WO2022237064A1 - 一种补锂浆料、正极片和锂离子电池 - Google Patents

一种补锂浆料、正极片和锂离子电池 Download PDF

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Publication number
WO2022237064A1
WO2022237064A1 PCT/CN2021/123200 CN2021123200W WO2022237064A1 WO 2022237064 A1 WO2022237064 A1 WO 2022237064A1 CN 2021123200 W CN2021123200 W CN 2021123200W WO 2022237064 A1 WO2022237064 A1 WO 2022237064A1
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lithium
slurry
mass
supplementing
replenishing
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PCT/CN2021/123200
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English (en)
French (fr)
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邹武元
叶秉杨
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江苏正力新能电池技术有限公司
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Priority to US18/282,779 priority Critical patent/US20240170649A1/en
Priority to DE112021006784.2T priority patent/DE112021006784T5/de
Publication of WO2022237064A1 publication Critical patent/WO2022237064A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • 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
    • H01M4/62—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
    • 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
    • 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
    • H01M2004/028—Positive electrodes
    • 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
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/26—Processes of manufacture
    • H01M4/28—Precipitating active material on the carrier
    • 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

Definitions

  • the invention relates to the field of lithium batteries, in particular to a lithium supplement slurry, a positive electrode sheet and a lithium ion battery.
  • the SEI film refers to a passivation layer covering the surface of the electrode material formed by the reaction between the electrode material and the electrolyte at the solid-liquid phase interface during the first charging and discharging process of the liquid lithium-ion battery.
  • the passivation film formed can effectively prevent solvent molecules from passing through, but Li+ can be freely inserted and extracted through the passivation layer, which has the characteristics of a solid electrolyte, so this passivation film is called "solid electrolyte interface film". "(solid electrolyte interface), referred to as SEI film.
  • the main components of the SEI film are LiF, Li 2 CO 3 and alkyl ester lithium, etc.
  • the lithium ions in these products mainly come from the active lithium in the positive electrode material, which directly leads to the decrease of the charge and discharge efficiency in the first week, and the subsequent With the dissolution and production of the SEI film, the loss of active lithium will be more serious.
  • some lithium ions cannot be completely extracted after being intercalated into the negative electrode material, resulting in the loss of active lithium, which in turn reduces the charge-discharge efficiency and cycle life.
  • lithium-supplementing materials are often highly alkaline, and directly mixed with positive active materials will make it difficult to disperse the entire positive electrode slurry, and it is easy to agglomerate and coagulate Glue makes the pole piece made of it have the problems of high resistance and large polarization.
  • One of the purposes of the present invention is to provide a lithium-replenishing slurry, which can be combined with the positive electrode in a better state.
  • the lithium-replenishing material used is not limited to lithium oxalate, and has wider applicability. And it does not contain a catalyst, and the addition amount of lithium supplement materials can be precisely designed.
  • a lithium-replenishing slurry comprising a lithium-replenishing material, a conductive agent and a binder; and satisfying the following relationship:
  • D50 is the average particle diameter of the lithium supplement material
  • B1 is the specific surface area of the lithium supplement material
  • B2 is the specific surface area of the conductive agent
  • M1 is the ratio of the mass of the lithium-replenishing material to the mass of the solid components in the lithium-replenishing slurry
  • M2 is the ratio of the mass of the conductive agent to the mass of the solid components in the lithium-supplementing slurry
  • M3 is the ratio of the mass of the binder to the mass of the solid components in the lithium-supplementing slurry.
  • the lithium-supplementing material includes at least one lithium-containing metal oxide that can be delithiated.
  • the lithium-replenishing material includes at least two kinds of the lithium-containing metal oxides
  • their mass accounts for the mass of the solid components in the lithium-replenishing slurry in terms of M1a, M1b, M1c, ..., M1n, respectively.
  • the specific surface area is calculated by B1a, B1b, B1c, ..., B1n
  • the specific surface area B1 of the lithium-replenishing material is 0.3-15m 2 /g; the average particle diameter D50 of the lithium-replenishing material is 0.5-12 ⁇ m; the mass of the lithium-replenishing material accounts for The ratio M1 of solid content mass is 70 to 95%.
  • the lithium-containing metal oxide is lithium phosphate, dilithium hydrogen phosphate, lithium sulfate, lithium sulfite, lithium molybdate, lithium oxalate, lithium titanate, lithium tetraborate, lithium metasilicate, lithium metamanganate , lithium tartrate, trilithium citrate in any one.
  • the conductive agent is composed of at least one conductive agent; when the conductive agent is mixed from at least two conductive agents, its mass accounts for the complementary
  • the specific surface area B2 of the conductive agent is 20-300 m 2 /g; the ratio M2 of the mass of the conductive agent to the mass of solid components in the lithium-supplementing slurry is 0.1-15%.
  • the conductive agent includes conductive carbon black, conductive graphite KS-6, conductive graphite SFG-6, Ketjen Black EC300J, Ketjen Black ECP, Ketjen Black ECP-600JD, carbon fiber, carbon nanotube, graphene, At least one of graphene oxide and vapor-phase grown carbon fibers.
  • the binder is at least one of polyvinylpyrrolidone, polyvinylidene fluoride, polyethylene oxide, polytetrafluoroethylene, sodium carboxymethyl cellulose, and a copolymer of styrene and butadiene ;
  • the ratio M3 of the mass of the binder to the mass of the solid components in the lithium-supplementing slurry is 0.1-20%.
  • the lithium-supplementing slurry further includes a dispersant; the mass of the dispersant accounts for 0.1-10% of the solid content in the lithium-supplementing slurry; the dispersant is polyoxyethylene dioleic acid Grease and/or Polytetraethylene Glycol Monoester.
  • the lithium-supplementing slurry also includes a solvent; the mass of the solvent accounts for 20% to 50% of the mass of the lithium-supplementing slurry.
  • the solvent is water, N-methyl-2-pyrrolidone, tetrahydrofuran, At least one of dimethylformamide or ethanol.
  • the second object of the present invention is to provide a positive electrode sheet, including a positive electrode coating and a lithium-replenishing coating coated on the positive electrode coating; the lithium-replenishing coating is composed of the lithium-replenishing slurry described in any of the above material made.
  • the thickness of the positive electrode coating and the thickness of the lithium-supplementing coating satisfy the following relationship: 1/10 ⁇ thickness of lithium-supplementing coating/thickness of positive electrode coating ⁇ 1/3.
  • the thickness of the lithium-supplementing coating is 5-100 ⁇ m; the thickness of the positive electrode coating is 50-300 ⁇ m.
  • the third object of the present invention is to provide a lithium ion battery, comprising the positive electrode sheet described in any of the above paragraphs.
  • the present invention has at least the following beneficial effects:
  • the lithium-supplementing slurry and the positive electrode slurry are dispersed and mixed separately, avoiding the problems that the positive electrode slurry is difficult to disperse, easy to agglomerate and gel when the lithium-supplementing material is directly added to the positive electrode slurry; through the design of the present invention, adding Lithium-replenishing materials, conductive agents and binders can achieve a better dispersion effect. After being coated on the positive electrode coating, the obtained positive electrode sheet has lower impedance and more excellent lithium-replenishing effect.
  • using the relational formula of the present invention can also accurately calculate the added content of the lithium-supplementing material, which effectively reduces the residue of the lithium-supplementing material after the first charge and discharge, and the utilization rate of the lithium-supplementing material is higher.
  • the lithium-replenishing slurry of the present invention has good compatibility with various positive electrode materials and negative electrode materials, and the lithium-replenishing slurry of the present invention is applied to lithium ion In the battery, the first cycle efficiency can be effectively improved, making it close to the first effect value of the positive electrode material itself.
  • the lithium-supplementing slurry provided by the present invention does not contain an active material catalyst, and the lithium-supplementing active material is not limited to lithium oxalate, which has wider applicability and lower cost.
  • the first aspect of the present application provides a lithium-replenishing slurry, including a lithium-replenishing material, a conductive agent, and a binder; and satisfies the following relationship:
  • D50 is the average particle diameter of the lithium supplement material
  • B1 is the specific surface area of the lithium supplement material
  • B2 is the specific surface area of the conductive agent
  • M1 is the ratio of the mass of the lithium-replenishing material to the mass of the solid components in the lithium-replenishing slurry
  • M2 is the ratio of the mass of the conductive agent to the mass of the solid components in the lithium-supplementing slurry
  • M3 is the ratio of the mass of the binder to the mass of the solid components in the lithium-supplementing slurry.
  • the above relational expression satisfies:
  • the lithium-supplementing material includes at least one delithiated lithium-containing metal oxide.
  • the mass of M1a, M1b, M1c, ..., M1n accounts for the solid content of the lithium-replenishing slurry
  • the proportion of mass, the specific surface area is calculated by B1a, B1b, B1c, ..., B1n
  • B1 M1a*B1a+M1b*B1b+...+M1n*B1n;
  • D50 M1a*D50a+M1b*D50b+...+M1n*D50n.
  • the specific surface area B1 of the lithium-supplementing material may be 0.3-15m 2 /g, 0.3-0.5m 2 /g, 0.5-1m 2 /g, 1-2.5m 2 / g , 2.5-5m 2 /g, 5-7.5m 2 /g, 7.5-9m 2 /g, 9-12m 2 /g, or 12-15m 2 /g;
  • the average particle size D50 of the lithium-supplementing material can be 0.5-12 ⁇ m, 0.5-1 ⁇ m, 1-2.5 ⁇ m, 2.5-5 ⁇ m, 5-7.5 ⁇ m, 7.5-10 ⁇ m, or 10-12 ⁇ m;
  • the ratio M1 of the mass of the lithium-replenishing material to the mass of the solid components in the lithium-replenishing slurry can be 70-95%, 70-75%, 75-80%, 80-85%, 85-90%, or 90-95%.
  • the specific surface area B1 of the lithium-supplementing material can be 0.5-10m 2 /g, 0.5-1.5m 2 /g, 1.5-3m 2 /g, 3-4.5m 2 /g, 4.5-6m 2 /g g, 6-7.5m 2 /g, 7.5-9m 2 /g, or 9-10m 2 /g;
  • the average particle diameter D50 of the lithium supplement material can be 1-10 ⁇ m, 1-2 ⁇ m, 2-3 ⁇ m, 3 ⁇ 4 ⁇ m, 4-5 ⁇ m, 5-6 ⁇ m, 6-7 ⁇ m, 7-8 ⁇ m, 8-9 ⁇ m, or 9-10 ⁇ m;
  • the ratio M1 of the mass of the lithium-replenishing material to the mass of the solid components in the lithium-replenishing slurry is 80-90%.
  • the specific surface area B1 of the lithium-supplementing material can be 0.5-10m 2 /g, 0.5-1.5m 2 /g, 1.5-3m 2 /g, 3-4.5m 2 /
  • the lithium-containing metal oxide is lithium phosphate, dilithium hydrogen phosphate, lithium sulfate, lithium sulfite, lithium molybdate, lithium oxalate, lithium titanate, lithium tetraborate, lithium metasilicate, metasilicate Any one of lithium manganate, lithium tartrate, and trilithium citrate.
  • the present invention controls the properties of lithium supplement materials, conductive agents and other related materials, so that various lithium supplement materials can be effectively applied to lithium supplement slurry, and is not limited to lithium supplement lithium oxalate materials .
  • the conductive agent is composed of at least one conductive agent; when the conductive agent is formed by mixing at least two conductive agents, its mass accounted for by M2a, M2b, M2c, ..., M2n respectively
  • the specific surface area B2 of the conductive agent may be 20-300m 2 /g, 20-50m 2 /g, 50-80m 2 /g, 80-100m 2 / g, 100-130m 2 /g .
  • _ _ _ _ _ _ _ _ _ _ The ratio M2 of the mass of the conductive agent to the mass of the solid components in the lithium-supplementing slurry can be 0.1-15%, 0.1-1%, 1-2%, 2-3%, 3-4%, 4- 5%, 5-6%, 6-7%, 7-8%, 8-9%, 9-10%, 10-11%, 11-12%, 12-13%, 13-14%, or 14 ⁇ 15%.
  • the specific surface area B2 of the conductive agent may be 50-120m 2 /g, 50-60m 2 /g, 60-70m 2 /g, 70-80m 2 /g, 80-90m 2 / g , 90 ⁇ 100m 2 /g, 100 ⁇ 110m 2 /g, or 110 ⁇ 120m 2 /g;
  • the ratio M2 of the mass of the conductive agent to the mass of the solid components in the lithium-supplementing slurry can be 5 ⁇ 10%, 5 ⁇ 5.5%, 5.5-6%, 6-6.5%, 6.5-7%, 7-7.5%, 7.5-8%, 8-8.5%, 8.5-9%, 9-9.5%, or 9.5-10%.
  • the specific surface area of the conductive agent When the specific surface area of the conductive agent is too large, it is easy to cause the lithium-replenishing slurry to be difficult to disperse, thereby affecting the lithium-replenishing efficiency; and when the specific surface area of the conductive agent is too small, the specific surface area of the lithium-replenishing material is similar to that of the conductive agent, and the electrostatic adsorption force is relatively weak. Weak, on the one hand, it cannot be well adsorbed on the surface of the lithium supplement material, so that it cannot better promote the lithium capacity, and on the other hand, it cannot form a good conductive network, which affects the efficiency of lithium supplementation.
  • the lithium-supplementing effect will be affected due to the incomplete performance of the lithium-supplementing material.
  • the amount of conductive agent added also has a great influence on the dispersion and mixing of lithium supplementation slurry and the effect of lithium supplementation. If the proportion is too large, it will lead to uneven dispersion of lithium supplementation slurry, which will affect the efficiency of lithium supplementation.
  • the amount of conductive agent added will affect the internal resistance of the cell and the energy density of the cell.
  • the proportion of the corresponding increase, the greater the resistance of the pole piece, and the energy density of the battery cell will be improved to a certain extent.
  • the conductive agent includes conductive carbon black, conductive graphite KS-6, conductive graphite SFG-6, Ketjen Black EC300J, Ketjen Black ECP, Ketjen Black ECP-600JD, carbon fiber, carbon nanotube, At least one of graphene, graphene oxide, and vapor-phase grown carbon fibers.
  • the conductive agent can prevent the dispersant from completely wrapping the lithium-supplementing material, which is more conducive to the development of lithium capacity.
  • the conductive agent used in the present invention is a carbon material, and its carbon atoms are hybridized by SP2, so the surface has a negative charge, which can be adsorbed on the surface through electrostatic adsorption.
  • the surface of the lithium-supplementing material forms a conductive layer, which prevents the lithium-supplementing material from being completely wrapped by the dispersant; in addition, the conductive agent also provides sufficient electronic channels, which greatly increases the probability of contact between the electrolyte and the lithium-supplementing material, and further improves the lithium-supplementing material. utilization rate.
  • the binder is polyvinylpyrrolidone, polyvinylidene fluoride, polyethylene oxide, polytetrafluoroethylene, sodium carboxymethyl cellulose, copolymer of styrene and butadiene At least one; the mass of the binder accounts for the proportion M3 of the solid component mass in the lithium-supplementing slurry can be 0.1-20%, 0.1-2.5%, 2.5-5%, 5-7.5%, 7.5-10% %, 10-12.5%, 12.5-15%, 15-17.5%, or 17.5-20%.
  • the ratio M3 of the mass of the binder to the mass of the solid components in the lithium-supplementing slurry can be 5-15%, 5-6%, 6-7%, 7-8%, 8-9% , 9-10%, 10-11%, 11-12%, 12-13%, 13-14%, or 14-15%.
  • the binder not only has the effect of binding, but also has the effect of dispersing, and works together with the above-mentioned dispersant to form greater steric hindrance between the particles of the lithium-replenishing material, and further promotes a more uniform dispersion of the lithium-replenishing slurry.
  • the lithium-supplementing slurry also includes a dispersant, the dispersant is polyoxyethylene dioleate and/or polytetraethylene glycol monofatty acid, the mass of the dispersant accounts for the
  • the mass ratio of the solid content in the lithium-supplementing slurry can be 0.1-10%, 0.1-1%, 1-2.5%, 2.5-5%, 5-7.5%, or 7.5-10%.
  • the dispersed The ratio of the mass of the agent to the mass of the solid components in the lithium-supplementing slurry can be 3-6%, 3-3.5%, 3.5-4%, 4-4.5%, 4.5-5%, 5-5.5%, or 5.5-6%.
  • the dispersant of this kind of non-ionic surfactant can help the lithium supplement slurry to disperse stably and uniformly.
  • the dispersant is too much, it will tightly wrap the lithium supplement material, hinder the capacity of lithium, and reduce the lithium ion channel. If it is too small, because of its short molecular chain, it cannot play the role of steric hindrance well, and then cannot form a stable lithium supplementation slurry.
  • the lithium-supplementing slurry also includes a solvent, and the solvent is at least one of water, N-methyl-2-pyrrolidone, tetrahydrofuran, dimethylformamide or ethanol; the mass of the solvent
  • the proportion of the mass of the lithium-supplementing slurry can be 20-50%, 20-25%, 25-30%, 30-35%, 35-40%, 40-45%, or 45-50%, preferably
  • the proportion of the mass of the solvent to the mass of the lithium-supplementing slurry can be 25-40%, 25-27.5%, 27.5-30%, 30-32.5%, 32.5-35%, 35-37.5%, Or 37.5 to 40%.
  • the viscosity of the lithium-supplementing slurry When the content of the solvent is low, the viscosity of the lithium-supplementing slurry is high, and the solid content is too high, which may easily cause uneven stirring. When the content of the solvent is too high, the viscosity of the lithium-supplementing slurry will be too low. If the fluidity of the slurry is too good during the coating process, it will also cause uneven coating of the slurry layer.
  • the solvent in this proportion can be better mixed with lithium supplement materials, conductive agents, dispersants, etc. to form a lithium supplement slurry with a relatively suitable viscosity, which can be evenly coated on the positive electrode coating to ensure the lithium supplement effect.
  • the second aspect of the present application provides a positive electrode sheet
  • the positive electrode sheet includes a positive electrode current collector, a positive electrode coating disposed on the positive electrode current collector, and a lithium-replenishing coating coated on the positive electrode coating; the lithium-replenishing coating
  • the layer is made from the lithium supplementation slurry described in this application.
  • the lithium-supplementing slurry can be coated on the positive electrode coating by means of continuous coating, gap coating or dot coating. Specifically, screen printing, gravure coating, extrusion (Slot-die) can be used. Any method of coating and transfer coating.
  • the positive electrode coating includes positive electrode active materials, and the specific types of positive electrode active materials are not subject to specific restrictions, and can be selected according to requirements.
  • the positive electrode active material of the positive electrode coating can be one or more of including but not limited to layered positive electrode active material, spinel type positive electrode active material, olivine type positive electrode active material, metal sulfide, etc.
  • the positive active material can also be modified, and the method for modifying the positive active material should be known to those skilled in the art. For example, methods such as coating and doping can be used to modify the positive active material.
  • the material used for the modification treatment may be one or more combinations including but not limited to Al, B, P, Zr, Si, Ti, Ge, Sn, Mg, Ce, W, etc.
  • the thickness of the positive electrode coating and the thickness of the lithium-supplementing coating satisfy the following relationship: 1/10 ⁇ thickness of lithium-supplementing coating/thickness of positive electrode coating ⁇ 1/3. If the thickness ratio is too low, the lithium-replenishing coating will be thin and cannot achieve a good lithium-replenishing effect; and if the thickness ratio is too high, the lithium-replenishing coating may be too thick, and the thickness of the positive electrode coating will be compressed, which is not conducive to The energy density of the battery cell increases, and at the same time, the internal resistance of the battery cell will also increase significantly.
  • the thickness of the positive electrode coating and the thickness of the lithium-supplementing coating can satisfy the following relationship: 1/10 ⁇ thickness of the lithium-supplementing coating/thickness of the positive coating ⁇ 1/8, 1 /8 ⁇ thickness of lithium-supplementing coating/thickness of positive electrode coating ⁇ 1/5, 1/5 ⁇ thickness of lithium-supplementing coating/thickness of positive electrode coating ⁇ 1/3.
  • the thickness of the lithium-supplementing coating can be 5-100 ⁇ m, 5-15 ⁇ m, 15-30 ⁇ m, 30-45 ⁇ m, 45-60 ⁇ m, 60-75 ⁇ m, or 75-100 ⁇ m; the positive electrode coating The thickness can be 50-300 ⁇ m, 50-80 ⁇ m, 80-100 ⁇ m, 100-130 ⁇ m, 130-160 ⁇ m, 160-200 ⁇ m, 200-230 ⁇ m, 230-260 ⁇ m, or 260-300 ⁇ m.
  • the thickness of the lithium-supplementing coating can be 10-50 ⁇ m, 10-15 ⁇ m, 15-20 ⁇ m, 20-30 ⁇ m, 30-35 ⁇ m, 35-40 ⁇ m, 40-45 ⁇ m, or 45-50 ⁇ m; the positive electrode
  • the thickness of the coating can be 100-200 ⁇ m, 100-110 ⁇ m, 110-120 ⁇ m, 120-130 ⁇ m, 130-140 ⁇ m, 140-150 ⁇ m, 150-160 ⁇ m, 160-170 ⁇ m, 170-180 ⁇ m, 180-190 ⁇ m, or 190-200 ⁇ m .
  • the third aspect of the present application provides a lithium ion battery, which includes the positive electrode sheet, the negative electrode sheet and the separator described above in the present application.
  • the method for preparing the lithium-ion battery should be known to those skilled in the art.
  • the positive electrode sheet, the separator and the negative electrode sheet can each be a layer, so that they can be cut into the target size and then stacked one after another. , can be further wound to the target size to form a battery cell, and can be further combined with an electrolyte to form a lithium-ion battery.
  • the specific type of the lithium-ion battery is not specifically limited, for example, it may include but not limited to a cylindrical battery, an aluminum case battery, or a pouch battery.
  • the negative electrode sheet generally includes a negative electrode current collector and a negative electrode active material layer located on the surface of the negative electrode current collector, and the negative electrode active material layer generally includes a negative electrode active material.
  • the negative electrode active material can be various materials suitable for the negative electrode active material of lithium-ion batteries in the art, for example, can include but not limited to graphite, soft carbon, hard carbon, carbon fiber, mesocarbon microspheres, silicon-based materials , tin-based materials, lithium titanate or other metals that can form alloys with lithium, etc., or one or more of them.
  • the graphite can be selected from one or more of artificial graphite, natural graphite and modified graphite;
  • the silicon-based material can be selected from one of elemental silicon, silicon oxide compounds, silicon-carbon composites, and silicon alloys One or more kinds;
  • the tin-based material can be selected from one or more of simple tin, tin oxide compounds, and tin alloys.
  • the negative electrode current collector is usually a structure or part that collects current.
  • the negative electrode current collector can be a variety of materials suitable for use as a lithium ion battery negative electrode collector in the art.
  • the negative electrode current collector can include but is not limited to Metal foil etc., more specifically may include but not limited to copper foil etc.
  • the separator can be a variety of materials suitable for lithium-ion battery separators in the art, for example, it can include but not limited to polyethylene, polypropylene, polyvinylidene fluoride, aramid fiber, polyethylene terephthalate , Polytetrafluoroethylene, polyacrylonitrile, polyimide, polyamide, polyester and natural fiber etc. one or more combinations.
  • Example 2-20 the lithium-ion power batteries of Examples 2-20 were prepared with reference to the settings of Example 1.
  • the positive electrode sheet of this comparative example does not contain a lithium-supplementing coating.
  • Example 1 The difference from Example 1 is that the positive electrode sheet of this comparative example contains a lithium-replenishing material, and the lithium-replenishing material is first mixed with the positive electrode slurry and then coated.
  • the positive electrode sheet of this comparative example does not contain a lithium-supplementing coating.
  • Example 21 The difference from Example 21 is that the positive electrode sheet of this comparative example contains a lithium-supplementing material, and the lithium-supplementing material is first mixed with the positive electrode slurry and then coated.
  • the battery with lithium iron phosphate and graphite system had an efficiency of 91.1% in the first week when no lithium supplement slurry was added; however, after introducing the lithium supplement slurry, the largest initial efficiency The efficiency can be increased to 97.9%, which is close to the first effect value of the lithium iron phosphate material itself.
  • the battery with the ternary NCM523 material and the silicon-oxygen negative electrode system had an efficiency of 73.6% in the first week without adding the lithium-supplementing slurry; but after introducing the lithium-supplementing slurry, the maximum first-efficiency can be increased to 88.83%, which is close to The first effect value of the ternary NCM523 material itself.
  • lithium supplementation effect of lithium-ion batteries shows a trend of first increasing and then decreasing. This is mainly because the effect of lithium supplementation is affected by many factors. The addition amount of lithium will have an impact on the effect of lithium supplementation. Only by synchronously controlling these factors can the first effect value be improved to the greatest extent.
  • the lithium-supplementing effect also shows a trend of first increasing and then decreasing, which is also the result of the joint action of the above-mentioned factors.
  • the design of the present invention to add lithium-supplementing materials, conductive agents, binders and dispersants, a better dispersion effect can be achieved, and after being coated on the positive electrode coating, the impedance of the obtained positive electrode sheet is even higher. Low, the effect of lithium supplementation is more excellent, effectively improving the first cycle efficiency, making it close to the first effect value of the positive electrode material itself.

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Abstract

一种补锂浆料、正极片和锂离子电池，将补锂浆料与正极浆料分开分散混合，避免了直接将补锂材料加入正极浆料中而导致正极浆料难以分散、易团聚和凝胶的问题；通过本发明设计添加的补锂材料、导电剂和粘结剂形成的补锂浆料，可以达到更好的分散效果，将其涂覆于正极涂层后，所得到的正极片的阻抗更低，补锂效果更加优异。此外，采用本发明补锂浆料的关系式还可以精准计算补锂材料的添加含量，有效减少了首次充放电后补锂材料的残留，补锂材料的利用率更高。

Description

一种补锂浆料、正极片和锂离子电池
本申请要求于2021年05月08日提交中国专利局、申请号为202110514352.9、发明名称为“一种补锂浆料、正极片和锂离子电池”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及锂电池领域，具体涉及一种补锂浆料、正极片和锂离子电池。
背景技术
SEI膜是指液态锂离子电池在首次充放电过程中，电极材料与电解液在固液相界面上发生反应，形成的一层覆盖于电极材料表面的钝化层。形成的这层钝化膜可以有效地阻止溶剂分子通过，但Li+却可以经过该钝化层自由地嵌入和脱出，具有固体电解质的特征，因此这层钝化膜被称为“固体电解质界面膜”(solid electrolyte interface)，简称SEI膜。SEI膜的主要成分为LiF、Li 2CO 3和烷基酯锂等，这些产物中的锂离子主要来源于正极材料中的活性锂，从而直接导致首周充放电效率的降低，并且后续随着SEI膜的溶解和生产，活性锂的损失会更加严重。此外，在电池循环过程中，还有一部分锂离子嵌入到负极材料后不能完全脱出，从而导致活性锂的损失，进而降低充放电效率和循环寿命。
目前大部分企业均在研究补锂材料的选择，寻找更好的补锂材料。当前的技术一般是将补锂材料直接作为一种物质加入到正极配方里，但补锂材料往往碱性高，直接与正极活性物混合使用，会导致整个正极浆料难以分散、易团聚和凝胶，使得其所制成的极片具有电阻高、极化大的问题。
此外，也有现有技术采取了提前制备补锂浆料，如中国专利申请CN110838573A，其公开了一种锂离子储能器件补锂浆料及其制备方法和应用，其中所述补锂浆料包含作为补锂活性物质的草酸锂、作为催化剂的过渡金属化合物和溶剂。但此种方法需要用到活性物质为催化剂，且只适合草酸锂作为补锂活性物质，无法精准设计补锂材料的添加量，有效存放时间短，适配性低，且仍无法解决电阻高、极化大的问题。
有鉴于此，确有必要提供一种解决上述问题的技术方案。
发明内容
本发明的目的之一在于：提供一种补锂浆料，本补锂浆料能以更好的状态与正极极片结合，采用的补锂材料并不局限于草酸锂，适用性更广，且不含催化剂，可精准设计补锂材料的添加量。
为了实现上述目的，本发明采用以下技术方案：
一种补锂浆料，包括补锂材料、导电剂和粘结剂；并满足以下关系式：
Figure PCTCN2021123200-appb-000001
其中，D50为所述补锂材料的平均粒径；
B1为所述补锂材料的比表面积；
B2为所述导电剂的比表面积；
M1为所述补锂材料的质量占所述补锂浆料里固体成分质量的比例；
M2为所述导电剂的质量占所述补锂浆料里固体成分质量的比例；
M3为所述粘结剂的质量占所述补锂浆料里固体成分质量的比例。
优选的，所述补锂材料包括至少一种可脱锂的含锂金属氧化物。
优选的，当所述补锂材料包括至少两种所述含锂金属氧化物时，分别以M1a、M1b、M1c、……、M1n计其质量占所述补锂浆料里固体成分质量的比例，以B1a、B1b、B1c、……、B1n计其比表面积，以D50a、D50b、D50c、……、D50n计其平均粒径；则满足关系式：M1＝M1a+M1b+M1c+……+M1n；B1＝M1a*B1a+M1b*B1b+……+M1n*B1n；D50＝M1a*D50a+M1b*D50b+……+M1n*D50n。
优选的，所述补锂材料的比表面积B1为0.3～15m 2/g；所述补锂材料的平均粒径D50为0.5～12μm；所述补锂材料的质量占所述补锂浆料里固体成分质量的比例M1为70～95％。
优选的，所述含锂金属氧化物为磷酸锂、磷酸氢二锂、硫酸锂、亚硫酸锂、钼酸锂、草酸锂、钛酸锂、四硼酸锂、偏硅酸锂、偏锰酸锂、酒石酸锂、柠檬酸三锂中的任意一种。
优选的，所述导电剂由至少一种导电剂组成；当所述导电剂由至少两种导电剂混合而成时，分别以M2a、M2b、M2c、……、M2n计其质量占所述补 锂浆料里固体成分质量的比例，以B2a、B2b、B2c、……、B2n计其比表面积；则满足关系式：M2＝M2a+M2b+M2c+……+M2n；B2＝M2a*B2a+M2b*B2b+……+M2n*B2n。
优选的，所述导电剂的比表面积B2为20～300m 2/g；所述导电剂的质量占所述补锂浆料里固体成分质量的比例M2为0.1～15％。
优选的，所述导电剂包括导电炭黑、导电石墨KS-6、导电石墨SFG-6、科琴黑EC300J、科琴黑ECP、科琴黑ECP-600JD、碳纤维、碳纳米管、石墨烯、氧化石墨烯、气相生长炭纤维中的至少一种。
优选的，所述粘结剂为聚乙烯吡咯烷酮、聚偏氟乙烯、聚环氧乙烷、聚四氟乙烯、羧甲基纤维素钠、苯乙烯与丁二烯的共聚物中的至少一种；所述粘结剂的质量占所述补锂浆料里固体成分质量的比例M3为0.1～20％。
优选的，该补锂浆料还包括分散剂；所述分散剂的质量占所述补锂浆料里的固体成分质量的比例为0.1～10％；所述分散剂为聚氧乙烯二油酸脂和/或聚四乙二醇单脂酸脂。
优选的，该补锂浆料还包括溶剂；所述溶剂的质量占所述补锂浆料的质量的比例为20～50％所述溶剂为水、N-甲基-2-吡咯烷酮、四氢呋喃、二甲基甲酰胺或乙醇中的至少一种。
本发明的目的之二在于，提供一种正极片，包括正极涂层和涂覆于所述正极涂层上的补锂涂层；所述补锂涂层由上述任一段所述的补锂浆料制成。
优选的，所述正极涂层的厚度和所述补锂涂层的厚度满足以下关系式：1/10<补锂涂层的厚度/正极涂层的厚度<1/3。
优选的，所述补锂涂层的厚度为5～100μm；所述正极涂层的厚度为50～300μm。
本发明的目的之三在于，提供一种锂离子电池，包括上述任一段所述的正极片。
相比于现有技术，本发明至少具有以下的有益效果：
1)本发明将补锂浆料与正极浆料分开分散混合，避免了直接将补锂材料加入正极浆料中而导致正极浆料难以分散、易团聚和凝胶的问题；通过本发明设计添加的补锂材料、导电剂和粘结剂，可以达到更好的分散效果，将其涂覆于 正极涂层后，所得到的正极片的阻抗更低，补锂效果更加优异。此外，采用本发明的关系式还可以精准计算补锂材料的添加含量，有效减少了首次充放电后补锂材料的残留，补锂材料的利用率更高。
2)通过合理配置补锂浆料中的各物质后，使得本发明的补锂浆料同各种正极材料和负极材料均具有良好的兼容性，将本发明的补锂浆料应用于锂离子电池中，可以有效提高首次循环效率，使其接近该正极材料自身的首效值。
3)本发明提供的补锂浆料不含活性物质催化剂，且补锂活性物质并不局限于草酸锂，适用性更广，成本更加低廉。
具体实施方式
本申请的第一方面提供一种补锂浆料，包括补锂材料、导电剂和粘结剂；并满足以下关系式：
Figure PCTCN2021123200-appb-000002
其中，D50为所述补锂材料的平均粒径；
B1为所述补锂材料的比表面积；
B2为所述导电剂的比表面积；
M1为所述补锂材料的质量占所述补锂浆料里固体成分质量的比例；
M2为所述导电剂的质量占所述补锂浆料里固体成分质量的比例；
M3为所述粘结剂的质量占所述补锂浆料里固体成分质量的比例。
在一些实施例中，上述关系式满足：
Figure PCTCN2021123200-appb-000003
Figure PCTCN2021123200-appb-000004
Figure PCTCN2021123200-appb-000005
Figure PCTCN2021123200-appb-000006
Figure PCTCN2021123200-appb-000007
Figure PCTCN2021123200-appb-000008
Figure PCTCN2021123200-appb-000009
Figure PCTCN2021123200-appb-000010
Figure PCTCN2021123200-appb-000011
Figure PCTCN2021123200-appb-000012
Figure PCTCN2021123200-appb-000013
Figure PCTCN2021123200-appb-000014
Figure PCTCN2021123200-appb-000015
Figure PCTCN2021123200-appb-000016
Figure PCTCN2021123200-appb-000017
Figure PCTCN2021123200-appb-000018
Figure PCTCN2021123200-appb-000019
Figure PCTCN2021123200-appb-000020
Figure PCTCN2021123200-appb-000021
或
Figure PCTCN2021123200-appb-000022
在一些实施例中，所述补锂材料包括至少一种可脱锂的含锂金属氧化物。
在一些实施例中，当所述补锂材料包括至少两种所述含锂金属氧化物时，分别以M1a、M1b、M1c、……、M1n计其质量占所述补锂浆料里固体成分质量的比例，以B1a、B1b、B1c、……、B1n计其比表面积，以D50a、D50b、D50c、……、D50n计其平均粒径；则关系式满足：M1＝M1a+M1b+M1c+……+M1n；B1＝M1a*B1a+M1b*B1b+……+M1n*B1n；D50＝M1a*D50a+M1b*D50b+……+M1n*D50n。
在一些实施例中，所述补锂材料的比表面积B1可以为0.3～15m 2/g、0.3～0.5m 2/g、0.5～1m 2/g、1～2.5m 2/g、2.5～5m 2/g、5～7.5m 2/g、7.5～9m 2/g、9～12m 2/g、或12～15m 2/g；所述补锂材料的平均粒径D50可以为0.5～12μm、0.5～1μm、1～2.5μm、2.5～5μm、5～7.5μm、7.5～10μm、或10～12μm；所述补锂材料的质量占所述补锂浆料里固体成分质量的比例M1可以为70～95％、70～75％、75～80％、80～85％、85～90％、或90～95％，补锂材料的质量占比如果过低，通常不利于电芯能量密度的提升，同时电芯的内阻也会明显增加。更优选的，所述补锂材料的比表面积B1可为0.5～10m 2/g、0.5～1.5m 2/g、1.5～3m 2/g、3～4.5m 2/g、4.5～6m 2/g、6～7.5m 2/g、7.5～9m 2/g、或9～10m 2/g；所述 补锂材料的平均粒径D50可为1～10μm、1～2μm、2～3μm、3～4μm、4～5μm、5～6μm、6～7μm、7～8μm、8～9μm、或9～10μm；所述补锂材料的质量占所述补锂浆料里固体成分质量的比例M1为80～90％。进一步地，所述补锂材料的比表面积B1为0.5～2.5m 2/g；所述补锂材料的平均粒径D50为3～6μm。
在一些实施例中，所述含锂金属氧化物为磷酸锂、磷酸氢二锂、硫酸锂、亚硫酸锂、钼酸锂、草酸锂、钛酸锂、四硼酸锂、偏硅酸锂、偏锰酸锂、酒石酸锂、柠檬酸三锂中的任意一种。相比于CN110838573A专利文件，本发明通过控制补锂材料、导电剂等相关材料的性质，使得多种补锂材料均可以有效应用到补锂浆料中，并不仅仅局限于草酸锂补锂材料。
在一些实施例中，所述导电剂由至少一种导电剂组成；当所述导电剂由至少两种导电剂混合而成时，分别以M2a、M2b、M2c、……、M2n计其质量占所述补锂浆料里固体成分质量的比例，以B2a、B2b、B2c、……、B2n计其比表面积；则满足关系式：M2＝M2a+M2b+M2c+……+M2n；B2＝M2a*B2a+M2b*B2b+……+M2n*B2n。
在一些实施例中，所述导电剂的比表面积B2可以为20～300m 2/g、20～50m 2/g、50～80m 2/g、80～100m 2/g、100～130m 2/g、130～150m 2/g、150～180m 2/g、180～20m 2/g、200～230m 2/g、230～250m 2/g、250～280m 2/g、或280～300m 2/g；所述导电剂的质量占所述补锂浆料里固体成分质量的比例M2可以为0.1～15％、0.1～1％、1～2％、2～3％、3～4％、4～5％、5～6％、6～7％、7～8％、8～9％、9～10％、10～11％、11～12％、12～13％、13～14％、或14～15％。更优选的，所述导电剂的比表面积B2可为50～120m 2/g、50～60m 2/g、60～70m 2/g、70～80m 2/g、80～90m 2/g、90～100m 2/g、100～110m 2/g、或110～120m 2/g；所述导电剂的质量占所述补锂浆料里固体成分质量的比例M2可为5～10％、5～5.5％、5.5～6％、6～6.5％、6.5～7％、7～7.5％、7.5～8％、8～8.5％、8.5～9％、9～9.5％、或9.5～10％。当导电剂的比表面积过大时，容易导致补锂浆料不易分散，进而影响补锂效率；而当导电剂的比表面积过小时，补锂材料的比表面积与导电剂相近，静电吸附力较弱，一方面无法较好的吸附在补锂材料表面，以致不能较好的促进锂容量的发挥，另一方面无法形成良好的导电网络，进而影响补锂效率。如此，即使精准计算补锂材料的添加量，也会因补锂材料发挥 不全而影响补锂效果。同样的，导电剂的添加量对于补锂浆料的分散混合、补锂效果也存在较大影响，比例过大，会导致补锂浆料分散不均，进而影响补锂效率。此外，导电剂添加量会影响电芯的内阻和电芯的能量密度。通常来说，导电剂占比越高，补锂材料的占比相应降低，极片电阻越小，而电芯能量密度会有一定程度的降低；相反，导电剂占比越低，补锂材料的占比相应提高，极片电阻越大，而电芯能量密度会有一定程度的提升。
在一些实施例中，所述导电剂包括导电炭黑、导电石墨KS-6、导电石墨SFG-6、科琴黑EC300J、科琴黑ECP、科琴黑ECP-600JD、碳纤维、碳纳米管、石墨烯、氧化石墨烯、气相生长炭纤维中的至少一种。导电剂可以阻止分散剂完全包裹补锂材料，更有利于锂容量的发挥，本发明采用的导电剂为碳材料，其碳原子采用SP2杂化，因此表面带有负电荷，可通过静电吸附在补锂材料表面，从而形成导电层，避免了补锂材料完全被分散剂包裹；此外，该导电剂也提供了足够的电子通道，大大增加了电解液与补锂材料接触的几率，进一步提高锂的利用率。
在一些实施例中，所述粘结剂为聚乙烯吡咯烷酮、聚偏氟乙烯、聚环氧乙烷、聚四氟乙烯、羧甲基纤维素钠、苯乙烯与丁二烯的共聚物中的至少一种；所述粘结剂的质量占所述补锂浆料里固体成分质量的比例M3可为0.1～20％、0.1～2.5％、2.5～5％、5～7.5％、7.5～10％、10～12.5％、12.5～15％、15～17.5％、或17.5～20％。优选的，所述粘结剂的质量占所述补锂浆料里固体成分质量的比例M3可为5～15％、5～6％、6～7％、7～8％、8～9％、9～10％、10～11％、11～12％、12～13％、13～14％、或14～15％。该粘结剂不仅具有粘结的效果，还具有分散的作用，与上述的分散剂共同作用使得补锂材料颗粒之间形成更大的空间位阻，进一步促进补锂浆料更均匀的分散。当粘结剂比例过小时，粘接作用不够，导致极片的膜片电阻较大，影响补锂效果；而比例过大时，电池极化大，也会影响补锂效果。
在一些实施例中，该补锂浆料还包括分散剂，所述分散剂为聚氧乙烯二油酸脂和/或聚四乙二醇单脂酸脂，所述分散剂的质量占所述补锂浆料里的固体成分质量的比例可为0.1～10％、0.1～1％、1～2.5％、2.5～5％、5～7.5％、或7.5～10％，优选的，所述分散剂的质量占所述补锂浆料里的固体成分质量的 比例可为3～6％、3～3.5％、3.5～4％、4～4.5％、4.5～5％、5～5.5％、或5.5～6％。此种非离子表面活性剂的分散剂可有助于补锂浆料稳定均匀的分散，当分散剂过多时，其会将补锂材料紧密包裹起来，阻碍了锂的容量发挥，减少了锂离子通道的数量和电子导电性，而如果太少，由于其分子链较短，则不能很好的起到空间位阻的作用，进而无法形成稳定的补锂浆料。
在一些实施例中，该补锂浆料还包括溶剂，所述溶剂为水、N-甲基-2-吡咯烷酮、四氢呋喃、二甲基甲酰胺或乙醇中的至少一种；所述溶剂的质量占所述补锂浆料的质量的比例可为20～50％、20～25％、25～30％、30～35％、35～40％、40～45％、或45～50％，优选的，所述溶剂的质量占所述补锂浆料的质量的比例可为25～40％、25～27.5％、27.5～30％、30～32.5％、32.5～35％、35～37.5％、或37.5～40％。当溶剂的含量较低时，补锂浆料的粘度较高，固含量太高，容易造成搅拌不均的情形，而当溶剂含量过高时，补锂浆料的粘度又会过低，涂覆过程中浆料流动性太好，也同样会造成浆料层涂覆不均的情形。该比例的溶剂可以更好的与补锂材料、导电剂、分散剂等混合，形成粘度较为适应的补锂浆料，可均匀地涂覆于正极涂层上，以保证补锂效果。
本申请的第二方面提供一种正极片，正极片包括正极集流体、设置在正极集流体上的正极涂层和涂覆于所述正极涂层上的补锂涂层；所述补锂涂层由本申请所述的补锂浆料制成。其中，本补锂浆料可采用连续涂覆、间隙涂覆或点状涂覆的方式涂覆于正极涂层上，具体的可采用丝网印刷、凹版涂覆、挤压(Slot-die)涂覆、转移涂覆中的任意一种方式。
其中，正极涂层包含正极活性物质，正极活性物质的具体种类均不受到具体的限制，可根据需求进行选择。例如，该正极涂层的正极活性物质，可以是包括但不限于层状正极活性物质、尖晶石型正极活性物质、橄榄石型正极活性物质、金属硫化物等中的一种或多种的组合，更具体的，所述正极活性物质可以是包括但不限于化学式如Li aNi xCo yM zO 2-bN b(其中0.95≤a≤1.2，x>0，y≥0，z≥0，且x+y+z＝1,0≤b≤1，M选自Mn，Al中的一种或多种的组合，N选自F,P,S中的一种或多种的组合)所示的化合物中的一种或多种的组合，所述正极活性物质还可以是包括但不限于LiC OO 2、LiNiO 2、LiVO 2、LiCrO 2、LiMn 2O 4、LiCoMnO 4、Li 2NiMn 3O 8、LiNi 0.5Mn 1.5O 4、LiCoPO 4、LiMnPO 4、 LiFePO 4、LiNiPO 4、LiCoFSO 4、CuS 2、FeS 2、MoS 2、NiS、TiS 2等中的一种或多种的组合。所述正极活性物质还可以经过改性处理，对正极活性物质进行改性处理的方法对于本领域技术人员来说应该是己知的，例如，可以采用包覆、掺杂等方法对正极活性物质进行改性，改性处理所使用的材料可以是包括但不限于Al，B，P、Zr、Si、Ti、Ge、Sn、Mg、Ce、W等中的一种或多种的组合。
在一些实施例中，所述正极涂层的厚度和所述补锂涂层的厚度满足以下关系式：1/10<补锂涂层的厚度/正极涂层的厚度<1/3。厚度比如果过低时，补锂涂层较薄，无法起到较好的补锂效果；而如果厚度比过高，则补锂涂层可能会过厚，正极涂层厚度被压缩，不利于电芯能量密度的提升，同时，电芯的内阻也会明显增加。
在一些实施例中，所述正极涂层的厚度和所述补锂涂层的厚度可满足以下关系式：1/10<补锂涂层的厚度/正极涂层的厚度<1/8、1/8<补锂涂层的厚度/正极涂层的厚度<1/5、1/5<补锂涂层的厚度/正极涂层的厚度<1/3。
在一些实施例中，所述补锂涂层的厚度可为5～100μm、5～15μm、15～30μm、30～45μm、45～60μm、60～75μm、或75～100μm；所述正极涂层的厚度可为50～300μm、50～80μm、80～100μm、100～130μm、130～160μm、160～200μm、200～230μm、230～260μm、或260～300μm。更优选的，所述补锂涂层的厚度可为10～50μm、10～15μm、15～20μm、20～30μm、30～35μm、35～40μm、40～45μm、或45～50μm；所述正极涂层的厚度可为100～200μm、100～110μm、110～120μm、120～130μm、130～140μm、140～150μm、150～160μm、160～170μm、170～180μm、180～190μm、或190～200μm。
本申请的第三方面提供一种锂离子电池，其包括本申请上文所述的正极片、负极片和隔离膜。制备所述锂离子电池的方法对于本领域技术人员来说应该是己知的，例如，所述正极片、隔离膜和负极片各自都可以是层体，从而可以裁剪成目标尺寸后依次叠放，还可以进一步卷绕至目标尺寸，以用于形成电芯，并可以进一步与电解液结合以形成锂离子电池。所述锂离子电池的具体类型没有具体限制，例如，可以是包括但不限于圆柱电池、铝壳电池或者软包电池等。
所述负极片通常包括负极集流体和位于负极集流体表面的负极活性物质层，所述负极活性物质层通常包括负极活性物质。所述负极活性物质可以是本领域各种适用于锂离子电池的负极活性物质的材料，例如，可以是包括但不限于石墨、软碳、硬碳、碳纤维、中间相碳微球、硅基材料、锡基材料、钛酸锂或其他能与锂形成合金的金属等中的一种或几种。其中，所述石墨可选自人造石墨、天然石墨以及改性石墨中的一种或几种；所述硅基材料可选自单质硅、硅氧化合物、硅碳复合物、硅合金中的一种或几种；所述锡基材料可选自单质锡、锡氧化合物、锡合金中的一种或几种。所述负极集流体通常是汇集电流的结构或零件，所述负极集流体可以是本领域各种适用于作为锂离子电池负极集流体的材料，例如，所述负极集流体可以是包括但不限于金属箔等，更具体可以是包括但不限于铜箔等。
所述隔离膜可以是本领域各种适用于锂离子电池隔膜的材料，例如，可以是包括但不限于聚乙烯、聚丙烯、聚偏氟乙烯、芳纶、聚对苯二甲酸乙二醇酯、聚四氟乙烯、聚丙烯腈、聚酰亚胺，聚酰胺、聚酯和天然纤维等中的一种或多种的组合。
为使本发明的技术方案和优点更加清楚，下面将结合具体实施方式，对本发明及其有益效果作进一步详细的描述，但本发明的实施方式不限于此。
实施例1
一种锂离子电池，包括正极片、负极片和设置于正极片和负极片之间的隔膜，其中，正极片采用磷酸铁锂作为正极活性物质制备正极涂层，然后将上述的补锂浆料挤压涂覆于正极涂层上得到补锂涂层，控制补锂涂层厚度/正极涂层厚度＝1/8，负极片则采用350mAh/g的石墨作为负极材料，组装得到锂离子动力电池。
同样的，参照实施例1的设置制备实施例2～20的锂离子动力电池。
对比例1
与实施例1不同的是，本对比例的正极片不含补锂涂层。
其他同实施例1，这里不再赘述。
对比例2
与实施例1不同的是，本对比例的正极片含补锂材料，该补锂材料先与 正极浆料进行混匀后再涂覆。
其他同实施例1，这里不再赘述。
具体的，实施例1～20和对比例1～2的相关设置及相同条件下的性能测试结果见如下表1。其中，关系式1指代
Figure PCTCN2021123200-appb-000023
表1
Figure PCTCN2021123200-appb-000024
Figure PCTCN2021123200-appb-000025
实施例21
一种锂离子电池，包括正极片、负极片和设置于正极片和负极片之间的隔膜，其中，正极片采用三元材料作为正极活性物质制备正极涂层，然后将上述的补锂浆料挤压涂覆于正极涂层上得到补锂涂层，控制补锂涂层厚度/正极涂层厚度＝1/5，负极片则采用650mAh/g的硅氧作为负极材料，组装得到锂离子动力电池。
同样的，参照实施例21的设置制备实施例22～35的锂离子动力电池。
对比例3
与实施例21不同的是，本对比例的正极片不含补锂涂层。
其他同实施例21，这里不再赘述。
对比例4
与实施例21不同的是，本对比例的正极片含补锂材料，该补锂材料先与正极浆料进行混匀后再涂覆。
其他同实施例21，这里不再赘述。
具体的，实施例21～35和对比例3～4的相关设置及相同条件下的性能测试结果见如下表2。其中，关系式1指代
Figure PCTCN2021123200-appb-000026
表2
Figure PCTCN2021123200-appb-000027
Figure PCTCN2021123200-appb-000028
由上述实施例1～35和对比例1～4的对比中可以看出，满足本发明关系式添加的补锂材料，所得到的锂离子电池的首周放电容量和首周效率均得到有效提升，说明本发明的补锂涂层能较好与正极涂层融合，补锂材料利用率更高，补锂效率更高，且并不局限于草酸锂，适用性更广。如实施例1～20和对比例1～2中，磷酸铁锂与石墨体系的电池，在没加补锂浆料时，首周效率为91.1％；但引入补锂浆料后，最大的首效能够提升到97.9％，接近磷酸铁锂材料自身的首效值。同样的，三元NCM523材料与硅氧负极体系的电池，在没加补锂浆料时，首周效率为73.6％；但引入补锂浆料后，最大的首效能够提升到88.83％，接近三元NCM523材料自身的首效值。
此外，由实施例1～35中也可以看出，相同含量的补锂材料，改变导电剂、粘结剂、分散剂等的含量，在满足本发明关系式的前提下，随着本关系式的升高，锂离子电池的补锂效果呈现先增加后减小的趋势。这主要是因为补锂效果受多种因素的影响，补锂材料的比表面积、补锂材料的粒径、补锂材料的添加量、导电剂的比表面积、导电剂的添加量以及粘结剂的添加量等均会对补锂效果产生影响，同步控制此些因素才能最大程度的提升首效值。另外，随着补锂 材料含量的增加，补锂效果同样是呈现先增加后减小的趋势，这也是上述多种因素的共同作用的结果。
综上分析，通过本发明设计添加的补锂材料、导电剂、粘结剂和分散剂，可以达到更好的分散效果，将其涂覆于正极涂层后，所得到的正极片的阻抗更低，补锂效果更加优异，有效提高首次循环效率，使其接近该正极材料自身的首效值。
根据上述说明书的揭示和教导，本发明所属领域的技术人员还能够对上述实施方式进行变更和修改。因此，本发明并不局限于上述的具体实施方式，凡是本领域技术人员在本发明的基础上所作出的任何显而易见的改进、替换或变型均属于本发明的保护范围。此外，尽管本说明书中使用了一些特定的术语，但这些术语只是为了方便说明，并不对本发明构成任何限制。

Claims (15)

  1. 一种补锂浆料，其特征在于，包括补锂材料、导电剂和粘结剂；并满足以下关系式：
    Figure PCTCN2021123200-appb-100001
    其中，D50为所述补锂材料的平均粒径；
    B1为所述补锂材料的比表面积；
    B2为所述导电剂的比表面积；
    M1为所述补锂材料的质量占所述补锂浆料里固体成分质量的比例；
    M2为所述导电剂的质量占所述补锂浆料里固体成分质量的比例；
    M3为所述粘结剂的质量占所述补锂浆料里固体成分质量的比例。
  2. 根据权利要求1所述的补锂浆料，其特征在于，所述补锂材料包括至少一种可脱锂的含锂金属氧化物。
  3. 根据权利要求2所述的补锂浆料，其特征在于，当所述补锂材料包括至少两种所述含锂金属氧化物时，分别以M1a、M1b、M1c、……、M1n计其质量占所述补锂浆料里固体成分质量的比例，以B1a、B1b、B1c、……、B1n计其比表面积，以D50a、D50b、D50c、……、D50n计其平均粒径；则满足关系式：M1＝M1a+M1b+M1c+……+M1n；
    B1＝M1a*B1a+M1b*B1b+……+M1n*B1n；
    D50＝M1a*D50a+M1b*D50b+……+M1n*D50n。
  4. 根据权利要求3所述的补锂浆料，其特征在于，所述补锂材料的比表面积B1为0.3～15m 2/g；所述补锂材料的平均粒径D50为0.5～12μm；所述补锂材料的质量占所述补锂浆料里固体成分质量的比例M1为70～95％。
  5. 根据权利要求2～4任一项所述的补锂浆料，其特征在于，所述含锂金属氧化物为磷酸锂、磷酸氢二锂、硫酸锂、亚硫酸锂、钼酸锂、草酸锂、钛酸锂、四硼酸锂、偏硅酸锂、偏锰酸锂、酒石酸锂、柠檬酸三锂中的任意一种。
  6. 根据权利要求1所述的补锂浆料，其特征在于，所述导电剂由至少一种导电剂组成；当所述导电剂由至少两种导电剂混合而成时，分别以M2a、M2b、M2c、……、M2n计其质量占所述补锂浆料里固体成分质量的比例， 以B2a、B2b、B2c、……、B2n计其比表面积；则满足关系式：
    M2＝M2a+M2b+M2c+……+M2n；B2＝M2a*B2a+M2b*B2b+……+M2n*B2n。
  7. 根据权利要求6所述的补锂浆料，其特征在于，所述导电剂的比表面积B2为20～300m 2/g；所述导电剂的质量占所述补锂浆料里固体成分质量的比例M2为0.1～15％。
  8. 根据权利要求1～4、6～7任一项所述的补锂浆料，其特征在于，所述导电剂包括导电炭黑、导电石墨、科琴黑、碳纤维、碳纳米管、石墨烯、氧化石墨烯、气相生长炭纤维中的至少一种。
  9. 根据权利要求1～4、6～7任一项所述的补锂浆料，其特征在于，所述粘结剂为聚乙烯吡咯烷酮、聚偏氟乙烯、聚环氧乙烷、聚四氟乙烯、羧甲基纤维素钠、苯乙烯与丁二烯的共聚物中的至少一种；所述粘结剂的质量占所述补锂浆料里固体成分质量的比例M3为0.1～20％。
  10. 根据权利要求1～4、6～7任一项所述的补锂浆料，其特征在于，还包括分散剂；所述分散剂的质量占所述补锂浆料里的固体成分质量的比例为0.1～10％；所述分散剂为聚氧乙烯二油酸脂和/或聚四乙二醇单脂酸脂。
  11. 根据权利要求1～4、6～7任一项所述的补锂浆料，其特征在于，还包括溶剂；所述溶剂的质量占所述补锂浆料的质量的比例为20～50％；所述溶剂为水、N-甲基-2-吡咯烷酮、四氢呋喃、二甲基甲酰胺、乙醇中的至少一种。
  12. 一种正极片，其特征在于，包括正极涂层和涂覆于所述正极涂层上的补锂涂层；所述补锂涂层由权利要求1～11任一项所述的补锂浆料制成。
  13. 根据权利要求12所述的正极片，其特征在于，所述正极涂层的厚度和所述补锂涂层的厚度满足以下关系式：1/10<补锂涂层的厚度/正极涂层的厚度<1/3。
  14. 根据权利要求13所述的正极片，其特征在于，所述补锂涂层的厚度为5～100μm；所述正极涂层的厚度为50～300μm。
  15. 一种锂离子电池，其特征在于，包括权利要求12～14任一项所述的正极片。
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