実験報告書様式（一般利用課題・成果公開利用）

MLF	 Experimental Report

提出日 Date of Report
13/04/08

課題番号 Project No.2012B0110

装置責任者 Name of responsible person

実験課題名 Title of experiment

Takashi Kamiyama

Lithium conduction mechanism of lithium superionic

装置名 Name of Instrument/（BL No.）

conductors Li4-xGe1-xPxS4 for all-solid-state lithium batteries

Super HRPD (BL-08)

実験責任者名 Name of principal investigator

実施日 Date of Experiment

Ryoji Kanno

2013/01/18-20

所属 Affiliation
Tokyo Institute of Technology

試料、実験方法、利用の結果得られた主なデータ、考察、結論等を、記述して下さい。（適宜、図表添付のこと）
Please report your samples, experimental method and results, discussion and conclusions. Please add figures andtables for better explanation.
1. 試料 Name of sample(s) and chemical formula, or compositions including physical form.

Powdered Li4-xGe1-xPxS4(x = 0.55 and 0.65) were synthesized by a solid state reaction. We
confirmed Li4-xGe1-xPxS4 formed solid solution range from 0.55 to 0.65 using X-ray diffraction
measurement. The structure of x = 0.5 - 0.65 were confirmed by the synchrotron X-ray
diffraction Rietveld refinement.
These compounds were iso-structural to Li10GeP2S12.
However, positions and occupancy values of lithium have not been clarified. These samples
show high lithium ionic conductivity.

2. 実験方法及び結果 （実験がうまくいかなかった場合、その理由を記述してください。）
Experimental method and results.

If you failed to conduct experiment as planned, please describe reasons.

Neutron diffraction data of Li3.45Ge0.45P0.55S4 and Li0.335Ge0.35P0.65S4 were taken at low
temperatures on a time-of-flight (TOF) neutron powder diffractometer at Super HRPD (BL08)
using the BS (Back Scattering) bank. Measurement temperatures were 5, 100, 135 and 200 K todetermine lithium positions. The specimen of ca. 1.5 cc is contained in a cylindrical vanadiumcell of dimensious 10 mm inradius, 20 mm in height. The data were analyzed by the Rietveld
method using the Z-Rietveld program. Figure 1 shows a preliminary Rietveld analysis result
using neutron diffraction data of Li3.45Ge0.45P0.55S4 measured at 200 K. Structural parameters are
summarized in Table 1. The structure was refined based on the structure model with Li1oGeP2S12
type structure investigated by the X-ray Rietveld analysis. Li site(Li(4) site) was suggested frompresent refinement structure. Li(4) forms twisted octahedra with sulfide anion and links toLi(1)S6 and Li(3)S6 octahedra which form lithium conduction path in the structure, by face andedge sharing. Structural changes against temperatures have been investigated.

12. 実験方法及び結果（つづき） Experimental method and results (continued)

This can give better understanding of lithium conduction mechanism.

Cell parameter: a=	   8.696036 Å, c= 12.620741 Å. Space group: P42/nmc. Rwp =4.25 %, Rp = 3.54 %, Re = 3.20 %, RB = 13.06 %, RF = 7.25 %, χ2 = 1.76

Table 1	  Rietveld refinement results for Li3.45Ge0.45P0.55S4 measured at 200 K.

Atom	  Site	  Occupancy	  x	  y	  z	  B	  /	  Å2 	 

Ge1	  P1	  P2	  S1	  S2	  S3	  Li1	  Li2	  Li3	  Li4	  4d	  4d	  2b	  8g	  8g	  8g	  16h	  4d	  8f	  4d	  0.675	  0.325	  1	  1	  1	  1	  0.5771	  (9)	  1	  0.5512	  (9)	  0.7406	  (3)	  	  0	  	   =	  x(Ge1)	  0	  0	  0	  0	  0.2504	  (9)	  0	  0.2473	  (9)	  0	  	  0	  =	  y(Ge1)	  0	  0.1892	  (7)	  0.2943	  (7)	  0.6977	  (8)	  0.2504	  (9)	  0.5	  0.2473	  (9)	  0	  	  0.6889	  (9)	  =	  z(Ge1)	  0.5	  0.4081	  (7)	  0.0982	  (7)	  0.7885	  (8)	  0.2003	  (9)	  0.9537	  (9)	  0	  0.2644	  (9)	  	  0.85	  0.85	  0.93	  0.64	  0.75	  0.09	  5.96	  3.18	  6.28	  2.46	  	  	  2