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WO2014090178A1 - Copolymère multiséquencé et électrolyte polymère - Google Patents

Copolymère multiséquencé et électrolyte polymère Download PDF

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Publication number
WO2014090178A1
WO2014090178A1 PCT/CN2013/089237 CN2013089237W WO2014090178A1 WO 2014090178 A1 WO2014090178 A1 WO 2014090178A1 CN 2013089237 W CN2013089237 W CN 2013089237W WO 2014090178 A1 WO2014090178 A1 WO 2014090178A1
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Prior art keywords
block copolymer
segment
mmol
poly
polymer electrolyte
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Inventor
Yang Yang
Shaofu FAN
Qiao CHEN
Gang Wu
Daisuke Izuhara
Hiroaki Umeda
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Toray Advanced Materials Research Laboratories China Co Ltd
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Toray Advanced Materials Research Laboratories China Co Ltd
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Priority claimed from CN201210537214.3A external-priority patent/CN103865011A/zh
Priority claimed from CN201210537254.8A external-priority patent/CN103872377A/zh
Application filed by Toray Advanced Materials Research Laboratories China Co Ltd filed Critical Toray Advanced Materials Research Laboratories China Co Ltd
Priority to CN201380051784.4A priority Critical patent/CN104684949B/zh
Priority to JP2015546834A priority patent/JP6311721B2/ja
Publication of WO2014090178A1 publication Critical patent/WO2014090178A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2438/00—Living radical polymerisation
    • C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP

Definitions

  • the present invention relates to a multi-block copolymer and a polymer electrolyte material used for lithium ion secondary battery.
  • Lithium ion secondary battery is a promising green chemical power source with higher energy density, higher output voltage, and shorter charging time than other secondary batteries, and thus it has great economic and social benefit.
  • liquid electrolyte has traditionally been used.
  • the liquid electrolyte is prone to leakage, which may cause safety problems and spoil long-term reliability.
  • solid electrolyte materials such as inorganic electrolyte or polymer electrolyte (solid) instead of liquid electrolytes.
  • the inorganic solid electrolyte potentially has the highest lithium ion conductivity among solid electrolyte materials.
  • it has drawbacks of low processability and high interfacial resistance to electrode. Accordingly, thanks to advantages in weight, flexibility and processability, research and development of solid polymer electrolyte have been actively pursued.
  • polyethylene oxide or polyoxyethylene, abbreviated as PEO
  • PEO polyoxyethylene
  • polymer electrolyte materials of prior art were insufficient to support lithium ion conductivity and mechanical property of electrolyte membranes at same time, failing to achieve long-term durability and industrially useful material for lithium ion battery.
  • polymer electrolyte material which has both high lithium ion conductivity and excellent mechanical properties, which achieves to form a polymer solid electrolyte battery with high energy density, high output voltage, short charging times, and high reliability.
  • the polymer of the present invention is a multi-block copolymer with PEO repeating unit in side chains and shows co-continuous phase separation morphology in all range of segment content.
  • the present invention it is possible to provide a polymer electrolyte material which has high lithium ion conductivity and excellent mechanical strength at same time, which also can form a polymer solid electrolyte battery with high energy density, high output voltage, short charging times, and high reliability.
  • the present invention is featured as follows;
  • a multi-block copolymer possesses the structure of formula (PI):
  • Co-continuous phase separation morphology is one kind of morphological structures for phase separation.
  • the type of morphology basically depends on the content of segment A or B in the copolymer.
  • the kind of phase separation morphology such as sphere, cylinder, lamellar, varies depending on the segment content of A or B, as reported in Macromolecules, 2007, 40, 4578-4585; Annual Review of Physical Chemistry, 41, 1990, 525.
  • co-continuous phase separation morphology can only be achieved in a narrow range of segment content and is always dependent of segment content.
  • the inventors have overcome the difficulty by making the multi-block copolymer with more than 4 alternately recurring segments as shown in formula (PI).
  • segment means a partial structure of multi-block polymer with formula weight of more than 2000 and combining one or more kinds of repeating units.
  • R r R 4 are independently H or CI -CIO alkyl; p is a positive integer.
  • formula (Zl) are preferably H or C1-C5 alkyl in terms of manufacturing cost, more preferably H or C1-C3 alkyl in terms of lithium ion conductivity, p is preferably a positive integer of 2-50 in terms of crystallinity and manufacturing cost, more preferably 5-30 in terms of ion conductivity.
  • segment A More preferable structure for segment A is as follows:
  • Rj ⁇ R 3 are independently H or CI ⁇ C 10 alkyl
  • R4 is — C-O— o irr— C- ⁇ / R 5 is H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-hexyl, or phenyl
  • m is an integer of 2 to 50
  • nj is an integer of 10 to 500.
  • R r R 3 are preferably H or C1-C5 alkyl in terms of manufacturing cost, more preferably H, methyl, ethyl in terms of lithium ion conductivity.
  • R 5 is preferably H, methyl, or ethyl for cost and ion conductivity reasons, m is preferably a positive integer of 5 to 30 and nj is preferably a positive integer of 20 to 300 in terms of manufacturing cost.
  • the copolymer has more than 4 alternately recurring segments (ABAB, BABA), and the PEO unit is located in its side chain, the crystallinity of the copolymer is reduced and higher lithium ion conductivity is achieved consequently.
  • R 6 ⁇ R 8 are independently H or C1-C10 alkyl
  • R 9 is phenyl, p-methyphenyl, m- methyl styrene, p-fluorophenyl, nitrile or carbomethoxy
  • n 2 is a positive integer of 10 to 500.
  • R 6 ⁇ R 8 are preferably H, methyl, or ethyl for manufacturing and cost advantages.
  • R 9 is preferably phenyl, p-methylphenyl or carbomethoxy for cost advantages.
  • n 2 is preferably 20 to 300 in terms of compatibility of ion conductivity and mechanical property.
  • the multi-block copolymer in the present invention can be prepared by living radical polymerization method, preferably Atom Transfer Radical Polymerization method (ATRP). Block number and reaction steps can be adjusted by halogen atoms of organic halogen initiator.
  • living radical polymerization method preferably Atom Transfer Radical Polymerization method (ATRP).
  • Block number and reaction steps can be adjusted by halogen atoms of organic halogen initiator.
  • Transition metal complex can be used as a catalyst.
  • transition metal halide it may be halide of copper, ruthenium, iron, rhenium, nickel or palladium.
  • it is preferably selected from the group consisting of copper bromide, copper chloride, dichlorotris(triphenylphosphine) ruthenium, dichlorotris(tributylphosphine) ruthenium, ferrous chloride and ferrous bromide.
  • ligand it may be amines or phosphines.
  • TPMA tris(2-pyridylmethyl)amine
  • Initiator used for the living radical polymerization may be organohalogen compound comprising one or two halogen atoms.
  • it is preferably selected from the group consisting of dichloromethane, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, 2,2-dichloroacetophenone, ethyl 2-bromopropionate, diphenylmethane, bromodiphenylmethane and tosyl chloride.
  • the number of halogen atoms will have an effect on the polymerization process and the number of blocks.
  • the reaction process should have (a+b+2n) steps to obtain the multi-block copolymer of formula (PI).
  • organohalogen compound with two halogen atoms when organohalogen compound with two halogen atoms is used, only n steps are required to obtain the same polymer.
  • the number of halogen atoms mentioned here refers to the number of halogen atoms which can be effectively induced, and does not include the ones without activity, for example, the halogen atom of acyl chloride can not be counted because of no activity for initiating reaction.
  • polymerization conditions used to prepare multi-block copolymers with block number greater than 3 should be more rigorous and complex. Such multi-block copolymers can not be obtained constantly by the conventional reaction conditions, because the growth of new segment becomes more difficult as the molecular weight increases.
  • special process or method should be introduced, for example, gradient temperature is used to obtain a homogeneous reaction system or bulk polymerization to increase activity.
  • tri-block copolymer of A-B-A type with one halogen atom is used as a macromolecular initiator and, because of high M n solubility, is not so good. If synthesis is carried out in a common way by directly heating, most of the macromolecular initiator is insoluble, and an asymmetrical reaction system is thus formed. Therefore, the system is firstly heated to low temperature in low rate, such as 50 ° C and 3 ° C/min, to completely dissolve the macromolecular initiator. Then, the system is further heated to final reaction temperature still in low rate and polymerization is conducted. Any method which is effective to increase uniformity for system or reactivity can be used to prepare the multi-block copolymer provided in the present invention.
  • low temperature in low rate such as 50 ° C and 3 ° C/min
  • Another object of the present invention is to provide a polymer electrolyte, comprising a multi-block copolymer described above and an electrolyte salt.
  • the number of blocks is greater than 3
  • co-continuous phase morphology can be achieved in a wide range of segment A content. This will lead to easy adjustment of ionic conductivity and mechanical properties of polymer electrolyte, and the overall performance of the polymer electrolyte can thus be greatly improved.
  • electrolyte salt used in the present invention. Suitable examples include alkali metal salts, quaternary ammonium salts or transition metal salts. For electrolytes that display a large dissociation constant within polymer electrolyte, lithium salts are preferred. For cost and performance advantages, lithium salts selected from the group consisting of lithium bis(trifluoromethane sulfonimide) (LiTFSI), lithium perchlorate (LiClO 4 ), lithium tri-fluoromethanesulfonate (L1CF 3 SO 3 ), lithium hexa- fluorophosphate (LiPF 6 ), lithium tetra-fluoroborate (LiBF 4 ) and mixtures thereof are preferably used.
  • LiTFSI lithium bis(trifluoromethane sulfonimide)
  • LiClO 4 lithium perchlorate
  • LiCF 3 SO 3 lithium tri-fluoromethanesulfonate
  • LiPF 6 lithium hexa- fluorophosphat
  • the amount of electrolyte salt added is typically within a range from 0.005 to 80 mol%, relative to the molar quantity of polyoxyethylene units in the copolymer. Considering balance of ionic conductivity and mechanical properties, the amount of the electrolyte salt is preferably 0.01 to 20 mol%.
  • the method of adding electrolyte salt to the copolymer is not restricted. Solution in tetrahydrofuran, chloroform, N- methyl pyrrolidone or toluene is preferably used, but mechanical mixing at room temperature or under heat can also be applied.
  • micro phase separation morphology especially co-continuous phase morphology can be achieved in a wide range of segment A content.
  • the content of segment A of 50-99% which is preferable in terms of high lithium ion conductivity can be achieved with co-continuous phase morphology.
  • Micro phase separation morphology, especially co-continuous phase morphology helps to keep the transport (ion conductive) properties of segment A and support (mechanical) properties of segment B at same time.
  • the sheet-like solid polymer electrolyte can be produced by any coating techniques, such as roll coating, curtain coating, spin coating, dipping, or casting. Using one of these techniques, film of polymer solid electrolyte is formed on the surface of a substrate, and the substrate is subsequently removed to yield the solid polymer electrolyte sheet.
  • Figure 1 is a transmission electron microscope photograph showing a cross-section of the electrolyte film in Example 1. Co-continuous phase morphology can be observed.
  • Figure 2 is a transmission electron microscope photograph showing a cross-section of the electrolyte film in Example 2. Co-continuous phase morphology can be observed.
  • Figure 3 is a transmission electron microscope photograph showing a cross-section of the multi-block copolymer in Comparative Example 1.
  • lamellar phase morphology can be observed.
  • Figure 4 is a transmission electron microscope photograph showing a cross-section of the electrolyte film in Comparative Example 3. When the content of segment A is 11.8 wt%, "sea-island" phase morphology can be observed.
  • Dichlorobenzene, 2,2-dichloroacetophenone, ethyl 2-bromopropionate purchased from Sigma-Aldrich Co. Ltd.
  • Dichloromethane purchased from Sinopharm Chemical Reagent Co. Ltd. and purified by refluxing with Na to remove water before using.
  • CuBr, CuCl purchased from Sinopharm Chemical Reagent Co. Ltd. and purified with acetic acid and methanol before using.
  • Dichlorotris (triphenylphosphine) ruthenium, ferrous bromide purchased from Sigma-Aldrich Co. Ltd. and used without further purification.
  • Lithium bis(trifluoromethane sulfonimide) LiTFSI
  • LiClO 4 lithium perchlorate
  • LiCF 3 SO 3 lithium tri-fluoromethanesulfonate
  • LiPF 6 lithium hexafluorophosphate
  • LiBF 4 lithium tetrafluorob orate
  • A. Number average molecular weight of polymer Gel Permeation Chromatography (GPC) (LC-20, Japan), tetrahydrofuran as solvent and mobile phase.
  • GPC Gel Permeation Chromatography
  • segment A in polymer (wt%): 1H NMR (JEOL ECX-400P, Japan), deuterochloroform as solvent.
  • Phase morphology Transmission Electron Microscope (TEM) (JEM2010, Japan), sampling by ice-embeding and slicing at -80 ° C .
  • D. Crystallinity Differential Scanning Calorimeter (DSC) (Q100, American), N 2 protection, -80 ° C ⁇ 200 ° C , 20 ° C/min.
  • DMA Dynamic Mechanical Analyzer
  • Lithium ion conductivity Electrochemical workstation (VSP Japan), polymer electrolyte membrane is put into the test unit (HS Test Cell, Japan Hohsen) in glove box and then tested after being kept more than 1 hour at ambient temperature (23 ° C).
  • Example 1 Preparation of quadri-block copolymer of A-B-A-B type and corresponding polymer electrolyte, in which poly (poly (ethylene glycol) methyl ether methacrylate) (denoted as P(PEGMA)) was used as segment A and polystyrene (denoted as PS) was used as segment B)
  • P(PEGMA) poly (poly (ethylene glycol) methyl ether methacrylate)
  • PS polystyrene
  • PEGMA-1 poly(ethylene glycol) methyl ether methacrylate
  • 45.3 mg (0.316 mmol) of CuBr and 98.65 mg (0.732 mmol) of bpy were added into the solution.
  • 57.2 mg (0.316 mmol) of ethyl 2-bromopropionate was added and heated to 90 ° C . After polymerization for 30 hours, the solution was cooled immediately in ice/water bath to stop the reaction.
  • the solution was diluted with THF and purified by passing through Al 2 O 3 column to remove catalyst/ligand. After removal of solvent, the reaction product was washed with diethyl ether anhydrous to remove unreacted monomers and purified P(PEGMA)-1 was obtained.
  • the P(PEGMA)-1 had a M n of 42000 and a M w /M n of 1.12, and the GPC curve thereof showed a single symmetrical peak.
  • the reaction product was washed with n-hexane to remove unreacted St, and purified white powder of P(PEGMA)-b-PS di-block copolymer (A-B type) was obtained.
  • the di-block copolymer had of a M n of 80000 and a M w /M n of 1.32, and the GPC curve thereof showed a single symmetrical peak, and the content of segment A (f A ) was 52.5 wt%.
  • the tri-block copolymer had a M n of 125000 and a M w /M n of 1.48, and the GPC curve thereof showed a single symmetrical peak, and the content of segment A (f A ) was 69.6 wt%.
  • reaction system was cooled immediately in ice/water bath to stop the polymerization.
  • the solution was diluted with THF and purified by passing through Al 2 O 3 column to remove catalyst/ligand. After removal of solvent, the reaction product was washed with n-hexane to remove unreacted monomers and the purified white powder of P(PEGMA)-b-PS-b-P(PEGMA)-b-PS quadri-block copolymer (A-B-A-B type) was obtained.
  • the quadri-block copolymer had a M n of 160000 and a M w /M n of 1.39, and the GPC curve thereof showed a single symmetrical peak, and the content of segment A (f A ) was 54.4 wt%.
  • phase morphology of the membrane was observed by TEM and it showed co-continuous phase morphology.
  • the initial modulus of the polymer solid electrolyte membrane was 4.2 MPa.
  • the membrane was put into a glove box for more than one week to completely remove water or solvent, and then assembled in a UFO cell.
  • the lithium ion conductivity thereof was found to be 8.9x l0 "4 S/cm by measuring at 23 ° C using an electrochemical workstation.
  • Example 2 Preparation of penta-block copolymer of A-B-A-B-A type and corresponding polymer electrolyte, in which P(PEGMA) was used as segment A and PS was used as segment B)
  • the quadri-block copolymer of P(PEGMA)-b-PS-b-P(PEGMA)-b-PS (A-B-A-B type) prepared in Example 1 was used as a macromolecular initiator to prepare penta-block copolymer.
  • the solution was diluted with THF and purified by passing through Al 2 O 3 column to remove catalyst/ligand. After removal of solvent, the reaction product was washed with diethyl ether anhydrous to remove unreacted monomers and purified white powder of P(PEGMA)-b-PS-b-P(PEGMA)-b-PS-b-P(PEGMA) penta-block copolymer (A-B-A-B-A type) was obtained.
  • the penta-block copolymer had a M n of 320000 and a M w /M n of 1.41, the GPC curve thereof showed a single symmetrical peak, and the content of segment A (f A ) was 77.2 wt%.
  • phase morphology of the membrane was observed by TEM and it showed co-continuous phase morphology.
  • the initial modulus of the polymer solid electrolyte membrane was 3.7 MPa.
  • the membrane was put into a glove box for more than one week to completely remove water or solvent, and then assembled in a UFO cell.
  • the lithium ion conductivity was found to be 3.5x 10 "3 S/cm by measuring at 23 ° C using electrochemical workstation.
  • Example 3 Preparation of penta-block copolymer of A-B-A-B-A type and corresponding polymer electrolyte, in which P(PEGMA) was used as segment A and PS was used as segment B)
  • the reaction product was washed with diethyl ether anhydrous to remove unreacted monomers and purified P(PEGMA)-2 was obtained.
  • the P(PEGMA)-2 had a M n of 6000 and a M w /M n of 1.14, and the GPC curve thereof showed a single symmetrical peak.
  • the reaction product was washed with n-hexane to remove unreacted St and purified white powder of PS-b-P(PEGMA)-b-PS tri-block copolymer (B-A-B type) was obtained.
  • the tri-block copolymer had a M n of 51000 and a M w /M n of 1.32, and the GPC curve thereof showed a single symmetrical peak, and the content of segment A (f A ) was 11.8 wt%.
  • reaction system was sealed, and after the tri-block copolymer was dissolved completely, the reaction temperature was raised to 90 ° C in a rate of 1.5 ° C/min. Polymerization was carried out for 100 hours. Then the reaction system was cooled immediately in ice/water bath to stop the polymerization. The solution was diluted with THF and purified by passing through Al 2 O 3 column to remove catalyst/ligand.
  • the reaction product was washed with diethyl ether anhydrous to remove unreacted monomers and purified white powder of P(PEGMA)-b-PS-b-P(PEGMA)-b-PS-b-P(PEGMA) penta-block copolymer (A-B-A-B-A type) was obtained.
  • the penta-block copolymer had a M n of 59000 and a M w /M n of 1.37, and the GPC curve thereof showed a single symmetrical peak, and the content of segment A (f A ) was 23.7 wt%.
  • phase morphology of the membrane was observed by TEM and it showed co-continuous phase morphology.
  • the initial modulus of the polymer solid electrolyte membrane was 3.9 MPa.
  • the membrane was put into a glove box for more than one week to completely remove water or solvent, and then assembled in a UFO cell.
  • the lithium ion conductivity was found to be 4.5 x lO "4 S/cm by measuring at 23 ° C using electrochemical workstation.
  • Example 4 Preparation of septu-block copolymer of B-A-B-A-B-A-B type and corresponding polymer electrolyte, in which P(PEGMA) was used as A segment and PS was used as B segment)
  • Penta-block copolymer of P(PEGMA)-b-PS-b-P(PEGMA)-b-PS-b -P(PEGMA) (A-B-A-B-A type) prepared in Example 3 was used as macromolecular initiator to prepare septu-block copolymer.
  • reaction system was cooled immediately in ice/water bath to stop the polymerization.
  • the solution was diluted with THF and purified by passing through Al 2 O 3 column to remove catalyst/ligand. After removal of solvent, the reaction product was washed with n-hexane to remove unreacted St and purified white powder of PS-b-P(PEGMA)-b-PS-b-P(PEGMA)-b-PS-b-P(PEGMA)-b-PS as hepta-block copolymer (B-A-B-A-B-A-B type) was obtained.
  • the hepta-block copolymer had a M n of 128000 and a M w /M n of 1.26, and the GPC curve thereof showed a single symmetrical peak, and the content of segment A (f A ) was 10.9 wt%.
  • Example 3-(3) By repeat of Example 3-(3) and Example 4-(l), multi-block copolymer with block number of nine, eleven, thirteen or more can be obtained.
  • phase morphology of the membrane was observed by TEM and it showed co-continuous phase morphology.
  • the initial modulus of the polymer solid electrolyte membrane was 4.7 MPa.
  • the membrane was put into a glove box for more than one week to completely remove water or solvent, and then assembled in a UFO cell.
  • the lithium ion conductivity was found to be 9.6> ⁇ 10 "4 S/cm at by measuring at 23 ° C using electrochemical workstation.
  • Example 5 Preparation of penta-block copolymer of A-B-A-B-A type and corresponding polymer electrolyte, in which poly(poly(ethylene glycol) ethylic ether allylbenzene) was used as segment A and poly(acrylonitrile) (denoted as PAN) was used as segment B)
  • the reaction product was washed with n-hexane to remove unreacted monomers and purified white powder of tri-block copolymer (B-A-B type) was obtained.
  • the tri-block copolymer had a M n of 73000 and a M w /M n of 1.35, and the GPC curve thereof showed a single symmetrical peak.
  • the penta-block copolymer had a M n of 96000 and a M w /M n of 1.56, and the GPC curve thereof showed a single symmetrical peak, and the content of segment A (f A ) was 80.2 wt%.
  • phase morphology of the membrane was observed by TEM and it showed co-continuous phase morphology.
  • the initial modulus of the polymer solid electrolyte membrane was 2.8 MPa.
  • the membrane was put into a glove box for more than one week to completely remove water or solvent, and then assembled in a UFO cell.
  • the lithium ion conductivity was found to be 6.2x l0 "4 S/cm by measuring at 23 ° C using electrochemical workstation.
  • Example 6 Preparation of penta-block copolymer of A-B-A-B-A type and corresponding polymer electrolyte, in which poly (poly (ethylene glycol) methacrylate) was used as segment A and poly(methyl acrylate) was used as segment B)
  • the solution was diluted with THF and purified by passing through Al 2 O 3 column to remove catalyst/ligand. After removal of solvent, the reaction product was washed with diethyl ether anhydrous to remove unreacted monomers and purified poly(poly(ethylene glycol) methacrylate) was obtained.
  • the poly(poly(ethylene glycol)methacrylate) had a M n of 75000 and a M w /M n of 1.24, and the GPC curve thereof showed a single symmetrical peak.
  • the reaction product was washed with n-hexane to remove unreacted monomers and purified white powder of tri-block copolymer (B-A-B type) was obtained.
  • the tri-block copolymer had a M n of 170000 and a M w /M n of 1.43, and the GPC curve thereof showed a single symmetrical peak.
  • reaction system was sealed, and after the tri-block copolymer was dissolved completely, the reaction temperature was raised to 90 ° C in a rate of 1.5 ° C/min. Polymerization was carried out for 100 hours. Then the reaction system was cooled immediately in ice/water bath to stop the polymerization. The solution was diluted with THF and purified by passing through Al 2 O 3 column to remove catalyst/ligand.
  • reaction product was washed with diethyl ether anhydrous to remove unreacted monomers and purified white powder of poly(poly(ethylene glycol) methacrylate)-b-poly(methyl acrylate)-b- poly(poly(ethylene glycol) methacrylate)-b-poly(methyl acrylate)-b- poly(poly(ethylene glycol) methacrylate) penta-block copolymer (A-B-A-B-A type) was obtained.
  • the penta-block copolymer had a M n of 430000 and a M w /M n of 1.48, and the GPC curve thereof showed a single symmetrical peak, and the content of segment A (f A ) was 77.9 wt%.
  • phase morphology of the membrane was observed by TEM and it showed co-continuous phase morphology.
  • the initial modulus of the polymer solid electrolyte membrane was 1.9 MPa.
  • the membrane was put into a glove box for more than one week to completely remove water or solvent, and then assembled in a UFO cell.
  • the lithium ion conductivity was found to be 5.3 x lO "4 S/cm by measuring at 23 ° C using electrochemical workstation.
  • Example 7 Preparation of penta-block copolymer of A-B-A-B-A type and corresponding polymer solid electrolyte, in which poly(poly(ethylene glycol) phenoxy acrylate) was used as segment A and poly(4-methyl phenyl-3- octylene) was used as segment B)
  • the reaction product was washed with diethyl ether anhydrous to remove unreacted monomers and purified poly(poly(ethylene glycol) phenoxy acrylate) was obtained.
  • the poly(poly(ethylene glycol)phenoxy acrylate) had a M n of 11000 and a M w /M n of 1.15, and the GPC curve thereof showed a single symmetrical peak.
  • the solution was diluted with THF and purified by passing through Al 2 O 3 column to remove catalyst/ligand. After removal of solvent, the reaction product was washed with n-hexane to remove unreacted monomers and purified white powder of tri-block copolymer (B-A-B type) was obtained.
  • the tri-block copolymer had a M n of 48000 and a M w /M n of 1.39, and the GPC curve thereof showed a single symmetrical peak.
  • reaction system was sealed and after the tri-block copolymer was dissolved completely, the reaction temperature was raised to 90 ° C in a rate of 1.5 ° C/min. Polymerization was carried out for 100 hours. Then the reaction system was cooled immediately in ice/water bath to stop the polymerization. The solution was diluted with THF and purified by passing through Al 2 O 3 column to remove catalyst/ligand.
  • reaction product was washed with diethyl ether anhydrous to remove unreacted monomers and purified white powder of poly(poly(ethylene glycol) phenoxy acrylate)-b-poly(4-methyl phenyl-3-octylene)-b-poly(poly(ethylene glycol) phenoxy acrylate)-b- Poly(4-methyl phenyl-3-octylene)-b-poly(poly(ethylene glycol) phenoxy acrylate) penta-block copolymer (A-B-A-B-A type) was obtained.
  • the penta-block copolymer had a M n of 83000 and a M w /M n of 1.54, and the GPC curve thereof showed a single symmetrical peak, and the content of segment A (f A ) was 55.4 wt%.
  • phase morphology of the membrane was observed by TEM and it showed co-continuous phase morphology.
  • the initial modulus of the polymer solid electrolyte membrane was 3.1 MPa.
  • the membrane was put into a glove box for more than one week to completely remove water or solvent, and then assembled in a UFO cell.
  • the lithium ion conductivity was found to be 9.2x l0 "4 S/cm by measuring at 23 ° C using electrochemical workstation.
  • polyoxyethylene having hydroxyl groups in both terminals can be prepared.
  • polyoxyethylene having bromine groups in both terminals can be prepared.
  • the tri-block copolymer had a M n of 51000 and a M w /M n of 1.25, and the GPC curve thereof showed a single symmetrical peak.
  • phase morphology of the membrane was observed by TEM and it showed lamellar phase morphology.
  • the polymer solid electrolyte had a crystallinity of 12.3%.
  • the segment A was synthesized as in Example 1 (1).
  • the di-block copolymer of A-B type was synthesized as in Example 1 (2).
  • phase morphology of the membrane was observed by TEM and no micro-phase morphology was observed.
  • polymer solid electrolytes with f A 10-70 wt% varied in a crystallinity range of 2-24.6%.
  • the lithium ion conductivity was found to be 3.6 x lO "6 S/cm by measuring at 23 ° C using electrochemical workstation.
  • the segment A was synthesized as in Example 3 (1).
  • the tri-block copolymer of B-A-B type was synthesized as in Example 3 (2).
  • phase morphology of the membrane was observed by TEM.
  • the membrane had co-continuous phase morphology and its f A was in ranges of 20-25 wt% and 60-65 wt%.
  • Polymer solid electrolytes having f A outside the above ranges had "sea-island" or lamellar phase morphology.
  • polymer solid electrolytes with f A 10 ⁇ 80 wt% varied in a crystallinity range of 0.7-21.5%.
  • a polymer solid electrolyte Membrane with f A 23.7 wt% was put into a glove box for more than one week to completely remove water or solvent, and then assembled in a UFO cell.

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  • Organic Chemistry (AREA)
  • Secondary Cells (AREA)
  • Graft Or Block Polymers (AREA)
  • Conductive Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne un copolymère multiséquencé comprenant un motif polyoxyéthylène dans une chaîne latérale et un électrolyte polymère contenant ledit copolymère multiséquencé. Le copolymère multiséquencé comprenant un nombre supérieur à 3 de séquences, sa cristallisation peut être complètement évitée, et ledit copolymère présente plus facilement une morphologie de séparation de phases, notamment une morphologie de phases co-continues, et présente donc une meilleure performance. Une morphologie de phases co-continues peut être obtenue pour ledit électrolyte polymère dans une large plage de teneurs en segment A. L'électrolyte polymère selon la présente invention présente ainsi des propriétés mécaniques et de conductivité ionique considérablement améliorées.
PCT/CN2013/089237 2012-12-13 2013-12-12 Copolymère multiséquencé et électrolyte polymère Ceased WO2014090178A1 (fr)

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