CN103107318A - Preparation method of composite positive pole material for lithium sulphur battery - Google Patents
Preparation method of composite positive pole material for lithium sulphur battery Download PDFInfo
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Abstract
The invention discloses a preparation method of a composite positive pole material of a lithium sulphur battery. The preparation method comprises the following steps of: (1) utilizing activation and nitrogen doping to simultaneously carry out modification on a carbon aerogel to obtain a modified carbon aerogel material; and (2) slowly adding the modified carbon aerogel in an organic sulfur solution, taking a supercritical fluid as an extraction agent to ultrasonically extract in an extraction kettle under room temperature, carrying out pressure reduction and separation, leaching by an ethanol eluting agent, and drying to obtain the modified carbon aerogel-sulfur composite positive pole material. The material prepared by the preparation method provided by the invention has the advantages that the sulfur content is high, the sulfur particles are small, the granularity is uniformly controllable, and the material simultaneously has higher conductibility, specific surface area and porosity. The recovery of the used organic solvent is simple in the preparation process, the extraction agent is circularly used through compression, the extraction efficiency is high, the operation is simple, and the pollution is not generated.
Description
Technical field
The invention belongs to new energy field, relate to a kind of lithium sulfur battery anode material preparation method, particularly a kind of charcoal-aero gel-sulphur composite positive pole preparation method.
Background technology
Along with portable type electronic product is universal, the fast development of energy storage technology and electric automobile, more and more higher to the requirement of lithium ion battery energy density and power density.There is prediction to claim, more than the energy density of following 4G mobile communication requirement battery reaches 500Wh/Kg.Lithium-sulfur cell has height ratio capacity (1675 mAh/g) and high-energy-density (2600 Wh/kg), positive electrode elemental sulfur aboundresources, cheap, environmental friendliness.So lithium-sulfur cell is the high-energy density secondary battery that has development potentiality and application prospect.But exist positive active material elemental sulfur poorly conductive, the intermediate product polysulfide of discharge process is soluble in electrolyte, and " effect of shuttling back and forth " occurs in electrolyte, causes irreversible loss and the capacity attenuation of active material.Simultaneously final discharging product Li
2The indissolubility of S and electrical insulating property make anodal and negative pole passivation.The sulphur positive electrode mainly has satisfactory electrical conductivity by elemental sulfur is adsorbed onto at present, on the carbon material of high-specific surface area and high porosity, forms the sulphur carbon composite.
Carbon material active carbon, acetylene black, the carbon nano-tube of reporting in the lithium-sulfur cell document at present all can not have both the excellent characteristic such as good conductivity, high-specific surface area and high porosity simultaneously.Large but the poor electric conductivity of active carbon specific area; Acetylene black conducts electricity very well but specific area is little; Specific surface area of carbon nanotube and conductivity are all general, and price.And carbon aerogel material is a kind of have good conductivity and material of high-specific surface area, and can also be further improved by the performance to its Modified Activated Carbon aerogel material, be badly in need of a kind of preparation method of exploitation and make charcoal-aero gel have both simultaneously higher conductivity, specific area and porosity to the charcoal-aero gel modifying and decorating.
Chinese patent CN102874791A discloses a kind of preparation method of carbon aerogel material.Potassium hydroxide is carried out the effect of single activation to the carbon aerogel material for preparing by sol-gel process, improved its specific area and pore volume, but after activation, pore volume increases, hole increases, carbon structure destroys, and electric conductivity weakens, and the transfer impedance of material with carbon element increases.
Chinese patent CN101891930A discloses a kind of method for preparing the sulfur-based composite anode material of carbon nano-tube with heat treatment, and this method is conducive to the dispersion of carbon nano-tube and the even distribution of sulphur, but in composite material, sulfur content is low and be difficult to control.
M. Rao etc. (Journal of Power Sources, 2012.Vol205:474-478) has reported Na
2S
xSolution and formic acid solution prepare the sulphur carbon composite by sulphur and the material with carbon element that chemical reaction produces in liquid phase.The sulfur granules that adopts this kind liquid phase preparation process to obtain is little, and composite material Uniform Dispersion and year sulfur content are high, but react S in building-up process
x 2++ 2H
+→ (x-1) S+H
2S has H
2The S toxic gas is emitted, contaminated environment.
Chinese patent CN102832379 A discloses a kind of preparation method of lithium sulfur battery anode material: elemental sulfur and organic solvent are mixed make elemental sulfur dissolve fully, Carbon Materials is added in sulphur-organic solution, stir, by naturally volatilizing or the method for heated volatile is removed solvent, get sulphur-carbon composite.This preparation method is simple, and it is high that composite material carries sulfur content, but by naturally volatilize or the heated volatile removal solvent time long; Volatilization process is slow, and sulphur can slow crystallization, causes that the sulfur granules of separating out is large and granularity is inhomogeneous.
Therefore, need a kind of method of modifying carbon aerogel material of exploitation badly, when carbon aerogel material surface area and pore volume are increased, have both better electric conductivity.Need develop simultaneously a kind of carbon sulphur content cloth even, carry sulfur content high and controlled, the sulfur granules granularity is little, and is pollution-free, and use carbon sulphur composite manufacture method simple to operate is to improve its chemical property.
Summary of the invention
The charcoal-aero gel that provides a kind of lithium-sulphur cell positive electrode to use-sulphur composite manufacture method is provided the object of the invention, and the charcoal-aero gel of the method preparation-sulphur composite material has both higher conductivity, specific area and porosity.In material, sulfur content is high, and sulfur granules is little, and granularity is controlled evenly.The organic solvent that uses in preparation technology reclaims simple, and extractant is compressed can be recycled, and extraction efficiency is high, and is simple to operate, pollution-free.
Purpose of the present invention is achieved through the following technical solutions: a kind of preparation method of lithium-sulfur battery composite anode material comprises the following steps successively: the modification of (1) charcoal-aero gel: the mass ratio in solid base, nitrogen source and charcoal-aero gel is 1:(1～5): the ratio of (1～5), getting solid base and nitrogen source adds in charcoal-aero gel simultaneously, mix, be placed under Muffle furnace argon gas or nitrogen inert atmosphere protection and be heated to 700～900 ℃, be incubated 1～5 hour; The solid product of gained is rinsed with dilute acid soln, then with the washing of distilled water or ethanol to neutral, 80～150 ℃ of dryings are activated+carbon aerogel material that the nitrating synchronous process is modified; The preparation of the charcoal-aero gel of (2) modifying-sulphur composite positive pole: under room temperature condition, elemental sulfur is dissolved in organic solvent to form mass concentration be 1～40% sulfur-containing organic solution, the charcoal-aero gel that slowly adds step (1) to make, the mass ratio of charcoal-aero gel and sulphur is 1:1～1:9, room temperature sonic oscillation 0.5～2 hour; Then solution is put into extraction kettle, extract take supercritical fluid as extractant, decompression separation, ethanol elution agent drip washing, 60～110 ℃ of lower vacuumizes, the charcoal-aero gel that obtains modifying-sulphur composite positive pole; Described organic solvent is the solvent good to the elemental sulfur dissolubility, and sulphur solubility in organic solvent is not less than 10g/L; Described supercritical fluid extraction agent is or sl. sol. solvent insoluble to elemental sulfur, and sulphur solubility in organic solvent is not more than 5g.
In preparation method of the present invention, described nitrogen source is: melamine, urea, n-propylamine, n-butylamine, triethylamine, ethamine, hydrazine, dimethylamine, methyl ethylamine, diethylamine, aniline, N-methyl-N-ethylo benzene, N, one or several in N-diethylaniline, ethylenediamine, pyridine, pyrroles, second two ammoniums, teabrom, hydroxide trimethyl ethyl ammonium.Wherein, most preferably be one or more in melamine, ethylenediamine, urea, pyridine, aniline, teabrom.
Solid base described in the present invention is preferably one or several in NaOH, potassium hydroxide, lithium hydroxide.Dilute acid soln is preferably one or more in watery hydrochloric acid, dilute sulfuric acid, rare nitric acid.
As preferably, organic solvent described in step of the present invention (2) is one or more in nitric sulfid, carbon tetrachloride, ortho-xylene, benzene, toluene, paraxylene.
As preferably, the supercritical fluid extraction agent described in step of the present invention (2) is preferably isopropyl alcohol, cyclohexane, ethane, ethene, propane, one or more in propylene.
In step of the present invention (1), use the heating-up temperature of Muffle furnace to be preferably 700～900 ℃, be incubated 1～5 hour; The ultrasonic concussion of room temperature 0.5～2 hour.
In preparation method of the present invention, the supercritical fluid extraction temperature described in step (2) is 20～250 ℃, and pressure is 25～30MPa, and the time is 20～60 minutes, and the flow of supercritical fluid is 500～1000 ml/min; Separating pressure is 3～7MPa, 40～60 ℃ of temperature.
The technique that the present invention adopts the doping of alkali activation+nitrogen synchronously to carry out has solved the problem that single activation and single nitrating effect bring.In preparation method's process that the doping of alkali activation+nitrogen is synchronously carried out, the alkali activation can activate the interface of charcoal-aero gel, more is conducive to effectively mixing of nitrogen, improves conductivity; The process of nitrogen doping simultaneously, the functional group of charcoal material surface changes, and more is conducive to reaming dilatation and interface activation in alkali activation process, obtains higher specific area and pore volume.Single activation and nitrating process are all at high temperature to carry out, activation+nitrating is synchronously processed the preparation method who modifies charcoal-aero gel can not only shorten man-hour, energy savings and cost, more can obtain to have both simultaneously high itrogen content of getter with nitrogen doped, the carbon aerogel material of high conductivity, high-specific surface area, high porosity, this material have that nanocarbon particle is formed by connecting take mesopore as main, and the continuous three-dimensional conductive network structure of cutting out controlled in the nanoscale aperture.After measured, the charcoal-aero gel specific area with the prepared modification of method of the present invention reaches 1500～2000m
2/ g, pore volume are 0.48～0.67cm
3/ g, itrogen content of getter with nitrogen doped reaches 8.5%～15.8at%, and density reaches 0.12 ~ 1.05 g ﹒ cm
-3, average pore size is 3～20 nm.
The present invention adopts the charcoal-aero gel that sulphur liquid phase in organic solvent infiltrates and modify with the method preparation of supercritical fluid extraction-sulphur composite material, and composite material sulphur carbon is evenly distributed, and sulfur content is up to 50～90%, and sulfur granules is little, and granularity is controlled evenly.The diffusion of supercritical fluid extraction agent is fast, and extraction time is short; And after supercritical fluid was diffused into liquid flux, solution dilution expanded, and reduces former organic solvent to the solvability of elemental sulfur, produces rapidly degree of supersaturation and crystallization and goes out the elemental sulfur small-particle, and particle flow is good, and epigranular is controlled; Part sulphur can be in the charcoal-aero gel duct or surface crystallization, and the fixedly sulphur of charcoal-aero gel is effective; Liquid organic solvent reclaims simple, and extractant is compressed can be recycled, and extraction efficiency is high, and is pollution-free.Method of the present invention is simple to operate, is easy in industrial enforcement and production in enormous quantities.
Adopt composite positive pole and the cathode of lithium of the present invention's preparation to be assembled into button cell, under room temperature at 0.2C(335mA/g) during constant-current discharge, first discharge specific capacity reaches 1328mAh/g, circulates after 50 times Capacitance reserve more than 550mAh/g.Carbon aerogel material and the compound specific discharge capacity that improves battery of sulphur that activation+nitrating synchronous treatment process is modified have improved the cycle performance of battery.
Description of drawings
Fig. 1 is the SEM figure of the activation that obtains by embodiment 1+carbon aerogel material that the nitrating synchronous treatment process is modified;
Fig. 2 is the SEM figure of the composite positive pole that obtains by embodiment 1;
Fig. 3 is the thermogravimetric curve figure of the composite positive pole that obtains by embodiment 1;
Fig. 4 is 50 the discharge capacity curve charts of lithium-sulfur cell that obtain by embodiment 1;
Fig. 5 is the lithium-sulfur battery composite anode material first charge-discharge curve in lithium-sulfur cell that obtains by embodiment 1.
Embodiment
Below in conjunction with embodiment, the present invention is described in further details, but should not be construed as limiting the scope of the invention.
Embodiment 1:
Get potassium hydroxide 4g and melamine 2g joins in the 1g charcoal-aero gel simultaneously, mix, pour in nickel crucible, be placed in and be heated to 800 ℃ under Muffle furnace argon gas or nitrogen inert atmosphere, be incubated 2 hours.The solid of gained is rinsed with dilution heat of sulfuric acid, then be washed till neutrality with distilled water or ethanol, 120 ℃ of dryings are activated+carbon aerogel material that the nitrating synchronous process is modified.The specific area of modified charcoal-aero gel is by 620 not modified m
2/ g is increased to 1958m
2/ g, pore volume is by 0.34 cm
3/ g is increased to 0.67cm
3/ g, itrogen content of getter with nitrogen doped reaches 15.8at%.
At ambient temperature, the 2g elemental sulfur is dissolved in forms sulfur content 5% organic sulfur solution in 40g carbon disulfide organic solvent, slowly add the carbon aerogel material of the modification of 0.37g, room temperature sonic oscillation 1 hour.Then solution is put into extraction kettle, extract take postcritical ethane fluid as extractant, extraction temperature is 40 ℃, pressure is 30MPa, and the time is 40 minutes, and the flow of supercritical fluid is 1000 ml/min, decompression separation, separating pressure is 7MPa, and separation temperature is 50 ℃, then uses ethanol elution agent drip washing.60 ℃ of vacuumizes obtain the charcoal-aero gel that sulfur content 79.2% modifies-sulphur anode composite material, and its SEM figure as shown in Figure 1.
The charcoal-aero gel for preparing-sulphur anode composite material is prepared electrode slice and button cell as follows, and carry out chemical property test: the carbon aerogel composite material, binding agent, conductive black that the prepared activation+nitrating of embodiment 1 is synchronously processed modification 7:1:2 in mass ratio evenly mixes, drip solvent NMP, be coated on aluminum foil current collector after grinding to form uniform sizing material, 60 ℃ of vacuumize 12 hours, obtain composite positive pole, its SEM figure as shown in Figure 2.The thermogravimetric curve figure of this material as shown in Figure 3.
Composite positive pole is struck out the electrode slice that diameter is 10mm.Take metal lithium sheet as negative pole, be assembled into the CR2025 button cell in being full of the glove box of argon gas, carrying out the constant current charge-discharge test at 25 ℃ with 0.2C, first discharge specific capacity is 1328mAh/g, the first charge-discharge curve as shown in Figure 5,50 discharge capacity curves of this battery are as shown in Figure 4.
Embodiment 2:
At ambient temperature, the 2g elemental sulfur is dissolved in forms sulfur content 20% organic sulfur solution in the 10g toluene organic solvent, slowly add the carbon aerogel material according to embodiment 1 method gained modification of 1.2g, room temperature sonic oscillation 1 hour.Then solution is put into extraction kettle, carry out anti-solution crystallization extraction take postcritical propylene fluid as extractant, extraction temperature is 150 ℃, and pressure is 28MPa, and the time is 50 minutes, and the flow of supercritical fluid is 500 ml/min; Decompression separation, separating pressure are 4MPa, and separation temperature is 45 ℃, then use ethanol elution agent drip washing.60 ℃ of vacuumizes obtain the charcoal-aero gel that sulfur content 58.4% modifies-sulphur anode composite material.
Embodiment 3:
At ambient temperature, the 2g elemental sulfur is dissolved in forms sulfur content 5% organic sulfur solution in 40g benzene organic solvent, slowly add 0.23g according to the carbon aerogel material of the modification of embodiment 1 method gained, room temperature sonic oscillation.Then solution is put into extraction kettle, carry out anti-solution crystallization extraction take postcritical cyclohexane fluid as extractant, extraction temperature is 300 ℃, and pressure is 30MPa, and the time is 55 minutes, and the flow of supercritical fluid is 900 ml/min; Decompression separation, separating pressure are 5MPa, and separation temperature is 40 ℃, then use ethanol elution agent drip washing.60 ℃ of vacuumizes obtain the charcoal-aero gel that sulfur content 88.9% modifies-sulphur anode composite material.
Embodiment 4:
Get NaOH 2g and ethylenediamine 2g adds in the 1g charcoal-aero gel simultaneously, mix, pour in nickel crucible, be placed in and be heated to 900 ℃ under Muffle furnace argon gas or nitrogen inert atmosphere, be incubated 1 hour.The solid of gained is rinsed with dilution heat of sulfuric acid, then be washed till neutrality with distilled water or ethanol, 150 ℃ of dryings are activated+the synchronous carbon aerogel material of modifying of nitrating.After 900 ℃ of potassium hydroxide activation, the specific area of charcoal-aero gel is by 620 m
2/ g is increased to 1620m
2/ g, pore volume is by 0.34 cm
3/ g is increased to 0.55cm
3/ g, itrogen content of getter with nitrogen doped reaches 14.1at%.
At ambient temperature, the 2g elemental sulfur is dissolved in forms sulfur content 1% organic sulfur solution in 200g ortho-xylene organic solvent, slowly add the carbon aerogel material of the modification of 0.9g, room temperature sonic oscillation 1 hour.Then solution is put into extraction kettle, carry out anti-solution crystallization extraction take postcritical ethene fluid as extractant, extraction temperature is 25 ℃, and pressure is 30MPa, and the time is 40 minutes, and the flow of supercritical fluid is 800 ml/min; Decompression separation, separating pressure are 3MPa, and separation temperature is 40 ℃, then use ethanol elution agent drip washing.80 ℃ of vacuumizes obtain the charcoal-aero gel that sulfur content 48.9% modifies-sulphur anode composite material.
Embodiment 5:
Get lithium hydroxide 2g and urea 4g adds in the 1g charcoal-aero gel simultaneously, mix, pour in nickel crucible, be placed in and be heated to 800 ℃ under Muffle furnace argon gas or nitrogen atmosphere, be incubated 3 hours.The solid of gained is rinsed with dilution heat of sulfuric acid, then be washed till neutrality with distilled water or ethanol, 80 ℃ of dryings are activated+the synchronous carbon aerogel material of modifying of nitrating.After 800 ℃ of potassium hydroxide activation, the specific area of modified charcoal-aero gel is by 620 not modified m
2/ g is increased to 1577m
2/ g, pore volume is by 0.34 cm
3/ g is increased to 0.52cm
3/ g, itrogen content of getter with nitrogen doped reaches 10.8at%.
At ambient temperature, the 2g elemental sulfur is dissolved in 20g carbon tetrachloride organic solvent forms sulfur content 10% organic sulfur solution, slowly add the carbon aerogel material after the modification of 0.8g, room temperature sonic oscillation 1 hour.Then solution is put into extraction kettle, carry out anti-solution crystallization extraction take postcritical propane fluid as extractant, extraction temperature is 120 ℃, pressure is 30MPa, and the time is 60 minutes, and the flow of supercritical fluid is 800 ml/min, decompression separation, separating pressure is 5MPa, and separation temperature is 60 ℃, then uses ethanol elution agent drip washing.90 ℃ of vacuumizes obtain the charcoal-aero gel that sulfur content 71.4% modifies-sulphur anode composite material.
The charcoal-aero gel for preparing-sulphur anode composite material is prepared electrode slice and button cell as follows, and carry out chemical property test: the carbon aerogel composite material, binding agent, conductive black that the prepared activation+nitrating of embodiment 1 is synchronously processed modification 7:1:2 in mass ratio evenly mixes, drip solvent NMP, be coated on aluminum foil current collector after grinding to form uniform sizing material, 60 ℃ of vacuumize 12 hours obtains composite positive pole.Composite positive pole is struck out the electrode slice that diameter is 10mm.Take metal lithium sheet as negative pole, be assembled into the CR2025 button cell in being full of the glove box of argon gas, carry out constant current charge-discharge test at 25 ℃ with 0.2C, first discharge specific capacity is 1260mAh/g, after this circulating battery 50 times, specific capacity is 510 mAh/g.
Embodiment 6:
Get potassium hydroxide 4g and pyridine 4g adds in the 1g charcoal-aero gel simultaneously, mix, pour in nickel crucible, be placed in and be heated to 800 ℃ under Muffle furnace argon gas or nitrogen inert atmosphere, be incubated 1 hour.The solid of gained is rinsed with dilution heat of sulfuric acid, then be washed till neutrality with distilled water or ethanol, drying is activated+the synchronous carbon aerogel material of modifying of nitrating.After 800 ℃ of potassium hydroxide activation, the specific area of charcoal-aero gel is by 620 m
2/ g is increased to 1661m
2/ g, pore volume is by 0.34 cm
3/ g is increased to 0.48cm
3/ g, itrogen content of getter with nitrogen doped reaches 12.1at%.
At ambient temperature, the 2g elemental sulfur is dissolved in forms sulfur content 40% organic sulfur solution in 5g carbon disulfide organic solvent, slowly add the carbon aerogel material of the modification of 0.7g, room temperature sonic oscillation 1 hour.Then solution is put into extraction kettle, carry out anti-solution crystallization extraction take postcritical isopropyl alcohol fluid as extractant, extraction temperature is 250 ℃, and pressure is 27MPa, and the time is 60 minutes, and the flow of supercritical fluid is 800 ml/min; Decompression separation, separating pressure are 3MPa, and separation temperature is temperature 45 C, then use ethanol elution agent drip washing.60 ℃ of vacuumizes obtain the charcoal-aero gel that sulfur content 69.1% modifies-sulphur anode composite material.
Embodiment 7:
Get potassium hydroxide 3g and aniline 3g adds in the 1g charcoal-aero gel simultaneously, mix, pour in nickel crucible, be placed in and be heated to 800 ℃ under Muffle furnace argon gas or nitrogen inert atmosphere, be incubated 1 hour.The solid of gained is rinsed with dilution heat of sulfuric acid, then be washed till neutrality with distilled water or ethanol, 100 ℃ of dryings are activated+the synchronous carbon aerogel material of modifying of nitrating.After 800 ℃ of potassium hydroxide activation, the specific area of charcoal-aero gel is by 620 m
2/ g is increased to 1725m
2/ g, pore volume is by 0.34 cm
3/ g is increased to 0.51cm
3/ g, itrogen content of getter with nitrogen doped reaches 11.9at%.
At ambient temperature, the 2g elemental sulfur is dissolved in forms sulfur content 10% organic sulfur solution in 20g paraxylene organic solvent, slowly add the carbon aerogel material of the modification of 0.37g, the ultrasonic concussion of room temperature 1 hour.Then solution is put into extraction kettle, carry out anti-solution crystallization extraction take postcritical ethane fluid as extractant, extraction temperature is 30 ℃, and pressure is 26MPa, and the time is 40 minutes, and the flow of supercritical fluid is 800 ml/min; Decompression separation, separating pressure are 5MPa, and separation temperature is 40 ℃ of temperature, then use ethanol elution agent drip washing.80 ℃ of vacuumizes obtain the charcoal-aero gel that sulfur content 79.8% modifies-sulphur anode composite material.
The charcoal-aero gel for preparing-sulphur anode composite material is prepared electrode slice and button cell as follows, and carry out chemical property test: the carbon aerogel composite material, binding agent, conductive black that the prepared activation+nitrating of embodiment 1 is synchronously processed modification 7:1:2 in mass ratio evenly mixes, drip solvent NMP, be coated on aluminum foil current collector after grinding to form uniform sizing material, 60 ℃ of vacuumize 12 hours obtains composite positive pole.Composite positive pole is struck out the electrode slice that diameter is 10mm.Take metal lithium sheet as negative pole, be assembled into the CR2025 button cell in being full of the glove box of argon gas, carry out constant current charge-discharge test at 25 ℃ with 0.2C, first discharge specific capacity is 1310mAh/g, after this circulating battery 50 times, specific capacity is 530mAh/g.
Embodiment 8:
Get NaOH 3g and teabrom 4g adds in the 1g charcoal-aero gel simultaneously, mix, pour in nickel crucible, be placed in and be heated to 800 ℃ under Muffle furnace argon gas or nitrogen inert atmosphere, be incubated 1 hour.The solid of gained is rinsed with dilution heat of sulfuric acid, then be washed till neutrality with distilled water or ethanol, 130 ℃ of dryings are activated+the synchronous carbon aerogel material of modifying of nitrating.After 800 ℃ of potassium hydroxide activation, the specific area of charcoal-aero gel is by 620 m
2/ g is increased to 1607m
2/ g, pore volume is by 0.34 cm
3/ g is increased to 0.61cm
3/ g, itrogen content of getter with nitrogen doped reaches 12.4at%.
At ambient temperature, the 2g elemental sulfur is dissolved in forms sulfur content 5% organic sulfur solution in 40g ortho-xylene organic solvent, slowly add the carbon aerogel material of the modification of 0.7g, room temperature sonic oscillation 1 hour.Then solution is put into extraction kettle, carry out anti-solution crystallization extraction take postcritical ethene fluid as extractant, extraction temperature is 35 ℃, and pressure is 30MPa, and the time is 40 minutes, and the flow of supercritical fluid is 600 ml/min; Decompression separation, separating pressure are 7MPa, and separation temperature is 40 ℃ of temperature, then use ethanol elution agent drip washing.60 ℃ of vacuumizes obtain the charcoal-aero gel that sulfur content 68.4% modifies-sulphur anode composite material.
Claims (9)
1. the preparation method of a lithium-sulfur battery composite anode material is characterized in that being followed successively by following steps:
(1) modification of charcoal-aero gel: be 1:(1～5 in solid base, nitrogen source and charcoal-aero gel mass ratio): the ratio of (1～5), getting solid base and nitrogen source adds in charcoal-aero gel simultaneously, mix, be placed under Muffle furnace argon gas or nitrogen inert atmosphere protection and be heated to 700～900 ℃, be incubated 1～5 hour; The solid product of gained is rinsed with dilute acid soln, then with the washing of distilled water or ethanol to neutral, 80～150 ℃ of dryings are activated+carbon aerogel material that the nitrating synchronous process is modified;
The preparation of the charcoal-aero gel of (2) modifying-sulphur composite positive pole: under room temperature condition, elemental sulfur is dissolved in organic solvent to form mass concentration be 1～40% sulfur-containing organic solution, the charcoal-aero gel that slowly adds step (1) to make, the mass ratio of charcoal-aero gel and sulphur is 1:1～1:9, room temperature sonic oscillation 0.5～2 hour; Then solution is put into extraction kettle, extract take supercritical fluid as extractant, decompression separation, ethanol elution agent drip washing, 60～110 ℃ of lower vacuumizes, the charcoal-aero gel that obtains modifying-sulphur composite positive pole; Described organic solvent is the solvent good to the elemental sulfur dissolubility, and sulphur solubility in organic solvent is not less than 10g/L; Described supercritical fluid extraction agent is or sl. sol. organic solvent insoluble to elemental sulfur, and sulphur solubility in this organic solvent is not more than 5g.
2. preparation method according to claim 1, it is characterized in that: the nitrogen source described in step (1) is: melamine, urea, n-propylamine, n-butylamine, triethylamine, ethamine, hydrazine, dimethylamine, methyl ethylamine, diethylamine, aniline, N-methyl-N-ethylo benzene, N, one or several in N-diethylaniline, ethylenediamine, pyridine, pyrroles, second two ammoniums, teabrom, hydroxide trimethyl ethyl ammonium.
3. preparation method according to claim 2, it is characterized in that: the nitrogen source described in step (1) is: a kind of in melamine, ethylenediamine, urea, pyridine, aniline, teabrom.
4. preparation method according to claim 1, it is characterized in that: the solid base described in step (1) is one or several in NaOH, potassium hydroxide, lithium hydroxide.
5. preparation method according to claim 1, it is characterized in that: the dilute acid soln described in step (1) is one or more in watery hydrochloric acid, dilute sulfuric acid, rare nitric acid.
6. preparation method according to claim 1, it is characterized in that: the organic solvent described in step (2) is one or more in carbon disulfide, carbon tetrachloride, ortho-xylene, benzene, toluene, paraxylene.
7. preparation method according to claim 1, it is characterized in that: the supercritical fluid extraction agent described in step (2) is isopropyl alcohol, cyclohexane, ethane, ethene, propane, one or more in propylene.
8. according to claim 1 ~ 7 one of described preparation methods, it is characterized in that: the supercritical fluid extraction temperature described in step (2) is 20～300 ℃, pressure is 25～30MPa, and the time is 20～60 minutes, and the flow of supercritical fluid is 500～1000 ml/min.
9. according to claim 1 ~ 7 one of described preparation methods, it is characterized in that: described in step (2), the separating pressure of decompression separation is 3～7MPa, the temperature of separation is 40～60 ℃.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103794768A (en) * | 2014-01-23 | 2014-05-14 | 浙江师范大学 | Sulfur-carbon composite material and preparation method of composite material |
| CN105480962A (en) * | 2015-12-23 | 2016-04-13 | 河南师范大学 | Preparation method of in-situ self-assembling N-doped super-hydrophilic carbon aerogel supercapacitor electrode material |
| CN107331857A (en) * | 2017-07-03 | 2017-11-07 | 宁波富理电池材料科技有限公司 | A kind of positive electrode of surface treatment, surface treatment method and lithium ion battery |
| CN111740091A (en) * | 2020-07-08 | 2020-10-02 | 中国科学院山西煤炭化学研究所 | Carbon aerogel @ sulfur composite material for lithium-sulfur battery positive electrode and preparation method thereof |
| CN112125283A (en) * | 2020-08-03 | 2020-12-25 | 浙江工业大学 | Method for preparing lithium sulfide by solid-liquid mixing and heating |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102832379A (en) * | 2012-09-29 | 2012-12-19 | 上海空间电源研究所 | Preparation method of positive material for lithium-sulfur battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102832379A (en) * | 2012-09-29 | 2012-12-19 | 上海空间电源研究所 | Preparation method of positive material for lithium-sulfur battery |
Non-Patent Citations (2)
| Title |
|---|
| H. TAMON ET.AL..: "CONTROL OF MESOPOROUS STRUCTURE OF ORGANIC AND CARBON AEROGELS", 《CARBON》 * |
| ZULAMITA ZAPATA-BENABITHE ET. AL..: "Preparation, surface characteristics, and electrochemical double-layer capacitance of KOH-activated carbon aerogels and their O- and N-doped derivatives", 《 JOURNAL OF POWER SOURCES》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103794768A (en) * | 2014-01-23 | 2014-05-14 | 浙江师范大学 | Sulfur-carbon composite material and preparation method of composite material |
| CN105480962A (en) * | 2015-12-23 | 2016-04-13 | 河南师范大学 | Preparation method of in-situ self-assembling N-doped super-hydrophilic carbon aerogel supercapacitor electrode material |
| CN107331857A (en) * | 2017-07-03 | 2017-11-07 | 宁波富理电池材料科技有限公司 | A kind of positive electrode of surface treatment, surface treatment method and lithium ion battery |
| CN111740091A (en) * | 2020-07-08 | 2020-10-02 | 中国科学院山西煤炭化学研究所 | Carbon aerogel @ sulfur composite material for lithium-sulfur battery positive electrode and preparation method thereof |
| CN111740091B (en) * | 2020-07-08 | 2022-05-17 | 中国科学院山西煤炭化学研究所 | Carbon aerogel @ sulfur composite material for lithium-sulfur battery positive electrode and preparation method thereof |
| CN112125283A (en) * | 2020-08-03 | 2020-12-25 | 浙江工业大学 | Method for preparing lithium sulfide by solid-liquid mixing and heating |
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| Publication number | Publication date |
|---|---|
| CN103107318B (en) | 2015-05-20 |
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