Liｲｵﾝ二次電池 固体電解質の研究

1 Li ( ) 2011/1/20 AC AC 2011/1/20Li .. Li3PS4 2011/1/20 Li3PS4( ) Li2S( 98%)+P2S5(Aldrich 99%) (Fritch Ar 380rpm 40h) XRD AC 0102030405060701030507090 XRD [cps]2 [ ] MultiFlex 40kV 40mA 2 /min 2011/1/20 2011/1 10 In (100 m )1, 2, 3mm10mm In (100 m ) 4, 6, 8mm In 4mm In 6mm In 8mm 1mm 2mm 3mm AC AC 2011/1/20Li+Li+Li+Li+Li+Li+Li+Li+Li+Li+L i+Li+Li+Li+Li+Li+Li+Li+Li+Li+Li+e-e-e-Li +e-e- rb ri ci cd rct Li (AC) AC Nyquist 2011/1/20 CdRctRbRiCiZwRb= rbRi= riCi= ciRct= rctZw.

2 Warburg Cd= cd 45 Z'-Z" ( )Warburg AC Li+Li+Li+Li+Li+Li+Li+Li+Li+Li+Li+Li+Li+L i+Li+Li+Li+Li+Li+Li+Li+e-e-e-Li+e-e- rb ri ci cd rct ( ) Ci Cd AC Solartron 1287( )+1255B( ) 1 MHz 20 C 100 CAC Ar Ar ( ) ( ( )) Ar -40 C 300 C (-40 C 100 C ) 4 ( ) ( 10mm) 100 C ..AC HcHpLpLc ( ) AC AC Nyquist (2mm In 4mm @20 C) AC ( 10mV ) AC 45 2011/1/20-2,000 -1,000 0 1,000 2,000 3,000 4,000 2,5003,5004,5005,5006,5007,5008,500-Z"[ ]Z'[ ]20 C 10mV20 C 20mV20 C 50mV20 C 100mV20 C 200mV20 C 500mV20 C 1000mV20 C 1100mV20 C 1200mV20 C 1300mV20 C 1500mV20 C 2000mV20 C 2500mV20 C 3000mV 45 Z'-Z" ( )Warburg -2,000 3,000 8,000 13,000 18,000 23,000 28,000 05,00010,00015,00020,00025,00030,000-Z"[ ]Z'[ ]20 C 10mV20 C 20mV20 C 50mV20 C 100mV20 C 200mV20 C 500mV20 C 1000mV20 C 1100mV20 C 1200mV20 C 1300mV20 C 1500mV20 C 2000mV20 C 2500mV20 C 3000mV AC AC Nyquist (@100 C)

3 2011/1/20 45 Z'-Z" ( )Warburg -50 50 150 250 350 450 0100200300400500-Z"[ ]Z'[ ]100 C 5mV100 C 10mV100 C 20mV100 C 50mV100 C 100mV100 C 2000mV100 C 2500mV100 C 3000mV2mm In 8mm 3mm In 6mm -10 0 10 20 30 180190200210220-Z"[ ]Z'[ ]100 C 1mV100 C 2mV100 C 5mV100 C 10mV100 C 50mV100 C 100mV100 C 200mV100 C 500mV100 C 1000mV100 C 1500mV100 C 2000mV100 C 2500mV100 C 2800mV100 C 3000mV100 C In 4mm In 6mm In 8mm 1mm 2mm 3mm AC 2011/1/20 45 Z'-Z" ( )Warburg RbRiCiRctZwCd@25 CRb[ ] b[S/cm]Ri[ ] i[S/cm]Ci[F]Rb+i[ ] b+i[S/cm]1mm 6mm * 10-42mm 4mm 10-42mm 6mm 10-42mm 8mm 10-43mm 6mm 10-4 Zview [S/cm] = [cm] R[ ] [cm2] 1mm 6mm 100 C 2 4 AC Nyquist AC AC ( )

4 2011/1/20 AC 200 C OK AC / AC HcHpLpLc2mm 2mm 30mmL 2011/1/20-1,500 -500 500 1,500 2,500 3,500 1,5002,5003,5004,5005,5006,500-Z"[ ]Z'[ ]25 C 10mV25 C 20mV25 C 50mV25 C 100mV25 C 200mV25 C 500mV25 C 1000mV25 C 1500mV25 C 2000mV25 C 2500mV25 C 3000mV-5,000 0 5,000 10,000 15,000 20,000 25,000 05,00010,00015,00020,00025,00030,000-Z"[ ]Z'[ ]25 C 10mV25 C 20mV25 C 50mV25 C 100mV25 C 200mV25 C 500mV25 C 1000mV25 C 1500mV25 C 2000mV25 C 2500mV25 C + + + + + + + + + + + + +06|Z| [ ]f [Hz]25 C 10mV25 C 20mV25 C 50mV25 C 100mV25 C 200mV25 C 500mV25 C 1000mV25 C 1500mV25 C 2000mV25 C 2500mV25 C 3000mV-90 -80 -70 -60 -50 -40 -30 -20 -10 0 10 + + + + + + +06 [deg]f [Hz]25 C 10mV25 C 20mV25 C 50mV25 C 100mV25 C 200mV25 C 500mV25 C 1000mV25 C 1500mV25 C 2000mV25 C 2500mV25 C 3000mVNyquist Bode AC (2mm 4mm @25 C) 2011/1/20Z = Rb+Ri/(1+ 2Ri2Ci2)+(Rct+ / 1/2)/{(1+ 1/2Cd )2+ 2Cd2(Rct+ / 1/2)2}- j[ Ri2Ci/(1+ 2Ri2Ci2) + {(1+ 1/2Cd ) / 1/2+ (Rct+ / 1/2)2} / {(1+ 1/2Cd )2+ 2Cd2(Rct+ / 1/2)2} ] = RT/(21/2n2F2Ar)/(D1/2c*)Zw= (1-j) / 1/2Z = Z' + jZ " = atan-1(Z"/Z') 45 Z'-Z" ( )Warburg RbRiCiRctZwCdAC 2011/1/20 LR1R2C2R4C4 ZwR3C3C1Z = R1+R2/(1+ 2R22C22) +R3/(1+ 2R32C32)+(R4 + / 1/2)/{(1+ 1/2C4 )2+ 2C42(R4+ / 1/2)2}- j[ - L + 1/ C1+ R22C2/(1+ 2R22C22) + R32C3/(1+ 2R32C32) + {(1+ 1/2C4 ) / 1/2+ C4(R4+ / 1/2)]}

5 2} / {(1+ 1/2C4 )2+ 2C42(R4+ / 1/2)2} ] = RT/(21/2n2F2Ar)/(D1/2c*)Zw= (1-j) / 1/2Z = Z' + jZ" = atan-1(Z"/Z') ( ) 2011/1/20 Nyquist Bode -400-300-200-100010020030040050060002004 006008001,0001,200-Z"[ ]Z' [ ]1 10 100 1000 10000 + + + +07|Z| [ ]f [Hz]-100 -80 -60 -40 -20 0 20 40 60 80 100 + + + +07 [deg]f [Hz]2 MHz L[H}R1[ ]R4[ ]C4[F] 2011/1/20