CN114824171A - Preparation method of multilayer battery pole piece and multilayer battery pole piece - Google Patents
Preparation method of multilayer battery pole piece and multilayer battery pole piece Download PDFInfo
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- CN114824171A CN114824171A CN202210481194.6A CN202210481194A CN114824171A CN 114824171 A CN114824171 A CN 114824171A CN 202210481194 A CN202210481194 A CN 202210481194A CN 114824171 A CN114824171 A CN 114824171A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000000835 fiber Substances 0.000 claims abstract description 42
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 28
- 239000011888 foil Substances 0.000 claims abstract description 25
- 238000000576 coating method Methods 0.000 claims abstract description 20
- 239000011248 coating agent Substances 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- 239000011149 active material Substances 0.000 claims description 21
- 239000006258 conductive agent Substances 0.000 claims description 21
- 239000011230 binding agent Substances 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 17
- 229920000767 polyaniline Polymers 0.000 claims description 17
- 239000013543 active substance Substances 0.000 claims description 16
- 239000006185 dispersion Substances 0.000 claims description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- 239000002033 PVDF binder Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- 238000009987 spinning Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 12
- 229920001940 conductive polymer Polymers 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 11
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 9
- 239000002041 carbon nanotube Substances 0.000 claims description 9
- 239000007773 negative electrode material Substances 0.000 claims description 8
- 229920000128 polypyrrole Polymers 0.000 claims description 8
- 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 claims description 7
- 238000010907 mechanical stirring Methods 0.000 claims description 6
- 239000007774 positive electrode material Substances 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 6
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 230000005686 electrostatic field Effects 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- 239000006245 Carbon black Super-P Substances 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 239000002134 carbon nanofiber Substances 0.000 claims description 3
- 239000004815 dispersion polymer Substances 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 abstract description 18
- 230000008595 infiltration Effects 0.000 abstract description 10
- 238000001764 infiltration Methods 0.000 abstract description 10
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 23
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 11
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 11
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 11
- 229940105329 carboxymethylcellulose Drugs 0.000 description 11
- 238000003756 stirring Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910021383 artificial graphite Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration 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
- 238000002791 soaking Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910007933 Si-M Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910008318 Si—M Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-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
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000002457 bidirectional effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 description 1
- 229940063834 carboxymethylcellulose sodium Drugs 0.000 description 1
- 239000006255 coating slurry Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 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
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
- H01M4/806—Nonwoven fibrous fabric containing only fibres
Abstract
The invention discloses a preparation method of a multilayer battery pole piece and the multilayer battery pole piece, wherein the preparation method of the multilayer battery pole piece comprises five steps of dispersing I, electrostatic spinning, dispersing II, coating and drying, and the multilayer battery pole piece comprises a foil layer, a nano conductive fiber layer and an active layer; the multilayer battery pole piece obtained by the preparation method not only can effectively increase the porosity of the pole piece and effectively improve the infiltration capacity of the electrolyte, but also can reduce the contact resistance between different layers, and meanwhile, the preparation method is simple and is convenient for industrial production.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a preparation method of a multilayer battery pole piece and the multilayer battery pole piece.
Background
The lithium ion battery generally comprises a battery pole piece, an isolating membrane and electrolyte, wherein the preparation method of the battery pole piece comprises the steps of taking a metal foil as a base material, coating slurry containing an active substance, a conductive agent and a binder on the base material in an extrusion or transfer coating mode, and drying to obtain the battery pole piece.
With the continuous improvement of energy density, the thickness of the traditional battery pole piece is correspondingly increased so as to improve the available capacity ratio, but the increase of the thickness of the battery pole piece can cause the difficulty of soaking electrolyte in the battery pole piece to be increased, and the insufficient soaking can cause the problems of insufficient capacity exertion, short cycle life and the like.
In order to improve the wetting effect of the electrolyte on the battery pole piece, two aspects of dynamics and thermodynamics can be considered. In the aspect of dynamics, the sufficient infiltration of the electrolyte is ensured by increasing the standing time after the liquid injection or properly increasing the infiltration temperature, and the disadvantage is that the production period and the production cost are increased. The thermodynamic method is to improve the infiltration effect by increasing the porosity of the battery pole piece, such as Chinese invention patent application No. 202010021572.3(CN113097442A) 'an electrode and its preparation method', its technical scheme disclosed includes the current collector, a plurality of via layers and a plurality of active layers, the via layers are composed of network structure of high polymer, when using, the high polymer is dissolved in the electrolyte and forms pore structure with controllable aperture size and distribution, the electrode structure adopts the via layers as the high polymer of electronic insulation, can greatly increase the contact resistance between each layer, and then influence the battery performance, meanwhile the preparation method adopted by the patent has the problem of coating twice or more, the technological requirement is higher, is not favorable to carry on the mass production.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a multilayer battery pole piece and the multilayer battery pole piece, which can effectively increase the porosity of the electrode piece, effectively improve the infiltration capacity of electrolyte, reduce the contact resistance between different layers, and are simple and convenient for industrial production.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of a multilayer battery pole piece comprises the following steps:
s1, dispersion I: dispersing a conductive polymer in a first solvent, performing ultrasonic dispersion or mechanical stirring uniformly, and performing defoaming treatment to obtain a spinning solution with the conductive polymer dispersion concentration of 1-30 wt%;
s2, electrostatic spinning: adding the spinning solution into an injector of an electrostatic spinning device, carrying out electrostatic spinning in a high-voltage electrostatic field, solidifying and forming the electrostatic spinning solution trickle in the air, receiving the electrostatic spinning solution trickle on a foil layer, and then carrying out vacuum drying at the temperature of 30-80 ℃ to obtain a nano conductive fiber layer with a net structure;
s3, dispersion II: dispersing an active substance, a conductive agent and a binder in a second solvent, and performing ultrasonic dispersion or mechanical stirring uniformly to obtain active substance slurry with the active substance ratio of 50-98 wt%, the conductive agent concentration of 0.1-10 wt% and the binder concentration of 0.5-30 wt%;
s4, coating: coating the active material slurry on the nano conductive fiber layer to obtain an active material layer;
s5, drying: and drying the composite layer consisting of the foil layer, the nano conductive fiber layer and the active material layer to obtain the multilayer battery pole piece.
Preferably, the conductive polymer in step S1 is polyaniline and/or polypyrrole, and the fiber diameter of the polyaniline and the polypyrrole is 10nm to 1000 nm.
Preferably, the thickness of the nano conductive fiber layer in the step S2 ranges from 0.1 μm to 100 μm, and the porosity of the nano conductive fiber layer is 10% to 60%.
Preferably, the thickness of the active material layer in the step S4 is in a range of 50 to 200 μm.
Preferably, the active material in step S3 is a positive electrode material or a negative electrode material, the conductive agent includes one or more of carbon black, acetylene black, super-P, carbon nanotubes, carbon nanofibers, graphene, and redox graphite, and the binder includes one or more of polyvinylidene fluoride, styrene-butadiene rubber, sodium carboxymethyl cellulose, and acrylonitrile multipolymer.
Preferably, the first solvent in step S1 includes one or more of ethanol, ethylene glycol, propanol, N-Dimethylformamide (DMF), N-methylpyrrolidone, and isopropanol; the second solvent in step S3 includes one or more of water, ethanol, ethylene glycol, propanol, N-methylpyrrolidone, and isopropanol.
Preferably, the foil layer in step S2 is composed of one of a metal, a metal mixture, a metal/organic composite, and a metal/inorganic composite.
The invention also provides a multilayer battery pole piece, and the multilayer battery pole piece prepared by the preparation method of the multilayer battery pole piece.
Compared with the prior art, the invention has the advantages that:
1) the nano conductive fiber layer is used as a coating matrix of the active layer, so that the toughness of the battery pole piece can be improved, the nano conductive fiber layer is of a net structure and has high porosity, the infiltration path of electrolyte can be increased, unidirectional infiltration is changed into bidirectional infiltration, and the nano conductive fiber can swell after being soaked in the electrolyte, so that the volume of the battery pole piece is increased, a certain amount of electrolyte can be reserved, and the cycle performance of the battery can be further improved;
2) the thickness, the fiber diameter and the porosity of the nano conductive fiber layer can be controlled by adjusting electrostatic spinning process parameters, and compared with the traditional porous battery pole piece, the nano conductive fiber layer has stronger electron conductivity;
3) the nano conductive fiber layer can conduct electrons, and the conductive state is mesh continuous conduction, so that the contact resistance between different layers of the battery pole piece is reduced, the electronic conductivity of the non-active layer is improved, and the multiplying power performance of the battery is improved;
4) the method of combining the electrostatic spinning process and the single coating process is adopted, so that multiple coatings are not needed, the process difficulty is reduced, and the industrial production is facilitated.
Drawings
FIG. 1 is a schematic cross-sectional view of a multi-layer battery plate according to the present invention;
FIG. 2 is a schematic view of an electrolyte wetting path.
In the figure, 1, a foil layer; 2. a layer of nano-conductive fibers; 3. an active layer; 4. and (3) an electrolyte.
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
Examples 1,
As shown in fig. 1, a multi-layer battery pole piece comprises a foil layer 1, a nano conductive fiber layer 2 and an active material layer 3 which are fixedly connected in sequence.
The foil layer 1 is composed of one of metal, metal mixture, metal/organic compound and metal/inorganic compound; the nano conductive fiber layer 2 is composed of conductive polymers, and the conductive polymers are composed of polyaniline and/or polypyrrole; the active material layer 3 includes an active material, a conductive agent and a binder, the active material is a positive electrode material or a negative electrode material, the conductive agent includes one or more of carbon black, acetylene black, super-P, carbon nanotubes, carbon nanofibers, graphene and redox graphite, and the binder includes one or more of polyvinylidene fluoride (PVDF), Styrene Butadiene Rubber (SBR), sodium carboxymethylcellulose (CMC) and acrylonitrile multipolymer.
Furthermore, the battery can be divided into a positive pole piece and a negative pole piece according to the application of the multilayer battery pole piece in the battery, when the multilayer battery pole piece is the positive pole piece, the active material adopts a positive pole material, and the positive pole material comprises one or more of lithium cobaltate, lithium iron phosphate or lithium nickel cobalt manganese oxide; when the multilayer battery pole piece is a negative pole piece, the active material adopts a negative pole material, the negative pole material comprises one or more of Si, SiOx, Si-M alloy and Si/C, SiOx/C, Si-M/C, wherein M is metal or metal oxide, and M is preferably Li or Li 2 O、Co、CoO、Fe、Fe 2 O 3 、Mg、MgO、Sn、SnO、Ti、TiO 2 And Ag, AgO or Cr, x is more than or equal to 0 and less than or equal to 2, and C is organic carbon, inorganic carbon, graphite, graphene, carbon nano tube or carbon fiber. In addition, the negative electrode material can also adopt one or more of artificial graphite, natural graphite, mesocarbon microbeads and lithium titanate.
When the multilayer battery pole piece is soaked in the electrolyte 4, the electrolyte 4 soaks the multilayer battery pole piece in two directions (see fig. 2), and the soaking effect of the electrolyte 4 on the battery pole piece is improved.
The preparation method of the multilayer battery pole piece comprises the following steps:
s1, dispersion I: dispersing a conductive polymer in a first solvent, performing ultrasonic dispersion or mechanical stirring uniformly, and performing defoaming treatment to obtain a spinning solution with the conductive polymer dispersion concentration of 1-30 wt%;
s2, electrostatic spinning: adding the spinning solution into an injector of an electrostatic spinning device, carrying out electrostatic spinning in a high-voltage electrostatic field, solidifying and forming the electrostatic spinning solution trickle in the air, receiving the electrostatic spinning solution trickle on a foil layer, and then carrying out vacuum drying at the temperature of 30-80 ℃ to obtain a nano conductive fiber layer with a net structure;
s3, dispersion II: dispersing an active substance, a conductive agent and a binder in a second solvent, and performing ultrasonic dispersion or mechanical stirring uniformly to obtain active substance slurry with the active substance ratio of 50-98 wt%, the conductive agent concentration of 0.1-10 wt% and the binder concentration of 0.5-30 wt%;
s4, coating: coating the active substance slurry on the nano conductive fiber layer to obtain an active substance layer;
s5, drying: and drying the composite layer consisting of the foil layer, the nano conductive fiber layer and the active material layer to obtain the multilayer battery pole piece.
The conductive polymer is polyaniline and/or polypyrrole, the fiber diameter of the polyaniline and the polypyrrole is 10 nm-1000 nm, and the fiber diameter is preferably 10 nm-100 nm.
The thickness range of the nano conductive fiber layer in the step S2 is 0.1 μm to 100 μm, and the thickness range is preferably 1 μm to 20 μm; the porosity of the nano conductive fiber layer is 10-60%, and the porosity is preferably 20-40%.
The thickness of the active material layer in step S4 is preferably in the range of 50 to 200 μm, and more preferably in the range of 100 to 200 μm.
The first solvent in the step S1 includes one or more of ethanol, ethylene glycol, propanol, N-methylpyrrolidone, N-Dimethylformamide (DMF), and isopropanol; the second solvent in step S3 includes one or more of water, ethanol, ethylene glycol, propanol, N-methylpyrrolidone, and isopropanol.
Examples 2,
Preparing a multilayer battery pole piece (positive pole piece) by the following specific steps:
s1, dispersion I: dispersing 10g of polyaniline in 40g of N, N-Dimethylformamide (DMF) organic solvent, mechanically stirring at 2000rpm for 2h, and filtering and defoaming to obtain a spinning solution with polyaniline dispersion concentration of 20 wt%;
s2, electrostatic spinning: adding the spinning solution into an injector of an electrostatic spinning device, carrying out electrostatic spinning under a high-voltage electrostatic field of 15kV, wherein the receiving distance is 13cm, the ambient temperature is 25 ℃, the air humidity is 40%, the thin flow of the electrostatic spinning solution is solidified and formed in the air and is received on a foil layer made of aluminum foil, the duration time of the electrostatic spinning is 20min, then carrying out vacuum drying for 6h at 60 ℃ and the vacuum degree of 50mbar to obtain a nano conductive fiber layer with a net structure, and the thickness of the obtained nano conductive fiber layer is 15 mu m;
s3, dispersion II: mixing nickel cobalt lithium manganate (NCM523), carbon nanotube conductive agents (CNTs) and a binder polyvinylidene fluoride (PVDF) according to a weight ratio of 97:0.5:2.5, then adding N-methylpyrrolidone (NMP) to enable the N-methylpyrrolidone to account for 45% of the weight of the whole mixture, and mechanically stirring for 5 hours at 3000rpm to obtain positive active material slurry;
s4, coating: coating the anode active substance slurry on the nano conductive fiber layer to obtain an active substance layer;
s5, drying: and drying the composite layer consisting of the foil layer, the nano conductive fiber layer and the active material layer to obtain the multilayer battery pole piece.
Examples 3,
Preparing a multilayer electrode plate (positive electrode plate) by using the preparation method of the multilayer battery plate: the difference from example 2 is that polypyrrole was used as the conductive polymer in step S1.
Examples 4,
Preparing a multilayer electrode plate (positive electrode plate) by using the preparation method of the multilayer battery plate: the difference from example 2 is that 0.5g of polyaniline was dispersed in 49.5g of N, N-Dimethylformamide (DMF) organic solvent in step S1, and a spinning solution having a polyaniline dispersion concentration of 1 wt% was obtained after filtration and deaeration treatment.
Examples 5,
Preparing a multilayer electrode plate (positive electrode plate) by using the preparation method of the multilayer battery plate: the difference from example 2 is that in step S1, 2.5g of polyaniline was dispersed in 47.5g of N, N-Dimethylformamide (DMF) organic solvent, and the solution was filtered and deaerated to obtain a spinning solution having a polyaniline dispersion concentration of 5 wt%.
Examples 6,
Preparing a multilayer electrode plate (positive electrode plate) by using the preparation method of the multilayer battery plate: the difference from example 2 is that, in step S1, 15g of polyaniline was dispersed in 35g of N, N-Dimethylformamide (DMF) organic solvent in step S1, and the solution was filtered and deaerated to obtain a spinning solution having a polyaniline dispersion concentration of 30 wt%.
Example 7,
Preparing a multilayer electrode plate (positive electrode plate) by using the preparation method of the multilayer battery plate: the difference from example 2 is that, in step S3, nickel cobalt lithium manganate (NCM523), carbon nanotube conductive agents (CNTs), and a binder polyvinylidene fluoride (PVDF) are mixed in a weight ratio of 60:10: 40.
Example 8,
Preparing a multilayer electrode plate (positive electrode plate) by using the preparation method of the multilayer battery plate: the difference from example 2 is that, in step S3, nickel cobalt lithium manganate (NCM523), carbon nanotube conductive agent (CNTs), binder polyvinylidene fluoride (PVDF) are mixed in a weight ratio of 98:0.5: 1.5.
Examples 9,
Preparing a multilayer electrode plate (positive electrode plate) by using the preparation method of the multilayer battery plate: the difference from example 2 is that, in step S3, nickel cobalt lithium manganate (NCM523), carbon nanotube conductive agent (CNTs), binder polyvinylidene fluoride (PVDF) were mixed in a weight ratio of 95:1: 4.
Examples 10,
Preparing a multilayer electrode plate (positive electrode plate) by using the preparation method of the multilayer battery plate: the difference from example 2 is that in step S3, the second solvent added is isopropanol.
Examples 11,
Preparing a multilayer electrode plate (positive electrode plate) by using the preparation method of the multilayer battery plate: the difference from example 2 is that the thickness of the dried nano conductive fiber layer is 10 μm.
Examples 12,
Preparing a multilayer electrode plate (positive electrode plate) by using the preparation method of the multilayer battery plate: the difference from example 2 is that the thickness of the dried nano conductive fiber layer is 50 μm.
Examples 13,
Preparing a multilayer electrode plate (positive electrode plate) by using the preparation method of the multilayer battery plate: the difference from example 2 is that the thickness of the dried nano conductive fiber layer is 100 μm.
Examples 14,
Preparing a multilayer electrode plate (positive electrode plate) by using the preparation method of the multilayer battery plate: the difference from example 2 is that in step S2, vacuum drying is performed at a temperature of 30 ℃ for 12 hours.
Examples 15,
Preparing a multilayer electrode plate (positive electrode plate) by using the preparation method of the multilayer battery plate: the difference from example 2 is that in step S2, the drying was carried out in vacuum at a temperature of 80 ℃ for 2 hours.
Examples 16,
Preparing a multilayer battery pole piece (negative pole piece) by the following specific steps:
s1, dispersion I: dispersing 8g of polyaniline in 32g of N, N-Dimethylformamide (DMF) organic solvent, mechanically stirring at 2000rpm for 2h, and filtering and defoaming to obtain a spinning solution with polyaniline dispersion concentration of 20 wt%;
s2, electrostatic spinning: adding the spinning solution into an injector of an electrostatic spinning device, carrying out electrostatic spinning under a high-voltage electrostatic field of 15kV, wherein the receiving distance is 15cm, the ambient temperature is 25 ℃, the air humidity is 40%, the thin flow of the electrostatic spinning solution is solidified and formed in the air and is received on a foil layer made of aluminum foil, the duration time of the electrostatic spinning is 30min, then carrying out vacuum drying for 6h at 60 ℃ and the vacuum degree of 50mbar to obtain a nano conductive fiber layer with a net structure, and the thickness of the obtained nano conductive fiber layer is 15 mu m;
s3, dispersion II: firstly weighing 3g of sodium carboxymethylcellulose (CMC), adding the CMC into 150g of water, mechanically stirring for 3h at the rotating speed of 1000rpm to obtain a CMC solution, then adding the artificial graphite, the binder sodium carboxymethylcellulose (CMC) and the binder Styrene Butadiene Rubber (SBR) into the CMC solution according to the weight ratio of 96.5:0.5:1.5:1.5, mixing and pulping, and mechanically stirring for 5h at the rotating speed of 2500rpm to obtain negative electrode active material slurry;
s4, coating: coating the negative electrode active material slurry on the nano conductive fiber layer to obtain an active material layer;
s5, drying: and drying the composite layer consisting of the foil layer, the nano conductive fiber layer and the active material layer to obtain the multilayer battery pole piece.
Comparative examples 1,
The positive pole piece is prepared by the following specific steps:
s1, dispersing: mixing nickel cobalt lithium manganate (NCM523), carbon nanotube conductive agents (CNTs) and a binder polyvinylidene fluoride (PVDF) according to a weight ratio of 97:0.5:2.5, then adding N-methylpyrrolidone (NMP) to enable the N-methylpyrrolidone to account for 45% of the weight of the whole mixture, and mechanically stirring for 5 hours at 3000rpm to obtain positive active material slurry;
s2, coating: coating the positive active material slurry on a foil layer made of aluminum foil to obtain an active material layer;
s3, drying: and drying the composite layer consisting of the foil layer and the active material layer to obtain the multilayer battery pole piece.
Comparative examples 2,
The preparation method comprises the following specific steps of:
s1, dispersing: firstly weighing 3g of sodium carboxymethylcellulose (CMC), adding the CMC into 150g of water, mechanically stirring for 3h at the rotating speed of 1000rpm to obtain a CMC organic solution, then adding artificial graphite, conductive graphite (SP), binder carboxymethylcellulose sodium (CMC) and binder Styrene Butadiene Rubber (SBR) into the CMC organic solution according to the weight ratio of 96.5:0.5:1.5:1.5, mixing and pulping, and mechanically stirring for 5h at the rotating speed of 2500rpm to obtain negative electrode active material slurry;
s2, coating: coating the negative electrode active material slurry on a foil layer made of aluminum foil to obtain an active material layer;
s3, drying: and drying the composite layer consisting of the foil layer and the active material layer to obtain the multilayer battery pole piece.
The battery pole pieces prepared in the second embodiment, the third embodiment, the fourth embodiment, the first comparative embodiment and the second comparative embodiment are respectively subjected to wettability tests, and the test data are shown in the following table 1:
the battery pole pieces prepared in the second embodiment, the fifth embodiment, the fourth embodiment and the first embodiment are assembled into a battery, and the battery pole pieces are respectively subjected to cycle performance tests, wherein the test data are shown in the following table 2:
as can be seen from table 1, compared with the comparative example, the multilayer battery pole piece obtained by the preparation method of the present invention has the advantages that the electrolyte absorption amount is significantly increased, and is increased by 0.41g to the maximum, and the absorption time is also significantly reduced, and is reduced by 273s to the maximum, which indicates that after the nano conductive fiber layer is added, the pole piece can retain more electrolyte, the electrolyte infiltration path is increased, and the infiltration rate is significantly increased. As can be seen from Table 2, the capacity retention rate in the cycle performance test of the battery prepared by the embodiment of the invention is not obviously different from that of the comparative example in the initial cycle period, and after 500 cycles, the difference is larger, which shows that the pole piece of the embodiment has excellent cycle performance.
Although preferred embodiments of the present invention have been described in detail hereinabove, it should be clearly understood that modifications and variations of the present invention are possible to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A preparation method of a multilayer battery pole piece is characterized by comprising the following steps: the method comprises the following steps:
s1, dispersion I: dispersing a conductive polymer in a first solvent, performing ultrasonic dispersion or mechanical stirring uniformly, and performing defoaming treatment to obtain a spinning solution with the conductive polymer dispersion concentration of 1-30 wt%;
s2, electrostatic spinning: adding the spinning solution into an injector of an electrostatic spinning device, carrying out electrostatic spinning in a high-voltage electrostatic field, solidifying and forming the electrostatic spinning solution trickle in the air, receiving the electrostatic spinning solution trickle on a foil layer, and then carrying out vacuum drying at the temperature of 30-80 ℃ to obtain a nano conductive fiber layer with a net structure;
s3, dispersion II: dispersing an active substance, a conductive agent and a binder in a second solvent, and performing ultrasonic dispersion or mechanical stirring uniformly to obtain active substance slurry with the active substance ratio of 50-98 wt%, the conductive agent concentration of 0.1-10 wt% and the binder concentration of 0.5-30 wt%;
s4, coating: coating the active substance slurry on the nano conductive fiber layer to obtain an active substance layer;
s5, drying: and drying the composite layer consisting of the foil layer, the nano conductive fiber layer and the active material layer to obtain the multilayer battery pole piece.
2. The method for preparing a multilayer battery pole piece according to claim 1, characterized in that: the conductive polymer in the step S1 is polyaniline and/or polypyrrole, and the fiber diameter of the polyaniline and the polypyrrole is 10nm to 1000 nm.
3. The method for preparing a multilayer battery pole piece according to claim 1, characterized in that: the thickness range of the nano conductive fiber layer in the step S2 is 0.1-100 μm, and the porosity of the nano conductive fiber layer is 10-60%.
4. The method for preparing a multilayer battery pole piece according to claim 1, characterized in that: the thickness of the active layer in the step S4 ranges from 50 μm to 200 μm.
5. The method for preparing a multilayer battery pole piece according to claim 1, characterized in that: the active matter in the step S3 is a positive electrode material or a negative electrode material, the conductive agent includes one or more of carbon black, acetylene black, super-P, carbon nanotubes, carbon nanofibers, graphene, and redox graphite, and the binder includes one or more of polyvinylidene fluoride, styrene butadiene rubber, sodium carboxymethyl cellulose, and acrylonitrile multipolymer.
6. The method for preparing a multilayer battery pole piece according to claim 1, characterized in that: the first solvent in the step S1 includes one or more of ethanol, ethylene glycol, propanol, N-Dimethylformamide (DMF), N-methylpyrrolidone, and isopropanol; the second solvent in step S3 includes one or more of water, ethanol, ethylene glycol, propanol, N-methylpyrrolidone, and isopropanol.
7. The method for preparing the multilayer battery pole piece according to claim 1, characterized in that: the foil layer in step S2 is composed of one of a metal, a metal mixture, a metal/organic composite, and a metal/inorganic composite.
8. A multilayer battery pole piece, characterized in that: the multilayer battery pole piece prepared by the preparation method of the multilayer battery pole piece according to any one of claims 1 to 7.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103165899A (en) * | 2012-12-07 | 2013-06-19 | 深圳市海太阳实业有限公司 | Positive pole piece and preparation method thereof and battery |
| CN104821391A (en) * | 2015-03-18 | 2015-08-05 | 江苏乐能电池股份有限公司 | Preparation method for rate type lithium ion battery |
| CN105336916A (en) * | 2014-06-20 | 2016-02-17 | 东莞新能源科技有限公司 | Lithium ion battery pole piece and preparation method thereof |
| CN108428900A (en) * | 2018-03-15 | 2018-08-21 | 重庆市紫建电子有限公司 | A kind of based lithium-ion battery positive plate and preparation method thereof |
| CN112750980A (en) * | 2020-12-30 | 2021-05-04 | 远景动力技术(江苏)有限公司 | Negative plate, preparation method thereof and diaphragm-free battery cell |
-
2022
- 2022-05-05 CN CN202210481194.6A patent/CN114824171B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103165899A (en) * | 2012-12-07 | 2013-06-19 | 深圳市海太阳实业有限公司 | Positive pole piece and preparation method thereof and battery |
| CN105336916A (en) * | 2014-06-20 | 2016-02-17 | 东莞新能源科技有限公司 | Lithium ion battery pole piece and preparation method thereof |
| CN104821391A (en) * | 2015-03-18 | 2015-08-05 | 江苏乐能电池股份有限公司 | Preparation method for rate type lithium ion battery |
| CN108428900A (en) * | 2018-03-15 | 2018-08-21 | 重庆市紫建电子有限公司 | A kind of based lithium-ion battery positive plate and preparation method thereof |
| CN112750980A (en) * | 2020-12-30 | 2021-05-04 | 远景动力技术(江苏)有限公司 | Negative plate, preparation method thereof and diaphragm-free battery cell |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115188919A (en) * | 2022-08-22 | 2022-10-14 | 蜂巢能源科技(无锡)有限公司 | Negative plate, preparation method thereof and battery |
| CN115188919B (en) * | 2022-08-22 | 2024-01-02 | 蜂巢能源科技(无锡)有限公司 | Negative plate, preparation method thereof and battery |
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