CN116285882B - Adhesive, negative electrode plate, battery and electricity utilization device - Google Patents
Adhesive, negative electrode plate, battery and electricity utilization device Download PDFInfo
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- CN116285882B CN116285882B CN202310578399.0A CN202310578399A CN116285882B CN 116285882 B CN116285882 B CN 116285882B CN 202310578399 A CN202310578399 A CN 202310578399A CN 116285882 B CN116285882 B CN 116285882B
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 54
- 239000000853 adhesive Substances 0.000 title claims abstract description 48
- 230000005611 electricity Effects 0.000 title description 2
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- 239000000178 monomer Substances 0.000 claims abstract description 67
- -1 4-amino-catechol alkene Chemical class 0.000 claims abstract description 59
- 229920000642 polymer Polymers 0.000 claims abstract description 49
- 150000002148 esters Chemical class 0.000 claims abstract description 40
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 70
- 239000007773 negative electrode material Substances 0.000 claims description 55
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- RZLXRFDFCORTQM-UHFFFAOYSA-N OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCCn1c(=O)n(CCO)c(=O)n(CCO)c1=O Chemical group OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCCn1c(=O)n(CCO)c(=O)n(CCO)c1=O RZLXRFDFCORTQM-UHFFFAOYSA-N 0.000 claims description 4
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- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 claims 1
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- 239000010405 anode material Substances 0.000 abstract description 10
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- 238000002156 mixing Methods 0.000 description 6
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- 229920002125 Sokalan® Polymers 0.000 description 5
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
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- 239000007774 positive electrode material Substances 0.000 description 5
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
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- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 3
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
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- 101150058243 Lipf gene Proteins 0.000 description 1
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- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
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- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J187/00—Adhesives based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
- C09J187/005—Block or graft polymers not provided for in groups C09J101/00 - C09J185/04
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/021—Block or graft polymers containing only sequences of polymers of C08C or C08F
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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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
- H01M4/621—Binders
- H01M4/622—Binders being polymers
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- 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
Abstract
The application discloses an adhesive, a negative pole piece, a battery and an electric device. The binder comprises a copolymer of a first polymer having the structural formula (1) and a second polymer having the structural formula (2) and a copolymer of a first monomer comprising at least one of urethane, a compound having the structural formula (2), tri (2-hydroxyethyl) isocyanurate triacrylate and (2-hydroxyethyl) methacrylate, and a second monomer comprising at least one of an ester obtained by dehydrating a compound having the structural formula (3) with an anhydride of alkene, 4-amino-catechol alkene acid ester, dopamine alkene hydrochloride, 1-amino catechol alkene acid ester, 3, 4-dihydroxyphenylalanine alkene acid ester,(1),(2),the weight average molecular weight of the binder is 20-300 ten thousand in the formula (3). The binder can inhibit expansion of the anode material.
Description
Technical Field
The application relates to the technical field of batteries, in particular to an adhesive, a negative electrode plate, a battery and an electric device.
Background
The silicon-based anode material has higher capacity, but has serious volume expansion in the cyclic charge and discharge process, so that the anode plate structure is loose, the conductivity of the battery is poor, and the SEI film (solid electrolyte film) on the surface of the anode plate can be continuously damaged, and electrolyte is continuously consumed, thereby reducing the cycle efficiency and the service life of the battery. However, the existing adhesive has poor inhibition effect on the expansion problem of the silicon-based material, and is difficult to alleviate the technical problems of reduced battery cycle performance, shortened service life and the like caused by the expansion of the silicon-based material.
Thus, current binders, negative electrode tabs, batteries, and electrical devices remain to be improved.
Disclosure of Invention
In view of the above problems, the application provides a binder, a negative electrode plate, a battery and an electric device, which aim to at least alleviate or even solve the technical problems of poor battery cycle performance, short service life and the like caused by expansion of a negative electrode material to a certain extent.
In one aspect of the application, the application provides an adhesive. In some embodiments of the application, the binder comprises a copolymer of a first polymer having the formula (1) and a second polymer having the formula (2) and a copolymer of a first monomer comprising at least one of a urethane, a compound having the formula (2), tris (2-hydroxyethyl) isocyanurate triacrylate, and (2-hydroxyethyl) methacrylate, and a second monomer comprising at least one of an ester having the formula (3) dehydrated with an anhydride of an alkene, 4-amino-catechol alkene ester, dopamine hydrochloride, 1-amino catechol alkene ester, 3, 4-dihydroxyphenylalanine alkene ester,
Formula (1),>(2),>(3),
wherein X comprises at least one of hydroxyl and mercapto, the number of carbon atoms in X is not more than 3, Y comprises at least one of hydroxyl and mercapto, the number of carbon atoms in Y is not more than 3, Z comprises at least one of amino and mercapto, the number of carbon atoms in Z is not more than 3, and the weight average molecular weight of the binder is 20-300 ten thousand.
The binder has a three-dimensional network structure, the first polymer can provide enough adhesive force and mechanical strength, and the second polymer has better elasticity and self-healing property, so that the binder can inhibit the expansion of the anode material at least to a certain extent, thereby improving the cycle performance of the battery and prolonging the service life of the battery; and the binder has proper molecular weight, is added into the cathode slurry, is not easy to agglomerate after being stirred and stood for a period of time, and is suitable for large-scale production of batteries.
In some embodiments of the application, the first polymer comprises at least one of the polymers of the following structural formula:
formula (1-1), a->(1-2),
formula (1-3), a->(1-4),
formula (1-5), a->(1-6),
Formulae (1-7).
In some embodiments of the application, the first monomer comprises at least one of the compounds of the following structural formula:
formula (2-1), a->(2-2),
(2-3),
(2-4),
formula (2-5), a->(2-6),
formula (2-7).
In some embodiments of the application, the second monomer comprises at least one of the following compounds of formula:
formula (3-1), a->(3-2),
formula (3-3), a->(3-4),
formula (3-5), a->Formula (3-6).
In some embodiments of the application, the binder satisfies at least one of the following conditions: x is hydroxy; the first monomer comprises 2-hydroxyethyl acrylate; the second monomer includes at least one of 4-amino-catechol methacrylate, 4-amino-catechol butenoate, and 4-amino-catechol pentenoate; the olefmic anhydride includes at least one of methacrylic anhydride, butenoic anhydride, and 4-pentenoic anhydride. Thus, the binder can effectively suppress expansion of the anode material, thereby improving cycle performance of the battery.
In some embodiments of the application, the binder has a weight average molecular weight of 100 to 200 tens of thousands. Therefore, the weight average molecular weight of the binder is in a proper range, so that the expansion of the anode material can be more effectively inhibited, the cycle performance of the battery is better, and the service life of the battery is longer.
In some embodiments of the application, X is hydroxy, the first monomer is 2-hydroxyethyl acrylate, and the second monomer is 4-amino-catechol methacrylate.
In some embodiments of the application, X is hydroxy, the first monomer is tris (2-hydroxyethyl) isocyanuric acid triacrylate, and the second monomer is 4-amino-catechol methacrylate.
In some embodiments of the application, X is hydroxy, the first monomer is a compound of structural formula (2-6), and the second monomer is 4-amino-catechol methacrylate.
In some embodiments of the application, X is hydroxy, the first monomer is 2-hydroxyethyl acrylate, and the second monomer is 1-amino catechol methacrylate.
In some embodiments of the application, the first polymer has the structural formula (1-6), the first monomer is 2-hydroxyethyl acrylate, and the second monomer is 4-amino-catechol methacrylate.
In another aspect of the application, the application provides a negative electrode tab. In some embodiments of the present application, the negative electrode tab includes a negative electrode current collector and a negative electrode active material layer on at least one side surface of the negative electrode current collector, the negative electrode active material layer including: a negative electrode active material comprising a silicon-based material and graphite, and the aforementioned binder. Thus, the negative electrode tab has all of the features and advantages of the binder described above and will not be described in detail herein. In general, the negative electrode active material layer of the negative electrode sheet has higher bonding strength with the negative electrode current collector, and the negative electrode sheet has good cycling stability in the cycling charge and discharge process.
In some embodiments of the present application, the anode active material layer further includes at least one of a viscous material and a conductive agent. The adhesive material is added to further improve the bonding strength between the anode active material layer and the anode current collector; the addition of the conductive agent can reduce the resistance of the battery.
In some embodiments of the application, the negative electrode tab satisfies at least one of the following conditions: the silicon-based material includes at least one of pre-lithiated silicon oxide, and silicon carbon; the graphite includes at least one of natural graphite and artificial graphite; the adhesive material includes at least one of styrene-butadiene rubber, polyamide imide, polyvinyl alcohol, polyethylene imine, polyimide, and poly (t-butyl acrylate-triethoxysilane); the weight average molecular weight of the viscous material is 4 ten thousand to 200 ten thousand; the conductive agent includes at least one of carbon nanotubes, carbon black, carbon fibers, and graphene; the negative electrode active material further includes at least one of hard carbon, soft carbon, ketjen black, mesophase carbon microspheres, graphene, and carbon fibers. The silicon-based material has higher capacity, and is beneficial to improving the capacity of the battery; the artificial graphite and the natural graphite have good circulation stability, and are beneficial to improving the circulation performance of the battery; the adhesive material can further improve the adhesive property between the negative electrode active material layer and the negative electrode current collector, and is beneficial to reducing the risk of falling off of the negative electrode active material layer on the negative electrode current collector; the molecular weight of the adhesive material is 4-200 ten thousand, so that the bonding strength of the negative current collector and the negative active material layer can be further improved; the conductive agent has better conductivity, and the addition of the conductive agent is beneficial to reducing the resistance of the battery; the negative electrode active material is added with one or more of hard carbon, soft carbon, ketjen black, mesophase carbon microspheres, graphene, carbon fibers and other materials, so that the cycle stability or conductivity of the battery can be further improved.
In some embodiments of the present application, the anode active material layer includes, based on the total mass of the anode active material layer: silicon-based materials with mass content of 0.85-59.82 wt%; 34-98.75 wt% of graphite; conductive agent with mass content of 0.1-5 wt%; the mass content of the binder is 0.1-5 wt%; the adhesive material comprises 0.1-5 wt% of adhesive material. The proportion of each component in the anode active material layer is proper, which is beneficial to further improving the overall performance of the anode piece.
In some embodiments of the present application, the negative electrode active material is composed of a silicon-based material and graphite, and the mass ratio of the silicon-based material to the graphite is 1:99-3:2. The mass ratio of the silicon-based material to the graphite is in the above range, so that the battery has excellent cycle stability and high capacity.
In yet another aspect of the application, the application provides a battery. In some embodiments of the application, the battery includes a positive electrode tab, a negative electrode tab, and an electrolyte, the negative electrode tab being the negative electrode tab described previously. Thus, the battery has all the features and advantages of the negative electrode tab described above, and will not be described in detail herein. Overall, the cell has a high capacity and good cycling stability.
In yet another aspect of the present application, an electrical device is provided. In some embodiments of the application, the power device comprises a battery as described above. Thus, the power utilization device has all the features and advantages of the battery described above, and will not be described in detail herein.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the application. Also, like reference numerals are used to designate like parts throughout the accompanying drawings. In the drawings:
fig. 1 shows a schematic structure of a battery according to an embodiment of the present application;
fig. 2 shows an exploded view of the battery of fig. 1;
fig. 3 is a schematic view showing the structure of a battery module according to an embodiment of the present application;
fig. 4 is a schematic view showing the structure of a battery pack according to an embodiment of the present application;
fig. 5 shows an exploded view of the battery pack of fig. 4;
fig. 6 shows a schematic structure of an electric device in which a battery is used as a power source according to an embodiment of the present application.
Reference numerals illustrate:
1: a battery pack; 2: an upper case; 3: a lower box body; 4: a battery module; 5: a battery; 51: a housing; 52: an electrode assembly; 53: and a cover plate.
Detailed Description
Embodiments of the technical scheme of the present application are described in detail below. The following examples are only for more clearly illustrating the technical aspects of the present application, and thus are merely examples, and are not intended to limit the scope of the present application.
Reference herein to "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment may be included in at least one embodiment of the application. The appearances of such phrases in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. Those of skill in the art will explicitly and implicitly appreciate that the embodiments described herein may be combined with other embodiments.
For simplicity, only a few numerical ranges are specifically disclosed herein. However, any lower limit may be combined with any upper limit to form a range not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and any upper limit may be combined with any other upper limit to form a range not explicitly recited. Furthermore, each separately disclosed point or individual value may itself be combined as a lower limit or upper limit with any other point or individual value or with other lower limit or upper limit to form a range not explicitly recited.
In the description of the present application, all numbers disclosed herein are approximate, whether or not words of "about" or "about" are used. The numerical value of each number may vary by less than 10% or reasonably as considered by those skilled in the art, such as 1%, 2%, 3%, 4% or 5%.
In the description of the embodiments of the present application, the term "and/or" is merely an association relationship describing an association object, and indicates that three relationships may exist, for example, a and/or B may indicate: a exists alone, A and B exist together, and B exists alone. In addition, the character "/" herein generally indicates that the front and rear associated objects are an "or" relationship.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs; the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application; the terms "comprising" and "having" and any variations thereof in the description of the application and the claims and the description of the drawings above are intended to cover a non-exclusive inclusion.
As one of the most potential negative electrode materials of the lithium ion battery with high energy density, the silicon-based negative electrode material has higher theoretical specific capacity and lower oxidation-reduction electrode potential, however, the silicon-based negative electrode material has serious volume change in the cyclic charge-discharge process, so that the electrode structure is loose, the conductivity of the battery is poor, the SEI film on the surface of the electrode is continuously damaged, electrolyte is consumed, more and thicker SEI film is formed, and the cycle efficiency and the service life of the battery are reduced. The composite negative electrode formed by the silicon-based material and the graphite also has the technical problems of reduced battery cycle stability, shortened service life and the like caused by the expansion of the negative electrode material.
In order to alleviate or even solve at least one of the above technical problems to a certain extent, a "spring net" binder may be added to the negative electrode, where the binder is obtained by cross-linking polymerization of two polymers, where the first polymer may provide higher strength and binding property, and the second polymer has a certain elasticity and self-healing ability, the "spring net" binder contains a large number of hydrogen bond sites such as amino groups, hydroxyl groups, mercapto groups, etc., and may form hydrogen bonds with peripheral hydroxyl groups, carboxyl groups, amino groups, etc., and the second polymer has a certain elasticity and self-healing ability, and may stretch and shrink during cyclic charge and discharge, and the second polymer itself has catechol functional groups, and two hydroxyl groups of the catechol functional groups may also form covalent bonds with silicon-based materials such as silicon oxygen, etc., so as to form a cross-linked network structure, and during cyclic charge and discharge, the "spring net" binder may bind the negative electrode material, improve the expansion problem of the negative electrode material, and thus may alleviate the technical problems such as decrease in battery cycle stability and shortened service life caused by expansion of the negative electrode material.
The spring net binder can be used as a binder of a lithium ion battery anode material, and can be applied to a composite anode material system containing pre-lithiated silica and graphite, a composite anode material system containing silicon carbon and graphite and the like.
The lithium ion battery with the addition of the "spring net" binder to the battery negative electrode material system can be used in electrical devices that use the battery as a power source or in various energy storage systems that use the battery as an energy storage element. The powered device may include, but is not limited to, a cell phone, tablet, notebook computer, electric toy, electric tool, battery car, electric car, ship, spacecraft, and the like. Among them, the electric toy may include fixed or mobile electric toys, such as game machines, electric car toys, electric ship toys, electric plane toys, and the like, and the spacecraft may include planes, rockets, space planes, and spacecraft, and the like.
In one aspect of the application, the application provides an adhesive. In some embodiments of the application, the binder may include a copolymer of a first polymer and a second polymer. The first polymer may have a structural formula of formula (1), the second polymer may be a copolymer of a first monomer and a second monomer, the first monomer may include at least one of urethane, a compound having a structural formula of formula (2), tri (2-hydroxyethyl) isocyanurate triacrylate, and (2-hydroxyethyl) methacrylate, etc., and the second monomer may include at least one of an ester having a structural formula of formula (3) dehydrated with an olefmic anhydride, 4-amino-catechol olefmic acid ester (an ester obtained by dehydrating 4-amino-1, 2-catechol hydrochloride with an olefmic anhydride), dopamine hydrochloride olefmic acid ester (an ester obtained by dehydrating dopamine hydrochloride with an olefmic anhydride), 1-amino catechol olefmic acid ester (an ester obtained by dehydrating amino catechol with an olefmic anhydride), 3, 4-dihydroxyphenylalanine olefmic acid ester (an ester obtained by dehydrating dopa (3, 4-dihydroxyphenylalanine) and olefmic anhydride), etc.
Formula (1),>(2),>formula (3).
In the formula (1), X may include at least one of a hydroxyl group, a mercapto group, and the like, and the number of carbon atoms in X is not more than 3, for example, the number of carbon atoms in X may be 0, 1, 2, or 3, and n is the degree of polymerization. In some embodiments of the present application, formula (1) may be of the formula:
formula (1-1), a->(1-2),
formula (1-3), a->(1-4),
formula (1-5), a->(1-6),
formulae (1-7).
The X comprises at least one of hydroxyl and sulfhydryl, and the hydroxyl, sulfhydryl and the like can play a role in forming hydrogen bonds with carboxyl, hydroxyl, amino and the like of an external material so as to promote the formation of a three-dimensional network structure; in addition, the mercapto group can form an inorganic lithium salt (for example, lithium sulfide) having a good lithium conductivity, and thus the lithium conductivity of the negative electrode can be improved. The number of carbon atoms in X is not more than 3, and X can rotate at a larger angle, so that the flexibility of the adhesive is enhanced.
In the formula (2), Y may include at least one of a hydroxyl group, a mercapto group, and the like, and the number of carbon atoms in Y is not more than 3, for example, the number of carbon atoms in Y may be 0, 1, 2, or 3. In some embodiments of the present application, formula (2) may be of the formula:
Formula (2-1), a->(2-2),
(2-3),
(2-4),
formula (2-5), a->(2-6),
formula (2-7).
Y comprises at least one of hydroxyl, sulfhydryl and the like, the hydroxyl and sulfhydryl contain hydrogen and have lone pair electrons, which can play a role in forming hydrogen bonds with carboxyl, hydroxyl, amino and the like in the external material and promote the formation of a three-dimensional network structure; in addition, the mercapto group can form an inorganic lithium salt such as lithium sulfide having a good lithium conductivity, and thus the lithium conductivity of the negative electrode can be increased. The number of carbon atoms in Y is not more than 3, and Y can rotate at a larger angle, so that the flexibility of the adhesive is improved.
In the formula (3), Z may include at least one of an amino group, a mercapto group, and the like, and the number of carbon atoms in Z is not more than 3, for example, the number of carbon atoms in Z may be 0, 1, 2, or 3. In some embodiments of the present application, formula (3) may be of the formula:
formula (3-1), a->(3-2),
formula (3-3), a->(3-4),
formula (3-5), a->Formula (3-6).
Z comprises at least one of amino, sulfhydryl and the like, and the amino, sulfhydryl and the like can form hydrogen bonds with carboxyl, hydroxyl, amino and the like in the external material to promote the formation of a three-dimensional network structure; the mercapto group can form an inorganic lithium salt (for example, lithium sulfide or the like) having a good lithium conductivity, and is thus advantageous in improving the lithium conductivity of the negative electrode. The number of carbon atoms in Z is not more than 3, Z can rotate at a larger angle, and is not easy to break.
Herein, the copolymer of the first polymer and the second polymer refers to a polymer obtained by cross-linking polymerization of the first polymer and the second polymer. The copolymer of the first monomer and the second monomer refers to a polymer obtained by copolymerizing the first monomer and the second monomer.
In some embodiments of the present application, the weight average molecular weight of the binder may be 20 to 300 tens of thousands, for example, the weight average molecular weight of the binder may be 20 to 50 to 70, 100 to 150 to 170, 200 to 260 to 300, etc., the binder has a suitable weight average molecular weight, may provide good adhesion performance, and may be less prone to agglomeration during preparation of the negative electrode slurry, and the negative electrode slurry after stirring may be left for 24 hours or even longer without agglomeration, which is advantageous for mass production of the negative electrode sheet or battery. The weight average molecular weight of the binder can be adjusted by controlling the reaction time, the reaction temperature, the proportion of the reaction raw materials, and the like. The first polymer is used as a main body of the binder, the higher the content of the first polymer is, the larger the weight average molecular weight of the binder is, when the weight average molecular weight is too large, the binding force of the binder is strong, agglomeration phenomenon can occur when slurry (here, the slurry is stirred) is stirred, the slurry of the cathodes is stuck together, the fluidity is poor, and a pole piece cannot be formed; if the weight average molecular weight is too small, the binder cannot provide sufficient binding strength, the binding force between the binder and the negative electrode active material and between the binder and the negative electrode current collector is weak, and the negative electrode active material layer is easily detached from the negative electrode current collector during the cyclic charge and discharge process, resulting in a decrease in the cyclic stability of the battery.
The negative electrode slurry is a slurry obtained by dispersing a negative electrode active material, a binder, a conductive agent, and the like in a dispersing agent such as water, and is coated on at least one surface of a negative electrode current collector, and after drying treatment, a negative electrode active material layer is formed on the surface of the negative electrode current collector.
As used herein, an olefinic anhydride has a carbon-carbon double bond and an anhydride group.
In some embodiments of the present application, the alkylene anhydride may include at least one of methacrylic anhydride, butenoic anhydride, 4-pentenoic anhydride, and the like. Wherein the structural formula of methacrylic anhydride is shown as formula (4), the structural formula of butenoic anhydride is shown as formula (5), and the structural formula of 4-pentenoic anhydride is shown as formula (6).
(4),>(5),
formula (6).
In some embodiments of the present application, the alkene anhydride may include methacrylic anhydride, and the second monomer may include at least one of an ester of a compound of formula (3) dehydrated with methacrylic anhydride, 4-amino-catechol methacrylate (an ester of 4-amino-1, 2-catechol hydrochloride dehydrated with methacrylic anhydride), dopamine methacrylate hydrochloride (an ester of dopamine hydrochloride dehydrated with methacrylic anhydride), 1-amino catechol methacrylate (an ester of amino catechol dehydrated with methacrylic anhydride), 3, 4-dihydroxyphenylalanine methacrylate (an ester of dopa (3, 4-dihydroxyphenylalanine) dehydrated with methacrylic anhydride), and the like.
In some embodiments of the present application, the alkene anhydride may include butene anhydride, and the second monomer may include at least one of an ester obtained by dehydrating a compound of formula (3) with butene anhydride, 4-amino-catechol butenoate (an ester obtained by dehydrating 4-amino-1, 2-catechol hydrochloride with butene anhydride), dopamine hydrochloride (an ester obtained by dehydrating dopamine hydrochloride with butene anhydride), 1-amino catechol butenoate (an ester obtained by dehydrating amino catechol with butene anhydride), 3, 4-dihydroxyphenylalanine butenoate (an ester obtained by dehydrating dopa (3, 4-dihydroxyphenylalanine) with butene anhydride), and the like.
In some embodiments of the present application, the alkene anhydride may include 4-pentenoic acid anhydride, and the second monomer may include at least one of an ester of the compound of formula (3) dehydrated with 4-pentenoic acid anhydride, 4-amino-catechol pentenoate (an ester of 4-amino-1, 2-catechol hydrochloride dehydrated with 4-pentenoic acid anhydride), dopamine pentenoate hydrochloride (an ester of dopamine hydrochloride dehydrated with 4-pentenoic acid anhydride), 1-amino catechol pentenoate (an ester of amino catechol dehydrated with 4-pentenoic acid anhydride), 3, 4-dihydroxyphenylalanine pentenoate (an ester of dopa (3, 4-dihydroxyphenylalanine) dehydrated with 4-pentenoic acid anhydride), and the like.
The independent first polymer has certain bonding performance, can provide stronger bonding effect for the anode active material layer and the anode current collector, but has poorer flexibility, the branched chain of the first polymer is difficult to rotate at a large angle, and the inhibition effect on the expansion of the anode material is poorer; the second polymer alone has insufficient adhesion to the anode active material layer and the anode current collector, is highly swollen in the electrolyte, and adversely affects the cycle stability of the battery. The adhesive provided by the application comprises a copolymer of a first polymer and a second polymer, wherein the part corresponding to the first polymer is used as a main body of the adhesive, so that higher mechanical strength and better adhesive property can be provided, the part corresponding to the second polymer has certain elasticity and self-healing property, stretching and shrinking can be carried out in the charge and discharge process, the adhesive is obtained by cross-linking polymerization of the first polymer and the second polymer, higher mechanical strength can be provided, flow and creep can be prevented, and meanwhile, the adhesive has a large number of repeated hydrogen bonds and catechol functional groups in each local area, the self-healing capacity can be generated, the microscopic stability of a three-dimensional network structure is enhanced, the adhesive of the three-dimensional network structure has certain shrinkage property, the expanded negative electrode active material can be effectively bound, the adhesive has excellent self-healing property, good stability can be kept, the negative electrode active material is not easy to break due to mechanical fatigue, the volume expansion of the negative electrode active material can be effectively inhibited, the cycle performance of a battery can be further improved, and the service life of the battery can be remarkably prolonged.
In some embodiments of the present application, the weight average molecular weight of the binder may be 100 to 200 tens of thousands, for example, the weight average molecular weight of the binder may be 100 tens of thousands, 120 tens of thousands, 140 tens of thousands, 150 tens of thousands, 180 tens of thousands, 200 tens of thousands, etc., the weight average molecular weight of the binder may be within the above range, the binder may provide sufficient adhesive strength to the anode active material and the anode current collector, and the anode slurry may remain in a uniformly dispersed state for a long period of time after stirring; in addition, the weight average molecular weight of the binder is in the above range, so that a strong binding force can be provided for the negative electrode active material layer and the negative electrode current collector, and the negative electrode slurry can be kept in a uniformly dispersed state for a long time after stirring; moreover, the binder can effectively inhibit the expansion of the anode active material during the cyclic charge and discharge process, so that the battery has excellent cyclic stability and long service life.
In some embodiments of the application, X may be a hydroxyl group, as shown in formula (1-1), where the first polymer is polyacrylic acid (PAA). Polyacrylic acid has higher strength and adhesive property, and the mechanical strength and adhesive property of the adhesive can be obviously improved by crosslinking and polymerization of the polyacrylic acid and the second polymer.
In some embodiments of the application, the first monomer may include 2-hydroxyethyl acrylate, as shown in formula (2-1). The polymer of the 2-hydroxyethyl acrylate has better elasticity, and the hydroxyl contained in the 2-hydroxyethyl acrylate can provide hydrogen bond sites, thereby being beneficial to forming a three-dimensional network structure adhesive with certain elasticity.
In some embodiments of the application, the second monomer may include an ester of 4-amino-1, 2-catechol hydrochloride dehydrated with an alkylene anhydride, for example, 4-amino-catechol methacrylate (an ester of 4-amino-1, 2-catechol hydrochloride dehydrated with methacrylic anhydride), 4-amino-catechol butenoate (an ester of 4-amino-1, 2-catechol hydrochloride dehydrated with butenoic anhydride), and 4-amino-catechol pentenoate (an ester of 4-amino-1, 2-catechol hydrochloride dehydrated with 4-pentenoic anhydride). The second monomer contains catechol functional group, the catechol functional group has certain elasticity, and two hydroxyl groups of the functional group can be dehydrated with the anode active material to form covalent bonds, and can also form hydrogen bonds with peripheral hydroxyl groups, amino groups and the like to form a crosslinked network structure, so that the expansion of the anode active material is inhibited.
In some embodiments of the application, X may be a hydroxyl group, the first monomer may be 2-hydroxyethyl acrylate, and the second monomer may be 4-amino-catechol methacrylate.
In some embodiments of the present application, X may be a hydroxyl group, the first monomer may be 2-hydroxyethyl acrylate, the second monomer is 4-amino-catechol methacrylate, and the binder has a weight average molecular weight of 170 ten thousand, so that a strong adhesion effect can be provided for the negative electrode active material layer and the negative electrode current collector, a high mechanical strength can be maintained, expansion of the negative electrode active material is effectively inhibited in a cyclic charge and discharge process, battery capacity "water jump" is not generated, and a good dynamic performance of the battery can be maintained, so that the battery has excellent cyclic stability and a long service life.
In some embodiments of the application, X may be hydroxyl, the first monomer may be 2-hydroxyethyl acrylate, the second monomer is 4-amino-catechol methacrylate, and the molar ratio of X, Y to Z in the binder is 32:8:1. Therefore, the weight average molecular weight of the binder is about 170 ten thousand, the binder can provide a stronger binding effect for the anode active material layer and the anode current collector, and meanwhile, the binder can also maintain a higher mechanical strength, and the expansion of the anode active material is effectively inhibited in the cyclic charge and discharge process, so that the battery has excellent cyclic stability and longer service life.
In some embodiments of the application, X may be a hydroxyl group, the first monomer may be tris (2-hydroxyethyl) isocyanuric acid triacrylate, and the second monomer may be 4-amino-catechol methacrylate.
In some embodiments of the application, X may be a hydroxyl group, the first monomer may be a compound of structural formula (2-6), and the second monomer may be 4-amino-catechol methacrylate.
In some embodiments of the application, X may be a hydroxyl group, the first monomer may be 2-hydroxyethyl acrylate, and the second monomer may be 1-amino catechol methacrylate.
In some embodiments of the application, the first polymer may have the formula (1-6), the first monomer may be 2-hydroxyethyl acrylate, and the second monomer may be 4-amino-catechol methacrylate.
The binder with proper molecular weight is formed by adopting the materials, so that the expansion of the anode active material in the charge and discharge process can be effectively inhibited, and the cycle performance of the battery is improved.
In another aspect of the application, the application provides a negative electrode tab. In some embodiments of the present application, the negative electrode tab may include a negative electrode current collector and a negative electrode active material layer on at least one side surface of the negative electrode current collector, and the negative electrode active material layer may include a negative electrode active material and the aforementioned binder. The negative electrode active material may include a silicon-based material and graphite, and thus, the negative electrode active material may have a high capacity of the silicon-based material and superior cycle stability and excellent electrical conductivity of the graphite at the same time.
The negative electrode active material layer in the negative electrode tab includes a negative electrode active material and the aforementioned binder, and thus, the negative electrode tab has all the features and advantages of the aforementioned binder, which are not described herein. In general, the negative electrode active material layer in the negative electrode plate and the negative electrode current collector have higher bonding strength, and the negative electrode plate is applied to a battery, so that the adhesive can effectively inhibit the expansion of the silicon-based material in the cyclic charge and discharge process, thereby obviously improving the cyclic stability of the battery.
In some embodiments of the application, the graphite may comprise at least one of natural graphite and synthetic graphite, e.g., the graphite may be natural graphite, synthetic graphite, or a mixture of natural graphite and synthetic graphite. The natural graphite and the artificial graphite have better stability and excellent conductivity, and the addition of the graphite into the negative electrode active material is beneficial to improving the conductivity and stability of the negative electrode active material layer.
In some embodiments of the present application, the silicon-based material may include at least one of pre-lithiated silicon oxide, silicon carbon, etc., each of which has a higher specific capacity, and the addition of the silicon-based material to the negative electrode active material is advantageous for improving the capacity of the battery. In some embodiments of the application, the silicon-based material may be pre-lithiated silicon oxide, or silicon carbon; in other embodiments of the present application, the silicon-based material may be a mixture of two or three of pre-lithiated silicon oxides, and silicon carbons.
In some embodiments of the present application, the anode active material may include at least one of hard carbon, soft carbon, ketjen black, mesophase carbon microspheres, graphene, carbon fibers, and the like in addition to the silicon-based material and graphite, and the addition of at least one of the above materials to the anode active material may improve the capacity, conductivity, and/or cycle stability of the anode to some extent.
In some embodiments of the present application, the negative electrode active material may include hard carbon, soft carbon, ketjen black, mesophase carbon microspheres, graphene, or carbon fibers in addition to the silicon-based material and graphite. In other embodiments of the present application, the anode active material may include two or more of hard carbon, soft carbon, ketjen black, mesophase carbon microspheres, graphene, and carbon fibers in addition to the silicon-based material and graphite.
In some embodiments of the present application, the anode active material layer may further include at least one of a viscous material, a conductive agent, and the like. According to some embodiments of the present application, the anode active material layer may further include an adhesive material or a conductive agent; in other embodiments of the present application, the anode active material layer may further include an adhesive material and a conductive agent.
The adhesive material can further improve the bonding strength between the negative electrode active material layer and the negative electrode current collector, thereby further improving the stability of the negative electrode plate. The conductive agent may further improve the conductive performance of the anode active material layer, thereby further reducing the resistance of the battery.
In some embodiments of the present application, the adhesive material may include at least one of Styrene Butadiene Rubber (SBR), polyamide imide (PAI), polyvinyl alcohol (PVA), polyethylenimine (PEI), polyimide (PI), and poly (t-butyl acrylate-triethoxysilane) (TBATEVS), etc. In some embodiments of the application, the adhesive material may be composed of one of the above materials; in other embodiments of the present application, the adhesive material may be composed of two or more of the above materials.
In some embodiments of the application, the viscous material may include styrene-butadiene rubber, which may provide a strong bond to the graphite and the negative current collector (e.g., copper foil).
The adhesive material has good adhesive property, and can form strong adhesive effect between graphite and the negative electrode current collector, so that the bonding strength between the negative electrode active material layer and the negative electrode current collector is further improved.
In some embodiments of the application, the weight average molecular weight of the viscous material may be in the range of 4 tens of thousands to 200 tens of thousands, for example, the weight average molecular weight of the viscous material may be 4 tens of thousands, 10 tens of thousands, 30 tens of thousands, 50 tens of thousands, 80 tens of thousands, 100 tens of thousands, 120 tens of thousands, 150 tens of thousands, 170 tens of thousands, 200 tens of thousands, etc.
The weight average molecular weight of the adhesive material is in the range, so that a stronger bonding effect can be formed between the graphite and the negative electrode current collector, and the structural stability of the negative electrode plate is further improved.
In some embodiments of the present application, the conductive agent may include at least one of carbon nanotubes, carbon black, carbon fibers, graphene, and the like. In some embodiments of the present application, the conductive agent may be carbon nanotubes, carbon black, carbon fibers, or graphene. In other embodiments of the present application, the conductive agent may be a mixture of two or more of carbon nanotubes, carbon black, carbon fibers, and graphene.
The conductive agent has good conductive agent, and the conductive agent is added into the anode active material layer, so that the conductive performance of the anode active material layer can be improved.
In some embodiments of the present application, the anode active material layer may include, based on the total mass of the anode active material layer: silicon-based materials with mass content of 0.85-59.82 wt%; 34-98.75 wt% of graphite; conductive agent with mass content of 0.1-5 wt%; the mass content of the binder is 0.1-5 wt%; the adhesive material comprises 0.1-5 wt% of adhesive material.
In some embodiments of the present application, the anode active material layer may include, based on the total mass of the anode active material layer: a silicon-based material having a mass content of 0.85wt%, 1wt%, 5wt%, 10wt%, 15wt%, 20wt%, 40wt%, 50wt%, or 59.82 wt%; 34wt%, 36wt%, 40wt%, 50wt%, 60wt%, 70wt%, 80wt%, 90wt% or 98.75wt% of graphite; a conductive agent in an amount of 0.1wt%, 0.5wt%, 1wt%, 3wt% or 5 wt%; a binder in an amount of 0.1wt%, 0.5wt%, 1.5wt%, 4wt% or 5 wt%; the mass content of the viscous material is 0.1wt%, 0.3wt%, 0.5wt%, 2wt% or 5 wt%.
The anode active material layer has proper content of each component, which is beneficial to improving the capacity of the battery, reducing the resistance of the battery and further improving the cycle stability of the battery.
In some embodiments of the present application, the negative electrode active material is composed of a silicon-based material and graphite, wherein the mass ratio of the silicon-based material to the graphite is 1:99 to 3:2, for example, the mass ratio of the silicon-based material to the graphite may be 1:99, 1:19, 1:9, 3:17, 1:4, 1:2, 1:1, 3:2, or the like. Thus, the mass ratio of the silicon-based material and graphite in the negative electrode active material is in the above range, and the negative active material layer can have higher capacity, good conductivity and better cycle stability.
In some embodiments of the present application, the negative electrode current collector may be a copper foil.
In some embodiments of the present application, the anode active material layer may be formed on one side surface or both side surfaces of the anode current collector by coating an anode slurry on one side surface or both side surfaces of the anode current collector, and drying.
In yet another aspect of the application, the application provides a battery. In some embodiments of the application, the battery may include a positive electrode tab, a negative electrode tab, and an electrolyte, and the negative electrode tab may be the negative electrode tab described previously. Thus, the battery has good cycle stability and long service life.
The battery is a battery that can be continuously used by activating an active material by means of charging after discharging.
In some embodiments of the application, the battery may be a lithium ion battery.
In some embodiments of the application, the battery comprises a positive electrode plate, a negative electrode plate and an electrolyte, wherein active ions are inserted and extracted back and forth between the positive electrode plate and the negative electrode plate in the charging and discharging process of the battery, and the electrolyte plays a role in conducting ions between the positive electrode plate and the negative electrode plate.
In some embodiments of the application, the electrolyte may be a solid electrolyte, a gel electrolyte, or an electrolyte solution.
In general, when the electrolyte is an electrolyte, the battery may further include an isolating film disposed between the positive electrode tab and the negative electrode tab, to isolate the positive electrode tab from the negative electrode tab.
In some embodiments of the present application, the separator film may include, but is not limited to, polyethylene porous film, polypropylene-polyethylene copolymer porous film, and the like.
In some embodiments of the application, the electrolyte may include an organic solvent, which may include, but is not limited to, ethylene Carbonate (EC), ethylmethyl carbonate (EMC), propylene Carbonate (PC), diethyl carbonate (DEC), dimethyl carbonate (DMC), etc., and a lithium salt, which may include, but is not limited to, lithium hexafluorophosphate, etc.
In some embodiments of the present application, the positive electrode tab may include a positive electrode current collector and a positive electrode active material layer on at least one side surface of the positive electrode current collector.
In some embodiments of the present application, the positive electrode current collector may be aluminum foil.
In some embodiments of the present application, the positive electrode active material layer may include a positive electrode active material, a binder for a positive electrode, a conductive agent for a positive electrode, and the like. In some embodiments of the present application, the positive electrode active material may include one or more of lithium iron phosphate, nickel cobalt manganese ternary material, lithium cobaltate, lithium manganate, lithium nickelate, lithium vanadate, and the like. In some embodiments of the present application, the binder for the positive electrode may include one or more of styrene-butadiene rubber, polyamideimide, polyvinyl alcohol, polyethylenimine, polyimide, poly (t-butyl acrylate-triethoxyvinylsilane), and the like. In some embodiments of the present application, the conductive agent for the positive electrode may include one or more of carbon nanotubes, carbon black, carbon fibers, graphene, and the like.
In some embodiments of the application, the battery may be cylindrical, square (square structured battery 5 is shown in fig. 1), or any other shape.
In some embodiments, the battery may include an outer package. The outer package is used for packaging the positive electrode plate, the negative electrode plate and the electrolyte. Specifically, referring to fig. 2, the exterior package of the battery 5 may include a housing 51 and a cover 53. The housing 51 may include a bottom plate and a side plate connected to the bottom plate, where the bottom plate and the side plate enclose a receiving chamber. The housing 51 has an opening communicating with the accommodation chamber, and the cover plate 53 can be provided to cover the opening to close the accommodation chamber.
As an example, the positive electrode tab, the negative electrode tab, and the separator may be formed into the electrode assembly 52 through a winding process or a lamination process. The electrode assembly 52 is enclosed in the receiving chamber, and an electrolyte fills the inner space of the electrode assembly 52. The number of electrode assemblies 52 included in the battery 5 may be one or more, and those skilled in the art may choose according to specific practical requirements.
In some embodiments, the exterior package of the battery may be a hard shell, such as a hard plastic shell, an aluminum shell, a steel shell.
In other embodiments, the outer package of the battery may also be a pouch, such as a pouch-type pouch. The soft bag can be made of plastic, such as one or more of polypropylene (PP), polybutylene terephthalate (PBT) and polybutylene succinate (PBS).
As an example, the batteries may be assembled into a battery module, and the number of batteries contained in the battery module may be one or more, and a specific number may be selected by one skilled in the art according to the application and capacity of the battery module. Fig. 3 is a battery module 4 as an example. Referring to fig. 3, in the battery module 4, a plurality of batteries 5 may be sequentially arranged in the longitudinal direction of the battery module 4. Of course, the arrangement may be performed in any other way. The plurality of batteries 5 may be further fixed by fasteners. The battery module 4 may further include a case having an accommodating space in which the plurality of batteries 5 are accommodated.
As an example, the above battery modules may be assembled into a battery pack, and the number of battery modules included in the battery pack may be one or more, and a specific number may be selected by those skilled in the art according to the application and capacity of the battery pack. Fig. 4 and 5 are battery packs 1 as an example. Referring to fig. 4 and 5, a battery case and a plurality of battery modules 4 disposed in the battery case may be included in the battery pack 1. The battery box includes an upper box body 2 and a lower box body 3, and the upper box body 2 can be covered on the lower box body 3 and forms a closed space for accommodating the battery module 4. The plurality of battery modules 4 may be arranged in the battery box in any manner.
In yet another aspect of the present application, an electrical device is provided. In some embodiments of the application, the power device comprises a battery as described above. Thus, the power utilization device has all the features and advantages of the battery described above, and will not be described in detail herein.
In some embodiments of the application, the powered device may include at least one of a battery, a battery module, and a battery pack. The battery, battery module or battery pack may be used as a power source for the powered device or as an energy storage unit for the powered device. The power utilization device may be a mobile device (e.g., a cell phone, a notebook computer), an electric vehicle (e.g., a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, an electric bicycle, an electric scooter, an electric golf cart, an electric truck), an electric train, a ship, a satellite, and an energy storage system, but is not limited thereto.
The power utilization device can select a battery, a battery module or a battery pack according to the use requirement thereof.
The electric device as one example may be a vehicle, as shown in fig. 6. The power utilization device comprises a pure electric vehicle, a hybrid electric vehicle or a plug-in hybrid electric vehicle. To meet the high power and high energy density requirements of the power device for the battery, a battery pack or battery module may be employed.
As another example, the power consumption device may include a cellular phone, a tablet computer, a notebook computer. The power utilization device is required to be light and thin, and a battery can be used as a power source.
The application is illustrated below by means of specific examples, which are given for illustrative purposes only and do not limit the scope of the application in any way, as will be understood by those skilled in the art. In addition, in the examples below, materials and equipment used are commercially available unless otherwise specified. If in the following examples specific treatment conditions and treatment methods are not explicitly described, the treatment may be performed using conditions and methods well known in the art.
Example 1
[ preparation of the second monomer ]
Sodium tetraborate (Na 2 B 4 O 7 10 g) and sodium bicarbonate (NaHCO) 3 4 g) was dissolved in 100mL deionized water and the oxygen was removed from the solution by bubbling argon through for 20 min. To a solution containing 4-amino-1, 2-catechol hydrochloride (10 g,29.1 mmol) and 25mL of tetrahydrofuran, 4.7mL of methacrylic anhydride (4.5 g,29.1 mmol) was slowly added dropwise, during which the pH of the solution was adjusted by continuously adding 1M NaOH lye to maintain it at 8 or more. The reaction was stirred at room temperature overnight, and Ar (argon) was introduced to protect the reaction system. The aqueous solution was washed twice with 50mL of ethyl acetate, at which time the pH of the aqueous solution was lowered to below 2, and extracted three times with 50mL of ethyl acetate. The resulting ethyl acetate solutions were combined and then dried over anhydrous magnesium sulfate (MgSO) 4 Drying, concentrating to about 30mL by using a rotary evaporator, adding 250mL of normal hexane into the mixture after intense stirring to obtain a suspension, standing the suspension at 40 ℃ overnight, and filtering to obtain gray powder. The powder was recrystallized in n-hexane solvent and dried to give 4.0g of the grey product 4-amino-catechol methacrylate, the second monomer.
[ preparation of the second Polymer ]
To the tube was added, in order, purified 2-hydroxyethyl acrylate (5.22 g,43.1 mmol), 4-amino-catechol methacrylate (0.66 g,2.87 mmol), azobisisobutyronitrile (AIBN) (76 mg,0.46 mmol), and 20mL of N, N-Dimethylformamide (DMF) solvent to obtain a solution. The solution was repeated three times by vacuum rotary evaporation, then sealed under vacuum, the solution was heated to 60 ℃ and stirred overnight. After the reaction was completed, 50mL of methanol was added to the reaction mixture for dilution, and precipitated in 400mL of diethyl ether and filtered. Then washing and precipitating twice in dichloroethane/diethyl ether mixed solvent, and then carrying out vacuum drying to obtain the product which is 3.5g of white viscous solid, namely the copolymer of the second polymer, 2-hydroxyethyl acrylate and 4-amino-catechol methacrylate.
[ preparation of binder ]
The first polymer is prepared by mixing PAA and the second polymer according to a mass ratio of 4:1 by using commercially available polyacrylic acid (PAA), and then heating, dehydrating and polycondensing to obtain the adhesive.
The method for testing the weight average molecular weight of the binder comprises the following steps: the weight average molecular weight of the binder was measured using a gel permeation chromatograph, and the binder was dissolved using tetrahydrofuran or N, N-dimethylformamide.
The weight average molecular weight of the binder in example 1 was 100 ten thousand.
[ preparation of Positive electrode sheet ]
Positive electrode active material nickel cobalt lithium manganate (NCM 523, liNi 0.5 Co 0.2 Mn 0.3 O 2 ) The adhesive polyvinylidene fluoride PVDF and the conductive agent Super P are prepared according to the mass ratio of 98:1:1, adding N-methyl pyrrolidone (NMP) as a dispersing agent, and stirring to be uniform in a vacuum state to obtain slurry. The resulting slurry was subjected to a treatment of 13.7mg/cm 2 The positive electrode sheet of example 1 was obtained by knife coating on an aluminum foil having a thickness of 13 μm, then oven-drying at 140 ℃, cold-pressing, and slitting.
[ preparation of negative electrode sheet ]
The pre-lithiated silica, the artificial graphite, the conductive agent acetylene black, the binder prepared in the example 1 and SBR are dispersed in dispersant deionized water according to the mass ratio of 14.55:82.45:1:1, and the mixture is stirred and uniformly mixed to obtain the negative electrode slurry. The cathode slurry was mixed at a concentration of 9.7mg/cm 2 Uniformly coating the surface density of the copper foil on a negative electrode current collector with the thickness of 7 mu m, and drying, cold pressing and separatingAnd cutting to obtain the negative electrode plate. Wherein Dv50 of the pre-lithiated silica is 3-20 μm, the components comprise lithium metasilicate, in the particles of the pre-lithiated silica, pure silicon crystal grains are mixed with silicon dioxide and lithium metasilicate, a carbon layer is wrapped on the outer side of the particles, and the diameter of the pure silicon crystal grains is 1-20 nm (the diameter of the pure silicon crystal grains is obtained by XRD test); the Dv50 of the artificial graphite is 5-20 mu m, and the specific surface area is 0.5m 2 /g~4m 2 /g。
[ electrolyte ]
In an argon atmosphere glove box (H 2 O<0.1ppm，O 2 <0.1 ppm), the organic solvents Ethylene Carbonate (EC) and ethylmethyl carbonate (EMC) were mixed uniformly in a volume ratio of 3:7, and 12.5wt% (based on the total mass of ethylene carbonate and ethylmethyl carbonate solvent) of LiPF was added to the mixed solvent 6 Stirring uniformly to make LiPF 6 Dissolving in the organic solvent to obtain electrolyte.
[ isolation Membrane ]
The separator used was a commercially available PP-PE copolymer microporous film (from Highway electronic technologies Co., ltd., model No. 20) having a thickness of 7 μm and an average pore diameter of 80 nm.
[ preparation of lithium ion Battery ]
And sequentially stacking the positive electrode plate, the isolating film and the negative electrode plate, enabling the isolating film to be positioned between the positive electrode plate and the negative electrode plate, playing a role in isolating the positive electrode plate and the negative electrode plate, and winding to obtain the bare cell. And placing the bare cell in an outer package, injecting the electrolyte and packaging to obtain the lithium ion battery.
Example 2
Unlike example 1, the weight average molecular weight of the binder was 170 ten thousand. The remaining parameters and steps were the same as in example 1.
Example 3
Unlike example 1, the weight average molecular weight of the binder was 200 ten thousand. The remaining parameters and steps were the same as in example 1.
Example 4
Unlike example 1, the weight average molecular weight of the binder was 300 ten thousand. The remaining parameters and steps were the same as in example 1.
Example 5
Different from example 2, when preparing the negative electrode plate, pre-lithiated silica, artificial graphite, a conductive agent acetylene black, a binder and SBR are dispersed in dispersant deionized water according to the mass ratio of 4.85:92.15:1:1:1, and the negative electrode slurry is obtained after uniform mixing. The remaining parameters and steps were the same as in example 2.
Example 6
Unlike example 5, when preparing the negative electrode sheet, silica, artificial graphite, acetylene black as a conductive agent, a binder and SBR are dispersed in deionized water as a dispersing agent according to a mass ratio of 4.85:92.15:1:1:1, and the negative electrode slurry is obtained after uniform mixing. Wherein Dv50 of the silicon oxide is 1-12 μm, and specific surface area is 0.5m 2 /g~8m 2 And/g, mixing pure silicon grains with silicon dioxide in the silicon oxide particles, and wrapping carbon outside, wherein the diameter of the pure silicon grains is 1-20 nm. The remaining parameters and steps were the same as in example 5.
Example 7
Unlike example 5, when preparing the negative electrode piece, silicon carbon, artificial graphite, conductive agent acetylene black, binder and SBR are dispersed in dispersant deionized water according to the mass ratio of 4.85:92.15:1:1:1, and the negative electrode slurry is obtained after uniform mixing. Wherein the Dv50 of the silicon carbon is 3-15 mu m, and the specific surface area is 1m 2 /g~12m 2 And/g. The remaining parameters and steps were the same as in example 5.
Example 8
Unlike example 1, the weight average molecular weight of the prepared binder was 20 ten thousand. The remaining parameters and steps were the same as in example 1.
Example 9
Unlike example 2, when preparing the negative electrode sheet, silica, artificial graphite, conductive agent acetylene black, binder and SBR are dispersed in dispersant deionized water according to the mass ratio of 14.55:82.45:1:1:1, and the negative electrode slurry is obtained after uniform mixing. The remaining parameters and steps were the same as in example 2.
Example 10
Unlike example 2, the first monomer used to prepare the binder material is tris (2-hydroxyethyl) isocyanuric acid triacrylate. The remaining parameters and steps were the same as in example 2.
Example 11
Unlike example 2, the first monomer used to prepare the binder material is a compound of structural formula (2-6). The remaining parameters and steps were the same as in example 2.
Example 12
Unlike example 2, the second monomer was 1-amino catechol methacrylate (an ester of amino catechol and methacrylic anhydride dehydrated). The remaining parameters and steps were the same as in example 2.
Example 13
Unlike example 2, the first polymer used to prepare the binder material has the structural formula (1-6). The remaining parameters and steps were the same as in example 2.
Comparative example 1
Unlike example 9, the molecular weight of the binder was 10 ten thousand. The remaining parameters and steps were the same as in example 9.
Comparative example 2
Unlike example 9, the molecular weight of the binder was 350 ten thousand. The remaining parameters and steps were the same as in example 9.
Comparative example 3
Unlike example 1, when preparing the negative electrode sheet, the binder prepared in example 1 was not added to the negative electrode slurry of example 1, but the binder was replaced with SBR, that is, the pre-lithiated silica, the artificial graphite, the conductive agent acetylene black, and SBR were dispersed in the dispersant deionized water according to a mass ratio of 14.55:82.45:1:2, and stirred, and mixed uniformly, to obtain the negative electrode slurry. The remaining parameters and steps were the same as in example 1.
The lithium ion battery samples in each of the examples and comparative examples were subjected to cycle performance test, and the results of the cycle performance test are recorded in table 1.
The method for testing the cycle performance comprises the following steps: the lithium ion batteries prepared in each example and comparative example were charged at a rate of 4C and discharged at a rate of 1C at 25C, and a continuous cycle test was performed in a 3% -97% soc (State of Charge) interval until the capacity of the lithium ion battery was less than 80% of the initial capacity, and the number of cycles was recorded and recorded as cycle life.
The specific surface area test method of the material comprises the following steps: materials such as silica, artificial graphite, silicon carbon, etc. in each of the examples and comparative examples can be tested using methods known in the art. For example, reference may be made to GB/T19587-2017, which is carried out using a nitrogen adsorption specific surface area analytical test method.
The test method of the particle size Dv50 of the material comprises the following steps: the particle size Dv50 of the material was tested by using a GB/T19077.1-2009 particle size distribution laser diffraction method. Under the irradiation of laser beams, the angle of scattered light of the particles is inversely related to the diameter of the particles, the scattered light intensity decays logarithmically with the increase of the angle, the energy distribution of the scattered light is directly related to the distribution of the diameter of the particles, and the particle size distribution characteristics of the particles can be obtained by receiving and measuring the energy distribution of scattered light.
Table 1 results of cycle performance test of each of examples and comparative examples
The mass contents of the prelithiated silica, silica and artificial graphite in table 1 were obtained based on the total mass of the negative electrode active material.
As can be seen from table 1, the binder provided by the application is added into different anode active material systems, and the weight average molecular weight of the binder is 20 ten thousand to 300 ten thousand, so that the cycle performance of the battery can be improved, and the service life of the battery can be prolonged. The binder is added into a composite negative electrode system of pre-lithiated silica and graphite, a composite negative electrode system of silica and graphite or a composite negative electrode system of silica carbon and graphite, so that the cycle stability of the battery can be remarkably improved. In the case of example 1 and comparative example 3, the binder according to the present application was added to the anode active material layer of example 1, and the expansion during charge and discharge of the anode material was effectively suppressed, and the cycle number was significantly increased and the cycle stability was significantly improved, as compared with comparative example 3. It should be noted that, for the composite anode of the above different systems, when the mass ratio of the silicon-based material and the graphite in the anode active material is changed, for example, when the mass ratio of the silicon-based material and the graphite in the anode active material is smaller than 1:19 or larger than 3:17, the cycle performance of the battery can be improved by adding the binder with the weight average molecular weight of 20 ten thousand to 300 ten thousand.
In addition, the binder having a weight average molecular weight of 20 to 300 tens of thousands has an effect of improving the cycle performance of the battery in this range. The binder in comparative example 1 has too small weight average molecular weight, the cycle performance test adopts a small cell, the small cell is a small lamination, the risk of falling off of the negative electrode active material layer is small, the outside is not clamped by a clamp, and the small cell can expand; if mass production is carried out, a large cell is produced and needs to be rolled up, two hard clamps are clamped outside the large cell, the stress is large, and the negative electrode active material layer is easy to fall off. The binder in comparative example 2 has too large weight average molecular weight, the binder has large viscosity, agglomeration can occur during slurry stirring, and in the case of experimental test, a small cell is manufactured, the cathode slurry is placed in a small pot for continuous stirring, and the risk of slurry agglomeration is reduced, so that the test of the small cell is completed; when the mass production is carried out, a large-scale stirring tank is adopted for stirring, after the slurry stirring is completed, the slurry is coated at the end after coming out of the stirring tank, and can be placed on a mass production line for a period of time, for example, the slurry can be placed for about 24 hours, the slurry is likely to be agglomerated in a pipeline, the pipeline is very long, the slurry is difficult to flow after agglomeration, the subsequent operation cannot be carried out, and the requirement and index of mass production are difficult to be met due to the excessive weight average molecular weight of the binder.
Rebound rate of full charge piece:
the negative electrode plate samples of the embodiment 1 and the comparative example 3 are subjected to rebound rate test, the thickness of the negative electrode plate is obtained by adopting vernier caliper test, the thickness D of the negative electrode plate after cold pressing is taken as a reference, the thickness D of the negative electrode plate after full filling is D, the rebound rate of the full filling is = [ (D-D)/D ]. Times.100%, wherein the rebound rate of the full filling of the negative electrode plate of the comparative example 3 is up to 42%, the improvement of the energy density of the graphite and silicon-based composite material is greatly limited, the cycle stability of a battery is also adversely affected, and after the adhesive provided by the application is added in the embodiment 1, the rebound rate of the full filling plate can be reduced to 30%, the rebound rate of the full filling plate can be obviously reduced, and the cycle performance of the battery is improved.
In the description of the present specification, reference to the terms "one embodiment," "another embodiment," "some embodiments," "other embodiments," and the like, means that a particular feature, structure, material, or characteristic described in connection with the embodiment is included in at least one embodiment of the application. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction. In addition, it should be noted that, in this specification, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated.
While embodiments of the present application have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the application, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the application.
Claims (12)
1. A binder comprising a copolymer of a first polymer having the structural formula (1) and a second polymer having the structural formula (2), the first monomer comprising at least one of a urethane, a compound having the structural formula (2), tris (2-hydroxyethyl) isocyanurate, and (2-hydroxyethyl) methacrylate, and the second monomer comprising at least one of an ester having the structural formula (3) dehydrated with an olefmic anhydride, an ester having the structural formula (3) dehydrated with 4-amino-1, 2-catechol hydrochloride, an ester having the structural formula (1) dehydrated with an olefmic anhydride, an ester having the structural formula (3, 4-dihydroxyphenylalanine), and an ester having the structural formula (4) dehydrated with an olefmic anhydride, the olefmic anhydride comprising at least one of methacrylic anhydride, butenic anhydride, and 4-pentenoic anhydride;
Formula (1),>(2),>(3),
wherein X comprises at least one of hydroxyl and mercapto, the number of carbon atoms in X is not more than 3, Y comprises at least one of hydroxyl and mercapto, the number of carbon atoms in Y is not more than 3, Z comprises at least one of amino and mercapto, the number of carbon atoms in Z is not more than 3, and the weight average molecular weight of the binder is 20-300 ten thousand.
2. The adhesive of claim 1, wherein at least one of the following conditions is satisfied:
the first polymer comprises at least one of the following polymers of the formula:
formula (1-1), a->(1-2),
formula (1-3), a->(1-4),
formula (1-5), a->(1-6),
formulas (1-7);
the first monomer comprises at least one of the following compounds:
formula (2-1), a->(2-2),
(2-3),
(2-4),
formula (2-5), a->(2-6),
formulas (2-7);
the second monomer comprises at least one of the following compounds of formula and esters obtained by dehydration of an alkene anhydride:
formula (3-1), a->(3-2),
formula (3-3), a->(3-4),
formula (3-5), a->Formula (3-6).
3. The adhesive according to claim 1 or 2, wherein at least one of the following conditions is satisfied:
x is hydroxy;
the first monomer comprises 2-hydroxyethyl acrylate;
the second monomer includes at least one of 4-amino-catechol methacrylate, 4-amino-catechol butenoate, and 4-amino-catechol pentenoate.
4. The binder of claim 1 wherein the weight average molecular weight of the binder is from 100 to 200 tens of thousands.
5. The adhesive according to any one of claims 1, 2 and 4, wherein the adhesive satisfies one of the following conditions:
x is hydroxyl, the first monomer is 2-hydroxyethyl acrylate, and the second monomer is 4-amino-catechol methacrylate;
x is hydroxyl, the first monomer is tri (2-hydroxyethyl) isocyanuric acid triacrylate, and the second monomer is 4-amino-catechol methacrylate;
x is hydroxyl, the first monomer is a compound with a structural formula (2-6), and the second monomer is 4-amino-catechol methacrylate;
x is hydroxyl, the first monomer is 2-hydroxyethyl acrylate, and the second monomer is 1-amino catechol methacrylate;
The structural formula of the first polymer is shown as the formula (1-6), the first monomer is 2-hydroxyethyl acrylate, and the second monomer is 4-amino-catechol methacrylate.
6. A negative electrode tab comprising a negative electrode current collector and a negative electrode active material layer on at least one side surface of the negative electrode current collector, the negative electrode active material layer comprising:
a negative electrode active material including a silicon-based material and graphite; and
the adhesive of any one of claims 1-5.
7. The negative electrode tab of claim 6, wherein the negative electrode active material layer further comprises at least one of an adhesive material and a conductive agent.
8. The negative electrode tab of claim 7, wherein at least one of the following conditions is satisfied:
the silicon-based material includes at least one of pre-lithiated silicon oxide, and silicon carbon;
the graphite includes at least one of natural graphite and artificial graphite;
the adhesive material includes at least one of styrene-butadiene rubber, polyamide imide, polyvinyl alcohol, polyethylene imine, polyimide, and poly (t-butyl acrylate-triethoxysilane);
The weight average molecular weight of the viscous material is 4 ten thousand to 200 ten thousand;
the conductive agent includes at least one of carbon nanotubes, carbon black, carbon fibers, and graphene;
the negative electrode active material further includes at least one of hard carbon, soft carbon, ketjen black, mesophase carbon microspheres, graphene, and carbon fibers.
9. The anode electrode tab according to claim 7, wherein the anode active material layer includes, based on the total mass of the anode active material layer:
silicon-based materials with mass content of 0.85-59.82 wt%;
34-98.75 wt% of graphite;
conductive agent with mass content of 0.1-5 wt%;
the mass content of the binder is 0.1-5 wt%;
the adhesive material comprises 0.1-5 wt% of adhesive material.
10. The negative electrode sheet according to any one of claims 6, 7 and 9, characterized in that the negative electrode active material is composed of a silicon-based material and graphite in a mass ratio of 1:99 to 3:2.
11. A battery comprising a positive electrode sheet, a negative electrode sheet and an electrolyte, wherein the negative electrode sheet is the negative electrode sheet of any one of claims 6 to 10.
12. An electrical device comprising the battery of claim 11.
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