CN114824171B - Preparation method of multi-layer battery pole piece and multi-layer battery pole piece - Google Patents
Preparation method of multi-layer battery pole piece and multi-layer battery pole piece Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000011149 active material Substances 0.000 claims abstract description 37
- 239000000835 fiber Substances 0.000 claims abstract description 36
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 28
- 239000011888 foil Substances 0.000 claims abstract description 24
- 238000000576 coating method Methods 0.000 claims abstract description 20
- 239000011248 coating agent Substances 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 19
- 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 25
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 20
- 239000006258 conductive agent Substances 0.000 claims description 20
- 239000011230 binding agent Substances 0.000 claims description 17
- 229920000767 polyaniline Polymers 0.000 claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 239000002002 slurry 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
- 229920002981 polyvinylidene fluoride Polymers 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 11
- 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 9
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 9
- 239000002041 carbon nanotube Substances 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 9
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 9
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 8
- 229920000128 polypyrrole Polymers 0.000 claims description 8
- 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
- 238000001132 ultrasonic dispersion 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
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 5
- 238000001291 vacuum drying Methods 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
- 239000007773 negative electrode material Substances 0.000 claims description 4
- 239000006230 acetylene black Substances 0.000 claims description 3
- 239000002134 carbon nanofiber Substances 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 19
- 230000008595 infiltration Effects 0.000 abstract description 14
- 238000001764 infiltration Methods 0.000 abstract description 14
- 238000009776 industrial production Methods 0.000 abstract description 2
- 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
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 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 6
- 239000002121 nanofiber Substances 0.000 description 6
- 239000006183 anode active material Substances 0.000 description 5
- 238000001914 filtration Methods 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
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910021383 artificial graphite Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000004519 manufacturing process 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
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910018068 Li 2 O 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
- 239000013543 active substance Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 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
- 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
- 239000004005 microsphere Substances 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
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Textile Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a multi-layer battery pole piece and the multi-layer battery pole piece, wherein the preparation method of the multi-layer battery pole piece comprises five steps of dispersing I, electrostatic spinning, dispersing II, coating and drying, and the multi-layer battery pole piece comprises a foil layer, a nano conductive fiber layer and an active material layer; the multi-layer battery pole piece obtained by the preparation method not only can effectively increase the porosity of the electrode piece and effectively improve the infiltration capacity of electrolyte, but also can reduce the contact resistance between different layers, and meanwhile, the preparation method is simpler 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 multi-layer battery pole piece and the multi-layer battery pole piece.
Background
The lithium ion battery is generally composed of a battery pole piece, a separation film and electrolyte, wherein the preparation method of the battery pole piece is to take a metal foil as a base material, coat slurry containing active matters, conductive agents and binders on the base material in an extrusion or transfer coating mode, and dry the base material to obtain the battery pole piece.
With the continuous improvement of energy density, the thickness of the traditional battery pole piece is correspondingly increased to improve the available capacity ratio, but the increase of the thickness of the battery pole piece can cause the increase of the difficulty of infiltration of electrolyte in the battery pole piece, and insufficient infiltration can cause the problems of insufficient capacity exertion, shortened cycle life and the like.
In order to improve the infiltration effect of the electrolyte on the battery pole piece, the electrolyte can be considered from the two aspects of dynamics and thermodynamics. In the aspect of dynamics, the sufficient infiltration of the electrolyte is ensured by increasing the standing time after the liquid filling 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 a battery pole piece, such as an electrode and a preparation method thereof in Chinese patent application No. 202010021572.3 (CN 113097442A), the technical scheme disclosed by the thermodynamic method comprises a current collector, a plurality of through hole layers and a plurality of active layers, wherein the through hole layers are formed by a network structure of high polymers, when the thermodynamic method is used, the high polymers are dissolved in electrolyte and form a pore structure with controllable pore size and distribution, and the electrode structure adopts the through hole layers which are electronically insulated, so that the contact resistance among all layers can be greatly increased, the battery performance is influenced, and meanwhile, the preparation method adopted by the thermodynamic method has the problem of coating for two or more times, so that the technological requirement is high, and the mass production is not facilitated.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a multi-layer battery pole piece and the multi-layer battery pole piece, which not only can effectively increase the porosity of the electrode pole piece and effectively improve the infiltration capacity of electrolyte, but also can reduce the contact resistance between different layers.
The technical scheme adopted for solving the technical problems is as follows:
the preparation method of the multilayer battery pole piece comprises the following steps:
s1, dispersing I: dispersing the conductive polymer in a first solvent, and carrying out ultrasonic dispersion or mechanical stirring uniformly to obtain spinning solution with the dispersion concentration of the conductive polymer being 1-30wt% after defoaming treatment;
s2, electrostatic spinning: adding spinning solution into an injector of an electrostatic spinning device, carrying out electrostatic spinning under a high-voltage electrostatic field, solidifying and forming an electrostatic spinning solution trickle in air, receiving the electrostatic spinning solution trickle on a foil layer, and then carrying out vacuum drying at a temperature of 30-80 ℃ to obtain a nano conductive fiber layer with a net structure;
s3, dispersing II: dispersing the active material, the conductive agent and the binder in a second solvent, and carrying out ultrasonic dispersion or mechanical stirring uniformly to obtain active material slurry with the active material accounting for 50-98 wt%, the conductive agent concentration being 0.1-10 wt% and the binder concentration being 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 the step S1 is polyaniline and/or polypyrrole, and the fiber diameter of polyaniline and polypyrrole is 10 nm-1000 nm.
Preferably, the thickness of the nanofiber layer in the step S2 is in the range of 0.1 μm to 100 μm, and the porosity of the nanofiber layer is 10% to 60%.
Preferably, the thickness of the active material layer in the step S4 is in the range of 50 μm to 200. Mu.m.
Preferably, the active material 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, a supplier-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 copolymer.
Preferably, 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 the step S3 comprises one or more of water, ethanol, glycol, propanol, N-methyl pyrrolidone and isopropanol.
Preferably, the foil layer in the step S2 is composed of one of metal, metal mixture, metal/organic composite, and metal/inorganic composite.
The invention also provides a multi-layer battery pole piece, which is prepared by adopting the preparation method of the multi-layer 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 material layer, so that the toughness of the battery pole piece can be increased, the nano conductive fiber layer is in a net structure, the porosity is larger, the infiltration path of electrolyte can be increased, one-way infiltration is changed into two-way infiltration, meanwhile, swelling can be generated after the nano conductive fiber is soaked by the electrolyte, the volume is increased, a certain 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 electronic conduction capability;
3) The nanometer conductive fiber layer can conduct electrons, the conductive state is netlike continuous conduction, contact resistance among different layers of the battery pole piece is reduced, the electron conductivity of the inactive material layer is improved, and the multiplying power performance of the battery is further improved;
4) The method combining electrostatic spinning and a single coating process is adopted, multiple coating is not needed, the process difficulty is reduced, and the industrial production is convenient.
Drawings
FIG. 1 is a schematic cross-sectional view of a multi-layered battery pole piece of the present invention;
fig. 2 is a schematic view of an electrolyte infiltration path.
In the figure, 1, a foil layer; 2. a nano conductive fiber layer; 3. an active layer; 4. and (3) an electrolyte.
Detailed Description
The invention is described in further detail below with reference to the embodiments of the drawings.
Example 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 a conductive polymer, and the conductive polymer is composed of polyaniline and/or polypyrrole; the active material layer 3 includes an active material, which is a positive electrode material or a negative electrode material, a conductive agent, which includes one or more of carbon black, acetylene black, a supplier-P, carbon nanotubes, carbon nanofibers, graphene, and redox graphite, and a binder, which includes one or more of polyvinylidene fluoride (PVDF), styrene-butadiene rubber (SBR), sodium carboxymethyl cellulose (CMC), and an acrylonitrile copolymer.
Further, according to the application of the multi-layer battery pole piece in the battery, the multi-layer battery pole piece can be divided into a positive pole piece and a negative pole piece, when the multi-layer battery pole piece is the positive pole piece, the active substance adopts a positive pole material, and the positive pole material comprises one or more of lithium cobaltate, lithium iron phosphate or lithium nickel cobalt manganate; when the multi-layer 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 a silicon-containing compound or a compound 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 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, mesophase carbon microspheres and lithium titanate.
When the multi-layer battery pole piece is immersed in the electrolyte 4, the electrolyte 4 is immersed in the multi-layer battery pole piece in a two-way manner (see fig. 2), so that the immersing 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, dispersing I: dispersing the conductive polymer in a first solvent, and carrying out ultrasonic dispersion or mechanical stirring uniformly to obtain spinning solution with the dispersion concentration of the conductive polymer being 1-30wt% after defoaming treatment;
s2, electrostatic spinning: adding spinning solution into an injector of an electrostatic spinning device, carrying out electrostatic spinning under a high-voltage electrostatic field, solidifying and forming an electrostatic spinning solution trickle in air, receiving the electrostatic spinning solution trickle on a foil layer, and then carrying out vacuum drying at a temperature of 30-80 ℃ to obtain a nano conductive fiber layer with a net structure;
s3, dispersing II: dispersing the active material, the conductive agent and the binder in a second solvent, and carrying out ultrasonic dispersion or mechanical stirring uniformly to obtain active material slurry with the active material accounting for 50-98 wt%, the conductive agent concentration being 0.1-10 wt% and the binder concentration being 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.
The conductive polymer is polyaniline and/or polypyrrole, the fiber diameter of polyaniline and polypyrrole is 10 nm-1000 nm, and the fiber diameter is preferably 10 nm-100 nm.
The thickness of the nanofiber layer in the step S2 is in the range of 0.1 μm to 100. Mu.m, preferably 1 μm to 20. Mu.m; 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 the step S4 is in the range of 50 μm to 200. Mu.m, and the thickness is preferably in the range of 100 μm to 200. Mu.m.
The first solvent in the step S1 comprises one or more of ethanol, ethylene glycol, propanol, N-methyl pyrrolidone, N-Dimethylformamide (DMF) and isopropanol; the second solvent in step S3 comprises one or more of water, ethanol, ethylene glycol, propanol, N-methylpyrrolidone, isopropanol.
EXAMPLE 2,
The multilayer battery pole piece (positive pole piece) is prepared by the following specific steps:
s1, dispersing I: dispersing 10g of polyaniline in 40g of N, N-Dimethylformamide (DMF) organic solvent, mechanically stirring for 2 hours at a rotating speed of 2000rpm, and filtering and defoaming to obtain a spinning solution with the 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 electrostatic spinning solution trickles are solidified and formed in the air and are received on a foil layer made of aluminum foil, the electrostatic spinning duration is 20min, then carrying out vacuum drying for 6h at 60 ℃ and the vacuum degree is 50mbar, and obtaining a nano conductive fiber layer with a net-shaped structure, wherein the thickness of the nano conductive fiber layer is 15 mu m;
s3, dispersing II: mixing nickel cobalt lithium manganate (NCM 523), carbon nanotube conductive agent (CNTs) and binder polyvinylidene fluoride (PVDF) according to the weight ratio of 97:0.5:2.5, then adding N-methyl pyrrolidone (NMP) to make the N-methyl pyrrolidone account for 45% of the total mixture weight, and mechanically stirring for 5 hours according to 3000rpm to obtain positive electrode active material slurry;
s4, coating: coating the anode 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.
EXAMPLE 3,
The preparation method of the multilayer battery pole piece comprises the steps of: the difference from example 2 is that polypyrrole is used as the conductive polymer in step S1.
EXAMPLE 4,
The preparation method of the multilayer battery pole piece comprises the steps of: the difference from example 2 is that in step S1, 0.5g of polyaniline was dispersed in 49.5g of N, N-Dimethylformamide (DMF) organic solvent, and the resultant was subjected to filtration and defoaming treatment to obtain a spinning solution having a polyaniline dispersion concentration of 1 wt%.
EXAMPLE 5,
The preparation method of the multilayer battery pole piece comprises the steps of: 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 resultant was subjected to filtration and defoaming treatment to obtain a spinning solution having a polyaniline dispersion concentration of 5 wt%.
EXAMPLE 6,
The preparation method of the multilayer battery pole piece comprises the steps of: 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 resultant was subjected to filtration and defoaming treatment to obtain a spinning solution having a polyaniline dispersion concentration of 30 wt%.
EXAMPLE 7,
The preparation method of the multilayer battery pole piece comprises the steps of: the difference from example 2 is that in step S3, lithium nickel cobalt manganate (NCM 523), carbon nanotube conductive agents (CNTs), binder polyvinylidene fluoride (PVDF) are mixed in a weight ratio of 60:10:40.
EXAMPLE 8,
The preparation method of the multilayer battery pole piece comprises the steps of: the difference from example 2 is that in step S3, lithium nickel cobalt manganate (NCM 523), carbon nanotube conductive agent (CNTs), binder polyvinylidene fluoride (PVDF) are mixed in a weight ratio of 98:0.5:1.5.
EXAMPLE 9,
The preparation method of the multilayer battery pole piece comprises the steps of: the difference from example 2 is that in step S3, lithium nickel cobalt manganate (NCM 523), carbon nanotube conductive agents (CNTs), binder polyvinylidene fluoride (PVDF) are mixed in a weight ratio of 95:1:4.
EXAMPLE 10,
The preparation method of the multilayer battery pole piece comprises the steps of: the difference from example 2 is that in step S3, the second solvent added is isopropanol.
EXAMPLE 11,
The preparation method of the multilayer battery pole piece comprises the steps of: the difference from example 2 is that the thickness of the dried nanofiber layer was 10 μm.
EXAMPLE 12,
The preparation method of the multilayer battery pole piece comprises the steps of: the difference from example 2 is that the thickness of the dried nanofiber layer was 50 μm.
EXAMPLE 13,
The preparation method of the multilayer battery pole piece comprises the steps of: the difference from example 2 is that the thickness of the dried nanofiber layer was 100 μm.
EXAMPLE 14,
The preparation method of the multilayer battery pole piece comprises the steps of: the difference from example 2 is that in step S2, the drying is performed in vacuum at a temperature of 30 c for a drying time of 12 hours.
EXAMPLE 15,
The preparation method of the multilayer battery pole piece comprises the steps of: the difference from example 2 is that in step S2, the drying is carried out in vacuum at a temperature of 80℃for a drying time of 2h.
EXAMPLE 16,
The multi-layer battery pole piece (negative pole piece) is prepared by the following specific steps:
s1, dispersing I: dispersing 8g of polyaniline in 32g of N, N-Dimethylformamide (DMF) organic solvent, mechanically stirring for 2 hours at a rotating speed of 2000rpm, and filtering and defoaming to obtain a spinning solution with the 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 electrostatic spinning solution trickles are solidified and formed in the air and are received on a foil layer made of aluminum foil, the electrostatic spinning duration is 30min, then vacuum drying is carried out for 6h under the vacuum degree of 50mbar at the temperature of 60 ℃, and the nano conductive fiber layer with a net-shaped structure is obtained, wherein the thickness of the obtained nano conductive fiber layer is 15 mu m;
s3, dispersing II: firstly, weighing 3g of sodium carboxymethyl cellulose (CMC), adding the sodium carboxymethyl cellulose (CMC) into 150g of water, mechanically stirring the mixture according to the rotating speed of 1000rpm for 3 hours to obtain CMC solution, then adding artificial graphite, binder sodium carboxymethyl cellulose (CMC) and 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 the mixture, and mechanically stirring the mixture according to the rotating speed of 2500rpm for 5 hours to obtain anode active material slurry;
s4, coating: coating the anode 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 example 1,
The positive electrode plate is prepared through the following specific steps:
s1, dispersing: mixing nickel cobalt lithium manganate (NCM 523), carbon nanotube conductive agent (CNTs) and binder polyvinylidene fluoride (PVDF) according to the weight ratio of 97:0.5:2.5, then adding N-methyl pyrrolidone (NMP) to make the N-methyl pyrrolidone account for 45% of the total mixture weight, and mechanically stirring for 5 hours according to 3000rpm to obtain positive electrode active material slurry;
s2, coating: coating positive 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 formed by the foil layer and the active material layer to obtain the multi-layer battery pole piece.
Comparative example 2,
The negative electrode plate is prepared through the following specific steps:
s1, dispersing: firstly, weighing 3g of sodium carboxymethyl cellulose (CMC), adding the sodium carboxymethyl cellulose (CMC) into 150g of water, mechanically stirring the mixture according to the rotating speed of 1000rpm for 3 hours to obtain CMC organic solution, then adding artificial graphite, conductive graphite (SP), adhesive sodium carboxymethyl cellulose (CMC) and adhesive 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 the mixture, and mechanically stirring the mixture according to the rotating speed of 2500rpm for 5 hours to obtain anode active material slurry;
s2, coating: coating the anode active material slurry on a foil layer made of aluminum foil to obtain an active material layer;
s3, drying: and drying the composite layer formed by the foil layer and the active material layer to obtain the multi-layer battery pole piece.
Wettability tests are respectively carried out on the battery pole pieces prepared in the second embodiment, the third embodiment, the fourth embodiment, the first comparative embodiment and the second comparative embodiment, and the test data are shown in the following table 1:
the battery pole pieces prepared in the second, fifth, fourth and comparative examples were assembled into batteries, and respectively subjected to cycle performance test, and the test data are shown in table 2 below:
as can be seen from Table 1, compared with the comparative example, the electrolyte absorption amount of the multi-layer battery pole piece obtained by the preparation method provided by the invention is obviously improved by 0.41g at maximum, the liquid absorption time is obviously reduced, and 273s at maximum, which means that after the nano conductive fiber layer is added, more electrolyte can be reserved on the pole piece, the electrolyte infiltration path is increased, and the infiltration rate is obviously improved. As is clear from Table 2, the battery prepared in the examples of the present invention has no significant difference in the cycle performance test capacity retention rate from the comparative example at the initial cycle, and a large difference occurs after 500 weeks of cycle, indicating that the pole pieces of the examples have excellent cycle performance.
While the preferred embodiments of the present invention have been described in detail, it is to be clearly understood that the same may be varied in many ways by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. A preparation method of a multilayer battery pole piece is characterized by comprising the following steps: the method comprises the following steps:
s1, dispersing I: dispersing the conductive polymer in a first solvent, and carrying out ultrasonic dispersion or mechanical stirring uniformly to obtain spinning solution with the dispersion concentration of the conductive polymer being 1-30wt% after defoaming treatment;
s2, electrostatic spinning: adding spinning solution into an injector of an electrostatic spinning device, carrying out electrostatic spinning under a high-voltage electrostatic field, solidifying and forming an electrostatic spinning solution trickle in air, receiving the electrostatic spinning solution trickle on a foil layer, and then carrying out vacuum drying at a temperature of 30-80 ℃ to obtain a nano conductive fiber layer with a net structure;
s3, dispersing II: dispersing the active material, the conductive agent and the binder in a second solvent, and carrying out ultrasonic dispersion or mechanical stirring uniformly to obtain active material slurry with the active material accounting for 50-98 wt%, the conductive agent concentration being 0.1-10 wt% and the binder concentration being 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: drying a composite layer consisting of the foil layer, the nano conductive fiber layer and the active material layer to obtain a multi-layer battery pole piece;
the conductive polymer in the step S1 is polyaniline and/or polypyrrole, and the fiber diameter of the polyaniline and the polypyrrole is 10 nm-1000 nm;
the first solvent in the step S1 comprises one or more of ethanol, glycol, propanol, N-Dimethylformamide (DMF), N-methylpyrrolidone and isopropanol; the second solvent in the step S3 comprises one or more of water, ethanol, glycol, propanol, N-methyl pyrrolidone and isopropanol.
2. The method for preparing the multi-layer battery pole piece according to claim 1, wherein: the thickness range of the nano conductive fiber layer in the step S2 is 0.1-100 mu m, and the porosity of the nano conductive fiber layer is 10-60%.
3. The method for preparing the multi-layer battery pole piece according to claim 1, wherein: the thickness of the active material layer in the step S4 is in the range of 50 μm to 200. Mu.m.
4. The method for preparing the multi-layer battery pole piece according to claim 1, wherein: the active material in the step S3 is a positive electrode material or a negative electrode material, the conductive agent comprises one or more of carbon black, acetylene black, a supplier-P, carbon nanotubes, carbon nanofibers, graphene and redox graphite, and the binder comprises one or more of polyvinylidene fluoride, styrene-butadiene rubber, sodium carboxymethyl cellulose and acrylonitrile multipolymer.
5. A multilayer battery pole piece, characterized in that: a multilayer battery pole piece prepared by the preparation method of the multilayer battery pole piece according to any one of claims 1 to 4.
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| 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 |
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| 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 |
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| 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 |
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