CN103985864B - A kind of manufacture method of lithium sulfur battery anode material - Google Patents
A kind of manufacture method of lithium sulfur battery anode material Download PDFInfo
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- CN103985864B CN103985864B CN201410206666.2A CN201410206666A CN103985864B CN 103985864 B CN103985864 B CN 103985864B CN 201410206666 A CN201410206666 A CN 201410206666A CN 103985864 B CN103985864 B CN 103985864B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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- H—ELECTRICITY
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- H01M10/00—Secondary cells; Manufacture thereof
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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Abstract
The invention discloses the manufacture method of a kind of lithium sulfur battery anode material, by polyacrylonitrile resin micropowder and kieselguhr with mass ratio 38～41:62～59, process premenstruum and be placed in the high temperature furnace of nitrogen displacement, under conditions of suitable extracting vacuum, thin slice viscose glue mud is made to become the kieselguhr thin slice comprising only carborundum composition.Then many lithium sulfides are dissolved in the NMP nmp solution containing many lithium sulfides 28～33wt% and impregnate 33～38min, after taking-up, again the kieselguhr thin slice containing many lithium sulfides and nmp solvent is placed in another high temperature furnace of nitrogen displacement, steam through dipping repeatedly and high temperature and obtain the lithium sulfur battery anode material containing many lithium sulfides 18～21wt%, preparation method of the present invention is simple, low cost, the lithium sulfur battery anode material of preparation has high the receiving ability of sulfur, relatively macroion transmittability and electric conductivity, can improve the high rate capability of lithium-sulfur cell and high cycle performance.
Description
Art
The present invention relates to a kind of lithium sulfur battery anode material and preparation method thereof, belong to new energy field.
Background technology
Along with the development of human society, becoming increasingly conspicuous of the problem such as energy shortage, environmental pollution, people are to change
Learning the understanding of power supply and require more and more higher, promoting people constantly to explore new electrochmical power source is main energy
Stocking system.In recent decades, the battery based on lithium metal has led the development of high performance chemical electric power source
Direction.Along with the successful commercialization of lithium ion battery, automobile-used lithium ion power is all carried out stepping up in countries in the world
The research of battery.But due to the factors such as energy density, safety, price, the acid of traditional lithium-ion battery such as cobalt
Lithium, LiMn2O4 and ferric phosphate lithium cell cannot meet the requirement of electric automobile as power source.
Lithium-sulfur cell is the high-energy density secondary battery of great development potentiality and application prospect.It has height
Beyond specific capacity and high-energy-density, sulfur as positive active material in source, cost and environmental friendliness
Aspect shows incomparable advantage, and at present, lithium-sulfur cell exists that cycle performance is poor, high rate performance needs
The problems such as further raising.And two that lithium-sulfur cell exists main problem is that on the one hand active substance sulfur
Material itself and final discharging product Li2S is the insulator of electronics and ion；On the other hand, in discharge process
Intermediate product polysulfide be easily soluble in electrolyte, these can cause active substance irreversible loss and
Capacity attenuation.To this end, how to suppress the diffusion of polysulfide, the electric conductivity improved in sulfur positive pole cyclic process
It it is the research emphasis of sulfur-based positive electrode material.
Academia mainly around suppression polysulfide diffusion and improved two aspects of positive electrode electric conductivity in recent years
Conduct a research.On material structure, first consider it is to be adsorbed on porous material skeleton, such as by elemental sulfur
The porous charcoal such as material with carbon element such as activated carbon, CNT, Graphene is combined with sulfur, prevents course of reaction from producing
Polysulfide be dissolved in electrolyte, spread by electrolyte, so contribute to minimizing shuttle back and forth effect and
Self-discharge phenomenon.These new material structure more or less improve the cyclical stability of electrode.But it is traditional
The general specific surface area of porous carbon material is less, and aperture size is single, and structural integrity is poor, aperture is difficult to regulate and control,
The adsorption activity material sulfur of material is limited in one's ability, cause the sulfur content in the composite positive pole of preparation relatively low,
Skewness, electric conductivity is poor, is assembled into circulating battery after a few, still has a large amount of active substance can be from
Dissolving in carbon structure duct, cause the loss of active substance, lithium-sulfur cell energy density is difficult to improve further.
This area is used in the urgent need to a kind of lithium-sulfur cell having good electric conductivity and hierarchical pore structure concurrently of exploitation
Positive electrode, the electric conductivity in the diffusion of suppression polysulfide, raising sulfur positive pole cyclic process, and then improve
The ion transport capability of positive electrode and electric conductivity, can effectively reduce discharge and recharge polarization, reduce the internal resistance of cell,
Improve the big the most forthright of lithium-sulfur cell.
A kind of employing at sulfur-containing compound lithium-sulfur cell is described in Chinese patent number No:02125137.1
The surface-coated layer of surface passivating material of positive electrode, its objective is to reduce sulfur-containing compound in discharge and recharge
The loss of sulfur in journey, but due to coated surface passivation layer be some Mg, Na, Ca, Si, Ti, V,
The carbonate of the chemical elements such as Sn, Ge, Ga, B, As, Zr or hydroxyl carbonate, can cause this electrode material
Electric conductivity reduce.
In Chinese patent number No:1143369.8, introduce one use sulfur-containing compound and conductive agent and glue
Several raw material such as mixture prepares the positive electrode of lithium-sulfur cell, owing to conductive agent is the molding of metal material
Material, the simultaneously impact of binding agent so that it is the electric conductivity of lithium sulfur battery anode material can be affected accordingly.
The manufacture of a kind of inorganic electrolyte is described in Chinese Patent Application No. code No:201310418375.5
Technique, wherein applies kieselguhr and is used as the backing material of a kind of electrolyte, wherein use polysiloxanes to have
Machine silicones, and kieselguhr come together preparation can with the material of adsorbing electrolyte material, but, due to system
Can be affected by polyorganosiloxane resin strand during standby carborundum, its voidage can be caused to decline.
In view of the disadvantage mentioned above of prior art, it is an object of the invention to overcome current lithium sulfur battery anode material
Deficiency, on the one hand uses many lithium sulfides that charge-discharge performance is excellent, on the other hand uses the kieselguhr containing carbon,
Make many lithium sulfides solution be adsorbed in easily wherein, in order to improve lithium salts dispersibility in kieselguhr, enter
And improve capacitance and the charge-discharge velocity of solid electrolyte, use this polymer of polyacrylonitrile resin simultaneously
Prepare conductive carrier, reduce lithium ion and anion obstruction of movement under the effect of voltage after lithium salts dissociation,
Thus improve the conductivity of this lithium sulfur battery anode material.
Summary of the invention
The present invention is directed to porous charcoal of the prior art and sulfur is combined the positive electrode obtained because there is adsorption activity
Material sulfur is limited in one's ability, electric conductivity is poor problem and make its application in the battery be limited to, it is therefore an objective to
It is to provide the lithium-sulphur cell positive electrode material of a kind of high energy high rate performance that can improve lithium-sulfur cell and high cycle performance
Material.
It is an object of the invention to realize by the following means.
A kind of manufacture method of lithium sulfur battery anode material, it is characterised in that by polyacrylonitrile resin micropowder and
Kieselguhr with mass ratio 38～41:62～59, adds in mixed at high speed agitator, add 28～33wt%/
Diatomaceous nmp solvent, under conditions of being sufficiently stirred for, being uniformly mixed into viscosity is 13800～19600Pa.s
Viscose glue mud, then viscose glue mud is needed to be fabricated to the thin slice of respective shapes according to lithium sulfur battery anode material
Material, is placed in sheeting in the high temperature furnace of nitrogen displacement, under conditions of suitable extracting vacuum,
Thin slice viscose glue mud is made to become the kieselguhr thin slice comprising only carborundum composition；Then it is placed on containing many lithium sulfides
In the nmp solution of 28～33wt%, impregnate 33～38min, after taking-up, will be molten containing many lithium sulfides and NMP
The kieselguhr thin slice of agent is placed in the high temperature furnace of nitrogen displacement, under conditions of suitable extracting vacuum, makes
Nmp solvent in kieselguhr thin slice fully evaporates, and dipping and the high temperature evaporation of 3～6 times goes out the most repeatedly
NMP, makes the lithium sulfur battery anode material containing many lithium sulfides 18～21wt% in kieselguhr thin slice.
Its concrete steps include:
1, in the 316L stainless steel cauldron of 1L, the guarantor being constantly passed through 360～480ml/min nitrogen
Protect down, addition 5.4～8.8mol electron level NMP, 1.0mol NaHS and 1.003mol sodium hydroxide,
Under 160～190rpm stirring conditions, slowly the temperature of reaction system is increased to 86～88 DEG C, adds simultaneously
Enter 0.4mol deionization anaerobic water, be subsequently adding 1.001mol lithium chloride, continue to raise the temperature of reaction system
Degree is to 170～190 DEG C, and under this temperature conditions, makes reaction system insulation 18～33min, until reactant
When system having tiny white crystal separate out, the water evaporates in reaction system is removed simultaneously, and stop adding
Heat；
2, by 1) the anhydrous response system that obtains is under the protection of nitrogen, and filtered while hot, by reaction system
White crystal filters out, and filtrate rejoins reaction system, add the Sublimed Sulfur in formula and deionization without
Oxygen water, treats that temperature rises to 88～118 DEG C, and backflow insulation 4～6h under this temperature conditions, until reaction
Time in system without Sublimed Sulfur powder, stop reaction system being heated, slowly by the temperature of reaction system simultaneously
Drop to room temperature, now, reaction system separates out the most light yellow or white pressed powder；Wherein reactor
Stirring intensity be 280～330rpm；
3, by 2) the light yellow or white solid powder that separates out filters out, containing many sulfur from reaction system
The filtrate that purity is 99.991wt% changing lithium is stand-by；
4, by formula polyacrylonitrile resin micropowder powder and kieselguhr, add 28～33wt%/silicon
The electron level nmp solvent of diatomaceous earth, under conditions of being sufficiently stirred for, be uniformly mixed into viscosity be 13800～
The viscose glue mud of 19600Pa.s, after homogenizer is sufficiently mixed uniformly, is pressed into 180～810 μ m-thick
Thin slice, and pre-buried 80～330 μm copper sheet in thin slice；
5) by 4) the molding kieselguhr viscose glue mud that obtains inserts in the high temperature furnace of 280～380 DEG C, in negative pressure be
Under conditions of 0.088～0.091MPa, process 16～38min, make kieselguhr shape, the most carefully extract copper out
Sheet；
6), by 5) gained thin slice inserts in the high temperature furnace of 1280～1380 DEG C, negative pressure be 0.098～
Under conditions of 0.0999MPa, process 81～88min, be cooled to room temperature in the normal temperature air room of anhydrous steam；
With the hydrogen on abjection polyacrylonitrile resin strand, oxygen atom；Prepared porosity is 81～88%, aperture be 3～
5um structure contains the kieselguhr thin slice of carborundum；
7), by 6) thin slice that obtains inserts 3) in nmp solution containing many lithium sulfides 28～33wt%, pass through
After dipping 33～38min taking-up, the kieselguhr thin slice containing many lithium sulfides and nmp solvent is placed in through nitrogen
Gas is replaced in the high temperature furnace that another temperature is 280～300 DEG C of 3～6 times, in suitably extraction negative pressure is
Under conditions of the vacuum of 0.068～0.088MPa, after the process time is 36～48min, normal through anhydrous steam
Warm air room is cooled to room temperature, thus obtains the kieselguhr thin slice of the many lithium sulfides of first impregnation；
8) by 7) thin slice that obtains inserts in the nmp solution containing many lithium sulfides again, impregnates 18～33min,
Insert again in nitrogen replaces the high temperature furnace that another temperature is 260～281 DEG C of 3～6 times, in suitably extraction
Under conditions of negative pressure is the vacuum of 0.088～0.091MPa, after the process time is 33～36min, through anhydrous
The normal temperature air room of steam is cooled to room temperature, thus obtains second time and impregnates the kieselguhr thin slice of many lithium sulfides；
9) by 8) thin slice that obtains uses 8) process conditions in step, through the dipping of repeatedly 2～4 times
Go out NMP with high temperature evaporation, make the lithium-sulphur cell positive electrode containing many lithium sulfides 18～21wt% in kieselguhr thin slice
Material；
The technical characterstic of the present invention:
1, the present invention is first with being dissolved in the lithium chloride of nmp solvent, its normal-temperature dissolution in nmp solvent
Degree can be up to 26g/100mlNMP, in order to improve the dissolubility of lithium chloride, needs to carry out solution system necessarily
The heat temperature raising of degree, further, since NMP is in a heated condition, can be because being allowed to oxygen with air contact
Change reaction and yellowing, and then reduce the purity of NMP, accordingly, it would be desirable to noble gas (such as: nitrogen)
To synthesis dicyandiamide solution protect, in order to avoid causing the generation of other side reactions, thus reduce lithium sulfide and/or
The purity of many lithium sulfides.
Secondly 2, the present invention utilizes the most common NaHS industrial raw materials, although this raw material at room temperature and
Nmp solvent it is also insoluble under conditions of heat temperature raising, but, under conditions of with the presence of anaerobic water, pass through
Add sodium hydroxide to react, generate the sodium sulfide little containing impurity level, heated by intensification the most again
Afterwards, there is ionic reaction wherein by sodium sulfide and lithium chloride, meanwhile, evaporating anaerobic therein
Under conditions of water, synthesize lithium sulfide, due to sodium chloride dissolubility in the nmp solvent of 150～160 DEG C only
Having 5mg/100mlNMP, the dissolubility at room temperature is also low-down, and lithium sulfide is dissolved in nmp solvent,
To this end, the present invention makes full use of lithium sulfide this characteristic of easy NMP, it is relatively easy to obtain lithium sulfide, its
Purpose is to be easily oxidized decomposition in atmosphere due to lithium sulfide, discharges hydrogen sulfide poison, uses this
The purpose of bright technological process is on the one hand to avoid the lithium sulfide synthesized not oxidized, and still further aspect is
In order to obtain highly purified anhydrous lithium sulfide.
3, the present invention in order to avoid lithium sulfide in the deionized water of aerobic oxidized, therefore, make full use of permissible
The condition utilized, it is simply that can by deionized water by physics or/and by the way of chemistry, by deionized water
Dissolved oxygen drops to the lowest degree, even completely removes, and to guarantee that lithium sulfide is not oxidized, and then improves many
The purity of lithium sulfide.
4, the present invention is in order to synthesize the many lithium sulfides raw material needed for lithium-sulfur cell.Owing to elemental sulfur is soluble in ethanol
Among, all can be soluble among nmp solvent according to the principles of chemistry of similar compatibility, elemental sulfur and lithium sulfide,
But due to the difference of dissolubility, aggregate velocity can be made to be affected, in order to improve aggregate velocity, the present invention
Make full use of the light water solvent that can make lithium sulfide that electrolysis occurs, aggregate velocity thus can be made relatively to use ethanol
Or ammonia is that solvent improves nearly 2 times, meanwhile, reduce cost nearly 40%, be more beneficial for realizing industry metaplasia
Produce.
5, the present invention is in order to make full use of reflux solvent and aqueous systems, is to ensure that temperature steady of synthetic system
Fixed, improve raw-material utilization rate, and then the productivity of many lithium sulfides is provided.
6, the present invention uses diatomaceous purpose to be to make full use of diatomaceous open structure, also utilizes silicon simultaneously
Diatomaceous earth can make kieselguhr sinter variously-shaped material into sinter molding, is conducive to being fabricated to lithium sulfur
Electrode material needed for battery.
7, the present invention is in order to increase the electric conductivity of electrode material, makes full use of polyacrylonitrile resin micropowder and is dissolved in and having
The characteristic of machine solvent, makes polyacrylonitrile resin micropowder and kieselguhr be sufficiently mixed all by the dissolving of organic solvent
Even, be conducive to making polyacrylonitrile resin micropowder be transformed into carborundum conductive material after forming processes subsequently
Preferably blend with kieselguhr, and carborundum be preferably uniformly distributed with kieselguhr among, beneficially lithium
Sulphur cell positive electrode material conductivity is more stable；Additionally the present invention uses the polyacrylonitrile of complete straight chain, its mesh
Be to utilize the very appearance carbonization of this resin because polyacrylonitrile resin is the original material of carbon fiber, thus not
Affected by molecular chain structure and cause its porosity to decline.
8, the present invention uses the purpose of many lithium sulfides compound that can be dissolved in nmp solvent, be make to have a lot
The nmp solution of the carborundum diatomite material many lithium sulfides of more preferable adsorption and permeation of micropore, so that carborundum
Conductive material preferably organically combines with many lithium sulfides, this be conducive to many lithium sulfides in charge and discharge process from
Solve and dissociate, simultaneously as diatomaceous micropore is while improving lithium sulfur battery anode material electric conductivity,
Being also prevented from the excessive dissociation of many lithium sulfides, beneficially lithium-sulfur cell charge and discharge cycles, to prevent lithium-sulfur cell from filling
The decay with number of times of electric discharge, to extend the service life of lithium-sulfur cell.
The technological process brief introduction of the present invention
A kind of manufacture method of lithium sulfur battery anode material, it is characterised in that by polyacrylonitrile resin micropowder and
Kieselguhr adds in mixed at high speed agitator with certain mass ratio, adds a certain proportion of nmp solvent,
Under conditions of being sufficiently stirred for, it is uniformly mixed into the viscose glue mud of certain viscosity, then by viscose glue mud according to lithium sulfur
Cell positive material need to be fabricated to the sheeting of respective shapes, sheeting is placed in and puts through nitrogen
In the high temperature furnace changed, under conditions of suitable extracting vacuum, make thin slice viscose glue mud become and comprise only carborundum
Then many lithium sulfides are dissolved in nmp solvent by the kieselguhr thin slice of part, form the finite concentration Han many lithium sulfides
Electron level nmp solution, then the kieselguhr thin slice after high-temperature process is immersed containing many lithium sulfides
In nmp solution, impregnate certain time, after taking-up, by the kieselguhr thin slice containing many lithium sulfides and nmp solvent
It is placed in another high temperature furnace of nitrogen displacement, under conditions of suitable extracting vacuum, makes kieselguhr thin slice
In nmp solvent fully evaporate, the dipping and the high temperature evaporation that are so repeated several times go out NMP, make kieselguhr
Containing a certain amount of lithium sulfur battery anode material of many lithium sulfides in thin slice.
The detailed description of the invention of the present invention
Embodiment 1
In the 316L stainless steel cauldron of 1L, under the protection being constantly passed through 360ml/min nitrogen, add
Enter 5.4molNMP, 1.0mol NaHS and 1.003mol sodium hydroxide, stir bar 160～190rpm
Under part, slowly the temperature of reaction system is increased to 86 DEG C, is simultaneously introduced 0.4mol deionization anaerobic water, so
Rear addition 1.001mol lithium chloride, continues to raise the temperature to 170 DEG C of reaction system, and in this temperature conditions
Under, making reaction system be incubated 33min, during until reaction system there being tiny white crystal separate out, will simultaneously
Water evaporates in reaction system removes, and stops heating；Under the protection of nitrogen, filtered while hot, will reaction
White crystal in system filters out, and filtrate rejoins reaction system, and the stirring intensity of reactor is
330rpm；Add the Sublimed Sulfur in formula and deionization anaerobic water, treat that temperature rises to 88 DEG C, and in this temperature
Backflow insulation 6h under the conditions of degree, until time in reaction system without Sublimed Sulfur powder, stops heating reaction system,
The temperature of reaction system is dropped to slowly room temperature simultaneously, now, reaction system separates out the most light yellow or
The pressed powder of white；Light yellow or the white solid powder separated out is filtered out from reaction system, contains
The filtrate having many lithium sulfides is stand-by；
By in formula polyacrylonitrile resin micropowder powder and kieselguhr, add 28wt%/kieselguhr electronics
The nmp solvent of level, under conditions of being sufficiently stirred for, is uniformly mixed into the viscose glue mud that viscosity is 13800Pa.s,
After homogenizer is sufficiently mixed uniformly, it is pressed into the thin slice of 180 μ m-thick, and pre-buried in thin slice
80 μm copper sheets；Molding kieselguhr viscose glue mud is inserted in the high temperature furnace of 280 DEG C, be 0.088MPa in negative pressure
Under conditions of, process 38min, make kieselguhr shape, the most carefully extract copper sheet out；Thin by extract out after copper sheet
Sheet is inserted in the high temperature furnace of 1280 DEG C, under conditions of negative pressure is 0.0999MPa, processes 88min, in nothing
The normal temperature air room of steam is cooled to room temperature；With the hydrogen on abjection polyacrylonitrile resin strand, oxygen atom；
Prepared porosity is 81%, and aperture is the kieselguhr thin slice that 3um structure contains carborundum；Then thin slice is put
Enter in the nmp solution containing many lithium sulfides 28wt%, after dipping 38min takes out, will be containing many lithium sulfides
The high temperature furnace that another temperature is 300 DEG C replacing 3 times through nitrogen it is placed in the kieselguhr thin slice of nmp solvent
In, under conditions of suitably extraction negative pressure is the vacuum of 0.088MPa, after the process time is 48min, through nothing
The normal temperature air room of steam is cooled to room temperature, thus obtains the kieselguhr thin slice of the many lithium sulfides of first impregnation；
Then thin slice is inserted again in the nmp solution that purity is 99.991wt% containing many lithium sulfides, dipping
33min, then insert in nitrogen replaces the high temperature furnace that another temperature is 260 DEG C of 6 times, in suitably extraction
Under conditions of negative pressure is the vacuum of 0.091MPa, after the process time is 36min, empty through the room temperature of anhydrous steam
Air chamber is cooled to room temperature, thus obtains second time and impregnates the kieselguhr thin slice of many lithium sulfides；Pass through the most again
Dipping and the high temperature evaporation of 2 times goes out NMP repeatedly, makes the lithium containing many lithium sulfides 18wt% in kieselguhr thin slice
Sulphur cell positive electrode material.
Embodiment 2
In the 316L stainless steel cauldron of 1L, under the protection being constantly passed through 480ml/min nitrogen, add
Enter 8.8molNMP, 1.0mol NaHS and 1.003mol sodium hydroxide, under 190rpm stirring condition,
Slowly the temperature of reaction system is increased to 88 DEG C, is simultaneously introduced 0.4mol deionization anaerobic water, is subsequently adding
1.001mol lithium chloride, continues to raise the temperature to 190 DEG C of reaction system, and under this temperature conditions, makes
Reaction system insulation 18min, during until there being tiny white crystal to separate out in reaction system, simultaneously by reactant
Water evaporates in system removes, and stops heating；Under the protection of nitrogen, filtered while hot, by reaction system
White crystal filter out, filtrate rejoins reaction system, and the stirring intensity of reactor is 330rpm；
Add the Sublimed Sulfur in formula and deionization anaerobic water, treat that temperature rises to 118 DEG C, and under this temperature conditions
Backflow insulation 4h, until time in reaction system without Sublimed Sulfur powder, stops heating reaction system, will simultaneously
The temperature of reaction system drops to room temperature slowly, now, separates out the most light yellow or white in reaction system
Pressed powder；Light yellow or the white solid powder separated out is filtered out, containing many sulfur from reaction system
The filtrate changing lithium is stand-by；
By in formula polyacrylonitrile resin micropowder powder and kieselguhr, add 33wt%/kieselguhr electronics
The nmp solvent of level, under conditions of being sufficiently stirred for, is uniformly mixed into the viscose glue mud that viscosity is 19600Pa.s,
After homogenizer is sufficiently mixed uniformly, it is pressed into the thin slice of 810 μ m-thick, and pre-buried in thin slice
330 μm copper sheets；Molding kieselguhr viscose glue mud is inserted in the high temperature furnace of 380 DEG C, be 0.088MPa in negative pressure
Under conditions of, process 16min, make kieselguhr shape, the most carefully extract copper sheet out；Thin by extract out after copper sheet
Sheet is inserted in the high temperature furnace of 1380 DEG C, under conditions of negative pressure is 0.098MPa, processes 81min, anhydrous
The normal temperature air room of steam is cooled to room temperature；With the hydrogen on abjection polyacrylonitrile resin strand, oxygen atom；
Prepared porosity is 88%, and aperture is the kieselguhr thin slice that 5um structure contains carborundum；Then thin slice is put
Enter in the nmp solution containing many lithium sulfides 33wt%, after dipping 33min takes out, will be containing many lithium sulfides
The high temperature furnace that another temperature is 300 DEG C replacing 6 times through nitrogen it is placed in the kieselguhr thin slice of nmp solvent
In, under conditions of suitably extraction negative pressure is the vacuum of 0.068MPa, after the process time is 36min, through nothing
The normal temperature air room of steam is cooled to room temperature, thus obtains the kieselguhr thin slice of the many lithium sulfides of first impregnation；
Then thin slice is inserted again in the nmp solution that purity is 99.991wt% containing many lithium sulfides, dipping
18min, then insert in nitrogen replaces the high temperature furnace that another temperature is 281 DEG C of 6 times, in suitably extraction
Under conditions of negative pressure is the vacuum of 0.088MPa, after the process time is 33min, empty through the room temperature of anhydrous steam
Air chamber is cooled to room temperature, thus obtains second time and impregnates the kieselguhr thin slice of many lithium sulfides；Pass through the most again
Dipping and the high temperature evaporation of 4 times goes out NMP repeatedly, makes in kieselguhr thin slice containing many lithium sulfides 21wt%'s
Lithium sulfur battery anode material.
Embodiment 3
In the 316L stainless steel cauldron of 1L, under the protection being constantly passed through 373ml/min nitrogen, add
Enter 5.9molNMP, 1.0mol NaHS and 1.003mol sodium hydroxide, under 171rpm stirring condition,
Slowly the temperature of reaction system is increased to 87 DEG C, is simultaneously introduced 0.4mol deionization anaerobic water, is subsequently adding
1.001mol lithium chloride, continues to raise the temperature to 173 DEG C of reaction system, and under this temperature conditions, makes
Reaction system insulation 21min, during until there being tiny white crystal to separate out in reaction system, simultaneously by reactant
Water evaporates in system removes, and stops heating；Under the protection of nitrogen, filtered while hot, by reaction system
White crystal filter out, filtrate rejoins reaction system, and the stirring intensity of reactor is 291rpm；
Add the Sublimed Sulfur in formula and deionization anaerobic water, treat that temperature rises to 91 DEG C, and under this temperature conditions
Backflow insulation 5.8h, until time in reaction system without Sublimed Sulfur powder, stops heating reaction system, simultaneously
The temperature of reaction system is dropped to slowly room temperature, now, reaction system separates out the most light yellow or white
Pressed powder；Light yellow or the white solid powder separated out is filtered out from reaction system, containing many
The filtrate of lithium sulfide is stand-by；
By in formula polyacrylonitrile resin micropowder powder and kieselguhr, add 29wt%/kieselguhr electronics
The nmp solvent of level, under conditions of being sufficiently stirred for, is uniformly mixed into the viscose glue mud that viscosity is 14340Pa.s,
After homogenizer is sufficiently mixed uniformly, it is pressed into the thin slice of 210 μ m-thick, and pre-buried in thin slice
100 μm copper sheets；Molding kieselguhr viscose glue mud is inserted in the high temperature furnace of 293 DEG C, be 0.089MPa in negative pressure
Under conditions of, process 36min, make kieselguhr shape, the most carefully extract copper sheet out；Thin by extract out after copper sheet
Sheet is inserted in the high temperature furnace of 1313 DEG C, under conditions of negative pressure is 0.0990MPa, processes 87min, in nothing
The normal temperature air room of steam is cooled to room temperature；With the hydrogen on abjection polyacrylonitrile resin strand, oxygen atom；
Prepared porosity is 81.3%, and aperture is the kieselguhr thin slice that 3.8um structure contains carborundum；Then by thin slice
Insert in the nmp solution containing many lithium sulfides 29wt%, after dipping 37min takes out, will be containing many sulfurations
The kieselguhr thin slice of lithium and nmp solvent is placed in the high temperature that another temperature is 290 DEG C replacing 5 times through nitrogen
In stove, under conditions of suitably extraction negative pressure is the vacuum of 0.084MPa, after the process time is 47min, warp
The normal temperature air room of anhydrous steam is cooled to room temperature, and the kieselguhr thus obtaining the many lithium sulfides of first impregnation is thin
Sheet；Then thin slice is inserted again in the nmp solution that purity is 99.991wt% containing many lithium sulfides, dipping
31min, then insert in nitrogen replaces the high temperature furnace that another temperature is 264 DEG C of 4 times, in suitably extraction
Under conditions of negative pressure is the vacuum of 0.090MPa, after the process time is 35min, empty through the room temperature of anhydrous steam
Air chamber is cooled to room temperature, thus obtains second time and impregnates the kieselguhr thin slice of many lithium sulfides；Pass through the most again
Dipping and the high temperature evaporation of 3 times goes out NMP repeatedly, makes in kieselguhr thin slice containing many lithium sulfides 18.4wt%
Lithium sulfur battery anode material.
Embodiment 4
In the 316L stainless steel cauldron of 1L, under the protection being constantly passed through 384ml/min nitrogen, add
Enter 6.4molNMP, 1.0mol NaHS and 1.003mol sodium hydroxide, under 179rpm stirring condition,
Slowly the temperature of reaction system is increased to 88 DEG C, is simultaneously introduced 0.4mol deionization anaerobic water, is subsequently adding
1.001mol lithium chloride, continues to raise the temperature to 176 DEG C of reaction system, and under this temperature conditions, makes
Reaction system insulation 31min, during until there being tiny white crystal to separate out in reaction system, simultaneously by reactant
Water evaporates in system removes, and stops heating；Under the protection of nitrogen, filtered while hot, by reaction system
White crystal filter out, filtrate rejoins reaction system, and the stirring intensity of reactor is 321rpm；
Add the Sublimed Sulfur in formula and deionization anaerobic water, treat that temperature rises to 104 DEG C, and under this temperature conditions
Backflow insulation 5.1h, until time in reaction system without Sublimed Sulfur powder, stops heating reaction system, simultaneously
The temperature of reaction system is dropped to slowly room temperature, now, reaction system separates out the most light yellow or white
Pressed powder；Light yellow or the white solid powder separated out is filtered out from reaction system, containing many
The filtrate of lithium sulfide is stand-by；
By in formula polyacrylonitrile resin micropowder powder and kieselguhr, add 28～33wt%/kieselguhr
The nmp solvent of electron level, under conditions of being sufficiently stirred for, being uniformly mixed into viscosity is the viscous of 15430Pa.s
Clay, after homogenizer is sufficiently mixed uniformly, is pressed into the thin slice of 330 μ m-thick, and in thin slice
Pre-buried 130 μm copper sheets；Molding kieselguhr viscose glue mud is inserted in the high temperature furnace of 311 DEG C, in negative pressure be
Under conditions of 0.088MPa, process 23min, make kieselguhr shape, the most carefully extract copper sheet out；To extract out
Thin slice after copper sheet is inserted in the high temperature furnace of 1303 DEG C, under conditions of negative pressure is 0.098MPa, processes
86min, is cooled to room temperature in the normal temperature air room of anhydrous steam；With on abjection polyacrylonitrile resin strand
Hydrogen, oxygen atom；Prepared porosity is 82.3%, and aperture is the kieselguhr thin slice that 3.7um structure contains carborundum；
Then thin slice is inserted in the nmp solution containing many lithium sulfides 30wt%, after dipping 36min takes out, will
Kieselguhr thin slice containing many lithium sulfides and nmp solvent is placed in replaces another temperature of 5 times through nitrogen and is
In the high temperature furnace of 291 DEG C, under conditions of suitably extraction negative pressure is the vacuum of 0.077MPa, the process time is
After 44min, it is cooled to room temperature through the normal temperature air room of anhydrous steam, thus obtains the many lithium sulfides of first impregnation
Kieselguhr thin slice；Then thin slice is inserted again the NMP that purity is 99.991wt% containing many lithium sulfides molten
In liquid, impregnate 29min, then insert in nitrogen replaces the high temperature furnace that another temperature is 274 DEG C of 5 times,
Under conditions of suitably extraction negative pressure is the vacuum of 0.090MPa, after the process time is 35min, through anhydrous steaming
The normal temperature air room of gas is cooled to room temperature, thus obtains second time and impregnates the kieselguhr thin slice of many lithium sulfides；
Dipping and high temperature evaporation through repeatedly 4 times go out NMP the most again, make in kieselguhr thin slice containing many sulfurations
The lithium sulfur battery anode material of lithium 20.1wt%.
Embodiment 5
In the 316L stainless steel cauldron of 1L, under the protection being constantly passed through 403ml/min nitrogen, add
Enter 7.1molNMP, 1.0mol NaHS and 1.003mol sodium hydroxide, under 179rpm stirring condition,
Slowly the temperature of reaction system is increased to 88 DEG C, is simultaneously introduced 0.4mol deionization anaerobic water, is subsequently adding
1.001mol lithium chloride, continues to raise the temperature to 179 DEG C of reaction system, and under this temperature conditions, makes
Reaction system insulation 32min, during until there being tiny white crystal to separate out in reaction system, simultaneously by reactant
Water evaporates in system removes, and stops heating；Under the protection of nitrogen, filtered while hot, by reaction system
White crystal filter out, filtrate rejoins reaction system, and the stirring intensity of reactor is 316rpm；
Add the Sublimed Sulfur in formula and deionization anaerobic water, treat that temperature rises to 109 DEG C, and under this temperature conditions
Backflow insulation 5.4h, until time in reaction system without Sublimed Sulfur powder, stops heating reaction system, simultaneously
The temperature of reaction system is dropped to slowly room temperature, now, reaction system separates out the most light yellow or white
Pressed powder；Light yellow or the white solid powder separated out is filtered out from reaction system, containing many
The filtrate of lithium sulfide is stand-by；
By in formula polyacrylonitrile resin micropowder powder and kieselguhr, add 31wt%/kieselguhr electronics
The nmp solvent of level, under conditions of being sufficiently stirred for, is uniformly mixed into the viscose glue mud that viscosity is 16418Pa.s,
Be sufficiently mixed after uniformly through homogenizer, be pressed into the thin slice of 440 μ m-thick, and in thin slice pre-buried 80～
330 μm copper sheets；Molding kieselguhr viscose glue mud is inserted in the high temperature furnace of 348 DEG C, be 0.089MPa in negative pressure
Under conditions of, process 34min, make kieselguhr shape, the most carefully extract copper sheet out；Thin by extract out after copper sheet
Sheet is inserted in the high temperature furnace of 1367 DEG C, under conditions of negative pressure is 0.0993MPa, processes 86min, in nothing
The normal temperature air room of steam is cooled to room temperature；With the hydrogen on abjection polyacrylonitrile resin strand, oxygen atom；
Prepared porosity is 83.8%, and aperture is the kieselguhr thin slice that 4.8um structure contains carborundum；Then by thin slice
Insert in the nmp solution containing many lithium sulfides 30wt%, after dipping 37min takes out, will be containing many sulfurations
The kieselguhr thin slice of lithium and nmp solvent is placed in the high temperature that another temperature is 297 DEG C replacing 6 times through nitrogen
In stove, under conditions of suitably extraction negative pressure is the vacuum of 0.081MPa, after the process time is 41min, warp
The normal temperature air room of anhydrous steam is cooled to room temperature, and the kieselguhr thus obtaining the many lithium sulfides of first impregnation is thin
Sheet；Then thin slice is inserted again in the nmp solution that purity is 99.991wt% containing many lithium sulfides, dipping
30min, then insert in nitrogen replaces the high temperature furnace that another temperature is 277 DEG C of 6 times, in suitably extraction
Under conditions of negative pressure is the vacuum of 0.090MPa, after the process time is 34min, empty through the room temperature of anhydrous steam
Air chamber is cooled to room temperature, thus obtains second time and impregnates the kieselguhr thin slice of many lithium sulfides；Pass through the most again
Dipping and the high temperature evaporation of 3 times goes out NMP repeatedly, makes in kieselguhr thin slice containing many lithium sulfides 20.7wt%
Lithium sulfur battery anode material.
Embodiment 6
In the 316L stainless steel cauldron of 1L, under the protection being constantly passed through 416ml/min nitrogen, add
Enter 7.8molNMP, 1.0mol NaHS and 1.003mol sodium hydroxide, under 181rpm stirring condition,
Slowly the temperature of reaction system is increased to 86 DEG C, is simultaneously introduced 0.4mol deionization anaerobic water, is subsequently adding
1.001mol lithium chloride, continues to raise the temperature to 181 DEG C of reaction system, and under this temperature conditions, makes
Reaction system insulation 29min, during until there being tiny white crystal to separate out in reaction system, simultaneously by reactant
Water evaporates in system removes, and stops heating；Under the protection of nitrogen, filtered while hot, by reaction system
White crystal filter out, filtrate rejoins reaction system, and the stirring intensity of reactor is 321rpm；
Add the Sublimed Sulfur in formula and deionization anaerobic water, treat that temperature rises to 111 DEG C, and under this temperature conditions
Backflow insulation 4.8h, until time in reaction system without Sublimed Sulfur powder, stops heating reaction system, simultaneously
The temperature of reaction system is dropped to slowly room temperature, now, reaction system separates out the most light yellow or white
Pressed powder；Light yellow or the white solid powder separated out is filtered out from reaction system, containing many
The filtrate of lithium sulfide is stand-by；
By in formula polyacrylonitrile resin micropowder powder and kieselguhr, add 31wt%/kieselguhr electronics
The nmp solvent of level, under conditions of being sufficiently stirred for, is uniformly mixed into the viscose glue mud that viscosity is 16780Pa.s,
After homogenizer is sufficiently mixed uniformly, it is pressed into the thin slice of 540 μ m-thick, and pre-buried in thin slice
200 μm copper sheets；Molding kieselguhr viscose glue mud is inserted in the high temperature furnace of 341 DEG C, be 0.088MPa in negative pressure
Under conditions of, process 33min, make kieselguhr shape, the most carefully extract copper sheet out；Thin by extract out after copper sheet
Sheet is inserted in the high temperature furnace of 1345 DEG C, under conditions of negative pressure is 0.0999MPa, processes 86min, in nothing
The normal temperature air room of steam is cooled to room temperature；With the hydrogen on abjection polyacrylonitrile resin strand, oxygen atom；
Prepared porosity is 84.3%, and aperture is the kieselguhr thin slice that 4.1um structure contains carborundum；Then by thin slice
Insert in the nmp solution containing many lithium sulfides 31wt%, after dipping 34min takes out, will be containing many sulfurations
The kieselguhr thin slice of lithium and nmp solvent is placed in the high temperature that another temperature is 286 DEG C replacing 3 times through nitrogen
In stove, under conditions of suitably extraction negative pressure is the vacuum of 0.084MPa, after the process time is 41min, warp
The normal temperature air room of anhydrous steam is cooled to room temperature, and the kieselguhr thus obtaining the many lithium sulfides of first impregnation is thin
Sheet；Then thin slice is inserted again in the nmp solution that purity is 99.991wt% containing many lithium sulfides, dipping
26min, then insert in nitrogen replaces the high temperature furnace that another temperature is 274 DEG C of 4 times, in suitably extraction
Under conditions of negative pressure is the vacuum of 0.091MPa, after processing time 36min, through the normal temperature air of anhydrous steam
Room is cooled to room temperature, thus obtains second time and impregnates the kieselguhr thin slice of many lithium sulfides；The most again through anti-
Dipping and the high temperature evaporation of multiple 4 times go out NMP, make the lithium containing many lithium sulfides 20.6wt% in kieselguhr thin slice
Sulphur cell positive electrode material.
Embodiment 7
In the 316L stainless steel cauldron of 1L, under the protection being constantly passed through 431ml/min nitrogen, add
Enter 8.1molNMP, 1.0mol NaHS and 1.003mol sodium hydroxide, under 184rpm stirring condition,
Slowly the temperature of reaction system is increased to 87 DEG C, is simultaneously introduced 0.4mol deionization anaerobic water, is subsequently adding
1.001mol lithium chloride, continues to raise the temperature to 184 DEG C of reaction system, and under this temperature conditions, makes
Reaction system insulation 24min, during until there being tiny white crystal to separate out in reaction system, simultaneously by reactant
Water evaporates in system removes, and stops heating；Under the protection of nitrogen, filtered while hot, by reaction system
White crystal filter out, filtrate rejoins reaction system, and the stirring intensity of reactor is 319rpm；
Add the Sublimed Sulfur in formula and deionization anaerobic water, treat that temperature rises to 117 DEG C, and under this temperature conditions
Backflow insulation 4.3h, until time in reaction system without Sublimed Sulfur powder, stops heating reaction system, simultaneously
The temperature of reaction system is dropped to slowly room temperature, now, reaction system separates out the most light yellow or white
Pressed powder；Light yellow or the white solid powder separated out is filtered out from reaction system, containing many
The filtrate of lithium sulfide is stand-by；
By in formula polyacrylonitrile resin micropowder powder and kieselguhr, add 32wt%/kieselguhr electronics
The nmp solvent of level, under conditions of being sufficiently stirred for, is uniformly mixed into the viscose glue mud that viscosity is 15670Pa.s,
After homogenizer is sufficiently mixed uniformly, it is pressed into the thin slice of 660 μ m-thick, and pre-buried in thin slice
260 μm copper sheets；Molding kieselguhr viscose glue mud is inserted in the high temperature furnace of 364 DEG C, be 0.090MPa in negative pressure
Under conditions of, process 29min, make kieselguhr shape, the most carefully extract copper sheet out；Thin by extract out after copper sheet
Sheet is inserted in the high temperature furnace of 1341 DEG C, under conditions of negative pressure is 0.0990MPa, processes 85min, in nothing
The normal temperature air room of steam is cooled to room temperature；With the hydrogen on abjection polyacrylonitrile resin strand, oxygen atom；
Prepared porosity is 85.8%, and aperture is the kieselguhr thin slice that 4.4um structure contains carborundum；Then by thin slice
Insert in the nmp solution containing many lithium sulfides 32wt%, after dipping 34min takes out, will be containing many sulfurations
The kieselguhr thin slice of lithium and nmp solvent is placed in the high temperature that another temperature is 294 DEG C replacing 3 times through nitrogen
In stove, under conditions of suitably extraction negative pressure is the vacuum of 0.085MPa, after the process time is 45min, warp
The normal temperature air room of anhydrous steam is cooled to room temperature, and the kieselguhr thus obtaining the many lithium sulfides of first impregnation is thin
Sheet；Then thin slice is inserted again in the nmp solution that purity is 99.991wt% containing many lithium sulfides, dipping
32min, then insert in nitrogen replaces the high temperature furnace that another temperature is 269 DEG C of 5 times, in suitably extraction
Under conditions of negative pressure is the vacuum of 0.091MPa, after the process time is 35min, empty through the room temperature of anhydrous steam
Air chamber is cooled to room temperature, thus obtains second time and impregnates the kieselguhr thin slice of many lithium sulfides；Pass through the most again
Dipping and the high temperature evaporation of 3 times goes out NMP repeatedly, makes in kieselguhr thin slice containing many lithium sulfides 19.90wt%
Lithium sulfur battery anode material.
Embodiment 8
In the 316L stainless steel cauldron of 1L, under the protection being constantly passed through 454ml/min nitrogen, add
Enter 8.3molNMP, 1.0mol NaHS and 1.003mol sodium hydroxide, under 186rpm stirring condition,
Slowly the temperature of reaction system is increased to 88 DEG C, is simultaneously introduced 0.4mol deionization anaerobic water, is subsequently adding
1.001mol lithium chloride, continues to raise the temperature to 186 DEG C of reaction system, and under this temperature conditions, makes
Reaction system insulation 31min, during until there being tiny white crystal to separate out in reaction system, simultaneously by reactant
Water evaporates in system removes, and stops heating；Under the protection of nitrogen, filtered while hot, by reaction system
White crystal filter out, filtrate rejoins reaction system, and the stirring intensity of reactor is 314rpm；
Add the Sublimed Sulfur in formula and deionization anaerobic water, treat that temperature rises to 114 DEG C, and under this temperature conditions
Backflow insulation 4.4h, until time in reaction system without Sublimed Sulfur powder, stops heating reaction system, simultaneously
The temperature of reaction system is dropped to slowly room temperature, now, reaction system separates out the most light yellow or white
Pressed powder；Light yellow or the white solid powder separated out is filtered out from reaction system, containing many
The filtrate of lithium sulfide is stand-by；
By in formula polyacrylonitrile resin micropowder powder and kieselguhr, add 30.5wt%/kieselguhr electricity
The nmp solvent of sub-level, under conditions of being sufficiently stirred for, is uniformly mixed into the viscose glue that viscosity is 16830Pa.s
Mud, after homogenizer is sufficiently mixed uniformly, is pressed into the thin slice of 740 μ m-thick, and pre-in thin slice
Bury 260 μm copper sheets；Molding kieselguhr viscose glue mud is inserted in the high temperature furnace of 369 DEG C, be 0.090MPa in negative pressure
Under conditions of, process 37min, make kieselguhr shape, the most carefully extract copper sheet out；Thin by extract out after copper sheet
Sheet is inserted in the high temperature furnace of 1373 DEG C, under conditions of negative pressure is 0.0994MPa, processes 87min, in nothing
The normal temperature air room of steam is cooled to room temperature；With the hydrogen on abjection polyacrylonitrile resin strand, oxygen atom；
Prepared porosity is 86.8%, and aperture is the kieselguhr thin slice that 4.6um structure contains carborundum；Then by thin slice
Insert in the nmp solution containing many lithium sulfides 31.3wt%, after dipping 37min takes out, will be containing many sulfur
The kieselguhr thin slice changing lithium and nmp solvent is placed in the height that another temperature is 297 DEG C replacing 5 times through nitrogen
In temperature stove, under conditions of suitably extraction negative pressure is the vacuum of 0.086MPa, after the process time is 39min,
It is cooled to room temperature through the normal temperature air room of anhydrous steam, thus obtains the kieselguhr of the many lithium sulfides of first impregnation
Thin slice；Then thin slice is inserted again in the nmp solution that purity is 99.991wt% containing many lithium sulfides, leaching
Stain 31min, then insert in nitrogen replaces the high temperature furnace that another temperature is 278 DEG C of 6 times, suitably taking out
Under conditions of taking the vacuum that negative pressure is 0.088MPa, after the process time is 36min, through the room temperature of anhydrous steam
Air chamber is cooled to room temperature, thus obtains second time and impregnates the kieselguhr thin slice of many lithium sulfides；Warp the most again
Dipping and the high temperature evaporation of crossing 4 times repeatedly go out NMP, make in kieselguhr thin slice containing many lithium sulfides 20.9wt%
Lithium sulfur battery anode material.
Embodiment 9
In the 316L stainless steel cauldron of 1L, under the protection being constantly passed through 474ml/min nitrogen, add
Enter 8.6molNMP, 1.0mol NaHS and 1.003mol sodium hydroxide, under 188rpm stirring condition,
Slowly the temperature of reaction system is increased to 88 DEG C, is simultaneously introduced 0.4mol deionization anaerobic water, is subsequently adding
1.001mol lithium chloride, continues to raise the temperature to 188 DEG C of reaction system, and under this temperature conditions, makes
Reaction system insulation 33min, during until there being tiny white crystal to separate out in reaction system, simultaneously by reactant
Water evaporates in system removes, and stops heating；Under the protection of nitrogen, filtered while hot, by reaction system
White crystal filter out, filtrate rejoins reaction system, and the stirring intensity of reactor is 330rpm；
Add the Sublimed Sulfur in formula and deionization anaerobic water, treat that temperature rises to 88～118 DEG C, and in this temperature strip
Backflow insulation 6h under part, until time in reaction system without Sublimed Sulfur powder, stops heating reaction system, with
Time the temperature of reaction system is dropped to room temperature slowly, now, reaction system separates out the most light yellow or white
The pressed powder of color；Light yellow or the white solid powder separated out is filtered out from reaction system, contains
The filtrate of many lithium sulfides is stand-by；
By in formula polyacrylonitrile resin micropowder powder and kieselguhr, add 33wt%/kieselguhr electronics
The nmp solvent of level, under conditions of being sufficiently stirred for, is uniformly mixed into the viscose glue mud that viscosity is 19600Pa.s,
After homogenizer is sufficiently mixed uniformly, it is pressed into the thin slice of 790 μ m-thick, and pre-buried in thin slice
310 μm copper sheets；Molding kieselguhr viscose glue mud is inserted in the high temperature furnace of 379 DEG C, be 0.091MPa in negative pressure
Under conditions of, process 38min, make kieselguhr shape, the most carefully extract copper sheet out；Thin by extract out after copper sheet
Sheet is inserted in the high temperature furnace of 1377 DEG C, under conditions of negative pressure is 0.0999MPa, processes 88min, in nothing
The normal temperature air room of steam is cooled to room temperature；With the hydrogen on abjection polyacrylonitrile resin strand, oxygen atom；
Prepared porosity is 87.4%, and aperture is the kieselguhr thin slice that 4.8um structure contains carborundum；Then by thin slice
Insert in the nmp solution containing many lithium sulfides 31wt%, after dipping 38min takes out, will be containing many sulfurations
The kieselguhr thin slice of lithium and nmp solvent is placed in the high temperature that another temperature is 300 DEG C replacing 3 times through nitrogen
In stove, under conditions of suitably extraction negative pressure is the vacuum of 0.088MPa, after the process time is 36min, warp
The normal temperature air room of anhydrous steam is cooled to room temperature, and the kieselguhr thus obtaining the many lithium sulfides of first impregnation is thin
Sheet；Then thin slice is inserted again in the nmp solution that purity is 99.991wt% containing many lithium sulfides, dipping
33min, then insert in nitrogen replaces the high temperature furnace that another temperature is 281 DEG C of 6 times, in suitably extraction
Under conditions of negative pressure is the vacuum of 0.091MPa, after the process time is 36min, empty through the room temperature of anhydrous steam
Air chamber is cooled to room temperature, thus obtains second time and impregnates the kieselguhr thin slice of many lithium sulfides；Pass through the most again
Dipping and the high temperature evaporation of 4 times goes out NMP repeatedly, makes in kieselguhr thin slice containing many lithium sulfides 20.8wt%
Lithium sulfur battery anode material.
Claims (3)
1. the manufacture method of a lithium sulfur battery anode material, it is characterised in that by polyacrylonitrile tree
Fat micropowder and kieselguhr, with mass ratio 38～41:62～59, add in mixed at high speed agitator,
Add the nmp solvent of account for kieselguhr quality 28～33%, under conditions of being sufficiently stirred for,
Be uniformly mixed into the viscose glue mud that viscosity is 13800～19600Pa s, then by viscose glue mud according to
Lithium sulfur battery anode material need to be fabricated to the sheeting of respective shapes, sheeting is put
In in the high temperature furnace that nitrogen is replaced, under conditions of suitable extracting vacuum, make thin slice viscose glue
Mud becomes the kieselguhr thin slice comprising only carborundum composition；Then it is placed on containing many lithium sulfides
In the nmp solution of 28～33wt%, impregnate 33～38min, after taking-up, will be containing many sulfur
The kieselguhr thin slice changing lithium and nmp solvent is placed in the high temperature furnace of nitrogen displacement, suitable
Under conditions of extracting vacuum, the nmp solvent in kieselguhr thin slice is made fully to evaporate,
Dipping and the high temperature evaporation of 3～6 times goes out NMP the most repeatedly, obtains containing in kieselguhr thin slice
There is the lithium sulfur battery anode material of many lithium sulfides 18～21wt%.
The manufacture method of lithium sulfur battery anode material the most according to claim 1, its feature exists
In, comprise following concrete manufacturing process:
1) in the 316L stainless steel cauldron of 1L, the speed with 360～480ml/min is not
Open close enter nitrogen, add 5.4～8.8molNMP, 1.0mol NaHS and 1.003mol hydrogen
Sodium oxide, under 160～190rpm stirring conditions, raises the temperature of reaction system slowly
To 86～88 DEG C, it is simultaneously introduced 0.4mol deionization anaerobic water, is subsequently adding 1.001mol
Lithium chloride, continues to raise the temperature to 170～190 DEG C of reaction system, and in this temperature conditions
Under, make reaction system insulation 18～33min, until reaction system has tiny white crystal
Separate out, after further the water evaporates in reaction system being removed, stop heating；
2) by 1) the anhydrous response system that obtains under the protection of nitrogen, filtered while hot, will be anti-
Answering the white crystal in system to filter out, filtrate rejoins reaction system, adds in formula
Sublimed Sulfur and deionization anaerobic water, treat that temperature rises to 88～118 DEG C, and in this temperature strip
Backflow insulation 4～6h under part, until time in reaction system without Sublimed Sulfur powder, stops reaction
System heats, and the temperature of reaction system drops to room temperature slowly, now, in reaction system
Separate out the most light yellow or white pressed powder；Wherein the stirring intensity of reactor be 280～
330rpm；
3) by 2) the light yellow or white solid powder that separates out filters out from reaction system,
The filtrate obtained is the nmp solution containing many lithium sulfides 28-33wt%, stand-by；
4), in the polyacrylonitrile resin micropowder powder mixed by formula with kieselguhr, then add
Enter to account for the 28 of kieselguhr quality～the nmp solvent of 33%, under conditions of being sufficiently stirred for, all
Even it is mixed into the viscose glue mud that viscosity is 13800～19600Pa s, fills through homogenizer
After point mix homogeneously, be pressed into the thin slice of 180～810 μ m-thick, and in thin slice pre-buried 80～
330 μm copper sheets；
5) by 4) the molding kieselguhr viscose glue mud that obtains inserts in the high temperature furnace of 280～380 DEG C,
Under conditions of negative pressure is 0.088～0.091Mpa, process 16～38min, make kieselguhr fixed
Type, the most carefully extracts copper sheet out；
6), by 5) gained thin slice inserts in the high temperature furnace of 1280～1380 DEG C, in negative pressure be
Under conditions of 0.098～0.0999Mpa, process 81～88min, empty at the room temperature of anhydrous steam
Air chamber is cooled to room temperature；With the hydrogen on abjection polyacrylonitrile resin strand, oxygen atom；Prepare
Porosity is 81～88%, and aperture is the kieselguhr thin slice that 3～5 μm contain carborundum；
7), by 6) thin slice that obtains inserts 3) obtained by containing many lithium sulfides 28～33wt%
Nmp solution in, through dipping 33～38min taking-up after, will be containing many lithium sulfides and NMP
The kieselguhr thin slice of solvent is placed in and replaces another temperature of 3～6 times through nitrogen is 280～300 DEG C
High temperature furnace in, under conditions of suitably extraction negative pressure is the vacuum of 0.068～0.088Mpa,
After the process time is 36～48min, it is cooled to room temperature through the normal temperature air room of anhydrous steam, this
Sample just obtains the kieselguhr thin slice of the many lithium sulfides of first impregnation；
8) by 7) thin slice that obtains inserts in the nmp solution containing many lithium sulfides again, dipping
18～33min, then insert that to replace another temperature of 3～6 times through nitrogen be 260～281 DEG C
High temperature furnace in, under conditions of suitably extraction negative pressure is the vacuum of 0.088～0.091Mpa,
After the process time is 33～36min, it is cooled to room temperature through the normal temperature air room of anhydrous steam, this
Sample just obtains second time and impregnates the kieselguhr thin slice of many lithium sulfides；
9) by 8) thin slice that obtains uses 8) process conditions in step, through repeatedly 2～
Dipping and the high temperature evaporation of 4 times go out NMP, obtain in kieselguhr thin slice containing many lithium sulfides
The lithium sulfur battery anode material of 18～21wt%.
A kind of manufacture method of lithium sulfur battery anode material,
It is characterized in that, the purity of the many lithium sulfides used be 99.991wt%, NMP be electron level
N-Methyl pyrrolidone.
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