CN105304882A - Preparation method of lithium-sulfur battery cathode material, lithium-sulfur battery cathode material and battery - Google Patents
Preparation method of lithium-sulfur battery cathode material, lithium-sulfur battery cathode material and battery Download PDFInfo
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- CN105304882A CN105304882A CN201410359876.5A CN201410359876A CN105304882A CN 105304882 A CN105304882 A CN 105304882A CN 201410359876 A CN201410359876 A CN 201410359876A CN 105304882 A CN105304882 A CN 105304882A
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Abstract
The invention discloses a preparation method of a lithium-sulfur battery cathode material, the lithium-sulfur battery cathode material and a battery. The preparation method comprises the following steps: respectively dissolving or dispersing 50-97wt% of a sulfur material and 3-50wt% of a conductive material in the same or different solvent(s) for mixing; stirring for 1 to 24 hours at the speed of 1000 to 6000 rpd/min; carrying out spray drying under the condition of 60-250 DEG C to obtain the lithium-sulfur battery cathode material, wherein the lithium-sulfur battery cathode material adopts micron-sized spherules of nano-micro structures.
Description
Technical field
The present invention relates to field of material technology, particularly relate to a kind of preparation method of lithium sulfur battery anode material, lithium sulfur battery anode material and battery.
Background technology
Lithium battery system, as a kind of high-efficiency energy-storage device be widely used, has more and more important effect at society.In future, it is more expected to large scale storage for electric automobile, clean energy resource (wind energy, solar energy, water energy and tidal energy etc.) and intelligent grid, has huge meaning to alleviating deficient etc. the significant problem injuring human development of greenhouse effect, global warming, fossil energy.Lithium-sulfur cell system, be the outstanding person in lithium battery system, its gravimetric energy density is far longer than existing lithium-ion battery system, is the focus of scientific research always.In addition, the cheap and aboundresources environmental friendliness again of its electrode material elemental sulfur, makes lithium-sulfur cell system great commercial value.
But lithium-sulfur cell many problems before practical application still have to be solved.Wherein, problem the most basic is the elemental sulfur as positive active material, is at room temperature typical electronics and ion insulator, and when 25 DEG C, conductivity is 5 × 10
-30siemens/cm.Usually sulphur and high conductivity material phase compound are improved the conductivity of electrode.And in the charge and discharge process of lithium-sulfur cell, the many sulphions of intermediate product are dissolved in electrolyte and effect of shuttling back and forth gradually, in addition end product lithium sulfide is had an appointment the volumetric expansion of 70%, active material sulphur is all made to be separated with high conductivity material, cause positive electrode utilization efficiency low, cycle performance of battery and high rate performance poor, battery is short.
For these problems, researcher had carried out a series of optimization to lithium sulfur system in the last few years.In positive electrode, be how key point by sulphur and the better compound of high conductivity material.Most Research approach is the material with carbon element preparing special construction, as highly ordered mesosize pores carbon series, classification meso-porous carbon material, carbon fiber etc.; With the carrier of these material with carbon elements as sulphur, obtain carbon-sulfur compound by heat treatment, ball milling, liquid phase method, the mode such as plasma-deposited; Some conducting polymers on the Surface coating of compound again, as poly(ethylene oxide), polyaniline, polypyrrole etc.The electrode material obtained like this is that skeleton forms conductive network with carbon, and the many sulphions of intermediate product that sulphur produces can be bound in the special hole of material with carbon element, and conducting polymer coating layer also serves enhancing conductivity, stops that many sulphions are dissolved in the effect of electrolyte.By these Optimized Approaches, the positive active material utilization efficiency of lithium-sulfur cell is improved, and cycle performance is also improved.But these Optimized Approaches are not enough to some extent.First, the material with carbon element preparing special construction improves the cost of lithium-sulfur cell; Moreover as plasma-deposited, liquid phase method, conducting polymer be coated etc., preparation technology is comparatively complicated, is difficult to large-scale production; And in general, in carbon-sulfur compound, carbon proportion is larger, and the circulation of positive electrode is more stable, but for whole combination electrode, its gravimetric energy density declines greatly.
Summary of the invention
Embodiments provide a kind of preparation method of lithium sulfur battery anode material, lithium sulfur battery anode material and battery.Described method technique is simple, ripe, applied widely, can be used in large-scale industrial production.Apply secondary cell prepared by preparation method provided by the invention, have the advantages that cycle performance is excellent and coulombic efficiency is high.
First aspect, embodiments provides a kind of preparation method for lithium sulfur battery anode material, and described method comprises:
The electric conducting material of the sulfur materials of 50wt%-97wt% and 3wt%-50wt% is dissolved or dispersed in identical or different solvent respectively, and mixes;
1-24 hour is stirred with the speed of 1000rpd/min-6000rpd/min;
Under 60 DEG C of-250 DEG C of conditions, carry out spraying dry, obtain described lithium sulfur battery anode material;
Wherein, described lithium sulfur battery anode material is the micron order bead with nano-micro structure.
Preferably, described under 60 DEG C of-250 DEG C of conditions, carry out spraying dry after, and described obtain described lithium sulfur battery anode material before, described method also comprises:
To the heat treatment 3 minutes-72 hours under 50 DEG C of-800 DEG C of conditions of the material after spraying dry.
Preferred further, described heat treated temperature is 155 DEG C-300 DEG C, and the time is 30 minutes-24 hours.
Preferably, described sulfur materials comprises: sublimed sulfur, sedimentation sulphur, crystallization sulphur, colloid sulphur, without any one or more in crystalline state sulphur, crystallite sulphur, nano-sulfur or molten sulfur.
Preferably, described electric conducting material comprises: any one or more in metal, metal oxide, material with carbon element, silicon materials, sulfide, organic conductive molecule or conducting polymer;
Wherein, described material with carbon element is the granular material with carbon element of dispersion, comprising: any one or more in carbon black, carbon aerogels, graphite, acetylene black, Ke Qinhei, activated carbon, Graphene, graphene oxide, nano-C particles, carbon nano-fiber, conductive carbon black, carbonaceous mesophase spherules, carbon ball, carbon nano-tube, ordered mesopore carbon or hierarchical porous structure carbon.
Further preferred, before being dissolved or dispersed in identical or different solvent respectively by the described electric conducting material by the sulfur materials of 50wt%-97wt% and 3wt%-50wt%, described method also comprises:
Described material with carbon element is carried out to the preliminary treatment of surface functionalization;
Wherein, described preliminary treatment is specially:
Described material with carbon element is dispersed in oxidizing liquid, by leaving standstill, heating, concussion and/or ultrasonic, magnetic agitation and/or high-speed stirred, after backflow, then through washing, suction filtration, centrifugal, evaporate, obtain the material with carbon element of described surface functionalization; Wherein, described oxidizing liquid comprises: one or more in the concentrated sulfuric acid, red fuming nitric acid (RFNA), hydrogen peroxide, liquor potassic permanganate, potassium chlorate solution or bromine water; Or
Described material with carbon element is placed in oxidizing gas heat-treat, obtains the material with carbon element of described surface functionalization; Wherein, described oxidizing gas comprises air, oxygen or carbon dioxide.
Preferably, described solvent and described sulfur materials and all chemical reaction does not occur with described electric conducting material, and the boiling point of described solvent is lower than 350 DEG C;
Described solvent specifically comprises: water, ethanol, acetone, carbon disulfide, isopentane, pentane, benzinum, hexane, cyclohexane, isooctane, trimethylpentane, pentamethylene, heptane, trichloroethylene/acetylene trichloride, carbon tetrachloride, propyl ether/propyl ether, toluene, paraxylene, chlorobenzene, o-dichlorohenzene, diethyl ether/ether, benzene, isobutanol, ethylene dichloride, n-butanol, butyl acetate/butyl acetate, propyl alcohol, methylisobutylketone, oxolane, ethyl acetate, isopropyl alcohol, chloroform, methyl ethyl ketone, pyridine, acetic acid, acetonitrile, aniline, dimethyl formamide, methyl alcohol, ethylene glycol, methyl-sulfoxide, n-methlpyrrolidone dimethylamine, 1,1-dichloroethanes, butanone, glycol dimethyl ether, triethylamine, propionitrile, 4-methyl-2 pentanone, ethylenediamine, glycol monomethyl ether, ethylene glycol monoethyl ether, dimethylbenzene, meta-xylene, ortho-xylene, cyclohexanone, cyclohexanol, nitrogen, nitrogen-dimethylacetylamide, phenol, 1,2-PD, orthoresol, nitrogen, nitrogen-dimethylaniline, metacresol, cresols, formamide, nitrobenzene, acetamide, HPT, quinoline, ethylene carbonate diethylene glycol (DEG), any one or more in succinonitrile or glycerine.
Second aspect, embodiments provides lithium sulfur battery anode material prepared by a kind of preparation method utilizing above-mentioned first aspect to provide, and the pattern of described lithium sulfur battery anode material is the micron order bead with nano-micro structure; The diameter of described micron order bead is 1 micron-20 microns;
Wherein, described micron order bead is made up of nano-structured particles, and the particle diameter of described nano-structured particles is 1nm-80nm.
The third aspect, embodiments provides a kind of battery comprising the lithium sulfur battery anode material of above-mentioned second aspect.
The preparation method of the lithium sulfur battery anode material of the embodiment of the present invention, technique is simple, ripe, applied widely, can be used in large-scale industrial production.
Accompanying drawing explanation
Below by drawings and Examples, the technical scheme of the embodiment of the present invention is described in further detail.
Preparation method's flow chart of the lithium sulfur battery anode material that Fig. 1 provides for the embodiment of the present invention;
Fig. 2 is the scanning electron microscope diagram of sulphur/multi-walled carbon nano-tubes compound prepared by the embodiment of the present invention 2;
Fig. 3 is the scanning electron microscope diagram of sulphur/multi-walled carbon nano-tubes compound prepared by the embodiment of the present invention 2;
Fig. 4 is the thermogravimetric analysis figure of sulphur/multi-walled carbon nano-tubes compound prepared by the embodiment of the present invention 2;
Fig. 5 is the charging and discharging curve of sulphur/multi-walled carbon nano-tubes compound as lithium sulfur battery anode material of the embodiment of the present invention 2 preparation;
Fig. 6 is the cyclic curve of sulphur/multi-walled carbon nano-tubes compound as lithium sulfur battery anode material of the embodiment of the present invention 2 preparation;
Fig. 7 is the scanning electron microscope diagram of sulphur/Ke Qinhei compound prepared by the embodiment of the present invention 4;
Fig. 8 is the thermogravimetric analysis figure of sulphur/Ke Qinhei compound prepared by the embodiment of the present invention 4;
Fig. 9 is the charging and discharging curve of sulphur/Ke Qinhei compound as lithium sulfur battery anode material of the embodiment of the present invention 4 preparation;
Figure 10 is the cyclic curve of sulphur/Ke Qinhei compound as lithium sulfur battery anode material of the embodiment of the present invention 4 preparation;
Figure 11 is the scanning electron microscope diagram of sulphur/multi-walled carbon nano-tubes/Ke Qinhei compound prepared by the embodiment of the present invention 14;
Figure 12 is the thermogravimetric analysis figure of sulphur/multi-walled carbon nano-tubes/Ke Qinhei compound prepared by the embodiment of the present invention 14;
Figure 13 is the charging and discharging curve of sulphur/multi-walled carbon nano-tubes/Ke Qinhei compound as lithium sulfur battery anode material of the embodiment of the present invention 14 preparation;
Figure 14 is the cyclic curve of sulphur/multi-walled carbon nano-tubes/Ke Qinhei compound as lithium sulfur battery anode material of the embodiment of the present invention 14 preparation;
Figure 15 is the thermogravimetric analysis figure of sulphur (ball milling)/multi-walled carbon nano-tubes/Ke Qinhei compound prepared by the embodiment of the present invention 80;
Figure 16 is the charging and discharging curve of sulphur (ball milling)/multi-walled carbon nano-tubes/Ke Qinhei compound as lithium sulfur battery anode material of the embodiment of the present invention 80 preparation;
Figure 17 is the cyclic curve of sulphur (ball milling)/multi-walled carbon nano-tubes/Ke Qinhei compound as lithium sulfur battery anode material of the embodiment of the present invention 80 preparation.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but is not intended to limit the scope of the invention.
Embodiment 1
The embodiment of the present invention 1 provides a kind of preparation method of lithium sulfur battery anode material, and as shown in Figure 1, described method comprises the steps:
Step 110, is dissolved or dispersed in the electric conducting material of the sulfur materials of 50-97wt% and 3-50wt% respectively in identical or different solvent, and mixes;
Concrete, sulfur materials comprises: sublimed sulfur, sedimentation sulphur, crystallization sulphur, colloid sulphur, without any one or more in crystalline state sulphur, crystallite sulphur, nano-sulfur or molten sulfur.
Electric conducting material is the electric conducting material with high conductivity, specifically comprises: any one or more in metal, metal oxide, material with carbon element, silicon materials, sulfide, organic conductive molecule or conducting polymer;
Wherein said material with carbon element is the granular carbon material of dispersion, specifically comprises: any one or more in carbon black, carbon aerogels, graphite, acetylene black, Ke Qinhei, activated carbon, Graphene, graphene oxide, nano-C particles, carbon nano-fiber, conductive carbon black, carbonaceous mesophase spherules, carbon ball, carbon nano-tube, ordered mesopore carbon or hierarchical porous structure carbon.
Described material with carbon element can more preferably: any one or multiple mixture of carbon nano-tube, Ke Qinhei, activated carbon, acetylene black, Graphene or graphene oxide.
Optionally, the preliminary treatment of surface functionalization can also be carried out in advance for material with carbon element:
Can described material with carbon element be dispersed in oxidizing liquid, by leaving standstill, heating, concussion and/or ultrasonic, magnetic agitation and/or high-speed stirred, after backflow, then through washing, suction filtration, centrifugal, evaporate, obtain the material with carbon element of described surface functionalization; Wherein, described oxidizing liquid comprises: one or more in the concentrated sulfuric acid, red fuming nitric acid (RFNA), hydrogen peroxide, liquor potassic permanganate, potassium chlorate solution or bromine water;
Or
Described material with carbon element can being placed in oxidizing gas, as heat-treated in the mist etc. of air, oxygen, carbon dioxide or oxygen and carbon dioxide, obtaining the material with carbon element of described surface functionalization.
If the particle size of selected sulfur materials or electric conducting material is larger, first by methods such as high-energy ball millings, scantling can be reduced to nanoscale and re-uses dissolution with solvents or dispersion.
Described solvent and described sulfur materials or all chemical reaction does not occur with described electric conducting material, dissolve each other, and the boiling point of described solvent is lower than 350 DEG C between selected solvent;
Described solvent specifically comprises: water, ethanol, acetone, carbon disulfide, isopentane, pentane, benzinum, hexane, cyclohexane, isooctane, trimethylpentane, pentamethylene, heptane, trichloroethylene/acetylene trichloride, carbon tetrachloride, propyl ether/propyl ether, toluene, paraxylene, chlorobenzene, o-dichlorohenzene, diethyl ether/ether, benzene, isobutanol, ethylene dichloride, n-butanol, butyl acetate/butyl acetate, propyl alcohol, methylisobutylketone, oxolane, ethyl acetate, isopropyl alcohol, chloroform, methyl ethyl ketone, pyridine, acetic acid, acetonitrile, aniline, dimethyl formamide, methyl alcohol, ethylene glycol, methyl-sulfoxide, n-methlpyrrolidone dimethylamine, 1,1-dichloroethanes, butanone, glycol dimethyl ether, triethylamine, propionitrile, 4-methyl-2 pentanone, ethylenediamine, glycol monomethyl ether, ethylene glycol monoethyl ether, dimethylbenzene, meta-xylene, ortho-xylene, cyclohexanone, cyclohexanol, nitrogen, nitrogen-dimethylacetylamide, phenol, 1,2-PD, orthoresol, nitrogen, nitrogen-dimethylaniline, metacresol, cresols, formamide, nitrobenzene, acetamide, HPT, quinoline, ethylene carbonate diethylene glycol (DEG), any one or more in succinonitrile or glycerine.
Described solvent can be preferably: one or more the mixture in carbon disulfide, ethanol, isopropyl alcohol, ether, benzene, toluene, n-methlpyrrolidone, acetone, cyclohexane or water.
Sulfur materials and electric conducting material can come into operation with arbitrary proportion in above-mentioned mass ratio range, and wherein, the mass percent of sulfur materials can be preferably 70wt%-97wt%.
The quality summation (gram) of described sulfur materials and described electric conducting material is 0.01-200% with the percentage of the volume (milliliter) of described solvent.Wherein, 0.5%-70% is preferably.
Be dissolved or dispersed in respectively after in identical or different solvent at sulfur materials and electric conducting material, material can be reached and better dissolve in a solvent or dispersion by suitable heating, concussion, magnetic agitation, high-speed stirred, the method such as ultrasonic.
In one example in which, described stirring can be magnetic agitation 1 hour at normal temperatures, ultrasonic 1 hour.
Step 120, stirs 1-24 hour with the speed of 1000rpd/min-6000rpd/min;
Concrete, after two kinds of solvents dissolved or dispersed with sulfur materials and electric conducting material mix, both mixing can be made by suitable heating, concussion, magnetic agitation, high-speed stirred, ultrasonic and combination evenly.
In a preferred example, under normal temperature, stir 5 hours with the speed of 2000rpd/min.
Step 130, carries out spraying dry under 60 DEG C of-250 DEG C of conditions, obtains described lithium sulfur battery anode material;
Concrete, described spray-dired condition is: suitably, design temperature should choose a temperature higher than the boiling point of mixed solvent for ring airspeed and sample rate, and mixed solvent refers to for spray-dired dissolved or dispersed with the mixed liquor of the solvent of material.Spray-dired temperature range is 60 DEG C-250 DEG C.Be preferably, 100 DEG C-180 DEG C.It should be noted that if the temperature of getting higher than or close to the burning-point of a certain component in mixed solvent, first mixed solvent can be heat-treated a period of time, carry out spraying dry again by after this component volatilization.
Optionally, after spray drying, can also to the material obtained after spraying dry heat treatment 3 minutes-72 hours under 50 DEG C of-800 DEG C of conditions, or preferably, under 155 DEG C of-300 DEG C of conditions, heat treatment 30 minutes-24 hours, obtains described lithium sulfur battery anode material.
The pattern of the lithium sulfur battery anode material obtained according to said method is the micron order bead with nano-micro structure.Wherein, the diameter of micron order bead is 1 micron-20 microns, can Controlling Technology by the diameter control of micron order bead for preparing at 3 microns-5 microns.Wherein, described micron order bead is made up of nano-structured particles, and the particle diameter of described nano-structured particles is 1nm-80nm, is preferably 10 nanometer-100 nanometers.
The preparation method of the lithium sulfur battery anode material that the embodiment of the present invention provides, technique is simple, ripe, applied widely, can be used in large-scale industrial production.
Below by embodiment 2-embodiment 89, the preparation method that above-described embodiment 1 provides is specifically described, and the battery performance be applied to by the lithium sulfur battery anode material that the method provided by each embodiment is prepared in battery is described after each embodiment.
Embodiment 2
The sublimed sulfur getting 1.5 grams is dissolved in the carbon disulfide solution of 15 milliliters, and normal temperature lower magnetic force stirs, and sulphur dissolves and obtains yellow solution.Get the multi-walled carbon nano-tubes of 1 gram, add ethanol to 100 milliliter, ultrasonic 1 hour, obtain the slurry of black favorable dispersibility.By above-mentioned two kinds of mixture sulphur-carbon disulfide and multi-walled carbon nano-tubes-ethanol mixing, the lower 2000 revs/min of high-speed stirred of normal temperature 5 hours.In whipping process, carbon disulfide and ethanol volatilize gradually, add in time into ethanol to cumulative volume 150 milliliters.After stirring terminates, the mixed slurry modest viscosity obtained.Carry out spraying dry to described mixed slurry, design temperature 120 DEG C, obtains lithium sulfur battery anode material.
In the present embodiment, lithium sulfur battery anode material is sulphur/multi-walled carbon nano-tubes compound.
Fig. 2 and Fig. 3 is respectively the scanning electron microscope diagram of sulphur/multi-walled carbon nano-tubes compound prepared by the present embodiment.Fig. 4 is the thermogravimetric analysis figure of sulphur/multi-walled carbon nano-tubes compound prepared by the present embodiment.
Lithium sulfur battery anode material is directly used as cell positive material, using lithium metal as negative material, assemble the battery obtained discharging by voltage for 1.2V with the multiplying power of 0.1/ hour, charging is tested under voltage is the condition of 3.0V, test result is shown in Fig. 5, the charging and discharging curve of first week, the tenth week and the 100 week is shown in Fig. 5, can have found out, first all specific discharge capacity 1510mAh/g.The cyclic curve schematic diagram of this battery has been shown in Fig. 6.
Embodiment 3
Preparation method with embodiment 2, spraying dry design temperature 150 DEG C.Method of testing is with above-described embodiment 2.
Embodiment 4
The sublimed sulfur getting 4 grams is dissolved in the carbon disulfide solution of 40 milliliters, and normal temperature lower magnetic force stirs, and sulphur dissolves and obtains yellow solution.Get the Ke Qinhei of 1 gram, add ethanol to 100 milliliter, ultrasonic 1 hour, obtain the slurry of black favorable dispersibility.By above-mentioned two kinds of mixture sulphur-carbon disulfide and Ke Qinhei-ethanol mixing, with 2000 revs/min of high-speed stirred 5 hours under normal temperature.In whipping process, carbon disulfide and ethanol volatilize gradually, add in time into ethanol to cumulative volume 150 milliliters.After stirring terminates, the mixed slurry modest viscosity obtained.Carry out spraying dry to described mixed slurry, design temperature 120 DEG C, obtains lithium sulfur battery anode material.
In the present embodiment, lithium sulfur battery anode material is sulphur/Ke Qinhei compound.
Fig. 7 is the scanning electron microscope diagram of sulphur/Ke Qinhei compound prepared by the present embodiment.Fig. 8 is the thermogravimetric analysis figure of sulphur/Ke Qinhei compound prepared by the present embodiment.
Lithium sulfur battery anode material is directly used as cell positive material, using lithium metal as negative material, assemble the battery that obtains with the multiplying power of 0.1/ hour in electric discharge by voltage for 1.5V, charge and to test under voltage is the condition of 2.8V, test result is shown in Fig. 9.The charging and discharging curve of first week, the tenth week and the 100 week is shown in Fig. 9, can have found out, first all specific discharge capacity 1274mAh/g.The cyclic curve schematic diagram of this battery has been shown in Figure 10.
Embodiment 5
Preparation method with embodiment 4, spraying dry design temperature 150 DEG C.Method of testing is with above-described embodiment 4.
Embodiment 6
Material with carbon element, with embodiment 2, is replaced to active carbon by multi-walled carbon nano-tubes by preparation method.Method of testing is with above-described embodiment 4.
Embodiment 7
Material with carbon element, with embodiment 2, is replaced to active carbon by multi-walled carbon nano-tubes by preparation method, spraying dry design temperature 150 DEG C.Method of testing is with above-described embodiment 4.
Embodiment 8
Material with carbon element, with embodiment 2, is replaced to acetylene black by multi-walled carbon nano-tubes by preparation method.Method of testing is with above-described embodiment 4.
Embodiment 9
Material with carbon element, with embodiment 2, is replaced to acetylene black by multi-walled carbon nano-tubes by preparation method, spraying dry design temperature 150 DEG C.Method of testing is with above-described embodiment 4.
Embodiment 10
Material with carbon element, with embodiment 2, is replaced to Graphene by multi-walled carbon nano-tubes by preparation method.Method of testing is with above-described embodiment 4.
Embodiment 11
Material with carbon element, with embodiment 2, is replaced to Graphene by multi-walled carbon nano-tubes by preparation method, spraying dry design temperature 150 DEG C.Method of testing is with above-described embodiment 4.
Embodiment 12
Material with carbon element, with embodiment 2, is replaced to graphene oxide by multi-walled carbon nano-tubes by preparation method.Method of testing is with above-described embodiment 4.
Embodiment 13
Material with carbon element, with embodiment 2, is replaced to graphene oxide by multi-walled carbon nano-tubes by preparation method, spraying dry design temperature 150 DEG C.Method of testing is with above-described embodiment 4.
Embodiment 14
The sublimed sulfur getting 4.5 grams is dissolved in the carbon disulfide solution of 45 milliliters, and normal temperature lower magnetic force stirs, and sulphur dissolves and obtains yellow solution.Get the multi-walled carbon nano-tubes of 0.95 gram Ke Qinhei and 0.05 gram, add ethanol to 100 milliliter, ultrasonic 1 hour, obtain the slurry of black favorable dispersibility.By above-mentioned two kinds of mixture sulphur-carbon disulfide and Ke Qinhei/multi-walled carbon nano-tubes-ethanol mixing, the lower 2000 revs/min of high-speed stirred of normal temperature 5 hours.In whipping process, carbon disulfide and ethanol volatilize gradually, add in time into ethanol to cumulative volume 150 milliliters.After stirring terminates, the mixed slurry modest viscosity obtained.Carry out spraying dry to described mixed slurry, design temperature 120 DEG C, obtains lithium sulfur battery anode material.
In the present embodiment, lithium sulfur battery anode material is sulphur/multi-walled carbon nano-tubes/Ke Qinhei compound.
Figure 11 is the scanning electron microscope diagram of sulphur/multi-walled carbon nano-tubes/Ke Qinhei compound prepared by the present embodiment.Figure 12 is the thermogravimetric analysis figure of sulphur/multi-walled carbon nano-tubes compound prepared by the present embodiment.
Lithium sulfur battery anode material is directly used as cell positive material, using lithium metal as negative material, assemble the battery that obtains with the multiplying power of 0.1/ hour in electric discharge by voltage for 1.5V, charge and to test under voltage is the condition of 2.8V, test result is shown in Figure 13.The charging and discharging curve of first week, the tenth week and the 100 week is shown in Figure 13, can have found out, first all specific discharge capacity 1220mAh/g.The cyclic curve schematic diagram of this battery has been shown in Figure 14.
Embodiment 15
Preparation method with embodiment 14, spraying dry design temperature 150 DEG C.Method of testing is with above-described embodiment 14.
Embodiment 16
Material with carbon element, with embodiment 14, is replaced to activated carbon by Ke Qinhei by preparation method.Method of testing is with above-described embodiment 14.
Embodiment 17
Material with carbon element, with embodiment 14, is replaced to activated carbon by Ke Qinhei by preparation method, spraying dry design temperature 150 DEG C.Method of testing is with above-described embodiment 14.
Embodiment 18
Material with carbon element, with embodiment 14, is replaced to acetylene black by Ke Qinhei by preparation method.Method of testing is with above-described embodiment 14.
Embodiment 19
Material with carbon element, with embodiment 14, is replaced to acetylene black by Ke Qinhei by preparation method, spraying dry design temperature 150 DEG C.Method of testing is with above-described embodiment 14.
Embodiment 20
Material with carbon element, with embodiment 14, is replaced to Graphene by Ke Qinhei by preparation method.Method of testing is with above-described embodiment 14.
Embodiment 21
Material with carbon element, with embodiment 14, is replaced to Graphene by Ke Qinhei by preparation method, spraying dry design temperature 150 DEG C.Method of testing is with above-described embodiment 14.
Embodiment 22
Material with carbon element, with embodiment 14, is replaced to graphene oxide by Ke Qinhei by preparation method.Method of testing is with above-described embodiment 14.
Embodiment 23
Material with carbon element, with embodiment 14, is replaced to graphene oxide by Ke Qinhei by preparation method, spraying dry design temperature 150 DEG C.Method of testing is with above-described embodiment 14.
Embodiment 24
The sublimed sulfur getting 2 grams is dissolved in the ethanolic solution of 900 milliliters, 40 DEG C of magnetic agitation, and sulphur is partly dissolved and obtains faint yellow suspension-turbid liquid.Get the multi-walled carbon nano-tubes of 1 gram, add ethanol to 100 milliliter, ultrasonic 1 hour, obtain the slurry of black favorable dispersibility.By above-mentioned two kinds of mixture sulphur-ethanol and multi-walled carbon nano-tubes-ethanol mixing, the lower 2000 revs/min of high-speed stirred of normal temperature 5 hours.After stirring terminates, the mixed slurry modest viscosity obtained.Carry out spraying dry to described mixed slurry, design temperature 120 DEG C, obtains lithium sulfur battery anode material.Method of testing is with above-described embodiment 14.
Embodiment 25
Preparation method with embodiment 24, spraying dry design temperature 150 DEG C.Method of testing is with above-described embodiment 14.
Embodiment 26
Material with carbon element, with embodiment 24, is replaced to Ke Qinhei by multi-walled carbon nano-tubes by preparation method.Method of testing is with above-described embodiment 14.
Embodiment 27
Material with carbon element, with embodiment 24, is replaced to Ke Qinhei by multi-walled carbon nano-tubes by preparation method, spraying dry design temperature 150 DEG C.Method of testing is with above-described embodiment 14.
Embodiment 28
Material with carbon element, with embodiment 24, is replaced to active carbon by multi-walled carbon nano-tubes by preparation method.Method of testing is with above-described embodiment 14.
Embodiment 29
Material with carbon element, with embodiment 24, is replaced to active carbon by multi-walled carbon nano-tubes by preparation method, spraying dry design temperature 150 DEG C.Method of testing is with above-described embodiment 14.
Embodiment 30
Material with carbon element, with embodiment 24, is replaced to acetylene black by multi-walled carbon nano-tubes by preparation method.Method of testing is with above-described embodiment 14.
Embodiment 31
Material with carbon element, with embodiment 24, is replaced to acetylene black by multi-walled carbon nano-tubes by preparation method, spraying dry design temperature 150 DEG C.Method of testing is with above-described embodiment 14.
Embodiment 32
Material with carbon element, with embodiment 24, is replaced to Graphene by multi-walled carbon nano-tubes by preparation method.Method of testing is with above-described embodiment 14.
Embodiment 33
Material with carbon element, with embodiment 24, is replaced to Graphene by multi-walled carbon nano-tubes by preparation method, spraying dry design temperature 150 DEG C.Method of testing is with above-described embodiment 14.
Embodiment 34
Material with carbon element, with embodiment 24, is replaced to graphene oxide by multi-walled carbon nano-tubes by preparation method.Method of testing is with above-described embodiment 14.
Embodiment 35
Material with carbon element, with embodiment 24, is replaced to graphene oxide by multi-walled carbon nano-tubes by preparation method, spraying dry design temperature 150 DEG C.Method of testing is with above-described embodiment 14.
Embodiment 36
The sublimed sulfur getting 4.5 grams is dissolved in the ethanolic solution of 2000 milliliters, 40 DEG C of magnetic agitation, and sulphur is partly dissolved and obtains faint yellow suspension-turbid liquid.Get the multi-walled carbon nano-tubes of 0.95 gram Ke Qinhei and 0.05 gram, add ethanol to 100 milliliter, ultrasonic 1 hour, obtain the slurry of black favorable dispersibility.By above-mentioned two kinds of mixture sulphur-ethanol and Ke Qinhei/multi-walled carbon nano-tubes-ethanol mixing, the lower 2000 revs/min of high-speed stirred of normal temperature 5 hours.After stirring terminates, the mixed slurry modest viscosity obtained.Carry out spraying dry to described mixed slurry, design temperature 120 DEG C, obtains lithium sulfur battery anode material.Method of testing is with above-described embodiment 14.
Embodiment 37
Preparation method with embodiment 36, spraying dry design temperature 150 DEG C.Method of testing is with above-described embodiment 14.
Embodiment 38
Material with carbon element, with embodiment 36, is replaced to activated carbon by Ke Qinhei by preparation method.Method of testing is with above-described embodiment 14.
Embodiment 39
Material with carbon element, with embodiment 36, is replaced to activated carbon by Ke Qinhei by preparation method, spraying dry design temperature 150 DEG C.Method of testing is with above-described embodiment 14.
Embodiment 40
Material with carbon element, with embodiment 36, is replaced to acetylene black by Ke Qinhei by preparation method.Method of testing is with above-described embodiment 14.
Embodiment 41
Material with carbon element, with embodiment 36, is replaced to acetylene black by Ke Qinhei by preparation method, spraying dry design temperature 150 DEG C.Method of testing is with above-described embodiment 14.
Embodiment 42
Material with carbon element, with embodiment 36, is replaced to Graphene by Ke Qinhei by preparation method.Method of testing is with above-described embodiment 14.
Embodiment 43
Material with carbon element, with embodiment 36, is replaced to Graphene by Ke Qinhei by preparation method, spraying dry design temperature 150 DEG C.Method of testing is with above-described embodiment 14.
Embodiment 44
Material with carbon element, with embodiment 36, is replaced to graphene oxide by Ke Qinhei by preparation method.Method of testing is with above-described embodiment 14.
Embodiment 45
Material with carbon element, with embodiment 36, is replaced to graphene oxide by Ke Qinhei by preparation method, spraying dry design temperature 150 DEG C.Method of testing is with above-described embodiment 14.
Embodiment 46
The sublimed sulfur getting 4.5 grams adds 50 ml deionized water, and high-energy ball milling wet-milling obtains flaxen suspension.Get the multi-walled carbon nano-tubes of 1 gram, add ethanol to 100 milliliter, ultrasonic 1 hour, obtain the slurry of black favorable dispersibility.By above-mentioned two kinds of mixture sulphur-deionized waters and multi-walled carbon nano-tubes-ethanol mixing, the lower 2000 revs/min of high-speed stirred of normal temperature 5 hours.In whipping process, add ethanol to cumulative volume 150 milliliters.After stirring terminates, the mixed slurry modest viscosity obtained.Carry out spraying dry to described mixed slurry, design temperature 130 DEG C, obtains lithium sulfur battery anode material.Method of testing is with above-described embodiment 14.
Embodiment 47
Preparation method with embodiment 46, spraying dry design temperature 150 DEG C.Method of testing is with above-described embodiment 14.
Embodiment 48
Material with carbon element, with embodiment 46, is replaced to Ke Qinhei by multi-walled carbon nano-tubes by preparation method.Method of testing is with above-described embodiment 14.
Embodiment 49
Material with carbon element, with embodiment 46, is replaced to Ke Qinhei by multi-walled carbon nano-tubes by preparation method, spraying dry design temperature 150 DEG C.Method of testing is with above-described embodiment 14.
Embodiment 50
Material with carbon element, with embodiment 46, is replaced to active carbon by multi-walled carbon nano-tubes by preparation method.Method of testing is with above-described embodiment 14.
Embodiment 51
Material with carbon element, with embodiment 46, is replaced to active carbon by multi-walled carbon nano-tubes by preparation method, spraying dry design temperature 150 DEG C.Method of testing is with above-described embodiment 14.
Embodiment 52
Material with carbon element, with embodiment 46, is replaced to acetylene black by multi-walled carbon nano-tubes by preparation method.Method of testing is with above-described embodiment 14.
Embodiment 53
Material with carbon element, with embodiment 46, is replaced to acetylene black by multi-walled carbon nano-tubes by preparation method, spraying dry design temperature 150 DEG C.Method of testing is with above-described embodiment 14.
Embodiment 54
Material with carbon element, with embodiment 46, is replaced to Graphene by multi-walled carbon nano-tubes by preparation method.Method of testing is with above-described embodiment 14.
Embodiment 55
Material with carbon element, with embodiment 46, is replaced to Graphene by multi-walled carbon nano-tubes by preparation method, spraying dry design temperature 150 DEG C.Method of testing is with above-described embodiment 14.
Embodiment 56
Material with carbon element, with embodiment 46, is replaced to graphene oxide by multi-walled carbon nano-tubes by preparation method.Method of testing is with above-described embodiment 14.
Embodiment 57
Material with carbon element, with embodiment 46, is replaced to graphene oxide by multi-walled carbon nano-tubes by preparation method, spraying dry design temperature 150 DEG C.Method of testing is with above-described embodiment 14.
Embodiment 58
Material with carbon element, with embodiment 46, is replaced to 0.95 Ke Keqinhei and 0.05 gram multi-walled carbon nano-tubes by 1 gram of multi-walled carbon nano-tubes by preparation method.Method of testing is with above-described embodiment 14.
Embodiment 59
Material with carbon element, with embodiment 46, is replaced to 0.95 Ke Keqinhei and 0.05 gram multi-walled carbon nano-tubes by 1 gram of multi-walled carbon nano-tubes by preparation method, spraying dry design temperature 150 DEG C.Method of testing is with above-described embodiment 14.
Embodiment 60
Material with carbon element, with embodiment 46, is replaced to 0.95 gram of active carbon and 0.05 gram of multi-walled carbon nano-tubes by 1 gram of multi-walled carbon nano-tubes by preparation method.Method of testing is with above-described embodiment 14.
Embodiment 61
Material with carbon element, with embodiment 46, is replaced to 0.95 gram of active carbon and 0.05 gram of multi-walled carbon nano-tubes by 1 gram of multi-walled carbon nano-tubes, spraying dry design temperature 150 DEG C by preparation method.Method of testing is with above-described embodiment 14.
Embodiment 62
Material with carbon element, with embodiment 46, is replaced to 0.95 gram of acetylene black and 0.05 gram of multi-walled carbon nano-tubes by 1 gram of multi-walled carbon nano-tubes by preparation method.Method of testing is with above-described embodiment 14.
Embodiment 63
Material with carbon element, with embodiment 46, is replaced to 0.95 gram of acetylene black and 0.05 gram of multi-walled carbon nano-tubes by 1 gram of multi-walled carbon nano-tubes, spraying dry design temperature 150 DEG C by preparation method.Method of testing is with above-described embodiment 14.
Embodiment 64
Material with carbon element, with embodiment 46, is replaced to 0.95 gram of Graphene and 0.05 gram of multi-walled carbon nano-tubes by 1 gram of multi-walled carbon nano-tubes by preparation method.Method of testing is with above-described embodiment 14.
Embodiment 65
Material with carbon element, with embodiment 46, is replaced to 0.95 gram of Graphene and 0.05 gram of multi-walled carbon nano-tubes by 1 gram of multi-walled carbon nano-tubes, spraying dry design temperature 150 DEG C by preparation method.Method of testing is with above-described embodiment 14.
Embodiment 66
Material with carbon element, with embodiment 46, is replaced to 0.95 gram of graphene oxide and 0.05 gram of multi-walled carbon nano-tubes by 1 gram of multi-walled carbon nano-tubes by preparation method.Method of testing is with above-described embodiment 14.
Embodiment 67
Material with carbon element, with embodiment 46, is replaced to 0.95 gram of graphene oxide and 0.05 gram of multi-walled carbon nano-tubes by 1 gram of multi-walled carbon nano-tubes, spraying dry design temperature 150 DEG C by preparation method.Method of testing is with above-described embodiment 14.
Embodiment 68
The sublimed sulfur getting 4.5 grams adds 50 milliliters of ethanol, high-energy ball milling wet-milling, obtains homogeneous flaxen suspension-turbid liquid.Get the multi-walled carbon nano-tubes of 1 gram, add ethanol to 100 milliliter, ultrasonic 1 hour, obtain the slurry of black favorable dispersibility.By above-mentioned two kinds of mixture sulphur-ethanol and multi-walled carbon nano-tubes-ethanol mixing, the lower 2000 revs/min of high-speed stirred of normal temperature 5 hours.In whipping process, add ethanol to cumulative volume 150 milliliters.After stirring terminates, the mixed slurry modest viscosity obtained.Carry out spraying dry to described mixed slurry, design temperature 120 DEG C, obtains lithium sulfur battery anode material.Method of testing is with above-described embodiment 14.
Embodiment 69
Preparation method with embodiment 68, spraying dry design temperature 150 DEG C.Method of testing is with above-described embodiment 14.
Embodiment 70
Material with carbon element, with embodiment 68, is replaced to Ke Qinhei by multi-walled carbon nano-tubes by preparation method.Method of testing is with above-described embodiment 14.
Embodiment 71
Material with carbon element, with embodiment 68, is replaced to Ke Qinhei by multi-walled carbon nano-tubes by preparation method, spraying dry design temperature 150 DEG C.Method of testing is with above-described embodiment 14.
Embodiment 72
Material with carbon element, with embodiment 68, is replaced to active carbon by multi-walled carbon nano-tubes by preparation method.Method of testing is with above-described embodiment 14.
Embodiment 73
Material with carbon element, with embodiment 68, is replaced to active carbon by multi-walled carbon nano-tubes by preparation method, spraying dry design temperature 150 DEG C.Method of testing is with above-described embodiment 14.
Embodiment 74
Material with carbon element, with embodiment 68, is replaced to acetylene black by multi-walled carbon nano-tubes by preparation method.Method of testing is with above-described embodiment 14.
Embodiment 75
Material with carbon element, with embodiment 68, is replaced to acetylene black by multi-walled carbon nano-tubes by preparation method, spraying dry design temperature 150 DEG C.Method of testing is with above-described embodiment 14.
Embodiment 76
Material with carbon element, with embodiment 68, is replaced to Graphene by multi-walled carbon nano-tubes by preparation method.Method of testing is with above-described embodiment 14.
Embodiment 77
Material with carbon element, with embodiment 68, is replaced to Graphene by multi-walled carbon nano-tubes by preparation method, spraying dry design temperature 150 DEG C.Method of testing is with above-described embodiment 14.
Embodiment 78
Material with carbon element, with embodiment 68, is replaced to graphene oxide by multi-walled carbon nano-tubes by preparation method.Method of testing is with above-described embodiment 14.
Embodiment 79
Material with carbon element, with embodiment 68, is replaced to graphene oxide by multi-walled carbon nano-tubes by preparation method, spraying dry design temperature 150 DEG C.Method of testing is with above-described embodiment 14.
Embodiment 80
Material with carbon element, with embodiment 68, is replaced to 0.95 Ke Keqinhei and 0.05 gram multi-walled carbon nano-tubes by 1 gram of multi-walled carbon nano-tubes by preparation method.Method of testing is with above-described embodiment 14.
In the present embodiment, lithium sulfur battery anode material is sulphur (ball milling)/multi-walled carbon nano-tubes/Ke Qinhei compound.
Figure 15 is the thermogravimetric analysis figure of sulphur (ball milling)/multi-walled carbon nano-tubes/Ke Qinhei compound prepared by the present embodiment.
Above-mentioned lithium sulfur battery anode material is directly used as cell positive material, using lithium metal as negative material, assemble the battery that obtains with the multiplying power of 0.1/ hour in electric discharge by voltage for 1.5V, charge and to test under voltage is the condition of 2.8V, test result is shown in Figure 16.The charging and discharging curve of first week, the tenth week and the 100 week is shown in Figure 16, can have found out, first all specific discharge capacity 1123mAh/g.The cyclic curve schematic diagram of this battery has been shown in Figure 17.
Embodiment 81
Material with carbon element, with embodiment 68, is replaced to 0.95 Ke Keqinhei and 0.05 gram multi-walled carbon nano-tubes by 1 gram of multi-walled carbon nano-tubes by preparation method, spraying dry design temperature 150 DEG C.Method of testing is with above-described embodiment 80.
Embodiment 82
Material with carbon element, with embodiment 68, is replaced to 0.95 gram of active carbon and 0.05 gram of multi-walled carbon nano-tubes by 1 gram of multi-walled carbon nano-tubes by preparation method.Method of testing is with above-described embodiment 80.
Embodiment 83
Material with carbon element, with embodiment 68, is replaced to 0.95 gram of active carbon and 0.05 gram of multi-walled carbon nano-tubes by 1 gram of multi-walled carbon nano-tubes, spraying dry design temperature 150 DEG C by preparation method.Method of testing is with above-described embodiment 80.
Embodiment 84
Material with carbon element, with embodiment 68, is replaced to 0.95 gram of acetylene black and 0.05 gram of multi-walled carbon nano-tubes by 1 gram of multi-walled carbon nano-tubes by preparation method.Method of testing is with above-described embodiment 80.
Embodiment 85
Material with carbon element 1 gram of multi-walled carbon nano-tubes, with embodiment 68, is replaced to 0.95 gram of acetylene black and 0.05 gram of multi-walled carbon nano-tubes, spraying dry design temperature 150 DEG C by preparation method.Method of testing is with above-described embodiment 80.
Embodiment 86
Material with carbon element, with embodiment 68, is replaced to 0.95 gram of Graphene and 0.05 gram of multi-walled carbon nano-tubes by 1 gram of multi-walled carbon nano-tubes by preparation method.Method of testing is with above-described embodiment 80.
Embodiment 87
Material with carbon element, with embodiment 68, is replaced to 0.95 gram of Graphene and 0.05 gram of multi-walled carbon nano-tubes by 1 gram of multi-walled carbon nano-tubes, spraying dry design temperature 150 DEG C by preparation method.Method of testing is with above-described embodiment 80.
Embodiment 88
Material with carbon element, with embodiment 68, is replaced to 0.95 gram of graphene oxide and 0.05 gram of multi-walled carbon nano-tubes by 1 gram of multi-walled carbon nano-tubes by preparation method.Method of testing is with above-described embodiment 80.
Embodiment 89
Material with carbon element, with embodiment 68, is replaced to 0.95 gram of graphene oxide and 0.05 gram of multi-walled carbon nano-tubes by 1 gram of multi-walled carbon nano-tubes, spraying dry design temperature 150 DEG C by preparation method.Method of testing is with above-described embodiment 80.
In above-described embodiment 2 to embodiment 89, the mass percent (carrying sulfur content) of sulfur materials used enters shown in following table 1 respectively.The test result of head week specific discharge capacity and the 100th week specific discharge capacity that the lithium sulfur battery anode material prepared each embodiment is used as battery prepared by cell positive material is as following table 1.
Table 1
Above-described embodiment; object of the present invention, technical scheme and beneficial effect are further described; be understood that; the foregoing is only the specific embodiment of the present invention; the protection range be not intended to limit the present invention; within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a preparation method for lithium sulfur battery anode material, is characterized in that, described method comprises:
The electric conducting material of the sulfur materials of 50wt%-97wt% and 3wt%-50wt% is dissolved or dispersed in identical or different solvent respectively, and mixes;
1-24 hour is stirred with the speed of 1000rpd/min-6000rpd/min;
Under 60 DEG C of-250 DEG C of conditions, carry out spraying dry, obtain described lithium sulfur battery anode material;
Wherein, described lithium sulfur battery anode material is the micron order bead with nano-micro structure.
2. preparation method according to claim 1, is characterized in that, described under 60 DEG C of-250 DEG C of conditions, carry out spraying dry after, and described obtain described lithium sulfur battery anode material before, described method also comprises:
To the heat treatment 3 minutes-72 hours under 50 DEG C of-800 DEG C of conditions of the material after spraying dry.
3. preparation method according to claim 2, is characterized in that, described heat treated temperature is 155 DEG C-300 DEG C, and the time is 30 minutes-24 hours.
4. preparation method according to claim 1, is characterized in that, described sulfur materials comprises: sublimed sulfur, sedimentation sulphur, crystallization sulphur, colloid sulphur, without any one or more in crystalline state sulphur, crystallite sulphur, nano-sulfur or molten sulfur.
5. preparation method according to claim 1, is characterized in that, described electric conducting material comprises: any one or more in metal, metal oxide, material with carbon element, silicon materials, sulfide, organic conductive molecule or conducting polymer;
Wherein, described material with carbon element is the granular material with carbon element of dispersion, comprising: any one or more in carbon black, carbon aerogels, graphite, acetylene black, Ke Qinhei, activated carbon, Graphene, graphene oxide, nano-C particles, carbon nano-fiber, conductive carbon black, carbonaceous mesophase spherules, carbon ball, carbon nano-tube, ordered mesopore carbon or hierarchical porous structure carbon.
6. preparation method according to claim 5, is characterized in that, before being dissolved or dispersed in identical or different solvent respectively by the described electric conducting material by the sulfur materials of 50wt%-97wt% and 3wt%-50wt%, described method also comprises:
Described material with carbon element is carried out to the preliminary treatment of surface functionalization;
Wherein, described preliminary treatment is specially:
Described material with carbon element is dispersed in oxidizing liquid, by leaving standstill, heating, concussion and/or ultrasonic, magnetic agitation and/or high-speed stirred, after backflow, then through washing, suction filtration, centrifugal, evaporate, obtain the material with carbon element of described surface functionalization; Wherein, described oxidizing liquid comprises: one or more in the concentrated sulfuric acid, red fuming nitric acid (RFNA), hydrogen peroxide, liquor potassic permanganate, potassium chlorate solution or bromine water; Or
Described material with carbon element is placed in oxidizing gas heat-treat, obtains the material with carbon element of described surface functionalization; Wherein, described oxidizing gas comprises air, oxygen or carbon dioxide.
7. preparation method according to claim 1, is characterized in that, described solvent and described sulfur materials and all chemical reaction does not occur with described electric conducting material, and the boiling point of described solvent is lower than 350 DEG C;
Described solvent specifically comprises: water, ethanol, acetone, carbon disulfide, isopentane, pentane, benzinum, hexane, cyclohexane, isooctane, trimethylpentane, pentamethylene, heptane, trichloroethylene/acetylene trichloride, carbon tetrachloride, propyl ether/propyl ether, toluene, paraxylene, chlorobenzene, o-dichlorohenzene, diethyl ether/ether, benzene, isobutanol, ethylene dichloride, n-butanol, butyl acetate/butyl acetate, propyl alcohol, methylisobutylketone, oxolane, ethyl acetate, isopropyl alcohol, chloroform, methyl ethyl ketone, pyridine, acetic acid, acetonitrile, aniline, dimethyl formamide, methyl alcohol, ethylene glycol, methyl-sulfoxide, n-methlpyrrolidone dimethylamine, 1,1-dichloroethanes, butanone, glycol dimethyl ether, triethylamine, propionitrile, 4-methyl-2 pentanone, ethylenediamine, glycol monomethyl ether, ethylene glycol monoethyl ether, dimethylbenzene, meta-xylene, ortho-xylene, cyclohexanone, cyclohexanol, nitrogen, nitrogen-dimethylacetylamide, phenol, 1,2-PD, orthoresol, nitrogen, nitrogen-dimethylaniline, metacresol, cresols, formamide, nitrobenzene, acetamide, HPT, quinoline, ethylene carbonate diethylene glycol (DEG), any one or more in succinonitrile or glycerine.
8. method according to claim 1, is characterized in that, the percentage of the quality summation of described sulfur materials and described electric conducting material and the volume of described solvent is 0.01-200% (grams per milliliter).
9. a lithium sulfur battery anode material prepared by the preparation method as described in claim as arbitrary in the claims 1-8, is characterized in that, the pattern of described lithium sulfur battery anode material is the micron order bead with nano-micro structure; The diameter of described micron order bead is 1 micron-20 microns;
Wherein, described micron order bead is made up of nano-structured particles, and the particle diameter of described nano-structured particles is 1nm-80nm.
10. one kind comprises the battery of the lithium sulfur battery anode material described in the claims 9.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105609733A (en) * | 2016-02-19 | 2016-05-25 | 钟玲珑 | Preparation method for boron-nitrogen-co-doped three-dimensional structured positive electrode material of lithium-sulfur battery |
| CN106169573A (en) * | 2016-10-06 | 2016-11-30 | 电子科技大学 | A kind of preparation method of the composite of graphene coated sulfur family simple substance |
| CN106784819A (en) * | 2016-12-30 | 2017-05-31 | 清华大学深圳研究生院 | A kind of lithium sulfur battery anode material and preparation method thereof |
| WO2017139982A1 (en) * | 2016-02-19 | 2017-08-24 | 肖丽芳 | Preparation method for boron-nitrogen codoped three-dimensionally structured lithium-sulfur battery positive electrode material |
| CN109378466A (en) * | 2018-12-08 | 2019-02-22 | 河南师范大学 | A kind of preparation method and product of spherical shape lithium sulfur battery anode material |
| CN110073458A (en) * | 2016-12-12 | 2019-07-30 | 韩国地质资源研究院 | The preparation method of accordion graphene complex, the complex thus prepared and the supercapacitor comprising complex |
| WO2020060132A1 (en) * | 2018-09-19 | 2020-03-26 | 주식회사 엘지화학 | Sulfur-carbon composite manufacturing method, sulfur-carbon composite manufactured thereby, cathode comprising same sulfur-carbon composite, and lithium secondary battery comprising same cathode |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101944596A (en) * | 2010-07-30 | 2011-01-12 | 中国科学院化学研究所 | Preparation method of silicon and carbon composite microspheres and application thereof |
| CN102082260A (en) * | 2011-01-07 | 2011-06-01 | 中国地质大学（武汉） | Preparation method of positive composite material of lithium battery |
| CN102903887A (en) * | 2011-07-28 | 2013-01-30 | 中国科学院大连化学物理研究所 | Sulfur electrode, and preparation and application thereof |
| WO2013049663A1 (en) * | 2011-09-30 | 2013-04-04 | The Regents Of The University Of California | Graphene oxide as a sulfur immobilizer in high performance lithium/sulfur cells |
| CN103560235A (en) * | 2013-11-15 | 2014-02-05 | 哈尔滨工业大学 | Graphene-coated sulfur/porous carbon composite positive electrode material and preparation method thereof |
-
2014
- 2014-07-25 CN CN201410359876.5A patent/CN105304882A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101944596A (en) * | 2010-07-30 | 2011-01-12 | 中国科学院化学研究所 | Preparation method of silicon and carbon composite microspheres and application thereof |
| CN102082260A (en) * | 2011-01-07 | 2011-06-01 | 中国地质大学（武汉） | Preparation method of positive composite material of lithium battery |
| CN102903887A (en) * | 2011-07-28 | 2013-01-30 | 中国科学院大连化学物理研究所 | Sulfur electrode, and preparation and application thereof |
| WO2013049663A1 (en) * | 2011-09-30 | 2013-04-04 | The Regents Of The University Of California | Graphene oxide as a sulfur immobilizer in high performance lithium/sulfur cells |
| CN103560235A (en) * | 2013-11-15 | 2014-02-05 | 哈尔滨工业大学 | Graphene-coated sulfur/porous carbon composite positive electrode material and preparation method thereof |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105609733A (en) * | 2016-02-19 | 2016-05-25 | 钟玲珑 | Preparation method for boron-nitrogen-co-doped three-dimensional structured positive electrode material of lithium-sulfur battery |
| WO2017139982A1 (en) * | 2016-02-19 | 2017-08-24 | 肖丽芳 | Preparation method for boron-nitrogen codoped three-dimensionally structured lithium-sulfur battery positive electrode material |
| CN106169573A (en) * | 2016-10-06 | 2016-11-30 | 电子科技大学 | A kind of preparation method of the composite of graphene coated sulfur family simple substance |
| CN110073458A (en) * | 2016-12-12 | 2019-07-30 | 韩国地质资源研究院 | The preparation method of accordion graphene complex, the complex thus prepared and the supercapacitor comprising complex |
| CN106784819A (en) * | 2016-12-30 | 2017-05-31 | 清华大学深圳研究生院 | A kind of lithium sulfur battery anode material and preparation method thereof |
| CN106784819B (en) * | 2016-12-30 | 2019-03-26 | 清华大学深圳研究生院 | A kind of lithium sulfur battery anode material and preparation method thereof |
| WO2020060132A1 (en) * | 2018-09-19 | 2020-03-26 | 주식회사 엘지화학 | Sulfur-carbon composite manufacturing method, sulfur-carbon composite manufactured thereby, cathode comprising same sulfur-carbon composite, and lithium secondary battery comprising same cathode |
| US11362325B2 (en) | 2018-09-19 | 2022-06-14 | Lg Energy Solution, Ltd. | Sulfur-carbon composite manufacturing method, sulfur-carbon composite manufactured thereby, cathode comprising same sulfur-carbon composite, and lithium secondary battery comprising same cathode |
| US11757091B2 (en) | 2018-09-19 | 2023-09-12 | Lg Energy Solution, Ltd. | Sulfur-carbon composite manufacturing method, sulfur-carbon composite manufactured thereby, cathode comprising same sulfur-carbon composite, and lithium secondary battery comprising same cathode |
| CN109378466A (en) * | 2018-12-08 | 2019-02-22 | 河南师范大学 | A kind of preparation method and product of spherical shape lithium sulfur battery anode material |
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