CN103985864A - Preparation method for anode material of lithium sulphur battery - Google Patents
Preparation method for anode material of lithium sulphur battery Download PDFInfo
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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
- H01M4/36—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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Abstract
The invention discloses a preparation method for an anode material of a lithium sulphur battery. The preparation method comprises the following steps: mixing polyacrylonitrile resin micropowder and kieselguhr as a mass ratio of (38-41) to (62-59), putting the mixture into a high temperature furnace through nitrogen replacement after pre-processing, and in a condition of proper vacuumizing, enabling lumpy mucilage mud to turn into lumpy kieselguhr which only contains a silicon carbide element; dissolving lithium polysulfide in an NMP (N-methylpyrrolidone) solution which contains 28-33% by weight of lithium polysulfide, soaking for 33-38 minutes, after taking out, and putting the lumpy kieselguhr which contains the lithium polysulfide and the NMP solvent into another high temperature furnace through nitrogen replacement, so that the anode material of the lithium sulphur battery which contains 18-21% by weight of lithium polysulfide through dipping and steaming at high temperature for many times. The manufacturing method for the anode material of the lithium sulphur battery, which is disclosed by the invention, is simple in preparation and low in cost; the prepared anode material of the lithium sulphur battery has high sulphur accommodation ability and relatively high ion transmission ability and conductivity, and the high rate performance and high cycle performance of the lithium sulphur battery can be improved.
Description
Affiliated field
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, the becoming increasingly conspicuous of the problems such as energy shortage, environmental pollution, people are to the understanding of chemical power source and require also more and more highlyer, and impelling people constantly to explore new chemical power source is main energy storage system.In recent decades, take lithium metal has led the developing direction of high-performance chemical power supply as basic battery.Along with the successful commercialization of lithium ion battery, countries in the world are all in the research that steps up to carry out vehicle lithium-ion power battery.But due to factors such as energy density, fail safe, prices, conventional lithium ion battery lithium as sour in cobalt, 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 that has development potentiality and application prospect.It has height
Beyond specific capacity and high-energy-density, sulphur is showing incomparable advantage as positive active material aspect source, cost and environmental friendliness, and at present, lithium-sulfur cell exists the problems such as cycle performance is poor, the further raising of high rate performance needs.And two main problems that lithium-sulfur cell exists are active material sulfur materials itself and final discharging product Li on the one hand
2s is the insulator of electronics and ion; On the other hand, the intermediate product polysulfide in discharge process is soluble in electrolyte, and these can cause irreversible loss and the capacity attenuation of active material.For this reason, how to suppress the diffusion of polysulfide, the conductivity improving in the anodal cyclic process of sulphur is the research emphasis of sulfenyl positive electrode.
Academia mainly spread and improved two aspects of positive electrode conductivity around inhibition polysulfide and conducted a research in recent years.On material structure, first consider it is that elemental sulfur is adsorbed on porous material skeleton, such as by porous charcoal as the material with carbon elements such as active carbon, carbon nano-tube, Graphene and sulphur compound, prevent that the polysulfide that course of reaction is produced is dissolved in electrolyte, by electrolyte, spread, contribute to like this to reduce shuttle back and forth effect and self-discharge phenomenon.These new material structures have more or less improved the cyclical stability of electrode.But the general specific area of traditional porous carbon material is less, aperture size is single, structural integrity is poor, aperture is difficult to regulation and control, the adsorption activity material sulphur of material is limited in one's ability, causes that sulfur content in the composite positive pole of preparation is lower, skewness, poor electric conductivity, be assembled into circulating battery after a few, still have a large amount of active materials from carbon structure duct, to dissolve, cause the loss of active material, lithium-sulfur cell energy density is difficult to further improve.
This area is in the urgent need to developing a kind of lithium-sulfur cell positive electrode that has good conductivity and hierarchical pore structure concurrently, suppress the diffusion of polysulfide, the conductivity in the anodal cyclic process of raising sulphur, and then ion transfer ability and the conductivity of raising positive electrode, can effectively reduce and discharge and recharge polarization, reduce the internal resistance of cell, improve the greatly doubly forthright of lithium-sulfur cell.
In Chinese patent number No:02125137.1, introduced a kind of employing at the surface-coated layer of surface passivating material of sulfur-containing compound lithium sulfur battery anode material, its objective is the loss that reduces sulfur-containing compound sulphur in charge and discharge process, but because coated surface passivation layer is carbonate or the hydroxyl carbonate of the chemical elements such as some Mg, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr, can cause the conductivity of this electrode material to reduce.
In Chinese patent number No:1143369.8, introduce a kind of positive electrode that adopts several raw material such as sulfur-containing compound and conductive agent and adhesive to prepare lithium-sulfur cell, because conductive agent is the moulding material of metal material, the impact of adhesive, makes the conductivity of its lithium sulfur battery anode material can be subject to corresponding impact simultaneously.
In Chinese Patent Application No. code No:201310418375.5, introduced a kind of manufacturing process of inorganic electrolyte, wherein apply diatomite and be used as a kind of electrolytical backing material, wherein adopt polysiloxanes organic siliconresin, with the diatomite material that preparation can adsorbing electrolyte material of coming together, but, owing to can be subject to the impact of polyorganosiloxane resin strand in preparing the process of carborundum, can cause its voidage to decline.
Above shortcoming in view of prior art, the object of the invention is to overcome the deficiency of current lithium sulfur battery anode material, adopt on the one hand many lithium sulfides of charge-discharge performance excellence, adopt on the other hand the diatomite that contains carbon, many lithium sulfides solution is adsorbed in wherein easily, in order to improve the dispersiveness of lithium salts in diatomite, and then capacitance and the charge-discharge velocity of raising solid electrolyte, adopt this polymer of polyacrylonitrile resin to prepare conductive carrier simultaneously, the obstruction that after reduction lithium salts dissociation, lithium ion and anion move under the effect of voltage, thereby improve the conductance of this lithium sulfur battery anode material.
Summary of the invention
The present invention is directed to the compound positive electrode obtaining of porous charcoal of the prior art and sulphur because existing adsorption activity material sulphur problem limited in one's ability, poor electric conductivity that its application in battery is limited to, object is to be to provide a kind of can improve the high energy high rate performance of lithium-sulfur cell and the lithium sulfur battery anode material of high cycle performance.
The object of the invention is to realize by following means.
A kind of manufacture method of lithium sulfur battery anode material, it is characterized in that, by polyacrylonitrile resin micro mist and diatomite with mass ratio 38～41:62～59, add in mixed at high speed blender, add again the diatomaceous nmp solvent of 28～33%wt/, under well-beaten condition, being uniformly mixed into viscosity is the viscose glue mud of 13800～19600pa.s, then by viscose glue mud according to the bulk material that need to be made into respective shapes of lithium sulfur battery anode material, bulk material is placed in to the high temperature furnace through nitrogen replacement, under the condition of suitable extracting vacuum, make block viscose glue mud become the block diatomite that only contains carborundum composition, then be placed on containing in the nmp solution of many lithium sulfide 28～33%wt, dipping 33～38min, after taking-up, the block diatomite that contains many lithium sulfides and nmp solvent is placed in to the high temperature furnace through nitrogen replacement, under the condition of suitable extracting vacuum, nmp solvent in block diatomite is fully evaporated, and the dipping of 3～6 times and high temperature evaporation go out NMP so repeatedly, make the lithium sulfur battery anode material that contains many lithium sulfide 18～21%wt in block diatomite.
Its concrete steps comprise:
1) in the 316L of 1L stainless steel cauldron, constantly passing under the protection of 360～480ml/min nitrogen, add 5.4～8.8mol electron level NMP, 1.0mol NaHS and 1.003mol NaOH, under 160～190rpm stirring condition, slowly the temperature of reaction system is elevated to 86～88 ℃, add 0.4mol deionization anaerobic water simultaneously, then add 1.001mol lithium chloride, continue temperature to 170～190 ℃ of rising reaction system, and under this temperature conditions, make reaction system insulation 18～33min, until while having tiny white crystal to separate out in reaction system, water evaporates in reaction system is removed simultaneously, and stop heating,
2) by 1) the anhydrous response system that obtains is under the protection of nitrogen, filter while hot, white crystal in reaction system is filtered out, filtrate rejoins reaction system, add sublimed sulfur and deionization anaerobic water in formula, treat that temperature rises to 88～118 ℃, and the insulation 4～6h that refluxes under this temperature conditions, until in reaction system during without sublimed sulfur powder, stop reaction system heating, the temperature of reaction system is dropped to room temperature slowly simultaneously, now, in reaction system, separate out a small amount of light yellow or white pressed powder; Wherein the stirring intensity of reactor is 280～330rpm;
3) by 2) the light yellow or white solid powder of separating out filters out from reaction system, and the filtrate that the purity that contains many lithium sulfides is 99.991%wt is stand-by;
4) by polyacrylonitrile resin micro mist powder and diatomite in formula, add again the diatomaceous electron level nmp solvent of 28～33%wt/, under well-beaten condition, being uniformly mixed into viscosity is the viscose glue mud of 13800～19600pa.s, after homogenizer fully mixes, be pressed into the thick thin slice of 180～810 μ m, and in thin slice pre-buried 80～330 μ m copper sheets;
5) by 4) the moulding diatomite viscose glue mud that obtains inserts in the high temperature furnace of 280～380 ℃, under the condition that is 0.088～0.091Mpa, processes 16～38min in negative pressure, makes diatomite sizing, then carefully extracts copper sheet out;
6), by 5) gained thin slice inserts in the high temperature furnace of 1280～1380 ℃, under the condition that is 0.098～0.0999Mpa, processes 81～88min in negative pressure, in the normal temperature air chamber of anhydrous steam, is cooled to normal temperature; To deviate from hydrogen, the oxygen atom on polyacrylonitrile resin strand; Making porosity is 81～88%, and aperture is the diatomite thin slice that 3～5um structure contains carborundum;
7), by 6) thin slice that obtains inserts 3) containing in the nmp solution of many lithium sulfide 28～33%wt, through flooding after 33～38min taking-up, it is the high temperature furnace of 280～300 ℃ that the block diatomite that contains many lithium sulfides and nmp solvent is placed in to another temperature through nitrogen replacement 3～6 times, suitably extracting under the condition of the vacuum that negative pressure is 0.068～0.088Mpa, after processing time is 36～48min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, so just obtains flooding for the first time the diatomite thin slice of many lithium sulfides;
8) by 7) thin slice that obtains inserts in the nmp solution that contains many lithium sulfides again, dipping 18～33min, insert again another temperature through nitrogen replacement 3～6 times and be in the high temperature furnace of 260～281 ℃, suitably extracting under the condition of the vacuum that negative pressure is 0.088～0.091Mpa, after processing time is 33～36min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, so just obtains flooding for the second time the diatomite thin slice of many lithium sulfides;
9) by 8) thin slice that obtains adopts 8) process conditions in step, through dipping and the high temperature evaporation of 2～4 times repeatedly, go out NMP, make the lithium sulfur battery anode material that contains many lithium sulfide 18～21%wt in block diatomite;
Technical characterstic of the present invention:
1, first the present invention utilizes the lithium chloride that can be dissolved in nmp solvent, its normal-temperature dissolution degree in nmp solvent can be up to 26g/100mlNMP, in order to improve the solubility of lithium chloride, need to carry out heat temperature raising to a certain degree to solution system, in addition, because NMP is under heating condition, can be because contacting and make it to occur oxidation reaction yellowing with air, and then the purity of reduction NMP, therefore, need to synthetic dicyandiamide solution, protect with inert gas (as: nitrogen), in order to avoid cause the generation of other side reactions, thereby reduce the purity of lithium sulfide and/or many lithium sulfides.
2, secondly the present invention utilizes very common NaHS industrial raw materials, although these raw material are also insoluble to nmp solvent under the condition of normal temperature and heat temperature raising, but, under the condition that has anaerobic water to exist, by adding NaOH to react with it, generation contains impurity level vulcanized sodium seldom, and then after heating by intensification, by vulcanized sodium and lithium chloride, there is therein ionic reaction, simultaneously, evaporating under the condition of anaerobic water wherein, synthetic lithium sulfide, because the solubility of sodium chloride in the nmp solvent of 150～160 ℃ only has 5mg/100mlNMP, solubility at normal temperature is also low-down, and lithium sulfide is dissolved in nmp solvent, for this reason, the present invention makes full use of this specific character of the easy NMP of lithium sulfide, comparatively be easy to obtain lithium sulfide, its objective is because lithium sulfide is easy to oxidized decomposition in air, discharge hydrogen sulfide poison gas, the object that adopts technological process of the present invention is that the lithium sulfide that can avoid on the one hand synthetic is not oxidized, in order to obtain highly purified anhydrous lithium sulfide on the one hand in addition.
3, the present invention is oxidized in the deionized water of aerobic for fear of lithium sulfide, therefore, make full use of utilizable condition, be exactly deionized water can be passed through to physics or/and the mode of chemistry, dissolved oxygen in deionized water is dropped to very low degree, remove even completely, not oxidized to guarantee lithium sulfide, and then improve the purity of many lithium sulfides.
4, the present invention is for the synthetic required many lithium sulfides raw material of lithium-sulfur cell.Because elemental sulfur is soluble among ethanol, according to the principles of chemistry of similar compatibility, elemental sulfur and lithium sulfide all can be soluble among nmp solvent, still, due to the difference of solubility, can make aggregate velocity be affected, in order to improve aggregate velocity, the present invention makes full use of the light water solvent that can make lithium sulfide generation electrolysis, and will make like this aggregate velocity is that solvent has improved nearly 2 times with ethanol or ammoniacal liquor, simultaneously, nearly reduce costs 40%, be more conducive to realize suitability for industrialized production.
5, the present invention is in order to make full use of reflux solvent and aqueous systems, is in order to guarantee temperature stable of synthetic system, to improve raw-material utilance, and then the productive rate of many lithium sulfides is provided.
6, to adopt diatomaceous object be to make full use of diatomaceous open structure in the present invention, also utilizes the diatomite can sinter molding simultaneously, can make diatomite sinter the material of various shapes into, is conducive to be made into the required electrode material of lithium-sulfur cell.
7, the present invention is in order to increase the conductivity of electrode material, make full use of the characteristic that polyacrylonitrile resin micro mist is dissolved in organic solvent, dissolving by organic solvent makes polyacrylonitrile resin micro mist fully mix with diatomite, being conducive to make polyacrylonitrile resin micro mist to be transformed into carborundum electric conducting material after forming processes subsequently merges with the diatom soil phase better, and carborundum be uniformly distributed better with diatomite among, be conducive to lithium sulfur battery anode material conductivity more stable; The present invention adopts the polyacrylonitrile of complete straight chain in addition, its objective is and utilizes this resin to hold very much with carbonization, because polyacrylonitrile resin is the original material of carbon fiber, thereby is not subject to the impact of molecular chain structure and causes its porosity to decline.
8, the present invention adopts the object of many lithium sulfides compound that can be dissolved in nmp solvent, it is the nmp solution that makes to have the many lithium sulfides of the better adsorption and permeation of very microporous carborundum diatomite material, thereby carborundum electric conducting material and many lithium sulfides are organically combined better, this is conducive to the dissociation of many lithium sulfides in charge and discharge process and dissociates, simultaneously, because diatomaceous micropore is when improving lithium sulfur battery anode material conductivity, also prevent the excessive dissociation of many lithium sulfides, be conducive to lithium-sulfur cell charge and discharge cycles, with prevent lithium-sulfur cell that discharge and recharge with decay number of times, to extend the useful life of lithium-sulfur cell.
Technological process brief introduction of the present invention
A kind of manufacture method of lithium sulfur battery anode material, it is characterized in that, polyacrylonitrile resin micro mist and diatomite are added in mixed at high speed blender with certain mass ratio, add again a certain proportion of nmp solvent, under well-beaten condition, be uniformly mixed into the viscose glue mud of certain viscosity, then by viscose glue mud according to the bulk material that need to be made into respective shapes of lithium sulfur battery anode material, bulk material is placed in to the high temperature furnace through nitrogen replacement, under the condition of suitable extracting vacuum, make block viscose glue mud become the block diatomite that only contains carborundum composition, then many lithium sulfides are dissolved in nmp solvent, form containing the certain density electron level nmp solution of many lithium sulfides, then the block diatomite after high-temperature process is immersed in the nmp solution that contains many lithium sulfides, dipping certain hour, after taking-up, the block diatomite that contains many lithium sulfides and nmp solvent is placed in to another high temperature furnace through nitrogen replacement, under the condition of suitable extracting vacuum, nmp solvent in block diatomite is fully evaporated, dipping and high temperature evaporation several times goes out NMP so repeatedly, make to contain in block diatomite a certain amount of lithium sulfur battery anode material of many lithium sulfides.
The specific embodiment of the present invention
Embodiment 1
In the 316L of 1L stainless steel cauldron, constantly passing under the protection of 360ml/min nitrogen, add 5.4molNMP, 1.0mol NaHS and 1.003mol NaOH, under 160～190rpm stirring condition, slowly the temperature of reaction system is elevated to 86 ℃, add 0.4mol deionization anaerobic water simultaneously, then add 1.001mol lithium chloride, continue the temperature to 170 ℃ of rising reaction system, and under this temperature conditions, make reaction system insulation 33min, until while having tiny white crystal to separate out in reaction system, water evaporates in reaction system is removed simultaneously, and stop heating, under the protection of nitrogen, filter while hot, the white crystal in reaction system is filtered out, filtrate rejoins reaction system, and the stirring intensity of reactor is 330rpm, add sublimed sulfur and deionization anaerobic water in formula, treat that temperature rises to 88 ℃, and the insulation 6h that refluxes under this temperature conditions, until in reaction system during without sublimed sulfur powder, stop reaction system heating, the temperature of reaction system is dropped to room temperature slowly simultaneously, now, in reaction system, separate out a small amount of light yellow or white pressed powder, light yellow or the white solid powder of separating out is filtered out from reaction system, and the filtrate of containing many lithium sulfides is stand-by,
By polyacrylonitrile resin micro mist powder and the diatomite in formula, the nmp solvent that adds again 28%wt/ diatomite electron level, under well-beaten condition, being uniformly mixed into viscosity is the viscose glue mud of 13800pa.s, after homogenizer fully mixes, be pressed into the thick thin slice of 180 μ m, and in thin slice pre-buried 80 μ m copper sheets; Moulding diatomite viscose glue mud is inserted in the high temperature furnace of 280 ℃, under the condition that is 0.088Mpa in negative pressure, process 38min, make diatomite sizing, then carefully extract copper sheet out; By extracting thin slice after copper sheet out and insert in the high temperature furnace of 1280 ℃, under the condition that is 0.0999Mpa in negative pressure, process 88min, in the normal temperature air chamber of anhydrous steam, be cooled to normal temperature; To deviate from hydrogen, the oxygen atom on polyacrylonitrile resin strand; Making porosity is 81%, and aperture is the diatomite thin slice that 3um structure contains carborundum; Then thin slice is inserted containing in the nmp solution of many lithium sulfides 28%wt, after dipping 38min takes out, it is the high temperature furnace of 300 ℃ that the block diatomite that contains many lithium sulfides and nmp solvent is placed in to another temperature through nitrogen replacement 3 times, suitably extracting under the condition of the vacuum that negative pressure is 0.088Mpa, after processing time is 48min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, so just obtains flooding for the first time the diatomite thin slice of many lithium sulfides; Then in the nmp solution that thin slice to be inserted again to the purity that contains many lithium sulfides be 99.991%wt, dipping 33min, insert again another temperature through nitrogen replacement 6 times and be in the high temperature furnace of 260 ℃, suitably extracting under the condition of the vacuum that negative pressure is 0.091Mpa, after processing time is 36min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, so just obtains flooding for the second time the diatomite thin slice of many lithium sulfides; And then go out NMP through dipping and the high temperature evaporation of 2 times repeatedly, make the lithium sulfur battery anode material that contains many lithium sulfides 18%wt in block diatomite.
Embodiment 2
In the 316L of 1L stainless steel cauldron, constantly passing under the protection of 480ml/min nitrogen, add 8.8molNMP, 1.0mol NaHS and 1.003mol NaOH, under 190rpm stirring condition, slowly the temperature of reaction system is elevated to 88 ℃, add 0.4mol deionization anaerobic water simultaneously, then add 1.001mol lithium chloride, continue the temperature to 190 ℃ of rising reaction system, and under this temperature conditions, make reaction system insulation 18min, until while having tiny white crystal to separate out in reaction system, water evaporates in reaction system is removed simultaneously, and stop heating, under the protection of nitrogen, filter while hot, the white crystal in reaction system is filtered out, filtrate rejoins reaction system, and the stirring intensity of reactor is 330rpm, add sublimed sulfur and deionization anaerobic water in formula, treat that temperature rises to 118 ℃, and the insulation 4h that refluxes under this temperature conditions, until in reaction system during without sublimed sulfur powder, stop reaction system heating, the temperature of reaction system is dropped to room temperature slowly simultaneously, now, in reaction system, separate out a small amount of light yellow or white pressed powder, light yellow or the white solid powder of separating out is filtered out from reaction system, and the filtrate of containing many lithium sulfides is stand-by,
By polyacrylonitrile resin micro mist powder and the diatomite in formula, the nmp solvent that adds again 33%wt/ diatomite electron level, under well-beaten condition, being uniformly mixed into viscosity is the viscose glue mud of 19600pa.s, after homogenizer fully mixes, be pressed into the thick thin slice of 810 μ m, and in thin slice pre-buried 330 μ m copper sheets; Moulding diatomite viscose glue mud is inserted in the high temperature furnace of 380 ℃, under the condition that is 0.088Mpa in negative pressure, process 16min, make diatomite sizing, then carefully extract copper sheet out; By extracting thin slice after copper sheet out and insert in the high temperature furnace of 1380 ℃, under the condition that is 0.098Mpa in negative pressure, process 81min, in the normal temperature air chamber of anhydrous steam, be cooled to normal temperature; To deviate from hydrogen, the oxygen atom on polyacrylonitrile resin strand; Making porosity is 88%, and aperture is the diatomite thin slice that 5um structure contains carborundum; Then thin slice is inserted containing in the nmp solution of many lithium sulfides 33%wt, after dipping 33min takes out, it is the high temperature furnace of 300 ℃ that the block diatomite that contains many lithium sulfides and nmp solvent is placed in to another temperature through nitrogen replacement 6 times, suitably extracting under the condition of the vacuum that negative pressure is 0.068Mpa, after processing time is 36min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, so just obtains flooding for the first time the diatomite thin slice of many lithium sulfides; Then in the nmp solution that thin slice to be inserted again to the purity that contains many lithium sulfides be 99.991%wt, dipping 18min, insert again another temperature through nitrogen replacement 6 times and be in the high temperature furnace of 281 ℃, suitably extracting under the condition of the vacuum that negative pressure is 0.088Mpa, after processing time is 33min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, so just obtains flooding for the second time the diatomite thin slice of many lithium sulfides; And then go out NMP through dipping and the high temperature evaporation of 4 times repeatedly, make the lithium sulfur battery anode material that contains many lithium sulfides 21%wt in block diatomite.
Embodiment 3
In the 316L of 1L stainless steel cauldron, constantly passing under the protection of 373ml/min nitrogen, add 5.9molNMP, 1.0mol NaHS and 1.003mol NaOH, under 171rpm stirring condition, slowly the temperature of reaction system is elevated to 87 ℃, add 0.4mol deionization anaerobic water simultaneously, then add 1.001mol lithium chloride, continue the temperature to 173 ℃ of rising reaction system, and under this temperature conditions, make reaction system insulation 21min, until while having tiny white crystal to separate out in reaction system, water evaporates in reaction system is removed simultaneously, and stop heating, under the protection of nitrogen, filter while hot, the white crystal in reaction system is filtered out, filtrate rejoins reaction system, and the stirring intensity of reactor is 291rpm, add sublimed sulfur and deionization anaerobic water in formula, treat that temperature rises to 91 ℃, and the insulation 5.8h that refluxes under this temperature conditions, until in reaction system during without sublimed sulfur powder, stop reaction system heating, the temperature of reaction system is dropped to room temperature slowly simultaneously, now, in reaction system, separate out a small amount of light yellow or white pressed powder, light yellow or the white solid powder of separating out is filtered out from reaction system, and the filtrate of containing many lithium sulfides is stand-by,
By polyacrylonitrile resin micro mist powder and the diatomite in formula, the nmp solvent that adds again 29%wt/ diatomite electron level, under well-beaten condition, being uniformly mixed into viscosity is the viscose glue mud of 14340pa.s, after homogenizer fully mixes, be pressed into the thick thin slice of 210 μ m, and in thin slice pre-buried 100 μ m copper sheets; Moulding diatomite viscose glue mud is inserted in the high temperature furnace of 293 ℃, under the condition that is 0.089Mpa in negative pressure, process 36min, make diatomite sizing, then carefully extract copper sheet out; By extracting thin slice after copper sheet out and insert in the high temperature furnace of 1313 ℃, under the condition that is 0.0990Mpa in negative pressure, process 87min, in the normal temperature air chamber of anhydrous steam, be cooled to normal temperature; To deviate from hydrogen, the oxygen atom on polyacrylonitrile resin strand; Making porosity is 81.3%, and aperture is the diatomite thin slice that 3.8um structure contains carborundum; Then thin slice is inserted containing in the nmp solution of many lithium sulfides 29%wt, after dipping 37min takes out, it is the high temperature furnace of 290 ℃ that the block diatomite that contains many lithium sulfides and nmp solvent is placed in to another temperature through nitrogen replacement 5 times, suitably extracting under the condition of the vacuum that negative pressure is 0.084Mpa, after processing time is 47min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, so just obtains flooding for the first time the diatomite thin slice of many lithium sulfides; Then in the nmp solution that thin slice to be inserted again to the purity that contains many lithium sulfides be 99.991%wt, dipping 31min, insert again another temperature through nitrogen replacement 4 times and be in the high temperature furnace of 264 ℃, suitably extracting under the condition of the vacuum that negative pressure is 0.090Mpa, after processing time is 35min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, so just obtains flooding for the second time the diatomite thin slice of many lithium sulfides; And then go out NMP through dipping and the high temperature evaporation of 3 times repeatedly, make the lithium sulfur battery anode material that contains many lithium sulfides 18.4%wt in block diatomite.
Embodiment 4
In the 316L of 1L stainless steel cauldron, constantly passing under the protection of 384ml/min nitrogen, add 6.4molNMP, 1.0mol NaHS and 1.003mol NaOH, under 179rpm stirring condition, slowly the temperature of reaction system is elevated to 88 ℃, add 0.4mol deionization anaerobic water simultaneously, then add 1.001mol lithium chloride, continue the temperature to 176 ℃ of rising reaction system, and under this temperature conditions, make reaction system insulation 31min, until while having tiny white crystal to separate out in reaction system, water evaporates in reaction system is removed simultaneously, and stop heating, under the protection of nitrogen, filter while hot, the white crystal in reaction system is filtered out, filtrate rejoins reaction system, and the stirring intensity of reactor is 321rpm, add sublimed sulfur and deionization anaerobic water in formula, treat that temperature rises to 104 ℃, and the insulation 5.1h that refluxes under this temperature conditions, until in reaction system during without sublimed sulfur powder, stop reaction system heating, the temperature of reaction system is dropped to room temperature slowly simultaneously, now, in reaction system, separate out a small amount of light yellow or white pressed powder, light yellow or the white solid powder of separating out is filtered out from reaction system, and the filtrate of containing many lithium sulfides is stand-by,
By polyacrylonitrile resin micro mist powder and the diatomite in formula, the nmp solvent that adds again 28～33%wt/ diatomite electron level, under well-beaten condition, being uniformly mixed into viscosity is the viscose glue mud of 15430pa.s, after homogenizer fully mixes, be pressed into the thick thin slice of 330 μ m, and in thin slice pre-buried 130 μ m copper sheets; Moulding diatomite viscose glue mud is inserted in the high temperature furnace of 311 ℃, under the condition that is 0.088Mpa in negative pressure, process 23min, make diatomite sizing, then carefully extract copper sheet out; By extracting thin slice after copper sheet out and insert in the high temperature furnace of 1303 ℃, under the condition that is 0.098Mpa in negative pressure, process 86min, in the normal temperature air chamber of anhydrous steam, be cooled to normal temperature; To deviate from hydrogen, the oxygen atom on polyacrylonitrile resin strand; Making porosity is 82.3%, and aperture is the diatomite thin slice that 3.7um structure contains carborundum; Then thin slice is inserted containing in the nmp solution of many lithium sulfides 30%wt, after dipping 36min takes out, it is the high temperature furnace of 291 ℃ that the block diatomite that contains many lithium sulfides and nmp solvent is placed in to another temperature through nitrogen replacement 5 times, suitably extracting under the condition of the vacuum that negative pressure is 0.077Mpa, after processing time is 44min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, so just obtains flooding for the first time the diatomite thin slice of many lithium sulfides; Then in the nmp solution that thin slice to be inserted again to the purity that contains many lithium sulfides be 99.991%wt, dipping 29min, insert again another temperature through nitrogen replacement 5 times and be in the high temperature furnace of 274 ℃, suitably extracting under the condition of the vacuum that negative pressure is 0.090Mpa, after processing time is 35min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, so just obtains flooding for the second time the diatomite thin slice of many lithium sulfides; And then go out NMP through dipping and the high temperature evaporation of 4 times repeatedly, make the lithium sulfur battery anode material that contains many lithium sulfides 20.1%wt in block diatomite.
Embodiment 5
In the 316L of 1L stainless steel cauldron, constantly passing under the protection of 403ml/min nitrogen, add 7.1molNMP, 1.0mol NaHS and 1.003mol NaOH, under 179rpm stirring condition, slowly the temperature of reaction system is elevated to 88 ℃, add 0.4mol deionization anaerobic water simultaneously, then add 1.001mol lithium chloride, continue the temperature to 179 ℃ of rising reaction system, and under this temperature conditions, make reaction system insulation 32min, until while having tiny white crystal to separate out in reaction system, water evaporates in reaction system is removed simultaneously, and stop heating, under the protection of nitrogen, filter while hot, the white crystal in reaction system is filtered out, filtrate rejoins reaction system, and the stirring intensity of reactor is 316rpm, add sublimed sulfur and deionization anaerobic water in formula, treat that temperature rises to 109 ℃, and the insulation 5.4h that refluxes under this temperature conditions, until in reaction system during without sublimed sulfur powder, stop reaction system heating, the temperature of reaction system is dropped to room temperature slowly simultaneously, now, in reaction system, separate out a small amount of light yellow or white pressed powder, light yellow or the white solid powder of separating out is filtered out from reaction system, and the filtrate of containing many lithium sulfides is stand-by,
By polyacrylonitrile resin micro mist powder and the diatomite in formula, the nmp solvent that adds again 31%wt/ diatomite electron level, under well-beaten condition, being uniformly mixed into viscosity is the viscose glue mud of 16418pa.s, after homogenizer fully mixes, be pressed into the thick thin slice of 440 μ m, and in thin slice pre-buried 80～330 μ m copper sheets; Moulding diatomite viscose glue mud is inserted in the high temperature furnace of 348 ℃, under the condition that is 0.089Mpa in negative pressure, process 34min, make diatomite sizing, then carefully extract copper sheet out; By extracting thin slice after copper sheet out and insert in the high temperature furnace of 1367 ℃, under the condition that is 0.0993Mpa in negative pressure, process 86min, in the normal temperature air chamber of anhydrous steam, be cooled to normal temperature; To deviate from hydrogen, the oxygen atom on polyacrylonitrile resin strand; Making porosity is 83.8%, and aperture is the diatomite thin slice that 4.8um structure contains carborundum; Then thin slice is inserted containing in the nmp solution of many lithium sulfides 30%wt, after dipping 37min takes out, it is the high temperature furnace of 297 ℃ that the block diatomite that contains many lithium sulfides and nmp solvent is placed in to another temperature through nitrogen replacement 6 times, suitably extracting under the condition of the vacuum that negative pressure is 0.081Mpa, after processing time is 41min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, so just obtains flooding for the first time the diatomite thin slice of many lithium sulfides; Then in the nmp solution that thin slice to be inserted again to the purity that contains many lithium sulfides be 99.991%wt, dipping 30min, insert again another temperature through nitrogen replacement 6 times and be in the high temperature furnace of 277 ℃, suitably extracting under the condition of the vacuum that negative pressure is 0.090Mpa, after processing time is 34min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, so just obtains flooding for the second time the diatomite thin slice of many lithium sulfides; And then go out NMP through dipping and the high temperature evaporation of 3 times repeatedly, make the lithium sulfur battery anode material that contains many lithium sulfides 20.7%wt in block diatomite.
Embodiment 6
In the 316L of 1L stainless steel cauldron, constantly passing under the protection of 416ml/min nitrogen, add 7.8molNMP, 1.0mol NaHS and 1.003mol NaOH, under 181rpm stirring condition, slowly the temperature of reaction system is elevated to 86 ℃, add 0.4mol deionization anaerobic water simultaneously, then add 1.001mol lithium chloride, continue the temperature to 181 ℃ of rising reaction system, and under this temperature conditions, make reaction system insulation 29min, until while having tiny white crystal to separate out in reaction system, water evaporates in reaction system is removed simultaneously, and stop heating, under the protection of nitrogen, filter while hot, the white crystal in reaction system is filtered out, filtrate rejoins reaction system, and the stirring intensity of reactor is 321rpm, add sublimed sulfur and deionization anaerobic water in formula, treat that temperature rises to 111 ℃, and the insulation 4.8h that refluxes under this temperature conditions, until in reaction system during without sublimed sulfur powder, stop reaction system heating, the temperature of reaction system is dropped to room temperature slowly simultaneously, now, in reaction system, separate out a small amount of light yellow or white pressed powder, light yellow or the white solid powder of separating out is filtered out from reaction system, and the filtrate of containing many lithium sulfides is stand-by,
By polyacrylonitrile resin micro mist powder and the diatomite in formula, the nmp solvent that adds again 31%wt/ diatomite electron level, under well-beaten condition, being uniformly mixed into viscosity is the viscose glue mud of 16780pa.s, after homogenizer fully mixes, be pressed into the thick thin slice of 540 μ m, and in thin slice pre-buried 200 μ m copper sheets; Moulding diatomite viscose glue mud is inserted in the high temperature furnace of 341 ℃, under the condition that is 0.088Mpa in negative pressure, process 33min, make diatomite sizing, then carefully extract copper sheet out; By extracting thin slice after copper sheet out and insert in the high temperature furnace of 1345 ℃, under the condition that is 0.0999Mpa in negative pressure, process 86min, in the normal temperature air chamber of anhydrous steam, be cooled to normal temperature; To deviate from hydrogen, the oxygen atom on polyacrylonitrile resin strand; Making porosity is 84.3%, and aperture is the diatomite thin slice that 4.1um structure contains carborundum; Then thin slice is inserted containing in the nmp solution of many lithium sulfides 31%wt, after dipping 34min takes out, it is the high temperature furnace of 286 ℃ that the block diatomite that contains many lithium sulfides and nmp solvent is placed in to another temperature through nitrogen replacement 3 times, suitably extracting under the condition of the vacuum that negative pressure is 0.084Mpa, after processing time is 41min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, so just obtains flooding for the first time the diatomite thin slice of many lithium sulfides; Then in the nmp solution that thin slice to be inserted again to the purity that contains many lithium sulfides be 99.991%wt, dipping 26min, insert again another temperature through nitrogen replacement 4 times and be in the high temperature furnace of 274 ℃, suitably extracting under the condition of the vacuum that negative pressure is 0.091Mpa, after processing time 36min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, so just obtains flooding for the second time the diatomite thin slice of many lithium sulfides; And then go out NMP through dipping and the high temperature evaporation of 4 times repeatedly, make the lithium sulfur battery anode material that contains many lithium sulfides 20.6%wt in block diatomite.
Embodiment 7
In the 316L of 1L stainless steel cauldron, constantly passing under the protection of 431ml/min nitrogen, add 8.1molNMP, 1.0mol NaHS and 1.003mol NaOH, under 184rpm stirring condition, slowly the temperature of reaction system is elevated to 87 ℃, add 0.4mol deionization anaerobic water simultaneously, then add 1.001mol lithium chloride, continue the temperature to 184 ℃ of rising reaction system, and under this temperature conditions, make reaction system insulation 24min, until while having tiny white crystal to separate out in reaction system, water evaporates in reaction system is removed simultaneously, and stop heating, under the protection of nitrogen, filter while hot, the white crystal in reaction system is filtered out, filtrate rejoins reaction system, and the stirring intensity of reactor is 319rpm, add sublimed sulfur and deionization anaerobic water in formula, treat that temperature rises to 117 ℃, and the insulation 4.3h that refluxes under this temperature conditions, until in reaction system during without sublimed sulfur powder, stop reaction system heating, the temperature of reaction system is dropped to room temperature slowly simultaneously, now, in reaction system, separate out a small amount of light yellow or white pressed powder, light yellow or the white solid powder of separating out is filtered out from reaction system, and the filtrate of containing many lithium sulfides is stand-by,
By polyacrylonitrile resin micro mist powder and the diatomite in formula, the nmp solvent that adds again 32%wt/ diatomite electron level, under well-beaten condition, being uniformly mixed into viscosity is the viscose glue mud of 15670pa.s, after homogenizer fully mixes, be pressed into the thick thin slice of 660 μ m, and in thin slice pre-buried 260 μ m copper sheets; Moulding diatomite viscose glue mud is inserted in the high temperature furnace of 364 ℃, under the condition that is 0.090Mpa in negative pressure, process 29min, make diatomite sizing, then carefully extract copper sheet out; By extracting thin slice after copper sheet out and insert in the high temperature furnace of 1341 ℃, under the condition that is 0.0990Mpa in negative pressure, process 85min, in the normal temperature air chamber of anhydrous steam, be cooled to normal temperature; To deviate from hydrogen, the oxygen atom on polyacrylonitrile resin strand; Making porosity is 85.8%, and aperture is the diatomite thin slice that 4.4um structure contains carborundum; Then thin slice is inserted containing in the nmp solution of many lithium sulfides 32%wt, after dipping 34min takes out, it is the high temperature furnace of 294 ℃ that the block diatomite that contains many lithium sulfides and nmp solvent is placed in to another temperature through nitrogen replacement 3 times, suitably extracting under the condition of the vacuum that negative pressure is 0.085Mpa, after processing time is 45min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, so just obtains flooding for the first time the diatomite thin slice of many lithium sulfides; Then in the nmp solution that thin slice to be inserted again to the purity that contains many lithium sulfides be 99.991%wt, dipping 32min, insert again another temperature through nitrogen replacement 5 times and be in the high temperature furnace of 269 ℃, suitably extracting under the condition of the vacuum that negative pressure is 0.091Mpa, after processing time is 35min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, so just obtains flooding for the second time the diatomite thin slice of many lithium sulfides; And then go out NMP through dipping and the high temperature evaporation of 3 times repeatedly, make the lithium sulfur battery anode material that contains many lithium sulfides 19.90%wt in block diatomite.
Embodiment 8
In the 316L of 1L stainless steel cauldron, constantly passing under the protection of 454ml/min nitrogen, add 8.3molNMP, 1.0mol NaHS and 1.003mol NaOH, under 186rpm stirring condition, slowly the temperature of reaction system is elevated to 88 ℃, add 0.4mol deionization anaerobic water simultaneously, then add 1.001mol lithium chloride, continue the temperature to 186 ℃ of rising reaction system, and under this temperature conditions, make reaction system insulation 31min, until while having tiny white crystal to separate out in reaction system, water evaporates in reaction system is removed simultaneously, and stop heating, under the protection of nitrogen, filter while hot, the white crystal in reaction system is filtered out, filtrate rejoins reaction system, and the stirring intensity of reactor is 314rpm, add sublimed sulfur and deionization anaerobic water in formula, treat that temperature rises to 114 ℃, and the insulation 4.4h that refluxes under this temperature conditions, until in reaction system during without sublimed sulfur powder, stop reaction system heating, the temperature of reaction system is dropped to room temperature slowly simultaneously, now, in reaction system, separate out a small amount of light yellow or white pressed powder, light yellow or the white solid powder of separating out is filtered out from reaction system, and the filtrate of containing many lithium sulfides is stand-by,
By polyacrylonitrile resin micro mist powder and the diatomite in formula, the nmp solvent that adds again 30.5%wt/ diatomite electron level, under well-beaten condition, being uniformly mixed into viscosity is the viscose glue mud of 16830pa.s, after homogenizer fully mixes, be pressed into the thick thin slice of 740 μ m, and in thin slice pre-buried 260 μ m copper sheets; Moulding diatomite viscose glue mud is inserted in the high temperature furnace of 369 ℃, under the condition that is 0.090Mpa in negative pressure, process 37min, make diatomite sizing, then carefully extract copper sheet out; By extracting thin slice after copper sheet out and insert in the high temperature furnace of 1373 ℃, under the condition that is 0.0994Mpa in negative pressure, process 87min, in the normal temperature air chamber of anhydrous steam, be cooled to normal temperature; To deviate from hydrogen, the oxygen atom on polyacrylonitrile resin strand; Making porosity is 86.8%, and aperture is the diatomite thin slice that 4.6um structure contains carborundum; Then thin slice is inserted containing in the nmp solution of many lithium sulfides 31.3%wt, after dipping 37min takes out, it is the high temperature furnace of 297 ℃ that the block diatomite that contains many lithium sulfides and nmp solvent is placed in to another temperature through nitrogen replacement 5 times, suitably extracting under the condition of the vacuum that negative pressure is 0.086Mpa, after processing time is 39min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, so just obtains flooding for the first time the diatomite thin slice of many lithium sulfides; Then in the nmp solution that thin slice to be inserted again to the purity that contains many lithium sulfides be 99.991%wt, dipping 31min, insert again another temperature through nitrogen replacement 6 times and be in the high temperature furnace of 278 ℃, suitably extracting under the condition of the vacuum that negative pressure is 0.088Mpa, after processing time is 36min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, so just obtains flooding for the second time the diatomite thin slice of many lithium sulfides; And then go out NMP through dipping and the high temperature evaporation of 4 times repeatedly, make the lithium sulfur battery anode material that contains many lithium sulfides 20.9%wt in block diatomite.
Embodiment 9
In the 316L of 1L stainless steel cauldron, constantly passing under the protection of 474ml/min nitrogen, add 8.6molNMP, 1.0mol NaHS and 1.003mol NaOH, under 188rpm stirring condition, slowly the temperature of reaction system is elevated to 88 ℃, add 0.4mol deionization anaerobic water simultaneously, then add 1.001mol lithium chloride, continue the temperature to 188 ℃ of rising reaction system, and under this temperature conditions, make reaction system insulation 33min, until while having tiny white crystal to separate out in reaction system, water evaporates in reaction system is removed simultaneously, and stop heating, under the protection of nitrogen, filter while hot, the white crystal in reaction system is filtered out, filtrate rejoins reaction system, and the stirring intensity of reactor is 330rpm, add sublimed sulfur and deionization anaerobic water in formula, treat that temperature rises to 88～118 ℃, and the insulation 6h that refluxes under this temperature conditions, until in reaction system during without sublimed sulfur powder, stop reaction system heating, the temperature of reaction system is dropped to room temperature slowly simultaneously, now, in reaction system, separate out a small amount of light yellow or white pressed powder, light yellow or the white solid powder of separating out is filtered out from reaction system, and the filtrate of containing many lithium sulfides is stand-by,
By polyacrylonitrile resin micro mist powder and the diatomite in formula, the nmp solvent that adds again 33%wt/ diatomite electron level, under well-beaten condition, being uniformly mixed into viscosity is the viscose glue mud of 19600pa.s, after homogenizer fully mixes, be pressed into the thick thin slice of 790 μ m, and in thin slice pre-buried 310 μ m copper sheets; Moulding diatomite viscose glue mud is inserted in the high temperature furnace of 379 ℃, under the condition that is 0.091Mpa in negative pressure, process 38min, make diatomite sizing, then carefully extract copper sheet out; By extracting thin slice after copper sheet out and insert in the high temperature furnace of 1377 ℃, under the condition that is 0.0999Mpa in negative pressure, process 88min, in the normal temperature air chamber of anhydrous steam, be cooled to normal temperature; To deviate from hydrogen, the oxygen atom on polyacrylonitrile resin strand; Making porosity is 87.4%, and aperture is the diatomite thin slice that 4.8um structure contains carborundum; Then thin slice is inserted containing in the nmp solution of many lithium sulfides 31%wt, after dipping 38min takes out, it is the high temperature furnace of 300 ℃ that the block diatomite that contains many lithium sulfides and nmp solvent is placed in to another temperature through nitrogen replacement 3 times, suitably extracting under the condition of the vacuum that negative pressure is 0.088Mpa, after processing time is 36min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, so just obtains flooding for the first time the diatomite thin slice of many lithium sulfides; Then in the nmp solution that thin slice to be inserted again to the purity that contains many lithium sulfides be 99.991%wt, dipping 33min, insert again another temperature through nitrogen replacement 6 times and be in the high temperature furnace of 281 ℃, suitably extracting under the condition of the vacuum that negative pressure is 0.091Mpa, after processing time is 36min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, so just obtains flooding for the second time the diatomite thin slice of many lithium sulfides; And then go out NMP through dipping and the high temperature evaporation of 4 times repeatedly, make the lithium sulfur battery anode material that contains many lithium sulfides 20.8%wt in block diatomite.
Claims (3)
1. the manufacture method of a lithium sulfur battery anode material, it is characterized in that, by polyacrylonitrile resin micro mist and diatomite with mass ratio 38～41:62～59, add in mixed at high speed blender, add again the diatomaceous nmp solvent of 28～33%wt/, under well-beaten condition, being uniformly mixed into viscosity is the viscose glue mud of 13800～19600pa.s, then by viscose glue mud according to the bulk material that need to be made into respective shapes of lithium sulfur battery anode material, bulk material is placed in to the high temperature furnace through nitrogen replacement, under the condition of suitable extracting vacuum, make block viscose glue mud become the block diatomite that only contains carborundum composition, then be placed on containing in the nmp solution of many lithium sulfide 28～33%wt, dipping 33～38min, after taking-up, the block diatomite that contains many lithium sulfides and nmp solvent is placed in to the high temperature furnace through nitrogen replacement, under the condition of suitable extracting vacuum, nmp solvent in block diatomite is fully evaporated, and the dipping of 3～6 times and high temperature evaporation go out NMP so repeatedly, make the lithium sulfur battery anode material that contains many lithium sulfide 18～21%wt in block diatomite.
2. the manufacture method of lithium sulfur battery anode material according to claim 1, is characterized in that, comprises following concrete manufacturing process:
1) in the 316L of 1L stainless steel cauldron, constantly passing under the protection of 360～480ml/min nitrogen, add 5.4～8.8molNMP, 1.0mol NaHS and 1.003mol NaOH, under 160～190rpm stirring condition, slowly the temperature of reaction system is elevated to 86～88 ℃, add 0.4mol deionization anaerobic water simultaneously, then add 1.001mol lithium chloride, continue temperature to 170～190 ℃ of rising reaction system, and under this temperature conditions, make reaction system insulation 18～33min, until while having tiny white crystal to separate out in reaction system, water evaporates in reaction system is removed simultaneously, and stop heating,
2) by 1) the anhydrous response system that obtains is under the protection of nitrogen, filter while hot, white crystal in reaction system is filtered out, filtrate rejoins reaction system, add sublimed sulfur and deionization anaerobic water in formula, treat that temperature rises to 88～118 ℃, and the insulation 4～6h that refluxes under this temperature conditions, until in reaction system during without sublimed sulfur powder, stop reaction system heating, the temperature of reaction system is dropped to room temperature slowly simultaneously, now, in reaction system, separate out a small amount of light yellow or white pressed powder; Wherein the stirring intensity of reactor is 280～330rpm;
3) by 2) the light yellow or white solid powder of separating out filters out from reaction system, and the filtrate of containing many lithium sulfides is stand-by;
4), by polyacrylonitrile resin micro mist powder and diatomite in formula, add again the diatomaceous nmp solvent of 28～33%wt/, under well-beaten condition, being uniformly mixed into viscosity is the viscose glue mud of 13800～19600pa.s, after homogenizer fully mixes, be pressed into the thick thin slice of 180～810 μ m, and in thin slice pre-buried 80～330 μ m copper sheets;
5) by 4) the moulding diatomite viscose glue mud that obtains inserts in the high temperature furnace of 280～380 ℃, under the condition that is 0.088～0.091Mpa, processes 16～38min in negative pressure, makes diatomite sizing, then carefully extracts copper sheet out;
6), by 5) gained thin slice inserts in the high temperature furnace of 1280～1380 ℃, under the condition that is 0.098～0.0999Mpa, processes 81～88min in negative pressure, in the normal temperature air chamber of anhydrous steam, is cooled to normal temperature; To deviate from hydrogen, the oxygen atom on polyacrylonitrile resin strand; Making porosity is 81～88%, and aperture is the diatomite thin slice that 3～5um structure contains carborundum;
7), by 6) thin slice that obtains inserts 3) containing in the nmp solution of many lithium sulfide 28～33%wt, through flooding after 33～38min taking-up, it is the high temperature furnace of 280～300 ℃ that the block diatomite that contains many lithium sulfides and nmp solvent is placed in to another temperature through nitrogen replacement 3～6 times, suitably extracting under the condition of the vacuum that negative pressure is 0.068～0.088Mpa, after processing time is 36～48min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, so just obtains flooding for the first time the diatomite thin slice of many lithium sulfides;
8) by 7) thin slice that obtains inserts in the nmp solution that contains many lithium sulfides again, dipping 18～33min, insert again another temperature through nitrogen replacement 3～6 times and be in the high temperature furnace of 260～281 ℃, suitably extracting under the condition of the vacuum that negative pressure is 0.088～0.091Mpa, after processing time is 33～36min, normal temperature air chamber through anhydrous steam is cooled to normal temperature, so just obtains flooding for the second time the diatomite thin slice of many lithium sulfides;
9) by 8) thin slice that obtains adopts 8) process conditions in step, through dipping and the high temperature evaporation of 2～4 times repeatedly, go out NMP, make the lithium sulfur battery anode material that contains many lithium sulfide 18～21%wt in block diatomite.
3. a kind of manufacture method of lithium sulfur battery anode material according to claim 1, is characterized in that, the purity of the many lithium sulfides that adopt is 99.991%wt, the 1-METHYLPYRROLIDONE that NMP is electron level.
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| CN106784999B (en) * | 2017-02-13 | 2019-04-09 | 桂林电器科学研究院有限公司 | A kind of lithium sulfide system solid electrolyte material and preparation method thereof of addition Li-Si alloy and silver-colored halogen compound |
| CN108346818A (en) * | 2018-01-19 | 2018-07-31 | 王顺良 | A kind of preparation method of the conductor cladding compound sodium-ion battery anode of sulphur |
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