Carbon nanoparticle-porous skeleton composite material, its composite with lithium metal, and their preparation methods and use

Abstract

Disclosed is a carbon nanoparticle-porous skeleton composite material, its composite with lithium metal, and their preparation methods and use. In the carbon nanoparticle-porous skeleton composite material, the porous skeleton is a carbon-based porous microsphere material with a diameter of 1 to 100 μm or a porous metal material having internal pores with a micrometer-scale pore size distribution, and the carbon nanoparticles are distributed in the pores and on the surface of the carbon-based porous microsphere material or the porous metal material. The carbon nanoparticle-porous skeleton composite material is mixed with a molten lithium metal to form a lithium-carbon nanoparticle-porous skeleton composite material. The carbon nanoparticles present in the material can better conduct lithium ions during the battery cycle, thereby inhibiting the formation of lithium dendrites, and improving the safety and cycle stability of the battery.

1 . A carbon nanoparticle-porous skeleton composite material, wherein the porous skeleton is a carbon-based porous microsphere material with a diameter of 1 to 100 μm or a porous metal material having internal pores with a micrometer-scale pore size distribution, and the carbon nanoparticles are distributed in the pores and on the surface of the carbon-based porous microsphere material or the porous metal material. 
     
     
         2 . The carbon nanoparticle-porous skeleton composite material according to  claim 1 , comprising the carbon-based porous microsphere material, wherein the carbon-based porous microsphere material comprises at least one selected from the group consisting of a carbon nanotube or carbon nanofiber microsphere material, graphite, mesocarbon microspheres, and porous activated carbon; and/or
 comprising the porous metal material, wherein the porous metal material comprises at least one selected from the group consisting of porous copper, porous aluminum, porous zinc, porous iron, porous nickel, porous gold, and porous silver; and/or   wherein the carbon nanoparticles comprise at least one selected from the group consisting of carbon black, acetylene black, Ketjen black, Timcal Super P conductive additive, and Cabot BP2000 carbon black.   
     
     
         3 . The carbon nanoparticle-porous skeleton composite material according to  claim 1 , wherein the carbon nanoparticles have a size of 1 to 500 nm. 
     
     
         4 . The carbon nanoparticle-porous skeleton composite material according to  claim 1 , wherein the carbon nanoparticles have a content of 20 to 500 wt % with respect to the porous skeleton. 
     
     
         5 . The carbon nanoparticle-porous skeleton composite material according to  claim 2 , comprising carbon nanotube or carbon nanofiber microsphere material, wherein the pores contained in the carbon nanotube or carbon nanofiber microsphere material have a pore size of 1 to 200 nm. 
     
     
         6 . A method for preparing the carbon nanoparticle-porous skeleton composite material according to  claim 1 , the method comprising:
 dispersing carbon nanotubes or carbon nanofibers in a solvent together with carbon nanoparticles to form a dispersion, and then spray drying the dispersion; or   immersing microscale porous graphite, mesocarbon microspheres, porous activated carbon or a porous metal material in a solution containing carbon nanoparticles, sonicating and then drying the resultant material.   
     
     
         7 . The method according to  claim 6 , comprising the dispersing carbon nanotubes or carbon nanofibers in a solvent together with carbon nanoparticles to form a dispersion, and then spray drying the dispersion, the dispersing and spray drying comprising:
 A. dispersing the carbon nanotubes/carbon nanofibers and the carbon nanoparticles in a dispersion solvent (surfactant-free) through a sonicatlon treatment to obtain a dispersion;   B. spraying the dispersion obtained in step A out through a nozzle of a spray dryer, at a preset air inlet temperature and a preset air outlet temperature, wherein the dispersion is kept under stirring during the spraying; and   C. cooling the resultant material, thereby obtaining the carbon nanoparticle-carbon nanotube/carbon nanofiber microsphere composite material.   
     
     
         8 . The method according to  claim 7 , wherein a mass ratio between the carbon nanoparticles and the carbon nanotubes/carbon nanofibers in step A is 0.5:1 to 8:1. 
     
     
         9 . The method according to  claim 7 , wherein the air inlet temperature is 190 to 210° C. 
     
     
         10 . The method according to  claim 6 , comprising the immersing microscale porous graphite, mesocarbon microspheres, porous activated carbon or a porous metal material in a solution containing carbon nanoparticles, sonicating and then drying the resultant material, wherein the solution containing carbon nanoparticles comprises an aqueous solution containing carbon nanoparticles. 
     
     
         11 . A metallic lithium-carbon nanoparticle-porous skeleton composite material, which comprises the carbon nanoparticle-porous skeleton composite material according to  claim 1 , and metallic lithium distributed in the pores and on the surface of the carbon nanoparticle-porous skeleton composite material. 
     
     
         12 . The lithium-carbon nanoparticle-porous skeleton composite material according to  claim 11 , wherein the metallic lithium is 1% to 95% by mass of the total mass of the lithium-carbon nanoparticle-porous skeleton composite material. 
     
     
         13 . A method for preparing a metallic lithium-carbon nanoparticle-porous skeleton composite material, the method comprising mixing a molten lithium metal with the carbon nanoparticle-porous skeleton composite material according to  claim 1 , and then cooling the mixture. 
     
     
         14 . The method according to  claim 13 , wherein the mixing the molten lithium metal with the carbon nanoparticle-carbon-based porous microsphere composite material comprises:
 mixing the lithium metal with the carbon-based porous microsphere material under stirring and heating; or   immersing the carbon nanoparticle-porous metal composite material in the molten lithium metal.   
     
     
         15 . The method according to  claim 14 , comprising the mixing the lithium metal with the carbon-based porous microsphere material under stirring and heating, wherein the mixing under stirring comprises a pre-stirring step and a rapid stirring step, wherein the pre-stirring step comprises stirring a mixture of the lithium metal and the carbon nanoparticle-porous skeleton composite material at a speed of 50 rpm to 100 rpm at 200° C. to 230° C. for 1 to 5 minutes, and the rapid stirring step comprises rapidly stirring at a speed of 150 rpm to 1000 rpm at 230° C. to 300° C. 
     
     
         16 . An electrode comprising the lithium-carbon nanoparticle-porous skeleton composite material according to  claim 11 . 
     
     
         17 . An electrochemical energy storage device comprising the electrode according to  claim 16 , wherein the electrochemical energy storage device comprises an electrochemical battery or a super-capacitor. 
     
     
         18 . The electrochemical energy storage device according to  claim 17 , wherein the electrochemical battery comprises a lithium battery, a metallic lithium-oxide battery, a metallic lithium-sulfur secondary battery, or a metallic lithium-air battery. 
     
     
         19 . The carbon nanoparticle-porous skeleton composite material according to  claim 1 , comprising the carbon-based porous microsphere material, wherein the carbon-based porous microsphere material comprises at least one selected from the group consisting of a carbon nanotube or carbon nanofiber microsphere material, graphite, mesocarbon microspheres, and porous activated carbon; and wherein the carbon nanoparticles comprise at least one selected from the group consisting of carbon black, acetylene black, Ketjen black, Timcal Super P conductive additive, and Cabot BP2000 carbon black. 
     
     
         20 . The carbon nanoparticle-porous skeleton composite material according to  claim 1 , comprising the porous metal material, wherein the porous metal material comprises at least one selected from the group consisting of porous copper, porous aluminum, porous zinc, porous iron, porous nickel, porous gold, and porous silver; and wherein the carbon nanoparticles comprise at least one selected from the group consisting of carbon black, acetylene black, Ketjen black, Timcal Super P conductive additive, and Cabot BP2000 carbon black.