CN115706296A - Secondary battery, battery module, battery pack, and electric device - Google Patents
Secondary battery, battery module, battery pack, and electric device Download PDFInfo
- Publication number
- CN115706296A CN115706296A CN202110902762.0A CN202110902762A CN115706296A CN 115706296 A CN115706296 A CN 115706296A CN 202110902762 A CN202110902762 A CN 202110902762A CN 115706296 A CN115706296 A CN 115706296A
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- China
- Prior art keywords
- acrylic copolymer
- optionally
- secondary battery
- negative electrode
- meth
- Prior art date
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- Pending
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- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- UMVBXBACMIOFDO-UHFFFAOYSA-N [N].[Si] Chemical class [N].[Si] UMVBXBACMIOFDO-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical class [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000005599 alkyl carboxylate group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- KTPIWUHKYIJBCR-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohex-4-ene-1,2-dicarboxylate Chemical compound C1C=CCC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 KTPIWUHKYIJBCR-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 description 1
- GNEPOXWQWFSSOU-UHFFFAOYSA-N dichloro-methyl-phenylsilane Chemical compound C[Si](Cl)(Cl)C1=CC=CC=C1 GNEPOXWQWFSSOU-UHFFFAOYSA-N 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002003 electrode paste Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- HGFAGBHAGYXJKZ-UHFFFAOYSA-N fluoromethanesulfonamide Chemical compound NS(=O)(=O)CF HGFAGBHAGYXJKZ-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
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- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 description 1
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- DMEJJWCBIYKVSB-UHFFFAOYSA-N lithium vanadium Chemical compound [Li].[V] DMEJJWCBIYKVSB-UHFFFAOYSA-N 0.000 description 1
- SBWRUMICILYTAT-UHFFFAOYSA-K lithium;cobalt(2+);phosphate Chemical compound [Li+].[Co+2].[O-]P([O-])([O-])=O SBWRUMICILYTAT-UHFFFAOYSA-K 0.000 description 1
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 150000004812 organic fluorine compounds Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000005054 phenyltrichlorosilane Substances 0.000 description 1
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
- 229920000196 poly(lauryl methacrylate) Polymers 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 1
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
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- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/531—Electrode connections inside a battery casing
- H01M50/534—Electrode connections inside a battery casing characterised by the material of the leads or tabs
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/572—Means for preventing undesired use or discharge
- H01M50/584—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries
- H01M50/586—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries inside the batteries, e.g. incorrect connections of electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/572—Means for preventing undesired use or discharge
- H01M50/584—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries
- H01M50/59—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries characterised by the protection means
- H01M50/593—Spacers; Insulating plates
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present application relates to a secondary battery, a battery module, a battery pack, and an electric device. The secondary battery includes a negative electrode plate, the negative electrode plate includes a negative electrode current collector, the negative electrode current collector includes: a negative electrode main body provided with a negative electrode active material layer on at least one surface thereof; and the negative electrode tab comprises a coating area, the coating area is provided with a glue layer, the glue layer is adjacent to the negative electrode active material layer, and the glue layer comprises a carboxylic ester polymer and a styrene-acrylic copolymer and/or a modified styrene-acrylic copolymer.
Description
Technical Field
The present application relates to the field of batteries, and in particular, to a secondary battery, a battery module, a battery pack, and an electric device.
Background
The safety of the secondary battery is one of the most concerned problems of the power battery. Many factors affect the safety of the secondary battery, such as the structural stability of the positive electrode material, the film-forming property of the SEI film on the surface of the negative electrode, the high-voltage resistance of the electrolyte, the flame retardancy, and the heat resistance of the separator. The safety risk of the battery is mainly caused by thermal runaway, which is mainly caused by that the heat generation rate is far higher than the heat dissipation rate, and the heat is accumulated in a large amount and cannot be dissipated. Not only the application of the material determines the safety performance of the battery core, but also the safety risk of the battery core caused by the imperfect preparation process in the preparation process of the battery, thereby causing internal short circuit and causing the ignition of the battery core.
In the winding process of the battery cell, the positive pole tab and the negative pole tab can be folded inwards due to the manufacturing process, the negative pole tab is overlapped to the positive pole side or the positive pole tab is overlapped to the negative pole side, the short circuit of the battery cell is caused in the working process, and the serious consequence is caused.
Disclosure of Invention
The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a secondary battery that can achieve both high cell safety and good manufacturing process.
In order to achieve the above object, the present invention provides a secondary battery comprising a negative electrode tab including a negative electrode current collector,
the negative electrode current collector includes:
a negative electrode main body provided with a negative electrode active material layer on a surface thereof; and
the negative pole tab comprises a coating area, a glue layer is arranged in the coating area,
the adhesive layer is adjacent to the negative electrode active material layer and comprises a carboxylic ester polymer and a styrene-acrylic copolymer and/or a modified styrene-acrylic copolymer.
Through will include the carboxylate polymer, and the glue film of phenylpropyl copolymer and/or modified phenylpropyl copolymer sets up in the coating area of negative pole utmost point ear, under the prerequisite that does not influence laser cutting, guarantee that the compatibility of glue film and negative pole active material layer is good, can not make the copper foil spill, further promote insulating nature, can ensure that the electric core of the secondary battery who makes does not also take place the short circuit when utmost point ear overlap joint, reduce electric core inefficacy proportion, the phenomenon that diaphragm edge drum limit can not appear in the course of working in the glue film simultaneously, the heat shrinkage factor of glue film is lower, the glue film is also good with the cohesiveness of mass flow body.
In some embodiments, the styrene acrylic copolymer and/or the modified styrene acrylic copolymer is present in the glue layer in an amount of 80 to 90wt%, optionally 82 to 86wt%, based on mass fraction. Set for above-mentioned scope through the content with the phenylpropyl copolymer in the glue film and/or modified phenylpropyl copolymer, can realize under the prerequisite that does not influence laser cutting, the glue film is good with the compatibility of negative pole active material layer, can not make the copper foil spill, further promote insulating nature, can ensure that the electric core of the secondary battery who makes does not also take place the short circuit when utmost point ear overlap joint, reduce electric core inefficacy proportion, the phenomenon that diaphragm edge was bloated limit can not appear in the course of working in the glue film simultaneously, further reduce the heat shrinkage factor of glue film, the cohesiveness of glue film and mass flow body is also good.
In some embodiments, the modified styrene-acrylic copolymer is one or more selected from the group consisting of an epoxy-modified styrene-acrylic copolymer, an organosilicon-modified styrene-acrylic copolymer, an organofluorine-modified styrene-acrylic copolymer, and a polyolefin-modified styrene-acrylic copolymer, optionally one or more selected from the group consisting of an epoxy-modified styrene-acrylic copolymer and an organofluorine-modified styrene-acrylic copolymer. By using the modified styrene-acrylic copolymer in the adhesive layer, the thermal shrinkage rate of the adhesive layer in the processing process can be further reduced, and the adhesive layer can be better prevented from falling off, so that the insulativity is further improved.
In some embodiments, the degree of crosslinking of the styrene acrylic copolymer and/or the modified styrene acrylic copolymer is 1% to 3%, optionally 1.5% to 2.5%.
In some embodiments, the number average molecular weight of the styrene acrylic copolymer and/or the modified styrene acrylic copolymer is from 1 to 10, optionally from 3 to 6, ten thousand. The number average molecular weight is measured by GPC (gel permeation chromatography).
The styrene-acrylic copolymer and/or the modified styrene-acrylic copolymer with specific crosslinking degree and number average molecular weight are used in the adhesive layer, so that the viscosity of the adhesive solution obtained from the polycarboxylate polymer and the styrene-acrylic copolymer and/or the modified styrene-acrylic copolymer is in a proper range, the adhesive solution is easy to coat and does not generate bubbles in the processing process, laser cutting is easy to perform, the continuous proportion of tab cutting in the processing process is reduced, and the heat shrinkage rate of the adhesive layer in the processing process is further reduced.
In some embodiments, the carboxylate polymer is one or more selected from the group consisting of poly (meth) acrylates, polymaleates, and polyvinyl acetates. By using the carboxylic ester polymer in the adhesive layer, a strong hydrogen bond acting force can be formed between the adhesive layer and the base material, so that the adhesive force is improved; and the polymer with low Tg can be formed, so that the processing stability is facilitated, the current collector cannot be shrunk in the gluing process, the heat shrinkage rate of the adhesive layer in the processing process is reduced, and the processing manufacturability of the adhesive layer can be improved.
In some embodiments, the carboxylate polymer is one or more selected from poly (meth) acrylates, optionally one or more selected from polyalkyl (meth) acrylates, polyhydroxyalkyl (meth) acrylates or polyalkenyl (meth) acrylates, optionally one or more selected from polymethyl (meth) acrylate, polyethyl (meth) acrylate, poly-n-butyl (meth) acrylate, polyisobutyl (meth) acrylate, polyhydroxyethyl (meth) acrylate, polylauryl (meth) acrylate and polyallyl (meth) acrylate. The number average molecular weight of the poly (meth) acrylate can be adjusted and set according to the performance and physical parameters of the adhesive layer, such as low Tg, high adhesive force, and the like. Through using above-mentioned poly (methyl) acrylate in the glue film, can further promote the adhesion, further reduce the heat shrinkage factor of glue film in the course of working to further improve the processing technology nature of glue film, and further promote the laser beam machining nature of negative pole utmost point ear, thereby further reduce utmost point ear in the course of working and cut continuous proportion.
In some embodiments, the carboxylate polymer has a degree of crosslinking of 1% to 3%, optionally 1.5% to 2.5%.
In some embodiments, the carboxylate polymer has a number average molecular weight of 10 to 20, optionally 14 to 18, ten thousand. The number average molecular weight is measured by GPC (gel permeation chromatography).
By using the polycarboxylate polymer with specific crosslinking degree and number average molecular weight in the adhesive layer, the viscosity of the adhesive solution obtained from the polycarboxylate polymer and the styrene-acrylic copolymer and/or the modified styrene-acrylic copolymer can be in a proper range, so that the adhesive solution is easy to coat and does not generate bubbles in the processing process, laser cutting is easy to perform, and the continuous proportion of tab cutting in the processing process is reduced.
In some embodiments, the adhesive layer further includes a colorant, optionally a colorant with a gray value of less than or equal to 1, optionally a colorant with a gray value of less than or equal to 0.5, and the colorant is added to the adhesive layer, so that the energy of laser absorbed by the adhesive layer can be increased, laser cutting is facilitated, and the continuous tab cutting proportion in the processing process is further reduced.
In some embodiments, the colorant in the subbing layer is a black pigment, optionally at least one of a black masterbatch, carbon black, graphite, and lithium iron phosphate. Through contain above-mentioned colorant in the glue film, can further improve the energy of the laser that the glue film absorbed to can promote laser cutting's goodness, the utmost point ear is cut continuous proportion in the further reduction course of working.
In some embodiments, the colorant is present in the subbing layer in an amount ≦ 2wt% based on the mass fraction, alternatively 1 to 2wt%. The content of the colorant in the adhesive layer is in the range, so that the optimal rate of laser cutting can be further improved, and the continuous proportion of tab cutting in the laser processing process is further reduced.
In some embodiments, the adhesive layer has a thermal shrinkage at 140 ℃ of 1% to 2%, optionally 1.4% to 1.6%. By setting the thermal shrinkage rate of the adhesive layer within the above range, the adhesive layer can be prevented from peeling off from the base material, so that the electrical core of the manufactured secondary battery is ensured not to have short circuit even when the tabs are lapped, the failure proportion of the electrical core is reduced, and the adhesive property of the adhesive layer and the base material is good.
In some embodiments, the area ratio occupied by the coating region in the anode tab is 1/3 to 2/3. The occupied area ratio of the coating area is within the range, the insulativity which can be achieved by coating can be ensured, the failure proportion of the battery cell is further reduced, the requirement for welding the tab is met, the tab is not interfered in welding, and the safety performance of the secondary battery is further improved.
In some embodiments, the glue layer further comprises a ceramic filler, optionally one or more selected from alumina, magnesia, calcia and silica. Through including ceramic filler in the glue film, can further improve the hardness of insulating nature and glue film to be favorable to laser cutting, the utmost point ear is cut continuous proportion in further reducing the course of working.
In some embodiments, the ceramic filler is present in the bondline in an amount ≦ 5wt%, optionally 1 to 4wt%, based on the mass fraction. The content of the ceramic filler in the adhesive layer is in a specific range, so that the insulativity and the hardness of the adhesive layer can be further improved, the laser cutting goodness is further improved, and the continuous proportion of tab cutting in the processing process is further reduced.
In some embodiments, the ceramic filler has a particle size of 10 to 100nm, optionally 20 to 60nm. The particle size of the ceramic filler is within the range, so that the processing performance of gluing can be ensured, the missing coating is avoided, the failure proportion of the battery cell is further reduced, and the safety performance of the battery is further improved.
A second aspect of the present application provides a battery module including the secondary battery according to the first aspect of the present application.
A third aspect of the present application provides a battery pack including the battery module according to the second aspect of the present application.
A fourth aspect of the present application provides an electric device including at least one of the secondary battery according to the first aspect of the present application, the battery module according to the second aspect of the present application, or the battery pack according to the third aspect of the present application.
The battery module, the battery pack, and the power consumption device of the present application include the secondary battery provided in the present application, and thus have at least the same advantages as the secondary battery.
Drawings
Fig. 1 is a schematic structural view of an embodiment of a negative electrode sheet of the present application.
Fig. 2 is a schematic view before cutting a negative electrode tab of the present application
Fig. 3 is a schematic diagram after cutting the anode tab of the present application.
Fig. 4 is a schematic view of a secondary battery according to an embodiment of the present application.
Fig. 5 is an exploded view of the secondary battery according to the embodiment of the present application shown in fig. 4.
Fig. 6 is a schematic view of a battery module according to an embodiment of the present application.
Fig. 7 is a schematic diagram of a battery pack according to an embodiment of the present application.
Fig. 8 is an exploded view of the battery pack of one embodiment of the present application shown in fig. 7.
Fig. 9 is a schematic diagram of an apparatus in which a secondary battery according to an embodiment of the present application is used as a power source.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, embodiments of the present application will be described in detail below with reference to the accompanying drawings. However, it should be understood by those of ordinary skill in the art that these examples are only for illustrating the technical solutions of the present application and are not limiting.
For the sake of brevity, some numerical ranges are specifically disclosed herein. However, any lower limit may be combined with any upper limit to form ranges 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. Also, although not explicitly recited, each point or individual value between endpoints of a range is encompassed within the range. Furthermore, each separately disclosed point or individual value may itself, as a lower or upper limit, be combined with any other point or individual value or with other lower or upper limits to form ranges not explicitly recited.
In the description herein, it is to be noted that, unless otherwise specified, "above" and "below" are inclusive, and "one or more" means "several" are two or more.
The above summary of the present application is not intended to describe each disclosed embodiment or every implementation of the present application. The following description more particularly exemplifies illustrative embodiments. At various points throughout this application, guidance is provided through a list of embodiments that can be used in various combinations. In each instance, the list is provided only as a representative group and should not be construed as exhaustive.
Secondary battery
A secondary battery refers to a battery that can be continuously used by activating an active material by means of charging after the battery is discharged. In general, a secondary battery includes a positive electrode tab, a negative electrode tab, a separator, and an electrolyte. In the process of charging and discharging the battery, active ions are embedded and separated back and forth between the positive pole piece and the negative pole piece. The barrier film sets up between positive pole piece and negative pole piece, and it can be to electronic insulation, prevents that inside from taking place the short circuit, makes active ion can see through and remove between positive negative pole simultaneously, plays the effect of keeping apart. The electrolyte plays a role in conducting ions between the positive pole piece and the negative pole piece.
[ negative electrode sheet ]
Fig. 1 is a schematic structural view of an embodiment of a negative electrode tab of the present application. As shown in fig. 1, the negative electrode tab 100 of the present application includes a negative electrode collector 30, and the negative electrode collector 30 includes: a negative electrode main body 301 having a negative electrode active material layer 20 provided on the surface of the negative electrode main body 301; and an anode tab 302, the anode tab 302 including a coated region in which the gel layer 10 is provided, the gel layer 10 being adjacent to the anode active material layer 20. The glue layer 10 and the negative electrode tab 302 are located in a tab region S shown by a dotted line in fig. 1. The subbing layer 10 includes a carboxylate polymer, and a styrene-acrylic copolymer and/or a modified styrene-acrylic copolymer, such as: the subbing layer 10 may include a carboxylic acid ester-based polymer, and a styrene-acrylic copolymer; alternatively, the adhesive layer 10 may also include a carboxylate polymer, and a modified styrene-acrylic copolymer; alternatively, the adhesive layer 10 may also include a carboxylate polymer, as well as a styrene-acrylic copolymer and a modified styrene-acrylic copolymer. The negative electrode active material layer 20 is provided on the surface of the negative electrode body 301 of the negative electrode collector 30, and the negative electrode collector 30 on which the negative electrode active material layer 20 is not provided is a negative electrode tab 302. In the embodiment shown in fig. 1, the anode active material layer 20 is provided on both surfaces of the anode main body portion 301 of the anode current collector 30, but is not limited thereto, and the anode active material layer 20 may be provided on only one surface of the anode main body portion 301 of the anode current collector 30.
Through the regional setting of coating at negative pole utmost point ear 302 contains the carboxylate polymer, and the glue film 10 of styrene-acrylic copolymer and/or modified styrene-acrylic copolymer, under the prerequisite that does not influence laser cutting, can guarantee that the compatibility of glue film 10 and negative pole active material layer 20 is good, can not make the copper foil spill, further promote insulating nature, can ensure that the electric core made by the negative pole piece does not also take place the short circuit when utmost point ear overlap joint, reduce electric core inefficacy proportion, the phenomenon that diaphragm edge drum limit can not appear in the course of working in the glue film simultaneously, and the heat shrinkage factor of glue film is lower, the glue film is also good with the current collector's of negative pole cohesiveness.
In some embodiments, the styrene-acrylic copolymer is a copolymer obtained by copolymerizing styrene and acrylic acid. The modified styrene-acrylic copolymer is a copolymer prepared by taking styrene and acrylic acid as main bodies and adding one or more of epoxy, organic silicon, organic fluorine, polyolefin and other modifiers for copolymerization. The styrene-acrylic copolymer and the modified styrene-acrylic copolymer can be obtained by polymerization using a polymerization method known in the art, for example, emulsion polymerization, solution polymerization, or the like. Among these, as the modifier such as epoxy, silicone, organofluorine, polyolefin, and the like, a commonly used modifier commonly used in the art for modifying styrene-acrylic copolymers can be used, and examples thereof include epoxy modifiers such as bisphenol a type epoxy resins, bisphenol S type epoxy resins, bisphenol F type epoxy resins, resorcinol diglycidyl ether epoxy resins, and tetrahydrophthalic acid diglycidyl ester epoxy resins; silicone modifiers such as dimethyldichlorosilane, methyltrichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, and methylphenyldichlorosilane; organic fluorine modifiers such as polytetrafluoroethylene, polyvinylidene fluoride, and polychlorotrifluoroethylene; styrene-butadiene-polypropylene emulsion, polypropylene and other polyolefin modifiers. In the preparation of the styrene-acrylic copolymer or the modified styrene-acrylic copolymer, a crosslinking agent can be used, so that the processing manufacturability of the adhesive layer and the hardness of the adhesive layer can be improved. The crosslinking agent is not particularly limited, and any crosslinking agent commonly used in the art can be used, and examples thereof include dicumyl peroxide and t-butyl peroxybenzoate. The styrene-acrylic copolymer and the modified styrene-acrylic copolymer may be synthesized by a common polymerization method or may be commercially available.
In some embodiments, the modified styrene-acrylic copolymer in the bondline 10 is one or more selected from the group consisting of an epoxy-modified styrene-acrylic copolymer, an organosilicon-modified styrene-acrylic copolymer, an organofluorine-modified styrene-acrylic copolymer, and a polyolefin-modified styrene-acrylic copolymer, optionally one or more selected from the group consisting of an epoxy-modified styrene-acrylic copolymer and an organofluorine-modified styrene-acrylic copolymer. By using the modified styrene-acrylic copolymer in the adhesive layer, the thermal shrinkage rate of the adhesive layer in the processing process can be further reduced, and the adhesive layer can be better prevented from falling off, so that the insulativity is further improved.
In some embodiments, the styrene acrylic copolymer and/or the modified styrene acrylic copolymer is present in the bondline 10 in an amount ranging from 80 to 90wt%, alternatively from 82 to 86wt%, based on mass fraction. Set for above-mentioned scope through the content with the styrene-acrylic copolymer in the glue film and/or modified styrene-acrylic copolymer, can realize under the prerequisite that does not influence laser cutting, the glue film is good with the compatibility of negative pole active material layer, can not make the copper foil spill, further promote insulating nature, can ensure that the electric core made by this negative pole piece does not also take place the short circuit when utmost point ear overlap joint, reduce electric core inefficacy proportion, the phenomenon that diaphragm edge drum limit can not appear in the course of working in the glue film simultaneously, further reduce the heat shrinkage factor of glue film, the glue film is also good with the cohesiveness of mass flow body.
In some embodiments, the degree of crosslinking of the styrene-acrylic copolymer and/or the modified styrene-acrylic copolymer is 1% to 3%, alternatively 1.5% to 2.5%;
in some embodiments, the number average molecular weight of the styrene acrylic copolymer and/or the modified styrene acrylic copolymer is from 1 to 10, optionally from 3 to 6, ten thousand. The number average molecular weight is measured by GPC (gel permeation chromatography).
By using the styrene-acrylic copolymer and/or the modified styrene-acrylic copolymer with a specific crosslinking degree and a specific number average molecular weight in the adhesive layer 10, the viscosity of the adhesive solution obtained from the polycarboxylate polymer and the styrene-acrylic copolymer and/or the modified styrene-acrylic copolymer can be in a proper range, so that the adhesive solution is easy to coat and does not generate bubbles in the processing process, the laser cutting is easy to perform, the continuous proportion of tab cutting in the processing process is reduced, and the heat shrinkage rate of the adhesive layer in the processing process is further reduced.
In some embodiments, the carboxylate polymer is one or more selected from the group consisting of poly (meth) acrylates, polymaleates, and polyvinyl acetates. By using the carboxylic ester polymer in the adhesive layer, a strong hydrogen bond acting force can be formed between the adhesive layer and the base material, so that the adhesive force is improved; and the polymer with low Tg can be formed, so that the processing stability is facilitated, the current collector cannot be shrunk in the gluing process, the heat shrinkage rate of the adhesive layer in the processing process is reduced, and the processing manufacturability of the adhesive layer can be improved. The carboxylic acid esters include alkyl carboxylates, alkenyl carboxylates, hydroxyalkyl carboxylates, cycloalkyl carboxylates, aryl carboxylates, and the like. Wherein the alkyl, alkenyl and hydroxyalkyl have 1 to 22, optionally 1 to 18, optionally 1 to 12 carbon atoms; the cycloalkyl group has 3 to 12, optionally 3 to 6, carbon atoms; the aryl group has 6 to 22, optionally 6 to 18, optionally 6 to 12 carbon atoms.
In some embodiments, the carboxylate polymer is one or more selected from poly (meth) acrylates, optionally one or more selected from polyalkyl (meth) acrylates, polyhydroxyalkyl (meth) acrylates, or polyalkenyl (meth) acrylates, optionally one or more selected from polymethyl (meth) acrylate, polyethyl (meth) acrylate, poly-n-butyl (meth) acrylate, polyisobutyl (meth) acrylate, polyhydroxyethyl (meth) acrylate, polylauryl (meth) acrylate, and polyallyl (meth) acrylate. Through using above-mentioned poly (methyl) acrylate in the glue film, can further promote the adhesion stress, further reduce the heat shrinkage factor of glue film in the course of working to further improve the processing technology nature of glue film, and further promote the laser beam machining nature of negative pole utmost point ear, thereby further reduce utmost point ear in the course of working and cut incessant proportion.
In some embodiments, the carboxylate polymer has a degree of crosslinking of 1% to 3%, alternatively 1.5% to 2.5%;
in some embodiments, the number average molecular weight of the carboxylate polymer is from 10 to 20 ten thousand, optionally from 14 to 18 ten thousand. The number average molecular weight is measured by GPC (gel permeation chromatography).
The polycarboxylate polymers with specific crosslinking degree and number average molecular weight are used in the adhesive layer, so that the viscosity of a glue solution obtained from the polycarboxylate polymers and the styrene-acrylic copolymer and/or the modified styrene-acrylic copolymer is in a proper range, the glue solution is easy to coat and does not generate bubbles in the processing process, laser cutting is easy to perform, the continuous proportion of tab cutting in the processing process is reduced, and the polycarboxylate polymers with specific crosslinking degree and number average molecular weight play a role of a suspension filler and improve the binding force on a current collector.
The carboxylic ester polymer can be obtained by polymerizing a carboxylic ester compound by a polymerization method known in the art, for example, radical polymerization, bulk polymerization, or the like. In the preparation of the carboxylic acid ester based polymer, a crosslinking agent may be used, whereby the processability of the adhesive layer and the hardness of the adhesive layer can be improved. The crosslinking agent is not particularly limited, and any crosslinking agent commonly used in the art can be used, and examples thereof include glycerol, diphenylmethane diisocyanate, and toluene diisocyanate. The carboxylic acid ester polymer may be a synthetic product obtained by polymerization by a common polymerization method, or may be a commercially available product.
In some embodiments, the glue layer 10 further comprises a colorant, optionally a colorant having a gray scale value of ≦ 1, optionally a colorant having a gray scale value of ≦ 0.5, optionally a black pigment, optionally at least one of black masterbatch, carbon black, graphite, and lithium iron phosphate. Through contain the colorant in the glue film, can improve the energy of the glue film absorbed laser to can promote laser cutting's goodness, the utmost point ear is cut constantly proportion in the further reduction course of working. The above-mentioned gray values can be measured by a method using a gray scanner.
In some embodiments, the colorant is present in the bondline 10 in an amount ≦ 2wt% based on the mass fraction, alternatively 1 to 2wt%. The content of the colorant in the adhesive layer is in the range, so that the optimal rate of laser cutting can be further improved, and the continuous proportion of tab cutting in the laser processing process is further reduced.
In some embodiments, the thermal shrinkage of the adhesive layer 10 at 140 ℃ is 1% to 2%, alternatively 1.4% to 1.6%. By making the thermal shrinkage rate of the adhesive layer within the above range, the adhesive layer can be prevented from peeling off from the base material, so that the electrical core made of the negative pole piece is ensured not to have short circuit even when the tabs are lapped, the failure proportion of the electrical core is reduced, and the adhesive property of the adhesive layer and the base material is good.
In some embodiments, the area ratio of the coating region in the anode tab 302 is 1/3 to 2/3. The occupied area ratio of the coating area is within the range, the insulativity which can be achieved by coating can be ensured, the failure proportion of the battery cell is further reduced, the tab welding requirement is met, the tab welding is not interfered, and the safety performance of the secondary battery is further improved.
In some embodiments, a ceramic filler, optionally one or more selected from alumina, magnesia, calcia, and silica, is also included in the bondline 10. Through contain ceramic packing in the glue film, can further improve the hardness of insulating nature and glue film to be favorable to laser cutting, the utmost point ear is cut continuous proportion in further reducing the course of working.
In some embodiments, the ceramic filler is present in the bondline 10 in an amount ≦ 5wt% and optionally 1 to 4wt% based on mass fraction. The content of the ceramic filler in the adhesive layer is in a specific range, so that the insulativity and the hardness of the adhesive layer can be further improved, the laser cutting goodness is further improved, and the continuous proportion of cutting the electrode lugs in the processing process is further reduced.
In some embodiments, the ceramic filler has a particle size of 10 to 100nm, optionally 20 to 60nm. By enabling the particle size of the ceramic filler to be within the range, the processing performance of gluing can be guaranteed, missing coating is avoided, the failure proportion of the battery cell is further reduced, and therefore the safety performance of the battery is further improved.
In the negative electrode sheet of the present application, the negative electrode active material layer 20 contains a negative electrode active material. The negative active material may use a negative active material commonly used in the art for preparing a negative electrode of a secondary battery, such as graphite, a silicon-based material, and the like. The graphite may include artificial graphite, natural graphite, or a mixture thereof. The silicon-based material can be one or more selected from elemental silicon, silicon-oxygen compounds (such as silicon monoxide), silicon-carbon compounds, silicon-nitrogen compounds and silicon alloys.
As an example, the anode current collector has two surfaces opposing in its own thickness direction, and the anode active material layer is provided on either or both of the two surfaces opposing the anode current collector.
In the negative electrode plate of the present application, the negative electrode current collector 30 may be a metal foil or a composite current collector. For example, as the metal foil, a copper foil can be used. The composite current collector may include a polymer base layer and a metal layer formed on at least one surface of the polymer base material. The composite current collector may be formed by forming a metal material (e.g., copper, a copper alloy, nickel, a nickel alloy, titanium, a titanium alloy, silver, a silver alloy, etc.) on a polymer material base material (e.g., a base material of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In the negative electrode sheet of the present application, the negative electrode active material layer generally contains a negative electrode active material, and an optional binder, an optional conductive agent, and other optional auxiliaries, and is generally formed by coating and drying a negative electrode slurry. The negative electrode slurry is generally formed by dispersing a negative electrode active material, an optional conductive agent, an optional binder, and other optional additives in a solvent and uniformly stirring. The solvent may be N-methylpyrrolidone (NMP) or deionized water.
As an example, the conductive agent may be selected from one or more of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
As an example, the binder may be selected from one or more of Styrene Butadiene Rubber (SBR), polyacrylic acid (PAA), sodium Polyacrylate (PAAs), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium Alginate (SA), polymethacrylic acid (PMAA), and carboxymethyl chitosan (CMCS).
Other optional adjuvants are, for example, thickeners such as sodium carboxymethylcellulose (CMC-Na), etc.
The negative electrode sheet of the present application can be produced by a general production method. Specifically, the carboxylic acid ester-based polymer and the styrene-acrylic copolymer and/or the modified styrene-acrylic copolymer may be dissolved in an aqueous solvent, which is water and a water-miscible organic solvent such as alcohols, ketones, esters, and the like, without being particularly limited. Further dissolving and dispersing the optional ceramic filler and the optional colorant in an aqueous solvent in which the carboxylic ester polymer, the styrene-acrylic copolymer and/or the modified styrene-acrylic copolymer are/is dissolved to obtain a glue solution; meanwhile, a negative electrode slurry is prepared. Then, as shown in fig. 2, the glue solution is applied to the coating region of the negative electrode tab 302 of the negative electrode collector 20, and the negative electrode slurry is applied to the negative electrode main body portion 301 of the negative electrode collector 20 and dried to obtain the negative electrode tab before tab cutting shown in fig. 2. As an example, the glue solution and the negative electrode paste may be coated simultaneously. Then, as shown in fig. 3, the negative electrode sheet shown in fig. 2 is cold-pressed, and the negative electrode tabs 302 are laser-cut, and a plurality of negative electrode tabs 302 are spaced apart from each other, thereby producing the negative electrode sheet shown in fig. 3. The shape of the negative electrode tab 302 is not particularly limited and may be selected as needed.
[ Positive electrode sheet ]
In a secondary battery, a positive electrode sheet generally includes a positive electrode current collector and a positive electrode active material layer including a positive electrode active material disposed on at least one surface of the positive electrode current collector.
In the secondary battery of the present application, the positive electrode active material layer includes a positive electrode active material. The positive active material may include, but is not limited to, lithium cobaltate, lithium nickel manganese aluminate, lithium iron phosphate, lithium vanadium phosphate, lithium cobalt phosphate, lithium manganese phosphate, lithium iron silicate, lithium vanadium silicate, lithium cobalt silicate, lithium manganese silicate, spinel-type lithium manganate, spinel-type lithium nickel manganate, lithium titanate, and the like. One or more of these can be used as the positive electrode active material.
The positive electrode active material layer may further optionally include a conductive agent. However, the kind of the conductive agent is not particularly limited, and those skilled in the art can select the conductive agent according to actual needs. As an example, the conductive agent may be selected from one or more of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
In the secondary battery of the present application, the positive current collector may employ a metal foil or a composite current collector. For example, as the metal foil, aluminum foil may be used. The composite current collector may include a polymer material base layer and a metal layer formed on at least one surface of the polymer material base layer. The composite current collector may be formed by forming a metal material (e.g., aluminum alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a polymer material base material (e.g., a base material of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
The positive electrode sheet of the present application can be prepared according to a method generally used in the art. Specifically, a coating layer may be formed on at least one surface of the current collector by a coating method such as gravure coating, spray coating, or the like, or a hot press compounding, or the like; the positive electrode active material, the conductive agent and the binder are dispersed in a solvent (such as N-methylpyrrolidone (NMP)) to prepare positive electrode slurry, the positive electrode slurry is coated on a current collector, and the positive electrode plate is obtained after the working procedures of drying, cold pressing and the like.
[ electrolyte ]
The electrolyte is not particularly limited in the embodiments of the present application, and may be selected according to requirements. For example, the electrolyte may be solid or liquid.
In some embodiments, the electrolyte is liquid and typically includes an electrolyte salt and a solvent.
As an example, the electrolyte salt may be selected from lithium hexafluorophosphate (LiPF) 6 ) Lithium tetrafluoroborate (LiBF) 4 ) Lithium perchlorate (LiClO) 4 ) Lithium hexafluoroarsenate (LiAsF) 6 ) Lithium bis (fluorosulfonyl) imide (LiFSI) or bis (tris)Lithium fluoromethanesulfonamide (LiTFSI), lithium trifluoromethanesulfonate (LiTFS), lithium difluorooxalato borate (LiDFOB), lithium dioxalate borate (LiBOB), lithium difluorophosphate (LiPO) 2 F 2 ) One or more of lithium difluorooxalate phosphate (LiDFOP) and lithium tetrafluorooxalate phosphate (LiTFOP).
As an example, the solvent may be selected from one or more of fluoroethylene carbonate (FEC), ethylene Carbonate (EC), propylene Carbonate (PC), ethyl Methyl Carbonate (EMC), diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), methyl Propyl Carbonate (MPC), ethyl Propyl Carbonate (EPC), butylene Carbonate (BC), methyl Formate (MF), methyl Acetate (MA), ethyl Acetate (EA), propyl Acetate (PA), methyl Propionate (MP), ethyl Propionate (EP), propyl Propionate (PP), methyl Butyrate (MB), ethyl Butyrate (EB), 1, 4-butyrolactone (GBL), sulfolane (SF), dimethyl sulfone (MSM), methyl ethyl sulfone (EMS), and diethyl sulfone (ESE).
In some embodiments, additives are also optionally included in the electrolyte. For example, a negative electrode film-forming additive, a positive electrode film-forming additive, an additive for improving the overcharge performance of the battery, an additive for improving the high-temperature performance of the battery, an additive for improving the low-temperature performance of the battery, and the like may be included in the electrolyte.
[ separator ]
The kind of the separator is not particularly limited in the embodiments of the present application, and any known separator having a porous structure used in a secondary battery may be used. For example, the separator may be selected from one or more of a glass fiber film, a non-woven fabric film, a polyethylene film, a polypropylene film, a polyvinylidene fluoride film, and a multi-layer composite film comprising one or more of them.
In some embodiments, the secondary battery may be a lithium ion secondary battery.
In some embodiments, the positive electrode tab, the separator, and the negative electrode tab may be manufactured into an electrode assembly through a winding process or a lamination process.
In some embodiments, the secondary battery may include an exterior package. The exterior package may be used to enclose the electrode assembly and the electrolyte.
In some embodiments, the outer package of the secondary battery may be a hard case, such as a hard plastic case, an aluminum case, a steel case, or the like. The outer package of the secondary 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), polybutylene succinate (PBS) and the like.
The shape of the secondary battery is not particularly limited in the embodiments of the present application, and may be a cylindrical shape, a square shape, or any other shape. Fig. 4 shows a secondary battery 5 having a square structure as an example.
In some embodiments, referring to fig. 5, the overwrap may include a housing 51 and a cover plate 53. The housing 51 may include a bottom plate and a side plate connected to the bottom plate, and the bottom plate and the side plate enclose to form an accommodating cavity. The housing 51 has an opening communicating with the accommodating chamber, and a cover plate 53 can be provided to cover the opening to close the accommodating chamber. 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. An electrode assembly 52 is enclosed in the receiving cavity. The electrolyte wets the electrode assembly 52. The number of the electrode assemblies 52 included in the secondary battery 5 may be one or several and may be adjusted as needed.
In some embodiments, the secondary batteries may be assembled into a battery module, and the number of the secondary batteries included in the battery module may be plural, and the specific number may be adjusted according to the application and capacity of the battery module.
Fig. 6 is a battery module 3 as an example. Referring to fig. 6, in the battery module 4, a plurality of secondary batteries 5 may be arranged in series along the longitudinal direction of the battery module 4. Of course, the arrangement may be in any other way. The plurality of secondary batteries 5 may be further fixed by a fastener.
Alternatively, the battery module 4 may further include a case having an accommodation space in which the plurality of secondary batteries 5 are accommodated.
In some embodiments, the battery modules may be assembled into a battery pack, and the number of the battery modules contained in the battery pack may be adjusted according to the application and the capacity of the battery pack.
Fig. 7 and 8 are a battery pack 1 as an example. Referring to fig. 7 and 8, a battery pack 1 may include a battery case and a plurality of battery modules 4 disposed in the battery case. The battery box comprises an upper box body 2 and a lower box body 3, wherein 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. A plurality of battery modules 4 may be arranged in any manner in the battery box.
Electric device
Another aspect of the present application provides an electrical device, which includes at least one of the negative electrode sheet, the secondary battery, the battery module, or the battery pack provided in the present application. The secondary battery may be used as a power source of the device and also as an energy storage unit of the device. The device may be, but is not limited to, a mobile device (e.g., a mobile phone, a laptop computer, etc.), 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, etc.), an electric train, a ship, a satellite, an energy storage system, etc.
The device may select a secondary battery, a battery module, or a battery pack according to its usage requirements.
Fig. 9 is an apparatus as an example. The device is a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle or the like. In order to meet the demand of the device for high power and high energy density of the secondary battery, a battery pack or a battery module may be employed.
As another example, the device may be a cell phone, a tablet, a laptop, etc. The device is generally required to be thin and light, and a secondary battery may be used as a power source.
Examples
Hereinafter, examples of the present application will be described. The following description of the embodiments is merely exemplary in nature and is in no way intended to limit the present disclosure. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available. The contents of the respective components in the examples of the present application are by mass unless otherwise specified.
Example 1
1. Preparing a positive pole piece:
LiNi serving as a positive electrode active material 0.6 Co 0.2 Mn 0.2 O 2 (NCM 622), acetylene black as a conductive agent and polyvinylidene fluoride (PVDF) as a binder are dissolved in N-methylpyrrolidone (NMP) as a solvent according to the weight ratio of 97.
2. Preparing a negative pole piece:
preparing anode slurry: mixing artificial graphite serving as a negative electrode active material, conductive carbon black (Super-P) serving as a conductive agent, styrene Butadiene Rubber (SBR) serving as a binder and sodium carboxymethyl cellulose (CMC) serving as a thickening agent according to a mass ratio of 97;
preparing glue solution: 20g of polymethyl methacrylate (number average molecular weight: 10 ten thousand, crosslinking degree: 1%) and 100g of epoxy-modified styrene-acrylic copolymer (number average molecular weight: 1 ten thousand, crosslinking degree: 1%) were dissolved in water;
and coating the negative electrode slurry on the surface of a negative electrode main body part of a negative electrode current collector, coating the glue solution on a coating area of a negative electrode lug, and then drying, cold pressing, laser cutting and the like to obtain a negative electrode piece. Wherein the area ratio of the glue layer coating area of the negative pole tab in the negative pole tab is 1/2.
3. And (3) isolation film:
polyethylene film was selected as the barrier film.
4. Electrolyte solution:
ethylene Carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC) were mixed in a volume ratio of 1 6 Dissolving in the mixtureIn the latter organic solvent, an electrolyte solution having a concentration of 1mol/L was prepared.
5. Preparation of secondary battery:
examples 2 to 43 and comparative examples 1 to 3 are similar to the preparation method of example 1, except that the relevant preparation parameters of the adhesive layer are changed as detailed in table 1;
for the negative electrode sheet and the secondary battery obtained in each of the above examples and comparative examples, performance tests were performed by the following methods, and the obtained results are shown in table 1.
1. Determination of compatibility:
the negative pole piece prepared in each embodiment and the comparative example is placed under a light source of a high-definition microscope, the compatible area of the adhesive layer and the active material layer is observed at a multiplying power of 100X, if the compatibility is not good, the copper leakage foil appears golden yellow, and the compatibility is judged through color. And taking different 5 positions on the negative pole piece for observing by a high-definition microscope. If gold color appears in any one of the visual fields, it is judged as "x", and if gold color does not appear in all the visual fields, it is judged as "o".
2. Measurement of insulating Properties:
the negative pole piece prepared in each embodiment and the comparative example is placed on a glass plate, positive and negative probes of an insulation resistance instrument are placed on the adhesive layer at a distance of 5 cm-10 cm, and the resistance value is measured by testing for 10s under the condition of direct current 220V.
3. Measurement of adhesion:
in the negative electrode sheets prepared in the above examples and comparative examples, 2 pieces of 20mm × 100mm test samples were each taken, adhered to two aluminum plates (100 mm × 25 mm) with a double-sided adhesive, and then the 2 pieces of test samples were adhered with a 5mm × 5mm double-sided adhesive, and subjected to a shear test using a tensile tester to test the adhesion.
4. Measurement of thermal shrinkage:
the glue solution was applied to a copper foil, and the width W1 of the wet film was immediately measured with a tape, and then dried in an oven at 120 ℃ for 1 hour, and the width W2 of the glue layer after drying was measured, and the thermal shrinkage was calculated by the formula η = (W1-W2)/W1.
5. And (3) testing the laser cutting of the negative pole piece:
10000 m of the negative pole piece prepared in each embodiment and comparative example are taken, laser cutting is carried out by a laser die cutting machine, and 5000 tabs are obtained by cutting together. The cutting-off ratio of the area of the tab coated with the adhesive layer during the laser cutting process was calculated by the following formula.
Constant cut ratio = 1-shaped tab/5000 pieces
6. Testing the short circuit failure proportion of the battery cell:
and manufacturing a battery by using the prepared negative pole piece. The measurement was performed using an insulation resistance meter. And judging the situation that the measured ohmic impedance value is less than 10 omega as that the electric core is short-circuited, counting the number of the short-circuited electric cores, and dividing the number of the short-circuited electric cores by the total number of the electric cores (N = 50000) to obtain a value as a failure proportion.
[ Table 1]
Note:
a-1: polymethyl methacrylate (number average molecular weight: 10 ten thousand, degree of crosslinking: 1%)
A-2: polyhydroxyethylmethacrylate (number average molecular weight: 20 ten thousand, degree of crosslinking: 3%)
A-3: polylauryl methacrylate (number average molecular weight: 14 ten thousand, degree of crosslinking: 1.5%)
A-4: poly (allyl methacrylate) (number average molecular weight: 18 ten thousand, degree of crosslinking: 2.5%)
A-5: polymaleic acid citrate (number average molecular weight: 12 ten thousand, degree of crosslinking: 1%)
B-1: bisphenol A type epoxy modified styrene-acrylic copolymer (number average molecular weight: 1 ten thousand, degree of crosslinking: 1%)
B-2: dimethyldichlorosilane-modified styrene-acrylic copolymer (number average molecular weight: 1.1 ten thousand, degree of crosslinking: 1.1%)
B-3: polytetrafluoroethylene modified styrene-acrylic copolymer (number average molecular weight: 1.2 ten thousand, degree of crosslinking: 1.1%)
B-4: polypropylene-modified styrene-acrylic copolymer (number average molecular weight: 0.98 ten thousand, degree of crosslinking: 0.9%)
B-5: styrene-acrylic copolymer (number average molecular weight: 1 ten thousand, degree of crosslinking: 1%)
B-6: bisphenol A type epoxy modified styrene-acrylic copolymer (number average molecular weight: 3 ten thousand, degree of crosslinking: 1.5%)
B-7: bisphenol A type epoxy modified styrene-acrylic copolymer (number average molecular weight: 6 ten thousand, degree of crosslinking: 2.5%)
B-8: bisphenol A type epoxy modified styrene-acrylic copolymer (number average molecular weight: 10 ten thousand, degree of crosslinking: 3%)
C-1: alumina (average particle diameter: 41 nm)
C-2: magnesium oxide (average particle diameter: 44 nm)
C-3: calcium oxide (average particle diameter: 42 nm)
C-4: silicon dioxide (average particle diameter: 46 nm)
D-1: carbon black
D-2: graphite (Gray value of 0.5)
D-3: lithium iron phosphate powder (Gray value 1)
As can be seen from the results of table 1 above,
in examples 1 to 18, compared with comparative examples 2 to 3, by disposing the adhesive layer including both the carboxylate polymer and the styrene-acrylic copolymer or both the carboxylate polymer and the modified styrene-acrylic copolymer in the coating region of the negative electrode tab, excellent compatibility between the adhesive layer and the negative electrode active material layer can be ensured, the insulation of the adhesive layer can be improved, the adhesion between the adhesive layer and the current collector can be improved, the thermal shrinkage rate of the adhesive layer in the processing process can be reduced, the laser processability of the tab can be improved, the cutting ratio of the tab is lowered, and the short circuit failure ratio of the battery cell can be reduced, thereby improving the safety;
in addition, the ceramic filler is further added into the adhesive layer comprising the carboxylic ester polymer and the styrene-acrylic copolymer or the modified styrene-acrylic copolymer, so that the insulativity and hardness of the adhesive layer can be further improved, and the adhesive property between the adhesive layer and the current collector is more excellent;
furthermore, by further adding a coloring agent into the adhesive layer comprising the carboxylic ester polymer and the styrene-acrylic copolymer or the modified styrene-acrylic copolymer, the adhesive property between the adhesive layer and the current collector can be more excellent, the continuous cutting proportion of the tab is further reduced, and the processing manufacturability of the tab is improved.
Examples 44 to 48
An anode sheet and a secondary battery were produced in the same manner as in example 38, except that the area ratio of the jelly-layer coated region of the tab in the anode tab was changed to 1/2 as shown in table 2. The cell short-circuit failure rate was measured in the same manner as described above, and the obtained results are shown in table 2 below.
[ Table 2]
| Area ratio of coating | Percentage of failure (%) | |
| Example 44 | 1/4 | 0.03％ |
| Example 45 | 1/3 | 0.01％ |
| Example 46 | 1/2 | 0％ |
| Practice ofExample 47 | 2/3 | 0.008％ |
| Example 48 | 5/6 | 0.02％ |
As is clear from the results of table 2 above, the failure rate of the battery cell can be further reduced by setting the area ratio of the coating region of the adhesive layer in the negative electrode tab to 1/3 to 2/3.
Examples 49 to 55
A negative electrode tab and a secondary battery were produced in the same manner as in example 38, except that fillers having particle diameters shown in table 3 were used. The cell short-circuit failure rate was measured in the same manner as described above, and the obtained results are shown in table 3 below. In addition, with respect to the obtained negative electrode sheet, the area of the coating region where the adhesive layer was not applied was measured by a vernier caliper, and the value obtained by dividing the area of the coating region where the adhesive layer was not applied by the total area of the coating region was taken as a missing coating ratio, and the obtained measurement results are shown in table 3.
[ Table 3]
| Particle size of ceramic filler | Ratio of skip coating (%) | Percentage of failure (%) | |
| Example 49 | 8 | 0.1％ | 0.03％ |
| Example 50 | 10 | 0.05％ | 0.01％ |
| Example 51 | 20 | 0％ | 0％ |
| Example 52 | 40 | 0％ | 0％ |
| Example 53 | 60 | 0％ | 0％ |
| Example 54 | 100 | 0.05％ | 0.01％ |
| Example 55 | 120 | 0.2％ | 0.5％ |
From the results of table 3 above, it is understood that by further adding a ceramic filler having a particle size within a specific range to the gel layer comprising the carboxylic acid ester-based polymer and the styrene-acrylic copolymer or the carboxylic acid ester-based polymer and the modified styrene-acrylic copolymer, the failure rate of the cell can be reduced while the skip coat rate is maintained in a low range.
It should be understood by those skilled in the art that the above embodiments are only some of the specific embodiments for implementing the present application, and that various changes and modifications in form and detail may be made therein in the actual application while remaining within the scope of the present application.
Claims (16)
1. A secondary battery comprises a negative pole piece, the negative pole piece comprises a negative pole current collector,
the negative electrode current collector includes:
a negative electrode main body provided with a negative electrode active material layer on at least one surface thereof; and
a negative electrode tab, the negative electrode tab comprising a coating area, the coating area being provided with a glue layer,
the adhesive layer is adjacent to the negative electrode active material layer and comprises a carboxylic ester polymer and a styrene-acrylic copolymer and/or a modified styrene-acrylic copolymer.
2. The secondary battery according to claim 1,
in the glue layer, the content of the styrene-acrylic copolymer and/or the modified styrene-acrylic copolymer is 80-90 wt% in terms of mass fraction, and optionally 82-86 wt%.
3. The secondary battery according to claim 1 or 2,
the modified styrene-acrylic copolymer is one or more selected from epoxy modified styrene-acrylic copolymer, organic silicon modified styrene-acrylic copolymer, organic fluorine modified styrene-acrylic copolymer and polyolefin modified styrene-acrylic copolymer, and optionally one or more selected from epoxy modified styrene-acrylic copolymer and organic fluorine modified styrene-acrylic copolymer.
4. The secondary battery according to any one of claims 1 to 3,
the styrene-acrylic copolymer and/or the modified styrene-acrylic copolymer satisfy at least one of the following conditions:
(1) The crosslinking degree of the styrene-acrylic copolymer and/or the modified styrene-acrylic copolymer is 1 to 3 percent, and optionally 1.5 to 2.5 percent;
(2) The number average molecular weight of the styrene-acrylic copolymer and/or the modified styrene-acrylic copolymer is 1 ten thousand to 10 ten thousand, optionally 3 ten thousand to 6 ten thousand.
5. The secondary battery according to any one of claims 1 to 4,
the carboxylate polymer is one or more selected from poly (meth) acrylate, polymaleate, polyalkenyl acetate, optionally one or more selected from poly (meth) acrylate, optionally one or more selected from polyalkyl (meth) acrylate, polyhydroxyalkyl (meth) acrylate, or polyalkenyl (meth) acrylate, optionally one or more selected from polymethyl (meth) acrylate, polyethyl (meth) acrylate, poly n-butyl (meth) acrylate, polyisobutyl (meth) acrylate, polyhydroxyethyl (meth) acrylate, polylauryl (meth) acrylate, and polyallyl (meth) acrylate.
6. The negative electrode tab of any one of claims 1 to 5,
the carboxylic ester polymer satisfies at least one of the following conditions:
(1) The degree of crosslinking of the carboxylic ester polymer is 1% to 3%, optionally 1.5% to 2.5%;
(2) The number average molecular weight of the carboxylic ester polymer is 10-20 ten thousand, optionally 14-18 ten thousand.
7. The secondary battery according to any one of claims 1 to 6,
the adhesive layer also comprises a colorant, and the grey value of the colorant is less than or equal to 1, optionally less than or equal to 0.5;
optionally, the colorant is a black pigment;
optionally, the colorant is at least one of black master batch, carbon black, graphite and lithium iron phosphate.
8. The secondary battery according to claim 7,
in the glue layer, the content of the colorant is less than or equal to 2wt% by mass fraction, optionally 1-2 wt%.
9. The secondary battery according to claim 1 to 8,
the thermal shrinkage of the adhesive layer at 140 ℃ is 1% to 2%, optionally 1.4% to 1.6%.
10. The secondary battery according to any one of claims 1 to 9,
the area proportion of the coating area in the negative pole tab is 1/3-2/3.
11. The secondary battery according to any one of claims 1 to 10,
the glue layer also comprises a ceramic filler, optionally one or more selected from alumina, magnesia, calcium oxide and silica.
12. The secondary battery according to claim 11,
in the glue layer, the content of the ceramic filler is less than or equal to 5wt% in terms of mass fraction, and optionally 1-4 wt%.
13. The secondary battery according to claim 11 or 12,
the ceramic filler has a particle size of 10 to 100nm, optionally 20 to 60nm.
14. A battery module comprising the secondary battery according to any one of claims 1 to 13.
15. A battery pack comprising the battery module of claim 14.
16. An electric device comprising at least one of the secondary battery according to any one of claims 1 to 13, the battery module according to claim 14, or the battery pack according to claim 15.
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| CN202110902762.0A CN115706296A (en) | 2021-08-06 | 2021-08-06 | Secondary battery, battery module, battery pack, and electric device |
| PCT/CN2022/091602 WO2023010924A1 (en) | 2021-08-06 | 2022-05-09 | Secondary battery, battery module, battery pack, and power device |
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| CN202110902762.0A CN115706296A (en) | 2021-08-06 | 2021-08-06 | Secondary battery, battery module, battery pack, and electric device |
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| WO (1) | WO2023010924A1 (en) |
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|---|---|---|---|---|
| JP2012248544A (en) * | 2006-10-02 | 2012-12-13 | Nec Energy Devices Ltd | Lithium polymer battery |
| CN105244456A (en) * | 2015-09-10 | 2016-01-13 | 中航锂电（洛阳）有限公司 | Insulating paint containing calcium fluoride, and preparation method, insulating coating, battery pole piece and lithium-ion battery |
| KR20160125720A (en) * | 2015-04-22 | 2016-11-01 | 주식회사 엘지화학 | Insulating Composition for Electrode of Secondary Battery and Electrode Comprising Electrode Tab Coated by the Same |
| CN110098409A (en) * | 2018-01-30 | 2019-08-06 | 宁德时代新能源科技股份有限公司 | Secondary battery current collector and secondary battery using same |
| CN111916645A (en) * | 2020-07-01 | 2020-11-10 | 江苏塔菲尔新能源科技股份有限公司 | Pole piece, preparation method of pole piece and battery |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4186260B2 (en) * | 1998-08-10 | 2008-11-26 | ソニー株式会社 | Thin battery |
| JP6936419B2 (en) * | 2019-03-01 | 2021-09-15 | 積水化学工業株式会社 | Electrodes for lithium-ion secondary batteries and lithium-ion secondary batteries |
| CN110911637B (en) * | 2019-12-05 | 2021-07-30 | 东莞塔菲尔新能源科技有限公司 | Negative plate, preparation method thereof and lithium ion battery |
| CN111640978A (en) * | 2020-07-10 | 2020-09-08 | 湖北亿纬动力有限公司 | Lithium ion battery and preparation method and application thereof |
-
2021
- 2021-08-06 CN CN202110902762.0A patent/CN115706296A/en active Pending
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- 2022-05-09 WO PCT/CN2022/091602 patent/WO2023010924A1/en unknown
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012248544A (en) * | 2006-10-02 | 2012-12-13 | Nec Energy Devices Ltd | Lithium polymer battery |
| KR20160125720A (en) * | 2015-04-22 | 2016-11-01 | 주식회사 엘지화학 | Insulating Composition for Electrode of Secondary Battery and Electrode Comprising Electrode Tab Coated by the Same |
| CN105244456A (en) * | 2015-09-10 | 2016-01-13 | 中航锂电（洛阳）有限公司 | Insulating paint containing calcium fluoride, and preparation method, insulating coating, battery pole piece and lithium-ion battery |
| CN110098409A (en) * | 2018-01-30 | 2019-08-06 | 宁德时代新能源科技股份有限公司 | Secondary battery current collector and secondary battery using same |
| CN111916645A (en) * | 2020-07-01 | 2020-11-10 | 江苏塔菲尔新能源科技股份有限公司 | Pole piece, preparation method of pole piece and battery |
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| WO2023010924A1 (en) | 2023-02-09 |
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