CN105336936A - Preparation method of sulfur-containing electrode material - Google Patents

Preparation method of sulfur-containing electrode material Download PDF

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Publication number
CN105336936A
CN105336936A CN201510675811.6A CN201510675811A CN105336936A CN 105336936 A CN105336936 A CN 105336936A CN 201510675811 A CN201510675811 A CN 201510675811A CN 105336936 A CN105336936 A CN 105336936A
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sulfur
porous
sulphur
component
filling
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CN105336936B (en
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杨玉洁
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Guangdong Candle Light New Energy Technology Co Ltd
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/04Processes of manufacture in general
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/04Processes of manufacture in general
    • H01M4/0402Methods of deposition of the material
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention belongs to the field of lithium sulfur battery, and relates to a preparation method of a sulfur-containing electrode material. The preparation method comprises following five steps: pretreatment of a porous material; filling of a sulfur-containing component number as No.1; filling aftertreatment; preparation of a material filled with a sulfur-containing component number as No.2; and preparation of a sulfur-containing electrode material finished product. In the step of pretreatment of the porous material, gas components in the structure of the porous material are released completely via long time high vacuum treatment so as to reserve enough space for filling of the sulfur-containing components; the sulfur-containing components to be filled are subjected to filling in a plurality of times, so that filling-compacting-filling (wherein compacting is filling aftereatment, when the porous material is filled with the sulfur-containing components, and the sulfur-containing components are at liquid/gas state, pressure larger than one atmospheric pressure is applied so as to press the sulfur-containing components into the deep parts of the porous structure) is realized, pores of the porous material are filled completely, and the sulfur-containing electrode material with a high sulfur-containing component content is obtained.

Description

A kind of preparation method of sulfur-bearing electrode material
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 easily there is exothermal decomposition reactions when overcharging in this positive electrode, not only make battery capacity obviously decline, cell safety is also 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 be provided: comprise the preliminary treatment of porous material, filling that label is the sulfur component of 1, preparation five key steps of filling reprocessing, being filled with preparation that label is the sulfur component material of 2 and finished product sulfur-bearing electrode material; At porous material pretreatment stage, by long-time, high vacuum, fully discharge the gas component in porous material hole structure, the filling for sulfur component reserves enough spaces; And will the sulfur component of filling be needed to fill several times, (namely compacting process fills last handling process can to reach the process of filling-compacting-recharge, sulfur component fill enter porous material after but still for liquid state/gaseous state time, applying is greater than 1 atmospheric air pressure, depths by sulfur component press-in hole structure), thus the hole of porous material is completely filled, prepare the sulfur-bearing electrode material that sulfur component ratio is higher.
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: distribute sulfur component: sulfur component is divided into n part (n >=2), and label be 1,2 ..., n is stand-by;
Step 2, the preliminary treatment of porous material: porous material is placed in temperature is more than or equal to 10 DEG C, atmospheric pressure is less than or equal to the environment of 3kpa, the retention time is more than or equal to 10s, obtains pretreated porous material; Porous material is placed in high vacuum environment, through the process of long period, can gas component fully in tap structure, and be the filling headspace of sulfur component;
Step 3, label is the filling of the sulfur component of 1: keep atmospheric pressure be less than or equal to 3kpa, the sulfur component being 1 by pretreated porous material and label is placed in same reactor, make label be 1 sulfur component enter in the pore space structure of porous material; In the process that porous material mixes with sulfur component, before sulfur component fills, keep high vacuum degree always, space reserved in porous material hole structure can be maintained, be convenient to abundant sulfur component filling enter in loose structure, thus improve sulfur component mass ratio in the composite;
Step 4, fill reprocessing: material step 3 obtained is held in the reactor of temperature greater than or equal to the fusing point of sulphur, and protective gas is passed in reactor, the air pressure of protective gas is made to be more than or equal to 0.1MPa, retention time is more than or equal to 5s, obtain being filled with the material (in actual mechanical process, can not lower the temperature, namely carry out the filling of lower a sulfur component) that label is the sulfur component of 1 under the fusing point being cooled to sulphur afterwards; From once fill completely different, filling part need fill sulfur component after, filler resistance of movement in hole is less, employing malleation time the easier bosom squeezed into into pore structure; Thus realize the filling completely of pore structure; Meanwhile, be filled into into the secondary sulfur component of pore structure bottommost layer, pore structure has stronger suction-operated to the lithium sulphur compound formed after embedding lithium, and therefore it can show more excellent chemical property;
Step 5, is filled with the preparation that label is the sulfur component material of 2: be the sulfur component material of 1 with the sulfur component material replacement label that label is 2, repeat the process of step 2 ~ step 4, namely obtain being filled with the sulfur component material that label is 2; As n=2, after completing this step, namely prepare finished product sulfur-bearing electrode material.
Step 6, the preparation of finished product sulfur-bearing electrode material: be the sulfur component material of 2 with the sulfur component material replacement label that label is 3-n, repeat the process of step 5 successively, label is respectively 3 ..., n sulfur component fill and enter in porous material and obtain finished product sulfur-bearing electrode material.
One as sulfur-bearing electrode material preparation method of the present invention is improved, and the porous material described in step 2 is at least one in porous carbon materials, functionalized porous's material with carbon element, metal polyporous material, functionalize metal's porous material; Particle diameter is 5nm ~ 200 μm, and bore dia is 0.2nm ~ 2 μm, and porosity is 30% ~ 98%.Substrate particles is excessive, and the material lithium ion prepared diffuses into granule interior diffusion length from top layer is comparatively large, and the high rate performance of material is poor, and substrate particles is too small, is unfavorable for the bulk density improving coating; Bore dia is too small, and sulfur molecule cannot be filled in pore structure, and bore dia is excessive, and hole reduces the suction-operated of lithium sulphur compound.
One as sulfur-bearing electrode material preparation method of the present invention is improved, label described in step 1 is respectively 1,2 ..., n n part sulfur component weight not etc., and the weight of the 1st part to n-th part increases gradually; During because starting most to fill, need to fill the small size pores of porous material hole structure profound level, filling small hole hole when resistance is large, and being filled with of less amount to be beneficial to when reducing extruding sulfur component to the resistance of depths aperture movement; And aperture itself needs the inventory of filling relatively less.
One as sulfur-bearing electrode material preparation method of the present invention is improved, the composition of n part sulfur-containing compound component described in step 1 is different, and along with the increase of label ordinal number, active force between sulfur component and porous material increases, active force between the component of rear filling and porous material is strong, can effectively fix the sulfur-containing compound of first filling; The weight of n part sulfur-containing compound can be identical.
One as sulfur-bearing electrode material preparation method of the present invention is improved, temperature described in step 2 is 110 DEG C ~ 450 DEG C, filling temp described in step 3 is 110 DEG C ~ 450 DEG C, in described environment, atmospheric pressure pressure is less than or equal to 1kpa, the described retention time is more than or equal to 30s, is gas component in microcellular structure, needs longer diffusion time due to what will get rid of, therefore must guarantee processing time long enough, the gas component in micropore could be got rid of completely;
One as sulfur-bearing electrode material preparation method of the present invention is improved; protective gas described in step 4 comprises at least one in inert gas, nitrogen and sulfur dioxide; therefore the gas that namely described protective gas does not react with sulphur under condition of the present invention can also be carbon dioxide, nitrogen dioxide etc.
One as sulfur-bearing electrode material preparation method of the present invention is improved, and sulfur component described in step 2 comprises at least one in sulphur simple substance, sulfur-based compound and sulfur compound.
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, 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, described conducting polymer is polyaniline, polypyrrole, polythiophene, polyacetylene etc., and inorganic oxide comprises aluminium oxide, silica, zirconia etc.
One as sulfur-bearing electrode material preparation method of the present invention is improved, and in the filling process of the sulfur component described in step 3, applies ultrasonic process to mixed sulfur component and pretreated porous material.
The present invention also comprises a kind of sulfur electrode material adopting the inventive method to prepare, this electrode material is made up of porous material and the sulfur component be filled in porous material, 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: at porous material pretreatment stage, and by long-time, high vacuum, fully discharge the gas component in porous material hole structure, the filling for sulfur component reserves enough spaces; And will the sulfur component of filling be needed to fill several times, (namely compacting process fills last handling process can to reach the process of filling-compacting-recharge, sulfur component fill enter porous material after but still for liquid state/gaseous state time, applying is greater than 1 atmospheric air pressure, depths by sulfur component press-in hole structure), thus the hole of porous material is completely filled, prepare the sulfur-bearing electrode material that sulfur component ratio is higher.And, after high vacuum, long period process, then filled in steps sulfur component, filler can enter the bosom of base material pore structure, and the bosom of pore structure has stronger adsorption capacity to lithium sulphur compound, and the battery performance therefore prepared is better.
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 example, select 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), be placed in 170 DEG C of environment again 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 preliminary treatment of porous material: select particle diameter 10 μm ~ 20 μm, aperture is 10nm ~ 50nm, porosity be the porous carbon materials of 80% as base material, be placed in 10 DEG C, the environment of 1kpa process 1min, obtain pretreated porous carbon materials; According to material with carbon element: the relationship between quality of elemental sulfur=3:7 is filled, and elemental sulfur is divided into two parts, the mass ratio of two parts is 2:5;
1st part of sulphur simple substance is filled: the air pressure keeping 1kpa, is warming up to 200 DEG C, is fully mixed (mass ratio is 3:2) by the porous carbon materials after process, make molten sulfur penetrate sufficiently in the pore structure of porous carbon materials with elemental sulfur;
Fill reprocessing: after the abundant filling porous material hole structure of molten sulfur, keep temperature to be 200 DEG C, in reactor, pass into the helium of 10MPa, retention time 1min, be cooled to 25 DEG C afterwards, lay down helium pressure, complete the filling of first part of sulphur simple substance;
2nd part of sulphur simple substance is filled: by completing, sulphur carbon complex that first time fills is placed in 200 DEG C, the environment of 1kpa processes 1min, it fully mixes with elemental sulfur (mass ratio is 3:5) afterwards, makes molten sulfur penetrate sufficiently in the pore structure of porous carbon materials;
Fill reprocessing: after the abundant filling porous material hole structure of molten sulfur, keep temperature to be 200 DEG C, in reactor, pass into the helium of 10MPa, retention time 1min, be cooled to 25 DEG C afterwards, lay down helium pressure, complete the filling of second part of sulphur simple substance; Thus obtain sulphur carbon composite.
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 preliminary treatment of porous material: select particle diameter 10 μm ~ 20 μm, aperture is 10nm ~ 50nm, porosity be the porous carbon materials of 80% as base material, be placed in 110 DEG C, the environment of 1kpa process 1min, obtain pretreated porous carbon materials; According to material with carbon element: the relationship between quality of elemental sulfur=3:7 is filled, and elemental sulfur is divided into two parts, the mass ratio of two parts is 2:5;
1st part of sulphur simple substance is filled: the air pressure keeping 1kpa, is warming up to 110 DEG C, is fully mixed (mass ratio is 3:2) by the porous carbon materials after process, make molten sulfur penetrate sufficiently in the pore structure of porous carbon materials with elemental sulfur;
Fill reprocessing: after the abundant filling porous material hole structure of molten sulfur, keep temperature to be 110 DEG C, in reactor, pass into the helium of 10MPa, retention time 1min, be cooled to 25 DEG C afterwards, lay down helium pressure, complete the filling of first part of sulphur simple substance;
2nd part of sulphur simple substance is filled: by completing, sulphur carbon complex that first time fills is placed in 110 DEG C, the environment of 1kpa processes 1min, it fully mixes with elemental sulfur (mass ratio is 3:5) afterwards, makes molten sulfur penetrate sufficiently in the pore structure of porous carbon materials;
Fill reprocessing: after the abundant filling porous material hole structure of molten sulfur, keep temperature to be 110 DEG C, in reactor, pass into the helium of 10MPa, retention time 1min, be cooled to 25 DEG C afterwards, lay down helium pressure, complete the filling of second part of sulphur simple substance; Thus obtain sulphur carbon composite.
Other is identical with embodiment 1, no longer repeats here.
Embodiment 3, as different from Example 1, the present embodiment comprises the steps:
The preliminary treatment of porous material: select particle diameter 10 μm ~ 20 μm, aperture is 10nm ~ 50nm, porosity be the porous carbon materials of 80% as base material, be placed in 450 DEG C, the environment of 1kpa process 1min, obtain pretreated porous carbon materials; According to material with carbon element: the relationship between quality of elemental sulfur=3:7 is filled, and elemental sulfur is divided into two parts, the mass ratio of two parts is 2:5;
1st part of sulphur simple substance is filled: the air pressure keeping 1kpa, is warming up to 450 DEG C, is fully mixed (mass ratio is 3:2) by the porous carbon materials after process, make molten sulfur penetrate sufficiently in the pore structure of porous carbon materials with elemental sulfur;
Fill reprocessing: after the abundant filling porous material hole structure of molten sulfur, keep temperature to be 450 DEG C, in reactor, pass into the helium of 10MPa, retention time 1min, be cooled to 25 DEG C afterwards, lay down helium pressure, complete the filling of first part of sulphur simple substance;
2nd part of sulphur simple substance is filled: by completing, sulphur carbon complex that first time fills is placed in 450 DEG C, the environment of 1kpa processes 1min, it fully mixes with elemental sulfur (mass ratio is 3:5) afterwards, makes molten sulfur penetrate sufficiently in the pore structure of porous carbon materials;
Fill reprocessing: after the abundant filling porous material hole structure of molten sulfur, keep temperature to be 450 DEG C, in reactor, pass into the helium of 10MPa, retention time 1min, be cooled to 25 DEG C afterwards, lay down helium pressure, complete the filling of second part of sulphur simple substance; Thus obtain sulphur carbon composite.
Other is identical with embodiment 1, no longer repeats here.
Embodiment 4, as different from Example 1, the present embodiment comprises the steps:
The preliminary treatment of porous material: select particle diameter 10 μm ~ 20 μm, aperture is 10nm ~ 50nm, porosity be the porous carbon materials of 80% as base material, be placed in 150 DEG C, the environment of 3kpa process 1min, obtain pretreated porous carbon materials; According to material with carbon element: the relationship between quality of elemental sulfur=3:7 is filled, and elemental sulfur is divided into two parts, the mass ratio of two parts is 2:5;
1st part of sulphur simple substance is filled: the air pressure keeping 3kpa, is warming up to 150 DEG C, is fully mixed (mass ratio is 3:2) by the porous carbon materials after process, make molten sulfur penetrate sufficiently in the pore structure of porous carbon materials with elemental sulfur;
Fill reprocessing: after the abundant filling porous material hole structure of molten sulfur, keep temperature to be 150 DEG C, in reactor, pass into the helium of 10MPa, retention time 1min, be cooled to 25 DEG C afterwards, lay down helium pressure, complete the filling of first part of sulphur simple substance;
2nd part of sulphur simple substance is filled: by completing, sulphur carbon complex that first time fills is placed in 150 DEG C, the environment of 3kpa processes 1min, it fully mixes with elemental sulfur (mass ratio is 3:5) afterwards, makes molten sulfur penetrate sufficiently in the pore structure of porous carbon materials;
Fill reprocessing: after the abundant filling porous material hole structure of molten sulfur, keep temperature to be 150 DEG C, in reactor, pass into the helium of 10MPa, retention time 1min, be cooled to 25 DEG C afterwards, lay down helium pressure, complete the filling of second part of sulphur simple substance; Thus obtain sulphur carbon composite.
Other is identical with embodiment 1, no longer repeats here.
Embodiment 5, as different from Example 1, the present embodiment comprises the steps:
The preliminary treatment of porous material: select particle diameter 10 μm ~ 20 μm, aperture is 10nm ~ 50nm, porosity be the porous carbon materials of 80% as base material, be placed in 150 DEG C, the environment of 0.1kpa process 1min, obtain pretreated porous carbon materials; According to material with carbon element: the relationship between quality of elemental sulfur=3:7 is filled, and elemental sulfur is divided into two parts, the mass ratio of two parts is 2:5;
1st part of sulphur simple substance is filled: the air pressure keeping 0.1kpa, is warming up to 150 DEG C, is fully mixed (mass ratio is 3:2) by the porous carbon materials after process, make molten sulfur penetrate sufficiently in the pore structure of porous carbon materials with elemental sulfur;
Fill reprocessing: after the abundant filling porous material hole structure of molten sulfur, keep temperature to be 150 DEG C, in reactor, pass into the helium of 10MPa, retention time 1min, be cooled to 25 DEG C afterwards, lay down helium pressure, complete the filling of first part of sulphur simple substance;
2nd part of sulphur simple substance is filled: by completing, sulphur carbon complex that first time fills is placed in 150 DEG C, the environment of 0.1kpa processes 1min, it fully mixes with elemental sulfur (mass ratio is 3:5) afterwards, makes molten sulfur penetrate sufficiently in the pore structure of porous carbon materials;
Fill reprocessing: after the abundant filling porous material hole structure of molten sulfur, keep temperature to be 150 DEG C, in reactor, pass into the helium of 10MPa, retention time 1min, be cooled to 25 DEG C afterwards, lay down helium pressure, complete the filling of second part of sulphur simple substance; Thus obtain sulphur carbon composite.
Other is identical with embodiment 1, no longer repeats here.
Embodiment 6, as different from Example 1, the present embodiment comprises the steps:
The preliminary treatment of porous material: select particle diameter 10 μm ~ 20 μm, aperture is 10nm ~ 50nm, porosity be the porous carbon materials of 80% as base material, be placed in 150 DEG C, the environment of 10pa process 1min, obtain pretreated porous carbon materials; According to material with carbon element: the relationship between quality of elemental sulfur=3:7 is filled, and elemental sulfur is divided into two parts, the mass ratio of two parts is 2:5;
1st part of sulphur simple substance is filled: the air pressure keeping 10pa, is warming up to 150 DEG C, is fully mixed (mass ratio is 3:2) by the porous carbon materials after process, make molten sulfur penetrate sufficiently in the pore structure of porous carbon materials with elemental sulfur;
Fill reprocessing: after the abundant filling porous material hole structure of molten sulfur, keep temperature to be 150 DEG C, in reactor, pass into the helium of 10MPa, retention time 1min, be cooled to 25 DEG C afterwards, lay down helium pressure, complete the filling of first part of sulphur simple substance;
2nd part of sulphur simple substance is filled: by completing, sulphur carbon complex that first time fills is placed in 150 DEG C, the environment of 10pa processes 1min, it fully mixes with elemental sulfur (mass ratio is 3:5) afterwards, makes molten sulfur penetrate sufficiently in the pore structure of porous carbon materials;
Fill reprocessing: after the abundant filling porous material hole structure of molten sulfur, keep temperature to be 150 DEG C, in reactor, pass into the helium of 10MPa, retention time 1min, be cooled to 25 DEG C afterwards, lay down helium pressure, complete the filling of second part of sulphur simple substance; Thus obtain sulphur carbon composite.
Other is identical with embodiment 1, no longer repeats here.
Embodiment 7, as different from Example 1, the present embodiment comprises the steps:
The preliminary treatment of porous material: select particle diameter 10 μm ~ 20 μm, aperture is 10nm ~ 50nm, porosity be the porous carbon materials of 80% as base material, be placed in 150 DEG C, the environment of 1pa process 1min, obtain pretreated porous carbon materials; According to material with carbon element: the relationship between quality of elemental sulfur=3:7 is filled, and elemental sulfur is divided into two parts, the mass ratio of two parts is 2:5;
1st part of sulphur simple substance is filled: the air pressure keeping 1pa, is warming up to 150 DEG C, is fully mixed (mass ratio is 3:2) by the porous carbon materials after process, make molten sulfur penetrate sufficiently in the pore structure of porous carbon materials with elemental sulfur;
Fill reprocessing: after the abundant filling porous material hole structure of molten sulfur, keep temperature to be 150 DEG C, in reactor, pass into the helium of 10MPa, retention time 1min, be cooled to 25 DEG C afterwards, lay down helium pressure, complete the filling of first part of sulphur simple substance;
2nd part of sulphur simple substance is filled: by completing, sulphur carbon complex that first time fills is placed in 150 DEG C, the environment of 1pa processes 1min, it fully mixes with elemental sulfur (mass ratio is 3:5) afterwards, makes molten sulfur penetrate sufficiently in the pore structure of porous carbon materials;
Fill reprocessing: after the abundant filling porous material hole structure of molten sulfur, keep temperature to be 150 DEG C, in reactor, pass into the helium of 10MPa, retention time 1min, be cooled to 25 DEG C afterwards, lay down helium pressure, complete the filling of second part of sulphur simple substance; Thus obtain sulphur carbon composite.
Other is identical with embodiment 1, no longer repeats here.
Embodiment 8, as different from Example 6, the present embodiment comprises the steps:
The preliminary treatment of porous material: select particle diameter 10 μm ~ 20 μm, aperture is 10nm ~ 50nm, porosity be the porous carbon materials of 80% as base material, be placed in 150 DEG C, the environment of 10pa process 10s, obtain pretreated porous carbon materials; According to material with carbon element: the relationship between quality of elemental sulfur=3:7 is filled, and elemental sulfur is divided into two parts, the mass ratio of two parts is 2:5;
1st part of sulphur simple substance is filled: the air pressure keeping 10pa, is warming up to 150 DEG C, is fully mixed (mass ratio is 3:2) by the porous carbon materials after process, make molten sulfur penetrate sufficiently in the pore structure of porous carbon materials with elemental sulfur;
Fill reprocessing: after the abundant filling porous material hole structure of molten sulfur, keep temperature to be 150 DEG C, in reactor, pass into the helium of 10MPa, retention time 1min, be cooled to 25 DEG C afterwards, lay down helium pressure, complete the filling of first part of sulphur simple substance;
2nd part of sulphur simple substance is filled: by completing, sulphur carbon complex that first time fills is placed in 150 DEG C, the environment of 10pa processes 10s, it fully mixes with elemental sulfur (mass ratio is 3:5) afterwards, makes molten sulfur penetrate sufficiently in the pore structure of porous carbon materials;
Fill reprocessing: after the abundant filling porous material hole structure of molten sulfur, keep temperature to be 150 DEG C, in reactor, pass into the helium of 10MPa, retention time 1min, be cooled to 25 DEG C afterwards, lay down helium pressure, complete the filling of second part of sulphur simple substance; Thus obtain sulphur carbon composite.
Other is identical with embodiment 6, no longer repeats here.
Embodiment 9, as different from Example 6, the present embodiment comprises the steps:
The preliminary treatment of porous material: select particle diameter 10 μm ~ 20 μm, aperture is 10nm ~ 50nm, porosity be the porous carbon materials of 80% as base material, be placed in 150 DEG C, the environment of 10pa process 30s, obtain pretreated porous carbon materials; According to material with carbon element: the relationship between quality of elemental sulfur=3:7 is filled, and elemental sulfur is divided into two parts, the mass ratio of two parts is 2:5;
1st part of sulphur simple substance is filled: the air pressure keeping 10pa, is warming up to 150 DEG C, is fully mixed (mass ratio is 3:2) by the porous carbon materials after process, make molten sulfur penetrate sufficiently in the pore structure of porous carbon materials with elemental sulfur;
Fill reprocessing: after the abundant filling porous material hole structure of molten sulfur, keep temperature to be 150 DEG C, in reactor, pass into the helium of 10MPa, retention time 1min, be cooled to 25 DEG C afterwards, lay down helium pressure, complete the filling of first part of sulphur simple substance;
2nd part of sulphur simple substance is filled: by completing, sulphur carbon complex that first time fills is placed in 150 DEG C, the environment of 10pa processes 30s, it fully mixes with elemental sulfur (mass ratio is 3:5) afterwards, makes molten sulfur penetrate sufficiently in the pore structure of porous carbon materials;
Fill reprocessing: after the abundant filling porous material hole structure of molten sulfur, keep temperature to be 150 DEG C, in reactor, pass into the helium of 10MPa, retention time 1min, be cooled to 25 DEG C afterwards, lay down helium pressure, complete the filling of second part of sulphur simple substance; Thus obtain sulphur carbon composite.
Other is identical with embodiment 6, no longer repeats here.
Embodiment 10, as different from Example 6, the present embodiment comprises the steps:
The preliminary treatment of porous material: select particle diameter 10 μm ~ 20 μm, aperture is 10nm ~ 50nm, porosity be the porous carbon materials of 80% as base material, be placed in 150 DEG C, the environment of 10pa process 5min, obtain pretreated porous carbon materials; According to material with carbon element: the relationship between quality of elemental sulfur=3:7 is filled, and elemental sulfur is divided into two parts, the mass ratio of two parts is 2:5;
1st part of sulphur simple substance is filled: the air pressure keeping 10pa, is warming up to 150 DEG C, is fully mixed (mass ratio is 3:2) by the porous carbon materials after process, make molten sulfur penetrate sufficiently in the pore structure of porous carbon materials with elemental sulfur;
Fill reprocessing: after the abundant filling porous material hole structure of molten sulfur, keep temperature to be 150 DEG C, in reactor, pass into the helium of 10MPa, retention time 1min, be cooled to 25 DEG C afterwards, lay down helium pressure, complete the filling of first part of sulphur simple substance;
2nd part of sulphur simple substance is filled: by completing, sulphur carbon complex that first time fills is placed in 150 DEG C, the environment of 10pa processes 5min, it fully mixes with elemental sulfur (mass ratio is 3:5) afterwards, makes molten sulfur penetrate sufficiently in the pore structure of porous carbon materials;
Fill reprocessing: after the abundant filling porous material hole structure of molten sulfur, keep temperature to be 150 DEG C, in reactor, pass into the helium of 10MPa, retention time 1min, be cooled to 25 DEG C afterwards, lay down helium pressure, complete the filling of second part of sulphur simple substance; Thus obtain sulphur carbon composite.
Other is identical with embodiment 6, no longer repeats here.
Embodiment 11, as different from Example 6, the present embodiment comprises the steps:
The preliminary treatment of porous material: select particle diameter 10 μm ~ 20 μm, aperture is 10nm ~ 50nm, porosity be the porous carbon materials of 80% as base material, be placed in 150 DEG C, the environment of 10pa process 1min, obtain pretreated porous carbon materials; According to material with carbon element: the relationship between quality of elemental sulfur=3:7 is filled, and elemental sulfur is divided into two parts, the mass ratio of two parts is 2:5;
1st part of sulphur simple substance is filled: the air pressure keeping 10pa, is warming up to 150 DEG C, is fully mixed (mass ratio is 3:2) by the porous carbon materials after process, make molten sulfur penetrate sufficiently in the pore structure of porous carbon materials with elemental sulfur;
Fill reprocessing: after the abundant filling porous material hole structure of molten sulfur, keep temperature to be 150 DEG C, in reactor, pass into the helium of 0.1MPa, retention time 30min, be cooled to 25 DEG C afterwards, lay down helium pressure, complete the filling of first part of sulphur simple substance;
2nd part of sulphur simple substance is filled: by completing, sulphur carbon complex that first time fills is placed in 150 DEG C, the environment of 10pa processes 1min, it fully mixes with elemental sulfur (mass ratio is 3:5) afterwards, makes molten sulfur penetrate sufficiently in the pore structure of porous carbon materials;
Fill reprocessing: after the abundant filling porous material hole structure of molten sulfur, keep temperature to be 150 DEG C, in reactor, pass into the helium of 0.1MPa, retention time 30min, be cooled to 25 DEG C afterwards, lay down helium pressure, complete the filling of second part of sulphur simple substance; Thus obtain sulphur carbon composite.
Other is identical with embodiment 6, no longer repeats here.
Embodiment 12, as different from Example 6, the present embodiment comprises the steps:
The preliminary treatment of porous material: select particle diameter 10 μm ~ 20 μm, aperture is 10nm ~ 50nm, porosity be the porous carbon materials of 80% as base material, be placed in 150 DEG C, the environment of 10pa process 1min, obtain pretreated porous carbon materials; According to material with carbon element: the relationship between quality of elemental sulfur=3:7 is filled, and elemental sulfur is divided into two parts, the mass ratio of two parts is 2:5;
1st part of sulphur simple substance is filled: the air pressure keeping 10pa, is warming up to 150 DEG C, is fully mixed (mass ratio is 3:2) by the porous carbon materials after process, make molten sulfur penetrate sufficiently in the pore structure of porous carbon materials with elemental sulfur;
Fill reprocessing: after the abundant filling porous material hole structure of molten sulfur, keep temperature to be 150 DEG C, in reactor, pass into the nitrogen of 100MPa, retention time 5s, be cooled to 25 DEG C afterwards, lay down nitrogen pressure, complete the filling of first part of sulphur simple substance;
2nd part of sulphur simple substance is filled: by completing, sulphur carbon complex that first time fills is placed in 150 DEG C, the environment of 10pa processes 1min, it fully mixes with elemental sulfur (mass ratio is 3:5) afterwards, makes molten sulfur penetrate sufficiently in the pore structure of porous carbon materials;
Fill reprocessing: after the abundant filling porous material hole structure of molten sulfur, keep temperature to be 150 DEG C, in reactor, pass into the nitrogen of 100MPa, retention time 5s, be cooled to 25 DEG C afterwards, lay down nitrogen pressure, complete the filling of second part of sulphur simple substance; Thus obtain sulphur carbon composite.
Other is identical with embodiment 6, no longer repeats here.
Embodiment 13, as different from Example 6, the present embodiment comprises the steps:
The preliminary treatment of porous material: 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 in 150 DEG C, the environment of 10pa process 1min, obtain pretreated porous carbon materials; According to material with carbon element: the relationship between quality of elemental sulfur=7:3 is filled, and elemental sulfur is divided into two parts, the mass ratio of two parts is 1:1;
1st part of sulphur simple substance is filled: the air pressure keeping 10pa, is warming up to 150 DEG C, is fully mixed (mass ratio is 7:1.5) by the porous carbon materials after process, make molten sulfur penetrate sufficiently in the pore structure of porous carbon materials with elemental sulfur;
Fill reprocessing: after the abundant filling porous material hole structure of molten sulfur, keep temperature to be 150 DEG C, in reactor, pass into the helium of 10MPa, retention time 1min, be cooled to 25 DEG C afterwards, lay down helium pressure, complete the filling of first part of sulphur simple substance;
2nd part of sulphur simple substance is filled: by completing, sulphur carbon complex that first time fills is placed in 150 DEG C, the environment of 10pa processes 1min, it fully mixes with elemental sulfur (mass ratio is 7:1.5) afterwards, makes molten sulfur penetrate sufficiently in the pore structure of porous carbon materials;
Fill reprocessing: after the abundant filling porous material hole structure of molten sulfur, keep temperature to be 150 DEG C, in reactor, pass into the helium of 10MPa, retention time 1min, be cooled to 25 DEG C afterwards, lay down helium pressure, complete the filling of second part of sulphur simple substance; Thus obtain sulphur carbon composite.
Other is identical with embodiment 6, no longer repeats here.
Embodiment 14, as different from Example 6, the present embodiment comprises the steps:
The preliminary treatment of porous material: 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 in 150 DEG C, the environment of 10pa process 1min, obtain pretreated porous carbon materials; According to material with carbon element: the relationship between quality of elemental sulfur=4:6 is filled, and elemental sulfur is divided into two parts, the mass ratio of two parts is 2:4;
1st part of sulphur simple substance is filled: the air pressure keeping 10pa, is warming up to 150 DEG C, is fully mixed (mass ratio is 4:2) by the porous carbon materials after process, make molten sulfur penetrate sufficiently in the pore structure of porous carbon materials with elemental sulfur;
Fill reprocessing: after the abundant filling porous material hole structure of molten sulfur, keep temperature to be 150 DEG C, in reactor, pass into the helium of 10MPa, retention time 1min, be cooled to 25 DEG C afterwards, lay down helium pressure, complete the filling of first part of sulphur simple substance;
2nd part of sulphur simple substance is filled: by completing, sulphur carbon complex that first time fills is placed in 150 DEG C, the environment of 10pa processes 1min, it fully mixes with elemental sulfur (mass ratio is 4:4) afterwards, makes molten sulfur penetrate sufficiently in the pore structure of porous carbon materials;
Fill reprocessing: after the abundant filling porous material hole structure of molten sulfur, keep temperature to be 150 DEG C, in reactor, pass into the helium of 10MPa, retention time 1min, be cooled to 25 DEG C afterwards, lay down helium pressure, complete the filling of second part of sulphur simple substance; Thus obtain sulphur carbon composite.
Other is identical with embodiment 6, no longer repeats here.
Embodiment 15, as different from Example 6, the present embodiment comprises the steps:
The preliminary treatment of porous material: select particle diameter 5 μm ~ 10 μm, aperture is 5nm ~ 20nm, porosity be the porous carbon materials of 98% as base material, be placed in 150 DEG C, the environment of 10pa process 1min, obtain pretreated porous carbon materials; According to material with carbon element: the relationship between quality of elemental sulfur=2:98 is filled, and elemental sulfur is divided into 3 parts, the mass ratio of 3 parts is 2:16:80;
1st part of sulphur simple substance is filled: the air pressure keeping 10pa, is warming up to 150 DEG C, is fully mixed (mass ratio is 2:2) by the porous carbon materials after process, make molten sulfur penetrate sufficiently in the pore structure of porous carbon materials with elemental sulfur;
Fill reprocessing: after the abundant filling porous material hole structure of molten sulfur, keep temperature to be 150 DEG C, in reactor, pass into the helium of 10MPa, retention time 1min, be cooled to 25 DEG C afterwards, lay down helium pressure, complete the filling of first part of sulphur simple substance;
2nd part of sulphur simple substance is filled: by completing, sulphur carbon complex that first time fills is placed in 150 DEG C, the environment of 10pa processes 1min, it fully mixes with elemental sulfur (mass ratio is 2:16) afterwards, makes molten sulfur penetrate sufficiently in the pore structure of porous carbon materials;
Fill reprocessing: after the abundant filling porous material hole structure of molten sulfur, keep temperature to be 150 DEG C, in reactor, pass into the helium of 10MPa, retention time 1min, be cooled to 25 DEG C afterwards, lay down helium pressure, complete the filling of second part of sulphur simple substance;
3rd part of sulphur simple substance is filled: by completing, sulphur carbon complex that first time fills is placed in 150 DEG C, the environment of 10pa processes 1min, it fully mixes with elemental sulfur (mass ratio is 2:80) afterwards, makes molten sulfur penetrate sufficiently in the pore structure of porous carbon materials;
Fill reprocessing: after the abundant filling porous material hole structure of molten sulfur, keep temperature to be 150 DEG C, in reactor, pass into the helium of 10MPa, retention time 1min, be cooled to 25 DEG C afterwards, lay down helium pressure, complete the filling of the 3rd part of sulphur simple substance; Thus obtain sulphur carbon composite.
Other is identical with embodiment 6, no longer repeats here.
Embodiment 16, as different from Example 6, the present embodiment comprises the steps:
The preliminary treatment of porous material: select particle diameter 10 μm ~ 20 μm, aperture is 10nm ~ 50nm, porosity is that the remodeling porous carbon materials of 80% is as base material (namely containing the porous carbon of part oxygen-containing functional group in surface and holes mechanism), be placed in 150 DEG C, the environment of 10pa processes 1min, obtain pretreated porous carbon materials; According to material with carbon element: elemental sulfur: the relationship between quality of carbon-sulfur polymer=2:6:2 is filled, and elemental sulfur and carbon-sulfur polymer is divided into twice and fills, and first time fills elemental sulfur, and second time fills carbon-sulfur polymer;
Sulphur simple substance is filled: the air pressure keeping 10pa, is warming up to 150 DEG C, is fully mixed (mass ratio is 2:6) by the porous carbon materials after process, make molten sulfur penetrate sufficiently in the pore structure of porous carbon materials with elemental sulfur;
Fill reprocessing: after the abundant filling porous material hole structure of molten sulfur, keep temperature to be 150 DEG C, in reactor, pass into the helium of 10MPa, retention time 1min, be cooled to 25 DEG C afterwards, lay down helium pressure, complete the filling of first part of sulphur simple substance;
Carbon-sulfur polymer is filled: by completing, sulphur carbon complex that elemental sulfur fills is placed in 150 DEG C, the environment of 10pa processes 1min, it fully mixes with carbon-sulfur polymer (mass ratio is 2:2) afterwards, makes carbon-sulfur polymer penetrate sufficiently in the pore structure of porous carbon materials;
Fill reprocessing: after the abundant filling porous material hole structure of molten sulfur, keep temperature to be 150 DEG C, in reactor, pass into the helium of 10MPa, retention time 1min, be cooled to 25 DEG C afterwards, lay down helium pressure, complete the filling of second part of sulphur simple substance; Thus obtain sulphur carbon composite.
Other is identical with embodiment 6, no longer repeats here.
Embodiment 17, as different from Example 16, the present embodiment comprises the steps:
The preliminary treatment of porous material: select particle diameter 10 μm ~ 20 μm, aperture is 10nm ~ 50nm, porosity be the porous aluminum material of 80% as base material, be placed in 150 DEG C, the environment of 10pa process 1min, obtain pretreated porous carbon materials; According to material with carbon element: elemental sulfur: the relationship between quality of carbon-sulfur polymer=2:6:2 is filled, and elemental sulfur and carbon-sulfur polymer is divided into twice and fills, and first time fills elemental sulfur, and second time fills carbon-sulfur polymer;
Other is identical with embodiment 16, 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=(V1-V2)/72 (mV/h) of battery core, acquired results is in table 1.
Table 1, different electrolyte battery core capacity, circulation volume conservation rate, self discharge speed:
Can be obtained by table 1, the sulfur-bearing electrode material that the present invention prepares 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 sulfur component is filled more abundant.
Can be obtained by embodiment 4 ~ embodiment 7, vacuum degree when improving preliminary treatment and fill, the sulfur-bearing electrode material prepared has more excellent performance, this is because the increase of vacuum degree, is conducive to getting rid of the gas component in porous material hollow structure more fully; Can be obtained by embodiment 6, embodiment 8 ~ embodiment 10, along with the prolongation of pretreatment time, battery performance improves gradually.
Can obtain from embodiment 1 ~ embodiment 17, 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, is divided into n part by sulfur component, wherein, n >=2, and label be 1,2 ..., n is stand-by;
Step 2, the preliminary treatment of porous material: porous material is placed in temperature is more than or equal to 10 DEG C, atmospheric pressure is less than or equal to the environment of 3kpa, the retention time is more than or equal to 10s, obtains pretreated porous material;
Step 3, label is the filling of the sulfur component of 1: keep atmospheric pressure be less than or equal to 3kpa, the sulfur component being 1 by pretreated porous material and label is placed in same reactor, make label be 1 sulfur component enter in the pore space structure of porous material;
Step 4, fill reprocessing: material step 3 obtained is held in the reactor of temperature greater than or equal to the fusing point of sulphur, and protective gas is passed in reactor, the air pressure of protective gas is made to be more than or equal to 0.1MPa, retention time is more than or equal to 5s, obtains being filled with the sulfur component material that label is 1 under the fusing point being cooled to sulphur afterwards;
Step 5, is filled with the preparation that label is the sulfur component material of 2: be the sulfur component material of 1 with the sulfur component material replacement label that label is 2, repeat step 3 ~ step 4, namely obtain being filled with the sulfur component material that label is 2;
Step 6, the preparation of finished product sulfur-bearing electrode material: be the sulfur component material of 2 with the sulfur component material replacement label that label is 3 ~ n, successively repeat step 5, label is respectively 3 ..., n sulfur component fill and enter in porous material and obtain finished product sulfur-bearing electrode material.
2. a preparation method for sulfur-bearing electrode material according to claim 1, is characterized in that, the porous material described in step 2 is at least one in porous carbon materials, functionalized porous's material with carbon element, metal polyporous material, functionalize metal's porous material; The particle diameter of described porous material is 5nm ~ 200 μm, and bore dia is 0.2nm ~ 2 μm, and porosity is 30% ~ 98%.
3. a preparation method for sulfur-bearing electrode material according to claim 1, is characterized in that, label described in step 1 is respectively 1,2 ..., n n part sulfur component weight not etc., and the weight of the 1st part to n-th part increases gradually.
4. a preparation method for sulfur-bearing electrode material according to claim 1, is characterized in that, the composition of n part sulfur-containing compound component described in step 1 is different, and along with the increase of label ordinal number, the active force between sulfur component and porous material increases.
5. a preparation method for sulfur-bearing electrode material according to claim 1, is characterized in that, the temperature described in step 2 is 110 DEG C ~ 450 DEG C, and in described environment, atmospheric pressure pressure is less than or equal to 1kpa, and the described retention time is more than or equal to 30s.
6. a preparation method for sulfur-bearing electrode material according to claim 1, is characterized in that, the protective gas described in step 4 comprises at least one in inert gas, nitrogen and sulfur dioxide.
7. 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.
8. a preparation method for sulfur-bearing electrode material according to claim 7, 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.
9. a preparation method for sulfur-bearing electrode material according to claim 1, is characterized in that, in the filling process of the sulfur component described in step 3, applies ultrasonic process to mixed sulfur component and pretreated porous material.
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 material and the sulfur component be filled in described porous material, the ratio that the quality of described sulfur component accounts for the quality of whole electrode material is 30% ~ 98%.
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CN106532043A (en) * 2016-12-29 2017-03-22 西安理工大学 Preparation method of carbon gel-loaded sulfur positive electrode material for lithium-sulfur battery
CN108269984A (en) * 2018-01-17 2018-07-10 国家纳米科学中心 A kind of lithium-sulfur cell flexible electrode material and its preparation method and application
CN111653728A (en) * 2019-03-04 2020-09-11 中南大学 Lithium-sulfur battery porous positive electrode and preparation method and application thereof

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Publication number Priority date Publication date Assignee Title
CN106532043A (en) * 2016-12-29 2017-03-22 西安理工大学 Preparation method of carbon gel-loaded sulfur positive electrode material for lithium-sulfur battery
CN106532043B (en) * 2016-12-29 2019-11-22 西安理工大学 A kind of preparation method of carbon gel sulfur loaded-lithium sulfur battery anode material
CN108269984A (en) * 2018-01-17 2018-07-10 国家纳米科学中心 A kind of lithium-sulfur cell flexible electrode material and its preparation method and application
CN108269984B (en) * 2018-01-17 2020-04-14 国家纳米科学中心 Flexible electrode material of lithium-sulfur battery and preparation method and application thereof
CN111653728A (en) * 2019-03-04 2020-09-11 中南大学 Lithium-sulfur battery porous positive electrode and preparation method and application thereof

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