CN113555540A - Fast-charging polymer lithium ion battery - Google Patents
Fast-charging polymer lithium ion battery Download PDFInfo
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- CN113555540A CN113555540A CN202110824197.0A CN202110824197A CN113555540A CN 113555540 A CN113555540 A CN 113555540A CN 202110824197 A CN202110824197 A CN 202110824197A CN 113555540 A CN113555540 A CN 113555540A
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- lithium ion
- fast
- carbon
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 32
- 229920000642 polymer Polymers 0.000 title claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 56
- 239000010410 layer Substances 0.000 claims abstract description 43
- 239000006258 conductive agent Substances 0.000 claims abstract description 36
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 26
- 239000002210 silicon-based material Substances 0.000 claims abstract description 26
- 239000013543 active substance Substances 0.000 claims abstract description 21
- 239000011230 binding agent Substances 0.000 claims abstract description 19
- 239000003792 electrolyte Substances 0.000 claims abstract description 19
- 239000007773 negative electrode material Substances 0.000 claims abstract description 14
- 239000007774 positive electrode material Substances 0.000 claims abstract description 14
- 229910013421 LiNixCoyMn1-x-yO2 Inorganic materials 0.000 claims abstract description 7
- 229910013427 LiNixCoyMn1−x−yO2 Inorganic materials 0.000 claims abstract description 7
- 229920001661 Chitosan Polymers 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 26
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 25
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 239000011883 electrode binding agent Substances 0.000 claims description 21
- 239000002002 slurry Substances 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 17
- 238000004132 cross linking Methods 0.000 claims description 14
- XNPOFXIBHOVFFH-UHFFFAOYSA-N N-cyclohexyl-N'-(2-(4-morpholinyl)ethyl)carbodiimide Chemical compound C1CCCCC1N=C=NCCN1CCOCC1 XNPOFXIBHOVFFH-UHFFFAOYSA-N 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 12
- 238000005096 rolling process Methods 0.000 claims description 12
- 239000011257 shell material Substances 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 8
- 229920000098 polyolefin Polymers 0.000 claims description 8
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 6
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 6
- 229920000131 polyvinylidene Polymers 0.000 claims description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 6
- 229910021384 soft carbon Inorganic materials 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910013716 LiNi Inorganic materials 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 238000010000 carbonizing Methods 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 239000012792 core layer Substances 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 4
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- VTHRQKSLPFJQHN-UHFFFAOYSA-N 3-[2-(2-cyanoethoxy)ethoxy]propanenitrile Chemical compound N#CCCOCCOCCC#N VTHRQKSLPFJQHN-UHFFFAOYSA-N 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 claims description 2
- 229910021385 hard carbon Inorganic materials 0.000 claims description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 239000005060 rubber Substances 0.000 claims description 2
- 239000000661 sodium alginate Substances 0.000 claims description 2
- 235000010413 sodium alginate Nutrition 0.000 claims description 2
- 229940005550 sodium alginate Drugs 0.000 claims description 2
- 238000007599 discharging Methods 0.000 abstract description 10
- 230000001351 cycling effect Effects 0.000 abstract description 9
- 239000011247 coating layer Substances 0.000 abstract 1
- 239000011258 core-shell material Substances 0.000 abstract 1
- 239000010405 anode material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000004005 microsphere Substances 0.000 description 5
- 229910014002 LiNi0.2Co0.3Mn0.5O2 Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000009792 diffusion process Methods 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
- 230000003628 erosive effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 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
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- HSFQBFMEWSTNOW-UHFFFAOYSA-N sodium;carbanide Chemical group [CH3-].[Na+] HSFQBFMEWSTNOW-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
Abstract
The invention belongs to the technical field of lithium ion batteries. A fast-charging polymer lithium ion battery comprises a positive electrode, a negative electrode, a diaphragm and electrolyte; the positive plate comprises a positive current collector and a positive material layer, wherein the positive material layer comprises a positive active substance, a positive conductive agent and a positive binder; the negative plate comprises a negative current collector and a negative material layer, wherein the negative material layer comprises a negative active substance, a negative conductive agent and a negative binder; the positive electrode active material has a core-shell structure and a shellLiNi with graphene-like coating layer0.5Mn1.5O4The nuclear layer is LiNixCoyMn1‑x‑yO2(ii) a The negative active material includes a silicon-based material and a carbon-based material. The battery has the advantages of good electrochemical performance and cycling stability, high charging and discharging efficiency, good quick charging performance, high energy density, long cycling life and good safety performance.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a fast-charging polymer lithium ion battery.
Background
The lithium ion battery has the characteristics of high energy density, high average output voltage, high output power, small self-discharge, high charge-discharge efficiency, no memory effect and the like, and has wide application fields. The polymer lithium battery is safe and stable, does not leak liquid, and can inhibit side reaction between an electrolyte solvent and a battery positive and negative agent. At present, the method for improving the energy density and the quick charge performance of the polymer lithium ion battery is mainly to adopt a new anode material or a new cathode material. The common positive active materials of the polymer lithium ion battery comprise ternary materials and binary materials, including lithium cobaltate, lithium manganate, lithium iron phosphate and the like, and the negative active materials are mostly graphite, but the effect of the existing positive and negative active materials on improving the electron energy density is limited.
Disclosure of Invention
The invention aims to solve the technical problem of providing a fast-charging polymer lithium ion battery which has the advantages of good electrochemical performance and cycling stability, high charging and discharging efficiency, good fast-charging performance, high energy density, long cycling life and good safety performance.
The technical scheme of the invention is as follows:
a fast-charging polymer lithium ion battery comprises a positive electrode, a negative electrode, a diaphragm and electrolyte; the positive plate comprises a positive current collector and a positive material layer, wherein the positive material layer comprises a positive active substance, a positive conductive agent and a positive binder; the negative plate comprises a negative current collector and a negative material layer, wherein the negative material layer comprises a negative active substance, a negative conductive agent and a negative binder; the positive active substance has a shell-core structure, and the shell layer is LiNi coated by graphene-like0.5Mn1.5O4The nuclear layer is LiNixCoyMn1-x-yO2X is more than or equal to 0.1 and less than or equal to 0.9, y is more than or equal to 0.05 and less than or equal to 0.9, x + y is more than or equal to 0.1 and less than or equal to 0.95, the shell material accounts for 5-25 percent of the mass of the core layer material, and LiNi0.5Mn1.5O4The mass accounts for 90-95% of the total mass of the shell material;
the negative active material comprises a silicon-based material and a carbon-based material, wherein the silicon-based material is one or more of a silicon material, a silicon-oxygen material and a silicon-carbon material, and the carbon-based material is one or more of graphite, soft carbon and hard carbon.
Further, the preparation method of the positive electrode active material comprises the following steps: LiNi serving as a lithium nickel manganese oxide material0.5Mn1.5O4/LiNixCoyMn1-x-yO2Mixing with liquid polyacrylonitrile oligomer-ethanol solution, heating for reaction, and carbonizing.
The binary anode material is used as a shell layer, the ternary anode material is used as a core layer, and the formed shell-core structure is stable, so that the stability of the anode active substance to the electrolyte can be improved, and the conductivity of the material and the cycle performance of the battery are improved. The graphene-like film is low in density, can improve the energy density of the battery, has good heat conduction performance, can conduct heat in a high-rate charging and discharging process, avoids overhigh local temperature, and can improve the electrochemical performance, rate performance and cycling stability of the battery.
Further, the preparation method of the positive active material comprises the following specific steps: stirring liquid polyacrylonitrile oligomer-ethanol solution with concentration of 50% at 90-120 deg.C for 9-12h, adding lithium nickel manganese oxide material LiNi0.5Mn1.5O4/LiNixCoyMn1-x-yO2Uniformly mixing, completely evaporating at 75-85 ℃, fully crosslinking at 200-220 ℃, calcining for 10-20h at 850-1000 ℃ in an air atmosphere, and carbonizing to obtain the anode active substance.
After the polyacrylonitrile oligomer is carbonized on the surface of the binary anode material, more oxygen-containing functional groups can be generated on the surface of the binary anode material, so that the polarity of the surface of the anode material can be improved, the interaction between an anode active substance and a copolymer is enhanced, the bonding strength between the active substance and an anode current collector is improved, the mechanical property of the anode composite material is improved, the infiltration effect of the anode composite material and an electrolyte is improved, and the power performance of a battery is improved.
Further, the positive current collector material is aluminum, copper or iron, and the thickness is 10-12 μm; the positive conductive agent is one or more of carbon black, carbon nano tubes and graphene; the positive adhesive is one or more of polyethylene oxide, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl alcohol, a copolymer of polyvinylidene fluoride and hexafluoropropylene, polyurethane, polyacrylate, sodium carboxymethylcellulose, polyolefin, styrene butadiene rubber, fluorinated rubber, sodium alginate and acrylic acid modified chitosan.
Furthermore, the negative electrode binder is prepared by crosslinking carboxymethyl chitosan, N-isopropyl acrylamide and 1-cyclohexyl-3- (2-morpholinoethyl) carbodiimide, wherein the molar ratio of the N-isopropyl acrylamide to the carboxymethyl chitosan is 1:10-20, and the molar ratio of the N-isopropyl acrylamide to the carboxymethyl chitosan is 1: 3-5.
Further, the preparation method of the negative electrode binder comprises the following steps: mixing carboxymethyl chitosan solution with N-isopropyl acrylamide and 1-cyclohexyl-3- (2-morpholinoethyl) carbodiimide, heating to 30-50 ℃, and carrying out crosslinking reaction for 10-15 h.
The negative binder carboxymethyl chitosan, N-isopropyl acrylamide and 1-cyclohexyl-3- (2-morpholinoethyl) carbodiimide form a polymer with a three-dimensional structure, and has good mechanical property and chemical resistance, the surface of the negative binder structure contains a large amount of hydroxyl, carboxyl and amino, the dispersibility of the negative conductive agent can be improved, the bonding strength between the negative conductive agent and the negative current collector can be enhanced, and the material has high stability, good electrochemical property and cycling stability. The addition of the N-isopropyl acrylamide can enable a cross-linked network to be more compact, reduce the porosity of a negative active material, improve the conductivity of the battery and improve the quick charging performance of the battery under the same energy density.
Further, the preparation method of the negative plate comprises the following steps: silicon-based materials, carbon-based materials, negative electrode conductive agents and negative electrode binders are mixed according to the mass ratio of 60-80: 15-30: 0.5-5: 1-5, uniformly mixing to obtain slurry A; silicon-based materials, carbon-based materials, negative electrode conductive agents and negative electrode binders are mixed according to the mass ratio of 10-20:70-80: 0.5-5: 1-5, uniformly mixing to obtain slurry B; and coating the slurry A on the negative current collector, drying, rolling, coating the slurry B, drying, rolling and baking again to obtain the negative plate. The arrangement of the double-layer negative electrode material layer can improve the quick charging capacity and the energy density of the battery.
Further, the negative current collector material is aluminum, and the thickness of the negative current collector material is 6-8 μm; the negative electrode conductive agent is one or more of acetylene black, carbon nano tubes and graphene.
Further, the diaphragm is a polyvinylidene fluoride-acrylate/ceramic/polyolefin composite film with the thickness of 10-15 μm, wherein the thickness ratio of the polyvinylidene fluoride-acrylate, the ceramic and the polyolefin composite film is 1: 1-3:6-8. The diaphragm has good high temperature resistance and corrosion resistance, small thermal shrinkage rate, high porosity, smooth lithium ion migration path, high charge-discharge efficiency of the battery and long cycle life.
Further, the electrolyte comprises the following components: ethylene Carbonate (EC) in a mass ratio of 5-6:1-3:2-3:4-6: propylene Carbonate (PC): diethyl carbonate (DEC): ethyl Propionate (EP): propyl Propionate (PP), 1-5 wt% of 1, 3-propanesultone, 1-3 wt% of succinonitrile, 1-3 wt% of ethylene glycol bis (propionitrile) ether, 0.1-0.5 wt% of lithium difluorooxalato borate, 0.1-0.2 wt% of 1-n-propylphosphoric anhydride and 5-15 wt% of lithium hexafluorophosphate. The lithium salt concentration in the electrolyte is high, the conductivity is high, lithium ions can be rapidly transferred during rapid charging and rapid discharging, high retention rate during high-rate discharging is ensured, and the cycle performance and rate performance of the battery can be improved.
The invention has the following beneficial effects:
the positive active substance has a shell-core structure, a graphene-like film is formed on the surface of the shell structure, and the film has a multilayer porous structure, so that the direct contact area of the active material and an electrolyte can be reduced, the erosion of the electrolyte to the positive active substance in the charge-discharge process is inhibited, and the material has high stability, good electrochemical performance and good cycling stability. The graphene-like structure has high porosity and specific surface area, can reduce contact impedance, can form a good electrode/electrolyte interface and a lithium ion transmission channel between an electrode and an electrolyte, shortens a lithium ion diffusion path, effectively reduces interface impedance, improves the charge and discharge multiplying power and the cycle stability of the battery, and has high charge and discharge efficiency and good safety performance. The cathode active material comprises a silicon-based material and a carbon-based material, has good conductivity, is beneficial to ion embedding, and improves the quick charging performance of the battery.
Detailed Description
The present invention will be described in detail with reference to examples, which are only preferred embodiments of the present invention and are not intended to limit the present invention.
In the examples and comparative examples of the present invention, except for the specific description, the positive electrode active material having a shell-core structure was used in which the shell layer was a graphene-like-coated LiNi0.5Mn1.5O4The nuclear layer is LiNi0.2Co0.3Mn0.5O2The shell layer material accounts for 25 percent of the mass of the core layer material, and LiNi accounts for0.5Mn1.5O4The mass accounts for 95 percent of the total mass of the shell material; the preparation method comprises the following specific steps: stirring liquid polyacrylonitrile oligomer-ethanol solution with concentration of 50% at 90-120 deg.C for 9-12h, adding lithium nickel manganese oxide material LiNi0.5Mn1.5O4/LiNi0.2Co0.3Mn0.5O2Uniformly mixing, completely evaporating at 75-85 ℃, fully crosslinking at 200-220 ℃, calcining for 10-20h at 850-1000 ℃ in an air atmosphere, and carbonizing to obtain the anode active substance.
The positive current collector material is aluminum foil, and the thickness is 10 mu m; the positive conductive agent is graphene and carbon black; the positive binder is sodium methyl cellulose and styrene butadiene rubber, and the mass ratio of the graphene to the carbon black to the sodium carboxymethyl cellulose to the styrene butadiene rubber is 55: 40:2:1.5.
The negative current collector material is aluminum foil, and the thickness is 6 mu m; the negative electrode conductive agent is acetylene black and a carbon nano tube in a mass ratio of 1: 1.
The used diaphragm is a polyvinylidene fluoride-acrylate/ceramic/polyolefin composite film with the thickness of 10 mu m, wherein the thickness ratio of the polyvinylidene fluoride-acrylate, the ceramic and the polyolefin composite film is 1: 2:7.
The electrolyte used comprises the following components: ethylene Carbonate (EC) in a mass ratio of 3:3:2:6: propylene Carbonate (PC): diethyl carbonate (DEC): ethyl Propionate (EP): propyl Propionate (PP), 1.5 wt% of 1, 3-propanesultone, 2.5 wt% of succinonitrile, 1.5 wt% of ethylene glycol bis (propionitrile) ether, 0.25 wt% of lithium difluorooxalato borate, 0.2 wt% of 1-n-propylphosphoric anhydride and 15 wt% of lithium hexafluorophosphate.
Example 1
A fast-charging polymer lithium ion battery comprises a positive electrode, a negative electrode, a diaphragm and electrolyte; the positive plate comprises a positive current collector and a positive material layer, wherein the positive material layer comprises a positive active material with a shell-core structure, a positive conductive agent and a positive binder; the negative plate comprises a negative current collector and a negative material layer, wherein the negative material layer comprises a negative active substance, a negative conductive agent and a negative binder; the negative electrode active material comprises a silicon-based material and a carbon-based material, wherein the silicon-based material is a silicon-carbon microsphere, the carbon-based material is graphite and soft carbon in a mass ratio of 1:1, and the negative electrode binder is acrylic acid modified chitosan; the preparation method of the negative plate comprises the following steps: mixing the components in a mass ratio of 80: 20: 1.8: and 2.5, uniformly mixing the silicon-based material, the carbon-based material, the negative electrode conductive agent and the negative electrode binder, coating the mixture on a negative electrode current collector, drying, rolling and baking again to obtain the negative electrode piece.
Example 2
A fast-charging polymer lithium ion battery comprises a positive electrode, a negative electrode, a diaphragm and electrolyte; the positive plate comprises a positive current collector and a positive material layer, wherein the positive material layer comprises a positive active material with a shell-core structure, a positive conductive agent and a positive binder; the negative plate comprises a negative current collector and a negative material layer, wherein the negative material layer comprises a negative active substance, a negative conductive agent and a negative binder; the negative active material comprises a silicon-based material and a carbon-based material, wherein the silicon-based material is a silicon-carbon microsphere, and the carbon-based material is graphite and soft carbon in a mass ratio of 1: 1; the negative electrode binder is prepared by crosslinking carboxymethyl chitosan, N-isopropyl acrylamide and 1-cyclohexyl-3- (2-morpholinoethyl) carbodiimide, wherein the molar ratio of the N-isopropyl acrylamide to the carboxymethyl chitosan is 1:20, and the molar ratio of the N-isopropyl acrylamide to the carboxymethyl chitosan is 1: 3; the preparation method of the negative plate comprises the following steps: mixing the components in a mass ratio of 80: 20: 1.8: and 2.5, uniformly mixing the silicon-based material, the carbon-based material, the negative electrode conductive agent and the negative electrode binder, coating the mixture on a negative electrode current collector, drying, rolling and baking again to obtain the negative electrode piece.
Example 3
A fast-charging polymer lithium ion battery comprises a positive electrode, a negative electrode, a diaphragm and electrolyte; the positive plate comprises a positive current collector and a positive material layer, wherein the positive material layer comprises a positive active material with a shell-core structure, a positive conductive agent and a positive binder; the negative plate comprises a negative current collector and a negative material layer, wherein the negative material layer comprises a negative active substance, a negative conductive agent and a negative binder; the negative active material comprises a silicon-based material and a carbon-based material, wherein the silicon-based material is a silicon-carbon microsphere, and the carbon-based material is graphite and soft carbon in a mass ratio of 1: 1;
the negative electrode binder is prepared by crosslinking carboxymethyl chitosan, N-isopropyl acrylamide and 1-cyclohexyl-3- (2-morpholinoethyl) carbodiimide, wherein the molar ratio of the N-isopropyl acrylamide to the carboxymethyl chitosan is 1:20, and the molar ratio of the N-isopropyl acrylamide to the carboxymethyl chitosan is 1: 3; the preparation method comprises the following steps: mixing a carboxymethyl chitosan solution with N-isopropyl acrylamide and 1-cyclohexyl-3- (2-morpholinoethyl) carbodiimide, heating to 40 ℃, and carrying out crosslinking reaction for 15 hours;
the preparation method of the negative plate comprises the following steps: silicon-based materials, carbon-based materials, negative electrode conductive agents and negative electrode binders are mixed according to a mass ratio of 80: 20: 1.8: 2.5, uniformly mixing to prepare slurry A; silicon-based materials, carbon-based materials, a negative electrode conductive agent and a negative electrode binder are mixed according to a mass ratio of 10:70: 0.5: 1, uniformly mixing to obtain slurry B; and coating the slurry A on the negative current collector, drying, rolling, coating the slurry B, drying, rolling and baking again to obtain the negative plate.
Comparative example 1
A fast-charging polymer lithium ion battery comprises a positive electrode, a negative electrode, a diaphragm and electrolyte; the positive plate comprises a positive current collector and a positive material layer, wherein the positive material layer comprises a positive active substance, a positive conductive agent and a positive binder; the positive active material is LiNi0.2Co0.3Mn0.5O2；
The negative plate comprises a negative current collector and a negative material layer, wherein the negative material layer comprises a negative active substance, a negative conductive agent and a negative binder; the negative active material comprises a silicon-based material and a carbon-based material, wherein the silicon-based material is a silicon-carbon microsphere, and the carbon-based material is graphite and soft carbon in a mass ratio of 1: 1;
the negative electrode binder is prepared by crosslinking carboxymethyl chitosan, N-isopropyl acrylamide and 1-cyclohexyl-3- (2-morpholinoethyl) carbodiimide, wherein the molar ratio of the N-isopropyl acrylamide to the carboxymethyl chitosan is 1:20, and the molar ratio of the N-isopropyl acrylamide to the carboxymethyl chitosan is 1: 3; the preparation method comprises the following steps: mixing a carboxymethyl chitosan solution with N-isopropyl acrylamide and 1-cyclohexyl-3- (2-morpholinoethyl) carbodiimide, heating to 40 ℃, and carrying out crosslinking reaction for 15 hours;
the preparation method of the negative plate comprises the following steps: silicon-based materials, carbon-based materials, negative electrode conductive agents and negative electrode binders are mixed according to a mass ratio of 80: 20: 1.8: 2.5, uniformly mixing to prepare slurry A; silicon-based materials, carbon-based materials, a negative electrode conductive agent and a negative electrode binder are mixed according to a mass ratio of 10:70: 0.5: 1, uniformly mixing to obtain slurry B; and coating the slurry A on the negative current collector, drying, rolling, coating the slurry B, drying, rolling and baking again to obtain the negative plate.
Comparative example 2
A fast-charging polymer lithium ion battery comprises a positive electrode, a negative electrode, a diaphragm and electrolyte; the positive plate comprises a positive current collector and a positive material layer, wherein the positive material layer comprises a positive active material with a shell-core structure, a positive conductive agent and a positive binder; the negative plate comprises a negative current collector and a negative material layer, wherein the negative material layer comprises a negative active substance, a negative conductive agent and a negative binder; the negative active material is silicon carbon microspheres;
the negative electrode binder is prepared by crosslinking carboxymethyl chitosan, N-isopropyl acrylamide and 1-cyclohexyl-3- (2-morpholinoethyl) carbodiimide, wherein the molar ratio of the N-isopropyl acrylamide to the carboxymethyl chitosan is 1:20, and the molar ratio of the N-isopropyl acrylamide to the carboxymethyl chitosan is 1: 3; the preparation method comprises the following steps: mixing a carboxymethyl chitosan solution with N-isopropyl acrylamide and 1-cyclohexyl-3- (2-morpholinoethyl) carbodiimide, heating to 40 ℃, and carrying out crosslinking reaction for 15 hours;
the preparation method of the negative plate comprises the following steps: mixing a negative electrode active material, a negative electrode conductive agent and a negative electrode binder according to a mass ratio of 100: 1.8: 2.5, uniformly mixing to prepare slurry A; mixing a negative electrode active material, a negative electrode conductive agent and a negative electrode binder according to a mass ratio of 80: 0.5: 1, uniformly mixing to obtain slurry B; and coating the slurry A on the negative current collector, drying, rolling, coating the slurry B, drying, rolling and baking again to obtain the negative plate.
The fast-charging polymer lithium ion batteries of examples 1 to 3 and comparative examples 1 to 2 of the present invention were tested for various properties:
1. the charge and discharge performance is as follows: charging to 4.45V at a constant current of 0.5C, standing for 30min, discharging to 2.0V at a constant current of 0.2C, and testing the charging and discharging efficiency of the battery;
2. cycle performance: at normal temperature, charging and discharging are carried out at a rate of 1.0C, and after the charging and discharging are carried out circularly after 500 weeks, the capacity retention rate of the battery is tested;
the test results are given in the following table:
| test items | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 |
| Charge-discharge efficiency/% | 98.89 | 99.31 | 99.85 | 98 | 98.25 |
| Capacity retention ratio/%) | 86 | 87.5 | 89 | 83 | 85 |
Therefore, the fast-charging polymer lithium ion battery has good charge-discharge efficiency and cycle performance.
The battery has the advantages of good electrochemical performance and cycling stability, high charging and discharging efficiency, good quick charging performance, high energy density, long cycling life and good safety performance.
Claims (10)
1. A fast-charging polymer lithium ion battery comprises a positive electrode, a negative electrode, a diaphragm and electrolyte; the positive plate comprises a positive current collector and a positive material layer, wherein the positive material layer comprises a positive active substance, a positive conductive agent and a positive binder; the negative plate comprises a negative current collector and a negative material layer, wherein the negative material layer comprises a negative active substance, a negative conductive agent and a negative binder; it is characterized in thatThe positive active material has a shell-core structure, and the shell layer is LiNi coated with graphene-like material0.5Mn1.5O4The nuclear layer is LiNixCoyMn1-x-yO2X is more than or equal to 0.1 and less than or equal to 0.9, y is more than or equal to 0.05 and less than or equal to 0.9, x + y is more than or equal to 0.1 and less than or equal to 0.95, the shell material accounts for 5-25 percent of the mass of the core layer material, and LiNi0.5Mn1.5O4The mass accounts for 90-95% of the total mass of the shell material;
the negative active material comprises a silicon-based material and a carbon-based material, wherein the silicon-based material is one or more of a silicon material, a silicon-oxygen material and a silicon-carbon material, and the carbon-based material is one or more of graphite, soft carbon and hard carbon.
2. The fast-charging polymer lithium ion battery according to claim 1, wherein the preparation method of the positive electrode active material comprises the following steps: LiNi serving as a lithium nickel manganese oxide material0.5Mn1.5O4/LiNixCoyMn1-x-yO2Mixing with liquid polyacrylonitrile oligomer-ethanol solution, heating for reaction, and carbonizing.
3. The fast-charging polymer lithium ion battery of claim 2, wherein the preparation method of the positive active material comprises the following specific steps: stirring liquid polyacrylonitrile oligomer-ethanol solution with concentration of 50% at 90-120 deg.C for 9-12h, adding lithium nickel manganese oxide material LiNi0.5Mn1.5O4/LiNixCoyMn1-x-yO2Uniformly mixing, completely evaporating at 75-85 ℃, fully crosslinking at 200-220 ℃, calcining for 10-20h at 850-1000 ℃ in an air atmosphere, and carbonizing to obtain the anode active substance.
4. The fast-charging polymer lithium ion battery according to claim 1, wherein the positive electrode current collector material is aluminum, copper or iron, and has a thickness of 10-12 μm; the positive conductive agent is one or more of carbon black, carbon nano tubes and graphene; the positive adhesive is one or more of polyethylene oxide, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl alcohol, a copolymer of polyvinylidene fluoride and hexafluoropropylene, polyurethane, polyacrylate, sodium carboxymethylcellulose, polyolefin, styrene butadiene rubber, fluorinated rubber, sodium alginate and acrylic acid modified chitosan.
5. The fast-charging polymer lithium ion battery of claim 1, wherein the negative electrode binder is prepared by crosslinking carboxymethyl chitosan with N-isopropyl acrylamide and 1-cyclohexyl-3- (2-morpholinoethyl) carbodiimide, and the molar ratio of the N-isopropyl acrylamide to the carboxymethyl chitosan is 1:10-20 and the molar ratio of the N-isopropyl acrylamide to the carboxymethyl chitosan is 1: 3-5.
6. The fast-charging polymer lithium ion battery of claim 5, wherein the preparation method of the negative electrode binder comprises the following steps: mixing carboxymethyl chitosan solution with N-isopropyl acrylamide and 1-cyclohexyl-3- (2-morpholinoethyl) carbodiimide, heating to 30-50 ℃, and carrying out crosslinking reaction for 10-15 h.
7. The fast-charging polymer lithium ion battery of claim 1, wherein the preparation method of the negative plate comprises the following steps: silicon-based materials, carbon-based materials, negative electrode conductive agents and negative electrode binders are mixed according to the mass ratio of 60-80: 15-30: 0.5-5: 1-5, uniformly mixing to obtain slurry A; silicon-based materials, carbon-based materials, negative electrode conductive agents and negative electrode binders are mixed according to the mass ratio of 10-20:70-80: 0.5-5: 1-5, uniformly mixing to obtain slurry B; and coating the slurry A on the negative current collector, drying, rolling, coating the slurry B, drying, rolling and baking again to obtain the negative plate.
8. The fast-charging polymer lithium ion battery of claim 1, wherein the negative current collector material is aluminum and has a thickness of 6-8 μm; the negative electrode conductive agent is one or more of acetylene black, carbon nano tubes and graphene.
9. The fast-charging polymer lithium ion battery according to claim 1, wherein the separator is a polyvinylidene fluoride-acrylate/ceramic/polyolefin composite film with a thickness of 10-15 μm, and the thickness ratio of the polyvinylidene fluoride-acrylate, ceramic and polyolefin composite films is 1: 1-3:6-8.
10. The fast-charging polymer lithium ion battery of claim 1, wherein the electrolyte comprises the following components: ethylene Carbonate (EC) in a mass ratio of 5-6:1-3:2-3:4-6: propylene Carbonate (PC): diethyl carbonate (DEC): ethyl Propionate (EP): propyl Propionate (PP), 1-5 wt% of 1, 3-propanesultone, 1-3 wt% of succinonitrile, 1-3 wt% of ethylene glycol bis (propionitrile) ether, 0.1-0.5 wt% of lithium difluorooxalato borate, 0.1-0.2 wt% of 1-n-propylphosphoric anhydride and 5-15 wt% of lithium hexafluorophosphate.
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