CN111916747A - 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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CN111916747A
CN111916747A CN202010801285.4A CN202010801285A CN111916747A CN 111916747 A CN111916747 A CN 111916747A CN 202010801285 A CN202010801285 A CN 202010801285A CN 111916747 A CN111916747 A CN 111916747A
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polymer
solid electrolyte
coating
active material
preset
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CN111916747B (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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    • 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

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; the aluminum foil is used as a positive current collector, and the outer surface of the aluminum foil is coated with a double-layer coating layer; wherein, the double-layer coating layer comprises a composite solid electrolyte coating coated on the aluminum foil and a positive active material coating coated on the composite solid electrolyte coating; a composite solid electrolyte coating includes a first conductive agent and a composite solid electrolyte. In addition, the invention also discloses a high-safety polymer battery based on the anode protection and a preparation method of the high-safety polymer battery based on the anode protection. The high-safety polymer battery positive plate, the polymer battery and the battery preparation method disclosed by the invention can effectively prevent the contact between the positive active material and the aluminum foil, prevent the occurrence of thermite reaction when the polymer battery is in safety failure, avoid the 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 increase of energy density of lithium ion batteries, consumers have higher and higher requirements on safety performance of lithium ion batteries. Positive electrode materials of high energy density layered crystal structure, e.g. LiNixCoyMnzO2(NCM)、LiCoO2With much attention paid to and research by the skilled worker, it is well known that the thermal stability of a high energy density positive electrode material during charging is a key factor affecting its application.
In the case of abuse of the lithium ion battery, internal short circuit may occur, joule heat accumulation caused by the internal short circuit may cause exothermic reactions of materials such as a large-area negative electrode, a large-area positive electrode, an electrolyte, a separator and the like, and further cause an exothermic chain reaction, which finally causes a thermal runaway problem of the lithium ion battery. 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 block the contact between the positive active material and the aluminum foil (as the positive current collector), prevent the occurrence of thermite reaction when the battery fails, and reduce the self-heating reaction, the method is one of effective methods for preventing the occurrence of heat spreading of the battery.
It should be noted that, the positive electrode active material is an oxide intercalated with lithium atoms, in a charged state, the positive electrode material is converted into an oxide by delithiation, the oxide and aluminum metal can generate an oxidation-reduction reaction under a high heat condition generated by thermal failure of the lithium ion battery, aluminum shows strong reducibility, and due to extremely low enthalpy of formation (-1645kJ/mol) of aluminum, a large amount of heat is released in a short time during the reaction, so that the thermal failure effect of the lithium ion battery can be aggravated.
People are always seeking improvement methods, such as coating the surface of a positive active material, doping elements and the like, but the surface of the positive 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 active material is coated with the inactive material, so that the contact between the positive active material and the aluminum foil cannot be effectively prevented.
Therefore, there is an urgent need to develop a technology that can effectively block the contact between the positive active material and the aluminum foil (as the positive current collector), prevent the occurrence of thermite reaction when the polymer battery is in safety failure, avoid the exothermic chain reaction of the battery, and improve the safety of the polymer battery.
Disclosure of Invention
The invention aims to provide a high-safety polymer battery positive plate, a polymer battery and a battery preparation method aiming at the technical defects in the prior art.
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;
the aluminum foil is used as a positive current collector, and the outer surface of the aluminum foil is coated with a double-layer coating layer;
wherein, the double-layer coating layer comprises a composite solid electrolyte coating coated on the aluminum foil and a positive 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 layer, a component 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 electrolyte comprises at least one of LLZO, LATP and LAGP, LLZO, LATP and LAG being oxide solid electrolytes;
wherein the first polymer solid 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 3-methacryloxypropylmethyldiethoxysilane and a vinyl-terminated polydimethylsiloxane;
the first polymer solid electrolyte also comprises a first polymerization initiator, and 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, LiClO4And LiPF6At least one of (1).
For the composite solid electrolyte coating, the component proportions are as follows:
wherein, the proportion of the first polymer in the first polymer solid electrolyte accounts for 5 to 30 percent of the total weight of the composite solid electrolyte coating;
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 mechanical enhancement type 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 to 20 percent of the total weight of the composite solid electrolyte coating;
wherein, the proportion of the first oxide solid electrolyte in the total weight of the composite solid electrolyte coating is 30-80%.
Wherein, the first polymerization initiator accounts for 0.01 to 1 percent 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;
the positive electrode active material coating is coated on the composite solid electrolyte coating, and the thickness of the single-layer positive electrode active material coating is 40-100 micrometers.
Preferably, the positive electrode active material coating layer 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, and the ratio of the components is as follows:
the positive active material accounts for 88 to 98 percent of the total weight of the positive active material coating;
the second polymer in the second polymer solid electrolyte accounts for 0.5 to 5 percent of the total weight of the positive active material coating;
the second lithium salt in the second polymer solid electrolyte accounts for 0.5 to 5 percent of the total weight of the positive active material coating;
the second conductive agent accounts for 0.5 to 10 percent of the total weight of the positive 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 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 nickel-rich material;
the second conductive agent included in the positive electrode active material coating layer comprises at least one of conductive nano materials such as carbon black, carbon nano tubes and graphene;
the second polymer solid electrolyte included in the positive active material coating layer 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 and LiClO4And LiPF6In (1)At least one of;
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 plate, a polymer battery negative electrode, a preset polymer electrolyte and a support membrane;
wherein, the polymer battery negative electrode is a lithium metal negative electrode plate or a traditional lithium ion battery negative electrode plate;
the material of the supporting 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 molecular solvent and a lithium salt, wherein:
presetting a polymer electrolyte monomer comprising at least one of ECA, PEG and MPEG-MA;
the preset polymer electrolyte monomer also comprises a preset mechanical enhancement polymer, and the preset mechanical enhancement polymer comprises at least one of 3-methacryloxypropyl methyldiethoxysilane and vinyl-terminated polydimethylsiloxane;
the preset polymer electrolyte also comprises a preset polymerization initiator, and 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, LiClO4And LiPF6At least one of;
in the preset polymer electrolyte, the weight contents of a preset polymer electrolyte monomer, lithium salt in the preset polymer electrolyte, a small molecular solvent and a polymerization initiator are respectively as follows:
5-60% of a preset polymer electrolyte monomer, 10-40% of lithium salt, 5-60% of a small molecular solvent and 0.01-0.1% of a 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, the positive electrode, the preset polymer electrolyte, the negative electrode and the support membrane are integrated by adopting a method of free radical in-situ initiation polymerization reaction, and finally the polymer battery is prepared.
In addition, the invention also provides a preparation method of the high-safety polymer battery based on the 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 positive active material coating on the composite solid electrolyte coating by adopting a roller coating or spraying process to obtain a positive electrode;
thirdly, integrating the anode, the preset polymer electrolyte, the cathode and the support membrane obtained in the second step by adopting a free radical in-situ initiation polymerization reaction 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 a first polymer solid electrolyte, a first lithium salt contained in a 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 on both sides by using a micro-gravure coating mode and adopting coating slurry of the composite solid electrolyte coating, drying and rolling for later use;
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 layer coating slurry;
step S22: coating a positive 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, assembling the polymer battery, and assembling the polymer battery dry cell to a pre-injection stage of a polymer monomer solution;
step S32: preparing a preset polymer electrolyte monomer in a preset polymer electrolyte, a lithium salt in the preset polymer electrolyte, a preset polymerization initiator and a small molecular solvent according to a preset proportion into a polymer monomer solution for later use;
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 at a negative pressure for standing, sealing, then carrying out 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 nano materials;
in step S11, a first oxide solid state electrolyte including at least one of nano materials having higher thermal stability such as LLZO, LATP, and LAGP oxide solid state electrolytes;
a first polymer in a first polymer solid electrolyte comprising 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 3-methacryloxypropylmethyldiethoxysilane and a vinyl-terminated polydimethylsiloxane;
the first polymer solid electrolyte also comprises a first polymerization initiator, and 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 electrolyte comprising LiFSI, LiTFSI, LiClO4And LiPF6At least one of;
in step S11, in the coating slurry of the composite solid electrolyte coating layer, the component ratio of each solid component is specifically as follows:
the first polymer solid electrolyte comprises a first polymer which accounts for 5 to 30 percent of the total weight of the composite solid electrolyte coating;
the first mechanical enhancement type 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 to 1 percent of the total weight of the composite solid electrolyte coating;
the first polymer solid electrolyte contains a first lithium salt which accounts for 0.5 to 30 percent 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 a lithium cobaltate material, a ternary material, and a nickel-rich 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 conductive nanomaterials such as carbon black, carbon nanotubes, and graphene;
in step S21, in the coating slurry of the positive active material coating layer, a second oxide solid electrolyte including at least one of nano materials having high 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 electrolyte comprising LiFSI, LiTFSI, LiClO4And LiPF6At least one of;
in step S21, in the coating slurry of the positive electrode active material coating layer, the solid component ratios are specifically as follows:
the positive active material accounts for 88 to 98 percent of the total weight of the positive active material coating;
the second polymer solid electrolyte comprises a second polymer which accounts for 0.5 to 5 percent of the total weight of the positive active material coating;
the second polymer solid electrolyte contains a second lithium salt which accounts for 0.5 to 5 percent of the total weight of the positive active material coating;
the second conductive agent accounts for 0.5 to 10 percent of the total weight of the positive active material coating;
a second oxide solid electrolyte (i.e., a second inorganic solid electrolyte) in a proportion of 0.5% to 5% by weight based on the total weight of the positive electrode active material coating layer;
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 method for preparing the composite solid electrolyte coating layer is: the coating is directly coated on an aluminum foil, and the thickness of the single-layer composite solid electrolyte coating is 0.5-5 microns;
in step S22, the positive electrode active material coating layer coated on the composite solid electrolyte coating layer has a thickness of 40 to 100 μm;
in step S32, presetting a preset polymer electrolyte monomer in the polymer electrolyte, including at least one of ECA, PEG, and MPEG-MA;
the preset polymer electrolyte monomer also comprises a preset mechanical enhancement polymer, and the preset mechanical enhancement polymer comprises at least one of 3-methacryloxypropyl methyldiethoxysilane and vinyl-terminated polydimethylsiloxane;
in step S32, the predetermined 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, lithium salt in polymer electrolyte is preset, including LiFSI, LiTFSI, LiClO4And LiPF6At least one of;
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: presetting 5-60% of polymer electrolyte monomer, 10-40% of lithium salt, 5-60% of micromolecular solvent and 0.01-0.1% of polymerization initiator;
wherein the preset mechanically enhanced polymer in the preset polymer electrolyte monomer accounts for 20-80% of the weight of the preset polymer electrolyte monomer.
In step S33, after the cell is sealed, the preset pressure of cold pressing and hot pressing is 0.001MPa to 0.5MPa, the temperature of hot pressing is 40 ℃ to 70 ℃, and the reaction time is 2 hours to 12 hours.
Compared with the prior art, the positive plate of the high-safety polymer battery, the polymer battery and the preparation method of the polymer battery are scientific in design, can effectively prevent the positive active material from contacting with the aluminum foil (serving as a positive current collector), prevent the occurrence of thermite reaction when the polymer battery fails, avoid the exothermic chain reaction of the battery, and improve the safety of the polymer battery, and have great practical significance.
Drawings
Fig. 1 is a flow chart of a method for preparing a high-safety polymer battery based on positive electrode protection according to the present invention.
Detailed Description
In order that those skilled in the art will better understand the technical solution of the present invention, the following detailed description of the present invention is provided in conjunction with the accompanying 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;
an 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 coating layer;
wherein the double-layer coating layer comprises a composite solid electrolyte coating coated on the aluminum foil and a positive active material coating coated on the composite solid electrolyte coating.
In the present invention, in a specific implementation, the composite solid electrolyte coating, including the first conductive agent and the composite solid electrolyte, has conductivity, lithium ion conductivity and thermal stability, and is used to isolate the positive active material from directly contacting the aluminum foil.
In the concrete implementation, 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 micrometers. The composite solid electrolyte coating coated on one surface of the aluminum foil is a single-layer composite solid electrolyte coating, and single-layer coating is performed.
In a specific implementation manner, in the composite solid electrolyte coating, the first conductive agent comprises at least one of carbon black, carbon nanotubes, graphene and other conductive nano materials.
In a specific implementation, in the composite solid electrolyte coating layer, the components of the composite solid electrolyte material are a composite solid electrolyte including a first oxide solid electrolyte and a first polymer solid electrolyte;
wherein, the first oxide solid electrolyte can specifically include at least one of nanometer inorganic solid electrolyte materials with higher thermal stability such as oxide solid electrolytes such as LLZO, LATP and LAGP;
wherein the first polymer solid 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, wherein the first mechanically reinforced polymer comprises at least one of silane coupling agents such as 3-methacryloxypropylmethyldiethoxysilane and vinyl-terminated polydimethylsiloxane;
specifically, the first polymer solid electrolyte further comprises a first polymerization initiator, and 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, LiClO4And LiPF6At least one of;
in particular, 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 accounts for 5 to 30 percent of the total weight of the composite solid electrolyte coating;
the first mechanical enhancement polymer (i.e. the first mechanical reinforcing agent) in the first polymer solid electrolyte accounts for 20-80% of 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 to 20 percent of the total weight of the composite solid electrolyte coating;
wherein, the proportion of the first oxide solid electrolyte in the total weight of the composite solid electrolyte coating is 30-80%.
Wherein, the first polymerization initiator accounts for 0.01 to 1 percent of the total weight of the composite solid electrolyte coating;
it should be noted that, for the present invention, for the composite solid electrolyte coating, the first oxide solid electrolyte (i.e., inorganic solid electrolyte) therein functions as: the mechanical strength of the isolating layer is increased, so that the application of the ultrathin aluminum foil is possible;
for a composite solid electrolyte coating, the first polymer solid electrolyte therein functions to: the flexibility of the isolating layer is increased, and meanwhile, the binding force with the positive electrode active material layer is increased; meanwhile, the composite solid electrolyte coating also has high lithium ion conductivity, so that the lithium ion conductivity of the anode bottom layer can be increased.
In the invention, in the specific implementation, for the high-safety polymer battery positive plate, the positive active material coating is coated on the composite solid electrolyte coating, and the thickness of the single-layer positive active material coating is preferably 40-100 micrometers;
the thickness of the double-layer positive electrode active material coating is 80-200 microns.
In the present invention, in a specific implementation, for the high-safety positive electrode sheet, the positive electrode active material coating coated on the composite solid electrolyte coating 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), where the second polymer solid electrolyte includes a second polymer and a second lithium salt, where the ratio of the components is as follows:
the positive active material accounts for 88 to 98 percent of the total weight of the positive active material coating;
the second polymer in the second polymer solid electrolyte accounts for 0.5 to 5 percent of the total weight of the positive active material coating;
the second lithium salt in the second polymer solid electrolyte accounts for 0.5 to 5 percent of the total weight of the positive active material coating;
the second conductive agent accounts for 0.5 to 10 percent of the total weight of the positive 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 active material coating.
In the invention, for the positive plate of the high-safety polymer battery, the positive active material contained in the positive active material coating comprises any one of the positive materials such as lithium cobaltate material, ternary material and high nickel material.
In the invention, for the positive plate of the high-safety polymer battery, the second conductive agent included in the positive active material coating comprises at least one of conductive nano materials such as carbon black, carbon nano tubes and graphene.
In the present invention, in a specific implementation manner, for the positive electrode plate of the high-safety polymer battery, the second polymer solid electrolyte included in the positive active material coating layer includes a second polymer and a second lithium salt, wherein the second polymer specifically includes at least one of PEO, PMMA, PVDF, PAN, and PPC, and the second lithium salt includes LiFSI, LiTFSI, LiClO4And LiPF6At least one of (1).
In the invention, particularly, for the high-safety polymer battery positive plate, the second oxide solid electrolyte (i.e. the second inorganic solid electrolyte) included in the positive active material coating layer can specifically include at least one of nano inorganic solid electrolyte materials with high thermal stability such as LLZO, LATP and LAGP;
it should be noted that, for the present invention, in view of 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 composite solid electrolyte coating with high thermal stability is constructed between the aluminum foil and the positive active material to block the contact between the positive active material and the aluminum foil, so as to prevent the occurrence of thermite reaction when the polymer battery fails safely, reduce the "self-heating reaction" of the battery, thereby avoiding the 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, which 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 particular to implementation, in the high-safety polymer battery, the polymer battery negative electrode is a lithium metal negative electrode sheet, and can also be a traditional lithium ion battery negative electrode sheet.
In the present invention, in a specific implementation, in the high-safety polymer battery, the material of the support film includes any one of PEO, PMMA, PVDF, PAN, PET, PI, and the like base films.
In the invention, in particular, a method of free radical in-situ initiation polymerization reaction (existing mature process) is adopted, and the anode, the preset polymer electrolyte, the cathode and the support membrane are integrated to finally prepare the polymer battery.
In the present invention, in a specific implementation, in the high-safety polymer battery, the predetermined polymer electrolyte includes a predetermined polymer electrolyte monomer, a small molecule solvent and a lithium salt, wherein:
the method comprises the following steps of presetting a polymer electrolyte monomer, wherein the preset polymer electrolyte monomer comprises at least one of ECA, PEG and MPEG-MA, and particularly, in specific implementation, the preset polymer electrolyte monomer also comprises a preset mechanically-enhanced polymer, and the preset mechanically-enhanced polymer comprises at least one of silane coupling agents such as 3-methacryloxypropylmethyldiethoxysilane and vinyl-terminated polydimethylsiloxane;
the preset polymer electrolyte also comprises a preset polymerization initiator, and 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;
in the high-safety polymer battery, the small-molecule solvent is adsorbed and encapsulated by the polymer electrolyte (i.e., the predetermined polymer electrolyte), and as a result, the small-molecule solvent is in a solid state and does not have fluidity.
Lithium salts including LiFSI, LiTFSI, LiClO4And LiPF6At least one of (1).
In particular, for the present invention, in the preset polymer electrolyte, the weight contents of the preset polymer electrolyte monomer, the lithium salt in the preset polymer electrolyte, the small molecule solvent and the polymerization initiator are respectively as follows:
5-60% of a preset polymer electrolyte monomer, 10-40% of lithium salt, 5-60% of a small molecular solvent and 0.01-0.1% of a 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 above high-safety polymer battery based on positive electrode protection, the present invention also provides a preparation method of the high-safety polymer battery based on positive electrode protection, comprising the steps of:
the method comprises the following steps of firstly, coating a layer of composite solid electrolyte coating on the outer surface (including the upper side surface, the lower side surface, the front side surface and the rear side surface) of an aluminum foil by adopting a micro-gravure coating process (which is a conventional mature process);
secondly, coating a layer of positive active material coating on the composite solid electrolyte coating (specifically the outer surface) by adopting a roller coating or spraying process (which is the existing mature process) to obtain a positive electrode;
and thirdly, integrating the anode, the preset polymer electrolyte, the cathode and the support membrane obtained in the second step by adopting a free radical in-situ initiation polymerization reaction method (which is 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 a first polymer solid electrolyte, a first lithium salt contained in a 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 on both sides (namely the upper side surface and the lower side surface with larger surface area in the aluminum foil which is transversely distributed) by adopting a micro-gravure coating mode and coating slurry of a composite solid electrolyte coating, drying and rolling for later use;
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 layer coating slurry;
step S22: and (3) coating a positive 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 positive electrode and the negative electrode (namely the negative electrode is the lithium metal negative plate) obtained in the second step (specifically, step S22), assembling the polymer battery, and assembling the polymer battery dry cell to a pre-injection stage of the polymer monomer solution.
Step S32: preparing a polymer monomer solution from a preset polymer electrolyte monomer, a small molecular solvent, a lithium salt and a preset polymerization initiator in a preset polymer electrolyte according to a preset proportion for later use.
Step S33: and (2) injecting the polymer monomer solution (i.e., 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 at a negative pressure for standing, sealing, cold-pressing and hot-pressing, and carrying out in-situ reaction at a preset temperature (e.g., 50 ℃) and a preset pressure (e.g., 0.3MPa), so as to finally obtain the polymer lithium ion battery.
In the present invention, in a specific implementation manner, 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 state electrolyte, including at least one of the oxide solid state electrolytes such as LLZO, LATP, and LAGP, is a nanomaterial having high thermal stability;
a first polymer in a first polymer solid 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 silane coupling agents such as 3-methacryloxypropylmethyldiethoxysilane and vinyl-terminated polydimethylsiloxane;
the first polymer solid electrolyte also comprises a first polymerization initiator, and 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 electrolyte comprising LiFSI, LiTFSI, LiClO4And LiPF6At least one of (1).
In the present invention, in step S11, the composition ratio of each solid component in the coating slurry of the composite solid electrolyte coating is specifically as follows:
the first polymer solid electrolyte comprises a first polymer which accounts for 5-30% of the total weight of the composite solid electrolyte coating (namely the dried composite solid electrolyte coating);
the first mechanical enhancement polymer (namely the first mechanical reinforcing agent) 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 to 1 percent of the total weight of the composite solid electrolyte coating;
the first polymer solid electrolyte comprises a first lithium salt which accounts for 0.5 to 30 percent 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 (i.e. the dried composite solid electrolyte coating).
In the present invention, in step S11, in a coating slurry of the composite solid electrolyte coating, a solvent used is NMP, and a solid content of the slurry (i.e., the composite solid electrolyte coating after drying) is 10% to 50%.
In the present invention, in step S21, in the coating slurry 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 nickel-rich material.
In the present invention, in step S21, the second conductive agent includes at least one of conductive nanomaterials such as carbon black, carbon nanotubes, and graphene in the coating slurry of the positive electrode active material coating layer.
In the present invention, in step S21, in the coating slurry of the positive electrode active material coating layer, the second oxide solid electrolyte includes at least one of nano materials having high 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 electrolyte comprising LiFSI, LiTFSI, LiClO4And LiPF6At least one of (1).
In the present invention, in step S21, specifically, the solid component ratios in the coating slurry of the positive electrode active material coating layer are as follows:
the positive active material accounts for 88 to 98 percent of the total weight of the positive active material coating (namely the dried positive active material coating);
the second polymer solid electrolyte comprises a second polymer which accounts for 0.5 to 5 percent of the total weight of the positive active material coating;
the second polymer solid electrolyte contains a second lithium salt which accounts for 0.5 to 5 percent of the total weight of the positive active material coating;
the second conductive agent accounts for 0.5 to 10 percent of the total weight of the positive 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 active material coating.
In the present invention, in step S21, in a specific implementation manner, the second solvent used in the coating slurry of the positive electrode active material coating layer is NMP, and the solid content of the slurry is 50% to 80%.
In the present invention, in a specific implementation manner, in step S12, the preparation method of the composite solid electrolyte coating includes: the coating is directly coated on an aluminum foil, and the thickness of the single-layer composite solid electrolyte coating is 0.5-5 microns.
In the invention, in step S22, the thickness of the single-layer positive electrode active material coating is 40 to 100 micrometers;
the thickness of the double-layer positive electrode active material coating is 80-200 microns.
In the present invention, in step S32, a preset polymer electrolyte monomer in the polymer electrolyte is preset, including at least one of ECA, PEG, and MPEG-MA; in particular, the preset polymer electrolyte monomer also comprises a preset mechanical enhancement polymer, and the preset mechanical enhancement polymer comprises at least one of silane coupling agents such as 3-methacryloxypropylmethyldiethoxysilane and vinyl-terminated polydimethylsiloxane;
in step S32, the predetermined 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, etc.;
in step S32, lithium salt in polymer electrolyte is preset, including LiFSI, LiTFSI, LiClO4And LiPF6At least one of;
specifically, in step S32, in the polymer monomer solution, 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 are as follows:
presetting 5-60% of a preset polymer electrolyte monomer, 10-40% of a lithium salt, 5-60% of a small molecular solvent and 0.01-0.1% of a polymerization initiator.
Wherein the preset mechanically enhanced polymer in the preset polymer electrolyte monomer accounts for 20-80% of the weight of the preset polymer electrolyte monomer.
In the invention, in step S33, the negative pressure is 1 Pa-500 Pa, the cold pressure is 0.01 MPA-1 MPa, the hot pressing temperature is 45-100 ℃, and the hot pressing time is 1-48 h.
In order to more clearly understand the technical solution of the present invention, the technical solution of the present invention is described below by specific examples.
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 active material coating on the solid electrolyte layer by adopting a roller coating process. And (3) adopting a free radical in-situ initiation polymerization reaction to integrate the anode, the preset polymer electrolyte, the cathode and the support membrane to prepare the polymer battery. The specific decomposition steps are as follows:
step one, preparing solid electrolyte slurry: the solid electrolyte layer coating slurry was prepared by uniformly mixing LLZO, CNT, PAN/PVDF, 3-methacryloxypropylmethyldiethoxysilane, LITFSI, NMP, etc. The coating slurry was distributed as a percentage by weight of solid materials, 40% LLZO, 10% PAN, 10% PVDF, 9.9% 3-methacryloxypropylmethyldiethoxysilane, 10% azobisisobutyronitrile 0.1% CNT, and 20% LiTFSI. The solvent of the slurry was NMP, and the solid content of the slurry was 30%. Fully mixing and uniformly dispersing the mixture by using a centrifugal dispersion machine to obtain mixed slurry;
preparing coating slurry of the positive 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 weight ratio of coating slurry of the positive electrode active material coating is NCM 811: CNT: PVDF: PPC: and preparing a positive electrode material layer coating slurry with solid content of 70 percent, wherein the LiTFSI is 93:2:2:1: 2.
Secondly, coating a solid electrolyte layer on the two sides of the aluminum foil in a micro-gravure coating mode, coating the two sides of the aluminum foil in a micro-gravure coating mode at a coating speed of 20 m/min and a single-side coating thickness of 5 microns at a drying temperature of 100 ℃, and rolling 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 coating thickness of one side is 80 microns, and the coating thickness of two sides is 160 microns; and (5) rolling the positive electrode at the drying temperature of 100 ℃.
And fourthly, respectively punching and drying the anode and the cathode, assembling the polymer battery, and assembling the polymer battery dry battery core to a pre-injection stage of the polymer monomer solution.
Fifthly, preparing a certain amount of polymer monomer, micromolecular solvent, lithium salt and polymerization initiator into polymer monomer solution for later use. The polymer electrolyte monomer, the micromolecular solvent, the lithium salt and the polymerization initiator respectively comprise the following components in percentage by weight: 10% of polymer electrolyte monomer (ECA), 10% of mechanical reinforced polymer (3-methacryloxypropylmethyldiethoxysilane), 50% of small molecular solvent, 29.9% of lithium salt (LiTFSI) and 0.1% of azobisisobutyronitrile.
And sixthly, injecting the polymer monomer solution obtained in the fifth step into the battery cell prepared in the fourth step, placing the battery cell in a dry atmosphere at the negative pressure of 300Pa for standing, sealing, cold-pressing at 0.01MPa and hot-pressing at 0.3MPa, and carrying out in-situ reaction at the temperature of 50 ℃ and the pressure of 0.3MPa for 12 hours 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 active material coating on the composite solid electrolyte coating by adopting a spraying process. And (3) adopting a free radical in-situ initiation polymerization reaction to integrate the anode, the solid electrolyte, the cathode and the support membrane to prepare the polymer battery. The method comprises the following steps:
step one, preparing solid electrolyte slurry: LATP, CNT, PMMA/PVDF, ethylene-terminated polydimethylsiloxane, LiFSI, NMP, and the like were uniformly mixed to prepare a solid electrolyte layer coating slurry. The coating slurry comprises the following solid raw materials in percentage by weight: LATP 40%, PMMA 10%, PVDF 10%, ethylene-terminated polydimethylsiloxane 19.5%, azobisisobutyronitrile 0.5%, CNT 10%, LiFSI 10%. The solvent of the slurry was NMP, and the solid content of the slurry was 30%. Fully mixing and uniformly dispersing the mixture by using a centrifugal dispersion machine to obtain mixed slurry;
preparing coating slurry of the positive 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 uniformly mixed, and the weight ratio of coating slurry of the positive electrode active material coating is NCM 622: CNT: PAN: PVDF: and (3) preparing positive electrode material layer coating slurry with the solid content of 70 percent, wherein the LiFSI is 93:2:1:2: 2.
Secondly, coating a solid electrolyte layer on the two sides of the aluminum foil in a micro-gravure coating mode, coating the two sides of the aluminum foil in a micro-gravure coating mode at a coating speed of 20 m/min and a single-side coating thickness of 4 microns at a drying temperature of 110 ℃, and rolling 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 coating thickness of one side is 60 micrometers, and the coating thickness of the two sides is 120 micrometers; and (5) rolling the positive electrode at the drying temperature of 100 ℃.
And fourthly, respectively punching and drying the anode and the cathode, assembling the polymer battery, and assembling the polymer battery dry battery core to a pre-injection stage of the polymer monomer solution.
Fifthly, preparing a certain amount of polymer monomer, micromolecular solvent, lithium salt and polymerization initiator into polymer monomer solution for later use. The polymer electrolyte monomer, the micromolecular solvent, the lithium salt and the polymerization initiator respectively comprise the following components in percentage by weight: 10% of polymer electrolyte monomer (PEG), 10% of mechanical reinforced polymer (ethylene-terminated polydimethylsiloxane), 60% of small molecular solvent, 19.9% of lithium salt (LiTFSI) and 0.5% of azodiisobutyronitrile.
And sixthly, injecting the polymer monomer solution obtained in the fifth step into the battery cell prepared in the fourth step, placing the battery cell in a dry atmosphere at the negative pressure of 300Pa for standing, sealing, cold-pressing at 0.01MPa and hot-pressing at 0.3MPa, and carrying out in-situ reaction at the temperature of 70 ℃ and the pressure of 0.3MPa for 6 hours 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 (3) adopting a free radical in-situ initiation polymerization reaction to integrate the anode, the solid electrolyte and the cathode support membrane to prepare the polymer battery. The method comprises the following steps:
step one, preparing solid electrolyte slurry: LaTP, CNT, PMMA/PVDF, 3-methacryloxypropylmethyldiethoxysilane, LiFSI, NMP and the like are uniformly mixed to prepare the solid electrolyte layer coating slurry. The coating slurry comprises 20 wt% of solid raw materials of LATP, 30 wt% of LLZO, 10 wt% of PMMA and PVDF10%, 9.5% of 3-methacryloxypropylmethyldiethoxysilane, 0.5% of azobisisobutyronitrile, 10% of CNT, and LiClO4The content was 10%. The solvent of the slurry was NMP, and the solid content of the slurry was 35%. Fully mixing and uniformly dispersing the mixture by using a centrifugal dispersion machine to obtain mixed slurry;
preparing coating slurry of the positive 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 uniformly mixed, and the weight ratio of coating slurry of the positive electrode active material coating is NCA: CNT: PAN: PVDF: and (3) preparing positive electrode material layer coating slurry with the solid content of 70 percent, wherein the LiFSI is 93:2:1:2: 2.
Secondly, coating a solid electrolyte layer on both sides of the aluminum foil in a micro-gravure coating mode, coating the aluminum foil on both sides in the micro-gravure coating mode at a coating speed of 20 m/min and a single-side coating thickness of 3 microns at a drying temperature of 110 ℃, and rolling 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 coating thickness of one side is 40 micrometers, and the coating thickness of the two sides is 80 micrometers; and (5) rolling the positive electrode at the drying temperature of 100 ℃.
And fourthly, punching and drying the positive electrode and the negative electrode, assembling the polymer battery, and assembling the polymer battery dry battery core to a pre-injection stage of the polymer monomer solution.
Fifthly, preparing a certain amount of polymer monomer, micromolecular solvent, lithium salt and polymerization initiator into polymer monomer solution for later use. The polymer electrolyte monomer, the micromolecular solvent, the lithium salt and the polymerization initiator respectively comprise the following components in percentage by weight: 10% of polymer electrolyte monomer (MPEG-MA), 10% of polymer electrolyte monomer (PEG), 10% of mechanically reinforced polymer (ethylene-terminated polydimethylsiloxane), 50% of small molecular solvent, 19.9% of lithium salt (LiTFSI) and 0.5% of azobisisobutyronitrile.
And sixthly, injecting the polymer monomer solution obtained in the fifth step into the battery cell prepared in the fourth step, placing the battery cell in a dry atmosphere at the negative pressure of 300Pa for standing, sealing, cold-pressing at 0.01MPa and hot-pressing at 0.2MPa, and carrying out in-situ reaction at the temperature of 40 ℃ and the pressure of 0.2MPa for 36 hours to obtain the polymer lithium ion battery.
Table 1: each example is based on the positive electrode and physical parameters of the solid electrolyte coating.
Figure BDA0002627481320000211
As can be seen from table 1, the thickness and conductivity of the anode protective solid electrolyte layer are controllable, and the anode protective solid electrolyte layer has high conductivity, high ion conductivity, high adhesion, high mechanical strength, and improved comprehensive performance of the lithium ion battery.
In conclusion, compared with the prior art, the high-safety polymer battery positive plate, the polymer battery and the battery preparation method provided by the invention have scientific design, can effectively prevent the contact between the positive active material and the aluminum foil (as the positive current collector), prevent the occurrence of thermite reaction when the polymer battery fails, avoid the exothermic chain reaction of the battery, improve the safety of the polymer battery, and have great practical significance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A high-safety polymer battery positive plate protected by a solid electrolyte coating is characterized by comprising an aluminum foil and a double-layer coating layer;
the aluminum foil is used as a positive current collector, and the outer surface of the aluminum foil is coated with a double-layer coating layer;
wherein, the double-layer coating layer comprises a composite solid electrolyte coating coated on the aluminum foil and a positive 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 layer, a component 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 electrolyte comprises at least one of LLZO, LATP and LAG, LLZO, LATP and LAG being oxide solid electrolytes;
wherein the first polymer solid 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 3-methacryloxypropylmethyldiethoxysilane and a vinyl-terminated polydimethylsiloxane;
the first polymer solid electrolyte also comprises a first polymerization initiator, and 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, LiClO4And LiPF6At least one of;
for the composite solid electrolyte coating, the component proportions are as follows:
wherein, the proportion of the first polymer in the first polymer solid electrolyte accounts for 5 to 30 percent of the total weight of the composite solid electrolyte coating;
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 mechanical enhancement type 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 to 20 percent of the total weight of the composite solid electrolyte coating;
wherein, the proportion of the first oxide solid electrolyte in the total weight of the composite solid electrolyte coating is 30-80%.
Wherein, the first polymerization initiator accounts for 0.01 to 1 percent of the total weight of the composite solid electrolyte coating;
2. the positive plate of the high-safety polymer battery as claimed in claim 1, wherein 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 μm;
the positive electrode active material coating is coated on the composite solid electrolyte coating, and the thickness of the single-layer positive electrode active material coating is 40-100 micrometers.
3. The positive electrode sheet for a high-safety polymer battery according to claim 1, wherein the positive active material coating layer comprises a positive 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 ratio of the components is as follows:
the positive active material accounts for 88 to 98 percent of the total weight of the positive active material coating;
the second polymer in the second polymer solid electrolyte accounts for 0.5 to 5 percent of the total weight of the positive active material coating;
the second lithium salt in the second polymer solid electrolyte accounts for 0.5 to 5 percent of the total weight of the positive active material coating;
the second conductive agent accounts for 0.5 to 10 percent of the total weight of the positive 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 active material coating.
4. The positive electrode sheet for a high-safety polymer battery as claimed in claim 3, wherein the positive active material coating layer comprises a positive active material including any one of a lithium cobaltate material, a ternary material and a nickel-rich material;
the second conductive agent included in the positive electrode active material coating layer comprises at least one of conductive nano materials such as carbon black, carbon nano tubes and graphene;
the second polymer solid electrolyte included in the positive active material coating layer 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 and LiClO4And LiPF6At least one of;
the second oxide solid electrolyte included in the positive electrode active material coating layer specifically includes at least one of LLZO, LATP, and LAGP.
5. A high-safety polymer battery based on positive electrode protection, which is characterized by comprising the positive electrode plate of the high-safety polymer battery according to any one of claims 1 to 4, a polymer battery negative electrode, a preset polymer electrolyte and a support film;
wherein, the polymer battery negative electrode is a lithium metal negative electrode plate or a traditional lithium ion battery negative electrode plate;
the material of the supporting 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 molecular solvent and a lithium salt, wherein:
presetting a polymer electrolyte monomer comprising at least one of ECA, PEG and MPEG-MA;
the preset polymer electrolyte monomer also comprises a preset mechanical enhancement polymer, and the preset mechanical enhancement polymer comprises at least one of 3-methacryloxypropyl methyldiethoxysilane and vinyl-terminated polydimethylsiloxane;
the preset polymer electrolyte also comprises a preset polymerization initiator, and 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, LiClO4And LiPF6At least one of;
in the preset polymer electrolyte, the weight contents of a preset polymer electrolyte monomer, lithium salt in the preset polymer electrolyte, a small molecular solvent and a polymerization initiator are respectively as follows:
presetting 5-60% of polymer electrolyte monomer, 10-40% of lithium salt, 5-60% of micromolecular solvent and 0.01-0.1% 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.
6. The high-safety polymer battery as claimed in claim 5, wherein the positive electrode, the pre-set polymer electrolyte, the negative electrode and the support film are integrated by a free radical in-situ initiation polymerization method to finally prepare the polymer battery.
7. A preparation method of a high-safety polymer battery based on positive electrode protection is characterized by comprising 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 positive active material coating on the composite solid electrolyte coating by adopting a roller coating or spraying process to obtain a positive electrode;
thirdly, integrating the anode, the preset polymer electrolyte, the cathode and the support membrane obtained in the second step by adopting a free radical in-situ initiation polymerization reaction 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 a first polymer solid electrolyte, a first lithium salt contained in a 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 on both sides by using a micro-gravure coating mode and adopting coating slurry of the composite solid electrolyte coating, drying and rolling for later use;
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 layer coating slurry;
step S22: coating a positive 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, assembling the polymer battery, and assembling the polymer battery dry cell to a pre-injection stage of a polymer monomer solution;
step S32: preparing a preset polymer electrolyte monomer in a preset polymer electrolyte, a lithium salt in the preset polymer electrolyte, a preset polymerization initiator and a small molecular solvent according to a preset proportion into a polymer monomer solution for later use;
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 at a negative pressure for standing, sealing, then carrying out 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.
8. The method of claim 7, wherein in step S11, in the coating slurry of the composite solid electrolyte coating layer, the second conductive agent comprises at least one of conductive nanomaterials such as carbon black, carbon nanotubes, and graphene;
in step S11, a first oxide solid state electrolyte including at least one of LLZO, LATP, and LAGP oxide solid state electrolytes, which are nanomaterials having higher thermal stability;
a first polymer in a first polymer solid electrolyte comprising 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 3-methacryloxypropylmethyldiethoxysilane and a vinyl-terminated polydimethylsiloxane;
the first polymer solid electrolyte also comprises a first polymerization initiator, and 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 electrolyte comprising LiFSI, LiTFSI, LiClO4And LiPF6At least one of;
in step S11, in the coating slurry of the composite solid electrolyte coating layer, the component ratio of each solid component is specifically as follows:
the first polymer solid electrolyte comprises a first polymer which accounts for 5 to 30 percent of the total weight of the composite solid electrolyte coating;
the first mechanical enhancement type 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 to 1 percent of the total weight of the composite solid electrolyte coating;
the first polymer solid electrolyte contains a first lithium salt which accounts for 0.5 to 30 percent 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%.
9. The method according to claim 7, wherein in the step S21, in the coating slurry 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 nickel-rich 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 conductive nanomaterials such as carbon black, carbon nanotubes, and graphene;
in step S21, in the coating slurry of the positive active material coating layer, a second oxide solid state electrolyte including at least one of LLZO, LATP, and LAGP, which are nanomaterials having higher thermal stability;
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 electrolyte comprising LiFSI, LiTFSI, LiClO4And LiPF6At least one of;
in step S21, in the coating slurry of the positive electrode active material coating layer, the solid component ratios are specifically as follows:
the positive active material accounts for 88 to 98 percent of the total weight of the positive active material coating;
the second polymer solid electrolyte comprises a second polymer which accounts for 0.5 to 5 percent of the total weight of the positive active material coating;
the second polymer solid electrolyte contains a second lithium salt which accounts for 0.5 to 5 percent of the total weight of the positive active material coating;
the second conductive agent accounts for 0.5 to 10 percent of the total weight of the positive active material coating;
a second oxide solid electrolyte (i.e., a second inorganic solid electrolyte) in a proportion of 0.5% to 5% by weight based on the total weight of the positive electrode active material coating layer;
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%.
10. The method of claim 7, wherein in step S12, the composite solid electrolyte coating is prepared by: the coating is directly coated on an aluminum foil, and the thickness of the single-layer composite solid electrolyte coating is 0.5-5 microns;
in step S22, the positive electrode active material coating layer coated on the composite solid electrolyte coating layer has a thickness of 40 to 100 μm;
in step S32, presetting a preset polymer electrolyte monomer in the polymer electrolyte, including at least one of ECA, PEG, and MPEG-MA;
the preset polymer electrolyte monomer also comprises a preset mechanical enhancement polymer, and the preset mechanical enhancement polymer comprises at least one of 3-methacryloxypropyl methyldiethoxysilane and vinyl-terminated polydimethylsiloxane;
in step S32, the predetermined 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, lithium salt in polymer electrolyte is preset, including LiFSI, LiTFSI, LiClO4And LiPF6At least one of;
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: presetting 5-60% of polymer electrolyte monomer, 10-40% of lithium salt, 5-60% of micromolecular solvent and 0.01-0.1% of polymerization initiator;
wherein the preset mechanically enhanced polymer in the preset polymer electrolyte monomer accounts for 20-80% of the weight of the preset polymer electrolyte monomer;
in step S33, after the cell is sealed, the preset pressure of cold pressing and hot pressing is 0.001MPa to 0.5MPa, the temperature of hot pressing is 40 ℃ to 70 ℃, and the reaction time is 2 hours to 12 hours.
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