CN111916747B - High-safety polymer battery positive plate, polymer battery and battery preparation method - Google Patents

High-safety polymer battery positive plate, polymer battery and battery preparation method Download PDF

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Publication number
CN111916747B
CN111916747B CN202010801285.4A CN202010801285A CN111916747B CN 111916747 B CN111916747 B CN 111916747B CN 202010801285 A CN202010801285 A CN 202010801285A CN 111916747 B CN111916747 B CN 111916747B
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polymer
coating
solid electrolyte
positive electrode
electrolyte
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CN111916747A (en
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孟繁慧
甄会娟
朱莎
高金辉
周江
伍绍中
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Tianjin Juyuan New Energy Technology Co ltd
Tianjin Lishen Battery JSCL
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Tianjin Juyuan New Energy Technology Co ltd
Tianjin Lishen Battery JSCL
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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
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0419—Methods of deposition of the material involving spraying
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • H01M4/0435—Rolling or calendering
    • 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
    • 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
    • H01M4/624—Electric conductive fillers
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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

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  • General Chemical & Material Sciences (AREA)
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  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
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Abstract

The invention discloses a high-safety polymer battery positive plate protected by a solid electrolyte coating, which comprises an aluminum foil and a double-layer coating layer; aluminum foil, as a positive current collector, coated with a double-layer coating layer on the outer surface thereof; wherein the double-layer coating layer comprises a composite solid electrolyte coating coated on the aluminum foil and a positive electrode active material coating coated on the composite solid electrolyte coating; a composite solid electrolyte coating comprising a first conductive agent and a composite solid electrolyte. In addition, the invention also discloses a high-safety polymer battery based on the positive electrode protection and a preparation method of the high-safety polymer battery based on the positive electrode protection. The high-safety polymer battery positive plate, the polymer battery and the battery preparation method can effectively block the contact between the positive electrode active material and the aluminum foil, prevent the thermit reaction from happening when the polymer battery is safe and invalid, avoid exothermic chain reaction of the battery and improve the safety of the polymer battery.

Description

High-safety polymer battery positive plate, polymer battery and battery preparation method
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a high-safety polymer battery positive plate, a polymer battery and a battery preparation method.
Background
With the improvement of the energy density of lithium ion batteries, consumers have increasingly higher requirements on the safety performance of the lithium ion batteries. Positive electrode materials of layered crystal structure with high energy density, e.g. LiNi x Co y Mn z O 2 (NCM)、LiCoO 2 Attention and technical studies have been paid, and it is known that the thermal stability of a high energy density cathode material during charging is a key factor affecting its application.
For the lithium ion battery, under the abuse condition, internal short circuit may occur, and joule heat accumulation caused by the internal short circuit may cause exothermic reaction of materials such as a large-area negative electrode, a large-area positive electrode, a large-area electrolyte, a large-area separator and the like, and further, exothermic chain reaction occurs, so that the problem of thermal runaway of the lithium ion battery is finally caused. In particular, when a material having poor thermal stability is used for the positive electrode, the probability of occurrence of thermal runaway is greater. In order to effectively prevent the contact between the positive electrode active material and the aluminum foil (serving as a positive electrode current collector), the generation of aluminothermic reaction when the battery is safe and invalid is prevented, and the self-heating reaction is reduced, so that the method is one of the more effective methods for preventing the generation of heat spreading of the battery.
The positive electrode active material is lithium atom intercalated oxide, the positive electrode material is delithiated to be converted into oxide in a charged state, the oxide and aluminum metal can generate oxidation-reduction reaction under the high-heat condition generated by thermal failure of the lithium ion battery, aluminum shows strong reducibility, and a large amount of heat is released in a short time during the reaction due to extremely low formation enthalpy (-1645 kJ/mol) of the aluminum, so that the thermal failure effect of the lithium ion battery is aggravated.
An improvement method is always sought, such as coating the surface of the positive electrode active material, doping elements, etc., but the surface of the positive electrode active material is coated with an inactive material with good thermal stability, so that the thermal stability of the material is improved to a certain extent, but the energy density of the material is reduced; meanwhile, the surface of the positive electrode active material is coated with the inactive material, so that the contact between the positive electrode active material and the aluminum foil can not be effectively blocked.
Therefore, there is an urgent need to develop a technology capable of effectively blocking the contact between the positive electrode active material and the aluminum foil (as the positive electrode current collector), preventing the thermit reaction from occurring when the safety of the polymer battery fails, avoiding the exothermic chain reaction of the battery, and improving the safety of the polymer battery.
Disclosure of Invention
The invention aims at overcoming the technical defects existing in the prior art and provides a high-safety polymer battery positive plate, a polymer battery and a battery preparation method.
Therefore, the invention provides a high-safety polymer battery positive plate protected by a solid electrolyte coating, which comprises an aluminum foil and a double-layer coating layer;
aluminum foil, as a positive current collector, coated with a double-layer coating layer on the outer surface thereof;
wherein the double-layer coating layer comprises a composite solid electrolyte coating coated on the aluminum foil and a positive electrode active material coating coated on the composite solid electrolyte coating;
a composite solid electrolyte coating comprising a first conductive agent and a composite solid electrolyte;
in the composite solid electrolyte coating, the first conductive agent includes at least one of carbon black, carbon nanotubes, and graphene;
in the composite solid electrolyte coating, the composition of the composite solid electrolyte material is a composite solid electrolyte including a first oxide solid electrolyte and a first polymer solid electrolyte;
wherein the first oxide solid state electrolyte comprises at least one of LLZO, LATP, and LAGP, the LLZO, LATP, and LAG being oxide solid state electrolytes;
Wherein the first polymer solid state electrolyte comprises a first polymer and a first lithium salt, wherein the first polymer specifically comprises at least one of PEO, PMMA, PVDF, PAN and PPC;
the first polymer solid state electrolyte further comprises a first mechanically reinforced polymer comprising at least one of 3-methacryloxypropyl methyl diethoxysilane and ethylene terminated polydimethylsiloxane;
the first polymer solid electrolyte also comprises a first polymerization initiator, wherein the first polymerization initiator comprises one of dibenzoyl peroxide, dilauroyl peroxide, tert-butyl peroxy-2-ethylhexanoate and azobisisobutyronitrile.
The first lithium salt comprises LiFSI, liTFSI, liClO 4 And LiPF 6 At least one of them.
For the composite solid electrolyte coating, the proportion of each component is as follows:
wherein the proportion of the first polymer in the first polymer solid electrolyte to the total weight of the composite solid electrolyte coating is 5-30%;
the first lithium salt in the first polymer solid electrolyte accounts for 0.5-30% of the total weight of the composite solid electrolyte coating;
the first mechanically reinforced polymer in the first polymer solid electrolyte accounts for 20-80% of the total weight of the first polymer solid electrolyte;
Wherein the first conductive agent accounts for 5-20% of the total weight of the composite solid electrolyte coating;
wherein the first oxide solid electrolyte accounts for 30-80% of the total weight of the composite solid electrolyte coating.
Wherein the first polymerization initiator accounts for 0.01-1% of the total weight of the composite solid electrolyte coating;
preferably, the composite solid electrolyte coating is directly coated on the aluminum foil, and the thickness of the single-layer composite solid electrolyte coating is 0.5-5 microns;
and the thickness of the single-layer positive electrode active material coating is 40-100 micrometers.
Preferably, the positive electrode active material coating layer includes a positive electrode active material, a second polymer solid electrolyte, a second conductive agent, and a second oxide solid electrolyte, wherein the second polymer solid electrolyte includes a second polymer and a second lithium salt, wherein the proportions of the components are as follows:
the positive electrode active material accounts for 88-98% of the total weight of the positive electrode active material coating;
the second polymer in the second polymer solid electrolyte accounts for 0.5% -5% of the total weight of the positive electrode active material coating;
The second lithium salt in the second polymer solid electrolyte accounts for 0.5-5% of the total weight of the positive electrode active material coating;
the second conductive agent accounts for 0.5-10% of the total weight of the positive electrode active material coating;
the second oxide solid electrolyte (i.e., the second inorganic solid electrolyte) accounts for 0.5 to 5 percent of the total weight of the positive electrode active material coating.
Preferably, the positive electrode active material coating layer includes a positive electrode active material including any one of a lithium cobaltate material, a ternary material, and a high nickel material;
the second conductive agent included in the positive electrode active material coating comprises at least one of carbon black, carbon nano-tubes, graphene and other conductive nano-materials;
the second polymer solid electrolyte included in the positive electrode active material coating comprises a second polymer and a second lithium salt, wherein the second polymer specifically comprises at least one of PEO, PMMA, PVDF, PAN and PPC, and the second lithium salt comprises LiFSI, liTFSI, liClO 4 And LiPF 6 At least one of (a) and (b);
the second oxide solid electrolyte included in the positive electrode active material coating layer specifically includes at least one of LLZO, LATP, and LAGP.
In addition, the invention also provides a high-safety polymer battery based on positive electrode protection, which comprises the high-safety polymer battery positive electrode plate, a polymer battery negative electrode, a preset polymer electrolyte and a support film;
the polymer battery cathode is a lithium metal cathode piece or a traditional lithium ion battery cathode piece;
the material of the support film comprises any one of PEO, PMMA, PVDF, PAN, PET and PI base films;
the preset polymer electrolyte comprises a preset polymer electrolyte monomer, a small molecule solvent and lithium salt, wherein:
presetting polymer electrolyte monomers, including at least one of ECA, PEG, MPEG-MA;
the pre-set polymer electrolyte monomer further comprises a pre-set mechanically reinforced polymer comprising at least one of 3-methacryloxypropyl methyl diethoxysilane and ethylene terminated polydimethylsiloxane;
the preset polymer electrolyte also comprises a preset polymerization initiator, wherein the preset polymerization initiator comprises one of dibenzoyl peroxide, dilauroyl peroxide, tert-butyl peroxy-2-ethylhexanoate and azobisisobutyronitrile;
the small molecule solvent comprises at least one of PC, EC, DEC, DMC, VC and FEC;
Lithium salts, including LiFSI, liTFSI, liClO 4 And LiPF 6 At least one of (a) and (b);
in the preset polymer electrolyte, the weight contents of the preset polymer electrolyte monomer, the lithium salt in the preset polymer electrolyte, the small molecular solvent and the polymerization initiator are as follows:
5 to 60 percent of preset polymer electrolyte monomer, 10 to 40 percent of lithium salt, 5 to 60 percent of small molecule solvent and 0.01 to 0.1 percent of polymerization initiator.
Wherein, the preset mechanical enhancement type polymer in the preset polymer electrolyte monomer accounts for 20 to 80 percent of the weight of the preset polymer electrolyte monomer.
Preferably, a method of free radical in-situ initiation polymerization reaction is adopted, the positive electrode, the preset polymer electrolyte, the negative electrode and the support film are integrated, and the polymer battery is finally prepared.
In addition, the invention also provides a preparation method of the high-safety polymer battery based on positive electrode protection, which comprises the following steps:
firstly, coating a layer of composite solid electrolyte coating on the outer surface of an aluminum foil by adopting a micro gravure coating process;
secondly, coating a layer of anode active material coating on the composite solid electrolyte coating by adopting a roller coating or spraying process to obtain an anode;
Thirdly, integrating the positive electrode, the preset polymer electrolyte, the negative electrode and the support film obtained in the second step by adopting a free radical in-situ polymerization reaction initiation method, and finally preparing and obtaining the polymer battery;
wherein, the first step specifically comprises the following steps:
step S11: uniformly mixing a first oxide solid electrolyte, a first conductive agent, a first polymer contained in the first polymer solid electrolyte, a first lithium salt contained in the first polymer solid electrolyte and a first solvent to prepare a coating slurry for obtaining a composite solid electrolyte coating;
step S12: coating the aluminum foil with coating slurry of a composite solid electrolyte coating by using a micro gravure coating mode, drying and rolling the aluminum foil for standby;
wherein, the second step specifically comprises the following steps:
step S21: uniformly mixing a positive electrode active material, a second conductive agent, a second oxide solid electrolyte, a second polymer contained in the second polymer solid electrolyte, a second lithium salt contained in the second polymer solid electrolyte and a second solvent to prepare a positive electrode active material coating slurry;
step S22: coating a positive electrode active material coating on the composite solid electrolyte coating obtained in the first step by adopting a roller coating or spraying process, and drying and rolling to obtain a positive electrode;
Wherein, the third step specifically comprises the following steps:
step S31: respectively punching and drying the anode and the cathode obtained in the second step, and assembling the polymer battery, wherein the polymer battery dry cell is assembled to the stage before injecting the polymer monomer solution;
step S32: preparing a polymer monomer solution from preset polymer electrolyte monomers in preset polymer electrolyte, lithium salt in the preset polymer electrolyte, a preset polymerization initiator and a small molecular solvent according to a preset proportion;
step S33: and (3) injecting the polymer monomer solution (namely the polymerization reaction mixed solution) obtained in the step (S32) into the polymer battery cell prepared in the step (S31), then placing the polymer battery cell in a dry atmosphere for negative pressure standing, sealing, cold pressing and hot pressing, and carrying out in-situ reaction at a preset temperature and a preset pressure to finally obtain the polymer lithium ion battery.
Preferably, in step S11, in the coating slurry of the composite solid electrolyte coating layer, the second conductive agent includes at least one of carbon black, carbon nanotubes, graphene and other conductive nanomaterials;
in step S11, a first oxide solid electrolyte including at least one of nano materials having higher thermal stability such as LLZO, LATP, and LAGP oxide solid electrolytes;
A first polymer in a first polymer solid state electrolyte comprising at least one of PEO, PMMA, PVDF, PAN and PPC;
the first polymer solid state electrolyte further comprises a first mechanically reinforced polymer comprising at least one of 3-methacryloxypropyl methyl diethoxysilane and ethylene terminated polydimethylsiloxane;
the first polymer solid electrolyte also comprises a first polymerization initiator, wherein the first polymerization initiator comprises one of dibenzoyl peroxide, dilauroyl peroxide, tert-butyl peroxy-2-ethylhexanoate and azobisisobutyronitrile.
A first lithium salt in a first polymer solid state electrolyte comprising LiFSI, liTFSI, liClO 4 And LiPF 6 At least one of (a) and (b);
in step S11, in the coating slurry of the composite solid electrolyte coating layer, the component proportions of the respective solid components are specifically as follows:
the first polymer solid electrolyte comprises 5% -30% of the first polymer accounting for the total weight of the composite solid electrolyte coating;
the first mechanically reinforced polymer in the first polymer solid electrolyte accounts for 20-80% of the total weight of the first polymer solid electrolyte;
Wherein the first polymerization initiator accounts for 0.01-1% of the total weight of the composite solid electrolyte coating;
the first polymer solid electrolyte comprises a first lithium salt accounting for 0.5-30% of the total weight of the composite solid electrolyte coating;
the first conductive agent accounts for 5% -20% of the total weight of the composite solid electrolyte coating;
the first oxide solid electrolyte accounts for 30% -80% of the total weight of the composite solid electrolyte coating;
in step S11, in the coating slurry of the composite solid electrolyte coating layer, the solvent used is NMP, and the solid content of the slurry is 10% to 50%.
Preferably, in step S21, in the coating slurry of the positive electrode active material coating layer, the positive electrode active material includes any one of positive electrode materials such as lithium cobaltate material, ternary material and high nickel material;
in step S21, in the coating slurry of the positive electrode active material coating layer, the second conductive agent includes at least one of carbon black, carbon nanotubes, graphene and other conductive nanomaterials;
in step S21, in the coating paste of the positive electrode active material coating layer, a second oxide solid electrolyte including at least one of nano materials having higher thermal stability such as LLZO, LATP, and LAGP;
A second polymer in a second polymer solid state electrolyte comprising at least one of PEO, PMMA, PVDF, PAN and PPC;
a second lithium salt in a second polymer solid state electrolyte comprising LiFSI, liTFSI, liClO 4 And LiPF 6 At least one of (a) and (b);
in step S21, in the coating slurry of the positive electrode active material coating layer, the proportions of the solid components are specifically as follows:
the proportion of the positive electrode active material accounting for 88-98% of the total weight of the positive electrode active material coating;
the second polymer solid electrolyte comprises a second polymer accounting for 0.5-5% of the total weight of the positive electrode active material coating;
the second polymer solid electrolyte contains second lithium salt which accounts for 0.5-5% of the total weight of the positive electrode active material coating;
the second conductive agent accounts for 0.5-10% of the total weight of the positive electrode active material coating;
a second oxide solid electrolyte (i.e., a second inorganic solid electrolyte) accounting for 0.5% -5% of the total weight of the positive electrode active material coating;
in step S21, in the coating slurry of the positive electrode active material coating layer, the second solvent used is NMP, and the solid content of the slurry is 50% to 80%.
Preferably, in step S12, the preparation method of the composite solid electrolyte coating layer is as follows: directly coating on the aluminum foil, wherein the thickness of the single-layer composite solid electrolyte coating is 0.5-5 micrometers;
in step S22, the thickness of the single-layer positive electrode active material coating layer coated on the composite solid electrolyte coating layer is 40-100 micrometers;
in step S32, presetting polymer electrolyte monomers in the preset polymer electrolyte, including at least one of ECA, PEG, MPEG-MA;
the pre-set polymer electrolyte monomer further comprises a pre-set mechanically reinforced polymer comprising at least one of 3-methacryloxypropyl methyl diethoxysilane and ethylene terminated polydimethylsiloxane;
in step S32, a preset polymerization initiator includes one of dibenzoyl peroxide, dilauroyl peroxide, tert-butyl peroxy-2-ethylhexanoate, and azobisisobutyronitrile;
in step S32, a small molecule solvent comprising at least one of PC, EC, DEC, DMC, VC and FEC;
in step S32, a lithium salt in the polymer electrolyte is preset, including LiFSI, liTFSI, liClO 4 And LiPF 6 At least one of (a) and (b);
in step S32, the weight contents of the preset polymer electrolyte monomer, the lithium salt in the preset polymer electrolyte, and the preset polymerization initiator in the polymer monomer solution are respectively: 5 to 60 percent of preset polymer electrolyte monomer, 10 to 40 percent of lithium salt, 5 to 60 percent of small molecule solvent and 0.01 to 0.1 percent of preset polymerization initiator;
wherein, the preset mechanical enhancement type polymer in the preset polymer electrolyte monomer accounts for 20 to 80 percent of the weight of the preset polymer electrolyte monomer.
In the step S33, after the cell is sealed, the preset pressure of cold pressing and hot pressing is 0.001-0.5 MPa, the temperature of hot pressing is 40-70 ℃, and the reaction time is 2-12 hours.
Compared with the prior art, the high-safety polymer battery positive plate, the polymer battery and the preparation method of the battery are scientific in design, can effectively block the contact between the positive electrode active material and the aluminum foil (serving as a positive electrode current collector), prevent thermit reaction when the polymer battery is safe and invalid, avoid exothermic chain reaction of the battery, improve the safety of the polymer battery, and have great practical significance.
Drawings
Fig. 1 is a flowchart of a preparation method of a high-safety polymer battery based on positive electrode protection.
Detailed Description
In order to better understand the aspects of the present invention, the present invention will be described in further detail with reference to the drawings and embodiments.
The invention provides a high-safety polymer battery positive plate protected by a solid electrolyte coating, which comprises an aluminum foil and a double-layer coating layer;
aluminum foil, as a positive electrode current collector, the outer surface (including upper and lower side surfaces and front and rear side surfaces) of which is coated with a double-layer coating layer;
wherein the double-layer coating layer comprises a composite solid electrolyte coating layer coated on the aluminum foil and a positive electrode active material coating layer coated on the composite solid electrolyte coating layer.
In the invention, the composite solid electrolyte coating comprises a first conductive agent and a composite solid electrolyte, has conductivity, lithium ion conductivity and thermal stability, and is used for isolating the positive electrode active material from direct contact with the aluminum foil.
In particular, the composite solid electrolyte coating is directly coated on the aluminum foil, and the thickness of the single-layer composite solid electrolyte coating is preferably 0.5-5 microns. The composite solid electrolyte coating layer coated on one surface of the aluminum foil is a single-layer composite solid electrolyte coating layer, and single-layer coating is performed.
In the composite solid electrolyte coating, the first conductive agent comprises at least one of carbon black, carbon nano tubes, graphene and other conductive nano materials.
In particular, in the composite solid electrolyte coating, the components of the composite solid electrolyte material are composite solid electrolytes comprising a first oxide solid electrolyte and a first polymer solid electrolyte;
the first oxide solid electrolyte can specifically include at least one of nano inorganic solid electrolyte materials with higher thermal stability, such as oxide solid electrolytes of LLZO, LATP, LAGP and the like;
wherein the first polymer solid state electrolyte comprises a first polymer and a first lithium salt, wherein the first polymer specifically comprises at least one of PEO, PMMA, PVDF, PAN and PPC.
The first polymer solid electrolyte further comprises a first mechanically reinforced polymer comprising at least one of a silane coupling agent such as 3-methacryloxypropyl methyl diethoxysilane and ethylene-terminated polydimethylsiloxane;
in particular implementation, the first polymer solid electrolyte also comprises a first polymerization initiator, wherein the first polymerization initiator comprises one of dibenzoyl peroxide, dilauroyl peroxide, tert-butyl peroxy-2-ethylhexanoate and azobisisobutyronitrile.
The first lithium salt comprises LiFSI, liTFSI, liClO 4 And LiPF 6 At least one of (a) and (b);
in particular implementation, for the composite solid electrolyte coating, the proportion of each component is as follows:
wherein the proportion of the first polymer in the first polymer solid electrolyte to the total weight of the composite solid electrolyte coating is 5-30%;
the first mechanically reinforced polymer (i.e., the first mechanical enhancer) in the first polymer solid electrolyte is present in an amount of 20% to 80% by weight based on the total weight of the first polymer solid electrolyte;
the first lithium salt in the first polymer solid electrolyte accounts for 0.5-30% of the total weight of the composite solid electrolyte coating;
wherein the first conductive agent accounts for 5-20% of the total weight of the composite solid electrolyte coating;
wherein the first oxide solid electrolyte accounts for 30-80% of the total weight of the composite solid electrolyte coating.
Wherein the first polymerization initiator accounts for 0.01-1% of the total weight of the composite solid electrolyte coating;
it should be noted that, in the present invention, the first oxide solid electrolyte (i.e., inorganic solid electrolyte) in the composite solid electrolyte coating layer functions as: the mechanical strength of the isolating layer is increased, so that the application of the ultrathin aluminum foil is possible;
For composite solid electrolyte coatings, the first polymer solid electrolyte therein functions as: while increasing the flexibility of the separator, increasing the adhesion with the positive electrode active material layer; meanwhile, the composite solid electrolyte coating also has high lithium ion conductivity, and can increase the lithium ion conductivity of the bottom layer of the positive electrode.
In the invention, for the high-safety polymer battery positive plate, the thickness of the single-layer positive electrode active material coating layer is preferably 40-100 micrometers;
the thickness of the double-layer positive electrode active material coating is 80-200 micrometers.
In the present invention, in particular implementation, for a high-safety positive electrode sheet, the positive electrode active material coating layer coated on the composite solid electrolyte coating layer includes a positive electrode active material, a second polymer solid electrolyte, a second conductive agent, and a second oxide solid electrolyte (i.e., a second inorganic solid electrolyte), wherein the second polymer solid electrolyte includes a second polymer and a second lithium salt, and the proportions of the components are as follows:
the positive electrode active material accounts for 88-98% of the total weight of the positive electrode active material coating;
The second polymer in the second polymer solid electrolyte accounts for 0.5% -5% of the total weight of the positive electrode active material coating;
the second lithium salt in the second polymer solid electrolyte accounts for 0.5-5% of the total weight of the positive electrode active material coating;
the second conductive agent accounts for 0.5-10% of the total weight of the positive electrode active material coating;
the second oxide solid electrolyte (i.e., the second inorganic solid electrolyte) accounts for 0.5 to 5 percent of the total weight of the positive electrode active material coating.
In the present invention, in particular, for the high-safety polymer battery positive electrode sheet, the positive electrode active material included in the positive electrode active material coating layer includes any one of positive electrode materials such as a lithium cobaltate material, a ternary material, and a high-nickel material.
In the invention, for the high-safety polymer battery positive electrode sheet, the second conductive agent included in the positive electrode active material coating comprises at least one of carbon black, carbon nano tubes, graphene and other conductive nano materials.
In particular embodiments of the present invention, for a high safety polymer battery positive electrode sheet, the positive electrode active material coating comprises a second polymer solid electrolyte comprising a second polymer and a second lithium salt, wherein the second polymer comprises at least one of PEO, PMMA, PVDF, PAN and PPC, and the second lithium salt comprises LiFSI, liTFSI, liClO 4 And LiPF 6 At least one of them.
In the present invention, in particular, for the positive electrode sheet of the high-safety polymer battery, the second oxide solid electrolyte (i.e., the second inorganic solid electrolyte) included in the positive electrode active material coating layer may include at least one of nano inorganic solid electrolyte materials LLZO, LATP, LAGP having higher thermal stability;
it should be noted that, for the present invention, for the thermal runaway phenomenon under the abuse condition of the existing high energy density battery, starting from the positive electrode side electrode structure of the polymer battery, a layer of composite solid electrolyte coating with high thermal stability is constructed between the aluminum foil and the positive electrode active material so as to obstruct the contact between the positive electrode active material and the aluminum foil, and the present invention aims to prevent the occurrence of thermit reaction when the polymer battery is safe and invalid, reduce the self-heating reaction of the battery, thereby avoiding exothermic chain reaction of the battery and further improving the safety of the polymer battery.
Based on the high-safety polymer battery positive plate protected by the solid electrolyte coating, the invention also provides a high-safety polymer battery based on positive electrode protection, and the battery comprises the high-safety polymer battery positive plate, a polymer battery negative electrode, a preset polymer electrolyte and a support film.
In the invention, in the high-safety polymer battery, the polymer battery negative electrode is a lithium metal negative electrode plate, and can also be a traditional lithium ion battery negative electrode plate.
In the present invention, in particular, in the high-safety polymer battery, the material of the support film includes any one of a PEO, PMMA, PVDF, PAN, PET base film and a PI base film.
In the invention, the positive electrode, the preset polymer electrolyte, the negative electrode and the support film are integrated by adopting a free radical in-situ polymerization reaction initiation method (the existing mature process), and finally the polymer battery is prepared.
In the present invention, in a high safety polymer battery, the preset polymer electrolyte comprises a preset polymer electrolyte monomer, a small molecule solvent and a lithium salt, wherein:
preset polymer electrolyte monomers comprising at least one of ECA, PEG, MPEG-MA, particularly, in particular, preset polymer electrolyte monomers further comprise preset mechanically reinforced polymers, wherein the preset mechanically reinforced polymers comprise at least one of silane coupling agents such as 3-methacryloxypropyl methyl diethoxy silane, ethylene-terminated polydimethylsiloxane and the like;
The preset polymer electrolyte also comprises a preset polymerization initiator, wherein the preset polymerization initiator comprises one of dibenzoyl peroxide, dilauroyl peroxide, tert-butyl peroxy-2-ethylhexanoate and azobisisobutyronitrile;
the small molecule solvent comprises at least one of PC, EC, DEC, DMC, VC, FEC and the like;
in the high-safety polymer battery, the small-molecule solvent is adsorbed and encapsulated by the polymer electrolyte (i.e., the preset polymer electrolyte), and as a result, the polymer electrolyte is in a solid state and no longer has fluidity.
Lithium salts, including LiFSI, liTFSI, liClO 4 And LiPF 6 At least one of them.
In particular, for the present invention, in the preset polymer electrolyte, the preset polymer electrolyte monomer, the lithium salt in the preset polymer electrolyte, the small molecular solvent and the polymerization initiator account for the following weight contents respectively:
5 to 60 percent of preset polymer electrolyte monomer, 10 to 40 percent of lithium salt, 5 to 60 percent of small molecule solvent and 0.01 to 0.1 percent of polymerization initiator.
Wherein, the preset mechanical enhancement type polymer in the preset polymer electrolyte monomer accounts for 20 to 80 percent of the weight of the preset polymer electrolyte monomer.
Referring to fig. 1, in order to prepare the high-safety polymer battery based on positive electrode protection provided by the invention, the invention also provides a preparation method of the high-safety polymer battery based on positive electrode protection, which comprises the following steps:
firstly, coating a layer of composite solid electrolyte coating on the outer surface (comprising an upper side surface, a lower side surface, a front side surface and a rear side surface) of an aluminum foil by adopting a micro gravure coating process (which is an existing mature process);
secondly, a roller coating or spraying process (which is the existing mature process) is adopted, and a layer of anode active material coating is coated on the composite solid electrolyte coating (specifically the outer surface) to obtain an anode;
and thirdly, integrating the positive electrode, the preset polymer electrolyte, the negative electrode and the support film obtained in the second step by adopting a free radical in-situ polymerization reaction initiation method (the existing mature process), and finally preparing the polymer battery.
In a specific implementation of the present invention, the first step specifically includes the following steps:
step S11: uniformly mixing a first oxide solid electrolyte, a first conductive agent, a first polymer contained in the first polymer solid electrolyte, a first lithium salt contained in the first polymer solid electrolyte and a first solvent to prepare a coating slurry for obtaining a composite solid electrolyte coating;
Step S12: coating slurry of a composite solid electrolyte coating is adopted to carry out double-sided coating on the aluminum foil (namely, the upper and lower side surfaces with larger surface area in the transversely distributed aluminum foil) by using a micro gravure coating mode, and drying and rolling are carried out for standby;
in a specific implementation of the present invention, the second step specifically includes the following steps:
step S21: uniformly mixing a positive electrode active material, a second conductive agent, a second oxide solid electrolyte, a second polymer contained in the second polymer solid electrolyte, a second lithium salt contained in the second polymer solid electrolyte and a second solvent to prepare a positive electrode active material coating slurry;
step S22: and (3) coating a positive electrode active material coating on the composite solid electrolyte coating obtained in the first step by adopting a roller coating or spraying process, and drying and rolling to obtain the positive electrode.
In a specific implementation of the present invention, the third step specifically includes the following steps:
step S31: and (3) respectively punching and drying the anode and the cathode (namely the cathode is a lithium metal cathode piece) obtained in the second step (specifically, the step S22), and assembling the polymer battery, wherein the dry battery core of the polymer battery is assembled to the stage before the injection of the polymer monomer solution.
Step S32: preparing a polymer monomer solution for later use from a preset polymer electrolyte monomer, a small molecular solvent, lithium salt in the preset polymer electrolyte and a preset polymerization initiator in a preset proportion.
Step S33: and (3) injecting the polymer monomer solution (namely the polymerization reaction mixed solution) obtained in the step (S32) into the polymer battery cell prepared in the step (S31), then placing the polymer battery cell in a dry atmosphere for negative pressure standing, sealing, cold pressing and hot pressing, and carrying out in-situ reaction at a preset temperature (for example, 50 ℃) and a preset pressure (for example, 0.3 MPa) to finally obtain the polymer lithium ion battery.
In a specific implementation of the present invention, in step S11, in the coating slurry of the composite solid electrolyte coating layer, the second conductive agent includes at least one of conductive nanomaterials such as carbon black, carbon nanotubes, and graphene.
In the present invention, in a specific implementation, in step S11, the first oxide solid electrolyte, including at least one of the oxide solid electrolytes of LLZO, LATP, and LAGP, is a nanomaterial with higher thermal stability;
a first polymer in a first polymer solid state electrolyte comprising at least one of PEO, PMMA, PVDF, PAN and PPC;
In particular, the first polymer solid electrolyte further comprises a first mechanically reinforced polymer comprising at least one of a silane coupling agent such as 3-methacryloxypropyl methyl diethoxysilane and ethylene-terminated polydimethylsiloxane;
the first polymer solid electrolyte also comprises a first polymerization initiator, wherein the first polymerization initiator comprises one of dibenzoyl peroxide, dilauroyl peroxide, tert-butyl peroxy-2-ethylhexanoate and azobisisobutyronitrile.
A first lithium salt in a first polymer solid state electrolyte comprising LiFSI, liTFSI, liClO 4 And LiPF 6 At least one of them.
In the present invention, in particular, in step S11, the coating slurry of the composite solid electrolyte coating layer contains the following components in proportion:
the first polymer solid electrolyte comprises a first polymer accounting for 5-30% of the total weight of the composite solid electrolyte coating (namely the dried composite solid electrolyte coating);
the first mechanically reinforced polymer (i.e., the first mechanical enhancer) in the first polymer solid electrolyte accounts for 20-80% of the total weight of the first polymer solid electrolyte;
Wherein the first polymerization initiator accounts for 0.01-1% of the total weight of the composite solid electrolyte coating;
the first polymer solid electrolyte comprises a first lithium salt accounting for 0.5-30% of the total weight of the composite solid electrolyte coating (namely the dried composite solid electrolyte coating);
the first conductive agent accounts for 5% -20% of the total weight of the composite solid electrolyte coating (namely the dried composite solid electrolyte coating);
the first oxide solid electrolyte accounts for 30-80% of the total weight of the composite solid electrolyte coating (namely the dried composite solid electrolyte coating).
In the present invention, in step S11, the solvent used in the coating slurry of the composite solid electrolyte coating layer is NMP, and the solid content of the slurry (i.e., the dried composite solid electrolyte coating layer) is 10% to 50%.
In a specific implementation of the present invention, in the step S21, the positive electrode active material coating layer is a coating slurry, and the positive electrode active material includes any one of positive electrode materials such as a lithium cobaltate material, a ternary material, and a high nickel material.
In a specific implementation of the present invention, in step S21, in the coating slurry of the positive electrode active material coating layer, the second conductive agent includes at least one of conductive nanomaterials such as carbon black, carbon nanotubes, and graphene.
In the present invention, in particular, in the coating slurry of the positive electrode active material coating layer, in step S21, a second oxide solid electrolyte including at least one of nano materials having higher thermal stability such as LLZO, LATP, and LAGP;
a second polymer in a second polymer solid state electrolyte comprising at least one of PEO, PMMA, PVDF, PAN and PPC;
a second lithium salt in a second polymer solid state electrolyte comprising LiFSI, liTFSI, liClO 4 And LiPF 6 At least one of them.
In the present invention, in particular, in step S21, in the coating slurry of the positive electrode active material coating layer, the proportions of the solid components are as follows:
the proportion of the positive electrode active material accounting for 88-98% of the total weight of the positive electrode active material coating (namely the dried positive electrode active material coating);
the second polymer solid electrolyte comprises a second polymer accounting for 0.5-5% of the total weight of the positive electrode active material coating;
the second polymer solid electrolyte contains second lithium salt which accounts for 0.5-5% of the total weight of the positive electrode active material coating;
the second conductive agent accounts for 0.5-10% of the total weight of the positive electrode active material coating;
The second oxide solid electrolyte (i.e., the second inorganic solid electrolyte) accounts for 0.5 to 5 percent of the total weight of the positive electrode active material coating.
In the present invention, in a specific implementation, in the step S21, in the coating slurry of the positive electrode active material coating layer, the second solvent used is NMP, and the solid content of the slurry is 50% to 80%.
In the present invention, in a specific implementation, in step S12, the preparation method of the composite solid electrolyte coating layer includes: directly coated on the aluminum foil, and the thickness of the single-layer composite solid electrolyte coating is 0.5-5 micrometers.
In the present invention, in a specific implementation, in step S22, the thickness of the single-layer positive electrode active material coating layer is 40-100 micrometers;
the thickness of the double-layer positive electrode active material coating is 80-200 micrometers.
In the present invention, in particular, in step S32, the preset polymer electrolyte monomers in the preset polymer electrolyte include at least one of ECA, PEG, MPEG to MA; in particular, the preset polymer electrolyte monomer further comprises a preset mechanical enhancement type polymer, and the preset mechanical enhancement type polymer comprises at least one of silane coupling agents such as 3-methacryloxypropyl methyl diethoxy silane, ethylene-terminated polydimethylsiloxane and the like;
In step S32, a preset polymerization initiator includes one of dibenzoyl peroxide, dilauroyl peroxide, tert-butyl peroxy-2-ethylhexanoate, and azobisisobutyronitrile;
in step S32, a small molecule solvent including at least one of PC, EC, DEC, DMC, VC, FEC and the like;
in step S32, a lithium salt in the polymer electrolyte is preset, including LiFSI, liTFSI, liClO 4 And LiPF 6 At least one of (a) and (b);
specifically, in step S32, the weight contents of the preset polymer electrolyte monomer in the preset polymer electrolyte, the lithium salt in the preset polymer electrolyte, and the preset polymerization initiator in the polymer monomer solution are as follows:
5 to 60 percent of preset polymer electrolyte monomer, 10 to 40 percent of lithium salt, 5 to 60 percent of micromolecular solvent and 0.01 to 0.1 percent of preset polymerization initiator.
Wherein, the preset mechanical enhancement type polymer in the preset polymer electrolyte monomer accounts for 20 to 80 percent of the weight of the preset polymer electrolyte monomer.
In the specific implementation of the invention, in the step S33, the negative pressure is 1 Pa-500 Pa, the cold pressing pressure is 0.01 MPA-1 MPa, the hot pressing temperature is 45-100 ℃, and the hot pressing time is 1 h-48 h.
In order to more clearly understand the technical scheme of the present invention, the technical scheme of the present invention is described below through specific embodiments.
Example 1.
The invention provides a preparation method of a high-safety polymer battery based on positive electrode protection, which adopts a micro gravure coating process to coat a composite solid electrolyte coating on an aluminum foil; and coating a positive electrode active material coating on the solid electrolyte layer by adopting a roller coating process. And adopting free radical in-situ initiation polymerization reaction to integrate the anode, the preset polymer electrolyte, the cathode and the support film to prepare the polymer battery. The specific decomposition steps are as follows:
first, preparing solid electrolyte slurry: the solid electrolyte layer coating slurry was prepared using LLZO, CNT, PAN/PVDF, 3-methacryloxypropyl methyl diethoxysilane, LITFSI, NMP, and the like, mixed well. The coating slurry was divided into 40% by weight of LLZO, 10% by weight of PAN, 10% by weight of PVDF, 9.9% by weight of 3-methacryloxypropyl methyldiethoxysilane, 10% by weight of azobisisobutyronitrile 0.1% by weight of cnt, and 20% by weight of LiTFSI. The solvent of the slurry was NMP, and the solid content of the slurry was 30%. Fully mixing and dispersing the mixture uniformly by using a centrifugal dispersing machine to obtain mixed slurry;
Preparing coating slurry of a positive electrode active material coating; the positive electrode active material, the second conductive agent, the oxide solid electrolyte, the second polymer contained in the second polymer solid electrolyte, the second lithium salt contained in the second polymer solid electrolyte, the second solvent and the like are uniformly mixed, and the coating slurry of the positive electrode active material coating is prepared by the following components in percentage by weight: CNT: PVDF: PPC: litfsi=93:2:2:1:2, positive electrode material layer coating slurry was prepared with a solids content of 70%.
Secondly, coating a solid electrolyte layer on the aluminum foil in a double-sided manner by using a micro-gravure coating manner, coating the aluminum foil in a double-sided manner by using a micro-gravure coating manner at a coating speed of 20 m/min and a single-sided coating thickness of 5 microns, and drying at 100 ℃ and winding for later use;
thirdly, coating a positive electrode material layer on the solid electrolyte layer by adopting a roller coating process, wherein the coating speed is 20 m/min, the single-sided coating thickness is 80 microns, and the double sides are 160 microns thick; and (5) drying at 100 ℃, and rolling the anode.
And fourthly, respectively punching and drying the anode and the cathode, and assembling the polymer battery, wherein the polymer battery dry cell is assembled to the stage before the injection of the polymer monomer solution.
And fifthly, preparing a certain amount of polymer monomer, a small molecular solvent, lithium salt and a polymerization initiator into a polymer monomer solution for later use. The polymer electrolyte monomer, the small molecular solvent, the lithium salt and the polymerization initiator respectively have the following weight contents: 10% of polymer electrolyte monomer (ECA), 10% of mechanical reinforced polymer (3-methacryloxypropyl methyl diethoxysilane), 50% of small molecule solvent, 29.9% of lithium salt (LiTFSI) and 0.1% of azodiisobutyronitrile.
And step six, injecting the polymer monomer solution obtained in the step five into the battery core prepared in the step four, placing the battery core in a dry atmosphere under the negative pressure of 300Pa, standing, sealing, cold pressing to 0.01MPa, hot pressing to 0.3MPa, and carrying out in-situ reaction for 12 hours at the temperature of 50 ℃ and the pressure of 0.3MPa to obtain the polymer lithium ion battery.
Example 2.
The invention provides a preparation method of a high-safety polymer battery based on positive electrode protection, which adopts a micro gravure coating process to coat a composite solid electrolyte coating on an aluminum foil; and coating a positive electrode active material coating on the composite solid electrolyte coating by adopting a spraying process. And adopting free radical in-situ initiation polymerization reaction to integrate the anode, the solid electrolyte, the cathode and the support film to prepare the polymer battery. The method comprises the following steps:
First, preparing solid electrolyte slurry: the solid electrolyte layer coating slurry was prepared using LATP, CNT, PMMA/PVDF, ethylene-terminated polydimethylsiloxane, liFSI, NMP, etc., mixed well. The coating slurry comprises the following solid raw materials in percentage by weight: LATP 40%, PMMA 10%, PVDF 10%, ethylene-blocked polydimethylsiloxane 19.5%, azobisisobutyronitrile 0.5%, CNT 10% and LiFSI 10%. The solvent of the slurry was NMP, and the solid content of the slurry was 30%. Fully mixing and dispersing the mixture uniformly by using a centrifugal dispersing machine to obtain mixed slurry;
preparing coating slurry of a positive electrode active material coating; the coating slurry of the positive electrode active material coating layer is prepared by uniformly mixing a positive electrode active material, a second conductive agent, a second oxide solid electrolyte, a second polymer contained in the second polymer solid electrolyte, a second lithium salt contained in the second polymer solid electrolyte, a second solvent and the like, wherein the weight ratio of the coating slurry of the positive electrode active material coating layer is NCM622: CNT: PAN: PVDF: lifsi=93:2:1:2:2, a positive electrode material layer coating slurry was prepared with a solid content of 70%.
Secondly, coating a solid electrolyte layer on the aluminum foil in a double-sided manner by using a micro-gravure coating manner, coating the aluminum foil in a double-sided manner by using a micro-gravure coating manner at a coating speed of 20 m/min and a single-sided coating thickness of 4 microns, and drying at 110 ℃ and winding for later use;
Thirdly, coating a positive electrode material layer on the solid electrolyte layer by adopting a roller coating process, wherein the coating speed is 20 m/min, the single-sided coating thickness is 60 microns, and the double sides are 120 microns thick; and (5) drying at 100 ℃, and rolling the anode.
And fourthly, respectively punching and drying the anode and the cathode, and assembling the polymer battery, wherein the polymer battery dry cell is assembled to the stage before the injection of the polymer monomer solution.
And fifthly, preparing a certain amount of polymer monomer, a small molecular solvent, lithium salt and a polymerization initiator into a polymer monomer solution for later use. The polymer electrolyte monomer, the small molecular solvent, the lithium salt and the polymerization initiator respectively have the following weight contents: 10% of polymer electrolyte monomer (PEG), 10% of mechanical reinforced polymer (ethylene-terminated polydimethylsiloxane), 60% of small molecule solvent, 19.9% of lithium salt (LiTFSI) and 0.5% of azodiisobutyronitrile.
And step six, injecting the polymer monomer solution obtained in the step five into the battery core prepared in the step four, placing the battery core in a dry atmosphere under the negative pressure of 300Pa, standing, sealing, cold pressing to 0.01MPa, hot pressing to 0.3MPa, and carrying out in-situ reaction for 6 hours at the temperature of 70 ℃ and the pressure of 0.3MPa to obtain the polymer lithium ion battery.
Example 3.
A preparation method of a high-safety polymer battery based on positive electrode protection adopts a micro-gravure coating process to coat a composite solid electrolyte layer on an aluminum foil; and coating a positive electrode material layer on the solid electrolyte layer by adopting a spraying process. And adopting free radical in-situ initiation polymerization reaction to integrate the anode, the solid electrolyte and the cathode support film to prepare the polymer battery. The method comprises the following steps:
first, preparing solid electrolyte slurry: the solid electrolyte layer coating slurry was prepared using LATP, CNT, PMMA/PVDF, 3-methacryloxypropyl methyl diethoxysilane, liFSI, NMP, etc., mixed well. The coating slurry was prepared from, by weight, 20% LATP, 30% LLZO, 10% PMMA, 10% PVDF, 9.5% 3-methacryloxypropyl methyl diethoxysilane, 0.5% azobisisobutyronitrile, 10% CNT, liClO 4 10%. The solvent of the slurry was NMP, and the solid content of the slurry was 35%. Fully mixing and dispersing the mixture uniformly by using a centrifugal dispersing machine to obtain mixed slurry;
preparing coating slurry of a positive electrode active material coating; the positive electrode active material, the second conductive agent, the second oxide solid electrolyte, the second polymer contained in the second polymer solid electrolyte, the second lithium salt contained in the second polymer solid electrolyte, the second solvent and the like are used for uniformly mixing, and the coating slurry of the positive electrode active material coating comprises the following components in parts by weight: CNT: PAN: PVDF: lifsi=93:2:1:2:2, a positive electrode material layer coating slurry was prepared with a solid content of 70%.
Secondly, coating a solid electrolyte layer on the aluminum foil in a double-sided manner by using a micro-gravure coating manner, coating the aluminum foil in a double-sided manner by using a micro-gravure coating manner at a coating speed of 20 m/min and a single-sided coating thickness of 3 microns, and drying at 110 ℃ and winding for later use;
thirdly, coating a positive electrode material layer on the solid electrolyte layer by adopting a roller coating process, wherein the coating speed is 30 m/min, the single-sided coating thickness is 40 microns, and the double sides are 80 microns thick; and (5) drying at 100 ℃, and rolling the anode.
Fourth, punching and drying the anode and the cathode, assembling the polymer battery, and assembling the dry battery core of the polymer battery to the stage before injecting the polymer monomer solution.
And fifthly, preparing a certain amount of polymer monomer, a small molecular solvent, lithium salt and a polymerization initiator into a polymer monomer solution for later use. The polymer electrolyte monomer, the small molecular solvent, the lithium salt and the polymerization initiator respectively have the following weight contents: 10% of polymer electrolyte monomer (MPEG-MA), 10% of polymer electrolyte monomer (PEG), 10% of mechanical reinforcement polymer (ethylene-terminated polydimethylsiloxane), 50% of small molecule solvent, 19.9% of lithium salt (LiTFSI) and 0.5% of azodiisobutyronitrile.
And step six, injecting the polymer monomer solution obtained in the step five into the battery core prepared in the step four, placing the battery core in a dry atmosphere under the negative pressure of 300Pa, standing, sealing, cold pressing to 0.01MPa, hot pressing to 0.2MPa, and carrying out in-situ reaction for 36 hours at the temperature of 40 ℃ and the pressure of 0.2MPa to obtain the polymer lithium ion battery.
Table 1: positive electrode and physical parameters based on solid electrolyte coating in each example.
As can be seen from table 1, the positive electrode protection solid electrolyte layer has controllable thickness and controllable conductivity, and simultaneously has high conductivity, high ionic conductivity, high binding power, high mechanical strength, and improved comprehensive performance of the lithium ion battery.
In summary, compared with the prior art, the high-safety polymer battery positive plate, the polymer battery and the preparation method of the battery are scientific in design, can effectively block the contact between the positive electrode active material and the aluminum foil (serving as a positive electrode current collector), prevent the thermit reaction from occurring when the polymer battery is safe and fails, avoid exothermic chain reaction of the battery, improve the safety of the polymer battery, and have great practical significance.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (7)

1. The high-safety polymer battery positive plate protected by the solid electrolyte coating is characterized by comprising an aluminum foil and a double-layer coating layer;
aluminum foil, as a positive current collector, coated with a double-layer coating layer on the outer surface thereof;
wherein the double-layer coating layer comprises a composite solid electrolyte coating coated on the aluminum foil and a positive electrode active material coating coated on the composite solid electrolyte coating;
a composite solid electrolyte coating comprising a first conductive agent and a composite solid electrolyte;
in the composite solid electrolyte coating, the first conductive agent includes at least one of carbon black, carbon nanotubes, and graphene;
in the composite solid electrolyte coating, the composition of the composite solid electrolyte material is a composite solid electrolyte including a first oxide solid electrolyte and a first polymer solid electrolyte;
wherein the first oxide solid state electrolyte comprises at least one of LLZO, LATP, and LAG, the LLZO, LATP, and LAG being oxide solid state electrolytes;
wherein the first polymer solid state electrolyte comprises a first polymer and a first lithium salt, wherein the first polymer specifically comprises at least one of PEO, PMMA, PVDF, PAN and PPC;
The first polymer solid state electrolyte further comprises a first mechanically reinforced polymer comprising at least one of 3-methacryloxypropyl methyl diethoxysilane and ethylene terminated polydimethylsiloxane;
the first polymer solid electrolyte also comprises a first polymerization initiator, wherein the first polymerization initiator comprises one of dibenzoyl peroxide, dilauroyl peroxide, tert-butyl peroxy-2-ethylhexanoate and azobisisobutyronitrile;
the first lithium salt comprises LiFSI, liTFSI, liClO 4 And LiPF 6 At least one of (a) and (b);
for the composite solid electrolyte coating, the proportion of each component is as follows:
wherein the proportion of the first polymer in the first polymer solid electrolyte to the total weight of the composite solid electrolyte coating is 20% -30%;
the first lithium salt in the first polymer solid electrolyte accounts for 0.5% -30% of the total weight of the composite solid electrolyte coating;
the first mechanically reinforced polymer in the first polymer solid electrolyte accounts for 20% -80% of the total weight of the first polymer solid electrolyte;
wherein the first mechanically reinforced polymer in the first polymer solid electrolyte comprises 9.5% or 9.9% of the total weight of the composite solid electrolyte coating;
Wherein the first conductive agent accounts for 5% -20% of the total weight of the composite solid electrolyte coating;
wherein the first oxide solid electrolyte accounts for 30% -80% of the total weight of the composite solid electrolyte coating;
wherein the first polymerization initiator accounts for 0.01% -1% of the total weight of the composite solid electrolyte coating;
the composite solid electrolyte coating is directly coated on the aluminum foil, and the thickness of the single-layer composite solid electrolyte coating is 3-5 microns;
and the thickness of the single-layer positive electrode active material coating is 40-80 microns.
2. The high safety polymer battery positive electrode sheet of claim 1, wherein the positive electrode active material coating comprises a positive electrode active material, a second polymer solid electrolyte, a second conductive agent, and a second oxide solid electrolyte, wherein the second polymer solid electrolyte comprises a second polymer and a second lithium salt, wherein the proportions of the components are as follows:
the positive electrode active material accounts for 88% -98% of the total weight of the positive electrode active material coating;
the second polymer in the second polymer solid electrolyte accounts for 0.5% -5% of the total weight of the positive electrode active material coating;
The second lithium salt in the second polymer solid electrolyte accounts for 0.5% -5% of the total weight of the positive electrode active material coating;
the second conductive agent accounts for 0.5% -10% of the total weight of the positive electrode active material coating;
the second oxide solid electrolyte accounts for 0.5% -5% of the total weight of the positive electrode active material coating.
3. The positive electrode sheet for a high-safety polymer battery according to claim 2, wherein the positive electrode active material coating layer comprises a positive electrode active material including any one of a lithium cobaltate material, a ternary material and a high-nickel material;
a second conductive agent included in the positive electrode active material coating layer, including at least one of carbon black, carbon nanotubes, and graphene;
a second polymer solid electrolyte comprising a second polymer and a second lithium salt, wherein the second polymer comprises PEO, PMMA, PVDF. At least one of PAN and PPC, the second lithium salt comprises LiFSI, liTFSI, liClO 4 And LiPF 6 At least one of (a) and (b);
the second oxide solid electrolyte included in the positive electrode active material coating layer specifically includes at least one of LLZO, LATP, and LAGP.
4. A high-safety polymer battery based on positive electrode protection, which is characterized by comprising the high-safety polymer battery positive electrode sheet according to any one of claims 1 to 3, a polymer battery negative electrode, a preset polymer electrolyte and a support film;
the polymer battery cathode is a lithium metal cathode piece or a traditional lithium ion battery cathode piece;
the material of the support film comprises any one of PEO, PMMA, PVDF, PAN, PET and PI base films;
the preset polymer electrolyte comprises a preset polymer electrolyte monomer, a small molecule solvent and lithium salt, wherein:
presetting polymer electrolyte monomers including at least one of ECA, PEG, MPEG-MA;
the pre-set polymer electrolyte monomer further comprises a pre-set mechanically reinforced polymer comprising at least one of 3-methacryloxypropyl methyl diethoxysilane and ethylene terminated polydimethylsiloxane;
the preset polymer electrolyte also comprises a preset polymerization initiator, wherein the preset polymerization initiator comprises one of dibenzoyl peroxide, dilauroyl peroxide, tert-butyl peroxy-2-ethylhexanoate and azobisisobutyronitrile;
the small molecule solvent comprises at least one of PC, EC, DEC, DMC, VC and FEC;
Lithium salts, including LiFSI, liTFSI, liClO 4 And LiPF 6 At least one of (a) and (b);
in the preset polymer electrolyte, the weight contents of the preset polymer electrolyte monomer, the lithium salt in the preset polymer electrolyte, the small molecular solvent and the polymerization initiator are as follows:
5% -60% of preset polymer electrolyte monomer, 10% -40% of lithium salt, 5% -60% of small molecule solvent and 0.01% -0.1% of polymerization initiator;
wherein, the preset mechanical reinforced polymer in the preset polymer electrolyte monomer accounts for 20-80% of the weight of the preset polymer electrolyte monomer;
and integrating the anode, the preset polymer electrolyte, the cathode and the support film by adopting a free radical in-situ polymerization reaction initiation method, and finally preparing the polymer battery.
5. The preparation method of the high-safety polymer battery based on positive electrode protection is characterized by comprising the following steps of:
firstly, coating a layer of composite solid electrolyte coating on the outer surface of an aluminum foil by adopting a micro gravure coating process;
secondly, coating a layer of anode active material coating on the composite solid electrolyte coating by adopting a roller coating or spraying process to obtain an anode;
thirdly, integrating the positive electrode, the preset polymer electrolyte, the negative electrode and the support film obtained in the second step by adopting a free radical in-situ polymerization reaction initiation method, and finally preparing and obtaining the polymer battery;
Wherein, the first step specifically comprises the following steps:
step S11: uniformly mixing a first oxide solid electrolyte, a first conductive agent, a first polymer contained in the first polymer solid electrolyte, a first lithium salt contained in the first polymer solid electrolyte and a first solvent to prepare a coating slurry for obtaining a composite solid electrolyte coating;
step S12: coating the aluminum foil with coating slurry of a composite solid electrolyte coating by using a micro gravure coating mode, drying and rolling the aluminum foil for standby;
wherein, the second step specifically comprises the following steps:
step S21: uniformly mixing a positive electrode active material, a second conductive agent, a second oxide solid electrolyte, a second polymer contained in the second polymer solid electrolyte, a second lithium salt contained in the second polymer solid electrolyte and a second solvent to prepare a positive electrode active material coating slurry;
step S22: coating a positive electrode active material coating on the composite solid electrolyte coating obtained in the first step by adopting a roller coating or spraying process, and drying and rolling to obtain a positive electrode;
wherein, the third step specifically comprises the following steps:
Step S31: respectively punching and drying the anode and the cathode obtained in the second step, and assembling the polymer battery, wherein the polymer battery dry cell is assembled to the stage before injecting the polymer monomer solution;
step S32: preparing a polymer monomer solution from preset polymer electrolyte monomers in preset polymer electrolyte, lithium salt in the preset polymer electrolyte, a preset polymerization initiator and a small molecular solvent according to a preset proportion;
step S33: injecting the polymer monomer solution obtained in the step S32 into the polymer battery cell prepared in the step S31, then placing the polymer battery cell in a dry atmosphere for negative pressure standing, sealing, cold pressing and hot pressing, and carrying out in-situ reaction at a preset temperature and a preset pressure to finally obtain the polymer lithium ion battery;
in step S11, in the coating slurry of the composite solid electrolyte coating layer, the first conductive agent includes at least one of carbon black, carbon nanotubes, and graphene;
in step S11, a first oxide solid electrolyte comprising at least one of LLZO, LATP, and LAGP oxide solid electrolytes;
a first polymer in a first polymer solid state electrolyte comprising at least one of PEO, PMMA, PVDF, PAN and PPC;
The first polymer solid state electrolyte further comprises a first mechanically reinforced polymer comprising at least one of 3-methacryloxypropyl methyl diethoxysilane and ethylene terminated polydimethylsiloxane;
the first polymer solid electrolyte also comprises a first polymerization initiator, wherein the first polymerization initiator comprises one of dibenzoyl peroxide, dilauroyl peroxide, tert-butyl peroxy-2-ethylhexanoate and azobisisobutyronitrile;
a first lithium salt in a first polymer solid state electrolyte comprising LiFSI, liTFSI, liClO 4 And LiPF 6 At least one of (a) and (b);
in step S11, in the coating slurry of the composite solid electrolyte coating layer, the component proportions of the respective solid components are specifically as follows:
the first polymer solid electrolyte comprises 20% -30% of the first polymer accounting for the total weight of the composite solid electrolyte coating;
the first mechanically reinforced polymer in the first polymer solid electrolyte accounts for 20% -80% of the total weight of the first polymer solid electrolyte;
wherein the first polymerization initiator accounts for 0.01% -1% of the total weight of the composite solid electrolyte coating;
the first polymer solid electrolyte comprises 0.5% -30% of a first lithium salt in the total weight of the composite solid electrolyte coating;
The first conductive agent accounts for 5% -20% of the total weight of the composite solid electrolyte coating;
the first oxide solid electrolyte accounts for 30% -80% of the total weight of the composite solid electrolyte coating;
in step S11, in the coating slurry of the composite solid electrolyte coating, the solvent used is NMP, and the solid content of the slurry is 10% -50%.
6. The method according to claim 5, wherein in the coating paste of the positive electrode active material coating layer, the positive electrode active material includes any one of a lithium cobaltate material, a ternary material, and a high nickel material;
in step S21, in the coating paste of the positive electrode active material coating layer, the second conductive agent includes at least one of carbon black, carbon nanotubes, and graphene conductive nanomaterial;
in step S21, in the coating paste of the positive electrode active material coating layer, a second oxide solid electrolyte including at least one of LLZO, LATP, and LAGP;
a second polymer in a second polymer solid state electrolyte comprising at least one of PEO, PMMA, PVDF, PAN and PPC;
a second lithium salt in a second polymer solid state electrolyte comprising LiFSI, liTFSI, liClO 4 And LiPF 6 At least one of (a) and (b);
in step S21, in the coating slurry of the positive electrode active material coating layer, the proportions of the solid components are specifically as follows:
the proportion of the positive electrode active material accounting for 88% -98% of the total weight of the positive electrode active material coating;
the second polymer solid electrolyte comprises a second polymer accounting for 0.5% -5% of the total weight of the positive electrode active material coating;
the second polymer solid electrolyte contains second lithium salt accounting for 0.5% -5% of the total weight of the positive electrode active material coating;
the second conductive agent accounts for 0.5% -10% of the total weight of the positive electrode active material coating;
the second oxide solid electrolyte accounts for 0.5% -5% of the total weight of the positive electrode active material coating;
in step S21, in the coating slurry of the positive electrode active material coating layer, the second solvent used is NMP, and the solid content of the slurry is 50% -80%.
7. The method of claim 6, wherein in step S12, the composite solid electrolyte coating is prepared by: directly coating on the aluminum foil, wherein the thickness of the single-layer composite solid electrolyte coating is 0.5-5 microns;
in step S22, the thickness of the single-layer positive electrode active material coating layer coated on the composite solid electrolyte coating layer is 40-100 micrometers;
In step S32, presetting polymer electrolyte monomers in the preset polymer electrolyte, including at least one of ECA, PEG, MPEG-MA;
the pre-set polymer electrolyte monomer further comprises a pre-set mechanically reinforced polymer comprising at least one of 3-methacryloxypropyl methyl diethoxysilane and ethylene terminated polydimethylsiloxane;
in step S32, a preset polymerization initiator includes one of dibenzoyl peroxide, dilauroyl peroxide, tert-butyl peroxy-2-ethylhexanoate, and azobisisobutyronitrile;
in step S32, a small molecule solvent comprising at least one of PC, EC, DEC, DMC, VC and FEC;
in step S32, a lithium salt in the polymer electrolyte is preset, including LiFSI, liTFSI, liClO 4 And LiPF 6 At least one of (a) and (b);
in step S32, the weight contents of the preset polymer electrolyte monomer, the lithium salt in the preset polymer electrolyte, and the preset polymerization initiator in the polymer monomer solution are respectively: 5% -60% of preset polymer electrolyte monomer, 10% -40% of lithium salt, 5% -60% of small molecule solvent and 0.01% -0.1% of preset polymerization initiator;
wherein, the preset mechanical enhancement type polymer in the preset polymer electrolyte monomer accounts for 20-80% of the weight of the preset polymer electrolyte monomer;
In the step S33, after the battery cell is sealed, the preset pressure of cold pressing and hot pressing is 0.001MPa-0.5 MPa, the temperature of hot pressing is 40-70 ℃, and the reaction time is 2-12 hours.
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