Electrolyte compositions

• US 3,976,509 A
• Filed: 04/04/1975
• Issued: 08/24/1976
• Est. Priority Date: 04/04/1975
• Status: Expired due to Term

• Current Assignee: Lockheed Missiles and Space Co Inc (Martin Marietta Corporation)
• Original Assignee: Lockheed Missiles and Space Co Inc (Martin Marietta Corporation)
• Inventors: Tsai, Keh Chi, Littauer, Ernest L.
• Primary Examiner(s): Walton, Donald L.
• Application Number:
  US05/564,984
• Time in Patent Office: 508 Days
• Field of Search: 136/6 F, 136/83 R, 136/154, 136/155, 252/62.2
• US Class Current: 429/341
• CPC Class Codes: H01M 6/26 Cells without oxidising active material, e.g. Volta cells

Abstract

In a reactive metal-water electrochemical cell, an alkaline electrolyte containing organic additives which reduce the parasitic direct corrosion reaction between the reactive metal and the water of the electrolyte. More particularly, the additives substantially reduce the activity of the water by forming inter-molecular hydrogen bonding between the organic additive and water. Illustratively, such organic additives include alcohols, nitrogen containing compounds such as amides, amines and hydrazine, and ketones, ethers and esters. Optionally, molarity of the electrolyte is controlled independent of water additions by chemically removing the reactive metal ions formed during discharge of the cell. This is accomplished by the controlled additions of precipitating agents to the electrolyte to form insoluble salts.

Claims

1. An electrochemical cell consisting essentially of a reactive metal anode highly reactive with water and spaced from a cathode by an electrically insulating film formed on said anode in the presence of water, an aqueous alkaline electrolyte in which said anode and cathode are immersed, said electrolyte permitting, at the anode, electrochemical dissolution of reactive metal to aqueous reactive metal ions, formation of an aqueous salt to a solid salt in the form of a porous film on the anode and, at the cathode, reduction of water, and an organic solvent in said electrolyte which reduces direct corrosion/parasitic reaction at said anode by hydrogen bonding with the water in said electrolyte while having only a minor inhibiting influence on said anode-cathode reactions, said organic solvent being at least one alcohol selected from the group of alcohols consisting of methyl alcohol, ethylene glycol, glycerol, ethyl alcohol, allyl alcohol and propyl alcohol.

2. An electrochemical cell in accordance with claim 1, wherein said alcohol is methanol present in an amount of from about 10 to about 40 volume percent.

3. An electrochemical cell in accordance with claim 1, wherein said electrolyte is an alkali metal hydroxide containing methanol.

4. An electrochemical cell consisting essentially of a reactive metal anode highly reactive with water and spaced from a cathode by an electrically insulating film formed on said anode in the presence of water, an aqueous alkaline electrolyte in which said anode and cathode are immersed, said electrolyte permitting, at the anode, electrochemical dissolution of reactive metal to aqueous reactive metal ions, formation of an aqueous salt to a solid salt in the form of a porous film on the anode and, at the cathode, reduction of water, and an organic solvent in said electrolyte which reduces direct corrosion/parasitic reaction at said anode by hydrogen bonding with the water in said electrolyte while having only a minor inhibiting influence on said anode-cathode reactions, said organic solvent being at least one amine selected from the group of amines consisting of ethyl amine, propyl amine, hydroxyl amine, ethylene diamine, diethylemetriamine, pyridine, aniline and dimethyl amine.

5. An electrochemical cell consisting essentially of a reactive metal anode highly reactive with water and spaced from a cathode by an electrically insulating film formed on said anode in the presence of water, an aqueous alkaline electrolyte in which said anode and cathode are immersed, said electrolyte permitting, at the anode, electrochemical dissolution of reactive metal to aqueous reactive metal ions, formation of an aqueous salt to a solid salt in the form of a porous film on the anode and, at the cathode, reduction of water, and an organic solvent in said electrolyte which reduces direct corrosion/parasitic reaction at said anode by hydrogen bonding with the water in said electrolyte while having only a minor inhibiting influence on said anode-cathode reactions, said organic solvent being at least one amide selected from the group of amides consisting of formamide, N-methyl-formamide, dimethylformamide, acetamide, N-methyl-acetamide, N, N-dimethylacetamide, and N-methyl propionamide.

6. An electrochemical cell consisting essentially of a reactive metal anode highly reactive with water and spaced from a cathode by an electrically insulating film formed on said anode in the presence of water, an aqueous alkaline electrolyte in which said anode and cathode are immersed, said electrolyte permitting, at the anode, electrochemical dissolution of reactive metal to aqueous reactive metal ions, formation of an aqueous salt to a solid salt in the form of a porous film on the anode and, at the cathode, reduction of water, and an organic solvent in said electrolyte which reduces direct corrosion/parasitic reaction at said anode by hydrogen bonding with the water in said electrolyte while having only a minor inhibiting influence on said anode-cathode reactions, said organic solvent being hydrazine.

7. An electrochemical cell consisting essentially of a rective metal anode highly reactive with water and spaced from a cathode by an electrically insulating film formed on said anode in the presence of water, an aqueous alkaline electrolyte in which said anode and cathode are immersed, said electrolyte permitting, at the anode, electrochemical dissolution of reactive metal to aqueous reactive metal ions, formation of an aqueous salt to a solid salt in the form of a porous film on the anode and, at the cathode, reduction of water, and an organic solvent in said electrolyte which reduces direct corrosion/parasitic reaction at said anode by hydrogen bonding with the water in said electrolyte while having only a minor inhibiting influence on said anode-cathode reactions, said organic solvent being at least one ketone selected from the group of ketones consisting of acetone, ethyl methyl ketone and diethyl ketone.

8. An electrochemical cell consisting essentially of a reactive metal anode highly reactive with water and spaced from a cathode by an electrically insulating film formed on said anode in the presence of water, an aqueous alkaline electrolyte in which said anode and cathode are immersed, said electrolyte permitting, at the anode, electrochemical dissolution of reactive metal to aqueous reactive metal ions, formation of an aqueous salt to a solid salt in the form of a porous film on the anode and, at the cathode, reduction of water, and an organic solvent in said electrolyte which reduces direct corrosion/parasitic reaction at said anode by hydrogen bonding with the water in said electrolyte while having only a minor inhibiting influence on said anode-cathode reactions, said organic solvent being at least one ether selected from the group of ethers consisting of biacetyl and ethy ether.

9. An electrochemical cell consisting essentially of a reactive metal anode highly reactive with water and spaced from a cathode by an electrically insulating film formed on said anode in the presence of water, an aqueous alkaline electrolyte in which said anode and cathode are immersed, said electrolyte permitting, at the anode, electrochemical dissolution of reactive metal to aqueous reactive metal ions, formation of an aqueous salt to a solid salt in the form of a porous film on the anode and, at the cathode, reduction of water, and an organic solvent in said electrolyte which reduces direct corrosion/parasitic reaction at said anode by hydrogen bonding with the water in said electrolyte while having only a minor inhibiting influence on said anode-cathode reactions, said organic solvent being at least one ester selected from the group of esters consisting of tetrahydrofuran, dioxan, methyl formate and methyl acetate.