表征和分析,ICP进行元素含量的测定,EIS、CV、恒流充放电测试进行电化学性能分析。过渡金属和柠檬酸摩尔比为1:1,调节p H=7,55℃合成A~E系列前驱体,400℃预烧4h,800℃煅烧12h,制备出的样品都具有层状结构,但有很强的吸湿性;经水洗处理未改变晶体结构,提高了该系列材料的电化学性能;实验证明,水洗溶出物为Li2Cr O4。其中,E样品水洗处理后(Li1.016Cr0.103Mn0.464Ni0.356O2)的电化学性能最好。继续对Li1.016Cr0.103Mn0.464Ni0.356O2优化,以水作溶剂、柠檬酸与过渡金属配比为1:1、85℃的反应温度、800℃下煅烧12h。合成的Li1.016Cr0.103Mn0.464Ni0.356O2具有典型的富锂层状的晶体结构。材料在2.0~4.8V,0.1C下首次放电比容量为190.2m Ah/g,经过20次充放电循环后,容量保持率为86.0%。利用溶胶凝胶法对Li1.016Cr0.103Mn0.464Ni0.356O2进行Co、Al掺杂,得到Li1.016Cr0.103Mn0.464-x Ni0.356Nx O2(x=0.01,0.02,0.03,0.04),讨论了不同掺杂量对Li1.016Cr0.103Mn0.464Ni0.356O2的晶体结构及电化学性能的影响。研究发现,1%Co掺杂的样品在小倍率下放电比容量略有提高。在0.1C和0.2C放电比容量分别达192.1m Ah/g、160.2m Ah/g;大倍率下循环稳定性显著提高,在0.5C和1.0C下,循环10次后,容量保持率分别为98.7%、102.0%。Al掺杂并没有改善材料的容量,但2%Al的掺杂的样品在0.5C下的稳定性能有了显著的提高。对Li1.016Cr0.103Mn0.464Ni0.356O2进行Al2O3和Mg O包覆研究。包覆量分别为1%、2%、3%、4%,其中,4%Al2O3包覆的材料在小倍率下其放电比容量虽然较纯样要低,但其0.5C和1C下放电容量定均比纯样要好,0.5C和1C放电容量分别为115.1m Ah/g和95.1m Ah/g。1%Mg O包覆的材料在大倍率下的放电容量均比纯样高,其在0.5C和1C放电容量分别为113.2和100.2m Ah/g。
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