WO2019019411A1 - 具有疏水包覆层的金属锂-骨架碳复合材料、其制备方法与应用 - Google Patents
具有疏水包覆层的金属锂-骨架碳复合材料、其制备方法与应用 Download PDFInfo
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- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to the field of battery technology, and more particularly to a lithium carbon composite material that can be used for a lithium battery.
- Lithium-ion batteries are widely used in electronic products and power vehicles due to their high capacity, high energy density and good cycle stability.
- the metal lithium negative electrode has the lowest reduction potential (-3.045V vs H 2 /H + ), ten times the theoretical capacity of the conventional graphite negative electrode (3860mA h g -1 , graphite negative electrode: 372mA h g -1 ) is called battery energy storage.
- next-generation lithium battery with lithium metal anode lithium-sulfur battery (theoretical energy density 2600Wh/kg), and lithium air battery (theoretical energy density 5210Wh/kg) are required to be much higher than the current energy density of lithium-ion batteries.
- the use of these batteries as a power source for a powered car is a car that has a longer range when fully charged, providing an excellent solution to the energy problems of today's world.
- metal lithium negative electrode must be performed under the condition of argon gas protection, which seriously increases the use cost and safety hazard of the metal lithium.
- dendrites will form on the surface, and the growth of dendrites may pierce the diaphragm and cause the positive and negative electrodes to meet and internal short circuit, releasing a large amount of heat, causing the battery to burn or even explode. .
- the main object of the present invention is to provide a metal lithium-skeletal carbon composite material having a hydrophobic coating layer, a preparation method thereof, an electrode containing the metal lithium-framework carbon composite material, and an electrochemical energy storage device, and protecting water and oxygen A method of sensitive active metal materials.
- a metal lithium-skeletal carbon composite having a hydrophobic coating layer comprising: a metallic lithium-skeletal carbon composite comprising a porous carbon material support and pores distributed at least in the porous carbon material support And a hydrophobic coating layer covering at least the metal lithium metal based nanoparticle-carbon composite material in the metal lithium-skeletal carbon composite material.
- a method for preparing the above metal lithium-skeletal carbon composite having a hydrophobic coating layer comprises: mixing a metal lithium-carbon skeleton composite material with an organic solvent in which a film-forming hydrophobic substance or a compound having a lithium reactive portion and a hydrophobic portion is dissolved; obtaining a metal having a hydrophobic coating layer by solid-liquid separation or evaporation Lithium-skeletal carbon composite.
- a method of protecting a material comprising an active metal that is sensitive to water and oxygen comprising forming a hydrophobic coating on the material, the hydrophobic coating coating at least the material Active metal in the middle.
- an electrode comprising the above-described metallic lithium-skeletal carbon composite material having a hydrophobic coating layer as an electrode material.
- an electrochemical energy storage device that includes the electrodes described above.
- the formed dense hydrophobic coating layer has the function of isolating water and oxygen, and the coated material can be stably present in the air;
- a coating layer formed of a compound having a lithium reactive portion and a hydrophobic portion has a dual function of a passivation layer and a hydrophobic layer;
- the hydrophobic coating layer has a certain mechanical strength, can withstand the volume change of the solid electrolyte interface film (SEI film) on the surface of the metal lithium-skeletal carbon composite material, improve the cycle stability, and inhibit the generation of dendrites;
- SEI film solid electrolyte interface film
- Example 1 is a schematic view showing an octadecyl phosphate-coated metal lithium-skeletal carbon composite material in Example 1;
- Example 2 is a scanning electron micrograph of the metal lithium-skeletal carbon composite material (a, b) and the octadecyl phosphate-metal lithium-skeletal carbon composite material (c, d) in Example 1.
- Example 3 is an EDS (energy spectrum) analysis result of the change of oxygen content of the metal lithium-skeletal carbon composite material and the octadecyl phosphate-metal lithium-skeletal carbon composite material in Example 1 before and after exposure to dry air for 1 hour.
- Example 4 is a test result of capacity stability of a metal lithium-skeletal carbon composite material and an octadecyl phosphate-metal lithium-skeletal carbon-carbon composite material in Example 1 in dry air.
- Example 5 is a graph showing the different number of cycles of the octadecyl phosphate-metal lithium-skeletal carbon composite/lithium half-cell and the lithium metal-skeletal carbon composite/lithium half-cell in the constant current charge and discharge test in Example 1. Voltage vs. capacity graph.
- Example 6 is an octadecyl phosphate-metal lithium-skeletal carbon composite material under the condition of 1 C rate in Example 1, metal lithium-skeletal carbon A composite material, a lithium sheet, and a discharge specific capacity vs. cycle number of a full battery composed of lithium iron phosphate, respectively.
- Figure 8 is a graph showing the results of the stability test of PMMA-metal lithium-skeletal carbon composite in Example 2 in air.
- Example 9 is an SEM image of a paraffin-metal lithium-skeletal carbon composite material in Example 3.
- Figure 10 is a graph showing the results of the stability test of the paraffin-metal lithium-skeletal carbon composite in Example 3 in air.
- Figure 11 is a SEM image of the dodecyl mercaptan-metal lithium-skeletal carbon composite material of Example 4.
- Figure 12 is a graph showing the stability test results of the dodecyl mercaptan-metal lithium-skeletal carbon composite material in Example 4 in air.
- Figure 13 is a SEM image of the phenylphosphoric acid-metal lithium-skeletal carbon composite material of Example 5.
- Figure 14 is a graph showing the results of the stability test of the phenylphosphoric acid-metal lithium-skeletal carbon composite material in the air in Example 5.
- Fig. 15 is a graph showing a constant current constant capacity test of the simulated battery in the fifth embodiment.
- One aspect of the present invention provides a metal lithium-skeletal carbon composite material having a hydrophobic coating layer, comprising a metal lithium-skeletal carbon composite material and a hydrophobic coating layer, wherein the metal lithium-skeletal carbon composite material comprises a porous carbon material carrier And a metal lithium distributed in at least pores of the porous carbon material carrier, the hydrophobic coating layer coating at least metal lithium in the metal lithium-skeletal carbon composite material.
- the hydrophobic coating layer can be composed of a film forming hydrophobic material that forms a hydrophobic film on the exposed surface of the metallic lithium-skeletal carbon composite.
- the film-forming hydrophobic material is selected from the group consisting of a film-forming hydrophobic polymer and a film-forming hydrophobic small molecule
- the film-forming hydrophobic polymer may include polymethyl methacrylate (PMMA), polyvinylidene fluoride. Ethylene (PVDF), polydimethylsiloxane (PDMS), etc.
- film-forming hydrophobic small molecules may include paraffin, white oil, benzotriazole, and the like.
- the hydrophobic coating layer may be composed of a compound having a lithium reactive portion and a hydrophobic portion, the lithium reactive portion reacts with the metallic lithium to passivate it, the hydrophobic portion forms a hydrophobic layer, and the hydrophobic layer is located at the most external.
- the compound having a lithium reactive moiety and a hydrophobic moiety may be a linear small molecule compound having a lithium reactive group (lithium reactive moiety) at one end and a hydrophobic organic molecular chain at the other end ( The hydrophobic portion), by virtue of the anchoring effect of the lithium reactive group reacting with metallic lithium, the hydrophobic organic molecular chain is assembled into a hydrophobic layer on the surface of the metallic lithium.
- linear small molecule compounds may include surfactants and the like.
- the lithium reactive portion of the compound having a lithium reactive moiety and a hydrophobic moiety comprises phosphoric acid At least one of a group, a thiol group, a carbonic acid group, and optionally a fluorinated silane group.
- the hydrophobic portion of the compound having a lithium reactive moiety and a hydrophobic moiety comprises a C 4 -C 22 alkyl group, a C 6 -C 24 aryl group, and a siloxane group At least one of these groups is optionally substituted with a hydrophobic substituent.
- the C 4 -C 22 alkyl group may preferably be a C 8 -C 22 alkyl group or a C 12 -C 22 alkyl group.
- the hydrophobic substituent may be selected from the group consisting of fluorine, perfluoro groups, siloxanes, and the like.
- the hydrophobic coating layer has a thickness of 1-100 nm, such as 10-50 nm.
- the hydrophobic coating layer has electrical and/or ionic conductivity.
- the material of the porous carbon material carrier in the metal lithium-skeletal carbon composite material includes any one of carbon nanotubes, porous carbon, carbon black, graphene, carbon fiber, acetylene black, carbon aerogel or Combination of two or more.
- the porous carbon material support has at least any one of a fine particulate solid aggregate structure, a spherical aggregate structure, a spheroidal aggregate structure, and a doughnut aggregate structure.
- the pores of the porous carbon material support have an average pore diameter of from 10 to 100 nm.
- the porous carbon material support has an average particle diameter of from 1 to 100 ⁇ m, preferably from 1 to 50 ⁇ m, or from 1 to 15 ⁇ m.
- the porous carbon material support has an electrical conductivity of from 1*10 -3 to 10 S ⁇ cm -1 .
- the porous carbon material support has a specific surface area of from 100 to 1500 m 2 /g.
- the porous carbon material carrier can withstand a maximum pressure of 20 MPa or more.
- the porous carbon material support comprises carbon fiber microspheres, porous carbon nanotube microspheres, and acetylene black.
- the carbon fiber microspheres and the porous carbon nanotube microspheres are formed by intertwining a carbon nanotube or a carbon nanofiber with a large amount of nanometer-scale pores on the inside and on the surface.
- Such microspheres have an approximately solid structure (like a wool-like structure), that is, the inside of the microspheres is filled with carbon nanotubes or carbon nanofibers, but nano-scale pores exist between the entangled agglomerated carbon nanotubes or carbon nanofibers, and these pores Can be used to hold metallic lithium particles.
- Acetylene black is a carbon black obtained by cooling and collecting carbon dioxide by acetylene gas at a high temperature to isolate the air, and the particle diameter may be 40-50 nm.
- the carbon nanotube microspheres are spherical or spheroidal particles having an average diameter of from 1 ⁇ m to 100 ⁇ m, preferably from 1 ⁇ m to 25 ⁇ m.
- the carbon nanotubes include any one or a combination of two or more of multi-walled carbon nanotubes, double-walled carbon nanotubes, and single-walled carbon nanotubes, optionally subjected to surface function. Processing.
- the group modified on the surface of the carbon nanotube may be selected from, but not limited to, a group such as -COOH, -OH, -NH 2 or the like.
- the carbon nanotube microspheres can be dispersed by dispersing the carbon nanotubes in a solvent, and then spray dried. Prepared by drying.
- the preparation method may include the following steps:
- the carbon nanotubes are dispersed by ultrasonic treatment into a dispersion solvent (without a surfactant) to obtain a dispersion;
- step B The dispersion obtained in the step A is sprayed through the nozzle of the spray dryer, and the inlet air temperature and the outlet air temperature are preset, and the solution is kept in a stirring state during the spraying process;
- Cooling that is, obtaining carbon nanotube microspheres.
- the solvent employs an organic and/or inorganic liquid capable of uniformly dispersing carbon nanotubes/carbon nanofibers and nanocarbon particles, for example, water, ammonia, hydrochloric acid solution, ethanol, acetone, isopropanol. Any combination of one or more.
- an organic and/or inorganic liquid capable of uniformly dispersing carbon nanotubes/carbon nanofibers and nanocarbon particles, for example, water, ammonia, hydrochloric acid solution, ethanol, acetone, isopropanol. Any combination of one or more.
- the solvent may be a mixture of ethanol and water in a volume ratio of 1:10.
- the conditions of spray drying may include: an inlet air temperature of 150 to 250 ° C, an outlet air temperature of 75 ° C or higher, such as 75 to 150 ° C, or 90 ° C or higher; a preferred spray drying condition includes The inlet air temperature is 190 to 210 ° C, and the outlet air temperature is 90 to 110 ° C.
- the spray rate during spray drying can range from 1 milliliter per minute to 100 liters per minute.
- the metallic lithium-skeletal carbon composite may be obtained by mixing molten metal with a porous framework carbon material and cooling.
- the mixing may include stirring and mixing the metallic lithium with the porous framework carbon material under heating (for example, about 200 ° C) or immersing the porous skeleton carbon material in the molten metallic lithium.
- the preparation of the metallic lithium-skeletal carbon composite is carried out in an inert atmosphere, for example in a glove box under argon atmosphere (water content ⁇ 10 ppm, oxygen content ⁇ 10 ppm).
- the lithium metal is supported in the metal lithium-skeletal carbon composite in an amount of from 10 to 90% by weight.
- Another aspect of the present invention provides a method for preparing the above metal lithium-skeletal carbon composite material having a hydrophobic coating layer, comprising: dissolving a metal lithium-carbon skeleton composite material with a film forming hydrophobic material or having lithium The reactive portion is mixed with an organic solvent of the compound of the hydrophobic portion; a metal lithium-skeletal carbon composite having a hydrophobic coating layer is obtained by solid-liquid separation or evaporation.
- metal lithium-carbon skeleton composite material film-forming hydrophobic substance
- compound having a lithium-reactive portion and a hydrophobic portion refer to the relevant description in the above section.
- the organic solvent used to dissolve the film-forming hydrophobic substance or the compound having a lithium reactive moiety and a hydrophobic moiety may include any one of n-hexane, tetrahydrofuran, cyclohexane, and N-methylpyrrolidone. kind or a combination of two or more.
- the metal lithium-carbon skeleton composite material is mixed before the metal lithium-carbon skeleton composite material is mixed with an organic solvent in which a film-forming hydrophobic substance or a compound having a lithium reactive portion and a hydrophobic portion is dissolved.
- an organic solvent in which a film-forming hydrophobic substance or a compound having a lithium reactive portion and a hydrophobic portion is dissolved.
- Dispersed in another organic solvent which may be the same as or different from the organic solvent in which the film-forming hydrophobic substance or the compound having a lithium reactive portion and a hydrophobic portion is dissolved, and is selected from n-hexane, tetrahydrofuran, and ring. Any one or a combination of two or more of hexane and N-methylpyrrolidone.
- the metal lithium-carbon skeleton composite is mixed with an organic solvent in which a film-forming hydrophobic substance or a compound having a lithium reactive portion and a hydrophobic portion is dissolved, under stirring.
- the solid-liquid separation used to obtain the metallic lithium-skeletal carbon composite having a hydrophobic coating comprises filtration, such as suction filtration, and the like.
- Another aspect of the present invention provides a method of protecting a material containing an active metal sensitive to water and oxygen, comprising forming a hydrophobic coating layer on the material, the hydrophobic coating layer covering at least the material Active metal.
- the material to be protected includes a metallic lithium-carbon skeleton composite, lithium foil, lithium powder, and metallic sodium.
- Another aspect of the present invention provides an electrode comprising the above-described metal lithium-skeletal carbon composite material having a hydrophobic coating layer as an electrode material.
- Another aspect of the invention provides an electrochemical energy storage device comprising the electrode described above.
- the electrochemical energy storage device comprises a metal lithium-oxide battery, a lithium ion battery, a lithium sulfur battery, or a metal lithium-air battery, and the like.
- Embodiment 1 is a metal lithium-skeletal carbon composite material having a hydrophobic coating layer, comprising:
- a metal lithium-skeletal carbon composite material comprising a porous carbon material support and metallic lithium distributed in at least pores of the porous carbon material support;
- a hydrophobic coating layer covering at least the metallic lithium in the metallic lithium-skeletal carbon composite.
- the hydrophobic coating layer is composed of a film-forming hydrophobic material covering an exposed surface of the metal lithium-skeletal carbon composite material;
- the film-forming hydrophobic substance is selected from the group consisting of a film-forming hydrophobic polymer, such as polymethyl methacrylate (PMMA), polyvinylidene fluoride (PVDF), poly 2 Methyl siloxane (PDMS), and film-forming hydrophobic small molecules such as paraffin, white oil, benzotriazole.
- Embodiment 3 is the metal lithium-skeletal carbon composite material according to Embodiment 1, wherein the hydrophobic coating layer is composed of a compound having a lithium reactive portion and a hydrophobic portion, the lithium reactive portion and the metal The lithium reacts to passivate it, and the hydrophobic portion forms an outer hydrophobic layer.
- hydrophobic moiety comprises at least one of a C 4 -C 22 alkyl group, a C 6 -C 24 aryl group and a siloxane group, these groups optionally being substituted by hydrophobicity Substituted.
- Embodiment 5 is the metal lithium-skeletal carbon composite according to embodiment 4, wherein the hydrophobic substituent comprises at least one of fluorine, a perfluoro group, and a siloxane.
- porous carbon material carrier material comprises carbon nanotubes, porous carbon, carbon black, Any one or a combination of two or more of graphene, carbon fiber, acetylene black, and carbon aerogel.
- porous carbon material carrier has at least a fine granular solid aggregate structure, a spherical aggregate structure, Any of a spheroidal aggregate structure and a doughnut-shaped aggregate structure;
- the pores of the porous carbon material carrier have an average pore diameter of 10 to 100 nm;
- the porous carbon material carrier has an average particle diameter of 1 to 15 ⁇ m;
- the porous carbon material carrier has a conductivity of 1*10 -3 to 10S ⁇ cm -1 ;
- the porous carbon material carrier has a specific surface area of 100 to 1500 m 2 /g;
- the porous carbon material carrier can withstand a maximum pressure of 20 MPa or more;
- the metal lithium is supported in the metal lithium-skeletal carbon composite in an amount of 10 to 50% by weight.
- Embodiment 10 is a method for preparing a metal lithium-skeletal carbon composite material having a hydrophobic coating layer according to any one of embodiments 1-9, comprising:
- a metal lithium-skeletal carbon composite material having a hydrophobic coating layer is obtained by solid-liquid separation or evaporation.
- the organic solvent comprises any one of n-hexane, tetrahydrofuran, cyclohexane, and N-methylpyrrolidone, or a combination of two or more thereof.
- Embodiment 12 is the method according to Embodiment 10 or 11, wherein the method further comprises dispersing the metal lithium-carbon skeleton composite material in an organic solvent, and dissolving the organic solvent and dissolving the organic solvent.
- the organic solvent of the membrane-type hydrophobic substance or the compound having a lithium-reactive portion and a hydrophobic portion is the same or different.
- Embodiment 13 is a method of protecting a material containing an active metal sensitive to water and oxygen, wherein the method comprises forming a hydrophobic coating layer on the material, the hydrophobic coating layer coating at least the material Active metal in the middle.
- Embodiment 14 is the method of embodiment 13, wherein the material comprises a metallic lithium-carbon skeleton composite, a lithium foil, a lithium powder, and a metallic sodium.
- hydrophobic coating layer is composed of a film-forming hydrophobic substance, or the hydrophobic coating layer is composed of a lithium-reactive portion and a hydrophobic portion.
- the embodiment 16 is an electrode, wherein the electrode comprises the metal lithium-skeletal carbon composite material having a hydrophobic coating layer according to any one of the embodiments 1-9 as an electrode material.
- DETAILED DESCRIPTION 17 is an electrochemical energy storage device including the electrode of embodiment 16.
- the embodiment 18 is the electrochemical energy storage device according to the specific embodiment 17, wherein the electrochemical energy storage device comprises a metal lithium-oxide battery, a lithium ion battery, a lithium sulfur battery or a metal lithium-air battery.
- Figure 1 shows a schematic of an octadecyl phosphate coated metal lithium-skeletal carbon composite.
- the phosphate group of octadecyl phosphate is bonded to the surface of metallic lithium and is passivated by reaction with metallic lithium, so the binding site corresponds to the passivation layer and the alkyl moiety of octadecyl phosphate (hydrophobic).
- the groups are arranged vertically on the surface of the metallic lithium to form a hydrophobic film (hydrophobic layer).
- Figure 2 shows a scanning electron micrograph of a metallic lithium-skeletal carbon composite (a, b) and an octadecyl phosphate-metal lithium-skeletal carbon composite (c, d). It can be seen that the prepared octadecyl phosphate-metal lithium-skeletal carbon composite particles still retain the spherical or spheroidal morphology of the original metallic lithium-skeletal carbon composite material, and have a narrow size distribution.
- Figure 3 shows the EDS (energy spectrum) analysis of the change in oxygen content of the lithium metal-skeletal carbon composite and the octadecyl phosphate-metal lithium-skeletal carbon composite before and after exposure to dry air for 1 h.
- Figure 4 shows the results of capacity stability tests of metallic lithium-skeletal carbon composites and octadecyl phosphate-metal lithium-skeletal carbon-carbon composites in dry air. Test conditions: temperature 25 ° C, relative humidity 50%.
- the octadecyl phosphate-metal lithium-skeletal carbon composite material has only a small increase in oxygen content after exposure to dry air for 1 h, and the capacity is not significantly attenuated, therefore, octadecyl phosphate -
- the metal lithium-skeletal carbon composite material can be stably stored in dry air.
- Figure 5 shows the voltage vs. octadecyl phosphate-metal lithium-skeletal carbon composite/lithium half-cell and metal lithium-skeletal carbon composite/lithium half-cell in different cycle times during constant current charge and discharge test.
- Figure 6 shows the discharge specific capacity vs.
- the octadecyl phosphate-metal lithium-skeletal carbon composite has no significant polarization during the cycle, so the material has good stability and circulation in a dry environment. stability.
- the full battery composed of the composite material and the lithium iron phosphate positive electrode has a positive and negative electrode capacity ratio of about 1 to 30. Under the condition of 1 C rate, the capacity is hardly attenuated after 300 cycles; the lithium-carbon nanotube microsphere composite
- the capacity retention rate after the full battery cycle of the negative electrode for 300 weeks was 82%; after the cycle of 250 times with the lithium battery as the negative electrode, the capacity retention rate suddenly decreased, and then the use could not be continued.
- Figure 7 is an SEM image of the material, from which it can be seen that PMMA is coated with a metallic lithium-skeletal carbon composite.
- Figure 8 shows the stability test of the material in air (test conditions: temperature 25 ° C, relative humidity 50%). This test shows that the material has a certain stability in air and has better air stability and processability than the metal lithium-skeletal carbon composite.
- Figure 9 is an SEM image of the material, from which it can be seen that paraffin wax is coated on the surface of the metallic lithium-skeletal carbon composite.
- Figure 10 shows the stability test of the material in air (test conditions: temperature 25 ° C, relative humidity 50%). This test shows that the material has a certain stability in air and has better air stability and processability than the metal lithium-skeletal carbon composite.
- Figure 11 is an SEM image of the material, from which it can be seen that dodecyl mercaptan is coated on the surface of the metallic lithium-skeletal carbon composite.
- Figure 12 shows the stability test of the material in air (test conditions: temperature 25 ° C, relative humidity 50%). This test shows that the material has a certain stability in air and has better air stability and processability than the metal lithium-skeletal carbon composite.
- Figure 13 is an SEM image of the material, from which it can be seen that phenyl phosphate is coated on the surface of the metallic lithium-skeletal carbon composite.
- Figure 14 shows the stability test of the material in air (test conditions: temperature 25 ° C, relative humidity 50%). This test shows that the material has a certain stability in air and has better air stability and processability than the metal lithium-skeletal carbon composite.
- Figure 15 is a graph showing the constant current constant capacity test curve of the simulated battery fabricated by using the lithium-carbon nanotube microsphere composite prepared in this example as a negative electrode (the material is pressed against the foamed copper as a working electrode, 15 mm of metallic lithium foil).
- the phosphate group also has a certain ionic conductivity, so the metal lithium-skeletal carbon material coated with phenyl phosphate is more than the uncoated one during the cycle. Low overpotential and better cycle life.
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Abstract
Description
Claims (18)
- 一种具有疏水包覆层的金属锂-骨架碳复合材料,其特征在于包括:金属锂-骨架碳复合材料,包括多孔碳材料载体和至少分布于所述多孔碳材料载体的孔隙中的金属锂;疏水包覆层,其至少包覆所述金属锂-骨架碳复合材料中的金属锂。
- 根据权利要求1所述的金属锂-骨架碳复合材料,其特征在于所述疏水包覆层由成膜性疏水物质组成,覆盖所述金属锂-骨架碳复合材料的暴露表面;优选所述成膜性疏水物质选自成膜性疏水高分子,例如聚甲基丙烯酸甲酯(PMMA)、聚偏氟乙烯(PVDF)、聚二甲基硅氧烷(PDMS),和成膜性疏水小分子,例如石蜡、白油、苯并三氮唑。
- 根据权利要求1所述的金属锂-骨架碳复合材料,其特征在于所述疏水包覆层由具有锂反应性部分和疏水性部分的化合物组成,所述锂反应性部分与金属锂反应以将其钝化,所述疏水性部分形成外部疏水层。
- 根据权利要求3所述的金属锂-骨架碳复合材料,其特征在于所述锂反应性部分包括磷酸基团、硫醇基团、碳酸基团和氟硅烷基团中的至少一种;和/或,所述疏水性部分包括C4-C22烷基基团、C6-C24芳基基团和硅氧烷基团中的至少一种,这些基团任选被疏水性取代基取代。
- 根据权利要求4所述的金属锂-骨架碳复合材料,其特征在于所述疏水性取代基包括氟、全氟基团和硅氧烷中的至少一种。
- 根据权利要求1-5中任一项所述的金属锂-骨架碳复合材料,其特征在于所述疏水包覆层具有10-50nm的厚度。
- 根据权利要求1-6中任一项所述的金属锂-骨架碳复合材料,其特征在于所述疏水包覆层具有电子绝缘性和/或离子导电性。
- 根据权利要求1-7中任一项所述的钝化的金属锂-骨架碳复合材料,其特征在于所述多孔碳材料载体的材料包括碳纳米管、多孔碳、炭黑、石墨烯、碳纤维、乙炔黑、碳气凝胶中的任意一种或两种以上的组合。
- 根据权利要求1-8中任一项所述的钝化的金属锂-骨架碳复合材料,其特征在于所述多孔碳材料载体至少具有微小颗粒状实体聚集结构、球形聚集结构、类球形聚集结构和面包圈形聚集 结构中的任意一种;和/或,所述多孔碳材料载体所含孔洞的平均孔径为10~100nm;和/或,所述多孔碳材料载体的平均粒径为1~15μm;和/或,所述多孔碳材料载体的电导率为1*10-3~10S·cm-1;和/或,所述多孔碳材料载体的比表面积为100~1500m2/g;和/或,所述多孔碳材料载体可承受的最高压力为20MPa以上;和/或,所述金属锂在金属锂-骨架碳复合材料中的担载量为10~50wt%。
- 一种用于制备根据权利要求1-9中任一项所述的具有疏水包覆层的金属锂-骨架碳复合材料的方法,其特征在于所述方法包括:将金属锂-碳骨架复合材料与溶解有成膜性疏水物质或者具有锂反应性部分和疏水性部分的化合物的有机溶剂混合;通过固液分离或蒸发,获得具有疏水包覆层的金属锂-骨架碳复合材料。
- 根据权利要求10所述的方法,其特征在于所述有机溶剂包括正己烷、四氢呋喃、环己烷、N-甲基吡咯烷酮中的任意一种或两种以上的组合。
- 根据权利要求10或11所述的方法,其特征在于所述方法还包括先将所述金属锂-碳骨架复合材料分散在有机溶剂中,所述分散用有机溶剂与溶解有成膜性疏水物质或者具有锂反应性部分和疏水性部分的化合物的有机溶剂相同或不同。
- 一种保护含对水、氧敏感的活性金属的材料的方法,其特征在于所述方法包括在所述材料上形成疏水包覆层,所述疏水包覆层至少包覆所述材料中的活性金属。
- 根据权利要求13所述的方法,其特征在于所述材料包括金属锂-碳骨架复合材料、锂箔,锂粉以及金属钠。
- 根据权利要求13或14所述的方法,其特征在于所述疏水包覆层由成膜性疏水物质组成,或者所述疏水包覆层由具有锂反应性部分和疏水性部分的化合物组成。
- 一种电极,其特征在于所述电极包含根据权利要求1-9中任一项所述的具有疏水包覆层的金属锂-骨架碳复合材料作为电极材料。
- 一种电化学储能装置,其特征在于包括权利要求16所述的电极。
- 根据权利要求17所述的电化学储能装置,其特征在于所述电化学储能装置包括金属锂-氧化物电池、锂离子电池、锂硫电池或金属锂-空气电池。
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KR1020197022415A KR102314200B1 (ko) | 2017-07-26 | 2017-10-11 | 소수성 피복층을 갖는 리튬 금속 골격 탄소 복합 재료, 이의 제조 방법 및 용도 |
US16/477,803 US11462741B2 (en) | 2017-07-26 | 2017-10-11 | Metallic lithium-skeleton carbon composite material having a hydrophobic cladding layer, preparation method and use thereof |
EP17918727.3A EP3660962A4 (en) | 2017-07-26 | 2017-10-11 | LITHIUM METALLIC-CARBON-MATRIX COMPOSITE MATERIAL HAVING A HYDROPHOBIC COATING LAYER AND ITS PREPARATION PROCESS AND USE |
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