CN105374999A - Preparation method of sulfur-containing electrode material - Google Patents
Preparation method of sulfur-containing electrode material Download PDFInfo
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- CN105374999A CN105374999A CN201510675236.XA CN201510675236A CN105374999A CN 105374999 A CN105374999 A CN 105374999A CN 201510675236 A CN201510675236 A CN 201510675236A CN 105374999 A CN105374999 A CN 105374999A
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the field of lithium sulfur batteries, and particularly relates to a preparation method of a sulfur-containing electrode material. The preparation method comprises the following four steps: preparation of a sulfur-containing precursor, filling of the precursor, loading of a sulfur-containing component and drying of the sulfur-containing component. The preparation method comprises the following steps: firstly preparing a saturated solution of sulfur at the temperature of T1, then mixing with a porous component at the temperature of T2 (which is greater than or equal to T1), soaking the pore structure of the porous base material in the solution, then cooling the temperature to T3 (which is smaller than T1) so that the sulfur in the saturated solution is automatically separated out and at that time the separated sulfur becomes into nano-particles deposited in the pore structure of the porous base material by controlling the temperature and increasing disturbance to realize the filling of the pore structure of the porous base material through the sulfur-containing component; and then filtering to remove unnecessary solution, and drying to obtain a sulfur-carbon compound. In the process, the viscosity of the sulfur-containing component dissolved in the solvent is relatively low, the sulfur-containing component can easily permeate and enter the pore structure of the porous base material, so that deep micropores of the porous base material can be sufficiently filled; and therefore, the sulfur content of the obtained material is relatively high, and the capacity of a correspondingly obtained battery is relatively high.
Description
Technical field
The invention belongs to lithium-sulfur cell field, particularly relate to a kind of preparation method of sulfur-bearing electrode material.
Background technology
Since 1991, material with carbon element is creationary applies to field of lithium ion battery, and bringing the revolutionary change in this field, namely efficient and the carrying out of safety is repeatedly after discharge and recharge, and it is just applied on mobile phone, video camera, notebook computer and other portable electronics widely.Compared with traditional plumbic acid, Ni-Cd, MH-Ni battery, lithium ion battery has higher specific volume energy density, weight/power ratio energy density, better environment friendly, less self discharge and longer cycle life etc., is 21st century desirable movable electrical appliances power supply, electric car power supply and electricity storage station electrical storage device.
But the new demand that along with the raising of sampling of living, people propose gentlier mobile electrical appliance, thinner, less, more lasting, price is lower, just new requirement is proposed to the power supply device of these equipment accordingly; Energy density is higher, low price; This wherein power supply device (battery) energy density and Consumer's Experience closely bound up, enjoy the concern of consumers in general, and the method that present stage improves battery energy density mainly concentrates on the new positive/negative material of exploitation, the positive electrode of development of new is particularly remarkable to battery energy density lifting effect.
Current commercial positive electrode is the lithium transition-metal oxide (as cobalt acid lithium, LiMn2O4) of stratiform or spinel structure and the LiFePO4 etc. of olivine structural mainly.Cobalt acid lithium (LiCoO
2) theoretical capacity relatively large (275mAh/g), but actual discharge capacity only about 160mAh/g, and its price is high, there is certain toxicity, and this positive electrode easily exothermal decomposition reactions occurring when overcharging, not only making battery capacity obviously decline, cell safety also being threatened simultaneously.LiMn2O4 (LiMn
2o
4) theoretical capacity be 148mAh/g, actual capacity is lower than 130mAh/g, and its compacted density is not high, and energy density is low, poor stability, in charge and discharge process, easily cause lattice deformability, causes cycle efficieny on the low side.LiFePO4 (LiFePO
4) theoretical capacity be 172mAh/g, but this positive electrode compacted density is low, and the battery core energy density prepared is corresponding less.Above-mentioned conventional anode material for lithium-ion batteries capacity is general not high, all there are some problems simultaneously yet, can not meet battery development requirement.
The theoretical specific capacity of elemental sulfur is 1675mAh/g, the theoretical specific capacity of the positive electrode used higher than current business far away, becomes the main trend of present battery development.But elemental sulfur itself is also non-conductive, just must can make electrode with conductive materials compound, and due to the introducing of the conductive agent as conductive component, the content of sulphur in positive pole coating can be caused to reduce significantly, thus reduce the energy density of lithium-sulfur cell; Lithium-sulfur cell is in charge and discharge process simultaneously, elemental sulfur can be converted into polysulfide, and polysulfide can be dissolved in liquid organic solution liquid, cause the loss of active material in cyclic process, more seriously, the sulfide dissolved will be separated out at negative pole and be formed dendrite, have the risk piercing through barrier film greatly, thus cause the fail safe extreme difference of battery.
In view of this, the necessary preparation method developing a kind of new sulfur-bearing electrode material, it can not only improve the ratio of sulphur in positive electrode, can also obtain positive electrode lithium sulfide to stronger adsorption capacity.
Summary of the invention
The object of the invention is to: for the deficiencies in the prior art, and a kind of preparation method of sulfur-bearing electrode material is provided: comprise the preparation of sulfur-bearing presoma, the filling of presoma, sulfur component load and dry four steps.First the saturated solution of sulphur at T1 temperature is prepared, be that the porous component of T2 (T2 >=T1) mixes afterwards with temperature, solution is allowed to immerse in the pore structure of porous substrate, cool to T3 (T3<T1) afterwards, sulphur then in saturated solution will be separated out automatically, now by control temperature and increase disturbance, make the sulphur of separating out become nano particle to fill and be deposited in the pore structure of porous substrate, realize the filling of sulfur component to porous substrate pore structure; Filter afterwards and remove redundant solution, after drying, namely obtain sulphur carbon complex.In above process, the sulfur component viscosity be dissolved in solvent is lower, can penetrate in the pore structure of porous substrate easily, therefore fully can fill the micropore of porous substrate profound level, therefore obtained material sulfur content is higher, and the corresponding battery capacity obtained is larger; Meanwhile, deep layer micropore has stronger adsorption capacity to lithium sulfide, and therefore electrode material has better cycle performance and lower self-discharge performance.
To achieve these goals, the present invention adopts following technical scheme:
A preparation method for sulfur-bearing electrode material, mainly comprises the steps:
Step 1, the preparation of sulfur-bearing presoma: be in the container of T1 in temperature, sulfur component and solvent is even, obtain sulfur-bearing presoma stand-by;
Step 2, the filling of presoma: presoma step 1 obtained and porous substrate are placed in same reactor, keeps presoma temperature T2, sulfur-bearing presoma is fully filled and enters in the pore space structure of porous substrate; In order to strengthen the power that presoma permeates in porous substrate pore structure further, can before presoma mixes with porous substrate, presoma is placed in the environment being less than or equal to 3kpa and is more than or equal to 10s process, the gas component in as far as possible many discharge porous substrate pore structures;
Step 3, sulfur component load: reduction is fully filled with the temperature of sulfur-bearing presoma porous substrate to T3, the sulfur component in presoma is separated out, and is filled in porous substrate pore space structure.
One as sulfur-bearing electrode material preparation method of the present invention is improved, and T1≤T2 is or/and T3≤T1.The saturated solution of sulphur at preparation T1 temperature, be that the porous component of T2 (T2 >=T1) mixes afterwards with temperature, solution is allowed to immerse in the pore structure of porous substrate, cool to T3 (T3<T1) afterwards, sulphur then in saturated solution will be separated out automatically, now by control temperature and increase disturbance, make the sulphur of separating out become nano particle to fill and be deposited in the pore structure of porous substrate, realize the filling of sulfur component to porous substrate pore structure; Filter afterwards and remove redundant solution, after drying, namely obtain sulphur carbon complex.In above process, the sulfur component viscosity be dissolved in solvent is lower, can penetrate in the pore structure of porous substrate easily, therefore fully can fill the micropore of porous substrate profound level, therefore obtained material sulfur content is higher, and the corresponding battery capacity obtained is larger; Meanwhile, deep layer micropore has stronger adsorption capacity to lithium sulfide, and therefore electrode material has better cycle performance and lower self-discharge performance.
One as sulfur-bearing electrode material preparation method of the present invention is improved, and sulfur component described in step 1 comprises at least one in sulphur simple substance, sulfur-based compound and sulfur compound; Described porous substrate comprises at least one in porous carbon materials, functionalized porous's material with carbon element, metal porous base material and functionalize metal's porous substrate, and described sulfur-bearing presoma is under temperature T1, the saturated solution of sulfur component.
One as sulfur-bearing electrode material preparation method of the present invention is improved, and described sulphur simple substance comprises sublimed sulfur and/or high purity sulphur; Described sulfur-based compound includes machine sulfide, Li2Sn and carbon-sulfur polymer (C
2s
v)
min at least one, wherein, n>=1,1≤v≤8,1≤m; Described sulfur compound comprises at least one in sulphur/carbon complex, sulphur/conductive polymer composite and sulphur/inorganic oxide, described conducting polymer is polyaniline, polypyrrole, polythiophene, polyacetylene etc., and inorganic oxide comprises aluminium oxide, silica, zirconia etc.; The particle diameter of described porous substrate is 5nm ~ 200 μm, and bore dia is 0.2nm ~ 2 μm, and porosity is 30% ~ 98%.
One as sulfur-bearing electrode material preparation method of the present invention is improved, described solvent be organic solvent or/and inorganic solvent, preparing the presoma that obtains is the saturated solution of sulfur component at T1 temperature.
One as sulfur-bearing electrode material preparation method of the present invention is improved, and described organic solvent comprises at least one class in arene, fat hydrocarbon, alicyclic hydrocarbon type, halogenated hydrocarbons, alcohols, ethers, ester class, ketone and diol, derivatives; Arene: benzene,toluene,xylene etc.; Fat hydrocarbon: pentane, hexane, octane etc.; Alicyclic hydrocarbon type: cyclohexane, cyclohexanone, toluene cyclohexanone etc.; Halogenated hydrocarbons: carbon tetrachloride, chlorobenzene, dichloro-benzenes, carrene etc.; Alcohols: methyl alcohol, ethanol, isopropyl alcohol etc.; Ethers: ether, expoxy propane etc.; Ester class: methyl acetate, ethyl acetate, propyl acetate etc.; Ketone: acetone, espeleton, methylisobutylketone etc.; Diol, derivatives: glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether etc.; Other: acetonitrile, pyridine, phenol etc., described inorganic solvent comprises at least one in water, inorganic acid, carbon disulfide, liquefied ammonia, liquid carbon dioxide, liquid nitrogen and liquid sulfur dioxide.
One as sulfur-bearing electrode material preparation method of the present invention is improved, in step 1, also surfactant is added with in described sulfur-bearing presoma, the addition of described surfactant is 0.01% ~ 20% of the quality of described sulfur-bearing presoma, the surfactant decomposed or gasification temperature is lower can be selected, reaction to be filled removes surfactant by heat treatment process after introducing, thus makes in final finished electrode material not containing surface active agent composition; Described surfactant comprises at least one in wetting agent, dispersant, bleeding agent, solubilizer, cosolvent and cosolvent; Described wetting agent is that anionic is or/and non-ionic wetting agent; Described dispersant is at least one class in fatty acid/aliphatic amide type/ester class, paraffin class, metal soap, low-molecular-weight wax class and HPMA; Described bleeding agent is that nonionic is or/and anionic bleeding agent.(described anionic wetting agents comprises at least one in alkyl sulfate, sulfonate, aliphatic acid or fatty acid ester sulfate, carboxylic soap class and phosphate; Described non-ionic wetting agent comprises at least one in polyvinylpyrrolidone, polyoxyethylated alkyl phenol, polyoxyethylene aliphatic alcohol ether and polyoxyethylene polyoxypropylene block copolymer; Described dispersant is at least one in vinyl bis-stearamides, oleic acid acyl, glyceryl monostearate, glyceryl tristearate, atoleine, microcrystalline wax, barium stearate, zinc stearate, calcium stearate, Tissuemat E and polyethylene glycol; Described nonionic penetrant comprises at least one in JFC (AEO), JFC-1 (APES), JFC-2 (polyoxyethylene ether compound), JFC-E (AEO); Described anionic bleeding agent comprises at least one in fast penetrant T (aerosol-OT salt), alkali-resistant penetrant AEP (aliphatic acid and ethylene oxide condensate) and seeping at high temperature agent JFC-M (polyoxyethylene ether compound); Described cosolvent comprises at least one in benzoic acid, Sodium Benzoate, salicylic acid, sodium salicylate, p-aminobenzoic acid, urethane, urea, acid amides, acetamide, borax and KI; Described cosolvent comprises at least one in ethanol, glycerine, propylene glycol and polyethylene glycol.)
One as sulfur-bearing electrode material preparation method of the present invention is improved, and in the filling process of the sulfur-bearing presoma described in step 2, applies ultrasonic process to mixed sulfur-bearing presoma or porous substrate; Or/and in loading process described in step 3, to at least one process applied in reactor in ultrasonic process, stirring and ball milling, when there being disturbance, the sulfur component particle size being filled in the presoma recrystallization precipitation in porous substrate pore structure can be less, easily obtain nanometer sulfur component granular deposit, and then be filled in pore structure.
One as sulfur-bearing electrode material preparation method of the present invention is improved; in the filling process of the sulfur-bearing presoma described in step 2; when molten sulfur fully infiltrates pretreated porous substrate; in reactor, pass into protective gas (as inert gas, nitrogen etc.), the air pressure after ventilation is less than or equal to 100MPa.
The present invention also comprises a kind of sulfur-bearing electrode material, this electrode material is prepared by method of the present invention, and be made up of porous substrate and the sulfur component be filled in described porous substrate, described sulfur component is nano particle, and the ratio that the quality of described sulfur component accounts for the quality of whole electrode material is 30% ~ 98%.
Beneficial effect of the present invention is: the saturated solution first preparing sulphur at T1 temperature, be that the porous component of T2 (T2 >=T1) mixes afterwards with temperature, solution is allowed to immerse in the pore structure of porous substrate, cool to T3 (T3<T1) afterwards, sulphur then in saturated solution will be separated out automatically, now by control temperature and increase disturbance, make the sulphur of separating out be that Nanoparticulate is deposited in the pore structure of porous substrate, realize the filling of sulfur component to porous substrate pore structure; Filter afterwards and remove redundant solution, after drying, namely obtain sulphur carbon complex.In above process, the sulfur component viscosity be dissolved in solvent is lower, can penetrate in the pore structure of porous substrate easily, therefore fully can fill the micropore of porous substrate profound level, therefore obtained material sulfur content is higher, and the corresponding battery capacity obtained is larger; Meanwhile, deep layer micropore has stronger adsorption capacity to lithium sulfide, and therefore electrode material has better cycle performance and lower self-discharge performance.
Embodiment
Below in conjunction with embodiment, the present invention and beneficial effect thereof are described in detail, but embodiments of the present invention are not limited thereto.
comparative exampleselect particle diameter 10 μm ~ 20 μm, aperture is 10nm ~ 50nm, porosity is that the porous carbon materials of 80% is as base material, mix with sulphur simple substance afterwards (mass ratio is 3:7), then be placed in 170 DEG C of environment and calcine 2h, being cooled to room temperature afterwards, to obtain sulphur carbon composite stand-by;
embodiment 1, be with comparative example difference, the present embodiment comprises the steps:
The preparation of sulfur-bearing presoma: at 40 DEG C, by sulphur simple substance, that carbon disulfide mixes the carbon disulfide saturated solution obtaining sulphur is stand-by;
Sulphur-containing solution is filled: select particle diameter 10 μm ~ 20 μm, aperture is 10nm ~ 50nm, porosity is that the porous carbon materials of 80% is as base material; In 45 DEG C of environment, above-mentioned solution is fully mixed with porous carbon base material, make solution constantly permeate in the pore structure immersing base material; Afterwards 10MPa nitrogen pressure is applied to material, dwell time 1min, obtain porous substrate pore structure completely by material that solution is filled;
The load of sulfur component: the material being filled with solution is cooled to 30 DEG C, applies ultrasonic wave process to material simultaneously, the sulfur component in supersaturated solution is separated out gradually in nanoparticle deposition in porous substrate pore structure;
Dry: above-mentioned material is filtered, be placed on 80 DEG C at vacuumize, obtain sulfur-bearing electrode material.
All the other are identical with comparative example, repeat no more.
embodiment 2, as different from Example 1, the present embodiment comprises the steps:
The preparation of sulfur-bearing presoma: at 10 DEG C, by sulphur simple substance, that carbon disulfide mixes the carbon disulfide saturated solution obtaining sulphur is stand-by;
Sulphur-containing solution is filled: select particle diameter 10 μm ~ 20 μm, aperture is 10nm ~ 50nm, porosity is that the porous carbon materials of 80% is as base material; In 30 DEG C of environment, above-mentioned solution is fully mixed with porous carbon base material, make solution constantly permeate in the pore structure immersing base material; Apply 10MPa nitrogen pressure to material afterwards, dwell time 1min, obtains porous substrate pore structure and is filled by solution completely;
Sulfur component load: the material being filled with solution is cooled to-10 DEG C, applies ultrasonic wave process to material simultaneously, makes the sulfur component in supersaturated solution separate out into nanoparticle deposition gradually in porous substrate pore structure;
Dry: above-mentioned material is filtered, be placed on 80 DEG C at vacuumize, obtain sulfur-bearing electrode material.
Other is identical with embodiment 1, no longer repeats here.
embodiment 3, as different from Example 1, the present embodiment comprises the steps:
The preparation of sulfur-bearing presoma: at 80 DEG C, by sulphur simple substance, that benzene mixes the benzene saturated solution obtaining sulphur is stand-by;
Sulphur-containing solution is filled: select particle diameter 10 μm ~ 20 μm, aperture is 10nm ~ 50nm, porosity is that the porous carbon materials of 80% is as base material; In 80 DEG C of environment, above-mentioned solution is fully mixed with porous carbon base material, make solution constantly permeate in the pore structure immersing base material; Apply 10MPa nitrogen pressure to material afterwards, dwell time 1min, obtains porous substrate pore structure and is filled by solution completely;
Sulfur component load: the material being filled with solution is cooled to 20 DEG C, applies ultrasonic wave process to material simultaneously, makes the sulfur component in supersaturated solution separate out into nanoparticle deposition gradually in porous substrate pore structure;
Dry: above-mentioned material is filtered, be placed on 80 DEG C at vacuumize, obtain sulfur-bearing electrode material.
Other is identical with embodiment 1, no longer repeats here.
embodiment 4, as different from Example 1, the present embodiment comprises the steps:
The preparation of sulfur-bearing presoma: at 70 DEG C, by sulphur simple substance, that carbon tetrachloride mixes the carbon tetrachloride saturated solution obtaining sulphur is stand-by;
Sulphur-containing solution is filled: select particle diameter 10 μm ~ 20 μm, aperture is 10nm ~ 50nm, porosity is that the porous carbon materials of 80% is as base material; In 75 DEG C of environment, above-mentioned solution is fully mixed with porous carbon base material, make solution constantly permeate in the pore structure immersing base material; Apply 10MPa nitrogen pressure to material afterwards, dwell time 1min, obtains porous substrate pore structure and is filled by solution completely;
Sulfur component load: the material being filled with solution is cooled to 120 DEG C, applies ultrasonic wave process to material simultaneously, makes the sulfur component in supersaturated solution separate out into nanoparticle deposition gradually in porous substrate pore structure;
Dry: above-mentioned material is filtered, be placed on 20 DEG C at vacuumize, obtain sulfur-bearing electrode material.
Other is identical with embodiment 1, no longer repeats here.
embodiment 5, as different from Example 1, the present embodiment comprises the steps:
The preparation of sulfur-bearing presoma: at 40 DEG C, by sulphur simple substance, sulphur carbon complex, carbon disulfide, that AEO (3) sulfosuccinic acid monoesters disodium MES (for 0.01% of solution quality) mixes the carbon disulfide saturated solution obtaining sulphur is stand-by;
Sulphur-containing solution is filled: select that particle diameter is 0.2nm ~ 1nm in 5nm ~ 10nm, aperture, porosity be the porous carbon materials of 30% as base material, be placed on afterwards in the environment of 3kpa and leave standstill 30min, the gas component in tap structure; In 45 DEG C of environment, above-mentioned solution is fully mixed with porous carbon base material, make solution constantly permeate in the pore structure immersing base material; Apply 100MPa nitrogen pressure to material afterwards, dwell time 30s, obtains porous substrate pore structure and is filled by solution completely;
Sulfur component load: the material being filled with solution is cooled to 10 DEG C, applies ultrasonic wave process to material simultaneously, makes the sulfur component in supersaturated solution separate out into nanoparticle deposition gradually in porous substrate pore structure;
Dry: above-mentioned material is filtered, be placed on 70 DEG C at vacuumize, obtain sulfur-bearing electrode material.
Other is identical with embodiment 1, no longer repeats here.
embodiment 6, as different from Example 1, the present embodiment comprises the steps:
The preparation of sulfur-bearing presoma: at 40 DEG C, by sulphur simple substance, sulphur carbon complex, carbon disulfide, that single Tryfac 5573 MAP (for 1% of solution quality) mixes the carbon disulfide saturated solution obtaining sulphur is stand-by;
Sulphur-containing solution is filled: select particle diameter 150 μm ~ 200 μm, aperture is 1 μm ~ 2 μm, porosity be the porous carbon materials of 60% as base material, be placed on afterwards in the environment of 300pa and leave standstill 3min, the gas component in tap structure; In 45 DEG C of environment, above-mentioned solution is fully mixed with porous carbon base material, make solution constantly permeate in the pore structure immersing base material; Apply 1MPa nitrogen pressure to material afterwards, dwell time 3h, obtains porous substrate pore structure and is filled by solution completely;
Sulfur component load: the material being filled with solution is cooled to 10 DEG C, applies ultrasonic wave process to material simultaneously, makes the sulfur component in supersaturated solution separate out into nanoparticle deposition gradually in porous substrate pore structure;
Dry: above-mentioned material is filtered, be placed on 70 DEG C at vacuumize, obtain sulfur-bearing electrode material.
embodiment 7, as different from Example 1, the present embodiment comprises the steps:
The preparation of sulfur-bearing presoma: at 40 DEG C, by sulphur simple substance, sulphur carbon complex, carbon disulfide, that lauryl sodium sulfate (for 20% of solution quality) mixes the carbon disulfide saturated solution obtaining sulphur is stand-by;
Sulphur-containing solution is filled: select particle diameter 5 μm ~ 10 μm, aperture is 5nm ~ 20nm, porosity be the porous carbon materials of 98% as base material, be placed on afterwards in the environment of 1pa and leave standstill 10s, the gas component in tap structure; In 45 DEG C of environment, above-mentioned solution is fully mixed with porous carbon base material, make solution constantly permeate in the pore structure immersing base material; Apply 10MPa nitrogen pressure to material afterwards, dwell time 10min, obtains porous substrate pore structure and is filled by solution completely;
Sulfur component load: the material being filled with solution is cooled to 10 DEG C, applies ultrasonic wave process to material simultaneously, makes the sulfur component in supersaturated solution separate out into nanoparticle deposition gradually in porous substrate pore structure;
Dry: above-mentioned material is filtered, be placed on 70 DEG C at vacuumize, obtain sulfur-bearing electrode material.
Other is identical with embodiment 1, no longer repeats here.
embodiment 8, as different from Example 1, the present embodiment comprises the steps:
The preparation of sulfur-bearing presoma: at 40 DEG C, by sulphur simple substance, that carbon disulfide mixes the carbon disulfide saturated solution obtaining sulphur is stand-by;
Sulphur-containing solution is filled: select particle diameter 10 μm ~ 20 μm, aperture is 10nm ~ 50nm, porosity is that the modified porous material with carbon element of 80% is as base material; In 45 DEG C of environment, above-mentioned solution is fully mixed with modified porous carbon substrate, make solution constantly permeate in the pore structure immersing base material; Apply 10MPa nitrogen pressure to material afterwards, dwell time 1min, obtains porous substrate pore structure and is filled by solution completely;
Sulfur component load: the material being filled with solution is cooled to 30 DEG C, applies stir process to material simultaneously, makes the sulfur component in supersaturated solution separate out into nanoparticle deposition gradually in porous substrate pore structure;
Dry: above-mentioned material is filtered, be placed on 80 DEG C at vacuumize, obtain sulfur-bearing electrode material.
Other is identical with embodiment 1, no longer repeats here.
embodiment 9, as different from Example 1, the present embodiment comprises the steps:
The preparation of sulfur-bearing presoma: at 40 DEG C, by sulphur simple substance, that carbon disulfide mixes the carbon disulfide saturated solution obtaining sulphur is stand-by;
Sulphur-containing solution is filled: select particle diameter 10 μm ~ 20 μm, aperture is 10nm ~ 50nm, porosity is that the porous aluminum material of 80% is as base material; In 45 DEG C of environment, above-mentioned solution is fully mixed with porous aluminum base material, make solution constantly permeate in the pore structure immersing base material; Apply 10MPa nitrogen pressure to material afterwards, dwell time 1min, obtains porous substrate pore structure and is filled by solution completely;
Sulfur component load: the material being filled with solution is cooled to 30 DEG C, applies stir process to material simultaneously, makes the sulfur component in supersaturated solution separate out into nanoparticle deposition gradually in porous substrate pore structure;
Dry: above-mentioned material is filtered, be placed on 80 DEG C at vacuumize, obtain sulfur-bearing electrode material.
Other is identical with embodiment 1, no longer repeats here.
The sulfur electrode material that comparative example, each embodiment are prepared and polytetrafluoroethylene, conductive carbon, solvent evenly after, be coated on aluminium foil, itemize obtains positive plate afterwards, reel with metal lithium bands, barrier film again and obtain naked battery core, select aluminum plastic film to be that exterior packaging material carries out closedtop, side seal, fluid injection, Vacuum Package, leaves standstill, changes into, shaping, degasification obtain finished product lithium-sulfur cell.
The present invention is tested as follows:
Volume test: by following flow process, volume test is carried out to the battery core that each embodiment and comparative example electrode material prepare in 25 DEG C of environment: leave standstill 3min; 0.5C constant-current discharge is to 1.5V; Leave standstill 3min; 0.5C constant current charge is to 3.8V, and constant voltage charge is to 0.05C; Leave standstill 3min; 0.5C constant-current discharge obtains discharge capacity D1 first to 1.5V; Complete volume test after leaving standstill 3min, acquired results is in table 1.
Loop test: by following flow process, loop test is carried out to the battery core that each embodiment and comparative example electrode material prepare in 25 DEG C of environment: leave standstill 3min; 0.5C constant-current discharge is to 1.5V; Leave standstill 3min; 0.5C constant current charge is to 3.8V, and constant voltage charge is to 0.05C; Leave standstill 3min; 0.5C constant-current discharge obtains discharge capacity D1 first to 1.5V; Leave standstill 3min, ", to 3.8V, constant voltage charge is to 0.05C for 0.5C constant current charge; Leave standstill 3min; 0.5C constant-current discharge obtains discharge capacity D1 first to 1.5V; Leave standstill 3min " repeat 299 times and obtain D300, complete loop test afterwards, calculated capacity conservation rate is D300/D1, and acquired results is in table 1.
Self discharge is tested: in 25 DEG C of environment, carry out self discharge test by following flow process to the battery core that each embodiment and comparative example electrode material prepare: leave standstill 3min; 0.5C constant current charge is to 3.0V, and constant voltage charge is to 0.05C; Test open circuit voltage V1 after leaving standstill 72h, leave standstill 72h afterwards again and test open circuit voltage V2, self-discharge rate=(the V1-V2)/72(mV/h of battery core), acquired results is in table 1.
Can be obtained by table 1, sulfur-bearing electrode material of the present invention assembles the lithium-sulfur cell obtained, and has higher capacity performance, cycle performance, and lower self discharge; This is the material because the present invention obtains, and makes full use of the profound pore structure of porous substrate, improves porous substrate to the load capacity of sulfur component; And profound pore structure has stronger suction-operated to lithium sulfide, the lithium sulfide therefore formed after the embedding lithium of sulfur-bearing electrode material will be tightly fixing by porous substrate, prevent it from dissolving and enter electrolyte and diffuse into negative pole precipitation.
Table 1, different electrolyte battery core capacity, circulation volume conservation rate, self discharge speed:
Can obtain from embodiment 1 ~ embodiment 9, the present invention has universality.
The announcement of book and instruction according to the above description, those skilled in the art in the invention can also change above-mentioned execution mode and revise.Therefore, the present invention is not limited to above-mentioned embodiment, and any apparent improvement of every those skilled in the art done by basis of the present invention, replacement or modification all belong to protection scope of the present invention.In addition, although employ some specific terms in this specification, these terms just for convenience of description, do not form any restriction to the present invention.
Claims (10)
1. a preparation method for sulfur-bearing electrode material, is characterized in that, mainly comprises the steps:
Step 1, the preparation of sulfur-bearing presoma: be in the container of T1 in temperature, sulfur component and solvent is even, obtain sulfur-bearing presoma stand-by;
Step 2, the filling of presoma: sulfur-bearing presoma step 1 obtained and porous substrate are placed in same reactor, keeps presoma temperature to be T2, sulfur-bearing presoma is fully filled and enters in the pore space structure of porous substrate;
Step 3, the load of sulfur component: reduction is fully filled with the temperature of the porous substrate of sulfur-bearing presoma to T3, the sulfur component in sulfur-bearing presoma is separated out, and is filled in the pore space structure of porous substrate;
Step 4, dry: porous substrate step 3 obtained is separated with sulfur-bearing presoma, dry under the fusing point of sulphur, remove solvent and namely obtain sulfur-bearing electrode material.
2. a preparation method for sulfur-bearing electrode material according to claim 1, is characterized in that, T1≤T2 is or/and T3≤T1.
3. a preparation method for sulfur-bearing electrode material according to claim 1, is characterized in that, sulfur component described in step 1 comprises at least one in sulphur simple substance, sulfur-based compound and sulfur compound; Described porous substrate comprises at least one in porous carbon materials, functionalized porous's material with carbon element, metal porous base material and functionalize metal's porous substrate, and described sulfur-bearing presoma is the saturated solution of the sulfur component under temperature T1.
4. a preparation method for sulfur-bearing electrode material according to claim 3, is characterized in that, described sulphur simple substance comprises sublimed sulfur and/or high purity sulphur; Described sulfur-based compound includes machine sulfide, Li
2s
nwith carbon-sulfur polymer (C
2s
v)
min at least one, wherein, n>=1,1≤v≤8,1≤m; Described sulfur compound comprises at least one in sulphur/carbon complex, sulphur/conductive polymer composite and sulphur/inorganic oxide; The particle diameter of described porous substrate is 5nm ~ 200 μm, and bore dia is 0.2nm ~ 2 μm, and porosity is 30% ~ 98%.
5. a preparation method for sulfur-bearing electrode material according to claim 1, is characterized in that, solvent described in step 1 be organic solvent or/and inorganic solvent, preparing the sulfur-bearing presoma that obtains is the saturated solution of sulfur component at T1 temperature.
6. a preparation method for sulfur-bearing electrode material according to claim 1, is characterized in that, described organic solvent comprises at least one class in arene, fat hydrocarbon, alicyclic hydrocarbon type, halogenated hydrocarbons, alcohols, ethers, ester class, ketone and diol, derivatives; Described inorganic solvent comprises at least one in water, inorganic acid, carbon disulfide, liquefied ammonia, liquid carbon dioxide, liquid nitrogen and liquid sulfur dioxide.
7. the preparation method of a sulfur-bearing electrode material according to claim 1, it is characterized in that, in step 1, be also added with surfactant in described sulfur-bearing presoma, the addition of described surfactant is 0.01% ~ 20% of the quality of described sulfur-bearing presoma; Described surfactant comprises at least one in wetting agent, dispersant, bleeding agent, solubilizer, cosolvent and cosolvent; Described wetting agent is that anionic is or/and non-ionic wetting agent; Described dispersant is at least one class in fatty acid/aliphatic amide type/ester class, paraffin class, metal soap, low-molecular-weight wax class and HPMA; Described bleeding agent is that nonionic is or/and anionic bleeding agent.
8. the preparation method of a sulfur-bearing electrode material according to claim 1, it is characterized in that, in the filling process of the sulfur-bearing presoma described in step 2, ultrasonic process is applied to mixed sulfur-bearing presoma or porous substrate, or/and in loading process described in step 3, at least one process applied in reactor in ultrasonic process, stirring and ball milling.
9. the preparation method of a sulfur-bearing electrode material according to claim 1; it is characterized in that; in the filling process of the sulfur-bearing presoma described in step 2; when molten sulfur fully infiltrates pretreated porous substrate; in reactor, pass into protective gas, the air pressure after ventilation is less than or equal to 100MPa.
10. the sulfur electrode material adopting method described in claim 1 to prepare, it is characterized in that: this electrode material is made up of porous substrate and the sulfur component be filled in described porous substrate, described sulfur component is nano particle, and the ratio that the quality of described sulfur component accounts for the quality of whole electrode material is 30% ~ 98%.
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| WO2019128644A1 (en) * | 2017-12-28 | 2019-07-04 | 桑德集团有限公司 | Aluminum-sulfur composite material, preparation method, and positive electrode material for lithium-sulfur battery |
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