Methods to visualize solid-state redox reaction of lead-tin silicate glass and their use to explore new materials for advanced lithium batteries

铅锡硅酸盐玻璃固态氧化还原反应的可视化方法及其在先进锂电池新材料探索中的应用

• 批准号: 09650910
• 负责人: OHZUKU Tsutomu
• 金额: $ 1.98万
• 依托单位: OSAKA CITY UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09650910/
• 关键词: electrochemistry; silicate glass; dilatometry; acoustic emission; lithium battery; insertion material; solid-state redox reaction

Research directed toward the better understanding of anomalous behavior on solid-state redox reactions of lead-tin silicate glass was carried out in the fiscal year of 1997-1998. Since X-ray diffraction was featureless, new methods to visualize and follow the phenomena took place in a solid matrix were necessary. Therefore, we have intensively developed the following new methods :(1) optical microscopy using optical microscope with CCD camera to see what are going on in a micrometer scale,(2) acoustic emission histometry using in-situ electrochemical cells with acoustic sensor and transducer, which is designed and fabricated in our laboratory, to detect cracking sounds of lead-tin silicate glass particles, and(3) dilatometry using home-made dilatometer with in-situ electrochemical cells which was designed to detect dimensional changes in 0.1 micrometer accuracy.These new methods worked very well to visualize and characterize the anomalous behaviors of lead-tin silicate (or borate) glass. The methods were also applied to lithium insertion materials consisting of lithium, transition metal, and oxygen ions, and the results were compared with those from lead-tin silicate glass. According to our results, lead-tin silicate glass or borate glass can be applied to a negative electrode material for lithium ion batteries although some improvement would be needed to erase cracking sound by acoustic emission histometry.As were stated above, we have successfully visualized phenomena which have not detect so far and gave useful information to materials chemists for advanced lithium batteries.

1997-1998财政年度进行了旨在更好地理解铅锡硅酸盐玻璃固态氧化还原反应异常行为的研究。由于X射线衍射是无特征的，因此需要新的方法来观察和跟踪在固体基质中发生的现象。为此，我们重点发展了以下新方法：（1）光学显微镜法，利用光学显微镜和CCD摄像机，在微米尺度上观察玻璃颗粒的行为;（2）声发射组织测量法，利用本实验室设计和制造的带有声传感器和换能器的原位电化学电池，检测铅锡硅酸盐玻璃颗粒的破裂声;（3）透射测量法，利用自制的原位电化学电池，检测铅锡硅酸盐（或硼酸盐）玻璃颗粒的尺寸变化，测量精度为0.1微米，这些新方法可以很好地观察和表征铅锡硅酸盐（或硼酸盐）玻璃的异常行为。该方法也适用于锂，过渡金属，和氧离子组成的嵌锂材料，并与铅锡硅酸盐玻璃的结果进行了比较。根据我们的研究结果，铅锡硅酸盐玻璃或硼酸盐玻璃可以应用于锂离子电池的负极材料，虽然需要一些改进来消除声发射组织测量的破裂声。如上所述，我们成功地观察到了迄今为止尚未发现的现象，并为先进锂电池的材料化学家提供了有用的信息。

项目成果

T.Ohzuka and A.Ueda: "Phenomiuological Expression of Solid-state Redox potentiats of LiCuO_2,LiCoy_2NiyO_2,and LiNiO_2,Insertion Electrodes" J.Electrochem.Socy. 144・8. 2780-2785 (1997)

T.Ohzuka 和 A.Ueda：“LiCuO_2、LiCoy_2NiyO_2 和 LiNiO_2 的固态氧化还原电位的现象学表达”，J.Electrochem.Socy 144・8（1997）。

K.Sawai,H.Tomura,and T.Ohzuku: "Acoustic Emission Histometry for Battery Material Research" Denki Kagaku. 66・3. 301-307 (1998)

K.Sawai、H.Tomura 和 T.Ohzuku：“电池材料研究的声发射组织测量”Denki Kagaku 66・3 (1998)。

T.Ohzuka,T.Yanagawa,M.Kouguchi,and A.Ueda: "An Innovative Insertion Material of LiAl1/4Ni3/4 O_2(R3m)for Lithium Ion(Shuttlecock) Batteries" J.Power Sources. 68. 131-134 (1997)

T.Ohzuka、T.Yanakawa、M.Kouguchi 和 A.Ueda：“用于锂离子（毽子）电池的 LiAl1/4Ni3/4 O_2(R3m) 的创新插入材料”J.Power Sources。

T.Ohzuka,S.Kitano,M.Iwanaga,H.Matsuno,A.Ueda: "Comparative study of Li[LixMn2-x] O_4 and LT-LiMnO_2 for Lithium-Ion Batteries" J.Power Sources. 68. 646-651 (1997)

T.Ohzuka、S.Kitano、M.Iwanaga、H.Matsuno、A.Ueda：“锂离子电池用 Li[LixMn2-x] O_4 和 LT-LiMnO_2 的比较研究”J.Power Sources。

T.Ohzuka,H.Tomura,and K.Sawai: "Monitoring of particle Fraotare by Acoustic Emission during charge and Discharge of Li/MnO_2 cells" J.Electrochem.Socy. 144・10. 3496-3500 (1997)

T.Ohzuka、H.Tomura 和 K.Sawai：“Li/MnO_2 电池充电和放电期间通过声发射监测粒子 Fraotare”J.Electrochem.Socy 144・10 (1997)。