WO2020125562A1 - Tin-containing anode material, anode and preparation method therefor and anode slurry thereof, secondary battery and electrical equipment - Google Patents

Tin-containing anode material, anode and preparation method therefor and anode slurry thereof, secondary battery and electrical equipment Download PDF

Info

Publication number
WO2020125562A1
WO2020125562A1 PCT/CN2019/125440 CN2019125440W WO2020125562A1 WO 2020125562 A1 WO2020125562 A1 WO 2020125562A1 CN 2019125440 W CN2019125440 W CN 2019125440W WO 2020125562 A1 WO2020125562 A1 WO 2020125562A1
Authority
WO
WIPO (PCT)
Prior art keywords
negative electrode
tin
binder
conductive agent
electrode material
Prior art date
Application number
PCT/CN2019/125440
Other languages
French (fr)
Chinese (zh)
Inventor
唐永炳
杨凯
刘齐荣
Original Assignee
深圳先进技术研究院
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 深圳先进技术研究院 filed Critical 深圳先进技术研究院
Publication of WO2020125562A1 publication Critical patent/WO2020125562A1/en

Links

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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • 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
    • H01M4/36—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
    • H01M4/387—Tin or alloys based on tin
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present application belongs to the field of batteries, and particularly relates to tin-containing negative electrode materials, negative electrodes, preparation methods thereof, negative electrode slurries, secondary batteries, and electrical equipment.
  • Tin-graphite dual ion batteries have the advantages of higher specific energy density and lower cost. Its working mechanism involves the following processes: during the charging process, the cation and the negative electrode are alloyed, and the anion intercalates into the graphite positive electrode; while during the discharge process, the negative electrode is dealloyed, and the anion is deintercalated from the graphite positive electrode. During the charging and discharging process, the negative electrode tin exhibits significant volume change and pulverization. Therefore, surface modification of tin anodes is of great significance in the development of tin-graphite dual ion batteries.
  • tin foil as a negative electrode current collector and active material is widely used in potassium ion batteries, sodium ion batteries and calcium ion batteries.
  • the dual-ion battery based on tin anode-graphite cathode has become a research hotspot due to its high power density.
  • the tin foil has a significant occurrence
  • the change in volume causes powdering of the electrodes, which causes the battery capacity to decay.
  • the current solution is to use carbon-coated tin foil to solve the problem of tin foil volume expansion and powdering.
  • this preparation method is complicated, and the formed carbon coating layer is prone to cracking, and cannot effectively solve the problem of volume expansion of the tin anode.
  • the first object of the present application is to provide a tin-containing anode material to alleviate the problem that the current tin anode tends to swell and pulverize during charging and discharging.
  • the second object of the present application is to provide a method for preparing a tin-containing negative electrode material.
  • the third object of the present application is to provide a negative electrode slurry containing the foregoing tin-containing negative electrode material.
  • the fourth object of the present application is to provide a negative electrode.
  • the raw material of the negative electrode includes the foregoing tin-containing negative electrode material, and the negative electrode has the advantage of good cycle performance.
  • the fifth object of the present application is to provide a secondary battery including the above-mentioned negative electrode, and the secondary battery has an advantage of good cycle performance.
  • the sixth object of the present application is to provide an electric device including the above secondary battery.
  • An aspect of the present application provides a tin-containing negative electrode material, which includes, by weight percentage, tin particles 70% to 90%, an elastic binder 5% to 15%, and a conductive agent 5% to 15%;
  • the tin particles are micron or nanoscale tin particles.
  • the technical solutions adopted in the embodiments of the present application further include: by weight percentage: tin particles 72% to 88%, elastic binder 6% to 14%, and conductive agent 6% to 14%.
  • the technical solution adopted in the embodiments of the present application further includes: by weight percentage: tin particles 75%-85%, elastic binder 8%-12% and conductive agent 8%-12%.
  • the elastic binder includes an alginate binder, a polysaccharide binder, a carboxymethyl cellulose salt binder, a polyolefin binder, At least one of polyurethane-based adhesive, polyester-based adhesive, polyamide-based adhesive, or polyimide-based adhesive.
  • the elastic binder includes calcium alginate, cyclodextrin polymer, gum arabic, xanthan gum, guar gum, locust bean gum, karaya gum, arabic resin -Polyacrylic acid copolymer, vinyl acetate resin, polyacrylic acid-polyvinyl alcohol copolymer, polyvinyl alcohol-polyethyleneimine copolymer, polyacrylic acid-carboxymethylcellulose sodium copolymer, ammonium polyacrylate, sodium polyacrylate At least one of sodium carboxymethyl cellulose or sodium alginate-carboxymethyl chitosan copolymer.
  • the conductive agent includes an organic conductive agent and/or an inorganic conductive agent
  • the organic conductive agent includes an ionic organic conductive agent and/or an electronic organic conductive agent
  • the ionic organic conductive agent includes: at least one of polyethylene oxide, polypropylene oxide, polyethylene succinate, polyethylene oxalate, or polyethylene glycol imine;
  • the electronic organic conductive agent includes at least one of polypyrrole, polyparaphenylene, polyphenylene sulfide, polythiophene, polyparaphenylene vinylene, and polyaniline;
  • the inorganic conductive agent includes a conductive carbon material and/or a conductive metal material.
  • the technical solutions adopted in the embodiments of the present application further include: 0.5% to 2% of the coupling agent in terms of weight percentage;
  • the coupling agent includes at least one of a chromium complex coupling agent, a silane coupling agent, a titanate coupling agent, or an aluminate coupling agent.
  • a method for preparing a tin-containing negative electrode material is provided.
  • the tin particles, the elastic binder, the conductive agent, and optionally the coupling agent are mixed to obtain the Tin anode material.
  • Another aspect of the present application provides a negative electrode slurry, which is obtained by mixing a tin-containing negative electrode material with an organic solvent;
  • Another aspect of the present application provides a negative electrode including a negative electrode current collector and a negative electrode material layer formed on the surface of the negative electrode current collector, the negative electrode material layer being prepared from the foregoing tin-containing negative electrode material.
  • Another aspect of the present application provides a secondary battery including a positive electrode, an electrolyte, a separator, and the above negative electrode;
  • the secondary battery includes a single ion battery and a dual ion battery
  • the dual ion battery includes a tin-graphite dual ion battery.
  • Another aspect of the present application provides an electric device including the above secondary battery.
  • the tin-containing negative electrode material provided in this application uses tin particles as the negative electrode active material, and a protective layer is formed on the surface of the tin particles by adding an elastic binder.
  • the protective layer solves the problem caused by the direct contact of the tin particles with the electrolyte Corrosion problem; on the other hand, because the elastic binder has a certain resistance to deformation, it can suppress the volume expansion and powdering of the negative electrode tin to a certain extent.
  • a binder that is in firm contact with tin particles and has elasticity, it acts as an artificial elastic SEI film while binding the negative electrode active material, which serves to isolate the tin particles from contacting the electrolyte and ensure the stable wrapping of the tin particle surface.
  • a conductive agent By adding a conductive agent, it can be matched with an elastic binder to improve the conductivity of the tin-containing negative electrode material.
  • the distance between the adhesive anchor point of the elastic adhesive and the tin particles will increase, and the use of the elastic adhesive can ensure the adhesive in the process The layer does not crack.
  • the percentage (%) or part refers to the weight percentage or part by weight relative to the composition.
  • the numerical range “a-b” represents an abbreviated representation of any combination of real numbers between a and b, where a and b are both real numbers.
  • the numerical range “6-22” means that all real numbers between “6-22” have been listed in this article, and “6-22" is just an abbreviated representation of these numerical combinations.
  • the forms of the "lower limit” and the upper limit disclosed in the “range” of this application may be one or more lower limits and one or more upper limits, respectively.
  • each reaction or operation step may be performed sequentially or in order.
  • the reaction methods herein are performed sequentially.
  • the present application provides a tin-containing negative electrode material, which includes, by weight percentage, tin particles 70% to 90%, an elastic binder 5% to 15%, and a conductive agent 5% to 15%.
  • the tin-containing negative electrode material provided in this application uses tin particles as the negative electrode active material, and a protective layer is formed on the surface of the tin particles by adding an elastic binder.
  • the protective layer solves the problem caused by the direct contact of the tin particles with the electrolyte Corrosion problem; on the other hand, because the elastic binder has a certain resistance to deformation, it can suppress the volume expansion and powdering of the negative electrode tin to a certain extent.
  • a binder that is in firm contact with tin particles and has elasticity, it acts as an artificial elastic SEI film while binding the negative electrode active material, which serves to isolate the tin particles from contacting the electrolyte and ensure the stable wrapping of the tin particle surface.
  • a conductive agent By adding a conductive agent, it can be matched with an elastic binder to improve the conductivity of the tin-containing negative electrode material.
  • the distance between the adhesive anchor point of the elastic adhesive and the tin particles will increase, and the use of the elastic adhesive can ensure the adhesive in the process The layer does not crack.
  • the content of tin particles in terms of weight percentage is typical but not limited, for example: 70%, 72%, 75%, 78%, 80%, 82%, 85%, 88 % Or 90%;
  • typical but non-limiting examples of elastic binders are: 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% or 15 %.
  • Typical but non-limiting examples of the conductive agent may be: 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, or 15%.
  • the percentage by weight includes: tin particles 72% to 88%, elastic binder 6% to 14% and conductive agent 6% to 14%, further preferably: tin particles 75% to 85%, elastic binder 8%-12% and conductive agent 8%-12%.
  • the structural stability of the tin-containing anode material can be further improved, thereby improving the cycle stability of the battery.
  • the tin particles are micron or nanoscale tin particles.
  • the micron or nanometer tin particles mean that the particle size of the tin particles is in the micron or nanometer range, for example, the tin particle size is in the range of several nanometers to tens of micrometers.
  • the small-scale negative electrode active material helps to increase the specific surface area and suppress the volume expansion of the material.
  • the use of anode materials containing micron or nanoscale tin particles can effectively solve the current problems of tin anodes prone to powdering and low rate performance.
  • the specific principles of using tin particles to solve the above problems are as follows:
  • the elastic binder includes alginate binders, polysaccharide binders, carboxymethyl cellulose salt binders, polyolefin binders, polyurethanes At least one of an adhesive, a polyester-based adhesive, a polyamide-based adhesive, or a polyimide-based adhesive.
  • the elastic binder may be calcium alginate (Ca-Alg for short), cyclodextrin polymer (CDp for short), gum arabic (GA for short), xanthan gum (XG for short), guar bean Gum (abbreviated as GG), locust bean gum (abbreviated as LBG), karaya gum (abbreviated as KG), Arabic resin-polyacrylic acid copolymer (abbreviated as GA-PAA), vinyl acetate resin (abbreviated as PVAc), polymer Acrylic acid-polyvinyl alcohol copolymer (abbreviated as PAA-PVA), polyvinyl alcohol-polyethyleneimine copolymer (abbreviated as PVA-PEI), polyacrylic acid-carboxymethyl cellulose sodium copolymer (abbreviated as PAA-CMC) ), ammonium polyacrylate (referred to as PAA-NH4), sodium polyacrylate grafted sodium carboxymethyl cellulose (referred to as
  • the above-mentioned elastic adhesive also covers some rubber-based adhesives, such as natural rubber NR, styrene-butadiene rubber SBR, butadiene rubber BR, isoprene rubber IR, neoprene CR, butyl rubber IIR, nitrile rubber NBR, hydrogenated nitrile rubber HNBR, ethylene propylene rubber EPM ⁇ EPDM, silicone rubber Q, fluorine rubber FPM, polyurethane rubber AU ⁇ EU, acrylic rubber ACM ⁇ AEM, chlorosulfonated polyethylene rubber CSM, chlorine At least one of ether rubber CO ⁇ ECO or chlorinated polyethylene rubber CM ⁇ CPE.
  • rubber-based adhesives such as natural rubber NR, styrene-butadiene rubber SBR, butadiene rubber BR, isoprene rubber IR, neoprene CR, butyl rubber IIR, nitrile rubber NBR, hydrogenated nitrile rubber HNBR,
  • the stability of the tin-containing negative electrode material during charge and discharge can be further improved, thereby further improving the cycle stability of the battery.
  • the conductive agent includes an organic conductive agent and/or an inorganic conductive agent.
  • the inorganic conductive agent includes a conductive carbon material and/or a conductive metal material.
  • the carbon conductive material may be conductive carbon black, conductive carbon spheres, conductive graphite, graphene, carbon nanotubes, carbon nanoribbons, carbon fiber, reduced graphene oxide;
  • the conductive metal material may be copper simple nanomaterials (nanowire, nanometer Tubes, nanosheets, nanoribbons, nanoparticles, etc.) or silver nanomaterials.
  • the organic conductive agent is an organic substance with a certain conductivity, and at the same time, the organic substance can have a certain adhesiveness. Therefore, when the conductive agent is an organic substance with a certain adhesion, it can not only function as a conductive agent but also as a binder. When an organic substance with a binder is used as a conductive agent, a coating layer can be formed on the surface of the tin particles, which further reduces the expansion of the tin particles and reduces the occurrence of pulverization.
  • the inorganic conductive agent has a particle structure and a large volume size. During the expansion of the tin particles, it will squeeze with it. The larger volume of conductive agent particles may crush the tin particles, destroy the material structure, and reduce the battery performance.
  • the use of organic conductive agents can be considered to be a more uniform conductive agent to a certain extent.
  • the use of an organic conductive agent can form a uniform polymer coating layer on the surface of the tin particles, which can protect the tin particles from being damaged while playing a bonding role.
  • another advantage of the cladding layer is that it can isolate the tin particles from the electrolyte to a greater extent, reduce the loss of materials and improve the conductivity.
  • the organic conductive agent includes an ionic organic conductive agent and/or an electronic organic conductive agent.
  • the ionic organic conductive agent may be, for example, at least one of polyethylene oxide, polypropylene oxide, polyethylene succinate, polyethylene oxalate, or polyethylene glycol imine, preferably Polyethylene oxide.
  • the electronic type organic conductive agent may be, for example, at least one of polypyrrole, polyparaphenylene, polyphenylene sulfide, polythiophene, polyparaphenylene vinylene, or polyaniline.
  • the tin-containing negative electrode material includes a coupling agent by 0.5% to 2% by weight.
  • Coupling agent is a kind of substance with two functional groups with different properties.
  • the biggest feature of its molecular structure is that the molecule contains two groups with different chemical properties, one is an inorganic-philic group, and it is easy to react with the surface of inorganic substances. ;
  • the other is an organophilic group that can chemically react with synthetic resins or other polymers or dissolve in hydrogen bonds. Therefore, the coupling agent is called "molecular bridge" to improve the interface between inorganic and organic substances, thereby greatly improving the performance of composite materials, such as physical properties, electrical properties, thermal properties and optical properties.
  • adding a coupling agent to the tin-containing negative electrode material can greatly improve the interface contact between the tin particles and the binder, while ensuring that the binder can evenly cover the tin particles, under the effect of bonding The tin particles and the adhesive are firmly attached, and the contact between the tin particles and the electrolyte is blocked.
  • a coupling agent to build a molecular bridge between the inorganic tin particles and the organic binder the adhesion of the binder is further increased by adding anchor points.
  • the adhesion between the binder and the anode current collector is poor, which may easily cause the tin particles to peel off from the anode current collector during the charging and discharging process, and the use of the coupling agent It can increase the binding force of tin particles and negative electrode current collector and reduce the occurrence of flaking.
  • typical but non-limiting coupling agents include at least one of chromium complex coupling agents, silane coupling agents, titanate coupling agents, or aluminate coupling agents.
  • the coupling agent may be a chromium complex coupling agent, silane coupling agent, titanate coupling agent, aluminate coupling agent, chromium complex coupling agent-silane coupling agent combination, silane Combination of coupling agent-titanate coupling agent or combination of titanate coupling agent-aluminate coupling agent, etc.
  • the present application provides a method for preparing a tin-containing negative electrode material, the preparation method is to mix the tin particles, the elastic binder, the conductive agent, and optionally the coupling agent, The tin-containing negative electrode material is obtained.
  • the tin-containing negative electrode material obtained by the preparation method has all the advantages of the above negative electrode material, and will not be described here.
  • the present application provides a negative electrode slurry, which is obtained by mixing the foregoing tin-containing negative electrode material with an organic solvent.
  • the preparation of the above tin-containing negative electrode material into a negative electrode slurry is more convenient for the preparation of batteries.
  • the negative electrode slurry may be prepared by mixing the tin particles, the elastic binder, the conductive agent, and the optional coupling agent, and grinding them uniformly. The negative electrode slurry is obtained.
  • This method is the preparation method of conventional slurry, the process is mature and stable, and it is convenient to operate.
  • the negative electrode slurry may be prepared, for example, by weighing tin particles, a binder, and a conductive agent at a certain weight ratio, placing each material in a mortar, and adding an appropriate amount of organic solvent to grind it uniformly. The negative electrode slurry is obtained.
  • the negative electrode slurry may be prepared by providing a suspension composed of tin particles and an organic solvent, and dissolving an optional coupling agent in the suspension, and then The binder and the conductive agent are added and mixed uniformly to obtain the negative electrode slurry.
  • the coupling agent is added to the suspension composed of tin particles and an organic solvent, which can make the coupling agent fully contact with the surface of the tin particles, a bonding reaction occurs, and then the binder is added, thereby increasing the tin particles and the binder The bonding strength between.
  • the present application provides a negative electrode including a negative electrode current collector and a negative electrode material layer formed on the surface of the negative electrode current collector.
  • the negative electrode material layer is prepared from the foregoing tin-containing negative electrode material.
  • the material of the negative electrode current collector is, for example, at least one kind or an alloy of at least one kind selected from aluminum, lithium, magnesium, vanadium, copper, iron, tin, zinc, nickel, titanium, or manganese.
  • the present application provides a method for preparing the foregoing negative electrode.
  • the negative electrode material layer is prepared on the surface of the negative electrode current collector using the foregoing tin-containing negative electrode material to obtain the negative electrode.
  • the above negative electrode slurry may be used to prepare the negative electrode.
  • the negative electrode slurry may be coated on the surface of the negative electrode current collector and dried to obtain the negative electrode.
  • the present application provides a secondary battery including a positive electrode, an electrolyte, a separator, and the above negative electrode.
  • the electrolyte and the separator are between the positive electrode and the negative electrode.
  • the secondary battery includes a single ion battery and a dual ion battery.
  • the above-mentioned negative electrode in this application can be used not only in conventional single ion battery systems, such as lithium ion batteries, sodium ion batteries, potassium ion batteries, but also in battery system of metal alloying reaction, especially suitable for tin metal reaction In the battery system, for example, tin-graphite-based sodium-based, potassium-based and calcium-based dual-ion battery systems, and so on.
  • the positive electrode includes a positive electrode current collector and a positive electrode material layer formed on the surface of the positive electrode current collector, and the positive electrode material layer includes a positive electrode active material, a positive electrode binder, and a positive electrode conductive agent.
  • the content of the positive electrode active material is 60-95 wt%
  • the content of the conductive agent is 2-30 wt%
  • the content of the binder is 3-10 wt%.
  • the positive electrode current collector is selected from at least one or an alloy of at least one of aluminum, lithium, magnesium, vanadium, copper, iron, tin, zinc, nickel, titanium, and manganese.
  • the positive electrode current collector is tin foil.
  • the positive electrode active material is graphite-based materials, including mesophase carbon microsphere graphite, natural graphite, expanded graphite, glassy carbon, carbon-carbon composite materials, carbon fiber, hard carbon, highly oriented graphite, carbon black, carbon nanotubes, graphene One or more kinds, preferably expanded graphite.
  • the positive electrode conductive agent may be, for example, at least one of conductive carbon black, conductive carbon spheres, conductive graphite, carbon nanotubes, conductive carbon fiber, graphene, or reduced graphene oxide.
  • the positive electrode conductive agent is conductive carbon black.
  • the positive electrode binder may be, for example, at least one of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, SBR rubber, or polyolefin.
  • the positive electrode binder is polyvinylidene fluoride.
  • the electrolyte salt in the electrolyte may be a lithium salt, a sodium salt, a potassium salt, a magnesium salt, a calcium salt, etc. according to the type of secondary battery.
  • the sodium salt may be selected from sodium tetrafluoroborate, sodium bistrifluoromethylsulfonimide, sodium bisfluorosulfonimide, sodium chloride, sodium sulfate, sodium thiosulfate, sodium carbonate , Sodium bicarbonate, sodium nitrate, sodium fluoride, sodium phenolate, sodium butyrate, sodium oxalate, sodium succinate, sodium salicylate, sodium iodoacetate, sodium perchlorate, sodium sarcosinate, sodium octyl sulfate , Sodium hexafluorophosphate, sodium silicate, sodium methyldiflavinate, sodium acetate, sodium 1,5-naphthalene disulfonate, sodium dichromate, sodium
  • the electrolyte solvent is selected from one or more of organic solvents such as esters, sulfones, ethers, nitriles or ionic liquids.
  • the solvent may be, for example, propylene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), methyl formate (MF), acetic acid Methyl ester (MA), N,N-dimethylacetamide (DMA), fluoroethylene carbonate (FEC), methyl propionate (MP), ethyl propionate (EP), ethyl acetate (EA) , ⁇ -butyrolactone (GBL), tetrahydrofuran (THF), 2-methyltetrahydrofuran (2MeTHF), 1,3-dioxolane (DOL), 4-methyl-1,3-dioxolane Alkane (4MeDOL), dimethoxymethane (DMM), 1,2-dimethoxypropane (DMP), triethylene glycol dimethyl ether (DG), dimethyl sulfone (MSM), dimethyl ether
  • the electrolyte may also contain additives, which may be one or more of organic additives such as esters, sulfones, ethers, nitriles or olefins, for example, fluoroethylene carbonate, vinylene carbonate, ethylene carbonate Ethylene, 1,3-propane sultone, 1,4-butane sultone, vinyl sulfate, propylene sulfate, ethylene sulfate, vinyl sulfite, propylene sulfite, dimethyl Sulfite, diethyl sulfite, ethylene sulfite, methyl chloroformate, dimethyl sulfoxide, anisole, acetamide, diazabenzene, m-diazepine, crown ether 12 -Crown-4, crown ether 18-crown-6, 4-fluoroanisole, fluorochain ether, difluoromethyl vinyl carbonate, trifluoromethyl vinyl carbonate,
  • the present application provides an electrical device.
  • the electrical equipment may be, for example, an electronic device, a power tool, an electric vehicle, or a power storage system.
  • the secondary battery of the embodiment of the present application has a good cycle stability effect. The same effect can also be obtained in electronic devices, power tools, electric vehicles, and power storage systems using the secondary battery of the embodiment of the present application.
  • the electronic device is an electronic device that uses a lithium ion battery as a power source for operation to perform various functions (for example, playing music).
  • a power tool is a power tool that uses a lithium ion battery as a driving power source to move moving parts (for example, a drill bit).
  • the electric vehicle is an electric vehicle that runs on a lithium ion battery as a driving power source, and may be an automobile (including a hybrid vehicle) equipped with other driving sources in addition to the lithium ion battery.
  • the power storage system is a power storage system that uses a lithium ion battery as a power storage source.
  • a lithium ion battery used as a power storage source
  • the power stored in the lithium ion battery is consumed as necessary to enable various devices such as home electronic products.
  • This embodiment is a negative electrode including a negative electrode current collector and a negative electrode material layer formed on the surface of the negative electrode current collector.
  • the raw material of the negative electrode material layer includes nano-tin particles, an elastic binder and a conductive agent.
  • the negative electrode current collector is tin foil
  • the elastic binder is calcium alginate
  • the conductive agent is polyethylene oxide PEO.
  • the preparation method of the negative electrode includes the following steps:
  • Examples 2 to 15 are each a negative electrode. The difference from Example 1 is that the elastic binder used is different, and the others are the same as Example 1. The selection of specific elastic binders of Examples 1 to 15 is shown in Table 1.
  • Examples 16 to 20 are each a negative electrode. The difference from Example 1 is that the conductive agent used is different, and the others are the same as Example 1. The selection of specific conductive agents in Examples 1 to 15 is shown in Table 2.
  • Examples 21 to 25 are respectively a negative electrode. Compared with Example 1, the types of raw materials are the same, but the difference is that the weight ratio of tin particles, elastic binder and conductive agent is different. The weight ratio of tin particles, elastic binder and conductive agent in Examples 21-25 is shown in Table 3.
  • Examples 26 to 28 are each a negative electrode.
  • the difference compared with Example 1 is that Examples 26 to 28 respectively add a coupling agent, and the amount of coupling agent added is 0.5% of the weight of the tin particles .
  • the compounding ratio of each raw material of Examples 26 to 28 is shown in Table 4.
  • This comparative example is a negative electrode, which is a metal tin sheet.
  • This comparative example is a negative electrode, which differs from Example 1 in that the binder used is different.
  • the binder in this comparative example is a PVDF binder, and the solvent used in the preparation process is an NMP solvent. Others are the same as in Example 1.
  • This embodiment is a tin-graphite dual ion battery, and its preparation method includes the following steps:
  • Tin-graphite dual-ion battery assembly in an inert gas-protected glove box, the prepared positive electrode, organic electrolyte, and the negative electrode in Example 1 are closely stacked in sequence, and then packaged into a button-type case to obtain a button Battery, complete battery assembly.
  • Examples 30 to 56 are respectively a tin-graphite dual ion battery, which differs from Example 29 in that the negative electrodes used in the batteries in Examples 30 to 56 respectively correspond to the negative electrodes provided in Examples 2 to 28 .
  • Comparative Examples 3 to 4 are respectively a tin-graphite dual ion battery, which is different from Example 29 in that the negative electrodes used in the batteries in Comparative Examples 3 to 4 respectively correspond to the negative electrodes provided in Comparative Examples 1 to 2 .
  • the electrical properties of the tin-graphite dual ion batteries in Examples 29 to 56 and Comparative Examples 3 to 4 were tested respectively.
  • the test item is the capacity retention rate of each group of batteries after 500 charge and discharge cycles.
  • the test results are listed in Table 5.

Abstract

A tin-containing anode material, an anode and a preparation method therefor and anode slurry thereof, a secondary battery and an electrical equipment, which relate to the field of batteries. The tin-containing anode material comprises the following in weight percentage: tin particles 70%-90%, an elastic adhesive 5%-15%, and a conductive agent 5%-15%. Using the described tin-containing anode material may relieve the existing technical problem in which circulation performance is poor due to expansion pulverization easily occurring when a tin metal anode is used as the anode of a battery, thus achieving the goal of improving the stability of battery circulation.

Description

含锡负极材料、负极及其制备方法与负极浆料、二次电池和用电设备Tin-containing anode material, anode and preparation method thereof, anode slurry, secondary battery and electrical equipment 技术领域Technical field
本申请属于电池领域，特别涉及含锡负极材料、负极及其制备方法与负极浆料、二次电池和用电设备。The present application belongs to the field of batteries, and particularly relates to tin-containing negative electrode materials, negative electrodes, preparation methods thereof, negative electrode slurries, secondary batteries, and electrical equipment.
背景技术Background technique
锡-石墨双离子电池具有比能量密度更高、成本更低的优点。它的工作机理涉及到如下过程：充电过程中，阳离子与负极发生合金化反应，阴离子插层进入石墨正极；而放电过程中，负极发生去合金化反应，阴离子从石墨正极脱嵌。由于在充放电过程中，负极锡呈现出显著的体积变化与粉化现象。所以，对锡负极进行表面改性在锡-石墨双离子电池的研发中具有重大意义。Tin-graphite dual ion batteries have the advantages of higher specific energy density and lower cost. Its working mechanism involves the following processes: during the charging process, the cation and the negative electrode are alloyed, and the anion intercalates into the graphite positive electrode; while during the discharge process, the negative electrode is dealloyed, and the anion is deintercalated from the graphite positive electrode. During the charging and discharging process, the negative electrode tin exhibits significant volume change and pulverization. Therefore, surface modification of tin anodes is of great significance in the development of tin-graphite dual ion batteries.
目前，锡箔作为负极集流体与活性材料广泛运用于钾离子电池、钠离子电池和钙电离子电池。近期，基于锡负极-石墨正极的双离子电池由于具有高的功率密度而成为研究的热点，但该类双离子电池在充放电过程中，由于阳离子与锡金属发生合金化反应，导致锡箔发生显著的体积变化，造成电极粉化，从而引起电池容量衰减。为了降低锡箔负极的体积膨胀，目前的解决方法有：利用碳包覆锡箔的方法解决锡箔体积膨胀和粉化的问题。然而，这种制备方法复杂，且形成的碳包覆层易发生破裂，并不能有效解决锡负极体积膨胀的问题。At present, tin foil as a negative electrode current collector and active material is widely used in potassium ion batteries, sodium ion batteries and calcium ion batteries. Recently, the dual-ion battery based on tin anode-graphite cathode has become a research hotspot due to its high power density. However, during the charging and discharging of this type of dual-ion battery, due to the alloying reaction between cations and tin metal, the tin foil has a significant occurrence The change in volume causes powdering of the electrodes, which causes the battery capacity to decay. In order to reduce the volume expansion of the tin foil negative electrode, the current solution is to use carbon-coated tin foil to solve the problem of tin foil volume expansion and powdering. However, this preparation method is complicated, and the formed carbon coating layer is prone to cracking, and cannot effectively solve the problem of volume expansion of the tin anode.
发明内容Summary of the invention
本申请的第一目的在于提供一种含锡负极材料，以缓解目前锡负极在充放 电过程中容易产生膨胀发生粉化的问题。The first object of the present application is to provide a tin-containing anode material to alleviate the problem that the current tin anode tends to swell and pulverize during charging and discharging.
本申请的第二目的在于提供一种含锡负极材料的制备方法。The second object of the present application is to provide a method for preparing a tin-containing negative electrode material.
本申请的第三目的在于提供一种包含上述含锡负极材料的负极浆料。The third object of the present application is to provide a negative electrode slurry containing the foregoing tin-containing negative electrode material.
本申请的第四目的在于提供一种负极，该负极的原料包括上述含锡负极材料，该负极具有循环性能好的优点。The fourth object of the present application is to provide a negative electrode. The raw material of the negative electrode includes the foregoing tin-containing negative electrode material, and the negative electrode has the advantage of good cycle performance.
本申请的第五目的在于提供一种二次电池，该二次电池包括上述负极，该二次电池具有循环性能好的优点。The fifth object of the present application is to provide a secondary battery including the above-mentioned negative electrode, and the secondary battery has an advantage of good cycle performance.
本申请的第六目的在于提供一种包括上述二次电池的用电设备。The sixth object of the present application is to provide an electric device including the above secondary battery.
为了实现本申请的上述目的，特采用以下技术方案：In order to achieve the above purpose of this application, the following technical solutions are specifically adopted:
本申请的一个方面，提供一种含锡负极材料，按重量百分比计包括：锡颗粒70％～90％、弹性粘结剂5％～15％和导电剂5％～15％；An aspect of the present application provides a tin-containing negative electrode material, which includes, by weight percentage, tin particles 70% to 90%, an elastic binder 5% to 15%, and a conductive agent 5% to 15%;
所述锡颗粒为微米级或纳米级的锡颗粒。The tin particles are micron or nanoscale tin particles.
本申请实施例采取的技术方案还包括：按重量百分比计包括：锡颗粒72％～88％、弹性粘结剂6％～14％和导电剂6％～14％。The technical solutions adopted in the embodiments of the present application further include: by weight percentage: tin particles 72% to 88%, elastic binder 6% to 14%, and conductive agent 6% to 14%.
本申请实施例采取的技术方案还包括：按重量百分比计包括：锡颗粒75％～85％、弹性粘结剂8％～12％和导电剂8％～12％。The technical solution adopted in the embodiments of the present application further includes: by weight percentage: tin particles 75%-85%, elastic binder 8%-12% and conductive agent 8%-12%.
本申请实施例采取的技术方案还包括：所述弹性粘结剂包括海藻酸盐类粘结剂、多糖类粘结剂、羧甲基纤维素盐粘结剂、聚烯烃类粘结剂、聚氨酯类粘结剂、聚酯类粘结剂、聚酰胺类粘结剂或聚亚胺类粘结剂中的至少一种。The technical solutions adopted in the embodiments of the present application further include: the elastic binder includes an alginate binder, a polysaccharide binder, a carboxymethyl cellulose salt binder, a polyolefin binder, At least one of polyurethane-based adhesive, polyester-based adhesive, polyamide-based adhesive, or polyimide-based adhesive.
本申请实施例采取的技术方案还包括：所述弹性粘结剂包括海藻酸钙、环糊精聚合物、***树胶、黄原胶、胍尔豆胶、刺槐豆胶、刺梧桐树胶、***树脂-聚丙烯酸共聚物、醋酸乙烯树脂、聚丙烯酸-聚乙烯醇共聚物、聚乙烯醇-聚乙烯亚胺共聚物、聚丙烯酸-羧甲基纤维素钠共聚物、聚丙烯酸铵、聚丙 烯酸钠接枝羧甲基纤维素钠或海藻酸钠-羧甲基壳聚糖共聚物中的至少一种。The technical solutions adopted in the examples of the present application further include: the elastic binder includes calcium alginate, cyclodextrin polymer, gum arabic, xanthan gum, guar gum, locust bean gum, karaya gum, arabic resin -Polyacrylic acid copolymer, vinyl acetate resin, polyacrylic acid-polyvinyl alcohol copolymer, polyvinyl alcohol-polyethyleneimine copolymer, polyacrylic acid-carboxymethylcellulose sodium copolymer, ammonium polyacrylate, sodium polyacrylate At least one of sodium carboxymethyl cellulose or sodium alginate-carboxymethyl chitosan copolymer.
本申请实施例采取的技术方案还包括：所述导电剂包括有机导电剂和/或无机导电剂；The technical solutions adopted in the embodiments of the present application further include: the conductive agent includes an organic conductive agent and/or an inorganic conductive agent;
所述有机导电剂包括离子型有机导电剂和/或电子型有机导电剂；The organic conductive agent includes an ionic organic conductive agent and/or an electronic organic conductive agent;
所述离子型有机导电剂包括：聚氧化乙烯、聚环氧丙烷、聚丁二酸乙二醇酯、聚葵二酸乙二酸酯或聚乙二醇亚胺中的至少一种；The ionic organic conductive agent includes: at least one of polyethylene oxide, polypropylene oxide, polyethylene succinate, polyethylene oxalate, or polyethylene glycol imine;
所述电子型有机导电剂包括聚吡咯、聚对苯撑、聚苯硫醚、聚噻吩、聚对苯撑乙烯、聚苯胺中的至少一种；The electronic organic conductive agent includes at least one of polypyrrole, polyparaphenylene, polyphenylene sulfide, polythiophene, polyparaphenylene vinylene, and polyaniline;
所述无机导电剂包括导电碳材料和/或导电金属材料。The inorganic conductive agent includes a conductive carbon material and/or a conductive metal material.
本申请实施例采取的技术方案还包括：按重量百分比计包括偶联剂0.5％～2％；The technical solutions adopted in the embodiments of the present application further include: 0.5% to 2% of the coupling agent in terms of weight percentage;
所述偶联剂包括铬络合物偶联剂、硅烷偶联剂、钛酸酯偶联剂或铝酸盐偶联剂中的至少一种。The coupling agent includes at least one of a chromium complex coupling agent, a silane coupling agent, a titanate coupling agent, or an aluminate coupling agent.
本申请的另一个方面，提供一种含锡负极材料的制备方法，将所述锡颗粒、所述弹性粘结剂和所述导电剂以及任选的所述偶联剂混合，得到所述含锡负极材料。In another aspect of the present application, a method for preparing a tin-containing negative electrode material is provided. The tin particles, the elastic binder, the conductive agent, and optionally the coupling agent are mixed to obtain the Tin anode material.
本申请的另一个方面，提供一种负极浆料，将含锡负极材料与有机溶剂混合后得到所述负极浆料；Another aspect of the present application provides a negative electrode slurry, which is obtained by mixing a tin-containing negative electrode material with an organic solvent;
将所述锡颗粒、所述弹性粘结剂和所述导电剂以及任选的偶联剂混合后研磨均匀，得到所述负极浆料；Mixing the tin particles, the elastic binder, the conductive agent, and the optional coupling agent, and grinding them evenly to obtain the negative electrode slurry;
或，提供锡颗粒与有机溶剂组成的悬浮液，并将任选的偶联剂溶于所述悬浮液中，再加入所述粘结剂和所述导电剂混合均匀，得到所述负极浆料。Or, provide a suspension composed of tin particles and an organic solvent, and dissolve the optional coupling agent in the suspension, and then add the binder and the conductive agent to mix evenly to obtain the negative electrode slurry .
本申请的另一个方面，提供一种负极，包括负极集流体和形成于所述负极 集流体表面的负极材料层，所述负极材料层由上述含锡负极材料制备而成。Another aspect of the present application provides a negative electrode including a negative electrode current collector and a negative electrode material layer formed on the surface of the negative electrode current collector, the negative electrode material layer being prepared from the foregoing tin-containing negative electrode material.
本申请的另一个方面，提供一种二次电池，包括正极、电解液、隔膜和上述负极；Another aspect of the present application provides a secondary battery including a positive electrode, an electrolyte, a separator, and the above negative electrode;
所述二次电池包括单离子电池和双离子电池；The secondary battery includes a single ion battery and a dual ion battery;
所述双离子电池包括锡-石墨双离子电池。The dual ion battery includes a tin-graphite dual ion battery.
本申请的另一个方面，提供一种用电设备，包括上述二次电池。Another aspect of the present application provides an electric device including the above secondary battery.
相对于现有技术，本申请实施例产生的有益效果在于：Compared with the prior art, the beneficial effects produced by the embodiments of the present application are as follows:
本申请提供的含锡负极材料，以锡颗粒为负极活性材料，通过添加弹性粘结剂在锡颗粒表面形成一层防护层，该防护层一方面解决了锡颗粒直接与电解液接触而造成的腐蚀问题；另一方面，由于弹性粘结剂具有一定的抗形变的能力，在一定程度上可以抑制负极锡的体积膨胀及粉化。The tin-containing negative electrode material provided in this application uses tin particles as the negative electrode active material, and a protective layer is formed on the surface of the tin particles by adding an elastic binder. On the one hand, the protective layer solves the problem caused by the direct contact of the tin particles with the electrolyte Corrosion problem; on the other hand, because the elastic binder has a certain resistance to deformation, it can suppress the volume expansion and powdering of the negative electrode tin to a certain extent.
通过使用与锡颗粒牢固接触且具有弹性的粘结剂，在粘结负极活性材料的同时作为人造弹性SEI膜，起到隔绝锡颗粒与电解液接触并保证稳定包裹锡颗粒表面的作用。通过添加导电剂，可以与弹性粘结剂相配合，提高含锡负极材料的导电性。By using a binder that is in firm contact with tin particles and has elasticity, it acts as an artificial elastic SEI film while binding the negative electrode active material, which serves to isolate the tin particles from contacting the electrolyte and ensure the stable wrapping of the tin particle surface. By adding a conductive agent, it can be matched with an elastic binder to improve the conductivity of the tin-containing negative electrode material.
在电池的充放电过程中，当锡颗粒发生膨胀时，弹性粘结剂与锡颗粒之间的粘附锚点相隔距离会增大，弹性粘结剂的使用可保证在该过程中粘结剂层不发生破裂。During the charging and discharging of the battery, when the tin particles expand, the distance between the adhesive anchor point of the elastic adhesive and the tin particles will increase, and the use of the elastic adhesive can ensure the adhesive in the process The layer does not crack.
具体实施方式detailed description
为了使本申请的目的、技术方案及优点更加清楚明白，下面将结合实施例对本申请的实施方案进行详细描述，但是本领域技术人员将会理解，下列实施 例仅用于说明本申请，而不应视为限制本申请的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。In order to make the purpose, technical solutions and advantages of the present application more clear, the embodiments of the present application will be described in detail in conjunction with the following examples, but those skilled in the art will understand that the following examples are only for illustrating the present application and not It should be considered as limiting the scope of this application. If no specific conditions are indicated in the examples, the conventional conditions or the conditions recommended by the manufacturer shall be used. The reagents or instruments used do not indicate the manufacturer, are all conventional products that can be obtained through commercial purchase.
需要说明的是：It should be noted:
本申请中，如果没有特别的说明，本文所提到的所有实施方式以及优选实施方法可以相互组合形成新的技术方案。In this application, unless otherwise specified, all the embodiments and preferred implementation methods mentioned herein can be combined with each other to form a new technical solution.
本申请中，如果没有特别的说明，本文所提到的所有技术特征以及优选特征可以相互组合形成新的技术方案。In this application, if there is no special description, all the technical features and preferred features mentioned in this document can be combined with each other to form a new technical solution.
本申请中，如果没有特别的说明，百分数(％)或者份指的是相对于组合物的重量百分数或重量份。In this application, unless otherwise specified, the percentage (%) or part refers to the weight percentage or part by weight relative to the composition.
本申请中，如果没有特别的说明，所涉及的各组分或其优选组分可以相互组合形成新的技术方案。In this application, unless otherwise specified, the involved components or their preferred components can be combined with each other to form a new technical solution.
本申请中，除非有其他说明，数值范围“a～b”表示a到b之间的任意实数组合的缩略表示，其中a和b都是实数。例如数值范围“6～22”表示本文中已经全部列出了“6～22”之间的全部实数，“6～22”只是这些数值组合的缩略表示。In this application, unless otherwise stated, the numerical range "a-b" represents an abbreviated representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "6-22" means that all real numbers between "6-22" have been listed in this article, and "6-22" is just an abbreviated representation of these numerical combinations.
本申请所公开的“范围”以下限和上限的形式，可以分别为一个或多个下限，和一个或多个上限。The forms of the "lower limit" and the upper limit disclosed in the "range" of this application may be one or more lower limits and one or more upper limits, respectively.
本申请中，除非另有说明，各个反应或操作步骤可以顺序进行，也可以按照顺序进行。优选地，本文中的反应方法是顺序进行的。In this application, unless otherwise stated, each reaction or operation step may be performed sequentially or in order. Preferably, the reaction methods herein are performed sequentially.
除非另有说明，本文中所用的专业与科学术语与本领域熟练人员所熟悉的意义相同。此外，任何与所记载内容相似或均等的方法或材料也可应用于本申请中。Unless otherwise stated, the technical and scientific terms used in this article have the same meaning as those familiar to those skilled in the art. In addition, any method or material similar to or equivalent to the described content can also be applied to this application.
一方面，本申请提供了一种含锡负极材料，按重量百分比计包括：锡颗粒70％～90％、弹性粘结剂5％～15％和导电剂5％～15％。On the one hand, the present application provides a tin-containing negative electrode material, which includes, by weight percentage, tin particles 70% to 90%, an elastic binder 5% to 15%, and a conductive agent 5% to 15%.
本申请提供的含锡负极材料，以锡颗粒为负极活性材料，通过添加弹性粘结剂在锡颗粒表面形成一层防护层，该防护层一方面解决了锡颗粒直接与电解液接触而造成的腐蚀问题；另一方面，由于弹性粘结剂具有一定的抗形变的能力，在一定程度上可以抑制负极锡的体积膨胀及粉化。The tin-containing negative electrode material provided in this application uses tin particles as the negative electrode active material, and a protective layer is formed on the surface of the tin particles by adding an elastic binder. On the one hand, the protective layer solves the problem caused by the direct contact of the tin particles with the electrolyte Corrosion problem; on the other hand, because the elastic binder has a certain resistance to deformation, it can suppress the volume expansion and powdering of the negative electrode tin to a certain extent.
通过使用与锡颗粒牢固接触且具有弹性的粘结剂，在粘结负极活性材料的同时作为人造弹性SEI膜，起到隔绝锡颗粒与电解液接触并保证稳定包裹锡颗粒表面的作用。通过添加导电剂，可以与弹性粘结剂相配合，提高含锡负极材料的导电性。By using a binder that is in firm contact with tin particles and has elasticity, it acts as an artificial elastic SEI film while binding the negative electrode active material, which serves to isolate the tin particles from contacting the electrolyte and ensure the stable wrapping of the tin particle surface. By adding a conductive agent, it can be matched with an elastic binder to improve the conductivity of the tin-containing negative electrode material.
在电池的充放电过程中，当锡颗粒发生膨胀时，弹性粘结剂与锡颗粒之间的粘附锚点相隔距离会增大，弹性粘结剂的使用可保证在该过程中粘结剂层不发生破裂。During the charging and discharging of the battery, when the tin particles expand, the distance between the adhesive anchor point of the elastic adhesive and the tin particles will increase, and the use of the elastic adhesive can ensure the adhesive in the process The layer does not crack.
本申请的含锡负极材料中，按重量百分比计，锡颗粒的含量典型但非限制性的例如可以为：70％、72％、75％、78％、80％、82％、85％、88％或90％；弹性粘结剂典型但非限制性的例如可以为：5％、6％、7％、8％、9％、10％、11％、12％、13％、14％或15％。导电剂典型但非限制性的例如可以为：5％、6％、7％、8％、9％、10％、11％、12％、13％、14％或15％。In the tin-containing negative electrode material of the present application, the content of tin particles in terms of weight percentage is typical but not limited, for example: 70%, 72%, 75%, 78%, 80%, 82%, 85%, 88 % Or 90%; typical but non-limiting examples of elastic binders are: 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14% or 15 %. Typical but non-limiting examples of the conductive agent may be: 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, or 15%.
在本申请的一些实施方式中，按重量百分比计包括：锡颗粒72％～88％、弹性粘结剂6％～14％和导电剂6％～14％，进一步优选为：锡颗粒75％～85％、弹性粘结剂8％～12％和导电剂8％～12％。In some embodiments of the present application, the percentage by weight includes: tin particles 72% to 88%, elastic binder 6% to 14% and conductive agent 6% to 14%, further preferably: tin particles 75% to 85%, elastic binder 8%-12% and conductive agent 8%-12%.
通过优化含锡负极材料的组成，可以进一步提高含锡负极材料的结构稳定性，从而提高电池的循环稳定性。By optimizing the composition of the tin-containing anode material, the structural stability of the tin-containing anode material can be further improved, thereby improving the cycle stability of the battery.
在本申请的一些实施方式中，所述锡颗粒为微米级或纳米级的锡颗粒。微米级或纳米级的锡颗粒是指锡颗粒的粒径在微米级或纳米级，例如锡颗粒的粒径在几纳米到几十微米范围内。In some embodiments of the present application, the tin particles are micron or nanoscale tin particles. The micron or nanometer tin particles mean that the particle size of the tin particles is in the micron or nanometer range, for example, the tin particle size is in the range of several nanometers to tens of micrometers.
小尺度的负极活性材料有助于增大比表面积，抑制材料的体积膨胀。利用包含微米级或纳米级锡颗粒的负极材料可以有效解决目前锡负极易出现粉化、倍率性能低的问题，具体的，利用该锡颗粒解决上述问题的具体原理如下：The small-scale negative electrode active material helps to increase the specific surface area and suppress the volume expansion of the material. The use of anode materials containing micron or nanoscale tin particles can effectively solve the current problems of tin anodes prone to powdering and low rate performance. Specifically, the specific principles of using tin particles to solve the above problems are as follows:
1)针对于膨胀粉化问题：Sn作为二次电池的负极时，由于在充放电过程中会发生合金化反应，从而导致材料本身在充放电过程中发生极大的不均匀的体积变化。对于常规金属箔负极而言，由于过大的尺寸导致金属箔无法适应剧烈的体积变化而出现粉化现象，并最终导致电池循环性能不佳。大量研究表明，降低材料的尺寸将会有效缓解体积变化导致的粉化问题，因此本申请通过将锡颗粒微米纳米化，并利用锡颗粒作为负极活性材料，在很大程度上缓解了膨胀粉化问题，有效提高电池的循环能力。1) For the problem of swelling and pulverization: When Sn is used as the negative electrode of a secondary battery, since the alloying reaction occurs during charging and discharging, the material itself undergoes extremely uneven volume changes during charging and discharging. For the conventional metal foil negative electrode, due to the excessive size, the metal foil cannot adapt to the drastic volume change and powdering occurs, which eventually leads to poor battery cycle performance. A large number of studies have shown that reducing the size of the material will effectively alleviate the pulverization problem caused by the volume change. Therefore, this application has greatly mitigated the expansion of pulverization by micronizing tin particles and using tin particles as negative electrode active materials. Problem, effectively improve the battery's cycling ability.
2)针对倍率不佳问题：在充放电过程中，传统利用Sn箔作为负极时，金属负极材料合金化后形成的合金导电性不佳，同时合金化过程的离子扩散过程相较于插层缓缓，导致金属负极表现出较差的倍率性能。本申请通过将Sn颗粒微米纳米化，增大了锡的比表面积，使得合金化位点大大增加，有效提高了金属合金化速度，进而改善金属材料作为负极的倍率性能。2) For the problem of poor magnification: In the process of charging and discharging, when Sn foil is traditionally used as the negative electrode, the alloy formed by alloying the metal negative electrode material has poor conductivity, and the ion diffusion process of the alloying process is slower than that of intercalation Slow, resulting in metal anodes showing poor rate performance. This application increases the specific surface area of tin by nanometerizing Sn particles, so that the alloying sites are greatly increased, and the metal alloying speed is effectively increased, thereby improving the rate performance of metal materials as negative electrodes.
在本申请的一些实施方式中，所述弹性粘结剂包括海藻酸盐类粘结剂、多糖类粘结剂、羧甲基纤维素盐粘结剂、聚烯烃类粘结剂、聚氨酯类粘结剂、聚酯类粘结剂、聚酰胺类粘结剂或聚亚胺类粘结剂中的至少一种。In some embodiments of the present application, the elastic binder includes alginate binders, polysaccharide binders, carboxymethyl cellulose salt binders, polyolefin binders, polyurethanes At least one of an adhesive, a polyester-based adhesive, a polyamide-based adhesive, or a polyimide-based adhesive.
例如，弹性粘结剂可以为海藻酸钙(简称为Ca-Alg)、环糊精聚合物(简称为CDp)、***树胶(简称为GA)、黄原胶(简称为XG)、胍尔豆胶 (简称为GG)、刺槐豆胶(简称为LBG)、刺梧桐树胶(简称为KG)、***树脂-聚丙烯酸共聚物(简称为GA-PAA)、醋酸乙烯树脂(简称为PVAc)、聚丙烯酸-聚乙烯醇共聚物(简称为PAA-PVA)、聚乙烯醇-聚乙烯亚胺共聚物(简称为PVA-PEI)、聚丙烯酸-羧甲基纤维素钠共聚物(简称为PAA-CMC)、聚丙烯酸铵(简称为PAA-NH4)、聚丙烯酸钠接枝羧甲基纤维素钠(简称为NaPPA-g-CMC)或海藻酸钠-羧甲基壳聚糖共聚物(简称为Alg-C-chitosan)中的至少一种。For example, the elastic binder may be calcium alginate (Ca-Alg for short), cyclodextrin polymer (CDp for short), gum arabic (GA for short), xanthan gum (XG for short), guar bean Gum (abbreviated as GG), locust bean gum (abbreviated as LBG), karaya gum (abbreviated as KG), Arabic resin-polyacrylic acid copolymer (abbreviated as GA-PAA), vinyl acetate resin (abbreviated as PVAc), polymer Acrylic acid-polyvinyl alcohol copolymer (abbreviated as PAA-PVA), polyvinyl alcohol-polyethyleneimine copolymer (abbreviated as PVA-PEI), polyacrylic acid-carboxymethyl cellulose sodium copolymer (abbreviated as PAA-CMC) ), ammonium polyacrylate (referred to as PAA-NH4), sodium polyacrylate grafted sodium carboxymethyl cellulose (referred to as NaPPA-g-CMC) or sodium alginate-carboxymethyl chitosan copolymer (referred to as Alg -C-chitosan).
另外，上述弹性粘结剂也涵盖一些橡胶类粘结剂，橡胶类粘结剂例如包括天然橡胶NR、丁苯橡胶SBR、顺丁橡胶BR、异戊橡胶IR、氯丁橡胶CR、丁基橡胶IIR、丁晴橡胶NBR、氢化丁晴橡胶HNBR、乙丙橡胶EPM\EPDM、硅橡胶Q、氟橡胶FPM、聚氨酯橡胶AU\EU、丙烯酸酯橡胶ACM\AEM、氯磺化聚乙烯橡胶CSM、氯醚橡胶CO\ECO或氯化聚乙烯橡胶CM\CPE中的至少一种。In addition, the above-mentioned elastic adhesive also covers some rubber-based adhesives, such as natural rubber NR, styrene-butadiene rubber SBR, butadiene rubber BR, isoprene rubber IR, neoprene CR, butyl rubber IIR, nitrile rubber NBR, hydrogenated nitrile rubber HNBR, ethylene propylene rubber EPM\EPDM, silicone rubber Q, fluorine rubber FPM, polyurethane rubber AU\EU, acrylic rubber ACM\AEM, chlorosulfonated polyethylene rubber CSM, chlorine At least one of ether rubber CO\ECO or chlorinated polyethylene rubber CM\CPE.
通过优化弹性粘结剂的种类，可以进一步提高含锡负极材料在充放电过程中的稳定性，进而提高电池的循环稳定性。By optimizing the type of elastic binder, the stability of the tin-containing negative electrode material during charge and discharge can be further improved, thereby further improving the cycle stability of the battery.
在本申请的一些实施方式中，所述导电剂包括有机导电剂和/或无机导电剂。In some embodiments of the present application, the conductive agent includes an organic conductive agent and/or an inorganic conductive agent.
无机导电剂包括导电碳材料和/或导电金属材料。例如，碳导电材料可以为导电炭黑、导电碳球、导电石墨、石墨烯、碳纳米管、碳纳米带、碳纤维、还原氧化石墨烯；导电金属材料可以为铜单质纳米材料(纳米线、纳米管、纳米片、纳米带、纳米颗粒等)或银单质纳米材料等。The inorganic conductive agent includes a conductive carbon material and/or a conductive metal material. For example, the carbon conductive material may be conductive carbon black, conductive carbon spheres, conductive graphite, graphene, carbon nanotubes, carbon nanoribbons, carbon fiber, reduced graphene oxide; the conductive metal material may be copper simple nanomaterials (nanowire, nanometer Tubes, nanosheets, nanoribbons, nanoparticles, etc.) or silver nanomaterials.
有机导电剂为具有一定导电能力的有机物，同时，该有机物可以带有一定的粘结性。因此，当导电剂为具有一定粘结的有机物时，其不仅能够起到导电 剂的作用，还可以起到粘结剂的作用。利用带有粘结剂的有机物作为导电剂时，可以在锡颗粒表面形成包覆层，进一步减少锡颗粒的膨胀，降低粉化情况的发生。The organic conductive agent is an organic substance with a certain conductivity, and at the same time, the organic substance can have a certain adhesiveness. Therefore, when the conductive agent is an organic substance with a certain adhesion, it can not only function as a conductive agent but also as a binder. When an organic substance with a binder is used as a conductive agent, a coating layer can be formed on the surface of the tin particles, which further reduces the expansion of the tin particles and reduces the occurrence of pulverization.
另外，无机导电剂为颗粒结构，体积尺寸较大，在锡颗粒膨胀过程中，会与其发生挤压，较大体积的导电剂颗粒可能会压破锡颗粒，破坏材料结构，降低电池性能。而有机导电剂的使用在一定程度上可认为是更为均匀的导电剂。有机导电剂的使用可在锡颗粒表面形成均匀的高分子包覆层，在起到粘结作用的同时，保护锡颗粒不受损伤。另外，包覆层的另一个优点是能较大程度地隔绝锡颗粒与电解液接触，减少材料的损耗并提高导电性。In addition, the inorganic conductive agent has a particle structure and a large volume size. During the expansion of the tin particles, it will squeeze with it. The larger volume of conductive agent particles may crush the tin particles, destroy the material structure, and reduce the battery performance. The use of organic conductive agents can be considered to be a more uniform conductive agent to a certain extent. The use of an organic conductive agent can form a uniform polymer coating layer on the surface of the tin particles, which can protect the tin particles from being damaged while playing a bonding role. In addition, another advantage of the cladding layer is that it can isolate the tin particles from the electrolyte to a greater extent, reduce the loss of materials and improve the conductivity.
其中，有机导电剂包括离子型有机导电剂和/或电子型有机导电剂。离子型有机导电剂例如可以为：聚氧化乙烯、聚环氧丙烷、聚丁二酸乙二醇酯、聚葵二酸乙二酸酯或聚乙二醇亚胺中的至少一种，优选为聚氧化乙烯。电子型有机导电剂例如可以为聚吡咯、聚对苯撑、聚苯硫醚、聚噻吩、聚对苯撑乙烯或聚苯胺中的至少一种。The organic conductive agent includes an ionic organic conductive agent and/or an electronic organic conductive agent. The ionic organic conductive agent may be, for example, at least one of polyethylene oxide, polypropylene oxide, polyethylene succinate, polyethylene oxalate, or polyethylene glycol imine, preferably Polyethylene oxide. The electronic type organic conductive agent may be, for example, at least one of polypyrrole, polyparaphenylene, polyphenylene sulfide, polythiophene, polyparaphenylene vinylene, or polyaniline.
在本申请的一些实施方式中，所述含锡负极材料按重量百分比计包括偶联剂0.5％～2％。In some embodiments of the present application, the tin-containing negative electrode material includes a coupling agent by 0.5% to 2% by weight.
偶联剂是一类具有两不同性质官能团的物质，其分子结构的最大特点是分子中含有化学性质不同的两个基团，一个是亲无机物的基团，易于与无机物表面起化学反应；另一个是亲有机物的基团，能与合成树脂或其它聚合物发生化学反应或生成氢键溶于其中。因此偶联剂被称作"分子桥"，用以改善无机物与有机物之间的界面作用，从而大大提高复合材料的性能，如物理性能、电性能、热性能和光性能等。Coupling agent is a kind of substance with two functional groups with different properties. The biggest feature of its molecular structure is that the molecule contains two groups with different chemical properties, one is an inorganic-philic group, and it is easy to react with the surface of inorganic substances. ; The other is an organophilic group that can chemically react with synthetic resins or other polymers or dissolve in hydrogen bonds. Therefore, the coupling agent is called "molecular bridge" to improve the interface between inorganic and organic substances, thereby greatly improving the performance of composite materials, such as physical properties, electrical properties, thermal properties and optical properties.
本上述实施方式中，在含锡负极材料中加入偶联剂可以极大地改善锡颗粒 和粘结剂之间的界面接触，在保证粘结剂可均匀覆盖锡颗粒的同时，在成键作用下使得锡颗粒与粘结剂附着牢固，隔绝锡颗粒和电解液的接触。另一方面，通过使用偶联剂在无机锡颗粒与有机粘结剂之间构建分子桥，通过增加锚固点的方式进一步增加粘结剂的附着力。另外，在充放电过程中由于锡负极活性材料的体积变化，粘结剂与负极集流体的附着力差，容易导致锡颗粒在充放电过程中从负极集流体上剥落，而偶联剂的使用可增加锡颗粒与负极集流体的结合力，减少剥落情况的发生。In the above embodiment, adding a coupling agent to the tin-containing negative electrode material can greatly improve the interface contact between the tin particles and the binder, while ensuring that the binder can evenly cover the tin particles, under the effect of bonding The tin particles and the adhesive are firmly attached, and the contact between the tin particles and the electrolyte is blocked. On the other hand, by using a coupling agent to build a molecular bridge between the inorganic tin particles and the organic binder, the adhesion of the binder is further increased by adding anchor points. In addition, due to the volume change of the tin anode active material during the charging and discharging process, the adhesion between the binder and the anode current collector is poor, which may easily cause the tin particles to peel off from the anode current collector during the charging and discharging process, and the use of the coupling agent It can increase the binding force of tin particles and negative electrode current collector and reduce the occurrence of flaking.
其中，偶联剂典型但非限制性的包括铬络合物偶联剂、硅烷偶联剂、钛酸酯偶联剂或铝酸盐偶联剂中的至少一种。例如，偶联剂可以为铬络合物偶联剂、硅烷偶联剂、钛酸酯偶联剂、铝酸盐偶联剂、铬络合物偶联剂-硅烷偶联剂的组合、硅烷偶联剂-钛酸酯偶联剂的组合或钛酸酯偶联剂-铝酸盐偶联剂的组合等等。Among them, typical but non-limiting coupling agents include at least one of chromium complex coupling agents, silane coupling agents, titanate coupling agents, or aluminate coupling agents. For example, the coupling agent may be a chromium complex coupling agent, silane coupling agent, titanate coupling agent, aluminate coupling agent, chromium complex coupling agent-silane coupling agent combination, silane Combination of coupling agent-titanate coupling agent or combination of titanate coupling agent-aluminate coupling agent, etc.
第二方面，本申请提供了一种含锡负极材料的制备方法，该制备方法是将所述锡颗粒、所述弹性粘结剂和所述导电剂以及任选的所述偶联剂混合，得到所述含锡负极材料。In a second aspect, the present application provides a method for preparing a tin-containing negative electrode material, the preparation method is to mix the tin particles, the elastic binder, the conductive agent, and optionally the coupling agent, The tin-containing negative electrode material is obtained.
利用该制备方法得到的含锡负极材料具备上述负极材料的全部优点，在此不再赘述。The tin-containing negative electrode material obtained by the preparation method has all the advantages of the above negative electrode material, and will not be described here.
第三方面，本申请提供了一种负极浆料，将上述含锡负极材料与有机溶剂混合后得到所述负极浆料。In a third aspect, the present application provides a negative electrode slurry, which is obtained by mixing the foregoing tin-containing negative electrode material with an organic solvent.
将上述含锡负极材料制备成负极浆料更方便电池的制备。The preparation of the above tin-containing negative electrode material into a negative electrode slurry is more convenient for the preparation of batteries.
在本申请的一些实施方式中，所述负极浆料可以通过以下方法制备得到：将所述锡颗粒、所述弹性粘结剂和所述导电剂以及任选的偶联剂混合后研磨均匀，得到所述负极浆料。In some embodiments of the present application, the negative electrode slurry may be prepared by mixing the tin particles, the elastic binder, the conductive agent, and the optional coupling agent, and grinding them uniformly. The negative electrode slurry is obtained.
该方法为常规浆料的制备方法，工艺成熟稳定，方便操作。This method is the preparation method of conventional slurry, the process is mature and stable, and it is convenient to operate.
该实施方式中，负极浆料例如可以通过以下方法制备得到：按一定重量比称取锡颗粒、粘结剂和导电剂，将各物料置于研钵中，滴加适量有机溶剂研磨均匀后，得到所述负极浆料。In this embodiment, the negative electrode slurry may be prepared, for example, by weighing tin particles, a binder, and a conductive agent at a certain weight ratio, placing each material in a mortar, and adding an appropriate amount of organic solvent to grind it uniformly. The negative electrode slurry is obtained.
在本申请的另一些实施方式中，所述负极浆料可以通过以下方法制备得到：提供锡颗粒与有机溶剂组成的悬浮液，并将任选的偶联剂溶于所述悬浮液中，再加入所述粘结剂和所述导电剂混合均匀，得到所述负极浆料。In other embodiments of the present application, the negative electrode slurry may be prepared by providing a suspension composed of tin particles and an organic solvent, and dissolving an optional coupling agent in the suspension, and then The binder and the conductive agent are added and mixed uniformly to obtain the negative electrode slurry.
先将偶联剂加入锡颗粒与有机溶剂组成的悬浮液中，可以使偶联剂与锡颗粒表面充分接触，发生键合反应，然后再加入粘结剂，从而提高锡颗粒与粘结剂之间的结合强度。First, the coupling agent is added to the suspension composed of tin particles and an organic solvent, which can make the coupling agent fully contact with the surface of the tin particles, a bonding reaction occurs, and then the binder is added, thereby increasing the tin particles and the binder The bonding strength between.
第四方面，本申请提供了一种负极，包括负极集流体和形成于所述负极集流体表面的负极材料层，所述负极材料层由上述含锡负极材料制备而成。According to a fourth aspect, the present application provides a negative electrode including a negative electrode current collector and a negative electrode material layer formed on the surface of the negative electrode current collector. The negative electrode material layer is prepared from the foregoing tin-containing negative electrode material.
其中，负极集流体的材质例如选自铝、锂、镁、钒、铜、铁、锡、锌、镍、钛或锰中的至少一种或至少一种的合金。The material of the negative electrode current collector is, for example, at least one kind or an alloy of at least one kind selected from aluminum, lithium, magnesium, vanadium, copper, iron, tin, zinc, nickel, titanium, or manganese.
第五方面，本申请提供了一种上述负极的制备方法，利用上述含锡负极材料在所述负极集流体表面制备所述负极材料层后，得到所述负极。According to a fifth aspect, the present application provides a method for preparing the foregoing negative electrode. The negative electrode material layer is prepared on the surface of the negative electrode current collector using the foregoing tin-containing negative electrode material to obtain the negative electrode.
为方便加工制备，可以将利用上述负极浆料制备该负极，例如，可以将负极浆料涂覆于所述负极集流体表面，干燥后得到所述负极。To facilitate processing and preparation, the above negative electrode slurry may be used to prepare the negative electrode. For example, the negative electrode slurry may be coated on the surface of the negative electrode current collector and dried to obtain the negative electrode.
第六方面，本申请提供了一种二次电池，包括正极、电解液、隔膜和上述负极。电解液和隔膜介于正极和负极之间。In a sixth aspect, the present application provides a secondary battery including a positive electrode, an electrolyte, a separator, and the above negative electrode. The electrolyte and the separator are between the positive electrode and the negative electrode.
其中，所述二次电池包括单离子电池和双离子电池。Wherein, the secondary battery includes a single ion battery and a dual ion battery.
本申请中的上述负极不仅可以用于常规的单离子电池体系，例如锂离子电池，钠离子电池，钾离子电池，还可以用于金属合金化反应的电池体系中，尤 其适用于于锡金属反应的电池体系中，例如基于锡-石墨的钠基、钾基以及钙基双离子电池体系等等。The above-mentioned negative electrode in this application can be used not only in conventional single ion battery systems, such as lithium ion batteries, sodium ion batteries, potassium ion batteries, but also in battery system of metal alloying reaction, especially suitable for tin metal reaction In the battery system, for example, tin-graphite-based sodium-based, potassium-based and calcium-based dual-ion battery systems, and so on.
通过选择不同的正极材料和电解液等原料与本申请提供的负极相匹配，可以得到多种形式的二次电池。By selecting different positive electrode materials, electrolytes and other raw materials to match the negative electrode provided in this application, various forms of secondary batteries can be obtained.
本申请的二次电池中，正极包括正极集流体和形成于正极集流体表面的正极材料层，而正极材料层包括正极活性材料、正极粘结剂和正极导电剂。其中，正极材料层中，正极活性材料的含量为60-95wt％，导电剂的含量为2-30wt％，粘结剂的含量为3-10wt％。In the secondary battery of the present application, the positive electrode includes a positive electrode current collector and a positive electrode material layer formed on the surface of the positive electrode current collector, and the positive electrode material layer includes a positive electrode active material, a positive electrode binder, and a positive electrode conductive agent. Among them, in the positive electrode material layer, the content of the positive electrode active material is 60-95 wt%, the content of the conductive agent is 2-30 wt%, and the content of the binder is 3-10 wt%.
正极集流体选自铝、锂、镁、钒、铜、铁、锡、锌、镍、钛、锰中的至少一种或至少一种的合金。优选地，正极集流体为锡箔。The positive electrode current collector is selected from at least one or an alloy of at least one of aluminum, lithium, magnesium, vanadium, copper, iron, tin, zinc, nickel, titanium, and manganese. Preferably, the positive electrode current collector is tin foil.
正极活性材料为石墨类材料，包括中间相碳微球石墨、天然石墨、膨胀石墨、玻璃碳、碳碳复合材料、碳纤维、硬碳、高取向石墨、炭黑、碳纳米管、石墨烯中的一种或几种，优选为膨胀石墨。The positive electrode active material is graphite-based materials, including mesophase carbon microsphere graphite, natural graphite, expanded graphite, glassy carbon, carbon-carbon composite materials, carbon fiber, hard carbon, highly oriented graphite, carbon black, carbon nanotubes, graphene One or more kinds, preferably expanded graphite.
正极导电剂例如可以为导电炭黑、导电碳球、导电石墨、碳纳米管、导电碳纤维、石墨烯或还原氧化石墨烯中的至少一种。优选地，所述正极导电剂为导电炭黑。The positive electrode conductive agent may be, for example, at least one of conductive carbon black, conductive carbon spheres, conductive graphite, carbon nanotubes, conductive carbon fiber, graphene, or reduced graphene oxide. Preferably, the positive electrode conductive agent is conductive carbon black.
正极粘结剂例如可以为聚偏氟乙烯、聚四氟乙烯、聚乙烯醇、羧甲基纤维素、SBR橡胶或聚烯烃类中的至少一种。优选地，正极粘结剂为聚偏氟乙烯。The positive electrode binder may be, for example, at least one of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, SBR rubber, or polyolefin. Preferably, the positive electrode binder is polyvinylidene fluoride.
电解液中电解质盐根据二次电池的种类可以为锂盐、钠盐、钾盐、镁盐或钙盐等等。以钠盐为例，钠盐例如可以选自四氟硼酸钠、双三氟甲基磺酰亚胺钠、双氟磺酰亚胺钠、氯化钠、硫酸钠、硫代硫酸钠、碳酸钠、碳酸氢钠、硝酸钠、氟化钠、苯酚钠、丁酸钠、草酸钠、丁二酸钠、水杨酸钠、碘乙酸钠、高氯酸钠、肌氨酸钠、辛基硫酸钠、六氟磷酸钠、硅酸钠、甲基二黄酸钠、醋 酸钠、1，5-萘二磺酸钠、重铬酸钠、硫氰酸钠、苯亚磺酸钠、透明质酸钠或烯丙基磺酸钠中的至少一种，优选为六氟磷酸钠，钠盐的浓度范围优选为1–4mol/L。The electrolyte salt in the electrolyte may be a lithium salt, a sodium salt, a potassium salt, a magnesium salt, a calcium salt, etc. according to the type of secondary battery. Taking the sodium salt as an example, the sodium salt may be selected from sodium tetrafluoroborate, sodium bistrifluoromethylsulfonimide, sodium bisfluorosulfonimide, sodium chloride, sodium sulfate, sodium thiosulfate, sodium carbonate , Sodium bicarbonate, sodium nitrate, sodium fluoride, sodium phenolate, sodium butyrate, sodium oxalate, sodium succinate, sodium salicylate, sodium iodoacetate, sodium perchlorate, sodium sarcosinate, sodium octyl sulfate , Sodium hexafluorophosphate, sodium silicate, sodium methyldiflavinate, sodium acetate, sodium 1,5-naphthalene disulfonate, sodium dichromate, sodium thiocyanate, sodium benzenesulfinate, sodium hyaluronate Or at least one of sodium allyl sulfonates, preferably sodium hexafluorophosphate, and the concentration range of the sodium salt is preferably 1 to 4 mol/L.
电解液溶剂选自酯类、砜类、醚类、腈类或离子液体等有机溶剂的一种或几种。The electrolyte solvent is selected from one or more of organic solvents such as esters, sulfones, ethers, nitriles or ionic liquids.
溶剂例如可以为碳酸丙烯酯(PC)、碳酸乙烯酯(EC)、碳酸二乙酯(DEC)、碳酸二甲酯(DMC)、碳酸甲乙酯(EMC)、甲酸甲酯(MF)、乙酸甲酯(MA)、N,N-二甲基乙酰胺(DMA)、氟代碳酸乙烯酯(FEC)、丙酸甲酯(MP)、丙酸乙酯(EP)、乙酸乙酯(EA)、γ-丁内酯(GBL)、四氢呋喃(THF)、2-甲基四氢呋喃(2MeTHF)、1,3-二氧环戊烷(DOL)、4-甲基-1,3-二氧环戊烷(4MeDOL)、二甲氧甲烷(DMM)、1,2-二甲氧丙烷(DMP)、三乙二醇二甲醚(DG)、二甲基砜(MSM)、二甲醚(DME)、亚硫酸乙烯酯(ES)、亚硫酸丙烯脂(PS)、亚硫酸二甲脂(DMS)、亚硫酸二乙脂(DES)、冠醚(12-冠-4)、1-乙基-3-甲基咪唑-六氟磷酸盐、1-乙基-3-甲基咪唑-四氟硼酸盐、1-乙基-3-甲基咪唑-双三氟甲基磺酰亚胺盐、1-丙基-3-甲基咪唑-六氟磷酸盐、1-丙基-3-甲基咪唑-四氟硼酸盐、1-丙基-3-甲基咪唑-双三氟甲基磺酰亚胺盐、1-丁基-1-甲基咪唑-六氟磷酸盐、1-丁基-1-甲基咪唑-四氟硼酸盐、1-丁基-1-甲基咪唑-双三氟甲基磺酰亚胺盐、N-丁基-N-甲基吡咯烷-双三氟甲基磺酰亚胺盐、1-丁基-1-甲基吡咯烷-双三氟甲基磺酰亚胺盐、N-甲基-N-丙基吡咯烷-双三氟甲基磺酰亚胺盐、N-甲,丙基哌啶-双三氟甲基磺酰亚胺盐或N-甲,丁基哌啶-双三氟甲基磺酰亚胺盐中至少一种。The solvent may be, for example, propylene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), methyl formate (MF), acetic acid Methyl ester (MA), N,N-dimethylacetamide (DMA), fluoroethylene carbonate (FEC), methyl propionate (MP), ethyl propionate (EP), ethyl acetate (EA) , Γ-butyrolactone (GBL), tetrahydrofuran (THF), 2-methyltetrahydrofuran (2MeTHF), 1,3-dioxolane (DOL), 4-methyl-1,3-dioxolane Alkane (4MeDOL), dimethoxymethane (DMM), 1,2-dimethoxypropane (DMP), triethylene glycol dimethyl ether (DG), dimethyl sulfone (MSM), dimethyl ether (DME) , Vinyl sulfite (ES), propylene sulfite (PS), dimethyl sulfite (DMS), diethyl sulfite (DES), crown ether (12-crown-4), 1-ethyl- 3-methylimidazole-hexafluorophosphate, 1-ethyl-3-methylimidazole-tetrafluoroborate, 1-ethyl-3-methylimidazole-bistrifluoromethylsulfonimide salt, 1-propyl-3-methylimidazole-hexafluorophosphate, 1-propyl-3-methylimidazole-tetrafluoroborate, 1-propyl-3-methylimidazole-bistrifluoromethylsulfonate Imide salt, 1-butyl-1-methylimidazole-hexafluorophosphate, 1-butyl-1-methylimidazole-tetrafluoroborate, 1-butyl-1-methylimidazole-bis Trifluoromethylsulfonimide salt, N-butyl-N-methylpyrrolidine-bistrifluoromethylsulfonimide salt, 1-butyl-1-methylpyrrolidine-bistrifluoromethyl Sulfoimide salt, N-methyl-N-propylpyrrolidine-bistrifluoromethylsulfonimide salt, N-methyl, propylpiperidine-bistrifluoromethylsulfonimide salt or N -At least one of methyl, butylpiperidine-bistrifluoromethylsulfonimide salt.
电解液还可以含有添加剂，该添加剂可以是酯类、砜类、醚类、腈类或烯烃类有机添加剂的一种或几种，例如可以为氟代碳酸乙烯酯、碳酸亚乙烯酯、 碳酸乙烯亚乙酯、1,3-丙磺酸内酯、1,4-丁磺酸内酯、硫酸乙烯酯、硫酸丙烯酯、硫酸亚乙酯、亚硫酸乙烯酯、亚硫酸丙烯酯、二甲基亚硫酸酯、二乙基亚硫酸酯、亚硫酸亚乙酯、氯代甲酸甲脂、二甲基亚砜、苯甲醚、乙酰胺、二氮杂苯、间二氮杂苯、冠醚12-冠-4、冠醚18-冠-6、4-氟苯甲醚、氟代链状醚、二氟代甲基碳酸乙烯酯、三氟代甲基碳酸乙烯酯、氯代碳酸乙烯酯、溴代碳酸乙烯酯、三氟乙基膦酸、溴代丁内酯、氟代乙酸基乙烷、磷酸酯、亚磷酸酯、磷腈、乙醇胺、碳化二甲胺、环丁基砜、1,3-二氧环戊烷、乙腈、长链烯烃、三氧化二铝、氧化镁、氧化钡、碳酸钠、碳酸钙、二氧化碳、二氧化硫或碳酸锂中的至少一种。The electrolyte may also contain additives, which may be one or more of organic additives such as esters, sulfones, ethers, nitriles or olefins, for example, fluoroethylene carbonate, vinylene carbonate, ethylene carbonate Ethylene, 1,3-propane sultone, 1,4-butane sultone, vinyl sulfate, propylene sulfate, ethylene sulfate, vinyl sulfite, propylene sulfite, dimethyl Sulfite, diethyl sulfite, ethylene sulfite, methyl chloroformate, dimethyl sulfoxide, anisole, acetamide, diazabenzene, m-diazepine, crown ether 12 -Crown-4, crown ether 18-crown-6, 4-fluoroanisole, fluorochain ether, difluoromethyl vinyl carbonate, trifluoromethyl vinyl carbonate, chlorovinyl carbonate, Bromoethylene carbonate, trifluoroethylphosphonic acid, bromobutyrolactone, fluoroacetoxyethane, phosphate, phosphite, phosphazene, ethanolamine, carbodimethylamine, cyclobutyl sulfone, 1, At least one of 3-dioxolane, acetonitrile, long-chain olefins, aluminum oxide, magnesium oxide, barium oxide, sodium carbonate, calcium carbonate, carbon dioxide, sulfur dioxide, or lithium carbonate.
第七方面，本申请提供了一种用电设备。In a seventh aspect, the present application provides an electrical device.
其中，用电设备例如可以为电子装置、电动工具、电动车辆、电力储存***。在本申请实施方式的二次电池具有较好的循环稳定性效果。在使用本申请实施方式的二次电池的电子装置、电动工具、电动车辆、以及电力储存***中也可以获得相同的效果。Among them, the electrical equipment may be, for example, an electronic device, a power tool, an electric vehicle, or a power storage system. The secondary battery of the embodiment of the present application has a good cycle stability effect. The same effect can also be obtained in electronic devices, power tools, electric vehicles, and power storage systems using the secondary battery of the embodiment of the present application.
其中，电子装置是使用锂离子电池作为操作的电源执行各种功能(例如，演奏音乐)的电子装置。Among them, the electronic device is an electronic device that uses a lithium ion battery as a power source for operation to perform various functions (for example, playing music).
电动工具是使用锂离子电池作为驱动电源来移动移动部件(例如，钻头)的电动工具。A power tool is a power tool that uses a lithium ion battery as a driving power source to move moving parts (for example, a drill bit).
电动车辆是依靠锂离子电池作为驱动电源运行的电动车辆，并且可以是除了锂离子电池之外还装备有其他驱动源的汽车(包括混合动力车)。The electric vehicle is an electric vehicle that runs on a lithium ion battery as a driving power source, and may be an automobile (including a hybrid vehicle) equipped with other driving sources in addition to the lithium ion battery.
电力储存***是使用锂离子电池作为电力储存源的电力储存***。例如，在家用电力储存***中，使电力储存在用作电力储存源的锂离子电池中，并且根据需要消耗储存在锂离子电池中的电力以能够使用诸如家用电子产品的各 种装置。The power storage system is a power storage system that uses a lithium ion battery as a power storage source. For example, in a home power storage system, power is stored in a lithium ion battery used as a power storage source, and the power stored in the lithium ion battery is consumed as necessary to enable various devices such as home electronic products.
下面将结合实施例和对比例对本申请做进一步详细的说明。The present application will be further described in detail in conjunction with examples and comparative examples below.
实施例1Example 1
本实施例是一种负极，包括负极集流体和形成于负极集流体表面的负极材料层，该负极材料层的原料包括纳米锡颗粒，弹性粘结剂和导电剂。其中，负极集流体为锡箔，弹性粘结剂为海藻酸钙，导电剂为聚氧化乙烯PEO。This embodiment is a negative electrode including a negative electrode current collector and a negative electrode material layer formed on the surface of the negative electrode current collector. The raw material of the negative electrode material layer includes nano-tin particles, an elastic binder and a conductive agent. Among them, the negative electrode current collector is tin foil, the elastic binder is calcium alginate, and the conductive agent is polyethylene oxide PEO.
该负极的制备方法包括以下步骤：The preparation method of the negative electrode includes the following steps:
S1)称取0.05g的导电剂聚氧化乙烯PEO溶于5mlN-甲基吡咯烷酮(NMP)中混合均匀，然后再加入0.05g的弹性粘结剂混合均匀后形成均一溶液；S1) Weigh 0.05g of conductive agent polyethylene oxide PEO dissolved in 5ml N-methylpyrrolidone (NMP) and mix well, then add 0.05g of elastic binder and mix well to form a uniform solution;
S2)将纳米锡颗粒0.4g清洗干净后，加入上述均一溶液中，混合均匀后得到负极浆料；S2) After 0.4g of nano-tin particles are cleaned, they are added to the above-mentioned homogeneous solution and mixed evenly to obtain a negative electrode slurry;
S3)将所得浆料涂覆于负极集流体表面，完全干燥后进行裁切，裁成直径为12mm的圆片，得到负极，放在真空干燥箱内备用。S3) Apply the obtained slurry to the surface of the negative electrode current collector, dry it completely, cut it, and cut it into 12 mm diameter discs to obtain the negative electrode, and put it in a vacuum drying box for use.
实施例2～15Examples 2 to 15
实施例2～15分别是一种负极，与实施例1的不同之处在于使用的弹性粘结剂不同，其他与实施例1均相同。实施例1～15的具体的弹性粘结剂的选择如表1所示。Examples 2 to 15 are each a negative electrode. The difference from Example 1 is that the elastic binder used is different, and the others are the same as Example 1. The selection of specific elastic binders of Examples 1 to 15 is shown in Table 1.
表1Table 1
Figure PCTCN2019125440-appb-000001
Figure PCTCN2019125440-appb-000001
Figure PCTCN2019125440-appb-000002
Figure PCTCN2019125440-appb-000002
实施例16～20Examples 16-20
实施例16～20分别是一种负极，与实施例1的不同之处在于使用的导电剂不同，其他与实施例1均相同。实施例1～15的具体的导电剂的选择如表2所示。Examples 16 to 20 are each a negative electrode. The difference from Example 1 is that the conductive agent used is different, and the others are the same as Example 1. The selection of specific conductive agents in Examples 1 to 15 is shown in Table 2.
表2Table 2
序号Serial number 导电高分子Conductive polymer
实施例1Example 1 PEOPEO
实施例16Example 16 聚环氧丙烷Polypropylene oxide
实施例17Example 17 聚丁二酸乙二醇酯Polyethylene succinate
实施例18Example 18 聚葵二酸乙二酸酯Polyoxalate
实施例19Example 19 聚乙二醇亚胺Polyethylene glycol imine
实施例20Example 20 PEO+聚乙二醇亚胺PEO+polyethylene glycol imine
实施例21～25Examples 21-25
实施例21～25分别是一种负极，与实施例1相比，原料种类相同，不同之处在于锡颗粒、弹性粘结剂和导电剂的重量比不同。实施例21～25中锡颗粒、弹性粘结剂和导电剂的重量比列于表3。Examples 21 to 25 are respectively a negative electrode. Compared with Example 1, the types of raw materials are the same, but the difference is that the weight ratio of tin particles, elastic binder and conductive agent is different. The weight ratio of tin particles, elastic binder and conductive agent in Examples 21-25 is shown in Table 3.
表3table 3
序号Serial number 锡颗粒:弹性高分子:导电剂Tin particles: elastic polymer: conductive agent
实施例1Example 1 8：1：18:1:1
实施例21Example 21 7.5：1：1.57.5: 1: 1.5
实施例22Example 22 7.5：1.5：17.5: 1.5: 1
实施例23Example 23 9：0.5：0.59:0.5:0.5
实施例24Example 24 8.5：1：0.58.5: 1:0.5
实施例25Example 25 8.5：0.5：18.5: 0.5: 1
实施例26～28Examples 26 to 28
实施例26～28分别是一种负极，与实施例1相比不同之处在于，实施例26～28分别添加了一种偶联剂，偶联剂的添加量均为锡颗粒重量的0.5％。实施例26～28各原料的配比列于表4。Examples 26 to 28 are each a negative electrode. The difference compared with Example 1 is that Examples 26 to 28 respectively add a coupling agent, and the amount of coupling agent added is 0.5% of the weight of the tin particles . The compounding ratio of each raw material of Examples 26 to 28 is shown in Table 4.
表4Table 4
序号Serial number 偶联剂Coupling agent
实施例1Example 1 //
实施例26Example 26 铝酸酯偶联剂Aluminate coupling agent
实施例27Example 27 钛酸酯偶联剂Titanate coupling agent
实施例28Example 28 硅烷偶联剂A silane coupling agent
对比例1Comparative Example 1
本对比例为一种负极，该负极为金属锡片。This comparative example is a negative electrode, which is a metal tin sheet.
对比例2Comparative Example 2
本对比例为一种负极，与实施例1的不同之处在于使用的粘结剂不同，该对比例中的粘结剂为PVDF粘结剂，制备过程中使用的溶剂为NMP溶剂。其他与实施例1均相同。This comparative example is a negative electrode, which differs from Example 1 in that the binder used is different. The binder in this comparative example is a PVDF binder, and the solvent used in the preparation process is an NMP solvent. Others are the same as in Example 1.
实施例29Example 29
本实施例是一种锡-石墨双离子电池，其制备方法包括以下步骤：This embodiment is a tin-graphite dual ion battery, and its preparation method includes the following steps:
S1)制备正极：将0.4g膨胀石墨、0.05g导电碳黑和0.05g聚四氟乙烯充分研磨后加入大约4ml氮甲基吡咯烷酮溶液中，获得均匀浆料；然后将浆料均匀的涂覆于涂炭铝箔(即正极集流体)表面，并真空干燥；对干燥所得电极片裁切成直径10mm的圆片，压实后作为正极备用；S1) Preparation of positive electrode: 0.4g expanded graphite, 0.05g conductive carbon black and 0.05g polytetrafluoroethylene are fully ground and added to about 4ml of nitromethylpyrrolidone solution to obtain a uniform slurry; then the slurry is evenly coated on Carbon-coated aluminum foil (ie, positive electrode current collector) surface, and vacuum drying; cut the dried electrode sheet into a 10mm diameter disc, and then use it as a positive electrode after compaction;
S2)制备电解液：称取一定量0.50钠盐加入到3ml碳酸乙烯酯/碳酸二甲酯/碳酸甲乙酯的混合溶液中，其中，碳酸乙烯酯：碳酸二甲酯：碳酸甲乙酯的体积比为1：1：1，充分搅拌溶解后在手套箱备用；S2) Preparation of electrolyte: Weigh a certain amount of 0.50 sodium salt into 3ml of ethylene carbonate/dimethyl carbonate/ethyl methyl carbonate mixed solution, where ethylene carbonate: dimethyl carbonate: ethyl methyl carbonate The volume ratio is 1:1:1, fully stirred and dissolved in the glove box for use;
S3)锡-石墨双离子电池组装：在惰性气体保护的手套箱中，将制备好的正极、有机电解液和实施例1中的负极依次紧密堆叠，然后将封装入扣式壳体，得到扣式电池，完成电池组装。S3) Tin-graphite dual-ion battery assembly: in an inert gas-protected glove box, the prepared positive electrode, organic electrolyte, and the negative electrode in Example 1 are closely stacked in sequence, and then packaged into a button-type case to obtain a button Battery, complete battery assembly.
实施例30～56Examples 30 to 56
实施例30～56分别是一种锡-石墨双离子电池，其与实施例29的不同之处在于，实施例30～56中的电池所用的负极分别依次对应实施例2～28所提供的负极。Examples 30 to 56 are respectively a tin-graphite dual ion battery, which differs from Example 29 in that the negative electrodes used in the batteries in Examples 30 to 56 respectively correspond to the negative electrodes provided in Examples 2 to 28 .
对比例3～4Comparative example 3～4
对比例3～4分别是一种锡-石墨双离子电池，其与实施例29的不同之处在于，对比例3～4中的电池所用的负极分别依次对应对比例1～2所提供的负极。Comparative Examples 3 to 4 are respectively a tin-graphite dual ion battery, which is different from Example 29 in that the negative electrodes used in the batteries in Comparative Examples 3 to 4 respectively correspond to the negative electrodes provided in Comparative Examples 1 to 2 .
分别测试实施例29～56和对比例3～4中的锡-石墨双离子电池电性能。测试项目为各组电池充放电循环500次后的容量保持率，测试结果列于表5。The electrical properties of the tin-graphite dual ion batteries in Examples 29 to 56 and Comparative Examples 3 to 4 were tested respectively. The test item is the capacity retention rate of each group of batteries after 500 charge and discharge cycles. The test results are listed in Table 5.
表5测试结果Table 5 Test results
序号Serial number 循环次数Cycles 容量保持率Capacity retention rate
实施例29Example 29 500500 93％93%
实施例30Example 30 500500 89％89%
实施例31Example 31 500500 90％90%
实施例32Example 32 500500 90％90%
实施例33Example 33 500500 90％90%
实施例34Example 34 500500 92％92%
实施例35Example 35 500500 91％91%
实施例36Example 36 500500 89％89%
实施例37Example 37 500500 93％93%
实施例38Example 38 500500 94％94%
实施例39Example 39 500500 90％90%
实施例40Example 40 500500 89％89%
实施例41Example 41 500500 90％90%
实施例42Example 42 500500 90％90%
实施例43Example 43 500500 90％90%
实施例44Example 44 500500 87％87%
实施例45Example 45 500500 89％89%
实施例46Example 46 500500 90％90%
实施例47Example 47 500500 89％89%
实施例48Example 48 500500 90％90%
实施例49Example 49 500500 88％88%
实施例50Example 50 500500 89％89%
实施例51Example 51 500500 88％88%
实施例52Example 52 500500 90％90%
实施例53Example 53 500500 91％91%
实施例54Example 54 500500 94％94%
实施例55Example 55 500500 95％95%
实施例56Example 56 500500 95％95%
对比例3Comparative Example 3 500500 82％82%
对比例4Comparative Example 4 500500 81％81%
从表5中的测试数据可以看出，利用本申请提供的方法得到的锡-石墨双 离子电池500次后的容量保持率要明显高于对比例3和对比例4，说明利用本申请提供的方法能显著提高锡-石墨双离子电池的循环性能。It can be seen from the test data in Table 5 that the capacity retention rate of the tin-graphite dual-ion battery obtained by the method provided in this application after 500 times is significantly higher than that in Comparative Example 3 and Comparative Example 4, indicating that the application provided by this application The method can significantly improve the cycle performance of tin-graphite dual ion batteries.
从实施例29-53中的数据可以看出，当弹性粘结剂的种类不同、导电剂不同以及弹性粘结剂和导电剂的添加量不同时，均会对电池的循环性能产生一定的影响。其中，弹性粘结剂的选择产生的影响较大，而导电剂的影响则相对较小。As can be seen from the data in Examples 29-53, when the types of elastic binders are different, the conductive agent is different, and the addition amounts of the elastic binder and the conductive agent are different, it will have a certain effect on the cycle performance of the battery . Among them, the influence of the choice of elastic binder is greater, while the influence of the conductive agent is relatively small.
从实施例29和实施例54-56中的数据可以看出，当添加偶联剂后，还可以进一步提高电池的循环性能，且不同的偶联剂对电池的循环性能也会有一定的影响。It can be seen from the data in Example 29 and Examples 54-56 that when the coupling agent is added, the cycle performance of the battery can be further improved, and different coupling agents will also have a certain effect on the cycle performance of the battery .
对所公开的实施例的上述说明，使本领域专业技术人员能够实现或使用本申请。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的，本文中所定义的一般原理可以在不脱离本申请的精神或范围的情况下，在其它实施例中实现。因此，本申请将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。The above description of the disclosed embodiments enables those skilled in the art to implement or use this application. Various modifications to these embodiments will be apparent to those skilled in the art. The general principles defined in this document can be implemented in other embodiments without departing from the spirit or scope of the present application. Therefore, the present application will not be limited to the embodiments shown in this document, but should conform to the widest scope consistent with the principles and novel features disclosed in this document.

Claims (13)

  1. 一种含锡负极材料，其特征在于，按重量百分比计包括：锡颗粒70％～90％、弹性粘结剂5％～15％和导电剂5％～15％；A tin-containing negative electrode material, characterized in that, by weight percentage, it includes: tin particles 70% to 90%, elastic binder 5% to 15% and conductive agent 5% to 15%;
    所述锡颗粒为微米级或纳米级的锡颗粒。The tin particles are micron or nanoscale tin particles.
  2. 根据权利要求1所述的含锡负极材料，其特征在于，按重量百分比计包括：锡颗粒72％～88％、弹性粘结剂6％～14％和导电剂6％～14％。The tin-containing negative electrode material according to claim 1, characterized in that, by weight percentage, it includes: tin particles 72% to 88%, elastic binder 6% to 14% and conductive agent 6% to 14%.
  3. 根据权利要求2所述的含锡负极材料，其特征在于，按重量百分比计包括：锡颗粒75％～85％、弹性粘结剂8％～12％和导电剂8％～12％。The tin-containing negative electrode material according to claim 2, characterized in that, by weight percentage, it includes: tin particles 75%-85%, elastic binder 8%-12% and conductive agent 8%-12%.
  4. 根据权利要求1所述的含锡负极材料，其特征在于，所述弹性粘结剂包括海藻酸盐类粘结剂、多糖类粘结剂、羧甲基纤维素盐粘结剂、聚烯烃类粘结剂、聚氨酯类粘结剂、聚酯类粘结剂、聚酰胺类粘结剂或聚亚胺类粘结剂中的至少一种。The tin-containing negative electrode material according to claim 1, wherein the elastic binder includes an alginate binder, a polysaccharide binder, a carboxymethyl cellulose salt binder, a polyolefin At least one of a binder, a polyurethane binder, a polyester binder, a polyamide binder, or a polyimide binder.
  5. 根据权利要求4所述的含锡负极材料，其特征在于，所述弹性粘结剂包括海藻酸钙、环糊精聚合物、***树胶、黄原胶、胍尔豆胶、刺槐豆胶、刺梧桐树胶、***树脂-聚丙烯酸共聚物、醋酸乙烯树脂、聚丙烯酸-聚乙烯醇共聚物、聚乙烯醇-聚乙烯亚胺共聚物、聚丙烯酸-羧甲基纤维素钠共聚物、聚丙烯酸铵、聚丙烯酸钠接枝羧甲基纤维素钠或海藻酸钠-羧甲基壳聚糖共聚物中的至少一种。The tin-containing negative electrode material according to claim 4, wherein the elastic binder comprises calcium alginate, cyclodextrin polymer, gum arabic, xanthan gum, guar gum, locust bean gum, thorn Indus gum, arabic resin-polyacrylic acid copolymer, vinyl acetate resin, polyacrylic acid-polyvinyl alcohol copolymer, polyvinyl alcohol-polyethyleneimine copolymer, polyacrylic acid-carboxymethylcellulose sodium copolymer, ammonium polyacrylate At least one of sodium polyacrylate grafted sodium carboxymethyl cellulose or sodium alginate-carboxymethyl chitosan copolymer.
  6. 根据权利要求1所述的含锡负极材料，其特征在于，所述导电剂包括有机导电剂和/或无机导电剂；The tin-containing negative electrode material according to claim 1, wherein the conductive agent comprises an organic conductive agent and/or an inorganic conductive agent;
    所述有机导电剂包括离子型有机导电剂和/或电子型有机导电剂；The organic conductive agent includes an ionic organic conductive agent and/or an electronic organic conductive agent;
    所述离子型有机导电剂包括：聚氧化乙烯、聚环氧丙烷、聚丁二酸乙二醇 酯、聚葵二酸乙二酸酯或聚乙二醇亚胺中的至少一种；The ionic organic conductive agent includes: at least one of polyethylene oxide, polypropylene oxide, polyethylene succinate, polyethylene oxalate, or polyethylene glycol imine;
    所述电子型有机导电剂包括聚吡咯、聚对苯撑、聚苯硫醚、聚噻吩、聚对苯撑乙烯、聚苯胺中的至少一种；The electronic organic conductive agent includes at least one of polypyrrole, polyparaphenylene, polyphenylene sulfide, polythiophene, polyparaphenylene vinylene, and polyaniline;
    所述无机导电剂包括导电碳材料和/或导电金属材料。The inorganic conductive agent includes a conductive carbon material and/or a conductive metal material.
  7. 根据权利要求1，4-6任一项所述的含锡负极材料，其特征在于，按重量百分比计包括偶联剂0.5％～2％；The tin-containing negative electrode material according to any one of claims 1, 4-6, characterized in that it comprises a coupling agent 0.5%-2% by weight percentage;
    所述偶联剂包括铬络合物偶联剂、硅烷偶联剂、钛酸酯偶联剂或铝酸盐偶联剂中的至少一种。The coupling agent includes at least one of a chromium complex coupling agent, a silane coupling agent, a titanate coupling agent, or an aluminate coupling agent.
  8. 一种权利要求1-7任一项所述的含锡负极材料的制备方法，其特征在于，将所述锡颗粒、所述弹性粘结剂和所述导电剂以及任选的所述偶联剂混合，得到所述含锡负极材料。A method for preparing a tin-containing negative electrode material according to any one of claims 1-7, characterized in that the tin particles, the elastic binder, the conductive agent, and optionally the coupling Agents are mixed to obtain the tin-containing negative electrode material.
  9. 一种负极浆料，其特征在于，将权利要求1-7任一项所述的含锡负极材料与有机溶剂混合后得到所述负极浆料；A negative electrode slurry, characterized in that the negative electrode slurry is obtained by mixing the tin-containing negative electrode material according to any one of claims 1 to 7 with an organic solvent;
    将所述锡颗粒、所述弹性粘结剂和所述导电剂以及任选的偶联剂混合后研磨均匀，得到所述负极浆料；Mixing the tin particles, the elastic binder, the conductive agent, and the optional coupling agent, and grinding them evenly to obtain the negative electrode slurry;
    或，提供锡颗粒与有机溶剂组成的悬浮液，并将任选的偶联剂溶于所述悬浮液中，再加入所述粘结剂和所述导电剂混合均匀，得到所述负极浆料。Or, provide a suspension composed of tin particles and an organic solvent, and dissolve the optional coupling agent in the suspension, and then add the binder and the conductive agent to mix evenly to obtain the negative electrode slurry .
  10. 一种负极，其特征在于，包括负极集流体和形成于所述负极集流体表面的负极材料层，所述负极材料层由权利要求1-7任一项所述的含锡负极材料制备而成。A negative electrode, characterized by comprising a negative electrode current collector and a negative electrode material layer formed on the surface of the negative electrode current collector, the negative electrode material layer is prepared from the tin-containing negative electrode material according to any one of claims 1-7 .
  11. 一种权利要求10所述的负极的制备方法，其特征在于，利用权利要求1-7任一项所述的含锡负极材料在所述负极集流体表面制备所述负极材料层后，得到所述负极；A method for preparing a negative electrode according to claim 10, characterized in that the tin-containing negative electrode material according to any one of claims 1 to 7 is used to prepare the negative electrode material layer on the surface of the negative electrode current collector to obtain State negative
    将权利要求9所述的负极浆料涂覆于所述负极集流体表面，干燥后得到所述负极。Applying the negative electrode slurry of claim 9 to the surface of the negative electrode current collector, and drying to obtain the negative electrode.
  12. 一种二次电池，其特征在于，包括正极、电解液、隔膜和权利要求11所述的负极；A secondary battery characterized by comprising a positive electrode, an electrolyte, a separator and the negative electrode of claim 11;
    所述二次电池包括单离子电池和双离子电池；The secondary battery includes a single ion battery and a dual ion battery;
    所述双离子电池包括锡-石墨双离子电池。The dual ion battery includes a tin-graphite dual ion battery.
  13. 一种用电设备，其特征在于，包括权利要求12所述的二次电池。An electric appliance, characterized by comprising the secondary battery according to claim 12.
PCT/CN2019/125440 2018-12-19 2019-12-14 Tin-containing anode material, anode and preparation method therefor and anode slurry thereof, secondary battery and electrical equipment WO2020125562A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201811561445.1 2018-12-19
CN201811561445.1A CN109671936B (en) 2018-12-19 2018-12-19 Tin-containing negative electrode material, negative electrode, preparation method of negative electrode material, negative electrode slurry, secondary battery and electric equipment

Publications (1)

Publication Number Publication Date
WO2020125562A1 true WO2020125562A1 (en) 2020-06-25

Family

ID=66143959

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/125440 WO2020125562A1 (en) 2018-12-19 2019-12-14 Tin-containing anode material, anode and preparation method therefor and anode slurry thereof, secondary battery and electrical equipment

Country Status (2)

Country Link
CN (1) CN109671936B (en)
WO (1) WO2020125562A1 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112408355A (en) * 2020-08-26 2021-02-26 中南大学 Preparation method of tin simple substance/Prussian blue framework @ carbon composite material
CN112456497A (en) * 2020-11-23 2021-03-09 北京工业大学 Si nanowire manufacturing method and Si nanowire lithium ion battery electrode manufacturing method
CN112909230A (en) * 2021-01-19 2021-06-04 江西科技师范大学 Electrode for absorbing composite tin elementary substance by using dunaliella salina and preparation method thereof
CN114447519A (en) * 2020-10-21 2022-05-06 安徽盟维新能源科技有限公司 Lithium battery diaphragm, lithium metal battery and preparation method thereof
CN116463885A (en) * 2023-03-29 2023-07-21 郑州大学 CS-FEC/CS-Arg-FEC multifunctional protection liquid for protecting paper cultural relics

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109671936B (en) * 2018-12-19 2021-10-29 深圳先进技术研究院 Tin-containing negative electrode material, negative electrode, preparation method of negative electrode material, negative electrode slurry, secondary battery and electric equipment
CN110277559B (en) * 2019-06-17 2022-02-01 南开大学 Polyimide conductive binder for silicon-based negative electrode of lithium ion battery
CN111769282B (en) * 2020-06-22 2021-10-22 上海交通大学 Application method of water-based binder in magnesium-sulfur battery
CN112563478B (en) * 2020-12-10 2022-05-03 深圳中科瑞能实业有限公司 Alloy type negative electrode slurry based on modification, preparation method and secondary battery
CN114335546B (en) * 2022-03-07 2022-05-10 北京壹金新能源科技有限公司 Binder for battery electrode and battery electrode

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1682393A (en) * 2002-09-20 2005-10-12 3M创新有限公司 Anode compositions having an elastomeric binder and an adhesion promoter
CN108155363A (en) * 2017-12-26 2018-06-12 深圳先进技术研究院 Application, aluminum honeycomb, preparation method and secondary cell of the polymeric coating layer in aluminum honeycomb
CN108346523A (en) * 2018-02-13 2018-07-31 清华大学 A kind of preparation method containing lithium an- ode of mixed type energy storage device
CN109671936A (en) * 2018-12-19 2019-04-23 深圳先进技术研究院 Containing tin negative pole material, cathode and preparation method thereof and negative electrode slurry, secondary cell and electrical equipment

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB201014707D0 (en) * 2010-09-03 2010-10-20 Nexeon Ltd Electroactive material
CN103346304B (en) * 2013-06-25 2015-04-22 南开大学 Tin-carbon composite material for lithium secondary battery negative electrode and preparation method thereof
CN107482222A (en) * 2017-09-05 2017-12-15 深圳市比克动力电池有限公司 Combined conductive agent, electrodes of lithium-ion batteries and lithium ion battery
CN108206285B (en) * 2017-12-12 2021-08-24 中国科学院物理研究所 Composite coated nano tin anode material and preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1682393A (en) * 2002-09-20 2005-10-12 3M创新有限公司 Anode compositions having an elastomeric binder and an adhesion promoter
CN108155363A (en) * 2017-12-26 2018-06-12 深圳先进技术研究院 Application, aluminum honeycomb, preparation method and secondary cell of the polymeric coating layer in aluminum honeycomb
CN108346523A (en) * 2018-02-13 2018-07-31 清华大学 A kind of preparation method containing lithium an- ode of mixed type energy storage device
CN109671936A (en) * 2018-12-19 2019-04-23 深圳先进技术研究院 Containing tin negative pole material, cathode and preparation method thereof and negative electrode slurry, secondary cell and electrical equipment

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112408355A (en) * 2020-08-26 2021-02-26 中南大学 Preparation method of tin simple substance/Prussian blue framework @ carbon composite material
CN112408355B (en) * 2020-08-26 2023-03-24 中南大学 Preparation method of tin simple substance/Prussian blue framework @ carbon composite material
CN114447519A (en) * 2020-10-21 2022-05-06 安徽盟维新能源科技有限公司 Lithium battery diaphragm, lithium metal battery and preparation method thereof
CN114447519B (en) * 2020-10-21 2024-01-26 安徽盟维新能源科技有限公司 Lithium battery diaphragm, lithium metal battery and preparation method of lithium battery diaphragm
CN112456497A (en) * 2020-11-23 2021-03-09 北京工业大学 Si nanowire manufacturing method and Si nanowire lithium ion battery electrode manufacturing method
CN112909230A (en) * 2021-01-19 2021-06-04 江西科技师范大学 Electrode for absorbing composite tin elementary substance by using dunaliella salina and preparation method thereof
CN116463885A (en) * 2023-03-29 2023-07-21 郑州大学 CS-FEC/CS-Arg-FEC multifunctional protection liquid for protecting paper cultural relics
CN116463885B (en) * 2023-03-29 2024-04-05 郑州大学 CS-FEC/CS-Arg-FEC multifunctional protection liquid for protecting paper cultural relics

Also Published As

Publication number Publication date
CN109671936B (en) 2021-10-29
CN109671936A (en) 2019-04-23

Similar Documents

Publication Publication Date Title
WO2020125562A1 (en) Tin-containing anode material, anode and preparation method therefor and anode slurry thereof, secondary battery and electrical equipment
US11326010B2 (en) Agent for dispersing electrically conductive carbon material, and dispersion of electrically conductive carbon material
Lingappan et al. The significance of aqueous binders in lithium-ion batteries
CN102576858B (en) Lithium ion secondary battery negative pole and lithium rechargeable battery
JP5953966B2 (en) Positive electrode composite
KR20150067049A (en) Conductive composition for rechargeable lithium battery, positive electrode for rechargeable lithium battery and rechargeable lithium battery including the same
WO2012114590A1 (en) Electrode for non-aqueous electrolyte secondary battery, method for producing same, and non-aqueous electrolyte secondary battery
JP2018518810A (en) Method for producing electrode slurry for lithium secondary battery
CN104241696A (en) Lithium ion battery with high energy density and preparation method of lithium ion battery with high energy density
WO2018170925A1 (en) Calcium ion secondary cell, and manufacturing method thereof
JP6101683B2 (en) Negative electrode for secondary battery, method for producing the same, and secondary battery
CN114497549B (en) Method for electrochemically preparing positive electrode lithium supplement material, lithium supplement material and lithium supplement slurry
WO2017216822A1 (en) Fast chargeable lithium ion batteries with nano-carbon coated anode material and imide anion based lithium salt electrolyte
TW201740603A (en) Nonaqueous secondary cell
WO2020125561A1 (en) Negative electrode material, negative electrode and preparation method therefor, negative electrode slurry, secondary battery and electric appliance
Yuan et al. In-situ crosslinked binder for high-stability S cathodes with greatly enhanced conduction and polysulfides anchoring
Jia et al. Novel rigid-flexible hydrogenated carboxyl nitrile rubber-guar gum binder for ultra-long cycle silicon anodes in lithium-ion batteries
WO2020066909A1 (en) Electrode for secondary batteries and lithium ion secondary battery
JP5707804B2 (en) Slurry composition for positive electrode of non-aqueous electrolyte secondary battery
CN108028365A (en) It is used to prepare the method for lithium ion secondary battery cathode
CN112164769A (en) Preparation method of silicon-based negative electrode material based on polyimide-based electrode binder
JP5232353B2 (en) Non-aqueous electrolyte secondary battery electrode composition, electrode and battery using the same
CN109935780B (en) Binder and preparation method thereof, negative electrode material composition, battery negative electrode and preparation method thereof, and lithium ion battery
CN114142028B (en) Negative electrode material, negative electrode sheet, preparation method and application thereof
JP2011181387A (en) Manufacturing method of electrode mixture for electrochemical element

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: 19899325

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 11-11-2021)

122 Ep: pct application non-entry in european phase

Ref document number: 19899325

Country of ref document: EP

Kind code of ref document: A1