WO2000028609A1

WO2000028609A1 - Solid polymer battery electrolyte and reactive metal-water battery

Info

Publication number: WO2000028609A1
Application number: PCT/US1999/026439
Authority: WO
Inventors: Mason K. Harrup; Eric S. Peterson; Frederick F. Stewart
Original assignee: Bechtel Bwxt Idaho, Llc
Priority date: 1998-11-11
Filing date: 1999-11-09
Publication date: 2000-05-18
Also published as: AU3098600A; US6146787A

Abstract

A reactive metal-water battery (10) includes an anode (12) comprising a metal in atomic or alloy form selected from the group consisting of periodic table Group 1A metals, periodic table Group 2A metals and mixtures thereof. The battery includes a cathode (14) comprising water. Such also includes a solid polymer electrolyte (16) comprising a polyphosphazene comprising ligands bonded with a phosphazene polymer backbone. The ligands comprise an aromatic ring containing hydrophobic portion and a metal ion carrier portion. The metal ion carrier portion is bonded at one location with the polymer backbone and at another location with the aromatic ring containing hydrophobic portion. The invention also contemplates such solid polymer electrolytes use in reactive metal/water batteries, and in any other battery.

Description

SOLID POLYMER BATTERY ELECTROLYTE AND REACTIVE METAL- WATER BATTERY

CONTRACTUAL ORIGIN OF THE INVENTION

The United States Government has rights in this invention pursuant to Contract No. DE-AC07-94ID 13223 between the United States Department of Energy and Lockheed Martin Idaho Technologies Company, now Contract No. DE-AC07-99ID13727 with Bechtel BWXT Idaho, LLC.

TECHNICAL FIELD

This invention relates generally to reactive metal-water batteries and to reactive metal-water battery solid polymer electrolytes.

BACKGROUND OF THE INVENTION

A battery is a device that converts the chemical energy contained in its active materials directly into electrical energy by means of an electrochemical oxidation-reduction reaction. This type of reaction involves the transfer of electrons from one material to another through an electric circuit when the battery is placed under a load. A battery typically comprises one or more electrochemical cells connected in series, parallel, or both, depending on desired output voltage and capacity. Each cell principally comprises an anode, a cathode, and an electrolyte. The anode, or negative electrode, gives up electrons to the external circuit and is oxidized during the electrochemical reaction. The cathode, or positive electrode, accepts electrons from the external circuit and is reduced during the electrochemical reaction. The electrolyte serves as the ionic conductor and provides the medium for transfer of ions inside the cell between the anode and the cathode, and typically comprises liquid, solid or gel materials. Some batteries are intended for single use, and once discharged are discarded (commonly termed as primary batteries). Other batteries are more readily designed to be recharged essentially to their original condition upon discharge (commonly termed as secondary batteries).

Periodic table Group 1A and Group 2 A metals, and particularly lithium, are attractive as battery anode materials because of their light weight, high voltage, high electrochemical equivalence, and good conductivity. One type of battery comprises a reactive metal-water battery, such as a Li-water battery. Such batteries today are principally fabricated for low power and long duration, but may find other uses. With such a battery, the reactive metals such as lithium serve as the anode. The cathode is principally comprised of water. The electrolyte can be solid or liquid. For lithium, the principal reactions are:

Anode Li - e^" ^→ Li⁺

Cathode H₂O + e^~ OH- +

VΆ₂

Overall Li + H₂O → LiOH + ^lΔΑ₂

However, as apparent from the overall electrochemical reaction,

lithium and water will also react directly with one another, essentially

resulting in parasitic corrosion of the anode when exposed to water.

The corrosion reaction is highly undesirable because it produces no

useful electrical energy and consumes active lithium. The reaction is

highly exothermic and can detrimentally accelerate local corrosion.

Further, the produced lithium hydroxide reacts with water and eventually precipitates as a monohydrate crystal. Accordingly, a principal challenge

with respect to reactive metal-water batteries is development of

techniques that minimize this parasitic corrosion, thereby extending

battery life and improving efficiency. With liquid electrolytes, this has

typically focused on liquid additives that enhance or result in formation

of a calcareous film upon the outer surface of the lithium metal as a

means of protecting the metal from contact with water. Work has also

been conducted in the past with solid polymer electrolytes, but without

much success due to one or both of low current output and water

permeability which shortens life.

Accordingly, needs remain for improved reactive metal-water batteries

and solid polymer electrolytes therefor. While the invention was

principally motivated in solving problems with respect to this particular

art area, the artisan will appreciate applicability of the invention in other

areas, with the invention only being limited by the accompanying claims

appropriately interpreted in accordance with the Doctrine of Equivalents.

SUMMARY OF INVENTION

In one implementation, a reactive metal-water battery includes an

anode comprising a metal in atomic or alloy form selected from the

group consisting of periodic table Group 1A metals, periodic table

Group 2A metals and mixtures thereof. The battery includes a cathode

comprising water. Such also includes a solid polymer electrolyte comprising a polyphosphazene comprising ligands bonded with a

phosphazene polymer backbone. The ligands comprise a aromatic ring

containing hydrophobic portion and a metal ion carrier portion. The

metal ion carrier portion is bonded at one location with the polymer

backbone and at another location with the aromatic ring containing

hydrophobic portion. The invention also contemplates such solid

polymer electrolytes use in reactive metal-water batteries, and in any

other battery.

BRIEF DESCRIPTION OF THE DRAWINGS

Preferred embodiments of the invention are described below with

reference to the following accompanying drawings.

Fig. 1 is a diagrammatic schematic of a reactive metal-water battery

in accordance with an aspect of the invention.

Fig. 2 is a diagrammatic representation of chemical formula of a

solid polymer battery electrolyte in accordance with but one aspect of

the invention.

DETAILED DESCRIPTION OF THE PREFERRED

EMBODIMENTS

This disclosure of the invention is submitted in furtherance of the

constitutional purposes of the U.S. Patent Laws "to promote the progress

of science and useful arts" (Article 1, Section 8). Referring to Fig. 1, a reactive metal-water battery system under load is designated with

numeral 10. Such comprises an anode 12, a cathode 14 and a solid

polymer electrolyte 16. The battery is illustrated as being subjected to

some suitable discharge load 18. In one implementation, anode 12

comprises a metal in atomic or alloy form selected from the group

consisting of periodic table Group 1A metals, periodic table Group 2 A

metals and mixtures thereof. Cathode 14 comprises water. An

electrode 20 is received within cathode 14, with the battery being

discharged through load 18 via a conductive line 22 extending from

anode 12 to electrode 20 and correspondingly cathode 14. Electrode 20

preferably comprises porous conductive copper, and effectively serves to

provide an enlarged conductive surface area from line 22 for electrical

communication with cathode 14.

An exemplary commercial version of a battery in accordance with the

invention would comprise components 12, 16 and 20 received within a

suitable housing and essentially void of cathode-water in storage. Upon

preparation for use, cathode-water would be provided relative to the

housing and the battery placed under load. For use in water such as in

oceanic applications, the housing might be provided to be suitably

permeable to water such that immersion in salt water results in seawater

permeating into the housing to function as a cathode material and

effectively "turn on" a pre-wired load 18. Solid polymer electrolyte 16 comprises a polyphosphazene material

comprising ligands bonded with a phosphazene polymer backbone. The

ligands comprise an aromatic ring containing hydrophobic portion and a

metal ion carrier portion. The metal ion carrier portion is bonded at

one location with the polymer backbone, and at another location with

the aromatic ring containing hydrophobic portion. The metal ion carrier

portion preferably does not include any aromatic ring. One preferred

desired effect from such a construction results in the polymer backbone

functioning as the core of the material which is surrounded by an ionic

conducting channel which is itself surrounded or otherwise protected by

a hydrophobic material which is ideally remote from the backbone core.

Another preferred desired effect of such a construction, when the battery

is not under load, is receipt or alignment of the reactive metal along the

polymer backbone and corresponding displacement of water therefrom by

the hydrophobic portion of the solid electrolyte material. The reactive

metal will preferably associate with exposed electron pairs of nitrogen

atoms on the backbone. Upon application of suitable load, metal ions

of the anode will displace relative to the nitrogen atoms of the polymer

backbone and be received by and transported/conducted along the ion

carrier portion, thus forming a desired electrical circuit of suitable and

desired conductivity. An example is described below with reference to

Fig. 2. The metal ion carrier portion preferably comprises an ether, such as

an oxyether or a thioether. More preferred are polyethers, alkeneoxy

ethers and alkeneoxy ether polymers. Examples are materials selected

from the group consisting of ethyleneoxy ethers, propyleneoxy ethers and

mixtures thereof. Further preferred are ethylene thioethers, propylene

thioethers, and mixtures thereof.

The hydrophobic portion preferably comprises an aromatic ring

(including heteroaromatic rings) having at least one hydrocarbon group

or halohydrocarbon group bonded therewith. Further, the hydrophobic

portion preferably comprises at least 7 carbon atoms, and further at least

one terminal hydrocarbon or halohydrocarbon group. Substituted phenols

are example preferred materials, such as hydrocarbon and

halohydrocarbon substituted phenols.

Performance enhancing additives can also of course be provided as

part of the battery or electrolyte. By way of example only, such

include ceramic precursors, substituted phosphazene trimers, and cross

linking materials or treatments.

Fig. 2 illustrates but one exemplary implementation of a solid

polymer battery electrolyte in accordance with the invention. Such

depicts a polyphosphazene polymer backbone 25 having associated

ligands 27. Ligands 27 comprise an ion channel or metal ion carrier

portion 32 bonded at one location with polymer backbone section 25.

Ligands 27 also comprise a hydrophobic portion bonded with metal ion carrier portions 32 at another location thereof. In the illustrated

example, the hydrophobic portion is depicted as 4-(2,2,3,3

tetramethylbutyl) phenol. The metal ion carrier portion is depicted as an

ethylenoxyether polymer, where "n" is an integer preferably falling from

1 to 16. The illustrated example depicts a homopolymer where all the

ligands are the same, but co-polymers are also of course contemplated

with varying ligands, at least an effective amount of which constitutes

the described metal ion carrier and hydrophobic portions.

One example and preferred technique in battery fabrication in

accordance with the invention will result in a coating of the solid

polymer electrolyte material to cover an entirety of the outer surface of

the lithium or other reactive metal anode. Such is preferably achieved

by dissolving the solid polymer electrolyte material in a suitable solvent,

such as tetrahydrofuran (THF). This liquid material is then brushed

onto the anode, or the anode dipped within the solvent/electrolyte

system, to fully coat the anode. The solid electrolyte can be formed by

combining a polyphosphazene, such as polydiclorophosphazene, with an

alkoxide comprising the ligands, such as a sodium alkoxide. The

sodium alkoxide, for example, can be produced by combining the

ligands in alcohol form with sodium. Alternate techniques of fabrication

are also, of course, possible. Example

One hundred ten (110) ml of Triton-X-114^™ was combined in a

vessel with 300 ml of anhydrous tetrahydrofuran. Triton-X-114™ is

available from Aldrich Chemical Company of Milwaukee, WI. Six (6)

grams of sodium was freshly cut, hexane-washed, dried and added to the

mixture. The mixture was stirred and heated at 65 °C under an Ar

atmosphere until the sodium was consumed.

A solution containing 10 grams of dichloropolyphosphazene was

dissolved in 300 ml of a solvent comprising a 1 : 1 by volume mix of

diglyme and THF. This solution was slowly added to the above

solution under an argon atmosphere. Two hundred (200) ml of

additional diglyme/THF solvent was added, and the mixture stirred.

Such was heated under an argon atmosphere for two days. Salts were

precipitated by multiple water addition and polymer washings with

subsequent combinations with THF. The polymer was ultimately

centrifuged and dried in vacuo to remove all water. One gram of the

resultant polymer was dissolved in 10 grams of THF, and provided with

approximately 4.6 weight percent LiBF₄ in solution. A lithium metal

anode was immersed in the subject solution to dip coat the lithium

metal anode. Such was subsequently dried in vacuum to remove the

casting solvent, thus forming a lithium anode coated with a solid

polymer electrolyte in accordance with an aspect of the disclosure. In compliance with the statute, the invention has been described in

language more or less specific as to structural and methodical features.

It is to be understood, however, that the invention is not limited to the

specific features shown and described, since the means herein disclosed

comprise preferred forms of putting the invention into effect. The

invention is, therefore, claimed in any of its forms or modifications

within the proper scope of the appended claims appropriately interpreted

in accordance with the doctrine of equivalents.

Claims

WE CLAIM:

1. A reactive metal-water battery comprising:

an anode comprising a metal in atomic or alloy form selected

from the group consisting of periodic table Group 1A metals, periodic

table Group 2A metals and mixtures thereof;

a cathode comprising water; and

a solid polymer electrolyte comprising a polyphosphazene

comprising ligands bonded with a phosphazene polymer backbone, the

ligands comprising an aromatic ring containing hydrophobic portion and

a metal ion carrier portion, the metal ion carrier portion being bonded at

one location with the polymer backbone and at another location with the

aromatic ring containing hydrophobic portion.

2. The reactive metal-water battery of claim 1 wherein the

aromatic ring is heteroaromatic.

3. The reactive metal -water battery of claim 1 wherein the

metal ion carrier portion is bonded to an aromatic ring of the

hydrophobic portion.

4. The reactive metal-water battery of claim 1 wherein the

metal ion carrier portion is void of any aromatic ring.

5. The reactive metal-water battery of claim 1 wherein metal

ion carrier portion comprises an oxyether.

6. The reactive metal-water battery of claim 1 wherein the

metal ion carrier portion comprises a thioether.

7. The reactive metal-water battery of claim 1 wherein the

metal ion carrier portion comprises a polyether.

8. The reactive metal-water battery of claim 1 wherein the

metal ion carrier portion comprises an alkeneoxy ether.

9. The reactive metal -water battery of claim 1 wherein the

metal ion carrier portion comprises an alkeneoxy ether polymer.

10. The reactive metal-water battery of claim 1 wherein the

metal ion carrier portion comprises a material selected from the group

consisting of ethyleneoxy ethers, propyleneoxy ethers and mixtures

thereof.

11. The reactive metal-water battery of claim 1 wherein the

hydrophobic portion comprises an aromatic ring having at least one

hydrocarbon group or halohydrocarbon group bonded therewith.

12. The reactive metal -water battery of claim 1 wherein the

hydrophobic portion comprises at least 7 carbon atoms.

13. The reactive metal-water battery of claim 1 wherein the

hydrophobic portion comprises at least one terminal hydrocarbon group.

14. The reactive metal-water battery of claim 1 wherein the

hydrophobic portion comprises at least one terminal halohydrocarbon

group.

15. The reactive metal -water battery of claim 1 wherein the

metal ion carrier portion comprises an alkeneoxy ether and the hydrophobic portion comprises an aromatic ring having at least one

hydrocarbon group or halohydrocarbon group bonded therewith.

16. A solid polymer battery electrolyte comprising a

polyphosphazene comprising ligands bonded with a phosphazene polymer

backbone, the ligands comprising an aromatic ring containing

hydrophobic portion and a metal ion carrier portion, the metal ion

carrier portion being bonded at one location with the polymer backbone

and at another location with the aromatic ring containing hydrophobic

portion.

17. The solid polymer battery electrolyte of claim 16 wherein

the aromatic ring is heteroaromatic.

18. The reactive metal -water battery of claim 16 wherein the

metal ion carrier portion is bonded to an aromatic ring of the

hydrophobic portion.

19. The reactive metal-water battery of claim 16 wherein the

metal ion carrier portion is void of any aromatic ring.

20. The solid polymer battery electrolyte of claim 16 wherein

metal ion carrier portion comprises an oxyether.

21. The solid polymer battery electrolyte of claim 16 wherein

the metal ion carrier portion comprises a thioether.

22. The solid polymer battery electrolyte of claim 16 wherein

the metal ion carrier portion comprises a polyether.

23. The solid polymer battery electrolyte of claim 16 wherein

the metal ion carrier portion comprises an alkeneoxy ether.

24. The solid polymer battery electrolyte of claim 16 wherein

the metal ion carrier portion comprises an alkeneoxy ether polymer.

25. The solid polymer battery electrolyte of claim 16 wherein

the metal ion carrier portion comprises a material selected from the

group consisting of ethyleneoxy ethers, propyleneoxy ethers and mixtures

thereof.

26. The solid polymer battery electrolyte of claim 16 wherein

the hydrophobic portion comprises an aromatic ring having at least one

hydrocarbon group bonded therewith.

27. The solid polymer battery electrolyte of claim 16 wherein

the hydrophobic portion comprises an aromatic ring having at least one

halohydrocarbon group bonded therewith.

28. The solid polymer battery electrolyte of claim 16 wherein

the hydrophobic portion comprises at least 7 carbon atoms.

29. The solid polymer battery electrolyte of claim 16 wherein

the hydrophobic portion comprises at least one terminal hydrocarbon or

halohydrocarbon group.

30. The solid polymer battery electrolyte of claim 16 wherein

the hydrophobic portion comprises at least 7 carbon atoms and at least

one terminal hydrocarbon or halohydrocarbon group.

31. The solid polymer battery electrolyte of claim 16 wherein

the metal ion carrier portion comprises an alkeneoxy ether and the

hydrophobic portion comprises an aromatic ring having at least one

hydrocarbon group or halohydrocarbon group bonded therewith.