锰掺杂对对纯化磷酸铁制备磷酸铁锂电池正极材料的影响
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摘要
以废弃磷化渣为原料,利用酸液水热过滤法对磷化渣提纯。将所得纯度较高的磷酸铁为铁源,通过加入锰盐来制备含有掺杂锰元素的前驱体,经过高温还原后可得到掺杂锰元素的磷酸亚铁锂/碳电池正极材料。利用X射线衍射仪、X射线荧光光谱仪、扫描电子显微镜和LAND测试仪对不同组成的磷酸铁锂/碳电池正极材料的颗粒形貌、物相及扣式电池的电化学性能进行表征。结果表明:掺杂锰元素的磷酸亚铁锂/碳材料在大倍率下仍能保持较高的容量保持率,这对于制作大倍率电池具有重要的意义。
The wasted phosphating slag as raw material was purified by acid hydrothermal filtration method. Used the obtained highpurity iron phosphate as an iron source, a manganese-containing precursor was prepared by adding a manganese salt. After reduction at high temperature, a lithium iron phosphate/carbon battery cathode material doped with manganese can be obtained. The particle morphology, phase and electrochemical properties of the lithium iron phosphate/carbon battery cathode materials with different compositions were characterized by x-ray diffractometer, energy dispersive x-ray diffraction, scanning electron microscope and LAND tester.The results show that the lithium iron phosphate/carbon material doped with manganese can maintain good capacity retention rate under large magnification, which is of great significance for making large rate batteries.
The wasted phosphating slag as raw material was purified by acid hydrothermal filtration method. Used the obtained highpurity iron phosphate as an iron source, a manganese-containing precursor was prepared by adding a manganese salt. After reduction at high temperature, a lithium iron phosphate/carbon battery cathode material doped with manganese can be obtained. The particle morphology, phase and electrochemical properties of the lithium iron phosphate/carbon battery cathode materials with different compositions were characterized by x-ray diffractometer, energy dispersive x-ray diffraction, scanning electron microscope and LAND tester.The results show that the lithium iron phosphate/carbon material doped with manganese can maintain good capacity retention rate under large magnification, which is of great significance for making large rate batteries.
引文
[1]田娟,陈文兴,蒋仁波.锌系磷化液废渣综合利用技术[J].现代化工, 2015(6):155-156.
[2] KANG H C, WANG G X, GUO H Y, et al. Facile synthesis and electrochemical performance of LiFePO4/C composites using Fe-P waste slag[J]. Industrial&Engineering Chemistry Research, 2012, 51(23):7923-7931.
[3]熊新宇,熊天庆,宋倩倩,等.金属表面处理磷化渣综合利用技术[J].冶金动力, 2015(2):43-45.
[4]刘肖强,张素娜,王利军,等.焙烧温度对提纯磷化渣制备LiFePO4/C正极材料的影响[J].上海第二工业大学学报, 2017, 34(1):26-30.
[5]林娟.锂离子电池正极材料LiFePO4的改性研究进展[J].广东化工, 2016, 43(11):135.
[6]舒进波,张金利,李.锰掺杂对于磷酸铁锂高倍率性能影响的研究[J].化工新型材料, 2014, 42(7):102-104.
[7]刘肖强,王利军,乔永民,等.磷化渣制备多元掺杂LiFePO4/C极材料的研究[J].电源技术, 2017, 41(10):1392-1395.
[8]张静,叶一斌,赖恒.掺锰磷酸铁锂的制备及电化学特性研究[J].福建师范大学学报(自然科学版), 2013, 29(1):53-57.
[9]宋翠环,孙军康,黄富强,等. Mn掺杂Li3Fe2(PO4)3正极材料的制备与表征[J].功能材料, 2009, 40(4):604-607.
[10] SONG X Z, CAO Y, ZHANG Y, et al. Preparation and characterization of nanoscale flaky iron phosphate from phosphating slag[C]//6th Annual International Conference on Material Science and Engineering(ICMSE2018),Suzhou, Jiangsu, China, June 22-24, 2018. IOP Conference Series:Materials Science and Engineering, 2018,397:012001.
[11]李玲玲.橄榄石结构LiMPO4(M=Fe、Mn)锂离子电池正极材料的溶剂热合成及其电学性能改性研究[D].杭州:浙江大学, 2016.
[12]程家顺.锂离子电池正极材料磷酸铁锂的合成及性能研究[D].长沙:中南大学, 2014.
[13]郑延辉,王明阳,张芬丽,等.锂离子电池新型负极材料的研究进展[J].河南化工, 2017, 34(9):13-17.
[14]陈路路,杨柳,刘双任,等. Mn掺杂改性{010}面择优生长的磷酸铁锂纳米片[J].西南民族大学学报(自然科学版), 2015, 41(3):373-378.
[15]王梦雪,李洪亮,阚光伟,等.不同锂源和碳源对RAPET法合成LiFePO4/C的影响[J].青岛大学学报(自然科学版), 2012, 25(1):37-41.
[16]谷和云,李昇,李二锐,等.镁离子掺杂磷酸铁锂的制备及其电化学性能[J].无机盐工业, 2016, 48(1):64-67.
[17] YUAN H, WANG X Y, WU Q, et al. Effects of Ni and Mn doping on physicochemical and electrochemical performances of LiFePO4/C[J]. Journal of Alloys and Compounds, 2016, 675:187-194.
[18] PADHI A K, NANJUNDASWAMY K S, GOODENOUGH J B D. Phospho-olivines as positive-electrode materials for rechargeable lithium batteries[J]. Journal of Electrochemical Society, 1997, 144(4):1188-1194.
[19]叶长福,郑会元,劳铭,等.过渡金属离子掺杂对磷酸铁锂性能的影响[J].材料导报, 2017, 31(1):29-32.
[20]从长杰,张向军,卢世刚,等.不同碳源对制备LiFePO4/C复合材料性能影响[J].电源技术, 2012,36(3):303-305.
[2] KANG H C, WANG G X, GUO H Y, et al. Facile synthesis and electrochemical performance of LiFePO4/C composites using Fe-P waste slag[J]. Industrial&Engineering Chemistry Research, 2012, 51(23):7923-7931.
[3]熊新宇,熊天庆,宋倩倩,等.金属表面处理磷化渣综合利用技术[J].冶金动力, 2015(2):43-45.
[4]刘肖强,张素娜,王利军,等.焙烧温度对提纯磷化渣制备LiFePO4/C正极材料的影响[J].上海第二工业大学学报, 2017, 34(1):26-30.
[5]林娟.锂离子电池正极材料LiFePO4的改性研究进展[J].广东化工, 2016, 43(11):135.
[6]舒进波,张金利,李.锰掺杂对于磷酸铁锂高倍率性能影响的研究[J].化工新型材料, 2014, 42(7):102-104.
[7]刘肖强,王利军,乔永民,等.磷化渣制备多元掺杂LiFePO4/C极材料的研究[J].电源技术, 2017, 41(10):1392-1395.
[8]张静,叶一斌,赖恒.掺锰磷酸铁锂的制备及电化学特性研究[J].福建师范大学学报(自然科学版), 2013, 29(1):53-57.
[9]宋翠环,孙军康,黄富强,等. Mn掺杂Li3Fe2(PO4)3正极材料的制备与表征[J].功能材料, 2009, 40(4):604-607.
[10] SONG X Z, CAO Y, ZHANG Y, et al. Preparation and characterization of nanoscale flaky iron phosphate from phosphating slag[C]//6th Annual International Conference on Material Science and Engineering(ICMSE2018),Suzhou, Jiangsu, China, June 22-24, 2018. IOP Conference Series:Materials Science and Engineering, 2018,397:012001.
[11]李玲玲.橄榄石结构LiMPO4(M=Fe、Mn)锂离子电池正极材料的溶剂热合成及其电学性能改性研究[D].杭州:浙江大学, 2016.
[12]程家顺.锂离子电池正极材料磷酸铁锂的合成及性能研究[D].长沙:中南大学, 2014.
[13]郑延辉,王明阳,张芬丽,等.锂离子电池新型负极材料的研究进展[J].河南化工, 2017, 34(9):13-17.
[14]陈路路,杨柳,刘双任,等. Mn掺杂改性{010}面择优生长的磷酸铁锂纳米片[J].西南民族大学学报(自然科学版), 2015, 41(3):373-378.
[15]王梦雪,李洪亮,阚光伟,等.不同锂源和碳源对RAPET法合成LiFePO4/C的影响[J].青岛大学学报(自然科学版), 2012, 25(1):37-41.
[16]谷和云,李昇,李二锐,等.镁离子掺杂磷酸铁锂的制备及其电化学性能[J].无机盐工业, 2016, 48(1):64-67.
[17] YUAN H, WANG X Y, WU Q, et al. Effects of Ni and Mn doping on physicochemical and electrochemical performances of LiFePO4/C[J]. Journal of Alloys and Compounds, 2016, 675:187-194.
[18] PADHI A K, NANJUNDASWAMY K S, GOODENOUGH J B D. Phospho-olivines as positive-electrode materials for rechargeable lithium batteries[J]. Journal of Electrochemical Society, 1997, 144(4):1188-1194.
[19]叶长福,郑会元,劳铭,等.过渡金属离子掺杂对磷酸铁锂性能的影响[J].材料导报, 2017, 31(1):29-32.
[20]从长杰,张向军,卢世刚,等.不同碳源对制备LiFePO4/C复合材料性能影响[J].电源技术, 2012,36(3):303-305.