WO2021175122A1 - 复合聚合物及其制备方法和应用 - Google Patents

复合聚合物及其制备方法和应用 Download PDF

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WO2021175122A1
WO2021175122A1 PCT/CN2021/077191 CN2021077191W WO2021175122A1 WO 2021175122 A1 WO2021175122 A1 WO 2021175122A1 CN 2021077191 W CN2021077191 W CN 2021077191W WO 2021175122 A1 WO2021175122 A1 WO 2021175122A1
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Prior art keywords
positive electrode
composite polymer
electrode slurry
polymer
performance
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English (en)
French (fr)
Inventor
李小栓
吕文彬
魏礼勇
徐赛
邓素祥
马忠龙
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Svolt Energy Technology Co Ltd
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Svolt Energy Technology Co Ltd
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Priority to EP21764485.5A priority Critical patent/EP4116355A4/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
    • B60L50/00—Electric propulsion with power supplied within the vehicle
    • B60L50/50—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells
    • B60L50/60—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells using power supplied by batteries
    • B60L50/64—Constructional details of batteries specially adapted for electric vehicles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/36—Furfuryl alcohol
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C09J171/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C09J171/14—Furfuryl alcohol polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the present disclosure relates to the technical field of lithium batteries and their applications, for example, to composite polymers and their preparation methods and applications.
  • Lithium-ion battery At present, most lithium-ion power battery cathodes use lithium iron phosphate and ternary materials. With the continuous improvement of energy density requirements, it is more and more difficult to continue to increase the energy density on the existing battery cell design system, especially for high-endurance electric vehicles. .
  • the present disclosure provides a composite polymer and its preparation method and application.
  • a composite polymer is provided, and the composite polymer is a block copolymer of polyfurfuryl alcohol and polyethylene oxide.
  • the binder commonly used in the positive electrode is polyvinylidene fluoride (PVDF), and there are three main interactions between the binder PVDF in the electrode: binder and active material particles The interaction between the binder and the current collector, the interaction between the binder molecule and the binder molecule.
  • the viscosity of the binder is an important process parameter. If the viscosity of the binder is too small, the viscosity of the prepared slurry will also be small, resulting in excessive fluidity of the slurry and prone to sedimentation, and poor storage stability.
  • the binder has no conductive effect, which increases the internal resistance of the battery and affects the performance of the battery.
  • the active material content and the binder content are often increased in the design of the battery cell system.
  • reducing the amount of binder will affect the homogenization process, reduce the stability of the slurry, and reduce the peel strength of the prepared pole piece, which makes the coating easy to peel from the current collector, which affects the performance of the electrical performance and is safe for the battery. Sex has a lot of hidden dangers.
  • the composite polymer is a chain polymer, a star polymer, or a dendritic polymer.
  • the average molecular weight of the composite polymer is 45,000-55,000, such as 46,000, 48,000, 50,000, 52,000, 54,000, and so on.
  • the solid content of the composite polymer is 1.2 wt% to 18 wt%, for example, 2 wt%, 4 wt%, 6 wt%, 8 wt%, 10 wt%, 12 wt%, 14 wt%, 16 wt%, etc.
  • the present disclosure provides a method for preparing the composite polymer in an embodiment, and the method includes the following steps:
  • the initiator, solvent, polyethylene oxide and furfuryl alcohol are mixed and stirred to obtain a composite polymer.
  • the furfuryl alcohol under the action of an initiator and a solvent, the furfuryl alcohol can be polymerized, and the polymerized furfuryl alcohol can be reacted with polyethylene oxide to obtain a block polymer of polyfurfuryl alcohol and polyethylene oxide.
  • the composite polymer contains structural parts similar to the binder, it is easier to fully mix with the positive electrode active material to form a uniform phase and improve the adhesion and peeling force of the pole piece. Furthermore, the composite polymer can quickly gelatinize after adding electrolyte, promote the transmission of electrons and ions inside the pole piece, and at the same time can avoid the existence of too much electrolyte inside the cell, thereby improving the safety performance of the battery.
  • the initiator is selected from at least one of oxalic acid and hydrochloric acid.
  • the initiator may be oxalic acid, hydrochloric acid, or a mixture of oxalic acid and hydrochloric acid.
  • the initiator is selected from oxalic acid.
  • the solvent is selected from at least one of N-methylpyrrolidone (NMP) and dimethyl sulfoxide.
  • NMP N-methylpyrrolidone
  • the solvent may be N-methylpyrrolidone or dimethyl sulfoxide, It can also be a mixture of N-methylpyrrolidone and dimethyl sulfoxide.
  • the mass ratio of the initiator to the solvent is (2-4): (90-98), where 2-4 can be 2.5, 3.0, 3.5, etc., and 90-98 can be 91 , 92, 93, 94, 95, 96, 97, etc.
  • a positive electrode slurry is provided.
  • the positive electrode slurry is composed of a positive electrode active material and a glue solution.
  • the glue solution is the composite polymer described in an embodiment of the disclosure or adopts the first
  • the resulting composite polymer was prepared by the method described in the examples.
  • the positive electrode slurry provided by one embodiment of the present disclosure has the above-mentioned composite polymer, which has the binding properties of a binder and can improve its compatibility with the positive electrode active material, so that the positive electrode active material is uniform. Dispersed in the pole piece, it improves the adhesion and peeling force of the pole piece, and improves the rate cycle performance of the battery. At the same time, it also has the properties of electrical conductivity and ion conduction. It can be used as a carrier for lithium ion transmission and assumes the role of the solvent in the electrolyte. Promote the transmission of lithium ions in the pole piece and improve the rate performance of the battery.
  • the positive electrode slurry does not need to add additional binders and conductive agents, and the reduction of material components in the slurry is also conducive to improving the consistency of the slurry, thereby improving the quality of the battery.
  • the composite polymer can also improve the mechanical properties of the pole piece, endow the pole piece with flexibility, can effectively alleviate the volume expansion of the pole piece during the charge and discharge process, maintain the stability of the electrode, and further improve the lithium ion in the pole piece.
  • the transmission speed is improved, and the magnification performance is improved.
  • the solid content of the positive electrode slurry is 50 wt% to 80 wt%, such as 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, and so on.
  • the viscosity of the positive electrode slurry is 3000-20000 cP, such as 4000 cP, 8000 cP, 12000 cP, 16000 cP, etc.
  • the positive active material is selected from at least one of nickel cobalt manganese (NCM) and lithium nickel cobalt aluminate (NCA).
  • NCM nickel cobalt manganese
  • NCA lithium nickel cobalt aluminate
  • the positive active material can be NCM, NCA, or A mixture of NCM and NCA.
  • a lithium battery is provided, and the lithium battery has a positive electrode sheet prepared from the positive electrode slurry described in an embodiment of the present disclosure.
  • a lithium battery provided by an embodiment of the present disclosure has a positive electrode sheet prepared from a positive electrode slurry composed of a positive electrode active material and the above-mentioned composite polymer, and because it has the above-mentioned composite polymer, the composite polymer has both a binder
  • the bonding performance of the battery can improve its compatibility with the positive electrode active material, so that the positive electrode active material is evenly dispersed in the electrode piece, improving the adhesion and peeling force of the electrode piece, improving the battery's rate cycle performance, and also having electrical conductivity It can be used as a carrier for lithium ion transmission, taking on the role of the solvent in the electrolyte to promote the transmission of lithium ions in the pole piece and improve the rate performance of the battery.
  • the composite polymer can also improve the mechanical properties of the pole piece, endow the pole piece with flexibility, can effectively alleviate the volume expansion of the pole piece during the charge and discharge process, maintain the stability of the electrode, and further improve the lithium ion in the pole piece.
  • the transmission speed is improved, and the magnification performance is improved.
  • a car is provided, and the car has the lithium battery described in an embodiment of the present disclosure.
  • the automobile provided by an embodiment of the present disclosure has the above-mentioned lithium battery, and because the lithium battery has a positive electrode sheet prepared from the above-mentioned positive electrode slurry, the lithium battery has better cycle performance and rate performance, and safety performance And the consistency is better. As a result, it is beneficial to improve the endurance and safety performance of the car.
  • FIG. 1 is an SEM image of the coating layer of the positive electrode sheet obtained in the embodiment
  • Figure 3 is a test curve of the cycle performance of the positive electrode sheet obtained in the embodiment and the comparative example at 0.5C;
  • Fig. 5 is an SEM image of the coating layer of the positive electrode sheet obtained in the comparative example.
  • the present disclosure proposes a composite polymer.
  • the composite polymer is a block copolymer of polyfurfuryl alcohol and polyethylene oxide.
  • the composite polymer contains structural parts similar to the binder, it is easier to fully mix with the positive electrode active material to form a uniform phase and improve the adhesion and peeling force of the pole piece.
  • the composite polymer can quickly gelatinize after adding electrolyte, promote the transmission of electrons and ions inside the pole piece, and at the same time can avoid the existence of too much electrolyte inside the cell, thereby improving the safety performance of the battery.
  • the composite polymer may be a chain polymer or a star polymer or a dendritic polymer, which can be selected by those skilled in the art according to needs and preparation processes.
  • the average molecular weight of the composite polymer is not particularly limited, and those skilled in the art can choose according to actual needs, for example, it can be 45,000-55,000, and the average molecular weight of an embodiment of the present disclosure is 50,000.
  • the viscosity of the composite polymer can be increased by increasing the reaction temperature, for example, the reaction temperature can be increased.
  • the solid content of the composite polymer is not particularly limited, for example, it can be 1.2 wt% to 18 wt%, and increasing the solid content can increase the viscosity of the polymer slurry.
  • the present disclosure proposes a method for preparing a composite polymer.
  • the method includes: mixing and stirring an initiator, a solvent, polyethylene oxide, and furfuryl alcohol to obtain a composite polymer Things.
  • the furfuryl alcohol can be polymerized, and the polymerized furfuryl alcohol can react with polyethylene oxide to obtain a block polymer of polyfurfuryl alcohol and polyethylene oxide.
  • the initiator and the solvent can be mixed and stirred first, and then the polyethylene oxide and furfuryl alcohol can be added and stirred and mixed to react, so as to obtain the composite polymer.
  • the specific types of initiator and solvent are not particularly limited, and those skilled in the art can select according to actual needs.
  • the initiator can be selected from at least one of oxalic acid and hydrochloric acid, and can be selected from Oxalic acid;
  • the solvent can be selected from at least one of N-methylpyrrolidone and dimethyl sulfoxide.
  • the use of the above-mentioned initiators and solvents is beneficial to reduce the cost, and at the same time makes the reaction rate easy to control.
  • the mass ratio of the initiator and the solvent is not particularly limited. For example, it can be 2-4:90-98. In an embodiment of the present disclosure, the mass ratio of the initiator and the solvent is 1:30. Too high a ratio will increase the viscosity of the slurry.
  • the furfuryl alcohol under the action of the initiator and the solvent, the furfuryl alcohol can be polymerized, and the polymerized furfuryl alcohol can be reacted with polyethylene oxide to obtain a block polymer of polyfurfuryl alcohol and polyethylene oxide.
  • the composite polymer contains structural parts similar to the binder, it is easier to fully mix with the positive electrode active material to form a uniform phase and improve the adhesion and peeling force of the pole piece. Furthermore, the composite polymer can quickly gelatinize after adding electrolyte, promote the transmission of electrons and ions inside the pole piece, and at the same time can avoid the existence of too much electrolyte inside the cell, thereby improving the safety performance of the battery.
  • the present disclosure proposes a positive electrode slurry.
  • the positive electrode slurry is composed of a positive electrode active material and a glue solution.
  • the glue solution is the above-mentioned composite polymer or the above-mentioned preparation composite.
  • the polymer method prepares the resulting composite polymer. Because it has the above-mentioned composite polymer, the composite polymer not only has the binding properties of the binder, and can improve its compatibility with the positive electrode active material, so that the positive electrode active material is uniformly dispersed in the pole piece, and the stickiness of the pole piece is improved.
  • the junction force and peeling force improve the rate cycle performance of the battery, and it also has the performance of electrical conductivity and ion conduction.
  • the positive electrode slurry does not need to add additional binders and conductive agents, and the reduction of material components in the slurry is also conducive to improving the consistency of the slurry, thereby improving the quality of the battery.
  • the composite polymer can also improve the mechanical properties of the pole piece, endow the pole piece with flexibility, can effectively alleviate the volume expansion of the pole piece during the charge and discharge process, maintain the stability of the electrode, and further improve the lithium ion in the pole piece.
  • the transmission speed is improved, and the magnification performance is improved.
  • the solid content and viscosity of the positive electrode slurry are not particularly limited, and those skilled in the art can choose according to actual needs.
  • the solid content can be 50wt%-80wt%, and the viscosity can be 3000-20000 cP. Too high solid content and viscosity of the slurry will reduce the consistency of the slurry.
  • the specific type of the positive electrode active material is not particularly limited, for example, it may be at least one of NCM and NCA.
  • the composite polymer not only has the binding properties of the binder, and can improve its compatibility with the positive electrode active material, so that the positive electrode active material can be uniformly dispersed.
  • the composite polymer improves the adhesion and peeling force of the pole piece, and improves the rate cycle performance of the battery.
  • it also has the properties of electrical conductivity and ion conduction. It can be used as a carrier for lithium ion transmission and assumes the role of the solvent in the electrolyte. The transmission of lithium ions in the pole piece improves the rate performance of the battery.
  • the positive electrode slurry does not need to add additional binders and conductive agents, and the reduction of the material components in the slurry is also conducive to improving the consistency of the slurry, thereby improving the quality of the battery.
  • the composite polymer can also improve the mechanical properties of the pole piece, endow the pole piece with flexibility, can effectively alleviate the volume expansion of the pole piece during the charge and discharge process, maintain the stability of the electrode, and further improve the lithium ion in the pole piece.
  • the transmission speed is improved, and the magnification performance is improved.
  • the present disclosure proposes a lithium battery.
  • the lithium battery has a positive electrode sheet prepared from the above-mentioned positive electrode slurry.
  • the lithium battery has a positive electrode sheet prepared from a positive electrode slurry composed of a positive electrode active material and the above-mentioned composite polymer.
  • the binding performance can improve its compatibility with the positive electrode active material, so that the positive electrode active material is evenly dispersed in the electrode piece, improving the adhesion and peeling force of the electrode piece, improving the battery's rate cycle performance, and it also has conductivity and
  • the ion-conducting performance can be used as a carrier for lithium ion transmission, taking on the role of the solvent in the electrolyte and synergistically promoting the transmission of lithium ions in the pole piece, and improving the rate performance of the battery.
  • the positive electrode slurry does not need to add additional binders and conductive agents, the reduction of the material components in the slurry is also conducive to improving the consistency of the slurry, thereby improving the quality of the battery.
  • the composite polymer can also improve the mechanical properties of the pole piece, endow the pole piece with flexibility, can effectively alleviate the volume expansion of the pole piece during the charge and discharge process, maintain the stability of the electrode, and further improve the lithium ion in the pole piece.
  • the transmission speed is improved, and the magnification performance is improved.
  • the present disclosure proposes an automobile.
  • the automobile has the above-mentioned lithium battery.
  • the lithium battery has a positive electrode sheet prepared from the above-mentioned positive electrode slurry, the lithium battery has better cycle performance and rate performance, and safety performance and The consistency is better. As a result, it is beneficial to improve the endurance and safety performance of the car.
  • This embodiment provides a composite polymer, which is a block copolymer of polyfurfuryl alcohol and polyethylene oxide.
  • the preparation method of the above-mentioned composite polymer includes the following steps:
  • the oxalic acid and NMP are sent to a homogenizer mixer according to the mass ratio of 1:30, then add polyethylene oxide (purchased from Acmec, brand name P39860) and stir, and finally add furfuryl alcohol and stir to obtain a brown glue liquid with a solid content of 1.2%.
  • the brown gum solution is a chain-shaped block copolymer of polyfurfuryl alcohol and polyethylene oxide, wherein the average molecular weight of the block copolymer of polyfurfuryl alcohol and polyethylene oxide is 50,000.
  • This embodiment provides a positive electrode slurry, which is composed of the composite polymer and the ternary material NCM.
  • the method for preparing the above-mentioned positive electrode slurry includes the following steps:
  • This embodiment provides a positive electrode sheet, which is composed of the positive electrode slurry and aluminum foil.
  • the preparation method of the above-mentioned positive electrode sheet includes the following steps:
  • This embodiment provides a composite polymer, which is a block copolymer of polyfurfuryl alcohol and polyethylene oxide.
  • the preparation method of the above-mentioned composite polymer includes the following steps:
  • the hydrochloric acid and dimethyl sulfoxide are sent to a homogenizer mixer according to the mass ratio of 1:49, then add polyethylene oxide (purchased from Acmec, brand name P39860) and stir, and finally add furfuryl alcohol and stir to obtain a brown solid content of 8% Glue liquid, the brown glue liquid is a block copolymer of chain polyfurfuryl alcohol and polyethylene oxide, wherein the average molecular weight of the block copolymer of polyfurfuryl alcohol and polyethylene oxide is 45,000.
  • This embodiment provides a positive electrode slurry, which is composed of the composite polymer and the ternary material NCA.
  • the method for preparing the above-mentioned positive electrode slurry includes the following steps:
  • This embodiment provides a positive electrode sheet, which is composed of the positive electrode slurry and aluminum foil.
  • the preparation method of the above-mentioned positive electrode sheet includes the following steps:
  • This embodiment provides a composite polymer, which is a block copolymer of polyfurfuryl alcohol and polyethylene oxide.
  • the preparation method of the above-mentioned composite polymer includes the following steps:
  • the oxalic acid and NMP are sent to a homogenizer mixer at a mass ratio of 2:45, then add polyethylene oxide (purchased from Acmec, brand name P39860) and stir, and finally add furfuryl alcohol and stir to obtain a brown glue with a solid content of 18%.
  • the brown gum solution is a chain-shaped block copolymer of polyfurfuryl alcohol and polyethylene oxide, wherein the average molecular weight of the block copolymer of polyfurfuryl alcohol and polyethylene oxide is 55,000.
  • This embodiment provides a positive electrode slurry, which is composed of the composite polymer and the ternary material NCM.
  • the method for preparing the above-mentioned positive electrode slurry includes the following steps:
  • This embodiment provides a positive electrode sheet, which is composed of the positive electrode slurry and aluminum foil.
  • the preparation method of the above-mentioned positive electrode sheet includes the following steps:
  • the binder polyvinylidene fluoride (purchased from Sigma, brand name SIG-182702) was used as the raw material of the positive electrode material.
  • This comparative example provides a positive electrode slurry, which is composed of the polyvinylidene fluoride and the ternary material NCM.
  • the method for preparing the above-mentioned positive electrode slurry includes the following steps:
  • This comparative example provides a positive electrode sheet composed of the positive electrode slurry and aluminum foil.
  • the preparation method of the above-mentioned positive electrode sheet includes the following steps:
  • Example 1 and Comparative Example 1 were tested as follows:
  • SEM Scanning electron microscope
  • Charging and discharging performance the positive electrode plate is tested for the battery, the test method: 0.33C constant current and constant voltage charging to 4.25V, cut-off current 0.05C, 0.33C discharge to 2.5V, to obtain its charging and discharging performance;
  • Cycle performance The positive electrode plate is subjected to battery test, the test method: 0.5C constant current and constant voltage charge to 4.25V, cut-off current 0.05C, 0.5C discharge to 2.5V. Repeat the above charging and discharging steps. When the discharge capacity is 80% of the initial discharge capacity, stop the test, obtain its cycle performance at 0.5C, and calculate its capacity retention rate;
  • Rate performance test the positive electrode plate, test method: 0.33C constant current and constant voltage charge to 4.25V, cut-off current 0.05C, different rate discharge: 0.1C, 0.33C, 0.5C, 1C, 2C, discharge to 2.5V, can get its rate performance under 0.1C, 0.33C, 0.5C, 1C and 2C;
  • Comparative Example 1 Analyzing Comparative Example 1 and Example 1, it can be found that the overall performance of Comparative Example 1 is not as good as that of Example 1.
  • the positive electrode sheet obtained by using the composite polymer of the present disclosure has better performance than the positive electrode sheet obtained by using polyvinylidene fluoride.
  • the positive electrode sheet obtained from the composite polymer of the present disclosure has low charge and discharge polarization and good charge and discharge performance.
  • Example 1 Compared with Comparative Example 1, the discharge capacity of Example 1 is higher at the same rate, and the change of the discharge capacity is smaller with the increase of the rate, and the performance is more stable.
  • the composite polymerization described in the present disclosure is adopted.
  • the resulting positive electrode sheet has better rate performance.

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Abstract

本文公布了一种复合聚合物及其制备方法和应用，所述复合聚合物为聚糠醇和聚氧化乙烯的嵌段共聚物。该复合聚合物具有较优的粘结性能和导电子和离子性能，有利于提高极片的品质和剥离力，提高电池的循环性能、倍率性能和安全性能。

Description

复合聚合物及其制备方法和应用 技术领域
本公开涉及锂电池及其应用技术领域，例如涉及复合聚合物及其制备方法和应用。
背景技术
随着社会的快速发展和进步，能源短缺及环境污染问题日益严重，人们对清洁能源变得日益重视；同时，随着新能源汽车日益普及以及能源动力发展日益扩大，促使人们开发更高能量密度的锂离子电池。目前锂离子动力电池正极大多采用磷酸铁锂和三元材料，随着对能量密度要求的不断提高，在现有电芯设计体系上继续提高能量密度越来越困难，尤其是高续航电动汽车方面。
传统的液态动力电池为了达到高电压和高能量密度，一般采用有机溶剂作为电解液，但有机电解液含有易燃物质，易造成安全隐患。随着动力电池尺寸型号的增大，可燃性有机溶剂的使用量增加，增大了热辐射，也使得电池更容易发热，增大了电池热失控的风险。新能源汽车自燃现象层出不穷，人们一直尝试开发安全可靠的新型电池。全固态电池因不含电解液成分可以更加稳定的存在，引起人们的普遍关注；但是，目前全固态电池技术尚不成熟，距离工业化还有很长的路要走。半固态电池作为液态电池与全固态电池的中间产品，可以减少电芯内部电解液的用量，在一定程度上改进了电芯的安全性能，是目前最接近也最易实现量产的过渡产品。
因此，现有锂电池有待进一步改进。
发明内容
本公开提供一种复合聚合物及其制备方法和应用。
本公开在一实施例中提供一种复合聚合物，所述复合聚合物为聚糠醇和聚氧化乙烯的嵌段共聚物。
在一些情况下，半固态电池的制作过程中，正极普遍采用的粘结剂为聚偏氟乙烯(PVDF)，粘结剂PVDF在电极中主要存在三种相互作用：粘结剂和活性物质颗粒之间的相互作用、粘结剂和集流体之间的相互作用、粘结剂分子和粘结剂分子之间的相互作用。粘结剂的粘度是重要的工艺参数，如果粘结剂的粘度太小，则制备的浆料粘度也较小，导致浆料的流动性过强且容易发生沉降现象，存储稳定性差，因此需要额外添加增稠剂；但如果粘结剂的粘度过大，又不利于活性物质和导电剂的分散，粘结剂没有导电作用，增加了电池内阻，影响电池性能发挥。为提升动力电池的能量密度和倍率性能，常在电芯体系设计中提高活性物质含量，降低粘结剂含量。而降低粘结剂的用量会影响到匀浆工艺，使浆料的稳定性降低，制备的极片剥离强度降低，进而使得涂层易从集流体上剥离，影响电性能的发挥，对电池安全性有很大隐患。
本公开提供的一实施例中，该复合聚合物自身具有电子和离子传输的特性，相比于传统的粘结剂材料，锂离子可以实现在其内部的自由传输；相比于普通离子聚合物，由于π*C＝C化学键形成电子云，增加了导电性。同时该复合聚合 物因其含有与粘结剂类似的结构部分，更易与正极活性物质充分混合，形成均匀相，提高极片粘结力和剥离力。进一步地，该复合聚合物可以在加入电解液后迅速凝胶化，促进电子和离子在极片内部的传输，同时也可以避免电芯内部太多电解液的存在，进而提高电池的安全性能。
在一实施例中，所述复合聚合物为链状聚合物或星型聚合物或树枝状聚合物。
在一实施例中，所述复合聚合物的平均分子量为45000-55000，例如46000、48000、50000、52000、54000等。
在一实施例中，所述复合聚合物的固含量为1.2wt％-18wt％，例如2wt％、4wt％、6wt％、8wt％、10wt％、12wt％、14wt％、16wt％等。
本公开在一实施例中提供一种所述的复合聚合物的制备方法，所述方法包括以下步骤：
将引发剂、溶剂、聚氧化乙烯和糠醇混合搅拌，得到复合聚合物。
本公开在一实施例中，在引发剂和溶剂的作用下，可使得糠醇发生聚合反应，并可使得聚合后的糠醇与聚氧化乙烯反应得到聚糠醇与聚氧化乙烯的嵌段聚合物。在聚糠醇和聚氧化乙烯的共同作用下，该复合聚合物自身具有电子和离子传输的特性，相比于传统的粘结剂材料，锂离子可以实现在其内部的自由传输；相比于普通离子聚合物，由于π*C＝C化学键形成电子云，增加了导电性。同时该复合聚合物因其含有与粘结剂类似的结构部分，更易与正极活性物质充分混合，形成均匀相，提高极片粘结力和剥离力。进一步地，该复合聚合物可以在加入电解液后迅速凝胶化，促进电子和离子在极片内部的传输，同时也可以避免电芯内部太多电解液的存在，进而提高电池的安全性能。
在一实施例中，所述引发剂选自草酸、盐酸中的至少之一，例如引发剂可以是草酸，也可以是盐酸，还可以是草酸和盐酸的混合物。
在一实施例中，所述引发剂选自草酸。
在一实施例中，所述溶剂选自N-甲基吡咯烷酮(NMP)、二甲基亚砜中的至少之一，例如溶剂可以是N-甲基吡咯烷酮，也可以是二甲基亚砜，还可以是N-甲基吡咯烷酮和二甲基亚砜的混合物。
在一实施例中，所述引发剂与所述溶剂的质量比为(2-4):(90-98)，其中，2-4可以为2.5、3.0、3.5等，90-98可以为91、92、93、94、95、96、97等。
本公开在一实施例中提供一种正极浆料，所述正极浆料由正极活性物质和胶液组成，所述胶液为本公开一实施例中所述的复合聚合物或采用本公开一实施例中所述的方法制备所得的复合聚合物。
本公开一实施例提供的正极浆料，因其具有上述复合聚合物，该复合聚合物既具有粘结剂的粘结性能，可提高其与正极活性物质的相容性，使得正极活性物质均匀分散于极片内，提高极片的粘结力和剥离力，提升电池的倍率循环性能，同时也具有导电和导离子的性能，可作为锂离子传输的载体，承担电解 液内溶剂的作用协同促进锂离子在极片内的传输，提升电池的倍率性能。由此可使得正极浆料无需另外添加粘结剂和导电剂，而浆料中物质组分的减少也有利于提升浆料的一致性，进而提升电池的品质。进一步地，复合聚合物还可以改进极片的机械性能，赋予极片柔韧性，可以有效缓解极片在充放电过程中的体积膨胀，保持电极的稳定性，进而进一步提高锂离子在极片内的传输速度，提升倍率性能。
在一实施例中，所述正极浆料的固含量为50wt％-80wt％，例如55wt％、60wt％、65wt％、70wt％、75wt％等。
在一实施例中，所述正极浆料的粘度为3000-20000cP，例如4000cP、8000cP、12000cP、16000cP等。
在一实施例中，所述正极活性物质选自镍钴锰(NCM)、镍钴铝酸锂(NCA)中的至少之一，例如正极活性物质可以是NCM，也可以是NCA，还可以是NCM和NCA的混合物。
本公开在一实施例中提供一种锂电池，所述锂电池具有由本公开一实施例所述的正极浆料制备得到的正极片。
本公开一实施例提供的锂电池，该锂电池具有由正极活性物质和上述复合聚合物组成的正极浆料制备的正极片，因其具有上述复合聚合物，该复合聚合物既具有粘结剂的粘结性能，可提高其与正极活性物质的相容性，使得正极活性物质均匀分散于极片内，提高极片的粘结力和剥离力，提升电池的倍率循环性能，同时也具有导电和导离子的性能，可作为锂离子传输的载体，承担电解液内溶剂的作用协同促进锂离子在极片内的传输，提升电池的倍率性能。同时因正极浆料无需另外添加粘结剂和导电剂，浆料中物质组分的减少也有利于提升浆料的一致性，进而提升电池的品质。进一步地，复合聚合物还可以改进极片的机械性能，赋予极片柔韧性，可以有效缓解极片在充放电过程中的体积膨胀，保持电极的稳定性，进而进一步提高锂离子在极片内的传输速度，提升倍率性能。
本公开在一实施例中提供一种汽车，所述汽车具有由本公开一实施例所述的锂电池。
本公开一实施例提供的汽车，因该汽车具有上述锂电池，而该锂电池因具有由上述正极浆料制备得到的正极片，使得锂电池具有较优的循环性能和倍率性能，且安全性能和一致性较好。由此，有利于提高该汽车的续航能力和安全性能。
本公开的附加方面和优点将在下面的描述中部分给出，部分将从下面的描述中变得明显，或通过本公开的实践了解到。
附图说明
附图用来提供对本公开技术方案的进一步理解，并且构成说明书的一部分，与本申请的实施例一起用于解释本公开的技术方案，并不构成对本公开技术方案的限制。
图1是实施例所得正极片的涂覆层的SEM图；
图2是实施例所得正极片的充放电性能测试曲线；
图3是实施例和对比例所得正极片在0.5C下的循环性能测试曲线；
图4是实施例和对比例所得正极片在0.1C、0.33C、0.5C、1C和2C下的倍率性能测试曲线；
图5是对比例所得正极片的涂覆层的SEM图。
具体实施例
下面结合附图并通过具体实施方式来进一步说明本公开的技术方案。
在本公开的一个方面，本公开提出了一种复合聚合物，根据本公开的实施例，该复合聚合物为聚糠醇和聚氧化乙烯的嵌段共聚物。该复合聚合物自身具有电子和离子传输的特性，相比于传统的粘结剂材料，锂离子可以实现在其内部的自由传输；相比于普通离子聚合物，由于π*C＝C化学键形成电子云，增加了导电性。同时该复合聚合物因其含有与粘结剂类似的结构部分，更易与正极活性物质充分混合，形成均匀相，提高极片粘结力和剥离力。进一步地，该复合聚合物可以在加入电解液后迅速凝胶化，促进电子和离子在极片内部的传输，同时也可以避免电芯内部太多电解液的存在，进而提高电池的安全性能。
根据本公开的一个实施例，复合聚合物可以为链状聚合物或星型聚合物或树枝状聚合物，本领域技术人员可以根据需要和制备工艺进行选择。进一步地，复合聚合物的平均分子量并不受特别限制，本领域技术人员可以根据实际需要进行选择，如可以为45000-55000，本公开一实施例的平均分子量为50000。需要说明的是，受反应温度影响，高温时可以生成平均分子量更高的聚合物，增大聚合物的粘度，由此，可以通过提高反应温度提高复合聚合物的粘度，如可以将反应温度提高至55℃。进一步地，复合聚合物的固含量也不受特别限制，如可以为1.2wt％-18wt％，提高固含量可以提高聚合物浆料粘度。
根据本公开实施例的复合聚合物，该复合聚合物自身具有电子和离子传输的特性，相比于传统的粘结剂材料，锂离子可以实现在其内部的自由传输；相比于普通离子聚合物，由于π*C＝C化学键形成电子云，增加了导电性。同时该复合聚合物因其含有与粘结剂类似的结构部分，更易与正极活性物质充分混合，形成均匀相，提高极片粘结力和剥离力。进一步地，该复合聚合物可以在加入电解液后迅速凝胶化，促进电子和离子在极片内部的传输，同时也可以避免电芯内部太多电解液的存在，进而提高电池的安全性能。
在本公开的再一个方面，本公开提出了一种制备复合聚合物的方法，根据本公开的实施例，该方法包括：将引发剂、溶剂、聚氧化乙烯和糠醇混合搅拌，以便得到复合聚合物。在引发剂和溶剂的作用下，可使得糠醇发生聚合反应，并可使得聚合后的糠醇与聚氧化乙烯反应得到聚糠醇与聚氧化乙烯的嵌段聚合物。具体地，可以先将引发剂和溶剂混合搅拌，之后再加入聚氧化乙烯和糠醇搅拌混合反应，以便得到复合聚合物。
根据本公开的一个实施例，引发剂和溶剂的具体类型并不受特别限制，本领域技术人员可以根据实际需要进行选择，如引发剂可以选自草酸、盐酸中的至少之一，可以选自草酸；溶剂可以选自N-甲基吡咯烷酮、二甲基亚砜中的至少之一。采用上述引发剂和溶剂有利于降低成本，同时使得反应速度易控制。在一些实施方式中，引发剂和溶剂的质量比也不受特别限制，如可以为2-4：90-98，本公开的一实施例中引发剂和溶剂的质量比为1：30，质量比过高会增加浆料的粘度。
根据本公开实施例的制备方法，在引发剂和溶剂的作用下，可使得糠醇发生聚合反应，并可使得聚合后的糠醇与聚氧化乙烯反应得到聚糠醇与聚氧化乙烯的嵌段聚合物。在聚糠醇和聚氧化乙烯的共同作用下，该复合聚合物自身具有电子和离子传输的特性，相比于传统的粘结剂材料，锂离子可以实现在其内部的自由传输；相比于普通离子聚合物，由于π*C＝C化学键形成电子云，增加了导电性。同时该复合聚合物因其含有与粘结剂类似的结构部分，更易与正极活性物质充分混合，形成均匀相，提高极片粘结力和剥离力。进一步地，该复合聚合物可以在加入电解液后迅速凝胶化，促进电子和离子在极片内部的传输，同时也可以避免电芯内部太多电解液的存在，进而提高电池的安全性能。
在本公开的又一个方面，本公开提出了一种正极浆料，根据本公开的实施例，该正极浆料由正极活性物质和胶液组成，胶液为上述复合聚合物或采用上述制备复合聚合物的方法制备所得的复合聚合物。因其具有上述复合聚合物，该复合聚合物既具有粘结剂的粘结性能，可提高其与正极活性物质的相容性，使得正极活性物质均匀分散于极片内，提高极片的粘结力和剥离力，提升电池的倍率循环性能，同时也具有导电和导离子的性能，可作为锂离子传输的载体，承担电解液内溶剂的作用协同促进锂离子在极片内的传输，提升电池的倍率性能。由此可使得正极浆料无需另外添加粘结剂和导电剂，而浆料中物质组分的减少也有利于提升浆料的一致性，进而提升电池的品质。进一步地，复合聚合物还可以改进极片的机械性能，赋予极片柔韧性，可以有效缓解极片在充放电过程中的体积膨胀，保持电极的稳定性，进而进一步提高锂离子在极片内的传输速度，提升倍率性能。
根据公开的一个实施例，正极浆料的固含量和粘度并不受特别限制，本领域技术人员可以根据实际需要进行选择，如固含量可以为50wt％-80wt％，粘度可以为3000-20000cP。浆料固含量和粘度过高会导致浆料一致性降低。进一步地，正极活性物质的具体类型也不受特别限制，如可以为NCM、NCA中的至少之一。
根据本公开实施例的正极浆料，因其具有上述复合聚合物，该复合聚合物既具有粘结剂的粘结性能，可提高其与正极活性物质的相容性，使得正极活性物质均匀分散于极片内，提高极片的粘结力和剥离力，提升电池的倍率循环性能，同时也具有导电和导离子的性能，可作为锂离子传输的载体，承担电解液内溶剂的作用协同促进锂离子在极片内的传输，提升电池的倍率性能。由此可 使得正极浆料无需另外添加粘结剂和导电剂，而浆料中物质组分的减少也有利于提升浆料的一致性，进而提升电池的品质。进一步地，复合聚合物还可以改进极片的机械性能，赋予极片柔韧性，可以有效缓解极片在充放电过程中的体积膨胀，保持电极的稳定性，进而进一步提高锂离子在极片内的传输速度，提升倍率性能。
在本公开的又一个方面，本公开提出了一种锂电池，根据本公开的实施例，该锂电池具有由上述正极浆料制备得到的正极片。根据本公开实施例的锂电池，该锂电池具有由正极活性物质和上述复合聚合物组成的正极浆料制备的正极片，因其具有上述复合聚合物，该复合聚合物既具有粘结剂的粘结性能，可提高其与正极活性物质的相容性，使得正极活性物质均匀分散于极片内，提高极片的粘结力和剥离力，提升电池的倍率循环性能，同时也具有导电和导离子的性能，可作为锂离子传输的载体，承担电解液内溶剂的作用协同促进锂离子在极片内的传输，提升电池的倍率性能。同时因正极浆料无需另外添加粘结剂和导电剂，浆料中物质组分的减少也有利于提升浆料的一致性，进而提升电池的品质。进一步地，复合聚合物还可以改进极片的机械性能，赋予极片柔韧性，可以有效缓解极片在充放电过程中的体积膨胀，保持电极的稳定性，进而进一步提高锂离子在极片内的传输速度，提升倍率性能。
在本公开的又一个方面，本公开提出了一种汽车，根据本公开的实施例，该汽车具有上述锂电池。根据本公开实施例的汽车，因该汽车具有上述锂电池，而该锂电池因具有由上述正极浆料制备得到的正极片，使得锂电池具有较优的循环性能和倍率性能，且安全性能和一致性较好。由此，有利于提高该汽车的续航能力和安全性能。
下面参考具体实施例，对本公开进行描述，需要说明的是，这些实施例仅仅是描述性的，而不以任何方式限制本公开。
实施例1
本实施例提供一种复合聚合物，所述复合聚合物为聚糠醇和聚氧化乙烯的嵌段共聚物。
上述复合聚合物的制备方法包括如下步骤：
将草酸与NMP按照质量比1：30送至匀浆搅拌机搅拌，然后加入聚氧化乙烯(购于Acmec，牌号为P39860)搅拌，最后加入糠醇搅拌，得到固含量为1.2％的棕色胶液，该棕色胶液为链状的聚糠醇和聚氧化乙烯的嵌段共聚物，其中该聚糠醇和聚氧化乙烯的嵌段共聚物的平均分子量为50000。
本实施例提供一种正极浆料，所述正极浆料由所述复合聚合物和三元材料NCM组成。
上述正极浆料的制备方法包括如下步骤：
往上述胶液中，即聚糠醇和聚氧化乙烯的嵌段共聚物中，加入三元材料NCM，搅拌得到固含量为50％、粘度为3000cP的正极浆料。
本实施例提供一种正极片，所述正极片由所述正极浆料和铝箔组成。
上述正极片的制备方法包括如下步骤：
采用自动涂布机涂布，调整涂布刮刀间隙，目标面密度为15mg/cm 2，把上述正极浆料涂到铝箔上，形成涂覆层，涂好的极片在120℃下烘烤10min，得到正极活性物质含量为80％的正极片。
实施例2
本实施例提供一种复合聚合物，所述复合聚合物为聚糠醇和聚氧化乙烯的嵌段共聚物。
上述复合聚合物的制备方法包括如下步骤：
将盐酸与二甲基亚砜按照质量比1：49送至匀浆搅拌机搅拌，然后加入聚氧化乙烯(购于Acmec，牌号为P39860)搅拌，最后加入糠醇搅拌，得到固含量为8％的棕色胶液，该棕色胶液为链状的聚糠醇和聚氧化乙烯的嵌段共聚物，其中该聚糠醇和聚氧化乙烯的嵌段共聚物的平均分子量为45000。
本实施例提供一种正极浆料，所述正极浆料由所述复合聚合物和三元材料NCA组成。
上述正极浆料的制备方法包括如下步骤：
往上述胶液中，即聚糠醇和聚氧化乙烯的嵌段共聚物中，加入三元材料NCM，搅拌得到固含量为80％、粘度为20000cP的正极浆料。
本实施例提供一种正极片，所述正极片由所述正极浆料和铝箔组成。
上述正极片的制备方法包括如下步骤：
采用自动涂布机涂布，调整涂布刮刀间隙，目标面密度为15mg/cm 2，把上述正极浆料涂到铝箔上，形成涂覆层，涂好的极片在120℃下烘烤10min，得到正极活性物质含量为80％的正极片。
实施例3
本实施例提供一种复合聚合物，所述复合聚合物为聚糠醇和聚氧化乙烯的嵌段共聚物。
上述复合聚合物的制备方法包括如下步骤：
将草酸与NMP按照质量比2：45送至匀浆搅拌机搅拌，然后加入聚氧化乙烯(购于Acmec，牌号为P39860)搅拌，最后加入糠醇搅拌，得到固含量为18％的棕色胶液，该棕色胶液为链状的聚糠醇和聚氧化乙烯的嵌段共聚物，其中该聚糠醇和聚氧化乙烯的嵌段共聚物的平均分子量为55000。
本实施例提供一种正极浆料，所述正极浆料由所述复合聚合物和三元材料NCM组成。
上述正极浆料的制备方法包括如下步骤：
往上述胶液中，即聚糠醇和聚氧化乙烯的嵌段共聚物中，加入三元材料NCM，搅拌得到固含量为65％、粘度为4500cP的正极浆料。
本实施例提供一种正极片，所述正极片由所述正极浆料和铝箔组成。
上述正极片的制备方法包括如下步骤：
采用自动涂布机涂布，调整涂布刮刀间隙，目标面密度为15mg/cm 2，把上 述正极浆料涂到铝箔上，形成涂覆层，涂好的极片在120℃下烘烤10min，得到正极活性物质含量为80％的正极片。
对比例1
本对比例以粘结剂聚偏氟乙烯(购于Sigma，牌号为SIG-182702)作为正极材料的原料。
本对比例提供一种正极浆料，所述正极浆料由所述聚偏氟乙烯和三元材料NCM组成。
上述正极浆料的制备方法包括如下步骤：
将粘结剂聚偏氟乙烯与溶剂NMP混合搅拌，然后加入导电剂SP混合搅拌，之后再加入三元材料NCM，并采用NMP调节浆料粘度，搅拌均匀后得到固含量为50％、粘度为3000cP的正极浆料。其中聚偏氟乙烯与NMP、SP、NCM的质量比为1.5：65：1：96。
本对比例提供一种正极片，所述正极片由所述正极浆料和铝箔组成。
上述正极片的制备方法包括如下步骤：
采用自动涂布机涂布，调整涂布刮刀间隙，目标面密度为15mg/cm 2，把上述正极浆料涂到铝箔上，形成涂覆层，涂好的极片在120℃下烘烤10min，得到正极活性物质含量为80％的正极片。
性能测试
将实施例1和对比例1进行如下测试：
(1)扫描电子显微镜(SEM)：将正极片涂覆层的形貌进行SEM测试。
测试结果汇总于图1(实施例1)和图5中(对比例1)。
(2)电池测试：
充放电性能：将所述正极片进行电池测试，测试方法：0.33C恒流恒压充电至4.25V，截止电流0.05C，0.33C放电至2.5V，得到其充放电性能；
测试结果汇总于图2中；
循环性能：将所述正极片进行电池测试，测试方法：0.5C恒流恒压充电至4.25V，截止电流0.05C，0.5C放电至2.5V。重复上述充电和放电工步，当放电容量是初始放电容量的80％时，停止测试，得到其在0.5C下的循环性能，并计算其容量保持率；
测试结果汇总于表1和图3中；
倍率性能：将所述正极片进行电池测试，测试方法：0.33C恒流恒压充电至4.25V，截止电流0.05C，不同倍率放电：0.1C，0.33C，0.5C，1C，2C，放电至2.5V，可得到其在0.1C、0.33C、0.5C、1C和2C下的倍率性能；
测试结果汇总于表1和图4中。
表1
Figure PCTCN2021077191-appb-000001
Figure PCTCN2021077191-appb-000002
分析表1数据可知，本公开所述复合聚合物所得的正极片容量保持率在90.2％以上，在不同倍率下进行放电，本公开所述复合聚合物所得的正极片随着倍率的提升，放电效率下降幅度较小，在1C倍率下，放电效率在89.6％以上，在2C倍率下，放电效率在80.6％以上，本公开所述复合聚合物所得的正极片兼具优异的循环性能和倍率性能。
分析对比例1与实施例1可以发现，对比例1的综合性能不如实施例1，采用本公开所述复合聚合物所得的正极片比采用聚偏氟乙烯所得的正极片性能优异。
分析图1和图5可知，与图5相比，图1在活性物质之间明显形成更加均匀的导电支状网络。
由图2可知，本公开所述复合聚合物所得的正极片充电和放电极化小，充放电性能好。
由图3可知，实施例1的容量保持率为96.7％，对比例1的容量保持率为74.66％，采用本公开所述复合聚合物所得的正极片循环性能更好。
由图4可知，实施例1相对于对比例1来说，在相同倍率下的放电量更高，且随着倍率的提升放电量的变化更小，性能更稳定，采用本公开所述复合聚合物所得的正极片倍率性能更好。

Claims (15)

  1. 一种复合聚合物，所述复合聚合物为聚糠醇和聚氧化乙烯的嵌段共聚物。
  2. 根据权利要求1所述的复合聚合物，其中，所述复合聚合物为链状聚合物或星型聚合物或树枝状聚合物。
  3. 根据权利要求1或2所述的复合聚合物，其中，所述复合聚合物的平均分子量为45000-55000。
  4. 根据权利要求1-3任一项所述的复合聚合物，其中，所述复合聚合物的固含量为1.2wt％-18wt％。
  5. 一种根据权利要求1-4任一项所述的复合聚合物的制备方法，所述制备方法包括如下步骤：
    将引发剂、溶剂、聚氧化乙烯和糠醇混合搅拌，得到所述复合聚合物。
  6. 根据权利要求5所述的制备方法，其中，所述引发剂选自草酸、盐酸中的至少之一。
  7. 根据权利要求5或6所述的制备方法，其中，所述引发剂选自草酸。
  8. 根据权利要求5-7任一项所述的制备方法，其中，所述溶剂选自N-甲基吡咯烷酮、二甲基亚砜中的至少之一。
  9. 根据权利要求5-8任一项所述的制备方法，其中，所述引发剂与所述溶剂的质量比为(2-4):(90-98)。
  10. 一种正极浆料，所述正极浆料由正极活性物质和胶液组成，所述胶液为权利要求1-4中任一项所述的复合聚合物或采用权利要求5-9中任一项所述的方法制备所得的复合聚合物。
  11. 根据权利要求10所述的正极浆料，其中，所述正极浆料的固含量为50wt％-80wt％。
  12. 根据权利要求10或11所述的正极浆料，其中，所述正极浆料的粘度为3000-20000cP。
  13. 根据权利要求10-12任一项所述的正极浆料，其中，所述正极活性物质选自NCM、NCA中的至少之一。
  14. 一种锂电池，所述锂电池具有由权利要求10-13任一项所述的正极浆料制备得到的正极片。
  15. 一种汽车，所述汽车具有权利要求14所述的锂电池。
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