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。系统中具有各种组合物的无定形材料，LI_2S-P_2S_5，LI_2S-P_2S_5-SIS_2和LI_2S-P_2S_5-GES_2通过机械铣削（mm）在室温下干燥的N_2大气中的机械铣削（mm）。这些玻璃材料的颗粒样品以10^<-4> scm^<-1>在25℃时的顺序表现出高电导率。发现玻璃材料的锂离子的传输数几乎是统一性，并且由于固体电解质的范围宽于10 v.2。在上述玻璃材料的多种条件下，通过热处理获得了高电导性玻璃陶瓷。在230左右加热后获得的玻璃陶瓷表现出与Li_ <4-x> ge_ <1 x> ge_ <1-x> p_xs_4中高电导性硫代硫代II相非常相似的X射线衍射模式，这表明在玻璃陶瓷中形成了来自机械式玻璃玻璃制度的thio-lisicon II类似物。高导电性玻璃陶瓷也通过元素起始材料的MM获得。 Li_2s，P和S的MM成功制备了玻璃液li_2s-P_2S_5样品。玻璃样品的特性和结构非常相似，这些样品是使用LI_2S和P_2S_5制备的样品中的样本。通过加热这种元素衍生的硫化物玻璃获得的玻璃陶瓷，与P_2S_5衍生的玻璃相似的玻璃陶瓷的特性与玻璃陶瓷相似。4。用玻璃陶瓷在系统中构建电化学细胞LI_2S-P_2S_5，通过MM和热处理作为电解质，LICOO_2，作为正电极，作为负电极作为正电极。全稳态的细胞暴露了出色的循环性能，即使在200个循环后，可逆的电荷递送容量也约为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: "Fast Lithium-Ion Conducting Glass-Ceramics in the System Li_2S-SiS_2-P_2S_5"Electrochem.Solid-State Lett.. 6・[3]. A47-A49 (2002)

A.Hayashi：“Li_2S-SiS_2-P_2S_5 系统中的快速锂离子导电玻璃陶瓷”Electrochem.Solid-State Lett.. 6・[3] (2002)。

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。