>6>, K 87Á å /¡ b%Ê'26ä$Î 7Á ¼ í7Á Ê d Û(Ô M 5 ä M …...b +)] )(++ + _>* + ...

(Ca2+) (Li+)

(Ca0.5CoO2)(PBA)

8-1-1 Ca0.5CoO2 CoO6Ca2+

LiCoO2 Ca0.5CoO2 Ca2+ ab

Ca2+

CaxCoO2

CaxCoO2 xCa2+ 2xe- CoO2 x = 0.5 Co3+/Co4+ CaxCoO2

Ca2+ x CoO6

- 72 -

Co Co

Ca0.5CoO2 Ca0.5CoO2

8-1-2 PBA5~6 Å

PBA AxM[M’(CN)6] nH2O MM’-PBA

Ax (K) M M’ (Fe) (PBA)Ax M M’ Fe, Co, Ni, Mn PBA CaFe[Fe(CN)6]

CaFe(II)[Fe(II)(CN)6] Ca2+ 2e- Fe(III)[Fe(III)(CN)6]

PBA Fe2+/Fe3+ Ca2+

1 PBA

Ca2+ PBAM’ = Fe MFe-PBA M

= Co, Ni, Mn MFe-PBA Ca2+ MFe-PBA

10 mol% Na2O2 Co3O4 Ar650 , 16 h O2 (1 L/min) 8-2-1

NaCoO2 XNaCoO2

- 73 -

10 mol% Ca(NO3)2 4H2O NaCoO2 Ar300 , 48 h 8-2-2

X Ca0.5CoO2 Ca0.5CoO2

(FE-SEM)X (EDX) 8-2-3

NaCa Na+

Ca2+ EDX

- 74 -

0.05 mol L-1 K3[Fe(CN)6] 0.1 mol L-1 MCl2 2 h

80 24 h M Ni Mn CoM = Ni 80 8-2-4

XMFe-PBA (M = Ni, Mn, Co)

MFe-PBA(FE-SEM) X (EDX)

8-2-5 MFe-PBA NiFe-PBACoFe-PBA MnFe-PBA 8-2-4

- 75 -

MnFe-PBA PBAMnFe-PBA XRD EDX

MFe-PBAK K MFe-PBA

Ca0.5CoO2 V2O570 25 5

80 , 12 hAg/Ag+ 0.5 mol L-1 Ca[N(SO2CF3)2]2/AN

Ar

Ca0.5CoO2Ca2+

80 mAhg-1 Ca0.5CoO2

30 50 Acm-2 80 mAhg-1 Ca0.5CoO2 1.3 V vs. Ag/Ag

+ -3.0 V vs. Ag/Ag+

- 76 -

8-3-1 Ca0.5CoO2Ca2+

Ca0.5CoO2

MFe-PBA NiFe-PBANiFe-PBA

NiFe-PBA70 20 10

80 10 1080 , 12 h

PBA150 6 h Ar

Ag/Ag+ 0.5 mol L-1 Ca[N(SO2CF3)2]2 /AN Ar

NiFe-PBA

30 25 Acm-2 1.0 V vs. Ag/Ag+ -1.0 V vs. Ag/Ag+

8-3-2 NiFe-PBA 0.2 ~ -0.1 V vs. Ag/Ag+

0.4 V vs. Ag/Ag+

Ca2+

NiFe-PBA

- 77 -

Ca0.5CoO2 80 mAhg-1

X 8-4-1 XRDSi 8-4-1 CoO6(001), (002)

Ca2+

Ca2+

- 78 -

Ca2+

EDXCo 8-4-2

8-4-2 CaCa0.5CoO2 Ca

2+ Ca2+

NiFe-PBA

X 8-4-3 XRDSi 8-4-3 NiFe-PBA (200),

(220) Ca2+

Ca2+

- 79 -

Ca2+

EDX Fe8-4-4 8-4-4 Ca PBA Ca2+

Ca NiFe-PBA Ca2+

K PBAK+ K

PBA K+ Ca2+ NiFe-PBA

Ca2+ NiFe-PBA X(XPS)

XPS 8-4-5 8-4-5 Fe 2p XPS NiFe-PBA Ca2+

Fe3+ Fe3+ Fe2+

NiFe-PBA Ca2+ Fe2+

Fe2+ Fe3+ 8-4-5 Ni 2p XPSNi2+

Ni2+ 863 eV NiNi Ca2+

- 80 -

Ca0.5CoO2(MFe-PBA) NaCoO2Ca0.5CoO2 M = Ni, Co, Mn

MFe-PBA

Ca0.5CoO2MFe-PBA NiFe-PBA

NiFe-PBA

- 81 -

1下版_150305（山下_豊橋技科大「平成26最終報告書」）本文34