CA2115654C - Ionically conductive polymer gels - Google Patents
Ionically conductive polymer gels Download PDFInfo
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- CA2115654C CA2115654C CA002115654A CA2115654A CA2115654C CA 2115654 C CA2115654 C CA 2115654C CA 002115654 A CA002115654 A CA 002115654A CA 2115654 A CA2115654 A CA 2115654A CA 2115654 C CA2115654 C CA 2115654C
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/168—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/164—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solvent
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
- H01M6/181—Cells with non-aqueous electrolyte with solid electrolyte with polymeric electrolytes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/22—Immobilising of electrolyte
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Abstract
A bulk ionically conductive polymer gel is prepared by dissolving a salt such as lithium trifluoromethanesulphonate (which would provide lithium ion conductors) in an organic compound such as N-formylpiperidine. The organic compound dissolves the salt at 20 °C but is not a solvent at 20 °C (though it is at 215 °C) for polyethylene terephthalate. The last-named is a crystallisable polymer which is added in a minor amount at a high temperature to the other components and provides the required mechanical rigidity for the product at lower temperatures.
Description
W0 93/07626 ~ ~ ~ ~ ~ ~ ~ PCf/GB92/01781 IONICALLY CONDUCTIVE POLYMER GELS
This invention relates to bulk sonically conductive polymer gels and their preparation, and to galvanic cells containing'~them.
The most commonly used electrolytes are fluid liquids which comprise solutions in a liquid solvent of solute ionic species.
Such fluid liquid electrolytes, on incorporation into a galvanic cell, permit migration of ions between the electrodes of the cell and, as a consequence, the provision of electric free energy to a closed external circuit. Despite their widespread use, such electrolytes nonetheless suffer from several disadvantages.
Thus, they are often corrosive, leading to leakage from cells and they do not provide a firm barrier between the electrodes when required to assist in stabilising the inter-electrode distance and in preventing physical loss of electrode material from the electrode surface.
In order, in part, to overcome the disadvantages inherent in fluid liquid electrolytes, particularly in relation to galvanic cells, cohsiderable effort has been expended in attempts to prov de solid or highly viscous polymeiric electrolytes which contain salts which display mobility, under appropriate conditions, of at least some of the ionic species present. The soitd polymeric electrolytes are capable of acting in thin film form as electrode separators and in solid-state cells can deform while maintaining good contact with the electrodes, thus minimising problems arising from mechanical strain arising either from mechanical stresses during use or volume changes during the charge/discharge cycle. A particular area of importance is in cells that do not depend upon water as a component of the electrolyte, such as lithium cells where water and other materials capable of reacting with lithium are undesirable. The potential uses for such materials are not limited to batteries but include, inter else, sensor devices and thermoelectric energy convectors.
2ms~4 -z-A prominent polymeric material for this purpose has been polyethylene oxide) (PEO), in which certain salts are soluble and can form complexes. The electrical and mechanical properties of such polymer electrolyte materials, although encouraging, require further enhancement before commercialisation cap be , envisaged. Improvements in the properties have been obtained using graft copolymers in which short polyethylene oxide) chains are present as pendant units attached to a long main chain. Such materials have been described in GB-A-2161488. Another means of improving the mechanical properties is to use block copolymers in which short polyethylene oxide) chains alternate with other units such as polysiloxane. Yet another means is to cross-link a polyethylene oxide) with an epoxy compound. In each case the polymer electrolyte contains a suitable salt complexed with the polymer to provide the ionic species required for conductivity.
In all these cases the conductivities reported at 25°C or at room temperature are at best about 10'4 Siemens per cm. These values are an order of magnitude less than a commonly cited target for commercial realisation of 10-3 Siemens per cm.
It is also possible to provide polymer electrolytes which consist of a mixture of a polymer, preferably of high molecular weight, with a compound of low molecular weight that is a solvent for the polymer in the range of temperatures in which the electrolyte is to .be used, together with an appropriate salt that is soluble in the polymer and in the compound of low molecular weight. For example, as disclosed in GB-A-2212504 and 2216132, polymer electrolytes consisting of poly-N,N-dimethylacrylamide or closely related poly-N-substituted acrylamide of high molecular weight plasticised with dimethylacetamide together with lithium trifluoromethane sulphonate (lithium triflate) as the salt component have been evaluated and found to exhibit good conductivities together with good mechanical properties. These polymer electrolytes are get-like in character, but the compound of low molecular weight must not exceed a certain limiting concentration above which the system loses its gel-like character and begins to flow. The ionic conductivity is higher at the higher concentrations of the compound of low molecular weight, but the material becomes increasingly more flexible. Conductivities of 7 x 10-3Scm-1 at 20°C are obtainable but this requires at least 60% or more of the low molecular weight compound and at this level the mechanical properties are poor. It has proved possible by cross-linking the polymer to improve the mechanical properties to a useful level with as much as 80% of the low molecular weight compound present, and thus to obtain conductivities at 20°C exceeding 10-3Scm-1. These products may prove of commercial interest, but the process for making the cross-linked polymer electrolyte film is somewhat complex for convenient incorporation into a process for cell manufacture.
This invention seeks to provide sonically conductive materials that provide high bulk ionic conductivities at ambient temperature together with good mechanical properties.
According to one aspect of the invention there is provided an sonically conductive ion-containing gel consisting of (s) from 20 to 40% by mass of a polymer and (ii) from 60 to 80% by mass of an organic compound, or mixture of organic compounds, that is not a solvent for the polymer at 20°C, and a salt soluble in the said compound or mixture of compounds at 20°C and dissolved therein at a concentration greater than 4% by mass based on said compound or mixture characterised in that the polymer is a crystallisable polymer selected from the group consisting of crystallisable polyesters, polyamides, polyethers and halo-substituted polyolefins and the gel has a bulk ionic 3a conductivity at 20°C and lOkHz greater than 10-4Siemens/cm and a dynamic modulus at lOHz greater than 104Pa.
Thus the gel consists of a minor amount of a crystallisable polymer such as a polyester, a major amount of an organic compound that is a solvent for a salt at 20°C
but is not a solvent for the crystallisable polymer at 20°C, and a salt dissolved in the organic compound at a concentration greater than 4% by mass based on the organic compound. The gel preferably has a dynamic modulus at lOHz greater than 105Pa and the said minor amount is typically 20-30%.
The ion-containing gels of this invention can provide better ionic conductivities both at ambient and elevated temperatures than polymer electrolytes based on polymer-salt complexes previously described and better mechanical properties than WO 93/0?626 PGT/GB92/O1?81 ': ~"' 21156~~
polymer electrolytes of good ionic conductivity based on polymer-salt-plasticising solvent complexes previously described.
The ion-containing gels of this invention can normally be regarded as thermoreversible gels in which the functions are physical associations, possibly corresponding with ci=ystal structures comprising only a small portion of the polymer chains.
The crystallisable polymer may itself be capable of complexing with the salt through containing, for example, ether or amide groups, but it is not essential that the crystallisable polymer should dissolve or complex with the salt. This contrasts with previously described ion-conducting electrolyte systems based upon polymers where it has been essential that the polymer should dissolve or complex the salt and desirable that the polymer should be non-crystallisable.
Suitable crystallisable polymers for use in this invention include crystallisable polyesters such as polyethylene terephthalate), poly(1,4-butylene terephthalate) and poly(3-oxybutanoate), crystailisable polyamides such as poly(hexa-methylene adipamide) and poly(Ln-phenylene isophthalamide), crystallisable polyethers and crystallisable substituted (e. g.
halo) polyolefins such as substituted polyvinylidenes. Further examples include polyhydroxybutyric acid, poly(metaxylylene adipamide), poly(vinylidene fluoride), polyoxymethylene and polyoxyethylene. The crystallisable polymer is normally dissolved at a high temperature in the other components and can provide the required mechanical rigidity for the product at lower temperatures. If inadequate crystallisable polymer is present, the mechanical properties and dimensional stability will suffer.
The crystallisable polymer is preferably of a sufficiently high molecular weight to form coherent films and fibres. In general, the higher the molecular weight of the polymer, the better the mechanical properties of the gel structure formed and the lower 21~~s~~
the concentration of the polymer required to maintain a gel structure, and the lower the concentration of polymer, the higher the conductivity.
Suitable organic compounds that are solvents for a salt at 20°C but are not solvents for the crystal l l sable polymer at -20°C
include amides (preferably tertiary amides) which may be cyclic such as dimethyl formamide, dimethyl acetamide, N-methyl-2-pyrrolidinone and N-formyi piperidine, sulphoxides and ethers (preferably polyfunctional) such as the dimethyl ethers of diethylene glycol, triethylene glycol and tetraethylene- glycol.
Mixtures of such compounds may also be used. Where its more modest oxidation-reduction stability is adequate, the solvent organic compound may be dimethyl sulphoxide. It wilt.. be understood that these compounds do become solvents for the crystallisable polymer at some temperature above 20°C, e.g: above 100°C or above 150°C. For use in batteries it is preferable that the organic compounds should be free from chemical groups that can react with electrode components. Thus for lithium batteries the organic compounds should not contain hydroxyl groups and should be as free of water as possible.
Suitable salts include alkali metal salts such as salts of lithium, sodium or potassium and substituted or unsubstituted ammonium. Lithium is particularly preferred because of the high solubility of many lithium salts in suitable organic compounds and the importance of lithium as an electrode material. The counterbalancing anion is preferably large and preferably a weak conjugate base. Examples include the aanovalent anions derived from higher halogens and pseudohalogens, for example Br-, I' and SCN- and complex inorganic, carboxylic and sulphonic, preferably perfluorinated alkyl carboxylic and sulphonic, monovalent anions, for example C104 , HgI3 , 8F4 , CF3C00-, and CF3S03'. The concentration of salt based in the organic compound should be greater than 4X by wei ght and l s 1 l ml ted at the upper end of the range by a saturation solubility of the salt in the organic WO 93/07626 ' PCT/GB92/01781 compound in the presence of the polymer. The salt is preferably present in the gel structure at a concentration such that it does not exceed its saturation solubility throughout the proposed temperature range of use. Hence, for each combination of organic compound and salt and intended temperature there is an optimum concentration of salt for the highest conductivities to be obtained.
Gels according to this invention may be prepared by forming a solution of the polymer in the organic compound at above 20°C
(preferably above 100°C such as above 150°C), incorporating the salt into the solution either by addition after it has been formed or simultaneously or preferably by solution in the organic compound before the addition of the polymer, then cooling the sol ution. Such cool i ng wi 11 be understood to be to a temperature below the critical solution temperature of the polymer in the mixture of the organic compound and the salt.
The present invention also provides a galvanic cell wherein the electrolyte comprises an sonically conductive gel as herein defined; and a battery of such cells.
~(AMPI.ES
The following Examples illustrate the invention.
TEST METHODS
CELL PREPARATION AND MEASUREMENT Of IONIC OONOUCTIVITY
Gel samples were re-heated~until they melted and then cast on to a stainless steel (ion-blocking) electrode. A second stainless steel electrode was rapidly brought into contact with the gel so that the gei was sandwiched between the electrodes and good contact with both electrodes was achieved. The contact area A and electrolyte thickness t were accurately known; in all cases A was 1.0 cm2 and t was in the range 0.86-1.69mm.
This invention relates to bulk sonically conductive polymer gels and their preparation, and to galvanic cells containing'~them.
The most commonly used electrolytes are fluid liquids which comprise solutions in a liquid solvent of solute ionic species.
Such fluid liquid electrolytes, on incorporation into a galvanic cell, permit migration of ions between the electrodes of the cell and, as a consequence, the provision of electric free energy to a closed external circuit. Despite their widespread use, such electrolytes nonetheless suffer from several disadvantages.
Thus, they are often corrosive, leading to leakage from cells and they do not provide a firm barrier between the electrodes when required to assist in stabilising the inter-electrode distance and in preventing physical loss of electrode material from the electrode surface.
In order, in part, to overcome the disadvantages inherent in fluid liquid electrolytes, particularly in relation to galvanic cells, cohsiderable effort has been expended in attempts to prov de solid or highly viscous polymeiric electrolytes which contain salts which display mobility, under appropriate conditions, of at least some of the ionic species present. The soitd polymeric electrolytes are capable of acting in thin film form as electrode separators and in solid-state cells can deform while maintaining good contact with the electrodes, thus minimising problems arising from mechanical strain arising either from mechanical stresses during use or volume changes during the charge/discharge cycle. A particular area of importance is in cells that do not depend upon water as a component of the electrolyte, such as lithium cells where water and other materials capable of reacting with lithium are undesirable. The potential uses for such materials are not limited to batteries but include, inter else, sensor devices and thermoelectric energy convectors.
2ms~4 -z-A prominent polymeric material for this purpose has been polyethylene oxide) (PEO), in which certain salts are soluble and can form complexes. The electrical and mechanical properties of such polymer electrolyte materials, although encouraging, require further enhancement before commercialisation cap be , envisaged. Improvements in the properties have been obtained using graft copolymers in which short polyethylene oxide) chains are present as pendant units attached to a long main chain. Such materials have been described in GB-A-2161488. Another means of improving the mechanical properties is to use block copolymers in which short polyethylene oxide) chains alternate with other units such as polysiloxane. Yet another means is to cross-link a polyethylene oxide) with an epoxy compound. In each case the polymer electrolyte contains a suitable salt complexed with the polymer to provide the ionic species required for conductivity.
In all these cases the conductivities reported at 25°C or at room temperature are at best about 10'4 Siemens per cm. These values are an order of magnitude less than a commonly cited target for commercial realisation of 10-3 Siemens per cm.
It is also possible to provide polymer electrolytes which consist of a mixture of a polymer, preferably of high molecular weight, with a compound of low molecular weight that is a solvent for the polymer in the range of temperatures in which the electrolyte is to .be used, together with an appropriate salt that is soluble in the polymer and in the compound of low molecular weight. For example, as disclosed in GB-A-2212504 and 2216132, polymer electrolytes consisting of poly-N,N-dimethylacrylamide or closely related poly-N-substituted acrylamide of high molecular weight plasticised with dimethylacetamide together with lithium trifluoromethane sulphonate (lithium triflate) as the salt component have been evaluated and found to exhibit good conductivities together with good mechanical properties. These polymer electrolytes are get-like in character, but the compound of low molecular weight must not exceed a certain limiting concentration above which the system loses its gel-like character and begins to flow. The ionic conductivity is higher at the higher concentrations of the compound of low molecular weight, but the material becomes increasingly more flexible. Conductivities of 7 x 10-3Scm-1 at 20°C are obtainable but this requires at least 60% or more of the low molecular weight compound and at this level the mechanical properties are poor. It has proved possible by cross-linking the polymer to improve the mechanical properties to a useful level with as much as 80% of the low molecular weight compound present, and thus to obtain conductivities at 20°C exceeding 10-3Scm-1. These products may prove of commercial interest, but the process for making the cross-linked polymer electrolyte film is somewhat complex for convenient incorporation into a process for cell manufacture.
This invention seeks to provide sonically conductive materials that provide high bulk ionic conductivities at ambient temperature together with good mechanical properties.
According to one aspect of the invention there is provided an sonically conductive ion-containing gel consisting of (s) from 20 to 40% by mass of a polymer and (ii) from 60 to 80% by mass of an organic compound, or mixture of organic compounds, that is not a solvent for the polymer at 20°C, and a salt soluble in the said compound or mixture of compounds at 20°C and dissolved therein at a concentration greater than 4% by mass based on said compound or mixture characterised in that the polymer is a crystallisable polymer selected from the group consisting of crystallisable polyesters, polyamides, polyethers and halo-substituted polyolefins and the gel has a bulk ionic 3a conductivity at 20°C and lOkHz greater than 10-4Siemens/cm and a dynamic modulus at lOHz greater than 104Pa.
Thus the gel consists of a minor amount of a crystallisable polymer such as a polyester, a major amount of an organic compound that is a solvent for a salt at 20°C
but is not a solvent for the crystallisable polymer at 20°C, and a salt dissolved in the organic compound at a concentration greater than 4% by mass based on the organic compound. The gel preferably has a dynamic modulus at lOHz greater than 105Pa and the said minor amount is typically 20-30%.
The ion-containing gels of this invention can provide better ionic conductivities both at ambient and elevated temperatures than polymer electrolytes based on polymer-salt complexes previously described and better mechanical properties than WO 93/0?626 PGT/GB92/O1?81 ': ~"' 21156~~
polymer electrolytes of good ionic conductivity based on polymer-salt-plasticising solvent complexes previously described.
The ion-containing gels of this invention can normally be regarded as thermoreversible gels in which the functions are physical associations, possibly corresponding with ci=ystal structures comprising only a small portion of the polymer chains.
The crystallisable polymer may itself be capable of complexing with the salt through containing, for example, ether or amide groups, but it is not essential that the crystallisable polymer should dissolve or complex with the salt. This contrasts with previously described ion-conducting electrolyte systems based upon polymers where it has been essential that the polymer should dissolve or complex the salt and desirable that the polymer should be non-crystallisable.
Suitable crystallisable polymers for use in this invention include crystallisable polyesters such as polyethylene terephthalate), poly(1,4-butylene terephthalate) and poly(3-oxybutanoate), crystailisable polyamides such as poly(hexa-methylene adipamide) and poly(Ln-phenylene isophthalamide), crystallisable polyethers and crystallisable substituted (e. g.
halo) polyolefins such as substituted polyvinylidenes. Further examples include polyhydroxybutyric acid, poly(metaxylylene adipamide), poly(vinylidene fluoride), polyoxymethylene and polyoxyethylene. The crystallisable polymer is normally dissolved at a high temperature in the other components and can provide the required mechanical rigidity for the product at lower temperatures. If inadequate crystallisable polymer is present, the mechanical properties and dimensional stability will suffer.
The crystallisable polymer is preferably of a sufficiently high molecular weight to form coherent films and fibres. In general, the higher the molecular weight of the polymer, the better the mechanical properties of the gel structure formed and the lower 21~~s~~
the concentration of the polymer required to maintain a gel structure, and the lower the concentration of polymer, the higher the conductivity.
Suitable organic compounds that are solvents for a salt at 20°C but are not solvents for the crystal l l sable polymer at -20°C
include amides (preferably tertiary amides) which may be cyclic such as dimethyl formamide, dimethyl acetamide, N-methyl-2-pyrrolidinone and N-formyi piperidine, sulphoxides and ethers (preferably polyfunctional) such as the dimethyl ethers of diethylene glycol, triethylene glycol and tetraethylene- glycol.
Mixtures of such compounds may also be used. Where its more modest oxidation-reduction stability is adequate, the solvent organic compound may be dimethyl sulphoxide. It wilt.. be understood that these compounds do become solvents for the crystallisable polymer at some temperature above 20°C, e.g: above 100°C or above 150°C. For use in batteries it is preferable that the organic compounds should be free from chemical groups that can react with electrode components. Thus for lithium batteries the organic compounds should not contain hydroxyl groups and should be as free of water as possible.
Suitable salts include alkali metal salts such as salts of lithium, sodium or potassium and substituted or unsubstituted ammonium. Lithium is particularly preferred because of the high solubility of many lithium salts in suitable organic compounds and the importance of lithium as an electrode material. The counterbalancing anion is preferably large and preferably a weak conjugate base. Examples include the aanovalent anions derived from higher halogens and pseudohalogens, for example Br-, I' and SCN- and complex inorganic, carboxylic and sulphonic, preferably perfluorinated alkyl carboxylic and sulphonic, monovalent anions, for example C104 , HgI3 , 8F4 , CF3C00-, and CF3S03'. The concentration of salt based in the organic compound should be greater than 4X by wei ght and l s 1 l ml ted at the upper end of the range by a saturation solubility of the salt in the organic WO 93/07626 ' PCT/GB92/01781 compound in the presence of the polymer. The salt is preferably present in the gel structure at a concentration such that it does not exceed its saturation solubility throughout the proposed temperature range of use. Hence, for each combination of organic compound and salt and intended temperature there is an optimum concentration of salt for the highest conductivities to be obtained.
Gels according to this invention may be prepared by forming a solution of the polymer in the organic compound at above 20°C
(preferably above 100°C such as above 150°C), incorporating the salt into the solution either by addition after it has been formed or simultaneously or preferably by solution in the organic compound before the addition of the polymer, then cooling the sol ution. Such cool i ng wi 11 be understood to be to a temperature below the critical solution temperature of the polymer in the mixture of the organic compound and the salt.
The present invention also provides a galvanic cell wherein the electrolyte comprises an sonically conductive gel as herein defined; and a battery of such cells.
~(AMPI.ES
The following Examples illustrate the invention.
TEST METHODS
CELL PREPARATION AND MEASUREMENT Of IONIC OONOUCTIVITY
Gel samples were re-heated~until they melted and then cast on to a stainless steel (ion-blocking) electrode. A second stainless steel electrode was rapidly brought into contact with the gel so that the gei was sandwiched between the electrodes and good contact with both electrodes was achieved. The contact area A and electrolyte thickness t were accurately known; in all cases A was 1.0 cm2 and t was in the range 0.86-1.69mm.
2 ~ 1 ~ s ~ ~ PGT/GB92/01781 _7_ The prepared cell was then immediately transferred to the chamber in which the conductivity measurements were carried out, which was flooded with dry nitrogen to present exposure of the cell to the atmosphere. Brass plates were used to provide electrical contact with both electrodes. The temperature of the sample was controlled by passing the dry nitrogen over a heat exchanger before it entered the chamber; a thermocouple positioned near to the cell was used to monitor the temperature, which was controlled by a Eurotherm temperature control upit.
A Solartron 1250 frequency response analyser and latterly a Schlumberger X260 impedance/gain-phase analyser were used to measure the complex admittance of the cell in the frequency range 0.1 Hz to 63 kHz. Due to the blocking nature of the electrodes, the real part of the admittance rose with frequency to a plateau.
The bulk gel electrolyte resistance Rb was calculated from the frequency-independent plateau observed in the real part of the admittance at frequencies above around 10 kHz. The ionic conductivity o was then calculated from the expression 1 t a = - x -Rb A
Measurement of Gel Modulus Gel electrolytes were cast into discs of diameter 25 mm and thickness approximately 2 mm (s0.3nm). These discs were placed between parallel circular disc platens of 25 mm diameter in a Rheometrics Dynamic Spectrometer RDS2, at ambient temperature (18°C to 23°C) in a nitrogen atmosphere, and squeezed under an axial load up to 1 kg to the measurement thickness H.
WO 93/07626 . . PGT/CB92/017$1 .
_$_ Two mechanical measurements were made:
1> Dynamic Modules Gl One of the disc platens oscillates sinusoidally about~~--its cylindrical axis of symmetry with an applied shear strain amplitude. Shear strain is measured at the circumference, or maximum radius R, using the maximum sine wave (zero to peak) angular displacement e, such that Strai n = ~
The in-phase component of the measured .sinusoidal shear stress is used to determine the dynamic modules Gl. First, therefore, stress is obtained from the torque or couple measured at the opposite platen using the formula:
toraue x 2000 x 98.07 tPa) Stress =
,r x R3 (with torque in gram centimetres). Then stress x cos8 Gl = strain where d is the phase lag between the stress and strain sine waves.
G~ was measured for frequencies between 0.016 Hz and 79.6 Hz.
Values of Gl away increase slightly with frequency and are quoted for 1X shear strain and 1O Hz frequency.
2) Relaxation Modules G(t) Using the same geometry, a step shear strain of 1X is applied. The stress then decays from its maximum as a function of time.
WO 93/07626 211 ~ ~ ~ 4 P~lGB92/01781 _ g _ step strain s ~
where ~ is a fixed angular displacement.
The relaxation modulus is then given by G(t) ~ Stress step strain where stress is the same as above.
_ The modulus G(t) is stated for lx strain after a relaxation time of 100 seconds.
xam~le 1 - PET-NMP
N-Methyl-2-pyrrolidinone (NMF) eras dried over a molecular sieve. Lithium trifluorc~methanesulphonate CF3S03Li (lithium triflate) was dried over phosphorous pentoxide for 48h.
Polyethylene terephthalate)(:PET) chips, of intrinsic viscosity 0.96 d1/g (17G in dichloroacetic acid at 25°C) were dried at 120C°
for 4h under reduced pressure'.
To 9.0g of molecular-sieve-dried N-methyl-2-pyrrolidihone were added 1.0g of dried polyethylene terephthalate) chips and 1.18g dried l thium triflate, all in a dried glass sample tube.
The tube was sealed and transferred to a silscone oft both at 200°C. The contehts were stirred intermittently and heated until the chips dissolved 'compsetely~ which occurred at a bath temperature of about 215°C. The solution was then allowed to 35, cool to room temperature. During cooling, the solution ceased to flow and solidified to a gel.
The gel was reheated until it flowed and was then cast under dry conditions in lsquid form on to one of the electrodes of the frequency response analyser System. It was sandwiched between WO 93/07626 . PGT/GB92/01781 -10_ the two electrodes and allowed to cool in situ to re-form the gel structure which was a flexible film with good recovery from deformat i on .
A series of conductivity measurements was carried out over a range of temperatures, and the results are shown graphicaTty in Figure 1. The conductivity at 25°C was found to be 10-3~2 Siemens per centimetre.
Exan»le 2 - PET-1FP
Example 1 was repeated using 1-formylpiperidine <1FP> instead of N-methyl-2-pyrrolidinone and 1.03g of lithium triflate instead of 1.18g. The conductivities over a range of temperature are shown graphically in Figure 1. The conductivity at 25°C was found to be 10-3~5 Siemer~s per centimetre.
Dynamic mechanical measurements were performed on several shaped samples prepared according to Examples 1 and 2 using both parallel plates and cone-and-plate sample holders. The samples were sub3ect to an alternating shear strain and the resulting shear stress measured and correlated against the input strain.
The measured shear moduli were generally independent of frequency over the range 0.1 to 500 rad/s and the shear relaxation modulus was determined to be about 103Pa. The dynamic modulus of all these samples was found to exceed 103Pa at 10 Hz.
,.w The accompanying drawing shows the results from these two Examples on a log-conductivity/inverse temperature plot.
~g~nl es 3 -~ 11 The general procedure adopted was as follows:-Dry lithium triflate was dissolved in the dry solvent at room temperature in a sealed dry flask using the molar proportion WO 93/07626 ~ ~ ~ ~ ~ ~ ~ PGT/GB92/01781 required of lithium triflate to solvent. A measured volume of the solution was added to a measured weight of the polymer in a dry vessel and the mixture was heated, with mechanical stirring, by means of an oil bath pre-set at a temperature above 150°G
sufficient to cause the polymer to diSSOlve. The vessel was sealed and quenched to room temperature to cause gel formation.
The conductivity and modulus measurements were made using the procedures already described.
The polymers used for these Examples (and for Exampl-es 1 and 2) were obtained as follows:-Poly(ethylene terephthalate) (PET) was a bottle-grade polymer of (n~ 0.96, in pellet form.
Poly(vinylidene fluoride) (PVDF> was obtained from Polysciences Inc. irr pellet form. It had a weight average molecular weight, according to the suppliers, of 100,000.
Polyhydroxybutyric acid (PHBA) was obtained from Aldrich in powder form. It had a weight average molecular weight, according to the suppliers, of 670,000.
Poly(metaxylylene adipamide) (MXD,6> was Mitsubishi Grade 6001.
Nylon 6,6 was obtained from ICI in the form of granules, Type 86600.
Polyoxymethylene was obtained from Aldrich in the form of beads.
Results of the conductivity and modulus measurements for Examples 3-11 are given in Table 1. In this Table the abbreviations are as follows:
DMF dimethyl formamide DMSO dimethyl sulphoxide TGDME tetraethylene glycol dimethyl ether NMP N-methyl pyrrolidinone OMA dimethyl acetamide The values of Gl are measured at 1X strain amplitude and a WO 93/07626 . ' PCTlGB92/A1781 -lz-frequency of 10 Hz. The values of G(t> are measured 2 minutes after application of a strain of 1X. Both G1 and G(t) are measured at~ambient temperature.
.fable .._.
Example Solvent PolymerConduct-DynamicRelax-Polymer Mass X Li conc. ivity mqdulusan on at triflate wtX 20C G (Pa) modulus of based total S cm-1 G(t)Pa) on solvent gel 3 PVDF DMF 16.8 26.5 6.6x10-33x105 2x105 4 PVDF OMSO 18.3 23.8 4.6x10-32x105 1x105 5 PVDF TGDME5.9 27.2 2.0x10-41x105 7x104 6 PET NMP 13.5 27.2 2.0x10-32x105 1x105 7 PHBA DMA 14.0 13.4 3.6x10'33x105 -8 PHBA DMA 14.0 21.8 i.5x10w31x105 7x104 9 MXD,6 NMP 13.5 12.6 2.4x10- 2x105 1x105 10 Nylon 6,6 NMP 13.5 7.9 2.2x10-34x104 -~
A Solartron 1250 frequency response analyser and latterly a Schlumberger X260 impedance/gain-phase analyser were used to measure the complex admittance of the cell in the frequency range 0.1 Hz to 63 kHz. Due to the blocking nature of the electrodes, the real part of the admittance rose with frequency to a plateau.
The bulk gel electrolyte resistance Rb was calculated from the frequency-independent plateau observed in the real part of the admittance at frequencies above around 10 kHz. The ionic conductivity o was then calculated from the expression 1 t a = - x -Rb A
Measurement of Gel Modulus Gel electrolytes were cast into discs of diameter 25 mm and thickness approximately 2 mm (s0.3nm). These discs were placed between parallel circular disc platens of 25 mm diameter in a Rheometrics Dynamic Spectrometer RDS2, at ambient temperature (18°C to 23°C) in a nitrogen atmosphere, and squeezed under an axial load up to 1 kg to the measurement thickness H.
WO 93/07626 . . PGT/CB92/017$1 .
_$_ Two mechanical measurements were made:
1> Dynamic Modules Gl One of the disc platens oscillates sinusoidally about~~--its cylindrical axis of symmetry with an applied shear strain amplitude. Shear strain is measured at the circumference, or maximum radius R, using the maximum sine wave (zero to peak) angular displacement e, such that Strai n = ~
The in-phase component of the measured .sinusoidal shear stress is used to determine the dynamic modules Gl. First, therefore, stress is obtained from the torque or couple measured at the opposite platen using the formula:
toraue x 2000 x 98.07 tPa) Stress =
,r x R3 (with torque in gram centimetres). Then stress x cos8 Gl = strain where d is the phase lag between the stress and strain sine waves.
G~ was measured for frequencies between 0.016 Hz and 79.6 Hz.
Values of Gl away increase slightly with frequency and are quoted for 1X shear strain and 1O Hz frequency.
2) Relaxation Modules G(t) Using the same geometry, a step shear strain of 1X is applied. The stress then decays from its maximum as a function of time.
WO 93/07626 211 ~ ~ ~ 4 P~lGB92/01781 _ g _ step strain s ~
where ~ is a fixed angular displacement.
The relaxation modulus is then given by G(t) ~ Stress step strain where stress is the same as above.
_ The modulus G(t) is stated for lx strain after a relaxation time of 100 seconds.
xam~le 1 - PET-NMP
N-Methyl-2-pyrrolidinone (NMF) eras dried over a molecular sieve. Lithium trifluorc~methanesulphonate CF3S03Li (lithium triflate) was dried over phosphorous pentoxide for 48h.
Polyethylene terephthalate)(:PET) chips, of intrinsic viscosity 0.96 d1/g (17G in dichloroacetic acid at 25°C) were dried at 120C°
for 4h under reduced pressure'.
To 9.0g of molecular-sieve-dried N-methyl-2-pyrrolidihone were added 1.0g of dried polyethylene terephthalate) chips and 1.18g dried l thium triflate, all in a dried glass sample tube.
The tube was sealed and transferred to a silscone oft both at 200°C. The contehts were stirred intermittently and heated until the chips dissolved 'compsetely~ which occurred at a bath temperature of about 215°C. The solution was then allowed to 35, cool to room temperature. During cooling, the solution ceased to flow and solidified to a gel.
The gel was reheated until it flowed and was then cast under dry conditions in lsquid form on to one of the electrodes of the frequency response analyser System. It was sandwiched between WO 93/07626 . PGT/GB92/01781 -10_ the two electrodes and allowed to cool in situ to re-form the gel structure which was a flexible film with good recovery from deformat i on .
A series of conductivity measurements was carried out over a range of temperatures, and the results are shown graphicaTty in Figure 1. The conductivity at 25°C was found to be 10-3~2 Siemens per centimetre.
Exan»le 2 - PET-1FP
Example 1 was repeated using 1-formylpiperidine <1FP> instead of N-methyl-2-pyrrolidinone and 1.03g of lithium triflate instead of 1.18g. The conductivities over a range of temperature are shown graphically in Figure 1. The conductivity at 25°C was found to be 10-3~5 Siemer~s per centimetre.
Dynamic mechanical measurements were performed on several shaped samples prepared according to Examples 1 and 2 using both parallel plates and cone-and-plate sample holders. The samples were sub3ect to an alternating shear strain and the resulting shear stress measured and correlated against the input strain.
The measured shear moduli were generally independent of frequency over the range 0.1 to 500 rad/s and the shear relaxation modulus was determined to be about 103Pa. The dynamic modulus of all these samples was found to exceed 103Pa at 10 Hz.
,.w The accompanying drawing shows the results from these two Examples on a log-conductivity/inverse temperature plot.
~g~nl es 3 -~ 11 The general procedure adopted was as follows:-Dry lithium triflate was dissolved in the dry solvent at room temperature in a sealed dry flask using the molar proportion WO 93/07626 ~ ~ ~ ~ ~ ~ ~ PGT/GB92/01781 required of lithium triflate to solvent. A measured volume of the solution was added to a measured weight of the polymer in a dry vessel and the mixture was heated, with mechanical stirring, by means of an oil bath pre-set at a temperature above 150°G
sufficient to cause the polymer to diSSOlve. The vessel was sealed and quenched to room temperature to cause gel formation.
The conductivity and modulus measurements were made using the procedures already described.
The polymers used for these Examples (and for Exampl-es 1 and 2) were obtained as follows:-Poly(ethylene terephthalate) (PET) was a bottle-grade polymer of (n~ 0.96, in pellet form.
Poly(vinylidene fluoride) (PVDF> was obtained from Polysciences Inc. irr pellet form. It had a weight average molecular weight, according to the suppliers, of 100,000.
Polyhydroxybutyric acid (PHBA) was obtained from Aldrich in powder form. It had a weight average molecular weight, according to the suppliers, of 670,000.
Poly(metaxylylene adipamide) (MXD,6> was Mitsubishi Grade 6001.
Nylon 6,6 was obtained from ICI in the form of granules, Type 86600.
Polyoxymethylene was obtained from Aldrich in the form of beads.
Results of the conductivity and modulus measurements for Examples 3-11 are given in Table 1. In this Table the abbreviations are as follows:
DMF dimethyl formamide DMSO dimethyl sulphoxide TGDME tetraethylene glycol dimethyl ether NMP N-methyl pyrrolidinone OMA dimethyl acetamide The values of Gl are measured at 1X strain amplitude and a WO 93/07626 . ' PCTlGB92/A1781 -lz-frequency of 10 Hz. The values of G(t> are measured 2 minutes after application of a strain of 1X. Both G1 and G(t) are measured at~ambient temperature.
.fable .._.
Example Solvent PolymerConduct-DynamicRelax-Polymer Mass X Li conc. ivity mqdulusan on at triflate wtX 20C G (Pa) modulus of based total S cm-1 G(t)Pa) on solvent gel 3 PVDF DMF 16.8 26.5 6.6x10-33x105 2x105 4 PVDF OMSO 18.3 23.8 4.6x10-32x105 1x105 5 PVDF TGDME5.9 27.2 2.0x10-41x105 7x104 6 PET NMP 13.5 27.2 2.0x10-32x105 1x105 7 PHBA DMA 14.0 13.4 3.6x10'33x105 -8 PHBA DMA 14.0 21.8 i.5x10w31x105 7x104 9 MXD,6 NMP 13.5 12.6 2.4x10- 2x105 1x105 10 Nylon 6,6 NMP 13.5 7.9 2.2x10-34x104 -~
11 POM NMP 13.5 20.5 2.9x10-45x104 3x104
Claims (18)
1. An ionically conductive ion-containing gel consisting of (i) from 20 to 40% by mass of a polymer and (ii) from 60 to 80% by mass of an organic compound, or mixture of organic compounds, that is not a solvent for the polymer at 20°C, and a salt soluble in the said compound or mixture of compounds at 20°C and dissolved therein at a concentration greater than 4% by mass based on said compound or mixture characterised in that the polymer is a crystallisable polymer selected from the group consisting of crystallisable polyesters, polyamides, polyethers and halo-substituted polyolefins and the gel has a bulk ionic conductivity at 20°C and 10kHz greater than 10 -4 Siemens/cm and a dynamic modulus at 10Hz greater than 10 4 Pa.
2. A gel according to claim 1, wherein the crystallisable polymer is of sufficiently high molecular weight to form a coherent film or fibre.
3. A gel as claimed in claim 1 or claim 2 characterised in that it is capable of deformation.
4. A gel according to claim 3, wherein the crystallisable polymer is polyethylene terephthalate), poly(1,4-butylene terephthalate), poly(3-oxybutanoate), polyhydroxybutyric acid, poly(hexamethylene adipamide), poly(metaxylylene adipamide), poly(m-phenylene isophthalamide), poly(vinylidene fluoride), polyoxymethylene or polyoxyethylene.
5. A gel according to any one of claims 1 to 4, whose dynamic modulus at 10Hz exceeds 10 4 Pa.
6. A gel according to any one of claims 1 to 5, whose dynamic modulus at 10Hz exceeds 10 5 Pa.
7. A gel according to any one of claims 1 to 6, wherein the said organic compound is a solvent for the crystallisable polymer at some temperature above 100°C.
8. A gel according to any one of claims 1 to 7, wherein said compound is an amide, a sulphoxide or an ether, or a mixture of such compounds is used.
9. A gel according to claim 8, wherein the amide is a tertiary amide.
10. A gel according to claim 8, wherein said compound is dimethyl formamide, dimethyl acetamide, N-methyl-2-pyrrolidinone, N-formyl piperidine, a dimethyl ether of diethylene glycol, triethylene glycol or tetraethylene glycol, or dimethyl sulphoxide.
11. A gel according to claim 10, wherein the salt is of an alkali metal salt or of optionally substituted ammonium.
12. A gel according to claim 11, wherein the alkali metal is lithium.
13. A gel according to any one of claims 1 to 12, wherein the anion of the salt is monovalent.
14. A gel according to claim 13, wherein the anion is Br-, I-, a pseudohalogen or a perfluorinated alkyl carboxylate or sulphonate.
15. A method of making a gel according to any one of claims 1 to 14, comprising forming a solution of the polymer in the organic compound at above 20°C, incorporating the salt beforehand, simultaneously or afterwards, and cooling the solution.
16. A method according to claim 15, wherein said solution is formed at above 100°C.
17. A method according to claim 16, wherein said solution is formed at above 150°C.
18. A galvanic cell wherein the electrolyte comprises a gel according to any one of claims 1 to 14.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB919121117A GB9121117D0 (en) | 1991-10-03 | 1991-10-03 | Ionically conductive polymer gels |
| GB9121117.7 | 1991-10-03 | ||
| PCT/GB1992/001781 WO1993007626A1 (en) | 1991-10-03 | 1992-09-29 | Ionically conductive polymer gels |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2115654A1 CA2115654A1 (en) | 1993-04-15 |
| CA2115654C true CA2115654C (en) | 2002-09-17 |
Family
ID=10702426
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002115654A Expired - Fee Related CA2115654C (en) | 1991-10-03 | 1992-09-29 | Ionically conductive polymer gels |
Country Status (8)
| Country | Link |
|---|---|
| US (3) | US5460903A (en) |
| EP (1) | EP0606293B1 (en) |
| JP (1) | JP3440248B2 (en) |
| CA (1) | CA2115654C (en) |
| DE (1) | DE69232172T2 (en) |
| ES (1) | ES2161695T3 (en) |
| GB (1) | GB9121117D0 (en) |
| WO (1) | WO1993007626A1 (en) |
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| CN1044484C (en) * | 1994-07-22 | 1999-08-04 | 中国科学院物理研究所 | Gel electrolyte film and its prepn. method |
| US5648011A (en) * | 1995-03-15 | 1997-07-15 | Micron Communications, Inc. | Structurally stable gelled electrolytes |
| US5658685A (en) * | 1995-08-24 | 1997-08-19 | Motorola, Inc. | Blended polymer gel electrolytes |
| US5637421A (en) * | 1995-09-13 | 1997-06-10 | The Johns Hopkins University | Completely polymeric charge storage device and method for producing same |
| JP3756232B2 (en) * | 1996-01-17 | 2006-03-15 | 宇部興産株式会社 | Nonaqueous electrolyte secondary battery |
| US5772934A (en) * | 1996-05-24 | 1998-06-30 | W. R. Grace & Co.-Conn. | Process to produce lithium-polymer batteries |
| US5830600A (en) * | 1996-05-24 | 1998-11-03 | Sri International | Nonflammable/self-extinguishing electrolytes for batteries |
| JP3710826B2 (en) | 1996-10-01 | 2005-10-26 | 日本ゼオン株式会社 | Polymer dispersion composition |
| US6120940A (en) * | 1996-10-30 | 2000-09-19 | The Johns Hopkins University | Electrochemical storage cell containing at least one electrode formulated from a phenylene-thienyl based polymer |
| KR100527322B1 (en) * | 1997-05-06 | 2006-01-27 | 소니 가부시끼 가이샤 | Sheet for Forming a Polymer Gel Electrolyte, Polymer Gel Electrolyte Using Such a Sheet and Method for the Manufacture Thereof |
| US6824920B1 (en) | 1997-06-03 | 2004-11-30 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary battery comprising composite particles |
| US6821675B1 (en) * | 1998-06-03 | 2004-11-23 | Matsushita Electric Industrial Co., Ltd. | Non-Aqueous electrolyte secondary battery comprising composite particles |
| US6653019B1 (en) | 1998-06-03 | 2003-11-25 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary cell |
| WO2000033402A1 (en) | 1998-12-02 | 2000-06-08 | Matsushita Electric Industrial Co., Ltd. | Non-aqueous electrolyte secondary cell and its charging method |
| EP1052712B1 (en) | 1998-12-02 | 2010-02-24 | Panasonic Corporation | Non-aqueous electrolyte secondary cell |
| GB0021466D0 (en) * | 2000-09-01 | 2000-10-18 | Univ Leeds Innovations Ltd | Extruded battery components |
| US6746794B2 (en) | 2001-06-12 | 2004-06-08 | Tech Drive, Inc | Thermal runaway inhibitors |
| US6706823B2 (en) | 2001-12-31 | 2004-03-16 | Bridgestone Corporation | Conductive gels |
| US20040091651A1 (en) * | 2002-11-01 | 2004-05-13 | Mark Rule | Pet copolymer composition with enhanced mechanical properties and stretch ratio, articles made therewith, and methods |
| US20050260371A1 (en) * | 2002-11-01 | 2005-11-24 | Yu Shi | Preform for low natural stretch ratio polymer, container made therewith and methods |
| KR101111419B1 (en) * | 2003-06-18 | 2012-02-15 | 더 코카콜라 컴파니 | Polyester composition for hot fill applications, containers made therewith, and methods |
| CA2479589C (en) * | 2003-09-04 | 2011-05-24 | Air Products And Chemicals, Inc. | Polyfluorinated boron cluster anions for lithium electrolytes |
| US20050221036A1 (en) * | 2004-04-01 | 2005-10-06 | The Coca-Cola Company | Polyester composition with enhanced gas barrier, articles made therewith, and methods |
| US7465517B2 (en) * | 2004-08-23 | 2008-12-16 | Air Products And Chemicals, Inc. | High purity lithium polyhalogenated boron cluster salts useful in lithium batteries |
| US7981388B2 (en) * | 2004-08-23 | 2011-07-19 | Air Products And Chemicals, Inc. | Process for the purification of lithium salts |
| US7572493B2 (en) * | 2005-05-11 | 2009-08-11 | The Coca-Cola Company | Low IV pet based copolymer preform with enhanced mechanical properties and cycle time, container made therewith and methods |
| US7820257B2 (en) * | 2005-05-11 | 2010-10-26 | The Coca-Cola Company | Preforms for preparing lightweight stretch blow molded PET copolymer containers and methods for making and using same |
| WO2007142731A2 (en) * | 2006-04-04 | 2007-12-13 | The Regents Of The University Of California | High elastic modulus polymer electrolytes |
| US8268197B2 (en) * | 2006-04-04 | 2012-09-18 | Seeo, Inc. | Solid electrolyte material manufacturable by polymer processing methods |
| US8513361B2 (en) * | 2007-12-28 | 2013-08-20 | Bridgestone Corporation | Interpolymers containing isobutylene and diene mer units |
| US8889301B2 (en) * | 2008-01-16 | 2014-11-18 | Seeo, Inc. | Gel polymer electrolytes for batteries |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6146935A (en) * | 1984-08-13 | 1986-03-07 | Nissan Motor Co Ltd | Variable light transmittance glass |
| US4908283A (en) * | 1986-10-09 | 1990-03-13 | Ube Industries, Ltd. | Preparation of ion conductive solid electrolyte |
| GB8717799D0 (en) * | 1987-07-28 | 1987-09-03 | Atomic Energy Authority Uk | Polymer electrolytes |
| DE3829541A1 (en) * | 1987-09-03 | 1989-03-16 | Ricoh Kk | LEAF-SHAPED ELECTRODE, METHOD FOR PRODUCING THE SAME AND SECONDARY BATTERY CONTAINING THIS |
| GB8727071D0 (en) * | 1987-11-19 | 1987-12-23 | Dobrowski S A | Solid polyacrylamide electrolyte |
| US5437804A (en) * | 1989-09-22 | 1995-08-01 | Yuasa Corporation | Solid polymer electrolyte |
| US4952293A (en) * | 1989-12-29 | 1990-08-28 | Xerox Corporation | Polymer electrodeposition process |
| JP2987474B2 (en) * | 1991-10-15 | 1999-12-06 | 第一工業製薬株式会社 | Solid electrolyte |
-
1991
- 1991-10-03 GB GB919121117A patent/GB9121117D0/en active Pending
-
1992
- 1992-09-29 EP EP92920233A patent/EP0606293B1/en not_active Expired - Lifetime
- 1992-09-29 WO PCT/GB1992/001781 patent/WO1993007626A1/en active IP Right Grant
- 1992-09-29 CA CA002115654A patent/CA2115654C/en not_active Expired - Fee Related
- 1992-09-29 JP JP50671193A patent/JP3440248B2/en not_active Expired - Fee Related
- 1992-09-29 DE DE69232172T patent/DE69232172T2/en not_active Expired - Fee Related
- 1992-09-29 ES ES92920233T patent/ES2161695T3/en not_active Expired - Lifetime
- 1992-09-29 US US08/196,199 patent/US5460903A/en not_active Expired - Lifetime
-
1995
- 1995-06-06 US US08/466,129 patent/US5639574A/en not_active Ceased
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1999
- 1999-06-17 US US09/334,740 patent/USRE37700E1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| USRE37700E1 (en) | 2002-05-14 |
| DE69232172T2 (en) | 2002-03-28 |
| ES2161695T3 (en) | 2001-12-16 |
| DE69232172D1 (en) | 2001-12-06 |
| EP0606293A1 (en) | 1994-07-20 |
| EP0606293B1 (en) | 2001-10-31 |
| JPH06511595A (en) | 1994-12-22 |
| US5460903A (en) | 1995-10-24 |
| GB9121117D0 (en) | 1991-11-13 |
| WO1993007626A1 (en) | 1993-04-15 |
| JP3440248B2 (en) | 2003-08-25 |
| CA2115654A1 (en) | 1993-04-15 |
| US5639574A (en) | 1997-06-17 |
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