CN102820456B - Porous carbon/sulfur composite material, its preparation method and application - Google Patents
Porous carbon/sulfur composite material, its preparation method and application Download PDFInfo
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- CN102820456B CN102820456B CN201210297395.7A CN201210297395A CN102820456B CN 102820456 B CN102820456 B CN 102820456B CN 201210297395 A CN201210297395 A CN 201210297395A CN 102820456 B CN102820456 B CN 102820456B
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Abstract
The invention discloses a porous carbon/sulfur composite material and its preparation method. The method comprises the following steps of: (1) adding water into a mixture of alginic acid and a metal hydroxide, and stirring them uniformly to obtain a reaction solution; (2) evaporating the water of the reaction solution, and then conducting heating under a non-oxidizing atmosphere so as to obtain a porous carbon material precursor; (3) treating the porous carbon material precursor with water or an acid solution, then drying the precursor so as to obtain a porous carbon material; and (4) heating a mixture of the porous carbon material and sulfur powder, thus obtaining the porous carbon/sulfur composite material. The invention also provides application of the porous carbon/sulfur composite material as a battery electrode material, especially its application as a lithium sulfur battery positive electrode material. Compared with the prior art, the preparation method of the porous carbon/sulfur composite material provided in the invention has the advantages of simple preparation method, easily available raw materials, suitability for mass production, and high degree of utility. The porous carbon/sulfur composite material provided in the invention can be directly used as a battery electrode material.
Description
Technical field
The present invention relates to a kind of porous carbon/sulphur composite material and preparation method thereof and application.
Background technology
Along with the extensive use of lithium ion battery in portable type electronic product, electric automobile and instant-plugging hybrid electric vehicle, in the urgent need to developing the more battery of high-energy-density.Be restricted owing to improving anode material for lithium-ion batteries capacity, the energy density of lithium ion battery is difficult to further increase considerably.Can bring again safety issue by the voltage platform raising energy density that increases positive electrode simultaneously.Forward positive electrode to " conversion reaction chemism " from " deintercalation mechanism ", be expected to obtain the material of height ratio capacity and specific energy.Elemental sulfur is one of the most promising material.Sulphur generates Li with lithium metal complete reaction
2s, cell reaction is S+2Li=Li
2s, is bielectron course of reaction, does not relate to the deintercalation reaction of lithium ion.Because the molecular weight of sulphur is low, therefore the theoretical specific capacity of sulphur is up to 1675mAhg
-1(be almost LiFePO
410 times), theoretical specific energy is 2600Wh Kg
-1.In addition, elemental sulfur is abundant at nature reserves, low toxicity, cheap, and therefore elemental sulfur is a kind of positive active material having a great attraction.
But sulphur positive electrode also faces some challenges, mainly comprises: 1) (room-temperature conductivity is 5 × 10 to the insulating properties of sulphur
-30s cm
-1), its ionic conductivity and electron conduction are all very low, make the chemical property variation of sulphur, and active material utilization is low; 2) polysulfide generating in charge and discharge process is soluble in electrolyte, and electrode active material reduces gradually, volume lowering; 3) due to the principle of shuttling back and forth, the polysulfide dissolving in electrolyte contacts with cathode of lithium through barrier film, generates insoluble lithium sulfide, and lithium sulfide poorly conductive causes cathode of lithium corrosion and the internal resistance of cell to increase, the capacity attenuation of final battery, cycle performance variation.
There is affinity on the surface of material with carbon element to sulphur, and between sulphur, there is stronger physisorption, therefore can be by elemental sulfur is mutually compound with the porous carbon materials with high conductivity, high-ratio surface or high pore capacities, sulphur is filled in the hole of porous carbon carrier inside and passage and prepares carbon sulphur composite material.In sulphur carbon composite, the yardstick of sulphur particle is restricted, and has effectively improved the conductivity of composite material, particle diameter and the ionic conduction distance of sulphur are reduced, and suppress the dissolving of intermediate product and the migration to negative pole, thus improve the utilance of elemental sulfur, further improve its cycle performance.In current document, mostly adopt template synthesis porous carbon materials, more compound with sulphur, prepare sulphur carbon composite, this method step is more, complex operation, experimental repeatability is bad, and high rate capability and the cycle performance of the sulphur carbon composite obtaining are poor.
Summary of the invention
The object of this invention is to provide a kind of hole carbon/sulphur composite material and preparation method thereof and application.
The preparation method of a kind of porous carbon/sulphur composite material provided by the present invention, comprises the steps:
(1) obtain reaction solution to adding water and stir in the mixture of alginic acid and metal hydroxides;
(2) this reaction solution is boiled off to moisture, then under nonoxidizing atmosphere, heat the precursor that obtains porous carbon materials;
(3) water or acid solution are processed the precursor of described porous carbon materials, and then drying obtains porous carbon materials;
(4) mixture of described porous carbon materials and sulphur powder is heated and obtain described porous carbon/sulphur composite material.
In above-mentioned preparation method, in step (1), described metal hydroxides can be selected from LiOH, NaOH, KOH, Mg (OH)
2and Ca (OH)
2in any one;
In the mixture of described alginic acid and metal hydroxides, the quality percentage composition of described metal hydroxides can be 1 ~ 90%, specifically can be 5% ~ 90%, 25% ~ 90%, 40% ~ 90%, 65% ~ 90%, 25%, 30%, 35%, 40%, 50%, 55%, 60%, 65%, 75% or 90%.
In above-mentioned preparation method, in step (2), described nonoxidizing atmosphere can be at least one in nitrogen, argon gas, hydrogen or helium;
The temperature of described heating can be 300 ~ 1000 ° of C, specifically can be 300 ° of C ~ 900 ° C, 500 ° of C～1000 ° C, 300 ° of C, 400 ° of C, 500 ° of C, 600 ° of C, 700 ° of C, 750 ° of C, 800 ° of C, 850 ° of C, 900 ° of C or 1000 ° of C;
The time of heating can be 0.5 ~ 72h, specifically can be 5h ~ 72h, 10h ~ 48h, 12h ~ 24h, 4h, 6h, 8h, 10h, 12h, 24h, 48h or 72h.
In above-mentioned preparation method, in step (3), described acid solution can be nitric acid, sulfuric acid, hydrochloric acid or the hydrofluoric acid of any concentration; The temperature of described processing can be 20 ° of C～150 ° C, specifically can be 20 ° of C ~ 70 ° C, 20 ° of C, 30 ° of C, 40 ° of C, 50 ° of C, 60 ° of C or 70 ° of C, the time of processing can be 0.5 ~ 72h, specifically can be 12h ~ 72h, 24h ~ 48h, 12h, 24h, 36h, 48h or 72h, the aperture of the porous carbon materials obtaining is 0.1nm ~ 100 μ m;
Described dry temperature can be 20 ° of C ~ 300 ° C, specifically can be 80 ° of C ~ 250 ° C, 150 ° of C ~ 250 ° C, 80 ° of C, 100 ° of C, 120 ° of C, 150 ° of C, 200 ° of C or 250 ° of C.
In above-mentioned preparation method, in step (4), in the mixture of described porous carbon materials and sulphur powder, the quality percentage composition of described sulphur powder can be 5% ~ 80%, as 15%, 20%, 25%, 35%, 40%, 45%, 50%, 55%, 60%, 75% or 80%.
The temperature of described heating can be 80 ~ 300 ° of C, specifically can be 80 ° of C ~ 250 ° C, 120 ° of C ~ 200 ° C, 80 ° of C, 120 ° of C, 130 ° of C, 140 ° of C, 150 ° of C, 160 ° of C, 170 ° of C, 180 ° of C, 190 ° of C, 200 ° of C, 220 ° of C, 230 ° of C, 250 ° of C or 300 ° of C;
Time can be 1 ~ 72h, specifically can be 10h ~ 72h, 10h ~ 48h, 10h, 24h, 36h, 40h, 48h, 60h or 72h.
The present invention also provides above-mentioned porous carbon/sulphur composite material in the application as in battery electrode material, particularly as the application of lithium sulfur battery anode material.
The present invention also provides a kind of energy storage elements, and described energy storage elements contains above-mentioned porous carbon/sulphur composite material, the preferred lithium-sulfur cell of this energy storage elements.
The present invention also provides a kind of portable electric appts, and described portable electric appts comprises above-mentioned energy storage elements; Described portable electric appts specifically can be mobile phone, camera, video camera, MP3, MP4 or notebook computer.
Compared with prior art, the preparation method of porous carbon/sulphur composite material provided by the invention is simple, and raw material is easy to get, suitable for mass production, and degree of being practical is high; Porous carbon/sulphur composite material provided by the invention, can directly use as the electrode material of battery.
Brief description of the drawings
Fig. 1 is the electron scanning micrograph of porous carbon/sulphur composite material of preparing of embodiment 1.
Fig. 2 is charging and discharging curve when porous carbon/sulphur composite material is as lithium sulfur battery anode material in embodiment 1.
Embodiment
The experimental technique using in following embodiment if no special instructions, is conventional method.
Material, reagent etc. used in following embodiment, if no special instructions, all can obtain from commercial channels.
Embodiment 1, prepare porous carbon/sulphur composite material
Take the mixture of alginic acid and NaOH, the mass ratio of NaOH is 50%, adds water, is uniformly mixed.Boil off moisture, under 700 ° of C, blanket of nitrogen heating 8h.React complete, add 50% aqueous sulfuric acid, after stirring at room temperature 24h, centrifugal washing with water for several times to neutral.Vacuumize under 80 ° of C, obtains porous carbon.The mixture that takes porous carbon and sulphur powder, the mass content of sulphur is 50%, after mixing, under air atmosphere, under 120 ° of C, heats 48h, obtains porous carbon/sulphur composite material.
The electron scanning micrograph of porous carbon/sulphur composite material prepared by the present embodiment as shown in Figure 1.
The Electrochemical Characterization of porous carbon/sulphur composite material:
Porous carbon/sulphur the composite material, carbon black and the binding agent that prepare are mixed and are made into slurry with mass ratio 80:10:10, be coated to equably and in aluminum foil current collector, obtain work electrode, using lithium sheet metal as to electrode, glass fibre membrane (Whatman company of Britain) is as barrier film, 1mol/L LiPF
6(solvent is ethylene carbonate and the dimethyl carbonate mixed liquor of volume ratio 1:1), as electrolyte, in glove box, assembling obtains Swagelok type battery.
The battery of above-mentioned assembling is carried out to charge-discharge test on LAND charge-discharge test instrument, and the interval that discharges and recharges of test is 1.0-3.0V.
As shown in Figure 2, synthetic porous carbon/sulphur composite material has good charging and discharging curve to result.Visible, when the synthetic porous carbon/sulphur composite material of the present invention is used as lithium sulfur battery anode material, there is chemical property.In the present embodiment, prepare Key Experiment condition and the simulated battery test result of porous carbon/sulphur composite material and list in table 1.
Embodiment 2, prepare porous carbon/sulphur composite material
Take the mixture of alginic acid and NaOH, the mass ratio of NaOH is 30%, adds water, is uniformly mixed.Boil off moisture, under 850 ° of C, blanket of nitrogen heating 6h.React complete, add 30% aqueous sulfuric acid, after stirring at room temperature 36h, centrifugal washing with water for several times to neutral.Vacuumize under 100 ° of C, obtains porous carbon.The mixture that takes porous carbon and sulphur powder, the mass content of sulphur is 45%, after mixing, under air atmosphere, under 250 ° of C, heats 10h, obtains porous carbon/sulphur composite material.
Test the chemical property of the porous carbon/sulphur composite material obtaining according to the method in embodiment 1, and Key Experiment condition and simulated battery test result that the present embodiment is prepared porous carbon/sulphur composite material are listed in table 1.
Embodiment 3, prepare porous carbon/sulphur composite material
Take the mixture of alginic acid and potassium hydroxide, the mass ratio of potassium hydroxide is 25%, adds water, is uniformly mixed.Boil off moisture, under 900 ° of C, argon atmospher heating 5h.React complete, add 20% aqueous solution of nitric acid, after stirring at room temperature 24h, centrifugal washing with water for several times to neutral.Dry under 150 ° of C in argon atmospher, obtain porous carbon.The mixture that takes porous carbon and sulphur powder, the mass content of sulphur is 40%, after mixing, under air atmosphere, under 160 ° of C, heats 36h, obtains porous carbon/sulphur composite material.
Test the chemical property of the porous carbon/sulphur composite material obtaining according to the method in embodiment 1, and Key Experiment condition and simulated battery test result that the present embodiment is prepared porous carbon/sulphur composite material are listed in table 1.
Embodiment 4, prepare porous carbon/sulphur composite material
Take the mixture of alginic acid and lithium hydroxide, the mass ratio of lithium hydroxide is 90%, adds water, is uniformly mixed.Boil off moisture, under 700 ° of C, blanket of nitrogen heating 10h.React complete, add 30% aqueous hydrochloric acid solution, after stirring at room temperature 24h, centrifugal washing with water for several times to neutral.Vacuumize under 250 ° of C, obtains porous carbon.The mixture that takes porous carbon and sulphur powder, the mass content of sulphur is 60%, after mixing, under air atmosphere, under 80 ° of C, heats 72h, obtains porous carbon/sulphur composite material.
Test the chemical property of the porous carbon/sulphur composite material obtaining according to the method in embodiment 1, and Key Experiment condition and simulated battery test result that the present embodiment is prepared porous carbon/sulphur composite material are listed in table 1.
Embodiment 5, prepare porous carbon/sulphur composite material
Take the mixture of alginic acid and lithium hydroxide, the mass ratio of lithium hydroxide is 40%, adds water, is uniformly mixed.Boil off moisture, under 1000 ° of C, blanket of nitrogen heating 5h.React complete, add 10% hydrofluoric acid aqueous solution, after stirring at room temperature 48h, centrifugal washing with water for several times to neutral.Vacuumize under 200 ° of C, obtains porous carbon.The mixture that takes porous carbon and sulphur powder, the mass content of sulphur is 20%, after mixing, under air atmosphere, under 230 ° of C, heats 36h, obtains porous carbon/sulphur composite material.
Test the chemical property of the porous carbon/sulphur composite material obtaining according to the method in embodiment 1, and Key Experiment condition and simulated battery test result that the present embodiment is prepared porous carbon/sulphur composite material are listed in table 1.
Embodiment 6, prepare porous carbon/sulphur composite material
Take the mixture of alginic acid and calcium hydroxide, the mass ratio of calcium hydroxide is 55%, adds water, is uniformly mixed.Boil off moisture, under 750 ° of C, argon atmospher heating 12h.React complete, add 15% hydrochloric acid aqueous acid, after stirring at room temperature 24h, centrifugal washing with water for several times to neutral.Vacuumize under 150 ° of C, obtains porous carbon.The mixture that takes porous carbon and sulphur powder, the mass content of sulphur is 80%, after mixing, under air atmosphere, under 300 ° of C, heats 24h, obtains porous carbon/sulphur composite material.
Test the chemical property of the porous carbon/sulphur composite material obtaining according to the method in embodiment 1, and Key Experiment condition and simulated battery test result that the present embodiment is prepared porous carbon/sulphur composite material are listed in table 1.
Embodiment 7, prepare porous carbon/sulphur composite material
Take the mixture of alginic acid and NaOH, the mass ratio of NaOH is 60%, adds water, is uniformly mixed.Boil off moisture, under 700 ° of C, blanket of nitrogen heating 8h.React complete, add 10% aqueous sulfuric acid, under 40 ° of C, stir after 48h, centrifugal washing with water for several times to neutral.Vacuumize under 150 ° of C, obtains porous carbon.The mixture that takes porous carbon and sulphur powder, the mass content of sulphur is 55%, after mixing, under air atmosphere, under 140 ° of C, heats 48h, obtains porous carbon/sulphur composite material.
Test the chemical property of the porous carbon/sulphur composite material obtaining according to the method in embodiment 1, and Key Experiment condition and simulated battery test result that the present embodiment is prepared porous carbon/sulphur composite material are listed in table 1.
Embodiment 8, prepare porous carbon/sulphur composite material
Take the mixture of alginic acid and calcium hydroxide, the mass ratio of calcium hydroxide is 30%, adds water, is uniformly mixed.Boil off moisture, under 700 ° of C, blanket of nitrogen heating 10h.React complete, add 30% aqueous sulfuric acid, after stirring at room temperature 36h, centrifugal washing with water for several times to neutral.Vacuumize under 150 ° of C, obtains porous carbon.The mixture that takes porous carbon and sulphur powder, the mass content of sulphur is 45%, after mixing, under air atmosphere, under 180 ° of C, heats 36h, obtains porous carbon/sulphur composite material.
Test the chemical property of the porous carbon/sulphur composite material obtaining according to the method in embodiment 1, and Key Experiment condition and simulated battery test result that the present embodiment is prepared porous carbon/sulphur composite material are listed in table 1.
Embodiment 9, prepare porous carbon/sulphur composite material
Take the mixture of alginic acid and magnesium hydroxide, the mass ratio of magnesium hydroxide is 35%, adds water, is uniformly mixed.Boil off moisture, under 750 ° of C, blanket of nitrogen heating 10h.React complete, add 10% aqueous hydrochloric acid solution, under 70 ° of C, stir after 48h, centrifugal washing with water for several times to neutral.Vacuumize under 150 ° of C, obtains porous carbon.The mixture that takes porous carbon and sulphur powder, the mass content of sulphur is 60%, after mixing, under air atmosphere, under 200 ° of C, heats 48h, obtains porous carbon/sulphur composite material.
Test the chemical property of the porous carbon/sulphur composite material obtaining according to the method in embodiment 1, and Key Experiment condition and simulated battery test result that the present embodiment is prepared porous carbon/sulphur composite material are listed in table 1.
Embodiment 10, prepare porous carbon/sulphur composite material
Take the mixture of alginic acid and calcium hydroxide, the mass ratio of calcium hydroxide is 30%, adds water, is uniformly mixed.Boil off moisture, under 700 ° of C, blanket of nitrogen heating 12h.React complete, add 25% aqueous sulfuric acid, after stirring at room temperature 12h, centrifugal washing with water for several times to neutral.Vacuumize under 150 ° of C, obtains porous carbon.The mixture that takes porous carbon and sulphur powder, the mass content of sulphur is 75%, after mixing, under air atmosphere, under 220 ° of C, heats 40h, obtains porous carbon/sulphur composite material.
Test the chemical property of the porous carbon/sulphur composite material obtaining according to the method in embodiment 1, and Key Experiment condition and simulated battery test result that the present embodiment is prepared porous carbon/sulphur composite material are listed in table 1.
Embodiment 11, prepare porous carbon/sulphur composite material
Take the mixture of alginic acid and NaOH, the mass ratio of NaOH is 55%, adds water, is uniformly mixed.Boil off moisture, under 800 ° of C, blanket of nitrogen heating 24h.React complete, add 10% aqueous sulfuric acid, under 30 ° of C, stir after 48h, centrifugal washing with water for several times to neutral.Vacuumize under 150 ° of C, obtains porous carbon.The mixture that takes porous carbon and sulphur powder, the mass content of sulphur is 60%, after mixing, under air atmosphere, under 150 ° of C, heats 60h, obtains porous carbon/sulphur composite material.
Test the chemical property of the porous carbon/sulphur composite material obtaining according to the method in embodiment 1, and Key Experiment condition and simulated battery test result that the present embodiment is prepared porous carbon/sulphur composite material are listed in table 1.
Embodiment 12, prepare porous carbon/sulphur composite material
Take the mixture of alginic acid and potassium hydroxide, the mass ratio of potassium hydroxide is 75%, adds water, is uniformly mixed.Boil off moisture, under 600 ° of C, blanket of nitrogen heating 5h.React complete, add the aqueous solution, after stirring at room temperature 72h, centrifugal washing with water for several times to neutral.Vacuumize under 150 ° of C, obtains porous carbon.The mixture that takes porous carbon and sulphur powder, the mass content of sulphur is 35%, after mixing, under air atmosphere, under 170 ° of C, heats 60h, obtains porous carbon/sulphur composite material.
Test the chemical property of the porous carbon/sulphur composite material obtaining according to the method in embodiment 1, and Key Experiment condition and simulated battery test result that the present embodiment is prepared porous carbon/sulphur composite material are listed in table 1.
Embodiment 13, prepare porous carbon/sulphur composite material
Take the mixture of alginic acid and NaOH, the mass ratio of NaOH is 65%, adds water, is uniformly mixed.Boil off moisture, under 500 ° of C, blanket of nitrogen heating 24h.React complete, add the aqueous solution, after stirring at room temperature 72h, centrifugal washing with water for several times to neutral.Vacuumize under 150 ° of C, obtains porous carbon.The mixture that takes porous carbon and sulphur powder, the mass content of sulphur is 25%, after mixing, under air atmosphere, under 130 ° of C, heats 48h, obtains porous carbon/sulphur composite material.
Embodiment 14, prepare porous carbon/sulphur composite material
Take the mixture of alginic acid and NaOH, the mass ratio of NaOH is 5%, adds water, is uniformly mixed.Boil off moisture, under 400 ° of C, blanket of nitrogen heating 48h.React complete, add 30% aqueous sulfuric acid, under 50 ° of C, stir after 24h, centrifugal washing with water for several times to neutral.Vacuumize under 150 ° of C, obtains porous carbon.The mixture that takes porous carbon and sulphur powder, the mass content of sulphur is 40%, after mixing, under air atmosphere, under 120 ° of C, heats 72h, obtains porous carbon/sulphur composite material.
Embodiment 15, prepare porous carbon/sulphur composite material
Take the mixture of alginic acid and potassium hydroxide, the mass ratio of potassium hydroxide is 65%, adds water, is uniformly mixed.Boil off moisture, under 300 ° of C, argon atmospher heating 72h.React complete, add 20% aqueous hydrochloric acid solution, under 60 ° of C, stir after 48h, centrifugal washing with water for several times to neutral.Vacuumize under 250 ° of C, obtains porous carbon.The mixture that takes porous carbon and sulphur powder, the mass content of sulphur is 40%, after mixing, under air atmosphere, under 150 ° of C, heats 36h, obtains porous carbon/sulphur composite material.
Test the chemical property of the porous carbon/sulphur composite material obtaining according to the method in embodiment 1, and Key Experiment condition and simulated battery test result that the present embodiment is prepared porous carbon/sulphur composite material are listed in table 1.
Embodiment 16, prepare porous carbon/sulphur composite material
Take the mixture of alginic acid and lithium hydroxide, the mass ratio of lithium hydroxide is 35%, adds water, is uniformly mixed.Boil off moisture, under 750 ° of C, blanket of nitrogen heating 12h.React complete, add 30% aqueous sulfuric acid, after stirring at room temperature 36h, centrifugal washing with water for several times to neutral.Vacuumize under 120 ° of C, obtains porous carbon.The mixture that takes porous carbon and sulphur powder, the mass content of sulphur is 15%, after mixing, under air atmosphere, under 190 ° of C, heats 48h, obtains porous carbon/sulphur composite material.
Test the chemical property of the porous carbon/sulphur composite material obtaining according to the method in embodiment 1, and Key Experiment condition and simulated battery test result that the present embodiment is prepared porous carbon/sulphur composite material are listed in table 1.
Preparation condition and the simulated battery test result of table 1, porous carbon/sulphur composite material material
Result by table 1 can find out, the present invention prepares porous carbon with alginic acid and metal hydroxides, more further compound with sulphur, can conveniently prepare porous carbon/sulphur composite material positive electrode.Utilize the inventive method not only can greatly reduce the preparation cost of material, and porous carbon/sulphur composite material positive electrode that the present invention obtains all show higher capacity.
Claims (8)
1. a preparation method for porous carbon/sulphur composite material, comprises the steps:
(1) obtain reaction solution to adding water and stir in the mixture of alginic acid and metal hydroxides;
(2) this reaction solution is boiled off to moisture, then under nonoxidizing atmosphere, heat the precursor that obtains porous carbon materials;
(3) water or acid solution are processed the precursor of described porous carbon materials, and then drying obtains porous carbon materials;
(4) mixture of described porous carbon materials and sulphur powder is heated and obtain described porous carbon/sulphur composite material;
In step (1), described metal hydroxides is selected from LiOH, NaOH and KOH any one;
In the mixture of described alginic acid and metal hydroxides, the quality percentage composition of described metal hydroxides is 1～90%;
In step (2), the temperature of described heating is 300～1000 DEG C, and the time of heating is 0.5～72h;
In step (4), in the mixture of described porous carbon materials and sulphur powder, the quality percentage composition of described sulphur powder is 5%～80%;
The temperature of described heating is 80～300 DEG C, and the time is 1～72h.
2. method according to claim 1, is characterized in that: in step (2), described nonoxidizing atmosphere is at least one in nitrogen, argon gas, hydrogen or helium.
3. method according to claim 1 and 2, is characterized in that: in step (3), described acid solution is nitric acid, sulfuric acid, hydrochloric acid or hydrofluoric acid; The temperature of described processing is 20 DEG C～150 DEG C, and the time of processing is 0.5～72h;
Described dry temperature is 20 DEG C～300 DEG C.
4. porous carbon/sulphur composite material that in claim 1-3, described in any one prepared by method.
Described in claim 4 porous carbon/sulphur composite material in the application as in battery electrode material.
6. an energy storage elements, is characterized in that: described energy storage elements contains porous carbon/sulphur composite material claimed in claim 4.
7. a portable electric appts, is characterized in that: described portable electric appts comprises energy storage elements claimed in claim 6.
8. electronic equipment according to claim 7, is characterized in that: described portable electric appts is mobile phone, camera, video camera, MP3, MP4 or notebook computer.
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| CN103606649B (en) * | 2013-11-21 | 2016-02-17 | 浙江工业大学 | A kind of electrolytic preparation method of sulphur/carbon composite |
| CN105990573B (en) * | 2015-03-06 | 2019-03-01 | 国家纳米科学中心 | A kind of N doping porous carbon/sulphur composite material and preparation method and purposes |
| JP6756742B2 (en) * | 2015-06-05 | 2020-09-16 | ローベルト ボツシユ ゲゼルシヤフト ミツト ベシユレンクテル ハフツングＲｏｂｅｒｔ Ｂｏｓｃｈ Ｇｍｂｈ | Sulfur-carbon composites containing microporous carbon nanosheets for lithium-sulfur batteries and the process for preparing them |
| CN105826540B (en) * | 2016-06-03 | 2018-10-02 | 合肥工业大学 | A kind of lithium-sulfur cell composite positive pole and the preparation method and application thereof |
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| CN110473710A (en) * | 2018-05-10 | 2019-11-19 | 北京化工大学 | Porous carbon materials and its preparation method and application |
| CN109167063A (en) * | 2018-08-15 | 2019-01-08 | 广东工业大学 | A kind of lithium anode and its preparation method and application of artificial solid electrolyte interface layer protection |
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| N. Jayaprakash等.Porous Hollow CarbonSulfur Composites for High-Power Lithium–Sulfur Batteries.《Angewandte Chemie》.2011,第123卷(第26期),第6026-6030页. * |
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