Environmentally assisted cracking of cathodically polarized nickel in LiAlCl sub 4 /SOCl sub 2 electrolyte

Journal Article · Thu Aug 01 04:00:00 EDT 1991 · Journal of the Electrochemical Society; (United States)

DOI:https://doi.org/10.1149/1.2085955· OSTI ID:7165613

Scully, J R ^[1]; Cieslak, W R; Bovard, F S ^[2]

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1. Center for Electrochemical Sciences and Engineering, Univ. of Virginia, Charlottesville, VA (US)
2. Sandia National Lab., Albuquerque, NM (US)

In this paper, the susceptibility of nickel to environmentally assisted cracking is investigated at potentials that are relevant to primary Li/SOCl{sub 2} batteries which utilize a 1.5M LiAlCl{sub 4}/SOCl{sub 2} electrolyte. Slow strain rate tests are performed on Ni under conditions which simulate exposure of Ni grid supporting the Li anode, Ni grid supporting the cathode, and exposure to the vapor phase above a LiAlCl{sub 4}/SOCl{sub 2} electrolyte. A mixture of transgranular and intergranular cracking is observed only when polycrystalline Ni is galvanically coupled to Li or polarized to potentials equal to or below 0.0 V vs. a Li/LiCl reference electrode. Under both of these circumstances, zero valent Li is produced from the cathodic reduction of a LiCl film which forms on exposed Ni surfaces. A Li-induced embrittlement mechanism is proposed whereby LiCl is precipitated from solution at fresh crack tips, solid Li metal is formed from cathodic reduction of LiCl, Li promotes initiation of cracks at the Ni surface, and crack advance occurs at sufficiently high rates to preclude Li diffusion into the Ni ahead of the crack tip, implying a surface-induced cracking process.

• DOE Contract Number: AC04-76DP00789
• OSTI ID: 7165613
• Journal Information: Journal of the Electrochemical Society; (United States), Journal Name: Journal of the Electrochemical Society; (United States) Vol. 138:8; ISSN 0013-4651; ISSN JESOA
• Country of Publication: United States
• Language: English

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74 ATOMIC AND MOLECULAR PHYSICS
ALKALI METAL COMPOUNDS
ALKALI METALS
CHEMICAL REACTIONS
CHEMISTRY
CHLORIDES
CHLORINE COMPOUNDS
CORROSION
CRACKING
DECOMPOSITION
DIFFUSION
DIRECT ENERGY CONVERTERS
ELECTRIC BATTERIES
ELECTROCHEMICAL CELLS
ELECTROCHEMISTRY
ELECTROLYTES
ELEMENTS
ENVIRONMENTAL EFFECTS
FUEL CELLS
HALIDES
HALOGEN COMPOUNDS
INTERGRANULAR CORROSION
LITHIUM
LITHIUM CHLORIDES
LITHIUM COMPOUNDS
LITHIUM HALIDES
LITHIUM-CHLORINE BATTERIES
LITHIUM-SULFUR BATTERIES
METAL-GAS BATTERIES
METAL-NONMETAL BATTERIES
METALS
NICKEL
PYROLYSIS
REDOX POTENTIAL
SOLID ELECTROLYTE FUEL CELLS
THERMOCHEMICAL PROCESSES
TRANSITION ELEMENTS