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A nonstoichiometric structural model to characterize changes in the nickel hydroxide electrode during cycling

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Abstract

Experimental capacities and mass changes are recorded using an electrochemical quartz crystal microbalance during the first nine charge and discharge cycles of nickel hydroxide thin films cycled in 3.0 weight percent (wt%) potassium hydroxide electrolyte. For the first time, the film capacities have been corrected for the oxygen evolution side reaction, and the data used as input into a point defect-containing structural model to track the changes that occur during short-term cycling. Variations in capacity and mass during formation and charge/discharge cycling are related to changes in the point defect parameters, thus providing a structural origin for the unique experimental variations observed here and often reported in the literature, but previously unexplained. Proton-, potassium-, and water-content vary in the active material during charge/discharge cycling. The observed capacity loss, or “capacity fade,” is explained by incomplete incorporation of potassium ions in (or near) the nickel vacancy during charge, as additional protons are then allowed to occupy the vacant lattice site. The increase in water content during reduction parallels the expansion of the electrode that is well known during cycling. This result confirms the origin of the swelling phenomenon as being caused by water incorporation. The model and methodology developed in this paper can be used to correlate electrochemical signatures with material chemical structure.

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Notes

  1. These four end-member materials have the same crystal structure. This structure is different from those proposed for α-Ni (OH)2 and β-Ni (OH)2. Coefficients, 2s and 3s, have been added to the traditional β, α, and γ designations of the “phases” to more clearly differentiate the unique materials, yet retain the connection to the older literature designations and Eq. 1 . Also the β forms are unambiguously defined.

Abbreviations

E :

electrode potential, V

F :

Faraday’s constant, 96487 C/eq.

I :

applied current, A

i o,ox :

exchange current for the oxygen evolution reaction, A

i ox :

current expended for oxygen evolution, A

m :

mass of the film, g

M :

molecular weight of the film, g/mole Ni

n :

the average proton occupancy of a nickel vacancy

Ox :

oxidation state

Q :

capacity per unit mass of film, C/g

R :

universal gas constant, 8.314 J/mol K

T :

temperature, K

t :

time, s

U ref,ox :

standard potential of the oxygen evolution reaction, V

V Ni :

a vacant nickel lattice site

x :

moles of vacancies per mole of lattice sites

X w :

moles of water per mole of lattice sites

y :

moles of vacancies occupied by potassium ions per mole of lattice sites

z :

moles of exchangeable protons on interlamellar H+ sites (0≤z≤1)

αa :

anodic transfer coefficient

Δ:

change in variable

ε:

efficiency of the nickel reaction

λ1 :

moles of OH− ions per mole Ni

λ2 :

moles of K+ ions per mole Ni

λ3 :

moles of water per mole Ni

λ4 :

number of electrons per mole Ni

1:

discharged state, nickel hydroxide

2:

charged state, oxyhydroxide

0:

as-deposited film

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Acknowledgements

The authors gratefully acknowledge the financial support from the Office of Research and Development of the United States Central Intelligence Agency and the US Department of Energy under Cooperative Agreement No. DE-FCO2–91ER75666.

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Author notes

  1. Venkat Srinivasan

    Present address: Environmental Energy Technologies Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA

Authors and Affiliations

  1. Center for Electrochemical Engineering, Department of Chemical Engineering, University of South Carolina, Columbia, SC 29208, USA

    Venkat Srinivasan & John W. Weidner

  2. Department of Chemistry, Michigan Technological University, 1400 Townsend Drive, Houghton, MI 49931, USA

    Bahne C. Cornilsen

Authors
  1. Venkat Srinivasan
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  2. Bahne C. Cornilsen
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  3. John W. Weidner
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Correspondence to John W. Weidner.

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Srinivasan, V., Cornilsen, B.C. & Weidner, J.W. A nonstoichiometric structural model to characterize changes in the nickel hydroxide electrode during cycling. J Solid State Electrochem 9, 61–76 (2005). https://doi.org/10.1007/s10008-004-0525-x

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