Preparation of High Lithium Ion Conducting Glass-Ceramics by Mechanical Milling

机械铣削制备高锂离子导电微晶玻璃

• 批准号: 13450359
• 负责人: TATSUMISAGO Masahiro
• 金额: $ 9.22万
• 依托单位: Osaka Prefecture 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 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-13450359/
• 关键词: Mechanical milling; Amorphous; Ion conduction; Glass-ceramic; Ball milling; Conductivity; Solid electrolyte; Solid state battery; 非結晶

1. Amorphous materials with various compositions in the systems Li_2S-P_2S_5, Li_2S-P_2S_5-SiS_2, and Li_2S-P_2S_5-GeS_2 were prepared by mechanical milling (MM) of crystalline starting materials in a dry N_2 atmosphere at room temperature. The pelletized samples of these glassy materials exhibited high conductivities in the order of 10^<-4> Scm^<-1> at 25℃. It was found that the transport number of lithium ions of the glassy materials was almost unity and the potential window as solid electrolytes was wider than 10 V.2. Highly conductive glass-ceramics were obtained by the heat treatment under a variety of conditions of the above glassy materials prepared by MM. The glass-ceramics obtained after heating at around 230℃ showed the X-ray diffraction patterns very similar to those of highly conductive thio-LISICON II phases in Li_<4-x>Ge_<1-x>P_xS_4, suggesting that the thio-LISICON II analogue is formed in the glass-ceramics derived from the mechanically milled glassy powder in these systems.3. The highly conductive glass-ceramics were also obtained by the MM of starting materials of elements. Glassy Li_2S-P_2S_5 samples were successfully prepared by the MM of Li_2S, P, and S. The properties and structure of the glassy samples are very similar those of the samples prepared using Li_2S and P_2S_5. The glass-ceramics obtained by the heating of such an element-derived sulfide glasses exhibited similar properties to the glass-ceramics from P_2S_5-derived glasses.4. Electrochemical cells were constructed using glass-ceramics in the system Li_2S-P_2S_5 obtained by MM and heat treatment as an electrolyte, LiCoO_2, as a positive electrode and indium as a negative electrode. The all-solid-state cell exhibited excellent cycling performances with the reversible charge-discharge capacities of about 100mAhg^<-1> even after 200 cycles.

1.以Li_2S-P_2S_5、Li_2S-P_2S_5-SiS_2和Li_2S-P_2S_5-GeS_2为原料，在室温干燥的N_2气氛中机械球磨制备了不同组成的非晶态材料。这些玻璃材料的造粒样品在25℃时表现出10^&lt；-4&gt；scm^&lt；-1&gt；数量级的高电导率。研究发现，锂离子在玻璃材料中的输运数几乎为1，固体电解质的电势窗口大于10V。在230℃左右加热得到的微晶玻璃，其X射线衍射图与Li_&lt；4-x&gt；Ge_&lt；1-x&gt；P_xS_4中高导电性的Thio-Lisicon II相的X射线衍射图非常相似，这表明Thio-LISICON II类似物是在这些系统中机械球磨玻璃粉末得到的微晶玻璃中形成的。以元素为原料，采用MM法制备了高导电性微晶玻璃。用Li_2S、P和S的MM法制备了Li_2S-P_2S_5玻璃样品，其性能和结构与用Li_2S和P_2S_5制备的样品非常相似，加热得到的微晶玻璃的性能与用P_2S_5玻璃制备的微晶玻璃相似。以MM法制备的Li_2S-P_2S_5微晶玻璃为电解液，LiCoO_2为正极，铟为负极，构建了电化学电池。全固态电池表现出良好的循环性能，即使在200次循环后，其可逆充放电容量仍可达100mAhg~(-1)。

项目成果

R.Komiya: "Solid State Lithium Secondary Batteries Using an Amorphous Solid Electrolyte in the System (100-x)(0.6Li_2S・0.4SiS_2)・xLi_4SiO_4 0btained by Mechanochemical Synthesis"Solid State Ionics. 140・[1-2]. 83-87 (2001)

R. Komiya：“通过机械化学合成获得的系统中使用非晶固体电解质的固态锂二次电池（100-x）（0.6Li_2S·0.4SiS_2）·xLi_4SiO_4 0”固态离子学140·[1-2]。 -87 (2001)

辰巳砂昌弘: "超イオン伝導ガラスの開発(総説)"機械の研究. 54・[2]. 19-26 (2002)

Masahiro Tatsumisuna：“超离子导电玻璃的开发（评论）”机械研究54・[2]。

F.Mizuno: "All Solid-State Lithium Secondary Batteries Using High Lithium Ion Conducting Li_2S-P_2S_5 Glass-Ceramics"Chem. Lett.. [12]. 1244-1245 (2002)

F.Mizuno：“使用高锂离子导电Li_2S-P_2S_5玻璃陶瓷的全固态锂二次电池”Chem.

A.Hayashi: "Preparation and Characterization of Lithium Ion Conducting Glass-Polymer Composites"Chem. Lett.. [8]. 814-815 (2001)

A.Hayashi：“锂离子导电玻璃-聚合物复合材料的制备和表征”Chem。

A.Hayashi: "Structural Investigation of SnO-B_2O_3 Glasses by Solid-State NMR and X-ray Photoelectron Spectroscopy"J. Non-Cryst. Solids. 306・[3]. 227-237 (2002)

A. Hayashi：“通过固态核磁共振和 X 射线光电子能谱研究 SnO-B_2O_3 玻璃”，J. 非晶体固体。 227-237 (2002)。