WO2020125561A1 - 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 - Google Patents

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 Download PDF

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WO2020125561A1
WO2020125561A1 PCT/CN2019/125438 CN2019125438W WO2020125561A1 WO 2020125561 A1 WO2020125561 A1 WO 2020125561A1 CN 2019125438 W CN2019125438 W CN 2019125438W WO 2020125561 A1 WO2020125561 A1 WO 2020125561A1
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Prior art keywords
negative electrode
metal
electrode material
binder
coupling agent
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PCT/CN2019/125438
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English (en)
French (fr)
Inventor
唐永炳
谢东豪
张苗
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深圳先进技术研究院
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Publication of WO2020125561A1 publication Critical patent/WO2020125561A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • 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 invention relates to the field of batteries, in particular to a negative electrode material, a negative electrode and a method for preparing the same, a negative electrode slurry, a secondary battery, and an electric device.
  • Lithium-ion batteries have the advantages of high energy density, high efficiency, long cycle life, no memory effect and fast discharge, so there is a huge market demand in consumer electronics and electric vehicles, power grid peaking, energy storage power supply, aerospace and other fields .
  • the development of anode materials with abundant reserves, low cost and easy availability, and excellent electrochemical performance is the current research and development direction.
  • lithium-ion battery anode materials include graphite anodes, silicon anodes, and metal anodes.
  • metal negative electrodes have also become a hot spot in current research.
  • lithium metal anodes have high capacity and good conductivity, but their charge-discharge mechanism is the lithium dissolution-deposition mechanism, which has potential safety problems due to the easy growth of dendrites.
  • the lithium resource reserves are very limited, resulting in Costs continue to rise during use; the development of metal anodes such as aluminum and tin not only increases the capacity of the anode but also solves the problem of limited lithium resource reserves.
  • the first object of the present invention is to provide a negative electrode material to alleviate at least one of the technical problems mentioned above.
  • the second object of the present invention is to provide a method for preparing a negative electrode material to obtain the above negative electrode material.
  • the third object of the present invention is to provide a negative electrode slurry containing the above negative electrode material.
  • the fourth object of the present invention is to provide a negative electrode.
  • the raw material of the negative electrode includes the aforementioned negative electrode material.
  • the negative electrode has the advantages of good cycle performance and high rate performance.
  • a fifth object of the present invention is to provide a secondary battery including the above-mentioned negative electrode, which has the advantages of good cycle performance and high rate performance.
  • a sixth object of the present invention is to provide an electric device including the above secondary battery.
  • a negative electrode material including metal nanosheets.
  • a method for preparing a negative electrode material, the metal nanosheet, the optional binder, the optional coupling agent, and the optional conductive agent are mixed to obtain the negative electrode material.
  • a negative electrode slurry is obtained by mixing the negative electrode material with an organic solvent.
  • An anode includes an anode material layer, and the anode material layer is prepared from the foregoing anode material.
  • a method for preparing a negative electrode After the negative electrode material layer is prepared by using the negative electrode material, the negative electrode is obtained.
  • a secondary battery includes the above negative electrode.
  • An electric device including the above secondary battery.
  • the present invention has the following beneficial effects:
  • the particle shape of the metal negative electrode active material is changed from the current conventional design.
  • the metal nanosheet with a two-dimensional shape is used as the negative electrode active material. Compared with the spherical metal particles, The metal nanosheet greatly reduces the surface curvature of the negative electrode active material particles, and at the same time has a high specific surface area.
  • the low-curvature surface increases the anchor point between the binder and the metal anode active material, which can ensure that the binder is stably attached to the surface of the metal nanosheet; at the same time, the two-dimensional structure of the metal nanosheet is easier to carry out in the thickness direction during the expansion process Expansion, thereby reducing the degree of stretching of the adhesive attached to the surface, thereby improving the current problems of metal negative electrode powdering and metal active materials easily splitting with the adhesive.
  • the present invention increases the specific surface area of the metal active material by nanometerizing the metal material, greatly increasing the alloying sites, effectively increasing the metal alloying speed, and thereby improving the rate performance of the metal active material as a negative electrode.
  • 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 form of the lower limit and the upper limit of the "range" disclosed in the present invention 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 invention provides a negative electrode material, including metal nanosheets.
  • the particle shape of the metal negative electrode active material is changed from the current conventional design.
  • the metal nanosheet with a two-dimensional shape is used as the negative electrode active material. Compared with the spherical metal particles, The metal nanosheet greatly reduces the surface curvature of the negative electrode active material particles, and at the same time has a high specific surface area.
  • the low-curvature surface increases the anchor point between the binder and the metal anode active material, which can ensure that the binder is stably attached to the surface of the metal nanosheet; at the same time, the two-dimensional structure of the metal nanosheet is easier to carry out in the thickness direction during the expansion process Expansion, thereby reducing the degree of stretching of the adhesive attached to the surface, thereby improving the current problems of metal negative electrode powdering and metal active materials easily splitting with the adhesive.
  • the present invention increases the specific surface area of the metal active material by nanometerizing the metal material, greatly increasing the alloying sites, effectively increasing the metal alloying speed, and thereby improving the rate performance of the metal active material as a negative electrode.
  • the metal nanosheet is a two-dimensional sheet-like structure, and its thickness belongs to a nanoscale size, for example, it can be 0.01 nm to several tens of nanometers. On a two-dimensional plane, its size is not specifically limited.
  • the thickness of the metal nanosheet may be, for example, 0.1 to 80 nm, preferably 0.1 to 50 nm, and more preferably 0.1 to 40 nm, wherein the thickness of the metal nanosheet is typical but not limited to, for example, 0.1 nm, 1nm, 5nm, 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm or 100nm.
  • the ratio of the area of the metal nanoplate to the thickness of the metal nanoplate is ⁇ 2, preferably 2 to 1000, and more preferably 2 to 100, wherein the ratio of the area of the metal nanoplate to the thickness of the metal nanoplate is typical but Non-limiting examples may be 2, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 500 or 1000.
  • the area of the metal nanosheet refers to the area of one side of the two-dimensional plane of the metal nanosheet, that is, the area of the side surface perpendicular to the thickness of the metal nanosheet.
  • the anode material containing the metal nanosheet can solve the problems that the current metal anode of the lithium ion battery is prone to pulverization and low rate performance.
  • the specific principle of using the metal nanosheet to solve the above problem is as follows.
  • the alloy formed after the metal negative electrode material is alloyed has poor conductivity, and the ion diffusion process of the alloying process is slow, resulting in metal
  • the negative electrode exhibits poor rate performance.
  • the invention increases the specific surface area of the metal negative electrode by nanometerizing the metal material, greatly increases the alloying sites, effectively improves the metal alloying speed, and further improves the rate performance of the metal material as the negative electrode.
  • the present invention does not specifically limit the types of metal nanoplates, and the metal of the metal nanoplates may be selected from Li, Al, Sn, Zn, Pd, Sb, Bi, Au, Ag, Pt, for example , Rh, Ir, Ru, Os, Li, Na, K, Mg, Ca, Cr, Mn, V, Ti, Fe, Co, Ni, Cu, Ga, Ge, Zr, Nb, Mo, Cd, In, Pb Or at least one of Pd or an alloy of at least one; preferably at least one of Li, Al, Sn, Mg, Zn, Sb, or Bi, or an alloy of at least one thereof.
  • the negative electrode material includes a binder
  • the binder includes an elastic binder and/or a conductive binder.
  • the elastic adhesive and the conductive adhesive are introduced, so that the adhesive has elasticity and conductivity.
  • the elastic adhesive may be added separately, or the conductive adhesive may be added separately, or the elastic adhesive and the conductive adhesive may be added at the same time.
  • a certain amount of conductive agent may be added.
  • no additional conductive agent can be added.
  • the distance between the adhesive anchor point of the adhesive and the metal nanosheet will increase, and the use of the elastic adhesive can ensure the bonding during the process
  • the agent layer does not crack.
  • the traditional conductive agent (such as carbon material) has a particle structure and a large volume size. During the expansion of the metal nanosheet, it will be squeezed with it. The larger volume of conductive particles may crush the metal nanosheet and damage the material structure. Reduce battery performance.
  • the use of conductive adhesive can be considered to be a more uniform conductive agent to a certain extent.
  • the use of the conductive adhesive can form a uniform polymer coating layer on the surface of the metal nanosheets, while protecting the metal nanosheets from damage while playing a bonding role.
  • another advantage of the cladding layer is that it can isolate the metal nanosheet from the electrolyte to a greater extent, reduce the loss of the material and improve the conductivity.
  • the elongation at break of the elastic binder is ⁇ 150%, preferably ⁇ 200%, wherein the elongation at break is typical but not limited, for example, it can be limited to 150%, 180 %, 200%, 300%, 500%, 800% or 1000%, etc.
  • the tensile strength of the elastic binder can be ensured to ensure that no breakage occurs during the volume expansion process.
  • the monomers of the elastic binder include at least styrene, olefin, diene, vinyl chloride, urethane, ester, amide or organic fluorine One, wherein the organic fluorines are preferably fluorine-containing olefins.
  • the styrene-based binder can be tough polystyrene TPS, styrene-isoprene-styrene block copolymer SIS, ethylene-butene copolymer is the middle elastic block linear tri-embedded copolymer SEBS , Hydrogenated styrene isoprene copolymer SEPS.
  • the olefin-based binder may be, for example, thermoplastic polyolefin elastomer TPO and polyolefin alloy thermoplastic elastomer TPV.
  • the diene-based binder may be, for example, thermoplastic polyimide elastomer TPI and thermoplastic polybutene elastomer TPB.
  • the vinyl chloride-based binder may be, for example, thermoplastic polyvinyl chloride elastomer TPVC and thermoplastic chlorinated polyethylene elastomer TCPE.
  • the urethane-based binder may be, for example, thermoplastic polyurethane elastomer rubber TPU.
  • the ester binder may be, for example, thermoplastic polyester elastomer TPEE.
  • the amide-based binder may be, for example, polyamide-based elastomer TPAE.
  • 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 conductive adhesive includes an electronic conductive adhesive and/or an ion conductive adhesive.
  • the conductive adhesive may be an electronic conductive adhesive, an ion conductive adhesive, or a combination of an electronic conductive adhesive and an ion conductive adhesive.
  • the electronically conductive adhesive includes at least one of polyaniline, polypyrrole, polythiophene, or polyacetylene.
  • the electronically conductive adhesive may be polyaniline, polypyrrole, polythiophene, polyacetylene, polyaniline-polypyrrole combination, polypyrrole-polythiophene combination, polythiophene and polyacetylene combination, or polyaniline-polypyrrole -Combination of polythiophenes.
  • the ion conductive adhesive includes at least one of polyethylene oxide, polypropylene oxide, polyethylene succinate, polyethylene sebacate, or polyethylene glycol imine.
  • the ion conductive adhesive may be polyethylene oxide, propylene oxide, polyethylene succinate, ethylene sebacate, polyethylene glycol imine, polyethylene oxide-ring Oxypropane combination or polyethylene glycol succinate-ethylene sebacate combination.
  • the weight ratio of the metal nanosheets to the binder is (0.1-50):1, preferably (1-20):1.
  • the adhesion between the metal nanosheets can be ensured, and the alloying reaction of the metal nanosheets itself can be ensured without interference.
  • the weight ratio of the metal nanosheet to the binder may be, for example, 0.1:1, 1:1, 5:1, 10:1, 15:1, 20:1, 25:1, 30:1. 35:1, 40:1, 45:1 or 50:1.
  • the negative electrode material includes a coupling agent.
  • 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 negative electrode material can greatly improve the interface contact between the metal nanosheet and the binder, while ensuring that the binder can evenly cover the metal nanosheet, while making the metal The nanosheet and the adhesive are firmly attached, and the contact between the metal nanosheet and the electrolyte is isolated.
  • the present invention builds a molecular bridge between the inorganic metal nanosheet and the organic binder by using a coupling agent, and further increases the adhesion of the binder by adding anchor points.
  • the adhesion between the binder and the current collector is poor, which may easily cause the metal nanosheets to peel off from the current collector during the charging and discharging process, and the use of the coupling agent can Increase the binding force between the metal nanosheet and the current collector to 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 weight ratio of the metal nanosheet to the coupling agent is (1-50):1, preferably (7-20):1.
  • the weight ratio of the metal nanosheet to the coupling agent may be, for example, 1:1, 5:1, 10:1, 15:1, 20:1, 25:1, 30:1, 35:1. 40:1, 45:1 or 50:1.
  • the negative electrode material includes a conductive agent.
  • a conductive agent is added to increase the conductivity of the negative electrode material.
  • the weight ratio of the conductive agent added to the negative electrode material may be, for example, 0.1% to 30%.
  • the conductive agent may be an ionic conductive agent or a non-ionic conductive agent.
  • the ionic conductive agent may be, for example, a compound of metal ions.
  • the lithium ion conductive agent may be lithium nitride, lithium carbonate, lithium phosphate, lithium sulfate, lithium silicate, lithium borate, lithium oxynitride, At least one of lithium lanthanum oxide, lithium titanium oxide, lithium titanium phosphate compound, lithium germanium phosphate compound, lithium silicon sulfide, lithium germanium sulfide, lithium phosphorus sulfide, or lithium germanium sulfide.
  • the non-ionic conductive agent includes conductive carbon materials and conductive metal materials.
  • the carbon conductive material may be conductive carbon black, conductive carbon spheres, conductive graphite, graphene, carbon nanotubes, carbon nanoribbons, carbon fibers, and reduced graphene oxide;
  • the conductive metal material may be elemental copper nanomaterials (nanowires, nanotubes, nanosheets, nanoribbons, nanoparticles, etc.) or elemental silver nanomaterials.
  • the metal nanosheets serve as the negative electrode active material to provide capacity for the battery.
  • the negative electrode material can use only the metal nanosheets as the negative electrode material.
  • the metal nanosheets are large-sized single
  • the sheet structure can also be used as a negative electrode material by selectively mixing small-sized metal nanosheets with a binder, a coupling agent, or a conductive agent.
  • the negative electrode material may be a mixture of metal nanosheets, a binder PVDF, and a conductive agent conductive carbon black, or a mixture of metal nanosheets, an elastic binder, a coupling agent, and a conductive agent, or a metal nanosheet And conductive adhesives.
  • the present invention provides a method for preparing a negative electrode material.
  • the method for preparing the negative electrode material comprises the metal nanosheet, the optional binder, the optional coupling agent, and the optional The conductive agent is mixed to obtain the negative electrode material.
  • the negative electrode material obtained by using the preparation method has all the advantages of the above negative electrode material, and will not be repeated here.
  • the present invention provides a negative electrode slurry, which is obtained by mixing the above negative electrode material with an organic solvent.
  • the negative electrode slurry can be prepared by the following method: the metal nanosheets and an organic solvent and optionally the binder, optionally the coupling agent and any The selected conductive agent is mixed and ground evenly to obtain the negative electrode slurry.
  • 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 can be prepared by, for example, the following method: Weighing the metal nanosheets, the binder, and the conductive agent according to a certain weight ratio, placing each material in a mortar, and adding an appropriate amount of organic solvent dropwise to grind evenly To obtain the negative electrode slurry.
  • the negative electrode slurry may be prepared by providing a suspension composed of metal nanosheets and an organic solvent, first dissolving the coupling agent in the suspension, and then adding The binder and the optional conductive agent are uniformly mixed to obtain the negative electrode slurry.
  • the coupling agent is first added to the suspension composed of the metal nanosheet and the organic solvent, which can make the coupling agent fully contact with the surface of the metal nanosheet and a bonding reaction occurs, and then the binder is added, thereby improving the adhesion between the metal nanosheet and the metal nanosheet The bonding strength between the cement.
  • the negative electrode slurry can be prepared by, for example, the following method:
  • Step B) Add a coupling agent to the suspension.
  • the dosage of the coupling agent is 0.1% to 5% of the mass of the metal nanosheets, stirring for 2 to 8 hours, so that the metal nanosheets are fully contacted with the coupling agent;
  • Step C) Add a binder, the dosage of the binder is 10% to 20% of the mass of the metal nanosheets, and stir for 6 to 12 hours to fully contact the metal nanosheets with the binder to obtain the negative electrode slurry.
  • the order of adding the metal nanosheets, the binder, the coupling agent, and the conductive agent can be adjusted according to the performance of the specific material, and is not specifically limited herein.
  • the present invention provides a negative electrode including a negative electrode material layer, the negative electrode material layer being prepared from the above negative electrode material.
  • the negative electrode includes only the negative electrode material layer, and the negative electrode material layer is prepared from the negative electrode material. After the negative electrode material is formed into a film, the negative electrode can be obtained.
  • the negative electrode includes a current collector, and the negative electrode material layer is formed on the surface of the current collector.
  • the current collector may be, for example, copper foil or aluminum foil.
  • the present invention provides a method for preparing the foregoing negative electrode. After the negative electrode material layer is prepared using the foregoing negative electrode material, the negative electrode is obtained.
  • the negative electrode slurry may be prepared using the foregoing negative electrode slurry.
  • the negative electrode slurry may be coated on the surface of the film-forming substrate or cast in a mold, dried and separated to obtain the negative electrode.
  • the negative electrode slurry is coated on the surface of the glass substrate, dried and separated to obtain the negative electrode.
  • a binder and an optional coupling agent are added dropwise to the obtained film layer, and dried to obtain the negative electrode.
  • a film-forming agent may be added to facilitate the film-forming of the metal nanosheets.
  • the film-forming agent may be, for example, graphene, nanotubes, or fiber fabrics. Wait.
  • the method of preparing a film layer containing metal nanosheets by suction filtration method may be, for example: dispersing the metal nanosheets and graphene in a weight ratio (3-20): 1 in an organic solvent by ultrasound, and then performing suction filtration on the resulting suspension
  • a solution containing a binder and a coupling agent is added dropwise on the surface until the composite film is infiltrated, and the negative electrode is obtained after drying again;
  • the weight ratio of the binder and the coupling agent is (10-50): 1, and the mass concentration of the solute in the solution is 10%-50%.
  • solute refers to binder and coupling agent.
  • Graphene can not only function as a conductor, but also as a film-forming agent to facilitate the adsorption of metal nanosheets.
  • the negative electrode includes a current collector and a negative electrode material layer
  • the negative electrode slurry may be coated on the surface of the current collector and dried to obtain the negative electrode.
  • the present invention provides a secondary battery including the above negative electrode.
  • the secondary battery includes a single ion battery and a dual ion battery.
  • the above negative electrode in the present invention 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 aluminum metal reaction In the battery system, for example, lithium ion-based dual ion batteries, various aluminum ion batteries, and so on.
  • the dual-ion battery system includes a dual-graphite-based lithium-based dual-ion battery system, an aluminum-graphite-based lithium-based dual-ion battery system, a tin-graphite-based sodium-based, potassium-based, and calcium-based dual-ion battery systems.
  • the present invention provides an electric device.
  • the electrical equipment may be, for example, an electronic device, a power tool, an electric vehicle, or a power storage system.
  • the lithium ion secondary battery in the embodiment of the present invention has better cycle stability and rate performance effects. The same effect can also be obtained in electronic devices, power tools, electric vehicles, and power storage systems that use the lithium ion battery of the embodiment of the present invention.
  • 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 be able to use various devices such as home electronic products.
  • This embodiment is a negative electrode material, including 80 mg metal nanosheets, 10 mg elastic binder, 10 mg conductive binder and 10 mg coupling agent, wherein the metal nanosheets are Sn nanosheets with a thickness in the range of 0.1-40 nm,
  • the elastic binder is SEBS
  • the conductive binder is polyethylene dioxythiophene (abbreviated as PEDOT)
  • the coupling agent is an aluminate coupling agent.
  • Examples 2 to 4 are each a negative electrode material. The difference from Example 1 is that the coupling agent is different.
  • the coupling agents in Examples 2 to 4 are respectively chromium complex coupling agent and titanate.
  • the coupling agent and the silane coupling agent are the same as in Example 1.
  • Examples 5 to 17 are respectively a negative electrode material. The difference from Example 1 is that the elastic binder is different.
  • the elastic binders in Examples 5 to 17 are respectively SEBS/PE blend and SEBS/ PP blend, SBS, TPO, TPI, TPVC, TPU, TPEE, TPF, SBR, NR, BR, FPM, the others are the same as in Example 1.
  • Examples 18 to 21 are respectively a negative electrode material. The difference from Example 1 is that the conductive binder is different.
  • the conductive binders in Examples 18 to 21 are respectively polypyrrole, polyaniline, PEO, and poly The ethylene glycol imine is the same as in Example 1.
  • This embodiment is a negative electrode material.
  • the difference from Embodiment 1 is that the metal nanosheets are different.
  • the metal nanosheets in this embodiment are Al nanosheets, and the others are the same as Embodiment 1.
  • This embodiment is a negative electrode material.
  • the difference from Embodiment 22 is that the conductive adhesive is different.
  • the conductive adhesive in this embodiment is PEO, and the others are the same as those in Embodiment 1.
  • This embodiment is a negative electrode material.
  • the difference from Embodiment 22 is that the elastic binder is different.
  • the elastic binder in this embodiment is SBR, and the other is the same as Embodiment 1.
  • composition of raw materials used in the negative electrode materials in Examples 1 to 24 is shown in Table 1.
  • This embodiment is a negative electrode material.
  • the difference from Embodiment 1 is that the thickness of the metal nanosheets in this embodiment is 50-80 nm. Among them, the thickness of the metal nanosheets is not a fixed value. The distribution of 50 to 80 nm is the same as that of Example 1.
  • This embodiment is a negative electrode material.
  • the difference from Embodiment 1 is that the thickness of the metal nanosheet in this embodiment is 100-200 nm.
  • the thickness of the metal nanosheet is not a fixed value, but is The distribution of 100 to 200 nm is the same as that of Example 1.
  • This embodiment is a negative electrode material.
  • the difference from Embodiment 1 is that the mass ratio of the metal nanosheet to the elastic binder in this embodiment is 5:1, and the others are the same as Embodiment 1.
  • This embodiment is a negative electrode material.
  • the difference from Embodiment 1 is that the mass ratio of the metal nanosheets to the elastic binder in this embodiment is 10:1, and the others are the same as Embodiment 1.
  • This embodiment is a negative electrode material.
  • the difference between this embodiment and embodiment 1 is that the mass ratio of the metal nanosheets to the coupling agent in this embodiment is 30:1, and the others are the same as embodiment 1.
  • This embodiment is a negative electrode material.
  • the difference from Embodiment 1 is that the mass ratio of the metal nanosheet to the coupling agent in this embodiment is 50:1, and the others are the same as Embodiment 1.
  • This embodiment is a negative electrode, and its preparation method includes the following steps:
  • the negative electrode slurry is coated on the surface of the copper foil, dried and cut into negative electrode pieces of suitable size to obtain a negative electrode.
  • This embodiment is a negative electrode, and its preparation method includes the following steps:
  • step S4 After the Sn nanosheet-graphene composite film is completely dried, the mixed solution obtained in step S3 is added dropwise on the surface until the composite film is completely wetted by the solution;
  • This comparative example is a negative electrode.
  • the negative electrode is a Sn sheet with a thickness of 50 microns.
  • This comparative example is a negative electrode.
  • the negative electrode is an Al sheet with a thickness of 50 microns.
  • A1) Disperse the metal nanosheets in 1.5ml of organic solvent by ultrasonic dispersion to form a uniform suspension; A2) Add the coupling agent to the suspension and stir for 2h;
  • step A3) Add an elastic binder and a conductive binder to the suspension obtained in step A2), and stir for 4 hours to obtain a negative electrode slurry.
  • the preparation method of the negative electrode is as follows: the obtained negative electrode slurry is coated on the surface of a copper foil and vacuum dried at 80°C; after drying, the coated copper foil is cut into negative electrode pieces of a suitable size to obtain a negative electrode.
  • the negative electrodes corresponding to the negative electrode materials of Examples 1-30 and the negative electrodes provided by Examples 31-32 and Comparative Examples 1-2 were used as battery negative electrodes, with lithium iron phosphate as the positive electrode and LiPF6/EC-DEC as the electrolyte , Where EC:DEC is 4:6, assembled into a battery.
  • Example 1 The batteries corresponding to Example 1 and Comparative Examples 1-2 were tested for rate performance, and the test results are shown in Table 3.
  • Example 1 Use the negative electrode material of Example 1 corresponding to the obtained negative electrode, and then use different positive electrode materials to prepare the positive electrode, using NaPF6/EC-EMC-DMC as the electrolyte, where EC: EMC: DMC is 1:1: 1, assembled into double ions battery. Among them, the selection of the positive electrode material in each battery is listed in Table 4. Then the electrical properties of the resulting battery were tested, and the test results are listed in Table 4.
  • Example 2 Compared with Example 1, compared with Example 1, the type of coupling agent has a certain influence on the electrical properties of the obtained negative electrode. It can be seen from Table 2 that the aluminate coupling agent and the titanate coupling agent are more effective in enhancing the interface between the metal nanosheet and the organic binder material.
  • Example 5-17 as compared with Example 1, the type of elastic binder has a certain influence on the electrical properties of the resulting negative electrode. It can be seen from Table 2 that TPE thermoplastic elastomers are more suitable for metal nanosheet negative electrodes than rubber-like materials, probably because TPE thermoplastic elastomers have a higher elastic modulus.
  • Examples 18-21 Compared with Example 1, Examples 18-21 have different conductive binders and have little effect on the electrical properties of the resulting negative electrode.
  • the data of Examples 25-30 and Comparative Example 1 can be seen that the thickness of the nano metal sheet, the mass ratio of the nano metal sheet to the elastic binder, and the mass ratio of the nano metal sheet to the coupling agent all affect the electrical properties of the negative electrode. There is a certain influence, when the thickness of the nano metal sheet is in the range of 0.1-40 nm, the performance is better; when the mass ratio of the nano metal sheet to the elastic binder (1-50): 1, and when the nano metal sheet and When the mass ratio of the coupling agent is (1-50):1, the obtained negative electrode has better electrical performance.
  • Example 31 and Example 32 are negative electrodes prepared by using different raw materials and methods. From the test data, it can be seen that the negative electrode prepared by different methods has certain differences in electrical properties, but compared with traditional negative electrodes , Its electrical performance has also improved.

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Abstract

一种负极材料、负极及其制备方法与负极浆料、二次电池和用电设备，涉及电池领域，负极材料包括金属纳米片；以及任选的弹性粘结剂、任选的导电粘结剂、任选的偶联剂以及任选的导电剂。负极材料能够缓解现有的金属负极作为电池时容易出现膨胀粉化、倍率性能差以及SEI膜不稳定的技术问题，达到提高电池循环稳定性和倍率性能的目的。

Description

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 技术领域
本发明涉及电池领域，尤其是涉及一种负极材料、负极及其制备方法与负极浆料、二次电池和用电设备。
背景技术
锂离子电池具有能量密度高、效率高、循环寿命长、无记忆效应和放电快速等优点，因而在消费电子产品和电动交通工具、电网调峰、储能电源、航空航天等领域有巨大市场需求。为应对锂离子电池目前面临的性能、成本及环境等方面的挑战，开发储量丰富、廉价易得、电化学性能优异的负极材料是目前研发方向。
现有已经商业化或者有商业化前景的锂离子电池负极材料包括石墨负极、硅负极以及金属负极等。为了得到低成本的负极，金属负极也已成为目前研究的热点。在金属负极中，锂金属负极虽然容量高并且导电性好，但是其充放电机理为锂的溶解-沉积机理，因易生长枝晶而具有潜在安全性问题，同时锂资源储量非常有限，导致在使用过程中成本不断攀升；铝和锡等金属负极的开发不仅提升了负极容量还解决了锂资源储量有限的问题。
但是利用金属箔作为负极极片时存在如下问题导致其循环性有待进一步提升：(1)金属负极合金化过程会产生巨大的体积膨胀，造成电极粉化引起容量衰减；(2)金属材料由于合金化位点有限，导致体相金属负极表现出较差的倍率性能；(3)由于金属负极体积在充放电过程中不断变化，表面的固体电解质膜(SEI膜)不稳定，在充放电过程中，SEI膜不断的生成-破裂-再生成，消耗锂离子和电解液。
为了解决上述问题，有研究人员利用球形的金属材料作为负极活性材料，但是本申请的申请人发现，球形颗粒的高表面曲率使得粘结剂聚合物链和纳米颗粒之间的锚固点的数量有限，不可避免地使一部分颗粒表面直接暴露于电解质中与电解质接触，因此，未能有效改善金属负极材料的上述问题。
有鉴于此，特提出本发明。
发明内容
本发明的第一目的在于提供一种负极材料，以缓解上述所提及技术问题中的至少一个。
本发明的第二目的在于提供一种负极材料的制备方法，以得到上述负极材料。
本发明的第三目的在于提供一种包含上述负极材料的负极浆料。
本发明的第四目的在于提供一种负极，该负极的原料包括上述负极材料，该负极具有循环性能好和倍率性能高的优点。
本发明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和倍率性能高的优点。
本发明的第六目的在于提供一种包括上述二次电池的用电设备。
为了实现本发明的上述目的，特采用以下技术方案：
一种负极材料，包括金属纳米片。
一种负极材料的制备方法，将所述金属纳米片、任选的所述粘结剂、任选的所述偶联剂以及任选的所述导电剂混合，得到所述负极材料。
一种负极浆料，将所述负极材料与有机溶剂混合后得到所述负极浆料。
一种负极，包括负极材料层，所述负极材料层由上述负极材料制备而成。
一种负极的制备方法，利用上述负极材料制备所述负极材料层后，得到所述负极。
一种二次电池，包括上述负极。
一种用电设备，包括上述二次电池。
与已有技术相比，本发明具有如下有益效果：
本发明提供的负极材料中，脱离目前的常规设计，对金属负极活性材料的颗粒形貌进行了改变，选用具有二维形貌的金属纳米片作为负极活性材料，相对于球形金属颗粒而言，金属纳米片大大降低了负极活性材料颗粒的表面曲率，同时具有较高的比表面积。低曲率表面增加了粘结剂与金属负极活性材料之间 的锚固点，能够保证粘结剂稳定附着在金属纳米片表面；同时，二维结构的金属纳米片在膨胀过程中更易在厚度方向进行膨胀，从而减少了表面附着的粘结剂的拉伸程度，进而改善了目前金属负极粉化、金属活性材料易与粘结剂分裂的问题。
另外，本发明通过将金属材料纳米化，增大金属活性材料的比表面积，使得合金化位点大大增加，有效提高了金属合金化速度，进而改善金属活性材料作为负极的倍率性能。
具体实施方式
下面将结合实施例对本发明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发明，而不应视为限制本发明的范围。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。
需要说明的是：
本发明中，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。
本发明中，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。
本发明中，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。
本发明中，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。
本发明中，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。
本发明所公开的“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。
本发明中，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。
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发明中。
一方面，本发明提供了一种负极材料，包括金属纳米片。
本发明提供的负极材料中，脱离目前的常规设计，对金属负极活性材料的颗粒形貌进行了改变，选用具有二维形貌的金属纳米片作为负极活性材料，相对于球形金属颗粒而言，金属纳米片大大降低了负极活性材料颗粒的表面曲率，同时具有较高的比表面积。低曲率表面增加了粘结剂与金属负极活性材料之间的锚固点，能够保证粘结剂稳定附着在金属纳米片表面；同时，二维结构的金属纳米片在膨胀过程中更易在厚度方向进行膨胀，从而减少了表面附着的粘结剂的拉伸程度，进而改善了目前金属负极粉化、金属活性材料易与粘结剂分裂的问题。
另外，本发明通过将金属材料纳米化，增大金属活性材料的比表面积，使得合金化位点大大增加，有效提高了金属合金化速度，进而改善金属活性材料作为负极的倍率性能。
本发明中，金属纳米片为二维片状结构，其厚度属于纳米级尺寸，例如可以为0.01nm到几十纳米，在二维平面上，其尺寸不受具体的限定。本发明中， 所述金属纳米片的厚度例如可以为0.1～80nm，优选为0.1～50nm，进一步优选为0.1～40nm，其中，金属纳米片的厚度典型但非限制性的例如可以为0.1nm、1nm、5nm、10nm、20nm、30nm、40nm、50nm、60nm、70nm、80nm或100nm。所述金属纳米片的面积与所述金属纳米片的厚度之比≥2，优选为2～1000，进一步优选为2～100，其中，金属纳米片的面积与金属纳米片的厚度之比典型但非限制性的例如可以为2、5、10、20、30、40、50、60、70、80、90、100、500或1000。其中，金属纳米片的面积是指金属纳米片二维平面的一侧的面积，即垂直于金属纳米片厚度的一侧表面的面积。
本发明中，包含该金属纳米片的负极材料可以解决目前锂离子电池的金属负极易出现粉化、倍率性能低的问题，具体的，利用该金属纳米片解决上述问题的具体原理如下。
1)针对于膨胀粉化问题：金属材料(如Li、Al、Sn等)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，因此本发明通过将金属材料纳米化，制备出金属纳米片，并利用金属纳米片作为负极活性材料，在很大程度上缓解了膨胀粉化问题，并有效提高电池的循环能力。
2)针对倍率不佳问题：在充放电过程中，传统利用金属箔片作为负极时，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较为缓慢，导致金属负极表现出较差的倍率性能。本发明通过将金属材料纳米化，增大了金属负极的比表面积，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。
3)针对SEI膜不稳定的问题：利用金属箔片作为负极时，或者利用球形金属颗粒作为负极时，在充放电过程中，金属在各个方向均有膨胀，从而导致SEI膜容易发生破裂。而将金属负极活性材料形成金属纳米片后，在充放电过程中，金属纳米片的膨胀收缩方向更大程度地在金属纳米片的厚度方向上进行，可以有效控制SEI膜的破裂。
可以理解的是，本发明并未对金属纳米片的种类做出具体限定，所述金属纳米片的金属例如可以选自Li、Al、Sn、Zn、Pd、Sb、Bi、Au、Ag、Pt、Rh、Ir、Ru、Os、Li、Na、K、Mg、Ca、Cr、Mn、V、Ti、Fe、Co、Ni、Cu、Ga、Ge、Zr、Nb、Mo、Cd、In、Pb或Pd中的至少一种或其中至少一种的合金；优选为Li、Al、Sn、Mg、Zn、Sb或Bi中的至少一种或其中至少一种的合金。
在本发明的一些实施方式中，所述负极材料包括粘结剂，所述粘结剂包括弹性粘结剂和/或导电粘结剂。
通过使用与金属纳米片牢固接触且具有弹性的粘结剂，在粘结金属活性材料的同时作为人造弹性SEI膜，起到隔绝金属纳米片与电解液并保证稳定包裹金属纳米片表面的作用。
本发明通过引入弹性粘结剂和导电粘结剂，从而使粘结剂具备弹性和导电性。需要说明的是，在引入粘结剂时，可以单独加入弹性粘结剂，也可以单独加入导电粘结剂，还可以同时加入弹性粘结剂和导电粘结剂。当只加入弹性粘结剂时，为了使保持负极材料的导电性，可以加入一定量的导电剂。当只加入导电粘结剂时，可以不用再额外加入导电剂。
在电池的充放电过程中，当金属纳米片发生膨胀时，粘结剂与金属纳米片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。
传统的导电剂(例如碳材料)为颗粒结构，体积尺寸较大，在金属纳米片膨胀过程中，会与其发生挤压，较大体积的导电颗粒可能会压破金属纳米片，破坏材料结构，降低电池性能。而导电粘结剂的使用在一定程度上可认为是更为均匀的导电剂。导电粘结剂的使用可在金属纳米片表面形成均匀的高分子包覆层，在起到粘结作用的同时，保护金属纳米片不受损伤。另外，包覆层的另一个优点是能较大程度地隔绝金属纳米片与电解液接触，减少材料的损耗并提高导电性。
在本发明进一步的实施方式中，所述弹性粘结剂的断裂伸长率≥150％，优选为≥200％，其中，断裂伸长率典型但非限制性的例如可以限定为150％、180％、200％、300％、500％、800％或1000％等等。
通过优化弹性粘结剂的断裂伸长率，可以保证弹性粘结剂的抗拉强度，以保证在体积膨胀过程中不会发生断裂。
在本发明的一些实施方式中，所述弹性粘结剂的单体包括苯乙烯类、烯烃类、双烯类、氯乙烯类、氨酯类、酯类、酰胺类或有机氟类中的至少一种，其中有机氟类优选为含氟烯烃。
其中，苯乙烯类粘结剂可以为韧性聚苯乙烯TPS，苯乙烯一异戊二烯一苯乙烯嵌段共聚物SIS，乙烯-丁烯共聚物为中间弹性嵌段的线性三嵌共聚物SEBS，氢化苯乙烯异戊二烯共聚物SEPS。烯烃类粘结剂例如可以为热塑性聚烯烃弹性体TPO，聚烯烃合金热塑性弹性体TPV。双烯类粘结剂例如可以为热塑性聚酰亚胺弹性体TPI，热塑性聚丁烯弹性体TPB。氯乙烯类粘结剂例如可以为热塑性聚氯乙烯弹性体TPVC和热塑性氯化聚乙烯弹性体TCPE。氨酯类粘结剂例如可以为热塑性聚氨酯弹性体橡胶TPU。酯类粘结剂例如可以为热 塑性聚酯弹性体TPEE。酰胺类粘结剂例如可以为聚酰胺类弹性体TPAE。
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。
在本发明的一些实施方式中，所述导电粘结剂包括电子导电粘结剂和/离子导电粘结剂。其中，和/或可以理解为，导电粘结剂可以为电子导电粘结剂、离子导电粘结剂或电子导电粘结剂与离子导电粘结剂的组合。
上述实施方式中，电子导电粘结剂包括聚苯胺、聚吡咯、聚噻吩或聚乙炔中的至少一种。例如，电子导电粘结剂可以为聚苯胺、聚吡咯、聚噻吩、聚乙炔、聚苯胺-聚吡咯的组合、聚吡咯-聚噻吩的组合、聚噻吩与聚乙炔的组合或聚苯胺-聚吡咯-聚噻吩的组合。离子导电粘结剂包括聚环氧乙烷、聚环氧丙烷、聚丁二酸乙二醇酯、聚癸二酸乙二醇酯或聚乙二醇亚胺中的至少一种。例如，离子导电粘结剂可以为聚环氧乙烷、环氧丙烷、聚丁二酸乙二醇酯、癸二酸乙二醇酯、聚乙二醇亚胺、聚环氧乙烷-环氧丙烷组合或聚丁二酸乙二醇酯-癸二酸乙二醇酯的组合。
在本发明的一些实施方式中，所述金属纳米片与所述粘结剂的重量比为(0.1～50):1，优选为(1～20):1。
通过优化金属纳米片与粘结剂的重量比，既可以保证金属纳米片之间的粘结力，又可以保证金属纳米片本身的合金化反应不受干扰。
上述实施方式中，金属纳米片与粘结剂的重量比例如可以为0.1:1、1:1、 5:1、10:1、15:1、20:1、25:1、30:1、35:1、40:1、45:1或50:1。
在本发明的一些实施方式中，所述负极材料包括偶联剂。
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。
本发明中，在负极材料中加入偶联剂可以极大地改善金属纳米片和粘结剂之间的界面接触，在保证粘结剂可均匀覆盖金属纳米片的同时，在成键作用下使得金属纳米片与粘结剂附着牢固，隔绝金属纳米片和电解液的接触。另一方面，本发明通过使用偶联剂在无机金属纳米片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金属负极活性材料的体积变化，粘结剂与集流体的附着力差，容易导致金属纳米片在充放电过程中从集流体上剥落，而偶联剂的使用可增加金属纳米片与集流体的结合力，减少剥落情况的发生。
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。
在本发明的一些实施方式中，所述金属纳米片与所述偶联剂的重量比为(1～50):1，优选为(7～20):1。
通过优化金属纳米片与偶联剂的重量比，既可以保证金属纳米片与粘结剂之间的粘结力，又可以保证金属纳米片本身的合金化反应不受干扰。
上述实施方式中，金属纳米片与偶联剂的重量比例如可以为1:1、5:1、10:1、15:1、20:1、25:1、30:1、35:1、40:1、45:1或50:1。
在本发明的一些实施方式中，所述负极材料中包括导电剂。添加导电剂以增加负极材料的导电性。其中，加入的导电剂的量占所述负极材料的重量比例如可以为0.1％～30％。
导电剂可以为离子型导电剂或非离子型导电剂。
其中，离子型导电剂例如可以为金属离子的化合物，以锂离子型导电剂为例，可以为氮化锂、碳酸锂、磷酸锂、硫酸锂、硅酸锂、硼酸锂、氮氧化磷锂、锂镧氧化物、锂钛氧化物、磷酸钛锂化合物、磷酸锗锂化合物、硅硫化锂、锗硫化锂、磷硫化锂或锗硫化磷锂中至少一种。
非离子型导电剂包括导电碳材料和导电金属材料，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。
通过上述分析可以看出，本发明的负极材料中，金属纳米片作为负极活性材料为电池提供容量，该负极材料中可以只用金属纳米片作为负极材料，此时金属纳米片为大尺寸的单片结构，同时，也可以将小尺寸的金属纳米片选择性的与粘结剂、偶联剂或导电剂混合作为负极材料使用。例如，该负极材料可以为金属纳米片、粘结剂PVDF和导电剂导电炭黑的混合物，也可以为金属纳米片、弹性粘结剂、偶联剂和导电剂混合物，还可以为金属纳米片和导电粘结剂的混合物。
第二方面，本发明提供了一种负极材料的制备方法，该制备方法是将所述金属纳米片、任选的所述粘结剂、任选的所述偶联剂以及任选的所述导电剂混合，得到所述负极材料。
利用该制备方法得到的负极材料具备上述负极材料的全部优点，在此不再赘述。
第三方面，本发明提供了一种负极浆料，将上述负极材料与有机溶剂混合后得到所述负极浆料。
将上述负极材料制备成负极浆料更方便电池的制备。
在本发明的一些实施方式中，所述负极浆料可以通过以下方法制备得到：将所述金属纳米片与有机溶剂以及任选的所述粘结剂、任选的所述偶联剂和任选的所述导电剂混合后研磨均匀，得到所述负极浆料。
该方法为常规浆料的制备方法，工艺成熟稳定，方便操作。
该实施方式中，负极浆料例如可以通过以下方法制备得到：按一定重量比称取金属纳米片、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。
在本发明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：提供金属纳米片与有机溶剂组成的悬浮液，先将偶联剂溶于所述悬浮液中，再加入粘结剂和任选的导电剂混合均匀，得到所述负极浆料。
先将偶联剂加入金属纳米片与有机溶剂组成的悬浮液中，可以使偶联剂与金属纳米片表面充分接触，发生键合反应，然后再加入粘结剂，从而提高金属纳米片与粘结剂之间的结合强度。
该实施方式中，负极浆料例如可以通过以下方法制备得到：
步骤A)将金属纳米片置于有机溶剂中超声分散，其比例为每80～100mg 金属纳米片分散于1～2ml有机溶剂中，超声分散时间为10～15分钟，得到悬浮液；
步骤B)向悬浮液中加入偶联剂，偶联剂的加入剂量为金属纳米片质量的0.1％～5％，搅拌2～8h，使金属纳米片充分与偶联剂接触；
步骤C)加入粘结剂，粘结剂的加入剂量为金属纳米片质量的10％～20％，搅拌6～12h，使金属纳米片与粘结剂充分接触，得到所述负极浆料。
需要说明的是，该实施方式中，金属纳米片、粘结剂、偶联剂和导电剂的加入顺序可以根据具体的材料的性能进行调整，在此不做具体的限定。
第四方面，本发明提供了一种负极，包括负极材料层，所述负极材料层由上述负极材料制备而成。
可以理解的是，在本发明的一些实施方式中，该负极只包括负极材料层，而该负极材料层由上述负极材料制备而成，将负极材料制备成膜后，可以得到该负极。
在本发明的另一些实施方式中，所述负极包括集流体，所述负极材料层形成于所述集流体表面。其中，该集流体例如可以为铜箔或铝箔。
第五方面，本发明提供了一种上述负极的制备方法，利用上述负极材料制备所述负极材料层后，得到所述负极。
为方便加工制备，可以将利用上述负极浆料制备该负极。
与上述负极的结构相对应，对于只包含负极材料层的负极，在本发明的一些实施方式中，可以将负极浆料涂覆于成膜基体表面或浇铸于模具中，干燥分离后得到所述负极，例如，将负极浆料涂覆于玻璃基板表面，干燥分离后得到所述负极。
或者，利用抽滤法制备含有金属纳米片的膜层后，再将粘结剂和任选的偶 联剂滴加于所得膜层中，干燥后得到所述负极。
需要说明的是，利用抽滤法制备含有金属纳米片的膜层的过程中，可以加入成膜剂以便于金属纳米片的成膜，成膜剂例如可以为石墨烯、纳米管或纤维织物等等。
利用抽滤法制备含有金属纳米片的膜层的方法例如可以为：将金属纳米片与石墨烯按重量比(3～20)：1超声分散于有机溶剂中，然后对所得悬浮液进行抽滤，得到金属纳米片-石墨烯复合膜，待复合膜干燥后在其表面滴加含有粘结剂和偶联剂的溶液至复合膜被浸润，再次干燥后得到所述负极；其中，含有粘结剂和偶联剂的溶液中，粘结剂和偶联剂的重量比为(10～50)：1，该溶液中溶质的质量浓度为10％～50％。其中，溶质指的是粘结剂和偶联剂。石墨烯既可以起到导电的作用，还可以起到成膜剂的作用，方便金属纳米片吸附到一起。
当负极包括集流体和负极材料层时，例如可以将负极浆料涂覆于集流体表面，干燥后得到所述负极。
第六方面，本发明提供了一种二次电池，包括上述负极。
其中，所述二次电池包括单离子电池和双离子电池。
本发明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，尤其适用于于铝金属反应的电池体系中，例如基于锂离子的双离子电池，各种铝离子电池等等。其中，双离子电池体系包括基于双石墨的锂基双离子电池体系，基于铝-石墨的锂基双离子电池体系，基于锡-石墨的钠基、钾基以及钙基双离子电池体系等。
通过选择不同的正极材料和电解液等原料与本发明提供的负极相匹配，可 以得到多种形式的二次电池。
第七方面，本发明提供了一种用电设备。
其中，用电设备例如可以为电子装置、电动工具、电动车辆、电力储存系统。在本发明实施方式的锂离子二次电池具有较好的循环稳定性和倍率性能效果。在使用本发明实施方式的锂离子电池的电子装置、电动工具、电动车辆、以及电力储存系统中也可以获得相同的效果。
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。
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。
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)。
电力储存系统是使用锂离子电池作为电力储存源的电力储存系统。例如，在家用电力储存系统中，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。
下面将结合实施例和对比例对本发明做进一步详细的说明。
实施例1
本实施例是一种负极材料，包括80mg金属纳米片、10mg弹性粘结剂、10mg导电粘结剂和10mg偶联剂，其中，金属纳米片为厚度为0.1～40nm范围内的Sn纳米片，弹性粘结剂为SEBS，导电粘结剂为聚乙烯二氧噻吩(缩写式为PEDOT)，偶联剂为铝酸酯偶联剂。
实施例2～4
实施例2～4分别是一种负极材料，与实施例1的不同之处在于偶联剂不同，实施例2～4中的偶联剂依次分别为铬络合物偶联剂、钛酸酯偶联剂、硅烷偶联剂，其他与实施例1相同。
实施例5～17
实施例5～17分别是一种负极材料，与实施例1的不同之处在于弹性粘结剂不同，实施例5～17中的弹性粘结剂依次分别为SEBS/PE共混物、SEBS/PP共混物、SBS、TPO、TPI、TPVC、TPU、TPEE、TPF、SBR、NR、BR、FPM，其他与实施例1相同。
实施例18～21
实施例18～21分别是一种负极材料，与实施例1的不同之处在于导电粘结剂不同，实施例18～21中的导电粘结剂依次分别为聚吡咯、聚苯胺、PEO、聚乙二醇亚胺，其他与实施例1相同。
实施例22
本实施例是一种负极材料，与实施例1的不同之处在于金属纳米片不同，本实施例中的金属纳米片为Al纳米片，其他与实施例1相同。
实施例23
本实施例是一种负极材料，与实施例22的不同之处在于导电粘结剂不同，本实施例中的导电粘结剂为PEO，其他与实施例1相同。
实施例24
本实施例是一种负极材料，与实施例22的不同之处在于弹性粘结剂不同，本实施例中的弹性粘结剂为SBR，其他与实施例1相同。
为了便于比较，将实施例1～24中的负极材料所用的原料组成列于表1。
表1实施例1～24负极材料的原料组成
Figure PCTCN2019125438-appb-000001
实施例25
本实施例是一种负极材料，与实施例1相同不同之处在于，本实施例中的金属纳米片的厚度为50～80nm，其中，金属纳米片的厚度并非为一个固定值，而是在50～80nm分布，其他与实施例1相同。
实施例26
本实施例是一种负极材料，与实施例1相同不同之处在于，本实施例中的金属纳米片的厚度为100～200nm，其中，金属纳米片的厚度并非为一个固定值，而是在100～200nm分布，其他与实施例1相同。
实施例27
本实施例是一种负极材料，与实施例1相同不同之处在于，本实施例中的金属纳米片与弹性粘结剂的质量比为5：1，其他与实施例1相同。
实施例28
本实施例是一种负极材料，与实施例1相同不同之处在于，本实施例中的金属纳米片与弹性粘结剂的质量比为10：1，其他与实施例1相同。
实施例29
本实施例是一种负极材料，与实施例1相同不同之处在于，本实施例中的金属纳米片与偶联剂的质量比为30：1，其他与实施例1相同。
实施例30
本实施例是一种负极材料，与实施例1相同不同之处在于，本实施例中的金属纳米片与偶联剂的质量比为50：1，其他与实施例1相同。
实施例31
本实施例是一种负极，其制备方法包括以下步骤：
S1)将80mg Sn纳米片、10mg导电石墨和10mg粘结剂PVDF以质量比 8：1：1置于研钵中，滴加适量NMP并研磨均匀，得到负极浆料；
S2)将负极浆料涂布于铜箔表面，干燥后裁切成合适尺寸大小的负极极片，得到负极。
实施例32
本实施例是一种负极，其制备方法包括以下步骤：
S1)将Sn纳米片与石墨烯按质量比8：1混合并超声分散于去离子水中，得到纳米片的悬浊液；
S2)对所得悬浊液进行真空抽滤，得到Sn纳米片-石墨烯的复合膜；
S3)配制弹性粘结剂和偶联剂的混合溶液，该混合溶液中，弹性粘结剂与偶联剂的质量比为20：1；
S4)待Sn纳米片-石墨烯的复合膜完全干燥后，在其表面滴加步骤S3所得混合溶液直至复合膜完全被溶液浸润；
S5)待复合膜再次干燥后裁切成极片，得到负极。
对比例1
本对比例是一种负极，该负极为Sn片，厚度为50微米。
对比例2
本对比例是一种负极，该负极为Al片，厚度为50微米。
先分别利用实施例1-30提供的负极材料制备成负极浆料，然后再将各组所得负极浆料涂覆于铜箔表面，于80℃真空干燥后，经裁切得到相应的负极。其中，负极浆料的制备过程如下：
A1)将金属纳米片分散于1.5ml有机溶剂中超声分散，形成均匀悬浊液；A2)在悬浊液中加入偶联剂，搅拌2h；
A3)在步骤A2)所得悬浊液中加入弹性粘结剂和导电粘结剂，搅拌4h，得到负极浆料。
负极的制备方法如下：将所得负极浆料涂布于铜箔表面，并于80℃真空干燥；干燥后将已涂布铜箔裁切为合适大小的负极极片，得到负极。
用实施例1-30的负极材料对应得到的负极以及用实施例31-32和对比例1-2提供的负极分别作为电池负极，以磷酸铁锂为正极，以LiPF6/EC-DEC为电解液，其中EC：DEC为4：6，组装成电池。
各组电池进行在0.5C下充放电400次后，测试各组电池的容量保持率和库伦效率，测试结果列于表2。
表2测试结果
Figure PCTCN2019125438-appb-000002
Figure PCTCN2019125438-appb-000003
对实施例1和对比例1-2对应的电池进行倍率性能测试，测试结果列于表3。
表3测试结果
Figure PCTCN2019125438-appb-000004
用实施例1的负极材料对应得到的负极，再以不同的正极材料制备正极，以NaPF6/EC-EMC-DMC为电解液，其中EC：EMC：DMC为1：1：1，组装成双离子电池。其中，各组电池中正极材料的选择列于表4。然后测试所得电池的电性能，测试结果列于表4。
表4
Figure PCTCN2019125438-appb-000005
实施例1-21以及实施例25-31中的数据均优于对比例1中的数据，而实施 例22-24的数据也明显优于对比例2的数据，说明，与传统金属负极相比，利用本发明提供的负极材料以及制备得到的负极，可以明显提升电池的循环性能。
实施例2-4与实施例1相比，偶联剂种类对所得负极的电性能有一定的影响。从表2中可以看出，铝酸酯偶联剂和钛酸酯偶联剂对于金属纳米片与有机粘结剂材料间的界面增强效果更为明显。
实施例5-17与实施例1相比，弹性粘结剂种类对所得负极的电性能有一定的影响。从表2中可以看出，TPE热塑性弹性体相较于橡胶类材料更适于金属纳米片负极，可能是因为TPE热塑性弹性体具备更高的弹性模量。
实施例18-21与实施例1相比，导电粘结剂不同，对所得负极的电性能影响不大。
实施例22-24将金属Sn纳米片替换为Al纳米片，依然得到良好的容量保持率，可知本发明对不同的金属材料均能产生相同效果。
实施例25-30与对比例1的数据可以看出，纳米金属片的厚度、纳米金属片与弹性粘结剂的质量比、纳米金属片与偶联剂的质量比，均对负极的电性能有一定的影响，当纳米金属片的厚度在0.1-40nm范围内时，性能更好；当纳米金属片与弹性粘结剂的质量比(1～50):1时，以及当纳米金属片与偶联剂的质量比为(1～50):1时，所得的负极的电性能更好。
实施例31和实施例32分别为利用不同的原料和方法制备得到的负极，从测试数据可以看出，利用不同的方法制备得到的负极，其电性能有一定的差异，但是与传统负极相比，其电性能也有所提升。
从表4中的测试数据可以看出，利用不同的正极材料装配钠双离子电池，从测试数据可以看出，该钠双离子电池具有较高的比容量和能量密度，说明本发明提供的负极材料可较好适用于双离子电池体系中。
尽管已用具体实施例来说明和描述了本发明，然而应意识到，在不背离本发明的精神和范围的情况下可以作出许多其它的更改和修改。因此，这意味着在所附权利要求中包括属于本发明范围内的所有这些变化和修改。

Claims (20)

  1. 一种负极材料，其特征在于，包括金属纳米片。
  2. 根据权利要求1所述的负极材料，其特征在于，所述金属纳米片的厚度为0.1～80nm；所述金属纳米片的面积与所述金属纳米片的厚度之比≥2。
  3. 根据权利要求1所述的负极材料，其特征在于，所述金属纳米片的金属选自Al、Sn、Zn、Pd、Sb、Bi、Au、Ag、Pt、Rh、Ir、Ru、Os、Li、Na、K、Mg、Ca、Cr、Mn、V、Ti、Fe、Co、Ni、Cu、Ga、Ge、Zr、Nb、Mo、Cd、In、Pb或Pd中的至少一种或其中至少一种的合金。
  4. 根据权利要求1所述的负极材料，其特征在于，所述负极材料包括粘结剂，所述粘结剂包括弹性粘结剂和/或导电粘结剂；所述金属纳米片与所述粘结剂的重量比为(0.1～50):1。
  5. 根据权利要求4所述的负极材料，其特征在于，所述弹性粘结剂的断裂伸长率≥150％。
  6. 根据权利要求4所述的负极材料，其特征在于，所述弹性粘结剂的单体包括苯乙烯类、烯烃类、双烯类、氯乙烯类、氨酯类、酯类、酰胺类或有机氟类中的至少一种，所述有机氟类为含氟烯烃。
  7. 根据权利要求4所述的负极材料，其特征在于，所述导电粘结剂包括电子导电粘结剂和/离子导电粘结剂。
  8. 根据权利要求7所述的负极材料，其特征在于，所述电子导电粘结剂包括聚苯胺、聚吡咯、聚噻吩或聚乙炔中的至少一种。
  9. 根据权利要求7所述的负极材料，其特征在于，所述离子导电粘结剂包括聚环氧乙烷、环氧丙烷、聚丁二酸乙二醇酯、癸二酸乙二醇酯或聚乙二醇亚胺 中的至少一种。
  10. 根据权利要求4所述的负极材料，其特征在于，所述负极材料包括偶联剂，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；所述金属纳米片与所述偶联剂的重量比为(1～50):1。
  11. 根据权利要求10所述的负极材料，其特征在于，所述负极材料中包括导电剂，所述导电剂占所述负极材料的重量比为0.1％～30％。
  12. 一种权利要求10所述的负极材料的制备方法，其特征在于，将所述金属纳米片、任选的所述粘结剂、任选的所述偶联剂以及任选的所述导电剂混合，得到所述负极材料。
  13. 一种负极浆料，其特征在于，将权利要求10所述的负极材料与有机溶剂混合后得到所述负极浆料。
  14. 一种权利要求13所述的负极浆料的制备方法，其特征在于，将所述金属纳米片与有机溶剂以及任选的所述粘结剂、任选的所述偶联剂和任选的所述导电剂混合后研磨均匀，得到所述负极浆料；或，提供金属纳米片与有机溶剂组成的悬浮液，先将偶联剂溶于所述悬浮液中，再加入粘结剂和任选的导电剂混合均匀，得到所述负极浆料。
  15. 一种负极，其特征在于，包括负极材料层，所述负极材料层由权利要求1-11任一项所述的负极材料制备而成；所述负极包括集流体，所述负极材料层形成于所述集流体表面。
  16. 一种权利要求15所述的负极的制备方法，其特征在于，利用权利要求1-11任一项所述的负极材料制备所述负极材料层后，得到所述负极。
  17. 根据权利要求16所述的制备方法，其特征在于，将权利要求13所述的负极浆料涂覆于成膜基体表面，干燥后得到所述负极；或，利用抽滤法制备含有 金属纳米片的膜层后，再将粘结剂和任选的偶联剂滴加于所得膜层中，干燥后得到所述负极。
  18. 根据权利要求16所述的制备方法，其特征在于，将权利要求13所述的负极浆料涂覆于集流体表面或浇铸于模具中，干燥分离后得到所述负极。
  19. 一种二次电池，其特征在于，包括权利要求15所述的负极。
  20. 一种用电设备，其特征在于，包括权利要求19所述的二次电池。
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