CN103700859B - Lithium-sulphur cell positive electrode graphene-based N doping multi-stage porous carbon nanometer sheet/sulphur composite material and its preparation method and application - Google Patents
Lithium-sulphur cell positive electrode graphene-based N doping multi-stage porous carbon nanometer sheet/sulphur composite material and its preparation method and application Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The invention discloses lithium-sulphur cell positive electrode graphene-based N doping multi-stage porous carbon nanometer sheet/sulphur composite material and its preparation method and application, carbon nanosheet is graphene-based N doping multi-stage porous carbon nanometer sheet, by using graphene oxide and nano silicon as double-template, on graphene oxide growth in situ polypyrrole, obtain after high temperature cabonization, activation of potassium hydroxide pore-creating, its carbon nanosheet thickness is 10-25nm, and specific area is 800-1600m
2g
-1, aperture integrated distribution is at 0.8-6nm, and structure is the class sandwich type of Graphene as carbon nanosheet intermediate layer.Enrich micropore, mesoporous and bigger serface carbon nanosheet can more sulphur active materials of load and effectively suppress the dissolving of polysulfide; Ultrathin nanometer sheet and micro-, mesoporously ensure that the diffusion of electrolyte and the transmission of ion.Such structure is worked in coordination with and is improve this carbon nanosheet/sulphur composite material and be applied to capacity, cyclical stability, coulombic efficiency and high rate performance in lithium-sulfur cell.
Description
Technical field
The invention belongs to electrochemical energy and field of nanometer material technology, relate to the crucial method for preparing anode material of lithium-sulfur rechargeable battery and application, particularly a kind of lithium-sulphur cell positive electrode graphene-based N doping multi-stage porous carbon nanometer sheet/sulphur composite material and its preparation method and application.
Background technology
The fast development of the aspects such as Current communications, portable electric appts, electric automobile and space technology is in the urgent need to developing the battery of more high-energy-density.Though the laboratory specific energy of current lithium ion battery reaches 250Whkg
-1, but by the restriction that positive electrode specific capacity improves further, its specific energy is difficult to improve a lot again, and will safety problem be aggravated by improving charging voltage with the approach increasing specific energy, thus develop new electrochemical energy storage system imperative.In new energy storage system, take lithium metal as negative pole, elemental sulfur is positive pole lithium-sulfur cell (Li/S battery) theoretical cell energy density can reach 2600Whkg
-1, sulphur positive electrode specific capacity is 1675mAhg
-1, much larger than the commercialization secondary cell that present stage uses, the operating voltage of lithium-sulfur cell, at about 2.0V, can meet the application demand of existing market, and Sulphur ressource is abundant and cheap.Therefore, lithium-sulfur cell has very large application advantage in new chemical industry power source development.But still there is some key difficult problem, one in the application of lithium-sulfur cell, as positive electrode sulphur ionic conductivity and electron conduction is all very low and discharging product insulation Li
2s separates out in the electrolytic solution and covers sulphur positive electrode surface, electrode utilization efficiency is low, specific capacity is low problems such as (specific capacities particularly under high power charging-discharging) that this causes; They are two years old, many lithium sulfides that lithium-sulfur cell charge and discharge process produces are soluble in organic electrolyte, the active material of electrode is reduced gradually, and due to " flying shuttle " phenomenon (shuttlemechanism), the many lithium sulfides dissolved can reach on the negative pole lithium sheet of battery through barrier film, thus cause the corrosion of battery cathode and the increase of the internal resistance of cell, cause the cycle performance of battery to be deteriorated, capacity is progressively decayed.The existence of an above-mentioned key difficult problem excites domestic and international researcher and studies interest greatly, multiclass carbon nanomaterial be added to improve sulphur simple substance in elemental sulfur positive pole electric conductivity, inhibit activities sulphur solution loss, thus improve the performance of lithium-sulfur cell further.As patent CN101986443 disclose a kind of high-temperature and high-pressure conditions under the hollow Nano carbon pipe prepared fill the method for the lithium sulfur battery anode material of sulphur, and have better cyclical stability, but its technical process is more loaded down with trivial details, limits its application development.Patent CN103050669 discloses meso-porous carbon material as carrier, assembling sulfur nano particles, although although the material with carbon element with two kinds of pore structures can assemble the element sulphur of high level, but blocks of large material with carbon element limits the infiltration of electrolyte, Ion transfer and electron transmission, thus have impact on the high rate performance of battery.The people such as Xin (JACS, 2012,134,18510) report microporous carbon carbon nano-tube coaxial material assembling Small molecular sulphur, solves many lithium sulfides problems of dissolution effectively.But, the aperture of microporous carbon hold the assembling amount that limits sulfur nano particles and cause its integral battery door capacity and discharge platform on the low side, thus have impact on the energy density of integral battery door.To sum up, although the research of lithium-sulfur rechargeable battery has achieved numerous breakthrough achievement, be not difficult to find that much research is only gone to solve for an a certain difficult problem and ignores other problems.Therefore, consider a few hang-up that lithium-sulfur cell faces and the new structure sulfenyl composite material that designs still has very positive meaning to improve lithium-sulfur cell performance by its application development comprehensively.
Summary of the invention
For above-mentioned lithium-sulfur cell Problems existing, first object of the present invention there is provided the graphene-based N doping multi-stage porous carbon nanometer sheet/sulphur composite material of a kind of lithium-sulphur cell positive electrode, this graphene-based N doping multi-stage porous carbon nanometer sheet/sulphur composite material is applied to the positive pole of lithium-sulfur cell, can improve the performance of lithium-sulfur cell.
Second object of the present invention is to provide a kind of preparation method of above-mentioned graphene-based N doping multi-stage porous carbon nanometer sheet/sulphur composite material.
3rd object of the present invention is to provide a kind of application process of graphene-based N doping multi-stage porous carbon nanometer sheet/sulphur composite material.
For realizing first object of the present invention, technical scheme of the present invention comprises graphene-based N doping multi-stage porous carbon nanometer sheet and utilizes the elemental sulfur of Physical penetration in graphene-based N doping multi-stage porous carbon nanometer sheet, and wherein elemental sulfur accounts for the 69-89wt% of total compound.
Further setting is graphene-based N doping multi-stage porous carbon nanometer sheet is that Graphene is inserted into the structure forming class sandwich type between amorphous conductive carbon.
Amorphous carbon is also called transition state carbon, is the large class of one in the allotrope of carbon, on carbon material is studied history, once exists side by side with graphite, diamond, and be considered to one of carbon three kinds of existences.
The common feature of amorphous carbon is:
(1) C/H atomic ratio is greater than 10;
(2) reflected ray in X-ray diffraction pattern is smudgy, is amorphous in general.But this kind of carbonaceous material, forms atom agglutination body unordered completely in a jumble, namely presents what is called completely amorphous unlike amorphous metal.The valence electron of carbon the most easily gets the low sp2 hybridized orbit of energy (see carbon atom hybridized orbit), forms hexagonal carbon network plane, though in inert gas diamond heating to 1800 DEG C, diamond also can be converted into graphite.
Also contain minimum (<30nm) the two-dimentional graphite aspect of diameter or three-dimensional graphite crystallite in amorphous carbon, crystallite edge exists a large amount of irregular key.Furan resin, through slowly carbonizing obtained glass-like carbon, except containing except a large amount of sp2 carbon, also contains many sp3 carbon.With the diamond thin that low temperature chemical vapor deposition method is obtained, although wherein carbon atom, based on sp3 bonding, also has a small amount of carbon atom with the mutual bonding of sp2 mode.
Further setting be in graphene-based N doping multi-stage porous carbon nanometer sheet amorphous conductive carbon be derive from carbonization at 700-900 DEG C, the pyrroles of activation of potassium hydroxide at 800 DEG C.
Further setting is the nitrogen-atoms of nitrogen element source in pyrroles of graphene-based N doping multi-stage porous carbon nanometer sheet doping, and its doping is about 2wt%.
Further setting is that graphene-based N doping multi-stage porous carbon nanometer sheet has hierarchical porous structure, and comprise micropore and mesoporous, aperture concentrates between 0.8-6nm, and specific area 800-1600m
2g
-1, pore volume 0.7-1.2cm
3g
-1.
Further setting is the thickness of graphene-based N doping multi-stage porous carbon nanometer sheet is 10-25nm.
For realizing second object of the present invention, technical scheme of the present invention comprises the following steps:
(1) preparation of graphene-based N doping multi-stage porous carbon nanometer sheet
Graphene oxide and nano silicon (particle diameter 5-8nm) are mixed by the mass ratio of 1:2, add pyrroles's (mass ratio of graphene oxide and pyrroles is 1:20-50), mix, stir under ice bath, add 50mL hydrochloric acid and ammonium persulfate (be 1:3 with the mass ratio of pyrroles), after continuing reaction 12h, filter, priority ethanol, water washs respectively, vacuumize, roasting 2h at nitrogen atmosphere 700-900 DEG C, the black powder obtained joins the hydrofluoric acid solution stirring of 20%, filter, dry, the product obtained mixes in ethanol with potassium hydroxide (mass ratio 1:1-3), ultrasonic, ethanol evaporation is to dry, to transfer in tube furnace roasting 1-5h at 800 DEG C, priority pickling, water washing product is to neutral, filter, dry, obtain graphene-based multi-stage porous nitrogen-doped carbon nanometer sheet.
(2) assembling of elemental sulfur
By the carbon nanosheet prepared by (1) and elemental sulfur in mass ratio 1:3-1:5 mix, and be sealed in measuring cup, heat 160 DEG C, constant temperature 10h, is cooled to room temperature, obtains corresponding carbon nanosheet/sulphur composite material.
For realizing the 3rd object of the present invention, technical scheme of the present invention is the positive pole graphene-based N doping multi-stage porous carbon nanometer sheet/sulphur composite material being applied to a kind of lithium-sulfur cell.
Further setting is that the positive pole of this lithium-sulfur cell is prepared by following steps:
Mixed according to the mass ratio of 8:1:1 by graphene-based N doping multi-stage porous carbon nanometer sheet/sulphur composite material, acetylene black and Polyvinylidene, be coated in aluminum foil current collector, vacuumize at 50-60 DEG C, then roll compacting, section obtain corresponding anode.
In addition, the present invention also provides a kind of lithium-sulfur cell, comprise positive pole, negative pole, electrolyte, barrier film and shell, described method preparation just very according to claim 9, described negative pole is lithium sheet, electrolyte is the glycol dimethyl ether and 1 of bis trifluoromethyl sulfonic acid imide li and lithium nitrate, 3-dioxane solution, wherein the molar concentration of bis trifluoromethyl sulfonic acid imide li is 1mol/l, the mass fraction 1% of lithium nitrate, glycol dimethyl ether and 1,3-dioxane volume ratio are 1:1.
In the present invention we by contrast different sulphur load capacity and carbon nanosheet structure on the impact of battery performance.Found that, when sulphur load capacity is 74%, be 1370mAhg at 0.5C multiplying power discharge capacity
-1, 1C multiplying power discharge capacity is 1200mAhg
-1, after circulation 100 circle, capacity still can reach 860mAhg
-1, show carbon nanosheet/good cyclical stability of sulphur composite material.The more important thing is, when multiplying power is increased to 10C, its discharge capacity still can reach 510mAhg
-1, this demonstrate that this materials application has good high rate performance in lithium-sulfur cell.When raising content to 83%, 89%, be reduced to 1120 and 965mAhg respectively at 1C multiplying power discharge capacity
-1.Contrast does not add the sample of Nano particles of silicon dioxide as template, and result shows, and lithium-sulfur cell discharges and only has 922mAhg under 0.5C multiplying power
-1; And when sample is not applied to by activation of potassium hydroxide in lithium-sulfur cell, its discharge capacity only has 952mAhg
-1.The two is all lower than the discharge capacity 1370mAhg optimizing rear carbon-sulfur compound
-1, its reason be do not use silicon dioxide as template or do not have the pore volume of the carbon nanosheet of activation of potassium hydroxide and specific area lower.
Compared with prior art, its main advantage is that carbon nanosheet/sulfur compound is applied to lithium-sulphur cell positive electrode and all improves a lot at electric capacity, discharge and recharge coulombic efficiency, cyclical stability and high rate performance in the present invention.This mainly owing to graphene-based N doping multi-stage porous carbon nanometer sheet novel structure, uniqueness prepared by the present invention, inserts the class sandwich structure formed between other conductive carbon layer, is conducive to the transmission of electronics with Graphene; Large specific area and abundant micropore and mesoporously reduce the dissolving of polysulfide and improve the load capacity of sulphur; Ultrathin nanometer sheet and hierarchical porous structure are convenient to diffusion and the ion transport of electrolyte.In addition, preparation technology is simple, the raw material that relates to and equipment cost low, there is better actual application value.
Below in conjunction with specification drawings and specific embodiments, the present invention is described further.
Accompanying drawing explanation
Carbon nanosheet scanning electron microscope (SEM) photograph prepared in Fig. 1 embodiment 1.
The scanning electron microscope (SEM) photograph of carbon nanosheet/sulphur composite material prepared in Fig. 2 embodiment 1.
The thermal multigraph of carbon nanosheet/sulphur composite material prepared in Fig. 3 embodiment 1.
Second circle charge/discharge capacity-voltage relationship figure of prepared carbon nanosheet/sulphur composite material in Fig. 4 embodiment 1.
The discharge and recharge different multiplying discharge capacity of prepared carbon nanosheet/sulphur composite material in Fig. 5 embodiment 1.
The charge and discharge cycles stability of carbon nanosheet/sulphur composite material prepared by Fig. 6 embodiment 1 and coulombic efficiency.
Embodiment
Below by embodiment, the present invention is specifically described; only be used to further illustrate the present invention; can not be interpreted as limiting the scope of the present invention, the technician in this field can make some nonessential improvement and adjustment according to the content of foregoing invention to the present invention.
embodiment 1
The synthesis of carbon nanosheet/sulphur composite material:
600mlH is added successively in beaker
2o, 100ml graphene oxide solution (1mgml
-1), 100mlSiO
2solution (2mgml
-1) and 4g pyrroles, magnetic agitation 1h in ice-water bath, then in beaker, add dense HCl and the 12gAPS aqueous solution of 50ml, suction filtration after reaction 12h, then with distillation washing, until filtrate is colourless, gained solid is placed in 110 DEG C of baking ovens and dries.Get 6 grams of above-mentioned solids in crucible, logical N
2, with 5 DEG C of min
-1naturally cool after being warming up to 850 DEG C of insulation 2h.Be transferred to 20% hydrofluoric acid solution, filter after stirring 2h, wash, product (PPG) after 110 DEG C of corresponding carbonizations of oven dry acquisition.Get this product 0.4g and be placed in beaker, successively add 2ml water, 20ml ethanol and 1.2gKOH solid, under stirring, heat solvent evaporated, be transferred in nickel crucible, logical N
2, with 5 DEG C of min
-1naturally cool after being warming up to 800 DEG C of insulation 1h, by gained solid priority hydrochloric acid and water washing extremely neutrality, filter in rear 110 DEG C of baking ovens and dry, obtain 1.2g graphene-based N doping multi-stage porous hydridization carbon nanosheet (APPG).Get the measuring cup that above-mentioned carbon nanosheet 0.04g is placed in band stopper, mixing 0.12g sulphur powder, after sealing, be placed in 160 DEG C of baking ovens to heat, after 10h, cooling is taken out, obtain carbon nanosheet/sulphur composite material (SAPPG-74%), analyzed by Fig. 3 (thermal multigraph), the content of its sulphur is 74%.
The preparation of positive pole and battery assembling:
By above-mentioned carbon-sulfur compound, acetylene black, PVDF in mass ratio 8:1:1 in pyrrolidones, stir 10h, pulp, coating machine is coated on aluminium foil, vacuumize 15h at 60 DEG C, take out, being cut into diameter is 1.4cm disk, obtain homemade lithium-sulphur cell positive electrode, assemble the assembled battery of lithium battery method routinely, its electrolyte is the glycol dimethyl ether and 1, the 3-dioxane mixed solution that contain 1mol/l bis trifluoromethyl sulfonic acid imide li and 1% lithium nitrate.
Battery performance conventionally test:
Adopt LAND test macro to carry out charge-discharge test under different current density to all embodiments, the voltage range of discharge and recharge is 1-3V, and the capacity of the battery assembled under 0.5C multiplying power is 1370mAhg
-1.
embodiment 2
APPG sample 0.4g prepared in Example 1, mixing 0.20g sulphur powder, after sealing, be placed in 160 DEG C of baking ovens and heat, after 10h, cooling is taken out, and obtains carbon nanosheet/sulphur composite material.By the method in embodiment 1, preparing electrode and assembled battery, and carry out performance conventionally test, is 1120mAhg at 0.5C multiplying power discharge capacity
-1.
embodiment 3
APPG sample 0.4g prepared in Example 1, mixing 0.36g sulphur powder, after sealing, be placed in 160 DEG C of baking ovens and heat, after 10h, cooling is taken out, and obtains carbon nanosheet/sulphur composite material.By the method in embodiment 1, preparing electrode and assembled battery, and carry out performance conventionally test, is 965mAhg at 0.5C multiplying power discharge capacity
-1.
embodiment 4
PPG sample 0.4g prepared in Example 1, mixing 0.10g sulphur powder, after sealing, be placed in 160 DEG C of baking ovens and heat, after 10h, cooling is taken out, and obtains carbon-sulfur compound.By the method in embodiment 1, preparing electrode and assembled battery, and carry out performance conventionally test, is 922mAhg at 0.5C multiplying power discharge capacity
-1.
embodiment 5
700mlH is added successively in beaker
2o, 100mlGO solution 1mg/ml and 4ml pyrroles, magnetic agitation 1h in ice-water bath, then in beaker, add dense HCl and 12gAPS100mlH of 100ml
2o solution, suction filtration after reaction 12h, then with distillation washing, until filtrate is colourless, gained solid is placed in 110 DEG C of baking ovens and dries.
Get 6 grams of above-mentioned solids in crucible, logical N
2, be warming up to cooling naturally after 850 DEG C of insulation 2h with 5 DEG C/min, obtain product (PG) after corresponding carbonization.Get this product 0.4g and be placed in beaker, successively add 2ml water, 20ml ethanol and 1.2gKOH solid, under stirring, heat solvent evaporated, be transferred in nickel crucible, logical N
2, naturally cool after being warming up to 800 DEG C of insulation 1h with 5 DEG C/min.By gained solid priority hydrochloric acid and water washing extremely neutrality, filter in rear 110 DEG C of baking ovens and dry, obtain 1.3g graphene-based multi-stage porous hydridization carbon nanosheet (APG).Get the measuring cup that above-mentioned carbon nanosheet 0.04g is placed in band stopper, mixing 0.10g sulphur powder, after sealing, be placed in 160 DEG C of baking ovens and heat, after 10h, cooling is taken out, and obtains corresponding carbon nanosheet/sulphur composite material.By the method in embodiment 1, preparing electrode and assembled battery, and carry out performance conventionally test, is 952mAhg at 0.5C multiplying power discharge capacity
-1.
embodiment 6
600mlH is added successively in beaker
2o, 100ml graphene oxide solution 1mg/ml, 100mlSiO
2solution 2mg/ml and 5g pyrroles, magnetic agitation 1h in ice-water bath, then in beaker, add dense HCl and the 15gAPS aqueous solution of 50ml, suction filtration after reaction 12h, then with distillation washing, until filtrate is colourless, gained solid is placed in 110 DEG C of baking ovens and dries.Get 6 grams of above-mentioned solids in crucible, logical N
2, naturally cool after being warming up to 850 DEG C of insulation 2h with 5 DEG C/min.Be transferred to 20% hydrofluoric acid solution, filter after stirring 2h, wash, product after 110 DEG C of corresponding carbonizations of oven dry acquisition.Get this product 0.4g and be placed in beaker, successively add 2ml water, 20ml ethanol and 1.2gKOH solid, under stirring, heat solvent evaporated, be transferred in nickel crucible, logical N
2, naturally cool after being warming up to 800 DEG C of insulation 1h with 5 DEG C/min, by gained solid priority hydrochloric acid and water washing extremely neutrality, filter in rear 110 DEG C of baking ovens and dry, obtain 1.2g graphene-based N doping multi-stage porous hydridization carbon nanosheet.Get the measuring cup that above-mentioned carbon nanosheet 0.04g is placed in band stopper, mixing 0.12g sulphur powder, after sealing, be placed in 160 DEG C of baking ovens and heat, after 10h, cooling is taken out, and obtains corresponding carbon nanosheet/sulphur composite material.By the method in embodiment 1, preparing electrode and assembled battery, and carry out performance conventionally test, is 1210mAhg at 0.5C multiplying power discharge capacity
-1.
embodiment 7
600mlH is added successively in beaker
2o, 100ml graphene oxide solution 1mg/ml, 100mlSiO
2solution 2mg/ml and 2g pyrroles, magnetic agitation 1h in ice-water bath, then in beaker, add dense HCl and the 6gAPS aqueous solution of 50ml, suction filtration after reaction 12h, then with distillation washing, until filtrate is colourless, gained solid is placed in 110 DEG C of baking ovens and dries.Get 6 grams of above-mentioned solids in crucible, logical N
2, naturally cool after being warming up to 850 DEG C of insulation 2h with 5 DEG C/min.Be transferred to 20% hydrofluoric acid solution, filter after stirring 2h, wash, product after 110 DEG C of corresponding carbonizations of oven dry acquisition.Get this product 0.4g and be placed in beaker, successively add 2ml water, 20ml ethanol and 1.2gKOH solid, under stirring, heat solvent evaporated, be transferred in nickel crucible, logical N
2, naturally cool after being warming up to 800 DEG C of insulation 1h with 5 DEG C/min, by gained solid priority hydrochloric acid and water washing extremely neutrality, filter in rear 110 DEG C of baking ovens and dry, obtain 1.2g graphene-based N doping multi-stage porous hydridization carbon nanosheet.Get the measuring cup that above-mentioned carbon nanosheet 0.04g is placed in band stopper, mixing 0.12g sulphur powder, after sealing, be placed in 160 DEG C of baking ovens and heat, after 10h, cooling is taken out, and obtains corresponding carbon nanosheet/sulphur composite material.By the method in embodiment 1, preparing electrode and assembled battery, and carry out performance conventionally test, is 910mAhg at 0.5C multiplying power discharge capacity
-1.
embodiment 8
600mlH is added successively in beaker
2o, 100ml graphene oxide solution (1mgml
-1), 100mlSiO
2solution (2mgml
-1) and 4g pyrroles, magnetic agitation 1h in ice-water bath, then in beaker, add dense HCl and the 12gAPS aqueous solution of 50ml, suction filtration after reaction 12h, then with distillation washing, until filtrate is colourless, gained solid is placed in 110 DEG C of baking ovens and dries.Get 6 grams of above-mentioned solids in crucible, logical N
2, with 5 DEG C of min
-1naturally cool after being warming up to 900 DEG C of insulation 2h.Be transferred to 20% hydrofluoric acid solution, filter after stirring 2h, wash, product after 110 DEG C of corresponding carbonizations of oven dry acquisition.Get this product 0.4g and be placed in beaker, successively add 2ml water, 20ml ethanol and 1.2gKOH solid, under stirring, heat solvent evaporated, be transferred in nickel crucible, logical N
2, with 5 DEG C of min
-1naturally cool after being warming up to 800 DEG C of insulation 1h, by gained solid priority hydrochloric acid and water washing extremely neutrality, filter in rear 110 DEG C of baking ovens and dry, obtain 1.2g graphene-based N doping multi-stage porous hydridization carbon nanosheet.Get the measuring cup that above-mentioned carbon nanosheet 0.04g is placed in band stopper, mixing 0.12g sulphur powder, after sealing, be placed in 160 DEG C of baking ovens and heat, after 10h, cooling is taken out, and obtains corresponding carbon nanosheet/sulphur composite material.By the method in embodiment 1, preparing electrode and assembled battery, and carry out performance conventionally test, is 1270mAhg at 0.5C multiplying power discharge capacity
-1.
embodiment 9
600mlH is added successively in beaker
2o, 100ml graphene oxide solution (1mgml
-1), 100mlSiO
2solution (2mgml
-1) and 4g pyrroles, magnetic agitation 1h in ice-water bath, then in beaker, add dense HCl and the 12gAPS aqueous solution of 50ml, suction filtration after reaction 12h, then with distillation washing, until filtrate is colourless, gained solid is placed in 110 DEG C of baking ovens and dries.Get 6 grams of above-mentioned solids in crucible, logical N
2, with 5 DEG C of min
-1naturally cool after being warming up to 700 DEG C of insulation 2h.Be transferred to 20% hydrofluoric acid solution, filter after stirring 2h, wash, product after 110 DEG C of corresponding carbonizations of oven dry acquisition.Get this product 0.4g and be placed in beaker, successively add 2ml water, 20ml ethanol and 1.2gKOH solid, under stirring, heat solvent evaporated, be transferred in nickel crucible, logical N
2, with 5 DEG C of min
-1naturally cool after being warming up to 800 DEG C of insulation 1h, by gained solid priority hydrochloric acid and water washing extremely neutrality, filter in rear 110 DEG C of baking ovens and dry, obtain 1.2g graphene-based N doping multi-stage porous hydridization carbon nanosheet (APPG).Get the measuring cup that above-mentioned carbon nanosheet 0.04g is placed in band stopper, mixing 0.12g sulphur powder, after sealing, be placed in 160 DEG C of baking ovens and heat, after 10h, cooling is taken out, and obtains corresponding carbon nanosheet/sulphur composite material.By the method in embodiment 1, preparing electrode and assembled battery, and carry out performance conventionally test, is 1150mAhg at 0.5C multiplying power discharge capacity
-1.
embodiment 10
The PPG0.4g taking preparation in embodiment 1 is placed in beaker, successively adds 2ml water, 20ml ethanol and 0.8gKOH solid, heats solvent evaporated under stirring, be transferred in nickel crucible, logical N
2, with 5 DEG C of min
-1naturally cool after being warming up to 800 DEG C of insulation 1h, by gained solid priority hydrochloric acid and water washing extremely neutrality, filter in rear 110 DEG C of baking ovens and dry, obtain 1.2g graphene-based N doping multi-stage porous hydridization carbon nanosheet.Get the measuring cup that above-mentioned carbon nanosheet 0.04g is placed in band stopper, mixing 0.12g sulphur powder, after sealing, be placed in 160 DEG C of baking ovens and heat, after 10h, cooling is taken out, and obtains corresponding carbon nanosheet/sulphur composite material.By the method in embodiment 1, preparing electrode and assembled battery, and carry out performance conventionally test, is 1050mAhg at 0.5C multiplying power discharge capacity
-1.
embodiment 11
The PPG0.4g taking preparation in embodiment 1 is placed in beaker, successively adds 2ml water, 20ml ethanol and 1.6gKOH solid, heats solvent evaporated under stirring, be transferred in nickel crucible, logical N
2, with 5 DEG C of min
-1naturally cool after being warming up to 800 DEG C of insulation 1h, by gained solid priority hydrochloric acid and water washing extremely neutrality, filter in rear 110 DEG C of baking ovens and dry, obtain 1.2g graphene-based N doping multi-stage porous hydridization carbon nanosheet (APPG).Get the measuring cup that above-mentioned carbon nanosheet 0.04g is placed in band stopper, mixing 0.12g sulphur powder, after sealing, be placed in 160 DEG C of baking ovens and heat, after 10h, cooling is taken out, and obtains corresponding carbon nanosheet/sulphur composite material.By the method in embodiment 1, preparing electrode and assembled battery, and carry out performance conventionally test, is 1190mAhg at 0.5C multiplying power discharge capacity
-1.
Claims (9)
1. the graphene-based N doping multi-stage porous carbon nanometer sheet/sulphur composite material for lithium-sulphur cell positive electrode, it is characterized in that: comprise graphene-based N doping multi-stage porous carbon nanometer sheet and utilize the elemental sulfur of Physical penetration in graphene-based N doping multi-stage porous carbon nanometer sheet, wherein elemental sulfur accounts for the 69-89wt% of total compound, graphene-based N doping multi-stage porous carbon nanometer sheet has hierarchical porous structure, comprise micropore and mesoporous, aperture concentrates between 0.8-6nm, and specific area 800-1600m
2g
-1, pore volume 0.7-1.2cm
3g
-1.
2. a kind of graphene-based N doping multi-stage porous carbon nanometer sheet/sulphur composite material for lithium-sulphur cell positive electrode according to claim 1, is characterized in that: graphene-based N doping multi-stage porous carbon nanometer sheet is that Graphene is inserted into the structure forming class sandwich type between amorphous conductive carbon.
3. a kind of graphene-based N doping multi-stage porous carbon nanometer sheet/sulphur composite material for lithium-sulphur cell positive electrode according to claim 2, is characterized in that: in graphene-based N doping multi-stage porous carbon nanometer sheet amorphous carbon be derive from carbonization at 700-900 DEG C, the pyrroles of activation of potassium hydroxide at 800 DEG C.
4. a kind of graphene-based N doping multi-stage porous carbon nanometer sheet/sulphur composite material for lithium-sulphur cell positive electrode according to claim 3, it is characterized in that: the nitrogen-atoms of nitrogen element source in pyrroles of graphene-based N doping multi-stage porous carbon nanometer sheet doping, its doping 2wt%.
5. a kind of graphene-based N doping multi-stage porous carbon nanometer sheet/sulphur composite material for lithium-sulphur cell positive electrode according to claim 1, is characterized in that: the thickness of graphene-based N doping multi-stage porous carbon nanometer sheet is 10-25nm.
6. prepare a method for the graphene-based N doping multi-stage porous carbon nanometer sheet/sulphur composite material for lithium-sulphur cell positive electrode as described in one of claim 1-5, it is characterized in that comprising the following steps:
(1) preparation of graphene-based N doping multi-stage porous carbon nanometer sheet
Be that the nano silicon of 5-8nm mixes by the mass ratio of 1:2 by graphene oxide and particle diameter, add pyrroles, the mass ratio of graphene oxide and pyrroles is 1:20-50, mix, stir under ice bath, add 50ml hydrochloric acid and ammonium persulfate, the addition of ammonium persulfate and the mass ratio of pyrroles are 1:3, after continuing reaction 12h, filter, priority ethanol, water washs respectively, vacuumize, roasting 2h at nitrogen atmosphere 700-900 DEG C, the black powder obtained joins the hydrofluoric acid solution stirring of 20%, filter, dry, the product obtained is that 1:1-4 mixes in ethanol with potassium hydroxide with mass ratio, ultrasonic, ethanol evaporation is to dry, to transfer in tube furnace roasting 1-5h at 800 DEG C, priority pickling, water washing product is to neutral, filter, dry, obtain graphene-based multi-stage porous nitrogen-doped carbon nanometer sheet,
(2) assembling of elemental sulfur
By the carbon nanosheet prepared by (1) and elemental sulfur in mass ratio 1:3-1:5 mix, and be sealed in measuring cup, heat 160 DEG C, constant temperature 10h, is cooled to room temperature, obtains corresponding carbon nanosheet/sulphur composite material.
7. an application for the graphene-based N doping multi-stage porous carbon nanometer sheet/sulphur composite material as described in one of claim 1-5, is characterized in that: the positive pole graphene-based N doping multi-stage porous carbon nanometer sheet/sulphur composite material being applied to a kind of lithium-sulfur cell.
8. the application of a kind of graphene-based N doping multi-stage porous carbon nanometer sheet/sulphur composite material according to claim 7, is characterized in that: the positive pole of this lithium-sulfur cell is prepared by following steps:
Mixed according to the mass ratio of 8:1:1 by graphene-based N doping multi-stage porous carbon nanometer sheet/sulphur composite material, acetylene black and Polyvinylidene, be coated in aluminum foil current collector, vacuumize at 50 DEG C, then roll compacting, section obtain corresponding anode.
9. a lithium-sulfur cell, comprise positive pole, negative pole, electrolyte, barrier film and shell, it is characterized in that: the described preparation of the step just very described in claim 8, described negative pole is lithium sheet, electrolyte is the glycol dimethyl ether and 1 of bis trifluoromethyl sulfonic acid imide li and lithium nitrate, 3-dioxane solution, wherein the molar concentration of bis trifluoromethyl sulfonic acid imide li is 1molL
-1, the mass fraction 1% of lithium nitrate, glycol dimethyl ether and 1,3-dioxane volume ratio are 1:1.
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Families Citing this family (32)
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Family Cites Families (3)
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| CN101986443A (en) * | 2010-05-25 | 2011-03-16 | 耿世达 | Lithium sulfur battery anode material and preparation method thereof |
| CN103050669B (en) * | 2011-10-17 | 2015-04-08 | 中国科学院大连化学物理研究所 | Carbon-sulphur composite used for cathode material of lithium sulphur battery as well as preparation method and application thereof |
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