New battery materials. Progress report, April 1,--September 30, 1977. [Far high-temperature Li cells]

Technical Report · Wed Mar 01 00:00:00 EST 1978

DOI:https://doi.org/10.2172/5073916· OSTI ID:5073916

Huggins, R. A.

Lithium ion conductivities of solid solutions formed between Li/sub 4/SiO/sub 4/ and Li/sub 5/AlO/sub 4/ were measured. The conductivity of Li/sub 4/./sub 5/Al./sub 5/Si./sub 5/O/sub 4/ is comparable to the best previously known lithium ion conductors. The structural type is that of Li/sub 4/SiO/sub 4/, and x-ray lattice parameters were determined across the range of solid solution. No solid solutions were found which had the Li/sub 5/AlO/sub 4/ (antiflourite) structure. Thermodynamic calculations based on available and estimated data suggest that lithium silicate is unstable with respect to attack by molten lithium at 700 K, and that Li/sub 5/AlO/sub 4/ may also be marginally unstable. Experimentally, the materials appear to have quite good stability at lower temperatures (300/sup 0/C), but both Li/sub 5/AlO/sub 4/ and Li/sub 4/./sub 4/Al./sub 4/Si./sub 6/O/sub 4/ were attacked at 720K within a period of a few hours. The intermetallic systems Li--Sb and Li--Bi and the oxide systems Li--Li/sub 2/Ti/sub 3/O/sub 7/ were studied as possible positive electrode systems for lithium batteries. Large lithium chemical diffusion coefficients were found in all 3 systems. Associated kinetic data (particle diffusion coefficients, partial conductivities, etc.) were calculated, and thermodynamic data (emf versus composition) were obtained. Beta LiAl was studied in considerable detail by coulometric titration and potentiostatic and galvaostatic transient techniques. Its range of existence was found to extend from 47 atom % to 55 atom % of lithium, between the voltages 300 to 70 mV with respect to pure lithium. Chemical diffusion coefficients in this phase are very large, lying between 2 x 10/sup -6/ cm/sup 2//s at the lithium-rich end and 10/sup -4/ cm/sup 2//s at the lithium-deficit end of its range of existence. 3 figures.

• Research Organization: Stanford Univ., Calif. (USA)
• DOE Contract Number: EC-77-S-02-4506
• OSTI ID: 5073916
• Report Number(s): COO-4506-1
• Country of Publication: United States
• Language: English

Related Subjects

25 ENERGY STORAGE
36 MATERIALS SCIENCE
ALUMINATES
IONIC CONDUCTIVITY
LITHIUM COMPOUNDS
METAL-METAL BATTERIES
ELECTRODES
ELECTROLYTES
METAL-NONMETAL BATTERIES
SILICATES
ALUMINIUM ALLOYS
ANTIMONY ALLOYS
BATTERY SEPARATORS
BISMUTH ALLOYS
DIFFUSION
HIGH TEMPERATURE
INTERMETALLIC COMPOUNDS
LITHIUM
LITHIUM ALLOYS
MATERIALS
SOLID SOLUTIONS
STABILITY
TITANATES
ALKALI METAL COMPOUNDS
ALKALI METALS
ALLOYS
ALUMINIUM COMPOUNDS
DISPERSIONS
ELECTRIC BATTERIES
ELECTRIC CONDUCTIVITY
ELECTRICAL PROPERTIES
ELECTROCHEMICAL CELLS
ELEMENTS
ENERGY STORAGE SYSTEMS
METALS
MIXTURES
OXYGEN COMPOUNDS
PHYSICAL PROPERTIES
PNICTIDES
SILICON COMPOUNDS
SOLUTIONS
TITANIUM COMPOUNDS
TRANSITION ELEMENT COMPOUNDS
250903* - Energy Storage- Batteries- Materials
Components
& Auxiliaries
360603 - Materials- Properties