Preparation of Amorphous Solid Electrolytes by Mechanical Milling

机械研磨制备非晶固体电解质

• 批准号: 11450336
• 负责人: TATSUMISAGO Masahiro
• 金额: $ 8.64万
• 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: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-11450336/
• 关键词: Mechanical milling; Amorphous; Ion conduction; Oxysulfide; Ball milling; Conductivity; Solid electrolyte; Solid state battery

1.Amorphous materials with various compositions in the oxysulfide system Li_2S-SiS_2-LixMOy (LixMOy=Li_4SiO_4, Li_3PO_4) were obtained by mechanical milling (MM) of crystalline starting materials in a dry N_2 atmosphere at room temperature. The pelletized samples 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 amorphous materials was almost unity and the potential window as solid electrolytes was wider than 10V.2.Several spectroscopic measurements like MAS NMR and XPS revealed that the local structure of the amorphous oxysulfide powders prepared by MM was very close to thata of the corresponding melt quenched glass. Furthermore, the formation of continuous amorphous phase with the inrease of milling tive incresed conductivity grastically from 10^<-10> to 10^<-4> Scm^<-1> at room temperature.3.The amorphous Li_2S-P_2S_5 sample prepared by MM exhibited high conductivity of 9x10^<-5> S cm^<-1> at room temperature. After the sample was heated up to the crystallization temperature, the conductivity decreased with a smaller slope in the cooling process. The conductivity of the heated sample was 6x10^<-4> S cm^<-1> at room temperature. It was revealed that the conductivity improvement with forming the. 80Li_2S・20P_2S_5 glass-ceramics was brought about by the softening of glassy powders and the formation of highly conductive Li_7PS_6 crystal.4.Electrochemical cells were constructed using amorphous matterials in the system Li_2S-SiS_2-Li_4SiO_4 obtained by MM as an electrolyte, LiCoO_2 as a positive electrode and indium as a negative electrode. The charge-discharge capacity decreased gradually from 90 to 70 mAhcm^<-2> till about the 10th cycle and became stable after the 10th cycle.

1.在室温下干燥N_2气氛中通过机械研磨(MM)得到硫氧化物体系Li_2S-SiS_2-LixMOy(LixMOy=Li_4SiO_4,Li_3PO_4)中不同组成的非晶材料，粒状样品表现出高电导率。 25℃时约为10^<-4>Scm^<-1>。非晶材料的锂离子传输数几乎一致，并且作为固体电解质的电位窗口宽于10V。2.MAS NMR和XPS等多项光谱测量表明，MM制备的非晶硫氧化物粉末的局部结构非常好。接近于相应的熔融淬火玻璃。此外，随着研磨的增加，连续非晶相的形成大大增加了电导率室温下从10^<-10>到10^<-4>S cm^<-1>。3.MM制备的非晶Li_2S-P_2S_5样品表现出9x10^<-5>S cm^<的高电导率- 1>在室温下，将样品加热至结晶温度后，在冷却过程中电导率以较小的斜率下降。室温下6x10^<-4>Scm^<-1>表明，形成80Li_2S·20P_2S_5玻璃陶瓷时电导率的提高是由于玻璃粉末的软化和高导电性Li_7PS_6的形成而引起的。 4.采用Li_2S-SiS_2-Li_4SiO_4体系中的非晶材料构建电化学电池MM作为电解质，LiCoO_2作为正极，铟作为负极，充放电容量从90mAhcm^-2逐渐下降到第10次循环左右，并在第10次循环后变得稳定。

项目成果

A.Hayashi: "Development of Lithium Ion Conducting Oxysulfide Glasses"Proc.7th Asian Conf.on Solid State Ionics. 177-186 (2000)

A.Hayashi：“锂离子导电氧硫化物玻璃的开发”Proc.7th Asian Conf.on Solid State Ionics。

A.Hayashi: "Preparation and Characterization of Lithium-Ion-Conducting Sulfide Glasses"Kinzoku. 70 [7]. 550-558 (2000)

A.Hayashi：“锂离子导电硫化物玻璃的制备和表征”Kinzoku。

A.Hayashi: "High-Resolution Solid-State NMR Studies of Ionically Conductive Li_2S-SiS_2-Li_2O-P_2O_5 Oxysulfide Glasses"Phys.Chem.Glasses. 40[3]. 140-145 (1999)

A.Hayashi：“离子导电Li_2S-SiS_2-Li_2O-P_2O_5硫氧化物玻璃的高分辨率固态核磁共振研究”Phys.Chem.Glasses。

A.Hayashi: "Crystallization of Li_2S-SiS_2 Based Lithium Ion Conducting Glasses"Phys.Chem.Glasses. 40・[6]. 333-338 (1999)

A.Hayashi：“Li_2S-SiS_2基锂离子导电玻璃的结晶”Phys.Chem.Glasses 40・[6]（1999）。

H.Morimoto: "Mechanochemical Synthesis of New Amorphous Materials of 60Li_2S・40SiS_2 with High Lithium Ion Conductivity"J.Am.Ceram.Soc.. 82・[5]. 1352-1354 (1999)

H.Morimoto：“具有高锂离子电导率的新型非晶材料60Li_2S·40SiS_2的机械化学合成”J.Am.Ceram.Soc.. 82·[5]（1999）。