CN110767880A - Lithium supplement slurry for lithium secondary battery and preparation method of lithium secondary battery - Google Patents

Lithium supplement slurry for lithium secondary battery and preparation method of lithium secondary battery Download PDF

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Publication number
CN110767880A
CN110767880A CN201810828004.7A CN201810828004A CN110767880A CN 110767880 A CN110767880 A CN 110767880A CN 201810828004 A CN201810828004 A CN 201810828004A CN 110767880 A CN110767880 A CN 110767880A
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lithium
binder
pole piece
slurry
secondary battery
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魏冠杰
史哲忠
布莱恩·托马斯·米本
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Micro Macro Power System (huzhou) Co Ltd
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Micro Macro Power System (huzhou) Co Ltd
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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
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/582—Halogenides
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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
    • 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

Abstract

The present invention provides a lithium supplement paste for a lithium secondary battery, comprising: a lithium-containing compound, a conductive agent, a binder, and an organic solvent, the binder being a binder soluble in a nonaqueous electrolyte solution. The lithium secondary battery obtained by the invention ensures that the cycle performance of the battery is unchanged, and the energy density of the lithium secondary battery is obviously improved.

Description

Lithium supplement slurry for lithium secondary battery and preparation method of lithium secondary battery
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a method for supplementing lithium to a positive pole piece or a diaphragm of a lithium ion battery.
Background
The lithium secondary battery using the non-aqueous electrolyte has advantages of high specific energy, little environmental pollution, etc. Since the introduction of commercial lithium secondary batteries was first introduced by sony corporation of japan in 1990, lithium secondary batteries have been widely used in electronic consumer products such as mobile phones, portable computers, and video cameras. With the continuous development of electronic product technologies such as smart phones and notebook computers, the energy density requirement of lithium secondary batteries is higher and higher.
In the first charge and discharge process of the non-aqueous electrolyte lithium secondary battery, due to the formation of a Solid Electrolyte Interface (SEI) film, the process consumes partially reversible lithium ions, resulting in a decrease in the amount of effective lithium ions, directly resulting in a loss of capacity of the battery, thereby reducing the energy density of the battery. The lithium secondary battery using the graphite carbon material as the negative electrode has a capacity loss rate of about 10% due to the negative electrode; the lithium secondary battery taking the silicon material, the silicon-oxygen material and the silicon alloy material as the negative electrode has lower first charge-discharge efficiency, higher capacity loss rate caused by the negative electrode and more obvious influence on the capacity of the whole battery. Therefore, it is necessary to supplement the irreversible capacity loss during the first lithium intercalation process by means of a lithium supplementation process.
At present, lithium supplement processes are mainly divided into two main categories: 1) a negative electrode lithium supplement process; 2) the lithium supplement process of the positive electrode, wherein the lithium supplement process of the negative electrode is the most common lithium supplement method, for example, the lithium supplement of lithium powder and the lithium supplement of lithium foil are the lithium supplement processes which are intensively developed by various manufacturers at present. The lithium powder lithium supplementing process adds a proper amount of lithium powder into the negative electrode through processes of spraying, homogenate adding and the like. Lithium supplement by lithium foil is also a new lithium supplement process in recent years, and metal lithium foil is rolled to a thickness of several micrometers, and then compounded and rolled with a negative electrode. After the battery is injected with liquid, the metal lithium reacts with the negative electrode rapidly and is embedded into the negative electrode material, so that the first efficiency of the material is improved. However, these methods have to face a problem of "safety of metallic lithium". The lithium metal is an alkali metal with high reaction activity and can react with water violently, so that the requirement of the lithium metal on the environment is very high, the two cathode lithium supplementing processes are required to invest huge resources to modify a production line and purchase expensive lithium supplementing equipment, and meanwhile, in order to ensure the lithium supplementing effect, the existing production process is required to be adjusted.
Compared with a negative electrode lithium supplement process with high difficulty and high input, the positive electrode lithium supplement is easier to realize, and the typical positive electrode lithium supplement process is that a small amount of high-capacity positive electrode materials are added in the positive electrode homogenizing process, and redundant Li elements are extracted from the high-capacity positive electrode materials and are inserted into a negative electrode to supplement irreversible capacity of first charge and discharge in the charging process. The anode lithium supplementing process has the greatest advantages of simple process, no need of changing the existing lithium ion battery production process, no need of expensive lithium supplementing equipment, and more importantly, the safety of the anode lithium supplementing process is very good. However, the proportion of active materials in the positive electrode may decrease during the lithium supplement process of the positive electrode, and the products after lithium supplement are inactive, thereby further improving the energy density of the lithium ion battery.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides a lithium supplementing method which is high in safety and low in cost, can supplement irreversible capacity loss in the process of lithium intercalation for the first time, and cannot cause the proportion of active substances of a positive electrode to be reduced, so that the energy density of a non-aqueous electrolyte lithium secondary battery is improved.
In order to achieve the above object, the present invention provides a lithium replenishing paste for a lithium secondary battery, comprising: a lithium-containing compound, a conductive agent, a binder, and an organic solvent, the binder being soluble in a non-aqueous electrolyte solution.
In the lithium supplement slurry, the adhesive has good compatibility with a carbonate solvent in a non-aqueous electrolyte, and can be slowly dissolved in the non-aqueous electrolyte under the wetting of the non-aqueous electrolyte. In one embodiment, the binder is at least one of Polymethylmethacrylate (PMMA), polyethylene oxide (PEO), and polyvinyl chloride (PVC).
The content of the binder in the lithium replenishment slurry is preferably such that the lithium-containing compound and the conductive agent can be attached to the surface of the positive electrode sheet (or separator) without increasing the viscosity of the electrolyte. In one embodiment, the binder is 2 to 20% by mass based on the total amount of the lithium-containing compound, the conductive agent and the binder. In one embodiment, the binder is 5 to 10% by mass based on the total amount of the lithium-containing compound, the conductive agent and the binder.
As an embodiment, the lithium-containing compound is selected from Li2O、Li3N、LiI、Li2At least one of S and lithium oxalate. The lithium-containing compound can be decomposed to generate lithium and gas in the formation and charging process of the lithium ion battery, the generated gas is extracted after the formation is finished, and lithium ions cannot be embedded into the lithium supplement layer. Therefore, the lithium-containing compound contributes a capacity at the time of charging to compensate for a capacity loss of the negative electrode forming the SEI film, reduces a lithium loss in the active material layer, and improves an energy density of the battery. After the formation is finished, a binder such as polymethyl methacrylate (PMMA) is slowly dissolved in the electrolyte along with the circulation, the separator and the positive electrode active material layer are restored to a state in which lithium is not replenished, and the separator and the positive electrode active material in the positive electrode active material layer can normally perform lithium ion extraction. As an embodiment, the lithium-containing compound is selected from Li2O and/or Li3At least one of N.
In the lithium supplement slurry, the amount of the lithium-containing compound is based on the condition that the irreversible loss of lithium ions in the charging and discharging process can be compensated. In one embodiment, the content of the lithium-containing compound may be 45 to 93% by mass based on the total amount of the lithium-containing compound, the conductive agent and the binder. In one embodiment, the content of the lithium-containing compound may be 60 to 90% by mass based on the total amount of the lithium-containing compound, the conductive agent and the binder.
In the present invention, if the amount of the lithium-containing compound is too large, the lithium-containing compound has poor conductivity, which is not favorable for the lithium ions to be deintercalated in a high-rate charge/discharge state, and the cycle performance of the battery obtained is poor.
The conductive agent in the lithium supplement slurry may be a conductive agent commonly used in a positive electrode of a lithium secondary battery, and as one embodiment, the conductive agent is selected from at least one of acetylene black (ACET), conductive carbon black (Super P), conductive graphite, carbon fiber (VGCF), carbon nanotube, and graphene.
The content of the conductive agent is based on the condition that the conductive agent can promote the decomposition of the lithium-containing compound in the lithium supplementing layer. In one embodiment, the conductive agent is 5 to 50% by mass based on the total amount of the lithium-containing compound, the conductive agent and the binder. In one embodiment, the conductive agent is 5 to 30% by mass based on the total amount of the lithium-containing compound, the conductive agent and the binder. In the present invention, the lithium-containing compound has poor conductivity and is not easily decomposed, and if the amount of the remaining lithium-containing compound is too large, the lithium-supplementing effect is not only impaired, but also the charge/discharge performance and cycle performance of the battery at a high rate are deteriorated. The conductive agent is added in the invention, so that the decomposition of the lithium-containing compound is obviously improved, and the charge-discharge performance and the cycle performance of the battery under high rate are promoted.
In one embodiment, the organic solvent is at least one selected from the group consisting of N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), N-Dimethylacetamide (DMAC), N-Diethylformamide (DEF), Dimethylsulfoxide (DMSO), and Tetrahydrofuran (THF).
The invention provides a preparation method of a lithium secondary battery, which comprises the following steps: 1) provided is a lithium replenishing slurry comprising: a lithium-containing compound, a conductive agent, a binder and an organic solvent, wherein the binder is a binder soluble in a non-aqueous electrolyte solution; 2) providing a positive pole piece, coating the lithium supplement slurry in the step 1) on the surface of the positive pole piece to prepare the positive pole piece with a lithium supplement layer on the surface; 3) and assembling the negative pole piece, the diaphragm, the non-aqueous electrolyte solution and the positive pole piece with the lithium supplementing layer on the surface into the lithium secondary battery.
The invention also provides a preparation method of the lithium secondary battery, which comprises the following steps: 1) provided is a lithium replenishing slurry comprising: a lithium-containing compound, a conductive agent, a binder and an organic solvent, wherein the binder is a binder soluble in a non-aqueous electrolyte solution; 2) providing a diaphragm, coating the lithium supplement slurry in the step 1) on the surface of the diaphragm to prepare the diaphragm with a lithium supplement layer on the surface; 3) and assembling the positive pole piece, the negative pole piece, the non-aqueous electrolyte solution and the diaphragm with the lithium supplement layer on the surface into the lithium secondary battery, wherein the lithium supplement layer on the surface of the diaphragm is opposite to the positive active material layer.
In the invention, the lithium supplement layer on the surface of the diaphragm needs to be opposite to the positive active material layer. The main purpose is to prevent the lithium supplement layer on the surface of the diaphragm from directly contacting with the negative electrode material to cause internal short circuit of the battery.
The lithium secondary battery obtained by the invention ensures that the cycle performance of the battery is unchanged, and the energy density of the lithium secondary battery is obviously improved.
In one embodiment, the positive active material in the positive electrode sheet is at least one selected from lithium iron phosphate, lithium cobaltate, lithium nickel cobalt manganese oxide, lithium rich manganese base, lithium nickelate, lithium manganate, lithium nickel manganese oxide, lithium manganese phosphate, lithium cobalt phosphate, lithium vanadium phosphate and lithium manganese silicate.
The preparation method of the lithium secondary battery further comprises the step of forming the lithium secondary battery.
The formation is to charge the prepared battery to the voltage of 4.5V by the current of 0.05C, and then to charge the battery by the constant voltage of 4.5V until the cut-off current is 0.0025C. The formation may be performed for charging the battery, and may be performed by oxidizing and decomposing a lithium-containing compound in the lithium supplement layer to generate lithium ions and a gas, and the generated gas may be extracted after the formation is completed, so that the lithium ions are inserted into the negative electrode.
In one embodiment, the separator is at least one selected from the group consisting of a woven film, a nonwoven film, a composite film, a separator paper, a roll-pressed film, a polypropylene film, and a polyethylene film.
In one embodiment, the solvent of the non-aqueous electrolyte solution includes at least one of dimethyl carbonate (DMC), diethyl carbonate (DEC), Propylene Carbonate (PC), Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC), Methyl Propyl Carbonate (MPC), methyl isopropyl carbonate (MIPC), Butylene Carbonate (BC), 1, 2-Dimethoxyethane (DME), dibutyl carbonate (DBC), methyl butyl carbonate (BMC), and dipropyl carbonate (DPC).
The lithium salt in the non-aqueous electrolyte is selected from lithium hexafluorophosphate (LiPF)6) And/or lithium tetrafluoroborate (LiBF)4)。
In one embodiment, the concentration of the lithium salt in the nonaqueous electrolyte is 0.2 to 2 mol/L. In one embodiment, the concentration of the lithium salt in the nonaqueous electrolyte is 0.8 to 1.5 mol/L.
In one embodiment, the thickness of the lithium supplement layer on the surface of the positive electrode plate or the lithium supplement layer of the separator is 2 to 15 μm. In one embodiment, the thickness of the lithium supplement layer on the surface of the positive electrode plate or the lithium supplement layer of the separator is 9-12 μm. In the invention, if the surface of the positive pole piece or the thickness of the lithium supplement layer of the diaphragm is too thick, namely the lithium-containing compound in the lithium supplement layer is too much, the decomposition of the excessive lithium-containing compound is incomplete in the charging and discharging process, and the lithium-containing compound has poor conductivity and is not beneficial to realizing the deintercalation of lithium ions in a high-rate charging and discharging state, so that the cycle performance of the lithium ion battery obtained by the condition that the surface of the positive pole piece or the thickness of the lithium supplement layer of the diaphragm is too thick is poor.
As an embodiment, a ratio of the thickness of the lithium supplement layer to the thickness of the positive electrode active material layer is 2: 100-30: 100. as an embodiment, a ratio of the thickness of the lithium supplement layer to the thickness of the positive electrode active material layer is 4: 100-20: 100.
as an embodiment, further comprising step 4): and (3) carrying out formation on the lithium secondary battery assembled in the step 3), decomposing the lithium-containing compound to produce lithium ions and gas, extracting the produced gas, and inserting the lithium ions into the negative electrode.
The present invention also provides a lithium secondary battery prepared by the above method.
The present invention additionally provides an electric vehicle including the lithium secondary battery.
The invention has the following advantages: 1) the lithium supplementing layer is coated on the surface of the positive pole piece or the diaphragm, the process is simple, the safety is high, the cost is low, the irreversible capacity loss in the process of lithium embedding for the first time can be supplemented, and the proportion of active substances of the positive pole cannot be reduced. 2) The added lithium supplement material can be decomposed when the lithium secondary battery is formed and charged, gas generated after decomposition can be removed after formation, and the generated lithium is used for forming an SEI film on a negative electrode, so that the consumption of lithium ions on a positive electrode is reduced, the irreversible capacity loss of the lithium ion battery is reduced, and the energy density of the lithium ion battery is improved. 3) After completion of the formation, the binder (PMMA, etc., which is well compatible with the nonaqueous electrolyte) used in the lithium-replenishing layer is slowly dissolved in the electrolyte solution, and then the separator and the positive electrode active material layer are restored to a state before lithium replenishment, and lithium ion desorption is normally performed. On the premise that the cycle performance of the positive active material is not affected, the loss of irreversible lithium ions in the positive active material is reduced, and the energy density of the battery is improved.
The lithium secondary battery of the present invention is not limited in its structure and its manufacturing process except that the active material of the positive electrode material, the active material of the negative electrode material, the separator and the nonaqueous electrolytic solution described in the present invention are used. For example, the positive electrode, the negative electrode and the separator can be prepared by the following method, and the battery can be assembled by the following method:
(a) positive electrode
The positive electrode for a lithium secondary battery can be produced by the following method.
First, a positive electrode active material, a conductive agent a, and a binder a are mixed, and a solvent a is added to prepare a slurry. The mixing ratio of the materials in the positive electrode slurry often determines the electrochemical performance of the lithium ion secondary battery. In general, the total mass of the solid material components in the positive electrode slurry is preferably set to 80 to 95 parts by mass, 2 to 15 parts by mass of the conductive agent a, and 1 to 18 parts by mass of the binder a, similarly to the positive electrode of a general lithium ion secondary battery, as 100 parts by mass of the total mass of the solid material components in the positive electrode slurry. The solvent A is selected from N-methylpyrrolidone (NMP).
The obtained positive electrode slurry was coated on the surface of a current collector made of a conductive substrate (aluminum foil), and dried to volatilize the solvent. If necessary, the electrode density may be increased by applying pressure by a roll method or the like. Thus, a sheet-like positive electrode can be produced. The sheet-shaped positive electrode can be cut in an appropriate size according to the target battery. The method for manufacturing the positive electrode is not limited to the illustrated method, and other methods may be employed. In the production of the positive electrode sheet, as the conductive agent a, for example, carbon, which may be amorphous carbon or crystalline carbon, including charcoal, coke, bone charcoal, sugar charcoal, activated carbon, carbon black, coke, graphitized mesocarbon microbeads (MCMB), soft carbon, hard carbon, graphite, and the like; the carbon can be carbon nano tube, graphite flake, fullerene, graphene and the like according to microstructure; from the aspect of micro morphology, the carbon can be carbon fiber, carbon tube, carbon sphere and the like. Carbon materials with high electronic conductivity and good structural strength are preferred. The drying time is 3-6 h; the drying temperature is 60-100 ℃.
The binder a plays a role of linking and fixing the positive electrode active material, and includes at least one of a hydrophilic polymer, that is, carboxymethyl cellulose (CMC), Methyl Cellulose (MC), Cellulose Acetate Phthalate (CAP), hydroxypropyl methyl cellulose (HPMC), hydroxypropyl methyl cellulose phthalate (HPMCP), polyvinyl alcohol (PVA), polyethylene oxide (PEO), and the like, and a hydrophobic polymer material, that is, at least one of a fluorine-based resin such as Polytetrafluoroethylene (PTFE), tetrafluoroethylene perfluoroalkyl vinyl ether copolymer (FEP), polyvinylidene fluoride (PVDF), polyethylene-tetrafluoroethylene copolymer (ETFE), and a rubber such as vinyl acetate copolymer, styrene-butadiene block copolymer (SBR), acrylic modified SBR resin (SBR-based latex), and arabic rubber. Among them, fluorine-based resins such as PTFE and PVDF are preferably used. Electronically conducting polymers have a very significant advantage as binders and are a direction of development for binders used in electrochemical devices.
The positive electrode active material, the conductive agent a and the binder a are added to an appropriate solvent, dispersed or dissolved, and mixed to prepare a slurry.
Coating the prepared slurry on a positive current collector, volatilizing and drying the solvent, and rolling. As a representative example, a coating apparatus (coater) may be used to coat the slurry on the surface of the current collector with a predetermined thickness. The coating thickness is not particularly limited, and may be appropriately set according to the shape or application of the positive electrode and the battery. After coating, the coating is dried to remove the solvent, a positive electrode active material layer with a predetermined thickness is formed on the surface of the current collector, and then rolling treatment is performed as necessary to obtain a positive electrode sheet with a target thickness. The drying time is 3-6 h; the drying temperature is 60-100 ℃.
(b) Negative electrode
The negative pole piece is prepared by mixing a negative active material, a conductive agent B, a binder B and a solvent B according to a certain proportion to prepare slurry, uniformly coating the slurry on a conductive matrix (copper foil), and drying and rolling the slurry. The negative active material is selected from artificial graphite or natural graphite. The drying time is 3-6 h; the drying temperature is 60-100 ℃.
The solvent B is selected from deionized water and/or N-methyl pyrrolidone (NMP).
In general, the total mass of the material components in the negative electrode slurry is set to 100 parts by mass, and similarly to the positive electrode of a general lithium ion secondary battery, it is preferable that the negative electrode active material content is set to 80 to 95 parts by mass, the conductive agent B content is set to 2 to 15 parts by mass, and the binder B content is set to 1 to 18 parts by mass.
As the conductive agent B in the electrode sheet, for example, carbon, which may be amorphous carbon or crystalline carbon, including charcoal, coke, bone charcoal, sugar charcoal, activated carbon, carbon black, coke, graphitized mesocarbon microbeads (MCMB), soft carbon, hard carbon, graphite, and the like; the carbon can be carbon nano tube, graphite flake, fullerene, graphene and the like according to microstructure; from the aspect of micro morphology, the carbon can be carbon fiber, carbon tube, carbon sphere and the like. In the embodiment of the invention, one or more of graphene, VGCF, acetylene black and KS-6 are used. The binder B plays a role of linking and fixing the positive electrode active material particles, and includes hydrophilic polymers, that is, carboxymethyl cellulose (CMC), Methyl Cellulose (MC), Cellulose Acetate Phthalate (CAP), hydroxypropyl methyl cellulose (HPMC), hydroxypropyl methyl cellulose phthalate (HPMCP), polyvinyl alcohol (PVA), polyethylene oxide (PEO), and the like, and hydrophobic polymer materials, that is, fluorine-based resins such as Polytetrafluoroethylene (PTFE), tetrafluoroethylene perfluoroalkyl vinyl ether copolymer (FEP), polyvinylidene fluoride (PVDF), polyethylene-tetrafluoroethylene copolymer (ETFE), and the like, and rubbers such as vinyl acetate copolymer, styrene-butadiene block copolymer (SBR), acrylic modified SBR resin (SBR-based latex), and arabic rubber.
Drawings
FIG. 1: the structure of the positive pole piece comprising the lithium supplement layer in the embodiment 1 is schematically shown;
FIG. 2: the structure of a polypropylene separator comprising a lithium supplement layer as described in example 7;
wherein, 1: a conductive base; 2: a positive electrode active material layer; 3: a lithium supplement layer; 4: a polyolefin-based separator; 5: and (5) supplementing lithium.
Detailed Description
The following specific examples describe the present invention in detail, however, the present invention is not limited to the following examples.
Example 1:
(1) mixing nickel cobalt lithium manganate (NCM523), a conductive agent Super P (conductive carbon black, SP) and polyvinylidene fluoride (a binder PVDF) according to a mass ratio of 93: 4: 3 was dispersed in N-methylpyrrolidone (NMP) to form a positive electrode active material slurry. Coating the positive active material slurry on the surface of an aluminum foil (conductive substrate), drying in an oven at 100 ℃ for 3h, and rolling to obtain the positive pole piece coated with a positive active material layer (with the thickness of 50 μm).
(2) Mixing Li3N, a conductive agent carbon fiber (VGCF), and a binder polymethyl methacrylate (PMMA) according to a mass ratio of 49: 49: 2 are dispersed in an organic solvent, N-methyl pyrrolidone (NMP), to form a lithium supplement slurry. And (3) coating the lithium supplement slurry on the surface of the positive pole piece obtained in the step (1), and then drying in a drying oven at 100 ℃ for 3h to finally form the lithium supplement positive pole piece with a 15-micron thick lithium supplement layer.
(3) Mixing artificial graphite, conductive carbon black (SP), sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR) according to a mass ratio of 96.5: 1:1: 1.5 in deionized water to form a negative electrode slurry. And coating the obtained negative electrode slurry on the surface of copper foil, drying for 3h in a 60 ℃ oven, and rolling to obtain a negative electrode plate.
(4) The positive pole piece obtained in the step (2), the negative pole piece obtained in the step (3) and electrolyte (lithium salt LiPF) with the concentration of 1mol/L6And a solvent EC: DEC: the volume ratio of EMC is 1:1:1), and assembling a polypropylene diaphragm to prepare the soft package battery.
Example 2:
(1) mixing nickel cobalt lithium manganate (NCM523), a conductive agent Super P (conductive carbon black, SP) and polyvinylidene fluoride (a binder PVDF) according to a mass ratio of 93: 4: 3 was dispersed in N-methylpyrrolidone (NMP) to form a positive electrode active material slurry. Coating the positive active material slurry on the surface of an aluminum foil (conductive substrate), drying in an oven at 100 ℃ for 3h, and rolling to obtain the pole piece coated with a positive active material layer (the thickness is 450 mu m).
(2) Mixing Li3N, a conductive agent (VGCF), and a polymethyl methacrylate (PMMA) adhesive in a mass ratio of 90: 5: 5 is dispersed in an organic solvent N-methyl pyrrolidone (NMP) to form a lithium supplement slurry. And (3) coating the lithium supplement slurry on the surface of the positive pole piece obtained in the step (1), and then drying in a drying oven at 100 ℃ for 3h to finally form the lithium supplement positive pole piece with a 15-micron thick lithium supplement layer.
(3) Mixing artificial graphite, conductive carbon black (SP), sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR) according to a mass ratio of 96.5: 1:1: 1.5 in deionized water to form a negative electrode slurry. And coating the obtained negative electrode slurry on the surface of copper foil, drying for 3h in a 60 ℃ oven, and rolling to obtain a negative electrode plate.
(4) The positive pole piece obtained in the step (2), the negative pole piece obtained in the step (3) and electrolyte (lithium salt LiPF) with the concentration of 1mol/L6And a solvent EC: DEC: the volume ratio of EMC is 1:1:1), and assembling a polypropylene diaphragm to prepare the soft package battery.
Example 3:
(1) mixing nickel cobalt lithium manganate (NCM523), a conductive agent Super P (conductive carbon black, SP) and polyvinylidene fluoride (a binder PVDF) according to a mass ratio of 93: 4: 3 was dispersed in N-methylpyrrolidone (NMP) to form a positive electrode active material slurry. The positive active material slurry was coated on the surface of an aluminum foil (conductive substrate), and then dried in an oven at 100 ℃ for 3 hours, and rolled, thereby coating a positive active material layer (thickness of 200 μm) on a pole piece.
(2) Mixing Li3N, a conductive agent (VGCF), and a binder polymethyl methacrylate (PMMA) in a mass ratio of 49: 46: 5 is dispersed in an organic solvent N-methyl pyrrolidone (NMP) to form a lithium supplement slurry. And (3) coating the lithium supplement slurry on the surface of the positive pole piece obtained in the step (1), and then drying in a drying oven at 100 ℃ for 3h to finally form the lithium supplement positive pole piece with a 15-micron thick lithium supplement layer.
(3) Mixing artificial graphite, conductive carbon black (SP), sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR) according to a mass ratio of 96.5: 1:1: 1.5 in deionized water to form a negative electrode slurry. And coating the obtained negative electrode slurry on the surface of copper foil, drying for 3h in a 60 ℃ oven, and rolling to obtain a negative electrode plate.
(4) The positive pole piece obtained in the step (2), the negative pole piece obtained in the step (3) and electrolyte (lithium salt LiPF) with the concentration of 1mol/L6And a solvent EC: DEC: the volume ratio of EMC is 1:1:1), and assembling a polypropylene diaphragm to prepare the soft package battery.
Example 4:
(1) mixing nickel cobalt lithium manganate (NCM523), a conductive agent Super P (conductive carbon black, SP) and polyvinylidene fluoride (a binder PVDF) according to a mass ratio of 93: 4: 3 was dispersed in N-methylpyrrolidone (NMP) to form a positive electrode active material slurry. The positive active material slurry was coated on the surface of an aluminum foil (conductive substrate), and then dried in an oven at 100 ℃ for 3 hours, and rolled, thereby coating a positive active material layer (thickness 150 μm) on a pole piece.
(2) Mixing Li2O, a conductive agent (VGCF), and a binder polymethyl methacrylate (PMMA) in a mass ratio of 49: 49: 2 are dispersed in an organic solvent, N-methyl pyrrolidone (NMP), to form a lithium supplement slurry. And (3) coating the lithium supplement slurry on the surface of the positive pole piece obtained in the step (1), and then drying in a drying oven at 100 ℃ for 3h to finally form the lithium supplement positive pole piece with a lithium supplement layer with the thickness of 6 microns.
(3) Mixing artificial graphite, conductive carbon black (SP), sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR) in a mass ratio of 96.5: 1:1: 1.5 in deionized water to form a negative electrode slurry. And coating the obtained negative electrode slurry on the surface of copper foil, drying for 3h in a 60 ℃ oven, and rolling to obtain a negative electrode plate.
(4) The positive pole piece obtained in the step (2), the negative pole piece obtained in the step (3) and electrolyte (lithium salt LiPF) with the concentration of 1mol/L6And a solvent EC: DEC: EMC (electro magnetic compatibility) volume ratio of 1:1:1) and assembling a polypropylene diaphragm to prepare the 5Ah soft package battery.
Example 5:
(1) mixing nickel cobalt lithium manganate (NCM523), a conductive agent Super P (conductive carbon black, SP) and polyvinylidene fluoride (a binder PVDF) according to a mass ratio of 93: 4: 3 was dispersed in N-methylpyrrolidone (NMP) to form a positive electrode active material slurry. The positive active material slurry was coated on the surface of an aluminum foil (conductive substrate), and then dried in an oven at 100 ℃ for 3 hours, and rolled, thereby coating a positive active material layer (thickness of 300 μm) on a pole piece.
(2) Mixing Li2O, a conductive agent (VGCF), and a binder polymethyl methacrylate (PMMA) in a mass ratio of 93: 4: 3 dispersing in organic solvent N-methyl pyrrolidone (NMP) to form lithium supplementing slurry. And (3) coating the lithium supplement slurry on the surface of the positive pole piece obtained in the step (1), and then drying in a drying oven at 100 ℃ for 3h to finally form the lithium supplement positive pole piece with a 12-micron thick lithium supplement layer.
(3) Mixing artificial graphite, conductive carbon black (SP), sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR) according to a mass ratio of 96.5: 1:1: 1.5 in deionized water to form a negative electrode slurry. And coating the obtained negative electrode slurry on the surface of copper foil, drying for 3h in a 60 ℃ oven, and rolling to obtain a negative electrode plate.
(4) The positive pole piece obtained in the step (2), the negative pole piece obtained in the step (3) and electrolyte (lithium salt LiPF) with the concentration of 1mol/L6And a solvent EC: DEC: the volume ratio of EMC is 1:1:1), and assembling a polypropylene diaphragm to prepare the soft package battery.
Example 6:
(1) lithium iron phosphate, a conductive agent Super P (conductive carbon black, SP) and polyvinylidene fluoride (a binder PVDF) are mixed according to a mass ratio of 93: 4: 3 was dispersed in N-methylpyrrolidone (NMP) to form a positive electrode active material slurry. The positive active material slurry was coated on the surface of an aluminum foil (conductive substrate), and then dried in an oven at 100 ℃ for 3 hours, and rolled, thereby coating a positive active material layer (thickness of 200 μm) on a pole piece.
(2) Mixing Li2O, a conductive agent (VGCF), and a binder polymethyl methacrylate (PMMA) in a mass ratio of 49: 5: 46 are dispersed in an organic solvent, N-methylpyrrolidone (NMP), to form a lithium-supplemented slurry. And (3) coating the lithium supplement slurry on the surface of the positive pole piece obtained in the step (1), and then drying in a drying oven at 100 ℃ for 3h to finally form the lithium supplement positive pole piece with a 10-micron thick lithium supplement layer.
(3) Mixing artificial graphite, conductive carbon black (SP), sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR) according to a mass ratio of 96.5: 1:1: 1.5 in deionized water to form a negative electrode slurry. And coating the obtained negative electrode slurry on the surface of copper foil, drying for 3h in a 60 ℃ oven, and rolling to obtain a negative electrode plate.
(4) The positive pole piece obtained in the step (2), the negative pole piece obtained in the step (3) and electrolyte (lithium salt LiPF) with the concentration of 1mol/L6And a solvent EC: DEC: the volume ratio of EMC is 1:1:1), and assembling a polypropylene diaphragm to prepare the soft package battery.
Example 7:
(1) mixing nickel cobalt lithium manganate (NCM523), a conductive agent Super P (conductive carbon black, SP) and polyvinylidene fluoride (a binder PVDF) according to a mass ratio of 93: 4: 3 was dispersed in N-methylpyrrolidone (NMP) to form a positive electrode active material slurry. The positive active material slurry was coated on the surface of an aluminum foil (conductive substrate), and then dried in an oven at 100 ℃ for 3 hours, and rolled, thereby coating a positive active material layer (50 μm) on the electrode sheet.
(2) Mixing Li3N, a conductive agent (VGCF), and a binder polymethyl methacrylate (PMMA) in a mass ratio of 49: 49: 2 are dispersed in an organic solvent, N-methyl pyrrolidone (NMP), to form a lithium supplement slurry. And coating the lithium supplement slurry on the surface of the polypropylene diaphragm, and drying in an oven at 60 ℃ for 3h to finally form the polypropylene diaphragm with a 15-micron-thick lithium supplement layer on the surface. And the lithium supplement layer on the surface of the diaphragm is opposite to the positive active material layer.
(3) Mixing artificial graphite, conductive carbon black (SP), sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR) according to a mass ratio of 96.5: 1:1: 1.5 in deionized water to form a negative electrode slurry. And coating the obtained negative electrode slurry on the surface of copper foil, drying for 3h in a 60 ℃ oven, and rolling to obtain a negative electrode plate.
(4) The positive pole piece obtained in the step (1), the polypropylene diaphragm obtained in the step (2), the negative pole piece obtained in the step (3) and electrolyte (lithium salt LiPF) with the concentration of 1mol/L6And a solvent EC: DEC: the volume ratio of EMC is 1:1:1), assembling and preparing the 5Ah soft package battery.
Example 8:
(1) mixing nickel cobalt lithium manganate (NCM523), a conductive agent Super P (conductive carbon black, SP) and polyvinylidene fluoride (a binder PVDF) according to a mass ratio of 93: 4: 3 was dispersed in N-methylpyrrolidone (NMP) to form a positive electrode active material slurry. The positive active material slurry was coated on the surface of an aluminum foil (conductive substrate), and then dried in an oven at 100 ℃ for 3 hours, and rolled, thereby coating a positive active material layer (thickness 450 μm) on a pole piece.
(2) Mixing Li3N, a conductive agent (VGCF), and a polymethyl methacrylate (PMMA) adhesive in a mass ratio of 90: 5: 5 is dispersed in an organic solvent N-methyl pyrrolidone (NMP) to form a lithium supplement slurry. And coating the lithium supplement slurry on the surface of the polypropylene diaphragm, and drying in an oven at 60 ℃ for 3h to finally form the polypropylene diaphragm with a 9-micron-thick lithium supplement layer on the surface. And the lithium supplement layer on the surface of the diaphragm is opposite to the positive active material layer.
(3) Mixing artificial graphite, conductive carbon black (SP), sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR) according to a mass ratio of 96.5: 1:1: 1.5 in deionized water to form a negative electrode slurry. And coating the obtained negative electrode slurry on the surface of copper foil, drying for 3h in a 60 ℃ oven, and rolling to obtain a negative electrode plate.
(4) The positive pole piece obtained in the step (1), the polypropylene diaphragm obtained in the step (2), the negative pole piece obtained in the step (3) and electrolyte (lithium salt LiPF) with the concentration of 1mol/L6And a solvent EC: DEC: the volume ratio of EMC is 1:1:1) assembling to prepare the soft package battery. After the obtained lithium ion battery was formed (charged to a voltage of 4.5V with a current of 0.05C and then charged to a constant voltage of 4.5V to a cutoff current of 0.0025C), the content of N element on the surface of the positive electrode sheet was detected by an energy spectrometer (EDS) (model: Ametek, EDAX Octane Plus EDS). The results are shown in Table 2.
Example 9:
(1) mixing nickel cobalt lithium manganate (NCM523), a conductive agent Super P (conductive carbon black, SP) and polyvinylidene fluoride (a binder PVDF) according to a mass ratio of 93: 4: 3 was dispersed in N-methylpyrrolidone (NMP) to form a positive electrode active material slurry. The positive active material slurry was coated on the surface of an aluminum foil (conductive substrate), and then dried in an oven at 100 ℃ for 3 hours, and rolled, thereby coating a positive active material layer (thickness of 300 μm) on a pole piece.
(2) Mixing Li3N, a conductive agent (VGCF), and a binder polymethyl methacrylate (PMMA) in a mass ratio of 49: 46: 5 dispersing in organic solvent N-methyl pyrrolidineIn ketone (NMP), a lithium-supplemented slurry was formed. And (3) coating the lithium supplement slurry on the surface of the positive pole piece obtained in the step (1), and then drying in an oven at 100 ℃ for 3h to finally form the polypropylene diaphragm with a 15-micron thick lithium supplement layer. And the lithium supplement layer on the surface of the diaphragm is opposite to the positive active material layer.
(3) Mixing artificial graphite, conductive carbon black (SP), sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR) according to a mass ratio of 96.5: 1:1: 1.5 in deionized water to form a negative electrode slurry. And coating the obtained negative electrode slurry on the surface of copper foil, drying for 3h in a 60 ℃ oven, and rolling to obtain a negative electrode plate.
(4) The positive pole piece obtained in the step (2), the negative pole piece obtained in the step (3) and electrolyte (lithium salt LiPF) with the concentration of 1mol/L6And a solvent EC: DEC: EMC (electro magnetic compatibility) volume ratio of 1:1:1) and assembling a polypropylene diaphragm to prepare the 5Ah soft package battery.
Example 10:
(1) mixing nickel cobalt lithium manganate (NCM523), a conductive agent Super P (conductive carbon black, SP) and polyvinylidene fluoride (a binder PVDF) according to a mass ratio of 93: 4: 3 was dispersed in N-methylpyrrolidone (NMP) to form a positive electrode active material slurry. The positive active material slurry was coated on the surface of an aluminum foil (conductive substrate), and then dried in an oven at 100 ℃ for 3 hours, and rolled, thereby coating a positive active material layer (thickness of 200 μm) on a pole piece.
(2) Mixing Li2O, a conductive agent (CNT), and a binder polymethyl methacrylate (PMMA) in a mass ratio of 93: 4: 3 dispersing in organic solvent N-methyl pyrrolidone (NMP) to form lithium supplementing slurry. And (3) coating the lithium supplement slurry on the surface of the positive pole piece obtained in the step (1), and then drying in a drying oven at 100 ℃ for 3h to finally form the polypropylene diaphragm with a 10-micron thick lithium supplement layer. And the lithium supplement layer on the surface of the diaphragm is opposite to the positive active material layer.
(3) Mixing artificial graphite, conductive carbon black (SP), sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR) according to a mass ratio of 96.5: 1:1: 1.5 in deionized water to form a negative electrode slurry. And coating the obtained negative electrode slurry on the surface of copper foil, drying for 3h in a 60 ℃ oven, and rolling to obtain a negative electrode plate.
(4) The positive pole piece obtained in the step (2) is processedThe negative pole piece obtained in the step (3) and electrolyte (lithium salt LiPF) with the concentration of 2mol/L6And a solvent EC: DEC: the volume ratio of EMC is 1:1:1), and assembling a polypropylene diaphragm to prepare the soft package battery.
Example 11:
(1) mixing nickel cobalt lithium manganate (NCM523), a conductive agent Super P (conductive carbon black, SP) and polyvinylidene fluoride (a binder PVDF) according to a mass ratio of 93: 4: 3 was dispersed in N-methylpyrrolidone (NMP) to form a positive electrode active material slurry. Coating the positive active material slurry on the surface of an aluminum foil (conductive substrate), drying in an oven at 100 ℃ for 3h, and rolling to obtain the positive pole piece coated with a positive active material layer (the thickness is 300 mu m).
(2) Mixing Li3N, a conductive agent carbon fiber (VGCF), a binder polyethylene oxide (PEO) according to a mass ratio of 49: 49: 2 are dispersed in an organic solvent, N-methyl pyrrolidone (NMP), to form a lithium supplement slurry. And (3) coating the lithium supplement slurry on the surface of the positive pole piece obtained in the step (1), and then drying in a drying oven at 100 ℃ for 3h to finally form the lithium supplement positive pole piece with a 15-micron thick lithium supplement layer.
(3) Mixing artificial graphite, conductive carbon black (SP), sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR) according to a mass ratio of 96.5: 1:1: 1.5 in deionized water to form a negative electrode slurry. And coating the obtained negative electrode slurry on the surface of copper foil, drying for 3h in a 60 ℃ oven, and rolling to obtain a negative electrode plate.
(4) The positive pole piece obtained in the step (2), the negative pole piece obtained in the step (3) and electrolyte (lithium salt LiPF) with the concentration of 2mol/L6And a solvent EC: DEC: the volume ratio of EMC is 1:1:1), and assembling a polypropylene diaphragm to prepare the soft package battery.
Example 12:
(1) mixing nickel cobalt lithium manganate (NCM523), a conductive agent Super P (conductive carbon black, SP) and polyvinylidene fluoride (a binder PVDF) according to a mass ratio of 93: 4: 3 was dispersed in N-methylpyrrolidone (NMP) to form a positive electrode active material slurry. Coating the positive active material slurry on the surface of an aluminum foil (conductive substrate), drying in an oven at 100 ℃ for 3h, and rolling to obtain the positive pole piece coated with a positive active material layer (the thickness is 300 mu m).
(2) Mixing Li3N, a conductive agent carbon fiber (VGCF), an adhesive and polyvinyl chloride (PVC) according to a mass ratio of 49: 49: 2 are dispersed in an organic solvent, N-methyl pyrrolidone (NMP), to form a lithium supplement slurry. And (3) coating the lithium supplement slurry on the surface of the positive pole piece obtained in the step (1), and then drying in a drying oven at 100 ℃ for 3h to finally form the lithium supplement positive pole piece with a 15-micron thick lithium supplement layer.
(3) Mixing artificial graphite, conductive carbon black (SP), sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR) amine in a mass ratio of 96.5: 1:1: 1.5 in deionized water to form a negative electrode slurry. And coating the obtained negative electrode slurry on the surface of copper foil, drying for 3h in a 60 ℃ oven, and rolling to obtain a negative electrode plate.
(4) The positive pole piece obtained in the step (2), the negative pole piece obtained in the step (3) and electrolyte (lithium salt LiPF) with the concentration of 1mol/L6And a solvent EC: DEC: the volume ratio of EMC is 1:1:1), and assembling a polypropylene diaphragm to prepare the soft package battery.
Comparative example 1:
(1) mixing nickel cobalt lithium manganate (NCM523), a conductive agent Super P (conductive carbon black, SP) and polyvinylidene fluoride (a binder PVDF) according to a mass ratio of 93: 4: 3 was dispersed in N-methylpyrrolidone (NMP) to form a positive electrode active material slurry. The positive active material slurry was coated on the surface of an aluminum foil (conductive substrate), and then dried in an oven at 100 ℃ for 3 hours, and rolled, thereby coating a positive active material layer (thickness 450 μm) on a pole piece.
(2) Mixing artificial graphite, conductive carbon black (SP), sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR) according to a mass ratio of 96.5: 1:1: 1.5 in deionized water to form a negative electrode slurry. And coating the obtained negative electrode slurry on the surface of copper foil, drying for 3h in a 60 ℃ oven, and rolling to obtain a negative electrode plate.
(3) The positive pole piece obtained in the step (1), the negative pole piece obtained in the step (2) and electrolyte (lithium salt LiPF) with the concentration of 1mol/L6And a solvent EC: DEC: the volume ratio of EMC is 1:1:1), and assembling a polypropylene diaphragm to prepare the soft package battery.
Comparative example 2:
(1) mixing nickel cobalt lithium manganate (NCM523), a conductive agent Super P (conductive carbon black, SP) and polyvinylidene fluoride (PVDF) according to a mass ratio of 93: 4: 3 was dispersed in N-methylpyrrolidone (NMP) to form a positive electrode active material slurry. The positive active material slurry was coated on the surface of an aluminum foil (conductive substrate), and then dried in an oven at 100 ℃ for 3 hours, and rolled, thereby coating a positive active material layer (thickness 450 μm) on a pole piece.
(2) Mixing Li3N, a conductive agent (VGCF), polyvinylidene fluoride (PVDF) according to a mass ratio of 90: 5: 5 is dispersed in an organic solvent N-methyl pyrrolidone (NMP) to form a lithium supplement slurry. And (3) coating the lithium supplement slurry on the surface of the positive pole piece obtained in the step (1), and then drying in an oven at 100 ℃ for 3h to finally form the polypropylene diaphragm with a 15-micron thick lithium supplement layer.
(3) Mixing artificial graphite, conductive carbon black (SP), sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR) according to a mass ratio of 96.5: 1:1: 1.5 in deionized water to form a negative electrode slurry. And coating the obtained negative electrode slurry on the surface of copper foil, drying for 3h in a 60 ℃ oven, and rolling to obtain a negative electrode plate.
(4) The positive pole piece obtained in the step (2), the negative pole piece obtained in the step (3) and electrolyte (lithium salt LiPF) with the concentration of 1mol/L6And a solvent EC: DEC: EMC (electro magnetic compatibility) volume ratio of 1:1:1) and assembling a polypropylene diaphragm to prepare the 5Ah soft package battery.
Comparative example 3:
(1) mixing nickel cobalt lithium manganate (NCM523), a conductive agent Super P (conductive carbon black, SP) and polyvinylidene fluoride (a binder PVDF) according to a mass ratio of 93: 4: 3 was dispersed in N-methylpyrrolidone (NMP) to form a positive electrode active material slurry. The positive active material slurry was coated on the surface of an aluminum foil (conductive substrate), and then dried in an oven at 100 ℃ for 3 hours, and rolled, thereby coating a positive active material layer (thickness 450 μm) on a pole piece.
(2) Mixing Li3N, adhesive polymethyl methacrylate (PMMA) according to a mass ratio of 18: 1 is dispersed in an organic solvent, N-methyl pyrrolidone (NMP), to form a lithium supplement slurry. And (3) coating the lithium supplement slurry on the surface of the positive pole piece obtained in the step (1), and then drying in an oven at 100 ℃ for 3h to finally form the polypropylene diaphragm with a 15-micron thick lithium supplement layer.
(3) Mixing artificial graphite, conductive carbon black (SP), sodium carboxymethylcellulose (CMC) and Styrene Butadiene Rubber (SBR) according to a mass ratio of 96.5: 1:1: 1.5 in deionized water to form a negative electrode slurry. And coating the obtained negative electrode slurry on the surface of copper foil, drying for 3h in a 60 ℃ oven, and rolling to obtain a negative electrode plate.
(4) The positive pole piece obtained in the step (2), the negative pole piece obtained in the step (3) and electrolyte (lithium salt LiPF) with the concentration of 1mol/L6And a solvent EC: DEC: EMC (electro magnetic compatibility) volume ratio of 1:1:1) and assembling a polypropylene diaphragm to prepare the 5Ah soft package battery. After the obtained lithium ion battery was formed (charged to a voltage of 4.5V with a current of 0.05C and then charged to a constant voltage of 4.5V to a cutoff current of 0.0025C), the content of N element on the surface of the positive electrode sheet was detected by an energy spectrometer (EDS) (model: Ametek, EDAX Octane Plus EDS). The results are shown in Table 3.
The battery performance test conditions of examples 1 to 12 and comparative examples 1 to 3 were: at normal temperature, the batteries prepared in examples 1 to 10 and comparative examples 1 to 3 were charged at a current density of 0.5C in a constant current and constant voltage manner, and discharged at a current density of 0.5C in a constant current and constant discharge manner. The charge and discharge cycle was repeated 100 times, with a charge cut-off voltage of 4.3V, a cut-off current of 0.025C, and a discharge cut-off voltage of 2.5V. The energy density and capacity retention rate after 100 cycles of the lithium ion batteries of examples 1 to 12 and comparative examples 1 to 3 were measured (see table 1).
Table 1: the energy density and the capacity retention rate of the lithium ion batteries in examples 1 to 12 and comparative examples 1 to 3 were improved.
Figure BDA0001742926360000151
Table 2: the content of N element on the surface of the positive electrode sheet obtained after formation of the lithium ion battery in example 8.
Element(s) Mass% Atom%
C 26.30 44.64
N 2.82 4.11
Mn 28.41 36.20
Co 13.27 4.93
Ni 8.71 3.01
Table 3: the content of the N element on the surface of the positive electrode sheet obtained after the formation of the battery of comparative example 3.
Element(s) Mass% Atom%
C 21.00 35.54
N 33.30 48.31
Mn 14.44 5.34
Co 9.18 3.17
Ni 22.08 7.64
From table 1, it can be seen that the positive electrode plate and the separator containing the lithium supplement layer obtained by the present invention can effectively compensate the irreversible capacity loss of the lithium secondary battery in the charging and discharging processes, so that the lithium secondary battery obtained by the present invention has a higher energy density.
As can be seen from comparative example 1 and examples 1 to 12, although the positive electrode sheet or separator used in the lithium secondary battery of the present invention includes the lithium supplement layer, the obtained lithium secondary battery always maintained the cycle performance equivalent to that of comparative example 1 (the positive electrode sheet or separator did not include the lithium supplement layer), and the energy density in the lithium secondary batteries obtained in examples 1 to 12 was significantly better than that of comparative example 1. The invention can effectively compensate the capacity loss of the lithium secondary battery in the charging and discharging process on the premise of ensuring that the cycle performance is not influenced.
From example 2 and comparative example 2, it can be seen that: the cycle performance of example 8 is significantly better than that of comparative example 2, which shows that when the binder (PVDF) in the lithium supplement layer of the positive electrode tab is a binder insoluble in the electrolyte, the lithium supplement layer of the positive electrode tab has a lithium supplement function, but the cycle performance and energy density of the obtained battery are significantly deteriorated.
As can be seen from example 2 and comparative example 3, when the conductive agent is not contained in the lithium supplement layer (comparative example 3), the energy density and cycle performance of the obtained lithium secondary battery are lower than those of the lithium secondary battery containing the conductive agent in the lithium supplement layer. As can be seen from the EDS test results of tables 2 and 3, the pole piece of comparative example 3 has more nitrogen element remained, and the pole piece of example 2 has less nitrogen element remained, which indicates that the lithium-containing compound in example 2 is fully decomposed during the charging and discharging process of the battery, while the lithium-containing compound in comparative example 3 is partially decomposed, but most of the lithium-containing compound is not fully decomposed, so that the addition of a certain amount of conductive agent to the lithium supplement layer promotes the decomposition of the lithium-containing compound.

Claims (16)

1. A lithium replenishing paste for a lithium secondary battery, comprising: a lithium-containing compound, a conductive agent, a binder, and an organic solvent, the binder being a binder soluble in a nonaqueous electrolyte solution.
2. The lithium replenishing slurry according to claim 1, wherein the binder is at least one of Polymethylmethacrylate (PMMA), polyethylene oxide (PEO), and polyvinyl chloride (PVC).
3. The lithium replenishing slurry according to claim 1, wherein the binder is contained in an amount of 2 to 20% by mass based on the total amount of the lithium-containing compound, the conductive agent and the binder.
4. The lithium replenishing slurry according to claim 1, wherein the lithium-containing compound is selected from Li2O、Li3N、LiI、Li2S and lithium oxalate.
5. The lithium replenishing slurry according to claim 1, wherein the content of the lithium-containing compound is 45 to 93% by mass based on the total amount of the lithium-containing compound, the conductive agent and the binder.
6. The lithium replenishing slurry according to claim 1, wherein the conductive agent is at least one selected from the group consisting of acetylene black, conductive carbon black, conductive graphite, carbon fiber, carbon nanotube, and graphene.
7. The lithium replenishing slurry according to claim 1, wherein the conductive agent is contained in an amount of 5 to 50% by mass based on the total amount of the lithium-containing compound, the conductive agent and the binder.
8. The lithium replenishing slurry according to claim 1, wherein the organic solvent is at least one selected from the group consisting of N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), N-Diethylformamide (DEF), Dimethylsulfoxide (DMSO), and Tetrahydrofuran (THF).
9. A method for preparing a lithium secondary battery, comprising the steps of: 1) provided is a lithium replenishing slurry comprising: a lithium-containing compound, a conductive agent, a binder and an organic solvent, wherein the binder is a binder soluble in a non-aqueous electrolyte solution; 2) providing a positive pole piece, coating the lithium supplement slurry in the step 1) on the surface of the positive pole piece to prepare the positive pole piece with a lithium supplement layer on the surface; 3) and assembling the negative pole piece, the diaphragm, the non-aqueous electrolyte solution and the positive pole piece with the lithium supplementing layer on the surface into the lithium secondary battery.
10. A method for preparing a lithium secondary battery, comprising the steps of: 1) provided is a lithium replenishing slurry comprising: a lithium-containing compound, a conductive agent, a binder and an organic solvent, wherein the binder is a binder soluble in a non-aqueous electrolyte solution; 2) providing a diaphragm, coating the lithium supplement slurry in the step 1) on the surface of the diaphragm to prepare the diaphragm with a lithium supplement layer on the surface; 3) assembling a positive pole piece, a negative pole piece, a non-aqueous electrolyte solution and the diaphragm with the lithium supplementing layer on the surface into a lithium secondary battery; and the lithium supplement layer on the surface of the diaphragm is opposite to the positive active material layer.
11. The method according to claim 9 or 10, wherein the solvent of the non-aqueous electrolyte solution comprises at least one of dimethyl carbonate (DMC), diethyl carbonate (DEC), Propylene Carbonate (PC), Ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC), Methyl Propyl Carbonate (MPC), methyl isopropyl carbonate (MIPC), Butylene Carbonate (BC), 1, 2-Dimethoxyethane (DME), dibutyl carbonate (DBC), methyl butyl carbonate (BMC), and dipropyl carbonate (DPC).
12. The production method according to claim 9 or 10, characterized in that: the thickness of the lithium supplement layer on the surface of the positive pole piece or the lithium supplement layer of the diaphragm is 2-15 mu m.
13. The production method according to claim 9 or 10, wherein a ratio of the thickness of the lithium supplement layer to the thickness of the positive electrode active material layer is 2: 100-30: 100.
14. the production method according to claim 9 or 10, characterized in that: further comprising step 4): and (3) carrying out formation on the lithium secondary battery assembled in the step 3), decomposing the lithium-containing compound to produce lithium ions and gas, extracting the produced gas, and inserting the lithium ions into the negative electrode.
15. A lithium secondary battery produced by the production method according to claim 9 or 10.
16. An electric vehicle comprising the lithium secondary battery according to claim 15.
CN201810828004.7A 2018-07-25 2018-07-25 Lithium supplement slurry for lithium secondary battery and preparation method of lithium secondary battery Pending CN110767880A (en)

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Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111509288A (en) * 2020-05-27 2020-08-07 陕西煤业化工技术研究院有限责任公司 Lithium supplementing method for improving first coulombic efficiency and cycle performance of lithium ion battery
CN111725500A (en) * 2020-06-22 2020-09-29 惠州亿纬锂能股份有限公司 Positive plate and preparation method and application thereof
CN111816822A (en) * 2020-06-18 2020-10-23 中国科学院化学研究所 Functional lithium-supplementing diaphragm and preparation method thereof
CN112151889A (en) * 2020-10-10 2020-12-29 惠州亿纬锂能股份有限公司 Positive pole piece of lithium ion battery and preparation method and application thereof
CN112448037A (en) * 2020-11-30 2021-03-05 广州天赐高新材料股份有限公司 Lithium supplementing composition, lithium supplementing electrolyte and lithium supplementing method for lithium secondary battery
CN112786313A (en) * 2019-11-04 2021-05-11 中国科学院大连化学物理研究所 Electrode slurry containing lithium nitride and preparation and application thereof
CN113381009A (en) * 2020-03-10 2021-09-10 中国科学院物理研究所 Lithium supplement material and preparation method and application thereof
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CN113471412A (en) * 2020-03-31 2021-10-01 北京卫蓝新能源科技有限公司 Composite conductive slurry, preparation method, positive pole piece and lithium ion battery
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WO2022237064A1 (en) * 2021-05-08 2022-11-17 江苏正力新能电池技术有限公司 Lithium supplementing slurry, positive plate, and lithium ion battery
WO2023283960A1 (en) * 2021-07-16 2023-01-19 宁德时代新能源科技股份有限公司 Positive pole piece, secondary battery and preparation method therefor, and battery module, battery pack and electrical device comprising secondary battery

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1697210A (en) * 2005-04-16 2005-11-16 谷亦杰 Composite positive plate of lithium ion battery and composition method
CN105702913A (en) * 2014-11-27 2016-06-22 比亚迪股份有限公司 Positive electrode and preparation method therefor, and lithium secondary battery
CN107068972A (en) * 2017-03-22 2017-08-18 江苏元景锂粉工业有限公司 The ternary material anode pole piece and its lithium ion battery of a kind of quick charge

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1697210A (en) * 2005-04-16 2005-11-16 谷亦杰 Composite positive plate of lithium ion battery and composition method
CN105702913A (en) * 2014-11-27 2016-06-22 比亚迪股份有限公司 Positive electrode and preparation method therefor, and lithium secondary battery
CN107068972A (en) * 2017-03-22 2017-08-18 江苏元景锂粉工业有限公司 The ternary material anode pole piece and its lithium ion battery of a kind of quick charge

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* Cited by examiner, † Cited by third party
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