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第七章 固体电解质电池及其应用 PowerPoint PPT Presentation


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第七章 固体电解质电池及其应用. 7.1 固体电解质简介 7.2 固体电解质工作原理 7.3 固体电解质的电子导电 7.4 固体电解质传感器的类型 7.5 固体电解质电池的应用. 7.1 固体电解质简介. 导电体通常可分为两大类。第一类是 金属导体,依靠自由电子导电 。当电流通过导体时,导体本身不发生任何化学变化。其电导率随温度升高而减小,称之为第一类导体。另一类是 电解质导体或第二类导体,它们导电是依靠离子的运动 ,因而导电时伴随有物质迁移,在相界面多有化学反应发生,其电导率随温度升高而增大。.

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第七章 固体电解质电池及其应用

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7.1

7.2

7.3

7.4

7.5


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7.1


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10-6 Scm-1


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ZrO211500C9%7%ZrO2

ZrO2Zr4+ CaOMgOY2O3Sc2O3ZrO2ZrO2ZrO2CaOZrO2ZrO2-CaOZrO2(CaO),


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6-3

7-3 CaOZrO2


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(CaO)(MgO)(Y2O3) 2


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7.2

  • ZrO2-CaO

    6-4E


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7.2

6-4


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7.2

  • 7-1

    1424

    7-2

    4


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7-17-2

7-3

7-4


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1 mol4FF=96500 C/mol

7-5

6-46-5

7-6

6-36-6

7-7

T

R8.314J/(molK)

F96500 0C mol-1

Nernst


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1

2

31


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(Pt)|[O]Fe|ZrO2-CaO|Cr2O3,Cr(Pt),1873KE=20mv.1/3 Cr2O3=2/3Cr(s)+1/2O2 (1),


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1/3 Cr2O3=2/3Cr(s)+1/2O2

1/2O2+2e=O-2: 1/3 Cr2O3 +2e = 2/3Cr(s)+O2-

: O-2 = 1/2O2+2e, 1/2O2 =[O]Fe,,:

O2- = [O]Fe +2e.

: 1/3 Cr2O3 =2/3Cr(s)+[O]Fe (3),

: :


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1/3 Cr2O3=2/3Cr(s)+1/2O2(1),

(1)+(2): 1/3 Cr2O3=2/3Cr(s)+[O]Fe (3),

ln[%O]= -2.464, [%O]=0.085


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7.4

  • 7.4.1

  • 7.4.2


7 4 1

7.4.1

O0 e

  • (7-9)

  • 7-10

  • O06-10

  • 7-11

  • 1/4


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(7-12)

1/4


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  • ti

  • (7-13)

  • ti1


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e=(e)Fue (7-14)

ue()7-117-14

e =KFue (7-15)

(7-15)

e=K"(7-16)


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Ke

i=nF(VO") ui

n=2 ui=i=Ki


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6-6Pe

7-6


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7-7


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e (Pe)=KePe-1/4=i

Ke=i/ Pe-1/4

6-15

e =i /Pe-1/4 (7-17)

h=i /Ph1/4 (7-18)

(7-17)(7-18)(6-13)

(7-19)


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7.2.2


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2.


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7-19

7-20

7-20


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7.3

1

2

3


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1


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SO2 SO3

AgOAgAg2SO4

Ag2SO4 = 2Ag + SO2 + O2

Ag2SO4 = 2Ag + SO3 + 1/2O2

Ag /Ag2SO4SO2/SO3Ag


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(+) Au | Pt, SO2, SO3, O2 | Li2SO4(x=0.77)-Ag2SO4 | (Ag2SO4)(), Ag | Au(-)

(-) Li2SO4 + 2Ag = 2Li+ + (Ag2SO4)+2e

(+) SO3 + 1/2O2 + 2Li+ +2e = Li2SO4

SO3 + 1/2O2 +2Ag = (Ag2SO4)


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(+)Mo | Mo + MoO2 | ZrO2(MgO) | ZrO2 +ZrSiO4 | [Si]Fe | Mo(-)

(ZrO2 + ZrSiO4)

2O2- + [Si] = (SiO2) ZrSiO4 + 4eMoO2 + 4e = Mo(s) + 2O2-

MoO2 + [Si] = (SiO2) ZrSiO4 + Mo(s)

ZrO2 + (SiO2)ZrSiO4 =ZrSiO4MoO2 + ZrO2 + [Si] = ZrSiO4 + Mo(s)


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7.5

1

ZrO2-CaOZrO2-MgOMo/MoO2Cr/Cr2O3

Mo|[O]Fe|ZrO2-CaO|Mo,MoO2|Mo (1)Mo|Cr,Cr2O3|ZrO2-CaO|[O]Fe|Mo (2)


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1

MoO2 = Mo + [O]

Mo + O2 = MoO2G0=-126700+34.18TO2=[O]FeG0=-56000-1.38Tlog[O]Fe=-(7725+10.08E)/T+3.885

24/3Cr+O2=2/3Cr2O3G0=-180360+40.90T

log[O]Fe=-(13580-10.08E)/T+4.62


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1AlNIr|Al,AlN|AlN|[N]Fe|Fe

[N] =1/2N21/2N2+2e=N2-

N2-=1/2N2+2e1/2N2+Al(l)=AlN

Al(l)+[N]=AlN G0=G0AlN-G0[N]=-78560+20.37TG=G0+RTln(1/fN[%N])=-nEFfN=1E=(mV)=67.3+126.9log[ppmN]1600Ir-Fe=-2mV

2.CaSCu,Cu2S|CaS-Y2O3|Fe,FeSCaS


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3.CaF2Ni,NiO,CaO|CaF2|CaO,Cu,Cu2O

F2+2e=2F-CaF2=Ca+F2Ca+1/2O2=CaOCu2O=2Cu+1/2O2Cu2O+CaF2+2e=CaO+2Cu+2F-

2F-=F2+2eF2+Ca=CaF2CaO=Ca+1/2O21/2O2+Ni=NiO2F-+CaO+Ni=NiO +CaF2+2e

Cu2O+Ni=NiO+2Cu1/2O2+CaF2=CaO+F2K=PF2/PO2

E = (RT/2F) ln (PF2II/PF2I)E=(RT/4F)ln(PO2II/PO2I)Ni,NiO|ZrO2-CaO|Cu,Cu2O


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CaSA,AxS,CaS|CaF2|CaSB,ByS

F2+2e=2F-CaF2=Ca+F2Ca+1/2S2=CaSByS=By+1/2S2CaF2+ByS+2e=yB+CaS+2F-

2F-=F2+2eF2+Ca=CaF2CaS=Ca+1/2S21/2S2+xA=AxSCaS+2F-+xA=AxS+CaF2+2e

ByS+xA=yB+AxS<1000


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CaF2

Au,Ag,Ag2S,CaS|CaF2|CaS,MnS,Mn|Au

F2+2e=2F-2F-+CaS=CaF2+1/2S2 (1), 1/2S2+Mn=MnS, F2+CaS+Mn+2e=CaF2+MnS

CaF2+1/2S2=CaS+2F- (2)2F-=F2+2e, Ag2S=2Ag+1/2S2, CaF2+Ag2S=2Ag+CaS+F2+2e (2)

Ag2S+Mn=MnS+2Ag(1)(2)PS2PF2


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Pt|Ni,NiO,CaO|CaF2|CaO,Cu,Cu2O|Pt

F2+2e=2F-, 2F-+CaO=CaF2+1/2O2, 1/2O2+Ni=NiO, F2+2e+CaO+Ni=NiO+CaF2 (1)

CaF2=Ca+2F-, 2F-=F2+2e, Ca+1/2O2+CaO, Cu2O=2Cu+1/2O2, CaF2+Cu2O=2Cu+CaO+F2+2e (2)

Cu2O+Ni=NiO+2Cu(1)(2)PO2PF2


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11

1)

Pt|Ma,MaO|ZrO2-CaO|Mx,MxO|Pt

MxO=Mx+1/2O21/2O2+2e=O2-

O2-=1/2O2+2e1/2O2+Ma=MaO

MxO+Ma=MaO+MxG=G0=G0MaO-G0MxO=-2EF G0MxO=G0MaO+2FE


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Pt|Ni,NiO| ZrO2-CaO|Cu,Cu2O|Pt

Cu2O+Ni=NiO+2Cu

G=G0=G0NiO-G0Cu2O= -2EF

G0Cu2O=G0NiO+2FE


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F=1=K+11


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Pt|Fe,TiO2,FeTiO3|ZrO2-CaO|Ni,NiO|Pt (a)

Pt|Fe,FeTiO3,Fe2TiO4|ZrO2-CaO|Ni,NiO|Pt (b)

a,

NiO=Ni+1/2O21/2O2+2e=O2-

O2-=1/2O2+2e1/2O2+Fe+TiO2=FeTiO3

NiO+Fe+TiO2=FeTiO3+Ni(a)G(a)=G0FeTiO3-G0NiO-G0TiO2=-2EF(a)

G0FeTiO3=G0NiO+G0TiO2-2FE(a)


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  • b

  • NiO=Ni+1/2O21/2O2+2e=O2-

  • O2-=1/2O2+2e1/2O2+Fe+FeTiO3=Fe2TiO4

  • NiO+Fe+FeTiO3=Fe2TiO4+Ni(b)

  • G(b)=G0Fe2TiO4-G0NiO-G0FeTiO3=-2EF(b)

  • G0Fe2TiO4=G0NiO+G0FeTiO3-2FE(b)


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2.

CaS


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1G0MnSPt|SO2(1atm),MnO,MnS|ZrO2-CaO|O2()|Pt

3/2O2()+6e=3O2-

3O2-+MnS=MnO+SO21atm+6e3/2O2()+MnS= MnO+SO2(1atm)G=G0+RTln(PSO2(1atm)/PO2()3/2)=-6EFG0MnS=G0MnO+G0SO2-(3/2)RTlnPO2()+6FE


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2G0NiSO4Pt|SO2(1atm),NiO,NiSO4|ZrO2-CaO|O2()|Pt

1/2O2()+2e=O2-

O2-+SO2+NiO=NiSO4+2e

1/2O2()+SO2(1atm)+NiO=NiSO4G=G0+RTln(1/PSO2(1atm)/PO2()1/2)=-2EF

G0NiSO4=G0NiO+G0SO2-(1/2)RTlnPO2()-2FE


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