WO2020119750A1 - Polymer, polymer electrolyte, polymer electrolyte membrane, non-aqueous electrolyte solution, and lithium ion battery - Google Patents

Polymer, polymer electrolyte, polymer electrolyte membrane, non-aqueous electrolyte solution, and lithium ion battery Download PDF

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WO2020119750A1
WO2020119750A1 PCT/CN2019/124768 CN2019124768W WO2020119750A1 WO 2020119750 A1 WO2020119750 A1 WO 2020119750A1 CN 2019124768 W CN2019124768 W CN 2019124768W WO 2020119750 A1 WO2020119750 A1 WO 2020119750A1
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polymer
polymer electrolyte
lithium
hydrogen
electrolyte
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PCT/CN2019/124768
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French (fr)
Chinese (zh)
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邓永红
徐洪礼
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深圳新宙邦科技股份有限公司
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Priority claimed from CN201811525129.9A external-priority patent/CN111326797B/en
Priority claimed from CN201811526856.7A external-priority patent/CN111320753B/en
Application filed by 深圳新宙邦科技股份有限公司 filed Critical 深圳新宙邦科技股份有限公司
Publication of WO2020119750A1 publication Critical patent/WO2020119750A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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

  • the invention belongs to the technical field of lithium ion batteries, and particularly relates to a polymer, a polymer electrolyte, a polymer electrolyte membrane, a non-aqueous electrolyte and a lithium ion battery.
  • lithium battery safety accidents have frequently exploded in recent years, such as cell phone explosions and electric vehicle burning accidents.
  • Safety issues have become a technical bottleneck that restricts the wider and deeper application of lithium ion batteries. .
  • Currently widely used lithium-ion batteries use small molecule liquid organic electrolytes, which have a low flash point and are highly flammable.
  • There are serious safety hazards under abnormal conditions such as overcharging and internal short circuits.
  • the polymer electrolyte has greatly improved the battery energy density, high temperature operating temperature range, cycle life and other aspects. It is expected to completely solve the battery safety problem and is one of the inevitable directions for the future development of energy storage devices.
  • polymer solid electrolyte Although the polymer solid electrolyte has the advantages of light weight, good flexibility, and easy film formation, the main problems of the polymer solid electrolyte reported in the literature at present are its easy crystallization, low conductivity, low lithium ion migration number, and electrochemical window Narrow, high energy density cathode materials (such as NCM and NCA, etc.) cannot be used.
  • polymer solid electrolytes also have the problem of high processing costs. Compared with small molecule liquid electrolytes, polymer solid electrolytes require new processing equipment and processes. Industrial higher cost.
  • the more common polymer solid-state electrolyte polymers mainly include polyethylene oxide, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, etc.
  • polymer electrolytes include: a polymer electrolyte disclosed in US Pat. No. 4,792,504, which is mainly composed of polyethylene dimethacrylate/polyalkylene oxide, but its electrochemical stability is poor, and its mechanical properties need to be improved.
  • polyethylene oxide (PEO)/lithium salt electrolytes have higher high-temperature ionic conductivity, but the mechanical properties of such polymers are poor, making it difficult to make self-supporting
  • the polymer electrolyte film has low lithium ion migration number and poor stability at high voltage, which greatly limits the application of this type of polymer electrolyte.
  • the present invention provides a polymer, polymer electrolyte, polymer electrolyte membrane, non-aqueous electrolyte, and lithium ion battery.
  • the present invention provides a polymer represented by the following general formula 1,
  • R 1 is a hydrocarbon group having 1 to 5 carbon atoms or hydrogen
  • R 2 is a hydrocarbon group having 1 to 5 carbon atoms or hydrogen
  • R 3 is -(CH 2 ) n -or -(CH 2 CH 2 O ) n -or-(CF 2 CF 2 O) n -, where n is 1-100
  • R 4 is -(CH 2 ) m -or-(CH 2 CH 2 O) m -or-(CF 2 CF 2 O) m -, where m takes a value of 1-100
  • p takes a value of 1-500.
  • the polymer electrolyte prepared by the polymer represented by the general formula 1 provided by the present invention has a conductivity (the conductivity at 60°C>10 -4 S/cm) and a high lithium ion migration number (>0.36), which has Good compatibility, thereby improving interface stability and long cycle performance.
  • Using the polymer shown in Formula 1 as a polymer electrolyte can avoid the safety hazards of low-flash point organic small molecule electrolytes, and greatly improves the safe use performance of lithium batteries.
  • the polymer represented by the general formula 1 provided by the present invention is an amorphous polymer with a low glass transition temperature, which is liquid at room temperature, and its viscosity can be adjusted by the processing temperature and the molecular weight.
  • the polymer electrolyte thus prepared can be directly poured into a lithium battery soft pack using equipment of the current lithium battery industry.
  • the polymer represented by Formula 1 provided by the present invention is an amorphous polymer with a low glass transition temperature ( ⁇ -39°C), which has room temperature as a polymer electrolyte Below is liquid, low viscosity, no crystallization, and good solubility.
  • the polymer is a non-crystalline liquid polymer, and its glass transition temperature is below -39°C.
  • R 1 is methyl, ethyl, propyl or hydrogen
  • R 2 is methyl, ethyl, propyl or hydrogen
  • R 3 is methyl, ethyl, propyl or hydrogen
  • R 4 is methyl, ethyl, propyl or hydrogen.
  • the present invention provides a method for preparing the polymer represented by Formula 1 as described above, including the following steps:
  • reaction product containing the polymer represented by Formula 1 is obtained by mixing and reacting with a catalyst.
  • a first solvent is further added, and the first solvent includes tetrahydrofuran.
  • the reaction product is cooled to room temperature, and the first solvent and the catalyst are distilled off under reduced pressure.
  • reaction product is washed with methanol or ether multiple times, and dried in vacuo to obtain a liquid polymer represented by Formula 1.
  • the catalyst includes one or more of triethylamine, ethylamine, propylamine, butylamine, benzoyl peroxide, and azobisisobutyronitrile.
  • the invention provides a polymer electrolyte including a first lithium salt and the polymer represented by Formula 1 as described above.
  • the mass percentage of the polymer represented by the general formula 1 is 20% to 95%.
  • the ion conductivity of the polymer electrolyte at 25°C is 1 ⁇ 10 -5 -6 ⁇ 10 -5 S/cm
  • the ion conductivity at 60°C is 2 ⁇ 10 -4 -6 ⁇ 10 -4 S/cm
  • the migration number of lithium ions at 60°C is greater than 0.36
  • the electrochemical window is above 5.1V.
  • the first lithium salt includes lithium perchlorate, lithium hexafluorophosphate, lithium dioxalate borate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, and lithium difluoromethanexanthimide.
  • the mass percentage of the first lithium salt is 5% to 80%.
  • the polymer electrolyte further includes an additive
  • the additive includes a polymer additive and/or inorganic particles
  • the total mass of the polymer electrolyte is 100%
  • the mass percentage of the additive is 0% ⁇ 60%, preferably 5% to 60%.
  • the polymer additive includes one of polyethylene oxide, polylactic acid, polycaprolactone, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, polyvinyl alcohol and polyvinylidene chloride or Multiple
  • the inorganic particles include one or more of silica, titania, alumina, zirconia, nickel oxide, silicon nitride, magnesium hydroxide, diatomaceous earth, montmorillonite, and kaolin.
  • the polymer electrolyte further includes a second solvent
  • the second solvent includes acetonitrile, dimethyl sulfoxide, sulfolane, dimethyl sulfite, acetone, tetrahydrofuran, chloroform, ethyl acetate, N , N-dimethylformamide and N,N-dimethylacetamide one or more.
  • the invention provides a polymer electrolyte membrane including the polymer electrolyte as described above.
  • porous support includes one or more of glass fiber cloth, non-woven cloth, silica aerogel, and cellulose film.
  • the present invention provides a non-aqueous electrolyte including a third solvent, a second lithium salt, and the polymer represented by Formula 1 as described above.
  • the third solvent is a mixture of cyclic carbonate and chain carbonate.
  • the second lithium salt includes one or more of LiPF 6 , LiBF 4 , LiBOB, LiDFOB, LiN(SO 2 CF 3 ) 2 and LiN(SO 2 F) 2 .
  • the present invention provides a lithium ion battery including a positive electrode and a negative electrode, and further including the polymer electrolyte as described above, or the polymer electrolyte membrane as described above, or the non-aqueous electrolyte as described above.
  • Example 1 is a nuclear magnetic resonance spectrum of the liquid polymer DEG-EDT provided in Example 1 of the present invention
  • Example 2 is a linear voltammetry scanning curve (LSV) of the liquid polymer electrolyte DEG-EDT provided in Example 1 of the present invention.
  • LSV linear voltammetry scanning curve
  • FIG. 3 is a cycle curve at 60° C. of a lithium iron phosphate/lithium metal button battery assembled with a liquid polymer electrolyte DEG-EDT provided in Example 1 of the present invention.
  • An embodiment of the present invention provides a polymer represented by the following general formula 1,
  • R 1 is a hydrocarbon group having 1 to 5 carbon atoms or hydrogen
  • R 2 is a hydrocarbon group having 1 to 5 carbon atoms or hydrogen
  • R 3 is -(CH 2 ) n -or -(CH 2 CH 2 O ) n -or-(CF 2 CF 2 O) n -, where n is 1-100
  • R 4 is -(CH 2 ) m -or-(CH 2 CH 2 O) m -or-(CF 2 CF 2 O) m -, where m takes a value of 1-100
  • p takes a value of 1-500.
  • the polymer is an amorphous liquid polymer, and its glass transition temperature is below -39°C.
  • R 1 is methyl, ethyl, propyl or hydrogen
  • R 2 is methyl, ethyl, propyl or hydrogen
  • R 3 is methyl, ethyl, propyl or Hydrogen
  • R 4 is methyl, ethyl, propyl or hydrogen.
  • the polymer represented by the general formula 1 can be prepared by using different diacrylates and different dithiols as monomers and using an efficient click chemistry method.
  • An embodiment of the present invention provides a method for preparing a polymer represented by Formula 1 as described above, including the following steps:
  • reaction product containing the polymer represented by Formula 1 is obtained by mixing and reacting with a catalyst.
  • the theoretical molar ratio of diacrylate and dithiol is 1:1, and in actual operation, in order to control the molecular weight, the molar ratio of the two can vary within the range of 1:0.1-1.9.
  • the reaction temperature may be 30°C-80°C, and the reaction time may be 2-8h.
  • a first solvent is further added.
  • the first solvent includes tetrahydrofuran.
  • the first solvent is an organic solvent that does not participate in the reaction between diacrylate and dithiol.
  • the first solvent may be tetrahydrofuran.
  • the reaction product is washed with methanol or ether multiple times, and dried in vacuo to obtain a liquid polymer represented by Formula 1.
  • vacuum drying conditions such as drying at 60°C for 24h.
  • the catalyst includes one or more of triethylamine, ethylamine, propylamine, butylamine, benzoyl peroxide, and azobisisobutyronitrile.
  • the theoretical addition amount (molar amount) of the catalyst is twice that of the diacrylate. In actual operation, the molar ratio of the catalyst to the diacrylate may be 1-3:1.
  • the polymer represented by Formula 1 of the present invention can be obtained by performing a polymerization reaction with diacrylate and dithiol as monomers.
  • the polymer represented by the general formula 1 can be applied to lithium ion batteries in various forms.
  • the polymer represented by the general formula 1 can be blended with the first lithium salt to obtain a polymer electrolyte (with or without addition Additive), and infiltrated with porous support to form a polymer electrolyte membrane; the polymer electrolyte can also be directly injected into a soft-pack battery as a polymer electrolyte; or the polymer represented by Formula 1 can be used as an additive Used in small molecule non-aqueous electrolyte to improve the performance of small molecule non-aqueous electrolyte.
  • the present invention provides a polymer electrolyte including a first lithium salt and the polymer represented by Formula 1 as described above.
  • the polymer shown in Formula 1 used in the polymer electrolyte provided by the present invention is an amorphous polymer, and its glass transition temperature is low, which is below -39°C, and the polymer electrolyte is in lithium
  • the normal use temperature of the ion battery is in a fluid state, and the molding process is simple.
  • the existing lithium ion battery industrial equipment for pouring electrolyte can be used to directly prepare a new type lithium battery, which greatly reduces the industrial processing cost.
  • the polymer electrolyte not only has an electrochemical window similar to a solid polymer electrolyte, but also has high ion conductivity and lithium ion migration number based on its fluidity characteristics, good resistance to lithium metal, and NCM or NCA can be used
  • the polymer electrolyte improves the interface stability and long cycle performance of the battery, is easy to scale production and practical application, and has good industrial application prospects.
  • the mass percentage of the polymer represented by Formula 1 is 20% to 95%.
  • the polymer electrolyte has an ion conductivity of 1 ⁇ 10 ⁇ 5 -6 ⁇ 10 ⁇ 5 S/cm at 25° C., and an ion conductivity of 2 ⁇ 10 ⁇ 4 -6 at 60° C. ⁇ 10 -4 S/cm, the migration number of lithium ions at 60°C is greater than 0.36, and the electrochemical window is above 5.1V.
  • the polymer electrolyte has the above-mentioned electrochemical parameter conditions, and can be used as a new type of polymer electrolyte in electrochemical energy batteries. It can be applied to lithium ion batteries, which improves the safety of lithium ion batteries and can solve The problem that the traditional PEO solid electrolyte is not resistant to high pressure provides a key supporting technology for the performance of lithium ion batteries with high specific capacity lithium metal anodes.
  • the first lithium salt includes lithium perchlorate, lithium hexafluorophosphate, lithium dioxalate borate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, and lithium difluoromethanexanthide One or more of them.
  • the mass percentage of the first lithium salt is 5% to 80%.
  • the polymer electrolyte further includes an additive
  • the additive includes a polymer additive and/or inorganic particles
  • the total mass of the polymer electrolyte is 100%
  • the mass percentage of the additive is 0 % To 60%, preferably 5% to 60%.
  • the polymer additives include polyethylene oxide, polylactic acid, polycaprolactone, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, polyvinyl alcohol, and polyvinylidene chloride. One or more.
  • the mass percentage of the polymer additive is 10%-50%.
  • the inorganic particles include one or more of silica, titania, alumina, zirconia, nickel oxide, silicon nitride, magnesium hydroxide, diatomaceous earth, montmorillonite, and kaolin.
  • the mass percentage of the inorganic particles is 0% to 40%.
  • the polymer electrolyte further includes a second solvent
  • the second solvent includes acetonitrile, dimethyl sulfoxide, sulfolane, dimethyl sulfite, acetone, tetrahydrofuran, chloroform, ethyl acetate , N,N-dimethylformamide and N,N-dimethylacetamide one or more.
  • the second solvent is used to increase the solubility of the first lithium salt and the additive in the polymer represented by the general formula 1, in specific operations, the polymer represented by the general formula 1 is dissolved in the second solvent A polymer solution is obtained, and then the first lithium salt and additives are added to the polymer solution and stirred until a uniform mixture is formed.
  • the second solvent may be removed by vacuum drying after the subsequent preparation of the polymer electrolyte membrane, or by vacuum drying before pouring the polymer electrolyte into the flexible packaging battery.
  • Another embodiment of the present invention provides a polymer electrolyte membrane including the polymer electrolyte as described above.
  • the polymer electrolyte membrane further includes a porous support including one or more of glass fiber cloth, non-woven cloth, silica aerogel, and cellulose film .
  • Another embodiment of the present invention provides a non-aqueous electrolyte, including a third solvent, a second lithium salt, and the polymer represented by Formula 1 as described above.
  • the third solvent is a mixture of cyclic carbonate and chain carbonate.
  • the second lithium salt includes one or more of LiPF 6 , LiBF 4 , LiBOB, LiDFOB, LiN(SO 2 CF 3 ) 2 and LiN(SO 2 F) 2 .
  • Another embodiment of the present invention provides a lithium ion battery including a positive electrode and a negative electrode, and further including the polymer electrolyte as described above, or the polymer electrolyte membrane as described above, or the non-aqueous electrolytic solution as described above.
  • the positive electrode includes a positive electrode active material.
  • the positive electrode active material is selected from LiNi x Co y Mn z L ( 1-xyz) O 2, LiCo x 'L (1-x') O 2, LiNi x "L 'y' Mn (2-x" -y ') O 4, Li z' MPO 4 at least one, where, L is Al, Sr, Mg, Ti, Ca, Zr, Zn, Si or at least one of Fe, 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, ⁇ y ⁇ 1, 0 ⁇ z ⁇ 1, 0 ⁇ x+y+z ⁇ 1, 0 ⁇ x' ⁇ 1, 0.3 ⁇ x" ⁇ 0.6, 0.01 ⁇ y' ⁇ 0.2, L'is Co, Al, Sr , Mg, Ti, Ca, Zr, Zn, Si, Fe at least one; 0.5 ⁇ z' ⁇ 1, M is at least one of Fe, Mn, Co.
  • the negative electrode includes a negative electrode active material.
  • the negative electrode active material is made of carbon material, metal alloy, lithium-containing oxide and silicon-containing material.
  • the lithium ion battery further includes a separator, and the separator is located between the positive electrode and the negative electrode.
  • This embodiment is used to explain the preparation method of the polymer electrolyte and the polymer electrolyte membrane disclosed in the present invention, including the following steps:
  • step (1) After the reaction is completed, the reaction mixture solution in step (1) is cooled to room temperature, the solvent tetrahydrofuran and the catalyst triethylamine are distilled off under reduced pressure, the product is washed 3 times with methanol or ether, and dried under vacuum at 60°C for 24h Get viscous liquid polymer DEG-EDT;
  • step (3) Dissolve 2.0 g of the liquid polymer DEG-EDT obtained in step (2) with 8 mL of anhydrous tetrahydrofuran to obtain a uniform polymer solution, then add 0.2 g of LiTFSI to the above uniform solution and stir at normal temperature Dissolve to obtain a uniform polymer electrolyte.
  • the polymer electrolyte was evenly poured on the glass fiber cloth placed in the polytetrafluoroethylene mold, the solvent was slowly volatilized at room temperature, and then vacuum dried at 100°C for 12 hours to obtain a polymer electrolyte membrane.
  • This embodiment is used to explain the preparation method of the polymer electrolyte and the polymer electrolyte membrane disclosed in the present invention, including the following steps:
  • step (1) After the reaction, the reaction mixture solution in step (1) was cooled to room temperature, the solvent tetrahydrofuran was distilled off under reduced pressure, the product was washed 3 times with methanol or ether, and dried under vacuum at 60°C for 24 hours to obtain a viscous liquid polymerization ⁇ DED-EDT;
  • step (3) Dissolve 2.0 g of the liquid polymer DED-EDT obtained in step (2) with 8 mL of anhydrous tetrahydrofuran to obtain a uniform polymer solution, then add 0.2 g of LiTFSI to the above uniform solution and stir at normal temperature Dissolve to obtain a uniform polymer electrolyte.
  • the polymer electrolyte was evenly poured on the glass fiber cloth placed in the polytetrafluoroethylene mold, the solvent was slowly volatilized at room temperature, and then vacuum dried at 100°C for 12 hours to obtain a polymer electrolyte membrane.
  • This embodiment is used to explain the preparation method of the polymer electrolyte and the polymer electrolyte membrane disclosed in the present invention, including the following steps:
  • step (1) After the reaction, the reaction mixture solution in step (1) was cooled to room temperature, the catalyst triethylamine was distilled off under reduced pressure, the product was washed 3 times with methanol or ether, and dried under vacuum at 60°C for 24 hours to obtain a thick Liquid polymer TGD-EDT;
  • step (3) Dissolve 2.0 g of the liquid polymer TGD-EDT obtained in step (2) with 8 mL of anhydrous tetrahydrofuran to obtain a uniform polymer solution, then add 0.2 g of LiTFSI to the above uniform solution and stir at normal temperature Dissolve to obtain a uniform polymer electrolyte.
  • the polymer electrolyte was evenly poured on the glass fiber cloth placed in the polytetrafluoroethylene mold, the solvent was slowly volatilized at room temperature, and then vacuum dried at 100°C for 12 hours to obtain a polymer electrolyte membrane.
  • This embodiment is used to explain the preparation method of the polymer electrolyte and the polymer electrolyte membrane disclosed in the present invention, including the following steps:
  • step (1) After the reaction, the reaction mixture solution in step (1) was cooled to room temperature, the catalyst triethylamine was distilled off under reduced pressure, the product was washed 3 times with methanol or ether, and dried under vacuum at 60°C for 24 hours to obtain a thick Liquid polymer TeED-EDT;
  • step (3) Dissolve 2.0 g of the liquid polymer TeED-EDT obtained in step (2) with 8 mL of anhydrous tetrahydrofuran to obtain a uniform polymer solution, then add 0.2 g of LiFSI to the above uniform solution and stir at normal temperature Dissolve to obtain a uniform polymer electrolyte.
  • the polymer electrolyte was evenly poured on the glass fiber cloth placed in the polytetrafluoroethylene mold, the solvent was slowly volatilized at room temperature, and then vacuum dried at 100°C for 12 hours to obtain a polymer electrolyte membrane.
  • This embodiment is used to explain the preparation method of the polymer electrolyte and the polymer electrolyte membrane disclosed in the present invention, including the following steps:
  • step (1) After the reaction, the reaction mixture solution in step (1) was cooled to room temperature, the catalyst triethylamine was distilled off under reduced pressure, the product was washed 3 times with methanol or ether, and dried under vacuum at 60°C for 24 hours to obtain a thick Liquid polymer BDMA-EGB;
  • step (3) Dissolve 2.0 g of the liquid polymer BDMA-EGB obtained in step (2) with 8 mL of anhydrous tetrahydrofuran to obtain a uniform polymer solution, then add 0.2 g of LiTFSI to the above uniform solution and stir at normal temperature Dissolve to obtain a uniform polymer electrolyte.
  • the polymer electrolyte was evenly poured on the glass fiber cloth placed in the polytetrafluoroethylene mold, the solvent was slowly volatilized at room temperature, and then vacuum dried at 100°C for 12 hours to obtain a polymer electrolyte membrane.
  • This embodiment is used to explain the preparation method of the polymer electrolyte and the polymer electrolyte membrane disclosed in the present invention, including the following steps:
  • step (1) After the reaction, the reaction mixture solution in step (1) was cooled to room temperature, the catalyst triethylamine was distilled off under reduced pressure, the product was washed 3 times with methanol or ether, and dried under vacuum at 60°C for 24 hours to obtain a thick Liquid polymer TGD-EGB;
  • step (3) Dissolve 2.0g of the liquid polymer TGD-EGB obtained in step (2) with 8mL of anhydrous tetrahydrofuran to obtain a uniform polymer solution, then add 0.2g of LiTFSI to the above uniform solution and stir at normal temperature Dissolve to obtain a uniform polymer electrolyte.
  • the polymer electrolyte was evenly cast on the glass fiber cloth placed in the polytetrafluoroethylene mold, the solvent was slowly volatilized at room temperature, and then vacuum dried at 100°C for 12 hours to obtain a polymer electrolyte membrane.
  • This comparative example is used to illustrate the preparation method of the polymer electrolyte and polymer electrolyte membrane disclosed in the present invention, including:
  • Example 1 The liquid polymer DEG-EDT prepared in Example 1 was subjected to a nuclear magnetic resonance test to obtain the nuclear magnetic resonance spectrum shown in FIG. 1.
  • Example 2 The polymer electrolyte prepared in Example 1 was subjected to a linear voltammetry curve test at 60°C to obtain a linear voltammetry curve as shown in FIG. 2.
  • the polymer electrolyte can withstand a voltage of 5.2 volts or more.
  • the polymer electrolyte membrane prepared in Example 1, the positive electrode lithium iron phosphate, and the negative electrode lithium metal were assembled to obtain a lithium iron phosphate/lithium metal battery, and the battery cycle test was performed at 60°C to obtain the cycle curve shown in FIG. 3.
  • the preparation process of the above lithium iron phosphate/lithium metal battery is: dissolving PVDF in NMP to obtain a polymer solution with a concentration of 0.1mol/L, according to the positive electrode active material, conductive carbon black and PVDF (that is, the solute in the above solution) to The mass ratio of 8:1:1 is milled evenly after mixing.
  • the above mixed slurry is evenly coated on aluminum foil, with a thickness of 100-200 ⁇ m, dried at 60°C, then dried in a vacuum oven at 120°C, rolled, punched, weighed, and then continued at 120°C It was dried in a vacuum oven and placed in a glove box to obtain a positive electrode; a lithium metal sheet was used as the negative electrode, and the polymer electrolyte membrane provided in Example 1 was used to assemble the battery.
  • the lithium iron phosphate/lithium metal battery assembled with the polymer electrolyte DEG-EDT has good cycle stability, and its capacity is still more than 90% of the initial value after 450 cycles.
  • Membrane thickness A micrometer (accuracy of 0.01mm) is used to test the thickness of the polymer electrolyte membrane. After compressing the sample of the polymer electrolyte membrane, randomly take 5 points and take the average.
  • Ionic conductivity sandwich the polymer electrolyte membrane with two pieces of stainless steel and place it in a 2025 type battery case.
  • Electrochemical window The polymer electrolyte membrane is sandwiched between a stainless steel sheet and a lithium sheet, and placed in a 2025 battery case.
  • the electrochemical working window is measured by a linear voltammetry at an electrochemical workstation.
  • the initial potential is 2.5V and the highest potential is 7V, scanning speed is 1mV/s.
  • T g glass transition temperature
  • T m melting temperature
  • Lithium ion migration number test using two lithium sheets to sandwich a polymer electrolyte membrane to make a non-blocking symmetric battery.
  • the compound represented by Formula 1 provided by the present invention is an amorphous polymer, it has no melting temperature.
  • the polymer provided by the present invention has a higher ionic conductivity and a wider electrochemical window, and can be effectively used as a polymer electrolyte of a lithium ion battery, effectively solving the traditional solid state
  • the problems of poor stability of polymer electrolytes and low ionic conductivity are non-crystalline polymers with a low glass transition temperature, which can effectively solve the problem of poor processing performance of traditional solid polymer electrolytes.

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Abstract

In order to overcome the problems of poor ion conductivity, stability, and processability of existing polymer electrolytes, the present invention provides a polymer represented by the following general formula 1, wherein R1 is a hydrocarbon group having 1 to 5 carbon atoms or a hydrogen; R2 is a hydrocarbon group having 1 to 5 carbon atoms or a hydrogen; R3 is -(CH2)n- or -(CH2CH2O)n- or -(CF2CF2O)n-, where n is 1 to 100; R4 is -(CH2)m- or -(CH2CH2O)m- or -(CF2CF2O)m-, where m is 1 to 100, and p is 1 to 500. Further disclosed are a polymer electrolyte, a polymer electrolyte membrane, a non-aqueous electrolyte solution, and a lithium ion battery containing the polymer. The polymer provided by the present invention can be processed using various processes, has a high ionic conductivity and a wide electrochemical window, and greater safety.

Description

聚合物、聚合物电解质、聚合物电解质膜、非水电解液及锂离子电池Polymer, polymer electrolyte, polymer electrolyte membrane, non-aqueous electrolyte and lithium ion battery 技术领域Technical field
本发明属于锂离子电池技术领域，具体涉及一种聚合物、聚合物电解质、聚合物电解质膜、非水电解液及锂离子电池。The invention belongs to the technical field of lithium ion batteries, and particularly relates to a polymer, a polymer electrolyte, a polymer electrolyte membrane, a non-aqueous electrolyte and a lithium ion battery.
背景技术Background technique
发展高效二次电池储能器件，对于改善火力发电污染、发展可持续能源、减少石油依赖、提高能源资源利用效率和解决雾霾等环境污染都具有非常重要的战略意义。近些年，随着智能电子设备、电动汽车和大型储能设备的广泛开发应用，作为其电力储备源的锂离子电池也随之得到长足的进步和发展。然而，目前的锂离子电池依然难以满足人们对更高能量密度的渴望，发展高比能量、高安全性的锂二次电池对新能源产业具有重要的意义和价值。The development of high-efficiency secondary battery energy storage devices has very important strategic significance for improving thermal power generation pollution, developing sustainable energy, reducing oil dependence, improving energy resource utilization efficiency, and solving environmental pollution such as smog. In recent years, with the extensive development and application of intelligent electronic equipment, electric vehicles and large-scale energy storage equipment, the lithium-ion battery as its power reserve source has also made considerable progress and development. However, the current lithium-ion battery is still difficult to meet people's desire for higher energy density, and the development of high specific energy and high safety lithium secondary batteries is of great significance and value to the new energy industry.
随着电池产业的发展和电池能量密度的进一步提高，近几年频频爆出锂电池安全事故，如手机***、电动汽车燃烧事故等，安全问题已成为制约锂离子电池更广泛深入应用的技术瓶颈。目前广泛使用的锂离子电池均采用小分子液态有机电解液，其闪点低而高度易燃，在过度充电、内部短路等异常情况下有严重的安全隐患。而高分子电解质在电池能量密度、高温工作温度区间、循环寿命等方面均有较大的提升，有望彻底解决电池的安全性问题，是未来储能器件的发展的必然方向之一。With the development of the battery industry and the further improvement of battery energy density, lithium battery safety accidents have frequently exploded in recent years, such as cell phone explosions and electric vehicle burning accidents. Safety issues have become a technical bottleneck that restricts the wider and deeper application of lithium ion batteries. . Currently widely used lithium-ion batteries use small molecule liquid organic electrolytes, which have a low flash point and are highly flammable. There are serious safety hazards under abnormal conditions such as overcharging and internal short circuits. The polymer electrolyte has greatly improved the battery energy density, high temperature operating temperature range, cycle life and other aspects. It is expected to completely solve the battery safety problem and is one of the inevitable directions for the future development of energy storage devices.
尽管高分子固态电解质具有质轻、柔韧性好、易成膜等优点，但是目前文献报道的高分子固态电解质主要存在的问题是其容易结晶、低电导率、低锂离子迁移数和电化学窗口窄，无法使用高能量密度的正极材料(如NCM和NCA等)，此外高分子固态电解质还存在加工成本高的问题，对比小分子液态电解质，高分子固态电解质需要全新的加工设备和工艺，工业成本较高。比较常见的聚合物固态电解质的聚合物主要包括聚氧化乙烯、聚偏氟乙烯、聚丙烯腈、聚甲基丙烯酸甲酯等。一些公开的聚合物电解质实例包括：专利US 4792504公开的一种聚合物电解质，其主要由聚二甲基丙烯酸乙二醇/聚环氧烷，但其电化学稳定较差，机械性能有待提高。作为一种最早也是最常见的聚合物固态电解质， 聚氧化乙烯(PEO)/锂盐型电解质的高温离子电导率较高，但是该类聚合物的机械性能较差，不易制得可自支撑的聚合物电解质薄膜，且锂离子迁移数低，在高电压下稳定性较差，因此极大地限制了该类聚合物电解质的应用。Although the polymer solid electrolyte has the advantages of light weight, good flexibility, and easy film formation, the main problems of the polymer solid electrolyte reported in the literature at present are its easy crystallization, low conductivity, low lithium ion migration number, and electrochemical window Narrow, high energy density cathode materials (such as NCM and NCA, etc.) cannot be used. In addition, polymer solid electrolytes also have the problem of high processing costs. Compared with small molecule liquid electrolytes, polymer solid electrolytes require new processing equipment and processes. Industrial higher cost. The more common polymer solid-state electrolyte polymers mainly include polyethylene oxide, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, etc. Some examples of disclosed polymer electrolytes include: a polymer electrolyte disclosed in US Pat. No. 4,792,504, which is mainly composed of polyethylene dimethacrylate/polyalkylene oxide, but its electrochemical stability is poor, and its mechanical properties need to be improved. As one of the earliest and most common polymer solid electrolytes, polyethylene oxide (PEO)/lithium salt electrolytes have higher high-temperature ionic conductivity, but the mechanical properties of such polymers are poor, making it difficult to make self-supporting The polymer electrolyte film has low lithium ion migration number and poor stability at high voltage, which greatly limits the application of this type of polymer electrolyte.
发明内容Summary of the invention
针对现有聚合物电解质存在离子传导性能、稳定性差的问题，本发明提供了一种聚合物、聚合物电解质、聚合物电解质膜、非水电解液及锂离子电池。In view of the problems of poor ion conductivity and poor stability of existing polymer electrolytes, the present invention provides a polymer, polymer electrolyte, polymer electrolyte membrane, non-aqueous electrolyte, and lithium ion battery.
本发明解决上述技术问题所采用的技术方案如下：The technical solutions adopted by the present invention to solve the above technical problems are as follows:
一方面，本发明提供了一种如下通式1所示的聚合物，In one aspect, the present invention provides a polymer represented by the following general formula 1,
Figure PCTCN2019124768-appb-000001
Figure PCTCN2019124768-appb-000001
其中，R 1为碳原子数为1-5的烃基或氢；R 2为碳原子数为1-5的烃基或氢；R 3为-(CH 2) n-或-(CH 2CH 2O) n-或-(CF 2CF 2O) n-，其中n取值为1-100；R 4为-(CH 2) m-或-(CH 2CH 2O) m-或-(CF 2CF 2O) m-，其中m取值为1-100；p取值为1-500。 Wherein, R 1 is a hydrocarbon group having 1 to 5 carbon atoms or hydrogen; R 2 is a hydrocarbon group having 1 to 5 carbon atoms or hydrogen; R 3 is -(CH 2 ) n -or -(CH 2 CH 2 O ) n -or-(CF 2 CF 2 O) n -, where n is 1-100; R 4 is -(CH 2 ) m -or-(CH 2 CH 2 O) m -or-(CF 2 CF 2 O) m -, where m takes a value of 1-100; p takes a value of 1-500.
本发明提供的通式1所示的聚合物制备得到的聚合物电解质电导率(60℃时的电导率>10 -4S/cm)和锂离子迁移数高(>0.36)，与锂金属具有良好的相容性，从而提高了界面稳定性与长循环性能。采用通式1所示的聚合物作为聚合物电解质可以避免低闪点的有机小分子电解质存在的安全隐患，大大提升了锂电池的安全使用性能。 The polymer electrolyte prepared by the polymer represented by the general formula 1 provided by the present invention has a conductivity (the conductivity at 60°C>10 -4 S/cm) and a high lithium ion migration number (>0.36), which has Good compatibility, thereby improving interface stability and long cycle performance. Using the polymer shown in Formula 1 as a polymer electrolyte can avoid the safety hazards of low-flash point organic small molecule electrolytes, and greatly improves the safe use performance of lithium batteries.
同时，根据本发明提供的通式1所示的聚合物，为非结晶性聚合物，其玻璃化温度低，在室温下即为液态，其粘度可以通过加工温度及分子量的大小来调控。由此制备的聚合物电解质可以使用目前锂电池产业的设备来直接灌注到锂电池软包中使用。对比现有的固态电解质所用聚合物，如PEO等，本发明提供的通式1所示的聚合物为非结晶性聚合物，玻璃化温度低(～-39℃)，作为聚合物电解质具有室温下即为液态、粘度低、无结晶现象、溶解性好的特点。At the same time, the polymer represented by the general formula 1 provided by the present invention is an amorphous polymer with a low glass transition temperature, which is liquid at room temperature, and its viscosity can be adjusted by the processing temperature and the molecular weight. The polymer electrolyte thus prepared can be directly poured into a lithium battery soft pack using equipment of the current lithium battery industry. Compared with the existing polymers used in solid electrolytes, such as PEO, etc., the polymer represented by Formula 1 provided by the present invention is an amorphous polymer with a low glass transition temperature (~-39°C), which has room temperature as a polymer electrolyte Below is liquid, low viscosity, no crystallization, and good solubility.
可选的，所述聚合物为非结晶性液态聚合物，其玻璃化转变温度为-39℃以 下。Optionally, the polymer is a non-crystalline liquid polymer, and its glass transition temperature is below -39°C.
可选的，所述R 1为甲基、乙基、丙基或氢；R 2为甲基、乙基、丙基或氢；所述R 3为甲基、乙基、丙基或氢；R 4为甲基、乙基、丙基或氢。 Optionally, R 1 is methyl, ethyl, propyl or hydrogen; R 2 is methyl, ethyl, propyl or hydrogen; R 3 is methyl, ethyl, propyl or hydrogen; R 4 is methyl, ethyl, propyl or hydrogen.
另一方面，本发明提供了如上所述的通式1所示的聚合物的制备方法，包括以下步骤：In another aspect, the present invention provides a method for preparing the polymer represented by Formula 1 as described above, including the following steps:
采用二丙烯酸酯和二硫醇作为单体，与催化剂混合反应得到包含通式1所示的聚合物的反应产物。Using diacrylate and dithiol as monomers, the reaction product containing the polymer represented by Formula 1 is obtained by mixing and reacting with a catalyst.
可选的，还加入有第一溶剂，所述第一溶剂包括四氢呋喃，反应完成后将反应产物冷却至室温，减压蒸馏除去第一溶剂和催化剂。Optionally, a first solvent is further added, and the first solvent includes tetrahydrofuran. After the reaction is completed, the reaction product is cooled to room temperature, and the first solvent and the catalyst are distilled off under reduced pressure.
可选的，反应结束后，使用甲醇或***多次洗涤反应产物，真空干燥得到液态的通式1所示的聚合物。Optionally, after the reaction is completed, the reaction product is washed with methanol or ether multiple times, and dried in vacuo to obtain a liquid polymer represented by Formula 1.
可选的，所述催化剂包括三乙胺、乙胺、丙胺、丁胺、过氧化苯甲酰和偶氮二异丁腈中的一种或多种。Optionally, the catalyst includes one or more of triethylamine, ethylamine, propylamine, butylamine, benzoyl peroxide, and azobisisobutyronitrile.
另一方面，本发明提供了一种聚合物电解质，包括第一锂盐以及如上所述的通式1所示的聚合物。In another aspect, the invention provides a polymer electrolyte including a first lithium salt and the polymer represented by Formula 1 as described above.
可选的，以所述聚合物电解质的总质量为100％计，所述通式1所示的聚合物的质量百分比为20％～95％。Optionally, based on the total mass of the polymer electrolyte being 100%, the mass percentage of the polymer represented by the general formula 1 is 20% to 95%.
可选的，所述聚合物电解质在25℃下的离子电导率为1×10 -5-6×10 -5S/cm，60℃下的离子电导率为2×10 -4-6×10 -4S/cm，60℃下的锂离子迁移数大于0.36，电化学窗口为5.1V以上。 Optionally, the ion conductivity of the polymer electrolyte at 25°C is 1×10 -5 -6×10 -5 S/cm, and the ion conductivity at 60°C is 2×10 -4 -6×10 -4 S/cm, the migration number of lithium ions at 60℃ is greater than 0.36, and the electrochemical window is above 5.1V.
可选的，所述第一锂盐包括高氯酸锂、六氟磷酸锂、二草酸硼酸锂、六氟砷酸锂、四氟硼酸锂、三氟甲基磺酸锂和双氟甲烷黄酰亚胺锂中的一种或多种；Optionally, the first lithium salt includes lithium perchlorate, lithium hexafluorophosphate, lithium dioxalate borate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, and lithium difluoromethanexanthimide. One or more
以所述聚合物电解质的总质量为100％计，所述第一锂盐的质量百分比为5％～80％。Based on the total mass of the polymer electrolyte being 100%, the mass percentage of the first lithium salt is 5% to 80%.
可选的，所述聚合物电解质还包括添加剂，所述添加剂包括高分子添加剂和/或无机颗粒，以所述聚合物电解质的总质量为100％计，所述添加剂的质量百分比为0％～60％，优选为5％～60％。Optionally, the polymer electrolyte further includes an additive, the additive includes a polymer additive and/or inorganic particles, the total mass of the polymer electrolyte is 100%, and the mass percentage of the additive is 0%~ 60%, preferably 5% to 60%.
可选的，所述高分子添加剂包括聚氧化乙烯、聚乳酸、聚己内酯、聚偏氟乙烯、聚丙烯腈、聚甲基丙烯酸甲酯、聚乙烯醇和聚偏氯乙烯中的一种或多种；Optionally, the polymer additive includes one of polyethylene oxide, polylactic acid, polycaprolactone, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, polyvinyl alcohol and polyvinylidene chloride or Multiple
所述无机物颗粒包括二氧化硅、二氧化钛、三氧化二铝、氧化锆、氧化镍、氮化硅、氢氧化镁、硅藻土、蒙脱土和高岭土中的一种或多种。The inorganic particles include one or more of silica, titania, alumina, zirconia, nickel oxide, silicon nitride, magnesium hydroxide, diatomaceous earth, montmorillonite, and kaolin.
可选的，所述聚合物电解质还包括第二溶剂，所述第二溶剂包括乙腈、二甲基亚砜、环丁砜、亚硫酸二甲酯、丙酮、四氢呋喃、三氯甲烷、乙酸乙酯、N,N-二甲基甲酰胺和N,N-二甲基乙酰胺中的一种或多种。Optionally, the polymer electrolyte further includes a second solvent, and the second solvent includes acetonitrile, dimethyl sulfoxide, sulfolane, dimethyl sulfite, acetone, tetrahydrofuran, chloroform, ethyl acetate, N , N-dimethylformamide and N,N-dimethylacetamide one or more.
另一方面，本发明提供了一种聚合物电解质膜，包括如上所述的聚合物电解质。In another aspect, the invention provides a polymer electrolyte membrane including the polymer electrolyte as described above.
可选的，还包括有多孔支撑物，所述多孔支撑物包括玻璃纤维布、无纺布、二氧化硅气凝胶和纤维素膜中的一种或多种。Optionally, a porous support is also included. The porous support includes one or more of glass fiber cloth, non-woven cloth, silica aerogel, and cellulose film.
另一方面，本发明提供了一种非水电解液，包括第三溶剂、第二锂盐和如上所述的通式1所示的聚合物。In another aspect, the present invention provides a non-aqueous electrolyte including a third solvent, a second lithium salt, and the polymer represented by Formula 1 as described above.
可选的，所述第三溶剂为环状碳酸酯和链状碳酸酯的混合物。Optionally, the third solvent is a mixture of cyclic carbonate and chain carbonate.
可选的，所述第二锂盐包括LiPF 6、LiBF 4、LiBOB、LiDFOB、LiN(SO 2CF 3) 2和LiN(SO 2F) 2中的一种或多种。 Optionally, the second lithium salt includes one or more of LiPF 6 , LiBF 4 , LiBOB, LiDFOB, LiN(SO 2 CF 3 ) 2 and LiN(SO 2 F) 2 .
另一方面，本发明提供了一种锂离子电池，包括正极和负极，还包括如上所述的聚合物电解质，或如上所述的聚合物电解质膜，或如上所述的非水电解液。On the other hand, the present invention provides a lithium ion battery including a positive electrode and a negative electrode, and further including the polymer electrolyte as described above, or the polymer electrolyte membrane as described above, or the non-aqueous electrolyte as described above.
附图说明BRIEF DESCRIPTION
图1是本发明实施例1提供的液态聚合物DEG-EDT的核磁共振谱图；1 is a nuclear magnetic resonance spectrum of the liquid polymer DEG-EDT provided in Example 1 of the present invention;
图2是本发明实施例1提供的液态聚合物电解质DEG-EDT的线性伏安扫描曲线(LSV)。2 is a linear voltammetry scanning curve (LSV) of the liquid polymer electrolyte DEG-EDT provided in Example 1 of the present invention.
图3是本发明实施例1提供的液态聚合物电解质DEG-EDT组装的磷酸铁锂/锂金属纽扣电池在60℃下的循环曲线。FIG. 3 is a cycle curve at 60° C. of a lithium iron phosphate/lithium metal button battery assembled with a liquid polymer electrolyte DEG-EDT provided in Example 1 of the present invention.
具体实施方式detailed description
为了使本发明所解决的技术问题、技术方案及有益效果更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。In order to make the technical problems, technical solutions and beneficial effects solved by the present invention clearer, the present invention will be further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention, and are not intended to limit the present invention.
本发明一实施例提供了一种如下通式1所示的聚合物，An embodiment of the present invention provides a polymer represented by the following general formula 1,
Figure PCTCN2019124768-appb-000002
Figure PCTCN2019124768-appb-000002
Figure PCTCN2019124768-appb-000003
Figure PCTCN2019124768-appb-000003
其中，R 1为碳原子数为1-5的烃基或氢；R 2为碳原子数为1-5的烃基或氢；R 3为-(CH 2) n-或-(CH 2CH 2O) n-或-(CF 2CF 2O) n-，其中n取值为1-100；R 4为-(CH 2) m-或-(CH 2CH 2O) m-或-(CF 2CF 2O) m-，其中m取值为1-100；p取值为1-500。 Wherein, R 1 is a hydrocarbon group having 1 to 5 carbon atoms or hydrogen; R 2 is a hydrocarbon group having 1 to 5 carbon atoms or hydrogen; R 3 is -(CH 2 ) n -or -(CH 2 CH 2 O ) n -or-(CF 2 CF 2 O) n -, where n is 1-100; R 4 is -(CH 2 ) m -or-(CH 2 CH 2 O) m -or-(CF 2 CF 2 O) m -, where m takes a value of 1-100; p takes a value of 1-500.
在一些实施例中，所述聚合物为非结晶性液态聚合物，其玻璃化转变温度为-39℃以下。In some embodiments, the polymer is an amorphous liquid polymer, and its glass transition temperature is below -39°C.
在一些实施例中，所述R 1为甲基、乙基、丙基或氢；R 2为甲基、乙基、丙基或氢；所述R 3为甲基、乙基、丙基或氢；R 4为甲基、乙基、丙基或氢。 In some embodiments, R 1 is methyl, ethyl, propyl or hydrogen; R 2 is methyl, ethyl, propyl or hydrogen; R 3 is methyl, ethyl, propyl or Hydrogen; R 4 is methyl, ethyl, propyl or hydrogen.
所述通式1所示的聚合物可采用不同的二丙烯酸酯和不同的二硫醇作为单体，采用高效的点击化学(click chemistry)的方法制备得到。The polymer represented by the general formula 1 can be prepared by using different diacrylates and different dithiols as monomers and using an efficient click chemistry method.
本发明一实施例提供了如上所述的通式1所示的聚合物的制备方法，包括以下步骤：An embodiment of the present invention provides a method for preparing a polymer represented by Formula 1 as described above, including the following steps:
采用二丙烯酸酯和二硫醇作为单体，与催化剂混合反应得到包含通式1所示的聚合物的反应产物。Using diacrylate and dithiol as monomers, the reaction product containing the polymer represented by Formula 1 is obtained by mixing and reacting with a catalyst.
其中，为获得高分子量的聚合物，二丙烯酸酯和二硫醇的理论摩尔比为1:1，实际操作时，为控制分子量，二者摩尔比可在1:0.1-1.9的范围内变动。Among them, in order to obtain high molecular weight polymers, the theoretical molar ratio of diacrylate and dithiol is 1:1, and in actual operation, in order to control the molecular weight, the molar ratio of the two can vary within the range of 1:0.1-1.9.
反应过程中采用氮气或惰性气体进行保护。反应温度可以为30℃-80℃，反应时间可以为2-8h。Nitrogen or inert gas is used for protection during the reaction. The reaction temperature may be 30°C-80°C, and the reaction time may be 2-8h.
在一些实施例中，还加入有第一溶剂，所述第一溶剂包括四氢呋喃，反应完成后将反应产物冷却至室温，减压蒸馏除去第一溶剂和催化剂。In some embodiments, a first solvent is further added. The first solvent includes tetrahydrofuran. After the reaction is completed, the reaction product is cooled to room temperature, and the first solvent and the catalyst are distilled off under reduced pressure.
所述第一溶剂采用不参与二丙烯酸酯和二硫醇之间反应的有机溶剂，具体的，所述第一溶剂可采用四氢呋喃。The first solvent is an organic solvent that does not participate in the reaction between diacrylate and dithiol. Specifically, the first solvent may be tetrahydrofuran.
在一些实施例中，反应结束后，使用甲醇或***多次洗涤反应产物，真空干燥得到液态的通式1所示的聚合物。真空干燥的条件没有特殊要求，例如为60℃干燥24h。In some embodiments, after the reaction is completed, the reaction product is washed with methanol or ether multiple times, and dried in vacuo to obtain a liquid polymer represented by Formula 1. There are no special requirements for the vacuum drying conditions, such as drying at 60°C for 24h.
在一些实施例中，所述催化剂包括三乙胺、乙基胺、丙基胺、丁基胺，过氧化苯甲酰和偶氮二异丁腈中的一种或多种。催化剂的理论添加量(摩尔量)为二丙烯酸酯的2倍，实际操作时，催化剂与二丙烯酸酯的摩尔比可以为1-3:1。In some embodiments, the catalyst includes one or more of triethylamine, ethylamine, propylamine, butylamine, benzoyl peroxide, and azobisisobutyronitrile. The theoretical addition amount (molar amount) of the catalyst is twice that of the diacrylate. In actual operation, the molar ratio of the catalyst to the diacrylate may be 1-3:1.
在化学合成领域，可以理解的，通过二丙烯酸酯和二硫醇作为单体，进行聚合反应，可以得到本发明通式1所示的聚合物。In the field of chemical synthesis, it can be understood that the polymer represented by Formula 1 of the present invention can be obtained by performing a polymerization reaction with diacrylate and dithiol as monomers.
所述通式1所示的聚合物可通过多种形式应用于锂离子电池中，比如，可将通式1所示的聚合物与第一锂盐共混得到聚合物电解质(加入或不加入添加剂)，并与多孔支撑物浸润复合而成聚合物电解质膜；也可将该聚合物电解质直接注入软包电池中作为聚合物电解质来使用；或是将通式1所示的聚合物作为添加剂加入至小分子非水电解液中使用，以提高小分子非水电解液的性能。The polymer represented by the general formula 1 can be applied to lithium ion batteries in various forms. For example, the polymer represented by the general formula 1 can be blended with the first lithium salt to obtain a polymer electrolyte (with or without addition Additive), and infiltrated with porous support to form a polymer electrolyte membrane; the polymer electrolyte can also be directly injected into a soft-pack battery as a polymer electrolyte; or the polymer represented by Formula 1 can be used as an additive Used in small molecule non-aqueous electrolyte to improve the performance of small molecule non-aqueous electrolyte.
以下对所述通式1所示的聚合物的不同应用进行具体说明：The different applications of the polymer represented by the general formula 1 are specifically described below:
本发明提供了一种聚合物电解质，包括第一锂盐以及如上所述的通式1所示的聚合物。The present invention provides a polymer electrolyte including a first lithium salt and the polymer represented by Formula 1 as described above.
相对于传统固态聚合物电解质，由本发明提供的聚合物电解质中采用的式1所示的聚合物为非结晶性聚合物，其玻璃化转变温度低，为-39℃以下，聚合物电解质在锂离子电池的正常使用温度下为流体态，成型工艺简单，可采用现有锂离子电池灌注电解液的工业设备来直接制备新型锂电池，极大地降低了工业加工成本。所述聚合物电解质不仅具有与固态聚合物电解质相似的电化学窗口，基于其流动性的特点，其离子电导率和锂离子迁移数也高、对锂金属耐受性好、可采用NCM或NCA等高能量密度的高能量密度正极材料来组装锂电池，该聚合物电解质提高了电池的界面稳定性与长循环性能，易于规模化生产及实际应用，具有良好的工业应用前景。Compared with the traditional solid polymer electrolyte, the polymer shown in Formula 1 used in the polymer electrolyte provided by the present invention is an amorphous polymer, and its glass transition temperature is low, which is below -39°C, and the polymer electrolyte is in lithium The normal use temperature of the ion battery is in a fluid state, and the molding process is simple. The existing lithium ion battery industrial equipment for pouring electrolyte can be used to directly prepare a new type lithium battery, which greatly reduces the industrial processing cost. The polymer electrolyte not only has an electrochemical window similar to a solid polymer electrolyte, but also has high ion conductivity and lithium ion migration number based on its fluidity characteristics, good resistance to lithium metal, and NCM or NCA can be used To assemble lithium batteries with high energy density cathode materials with high energy density, the polymer electrolyte improves the interface stability and long cycle performance of the battery, is easy to scale production and practical application, and has good industrial application prospects.
在一些实施例中，以所述聚合物电解质的总质量为100％计，所述通式1所示的聚合物的质量百分比为20％～95％。In some embodiments, based on the total mass of the polymer electrolyte being 100%, the mass percentage of the polymer represented by Formula 1 is 20% to 95%.
在一些实施例中，所述聚合物电解质在25℃下的离子电导率为1×10 -5-6×10 -5S/cm，60℃下的离子电导率为2×10 -4-6×10 -4S/cm，60℃下的锂离子迁移数大于0.36，电化学窗口为5.1V以上。 In some embodiments, the polymer electrolyte has an ion conductivity of 1×10 −5 -6×10 −5 S/cm at 25° C., and an ion conductivity of 2×10 −4 -6 at 60° C. ×10 -4 S/cm, the migration number of lithium ions at 60℃ is greater than 0.36, and the electrochemical window is above 5.1V.
所述聚合物电解质具备上述电化学参数条件，可作为一种新型聚合物电解质在电化学能源电池中的应用，将其应用于锂离子电池中，提高了锂离子电池的安全性，同时能够解决传统PEO固态电解质不耐高压的问题，为高比容量锂金属负极的锂离子电池的性能发挥提供关键支撑技术。The polymer electrolyte has the above-mentioned electrochemical parameter conditions, and can be used as a new type of polymer electrolyte in electrochemical energy batteries. It can be applied to lithium ion batteries, which improves the safety of lithium ion batteries and can solve The problem that the traditional PEO solid electrolyte is not resistant to high pressure provides a key supporting technology for the performance of lithium ion batteries with high specific capacity lithium metal anodes.
在一些实施例中，所述第一锂盐包括高氯酸锂、六氟磷酸锂、二草酸硼酸锂、六氟砷酸锂、四氟硼酸锂、三氟甲基磺酸锂和双氟甲烷黄酰亚胺锂中的一种或多种。In some embodiments, the first lithium salt includes lithium perchlorate, lithium hexafluorophosphate, lithium dioxalate borate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, and lithium difluoromethanexanthide One or more of them.
以所述聚合物电解质的总质量为100％计，所述第一锂盐的质量百分比为5％～80％。Based on the total mass of the polymer electrolyte being 100%, the mass percentage of the first lithium salt is 5% to 80%.
在一些实施例中，所述聚合物电解质还包括添加剂，所述添加剂包括高分子添加剂和/或无机颗粒，以所述聚合物电解质的总质量为100％计，所述添加剂的质量百分比为0％～60％，优选为5％～60％。In some embodiments, the polymer electrolyte further includes an additive, the additive includes a polymer additive and/or inorganic particles, the total mass of the polymer electrolyte is 100%, and the mass percentage of the additive is 0 % To 60%, preferably 5% to 60%.
在更优选的实施例中，所述高分子添加剂包括聚氧化乙烯、聚乳酸、聚己内酯、聚偏氟乙烯、聚丙烯腈、聚甲基丙烯酸甲酯、聚乙烯醇和聚偏氯乙烯中的一种或多种。In a more preferred embodiment, the polymer additives include polyethylene oxide, polylactic acid, polycaprolactone, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, polyvinyl alcohol, and polyvinylidene chloride. One or more.
以所述聚合物电解质的总质量为100％计，所述高分子添加剂的质量百分比为10％～50％。Based on the total mass of the polymer electrolyte being 100%, the mass percentage of the polymer additive is 10%-50%.
所述无机物颗粒包括二氧化硅、二氧化钛、三氧化二铝、氧化锆、氧化镍、氮化硅、氢氧化镁、硅藻土、蒙脱土和高岭土中的一种或多种。The inorganic particles include one or more of silica, titania, alumina, zirconia, nickel oxide, silicon nitride, magnesium hydroxide, diatomaceous earth, montmorillonite, and kaolin.
以所述聚合物电解质的总质量为100％计，所述无机物颗粒的质量百分比为0％～40％。Based on the total mass of the polymer electrolyte being 100%, the mass percentage of the inorganic particles is 0% to 40%.
在一些实施例中，所述聚合物电解质还包括第二溶剂，所述第二溶剂包括乙腈、二甲基亚砜、环丁砜、亚硫酸二甲酯、丙酮、四氢呋喃、三氯甲烷、乙酸乙酯、N,N-二甲基甲酰胺和N,N-二甲基乙酰胺中的一种或多种。In some embodiments, the polymer electrolyte further includes a second solvent, the second solvent includes acetonitrile, dimethyl sulfoxide, sulfolane, dimethyl sulfite, acetone, tetrahydrofuran, chloroform, ethyl acetate , N,N-dimethylformamide and N,N-dimethylacetamide one or more.
所述第二溶剂用于提高第一锂盐和添加剂在所述通式1所示的聚合物中的溶解度，具体操作时，将通式1所示的聚合物溶解于所述第二溶剂中得到聚合物溶液，再将第一锂盐和添加剂加入至聚合物溶液中搅拌至形成均一的混合物。The second solvent is used to increase the solubility of the first lithium salt and the additive in the polymer represented by the general formula 1, in specific operations, the polymer represented by the general formula 1 is dissolved in the second solvent A polymer solution is obtained, and then the first lithium salt and additives are added to the polymer solution and stirred until a uniform mixture is formed.
所述第二溶剂可在后续制备聚合物电解质膜后通过真空干燥去除，或是在将聚合物电解质灌注于软包装电池之前通过真空干燥去除。The second solvent may be removed by vacuum drying after the subsequent preparation of the polymer electrolyte membrane, or by vacuum drying before pouring the polymer electrolyte into the flexible packaging battery.
本发明的另一实施例提供了一种聚合物电解质膜，包括如上所述的聚合物电解质。Another embodiment of the present invention provides a polymer electrolyte membrane including the polymer electrolyte as described above.
在一些实施例中，所述聚合物电解质膜还包括有多孔支撑物，所述多孔支撑物包括玻璃纤维布、无纺布、二氧化硅气凝胶和纤维素膜中的一种或多种。In some embodiments, the polymer electrolyte membrane further includes a porous support including one or more of glass fiber cloth, non-woven cloth, silica aerogel, and cellulose film .
本发明的另一实施例提供了一种非水电解液，包括第三溶剂、第二锂盐和如上所述的通式1所示的聚合物。Another embodiment of the present invention provides a non-aqueous electrolyte, including a third solvent, a second lithium salt, and the polymer represented by Formula 1 as described above.
在一些实施例中，所述第三溶剂为环状碳酸酯和链状碳酸酯的混合物。In some embodiments, the third solvent is a mixture of cyclic carbonate and chain carbonate.
在一些实施例中，所述第二锂盐包括LiPF 6、LiBF 4、LiBOB、LiDFOB、LiN(SO 2CF 3) 2和LiN(SO 2F) 2中的一种或多种。 In some embodiments, the second lithium salt includes one or more of LiPF 6 , LiBF 4 , LiBOB, LiDFOB, LiN(SO 2 CF 3 ) 2 and LiN(SO 2 F) 2 .
本发明的另一实施例提供了一种锂离子电池，包括正极和负极，还包括如上所述的聚合物电解质，或如上所述的聚合物电解质膜，或如上所述的非水电 解液。Another embodiment of the present invention provides a lithium ion battery including a positive electrode and a negative electrode, and further including the polymer electrolyte as described above, or the polymer electrolyte membrane as described above, or the non-aqueous electrolytic solution as described above.
所述正极包括正极活性材料。The positive electrode includes a positive electrode active material.
所述正极活性材料选自LiNi xCo yMn zL (1-x-y-z)O 2、LiCo x’L (1-x’)O 2、LiNi x”L’ y’Mn (2-x”-y’)O 4、Li z’MPO 4中的至少一种，其中，L为Al、Sr、Mg、Ti、Ca、Zr、Zn、Si或Fe中的至少一种，0≤x≤1，0≤y≤1，0≤z≤1，0＜x+y+z≤1，0<x’≤1，0.3≤x”≤0.6，0.01≤y’≤0.2，L’为Co、Al、Sr、Mg、Ti、Ca、Zr、Zn、Si、Fe中的至少一种；0.5≤z’≤1，M为Fe、Mn、Co中的至少一种。 The positive electrode active material is selected from LiNi x Co y Mn z L ( 1-xyz) O 2, LiCo x 'L (1-x') O 2, LiNi x "L 'y' Mn (2-x" -y ') O 4, Li z' MPO 4 at least one, where, L is Al, Sr, Mg, Ti, Ca, Zr, Zn, Si or at least one of Fe, 0≤x≤1, 0≤y≤1, ≤y≤1, 0≤z≤1, 0<x+y+z≤1, 0<x'≤1, 0.3≤x"≤0.6, 0.01≤y'≤0.2, L'is Co, Al, Sr , Mg, Ti, Ca, Zr, Zn, Si, Fe at least one; 0.5≤z'≤1, M is at least one of Fe, Mn, Co.
所述负极包括负极活性材料。The negative electrode includes a negative electrode active material.
所述负极活性材料由碳材料、金属合金、含锂氧化物及含硅材料制得。The negative electrode active material is made of carbon material, metal alloy, lithium-containing oxide and silicon-containing material.
在一些实施例中，所述锂离子电池还包括有隔膜，所述隔膜位于所述正极和负极之间。In some embodiments, the lithium ion battery further includes a separator, and the separator is located between the positive electrode and the negative electrode.
以下通过实施例对本发明进行进一步的说明。The present invention will be further described in the following examples.
实施例1Example 1
本实施例用于说明本发明公开的聚合物电解质及聚合物电解质膜的制备方法，包括以下步骤：This embodiment is used to explain the preparation method of the polymer electrolyte and the polymer electrolyte membrane disclosed in the present invention, including the following steps:
(1)将0.2mol乙二醇二甲基丙烯酸酯(DEG)、0.2mol乙二硫醇(EDT)与0.4mol催化剂三乙胺溶于100mL四氢呋喃中，在氮气气氛保护下于60℃反应6小时；(1) Dissolve 0.2mol ethylene glycol dimethacrylate (DEG), 0.2mol ethanedithiol (EDT) and 0.4mol catalyst triethylamine in 100mL tetrahydrofuran, and react at 60℃ under the protection of nitrogen atmosphere 6 hour;
(2)反应结束后，将步骤(1)中反应混合溶液冷却至室温，减压蒸馏除去溶剂四氢呋喃和催化剂三乙胺，使用甲醇或***洗涤产物3次后，在60℃条件下真空干燥24h得到粘稠液态聚合物DEG-EDT；(2) After the reaction is completed, the reaction mixture solution in step (1) is cooled to room temperature, the solvent tetrahydrofuran and the catalyst triethylamine are distilled off under reduced pressure, the product is washed 3 times with methanol or ether, and dried under vacuum at 60°C for 24h Get viscous liquid polymer DEG-EDT;
(3)将2.0g步骤(2)中得到的液态聚合物DEG-EDT用8mL无水四氢呋喃溶解得到均一的聚合物溶液，然后将0.2g的LiTFSI加入到上述均一的溶液中，在常温下搅拌溶解，得到均匀的聚合物电解质。将聚合物电解质均匀浇注到置于聚四氟乙烯模具中的玻璃纤维布上，在室温下缓慢挥发溶剂后在100℃真空干燥12h，得到聚合物电解质膜。(3) Dissolve 2.0 g of the liquid polymer DEG-EDT obtained in step (2) with 8 mL of anhydrous tetrahydrofuran to obtain a uniform polymer solution, then add 0.2 g of LiTFSI to the above uniform solution and stir at normal temperature Dissolve to obtain a uniform polymer electrolyte. The polymer electrolyte was evenly poured on the glass fiber cloth placed in the polytetrafluoroethylene mold, the solvent was slowly volatilized at room temperature, and then vacuum dried at 100°C for 12 hours to obtain a polymer electrolyte membrane.
实施例2Example 2
本实施例用于说明本发明公开的聚合物电解质及聚合物电解质膜的制备方法，包括以下步骤：This embodiment is used to explain the preparation method of the polymer electrolyte and the polymer electrolyte membrane disclosed in the present invention, including the following steps:
(1)将0.2mol二乙二醇二甲基丙烯酸酯(DED)、0.2mol乙二硫醇(EDT)与0.4mol催化剂偶氮二异丁腈溶于100mL四氢呋喃中，在氮气气氛保护下于30℃反应6小时；(1) Dissolve 0.2 mol of diethylene glycol dimethacrylate (DED), 0.2 mol of ethylene dithiol (EDT) and 0.4 mol of catalyst azobisisobutyronitrile in 100 mL of tetrahydrofuran, under the protection of nitrogen atmosphere at 30 ℃ 6 hours reaction;
(2)反应结束后，将步骤(1)中反应混合溶液冷却至室温，减压蒸馏除去溶剂四氢呋喃，使用甲醇或***洗涤产物3次后，在60℃条件下真空干燥24h得到粘稠液态聚合物DED-EDT；(2) After the reaction, the reaction mixture solution in step (1) was cooled to room temperature, the solvent tetrahydrofuran was distilled off under reduced pressure, the product was washed 3 times with methanol or ether, and dried under vacuum at 60°C for 24 hours to obtain a viscous liquid polymerization物DED-EDT;
(3)将2.0g步骤(2)中得到的液态聚合物DED-EDT用8mL无水四氢呋喃溶解得到均一的聚合物溶液，然后将0.2g的LiTFSI加入到上述均一的溶液中，在常温下搅拌溶解，得到均匀的聚合物电解质。将聚合物电解质均匀浇注到置于聚四氟乙烯模具中的玻璃纤维布上，在室温下缓慢挥发溶剂后在100℃真空干燥12h，得到聚合物电解质膜。(3) Dissolve 2.0 g of the liquid polymer DED-EDT obtained in step (2) with 8 mL of anhydrous tetrahydrofuran to obtain a uniform polymer solution, then add 0.2 g of LiTFSI to the above uniform solution and stir at normal temperature Dissolve to obtain a uniform polymer electrolyte. The polymer electrolyte was evenly poured on the glass fiber cloth placed in the polytetrafluoroethylene mold, the solvent was slowly volatilized at room temperature, and then vacuum dried at 100°C for 12 hours to obtain a polymer electrolyte membrane.
实施例3Example 3
本实施例用于说明本发明公开的聚合物电解质及聚合物电解质膜的制备方法，包括以下步骤：This embodiment is used to explain the preparation method of the polymer electrolyte and the polymer electrolyte membrane disclosed in the present invention, including the following steps:
(1)将0.2mol三乙二醇二甲基丙烯酸酯(TGD)、0.2mol乙二硫醇(EDT)与0.4mol催化剂三乙胺混合后搅拌，在氮气气氛保护下于50℃反应6小时；(1) Mix 0.2 mol of triethylene glycol dimethacrylate (TGD), 0.2 mol of ethylene dithiol (EDT) with 0.4 mol of catalyst triethylamine, stir, and react at 50°C for 6 hours under a nitrogen atmosphere ;
(2)反应结束后，将步骤(1)中反应混合溶液冷却至室温，减压蒸馏除去催化剂三乙胺，使用甲醇或***洗涤产物3次后，在60℃条件下真空干燥24h得到粘稠液态聚合物TGD-EDT；(2) After the reaction, the reaction mixture solution in step (1) was cooled to room temperature, the catalyst triethylamine was distilled off under reduced pressure, the product was washed 3 times with methanol or ether, and dried under vacuum at 60°C for 24 hours to obtain a thick Liquid polymer TGD-EDT;
(3)将2.0g步骤(2)中得到的液态聚合物TGD-EDT用8mL无水四氢呋喃溶解得到均一的聚合物溶液，然后将0.2g的LiTFSI加入到上述均一的溶液中，在常温下搅拌溶解，得到均匀的聚合物电解质。将聚合物电解质均匀浇注到置于聚四氟乙烯模具中的玻璃纤维布上，在室温下缓慢挥发溶剂后在100℃真空干燥12h，得到聚合物电解质膜。(3) Dissolve 2.0 g of the liquid polymer TGD-EDT obtained in step (2) with 8 mL of anhydrous tetrahydrofuran to obtain a uniform polymer solution, then add 0.2 g of LiTFSI to the above uniform solution and stir at normal temperature Dissolve to obtain a uniform polymer electrolyte. The polymer electrolyte was evenly poured on the glass fiber cloth placed in the polytetrafluoroethylene mold, the solvent was slowly volatilized at room temperature, and then vacuum dried at 100°C for 12 hours to obtain a polymer electrolyte membrane.
实施例4Example 4
本实施例用于说明本发明公开的聚合物电解质及聚合物电解质膜的制备方法，包括以下步骤：This embodiment is used to explain the preparation method of the polymer electrolyte and the polymer electrolyte membrane disclosed in the present invention, including the following steps:
(1)将0.2mol四乙二醇二甲基丙烯酸酯(TeED)、0.2mol乙二硫醇(EDT)与0.4mol催化剂三乙胺混合后搅拌，在氮气气氛保护下于80℃反应6小时；(1) Mix 0.2 mol of tetraethylene glycol dimethacrylate (TeED), 0.2 mol of ethylene dithiol (EDT) with 0.4 mol of catalyst triethylamine, stir, and react at 80°C for 6 hours under the protection of nitrogen atmosphere ;
(2)反应结束后，将步骤(1)中反应混合溶液冷却至室温，减压蒸馏除去催化剂三乙胺，使用甲醇或***洗涤产物3次后，在60℃条件下真空干燥24h得到粘稠液态聚合物TeED-EDT；(2) After the reaction, the reaction mixture solution in step (1) was cooled to room temperature, the catalyst triethylamine was distilled off under reduced pressure, the product was washed 3 times with methanol or ether, and dried under vacuum at 60°C for 24 hours to obtain a thick Liquid polymer TeED-EDT;
(3)将2.0g步骤(2)中得到的液态聚合物TeED-EDT用8mL无水四氢呋喃溶解得到均一的聚合物溶液，然后将0.2g的LiFSI加入到上述均一的溶液中，在常温下搅拌溶解，得到均匀的聚合物电解质。将聚合物电解质均匀浇注到置于聚四氟乙烯模具中的玻璃纤维布上，在室温下缓慢挥发溶剂后在100℃真空干燥12h，得到聚合物电解质膜。(3) Dissolve 2.0 g of the liquid polymer TeED-EDT obtained in step (2) with 8 mL of anhydrous tetrahydrofuran to obtain a uniform polymer solution, then add 0.2 g of LiFSI to the above uniform solution and stir at normal temperature Dissolve to obtain a uniform polymer electrolyte. The polymer electrolyte was evenly poured on the glass fiber cloth placed in the polytetrafluoroethylene mold, the solvent was slowly volatilized at room temperature, and then vacuum dried at 100°C for 12 hours to obtain a polymer electrolyte membrane.
实施例5Example 5
本实施例用于说明本发明公开的聚合物电解质及聚合物电解质膜的制备方法，包括以下步骤：This embodiment is used to explain the preparation method of the polymer electrolyte and the polymer electrolyte membrane disclosed in the present invention, including the following steps:
(1)将0.2mol二甲基丙烯酸1,4-丁二醇酯(BDMA)、0.2mol双(3-巯基丙酸)乙二醇(EGB)与0.4mol催化剂三乙胺混合后搅拌，在氮气气氛保护下于60℃反应6小时；(1) Mix 0.2mol 1,4-butanediol dimethacrylate (BDMA), 0.2mol bis(3-mercaptopropionic acid) ethylene glycol (EGB) with 0.4mol catalyst triethylamine and stir, Under the protection of nitrogen atmosphere, react at 60℃ for 6 hours;
(2)反应结束后，将步骤(1)中反应混合溶液冷却至室温，减压蒸馏除去催化剂三乙胺，使用甲醇或***洗涤产物3次后，在60℃条件下真空干燥24h得到粘稠液态聚合物BDMA-EGB；(2) After the reaction, the reaction mixture solution in step (1) was cooled to room temperature, the catalyst triethylamine was distilled off under reduced pressure, the product was washed 3 times with methanol or ether, and dried under vacuum at 60°C for 24 hours to obtain a thick Liquid polymer BDMA-EGB;
(3)将2.0g步骤(2)中得到的液态聚合物BDMA-EGB用8mL无水四氢呋喃溶解得到均一的聚合物溶液，然后将0.2g的LiTFSI加入到上述均一的溶液中，在常温下搅拌溶解，得到均匀的聚合物电解质。将聚合物电解质均匀浇注到置于聚四氟乙烯模具中的玻璃纤维布上，在室温下缓慢挥发溶剂后在100℃真空干燥12h，得到聚合物电解质膜。(3) Dissolve 2.0 g of the liquid polymer BDMA-EGB obtained in step (2) with 8 mL of anhydrous tetrahydrofuran to obtain a uniform polymer solution, then add 0.2 g of LiTFSI to the above uniform solution and stir at normal temperature Dissolve to obtain a uniform polymer electrolyte. The polymer electrolyte was evenly poured on the glass fiber cloth placed in the polytetrafluoroethylene mold, the solvent was slowly volatilized at room temperature, and then vacuum dried at 100°C for 12 hours to obtain a polymer electrolyte membrane.
实施例6Example 6
本实施例用于说明本发明公开的聚合物电解质及聚合物电解质膜的制备方法，包括以下步骤：This embodiment is used to explain the preparation method of the polymer electrolyte and the polymer electrolyte membrane disclosed in the present invention, including the following steps:
(1)将0.2mol三乙二醇二甲基丙烯酸酯(TGD)、0.2mol双(3-巯基丙酸)乙二醇(EGB)与0.4mol催化剂偶氮二异丁腈(AIBN)混合后搅拌，在氮气气氛保护下于70℃反应6小时；(1) After mixing 0.2mol triethylene glycol dimethacrylate (TGD), 0.2mol bis(3-mercaptopropionic acid) ethylene glycol (EGB) and 0.4mol catalyst azobisisobutyronitrile (AIBN) Stir and react at 70°C for 6 hours under a nitrogen atmosphere;
(2)反应结束后，将步骤(1)中反应混合溶液冷却至室温，减压蒸馏除 去催化剂三乙胺，使用甲醇或***洗涤产物3次后，在60℃条件下真空干燥24h得到粘稠液态聚合物TGD-EGB；(2) After the reaction, the reaction mixture solution in step (1) was cooled to room temperature, the catalyst triethylamine was distilled off under reduced pressure, the product was washed 3 times with methanol or ether, and dried under vacuum at 60°C for 24 hours to obtain a thick Liquid polymer TGD-EGB;
(3)将2.0g步骤(2)中得到的液态聚合物TGD-EGB用8mL无水四氢呋喃溶解得到均一的聚合物溶液，然后将0.2g的LiTFSI加入到上述均一的溶液中，在常温下搅拌溶解，得到均匀的聚合物电解质。将聚合物电解质均匀浇注到置于聚四氟乙烯模具中的玻璃纤维布上，在室温下缓慢挥发溶剂后在100℃真空干燥12h，得到聚合物电解质膜。(3) Dissolve 2.0g of the liquid polymer TGD-EGB obtained in step (2) with 8mL of anhydrous tetrahydrofuran to obtain a uniform polymer solution, then add 0.2g of LiTFSI to the above uniform solution and stir at normal temperature Dissolve to obtain a uniform polymer electrolyte. The polymer electrolyte was evenly cast on the glass fiber cloth placed in the polytetrafluoroethylene mold, the solvent was slowly volatilized at room temperature, and then vacuum dried at 100°C for 12 hours to obtain a polymer electrolyte membrane.
对比例1Comparative Example 1
本对比例用于对比例说明本发明公开的聚合物电解质及聚合物电解质膜的制备方法，包括：This comparative example is used to illustrate the preparation method of the polymer electrolyte and polymer electrolyte membrane disclosed in the present invention, including:
采用常规的PEO制作聚合物电解质及聚合物电解质膜。Use conventional PEO to make polymer electrolyte and polymer electrolyte membrane.
性能测试Performance Testing
对实施例1制备得到的液态聚合物DEG-EDT进行核磁共振测试，得到如图1所示的核磁共振谱图。The liquid polymer DEG-EDT prepared in Example 1 was subjected to a nuclear magnetic resonance test to obtain the nuclear magnetic resonance spectrum shown in FIG. 1.
由图1可知，合成的聚合物核磁共振谱图符合预期，可证明合成出正确的目标产物。It can be seen from Figure 1 that the synthesized polymer NMR spectrum is as expected, which can prove that the correct target product is synthesized.
对实施例1制备得到的聚合物电解质在60℃条件下进行线性伏安扫描曲线测试，得到如图2所示的线性伏安扫描曲线。The polymer electrolyte prepared in Example 1 was subjected to a linear voltammetry curve test at 60°C to obtain a linear voltammetry curve as shown in FIG. 2.
由图2可知，聚合物电解质可以耐受5.2伏以上的电压。It can be seen from FIG. 2 that the polymer electrolyte can withstand a voltage of 5.2 volts or more.
将实施例1制备得到的聚合物电解质膜、正极磷酸铁锂、负极锂金属组装得到磷酸铁锂/锂金属电池，在60℃条件下进行电池循环测试，得到如图3所示的循环曲线。The polymer electrolyte membrane prepared in Example 1, the positive electrode lithium iron phosphate, and the negative electrode lithium metal were assembled to obtain a lithium iron phosphate/lithium metal battery, and the battery cycle test was performed at 60°C to obtain the cycle curve shown in FIG. 3.
上述磷酸铁锂/锂金属电池的制备过程为：将PVDF溶解于NMP中，得到浓度为0.1mol/L的聚合物溶液，按照正极活性物质、导电炭黑和PVDF(即上述溶液中溶质)以8：1：1的质量比混合后研磨均匀。将上述混合浆料均匀地涂敷在铝箔上，厚度为100-200μm，先于60℃下烘干，再于120℃真空烘箱中烘干，辊压，冲片，称重后继续在120℃真空烘箱中烘干，放置于手套箱中，得到正极；使用锂金属片作为负极，实施例1提供的聚合物电解质膜来组装电池。The preparation process of the above lithium iron phosphate/lithium metal battery is: dissolving PVDF in NMP to obtain a polymer solution with a concentration of 0.1mol/L, according to the positive electrode active material, conductive carbon black and PVDF (that is, the solute in the above solution) to The mass ratio of 8:1:1 is milled evenly after mixing. The above mixed slurry is evenly coated on aluminum foil, with a thickness of 100-200 μm, dried at 60°C, then dried in a vacuum oven at 120°C, rolled, punched, weighed, and then continued at 120°C It was dried in a vacuum oven and placed in a glove box to obtain a positive electrode; a lithium metal sheet was used as the negative electrode, and the polymer electrolyte membrane provided in Example 1 was used to assemble the battery.
由图3可知，在60℃条件下，采用聚合物电解质DEG-EDT组装的磷酸铁锂/锂金属电池的循环稳定性良好，循环450圈后其容量仍为初始值的90％以上。It can be seen from FIG. 3 that at 60° C., the lithium iron phosphate/lithium metal battery assembled with the polymer electrolyte DEG-EDT has good cycle stability, and its capacity is still more than 90% of the initial value after 450 cycles.
对上述实施例1～6及对比例1制备得到的聚合物电解质膜进行如下性能测试：The polymer electrolyte membranes prepared in the above Examples 1 to 6 and Comparative Example 1 were subjected to the following performance tests:
膜厚度：采用千分尺(精度0.01mm)测试聚合物电解质膜厚度，压实后的聚合物电解质膜样品上任意取5个点并取平均值。Membrane thickness: A micrometer (accuracy of 0.01mm) is used to test the thickness of the polymer electrolyte membrane. After compressing the sample of the polymer electrolyte membrane, randomly take 5 points and take the average.
离子电导率：用两片不锈钢夹住聚合物电解质膜，放在2025型电池壳中，锂离子电导率采用电化学交流阻谱来测量，采用公式：σ＝L/AR b，其中L为聚合物电解质膜的膜厚度，A为不锈钢片面积，R b为阻抗仪测量得出的阻抗。 Ionic conductivity: sandwich the polymer electrolyte membrane with two pieces of stainless steel and place it in a 2025 type battery case. The lithium ion conductivity is measured by electrochemical AC resistance spectroscopy, using the formula: σ=L/AR b , where L is polymerization Thickness of the electrolyte membrane, A is the area of the stainless steel sheet, R b is the impedance measured by the impedance meter.
电化学窗口：以不锈钢片和锂片夹住聚合物电解质膜，放在2025型电池壳中，电化学工作窗口以电化学工作站进行线性伏安扫描测量，起始电位为2.5V，最高电位为7V，扫描速度为1mV/s。Electrochemical window: The polymer electrolyte membrane is sandwiched between a stainless steel sheet and a lithium sheet, and placed in a 2025 battery case. The electrochemical working window is measured by a linear voltammetry at an electrochemical workstation. The initial potential is 2.5V and the highest potential is 7V, scanning speed is 1mV/s.
玻璃化转变温度(T g)与熔融温度(T m)的检测：采用差示扫描量热仪(DSC)检测纯聚合物的玻璃化温度，放置聚合物于铝制坩埚中并放入DSC的检测炉体中，DSC加热速率采用20℃/min，起始温度为-80℃，最高温度为100℃。 Detection of glass transition temperature (T g ) and melting temperature (T m ): the differential scanning calorimeter (DSC) is used to detect the glass transition temperature of pure polymer. The polymer is placed in an aluminum crucible and placed in DSC In the detection furnace, the DSC heating rate is 20℃/min, the initial temperature is -80℃, and the maximum temperature is 100℃.
锂离子迁移数测试：用两片锂片夹住聚合物电解质膜制作无阻塞电池的对称电池，锂离子迁移数采用稳态电流法来测量，采用公式：t Li+＝I s(ΔV-I sR s)/I 0(ΔV-I 0R 0)，式中，I 0为初始电流，即极化前的电流，I s称为稳态电流，即极化后的电流，R 0和R s分别是指极化前后的阻抗，可由交流阻抗法测得；ΔV是指极化电压。 Lithium ion migration number test: using two lithium sheets to sandwich a polymer electrolyte membrane to make a non-blocking symmetric battery. The lithium ion migration number is measured by the steady-state current method, using the formula: t Li+ =I s (ΔV-I s R s )/I 0 (ΔV-I 0 R 0 ), where I 0 is the initial current, that is, the current before polarization, I s is called the steady-state current, that is, the current after polarization, R 0 and R s refers to the impedance before and after polarization, respectively, which can be measured by the AC impedance method; ΔV refers to the polarization voltage.
由于本发明提供的通式1所示的化合物为非结晶性聚合物，无熔融温度。Since the compound represented by Formula 1 provided by the present invention is an amorphous polymer, it has no melting temperature.
得到的测试结果填入表1。The obtained test results are filled in Table 1.
表1Table 1
Figure PCTCN2019124768-appb-000004
Figure PCTCN2019124768-appb-000004
从表1的测试结果可以看出，本发明提供的聚合物具有较高的离子电导率以及较宽的电化学窗口，能够有效地作为一种锂离子电池的聚合物电解质使用，有效解决传统固态聚合物电解质稳定性差和离子电导率低的问题。并且，通式1和通式2所示的化合物为非结晶性聚合物，玻璃化转变温度较低，可有效解决传统固态聚合物电解质加工性能差的问题。It can be seen from the test results in Table 1 that the polymer provided by the present invention has a higher ionic conductivity and a wider electrochemical window, and can be effectively used as a polymer electrolyte of a lithium ion battery, effectively solving the traditional solid state The problems of poor stability of polymer electrolytes and low ionic conductivity. In addition, the compounds represented by Formula 1 and Formula 2 are non-crystalline polymers with a low glass transition temperature, which can effectively solve the problem of poor processing performance of traditional solid polymer electrolytes.
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modification, equivalent replacement and improvement made within the spirit and principle of the present invention should be included in the protection of the present invention Within range.

Claims (11)

  1. 如下通式1所示的聚合物，其特征在于，The polymer represented by the following general formula 1 is characterized in that
    Figure PCTCN2019124768-appb-100001
    Figure PCTCN2019124768-appb-100001
    其中，R 1为碳原子数为1-5的烃基或氢；R 2为碳原子数为1-5的烃基或氢；R 3为-(CH 2) n-或-(CH 2CH 2O) n-或-(CF 2CF 2O) n-，其中n取值为1-100；R 4为-(CH 2) m-或-(CH 2CH 2O) m-或-(CF 2CF 2O) m-，其中m取值为1-100；p取值为1-500。 Wherein, R 1 is a hydrocarbon group having 1 to 5 carbon atoms or hydrogen; R 2 is a hydrocarbon group having 1 to 5 carbon atoms or hydrogen; R 3 is -(CH 2 ) n -or -(CH 2 CH 2 O ) n -or-(CF 2 CF 2 O) n -, where n is 1-100; R 4 is -(CH 2 ) m -or-(CH 2 CH 2 O) m -or-(CF 2 CF 2 O) m -, where m takes a value of 1-100; p takes a value of 1-500.
  2. 根据权利要求1所述的聚合物，其特征在于，所述聚合物为非结晶性液态聚合物，其玻璃化转变温度为-39℃以下。The polymer according to claim 1, wherein the polymer is an amorphous liquid polymer, and its glass transition temperature is -39°C or lower.
  3. 根据权利要求1所述的聚合物，其特征在于，所述R 1为甲基、乙基、丙基或氢；R 2为甲基、乙基、丙基或氢；所述R 3为甲基、乙基、丙基或氢；R 4为甲基、乙基、丙基或氢。 The polymer according to claim 1, wherein R 1 is methyl, ethyl, propyl or hydrogen; R 2 is methyl, ethyl, propyl or hydrogen; and R 3 is methyl Radical, ethyl, propyl or hydrogen; R 4 is methyl, ethyl, propyl or hydrogen.
  4. 一种聚合物电解质，其特征在于，包括第一锂盐以及如权利要求1～3任意一项所述的聚合物。A polymer electrolyte characterized by comprising a first lithium salt and the polymer according to any one of claims 1 to 3.
  5. 根据权利要求4所述的聚合物电解质，其特征在于，以所述聚合物电解质的总质量为100％计，所述聚合物的质量百分比为20％～95％。The polymer electrolyte according to claim 4, wherein the mass percentage of the polymer is 20% to 95% based on the total mass of the polymer electrolyte being 100%.
  6. 根据权利要求4所述的聚合物电解质，其特征在于，所述聚合物电解质在25℃下的离子电导率为1×10 -5-6×10 -5S/cm，60℃下的离子电导率为2×10 -4-6×10 -4S/cm，60℃下的锂离子迁移数大于0.36，电化学窗口为5.1V以上。 The polymer electrolyte according to claim 4, wherein the ion conductivity of the polymer electrolyte at 25°C is 1×10 -5 -6×10 -5 S/cm, and the ion conductivity at 60°C The rate is 2×10 -4 -6×10 -4 S/cm, the migration number of lithium ions at 60°C is greater than 0.36, and the electrochemical window is above 5.1V.
  7. 根据权利要求4所述的聚合物电解质，其特征在于，所述第一锂盐包括高氯酸锂、六氟磷酸锂、二草酸硼酸锂、六氟砷酸锂、四氟硼酸锂、三氟甲基磺酸锂和双氟甲烷黄酰亚胺锂中的一种或多种；The polymer electrolyte according to claim 4, wherein the first lithium salt comprises lithium perchlorate, lithium hexafluorophosphate, lithium dioxalate borate, lithium hexafluoroarsenate, lithium tetrafluoroborate, trifluoromethanesulfonate One or more of lithium acid lithium and lithium difluoromethane xanthimide;
    以所述聚合物电解质的总质量为100％计，所述第一锂盐的质量百分比为5％～80％。Based on the total mass of the polymer electrolyte being 100%, the mass percentage of the first lithium salt is 5% to 80%.
  8. 根据权利要求4所述的聚合物电解质，其特征在于，所述聚合物电解质还包括添加剂，所述添加剂包括高分子添加剂和/或无机颗粒，以所述聚合物电解质的总质量为100％计，所述添加剂的质量百分比为0％～60％；The polymer electrolyte according to claim 4, characterized in that the polymer electrolyte further comprises additives, and the additives include polymer additives and/or inorganic particles, based on the total mass of the polymer electrolyte being 100% , The mass percentage of the additive is 0% to 60%;
    所述高分子添加剂包括聚氧化乙烯、聚乳酸、聚己内酯、聚偏氟乙烯、聚丙烯腈、聚甲基丙烯酸甲酯、聚乙烯醇和聚偏氯乙烯中的一种或多种；The polymer additive includes one or more of polyethylene oxide, polylactic acid, polycaprolactone, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, polyvinyl alcohol, and polyvinylidene chloride;
    所述无机物颗粒包括二氧化硅、二氧化钛、三氧化二铝、氧化锆、氧化镍、氮化硅、氢氧化镁、硅藻土、蒙脱土和高岭土中的一种或多种。The inorganic particles include one or more of silica, titania, alumina, zirconia, nickel oxide, silicon nitride, magnesium hydroxide, diatomaceous earth, montmorillonite, and kaolin.
  9. 一种聚合物电解质膜，其特征在于，包括如权利要求4～8任意一项所述的聚合物电解质。A polymer electrolyte membrane, characterized by comprising the polymer electrolyte according to any one of claims 4 to 8.
  10. 一种非水电解液，其特征在于，包括如权利要求1～3任意一项所述的聚合物。A non-aqueous electrolyte, characterized by comprising the polymer according to any one of claims 1 to 3.
  11. 一种锂离子电池，包括正极和负极，其特征在于，还包括如权利要求4～8任意一项所述的聚合物电解质，或如权利要求9所述的聚合物电解质膜，或权利要求10所述的非水电解液。A lithium ion battery, comprising a positive electrode and a negative electrode, characterized in that it further comprises the polymer electrolyte according to any one of claims 4 to 8, or the polymer electrolyte membrane according to claim 9, or claim 10. The non-aqueous electrolyte.
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