STADIES FOR SYNTHESIS OF LAYERED SOLIDE SOLUTION TYPE CATHODE MATERIALS AND ITS ELECTROCHEMICAL LITHIUM INTERCLATION BEHAVIOR.

层状固溶体型正极材料的合成及其电化学嵌锂行为的研究。

• 批准号: 13450358
• 负责人: MASAKI Yoshio
• 金额: $ 5.95万
• 依托单位: Saga University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-13450358/
• 关键词: LITHIUM ION BATTERY; CATHODE MATERIAL; SOLID SOLUTION; LAYERED STRACTURE; LiCrO_2; LiNiO_2; Li_2MnO_3; Li_2TiO_3; 3>O_3; Li_2TiO_3; 正極材料; リチウム電子; LiNiO_2; LiCrO_2; Li_2MnO_3

It is found that layered LiNiO_2 forms electroactive solid solution with similar layered Li_2MnO_3 in the all composition range. Though low temperature phase Li_2TiO_3 has same structure with Li_2MnO_3, the structure of solid solution between LiNiO_2 and Li_2TiO_3 changes from layered structure to rock salt structure as the increase in Ti content because of enhanced cation mixing. On the other hand, LiCrO_2 forms layered solid solution with Li_2TiO_3. The solid solution with Ni/Ti=1 shows largest capacity of more than 170 mAh/g. It is finally confirmed that LiCrO_2-Li_2MnO_3 and LiCrO_2-Li_2TiO_3 solid solutions have similar electrochemical and crystallographic properties, however, LiNiO_2-Li_2MnO_3 system is different from LiNiO_2-Li_2TiO_3 system in both character.LiNiXMn_yCo_<1-x-y>O_2 with lower Mn content of y<0.5 is electroactive material. LiNi_<1/3>Mn_<1/3>Co_<1/3>O_2 with high capacity is a typical compound among LiNi_xMn_yCo_<1-x-y>O_2 and it will be considered as a solid solu … More tion between LiNi_<1/2>Mn_<1/2>O_2 and LiCoO_2. Electrochemical property of LiNi_<1/3>Mn_<1/3>Co_<1/3>O_2 extremely depends on preparation process, and we have found that the battery performance can be predicted from the shape of initial charge curve. The essential reason for lower performance would be due to the presence of impurity, NiO, as a result, electroactive solid solution with Li_2MnO_3, which shows lower performance than pure LiNi_<1/3>Mn_<1/3>Co_<1/3>O_2, is formed.The research for LiNi_<1/2>Mn_<1/2-x>Ti_xO_2 has been carried out in order to clarify the difference between Mn and Ti in the formation of solid solution. In the course of study, complete Ti substituted compound, LiNi_<1/2>Mn_<1/2-x>Ti_xO_2 with rock salt structure, delivers more than 150 mAh/g at 50 ℃. This fact indicates the possibility of excellent cathode materials with rock salt structure, which has been considered unsuitable because of difficulty in Li diffusion. This finding would lead to the development of rock salt type electrode materials. The new material shows low reproducibility in electrochemical property at room temperature, however, enhanced properties are confirmed by the formation of solid solution with Li_2TiO_3. Less

发现层状LiNiO_2与层状Li_2MnO_3在所有组成范围内都形成电活性固溶体。低温相Li_2TiO_3与Li_2MnO_3具有相同的结构，但随着Ti含量的增加，LiNiO_2与Li_2TiO_3之间的固溶体结构由层状结构向岩盐结构转变，这是由于阳离子混合作用增强所致。LiCrO_2与Li_2TiO_3形成层状固溶体。当Ni/Ti=1时，固溶体的最大容量可达170 mAh/g。最后确定了LiCrO_2-Li_2MnO_3和LiCrO_2-Li_2TiO_3固溶体具有相似的电化学和晶体学性质，而LiNiO_2-Li_2MnO_3体系与LiNiO_2-Li_2TiO_3体系在这两个性质上都有所不同，<1-x-y>Mn含量较低（y&lt;0.5）的LiNiXMn_yCo_ O_2是电活性材料。LiNi_（1/3）Mn_（1/3）Co_（1/3）O_2是LiNi_xMn_yCo_ O_2中的一种典型的高容量化合物<1-x-y>，可以认为它是一种固溶体，在LiNi_（1/3）Mn_（1/3）Co_（1/3）O_2中的一种。 ...更多信息 LiNi_（1/2）Mn_（1/2）O_2与LiCoO_2之间存在着一定的相互作用。LiNi_（1/3）Mn_（1/3）Co_（1/3）O_2的电化学性能与制备工艺有很大的关系，首次充电曲线的形状可以预测电池的性能。LiNi_（1/3）Mn_（1/3）Co_（1/3）O_2电活性固溶体的电活性低于纯LiNi_（1/3）Mn_（1/3）Co_（1/3）O_2，LiNi_（1/2）Mn_（1/2-x）Ti_xO_（1/2-x）为了澄清锰和钛在固溶体形成方面的差异，进行了2。在研究过程中，得到了具有岩盐结构的完全钛取代化合物LiNi_（1/2）Mn_（1/2-x）Ti_xO_2，在50 ℃时的放电容量大于150 mAh/g。这一事实表明具有岩盐结构的优良阴极材料的可能性，岩盐结构由于Li扩散困难而被认为是不合适的。这一发现将导致岩盐型电极材料的发展。新材料在室温下的电化学性能表现出较低的可重复性，但与Li_2TiO_3形成的固溶体证实了其性能的增强。少

项目成果

L.Zhang, H.Noguchi, M.Yoshio: "Synthesis and electrochemical properties of layered Li-Ni-Mn-O compounds"J.Power Sources. 110. 57-64 (2002)

L.Zhang，H.Noguchi，M.Yoshio：“层状Li-Ni-Mn-O化合物的合成和电化学性能”J.Power Sources。

D.Li: "Preparation of Li_<1+x>Ni_<0.5>Ti_<0.5>O_2 by spray dry method and its temperature dependence of electrochemical behaviour"ITE Letters. 4. 573-578 (2003)

D.Li：“喷雾干燥法制备Li_<1x>Ni_<0.5>Ti_<0.5>O_2及其电化学行为的温度依赖性”ITE Letters。

L.Zhang, H.Noguchi, M.Yoshio: "Synthesis and electrochemical properties of layered Li-Ni-Mn-O compounds"J.Power Sources. 117. 57-64 (2002)

L.Zhang，H.Noguchi，M.Yoshio：“层状Li-Ni-Mn-O化合物的合成和电化学性能”J.Power Sources。

野口英行, 芳尾真幸: "電子とイオンの機能化学シリーズNo.3"次世代型リチウム二次電池"第4節"リチウム二次電池材料技術正極総論(1)"エヌティーエス. 31 (2003)

Hideyuki Noguchi、Masayuki Yoshio：《电子和离子功能化学系列第3期》下一代锂二次电池》第4节《锂二次电池材料技术正极概述(1)》NTS.31(2003))

L.Zhang, X.Wang, H.Noguchi, M.Yoshio, K.Takada, T.Sakaki: "Electrochemical and ex situ XRD investigations on (1-x)LiNiO_2 xLi_2TiO_3(0.05<x<0.5)"Electrochimca Acta. (in press).

L.Zhang、X.Wang、H.Noguchi、M.Yoshio、K.Takada、T.Sakaki：“(1-x)LiNiO_2 xLi_2TiO_3(0.05<x<0.5) 的电化学和异位 XRD 研究”《电化学学报》。