EP0329675A1 - Polymer mit ionenleitfähigkeit - Google Patents

Polymer mit ionenleitfähigkeit

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Publication number
EP0329675A1
EP0329675A1 EP19870907115 EP87907115A EP0329675A1 EP 0329675 A1 EP0329675 A1 EP 0329675A1 EP 19870907115 EP19870907115 EP 19870907115 EP 87907115 A EP87907115 A EP 87907115A EP 0329675 A1 EP0329675 A1 EP 0329675A1
Authority
EP
European Patent Office
Prior art keywords
block
polymer
polystyrene
polymer according
sequences
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.)
Ceased
Application number
EP19870907115
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English (en)
French (fr)
Inventor
Jeremy Roger Martin Giles
James Richard Maccallum
Fiona Mary Chemistry Department Gray
Colin Angus Vincent
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UK Secretary of State for Defence
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UK Secretary of State for Defence
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Publication date
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Publication of EP0329675A1 publication Critical patent/EP0329675A1/de
Ceased legal-status Critical Current

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/04—Oxidation
    • C08C19/06—Epoxidation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/122—Ionic conductors

Definitions

  • This invention relates to polymeric materials; in addition this invention relates to ionically conducting polymeric materials and their preparation and their use in cells, for example galvanic cells, or other electrical or electrochemical devices, or heterogeneous phase processes, for example, solute separation and extraction.
  • the electrolytes most commonly used in electrolytic cells are liquids in the form of solutions containing ionic species, which allow migration of ions between the electrodes of the cell.
  • the electrolytes used suffer from several disadvantages in that they are often corrosive and toxic and present handling and storage difficulties through spillage or leakage from the cell.
  • the routes involve the use of for example, an oxyalkane coordinating unit in the form of an olig omeric sequence such as poly (ethylene glycol) linked by flexible groups at -OH termini to form both linear or crosslinked polymers, so that crystalline, non-conducting phases are essentially eliminated.
  • an oxyalkane coordinating unit in the form of an olig omeric sequence such as poly (ethylene glycol) linked by flexible groups at -OH termini to form both linear or crosslinked polymers, so that crystalline, non-conducting phases are essentially eliminated.
  • the physical form of the electrolyte prepared can be controlled by the nature of the constituent parts of the resultant electrolyte and the degree and nature of any crosslinking.
  • This invention is concerned with the use of an alternative class of polymer for use as electrolytes whereby the largely amorphous nature of the material, necessary for high ion conduction is retained yet the mechanical integrity is sufficient to allow application in a useful device.
  • Alternative routes to enhanced mechanical integrity, described in the patent application 8520902 include the use of filler particles or the introduction of controlled crosslinking.
  • a novel polymer comprising an ABA triblock copolymer; the A block material being rigid having a transition temperature away from its rigid phase above 70°C, the B block material being wholly or partly ion-coordinating, elastomeric or amorphous, the B/A block length ratio being greater than 1, and.
  • phase separation between the A and B blocks may or may not occur.
  • the A block forms phases or domains embedded in a matrix of the B block.
  • the A block polymeric component is either glassy and below its glass transition temperature or predominantly crystalline and below its melting point, when in the intended temperature range of use.
  • the B block polymeric component has a glass transition temperature below the intended operating temperature range, and ideally as low as possible, eg -20°C or preferably even lower, eg less than -40oC.
  • the intended temperature range of use, or operating temperature range is generally around ambientr eg 20°C or above, eg up to 60oC.
  • phase separation between the A and B blocks occurs, as mentioned above, and this may be encouraged or caused to occur by making a blend of the polymer with a polymer which is compatible with the A block material and incompatible with the B phase component.
  • 'compatible' herein is included irascible without phase separation.
  • phase separation and aggregation of A blocks occurs as a result of the thermo-dynamic incompatibility of the component blocks.
  • the rigid domains of A block form throughout the polymer and may form a relatively rigid macrolattice.
  • a polymer of this type having a B block which is elastomeric, of low glass transition temperature (below the required operating temperature range) and ion coordinating resulting in a high ion mobility, and A blocks which form rigid phases or domains which soften or melt at high temperatures eg above 70°C, and are embedded and dispersed within the surrounding elastomeric or amorphous phase may have physical properties which can easily be controlled, for example, the tensile strength.
  • This aspect is a most important part of the invention: the ability to control the mechanical properties eg to obtain a high modulus and low creep characteristic while maintaining a conductivity, obtained from high frequency ac impedance methods of greater than 10 -6 and preferably greater than 5 x 10 -6 S cm -1 at 25oC and simultaneously having a thermoplastic material, which may be soluble in an appropriate solvent.
  • polymers of th invention may be used as components of polymeric electrolytes.
  • the A blocks are of equal length.
  • the B/A block length ratio is controlled, with length (B) greater than length (A), so that the preferred morphology, of near spherical domains of A surrounded by elastomeric B regions, is adopted.
  • the lengths of the A blocks and the B/A block length ratio will also influence the occurrence or non occurrence of phase separation in the polymer.
  • the size of the A block phases or domains when phase separation occurs may also be dependent upon the block lengths, and larger block lengths will lead to larger phases or domains.
  • the exact morphology of the A domains will also depend upon physical treatment received by the polymer, for example solution casting, melt forming and any applied stress. For example stretching or extrusion is likely to elongate or flatten the domains.
  • Blending of the ABA triblock copolymer of the invention with an A-phase compatible material, as mentioned above, may also be used to influence the size and/or shape of the A block domains. If the added material has a high glass transition temperature and the subsequent blended A phase retains a glass transition temperature above 70°C, then the blending polymer may be used to increase the volume fraction of the rigid A phase, and hence alter the physical properties of the polymer.
  • the average A block diameter for the preferred spherical domains is less than 1 ⁇ m, preferably less than 1000 ⁇ .
  • Such domain sizes are generally sufficient to produce a high modulus material without Impairing the conducting nature of the B phase.
  • Materials according to the invention may also be made with anisotropic physical (eg the extent of swelling caused by a solvent selective to the B block), mechanical or ion conducting properties.
  • This anisotropy may be achieved by modification of the A/B block size ratio, the forming and manipulation of the material (eg solvent casting, melt forming, extrusion), and/or blending of an ABA triblock copolymer with an A-block compatible polymer as described above.
  • a phase regions may adopt shapes which are essentially spheres, lamellae or cylinders (fibres), the non- spherical shapes giving rise to anisotropy.
  • the general morphological properties of ABA triblock copolymers are described by H G Elias (given above) and by D G Allport and W H Janes in 'Block Copolymers' 1974 (Applied Science).
  • Blends of the ABA tribolck polymers of the invention with materials other than or in addition to A-compatible materials may be made.
  • a polymer, oligomer, or low mass substance or combination of such may be blended with the ABA copolymer, being compatible with the B block component and incompatible with the A phase component.
  • This possibility may be used to provide physical and material contact with the surroundings of the ABA triblock copolymer when in its application environment.
  • Such an agent added to and blended with the B phase component may act as plasticizer. by lowering the glass transition temperature of the phase.
  • the added agent may also be ion coordinating; for other applications the added agent may perform another active function.
  • materials may be blended with the ABA triblock copolymer which are compatible with both the A and B blocks of the copolymer.
  • blends using the ABA triblock polymers of this invention may be formed by introduction of substances to both the A and B block phases so that three or more starting substances are used in the preparation of the required material.
  • the quantity of material which is blended with the ABA triblock copolymer may be limited by the necessity to retain desirable physical and/or conduction properties, whether the added material is blended with the A or B block.
  • the blended mixture may contain a 2:1 weight ratio of ABA triblock copolymer and blending agents without detriment to at least the conducting properties of the material, and in the case of a B-compatible blend an improvement in the conductivity relative to the ABA triblock copolymer alone is possible.
  • the chemical nature of the B and A blocks will now be discussed.
  • the B blocks are ion-coordinating, andthe atom in the B block responsible for ion coordination is preferably oxygen in an oxyalkane sequence, preferably a polyoxyethylene sequence, ie:
  • This sequence may be present in either the B block polymer main chain or in side chains or cross links attached to the B block chain.
  • the ion coordinating B block is elastomeric or amorphous. It is therefore desirable to have only short oxyalkane sequences or oligomers either as main chain, side chain or cross link components so as to reduce the amount of ambient temperature crystallisation.
  • B-block plasticisers may be mixed with or blended with the polymer, for example low mass (less than ca 800) polyethylene glycol dimethyl ether.
  • m should be an integer 3 - 10, and when in a side chain or cross link, 2 -22 for example 7 - 17.
  • oxyalkane sequences or oligomers may be linked together or linked to the B-block chain (when present in a side chain) by chain extender or linking groups or sequences thereof. These are desirably flexible to increase polymer chain mobility.
  • the links between the oxyalkane sequences or oligomers or between these and the B block main chain may be or include ether links (-O-), methylene (-CH 2 -) ester (-COO-), urethane (-NH-COO-), phosphazine, phosphate ester, siloxane or combinations of these such as (CH 2 ) n where n is 2-12 ('polymethylene'), -(CH-)- n NHCOO- and oxymethylene -OCH 2 -.
  • linking groups include those described in UK Patent Applications 8421193, 8421194 and 8520902, for example
  • each R is Independently selected from C 1-20 alkyl;
  • L is -O-, 1,4 - phenyl, -(CH 2 )- n or -(CH 2 CH 2 O)- m , m being as defined above, and n is less than 12, and g is an integer between 1 and 100.
  • R 1 R 11 C (R 1 R 11 ) or C(R 1 R 11 ) OC (R 1 R 11 ) where R 1 and R 11 are independently selected from H, C 1-20 alkyl alkanoyl, or alkoxy.
  • R is alkoxy, preferably methoxy or ethoxy, and T is -O-,
  • the B block may also contain covalently attached anions, such as -CF 2 CF 2 SO 3 It is preferred that the B block polymer is essentially free from crosslinking or that the crosslink density is low such that the B block behaves as a linear chain elastomer. In order to generate an oxyalkane copolymer of a sufficiently high molecular weight so as to act as an effective B block, a low concentration of crosslinks may be necessary.
  • the polyoxyalkane sequences or oligomers are preferably attached to the B block main chain by a linking group, and may be terminated by hydrogen or by an alkyl group containing 1- 6 carbon atoms so that the side chain has a structure:
  • m is as defined above, X is the linking group and R is the alkyl or hydrogen, methyl being preferred, m is preferably chosen so as to give the polyoxyalkane side chain (not counting X) a molecular mass between 100 and 850, for example 750.
  • the B block polymer main chain may have a variety of structures.
  • a preferred structure is one derived from a cis-1, 4 polybutadiene chain onto which are grafted the preferred polyoxyalkane sequences or oligomers, at some of the unsaturated sites in the chain, using a suitable linking group X as described above to link the polyoxyalkane sequence to the main chain.
  • suitable polymers for the B block include those described in UK Patent Applications 8421193, 842119 4 and 9520902 where main-chain, side-chain and crosslink oxyalkane, preferably oxyethylene, sequences or oligomers derived from, for example, siloxane, methylene or phosphate ester groups or groupings are described.
  • Additional preferred structural types include main chain homo or co polymers containing the units:
  • R 1 and R 2 are independently selected from C 1- 6 alkyl, preferably methyl or ethyl, or -(CH 2 )- d (OCH 2 CH 2 ) n -OR 7 or -(OCH 2 CH 2 )- n OR 7 where n is
  • R 3 and R 4 are independently selected from C 1-6 alkyl, preferably methyl or ethyl or -(OCH 2 CH 2 ) m OR 7 where m is 2-22,
  • R 5 - R 7 are independently selected from C 1 - 6 alkyl and H, and are preferably H or CH 3 , R 8 is -(CH 2 )- g where g is an integer 2 -8 and p is an integer 3 - 10, defining the average length of the oxyalkane units.
  • the A phase is rigid and softens or melts above 70°C. It is also preferred that there is no appreciable crosslinking in the A block component so that the triblock copolymer may be soluble in a known solvent.
  • any polymer of high glass transition, and, or alternatively, with a high melting transition and a large crystalline content, that is incompatible with the chosen B block component may be used.
  • Suitable polymers for the A block component include polystyrene, poly ( ⁇ -methylstyrene) polyurethanes and poly (p-xylylene), and these are preferred. In preparing a required ABA triblock copolymer a number of synthetic approaches are possible.
  • Either the preferred B block polymer may be formed and the A blocks polymerised onto the B block chain ends, or alternatively the A blocks may be independently polymerised and then bonded to the chain ends of the preformed B block.
  • Other methods of preparation will be apparent to those skilled in the art.
  • any suitably substituted vinyl monomer may be copolymerised, where possible with a vinyl monomer derived from the preferred stru ⁇ tual types given, where this is possible, for example:-
  • polysiloxanes may be prepared by the controlled hydrolysis of compounds of the type:
  • polysiloxanes may also be prepared from commercially available poly (hydrogen methyl/dimethyl siloxanes) by a reaction such as:
  • a poly (ethylene glycol) of suitable molecular weight, eg 400 is reacted with dichloro or dibromo methane in basic conditions, eg in the presence of KOH as described in GB 8520902 to form an elastomeric polymer of high ionic conductivity when complexed with for example LiCF 3 SO 3 .
  • the synthetic conditions are chosen such that the end groups of the polymer are -CH 2 Br (eg an excess of dibromomethane) then a photochemically initiated radical polymerisation of the A block monomer, for example styrene, can be initiated to yield the desired triblock copolymer.
  • a photochemically initiated radical polymerisation of the A block monomer for example styrene
  • the B block polymer just described has -CH 2 OH end groups then these may be reacted with an alkyl diisocyanate to yield a polymer with isocyanate end group functions; the polymer so formed may be further reacted with cumene hydroperoxide to form peroxy end group functions which can be cleaved to form free radical active centres and thus again initiate A block formation in the presence of a suitable monomer, for example styrene.
  • a suitable monomer for example styrene.
  • a further ABA triblock copolymer with A blocks composed of linear polyurethane segments formed from a diisocyanate and low molecular weight glycol, preferably poorly or non salt coordinating, and B block from the above described polymer generated by reaction of poly (ethylene glycol) Mwt 400 with dibromo or dichloro methane and having CH 2 OH end groups may be prepared as follows.
  • the B block polymer may be treated with a diisocyanate, aliphatic or aromatic to generate a polymer, isocyanate end-group functionalised. This polymer may now be reacted with further diisocyanate and a low molecular weight glycol to form the A blocks.
  • a preformed polyurethane may be bonded to the B block polymer, with the end groups of each A or B block forming polymer chosen in order to allow urethane linking.
  • a catalyst may be used, and in general techniques and reagents described in the
  • a further synthetic procedure is to modify the B block sequence of an existing or preprepared ABA triblock copolymer by grafting on oxyalkane sequances as side chains at appropriate positions.
  • a preferred starting point is an ABA triblock copolymer having a B-block which is poly (cis-1,4 butadiene).
  • the A block component may be one of the preferred polymers referred to above, so that this starting point is for example a polystyrene - poly cis -1,4-butadiene-polystyrene ("PS-PBD-PS”) ABA triblock polymer.
  • PS-PBD-PS polystyrene - poly cis -1,4-butadiene-polystyrene
  • These starting materials are either commercially available or may be prepared by known methods.
  • Suitable reagents for the first two steps are m-chloroperbenzoic acid and LiAlH 4 respectively. Their use leads to a minimum number of unwanted side reactions.
  • introduction of the required degree of -OH functionalisation may be achieved.
  • the method of epoxid-ation of the diene is preferred as this reduces the possibility of cross-linking.
  • Preferred methods are to form an ether link via for example formation of a tosyl - terminated polyoxyalkane sequence and reaction of this with the -OH groups, or formation of urethane links, by formation of an isocyanate-terminated polyoxyalkane sequence and reaction of this with the -OH groups.
  • Other types of link are also suitable in these polymers, for example ester links formed by reaction of a carboxylic acid terminated polyoxyalkane sequence with the -OH group of the B block of the polymer.
  • linking group X may bean, ether-type linkage (ie X is an oxygen atom), or a urethane-type linkage (eg X is
  • X is -OCO-(CH 2 ) p -COO- where p is 1-12, preferably 2).
  • R is preferably methyl.
  • poly cis -1,4 butadiene The structure of poly cis -1,4 butadiene is shown ideally below:
  • the polymeric chain has at least 80-85% of the double bonds in the cis - configuration.
  • the B block of the particularly preferred polymers of the invention will therefore contain such repeating units, and may also contain a proportion at least of randomly distributed units having structures selected from the following:
  • the preferred average molar, masses in the starting material for the A-block polystyrene segments are-about 10,000- 40,000 each and for the B block about 40,000 up to about 150,000 typically about 100,000. These molar masses are found to give the desired structure of the polymer as discussed above.
  • a suitable A- compatible blending material is polystyrene, when the A block is also polystyrene, and may have a similar molar mass to that of the A block eg 20,000.
  • a suitable B-compatible blending material is for example polyethylene glycol dimethyl ether (of average molar mass ca 400), polyethylene glycol or other low molecular mass (eg ca 400) material when for example the B block is methoxy polyethylene glycol grafted polybutadiene.
  • the polymer may also be blended with high molar mass polyethylene oxide, for example of molar mass 1-6x10 6 .
  • a block and B block compatible material When it is desired to blend both A block and B block compatible material with this preferred polymer then the A- and B- block compatible materials referred to above may be used.
  • the starting point for the epoxldisation and -OH funtionalisation process described above is an ABA triblock polymer having a PBD B-block and A blocks which are the preferred A-block polymers mentioned above, in particular polystyrene, the epoxidised or -CH functionalised intermediates may also be novel and useful materials.
  • the invention further provides a polymer having a structure based upon an ABA triblock copolymer .
  • the A- blocks are selected from polystyrene, poly ( ⁇ -methylstyrene), polyurethanes and poly (p-xylylene), especially polystyrene
  • epoxidised and hyiroxy-functionallsed polymers may be ion coordinating by virtue of the presence of the oxygen atom in the epoxide or hydroxy group in the PBD B-block, and therefore they are encompassed by the polymers of the first aspect of the invention described above. They may therefore be made into polymeric electrolytes by inclusion of an ionic salt.
  • these epoxidised and -OH functionalised polymers may also be used for other purposes, eg structural polymers.
  • the epoxidised material at least has properties similar to the epoxidised natural rubber referred to above.
  • a further preferred ABA triblock polymer of this invention is one in which the A blocks are selected from polystyrene, poly ( ⁇ - methylstyrene), polyurethanes and poly (p-xylylene), preferably polystyrene, and the B block consists either wholly of polyethylene oxide, ie (CH 2 CH 2 O) m sequences, or of (CH 2 CH 2 O) m sequences joined by linker groups.
  • This polymer has the polyethylene oxide sequences in its B block main chain.
  • the B block consists ideally of two (CH 2 CH 2 O) sequences joined at or close to the mid point of the 3 block by a linker group.
  • linker groups in this case include the links between the oxyalkane sequences or oligomers discussed above, ie they may be or include ether, methylene, ester, urethane, (CH2)- n NHCOO- and oxymethylene OCH 2 .
  • Such an ABA triblock polymer may be prepared by first prepar- ing an A-polyethylene oxide iiblock polymer with a functional terminus, particularly -OH on the polyethylene oxide segment. Two such diblock polymers may then be combined via a suitable linking molecule to form a linking group in the resulting ABA triblock copolymer. For example two such diblock polymers may be reacted with a dihalomethane ani potassium hydroxide to leave a -GH 2 - linker when the functional terminus is -OH.
  • a diisocyanate such as OCN-(CH 2 )- r NCO where r is an integer may be used when the function al terminus is -OH to form a urethane link eg -OOCNH(CH 2 ) r NHCOO.
  • a dicarboxylic acid, or an anhydride such as succinic anhydride may be used to introduce an ester linker, eg -OOC(CH 2 ) r COO when the functional terminus is -OH.
  • Other linkers which are suitable for joining two -OH terminated polyethylene oxide sequences will be apparent to those skilled in the field.
  • Typical molar masses for the A blocks are 10,000 - 40,000 and for the B block about 120 - 3,000 preferably as low as possible.
  • Short polyethylene oxide sequences are preferred.
  • the ABA triblock copolymers of the invention may be used to form a polymeric electrolyte, and according to a further aspect of the invention there is provided a polymeric electrolyte comprising an ABA triblock copolymer as described above and having an ionic salt complexed with the B-block. This electrolyte is therefore a solid solution electrolyte.
  • polymers in which phase separation of the A blocks, as described above, has occurred are preferred, for ex ample those based upon a PS-PBD-PS ABA triblock polymer as described above.
  • the ionic salt complexed with the B block of the ABA triblock copolymer to form a solid solution electrolyte is preferably the salt of an alkali or alkaline earth metal, this includes lithium, sodium, magnesium, potassium or calcium salts; alternatively an ammonium or alkyl ammonium salt containing the cation R 4 N where the R groups are selected from alkyl, optionally substituted alkyl or H, may be used.
  • the anion of the salt may be any commonly used anion, but is preferably a relatively large anion of a strong acid, for example, perch lorate C10 ⁇ 4 , trifluoromethanesulphonate CF 3 SO 3 ⁇ , BF 4 ⁇ , PF 6 ⁇ ,. SCN ⁇ ,
  • LiCF 3 SO 3 is a preferred salt.
  • the B block contains covalently attached anions, eg -CF 2 CF 2 SO 3 ⁇ with associated ionically-bound cations eg Li ions, an added salt may be unnecessary, or a salt may be added.
  • anions eg -CF 2 CF 2 SO 3 ⁇ with associated ionically-bound cations eg Li ions
  • the polymeric electrolyte of this aspect of the invention may be made in a number of ways, all intended to disperse and dissolve the salt in the ABA triblock copolymer.
  • Known methods may be used, for example mixing together the polymer and salt and then melting them together to form a complex and then extruding the mixture into a thin film.
  • Another method involves milling the salt and the polymer together at a low temperature, followed by forming the electrolyte into a film with heat and pressure.
  • a third method involves dissolving the salt and the polymer together in a suitable solvent at an appropriate concentration, and forming the mixture into a film by solvent evaporation.
  • suitable solvents include for example THF.
  • Some solvents such as nitromethane encourage phase separation between the A and B blocks, and the use of such solvents is preferred as this has in some cases been found to lead to improved electrolyte performance. Mixtures of solvents may also be used.
  • the polymer may be immersed in a solution of the salt in a suitable solvent which does not dissolve the polymer, eg an alcohol such as methanol. The salt thereby partitions between the solution and the B block of the polymer, and is incorporated into the polymer.
  • the oxygen for cation binding to cation concentration in the electrolyte should be between 4:1 and 50:1.
  • the polymeric electrolyte according to the invention is preferably a solid, in the sense of resisting creep during cell assembly.
  • the electrolytes described herein may be used in any application where a solid solution. electrolyte. is possible. andl desired.
  • One such application is in a galvanic or photogalvanic cell comprising an anode, a cathode and an electrolyte sandwiched between the said electrodes, in which the electrolyte comprises a polymeric electrolyte according to the invention described herein.
  • a battery comprising a plurality of such cells.
  • the galvanic cells and batteries of such may be manufactured in known ways. They may be either primary or secondary (rechargeable) cells or batteries for a variety of applications for example, electric vehicles, back-up power sources for use in for example computers, heart pacemakers and integrated power sources for electronic circuitry.
  • the batteries may be connected in either series or parallel or a combination of such depending on whether maximum voltage or current or some compromise is required as output.
  • the thickness of the individual cells can be made extremely small while maintaining a high contact surface area, and it is thus possible to incorporate many cells, for example 1000 or more, in a compact battery structure.
  • the anode is lithium metal or an alloy for example, lithium-aluminium or lithium-silicon so that the anode is reversible to the li/li+ couple.
  • the ABA triblock copolymer electrolyte is complexed with a lithium salt and that the cathode is a lithium ion intercalation material, such as TiS 2 , although an electrolyte and possibly conducting particles such as carbon black may be mixed with the cathode material.
  • the anode and cathode may be conventional as may the encapsulation of the cell and/or its assembly within the battery.
  • the cell may be formed using the techniques described in US Patent 4303748.
  • the polymers of the invention may also be used in a heterogeneous phase process, for example, solute separation and extraction, wherein a salt complexed with the B-phase should not be required.
  • the solute to be concentrated in the stationary phase formed entirely or in part by a polymer of this invention may be for example an ionic salt or an organic material or an inorganic material or combination of such, possibly covalently bound together.
  • the solute in solution could for example be passed through a column containing such a polymer.
  • the polymer could be rendered less soluble in such an application by. cross-linking ih the A block.
  • polymers of this invention are where the polymer would act as a membrane between different, usually liquid and solid phases forming a semi-permeable barrier allowing physical contact and transfer of material between said phases.
  • the first stage of the synthesis was the epoxidation of a fraction of the polybutadiene carbon-carbon double bonds by reaction with m - chloroperbenzoic acid followed by reduction of the product with lithium aluminium hydride to generate hydroxyl- functional groupings:
  • the reduction of the polymeric epoxide was similar to A above except that the isolated hydroxylated product was soluble in methanol preventing the use of a reprecipitation purification route. Instead the CH 2 Cl 2 product solution obtained was evaporated down and residual water present poured off. The polymer was redissolved in CH 2 Cl 2 , dried over molecular sieves, and the solvent removed. Product (III), 52% hydroxylated was finally dried under vacuum at 50°C.
  • Methoxy polyethylene glycols of average molar mass ranges of 550 and 750 were used.
  • the method involves a condensation reaction to generate a urethane linkage at the grafting site.
  • a dibutyl tin dilaurate catalyst was used.
  • Electrolytes from polymer (IX) A film of (IX) having B-phase complexed with LICF 3 SO 3 (to give B-phase oxygen-for-lithium-binding to lithium molar ratio of either 50, 30, 16 or 7) was prepared from a THF solution of (IX) and the salt at room temperature. The solvent was evaporated under vacuum to leave a solid electrolyte. This was heated to 110-120°C in vacuum for 4-5 hours. After cooling the sample to room temperature further manipulations were carried out under argon-atmosphere glovebox conditions. The material was mounted between electrode anvils and pressed at room temperature from a 5mm diameter pellet to a 13mm diameter film.
  • the films were heated to 110-120°C for 1 hour, without the application of pressure, then slowly cooled (ca. 1°C min -1 ) to room temperature.
  • the electrodes - electrolyte film assembly was transferred to a variable-temperature conductivity cell for ac impedance analysis.
  • the electrodes were. steel and ion-blocking. Films examined were typically 100-300 ⁇ m in thickness and their response characteristics were recorded over a frequency range of 1 MHz to 1 Hz, at a series of temperatures. Log 10 (conductivity/S cm -1 ) against reciprocal temperature (K -1 ) is plotted in Fig 1.
  • the polymer was milled at close to -196°C and then milled under similar conditions with an appropriate quantity of LiCF 3 SO 3 added so that a homogeneous material was generated.
  • An electrolyte was prepared in a similar manner to those described in Example 4, by solid-state milling and press ing.
  • a plot of log 10 (conductivity/S cm -1 ) versus reciprocal temperature (K -1 ) for an electrolyte with 0/Li - 16 is given in Fig 4. At 25°C the conductivity was 4.0 x 10 -6 S cm -1 .
  • Electrolyte films were prepared in a similar way to those of Example 3.
  • a film of (XIl) containing. LiCF 3 SO 3 to a concentration resulting in a B-phase 0/Li molar ratio of 16 had a conductivity at 25°C of 1.0 x 10 -5 S cm -1 .
  • Example 7
  • Blending of ABA triblock polymers (a) with A - block compatible material Blending of ABA triblock polymers (a) with A - block compatible material.
  • Method 2 A catalysed procedure.
  • Example 10 Electrolytes from (XV), and analogue (XVI) with glycol mass 750, both prepared by the route given in Example 9
  • Polyethylene oxide (mass 4 x 10 6 ), graft copolymer (VIII) and Li CF 3 SO 3 (to give an oxygen-to-lithiumion molar ratio of 10) were ground togetherin a ball-mill at liquid nitrogen temperatures. Mixtures were prepared containing 25 or 50% wt polyethylene oxide, based on total polymer content.
  • the resultant polystyrene ethylene oxide end-capped polymer was isolated by pouring the reaction solution into a 16 - foli excess of n-heptane.
  • step G Formation of the polystyrene -polyethylene oxide - polystyrene ABA triblock copolymer by coupling the -OH termini of the ethylene oxide blocks of the diblock polymer prepared in B above.
  • the preparative route of step G is summarised by the equation:

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EP19870907115 1986-10-27 1987-10-27 Polymer mit ionenleitfähigkeit Ceased EP0329675A1 (de)

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GB8625659A GB8625659D0 (en) 1986-10-27 1986-10-27 Polymeric ion conductors
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US4943626A (en) * 1988-07-29 1990-07-24 The Dow Chemical Company Primary polyether active hydrogen compounds which are prepared from linked, protectively initiated polyalkyleneoxides
US5523180A (en) * 1992-06-16 1996-06-04 Centre National De La Recherche Scientifique Ionically conductive material having a block copolymer as the solvent
JP3528210B2 (ja) * 1993-08-24 2004-05-17 栗田工業株式会社 水処理用触媒
US5755985A (en) * 1994-09-06 1998-05-26 Hydro-Quebec LPB electrolyte compositions based on mixtures of copolymers and interpenetrated networks
JPH1167274A (ja) 1997-08-22 1999-03-09 Daikin Ind Ltd リチウム二次電池及び高分子ゲル電解質並びにリチウム二次電池用結着剤
DE19855889A1 (de) * 1998-12-03 2000-06-08 Basf Ag Für elektrochemische Zellen geeignete Membran
SE516891C2 (sv) * 1999-06-14 2002-03-19 Ericsson Telefon Ab L M Bindemedel och/eller elektrolytmateriel för en elektrod i en battericell, elektrod för en battericell samt förfarande för framställning av ett bindemedel och/eller elektrolytmaterial för en elektrod
ATE290565T1 (de) * 2000-02-24 2005-03-15 Michelin Soc Tech Vulkanisierbare kautschukmischung zur herstellung eines luftreifens und luftreifen, der eine solche zusammensetzung enthält
TW527745B (en) * 2000-11-21 2003-04-11 Dainichiseika Color Chem Solidifying material for cell electrolyte solution, and cell comprising the solidifying material
PL1709126T3 (pl) * 2004-01-08 2008-10-31 Hercules Inc Zgodny z pigmentami, syntetyczny zagęszczacz do farb
FR2899235B1 (fr) * 2006-03-31 2012-10-05 Arkema Electrolytes polymeres solides a base de copolymeres triblocs notamment polystyrene-poly(oxyethylene)-polystyrene
US8268197B2 (en) 2006-04-04 2012-09-18 Seeo, Inc. Solid electrolyte material manufacturable by polymer processing methods
WO2007142731A2 (en) 2006-04-04 2007-12-13 The Regents Of The University Of California High elastic modulus polymer electrolytes
EP2396848B1 (de) * 2009-02-11 2014-11-19 Dow Global Technologies LLC Hochleitfähige polymerelektrolyte und sekundärbatterien damit

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US3663659A (en) * 1970-05-22 1972-05-16 Us Health Education & Welfare Process for the preparation of hydroxylated block polymers
EP0190306B2 (de) * 1984-08-21 1993-12-22 The Secretary of State for Defence in Her Britannic Majesty's Government of the United Kingdom of Great Britain and Polymerer elektrolyt

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GB2215726A (en) 1989-09-27
GB2215726B (en) 1991-05-15

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