CN113555541A - High-energy-density lithium ion battery - Google Patents
High-energy-density lithium ion battery Download PDFInfo
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- CN113555541A CN113555541A CN202110824881.9A CN202110824881A CN113555541A CN 113555541 A CN113555541 A CN 113555541A CN 202110824881 A CN202110824881 A CN 202110824881A CN 113555541 A CN113555541 A CN 113555541A
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- lithium ion
- lini
- ion battery
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 35
- 239000013543 active substance Substances 0.000 claims abstract description 33
- 239000011230 binding agent Substances 0.000 claims abstract description 31
- 239000006258 conductive agent Substances 0.000 claims abstract description 30
- 239000002131 composite material Substances 0.000 claims abstract description 29
- 239000011257 shell material Substances 0.000 claims abstract description 25
- 239000003792 electrolyte Substances 0.000 claims abstract description 19
- 239000010410 layer Substances 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims abstract description 14
- 229910013716 LiNi Inorganic materials 0.000 claims abstract description 12
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 10
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 10
- 239000012792 core layer Substances 0.000 claims abstract description 9
- 229910013421 LiNixCoyMn1-x-yO2 Inorganic materials 0.000 claims abstract description 8
- 229910013427 LiNixCoyMn1−x−yO2 Inorganic materials 0.000 claims abstract description 8
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 claims abstract description 7
- 239000002002 slurry Substances 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 27
- 239000002105 nanoparticle Substances 0.000 claims description 24
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 22
- 239000011572 manganese Substances 0.000 claims description 18
- 239000011248 coating agent Substances 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 238000005096 rolling process Methods 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 11
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 10
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 10
- 239000007774 positive electrode material Substances 0.000 claims description 10
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 10
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 10
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000010000 carbonizing Methods 0.000 claims description 5
- 239000007788 liquid Substances 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 238000003756 stirring Methods 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
- 229920001661 Chitosan Polymers 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 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
- 238000010438 heat treatment Methods 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
- 239000005543 nano-size silicon particle Substances 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 229920000098 polyolefin 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
- 235000012239 silicon dioxide Nutrition 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
- 230000001351 cycling effect Effects 0.000 abstract description 6
- 239000010405 anode material Substances 0.000 description 6
- 229920006124 polyolefin elastomer Polymers 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000011883 electrode binding agent Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 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
- VTHRQKSLPFJQHN-UHFFFAOYSA-N 3-[2-(2-cyanoethoxy)ethoxy]propanenitrile Chemical compound N#CCCOCCOCCC#N VTHRQKSLPFJQHN-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000011889 copper foil Substances 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
- 230000000694 effects Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention belongs to the technical field of lithium ion batteries. A lithium ion battery with high energy density comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein the positive plate comprises a positive current collector and a positive composite material, and the positive composite material comprises a positive active substance, a positive conductive agent and a binder; the positive conductive agent comprises lithium iron phosphate coated by carbon nano tubes; 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 lithium ion battery has higher energy density, electrochemical performance, rate capability and cycling stability.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a lithium ion battery with high energy density.
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 anode material of the lithium ion battery mainly comprises lithium cobaltate, lithium manganate, lithium nickelate, ternary material, lithium iron phosphate and the like. The lithium iron phosphate positive electrode material has the characteristics of high safety, long service life, low cost and high voltage platform, but the lithium iron phosphate has poor conductivity, and when the battery is charged and discharged at high multiplying power due to slow diffusion of lithium ions, the lithium iron phosphate system lithium ion battery has low energy density, small compaction density, small gram capacity, slow charging rate and poor cruising ability. Therefore, a lithium iron phosphate system lithium ion battery having high energy density and good electrochemical performance is required.
Disclosure of Invention
The invention aims to solve the technical problem of providing a lithium ion battery with high energy density, which has higher energy density, electrochemical performance, rate capability and cycling stability.
The technical scheme of the invention is as follows:
a lithium ion battery with high energy density comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein the positive plate comprises a positive current collector and a positive composite material, and the positive composite material comprises a positive active substance, a positive conductive agent and a binder; the positive conductive agent comprises lithium iron phosphate coated by carbon nano tubes; 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.
Further, the positive current collector is a porous current collector, the porous current collector is made of aluminum, copper or iron, the thickness is 10-50 μm, the porosity is 10-60%, and the pore diameter is 1-20 μm.
The hole structure on the current collector can be a through hole and a non-through hole, the density of the positive current collector is low, and the positive composite material can be embedded in the oxide film hole structure, so that the bonding strength and the coating amount of the positive material and the current collector are improved, and the energy density and the conductivity of the battery are improved. The contact area of the electrolyte and the positive current collector can be improved, the holding capacity of the battery electrolyte is obviously improved, and the cycle life of the battery is greatly prolonged.
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 charge and discharge 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-yO2Mixing uniformly, evaporating completely at 75-85 deg.C, fully crosslinking at 200-220 deg.C, calcining at 850-1000 deg.C in air atmosphereAnd carbonizing for 10-20h to obtain the positive 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 binder 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.
Further, the cathode composite material further comprises inorganic nanoparticles.
Further, the inorganic oxide nano particles account for 0.1-5% of the mass of the positive electrode composite material; the inorganic oxide nano particles comprise one or more of nano silicon dioxide, nano aluminum oxide and nano lithium carbonate.
Under the action of the adhesive, the nano inorganic filler can fill the pores on the surface of the positive active material, reduce the specific surface area, reduce the side reaction of the electrolyte to the positive active material and prevent the lattice collapse.
Further, the preparation method of the positive plate comprises the following steps: mixing a positive electrode active substance, a positive electrode conductive agent and a binder according to a mass ratio of 90-95: 0.5-5: 1-5, uniformly mixing to obtain slurry A; mixing inorganic oxide nano particles and a binder according to the mass ratio of 3-5: 0.5-2, and preparing slurry B; and coating the slurry A on the positive current collector, drying, rolling, coating the slurry B, drying, rolling and baking again to obtain the positive plate.
The invention has the following beneficial effects:
the conductive agent is lithium iron phosphate coated by the carbon nano tube, the lithium iron phosphate is embedded in the hexagonal structure of the carbon nano tube, a three-dimensional conductive net structure is obtained, and the material has high electrochemical properties such as conductivity, specific capacity and rate capability, so that the exertion of high specific energy of the battery is ensured, and the rate capability of the battery is improved. The lithium ion can be provided for the positive active material, the internal resistance can be reduced, and the energy density and the cycle performance of the battery are improved.
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, and improves the charge-discharge multiplying power and the cycling stability 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 embodiment and the comparative example of the high-energy-density lithium ion battery, the negative electrode comprises a negative electrode current collector, a negative electrode conductive agent and a negative electrode binder; the negative electrode current collector is a 6-micron copper foil, the negative electrode conductive agent is graphite and conductive carbon black, the negative electrode binder is sodium carboxymethyl cellulose and styrene butadiene rubber, and the mass ratio of the graphite to the conductive carbon black to the sodium carboxymethyl cellulose to the styrene butadiene rubber is 60: 36:1.5:2.3.
The diaphragm is 7 mu mPE basal membrane +2 mu m ceramic +1 mu mVDF glue layer.
The electrolyte comprises the following components: ethylene Carbonate (EC) in a mass ratio of 25:10:15:20: 30: propylene Carbonate (PC): diethyl carbonate (DEC): ethyl Propionate (EP): propyl Propionate (PP), 1, 3-propanesulfonic acid lactone 4 wt%, succinonitrile 2 wt%, ethylene glycol bis (propionitrile) ether 1.5 wt%, lithium difluorophosphate 0.5 wt%, 1-n-propylphosphoric anhydride 0.2 wt%, LiPF 615 wt%.
The preparation method of the positive active material used in the examples was: 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.
The positive electrode conductive agent is graphene.
Example 1
A lithium ion battery with high energy density comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein the positive plate comprises a positive current collector and a positive composite material, and the positive composite material comprises a positive active substance, a positive conductive agent and a binder; the positive conductive agent comprises lithium iron phosphate coated by carbon nano tubes; the positive active substance has a shell-core structure, and the shell layer is LiNi coated by graphene-like0.5Mn1.5O4The nuclear layer is LiNi0,9Co0.05Mn0.05O2The shell material accounts for 15 percent of the mass of the core layer material, and LiNi accounts for0.5Mn1.5O4The mass accounts for 90 percent of the total mass of the shell material; the binder is sodium carboxymethylcellulose, polyolefin and styrene butadiene rubber in a mass ratio of 0.6:1.5: 3.
The preparation method of the positive plate comprises the following steps: the method comprises the following steps of mixing a positive active substance, a positive conductive agent and a binder according to a mass ratio of 90: 1.5: 2.5, uniformly mixing to prepare slurry A; and coating the slurry A on a 35-micron aluminum foil, drying, rolling, and baking again to obtain the positive plate.
Example 2
A lithium ion battery with high energy density comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein the positive plate comprises a positive current collector and a positive composite material, and the positive composite material comprises a positive active substance, a positive conductive agent and a binder; the positive conductive agent comprises lithium iron phosphate coated by carbon nano tubes; the positive active substance has a shell-core structure, and the shell layer is coated by graphene-likeLiNi of (2)0.5Mn1.5O4The nuclear layer is LiNi0,9Co0.05Mn0.05O2The shell material accounts for 15 percent of the mass of the core layer material, and LiNi accounts for0.5Mn1.5O4The mass accounts for 90 percent of the total mass of the shell material; the binder is sodium carboxymethylcellulose, polyolefin and styrene butadiene rubber in a mass ratio of 0.6:1.5: 3; the positive current collector is a porous current collector, the porous current collector is made of aluminum, the thickness is 35 mu m, the porosity is 60%, and the pore diameter is 10 mu m.
The preparation method of the positive plate comprises the following steps: the method comprises the following steps of mixing a positive active substance, a positive conductive agent and a binder according to a mass ratio of 90: 1.5: 2.5, uniformly mixing to prepare slurry A; and coating the slurry A on a 35-micron aluminum foil, drying, rolling, and baking again to obtain the positive plate.
Example 3
A lithium ion battery with high energy density comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein the positive plate comprises a positive current collector and a positive composite material, and the positive composite material comprises a positive active substance, a positive conductive agent, inorganic oxide nanoparticles and a binder; the positive conductive agent comprises lithium iron phosphate coated by carbon nano tubes; the positive active substance has a shell-core structure, and the shell layer is LiNi coated by graphene-like0.5Mn1.5O4The nuclear layer is LiNi0,9Co0.05Mn0.05O2The shell material accounts for 15 percent of the mass of the core layer material, and LiNi accounts for0.5Mn1.5O4The mass accounts for 90 percent of the total mass of the shell material; the binder is sodium carboxymethylcellulose, polyolefin and styrene butadiene rubber in a mass ratio of 0.6:1.5: 3; the positive current collector is a porous current collector, the porous current collector is made of aluminum, the thickness is 35 microns, the porosity is 60%, and the pore diameter is 10 microns; the inorganic oxide nanoparticles account for 2.5% of the mass of the positive electrode composite material, and the inorganic oxide nanoparticles account for nano aluminum oxide and nano lithium carbonate in a mass ratio of 1: 1.
The preparation method of the positive plate comprises the following steps: mixing a positive electrode active substance, a positive electrode conductive agent and a binder according to a mass ratio of 90-95: 0.5-5: 1-5, uniformly mixing to obtain slurry A; mixing inorganic oxide nano particles and a binder according to the mass ratio of 3-5: 0.5-2, and preparing slurry B; and coating the slurry A on the positive current collector, drying, rolling, coating the slurry B, drying, rolling and baking again to obtain the positive plate.
Comparative example 1
A lithium ion battery with high energy density comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein the positive plate comprises a positive current collector and a positive composite material, and the positive composite material comprises a positive active substance, a positive conductive agent, inorganic oxide nanoparticles and a binder; the positive conductive agent comprises lithium iron phosphate coated by carbon nano tubes; the positive active substance has a shell-core structure, and the shell layer is LiNi0.5Mn1.5O4The nuclear layer is LiNi0,9Co0.05Mn0.05O2The shell layer material accounts for 15 percent of the mass of the core layer material; the binder is sodium carboxymethylcellulose, polyolefin and styrene butadiene rubber in a mass ratio of 0.6:1.5: 3; the positive current collector is a porous current collector, the porous current collector is made of aluminum, the thickness is 35 microns, the porosity is 60%, and the pore diameter is 10 microns; the inorganic oxide nanoparticles account for 2.5% of the mass of the positive electrode composite material, and the inorganic oxide nanoparticles account for nano aluminum oxide and nano lithium carbonate in a mass ratio of 1: 1.
The preparation method of the positive plate comprises the following steps: mixing a positive electrode active substance, a positive electrode conductive agent and a binder according to a mass ratio of 90-95: 0.5-5: 1-5, uniformly mixing to obtain slurry A; mixing inorganic oxide nano particles and a binder according to the mass ratio of 3-5: 0.5-2, and preparing slurry B; and coating the slurry A on the positive current collector, drying, rolling, coating the slurry B, drying, rolling and baking again to obtain the positive plate.
Comparative example 2
A lithium ion battery with high energy density comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein the positive plate comprises a positive current collector and a positive composite material, and the positive composite material comprises a positive active substance, a positive conductive agent, inorganic oxide nanoparticles and a binder; the positive electrode conductive agent comprises carbon nanoLithium iron phosphate coated by a rice tube; the positive active material is LiNi0,9Co0.05Mn0.05O2(ii) a The binder is sodium carboxymethylcellulose, polyolefin and styrene butadiene rubber in a mass ratio of 0.6:1.5: 3; the positive current collector is a porous current collector, the porous current collector is made of aluminum, the thickness is 35 microns, the porosity is 60%, and the pore diameter is 10 microns; the inorganic oxide nanoparticles account for 2.5% of the mass of the positive electrode composite material, and the inorganic oxide nanoparticles account for nano aluminum oxide and nano lithium carbonate in a mass ratio of 1: 1.
The preparation method of the positive plate comprises the following steps: mixing a positive electrode active substance, a positive electrode conductive agent and a binder according to a mass ratio of 90-95: 0.5-5: 1-5, uniformly mixing to obtain slurry A; mixing inorganic oxide nano particles and a binder according to the mass ratio of 3-5: 0.5-2, and preparing slurry B; and coating the slurry A on the positive current collector, drying, rolling, coating the slurry B, drying, rolling and baking again to obtain the positive plate.
Comparative example 3
A lithium ion battery with high energy density comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein the positive plate comprises a positive current collector and a positive composite material, and the positive composite material comprises a positive active substance, a positive conductive agent, inorganic oxide nanoparticles and a binder; the positive electrode conductive agent comprises carbon nanotubes; the positive active substance has a shell-core structure, and the shell layer is LiNi coated by graphene-like0.5Mn1.5O4The nuclear layer is LiNi0,9Co0.05Mn0.05O2The shell material accounts for 15 percent of the mass of the core layer material, and LiNi accounts for0.5Mn1.5O4The mass accounts for 90 percent of the total mass of the shell material; the binder is sodium carboxymethylcellulose, polyolefin and styrene butadiene rubber in a mass ratio of 0.6:1.5: 3; the positive current collector is a porous current collector, the porous current collector is made of aluminum, the thickness is 35 microns, the porosity is 60%, and the pore diameter is 10 microns; the inorganic oxide nanoparticles account for 2.5% of the mass of the positive electrode composite material, and the inorganic oxide nanoparticles account for nano aluminum oxide and nano lithium carbonate in a mass ratio of 1: 1.
The preparation method of the positive plate comprises the following steps: mixing a positive electrode active substance, a positive electrode conductive agent and a binder according to a mass ratio of 90-95: 0.5-5: 1-5, uniformly mixing to obtain slurry A; mixing inorganic oxide nano particles and a binder according to the mass ratio of 3-5: 0.5-2, and preparing slurry B; and coating the slurry A on the positive current collector, drying, rolling, coating the slurry B, drying, rolling and baking again to obtain the positive plate.
The lithium ion battery with high energy density of the invention is tested for each performance of 3 examples and 3 comparative examples, and the test results are shown in the following table:
therefore, the lithium ion battery has higher energy density and capacity retention rate.
The lithium ion battery has higher energy density, electrochemical performance, rate capability and cycling stability.
Claims (8)
1. A lithium ion battery with high energy density comprises a positive plate, a negative plate, a diaphragm and electrolyte, and is characterized in that the positive plate comprises a positive current collector and a positive composite material, and the positive composite material comprises a positive active substance, a positive conductive agent and a binder; the positive conductive agent comprises lithium iron phosphate coated by carbon nano tubes; 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.
2. The high energy density lithium ion battery of claim 1, wherein the positive electrode current collector is a porous current collector made of aluminum, copper or iron, and has a thickness of 10-50 μm, a porosity of 10-60%, and a pore size of 1-20 μm.
3. The high energy density lithium ion battery according to claim 1, wherein the positive electrode active material is prepared by a method comprising: 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.
4. The lithium ion battery with high energy density according to claim 3, wherein the preparation method of the positive electrode 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.
5. The high energy density lithium ion battery of claim 1, wherein the binder is one or more of polyethylene oxide, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl alcohol, a copolymer of polyvinylidene fluoride and hexafluoropropylene, polyurethane, polyacrylate, sodium carboxymethyl cellulose, polyolefin, styrene butadiene rubber, fluorinated rubber, sodium alginate, acrylic modified chitosan.
6. The high energy density lithium ion battery of claim 1, wherein the positive electrode composite further comprises inorganic nanoparticles.
7. The high energy density lithium ion battery of claim 1, wherein the inorganic oxide nanoparticles are 0.1-5% of the mass of the positive electrode composite; the inorganic oxide nano particles comprise one or more of nano silicon dioxide, nano aluminum oxide and nano lithium carbonate.
8. The high energy density lithium ion battery according to claim 6 or 7, wherein the method for preparing the positive electrode sheet comprises the steps of: mixing a positive electrode active substance, a positive electrode conductive agent and a binder according to a mass ratio of 90-95: 0.5-5: 1-5, uniformly mixing to obtain slurry A; mixing inorganic oxide nano particles and a binder according to the mass ratio of 3-5: 0.5-2, and preparing slurry B; and coating the slurry A on the positive current collector, drying, rolling, coating the slurry B, drying, rolling and baking again to obtain the positive plate.
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