WO2019019414A1 - 多孔碳骨架-纳米颗粒复合材料、其金属锂复合物、它们的制备方法及应用 - Google Patents

多孔碳骨架-纳米颗粒复合材料、其金属锂复合物、它们的制备方法及应用 Download PDF

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WO2019019414A1
WO2019019414A1 PCT/CN2017/105680 CN2017105680W WO2019019414A1 WO 2019019414 A1 WO2019019414 A1 WO 2019019414A1 CN 2017105680 W CN2017105680 W CN 2017105680W WO 2019019414 A1 WO2019019414 A1 WO 2019019414A1
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carbon
lithium
nanoparticle composite
porous carbon
carbon skeleton
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PCT/CN2017/105680
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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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    • H—ELECTRICITY
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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    • 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
    • H—ELECTRICITY
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    • 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
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    • 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
    • H01M4/40—Alloys based on alkali metals
    • H—ELECTRICITY
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    • 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
    • H01M4/40—Alloys based on alkali metals
    • H01M4/405—Alloys based on lithium
    • H—ELECTRICITY
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • H01M4/42—Alloys based on zinc
    • H—ELECTRICITY
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    • 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
    • H01M4/46—Alloys based on magnesium or aluminium
    • H—ELECTRICITY
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    • 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
    • H01M4/46—Alloys based on magnesium or aluminium
    • H01M4/466—Magnesium based
    • H—ELECTRICITY
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • 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
    • 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 technical field of nano materials, in particular to a porous carbon skeleton-nanoparticle composite material, a metal lithium composite thereof, a preparation method thereof and application thereof.
  • a lithium battery is a secondary battery (rechargeable battery) that operates mainly by moving lithium ions between a positive electrode and a negative electrode.
  • Li + is intercalated and deintercalated between the two electrodes: during charging, Li + is deintercalated from the positive electrode, embedded in the negative electrode through the electrolyte, and reversed when discharged.
  • Lithium batteries have been widely used in electronic products, smart grids, etc. due to their high energy density, environmental friendliness and good cycle stability.
  • the energy density of traditional lithium-ion batteries can no longer meet the increasing energy requirements, so lithium batteries with higher energy density have been developed. It is currently the biggest research hotspot in the energy field.
  • the lithium metal anode Since the lithium metal anode has ten times the specific capacity of the conventional graphite anode, reaching 3860 mAh/g, and the metal lithium has the most negative potential and the lightest density, the battery energy density of the lithium anode will be greatly improved.
  • the lithium metal negative electrode can provide lithium ions for the positive electrode, and thus can be combined with a lithium-ion positive electrode having a higher energy density such as sulfur, air, etc. to form a high-energy density lithium sulfur-lithium air battery.
  • the metal lithium anode is prone to dendrites during the cycle, which will pierce the battery separator and cause a short circuit to release a huge heat, causing a series of safety accidents such as battery burning and explosion.
  • the interface instability of the metal lithium during the cycle causes the internal internal resistance of the battery to increase, causing the battery cycle capacity to be attenuated. Therefore, there is a need to improve the safety and cycle life of a battery using a lithium negative electrode.
  • the main object of the present invention is to provide a porous carbon skeleton-nanoparticle composite material, a metal lithium composite thereof, a preparation method thereof, an electrode comprising the same, and a lithium battery, which can reduce nucleation energy when metal lithium is bonded to a porous carbon skeleton Or increase the affinity of lithium to the framework carbon to improve the safety and/or cycle stability of the battery.
  • a porous carbon skeleton-nanoparticle composite wherein the nanoparticles are lithium reactive metals or oxide nanoparticles thereof, distributed within and on the pores of the porous carbon skeleton.
  • a method of preparing the above porous carbon skeleton-nanoparticle composite material comprising dispersing carbon nanotubes or carbon nanofibers having surface-loaded nanoparticles in a solvent to form a dispersion, and then spray-drying; or The carbon nanotubes or the carbon nanofibers and the nanoparticles are dispersed together in a solvent to form a dispersion, and then spray-dried; or the carbon-based porous material is dispersed in a colloidal solution of the nanoparticles, followed by spray drying.
  • a pore carbon skeleton-nanoparticle composite-metal lithium composite comprising the porous carbon skeleton-nanoparticle composite material described above and a metal distributed in and on the pores of the porous carbon skeleton. lithium.
  • a method of preparing a porous carbon skeleton-nanoparticle composite-metal lithium composite comprising: mixing molten metal lithium with the above porous carbon skeleton-nanoparticle composite, and then cooling.
  • a method of increasing lithium deposition efficiency when metal lithium is bonded to a porous carbon skeleton comprising: forming the above porous carbon skeleton-nanoparticle composite material, and then mixing the molten metal lithium with the same
  • an electrode comprising the above porous carbon skeleton-nanoparticle composite-metal lithium composite as an active material is provided.
  • a lithium battery comprising the electrode described above as a negative electrode.
  • the nanoparticles existing in the porous carbon skeleton act as a nucleation site of lithium when the metal lithium is combined with the porous carbon skeleton, and reduce nucleation energy; or improve the affinity with the skeleton carbon by reacting with lithium, thereby improving Lithium deposition efficiency.
  • the nanoparticles inside the porous carbon skeleton promote the deposition of metallic lithium into the interior of the material, and thus have more excellent cycle stability when used for the negative electrode material of the battery.
  • Porous carbon skeleton-nanoparticle composite material-metal lithium composite has a large specific surface area, can greatly reduce the current density, effectively inhibit the formation of lithium dendrites, thereby improving the safety of the battery.
  • Porous carbon skeleton-nanoparticle composite-metal lithium composite is simple in preparation process and suitable for mass production.
  • Example 1 is a transmission electron micrograph of a gold nanoparticle (a) and a gold nanoparticle-skeletal carbon composite (b) prepared in Example 1;
  • Example 2 is a scanning electron micrograph of a gold nanoparticle-skeletal carbon composite (a, b) and a metal lithium-gold nanoparticle-skeletal carbon composite (c, d) prepared in Example 1;
  • FIG. 3 is a voltage-capacity curve diagram of a metal lithium-skeletal carbon-gold nanoparticle composite material/lithium half-cell, metal lithium-skeletal carbon material/lithium half-cell constant current charge-discharge test in the first embodiment. ;
  • Example 4 is a TEM image of carbon nanotube-loaded gold nanoparticles in Example 2.
  • Example 5 is a scanning electron microscope (SEM) photograph of the metal lithium-skeletal carbon-gold nanoparticle composite material of Example 2. The magnification on the left is 1000 times and the magnification on the right is 15,000 times.
  • Example 6 is a constant current constant capacity test curve of a simulated battery fabricated by using the metal lithium-skeletal carbon-gold nanoparticle composite material prepared in Example 2 as a negative electrode.
  • Example 7 is a TEM image of acetylene black-loaded gold nanoparticles in Example 3.
  • Example 8 is a constant current constant capacity test curve of a simulated battery fabricated by using the metal lithium-acetylene black-gold nanoparticle composite material prepared in Example 3 as a negative electrode.
  • Example 10 is a scanning electron microscope (SEM) photograph of a lithium magnesium alloy-skeletal carbon composite prepared in Example 4, with a magnification of 15,000 times.
  • Fig. 11 is a constant current constant capacity test curve of a simulated battery fabricated by using the lithium magnesium alloy-skeletal carbon composite material prepared in Example 4 as a negative electrode.
  • Figure 12 is a TEM image of the carbon skeleton-silver nanoparticle composite material of Example 5.
  • Example 13 is an SEM image of the metal lithium-skeletal carbon-silver nanoparticle composite material of Example 5. The magnification on the left is 1000 times and the right image is 5000 times.
  • Fig. 14 is a graph showing a constant current constant capacity test of a simulated battery produced by using the composite material prepared in Example 5 as a negative electrode.
  • Fig. 15 is a graph showing the results of lithium loading test of the metal lithium-skeletal carbon-zinc oxide particle composite material of Example 6.
  • Figure 16 is a SEM image of the metal lithium-skeletal carbon-zinc oxide particle composite material of Example 6.
  • Example 17 is a constant current constant capacity test curve of a simulated battery fabricated by using the composite material prepared in Example 6 as a negative electrode.
  • Porous carbon skeleton-nanoparticle composite
  • One aspect of the present invention provides a porous carbon skeleton-nanoparticle composite, wherein the nanoparticles are lithium reactive metals or oxide nanoparticles thereof, distributed in and on pores of the porous carbon skeleton.
  • the porous carbon skeleton has a particle size of 1-100 micrometers (preferably 1-25 micrometers), and has inner-scale and surface-scale nano-scale pores (a pore size distribution may be 1 to 200 nm, for example, 1 to 50 nm).
  • Carbon based porous material may have various shapes such as a sheet-like, spherical or spheroidal particle shape, preferably spherical or spheroidal.
  • the porous carbon skeleton is composed of carbon nanotubes, carbon nanofibers, carbon black, acetylene black, ketjen black, ultra-high conductivity agent Super P, graphite, mesocarbon microbeads, and porous activated carbon.
  • the porous carbon skeleton is a microsphere formed by intertwining a carbon nanotube or a carbon nanofiber with each other and having nanoscale pores on the inside and on the surface.
  • Such microspheres have an approximately solid structure (like a bristle structure), that is, the inside of the microspheres is filled with carbon nanotubes or carbon nanofibers, but there are nanoscale pores between the intertwined agglomerated carbon nanotubes or carbon nanofibers.
  • the carbon nanotubes or carbon nanofiber microspheres have at least any one of a microscopic spherical solid aggregate structure, a spherical aggregate structure, a spheroidal aggregate structure, a porous spherical aggregate structure, and a doughnut-shaped aggregate structure.
  • 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 passing through a surface.
  • Functional 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 nanoparticles have a particle size of from 1 to 20 nm, preferably from 2 to 10 nm.
  • the nanoparticle may be included in the porous carbon skeleton-nanoparticle composite in an amount of 1 to 50% by weight, preferably 2 to 20% by weight.
  • the lithium reactive metal forming the nanoparticles is selected from at least one of gold, silver, magnesium, platinum, aluminum, and zinc.
  • the lithium reactive metal oxide may include zinc oxide nanoparticles or the like.
  • One aspect of the present invention provides a method of preparing a porous carbon skeleton-nanoparticle composite, comprising: dispersing carbon nanotubes or carbon nanofibers loaded with nanoparticles in a solvent, or carbon-based porous materials together with nanoparticles The dispersion is formed and then spray dried; or the lithium carbon skeleton-porous carbon skeleton material is delithiated to obtain a porous carbon skeleton-nanoparticle composite.
  • the porous carbon skeleton-nanoparticle composite can be obtained by delithiation of a lithium alloy-porous carbon skeleton material (for example, delithiation by discharge treatment).
  • the lithium alloy-porous carbon skeleton material may be formed into a lithium magnesium alloy-skeletal carbon composite anode, which is removed from the lithium metal in the lithium magnesium alloy inside the material during discharge, leaving the metal magnesium particles to form a porous Carbon skeleton - metal magnesium nanoparticle composite.
  • the porous carbon skeleton-nanoparticle composite may be prepared by dispersing carbon nanotubes or carbon nanofibers having surface-loaded nanoparticles in a solvent to form a dispersion, followed by spray drying.
  • carbon nanotubes or carbon nanofibers having surface-loaded nanoparticles may be obtained by forming metal nanoparticles on the surface of carbon nanotubes or carbon nanofibers.
  • the surface of the carbon nanotube or carbon nanofiber contains a metal binding group (eg, a sulfhydryl group).
  • the method of preparing a porous carbon skeleton-nanoparticle composite from carbon nanotubes or carbon nanofibers having surface-loaded nanoparticles may include the following steps:
  • 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 a porous carbon skeleton-nanoparticle composite material.
  • 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 at spray drying can range from 1 milliliter per minute to 100 liters per minute.
  • the porous carbon skeleton-nanoparticle composite may be prepared by dispersing carbon nanotubes or carbon nanofibers together with nanoparticles in a solvent to form a dispersion, followed by spray drying.
  • the porous carbon skeleton-nanoparticle composite can be prepared by dispersing a carbon-based porous material in a colloidal solution of nanoparticles and then spray drying.
  • One aspect of the present invention provides a porous carbon skeleton-nanoparticle composite-metal lithium composite comprising the above porous carbon skeleton-nanoparticle composite material, and pores distributed in the porous carbon skeleton-nanoparticle composite material Inside and on the surface A metal lithium in which a porous carbon skeleton-nanoparticle composite material is used as a skeleton-supporting metal lithium, and metallic lithium exists in a simple substance or a surface thereof.
  • the mass of metallic lithium is from 1% to 70%, preferably from 10% to 70%, more preferably from 20% to 70%, by total mass of the composite.
  • One aspect of the present invention provides a method of producing a porous carbon skeleton-nanoparticle composite-metal lithium composite, comprising: mixing molten metal lithium with the above porous carbon skeleton-nanoparticle composite, and then cooling.
  • the mixing of the molten metallic lithium with the porous carbon skeleton-nanoparticle composite can include agitating and mixing the metallic lithium with the porous carbon skeleton-nanoparticle composite under heating (eg, about 200 ° C).
  • the mixing of the molten metallic lithium with the porous carbon skeleton-nanoparticle composite may include the step of immersing the porous carbon skeleton-nanoparticle composite in molten metallic lithium.
  • the porous carbon skeleton-nanoparticle composite material of the invention can have various uses, including improving the deposition efficiency of metallic lithium when metal lithium is bonded to the porous carbon skeleton, and forming a porous carbon skeleton-nanoparticle composite material-metal lithium composite formed with metallic lithium.
  • the material can be used as a negative electrode material for the battery, which enables the battery to have more excellent cycle stability and improve the safety of the battery.
  • One aspect of the present invention provides a method for improving lithium deposition efficiency when metal lithium is bonded to a porous carbon skeleton, comprising: forming a porous carbon skeleton-nanoparticle composite material of the present invention, and then mixing the molten lithium metal with the same Porous carbon skeleton-nanoparticle composite-metal lithium composite.
  • Another aspect of the present invention provides an electrode comprising the above porous carbon skeleton-nanoparticle composite-metal lithium composite as an active material.
  • Still another aspect of the present invention provides a lithium battery comprising the above electrode.
  • the lithium battery includes a primary lithium battery, a secondary lithium battery, a metal lithium-oxide battery, a metal lithium-sulfur secondary battery, or a metal lithium-air battery.
  • 1 is a porous carbon skeleton-nanoparticle composite in which the nanoparticles are lithium reactive metals or oxide nanoparticles thereof, distributed in and on the pores of the porous carbon skeleton.
  • Embodiment 2 is the porous carbon skeleton-nanoparticle composite according to Embodiment 1, wherein the porous carbon skeleton is a carbon-based porous material having a particle diameter of 1-100 ⁇ m and having nanometer-scale pores inside and on the surface.
  • the carbon-based porous material is formed of one or more of carbon nanotubes, carbon nanofibers, carbon black, acetylene black, ketjen black, Super P, graphite, mesocarbon microbeads, and porous activated carbon. .
  • porous carbon skeleton-nanoparticle composite material according to the embodiment 1 or 2, wherein the porous carbon skeleton is formed by intertwining and agglomerating carbon nanotubes or carbon nanofibers, internal and surface Microspheres with nanoscale pores.
  • porous carbon skeleton-nanoparticle composite material wherein the carbon nanotube or carbon nanofiber microsphere has at least a microscopic spherical solid aggregate structure, a spherical aggregate structure, and a spherical aggregate structure. Any one of a porous spherical aggregate structure and a doughnut-shaped aggregate structure.
  • the fifth embodiment is the porous carbon skeleton-nanoparticle composite material according to the embodiment 3 or 4, wherein the carbon nanotubes include any of multi-walled carbon nanotubes, double-walled carbon nanotubes, and single-walled carbon nanotubes. One or a combination of two or more, the carbon nanotubes are optionally subjected to surface functionalization.
  • porous carbon skeleton-nanoparticle composite according to any one of the embodiments 1 to 5, wherein the nanoparticles have a particle diameter of 1 to 20 nm, preferably 2 to 10 nm.
  • porous carbon skeleton-nanoparticle composite according to any one of the embodiments 1 to 6, wherein the lithium reactive metal is selected from the group consisting of gold, silver, magnesium, platinum, aluminum, and zinc. At least one.
  • porous carbon skeleton-nanoparticle composite according to any one of the embodiments 1-7, wherein the nanoparticle is contained in the porous carbon skeleton-nanoparticle composite in an amount of 1 to 50% by weight. .
  • Embodiment 9 is a method for producing the porous carbon skeleton-nanoparticle composite according to any one of Embodiments 1 to 8, which comprises carbon nanotubes or carbon nanofibers having nanoparticles supported on a surface thereof. Disperse in a solvent to form a dispersion, and then spray-dry; or disperse carbon nanotubes or carbon nanofibers together with nanoparticles in a solvent to form a dispersion, and then spray-dry; or disperse the carbon-based porous material in a colloidal solution of nanoparticles Medium and then spray dried.
  • Embodiment 10 is the method of embodiment 9, wherein the carbon nanotubes or carbon nanofibers having surface-loaded nanoparticles can be obtained by forming metal nanoparticles on the surface of the carbon nanotubes or carbon nanofibers.
  • the dispersing solvent comprises a combination of any one or more of water, ammonia, hydrochloric acid, ethanol, acetone, isopropanol .
  • inlet air temperature is 190 to 210 ° C
  • outlet air temperature is 90 to 110 ° C.
  • the spray rate is from 1 ml/min to 100 l/min.
  • the present invention is a porous carbon skeleton-nanoparticle composite-metal lithium composite comprising the porous carbon skeleton-nanoparticle composite according to any one of the embodiments 1-8 and distributed on the porous carbon.
  • the embodiment 15 is the porous carbon skeleton-nanoparticle composite-metal lithium composite according to the specific embodiment 14, wherein the mass of the metallic lithium is the overall quality of the porous carbon skeleton-nanoparticle composite-metal lithium composite 1% to 70%.
  • the embodiment 16 is a method for producing a porous carbon skeleton-nanoparticle composite-metal lithium composite, comprising: the molten metal lithium and the porous carbon skeleton-nano according to any one of embodiments 1-8.
  • the particulate composite is mixed and then cooled.
  • Embodiment 17 is the method of embodiment 16 wherein the mixing of the molten metallic lithium with the porous carbon skeleton-nanoparticle composite comprises:
  • porous carbon skeleton-nanoparticle composite is immersed in molten metal lithium.
  • Embodiment 18 is a method for improving lithium deposition efficiency when metal lithium is bonded to a porous carbon skeleton, comprising: forming the porous carbon skeleton-nanoparticle composite material according to any one of Embodiments 1-8, and then The molten lithium metal is mixed therewith.
  • Embodiment 19 is an electrode comprising the porous carbon skeleton-nanoparticle composite-metal lithium composite described in Embodiment 14 or 15 as an active material.
  • Embodiment 20 is a lithium battery comprising the electrode described in Embodiment 19 as a negative electrode.
  • nano gold colloid solution After boiling 500g of 0.01wt% chloroauric acid solution, 15ml of 1wt% sodium citrate solution was added thereto, and the nano gold colloid solution was obtained by boiling for 5 minutes, and then 5g carbon nanotubes (Shandong Dazhan Nano Material Co., Ltd.) were dispersed in 3000mL.
  • the inlet air temperature of the spray dryer was set to 200 ° C
  • the outlet air temperature was set at 150 ° C
  • the spray pressure was set to 40 MPa
  • injection volume was set.
  • a skeleton carbon-gold nanoparticle composite material was obtained.
  • the lithium metal and the skeleton carbon-gold nanoparticle composite material are placed in a heater, heated to 200 degrees Celsius, and the molten metal lithium is stirred together with the carbon material. After the stirring is completed, the mixture is cooled to room temperature to obtain lithium-carbon composite nanoparticles. Through the weighing test, the mass percentage of metallic lithium in the material was 53%.
  • Figure 1 is a transmission electron micrograph of gold nanoparticles (a) and gold nanoparticle-skeletal carbon composites (b).
  • 2 is a scanning electron micrograph of a gold nanoparticle-skeletal carbon composite (a, b) and a metallic lithium-gold nanoparticle-skeletal carbon composite (c, d). It can be seen that the gold nanoparticle-skeletal carbon composite has the same morphology as the framework carbon (carbon nanotube microspheres) (Fig. 2a and 2b), except that gold nanoparticles are distributed on the pores and surface of the framework carbon (Fig. 1b).
  • 3 is a voltage vs. capacity curve for different cycles of metal lithium-skeletal carbon-gold nanoparticle composite/lithium half-cell, metal lithium-skeletal carbon material/lithium half-cell constant current charge-discharge test.
  • the original metal lithium-skeletal carbon material is charged and discharged with constant current of the battery, and the overpotential of the battery is sharply increased, and is increased by about 3 V after 200 cycles, and the metal lithium-skeletal carbon in the present invention is improved.
  • the overpotential of the gold nanoparticle composite is only increased by 0.4V, so the material of the present invention has a better cycle life than the metallic lithium-skeletal carbon material.
  • thiolated multi-walled carbon nanotubes (Shandong Dazhan Nano Material Co., Ltd.) was ultrasonically dispersed in 100ml of a 1:10 mixture of ethanol and deionized water, and then 1.5M citric acid solution was added thereto. Its pH is adjusted to 1. Further, 1.5 mL of a 3 mM concentration of chloroauric acid solution was added thereto, and the mixture was thoroughly stirred and mixed to obtain a precursor.
  • the inlet air temperature of the spray dryer was set to 200 ° C, and the outlet temperature was set at At 150 ° C, the spray pressure was set to 40 MPa, and the injection amount was set to 500 mL / h. Further, 10 g of metallic lithium and 5 g of the skeleton carbon-gold nanoparticles obtained in the above step were stirred and mixed by heating (about 200 ° C), and after cooling the product, a metallic lithium-skeletal carbon-gold nanoparticle composite was obtained. Through the weighing test, the mass percentage of metallic lithium in the material was 52%.
  • the skeleton carbon material (the carbon nanotube microspheres containing no gold nanoparticles) was prepared according to the above spray drying method, and the molten metal lithium was heated and stirred with the carbon material, and cooled. To room temperature, a metallic lithium-skeletal carbon composite was obtained. Through the weighing test, the mass percentage of metallic lithium in the material is 50%.
  • Figure 4 is a TEM image of a carbon nanotube loaded gold nanoparticle.
  • Fig. 5 is a scanning electron microscope (SEM) photograph of the metal lithium-skeletal carbon-gold nanoparticle composite material at a magnification of 1000 times and 15000 times.
  • Figure 6 shows the constant current constant capacity test curve of the prepared lithium metal-skeleton carbon-gold nanoparticle composite material as a negative electrode.
  • the pole piece prepared by the material is a negative electrode, and the metal lithium foil is used as a positive electrode at 0.5 mA. current density / cm 2, the capacity density of 0.5 mAh / cm 2 to make constant current charge-discharge cycle test of 200 cycles).
  • the lithium-carbon nanotube microsphere composite material has a small polarization voltage at the beginning, indicating that the material has a large specific surface area, which can greatly reduce the current density and effectively inhibit the formation of lithium dendrites. And because of the presence of gold nanoparticles, it promotes the deposition of lithium metal inside the material, so the material has better cycle stability than the metal lithium-skeletal carbon composite. As shown in the figure, the original metal lithium-skeletal carbon material is charged and discharged with the constant current of the battery, and the overpotential of the battery is sharply increased.
  • the increase is about 3V, and the metal lithium-skeletal carbon-gold nanoparticle composite
  • the overpotential of the material is only increased by 1V, so the metal lithium-skeletal carbon-gold nanoparticle composite of the present invention has a better cycle life than the metallic lithium-skeletal carbon material.
  • the temperature was set to 150 ° C at 200 ° C, the spray pressure was set to 40 MPa, and the injection amount was set to 500 mL / h.
  • 10g of metallic lithium is mixed with 5g of the above carbon particle-gold nanoparticle composite material, placed in a heater, heated to 200 degrees Celsius, melted The molten metal lithium is stirred together with the carbon material, and after stirring, it is cooled to room temperature to obtain a metal lithium-carbon particle-gold nanoparticle composite material. Through the weighing test, the mass percentage of metallic lithium in the material was 34%.
  • the mass percentage of metallic lithium in the material was 31%.
  • Figure 7 is a TEM image of acetylene black loaded gold nanoparticles.
  • Fig. 8 is a graph showing a constant current constant capacity test curve of a simulated battery fabricated by using the prepared lithium metal-acetylene black-gold nanoparticle composite as a negative electrode. It can be seen from the figure that the lithium-skeleton carbon-gold nanoparticle composite material has a small polarization voltage at the beginning, indicating that the material has a large specific surface area, which can greatly reduce the current density and effectively inhibit the formation of lithium dendrites. And because of the presence of gold nanoparticles, it promotes the deposition of lithium metal inside the material, so the material has better cycle stability than the metal lithium-skeletal carbon composite.
  • 10 g of multi-walled carbon nanotubes were dispersed in a mixed solution of 100 ml of ethanol and 1000 ml of deionized water, ultrasonically dispersed for 2 h, and then spray-dried and granulated.
  • the inlet air temperature of the spray dryer was set to 200 ° C, and the outlet temperature was set at At 150 ° C, the spray pressure was set to 40 MPa, and the injection amount was set to 500 mL / h.
  • the obtained carbon nanotube microspheres have a spherical aggregation structure, wherein the carbon nanotube microspheres have an average diameter of 5 ⁇ m, an electrical conductivity of 10 S ⁇ cm-1, a maximum withstand pressure of 20 MPa, and a specific surface area of 255 m 2 /g, And the pore diameter of the carbon nanotube microspheres is from 20 nm to 100 nm.
  • Figure 9 shows the lithium loading test curve for the composite.
  • Figure 10 shows a scanning electron microscope (SEM) photograph of the lithium magnesium alloy-skeletal carbon composite material at a magnification of 15,000 times.
  • Fig. 11 is a graph showing a constant current constant capacity test curve of a simulated battery fabricated by using the prepared lithium magnesium alloy-skeletal carbon composite as a negative electrode. It can be seen from the figure that the lithium-magnesium alloy-skeletal carbon composite material has a small polarization voltage at the beginning, indicating that the material has a large specific surface area, which can greatly reduce the current density and effectively inhibit the formation of lithium dendrites. And because of the presence of magnesium particles in the alloy, it promotes the deposition of metallic lithium inside the material, so the material has better cycle stability than the metallic lithium-skeletal carbon composite.
  • Figure 12 is a TEM image of a carbon skeleton-silver nanoparticle composite. It can be seen from the figure that silver nanoparticles enter the interior of the framework carbon material.
  • Figure 13 is an SEM image of a metallic lithium-skeletal carbon-silver nanoparticle composite material, the magnification on the left is 1000 times and the right is 5000 times.
  • Figure 14 shows a constant current constant capacity test curve of a simulated battery fabricated by using the prepared composite material as a negative electrode. It can be seen from the figure that the material has a small polarization voltage at the beginning, indicating that the material has a large specific surface area, which can greatly reduce the current density and effectively inhibit the formation of lithium dendrites.
  • the material has excellent cycle stability. It can be seen from the figure that the original metal lithium-skeletal carbon material is charged and discharged with the constant current of the battery, and the overpotential of the battery is sharply increased, and is increased by about 3 V after 200 cycles, and the metal lithium-skeletal carbon-gold nanoparticle composite material is increased. The overpotential has only increased by 0.8V, so the metal lithium-skeletal carbon-gold nanoparticle composite of the present invention has a better cycle life than the metallic lithium-skeletal carbon material.
  • Figure 15 shows the lithium loading test of the metal lithium-skeletal carbon-zinc oxide particle composite.
  • the specific capacity of the metal lithium-skeletal carbon-zinc oxide particle composite was improved by comparison with the metal lithium-skeletal carbon composite.
  • Figure 16 is an SEM image of a metallic lithium-skeletal carbon-zinc oxide particle composite.
  • Fig. 17 is a graph showing the constant current constant capacity test curve of the simulated battery fabricated by using the composite material prepared in this example as a negative electrode. It can be seen from the figure that the material has a small polarization voltage at the beginning, indicating that the material has a large specific surface area, which can greatly reduce the current density and effectively inhibit the formation of lithium dendrites.

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Abstract

一种多孔碳骨架-纳米颗粒复合材料、其金属锂复合物、它们的制备方法及应用。该多孔碳骨架-纳米颗粒复合材料包含分布于多孔碳骨架的孔隙内及表面上的锂反应性金属或其氧化物纳米颗粒。该多孔碳骨架-纳米颗粒复合材料可以降低金属锂结合于多孔碳骨架时的成核能或者提高锂与骨架碳的亲和性，提高电池的安全性和/或循环稳定性。

Description

多孔碳骨架-纳米颗粒复合材料、其金属锂复合物、它们的制备方法及应用 技术领域
本发明涉及纳米材料技术领域，特别涉及一种多孔碳骨架-纳米颗粒复合材料、其金属锂复合物、它们的制备方法及应用。
背景技术
锂电池是一种二次电池(充电电池)，它主要依靠锂离子在正极和负极之间移动来工作。在充放电过程中，Li+在两个电极之间往返嵌入和脱嵌：充电时，Li+从正极脱嵌，经过电解质嵌入负极，放电时则相反。锂电池由于具有高能量密度，环境友好性以及良好的循环稳定性等特性，因此已经广泛的运用在了电子产品，智能电网等领域。然而，目前的电子产品内部元器件越来越复杂以及电动汽车产业快速兴起，传统的锂离子电池的能量密度已经不能够满足日益增长的能耗要求，因此开发出具有更高能量密度的锂电池是目前能源领域最大的研究热点问题。
由于金属锂负极具有十倍于传统石墨负极的比容量，达到了3860mAh/g，并且金属锂具有最负的电位和最轻的密度，因此采用锂负极的电池能量密度将会有极大的提高。此外，锂金属负极可以为正极提供锂离子，因此可以和能量密度更高的无锂正极如硫，空气等组成高能量密度的锂硫-锂空气电池。不幸的是，金属锂负极在循环过程中容易产生枝晶，该枝晶会刺穿电池隔膜引起短路放出巨大的热，引发电池燃烧，爆炸等一系列安全事故。此外金属锂在循环过程中的界面不稳定性使得电池内部内阻增加，引起电池循环容量衰减。因此，需要提高采用锂负极的电池的安全性和循环寿命。
发明内容
本发明的主要目的在于提供一种多孔碳骨架-纳米颗粒复合材料、其金属锂复合物、它们的制备方法、包含它们的电极和锂电池，可以降低金属锂结合于多孔碳骨架时的成核能或者提高锂与骨架碳的亲和性，提高电池的安全性和/或循环稳定性。
本发明采用的技术方案包括：
在一些实施方式中提供了一种多孔碳骨架-纳米颗粒复合材料，其中所述纳米颗粒是锂反应性金属或其氧化物纳米颗粒，分布于所述多孔碳骨架的孔隙内及表面上。
在一些实施方式中提供了一种制备上述多孔碳骨架-纳米颗粒复合材料的方法，包括将表面负载有纳米颗粒的碳纳米管或碳纳米纤维分散于溶剂中形成分散液，然后喷雾干燥；或者将碳纳米管或碳纳米纤维和纳米颗粒一起分散于溶剂中形成分散液，然后喷雾干燥；或者将碳基多孔材料分散于纳米颗粒的胶体溶液中，然后喷雾干燥。
在一些实施方式中提供了一种孔碳骨架-纳米颗粒复合材料-金属锂复合物，包括上述的多孔碳骨架-纳米颗粒复合材料和分布于所述多孔碳骨架的孔隙内及表面上的金属锂。
在一些实施方式中提供了一种制备多孔碳骨架-纳米颗粒复合材料-金属锂复合物的方法，包括：将熔融的金属锂与上述的多孔碳骨架-纳米颗粒复合材料混合，然后冷却。
在一些实施方式中提供了一种在金属锂结合于多孔碳骨架时提高锂沉积效率的方法，包括：形成上述的多孔碳骨架-纳米颗粒复合材料，然后将熔融的金属锂与其混合
在一些实施方式中提供了一种电极，包含上述多孔碳骨架-纳米颗粒复合材料-金属锂复合物作为活性材料。
在一些实施方式中提供了一种锂电池，包含上述的电极作为负极。
本发明具有以下有益效果中的至少一种：
(1)存在于多孔碳骨架中的纳米颗粒在金属锂与多孔碳骨架结合时，充当锂的成核位点，降低成核能；或者通过与锂反应，提高与骨架碳的亲和性，提高锂沉积效率。
(2)多孔碳骨架内部的纳米颗粒促进金属锂沉积进入材料内部，因此在用于电池的负极材料时具有更加出色的循环稳定性。
(3)多孔碳骨架-纳米颗粒复合材料-金属锂复合物具有大的比表面积，能极大地降低电流密度，有效抑制锂枝晶的生成，从而提高电池的安全性。
(4)多孔碳骨架-纳米颗粒复合材料-金属锂复合物制备工艺简单，适合批量生产。
附图说明
图1为实施例1制备的金纳米颗粒(a)和金纳米颗粒-骨架碳复合物(b)的透射电镜图片；
图2为实施例1制备的金纳米颗粒-骨架碳复合物(a,b)和金属锂-金纳米颗粒-骨架碳复合物(c,d)的扫描电镜图片；
图3为实施例1中金属锂-骨架碳-金纳米颗粒复合材料/锂半电池，金属锂-骨架碳材料/锂半电池恒流充放电测试过程中不同循环次数时的电压-容量曲线图；
图4为实施例2中碳纳米管负载金纳米颗粒的TEM图；
图5为实施例2中金属锂-骨架碳-金纳米颗粒复合材料的扫描电子显微镜(SEM)照片，左图放大倍数为1000倍，右图放大倍数为15000倍。
图6为实施例2中制备的金属锂-骨架碳-金纳米颗粒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。
图7为实施例3中乙炔黑负载金纳米颗粒TEM图。
图8为实施例3中制备的金属锂-乙炔黑-金纳米颗粒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。
图9为实施例4中制备的骨架碳-镁纳米颗粒和碳纳米管微球骨架的载锂量测试曲线。
图10为实施例4中制备的锂镁合金-骨架碳复合材料的扫描电子显微镜(SEM)照片，放大倍数为15000倍。
图11为实施例4中制备的锂镁合金-骨架碳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。
图12为实施例5中碳骨架-银纳米颗粒复合材料TEM图。
图13为实施例5中金属锂-骨架碳-银纳米颗粒复合材料的SEM图，左图放大倍数为1000倍，右图为5000倍。
图14为实施例5中制备的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。
图15为实施例6中金属锂-骨架碳-氧化锌颗粒复合材料的载锂量测试结果图。
图16为实施例6中金属锂-骨架碳-氧化锌颗粒复合材料的SEM图。
图17为实施例6中制备的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
具体实施方式
多孔碳骨架-纳米颗粒复合材料：
本发明的一个方面提供一种多孔碳骨架-纳米颗粒复合材料，其中所述纳米颗粒是锂反应性金属或其氧化物纳米颗粒，分布于所述多孔碳骨架的孔隙内及表面上。
在一些实施例中，所述多孔碳骨架是粒径为1-100微米(优选为1-25微米)、内部和表面具有纳米尺度孔隙(孔径分布可以为1～200nm，例如1～50nm)的碳基多孔材料。多孔碳骨架可以具有各种形状，例如片状、球形或类球状颗粒形状，优选为球形或类球形。
在一些实施例中，所述多孔碳骨架由碳纳米管、碳纳米纤维、炭黑、乙炔黑、科琴黑、特密高导电剂Super P、石墨、中间相碳微球和多孔活性炭中的一种或多种形成。
在一些实施例中，所述多孔碳骨架是由碳纳米管或碳纳米纤维相互交缠团聚而形成的、内部和表面上具有纳米尺度孔隙的微球。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。
在一些实施例中，所述碳纳米管或碳纳米纤维微球至少具有微小球状实体聚集结构、球形聚集结构、类球形聚集结构、多孔球形聚集结构和面包圈形聚集结构中的任意一种。
在一些实施例中，所述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，所述纳米颗粒的粒径为1-20nm，优选2-10nm。
在一些实施例中，所述纳米颗粒在多孔碳骨架-纳米颗粒复合材料中的含量可以为1～50wt％，优选为2～20wt％
在一些实施例中，形成纳米颗粒的锂反应性金属选自金、银、镁、铂、铝和锌中的至少一种。锂反应性金属氧化物可以包括氧化锌纳米颗粒等。
制备多孔碳骨架-纳米颗粒复合材料的方法：
本发明的一个方面提供一种制备多孔碳骨架-纳米颗粒复合材料的方法，包括：将负载有纳米颗粒的碳纳米管或碳纳米纤维分散于溶剂中，或者将碳基多孔材料和纳米颗粒一起形成分散液，然后喷雾干燥；或者通过将锂合金-多孔碳骨架材料脱锂，获得多孔碳骨架-纳米颗粒复合材料。
关于“纳米颗粒”，参见上面的“多孔碳骨架-纳米颗粒复合材料”部分中的相关描述。
在一些实施例中，多孔碳骨架-纳米颗粒复合材料可以通过将锂合金-多孔碳骨架材料脱锂(例如通过放电处理脱锂)而获得。例如，可以将锂合金-多孔碳骨架材料形成锂镁合金-骨架碳复合负极，该材料在进行放电时材料内部的锂镁合金中的金属锂被脱掉，留下了金属镁颗粒，形成多孔碳骨架-金属镁纳米颗粒复合材料。
在一些实施例中，多孔碳骨架-纳米颗粒复合材料可以通过将表面负载有纳米颗粒的碳纳米管或碳纳米纤维分散于溶剂中形成分散液，然后喷雾干燥而制备。
在一些实施例中，表面负载有纳米颗粒的碳纳米管或碳纳米纤维可以通过在碳纳米管或碳纳米纤维表面形成金属纳米颗粒而获得。优选地，碳纳米管或碳纳米纤维表面含有金属结合基团(例如巯基)。
在一些实施例中，由表面负载有纳米颗粒的碳纳米管或碳纳米纤维制备多孔碳骨架-纳米颗粒复合材料的方法可以包括如下步骤：
A、将表面负载有纳米颗粒的碳纳米管或碳纳米纤维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，即获得多孔碳骨架-纳米颗粒复合材料。
在一些实施例中，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。
在另外的实施例中，多孔碳骨架-纳米颗粒复合材料可以通过将碳纳米管或碳纳米纤维和纳米颗粒一起分散于溶剂中形成分散液，然后喷雾干燥而制备。
关于“喷雾干燥”的具体步骤和条件，参见上述描述。
在另外的实施例中，多孔碳骨架-纳米颗粒复合材料可以通过碳基多孔材料分散于纳米颗粒的胶体溶液中，然后喷雾干燥而制备。
关于“碳基多孔材料”，参见上面的“多孔碳骨架-纳米颗粒复合材料”部分中的相关描述。
多孔碳骨架-纳米颗粒复合材料-金属锂复合物
本发明的一个方面提供一种多孔碳骨架-纳米颗粒复合材料-金属锂复合物，其包含上述的多孔碳骨架-纳米颗粒复合材料，和分布于所述多孔碳骨架-纳米颗粒复合材料的孔隙内及表面上的 金属锂，其中，多孔碳骨架-纳米颗粒复合材料作为骨架负载金属锂，金属锂以单质形式存在于其中或其表面上。
在一些实施例中，金属锂的质量为所述复合材料总质量的1％～70％，优选10％～70％，更优选20％～70％。
制备多孔碳骨架-纳米颗粒复合材料-金属锂复合物的方法
本发明的一个方面提供一种制备多孔碳骨架-纳米颗粒复合材料-金属锂复合物的方法，包括：将熔融的金属锂与上述的多孔碳骨架-纳米颗粒复合材料混合，然后冷却。
在一些实施例中，熔融的金属锂与多孔碳骨架-纳米颗粒复合材料的混合可以包括将金属锂与多孔碳骨架-纳米颗粒复合材料在加热下(例如约200℃)搅拌混合。
在一些实施例中，熔融的金属锂与多孔碳骨架-纳米颗粒复合材料的混合可以包括将多孔碳骨架-纳米颗粒复合材料浸入熔融金属锂中的步骤。
多孔碳骨架-纳米颗粒复合材料的用途
本发明的多孔碳骨架-纳米颗粒复合材料可以具有多种用途，包括在金属锂结合于多孔碳骨架时提高金属锂沉积效率，与金属锂形成的多孔碳骨架-纳米颗粒复合材料-金属锂复合物可以用作电池的负极材料，使电池具有更加出色的循环稳定性并且提高电池的安全性。
本发明的一个方面提供一种在金属锂结合于多孔碳骨架时提高锂沉积效率的方法，包括：形成本发明的多孔碳骨架-纳米颗粒复合材料，然后将熔融的金属锂与其混合，制得多孔碳骨架-纳米颗粒复合材料-金属锂复合物。
本发明的另一个方面提供一种电极，包含上述的多孔碳骨架-纳米颗粒复合材料-金属锂复合物作为活性材料。
本发明的再一个方面提供一种锂电池，其包括上述的电极。
在一些实施例中，锂电池包括一次锂电池、二次锂电池、金属锂-氧化物电池、金属锂-硫二次电池或金属锂-空气电池。
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是一种多孔碳骨架-纳米颗粒复合材料，其中所述纳米颗粒是锂反应性金属或其氧化物纳米颗粒，分布于所述多孔碳骨架的孔隙内及表面上。
具体实施方式2是根据具体实施方式1所述的多孔碳骨架-纳米颗粒复合材料，其中所述多孔碳骨架是粒径为1-100微米的、内部和表面具有纳米尺度孔隙的碳基多孔材料，优选地，所述碳基多孔材料由碳纳米管、碳纳米纤维、炭黑、乙炔黑、科琴黑、Super P、石墨、中间相碳微球和多孔活性炭中的一种或多种形成。
具体实施方式3是根据具体实施方式1或2所述的多孔碳骨架-纳米颗粒复合材料，其中所述多孔碳骨架是由碳纳米管或碳纳米纤维相互交缠团聚而形成的、内部和表面上具有纳米尺度孔隙的微球。
具体实施方式4是根据具体实施方式3所述的多孔碳骨架-纳米颗粒复合材料，其中所述碳纳米管或碳纳米纤维微球至少具有微小球状实体聚集结构、球形聚集结构、类球形聚集结构、多孔球形聚集结构和面包圈形聚集结构中的任意一种。
具体实施方式5是根据具体实施方式3或4所述的多孔碳骨架-纳米颗粒复合材料，其中述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。
具体实施方式6是根据具体实施方式1-5中任一项所述的多孔碳骨架-纳米颗粒复合材料，其中所述纳米颗粒的粒径为1-20nm，优选2-10nm。
具体实施方式7是根据具体实施方式1-6中任一项所述的多孔碳骨架-纳米颗粒复合材料，其中所述锂反应性金属选自金、银、镁、铂、铝和锌中的至少一种。
具体实施方式8是根据具体实施方式1-7中任一项所述的多孔碳骨架-纳米颗粒复合材料，其中所述纳米颗粒在多孔碳骨架-纳米颗粒复合材料中的含量为1～50wt％。
具体实施方式9是一种用于制备具体实施方式1-8中任一项所述的多孔碳骨架-纳米颗粒复合材料的方法，其中包括将表面负载有纳米颗粒的碳纳米管或碳纳米纤维分散于溶剂中形成分散液，然后喷雾干燥；或者将碳纳米管或碳纳米纤维和纳米颗粒一起分散于溶剂中形成分散液，然后喷雾干燥；或者将碳基多孔材料分散于纳米颗粒的胶体溶液中，然后喷雾干燥。
具体实施方式10是根据具体实施方式9所述的方法，其中所述表面负载有纳米颗粒的碳纳米管或碳纳米纤维可以通过在碳纳米管或碳纳米纤维表面形成金属纳米颗粒而获得。
具体实施方式11是根据具体实施方式9-10中任一项所述的方法，其中所述碳纳米管或碳纳米纤维表面含有金属结合基团。
具体实施方式12是根据具体实施方式9-11中任一项所述的方法，其中所述分散溶剂包括水、氨水、盐酸溶液、乙醇、丙酮、异丙醇的任意一种或多种的组合。
具体实施方式13是根据具体实施方式9-12所述的方法，其中进风温度为190～210℃，出风温度为90～110℃，
和/或，喷雾速度为1毫升/分钟至100升/分钟。
具体实施方式14是一种多孔碳骨架-纳米颗粒复合材料-金属锂复合物，包括具体实施方式1-8中任一项所述的多孔碳骨架-纳米颗粒复合材料和分布于所述多孔碳骨架的孔隙内及表面上的金属锂。
具体实施方式15是根据具体实施方式14所述的多孔碳骨架-纳米颗粒复合材料-金属锂复合物，其中金属锂的质量为所述多孔碳骨架-纳米颗粒复合材料-金属锂复合物整体质量的1％～70％。
具体实施方式16是一种制备多孔碳骨架-纳米颗粒复合材料-金属锂复合物的方法，包括：将熔融的金属锂与具体实施方式1-8中任一项所述的多孔碳骨架-纳米颗粒复合材料混合，然后冷却。
具体实施方式17是根据具体实施方式16所述的方法，其中熔融的金属锂与多孔碳骨架-纳米颗粒复合材料的混合包括：
将金属锂与多孔碳骨架-纳米颗粒复合材料在加热下搅拌混合；
或者将多孔碳骨架-纳米颗粒复合材料浸入熔融金属锂中。
具体实施方式18是一种在金属锂结合于多孔碳骨架时提高锂沉积效率的方法，包括：形成具体实施方式1-8中任一项所述的多孔碳骨架-纳米颗粒复合材料，然后将熔融的金属锂与其混合。
具体实施方式19是一种电极，其包含具体实施方式14或15所述的多孔碳骨架-纳米颗粒复合材料-金属锂复合物作为活性材料。
具体实施方式20是一种锂电池，其包含具体实施方式19所述的电极作为负极。
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。
实施例1
将0.01wt％氯金酸溶液500g煮沸后向其中加入15ml 1wt％柠檬酸钠溶液，保持沸腾状态5min得到纳米金胶体溶液，再取5g碳纳米管(山东大展纳米材料有限公司)分散于3000mL的纳米金胶体溶液中，超声分散2h后喷雾干燥造粒，喷雾干燥机的进风温度设定为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，得到骨架碳-金纳米颗粒复合材料。将金属锂与骨架碳-金纳米颗粒复合材料置于加热器中，加热至200摄氏度，熔融的金属锂与该碳材料一起搅拌，搅拌结束之后，冷却至室温，得到锂-碳复合纳米颗粒。通过称重测试，材料中金属锂质量百分数为53％。
图1为金纳米颗粒(a)和金纳米颗粒-骨架碳复合物(b)的透射电镜图片。图2为金纳米颗粒-骨架碳复合物(a,b)和金属锂-金纳米颗粒-骨架碳复合物(c,d)的扫描电镜图片。可以看出，金纳米颗粒-骨架碳复合物具有与骨架碳(碳纳米管微球)相同的形貌(图2a和2b)，只是在骨架碳的孔隙和表面上分布有金纳米颗粒(图1b)。
作为比较，仅使用碳纳米管，按照上述喷雾干燥方法制备骨架碳材料(不含金纳米颗粒的碳纳米管微球)，并且熔融的金属锂与该碳材料一起加热搅拌，冷却至室温，得到金属锂-骨架碳复合物。通过称重测试，材料中金属锂质量百分数为50％。
图3为金属锂-骨架碳-金纳米颗粒复合材料/锂半电池，金属锂-骨架碳材料/锂半电池恒流充放电测试过程中不同循环次数时，电压vs.容量曲线。如图所示，原始的金属锂-骨架碳材料随着电池恒流充放电进行，电池的过电势急剧增大，200个循环后增加了约3V，而本发明中提高的金属锂-骨架碳-金纳米颗粒复合材料的过电势仅仅增加了0.4V，因此本发明中的材料比金属锂-骨架碳材料有着更好的循环寿命。
实施例2
取100mg巯基化多壁碳纳米管(山东大展纳米材料有限公司)超声分散于100ml体积比为1：10的乙醇与去离子水的混合液中，再向其中加入1.5M的柠檬酸溶液将其pH值调节至1。再向其中加入1.5mL的3mM浓度的氯金酸溶液，充分搅拌混合后得到前驱体。将前驱体置于紫外灯下(紫 外灯型号；GE.R 500W Helios Italquartz,250-450nm,λmax＝360nm)保持磁力搅拌的状态下保持光照60min，金纳米颗粒在碳管的表面原位还原，得到碳纳米管负载金纳米颗粒。将5g碳纳米管负载金纳米颗粒分散于100ml乙醇和1000ml去离子水的混合溶液中超声分散2h后喷雾干燥造粒，喷雾干燥机的进风温度设定为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。再称取10g金属锂与5g上步骤中所得的骨架碳-金纳米颗粒经过加热(约200℃)搅拌混合，待产物冷却后得到金属锂-骨架碳-金纳米颗粒复合材料。通过称重测试，材料中金属锂质量百分数为52％。
作为比较，仅使用巯基化多壁碳纳米管，按照上述喷雾干燥方法制备骨架碳材料(不含金纳米颗粒的碳纳米管微球)，并且熔融的金属锂与该碳材料一起加热搅拌，冷却至室温，得到金属锂-骨架碳复合物。通过称重测试，材料中金属锂质量百分数为50％。
图4为碳管负载金纳米颗粒TEM图。图5为所述金属锂-骨架碳-金纳米颗粒复合材料的扫描电子显微镜(SEM)照片，放大倍数为1000倍和15000倍。图6显示了制备的金属锂-骨架碳-金纳米颗粒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(该材料制备的极片为负极，金属锂箔作为正极，以0.5mA/cm2的电流密度，0.5mAh/cm2的容量密度做恒流充放电循环测试，循环数为200个)。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。并且由于金纳米颗粒的存在，在材料内部起到促进金属锂沉积的作用，因此该材料比金属锂-骨架碳复合材料具有更加出色的循环稳定性。如图所示，原始的金属锂-骨架碳材料随着电池恒流充放电进行，电池的过电势急剧增大，200个循环后增加了约3V，而金属锂-骨架碳-金纳米颗粒复合材料的过电势仅仅增加了1V，因此本发明的金属锂-骨架碳-金纳米颗粒复合材料比金属锂-骨架碳材料有着更好的循环寿命。
实施例3
将0.01wt％氯金酸溶液500g煮沸后向其中加入15ml 1wt％柠檬酸钠溶液，保持沸腾状态5min得到纳米金胶体溶液。取5g乙炔黑分散于3000mL的纳米金胶体溶液中，超声分散2h后喷雾干燥造粒，得到碳颗粒-金纳米颗粒复合材料超声分散2h后喷雾干燥造粒，喷雾干燥机的进风温度设定为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。取10g金属锂与5g上述碳颗粒-金纳米颗粒复合材料混合后置于加热器中，加热至200摄氏度，熔 融的金属锂与碳材料一起搅拌，搅拌结束之后，冷却至室温，得到金属锂-碳颗粒-金纳米颗粒复合材料。通过称重测试，材料中金属锂质量百分数为34％。
作为比较，仅使用乙炔黑，按照上述喷雾干燥方法制备骨架碳材料，并且熔融的金属锂与该碳材料一起加热搅拌，冷却至室温，得到金属锂-骨架碳复合物。通过称重测试，材料中金属锂质量百分数为31％。
图7为乙炔黑负载金纳米颗粒TEM图。图8显示了制备的金属锂-乙炔黑-金纳米颗粒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。从该图可以看出，锂-骨架碳-金纳米颗粒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。并且由于金纳米颗粒的存在，在材料内部起到促进金属锂沉积的作用，因此该材料比金属锂-骨架碳复合材料具有更加出色的循环稳定性。
实施例4
取10g多壁碳纳米管分散于100ml乙醇和1000ml去离子水的混合溶液中的，超声分散2h后喷雾干燥造粒，喷雾干燥机的进风温度设定为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。所得到的碳纳米管微球具有球形聚集结构，其中所述碳纳米管微球的平均直径为5μm，电导率为10S·cm-1，最大可承受压力为20MPa，比表面积为255m2/g，并且所述碳纳米管微球所含孔隙的孔径为20nm至100nm。
称取1g金属镁与9g金属锂在惰性气体环境中熔融混合，冷却后得到10％wt镁含量的锂镁合金。再称取10g锂镁合金与5g上步骤中所得的碳纳米管微球经过加热搅拌混合，待产物冷却后得到锂镁合金-骨架碳复合负极。该材料在进行放电时材料内部的锂镁合金中的金属锂被脱掉，留下了金属镁颗粒，获得骨架碳-镁纳米颗粒。
取10g金属锂与5g上述骨架碳-镁纳米颗粒复合材料混合后置于加热器中，加热至200摄氏度，熔融的金属锂与碳材料一起搅拌，搅拌结束之后，冷却至室温，得到金属锂-碳颗粒-镁纳米颗粒复合材料。通过称重测试，材料中金属锂质量百分数为62％。
取10g金属锂与5g上述碳纳米管微球混合后置于加热器中，加热至200摄氏度，熔融的金属锂与碳材料一起搅拌，搅拌结束之后，冷却至室温，得到金属锂-碳纳米管微球复合材料。通过称重测试，材料中金属锂质量百分数为50％。
图9显示了所述复合材料的载锂量测试曲线。图10显示了所述锂镁合金-骨架碳复合材料的扫描电子显微镜(SEM)照片，放大倍数为15000倍。图11显示了制备的锂镁合金-骨架碳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。从该图可以看出，锂镁合金-骨架碳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。并且由于合金中镁颗粒的存在，在材料内部起到促进金属锂沉积的作用，因此该材料比金属锂-骨架碳复合材料具有更加出色的循环稳定性。
实施例5
5ml无水乙二醇加热至169℃，保持1h，再向其中同时加入3ml 0.25M的硝酸银的乙二醇溶液，和0.375M的聚乙烯吡咯烷酮(分子量55000)的乙二醇溶液，加入速度0.375ml/min，保持温度为160℃反应45min，将产物离心，在用去离子水洗涤后得到银纳米颗粒。
取1g银纳米颗粒和9g碳纳米管在体积比为10：1的去离子水与无水乙醇的混合液中超声分散2h后喷雾干燥造粒，喷雾干燥机的进风温度设定为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，得到骨架碳-银纳米颗粒复合材料。将金属锂与碳骨架碳-银纳米颗粒复合材料置于加热器中，加热至200摄氏度，熔融的金属锂与碳材料一起搅拌，搅拌结束之后，冷却至室温，得到金属锂-骨架碳-银纳米颗粒复合材料。通过称重测试，材料中金属锂质量百分数为50％。
图12为碳骨架-银纳米颗粒复合材料TEM图，从图中可以看出银纳米颗粒进入了骨架碳材料的内部。图13为金属锂-骨架碳-银纳米颗粒复合材料的SEM图，左图放大倍数为1000倍，右图为5000倍。图14显示了制备的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。从该图可以看出，该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。并且由于银纳米颗粒的存在，在材料内部起到促进金属锂沉积的作用，因此该材料具有出色的循环稳定性。通过该图可知原始的金属锂-骨架碳材料随着电池恒流充放电进行，电池的过电势急剧增大，200个循环后增加了约3V，而金属锂-骨架碳-金纳米颗粒复合材料的过电势仅仅增加了0.8V，因此本发明的金属锂-骨架碳-金纳米颗粒复合材料比金属锂-骨架碳材料有着更好的循环寿命。
实施例6
取9g碳纳米管，1g氧化锌试剂(阿拉丁试剂有限公司)在体积比为10：1的去离子水与无水乙醇的混合液中超声分散2h后喷雾干燥造粒，喷雾干燥机的进风温度设定为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。得到骨架碳-氧化锌颗粒复合材料。将金属锂与碳骨架碳-氧化锌颗粒复合材料置于加热器中，加热至200摄氏度，熔融的金属锂与碳材料一起搅拌，搅拌结束之后，冷却至室温，得到金属锂-骨架碳-氧化锌颗粒复合材料。通过称重测试，材料中金属锂质量百分数为56％。
作为比较，仅使用碳纳米管，按照上述喷雾干燥方法制备骨架碳材料(不含纳米颗粒的碳纳米管微球)，并且熔融的金属锂与该碳材料一起加热搅拌，冷却至室温，得到金属锂-骨架碳复合物。通过称重测试，材料中金属锂质量百分数为50％。
图15为金属锂-骨架碳-氧化锌颗粒复合材料的载锂量测试，通过与金属锂-骨架碳复合材料对比，发现金属锂-骨架碳-氧化锌颗粒复合材料的比容量有了提高。图16为金属锂-骨架碳-氧化锌颗粒复合材料的SEM图。图17显示了本实施例制备的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。从该图可以看出，该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。
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 (20)

  1. 一种多孔碳骨架-纳米颗粒复合材料，其特征在于所述纳米颗粒是锂反应性金属或其氧化物纳米颗粒，分布于所述多孔碳骨架的孔隙内及表面上。
  2. 根据权利要求1所述的多孔碳骨架-纳米颗粒复合材料，其特征在于所述多孔碳骨架是粒径为1-100微米的、内部和表面具有纳米尺度孔隙的碳基多孔材料，优选地，所述碳基多孔材料由碳纳米管、碳纳米纤维、炭黑、乙炔黑、科琴黑、Super P、石墨、中间相碳微球和多孔活性炭中的一种或多种形成。
  3. 根据权利要求1或2所述的多孔碳骨架-纳米颗粒复合材料，其特征在于所述多孔碳骨架是由碳纳米管或碳纳米纤维相互交缠团聚而形成的、内部和表面上具有纳米尺度孔隙的微球。
  4. 根据权利要求3所述的多孔碳骨架-纳米颗粒复合材料，其特征在于所述碳纳米管或碳纳米纤维微球至少具有微小球状实体聚集结构、球形聚集结构、类球形聚集结构、多孔球形聚集结构和面包圈形聚集结构中的任意一种。
  5. 根据权利要求3或4所述的多孔碳骨架-纳米颗粒复合材料，其特征在于述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。
  6. 根据权利要求1-5中任一项所述的多孔碳骨架-纳米颗粒复合材料，其特征在于所述纳米颗粒的粒径为1-20nm，优选2-10nm。
  7. 根据权利要求1-6中任一项所述的多孔碳骨架-纳米颗粒复合材料，其特征在于所述锂反应性金属选自金、银、镁、铂、铝和锌中的至少一种。
  8. 根据权利要求1-7中任一项所述的多孔碳骨架-纳米颗粒复合材料，其特征在于所述纳米颗粒在多孔碳骨架-纳米颗粒复合材料中的含量为1～50wt％。
  9. 一种用于制备权利要求1-8中任一项所述的多孔碳骨架-纳米颗粒复合材料的方法，其特征在于包括将表面负载有纳米颗粒的碳纳米管或碳纳米纤维分散于溶剂中形成分散液，然后喷雾干燥；或者将碳纳米管或碳纳米纤维和纳米颗粒一起分散于溶剂中形成分散液，然后喷雾干燥；或者将碳基多孔材料分散于纳米颗粒的胶体溶液中，然后喷雾干燥。
  10. 根据权利要求9所述的方法，其特征在于所述表面负载有纳米颗粒的碳纳米管或碳纳米纤维可以通过在碳纳米管或碳纳米纤维表面形成金属纳米颗粒而获得。
  11. 根据权利要求9-10中任一项所述的方法，其特征在于所述碳纳米管或碳纳米纤维表面含有金属结合基团。
  12. 根据权利要求9-11中任一项所述的方法，其特征在于所述分散溶剂包括水、氨水、盐酸溶液、乙醇、丙酮、异丙醇的任意一种或多种的组合。
  13. 根据权利要求9-12所述的方法，其特征在于进风温度为190～210℃，出风温度为90～110℃，
    和/或，喷雾速度为1毫升/分钟至100升/分钟。
  14. 一种多孔碳骨架-纳米颗粒复合材料-金属锂复合物，包括权利要求1-8中任一项所述的多孔碳骨架-纳米颗粒复合材料和分布于所述多孔碳骨架的孔隙内及表面上的金属锂。
  15. 根据权利要求14所述的多孔碳骨架-纳米颗粒复合材料-金属锂复合物，其特征在于金属锂的质量为所述多孔碳骨架-纳米颗粒复合材料-金属锂复合物整体质量的1％～70％。
  16. 一种制备多孔碳骨架-纳米颗粒复合材料-金属锂复合物的方法，包括：将熔融的金属锂与权利要求1-8中任一项所述的多孔碳骨架-纳米颗粒复合材料混合，然后冷却。
  17. 根据权利要求16所述的方法，其特征在于熔融的金属锂与多孔碳骨架-纳米颗粒复合材料的混合包括：
    将金属锂与多孔碳骨架-纳米颗粒复合材料在加热下搅拌混合；
    或者将多孔碳骨架-纳米颗粒复合材料浸入熔融金属锂中。
  18. 一种在金属锂结合于多孔碳骨架时提高锂沉积效率的方法，包括：形成权利要求1-8中任一项所述的多孔碳骨架-纳米颗粒复合材料，然后将熔融的金属锂与其混合。
  19. 一种电极，其包含权利要求14或15所述的多孔碳骨架-纳米颗粒复合材料-金属锂复合物作为活性材料。
  20. 一种锂电池，其包含权利要求19所述的电极作为负极。
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