CN114050225A - Electrode plate and lithium ion battery containing same - Google Patents
Electrode plate and lithium ion battery containing same Download PDFInfo
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- CN114050225A CN114050225A CN202111145021.9A CN202111145021A CN114050225A CN 114050225 A CN114050225 A CN 114050225A CN 202111145021 A CN202111145021 A CN 202111145021A CN 114050225 A CN114050225 A CN 114050225A
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- lithium
- less
- inorganic particles
- conductive
- electrode sheet
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 38
- 238000000576 coating method Methods 0.000 claims abstract description 41
- 239000011248 coating agent Substances 0.000 claims abstract description 39
- 239000010954 inorganic particle Substances 0.000 claims abstract description 34
- 239000000853 adhesive Substances 0.000 claims abstract description 16
- 230000001070 adhesive effect Effects 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 11
- 239000007772 electrode material Substances 0.000 claims abstract description 11
- 239000004020 conductor Substances 0.000 claims abstract description 10
- 239000003792 electrolyte Substances 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 16
- 239000002033 PVDF binder Substances 0.000 claims description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 239000005033 polyvinylidene chloride Substances 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 7
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims description 6
- -1 nickel-cobalt-aluminum Chemical compound 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 239000011853 conductive carbon based material Substances 0.000 claims description 4
- 229920001940 conductive polymer Polymers 0.000 claims description 4
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 4
- 239000007769 metal material Substances 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002861 polymer material Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 4
- CVJYOKLQNGVTIS-UHFFFAOYSA-K aluminum;lithium;titanium(4+);phosphate Chemical compound [Li+].[Al+3].[Ti+4].[O-]P([O-])([O-])=O CVJYOKLQNGVTIS-UHFFFAOYSA-K 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 3
- 229910016838 LixGeyPzSw Inorganic materials 0.000 claims description 2
- 229910016983 LixLayTiO3 Inorganic materials 0.000 claims description 2
- MKGYHFFYERNDHK-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[Ti+4].[Li+] Chemical compound P(=O)([O-])([O-])[O-].[Ti+4].[Li+] MKGYHFFYERNDHK-UHFFFAOYSA-K 0.000 claims description 2
- PPVYRCKAOVCGRJ-UHFFFAOYSA-K P(=S)([O-])([O-])[O-].[Ge+2].[Li+] Chemical compound P(=S)([O-])([O-])[O-].[Ge+2].[Li+] PPVYRCKAOVCGRJ-UHFFFAOYSA-K 0.000 claims description 2
- 229910020213 PB(Mg3Nb2/3)O3-PbTiO3 Inorganic materials 0.000 claims description 2
- 229910020210 Pb(Mg3Nb2/3)O3—PbTiO3 Inorganic materials 0.000 claims description 2
- 229910020294 Pb(Zr,Ti)O3 Inorganic materials 0.000 claims description 2
- 229910002370 SrTiO3 Inorganic materials 0.000 claims description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 2
- YWJVFBOUPMWANA-UHFFFAOYSA-H [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O YWJVFBOUPMWANA-UHFFFAOYSA-H 0.000 claims description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 2
- 229910002113 barium titanate Inorganic materials 0.000 claims description 2
- 239000002134 carbon nanofiber Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910000449 hafnium oxide Inorganic materials 0.000 claims description 2
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims description 2
- 229910021385 hard carbon Inorganic materials 0.000 claims description 2
- 229910000659 lithium lanthanum titanates (LLT) Inorganic materials 0.000 claims description 2
- 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 2
- 239000002931 mesocarbon microbead Substances 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 229910021382 natural graphite Inorganic materials 0.000 claims description 2
- 239000007773 negative electrode material Substances 0.000 claims description 2
- 229920000767 polyaniline Polymers 0.000 claims description 2
- 229920000128 polypyrrole Polymers 0.000 claims description 2
- 229920000123 polythiophene Polymers 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910021384 soft carbon Inorganic materials 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 2
- 229910019483 (LiAlTiP)xOy Inorganic materials 0.000 claims 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims 1
- 239000013543 active substance Substances 0.000 claims 1
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 claims 1
- 238000012360 testing method Methods 0.000 description 9
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 6
- 239000006258 conductive agent Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910010116 LiAlTiP Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000013100 final test Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- BHZCMUVGYXEBMY-UHFFFAOYSA-N trilithium;azanide Chemical compound [Li+].[Li+].[Li+].[NH2-] BHZCMUVGYXEBMY-UHFFFAOYSA-N 0.000 description 1
- 238000010200 validation analysis Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to an electrode plate and a lithium ion battery containing the electrode plate, which comprises a current collector, an electrode active material layer, an organic/inorganic composite porous coating between the current collector and the electrode active material layer and/or an organic/inorganic composite porous coating on the electrode active material layer; the organic/inorganic composite porous coating comprises a high-molecular adhesive, a conductive material and inorganic particles; the inorganic particles are selected from at least one of the following particles: a. first inorganic particles having a dielectric constant of 5 or more; b. a second type of inorganic particles consisting of an inorganic solid-state electrolyte. The invention provides an electrode plate and a lithium ion battery containing the same, which can improve the safety performance of the lithium ion battery and simultaneously improve the electrochemical performance of the lithium ion battery.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to an electrode plate and a lithium ion battery containing the same.
Background
Lithium ion secondary batteries have the advantages of high voltage, high energy density, long cycle life and the like, and are the secondary batteries with the widest application range at present. However, under some special conditions, such as mechanical damage caused by extrusion, heavy impact or puncture, the lithium ion battery is easy to be ignited and exploded, thereby causing serious potential safety hazard. Thus greatly limiting the application development in some fields.
According to a large number of research results, the biggest cause of the potential safety hazards is the occurrence of internal short circuit of the battery, and when the internal short circuit occurs, the lithium ion battery can emit a large amount of heat in a short time, so that the lithium ion battery can be ignited and exploded. There are many modes of short circuit in the battery, wherein the short circuit between the positive current collector and the negative plate is the mode which transfers heat most quickly and is the most dangerous.
In order to avoid short circuit in the battery, the safety performance of the lithium ion battery is improved by using the characteristics of the PTC. PTC is incorporated into the electrode active material in a manner that, although it has a safety effect, affects the electrochemical performance of the battery. There is also a method of directly coating PTC on a current collector, but in this manner, when an electrode active material slurry is coated, a solvent of the slurry dissolves the PTC coating, and the PTC material is easily extruded to the edge during the rolling process, thereby causing a failure to achieve a desired effect of improving safety. Meanwhile, some inorganic fillers are added into slurry similar to PTC components and coated on a current collector to achieve the desired safety performance, but the added inorganic fillers have low ionic conductivity, so that the performance of the battery cell may be affected.
Disclosure of Invention
The invention aims to solve the problems, and provides an electrode plate and a lithium ion battery containing the electrode plate, which can improve the safety performance and the electrochemical performance of the lithium ion battery at the same time.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
an electrode plate comprises a current collector, an electrode active material layer, an organic/inorganic composite porous coating between the current collector and the electrode active material layer and/or an organic/inorganic composite porous coating on the electrode active material layer; the organic/inorganic composite porous coating comprises a high-molecular adhesive, a conductive material and inorganic particles; the inorganic particles are selected from at least one of the following particles: a. First inorganic particles having a dielectric constant of 5 or more; b. a second type of inorganic particles consisting of an inorganic solid-state electrolyte.
Further, the first inorganic particles are selected from BaTiO3、Pb(Zr，Ti)O3(PZT)、 Pb1-xLaxZr1-yTiO3(PLZT), hafnium oxide (HfO)2)、Pb(Mg3Nb2/3)O3-PbTiO3(PMT-PT)、SrTiO3、SnO2、 CeO2、MgO、NiO、CaO、ZnO、ZrO2、Y2O3、Al2O3、TiO2At least one of (1).
Further, the second type of inorganic particles are inorganic particles having lithium ion conductivity, that is, inorganic particles containing lithium element and capable of conducting lithium ions without storing lithium.
Further, the second inorganic particles are selected from lithium phosphate Li3PO4(ii) a Lithium titanium phosphate LixTiy (PO)4)3X is more than 0 and less than 2, and y is more than 0 and less than 3; lithium titanium aluminum phosphate LixAlyTiz (PO)4)3，0＜x＜2，0＜y＜1，0＜z＜3；(LiAlTiP) xOyThe x is more than 0 and less than 4, and the y is more than 0 and less than 13; lithium lanthanum titanate LixLayTiO3X is more than 0 and less than 2, and y is more than 0 and less than 3; lithium germanium thiophosphate LixGeyPzSw, x is more than 0 and less than 4, y is more than 0 and less than 1, z is more than 0 and less than 1, and w is more than 0 and less than 5; and lithium nitride LixNy, wherein 0 < x < 4 and 0 < y < 2, or at least one of the modified materials of the materials.
Further, the conductive material is selected from at least one of a conductive carbon-based material, a conductive metal material and a conductive polymer material; wherein the conductive carbon-based material is selected from at least one of conductive carbon black, acetylene black, graphite, graphene, carbon nanotubes and carbon nanofibers; the conductive metal material is selected from at least one of Al powder, Ni powder and gold powder; the conductive polymer material is selected from at least one of conductive polythiophene, conductive polypyrrole and conductive polyaniline.
Further, the polymer adhesive is at least one selected from polyvinylidene fluoride (PVDF), carboxylic acid modified PVDF, acrylic acid modified PVDF, polyvinylidene chloride (PVDC), carboxylic acid modified PVDC, acrylic acid modified PVDC, PVDF copolymer and PVDC copolymer.
The particle size of the inorganic particles is not particularly limited, but the average particle size D is preferably 10nm or less and D or less and 6um or less; the thickness H of the coating is 1um or more and 15um or less, preferably 2um or more and 10um or less.
Further, in the organic/inorganic composite porous coating, the weight percentage of the inorganic particles is 15-60%, the weight percentage of the polymer adhesive is 35-80%, and the weight percentage of the conductive material is 5-20%.
Further, the positive active material is selected from one or more of lithium cobaltate, a nickel-cobalt-manganese ternary material, a nickel-cobalt-aluminum ternary material, a nickel-cobalt-manganese-aluminum quaternary material, lithium iron phosphate, lithium manganese iron phosphate, lithium vanadium phosphate and lithium manganate; the negative active material is selected from one or more of natural graphite, artificial graphite, mesocarbon microbeads, hard carbon, soft carbon, silicon carbon and silica.
The invention also protects the lithium ion battery containing the electrode plate.
Compared with the prior art, the invention has the beneficial effects that:
(1) the polymer adhesive in the electrode plate coating has two functions, one is the adhesive which can be used as the coating, and the other is combined with the conductive agent to play a role similar to PTC.
(2) The conductive agent in the electrode plate coating has two functions, one is to increase the conductivity of the coating, and the other is to combine with the adhesive to play a role similar to PTC.
(3) The inorganic particles in the electrode plate coating have four functions, one function is to prevent NMP in slurry from directly dissolving the adhesive of the coating, and the second function is to prevent the conductive agent and the adhesive from being extruded unevenly when the electrode plate is rolled, so that the safety function which the electrode plate should exert is lost; the third is that the conductivity of lithium ion can be improved, the multiplying power of the battery can be improved, and the electrochemical properties such as low-temperature discharge and circulation can be improved; and the fourth is that the wettability of the electrolyte can be improved, so that the multiplying power of the battery, the electrochemical performances of low-temperature discharge, circulation and the like are improved.
Detailed Description
The above-mentioned contents of the present invention are further described in detail by way of examples below, but it should not be understood that the scope of the above-mentioned subject matter of the present invention is limited to the following examples, and any technique realized based on the above-mentioned contents of the present invention falls within the scope of the present invention.
Examples
A preparation method of an electrode plate and a lithium ion battery containing the electrode plate comprises the following steps:
the preparation steps of the coating are as follows: the coating is prepared by uniformly stirring a polymer adhesive, a conductive material, inorganic particles and an NMP solvent in a certain proportion, coating the mixture on a current collector (a positive current collector or a negative current collector), and drying the current collector. The main materials used in the coatings of the various embodiments are as follows: high-molecular adhesive: PVDF, conductive material: SP; inorganic particles: lithium iron phosphate, lithium aluminum titanium phosphate, aluminum oxide; the materials are common and common materials in the field of lithium battery industry.
The preparation method of the electrode positive plate comprises the following steps:
positive electrode sheet with coating: and uniformly stirring 96% of NCM, 2% of SP and 2% of PVDF by taking NMP as a solvent, coating the mixture on the positive current collector coated with the coating, drying at 90 ℃, rolling, cutting, drying at 110 ℃ for 4 hours under a vacuum condition, and welding tabs to prepare the positive pole piece of the lithium ion secondary battery meeting the requirements.
Conventional positive electrode sheet 1 #: the same preparation method as described above except that the surface of the aluminum foil of the current collector is added with no coating at all.
The preparation method of the electrode negative plate comprises the following steps:
negative pole piece with coating: the main material graphite, the conductive agent SP, the thickening agent CMC and the adhesive SBR are mixed according to the mass ratio: adding 96.8:1:1:1.2 into solvent deionized water, uniformly mixing to prepare negative electrode slurry, then coating the negative electrode slurry on a negative electrode current collector with a coating, drying at 85 ℃, rolling and cutting. And drying for 6h under the vacuum condition at the temperature of 130 ℃, and welding electrode lugs to prepare the lithium ion battery negative electrode piece meeting the requirements.
Conventional negative electrode sheet 1 #: the same preparation method as described above except that the surface of the copper foil of the current collector is added with no coating at all.
Preparing an electrolyte: and mixing ethylene carbonate, propylene carbonate and propyl propionate according to the mass ratio of 2:1:3 in a glove box filled with argon, slowly adding 1mol/L lithium hexafluorophosphate into the mixed solution, and uniformly stirring to obtain the lithium ion battery electrolyte of the embodiment.
The preparation method of the battery comprises the following steps: and sequentially laminating the positive plate and the negative plate prepared by the method and a polyethylene diaphragm with the thickness of 12 mu m to form a square roll core, packaging the roll core into a polymer soft package battery shell (made of an aluminum plastic film), then vacuum baking and injecting the prepared electrolyte, and after packaging, standing, forming, degassing, aging and capacity grading, obtaining the polymer soft package lithium ion battery.
And (3) electrochemical performance testing:
1)0.7C cycle performance test: charging the formed battery to 4.35V at a constant current and a constant voltage of 0.7C and stopping the current at 0.02C at 25 ℃, standing for 10min, and discharging to 3.0V at a constant current of 0.7C. The test is stopped when the charge-discharge circulation is carried out until the capacity is attenuated to be below 80 percent of the first discharge specific capacity;
2) and (3) needle punching test: at 25 ℃, the lithium ion battery after capacity grading is firstly discharged to 3.0V at 0.2C, and is charged to 4.35V at constant current and constant voltage of 0.5C after being stood for 10min, and the lithium ion battery is cut off at 0.02C. By using
The high temperature resistant steel needle penetrates from the direction vertical to the battery pole plate at the speed of 25 +/-5 mm/s, the penetrating position is close to the geometric center of the punctured surface, the steel needle stays in the battery, and whether the battery has the phenomena of fire and explosion or not is observed.
3) And (3) testing the impact of the weight: at 25 ℃, the lithium ion battery after capacity grading is firstly discharged to 3.0V at 0.2C, and is charged to 4.35V at constant current and constant voltage of 0.5C after being stood for 10min, and the lithium ion battery is cut off at 0.02C. Placing the battery on the surface of the platform, transversely placing a metal rod with the diameter of 15.8 +/-0.2 mm on the upper surface of the geometric center of the battery, adopting a weight with the mass of 9.1kg +/-0.1 kg to impact the surface of the battery with the metal rod in a free falling state from a high position with the mass of 610mm +/-25 mm, and observing whether the phenomena of fire and explosion occur or not within 6 hours.
4) And (3) testing the PTC effect: at 25 ℃, the lithium ion battery after capacity grading is firstly discharged to 3.0V at 0.2C, and is charged to 4.35V at constant current and constant voltage of 0.5C after being stood for 10min, and the lithium ion battery is cut off at 0.02C. And testing the alternating current internal resistance of the battery cell, then placing the battery cell at the constant temperature of 130 ℃ for 1h, testing the alternating current resistance, and calculating the increase rate of the alternating current resistance.
5) And (3) rate discharge performance test: at 25 ℃, the lithium ion battery after capacity grading is firstly discharged to 3.0V at 0.2C, and is charged to 4.35V at constant current and constant voltage of 0.5C after being stood for 10min, and the temperature is cut off at 0.02C. Then, the solution is put to 3.0V at different magnifications of 0.2C/0.5C/1C/1.5C/2C.
6) High and low temperature discharge performance: at 25 ℃, the lithium ion battery after capacity grading is firstly discharged to 3.0V at 0.2C, and is charged to 4.35V at constant current and constant voltage of 0.5C after being stood for 10min, and the temperature is cut off at 0.02C. Then put to 3.0V at 0.2C at different temperatures of 25 ℃/55 ℃/0 ℃/10 ℃/-20 ℃.
Results of Performance testing
In the examples, the specific materials and amounts listed in table 1-1 were prepared according to the methods and procedures described in "preparation method" to obtain the corresponding coating layer, positive electrode sheet, negative electrode sheet and battery, and then tested according to the method specified in "performance test of battery". To ensure the accuracy of the data, 5 cells (10 cells for each of the needle punched and weight impacted) were prepared and tested independently, and the final test results were averaged as shown in tables 1-2, tables 1-3, and tables 1-4:
TABLE 1-1 Pole piece compositions
Tables 1-2 examples 1-5 lithium ion battery performance test results (verification of coating impact)
Comparing examples 1 and 2, 1 and 3/4/5, it can be seen that: the coating can improve the safety performance of battery core needling and weight impact no matter at the anode or the cathode, and the low-temperature discharge and cycle performance of the battery core can be greatly improved by adding the LATP. The increase rate of the alternating current internal resistance of the battery cell at high temperature can be obviously improved by adding the inorganic particles, so that the passing rate of the battery cell after needle punching and weight impact is improved.
Tables 1-3 examples 1 and 6-9 lithium ion battery performance test results (validation of the effect of different material coatings)
Comparing examples 1 and 6-7, it can be seen that: different inorganic particle types in the coating are helpful for improving the safety performance of electric core needling and heavy object impact. The coating added with the alumina particles has the most obvious increase rate of alternating current internal resistance of the battery cell at high temperature, but has the greatest influence on the performance of the battery cell; the addition of the LATP particles greatly improves the electrical property, particularly the low-temperature discharge and cycle performance; while at the same time. A small amount of alumina is added into the LATP to play a synergistic role, so that the increase rate of the alternating internal resistance is increased compared with that of the LATP, and the electrical property is improved. Probably because the dielectric constant of the aluminum oxide is 9-10, the dissociation degree of lithium salt in the electrolyte can be increased, so that the ionic conductivity of the electrolyte is improved, meanwhile, the liquid absorption of an electrode plate can be increased due to the porous characteristic of the aluminum oxide, and the obvious performance of the battery is greatly improved by cooperating with the high ionic conductivity and the porous structure of the LATP.
Tables 1-4 test results for lithium ion battery performance of examples 1 and 9-20 (to verify the effect of different component contents in the coating)
Comparing examples 1 and 9-20, it can be seen that: the content of the inorganic particles in the coating is too high or too low, so that the safety performance of the battery cell cannot be greatly improved; the conductive agent in the coating helps the electrical performance of the battery. The LATP can also greatly improve the electrical performance of the cell, which may be due to the high ionic conductivity and the porous structure thereof, which increase the wettability of the electrolyte, thus improving the electrical performance to a certain extent.
In summary, the invention preferably selects the inorganic particle LATP which can improve the safety performance, the electrical performance, especially the low-temperature discharge and the cycle performance, and preferably selects the content ranges of all the components: 35-80% of high molecular adhesive, 5-20% of conductive material and 15-60% of inorganic particles.
The above description is only a preferred embodiment of the present invention, and should not be taken as limiting the invention in any way, and any person skilled in the art can make any simple modification, equivalent replacement, and improvement on the above embodiment without departing from the technical spirit of the present invention, and still fall within the protection scope of the technical solution of the present invention.
Claims (10)
1. An electrode sheet, comprising: comprises a current collector, an electrode active material layer, an organic/inorganic composite porous coating between the current collector and the electrode active material layer and/or an organic/inorganic composite porous coating on the electrode active material layer; the organic/inorganic composite porous coating comprises a high-molecular adhesive, a conductive material and inorganic particles; the inorganic particles are selected from at least one of the following particles: a. first inorganic particles having a dielectric constant of 5 or more; b. a second type of inorganic particles consisting of an inorganic solid-state electrolyte.
2. The electrode sheet of claim 1, wherein: the first type of inorganic particles are selected from BaTiO3、Pb(Zr，Ti)O3(PZT)、Pb1-xLaxZr1-yTiO3(PLZT), hafnium oxide (HfO)2)、Pb(Mg3Nb2/3)O3-PbTiO3(PMT-PT)、SrTiO3、SnO2、CeO2、MgO、NiO、CaO、ZnO、ZrO2、Y2O3、Al2O3、TiO2At least one of (1).
3. The electrode sheet of claim 1, wherein: the second type of inorganic particles are inorganic particles having lithium ion conductivity, that is, inorganic particles containing a lithium element and capable of conducting lithium ions without storing lithium.
4. The electrode sheet of claim 1, wherein: the second inorganic particles are selected from lithium phosphate Li3PO4(ii) a Lithium titanium phosphate LixTiy (PO)4)3X is more than 0 and less than 2, and y is more than 0 and less than 3; lithium titanium aluminum phosphate LixAlyTiz (PO)4)3，0＜x＜2，0＜y＜1，0＜z＜3；(LiAlTiP)xOyThe x is more than 0 and less than 4, and the y is more than 0 and less than 13; lithium lanthanum titanate LixLayTiO3X is more than 0 and less than 2, and y is more than 0 and less than 3; lithium germanium thiophosphate LixGeyPzSw, x is more than 0 and less than 4, y is more than 0 and less than 1, z is more than 0 and less than 1, and w is more than 0 and less than 5; the lithium nitride LixNy has x more than 0 and less than 4 and y more than 0 and less than 2; sulfide, etc. or at least one of the above modification materials.
5. The electrode sheet of claim 1, wherein: the conductive material is selected from at least one of conductive carbon-based materials, conductive metal materials and conductive polymer materials; wherein the conductive carbon-based material is selected from at least one of conductive carbon black, acetylene black, graphite, graphene, carbon nanotubes and carbon nanofibers; the conductive metal material is selected from at least one of Al powder, Ni powder and gold powder; the conductive polymer material is selected from at least one of conductive polythiophene, conductive polypyrrole and conductive polyaniline.
6. The electrode sheet of claim 1, wherein: the high molecular adhesive is at least one selected from polyvinylidene fluoride (PVDF), carboxylic acid modified PVDF, acrylic acid modified PVDF, polyvinylidene chloride (PVDC), carboxylic acid modified PVDC, acrylic acid modified PVDC, PVDF copolymer and PVDC copolymer.
7. The electrode sheet of claim 1, wherein: the average particle size D of the inorganic particles is not less than 10nm and not more than 6 um; the thickness H of the coating is more than or equal to 1um and less than or equal to 15 um.
8. The electrode sheet of claim 1, wherein: in the organic/inorganic composite porous coating, the weight percentage of inorganic particles is 15-60%, the weight percentage of polymer adhesive is 35-80%, and the weight percentage of conductive material is 5-20%.
9. The electrode sheet of claim 1, wherein: the positive active substance is selected from one or more of lithium cobaltate, a nickel-cobalt-manganese ternary material, a nickel-cobalt-aluminum ternary material, a nickel-cobalt-manganese-aluminum quaternary material, lithium iron phosphate, lithium manganese iron phosphate, lithium vanadium phosphate and lithium manganate; the negative active material is selected from one or more of natural graphite, artificial graphite, mesocarbon microbeads, hard carbon, soft carbon, silicon carbon and silica.
10. A lithium ion battery, characterized by: an electrode sheet comprising the electrode assembly of any one of claims 1 to 9.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117039114A (en) * | 2023-08-29 | 2023-11-10 | 深圳市贝特瑞新能源技术研究院有限公司 | Rechargeable high-safety lithium battery |
| WO2023246178A1 (en) * | 2022-06-23 | 2023-12-28 | 中国第一汽车股份有限公司 | Fibrillated mesh electrode, solid electrolyte membrane, energy storage device and vehicle |
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| CN109755463A (en) * | 2017-11-08 | 2019-05-14 | 宁德时代新能源科技股份有限公司 | Electrode pole piece, electrochemical device and safety coating |
| CN111697230A (en) * | 2020-05-07 | 2020-09-22 | 天津力神电池股份有限公司 | High-safety composite positive plate, preparation method thereof and lithium ion battery applying high-safety composite positive plate |
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