CN114843706A - Battery and electronic equipment - Google Patents
Battery and electronic equipment Download PDFInfo
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- CN114843706A CN114843706A CN202210517358.6A CN202210517358A CN114843706A CN 114843706 A CN114843706 A CN 114843706A CN 202210517358 A CN202210517358 A CN 202210517358A CN 114843706 A CN114843706 A CN 114843706A
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- battery
- adhesive layer
- diaphragm
- positive plate
- layer
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- 239000012790 adhesive layer Substances 0.000 claims abstract description 47
- 239000010410 layer Substances 0.000 claims abstract description 44
- 239000002033 PVDF binder Substances 0.000 claims abstract description 40
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 40
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 34
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 229920001577 copolymer Polymers 0.000 claims abstract description 5
- 239000003292 glue Substances 0.000 claims description 16
- 239000011230 binding agent Substances 0.000 claims description 12
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical group FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 11
- 239000000919 ceramic Substances 0.000 claims description 11
- 239000006258 conductive agent Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 5
- 239000007773 negative electrode material Substances 0.000 claims description 5
- 229920000098 polyolefin Polymers 0.000 claims description 5
- 239000007774 positive electrode material Substances 0.000 claims description 5
- 238000012360 testing method Methods 0.000 abstract description 18
- 238000007086 side reaction Methods 0.000 abstract description 13
- 102000004310 Ion Channels Human genes 0.000 abstract description 7
- 230000017525 heat dissipation Effects 0.000 abstract description 7
- 239000003792 electrolyte Substances 0.000 abstract description 6
- 238000007334 copolymerization reaction Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011267 electrode slurry Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000004880 explosion Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 238000004804 winding Methods 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
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention provides a battery and electronic equipment, wherein the battery comprises a positive plate, a diaphragm and a negative plate, and the diaphragm is arranged between the positive plate and the negative plate; the diaphragm comprises a substrate layer, a first adhesive layer and a second adhesive layer, wherein the first adhesive layer and the second adhesive layer are respectively arranged on two opposite side faces of the substrate layer, the diaphragm is fixed on the positive plate through the first adhesive layer, and the first adhesive layer comprises acrylic acid modified copolymerization polyvinylidene fluoride. Therefore, the acrylic acid modified copolymer polyvinylidene fluoride is arranged in the first adhesive layer, so that the viscosity of the first adhesive layer is reduced, the adhesion between the diaphragm and the positive plate is reduced, the positive plate and the electrolyte can generate side reaction to generate heat and generate gas under the limit environment of furnace temperature test, the first adhesive layer can fall off from the positive plate when the positive plate generates side reaction, the heat dissipation is accelerated, the ion channel is cut off, and the safety of the battery is improved.
Description
Technical Field
The present invention relates to the field of battery technologies, and in particular, to a battery and an electronic device.
Background
Lithium ion batteries have numerous advantages and are used on a large scale. In order to reduce the occurrence of instability in the interior of the cell under high voltage electrochemical systems, the cell needs to be subjected to an oven temperature (Hotbox) test. Particularly in the quick-charging battery, the amorphous carbon coating amount of the quick-charging battery is large, so that the thermal stability of graphite is reduced, and the thermal stability of the battery is further reduced.
At present, an organic solvent acetone is generally used in the manufacturing process of the battery diaphragm to improve the passing rate of furnace temperature tests, and the macroporous oil-based diaphragm using the organic solvent acetone is gradually replaced along with the increasing requirement on environmental protection. The gravure oil-based separator was designed, but the oven temperature disadvantage of the gravure oil-based separator was significant at the comparative limit.
It can be seen that the battery in the prior art has the problem of low safety.
Disclosure of Invention
The embodiment of the invention provides a battery and electronic equipment, which aim to solve the problem of low battery safety in the prior art.
The embodiment of the invention provides a battery, which comprises a positive plate, a diaphragm and a negative plate, wherein the diaphragm is arranged between the positive plate and the negative plate;
the diaphragm comprises a substrate layer, and a first adhesive layer and a second adhesive layer which are respectively arranged on two opposite side faces of the substrate layer, the diaphragm is fixed on the positive plate through the first adhesive layer, and the first adhesive layer comprises acrylic acid modified copolymer polyvinylidene fluoride.
Optionally, the acrylic modified co-polyvinylidene fluoride has the structural formula:
wherein R is-H or-CH 3 M is the content of vinylidene fluoride chain segments, and n is the content of acrylic acid chain segments.
Alternatively, the vinylidene fluoride segment content m is from 0.95 to 0.995 and the acrylic acid segment content n is from 0.005 to 0.05.
Alternatively, the acrylic-modified co-polyvinylidene fluoride has a molecular weight of 30 to 60 ten thousand.
Optionally, the peel force of the separator from the positive electrode sheet is less than 10N/m.
Optionally, the thickness of the first adhesive layer is less than or equal to the thickness of the second adhesive layer.
Optionally, the separator further comprises a ceramic layer disposed between the substrate layer and the first glue layer.
Optionally, the substrate layer comprises a polyolefin material.
Optionally, the positive electrode sheet includes a positive electrode active material, a first conductive agent, and a first binder, and the negative electrode sheet includes a negative electrode active material, a second conductive agent, and a second binder.
Optionally, when the battery core is wound, the ceramic layer winds the positive electrode sheet.
The embodiment of the invention also provides electronic equipment comprising the battery.
In the embodiment of the invention, the acrylic acid modified co-polyvinylidene fluoride is arranged in the first adhesive layer, so that the viscosity of the first adhesive layer is reduced, the adhesion between the diaphragm and the positive plate is reduced, the positive plate can generate side reaction with electrolyte to generate heat and generate gas under the limit environment of furnace temperature test, the first adhesive layer can fall off from the positive plate when the positive plate generates side reaction, the heat dissipation is accelerated, and an ion channel is cut off, so that the safety of the battery is improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required to be used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without inventive labor.
Fig. 1 is a schematic structural view of a separator of a battery according to an embodiment of the present invention;
fig. 2 is a second schematic structural diagram of a battery separator according to an embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The terms first, second and the like in the description and in the claims of the present invention are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It will be appreciated that the structures so used are interchangeable under appropriate circumstances such that embodiments of the invention can be practiced in sequences other than those illustrated or described herein, and the terms "first," "second," and the like are generally used herein in a generic sense and do not limit the number of terms, e.g., a first term can be one or more than one. In addition, "and/or" in the specification and claims means at least one of connected objects, a character "/" generally means that a preceding and succeeding related objects are in an "or" relationship.
An embodiment of the present invention provides a battery, as shown in fig. 1 to 2, including a positive plate, a separator 10, and a negative plate, where the separator 10 is disposed between the positive plate and the negative plate;
the diaphragm 10 comprises a substrate layer 101, and a first adhesive layer 102 and a second adhesive layer 103 which are respectively arranged on two opposite sides of the substrate layer 101, the diaphragm 10 is fixed on the positive plate through the first adhesive layer 102, and the first adhesive layer 102 comprises acrylic acid modified copolymer polyvinylidene fluoride.
In this embodiment, the acrylic acid modified polyvinylidene fluoride is disposed in the first adhesive layer 102, so that the viscosity of the first adhesive layer 102 is reduced, and the adhesion between the separator 10 and the positive electrode plate is reduced, the positive electrode plate can generate a side reaction with the electrolyte to generate heat and generate gas under the limit environment of the furnace temperature test, and the first adhesive layer 102 can fall off from the positive electrode plate when the side reaction occurs to the positive electrode plate, so as to accelerate heat dissipation and cut off an ion channel, and thus, the safety of the battery is improved.
The polyvinylidene fluoride PVDF has excellent adhesion, and when a glue layer of the PVDF is adhered to a positive plate, the separation of the diaphragm 10 and the positive plate is difficult under the limit environment of furnace temperature test, so that the situation of battery short circuit and even explosion is easy to occur. The negative electrode sheet has less side reactions with the electrolyte, and the second adhesive layer 103 may include PVDF to enhance the adhesion stability of the separator 10 to the negative electrode sheet.
Alternatively, the acrylic modified co-polyvinylidene fluoride has the formula:
wherein R may be-H or-CH 3 M may be a vinylidene fluoride segment content, and n may be an acrylic segment content.
In the present embodiment, the separator 10 may be a gravure oil-based coated separator, and when a gravure oil-based coated separator is used for a battery, the battery has the characteristics of good adhesion and excellent cycle stability, but the furnace temperature pass rate of the separator is low, and the furnace temperature disadvantage is significant at the comparative limit. The PVDF in the first gel layer 102 of the separator 10 is modified so that the PVDF is acrylic modified to form acrylic modified co-polyvinylidene fluoride, in other words, the acrylic modified co-polyvinylidene fluoride can be polymerized from the polymerized monomers vinylidene fluoride and acrylic monomers. The reaction formula can be as follows:
in the above reaction formula: the acrylic monomer may be selected from acrylic acid or methacrylic acid, i.e. R may be-H or-CH 3; in the polymer chain segment of the modified PVDF structural formula, the content of the vinylidene fluoride chain segment can be m, and the content of the acrylic acid or methacrylic acid chain segment can be n.
Wherein the vinylidene fluoride segment content m may be 0.95 to 0.995 and the acrylic acid segment content n may be 0.005 to 0.05. The viscosity of the first adhesive layer 102 is reduced, so that the adhesion between the diaphragm 10 and the positive plate is reduced, the diaphragm 10 falls off from the positive plate in the limit environment of furnace temperature test, heat dissipation is accelerated, an ion channel is cut off, the situations of short circuit, even explosion and the like in the battery are reduced, and the safety of the battery is improved.
Alternatively, the molecular weight of the acrylic modified co-polyvinylidene fluoride may be 30 to 60 ten thousand to reduce the viscosity of the first adhesive layer 102, and at the same time, the battery has the separator 10 stably bonded to the positive electrode sheet under normal operation conditions to balance the viscosity of the first adhesive layer 102.
Alternatively, the peeling force of the separator 10 from the positive electrode sheet is less than 10N/m. The requirements of the furnace temperature test are different according to different battery models. Thus, when the adhesive layer on the diaphragm 10 is modified, the content of the vinylidene fluoride chain segment and the content of the acrylic acid or methacrylic acid chain segment can be adjusted as required, so that the peeling force of the diaphragm 10 and the positive plate is less than 10N/m, the first adhesive layer 102 can fall off from the positive plate when the positive plate has side reaction, the heat dissipation is accelerated, the ion channel is cut off, and the safety of the battery is improved.
Further, the peeling force of the separator 10 from the positive electrode sheet may be less than 5N/m to increase the speed at which the separator 10 is peeled off from the positive electrode sheet.
In some alternative embodiments, the thickness of the first glue layer 102 may be equal to the thickness of the second glue layer 103. The adhesiveness between the separator 10 and the positive electrode sheet is reduced by providing the acrylic acid-modified co-polyvinylidene fluoride in the first adhesive layer 102 so that the adhesiveness of the first adhesive layer 102 is reduced; the second glue layer 103 may include PVDF to enhance the stability of the adhesion of the separator 10 to the negative electrode sheet. Under the limit environment of furnace temperature test, the positive plate can generate side reaction with the electrolyte to generate heat and generate gas, the first adhesive layer 102 can fall off from the positive plate when the positive plate generates side reaction, heat dissipation is accelerated, and an ion channel is cut off, so that the safety of the battery is improved.
In other alternative embodiments, the thickness of the first glue layer 102 may be less than the thickness of the second glue layer 103. Also, the acrylic acid modified copolymer polyvinylidene fluoride is provided in the first adhesive layer 102, so that the viscosity of the first adhesive layer 102 is reduced, thereby reducing the adhesiveness between the separator 10 and the positive electrode sheet; the second glue layer 103 may include PVDF to enhance the stability of the adhesion of the separator 10 to the negative electrode sheet. The thickness of the first adhesive layer 102 is smaller than that of the second adhesive layer 103 to further reduce the viscosity reduction of the first adhesive layer 102, and to improve the speed of the separation of the separator 10 from the positive electrode sheet in the event of side reaction, thereby improving the safety of the battery.
Optionally, the separator 10 may further include a ceramic layer 104, the ceramic layer 104 being disposed between the substrate layer 101 and the first glue layer 102.
In the process of manufacturing the positive plate, the diaphragm 10 and the negative plate into the battery cell, the diaphragm 10 is easy to shrink through the processes of heating, pressurizing and the like, so that the positive plate and the negative plate are in direct contact, and the situations of short circuit, even explosion and the like occur. The ceramic layer 104 is arranged in the diaphragm 10, and during winding, the ceramic layer 104 in the diaphragm 10 winds the positive plate and is supported by the ceramic layer 104, so that the positive plate and the negative plate are arranged at intervals through the diaphragm 10 in the production and use processes of the battery, the stability of the diaphragm 10 is enhanced, and the safety of the battery is improved.
Optionally, the substrate layer 101 comprises a polyolefin material. A porous film of a polyolefin material is used as the base material layer 101, and the lithium ion passage rate is increased.
Alternatively, the positive electrode sheet includes a positive electrode active material, a first conductive agent, and a first binder, and the negative electrode sheet includes a negative electrode active material, a second conductive agent, and a second binder.
The preparation of the positive electrode sheet can be described as follows:
mixing the positive active material, the first conductive agent and the first binder according to a certain proportion, adding N-methyl pyrrolidone, stirring and dispersing to prepare positive slurry. Wherein, in the positive electrode slurry, the solid components contained 96.5 wt% of Lithium Cobaltate (LCO), 1.5 wt% of conductive carbon black and 2 wt% of polyvinylidene fluoride (PVDF). And coating the positive slurry on a positive current collector by coating equipment (double-sided coating), drying, slitting and flaking to prepare the positive pole piece.
Wherein, the positive active material can be at least one of lithium cobaltate, lithium iron phosphate, lithium nickel cobalt manganese oxide and lithium nickel cobalt aluminate;
the first conductive agent can be at least one of conductive graphite, ultrafine graphite, acetylene black, conductive carbon black SP, superconducting carbon black, carbon nanotubes and conductive carbon fibers;
the first binder is at least one selected from polyvinylidene fluoride, polytetrafluoroethylene, sodium carboxymethylcellulose, styrene butadiene rubber, polyurethane, polyvinyl alcohol, polyvinylidene fluoride and vinylidene fluoride-fluorinated olefin copolymer.
The preparation of the negative electrode sheet can be described as follows:
mixing the negative electrode active material, the second conductive agent, the second binder and the thickening agent according to a certain proportion, adding deionized water, stirring and dispersing to prepare negative electrode slurry. The negative electrode slurry comprises 96.9% of artificial graphite, 0.5% of conductive carbon black, 1.3% of sodium carboxymethyl cellulose (CMC) and 1.3% of Styrene Butadiene Rubber (SBR), and then the negative electrode slurry is coated on a negative electrode current collector (double-sided coating), and the negative electrode pole piece is obtained through drying, slitting and sheet making.
Wherein, the negative active material can be at least one of artificial graphite, natural graphite, silicon and lithium titanate;
the second conductive agent can be at least one of conductive graphite, ultrafine graphite, acetylene black, conductive carbon black SP, superconducting carbon black, carbon nano tubes and conductive carbon fibers;
the second binder is at least one selected from polyvinylidene fluoride, polytetrafluoroethylene, sodium carboxymethylcellulose, styrene butadiene rubber, polyurethane, polyvinyl alcohol, polyvinylidene fluoride and vinylidene fluoride-fluorinated olefin copolymer.
The preparation of the separator 10 can be described as follows:
the ceramic layer 104 is formed by using a porous film of polyolefin as the base layer 101, polyvinylidene fluoride as the binder, and alumina as the ceramic particles. The slurry obtained above was coated on opposite sides of the substrate layer 101 by means of gravure coating, wherein the glue coat layer of the ceramic layer 104 was coated using modified PVDF as a binder, thereby producing the battery separator 10.
The modified PVDF, i.e., the first adhesive layer 102, is obtained by emulsion polymerization using the same polymerization method as homopolymerized PVDF, and the polymer monomers thereof may be vinylidene fluoride and acrylic monomers, and the reaction formula is as follows:
in the above reaction formula: the acrylic monomer can be acrylic acid or methacrylic acid, namely R is-H or-CH 3; the polymer segment of the modified PVDF structural formula contains m of vinylidene fluoride segment, n of acrylic acid or methacrylic acid segment, wherein m is 0.95-0.995, and n is 0.005-0.05.
Wherein, the molecular weight of the acrylic acid modified copolymerization polyvinylidene fluoride can be selected from 30 to 60 ten thousand.
The preparation of the battery can be described as follows:
the positive plate, the negative plate, the diaphragm 10 and the aluminum plastic film are manufactured into the battery together, then the procedures of liquid injection, aging, formation, sorting and the like are carried out, and finally the electrochemical performance and the safety performance (mainly needle abuse) of the battery are tested. The preparation environment temperature of the electrode material is kept at 20-30 ℃, and the humidity is less than or equal to 40% RH.
The preparation of the electrode material uses equipment including: the device comprises a stirrer, a coating machine, a roller press, a splitting machine, a pelleter, an ultrasonic spot welding machine, a top side sealing machine, an ink-jet printer, a film sticking machine, a liquid injection machine, a formation cabinet, a cold press, a separation cabinet, a vacuum oven and the like.
The battery produced in the above manner was designated as example 1, and example 2 and comparative example 1 were set simultaneously.
Embodiment 2 is different from embodiment 1 in that the thickness of the first glue layer 102 is smaller than that of the second glue layer 103.
Comparative example 1 is different from example 1 in that comparative example 1 uses a conventional gravure oil-based separator, and the first glue layer 102 does not include acrylic modified co-polyvinylidene fluoride.
The batteries of example 1, example 2 and comparative example 1 were subjected to an oven temperature test and a positive electrode tab peel force test, respectively.
The lithium ion batteries of the above examples and comparative examples were subjected to an oven temperature test, which was as follows: firstly, charging the battery to an upper limit voltage +30mV (0.02C cutoff) at 0.2C, and testing the initial state of the battery, including voltage, internal resistance, thickness and the like; then the battery is put into an oven and heated at the initial temperature of 25 plus or minus 3 ℃, the temperature rise rate is 5 plus or minus 2 ℃, the temperature rises to 130 plus or minus 2 ℃, and the test is finished after the temperature is kept for 60 min. The pass criteria were: the battery core does not catch fire or explode.
The positive plate peeling force test method can be as follows: and taking the battery cores of the embodiment 1, the embodiment 2 and the comparative example 1, disassembling the battery cores in a drying room in a full-power state, taking the position where the diaphragm is bonded with the positive plate, and placing the position on a tensile machine for testing to obtain the bonding force of the diaphragm and the positive plate.
The results of the oven temperature test and the positive electrode tab peel force test performed on the batteries of example 1, example 2 and comparative example 1, respectively, are shown in table 1 below:
| stripping force/N.m-1 of diaphragm and positive plate | Furnace temperature pass rate | |
| Example 1 | 8.9 | 4/5PASS |
| Example 2 | 4.6 | 5/5PASS |
| Comparative example 1 | 12.2 | 0/5PASS |
As can be seen from the results in table 1, comparative example 1 is poor in safety and cannot satisfy the safety performance requirements of the lithium ion battery. The safety of the embodiment 1 and the embodiment 2 of the invention is higher than that of the comparative example 1, that is, the acrylic acid modified and copolymerized polyvinylidene fluoride is arranged in the first adhesive layer 102, so that the viscosity of the first adhesive layer 102 is reduced, the adhesion between the diaphragm 10 and the positive plate is reduced, the positive plate can generate heat and generate gas through side reaction with the electrolyte in a limit environment of furnace temperature test, the first adhesive layer 102 can fall off from the positive plate when the side reaction occurs in the positive plate, the heat dissipation is accelerated, the ion channel is cut off, and the safety of the battery is improved.
Because the safety of the embodiment 2 is better, the embodiment 2 can be selected in practical application. In embodiment 2, the thickness of the diaphragm 10 is also reduced after the sizing amount of the first glue layer 102 is reduced, which is beneficial to improving the energy density.
The embodiment of the invention also provides electronic equipment comprising the battery.
The electronic device may be a notebook computer, a smart phone, or the like, and is not limited herein. The implementation manner of the embodiment of the battery is also suitable for the embodiment of the electronic device, and can achieve the same technical effect, which is not described herein again.
It should be noted that, in this document, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element. Furthermore, it should be noted that the scope of the methods and apparatus of embodiments of the present invention is not limited to performing functions in the order discussed, but may include performing functions in a substantially simultaneous manner or in a reverse order depending on the functionality involved, e.g., the methods described may be performed in an order different than that described, and various steps may be added, omitted, or combined. In addition, features described with reference to certain examples may be combined in other examples.
While the present invention has been described with reference to the particular illustrative embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but is intended to cover various modifications, equivalent arrangements, and equivalents thereof, which may be made by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The battery is characterized by comprising a positive plate, a diaphragm and a negative plate, wherein the diaphragm is arranged between the positive plate and the negative plate;
the diaphragm comprises a substrate layer, and a first adhesive layer and a second adhesive layer which are respectively arranged on two opposite side faces of the substrate layer, the diaphragm is fixed on the positive plate through the first adhesive layer, and the first adhesive layer comprises acrylic acid modified copolymer polyvinylidene fluoride.
2. The battery of claim 1, wherein the acrylic-modified co-polyvinylidene fluoride has the formula:
wherein R is-H or-CH 3 M is the content of vinylidene fluoride chain segments, and n is the content of acrylic acid chain segments.
3. The battery according to claim 2, wherein the vinylidene fluoride segment content m is 0.95 to 0.995 and the acrylic segment content n is 0.005 to 0.05.
4. The battery according to claim 1, wherein the acrylic-modified co-polyvinylidene fluoride has a molecular weight of 30 to 60 ten thousand.
5. The battery according to claim 1, wherein the peel force of the separator from the positive electrode sheet is less than 10N/m.
6. The battery of claim 1, wherein the thickness of the first glue layer is less than or equal to the thickness of the second glue layer.
7. The battery of claim 1, wherein the separator further comprises a ceramic layer disposed between the substrate layer and the first bondline.
8. The battery of claim 1, wherein the substrate layer comprises a polyolefin material.
9. The battery according to claim 1, wherein the positive electrode tab includes a positive electrode active material, a first conductive agent, and a first binder, and the negative electrode tab includes a negative electrode active material, a second conductive agent, and a second binder.
10. An electronic device characterized by comprising the battery according to any one of claims 1 to 9.
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