WO2019019412A1 - 纳米碳颗粒-多孔骨架复合材料、其金属锂复合物、它们的制备方法及应用 - Google Patents

纳米碳颗粒-多孔骨架复合材料、其金属锂复合物、它们的制备方法及应用 Download PDF

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WO2019019412A1
WO2019019412A1 PCT/CN2017/105676 CN2017105676W WO2019019412A1 WO 2019019412 A1 WO2019019412 A1 WO 2019019412A1 CN 2017105676 W CN2017105676 W CN 2017105676W WO 2019019412 A1 WO2019019412 A1 WO 2019019412A1
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Prior art keywords
carbon
porous
lithium
rule
particle
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PCT/CN2017/105676
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English (en)
French (fr)
Inventor
郭峰
王亚龙
康拓
刘承浩
陈鹏
沈炎宾
卢威
陈立桅
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China Energy Cas Technology Co Ltd
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China Energy Cas Technology Co Ltd
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Priority to JP2019560436A priority Critical patent/JP2020509566A/ja
Priority to EP17919284.4A priority patent/EP3660963A4/en
Priority to KR1020217020010A priority patent/KR20210084657A/ko
Priority to US16/477,791 priority patent/US20200123008A1/en
Priority to KR1020197022378A priority patent/KR20190099062A/ko
Publication of WO2019019412A1 publication Critical patent/WO2019019412A1/zh
Anticipated expiration legal-status Critical
Priority to US17/733,367 priority patent/US11866332B2/en
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Definitions

  • the invention relates to a nano composite material, in particular to a nano carbon particle-porous skeleton composite material, a metal lithium composite thereof, a preparation method thereof and application thereof.
  • Lithium batteries have been widely used in consumer electronics, electric vehicles and energy storage due to their high specific energy and long cycle life.
  • a lithium battery is a compound containing lithium as a positive electrode, and graphite is used as a negative electrode, and a specific capacity limit of a graphite-based negative electrode material is about 370 mAh/g. It is difficult to further increase the energy density of a lithium battery based on such a negative electrode material. Adapt to the market demand for higher energy density lithium batteries. Since the lithium metal anode has a high specific capacity (3860 mAh/g) and a low electrode potential (-3.04 V vs. standard hydrogen electrode), the lithium battery is widely used for consumption due to its high specific energy, long cycle life, and high voltage.
  • the lithium metal anode has a high specific capacity (3860 mAh/g), a low electrode potential (-3.04 V vs SHE) and a small density (0.59 g/cm 3 ).
  • the use of metallic lithium as the battery anode can significantly improve lithium.
  • metallic lithium is used as the negative electrode of the battery to provide lithium ions, and the positive electrode can be made of a lithium-free material such as sulfur or air.
  • the lithium metal negative battery continuously forms dendrites and "dead lithium" during the cycle, resulting in low coulombic efficiency and short cycle life. More importantly, the growth of dendrites may pierce the diaphragm and cause the positive and negative electrodes to meet and cause an internal short circuit, resulting in the release of a large amount of heat, causing the battery to burn or even explode.
  • the above problems have greatly limited the application of metallic lithium negative electrodes in recent decades.
  • the main object of the present invention is to provide a nano carbon particle-porous skeleton composite material, a metal lithium composite thereof, a preparation method thereof, an electrode comprising the same, and an electrochemical battery for suppressing formation of metal lithium dendrites and improving the battery Safety and / or cycle stability.
  • a nanocarbon particle-porous framework composite wherein the porous framework is a carbon-based porous microsphere material having a diameter of 1-100 micrometers, or a porous metal having internal pores having a pore size distribution of a micrometer size.
  • the material, the nano carbon particles are distributed in the pores and on the surface of the carbon-based porous microsphere material or the porous metal material.
  • a method for preparing a nanocarbon particle-porous skeleton composite material comprises: dispersing carbon nanotubes or carbon nanofibers together with nano carbon particles in a solvent to form a dispersion, and then spray drying; or The micron-sized porous graphite, mesocarbon microbeads, porous activated carbon or porous metal material are immersed in the nanocarbon particle solution, sonicated, and then dried.
  • a lithium-nanocarbon particle-porous framework composite comprising the nanocarbon particle-porous framework composite described above, and distributed in pores of the nanocarbon particle-porous framework composite and Metallic lithium on the surface.
  • a method of preparing a metallic lithium-nanocarbon particle-porous framework composite comprising: mixing molten lithium metal with the nanocarbon particle-porous framework composite described above, and then cooling.
  • an electrode comprising the lithium-carbon nanoparticle-porous framework composite described above is provided.
  • an electrochemical energy storage device comprising the above electrode, wherein the electrochemical energy storage device comprises an electrochemical cell or a supercapacitor,
  • the nano carbon particles-porous skeleton composite material is mixed with molten metal lithium to form a lithium-nano carbon particle-porous skeleton composite material, and the nano carbon particles present in the material can better conduct lithium ions during battery cycling. Thereby, the formation of metal lithium dendrites is suppressed, and the safety of the battery is improved.
  • Lithium-nanocarbon particles-porous skeleton composite materials can be used as a negative electrode material for batteries to improve the cycle stability of the battery.
  • Metal lithium-nano carbon particles-porous skeleton composite materials can be applied to various lithium batteries, and can be applied to metal lithium-oxide batteries, metal lithium-polymer batteries, and rechargeable lithium ion batteries.
  • Example 1 shows a scanning electron micrograph of the acetylene black-carbon nanotube microsphere composite material (a, b) and lithium carbon micron composite particles (c, d) obtained in Example 1.
  • Figure 2 is an enlarged scanning electron micrograph (magnification 20000) of Figure 1b.
  • Fig. 3 shows the results of a half-cell cycle performance test conducted by the lithium carbon micron composite particles of Example 1 and lithium sheets, respectively, in a half-cell, at a current density of 0.5 mA cm -2 and a capacity of 0.5 mAh cm -2 .
  • Example 4 shows the lithium carbon micron composite particles of Example 1, the lithium sheets are respectively composed of a half-cell, a current density of 0.5 mA cm -2 , and the electrode morphology after a cycle of 0.5 mAh cm -2 (a, b is Lithium carbon micron composite particles, c, d are lithium sheets).
  • Fig. 5 is a graph showing the voltage-capacity curves of the lithium carbon microcomposite particles/lithium half-cells of Example 1 at different cycle times during the constant current charge and discharge test.
  • Fig. 6 is a view showing the test results of the capacity retention ratio at different cycle times under the condition of 1 C rate for the lithium carbon micron composite particles of Example 1 and the lithium battery composed of lithium iron phosphate and lithium iron phosphate, respectively.
  • Figure 7 shows a comparison of the microsphere materials formed separately without the carbon nanoparticles and the nanocarbon-containing particles, the left panel is the microsphere material obtained in Example 2, and the right panel is the microsphere material obtained in Example 1.
  • Fig. 8 shows the results of a half-cell cycle performance test in which lithium-carbon micron composite particles and lithium sheets of Example 2 were respectively composed of half-cells at a current density of 0.5 mA cm -2 and a capacity of 0.5 mAh cm -2 .
  • Figure 9 shows a scanning electron microscope (SEM) photograph of the lithium-carbon fiber microsphere composite of Example 5.
  • Fig. 10 is a graph showing the constant current charge and discharge curve of the lithium-carbon fiber microsphere composite of Example 5 as a negative electrode.
  • Fig. 11 is a view showing the test results of the half-cell cycle performance of the metal lithium-nickel skeleton carbon material-constituting half-cell of Example 6 under the conditions of a current density of 0.5 mA cm -2 and a capacity of 0.5 mAh cm -2 .
  • Fig. 12 is a view showing the test results of the capacity retention ratio at different cycle times under the condition of 1 C rate for the full battery composed of the metal lithium-nickel skeleton carbon material of Example 6.
  • Nano carbon particles - porous skeleton composite Nano carbon particles - porous skeleton composite:
  • One aspect of the present invention provides a nanocarbon particle-porous skeleton composite comprising a porous framework material composed of a carbon-based porous microsphere material having a diameter of 1 to 100 ⁇ m or a porous metal material having an internal pore having a pore size distribution of a micrometer. And nanocarbon particles distributed in and on the pores of the porous framework material.
  • the carbon-based porous microsphere material comprises at least one of carbon nanotube or carbon nanofiber microsphere material, graphite, mesocarbon microbeads, and porous activated carbon.
  • the carbon nanotube or carbon nanofiber microsphere material is formed by intertwining a carbon nanotube or carbon nanofiber with one another, with a plurality of nanoscale pores on the interior 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 It can be used to hold nano carbon particles and metallic lithium particles.
  • the carbon nanotube or carbon nanofiber microsphere material is spherical or spheroidal particles, and the average diameter may be 1 ⁇ m to 100 ⁇ m, preferably 1 ⁇ m to 25 ⁇ m; and the specific surface area may be 100 to 1500 m 2 /g. Preferably, it is 150 to 500 m 2 /g; and the pores contained in the microspheres may have a pore size distribution of from 1 to 200 nm, preferably from 1 to 50 nm.
  • the microspheres containing nano carbon particles and the microspheres containing no carbon nanoparticles did not change significantly in the morphology, except that the pore volume decreased, for example, from 2.0 to 1.4 cm 3 g -1 .
  • the carbon nanotube or carbon nanofiber microsphere material has at least any one of a microspherical 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 graphite, mesocarbon microbeads, and porous activated carbon are in the form of flakes, spheres, or spheroidal particles, and may have an average diameter of 50 ⁇ m to 500 ⁇ m, preferably 100 ⁇ m to 200 ⁇ m; and a specific surface area of 100 to 1000 m. 2 / g, preferably 100 to 500 m 2 /g; the pores contained may have a pore size distribution of 20 to 500 nm, preferably 20 to 100 nm.
  • the porous metal material comprises at least one of porous copper, porous aluminum, porous zinc, porous iron, porous nickel, porous gold, and porous silver.
  • the porous metal material may have pores having a pore size distribution of from 100 to 1000 ⁇ m, preferably from 100 to 500 ⁇ m, and a specific surface area of from 50 to 500 m 2 /g, preferably from 50 to 200 m 2 /g.
  • the nanocarbon particles include at least one of carbon black (eg, Degussa carbon black), acetylene black, Ketjen black, Super High Conductivity Agent Super P, and Cabot BP2000.
  • carbon black eg, Degussa carbon black
  • acetylene black e.g., Ketjen black
  • Super High Conductivity Agent Super P e.g., Cabot BP2000.
  • the nanocarbon particles may have a size of from 1 to 500 nm, preferably from 50 to 200 nm.
  • the content of the nanocarbon particles in the nanocarbon particle-porous skeleton composite relative to the porous skeleton may be 20 to 500 wt%, preferably 50 to 200 wt%.
  • An aspect of the invention provides a method for preparing a nano carbon particle-porous skeleton composite material, comprising: dispersing carbon nanotubes or carbon nanofibers together with nano carbon particles in a solvent to form a dispersion, and then spray drying; or, The micron-sized porous graphite, mesocarbon microbeads, porous activated carbon or porous metal material are immersed in the nanocarbon particle solution, sonicated, and then dried.
  • the nanocarbon particle-carbon nanotube or carbon nanofiber microsphere composite may be prepared by a spray drying method, for example, the preparation method 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 nano carbon particles-carbon nanotube/carbon nanofiber microsphere composite material.
  • the mass ratio between the nanocarbon particles and the carbon nanotubes/carbon nanofibers in step A may be from 0.5:1 to 8:1, preferably from 0.5:1 to 5:1, more preferably 0.5:1. Until 2:1.
  • nanocarbon particles and “carbon nanotubes/carbon nanofibers”, see the relevant description in the "Nanocarbon particles-porous skeleton composites” section above.
  • the concentration of the carbon nanotubes/carbon nanofibers in the dispersion may be from 10 to 50 g/L, preferably from 10 to 15 g/L.
  • 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 nanocarbon particle-porous framework composite is prepared by impregnation ultrasonication using micron-sized porous graphite, mesocarbon microbeads, porous activated carbon, or a porous metal material as the porous framework material.
  • the immersion ultrasonic method may include immersing micron-sized porous graphite, mesophase carbon microspheres, porous activated carbon or porous metal material in a nano carbon particle solution, sonicating, and then drying.
  • the nanocarbon particle solution comprises an aqueous solution of nanocarbon particles, or a solution in an ethanol solvent or a mixed solvent of ethanol and water.
  • the concentration of the nanocarbon particles in the nanocarbon particle solution may range from 5 to 50 g/L, preferably from 10 to 30 g/L.
  • One aspect of the present invention provides a metal lithium-carbon nanoparticle-porous skeleton composite material comprising the above-described nano carbon particle-porous skeleton composite material, and distributed in pores of the nano carbon particle-porous skeleton composite material and Metallic lithium on the surface,
  • the nano-carbon particle-porous skeleton composite material is used as a skeleton-supporting metal lithium, and the metallic lithium exists in the form of a simple substance in the pores or on the surface thereof (mainly inside the pores, and the surface has less metallic lithium).
  • the mass of metallic lithium is from 1% to 95%, 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 preparing a metal lithium-carbon nanoparticle-porous skeleton composite comprising: mixing molten metal lithium with the above-described nanocarbon particle-porous skeleton composite, and then cooling.
  • the mixing of the molten metallic lithium with the nanocarbon particle-carbon based porous microsphere composite can include agitating and mixing the metallic lithium with the carbon-based porous microsphere material under heating.
  • the agitation mixing can include a pre-stirring step and a rapid agitation step, wherein the pre-stirring step includes metal lithium and nano-carbon particles-porous at a relatively low temperature (eg, about 200 ° C - 230 ° C)
  • a relatively low temperature eg, about 200 ° C - 230 ° C
  • the mixture of skeleton composites is stirred at a low speed (for example, about 50 rpm to 100 rpm) for a short period of time (for example, 1-5 minutes), and the rapid stirring step is included at a relatively high temperature (for example, about 230 ° C - 300 °C) Rapid agitation (for example, about 150 rpm to 1000 rpm, preferably 200 rpm to 800 rpm).
  • the mixing of the molten metallic lithium with the nanocarbon particulate-porous metal composite may include the step of immersing the nanocarbon particulate-porous metal composite in molten metallic lithium.
  • the mass of metallic lithium is from 1% to 95%, preferably from 10% to 70%, more preferably from 20% to 70%, by total mass of the composite.
  • One aspect of the present invention provides an electrode comprising the above-described metal lithium-carbon nanoparticle-porous skeleton composite material as an electrode material.
  • the metallic lithium-nanocarbon particle-porous framework composite can be used as an active material for a battery negative electrode or (in the case of a porous metal skeleton) directly used as an electrode.
  • One aspect of the invention provides an electrochemical energy storage device comprising the electrodes described above.
  • the electrochemical energy storage device is an electrochemical cell that acts as a battery negative electrode.
  • the electrochemical cell comprises a lithium battery, a metal lithium-oxide battery, a metal lithium-sulfur secondary battery, or a metal lithium-air battery.
  • the electrochemical energy storage device is a supercapacitor that acts as one electrode sheet for a supercapacitor.
  • the lithium-nanocarbon particle-porous skeleton composite material provided by the invention when applied to an electrochemical battery, the nano carbon particles present in the material can better conduct lithium ions during battery cycling, thereby inhibiting metal lithium branches
  • the formation of crystals improves the safety of the battery and also improves the cycle stability of the battery.
  • porous skeleton is a carbon-based porous microsphere material having a diameter of 1 to 100 ⁇ m, or a porous metal material having internal pores having a pore size distribution of a micrometer,
  • the nanocarbon particles are distributed in and on the pores of the carbon-based porous microsphere material or the porous metal material.
  • Embodiment 2 is the nano carbon particle-porous skeleton composite material according to Embodiment 1, wherein the carbon-based porous microsphere material comprises carbon nanotube or carbon nanofiber microsphere material, graphite, mesophase carbon microsphere And at least one of porous activated carbon, wherein the carbon nanotube or carbon nanofiber microsphere material is formed by intertwining a carbon nanotube or a carbon nanofiber, and the inside of the microsphere is filled with carbon nanotubes or carbon nanofibers, and the inside And a large number of nanoscale pores on the surface;
  • the porous metal material includes at least one of porous copper, porous aluminum, porous zinc, porous iron, porous nickel, porous gold, and porous silver.
  • the nano carbon particles include at least one of carbon black, acetylene black, ketjen black, super high conductivity agent Super P, and Cabot BP2000.
  • the third embodiment is the nano carbon particle-porous skeleton composite material according to the embodiment 1 or 2, wherein the nano carbon particles may have a size of 1 to 500 nm, preferably 50 to 200 nm.
  • nano carbon particle-porous skeleton composite according to any one of the embodiments 1 to 3, wherein the content of the nano carbon particles relative to the porous skeleton is 20 to 500 wt%.
  • nano carbon particle-porous skeleton composite material according to any one of the embodiments 2-4, wherein the carbon nanotube or carbon nanofiber microsphere material has a specific surface area of 100 to 1500 m 2 / g;
  • the carbon nanotube or carbon nanofiber microsphere material has a pore diameter of 1 to 200 nm;
  • the carbon nanotube or carbon nanofiber microsphere material has at least one of a microscopic spherical solid aggregate structure, a spherical aggregate structure, a spherical aggregate structure, a porous spherical aggregate structure, and a doughnut 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 subjected to surface functionalization deal with.
  • micron-sized porous graphite, mesocarbon microbeads, porous activated carbon or porous metal material are immersed in a nanocarbon particle solution, sonicated, and then dried.
  • Embodiment 7 is the method of embodiment 6, wherein the method of spray drying the carbon nanotubes or carbon nanofibers together with the nano carbon particles comprises the steps of:
  • 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 nano carbon particles-carbon nanotube/carbon nanofiber microsphere composite material.
  • step A is a method according to a specific embodiment 7, wherein the mass ratio between the nano carbon particles and the carbon nanotubes/carbon nanofibers in step A is from 0.5:1 to 8:1;
  • the concentration of the carbon nanotubes/carbon nanofibers in the dispersion is 10 to 50 g/L;
  • the dispersing solvent includes any one or a combination of water, ammonia water, hydrochloric acid solution, ethanol, acetone, and isopropyl alcohol.
  • 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.
  • Embodiment 8 is the method of embodiment 6, wherein the nano carbon particle solution comprises an aqueous solution of nano carbon particles;
  • the concentration of the nano carbon particles in the nano carbon particle solution is 5 to 50 g/L.
  • the embodiment 10 is a metal lithium-carbon nanoparticle-porous skeleton composite material, comprising the nano carbon particle-porous skeleton composite material according to any one of embodiments 1 to 5, and distributed to the nanocarbon Metallic lithium in and on the pores of the particle-porous framework composite.
  • Embodiment 11 is the lithium-nano carbon particle-porous skeleton composite material according to Embodiment 10, wherein the mass of the metal lithium is 1% to 95% of the total mass of the lithium-nano carbon particle-porous skeleton composite material. .
  • FIG. 12 is a method of preparing a metal lithium-carbon nanoparticle-porous skeleton composite material, comprising: compounding molten lithium metal with the nano carbon particle-porous skeleton according to any one of embodiments 1-5. The materials are mixed and then cooled.
  • Embodiment 13 is the method of embodiment 11, wherein the mixing of the molten metallic lithium with the nanocarbon particle-carbon based porous microsphere composite comprises:
  • the nanocarbon particle-porous metal composite is immersed in molten metal lithium.
  • Embodiment 14 is the method of embodiment 13, wherein the agitation mixing comprises a pre-stirring step and a rapid stirring step, wherein the pre-stirring step comprises metal lithium and nano-carbon particles-porous skeleton composite at 200 ° C to 230 ° C
  • the mixture is stirred at 50 rpm to 100 rpm for 1-5 minutes, and the rapid stirring step includes rapid stirring at 230 rpm to 1000 ° C at 150 rpm to 1000 rpm.
  • Embodiment 15 is an electrode comprising the lithium-nanocarbon particle-porous skeleton composite material described in Embodiment 10 or 11.
  • DETAILED DESCRIPTION 16 is an electrochemical energy storage device comprising the electrode of embodiment 15; the electrochemical energy storage device comprising an electrochemical cell or a supercapacitor.
  • Embodiment 17 is the electrochemical energy storage device according to Embodiment 16, wherein the electrochemical cell comprises a lithium battery, a metal lithium-oxide battery, a metal lithium-sulfur secondary battery, or a metal lithium-air battery.
  • an acetylene black-carbon nanotube microsphere composite material was obtained.
  • the composite was subjected to nitrogen adsorption desorption test, and the specific surface area of the microspheres was 103 m 2 /g, and the average pore diameter was 15.2 nm.
  • Example 1 shows a scanning electron micrograph of the acetylene black-carbon nanotube microsphere composite material (a, b) and lithium carbon micron composite particles (c, d) obtained in Example 1.
  • FIG. 2 is an enlarged scanning electron micrograph (magnification 20000) of FIG. 1b, in which the particulate matter in the circle is a carbon nanoparticle (acetylene black nanoparticle).
  • the left figure shows the cycle curve when using lithium carbon micron composite particles
  • the right picture shows the lithium film cycle curve.
  • the lithium carbon micron composite particles exhibit a small polarization voltage at the beginning compared with the lithium metal sheet, indicating that the material has a large specific surface area, and the post-cycle polarization voltage is There are no major changes that demonstrate the stability of the material structure and the surface solid electrolyte interface (SEI) layer during the cycle.
  • SEI surface solid electrolyte interface
  • Figure 4 shows lithium-carbon micron composite particles, lithium sheets respectively composed of half-cells, 0.5 mA cm -2 current density, 0.5 mAh cm -2 capacity after 200 cycles of electrode morphology (a, b is lithium carbon micro-composite Particles, c, d are lithium flakes).
  • a, b is lithium carbon micro-composite Particles, c, d are lithium flakes.
  • the lithium-carbon micron composite material retains the grain structure after the cycle, which proves the stability of the material structure during the cycle.
  • Figure 5 shows the voltage-capacity curve (current magnitude of 0.74 mA/cm -2 ) for lithium carbon micron composite particles/lithium half cells at different cycle times during constant current charge and discharge testing.
  • the capacity of the lithium carbon micron composite particles is basically unchanged after 500 cycles of 1C rate, indicating that the surface SEI layer is stable when the material is recycled, and metal lithium is not always consumed.
  • a lithium-carbon micro-composite particle and a lithium battery are respectively combined with a lithium iron phosphate composite battery (20 to 40 mg of lithium carbon micro-composite particles are pressed on a copper foam having a diameter of 1.5 cm and a thickness of 1 mm, and the material is used as a negative electrode; Iron lithium (LFP) electrode pole piece (produced by Suzhou Naxin New Energy Technology Co., Ltd., surface density is 0.7mAh/cm 2 ) as a positive electrode composed of 2025 button battery), at 1C rate (positive and negative electrode capacities are 1.4mAh and Under the condition of 40 mAh), the capacity retention rate under different cycle times was measured.
  • Figure 6 shows the test results. As shown in Fig.
  • a carbon nanotube microsphere material was prepared in the same manner as in Example 1 except that acetylene black was not used.
  • the microsphere material had a specific surface area of 151 m 2 /g and an average pore diameter of 18.7 nm.
  • Figure 7 shows a comparison of the microsphere materials formed without the nanocarbon particles (left) and the nanocarbon particles (right). It can be seen from the figure that the morphology of the microsphere material did not change significantly after the addition of carbon nanoparticles.
  • lithium carbon micron composite particles were prepared in the same manner as in Example 1, and the mass percentage of lithium in the lithium carbon micron composite particles was 40.4%.
  • the lithium carbon micron composite particles and the lithium sheets obtained above were respectively made into a half-cell, and the half-cell cycle performance test was carried out under the condition of a current density of 0.5 mA cm -2 and a capacity of 0.5 mAh cm -2 .
  • Figure 8 shows the results of the half-cell cycle performance test. As shown in FIG. 8, the lithium carbon micron composite particles of Example 2 were used to form a half-cell. As the number of cycles increased, the polarization voltage of the sample continued to increase, indicating that the surface of the sample surface gradually thickened due to the lithium metal. Caused by continuous reaction with the electrolyte.
  • the nanocarbon particle-porous skeleton composite material and the lithium carbon micron composite particles were prepared in the same manner as in Example 1 except that the acetylene black in Example 1 was replaced with Ketjen black ECP 600JD.
  • the mass percentage of lithium in the lithium carbon micron composite particles was 60.0%.
  • the morphology and performance test results of the obtained materials were similar to those of Example 1.
  • the nanocarbon particle-porous skeleton composite material and the lithium carbon micron composite particles were prepared in the same manner as in Example 1 except that the acetylene black in Example 1 was replaced with Dexter carbon black (Printex XE-2).
  • the mass percentage of lithium in the lithium carbon micron composite particles was 51.8%.
  • the morphology and performance test results of the obtained materials were similar to those of Example 1.
  • the morphology is similar to the acetylene black-carbon nanotube microsphere composite of Example 1.
  • the composite was subjected to nitrogen adsorption desorption test, and the specific surface area of the microspheres was 98 m 2 /g, and the average pore diameter was 13.1 nm.
  • Figure 10 shows a constant current charge and discharge curve of a lithium-carbon fiber microsphere composite as a negative electrode. It can be seen from the figure that the lithium-carbon fiber 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 branch crystals. Avoid battery safety hazards due to dendrite short circuit, and thus more likely to be applied in practical high energy density battery systems.
  • a porous metal nickel (pore size distribution of 100-500 ⁇ m) skeleton material having a diameter of 1.5 cm and a thickness of 500-1000 ⁇ m was placed in 100 mL of an aqueous solution of acetylene black (Alfa Aesar) at a concentration of 20 g/L, and then the solution was Ultrasonic dispersion treatment was carried out for 1 h.
  • the obtained mixture was allowed to stand in an oven at 80 ° C for 24 hours to obtain a porous metal nickel skeleton material containing nano carbon particles.
  • a porous metal nickel skeleton material containing nano-sized carbon particles is immersed in molten metal lithium to obtain a metal lithium-nickel skeleton material.
  • the mass percentage of lithium in the metallic lithium-nickel skeleton material was 50.0% [(mass of metallic lithium-nickel skeleton material - mass of metallic nickel skeleton) / mass of metallic lithium-nickel skeleton material].
  • the lithium metal-nickel skeleton carbon material was composed of a half-cell, a current density of 0.5 mA cm -2 , and a capacity of 0.5 mAh cm -2 , and the half-cell cycle performance was tested.
  • the results are shown in FIG. It can be seen from Fig. 11 that the polarization voltage is basically unchanged after 200 cycles of the sample, and the slight increase is caused by the gradual thickening of the surface SEI layer; and the stability of the capacity and coulombic efficiency under the full battery test condition further indicates the material structure and surface. The stability of the SEI layer.
  • a full battery composed of a metal lithium-nickel skeleton carbon material and lithium iron phosphate was measured for capacity retention at different cycle times under a condition of 1 C rate, and the results are shown in FIG.

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Abstract

一种纳米碳颗粒-多孔骨架复合材料、其金属锂复合物、它们的制备方法及应用。纳米碳颗粒-多孔骨架复合材料中，多孔骨架是直径1-100微米的碳基多孔微球材料，或是具有微米尺度孔径分布的内部孔隙的多孔金属材料，纳米碳颗粒分布于碳基多孔微球材料或多孔金属材料的孔隙内及表面上。纳米碳颗粒-多孔骨架复合材料与熔融金属锂混合形成锂-纳米碳颗粒-多孔骨架复合材料，存在于该材料中的纳米碳颗粒可以在电池循环过程中更好地传导锂离子，从而抑制金属锂枝晶的生成，提高电池的安全性和循环稳定性。

Description

纳米碳颗粒-多孔骨架复合材料、其金属锂复合物、它们的制备方法及应用 技术领域
本发明涉及一种纳米复合材料，特别涉及一种纳米碳颗粒-多孔骨架复合材料、其金属锂复合物、它们的制备方法及应用。
背景技术
锂电池因其高的比能量、长的循环寿命等优点，已经广泛应用于消费电子，电动汽车和储能等领域。但是目前锂电池是以含有锂元素的化合物作为正极，和石墨作为负极，而石墨类负极材料的比容量极限约为370mAh/g，基于这种负极材料已经难以进一步提高锂电池的能量密度，难以适应市场对更高能量密度锂电池的需求。由于金属锂负极具有高的比容量(3860mAh/g)，低的电极电势(-3.04V vs标准氢电极)，锂电池因其高的比能量、长的循环寿命，高电压而广泛应用于消费电子、电动汽车和储能等领域。金属锂负极具有高的比容量(3860mAh/g)，低的电极电势(-3.04V vs SHE)和小的密度(0.59g/cm3)一系列优势，采用金属锂作为电池负极能明显提高锂电池的能量密度。同时金属锂作为电池负极，可以提供锂离子，那么正极可以采用容量更高的不含锂元素的材料，例如硫，空气。
然而，金属锂负极电池在循环过程中不断形成枝晶和“死锂”，导致库伦效率低、循环寿命短。更重要的是，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，导致释放出大量的热，造成电池的燃烧甚至爆炸。上述问题使金属锂负极在近几十年的应用受到极大的限制。
发明内容
本发明的主要目的在于提供一种纳米碳颗粒-多孔骨架复合材料、其金属锂复合物、它们的制备方法、包含它们的电极和电化学电池，用以抑制金属锂枝晶的生成，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纳米碳颗粒-多孔骨架复合材料，其中所述多孔骨架是直径1-100微米的碳基多孔微球材料，或是具有微米尺度孔径分布的内部孔隙的多孔金属材料，所述纳米碳颗粒分布于所述碳基多孔微球材料或所述多孔金属材料的孔隙内及表面上。
在一些实施方式中提供了一种制备纳米碳颗粒-多孔骨架复合材料的方法，包括：将碳纳米管或碳纳米纤维与纳米碳颗粒一起分散于溶剂中形成分散液，然后喷雾干燥；或者将微米级多孔石墨、中间相碳微球、多孔活性炭或者多孔金属材料浸渍在纳米碳颗粒溶液中，超声处理，然后干燥。
在一些实施方式中提供了一种锂-纳米碳颗粒-多孔骨架复合材料，其包括上述的纳米碳颗粒-多孔骨架复合材料，和分布于所述纳米碳颗粒-多孔骨架复合材料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金属锂-纳米碳颗粒-多孔骨架复合材料的方法，包括：将熔融的金属锂与上述的纳米碳颗粒-多孔骨架复合材料混合，然后冷却。
在一些实施方式中提供了一种电极，其包含上述锂-纳米碳颗粒-多孔骨架复合材料。
在一些实施方式中提供了一种包括上述电极的电化学储能装置，其中所述电化学储能装置包括电化学电池或超级电容器，
本发明具有以下有益效果中的至少一种：
(1)纳米碳颗粒-多孔骨架复合材料与熔融金属锂混合形成锂-纳米碳颗粒-多孔骨架复合材料，存在于该材料中的纳米碳颗粒可以在电池循环过程中更好地传导锂离子，从而抑制金属锂枝晶的生成，提高电池的安全性。
(2)锂-纳米碳颗粒-多孔骨架复合材料可以用作电池的负极材料，提高电池的循环稳定性。
(3)制备工艺简单，适合批量生产。
(4)金属锂-纳米碳颗粒-多孔骨架复合材料可以应用于各式各样的锂电池，可应用于金属锂-氧化物电池，金属锂-聚合物电池，可充电锂离子电池。
附图说明
图1显示了实施例1中获得的乙炔黑-碳纳米管微球复合材料(a,b)和锂碳微米复合颗粒(c,d)的扫描电镜图。
图2是图1b的放大的扫描电镜图(放大倍数20000)。
图3显示了由实施例1的锂碳微米复合颗粒、锂片分别组成半电池，在0.5mA cm-2电流密度，0.5mAh cm-2的容量条件下，进行半电池循环性能测试的结果。
图4显示了实施例1的锂碳微米复合颗粒，锂片分别组成半电池，0.5mA cm-2电流密度，0.5mAh cm-2的容量条件下循环200圈后电极形貌(a，b为锂碳微米复合颗粒，c，d为锂片)。
图5显示了实施例1的锂碳微米复合颗粒/锂半电池在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6显示了实施例1的锂碳微米复合颗粒和锂片分别与磷酸铁锂组成的全电池，在1C倍率条件下，不同循环次数下的容量保持率的测试结果。
图7显示了不含纳米碳颗粒和含纳米碳颗粒时分别形成的微球材料的对比图，左图为实施例2获得的微球材料，右图为实施例1获得的微球材料。
图8显示了实施例2的锂碳微米复合颗粒、锂片分别组成半电池，在0.5mA cm-2电流密度，0.5mAh cm-2的容量条件下，进行半电池循环性能测试的结果。
图9显示了实施例5的锂-碳纤维微球复合材料的扫描电子显微镜(SEM)照片。
图10显示了实施例5的锂-碳纤维微球复合材料作为负极的恒流充放电曲线。
图11显示了实施例6的金属锂-镍骨架碳材料组成半电池，在0.5mA cm-2电流密度，0.5mAh cm-2的容量条件下，半电池循环性能的测试结果。
图12显示了实施例6的金属锂-镍骨架碳材料与磷酸铁锂组成的全电池，在1C倍率条件下，不同循环次数下的容量保持率的测试结果。
具体实施方式
纳米碳颗粒-多孔骨架复合材料：
本发明的一个方面提供一种纳米碳颗粒-多孔骨架复合材料，其包含由直径1-100微米的碳基多孔微球材料或具有微米尺度孔径分布的内部孔隙的多孔金属材料构成的多孔骨架材料，和分布于多孔骨架材料的孔隙内及表面上的纳米碳颗粒。
在一些实施例中，所述碳基多孔微球材料包括碳纳米管或碳纳米纤维微球材料、石墨、中间相碳微球和多孔活性炭中的至少一种。
在一些实施例中，所述碳纳米管或碳纳米纤维微球材料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纳米碳颗粒和金属锂颗粒。
在一些实施例中，所述碳纳米管或碳纳米纤维微球材料为球形或类球状颗粒，平均直径可以为1μm～100μm，优选为1μm～25μm；比表面积可以为100～1500m2/g，优选为150～500m2/g； 微球内所含孔隙的孔径分布可以为1～200nm，优选为1～50nm。含纳米碳颗粒的微球和不含纳米碳颗粒的微球在形貌结构未发生明显变化，只是孔容减小，例如，从2.0减小至1.4cm3g-1。
在一些实施例中，所述碳纳米管或碳纳米纤维微球材料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，所述石墨、中间相碳微球和多孔活性炭为片状、球形或类球状颗粒形状，平均直径可以为50μm～500μm，优选为100μm～200μm；比表面积可以为100～1000m2/g，优选为100～500m2/g；所含孔隙的孔径分布可以为20～500nm，优选为20～100nm。
在一些实施例中，多孔金属材料包括多孔铜，多孔铝，多孔锌，多孔铁，多孔镍，多孔金和多孔银中的至少一种。
在一些实施例中，多孔金属材料的所含孔隙的孔径分布可以为100～1000μm，优选为100～500μm；比表面积可以为50～500m2/g，优选为50～200m2/g。
在一些实施例中，所述纳米碳颗粒包括炭黑(例如德固赛炭黑)，乙炔黑，科琴黑，特密高导电剂Super P，卡博特BP2000中的至少一种。
在一些实施例中，所述纳米碳颗粒的尺寸可以为1-500nm，优选50-200nm。
在一些实施例中，所述纳米碳颗粒-多孔骨架复合材料中纳米碳颗粒相对于多孔骨架的含量可以为20～500wt％，优选为50～200wt％。
制备纳米碳颗粒-多孔骨架复合材料的方法：
本发明的一个方面提供一种制备纳米碳颗粒-多孔骨架复合材料的方法，包括：将碳纳米管或碳纳米纤维与纳米碳颗粒一起分散于溶剂中形成分散液，然后喷雾干燥；或者，将微米级多孔石墨、中间相碳微球、多孔活性炭或者多孔金属材料浸渍在纳米碳颗粒溶液中，超声处理，然后干燥。
在一些实施例中，纳米碳颗粒-碳纳米管或碳纳米纤维微球复合材料可以通过喷雾干燥方法制备，例如，该制备方法可以包括如下步骤：
A、将碳纳米管/碳纳米纤维和纳米碳颗粒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，即获得纳米碳颗粒-碳纳米管/碳纳米纤维微球复合材料。
在一些实施例中，步骤A中纳米碳颗粒与碳纳米管/碳纳米纤维之间的质量比可以为0.5：1至8：1，优选为0.5：1至5：1，更优选0.5：1至2：1。
关于“纳米碳颗粒”和“碳纳米管/碳纳米纤维”，参见上面的“纳米碳颗粒-多孔骨架复合材料”部分中的相关描述。
在一些实施例中，碳纳米管/碳纳米纤维在分散液中的浓度可以为10～50g/L，优选10～15g/L。
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。
在一些实施例中，使用微米级多孔石墨、中间相碳微球、多孔活性炭或者多孔金属材料作为多孔骨架材料，采用浸渍超声方法制备纳米碳颗粒-多孔骨架复合材料。所述浸渍超声方法可以包括：将微米级多孔石墨、中间相碳微球、多孔活性炭或者多孔金属材料浸渍在纳米碳颗粒溶液中，超声处理，然后干燥。
在一些实施例中，所述纳米碳颗粒溶液包括纳米碳颗粒的水溶液，或者在乙醇溶剂或在乙醇和水混合溶剂中的溶液。
在一些实施例中，纳米碳颗粒在纳米碳颗粒溶液中的浓度可以为5～50g/L，优选10～30g/L。
金属锂-纳米碳颗粒-多孔骨架复合材料
本发明的一个方面提供一种金属锂-纳米碳颗粒-多孔骨架复合材料，其包含上述的纳米碳颗粒-多孔骨架复合材料，和分布于所述纳米碳颗粒-多孔骨架复合材料的孔隙内及表面上的金属锂， 其中，纳米碳颗粒-多孔骨架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孔隙中或其表面上(以孔隙内部为主，表面的金属锂较少)。
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％～95％，优选10％～70％，更优选20％～70％。
制备金属锂-纳米碳颗粒-多孔骨架复合材料的方法
本发明的一个方面提供一种制备金属锂-纳米碳颗粒-多孔骨架复合材料的方法，包括：将熔融的金属锂与上述的纳米碳颗粒-多孔骨架复合材料混合，然后冷却。
在一些实施例中，熔融的金属锂与纳米碳颗粒-碳基多孔微球复合材料的混合可以包括将金属锂与碳基多孔微球材料在加热下搅拌混合。
在一些实施例中，所述搅拌混合可以包括预搅拌步骤和快速搅拌步骤，其中预搅拌步骤包括在相对较低的温度(例如，约200℃-230℃)将金属锂与纳米碳颗粒-多孔骨架复合材料的混合物低速搅拌(例如，约50转/分钟-100转/分钟)较短时间(例如1-5分钟)，快速搅拌步骤包括在相对较高的温度(例如，约230℃-300℃)快速搅拌(例如，约150转/分钟-1000转/分钟，优选200转/分钟-800转/分钟)。
关于“碳基多孔微球材料”，参见“纳米碳颗粒-多孔骨架复合材料”部分中的相关描述。
在一些实施例中，熔融的金属锂与纳米碳颗粒-多孔金属复合材料的混合可以包括将纳米碳颗粒-多孔金属复合材料浸入熔融金属锂中的步骤。
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％～95％，优选10％～70％，更优选20％～70％。
金属锂-纳米碳颗粒-多孔骨架复合材料的用途
本发明的一个方面提供一种电极，包含上述的金属锂-纳米碳颗粒-多孔骨架复合材料作为电极材料。
在一些实施例中，金属锂-纳米碳颗粒-多孔骨架复合材料可以用作电池负极的活性材料或者(在采用多孔金属骨架的情况下)直接用作电极。
本发明的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，电化学储能装置是电化学电池，所述电极用作电池负极。
在一些实施例中，电化学电池包括锂电池、金属锂-氧化物电池、金属锂-硫二次电池或金属锂-空气电池。
在一些实施例中，电化学储能装置是超级电容器，所述电极用作超级电容器的一个电极片。
本发明提供的锂-纳米碳颗粒-多孔骨架复合材料，在应用于电化学电池时，存在于该材料中的纳米碳颗粒可以在电池循环过程中更好地传导锂离子，从而抑制金属锂枝晶的生成，从而提高电池的安全性，并且也可以提高电池的循环稳定性。
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是一种纳米碳颗粒-多孔骨架复合材料，其中所述多孔骨架是直径1-100微米的碳基多孔微球材料，或是具有微米尺度孔径分布的内部孔隙的多孔金属材料，所述纳米碳颗粒分布于所述碳基多孔微球材料或所述多孔金属材料的孔隙内及表面上。
具体实施方式2是根据具体实施方式1所述的纳米碳颗粒-多孔骨架复合材料，其中所述碳基多孔微球材料包括碳纳米管或碳纳米纤维微球材料、石墨、中间相碳微球和多孔活性炭中的至少一种，其中所述碳纳米管或碳纳米纤维微球材料由碳纳米管或碳纳米纤维相互交缠团聚而形成，微球内部充满碳纳米管或碳纳米纤维，内部和表面上具有大量纳米尺度孔隙；
和/或，所述多孔金属材料包括多孔铜，多孔铝，多孔锌，多孔铁，多孔镍，多孔金和多孔银中的至少一种，
和/或，所述纳米碳颗粒包括炭黑，乙炔黑，科琴黑，特密高导电剂Super P，卡博特BP2000中的至少一种。
具体实施方式3是根据具体实施方式1或2所述的纳米碳颗粒-多孔骨架复合材料，其中纳米碳颗粒的尺寸可以为1-500nm，优选50-200纳米。
具体实施方式4是根据具体实施方式1-3中任一项所述的纳米碳颗粒-多孔骨架复合材料，其中所述纳米碳颗粒相对于所述多孔骨架的含量为20-500wt％。
具体实施方式5是根据具体实施方式2-4中任一项所述的纳米碳颗粒-多孔骨架复合材料，其中所述碳纳米管或碳纳米纤维微球材料的比表面积为100～1500m2/g；
和/或，所述碳纳米管或碳纳米纤维微球材料所含孔隙的孔径为1～200nm；
和/或，所述碳纳米管或碳纳米纤维微球材料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；
和/或，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。
具体实施方式6是一种制备具体实施方式1-5中任一项所述的纳米碳颗粒-多孔骨架复合材料的方法，包括：
将碳纳米管或碳纳米纤维与纳米碳颗粒一起分散于溶剂中形成分散液，然后喷雾干燥；
或者，将微米级多孔石墨、中间相碳微球、多孔活性炭或者多孔金属材料浸渍在纳米碳颗粒溶液中，超声处理，然后干燥。
具体实施方式7是根据具体实施方式6所述的方法，其中将碳纳米管或碳纳米纤维与纳米碳颗粒一起喷雾干燥的方法包括如下步骤：
A、将碳纳米管/碳纳米纤维和纳米碳颗粒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，即获得纳米碳颗粒-碳纳米管/碳纳米纤维微球复合材料。
具体实施方式8是根据具体实施方式7所述的方法，其中步骤A中纳米碳颗粒与碳纳米管/碳纳米纤维之间的质量比0.5：1至8：1；
和/或，碳纳米管/碳纳米纤维在分散液中的浓度为10～50g/L；
和/或，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9是根据具体实施方式7或8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8是根据具体实施方式6所述的方法，其中所述纳米碳颗粒溶液包括纳米碳颗粒水溶液；
和/或，纳米碳颗粒在纳米碳颗粒溶液中的浓度为5～50g/L。
具体实施方式10是一种金属锂-纳米碳颗粒-多孔骨架复合材料，其中包括具体实施方式1-5中任一项所述的纳米碳颗粒-多孔骨架复合材料，和分布于所述纳米碳颗粒-多孔骨架复合材料的孔隙内及表面上的金属锂。
具体实施方式11是根据具体实施方式10所述的锂-纳米碳颗粒-多孔骨架复合材料，其中金属锂的质量为所述锂-纳米碳颗粒-多孔骨架复合材料整体质量的1％～95％。
具体实施方式12是一种制备金属锂-纳米碳颗粒-多孔骨架复合材料的方法，包括：将熔融的金属锂与具体实施方式1-5中任一项所述的纳米碳颗粒-多孔骨架复合材料混合，然后冷却。
具体实施方式13是根据具体实施方式11所述的方法，其中熔融的金属锂与纳米碳颗粒-碳基多孔微球复合材料的混合包括：
将金属锂与碳基多孔微球材料在加热下搅拌混合；
或者将纳米碳颗粒-多孔金属复合材料浸入熔融金属锂中。
具体实施方式14是根据具体实施方式13所述的方法，其中搅拌混合包括预搅拌步骤和快速搅拌步骤，其中预搅拌步骤包括在200℃-230℃将金属锂与纳米碳颗粒-多孔骨架复合材料的混合物以50转/分钟-100转/分钟搅拌1-5分钟，快速搅拌步骤包括在230℃-300℃以150转/分钟-1000转/分钟进行快速搅拌。
具体实施方式15是一种电极，其包含具体实施方式10或11所述的锂-纳米碳颗粒-多孔骨架复合材料。
具体实施方式16是一种电化学储能装置，其中包括具体实施方式15所述的电极；所述电化学储能装置包括电化学电池或超级电容器。
具体实施方式17是根据具体实施方式16的电化学储能装置，其中电化学电池包括锂电池、金属锂-氧化物电池、金属锂-硫二次电池或金属锂-空气电池。
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
首先将2g外径为20-30nm的多壁碳纳米管(中国科学院成都有机化学有限公司)和2g乙 炔黑(Alfa Aesar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，干燥后即得到乙炔黑-碳纳米管微球复合材料。对该复合材料进行氮气吸附脱附测试，微球比表面积为103m2/g，平均孔径为15.2nm。
称取100mg电池级金属锂和100mg上述乙炔黑-碳纳米管微球复合材料，置于对金属锂惰性的加热器中，加热至200摄氏度以50转/分钟预搅拌2分钟后在230摄氏度条件下以200转/分钟搅拌20分钟，混合结束，降温至室温，整个过程在氩气保护的手套箱中进行，水分含量低于10ppm，氧气含量低于10ppm。得到锂-碳复合微米颗粒。通过称重测试，锂在锂碳微米复合颗粒中的质量百分数为67.3％。
图1显示了实施例1中获得的乙炔黑-碳纳米管微球复合材料(a,b)和锂碳微米复合颗粒(c,d)的扫描电镜图。
图2是图1b的放大的扫描电镜图(放大倍数20000)，圆圈中的颗粒状物质的即为碳纳米颗粒(乙炔黑纳米颗粒)。
取上述获得的锂碳微米复合颗粒、锂片分别组成半电池(取上述获得的锂碳微米复合颗粒20～40mg压在直径为1.5cm，厚度为1mm的泡沫铜上，将该材料作为负极；将厚度为400μm，直径为1.5cm的锂片作为正极；采用Celgard隔膜与上述正、负极材料组成2025扣式电池)，在0.5mA cm-2电流密度，0.5mAh cm-2的容量条件下，进行半电池循环性能测试。图3显示了半电池循环性能测试结果，左图为采用锂碳微米复合颗粒时的循环曲线，右图为锂片循环曲线。从图中可以看出，与金属锂片相比，锂碳微米复合颗粒在开始阶段便表现出很小的极化电压，表明该材料所具有的大的比表面积，而循环后期极化电压并没有大的变化，证明了循环过程中材料结构和表面固体电解质界面(SEI)层)的稳定。
图4显示了锂碳微米复合颗粒，锂片分别组成半电池，0.5mA cm-2电流密度，0.5mAh cm-2的容量条件下循环200圈后电极形貌(a，b为锂碳微米复合颗粒，c，d为锂片)。对于锂片，经过循环后样品表面布满了枝晶，这给电池带来极大的安全隐患。反观锂碳微米复合材料，经过循环后样品仍保持颗粒结构，再次证明了循环过程中该材料结构的稳定性。
图5显示了锂碳微米复合颗粒/锂半电池在恒流充放电测试过程中不同循环次数时的电压-容量曲线(电流大小为0.74mA/cm-2)。在1C倍率条件下循环500圈后锂碳微米复合颗粒的容量基本不变，表明材料在循环时表面SEI层较稳定，不会一直消耗金属锂。
取锂碳微米复合颗粒和锂片分别与磷酸铁锂组成的全电池(取锂碳微米复合颗粒20～40mg压在直径为1.5cm，厚度为1mm的泡沫铜上，将该材料作为负极；磷酸铁锂(LFP)电极极片(苏州纳新新能源科技有限公司生产。面密度为0.7mAh/cm2)作为正极组成2025扣式电池)，在1C倍率(正、负极容量分别为1.4mAh和40mAh)条件下，测量不同循环次数下的容量保持率。图6显示了测试结果。如图6所示，1C倍率条件下循环600圈之后，锂碳微米复合颗粒与磷酸铁锂组成的全电池的放电容量保持率为92.8％，而以锂片为负极的全电池，容量一直下降，循环150次后几乎没有容量。
实施例2
除了不使用乙炔黑外，以与实施例1相同的方法制备碳纳米管微球材料。该微球材料的比表面积为151m2/g，平均孔径为18.7nm。图7显示了不含纳米碳颗粒(左图)和含纳米碳颗粒(右图)时分别形成的微球材料的对比图。从图中可见，加入碳纳米颗粒后微球材料的形貌结构并未发生明显变化。
采用上述碳纳米管微球材料，以与实施例1相同的方法制备锂碳微米复合颗粒，锂在锂碳微米复合颗粒中的质量百分数为40.4％。
取上述获得的锂碳微米复合颗粒、锂片分别组成半电池，在0.5mA cm-2电流密度，0.5mAh cm-2的容量条件下，进行半电池循环性能测试。图8显示了半电池循环性能测试结果。如图8所示，采用实施例2的锂碳微米复合颗粒形成半电池，随着循环次数的增加，样品的极化电压持续增大，表明样品表面SEI层逐渐变厚，这是由于金属锂与电解液持续反应导致的。
实施例3
以与实施例1相同的方法制备纳米碳颗粒-多孔骨架复合材料和锂碳微米复合颗粒，只是用科琴黑(Ketjen black ECP 600JD)代替实施例1中的乙炔黑。锂在锂碳微米复合颗粒中的质量百分数为60.0％。所得材料的形貌和性能测试结果与实施例1类似。
实施例4
以与实施例1相同的方法制备纳米碳颗粒-多孔骨架复合材料和锂碳微米复合颗粒，只是用德固赛炭黑(Printex XE-2)代替实施例1中的乙炔黑。锂在锂碳微米复合颗粒中的质量百分数为51.8％。所得材料的形貌和性能测试结果与实施例1类似。
实施例5
首先将2g碳纳米纤维(Alfa Aesar公司)和2g乙炔黑(Alfa Aesar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，干燥后即得到乙炔黑-碳纳米纤维微球复合材料，形貌与实施例1中的乙炔黑-碳纳米管微球复合材料类似。对该复合材料进行氮气吸附脱附测试，微球比表面积为98m2/g，平均孔径为13.1nm。
称取100mg电池级金属锂和100mg上述乙炔黑-碳纳米纤维微球复合材料，置于对金属锂惰性的加热器中，加热至200摄氏度以50转/分钟预搅拌2分钟后在230摄氏度条件下以200转/分钟搅拌20分钟，混合结束，降温至室温，整个过程在氩气保护的手套箱中进行，水分含量低于10ppm，氧气含量低于10ppm。得到锂-碳复合微米颗粒。通过称重测试，锂在锂碳微米复合颗粒中的质量百分数为36.3％。图9显示了所述锂-碳纤维微球复合材料的扫描电子显微镜(SEM)照片，其中左图的放大倍数为1000倍，右图的放大倍数为25000倍。
图10显示了锂-碳纤维微球复合材料作为负极的恒流充放电曲线。从该图可以看出，锂-碳纤维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，有效抑制锂支晶的生成。避免由于枝晶短路带来的电池安全隐患，从而更有可能应用于实际的高能量密度电池体系中。
实施例6
将2g直径为1.5cm，厚度为500-1000μm的多孔金属镍(孔径分布在100-500μm)骨架材料置于100mL，浓度为20g/L的乙炔黑(Alfa Aesar公司)水溶液中，随后将该溶液进行超声分散处理1h。将得到的混合物在80℃烘箱中静置干燥24h后得到包含纳米碳颗粒的多孔金属镍骨架材料。将包含纳米级碳颗粒的多孔金属镍骨架材料浸入熔融的金属锂中，即得到金属锂-镍骨架材料。通过称重测试，锂在金属锂-镍骨架材料中的质量百分数为50.0％[(金属锂-镍骨架材料的质量—金属镍骨架的质量)/金属锂-镍骨架材料的质量]。
将该金属锂-镍骨架碳材料组成半电池，0.5mA cm-2电流密度，0.5mAh cm-2的容量条件下，测试半电池循环性能，结果如图11所示。从图11可以看出，样品循环200圈后极化电压基本不变，略微增加是由于表面SEI层逐渐变厚造成的；而全电池测试条件下容量和库仑效率的稳定进一步表明材料结构和表面SEI层的稳定。另外，将金属锂-镍骨架碳材料与磷酸铁锂组成的全电池在1C倍率条件下测量不同循环次数下的容量保持率，结果如图12所示。
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. [根据细则26改正14.11.2017]　
    一种纳米碳颗粒-多孔骨架复合材料，其特征在于所述多孔骨架是直径1-100微米的碳基多孔微球材料，或是具有微米尺度孔径分布的内部孔隙的多孔金属材料，所述纳米碳颗粒分布于所述碳基多孔微球材料或所述多孔金属材料的孔隙内及表面上。
  2. [根据细则26改正14.11.2017]　
    根据权利要求1所述的纳米碳颗粒-多孔骨架复合材料，其特征在于所述碳基多孔微球材料包括碳纳米管或碳纳米纤维微球材料、石墨、中间相碳微球和多孔活性炭中的至少一种，其中所述碳纳米管或碳纳米纤维微球材料由碳纳米管或碳纳米纤维相互交缠团聚而形成，微球内部充满碳纳米管或碳纳米纤维，内部和表面上具有大量纳米尺度孔隙；
    和/或，所述多孔金属材料包括多孔铜，多孔铝，多孔锌，多孔铁，多孔镍，多孔金和多孔银中的至少一种，
    和/或，所述纳米碳颗粒包括炭黑，乙炔黑，科琴黑，特密高导电剂Super P，卡博特BP2000中的至少一种。
  3. [根据细则26改正14.11.2017]　
    根据权利要求1或2所述的纳米碳颗粒-多孔骨架复合材料，其特征在于纳米碳颗粒的尺寸可以为1-500nm，优选50-200纳米。
  4. [根据细则26改正14.11.2017]　
    根据权利要求1-3中任一项所述的纳米碳颗粒-多孔骨架复合材料，其特征在于所述纳米碳颗粒相对于所述多孔骨架的含量为20-500wt％。
  5. [根据细则26改正14.11.2017]　
    根据权利要求2-4中任一项所述的纳米碳颗粒-多孔骨架复合材料，其特征在于所述碳纳米管或碳纳米纤维微球材料的比表面积为100～1500m2/g；
    和/或，所述碳纳米管或碳纳米纤维微球材料所含孔隙的孔径为1～200nm；
    和/或，所述碳纳米管或碳纳米纤维微球材料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；
    和/或，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。
  6. [根据细则26改正14.11.2017]　
    一种制备权利要求1-5中任一项所述的纳米碳颗粒-多孔骨架复合材料的方法，包括：
    将碳纳米管或碳纳米纤维与纳米碳颗粒一起分散于溶剂中形成分散液，然后喷雾干燥；
    或者，将微米级多孔石墨、中间相碳微球、多孔活性炭或者多孔金属材料浸渍在纳米碳颗粒溶液中，超声处理，然后干燥。
  7. [根据细则26改正14.11.2017]　
    根据权利要求6所述的方法，其特征在于将碳纳米管或碳纳米纤维与纳米碳颗粒一起喷雾干燥的方法包括如下步骤：
    A、将碳纳米管/碳纳米纤维和纳米碳颗粒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，即获得纳米碳颗粒-碳纳米管/碳纳米纤维微球复合材料。
  8. [根据细则26改正14.11.2017]　
    根据权利要求7所述的方法，其特征在于步骤A中纳米碳颗粒与碳纳米管/碳纳米纤维之间的质量比0.5：1至8：1；
    和/或，碳纳米管/碳纳米纤维在分散液中的浓度为10～50g/L；
    和/或，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。
  9. [根据细则26改正14.11.2017]　
    根据权利要求7或8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。
  10. [根据细则26改正14.11.2017]　
    根据权利要求6所述的方法，其特征在于所述纳米碳颗粒溶液包括纳米碳颗粒水溶液；
    和/或，纳米碳颗粒在纳米碳颗粒溶液中的浓度为5～50g/L。
  11. [根据细则26改正14.11.2017]　
    一种金属锂-纳米碳颗粒-多孔骨架复合材料，其特征在于包括权利要求1-5中任一项所述的纳米碳颗粒-多孔骨架复合材料，和分布于所述纳米碳颗粒-多孔骨架复合材料的孔隙内及表面上的金属锂。
  12. [根据细则26改正14.11.2017]　
    根据权利要求10所述的锂-纳米碳颗粒-多孔骨架复合材料，其特征在于金属锂的质量为所述锂-纳米碳颗粒-多孔骨架复合材料整体质量的1％～95％。
  13. [根据细则26改正14.11.2017]　
    一种制备金属锂-纳米碳颗粒-多孔骨架复合材料的方法，包括：将熔融的金属锂与权利要求1-5中任一项所述的纳米碳颗粒-多孔骨架复合材料混合，然后冷却。
  14. [根据细则26改正14.11.2017]　
    根据权利要求12所述的方法，其特征在于熔融的金属锂与纳米碳颗粒-碳基多孔微球复合材料的混合包括：
    将金属锂与碳基多孔微球材料在加热下搅拌混合；
    或者将纳米碳颗粒-多孔金属复合材料浸入熔融金属锂中。
  15. [根据细则26改正14.11.2017]　
    根据权利要求13所述的方法，其特征在于搅拌混合包括预搅拌步骤和快速搅拌步骤，其中预搅拌步骤包括在200℃-230℃将金属锂与纳米碳颗粒-多孔骨架复合材料的混合物以50转/ 分钟-100转/分钟搅拌1-5分钟，快速搅拌步骤包括在230℃-300℃以150转/分钟-1000转/分钟进行快速搅拌。
  16. [根据细则26改正14.11.2017]　
    一种电极，其包含权利要求10或11所述的锂-纳米碳颗粒-多孔骨架复合材料。
  17. [根据细则26改正14.11.2017]　
    一种电化学储能装置，其包括权利要求15所述的电极；所述电化学储能装置包括电化学电池或超级电容器。
  18. [根据细则26改正14.11.2017]　
    根据权利要求16的电化学储能装置，其特征在于电化学电池包括锂电池、金属锂-氧化物电池、金属锂-硫二次电池或金属锂-空气电池。
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