锂离子电池正极材料结构的量子化学研究-物理化学专业论文.docxVIP

重庆大学硕士学位论文 重庆大学硕士学位论文 英文摘要 ABSTRACT The layered LiC002，LiNi02 and the spinel LiMn204 common cathode materials for lithium—ion cells．There are few theoretic articles about the relationship between the electronic structure and performance of electrode material of lithium—ion eells．In this thesis，the rule of electronic structure changes after intercalation and substitution in the layered LiC002，LiNi02 and the spinel LiMn204 has been studied by using quantum chemical ab initio and density fimcfion theory(DFT)． Some models wim】7。4l，56 and 65 atoms have been calculated wi也 Ganssian98W．However,only the results of the two models witll 1 7 and 4l atoms could be gained．In order to determine the calculating method and basis set，the model of LisMn40s”is selected as all example．According to calculation speed and the dlaracteristics oftlle model．the method RHF and the basis STO一5(Ⅳ6—31G+are finally determined respectively．This calculation Can fairly explain$onle experiments results． ThemainWOrkofthisthesisiSto study ofelectronic structure ofcathodematerial Some structure parameters，such total energy,atomic net charge，atomic overlap population，of the model Li5Mn408”，Li5Mnl2024’，Li7C0602。1孓，Li7Ni602015_， Li5C02Mn208”，Li5Ni2Mn20s+are calculated．The following results have been concluded： (a)Ab initio has its advantages in the calculating of atom cluster containing transition metal，especially in precision and total energy calculations， (b)Lithium has been existing ionic state in lithium—manganese oxides and the layered materials after losing electron partially． fc)The total energy of manganate-exides materials decreases after intercalation lithium．The electrovalent bond weakens and the covalent bond stren【gl!hen between manganese and oxygen due to ion polarization effect，which makes the spine／structure more stable． (d)Thc total energy of the layered material decreases after intercalation lithium． The net charge of transition metal atom has decreased result of the static effect of lit