WO2022052425A1 - 一种电解质材料及其制备方法和应用 - Google Patents

一种电解质材料及其制备方法和应用 Download PDF

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Publication number
WO2022052425A1
WO2022052425A1 PCT/CN2021/077549 CN2021077549W WO2022052425A1 WO 2022052425 A1 WO2022052425 A1 WO 2022052425A1 CN 2021077549 W CN2021077549 W CN 2021077549W WO 2022052425 A1 WO2022052425 A1 WO 2022052425A1
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Prior art keywords
flame retardant
preparation
electrolyte material
lithium salt
emulsifier
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PCT/CN2021/077549
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English (en)
French (fr)
Inventor
吕文彬
邓素祥
陈少杰
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Svolt Energy Technology Co Ltd
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Svolt Energy Technology Co Ltd
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Priority to US18/023,697 priority Critical patent/US20230307721A1/en
Priority to JP2022548855A priority patent/JP7473660B2/ja
Priority to EP21865488.7A priority patent/EP4187672A4/en
Priority to KR1020227034526A priority patent/KR102806239B1/ko
Publication of WO2022052425A1 publication Critical patent/WO2022052425A1/zh
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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
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • 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
    • H01M4/139—Processes of manufacture
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/30—Arrangements for facilitating escape of gases
    • H01M50/383—Flame arresting or ignition-preventing means
    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0094—Composites in the form of layered products, e.g. coatings
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present disclosure relates to the field of battery technology, for example, to an electrolyte material and a preparation method and application thereof.
  • Solid-state batteries can be divided into: 1 semi-solid batteries; 2 all-solid-state batteries, in which the positive and negative diaphragms of all-solid-state batteries are in solid-solid contact, and the Li+ conduction resistance is relatively large, and the current performance is difficult to reach the traditional liquid state.
  • Battery level as a transition state between traditional liquid batteries and all-solid-state batteries, semi-solid batteries are very close to traditional liquid batteries in terms of preparation operability, battery rate performance, and cycle performance, and their safety performance is even better than traditional liquid batteries. Battery.
  • Polymer solid electrolytes have attracted much attention as safe and low-density materials, but adding polymer solid electrolytes to electrodes using traditional methods can also be problematic because the polymer electrolyte material itself is very soft and has a relatively low Young's modulus. Low, during the rolling process of the battery after adding, because the electrolyte is very soft, the electrode will expand greatly, and the compaction density is difficult to increase.
  • All-solid-state batteries can exist more stably inside the cells because they do not contain electrolyte components, which has attracted widespread attention; however, at present, all-solid-state batteries Battery technology is still immature, and there is still a long way to go before industrialization.
  • semi-solid batteries can reduce the amount of electrolyte inside the cells and improve the safety of the cells to a certain extent. The performance is currently the closest and easiest transition product to mass production.
  • the role of the electrolyte in the thermal runaway process of lithium-ion batteries is very critical. At present, from the perspective of materials, there are many safety improvement strategies to prevent lithium-ion batteries from thermal runaway, fire, combustion and explosion.
  • the use of flame retardant electrolytes is the most economical, simple and effective strategy. , which can effectively reduce the risk of thermal runaway combustion and explosion of lithium-ion batteries, and greatly reduce the injury to personnel and property caused by thermal runaway; however, adding flame retardants to batteries often reduces the cycle performance and rate performance of the battery, and affects the electrical performance of the battery. The effect of flame retardant is great, and if the added amount is small, it will not play a flame retardant effect, so the performance of the current battery with flame retardant is not very ideal, and it is difficult to take into account the flame retardant performance and electrochemical performance.
  • CN105261742A discloses a sulfur-based semi-solid lithium battery and a preparation method thereof.
  • the battery is formed by stacking a semi-solid sulfur-based positive electrode, a semi-solid electrolyte and a lithium sheet negative electrode;
  • the sulfur-based material and the carbon conductive agent are mixed into a semi-solid state, and then formed by using aluminum foil or nickel mesh as the current collector;
  • the semi-solid electrolyte is mixed with porous inorganic oxide and lithium salt-containing polymer;
  • the lithium salt-containing polymer is Composed of a fluid-dynamic polymer mixed with lithium salts.
  • CN110265715A discloses a special gelling agent for semi-solid electrolytes of lithium batteries and a preparation method.
  • the gelling agent is prepared by mixing and grinding a polymer matrix, hydroxypropyl methylcellulose and a flame retardant to obtain composite particles, and then Hydrogen polysilazane, porous inorganic matter and ammonia water are mixed and sprayed on the surface of the composite particles, and finally the coated composite particles and dispersant are completely dispersed by an airflow mixer.
  • the present disclosure provides an electrolyte material and a preparation method and application thereof.
  • an electrolyte material which includes a core body and a shell coated outside the core body, the core body includes flame retardant particles, and the shell includes an ion conductive polymer;
  • the ionically conductive polymer includes a combination of a lithium salt and a polymer electrolyte.
  • an ion-conductive polymer material is used to coat a flame retardant to form a core-shell material, and this material is added to the electrode sheet.
  • the battery encounters safety problems, such as acupuncture, acupuncture, Compression, shock, electrical abuse conditions such as overcharge, forced short circuit, thermal abuse conditions such as hot box, thermal shock, etc., the battery will generate heat due to internal short circuit, during the heating process, the ion conductive polymer electrolyte melts and ruptures , the flame retardant is released, and the flame retardant plays a flame retardant role, preventing the thermal runaway of the battery in a short time and achieving the purpose of safe departure of personnel. Under normal use, the flame retardant is wrapped by the polymer electrolyte and will not affect the battery. excellent cycle performance and rate capability, resulting in excellent electrochemical performance.
  • the polymer electrolyte has good elasticity, which can reduce the swelling of the negative electrode. Compared with the conventional electrode adding polymer electrolyte, it is difficult to improve the compaction density.
  • the polymer electrolyte is fully dispersed in the electrode pole piece, which significantly increases the solid electrolyte content, ensures the uniform distribution of the solid electrolyte, improves the lithium ion channel, and ensures the normal migration of lithium ions in the pole piece. It will affect the electrical performance of the battery, and it can also ensure that the electrode has a high compaction density, and the pole piece is not prone to high elongation.
  • the electrolyte material provided by an embodiment of the present disclosure is used in the electrode and pole pieces.
  • the ion-conductive polymer electrolyte melts and ruptures, releasing the flame retardant, and the flame retardant
  • the flame retardant acts as a flame retardant, preventing the thermal runaway of the battery in a short period of time and achieving the purpose of safe departure of personnel.
  • the flame retardant is wrapped by the polymer electrolyte, which will not affect the cycle performance and rate performance of the battery. Excellent electrochemical performance.
  • the electrolyte material provided by an embodiment of the present disclosure is used for an electrode pole piece, which can improve the compaction density and reduce the expansion of the negative electrode.
  • the mass proportion of the flame retardant in the electrolyte material is 5-20%, such as 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% %, 15%, 16%, 17%, 18%, 19%, etc. In one embodiment, the mass proportion of the flame retardant in the electrolyte material is 10%.
  • the proportion of the flame retardant is 5-20%, so as to obtain the effect of no fire in the acupuncture and hot box experiments. If the proportion is too low, it will lead to fire, and if the proportion is too high, the battery will be damaged. Reduced capacity.
  • the diameter of the core body is 0.5-10 ⁇ m, such as 1 ⁇ m, 2 ⁇ m, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m and the like.
  • the thickness of the casing is 100-500 nm, such as 150 nm, 200 nm, 250 nm, 300 nm, 350 nm, 400 nm, 450 nm, and the like.
  • the flame retardant includes trimethyl phosphate (TMP), triethyl phosphate (TEP), tributyl phosphate (TBP), tris(2,2,2-trifluoroethyl)idene Any one or a combination of at least two of phosphate ester (TFP), triphenyl phosphate (TPP), phosphite or phosphazene flame retardant materials.
  • TMP trimethyl phosphate
  • TPP triethyl phosphate
  • TBP tributyl phosphate
  • TPP tris(2,2,2-trifluoroethyl)idene
  • the lithium salt accounts for 1-20% of the mass of the ion conductive polymer, such as 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% %, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, etc., in one embodiment, the lithium salt accounts for 12% of the mass of the ion conductive polymer %.
  • the lithium salt includes lithium perchlorate (LiClO 4 ), lithium bistrifluoromethanesulfonimide (LiTFSI), lithium bisfluorosulfonimide (LiFSI), lithium bisoxalatoborate (LiBOB) or lithium tetrafluoroborate (LiBF 4 ) any one or a combination of at least two.
  • LiTFSI lithium bistrifluoromethanesulfonimide
  • LiFSI lithium bisfluorosulfonimide
  • LiBOB lithium bisoxalatoborate
  • LiBF 4 lithium tetrafluoroborate
  • the melting temperature of the polymer electrolyte is 150-250°C, such as 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, etc. In one embodiment, the melting temperature of the polymer electrolyte is 200°C.
  • the above-mentioned melting temperature is selected, so that the electrolyte becomes a liquid after melting. If the melting temperature is too low, the polymer electrolyte will be non-liquid, and the flame retardant cannot be uniformly coated. lead to the oxidative decomposition of polymer electrolytes.
  • the polymer electrolyte includes polyethylene oxide (PEO), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), polyvinylidene fluoride (PVdF), polyethylene glycol ( PEG), polyethylene glycol diacrylate (PEGDA) or polyvinylene carbonate (PVCA) or a combination of at least two.
  • PEO polyethylene oxide
  • PAN polyacrylonitrile
  • PMMA polymethyl methacrylate
  • PVdF polyvinylidene fluoride
  • PEG polyethylene glycol
  • PEGDA polyethylene glycol diacrylate
  • PVCA polyvinylene carbonate
  • the polymer electrolyte contains the same molecular segments as the binder commonly used in the electrode slurry, it has better affinity and flexibility with the binder, and is more electrode-friendly. Bonding properties between active substances.
  • the polymer electrolyte contains the same segments as the binder, and the same segments are entangled with each other, which will reduce the expansion of the silicon anode.
  • the polymer electrolyte is incompatible with the electrolyte and cannot be dissolved in the electrolyte, which reduces the electrolyte becoming more viscous due to the dissolution of the polymer, reduces the electrical conductivity, and reduces the rate performance and cycle performance.
  • an emulsifier is present between the flame retardant particles and the ionically conductive polymer.
  • the emulsifier is deposited on the surface of the flame retardant particles.
  • an emulsifier is deposited on the surface of the flame retardant particles, because the surface of the emulsifier has hydrophilic and lipophilic groups, and the use of the emulsifier can make the polymer electrolyte more easily combined with the flame retardant microspheres to obtain a package. For an even and dense effect.
  • the emulsifier includes polyethylene glycol, sodium lauryl sulfonate, fatty acid polyoxyethylene ether, gum arabic, sodium alkylbenzene sulfonate, monoglyceryl isostearate, polyoxyethylene Ethane-polyoxypropylene copolymer, cetyltrimethylammonium bromide, styrene maleic anhydride copolymer, non-ionic paraffin micro-emulsifier (NMP), cationic paraffin micro-emulsifier (CMP), anionic paraffin Emulsifier (AMP), OP-10, OP-15, Perigua O-10, water-in-oil waste oil emulsifier (EEO), water-in-oil diesel emulsifier (EDO) or water-in-oil animal and vegetable oil emulsifier any one or a combination of at least two agents (EAP).
  • NMP non-ionic paraffin micro-emulsifier
  • CMP cationic paraffin micro-
  • a method for preparing an electrolyte material which includes: mixing and dispersing a flame retardant dispersion liquid, a polymer monomer, a lithium salt and an initiator to obtain a mixed solution , stirring and heating, and keeping the reaction temperature to obtain the electrolyte material.
  • the preparation method of an electrolyte material provided by an embodiment of the present disclosure can prepare an electrolyte material with a core-shell structure, and the preparation method is simple in operation, inexpensive in materials, obvious in flame retardant effect, and does not affect other performances of the battery.
  • the preparation method is performed in an argon atmosphere.
  • the preparation method further includes using a reflux condensing device.
  • the temperature of the dispersion is 80-90°C, such as 81°C, 82°C, 83°C, 84°C, 85°C, 86°C, 87°C, 88°C, 89°C, and the like.
  • the initiator includes at least one of azobisisobutyronitrile (AIBN) or azobisisoheptanenitrile (V65).
  • AIBN azobisisobutyronitrile
  • V65 azobisisoheptanenitrile
  • the mass proportion of the polymer monomer is 70-90%, for example, 72%, 74%, 76% , 78%, 80%, 82%, 84%, 86%, 88%, etc., in one embodiment, based on the total mass of the polymer monomer, lithium salt and initiator as 100%, the polymer monomer The mass of the body is 80%.
  • the mass proportion of the lithium salt is 10-30%, for example, 11%, 12%, 13%, 14%, based on 100% of the total mass of the polymer monomer, lithium salt and initiator. %, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, etc. in a In the embodiment, the mass proportion of the lithium salt is 19.5% based on the total mass of the polymer monomer, the lithium salt and the initiator being 100%.
  • the mass proportion of the initiator is 0.2-1%, for example, 0.3%, 0.4%, 0.5%, 0.6%, based on 100% of the total mass of the polymer monomer, lithium salt and initiator. %, 0.7%, 0.8%, 0.9%, etc. In an embodiment, based on the total mass of the polymer monomer, lithium salt and initiator being 100%, the mass proportion of the initiator is 0.5%.
  • the heating temperature is 60-80°C, such as 62°C, 64°C, 66°C, 68°C, 70°C, 72°C, 74°C, 76°C, 78°C, and the like.
  • the time of the incubation reaction is 2-5h, such as 2h, 3h, 4h and the like.
  • the preparation method of the flame retardant dispersion includes: mixing and dispersing the flame retardant and a dispersant to obtain the flame retardant dispersion.
  • the dispersing agent includes an organic liquid or an inorganic liquid with a boiling point higher than 100° C., which does not react with the flame retardant and is immiscible with the flame retardant.
  • the temperature of the dispersion in the preparation method of the flame retardant dispersion liquid is 20-30°C, such as 21°C, 22°C, 23°C, 24°C, 25°C, 26°C, 27°C, 28°C, 29°C, etc.
  • the particle size of the flame retardant in the flame retardant dispersion liquid is 0.1 ⁇ m-10 ⁇ m, such as 1 ⁇ m, 2 ⁇ m, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, and the like.
  • the flame retardant dispersion is emulsified prior to the mixing of the flame retardant dispersion, polymer monomer, lithium salt and initiator.
  • the emulsification method includes: adding an emulsifier solution to the flame retardant dispersion liquid to perform emulsification.
  • the emulsifier includes polyethylene glycol, sodium lauryl sulfonate, fatty acid polyoxyethylene ether, gum arabic, sodium alkylbenzene sulfonate, monoglyceryl isostearate, polyoxyethylene Ethane-polyoxypropylene copolymer, cetyltrimethylammonium bromide, styrene maleic anhydride copolymer, non-ionic paraffin micro-emulsifier (NMP), cationic paraffin micro-emulsifier (CMP), anionic paraffin Emulsifier (AMP), OP-10, OP-15, Perigua O-10, water-in-oil waste oil emulsifier (EEO), water-in-oil diesel emulsifier (EDO) or water-in-oil animal and vegetable oil emulsifier any one or a combination of at least two agents (EAP).
  • NMP non-ionic paraffin micro-emulsifier
  • CMP cationic paraffin micro-
  • the method for emulsification includes: using the diluted 10% emulsifier, flame retardant and deionized water for emulsification treatment, and emulsification at 10000-15000 r/min rotation speed for 30 minutes.
  • the pH of the flame retardant dispersion is adjusted to 3-4 prior to the mixing of the flame retardant dispersion, polymer monomer, lithium salt and initiator.
  • the method of adjusting the pH includes adjusting with an acetic acid solution, and in one embodiment, the method of adjusting the pH includes adjusting with a 10% acetic acid solution.
  • the preparation method further includes: after the heat preservation reaction, drying is performed to obtain the electrolyte material in the form of powder particles.
  • the drying is performed in an argon atmosphere.
  • the drying temperature is 70-90°C, such as 72°C, 74°C, 76°C, 78°C, 80°C, 82°C, 84°C, 86°C, 88°C, etc., in one embodiment , the drying temperature is 80°C.
  • the drying time is 20-30h, such as 22h, 24h, 26h, 28h, etc. In one embodiment, the drying time is 24h.
  • the powdered granular electrolyte material is stored in an argon atmosphere.
  • the preparation method includes the following steps:
  • the steps (1) to (6) are all carried out in an argon atmosphere.
  • An embodiment of the present disclosure provides an electrode slurry including the electrolyte material according to an embodiment of the present disclosure.
  • the electrode slurry includes positive electrode slurry or negative electrode slurry.
  • the mass percentage of the electrolyte material in the electrode slurry is 1-20%, such as 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, etc.
  • the electrode paste includes a binder.
  • the adhesive comprises polyvinylidene fluoride (PVDF), polyvinylpyrrolidone (PVP), styrene butadiene rubber (SBR), carboxymethyl cellulose (CMC), polyacrylic acid (PAA), Any one or a combination of at least two of polyethylene oxide (PEO), polyacrylonitrile (PAN), chitosan series, sodium alginate series or natural rubber series (Binder).
  • PVDF polyvinylidene fluoride
  • PVP polyvinylpyrrolidone
  • SBR styrene butadiene rubber
  • CMC carboxymethyl cellulose
  • PAA polyacrylic acid
  • the preparation method of the electrode slurry includes adding the electrolyte material according to an embodiment of the present disclosure during the homogenization process.
  • the present disclosure does not specifically limit the method for homogenizing and the order of adding electrolyte materials, and merely provides a method for homogenizing positive electrode slurry and a method for homogenizing negative electrode slurry.
  • the negative electrode slurry includes the method shown in FIG. 3 , the method shown in FIG. 4 and the method shown in FIG. 5 .
  • Those skilled in the art can prepare according to the aforementioned methods, and can also prepare according to other methods.
  • an electrode sheet whose surface is coated with the electrolyte slurry according to an embodiment of the present disclosure.
  • the electrode sheet includes a positive electrode sheet or a negative electrode sheet.
  • the base material of the electrode sheet includes aluminum foil or copper foil.
  • the preparation method of the electrode sheet includes: coating the electrode slurry according to an embodiment of the present disclosure on a substrate, followed by rolling.
  • the thickness of the coating is 0.1-100 ⁇ m, such as 1 ⁇ m, 10 ⁇ m, 20 ⁇ m, 30 ⁇ m, 40 ⁇ m, 50 ⁇ m, 60 ⁇ m, 70 ⁇ m, 80 ⁇ m, 90 ⁇ m and the like.
  • the width of the coating is 0.1-1000mm, such as 20mm, 50mm, 100mm, 200mm, 300mm, 400mm, 500mm, 600mm, 700mm, 800mm, 900mm, and the like.
  • the areal density of the coating is 0.1 mg/cm 2 -100 mg/cm 2 , such as 2 mg/cm 2 , 10 mg/cm 2 , 20 mg/cm 2 , 30 mg/cm 2 , 40 mg/cm 2 , 50 mg/cm 2 , 60 mg/cm 2 , 70 mg/cm 2 , 80 mg/cm 2 , 90 mg/cm 2 , etc., in one embodiment, the surface density of the coating is 5 mg/cm 2 .
  • the coating method includes any one or a combination of at least two of blade coating, transfer coating or extrusion coating. In one embodiment, the coating method includes transfer coating. coating.
  • the rolling is performed under dry conditions.
  • the dew point temperature of the drying room is below -50°C, such as -60°C, -70°C, -80°C, and the like.
  • the temperature of the rolling is 180°C-250°C, such as 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, etc.
  • the temperature was 180°C.
  • the rolling pressure is 50MPa-500Mpa, such as 100MPa, 200MPa, 300MPa, 400MPa, etc. In one embodiment, the rolling pressure is 300Mpa.
  • the diameter of the rolling roller is 0.1mm-1000mm, such as 10mm, 10mm, 100mm, 200mm, 300mm, 400mm, 500mm, 600mm, 700mm, 800mm, 900mm, etc.
  • the roll diameter of the rolling was 500 mm.
  • the thickness of the electrode paste after rolling is 0.1-50 ⁇ m, such as 5 ⁇ m, 10 ⁇ m, 15 ⁇ m, 20 ⁇ m, 25 ⁇ m, 30 ⁇ m, 35 ⁇ m, 40 ⁇ m, 45 ⁇ m, and the like.
  • the rolling density is 2.6-4.0 mg/cm 3 , such as 2.8 mg/cm 3 , 3 mg/cm 3 , 3.2 mg/cm 3 , and 3.4 mg/cm 3 . 3. 3.6 mg/cm 3 , 3.8 mg/cm 3 , etc., in one embodiment, in the positive electrode sheet, the rolling density is 3.6 mg/cm 3 .
  • the rolling density is 1.0-1.8 mg/cm 3 , for example, 1.1 mg/cm 3 , 1.2 mg/cm 3 , 1.3 mg/cm 3 , 1.4 mg/cm 3 . cm 3 , 1.5 mg/cm 3 , 1.6 mg/cm 3 , 1.7 mg/cm 3 , etc., in one embodiment, in the negative electrode sheet, the rolling density is 1.6 mg/cm 3 .
  • An embodiment of the present disclosure provides a battery cell including the electrode sheet described in an embodiment of the present disclosure.
  • the battery cells are semi-solid battery cells.
  • An embodiment of the present disclosure provides a battery including the battery cell according to an embodiment of the present disclosure.
  • the flame retardant@ion conductive polymer electrolyte core-shell material will not be oxidized due to the high voltage of the positive electrode or reduced due to the low voltage of the negative electrode at the positive and negative electrodes.
  • the conductive polymer electrolyte core structure can play the role of conducting lithium ions, and the battery will not reduce the rate performance due to the addition of electrolyte materials.
  • the battery heats up, the core-shell structure is heated, melts and ruptures, and the flame retardant overflows, which plays the role of flame retardant and fire extinguishing, which is of great significance in safety.
  • the battery is a semi-solid battery.
  • the battery is a lithium battery.
  • the semi-solid battery can be assembled in many ways.
  • the pole pieces can be assembled by lamination or by winding.
  • the method of assembling the battery is not limited; After the liquid is aged at 45°C for 24 hours, the formation process is carried out.
  • the injection and formation processes are not limited; the assembled battery can be a soft pack battery, a square aluminum shell battery, or a cylindrical battery. In one embodiment, the assembled battery For soft pack battery.
  • An embodiment of the present disclosure provides an application of the battery according to an embodiment of the present disclosure, where the battery is applied to electronic products or new energy vehicles.
  • FIG. 1 is a homogenization method of positive electrode slurry in an embodiment of the present disclosure.
  • FIG. 2 is a homogenization method of positive electrode slurry in an embodiment of the present disclosure.
  • FIG. 3 is a homogenization method of negative electrode slurry in an embodiment of the present disclosure.
  • FIG. 4 is a homogenizing method of negative electrode slurry in an embodiment of the present disclosure.
  • FIG. 5 is a homogenization method of negative electrode slurry in an embodiment of the present disclosure.
  • FIG. 6 is a schematic diagram of the preparation process of the electrolyte material according to the embodiment of the present disclosure.
  • FIG. 7 is a schematic diagram of the morphological change of the electrolyte material according to the embodiment of the present disclosure.
  • FIG. 8 is a schematic diagram of an internal layered structure of an electrolyte material according to an embodiment of the present disclosure.
  • FIG. 9 is a schematic diagram of an external layered structure of an electrolyte material according to an embodiment of the present disclosure.
  • 10a is a scanning electron microscope (SEM) photograph of an electrolyte material of an embodiment of the present disclosure.
  • Figure 10b is a SEM photograph of the electrolyte material of an embodiment of the present disclosure.
  • FIG. 11 is a graph of the temperature-voltage test data of a 5Ah nickel-cobalt-manganese ternary-graphite (NCM-Gr) cell of an application example of the present disclosure through a 150° C. hot box experiment.
  • NCM-Gr nickel-cobalt-manganese ternary-graphite
  • Fig. 12a is a state diagram of a 5Ah NCM-Gr battery cell of an application example of the present disclosure after passing through a 150°C hot box.
  • Figure 12b is a state diagram of the 5Ah NCM-Gr battery cell of the comparative application example after passing through a 150°C hot box.
  • Figure 13a is a comparison diagram of acupuncture safety of the 5Ah NCM-Gr battery cell of the application example of the present disclosure.
  • Figure 13b is a comparison diagram of acupuncture safety of the 5Ah NCM-Gr battery cell of the comparative application example.
  • FIG. 14 is a graph of 1C cycle life data of a 5Ah NCM-Gr battery cell of an application example of the present disclosure.
  • This embodiment provides an electrolyte material (flame retardant@ionic conductive polymer electrolyte core-shell material), the preparation method of which is as follows (the following steps are all carried out in an argon atmosphere, and a condensation reflux device is used, as shown in FIG. 6 ) :
  • the preparation process of this embodiment includes first depositing an emulsifier on the surface of the flame retardant particles, and then coating the ion conductive polymer, as shown in FIG. 7 .
  • FIG 8 The schematic diagram of the internal layered structure of the flame retardant@ion conductive polymer electrolyte core-shell material prepared in this example is shown in Figure 8, the schematic diagram of the external structure is shown in Figure 9, and the SEM photos are shown in Figures 10a and 10b.
  • This embodiment provides an electrolyte material, the preparation method of which is as follows (the following steps are all performed in an argon atmosphere):
  • This embodiment provides an electrolyte material, the preparation method of which is as follows (the following steps are all performed in an argon atmosphere):
  • step (4) the polymer monomer used is ethylene ethylene carbonate, and the obtained polymer electrolyte is polyethylene ethylene carbonate (melting temperature is 210° C.).
  • step (4) the polymer monomer used is triethylene glycol diacrylate, and the obtained polymer electrolyte is polytriethylene glycol diacrylate (melting temperature is 250° C.). ).
  • step (4) the polymer monomer used is 1.6-hexanediol diacrylate, and the obtained polymer electrolyte is 1.6-hexanediol polydiacrylate (melting temperature is 1.6-hexanediol). 140°C).
  • step (4) the polymer monomer used is pentaerythritol tetraacrylate, and the obtained polymer electrolyte is polypentaerythritol tetraacrylate (melting temperature is 260° C.).
  • the mass proportion of the flame retardant in the electrolyte material is 5% (Example 8), 20% (Example 9), 3% (Example 10), 25% (Example 11) .
  • Example 4 The difference from Example 4 is that the preparation method of the electrolyte material is as follows:
  • Positive electrode slurry prepared according to the method shown in Figure 1, to obtain a positive electrode slurry with an electrolyte material content of 10%;
  • the negative electrode slurry is prepared according to the method shown in FIG. 3 to obtain a negative electrode slurry with an electrolyte material content of 10%;
  • Positive electrode sheet coat the prepared positive electrode slurry on the aluminum foil with a coating thickness of 50 ⁇ m, a coating width of 500 mm, and a coating length of 10 m; coating surface density: 5 mg/cm 2 ; coating method: Transfer coating; rolling under the drying condition of dew point -50°C, rolling temperature is 180°C, pressure is 300Mpa, roll diameter is 500mm, thickness after rolling is 25 ⁇ m, and compaction density is 3.6mg/cm 3 ;
  • Negative electrode sheet coat the prepared negative electrode slurry on the aluminum foil, the coating thickness is 50 ⁇ m, the coating width is 500 mm, and the coating length is 10 m; coating surface density: 5 mg/cm2; coating method: transfer Coating; rolling under the drying condition of dew point -50°C, the rolling temperature is 180°C, the pressure is 300Mpa, the roller diameter is 500mm, the thickness after rolling is 25 ⁇ m, and the compaction density is 1.6mg/cm 3 .
  • Semi-solid battery (soft pack): The positive and negative electrode sheets are assembled by lamination. After the assembly, the battery is injected with liquid. After the liquid injection, it is aged at a high temperature of 45 °C for 24 hours. battery cells).
  • Figure 11 is a graph of the temperature-voltage test data of the 5Ah NCM-Gr cell in the application example 1 passing through the 150°C hot box.
  • the figure shows that the NCM-Gr cell with the addition of flame retardant@ion conductive polymer can pass the 150°C hot box smoothly. , which proves that the material has excellent flame retardant properties.
  • Figures 12a and 12b are the state diagrams of the 5Ah NCM-Gr battery cells of Application Example 1 and Comparative Application Example 2 respectively after passing through a 150°C hot box.
  • Figure 12a is basically damaged, while Figure 12b has been burned, which proves that the electrolyte material provided by the present disclosure The flame retardant performance of the battery can be effectively improved, and the safety is higher.
  • Figures 13a and 13b are the comparison charts of the acupuncture safety of the 5Ah NCM-Gr battery cells of Application Example 1 and Comparative Application Example 2, respectively.
  • the acupuncture can be passed smoothly, while the acupuncture in Figure 13b caught fire, which further proves
  • the electrolyte material of the present application can effectively improve the flame retardant performance of the battery.
  • Figure 14 is a graph of the 1C cycle life data of the 5Ah NCM-Gr battery cell of Application Example 1. The figure shows that after 200 cycles, the capacity retention rate is still 93.7%, which proves that the electrolyte material provided by the present disclosure is applied to the battery and can Obtain good cycle performance.
  • the temperature box is raised from room temperature to 150 ⁇ 2°C at a rate of 5°C/min, and the heating is stopped after maintaining this temperature for 30 minutes;
  • the first effect test conditions the ambient temperature is 25 °C;
  • Constant current and constant voltage charging 0.05C constant current charging (CC) for 22h to 4.25V, constant voltage charging (CV) to 0.01C;
  • Cycle performance test conditions the test temperature is 25 °C;
  • the rate performance of 1C/0.33C is obtained by the test. Under other conditions, the rate performance test parameters of 0.1C/0.1C, 0.33C/0.33C, 0.33/0.5C, and 0.33/2C refer to the above conditions.
  • the electrolyte material provided by the present disclosure is applied in a semi-solid battery, and has excellent flame retardant performance, as well as excellent cycle performance and rate performance.

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Abstract

本文公布一种电解质材料及其制备方法和应用，电解质材料包括核体和包覆在核体外的壳体，核体包括阻燃剂颗粒，壳体包括离子导电聚合物，其中，离子导电聚合物包括锂盐和聚合物电解质的组合。

Description

一种电解质材料及其制备方法和应用 技术领域
本公开涉及电池技术领域，例如涉及一种电解质材料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，人们对于清洁能源需求变得日益重视；同时，新能源汽车日益普及，对于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。目前商用锂电池已经出现能量密度的瓶颈，在高能量密度方面很难有提升，固态电池作为下一代电池已经被提到了前沿位置，但是固态电池研发难度大，工艺要求较高，目前还不能马上实现量产，因此半固态电池作为一种过渡产品应运而生。
固态电池从制备方法上划分主要可以分为：①半固态电池；②全固态电池，其中全固态电池正负极隔膜之间是固固接触，Li+传导阻力较大，目前性能很难达到传统液态电池水准；半固态电池作为传统液态电池到全固态电池中间的过渡态，无论在制备的可操作性、电池的倍率性能、循环性能都与传统液态电池十分接近，安全性能更是优于传统液态电池。
聚合物固态电解质作为安全、密度小的材料非常受到关注，但是将聚合物固态电解质使用传统方法添加到电极中，也会有很大问题，因为聚合物电解质材料本身很软，杨氏模量较低，添加后电池在辊压过程中，由于电解质很软，会造成电极延展较大，压实密度很难提升。
新能源汽车自燃现象层出不穷，人们一直尝试开发更加安全可靠的新型电池，全固态电池因其不含电解液成分，在电芯内部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，在一定程度上改善电芯的安全性能，是目前最接近也最易实现量产的过渡产品。
电解液在锂离子电池热失控过程中扮演的角色非常关键，目前，从材料角度看，防止锂离子电池热失控起火燃烧爆炸的安全性改进策略众多，采用阻燃电解质是最经济简单有效的策略，能够有效地降低锂离子电池热失控燃烧爆炸风险，并极大降低热失控带来的人员财产伤害；但是在电池中添加阻燃剂往往会降低电池的循环性能和倍率性能，对电池电性能的影响很大，如果添加量较少也不会起到阻燃作用，所以目前添加阻燃剂的电池性能都不是很理想，难以兼顾阻燃性能和电化学性能。
CN105261742A公开了一种硫系半固态锂电池及其制备方法，该电池由半固态硫系正极、半固态电解质与锂片负极堆叠形成；该半固态硫系正极是先由含锂盐聚合物、硫系材料、碳导电剂混合成半固态，再以铝箔或镍网为集流体形成；该半固态电解质是由多孔无机氧化物与含锂盐聚合物混合而成；该含锂盐聚合物是由流动态聚合物与锂盐混合而成。
CN110265715A公开了一种锂电池半固态电解质专用凝胶剂及制备方法，所述凝胶剂是先将聚合物基体与羟丙基甲基纤维素、阻燃剂混合研磨得到复合微粒，然后将全氢聚硅氮烷、多孔无机物与氨水混合后喷覆在复合微粒表面，最后将制得包覆型复合微粒与分散剂利用气流混合机完全分散而制得。
因此，本领域亟待开发一种能够兼具阻燃性能以及电化学性能的电解质材料。
发明内容
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。
本公开提供一种电解质材料及其制备方法和应用。
本公开在一实施例中提供一种电解质材料，包括核体和包覆在核体外的壳体，所述核体包括阻燃剂颗粒，所述壳体包括离子导电聚合物；
所述离子导电聚合物包括锂盐和聚合物电解质的组合。
本公开在一实施例中使用离子导电聚合物材料包覆阻燃剂形成一种核壳材料，将此材料添加到电极极片中，电池遇到安全性问题，机械滥用条件下如针刺、压缩、冲击的情况，电滥用条件下如过充电、强制短路，热滥用条件下如热箱、热冲击等情况发生，电池会由于内短路发热，在发热过程中，离子导电聚合物电解质融化破裂，释放出阻燃剂，阻燃剂发挥阻燃作用，在短时间内阻止电池热失控，达到人员安全离开的目的，在正常使用状态下，阻燃剂被聚合物电解质包裹，不会影响电池的循环性能和倍率性能，从而具有优异的电化学性能。
此外，聚合物电解质具有很好的弹性，可以降低负极的膨胀。相比于常规添加聚合物电解质的电极，很难提高压实密度的情况，本公开中，通过添加一种阻燃剂@离子导电聚合物电解质核壳材料应用于半固态电池从而达到提高半固态电池安全性，同时又使聚合物电解质充分分散在电极极片中，显著提高固态电解质含量，保证了固态电解质的均匀分布，提高了锂离子通道，保证锂离子在极片内的正常迁移，不会影响电池的电性能，还可以保证电极有较高的压实密度，而且极片不容易发生较高延展。
本公开一实施例提供的电解质材料用于电极极片中，在电池遇到安全性问 题，内短路发热时，在发热过程中，离子导电聚合物电解质融化破裂，释放出阻燃剂，阻燃剂发挥阻燃作用，在短时间内阻止电池热失控，达到人员安全离开的目的，在正常使用状态下，阻燃剂被聚合物电解质包裹，不会影响电池的循环性能和倍率性能，从而具有优异的电化学性能。
本公开一实施例提供的电解质材料用于电极极片，可以提高压实密度，同时降低负极膨胀。
在一实施例中，所述电解质材料中阻燃剂的质量占比为5-20％，例如6％、7％、8％、9％、10％、11％、12％、13％、14％、15％、16％、17％、18％、19％等，在一实施例中，所述电解质材料中阻燃剂的质量占比为10％。
本公开提供的一实施例中使阻燃剂的占比为5-20％，从而获得针刺和热箱实验不起火效果，占比过低，会导致着火，占比过高，会导致电池容量降低。
在一实施例中，所述核体的直径为0.5～10μm，例如1μm、2μm、3μm、4μm、5μm、6μm、7μm、8μm、9μm等。
在一实施例中，所述壳体的厚度为100-500nm，例如150nm、200nm、250nm、300nm、350nm、400nm、450nm等。
在一实施例中，所述阻燃剂包括磷酸三甲酯(TMP)、磷酸三乙酯(TEP)、磷酸三丁酯(TBP)、三(2,2,2-三氟乙基)亚磷酸酯(TFP)、磷酸三苯酯(TPP)、亚磷酸酯或磷腈类阻燃材料中的任意一种或至少两种组合。
在一实施例中，所述锂盐占所述离子导电聚合物质量的1～20％，例如2％、3％、4％、5％、6％、7％、8％、9％、10％、11％、12％、13％、14％、15％、16％、17％、18％、19％等，在一实施例中，所述锂盐占所述离子导电聚合物质量的12％。
在一实施例中，所述锂盐包括高氯酸锂(LiClO 4)、双三氟甲烷磺酰亚胺锂 (LiTFSI)、双氟磺酰亚胺锂(LiFSI)、双乙二酸硼酸锂(LiBOB)或四氟硼酸锂(LiBF 4)中的任意一种或至少两种组合。
在一实施例中，所述聚合物电解质的熔融温度为150-250℃，例如160℃、170℃、180℃、190℃、200℃、210℃、220℃、230℃、240℃等，在一实施例中，所述聚合物电解质的熔融温度为200℃。
本公开提供的一实施例中选用上述熔融温度，从而使电解质熔融后成为液体效果，熔融温度过低，会导致聚合物电解质非液态，不能够均匀包覆阻燃剂，熔融温度过高，会导致聚合物电解质氧化分解。
在一实施例中，所述聚合物电解质包括聚氧化乙烯(PEO)、聚丙烯腈(PAN)、聚甲基丙烯酸甲酯(PMMA)、聚偏二氟乙烯(PVdF)、聚乙二醇(PEG)、聚乙二醇二丙烯酸酯(PEGDA)或聚碳酸亚乙烯酯(PVCA)中的任意一种或至少两种组合。
本公开提供的一实施例中，聚合物电解质因其含有与电极浆料中常用的粘接剂相同的分子链段，其与粘接剂具有更好的亲和性和柔韧性，更有电极活性物质之间的粘结性能。聚合物电解质含有与粘结剂相同的链段，相同链段相互缠结，更会减小硅负极的膨胀。同时，聚合物电解质与电解液不相容，不能够溶解在电解液中，减少电解液因为聚合物溶出而变得更加粘稠，降低电导率，导致倍率性能和循环性能下降。
在一实施例中，在所述阻燃剂颗粒和所述离子导电聚合物之间存在乳化剂。
在一实施例中，所述乳化剂沉积在所述阻燃剂颗粒表面。
在一实施例中，在阻燃剂颗粒表面沉积乳化剂，这是由于乳化剂表面有亲水亲油基团，使用乳化剂可以使聚合物电解质更容易与阻燃剂微球结合从而获 得包覆均匀且密实的效果。
在一实施例中，所述乳化剂包括聚乙二醇、十二烷基磺酸钠、脂肪酸聚氧乙烯醚、阿拉伯胶、烷基苯磺酸钠、异硬脂酸单甘油酯、聚氧乙烷-聚氧丙烷共聚体、十六烷基三甲基溴化铵、苯乙烯马来酸酐共聚物中、非离子石蜡微乳化剂(NMP)、阳离子石蜡微乳化剂(CMP)、阴离子石蜡乳化剂(AMP)、OP-10、OP-15、平平加O-10、油包水型废机油乳化剂(EEO)、油包水型柴油乳化剂(EDO)或油包水型动植物油乳化剂(EAP)的任意一种或至少两种组合。
本公开在一实施例中提供一种本公开一实施例所述的电解质材料的制备方法，包括：将阻燃剂分散液、聚合物单体、锂盐和引发剂混合，分散，得到混合溶液，搅拌并加热，保温反应，得到所述电解质材料。
本公开一实施例提供的电解质材料的制备方法能够制备得到具有核壳结构的电解质材料，且该制备方法操作简单、材料便宜、阻燃效果明显且不影响电池其他性能。
在一实施例中，所述制备方法在氩气氛围中进行。
在一实施例中，所述制备方法还包括使用回流冷凝设备。
在一实施例中，所述分散的温度为80-90℃，例如81℃、82℃、83℃、84℃、85℃、86℃、87℃、88℃、89℃等。
在一实施例中，所述引发剂包括偶氮二异丁腈(AIBN)或偶氮二异庚腈(V65)至少之一。
在一实施例中，以聚合物单体、锂盐和引发剂的总质量为100％计，所述聚合物单体的质量占比为70-90％，例如72％、74％、76％、78％、80％、82％、84％、86％、88％等，在一实施例中，以聚合物单体、锂盐和引发剂的总质量为100％ 计，所述聚合物单体的质量占比为80％。
在一实施例中，以聚合物单体、锂盐和引发剂的总质量为100％计，所述锂盐的质量占比为10-30％，例如11％、12％、13％、14％、15％、16％、17％、18％、19％、20％、21％、22％、23％、24％、25％、26％、27％、28％、29％等，在一实施例中，以聚合物单体、锂盐和引发剂的总质量为100％计，所述锂盐的质量占比为19.5％。
在一实施例中，以聚合物单体、锂盐和引发剂的总质量为100％计，所述引发剂的质量占比为0.2-1％，例如0.3％、0.4％、0.5％、0.6％、0.7％、0.8％、0.9％等，在一实施例中，以聚合物单体、锂盐和引发剂的总质量为100％计，所述引发剂的质量占比为0.5％。
在一实施例中，所述加热的温度为60-80℃，例如62℃、64℃、66℃、68℃、70℃、72℃、74℃、76℃、78℃等。
在一实施例中，所述保温反应的时间为2-5h，例如2h、3h、4h等。
在一实施例中，所述阻燃剂分散液的制备方法包括：将阻燃剂与分散剂混合，分散，得到所述阻燃剂分散液。
在一实施例中，所述分散剂包括沸点高于100℃且与阻燃剂不发生反应、与阻燃剂不互溶的有机液体或无机液体。
在一实施例中，所述阻燃剂分散液的制备方法中所述分散的温度为20-30℃，例如21℃、22℃、23℃、24℃、25℃、26℃、27℃、28℃、29℃等。
在一实施例中，所述阻燃剂分散液中阻燃剂的粒径为0.1μm-10μm，例如1μm、2μm、3μm、4μm、5μm、6μm、7μm、8μm、9μm等。
在一实施例中，在所述将阻燃剂分散液、聚合物单体、锂盐和引发剂混合之前，将所述阻燃剂分散液进行乳化。
在一实施例中，所述乳化的方法包括：在所述阻燃剂分散液中添加乳化剂溶液，进行乳化。
在一实施例中，所述乳化剂包括聚乙二醇、十二烷基磺酸钠、脂肪酸聚氧乙烯醚、阿拉伯胶、烷基苯磺酸钠、异硬脂酸单甘油酯、聚氧乙烷-聚氧丙烷共聚体、十六烷基三甲基溴化铵、苯乙烯马来酸酐共聚物中、非离子石蜡微乳化剂(NMP)、阳离子石蜡微乳化剂(CMP)、阴离子石蜡乳化剂(AMP)、OP-10、OP-15、平平加O-10、油包水型废机油乳化剂(EEO)、油包水型柴油乳化剂(EDO)或油包水型动植物油乳化剂(EAP)的任意一种或至少两种组合。
在一实施例中，所述进行乳化的方法包括：使用已稀释好的10％乳化剂、阻燃剂和去离子水进行乳化处理，在10000～15000r/min转速下乳化30min。
在一实施例中，在所述将阻燃剂分散液、聚合物单体、锂盐和引发剂混合之前，将所述阻燃剂分散液的pH调节至3-4。
在一实施例中，所述调节pH的方法包括使用乙酸溶液进行调节，在一实施例中，所述调节pH的方法包括使用10％的乙酸溶液进行调节。
在一实施例中，所述制备方法还包括：所述保温反应之后，进行干燥，得到粉体颗粒状的电解质材料。
在一实施例中，所述干燥在氩气氛围中进行。
在一实施例中，所述干燥的温度为70-90℃，例如72℃、74℃、76℃、78℃、80℃、82℃、84℃、86℃、88℃等，在一实施例中，所述干燥的温度为80℃。
在一实施例中，所述干燥的时间为20-30h，例如22h、24h、26h、28h 等，在一实施例中，所述干燥的时间为24h。
在一实施例中，所述粉体颗粒状的电解质材料在氩气氛围中保存。
在一实施例中，所述制备方法包括如下步骤：
(1)将阻燃剂与分散剂混合，在20-30℃下分散，得到阻燃剂的粒径为0.1μm-10μm的阻燃剂分散液；
(2)在所述阻燃剂分散液中添加乳化剂溶液，使用蒸馏水进行乳化处理；
(3)使用10％乙酸溶液将所述阻燃剂分散液的pH调节至3-4；
(4)将所述阻燃剂分散液、聚合物单体、锂盐和引发剂混合，在80-90℃下分散，得到聚合物单体含量为70-90％、锂盐含量为10-30％、引发剂含量为0.2-1％的混合溶液；
(5)将所述混合溶液搅拌并加热至60-80℃，保温反应2-5h，得到所述电解质材料；
(6)在70-90℃干燥20-30h，得到粉体颗粒状的电解质材料；
所述步骤(1)至(6)均在氩气氛围中进行。
本公开一实施例中提供一种包含本公开一实施例所述的电解质材料的电极浆料。
在一实施例中，所述电极浆料包括正极浆料或负极浆料。
在一实施例中，所述电解质材料占所述电极浆料的质量百分比为1-20％，例如2％、3％、4％、5％、6％、7％、8％、9％、10％、11％、12％、13％、14％、15％、16％、17％、18％、19％等。
在一实施例中，所述电极浆料中包括粘接剂。
在一实施例中，所述粘接剂包括聚偏二氟乙烯(PVDF)、聚乙烯吡咯烷酮 (PVP)、丁苯橡胶(SBR)、羟甲基纤维素(CMC)、聚丙烯酸(PAA)、聚环氧乙烯(PEO)、聚丙烯腈(PAN)、壳聚糖系列、海藻酸钠系列或天然胶系列(Binder)中的任意一种或至少两种组合。
在一实施例中，所述电极浆料的制备方法包括在匀浆的过程中添加本公开一实施例所述的电解质材料。
本公开对于匀浆的方法以及电解质材料的添加顺序不做具体限定，仅示例性的提供正极浆料的匀浆方法和负极浆料的匀浆方法，其中，正极浆料的匀浆方法包括如图1所示的方法和如图2所示的方法，负极浆料包括如图3所示的方法、如图4所示的方法以及如图5所示的方法。本领域技术人员可以按照前述方法进行制备，也可以按照其他方法制备。
本公开在一实施例中提供一种表面涂覆有本公开一实施例所述的电解质浆料的电极片。
在一实施例中，所述电极片包括正极电极片或负极电极片。
在一实施例中，所述电极片的基材包括铝箔或铜箔。
在一实施例中，所述电极片的制备方法包括：在基材上涂布本公开一实施例所述的电极浆料，随后进行辊压。
在一实施例中，所述涂布的厚度为0.1-100μm，例如1μm、10μm、20μm、30μm、40μm、50μm、60μm、70μm、80μm、90μm等。
在一实施例中，所述涂布的宽度为0.1-1000mm，例如20mm、50mm、100mm、200mm、300mm、400mm、500mm、600mm、700mm、800mm、900mm等。
在一实施例中，所述涂布的面密度为0.1mg/cm 2-100mg/cm 2，例如2mg/cm 2、 10mg/cm 2、20mg/cm 2、30mg/cm 2、40mg/cm 2、50mg/cm 2、60mg/cm 2、70mg/cm 2、80mg/cm 2、90mg/cm 2等，在一实施例中，所述涂布的面密度为5mg/cm 2。
在一实施例中，所述涂布的方法包括刮刀涂布、转移涂布或挤压涂布中的任意一种或至少两种组合，在一实施例中，所述涂布的方法包括转移涂布。
在一实施例中，所述辊压在干燥条件下进行。
在一实施例中，所述干燥间的露点温度在-50℃以下，例如-60℃、-70℃、-80℃等。
在一实施例中，所述辊压的温度为180℃-250℃，例如190℃、200℃、210℃、220℃、230℃、240℃等，在一实施例中，所述辊压的温度为180℃。
在一实施例中，所述辊压的压力为50MPa-500Mpa，例如100MPa、200MPa、300MPa、400MPa等，在一实施例中，所述辊压的压力为300Mpa。
在一实施例中，所述辊压的辊直径为0.1mm-1000mm，例如10mm、10mm、100mm、200mm、300mm、400mm、500mm、600mm、700mm、800mm、900mm等，在一实施例中，所述辊压的辊直径为500mm。
在一实施例中，所述辊压后电极浆料的厚度为0.1-50μm，例如5μm、10μm、15μm、20μm、25μm、30μm、35μm、40μm、45μm等。
在一实施例中，所述正极电极片中，辊压的压实密度为2.6-4.0mg/cm 3，例如2.8mg/cm 3、3mg/cm 3、3.2mg/cm 3、3.4mg/cm 3、3.6mg/cm 3、3.8mg/cm 3等，在一实施例中，所述正极电极片中，辊压的压实密度为3.6mg/cm3。
在一实施例中，所述负极电极片中，辊压的压实密度为1.0-1.8mg/cm 3，例如1.1mg/cm 3、1.2mg/cm 3、1.3mg/cm 3、1.4mg/cm 3、1.5mg/cm 3、1.6mg/cm 3、1.7mg/cm 3等，在一实施例中，所述负极电极片中，辊压的压实密度为1.6mg/cm 3。
本公开一实施例中提供一种包含本公开一实施例所述的电极片的电池电芯。
在一实施例中，所述电池电芯为半固态电池电芯。
本公开一实施例中提供一种包含本公开一实施例所述的电池电芯的电池。
本公开一实施例提供的电池在使用过程中，阻燃剂@离子导电聚合物电解质核壳材料在正负极不会因为正极的高压被氧化，也不会因为负极的低电压被还原，离子导电聚合物电解质核结构可以起到导通锂离子的作用，电池不会因为添加电解质材料而降低倍率性能。电池在热滥用，电滥用，机械滥用过程中，电池发热，核壳结构受热融化破裂，阻燃剂溢出，起到阻燃灭火的作用，在安全性中意义重大。
在一实施例中，所述电池为半固态电池。
在一实施例中，所述电池为锂电池。
本公开中，所述半固态电池的组装方式可以是很多种，极片可以通过叠片方式进行组装，也可以通过卷绕方式进行组装，组装电池方法不限定；组装后电池进行注液，注液后45℃高温老化24h，之后进行化成流程，注液及化成流程不限定；组装的电池可以是软包电池，也可以是方形铝壳电池，圆柱电池，在一实施例中，组装的电池为软包电池。
本公开一实施例中提供一种本公开一实施例所述的电池的应用，所述电池应用于电子产品或新能源汽车。
在阅读并理解了附图和详细描述后，可以明白其他方面。
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，与本公开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是本公开的一实施例中正极浆料的匀浆方法。
图2是本公开的一实施例中正极浆料的匀浆方法。
图3是本公开的一实施例中负极浆料的匀浆方法。
图4是本公开的一实施例中负极浆料的匀浆方法。
图5是本公开的一实施例中负极浆料的匀浆方法。
图6是本公开实施例的电解质材料的制备流程示意图。
图7是本公开实施例的电解质材料的形态变化示意图。
图8是本公开实施例的电解质材料的内部层状结构示意图。
图9是本公开实施例的电解质材料的外部层状结构示意图。
图10a是本公开实施例的电解质材料的扫描电镜(SEM)照片。
图10b是本公开实施例的电解质材料的SEM照片。
图11是本公开应用例的5Ah镍钴锰三元-石墨(NCM-Gr)电芯通过150℃热箱实验温度-电压测试数据图。
图12a是本公开应用例的5Ah NCM-Gr电池电芯通过150℃热箱后状态图。
图12b是对比应用例的5Ah NCM-Gr电池电芯通过150℃热箱后状态图。
图13a是本公开应用例的5Ah NCM-Gr电池电芯的针刺安全性对比图。
图13b是对比应用例的5Ah NCM-Gr电池电芯的针刺安全性对比图。
图14是本公开应用例的5Ah NCM-Gr电池电芯1C循环寿命数据图。
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。
实施例1
本实施例提供一种电解质材料(阻燃剂@离子导电聚合物电解质核壳材料)，其制备方法如下(以下步骤均在氩气氛围中进行，且采用冷凝回流装置， 如果图6所示)：
(1)将10g阻燃剂(乙氧基五氟环磷腈)与30g分散剂(去离子水)混合，在25℃下分散，得到阻燃剂分散液(粒径为5μm)；
(2)在所述阻燃剂分散液中添加1g乳化剂溶液(10％的OP-10水溶液)，使用蒸馏水进行乳化处理；
(3)使用10％乙酸溶液将所述阻燃剂分散液的pH调节至3-4；
(4)将所述阻燃剂分散液、聚合物单体(碳酸亚乙烯酯)、锂盐(LITFSI)和引发剂(偶氮二异丁腈)混合，在85℃下分散，得到聚合物单体含量为80％、锂盐含量为19.5％、引发剂含量为0.5％(以聚合物单体、锂盐和引发剂的总质量为100％计)的混合溶液；
(5)将所述混合溶液搅拌并加热至70℃，保温反应4h，得到所述电解质材料。
(6)在80℃干燥24h，得到粉体颗粒状的电解质材料(以阻燃剂为核，聚碳酸亚乙烯酯为壳(熔融温度为180℃)，阻燃剂质量占比为10％)。
本实施例的制备过程包括先在阻燃剂颗粒表面沉积乳化剂，再包覆离子导电聚合物，如图7所示。
本实施例制备得到的阻燃剂@离子导电聚合物电解质核壳材料的内部层状结构示意图如图8，外部结构示意图如图9，SEM照片如图10a和10b。
实施例2
本实施例提供一种电解质材料，其制备方法如下(以下步骤均在氩气氛围中进行)：
(1)将10g阻燃剂(六氟环磷腈)与30g分散剂(去离子水)混合，在20℃ 下分散，得到阻燃剂分散液(粒径为0.1μm)；
(2)在所述阻燃剂分散液中添加1g乳化剂溶液(10％的OP-10水溶液)，使用蒸馏水进行乳化处理；
(3)使用10％乙酸溶液将所述阻燃剂分散液的pH调节至3-4；
(4)将所述阻燃剂分散液、聚合物单体(丙烯腈)、锂盐(LITFSI)和引发剂(偶氮二异丁腈)混合，在80℃下分散，得到聚合物单体含量为70％、锂盐含量为29％、引发剂含量为1％(以聚合物单体、锂盐和引发剂的总质量为100％计)的混合溶液；
(5)将所述混合溶液搅拌并加热至60℃，保温反应5h，得到所述电解质材料。
(6)在70℃干燥30h，得到粉体颗粒状的电解质材料(以阻燃剂为核，聚丙烯腈为壳(熔融温度为205℃)，阻燃剂质量占比为10％)。
实施例3
本实施例提供一种电解质材料，其制备方法如下(以下步骤均在氩气氛围中进行)：
(1)将10g阻燃剂(三(2,2,2-三氟乙基)亚磷酸酯)与30g分散剂(无水乙醇)混合，在30℃下分散，得到阻燃剂分散液(粒径为10μm)；
(2)在所述阻燃剂分散液中添加1g乳化剂溶液(10％的OP-10水溶液)，使用蒸馏水进行乳化处理；
(3)使用10％乙酸溶液将所述阻燃剂分散液的pH调节至3-4；
(4)将所述阻燃剂分散液、聚合物单体(具体为甲基丙烯酸甲酯)、锂盐(具体为LiTFSI)和引发剂(具体为偶氮二异丁腈)混合，在90℃下分散，得 到聚合物单体含量为89.8％、锂盐含量为10％、引发剂含量为0.2％(以聚合物单体、锂盐和引发剂的总质量为100％计)的混合溶液；
(5)将所述混合溶液搅拌并加热至70℃，保温反应4h，得到所述电解质材料。
(6)在80℃干燥24h，得到粉体颗粒状的电解质材料(以阻燃剂为核，聚甲基丙烯酸甲酯为壳(熔融温度为196℃)，阻燃剂质量占比为10％)。
实施例4
与实施例1的区别在于，步骤(4)中，所使用的聚合物单体为碳酸乙烯亚乙酯，得到的聚合物电解质为聚碳酸乙烯亚乙酯(熔融温度为210℃)。
实施例5
与实施例1的区别在于，步骤(4)中，所使用的聚合物单体为三乙二醇二丙烯酸酯，得到的聚合物电解质为聚三乙二醇二丙烯酸酯(熔融温度为250℃)。
实施例6
与实施例1的区别在于，步骤(4)中，所使用的聚合物单体为二丙烯酸1.6-己二醇酯，得到的聚合物电解质为聚二丙烯酸1.6-己二醇酯(熔融温度为140℃)。
实施例7
与实施例1的区别在于，步骤(4)中，所使用的聚合物单体为季戊四醇四丙烯酸酯，得到的聚合物电解质为聚季戊四醇四丙烯酸酯(熔融温度为260℃)。
实施例8-11
与实施例的区别在于，电解质材料中阻燃剂的质量占比分别为5％(实施例8)、20％(实施例9)、3％(实施例10)、25％(实施例11)。
对比例1
与实施例4的区别在于，电解质材料的制备方法如下：
(1)将3g阻燃剂(乙氧基五氟环磷腈)与30g聚合物电解质(聚碳酸乙烯亚乙酯，熔融温度为210℃)和锂盐(具体为LITFSI)混合，在85℃下分散，得到聚合物电解质含量为80％、锂盐含量为19.5％、引发剂含量为0.5％(以聚合物电解质、锂盐和引发剂的总质量为100％计)的混合溶液，以阻燃剂和聚合物电解质的总质量为100％计，所述阻燃剂的质量百分比为10％；得到的聚合物电解质与阻燃剂简单共混材料。
应用例1-11、对比应用例1
上述应用例分别制备一种半固态电池电芯，分别采用实施例1-11、对比例1的电解质材料，具体方法如下：
(1)正极浆料：按照如图1所示的方法制备，得到电解质材料含量为10％的正极浆料；
(2)负极浆料，按照如图3所示的方法制备，得到电解质材料含量为10％的负极浆料；
(3)正极电极片：将制备好的正极浆料涂布在铝箔上，涂布厚度50μm，涂布宽度500mm，涂布长度为10m；涂布面密度：5mg/cm 2；涂布方法：转移涂布；在露点-50℃的干燥条件下辊压，辊压温度为180℃，压力为300Mpa，辊直径为500mm，辊压后厚度25μm，压实密度为3.6mg/cm 3；
(4)负极电极片：将制备好的负极浆料涂布在铝箔上，涂布厚度50μm，涂布宽度500mm，涂布长度为10m；涂布面密度：5mg/cm2；涂布方法：转移涂布；在露点-50℃的干燥条件下辊压，辊压温度为180℃，压力为300Mpa，辊直径为500mm，辊压后厚度25μm，压实密度为1.6mg/cm 3。
(5)半固态电池(软包)：正负电极片通过叠片方式进行组装，组装后电池进行注液，注液后45℃高温老化24h，之后进行化成流程，得到成品(5Ah NCM-Gr电池电芯)。
对比应用例2
与应用例1的区别在于，步骤(1)和步骤(2)中均不添加电解质材料。
图11为应用例1的5Ah NCM-Gr电芯通过150℃热箱实验温度-电压测试数据图，图中显示添加阻燃剂@离子导电聚合物的NCM-Gr电池可以顺利通过150℃热箱，证明本材料的阻燃特性优秀。
图12a和12b分别为应用例1和对比应用例2的5Ah NCM-Gr电池电芯通过150℃热箱后状态图，图12a基本无损，而图12b中已烧毁，证明本公开提供的电解质材料能够有效的提高电池的阻燃性能，安全性更高。
图13a和13b分别为应用例1和对比应用例2的5Ah NCM-Gr电池电芯的针刺安全性对比图，图13a中可以顺利通过针刺，而图13b中针刺发生起火，进一步证明本申请的电解质材料能够有效的提高电池的阻燃性能。
图14为应用例1的5Ah NCM-Gr电池电芯1C循环寿命数据图，图中显示，循环200次后，容量保持率仍有93.7％，证明本公开提供的电解质材料应用于电池中，能够获得良好的循环性能。
性能测试
分别针对上述应用例和对比应用例得到的5Ah NCM-Gr电芯进行如下性能测试：
(1)阻燃性能测试：按照针刺及热箱进行测试；
安全性(针刺测试)条件：
参照GBT31485-2015电动汽车用动力蓄电池安全要求及试验方法，步骤如下：
a)单体电池充电；
b)用φ6.5mm的耐高温钢针(针尖的圆锥角度为50°，针的表面光洁、无锈蚀、氧化层及油污)，以25mm/s的速度，从垂直于蓄电池极板的方向贯穿，贯穿位置靠近所刺面的几何中心，钢针停留在电池中；
c)观察1h。
(1)阻燃性能测试：按照针刺及热箱进行测试；
安全性(热箱测试)条件：
a)单体电池充电；
b)将单体电池放入温度箱，对于锂离子电池，温度箱按照5℃/min的速率由室温升至150±2℃，并保持此温度30min后停止加热；
c)观察1h。
(2)循环性能测试：
首效测试条件：环境温度为25℃；
a)恒流恒压充电：0.05C恒流充电(CC)22h至4.25V，恒压充电(CV)至0.01C；
b)静置10min；
c)恒流放电(DC)：0.05C DC至2.5V。
循环性能测试条件：测试温度为25℃；
a)恒流恒压充电：1C CC至4.25V，CV至0.05C；
b)静置5min；c)恒流放电：1C DC至2.5V；
d)循环步骤a)-步骤c)100次。
(3)倍率性能测试：
测试条件：
a)恒流恒压充电：0.33C CC 4h至4.25V，CV至0.05C；
b)静置5min；
c)恒流放电：0.33C DC至2.5V；
d)静置5min；
e)恒流恒压充电：0.33C CC 4h至4.25V，CV至0.05C；
f)静置5min；
g)恒流放电：1C DC至2.5V。
测试得到1C/0.33C的倍率性能，其他条件下0.1C/0.1C、0.33C/0.33C、0.33/0.5C、0.33/2C的倍率性能测试参数参照上述条件。
上述测试结果如表1所示。
表1
Figure PCTCN2021077549-appb-000001
Figure PCTCN2021077549-appb-000002
由表1可知，本公开提供的电解质材料应用于半固态电池中，具有优异的阻燃性能，同时具有优异的循环性能和倍率性能。
通过对比实施例1、4-7可知，当聚合物电解质的熔融指数在150-250℃范围之内时(实施例1、4、5)，电池具有更佳的阻燃性能、循环性能和倍率性能。
通过对比实施例1、8-11可知，当电解质材料中阻燃剂的质量占比为5-20％时(实施例1、8、9)，电池具有更佳的阻燃性能、循环性能和倍率性能。

Claims (40)

  1. 一种电解质材料，包括核体和包覆在核体外的壳体，所述核体包括阻燃剂颗粒，所述壳体包括离子导电聚合物；
    所述离子导电聚合物包括锂盐和聚合物电解质的组合。
  2. 根据权利1所述的电解质材料，其中，所述电解质材料中阻燃剂的质量占比为5-20％。
  3. 根据权利要求1或2所述的电解质材料，其中，所述核体的直径为0.5～10μm。
  4. 根据权利要求1-3中任一项所述的电解质材料，其中，所述壳体的厚度为100-500nm。
  5. 根据权利1-4中任一项所述的电解质材料，其中，所述阻燃剂包括磷酸三甲酯、磷酸三乙酯、磷酸三丁酯、三(2,2,2-三氟乙基)亚磷酸酯、磷酸三苯酯、亚磷酸酯或磷腈类阻燃材料中的任意一种或至少两种组合。
  6. 根据权利要求1-5中任一项所述的电解质材料，其中，所述锂盐占所述离子导电聚合物质量的1～20％。
  7. 根据权利要求1-6中任一项所述的电解质材料，其中，所述锂盐包括高氯酸锂、双三氟甲烷磺酰亚胺锂、双氟磺酰亚胺锂、双乙二酸硼酸锂或四氟硼酸锂中的任意一种或至少两种组合。
  8. 根据权利要求1-7中任一项所述的电解质材料，其中，所述聚合物电解质的熔融温度为150-250℃。
  9. 根据权利要求1-8中任一项所述的电解质材料，其中，所述聚合物电解质包括聚氧化乙烯、聚丙烯腈、聚甲基丙烯酸甲酯、聚偏二氟乙烯、聚乙二醇、聚乙二醇二丙烯酸酯或聚碳酸亚乙烯酯中的任意一种或至少两种组合。
  10. 根据权利要求1-9中任一项所述的电解质材料，还包括，在所述阻燃剂颗粒和所述离子导电聚合物之间存在乳化剂。
  11. 根据权利要求10所述的电解质材料，其中，所述乳化剂沉积在所述阻燃剂颗粒表面。
  12. 根据权利要求10或11所述的电解质材料，其中，所述乳化剂包括聚乙二醇、十二烷基磺酸钠、脂肪酸聚氧乙烯醚、阿拉伯胶、烷基苯磺酸钠、异硬脂酸单甘油酯、聚氧乙烷-聚氧丙烷共聚体、十六烷基三甲基溴化铵、苯乙烯马来酸酐共聚物中、非离子石蜡微乳化剂、阳离子石蜡微乳化剂、阴离子石蜡乳化剂、OP-10、OP-15、平平加O-10、油包水型废机油乳化剂、油包水型柴油乳化剂或油包水型动植物油乳化剂的任意一种或至少两种组合。
  13. 一种根据权利要求1-12中任一项所述的电解质材料的制备方法，包括：将阻燃剂分散液、聚合物单体、锂盐和引发剂混合，分散，得到混合溶液，搅拌并加热，保温反应，得到所述电解质材料。
  14. 根据权利要求13所述的制备方法，其中，所述制备方法在氩气氛围中进行。
  15. 根据权利要求13或14所述的制备方法，还包括，使用回流冷凝设备。
  16. 根据权利要求13-15中任一项所述的制备方法，其中，所述分散的温度为80-90℃。
  17. 根据权利要求13-16中任一项所述的制备方法，其中，所述引发剂包括偶氮二异丁腈或偶氮二异庚腈至少之一。
  18. 根据权利要求13-17中任一项所述的制备方法，其中，以聚合物单体、锂盐和引发剂的总质量为100％计，所述聚合物单体的质量占比为70-90％。
  19. 根据权利要求13-18中任一项所述的制备方法，其中，以聚合物单体、锂盐和引发剂的总质量为100％计，所述锂盐的质量占比为1-20％。
  20. 根据权利要求13-19中任一项所述的制备方法，其中，以聚合物单体、锂盐和引发剂的总质量为100％计，所述引发剂的质量占比为0.1-1％。
  21. 根据权利要求13-20中任一项所述的制备方法，其中，所述加热的温度为60-80℃。
  22. 根据权利要求13-21中任一项所述的制备方法，其中，所述保温反应的时间为2-5h。
  23. 根据权利要求13-21中任一项所述的制备方法，其中，所述阻燃剂分散液的制备方法包括：将阻燃剂与分散剂混合，分散，得到所述阻燃剂分散液。
  24. 根据权利要求23所述的制备方法，其中，所述阻燃剂分散液的制备方法中所述分散的温度为20-30℃。
  25. 根据权利要求13-24中任一项所述的制备方法，其中，所述阻燃剂分散液中阻燃剂的粒径为0.1μm-10μm。
  26. 根据权利要求13-25中任一项所述的制备方法，还包括：在所述将阻燃剂分散液、聚合物单体、锂盐和引发剂混合之前，将所述阻燃剂分散液进行乳化。
  27. 根据权利要求26所述的制备方法，其中，所述乳化的方法包括：在所述阻燃剂分散液中添加乳化剂溶液，进行乳化。
  28. 根据权利要求13-27所述的制备方法，还包括：在所述将阻燃剂分散液、聚合物单体、锂盐和引发剂混合之前，将所述阻燃剂分散液的pH调节至3-4。
  29. 根据权利要求28所述的制备方法，其中，所述调节pH的方法包括使 用乙酸溶液进行调节。
  30. 根据权利要求13-29中任一项所述的制备方法，还包括：所述保温反应之后，进行干燥，得到粉体颗粒状的电解质材料。
  31. 根据权利要求30所述的制备方法，其中，所述干燥在氩气氛围中进行。
  32. 根据权利要求30或31所述的制备方法，其中，所述干燥的温度为70-90℃。
  33. 根据权利要求30-32中任一项所述的制备方法，其中，所述干燥的时间为20-30h。
  34. 根据权利要求30-33中任一项所述的制备方法，还包括：所述粉体颗粒状的电解质材料在氩气氛围中保存。
  35. 根据权利要求13所述的制备方法，其中，所述制备方法包括如下步骤：
    (1)将阻燃剂与分散剂混合，在20-30℃下分散，得到阻燃剂的粒径为0.1μm-10μm的阻燃剂分散液；
    (2)在所述阻燃剂分散液中添加乳化剂溶液，使用蒸馏水进行乳化处理；
    (3)使用10％乙酸溶液将所述阻燃剂分散液的pH调节至3-4；
    (4)将所述阻燃剂分散液、聚合物单体、锂盐和引发剂混合，在80-90℃下分散，得到聚合物单体含量为70-90％、锂盐含量为10-30％、引发剂含量为0.2-1％的混合溶液；
    (5)将所述混合溶液搅拌并加热至60-80℃，保温反应2-5h，得到所述电解质材料；
    (6)在70-90℃干燥20-30h，得到粉体颗粒状的电解质材料；
    所述步骤(1)至(6)均在氩气氛围中进行。
  36. 一种包含权利要求1-12中任一项所述的电解质材料的电极浆料。
  37. 一种表面涂覆有权利要求36所述的电解质浆料的电极片。
  38. 一种包含权利要求37所述的电极片的电池电芯。
  39. 一种包含权利要求38所述的电池电芯的电池。
  40. 一种权利要求39所述的电池的应用，其中，所述电池应用于电子产品或新能源汽车。
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