CN113328098A - Negative plate and lithium ion battery comprising same - Google Patents
Negative plate and lithium ion battery comprising same Download PDFInfo
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- CN113328098A CN113328098A CN202110785660.5A CN202110785660A CN113328098A CN 113328098 A CN113328098 A CN 113328098A CN 202110785660 A CN202110785660 A CN 202110785660A CN 113328098 A CN113328098 A CN 113328098A
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- negative electrode
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 31
- 239000000654 additive Substances 0.000 claims abstract description 48
- 230000000996 additive effect Effects 0.000 claims abstract description 46
- 239000003792 electrolyte Substances 0.000 claims abstract description 36
- 239000007773 negative electrode material Substances 0.000 claims description 19
- 239000011230 binding agent Substances 0.000 claims description 16
- 239000006258 conductive agent Substances 0.000 claims description 14
- -1 nitrile compounds Chemical class 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000011356 non-aqueous organic solvent Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 125000001165 hydrophobic group Chemical group 0.000 claims description 3
- CDUWJQGFRQTJHB-UHFFFAOYSA-N 1,3,2-dioxathiole 2,2-dioxide Chemical compound O=S1(=O)OC=CO1 CDUWJQGFRQTJHB-UHFFFAOYSA-N 0.000 claims description 2
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 2
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- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims description 2
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- 230000005012 migration Effects 0.000 abstract description 12
- 238000013508 migration Methods 0.000 abstract description 12
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- 239000002033 PVDF binder Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
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- 239000002210 silicon-based material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
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- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- ZVLDJSZFKQJMKD-UHFFFAOYSA-N [Li].[Si] Chemical compound [Li].[Si] ZVLDJSZFKQJMKD-UHFFFAOYSA-N 0.000 description 1
- MKPXGEVFQSIKGE-UHFFFAOYSA-N [Mg].[Si] Chemical compound [Mg].[Si] MKPXGEVFQSIKGE-UHFFFAOYSA-N 0.000 description 1
- HIVGXUNKSAJJDN-UHFFFAOYSA-N [Si].[P] Chemical compound [Si].[P] HIVGXUNKSAJJDN-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
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- 229910045601 alloy Inorganic materials 0.000 description 1
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- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
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- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
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- 239000003273 ketjen black Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
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- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- MCSINKKTEDDPNK-UHFFFAOYSA-N propyl propionate Chemical compound CCCOC(=O)CC MCSINKKTEDDPNK-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
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- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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Images
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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
- H01M2004/027—Negative 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a negative plate and a lithium ion battery comprising the same. According to the invention, the additive is added into the negative plate, and the additive can be dissolved in the electrolyte after being injected into the battery, so that an ion channel is formed in the negative plate, the migration rate of lithium ions is improved, and the charging rate of the battery is improved. If the additive is an electrolyte auxiliary agent, the additive not only can be used for forming holes in the negative plate, but also can be dissolved in electrolyte to serve as the electrolyte auxiliary agent, so that the requirement on electrical property is met, and the cost is saved.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a negative plate and a lithium ion battery comprising the same.
Background
In recent years, lithium ion batteries have been widely used in the fields of smart phones, tablet computers, smart wearing, electric tools, electric automobiles, and the like. With the acceleration of life rhythm and the development of electronic products, the demands of consumers on shortening the charging time of the lithium ion battery and improving the energy density of the lithium ion battery are more urgent.
The lithium ion battery needs to reduce the coating thickness of the pole piece, shorten the migration distance of lithium ions and improve the migration rate of the lithium ions in order to realize the purpose of quick charge. However, in order to meet the requirement of high energy density of the battery cell, the thickness of the pole piece is generally required to be increased, which is in contradiction with the reduction of the thickness of the pole piece for realizing quick charge. Therefore, how to increase the energy density of the lithium ion battery while achieving fast charge is urgently needed to be solved.
Disclosure of Invention
In order to solve the problem that the energy density and the charging speed of a lithium ion battery in the prior art cannot be considered at the same time, the invention provides a negative plate and the lithium ion battery comprising the same. According to the invention, the additive capable of being dissolved in the electrolyte is introduced into the negative plate, so that the negative plate can be internally subjected to hole forming, ion channels are increased, and the migration rate of lithium ions is improved. The lithium ion battery obtained by the method does not lose energy density, and can meet the requirement of quick charge.
The purpose of the invention is realized by the following technical scheme:
the negative plate comprises a negative current collector and a negative active material layer coated on the surface of one side or two sides of the negative current collector, wherein the negative active material layer comprises a negative active material, a conductive agent, a binder and an additive, and the additive is a substance which can be partially or completely dissolved in electrolyte.
According to the invention, the electrolyte comprises a non-aqueous organic solvent in which the additive is partially or completely soluble.
According to the invention, the additive is selected from substances containing hydrophobic groups that are partially or completely soluble in the electrolyte. Illustratively, the additive is selected from at least one of polyethylene oxide, nitrile compounds, carbonate compounds, and sulfur-containing compounds.
In the invention, the additive contains hydrophobic groups which are easily adsorbed on the surface of the negative active material, when the negative plate containing the additive is soaked in the electrolyte, the additive is partially or completely dissolved in the electrolyte, and a fresh exposed interface is generated on the surface of the negative active material, so that Li can be further increased in the process+And the transmission channel improves the dynamic performance of the lithium ion battery.
In the invention, when the negative electrode slurry is prepared, the additive, the negative electrode active material, the conductive agent and the binder are added into the negative electrode slurry together, and the negative electrode sheet containing the additive can be prepared after coating. The negative pole piece is assembled into a battery core, and then liquid is injected, because the electrolyte is usually a non-aqueous organic solvent, the added additive can be partially or completely dissolved into the electrolyte, on one hand, the negative pole piece can generate pores (the porosity of the negative pole piece can be improved by 1% -3%), a micro-channel is formed, the migration of lithium ions is facilitated, the migration rate is improved, and the quick charge of the battery is realized; on the other hand, the additive is dissolved into the electrolyte after liquid injection, so that the electrolyte is not influenced, and the additive dissolved into the electrolyte can also serve as an electrolyte auxiliary agent to further improve the electrical performance of the battery.
According to the invention, the polyethylene oxide has a number average molecular weight of 5 to 200 ten thousand, for example 10 to 100 ten thousand. When the molecular weight is more than 200 ten thousand, the ethylene oxide molecules are easy to react to form a ring structure, and the phenomenon of overhigh viscosity of slurry is easy to occur during the batching, thus being not beneficial to the production.
According to the present invention, the nitrile compound includes at least one of succinonitrile, glutaronitrile, adiponitrile, pimelonitrile, octanedionitrile, glycerol trinitrile, ethoxypentafluorophosphazene, and 1,3, 6-hexanetrinitrile.
According to the invention, the carbonate compound comprises at least one of ethylene carbonate, fluoroethylene carbonate and ethylene carbonate.
According to the present invention, the sulfur-containing compound includes at least one of 1, 3-propane sultone, 1, 3-propene sultone, vinyl sulfate, and vinylene sulfate.
According to the invention, the negative electrode active material layer comprises the following components in percentage by mass: 85-98.9 wt% of negative electrode active material, 0.5-5 wt% of conductive agent, 0.5-5 wt% of binder and 0.1-5 wt% of additive.
Illustratively, the content of the negative electrode active material is 85 wt%, 86 wt%, 87 wt%, 88 wt%, 89 wt%, 90 wt%, 91 wt%, 92 wt%, 93 wt%, 94 wt%, 95 wt%, 96 wt%, 97 wt%, 98 wt%, or 98.9 wt% based on the total mass of the negative electrode active material layer.
Illustratively, the content of the conductive agent is 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, or 5 wt% of the total mass of the anode active material layer.
Illustratively, the additive is present in an amount of 0.1 wt%, 0.15 wt%, 0.25 wt%, 0.55 wt%, 0.65 wt%, 0.70 wt%, 0.75 wt%, 0.85 wt%, 0.90 wt%, 1.0 wt%, 1.2 wt%, 1.5 wt%, 2 wt%, 3 wt%, 4 wt%, or 5 wt% based on the total mass of the anode active material layer. When the additive content is more than 5 wt%, that is, the additive content is too high, the negative electrode active material is reduced, and the energy density of the battery is reduced; when the content of the additive is less than 0.1 wt%, namely the content of the additive is too low, the pore-forming quantity of the additive is small, and the migration rate of lithium ions is not obviously improved.
Illustratively, the content of the binder is 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, or 5 wt% of the total mass of the anode active material layer.
According to the present invention, the anode active material is selected from a silicon-based material and/or a carbon-based material.
Wherein the carbon-based material is selected from at least one of artificial graphite, natural graphite, hard carbon, soft carbon, mesophase microspheres, fullerene and graphene.
Wherein the silicon-based material is selected from at least one of nano silicon, SiOx (0< x <2), aluminum-silicon alloy, magnesium-silicon alloy, borosilicate alloy, phosphorus-silicon alloy and lithium-silicon alloy.
According to the invention, the conductive agent comprises one or more of conductive carbon black, Ketjen black, conductive fibers, conductive polymers, acetylene black, carbon nanotubes, graphene, flake graphite, conductive oxides and metal particles.
According to the invention, the binder is selected from at least one of polyvinylidene fluoride and its copolymer derivative, polytetrafluoroethylene and its copolymer derivative, polyacrylic acid and its copolymer derivative, polyvinyl alcohol and its copolymer derivative, polystyrene-butadiene rubber and its copolymer derivative, polyimide and its copolymer derivative, polyethyleneimine and its copolymer derivative, polyacrylate and its copolymer derivative, and sodium carboxymethylcellulose and its copolymer derivative.
According to the invention, the single-side surface density of the negative plate is 1-25 mg/cm2。
According to the present invention, the thickness of the anode active material layer (the thickness of the one-sided anode active material layer after roll pressing) is 10 μm to 150 μm, preferably 30 μm to 100 μm, such as 10 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm or 150 μm.
The invention also provides a preparation method of the negative plate, which comprises the following steps:
uniformly mixing a solvent, a negative electrode active material, a conductive agent, a binder and an additive to prepare negative electrode slurry; and coating the negative electrode slurry on the surface of the negative electrode current collector, and drying to obtain the negative electrode sheet.
According to the invention, the negative electrode slurry contains 100-300 parts by mass of a solvent, 85-98.9 parts by mass of a negative electrode active material, 0.5-5 parts by mass of a conductive agent, 0.1-5 parts by mass of an additive and 0.5-5 parts by mass of a binder.
According to the invention, the solvent is selected from at least one of water, acetonitrile, benzene, toluene, xylene, acetone, tetrahydrofuran, hydrofluoroether, N-methylpyrrolidone.
According to the present invention, the negative electrode slurry is preferably sieved, for example, 200 mesh.
According to the invention, the drying temperature is 70-110 ℃, and the drying time is 12-36 hours.
The invention also provides a lithium ion battery, which comprises a negative plate, a positive plate and electrolyte; the negative plate is the negative plate.
According to the invention, the electrolyte also comprises the above-mentioned additives.
According to the invention, the additive in the electrolyte is obtained by dissolving the additive in the negative electrode sheet into the electrolyte.
The invention has the beneficial effects that:
the invention provides a negative plate and a lithium ion battery comprising the same. According to the invention, the additive is added into the negative plate, and the additive can be dissolved in the electrolyte after being injected into the battery, so that an ion channel is formed in the negative plate, the migration rate of lithium ions is improved, and the charging rate of the battery is improved. If the additive is an electrolyte auxiliary agent, the additive not only can be used for forming holes in the negative plate, but also can be dissolved in electrolyte to serve as the electrolyte auxiliary agent, so that the requirement on electrical property is met, and the cost is saved.
Drawings
FIG. 1: the mechanism of action of the additives of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Comparative example 1
1) Preparing a positive plate:
mixing 95g of positive electrode active material lithium cobaltate, 2g of binder polyvinylidene fluoride (PVDF), 2g of conductive agent conductive carbon black and 1g of conductive agent carbon nano tube, adding 200g of N-methyl pyrrolidone (NMP), and stirring under the action of a vacuum stirrer until a mixed system becomes positive electrode slurry with uniform fluidity; uniformly coating the positive electrode slurry on an aluminum foil with the thickness of 12 mu m; drying the positive plate at 100 ℃ for 36 hours, then carrying out vacuum treatment to obtain a pole piece, rolling the pole piece, and cutting to obtain a positive plate;
2) preparing a negative plate:
preparing 96.9g of graphite, 0.5g of conductive agent SP, 1.3g of binder carboxymethylcellulose sodium (CMC), 1.3g of binder Styrene Butadiene Rubber (SBR) and 300g of deionized water into slurry by a wet process, coating the slurry on the surface of a copper foil of a negative current collector, and drying, rolling and die-cutting to obtain a negative plate;
3) preparing an electrolyte:
uniformly mixing ethylene carbonate, propylene carbonate, diethyl carbonate and n-propyl propionate according to the mass ratio of 20:10:15:55 in a glove box filled with argon and qualified in water oxygen content, and then rapidly adding 1mol/L of fully dried lithium hexafluorophosphate (LiPF)6) Uniformly stirring to prepare electrolyte;
4) preparation of lithium ion battery
And preparing a lithium ion battery cell from the obtained positive plate and the negative plate, and carrying out liquid injection packaging and welding to obtain the lithium ion battery.
Example 1
Other operations are the same as comparative example 1, except that the preparation of the negative electrode sheet:
preparing 96.9g of graphite, 0.5g of polyethylene oxide (molecular weight is 10W), 0.5g of conductive agent SP, 1.3g of binder carboxymethyl cellulose sodium (CMC), 1.3g of binder Styrene Butadiene Rubber (SBR) and 300g of deionized water into slurry by a wet process, coating the slurry on the surface of a copper foil of a negative current collector, and drying, rolling and die-cutting to obtain a negative plate.
Example 2
Other operations are the same as comparative example 1, except that the preparation of the negative electrode sheet:
preparing 96.9g of graphite, 0.5g of polyethylene oxide (molecular weight of 100W), 0.5g of conductive agent SP, 1.3g of binder carboxymethyl cellulose sodium (CMC), 1.3g of binder Styrene Butadiene Rubber (SBR) and 300g of deionized water into slurry by a wet process, coating the slurry on the surface of a copper foil of a negative current collector, and drying, rolling and die-cutting to obtain a negative plate.
And (3) performance testing:
(1) and (3) testing the rate charging performance of the battery:
the test is carried out at the temperature of 25 +/-5 ℃, and the test process is as follows:
1. standing for 10 min;
2. discharging to lower limit voltage of 3.0V at 0.2C;
3. standing for 10 min;
4. charging at a certain multiplying power (0.2C/0.5C/1C/1.5C/2C), and cutting off current of 0.05C; wherein, constant current charging capacity Q1, total charging capacity Q2 are recorded;
5. standing for 10 min;
6. discharging to lower limit voltage of 3.0V at 0.2C in a constant temperature environment;
7. standing for 10 min.
8. A constant current charging ratio (constant current charging ratio: constant current charging capacity Q1/total charging capacity Q2 × 100%), i.e., a value of constant current charging capacity Q1/total charging capacity Q2, was calculated.
Table 1 rate charging performance of batteries prepared in examples 1 to 2 and comparative example 1
| Item | Example 1 | Example 2 | Comparative example 1 |
| 0.2C | 94.46％ | 94.45％ | 93.66％ |
| 0.5C | 86.30％ | 86.21％ | 84.72％ |
| 1.0C | 76.44％ | 77.66％ | 72.66％ |
| 1.5C | 64.65％ | 65.19％ | 59.98％ |
| 2.0C | 49.52％ | 50.77％ | 44.77％ |
(2) And (3) testing the rate discharge performance of the battery:
the test is carried out at the temperature of 25 +/-5 ℃, and the test process is as follows:
1. standing for 10 min;
2. discharging to lower limit voltage of 3.0V at 0.2C;
3. standing for 10 min;
4. 0.7C is full, and the cut-off current is 0.05C;
5. standing for 10 min;
6. discharging at a constant temperature in a constant-temperature environment at a certain multiplying power (0.2C/0.5C/1C/1.5C/2C/3C) until the lower limit voltage is 3.0V;
7. standing for 10 min;
8. the capacity retention rate (the capacity retention rate discharged in comparison with 0.2C) was calculated, i.e., the values of 0.5C/0.2C, 1.0C/0.2C, 1.5C/0.2C, 2C/0.2C, and 3C/0.2C.
Table 2 rate discharge performance of batteries prepared in examples 1 to 2 and comparative example 1
| Item | Example 1 | Example 2 | Comparative example 1 |
| 0.5C/0.2C | 98.87％ | 98.82％ | 98.75％ |
| 1C/0.2C | 96.40％ | 96.54％ | 96.23％ |
| 1.5C/0.2C | 93.51％ | 94.40％ | 91.49％ |
| 2C/0.2C | 88.88％ | 89.89％ | 85.45％ |
| 3C/0.2C | 75.98％ | 78.33％ | 68.01％ |
As can be seen from tables 1 and 2, the battery composed of the negative electrode sheet of the present invention is more suitable for a fast charge system, which is mainly because the negative electrode sheet of the present invention includes the additive, the additive is dissolved in the electrolyte after contacting with the electrolyte, and the negative electrode sheet after being dissolved has pores to form microchannels, which is helpful for the migration of lithium ions, improves the migration rate, and realizes the fast charge of the battery.
(3) And (3) testing the porosity of the negative plate:
the test process is as follows: flatly laying the pole piece on a glass desktop, cutting the pole piece into a certain size, measuring the thickness of the pole piece by a ten-thousandth micrometer, and calculating the volume of the pole piece to be V1; then putting the pole piece into testing equipment, opening a gas valve, introducing helium gas, and testing the true volume V2 of the pole piece; the porosity of the pole piece was obtained according to the formula (V1-V2)/V1 × 100%, and the test results are shown in table 3.
Table 3 porosity test of negative electrode sheets prepared in examples 1 to 2 and comparative example 1
As can be seen from table 3, the porosity of the negative electrode sheet (injected liquid) after the negative electrode sheet is assembled into the lithium ion battery is significantly improved, which indicates that the additive in the negative electrode sheet can be well dissolved in the electrolyte, and the negative electrode sheet can have pores after being dissolved (the porosity of the negative electrode sheet can be improved by 1% to 3%), form a microchannel, contribute to the migration of lithium ions, and improve the migration rate.
(4) And (3) energy density testing:
the thickness (unit mm) of the battery was measured using a 600g PPG thickness gauge, and the length and width (unit mm) were determined based on the model of the battery and were regarded as fixed values. Energy Density (ED, unit Wh/L) is the sort discharge Energy value (Wh)/cell thickness/cell length/cell width 1000, and the test results are shown in table 4.
Table 4 energy density test of the batteries prepared in examples 1 to 2 and comparative example 1
| Energy density Wh/L | |
| Comparative example 1 | 721.5 |
| Example 1 | 720.8 |
| Example 2 | 719.8 |
As can be seen from table 4, the energy density of the battery composed of the cathode sheets added with the additive is not significantly reduced, and at the same time, the quick charge capacity of the battery is further improved, which indicates that the battery of the present invention does not lose the energy density, and can meet the requirement of quick charge.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The negative plate comprises a negative current collector and a negative active material layer coated on the surface of one side or two sides of the negative current collector, wherein the negative active material layer comprises a negative active material, a conductive agent, a binder and an additive, and the additive is a substance which can be partially or completely dissolved in electrolyte.
2. The negative electrode sheet of claim 1, wherein the electrolyte comprises a non-aqueous organic solvent, and the additive is partially or completely soluble in the non-aqueous organic solvent.
3. The negative electrode sheet according to claim 1 or 2, wherein the additive is selected from substances that contain hydrophobic groups and are partially or completely soluble in the electrolyte.
4. The negative electrode sheet according to claim 3, wherein the additive is at least one selected from the group consisting of polyethylene oxide, nitrile compounds, carbonate compounds, and sulfur-containing compounds.
5. The negative electrode sheet according to claim 4, wherein the polyethylene oxide has a number average molecular weight of 5 to 200 ten thousand.
6. The negative electrode sheet according to claim 4, wherein the nitrile compound comprises at least one of succinonitrile, glutaronitrile, adiponitrile, pimelonitrile, octanedionitrile, glycerol trinitrile, ethoxypentafluorophosphazene, and 1,3, 6-hexanetrinitrile; and/or the presence of a gas in the gas,
the carbonate compound comprises at least one of ethylene carbonate, fluoroethylene carbonate and ethylene carbonate; and/or the presence of a gas in the gas,
the sulfur-containing compound includes at least one of 1, 3-propane sultone, 1, 3-propene sultone, vinyl sulfate and vinylene sulfate.
7. The negative electrode sheet according to any one of claims 1 to 6, wherein the negative electrode active material layer comprises the following components in percentage by mass: 85-98.9 wt% of negative electrode active material, 0.5-5 wt% of conductive agent, 0.5-5 wt% of binder and 0.1-5 wt% of additive.
8. The negative electrode sheet according to any one of claims 1 to 7, wherein the thickness of the negative electrode active material layer is 10 μm to 150 μm.
9. A lithium ion battery comprises a negative plate, a positive plate and electrolyte; the negative electrode sheet is the negative electrode sheet according to any one of claims 1 to 8.
10. The lithium ion battery according to claim 9, wherein the electrolyte also comprises the additive in the negative electrode sheet according to any one of claims 1 to 8; and/or the additive in the electrolyte is obtained by dissolving the additive in the negative electrode sheet of any one of claims 1 to 8 in the electrolyte.
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