CN112701277A - Lithium ion battery prelithiation additive and application thereof - Google Patents
Lithium ion battery prelithiation additive and application thereof Download PDFInfo
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- CN112701277A CN112701277A CN202011545811.1A CN202011545811A CN112701277A CN 112701277 A CN112701277 A CN 112701277A CN 202011545811 A CN202011545811 A CN 202011545811A CN 112701277 A CN112701277 A CN 112701277A
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 79
- 239000000654 additive Substances 0.000 title claims abstract description 65
- 230000000996 additive effect Effects 0.000 title claims abstract description 65
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 50
- 239000007774 positive electrode material Substances 0.000 claims abstract description 40
- 239000011572 manganese Substances 0.000 claims abstract description 27
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 15
- 238000006138 lithiation reaction Methods 0.000 claims abstract description 11
- 229910008096 Li1+aNixCoyMn1-x-yO2 Inorganic materials 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000002002 slurry Substances 0.000 claims description 46
- 239000010405 anode material Substances 0.000 claims description 31
- 239000007773 negative electrode material Substances 0.000 claims description 31
- 239000002904 solvent Substances 0.000 claims description 30
- 239000011230 binding agent Substances 0.000 claims description 28
- 239000006258 conductive agent Substances 0.000 claims description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
- 239000002131 composite material Substances 0.000 claims description 26
- 239000011248 coating agent Substances 0.000 claims description 22
- 238000000576 coating method Methods 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 22
- 238000005096 rolling process Methods 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 19
- 230000004913 activation Effects 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 239000002153 silicon-carbon composite material Substances 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 11
- 238000003475 lamination Methods 0.000 claims description 10
- 238000004804 winding Methods 0.000 claims description 10
- 230000001351 cycling effect Effects 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 3
- 239000012798 spherical particle Substances 0.000 claims description 3
- 239000013589 supplement Substances 0.000 abstract description 17
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 230000001276 controlling effect Effects 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 239000010406 cathode material Substances 0.000 description 19
- 239000002041 carbon nanotube Substances 0.000 description 18
- 229910021393 carbon nanotube Inorganic materials 0.000 description 18
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 10
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 7
- 239000002033 PVDF binder Substances 0.000 description 7
- 239000006182 cathode active material Substances 0.000 description 7
- 239000011889 copper foil Substances 0.000 description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- GWWAIWVRXPPMOU-UHFFFAOYSA-N [Li].[Pt] Chemical compound [Li].[Pt] GWWAIWVRXPPMOU-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 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 description 1
- 229910018632 Al0.05O2 Inorganic materials 0.000 description 1
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 1
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 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 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 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
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- -1 smart phones Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a lithium ion battery prelithiation additive, the chemical formula of the additive is Li1+aNixCoyMn1‑x‑yO2Wherein, 0<a<1,0<x<0.5,0≤y<0.5. According to the invention, a high-capacity lithium-rich manganese-based positive electrode material is used as a lithium ion battery prelithiation additive, and is compounded with the lithium ion battery positive electrode material by regulating and controlling the first coulombic efficiency of the lithium-rich manganese-based positive electrode material, so that lithium is supplemented to a negative electrode in the charge-discharge process of a battery system, and the lithium-rich material can realize stable low coulombic efficiency circulation in the circulation process, and can supplement lithium to the negative electrode continuously. Pre-lithiation of lithium ion battery by using high-capacity lithium-rich manganese-based positive electrode materialThe additive, the battery manufacturing and using safety are one of the important methods for solving the problem of poor cycle stability of the high specific energy battery.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a lithium ion battery prelithiation additive and application thereof.
Background
In recent years, with the rapid growth of various consumer electronic products such as smart phones, tablet computers, electronic bracelets and the like, the market of energy-saving and environment-friendly electric vehicles and the initial development of the market of energy storage batteries, the market of lithium ion batteries serving as power supplies of these products is rapidly developing. The lithium ion battery is a secondary battery with the characteristics of environmental protection, high energy density, long cycle life and the like. Along with the expansion of the use range and the increasing dependence degree of the lithium ion battery, the requirements on various performance indexes of the lithium ion battery are higher and higher, particularly the energy density and the safety performance. In terms of energy density. The high energy density lithium ion battery usually needs high specific energy anode and cathode materials, the cathode material usually selects a silicon-carbon composite cathode material, the gram discharge capacity of the silicon-carbon composite cathode material is more than 1000mAh/g, but the silicon-carbon composite cathode material has large first irreversible capacity, and the application possibility of the silicon-carbon composite cathode material is seriously limited.
In order to solve the problem of realizing a high specific energy battery system and simultaneously solving the problem of poor cycling stability, a pre-lithiation technology is developed to realize lithium supplement in the first circle of charging and discharging process of the battery and lithium supplement in the cycling process of the battery, a plurality of research attempts are carried out at home and abroad in recent years, but most of the materials such as lithium belts, lithium platinum, metal lithium powder and the like are added into the battery system and are embedded into a negative electrode material in the form of extra lithium ions in the first circle of charging process, so that enough lithium ions can be moved back to a positive electrode material in the discharging process of the material, the first irreversible capacity of the battery is obviously reduced, and the cycling stability is further improved simultaneously.
In order to solve the problem of realizing a high specific energy battery system and simultaneously solving the problem of poor cycling stability, a pre-lithiation technology is developed to realize lithium supplement in the first circle of charging and discharging process of the battery and lithium supplement technology in the cycling process of the battery, a plurality of research attempts are carried out at home and abroad in recent years, but most of the materials such as lithium belts, lithium platinum, metal lithium powder and the like are added into the battery system and are embedded into a negative electrode material in the form of extra lithium ions in the first circle of charging process, so that enough lithium ions can be moved back to a positive electrode material in the discharging process of the material, the first irreversible capacity of the battery is obviously reduced, and the cycling stability is further improved simultaneously.
However, no matter the lithium ribbon, lithium platinum and metal lithium powder are easy to have severe chemical reaction with water in the air to cause serious potential safety hazards such as combustion and the like, so that the requirements on the environment in the operation process of the lithium supplement method are extremely strict, particularly the requirements on water control and human operation control in the production process of the battery are extremely strict, only a few domestic and foreign household battery enterprises can have the lithium supplement technology for the battery at present, but accidents inevitably occur in the battery production process under many conditions, and serious accidents are caused.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a lithium ion battery prelithiation additive and an application thereof, wherein the lithium ion battery prelithiation additive provided by the present invention is safe and convenient to use, and can solve the problem of poor cycle stability of a high specific energy battery when applied to lithium ion battery prelithiation.
The invention provides a lithium ion battery prelithiation additive, the chemical formula of the additive is Li1+ aNixCoyMn1-x-yO2Wherein, 0<a<1,0<x<0.5,0≤y<0.5,
Preferably, the secondary spherical particles of the additive have a particle size of 3 to 30 μm; the surface area of the lithium-rich manganese-based positive electrode material is 3-8 m2/g。
Preferably, the first charge capacity of the additive is 250-400 mAh/g, the first charge-discharge coulombic efficiency is 40-90%, and the coulombic efficiency in the material circulation process after the second cycle is 95-100.5%.
The invention also provides a battery prelithiation method, which comprises the following steps:
adding a prelithiation additive to a lithium ion battery, and then performing a first cycle of charging activation on the lithium ion battery.
Preferably, the method for adding the prelithiation additive to the lithium ion battery is as follows:
a) mixing and stirring a pre-lithiation additive, a positive electrode material, a conductive agent, a binder and a solvent to obtain a lithium ion battery composite positive electrode material slurry;
b) coating the composite anode material slurry on an anode current collector, and drying, slicing and rolling a pole piece to obtain an anode material pole piece;
c) mixing and stirring a negative electrode active material, a conductive agent, a binder and a solvent to obtain a slurry of the negative electrode material of the lithium ion battery;
d) coating the negative electrode material slurry on a negative electrode current collector, and drying, slicing and rolling a pole piece to obtain a negative electrode material pole piece;
e) assembling the positive pole piece and the negative pole piece into a battery cell in a lamination or winding mode;
f) and baking the battery core, injecting electrolyte and forming to obtain the lithium ion battery.
Preferably, the mass ratio of the prelithiation additive to the positive electrode material is (2-25): 100.
preferably, the negative electrode active material is a graphite negative electrode or a graphite silicon carbon composite negative electrode.
Preferably, the activation voltage of the first circle of charging activation is more than or equal to 4.45V.
Compared with the prior art, the invention provides the lithium ion battery prelithiation additive, and the chemical formula of the additive is Li1+aNixCoyMn1-x-yO2Wherein, 0<a<1,0<x<0.5,0≤y<0.5,. According to the invention, a high-capacity lithium-rich manganese-based positive electrode material is used as a lithium ion battery prelithiation additive, and is compounded with the lithium ion battery positive electrode material by regulating and controlling the first coulombic efficiency of the lithium-rich manganese-based positive electrode material, so that lithium is supplemented to a negative electrode in the charge-discharge process of a battery system, and the lithium-rich material can realize stable low coulombic efficiency circulation in the circulation process, and can supplement lithium to the negative electrode continuously. The high-capacity lithium-rich manganese-based positive electrode material is used as the pre-lithiation additive of the lithium ion battery, and the safety in battery manufacturing and use is one of important methods for solving the problem of poor cycle stability of the high specific energy battery.
Detailed Description
The invention provides a lithium ion battery prelithiation additive, the chemical formula of the additive is Li1+ aNixCoyMn1-x-yO2Wherein, 0<a<1,0<x<0.5,0≤y<0.5。
In the present invention, 0< a <1, preferably 0.1< a <0.9, and more preferably 0.1< a < 0.6;
0< x <0.5, preferably 0.01< x <0.4, further preferably 0.05< x <0.4, more preferably 0.1< x < 0.2;
0. ltoreq. y <0.5, preferably 0. ltoreq. y <0.4, more preferably 0. ltoreq. y <0.3, and still more preferably 0. ltoreq. y < 0.2.
In some embodiments of the invention, the prelithiation additive is selected from Li1.12Ni0.133Co0.133Mn0.554O2；
In some embodiments of the invention, the prelithiation additive is selected from Li1.18Ni0.15Co0.15Mn0.45O2；
In some embodiments of the invention, the prelithiation additive is selected from Li1.6Ni0.2Mn0.6O2；
In some embodiments of the invention, the prelithiation additive is selected from Li1.5Ni0.2Co0.1Mn0.55O2。
In the present invention, the secondary spherical particles of the additive have a particle diameter of 3 to 30 μm, preferably 5 to 25 μm, and more preferably 10 to 20 μm; the surface area of the lithium-rich manganese-based positive electrode material is 3-8 m2Preferably 4 to 7 m/g2(iv)/g, more preferably 5 to 6m2/g。
In the invention, the first charge capacity of the additive is 250-400 mAh/g, the first charge-discharge coulombic efficiency is 40-90%, and the coulombic efficiency of the additive in the second and later circulation processes is 95-100.5%.
The lithium can be supplemented to the negative electrode in the first circle of charging and discharging process of the battery, the problem that the energy density is influenced by low first coulomb efficiency of the negative electrode of the battery is solved, and meanwhile, the lithium can be supplemented to the negative electrode in each circle of the battery circulating process, so that the circulating stability of the battery is improved.
The invention also provides a battery prelithiation method, which comprises the following steps:
adding a prelithiation additive to a lithium ion battery, and then performing a first cycle of charging activation on the lithium ion battery.
The method for adding the prelithiation additive to the lithium ion battery comprises the following steps:
a) mixing and stirring a pre-lithiation additive, a positive electrode material, a conductive agent, a binder and a solvent to obtain a lithium ion battery composite positive electrode material slurry;
b) coating the composite anode material slurry on an anode current collector, and drying, slicing and rolling a pole piece to obtain an anode material pole piece;
c) mixing and stirring a negative electrode active material, a conductive agent, a binder and a solvent to obtain a slurry of the negative electrode material of the lithium ion battery;
d) coating the negative electrode material slurry on a negative electrode current collector, and drying, slicing and rolling a pole piece to obtain a negative electrode material pole piece;
e) assembling the positive pole piece and the negative pole piece into a battery cell in a lamination or winding mode;
f) and baking the battery core, injecting electrolyte and forming to obtain the lithium ion battery.
Specifically, the pre-lithiation additive, the positive electrode material, the conductive agent, the binder and the solvent are mixed and stirred to obtain the composite positive electrode material slurry of the lithium ion battery.
Wherein the mass ratio of the pre-lithiation additive to the positive electrode material is (2-25): 100, preferably (5-20): 100, more preferably (10 to 15): 100.
the prelithiation additive is the prelithiation additive described above.
The positive electrode material, the conductive agent, the binder and the solvent are not particularly limited in the present invention, and may be any kind known to those skilled in the art to be usable in a lithium ion battery.
In the invention, the anode material is selected from one or more of lithium iron phosphate, ternary materials, lithium manganate, lithium silicate, lithium nickel manganese oxide and lithium-rich manganese-based anode materials;
the conductive agent is selected from one or more of conductive carbon black, carbon nano tubes and graphene;
the binder is selected from one or more of PVDF, sodium carboxymethylcellulose, polyacrylic acid and sodium alginate;
the solvent is selected from N, N-methyl pyrrolidone.
The mass ratio of the positive electrode material to the conductive agent to the binder to the solvent is 80-95: 10-2: 10-3.
And then, coating the composite anode material slurry on an anode current collector, and drying, slicing and rolling the anode current collector to obtain an anode material pole piece.
Wherein the positive electrode current collector is selected from aluminum foil.
The present invention is not particularly limited to the specific method of coating, drying, slicing, and rolling, and may be any method known to those skilled in the art.
The invention also mixes and stirs the cathode active material, the conductive agent, the binding agent and the solvent to obtain the slurry of the cathode material of the lithium ion battery.
The negative active material is a graphite negative electrode or a graphite silicon-carbon composite negative electrode.
Specific kinds of the conductive agent, the binder, and the solvent are not particularly limited, and may be those known to those skilled in the art.
And then, coating the negative electrode material slurry on a negative electrode current collector, and drying, slicing and rolling the pole piece to obtain a negative electrode material pole piece. In the present invention, the negative electrode current collector is preferably a copper foil.
The present invention is not particularly limited to the specific method of coating, drying, slicing, and rolling, and may be any method known to those skilled in the art.
The invention has no special limitation on the preparation sequence of the positive pole piece and the negative pole piece.
Then, assembling the positive pole piece and the negative pole piece into a battery cell in a lamination or winding mode;
and finally, baking the battery core, injecting electrolyte and forming to obtain the lithium ion battery.
The method for assembling the battery cell, baking the battery cell, injecting the electrolyte and forming the battery cell is not particularly limited, and the method known by the person skilled in the art can be used.
And after the lithium ion battery is obtained, carrying out first-circle charging activation on the lithium ion battery. The lithium-rich material of the pre-lithiation additive supplements lithium to a negative electrode in the first charge and discharge process of a battery system, and the activation voltage of the lithium-rich material is higher than 4.45V.
The battery prelithiation method provided by the invention is simple to implement and does not generate potential safety hazard, the prelithiation additive serving as an ideal anode material in the later period does not influence the normal circulation of a battery system, the discharge gram capacity of the prelithiation additive is higher than that of a common anode material, and the energy density of the battery system is improved to a certain extent
According to the invention, a high-capacity lithium-rich manganese-based positive electrode material is used as a lithium ion battery prelithiation additive, and is compounded with the lithium ion battery positive electrode material according to a certain proportion by regulating and controlling the first coulombic efficiency of the lithium-rich manganese-based positive electrode material, so that lithium is supplemented to a negative electrode in the charge-discharge process of a battery system, and the lithium-rich material can realize stable low coulombic efficiency circulation in the circulation process, and can supplement lithium to the negative electrode continuously. The high-capacity lithium-rich manganese-based positive electrode material is used as the pre-lithiation additive of the lithium ion battery, and the safety in battery manufacturing and use is one of important methods for solving the problem of poor cycle stability of the high specific energy battery.
The prelithiation additive provided by the invention effectively overcomes the serious potential safety hazards that no matter the lithium belt, lithium platinum and metal lithium powder are easy to generate violent chemical reaction with water in the air to cause combustion and the like, and the requirement on the environment in the operation process of the lithium supplement method is very strict, especially the requirement on the moisture control in the production process of batteries, including the manual operation control is very strict, only a few domestic and foreign household battery enterprises can have the battery lithium supplement technology at present, but the occurrence of accidents in the battery manufacturing process which are inevitable under many conditions is also frequently reported, so that the occurrence of serious accidents is caused.
For further understanding of the present invention, the lithium ion battery prelithiation additive and its application provided by the present invention are described below with reference to the following examples, and the scope of the present invention is not limited by the following examples.
The reagents used in the following examples are all commercially available.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Example 1
A lithium ion battery prelithiation additive and a method for using the same in battery prelithiation comprises the following steps;
a) the positive electrode material LiNi0.8Co0.1Mn0.1O2With a prelithiation additive lithium-rich manganese-based positive electrode material Li1.12Ni0.133Co0.133Mn0.554O2Mixing according to the mass percentage of 80% to 5%, simultaneously adding 2.5% of SP + 10% of carbon nano tube composite conductive agent, 2.5% of binder PVDF and solvent NMP (the solvent amount is 35% of the concentration of the slurry) into a material mixing kettle, and stirring to obtain the lithium ion battery composite anode material slurry;
b) coating the composite anode material slurry on an anode current collector, drying a pole piece, slicing and rolling to obtain an anode material pole piece for later use
c) Similarly, the cathode active material silicon-carbon composite cathode material has a discharge gram capacity of 850mAh/g, a conductive agent SP + carbon nano tube and a binder CMC, and the ratio of the conductive agent SP + carbon nano tube to the binder CMC is as follows (95: 1+1: 3) adding deionized water as a solvent with the mass ratio of 45% into the mixture, adding the mixture into a batching kettle, and stirring to obtain slurry of the lithium ion battery cathode material;
d) coating the negative electrode material slurry on a negative electrode current collector copper foil, drying a pole piece, slicing and rolling to obtain a negative electrode material pole piece for later use,
e) assembling the positive and negative pole pieces into a 25Ah battery cell in a lamination or winding mode;
f) baking the battery core, injecting electrolyte, and forming to obtain the lithium ion battery
g) Charging the first circle of the battery to 4.55V for activation, and carrying out first circle of negative electrode lithium supplement
The first efficiency of the full battery reaches 93%, the energy density of the full battery reaches 365Wh/Kg, and the capacity retention rate of the full battery is 92% after 500 cycles within the voltage range of 2.8-4.45V. Is suitable for the basic application requirements of high specific energy power batteries.
Example 2
A lithium ion battery prelithiation additive and a method for using the same in battery prelithiation comprises the following steps;
a) the positive electrode material LiNi0.6Co0.2Mn0.2O2With a prelithiation additive lithium-rich manganese-based positive electrode material Li1.12Ni0.133Co0.133Mn0.554O2Mixing 80% to 10% by mass, adding 2.5% of SP + 5% of graphene composite conductive agent, 2.5% of binder PVDF and solvent NMP (the solvent amount accounts for 40% of the mass of the slurry) into a material mixing kettle, and stirring to obtain the lithium ion battery composite anode material slurry;
b) coating the composite anode material slurry on an anode current collector, drying a pole piece, slicing and rolling to obtain an anode material pole piece for later use
c) Similarly, the cathode active material graphite cathode material has a discharge gram capacity of 450mAh/g, a conductive agent SP + carbon nano tube, a binder CMC, and a carbon nano tube powder prepared according to the following formula (90: 2+2: 6) adding 35% by mass of solvent, namely deionized water, SBR, into the proportioning kettle, and stirring to obtain lithium ion battery cathode material slurry;
d) coating the negative electrode material slurry on a negative electrode current collector copper foil, drying a pole piece, slicing and rolling to obtain a negative electrode material pole piece for later use,
e) assembling the positive and negative pole pieces into a 25Ah battery cell in a lamination or winding mode;
f) baking the battery core, injecting electrolyte, and forming to obtain the lithium ion battery
g) Charging the first circle of the battery to 4.6V for activation, and performing first circle of negative electrode lithium supplement
The first efficiency of the full battery reaches 96%, the energy density of the full battery reaches 265Wh/Kg, and the capacity retention rate of the full battery is 95% after 500 cycles within the voltage range of 2.8-4.35V. The method is suitable for basic requirements of power battery application.
Example 3
A lithium ion battery prelithiation additive and a method for using the same in battery prelithiation comprises the following steps;
a) the positive electrode material LiNi0.8Co0.1Mn0.1O2With a prelithiation additive lithium-rich manganese-based positive electrode material Li1.18Ni0.15Co0.15Mn0.45O2Mixing according to the mass percentage of 80% to 12%, simultaneously adding 2% of SP + 3% of carbon nano tube composite conductive agent, 3% of binder PVDF and solvent NMP (the solvent amount accounts for 30% of the mass of the slurry) into a batching kettle, and stirring to obtain the lithium ion battery composite anode material slurry;
b) coating the composite anode material slurry on an anode current collector, drying a pole piece, slicing and rolling to obtain an anode material pole piece for later use
c) Similarly, the cathode active material silicon-carbon composite cathode material has a discharge gram capacity of 850mAh/g, a conductive agent SP + carbon nano tube and a binder CMC, and the ratio of the conductive agent SP + carbon nano tube to the binder CMC is as follows (95: 1+1: 3) adding deionized water as a solvent with the mass ratio of 45% into the mixture, adding the mixture into a batching kettle, and stirring to obtain slurry of the lithium ion battery cathode material;
d) coating the negative electrode material slurry on a negative electrode current collector copper foil, drying a pole piece, slicing and rolling to obtain a negative electrode material pole piece for later use,
e) assembling the positive and negative pole pieces into a 25Ah battery cell in a lamination or winding mode;
f) baking the battery core, injecting electrolyte, and forming to obtain the lithium ion battery
g) Charging the first circle of the battery to 4.55V for activation, and carrying out first circle of negative electrode lithium supplement
The first efficiency of the full battery reaches 93%, the energy density of the full battery reaches 365Wh/Kg, and the capacity retention rate of the full battery is 92% after 500 cycles within the voltage range of 2.8-4.45V. Is suitable for the basic application requirements of high specific energy power batteries.
Example 4
A lithium ion battery prelithiation additive and a method for using the same in battery prelithiation comprises the following steps;
a) the positive electrode material LiNi0.5Co0.2Mn0.3O2With a prelithiation additive lithium-rich manganese-based positive electrode material Li1.6Ni0.2Mn0.6O2Mixing according to the mass percentage of 90% to 3%, simultaneously adding 2% of SP + 2% of carbon nano tube composite conductive agent, 3% of binder PVDF and solvent NMP (the solvent amount accounts for 35% of the mass of the slurry) into a batching kettle, and stirring to obtain the lithium ion battery composite anode material slurry;
b) coating the composite anode material slurry on an anode current collector, drying a pole piece, slicing and rolling to obtain an anode material pole piece for later use
c) Similarly, the cathode active material silicon-carbon composite cathode material has the discharge gram capacity of 950mAh/g, a conductive agent SP + carbon nano tube and a binder CMC, and the ratio of the conductive agent SP + carbon nano tube to the binder CMC is as follows (95: 0.5+0.5: 4) adding deionized water as a solvent with the mass ratio of 45% into the mixture, adding the mixture into a batching kettle, and stirring to obtain slurry of the lithium ion battery cathode material;
d) coating the negative electrode material slurry on a negative electrode current collector copper foil, drying a pole piece, slicing and rolling to obtain a negative electrode material pole piece for later use,
e) assembling the positive and negative pole pieces into a 25Ah battery cell in a lamination or winding mode;
f) baking the battery core, injecting electrolyte, and forming to obtain the lithium ion battery
g) Charging the first circle of the battery to 4.55V for activation, and carrying out first circle of negative electrode lithium supplement
The first efficiency of the full battery reaches 95%, the energy density of the full battery reaches 325Wh/Kg, and the capacity retention rate of the full battery is 95% after 1000 cycles within the voltage range of 2.8-4.45V. Is suitable for the basic application requirements of high specific energy power batteries.
Example 5
A lithium ion battery prelithiation additive and a method for using the same in battery prelithiation comprises the following steps;
a) the positive electrode material LiNi0.9Co0.05Al0.05O2With a prelithiation additive lithium-rich manganese-based positive electrode material Li1.5Ni0.2Co0.1Mn0.55O2Mixing according to the mass percentage of 87% to 3%, simultaneously adding 2% of SP + 4% of carbon nano tube composite conductive agent, 4% of binder PVDF and solvent NMP (the solvent amount accounts for 39% of the mass of the slurry) into a material mixing kettle, and stirring to obtain the lithium ion battery composite anode material slurry;
b) coating the composite anode material slurry on an anode current collector, drying a pole piece, slicing and rolling to obtain an anode material pole piece for later use
c) Similarly, the cathode active material silicon-carbon composite cathode material has a discharge gram capacity of 1050mAh/g, a conductive agent SP + carbon nano tube, a binder CMC, and a carbon nano tube powder prepared according to the following steps of (95: 0.5+0.5: 4) adding deionized water as a solvent with the mass ratio of 40% into the mixture according to the proportion, and adding the mixture into a batching kettle to stir to obtain slurry of the lithium ion battery cathode material;
d) coating the negative electrode material slurry on a negative electrode current collector copper foil, drying a pole piece, slicing and rolling to obtain a negative electrode material pole piece for later use,
e) assembling the positive and negative pole pieces into a 25Ah battery cell in a lamination or winding mode;
f) baking the battery core, injecting electrolyte, and forming to obtain the lithium ion battery
g) Charging the first circle of the battery to 4.65V for activation, and performing first circle of negative electrode lithium supplement
The first efficiency of the full cell reaches 95%, the energy density of the full cell reaches 375Wh/Kg, and the capacity retention rate of the full cell is 97% after 1000 cycles within the voltage range of 2.8-4.45V. Is suitable for the basic application requirements of high specific energy power batteries.
Comparative example 1
A lithium ion battery prelithiation additive and a method for using the same in battery prelithiation comprises the following steps;
a) 85% of positive electrode material LiNi0.8Co0.1Mn0.1O2Simultaneously adding 2.5% of SP + 10% of carbon nanotube composite conductive agent, 2.5% of binder PVDF and solvent NMP (the solvent amount is 35% of the slurry concentration) into a batching kettle, and stirring to obtain the lithium ion battery composite anode material slurry;
b) coating the composite anode material slurry on an anode current collector, drying a pole piece, slicing and rolling to obtain an anode material pole piece for later use
c) Similarly, the cathode active material silicon-carbon composite cathode material has a discharge gram capacity of 850mAh/g, a conductive agent SP + carbon nano tube and a binder CMC, and the ratio of the conductive agent SP + carbon nano tube to the binder CMC is as follows (95: 1+1: 3) adding deionized water as a solvent with the mass ratio of 45% into the mixture, adding the mixture into a batching kettle, and stirring to obtain slurry of the lithium ion battery cathode material;
d) coating the negative electrode material slurry on a negative electrode current collector copper foil, drying a pole piece, slicing and rolling to obtain a negative electrode material pole piece for later use,
e) assembling the positive and negative pole pieces into a 25Ah battery cell in a lamination or winding mode;
f) baking the battery core, injecting electrolyte, and forming to obtain the lithium ion battery
g) Charging the first circle of the battery to 4.55V to form
The first efficiency of the full cell reaches 89%, the energy density of the full cell reaches 295Wh/Kg, and the capacity retention rate of the full cell is 80% after 500 cycles within the voltage range of 2.8-4.45V.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. The lithium ion battery prelithiation additive is characterized in that the chemical formula of the additive is Li1+ aNixCoyMn1-x-yO2Wherein, 0<a<1,0<x<0.5,0≤y<0.5。
2. The prelithiation additive of claim 1, wherein the secondary spherical particles of the additive have a particle size of 3 μ ι η to 30 μ ι η; the surface area of the lithium-rich manganese-based positive electrode material is 3-8 m2/g。
3. The prelithiation additive of claim 1, wherein the additive has a first charge capacity of 250-400 mAh/g, a first cycle charge-discharge coulombic efficiency of 40-90%, and a second and subsequent cycles of material cycling with coulombic efficiency of 95-100.5%.
4. A battery prelithiation method comprising the steps of:
adding a prelithiation additive to a lithium ion battery, and then performing a first cycle of charging activation on the lithium ion battery.
5. The prelithiation method according to claim 4, wherein the method of adding the prelithiation additive to the lithium ion battery is:
a) mixing and stirring a pre-lithiation additive, a positive electrode material, a conductive agent, a binder and a solvent to obtain a lithium ion battery composite positive electrode material slurry;
b) coating the composite anode material slurry on an anode current collector, and drying, slicing and rolling a pole piece to obtain an anode material pole piece;
c) mixing and stirring a negative electrode active material, a conductive agent, a binder and a solvent to obtain a slurry of the negative electrode material of the lithium ion battery;
d) coating the negative electrode material slurry on a negative electrode current collector, and drying, slicing and rolling a pole piece to obtain a negative electrode material pole piece;
e) assembling the positive pole piece and the negative pole piece into a battery cell in a lamination or winding mode;
f) and baking the battery core, injecting electrolyte and forming to obtain the lithium ion battery.
6. The prelithiation method according to claim 5, wherein the mass ratio of the prelithiation additive to the positive electrode material is (2-25): 100.
7. the prelithiation method of claim 5, wherein the negative active material is a graphite negative electrode or a graphite silicon carbon composite negative electrode.
8. The prelithiation method of claim 4, wherein the activation voltage of the first charge activation is 4.45V or more.
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