CN114142003A - Composite positive electrode slurry, lithium ion secondary battery and preparation method thereof - Google Patents
Composite positive electrode slurry, lithium ion secondary battery and preparation method thereof Download PDFInfo
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- CN114142003A CN114142003A CN202111306142.7A CN202111306142A CN114142003A CN 114142003 A CN114142003 A CN 114142003A CN 202111306142 A CN202111306142 A CN 202111306142A CN 114142003 A CN114142003 A CN 114142003A
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- Prior art keywords
- lithium
- sodium
- positive electrode
- lithium ion
- ion secondary
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 103
- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 239000011267 electrode slurry Substances 0.000 title claims description 18
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000011734 sodium Substances 0.000 claims abstract description 60
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 52
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 52
- 239000006256 anode slurry Substances 0.000 claims abstract description 28
- 239000007773 negative electrode material Substances 0.000 claims abstract description 20
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 claims abstract description 15
- 239000013543 active substance Substances 0.000 claims abstract description 8
- 239000007774 positive electrode material Substances 0.000 claims description 44
- -1 polypropylene Polymers 0.000 claims description 33
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 26
- 229910052744 lithium Inorganic materials 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 23
- 239000011248 coating agent Substances 0.000 claims description 21
- 238000000576 coating method Methods 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 19
- 239000011230 binding agent Substances 0.000 claims description 17
- 239000006258 conductive agent Substances 0.000 claims description 15
- 239000006257 cathode slurry Substances 0.000 claims description 13
- 239000003792 electrolyte Substances 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000004698 Polyethylene Substances 0.000 claims description 8
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229910021385 hard carbon Inorganic materials 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims description 6
- 159000000002 lithium salts Chemical class 0.000 claims description 6
- 239000012982 microporous membrane Substances 0.000 claims description 6
- 159000000000 sodium salts Chemical class 0.000 claims description 6
- 229910021384 soft carbon Inorganic materials 0.000 claims description 5
- 239000003125 aqueous solvent Substances 0.000 claims description 4
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 4
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 claims description 4
- 229960003351 prussian blue Drugs 0.000 claims description 4
- 239000013225 prussian blue Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000002931 mesocarbon microbead Substances 0.000 claims description 3
- 229910021382 natural graphite Inorganic materials 0.000 claims description 3
- JGTNAGYHADQMCM-UHFFFAOYSA-N perfluorobutanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-N 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 3
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 3
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 3
- QBJDFZSOZNDVDE-UHFFFAOYSA-M sodium;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F QBJDFZSOZNDVDE-UHFFFAOYSA-M 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 239000008151 electrolyte solution Substances 0.000 claims 2
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 24
- 238000000034 method Methods 0.000 abstract description 19
- 238000007599 discharging Methods 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 11
- 230000002441 reversible effect Effects 0.000 abstract description 11
- 239000002002 slurry Substances 0.000 abstract description 4
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 16
- 238000001035 drying Methods 0.000 description 10
- 238000011056 performance test Methods 0.000 description 10
- 229910021260 NaFe Inorganic materials 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 239000010406 cathode material Substances 0.000 description 8
- 239000002033 PVDF binder Substances 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 7
- 229910019142 PO4 Inorganic materials 0.000 description 6
- ZMVMBTZRIMAUPN-UHFFFAOYSA-H [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZMVMBTZRIMAUPN-UHFFFAOYSA-H 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229910000859 α-Fe Inorganic materials 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000006182 cathode active material Substances 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 239000002985 plastic film Substances 0.000 description 5
- 229920006255 plastic film Polymers 0.000 description 5
- 238000005096 rolling process Methods 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 238000004804 winding Methods 0.000 description 5
- 229910010710 LiFePO Inorganic materials 0.000 description 4
- 239000010405 anode material Substances 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 229910013733 LiCo Inorganic materials 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
Images
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
- 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
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
-
- 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
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides composite anode slurry, a lithium ion secondary battery and a preparation method thereof, and relates to the technical field of electrochemical energy storage. According to the invention, the lithium transition metal oxide and the sodium-containing active component are introduced into the positive active substance of the composite positive slurry, so that sodium ions and lithium ions which are separated from the positive electrode prepared from the composite positive slurry in the charging and discharging processes of the lithium ion battery can be respectively stored in different active positions of the negative electrode material according to the characteristics of different radiuses, thereby improving the comprehensive utilization rate of the active points of the negative electrode material in the lithium ion battery, enabling the negative electrode to have higher reversible specific capacity, and improving the first-time efficiency of the battery and the energy density of the lithium ion secondary battery.
Description
Technical Field
The invention relates to the technical field of electrochemical energy storage, in particular to composite anode slurry, a lithium ion secondary battery and a preparation method thereof.
Background
Since the commercialization of lithium ion batteries in the 90's of the last century, lithium ion batteries have been widely used with many advantages such as high energy density, high charge and discharge voltage, high energy conversion efficiency, low self-discharge, and no memory effect. However, with the progress of technology and the increase in consumer demand, portable devices such as mobile phones and notebook computers are becoming smaller and thinner, and higher demands are being made on the energy density of lithium ion batteries.
However, the loss of irreversible capacity during the first charge and discharge of a lithium ion battery limits the improvement of the energy density of the battery. At present, most commercial lithium batteries adopt a lithium transition metal oxide/carbon system, and the most common lithium transition metal oxide/graphite system; because lithium ions can only be inserted into the interlayer of the negative electrode material in the charging and discharging processes of the lithium ion battery, the utilization rate of the active points of the negative electrode material is not high, the reversible specific capacity is low, the first efficiency is low, and the improvement of the energy density of the lithium ion secondary battery is restricted.
Disclosure of Invention
The invention solves the problems that the utilization rate of the active points of the lithium ion battery negative electrode material is low, the reversible specific capacity is low, and the energy density of the lithium ion secondary battery is restricted to be improved.
In order to solve the above problems, the present invention provides a composite cathode slurry for a cathode of a lithium ion battery, including a cathode active material, a conductive agent, a binder and a solvent, wherein the cathode active material includes a lithium transition metal oxide and a sodium-containing active component.
Further, the weight percentage of the sodium-containing active component in the positive active material is 5% -30%.
Further, the lithium transition metal oxide includes at least one of lithium cobaltate, lithium manganate, lithium nickelate, lithium iron phosphate, lithium vanadium phosphate or ternary material.
Further, the sodium-containing active component includes at least one of a sodium-containing oxide material, a polyanionic material, or a prussian blue material.
Further, the mass ratio of the positive electrode active material, the conductive agent, the binder, and the solvent includes: 100: (0.5-5): (0.5-10): (40-150).
Compared with the prior art, the composite anode slurry has the advantages that the lithium transition metal oxide and the sodium-containing active component are introduced into the anode active substance of the composite anode slurry, so that sodium ions and lithium ions which are separated from an anode prepared from the composite anode slurry in the charging and discharging process of a lithium ion battery can be respectively stored in different active positions of an anode material according to the characteristics of different radiuses, the comprehensive utilization rate of active points of the anode material in the lithium ion battery is improved, the anode has higher reversible specific capacity, and the primary efficiency of the battery and the energy density of the lithium ion secondary battery are improved. Meanwhile, the invention reduces the using amount of lithium element, saves lithium resource and reduces the cost of the battery by introducing the sodium element with relatively rich reserve into the composite anode slurry.
The invention also provides a lithium ion secondary battery which comprises a positive electrode, a negative electrode, electrolyte and a diaphragm arranged between the positive electrode and the negative electrode, wherein the positive electrode comprises the composite positive electrode slurry.
Further, the negative electrode comprises a negative active material, and the negative active material comprises at least one of artificial graphite, natural graphite, mesocarbon microbeads, hard carbon, soft carbon or silicon carbon.
Further, the diaphragm comprises one of a polypropylene microporous membrane, a polyethylene microporous membrane, a glass fiber felt or a three-layer composite diaphragm.
Further, the electrolyte includes a lithium salt, a sodium salt, and a nonaqueous solvent; wherein the lithium salt comprises at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium perchlorate, lithium trifluoromethanesulfonate, lithium perfluorobutylsulfonate, lithium aluminate, lithium chloroaluminate, lithium fluorosulfonylimide, lithium chloride or lithium iodide; the sodium salt comprises at least one of sodium hexafluorophosphate, sodium tetrafluoroborate, sodium hexafluoroarsenate, sodium perchlorate, sodium trifluromethyl sulfonate, sodium perfluorobutyl sulfonate, sodium chloroaluminate or sodium fluorosulfonylimide; the non-aqueous solvent includes at least one of a fluorine-containing cyclic organic ester, a sulfur-containing cyclic organic ester, or an unsaturated bond-containing cyclic organic ester.
Compared with the prior art, the advantages of the lithium ion secondary battery are the same as those of the composite cathode slurry, and are not described again.
The invention also provides a preparation method of the lithium ion secondary battery, which comprises the following steps:
step S1: preparing composite anode slurry, and coating the composite anode slurry on the surface of a current collector to obtain an anode;
step S2: and preparing a negative electrode, and assembling the positive electrode, the negative electrode, the diaphragm and the electrolyte to obtain the lithium ion secondary battery.
Compared with the prior art, the advantages of the preparation method of the lithium ion secondary battery are the same as those of the composite cathode slurry, and are not repeated herein.
Drawings
Fig. 1 is a flow chart illustrating the preparation of a lithium ion secondary battery according to an embodiment of the present invention.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
It is noted that the description of the term "some specific embodiments" in the description of the embodiments herein is intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. Throughout this specification, the schematic representations of the terms used above do not necessarily refer to the same implementation or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The embodiment of the invention provides composite anode slurry, which is used for an anode of a lithium ion battery and comprises an anode active substance, a conductive agent, a binder and a solvent, wherein the anode active substance comprises a lithium transition metal oxide and a sodium-containing active component.
According to the composite anode slurry disclosed by the embodiment of the invention, the lithium transition metal oxide and the sodium-containing active component are introduced into the anode active substance of the composite anode slurry, so that sodium ions and lithium ions which are separated from an anode prepared from the composite anode slurry in the charging and discharging process of a lithium ion battery can be respectively stored in different active positions of an anode material according to the characteristics of different radiuses, and therefore, the comprehensive utilization rate of active points of the anode material in the lithium ion battery is favorably improved, the anode has higher reversible specific capacity, the first efficiency of the battery is favorably improved, and the energy density of the lithium ion secondary battery is further improved. Meanwhile, the embodiment of the invention introduces the sodium element with relatively rich reserves into the composite anode slurry, thereby reducing the using amount of the lithium element, saving the lithium resource and reducing the cost of the battery.
In some specific embodiments, the sodium-containing active component accounts for 5% to 30% of the weight of the positive active material.
The composite cathode slurry provided by the embodiment of the invention improves the first efficiency of the battery by utilizing the synergistic effect of lithium ions and sodium ions, and improves the energy density of the battery. However, the radius of the sodium ions is large, so that the migration speed of the sodium ions in the pole piece is low, if the content of the sodium-containing active component in the composite anode slurry is too high, the rate performance of the battery is poor, and therefore the sodium-containing active component is controlled to be 5-30% of the weight percentage of the anode active material, so that the energy density of the battery can be considered, and the influence on the rate performance of the battery can be reduced.
In some specific embodiments, the lithium transition metal oxide comprises at least one of lithium cobaltate, lithium manganate, lithium nickelate, lithium iron phosphate, lithium vanadium phosphate, or a ternary material. Therefore, the material selection range is wide, and cost control is facilitated.
In some specific embodiments, the sodium-containing active component comprises at least one of a sodium-containing oxide material, a polyanionic material, or a prussian blue-based material.
The general structural formula of the sodium-containing oxide material in the embodiment of the invention is Nax2M1O2M1 is at least one of transition metal elements; the structural general formula of the polyanion material is Nax3M2y3(Xa3Ob3)z3Zw3Wherein M2 is at least one of Ti, V, Cr, Mn, Fe, Co, Ni, Ca, Mg, Al and Nb, and X is at least one of Si, S, P, As, B, Mo, W and Ge; z is F or OH, and the values of x3, y3, Z3, w3, a3 and b3 meet the charge balance; the structural general formula of the Prussian blue material is Ax4Mb4[M(CN)6]y4·nH2O, wherein x4 is more than or equal to 0 and less than or equal to 2, y4 is more than or equal to 0 and less than or equal to 1, A is alkali metal ions, M is one of Mn and Fe, and the values of x4, y4 and b4 meet the charge balance.
In some specific embodiments, the mass ratio of the positive electrode active material, the conductive agent, the binder, and the solvent includes: 100: (0.5-5): (0.5-10): (40-150).
Wherein, the conductive agent is preferably at least one of carbon black, acetylene black, carbon fiber and flake graphite; the binder is preferably polyvinylidene fluoride; the solvent is preferably azomethylpyrrolidone. Therefore, the composite anode slurry provided by the embodiment of the invention can simultaneously provide sodium ions and lithium ions during charging through the synergistic effect of the anode active material, the conductive agent, the binder and the solvent in a certain proportion, so that the comprehensive utilization rate of the active points of the cathode material is improved, the reversible specific capacity of the cathode is improved, the first efficiency of the battery is improved, and the energy density of the lithium ion secondary battery is further improved through the synergistic effect of the sodium ions and the lithium ions.
The invention also provides a lithium ion secondary battery which comprises a positive electrode, a negative electrode, electrolyte and a diaphragm arranged between the positive electrode and the negative electrode, wherein the positive electrode comprises the composite positive electrode slurry.
In the prior art, a lithium ion secondary battery of a transition metal oxide/carbon system is generally adopted, and in the charging and discharging processes, on one hand, because lithium ions can only be inserted into the interlayer position of a negative electrode material, the utilization rate of an active point of the negative electrode material is low, and the reversible specific capacity of the negative electrode is low; on the other hand, a part of the lithium ions reacts with the electrolyte to form a solid electrolyte film (SEI film), and a part of the lithium ions are lost, thereby reducing the energy density of the battery. Therefore, in order to improve the efficiency and reduce the irreversible capacity of the first charging, the common mode adopted in the industry is a negative electrode lithium supplement technology, but the method has the following defects: because the activity of lithium is very high, the lithium is required to be prepared in a dry environment for isolating moisture, so that the process is complex, the difficulty of mass production is very high, and the cost is high.
Therefore, in order to improve the utilization rate of active points of a negative electrode material in the lithium ion secondary battery and improve the first efficiency of the lithium ion secondary battery, the invention introduces a lithium transition metal oxide and a sodium-containing active component into the positive electrode of the lithium ion secondary battery, wherein the lithium transition metal oxide provides a lithium ion sodium-containing active substance in the charging and discharging process and provides sodium ions in the charging and discharging process, thereby realizing energy storage and release through reversible insertion and extraction of two different ions of the lithium ions and the sodium ions between the positive electrode and the negative electrode.
The sodium element and the lithium element in the embodiment of the invention are positioned in the same main group, and the chemical properties and the physical properties of the sodium element and the lithium element are similar, so that when the sodium ion and the lithium ion are used for the lithium ion secondary battery, the sodium ion and the lithium ion have similar working principle and energy storage mechanism, and the sodium-containing active component is introduced into the anode slurry of the lithium ion secondary battery, so that the smooth operation of the charging and discharging process of the lithium ion secondary battery can be ensured; and because the radius of lithium ions is different from that of sodium ions, the radius of sodium ions is greater than that of lithium ions, when the composite anode slurry simultaneously comprising sodium ions and lithium ions is used for a lithium ion secondary battery, in the charging process, the composite anode slurry simultaneously provides the lithium ions and the sodium ions, and after the lithium ions and the sodium ions are embedded into a negative electrode, the sodium ions and the lithium ions are respectively stored in different active positions of the negative electrode material due to the different radii of the lithium ions and the sodium ions, so that the comprehensive utilization rate of active points of the negative electrode material is improved, the negative electrode has higher reversible specific capacity, the primary efficiency of the battery is improved, and the energy density of the lithium ion secondary battery is improved.
In addition, the radius of the sodium ions is larger than that of the lithium ions, the lithium ions are embedded into the interlayer position of the negative electrode material in the charging process, and a part of the sodium ions are adsorbed at the micropores, defects and the surface of the negative electrode material, so that the part of the sodium ions are easier to be separated from the negative electrode material, the reversible specific capacity of the negative electrode is further improved, the initial efficiency of the battery is improved, and the energy density of the lithium ion secondary battery is improved.
In addition, sodium ions are introduced into the composite cathode slurry, so that the loss of lithium ions caused by the generation of an SEI (solid electrolyte interphase) film is compensated; meanwhile, the reserves of the sodium element are richer than those of the lithium element and are not widely distributed, so that the cost of the sodium element is far lower than that of the lithium element; by introducing sodium ions into the positive electrode slurry, the amount of lithium is reduced on the basis of ensuring normal charging and discharging of the battery, improving the first efficiency of the battery and improving the energy density of the battery, so that the energy is saved and the cost of the battery is reduced.
In some specific embodiments, the negative electrode includes a negative active material including at least one of artificial graphite, natural graphite, mesocarbon microbeads, hard carbon, soft carbon, or silicon carbon.
In some specific embodiments, the separator comprises one of a polypropylene microporous membrane, a polyethylene microporous membrane, a glass fiber mat, or a three-layer composite separator.
In some specific embodiments, the electrolyte comprises a lithium salt, a sodium salt, and a non-aqueous solvent; wherein the lithium salt comprises at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium perchlorate, lithium trifluoromethanesulfonate, lithium perfluorobutylsulfonate, lithium aluminate, lithium chloroaluminate, lithium fluorosulfonylimide, lithium chloride or lithium iodide; the sodium salt comprises at least one of sodium hexafluorophosphate, sodium tetrafluoroborate, sodium hexafluoroarsenate, sodium perchlorate, sodium trifluromethyl sulfonate, sodium perfluorobutyl sulfonate, sodium chloroaluminate or sodium fluorosulfonylimide; the non-aqueous solvent includes at least one of a fluorine-containing cyclic organic ester, a sulfur-containing cyclic organic ester, or an unsaturated bond-containing cyclic organic ester.
The embodiment of the invention also provides a preparation method of the lithium ion secondary battery, which comprises the following steps:
step S1: preparing composite anode slurry, and coating the composite anode slurry on the surface of a current collector to obtain an anode;
step S2: and preparing a negative electrode, and assembling the positive electrode, the negative electrode, the diaphragm and the electrolyte to obtain the lithium ion secondary battery.
The advantages of the method for preparing a lithium ion secondary battery according to the embodiment of the present invention over the prior art are the same as the advantages of the composite cathode slurry and the lithium ion secondary battery over the prior art, and are not described herein again.
Example 1
The method for manufacturing the lithium-ion secondary battery according to the embodiment is as follows:
step S1: lithium cobaltate (LiCO) with the mass fraction of 90 percent is adopted2) And 10 percent of sodium ferrite-based ternary cathode material (NaFe)1/3Ni1/3Mn1/3O2) As the positive electrode active material, carbon black in an amount of 0.5% by weight of the positive electrode active material was used as a conductive agent, polyvinylidene fluoride in an amount of 10% by weight of the positive electrode active material was used as a binder, and azomethylpyrrolidone in an amount of 150% by weight of the positive electrode active material was used as a solvent, and the positive electrode active material, the conductive agent, the binder, and the solvent were uniformly mixed to prepare a composite positive electrode slurry. Coating the two sides of the obtained composite anode slurry on an aluminum foil with the thickness of 16 mu m, wherein the coating thickness is 200 mu m; drying, rolling and slicing to obtain a positive electrode; the energy density of the obtained positive electrode is 1.0mAh/cm2；
Step S2: hard carbon is used as a negative active material (the specific capacity is 650mAh/g, the first efficiency of the full battery is 75 percent) to prepare negative slurry; coating the negative electrode slurry on the copper foil with 12 mu m on both sidesThe coating thickness is 50 μm, and the negative electrode is obtained after drying; the energy density of the obtained cathode is 1.1mAh/cm2；
Taking the obtained anode, the obtained cathode and a 20-micron PE porous membrane as a diaphragm, winding the diaphragm with the cathode/the diaphragm/the anode in an environment with controlled humidity to prepare a pole core, encapsulating the pole core in an aluminum-plastic film, and carrying out heat sealing on the pole core to prepare a battery core; and injecting the electrolyte into the battery cell, and standing to obtain the lithium ion secondary battery.
Electrochemical performance tests were performed on the prepared lithium ion secondary batteries, and the first efficiency was calculated, and the results are detailed in table 1.
Comparative example 1
In addition to example 1, the positive electrode active material in step S1 was replaced with lithium cobaltate (LiCO)2) Otherwise, the same contents as in example 1 were applied.
Electrochemical performance tests were performed on the prepared lithium ion secondary batteries, and the first efficiency was calculated, and the results are detailed in table 1.
Therefore, the sodium ferrite-based ternary cathode material (NaFe) is not added1/3Ni1/3Mn1/3O2) The first discharge capacity, the first charge capacity and the first efficiency of the positive active material are lower than those of the positive active material added with the sodium-containing active component (namely, the sodium-based ternary positive material (NaFe)1/3Ni1/3Mn1/3O2) ) a lithium ion secondary battery. Therefore, the composite anode slurry introduces the sodium-containing active component, which is beneficial to improving the comprehensive utilization rate of the active points of the cathode material in the lithium ion battery, so that the cathode has higher reversible specific capacity, and the first efficiency of the battery and the energy density of the lithium ion secondary battery are improved.
Example 2
The method for manufacturing the lithium-ion secondary battery according to the embodiment is as follows:
step S1: lithium cobaltate (LiCO) with the mass fraction of 90 percent is adopted2) And 10 percent of sodium ferrite-based ternary cathode material (NaFe)1/3Ni1/3Mn1/3O2) As the positive electrode active material, carbon fibers having a weight of 1% of the weight of the positive electrode active material were used as the conductive materialThe composite positive electrode slurry is prepared by uniformly mixing the positive electrode active material, the conductive agent, the binder and the solvent by using polyvinylidene fluoride accounting for 8% of the weight of the positive electrode active material as the binder and azomethidone accounting for 120% of the weight of the positive electrode active material as the solvent. Coating the two sides of the obtained composite anode slurry on an aluminum foil with the thickness of 16 mu m, wherein the coating thickness is 200 mu m; drying, rolling and slicing to obtain a positive electrode; the energy density of the obtained positive electrode is 1.0mAh/cm2；
Step S2: preparing cathode slurry by using soft carbon as a cathode active material (the specific capacity is 300mAh/g, the first efficiency of a full battery is 80%); coating the two sides of the negative electrode slurry on a copper foil with the thickness of 100 mu m, and drying to obtain a negative electrode; the energy density of the obtained cathode is 1.1mAh/cm2；
Taking the obtained anode, the obtained cathode and a 20-micron PE porous membrane as diaphragms, winding the cathode/diaphragm/anode in a humidity-controlled environment to obtain a pole core, packaging the pole core in an aluminum-plastic film, and performing heat sealing on the pole core to obtain a battery cell; and injecting the electrolyte into the battery cell, and standing to obtain the lithium ion secondary battery.
Electrochemical performance tests were performed on the prepared lithium ion secondary batteries, and the first efficiency was calculated, and the results are detailed in table 1.
Comparative example 2
In addition to example 2, the positive electrode active material in step S1 was replaced with lithium cobaltate (LiCO)2) Otherwise, the same contents as in example 2 were applied.
Electrochemical performance tests were performed on the prepared lithium ion secondary batteries, and the first efficiency was calculated, and the results are detailed in table 1.
Therefore, the sodium ferrite-based ternary cathode material (NaFe) is not added1/3Ni1/3Mn1/3O2) The first discharge capacity, the first charge capacity and the first efficiency of the positive active material are lower than those of the positive active material added with the sodium-containing active component (namely, the sodium-based ternary positive material (NaFe)1/3Ni1/3Mn1/3O2) ) a lithium ion secondary battery.
Example 3
The method for manufacturing the lithium-ion secondary battery according to the embodiment is as follows:
step S1: adopting a ternary material (LiCo) with the mass fraction of 95 percent1/3Ni1/3Mn1/3O2) And 5 percent of sodium ferrite-based ternary cathode material (NaFe)1/3Ni1/3Mn1/3O2) Uniformly mixing the positive electrode active material, the conductive agent, the binder and the solvent by using acetylene black accounting for 2% of the weight of the positive electrode active material as a conductive agent, polyvinylidene fluoride accounting for 4% of the weight of the positive electrode active material as a binder and azomethylpyrrolidone accounting for 100% of the weight of the positive electrode active material as a solvent to prepare composite positive electrode slurry; coating the two sides of the obtained composite anode slurry on an aluminum foil with the thickness of 16 mu m, wherein the coating thickness is 200 mu m; drying, rolling and slicing to obtain a positive electrode; the energy density of the obtained positive electrode is 1.0mAh/cm2；
Step S2: preparing cathode slurry by using soft carbon as a cathode active material (the specific capacity is 300mAh/g, the first efficiency of a full battery is 80%); coating the two sides of the negative electrode slurry on a copper foil with the thickness of 100 mu m, and drying to obtain a negative electrode; the energy density of the obtained cathode is 1.1mAh/cm2；
Winding the obtained anode, the obtained cathode and a 20-micron PE porous membrane as a diaphragm in a humidity-controlled environment by using the cathode/diaphragm/anode to prepare a pole core, packaging the pole core in an aluminum-plastic film, and performing heat sealing on the pole core to prepare a battery cell; and injecting the electrolyte into the battery cell, and standing to obtain the lithium ion secondary battery.
Electrochemical performance tests were performed on the prepared lithium ion secondary batteries, and the first efficiency was calculated, and the results are detailed in table 1.
Comparative example 3
On the basis of example 3, the positive electrode active material in step S1 was replaced with a ternary material (LiCo)1/3Ni1/ 3Mn1/3O2) Otherwise, the same contents as in example 3 were applied.
Electrochemical performance tests were performed on the prepared lithium ion secondary batteries, and the first efficiency was calculated, and the results are detailed in table 1.
Therefore, the sodium ferrite-based ternary cathode material (NaFe) is not added1/3Ni1/3Mn1/3O2) The first discharge capacity, the first charge capacity and the first efficiency of the positive active material are lower than those of the positive active material added with the sodium-containing active component (namely, the sodium-based ternary positive material (NaFe)1/3Ni1/3Mn1/3O2) ) a lithium ion secondary battery.
Example 4
The method for manufacturing the lithium-ion secondary battery according to the embodiment is as follows:
step S1: adopting 85% lithium iron phosphate (LiFePO)4) Mixing with 15% vanadium sodium phosphate (Na)3V2(PO4)3) Uniformly mixing a positive electrode active material, a conductive agent, a binder and a solvent to prepare a composite positive electrode slurry, wherein the positive electrode active material is flake graphite with the weight of 3% of the weight of the positive electrode active material as the conductive agent, the polyvinylidene fluoride with the weight of 2% of the weight of the positive electrode active material as the binder, and the azomethidone with the weight of 60% of the weight of the positive electrode active material as the solvent; coating the two sides of the obtained composite anode slurry on an aluminum foil with the thickness of 16 mu m, wherein the coating thickness is 200 mu m; drying, rolling and slicing to obtain a positive electrode; the energy density of the obtained positive electrode is 1.0mAh/cm2；
Step S2: adopting artificial graphite as a negative active material (the specific capacity is 340mAh/g, the first efficiency of a full battery is 88%), and preparing negative slurry; coating the two sides of the negative electrode slurry on a copper foil with the thickness of 12 mu m, wherein the coating thickness is 80 mu m, and drying to obtain a negative electrode; the energy density of the obtained cathode is 1.1mAh/cm2；
Taking the obtained anode, the obtained cathode and a 20-micron PE porous membrane as diaphragms, winding the cathode/diaphragm/anode in a humidity-controlled environment to obtain a pole core, packaging the pole core in an aluminum plastic film, and performing heat sealing on the pole core to obtain a battery cell; and injecting the electrolyte into the battery cell, and standing to obtain the lithium ion secondary battery.
Electrochemical performance tests were performed on the prepared lithium ion secondary batteries, and the first efficiency was calculated, and the results are detailed in table 1.
Comparative example 4
In addition to example 4, the positive electrode active material in step S1 was replaced with lithium iron phosphate (LiFePO)4) Otherwise, the same contents as in example 4 were applied.
Electrochemical performance tests were performed on the prepared lithium ion secondary batteries, and the first efficiency was calculated, and the results are detailed in table 1.
Thus, it can be seen that sodium vanadium phosphate (Na) was not added3V2(PO4)3) The first discharge capacity, the first charge capacity and the first efficiency of the positive electrode active material are lower than those of the positive electrode active material added with the sodium-containing active component (sodium vanadium phosphate (Na)3V2(PO4)3) ) a lithium ion secondary battery.
Example 5
The method for manufacturing the lithium-ion secondary battery according to the embodiment is as follows:
step S1: lithium iron phosphate (LiFePO) with the mass fraction of 90 percent is adopted4) Mixing with 30% vanadium sodium phosphate (Na)3V2(PO4)3) Uniformly mixing carbon black serving as a positive electrode active material, wherein the weight of the carbon black is 5% of the weight of the positive electrode active material, polyvinylidene fluoride serving as a binder, the weight of the polyvinylidene fluoride serving as 0.5% of the weight of the positive electrode active material, and azomethidone serving as a solvent, wherein the weight of the azomethidone is 40% of the weight of the positive electrode active material, so as to prepare composite positive electrode slurry; coating the two sides of the obtained composite anode slurry on an aluminum foil with the thickness of 16 mu m, wherein the coating thickness is 200 mu m; drying, rolling and slicing to obtain a positive electrode; the energy density of the obtained positive electrode is 1.0mAh/cm2；
Step S2: preparing cathode slurry by using hard carbon as a cathode active material (the specific capacity is 550mAh/g, the first efficiency of a full battery is 76%); coating the two sides of the negative electrode slurry on a copper foil with the thickness of 12 mu m, wherein the coating thickness is 40 mu m, and drying to obtain a negative electrode; the energy density of the obtained cathode is 1.1mAh/cm2；
Winding the obtained anode, the obtained cathode and a 20-micron PE porous membrane as a diaphragm in an environment with controlled humidity to obtain a pole core, packaging the pole core in an aluminum plastic film, and performing heat sealing on the pole core to obtain a battery cell; and injecting the electrolyte into the battery cell, and standing to obtain the lithium ion secondary battery.
Electrochemical performance tests were performed on the prepared lithium ion secondary batteries, and the first efficiency was calculated, and the results are detailed in table 1.
Comparative example 5
In addition to example 5, the positive electrode active material in step S1 was replaced with lithium iron phosphate (LiFePO)4) Otherwise, the same contents as in example 5 were applied.
Electrochemical performance tests were performed on the prepared lithium ion secondary batteries, and the results are detailed in table 1.
Thus, it can be seen that sodium vanadium phosphate (Na) was not added3V2(PO4)3) The first discharge capacity, the first charge capacity and the first efficiency of the positive electrode active material are lower than those of the positive electrode active material added with the sodium-containing active component (sodium vanadium phosphate (Na)3V2(PO4)3) ) a lithium ion secondary battery.
Electrochemical tests were carried out on the cells prepared in the above examples and comparative examples according to the following method:
the design capacity of the cells prepared in each example and comparative example was 450mAh (0.5C discharge). The batteries prepared in examples 1 to 3 and comparative examples 1 to 3 were charged at room temperature at 0.2mAh/cm 2; the upper limit voltage of the battery is 4.2V and is 0.5mAh/cm2Discharging, wherein the lower limit voltage is 2.5V; the batteries obtained in example 4 and example 5 and the batteries obtained in comparative example 4 and comparative example 5 were used at a rate of 0.2mAh/cm2Charging; the upper limit voltage of the battery is 3.7V and is 0.5mAh/cm2Discharging, wherein the lower limit voltage is 2.0V; the first charge capacity and discharge capacity were measured and shown in table 1.
TABLE 1
| First discharge capacity (mAh) | First time charging capacity (mAh) | First time efficiency | |
| Example 1 | 489 | 609 | 80.3％ |
| Comparative example 1 | 445 | 591 | 75.2％ |
| Example 2 | 473 | 575 | 82.3％ |
| Comparative example 2 | 438 | 552 | 79.3％ |
| Example 3 | 476 | 564 | 84.5％ |
| Comparative example 3 | 439 | 545 | 80.5％ |
| Example 4 | 475 | 534 | 89.1％ |
| Comparative example 4 | 448 | 511 | 87.6％ |
| Example 5 | 496 | 603 | 82.6％ |
| Comparative example 5 | 445 | 585 | 75.7％ |
As can be seen from the comparison of the data of each example with the data of the corresponding comparative example, under the same conditions, the battery using the composite cathode slurry simultaneously including the lithium transition metal oxide and the sodium-containing active component has higher first efficiency and battery capacity than the battery using a single lithium transition metal oxide; and when the negative active material selects hard carbon, the effect of improving the first efficiency is more obvious.
Although the present disclosure has been described above, the scope of the present disclosure is not limited thereto. Various changes and modifications may be effected therein by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present disclosure, and these changes and modifications are intended to be within the scope of the present disclosure.
Claims (10)
1. The composite cathode slurry is used for a cathode of a lithium ion battery and is characterized by comprising a cathode active substance, a conductive agent, a binder and a solvent, wherein the cathode active substance comprises a lithium transition metal oxide and a sodium-containing active component.
2. The composite positive electrode slurry according to claim 1, wherein the sodium-containing active component accounts for 5 to 30% by weight of the positive electrode active material.
3. The composite cathode slurry according to claim 1, wherein the lithium transition metal oxide comprises at least one of lithium cobaltate, lithium manganate, lithium nickelate, lithium iron phosphate, lithium vanadium phosphate, or a ternary material.
4. The composite cathode slurry according to claim 1, wherein the sodium-containing active component comprises at least one of a sodium-containing oxide material, a polyanionic material, or a prussian blue material.
5. The composite positive electrode slurry according to claim 1, wherein a mass ratio of the positive electrode active material, the conductive agent, the binder, and the solvent includes: 100: (0.5-5): (0.5-10): (40-150).
6. A lithium ion secondary battery comprising a positive electrode, a negative electrode, an electrolytic solution, and a separator interposed between the positive electrode and the negative electrode, the positive electrode comprising the composite positive electrode slurry according to any one of claims 1 to 5.
7. The lithium ion secondary battery of claim 6, wherein the negative electrode comprises a negative active material comprising at least one of artificial graphite, natural graphite, mesocarbon microbeads, hard carbon, soft carbon, or silicon carbon.
8. The lithium ion secondary battery of claim 6, wherein the separator comprises one of a polypropylene microporous membrane, a polyethylene microporous membrane, a glass fiber mat, or a three-layer composite separator.
9. The lithium ion secondary battery according to claim 6, wherein the electrolytic solution includes a lithium salt, a sodium salt, and a nonaqueous solvent; wherein the lithium salt comprises at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium perchlorate, lithium trifluoromethanesulfonate, lithium perfluorobutylsulfonate, lithium aluminate, lithium chloroaluminate, lithium fluorosulfonylimide, lithium chloride or lithium iodide; the sodium salt comprises at least one of sodium hexafluorophosphate, sodium tetrafluoroborate, sodium hexafluoroarsenate, sodium perchlorate, sodium trifluromethyl sulfonate, sodium perfluorobutyl sulfonate, sodium chloroaluminate or sodium fluorosulfonylimide; the non-aqueous solvent includes at least one of a fluorine-containing cyclic organic ester, a sulfur-containing cyclic organic ester, or an unsaturated bond-containing cyclic organic ester.
10. A method for producing a lithium-ion secondary battery according to any one of claims 6 to 9, characterized by comprising the steps of:
step S1: preparing composite anode slurry, and coating the composite anode slurry on the surface of a current collector to obtain an anode;
step S2: and preparing a negative electrode, and assembling the positive electrode, the negative electrode, the diaphragm and the electrolyte to obtain the lithium ion secondary battery.
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