CA1304444C - Polymer solid electrolyte and a polymer solid electrolyte battery - Google Patents
Polymer solid electrolyte and a polymer solid electrolyte batteryInfo
- Publication number
- CA1304444C CA1304444C CA000567941A CA567941A CA1304444C CA 1304444 C CA1304444 C CA 1304444C CA 000567941 A CA000567941 A CA 000567941A CA 567941 A CA567941 A CA 567941A CA 1304444 C CA1304444 C CA 1304444C
- Authority
- CA
- Canada
- Prior art keywords
- polymer solid
- solid electrolyte
- polyether
- crosslinked
- stands
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 71
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 62
- 229920000570 polyether Polymers 0.000 claims abstract description 46
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 44
- 239000003792 electrolyte Substances 0.000 claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 12
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 10
- 230000000737 periodic effect Effects 0.000 claims description 10
- 230000006872 improvement Effects 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 abstract description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 36
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 19
- 239000000243 solution Substances 0.000 description 19
- 229910052786 argon Inorganic materials 0.000 description 18
- 150000001450 anions Chemical class 0.000 description 17
- 239000007789 gas Substances 0.000 description 17
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 15
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 15
- 238000000034 method Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 150000001768 cations Chemical class 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 10
- -1 perchloric acid ions Chemical class 0.000 description 10
- 238000007599 discharging Methods 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 8
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 8
- JJLKTTCRRLHVGL-UHFFFAOYSA-L [acetyloxy(dibutyl)stannyl] acetate Chemical compound CC([O-])=O.CC([O-])=O.CCCC[Sn+2]CCCC JJLKTTCRRLHVGL-UHFFFAOYSA-L 0.000 description 8
- 229940113088 dimethylacetamide Drugs 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 7
- 239000004745 nonwoven fabric Substances 0.000 description 7
- 229920001155 polypropylene Polymers 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 238000006467 substitution reaction Methods 0.000 description 7
- 230000033001 locomotion Effects 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 238000006073 displacement reaction Methods 0.000 description 4
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 150000001350 alkyl halides Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910006145 SO3Li Inorganic materials 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000000415 inactivating effect Effects 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000000452 restraining effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 102220532636 Sperm protein associated with the nucleus on the X chromosome N1_L44A_mutation Human genes 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 239000012345 acetylating agent Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000011243 crosslinked material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- WCRDXYSYPCEIAK-UHFFFAOYSA-N dibutylstannane Chemical compound CCCC[SnH2]CCCC WCRDXYSYPCEIAK-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 150000002641 lithium Chemical group 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Substances OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920001308 poly(aminoacid) Polymers 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
- Primary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A polymer solid electrolyte comprises a crosslinked polyether in which a salt is dissolved, and which has a crosslinked structure of the formula:
where R stands for -CnH2n+1 or -COCnH2+1, n?1.
It is suitable as an electrolyte and a separator for a battery, especially a lithium battery which can be recharged.
Batteries including such electrolyte are also disclosed.
A polymer solid electrolyte comprises a crosslinked polyether in which a salt is dissolved, and which has a crosslinked structure of the formula:
where R stands for -CnH2n+1 or -COCnH2+1, n?1.
It is suitable as an electrolyte and a separator for a battery, especially a lithium battery which can be recharged.
Batteries including such electrolyte are also disclosed.
Description
~304~
POLYMER SOLID ELECTROLYTE AND A
POLYMER SOLID ELECTROLYTE BATTERY
BACKGROUND OF THE INVENTION
Field of the Invention:
This invention relates to a polymer solid electro-lyte and a battery made by employing a polymer solid electro-lyte.
Description of the Prior Art:
A great deal of research work has been made, and is under way, for exploring the possibility of using polymer solid electrolytes in batteries, displays, etc. Referring by way of example to the use of a polymer solid electrolyte in a lithium battery, it is interposed between a positive electrode and a negative electrode. There have been pro-posed a variety of series of materials for polymer solid electrolytes, including a series of polyethylene oxides, a series of polyphosphazenes and a series of polyamino acids.
A solid electrolyte battery has a number of advan-tages. For example, it is leakage-free, has a high energy density, is inexpensive, and is easy to form in a layer built structure. The material which has so far been tested more extensively than any other material is a series of linear polyethers. This series of materials, however, have a melting point (about 60C) and are used only at a tempera-~ ture above their melting point, since at a temperature below :
:: :: ~:: : ;
. -~ '. - ` - ' ' , ~ ' .
~36)4~
their melting point, the mol-ten salt undergoes crystalli-zation and fails to exhibit a satisfactorily high ionic conduc-tivity.
A series of crosslinked polyethers have been pro-posed to improve the linear polyethers. These ma-terials have no melting point. ~ven at or around an ordinary room temperature, therefore, the molten salt hardly undergoes any crystallization, but shows a relatively good ionic con-ductivi-ty. Trifunctional polyethers which are crosslinked with diisocyanates, such as tolylene 2,4-diisocyanate and hexamethylene diisocyanate, are, among others, suitable for use on an industrial basis. They are easy to produce and a thin film thereof is easy to form. They are expected to be particularly useful as electrolyte for a rechargeable battery having a lithium anode.
A number of problems, however, arises from the use of any such crosslinked material in a common type of battery in which an intercalation type metal compound is used as a cathode, and lithium as an anode. The first problem resides in a reduction of performance which occurs to the battery during its storage. The active hydrogen in -the polymer solid electrolyte reacts with lithium during the storage of the battery and thereby raises its internal resistance resulting in a lowering of its capacity. The active hydro-gen means hydrogen in an -OH group or in an -~H group, which eacts dir~ctly with an alkali or alkaline earth metal,
POLYMER SOLID ELECTROLYTE AND A
POLYMER SOLID ELECTROLYTE BATTERY
BACKGROUND OF THE INVENTION
Field of the Invention:
This invention relates to a polymer solid electro-lyte and a battery made by employing a polymer solid electro-lyte.
Description of the Prior Art:
A great deal of research work has been made, and is under way, for exploring the possibility of using polymer solid electrolytes in batteries, displays, etc. Referring by way of example to the use of a polymer solid electrolyte in a lithium battery, it is interposed between a positive electrode and a negative electrode. There have been pro-posed a variety of series of materials for polymer solid electrolytes, including a series of polyethylene oxides, a series of polyphosphazenes and a series of polyamino acids.
A solid electrolyte battery has a number of advan-tages. For example, it is leakage-free, has a high energy density, is inexpensive, and is easy to form in a layer built structure. The material which has so far been tested more extensively than any other material is a series of linear polyethers. This series of materials, however, have a melting point (about 60C) and are used only at a tempera-~ ture above their melting point, since at a temperature below :
:: :: ~:: : ;
. -~ '. - ` - ' ' , ~ ' .
~36)4~
their melting point, the mol-ten salt undergoes crystalli-zation and fails to exhibit a satisfactorily high ionic conduc-tivity.
A series of crosslinked polyethers have been pro-posed to improve the linear polyethers. These ma-terials have no melting point. ~ven at or around an ordinary room temperature, therefore, the molten salt hardly undergoes any crystallization, but shows a relatively good ionic con-ductivi-ty. Trifunctional polyethers which are crosslinked with diisocyanates, such as tolylene 2,4-diisocyanate and hexamethylene diisocyanate, are, among others, suitable for use on an industrial basis. They are easy to produce and a thin film thereof is easy to form. They are expected to be particularly useful as electrolyte for a rechargeable battery having a lithium anode.
A number of problems, however, arises from the use of any such crosslinked material in a common type of battery in which an intercalation type metal compound is used as a cathode, and lithium as an anode. The first problem resides in a reduction of performance which occurs to the battery during its storage. The active hydrogen in -the polymer solid electrolyte reacts with lithium during the storage of the battery and thereby raises its internal resistance resulting in a lowering of its capacity. The active hydro-gen means hydrogen in an -OH group or in an -~H group, which eacts dir~ctly with an alkali or alkaline earth metal,
- 2 -, :
.
~L3(:~4~
or their ions. If a polyether crosslinked with isocyanate is used as the elec-trolyte, it means hydrogen in the urethane bond ~HC00~.
The second problem resides in the poor charging and discharging repeatability of the battery. This is appar-ently due to the fact that the polymer solid electrolyte is a bi-ionic conductor. If a common type of battery as hereinabove mentioned is discharged, anions (lithium ions) move from the anode to the cathode and lithium is inter-calated in the cathode. The anions in the polymerelectrolyte (e.g. perchloric acid ions in a battery containing molten lithium perchlorate) move toward the anode. However, the anode does not accept the anions, but the anions cause polarization in the electrolyte layer in the vicinity of the anode. If the battery is, then, charged, the cations which have been intercalated in the cathode can reversibly move to the anode through the electrolyte, but the anions which have polarized in the vicinity of the anode can return to their place of origin only very slowlyO As a result, the ions in the polymer have a low degree of reversibility leading to a great reduction of battery capacity with its repeated charging and discharging. Attempts have, therefore, been made to synthesize a single-ionic mobile polymer solid electro-lyte in which only -the cations are mobile, while the anions are fixed to the polymer chain. They have, however, been ~ ~ ~unsuccessful because of a great reduction of ionic conducti-:
~ _ : ~ , ... ,. ~.~ . ~ . .. . . .
- : , , ~ - . ~ ' --4~4 vity, or ~or other reasons SUMMARY OF THE INVENTION
It is an object of this invention to provide a polymer solid electrolyte which can be stored for a long time without lowering its quality, and a battery which includes a polymer solid electrolyte and can maintain its proper performance for a long time.
It is another object of this invention to provide a polymer solid electrolyte battery which permits repeaked charging and discharging without suffering from any substantial reduction of capacity.
In accordance with one aspect of the invention there is provided in a polymer solid electrolyte comprising a cross-linked polyether, the improvement wherein said crosslinked polyether has a structure of the formula:
~ o Icl 7 ~
O R
where R stands for -CnH2n~1 or -COCnH2~1, n21.
In accordance with another aspect of the invention there is provided in a polymer solid electrolyte comprising a polyether crosslinked with a urethane bond, the improvement which contains a substance which can replace an active hydrogen atom in said urethane bond with - C2H2n~1 or -COCnH2n~1, n21.
In accordance with another aspect of the invention there is provided in a polymer solid electrolyte comprising a crosslinked polyether, the improvement wherein said '' .
~3~4~44 crosslinked polyether has a crosslinked structure of the formula:
f O - C - N
O M
where M stands for an element of Group I of the periodic table other than a hydrogen atom.
BRIEF DESCRIPTION OF THE DRAWING
FIGURE 1 is a partly cutaway view of a test cell used for testing a polymer solid electrolyte embodying this invention;
FIGURE 2 is a graph comparing batteries embodying this invention and known in the art with respect to their capacity varying during storage; and FIGURE 3 is a graph comparing the results of charging and discharging cycle life tests conducted on the batteries embodying this invention and known in the art.
In FIGURE 1, 1 is a O.1 mm thick layer of lithium, 2 is a Teflon~ ring, 3 is a battery test sheet having a lower polymer portion and an upper portion formed from an active substance defining an anode, 4 is a titanium current collector, 5 is a teflon washer for thickness adjustment, 6 i- a hermetic :~ ~
*trade mark 4a :
~1.3~
seal, 7 is an anode current collector, 8 is a cell, and 9 is a cell cover.
DETAILED DESCRIPTION OF THE INVENTION
According to this invention, there is provided a polymer solid electrolyte formed from a crosslinked poly-ether having a crosslinked structure of the formula O - C - N t , where R stands for an inert group which is O R not a hydrogen atom.
There is also provided a polymer solid electrolyte which comprises a crosslinked polyether crosslinked with a urethane bond, and contains a substance which can replace an active hydrogen atom in the urethane bond with another inert group.
There is also provided a polymer solid electrolyte which comprises a crosslinked polyether having a crosslinked structure of the formula ~ O - C - ~ t, where M stands for O M
an element of Group I of the periodic table other than a hydrogen atom.
There is also provided a polymer solid electrolyte - - comp~rising a crosslinked polyether in which a salt is dis-solved, and which contains at least one group selected from among -503M', -COOM', -PO(OM')2 and -PH(O)(OM'), where M' stands for an element of Group I of the periodic table.
There is also provided a polymer solid electrolyte comprising a crosslinked polyether in which an inorganic .
.
~ :
, ~3~
salt is dissolved, and further containing 0.5 to 10 mols, per mol of the inorganic salt, of a substance having a large molecular shape and containing at least one group selected from among -SO3M', -COOM', -PO(OM')2 and -PH(O)(OM').
According to thls invention, there is also provided a polymer solid electrolyte battery which contains any of the polymer solid electrolytes as hereinabove described.
There is also provided a polymer solid electrolyte battery which contains only in the vicinity of an anode a polymer solid electrolyte comprising a crosslinked polyether having a crosslinked structure of the formula ~ O - C - N ~.
O M
Although the active hydrogen in the polymer solid electrolyte lowers the performance of the battery during its storage, it is possible to obtain a polymer solid electro-lyte having a long storage life if the active hydrogen is inactivated. Various methods are available for inactivat-ing the active hydrogen. Alkylation and acylation are typical of those methods. An alkylating or acylating agent can be added to a polymer solid electrolyte to prevent its displacement reaction with metallic lithium, etc. The inactivating treatment can alternativeIy be introduced into the latter part of a process for producing a polymer solid electrolyte to replace any active element with an inert group before a product is fabricated.
Referring by way of example to a polyamine solid ~'~ ' ' ' ` ' ` ' ' ' ' .
~3a~4~
electrolyte, it has a structure of the formula:
COCHNH ~n CH2CH2COO (CH2CH20) mCH3 The hydrogen of the -NH- group is liable to undergo a dis-placement reaction with lithium, etc. This displacement reaction can be prevented if an alkyl halide, such as methyl iodide, is added to the electrolyte. The alkyl portion of the alkyl halide replaces the hydrogen as soon as the metal ion is going to attack it, as shown by the following formula:
-NH- + M RX~ [-NM-] RX~ -NR-where M stands for a metal, R stands for an alkyl group, and X stands for a halogen.
The displacement reaction can also be prevented in accordance with a similar mechanism if an acylating agent, such as acetic anhydride, is added to the electrolyte, as shown by the following formula:
- CH3COR' CH3COR' -NH- + M ~ [-NM-] ~ -NCOCH3 It is also possible to obtain a polymer solid electro-lyte which is inert to lithium, etc. if the electrolyte is treated with an alkyl metal, such as butyl lithium, and is, : then, alkylated with an alkyl halide, such as methyl iodide, as shown below:
-NH- + RM - -NM- + RH
: 25 -NM- + RX --~ -NR- + MX
It is also possible to inactivate a polymer solid .
~3~44~
electrolyte if it is treated with an acetylating agent, such as acetyl chloride, as shown below:
-NH- + CH3COX -NCOCH3- + HX
If the electrolyte is only treated with an alkyl metal, such as butyl or phenyl lithium, it is rendered inert to lithium, etc., as active hydrogen H is replaced by the metal M.
It is desirable to employ a polymer solid electro-lyte having a large cation transfer number in order to ob-tain a battery having an improved adaptability for repeated charging and discharging. In order to raise the cation transfer number of an inorganic salt dissolved in a polymer solid electrolyte, of which salt the greater part is dissoci-ated into anions and cations, it is necessary to restrain the movement of the anions.
If a group replacing a hydrogen atom in a polymer solid electrolyte containing a urethane bond is highly electron-donative, or is ionic as in the case of a metal, resonance is liable to occur to the urethane bond. In other words, electrons are strongly attracted to the oxygen atoms and there arises a deficiency of electrons on the nitrogen atom, as shown below:
~ O - C - N ~ - O - C = N -O R O R~
S ~, +
- O - C - N - _ - O - C - N -+
O ~ O M
. ,~-.. ,.. ,-., , ~3~ 4 The anions separated from the inorganic salt combine with the nitrogen atom weakly and their movement is, therefore, restrained, while the transfer of the cations is enhanced.
If the group replacing the hydrogen atom is a metal, the transfer of cations can be enhanced still more effec-tively. As the cations of the metal which are rendered still more ionic by resonance can function as carrier ions, they increase the carrier ions in the polymer solid electro-lyte and thereby raise the mobility of cations therein.
When the polymer solid electrolyte of this invention obtained by the substitution of a metal for hydrogen is used to make a battery, however, it is possible to use a known polymer (i.e. a polyether crosslinked with an isocyanate), too, as far as the interfacial area between the active mate-rial defining the anode and the electrolyte is concerned, without causing any reduction of battery capacity during its storage, or of its charging and discharging cycle life.
It would rather be better to say that the polymer of this invention can be used more effectively for that portion of the electrolyte which excludes at least the interfacial area between the anode material and the electrolyte.
Therefore, it is desirable that the hydrogen atom of the urethane group in the polymer not be replaced by a lithium atom in the surface of at least one side of a sheet 25~ of electrolyte, so that the electrolyte of this invention obtained by the substitution of a metal may fully exhibit _ g _ ,. ....
~L3~4~
its advantages.
Various methods can be employed for making a sheet of polymer solid electrolyte according to this invention.
According to one method, one surface of a sheet of polyether crosslinked with isocyanate is coated with a reactant solu-tion, so that the substitution of lithium may occur to only one surface -thereof. According to another method, the whole sheet is dipped in a reactant solution so that the substitution of lithium may occur to both surfaces of the sheet, and a hydrogen atom, or alkyl group is, then, substi-tuted for the lithium on one of its surfaces. According to still another method, the substitution of lithium is caused to occur to both surfaces of a sheet and a polyether crosslinked with isocyanate is, then, formed on one of its surfaces. ~hese methods are merely illustrative of a variety of methods which can be employed for making a sheet of this invention having one surface to which the substitu-tion of lithium occurs, while no such substi-tution occurs to the other surface thereof.
The addition of a metal salt having giant anions, as well as the inorganic salt, to the polymer solid electro-~ lyte is another method of restraining the movement of anions ; and thereby reali~ing a high cation transfer number. The electrostatic impact of the giant anions restrains the move-ment of anions of the inorganic salt. This method adapts ; the action of a cation e-xchange membrane.
~ ~.
~3 1)4~
The giant anions can be formed from the crosslinked polymer defining the polymer solid electrolyte itself, or can also be obtained by adding a metal salt with anions having a certain molecular weight. In the former case, the giant anions can be obtained by the chemical modifica-tion of a part of the crosslinked polymer, e.g. adding a -SO3Li group, while in the latter case, they can be obtained by adding a substance such as CnH2n+l(CH2CH2O)mSO3Li.
If the latter method is employed for making a polymer solid electrolyte, it is desirable that the substance as hereinabove mentioned be added to the polymer when it is crosslinked. The amount in which it is added has a certain range. It is necessary to add at least the amount in which the substance can begin to show the effect of restraining the movement of anions, but the addition of too large an amount prevents the crosslinking of the polymer. Although the amount may somewhat differ with the substance which is employed, it is generally in the range of 0.5 to 10 mols per mol of the inorganic salt when the latter salt is used in the amount which is optimum for the ionic conductivity of the polymer solid electrolyte.
The invention will now be described in further detail with reference to several examples thereof. In the follow-~ ing examples, the working atmosphere was composed of dry air having a relative humidity not exceeding -50%, and the poly-ethers were of the triol type containing an ethylene oxide :
~: , L3~4~
structure and a propylene oxide structure in a structural ratio of 8:2 and having a molecular weight of about 3000, unless otherwise noted. Prior to use, they were dried at a temperature of 100C in a vacuum, while being stirred by a magnetic stirrer in a three~necked flask.
A solution of lithium perchlorate and!polyether was prepared as will hereinafter be described. The polyether to be dissolved was added to an acetone solution containing one part by weight of lithium perchlorate for 10 parts by weight of polyether, and the solution was heated at a tempera-ture of 100C in a vacuum, while being stirred by a magnetic stirrer in a three-necked flask, until no distillate formed.
A paste of an active material forming the cath~de was prepared as will hereinafter be described. Eleven parts of a solution of lithium perchlorate and polyether, two parts of dimethylacetamide, an equivalent amount of hexamethylene diisocyanate and 0.006 part of di-n-butyltin diacetate were fully mixed to form a first mixture. Nine parts of a vanadium oxide powder and one part of acetylene black were fully mixed and their mixture was dried. The latter mixture was added to the first mixture and they were fully kneaded together to form a paste. The paste was used immediately after its preparation.
Five parts of a dry polyether, one part of dimethyl-acetamide, an equivalent amount of hexamethylene diisocyanate ' .
9L304~
and 0.003 part of di-n-butyltin diacetate were fully mixed together. The mixture was coated on a 50 micron nonwoven fabric of polypropylene and it was left to stand at a tem-perature of 80C for 16 hours in an argon gas atmosphere to form a sheet.
The sheet was dlpped in a 0.1 mol/1 n-hexane solution of n-butyl lithium in an argon gas atmosphere and was left therein for three hours. Then, it was transferred into a 0.02 wt.% n-hexane solution of methyl iodide and after one hour of immersion, it was washed with n-hexane and the n-hexane was thereafter removed by volatilization.
Then, the sheet was dipped in a 0.04 mol/l acetone solution of lithium perchlorate in a totally closed vessel and was left therein for 20 minutes, whereby lithium per-chlorate was dissolved in the sheet. Then, the paste of the active material forming thecathode,which had been pre-pared as herelnabove described, was coated on the upper surface of the sheet. The sheet was left to stand at a temperature of 80C for 16 hours in an argon gas atmosphere and was, then, dried at the same temperature for 48 hours in a vacuum. Then, the sheet was incorporated into a battery test cell, which will hereinafter be referred to as "CeIl I"
EX~MPLE 2 Two parts of dimethylacetamide, an equivalent amount of hexamethylene diisocyanate, 0.006 part of di-n-butyltin ~L3()~L~4~L
diacetate and two parts of methyl iodide were fully mixed in 11 parts of a solution of lithium perchlorate and poly-ether. The mixture was coated on a 50 micron nonwoven fabric of polypropylene and it was left to stand at a tem-perature of 80C for 16 hours in an argon gas atmosphere to form a sheet. The paste as hereinabove described was coated on the upper surface of the sheet. The sheet was left at a temperature of 80C for 16 hours in an argon sas atmosphere and was dried. Then, it was incorporated into a battery test cell, which will hereinafter be referred to as "Cell II".
Five parts of a dry polyether, one part of dimethyl-acetamide, an e~uivalent amount of hexamethylene diisocyanate and 0.003 part of di-n-butyltin diacetate were fully mixed together. The mixture was coated on a 50 micron nonwoven fabric of polypropylene and it was left at a temperature of 80C for 16 hours in an argon gas atmosphere to form a sheet.
The sheet was dipped in a 0.1 mol/l n~-hexane solution of n-butyl lithium in an argon gas atmosphere and was left therein for three hours. Then, it was washed with n-hexane and the n-hexane was removed by volatilization.
Then, the sheet was dipped in a 0.04 mol/l acetone solution of lithium perGhlorate in a totally closed vessel and was left therein for 20 minutes, whereby lithium per-chlorate was diss~olved in the sheet. The paste as herein-' ~
~L3044~L
above described was coated on the upper surface of the sheet. The sheet was left to stand at a temperature of 80C for 16 hours in an argon gas atmosphere and was dried at the same temperature for 48 hours in a vacuum. It was incorporated into a battery test cell, which will herein-after be referred to as "Cell III".
Five parts of a dry polyether, one part of dimethyl-acetamlde, an equivalent amount of hexamethylene diisocyanate and 0.003 part of di-n-butyltin diacetate were fully mixed toyether. The mixture was coated on a 50 micron nonwoven fabric of polypropylene and it was left to stand at a tempera-ture of 80C for 16 hours in an argon gas atmosphere to form a sheet. The sheet was dipped in a 0.1 mol/l n-hexane solu-tion of n-butyl lithium in an argon gas atmosphere and was left therein for three hours. Then, it was washed with n-hexane and the n-hexane was removed by volatilization. The sheet was, then, dipped in a 0.04 mol/l acetone solution of lithium perchlorate in a totally closed vessel and was left therein for 20 minutes, whereby lithium perchlorate was dissolved in the sheet.
Two parts of dimethylacetamide, an equivalent amount of hexamethylene diisocyanate and 0.006 part of di-n-butyltin diacetate were fully mixed in 11 parts of a solution of lithium perchlorate and poIyether. The mixture was applied to the . upper surface of the sheet to form a thin layer thereon and ~3~4~44 the sheet was left to stand at a temperature of 80C for 16 hours in an argon gas atmosphere.
The paste as hereinabove described was coated on the upper surface of the sheet. Then, the sheek was left to stand at a temperature of 80C for 16 hours in an argon gas atmosphere and was dried at the same temperature for 48 hours in a vacuum. It was incorporated into a battery test cell, which will hereinafter be referred to as "Cell IV".
A part of the hydroxyl groups in the same polyether as had been employed in the foregoing examples were esterified and neutralized with lithium chloride to form -So3Li groups.
The terminal -OH and -SO3Li groups in the polyether had a ratio of 9:1.
Lithium perchlorate was dissolved in the polyether by the method which had been employed in the foregoing examples. Two parts of dimethylacetamide, an equivalent amount of hexamethylene diisocyanate and 0.006 part of di-n-butyltin diacetate were fully mixed in ll parts of a solu-tion of lithium perchlorate and polyether. The mixture was coated on a 50 micron nonwoven fabric of polypropylene and it was left to stand at a temperature of 80C for 16 hours in an argon gas atmosphere to form a sheet. Then, the paste as hereinabove described was coated on the upper surface of the sheet. The sheek was left to stand at a temperature of 80C for 16 hours in an argon gas atmosphere and was dried , :
, ~3~L44A
at the same temperature for 48 hours in a vacuum. It was incorporated into a battery test cell, which will hereinafter be referred to as "Cell V".
An equivalent amount of hexamethylene diisocyanate, 0.006 part of di-n butyltin diacetate, and a solution which had been prepared by dissolving 4 parts of a substance of the formula C12H25(CH2CH2O)4SO3Li in four parts of dimethyl-acetamide were fully mixed in 11 parts of a solution of lithium perchlorate and polyether. The mixture was coated on a 50 micron nonwoven fabric of polypropylene and it was left to stand at a temperature of 80C for 16 hours in an argon gas atmosphere to form a sheet. The paste as herein-above described was coated on the upper surface of the sheet and the sheet was left to stand at a temperature of 80C for 16 hours in an argon gas atmosphere. Then, the sheet was dried at the same temperature for 48 hours in a vacuum and was incorporated into a battery test cell, which will here-inafter be referred to as "Cell VI".
A comparati~e cell was prepared in accordance with the prior art. Two parts of dimethylacetamide, an equivalent amount of hexamethylene diisocyanate and 0.006 part of di- -n-butyltin diacetate were fully mixed in 11 parts of a solu-tion of lithium perchlorate and polyether The mixture was coated on a 50 micron nonwoven fabric of polypropylene and was left to stand at a temperature of 80C for 16 hours in ~:
~ ::
130~44 an argon gas atmosphere to form a sheet. The paste as hereinbefore described was coated on the upper surface of the sheet and the sheet was left to stand at a temperature of 80C for 16 hours in an argon gas atmosphere. Then, it was dried at the same temperature for 48 hours in a vacuum and was incorporated into a battery test cell, which will hereinafter ~e referred to as "Cell VII".
Thirty cells of each of the seven types I to VII
were prepared and were tested for their variation of capacity during storage and their charging and discharging cycle life.
Twenty cells of each type were tested for variation of capacity during storage. They were placed in a thermo-static oven of the recirculation type having a temperature of 80C. Five cells were taken out of the oven and tested upon lapse of each of 0, 7.5, 15, and 30 days. The test was conducted by a constant current discharge of 13 ~
(10 ~A/cm2) at a temperature of 80C until a final discharg-ing voltage of 2 V was reached. The results are shown in FIGURE 2.
Ten cells of each type were tested for their cycle life. They were placed in a thermostatic oven of the re-circulation type having a temperature of 80C and were caused to discharge a current of 52 ~A (40 ~/c~ ), while they were charged with a current of 26 ~A (20/uA/cm2), until a final discharging voltage of 2.0 V and a final charging voltage of 4.0 V were reached. The results are shown in , : ~
13~
FIGURE 3 .
The results shown in FIGURES 2 and 3 confirm that the batteries of this invention are superior to the conven-tional one.
As is obvious from the foregoing description, this lnvention provides a polymer solid electrolyte which can be stored for a long time without suffering from any reduction of quality, and a battery which does not lower its perform-ance for a long time. It also provides a polymer solid electrolyte battery which can be charged and discharged for a large number of times repeatedly without having any sub-stantial reduction of capacity.
: ~ - 19 -. .
' '
.
~L3(:~4~
or their ions. If a polyether crosslinked with isocyanate is used as the elec-trolyte, it means hydrogen in the urethane bond ~HC00~.
The second problem resides in the poor charging and discharging repeatability of the battery. This is appar-ently due to the fact that the polymer solid electrolyte is a bi-ionic conductor. If a common type of battery as hereinabove mentioned is discharged, anions (lithium ions) move from the anode to the cathode and lithium is inter-calated in the cathode. The anions in the polymerelectrolyte (e.g. perchloric acid ions in a battery containing molten lithium perchlorate) move toward the anode. However, the anode does not accept the anions, but the anions cause polarization in the electrolyte layer in the vicinity of the anode. If the battery is, then, charged, the cations which have been intercalated in the cathode can reversibly move to the anode through the electrolyte, but the anions which have polarized in the vicinity of the anode can return to their place of origin only very slowlyO As a result, the ions in the polymer have a low degree of reversibility leading to a great reduction of battery capacity with its repeated charging and discharging. Attempts have, therefore, been made to synthesize a single-ionic mobile polymer solid electro-lyte in which only -the cations are mobile, while the anions are fixed to the polymer chain. They have, however, been ~ ~ ~unsuccessful because of a great reduction of ionic conducti-:
~ _ : ~ , ... ,. ~.~ . ~ . .. . . .
- : , , ~ - . ~ ' --4~4 vity, or ~or other reasons SUMMARY OF THE INVENTION
It is an object of this invention to provide a polymer solid electrolyte which can be stored for a long time without lowering its quality, and a battery which includes a polymer solid electrolyte and can maintain its proper performance for a long time.
It is another object of this invention to provide a polymer solid electrolyte battery which permits repeaked charging and discharging without suffering from any substantial reduction of capacity.
In accordance with one aspect of the invention there is provided in a polymer solid electrolyte comprising a cross-linked polyether, the improvement wherein said crosslinked polyether has a structure of the formula:
~ o Icl 7 ~
O R
where R stands for -CnH2n~1 or -COCnH2~1, n21.
In accordance with another aspect of the invention there is provided in a polymer solid electrolyte comprising a polyether crosslinked with a urethane bond, the improvement which contains a substance which can replace an active hydrogen atom in said urethane bond with - C2H2n~1 or -COCnH2n~1, n21.
In accordance with another aspect of the invention there is provided in a polymer solid electrolyte comprising a crosslinked polyether, the improvement wherein said '' .
~3~4~44 crosslinked polyether has a crosslinked structure of the formula:
f O - C - N
O M
where M stands for an element of Group I of the periodic table other than a hydrogen atom.
BRIEF DESCRIPTION OF THE DRAWING
FIGURE 1 is a partly cutaway view of a test cell used for testing a polymer solid electrolyte embodying this invention;
FIGURE 2 is a graph comparing batteries embodying this invention and known in the art with respect to their capacity varying during storage; and FIGURE 3 is a graph comparing the results of charging and discharging cycle life tests conducted on the batteries embodying this invention and known in the art.
In FIGURE 1, 1 is a O.1 mm thick layer of lithium, 2 is a Teflon~ ring, 3 is a battery test sheet having a lower polymer portion and an upper portion formed from an active substance defining an anode, 4 is a titanium current collector, 5 is a teflon washer for thickness adjustment, 6 i- a hermetic :~ ~
*trade mark 4a :
~1.3~
seal, 7 is an anode current collector, 8 is a cell, and 9 is a cell cover.
DETAILED DESCRIPTION OF THE INVENTION
According to this invention, there is provided a polymer solid electrolyte formed from a crosslinked poly-ether having a crosslinked structure of the formula O - C - N t , where R stands for an inert group which is O R not a hydrogen atom.
There is also provided a polymer solid electrolyte which comprises a crosslinked polyether crosslinked with a urethane bond, and contains a substance which can replace an active hydrogen atom in the urethane bond with another inert group.
There is also provided a polymer solid electrolyte which comprises a crosslinked polyether having a crosslinked structure of the formula ~ O - C - ~ t, where M stands for O M
an element of Group I of the periodic table other than a hydrogen atom.
There is also provided a polymer solid electrolyte - - comp~rising a crosslinked polyether in which a salt is dis-solved, and which contains at least one group selected from among -503M', -COOM', -PO(OM')2 and -PH(O)(OM'), where M' stands for an element of Group I of the periodic table.
There is also provided a polymer solid electrolyte comprising a crosslinked polyether in which an inorganic .
.
~ :
, ~3~
salt is dissolved, and further containing 0.5 to 10 mols, per mol of the inorganic salt, of a substance having a large molecular shape and containing at least one group selected from among -SO3M', -COOM', -PO(OM')2 and -PH(O)(OM').
According to thls invention, there is also provided a polymer solid electrolyte battery which contains any of the polymer solid electrolytes as hereinabove described.
There is also provided a polymer solid electrolyte battery which contains only in the vicinity of an anode a polymer solid electrolyte comprising a crosslinked polyether having a crosslinked structure of the formula ~ O - C - N ~.
O M
Although the active hydrogen in the polymer solid electrolyte lowers the performance of the battery during its storage, it is possible to obtain a polymer solid electro-lyte having a long storage life if the active hydrogen is inactivated. Various methods are available for inactivat-ing the active hydrogen. Alkylation and acylation are typical of those methods. An alkylating or acylating agent can be added to a polymer solid electrolyte to prevent its displacement reaction with metallic lithium, etc. The inactivating treatment can alternativeIy be introduced into the latter part of a process for producing a polymer solid electrolyte to replace any active element with an inert group before a product is fabricated.
Referring by way of example to a polyamine solid ~'~ ' ' ' ` ' ` ' ' ' ' .
~3a~4~
electrolyte, it has a structure of the formula:
COCHNH ~n CH2CH2COO (CH2CH20) mCH3 The hydrogen of the -NH- group is liable to undergo a dis-placement reaction with lithium, etc. This displacement reaction can be prevented if an alkyl halide, such as methyl iodide, is added to the electrolyte. The alkyl portion of the alkyl halide replaces the hydrogen as soon as the metal ion is going to attack it, as shown by the following formula:
-NH- + M RX~ [-NM-] RX~ -NR-where M stands for a metal, R stands for an alkyl group, and X stands for a halogen.
The displacement reaction can also be prevented in accordance with a similar mechanism if an acylating agent, such as acetic anhydride, is added to the electrolyte, as shown by the following formula:
- CH3COR' CH3COR' -NH- + M ~ [-NM-] ~ -NCOCH3 It is also possible to obtain a polymer solid electro-lyte which is inert to lithium, etc. if the electrolyte is treated with an alkyl metal, such as butyl lithium, and is, : then, alkylated with an alkyl halide, such as methyl iodide, as shown below:
-NH- + RM - -NM- + RH
: 25 -NM- + RX --~ -NR- + MX
It is also possible to inactivate a polymer solid .
~3~44~
electrolyte if it is treated with an acetylating agent, such as acetyl chloride, as shown below:
-NH- + CH3COX -NCOCH3- + HX
If the electrolyte is only treated with an alkyl metal, such as butyl or phenyl lithium, it is rendered inert to lithium, etc., as active hydrogen H is replaced by the metal M.
It is desirable to employ a polymer solid electro-lyte having a large cation transfer number in order to ob-tain a battery having an improved adaptability for repeated charging and discharging. In order to raise the cation transfer number of an inorganic salt dissolved in a polymer solid electrolyte, of which salt the greater part is dissoci-ated into anions and cations, it is necessary to restrain the movement of the anions.
If a group replacing a hydrogen atom in a polymer solid electrolyte containing a urethane bond is highly electron-donative, or is ionic as in the case of a metal, resonance is liable to occur to the urethane bond. In other words, electrons are strongly attracted to the oxygen atoms and there arises a deficiency of electrons on the nitrogen atom, as shown below:
~ O - C - N ~ - O - C = N -O R O R~
S ~, +
- O - C - N - _ - O - C - N -+
O ~ O M
. ,~-.. ,.. ,-., , ~3~ 4 The anions separated from the inorganic salt combine with the nitrogen atom weakly and their movement is, therefore, restrained, while the transfer of the cations is enhanced.
If the group replacing the hydrogen atom is a metal, the transfer of cations can be enhanced still more effec-tively. As the cations of the metal which are rendered still more ionic by resonance can function as carrier ions, they increase the carrier ions in the polymer solid electro-lyte and thereby raise the mobility of cations therein.
When the polymer solid electrolyte of this invention obtained by the substitution of a metal for hydrogen is used to make a battery, however, it is possible to use a known polymer (i.e. a polyether crosslinked with an isocyanate), too, as far as the interfacial area between the active mate-rial defining the anode and the electrolyte is concerned, without causing any reduction of battery capacity during its storage, or of its charging and discharging cycle life.
It would rather be better to say that the polymer of this invention can be used more effectively for that portion of the electrolyte which excludes at least the interfacial area between the anode material and the electrolyte.
Therefore, it is desirable that the hydrogen atom of the urethane group in the polymer not be replaced by a lithium atom in the surface of at least one side of a sheet 25~ of electrolyte, so that the electrolyte of this invention obtained by the substitution of a metal may fully exhibit _ g _ ,. ....
~L3~4~
its advantages.
Various methods can be employed for making a sheet of polymer solid electrolyte according to this invention.
According to one method, one surface of a sheet of polyether crosslinked with isocyanate is coated with a reactant solu-tion, so that the substitution of lithium may occur to only one surface -thereof. According to another method, the whole sheet is dipped in a reactant solution so that the substitution of lithium may occur to both surfaces of the sheet, and a hydrogen atom, or alkyl group is, then, substi-tuted for the lithium on one of its surfaces. According to still another method, the substitution of lithium is caused to occur to both surfaces of a sheet and a polyether crosslinked with isocyanate is, then, formed on one of its surfaces. ~hese methods are merely illustrative of a variety of methods which can be employed for making a sheet of this invention having one surface to which the substitu-tion of lithium occurs, while no such substi-tution occurs to the other surface thereof.
The addition of a metal salt having giant anions, as well as the inorganic salt, to the polymer solid electro-~ lyte is another method of restraining the movement of anions ; and thereby reali~ing a high cation transfer number. The electrostatic impact of the giant anions restrains the move-ment of anions of the inorganic salt. This method adapts ; the action of a cation e-xchange membrane.
~ ~.
~3 1)4~
The giant anions can be formed from the crosslinked polymer defining the polymer solid electrolyte itself, or can also be obtained by adding a metal salt with anions having a certain molecular weight. In the former case, the giant anions can be obtained by the chemical modifica-tion of a part of the crosslinked polymer, e.g. adding a -SO3Li group, while in the latter case, they can be obtained by adding a substance such as CnH2n+l(CH2CH2O)mSO3Li.
If the latter method is employed for making a polymer solid electrolyte, it is desirable that the substance as hereinabove mentioned be added to the polymer when it is crosslinked. The amount in which it is added has a certain range. It is necessary to add at least the amount in which the substance can begin to show the effect of restraining the movement of anions, but the addition of too large an amount prevents the crosslinking of the polymer. Although the amount may somewhat differ with the substance which is employed, it is generally in the range of 0.5 to 10 mols per mol of the inorganic salt when the latter salt is used in the amount which is optimum for the ionic conductivity of the polymer solid electrolyte.
The invention will now be described in further detail with reference to several examples thereof. In the follow-~ ing examples, the working atmosphere was composed of dry air having a relative humidity not exceeding -50%, and the poly-ethers were of the triol type containing an ethylene oxide :
~: , L3~4~
structure and a propylene oxide structure in a structural ratio of 8:2 and having a molecular weight of about 3000, unless otherwise noted. Prior to use, they were dried at a temperature of 100C in a vacuum, while being stirred by a magnetic stirrer in a three~necked flask.
A solution of lithium perchlorate and!polyether was prepared as will hereinafter be described. The polyether to be dissolved was added to an acetone solution containing one part by weight of lithium perchlorate for 10 parts by weight of polyether, and the solution was heated at a tempera-ture of 100C in a vacuum, while being stirred by a magnetic stirrer in a three-necked flask, until no distillate formed.
A paste of an active material forming the cath~de was prepared as will hereinafter be described. Eleven parts of a solution of lithium perchlorate and polyether, two parts of dimethylacetamide, an equivalent amount of hexamethylene diisocyanate and 0.006 part of di-n-butyltin diacetate were fully mixed to form a first mixture. Nine parts of a vanadium oxide powder and one part of acetylene black were fully mixed and their mixture was dried. The latter mixture was added to the first mixture and they were fully kneaded together to form a paste. The paste was used immediately after its preparation.
Five parts of a dry polyether, one part of dimethyl-acetamide, an equivalent amount of hexamethylene diisocyanate ' .
9L304~
and 0.003 part of di-n-butyltin diacetate were fully mixed together. The mixture was coated on a 50 micron nonwoven fabric of polypropylene and it was left to stand at a tem-perature of 80C for 16 hours in an argon gas atmosphere to form a sheet.
The sheet was dlpped in a 0.1 mol/1 n-hexane solution of n-butyl lithium in an argon gas atmosphere and was left therein for three hours. Then, it was transferred into a 0.02 wt.% n-hexane solution of methyl iodide and after one hour of immersion, it was washed with n-hexane and the n-hexane was thereafter removed by volatilization.
Then, the sheet was dipped in a 0.04 mol/l acetone solution of lithium perchlorate in a totally closed vessel and was left therein for 20 minutes, whereby lithium per-chlorate was dissolved in the sheet. Then, the paste of the active material forming thecathode,which had been pre-pared as herelnabove described, was coated on the upper surface of the sheet. The sheet was left to stand at a temperature of 80C for 16 hours in an argon gas atmosphere and was, then, dried at the same temperature for 48 hours in a vacuum. Then, the sheet was incorporated into a battery test cell, which will hereinafter be referred to as "CeIl I"
EX~MPLE 2 Two parts of dimethylacetamide, an equivalent amount of hexamethylene diisocyanate, 0.006 part of di-n-butyltin ~L3()~L~4~L
diacetate and two parts of methyl iodide were fully mixed in 11 parts of a solution of lithium perchlorate and poly-ether. The mixture was coated on a 50 micron nonwoven fabric of polypropylene and it was left to stand at a tem-perature of 80C for 16 hours in an argon gas atmosphere to form a sheet. The paste as hereinabove described was coated on the upper surface of the sheet. The sheet was left at a temperature of 80C for 16 hours in an argon sas atmosphere and was dried. Then, it was incorporated into a battery test cell, which will hereinafter be referred to as "Cell II".
Five parts of a dry polyether, one part of dimethyl-acetamide, an e~uivalent amount of hexamethylene diisocyanate and 0.003 part of di-n-butyltin diacetate were fully mixed together. The mixture was coated on a 50 micron nonwoven fabric of polypropylene and it was left at a temperature of 80C for 16 hours in an argon gas atmosphere to form a sheet.
The sheet was dipped in a 0.1 mol/l n~-hexane solution of n-butyl lithium in an argon gas atmosphere and was left therein for three hours. Then, it was washed with n-hexane and the n-hexane was removed by volatilization.
Then, the sheet was dipped in a 0.04 mol/l acetone solution of lithium perGhlorate in a totally closed vessel and was left therein for 20 minutes, whereby lithium per-chlorate was diss~olved in the sheet. The paste as herein-' ~
~L3044~L
above described was coated on the upper surface of the sheet. The sheet was left to stand at a temperature of 80C for 16 hours in an argon gas atmosphere and was dried at the same temperature for 48 hours in a vacuum. It was incorporated into a battery test cell, which will herein-after be referred to as "Cell III".
Five parts of a dry polyether, one part of dimethyl-acetamlde, an equivalent amount of hexamethylene diisocyanate and 0.003 part of di-n-butyltin diacetate were fully mixed toyether. The mixture was coated on a 50 micron nonwoven fabric of polypropylene and it was left to stand at a tempera-ture of 80C for 16 hours in an argon gas atmosphere to form a sheet. The sheet was dipped in a 0.1 mol/l n-hexane solu-tion of n-butyl lithium in an argon gas atmosphere and was left therein for three hours. Then, it was washed with n-hexane and the n-hexane was removed by volatilization. The sheet was, then, dipped in a 0.04 mol/l acetone solution of lithium perchlorate in a totally closed vessel and was left therein for 20 minutes, whereby lithium perchlorate was dissolved in the sheet.
Two parts of dimethylacetamide, an equivalent amount of hexamethylene diisocyanate and 0.006 part of di-n-butyltin diacetate were fully mixed in 11 parts of a solution of lithium perchlorate and poIyether. The mixture was applied to the . upper surface of the sheet to form a thin layer thereon and ~3~4~44 the sheet was left to stand at a temperature of 80C for 16 hours in an argon gas atmosphere.
The paste as hereinabove described was coated on the upper surface of the sheet. Then, the sheek was left to stand at a temperature of 80C for 16 hours in an argon gas atmosphere and was dried at the same temperature for 48 hours in a vacuum. It was incorporated into a battery test cell, which will hereinafter be referred to as "Cell IV".
A part of the hydroxyl groups in the same polyether as had been employed in the foregoing examples were esterified and neutralized with lithium chloride to form -So3Li groups.
The terminal -OH and -SO3Li groups in the polyether had a ratio of 9:1.
Lithium perchlorate was dissolved in the polyether by the method which had been employed in the foregoing examples. Two parts of dimethylacetamide, an equivalent amount of hexamethylene diisocyanate and 0.006 part of di-n-butyltin diacetate were fully mixed in ll parts of a solu-tion of lithium perchlorate and polyether. The mixture was coated on a 50 micron nonwoven fabric of polypropylene and it was left to stand at a temperature of 80C for 16 hours in an argon gas atmosphere to form a sheet. Then, the paste as hereinabove described was coated on the upper surface of the sheet. The sheek was left to stand at a temperature of 80C for 16 hours in an argon gas atmosphere and was dried , :
, ~3~L44A
at the same temperature for 48 hours in a vacuum. It was incorporated into a battery test cell, which will hereinafter be referred to as "Cell V".
An equivalent amount of hexamethylene diisocyanate, 0.006 part of di-n butyltin diacetate, and a solution which had been prepared by dissolving 4 parts of a substance of the formula C12H25(CH2CH2O)4SO3Li in four parts of dimethyl-acetamide were fully mixed in 11 parts of a solution of lithium perchlorate and polyether. The mixture was coated on a 50 micron nonwoven fabric of polypropylene and it was left to stand at a temperature of 80C for 16 hours in an argon gas atmosphere to form a sheet. The paste as herein-above described was coated on the upper surface of the sheet and the sheet was left to stand at a temperature of 80C for 16 hours in an argon gas atmosphere. Then, the sheet was dried at the same temperature for 48 hours in a vacuum and was incorporated into a battery test cell, which will here-inafter be referred to as "Cell VI".
A comparati~e cell was prepared in accordance with the prior art. Two parts of dimethylacetamide, an equivalent amount of hexamethylene diisocyanate and 0.006 part of di- -n-butyltin diacetate were fully mixed in 11 parts of a solu-tion of lithium perchlorate and polyether The mixture was coated on a 50 micron nonwoven fabric of polypropylene and was left to stand at a temperature of 80C for 16 hours in ~:
~ ::
130~44 an argon gas atmosphere to form a sheet. The paste as hereinbefore described was coated on the upper surface of the sheet and the sheet was left to stand at a temperature of 80C for 16 hours in an argon gas atmosphere. Then, it was dried at the same temperature for 48 hours in a vacuum and was incorporated into a battery test cell, which will hereinafter ~e referred to as "Cell VII".
Thirty cells of each of the seven types I to VII
were prepared and were tested for their variation of capacity during storage and their charging and discharging cycle life.
Twenty cells of each type were tested for variation of capacity during storage. They were placed in a thermo-static oven of the recirculation type having a temperature of 80C. Five cells were taken out of the oven and tested upon lapse of each of 0, 7.5, 15, and 30 days. The test was conducted by a constant current discharge of 13 ~
(10 ~A/cm2) at a temperature of 80C until a final discharg-ing voltage of 2 V was reached. The results are shown in FIGURE 2.
Ten cells of each type were tested for their cycle life. They were placed in a thermostatic oven of the re-circulation type having a temperature of 80C and were caused to discharge a current of 52 ~A (40 ~/c~ ), while they were charged with a current of 26 ~A (20/uA/cm2), until a final discharging voltage of 2.0 V and a final charging voltage of 4.0 V were reached. The results are shown in , : ~
13~
FIGURE 3 .
The results shown in FIGURES 2 and 3 confirm that the batteries of this invention are superior to the conven-tional one.
As is obvious from the foregoing description, this lnvention provides a polymer solid electrolyte which can be stored for a long time without suffering from any reduction of quality, and a battery which does not lower its perform-ance for a long time. It also provides a polymer solid electrolyte battery which can be charged and discharged for a large number of times repeatedly without having any sub-stantial reduction of capacity.
: ~ - 19 -. .
' '
Claims (11)
1. In a polymer solid electrolyte comprising a cross-linked polyether, the improvement wherein said crosslinked polyether has a structure of the formula:
where R stands for -CnH2n+1 or -COCnH2n+1, n?1.
where R stands for -CnH2n+1 or -COCnH2n+1, n?1.
2. A polymer solid electrolyte battery comprising a positive electrode, a negative electrode, and a polymer solid electrolyte comprising a crosslinked polyether having a crosslinked structure of the formula:
where R stands for -CnH2n+1 or -COCnH2n+1, n?1.
where R stands for -CnH2n+1 or -COCnH2n+1, n?1.
3. A polymer solid electrolyte comprising a polyether crosslinked with a urethane bond, the improvement which contains a substance which can replace an active hydrogen atom in said urethane bond with -C2H2n+1 or -COCnH2n+1, n?1.
4. A polymer solid electrolyte battery comprising a positive electrode, a negative electrode, and a polymer solid electrolyte comprising a polyether crosslinked with a urethane bond, said electrolyte containing a substance which can replace an active hydrogen atom in said urethane bond with -C2H2n+1 or -COCnH2n+1, n?1.
5. In a polymer solid electrolyte comprising a cross-linked polyether, the improvement wherein said crosslinked polyether has a crosslinked structure of the formula:
where M stands for an element of Group I of the periodic table other than a hydrogen atom.
where M stands for an element of Group I of the periodic table other than a hydrogen atom.
6. A polymer solid electrolyte battery comprising a positive electrode, a negative electrode, and a polymer solid electrolyte comprising a crosslinked polyether having a crosslinked structure of the formula:
where M stands for an element of Group I of the periodic table other than a hydrogen atom.
where M stands for an element of Group I of the periodic table other than a hydrogen atom.
7. In a polymer solid electrolyte comprising a cross-linked polyether in which a salt is dissolved, the improve-ment wherein said crosslinked polyether contains at least one group selected from among -SO3M', -COOM', -Po(OM')2 and -PH(O)(OM'), where M' stands for an element of Group I of the periodic table.
8. A polymer solid electrolyte battery comprising a positive electrode, a negative electrode, and a polymer solid electrolyte comprising a crosslinked polyether in which a salt is dissolved, and which contains at least one group selected from among -SO3M', -COOM', -PO(OM')2 and -PH(O)(OM'), where M' stands for an element of Group I
of the periodic table.
of the periodic table.
9. In a battery including a polymer solid electrolyte comprising a crosslinked polyether having a crosslinked structure of the formula:
where M stands for an element of Group I of the periodic table other than a hydrogen atom, the improvement wherein said electrolyte is employed only in the vicinity of a negative electrode.
where M stands for an element of Group I of the periodic table other than a hydrogen atom, the improvement wherein said electrolyte is employed only in the vicinity of a negative electrode.
10. In a polymer solid electrolyte comprising a cross-linked polyether in which an inorganic salt is dissolved, the improvement which contains 0.5 to 10 mols, per mol of said inorganic salt, of a substance containing at least one group selected from among -SO3M', -COOM', -PO(OM')2 and -PH(O)(OM'), where M' stands for an element of Group I of the periodic table, and having a large molecular shape.
11. A polymer solid electrolyte battery comprising a positive electrode, a negatice electrode, and a polymer solid electrolyte comprising a crosslinked polyether in which an inorganic salt is dissolved, and further containing 0.5 to 10 mols, per mol of said inorganic salt, of a substance con-taining at least one group selected from among -SO3M', -COOM', -PO(OM')2 and -PH(O)(OM'), where M' stands for an element of Group I of the periodic table, and having a large molecular shape.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP165008/62 | 1987-06-30 | ||
| JP16500887A JPS6410503A (en) | 1987-06-30 | 1987-06-30 | Polymer solid electrolyte and cell using it |
| JP63021606A JPH01197974A (en) | 1988-02-01 | 1988-02-01 | Polymer solid electrolyte and polymer solid electrolyte cell |
| JP21606/63 | 1988-02-01 | ||
| JP63052933A JPH01227365A (en) | 1988-03-07 | 1988-03-07 | Polymer solid electrolyte and polymer solid electrolyte battery |
| JP52933/63 | 1988-03-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1304444C true CA1304444C (en) | 1992-06-30 |
Family
ID=27283489
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000567941A Expired - Lifetime CA1304444C (en) | 1987-06-30 | 1988-05-27 | Polymer solid electrolyte and a polymer solid electrolyte battery |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4844995A (en) |
| EP (2) | EP0297717B1 (en) |
| CA (1) | CA1304444C (en) |
| DE (1) | DE3852152T2 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4952466A (en) * | 1987-01-16 | 1990-08-28 | The Dow Chemical Company | Solid electrolyte battery |
| DE3920129A1 (en) * | 1988-06-21 | 1989-12-28 | Ricoh Kk | ELECTROCHEMICAL DEVICE |
| US5006431A (en) * | 1989-02-23 | 1991-04-09 | Hope Henry F | Solid state polymer electrolyte for batteries |
| US5016991A (en) * | 1989-03-27 | 1991-05-21 | Ford Motor Company | Flexible, solid electrolyte useful in electrochromic devices |
| US5786110A (en) * | 1992-06-22 | 1998-07-28 | Arizona Board Of Regents | Alkali-metal-ion conducting electrolytes |
| US5453335A (en) * | 1992-12-23 | 1995-09-26 | Arthur D Little, Inc. | Ion-conductive polymer and electrolyte additives |
| US5409786A (en) * | 1993-02-05 | 1995-04-25 | Eveready Battery Company, Inc. | Inactive electrochemical cell having an ionically nonconductive polymeric composition activated by electrolyte salt solution |
| US5482795A (en) * | 1994-05-25 | 1996-01-09 | Chaloner-Gill; Benjamin | Solid electrolyte utilizing a polymeric matrix obtained by the polymerization of a substituted allylic chloroformate |
| US6514640B1 (en) * | 1996-04-23 | 2003-02-04 | Board Of Regents, The University Of Texas System | Cathode materials for secondary (rechargeable) lithium batteries |
| US6562520B1 (en) * | 1999-11-22 | 2003-05-13 | Hitachi Maxell, Ltd. | Polymer electrolyte and rechargeable cell comprising the same |
| WO2001073883A2 (en) * | 2000-03-24 | 2001-10-04 | Cymbet Corporation | Low-temperature fabrication of thin-film energy-storage devices |
| USD569054S1 (en) * | 2004-10-01 | 2008-05-13 | Ecoguard Systems Ltd. | Apparatus for removing deposits from underwater structures |
| WO2013062997A1 (en) | 2011-10-28 | 2013-05-02 | Lubrizol Advanced Materials, Inc. | Polyurethane-based electrode binder compositions and electrodes thereof for electrochemical cells |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1116759A (en) * | 1952-01-03 | 1956-05-11 | Bayer Ag | Process for the production of modified polyureas |
| US3551711A (en) * | 1969-01-21 | 1970-12-29 | Hermetic Coil Co Inc | Encapsulated electric motor having p-m rotor and claw tooth station |
| US4118354A (en) * | 1972-11-24 | 1978-10-03 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Polyurethane hydrogel and method for the production of the same |
| IE51643B1 (en) * | 1980-10-15 | 1987-01-21 | Smith & Nephew Ass | Coated articles and materials suitable for coating |
| DE3277830D1 (en) * | 1981-11-03 | 1988-01-21 | Comp Generale Electricite | Process for manufacturing a polymeric solid electrolyte for an electrochemical generator |
| GB2119162B (en) * | 1982-04-16 | 1985-11-20 | Atomic Energy Authority Uk | Solid state electrochemical cell |
| FR2557735B1 (en) * | 1984-01-02 | 1986-04-25 | Elf Aquitaine | NOVEL MACROMOLECULAR MATERIAL WITH ION CONDUCTION AND MANUFACTURING METHOD THEREOF |
| GB2164047B (en) * | 1984-08-21 | 1989-05-24 | Secr Defence | Polymeric electrolytes |
| US4618630A (en) * | 1984-08-27 | 1986-10-21 | The Dow Chemical Co. | Organic polymer composition containing an antistatic agent comprising a nonvolatile ionizable metal salt and a salt or ester of a carboxylic acid |
| EP0213985B1 (en) * | 1985-07-12 | 1989-09-13 | Societe Nationale Elf Aquitaine | Macromolecular material with ion conductivity |
| US4654279A (en) * | 1986-07-10 | 1987-03-31 | The United States Of America As Represented By The Secretary Of The Navy | Interpenetrating-network polymeric electrolytes |
-
1988
- 1988-05-23 EP EP88304649A patent/EP0297717B1/en not_active Expired - Lifetime
- 1988-05-23 EP EP93201935A patent/EP0572099A3/en not_active Withdrawn
- 1988-05-23 DE DE3852152T patent/DE3852152T2/en not_active Expired - Fee Related
- 1988-05-24 US US07/197,968 patent/US4844995A/en not_active Expired - Lifetime
- 1988-05-27 CA CA000567941A patent/CA1304444C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| EP0297717A3 (en) | 1991-07-24 |
| EP0297717B1 (en) | 1994-11-23 |
| US4844995A (en) | 1989-07-04 |
| EP0572099A2 (en) | 1993-12-01 |
| EP0572099A3 (en) | 1996-04-24 |
| EP0297717A2 (en) | 1989-01-04 |
| DE3852152T2 (en) | 1995-04-06 |
| DE3852152D1 (en) | 1995-01-05 |
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