WO2019019411A1 - 具有疏水包覆层的金属锂-骨架碳复合材料、其制备方法与应用 - Google Patents

具有疏水包覆层的金属锂-骨架碳复合材料、其制备方法与应用 Download PDF

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WO2019019411A1
WO2019019411A1 PCT/CN2017/105675 CN2017105675W WO2019019411A1 WO 2019019411 A1 WO2019019411 A1 WO 2019019411A1 CN 2017105675 W CN2017105675 W CN 2017105675W WO 2019019411 A1 WO2019019411 A1 WO 2019019411A1
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lithium
hydrophobic
carbon composite
skeletal
metal lithium
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PCT/CN2017/105675
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English (en)
French (fr)
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康拓
陈立桅
卢威
沈炎宾
王亚龙
郭峰
刘承浩
陈鹏
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中能中科（天津）新能源科技有限公司
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Priority to JP2019560435A priority Critical patent/JP6994049B2/ja
Priority to KR1020197022415A priority patent/KR102314200B1/ko
Priority to US16/477,803 priority patent/US11462741B2/en
Priority to EP17918727.3A priority patent/EP3660962A4/en
Publication of WO2019019411A1 publication Critical patent/WO2019019411A1/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
    • H01M4/62—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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
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    • 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
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • 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
    • 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 invention relates to the field of battery technology, and more particularly to a lithium carbon composite material that can be used for a lithium battery.
  • Lithium-ion batteries are widely used in electronic products and power vehicles due to their high capacity, high energy density and good cycle stability.
  • the metal lithium negative electrode has the lowest reduction potential (-3.045V vs H 2 /H + ), ten times the theoretical capacity of the conventional graphite negative electrode (3860mA h g -1 , graphite negative electrode: 372mA h g -1 ) is called battery energy storage.
  • next-generation lithium battery with lithium metal anode lithium-sulfur battery (theoretical energy density 2600Wh/kg), and lithium air battery (theoretical energy density 5210Wh/kg) are required to be much higher than the current energy density of lithium-ion batteries.
  • the use of these batteries as a power source for a powered car is a car that has a longer range when fully charged, providing an excellent solution to the energy problems of today's world.
  • metal lithium negative electrode must be performed under the condition of argon gas protection, which seriously increases the use cost and safety hazard of the metal lithium.
  • dendrites will form on the surface, and the growth of dendrites may pierce the diaphragm and cause the positive and negative electrodes to meet and internal short circuit, releasing a large amount of heat, causing the battery to burn or even explode. .
  • the main object of the present invention is to provide a metal lithium-skeletal carbon composite material having a hydrophobic coating layer, a preparation method thereof, an electrode containing the metal lithium-framework carbon composite material, and an electrochemical energy storage device, and protecting water and oxygen A method of sensitive active metal materials.
  • a metal lithium-skeletal carbon composite having a hydrophobic coating layer comprising: a metallic lithium-skeletal carbon composite comprising a porous carbon material support and pores distributed at least in the porous carbon material support And a hydrophobic coating layer covering at least the metal lithium metal based nanoparticle-carbon composite material in the metal lithium-skeletal carbon composite material.
  • a method for preparing the above metal lithium-skeletal carbon composite having a hydrophobic coating layer comprises: mixing a metal lithium-carbon skeleton composite material with an organic solvent in which a film-forming hydrophobic substance or a compound having a lithium reactive portion and a hydrophobic portion is dissolved; obtaining a metal having a hydrophobic coating layer by solid-liquid separation or evaporation Lithium-skeletal carbon composite.
  • a method of protecting a material comprising an active metal that is sensitive to water and oxygen comprising forming a hydrophobic coating on the material, the hydrophobic coating coating at least the material Active metal in the middle.
  • an electrode comprising the above-described metallic lithium-skeletal carbon composite material having a hydrophobic coating layer as an electrode material.
  • an electrochemical energy storage device that includes the electrodes described above.
  • the formed dense hydrophobic coating layer has the function of isolating water and oxygen, and the coated material can be stably present in the air;
  • a coating layer formed of a compound having a lithium reactive portion and a hydrophobic portion has a dual function of a passivation layer and a hydrophobic layer;
  • the hydrophobic coating layer has a certain mechanical strength, can withstand the volume change of the solid electrolyte interface film (SEI film) on the surface of the metal lithium-skeletal carbon composite material, improve the cycle stability, and inhibit the generation of dendrites;
  • SEI film solid electrolyte interface film
  • Example 1 is a schematic view showing an octadecyl phosphate-coated metal lithium-skeletal carbon composite material in Example 1;
  • Example 2 is a scanning electron micrograph of the metal lithium-skeletal carbon composite material (a, b) and the octadecyl phosphate-metal lithium-skeletal carbon composite material (c, d) in Example 1.
  • Example 3 is an EDS (energy spectrum) analysis result of the change of oxygen content of the metal lithium-skeletal carbon composite material and the octadecyl phosphate-metal lithium-skeletal carbon composite material in Example 1 before and after exposure to dry air for 1 hour.
  • Example 4 is a test result of capacity stability of a metal lithium-skeletal carbon composite material and an octadecyl phosphate-metal lithium-skeletal carbon-carbon composite material in Example 1 in dry air.
  • Example 5 is a graph showing the different number of cycles of the octadecyl phosphate-metal lithium-skeletal carbon composite/lithium half-cell and the lithium metal-skeletal carbon composite/lithium half-cell in the constant current charge and discharge test in Example 1. Voltage vs. capacity graph.
  • Example 6 is an octadecyl phosphate-metal lithium-skeletal carbon composite material under the condition of 1 C rate in Example 1, metal lithium-skeletal carbon A composite material, a lithium sheet, and a discharge specific capacity vs. cycle number of a full battery composed of lithium iron phosphate, respectively.
  • Figure 8 is a graph showing the results of the stability test of PMMA-metal lithium-skeletal carbon composite in Example 2 in air.
  • Example 9 is an SEM image of a paraffin-metal lithium-skeletal carbon composite material in Example 3.
  • Figure 10 is a graph showing the results of the stability test of the paraffin-metal lithium-skeletal carbon composite in Example 3 in air.
  • Figure 11 is a SEM image of the dodecyl mercaptan-metal lithium-skeletal carbon composite material of Example 4.
  • Figure 12 is a graph showing the stability test results of the dodecyl mercaptan-metal lithium-skeletal carbon composite material in Example 4 in air.
  • Figure 13 is a SEM image of the phenylphosphoric acid-metal lithium-skeletal carbon composite material of Example 5.
  • Figure 14 is a graph showing the results of the stability test of the phenylphosphoric acid-metal lithium-skeletal carbon composite material in the air in Example 5.
  • Fig. 15 is a graph showing a constant current constant capacity test of the simulated battery in the fifth embodiment.
  • One aspect of the present invention provides a metal lithium-skeletal carbon composite material having a hydrophobic coating layer, comprising a metal lithium-skeletal carbon composite material and a hydrophobic coating layer, wherein the metal lithium-skeletal carbon composite material comprises a porous carbon material carrier And a metal lithium distributed in at least pores of the porous carbon material carrier, the hydrophobic coating layer coating at least metal lithium in the metal lithium-skeletal carbon composite material.
  • the hydrophobic coating layer can be composed of a film forming hydrophobic material that forms a hydrophobic film on the exposed surface of the metallic lithium-skeletal carbon composite.
  • the film-forming hydrophobic material is selected from the group consisting of a film-forming hydrophobic polymer and a film-forming hydrophobic small molecule
  • the film-forming hydrophobic polymer may include polymethyl methacrylate (PMMA), polyvinylidene fluoride. Ethylene (PVDF), polydimethylsiloxane (PDMS), etc.
  • film-forming hydrophobic small molecules may include paraffin, white oil, benzotriazole, and the like.
  • the hydrophobic coating layer may be composed of a compound having a lithium reactive portion and a hydrophobic portion, the lithium reactive portion reacts with the metallic lithium to passivate it, the hydrophobic portion forms a hydrophobic layer, and the hydrophobic layer is located at the most external.
  • the compound having a lithium reactive moiety and a hydrophobic moiety may be a linear small molecule compound having a lithium reactive group (lithium reactive moiety) at one end and a hydrophobic organic molecular chain at the other end ( The hydrophobic portion), by virtue of the anchoring effect of the lithium reactive group reacting with metallic lithium, the hydrophobic organic molecular chain is assembled into a hydrophobic layer on the surface of the metallic lithium.
  • linear small molecule compounds may include surfactants and the like.
  • the lithium reactive portion of the compound having a lithium reactive moiety and a hydrophobic moiety comprises phosphoric acid At least one of a group, a thiol group, a carbonic acid group, and optionally a fluorinated silane group.
  • the hydrophobic portion of the compound having a lithium reactive moiety and a hydrophobic moiety comprises a C 4 -C 22 alkyl group, a C 6 -C 24 aryl group, and a siloxane group At least one of these groups is optionally substituted with a hydrophobic substituent.
  • the C 4 -C 22 alkyl group may preferably be a C 8 -C 22 alkyl group or a C 12 -C 22 alkyl group.
  • the hydrophobic substituent may be selected from the group consisting of fluorine, perfluoro groups, siloxanes, and the like.
  • the hydrophobic coating layer has a thickness of 1-100 nm, such as 10-50 nm.
  • the hydrophobic coating layer has electrical and/or ionic conductivity.
  • the material of the porous carbon material carrier in the metal lithium-skeletal carbon composite material includes any one of carbon nanotubes, porous carbon, carbon black, graphene, carbon fiber, acetylene black, carbon aerogel or Combination of two or more.
  • the porous carbon material support has at least any one of a fine particulate solid aggregate structure, a spherical aggregate structure, a spheroidal aggregate structure, and a doughnut aggregate structure.
  • the pores of the porous carbon material support have an average pore diameter of from 10 to 100 nm.
  • the porous carbon material support has an average particle diameter of from 1 to 100 ⁇ m, preferably from 1 to 50 ⁇ m, or from 1 to 15 ⁇ m.
  • the porous carbon material support has an electrical conductivity of from 1*10 -3 to 10 S ⁇ cm -1 .
  • the porous carbon material support has a specific surface area of from 100 to 1500 m 2 /g.
  • the porous carbon material carrier can withstand a maximum pressure of 20 MPa or more.
  • the porous carbon material support comprises carbon fiber microspheres, porous carbon nanotube microspheres, and acetylene black.
  • the carbon fiber microspheres and the porous carbon nanotube microspheres are formed by intertwining a carbon nanotube or a carbon nanofiber with a large amount of nanometer-scale pores on the inside and on the surface.
  • Such microspheres have an approximately solid structure (like a wool-like structure), that is, the inside of the microspheres is filled with carbon nanotubes or carbon nanofibers, but nano-scale pores exist between the entangled agglomerated carbon nanotubes or carbon nanofibers, and these pores Can be used to hold metallic lithium particles.
  • Acetylene black is a carbon black obtained by cooling and collecting carbon dioxide by acetylene gas at a high temperature to isolate the air, and the particle diameter may be 40-50 nm.
  • the carbon nanotube microspheres are spherical or spheroidal particles having an average diameter of from 1 ⁇ m to 100 ⁇ m, preferably from 1 ⁇ m to 25 ⁇ m.
  • the carbon nanotubes include any one or a combination of two or more of multi-walled carbon nanotubes, double-walled carbon nanotubes, and single-walled carbon nanotubes, optionally subjected to surface function. Processing.
  • the group modified on the surface of the carbon nanotube may be selected from, but not limited to, a group such as -COOH, -OH, -NH 2 or the like.
  • the carbon nanotube microspheres can be dispersed by dispersing the carbon nanotubes in a solvent, and then spray dried. Prepared by drying.
  • the preparation method may include the following steps:
  • the carbon nanotubes are dispersed by ultrasonic treatment into a dispersion solvent (without a surfactant) to obtain a dispersion;
  • step B The dispersion obtained in the step A is sprayed through the nozzle of the spray dryer, and the inlet air temperature and the outlet air temperature are preset, and the solution is kept in a stirring state during the spraying process;
  • Cooling that is, obtaining carbon nanotube microspheres.
  • the solvent employs an organic and/or inorganic liquid capable of uniformly dispersing carbon nanotubes/carbon nanofibers and nanocarbon particles, for example, water, ammonia, hydrochloric acid solution, ethanol, acetone, isopropanol. Any combination of one or more.
  • an organic and/or inorganic liquid capable of uniformly dispersing carbon nanotubes/carbon nanofibers and nanocarbon particles, for example, water, ammonia, hydrochloric acid solution, ethanol, acetone, isopropanol. Any combination of one or more.
  • the solvent may be a mixture of ethanol and water in a volume ratio of 1:10.
  • the conditions of spray drying may include: an inlet air temperature of 150 to 250 ° C, an outlet air temperature of 75 ° C or higher, such as 75 to 150 ° C, or 90 ° C or higher; a preferred spray drying condition includes The inlet air temperature is 190 to 210 ° C, and the outlet air temperature is 90 to 110 ° C.
  • the spray rate during spray drying can range from 1 milliliter per minute to 100 liters per minute.
  • the metallic lithium-skeletal carbon composite may be obtained by mixing molten metal with a porous framework carbon material and cooling.
  • the mixing may include stirring and mixing the metallic lithium with the porous framework carbon material under heating (for example, about 200 ° C) or immersing the porous skeleton carbon material in the molten metallic lithium.
  • the preparation of the metallic lithium-skeletal carbon composite is carried out in an inert atmosphere, for example in a glove box under argon atmosphere (water content ⁇ 10 ppm, oxygen content ⁇ 10 ppm).
  • the lithium metal is supported in the metal lithium-skeletal carbon composite in an amount of from 10 to 90% by weight.
  • Another aspect of the present invention provides a method for preparing the above metal lithium-skeletal carbon composite material having a hydrophobic coating layer, comprising: dissolving a metal lithium-carbon skeleton composite material with a film forming hydrophobic material or having lithium The reactive portion is mixed with an organic solvent of the compound of the hydrophobic portion; a metal lithium-skeletal carbon composite having a hydrophobic coating layer is obtained by solid-liquid separation or evaporation.
  • metal lithium-carbon skeleton composite material film-forming hydrophobic substance
  • compound having a lithium-reactive portion and a hydrophobic portion refer to the relevant description in the above section.
  • the organic solvent used to dissolve the film-forming hydrophobic substance or the compound having a lithium reactive moiety and a hydrophobic moiety may include any one of n-hexane, tetrahydrofuran, cyclohexane, and N-methylpyrrolidone. kind or a combination of two or more.
  • the metal lithium-carbon skeleton composite material is mixed before the metal lithium-carbon skeleton composite material is mixed with an organic solvent in which a film-forming hydrophobic substance or a compound having a lithium reactive portion and a hydrophobic portion is dissolved.
  • an organic solvent in which a film-forming hydrophobic substance or a compound having a lithium reactive portion and a hydrophobic portion is dissolved.
  • Dispersed in another organic solvent which may be the same as or different from the organic solvent in which the film-forming hydrophobic substance or the compound having a lithium reactive portion and a hydrophobic portion is dissolved, and is selected from n-hexane, tetrahydrofuran, and ring. Any one or a combination of two or more of hexane and N-methylpyrrolidone.
  • the metal lithium-carbon skeleton composite is mixed with an organic solvent in which a film-forming hydrophobic substance or a compound having a lithium reactive portion and a hydrophobic portion is dissolved, under stirring.
  • the solid-liquid separation used to obtain the metallic lithium-skeletal carbon composite having a hydrophobic coating comprises filtration, such as suction filtration, and the like.
  • Another aspect of the present invention provides a method of protecting a material containing an active metal sensitive to water and oxygen, comprising forming a hydrophobic coating layer on the material, the hydrophobic coating layer covering at least the material Active metal.
  • the material to be protected includes a metallic lithium-carbon skeleton composite, lithium foil, lithium powder, and metallic sodium.
  • Another aspect of the present invention provides an electrode comprising the above-described metal lithium-skeletal carbon composite material having a hydrophobic coating layer as an electrode material.
  • Another aspect of the invention provides an electrochemical energy storage device comprising the electrode described above.
  • the electrochemical energy storage device comprises a metal lithium-oxide battery, a lithium ion battery, a lithium sulfur battery, or a metal lithium-air battery, and the like.
  • Embodiment 1 is a metal lithium-skeletal carbon composite material having a hydrophobic coating layer, comprising:
  • a metal lithium-skeletal carbon composite material comprising a porous carbon material support and metallic lithium distributed in at least pores of the porous carbon material support;
  • a hydrophobic coating layer covering at least the metallic lithium in the metallic lithium-skeletal carbon composite.
  • the hydrophobic coating layer is composed of a film-forming hydrophobic material covering an exposed surface of the metal lithium-skeletal carbon composite material;
  • the film-forming hydrophobic substance is selected from the group consisting of a film-forming hydrophobic polymer, such as polymethyl methacrylate (PMMA), polyvinylidene fluoride (PVDF), poly 2 Methyl siloxane (PDMS), and film-forming hydrophobic small molecules such as paraffin, white oil, benzotriazole.
  • Embodiment 3 is the metal lithium-skeletal carbon composite material according to Embodiment 1, wherein the hydrophobic coating layer is composed of a compound having a lithium reactive portion and a hydrophobic portion, the lithium reactive portion and the metal The lithium reacts to passivate it, and the hydrophobic portion forms an outer hydrophobic layer.
  • hydrophobic moiety comprises at least one of a C 4 -C 22 alkyl group, a C 6 -C 24 aryl group and a siloxane group, these groups optionally being substituted by hydrophobicity Substituted.
  • Embodiment 5 is the metal lithium-skeletal carbon composite according to embodiment 4, wherein the hydrophobic substituent comprises at least one of fluorine, a perfluoro group, and a siloxane.
  • porous carbon material carrier material comprises carbon nanotubes, porous carbon, carbon black, Any one or a combination of two or more of graphene, carbon fiber, acetylene black, and carbon aerogel.
  • porous carbon material carrier has at least a fine granular solid aggregate structure, a spherical aggregate structure, Any of a spheroidal aggregate structure and a doughnut-shaped aggregate structure;
  • the pores of the porous carbon material carrier have an average pore diameter of 10 to 100 nm;
  • the porous carbon material carrier has an average particle diameter of 1 to 15 ⁇ m;
  • the porous carbon material carrier has a conductivity of 1*10 -3 to 10S ⁇ cm -1 ;
  • the porous carbon material carrier has a specific surface area of 100 to 1500 m 2 /g;
  • the porous carbon material carrier can withstand a maximum pressure of 20 MPa or more;
  • the metal lithium is supported in the metal lithium-skeletal carbon composite in an amount of 10 to 50% by weight.
  • Embodiment 10 is a method for preparing a metal lithium-skeletal carbon composite material having a hydrophobic coating layer according to any one of embodiments 1-9, comprising:
  • a metal lithium-skeletal carbon composite material having a hydrophobic coating layer is obtained by solid-liquid separation or evaporation.
  • the organic solvent comprises any one of n-hexane, tetrahydrofuran, cyclohexane, and N-methylpyrrolidone, or a combination of two or more thereof.
  • Embodiment 12 is the method according to Embodiment 10 or 11, wherein the method further comprises dispersing the metal lithium-carbon skeleton composite material in an organic solvent, and dissolving the organic solvent and dissolving the organic solvent.
  • the organic solvent of the membrane-type hydrophobic substance or the compound having a lithium-reactive portion and a hydrophobic portion is the same or different.
  • Embodiment 13 is a method of protecting a material containing an active metal sensitive to water and oxygen, wherein the method comprises forming a hydrophobic coating layer on the material, the hydrophobic coating layer coating at least the material Active metal in the middle.
  • Embodiment 14 is the method of embodiment 13, wherein the material comprises a metallic lithium-carbon skeleton composite, a lithium foil, a lithium powder, and a metallic sodium.
  • hydrophobic coating layer is composed of a film-forming hydrophobic substance, or the hydrophobic coating layer is composed of a lithium-reactive portion and a hydrophobic portion.
  • the embodiment 16 is an electrode, wherein the electrode comprises the metal lithium-skeletal carbon composite material having a hydrophobic coating layer according to any one of the embodiments 1-9 as an electrode material.
  • DETAILED DESCRIPTION 17 is an electrochemical energy storage device including the electrode of embodiment 16.
  • the embodiment 18 is the electrochemical energy storage device according to the specific embodiment 17, wherein the electrochemical energy storage device comprises a metal lithium-oxide battery, a lithium ion battery, a lithium sulfur battery or a metal lithium-air battery.
  • Figure 1 shows a schematic of an octadecyl phosphate coated metal lithium-skeletal carbon composite.
  • the phosphate group of octadecyl phosphate is bonded to the surface of metallic lithium and is passivated by reaction with metallic lithium, so the binding site corresponds to the passivation layer and the alkyl moiety of octadecyl phosphate (hydrophobic).
  • the groups are arranged vertically on the surface of the metallic lithium to form a hydrophobic film (hydrophobic layer).
  • Figure 2 shows a scanning electron micrograph of a metallic lithium-skeletal carbon composite (a, b) and an octadecyl phosphate-metal lithium-skeletal carbon composite (c, d). It can be seen that the prepared octadecyl phosphate-metal lithium-skeletal carbon composite particles still retain the spherical or spheroidal morphology of the original metallic lithium-skeletal carbon composite material, and have a narrow size distribution.
  • Figure 3 shows the EDS (energy spectrum) analysis of the change in oxygen content of the lithium metal-skeletal carbon composite and the octadecyl phosphate-metal lithium-skeletal carbon composite before and after exposure to dry air for 1 h.
  • Figure 4 shows the results of capacity stability tests of metallic lithium-skeletal carbon composites and octadecyl phosphate-metal lithium-skeletal carbon-carbon composites in dry air. Test conditions: temperature 25 ° C, relative humidity 50%.
  • the octadecyl phosphate-metal lithium-skeletal carbon composite material has only a small increase in oxygen content after exposure to dry air for 1 h, and the capacity is not significantly attenuated, therefore, octadecyl phosphate -
  • the metal lithium-skeletal carbon composite material can be stably stored in dry air.
  • Figure 5 shows the voltage vs. octadecyl phosphate-metal lithium-skeletal carbon composite/lithium half-cell and metal lithium-skeletal carbon composite/lithium half-cell in different cycle times during constant current charge and discharge test.
  • Figure 6 shows the discharge specific capacity vs.
  • the octadecyl phosphate-metal lithium-skeletal carbon composite has no significant polarization during the cycle, so the material has good stability and circulation in a dry environment. stability.
  • the full battery composed of the composite material and the lithium iron phosphate positive electrode has a positive and negative electrode capacity ratio of about 1 to 30. Under the condition of 1 C rate, the capacity is hardly attenuated after 300 cycles; the lithium-carbon nanotube microsphere composite
  • the capacity retention rate after the full battery cycle of the negative electrode for 300 weeks was 82%; after the cycle of 250 times with the lithium battery as the negative electrode, the capacity retention rate suddenly decreased, and then the use could not be continued.
  • Figure 7 is an SEM image of the material, from which it can be seen that PMMA is coated with a metallic lithium-skeletal carbon composite.
  • Figure 8 shows the stability test of the material in air (test conditions: temperature 25 ° C, relative humidity 50%). This test shows that the material has a certain stability in air and has better air stability and processability than the metal lithium-skeletal carbon composite.
  • Figure 9 is an SEM image of the material, from which it can be seen that paraffin wax is coated on the surface of the metallic lithium-skeletal carbon composite.
  • Figure 10 shows the stability test of the material in air (test conditions: temperature 25 ° C, relative humidity 50%). This test shows that the material has a certain stability in air and has better air stability and processability than the metal lithium-skeletal carbon composite.
  • Figure 11 is an SEM image of the material, from which it can be seen that dodecyl mercaptan is coated on the surface of the metallic lithium-skeletal carbon composite.
  • Figure 12 shows the stability test of the material in air (test conditions: temperature 25 ° C, relative humidity 50%). This test shows that the material has a certain stability in air and has better air stability and processability than the metal lithium-skeletal carbon composite.
  • Figure 13 is an SEM image of the material, from which it can be seen that phenyl phosphate is coated on the surface of the metallic lithium-skeletal carbon composite.
  • Figure 14 shows the stability test of the material in air (test conditions: temperature 25 ° C, relative humidity 50%). This test shows that the material has a certain stability in air and has better air stability and processability than the metal lithium-skeletal carbon composite.
  • Figure 15 is a graph showing the constant current constant capacity test curve of the simulated battery fabricated by using the lithium-carbon nanotube microsphere composite prepared in this example as a negative electrode (the material is pressed against the foamed copper as a working electrode, 15 mm of metallic lithium foil).
  • the phosphate group also has a certain ionic conductivity, so the metal lithium-skeletal carbon material coated with phenyl phosphate is more than the uncoated one during the cycle. Low overpotential and better cycle life.

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Abstract

公开了一种具有疏水包覆层的金属锂-骨架碳复合材料、其制备方法、含有该金属锂-骨架碳复合材料的电极和电化学储能装置，以及保护含对水、氧敏感的活性金属材料的方法。具有疏水包覆层的金属锂-骨架碳复合材料包括：金属锂-骨架碳复合材料，包括多孔碳材料载体和至少分布于所述多孔碳材料载体的孔隙中的金属锂；疏水包覆层，其至少包覆所述金属锂-骨架碳复合材料中的金属锂。由于疏水包覆层具有隔绝水和氧的功能，具有疏水包覆层的金属锂-骨架碳复合材料可以稳定存在于空气中，采用具有疏水包覆层的金属锂-骨架碳复合材料作为锂电池的负极可以提高电池的安全性和循环寿命。

Description

具有疏水包覆层的金属锂-骨架碳复合材料、其制备方法与应用 技术领域
本发明涉及电池技术领域，尤其涉及可用于锂电池的锂碳复合材料。
背景技术
自从1991年Sony公司将锂电池正式投向市场之后，在过去的20年内，锂离子电池得到了充分的发展。锂离子电池由于其高容量，高能量密度以及良好的循环稳定性，广泛运用于电子产品以及动力汽车上。金属锂负极由于具有最低的还原电势(-3.045V vs H2/H+)，十倍于传统石墨负极的理论容量(3860mA h g-1,石墨负极:372mA h g-1)被称为电池储能界的“圣杯”。此外需要用到金属锂负极的下一代锂电池，锂硫电池(理论能量密度2600Wh/kg)；锂空气电池(理论能量密度5210Wh/kg)都极大高于目前锂离子电池的能量密度，若采用这些电池作为动力汽车的电源则是的汽车在充满电后有更长的行驶里程，从而为当今世界的能源问题提供了一个极好的解决方案。
然而，金属锂化学性质极为活泼，会与空气中的氧气和水剧烈反应，放出大量的热。因此，对于金属锂负极的操作必须在氩气保护的条件下进行，严重增加了金属锂的使用成本以及安全隐患。此外，金属锂负极在循环过程中，表面会形成枝晶，而枝晶的生长有可能会刺穿隔膜造成正负极相接而发生内部短路，释放出大量的热，造成电池的燃烧甚至爆炸。
发明内容
本发明的主要目的在于提供具有疏水包覆层的金属锂-骨架碳复合材料、其制备方法、含有该金属锂-骨架碳复合材料的电极和电化学储能装置，以及保护含对水、氧敏感的活性金属的材料的方法。
本发明采用的技术方案包括：
在一些实施例中提供一种具有疏水包覆层的金属锂-骨架碳复合材料，其包括：金属锂-骨架碳复合材料，包括多孔碳材料载体和至少分布于所述多孔碳材料载体的孔隙中的金属锂；和疏水包覆层，至少包覆所述金属锂-骨架碳复合材料中的金属锂金属基纳米颗粒-碳复合材料。
在一些实施例中提供一种用于制备上述具有疏水包覆层的金属锂-骨架碳复合材料的方法， 包括：将金属锂-碳骨架复合材料与溶解有成膜性疏水物质或者具有锂反应性部分和疏水性部分的化合物的有机溶剂混合；通过固液分离或蒸发，获得具有疏水包覆层的金属锂-骨架碳复合材料。
在一些实施例中提供一种保护含对水、氧敏感的活性金属的材料的方法，所述方法包括在所述材料上形成疏水包覆层，所述疏水包覆层至少包覆所述材料中的活性金属。
在一些实施例中提供一种电极，所述电极包含上述具有疏水包覆层的金属锂-骨架碳复合材料作为电极材料。
在一些实施例中提供一种电化学储能装置，其包括上述电极。
本发明具有以下有益效果中的至少一种：
(1)形成的致密疏水包覆层具有隔绝水和氧的功能，被包覆的材料可以稳定存在于空气中；
(2)具有锂反应性部分和疏水性部分的化合物形成的包覆层具有钝化层和疏水层的双重作用；
(3)疏水包覆层具有一定的机械强度，能够承受金属锂-骨架碳复合材料表面的固体电解质界面膜(SEI膜)的体积变化，提高其循环稳定性，抑制枝晶的产生；
(4)采用具有疏水包覆层的金属锂-骨架碳复合材料作为锂电池的负极可以提高电池的安全性和循环寿命。
附图说明
图1为实施例1中十八烷基磷酸酯包覆金属锂-骨架碳复合材料的示意图；
图2为实施例1中金属锂-骨架碳复合材料(a,b)和十八烷基磷酸酯-金属锂-骨架碳复合材料(c,d)的扫描电镜图片。
图3为实施例1中金属锂-骨架碳复合材料与十八烷基磷酸酯-金属锂-骨架碳复合材料在干燥空气中暴露1h前后的氧含量变化的EDS(能谱)分析结果。
图4为实施例1中金属锂-骨架碳复合材料和十八烷基磷酸酯-金属锂-骨架碳碳复合材料在干燥空气中的容量稳定性测试结果。
图5为实施例1中十八烷基磷酸酯-金属锂-骨架碳复合材料/锂半电池和金属锂-骨架碳复合材料/锂半电池在恒流充放电测试过程中不同循环次数时，电压vs.容量曲线图。
图6为实施例1中1C倍率条件下十八烷基磷酸酯-金属锂-骨架碳复合材料，金属锂-骨架碳 复合材料，锂片，分别与磷酸铁锂组成的全电池的放电比容量vs.循环次数图。
图7为实施例2中PMMA-金属锂-骨架碳复合材料的SEM图。
图8为实施例2中PMMA-金属锂-骨架碳复合材料在空气中的稳定性测试结果。
图9为实施例3中石蜡-金属锂-骨架碳复合材料的SEM图。
图10为实施例3中石蜡-金属锂-骨架碳复合材料在空气中的稳定性测试结果。
图11为实施例4中十二烷基硫醇-金属锂-骨架碳复合材料的SEM图。
图12为实施例4中十二烷基硫醇-金属锂-骨架碳复合材料在空气中的稳定性测试结果。
图13为实施例5中苯基磷酸-金属锂-骨架碳复合材料的SEM图。
图14为实施例5中苯基磷酸-金属锂-骨架碳复合材料在空气中的稳定性测试结果。
图15为实施例5中模拟电池的恒流恒容量测试曲线。
具体实施方式
本发明的一个方面提供一种具有疏水包覆层的金属锂-骨架碳复合材料，包含金属锂-骨架碳复合材料和疏水包覆层，其中，金属锂-骨架碳复合材料包括多孔碳材料载体和至少分布于所述多孔碳材料载体的孔隙中的金属锂，疏水包覆层至少包覆所述金属锂-骨架碳复合材料中的金属锂。
在一些实施例中，疏水包覆层可以由成膜性疏水物质组成，所述成膜性疏水物质在金属锂-骨架碳复合材料的暴露表面上形成疏水膜。
在一些具体的实施例中，成膜性疏水物质选自成膜性疏水高分子和成膜性疏水小分子，成膜性疏水高分子可以包括聚甲基丙烯酸甲酯(PMMA)、聚偏氟乙烯(PVDF)、聚二甲基硅氧烷(PDMS)等；成膜性疏水小分子可以包括石蜡、白油、苯并三氮唑等。
在一些实施例中，疏水包覆层可以由具有锂反应性部分和疏水性部分的化合物组成，锂反应性部分与金属锂反应以将其钝化，疏水性部分形成疏水层，疏水层位于最外部。
在一些具体的实施例中，具有锂反应性部分和疏水性部分的化合物可以是线性小分子化合物，一端具有锂反应性基团(锂反应性部分)，另一端为疏水性的有机分子链(疏水性部分)，借助锂反应性基团与金属锂反应的锚固效应，疏水性的有机分子链在金属锂表面组装成疏水层。这样的线性小分子化合物的实例可以包括表面活性剂等。
在一些具体的实施例中，具有锂反应性部分和疏水性部分的化合物的锂反应性部分包括磷酸 基团、硫醇基团、碳酸基团和任选氟化的硅烷基团中的至少一种。
在一些具体的实施例中，具有锂反应性部分和疏水性部分的化合物的疏水性部分包括C4-C22烷基基团、C6-C24芳基基团和硅氧烷基团中的至少一种，这些基团任选被疏水性取代基取代。C4-C22烷基可以优选为C8-C22烷基，或者C12-C22烷基。疏水性取代基可以选自氟、全氟基团、硅氧烷等。
在一些实施例中，疏水包覆层具有1-100nm的厚度，例如10-50nm。
在一些实施例中，疏水包覆层具有电子绝缘性和/或离子导电性。
在一些实施例中，金属锂-骨架碳复合材料中的多孔碳材料载体的材料包括碳纳米管、多孔碳、炭黑、石墨烯、碳纤维、乙炔黑、碳气凝胶中的任意一种或两种以上的组合。
在一些具体的实施例中，多孔碳材料载体至少具有微小颗粒状实体聚集结构、球形聚集结构、类球形聚集结构和面包圈形聚集结构中的任意一种。
在一些具体的实施例中，多孔碳材料载体所含孔洞的平均孔径为10～100nm。
在一些具体的实施例中，多孔碳材料载体的平均粒径为1～100μm，优选1-50μm，或者1-15μm。
在一些具体的实施例中，多孔碳材料载体的电导率为1*10-3～10S·cm-1。
在一些具体的实施例中，多孔碳材料载体的比表面积为100～1500m2/g。
在一些具体的实施例中，多孔碳材料载体的可承受的最高压力为20MPa以上。
在一些具体的实施例中，多孔碳材料载体包括碳纤维微球、多孔碳纳米管微球和乙炔黑。碳纤维微球和多孔碳纳米管微球由碳纳米管或碳纳米纤维相互交缠团聚而形成，内部和表面上具有大量纳米尺度孔隙。这样的微球具有近似实心的结构(类似毛线团结构)，即微球内部充满碳纳米管或碳纳米纤维，但是交缠团聚的碳纳米管或碳纳米纤维之间存在纳米尺度孔隙，这些孔隙可以用于容纳金属锂颗粒。乙炔黑是通过乙炔气在高温下隔绝空气进行热裂解后，冷却收集制得的炭黑，粒径可以为40-50纳米。
在一些具体实施例中，碳纳米管微球为球形或类球状颗粒，平均直径可以为1μm～100μm，优选为1μm～25μm。
在一些具有实施例中，碳纳米管包括多壁碳纳米管、双壁碳纳米管和单壁碳纳米管中的任意一种或两种以上的组合，所述碳纳米管任选经过表面功能化处理。修饰于碳纳米管表面的基团可选自但不限于-COOH、-OH、-NH2等基团。
在一些实施例中，碳纳米管微球可以通过将碳纳米管分散于溶剂中形成分散液，然后喷雾干 燥而制备。例如，制备方法可以包括以下步骤：
A、将碳纳米管通过超声处理分散到分散溶剂(不含表面活性剂)中，获得分散液；
B、将步骤A中获得的分散液通过喷雾干燥机的喷嘴喷出，预设定进风温度和出风温度，喷雾过程中保持溶液为搅拌状态；
C、冷却，即获得碳纳米管微球。
在一些具有实施例中，所述溶剂采用能够使碳纳米管/碳纳米纤维和纳米碳颗粒均匀分散的有机和/或无机液体，例如，水、氨水、盐酸溶液、乙醇、丙酮、异丙醇的任意一种或多种的组合。
在一些具有实施例中，所述溶剂可以是体积比为1:10的乙醇与水的混合物。
在一些具体实施例中，喷雾干燥的条件可以包括：进风温度为150～250℃，出风温度为75℃以上，如75～150℃，或者为90℃以上；一个优选的喷雾干燥条件包括：进风温度为190～210℃，出风温度为90～110℃。
在一些具体实施例中，喷雾干燥时的喷雾速度可以为1毫升/分钟至100升/分钟。
在一些实施例中，金属锂-骨架碳复合材料可以通过将熔融金属锂与多孔骨架碳材料混合，冷却后获得。所述混合可以包括将金属锂与多孔骨架碳材料在加热下(例如约200℃)搅拌混合或者将多孔骨架碳材料浸入熔融金属锂中。金属锂-骨架碳复合材料的制备在惰性气氛中进行，例如在氩气气氛的手套箱中(水含量<10ppm，氧气含量<10ppm)。
在一些具体的实施例中，金属锂在金属锂-骨架碳复合材料中的担载量为10～90wt％。
本发明的另一个方面提供一种用于制备上述具有疏水包覆层的金属锂-骨架碳复合材料的方法，包括：将金属锂-碳骨架复合材料与溶解有成膜性疏水物质或者具有锂反应性部分和疏水性部分的化合物的有机溶剂混合；通过固液分离或蒸发，获得具有疏水包覆层的金属锂-骨架碳复合材料。
关于“金属锂-碳骨架复合材料”、“成膜性疏水物质”和“具有锂反应性部分和疏水性部分的化合物”，参见上述部分中的相关描述。
在一些实施例中，用于溶解有成膜性疏水物质或者具有锂反应性部分和疏水性部分的化合物的有机溶剂可以包括正己烷、四氢呋喃、环己烷、N-甲基吡咯烷酮中的任意一种或两种以上的组合。
在一些实施例中，在金属锂-碳骨架复合材料与溶解有成膜性疏水物质或者具有锂反应性部分和疏水性部分的化合物的有机溶剂混合之前，将所述金属锂-碳骨架复合材料分散在另一有机溶剂中，所述另一有机溶剂可以与溶解有成膜性疏水物质或者具有锂反应性部分和疏水性部分的化合物的有机溶剂相同或不同，选自正己烷、四氢呋喃、环己烷、N-甲基吡咯烷酮中的任意一种或两种以上的组合。
在一些实施例中，金属锂-碳骨架复合材料与溶解有成膜性疏水物质或者具有锂反应性部分和疏水性部分的化合物的有机溶剂混合在搅拌下进行。
在一些实施例中，用于获得具有疏水包覆层的金属锂-骨架碳复合材料的固液分离包括过滤，例如抽滤等。
本发明的另一个方面提供一种保护含对水、氧敏感的活性金属的材料的方法，包括在所述材料上形成疏水包覆层，所述疏水包覆层至少包覆所述材料中的活性金属。
在一些实施例中，被保护的材料包括金属锂-碳骨架复合材料、锂箔，锂粉以及金属钠。
关于疏水包覆层及其形成方法，参见上述部分中的相关描述。
本发明的另一个方面提供一种电极，其包含上述的具有疏水包覆层的金属锂-骨架碳复合材料作为电极材料。
本发明的另一个方面提供一种电化学储能装置，其包括上述的电极。
在一些实施例中，电化学储能装置包括金属锂-氧化物电池、锂离子电池、锂硫电池或金属锂-空气电池等。
下列具体实施方式意在示例性地而非限定性地说明本公开。
具体实施方式1是一种具有疏水包覆层的金属锂-骨架碳复合材料，其包括：
金属锂-骨架碳复合材料，包括多孔碳材料载体和至少分布于所述多孔碳材料载体的孔隙中的金属锂；
疏水包覆层，其至少包覆所述金属锂-骨架碳复合材料中的金属锂。
具体实施方式2是根据具体实施方式1所述的金属锂-骨架碳复合材料，其中所述疏水包覆层由成膜性疏水物质组成，覆盖所述金属锂-骨架碳复合材料的暴露表面；优选所述成膜性疏水物质选自成膜性疏水高分子，例如聚甲基丙烯酸甲酯(PMMA)、聚偏氟乙烯(PVDF)、聚二 甲基硅氧烷(PDMS)，和成膜性疏水小分子，例如石蜡、白油、苯并三氮唑。
具体实施方式3是根据具体实施方式1所述的金属锂-骨架碳复合材料，其中所述疏水包覆层由具有锂反应性部分和疏水性部分的化合物组成，所述锂反应性部分与金属锂反应以将其钝化，所述疏水性部分形成外部疏水层。
具体实施方式4是根据具体实施方式3所述的金属锂-骨架碳复合材料，其中所述锂反应性部分包括磷酸基团、硫醇基团、碳酸基团和氟硅烷基团中的至少一种；
和/或，所述疏水性部分包括C4-C22烷基基团、C6-C24芳基基团和硅氧烷基团中的至少一种，这些基团任选被疏水性取代基取代。
具体实施方式5是根据具体实施方式4所述的金属锂-骨架碳复合材料，其中所述疏水性取代基包括氟、全氟基团和硅氧烷中的至少一种。
具体实施方式6是根据具体实施方式1-5中任一项所述的金属锂-骨架碳复合材料，其中所述疏水包覆层具有10-50nm的厚度。
具体实施方式7是根据具体实施方式1-6中任一项所述的金属锂-骨架碳复合材料，其中所述疏水包覆层具有电子绝缘性和/或离子导电性。
具体实施方式8是根据具体实施方式1-7中任一项所述的钝化的金属锂-骨架碳复合材料，其中所述多孔碳材料载体的材料包括碳纳米管、多孔碳、炭黑、石墨烯、碳纤维、乙炔黑、碳气凝胶中的任意一种或两种以上的组合。
具体实施方式9是根据具体实施方式1-8中任一项所述的钝化的金属锂-骨架碳复合材料，其中所述多孔碳材料载体至少具有微小颗粒状实体聚集结构、球形聚集结构、类球形聚集结构和面包圈形聚集结构中的任意一种；
和/或，所述多孔碳材料载体所含孔洞的平均孔径为10～100nm；
和/或，所述多孔碳材料载体的平均粒径为1～15μm；
和/或，所述多孔碳材料载体的电导率为1*10-3～10S·cm-1；
和/或，所述多孔碳材料载体的比表面积为100～1500m2/g；
和/或，所述多孔碳材料载体可承受的最高压力为20MPa以上；
和/或，所述金属锂在金属锂-骨架碳复合材料中的担载量为10～50wt％。
具体实施方式10是一种用于制备根据具体实施方式1-9中任一项所述的具有疏水包覆层的金属锂-骨架碳复合材料的方法，包括：
将金属锂-碳骨架复合材料与溶解有成膜性疏水物质或者具有锂反应性部分和疏水性部分的化合物的有机溶剂混合；
通过固液分离或蒸发，获得具有疏水包覆层的金属锂-骨架碳复合材料。
具体实施方式11是根据具体实施方式10所述的方法，其中所述有机溶剂包括正己烷、四氢呋喃、环己烷、N-甲基吡咯烷酮中的任意一种或两种以上的组合。
具体实施方式12是根据具体实施方式10或11所述的方法，其中所述方法还包括先将所述金属锂-碳骨架复合材料分散在有机溶剂中，所述分散用有机溶剂与溶解有成膜性疏水物质或者具有锂反应性部分和疏水性部分的化合物的有机溶剂相同或不同。
具体实施方式13是一种保护含对水、氧敏感的活性金属的材料的方法，其中所述方法包括在所述材料上形成疏水包覆层，所述疏水包覆层至少包覆所述材料中的活性金属。
具体实施方式14是根据具体实施方式13所述的方法，其中所述材料包括金属锂-碳骨架复合材料、锂箔，锂粉以及金属钠。
具体实施方式15是根据具体实施方式13或14所述的方法，其中所述疏水包覆层由成膜性疏水物质组成，或者所述疏水包覆层由具有锂反应性部分和疏水性部分的化合物组成。
具体实施方式16是一种电极，其中所述电极包含根据具体实施方式1-9中任一项所述的具有疏水包覆层的金属锂-骨架碳复合材料作为电极材料。
具体实施方式17是一种电化学储能装置，其中包括具体实施方式16所述的电极。
具体实施方式18是根据具体实施方式17所述的电化学储能装置，其中所述电化学储能装置包括金属锂-氧化物电池、锂离子电池、锂硫电池或金属锂-空气电池。
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。此外，下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
又及，在如下实施例之中所采用的各种产品结构参数、各种反应参与物及工艺条件均是较为典型的范例，但经过本案发明人大量试验验证，于上文所列出的其它不同结构参数、其它类型的反应参与物及其它工艺条件也均是适用的，并也均可达成本发明所声称的技术效果。
合成实施例1
首先将2g未经任何化学处理的多壁碳纳米管(上海鹏芯新材料科技有限公司)加入200mL去离子水，后加入20mL无水乙醇。密封搅拌，130W超声探头超声处理5小时，使样品均匀分散。完毕后将样品加入喷雾干燥机。进风温度设定为200℃，出风温度设定在150℃，喷雾压力设定为40MPa，进样量设定为500mL/h，干燥后即得到多孔碳纳米管微球材料。对微球进行氮气吸附脱附测试，微球比表面积为151m2/g，平均孔径为18.7nm。
称取100mg电池级金属锂和100mg多孔碳纳米管微球(碳纳米管通过喷雾干燥获得，平均孔径为18.7nm)置于对金属锂惰性的加热器中，加热至200℃(高于金属锂的熔点)，搅拌，持续6分钟，混合结束，降温至室温，整个过程在氩气气氛中进行。得到金属锂-多孔碳纳米管微球复合材料(锂-碳骨架复合材料)，通过称重对比未吸收金属锂的碳纳米管微球的重量，测得其中金属锂的负载量为15.0％。
实施例1
取1g合成实施例1制备的金属锂-骨架碳复合材料分散于8g正己烷溶液中，再向其中加入10ml的0.1％wt十八烷基磷酸酯的四氢呋喃溶液，常温搅拌反应10min，搅拌结束后滤掉液体，将粉末烘干后得到将磷酸酯-金属锂-骨架碳复合材料。
图1显示了十八烷基磷酸酯包覆金属锂-骨架碳复合材料的示意图。图中十八烷基磷酸酯的磷酸基团结合于金属锂表面，通过与金属锂反应使其钝化，因此结合部位相当于钝化层，而十八烷基磷酸酯的烷基部分(疏水基团)在金属锂表面上垂直排列，组成疏水膜(疏水层)。
图2显示了金属锂-骨架碳复合材料(a,b)和十八烷基磷酸酯-金属锂-骨架碳复合材料(c,d)的扫描电镜图片。可以看出，制备出的十八烷基磷酸酯-金属锂-骨架碳复合颗粒仍保原有金属锂-骨架碳复合材料的球形或类球形形貌，具有较窄的尺寸分布。
图3显示了金属锂-骨架碳复合材料与十八烷基磷酸酯-金属锂-骨架碳复合材料在干燥空气中暴露1h前后的氧含量变化的EDS(能谱)分析结果。图4显示了金属锂-骨架碳复合材料和十八烷基磷酸酯-金属锂-骨架碳碳复合材料在干燥空气中的容量稳定性测试结果。测试条件：温度25℃，相对湿度50％。从图3和4可以看出，十八烷基磷酸酯-金属锂-骨架碳复合材料在干燥空气中暴露1h后氧含量仅少量增加，并且容量无明显衰减，因此，十八烷基磷酸酯-金属锂-骨架碳复合材料可以稳定保存于干燥空气中。
图5显示了十八烷基磷酸酯-金属锂-骨架碳复合材料/锂半电池和金属锂-骨架碳复合材料/锂 半电池在恒流充放电测试过程中不同循环次数时，电压vs.容量曲线图(将材料压于泡沫铜作为工作电极，15毫米的金属锂箔作为锂电池的对电极；电解液为1mol/L的LiPF6的三组分混合溶剂EC:DMC:EMC＝1:1:1(体积比v/v/v)，聚丙烯微孔薄膜为隔膜组装成模拟电池)。图6显示了1C倍率条件下十八烷基磷酸酯-金属锂-骨架碳复合材料，金属锂-骨架碳复合材料，锂片，分别与磷酸铁锂组成的全电池的放电比容量vs.循环次数图(将材料压于泡沫铜作为负极，磷酸铁锂(苏州纳新新能源科技有限公司)为正极；电解液为1mol/L的LiPF6的三组分混合溶剂EC:DMC:EMC＝1:1:1(体积比v/v/v)，聚丙烯微孔薄膜为隔膜组装成模拟电池)。在与锂片组成的半电池测试过程中，十八烷基磷酸酯-金属锂-骨架碳复合材料在循环过程中没有明显的极化，因此该材料具有良好的干燥环境中的稳定性以及循环稳定性。由该复合材料与磷酸铁锂正极组成的全电池，正负极容量配比约为1～30，1C倍率条件下，循环300周之后，容量几乎不衰减；以锂-碳纳米管微球复合物为负极的全电池循环300周之后的容量保持率为82％；以锂片为负极的全电池，循环250次之后，容量保持率骤然下降，之后无法再继续使用。
实施例2
取1g合成实施例1制备的金属锂-骨架碳复合材料分散于8g正己烷溶液中，再向其中加入20ml的0.1％wt的PMMA的四氢呋喃溶液，剧烈搅拌后，PMMA析出沉淀于金属锂-骨架碳复合材料表面。将其进行过滤，洗涤，烘干后得到PMMA-金属锂-骨架碳复合材料。
图7为该材料的SEM图，从图中可以看出PMMA包覆在了金属锂-骨架碳复合材料。图8为该材料在空气中的稳定性测试，(测试条件：温度25℃，相对湿度50％)。该测试表明材料在空气中具有一定的稳定性，比金属锂-骨架碳复合材料具有了更加出色的空气稳定性以及可加工性。
实施例3
取1g合成实施例1制备的金属锂-骨架碳复合材料分散于8g正己烷溶液中，再向其中加入20ml的0.1％wt的石蜡的正己烷溶液，保持搅拌同时加热蒸干溶剂，石蜡析出沉淀于金属锂-骨架碳复合材料表面，得到石蜡-金属锂-骨架碳复合材料。
图9为该材料的SEM图，从图中可以看出石蜡包覆在了金属锂-骨架碳复合材料表面。图10为该材料在空气中的稳定性测试，(测试条件：温度25℃，相对湿度50％)。该测试表明材料在空气中具有一定的稳定性，比金属锂-骨架碳复合材料具有更加出色的空气稳定性以及可加工性。
实施例4
取1g合成实施例1制备的金属锂-骨架碳复合材料分散于8g正己烷溶液中，再向其中加入10ml的0.1％wt的十二烷基硫醇的正己烷溶液，保持搅拌10min，待反应结束后将产物抽滤，洗涤，得到十二烷基硫醇-金属锂-骨架碳复合材料。
图11为该材料的SEM图，从图中可以看出十二烷基硫醇包覆在了金属锂-骨架碳复合材料表面。图12为该材料在空气中的稳定性测试，(测试条件：温度25℃，相对湿度50％)。该测试表明材料在空气中具有一定的稳定性，比金属锂-骨架碳复合材料具有更加出色的空气稳定性以及可加工性。
实施例5
取1g合成实施例1制备的金属锂-骨架碳复合材料分散于8g正己烷溶液中，再向其中加入10ml的0.1％wt苯基磷酸的正己烷溶液，保持搅拌10min，待反应结束后将产物抽滤，洗涤，得到苯基磷酸-金属锂-骨架碳复合材料。
图13为该材料的SEM图，从图中可以看出苯基磷酸包覆在了金属锂-骨架碳复合材料表面。图14为该材料在空气中的稳定性测试，(测试条件：温度25℃，相对湿度50％)。该测试表明材料在空气中具有一定的稳定性，比金属锂-骨架碳复合材料具有更加出色的空气稳定性以及可加工性。图15显示了该实施例中制备的锂-碳纳米管微球复合材料作为负极所制造的模拟电池的恒流恒容量测试曲线(将材料压于泡沫铜作为工作电极，15毫米的金属锂箔作为锂电池的对电极。电解液为1mol/L的LiPF6的三组分混合溶剂EC:DMC:EMC＝1:1:1(体积比v/v/v)，聚丙烯微孔薄膜为隔膜组装成模拟电池)。从该图可以看出，锂-碳纳米管微球复合材料在开始时极化电压很小，表明材料具有大的比表面积，能极大地降低电流密度，有效抑制锂枝晶的生成，避免由于枝晶短路带来的电池安全隐患。此外，由于苯基具有一定的离子导电率，磷酸基团也具有一定的离子导电率，因此经过苯基磷酸包覆后的金属锂-骨架碳材料比未经包覆的在循环过程中有更低的过电势以及更好的循环寿命。
应当理解，以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (18)

  1. 一种具有疏水包覆层的金属锂-骨架碳复合材料，其特征在于包括：
    金属锂-骨架碳复合材料，包括多孔碳材料载体和至少分布于所述多孔碳材料载体的孔隙中的金属锂；
    疏水包覆层，其至少包覆所述金属锂-骨架碳复合材料中的金属锂。
  2. 根据权利要求1所述的金属锂-骨架碳复合材料，其特征在于所述疏水包覆层由成膜性疏水物质组成，覆盖所述金属锂-骨架碳复合材料的暴露表面；优选所述成膜性疏水物质选自成膜性疏水高分子，例如聚甲基丙烯酸甲酯(PMMA)、聚偏氟乙烯(PVDF)、聚二甲基硅氧烷(PDMS)，和成膜性疏水小分子，例如石蜡、白油、苯并三氮唑。
  3. 根据权利要求1所述的金属锂-骨架碳复合材料，其特征在于所述疏水包覆层由具有锂反应性部分和疏水性部分的化合物组成，所述锂反应性部分与金属锂反应以将其钝化，所述疏水性部分形成外部疏水层。
  4. 根据权利要求3所述的金属锂-骨架碳复合材料，其特征在于所述锂反应性部分包括磷酸基团、硫醇基团、碳酸基团和氟硅烷基团中的至少一种；
    和/或，所述疏水性部分包括C4-C22烷基基团、C6-C24芳基基团和硅氧烷基团中的至少一种，这些基团任选被疏水性取代基取代。
  5. 根据权利要求4所述的金属锂-骨架碳复合材料，其特征在于所述疏水性取代基包括氟、全氟基团和硅氧烷中的至少一种。
  6. 根据权利要求1-5中任一项所述的金属锂-骨架碳复合材料，其特征在于所述疏水包覆层具有10-50nm的厚度。
  7. 根据权利要求1-6中任一项所述的金属锂-骨架碳复合材料，其特征在于所述疏水包覆层具有电子绝缘性和/或离子导电性。
  8. 根据权利要求1-7中任一项所述的钝化的金属锂-骨架碳复合材料，其特征在于所述多孔碳材料载体的材料包括碳纳米管、多孔碳、炭黑、石墨烯、碳纤维、乙炔黑、碳气凝胶中的任意一种或两种以上的组合。
  9. 根据权利要求1-8中任一项所述的钝化的金属锂-骨架碳复合材料，其特征在于所述多孔碳材料载体至少具有微小颗粒状实体聚集结构、球形聚集结构、类球形聚集结构和面包圈形聚集 结构中的任意一种；
    和/或，所述多孔碳材料载体所含孔洞的平均孔径为10～100nm；
    和/或，所述多孔碳材料载体的平均粒径为1～15μm；
    和/或，所述多孔碳材料载体的电导率为1*10-3～10S·cm-1；
    和/或，所述多孔碳材料载体的比表面积为100～1500m2/g；
    和/或，所述多孔碳材料载体可承受的最高压力为20MPa以上；
    和/或，所述金属锂在金属锂-骨架碳复合材料中的担载量为10～50wt％。
  10. 一种用于制备根据权利要求1-9中任一项所述的具有疏水包覆层的金属锂-骨架碳复合材料的方法，其特征在于所述方法包括：
    将金属锂-碳骨架复合材料与溶解有成膜性疏水物质或者具有锂反应性部分和疏水性部分的化合物的有机溶剂混合；
    通过固液分离或蒸发，获得具有疏水包覆层的金属锂-骨架碳复合材料。
  11. 根据权利要求10所述的方法，其特征在于所述有机溶剂包括正己烷、四氢呋喃、环己烷、N-甲基吡咯烷酮中的任意一种或两种以上的组合。
  12. 根据权利要求10或11所述的方法，其特征在于所述方法还包括先将所述金属锂-碳骨架复合材料分散在有机溶剂中，所述分散用有机溶剂与溶解有成膜性疏水物质或者具有锂反应性部分和疏水性部分的化合物的有机溶剂相同或不同。
  13. 一种保护含对水、氧敏感的活性金属的材料的方法，其特征在于所述方法包括在所述材料上形成疏水包覆层，所述疏水包覆层至少包覆所述材料中的活性金属。
  14. 根据权利要求13所述的方法，其特征在于所述材料包括金属锂-碳骨架复合材料、锂箔，锂粉以及金属钠。
  15. 根据权利要求13或14所述的方法，其特征在于所述疏水包覆层由成膜性疏水物质组成，或者所述疏水包覆层由具有锂反应性部分和疏水性部分的化合物组成。
  16. 一种电极，其特征在于所述电极包含根据权利要求1-9中任一项所述的具有疏水包覆层的金属锂-骨架碳复合材料作为电极材料。
  17. 一种电化学储能装置，其特征在于包括权利要求16所述的电极。
  18. 根据权利要求17所述的电化学储能装置，其特征在于所述电化学储能装置包括金属锂-氧化物电池、锂离子电池、锂硫电池或金属锂-空气电池。
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