掺锰对磷酸铁锂正极材料的性能影响研究.docVIP

掺Mn2+对LiMnxFe1－xa potential candidate for the cathode material of the lithium secondary battery. However, poor electronic conductivity and lower Li+ diffusion rate limit its development. The modified LiFePO4 was prepared through solid state sintering，which was covered by Carbon or/and doped with Mn2+. These compounds were characterized by XRD, SEM, galvanostatic charge–discharge test. It is found that the sample-LiMn0.1Fe0.9PO4/C covered 5% carbon and doped with 10% Mn2+ was of higher tap density (1.12g/cm3), and its initial charge and discharge capacity was 160.2 mAh/g and 144.1 mAh/g at 0.1C respectively. The sample with only covered by 5% carbon was the most excellent in electrochemical performance. Its 0.1C charge capacity and discharge capacity was 163.7 mAh/g and 151.3 mAh/g respectively, and that its tap density was only 1.05g/cm3. A new explanation for Mn2+ doping effect in LiFePO4 is presented which can take into account the electrochemical performance. The explanation makes use of separating the initial charge/discharge capacities to explain the drop of capacity of sample doped with Mn2+. The way of improving electrochemical performance of LiFePO4 using doping will also be discussed. Keywords:Li-ion battery, Cathode material, LiFePO4, Lithium iron phosphate, Carbon covering, Doping, Nanomaterial _______________________________________________ 作者简介：刘和平（1982－），男，湖南人，硕士研究生，主要研究为锂离子电池正极材料 E-mail：liuheping001@163.com Biography: Liu He-ping(1982－), male , candidate for master. 联系人： 苏玉长（1964－），男，博士生导师；E-mail：ycsu@ 磷酸铁锂以其成本低，环境友好，热稳定性好，电化学性能优异，成为了锂离子电池正极材料领域的新宠。但是，LiFePO4（LFP）因为体电导率差，Li离子扩散速率低，严重限制了它在电池领域的运用。目前主要从三个方面来克服其缺陷。一是细化晶粒，减少Li+的扩散路径，可以显著提高材料的倍率性；二是表面包覆导电材料，如碳[1-8]，金属[19]等；三是掺杂元素，来提高体电导率，这方面报道比较多的是取代Li位的掺杂[9-15]。Li位掺杂可以使体导电率得以显著提高，但由于Li的扩散是沿着b轴进行的，所以锂位的掺杂会阻碍Li+的扩散通道，不利于Li+的扩散。Fe位掺杂也可以稳定晶体结构，同时提高电导率。而且，它不会阻挡Li的扩散路径[16-17]。 铁位掺杂Mn2＋来提高电导率和稳定结构的研究已有报道[17]，但还不够深入。其中，Mn2＋的掺杂可以使晶胞参数增大，Li+的扩散由磷酸铁锂中的两相界面控制转变为纯一维单相扩散控制过程。可望改善磷酸铁锂的综合电化学性能。 本文选择研究了包覆碳并掺杂Mn2＋的磷酸铁锂正极材