Aqueous lithium air batteries

Patent metadata

Field	Value
Publication number	US-9660311-B2
Application number	US-201213588911-A
Country	US
Kind code	B2
Filing date	Aug 17, 2012
Priority date	Aug 19, 2011
Publication date	May 23, 2017
Grant date	May 23, 2017

Abstract

Aqueous Li/Air secondary battery cells are configurable to achieve high energy density and prolonged cycle life. The cells include a protected a lithium metal or alloy anode and an aqueous catholyte in a cathode compartment. The aqueous catholyte comprises an evaporative-loss resistant and/or polyprotic active compound or active agent that partakes in the discharge reaction and effectuates cathode capacity for discharge in the acidic region. This leads to improved performance including one or more of increased specific energy, improved stability on open circuit, and prolonged cycle life, as well as various methods, including a method of operating an aqueous Li/Air cell to simultaneously achieve improved energy density and prolonged cycle life.

First claim

What is claimed:

1. An alkali metal/oxygen battery cell, the cell comprising:
an anode comprising an alkali metal electroactive component material;
an open-to-ambient-air cathode on or at which molecular oxygen obtained from the ambient air is electro-reduced during cell discharge, the cathode in alkali metal ion communication with the anode;
an aqueous catholyte comprising water and one or more evaporative-loss resistant and polyprotic active compounds dissolved in water that partake in a cell discharge reaction and effectuate cathode capacity for discharge below pH 7, the catholyte in contact with said cathode, wherein the one or more evaporative-loss resistant and polyprotic active compounds comprises a polyprotic acid that dissociates over the course of discharge, thus yielding two or more active protons per acid molecule in the catholyte that partake in the cell reaction as the discharge proceeds; and
a protective membrane architecture interposed between the cathode and the anode, the protective membrane architecture having a first and second major surface, the first surface adjacent to the cathode and in contact with the catholyte and the second surface adjacent to the anode;
wherein the protective membrane architecture solely allows through transport of the alkali metal ion and prevents liquids from contacting the alkali metal anode; and

wherein the polyprotic acid comprises a species that dissociates over the course of discharge yielding two or more active protons per acid molecule in the catholyte that partake in the cell reaction as the discharge proceeds selected from the group consisting of:
a carboxylic acid, the acid represented by the following general formula

wherein R 1 represents an organic radical,
wherein R 2 represents H or an organic radical,
wherein R 3 represents H or an organic radical, and
wherein at least one of the organic radicals represented by R 1 , R 2 or R 3 comprises a carboxyl group;
an amino acid, the amino acid represented by the following general formula

wherein R represents an aliphatic or aromatic optionally substituted organic divalent radical;
a hydroxy acid, the hydroxy acid represented by the following general formula

wherein R represents an aliphatic or aromatic optionally substituted organic divalent radical;
a metal acid salt of a polycarboxylic acid comprising a carboxylate anion, two or more acidic protons, and one or more metal cations or a neutral or acid onium salt of polycarboxylic acid comprising a carboxylate anion, one or more onium cations, and two or more acidic protons if the onium salt is an acid onium salt;
an inorganic acid salt selected from the group consisting of lithium dihydrogen phosphate and lithium hydrogen selenite, and combinations thereof;
a carboxylic acid derivative, wherein the hydroxyl moiety of the carboxyl group is replaced by an atom or a group of atoms comprising an electronegative atom, and the chemical group is not a hydroxyl group;
an ester of an inorganic acid represented by the general formula X(OR) n
wherein R is an aliphatic or aromatic optionally substituted organic radical,
X=N(═O) 2 , S(═O) 2 , or P═O, and
n is basicity of an acid from which the ester was derived;
a phenol represented by the general formula

wherein R 1 -R 5 are an aliphatic or aromatic optionally substituted organic radical;
an aminium salt;
an amphoteric hydroxide;
a polyprotic organic acid; and
an organic acid having a vapor pressure less than that of acetic acid.

2. The cell of claim 1 , wherein the catholyte comprises:
water; and
a carboxylic acid dissolved in water, the acid represented by the following general formula

wherein R 1 represents an organic radical;
wherein R 2 represents H or an organic radical; and
wherein R 3 represents H or an organic radical;
wherein at least one of the organic radicals represented by R 1 , R 2 or R 3 comprises a carboxyl group.

3. The cell of claim 2 , wherein the carboxylic acid is malonic acid, thus R 2 and R 3 represent H and R 1 represents a carboxyl group.

4. The cell of claim 2 , wherein at least one of R 1 , R 2 and R 3 represents an organic radical selected from the group consisting of an optionally substituted C 1 -C 10 alkyl group, optionally substituted C 2 -C 10 alkenyl group, optionally substituted C 2 -C 10 alkynyl group.

5. The cell of claim 2 , wherein at least one of R 1 , R 2 and R 3 represents an organic radical selected from the group consisting of an optionally substituted C 4 -C 10 cycloalkyl, optionally substituted C 4 -C 10 cycloalkenyl, and optionally substituted 3-10 membered heterocycle.

6. The cell of claim 2 , wherein at least one of R 1 , R 2 and R 3 represent an organic radical selected from the group consisting of an optionally substituted carbo- and heterocyclic 5-10 membered aryl.

7. The cell of claim 2 , wherein the carboxylic acid is selected from the group consisting of malonic acid, glutaric acid, and methylsuccinic acid.

8. The cell of claim 2 , wherein the equivalent weight of the acid that partakes in the cell discharge reaction, is selected from the range of values consisting of 50-70 g/equivalent of H + ; 71-90 g/equivalent of H + ; 91-110 g/equivalent of H + .

9. The cell of claim 2 , wherein the concentration of the carboxylic acid in the catholyte is between 0.05 molar and 1 molar.

10. The cell of claim 2 , wherein the catholyte is saturated with carboxylic acid and further comprises solid phase carboxylic acid in contact with its solution.

11. The cell of claim 2 , wherein the catholyte is saturated with the carboxylic acid.

12. The cell of claim 3 , wherein the concentration of malonic acid in the catholyte is selected from the molar range consisting of 0.5 molar to 2 molar, 2 molar to 4 molar, and greater than 4 molar.

13. The cell of claim 2 , further comprising a lithium salt dissolved in water.

14. The cell of claim 1 wherein the pH of the catholyte prior to initial discharge is less than 7.

15. The cell of claim 1 , wherein the catholyte comprises:
water; and
an amino acid dissolved in water, the amino acid represented by the following general formula

wherein R represents an aliphatic or aromatic optionally substituted organic divalent radical.

16. The cell of claim 1 , wherein the catholyte comprises:
water; and
a hydroxy acid dissolved in water, the hydroxy acid represented by the following general formula

wherein R represents an aliphatic or aromatic optionally substituted organic divalent radical.

17. The cell of claim 1 , wherein the catholyte comprises:
a metal acid salt of a polycarboxylic

Assignees

• Visco Steven J
• Nimon Yevgeniy S
• De Jonghe Lutgard C
• Petrov Alexei
• Goncharenko Nikolay
• Polyplus Battery Co Inc

Inventors

• Visco Steven J
• Nimon Yevgeniy S
• De Jonghe Lutgard C
• Petrov Alexei
• Goncharenko Nikolay

Classifications

• H01M12/08 Primary

  composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type · CPC title

• H01M2300/0005

  Acid electrolytes · CPC title

• Y02E60/128

  Cross-Sectional Technologies · mapped topic

• Y02E60/10

  Energy storage using batteries · CPC title