WO2006051323A1 - Électrolyte polymère - Google Patents

Électrolyte polymère Download PDF

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Publication number
WO2006051323A1
WO2006051323A1 PCT/GB2005/004372 GB2005004372W WO2006051323A1 WO 2006051323 A1 WO2006051323 A1 WO 2006051323A1 GB 2005004372 W GB2005004372 W GB 2005004372W WO 2006051323 A1 WO2006051323 A1 WO 2006051323A1
Authority
WO
WIPO (PCT)
Prior art keywords
repeating unit
alkylene
chain
polymer
polymer electrolyte
Prior art date
Application number
PCT/GB2005/004372
Other languages
English (en)
Inventor
Peter V. Wright
Yungui Zheng
Jianguo Liu
Original Assignee
The University Of Sheffield
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from GB0425159A external-priority patent/GB0425159D0/en
Application filed by The University Of Sheffield filed Critical The University Of Sheffield
Publication of WO2006051323A1 publication Critical patent/WO2006051323A1/fr

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • 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
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/02—Aliphatic polycarbonates
    • 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
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/18—Block or graft polymers
    • C08G64/183—Block or graft polymers containing polyether sequences
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • R 1 is alkylene or a benzene nucleus
  • R 2 is oxygen, alkylene, phenylene or CH 2
  • R 3 is alkyl, phenyl, alkyl-phenyl, or a substantially straight chain hydrocarbon, preferably -(CH2) m -H where 30 > m ⁇ 5, more preferably m is 12, 16 or 18; 8 > n > 3 and 3 > r > 2.
  • A is alkylene or phenylene, preferably (CH 2 ) t 6 ⁇ t ⁇ 2;
  • 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 (CH 2 ) m where 30 > m > 5 or B is -0-C 6 H 4 -O- (CH 2 ) I2 -O-C 6 H 4 -O- ; 40 > x > 20.
  • the second ionic bridge polymer may be bonded to at least one end of the ion conducting polymer.
  • R 5 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.
  • the repeating units of the ion conducting polymer are represented by PO2-sc in the case of a main-chain second repeating unit configured to be non-coordinating with the metal cation and PO5-sc for a main- chain first repeating unit configured for coordination of the cation.
  • PO2-sc comprises a single oxyethylene linkage within the repeating unit - optionally in addition to a hydrocarbon side-chain extending from the main-chain.
  • PO5-sc comprises four oxyethylene linkages within the repeating unit (i.e. the main-chain repeating unit comprises five oxygens available for cation coordination) optionally in addition to a hydrocarbon side-chain.
  • FIG. 1 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.
  • the electrolyte system adopts a well-defined morphology where the ion conducting polymer is arranged 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 and PO2-sc, respectively.
  • Ionic bridge polymer 101 (1 BP or 2BP) provides a binding function being interdispersed between the micellar or lamellar regions. Ion transport therefore occurs between regions 100 and 101 where, for example, the electrolyte complex is provided between electrods of a battery.
  • FIG. 2 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; PO2-sc repeating units 201 ; hydrocarbon side-chain repeating units 202; metal cation 203; coordinating atoms 204; de-coupled anions 205; neutrally charged salt 206 and charged salt complex 208.
  • 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 organisation of main-chain first and second repeating units 200, 201.
  • the PO5-sc repeating units 200 are organised into substantially helical ion coordinating regions 200 within the channel predominately formed by the PO2-sc repeating units 201.
  • 1BP 101 acts as an ionic bridge or 'glue' between lamellar or micellar regions.
  • a second 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.
  • FIG. 3 there is illustrated a schematic view of the electrolyte complex comprising a lamellar morphology the lamellar layers of ion conducting polymer 300 being separated by layers of 1 BP 301.
  • interdigitation of the ionophobic hydrocarbon side-chains 202 and interaction between the metal salt and the ionophilic main-chain repeating units PO2-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.
  • the skeletal polymer backbone may comprise solely polyester or polyether-ester repeating units.
  • the polyether-ester repeating units may be interdispersed amongst polyether repeating units.
  • PO5-SC may be represented by specific formula (II):
  • 2BP may be represented by specific formula (IV):
  • compound (I)) are incorporated within the main-chain polymer backbone.
  • 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.
  • Copolymers of compound (I) and compound (II) mixed polyether skeletal sequences were obtained from reactions involving appropriate molar proportions of the three types of monomer 5-alkyloxy ⁇ 1,3-bis(bromomethyl)benzene, 5- alkyloxybenzene-1 ,3-dimethanol and tetraethylene glycol.
  • a proportion of tetraethylene glycol was replaced by the alkyloxybenzene-1 ,3-dimethanol.
  • the relative monomer proportions were determined by solubility considerations rather than stoichiometry owing to the amphiphilic nature of the side chain bearing monomers and the polymer product.
  • the aliphatic compound (II) variant mostly melts at 45°C.
  • 1 H NMR(400MHz, CDCI 3 ): ⁇ 0.86(t, 3H, CH 3 ), 1.22 (s, 34H, alkyl chain 17CH 2 ), 1.75 (m, 1 H, CH), 3.60(t, 8H, OCH 2 ).
  • the polymer of general formula (II) was prepared by heating with gentle stirring at 6O 0 C of 1.00g (0.00264mol) 5- hexadecyloxybenzene -1 , 3- dimethanol, and 3g (0.04mol) potassium hydroxide in 5ml dimethyl sulphoxide for 7 days.
  • the polymer was precipitated in water; the mixture was neutralized by addition of concentrated acetic acid and extracted into chloroform. After evaporation of the chloroform, the residue was washed with hot water several times to remove inorganic salt and finally with hot methanol several times to remove the monomer.
  • the polymer poly[2,5,8,11-tetraoxadodecamethylene(5-hexadecyloxy-1 ,3- phenylene] (100%) was prepared as above but the molar equivalent of Methylene glycol was used. The yield is (75%).
  • CDCI 3 CDCI 3 ; standard SiMe 4 ) 0.86 (3H, t, CH 3 ), 1.25 (25H, s, 12CH 2 ), 1.45 (2H, m, ⁇ -
  • the above compound (lll)-derivative may be prepared by a ring opening cationic polymerisation.
  • the cyclic ether may be cleaved with BF 3 /dietherate so as to generate the required polyalkylene oxide.
  • Such a process may similarly be employed for other similar compound (I I Invariants.
  • the ionophobic character of the resulting polymer may be selectively adjusted by varying the relative amount of the cyclic ether containing at least one side group, during polymerisation of the above compound
  • electrolyte systems may be provided with enhanced mechanical properties being advantageous in the manufacture of batteries.
  • Polyesters may be prepared by condensation of 5-hexadecyIoxybenzene -1 , 3-dimethanol with diacyl chlorides in basic media. The reaction would be performed with equimolar proportions of reagents in a solvent mixture such as THF/pyridine. Alternatively, the benzylic functions may be sufficiently reactive to support an interfacial mechanism.
  • a polyether-ketone would be obtained from the Williamson condensation of equimolar proportions of 5-hexadecyloxy-1 ,3-bis(bromomethyl)benzene with dihydroxy acetone.
  • Li salts 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, LiCIO 4 , LiBF 4 , LiCF 3 SO 3 , or Li(CF 3 SO 2 )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 5O 0 C).
  • a galvanic cell utilising a polymer electrolyte according to the present invention comprises two electrods, an anode being lithium metal and a cathode being an inorganic particulate.
  • anode being lithium metal
  • a cathode being an inorganic particulate.
  • ceramic particles may be set in a matrix of the polymer electrolyte.
  • the inventors have realised that by locating at the anode a polymer electrolyte comprising predominantly polyether repeating units, according to the present invention, the electrolyte - anode junction does not degrade during use and charging of the galvanic cell.
  • PEO PEO, PO1-SC, PO ⁇ -sc, P-nsc, 1 BP and/or 2BP.
  • the system is optimised to allow subsequent ion transport throughout life of the battery. Additionally, this 'tunnelling' of the Li + ions at the lower temperatures of 25-40°C, may obviate the requirement to raise the temperature of the cell up to for example 110 0 C.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Dispersion Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Conductive Materials (AREA)
  • Secondary Cells (AREA)

Abstract

La présente invention concerne un électrolyte polymère configuré pour assurer un transport ionique, ledit électrolyte polymère comprenant : un premier motif récurrent à chaîne principale configuré pour constituer un site de coordination principal pour un ion, ledit premier motif récurrent étant dispersé dans un second motif récurrent à chaîne principale pour former un canal de coordination d’ions, ledit second motif récurrent étant moins fortement coordinateur d’ions que ledit premier motif récurrent. Ledit électrolyte polymère est configuré pour assurer un transport ionique à l’intérieur dudit canal de coordination qui fait appel à une coordination et à une libération dudit ion par ledit site de coordination principal.
PCT/GB2005/004372 2004-11-15 2005-11-11 Électrolyte polymère WO2006051323A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB0425159.1 2004-11-15
GB0425159A GB0425159D0 (en) 2004-11-15 2004-11-15 Polymer electrolyte
GB0509796A GB2420121A (en) 2004-11-15 2005-05-13 Polymer Electrolyte
GB0509796.9 2005-05-13

Publications (1)

Publication Number Publication Date
WO2006051323A1 true WO2006051323A1 (fr) 2006-05-18

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PCT/GB2005/004372 WO2006051323A1 (fr) 2004-11-15 2005-11-11 Électrolyte polymère

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3890279A (en) * 1973-12-10 1975-06-17 Du Pont Thermoplastic copolyester elastomer
JPS6230148A (ja) * 1985-07-31 1987-02-09 Nissan Chem Ind Ltd 新規なイオン伝導性高分子複合体
EP0566169A2 (fr) * 1992-02-17 1993-10-20 ENICHEM S.p.A. Polymères conducteurs avec conductance ionique
EP0657484A1 (fr) * 1993-12-09 1995-06-14 Hydro-Quebec Copolyéthers réticulables et leur utilisation comme électrolytes polymères
US6201071B1 (en) * 1997-06-25 2001-03-13 Daiso Co., Ltd. Polyether copolymer, solid polymer electrolyte and battery
EP1113517A2 (fr) * 1999-12-27 2001-07-04 Sumitomo Chemical Company, Limited Electrolyte polymère et son procédé de fabrication
US20040218346A1 (en) * 2000-07-10 2004-11-04 Showa Denko K.K. Polymerizable composition and use thereof
WO2004102692A2 (fr) * 2003-05-13 2004-11-25 The University Of Sheffield Electrolyte polymere

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3890279A (en) * 1973-12-10 1975-06-17 Du Pont Thermoplastic copolyester elastomer
JPS6230148A (ja) * 1985-07-31 1987-02-09 Nissan Chem Ind Ltd 新規なイオン伝導性高分子複合体
EP0566169A2 (fr) * 1992-02-17 1993-10-20 ENICHEM S.p.A. Polymères conducteurs avec conductance ionique
EP0657484A1 (fr) * 1993-12-09 1995-06-14 Hydro-Quebec Copolyéthers réticulables et leur utilisation comme électrolytes polymères
US6201071B1 (en) * 1997-06-25 2001-03-13 Daiso Co., Ltd. Polyether copolymer, solid polymer electrolyte and battery
EP1113517A2 (fr) * 1999-12-27 2001-07-04 Sumitomo Chemical Company, Limited Electrolyte polymère et son procédé de fabrication
US20040218346A1 (en) * 2000-07-10 2004-11-04 Showa Denko K.K. Polymerizable composition and use thereof
WO2004102692A2 (fr) * 2003-05-13 2004-11-25 The University Of Sheffield Electrolyte polymere
WO2004102693A2 (fr) * 2003-05-13 2004-11-25 The University Of Sheffield Electrolyte polymerique

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 198711, Derwent World Patents Index; Class A23, AN 1987-076524, XP002368286 *
DIAS F B ET AL: "Ionic conduction of lithium, sodium and magnesium salts within organised smectic liquid crystal polymer electrolytes", ELECTROCHIMICA ACTA, ELSEVIER SCIENCE PUBLISHERS, BARKING, GB, vol. 43, no. 10-11, 30 April 1998 (1998-04-30), pages 1217 - 1224, XP004134178, ISSN: 0013-4686 *
DIAS F B ET AL: "Ionic conductivity of a novel smectic polymer electrolyte", SOLID STATE IONICS, NORTH HOLLAND PUB. COMPANY. AMSTERDAM, NL, vol. 85, no. 1, May 1996 (1996-05-01), pages 43 - 49, XP004050471, ISSN: 0167-2738 *
DIAS F B ET AL: "SMECTIC PHASES IN A NOVEL ALKYL-SUBSTITUTED POLYETHER AND ITS COMPLEX WITH LITHIUM TETRAFLUOROBORATE", MACROMOLECULAR: RAPID COMMUNICATIONS, WILEY VCH VERLAG, WEINHEIM, DE, vol. 15, 1994, pages 961 - 969, XP002302979, ISSN: 1022-1336 *
MERTENS I J A ET AL: "NOVEL POLYMER ELECTROLYTES BASED ON AMORPHOUS POLY(ETHER-ESTER)S CONTAINING 1,4,7-TRIOXANONYL MAIN CHAIN UNITS. IONIC CONDUCTIVITY VERSUS POLYMER CHAIN MOBILITY", MACROMOLECULES, ACS, WASHINGTON, DC, US, vol. 32, no. 10, 18 May 1999 (1999-05-18), pages 3314 - 3324, XP000829765, ISSN: 0024-9297 *
ZHENG Y ET AL: "SELF-TRACKING IN SOLVENT-FREE, LOW-DIMENSIONAL POLYMER ELECTROLYTE BLENDS WIH LITHIUM SALTS GIVING HIGH AMBIENT DC CONDUCTIVITY", CHEMICAL COMMUNICATIONS - CHEMCOM, ROYAL SOCIETY OF CHEMISTRY, GB, 2000, pages 1459 - 1460, XP002302977, ISSN: 1359-7345 *
ZHENG Y. & AL: "Insertion of ionophobic components into amphiphilic low-dimensional polymer elctrolytes", ELECTROCHIMICA ACTA, vol. 45, 2000, pages 1161 - 1165, XP002367043 *

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