CN109216650B - Battery electrode, preparation method thereof and all-solid-state battery - Google Patents

Battery electrode, preparation method thereof and all-solid-state battery Download PDF

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CN109216650B
CN109216650B CN201710525173.9A CN201710525173A CN109216650B CN 109216650 B CN109216650 B CN 109216650B CN 201710525173 A CN201710525173 A CN 201710525173A CN 109216650 B CN109216650 B CN 109216650B
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CN109216650A (en
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高磊
刘荣华
李元姣
单军
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BYD Co Ltd
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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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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

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Abstract

The invention relates to the field of all-solid batteries, in particular to a battery electrode, a preparation method thereof and an all-solid battery. The battery electrode includes: the electrode material layer contains a polymer matrix and an electrode active material, and the polymer matrix is a cross-linked polymer. The battery electrode and the electrolyte layer provided by the invention have higher ionic conductivity and mechanical strength, so that the battery has better specific capacity, cycle life and the like.

Description

Battery electrode, preparation method thereof and all-solid-state battery
Technical Field
The invention relates to the field of all-solid batteries, in particular to a battery electrode, a preparation method thereof and an all-solid battery.
Background
At present, liquid electrolyte is mostly used as a conductive substance in lithium ion batteries on the market, but in the using process, the liquid electrolyte is volatile, flammable and explosive, so that a plurality of safety problems are caused; and lithium dendrites are easy to grow out, so that the application of the metal lithium as a negative electrode in a battery is limited. Therefore, Solid Polymer Electrolytes (SPE) have been proposed to replace liquid electrolytes. The solid polymer electrolyte membrane not only functions as ion conduction, but also prevents contact between the positive and negative electrodes. And because of its strong plasticity, can make into the film of different shapes according to different demands, the pliability is good, can bear the pressure of electrode in the charge-discharge process, and high temperature stability is good, has greatly improved the security of lithium cell.
CN105680091A discloses a high-performance all-solid-state lithium ion battery and a preparation method thereof, in the application, a polymer electrolyte modified by a lithium super-ion conductor is penetrated through the whole all-solid-state lithium ion battery system, so that the transmission rate of lithium ions is improved, and the multiplying power charge and discharge capacity of the all-solid-state lithium ion battery is improved; however, this method has several major disadvantages: firstly, the preparation process of the negative pole piece is complex, and the lithium powder has high requirement on the environment; secondly, the negative electrode needs to mix the lithium powder with the super-ion conductor and the polymer, and the mixture is difficult to mix uniformly, so that the uniformity of a pole piece is poor, and the consistency of the battery is poor; the positive pole piece and the negative pole piece can be manufactured into a battery only by soaking in the polymer electrolyte, and after soaking, the gel-state polymer electrolyte is bonded with the pole pieces, so that the complexity of the lamination process and the difficulty of correct lamination are increased; and fourthly, the ionic conductivity of the polymer electrolyte is low, and the difference from the commercial application requirement is large.
CN105489932A discloses a method for preparing a lithium ion battery polymer electrolyte film by an ultraviolet crosslinking method. The solid electrolyte membrane is prepared by ultraviolet crosslinking monomer Methyl Methacrylate (MMA) and mixing polyurethane acrylate (PUA) and ionic liquid (DEYTFSI and Py13TFSI), and the mechanical strength and the ionic conductivity of the electrolyte membrane are improved to a certain degree. However, this method also has several major disadvantages: firstly, the preparation process is complex and has various steps; secondly, the ionic conductivity of the used polymers PUA and PMMA is not high, the ionic conductivity of the polymer electrolyte membrane is mainly improved by adding ionic liquid, and the ionic liquid has higher cost and is not suitable for industrial production; and dibenzoyl peroxide as the initiator for ultraviolet crosslinking is extremely unstable, and has the risk of ignition and explosion when meeting light, high temperature and reducing agent, so that the risk in the operation process is high.
Disclosure of Invention
The invention aims to provide a battery electrode with high specific capacity, a preparation method thereof and an all-solid-state battery.
In order to achieve the above object, an aspect of the present invention provides a battery electrode, comprising: the electrode material layer comprises a polymer matrix and an electrode active material dispersed in the polymer matrix, wherein the polymer matrix is a cross-linked polymer;
wherein the crosslinked polymer contains a crosslinked structure provided by a crosslinking agent and a copolymer chain linked to the crosslinked structure, the copolymer chain being provided by a crosslinkable copolymer containing a structural unit represented by formula (1), a structural unit represented by formula (2), and a structural unit represented by formula (3), wherein the crosslinkable copolymer is linked to the crosslinking agent through at least a part of the structural unit represented by formula (3) to provide the copolymer chain;
Figure BDA0001338376640000021
wherein R is H or C1-C4 alkyl, L is C0-C4 alkylene or-R1-O-R2-，R1Is C0-C4 alkylene, R2Is C0-C4 alkylene;
the crosslinking agent is one or more of acrylate crosslinking agents containing at least two acrylate groups, and the acrylate groups are groups shown in a formula (4): -O-C (O) -C (R') ═ CH2R' is H or C1-C4 alkyl.
In a second aspect, the present invention provides a method for preparing a battery electrode, the method comprising:
(1) providing an electrode paste containing an electrode active material, a crosslinkable copolymer, a crosslinking agent, and a photoinitiator;
(2) coating the electrode slurry obtained in the step (1) on an electrode current collector, drying, and then crosslinking and curing under the irradiation of ultraviolet light to form an electrode material layer on the electrode current collector;
wherein the crosslinkable copolymer contains a structural unit represented by formula (1), a structural unit represented by formula (2), and a structural unit represented by formula (3);
Figure BDA0001338376640000031
wherein R is H or C1-C4 alkyl, L is C0-C4 alkylene or-R1-O-R2-，R1Is C0-C4 alkylene, R2Is C0-C4 alkylene;
the crosslinking agent is one or more of acrylate crosslinking agents containing at least two acrylate groups, and the acrylate groups are groups shown in a formula (4): -O-C (O) -C (R')＝CH2R' is H or C1-C4 alkyl.
In a third aspect, the invention provides a battery electrode made by the above method.
A fourth aspect of the present invention provides an all-solid battery, wherein the all-solid battery includes: the battery comprises an electrode, an electrolyte layer and a negative electrode, wherein the positive electrode and/or the negative electrode is the battery electrode.
The battery electrode and the electrolyte layer provided by the invention have higher ionic conductivity and mechanical strength, so that the battery has better specific capacity, cycle life and the like; the battery manufacturing process is greatly simplified, the manufacturing cost is reduced, the operability is improved, the continuous production can be realized, the production/manufacturing efficiency is improved, and the high-capacity battery can be prepared.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In one aspect, the present invention provides a battery electrode, comprising: the electrode material layer comprises a polymer matrix and an electrode active material dispersed in the polymer matrix, wherein the polymer matrix is a cross-linked polymer;
wherein the crosslinked polymer contains a crosslinked structure provided by a crosslinking agent and a copolymer chain linked to the crosslinked structure, the copolymer chain being provided by a crosslinkable copolymer containing a structural unit represented by formula (1), a structural unit represented by formula (2), and a structural unit represented by formula (3), wherein the crosslinkable copolymer is linked to the crosslinking agent through at least a part of the structural unit represented by formula (3) to provide the copolymer chain;
Figure BDA0001338376640000041
wherein R is H or C1-C4 alkyl, L is C0-C4 alkylene or-R1-O-R2-，R1Is C0-C4 alkylene, R2Is C0-C4 alkylene;
the crosslinking agent is one or more of acrylate crosslinking agents containing at least two acrylate groups, and the acrylate groups are groups shown in a formula (4): -O-C (O) -C (R') ═ CH2R' is H or C1-C4 alkyl.
According to the invention, in the crosslinked polymer, the double bond of the crosslinking agent and the double bond of the structural unit represented by formula (3) of the crosslinkable copolymer initiate polymerization, and a plurality of double bonds of the one molecular crosslinking agent may be bonded to double bonds of a plurality of structural units represented by formula (3) of the crosslinkable copolymer, or double bonds of a plurality of structural units represented by formula (3) of the crosslinkable copolymer may be bonded to double bonds of a plurality of crosslinking agents, thereby forming the crosslinked polymer of a three-dimensional network structure. When such a crosslinked polymer is used as a polymer matrix, the ionic conductivity and mechanical strength can be improved.
In the present invention, specific examples of the alkyl group having C1 to C4 may be, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group or a tert-butyl group.
Specific examples of the alkylene group having C0-C4 may be, for example, an alkylene group having C0, -CH2-、-CH2CH2-、-CH2CH2CH2-、-CH(CH3)CH2-、-CH2CH(CH3)-、-CH2CH2CH2CH2-and the like. Wherein said alkylene group of C0 means absent or a linking bond, i.e. the groups on both sides of the group will be directly linked.
Preferably, R is H, methyl or ethyl, L is C0 alkylene, -CH2-、-CH2CH2-、-CH2CH2CH2-、-O-、-O-CH2-、-O-CH2CH2-、-CH2-O-、-CH2-O-CH2-、-CH2-O-CH2CH2-、-CH2CH2-O-、-CH2CH2-O-CH2-or-CH2CH2-O-CH2CH2-; r' is H, methyl or ethyl.
According to the present invention, the molar ratio of the structural unit represented by formula (1), the structural unit represented by formula (2) and the structural unit represented by formula (3) in the crosslinkable copolymer may vary within a wide range, and it is preferable that the molar ratio of the structural unit represented by formula (1), the structural unit represented by formula (2) and the structural unit represented by formula (3) is 100: 0.5-25: 0.5-20, preferably 100: 1-21: 0.5-15, more preferably 100: 1-15: 1-10, more preferably 100: 1-8: 1-6. In a most preferred embodiment, the structural unit of the crosslinkable copolymer is composed of a structural unit represented by formula (1), a structural unit represented by formula (2), and a structural unit represented by formula (3). The crosslinkable copolymer is preferably a linear random copolymer composed of a structural unit represented by the formula (1), a structural unit represented by the formula (2) and a structural unit represented by the formula (3).
According to the present invention, the weight average molecular weight of the crosslinkable copolymer may vary within a relatively wide range, preferably the weight average molecular weight of the crosslinkable copolymer is 5,000-5,000,000g/mol, preferably 50,000-1,000,000g/mol, more preferably 50,000-500,000g/mol, still more preferably 50,000-95,000g/mol, for example 60,000-95,000 g/mol.
According to the invention, the cross-linking agent is one or more of acrylate cross-linking agents containing at least two acrylate groups, and the acrylate groups of the group shown in the formula (4) can be acrylate groups, methacrylate groups and the like. The crosslinking agent used in the present invention is a small molecule crosslinking agent, preferably, the crosslinking agent is ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, 1, 3-propylene glycol dimethacrylate, 1, 2-propylene glycol dimethacrylate, 1, 3-propylene glycol diacrylate, 1, 2-propylene glycol diacrylate, 1, 4-butylene glycol dimethacrylate, 1, 3-butylene glycol dimethacrylate, 1, 4-butylene glycol diacrylate, 1-diacrylate, one or more of 3-butanediol ester, pentaerythritol diacrylate, pentaerythritol triacrylate and pentaerythritol tetraacrylate, more preferably one or more of triethylene glycol dimethacrylate, triethylene glycol diacrylate, pentaerythritol triacrylate and pentaerythritol tetraacrylate.
According to the invention, the crosslinking agent provides a crosslinking building block content which depends on the desired degree of crosslinking of the crosslinked polymer, preferably the copolymer chain content is from 60 to 95% by weight, preferably from 70 to 92% by weight, more preferably from 70 to 90% by weight, for example from 72 to 80% by weight, based on the weight of the polymer matrix. Preferably, the cross-linked structure is present in an amount of 5 to 40 wt.%, preferably 8 to 30 wt.%, more preferably 20 to 30 wt.%, for example 21 to 25 wt.%.
According to the present invention, the amount ratio of the electrode active material and the polymer matrix may vary within a wide range, and preferably, the polymer matrix is contained in an amount of 5 to 100 parts by weight, preferably 10 to 80 parts by weight, and more preferably 20 to 50 parts by weight, relative to 100 parts by weight of the electrode active material.
In a preferred embodiment of the present invention, the content of the structural moiety provided by the crosslinkable copolymer in the polymer matrix is 5 to 70 parts by weight and the content of the structural moiety provided by the crosslinking agent is 1 to 20 parts by weight, relative to 100 parts by weight of the electrode active material. Preferably, the amount of the moiety provided by the crosslinkable copolymer is 10 to 60 parts by weight and the amount of the moiety provided by the crosslinking agent is 2 to 15 parts by weight. More preferably, the moiety provided by the cross-linkable copolymer is present in an amount of 20 to 30 parts by weight (e.g., 25 to 29 parts by weight) and the moiety provided by the cross-linking agent is present in an amount of 4 to 12 parts by weight (e.g., 6 to 8 parts by weight).
When the electrode is a positive electrode, the electrode active material is a positive electrode active material, and the formed electrode material layer is a positive electrode material layer; when the electrode is a negative electrode, the electrode active material is a negative electrode active material, the formed electrode material layer is a negative electrode material layer, and the electrode active material is a negative electrode material layer.
When the electrode material layer is a positive electrode material layer, the obtained electrode is a positive electrode, wherein the specific types of the positive electrode active materials are not particularly limited, are all conventional raw materials, and can be selected according to requirements. For example, the positive active material includes, but is not limited to, lithium cobaltate (LiCoO)2) Lithium manganate (LiMn)2O4) Lithium manganate, ternary material (lithium transition metal oxide) and lithium iron phosphate (LiFePO)4) One or more of (a).
According to the present invention, when the electrode material layer is a positive electrode material layer, the positive electrode material layer may further contain a lithium salt, a conductive agent, and a binder. Preferably, the lithium salt is contained in an amount of 1 to 20 parts by weight, preferably 5 to 15 parts by weight, relative to 100 parts by weight of the positive electrode active material; the content of the conductive agent is 5-20 parts by weight, preferably 6-15 parts by weight; the content of the binder is 1 to 20 parts by weight, preferably 2 to 15 parts by weight.
The specific types of the lithium salt, the conductive agent and the binder are not particularly limited, and are all conventional raw materials and can be selected according to requirements.
For example, the lithium salt is LiClO4(lithium perchlorate) and LiPF6(lithium hexafluorophosphate), LiBF4(lithium tetrafluoroborate), LiBOB (lithium dioxalate borate), LiN (SO)2CF3)2Lithium bistrifluoro (methylsulfonate) imide), LiCF3SO3(lithium trifluoromethanesulfonate) and LiN (SO)2CF2CF3)2One or more of (a).
For example, the conductive agent may be selected from one or more of superconducting carbon, conductive carbon black, conductive graphite, carbon nanotubes, graphene, and carbon nanofibers.
For example, the binder may be selected from one or more of polyvinylidene fluoride (PVDF), Styrene Butadiene Rubber (SBR), and sodium carboxymethylcellulose (CMC).
When the electrode material layer is the negative electrode material layer, the obtained electrode is a negative electrode, wherein the specific types of the negative electrode active materials are not particularly limited, are all conventional raw materials, and can be selected according to requirements. For example, the negative active material includes, but is not limited to, one or more of graphite, activated carbon, graphene, carbon nanotubes, silicon carbon composites, and the like.
According to the present invention, when the electrode material layer is an anode material layer, the anode material layer may further contain a lithium salt, a binder, and a thickener. Preferably, the lithium salt is contained in an amount of 1 to 20 parts by weight, preferably 1 to 5 parts by weight, relative to 100 parts by weight of the negative electrode active material; the content of the binder is 1-20 parts by weight, preferably 1-5 parts by weight; the content of the thickener is 1 to 20 parts by weight, preferably 1 to 5 parts by weight.
The specific types of the lithium salt, the binder and the thickener are not particularly limited, and are all conventional raw materials, and can be selected according to requirements.
Wherein the lithium salt and binder are as described above.
The thickening agent can be one or more of methylcellulose, carboxymethyl cellulose and the like.
According to the present invention, preferably, the thickness of the electrode material layer is 10 to 100 μm (single-sided thickness).
According to the present invention, the electrode current collector is not particularly limited, and an electrode current collector conventional in the art, for example, a copper foil, an aluminum foil, etc., may be used, and the thickness thereof may be, for example, 1 to 100 μm.
In a second aspect, the present invention provides a method for preparing a battery electrode, the method comprising:
(1) providing an electrode paste containing an electrode active material, a crosslinkable copolymer, a crosslinking agent, and a photoinitiator;
(2) coating the electrode slurry obtained in the step (1) on an electrode current collector, drying, and then crosslinking and curing under the irradiation of ultraviolet light to form an electrode material layer on the electrode current collector;
wherein the crosslinkable copolymer contains a structural unit represented by formula (1), a structural unit represented by formula (2), and a structural unit represented by formula (3);
Figure BDA0001338376640000091
wherein R is H or C1-C4 alkyl, L is C0-C4 alkylene or-R1-O-R2-，R1Is C0-C4 alkylene, R2Is C0-C4 alkylene;
the crosslinking agent is one or more of acrylate crosslinking agents containing at least two acrylate groups, and the acrylate groups are groups shown in a formula (4): -O-C (O) -C (R') ═ CH2R' is H or C1-C4 alkyl.
The choice of groups and species of the crosslinkable copolymer, the choice of groups and species of the crosslinking agent, and the invention are as described above and will not be described in detail herein.
The crosslinkable copolymer according to the present invention may be prepared by a method conventional in the art, or may be a commercially available product according to the present invention, and the present invention is not particularly limited thereto.
The amounts of the crosslinkable copolymer and the crosslinking agent to be used may be selected according to the amounts of the respective crosslinkable polymers described above, and preferably the crosslinkable copolymer is used in an amount of 60 to 95% by weight, preferably 70 to 92% by weight, more preferably 70 to 90% by weight, for example 72 to 80% by weight, based on the total weight of the crosslinkable copolymer and the crosslinking agent. Preferably, the cross-linking agent is used in an amount of 5 to 40 wt%, preferably 8 to 30 wt%, more preferably 20 to 30 wt%, for example 21 to 25 wt%.
According to the present invention, it is preferable that the crosslinkable copolymer and the crosslinking agent are used in a total amount of 5 to 100 parts by weight, preferably 10 to 80 parts by weight, and more preferably 20 to 50 parts by weight, relative to 100 parts by weight of the electrode active material.
According to the present invention, preferably, the photoinitiator is one or more of 2-hydroxy-2-methyl propiophenone, ethyl (2,4, 6-trimethylbenzoyl) phosphonate, ethyl 4-dimethylaminobenzoate, 1-hydroxycyclohexyl phenyl ketone, benzoin dimethyl ether, methyl o-benzoylbenzoate and 4-chlorobenzophenone. The photoinitiator may be used in a wide range, and is preferably used in an amount of 2 to 15 wt%, preferably 3 to 8 wt%, based on the total weight of the crosslinkable copolymer, the crosslinking agent and the silane coupling agent-modified inorganic nanoparticles.
According to the present invention, when the prepared electrode is a positive electrode, the electrode material layer is a negative electrode material layer, and the electrode active material is a positive electrode active material. The electrode slurry can also be introduced with a lithium salt, a conductive agent and a binder. Preferably, the lithium salt is contained in an amount of 1 to 20 parts by weight, preferably 5 to 15 parts by weight, relative to 100 parts by weight of the positive electrode active material; the content of the conductive agent is 5-50 parts by weight, preferably 6-20 parts by weight; the content of the binder is 1 to 20 parts by weight, preferably 2 to 15 parts by weight. Wherein the lithium salt, the conductive agent and the binder are as defined above, and the present invention is not described herein again.
According to the invention, when the prepared electrode is a negative electrode, the electrode material layer is a negative electrode material layer, the electrode active material is a negative electrode active material, and lithium salt, a binder and a thickening agent are also introduced into the electrode slurry. Preferably, the lithium salt is contained in an amount of 1 to 20 parts by weight, preferably 1 to 5 parts by weight, relative to 100 parts by weight of the negative electrode active material; the content of the binder is 1-20 parts by weight, preferably 1-5 parts by weight; the content of the thickener is 1 to 20 parts by weight, preferably 1 to 5 parts by weight. Wherein the lithium salt, binder and thickener are as defined above, and the present invention is not described herein in detail.
According to the present invention, the electrode slurry further includes a dispersion solvent used, which may be, for example, one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, tetrahydrofuran, chloroform, dichloromethane, and acetonitrile. The amount of the dispersion solvent to be used may vary within a wide range, and is preferably 10 to 1000 parts by weight, preferably 20 to 800 parts by weight, more preferably 100 to 500 parts by weight, for example 200 to 400 parts by weight, relative to 100 parts by weight of the electrode active material.
According to the preparation method of the battery electrode, the electrode slurry is coated on the electrode current collector in the step (2), and is dried to form a semi-dry film on the current collector, and then the semi-dry film is crosslinked and cured by ultraviolet irradiation, so that an electrode material layer can be formed on the current collector. The ultraviolet irradiation may be performed by any conventional ultraviolet irradiation method in the art, and the present invention is not particularly limited thereto. The time for crosslinking and curing is 30s-15min, preferably 2-10 min.
According to the present invention, by the above method, a transparent crosslinked polymer film (i.e., an electrode material layer) may be formed on the surface of the electrode current collector, and the method may further comprise drying the current collector having the electrode material layer attached thereto obtained in step (2) to remove residual solvent, moisture, and the like, for example, at 40 to 80 ℃ for 10 to 30 hours.
After the electrode material layer is formed, the same electrode material layer may be formed on the other surface of the electrode current collector in the same manner, thereby forming a battery electrode having the electrode material layer of the present invention on both surfaces.
In a third aspect, the invention provides a battery electrode made by the above method.
A fourth aspect of the present invention provides an all-solid battery, wherein the all-solid battery includes: the battery comprises an electrode, an electrolyte layer and a negative electrode, wherein the positive electrode and/or the negative electrode is the battery electrode.
According to the present invention, the electrolyte layer is preferably specially configured, and the electrolyte layer is a polymer electrolyte membrane attached to the positive electrode and/or the negative electrode, the polymer electrolyte membrane containing a polymer matrix and a lithium salt dispersed in the polymer matrix. The polymer matrix and lithium salt are as described above.
According to the present invention, the lithium salt is preferably present in an amount of 10 to 30 wt.%, preferably 15 to 27 wt.%, more preferably 18 to 22 wt.%, based on the total weight of the polymer matrix.
In another preferred embodiment, the electrolyte layer is a polymer electrolyte membrane attached to a positive electrode and/or a negative electrode, and the polymer electrolyte membrane is prepared by a method comprising:
(a) providing an electrolyte paste comprising a lithium salt, a cross-linkable copolymer, a cross-linking agent, and a photoinitiator;
(b) coating the electrolyte slurry on the anode and/or the cathode, drying, and then crosslinking and curing under the irradiation of ultraviolet light to form an electrolyte layer on the anode and/or the cathode;
wherein the crosslinkable copolymer, the crosslinking agent and the photoinitiator are as described hereinbefore.
According to the present invention, the organic solvent used for the electrolyte slurry may be, for example, one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, tetrahydrofuran, chloroform, dichloromethane, and acetonitrile. The amount of the organic solvent may vary within wide limits, preferably from 20 to 100 parts by weight, preferably from 30 to 80 parts by weight, relative to 100 parts by weight of crosslinkable copolymer.
The crosslinking and curing may further include drying the positive electrode and/or negative electrode having the electrolyte layer attached thereto obtained in step (b) to remove residual solvent, moisture, and the like, for example, at 40 to 80 ℃ for 10 to 30 hours, as described above.
After the electrolyte layer is formed, the same electrolyte layer may be formed on the other surface of the positive electrode and/or the negative electrode in the same manner, thereby forming the positive electrode and/or the negative electrode having the electrolyte layer of the present invention on both surfaces. Wherein, after the electrolyte layer is formed on both sides, hot pressing (for example, hot pressing at 50-70 ℃) can be carried out to improve the bonding strength of the electrolyte layer and the battery electrode.
According to the invention, the thickness of the electrolyte layer may be, for example, 10 to 200 μm (single-sided thickness).
According to the present invention, the negative electrode of the battery may be a negative electrode conventional in the art, and may be, for example, a negative electrode current collector having metal lithium attached to the surface thereof. The negative electrode collector may be, for example, a copper foil, a copper mesh, or the like.
According to the present invention, preferably, the positive electrode and the negative electrode are both the respective positive electrode and negative electrode obtained by the present invention.
According to the invention, the all-solid-state battery can be obtained by welding the positive electrode and the negative electrode with the upper electrode lugs, superposing the positive electrode and the negative electrode, and placing the superposed positive electrode and the negative electrode in the aluminum plastic film for sealing and pressing.
The battery of the invention can obtain higher specific capacity, cycle life and the like by adopting the battery electrode, particularly matching with the electrolyte layer.
The present invention will be described in detail below by way of examples.
In the following examples:
crosslinkable copolymer No. 1 is a copolymer available from seiko chemical company, which is a structural unit represented by formula (1), a structural unit represented by formula (2), and a structural unit represented by formula (3) (R ═ H, L ═ CH)2-O-CH2-) wherein the molar ratio of the structural unit represented by formula (1), the structural unit represented by formula (2) and the structural unit represented by formula (3) is 93:6:1, and the weight-average molecular weight is 95,000 g/mol.
Crosslinkable copolymer No. 2 is a copolymer available from seiko chemical company, which is a structural unit represented by formula (1), a structural unit represented by formula (2), and a structural unit represented by formula (3) (R ═ H, L ═ CH)2-O-CH2-) wherein the molar ratio of the structural unit represented by formula (1), the structural unit represented by formula (2) and the structural unit represented by formula (3) is 96:1:3, and the weight-average molecular weight is 80,000 g/mol.
Crosslinkable copolymer No. 3 is a copolymer available from seiko chemical company, which is a structural unit represented by formula (1), a structural unit represented by formula (2), and a structural unit represented by formula (3) (R ═ H, L ═ CH)2-O-CH2-) wherein the molar ratio of the structural unit represented by formula (1), the structural unit represented by formula (2) and the structural unit represented by formula (3) is 90:5:5, and the weight-average molecular weight is 70,000 g/mol.
Crosslinkable copolymer No. 4 was a copolymer available from cheng chemical company, which was a structural unit represented by formula (1), a structural unit represented by formula (2), and a structural unit represented by formula (3) (R ═ H, L ═ CH)2-O-CH2-) wherein the molar ratio of the structural unit represented by formula (1), the structural unit represented by formula (2) and the structural unit represented by formula (3) is 93:6:1, and the weight-average molecular weight is 50,000 g/mol.
Crosslinkable copolymer No. 5 was a copolymer available from seiko chemical company, which was a structural unit represented by formula (1), a structural unit represented by formula (2), and a structural unit represented by formula (3) (R ═ H, L ═ CH)2-O-CH2-) wherein the molar ratio of the structural unit represented by formula (1), the structural unit represented by formula (2) and the structural unit represented by formula (3) is 93:6:1, and the weight-average molecular weight is 200,000 g/mol.
Crosslinkable copolymer No. 6 was a copolymer available from cheng chemical company, which was a structural unit represented by formula (1), a structural unit represented by formula (2), and a structural unit represented by formula (3) (R ═ H, L ═ CH)2-O-CH2-) wherein the molar ratio of the structural unit represented by formula (1), the structural unit represented by formula (2) and the structural unit represented by formula (3) is 93:6:1, and the weight-average molecular weight is 40,000 g/mol.
Copolymer 7# is a copolymer available from Nikkiso Co., Ltd, and is a random copolymer composed of a structural unit represented by formula (1) and a structural unit represented by formula (2), wherein the molar ratio of the structural unit represented by formula (1) to the structural unit represented by formula (2) is 12:1, and the weight average molecular weight is 95,000 g/mol.
Polyvinylidene fluoride: product commercially available from Aladdin Industrial Co. having a weight average molecular weight of 1.5X 105～5×105g/mol。
PEO: product commercially available from Aladdin Industrial Co. having a weight average molecular weight of 105～5×106g/mol。
Example 1
This example is for explaining the battery positive electrode, the method for producing the same, and the all-solid-state battery of the invention.
Preparing a battery positive plate:
(1) 50 parts by weight of positive electrode material LiFePO412.5 parts by weight of crosslinkable copolymer 1#, 6.1 parts by weight of LiN (SO)2CF2CF3)2Dispersing 5.2 parts by weight of pentaerythritol tetraacrylate, 1.2 parts by weight of 2-hydroxy-2-methyl propyl ketone, 5 parts by weight of polyvinylidene fluoride and 5 parts by weight of conductive graphite in 200 parts by weight of N-methyl pyrrolidone solvent to obtain positive electrode slurry;
(2) coating the positive electrode slurry on two sides of an aluminum foil (with the thickness of 20 microns), drying for 1h at 60 ℃, then irradiating for 5min by using an ultraviolet curing instrument, then continuously drying for 24h at 60 ℃, and rolling to prepare a battery positive plate, wherein the thickness of a positive electrode material layer formed by the positive electrode slurry is 50 microns (the thickness of a single side).
Forming an electrolyte layer:
(1) 50 parts by weight of crosslinkable copolymer 1#, 20 parts by weight of LiN (SO)2CF2CF3)220 parts by weight of pentaerythritol tetraacrylate and 4.8 parts by weight of 2-hydroxy-2-methylpropanone were dispersed in 25 parts by weight of N-methylpyrrolidone solvent to obtain an electrolyte slurry;
(2) coating the electrolyte slurry on one surface of the battery positive plate, drying at 60 ℃ for 1h, irradiating for 5min by using an ultraviolet curing instrument to form a cured film to form an electrolyte layer, continuing to dry at 60 ℃ for 24h, forming the same electrolyte layer on the reverse surface of the battery positive plate by using the same method after drying, and hot-pressing at 60 ℃ to obtain the positive electrode with the electrolyte layer attached, wherein the thickness of the electrolyte layer is 50 microns (single-side thickness).
Assembling the battery:
cutting the positive electrode and the lithium-coated copper foil attached with the electrolyte layer into slices (a negative electrode, the same below) in a glove box containing high-purity Ar atmosphere, welding a tab by using a spot welding machine, laminating the positive electrode and the negative electrode, placing the laminated slices in an aluminum-plastic film for sealing, taking out, and carrying out hot pressing at 60 ℃ for 1 h; thus, battery C1 was produced.
Example 2
This example is for explaining the battery positive electrode, the method for producing the same, and the all-solid-state battery of the invention.
Preparing a battery positive plate:
(1) 60 parts by weight of LiCoO as a positive electrode material215 parts by weight of crosslinkable copolymer 2#, 4.88 parts by weight of LiN (SO)2CF2CF3)2Dispersing 4.16 parts by weight of pentaerythritol tetraacrylate, 0.96 part by weight of 4-dimethylaminoethyl benzoate, 4 parts by weight of polyvinylidene fluoride and 5 parts by weight of conductive carbon black in 240 parts by weight of N, N-dimethylformamide solvent to obtain positive electrode slurry;
(2) coating the positive electrode slurry on two sides of an aluminum foil (with the thickness of 20 microns), drying for 1h at 60 ℃, then irradiating for 10min by using an ultraviolet curing instrument, then continuously drying for 24h at 60 ℃, and rolling to prepare a battery positive electrode plate, wherein the thickness of a positive electrode material layer formed by the positive electrode slurry is 30 microns (the thickness of a single side).
Forming an electrolyte layer:
(1) 50 parts by weight of crosslinkable copolymer 2#, 15 parts by weight of LiN (SO)2CF2CF3)213.8 parts by weight of pentaerythritol tetraacrylate and 3.2 parts by weight of ethyl 4-dimethylaminobenzoate were dispersed in 30 parts by weight of N, N-dimethylformamide solvent to obtain an electrolyte slurry;
(2) coating the electrolyte slurry on one surface of the battery positive plate, drying at 60 ℃ for 1h, irradiating for 10min by using an ultraviolet curing instrument to form a cured film to form an electrolyte layer, continuing to dry at 60 ℃ for 24h, forming the same electrolyte layer on the reverse surface of the battery positive plate by using the same method after drying, and hot-pressing at 60 ℃ to obtain the positive electrode with the electrolyte layer attached, wherein the thickness of the electrolyte layer is 30 mu m (single-side thickness).
Assembling the battery:
cutting the positive electrode and the lithium-coated copper foil attached with the electrolyte layer into slices in a glove box containing high-purity Ar atmosphere, welding a tab by using a spot welding machine, laminating the positive electrode and the negative electrode, placing the laminated sheets in an aluminum plastic film for sealing, taking out, and carrying out hot pressing for 1h at 60 ℃; thus, battery C2 was produced.
Example 3
This example is for explaining the battery positive electrode, the method for producing the same, and the all-solid-state battery of the invention.
Preparing a battery positive plate:
(1) 70 parts by weight of LiCoO as a positive electrode material220 parts by weight of crosslinkable copolymer 3#, 3.66 parts by weight of LiBOB, 6.12 parts by weight of pentaerythritol tetraacrylate, 1.72 parts by weight of 2-hydroxy-2-methyl propyl ketone, 3 parts by weight of polyvinylidene fluoride and 6 parts by weight of conductive graphite are dispersed in 280 parts by weight of acetonitrile solvent to obtain positive electrode slurry;
(2) coating the positive electrode slurry on two sides of an aluminum foil (with the thickness of 20 microns), drying for 1h at 60 ℃, then irradiating for 6min by using an ultraviolet curing instrument, then continuously drying for 24h at 60 ℃, and rolling to prepare a battery positive plate, wherein the thickness of a positive electrode material layer formed by the positive electrode slurry is 20 microns (the thickness of a single side).
Forming an electrolyte layer:
(1) dispersing 50 parts by weight of crosslinkable copolymer 3#, 12 parts by weight of LiBOB, 15.3 parts by weight of pentaerythritol tetraacrylate and 4.3 parts by weight of ethyl 4-dimethylaminobenzoate in 30 parts by weight of acetonitrile solvent to obtain electrolyte slurry;
(2) coating the electrolyte slurry on one surface of the battery positive plate, drying at 60 ℃ for 1h, irradiating for 6min by using an ultraviolet curing instrument to form a cured film to form an electrolyte layer, continuing to dry at 60 ℃ for 24h, forming the same electrolyte layer on the reverse surface of the battery positive plate by using the same method after drying, and hot-pressing at 60 ℃ to obtain the positive electrode with the electrolyte layer attached, wherein the thickness of the electrolyte layer is 20 mu m (single-side thickness).
Assembling the battery:
cutting the positive electrode and the lithium-coated copper foil attached with the electrolyte layer into slices in a glove box containing high-purity Ar atmosphere, welding a tab by using a spot welding machine, laminating the positive electrode and the negative electrode, placing the laminated sheets in an aluminum plastic film for sealing, taking out, and carrying out hot pressing for 1h at 60 ℃; thus, battery C3 was produced.
Example 4
This example is intended to illustrate the negative electrode for a battery, the method for producing the same, and an all-solid battery of the present invention.
The method of embodiment 1, except that:
preparing a battery negative plate:
(1) 80 parts by weight of graphite, 7.9 parts by weight of crosslinkable copolymer 1#, 3.9 parts by weight of LiN (SO)2CF2CF3)23.4 parts by weight of pentaerythritol tetraacrylate, 0.8 part by weight of 2-hydroxy-2-methyl propyl phenyl ketone, 2.4 parts by weight of styrene butadiene rubber and 1.6 parts by weight of carboxymethyl cellulose are dispersed in 320 parts by weight of N-methyl pyrrolidone solvent to obtain negative electrode slurry;
(2) coating the negative electrode slurry on two sides of a copper foil (with the thickness of 20 microns), drying for 1h at 60 ℃, then irradiating for 5min by using an ultraviolet curing instrument, then continuously drying for 24h at 60 ℃, and rolling to prepare a battery negative electrode sheet, wherein the thickness of a negative electrode material layer formed by the negative electrode slurry is 50 microns (the thickness of a single side).
Thus, battery C4 was produced.
Example 5
This example is for explaining the battery positive electrode, the method for producing the same, and the all-solid-state battery of the invention.
The method of embodiment 1, except that:
preparing a battery positive plate: positive electrode material LiFePO4The amount of the cross-linkable copolymer 1# was 50 parts by weight, the amount of the cross-linkable copolymer 1# was 5 parts by weight, the amount of the pentaerythritol tetraacrylate was 2.1 parts by weight, and the amount of the 2-hydroxy-2-methylpropanone was 0.65 parts by weight.
Finally, cell C5 was obtained.
Example 6
This example is for explaining the battery positive electrode, the method for producing the same, and the all-solid-state battery of the invention.
The method of embodiment 1, except that:
preparing a battery positive plate: positive electrode material LiFePO4The amount of the cross-linkable copolymer 1# was 50 parts by weight, the amount of the cross-linkable copolymer 1# was 25 parts by weight, the amount of the pentaerythritol tetraacrylate was 7.5 parts by weight, and the amount of the 2-hydroxy-2-methylpropanone was 2 parts by weight.
Finally, cell C6 was obtained.
Examples 7 to 9
This example is for explaining the battery positive electrode, the method for producing the same, and the all-solid-state battery of the invention.
Batteries C7, C8, and C9 were prepared according to the method described in example 1, except that crosslinkable copolymers 4#, 5#, and 6# were used instead of crosslinkable copolymer 1#, respectively, in preparing the positive electrode sheet of the battery and forming the electrolyte layer.
Comparative example 1
Preparing a battery positive plate:
(1) 50 parts by weight of positive electrode material LiFePO420 parts by weight of PEO, 6.1 parts by weight of LiN (SO)2CF2CF3)2Dispersing 20 parts by weight of polyvinylidene fluoride and 5 parts by weight of conductive graphite in 200 parts by weight of N-methylpyrrolidone solvent to obtain positive electrode slurry;
(2) coating the positive electrode slurry on two sides of an aluminum foil (with the thickness of 20 microns), drying for 24h at 60 ℃, and rolling to prepare a battery positive plate, wherein the thickness of a positive electrode material layer formed by the positive electrode slurry is 50 microns (the thickness of a single side).
Forming an electrolyte layer:
(1) 40 parts by weight of PEO and 10 parts by weight of LiN (SO)2CF2CF3)2Dispersing in 30 parts by weight of an N-methylpyrrolidone solvent to obtain an electrolyte slurry;
(2) the electrolyte slurry was applied to one surface of the positive electrode sheet of the above-mentioned battery, dried at 60 ℃ for 24 hours, and after drying, the same electrolyte layer was formed on the reverse surface of the positive electrode sheet of the battery by the same method, and hot-pressed at 60 ℃ to obtain a positive electrode having an electrolyte layer attached thereto, the electrolyte layer having a thickness of 50 μm (one-sided thickness).
Assembling the battery:
cutting the positive electrode and the lithium-coated copper foil attached with the electrolyte layer into slices in a glove box containing high-purity Ar atmosphere, welding a tab by using a spot welding machine, laminating the positive electrode and the negative electrode, placing the laminated sheets in an aluminum plastic film for sealing, taking out, and carrying out hot pressing for 1h at 60 ℃; thus, battery DC1 was produced.
Comparative example 2
According to the method described in example 1, except that copolymer # 7 was used in place of crosslinkable copolymer # 1 in the preparation of the positive electrode sheet for a battery and in the formation of the electrolyte layer, the corresponding positive electrode sheet for a battery and battery DC2 were obtained.
Test example 1
The peel strength and the compacted density of the electrode tabs of the batteries in the above examples, and the specific capacity of the resulting batteries were tested, and the results are shown in table 1, in which:
testing the peel strength of the electrode slice: the universal testing machine of WDW-0.5 of Shenzhen Junrui testing instrument Limited is adopted for testing, and the universal testing machine specifically comprises the following components: cutting the electrode sheet into a sample with a length and width of 60 × 20mm, adhering the back surface of the electrode sheet to a stainless steel plate A for testing by using an adhesive tape, adhering an adhesive tape with a width of 18mm to the back surface of the electrode sheet, exposing a part of the adhesive tape, adhering the adhesive tape to a stainless steel plate B, clamping the stainless steel plate A, B on a testing machine, and testing the peel strength at a speed of 30mm/min under the conditions of 25 ℃ and a relative humidity of less than 5% RH.
Electrode compaction density test: the universal testing machine of WDW-0.5 of Shenzhen Junrui testing instrument Limited is adopted for testing, and the universal testing machine specifically comprises the following components: respectively measuring the thickness of the electrode slice and the aluminum foil by using a digital display micrometer, recording the thickness as L (mum), cutting the electrode into a wafer with the diameter of 13mm, weighing the mass as m (mg); compacted density, expressed as ρ, ρ ═ m × 10-3/(3.14×(1.3/2)2×L×10-4)＝7.54m/L g/cm3。
Specific capacity test: the method adopts a blue battery test system (CT2001C, blue electronic corporation of Wuhan city) to carry out charge and discharge test on the battery, and comprises the following specific processes: and (3) carrying out constant-current charge-discharge mode test on the lithium ion batteries by using a charge-discharge instrument at 60 ℃, wherein the charge cut-off voltage is 4.0V, the discharge cut-off voltage is 3.0V, and the charge-discharge multiplying power is 0.5C, and the first specific capacity and the circulating 20-time specific capacity of each lithium ion battery are obtained through test.
TABLE 1
Figure BDA0001338376640000201
As can be seen from Table 1, the electrode sheet obtained by the invention has higher glass strength and compacted density, is suitable for being used as an electrode sheet of a lithium battery, and the obtained battery also has higher specific capacity and long cycle life.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (55)

1. A battery electrode, comprising: the electrode comprises an electrode current collector and an electrode material layer attached to the surface of the electrode current collector, wherein the electrode material layer contains a polymer matrix and an electrode active material, and the polymer matrix is a cross-linked polymer;
wherein the crosslinked polymer contains a crosslinked structure provided by a crosslinking agent and a copolymer chain linked to the crosslinked structure, the copolymer chain being provided by a crosslinkable copolymer containing a structural unit represented by formula (1), a structural unit represented by formula (2), and a structural unit represented by formula (3), wherein the crosslinkable copolymer is linked to the crosslinking agent through at least a part of the structural unit represented by formula (3) to provide the copolymer chain;
formula (1):
Figure 910122DEST_PATH_IMAGE001
formula (2):
Figure 296104DEST_PATH_IMAGE002
formula (3):
Figure 75841DEST_PATH_IMAGE003
，
wherein R is H or C1-C4 alkyl, L is C0-C4 alkylene or-R1-O-R2-，R1Is C0-C4 alkylene, R2Is C0-C4 alkylene;
the crosslinking agent is one or more of acrylate crosslinking agents containing at least two acrylate groups, wherein the acrylate groups are groups shown in a formula (4), and the formula (4): -O-C (O) -C (R') = CH2R' is H or C1-C4 alkyl;
the content of the polymer matrix is 20 to 50 parts by weight with respect to 100 parts by weight of the electrode material.
2. The battery electrode of claim 1, wherein R is H, methyl, or ethyl, and L is a C0 alkylene, -CH2-、-CH2CH2-、-CH2CH2CH2-、-O-、-O-CH2-、-O-CH2CH2-、-CH2-O-、-CH2-O-CH2-、-CH2-O-CH2CH2-、-CH2CH2-O-、-CH2CH2-O-CH2-or-CH2CH2-O-CH2CH2-; r' is H, methyl or ethyl.
3. The battery electrode according to claim 2, wherein the crosslinkable copolymer has a molar ratio of the structural unit represented by formula (1), the structural unit represented by formula (2), and the structural unit represented by formula (3) of 100: 0.5-25: 0.5-20.
4. The battery electrode according to claim 3, wherein the crosslinkable copolymer has a molar ratio of the structural unit represented by formula (1), the structural unit represented by formula (2), and the structural unit represented by formula (3) of 100: 1-21: 0.5-15.
5. The battery electrode according to claim 4, wherein the crosslinkable copolymer has a molar ratio of the structural unit represented by formula (1), the structural unit represented by formula (2), and the structural unit represented by formula (3) of 100: 1-15: 1-10.
6. The battery electrode according to claim 5, wherein the crosslinkable copolymer has a molar ratio of the structural unit represented by formula (1), the structural unit represented by formula (2), and the structural unit represented by formula (3) of 100: 1-8: 1-6.
7. The battery electrode of claim 2, wherein the crosslinkable copolymer has a weight average molecular weight of 5,000-5,000,000 g/mol.
8. The battery electrode of claim 7, wherein the crosslinkable copolymer has a weight average molecular weight of 50,000-1,000,000 g/mol.
9. The battery electrode of claim 8, wherein the cross-linkable copolymer has a weight average molecular weight of 50,000-500,000 g/mol.
10. The battery electrode of claim 9, wherein the cross-linkable copolymer has a weight average molecular weight of 50,000-95,000 g/mol.
11. The battery electrode of any of claims 1-10, wherein the copolymer chain is present in an amount of 60-95 wt% based on the weight of the polymer matrix.
12. The battery electrode of claim 11, wherein the copolymer chains are present in an amount of 70-92 wt%, based on the weight of the polymer matrix.
13. The battery electrode of claim 12, wherein the copolymer chain is present in an amount of 70-90 wt%, based on the weight of the polymer matrix; the content of the crosslinked structure is 5 to 40% by weight.
14. The battery electrode according to claim 13, wherein the content of the crosslinked structure is 8 to 30 wt%.
15. The battery electrode of claim 11, wherein the crosslinker is ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, 1, 3-propylene glycol dimethacrylate, 1, 2-propylene glycol dimethacrylate, 1, 3-propylene glycol diacrylate, 1, 2-propylene glycol diacrylate, 1, 4-butylene glycol dimethacrylate, 1, 3-butylene glycol dimethacrylate, 1, 4-butylene glycol diacrylate, 1, 3-butylene glycol diacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and mixtures thereof, One or more of pentaerythritol diacrylate, pentaerythritol triacrylate, and pentaerythritol tetraacrylate.
16. The battery electrode of claim 15, wherein the cross-linking agent is one or more of triethylene glycol dimethacrylate, triethylene glycol diacrylate, pentaerythritol triacrylate, and pentaerythritol tetraacrylate.
17. The battery electrode according to any one of claims 1 to 10, wherein the electrode material layer is a positive electrode material layer, the electrode active material is a positive electrode active material, and the positive electrode material layer further contains a lithium salt, a conductive agent, and a binder; the content of the lithium salt is 1-20 parts by weight with respect to 100 parts by weight of the positive electrode active material; the content of the conductive agent is 5-20 parts by weight; the content of the binder is 1-20 parts by weight.
18. The battery electrode according to claim 17, wherein the lithium salt is contained in an amount of 5 to 15 parts by weight, relative to 100 parts by weight of the positive electrode active material; the content of the conductive agent is 6-15 parts by weight; the content of the binder is 2-15 parts by weight.
19. The battery electrode of claim 17, wherein the lithium salt is LiClO4、LiPF6、LiBF4、LiBOB、LiN(SO2CF3)2、LiCF3SO3And LiN (SO)2CF2CF3)2One or more of (a).
20. The battery electrode of any one of claims 1-10, wherein the electrode material layer is a negative electrode material layer, the electrode active material is a negative electrode active material, and the negative electrode material layer further contains a lithium salt, a binder, and a thickener; the content of the lithium salt is 1 to 20 parts by weight with respect to 100 parts by weight of the negative active material; the content of the binder is 1-20 parts by weight; the content of the thickening agent is 1-20 parts by weight.
21. The battery electrode according to claim 20, wherein the lithium salt is contained in an amount of 1 to 5 parts by weight, relative to 100 parts by weight of the negative electrode active material; the content of the binder is 1-5 parts by weight; the content of the thickening agent is 1-5 parts by weight.
22. The battery electrode of claim 20, wherein the lithium salt is LiClO4、LiPF6、LiBF4、LiBOB、LiN(SO2CF3)2、LiCF3SO3And LiN (SO)2CF2CF3)2One or more of (a).
23. The battery electrode according to any one of claims 1 to 10, wherein the thickness of the electrode material layer is 10 to 100 μm.
24. A method of making a battery electrode, the method comprising:
(1) providing an electrode paste containing an electrode active material, a crosslinkable copolymer, a crosslinking agent, and a photoinitiator;
(2) coating the electrode slurry obtained in the step (1) on an electrode current collector, drying, and then crosslinking and curing under the irradiation of ultraviolet light to form an electrode material layer on the electrode current collector;
wherein the crosslinkable copolymer contains a structural unit represented by formula (1), a structural unit represented by formula (2), and a structural unit represented by formula (3);
formula (1):
Figure 674313DEST_PATH_IMAGE001
formula (2):
Figure 754264DEST_PATH_IMAGE002
formula (3):
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，
wherein R is H or C1-C4 alkyl, L is C0-C4 alkylene or-R1-O-R2-，R1Is C0-C4 alkylene, R2Is C0-C4 alkylene;
the crosslinking agent is one or more of acrylate crosslinking agents containing at least two acrylate groups, wherein the acrylate groups are groups shown in a formula (4), and the formula (4): -O-C (O) -C (R') = CH2R' is H or C1-C4 alkyl;
the crosslinkable copolymer and the crosslinking agent are used in a total amount of 20 to 50 parts by weight with respect to 100 parts by weight of the electrode active material.
25. The method of claim 24, wherein R is H, methyl, or ethyl, and L is C0 alkylene, -CH2-、-CH2CH2-、-CH2CH2CH2-、-O-、-O-CH2-、-O-CH2CH2-、-CH2-O-、-CH2-O-CH2-、-CH2-O-CH2CH2-、-CH2CH2-O-、-CH2CH2-O-CH2-or-CH2CH2-O-CH2CH2-; r' is H, methyl or ethyl.
26. The method according to claim 24, wherein the crosslinkable copolymer has a molar ratio of the structural unit represented by formula (1), the structural unit represented by formula (2), and the structural unit represented by formula (3) of 100: 0.5-25: 0.5-20.
27. The method according to claim 26, wherein the molar ratio of the structural unit represented by formula (1), the structural unit represented by formula (2), and the structural unit represented by formula (3) is 100: 1-21: 0.5-15.
28. The method according to claim 27, wherein the molar ratio of the structural unit represented by formula (1), the structural unit represented by formula (2), and the structural unit represented by formula (3) is 100: 1-15: 1-10.
29. The method according to claim 28, wherein the molar ratio of the structural unit represented by formula (1), the structural unit represented by formula (2), and the structural unit represented by formula (3) is 100: 1-8: 1-6.
30. The method as claimed in claim 24, wherein the crosslinkable copolymer has a weight average molecular weight of 5,000-5,000,000 g/mol.
31. The method as claimed in claim 30, wherein the crosslinkable copolymer has a weight average molecular weight of 50,000-1,000,000 g/mol.
32. The method as claimed in claim 31, wherein the crosslinkable copolymer has a weight average molecular weight of 50,000-500,000 g/mol.
33. The method as claimed in claim 32, wherein the crosslinkable copolymer has a weight average molecular weight of 50,000-95,000 g/mol.
34. The method of any one of claims 24-33, wherein the crosslinker is ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, 1, 3-propylene glycol dimethacrylate, 1, 2-propylene glycol dimethacrylate, 1, 3-propylene glycol diacrylate, 1, 2-propylene glycol diacrylate, 1, 4-butylene glycol dimethacrylate, 1, 3-butylene glycol dimethacrylate, 1, 4-butylene glycol diacrylate, 1-diacrylate, 3-butanediol ester, pentaerythritol diacrylate, pentaerythritol triacrylate and pentaerythritol tetraacrylate.
35. The method of claim 34, wherein the cross-linking agent is one or more of triethylene glycol dimethacrylate, triethylene glycol diacrylate, pentaerythritol triacrylate, and pentaerythritol tetraacrylate.
36. The method of any one of claims 24-33, wherein the cross-linkable copolymer is present in an amount of 60 to 95 weight percent, based on the total weight of the cross-linkable copolymer and the cross-linking agent; the amount of the cross-linking agent is 5 to 40 wt%.
37. The method of claim 36, wherein the cross-linkable copolymer is present in an amount of 70 to 92 weight percent based on the total weight of the cross-linkable copolymer and the cross-linking agent.
38. The method of claim 37, wherein the cross-linkable copolymer is present in an amount of 70 to 90 weight percent based on the total weight of the cross-linkable copolymer and the cross-linking agent.
39. The method of claim 36, wherein the crosslinking agent is present in an amount of 8 to 30 wt%, based on the total weight of the crosslinkable copolymer and the crosslinking agent.
40. The method of any one of claims 24-33, wherein the electrode material layer is a positive electrode material layer, the electrode active material is a positive electrode active material, and the electrode slurry further incorporates a lithium salt, a conductive agent, and a binder; the content of the lithium salt is 1 to 20 parts by weight with respect to 100 parts by weight of the electrode active material; the content of the conductive agent is 5-20 parts by weight; the content of the binder is 1-20 parts by weight.
41. The method according to claim 40, wherein the lithium salt is contained in an amount of 5-15 parts by weight, relative to 100 parts by weight of the electrode active material; the content of the conductive agent is 6-15 parts by weight; the content of the binder is 2-15 parts by weight.
42. The method of claim 40, wherein said lithium salt is LiClO4、LiPF6、LiBF4、LiBOB、LiN(SO2CF3)2、LiCF3SO3And LiN (SO)2CF2CF3)2One or more of (a).
43. The method of any one of claims 24-33, wherein the electrode material layer is a negative electrode material layer, the electrode active material is a negative electrode active material, and the electrode slurry further incorporates a lithium salt, a binder, and a thickener; the content of the lithium salt is 1 to 20 parts by weight with respect to 100 parts by weight of the negative active material; the content of the binder is 1-20 parts by weight; the content of the thickening agent is 1-20 parts by weight.
44. The method of claim 43, wherein the lithium salt is present in an amount of 1 to 5 parts by weight per 100 parts by weight of the negative active material; the content of the binder is 1-5 parts by weight; the content of the thickening agent is 1-5 parts by weight.
45. The method of claim 44, wherein the lithium salt is LiClO4、LiPF6、LiBF4、LiBOB、LiN(SO2CF3)2、LiCF3SO3And LiN (SO)2CF2CF3)2One or more of (a).
46. A process according to any one of claims 24 to 33, wherein the photoinitiator is one or more of 2-hydroxy-2-methylpropiophenone, ethyl (2,4, 6-trimethylbenzoyl) phosphonate, ethyl 4-dimethylaminobenzoate, 1-hydroxycyclohexylphenylketone, benzoin dimethyl ether, methyl o-benzoylbenzoate and 4-chlorobenzophenone.
47. The method of claim 46, wherein the photoinitiator is present in an amount of 2 to 15 weight percent, based on the total weight of the crosslinkable copolymer and the crosslinking agent.
48. The method of claim 47, wherein the photoinitiator is present in an amount of 3 to 8 weight percent, based on the total weight of the crosslinkable copolymer and crosslinker.
49. The method of any one of claims 24-33, wherein the electrode material layer has a thickness of 10-100 μ ι η.
50. A battery electrode made by the method of any one of claims 24-49.
51. An all-solid battery, wherein the all-solid battery comprises: a positive electrode, an electrolyte layer and a negative electrode, the positive and/or negative electrode being a battery electrode as claimed in any one of claims 1 to 23 and 50.
52. The all-solid battery according to claim 51, wherein the electrolyte layer is a polymer electrolyte membrane attached to the positive electrode and/or the negative electrode, the polymer electrolyte membrane containing a polymer matrix and a lithium salt dispersed in the polymer matrix, the polymer matrix being the polymer matrix defined in claims 1 to 23.
53. The all-solid battery according to claim 51, wherein the electrolyte layer is a polymer electrolyte membrane attached to a positive electrode and/or a negative electrode, and the polymer electrolyte membrane is prepared by a method comprising:
(a) providing an electrolyte paste comprising a lithium salt, a cross-linkable copolymer, a cross-linking agent, and a photoinitiator;
(b) coating the electrolyte slurry on the anode and/or the cathode, drying, and then crosslinking and curing under the irradiation of ultraviolet light to form an electrolyte layer on the anode and/or the cathode;
wherein the crosslinkable copolymer, the crosslinking agent and the photoinitiator are as defined in claims 24 to 48.
54. The all-solid battery according to any one of claims 51 to 53, wherein the thickness of the electrolyte layer is 10 to 200 μm.
55. The all-solid battery according to any one of claims 51 to 53, wherein the negative electrode is a negative electrode collector having metallic lithium attached to a surface thereof.
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