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    Losses in Fuel Cells

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    Ljubodrag Samardzic
    This document discusses losses in fuel cells and fuel cell reaction kinetics. It provides equations for electrode kinetics, the Butler-Volmer equation, and exchange current density. Improving kinetic performance involves increasing reactant concentration, exchange current density, temperature, or the number of reaction sites. The simplified Butler-Volmer equation shows that at small overpotentials, current is directly proportional to exchange current density, while at large overpotentials the Tafel equation applies. Understanding catalyst behavior requires studying reactions like hydrogen and oxygen dissociation using density functional theory.

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    © All Rights Reserved
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    Losses in Fuel Cells

    Uploaded by

    Ljubodrag Samardzic
    28 views13 pages
    This document discusses losses in fuel cells and fuel cell reaction kinetics. It provides equations for electrode kinetics, the Butler-Volmer equation, and exchange current density. Improving kinetic performance involves increasing reactant concentration, exchange current density, temperature, or the number of reaction sites. The simplified Butler-Volmer equation shows that at small overpotentials, current is directly proportional to exchange current density, while at large overpotentials the Tafel equation applies. Understanding catalyst behavior requires studying reactions like hydrogen and oxygen dissociation using density functional theory.

    Original Description:

    Fuel cells lecture 3

    Original Title

    721

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    This document discusses losses in fuel cells and fuel cell reaction kinetics. It provides equations for electrode kinetics, the Butler-Volmer equation, and exchange current density. Improving kinetic performance involves increasing reactant concentration, exchange current density, temperature, or the number of reaction sites. The simplified Butler-Volmer equation shows that at small overpotentials, current is directly proportional to exchange current density, while at large overpotentials the Tafel equation applies. Understanding catalyst behavior requires studying reactions like hydrogen and oxygen dissociation using density functional theory.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    28 views13 pages

    Losses in Fuel Cells

    Uploaded by

    Ljubodrag Samardzic
    This document discusses losses in fuel cells and fuel cell reaction kinetics. It provides equations for electrode kinetics, the Butler-Volmer equation, and exchange current density. Improving kinetic performance involves increasing reactant concentration, exchange current density, temperature, or the number of reaction sites. The simplified Butler-Volmer equation shows that at small overpotentials, current is directly proportional to exchange current density, while at large overpotentials the Tafel equation applies. Understanding catalyst behavior requires studying reactions like hydrogen and oxygen dissociation using density functional theory.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    of 13

    Losses in Fuel Cells

    Fuel Cell Reaction Kinetics


    Electrode Kinetic

    Current = Charge/Time
    dQ nFdN
    i= =
    dt dt
    t
    ⇔ ∫ idt = Q = nFN
    0i
    j = [ A / cm 2 ] Heterogeneous
    H t process
    A
    H2 ⇔ 2H++2e-

    H2 + M → M ⋅⋅⋅ H2
    M ⋅ ⋅ ⋅ H 2 + M → 2( M ⋅ ⋅ ⋅ H )
    M ⋅ ⋅ ⋅ H → M + e− + H +
    Electrode Kinetic

    ⎛ −Δ
    ΔG
    G1 ⎞
    ⎜ ⎟
    Probability of P = Ke ⎝ RT ⎠
    act
    activation
    ⎛ − ΔG1 ⎞
    ⎜ ⎟
    F
    Forwardd
    v = KcR f1 Pact = KcR f1e
    * * ⎝ RT ⎠
    reaction rate 1
    ⎛ − ΔG2 ⎞
    Backward ⎜ ⎟
    reaction rate v2 = KcP f 2 Pact = KcP f 2 e
    * * ⎝ RT ⎠

    ⎛ − ΔG1 ⎞ ⎛ − ΔG2 ⎞
    ⎜ ⎟ ⎜ ⎟
    v = v1 − v2 = KcR* f1e ⎝ RT ⎠
    − KcP* f 2 e ⎝ RT ⎠

    Rate of reaction ⎛ − ΔG1 ⎞ ⎛ − ΔG1 − ΔGrxn ⎞


    ⎜ ⎟ ⎜ ⎟
    = KcR* f1e ⎝ RT ⎠
    − KcP* f 2 e ⎝ RT ⎠
    Equilibrium Potential: Galvani Potential
    Conversion to current density
    ⎛ − ΔG1 ⎞ ⎛ − ΔG1 − ΔGrxn ⎞
    ⎜ ⎟ ⎜ ⎟
    j = nFv = nFc f e *
    R 1
    ⎝ RT ⎠
    − nFc f 2 e*
    P
    ⎝ RT ⎠

    = j1 − j2

    At equilibrium
    j = j1 − j2 = 0
    j1 = j2 = j0 :E
    :Exchange
    h C
    Currentt D
    Density
    it
    ⎛ − ΔG1 ⎞ ⎛ − ΔG + + ⎞
    ⎜ +αnFΔφ ⎟ ⎜ ⎟
    ⎜ RT ⎟
    j1 = nFcR* f1e ⎝ RT ⎠
    = nFcR* fe ⎝ ⎠

    ⎛ − ΔG1 − ΔGrxn ⎞ ⎛ − ΔG + + ⎞
    ⎜ + nFΔφ ⎟ ⎜ ⎟
    ⎜ RT ⎟
    j2 = nFcP* f 2 e ⎝ RT ⎠
    = nFcP* fe ⎝ ⎠
    Bultler-Volmer Equation: Non-Equilibrium

    ⎛ αnFη ⎞
    ⎜ ⎟
    j1 = j0 e ⎝ RT ⎠

    ⎛ (1−α ) nFη ⎞
    −⎜ ⎟
    j 2 = j0 e ⎝ RT ⎠

    ⎛ ⎛⎜ αRT
    nFη ⎞
    ⎟ ⎟⎞
    ⎛ (1−α ) nFη ⎞
    −⎜
    j = j0 ⎜ e ⎝ ⎠
    −e ⎝ RT ⎠⎟
    ⎜ ⎟
    ⎝ ⎠
    ⎛ C ⎛⎜ αRT nFη ⎞
    ⎟ C ⎟⎞
    ⎛ (1−α ) nFη ⎞
    −⎜
    ⎜
    j = j0 0 e R ⎝ ⎠
    − 0e P ⎝ RT ⎠⎟
    ⎜ CR C ⎟
    ⎝ P ⎠

    Bulter-Volmer Equation
    Bultler-Volmer Equation: Non-Equilibrium
    ⎛ C ⎛⎜ αRT
    nFη ⎞
    ⎟ C − ⎜ ⎟⎞
    ⎛ (1−α ) nFη ⎞

    j = j0 ⎜ 0 e
    R ⎝ ⎠
    − 0e
    P ⎝ RT ⎠⎟
    ⎜ CR C ⎟
    ⎝ P ⎠
    Exchange Current Density Effect
    ⎛ C ⎛⎜ αRT
    nFη ⎞
    ⎟ C − ⎜ ⎟⎞
    ⎛ (1−α ) nFη ⎞

    j = j0 ⎜ 0 e ⎝
    R ⎠
    − 0e⎝
    P RT ⎠⎟
    ⎜ CR C ⎟
    ⎝ P ⎠
    Improving Kinetic

    ⎛ C ⎜⎛ αRT
    nFη ⎞
    ⎟ C ⎟⎞
    ⎛ (1−α ) nFη ⎞
    −⎜
    ⎜
    j = j0 0 e
    R ⎝ ⎠
    − 0e
    P ⎝ RT ⎠⎟
    ⎜ CR C ⎟
    ⎝ P ⎠
    1. CR: Increase
    1 I reactant concentration
    i
    2. Increase j0
    ⎛ − ΔG + + ⎞
    ⎜ ⎟
    ⎜ RT ⎟
    j0 = nFC * fe ⎝ ⎠

    • Decrease the activation energy (G++)


    • Increase T
    • Increase reaction site (equivalent to C*)
    Simplified B-V Equation
    1. When ηact is very small

    nFη act
    j = j0
    RT

    1. When ηact is large


    αnFη act
    RT RT
    j = j0 e RT
    or η act = − ln j0 + ln j
    αnF αnF
    = a + b log j
    Tafel Equation
    B-V Equation: Practical Consideration
    Hydrogen

    Oxygen

    Triple Phase Boundary


    Understanding Catalyst via DFT

    Hydrogen dissociation

    Oxygen dissociation
    O2 Dissociation & Incorporation

    by Prof. F. B. Prinz, Stanford University

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