High power performance by defect introduction into spinel oxides for the usage of large-scale lithium ion battery

通过在尖晶石氧化物中引入缺陷来实现高功率性能，用于大型锂离子电池

• 批准号: 15350118
• 负责人: WAKIHARA Masataka
• 金额: $ 9.54万
• 依托单位: Tokyo Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-15350118/
• 关键词: spinel structure; lithium ion battery; high power performance; order-disorder structure; defect chemistry; 次世代リチウムイオン電池; 高電位正極; スピネル型酸化物; 酸素分圧制御; XANES; 分子動力学シミュレーション

Development of the cathode materials for Li ion battery is vital to meet the demands of portable devices, future usages of electric vehicles and so on. Among the cathodes, LiMn_2O_4 and related oxides has gained much attention because of its low cost, low toxicity, and relatively high energy density. Especially, LiNi_<0.5>Mn_<1.5>O_4 has received much attention because of its high discharge capacity, good cyclability, and dominant plateau at around 4.7 V, whereas other materials showed two plateaus at 〜4 and 5 V. In this study, the improvement of rate performance was attempted by introducing defects into spinel oxides. In addition, it was aimed to reveal the factors affecting rate performance from the viewpoint of defect chemistry. Spinel type oxide, LiNi_<0.5>Mn_<1.5>O_4 was synthesized with various temperatures and investigated their stoichiometry, crystal structures and electrochemical properties. Under oxygen atmosphere, a sudden increase of nonstoichiometry occurred with endothermes at around 760℃. In addition, infrared spectroscopic study revealed that ordered arrangement of Ni and Mn in octahedral sites was partially collapsed by the increase of nonstoichiometry. The electrochemical performance for the samples quenched from above and below 760℃ in oxygen atmosphere were investigated, and the samples quenched above 760℃ showed better rate-performance than those quenched below 760℃ Accordingly, the synthesis temperature of LiNi_<0.5>Mn_<1.5>O_4 was the key factor for controlling the arrangement of Ni and Mn, nonstoichiometry and electrochemical properties.

锂离子电池正极材料的开发对于满足便携式设备、电动汽车的未来使用等需求至关重要。在正极材料中，LiMn_2O_4及相关氧化物因其低成本、低毒性和相对较高的能量密度而备受关注。特别是，LiNi_<0.5>Mn_<1.5>O_4因其高放电容量、良好的循环性能以及在4.7V左右的主导平台而备受关注，而其他材料在〜4和5V处表现出两个平台。在本研究中，尝试通过在尖晶石氧化物中引入缺陷来改善倍率性能。此外，旨在从缺陷化学的角度揭示影响倍率性能的因素。在不同温度下合成了尖晶石型氧化物LiNi_<0.5>Mn_<1.5>O_4，并研究了其化学计量、晶体结构和电化学性能。在氧气气氛下，非化学计量突然增加，在760℃左右吸热。此外，红外光谱研究表明，随着非化学计量的增加，Ni和Mn在八面体位点上的有序排列被部分破坏。研究了760℃以上和760℃以下淬火样品在氧气气氛中的电化学性能，760℃以上淬火样品比760℃以下淬火样品表现出更好的倍率性能。因此，LiNi_<0.5>Mn_<1.5>O_4的合成温度是控制Ni和Mn排列、非化学计量和化学计量的关键因素。 电化学性能。

项目成果

Changes in Electronic Structure between Cobalt and Oxide Ions of Lithium Cobalt Phosphate as 4.8 V Positive Elecrode Material

4.8V正极材料磷酸钴锂钴离子与氧离子电子结构的变化

• 发表时间: 2004
• 期刊: Chem. Mater. 16
• 作者: 中山将伸;後藤哲;内本喜晴;脇原将孝;北島義典
• 通讯作者: 北島義典

Polymer electrolyte for Li ion battery

锂离子电池用聚合物电解质

• 发表时间: 2005
• 期刊: 未来材料 2
• 作者: 白川淳一;脇原将孝ほか;門磨義浩;宮代一;白川淳一;脇原将孝;脇原将孝
• 通讯作者: 脇原将孝

Investigation on cycleability in Li_xLa_<1/3>NbO_3 electrode material for rechargeable lithium ion battery

锂离子电池Li_xLa_<1/3>NbO_3电极材料循环性能研究

• 发表时间: 2005
• 期刊: J. Power Sources 146
• 作者: 中山将伸;脇原将孝ほか
• 通讯作者: 脇原将孝ほか

High-Rate-Capable Lithium-Ion Battery Based on Surface-Modified Natural Graphite Anode and Substituted Spinel Cathode for Hybrid Electric Vehicles

用于混合动力汽车的基于表面改性天然石墨阳极和替代尖晶石阴极的高倍率锂离子电池

• 发表时间: 2005
• 期刊: J. Electrochem. Soc. 152
• 作者: 原大周;白川淳一;生田博正;内本喜晴;脇原将孝;H.Ando et al.;I.R.M.Kottegoda;T.Furuta et al.;古田寿昭;I.R.M.Kottegoda
• 通讯作者: I.R.M.Kottegoda

Masanobu Nakayama, Kazuomi Imaki, Wonkyung Ra, Hiromasa Ikuta, Yoshiharu Uchimoto, Masataka Wakihara: "Using X-ray Absorption Spectroscopy to Measure Changes of Electronic Structure Accompanying Lithium Insertion into the Perovskite Type Oxides"Chem.Mater

Masanobu Nakayama、Kazuomi Imaki、Wonkyung Ra、Hiromasa Ikuta、Yoshiharu Uchimoto、Masataka Wakihara：“使用 X 射线吸收光谱测量伴随锂插入钙钛矿型氧化物中电子结构的变化”Chem.Mater