CN102820456A - 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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- CN102820456A CN102820456A CN2012102973957A CN201210297395A CN102820456A CN 102820456 A CN102820456 A CN 102820456A CN 2012102973957 A CN2012102973957 A CN 2012102973957A CN 201210297395 A CN201210297395 A CN 201210297395A CN 102820456 A CN102820456 A CN 102820456A
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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, press for and develop the more battery of high-energy-density.Be restricted owing to improve the anode material for lithium-ion batteries capacity, the energy density of lithium ion battery is difficult to further increase considerably.Improve energy density through the voltage platform that increases positive electrode simultaneously and can bring safety issue again.Forward positive electrode to " conversion reaction chemism " from " taking off embedding 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 the lithium metal complete reaction
2S, cell reaction are S+2Li=Li
2S is the bielectron course of reaction, and the embedding of taking off that does not relate to lithium ion is reacted.Because the molecular weight of sulphur is low, so the theoretical specific capacity of sulphur is up to 1675mAhg
-1(almost be LiFePO
410 times), theoretical specific energy then is 2600Wh Kg
-1In addition, elemental sulfur is abundant at the nature reserves, low toxicity, cheap, so elemental sulfur is a kind of positive active material that haves a great attraction.
But the 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 that generates in the charge and discharge process is soluble in the electrolyte, and electrode active material reduces gradually, and capacity reduces; 3) owing to shuttling back and forth principle, the polysulfide that dissolves in the electrolyte passes barrier film and contacts with cathode of lithium, generates insoluble lithium sulfide, and the lithium sulfide poorly conductive causes the 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 stronger physisorption is arranged between the sulphur; Therefore can sulphur be filled in inner hole of porous carbon carrier and the passage prepare carbon sulphur composite material through elemental sulfur is mutually compound with the porous carbon materials with high conductivity, high-ratio surface or high pore capacities.In the sulphur carbon composite, the yardstick of sulphur particle is restricted, and has effectively improved the conductivity of composite material; The particle diameter and the ionic conduction distance of sulphur have been reduced; And suppress the dissolving of intermediate product and to the migration of negative pole, thus improve the utilance of elemental sulfur, further improve its cycle performance.Adopt template to prepare porous carbon materials in the current document mostly, compound with sulphur again, preparation sulphur carbon composite, this method step is more, complex operation, experimental repeatability is bad, and the high rate capability and the cycle performance of the sulphur carbon composite that obtains are relatively poor.
Summary of the invention
The purpose 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 provided by the present invention/sulphur composite material comprises the steps:
(1) in the mixture of alginic acid and metal hydroxides, adds entry and stir and obtain reaction solution;
(2) this reaction solution is boiled off moisture, under nonoxidizing atmosphere, heat the precursor that obtains porous carbon materials then;
(3) water or acid solution are handled the precursor of said porous carbon materials, obtain porous carbon materials through drying then;
(4) mixture of said porous carbon materials and sulphur powder is heated promptly get said porous carbon/sulphur composite material.
Among the above-mentioned preparation method, in the step (1), said metal hydroxides can be selected from LiOH, NaOH, KOH, Mg (OH)
2And Ca (OH)
2In any one;
In the mixture of said alginic acid and metal hydroxides; The quality percentage composition of said 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%.
Among the above-mentioned preparation method, in the step (2), said nonoxidizing atmosphere can be in nitrogen, argon gas, hydrogen or the helium at least a;
The temperature of said 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.
Among the above-mentioned preparation method, in the step (3), said acid solution can be nitric acid, sulfuric acid, hydrochloric acid or the hydrofluoric acid of any concentration; Said treatment temperature 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 handling 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 that obtains is 0.1nm ~ 100 μ m;
The temperature of said drying 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.
Among the above-mentioned preparation method, in the step (4), in the mixture of said porous carbon materials and sulphur powder, the quality percentage composition of said sulphur powder can be 5% ~ 80%, as 15%, 20%, 25%, 35%, 40%, 45%, 50%, 55%, 60%, 75% or 80%.
The temperature of said 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 as the application in the battery electrode material, particularly as the application of lithium-sulphur cell positive electrode material.
The present invention also provides a kind of energy storage elements, and said 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 said portable electric appts comprises above-mentioned energy storage elements; Said 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 provided by the invention/sulphur composite material is simple, and raw material is easy to get, suitable for mass production, and degree of being practical is high; Porous carbon provided by the invention/sulphur composite material can be directly uses as the electrode material of battery.
Description of drawings
Fig. 1 is the electron scanning micrograph of the porous carbon/sulphur composite material of embodiment 1 preparation.
Fig. 2 is the charging and discharging curve of porous carbon among the embodiment 1/sulphur composite material during as the lithium-sulphur cell positive electrode material.
Embodiment
Employed experimental technique is conventional method like no specified otherwise among the following embodiment.
Used material, reagent etc. like no specified otherwise, all can obtain from commercial sources among the following embodiment.
Take by weighing the mixture of alginic acid and NaOH, the mass ratio of NaOH is 50%, adds entry, mixes.Boil off moisture, under 700 ° of C, blanket of nitrogen heating 8h.Reaction finishes, and adds 50% aqueous sulfuric acid, and is behind the stirring at room 24h, centrifugal extremely neutral for several times with water washing.Vacuumize under 80 ° of C obtains porous carbon.Take by weighing the mixture of porous carbon and sulphur powder, the mass content of sulphur is 50%, and after mixing, under air atmosphere, 120 ° of C heat 48h down, obtain porous carbon/sulphur composite material.
The electron scanning micrograph of the porous carbon/sulphur composite material of present embodiment preparation is as shown in Figure 1.
The chemical property of porous carbon/sulphur composite material characterizes:
The porous carbon for preparing/sulphur composite material, carbon black and binding agent are made into slurry with mass ratio 80:10:10 mixing; Be coated to equably and obtain work electrode on the aluminum foil current collector; With the lithium sheet metal as to electrode; Glass fibre membrane (Britain Whatman company) 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, assembling obtains Swagelok type battery in glove box.
The battery of above-mentioned assembling is carried out charge-discharge test on LAND charge-discharge test appearance, the interval that discharges and recharges of test is 1.0-3.0V.
The result is as shown in Figure 2, and synthetic porous carbon/sulphur composite material has good charging and discharging curve.Thus it is clear that, when the porous carbon that the present invention synthesizes/sulphur composite material is used as the lithium-sulphur cell positive electrode material, have chemical property.The Key Experiment condition and the simulated battery test result that prepare porous carbon/sulphur composite material in the present embodiment are listed in table 1.
Embodiment 2, preparation porous carbon/sulphur composite material
Take by weighing the mixture of alginic acid and NaOH, the mass ratio of NaOH is 30%, adds entry, mixes.Boil off moisture, under 850 ° of C, blanket of nitrogen heating 6h.Reaction finishes, and adds 30% aqueous sulfuric acid, and is behind the stirring at room 36h, centrifugal extremely neutral for several times with water washing.Vacuumize under 100 ° of C obtains porous carbon.Take by weighing the mixture of porous carbon and sulphur powder, the mass content of sulphur is 45%, and after mixing, under air atmosphere, 250 ° of C heat 10h down, obtain porous carbon/sulphur composite material.
The chemical property of the porous carbon/sulphur composite material that obtains according to the method among the embodiment 1 test, and Key Experiment condition and simulated battery test result that present embodiment prepares porous carbon/sulphur composite material are listed in table 1.
Embodiment 3, preparation porous carbon/sulphur composite material
Take by weighing the mixture of alginic acid and potassium hydroxide, the mass ratio of potassium hydroxide is 25%, adds entry, mixes.Boil off moisture, under 900 ° of C, argon atmospher heating 5h.Reaction finishes, and adds 20% aqueous solution of nitric acid, and is behind the stirring at room 24h, centrifugal extremely neutral for several times with water washing.150 ° of C are dry down in the argon atmospher, obtain porous carbon.Take by weighing the mixture of porous carbon and sulphur powder, the mass content of sulphur is 40%, and after mixing, under air atmosphere, 160 ° of C heat 36h down, obtain porous carbon/sulphur composite material.
The chemical property of the porous carbon/sulphur composite material that obtains according to the method among the embodiment 1 test, and Key Experiment condition and simulated battery test result that present embodiment prepares porous carbon/sulphur composite material are listed in table 1.
Embodiment 4, preparation porous carbon/sulphur composite material
Take by weighing the mixture of alginic acid and lithium hydroxide, the mass ratio of lithium hydroxide is 90%, adds entry, mixes.Boil off moisture, under 700 ° of C, blanket of nitrogen heating 10h.Reaction finishes, and adds 30% aqueous hydrochloric acid solution, and is behind the stirring at room 24h, centrifugal extremely neutral for several times with water washing.Vacuumize under 250 ° of C obtains porous carbon.Take by weighing the mixture of porous carbon and sulphur powder, the mass content of sulphur is 60%, and after mixing, under air atmosphere, 80 ° of C heat 72h down, obtain porous carbon/sulphur composite material.
The chemical property of the porous carbon/sulphur composite material that obtains according to the method among the embodiment 1 test, and Key Experiment condition and simulated battery test result that present embodiment prepares porous carbon/sulphur composite material are listed in table 1.
Embodiment 5, preparation porous carbon/sulphur composite material
Take by weighing the mixture of alginic acid and lithium hydroxide, the mass ratio of lithium hydroxide is 40%, adds entry, mixes.Boil off moisture, under 1000 ° of C, blanket of nitrogen heating 5h.Reaction finishes, and adds 10% hydrofluoric acid aqueous solution, and is behind the stirring at room 48h, centrifugal extremely neutral for several times with water washing.Vacuumize under 200 ° of C obtains porous carbon.Take by weighing the mixture of porous carbon and sulphur powder, the mass content of sulphur is 20%, and after mixing, under air atmosphere, 230 ° of C heat 36h down, obtain porous carbon/sulphur composite material.
The chemical property of the porous carbon/sulphur composite material that obtains according to the method among the embodiment 1 test, and Key Experiment condition and simulated battery test result that present embodiment prepares porous carbon/sulphur composite material are listed in table 1.
Embodiment 6, preparation porous carbon/sulphur composite material
Take by weighing the mixture of alginic acid and calcium hydroxide, the mass ratio of calcium hydroxide is 55%, adds entry, mixes.Boil off moisture, under 750 ° of C, argon atmospher heating 12h.Reaction finishes, and adds 15% hydrochloric acid aqueous acid, and is behind the stirring at room 24h, centrifugal extremely neutral for several times with water washing.Vacuumize under 150 ° of C obtains porous carbon.Take by weighing the mixture of porous carbon and sulphur powder, the mass content of sulphur is 80%, and after mixing, under air atmosphere, 300 ° of C heat 24h down, obtain porous carbon/sulphur composite material.
The chemical property of the porous carbon/sulphur composite material that obtains according to the method among the embodiment 1 test, and Key Experiment condition and simulated battery test result that present embodiment prepares porous carbon/sulphur composite material are listed in table 1.
Embodiment 7, preparation porous carbon/sulphur composite material
Take by weighing the mixture of alginic acid and NaOH, the mass ratio of NaOH is 60%, adds entry, mixes.Boil off moisture, under 700 ° of C, blanket of nitrogen heating 8h.Reaction finishes, and adds 10% aqueous sulfuric acid, and is after 40 ° of C stir 48h down, centrifugal extremely neutral for several times with water washing.Vacuumize under 150 ° of C obtains porous carbon.Take by weighing the mixture of porous carbon and sulphur powder, the mass content of sulphur is 55%, and after mixing, under air atmosphere, 140 ° of C heat 48h down, obtain porous carbon/sulphur composite material.
The chemical property of the porous carbon/sulphur composite material that obtains according to the method among the embodiment 1 test, and Key Experiment condition and simulated battery test result that present embodiment prepares porous carbon/sulphur composite material are listed in table 1.
Embodiment 8, preparation porous carbon/sulphur composite material
Take by weighing the mixture of alginic acid and calcium hydroxide, the mass ratio of calcium hydroxide is 30%, adds entry, mixes.Boil off moisture, under 700 ° of C, blanket of nitrogen heating 10h.Reaction finishes, and adds 30% aqueous sulfuric acid, and is behind the stirring at room 36h, centrifugal extremely neutral for several times with water washing.Vacuumize under 150 ° of C obtains porous carbon.Take by weighing the mixture of porous carbon and sulphur powder, the mass content of sulphur is 45%, and after mixing, under air atmosphere, 180 ° of C heat 36h down, obtain porous carbon/sulphur composite material.
The chemical property of the porous carbon/sulphur composite material that obtains according to the method among the embodiment 1 test, and Key Experiment condition and simulated battery test result that present embodiment prepares porous carbon/sulphur composite material are listed in table 1.
Embodiment 9, preparation porous carbon/sulphur composite material
Take by weighing the mixture of alginic acid and magnesium hydroxide, the mass ratio of magnesium hydroxide is 35%, adds entry, mixes.Boil off moisture, under 750 ° of C, blanket of nitrogen heating 10h.Reaction finishes, and adds 10% aqueous hydrochloric acid solution, and is after 70 ° of C stir 48h down, centrifugal extremely neutral for several times with water washing.Vacuumize under 150 ° of C obtains porous carbon.Take by weighing the mixture of porous carbon and sulphur powder, the mass content of sulphur is 60%, and after mixing, under air atmosphere, 200 ° of C heat 48h down, obtain porous carbon/sulphur composite material.
The chemical property of the porous carbon/sulphur composite material that obtains according to the method among the embodiment 1 test, and Key Experiment condition and simulated battery test result that present embodiment prepares porous carbon/sulphur composite material are listed in table 1.
Embodiment 10, preparation porous carbon/sulphur composite material
Take by weighing the mixture of alginic acid and calcium hydroxide, the mass ratio of calcium hydroxide is 30%, adds entry, mixes.Boil off moisture, under 700 ° of C, blanket of nitrogen heating 12h.Reaction finishes, and adds 25% aqueous sulfuric acid, and is behind the stirring at room 12h, centrifugal extremely neutral for several times with water washing.Vacuumize under 150 ° of C obtains porous carbon.Take by weighing the mixture of porous carbon and sulphur powder, the mass content of sulphur is 75%, and after mixing, under air atmosphere, 220 ° of C heat 40h down, obtain porous carbon/sulphur composite material.
The chemical property of the porous carbon/sulphur composite material that obtains according to the method among the embodiment 1 test, and Key Experiment condition and simulated battery test result that present embodiment prepares porous carbon/sulphur composite material are listed in table 1.
Embodiment 11, preparation porous carbon/sulphur composite material
Take by weighing the mixture of alginic acid and NaOH, the mass ratio of NaOH is 55%, adds entry, mixes.Boil off moisture, under 800 ° of C, blanket of nitrogen heating 24h.Reaction finishes, and adds 10% aqueous sulfuric acid, and is after 30 ° of C stir 48h down, centrifugal extremely neutral for several times with water washing.Vacuumize under 150 ° of C obtains porous carbon.Take by weighing the mixture of porous carbon and sulphur powder, the mass content of sulphur is 60%, and after mixing, under air atmosphere, 150 ° of C heat 60h down, obtain porous carbon/sulphur composite material.
The chemical property of the porous carbon/sulphur composite material that obtains according to the method among the embodiment 1 test, and Key Experiment condition and simulated battery test result that present embodiment prepares porous carbon/sulphur composite material are listed in table 1.
Embodiment 12, preparation porous carbon/sulphur composite material
Take by weighing the mixture of alginic acid and potassium hydroxide, the mass ratio of potassium hydroxide is 75%, adds entry, mixes.Boil off moisture, under 600 ° of C, blanket of nitrogen heating 5h.Reaction finishes, and adds the aqueous solution, and is behind the stirring at room 72h, centrifugal extremely neutral for several times with water washing.Vacuumize under 150 ° of C obtains porous carbon.Take by weighing the mixture of porous carbon and sulphur powder, the mass content of sulphur is 35%, and after mixing, under air atmosphere, 170 ° of C heat 60h down, obtain porous carbon/sulphur composite material.
The chemical property of the porous carbon/sulphur composite material that obtains according to the method among the embodiment 1 test, and Key Experiment condition and simulated battery test result that present embodiment prepares porous carbon/sulphur composite material are listed in table 1.
Embodiment 13, preparation porous carbon/sulphur composite material
Take by weighing the mixture of alginic acid and NaOH, the mass ratio of NaOH is 65%, adds entry, mixes.Boil off moisture, under 500 ° of C, blanket of nitrogen heating 24h.Reaction finishes, and adds the aqueous solution, and is behind the stirring at room 72h, centrifugal extremely neutral for several times with water washing.Vacuumize under 150 ° of C obtains porous carbon.Take by weighing the mixture of porous carbon and sulphur powder, the mass content of sulphur is 25%, and after mixing, under air atmosphere, 130 ° of C heat 48h down, obtain porous carbon/sulphur composite material.
Embodiment 14, preparation porous carbon/sulphur composite material
Take by weighing the mixture of alginic acid and NaOH, the mass ratio of NaOH is 5%, adds entry, mixes.Boil off moisture, under 400 ° of C, blanket of nitrogen heating 48h.Reaction finishes, and adds 30% aqueous sulfuric acid, and is after 50 ° of C stir 24h down, centrifugal extremely neutral for several times with water washing.Vacuumize under 150 ° of C obtains porous carbon.Take by weighing the mixture of porous carbon and sulphur powder, the mass content of sulphur is 40%, and after mixing, under air atmosphere, 120 ° of C heat 72h down, obtain porous carbon/sulphur composite material.
Embodiment 15, preparation porous carbon/sulphur composite material
Take by weighing the mixture of alginic acid and potassium hydroxide, the mass ratio of potassium hydroxide is 65%, adds entry, mixes.Boil off moisture, under 300 ° of C, argon atmospher heating 72h.Reaction finishes, and adds 20% aqueous hydrochloric acid solution, and is after 60 ° of C stir 48h down, centrifugal extremely neutral for several times with water washing.Vacuumize under 250 ° of C obtains porous carbon.Take by weighing the mixture of porous carbon and sulphur powder, the mass content of sulphur is 40%, and after mixing, under air atmosphere, 150 ° of C heat 36h down, obtain porous carbon/sulphur composite material.
The chemical property of the porous carbon/sulphur composite material that obtains according to the method among the embodiment 1 test, and Key Experiment condition and simulated battery test result that present embodiment prepares porous carbon/sulphur composite material are listed in table 1.
Embodiment 16, preparation porous carbon/sulphur composite material
Take by weighing the mixture of alginic acid and lithium hydroxide, the mass ratio of lithium hydroxide is 35%, adds entry, mixes.Boil off moisture, under 750 ° of C, blanket of nitrogen heating 12h.Reaction finishes, and adds 30% aqueous sulfuric acid, and is behind the stirring at room 36h, centrifugal extremely neutral for several times with water washing.Vacuumize under 120 ° of C obtains porous carbon.Take by weighing the mixture of porous carbon and sulphur powder, the mass content of sulphur is 15%, and after mixing, under air atmosphere, 190 ° of C heat 48h down, obtain porous carbon/sulphur composite material.
The chemical property of the porous carbon/sulphur composite material that obtains according to the method among the embodiment 1 test, and Key Experiment condition and simulated battery test result that present embodiment prepares porous carbon/sulphur composite material are listed in table 1.
The preparation condition and the simulated battery test result of table 1, porous carbon/sulphur composite material material
Result by table 1 can find out that the present invention prepares porous carbon with alginic acid and metal hydroxides, and is further compound with sulphur again, can conveniently prepare porous carbon/sulphur composite material positive electrode.Utilize the inventive method not only can reduce the preparation cost of material greatly, and porous carbon/sulphur composite material positive electrode that the present invention obtains has all shown higher capacity.
Claims (10)
1. the preparation method of porous carbon/sulphur composite material comprises the steps:
(1) in the mixture of alginic acid and metal hydroxides, adds entry and stir and obtain reaction solution;
(2) this reaction solution is boiled off moisture, under nonoxidizing atmosphere, heat the precursor that obtains porous carbon materials then;
(3) water or acid solution are handled the precursor of said porous carbon materials, obtain porous carbon materials through drying then;
(4) mixture of said porous carbon materials and sulphur powder is heated promptly get said porous carbon/sulphur composite material.
2. preparation method according to claim 1 is characterized in that: in the step (1), said metal hydroxides is selected from LiOH, NaOH, KOH, Mg (OH)
2And Ca (OH)
2In any one;
In the mixture of said alginic acid and metal hydroxides, the quality percentage composition of said metal hydroxides is 1 ~ 90%.
3. method according to claim 1 and 2 is characterized in that: in the step (2), said nonoxidizing atmosphere is at least a in nitrogen, argon gas, hydrogen or the helium;
The temperature of said heating is 300 ~ 1000 ° of C, and the time of heating is 0.5 ~ 72h.
4. according to each described method among the claim 1-3, it is characterized in that: in the step (3), said acid solution is nitric acid, sulfuric acid, hydrochloric acid or hydrofluoric acid; Said treatment temperature is 20 ° of C～150 ° C, and the time of processing is 0.5 ~ 72h;
The temperature of said drying is 20 ° of C ~ 300 ° C.
5. according to each described method among the claim 1-4, it is characterized in that: in the step (4), in the mixture of said porous carbon materials and sulphur powder, the quality percentage composition of said sulphur powder is 5% ~ 80%;
The temperature of said heating is 80 ~ 300 ° of C, and the time is 1 ~ 72h.
6. porous carbon/sulphur composite material that each said method prepares among the claim 1-5.
7. the said porous carbon of claim 6/sulphur composite material is as the application in the battery electrode material;
8. energy storage elements, it is characterized in that: said energy storage elements contains the described porous carbon of claim 6/sulphur composite material.
9. portable electric appts, it is characterized in that: said portable electric appts comprises the described energy storage elements of claim 8.
10. electronic equipment according to claim 9 is characterized in that: said portable electric appts is mobile phone, camera, video camera, MP3, MP4 or notebook computer.
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| CN103187560A (en) * | 2013-03-30 | 2013-07-03 | 浙江工业大学 | Sulfur-carbon composite material with imitation animal scaly structure and application thereof |
| CN103606649A (en) * | 2013-11-21 | 2014-02-26 | 浙江工业大学 | Electrolysis preparation method of sulfur/carbon composite material |
| CN105826540A (en) * | 2016-06-03 | 2016-08-03 | 合肥工业大学 | Lithium-sulfur battery composite anode material and preparation method and application thereof |
| CN105990573A (en) * | 2015-03-06 | 2016-10-05 | 国家纳米科学中心 | Nitrogen-doped porous carbon/sulfur composite material and preparing method and application thereof |
| CN106099110A (en) * | 2016-07-11 | 2016-11-09 | 杭州电子科技大学 | A kind of method utilizing algae to prepare Li S cell positive material as carbon source |
| CN107615526A (en) * | 2015-06-05 | 2018-01-19 | 罗伯特·博世有限公司 | Sulphur carbon composite comprising micropore carbon nanosheet for lithium-sulfur cell and preparation method thereof |
| 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 |
| CN110473710A (en) * | 2018-05-10 | 2019-11-19 | 北京化工大学 | Porous carbon materials and its preparation method and application |
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| CN103187560B (en) * | 2013-03-30 | 2016-02-24 | 浙江工业大学 | A kind of sulphur carbon composite of imitative animal sclay texture and application thereof |
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| CN105990573A (en) * | 2015-03-06 | 2016-10-05 | 国家纳米科学中心 | Nitrogen-doped porous carbon/sulfur composite material and preparing method and application thereof |
| 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 |
| CN107615526A (en) * | 2015-06-05 | 2018-01-19 | 罗伯特·博世有限公司 | Sulphur carbon composite comprising micropore carbon nanosheet for lithium-sulfur cell and preparation method thereof |
| CN105826540A (en) * | 2016-06-03 | 2016-08-03 | 合肥工业大学 | Lithium-sulfur battery composite anode material and preparation method and application thereof |
| CN106099110A (en) * | 2016-07-11 | 2016-11-09 | 杭州电子科技大学 | A kind of method utilizing algae to prepare Li S cell positive material as carbon source |
| CN106099110B (en) * | 2016-07-11 | 2018-09-21 | 杭州电子科技大学 | A method of making carbon source using algae and prepares Li-S cell positive materials |
| CN110473710A (en) * | 2018-05-10 | 2019-11-19 | 北京化工大学 | Porous carbon materials and its preparation method and application |
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