Elektrosorpcja wodoru w cienkich Elektrosorpcja wodoru w cienkich warstwach palladu warstwach palladu

domieszkowanych azotemdomieszkowanych azotem

Pracownia ElektroanalizyPracownia Elektroanalizy Kierownik pracy: Dr Rafał JurczakowskiKierownik pracy: Dr Rafał Jurczakowski

Piotr PołczyńskiPiotr Połczyński

Jakie zastosowaniaJakie zastosowania znajduje badanie znajduje badanie procesprocesówów ads adsorpcjiorpcji i abs i absorpcjiorpcji wodoru w wodoru w

metalach?metalach?

Czujniki wodorowe

Otrzymywanie wodoru. Elektroliza

Ogniwa paliwowe

Korozja wodorowa

Silniki spalinowe

Magazyn wodoru

Fitf wodoru- oczyszczanie

PalladPallad Należy do platynowców lekkichNależy do platynowców lekkich

WŁAŚCIWOŚCI FIZYKOCHEMICZNEWŁAŚCIWOŚCI FIZYKOCHEMICZNE• Liczba atomowa 46Liczba atomowa 46• masa atomowa 106,42 masa atomowa 106,42 • Temperatura topnienia 1554,9 °CTemperatura topnienia 1554,9 °C• gęstość 12,0 g/cm3gęstość 12,0 g/cm3• Niska zawartość w środowisku około 10-4 ppmNiska zawartość w środowisku około 10-4 ppm• Cena palladu za uncje 456,25$ Notowanie z 28.05.2010Cena palladu za uncje 456,25$ Notowanie z 28.05.2010• Struktura krystalograficzna fccStruktura krystalograficzna fcc

Czysty pochłania 850 objętości wodoru na jedną Czysty pochłania 850 objętości wodoru na jedną objętość palladu [H]/[Pd]~0.7objętość palladu [H]/[Pd]~0.7

Najlepiej przebadany z różnych układów Najlepiej przebadany z różnych układów absorbujących wodórabsorbujących wodór

Faza Faza αα i i ββ ALFA: Zawiera mało ALFA: Zawiera mało

wodoru, roztwór.wodoru, roztwór.

BETA: Zawiera BETA: Zawiera znacznie więcej znacznie więcej zaabsorbowanego zaabsorbowanego wodoru, struktura wodoru, struktura wodorku, zmiana wodorku, zmiana stałej sieciowej.stałej sieciowej.

Obie fazy mogą Obie fazy mogą współistniećwspółistnieć

B. Baranowski et al. J. Chem. Soc. Faraday Trans. I, 62 (1972) 824

Struktura pasma przewodnictwaStruktura pasma przewodnictwa Zamiana stałej sieciowej wpływa na Zamiana stałej sieciowej wpływa na

na szerokość pasma przewodnictwa. na szerokość pasma przewodnictwa.

Ludwig A. Kibler, et al. Angew. Chem. Int. Ed. 2005, 44

Ludwig A. Kibler, et al. Angew. Chem. Int. Ed. 2005, 44

Energia adsorbcji wodoru zależy liniowo Energia adsorbcji wodoru zależy liniowo położenia środka pasma przewodnictwapołożenia środka pasma przewodnictwa

Elektroosadzanie PdElektroosadzanie Pd

Na złotej elektrodzie Na złotej elektrodzie Z Roztworu chlorku PalladuZ Roztworu chlorku Palladu

Praca doktorska Pierre-Philippe GRAND, UNIVERSITÉ

PIERRE ET MARIE CURIE (PARIS VI),

Praca magisterska A. Januszewskiej

Cienkie warstwy Cienkie warstwy

Domieszkowanie azotemDomieszkowanie azotem

atomy palladu

warstwa

Pd-N

implantowane jony

Metody badania sorpcji Metody badania sorpcji wodoruwodoru

Volumetryczne Volumetryczne Aparatem Novela SievertaAparatem Novela Sieverta

Elektochemicznie

2H2

1eH

21

2

lnHp

H

F

RTE

)abs(HMeHM

Mechanizmy Elektrosorpcji wodoruMechanizmy Elektrosorpcji wodoru

Absorpcja bezpośrednia Absorpcja bezpośrednia

HH++ + Me + e + Me + e-- Me-H (ads.) Volmer Me-H (ads.) Volmer

HH++ + Me + e + Me + e-- Me-H (abs.) Me-H (abs.)

Absorpcja pośredniaAbsorpcja pośrednia

HH++ + Me + e + Me + e-- Me-H (ads.) Me-H (ads.)

Me- H (ads.)Me- H (ads.)Me- H (abs.)Me- H (abs.)

Wydzielanie wodoru Wydzielanie wodoru

HH++ + Me-H (ads.) + e + Me-H (ads.) + e-- Me+H Me+H2 2 HeyrovskiHeyrovski

Me-H (ads.) + Me-H (ads.) Me-H (ads.) + Me-H (ads.) Me+H Me+H22 Tafel Tafel

Pomiar impedancji

ac

ac

Impedancja

Z=Zre+i*Zim

Impedancja

Rp

Nachylenie krzywej E-I odpowiada oporowi:

Rp (ω →0)

R1 CPE1

Element Freedom Value Error Error %R1 Free(+) 9,536 N/A N/ACPE1-T Free(+) 0,00013011 N/A N/ACPE1-P Free(+) 0,90183 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\linia.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

Rs CPEdlR1 CPE1

Element Freedom Value Error Error %R1 Free(+) 9,536 N/A N/ACPE1-T Free(+) 0,00013011 N/A N/ACPE1-P Free(+) 0,90183 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\linia.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

Rs CPEdl

R1 CPE1

R2

Element Freedom Value Error Error %R1 Free(+) 9,866 N/A N/ACPE1-T Free(+) 0,12184 N/A N/ACPE1-P Free(+) 0,86934 N/A N/AR2 Free(+) 35,27 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\1_pó³kole.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

CPEdl

Rct

RsR1 CPE1

R2

Element Freedom Value Error Error %R1 Free(+) 9,866 N/A N/ACPE1-T Free(+) 0,12184 N/A N/ACPE1-P Free(+) 0,86934 N/A N/AR2 Free(+) 35,27 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\1_pó³kole.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

CPEdl

Rct

Rs

R1 CPE1

R2 CPE2

Element Freedom Value Error Error %R1 Free(+) 9,065 N/A N/ACPE1-T Free(+) 0,00031678 N/A N/A

CPE1-P Free(+) 0,77337 N/A N/AR2 Free(+) 4,437 N/A N/ACPE2-T Free(+) 0,0020827 N/A N/ACPE2-P Free(+) 0,96429 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\1_pó³kole+linia.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100

Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

Rs CPEdl

Rct CPEH-UPD

R1 CPE1

R2 CPE2

Element Freedom Value Error Error %R1 Free(+) 9,065 N/A N/ACPE1-T Free(+) 0,00031678 N/A N/A

CPE1-P Free(+) 0,77337 N/A N/AR2 Free(+) 4,437 N/A N/ACPE2-T Free(+) 0,0020827 N/A N/ACPE2-P Free(+) 0,96429 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\1_pó³kole+linia.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100

Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

Rs CPEdl

Rct CPEH-UPD

R1 CPE1

R2 CPE2

R3

Element Freedom Value Error Error %R1 Free(+) 8,334 N/A N/ACPE1-T Free(+) 0,00011692 N/A N/ACPE1-P Free(+) 0,85318 N/A N/AR2 Free(+) 6,188 N/A N/ACPE2-T Free(+) 0,087259 N/A N/ACPE2-P Free(+) 0,53929 N/A N/AR3 Free(+) 11,93 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\2_pó³kola.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

RsCPEdl

Rct CPE H-UPD

Rct HER

R1 CPE1

R2 CPE2

R3

Element Freedom Value Error Error %R1 Free(+) 8,334 N/A N/ACPE1-T Free(+) 0,00011692 N/A N/ACPE1-P Free(+) 0,85318 N/A N/AR2 Free(+) 6,188 N/A N/ACPE2-T Free(+) 0,087259 N/A N/ACPE2-P Free(+) 0,53929 N/A N/AR3 Free(+) 11,93 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\2_pó³kola.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

RsCPEdl

Rct CPE H-UPD

Rct HER

-Z’

Z’Rs

R1 CPE1

R2 W1

Element Freedom Value Error Error %R1 Free(+) 18,89 N/A N/ACPE1-T Free(+) 4,6262E-05 N/A N/ACPE1-P Free(+) 0,87858 N/A N/AR2 Free(+) 82,72 N/A N/AW1-R Free(+) 261,3 N/A N/AW1-T Free(+) 1,117 N/A N/AW1-P Free(+) 0,45831 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\warburg.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

CPEdl

Rct Zw

RsR1 CPE1

R2 W1

Element Freedom Value Error Error %R1 Free(+) 18,89 N/A N/ACPE1-T Free(+) 4,6262E-05 N/A N/ACPE1-P Free(+) 0,87858 N/A N/AR2 Free(+) 82,72 N/A N/AW1-R Free(+) 261,3 N/A N/AW1-T Free(+) 1,117 N/A N/AW1-P Free(+) 0,45831 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\warburg.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

CPEdl

Rct Zw

Rs

Elektrochemiczna spektroskopia impedancyjna - obwody zastępcze

R1 CPE1

Element Freedom Value Error Error %R1 Free(+) 9,536 N/A N/ACPE1-T Free(+) 0,00013011 N/A N/ACPE1-P Free(+) 0,90183 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\linia.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

Rs CPEdlR1 CPE1

Element Freedom Value Error Error %R1 Free(+) 9,536 N/A N/ACPE1-T Free(+) 0,00013011 N/A N/ACPE1-P Free(+) 0,90183 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\linia.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

Rs CPEdl

R1 CPE1

R2

Element Freedom Value Error Error %R1 Free(+) 9,866 N/A N/ACPE1-T Free(+) 0,12184 N/A N/ACPE1-P Free(+) 0,86934 N/A N/AR2 Free(+) 35,27 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\1_pó³kole.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

CPEdl

Rct

RsR1 CPE1

R2

Element Freedom Value Error Error %R1 Free(+) 9,866 N/A N/ACPE1-T Free(+) 0,12184 N/A N/ACPE1-P Free(+) 0,86934 N/A N/AR2 Free(+) 35,27 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\1_pó³kole.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

CPEdl

Rct

Rs

R1 CPE1

R2 CPE2

Element Freedom Value Error Error %R1 Free(+) 9,065 N/A N/ACPE1-T Free(+) 0,00031678 N/A N/A

CPE1-P Free(+) 0,77337 N/A N/AR2 Free(+) 4,437 N/A N/ACPE2-T Free(+) 0,0020827 N/A N/ACPE2-P Free(+) 0,96429 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\1_pó³kole+linia.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100

Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

Rs CPEdl

Rct CPEH-UPD

R1 CPE1

R2 CPE2

Element Freedom Value Error Error %R1 Free(+) 9,065 N/A N/ACPE1-T Free(+) 0,00031678 N/A N/A

CPE1-P Free(+) 0,77337 N/A N/AR2 Free(+) 4,437 N/A N/ACPE2-T Free(+) 0,0020827 N/A N/ACPE2-P Free(+) 0,96429 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\1_pó³kole+linia.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100

Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

Rs CPEdl

Rct CPEH-UPD

R1 CPE1

R2 CPE2

R3

Element Freedom Value Error Error %R1 Free(+) 8,334 N/A N/ACPE1-T Free(+) 0,00011692 N/A N/ACPE1-P Free(+) 0,85318 N/A N/AR2 Free(+) 6,188 N/A N/ACPE2-T Free(+) 0,087259 N/A N/ACPE2-P Free(+) 0,53929 N/A N/AR3 Free(+) 11,93 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\2_pó³kola.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

RsCPEdl

Rct CPE H-UPD

Rct HER

R1 CPE1

R2 CPE2

R3

Element Freedom Value Error Error %R1 Free(+) 8,334 N/A N/ACPE1-T Free(+) 0,00011692 N/A N/ACPE1-P Free(+) 0,85318 N/A N/AR2 Free(+) 6,188 N/A N/ACPE2-T Free(+) 0,087259 N/A N/ACPE2-P Free(+) 0,53929 N/A N/AR3 Free(+) 11,93 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\2_pó³kola.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

RsCPEdl

Rct CPE H-UPD

Rct HER

-Z’

Z’Rs Rct

R1 CPE1

R2 W1

Element Freedom Value Error Error %R1 Free(+) 18,89 N/A N/ACPE1-T Free(+) 4,6262E-05 N/A N/ACPE1-P Free(+) 0,87858 N/A N/AR2 Free(+) 82,72 N/A N/AW1-R Free(+) 261,3 N/A N/AW1-T Free(+) 1,117 N/A N/AW1-P Free(+) 0,45831 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\warburg.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

CPEdl

Rct Zw

RsR1 CPE1

R2 W1

Element Freedom Value Error Error %R1 Free(+) 18,89 N/A N/ACPE1-T Free(+) 4,6262E-05 N/A N/ACPE1-P Free(+) 0,87858 N/A N/AR2 Free(+) 82,72 N/A N/AW1-R Free(+) 261,3 N/A N/AW1-T Free(+) 1,117 N/A N/AW1-P Free(+) 0,45831 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\warburg.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

CPEdl

Rct Zw

Rs

Stosowane obwody zastępcze

R1 CPE1

Element Freedom Value Error Error %R1 Free(+) 9,536 N/A N/ACPE1-T Free(+) 0,00013011 N/A N/ACPE1-P Free(+) 0,90183 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\linia.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

Rs CPEdlR1 CPE1

Element Freedom Value Error Error %R1 Free(+) 9,536 N/A N/ACPE1-T Free(+) 0,00013011 N/A N/ACPE1-P Free(+) 0,90183 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\linia.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

Rs CPEdl

R1 CPE1

R2

Element Freedom Value Error Error %R1 Free(+) 9,866 N/A N/ACPE1-T Free(+) 0,12184 N/A N/ACPE1-P Free(+) 0,86934 N/A N/AR2 Free(+) 35,27 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\1_pó³kole.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

CPEdl

Rct

RsR1 CPE1

R2

Element Freedom Value Error Error %R1 Free(+) 9,866 N/A N/ACPE1-T Free(+) 0,12184 N/A N/ACPE1-P Free(+) 0,86934 N/A N/AR2 Free(+) 35,27 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\1_pó³kole.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

CPEdl

Rct

Rs

R1 CPE1

R2 CPE2

Element Freedom Value Error Error %R1 Free(+) 9,065 N/A N/ACPE1-T Free(+) 0,00031678 N/A N/A

CPE1-P Free(+) 0,77337 N/A N/AR2 Free(+) 4,437 N/A N/ACPE2-T Free(+) 0,0020827 N/A N/ACPE2-P Free(+) 0,96429 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\1_pó³kole+linia.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100

Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

Rs CPEdl

Rct CPEH-UPD

R1 CPE1

R2 CPE2

Element Freedom Value Error Error %R1 Free(+) 9,065 N/A N/ACPE1-T Free(+) 0,00031678 N/A N/A

CPE1-P Free(+) 0,77337 N/A N/AR2 Free(+) 4,437 N/A N/ACPE2-T Free(+) 0,0020827 N/A N/ACPE2-P Free(+) 0,96429 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\1_pó³kole+linia.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100

Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

Rs CPEdl

Rct CPEH-UPD

R1 CPE1

R2 CPE2

R3

Element Freedom Value Error Error %R1 Free(+) 8,334 N/A N/ACPE1-T Free(+) 0,00011692 N/A N/ACPE1-P Free(+) 0,85318 N/A N/AR2 Free(+) 6,188 N/A N/ACPE2-T Free(+) 0,087259 N/A N/ACPE2-P Free(+) 0,53929 N/A N/AR3 Free(+) 11,93 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\2_pó³kola.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

RsCPEdl

Rct CPE H-UPD

Rct HER

R1 CPE1

R2 CPE2

R3

Element Freedom Value Error Error %R1 Free(+) 8,334 N/A N/ACPE1-T Free(+) 0,00011692 N/A N/ACPE1-P Free(+) 0,85318 N/A N/AR2 Free(+) 6,188 N/A N/ACPE2-T Free(+) 0,087259 N/A N/ACPE2-P Free(+) 0,53929 N/A N/AR3 Free(+) 11,93 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\2_pó³kola.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

RsCPEdl

Rct CPE H-UPD

Rct HER

-Z’

Z’Rs Rct

R1 CPE1

R2 W1

Element Freedom Value Error Error %R1 Free(+) 18,89 N/A N/ACPE1-T Free(+) 4,6262E-05 N/A N/ACPE1-P Free(+) 0,87858 N/A N/AR2 Free(+) 82,72 N/A N/AW1-R Free(+) 261,3 N/A N/AW1-T Free(+) 1,117 N/A N/AW1-P Free(+) 0,45831 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\warburg.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

CPEdl

Rct Zw

RsR1 CPE1

R2 W1

Element Freedom Value Error Error %R1 Free(+) 18,89 N/A N/ACPE1-T Free(+) 4,6262E-05 N/A N/ACPE1-P Free(+) 0,87858 N/A N/AR2 Free(+) 82,72 N/A N/AW1-R Free(+) 261,3 N/A N/AW1-T Free(+) 1,117 N/A N/AW1-P Free(+) 0,45831 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\warburg.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

CPEdl

Rct Zw

Rs

Stosowane obwody zastępcze

R1 CPE1

Element Freedom Value Error Error %R1 Free(+) 9,536 N/A N/ACPE1-T Free(+) 0,00013011 N/A N/ACPE1-P Free(+) 0,90183 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\linia.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

Rs CPEdlR1 CPE1

Element Freedom Value Error Error %R1 Free(+) 9,536 N/A N/ACPE1-T Free(+) 0,00013011 N/A N/ACPE1-P Free(+) 0,90183 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\linia.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

Rs CPEdl

R1 CPE1

R2

Element Freedom Value Error Error %R1 Free(+) 9,866 N/A N/ACPE1-T Free(+) 0,12184 N/A N/ACPE1-P Free(+) 0,86934 N/A N/AR2 Free(+) 35,27 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\1_pó³kole.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

CPEdl

Rct

RsR1 CPE1

R2

Element Freedom Value Error Error %R1 Free(+) 9,866 N/A N/ACPE1-T Free(+) 0,12184 N/A N/ACPE1-P Free(+) 0,86934 N/A N/AR2 Free(+) 35,27 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\1_pó³kole.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

CPEdl

Rct

Rs

R1 CPE1

R2 CPE2

Element Freedom Value Error Error %R1 Free(+) 9,065 N/A N/ACPE1-T Free(+) 0,00031678 N/A N/A

CPE1-P Free(+) 0,77337 N/A N/AR2 Free(+) 4,437 N/A N/ACPE2-T Free(+) 0,0020827 N/A N/ACPE2-P Free(+) 0,96429 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\1_pó³kole+linia.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100

Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

Rs CPEdl

Rct CPEH-UPD

R1 CPE1

R2 CPE2

Element Freedom Value Error Error %R1 Free(+) 9,065 N/A N/ACPE1-T Free(+) 0,00031678 N/A N/A

CPE1-P Free(+) 0,77337 N/A N/AR2 Free(+) 4,437 N/A N/ACPE2-T Free(+) 0,0020827 N/A N/ACPE2-P Free(+) 0,96429 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\1_pó³kole+linia.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100

Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

Rs CPEdl

Rct CPEH-UPD

R1 CPE1

R2 CPE2

R3

Element Freedom Value Error Error %R1 Free(+) 8,334 N/A N/ACPE1-T Free(+) 0,00011692 N/A N/ACPE1-P Free(+) 0,85318 N/A N/AR2 Free(+) 6,188 N/A N/ACPE2-T Free(+) 0,087259 N/A N/ACPE2-P Free(+) 0,53929 N/A N/AR3 Free(+) 11,93 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\2_pó³kola.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

RsCPEdl

Rct CPE H-UPD

Rct HER

R1 CPE1

R2 CPE2

R3

Element Freedom Value Error Error %R1 Free(+) 8,334 N/A N/ACPE1-T Free(+) 0,00011692 N/A N/ACPE1-P Free(+) 0,85318 N/A N/AR2 Free(+) 6,188 N/A N/ACPE2-T Free(+) 0,087259 N/A N/ACPE2-P Free(+) 0,53929 N/A N/AR3 Free(+) 11,93 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\2_pó³kola.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

RsCPEdl

Rct CPE H-UPD

Rct HER

-Z’

Z’Rs Rct

R1 CPE1

R2 W1

Element Freedom Value Error Error %R1 Free(+) 18,89 N/A N/ACPE1-T Free(+) 4,6262E-05 N/A N/ACPE1-P Free(+) 0,87858 N/A N/AR2 Free(+) 82,72 N/A N/AW1-R Free(+) 261,3 N/A N/AW1-T Free(+) 1,117 N/A N/AW1-P Free(+) 0,45831 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\warburg.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

CPEdl

Rct Zw

RsR1 CPE1

R2 W1

Element Freedom Value Error Error %R1 Free(+) 18,89 N/A N/ACPE1-T Free(+) 4,6262E-05 N/A N/ACPE1-P Free(+) 0,87858 N/A N/AR2 Free(+) 82,72 N/A N/AW1-R Free(+) 261,3 N/A N/AW1-T Free(+) 1,117 N/A N/AW1-P Free(+) 0,45831 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\warburg.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

CPEdl

Rct Zw

Rs

Stosowane obwody zastępcze

R1 CPE1

Element Freedom Value Error Error %R1 Free(+) 9,536 N/A N/ACPE1-T Free(+) 0,00013011 N/A N/ACPE1-P Free(+) 0,90183 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\linia.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

Rs CPEdlR1 CPE1

Element Freedom Value Error Error %R1 Free(+) 9,536 N/A N/ACPE1-T Free(+) 0,00013011 N/A N/ACPE1-P Free(+) 0,90183 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\linia.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

Rs CPEdl

R1 CPE1

R2

Element Freedom Value Error Error %R1 Free(+) 9,866 N/A N/ACPE1-T Free(+) 0,12184 N/A N/ACPE1-P Free(+) 0,86934 N/A N/AR2 Free(+) 35,27 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\1_pó³kole.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

CPEdl

Rct

RsR1 CPE1

R2

Element Freedom Value Error Error %R1 Free(+) 9,866 N/A N/ACPE1-T Free(+) 0,12184 N/A N/ACPE1-P Free(+) 0,86934 N/A N/AR2 Free(+) 35,27 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\1_pó³kole.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

CPEdl

Rct

Rs

R1 CPE1

R2 CPE2

Element Freedom Value Error Error %R1 Free(+) 9,065 N/A N/ACPE1-T Free(+) 0,00031678 N/A N/A

CPE1-P Free(+) 0,77337 N/A N/AR2 Free(+) 4,437 N/A N/ACPE2-T Free(+) 0,0020827 N/A N/ACPE2-P Free(+) 0,96429 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\1_pó³kole+linia.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100

Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

Rs CPEdl

Rct CPEH-UPD

R1 CPE1

R2 CPE2

Element Freedom Value Error Error %R1 Free(+) 9,065 N/A N/ACPE1-T Free(+) 0,00031678 N/A N/A

CPE1-P Free(+) 0,77337 N/A N/AR2 Free(+) 4,437 N/A N/ACPE2-T Free(+) 0,0020827 N/A N/ACPE2-P Free(+) 0,96429 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\1_pó³kole+linia.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100

Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

Rs CPEdl

Rct CPEH-UPD

R1 CPE1

R2 CPE2

R3

Element Freedom Value Error Error %R1 Free(+) 8,334 N/A N/ACPE1-T Free(+) 0,00011692 N/A N/ACPE1-P Free(+) 0,85318 N/A N/AR2 Free(+) 6,188 N/A N/ACPE2-T Free(+) 0,087259 N/A N/ACPE2-P Free(+) 0,53929 N/A N/AR3 Free(+) 11,93 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\2_pó³kola.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

RsCPEdl

Rct CPE H-UPD

Rct HER

R1 CPE1

R2 CPE2

R3

Element Freedom Value Error Error %R1 Free(+) 8,334 N/A N/ACPE1-T Free(+) 0,00011692 N/A N/ACPE1-P Free(+) 0,85318 N/A N/AR2 Free(+) 6,188 N/A N/ACPE2-T Free(+) 0,087259 N/A N/ACPE2-P Free(+) 0,53929 N/A N/AR3 Free(+) 11,93 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\2_pó³kola.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

RsCPEdl

Rct CPE H-UPD

Rct HER

-Z’

Z’Rs Rct

Stosowane obwody zastępcze

R1 CPE1

R2 W1

Element Freedom Value Error Error %R1 Free(+) 18,89 N/A N/ACPE1-T Free(+) 4,6262E-05 N/A N/ACPE1-P Free(+) 0,87858 N/A N/AR2 Free(+) 82,72 N/A N/AW1-R Free(+) 261,3 N/A N/AW1-T Free(+) 1,117 N/A N/AW1-P Free(+) 0,45831 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\warburg.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

CPEdl

Rct Zw

RsR1 CPE1

R2 W1

Element Freedom Value Error Error %R1 Free(+) 18,89 N/A N/ACPE1-T Free(+) 4,6262E-05 N/A N/ACPE1-P Free(+) 0,87858 N/A N/AR2 Free(+) 82,72 N/A N/AW1-R Free(+) 261,3 N/A N/AW1-T Free(+) 1,117 N/A N/AW1-P Free(+) 0,45831 N/A N/A

Data File:Circuit Model File: E:\Maciek\!PROGRAMY\warburg.mdlMode: Run Fitting / Selected Points (0 - 0)Maximum Iterations: 100Optimization Iterations: 0Type of Fitting: ComplexType of Weighting: Calc-Modulus

CPEdl

Rct Zw

Rs

Układy zastępcze

Prosty

Złożony

R1- opór elektrolitu CPE1- Pojemność

warstwy podwójnej R2- opór przeniesienia

ładunku CPE2- Pojemność

pochłoniętego wodoru R3- opór wydzielania

gazowego wodoru

Cele pracyCele pracy

Badanie sorpcji wodoru w cienkich Badanie sorpcji wodoru w cienkich warstwach stopów Pd-N.warstwach stopów Pd-N.

Wpływ składu stopu na ilość Wpływ składu stopu na ilość zaabsorbowanego wodoru (izotermy zaabsorbowanego wodoru (izotermy adsorbcji).adsorbcji).

Wpływ składu stopu na kinetykę reakcji Wpływ składu stopu na kinetykę reakcji elektrosorpcji wodoru.elektrosorpcji wodoru.

Odróżnienie wodoru adsorbowanego i Odróżnienie wodoru adsorbowanego i absorbowanego na badanych stopach.absorbowanego na badanych stopach.

Próba korelacji paramentów Próba korelacji paramentów termodynamicznych z właściwościami termodynamicznych z właściwościami elektronowymi dla Pd-N-H elektronowymi dla Pd-N-H

Wstępne wyniki badańWstępne wyniki badań

-0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4

-200

-150

-100

-50

0

50

100

150

I /

A

E / V

Dziekuje za uwageDziekuje za uwage