GB2401609A

GB2401609A - Polymer electrolyte

Info

Publication number: GB2401609A
Application number: GB0310953A
Authority: GB
Inventors: Peter V Wright; Jianguo Lui; Yungui Zheng
Original assignee: University of Sheffield
Current assignee: University of Sheffield
Priority date: 2003-05-13
Filing date: 2003-05-13
Publication date: 2004-11-17
Anticipated expiration: 2023-05-13
Also published as: GB2401609B; GB0310953D0

Abstract

A polymer electrolyte being configured to provide ion transport, the polymer electrolyte comprising: a main-chain first repeating unit configured to provide a primary ion coordinating site, a plurality of main-chain repeating units being arranged as a substantially helical ion coordinating channel. The polymer electrolyte further comprising and being characterised by: a main-chain second repeating unit being interdispersed between the main-chain first repeating unit. The second repeating unit being configured to provide a secondary ion coordinating site within the coordinating channel. The secondary ion coordinating site being less coordinating than the primary ion coordinating site; wherein the polymer electrolyte is configured to provide ion transport within the coordinating channel involving ion transport between the primary ion coordinating site and the secondary ion coordinating site.

Description

POLYMER ELECTROLYTE

Field of the Invention

The present invention relates to polymers and in particular, although not exclusively, to organised polymer electrolyte complexes configured for ion transport.

Background to the Invention

Within the field of polymer electrolytes four distinct types of material, reflecting four different mechanistic approaches to ion mobility, have been recognised. i) The translation of lithium salts through liquid solvents in gels or hybrid' materials of various kinds. ii) Solvent-free, salt - polymer complexed systems in which the ion motion is coupled to the micro-brownian motion of segments of the polymer chains above the glass or melting transitions of the system. iii) 'Single-ion' systems, in which the lithium ion moves by a hopping process between anionic sites fixed to the polymer chain, or systems with reduced mobility of anions (solvent containing or solvent -free). iv) Solvent- free, salt-polymer complexed systems in which ion mobility is uncoupled to the motions of polymer chain segments. À

The drive towards solvent-free polymer electrolytes stems from the hazards associated with the highly reactive lithium (currently used within batteries) in contact with low-molecular weight solvents. This is especially apparent for heavy-duty battery applications in which operation at elevated À À temperatures might be anticipated. Accordingly a very real risk of fire and À.e e.

explosion is to be associated with heavy-duty applications of such conventional lithium - organic solvent batteries.

Conventionally, solvent-free polymer electrolytes have been largely based upon complexes of lithium salts in amorphous forms of polyethylene oxide (PEO), this polymer dissolves lithium salts to give semi-crystalline or fully amorphous complex phases where ion migration through the amorphous P0989.spec phases gives rise to significant conductivity; M.B. Armand, in J.R. MacCallum, C.A. Vincent (Eds) Polymer Electrolyte Reviews 1, Elsevier, London, 1987, Chapter 1; .G.Cameron and M.D.lngram, in J.R. MacCallum, C.A. Vincent (Eds) Polymer Electrolyte Reviews 2, Elsevier, London, 1989, Chapter 5.; F. M. Gray, Polymer Electrolytes, the Royal Society of Chemistry, Cambridge, UK, 1997, Chapter 1. Ion mobilities in these systems are free-volume dependent and are essentially coupled to the segmental mobilities of the rubbery polymer, the conductivity, c,, generally following a strong temperature dependence. Whilst conductivities at temperatures above cat 80 C approach 10-3 S cam, which is adequate for successful operation of lithium batteries at such temperatures, a variety of strategies have thus far failed to bring about conductivities greater than cat 10-4 S cm' at ambient temperatures (ca. 25 C).

In particular, the application of amorphous forms of PEO in ambient temperature batteries, requiring conductivities of cat 10-3 S cm, is prohibited due to their low ambient conductivity. Other amorphous systems giving conductivities between 10-4 to 10-5 S cm' have been proposed C. A. Angell. C. Liu and E Sanchez. Nature. 1993. 362. 137.; F. Croce. C. Appetecchi.L. Persi and B. Scrosati. Nature. 1998.394.456. À

In an attempt to address the low ambient temperature conductivities associated with PEO based electrolytes, various extended helical crystalline structures of PEO-alkyl salt complexes have been proposed forming organised low-dimensional polymer complexes, Y. Chatani and S. Okamura. Polymer. À À À

1987 28. 1815.; P. Lighffoot. M. A. Mehta and P. G. Bruce. Science. 1993. 262.

À ....

883.; Y. G. Andreev. P. Lighffoot. And P. g. Bruce. J. Appl. Crystallogr., 1997.

18. 294; F. B. Dias. J. P. Voss. S. V. Batty. P. V. Wright and G. Ungar.

Macromol. Rapid Common., 1994.15. 961.; F. B. Dias. S. V. Batty. G. Ungar. J.

P. Voss. And P. V. Wright. J. Chem. Soc., Faraday Trans., 1996. 92. 2599.; P. V. Wright. Y. Zheng. D Bhatt. T. Richardson and G. Ungar. Polym. Int., 1998.

47. 34.; Y. Zheng. P. V. Wright and G. Ungar. Electrochim. Acta. 2000., 45.

1161.; Y. Zheng. A Gibaud. N. cowlam. T. H. Richardson. G. Ungar and P. V. P0989.spec Wright. J Mater. Chem., 2000. 10. 69, Yungui Zheng, Fusiong Chia, Goran Ungar and Peter. V. Wright, Chem. Commun., 2000, 1459-1460.

Of these most recent solvent-free low-dimensional polymer electrolyte blends, a helical polymer backbone provides support for alkyl side-chains which interdigitate in a hexagonal lattice layer between the polyether helical backbones. Cations are encapsulated within the helices, one per repeat uniVhelical turn, where the anions lie in the interhelical spaces. These three- component systems incorporate a long chain n-alkyl or alkane molecule, the inclusion of which provides increased conductivities resulting from highly- organised lamellar textures where the long chain n-alkyl or alkane molecule is embedded between lamellar layers.

However, such solvent-free polymer electrolyte complexes still exhibit unsatisfactory temperature dependent conductivities in addition to unsatisfactory conductivity levels at ambient temperature.

What is required therefore is a solvent-free electrolyte exhibiting reduced temperature dependent conductivities and/or increased conductivity at ambient À À temperature operating conditions. À À

s : . . Summarv of the Invention The inventors provide improved solventfree polymer electrolytes capable of conductivities over the range 10 S cm' to 1 o-2 S cm, at ambient temperatures.

:.. 25 : : According to known solvent-free electrolyte complexes ion migration is provided via helical ionophilic polyether based coordinating channels, providing in turn, ion motion being largely de-coupled notwithstanding minimal local conformational motions of the polyether backbones. Following a realisation of enhanced ion mobility in such ionophilic channels, the inventors provide ion coordinating pathways being configured with oxygen-rich primary ion coordinating sites and oxygendeficient secondary ion coordinating sites. Owing to the P0989.spec creation of ion conducting channels within an ordered polymer complex comprising regions of ion coordinating sites being interdispersed with coordinating site 'spaces' or 'voids' entranced ion mobility is achieved.

The inventors provide both a polymer electrolyte and a method of synthesising the same so as to provide a 'tunable' polymeric selforganising ion conducting species configured to provide adjustable levels of ion conductivity, being dependent upon a ratio of primary ion conducting sites (oxygen-rich) to secondary ion conducting sites (oxygendeficient) within the ion conducting 1 0 channel(s).

According to specific embodiments of the present invention the ratio of primary ion coordinating sites to secondary ion coordinating sites may be greater or less being dependent upon the synthetic route employed. For example, reactants, solvents and/or reaction parameters may be varied so as to achieve a desired ratio of primary ion coordinating sites to secondary ion coordinating sites.

Particularly, relative proportions of a co-solvent of dimethylsulphoxide (DMSO) and tetrahydrofuran (THE) may be varied. For example, variation of a type and/or molar quantity of a more polar solvent within a co-or multisolvent system À À . may be utilised in order to selectively synthesis a copolymer of desired oxygen À . rich to oxygen-deficient repeating unit content forming the main-chain polymeric : . . backbone.

- :

According to a specific implementation of the present invention ion À À:. 25 coordinating channels are formed from polyether backbones involving an oxygen : : rich repeating unit, providing primary ion coordinating sites, being interdispersed with an oxygen-deficient repeating unit providing secondary ion coordinating sites, the secondary ion coordination sites being configured to coordinate ions to a lesser extent than the primary sites.

Additional components within the polymer electrolyte complex may R comprise a first and/or second ionic bridge polymer configured to enhance P0989.spec conductivity levels and reduce temperature dependent conductivity characteristics. In response to a de-blending heating process, the ion conducting polymer(s) establish a lamellar and/or micellar morphology, the ion coordinating channels being provided in such organised textures. This first and/or second ionic bridge polymer(s) sit(s) between the lamellar or micellar regions serving to provide an ionic bridge between amphiphilic channels so as to offset any reduction in conductivity resulting from ion conducting polymer lattice shrinkage in response to temperature reduction.

10According to a further specific implementation of the present invention the ionophilic coordinating channels may be constructed solely from the secondary ion coordinating sites.

According to a first aspect of the present invention, there is provided a polymer electrolyte being configured to provide ion transport, said polymer electrolyte comprising: a main-chain first repeating unit configured to provide a primary ion coordinating site, a plurality of main-chain repeating units being arranged as a substantially helical ion coordinating channel; said polymer electrolyte further comprising and being characterized by: a main-chain second repeating unit being interdispersed between said main-chain first repeating unit, À . said second repeating unit being configured to provide a secondary ion À . coordinating site within said coordinating channel, said secondary ion coordinating site being less strongly coordinating then said primary ion coordinating site; wherein said polymer electrolyte is configured to provide ion À À:. 25 transport within said coordinating channel involving ion transport between said : : primary ion coordinating site and said secondary ion coordinating site.

Preferably, said main-chain first repeating unit and/or said main-chain second repeating unit comprise a hydrocarbon side-chain extending from said main-chain repeating unit, said hydrocarbon side-chain being configured to interdigitate with hydrocarbon side-chains of neighbouring main-chain repeating units.

P0989.spec Preferably, said ion coordinating channel is oxygen-rich at said primary ion I coordinating site; and said ion coordinating channel is oxygen-deficient at said secondary ion coordinating site.

Preferably, said main-chain first repeating unit comprises a plurality of ethylene oxide repeating units and said main-chain second repeating unit comprises at least one methylene oxide repeating unit.

Preferably, said polymer electrolyte comprises a plurality of substantially helical ion coordinating channels being formed from a plurality of main-chain first and second repeating units arranged as a lattice by interdigitation of the hydrocarbon side-chains.

Preferably, ions being transported within said coordinating channel are substantially decoupled from conformational motion of said main-chain first and second repeating unit.

Preferably, the polymer electrolyte comprises a second polymer comprising ionophilic polyoxyalkylene units. 20 .

Preferably, the second polymer is positioned between said lattice of said : . . plurality of main-chain first and second repeating units. !

According to a second aspect of the present invention, there is provided a À À À:. 25 copolymer comprising repeating units being represented by general formula (1) :' ': and (2): 72_R3 tRWo; (1) R2_R3 FOR TO/ t (2) P0989.spec where R' is alkylene or a benzene nucleus; R2 is oxygen, nitrogen, alkylene, phenylene or CH2; R3 is alkyl, phenyl or alkyl-phenyl and 8 An 22, preferably n is5.

Preferably, R' is a benzene nucleus, R2 is oxygen and R3 is a substantially straight chain hydrocarbon preferably -(CH2)m-H where 30 2 m 2 5, more preferably m is 12, 16 or 18.

Preferably, Ri is CH, R2 is oxygen and R3 is a substantially straight chain I hydrocarbon preferably-(CH2)m-H where 30 Am 25, more preferably m is 12, 160r18.

According to a third aspect of the present invention, there is provided a polymer blend comprising a first copolymer and a second copolymer, said first copolymer comprising repeating units being represented by general formula (1) and (2): a- R2_R3 tRo; (1) ace R2-R3 À. 1 A. R1: :: (2) À where R' is alkylene or a benzene nucleus; R2 is oxygen, nitrogen, alkylene, ! a....t phenylene or CH2; R3 is alkyl, phenyl or alkyl-phenyl and 8 En 22, preferably n is 5; and said second copolymer comprising repeating units being represented by general formula (3): :0 - (A- O -)x B (3) P0989.spec where A is alkylene or phenylene; B is alkylene, phenylene, alkylene ether, phenylene ether, alkylene-phenylene ether, alkoxy-phenylene ether or alkyl- phenylene ether; 40 2x 220.

According to specific implementations of compound (3) the alkoxy or alkyl component may comprise -(CH2)m-H where 30 Em 25, more preferably m is 12, 16 or 18.

Preferably, R' is a benzene nucleus; R2 is oxygen and R3 is a substantially straight chain hydrocarbon preferably-(CH2)m-H where 30 Am 25, more I preferably m is 12, 16 or 18; A is (CH2)4; B is a substantially straight chain hydrocarbon preferably (CH2)m or B is -OC6H4-O-(CH2)2-O-C6H4-O-.

Preferably, R' is CH, R2 is oxygen and R3 is a substantially straight chain hydrocarbon preferably-(CH2)m-H where 30 Am 25, more preferably m is 12, 16 or 18; A is (CH2)4; B is a substantially straight chain hydrocarbon preferably (CH2)m or B is -O-C6H4-O-(CH2)42-O-C6H4-O According to a fourth aspect of the present invention, there is provided a polymer electrolyte being configured to provide ion transport, said polymer À. electrolyte comprising: a main-chain polyether repeating unit being configured to . provide ion transport; an alkylene group or a benzene nucleus being interdispersed within said polyether repeating unit; said polymer electrolyte further comprising and being characterized by: a hydrocarbon side-chain extending from À a:..; 25 said alkylene group or said benzene nucleus, said hydrocarbon side-chain being :'': configured to interdigitate with hydrocarbon side-chains of neighbouring polyether repeating units; wherein ion transport is provided within a coordinating channel formed by said polyether repeating unit.

Preferably, said hydrocarbon side-chain is alkyl, phenyl or a substantially straight chain hydrocarbon preferably -(CH2)m-H where 30 2 m 2 5, more preferably m is 12, 16 or 18.

P0989.spec Preferably, said hydrocarbon side-chain is provided on each alkylene group or benzene nucleus within a plurality of repeating units.

Preferably, said hydrocarbon side-chain extends from some of the alkylene groups or benzene nuclei of a plurality of repeating units.

Preferably, said polymer electrolyte is arranged as a lattice, said lattice comprising ionophilic regions of polyether repeating units and ionophobic regions of hydrocarbon side-chains.

According to a fifth aspect of the present invention, there is provided a polymer comprising a repeating unit being represented by general formula (2): R2_R3 OUR O/ (2) where R' is alkylene or a benzene nucleus; R2 is oxygen or nitrogen, alkylene, phenylene or CH2; R3 is alkyl, phenyl, alkyl-phenyl or hydrogen.

Preferably, R. is a benzene nucleus, R2 is oxygen and R3 is a substantially I À. ..

: . straight chain hydrocarbon preferably -(CH2)m-H where 30 m 2 5, more preferably m is 12, 16or18. À Àe À À

Preferably, R' is CH, R2 is oxygen and R3 is a substantially straight chain Àe hydrocarbon preferably-(CH2)m-H where 30 Em >5, more preferably m is 12, :. .. 16or18. : 25 À

Preferably, R' is CH or a benzene nucleus, R2 is CH2 and R3 is a substantially straight chain hydrocarbon preferably-(CH2)m-H where 30 2m > 5, more preferably m is 12, 16 or 18.

P0989.spec According to a sixth aspect of the present invention, there is provided a polymer electrolyte being configured to provide ion transport, said polymer electrolyte comprising: an ion conducting polymer being represented by general formula (2): R2 R3 try HO:} (2) where R' is alkylene or a benzene nucleus; R2 is oxygen, nitrogen, alkylene, phenylene or CH2; R3 is alkyl, phenyl or alkyl-phenyl; and an ionic bridge polymer being represented by general formula (3): tO-(A-O-)x-B (3) 10where A is alkylene or phenylene; B is alkylene, phenylene, alkylene ether, phenylene ether, alkylene-phenylene ether, alkoxy-phenylene ether or alkyl phenylene ether;; 40 2x 220.

Preferably, R' is a benzene nucleus; R2 is oxygen and R3 is a substantially 15straight chain hydrocarbon preferably-(CH2)m-H where 30 Em 25, more I preferably m is 12, 16 or 18; A is (CH2)4; B is a substantially straight chain À À hydrocarbon preferably (CH2)m or B is -O-C6H4-O-(CH2)42-O-C6H4- O-. À À.

Preferably, R' is CH, R2 is oxygen and R3 is a substantially straight chain À.

hydrocarbon preferably-(CH2)m-H where 30 Am 25, more preferably m is 12, l 16 or 18; A is (CH2)4; B is a substantially straight chain hydrocarbon preferably : (CH2)m or B is -O-C6H4-O-(CH2)2-O-C6H4-O. . À

According to a specific implementation of the present invention, a galvanic cell is provided comprising the polymer electrolyte/polymer blend as detailed herein, in particular the galvanic cell is configured for lithium ion transference.

Optionally, the galvanic cell may be solvent free where electrolytedecoupled ion P0989.spec transport occurs via ionophilic repeating unit channels between a cathode and anode.

According to a seventh aspect of the present invention, there is provided a galvanic cell comprising a polymer electrolyte being formed from a first copolymer comprising repeating units being represented by general formula (4) and (5): O - (cH2)m H \o/: (4) O- (CH2)m H |0/ (5) ; where 30 Am >5 and 8 An >2, preferably m is 12, 16 or 18 and n is 5; and a second copolymer comprising repeating units being represented by general formula (3): LO - (A - O -)x- BE (3) À.. À ..

: . where A is alkylene or phenylene, preferably (CH2)4; B is alkylene, ! phenylene, alkylene ether, phenylene ether, alkylene-phenylene ether, alkoxy phenylene ether or alkyl-phenylene ether;, preferably a substantially straight À À chain hydrocarbon, preferably (CH2)m where 30 Am >5 or B is -O-C6H4-O À.e À À (CH2)12-O-C6H4-O-; 40 2x '0.

Preferably, the galvanic cell, comprising an electrolyte, further comprises a lithium salt being represented by general formula (6): P0989. spec Li X (6) where X is CIO4-, BF4- CF3SO3- and/or (CF3SO2)N-; wherein said electrolyte is operable with conductivities in the range 10-4 to 1 o2 at ambient temperature.

According to an eighth aspect of the present invention, there is provided a process for the preparation of a polymer being represented by general formula (1) -R33; ( 1) where R' is alkylene or a benzene nucleus, R2 is oxygen, alkylene, phenylene or CH2; R3 is alkyl, phenyl, a substantially straight chain hydrocarbon preferably-(CH2)m-H where 30 Em 25, more preferably m is 12, 16 or 18; 8 on 2 2, preferably n is 5; said process comprising the steps of: (a) reacting a compound being represented by general formula (7): >-R3 where Y is a halogen, preferably Br or Cl; with a compound being A. À represented by general formula (8): À À- H O:(CH2)2Ot(CH2)2- OH (8) À:.

where 7 2p 21, preferably p is 3. À.e Àe À

Preferably, compounds (7) and (8) are reacted in a solvent mixture of DMSO: THF. ! P0989.spec According to a ninth aspect of the present invention, there is provided a process for the preparation of a copolymer, said copolymer comprising repeating units being represented by general formula (1) and (2): R2_R3 tRWo; (1) R2_R3 TAR O/ (2) where R' is alkylene or a benzene nucleus; R2 is oxygen, alkylene, phenylene or CH2; R3 is alkyl, phenyl or a substantially straight chain hydrocarbon, preferably-(CH2)m-H where 30 Em 25, more preferably m is 12, 16 or 18; 8 On 22, preferably n is 5; said process comprising the steps of: (a) reacting a compound being represented by the general formula (7): R2_R3 Y-CH2-R1-CH2-Y ( ) where Y is a halogen, preferably Cl or Br; with a compound being represented by general formula (8): À. .. À À

H O(CH2)2 - Ot(CH2)2 - OH (8) À .. . where 7 2p 21, preferably p is 3. À:

Preferably, the process further comprises reacting compound (7) and À À compound (8) in a solvent mixture of DMSO:THF. À .. À

Preferably, an order and a multiplicity of repeating units of compound (2) relative to compound (1) within said copolymer is dependent upon a ratio of DMSO to THE forming the co-solvent. That is an amount and distribution of P0989.spec compound (2) relative to compound (1) forming the copolymer may be 'tailored' by variation of a ratio of DMSO to THE.

According to a tenth aspect of the present invention, there is provided a process for the preparation of a compound being represented by the general formula (2): :R307 (2) where R' is alkylene or a benzene nucleus; R2 is oxygen, alkylene, phenylene or CH2; R3 is alkyl or phenyl, a substantially straight chain 10hydrocarbon, preferably-(CH2)m-H where 30 Am 25, more preferably m is 12, 16 or 18; the process comprising the steps of: (a) reacting a compound of general formula (7): R2_R3 Y- CH2- R1 CH2- Y ( ) 15where R. is alkylene or a benzene nucleus, R2 is oxygen, alkylene, phenylene or CH2; R3 is alkyl, phenyl, or a substantially straight chain À. .- : .. hydrocarbon, preferably-(CH2)m-H where 30 Am 25, more preferably m is 12, 16 À.e.

À or 18; said process comprising the steps of: with a compound being represented by general formula (9): Àe

A q q R'-R

H O - CH2-R.-CH2 - OH (9) À .. 20 À-r Preferably, compounds (7) and (9) are reacted in a solvent mixture of DMSO:THF.

P0989.spec According to an eleventh aspect of the present invention, there is provided a process for the preparation of a polymer electrolyte comprising the steps of: (a) forming an ion conducting polymeric material having repeating units being represented by general formula (2): R2_R3 tR O (2) where R' is alkylene or a benzene nucleus; R2 is oxygen, alkylene, phenylene or CH2; R3 is alkyl, phenyl, or a substantially straight chain hydrocarbon, preferably-(CH2)m-H where 30 Am 25, more preferably m is 12, 16 or 18; (b) heating said polymer electrolyte above a transition temperature.

Preferably, the process further comprises the steps of: (c) prior to said heating step (b) blending compound (2) with a compound being represented by general formula (1): e À. R2-R

e. tR Wo; (1) À .. À

air 8 An 22, preferably n is 5.

. Preferably, the process further comprises the step of: a.... À

(d) prior to said heating step (b) blending compound (2) with an ionic bridge polymer, said ionic bridge polymer being represented by general formula (3): P0989.spec tO - (A- O -)x - B (3) where A is alkylene or phenylene, preferably (CH2)4; B is alkylene, phenylene, alkylene ether, phenylene ether, alkylene-phenylene ether, alkoxy phenylene ether or alkyl-phenylene ether;, preferably a substantially straight chain hydrocarbon, preferably (CH2)m where 30 Am 25 or B is -O-C6H4-O (CH2)l2-O-C6H4-o-; 40 2x 220.

Preferably, the process further comprises the step of: (e) prior to said heating step (b) blending compound (2) and compound (1) with an ionic bridge polymer, said ionic polymer being represented by general formula (3): tO-(A-O-)X-B (3) where A is alkylene or phenylene, preferably (CH2)4; B is alkylene, phenylene, alkylene ether, phenylene ether, alkylene-phenylene ether, alkoxy phenylene ether or alkyl- phenylene ether;, preferably a substantially straight chain hydrocarbon, preferably (CH2)m where 30 Am 25 or B is -O-C6H4-O (CH2)12-O-C6H4-O-; 40 2x 220. c e

: I. 20 Preferably, said transition temperature is above a melting or glass transition temperature of compound (1). À

À HA Preferably, said transition temperature is between ambient and 11 0 C.

Preferably, following said heating step (b) said polymer electrolyte comprises a lamellar, micellar or lamellar-micellar complex morphology.

P0989.spec Preferably, said second ionic bridge polymer is represented by the general formula (10): R5-OLD-O iR5 (10) where D is alkylene or phenylene, preferably (CH2)r, where 5 or 22, preferably r is 4; R5 is alkyl, phenyl, a straight chain or branched aliphatic hydrocarbon preferably C'8H37; 40 As 220.

According to a specific implementation of the present invention the second ionic bridge polymer may be bonded to at least one end of the ion conducting polymer. For example, R5 of general formula (10) may be replaced with the repeating unit, being represented by general formula (2) . Accordingly, the second ionic bridge polymer is maintained at the interface between the amphiphilic ion coordinating regions and the interdispersed first ionic bridge polymer.

Accordingly enhanced conductivity of the polymer electrolyte may be associated with the ionic bridge-ion conducting polymer hybrid species due to the even distribution of the second ionic bridge polymer at the interface with the first ionic bridge polymer. The bonding of the second ionic bridge polymer to the end units of the ion coordinating regions or channels may avoid a requirement to Àe À. incorporate the separate and mobile second ionic bridge polymer in combination with the first ionic bridge polymer. Àe À:.

A possible synthetic route for the preparation of the above second ionic À :.. 25 bridge polymer- ion conducting polymer hybrid species involves the preparation of the ion conducting polymer followed by introduction of the second ionic bridge polymer within a suitable solvent medium. The second ionic bridge polymer is therefore "tagged" onto the end of the ion conducting polymer following the polymerization of the ion conducting polymer.

Po989 spec

Brief Description of the Drawinns

For a better understanding of the invention and to show how the same may be carried into effect, there will now be described by way of example only, specific embodiments, methods and processes according to the present invention with reference to the accompanying drawings in which: Fig. 1 illustrates schematically an organised, de-blended electrolyte complex; 10Fig. 2 illustrates schematically an ion conducting channel within the electrolyte complex; Fig. 3 illustrates schematically the electrolyte complex arranged as a lamellar texture; Fig. 4 is a log conductivity vs 1/T plot for an electrolyte system according to a specific implementation of the present invention; Fig. 5 is a log conductivity vs 1/T plot for an electrolyte system according to a specific implementation of the present invention; À À - Detailed Description of a Specific Mode for Carrvina Out the Invention Àe There will now be described by way of example a specific mode . contemplated by the inventors. In the following description numerous specific Àe details are set forth in order to provide a thorough understanding. It will be apparent however, to one skilled in the art, that the present invention may be À À = : practiced without limitation to these specific details. In other instances, well : known methods and structures have not been described in detail so as not to

unnecessarily obscure the description. 30!

Within this specification the repeating units of the ion conducting polymer are represented by PO1-sc in the case of a main-chain second repeating unit P0989.spec comprising secondary ion coordinating sites and PO5-sc for a main-chain first repeating unit comprising primary ion coordinating sites. According to specific implementations of the present invention PO1-sc involves a single alkylene oxide repeating unit optionally in addition to a hydrocarbon side-chain extending from the main-chain and PO5-sc comprises five alkylene oxide repeating units optionally in addition to a hydrocarbon side-chain. This nomenclature does in no way restrict the present invention to utilisation of an ion conducting polymer comprising specifically one or five alkylene oxide repeating units within the main- chain. As will be appreciated by those skilled in the art, the present invention may include any number ofalkylene oxide repeating units (single or plurality) forming part of the main-chain, in accordance with the teachings of the present invention.

Additionally, within this specification a first ionic bridge polymer is represented by 1 BP and a second ionic bridge polymer is represented by 2BP.

Referring to Figure 1 herein there is illustrated a schematic view of the polymer electrolyte comprising an ion conducting polymer 100 and a first ionic bridge polymer 101, exhibiting an ordered morphology.

Following a de-blending process, described below, the electrolyte system Àe À adopts a well-defined morphology where the ion conducting polymer is arranged! Ale. in discreet lamellar or micellar regions, ion transport within such regions being provided by the amphiphilic main-chain first and second repeating units, PO5-sc À À and PO1-sc, respectively. Ionic bridge polymer 101 (I BP or 2BP) provides a binding function being interdispersed between the micellar or lamellar regions. À

Ion transport therefore occurs between regions 100 and 101 where, for example, the electrolyte complex is provided between electrodes of a battery.

Referring to Figure 2 herein there is illustrated a schematic view of a coordinating channel of the electrolyte system as detailed with reference to Figure 1 herein comprising PO5-sc repeating units 200; PO1-sc repeating units P0989.spec 201; hydrocarbon side-chain repeating units 202; metal ions 203; coordinating atoms 204 and complex anions 205.

Following the de-blending process, described below, the electrolyte system adopts a well-defined morphology being arranged into ionophobic repeating unit regions involving an interdigitation of side-chains 202 as detailed with reference to Figure 3 herein, and ionophilic repeating unit regions or channels resulting from the organization of main-chain first and second repeating units 200, 201.

According to the specific implementation of the present invention the PO5sc repeating units 200 are arranged as a substantially helical ion coordinating channel 200, the PO1-sc repeating units 201 being interdispersed between this helical structure.

Accordingly, the main-chain ion conducting polymer backbone comprised 'spaces' or 'voids' 201 as detailed with reference to Figure 2 herein wherein metal ion transport 203 is enhanced within the ionophilic coordinating channel. By allowing the anions a degree of motional freedom due to the breaks 201 within channel 200, enhanced ion transport is achieved ultimately providing enhanced conductivity. A cation 'jump' motion promoted by local anion mobility may be envisaged within the coordinating channel. Accordingly, an electrolyte complex is provided allowing de-coupled ion motion within a plurality of coordinating À. e. I channels formed from oxygen-rich primary ion coordinating sites 200 being À. interdispersed with oxygen-deficient secondary ion coordinating sites 201. À À. À À

1BP 101 acts as an ionic bridge or 'glue' between lamellar or micellar regions. According to specific implementations of the present invention a second À : ionic bridge polymer 2BP 206 is provided, acting as an interface between ion conducting polymer regions 100 and ionic bridge 101. Incorporation of 2BP increases the observed conductivity in addition to weakening the temperature dependence of conductivity. I P0989.spec Due to a relative motional freedom enjoyed by 1BP and/or 2BP within the electrolyte system, on cooling the electrolyte an otherwise observed decrease in ion conductivity due to shrinkage and/or a freezing of the hydrocarbon ionophobic regions is offset by the 'glue'-like effect of the interdispersed 1BP and/or 2BP serving as an ionic bridge. Ion conductivity is therefore not substantially decreased following a decrease in temperature on passing through the melting and/or glass transition temperature of the interdigitated side-chains.

Referring to Figure 3 herein there is illustrated a schematic view of the electrolyte complex as detailed with reference to Figure 2 herein comprising a lamellar morphology the lamellar layers of ion conducting polymer 300 being separated by layers of 1 BP 301.

As will be appreciated by those skilled in the art, following the deblending process detailed below, interdigitation of the ionophobic hydrocarbon side-chains 202 and interaction between the metal salt and the ionophilic main-chain repeating units PO1-sc and PO5-sc provides an organised lamellar morphology.

Incorporation of 2BP within the complex, may to serve to facilitate regular termination of the main-chains in turn promoting aggregation and a possible micellar morphology.

À. e. 1 The polymer electrolyte according to the present invention, within a battery, see.

Aprovides for enhanced conductivity due to ion coordination within the coordinating channels resulting from ion oxygen-rich, ion oxygendeficient coordination of the polyalkylene oxide repeating units. À

: According to a second embodiment of the present invention ion transference is provided via ion coordinating channels comprising PO1-sc without incorporation or substantial incorporation of PO5-sc. A polymer electrolyte comprising a main-chain backbone of PO1-sc may provide mechanical advantages resulting from the increased chain rigidity. Electrolyte films of P0989.spec increased durability may therefore be provided in turn providing a more compact lightweight battery.

According to the second specific embodiment of the present invention 1 BP and/or 2BP are utilised to maintain conductivity at ambient and reduced temperatures, such ionic bridge polymers serving to offset any temperature I dependent conductivity effect on passing through the hydrocarbon side-chain melting and/or glass transition temperature(s).

10There will now be described specific examples according to certain aspects of the present invention.

PO1-sc may be represented by specific formula (1): o - C,6H33 0 (1) PO5sc may be represented by specific formula (11): o - C,6H33 e 1 À. 11(o: (11) . 1 BP may be represented by specific formula (111): À O:(CH2)4 03(CH2),2 (11) À À . : .: 2BP may be represented by specific formula (IV) C18H32 - Ol(CH2)4 - OtC18H37 (IV) P0989.spec Referring to Figure 4 herein there is illustrated AC conductivities measured by complex impedance spectroscopy as a log vs 1/T plot for the electrolyte system comprising the ion conducting polymer formed as a copolymer of compound (I) and (Il): compound (111): LiBF4 in molar ratios (1:1:1.2). During an initial heating (de-blending process) up to cat 100 C the conductivity rose steeply 400. On cooling 401 the conductivity remained high down to ambient temperature where following a second heating cycle 402 and cooling cycle 403, the conductivities remained high exhibiting reduced temperature dependence of the first heating cycle. Accordingly, conductivities within the range 10-2 to 10-4 S cmi have been observed with this system.

Enhanced ion conductivity is provided along the ionophilic main-chain polymer backbone due to the creation of 'spaces' within the main-chain backbone involving the copolymer of compounds (I) and (II) as detailed with reference to Figure 2 herein. Interdigitation of the C,6H33 hydrocarbon side-chains provides a well-defined electrolyte morphology allowing substantially de-coupled ion mobility notwithstanding minor local conformational motions of the polyether main-chains.

Referring to Figure 5 there is illustrated AC conductivities measured by complex impedance spectroscopy as a log cs vs 1/T plot for the ion conducting polymer formed as a copolymer of compounds (I) and (Il): compound (111): . . compound (IV): LiBF4 in molar ratios (1:0.8:0.2:1.2). As observed with reference À to Figure 4 herein following a first initial heating 500, consistently high *, conductivities are maintained during and following a first cooling cycle 501, a . . second heating cycle 502 and subsequent cooling cycle 503. Due to the incorporation of the 'surfactant' compound (IV), elevated AC conductivities are : observed for this system as compared with the system of Figure 4 herein. balm *

According to specific implementations of the present invention as a weight fraction the electrolyte system comprises 1 BP or 1 BP/2BP present as <ca. 50%.

P0989.spec Referring to Figures 4 and 5 herein the de-blending process establishing the lamellar or micellar morphologies is onset by initial heating cycle 400, 500, the established morphology being maintained through the first and successive cooling cycles providing in turn enhanced electrolyte ion conductivities having reduced temperature- dependent characteristics.

DC polarization measurements using lithium electrodes gave ambient conductivities in the range 10-3 to 1 o-2 S cm' in good accord with AC impedance measurements. Such DC conductivities thereby implying Li+ transport between electrodes. Moreover, conductivities of the order 10-2 S cm' were observed at ambient temperature; such conductivities being established and maintained following an initial "electrolyte-ordering".

There will now be described specific preparations and examples to illustrate specific aspects of the present invention.

General Preparation Procedure for Compound (I) and (II) Copolymer According to the present invention, the copolymer of compound (I) and (II) was prepared in dry DMSO: THF co-solvent. By adjusting the relative proportions of DMSO to THF a tunable synthetic procedure is provided whereby a desired amount of main-chain first repeating units (compound (II)) and main-chain À .. second repeating units (compound (I)) are incorporated within the main-chain polymer backbone. Accordingly, the aforementioned substantially helical ion À À coordinating channel is formed from compound (II) being interdispersed with ion coordinating 'spaces' resulting from incorporation of compound (I). In particular, À 9 : increasing the amount of DMSO (being a substantially polar solvent) has the :: effect of increasing aggregation of the hydrocarbon side-chains thereby promoting synthesis of an ion conducting polymer being compound (I) rich.

Conversely, if the molar concentration of THF is increased, aggregation of the hydrocarbon side-chains is less and an ion conducting polymer having enhanced main-chain second repeating unit content (compound (II)) may be obtained.

P0989.spec Synthesis of 5-hydroxybenzene-1,3-dicarboxylic acid diethyl ester

OH OH

HO2C EtOH,'CO2Et 36.5g (0.2mol) 5-hydroxyisophthalic acid, 150ml ethanol and 2ml concentrated sulphuric acid were reflexed for 3 furs. The ethanol was removed under vacuum and the white crystals were washed with water and then dissolved in 200ml ethyl acetate. The solution was washed sequentially with aqueous sodium bicarbonate solution and water and finally dried over magnesium sulphate. After concentrating the solution under vacuum, white needles separated. The yield of 5-hydroxybenzene-1,3dicarboxylic acid diethyl ester, m.p. 106 C, was 43.4g (91%). IR: 3291.4, 2985, 2907, 1804 - 1700, 1400-1250 cm'.

Synthesis of 5-hexadecyloxybenzene-1,3-dicarboxylic acid diethyl ester OH O C, 6 H33 EtO Cam' C'6H33Br CO2Et À Àe À À 16.5g (0.069mol) 5-hydroxybenzene-1,3-dicarboxylic acid diethyl ester, 21g À e.

(0.069mol) 1 -bromohexadecane and 120ml acetone were reflexed in the presence of 11.9g (0.086mol) potassium carbonate for 24 furs. After addition of À..

100ml water, the solution was extracted with pentane. The pentane solution was washed with aqueous potassium hydroxide solution, water and then dried over magnesium sulphate. The solvent was evaporated under reduced pressure. The yield of 5-hexadecyloxybenzene-1,3-dicarboxylic acid diethyl ester, m.p.45 C, was 24g (75%). IR: 3042, 2935, 1724, 1608, 1501, 1475 and 1251 cm'.

P0989.spec Synthesis of 5-hexadecyloxybenzene-1,3-dimethanol 0 cue H33 Oc'6 H33 EtO2C'[ 'CO2Et HOCH2J CH2OH 15g (0.0325mol) 5-hexadecyloxybenzene-1,3-dicarboxylic acid diethyl ester was reduced using 3.19 (0.082mol) lithium aluminium hydride by refluxing in ethyl ether for 4 furs. Ethyl acetate was added into the solution to decompose the remaining lithium aluminium hydride. The solution was poured into cooled 20% sulphuric acid. The mixture was extracted with chloroform. After drying over magnesium sulphate, the extract was evaporated under reduced pressure. The crude product was recrystallized from dichloromethane to afford white crystals.

The yield of 5-hexadecyloxy benzene-1,3-dimethanol, m.p.90 C, was 1Og (81%).

IR: 3256, 3060, 2917, 1600, 1472, 1150 and 1031 cm'. Elemental analysis, required: (%) C (76.19), H(11.11); found: (%) C (76.07), H (11.40).

HNMR(CDCI3) 0.85 (t, 3H), 1.25 (s 24H), 1.45 (5 peaks, 2H), 1.75 (5 peaks, 2H), 3.9 (t 2H), 4.65 ( d, 4H), 6.85 (s, 2H), 6.95 (s, 1 H).

Synthesis of 5-hexadecylaxy-1,3-bis(bromomethyl)benzene À . À OC16H33 Ocl6H33 1 1 À . HOH2C/\CH2OH BrH2C/\CH2Br :. 5 g of 5-hexadecyloxybenzene -1, 3-dimethanol was suspended in 20 ml dry ethyl ether and stirred under a dry atmosphere and cooled down to 0 C. Into the suspension, 3.18g of phosphorous tribromide was added drop-wise, while keeping the temperature of the mixture below 5 C. After completion of the addition, the solution was allowed to warm up to room temperature and stirred for furs. The reaction mixture was then poured into a crushed ice bath, the separated organic layer was washed with a 10% sodium carbonate in water P0989.spec solution. The product was dried over anhydrous potassium carbonate and the solvents evaporated to yield white crystals. AH NMR(CDCI3): 0.85 (t, 3H), 1.25 (s, 28H), 1.45 (5 peaks, 2H), 1.75 (5 peaks, 2H), 3.95 (t, 2H), 4.40 (s, 4H), 6.85 (s, 2H). 6.95 (s,1 H). Elemental analysis: Br, required 31.68%, found 31. 49%.

Synthesis of Polymer compound (II) Oc,6H33 Ocl6H33 HO(CH2CH2O)3CH2CH2OH BrH2C\CH2Br KOH 4O:n Compound (II), was prepared by heating with gentle stirring at 350 C of 1g (0.002mol) 5-hexadecyloxy-1,3-bis(bromomethyl)benzene, 0.385g (0.002mol) tetraethylene glycol, and 0.44g (0.008mol) potassium hydroxide in 1ml dimethyl sulphoxide and 1 ml THF for 3 hours. The polymer was precipitated in water. The mixture was neutralized with concentrated acetic acid. The polymer was separated and washed with hot water 3 times to remove inorganic salt and finally with hot methanol 3 times to remove monomer. 1H NMR(CDCI3) 6: 0.85 (t, 3H), 1.25 (s, 28H), 1.75 (5 peaks, 2H), 3.65 (d, 15H), 3.95 (t, 2H), 4.50 (s, 4H), 6.80 Àe e.

(d, 3H). Hot stage microscopy indicates that the polymer melts at 27 C. The FTIR À.e À .. spectrum shows that the peak of OH group (3256 cm1) is not present. À e. À À . À À e ee.

Svnthesis of compound (I) [example 11 À À À Àe OC16H33 OC16H33 OC16H33 grHzC/CH2Br HOCH:- 'CH2OH O/t P0989.spec Compound (I), was prepared by heating with gentle stirring at 60 C of 1g (0.002mol) 5-hexadecyloxy-1,3-bis(bromomethyl)benzene, 0.75g (0.002mol) 5hexadecyloxybenzene -1,3-dimethanol, and 0.44g (0.008mol) potassium hydroxide in 1 ml dimethyl sulphoxide and 1 ml THE for 3 days. The polymer was precipitated in water. The mixture was neutralized with concentrated acetic acid.

The polymer was separated and washed with hot water 3 times to remove inorganic salt and finally with hot methanol 3 times to remove monomer. 'H NMR(CDCI3) 8: 0.85 (t, 3H), 1.25 (s, 27H), 1.45 (5 peaks, 2H), 1.75 (5 peaks, 2H), 3.95 (t, 2H), 4.50 (s, 4H), 6.85 (d, 3H). Tm = 42 C (hot stage optical microscopy). The FTIR spectrum shows that the OH peak (3256 cm-') is not present.

Synthesis of Compound (I)-(ll) Copolymer oCl6H33 C16H33 oCl6H33 HO(CH2CH2O)3CH2CH2O BrH2\CH2Br KOH \O/\\O/ The copolymer of compound (I)(ll), was prepared by heating with gentle a. Àe À . stirring at 60 C of 1g (0.002mol) 5-hexadecyloxy-1,3-bis(bromomethyl)benzene, À..

0.385g (0.002mol) tetraethylene glycol, and 0.88g (0.016mol) potassium hydroxide in 2ml dimethyl sulphoxide for 20 min. The polymer was precipitated in À . water. The mixture was neutralized with concentrated acetic acid. The polymer was separated and washed with hot water 3 times to remove inorganic salt and À . : finally with hot methanol 3 times to remove monomer. H NMR(CDCI3) 8: 0. 85 (t, : : 3H), 1.25 (s, 28H), 1.45 (5 peaks, 2H), 1.75 (5 peaks, 2H), 3.60 (2 main peaks, 10.6H), 3.95 (t, 1.6H), 4.50 (s, 3.3H), 6.80 (d, 2.7H). The GPC gave molar mass averages, Mw = 70.5 x 103, Mz = 4.9 x 106. Hot stage microscopy indicates that the polymer melts at 28 C. The FTIR spectrum shows that the peak of OH group (3256 cm-') is not present. The ratio [ethoxy hydrogens(6 3.60)] / [ aromatic P0989.spec hydrogens(d 6.8)] = (3 / 2.7) x (10.6 / 16) = 0.74 indicates 26% of compound (I) units in the copolymer.

Synthesis of *Compound (111) HO-[-(-CH2')4 - lx -H KOH -A -{O-[-(-CH 2)4 O-]x -R-} *where x 23 where R= At- CH212 l *Compound (111) was prepared by standard Williamson condensation of hydroxy-terminated polytetrahydrofuran (Mn = 1688 g mold) with 1,12- dibromododecane and excess powdered KOH (8 molar ratio) at 90 C.

*compound (111) was purified by washing with dilute aqueous acetic acid followed by water and dried under vacuum. . Gel permeation chromatography showed that <Mw> = 2.5 x 104. IR: 2940cm', 2859cm1 (CH2 stretch) and 1113cm1 (C-O stretch). DSC of *compound (111) indicates that the polymer melts at 24 C.

Synthesis of *Compound (IV) CaH37Br H0- CH2CH2CH2CH2Cx H KOH ' C'3H370( CH2CH2CH2CH2x C,H À... À À...

*Where x is 45. À . À- *

*Compound (IV) was prepared by standard Williamson condensation of * 8.44g (0.005mol) hydroxy-terminated polytetrahydrofuran (Mn = 1688 g mold) l À with 3.33g (0.005mol) 1-bromododecane and excess powdered (8 molar ratio) À 2.24g KOH in 40ml dimethyl sulphoxide for 7 days at 90 C. *Compound (IV) was purified by washing with dilute aqueous acetic acid followed by water and dried under vacuum. The GPC result gave molar mass averages Mn = 3250; Mw = 4724. DSC of *compound (IV) indicates that the polymer melts over the range 10 P0989.spec - 35 C. IR 3482 (vOH), shoulder 3000-2950 (v-CH3) 2923, 2798, 2740, (vCH2) 1110 (vC-O) Synthesis of diethyl 2-octadecyl propandioate, synthesis of diethyl 2 octadecyl propanedioate After dissolving 2.3g of Na (0.1 mole) in 250ml anhydrous EtOH, 16g of diethylmalonate (0.1 mole) was added dropwise under argon. After one hour at 50 C, 33.3g (0.1 mole) of 1-bromooctadecane was added and the mixture stirred for 15h. The solution was concentrated to dryness and washed with hot CHCI3.

The precipitate of NaBr is filtered and the solution dried over MgSO4. After evaporation, a yellow oil was obtained and distilled to give, 23g of diethyl 2- octadecyl propanedioate, yield 56%, bp: 185-190 C /0.04 torn Mp: 28 C. IR: 2918cm' (CH3 stretch), 2850cm4 (CH2 stretch) and 1733cm' (C=0 stretch).

Ref: M.V.D. Nguyen, M.E. Brik, B.N. Ouvrard, J. Courtieu, L. Nicolas and A. Gaudemer, Bull. Soc. Chim. Belg., 1996, 105(14), 181-3.

Synthesis of 2-octadecyl propane-1,3-diol À.. .

23g (0.056mol) diethyl 2-octadecyl propanedioate was reduced using 5.4g (0.14mol) lithium aluminium hydride by refluxing in ethyl ether for 6 furs. Ethyl À - acetate was added into the solution to decompose the extra lithium aluminium hydride. The solution was poured into cooled 20% sulphuric acid. Collect the À . :.. 25 white solid after ether was evaporated. Wash the solid with water, aqueous : : K2CO3 solution and then water. After drying in an oven, the product was extracted in dichloromethane using a soxhlet apparatus and evaporation of the solvent gave the pure white product. The yield of 2- octadecyl propane-1,3-diol, m.p.88 C, was 15g (81%).

P0989.spec Synthesis of Aliphatic Compound (II) Variant 8H37 1 8 H37 /CH\ Br (-CH2CH2OtCH2CH2Br CH HOCH2 cH2OH NaH/DMF -OCH2 CH2 t OCH2 CH2 on 1.64g (0.05mol) 2-octadecyl propane-1,3-diol and 0.24g (0.05mol) NaH were mixed under an argon atmosphere,.and 15ml DMF was added. The mixture was heated slowly with stirring to 90 C over 1 hour. 1.6g of tetraethyleneglycol dibromide in 5ml DMF was added dropwise into the reaction and stirring was maintained at this temperature for 1 day. A second portion of 0.24g NaH was then added and stirring continued at 90 C for a further 3 days. After the reaction mixture was cooled, water was added, followed acetic acid to neutralize the solution. The solid was separated by filtration and twice washed with water. The solid was precipitated from methanol. The aliphatic compound (II) variant, mostly melts at 45 C. H NMR(400MHz, CDCI3): 6=0.86(t, 3H, CH3), 1.22 (s, 34H, alkyl chain 17CH2),1.75 (m, 1 H. CH), 3.60(t, 8H, OCH2).

Synthesis of Compound (I) [example 2] OCl6H33 OCl6H33 À ' HOCH2/'CH2OH \ À:- : :. .. Compound (II), was prepared by heating with gentle stirring at 60 C of 1.00g (0.00264mol) 5- hexadecyloxybenzene -1, 3-dimethanol, and 2.24g (0.04mol) potassium hydroxide in 5ml dimethyl sulphoxide for 7 days. The polymer was precipitated in water; the mixture was neutralized with concentrated acetic acid and extracted into chloroform. After evaporation of the chloroform, the residue was washed with hot water to remove inorganic salt and finally with hot methanol several times to remove the monomer. The GPC result gave molar P0989.spec mass averages Mw =10,000. DSC indicates that the polymer melts at 36 C. NMR (6 4.5)shows only 2-3 a - hydrogens of the two -CH2-attached to the benzene nucleus in the main chain. The FTIR spectrum shows that part of the peak of OH group disappears.

Synthisis of compound (111)-derivatives:O(- CH2 - )3 Ot Rem The above compound (111)-derivative may be prepared by a ring opening cationic polymerization. The cyclic ether may be cleaved with BF3/dietherate so as to generate the required polyalkylene oxide. Such a process may similarly be 1 0 employed for other similar compound (111)-variants.

According to the compound (111)-derivatives the R group is derived from a cyclic ether whereby copolymers may be synthesized involving cyclic ether ring opening polymerizations providing in turn high molecular weight polymers (Mw ca 105). Where the compound (111)-derivative comprises -(CH2)3- the cyclic ether derived R group may optionally comprise additional hydrocarbon side groups appended to the cyclic ether ring (for example methyl groups). Such side groups enhance the hydrophobic character of the polymer. e-Àe e e Àe

. 20 Specific examples of the compound (111)-derivative copolymers comprise: ee. À

- [ - (CH2)3 - O - ] - [ - (CH2)4 - O - ] -; or À e en e [ (CH2)3 - O - ] - [ - CH2 - C(CH3)2 - CH2 - O - ] -; where repeating units À - are randomly mixed. Moreover, the ionophobic character of the resulting polymer À e may be selectively adjusted by varying the relative amount of the cyclic ether containing at least one side group, during polymerization of the above compound (11 1)-derivatives.

P0989.spec Accordingly and owing to the large polymer molecular weight distributions, electrolyte systems may be provided with enhanced mechanical properties being advantageous in the manufacture of batteries.

Electrolyte Prenaration Complexes were prepared by mixing the ion conducting polymer with 1BP and/or 2BP together with appropriate molar proportion of Li salt, being selected from, for example, LiCI04, LiBF4, LiCF3SO3, or Li(CF3SO2)N, in a mixed solvent of dichloromethane/acetone. After removal of solvent with simultaneous stirring complexes were dried under vacuum at 50 C-60 C.

An alternative preparation of the electrolytes may involve the known process of freeze-drying, following which the highly expanded polymer is collapsed as a powder and gently sintered below the de-blending temperature (ca. below 50 C).

Cell Prenaration The Li electrodes were prepared under an atmosphere of dry argon from Li, pellets mounted in counter-sunk cavities (500,um deep) in stainless steel strips.

Cells having ITO electrodes were prepared using cellulose acetate spacers (100 20,um). Complex impedance measurements and DC polarizations were performed using a Solartron 1287A electrochemical interface in conjunction with a 1250 frequency response analyser. À À- À À

Metal alloys, in particular, lithium cobalt oxides, manganese oxides or tin based alloys may also be utilised within the cell as cathodic electrodes being configured with a "binder" between particles and between electrode and À.- electrolyte, the ''binder'! possibly being selected from any one or a combination of À . PEO, PO1-sc, PO5-sc, P-nsc, 1 BP and/or 2BP.

P0989.spec

Claims

Claims: 1. A polymer electrolyte being configured to provide ion

transport, said polymer electrolyte comprising: a main-chain first repeating unit configured to provide a primary ion coordinating site, a plurality of main-chain repeating units being arranged as a substantially helical ion coordinating channel; said polymer electrolyte further comprising and being characterized by: a main-chain second repeating unit being interdispersed between said main-chain first repeating unit, said second repeating unit being configured to provide a secondary ion coordinating site within said coordinating channel, said secondary ion coordinating site being less strongly coordinating then said primary ion coordinating site; wherein said polymer electrolyte is configured to provide ion transport within said coordinating channel involving ion transport between said primary ion coordinating site and said secondary ion coordinating site.

À
2. The polymer electrolyte as claimed in claim 1 wherein said main À . chain first repeating unit and/or said main-chain second repeating unit comprise a hydrocarbon side-chain extending from said main-chain repeating unit, said À À hydrocarbon side-chain being configured to interdigitate with hydrocarbon side À.

chains of neighbouring main-chain repeating units. À À À.-
3. The polymer electrolyte as claimed in claims 1 or 2 wherein said ion À . coordinating channel is oxygen-rich at said primary ion coordinating site; and said ion coordinating channel is oxygen-deficient at said secondary ion coordinating site.

P0989.spec
4. The polymer electrolyte as claimed in any one of claims 1 to 3 wherein said main-chain first repeating unit comprises a plurality of ethylene oxide repeating units and said main-chain second repeating unit comprises at least one methylene oxide repeating unit.
5. The polymer electrolyte as claimed in any one of claims 1 to 4 wherein said polymer electrolyte comprises a plurality of substantially helical ion coordinating channels being formed from a plurality of main-chain first and second repeating units arranged as a lattice by interdigitation of the hydrocarbon 1 0 side-chains.
6. The polymer electrolyte as claimed in any one of claims 1 to 5 wherein ions being transported within said coordinating channel are substantially decoupled from conformational motion of said main-chain first and second repeating unit.
7. The polymer electrolyte as claimed in claims 5 or 6 further comprising: a second polymer comprising ionophilic polyoxyalkylene units. À. Àe À À
8. The polymer electrolyte as claimed in claim 7 wherein said second polymer is positioned between said lattice of said plurality of mainchain first and À À À À second repeating units.

À - ! :. .
9. A copolymer comprising repeating units being represented by #. -e general formula (1) and (2): À . i P0989.spec R2_R3 tR1: (1) o R2_R3 MAR': (-he (2) where R' is alkylene or a benzene nucleus; R2 is oxygen, nitrogen, alkylene, phenylene or CH2; R3 is alkyl, phenyl or alkyl-phenyl and 8 on 22, preferably n is5.
10. The copolymer as claimed in claim 9 wherein R. is a benzene nucleus, R2 is oxygen and R3 is a substantially straight chain hydrocarbon preferably-(CH2)m-H where 30 >m 25, more preferably m is 12, 16 or 18.
11. The copolymer as claimed in claim 9 wherein R. is CH, R2 is oxygen and R3 is a substantially straight chain hydrocarbon preferably-(CH2)m-H where 30 Em 25, more preferably m is 12, 16 or 18.
12. A polymer blend comprising a first copolymer and a second copolymer, said first copolymer comprising repeating units being represented by À general formula (1) and (2): À- À.

À- R2_R3 tR1 (1) : . O I..

À R<-R MAR': (-he (2) P0989.spec where R' is alkylene or a benzene nucleus; R2 is oxygen, nitrogen, alkylene, phenylene or CH2; R3 is alkyl, phenyl or alkyl-phenyl and 8 An 22, preferably n is 5; and said second copolymer comprising repeating units being represented by general formula (3): tO-(A-O-)x-B (3) where A is alkylene or phenylene; B is alkylene, phenylene, alkylene ether, phenylene ether, alkylene-phenylene ether, alkoxy-phenylene ether or alkyl phenylene ether; 40 2x 220.
13. The polymer blend as claimed in claim 12 wherein R' is a benzene; nucleus; R2 is oxygen and R3 is a substantially straight chain hydrocarbon preferably-(CH2)m-H where 30 Am 25, more preferably m is 12, 16 or 18; A is (CH2)4; B is a substantially straight chain hydrocarbon preferably (CH2)m or B is - l O-C6H4-O-(CH2),2-O-C6H4-O
14. The polymer blend as claimed in claim 12 wherein R' is CH, R2 is oxygen and R3 is a substantially straight chain hydrocarbon preferably - (CH2)m-H where 30 Am 25, more preferably m is 12, 16 or 18; A is (CH2)4; B is a substantially straight chain hydrocarbon preferably (CH2)m or B is -O-C6H4-O he (CH2).2-O-C6H4-O-.
15. A polymer electrolyte being configured to provide ion transport, said À'.. 25 polymer electrolyte comprising: À... e À a main-chain polyether repeating unit being configured to provide ion transport; P0989.spec an alkylene group or benzene nucleus being interdispersed within said polyether repeating unit; said polymer electrolyte further comprising and being characterized by: a hydrocarbon side-chain extending from said alkylene group or said benzene nucleus, said hydrocarbon side-chain being configured to interdigitate with hydrocarbon side-chains of neighbouring polyether repeating units; ; wherein ion transport is provided within a coordinating channel formed by said polyether repeating unit.
16. The polymer electrolyte as claimed in claim 15, wherein said hydrocarbon side-chain is alkyl, phenyl or a substantially straight chain i hydrocarbon preferably-(CH2)m-H where 30 Am 25, more preferably m is 12, 160r18.
17. The polymer electrolyte as claimed in claims 15 or 16 wherein said hydrocarbon side-chain is provided on each alkylene group or benzene nucleus of a plurality of repeating units. À. as

À a a I À
18. The polymer electrolyte as claimed in claims 15 or 16 wherein said hydrocarbon side-chain extends from some of the alkylene groups or benzene À À À. ' nuclei of a plurality of repeating units.

À 25
19. The polymer electrolyte as claimed in any one of claims 15 to 18 ece .a. wherein said polymer electrolyte is arranged as a lattice, said lattice comprising a ionophilic regions of polyether repeating units and ionophobic regions of hydrocarbon side-chains.
20. A polymer comprising a repeating unit being represented by general formula (2): P0989.spec

20. A polymer comprising a repeating unit being represented by general formula (2): P0989.spec R2_R3 tR who/+ (2) where R1 is alkylene or a benzene nucleus; R2 is oxygen or nitrogen, alkylene, phenylene or CH2; R3 is alkyl, phenyl, alkyl-phenyl or hydrogen.

21. The polymer as claimed in claim 20 wherein R1 is a benzene nucleus, R2 is oxygen and R3 is a substantially straight chain hydrocarbon preferably-(CH2)m-H where 30 Em 25, more preferably m is 12, 16 or 18.

22. The polymer as claimed in claim 20 wherein R. is CH, R2 is oxygen and R3 is a substantially straight chain hydrocarbon preferably -(CH2)m-H where >m 25, more preferably m is 12, 16 or 18.

23. The polymer as claimed in claim 20 wherein R1 is CH or a benzene nucleus, R2 is CH2 and R3 is a substantially straight chain hydrocarbon preferably -(CH2)m-H where 30 >m 25, more preferably m is 12, 16 or 18.

24. A polymer electrolyte being configured to provide ion transport, said polymer electrolyte comprising: À.ee. 20 an ion conducting polymer being represented by general formula (2): i À À. À

À À e R2_R3 : tR1Wo/ t (2) À À À À.

: , where R1 is alkylene or a benzene nucleus; R2 is oxygen, nitrogen, alkylene, phenylene or CH2; R3 is alkyl, phenyl or alkyl-phenyl; and an ionic bridge polymer being represented by general formula (3): P0989.spec tO-(A-O-)X-B (3) where A is alkylene or phenylene; B is alkylene, phenylene, alkylene ether, phenylene ether, alkylene-phenylene ether, alkoxy-phenylene ether or alkyl- phenylene ether; 40 2x 220.

25. The polymer electrolyte as claimed in claim 24 wherein R' is a benzene nucleus; R2 is oxygen and R3 is a substantially straight chain hydrocarbon preferably-(CH2)m-H where 30 Am 25, more preferably m is 12, 16 or 18; A is (CH2)4; B is a substantially straight chain hydrocarbon preferably (CH2)m or B is -O-C6H4-O-(CH2)12-O-C6H4-O-.

26. The polymer electrolyte as claimed in claim 25 wherein R. is CH, R2 is oxygen and R3 is a substantially straight chain hydrocarbon preferably (CH2)m-H where 30 Am >5, more preferably m is 12,16 or 18; A is (CH2)4; B is a substantially straight chain hydrocarbon preferably (CH2)m or B is O-C6H4-O (CH2),=0-C6H4-O-.

27. A galvanic cell comprising a polymer electrolyte according to claim 1. A 20 À

28. A galvanic cell comprising a polymer blend according to claim 12. À À. À À À.

À 29. A galvanic cell comprising a polymer blend according to claim 15. À

30. A galvanic cell comprising a polymer electrolyte, said polymer À.e electrolyte comprising a polymer according to claim 20.

31. A galvanic cell comprising a polymer electrolyte, said polymer electrolyte comprising a polymer according to claim 24.

P0989.spec 32. The galvanic cell as claimed in any one of claims 27 to 31 configured for lithium ion transference.

33. The galvanic cell as claimed in claim 32 wherein said galvanic cell is a solvent free battery.

34. The galvanic cell as claimed in claims 32 or 33 wherein electrolytedecoupled ion transport occurs via ionophilic repeating unit channels between a cathode and anode.

35. A galvanic cell comprising a polymer electrolyte being formed from a first copolymer comprising repeating units being represented by general formula (4) and (5): O - (CH2)m - H By.

\0/; (4) O- (CH2)m - H 2 0/] (5) e 2' where 30 Am 25 and 8 An 22, preferably m is 12, 16 or 18 and n is 5; and a second copolymer comprising repeating units being represented by general formula (3): TO - (A - O -)xBE (3) P0989.spec where A is alkylene or phenylene, preferably (CH2)4; B is alkylene, phenylene, alkylene ether, phenylene ether, alkylene-phenylene ether, alkoxy phenylene ether or alkyl-phenylene ether;, preferably a substantially straight chain hydrocarbon, preferably (CH2)m where 30 Em 25 or B is -O- C6H4-O (CH2),2-O-C6H4-O-; 40 2x 220.

36. The galvanic cell, comprising an electrolyte, as claimed in any one of claims 27 to 35 further comprising a lithium salt being represented by general formula (6): Li X (6) where X is CIO4-, BF4- CF3SO3- and/or (CF3SO2)N-; wherein said electrolyte is operable with conductivities in the range 10-4 to 10-2 at ambient temperature.

37. A process for the preparation of a polymer being represented by general formula (1): (1) : .. . where R1 is alkylene or a benzene nucleus, R2 is oxygen, alkylene, Àe- e phenylene or CH2; R3 is alkyl, phenyl, a substantially straight chain hydrocarbon preferably-(CH2)m-H where 30 Am 25, more preferably m is 12, 16 or 18; 8 An 2 À . 2, preferably n is 5; said process comprising the steps of: : . 25 (a) reacting a compound being represented by general formula (7): y 1 CH Y (7) - CH2 - R - 2 P0989.spec where Y is a halogen, preferably Br or Cl; with a compound being represented by general formula (8): H O(CH2)2- Ot(CH2)2- OH (8) where 7 2p 21, preferably p is 3.

38. The process as claimed in claim 37 wherein compounds (7) and (8) are reacted in a solvent mixture of DMSO: THE.

39. A process for the preparation of a copolymer, said copolymer comprising repeating units being represented by general formula (1) and (2): R2_R3 tR Wo; ( 1) R2_R3 try I/ (2) where R1 is alkylene or a benzene nucleus; R2 is oxygen, alkylene, phenylene or CH2; R3 is alkyl, phenyl or a substantially straight chain hydrocarbon, preferably-(CH2)m-H where 30 Am 25, more preferably m is 12, 16 or 18; 8 An 22, preferably n is 5 À me À e said process comprising the steps of: (a) reacting a compound being represented by the general formula (7): À.e À À R2_R3 Y- CH2- R1 CH2 -Y ( ) P0989.spec where Y is a halogen, preferably Cl or Br; with a compound being represented by general formula (8): H Ot(CH2)2 - Ot(CH2)2 - OH (8) where 7 2p 21, preferably p is 3.

40. The process as claimed in claim 39 further comprising reacting compound (7) and compound (8) in a solvent mixture of DMSO:THF.

41. The process as claimed in claim 40 wherein an order and a multiplicity of repeating units of compound (2) relative to compound (1) within said copolymer is dependent upon a ratio of DMSO to THE forming the solvent mixture.

42. A process for the preparation of a compound being represented by the general formula (2): :O/] (2) where R1 is alkylene or a benzene nucleus; R2 is oxygen, alkylene, À. . phenylene or CH2; R3 is alkyl or phenyl, a substantially straight chain hydrocarbon, preferably-(CH2)m-H where 30 Am 25, more preferably m is 12, 16 À. e . 20 or 18; À . : the process comprising the steps of: À..e À (a) reacting a compound of general formula (7): Y - CH2 - of- CH2 - Y (7) P0989.spec where R1 is alkylene or a benzene nucleus, R2 is oxygen, alkylene, phenylene or CH2; R3 is alkyl, phenyl, or a substantially straight chain hydrocarbon, preferably-(CH2)m-H where 30 Em 25, more preferably m is 12, 16 or 18; said process comprising the steps of: with a compound being represented by general formula (9): R2_R3 H O - CH2-R1_ CH2 - OH (9) 43. The process as claimed in claim 42 wherein compounds (7) and (9) are reacted in a solvent mixture of DMSO:THF.

44. A process for the preparation of a polymer electrolyte comprising the steps of: (a) forming an ion conducting polymeric material having repeating units being represented by general formula (2): R2_R3 {_R1: (: (2) À e À À.e.

À. where R' is alkylene or a benzene nucleus; R2 is oxygen, alkylene, phenylene or CH2; R3 is alkyl, phenyl, or a substantially straight chain À.

hydrocarbon, preferably-(CH2)m-H where 30 Am 25, more preferably m is 12, 16 or 18; À - -- : 2 (b) heating said polymer electrolyte above a transition temperature.

45. The process as claimed in claim 44 further comprising the steps of: (c) prior to said heating step (b) blending compound (2) with a compound being represented by general formula (1): P0989.spec R2_R3 tRWo (1) 8 on 22, preferably n is 5.

46. The process as claimed in claim 44 further comprising the step of: (d) prior to said heating step (b) blending compound (2) with an ionic bridge polymer, said ionic bridge polymer being represented by general formula (3) TO - (A- O -)x- B (3) where A is alkylene or phenylene, preferably (CH2)4; B is alkylene, phenylene, alkylene ether, phenylene ether, alkylene-phenylene ether, alkoxy phenylene ether or alkyl- phenylene ether;, preferably a substantially straight chain hydrocarbon, preferably (CH2)m where 30 Am 25 or B is -O-C6H4-O (CH2)l2-O-C6H4-O-; 40 2x 220.

47. The process as claimed in claim 45 further comprising the step of: À. À- À A..

(e) prior to said heating step (b) blending compound (2) and compound (1) with an ionic bridge polymer, said ionic polymer being represented by general formula(3): À:.

: TO - (A- O -)x- B (3) e À . where A is alkylene or phenylene, preferably (CH2)4; B is alkylene, phenylene, alkylene ether, phenylene ether, alkylene-phenylene ether, alkoxy phenylene ether or alkyl- phenylene ether;, preferably a substantially straight chain hydrocarbon, preferably (CH2)m where 30 Am 25 or B is -O-C6H4-O (CH2)l2-O-C6H4-O-; 40 2x 220.

P0989.spec 48. The process as claimed in any one of claims 44 to 47 wherein said transition temperature is above a melting or glass transition temperature of compound (1).

49. The process as claimed in claim 48 wherein said transition temperature is between ambient and 11 SAC.

50. The process as claimed in any one of claims 44 to 49 wherein following said heating step (b) said polymer electrolyte comprises a lamellar, micellar or lamellar-micellar complex morphology. À* Àe À À ose. À

À - .. À À. À À À.e À.. À À

À. - . I. À . P0989.spec Amendments to the claims have been filed as follows 1. A polymer electrolyte being configured to provide ion transport, said polymer electrolyte comprising: a main-chain first repeating unit configured to provide a primary ion coordinating site, a plurality of main-chain repeating units being arranged as a substantially helical ion coordinating channel; said polymer electro!.e further comprising and being characterized by: a main-chain second repeating unit being interdispersed between said main-chain first repeating unit, said second repeating unit being configured to provide a secondary ion coordinating site within said coordinating channel, said secondary ion coordinating site being less strongly coordinating than said primary ion coordinating site; wherein said polymer electrolyte is configured to provide ion transport within said coordinating channel involving ion transport between said primary ion coordinating site and said secondary ion coordinating site.

2. The polymer electrolyte as claimed in claim 1 wherein said main chain first repeating unit and/or said main-chain second repeating unit comprise a hydrocarbon side-chain extending from said main-chain repeating unit, said hydrocarbon side-chain being configured to interdigitate with hydrocarbon side chains of neighbouring main-chain repeating units.

3. The polymer electrolyte as claimed in claims 1 or 2 wherein said ion coordinating channel is oxygen-rich at said primary ion coordinating site; and said ion coordinating channel is oxygen-deficient at said secondary ion coordinating site.

P0989.spec an alkylene group or benzene nucleus being interdispersed within said poiyether repeating unit; a hydrocarbon side-chain extending from said alkylene group or said benzene nucleus, said hydrocarbon sidechain being configured to interdigitate with hydrocarbon side-chains of neighbouring polyether repeating units; said polymer electrolyte characterized in that: To said main-chain polyether repeating unit comprises a single methylene-oxy methylene linkage; wherein ion transport may be provided within a coordinating channel formed by said repeating unit.

16. The polymer electrolyte as claimed in claim 15, wherein said hydrocarbon side-chain is alkyl, phenyl or a substantially straight chain hydrocarbon preferably-(CH2)m-H where 30 2 m > 5, more preferably m is 12 1 6 or 1 8.

17. The polymer electrolyte as claimed in claims 15 or 16 wherein said hydrocarbon side-chain is provided on each alkylene group or benzene nucleus of a plurality of repeating units.

1&. The polymer electrolyte as claimed in claims 15 or 16 wherein said hydrocarbon side-chain extends from some of the alkylene groups or benzene nuclei of a plurality of repeating units.

19. The polymer electrolyte as claimed in any one of claims 15 to 18 wherein said polymer electrolyte is arranged as a lattice, said lattice comprising ionophilic regions of polyether repeating units and ionophobic regions of hydrocarbon side-chains.