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.本文报道了在室温干燥N2气氛下，用机械球磨法制备了Li_2S-SiS_2-LixMOy（LixMOy=Li_4SiO_4，Li_3PO_4）系非晶材料。颗粒化样品在25℃下表现出约10 μ Scm 2的高电导率<-4><-1>。结果表明，非晶态材料的锂离子输运数几乎为1，作为固体电解质的电位窗口大于10 V。2. MASNMR和XPS等光谱测试表明，MM法制备的非晶态硫氧化物粉末的局域结构与相应的熔融淬火玻璃非常接近。3<-10><-4><-1>.采用MM法制备的Li_2S-P_2S_5非晶样品，室温电导率为9 × 10 <-5><-1>~（-5）S cm ~（-1）。当样品升温至晶化温度后，电导率随温度的升高而下降，但下降的斜率较小。加热样品的电导率在室温下为6 × 10 - <-4>4S cm-3<-1>。结果表明，导电性的改善与形成的。以MM法制备的Li_2S-SiS_2-Li_4SiO_4系统非晶态材料为电解质，LiCoO_2为正极，铟为负极，制备了电化学电池。充放电容量从90至70 mAhcm-3逐渐降低<-2>直到约第10次循环，并且在第10次循环之后变得稳定。

项目成果

A.Hayashi: "Structural Change Accompanying Crystallization in the Lithium Ion Conductive Li_2S-SiS_2-Li_3PO_4 Oxysulfide Glasses"J.Ceram.Soc.Jpn.. 107・[6]. 510-516 (1999)

A.Hayashi：“锂离子导电Li_2S-SiS_2-Li_3PO_4硫氧化物玻璃中伴随结晶的结构变化”J.Ceram.Soc.Jpn.. 107・[6]（1999）。

A.Hayashi: "High-Resolution Solid-State NMR Studies of Ionically Conductive Li_2S-SiS_2-Li_2-P_2O_5 Oxysulfide Glasses"Phys.Chem.Glasses.. 40 [3]. 140-145 (1999)

A.Hayashi：“离子导电Li_2S-SiS_2-Li_2-P_2O_5硫氧化物玻璃的高分辨率固态NMR研究”Phys.Chem.Glasses.. 40 [3]。

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。

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: "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。