Development of new polyanionic cathode/anode active materials for post Li-ion batteries

后置锂离子电池新型聚阴离子正极/负极活性材料的开发

• 批准号: 14205124
• 负责人: OKADA Shigeto
• 金额: $ 28.95万
• 依托单位: KYUSHU UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2004
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-14205124/
• 关键词: Lithium-ion battery; Cathode active material; Intercalation; Host compound

Our research of realize low-cost and high-energy density post Li-ion batteries for EV use can be summarized as follows;1)New synthesis process for iron phosphate :a)High temperature melting synthesis for LiFePO_4 :In order to use low reactive iron oxide as starting material, FeO was melted with P_2O_5 and LiOH-H_2O at 1500 ℃ for a few minutes and cooled in an Ar atmosphere. The slow-cooled sample with 140 mAh/g shows a similar profile to solid-state synthesized olivine LiFePO_4, though the quenched amorphous sample shows a monotonically decreasing discharge profile with poor capacity.b)Low temperature soft chemistry method for FePO_4 :In the use of low cost iron powder as a starting material, metallic iron powder and P_2O_5 were reacted in water at room temperature. The highest capacity obtained by annealing at 500 ℃ was 153 mAh/g.2)Pyrophosphate systemWe could obtained LiVP_2O_7 andTiP_2O_7 as new compounds. They show both M^<2+>/M^<3+> and M^<3+>/M^<4+> redox reactions on charge/discharge cycle. Moreover, (MoO_2)_2P_2O_7 shows the largest reversible capacity (150 mAh/g) as a cathode fur Na battery.3)Borate systemWe synthesized the calcite-type iron borate (FeBO_3) as polyanionic anode with higher capacity than that of graphite. In order to reduce the voltage, the redox couple replacement from Fe to V or Ti could be done successfully.4)Silicate systemWe could synthesized the single-phase Li_2CoSiO_4. The theoretical capacity of the olivine-type silicate is two times larger than that of the olivine-type phosphate such as LiFePO_4.5)Fluoro-phosphate systemAs a new fluorophosphate system, single phase Li_2CoPO_4F could be obtained by solid-state synthesis method and the structure was identified by neutron diffraction. The theoretical capacity is two times larger than that of LiFePO_4 and the cell voltage is 4.8 V.versus Li.

我们在实现低成本、高能量密度的电动汽车用后置锂离子电池方面的研究可概括如下：1）磷酸铁新合成工艺：a）高温熔融合成LiFePO_4：为了使用低反应活性以氧化铁为原料，将FeO与P_2O_5和LiOH-H_2O在1500℃下熔融几分钟，并在Ar气氛中缓慢冷却至140℃。 mAh/g 显示出与固态合成橄榄石 LiFePO_4 相似的曲线，尽管淬火非晶样品显示出单调递减的放电曲线且容量较差。 b) FePO_4 的低温软化学方法：使用低成本铁粉作为材料以金属铁粉和P_2O_5为原料，在室温下在水中反应，500℃退火得到的最高容量为153。 mAh/g.2)焦磷酸体系我们得到了LiVP_2O_7和TiP_2O_7作为新化合物，它们在充电时同时表现出M^<2+>/M^<3+>和M^<3+>/M^<4+>氧化还原反应。此外，(MoO_2)_2P_2O_7作为Na正极显示出最大的可逆容量(150mAh/g)。 3）硼酸盐体系我们合成了比石墨容量更高的方解石型硼酸铁（FeBO_3）作为聚阴离子负极，为了降低电压，可以成功地实现从Fe到V或Ti的氧化还原电对置换。4。 )硅酸盐体系我们可以合成单相Li_2CoSiO_4，橄榄石型硅酸盐的理论容量比橄榄石型磷酸盐大两倍。 LiFePO_4.5)氟磷酸盐体系作为一种新型的氟磷酸盐体系，采用固相合成方法可以得到单相Li_2CoPO_4F，并通过中子衍射鉴定其结构，其理论容量比LiFePO_4大2倍，电池电压为1.5倍。 4.8 V. 与 Li。

项目成果

Electrochemical Sodium Insertion into the 3D-framework of Na_3M_2(PO_4)_3 (M=Fe, V)

• DOI: 10.15017/7951
• 发表时间: 2002
• 期刊: The reports of Institute of Advanced Material Study Kyushu University
• 作者: Y. Uebou;上坊 泰史;T. Kiyabu;木藪 敏康;S. Okada;岡田 重人;J. Yamaki;山木 準一;ヤスシ ウエボウ;トシヤス キヤブ

J.Yamaki et al.: "Phase Separation of Intercalation Electrode"Ionics. 8. 53-61 (2002)

J.Yamaki 等人：“嵌入电极的相分离”离子学。

Y.Uebo et al.: "Cathode Properties of Pyrophosphates for Rechargeable Lithium Batteries"Solid State Ionics. 148. 323-328 (2002)

Y.Uebo 等人：“可充电锂电池焦磷酸盐的阴极特性”固态离子学。

2次電池正極材料の製造方法、および2次電池

二次电池正极材料的制造方法及二次电池

• 发表时间: 2003

非水電解質二次電池正極活物質

非水电解质二次电池正极活性物质

• 发表时间: 2004