CN117954713A - Positive plate, and preparation method, system and application thereof - Google Patents
Positive plate, and preparation method, system and application thereof Download PDFInfo
- Publication number
- CN117954713A CN117954713A CN202410131192.3A CN202410131192A CN117954713A CN 117954713 A CN117954713 A CN 117954713A CN 202410131192 A CN202410131192 A CN 202410131192A CN 117954713 A CN117954713 A CN 117954713A
- Authority
- CN
- China
- Prior art keywords
- positive electrode
- coating
- positive
- base layer
- current collector
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title abstract description 22
- 239000011248 coating agent Substances 0.000 claims abstract description 88
- 238000000576 coating method Methods 0.000 claims abstract description 88
- 239000000463 material Substances 0.000 claims abstract description 29
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 28
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- 239000007774 positive electrode material Substances 0.000 claims description 77
- 238000001035 drying Methods 0.000 claims description 46
- 239000010410 layer Substances 0.000 claims description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 239000011267 electrode slurry Substances 0.000 claims description 12
- 239000011247 coating layer Substances 0.000 claims description 11
- 229920002873 Polyethylenimine Polymers 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 9
- 238000007598 dipping method Methods 0.000 claims description 9
- 239000011268 mixed slurry Substances 0.000 claims description 9
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002041 carbon nanotube Substances 0.000 claims description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000004020 conductor Substances 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims description 5
- 239000006258 conductive agent Substances 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 4
- GFAUNYMRSKVDJL-UHFFFAOYSA-N formyl chloride Chemical compound ClC=O GFAUNYMRSKVDJL-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000004193 piperazinyl group Chemical group 0.000 claims description 4
- SXYFKXOFMCIXQW-UHFFFAOYSA-N propanedioyl dichloride Chemical compound ClC(=O)CC(Cl)=O SXYFKXOFMCIXQW-UHFFFAOYSA-N 0.000 claims description 4
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229920006037 cross link polymer Polymers 0.000 claims description 3
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 3
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 claims description 3
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 abstract description 13
- 238000004090 dissolution Methods 0.000 abstract description 12
- 229910052723 transition metal Inorganic materials 0.000 abstract description 11
- 150000003624 transition metals Chemical class 0.000 abstract description 10
- 238000009736 wetting Methods 0.000 abstract description 2
- 239000011572 manganese Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000008595 infiltration Effects 0.000 description 5
- 238000001764 infiltration Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011029 spinel Substances 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910001428 transition metal ion Inorganic materials 0.000 description 3
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- TXIOGJHPPVXTOY-UHFFFAOYSA-N 1-ethyl-4-methylpiperazine Chemical compound CCN1CCN(C)CC1 TXIOGJHPPVXTOY-UHFFFAOYSA-N 0.000 description 1
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- -1 diformyl chloride Chemical compound 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- JSSXHAMIXJGYCS-UHFFFAOYSA-N piperazin-4-ium-2-carboxylate Chemical compound OC(=O)C1CNCCN1 JSSXHAMIXJGYCS-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to the technical field of batteries, in particular to a positive plate, and a preparation method, a system and application thereof. The positive plate comprises a positive current collector, a positive material base layer and a functional coating, wherein the positive material base layer is positioned on at least one side surface of the positive current collector, and the functional coating is positioned on the surface of the positive material base layer, which is far away from the positive current collector; the functional coating comprises a high molecular polymer and a polymer of acyl chloride compounds, and is doped with a carbon material. The positive plate disclosed by the invention can be used for relieving the dissolution of transition metal, guaranteeing the wetting performance of electrolyte and effectively improving the comprehensive performance of a battery.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a positive plate, and a preparation method, a system and application thereof.
Background
Manganese-rich anode materials such as lithium iron phosphate, spinel lithium nickel manganese oxide and lithium-rich manganese base are widely focused due to cost advantages, and compared with lithium iron phosphate and ternary materials, the electrochemical performance of the manganese-rich anode materials is influenced by the structural evolution of the anode, electrolyte decomposition, particle breakage and the like, and meanwhile, serious transition metal dissolution phenomenon (especially Mn) is not small in damage to the electrochemical performance of a battery cell. The transition metal ions dissolved out by the positive electrode can be deposited on the negative electrode side, so that the SEI film is continuously destroyed, and the electrolyte is catalyzed to decompose and reconstruct new SEI, which consumes active lithium ions for electrochemical circulation, and meanwhile, the SEI is continuously thickened, the impedance of the battery is greatly increased by the SEI which is continuously thickened, and the electrochemical stability of the battery is influenced. It is reported that transition metal ions can enter the graphite negative electrode sheet layer to cause the damage of the graphite lamellar structure.
At present, most of the means of solid phase coating of the positive electrode are adopted to relieve the dissolution of transition metal in the structure of the positive electrode material, but the solid phase coating is punctiform coating, so that the coating integrity is limited, and the dissolution of the transition metal cannot be effectively inhibited. While the complete CEI film is formed on the surface of the positive electrode by adding the positive electrode film forming additive, the dissolution of transition metal can be relieved to a certain extent, but the method does not achieve a good effect, and a large amount of transition metal ions still exist on the side of the negative electrode after circulation.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a positive plate which can relieve the dissolution of transition metal, ensure the infiltration performance of electrolyte and effectively improve the comprehensive performance of a battery.
The invention further aims to provide a preparation method of the positive plate, which is simple and efficient, and can obtain the positive plate with excellent electrochemical performance.
Another object of the present invention is to provide a battery.
It is another object of the present invention to provide a powered device.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
the positive plate comprises a positive current collector, a positive material base layer and a functional coating, wherein the positive material base layer is positioned on at least one side surface of the positive current collector, the functional coating is positioned on the surface, far away from the positive current collector, of the positive material base layer, the functional coating comprises a high-molecular polymer and a polymer of an acyl chloride compound, and carbon materials are doped in the functional coating.
In one embodiment, the high molecular polymer is at least one of polyethylenimine and an organic compound containing a piperazine group.
In one embodiment, the carbon material includes at least one of graphene oxide, carbon nanotubes, and conductive carbon black.
In one embodiment, the carbon material may be partially or fully replaced with a liquid-retaining material; the liquid-retaining material includes at least one of alumina and a low activity phosphate cross-linked polymer.
In one embodiment, the mass ratio of the high molecular polymer to the carbon material is (1 to 9): (1-2).
In one embodiment, the acid chloride compound includes at least one of trimesoyl chloride, terephthaloyl chloride, isophthaloyl chloride, malonyl chloride, and 1,2,4, 5-benzenetetra (formyl chloride).
In one embodiment, the functional coating has a thickness of 2 to 15 μm.
In one embodiment, the positive electrode material base layer includes a positive electrode active material, a conductive material, and a binder; the mass ratio of the positive electrode active material, the conductive material and the binder is (7.5-9): (0.5-1.3): (0.5-1.2).
In one embodiment, the positive electrode active material includes at least one of lithium manganate, lithium nickel manganate, lithium iron manganese phosphate, and ternary materials in the positive electrode material base layer.
The preparation method of the positive plate comprises the following steps:
Coating positive electrode slurry on at least one side surface of a positive electrode current collector, and drying to obtain a positive electrode material base layer; coating a mixed slurry of a carbon material, a high molecular polymer and water on the surface of the positive electrode material base layer, and drying to obtain a first coating to obtain a positive electrode material belt; and immersing the positive electrode material belt in an organic solution of an acyl chloride compound, and drying to obtain the functional coating.
In one embodiment, the mixed slurry has a solids content of 5% to 15%.
In one embodiment, the positive electrode slurry includes a positive electrode active material, a conductive agent, a binder, and a solvent; the solid content of the positive electrode slurry is 40% -70%.
In one embodiment, the concentration of the acid chloride compound is 0.02% to 0.5%;
In one embodiment, the method further comprises: and cutting the positive electrode material belt with the prepared functional coating.
The system for implementing the preparation method of the positive plate comprises a current collector supply device, a first coating device, a positive electrode material coating device, a first drying device, an acyl chloride compound solution containing device and a second drying device; the current collector supply device is used for providing a current collector; the positive electrode material coating device is used for coating a positive electrode material base layer on at least one side surface of the current collector; the first coating device is used for coating a first coating on the surface of the positive electrode material base layer; the first drying device is used for carrying out first drying treatment on the positive electrode material belt coated with the first coating and the positive electrode material base layer; the acyl chloride compound solution containing device is used for carrying out dipping treatment on the positive electrode material belt subjected to the first drying treatment so as to form a functional coating; the second drying device is used for carrying out second drying treatment on the positive electrode material belt subjected to the dipping treatment.
A battery comprises the positive plate or the positive plate prepared by the preparation method of the positive plate.
An electric device comprises the battery.
Compared with the prior art, the invention has the beneficial effects that:
(1) The functional coating is arranged on the positive plate, so that the dissolution of transition metal can be relieved, and meanwhile, the infiltration performance of electrolyte is ensured, and the comprehensive performance of the battery cell is effectively improved.
(2) According to the system disclosed by the invention, the positive plate can be efficiently prepared through the cooperation of all the devices, and the excellent electrochemical performance of the positive plate can be ensured.
(3) The battery of the invention has excellent cycle performance, multiplying power performance and safety performance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic diagram of a positive electrode sheet preparation system of the present invention.
Reference numerals:
1-current collector supply device, 2-positive electrode material coating device, 3-first coating device, 4-first drying device, 5-acyl chloride compound solution holding device, 6-second drying device, 7-auxiliary device.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
According to one aspect of the invention, the invention relates to a positive plate, which comprises a positive current collector, a positive material base layer and a functional coating, wherein the positive material base layer is positioned on at least one side surface of the positive current collector, and the functional coating is positioned on the surface of the positive material base layer away from the positive current collector; the functional coating comprises a high molecular polymer and a polymer of acyl chloride compounds, and is doped with a carbon material.
According to the invention, the coating with the electrical selectivity function is constructed on the surface of the positive electrode in situ, so that the dissolution of the transition metal element of the positive electrode is further relieved, and the cycle performance of the battery is improved. The specific principle is as follows: the functional coating with electrical selectivity can effectively realize high-selectivity separation of monovalent/divalent cations, which is mainly beneficial to that the repulsive force of the functional coating on the divalent cations is obviously higher than that of the monovalent cations, so that monovalent lithium ions can smoothly pass through the coating to realize normal lithium ion deintercalation, and divalent manganese ions are intercepted at the same time, so that the reduction of the cycle performance of the battery caused by the dissolution of the manganese ions is reduced; according to the invention, a small amount of carbon material is doped in the coating to serve as a polymerized connection point of the functional coating, so that the problem of electrolyte infiltration can be solved while the dissolution of transition metal is relieved, and the comprehensive performance of the battery cell is effectively improved.
In one embodiment, the high molecular polymer is at least one of polyethylenimine and an organic compound containing a piperazine group. The organic matter containing piperazine groups includes piperazine, piperazine-2-carboxylic acid, or 1-ethyl-4-methylpiperazine.
In one embodiment, the carbon material includes at least one of Graphene Oxide (GO), carbon Nanotubes (CNT), and conductive carbon black. The carbon material may be selected from any one of the above, or a combination of at least two thereof, for example, a combination of graphene oxide and carbon nanotubes, a combination of graphene oxide, carbon nanotubes and conductive carbon black, or the like.
In one embodiment, the carbon material may be partially or fully replaced with a liquid-retaining material; the liquid-retaining material includes at least one of alumina and a low activity phosphate cross-linked polymer. In one embodiment, the liquid retaining material is 5% to 50% of the carbon material by mass.
In one embodiment, the mass ratio of the high molecular polymer to the carbon material is (1 to 9): (1-2), e.g., 1:1, 1:1.5, 1:2, 1.5:1, 2:1, 3:1, 3:2, 5:1, 8:1, 9:2, 9:5, etc. The high polymer and the carbon material are in proper proportion, so that the dissolution of transition metal is relieved, and the electrolyte infiltration problem is improved.
In one embodiment, the acid chloride compound includes at least one of trimesoyl chloride, terephthaloyl chloride, isophthaloyl chloride, malonyl chloride, and 1,2,4, 5-benzenetetra (formyl chloride). The acid chloride compound may be any one of the above, or a combination of at least two thereof, for example, a combination of trimesoyl chloride and terephthaloyl chloride, a combination of isophthaloyl chloride and malonyl chloride, or the like.
In one embodiment, the functional coating has a thickness of 2 to 15 μm, for example 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10m, 15 μm, etc.
In one embodiment, the positive electrode material base layer includes a positive electrode active material, a conductive material, and a binder; the mass ratio of the positive electrode active material, the conductive material and the binder is (7.5-9): (0.5-1.3): (0.5-1.2), e.g., 7.5:1.3:1.2, 8:1:1, 8.5:1:0.5, 9:0.5:0.5, etc. In one embodiment, the positive electrode active material includes at least one of lithium manganate, lithium nickel manganate, lithium iron manganese phosphate, and ternary materials in the positive electrode material base layer.
According to another aspect, the invention relates to a method for preparing a positive plate, comprising the steps of:
Coating positive electrode slurry on at least one side surface of a positive electrode current collector, and drying to obtain a positive electrode material base layer; coating a mixed slurry of a carbon material, a high molecular polymer and water on the surface of the positive electrode material base layer, and drying to obtain a first coating to obtain a positive electrode material belt; and immersing the positive electrode material belt in an organic solution of an acyl chloride compound, and drying to obtain the functional coating.
According to the preparation method, through the cooperation of the steps, the dissolution of transition metal can be relieved, and meanwhile, the infiltration of electrolyte is ensured, so that the comprehensive performance of the battery is effectively improved.
In one embodiment, the mixed slurry has a solids content of 5% to 15%, including but not limited to 5%, 8%, 10%, 15%, etc.
In one embodiment, the positive electrode slurry includes a positive electrode active material, a conductive agent, a binder, and a solvent; the solid content of the positive electrode slurry is 40% -70%, including but not limited to 40%, 50%, 60%, 70% and the like. The solvent includes water, such as deionized water.
In one embodiment, the concentration of the acid chloride-based compound is 0.02% to 0.5%, including but not limited to 0.02%, 0.1%, 0.2%, 0.5%, etc. The organic solvent comprises cyclohexane.
In one embodiment, the method further comprises: and cutting the positive electrode material belt with the prepared functional coating. When the positive current collector is a current collector material belt, the current collector material belt is further cut to meet the size of the pole piece.
According to another aspect of the invention, the invention relates to a system for implementing the preparation method of the positive plate, comprising a current collector supply device, a first coating device, a positive electrode material coating device, a first drying device, an acyl chloride compound solution containing device and a second drying device; the current collector supply device is used for providing a current collector; the positive electrode material coating device is used for coating a positive electrode material base layer on at least one side surface of the current collector; the first coating device is used for coating a first coating on the surface of the positive electrode material base layer; the first drying device is used for carrying out first drying treatment on the positive electrode material belt coated with the first coating and the positive electrode material base layer; the acyl chloride compound solution containing device is used for carrying out dipping treatment on the positive electrode material belt subjected to the first drying treatment so as to form a functional coating; the second drying device is used for carrying out second drying treatment on the positive electrode material belt subjected to the dipping treatment.
According to the system disclosed by the invention, the positive plate can be efficiently prepared through the cooperation of all the devices, and the excellent electrochemical performance of the positive plate can be ensured.
In one embodiment, the system further comprises a cutting device for cutting the second dried positive electrode material strip.
According to another aspect of the invention, the invention also relates to a battery, which comprises the positive plate or the positive plate prepared by the preparation method of the positive plate.
In one embodiment, the battery includes the positive electrode sheet, the negative electrode sheet, the separator, and the electrolyte. The battery of the invention has excellent electrochemical properties.
According to another aspect, the invention also relates to a powered device comprising said battery. The electric equipment comprises an electric automobile and the like.
The following is a further explanation in connection with specific examples, comparative examples, and figures.
Example 1
The preparation method of the positive plate comprises the following steps:
Coating positive electrode slurry on the two side surfaces of a positive electrode current collector, wherein the positive electrode slurry is formed by mixing spinel lithium nickel manganese oxide, a conductive agent SP, an adhesive LA133 and water, and the mass ratio of the spinel lithium nickel manganese oxide to the conductive agent SP to the adhesive LA133 is 8:1:1, the solid content of the positive electrode slurry is 60%; and drying at 80 ℃ to obtain a positive electrode material base layer with the thickness of 70 mu m.
Coating a mixed slurry of a carbon material, polyethyleneimine and water on the surface of a positive electrode material base layer, wherein the preparation of the mixed slurry comprises the following steps: mixing a carbon material, polyethyleneimine and deionized water, and uniformly stirring, wherein the mass ratio of the carbon material to the polyethyleneimine is 1:1, the carbon material is conductive carbon black, and the solid content of the mixed slurry is 5%; and drying at 80 ℃ to obtain a first coating, wherein the thickness of the first coating is 2 mu m, and the first coating reaches the positive electrode material belt.
Dipping the positive electrode material belt into an organic solution of an acyl chloride compound, wherein the acyl chloride compound is trimesoyl chloride, the organic solvent is cyclohexane, and the concentration of the acyl chloride compound is 0.1%; and drying at 80 ℃ for 24 hours to obtain the functional coating.
And further cutting the positive electrode material belt with the obtained functional layer.
Example 2
A preparation method of a positive electrode sheet was the same as in example 1 except that the thickness of the first coating layer was 4. Mu.m.
Example 3
A preparation method of a positive electrode sheet was the same as in example 1 except that the thickness of the first coating layer was 6. Mu.m.
Example 4
A preparation method of a positive electrode sheet was the same as in example 1 except that the thickness of the first coating layer was 8. Mu.m.
Example 5
The preparation method of the positive plate comprises the following steps of removing carbon materials and polyethyleneimine according to a mass ratio of 2:1, and the other conditions are the same as in example 2.
Example 6
The preparation method of the positive plate comprises the following steps of removing carbon materials and polyethyleneimine according to a mass ratio of 1:2, and the other conditions are the same as in example 2.
Example 7
A preparation method of a positive plate comprises the following steps of removing carbon materials and polyethyleneimine according to a mass ratio of 1:3, and the other conditions are the same as in example 2.
Example 8
The preparation method of the positive plate is the same as in example 1 except that the carbon material is replaced by graphene oxide, carbon nanotubes and aluminum oxide in a mass ratio of 1:1:0.4.
Example 9
A preparation method of a positive plate comprises the steps of removing 1,2,4, 5-benzene tetra (formyl chloride) and m-benzene diformyl chloride with the mass ratio of 1:1 from acyl chloride compounds, and the other conditions are the same as in example 1.
Example 10
The system used for carrying out the method for producing the positive electrode sheet in examples 1 to 9 includes, as shown in fig. 1, a current collector supply device 1, a first coating device 3, a positive electrode material coating device 2, a first drying device 4, an acid chloride-based compound solution containing device 5, a second drying device 6, and an auxiliary device 7.
The current collector supply device 1 is used for providing a current collector; the positive electrode material coating device 2 is used for coating a positive electrode material base layer on one side surface of the current collector, and the first coating device 3 is used for coating a first coating on the surface of the positive electrode material base layer; the first drying device 4 is used for performing first drying treatment on the positive electrode material belt coated with the first coating layer and the positive electrode material base layer; the acyl chloride compound solution containing device 5 is used for carrying out dipping treatment on the positive electrode material belt subjected to the first drying treatment so as to form a functional coating; the second drying device 6 is used for performing a second drying treatment on the positive electrode material belt subjected to the impregnation treatment. The auxiliary device 7 is used for assisting the operation of the current collector material belt.
Specifically, the current collector supply device 1 releases a current collector material tape, the positive electrode material coating device 2 coats a positive electrode material base layer on the surface of the current collector material tape, and the first coating device 3 coats a first coating layer on the surface of the positive electrode material base layer; the current collector material belt is subjected to first drying treatment by a first drying device 4; then carrying out dipping treatment in an acyl chloride compound solution containing device 5 to form a functional coating; and then the second drying treatment is performed by the second drying device 6.
Comparative example 1
According to the method of example 1, a positive electrode material base layer is prepared on the surface of a positive electrode current collector to obtain a positive electrode plate.
Experimental example
The positive electrode sheets obtained in examples 1 to 9 and comparative example 1 were each prepared to obtain a battery, specifically comprising: and assembling the positive plate and the graphite negative electrode into a single-piece battery, and completing the assembly of the single-piece battery in a glove box filled with inert gas, wherein the contents of H 2 O and O 2 are both lower than 0.1ppm. 1M LiPF 6 (solvents EC, EMC and DEC, volume of EC: EMC and DEC = 1:1) +5% FEC (fluoroethylene carbonate, percentage of total electrolyte mass) +1% vinylene carbonate (percentage of total electrolyte mass) was used as electrolyte. Constant current charge/discharge testing was performed at room temperature using the LAND CT2001A battery test system, with the test procedure: 1C was charged to 4.9V and 1C was discharged to 3.5V, and the test was cycled.
The results of the performance test of the battery are shown in table 1.
Table 1 performance test of battery
As can be seen from Table 1, in comparative examples 1 to 4, as the coating thickness increases from 2 μm to 15 μm, the Mn content of the surface of the negative electrode sheet disassembled after 100 cycles is significantly reduced: in the process of increasing the thickness from 2 μm to 8 μm, the content of Mn element is rapidly reduced, and the corresponding battery cycle stability is improved from a retention rate of 85% for 100 circles to a retention rate of 94% for 100 circles, which is superior to the capacity retention rate of the battery obtained by the positive electrode sheet of comparative example 1; if the thickness of the coating layer is further increased, capacity exertion and cycle stability may be rapidly deteriorated, and when the thickness of the coating layer is too high, the thick organic coating layer which is subsequently cured also influences the wetting of the electrolyte to a certain extent, and meanwhile, part of unreacted polyethyleneimine monomer can remain in the organic coating layer which is subsequently cured, so that the screening effect of the organic coating layer on monovalent/divalent positive ions is reduced.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. The positive plate is characterized by comprising a positive current collector, a positive material base layer and a functional coating, wherein the positive material base layer is positioned on at least one side surface of the positive current collector, and the functional coating is positioned on the surface of the positive material base layer, which is far away from the positive current collector;
the functional coating comprises a high molecular polymer and a polymer of acyl chloride compounds, and is doped with a carbon material.
2. The positive electrode sheet according to claim 1, characterized by comprising at least one of the following features (1) to (4):
(1) The high molecular polymer comprises at least one of polyethylenimine and organic matters containing piperazine groups;
(2) The carbon material comprises at least one of graphene oxide, carbon nanotubes and conductive carbon black;
(3) The carbon material may be partially or fully replaced by a liquid-retaining material; the liquid-retaining material comprises at least one of alumina and a low activity phosphate cross-linked polymer;
(4) The mass ratio of the high molecular polymer to the carbon material is (1-9): (1-2).
3. The positive electrode sheet according to claim 1, wherein the acid chloride-based compound comprises at least one of trimesoyl chloride, terephthaloyl chloride, isophthaloyl chloride, malonyl chloride, and 1,2,4, 5-benzenetetra (formyl chloride).
4. The positive electrode sheet according to claim 1, wherein the functional coating layer has a thickness of 2 to 15 μm.
5. The positive electrode sheet according to claim 1, characterized by comprising at least one of the following features (1) to (2):
(1) The positive electrode material base layer comprises a positive electrode active material, a conductive material and a binder; the mass ratio of the positive electrode active material, the conductive material and the binder is (7.5-9): (0.5-1.3): (0.5-1.2);
(2) In the positive electrode material base layer, the positive electrode active material comprises at least one of lithium manganate, lithium nickel manganate, lithium iron manganese phosphate and ternary materials.
6. The method for producing a positive electrode sheet according to any one of claims 1 to 5, comprising the steps of:
Coating positive electrode slurry on at least one side surface of a positive electrode current collector, and drying to obtain a positive electrode material base layer; coating a mixed slurry of a carbon material, a high molecular polymer and water on the surface of the positive electrode material base layer, and drying to obtain a first coating to obtain a positive electrode material belt;
and immersing the positive electrode material belt in an organic solution of an acyl chloride compound, and drying to obtain the functional coating.
7. The method of producing a positive electrode sheet according to claim 6, characterized by comprising at least one of the following features (1) to (4):
(1) The solid content of the mixed slurry is 5% -15%;
(2) The positive electrode slurry comprises a positive electrode active material, a conductive agent, a binder and a solvent; the solid content of the positive electrode slurry is 40% -70%;
(3) The concentration of the acyl chloride compound is 0.02% -0.5%;
(4) Further comprises: and cutting the positive electrode material belt with the prepared functional coating.
8. The system for carrying out the method for producing a positive electrode sheet according to claim 6 or 7, characterized by comprising a current collector supply device, a first coating device, a positive electrode material coating device, a first drying device, an acid chloride compound solution containing device, and a second drying device;
The current collector supply device is used for providing a current collector; the positive electrode material coating device is used for coating a positive electrode material base layer on at least one side surface of the current collector; the first coating device is used for coating a first coating on the surface of the positive electrode material base layer; the first drying device is used for carrying out first drying treatment on the positive electrode material belt coated with the first coating and the positive electrode material base layer; the acyl chloride compound solution containing device is used for carrying out dipping treatment on the positive electrode material belt subjected to the first drying treatment so as to form a functional coating; the second drying device is used for carrying out second drying treatment on the positive electrode material belt subjected to the dipping treatment.
9. A battery comprising the positive electrode sheet according to any one of claims 1 to 5, or the positive electrode sheet produced by the method for producing a positive electrode sheet according to claim 6 or 7.
10. A powered device comprising the battery of claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410131192.3A CN117954713A (en) | 2024-01-30 | 2024-01-30 | Positive plate, and preparation method, system and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410131192.3A CN117954713A (en) | 2024-01-30 | 2024-01-30 | Positive plate, and preparation method, system and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117954713A true CN117954713A (en) | 2024-04-30 |
Family
ID=90803576
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410131192.3A Pending CN117954713A (en) | 2024-01-30 | 2024-01-30 | Positive plate, and preparation method, system and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117954713A (en) |
-
2024
- 2024-01-30 CN CN202410131192.3A patent/CN117954713A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110176591B (en) | Aqueous zinc ion secondary battery and preparation method of anode based on organic electrode material | |
| CN1126185C (en) | Electrode for nonaqueous electrolyte battery | |
| CN109103399B (en) | Functional diaphragm for lithium-sulfur battery, preparation method of functional diaphragm and application of functional diaphragm in lithium-sulfur battery | |
| CN103904291B (en) | Aquo-lithium ion battery electrode and preparation method thereof, aquo-lithium ion battery | |
| CN110556493B (en) | Functional composite diaphragm of lithium/sodium secondary battery and preparation method thereof | |
| JP4088755B2 (en) | Nonaqueous electrolyte secondary battery | |
| CN103647104A (en) | Lithium-sulfur battery | |
| JP4632020B2 (en) | Non-aqueous electrolyte secondary battery | |
| CN111916640A (en) | Lithium sulfur battery WS2/CNTs modified diaphragm and preparation method thereof | |
| CN110518293A (en) | A kind of preparation method of solid lithium ion battery | |
| JP2005209498A6 (en) | Non-aqueous electrolyte secondary battery | |
| CN107731542B (en) | A kind of solid state battery capacitor | |
| CN112615111A (en) | High-liquid-retention self-repairing diaphragm, preparation method thereof and lithium ion battery | |
| CN104900847A (en) | Sulfur electrode preparation method by in-situ polymerization of pyrrole monomer | |
| CN117096273B (en) | Protective layer modified lithium metal composite negative electrode, preparation method thereof and battery | |
| CN112615057B (en) | Preparation method of solid-state lithium ion battery and solid-state lithium ion battery | |
| JP2002008730A (en) | Lithium secondary battery | |
| CN109950454B (en) | Functional diaphragm of lithium-sulfur battery and preparation method thereof | |
| CN115863738A (en) | Secondary lithium battery using composite quasi-solid electrolyte membrane and preparation method thereof | |
| CN114743803A (en) | High-voltage hybrid lithium ion supercapacitor and preparation method thereof | |
| CN117954713A (en) | Positive plate, and preparation method, system and application thereof | |
| CN114883749A (en) | Fluorine-containing diaphragm, negative electrode interface modification material, method for performing interface modification on negative electrode material and battery | |
| JP2008060028A (en) | Power storage device | |
| CN114243098A (en) | Composite solid electrolyte and preparation method and application thereof | |
| JP2014072129A (en) | Electrode for power storage device and power storage device using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |