CN103915624A - 一种碳包覆、掺杂金属元素的锂离子电池正极材料 - Google Patents

一种碳包覆、掺杂金属元素的锂离子电池正极材料 Download PDF

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CN103915624A
CN103915624A CN201410128333.2A CN201410128333A CN103915624A CN 103915624 A CN103915624 A CN 103915624A CN 201410128333 A CN201410128333 A CN 201410128333A CN 103915624 A CN103915624 A CN 103915624A
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张波
林道松
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Lin Daoyong
Shanghai Yiding New Material Technology Co ltd
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Abstract

本发明涉及一种表面包覆碳、且掺杂金属离子的锂离子电池正极材料，该正极材料的组成为：LixCo025Mn07V0.3Oy/C，其中x＝1-2，y＝2-4，其制备方法包括如下步骤：1)采用氢氧化物共沉淀法制备Co025Mn07V0.3(OH)2前驱体：按化学计量比将硫酸钴、硫酸锰和硫酸钒溶于去离子水中，浓度为2.5-3mol／L，搅拌均匀，随后加入反应釜中，加入氨水和氢氧化钠溶液调节pH值达到10-10.5，在60-80℃的水浴中蒸发水分至溶胶，冷却至室温，之后将溶胶置于马弗炉中通入氩气加热，直至样品完全干燥；2)正极材料的制备：将前驱体与LiCO3按比例混合均匀，采用三级煅烧工艺：在550-600℃下预烧2-3h，随炉冷却，冷却后研磨；再在850-900℃下煅烧8-9h，随炉冷却，冷却后继续研磨；最后在950-1000℃下煅烧2-3h，自然冷却，冷却后研磨，过筛，得到所需正极材料。

Description

一种碳包覆、掺杂金属元素的锂离子电池正极材料
技术领域
本发明属于锂离子电池正极材料技术领域，具体涉及一种碳包覆的、掺杂金属元素的锂离子电池正极材料及其制备方法。
背景技术
锂离子电池具有能量密度高、工作电压高、循环寿命长、无记忆效应、可快速充放电等优点，应用广泛。从1991年索尼公司发布首个商用锂离子电池到现在，其正极材料主要有LiCoO2、LiNiO2、层状LiM-nO2、NCM(镍钴锰酸锂三元材料)、尖晶石型LiMn2O4、NVA(镍钴铝酸锂材料)、LiMPO4(M＝Fe、Mn、Ni、Co)、富锂材料xLi2MO3·(1-x)LiM'O2、Li3V2(PO4)3等化合物及其改性复合物。LiCoO2是市场化最成功的正极材料，也是目前市场占有率最高的材料，但是LiCoO2电池轻度过充(4.4V)就会导致热稳定性和循环性变差；LiNiO2结构稳定性差的问题不能根本解决，也限制其应用；层状LiMnO2循环稳定性较差，难以直接合成；NCM和NCA材料浸泡于电解质中会引起锂溶出、材料结构退化和容量损失。另外，三元材料与电解质的相容性也是一个需要解决的重要问题，随着钴价的不断上涨，成本可能会成为限制其在大型电池中使用的一个重要因素。尖晶石型高温循环性能和储存性能存在问题，造成电池容量损失，电解液氧化分解产生酸性物质使Mn溶解，影响电池寿命；LiFePO4中Fe2+化学性能较活泼，导致材料一致性较差，其电压平台较低，振实密度较低，导致体积和重量比能量较低。
发明内容
本发明针对现有正极材料存在的缺陷，提供了一种碳包覆的、掺杂金属元素的锂离子电池正极材料及其制备方法。本方法制备过程简单，反应周期短，节约成本易于控制。通过适量金属元素掺杂，一定程度上降低了阻抗，从而提高了材料的放电性能。
本发明的目的通过以下技术方案来实现：一种表面包覆碳、且掺杂金属离子的锂离子电池正极材料，所述正极材料的组成为：LixCo0.25Mn0.7V0.3Oy/C，其中x＝1～2，y＝2～4，所述正极材料的制备方法包括如下步骤：
1)采用氢氧化物共沉淀法制备Co0.25Mn0.7V0.3(OH)2前驱体
按化学计量比将硫酸钴、硫酸锰和硫酸钒溶于去离子水中，浓度为2.5-3mol／L，搅拌均匀，随后加入反应釜中，加入氨水和氢氧化钠溶液调节pH值达到10-10.5，在60-80℃的水浴中蒸发水分至溶胶，冷却至室温，之后将溶胶置于马弗炉中通入氩气加热，直至样品完全干燥；
2)正极材料的制备
将前驱体与LiCO3按比例混合均匀，采用三级煅烧工艺：
在550-600℃下预烧2-3h，随炉冷却，冷却后研磨；
再在850-900℃下煅烧8-9h，随炉冷却，冷却后继续研磨；
最后在950-1000℃下煅烧2-3h，自然冷却，冷却后研磨，过筛，得到所需正极材料。
进一步的，所述组成为：Li1.5Co0.25Mn0.7V0.3O4／C。
更进一步的，所述预烧温度为580℃，预烧时间为2.5h，煅烧温度为980℃，煅烧时间为8.5h。
更进一步的，所述研磨为采用行星式球磨机进行高速研磨。
本发明的表面包覆碳、且掺杂金属离子的锂离子电池正极材料，由于表面包覆碳和金属离子掺杂的引入提高了电极材料的电学性能，表面包覆碳降低了电化学阻抗，金属离子掺杂改善了正极材料的微观结构缺陷，提高离子通透性，进而提高电极材料的电学性能；
本发明电极材料的后处理采用三级煅烧工艺：优于现有技术中常规的一次和两次煅烧工艺，利于表面碳包覆和金属离子的掺杂过程的充分进行，并且前两次煅烧采用随炉冷却，对于电极材料晶像组织的改善尤为关键。后处理的三级煅烧工艺也确保了电极材料放电性能的提升。
本发明的锂离子电池正极材料通过组装成电池后，在一定电流密度下放电容量和平台率都得到较大提升。例如在7mA／g电流密度下放电容量达到144-152mAh／g，3.8V以上平台率为94.3-97.1％。
具体实施方式
实施例1
采用氢氧化物共沉淀法制备Co0.25Mn0.7V0.3(OH)2前驱体，按化学计量比将硫酸钴、硫酸锰和硫酸钒溶于去离子水中，浓度为2.5mol／L，搅拌均匀，随后加入反应釜中，加入氨水和氢氧化钠溶液调节pH值达到10.5，在70℃的水浴中蒸发水分至溶胶，冷却至室温，之后将溶胶置于马弗炉中通入氩气加热，直至样品完全干燥；将前驱体与LiCO3按比例混合均匀，在580℃下预烧2.5h，冷却后研磨，再在980℃下煅烧8.5h，待材料冷却后研磨，过筛，最终得到所需正极材料，其组成为：Li1.5Co0.25Mn0.7V0.3O4／C。
将上述材料通过组装成电池后，在7mA/g电流密度下放电容量达到148mAh／g，3.8V以上平台率为96.0％，采用相同的测试方法，LiCoO2的放电容量和平台率为131mAh／g和86.7％。
实施例2
采用氢氧化物共沉淀法制备Co0.25Mn0.7V0.3(OH)2前驱体，按化学计量比将硫酸钴、硫酸锰和硫酸钒溶于去离子水中，浓度为2.5mol／L，搅拌均匀，随后加入反应釜中，加入氨水和氢氧化钠溶液调节pH值达到10，在80℃的水浴中蒸发水分至溶胶，冷却至室温，之后将溶胶置于马弗炉中通入氩气加热，直至样品完全干燥；将前驱体与LiCO3按比例混合均匀，在550℃下预烧3h，冷却后研磨，再在950℃下煅烧9h，待材料冷却后研磨，过筛，最终得到所需正极材料，其组成为：Li2Co0.25Mn0.7V0.3O3／C。
将上述材料通过组装成电池后，在7mA/g电流密度下放电容量达到145mAh／g，3.SV以上平台率为95，2％，采用相同的测试方法，NCM的放电容量和平台率为129mAh／g和90.6％。
以上内容是结合具体的优选实施方式对本发明所作的进一步详细说明，不能认定本发明的具体实施只局限于这些说明。对于本发明所属技术领域的普通技术人员来说，在不脱离本发明构思的前提下做出若干替代或明显变型，而且性能或用途相同，都应当视为属于本发明的保护范围。

Claims (4)

1.一种表面包覆碳、且掺杂金属离子的锂离子电池正极材料，其特征在于：所述正极材料的组成为：LixCo025Mn0.7V0.3Oy／C，其中x＝1～2，y＝2～4，所述正极材料的制备方法包括如下步骤：
1)采用氢氧化物共沉淀法制备Co0.25Mn0.7V03(OH)2前驱体
按化学计量比将硫酸钴、硫酸锰和硫酸钒溶于去离子水中，浓度为2.5-3mol／L，搅拌均匀，随后加入反应釜中，加入氨水和氢氧化钠溶液调节pH值达到10-10.5，在60-80℃的水浴中蒸发水分至溶胶，冷却至室温，之后将溶胶置于马弗炉中通入氩气加热，直至样品完全干燥；
2)正极材料的制备
将前驱体与LiCO3按比例混合均匀，采用三级煅烧工艺：
在550-600℃下预烧2-3h，随炉冷却，冷却后研磨；
再在850-900℃下煅烧8-9h，随炉冷却，冷却后继续研磨；
最后在950-1000℃下煅烧2-3h，自然冷却，冷却后研磨，过筛，得到所需正极材料。
2.如权利要求1所述的方法，其特征在于，所述组成为：Li1.5Co025Mn0.7V0.3O4／C。
3.如权利要求1-2所述的方法，其特征在于，所述预烧温度为580℃，预烧时问为2.5h，煅烧温度为980℃，煅烧时间为8.5h。
4.如权利要求1-3所述的方法，其特征在于，所述研磨为采用行星式球磨机进行高速研磨。
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CN108183207A (zh) * 2017-12-23 2018-06-19 湖南佳纳能源科技有限公司 一种复合锰矿制备锂电池正极材料的方法
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