WO2022237106A1 - 一种无钴正极材料浆料及其制备方法和应用技术领域 - Google Patents

一种无钴正极材料浆料及其制备方法和应用技术领域 Download PDF

Info

Publication number
WO2022237106A1
WO2022237106A1 PCT/CN2021/130820 CN2021130820W WO2022237106A1 WO 2022237106 A1 WO2022237106 A1 WO 2022237106A1 CN 2021130820 W CN2021130820 W CN 2021130820W WO 2022237106 A1 WO2022237106 A1 WO 2022237106A1
Authority
WO
WIPO (PCT)
Prior art keywords
cobalt
positive electrode
parts
free
material slurry
Prior art date
Application number
PCT/CN2021/130820
Other languages
English (en)
French (fr)
Inventor
常兴奇
Original Assignee
蜂巢能源科技有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 蜂巢能源科技有限公司 filed Critical 蜂巢能源科技有限公司
Priority to US18/289,985 priority Critical patent/US20240250262A1/en
Priority to EP21941670.8A priority patent/EP4325604A1/en
Publication of WO2022237106A1 publication Critical patent/WO2022237106A1/zh

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present disclosure relates to lithium-ion batteries, for example, to a cobalt-free cathode material slurry and a preparation method and application thereof.
  • Lithium-ion batteries have the advantages of high energy density, no memory effect, wide operating temperature, high voltage window, etc., and are widely used in high energy density battery products. While improving the energy density of batteries, how to reduce the production cost of batteries and improve the safety of batteries has become an urgent problem to be solved by various battery industries.
  • CN109755511A discloses a lithium-ion battery positive electrode material and a preparation method thereof.
  • the disclosed lithium-ion battery positive electrode material includes a positive electrode active material and an electron-conductive polymer and an ion-conductive polymer coated sequentially on the surface of the positive electrode active material from the inside to the outside.
  • Its disclosed preparation method is: the preparation of polysulfone polymer (electron-conductive polymer) containing triphenylamine structure in the main chain; the preparation of oxyxanthone-modified polymer (ion-conductive polymer); Molecular coating; ion-conducting polymer coating; spray-drying to obtain the polysulfone polymer and the modified polymer containing triphenylamine in the main chain that are sequentially coated on the surface of the positive electrode active material from the inside to the outside.
  • Lithium-ion battery cathode material the disclosed lithium-ion battery cathode material can significantly increase the energy density and power density of the battery, and can improve the cycle performance, rate performance, capacity retention and safety performance of the battery.
  • CN112038642A discloses a lithium-ion battery positive electrode slurry and its preparation method and application, and its disclosed slurry includes: positive electrode active material, conductive agent, binding agent, metaphosphate and organic solvent; based on the positive electrode active material, The total mass of the conductive agent, the binder and the metaphosphate, the content of the metaphosphate is 0.5%-1.9%.
  • metaphosphate is added to the positive electrode slurry, metaphosphate is directly wrapped on the surface of the positive electrode active material during dispersion, which can not only enhance its electronic conductivity, improve the first Coulombic efficiency and gram capacity of the battery, but also reduce the positive electrode active material and The contact area of the electrolyte reduces the occurrence of side reactions.
  • metaphosphate is weakly acidic, and can neutralize the residual alkali on the surface of the positive electrode active material under a certain voltage.
  • Nickel and manganese elements are mixed, rich in the surface of the material, and easily oxidized with the carbonate solvent in the electrolyte under the action of voltage and potential.
  • the reduction reaction causes battery gas production and loss of active lithium; in addition, mixed Ni and Mn elements are likely to cause poor battery performance at high temperatures.
  • high temperature gas production is intensified.
  • SEI solid-liquid contact film
  • the mixture of nickel-manganese oxides on the surface is stored in the air, it is easy to react with moisture and oxygen in the air, exposing active lithium, forming lithium oxide and causing irreversible loss of material capacity.
  • the positive electrode material is easily affected by environmental factors during the storage process. In the presence of moisture and oxygen in the air, it is easy to cause the stripping of lithium and nickel elements in the material, forming impurities of nickel hydroxide and lithium oxide, causing the capacity of the material to decrease.
  • the positive electrode material when the slurry is baked and rolled at high temperature, under the influence of temperature, the positive electrode material will accelerate the reaction with oxygen and moisture in the air to form more impurities; these nickel impurities are easily dissolved by electrolysis The liquid deposits on the surface of the negative electrode during charging and discharging, forming nickel dendrites, which poses a safety risk.
  • the present disclosure provides a cobalt-free cathode material slurry and a preparation method and application thereof.
  • the positive electrode sheet formed by the cobalt-free positive electrode material slurry provided by the present disclosure can better isolate air and moisture, protect the core component of the cobalt-free positive electrode material, reduce the occurrence of side reactions, reduce the generation of impurities in the working process, and have stable performance.
  • the further formed lithium-ion battery has high initial discharge capacity, capacity retention rate and initial Coulombic efficiency, and has high safety.
  • the present disclosure provides a cobalt-free positive electrode material slurry, the cobalt-free positive electrode material slurry includes a cobalt-free positive electrode material, a solvent, a sulfone compound containing an unsaturated bond, and an additive;
  • the parts by weight of the solvent are 25-40 parts, such as 26 parts, 28 parts, 30 parts, 32 parts, 34 parts, 36 parts parts, 38 parts, etc.
  • the parts by weight of sulfone compounds containing unsaturated bonds are 1-7 parts, such as 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts parts, 6 parts, 6.5 parts, etc.
  • the cobalt-free cathode material slurry includes a sulfone compound containing an unsaturated bond, and the sulfone compound containing an unsaturated bond cooperates with a solvent to increase the viscosity of the cobalt-free cathode material on the one hand; on the other hand, the formed
  • the surface of the cobalt-free positive electrode material can better isolate air and moisture, and protect the core component positive electrode material. Therefore, the lithium-ion battery formed by using the cobalt-free positive electrode material slurry has a higher initial discharge capacity, capacity retention rate and initial discharge capacity. Coulombic efficiency, high security.
  • the parts by weight of the solvent and the sulfone compound containing an unsaturated bond are 25-40 parts and 1-7 parts respectively, and the solvent and the sulfone compound containing an unsaturated bond play a synergistic effect and cooperate with each other under a specific ratio.
  • the obtained lithium ion battery has high initial discharge capacity, capacity retention rate and initial coulombic efficiency, and has high safety.
  • the weight part of the cobalt-free positive electrode material is 90-96 parts, such as 91 parts, 92 parts, 93 parts, 94 parts, 95 parts and so on.
  • the parts by weight of the auxiliary agent are 4-10 parts, such as 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, etc.
  • the cobalt-free positive electrode material includes Li x Ni y Mnz O 2 ;
  • x is 1-1.1 (such as 1.02, 1.04, 1.06, 1.08, etc.)
  • y is 0.7-0.8 (such as 0.72, 0.73, 0.74, 0.75, 0.76, 0.77, 0.78, 0.79, etc.)
  • the solvent includes any one or a combination of at least two of N-methylpyrrolidone (NMP), acetone, dimethyl sulfoxide or tetrahydrofuran.
  • NMP N-methylpyrrolidone
  • acetone dimethyl sulfoxide or tetrahydrofuran.
  • the solvent is NMP.
  • NMP is cheap, and the performance of the formed cathode material slurry is stable.
  • the sulfone compounds containing unsaturated bonds include any one or a combination of at least two of divinyl sulfone (DVS), trivinyl sulfone or propylene sulfone, wherein typical but not limiting
  • the combination includes: the combination of divinyl sulfone and trivinyl sulfone, the combination of trivinyl sulfone and propylene sulfone, the combination of divinyl sulfone, trivinyl sulfone and propylene sulfone, etc.
  • the sulfone compound containing unsaturated bonds is DVS.
  • DVS is used in conjunction with the solvent NMP because DVS has good solubility in NMP and DVS is low in cost.
  • the auxiliary agent includes at least one of a binder and a conductive agent.
  • the binder includes any one or a combination of at least two of polyvinylidene fluoride, polyacrylonitrile or polyacrylic acid, wherein typical but non-limiting combinations include: vinylidene fluoride and polyvinylidene fluoride A combination of acrylonitrile, a combination of polyacrylonitrile and polyacrylic acid, a combination of polyvinylidene fluoride, polyacrylonitrile and polyacrylic acid, etc.
  • the conductive agent includes any one or a combination of at least two of conductive carbon black, carbon nanotubes or graphene, wherein typical but non-limiting combinations include: conductive carbon black and carbon nanotubes The combination of carbon nanotubes and graphene, the combination of conductive carbon black, carbon nanotubes and graphene, etc.
  • the present disclosure provides a method for preparing the above-mentioned cobalt-free cathode material slurry.
  • the preparation method includes the following steps: after mixing the cobalt-free cathode material, a solvent and an auxiliary agent, and then mixing the obtained mixed material with The sulfone compounds with saturated bonds are mixed below 60°C (for example, 55°C, 50°C, 45°C, 40°C, 35°C, 30°C, 25°C, etc.) to obtain the cobalt-free cathode material slurry.
  • a sulfone compound containing an unsaturated bond is added at the end, and mixed at a lower temperature, which is conducive to the formation of a cobalt-free cathode material slurry with stable performance, which is convenient Form the positive pole piece.
  • the present disclosure provides a positive electrode sheet, wherein the raw material for preparing the positive electrode sheet includes the above-mentioned cobalt-free positive electrode material slurry.
  • the present disclosure provides a method for preparing the above-mentioned positive electrode sheet.
  • the preparation method includes the following steps: coating the cobalt-free positive electrode material slurry on a substrate and heating to obtain the positive electrode sheet.
  • the current thick electrodes are mainly realized by increasing the surface density of the coating.
  • the electrode sheet has a high compaction density, which results in poor performance of the electrolyte wetting the electrode sheet and excessive rebound of the electrode.
  • cobalt-free is mainly Ni and Mn binary materials, its surface is highly alkaline, has poor conductivity and has metal residues. These metal residues have the risk of being dissolved into the electrolyte, which increases the self-discharge phenomenon of the battery and improves the safety of the battery. decline.
  • the present disclosure is heated during preparation.
  • the solvent carries sulfone compounds containing unsaturated bonds to volatilize, part of the sulfone compounds volatilize into the air, and part of the sulfone compounds generate polymerization and crosslinking on the surface of the coating during volatilization.
  • a thin polymer layer is obtained on the surface of the coating, which can better isolate air and moisture, protect the positive electrode material, reduce the formation of impurities, improve the safety of the battery, and the process is simple without increasing the process. improve battery performance.
  • the heating temperature is 60-150°C, such as 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C , 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, etc.
  • the sulfone compound can polymerize and cross-link on the surface of the coating to the greatest extent, and the loss rate is low.
  • the heating temperature is 100-150°C, such as 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, etc.
  • the heating time is greater than or equal to 30 seconds, such as 40 seconds, 50 seconds, 60 seconds, 70 seconds and so on.
  • the preparation method includes the following steps: coating the cobalt-free cathode material slurry on a current collector, and heating at 60-150° C. for more than 30 seconds to obtain the cathode sheet.
  • the present disclosure provides a battery in an embodiment, and the battery includes the above-mentioned positive electrode sheet.
  • the positive electrode sheet formed by the cobalt-free positive electrode material slurry in the present disclosure can better isolate air and moisture, protect the core component positive electrode material, reduce the occurrence of side reactions, reduce the generation of impurities in the working process, and have stable performance.
  • Advanced lithium-ion batteries have high initial discharge capacity, capacity retention rate and initial Coulombic efficiency, and are highly safe.
  • the DVS in the positive electrode cobalt-free positive electrode material slurry of the present disclosure is in the range of 2-6 parts, the performance of the obtained lithium ion battery is better, the first discharge capacity is above 166mAh/g, the first coulombic efficiency is above 65%, and the capacity The retention rate is above 57%, the initial discharge capacity of the lithium-ion battery obtained with 2 parts of DVS is 183mAh/g, the initial Coulombic efficiency is 81%, and the capacity retention rate after 500 cycles is 80%.
  • Fig. 1 is a graph showing the relationship between the capacity retention rate and time of the lithium-ion batteries formed in the application example and the application comparison example.
  • the present disclosure proposes a cobalt-free positive electrode slurry.
  • the cobalt-free positive electrode slurry includes a cobalt-free positive electrode material, a solvent, a sulfone compound containing an unsaturated bond, and a cobalt-free positive electrode slurry. agent; based on 100 parts by weight of the cobalt-free positive electrode material and additives, the parts by weight of the solvent is 25-40 parts, and the parts by weight of the sulfone compound containing unsaturated bonds is 1- 7 servings.
  • the cobalt-free positive electrode material slurry includes a sulfone compound containing an unsaturated bond, and the sulfone compound containing an unsaturated bond acts synergistically with a solvent, and the first aspect can increase the viscosity of the cobalt-free positive electrode material; the second aspect is to form The surface of the cobalt-free positive electrode material can better isolate air and moisture, and protect the core component positive electrode material.
  • the solvent under a specific ratio and the sulfone compound containing an unsaturated bond play a synergistic role and cooperate with each other to obtain lithium Ion batteries have higher first-time discharge capacity, capacity retention rate and first-time Coulombic efficiency, and higher safety. Therefore, the lithium-ion battery formed by using the cobalt-free positive electrode material slurry has higher first-time discharge capacity and capacity retention rate. And the first Coulombic efficiency, higher security.
  • the parts by weight of the cobalt-free cathode material are 90-96 parts.
  • the parts by weight of the auxiliary agent are 4-10 parts.
  • the solvent may be any one or a combination of at least two of NMP, acetone, dimethyl sulfoxide or tetrahydrofuran.
  • the solvent of an embodiment of the present disclosure is NMP.
  • NMP is cheap, and the performance of the formed cathode material slurry is stable.
  • the sulfone compound containing an unsaturated bond includes any one or a combination of at least two of DVS, trivinyl sulfone or propylene sulfone.
  • the sulfone compound containing unsaturated bonds is DVS.
  • DVS is used in combination with NMP, because DVS has good solubility in NMP and the cost of DVS is low.
  • the specific type of the auxiliary agent is not particularly limited, and those skilled in the art can select according to actual needs, for example, the auxiliary agent can be selected from at least one of a binder and a conductive agent.
  • the specific type of adhesive is not particularly limited, and those skilled in the art can choose according to actual needs, such as the adhesive can be selected from any of polyvinylidene fluoride, polyacrylonitrile or polyacrylic acid.
  • the adhesive is selected from polyvinylidene fluoride.
  • the specific type of conductive agent is not particularly limited, and those skilled in the art can select according to actual needs, such as conductive agent can be selected from any one of conductive carbon black, carbon nanotubes or graphene Or a combination of at least two, in one embodiment, the conductive agent is selected from conductive carbon black.
  • the present disclosure proposes a method for preparing a cobalt-free positive electrode material slurry.
  • the preparation method includes the following steps: mixing the cobalt-free positive electrode material, a solvent and an additive Afterwards, the obtained mixed material is mixed with a sulfone compound containing an unsaturated bond at a temperature below 60° C. to obtain the cobalt-free cathode material slurry.
  • the sulfone compound containing unsaturated bonds is added at the end, and mixed at a lower temperature, which is conducive to the formation of a cobalt-free positive electrode material slurry with stable performance, and facilitates the formation of positive electrode sheets.
  • the present disclosure provides a positive electrode sheet.
  • the raw material for preparing the positive electrode sheet includes the above-mentioned cobalt-free positive electrode material slurry.
  • the present disclosure proposes a method for preparing the above-mentioned positive electrode sheet.
  • the preparation method includes the following steps: coating the cobalt-free positive electrode material slurry on the substrate , heated to obtain the positive electrode sheet.
  • the current thick electrodes are mainly realized by increasing the surface density of the coating.
  • the electrode sheet has a high compaction density, which results in poor performance of the electrolyte wetting the electrode sheet and excessive rebound of the electrode.
  • cobalt-free is mainly Ni and Mn binary materials, its surface is highly alkaline, has poor conductivity and has metal residues. These metal residues have the risk of being dissolved into the electrolyte, which increases the self-discharge phenomenon of the battery and improves the safety of the battery. decline.
  • heating is carried out during the preparation, and during heating, the solvent carries sulfone compounds containing unsaturated bonds to volatilize, part of the sulfone compounds volatilizes into the air, and part of the sulfone compounds volatilizes in the coating
  • the surface is polymerized and crosslinked, and a thin polymer layer is obtained on the surface of the coating.
  • the polymer layer can better isolate air and moisture, protect the positive electrode material, reduce the formation of impurities, and improve the safety of the battery.
  • the process is simple. Improve the performance of the battery without increasing the process.
  • the heating temperature is 60-150°C. At this temperature, the sulfone compound can polymerize and cross-link on the surface of the coating to the greatest extent, and the loss rate is low. In one embodiment, the heating temperature may be 100-150°C.
  • the heating time is greater than or equal to 30 seconds, and in one embodiment, the heating time is 30 seconds.
  • heating can meet the requirements in a relatively short time.
  • the preparation method includes the following steps: coating the cobalt-free cathode material slurry on a current collector, and heating at 60-150° C. for more than 30 seconds to obtain the cathode sheet.
  • This embodiment provides a cobalt-free cathode material slurry, which is composed of 95 parts by weight of a cobalt-free cathode material (LiNi 0.7 Mn 0.3 O 2 ), 1.5 parts of a binder (polyvinylidene fluoride Ethylene, purchased from Sinopharm Chemical Reagent Network), 3.5 parts of conductive agent (conductive carbon black, purchased from Pioneer Technology), 30 parts of solvent (NMP) and 2 parts of sulfone compounds (DVS) containing unsaturated bonds.
  • a cobalt-free cathode material LiNi 0.7 Mn 0.3 O 2
  • a binder polyvinylidene fluoride Ethylene, purchased from Sinopharm Chemical Reagent Network
  • conductive agent conductive carbon black, purchased from Pioneer Technology
  • NMP solvent
  • DVS sulfone compounds
  • the preparation method of the above-mentioned cobalt-free cathode material slurry comprises the following steps:
  • the binder After mixing the cobalt-free positive electrode material, the binder, the conductive agent and the solvent, add a sulfone compound containing an unsaturated bond, and mix uniformly at 25° C. to obtain the cobalt-free positive electrode material slurry.
  • embodiment 2-5 The difference between embodiment 2-5 and embodiment 1 is that the parts by weight of DVS are respectively 3 parts (embodiment 2), 4 parts (embodiment 3), 5 parts (embodiment 4) and 6 parts (embodiment 5) , all the other are identical with embodiment 1.
  • This embodiment provides a cobalt-free cathode material slurry, which consists of 95 parts by weight of a cobalt-free cathode material (Li1.1Ni 0.8 Mn 0.2 O 2 ), 1 part of a binder (poly Acrylic acid, purchased from Sinopharm Chemical Reagent Network), 3 parts of conductive agent (carbon nanotubes, purchased from Pioneer Technology), 25 parts of solvent (NMP) and 1 part of sulfone compound (DVS) containing unsaturated bonds.
  • a cobalt-free cathode material Li1.1Ni 0.8 Mn 0.2 O 2
  • a binder poly Acrylic acid, purchased from Sinopharm Chemical Reagent Network
  • conductive agent carbon nanotubes, purchased from Pioneer Technology
  • NMP solvent
  • DVS sulfone compound
  • the preparation method of the above-mentioned cobalt-free cathode material slurry comprises the following steps:
  • This embodiment provides a cobalt-free positive electrode material slurry, which consists of 91 parts by weight of a cobalt-free positive electrode material (LiNi 0.7 Mn 0.3 O 2 ), 7 parts of a binder (polyvinylidene fluoride Ethylene PVDF, purchased from Sinopharm Chemical Reagent Network), 4 parts of conductive agent (conductive carbon black, purchased from Pioneer Technology), 40 parts of solvent (NMP) and 7 parts of sulfone compounds (DVS) containing unsaturated bonds.
  • a cobalt-free positive electrode material LiNi 0.7 Mn 0.3 O 2
  • a binder polyvinylidene fluoride Ethylene PVDF, purchased from Sinopharm Chemical Reagent Network
  • conductive agent conductive carbon black, purchased from Pioneer Technology
  • NMP solvent
  • DVS sulfone compounds
  • the preparation method of the above-mentioned cobalt-free cathode material slurry comprises the following steps:
  • Example 1 The difference between this comparative example and Example 1 is that no DVS is added, and the rest are the same as Example 1.
  • This application example provides a positive electrode sheet.
  • the raw material for the preparation of the positive electrode sheet includes the cobalt-free positive electrode material slurry described in Example 1.
  • the preparation method of the above-mentioned positive pole piece comprises the following steps:
  • the cobalt-free cathode material slurry was coated on a substrate (aluminum foil, purchased from Chalco), and heated at 100° C. for 30 seconds to obtain the cathode sheet.
  • a button battery, metal lithium sheet, diaphragm, positive electrode sheet described in Application Examples 1-16 and Application Comparative Example 1 are used to assemble in sequence (the diaphragm separates the positive electrode and lithium sheet), and then the ethylene carbonate of 1M lithium iron phosphate is added to the electrolyte A mixed solvent with ethyl methyl carbonate, sealed, assembled into a lithium-ion battery.
  • the assembled lithium-ion battery was tested for electrical performance on an electrochemical test cabinet.
  • the specific process was as follows: charge at 0.3C to 4.3V at 25°C, leave it for 2 minutes, charge it at 0.2C to 4.3V, leave it for 2 minutes, and then charge it at 0.1 Charge C to 4.3V, rest for 2min, then charge to 4.3V at 0.05C, rest for 5min, discharge to 2.8V at 0.3C, and repeat the above steps in a cycle.
  • the test items include the first discharge capacity, the first Coulombic efficiency and the capacity retention rate after 500 cycles.
  • test results are shown in Figure 1, and the test data are summarized in Table 1.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

本文公布了一种无钴正极材料浆料及其制备方法和应用，所述无钴正极材料浆料包括无钴正极材料、溶剂、含有不饱和键的砜类化合物和助剂，以所述无钴正极材料和助剂的总重量份数为100份计，所述溶剂的重量份数为25-40份，含有不饱和键的砜类化合物的重量份数为1-7份。该无钴正极材料浆料形成的正极极片能较好地隔绝空气与水分，保护核心组分无钴正极材料，其形成的锂离子电池具有较高的首次放电容量、容量保持率和首次库伦效率，安全性较高。

Description

一种无钴正极材料浆料及其制备方法和应用技术领域
本公开涉及锂离子电池，例如涉及一种无钴正极材料浆料及其制备方法和应用。
背景技术
锂离子电池具有能量密度高、无记忆效应、宽的使用温度、高的电压窗口等的优势广泛用于高能量密度的电池产品。在提高电池能量密度的同时，如何降低电池的生产成本、提高电池的安全性成为各个电池产业迫切解决的难题。
CN109755511A公开了一种锂离子电池正极材料及其制备方法，其公开的锂离子电池正极材料包括正极活性物质和在正极活性物质表面从里到外依次包覆的电子导电高分子和离子导电高分子；其公开的制备方法为：主链含有三苯胺结构的聚氮苯砜聚合物(电子导电高分子)的制备；含氧吨酮改性高分子(离子导电高分子)的制备；电子导电高分子包覆；离子导电高分子包覆；喷雾干燥，得到在正极活性物质表面从里到外依次包覆有主链含有三苯胺结构的聚氮苯砜聚合物和含氧吨酮改性高分子的锂离子电池正极材料；其公开的锂离子电池正极材料能够显著提高电池的能量密度和功率密度，且能够改善电池的循环性能、倍率性能、容量保持率和安全性能。
CN112038642A公开了一种锂离子电池正极浆料及其制备方法和应用，其公开的浆料包括：正极活性材料、导电剂、粘结剂、偏磷酸盐和有机溶剂；基于所述正极活性材料、导电剂、粘结剂和偏磷酸盐的总质量，所述偏磷酸盐的含量为0.5％-1.9％。将偏磷酸盐添加到正极浆料当中，偏磷酸盐在分散时直接包裹在正极活性物质表面，不仅可以增强其电子电导率，提高电池的首次库伦效率和克容量，还可以减少正极活性物质和电解液的接触面积，减少副反应的发生，此外，偏磷酸盐呈弱酸性，在一定的电压下，可以中和正极活性物质表面的残碱。
综上所述，开发一种能形成极片时杂质生成量少且性能稳定的正极极片的正极浆料至关重要。
发明内容
对于正极材料来说，很多存在镍(Ni)锰(Mn)元素，镍锰元素存在混排现象，富含在材料表面，在电压电位的作用下易与电解液中的碳酸酯类溶剂发生氧化还原反应，造成电池产气及活性锂的损失；此外，混排的Ni、Mn元素容易造成电池在高温下性能表现不佳，通俗来说就是高温产气现象加剧，高温下，材料表面残余的三价镍元素在接触到电解液，在电位作用下，持续催化电解液分解，在表面形成一个厚的固液接触膜(SEI)，较厚的SEI造成电池电阻增大，电池产热现象加剧，电池自放电现象加剧，严重影响电池的存储性能。
此外，表面的镍锰氧化物的混合物在空气中存放时，易与空气中的水分和氧气反应，暴露出活性锂，形成氧化锂造成材料容量的不可逆损失。正极材料在存放过程中易受到环境因素的影响，在空气中的水分和氧的存在下，易造成材料中的锂和镍元素的剥离，形成氢氧化镍和氧化锂的杂质，引起材料容量的 衰退，同时，在浆料经过高温烘烤和辊压阶段，在温度的影响下，正极材料会加速与空气中的氧和水分反应，形成更多的杂质；这些镍元素杂质，极易溶解电解液，随着充放电过程沉积在负极表面，形成镍枝晶，存在安全性风险。
本公开提供一种无钴正极材料浆料及其制备方法和应用。本公开提供的无钴正极材料浆料形成的正极极片能较好地隔绝空气与水分，保护核心组分无钴正极材料，减少副反应的发生，降低工作过程中杂质的产生，性能稳定，进一步形成的锂离子电池具有较高的首次放电容量、容量保持率和首次库伦效率，安全性较高。
本公开在一实施例中提供一种无钴正极材料浆料，所述无钴正极材料浆料包括无钴正极材料、溶剂、含有不饱和键的砜类化合物和助剂；
以所述无钴正极材料和助剂的总重量份数为100份计，所述溶剂的重量份数为25-40份，例如26份、28份、30份、32份、34份、36份、38份等，含有不饱和键的砜类化合物的重量份数为1-7份，例如1.5份、2份、2.5份、3份、3.5份、4份、4.5份、5份、5.5份、6份、6.5份等。
该无钴正极材料浆料中包括含有不饱和键的砜类化合物，所述含有不饱和键的砜类化合物与溶剂协同作用，一方面可以提升无钴正极材料的粘度；另一方面，形成的无钴正极材料表面能较好地隔绝空气与水分，保护核心组分正极材料，因此，利用所述无钴正极材料浆料形成的锂离子电池具有较高的首次放电容量、容量保持率和首次库伦效率，安全性较高。所述溶剂和含有不饱和键的砜类化合物的重量份数分别为25-40份和1-7份，特定配比下的溶剂和含有不饱和键的砜类化合物发挥协同作用，相互配合，所得锂离子电池具有较高的首次放电容量、容量保持率和首次库伦效率，安全性较高。
在一实施例中，所述无钴正极材料的重量份数为90-96份，例如91份、92份、93份、94份、95份等。
在一实施例中，所述助剂的重量份数为4-10份，例如5份、6份、7份、8份、9份等。
在一实施例中，所述无钴正极材料包括Li xNi yMn zO 2；
其中，x为1-1.1(例如1.02、1.04、1.06、1.08等)，y为0.7-0.8(例如0.72、0.73、0.74、0.75、0.76、0.77、0.78、0.79等)，z为0.2-0.5(例如0.25、0.3、0.35、0.4、0.45等)，y+z＝1。
在一实施例中，所述溶剂包括N-甲基吡咯烷酮(NMP)、丙酮、二甲基亚砜或四氢呋喃中的任意一种或至少两种的组合。
在一实施例中，所述溶剂为NMP。NMP作为溶剂，价格便宜，所形成的正极材料浆料性能稳定。
在一实施例中，所述含有不饱和键的砜类化合物包括二乙烯基砜(DVS)、三乙烯基砜或丙烯砜中的任意一种或至少两种的组合，其中典型但非限制性的组合包括：二乙烯基砜和三乙烯基砜的组合，三乙烯基砜和丙烯砜的组合，二乙烯基砜、三乙烯基砜和丙烯砜的组合等。
在一实施例中，所述含有不饱和键的砜类化合物为DVS。DVS与溶剂NMP配合使用，原因在于DVS在NMP中溶解性良好，而且DVS成本低廉。
在一实施例中，所述助剂包括粘结剂、导电剂中的至少之一。
在一实施例中，所述粘结剂包括聚偏氟乙烯、聚丙烯腈或聚丙烯酸中的任意一种或至少两种的组合，其中典型但非限制性的组合包括：偏氟乙烯和聚丙烯腈的组合，聚丙烯腈和聚丙烯酸的组合，聚偏氟乙烯、聚丙烯腈和聚丙烯酸的组合等。
在一实施例中，所述导电剂包括导电炭黑、碳纳米管或石墨烯中的任意一种或至少两种的组合，其中典型但非限制性的组合包括：导电炭黑和碳纳米管的组合，碳纳米管和石墨烯的组合，导电炭黑、碳纳米管和石墨烯的组合等。
本公开在一实施例中提供一种上述无钴正极材料浆料的制备方法，所述制备方法包括如下步骤：将无钴正极材料、溶剂和助剂混合后，再将所得混合物料与含有不饱和键的砜类化合物在60℃以下(例如55℃、50℃、45℃、40℃、35℃、30℃、25℃等)混合，得到所述无钴正极材料浆料。
本公开在一实施例中，所述无钴正极材料浆料制备时最后加入含有不饱和键的砜类化合物，且在较低温度下混合，利于形成性能稳定的无钴正极材料浆料，便于形成正极极片。
本公开在一实施例中提供一种正极极片，所述正极极片的制备原料包括上述无钴正极材料浆料。
本公开在一实施例中提供一种上述正极极片的制备方法，所述制备方法包括如下步骤：将所述无钴正极材料浆料涂覆于基底，加热，得到所述正极极片。
目前的厚电极，尤其是无钴电池厚电极，主要通过增加涂布面密度来实现，为保证极片厚度，采用多次辊压的方式制备厚电极极片；但是通过这种方法制备的厚电极片，压实密度大，造成电解液润湿极片的性能较差，电极反弹过大的缺点。其次，由于无钴为Ni、Mn二元材料为主，其表面碱性较大，导电性差且存在金属残余，这些金属残余存在溶解到电解液的风险，增加电池的自放电现象，电池安全性下降。
本公开在制备时进行加热，在加热时，溶剂携带含有不饱和键的砜类化合物发生挥发，一部分砜类化合物挥发至空气中，一部分砜类化合物在挥发时在涂层表面产生聚合交联，在涂层表面得到一层薄聚合物层，该聚合物层能较好地隔绝空气与水分，保护正极材料，减少杂质的形成，提高电池的安全性，且工艺简单，在不增加工序的前提下提高电池的性能。
在一实施例中，所述加热的温度为60-150℃，例如65℃、70℃、75℃、80℃、85℃、90℃、95℃、100℃、105℃、110℃、115℃、120℃、125℃、130℃、135℃、140℃、145℃等。该温度下砜类化合物能最大程度上在涂层表面聚合交联，损失率较低。
在一实施例中，所述加热的温度为100-150℃，例如105℃、110℃、115℃、120℃、125℃、130℃、135℃、140℃、145℃等。
在一实施例中，所述加热的时间大于等于30秒，例如40秒、50秒、60秒、70秒等。
在一实施例中，所述制备方法包括如下步骤：将所述无钴正极材料浆料涂覆于集流体，在60-150℃下加热30秒以上，得到所述正极极片。
本公开在一实施例中提供一种电池，所述电池包括上述所述的正极极片。
本公开所述无钴正极材料浆料形成的正极极片能较好地隔绝空气与水分，保护核心组分正极材料，减少副反应的发生，降低工作过程中杂质的产生，性能稳定，其形成的锂离子电池具有较高的首次放电容量、容量保持率和首次库伦效率，安全性较高。其中，本公开所述正极无钴正极材料浆料中DVS在2-6份范围内时，所得锂离子电池性能较好，首次放电容量在166mAh/g以上，首次库伦效率在65％以上，容量保持率在57％以上，DVS为2份所得锂离子电池首次放电容量为183mAh/g，首次库伦效率为81％，循环500圈后容量保持率为80％。
本公开的附加方面和优点将在下面的描述中部分给出，部分将从下面的描述中变得明显，或通过本公开的实践了解到。
附图说明
附图用来提供对本公开技术方案的进一步理解，并且构成说明书的一部分，与本申请的实施例一起用于解释本公开的技术方案，并不构成对本公开技术方案的限制。
图1是应用例和应用对比例形成的锂离子电池的容量保持率与时间的关系图。
具体实施例
下面结合附图并通过具体实施方式来进一步说明本公开的技术方案。
在本公开的一个方面，本公开提出了一种无钴正极浆料，根据本公开的实施例，该无钴正极浆料包括无钴正极材料、溶剂、含有不饱和键的砜类化合物和助剂；以所述无钴正极材料和助剂的总重量份数为100份计，所述溶剂的重量份数为25-40份，含有不饱和键的砜类化合物的重量份数为1-7份。该无钴正极材料浆料中包括含有不饱和键的砜类化合物，所述含有不饱和键的砜类化合物与溶剂协同作用，第一方面可以提升无钴正极材料的粘度；第二方面，形成的无钴正极材料表面能较好地隔绝空气与水分，保护核心组分正极材料，第三方面，特定配比下的溶剂和含有不饱和键的砜类化合物发挥协同作用，相互配合，所得锂离子电池具有较高的首次放电容量、容量保持率和首次库伦效率，安全性较高，因此，利用所述无钴正极材料浆料形成的锂离子电池具有较高的首次放电容量、容量保持率和首次库伦效率，安全性较高。
根据本公开的一个实施例，所述无钴正极材料的重量份数为90-96份。
根据本公开的一个实施例，所述助剂的重量份数为4-10份。
根据本公开的一个实施例，所述无钴正极材料包括Li xNi yMn zO 2；其中，x为1-1.1，y为0.7-0.8，z为0.2-0.5，y+z＝1。
根据本公开的一个实施例，所述溶剂可以为NMP、丙酮、二甲基亚砜或四氢呋喃中的任意一种或至少两种的组合。本公开一实施例的溶剂为NMP。NMP作为溶剂，价格便宜，所形成的正极材料浆料性能稳定。
根据本公开的一个实施例，所述含有不饱和键的砜类化合物包括DVS、三乙烯基砜或丙烯砜中的任意一种或至少两种的组合。在一个实施例中，所述含有不饱和键的砜类化合物为DVS。
根据本公开的一个实施例，DVS与NMP配合使用，原因在于DVS在NMP中溶解性良好，DVS成本低廉。
根据本公开的一个实施例，助剂的具体类型不受特别限制，本领域技术人员可以根据实际需要进行选择，如助剂可以选自粘结剂、导电剂中的至少之一。
根据本公开的一个实施例，粘接剂的具体类型不受特别限制，本领域技术人员可以根据实际需要进行选择，如粘结剂可以选择聚偏氟乙烯、聚丙烯腈或聚丙烯酸中的任意一种或至少两种的组合，在一实施例中，粘接剂选自聚偏氟乙烯。
根据本公开的一个实施例，导电剂的具体类型不受特别限制，本领域技术人员可以根据实际需要进行选择，如导电剂可以选自导电炭黑、碳纳米管或石墨烯中的任意一种或至少两种的组合，在一实施例中，导电剂选自导电炭黑。
在本公开的再一个方面，本公开提出了一种无钴正极材料浆料的制备方法，根据本公开的实施例，所述制备方法包括如下步骤：将无钴正极材料、溶剂和助剂混合后，再将所得混合物料与含有不饱和键的砜类化合物在60℃以下混合，得到所述无钴正极材料浆料。所述无钴正极材料浆料制备时最后加入含有不饱和键的砜类化合物，且在较低温度下混合，利于形成性能稳定的无钴正极材料浆料，便于形成正极极片。
在本公开的再一个方面，本公开提出了一种正极极片，根据本公开的实施例，所述正极极片的制备原料包括上述无钴正极材料浆料。
在本公开的再一个方面，本公开提出了一种上述正极极片的制备方法，根据本公开的实施例，所述制备方法包括如下步骤：将所述无钴正极材料浆料涂覆于基底，加热，得到所述正极极片。
目前的厚电极，尤其是无钴电池厚电极，主要通过增加涂布面密度来实现，为保证极片厚度，采用多次辊压的方式制备厚电极极片；但是通过这种方法制备的厚电极片，压实密度大，造成电解液润湿极片的性能较差，电极反弹过大的缺点。其次，由于无钴为Ni、Mn二元材料为主，其表面碱性较大，导电性差且存在金属残余，这些金属残余存在溶解到电解液的风险，增加电池的自放电现象，电池安全性下降。
根据本公开的一个实施例，在制备时进行加热，在加热时，溶剂携带含有不饱和键的砜类化合物发生挥发，一部分砜类化合物挥发至空气中，一部分砜类化合物在挥发时在涂层表面产生聚合交联，在涂层表面得到一层薄聚合物层，该聚合物层能较好地隔绝空气与水分，保护正极材料，减少杂质的形成，提高 电池的安全性，且工艺简单，在不增加工序的前提下提高电池的性能。
根据本公开的一个实施例，所述加热的温度为60-150℃。该温度下砜类化合物能最大程度上在涂层表面聚合交联，损失率较低。在一实施例中，所述加热的温度可以为100-150℃。
根据本公开的一个实施例，所述加热的时间大于等于30秒，在一实施例中，所述加热的时间为30秒。本公开中加热在较短时间内即可达到要求。
根据本公开的一个实施例，所述制备方法包括如下步骤：将所述无钴正极材料浆料涂覆于集流体，在60-150℃下加热30秒以上，得到所述正极极片。
下面参考具体实施例，对本公开进行描述，需要说明的是，这些实施例仅仅是描述性的，而不以任何方式限制本公开。
实施例1
本实施例提供一种无钴正极材料浆料，所述无钴正极材料浆料按照重量份数由95份无钴正极材料(LiNi 0.7Mn 0.3O 2)，1.5份粘结剂(聚偏氟乙烯，购于国药化学试剂网)，3.5份导电剂(导电炭黑，购于先锋科技)，30份溶剂(NMP)和2份含有不饱和键的砜类化合物(DVS)组成。
上述无钴正极材料浆料的制备方法包括如下步骤：
将无钴正极材料、粘结剂、导电剂和溶剂混合后，再加入含有不饱和键的砜类化合物，在25℃下混合均匀，得到所述无钴正极材料浆料。
实施例2-5
实施例2-5与实施例1的区别在于DVS的重量份数分别为3份(实施例2)、4份(实施例3)、5份(实施例4)和6份(实施例5)，其余均与实施例1相同。
实施例6
本实施例提供一种无钴正极材料浆料，所述无钴正极材料浆料按照重量份数由95份无钴正极材料(Li1.1Ni 0.8Mn 0.2O 2)，1份粘结剂(聚丙烯酸，购于国药化学试剂网)，3份导电剂(碳纳米管，购于先锋科技)，25份溶剂(NMP)和1份含有不饱和键的砜类化合物(DVS)组成。
上述无钴正极材料浆料的制备方法包括如下步骤：
将无钴正极材料、粘结剂、导电剂和溶剂混合后，再加入含有不饱和键的砜类化合物，在45℃下混合均匀，得到所述正极材料浆料。
实施例7
本实施例提供一种无钴正极材料浆料，所述无钴正极材料浆料按照重量份数由91份无钴正极材料(LiNi 0.7Mn 0.3O 2)，7份粘结剂(聚偏氟乙烯PVDF，购于国药化学试剂网)，4份导电剂(导电炭黑，购于先锋科技)，40份溶剂(NMP)和7份含有不饱和键的砜类化合物(DVS)组成。
上述无钴正极材料浆料的制备方法包括如下步骤：
将无钴正极材料、粘结剂、导电剂和溶剂混合后，再加入含有不饱和键的砜类化合物，在50℃下混合均匀，得到所述正极材料浆料。
实施例8
本实施例与实施例1的区别在于DVS的重量份数为0.5份，其余均与实施例1相同。
实施例9
本实施例与实施例1的区别在于DVS的重量份数为8份，其余均与实施例1相同。
实施例10
本实施例与实施例1的区别在于NMP的重量份数为50份，其余均与实施例1相同。
实施例11
本实施例与实施例1的区别在于NMP的重量份数为20份，其余均与实施例1相同。
对比例1
本对比例与实施例1的区别在于不添加DVS，其余均与实施例1相同。
应用例1
本应用例提供一种正极极片，所述正极极片的制备原料包括实施例1所述的无钴正极材料浆料。
上述正极极片的制备方法包括如下步骤：
将所述无钴正极材料浆料涂覆于基底(铝箔，购于中国铝业)，在100℃下加热30秒，得到所述正极极片。
应用例2-11
应用例2-11与应用例1的区别在于所述无钴正极材料浆料分别为实施例2-11所述无钴正极材料浆料，其余均与应用例1相同。
应用例12-15
应用例12-15与应用例1的区别在于加热温度分别为60℃(应用例12)、150℃(应用例13)、40℃(应用例14)和160℃(应用例15)，其余均与应用例1相同。
应用例16
本应用例与应用例1的区别在于加热时间为20秒，其余均与应用例1相同。
应用对比例1
本应用对比例与应用例1的区别在于所述无钴正极材料浆料为对比例1所述无钴正极材料浆料，其余均与应用例1相同。
性能测试
将采用纽扣电池，金属锂片，隔膜，应用例1-16和应用对比例1所述正极极片依次组装(隔膜隔开正极和锂片)，再加入电解液1M磷酸铁锂的碳酸乙烯酯和碳酸甲乙酯的混合溶剂，密封完毕，组装成锂离子电池。
将组装成的锂离子电池在电化学测试柜上进行电性能测试，具体过程为：25℃下以0.3C充电至4.3V，搁置2min，再以0.2C充电至4.3V，搁置2min，再以0.1C充电至4.3V，搁置2min，再以0.05C充电至4.3V，搁置5min，以0.3C 放电至2.8V，循环重复以上步骤。测试项目包括首次放电容量、首次库伦效率和循环500圈后容量保持率。
测试结果如图1所示，测试数据汇总于表1。
表1
Figure PCTCN2021130820-appb-000001
分析表1数据可知，实施例1-5中，DVS在2-6份范围内，所得锂离子电池的首次放电容量在166mAh/g以上，首次库伦效率在65％以上，容量保持率在57％以上，实施例1中加入2份DVS所得锂离子电池的首次放电容量为183mAh/g，首次库伦效率为81％，循环500圈后容量保持率为80％，本公开所述无钴正极材料浆料形成的锂离子电池具有较好的首次放电容量、首次库伦效率和容量保持率。
分析应用对比例1与应用例1可知，应用对比例1的性能不如应用例1，表1中未加入DVS的容量保持率明显低于加入DVS的容量保持率，容量保持率与时间的变化关系如图1所示，证明所述无钴正极材料浆料不添加含有不饱和键的砜类化合物形成的锂离子电池性能较差。
分析应用例8-11与应用例1可知，应用例8-11不如应用例1，证明溶剂在25-40重量份和含有不饱和键的砜类化合物在1-7重量份，该配比下的无钴正极材料浆料形成的锂离子电池性能较好。
分析应用例12-15可知，应用例14-15的性能不如应用例12-13，证明在制备正极极片时，加热温度在60-150℃范围内形成的正极极片性能更佳，利于锂离子电池综合性能的提升。
分析应用例16与应用例1可知，应用例16的性能不如应用例1，证明在制备正极极片时，加热时间在大于等于30秒时形成的正极极片性能更佳，利于锂离子电池综合性能的提升。

Claims (10)

  1. 一种无钴正极材料浆料，所述无钴正极材料浆料包括无钴正极材料、溶剂、含有不饱和键的砜类化合物和助剂；
    以所述无钴正极材料和助剂的总重量份数为100份计，所述溶剂的重量份数为25-40份，含有不饱和键的砜类化合物的重量份数为1-7份。
  2. 根据权利要求1所述的无钴正极材料浆料，其中，所述无钴正极材料包括Li xNi yMn zO 2；
    所述x为1-1.1，y为0.7-0.8，z为0.2-0.5，y+z＝1。
  3. 根据权利要求1或2所述的无钴正极材料浆料，其中，所述溶剂包括N-甲基吡咯烷酮、丙酮、二甲基亚砜或四氢呋喃中的任意一种或至少两种的组合。
  4. 根据权利要求1-3任一项所述的无钴正极材料浆料，其中，所述含有不饱和键的砜类化合物包括二乙烯基砜、三乙基烯基砜或丙烯砜中的任意一种或至少两种的组合。
  5. 根据权利要求1-4任一项所述的无钴正极材料浆料，其中，所述助剂包括粘结剂、导电剂中的至少之一。
  6. 一种根据权利要求1-5任一项所述的无钴正极材料浆料的制备方法，所述制备方法包括如下步骤：将无钴正极材料、溶剂和助剂混合后，再将所得混合物料与含有不饱和键的砜类化合物在60℃以下混合，得到所述无钴正极材料浆料。
  7. 一种正极极片，所述正极极片的制备原料包括权利要求1-5任一项所述的无钴正极材料浆料。
  8. 一种根据权利要求7所述的正极极片的制备方法，所述制备方法包括如下步骤：将所述无钴正极材料浆料涂覆于基底，加热，得到所述正极极片。
  9. 根据权利要求8所述的制备方法，其中，所述加热的温度为60-150℃，所述加热的时间大于等于30秒。
  10. 一种电池，所述电池包括权利要求7所述的正极极片。
PCT/CN2021/130820 2021-05-13 2021-11-16 一种无钴正极材料浆料及其制备方法和应用技术领域 WO2022237106A1 (zh)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US18/289,985 US20240250262A1 (en) 2021-05-13 2021-11-16 Cobalt-free positive electrode material slurry, preparation method therefor and application technical field thereof
EP21941670.8A EP4325604A1 (en) 2021-05-13 2021-11-16 Cobalt-free positive electrode material slurry, preparation method therefor and application technical field thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202110519766.0 2021-05-13
CN202110519766.0A CN112952100B (zh) 2021-05-13 2021-05-13 一种无钴正极材料浆料及其制备方法和应用

Publications (1)

Publication Number Publication Date
WO2022237106A1 true WO2022237106A1 (zh) 2022-11-17

Family

ID=76233779

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/130820 WO2022237106A1 (zh) 2021-05-13 2021-11-16 一种无钴正极材料浆料及其制备方法和应用技术领域

Country Status (4)

Country Link
US (1) US20240250262A1 (zh)
EP (1) EP4325604A1 (zh)
CN (1) CN112952100B (zh)
WO (1) WO2022237106A1 (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112952100B (zh) * 2021-05-13 2021-07-30 蜂巢能源科技有限公司 一种无钴正极材料浆料及其制备方法和应用

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104303346A (zh) * 2012-03-27 2015-01-21 江森自控技术公司 用于高压锂离子电池单元的聚砜涂层
CN109755511A (zh) 2018-12-24 2019-05-14 刘小龙 一种锂离子电池正极材料及其制备方法
CN111933945A (zh) * 2020-08-12 2020-11-13 安普瑞斯（无锡）有限公司 一种高容量的锂离子电池极片及含有该极片的锂离子二次电池
CN111933894A (zh) * 2020-08-12 2020-11-13 安普瑞斯（无锡）有限公司 一种原位聚合的有机无机复合固态电池
CN111933944A (zh) * 2020-08-12 2020-11-13 安普瑞斯（无锡）有限公司 一种电极极片及含有该极片的锂离子二次电池
CN112038642A (zh) 2020-09-25 2020-12-04 昆山宝创新能源科技有限公司 锂离子电池正极浆料及其制备方法和应用
CN112952100A (zh) * 2021-05-13 2021-06-11 蜂巢能源科技有限公司 一种无钴正极材料浆料及其制备方法和应用

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1691375A (zh) * 2004-04-30 2005-11-02 中国电子科技集团公司第十八研究所 一种含辅助粘接剂电极的制造方法
CN106558698B (zh) * 2015-09-29 2020-03-20 比亚迪股份有限公司 锂离子电池正极浆料和正极片及其制备方法以及锂离子电池
CN107492660B (zh) * 2016-06-13 2020-04-24 宁德新能源科技有限公司 正极浆料、正极片及锂离子电池
CN109216650B (zh) * 2017-06-30 2021-04-20 比亚迪股份有限公司 电池电极及其制备方法和全固态电池
CN110800141B (zh) * 2017-09-12 2024-01-02 住友精化株式会社 非水电解质二次电池用电极合剂
US11626585B2 (en) * 2018-10-09 2023-04-11 City University Of Hong Kong Electrode material and a method of preparing the same
CN111916823A (zh) * 2020-06-24 2020-11-10 珠海冠宇电池股份有限公司 一种锂离子电池用非水电解液及使用该非水电解液的锂离子电池

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104303346A (zh) * 2012-03-27 2015-01-21 江森自控技术公司 用于高压锂离子电池单元的聚砜涂层
CN109755511A (zh) 2018-12-24 2019-05-14 刘小龙 一种锂离子电池正极材料及其制备方法
CN111933945A (zh) * 2020-08-12 2020-11-13 安普瑞斯（无锡）有限公司 一种高容量的锂离子电池极片及含有该极片的锂离子二次电池
CN111933894A (zh) * 2020-08-12 2020-11-13 安普瑞斯（无锡）有限公司 一种原位聚合的有机无机复合固态电池
CN111933944A (zh) * 2020-08-12 2020-11-13 安普瑞斯（无锡）有限公司 一种电极极片及含有该极片的锂离子二次电池
CN112038642A (zh) 2020-09-25 2020-12-04 昆山宝创新能源科技有限公司 锂离子电池正极浆料及其制备方法和应用
CN112952100A (zh) * 2021-05-13 2021-06-11 蜂巢能源科技有限公司 一种无钴正极材料浆料及其制备方法和应用

Also Published As

Publication number Publication date
US20240250262A1 (en) 2024-07-25
CN112952100A (zh) 2021-06-11
CN112952100B (zh) 2021-07-30
EP4325604A1 (en) 2024-02-21

Similar Documents

Publication Publication Date Title
JP5757148B2 (ja) リチウムイオン二次電池用負極活物質及びその負極活物質を用いたリチウムイオン二次電池
US20050186474A1 (en) Positive electrodes for lithium batteries and their methods of fabrication
CN111276674B (zh) 一种改性石墨负极材料及其制备方法及含该改性石墨负极的电池
CN109004229B (zh) 一种锂离子电池正极材料添加剂及其正极材料和锂离子二次电池
CN114023965B (zh) 固态锂电池
WO2024011702A1 (zh) 一种锂离子电池
WO2011070748A1 (ja) 非水電解質二次電池及びその充電方法
CN112371187B (zh) 一种用于锂硫电池的仿生催化剂及制备方法、正极材料、正极极片及制备方法
US20130252102A1 (en) Nonaqueous Electrolyte Rechargeable Battery Having Electrode Containing Conductive Polymer
CN111883765A (zh) 锂电池正极活性材料及其制备方法和锂电池
JP2000011991A (ja) 有機電解液二次電池
WO2022237106A1 (zh) 一种无钴正极材料浆料及其制备方法和应用技术领域
US9899681B2 (en) Positive electrode for secondary batteries, secondary battery, and method for producing positive electrode for secondary batteries
CN109216692B (zh) 改性三元正极材料及其制备方法、锂离子电池
KR101142533B1 (ko) 금속계 아연 음극 활물질 및 이를 이용한 리튬이차전지
CN103840153B (zh) 一种高镍基锂电池正极材料及其制备方法
CN113690544A (zh) 一种锂金属电池隔膜及其制备方法和锂金属电池
KR101639313B1 (ko) 리튬 이차전지용 양극 및 이를 포함하는 리튬 이차전지
CN108933310B (zh) 一种高容量高功率型锂离子/空气混合电池系统
KR20060021252A (ko) 지르코니아로 코팅된 이차 전지용 양극활물질 및 그제조방법, 그리고 이를 사용한 이차전지
EP3846271A1 (en) Slurry composition for all-solid-state secondary battery, solid-electrolyte-containing layer, and all-solid-state secondary battery
CN111902975A (zh) 锂硫二次电池用阳极活性物质及其制备方法
US20160293939A1 (en) Positive Electrode Material, Positive Electrode For Non-Aqueous Electrolyte Secondary Battery, And Non-Aqueous Electrolyte Secondary Battery
KR101860367B1 (ko) 리튬이차전지용 양극 활물질 및 이의 제조 방법
CN113097483A (zh) 应用于高镍三元正极材料导电剂的制备方法及应用

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21941670

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 202337076334

Country of ref document: IN

Ref document number: 18289985

Country of ref document: US

WWE Wipo information: entry into national phase

Ref document number: 2021941670

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2021941670

Country of ref document: EP

Effective date: 20231113

NENP Non-entry into the national phase

Ref country code: DE