CN111161904B - Preparation method of light high-conductivity porous conductive agent and application of light high-conductivity porous conductive agent in battery electrode - Google Patents
Preparation method of light high-conductivity porous conductive agent and application of light high-conductivity porous conductive agent in battery electrode Download PDFInfo
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- CN111161904B CN111161904B CN202010007297.XA CN202010007297A CN111161904B CN 111161904 B CN111161904 B CN 111161904B CN 202010007297 A CN202010007297 A CN 202010007297A CN 111161904 B CN111161904 B CN 111161904B
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- 239000006258 conductive agent Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 188
- 239000000243 solution Substances 0.000 claims abstract description 142
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 134
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 117
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000000017 hydrogel Substances 0.000 claims abstract description 91
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 73
- 150000003839 salts Chemical class 0.000 claims abstract description 73
- 238000001035 drying Methods 0.000 claims abstract description 66
- 238000003756 stirring Methods 0.000 claims abstract description 54
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 40
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000011780 sodium chloride Substances 0.000 claims abstract description 37
- 239000000843 powder Substances 0.000 claims abstract description 33
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- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052709 silver Inorganic materials 0.000 claims abstract description 23
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 21
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 15
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- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 15
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- 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
Abstract
The invention relates to a conductive agent and a synthesis technology thereof, and aims to provide a preparation method of a light high-conductivity porous conductive agent and application of the light high-conductivity porous conductive agent in a battery electrode. The method comprises the following steps: adding the NaCl/KCl mixed solution into the hydrogel thiourea solution, and uniformly stirring; flash freezing and vacuum drying to obtain salt-containing rubber powder, deep dewatering and carbonizing; ball-milling, crushing, washing and drying to obtain sulfur-nitrogen-containing porous carbon; adding into saturated solution of sodium sulfide; performing ultrasonic treatment to obtain sodium sulfide supported porous carbon; dispersing in silver ammonia solution, stirring and reacting; adding molten salt to reduce silver sulfide into metallic silver; and filtering, washing and drying to obtain the silver-supported porous carbon serving as the conductive agent. The product of the invention has the characteristics of small density and equal contact area, and the silver coating on the carbon wall further improves the electronic conduction capability of the porous carbon, thereby being beneficial to improving the energy density of the battery. The electrode impedance is greatly reduced, and the power density of the lithium ion battery is improved. The synthetic method is green and low in cost.
Description
Technical Field
The invention relates to a conductive agent and a synthesis technology thereof, in particular to a conductive agent which adopts a porous structure to reduce the specific gravity of the conductive agent and adopts silver-plated carbon surface to strengthen electronic conduction and a preparation method thereof, and is used for preparing various lithium battery electrodes.
Background
The battery electrode needs to have good mass transfer capacity, high ion conductivity and high electron conductivity to improve the performance of the battery. In order to improve the mass transfer capacity, the electrode material is often micron-sized or nano-sized particles, and the particles are often connected through a conductive agent to improve the conductivity of the electrode. The micro-or nano-scale electrode material particles also require a binder to bind them together with the binder to form an electrode. Since the binder is generally an insulator, the influence on the conductivity of the electrode performance is significant, and the addition of a conductive agent is indispensable for reducing the influence of the binder.
Taking the electrode conductive agent of the lithium ion battery as an example, the conductive carbon materials of the traditional conductive agents such as acetylene black, super P, Ketjen black and the like are all solid particles, and 10-20 wt% of the conductive agent is usually added in the electrode material relative to active substances to meet the requirement of electrode conductivity. Therefore, it is one of the important measures currently studied to reduce the amount of the conductive agent as much as possible to increase the energy density of the battery while maintaining the conductivity.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provides a preparation method of a light high-conductivity porous conductive agent and application of the light high-conductivity porous conductive agent in a battery electrode.
In order to solve the technical problem, the solution of the invention is as follows:
the preparation method of the lightweight high-conductivity porous conductive agent comprises the following steps:
(1) taking 4g of hydrogel material, heating to 90 ℃, and dissolving in 10mL of deionized water to obtain a hydrogel solution; 1.5-10 g of thiourea is taken, heated to 90 ℃ and dissolved in 10mL of deionized water to obtain thiourea solution; adding the thiourea solution into the hydrogel solution, dropwise adding 0.5mL of 10wt% hydrochloric acid into a water bath at 90 ℃, and fully stirring to obtain a hydrogel thiourea solution;
(2) dissolving 5-30 g of a NaCl/KCl mixture in 40mL of deionized water, wherein the mass ratio of NaCl to KCl is 45: 55; adding the obtained solution into a hydrogel thiourea solution, stirring uniformly, directly spraying into a Dewar flask filled with liquid nitrogen at 90 ℃ through a sprayer for flash freezing, and rapidly cooling from 90 ℃ to the temperature of the liquid nitrogen; then transferring to a freezing vacuum drier for drying for 24 hours to obtain salt-containing rubber powder; transferring it to a tube furnace in N2Under the protection of atmosphere at 20 deg.C for min-1The temperature is increased to 160 ℃ at a certain speed, and the dehydration is carried out for 2 hours at a constant temperature and in a deep way; followed by a heating at 10 ℃ for min-1Raising the temperature to 900 ℃ at a constant temperature, and carbonizing for 4 hours; cooling to room temperature, solidifying the molten salt and keeping the porous carbon material on the molten salt; taking a porous carbon material, carrying out ball milling and crushing, washing with ionized water, carrying out suction filtration, and drying to obtain sulfur-nitrogen-containing porous carbon;
(3) taking 10-30 g of sulfur-nitrogen-containing porous carbon, and adding into 100mL of sodium sulfide saturated solution; dipping for 2h after ultrasonic treatment for 10min to ensure that the porous carbon is adsorbed and vulcanized; drying after filtering to obtain the sodium sulfide supported porous carbon;
(4) taking 50mL of silver nitrate solution with the mass concentration of 2 wt%, and dropwise adding 2 wt% of dilute ammonia water under ultrasonic waves until the precipitate is just completely dissolved to obtain silver ammonia solution; dispersing 5-15 g of the sodium sulfide-loaded porous carbon into a silver-ammonia solution, and stirring for reacting for 2 hours to obtain the silver sulfide-loaded porous carbon; transferring the mixture into an aluminum beaker, adding 5g of the molten salt obtained in the step (2), and stirring the mixture for 24 hours at the rotating speed of 10-60 rpm to reduce the silver sulfide into metallic silver; and filtering, washing with deionized water, and drying to obtain the silver-supported porous carbon serving as the conductive agent.
In the present invention, the hydrogel material refers to a hydrophilic (water-soluble) natural polymer or synthetic polymer capable of forming a hydrogel by chemical crosslinking or physical crosslinking; wherein the natural polymer is polysaccharide polymer (starch, cellulose, alginic acid, hyaluronic acid, and chitosan) or polypeptide polymer (such as agar, gelatin, acacia, and guar gum); the synthetic polymer is polyalcohol (such as polyethylene glycol, polyvinyl alcohol), polyacrylic acid or its derivatives (such as sodium polyacrylate, sodium polymethacrylate, polyacrylamide, and poly-N-polyacrylamide).
In the present invention, the frequency of the ultrasonic vibration is 40 kHz.
The invention further provides an application method of the conductive agent in preparing a battery electrode, which comprises the following steps: taking an electrode material, a conductive agent and a binder according to the mass ratio of 80: 10, grinding and uniformly mixing, adding NMP (N-methyl pyrrolidone) serving as a dispersing agent, and preparing into paste; after drying in the shade, the coating is applied to a collector at 100 ℃ and 100Kg cm-2And (4) pressing and forming under pressure to obtain the electrode.
In the invention, the electrode is a negative electrode in the lithium ion battery, and a collector of the electrode is a copper film; or the positive electrode in the lithium ion battery, and the collector is an aluminum film.
In the present invention, the electrode material is any one of: negative electrode material in lithium ion batteries (commercial lithium intercalation material): graphite, nano-silicon, lithium titanate or carbon-coated tin; cathode material in lithium ion battery: lithium cobaltate, lithium iron phosphate, lithium manganate or ternary cathode materials.
The invention further provides an application method in the preparation of the lithium ion battery, which takes lithium-containing transition metal oxide as a positive electrode material, metal lithium or graphite as a negative electrode material and microporous polypropylene as a diaphragm; respectively arranging a positive electrode material and a negative electrode material on two sides of a diaphragm in opposite directions to form a sandwich structure, wherein electrolyte is arranged in the sandwich structure; the positive electrode and the negative electrode of the battery use the silver-supported porous carbon as a conductive agent; the electrolyte is LiPF6As solute, the mixture of ethylene carbonate, propylene carbonate and dimethyl carbonate is solvent, the mass ratio of ethylene carbonate, propylene carbonate and dimethyl carbonate is 4: 2: 4, and LiPF in electrolyte6At a concentration of 1mol L-1。
Description of the inventive principles:
the method is characterized in that saccharide compounds (monosaccharide and polysaccharide) and NaCl/KCl inorganic salt are uniformly mixed, and then the molten salt has high-temperature stability, low vapor pressure in a wide temperature range, low viscosity, good conductivity, high ion migration and diffusion speed and high heat capacity when being subjected to high-temperature treatment, and has the capability of dissolving various materials. The saccharide compound is chloridized and cracked into small molecular intermediate in high-temperature ion solution with strong polarity to complete three-dimensional sp3Hybrid C-Cl bonding to two-dimensional sp2And (3) converting the hybridized C-C bond, and then carrying out structural rearrangement in a high-temperature environment to form a graphite structure. The process is simple and feasible, the raw materials are cheap and easy to obtain, the environmental pollution is low, the byproducts are few, the product is easy to treat, and the method has the characteristics of industrial production.
Hydrolyzing the sugar at high salt and high temperature to convert the sugar into 5-hydroxymethyl-2-furfural (HMF), heating the mixture of the sugar and urea at 50-200 ℃, and reacting to obtain the partially polymerized soluble urea-formaldehyde resin. Porous resin can be obtained by using a flash freezing technology and a freeze drying technology as a precursor, and porous carbon is obtained after deep carbonization.
The carbon material is doped with N and S, so that the hydrophilicity of the carbon material can be effectively improved, the electrolyte wettability is improved, lone-pair electrons of N and S doped atoms participate in electron conjugation of graphite rings of the carbon material, the concentration of electrons on the rings is increased, and the concentration of carriers is improved, so that the conductivity of the carbon material can be effectively improved.
The natural hydrophilic polymer includes polysaccharides (starch, cellulose, alginic acid, hyaluronic acid, and chitosan) and polypeptides such as agar, gelatin, gum arabic, and guar gum. The synthesized hydrophilic polymer comprises alcohol, acrylic acid and derivatives thereof (polyacrylic acid, polymethacrylic acid, polyacrylamide and poly-N-polyacrylamide) which are dissolved in water at high temperature and then cooled to a certain temperature to form hydrogel, and the hydrogel is freeze-dried to form porous xerogel. The salt in the saline gel powder obtained by freeze drying after the liquid nitrogen flash freezing exists in a microcrystalline form and is used as a template for forming porous carbon. Thiourea in the rubber powder is polymerized with the rubber powder in the dehydration process at 160 ℃, and the sulfur-nitrogen-carbon-containing material is obtained in the subsequent carbonization process at 900 ℃.
When the hydrogel thiourea solution is sprayed into liquid nitrogen through a sprayer, the fog drops quickly form a surface shell layer to isolate the gel fog drops from the liquid nitrogen. The temperature of the solution in the shell is continuously reduced, the mixture of the colloidal molecules and the thiourea and the eutectic of the sodium chloride and the potassium chloride are separated out, meanwhile, the free water in the gel is quickly frozen, and the mixture of the colloidal molecules and the thiourea and the eutectic are pushed to the boundary to form micropores. The eutectic in the gel is countless ice crystal seeds, and the ice is frozen and solidified instantly. During the subsequent vacuum freeze-drying process, the ice sublimes, forming cavities between the mixture of colloidal molecules and thiourea and the co-crystals. And in the subsequent calcining process, the temperature is raised to 160 ℃, colloid molecules are hydrolyzed and dehydrated, thiourea is polymerized, the framework is formed, and the temperature is raised to 900 ℃ to be completely carbonized to form the carbon thin wall. The eutectic of sodium chloride and potassium chloride becomes the fused salt, discharges from porous carbon, because the huge difference of porous carbon and fused salt density, the porous carbon come-up that forms is on the fused salt, the separation of the porous carbon of being convenient for and eutectic salt, the sulphur nitrogen containing porous carbon that obtains behind the residual eutectic salt template of deionized water removal porous carbon possesses good hydrophilicity, adsorbs the sodium sulfide molecule. The eutectic salt of sodium chloride and potassium chloride is used as the template, so that the melting point of the salt template is reduced, the fluidity is increased, the molten salt can be discharged from the micropores more smoothly during the carbonization of colloid molecules, the separation of the porous carbon and the salt template is facilitated, and the eutectic salt can be recycled.
And when the sulfur-nitrogen-containing porous carbon is immersed in the sodium sulfide saturated solution, the porous carbon adsorbs sodium sulfide, and after filtration and drying, the sodium sulfide saturated solution in the pores is separated out on the wall of the porous carbon to obtain the sodium sulfide-loaded porous carbon. When the porous carbon that sodium sulfide bore weight adds to silver ammonia solution, silver ammonia solution diffusion gets into the cavity of porous carbon and reacts with sodium sulfide and generates silver sulfide and load in the carbon wall, moves to aluminium beaker when the product, when adding eutectic salt water low-speed stirring, the porous carbon particle constantly contacts with aluminium beaker wall, forms short-lived microbattery, takes place the silver sulfide reduction to metallic silver from this:
3Ag2S+2Al+6H2O＝6Ag+2Al(OH)3↓+3H2S↑
and filtering, washing with deionized water, and drying to obtain the silver-supported porous carbon.
Compared with the prior art, the invention has the beneficial effects that:
1. different from the conventional solid carbon conductive agent, the silver-supported porous carbon obtained by the invention has the characteristics of small density and equal contact area, and the silver plating layer on the carbon wall further improves the electron conductivity of the porous carbon. The electrode material is added with less conductive agent than the traditional conductive agent, but can obtain better electrode conductivity, which is beneficial to improving the energy density of the battery.
2. According to the method, the eutectic salt of sodium chloride and potassium chloride is used as the template, the fluidity of the molten salt is increased, the automatic separation of the salt template and the porous carbon is realized, the residual salt in the porous carbon can be eluted by using water, and the synthesis method is more green and has lower cost.
3. The silver sulfide is used as an intermediate to realize silver plating on the carbon wall, so that the difficulty of uneven direct silver plating on the carbon wall is overcome. Compared with the traditional conductive agent, the obtained silver-supported porous carbon has better conductivity, can greatly reduce the electrode impedance, and improves the power density of the lithium ion battery.
4. Different from the discharge of waste liquid of the traditional chemical plating, the preparation method of the conductive agent is environment-friendly and green, and realizes no waste liquid discharge.
Drawings
Fig. 1 is a scanning electron micrograph of the silver-supported porous carbon obtained in example 10.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments.
Example 1: preparation of starch hydrogel thiourea solution
4g of water-soluble starch is heated to 90 ℃ and dissolved in 10mL of deionized water, and 1.5g of thiourea is heated to 90 ℃ and dissolved in 10mL of deionized water. And adding the thiourea solution into the hydrogel solution, placing the hydrogel solution into a water bath at 90 ℃, dropwise adding 0.5mL of 10wt% hydrochloric acid, and fully stirring to obtain the starch hydrogel thiourea solution.
Example 2: preparation of cellulose hydrogel thiourea solution
4g of water-soluble cellulose is heated to 90 ℃ and dissolved in 10mL of deionized water, and 5g of thiourea is heated to 90 ℃ and dissolved in 10mL of deionized water. And adding the thiourea solution into the hydrogel solution, placing the hydrogel solution into a water bath at 90 ℃, dropwise adding 0.5mL of 10wt% hydrochloric acid, and fully stirring to obtain the cellulose hydrogel thiourea solution.
Example 3: preparation of alginic acid hydrogel thiourea solution
4g of alginic acid is heated to 90 ℃ and dissolved in 10mL of deionized water, and 10g of thiourea is heated to 90 ℃ and dissolved in 10mL of deionized water. And adding the thiourea solution into the hydrogel solution, placing the hydrogel solution into a water bath at 90 ℃, dropwise adding 0.5mL of 10wt% hydrochloric acid, and fully stirring to obtain the alginic acid hydrogel thiourea solution.
Example 4: preparation of hyaluronic acid rubber powder
4g of hyaluronic acid is heated to 90 ℃ and dissolved in 10mL of deionized water, and 5g of thiourea is heated to 90 ℃ and dissolved in 10mL of deionized water. And adding the thiourea solution into the hydrogel solution, placing the hydrogel solution into a water bath at 90 ℃, dropwise adding 0.5mL of 10wt% hydrochloric acid, and fully stirring to obtain the hyaluronic acid hydrogel thiourea solution.
And dissolving 20g of NaCl/KCl mixture (the mass ratio of NaCl to KCl is 45:55) in 40mL of deionized water in another 1 beaker, adding the mixture into the hyaluronic acid hydrogel thiourea solution, stirring uniformly, directly spraying the hydrogel thiourea solution into a Dewar flask filled with liquid nitrogen through a sprayer at 90 ℃ for flash freezing, directly quenching the solution from 90 ℃ to the temperature of the liquid nitrogen, transferring the solution to a freezing vacuum dryer, and drying for 24 hours to obtain the salt-containing hyaluronic acid rubber powder.
Example 5: preparation of chitosan colloidal powder
4g of chitosan is heated to 90 ℃ and dissolved in 10mL of deionized water, and 5g of thiourea is heated to 90 ℃ and dissolved in 10mL of deionized water. And adding the thiourea solution into the hydrogel solution, placing the hydrogel solution into a water bath at 90 ℃, dropwise adding 0.5mL of 10wt% hydrochloric acid, and fully stirring to obtain the chitosan hydrogel thiourea solution.
And dissolving 5g of NaCl/KCl mixture (the mass ratio of NaCl to KCl is 45:55) in 40mL of deionized water in another 1 beaker, adding the mixture into the chitosan hydrogel thiourea solution, stirring uniformly, directly spraying the hydrogel thiourea solution into a Dewar flask filled with liquid nitrogen through a sprayer at 90 ℃ for flash freezing, directly quenching from 90 ℃ to the temperature of the liquid nitrogen, and transferring to a freezing vacuum dryer for drying for 24 hours to obtain the salt-containing chitosan gel powder.
Example 6: preparation of agar gel powder
Agar 4g was heated to 90 ℃ and dissolved in 10mL deionized water, and thiourea 5g was heated to 90 ℃ and dissolved in 10mL deionized water. And adding the thiourea solution into the hydrogel solution, placing the hydrogel solution into a water bath at 90 ℃, dropwise adding 0.5mL of 10wt% hydrochloric acid, and fully stirring to obtain the agar hydrogel thiourea solution.
And dissolving 15g of NaCl/KCl mixture (the mass ratio of NaCl to KCl is 45:55) in 40mL of deionized water in another 1 beaker, adding the mixture into the agar hydrogel thiourea solution, stirring uniformly, directly spraying the hydrogel thiourea solution into a Dewar flask filled with liquid nitrogen through a sprayer at 90 ℃ for flash freezing, directly quenching the solution from 90 ℃ to the temperature of the liquid nitrogen, and transferring the solution to a freeze vacuum dryer for drying for 24 hours to obtain the salt-containing agar gel powder.
Example 7: preparation of gelatin powder
4g of gelatin is heated to 90 ℃ and dissolved in 10mL of deionized water, and 5g of thiourea is heated to 90 ℃ and dissolved in 10mL of deionized water. And adding the thiourea solution into the hydrogel solution, placing the hydrogel solution into a water bath at 90 ℃, dropwise adding 0.5mL of 10wt% hydrochloric acid, and fully stirring to obtain the gelatin hydrogel thiourea solution.
And dissolving 30g of NaCl/KCl mixture (the mass ratio of NaCl to KCl is 45:55) in 40mL of deionized water in another 1 beaker, adding the mixture into the gelatin hydrogel thiourea solution, stirring uniformly, directly spraying the hydrogel thiourea solution into a Dewar flask filled with liquid nitrogen through a sprayer at 90 ℃ for flash freezing, directly quenching the solution from 90 ℃ to the temperature of the liquid nitrogen, and transferring the solution to a freeze vacuum dryer for drying for 24 hours to obtain the salt-containing gelatin powder.
Example 8: sulfur-nitrogen-containing macroporous carbon prepared from Arabic gum
4g of Arabic gum is heated to 90 ℃ and dissolved in 10mL of deionized water, and 5g of thiourea is heated to 90 ℃ and dissolved in 10mL of deionized water. And adding the thiourea solution into the hydrogel solution, placing the hydrogel solution into a water bath at 90 ℃, dropwise adding 0.5mL of 10wt% hydrochloric acid, and fully stirring to obtain the acacia gum hydrogel thiourea solution.
Dissolving 15g of NaCl/KCl mixture (the mass ratio of NaCl to KCl is 45:55) in 40mL of deionized water, adding the deionized water into the acacia gum hydrogel thiourea solution, stirring uniformly, directly spraying the acacia gum hydrogel thiourea solution into a Dewar flask filled with liquid nitrogen for flash freezing at 90 ℃, directly quenching the solution from 90 ℃ to the temperature of the liquid nitrogen, transferring the solution to a freezing vacuum dryer for drying for 24 hours to obtain saliferous acacia gum powder, putting the saliferous acacia gum powder into a tubular furnace, and drying in an N-shaped vacuum furnace2Under the protection of atmosphere at 20 deg.C for min-1The temperature is increased to 160 ℃ at a constant speed, the deep dehydration is carried out for 2 hours, and then the dehydration is carried out for 10min-1And heating to 900 ℃, carbonizing at constant temperature for 4h, cooling to room temperature, solidifying the molten salt, reserving the porous carbon material on the molten salt, ball-milling and crushing the porous carbon material, washing with ionized water, filtering, and drying to obtain the sulfur-nitrogen-containing porous carbon.
Example 9: preparation of porous carbon supported by sodium sulfide
Heating 4g of guar gum to 90 ℃ and dissolving in 10mL of deionized water, and heating 5g of thiourea to 90 ℃ and dissolving in 10mL of deionized water. And adding the thiourea solution into the hydrogel solution, placing the hydrogel solution into a water bath at 90 ℃, dropwise adding 0.5mL of 10wt% hydrochloric acid, and fully stirring to obtain the guar gum and thiourea gel solution.
Dissolving 15g of NaCl/KCl mixture (the mass ratio of NaCl to KCl is 45:55) in 40mL of deionized water in another 1 beaker, adding the mixture into guar gum gel thiourea solution, stirring uniformly, directly spraying the guar gum gel thiourea solution into a Dewar flask filled with liquid nitrogen through a sprayer at 90 ℃ for flash freezing, directly quenching the solution from 90 ℃ to the temperature of the liquid nitrogen, transferring the solution to a freezing vacuum dryer for drying for 24 hours to obtain salt-containing guar gum powder, putting the salt-containing guar gum powder into a tubular furnace, and drying in N for 24 hours2Under the protection of atmosphere at 20 deg.C for min-1The temperature is increased to 160 ℃ at a constant speed, the deep dehydration is carried out for 2 hours, and then the dehydration is carried out for 10min-1The temperature is increased to 900 ℃, the mixture is carbonized for 4 hours at constant temperature, the mixture is cooled to room temperature, the molten salt is solidified, and the porous carbon material is left on the molten saltAnd taking the porous carbon material, ball-milling and crushing, washing with ionized water, carrying out suction filtration and drying to obtain the sulfur-nitrogen-containing porous carbon.
Taking 100mL of sodium sulfide saturated solution, adding 10g of the sulfur-nitrogen containing porous carbon, performing ultrasonic treatment for 10min, and then soaking for 2 h; and adsorbing sodium sulfide on the porous carbon, filtering and drying to obtain the sodium sulfide supported porous carbon.
Example 10: preparation of silver-supported porous carbon
Heating 4g of polyethylene glycol to 90 ℃ and dissolving in 10mL of deionized water, and heating 5g of thiourea to 90 ℃ and dissolving in 10mL of deionized water. And adding the thiourea solution into the hydrogel solution, placing the hydrogel solution into a water bath at 90 ℃, dropwise adding 0.5mL of 10wt% hydrochloric acid, and fully stirring to obtain the polyethylene glycol hydrogel thiourea solution.
Dissolving 15g of NaCl/KCl mixture (the mass ratio of NaCl to KCl is 45:55) in 40mL of deionized water, adding the deionized water into the polyethylene glycol hydrogel thiourea solution, stirring uniformly, directly spraying the polyethylene glycol hydrogel thiourea solution into a Dewar flask filled with liquid nitrogen for flash freezing through a sprayer at 90 ℃, directly quenching the solution from 90 ℃ to the temperature of the liquid nitrogen, transferring the solution to a freezing vacuum dryer for drying for 24 hours to obtain salt-containing polyethylene glycol powder, putting the salt-containing polyethylene glycol powder into a tubular furnace, and drying in an N-shaped furnace2Under the protection of atmosphere at 20 deg.C for min-1The temperature is increased to 160 ℃ at a constant speed, the deep dehydration is carried out for 2 hours, and then the dehydration is carried out for 10min-1And heating to 900 ℃, carbonizing at constant temperature for 4h, cooling to room temperature, solidifying the molten salt, reserving the porous carbon material on the molten salt, ball-milling and crushing the porous carbon material, washing with ionized water, filtering, and drying to obtain the sulfur-nitrogen-containing porous carbon.
Taking 100mL of sodium sulfide saturated solution, adding 20g of the sulfur-nitrogen containing porous carbon, performing ultrasonic treatment for 10min, and then soaking for 2 h; and adsorbing sodium sulfide on the porous carbon, filtering and drying to obtain the sodium sulfide supported porous carbon.
50mL of 2 wt% silver nitrate solution is introduced into a beaker, and 2 wt% diluted ammonia water is dropwise added under ultrasound until the precipitate is just completely dissolved to obtain the silver ammonia solution. And (3) dispersing 5g of the sodium sulfide-supported porous carbon into the silver-ammonia solution, stirring and reacting for 2h to obtain the silver sulfide-supported porous carbon, transferring to an aluminum beaker, adding 5g of the molten salt, stirring at a low speed (10rpm) for 24h, reducing the silver sulfide into metallic silver, filtering, washing with deionized water, and drying to obtain the silver-supported porous carbon.
Example 11: preparation of negative electrode of lithium ion battery
4g of polyvinyl alcohol is taken and heated to 90 ℃ to be dissolved in 10mL of deionized water, and 5g of thiourea is taken and heated to 90 ℃ to be dissolved in 10mL of deionized water. And adding the thiourea solution into the hydrogel solution, placing the hydrogel solution into a water bath at 90 ℃, dropwise adding 0.5mL of 10wt% hydrochloric acid, and fully stirring to obtain the polyvinyl alcohol hydrogel thiourea solution.
Dissolving 15g of NaCl/KCl mixture (the mass ratio of NaCl to KCl is 45:55) in 40mL of deionized water in another 1 beaker, adding the mixture into the polyvinyl alcohol hydrogel thiourea solution, stirring uniformly, directly spraying the polyvinyl alcohol hydrogel thiourea solution into a Dewar flask filled with liquid nitrogen for flash freezing at 90 ℃, directly quenching the solution from 90 ℃ to the temperature of the liquid nitrogen, transferring the solution to a freezing vacuum dryer for drying for 24 hours to obtain salt-containing polyvinyl alcohol powder, putting the salt-containing polyvinyl alcohol powder into a tubular furnace, and putting the salt-containing polyvinyl alcohol powder into the tubular furnace in a N atmosphere2Under the protection of atmosphere at 20 deg.C for min-1The temperature is increased to 160 ℃ at a constant speed, the deep dehydration is carried out for 2 hours, and then the dehydration is carried out for 10min-1And heating to 900 ℃, carbonizing at constant temperature for 4h, cooling to room temperature, solidifying the molten salt, reserving the porous carbon material on the molten salt, ball-milling and crushing the porous carbon material, washing with ionized water, filtering, and drying to obtain the sulfur-nitrogen-containing porous carbon.
Taking 100mL of sodium sulfide saturated solution, adding 30g of the sulfur-nitrogen containing porous carbon, performing ultrasonic treatment for 10min, and then soaking for 2 h; and adsorbing sodium sulfide on the porous carbon, filtering and drying to obtain the sodium sulfide supported porous carbon.
50mL of 2 wt% silver nitrate solution is introduced into a beaker, and 2 wt% diluted ammonia water is dropwise added under ultrasound until the precipitate is just completely dissolved to obtain the silver ammonia solution. And (3) dispersing 10g of the sodium sulfide-supported porous carbon into the silver-ammonia solution, stirring and reacting for 2h to obtain the silver sulfide-supported porous carbon, transferring to an aluminum beaker, adding 5g of the molten salt, stirring at a low speed (20rpm) for 24h, reducing the silver sulfide into metallic silver, filtering, washing with deionized water, and drying to obtain the silver-supported porous carbon.
Taking graphite material from vendor, and carrying silver loadGrinding and uniformly mixing the porous carbon and PVDF in a mass ratio of 8:1:1, adding NMP (N-methyl pyrrolidone) serving as a dispersing agent, preparing into paste, coating the paste on a copper film, drying the paste in the shade, and drying the paste at 100 ℃ under 100Kg cm-2Pressing and forming under the pressure of the graphite anode to obtain the graphite anode.
The graphite material is changed into nano silicon, lithium titanate, carbon-coated tin and the like, and the silicon cathode, the lithium titanate cathode, the tin cathode and the like are respectively obtained by adopting the same process.
Example 12: preparation of positive electrode of lithium ion battery
Heating 4g of polyacrylic acid to 90 ℃ to dissolve in 10mL of deionized water, and heating 5g of thiourea to 90 ℃ to dissolve in 10mL of deionized water. And adding the thiourea solution into the hydrogel solution, placing the hydrogel solution into a water bath at 90 ℃, dropwise adding 0.5mL of 10wt% hydrochloric acid, and fully stirring to obtain the polyacrylic acid hydrogel thiourea solution.
Dissolving 15g of NaCl/KCl mixture (the mass ratio of NaCl to KCl is 45:55) in 40mL of deionized water in another 1 beaker, adding the mixture into polyacrylic acid hydrogel thiourea solution, stirring uniformly, directly spraying the polyacrylic acid hydrogel thiourea solution into a Dewar flask filled with liquid nitrogen for flash freezing at 90 ℃ through a sprayer, directly quenching the solution from 90 ℃ to the temperature of the liquid nitrogen, transferring the solution to a freezing vacuum dryer for drying for 24 hours to obtain salt-containing polyacrylic acid powder, putting the salt-containing polyacrylic acid powder into a tubular furnace, and drying in N for 24 hours2Under the protection of atmosphere at 20 deg.C for min-1The temperature is increased to 160 ℃ at a constant speed, the deep dehydration is carried out for 2 hours, and then the dehydration is carried out for 10min-1And heating to 900 ℃, carbonizing at constant temperature for 4h, cooling to room temperature, solidifying the molten salt, reserving the porous carbon material on the molten salt, ball-milling and crushing the porous carbon material, washing with ionized water, filtering, and drying to obtain the sulfur-nitrogen-containing porous carbon.
Taking 100mL of sodium sulfide saturated solution, adding 30g of the sulfur-nitrogen containing porous carbon, performing ultrasonic treatment for 10min, and then soaking for 2 h; and adsorbing sodium sulfide on the porous carbon, filtering and drying to obtain the sodium sulfide supported porous carbon.
50mL of 2 wt% silver nitrate solution is introduced into a beaker, and 2 wt% diluted ammonia water is dropwise added under ultrasound until the precipitate is just completely dissolved to obtain the silver ammonia solution. And (3) dispersing 15g of the sodium sulfide-supported porous carbon in the silver-ammonia solution, stirring and reacting for 2h to obtain the silver sulfide-supported porous carbon, transferring to an aluminum beaker, adding 5g of the molten salt, stirring at a low speed (30rpm) for 24h, reducing the silver sulfide into metallic silver, filtering, washing with deionized water, and drying to obtain the silver-supported porous carbon.
Grinding and mixing lithium cobaltate material, the silver-supported porous carbon and PVDF uniformly, adding NMP as dispersant, making into paste, coating on aluminum film, drying in the shade, and drying at 100 deg.C under 100Kg cm-2And (3) pressing and forming under the pressure of the pressure to obtain the lithium cobaltate anode, wherein the mass ratio of the lithium cobaltate to the acetylene black to the binder is 80: 10.
And replacing the lithium cobaltate material with lithium iron phosphate, lithium manganate, a ternary material and the like, and respectively obtaining a lithium iron phosphate anode, a lithium manganate anode, a ternary material anode and the like by adopting the same process.
Example 13: preparation of lithium iron phosphate battery
4g of sodium polyacrylate is heated to 90 ℃ and dissolved in 10mL of deionized water, and 5g of thiourea is heated to 90 ℃ and dissolved in 10mL of deionized water. And adding the thiourea solution into the hydrogel solution, placing the hydrogel solution into a water bath at 90 ℃, dropwise adding 0.5mL of 10wt% hydrochloric acid, and fully stirring to obtain the sodium polyacrylate hydrogel thiourea solution.
Dissolving 15g of NaCl/KCl mixture (the mass ratio of NaCl to KCl is 45:55) in 40mL of deionized water, adding the deionized water into the sodium polyacrylate hydrogel thiourea solution, stirring uniformly, directly spraying the sodium polyacrylate hydrogel thiourea solution into a Dewar flask filled with liquid nitrogen through a sprayer at 90 ℃ for flash freezing, directly quenching the solution from 90 ℃ to the temperature of the liquid nitrogen, transferring the solution to a freezing vacuum dryer for drying for 24 hours to obtain salt-containing polyacrylic acid powder, putting the salt-containing polyacrylic acid powder into a tubular furnace, and putting the salt-containing polyacrylic acid powder into the tubular furnace in N2Under the protection of atmosphere at 20 deg.C for min-1The temperature is increased to 160 ℃ at a constant speed, the deep dehydration is carried out for 2 hours, and then the dehydration is carried out for 10min-1And heating to 900 ℃, carbonizing at constant temperature for 4h, cooling to room temperature, solidifying the molten salt, reserving the porous carbon material on the molten salt, ball-milling and crushing the porous carbon material, washing with ionized water, filtering, and drying to obtain the sulfur-nitrogen-containing porous carbon.
Taking 100mL of sodium sulfide saturated solution, adding 30g of the sulfur-nitrogen containing porous carbon, performing ultrasonic treatment for 10min, and then soaking for 2 h; and adsorbing sodium sulfide on the porous carbon, filtering and drying to obtain the sodium sulfide supported porous carbon.
50mL of 2 wt% silver nitrate solution is introduced into a beaker, and 2 wt% diluted ammonia water is dropwise added under ultrasound until the precipitate is just completely dissolved to obtain the silver ammonia solution. And (3) dispersing 15g of the sodium sulfide-supported porous carbon in the silver-ammonia solution, stirring and reacting for 2h to obtain the silver sulfide-supported porous carbon, transferring to an aluminum beaker, adding 5g of the molten salt, stirring at a low speed (40rpm) for 24h, reducing the silver sulfide into metallic silver, filtering, washing with deionized water, and drying to obtain the silver-supported porous carbon.
Grinding and mixing commercial lithium iron phosphate material, the silver-supported porous carbon and PVDF uniformly, adding NMP as dispersant, preparing into paste, coating on aluminum film, drying in the shade, and drying at 100 deg.C under 100Kg cm-2The lithium iron phosphate anode is obtained by pressing and molding under the pressure, wherein the mass ratio of the lithium iron phosphate, the acetylene black and the binder is 80: 10.
Taking the graphite negative electrode obtained in the embodiment 11, enabling the electrode material side to face to form a sandwich structure with a vendor microporous polypropylene diaphragm, and internally containing an electrolyte; the electrolyte is LiPF6As solute, the mixture of ethylene carbonate, propylene carbonate and dimethyl carbonate is solvent, the mass ratio of ethylene carbonate, propylene carbonate and dimethyl carbonate is 4: 2: 4, and LiPF in electrolyte6At a concentration of 1mol L-1And obtaining the lithium iron phosphate battery.
Example 14: lithium manganate battery preparation
4g of sodium polymethacrylate is heated to 90 ℃ and dissolved in 10mL of deionized water, and 5g of thiourea is heated to 90 ℃ and dissolved in 10mL of deionized water. And adding the thiourea solution into the hydrogel solution, placing the hydrogel solution into a water bath at 90 ℃, dropwise adding 0.5mL of 10wt% hydrochloric acid, and fully stirring to obtain the sodium polymethacrylate hydrogel thiourea solution.
Dissolving 15g of NaCl/KCl mixture (the mass ratio of NaCl to KCl is 45:55) in 40mL of deionized water in another 1 beaker, adding the mixture into the sodium polymethacrylate hydrogel thiourea solution, stirring uniformly, and directly adding the sodium polymethacrylate sodium solution through a sprayer at 90 DEGSpraying the gel thiourea solution into a Dewar flask filled with liquid nitrogen for flash freezing, directly quenching from 90 deg.C to liquid nitrogen temperature, transferring to a freeze vacuum drier for drying for 24 hr to obtain salt-containing sodium polymethacrylate powder, placing in a tube furnace, and performing flash freezing in N2Under the protection of atmosphere at 20 deg.C for min-1The temperature is increased to 160 ℃ at a constant speed, the deep dehydration is carried out for 2 hours, and then the dehydration is carried out for 10min-1And heating to 900 ℃, carbonizing at constant temperature for 4h, cooling to room temperature, solidifying the molten salt, reserving the porous carbon material on the molten salt, ball-milling and crushing the porous carbon material, washing with ionized water, filtering, and drying to obtain the sulfur-nitrogen-containing porous carbon.
Taking 100mL of sodium sulfide saturated solution, adding 30g of the sulfur-nitrogen containing porous carbon, performing ultrasonic treatment for 10min, and then soaking for 2 h; and adsorbing sodium sulfide on the porous carbon, filtering and drying to obtain the sodium sulfide supported porous carbon.
50mL of 2 wt% silver nitrate solution is introduced into a beaker, and 2 wt% diluted ammonia water is dropwise added under ultrasound until the precipitate is just completely dissolved to obtain the silver ammonia solution. And (3) dispersing 15g of the sodium sulfide-supported porous carbon in the silver-ammonia solution, stirring and reacting for 2h to obtain the silver sulfide-supported porous carbon, transferring to an aluminum beaker, adding 5g of the molten salt, stirring at a low speed (50rpm) for 24h, reducing the silver sulfide into metallic silver, filtering, washing with deionized water, and drying to obtain the silver-supported porous carbon.
Grinding and mixing commercially available lithium manganate material, the silver-supported porous carbon and PVDF uniformly, adding NMP as dispersant to prepare paste, coating the paste on an aluminum film, drying in the shade, and drying at 100 ℃ under 100Kg cm-2The lithium manganate anode is obtained by pressing and forming under the pressure of the pressure, wherein the mass ratio of the lithium manganate, the acetylene black and the binder is 80: 10.
Taking the graphite negative electrode obtained in the embodiment 11, enabling the electrode material side to face to form a sandwich structure with a vendor microporous polypropylene diaphragm, and internally containing an electrolyte; the electrolyte is LiPF6As solute, the mixture of ethylene carbonate, propylene carbonate and dimethyl carbonate is solvent, the mass ratio of ethylene carbonate, propylene carbonate and dimethyl carbonate is 4: 2: 4, and LiPF in electrolyte6At a concentration of 1mol L-1And obtaining the lithium manganate battery.
Example 15: preparation of ternary material lithium battery
4g of polyacrylamide is heated to 90 ℃ and dissolved in 10mL of deionized water, and 5g of thiourea is heated to 90 ℃ and dissolved in 10mL of deionized water. And adding the thiourea solution into the hydrogel solution, placing the hydrogel solution into a water bath at 90 ℃, dropwise adding 0.5mL of 10wt% hydrochloric acid, and fully stirring to obtain the polyacrylamide hydrogel thiourea solution.
Dissolving 15g of NaCl/KCl mixture (the mass ratio of NaCl to KCl is 45:55) in 40mL of deionized water, adding the deionized water into the polyacrylamide hydrogel thiourea solution, stirring uniformly, directly spraying the polyacrylamide hydrogel thiourea solution into a Dewar flask filled with liquid nitrogen for flash freezing through a sprayer at 90 ℃, directly quenching the solution from 90 ℃ to the temperature of the liquid nitrogen, transferring the solution to a freezing vacuum dryer for drying for 24 hours to obtain salt-containing polyacrylamide powder, putting the salt-containing polyacrylamide powder into a tubular furnace, and putting the salt-containing polyacrylamide powder into the tubular furnace for N2Under the protection of atmosphere at 20 deg.C for min-1The temperature is increased to 160 ℃ at a constant speed, the deep dehydration is carried out for 2 hours, and then the dehydration is carried out for 10min-1And heating to 900 ℃, carbonizing at constant temperature for 4h, cooling to room temperature, solidifying the molten salt, reserving the porous carbon material on the molten salt, ball-milling and crushing the porous carbon material, washing with ionized water, filtering, and drying to obtain the sulfur-nitrogen-containing porous carbon.
Taking 100mL of sodium sulfide saturated solution, adding 30g of the sulfur-nitrogen containing porous carbon, performing ultrasonic treatment for 10min, and then soaking for 2 h; and adsorbing sodium sulfide on the porous carbon, filtering and drying to obtain the sodium sulfide supported porous carbon.
50mL of 2 wt% silver nitrate solution is introduced into a beaker, and 2 wt% diluted ammonia water is dropwise added under ultrasound until the precipitate is just completely dissolved to obtain the silver ammonia solution. And (3) dispersing 15g of the sodium sulfide-supported porous carbon in the silver-ammonia solution, stirring and reacting for 2h to obtain the silver sulfide-supported porous carbon, transferring to an aluminum beaker, adding 5g of the molten salt, stirring at a low speed (60rpm) for 24h, reducing the silver sulfide into metallic silver, filtering, washing with deionized water, and drying to obtain the silver-supported porous carbon.
Grinding and mixing the ternary cathode material, the silver-supported porous carbon and PVDF uniformly, adding NMP as a dispersing agent, preparing into paste, coating the paste on an aluminum film, and drying in the shadeThen, at 100 ℃ under 100Kg cm-2The anode is obtained by pressing and molding under the pressure of the raw materials, wherein the mass ratio of the ternary anode material, the acetylene black and the binder is 80: 10.
Taking the graphite negative electrode obtained in the embodiment 11, enabling the electrode material side to face to form a sandwich structure with a vendor microporous polypropylene diaphragm, and internally containing an electrolyte; the electrolyte is LiPF6As solute, the mixture of ethylene carbonate, propylene carbonate and dimethyl carbonate is solvent, the mass ratio of ethylene carbonate, propylene carbonate and dimethyl carbonate is 4: 2: 4, and LiPF in electrolyte6At a concentration of 1mol L-1And obtaining the ternary material lithium battery.
Example 16: metal lithium battery
4g of poly-N-polyacrylamide is heated to 90 ℃ and dissolved in 10mL of deionized water, and 5g of thiourea is heated to 90 ℃ and dissolved in 10mL of deionized water. And adding the thiourea solution into the hydrogel solution, putting the hydrogel solution into a water bath at 90 ℃, dropwise adding 0.5mL of 10wt% hydrochloric acid, and fully stirring to obtain the poly-N-polyacrylamide hydrogel thiourea solution.
Dissolving 15g of NaCl/KCl mixture (the mass ratio of NaCl to KCl is 45:55) in 40mL of deionized water, adding the deionized water into the poly-N-polyacrylamide hydrogel thiourea solution, stirring uniformly, then directly spraying the poly-N-polyacrylamide hydrogel thiourea solution into a Dewar flask filled with liquid nitrogen through a sprayer at 90 ℃, carrying out flash freezing, directly quenching from 90 ℃ to the temperature of the liquid nitrogen, transferring to a freeze vacuum dryer, drying for 24 hours to obtain salt-containing poly-N-polyacrylamide powder, putting into a tubular furnace, and putting into a N-shaped furnace2Under the protection of atmosphere at 20 deg.C for min-1The temperature is increased to 160 ℃ at a constant speed, the deep dehydration is carried out for 2 hours, and then the dehydration is carried out for 10min-1And heating to 900 ℃, carbonizing at constant temperature for 4h, cooling to room temperature, solidifying the molten salt, reserving the porous carbon material on the molten salt, ball-milling and crushing the porous carbon material, washing with ionized water, filtering, and drying to obtain the sulfur-nitrogen-containing porous carbon.
Taking 100mL of sodium sulfide saturated solution, adding 30g of the sulfur-nitrogen containing porous carbon, performing ultrasonic treatment for 10min, and then soaking for 2 h; and adsorbing sodium sulfide on the porous carbon, filtering and drying to obtain the sodium sulfide supported porous carbon.
50mL of 2 wt% silver nitrate solution is introduced into a beaker, and 2 wt% diluted ammonia water is dropwise added under ultrasound until the precipitate is just completely dissolved to obtain the silver ammonia solution. And (3) dispersing 15g of the sodium sulfide-supported porous carbon in the silver-ammonia solution, stirring and reacting for 2h to obtain the silver sulfide-supported porous carbon, transferring to an aluminum beaker, adding 5g of the molten salt, stirring at a low speed (10rpm) for 24h, reducing the silver sulfide into metallic silver, filtering, washing with deionized water, and drying to obtain the silver-supported porous carbon.
Grinding and mixing vendor ternary cathode material, the above silver-supported porous carbon and PVDF uniformly, adding NMP as dispersant, concocting into paste, coating onto aluminum film, drying in the shade, and drying at 100 deg.C under 100Kg cm-2The anode is obtained by pressing and molding under the pressure of the raw materials, wherein the mass ratio of the ternary anode material, the acetylene black and the binder is 80: 10.
Taking a metal lithium sheet of vendor as a negative electrode, enabling the electrode material side to face to form a sandwich structure with a microporous polypropylene diaphragm of vendor, and internally arranging an electrolyte; the electrolyte is LiPF6As solute, the mixture of ethylene carbonate, propylene carbonate and dimethyl carbonate is solvent, the mass ratio of ethylene carbonate, propylene carbonate and dimethyl carbonate is 4: 2: 4, and LiPF in electrolyte6At a concentration of 1mol L-1And obtaining the metal lithium battery.
Finally, the foregoing disclosure is directed to only certain embodiments of the invention. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
Claims (7)
1. The preparation method of the light high-conductivity porous conductive agent is characterized by comprising the following steps:
(1) taking 4g of hydrogel material, heating to 90 ℃, and dissolving in 10mL of deionized water to obtain a hydrogel solution; 1.5-10 g of thiourea is taken, heated to 90 ℃ and dissolved in 10mL of deionized water to obtain thiourea solution; adding the thiourea solution into the hydrogel solution, dropwise adding 0.5mL of 10wt% hydrochloric acid into a water bath at 90 ℃, and fully stirring to obtain a hydrogel thiourea solution;
(2) dissolving 5-30 g of a NaCl/KCl mixture in 40mL of deionized water, wherein the mass ratio of NaCl to KCl is 45: 55; adding the obtained solution into a hydrogel thiourea solution, stirring uniformly, directly spraying into a Dewar flask filled with liquid nitrogen at 90 ℃ through a sprayer for flash freezing, and rapidly cooling from 90 ℃ to the temperature of the liquid nitrogen; then transferring to a freezing vacuum drier for drying for 24 hours to obtain salt-containing rubber powder; transferring it to a tube furnace in N2Under the protection of atmosphere at 20 deg.C for min-1The temperature is increased to 160 ℃ at a certain speed, and the dehydration is carried out for 2 hours at a constant temperature and in a deep way; followed by a heating at 10 ℃ for min-1Raising the temperature to 900 ℃ at a constant temperature, and carbonizing for 4 hours; cooling to room temperature, solidifying the molten salt and keeping the porous carbon material on the molten salt; taking a porous carbon material, carrying out ball milling and crushing, washing with ionized water, carrying out suction filtration, and drying to obtain sulfur-nitrogen-containing porous carbon;
(3) taking 10-30 g of sulfur-nitrogen-containing porous carbon, and adding into 100mL of sodium sulfide saturated solution; dipping for 2h after ultrasonic treatment for 10min to ensure that the porous carbon is adsorbed and vulcanized; drying after filtering to obtain the sodium sulfide supported porous carbon;
(4) taking 50mL of silver nitrate solution with the mass concentration of 2 wt%, and dropwise adding 2 wt% of dilute ammonia water under ultrasonic waves until the precipitate is just completely dissolved to obtain silver ammonia solution; dispersing 5-15 g of the sodium sulfide-loaded porous carbon into a silver-ammonia solution, and stirring for reacting for 2 hours to obtain the silver sulfide-loaded porous carbon; transferring the mixture into an aluminum beaker, adding 5g of the molten salt obtained in the step (2), and stirring the mixture for 24 hours at the rotating speed of 10-60 rpm to reduce the silver sulfide into metallic silver; and filtering, washing with deionized water, and drying to obtain the silver-supported porous carbon serving as the conductive agent.
2. The method according to claim 1, wherein the hydrogel material is a hydrophilic natural polymer or synthetic polymer capable of forming a hydrogel by chemical crosslinking or physical crosslinking; wherein the natural polymer is polysaccharide polymer or polypeptide polymer; the synthetic polymer is polyol, polyacrylic acid or derivatives thereof.
3. The method of claim 1, wherein the ultrasonic vibration has a frequency of 40 kHz.
4. A method of using the conductive agent prepared by the method of claim 1 in the preparation of a battery electrode, comprising: taking an electrode material, a conductive agent and a binder according to the mass ratio of 80: 10, grinding and uniformly mixing, adding NMP serving as a dispersing agent, and preparing into paste; after drying in the shade, the coating is applied to a collector at 100 ℃ and 100Kg cm-2And (4) pressing and forming under pressure to obtain the electrode.
5. The method of claim 4, wherein the electrode is a negative electrode in a lithium ion battery, and a collector thereof is a copper film; or the positive electrode in the lithium ion battery, and the collector is an aluminum film.
6. The method of claim 4, wherein the electrode material is any one of: negative electrode materials in lithium ion batteries: graphite, nano-silicon, lithium titanate or carbon-coated tin; cathode material in lithium ion battery: lithium cobaltate, lithium iron phosphate, lithium manganate or ternary cathode materials.
7. The method for applying the conductive agent prepared by the method of claim 1 in the preparation of lithium ion batteries is characterized in that lithium-containing transition metal oxide is used as a positive electrode material, metallic lithium or graphite is used as a negative electrode material, and microporous polypropylene is used as a diaphragm; respectively arranging a positive electrode material and a negative electrode material on two sides of a diaphragm in opposite directions to form a sandwich structure, wherein electrolyte is arranged in the sandwich structure; the positive electrode and the negative electrode of the battery use the silver-supported porous carbon as a conductive agent;
the electrolyte is LiPF6As solute, the mixture of ethylene carbonate, propylene carbonate and dimethyl carbonate is solvent, the mass ratio of ethylene carbonate, propylene carbonate and dimethyl carbonate is 4: 2: 4, and LiPF in electrolyte6At a concentration of 1mol L-1。
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