CN117174909A - Aqueous organic positive electrode slurry and preparation method and application thereof - Google Patents
Aqueous organic positive electrode slurry and preparation method and application thereof Download PDFInfo
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- 239000011267 electrode slurry Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000002612 dispersion medium Substances 0.000 claims abstract description 34
- 239000006258 conductive agent Substances 0.000 claims abstract description 29
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000007774 positive electrode material Substances 0.000 claims abstract description 20
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 19
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011230 binding agent Substances 0.000 claims abstract description 15
- 239000011630 iodine Substances 0.000 claims abstract description 15
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- -1 benzoquinone compound Chemical class 0.000 claims description 10
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 7
- 239000006229 carbon black Substances 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 239000004642 Polyimide Substances 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- 239000003292 glue Substances 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000011888 foil Substances 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 239000002134 carbon nanofiber Substances 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 229920001940 conductive polymer Polymers 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 229920001197 polyacetylene Polymers 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 2
- 229920000128 polypyrrole Polymers 0.000 claims description 2
- 229920001021 polysulfide Polymers 0.000 claims description 2
- 239000005077 polysulfide Substances 0.000 claims description 2
- 150000008117 polysulfides Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920000123 polythiophene Polymers 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 12
- 239000013543 active substance Substances 0.000 abstract description 10
- 239000002002 slurry Substances 0.000 abstract description 7
- 238000005056 compaction Methods 0.000 abstract description 6
- 238000009826 distribution Methods 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 13
- 238000012360 testing method Methods 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 4
- 239000010405 anode material Substances 0.000 description 4
- 229910001425 magnesium ion Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 description 1
- 229940076442 9,10-anthraquinone Drugs 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical group COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage 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
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a water-based organic positive electrode slurry, a preparation method and application thereof, wherein the water-based organic positive electrode slurry comprises an organic positive electrode active substance, a dispersion medium, a binder, a conductive agent and water, and the dispersion medium comprises iodine simple substance and/or naphthalene; by adding the iodine simple substance and/or naphthalene into the slurry as a dispersion medium, the particle size distribution of the organic positive electrode active material in the homogenizing process is effectively reduced, the dispersibility of the conductive agent in the homogenizing process is effectively improved, the aqueous organic positive electrode slurry has excellent conductive performance under the condition of low conductive agent addition, the aqueous organic positive electrode sheet prepared further has low sheet resistivity, proper sheet porosity and high compaction density, and the capacity and the cycle performance of a lithium ion battery prepared by adopting the aqueous organic positive electrode sheet are further effectively improved.
Description
Technical Field
The invention belongs to the technical field of slurry, and particularly relates to aqueous organic positive electrode slurry, and a preparation method and application thereof.
Background
Lithium ion batteries are widely used due to their light weight, high power, long life, and the like. Currently, the commercial lithium ion battery anode material mainly comprises inorganic materials of Lithium Cobalt Oxide (LCO), lithium Manganate (LMO), lithium iron phosphate (LFP), ternary materials of lithium Nickel Cobalt Manganate (NCM) and lithium Nickel Cobalt Aluminate (NCA)), however, as the demand of people for lithium ion batteries is higher and higher, limited lithium resources are continuously paid attention to, and development of a plurality of novel energy sources is gradually carried out.
The organic active substance can be artificially synthesized, and breaks through the barrier of the theoretical capacity of the existing inorganic material by designing the structure of the organic active substance, and meanwhile, the organic active substance has the characteristics of wide sources of raw materials, abundant resources, compliance with the national green sustainable development strategy and the like, and is paid attention to. CN108470940a discloses a full organic magnesium ion battery, comprising an anode, a cathode, electrolyte, a diaphragm and a packaging material; the anode is made of polyimide anode material, the cathode is made of P-type organic polymer anode material, and the electrolyte is an organic electrolyte solution containing magnesium electrolyte salt; the anode material and the cathode material comprise organic active substances, conductive agents, binders and current collectors, and the conventional organic electrolyte based on magnesium salts is matched with an organic polymer cathode to construct a magnesium ion battery; the P-type organic polymer electrode material is used for the positive electrode of the magnesium ion battery, and energy storage is carried out by combining/removing anions; the all-organic magnesium ion battery based on the polyimide cathode and the P-type polymer cathode has good cycle performance and multiplying power performance, higher output voltage, simple preparation and lower cost.
However, compared with inorganic materials, the organic active material has the defects of lower hardness and extremely poor conductivity, and is easy to dissolve in electrolyte, and further, more conductive agents are needed to be added into the positive electrode slurry to improve the conductivity of the slurry, so that the organic positive electrode slurry is difficult to homogenize, and meanwhile, the further prepared positive electrode plate has the problems of low compaction density and easy cracking, poor cycle performance of the finally prepared battery, and the like.
Therefore, in order to solve the above-mentioned problems, development of an aqueous organic positive electrode slurry having excellent dispersion properties and conductivity properties is urgently required.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide aqueous organic positive electrode slurry, a preparation method and application thereof, wherein the aqueous organic positive electrode slurry comprises an organic positive electrode active material, a dispersion medium, a binder, a conductive agent and water, the dispersion medium comprises iodine simple substance and/or naphthalene, the dispersibility of the organic positive electrode active material and the conductive agent is effectively improved by adding the iodine simple substance and/or the naphthalene into the slurry as the dispersion medium, the obtained organic positive electrode slurry has excellent dispersibility, the aqueous organic positive electrode sheet further prepared has lower sheet resistivity, higher compaction density and proper sheet porosity, and the finally prepared lithium ion battery has higher capacity, excellent multiplying power performance and cycle performance.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an aqueous organic positive electrode slurry comprising an organic positive electrode active material, a dispersion medium, a binder, a conductive agent, and water;
the dispersion medium comprises elemental iodine and/or naphthalene.
The aqueous organic positive electrode slurry provided by the invention comprises an organic positive electrode active material, a dispersion medium, a conductive agent, a binder and water, wherein the dispersion medium comprises iodine simple substance and/or naphthalene; according to the method, iodine simple substance and/or naphthalene which are high in hardness and capable of volatilizing are added into the aqueous organic positive electrode slurry to serve as a dispersion medium, the dispersion medium can be used for continuously colliding with organic positive electrode active substances in the process of homogenizing, so that particle size distribution of the organic positive electrode active substances after homogenizing is greatly reduced, dispersibility of a conductive agent in the process of homogenizing is effectively improved, coating rate of the conductive agent on the surface of the organic positive electrode active substances is higher, aqueous organic positive electrode slurry with excellent conductivity can be obtained under the condition that the addition amount of the conductive agent is low, the proportion of the conductive agent in the aqueous organic positive electrode slurry is effectively reduced, the aqueous organic positive electrode plate which is further manufactured has lower resistivity, and meanwhile, the dispersion medium can be volatilized partially or completely in the process of manufacturing the aqueous organic positive electrode plate, and is not left, normal use of the organic positive electrode plate is not affected, and finally the aqueous organic positive electrode plate with lower resistivity, higher porosity and good cycle performance of a battery can be manufactured into a positive electrode plate with higher cycling capacity.
Preferably, the organic positive electrode active material includes a conductive polymer.
Preferably, the organic positive electrode active material includes any one or a combination of at least two of polyacetylene, polyphenyl, polypyrrole, polythiophene, an active polysulfide, a benzoquinone compound, or an anthraquinone compound, and further preferably a benzoquinone compound and/or an anthraquinone compound.
Preferably, the dispersion medium comprises elemental iodine and/or naphthalene.
The mass of the dispersion medium is preferably 0.1 to 50%, for example, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% or 50%, etc., and more preferably 5 to 30%, based on 100% of the mass of the organic positive electrode active material.
As a preferable technical scheme of the invention, the mass of the dispersion medium in the aqueous organic slurry is further limited to 5-30%, if the content of the dispersion medium in the aqueous organic positive electrode slurry is too high, the porosity of the further prepared organic positive electrode plate is easily too high, and the compaction density is reduced; if the content of the dispersion medium in the aqueous organic positive electrode slurry is too low, the porosity of the organic positive electrode sheet is liable to be small, and the dispersion of the conductive agent becomes poor, so that the resistivity of the further prepared organic positive electrode sheet becomes large.
Preferably, the binder comprises any one or a combination of at least two of styrene butadiene rubber, carboxymethyl cellulose, polyacrylic acid, polyacrylonitrile, polyacrylate, polytetrafluoroethylene or polyimide.
Preferably, the binder is 1 to 15% by mass, for example, 2%, 4%, 6%, 8%, 10%, 12% or 14% by mass, based on 100% by mass of the organic positive electrode active material.
Preferably, the conductive agent includes any one or a combination of at least two of carbon black, conductive graphite, carbon nanotubes or carbon nanofibers, and further preferably a combination of carbon black and carbon nanotubes.
Preferably, the conductive agent is 0.5 to 15% by mass, for example, 2%, 4%, 6%, 8%, 10%, 12% or 14% by mass, based on 100% by mass of the organic positive electrode active material.
Preferably, the aqueous organic positive electrode slurry has a solid content of 30 to 65%, for example, 32%, 34%, 36%, 38%, 40%, 41%, 42%, 43%, 44%, 50%, 58%, or the like.
Preferably, the aqueous organic positive electrode slurry has a viscosity of 4500 to 7500 mPa-s, for example 4700 mPa-s, 4900 mPa-s, 5100 mPa-s, 5300 mPa-s, 5500 mPa-s, 5700 mPa-s, 5900 mPa-s, 6200 mPa-s, 6400 mPa-s, 6600 mPa-s, 6800 mPa-s, 7000 mPa-s, 7200 mPa-s, or the like.
Preferably, the fineness of the aqueous organic positive electrode slurry is not higher than 35 μm, for example 34 μm, 33 μm, 32 μm, 31 μm, 30 μm, 29 μm, 28 μm, 27 μm, 26 μm, 25 μm or the like.
In a second aspect, the present invention provides a method for preparing the aqueous organic positive electrode slurry according to the first aspect, the method comprising the steps of:
(1) Mixing the conductive agent and part of the binder to obtain conductive glue solution;
(2) Mixing the dispersion medium with the conductive adhesive solution obtained in the step (1), adding an organic positive electrode active material for mixing, adding the rest of the adhesive for mixing, and finally adding water for mixing to obtain the aqueous organic positive electrode slurry.
Preferably, the temperature of the mixing in step (2) is not higher than 30 ℃, e.g. 29 ℃, 28 ℃, 27 ℃, 26 ℃, 25 ℃, 24 ℃, 23 ℃, 22 ℃, 21 ℃, 20 ℃, etc.
Preferably, the mixing in step (2) is performed under stirring.
Preferably, the stirring speed is 500-10000 rpm, such as 1000r/min, 2000r/min, 3000r/min, 4000r/min, 5000r/min, 6000r/min, 7000r/min, 8000r/min, 9000r/min, etc.
Preferably, the mixing time of step (2) is each independently 5 to 480min, e.g. 10min, 50min, 100min, 150min, 200min, 250min, 300min, 350min, 400min or 450min, etc.
In a third aspect, the present invention provides an aqueous organic positive electrode sheet, which includes a positive electrode current collector and the aqueous organic positive electrode slurry according to the first aspect attached to the surface of the positive electrode current collector after drying.
Preferably, the positive electrode current collector is carbon-coated aluminum foil.
Preferably, the drying includes a first drying and a second drying.
Preferably, the temperature of the first drying is 50 to 90 ℃, for example 55 ℃, 65 ℃, 75 ℃,80 ℃, 85 ℃, or the like.
Preferably, the temperature of the second drying is 90 to 140 ℃, for example 95 ℃, 105 ℃, 115 ℃, 125 ℃, 135 ℃, or the like.
During the above-described first drying and second drying, the dispersion medium in the organic positive electrode slurry may be partially or even totally volatilized by heat.
In a fourth aspect, the invention provides a lithium ion battery comprising the aqueous organic positive electrode sheet according to the third aspect.
Compared with the prior art, the invention has the following beneficial effects:
the aqueous organic positive electrode slurry provided by the invention comprises an organic active substance, a dispersion medium, a binder, a conductive agent and water, wherein the dispersion medium comprises iodine simple substance and/or naphthalene; by adding iodine simple substance and/or naphthalene into the aqueous organic positive electrode slurry as a dispersion medium, the particle size distribution of the organic positive electrode active material in the homogenizing process can be effectively reduced, the dispersibility of the conductive agent can be effectively improved, the coating effect of the conductive agent on the surface of the organic positive electrode active material can be improved, the organic positive electrode slurry still has excellent conductive performance under the condition of lower conductive agent addition, and the further prepared organic positive electrode sheet has lower sheet resistivity, proper sheet porosity and higher compaction density, so that the capacity, the circulation performance and the multiplying power performance of a lithium ion battery prepared by adopting the organic positive electrode sheet are effectively improved.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Preparation example 1
An organic anthraquinone material, in particular 9, 10-anthraquinone, has the structural formula:
preparation example 2
An organic benzoquinone material, specifically p-benzoquinone, has the structural formula:
examples 1 to 9 and comparative examples 1 to 2
An aqueous organic positive electrode slurry with specific compositions shown in table 1;
in Table 1, the amounts of the respective components are "parts by weight", the organic anthraquinone material is derived from preparation example 1, the organic benzoquinone material is derived from preparation example 2, and the molecular weight of the polyacrylic acid is about 50 ten thousand;
TABLE 1
The preparation method of the aqueous organic positive electrode slurry provided in examples 1 to 9 and comparative examples 1 to 2 comprises the following steps:
(1) Dispersing the conductive agent and part of the binder at a high speed for 30min under the condition of a rotating speed of 3000r/min to obtain conductive glue solution;
(2) Dispersing the conductive glue solution and the dispersion medium obtained in the step (1) at a high speed for 30min under the condition of a rotating speed of 3000r/min at a temperature of 25 ℃, adding an organic active substance, continuing to disperse at a high speed for 3h under the condition of a rotating speed of 3000r/min, adding the rest of the binder, dispersing at a high speed for 30min under the condition of a rotating speed of 2000r/min, and finally adding deionized water to adjust the viscosity of the slurry to 5000 mPa.s and the fineness of the slurry to be less than or equal to 35 mu m, thereby obtaining the aqueous organic positive electrode slurry.
Application example 1
A lithium ion button cell comprises a positive electrode, a negative electrode, a diaphragm and electrolyte;
wherein, the positive electrode is a water-based organic positive electrode plate, and the specific preparation method comprises the following steps: the aqueous organic positive electrode slurry obtained in example 1 was subjected to a single-sided surface density of 6mg/cm 2 Coating on carbon-coated aluminum foil, drying at 70deg.C, and rolling under 100MPa to obtain pole piece with compaction density of 1.1g/cm 3 Finally, drying at 110 ℃ to obtain a water-based organic positive electrode plate;
the negative electrode is lithium metal;
the diaphragm is a 9+2+2 double-layer coated ceramic diaphragm;
the electrolyte is diethylene glycol dimethyl ether;
the preparation process of the button lithium ion battery provided by the application example comprises the following steps: and assembling the aqueous organic positive electrode plate, the diaphragm and the metallic lithium, and dropwise adding electrolyte to obtain the lithium ion button cell.
Application examples 2 to 9
The lithium ion button cell was different from application example 1 only in that the aqueous organic positive electrode slurries provided in examples 2 to 9 were used in place of the aqueous organic positive electrode slurry provided in example 1, and reference was made to application example 1 for other substances, amounts of use and preparation processes.
Comparative application examples 1 to 2
The lithium ion button cell was different from application example 1 only in that the aqueous organic positive electrode slurries provided in comparative examples 1 to 2 were used in place of the aqueous organic positive electrode slurry provided in example 1, respectively, and reference was made to application example 1 for other substances, amounts and preparation processes.
Performance test:
(1) Interface resistance: using a diaphragm resistance test system, and adopting a two-probe method to test;
(2) Volume resistivity: testing by adopting a four-probe resistance tester;
(3) Porosity: the test was performed using the hexadecane absorption method.
The aqueous organic positive electrode sheets in application examples 1 to 9 and comparative application examples 1 to 2 were tested according to the above test method, and the test results are shown in table 2:
TABLE 2
As can be seen from the data in table 2:
the aqueous organic positive electrode plate of the aqueous organic positive electrode slurry provided by the invention has excellent conductivity and proper porosity;
specifically, the interface resistance of the aqueous organic positive electrode sheet provided in application examples 1 to 4 is 0.15 to 0.20 Ω·m, the volume resistivity is 4.13 to 4.88 Ω·cm, and the porosity is 32.37 to 38.11%;
as can be seen from the data of comparative application examples 1 and 1, comparative application examples 4 and 2, the interface resistance and volume resistivity of the aqueous organic positive electrode sheets provided in comparative application examples 1 to 2 are both high, which indicates that the aqueous organic positive electrode slurry prepared without adding the dispersion medium has poor dispersibility, and further the conductivity of the aqueous organic positive electrode sheet prepared further is poor;
as can be seen from comparing the data of application examples 1 and 5, the interfacial resistance and the volume resistance of the organic positive electrode sheet provided in application example 5 are also increased, which indicates that the effect of improving the dispersibility of naphthalene serving as a dispersion medium on the organic positive electrode slurry is slightly worse than that of iodine simple substance;
further comparing the data of application example 1 and application examples 6 to 7, it can be seen that too low an addition amount of the dispersion medium (elemental iodine) can lead to limited improvement of the conductivity of the obtained organic positive electrode sheet, while too high an addition amount of the dispersion medium (elemental iodine) can lead to too high porosity of the obtained organic positive electrode sheet;
finally, as can be seen from the comparison of the data of application examples 1 and 8 to 9, the conductivity of the aqueous organic positive electrode slurry is also affected by the type of the conductive agent, and the conductivity of the aqueous organic positive electrode sheet is reduced by using only carbon black or only carbon nanotubes as the conductive agent.
(4) Specific capacity of first discharge: testing was performed at a temperature of 25℃and a current density of 8 mA/g;
(5) Cycle number at 80% soc: the test was carried out at a temperature of 25℃and a current density of 8 mA/g.
The lithium ion button cells in the application examples 1 to 9 and comparative application examples 1 to 2 were tested according to the above test methods, and the test results are shown in table 3:
TABLE 3 Table 3
| Specific capacity for initial discharge (mAh/g) | Cycle number/number at 80% SOC | |
| Application example 1 | 172.8 | 45 |
| Application example 2 | 173.1 | 43 |
| Application example 3 | 174.2 | 53 |
| Application example 4 | 173.3 | 41 |
| Application example 5 | 169.4 | 40 |
| Application example 6 | 141.2 | 11 |
| Application example 7 | 149.7 | 22 |
| Application example 8 | 164.5 | 35 |
| Application example 9 | 166.9 | 39 |
| Comparative application example 1 | 143.5 | 10 |
| Comparative application example 2 | 140.1 | 9 |
From the data in table 3, it can be seen that:
the lithium ion button cell finally prepared by adopting the aqueous organic positive electrode slurry provided by the invention has higher specific discharge capacity and excellent cycle performance;
specifically, the lithium ion button cell provided in application examples 1-4 has a first discharge specific capacity of 172.8-174.2 mAh/g at 25 ℃ and a cycle number of 41-53 times at 80% SOC;
as can be seen from comparing the data of application example 1 and comparative application example 1, application example 4 and comparative application example 2, the dispersibility of the aqueous organic positive electrode slurry without the dispersion medium is poor, which results in higher interfacial resistance and volume resistance of the further prepared aqueous organic positive electrode sheet, and further results in lower cycle performance and specific discharge capacity of the further obtained lithium ion button cell;
as can be seen from comparing the data of application examples 1 and 5, the cycling performance and specific discharge capacity of the lithium ion button cell provided in application example 5 are also reduced, further illustrating that the dispersing effect of iodine simple substance is better than that of naphthalene as dispersing medium;
further comparing the data of application example 1 and application examples 6 to 9, it can be seen that the amount of the dispersion medium added and the kind of the conductive agent also affect the discharge gram capacity and cycle performance of the lithium ion button cell by affecting the conductivity and porosity of the organic positive electrode sheet.
The applicant states that the present invention is described by way of the above examples as an aqueous organic positive electrode slurry, and a method of preparing the same and applications thereof, but the present invention is not limited to the above examples, i.e., it is not meant that the present invention must be practiced in dependence upon the above examples. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (10)
1. An aqueous organic positive electrode slurry, characterized in that the aqueous organic positive electrode slurry comprises an organic positive electrode active material, a dispersion medium, a binder, a conductive agent and water;
the dispersion medium comprises elemental iodine and/or naphthalene.
2. The aqueous organic positive electrode slurry according to claim 1, wherein the organic positive electrode active material comprises a conductive polymer;
preferably, the organic positive electrode active material includes any one or a combination of at least two of polyacetylene, polyphenyl, polypyrrole, polythiophene, active polysulfide, benzoquinone compound, or anthraquinone compound, and further preferably benzoquinone compound and/or anthraquinone compound;
preferably, the dispersion medium has a mass of 0.1 to 50%, more preferably 5 to 30%, based on 100% of the mass of the organic positive electrode active material.
3. The aqueous organic positive electrode slurry according to claim 1 or 2, wherein the binder comprises any one or a combination of at least two of styrene-butadiene rubber, carboxymethyl cellulose, polyacrylic acid, polyacrylonitrile, polyacrylate, polytetrafluoroethylene, or polyimide;
preferably, the binder is 1 to 15% by mass based on 100% by mass of the organic positive electrode active material.
4. The aqueous organic positive electrode slurry according to any one of claims 1 to 3, wherein the conductive agent comprises any one or a combination of at least two of carbon black, conductive graphite, carbon nanotubes or carbon nanofibers, preferably a combination of carbon black and carbon nanotubes;
preferably, the conductive agent is 0.5 to 15% by mass based on 100% by mass of the organic positive electrode active material.
5. The aqueous organic positive electrode slurry according to any one of claims 1 to 4, wherein the aqueous organic positive electrode slurry has a solid content of 30 to 65%;
preferably, the aqueous organic positive electrode slurry has a viscosity of 4500 to 7500mpa·s;
preferably, the fineness of the aqueous organic positive electrode slurry is not higher than 35 μm.
6. A method for producing the aqueous organic positive electrode slurry according to any one of claims 1 to 5, comprising the steps of:
(1) Mixing the conductive agent and part of the binder to obtain conductive glue solution;
(2) Mixing the dispersion medium with the conductive adhesive solution obtained in the step (1), adding an organic positive electrode active material for mixing, adding the rest of the adhesive for mixing, and finally adding water for mixing to obtain the aqueous organic positive electrode slurry.
7. The method of claim 6, wherein the temperature of the mixing in step (2) is no higher than 30 ℃;
preferably, the mixing in step (2) is carried out under stirring;
preferably, the stirring speed is 500-10000 rpm;
preferably, the mixing time of step (2) is each independently from 5 to 480 minutes.
8. An aqueous organic positive electrode sheet, characterized in that the aqueous organic positive electrode sheet comprises a positive electrode current collector and the aqueous organic positive electrode slurry according to any one of claims 1 to 5 attached to the surface of the positive electrode current collector after drying.
9. The aqueous organic positive electrode sheet according to claim 8, wherein the positive electrode current collector is a carbon-coated aluminum foil;
preferably, the drying comprises a first drying and a second drying;
preferably, the temperature of the first drying is 50-90 ℃;
preferably, the temperature of the second drying is 90-140 ℃.
10. A lithium ion battery comprising the aqueous organic positive electrode sheet of claim 8.
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| CN202311336715.XA CN117174909A (en) | 2023-10-16 | 2023-10-16 | Aqueous organic positive electrode slurry and preparation method and application thereof |
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| CN202311336715.XA CN117174909A (en) | 2023-10-16 | 2023-10-16 | Aqueous organic positive electrode slurry and preparation method and application thereof |
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