CN103700859A - Graphene-based nitrogen-doped hierachical-pore carbon nanosheet/sulfur composite material for cathode of lithium sulfur battery, as well as preparation method and application of graphene-based nitrogen-doped hierachical-pore carbon nanosheet/sulfur composite material - Google Patents
Graphene-based nitrogen-doped hierachical-pore carbon nanosheet/sulfur composite material for cathode of lithium sulfur battery, as well as preparation method and application of graphene-based nitrogen-doped hierachical-pore carbon nanosheet/sulfur composite material Download PDFInfo
- Publication number
- CN103700859A CN103700859A CN201310743270.7A CN201310743270A CN103700859A CN 103700859 A CN103700859 A CN 103700859A CN 201310743270 A CN201310743270 A CN 201310743270A CN 103700859 A CN103700859 A CN 103700859A
- Authority
- CN
- China
- Prior art keywords
- graphene
- based nitrogen
- composite material
- lithium
- stage porous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/5835—Comprising fluorine or fluoride salts
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a graphene-based nitrogen-doped hierachical-pore carbon nanosheet/sulfur composite material for a cathode of a lithium sulfur battery, as well as a preparation method and application of the graphene-based nitrogen-doped hierachical-pore carbon nanosheet/sulfur composite material. The carbon nanosheet is a graphene-based nitrogen-doped hierachical-pore carbon nanosheet, and is prepared by the steps of growing poly-pyrrole on graphene oxide in situ, performing carbonization at high temperature, activating by using potassium hydroxide and forming pores, wherein the graphene oxide and nano-silicon dioxide serve as double templates; the thickness of the carbon nanosheet is 10 to 25 nm; the specific surface area is 800 to 1,600 m<2>/g; the pore diameter of the carbon nanosheet is distributed into the range of 0.8 to 6 nm in a concentrated way; the structure of the carbon nanosheet is a sandwich-like type which adopts graphene as the interlayer of the carbon nanosheet. The carbon nanosheet with abundant micro-pores, meso-pores and large specific surface area can load more sulfur active substances and can effectively inhibit dissolution of polysulfide. The ultrathin nanosheet, and the micro-pores and meso-pores guarantee diffusion of electrolyte and transmission of ions. According to the structure, the capacity, the cycling stability, the coulombic efficiency and the rate performance of the carbon nanosheet/sulfur composition material applied to the lithium sulfur battery are improved synergistically.
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 thereof, particularly graphene-based nitrogen doping multi-stage porous carbon nanometer sheet/sulphur composite material and its preparation method and application for a kind of lithium-sulphur cell positive electrode.
Background technology
The fast development of the aspects such as current communication, portable electric appts, electric automobile and space technology is in the urgent need to developing the more battery of high-energy-density.Though the laboratory specific energy of lithium ion battery has reached 250Wh kg at present
-1, but the restriction that further improved by positive electrode specific capacity, its specific energy is difficult to improve a lot again, and to increase the approach of specific energy, will aggravate safety problem by improving charging voltage, thereby it is imperative to develop new electrochemical energy storage system.In new energy storage system, take lithium metal as negative pole, elemental sulfur are as the theoretical energy content of battery density reachable of anodal lithium-sulfur cell (Li/S battery) is to 2600Wh kg
-1, the anodal specific capacity of sulphur is 1675mA h g
-1, much larger than the commercialization secondary cell that present stage is used, the operating voltage of lithium-sulfur cell, in 2.0V left and right, can meet the application demand of existing market, and sulphur aboundresources and cheap.Therefore, lithium-sulfur cell has very large application advantage in following chemical power source development.Yet the application of lithium-sulfur cell still exists some key difficult problem, one, as ionic conductivity and the electron conduction Li that all very low and discharging product insulate of positive electrode sulphur
2s separates out and covers the anodal surface of sulphur, problems such as (the particularly specific capacities under high power charging-discharging) that this causes, and electrode utilization efficiency is low, specific capacity is low in electrolyte; 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 (shuttle mechanism), the many lithium sulfides that dissolve can reach on the negative pole lithium sheet of battery through barrier film, thereby cause the corrosion of battery cathode and the increase of the internal resistance of cell, cause the cycle performance variation of battery, capacity is progressively decayed.The existence of an above-mentioned key difficult problem has excited domestic and international researcher to study greatly interest, multiclass carbon nanomaterial has been added to the electric conductivity that improves sulphur simple substance in elemental sulfur positive pole, the solution loss that suppresses active sulfur, thereby further improves the performance of lithium-sulfur cell.As patent CN 101986443 discloses the hollow Nano carbon pipe of preparing under a kind of high-temperature and high-pressure conditions, 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, has limited its application development.Patent CN103050669 discloses meso-porous carbon material as carrier, assembling sulfur nano particles, although can assemble the element sulphur of high level although there is the material with carbon element of two kinds of pore structures, but blocks of large material with carbon element has limited infiltration, ion migration and the electronics transmission of electrolyte, thereby affected the high rate performance of battery.The people such as Xin (JACS, 2012,134,18510) report microporous carbon carbon nano-tube is assembled little molecular sulfur with shaft material, effectively solves many lithium sulfides problems of dissolution.Yet, the aperture tolerance limit system of microporous carbon sulfur nano particles assembling amount and cause its integral battery door capacity and discharge platform on the low side, thereby affected the energy density of integral battery door.To sum up, although the research of lithium-sulfur rechargeable battery has obtained numerous breakthrough achievements, be not difficult to find that much research only removes to solve and ignore other problems for an a certain difficult problem.Therefore, consider several hang-ups that lithium-sulfur cell faces and the new structure sulfenyl composite material designing improved lithium-sulfur cell performance and will its application development still be had to very positive meaning comprehensively.
Summary of the invention
The problem existing for above-mentioned lithium-sulfur cell, first object of the present invention has been to provide graphene-based nitrogen doping multi-stage porous carbon nanometer sheet/sulphur composite material for a kind of lithium-sulphur cell positive electrode, this graphene-based nitrogen 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 nitrogen doping multi-stage porous carbon nanometer sheet/sulphur composite material.
The 3rd object of the present invention is to provide a kind of application process of graphene-based nitrogen doping multi-stage porous carbon nanometer sheet/sulphur composite material.
For realizing first object of the present invention, technical scheme of the present invention is to comprise graphene-based nitrogen doping multi-stage porous carbon nanometer sheet and utilize physics to permeate the elemental sulfur in graphene-based nitrogen doping multi-stage porous carbon nanometer sheet, and wherein elemental sulfur accounts for the 69-89wt% of total compound.
Further arrange is that graphene-based nitrogen doping multi-stage porous carbon nanometer sheet is that Graphene is inserted into the structure that forms class sandwich type between amorphous conductive carbon.
Amorphous carbon is called again transition state carbon, is the large class in the allotrope of carbon, on carbon material is studied history, once exists side by side with graphite, diamond, is considered to one of three kinds of existences of carbon.
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 class carbonaceous material forms completely mixed and disorderly unordered atom agglutination body unlike amorphous metal, presents what is called completely amorphous.The valence electron of carbon is the most easily got the sp2 hybridized orbit that energy is low (seeing carbon atom hybridized orbit), forms hexagonal carbon network plane, though in inert gas diamond heating to 1800 ℃, diamond also can be converted into graphite.
In amorphous carbon, also contain the two-dimentional graphite aspect of diameter minimum (<30nm) or three-dimensional graphite microcrystal, on crystallite edge, have a large amount of irregular keys.Furan resin, through the glass charcoal that slowly charing makes, except containing a large amount of sp2 carbon, also contains many sp3 carbon.The diamond thin making by low temperature chemical vapor deposition method, although wherein carbon atom be take sp3 bonding as main, also has a small amount of carbon atom with the mutual bonding of sp2 mode.
Further arrange is that in graphene-based nitrogen doping multi-stage porous carbon nanometer sheet, amorphous conductive carbon is the polypyrrole that derives from potassium hydroxide activation at carbonization at 700-900 ℃, 800 ℃.
Further arrange is that the nitrogen element that graphene-based nitrogen doping multi-stage porous carbon nanometer sheet is adulterated derives from the nitrogen-atoms in polypyrrole, the about 2wt% of its doping.
Further arranging is that graphene-based nitrogen doping multi-stage porous carbon nanometer sheet has hierarchical porous structure, comprises micropore and mesoporous, and aperture concentrates between 0.8-6 nm, and specific area 800-1600 m
2g
-1, pore volume 0.7-1.2 cm
2g
-1.
Further setting is that the thickness of graphene-based nitrogen doping multi-stage porous carbon nanometer sheet is 10-25 nm.
For realizing second object of the present invention, technical scheme of the present invention is to comprise the following steps:
1) preparation of graphene-based nitrogen doping multi-stage porous structure carbon nanosheet
The mass ratio of graphene oxide and nano silicon (particle diameter 5-8nm) being pressed to 1:2 mixes, add pyrroles's (graphene oxide and pyrroles's mass ratio is 1:20-50), mix, under ice bath, stir, add 50mL hydrochloric acid and ammonium persulfate (with pyrroles's mass ratio be 1:3), continue after reaction 12h, filter, priority ethanol, water washs respectively, vacuumize, roasting 2h at nitrogen atmosphere 700-900 ℃, the black powder obtaining joins 20% hydrofluoric acid solution stirring, filter, dry, the product obtaining mixes in ethanol with potassium hydroxide (mass ratio 1:1-3), ultrasonic, ethanol evaporation is to dry, transfer in tube furnace roasting 1-5h at 800 ℃, 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 1) prepared carbon nanosheet and elemental sulfur in mass ratio 1:3-1:5 mix, and be sealed in measuring cup, heat 160 ℃, 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 graphene-based nitrogen doping multi-stage porous carbon nanometer sheet/sulphur composite material to be applied to a kind of positive pole of lithium-sulfur cell.
The positive pole that further setting is this lithium-sulfur cell is prepared by following steps:
Graphene-based nitrogen doping multi-stage porous carbon nanometer sheet/sulphur composite material, acetylene black and Polyvinylidene are mixed according to the mass ratio of 8:1:1, be coated in aluminum foil current collector, vacuumize at 50-60 ℃, 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 claimed in 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 are by the different sulphur load capacity of contrast and the impact of carbon nanosheet structure on battery performance.Found that, when sulphur load capacity is 74%, under 0.5C multiplying power, discharge capacity is 1370 mA h g
-1, under 1C multiplying power, discharge capacity is 1200 mA h g
-1, after circulation 100 circles, capacity still can reach 860 mA h g
-1, demonstrated the good cyclical stability of carbon nanosheet/sulphur composite material.The more important thing is, when multiplying power is increased to 10C, its discharge capacity still can reach 510 mA h g
-1, this has proved that this material is applied to lithium-sulfur cell and has good high rate performance.When improving content to 83%, 89%, under 1C multiplying power, discharge capacity is reduced to respectively 1120 and 965 mA h g
-1.Contrast does not add Nano particles of silicon dioxide as the sample of template, result demonstration, and lithium-sulfur cell discharges and only has 922 mA h g under 0.5C multiplying power
-1; And work as sample not with potassium hydroxide activation and be applied in lithium-sulfur cell, its discharge capacity only has 952 mA h g
-1.The two is all lower than the discharge capacity 1370 mA h g that optimize rear carbon-sulfur compound
-1, its reason is do not use silicon dioxide as template or do not have pore volume and the specific area of carbon nanosheet of potassium hydroxide activation lower.
The present invention compared with prior art, its main advantage be carbon nanosheet/sulfur compound be applied to lithium-sulphur cell positive electrode at electric capacity, discharge and recharge coulombic efficiency, cyclical stability and high rate performance and all improve a lot.Graphene-based nitrogen doping multi-stage porous carbon nanometer sheet novel structure, uniqueness that this mainly prepares owing to the present invention, insert the class sandwich structure forming between other conductive carbon layer with Graphene, be conducive to the transmission of electronics; Large specific area and abundant micropore and the mesoporous load capacity that reduces the dissolving of polysulfide and improve sulphur; Ultrathin nanometer sheet and hierarchical porous structure are convenient to diffusion and the ion transport of electrolyte.In addition, preparation technology's raw material and equipment cost simple, that relate to is low, has better actual application value.
Below in conjunction with specification drawings and specific embodiments, the present invention is described further.
Accompanying drawing explanation
Prepared carbon nanosheet scanning electron microscope (SEM) photograph in Fig. 1 embodiment 1.
The scanning electron microscope (SEM) photograph of prepared carbon nanosheet/sulphur composite material in Fig. 2 embodiment 1.
The thermal multigraph of prepared carbon nanosheet/sulphur composite material in Fig. 3 embodiment 1.
Second of prepared carbon nanosheet/sulphur composite material circle charge/discharge capacity-voltage relationship figure in Fig. 4 embodiment 1.
In Fig. 5 embodiment 1, prepared carbon nanosheet/sulphur composite material discharges and recharges discharge capacity under different multiplying.
The charge and discharge cycles stability of prepared carbon nanosheet/sulphur composite material and coulomb efficiency in Fig. 6 embodiment 1.
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 to the present invention according to the content of foregoing invention.
Synthesizing of carbon nanosheet/sulphur composite material:
In beaker, add successively 600 mlH
2o, 100 ml graphene oxide solution (1mg ml
-1), 100 ml SiO
2solution (2mg ml
-1) and 4 g pyrroles, magnetic agitation 1 h in ice-water bath, then add the dense HCl of 50ml and the 12 g APS aqueous solution in beaker, suction filtration after reaction 12 h, then with distillation washing, until filtrate is colourless, gained solid is placed in to 110 ℃ of baking ovens and dries.Get 6 grams of above-mentioned solids in crucible, logical N
2, with 5 ℃ of min
-1be warming up to 850 ℃ of insulations naturally cooling after 2 h.Be transferred to 20% hydrofluoric acid solution, after stirring 2h, filter, wash, product (PPG) after 110 ℃ of corresponding carbonizations of oven dry acquisition.Get this product 0.4g and be placed in beaker, successively add 2ml water, 20ml ethanol and 1.2g KOH solid, stir lower heating solvent evaporated, be transferred in nickel crucible logical N
2, with 5 ℃ of min
-1be warming up to 800 ℃ of insulations naturally cooling after 1 h, successively use hydrochloric acid and water washing to neutral gained solid, filter in rear 110 ℃ of baking ovens and dry, obtain the graphene-based nitrogen of the 1.2g multi-stage porous hydridization carbon nanosheet (APPG) that adulterates.Get above-mentioned carbon nanosheet 0.04g and be placed in the measuring cup with stopper, mix 0.12g sulphur powder, after sealing, be placed in 160 ℃ of baking ovens and heat, cooling taking-up after 10h, obtains carbon nanosheet/sulphur composite material (S@APPG-74%), by Fig. 3 (thermal multigraph), analyze, the content of its sulphur is 74%.
Anodal preparation and battery assembling:
By above-mentioned carbon-sulfur compound, acetylene black, PVDF in mass ratio 8:1:1 in pyrrolidones, stir 10h, pulp, on coating machine, be coated on aluminium foil, vacuumize 15h at 60 ℃, takes out, and being cut into diameter is 1.4cm disk, obtain homemade lithium-sulphur cell positive electrode, assemble routinely the assembled battery of lithium battery method, its electrolyte is the glycol dimethyl ether and 1 containing 1mol/l bis trifluoromethyl sulfonic acid imide li and 1% lithium nitrate, 3-dioxane mixed solution.
Battery performance conventionally test:
Adopt LAND test macro to carry out charge-discharge test under different current densities to all embodiment, the voltage range discharging and recharging is 1-3V, and the capacity of the battery of assembling under 0.5C multiplying power is 1370 mA h g
-1.
embodiment 2
Get APPG sample 0.4g prepared in embodiment 1, mix 0.20g sulphur powder, after sealing, be placed in 160 ℃ of baking ovens and heat, cooling taking-up after 10h, obtains carbon nanosheet/sulphur composite material.Press the method in embodiment 1, prepare electrode and assembled battery, and carry out performance conventionally test, under 0.5C multiplying power, discharge capacity is 1120 mA h g
-1.
embodiment 3
Get APPG sample 0.4g prepared in embodiment 1, mix 0.36g sulphur powder, after sealing, be placed in 160 ℃ of baking ovens and heat, cooling taking-up after 10h, obtains carbon nanosheet/sulphur composite material.Press the method in embodiment 1, prepare electrode and assembled battery, and carry out performance conventionally test, under 0.5C multiplying power, discharge capacity is 965 mA h g
-1.
Get PPG sample 0.4g prepared in embodiment 1, mix 0.10g sulphur powder, after sealing, be placed in 160 ℃ of baking ovens and heat, cooling taking-up after 10h, obtains carbon-sulfur compound.Press the method in embodiment 1, prepare electrode and assembled battery, and carry out performance conventionally test, under 0.5C multiplying power, discharge capacity is 922 mA h g
-1.
In beaker, add successively 700 mlH
2o, 100 ml GO solution 1mg/ml and 4ml pyrroles, magnetic agitation 1 h in ice-water bath, then add the dense HCl of 100 ml and 12 g APS 100ml H in beaker
2o solution, suction filtration after reaction 12 h, then with distillation washing, until filtrate is colourless, gained solid is placed in to 110 ℃ of baking ovens and dries.
Get 6 grams of above-mentioned solids in crucible, logical N
2, with 5 ℃/min, be warming up to 850 ℃ of insulations naturally cooling after 2 h, obtain product (PG) after corresponding carbonization.Get this product 0.4g and be placed in beaker, successively add 2ml water, 20ml ethanol and 1.2g KOH solid, stir lower heating solvent evaporated, be transferred in nickel crucible logical N
2, with 5 ℃/min, be warming up to 800 ℃ of insulations naturally cooling after 1 h.Successively use hydrochloric acid and water washing to neutral gained solid, filter in rear 110 ℃ of baking ovens and dry, obtain 1.3g graphene-based multi-stage porous hydridization carbon nanosheet (APG).Get above-mentioned carbon nanosheet 0.04g and be placed in the measuring cup with stopper, mix 0.10g sulphur powder, after sealing, be placed in 160 ℃ of baking ovens and heat, cooling taking-up after 10h, obtains corresponding carbon nanosheet/sulphur composite material.Press the method in embodiment 1, prepare electrode and assembled battery, and carry out performance conventionally test, under 0.5C multiplying power, discharge capacity is 952 mA h g
-1.
embodiment 6
In beaker, add successively 600 mlH
2o, 100 ml graphene oxide solution 1mg/ml, 100 ml SiO
2solution 2mg/ml and 5 g pyrroles, magnetic agitation 1 h in ice-water bath, then add the dense HCl of 50ml and the 15 g APS aqueous solution in beaker, suction filtration after reaction 12 h, then with distillation washing, until filtrate is colourless, gained solid is placed in to 110 ℃ of baking ovens and dries.Get 6 grams of above-mentioned solids in crucible, logical N
2, with 5 ℃/min, be warming up to 850 ℃ of insulations naturally cooling after 2 h.Be transferred to 20% hydrofluoric acid solution, after stirring 2h, filter, wash, product after 110 ℃ of corresponding carbonizations of oven dry acquisition.Get this product 0.4g and be placed in beaker, successively add 2ml water, 20ml ethanol and 1.2g KOH solid, stir lower heating solvent evaporated, be transferred in nickel crucible logical N
2, with 5 ℃/min, be warming up to 800 ℃ of insulations naturally cooling after 1 h, successively use hydrochloric acid and water washing to neutral gained solid, filter in rear 110 ℃ of baking ovens and dry, obtain the graphene-based nitrogen of the 1.2g multi-stage porous hydridization carbon nanosheet that adulterates.Get above-mentioned carbon nanosheet 0.04g and be placed in the measuring cup with stopper, mix 0.12g sulphur powder, after sealing, be placed in 160 ℃ of baking ovens and heat, cooling taking-up after 10h, obtains corresponding carbon nanosheet/sulphur composite material.Press the method in embodiment 1, prepare electrode and assembled battery, and carry out performance conventionally test, under 0.5C multiplying power, discharge capacity is 1210 mA h g
-1.
embodiment 7
In beaker, add successively 600 mlH
2o, 100 ml graphene oxide solution 1mg/ml, 100 ml SiO
2solution 2mg/ml and 2 g pyrroles, magnetic agitation 1 h in ice-water bath, then add the dense HCl of 50ml and the 6 g APS aqueous solution in beaker, suction filtration after reaction 12 h, then with distillation washing, until filtrate is colourless, gained solid is placed in to 110 ℃ of baking ovens and dries.Get 6 grams of above-mentioned solids in crucible, logical N
2, with 5 ℃/min, be warming up to 850 ℃ of insulations naturally cooling after 2 h.Be transferred to 20% hydrofluoric acid solution, after stirring 2h, filter, wash, product after 110 ℃ of corresponding carbonizations of oven dry acquisition.Get this product 0.4g and be placed in beaker, successively add 2ml water, 20ml ethanol and 1.2g KOH solid, stir lower heating solvent evaporated, be transferred in nickel crucible logical N
2, with 5 ℃/min, be warming up to 800 ℃ of insulations naturally cooling after 1 h, successively use hydrochloric acid and water washing to neutral gained solid, filter in rear 110 ℃ of baking ovens and dry, obtain the graphene-based nitrogen of the 1.2g multi-stage porous hydridization carbon nanosheet that adulterates.Get above-mentioned carbon nanosheet 0.04g and be placed in the measuring cup with stopper, mix 0.12g sulphur powder, after sealing, be placed in 160 ℃ of baking ovens and heat, cooling taking-up after 10h, obtains corresponding carbon nanosheet/sulphur composite material.Press the method in embodiment 1, prepare electrode and assembled battery, and carry out performance conventionally test, under 0.5C multiplying power, discharge capacity is 910 mA h g
-1.
embodiment 8
In beaker, add successively 600 mlH
2o, 100 ml graphene oxide solution (1mg ml
-1), 100 ml SiO
2solution (2mg ml
-1) and 4 g pyrroles, magnetic agitation 1 h in ice-water bath, then add the dense HCl of 50ml and the 12 g APS aqueous solution in beaker, suction filtration after reaction 12 h, then with distillation washing, until filtrate is colourless, gained solid is placed in to 110 ℃ of baking ovens and dries.Get 6 grams of above-mentioned solids in crucible, logical N
2, with 5 ℃ of min
-1be warming up to 900 ℃ of insulations naturally cooling after 2 h.Be transferred to 20% hydrofluoric acid solution, after stirring 2h, filter, wash, product after 110 ℃ of corresponding carbonizations of oven dry acquisition.Get this product 0.4g and be placed in beaker, successively add 2ml water, 20ml ethanol and 1.2g KOH solid, stir lower heating solvent evaporated, be transferred in nickel crucible logical N
2, with 5 ℃ of min
-1be warming up to 800 ℃ of insulations naturally cooling after 1 h, successively use hydrochloric acid and water washing to neutral gained solid, filter in rear 110 ℃ of baking ovens and dry, obtain the graphene-based nitrogen of the 1.2g multi-stage porous hydridization carbon nanosheet that adulterates.Get above-mentioned carbon nanosheet 0.04g and be placed in the measuring cup with stopper, mix 0.12g sulphur powder, after sealing, be placed in 160 ℃ of baking ovens and heat, cooling taking-up after 10h, obtains corresponding carbon nanosheet/sulphur composite material.Press the method in embodiment 1, prepare electrode and assembled battery, and carry out performance conventionally test, under 0.5C multiplying power, discharge capacity is 1270 mA h g
-1.
embodiment 9
In beaker, add successively 600 mlH
2o, 100 ml graphene oxide solution (1mg ml
-1), 100 ml SiO
2solution (2mg ml
-1) and 4 g pyrroles, magnetic agitation 1 h in ice-water bath, then add the dense HCl of 50ml and the 12 g APS aqueous solution in beaker, suction filtration after reaction 12 h, then with distillation washing, until filtrate is colourless, gained solid is placed in to 110 ℃ of baking ovens and dries.Get 6 grams of above-mentioned solids in crucible, logical N
2, with 5 ℃ of min
-1be warming up to 700 ℃ of insulations naturally cooling after 2 h.Be transferred to 20% hydrofluoric acid solution, after stirring 2h, filter, wash, product after 110 ℃ of corresponding carbonizations of oven dry acquisition.Get this product 0.4g and be placed in beaker, successively add 2ml water, 20ml ethanol and 1.2g KOH solid, stir lower heating solvent evaporated, be transferred in nickel crucible logical N
2, with 5 ℃ of min
-1be warming up to 800 ℃ of insulations naturally cooling after 1 h, successively use hydrochloric acid and water washing to neutral gained solid, filter in rear 110 ℃ of baking ovens and dry, obtain the graphene-based nitrogen of the 1.2g multi-stage porous hydridization carbon nanosheet (APPG) that adulterates.Get above-mentioned carbon nanosheet 0.04g and be placed in the measuring cup with stopper, mix 0.12g sulphur powder, after sealing, be placed in 160 ℃ of baking ovens and heat, cooling taking-up after 10h, obtains corresponding carbon nanosheet/sulphur composite material.Press the method in embodiment 1, prepare electrode and assembled battery, and carry out performance conventionally test, under 0.5C multiplying power, discharge capacity is 1150 mA h g
-1.
The PPG 0.4g that takes preparation in embodiment 1 is placed in beaker, successively adds 2ml water, 20ml ethanol and 0.8g KOH solid, stirs lower heating solvent evaporated, is transferred in nickel crucible logical N
2, with 5 ℃ of min
-1be warming up to 800 ℃ of insulations naturally cooling after 1 h, successively use hydrochloric acid and water washing to neutral gained solid, filter in rear 110 ℃ of baking ovens and dry, obtain the graphene-based nitrogen of the 1.2g multi-stage porous hydridization carbon nanosheet that adulterates.Get above-mentioned carbon nanosheet 0.04g and be placed in the measuring cup with stopper, mix 0.12g sulphur powder, after sealing, be placed in 160 ℃ of baking ovens and heat, cooling taking-up after 10h, obtains corresponding carbon nanosheet/sulphur composite material.Press the method in embodiment 1, prepare electrode and assembled battery, and carry out performance conventionally test, under 0.5C multiplying power, discharge capacity is 1050 mA h g
-1.
embodiment 11
The PPG 0.4g that takes preparation in embodiment 1 is placed in beaker, successively adds 2ml water, 20ml ethanol and 1.6g KOH solid, stirs lower heating solvent evaporated, is transferred in nickel crucible logical N
2, with 5 ℃ of min
-1be warming up to 800 ℃ of insulations naturally cooling after 1 h, successively use hydrochloric acid and water washing to neutral gained solid, filter in rear 110 ℃ of baking ovens and dry, obtain the graphene-based nitrogen of the 1.2g multi-stage porous hydridization carbon nanosheet (APPG) that adulterates.Get above-mentioned carbon nanosheet 0.04g and be placed in the measuring cup with stopper, mix 0.12g sulphur powder, after sealing, be placed in 160 ℃ of baking ovens and heat, cooling taking-up after 10h, obtains corresponding carbon nanosheet/sulphur composite material.Press the method in embodiment 1, prepare electrode and assembled battery, and carry out performance conventionally test, under 0.5C multiplying power, discharge capacity is 1190 mA h g
-1.
Claims (9)
1. the doping of the graphene-based nitrogen for lithium-sulphur cell positive electrode multi-stage porous carbon nanometer sheet/sulphur composite material, it is characterized in that: comprise graphene-based nitrogen doping multi-stage porous carbon nanometer sheet and utilize physics to permeate the elemental sulfur in graphene-based nitrogen doping multi-stage porous carbon nanometer sheet, wherein elemental sulfur accounts for the 69-89wt% of total compound, graphene-based nitrogen doping multi-stage porous carbon nanometer sheet has hierarchical porous structure, comprise micropore and mesoporous, aperture concentrates between 0.8-6 nm, and specific area 800-1600 m
2g
-1, pore volume 0.7-1.2 cm
2g
-1.
2. a kind of graphene-based nitrogen 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 nitrogen doping multi-stage porous carbon nanometer sheet is that Graphene is inserted into the structure that forms class sandwich type between amorphous conductive carbon.
3. a kind of doping of the graphene-based nitrogen for lithium-sulphur cell positive electrode multi-stage porous carbon nanometer sheet/sulphur composite material according to claim 2, is characterized in that: in graphene-based nitrogen doping multi-stage porous carbon nanometer sheet, amorphous carbon is the polypyrrole that derives from potassium hydroxide activation at carbonization at 700-900 ℃, 800 ℃.
4. a kind of doping of the graphene-based nitrogen for lithium-sulphur cell positive electrode multi-stage porous carbon nanometer sheet/sulphur composite material according to claim 3, it is characterized in that: the nitrogen element of graphene-based nitrogen doping multi-stage porous carbon nanometer sheet doping derives from the nitrogen-atoms in polypyrrole, the about 2wt% of its doping.
5. a kind of graphene-based nitrogen 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 nitrogen doping multi-stage porous carbon nanometer sheet is 10-25 nm.
6. a method of preparing the graphene-based nitrogen doping multi-stage porous carbon nanometer sheet/sulphur composite material for lithium-sulphur cell positive electrode as described in one of claim 1-5, is characterized in that comprising the following steps:
(1) preparation of graphene-based nitrogen doping multi-stage porous structure carbon nanosheet
The nano silicon that is 5-8nm by graphene oxide and particle diameter mixes by the mass ratio of 1:2, add pyrroles, graphene oxide and pyrroles's mass ratio is 1:20-50, mix, under ice bath, stir, add 50ml hydrochloric acid and ammonium persulfate, the addition of ammonium persulfate and pyrroles's mass ratio are 1:3, continue after reaction 12h, filter, priority ethanol, water washs respectively, vacuumize, roasting 2h at nitrogen atmosphere 700-900 ℃, the black powder obtaining joins 20% hydrofluoric acid solution stirring, filter, dry, the product obtaining be take mass ratio and in ethanol, is mixed as 1:1-4 with potassium hydroxide, ultrasonic, ethanol evaporation is to dry, transfer in tube furnace roasting 1-5h at 800 ℃, 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 1) prepared carbon nanosheet and elemental sulfur in mass ratio 1:3-1:5 mix, and be sealed in measuring cup, heat 160 ℃, constant temperature 10h, is cooled to room temperature, obtains corresponding carbon nanosheet/sulphur composite material.
7. an application for the graphene-based nitrogen 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 that graphene-based nitrogen doping multi-stage porous carbon nanometer sheet/sulphur composite material is applied to a kind of lithium-sulfur cell.
8. the application of a kind of graphene-based nitrogen 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:
Graphene-based nitrogen doping multi-stage porous carbon nanometer sheet/sulphur composite material, acetylene black and Polyvinylidene are mixed according to the mass ratio of 8:1:1, be coated in aluminum foil current collector, vacuumize at 50 ℃, 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: described method preparation just very claimed 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 1mol L
-1, the mass fraction 1% of lithium nitrate, glycol dimethyl ether and 1,3-dioxane volume ratio are 1:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310743270.7A CN103700859B (en) | 2013-12-30 | 2013-12-30 | Lithium-sulphur cell positive electrode graphene-based N doping multi-stage porous carbon nanometer sheet/sulphur composite material and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310743270.7A CN103700859B (en) | 2013-12-30 | 2013-12-30 | Lithium-sulphur cell positive electrode graphene-based N doping multi-stage porous carbon nanometer sheet/sulphur composite material and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103700859A true CN103700859A (en) | 2014-04-02 |
| CN103700859B CN103700859B (en) | 2016-01-06 |
Family
ID=50362316
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310743270.7A Active CN103700859B (en) | 2013-12-30 | 2013-12-30 | Lithium-sulphur cell positive electrode graphene-based N doping multi-stage porous carbon nanometer sheet/sulphur composite material and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103700859B (en) |
Cited By (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104294584A (en) * | 2014-09-29 | 2015-01-21 | 黄勇 | Fabric with doped-type graphene coating and preparation process of fabric |
| CN104733695A (en) * | 2015-03-27 | 2015-06-24 | 浙江大学 | Carbon/sulfur composite material for lithium-sulfur battery cathode as well as preparation method and application |
| CN104882594A (en) * | 2015-04-16 | 2015-09-02 | 中国人民解放军国防科学技术大学 | Three-dimensional graphene-hollow carbon sphere nano composite and preparation method thereof |
| CN105304958A (en) * | 2014-06-12 | 2016-02-03 | 清华大学 | Manufacturing method for long-life lithium sulfur battery positive electrode |
| CN105514395A (en) * | 2016-02-04 | 2016-04-20 | 西安理工大学 | Method for preparing cathode material of graphene-doped lithium sulfur battery by adopting microwave liquid phase process |
| CN105958041A (en) * | 2016-07-18 | 2016-09-21 | 扬州大学 | Method for preparing hollow microporous carbon sphere coated nanometer sulfur molecular material |
| CN106450423A (en) * | 2016-09-30 | 2017-02-22 | 上海空间电源研究所 | High-specific-energy flexible integrated electrode and preparation method therefor |
| CN106602010A (en) * | 2016-12-12 | 2017-04-26 | 成都育芽科技有限公司 | Preparation method and application of graphene-coated sulfur-selenium co-impregnated porous carbon positive electrode material |
| CN106744827A (en) * | 2016-11-22 | 2017-05-31 | 华中科技大学 | A kind of method for carrying out controllable pore-creating to Graphene using microwave burning |
| CN106848210A (en) * | 2015-12-03 | 2017-06-13 | 财团法人工业技术研究院 | Electrode, preparation method of electrode and battery |
| JP2017521847A (en) * | 2014-06-11 | 2017-08-03 | 中国科学院蘇州納米技術与納米倣生研究所Ｓｕｚｈｏｕ Ｉｎｓｔｉｔｕｔｅ Ｏｆ Ｎａｎｏ−Ｔｅｃｈ Ａｎｄ Ｎａｎｏ−Ｂｉｏｎｉｃｓ（Ｓｉｎａｎｏ），Ｃｈｉｎｅｓｅ Ａｃａｄｅｍｙ Ｏｆ Ｓｃｉｅｎｃｅ | Nano-sulfur cathode composite coated with nitrogen-doped graphene, its preparation method and application |
| CN107546381A (en) * | 2017-08-29 | 2018-01-05 | 中国科学院福建物质结构研究所 | It is a kind of that lithium sulfur battery anode material is used as using ionomer derivative carbon material |
| 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 |
| CN107732202A (en) * | 2017-10-16 | 2018-02-23 | 河源广工大协同创新研究院 | A kind of preparation method of lithium sulfur battery anode material |
| CN108400343A (en) * | 2018-02-13 | 2018-08-14 | 山东大学 | A kind of nitrogen load carbon nanosheet lithium oxygen battery anode catalytic agent material and preparation method thereof that high-performance cobalt granule is modified |
| CN109360956A (en) * | 2018-09-30 | 2019-02-19 | 桑德集团有限公司 | A kind of positive electrode and preparation method thereof, lithium-sulfur cell |
| CN109592676A (en) * | 2018-12-14 | 2019-04-09 | 东华大学 | The preparation method of the derivative carbon nano-composite material of growth carbon nanosheet matrix on a kind of graphene oxide |
| CN109742338A (en) * | 2018-12-13 | 2019-05-10 | 温州大学 | Tetra- serobilas of G-/hemachrome enzyme/carbon nano tube compound material preparation method and its application in lithium-sulfur cell |
| CN109830683A (en) * | 2019-02-18 | 2019-05-31 | 山东星火科学技术研究院 | A kind of preparation method of the powerful nitrogen-doped graphene negative electrode material of high capacity |
| CN109860529A (en) * | 2018-12-06 | 2019-06-07 | 盐城工学院 | A kind of high-performance porous carbon-tin oxide monodisperse composite balls negative electrode material and its preparation method and application |
| CN110034288A (en) * | 2019-04-15 | 2019-07-19 | 深圳市高能达电池有限公司 | A kind of lithium-sulphur cell positive electrode graphene grafted polypyrrole nanotube/sulphur composite material preparation method |
| CN110655060A (en) * | 2019-09-03 | 2020-01-07 | 中国农业科学院油料作物研究所 | Double-sided amphiphilic carrier and preparation method and application thereof |
| CN111211300A (en) * | 2020-01-10 | 2020-05-29 | 南昌大学 | Metallic nickel/nitrogen doped carbon nanotube and lithium-sulfur battery composite positive electrode material thereof |
| CN111211310A (en) * | 2020-01-16 | 2020-05-29 | 中南大学 | Nickel boride/boron-doped porous carbon material, preparation thereof and application thereof in lithium-sulfur battery |
| CN111834635A (en) * | 2020-07-02 | 2020-10-27 | 华中科技大学 | Monoatomic molybdenum-nitrogen-carbon nanosheet material with dispersed molybdenum, and preparation and application thereof |
| CN112201484A (en) * | 2020-08-24 | 2021-01-08 | 温州大学 | Two-dimensional ultrathin carbon nanosheet and preparation method and application thereof |
| CN112242547A (en) * | 2020-10-19 | 2021-01-19 | 苏州科技大学 | Preparation method of electronic skin biofuel cell and biofuel cell |
| CN112479176A (en) * | 2020-10-26 | 2021-03-12 | 温州大学 | 3D carbon foam material, preparation method and application thereof |
| IT201900016178A1 (en) * | 2019-09-12 | 2021-03-12 | Fondazione St Italiano Tecnologia | PROCESS FOR THE PRODUCTION OF A SULFUR-CARBON COMPOSITE MATERIAL, COMPOSITE MATERIAL SO OBTAINED AND ELECTRODE FOR LITHIUM-SULFUR BATTERIES PRODUCED WITH THE MATERIAL |
| CN114050266A (en) * | 2021-11-23 | 2022-02-15 | 珠海鹏辉能源有限公司 | Selenium disulfide composite nitrogen-doped reduced graphene oxide cathode material and preparation method thereof, lithium-selenium disulfide battery and electric equipment |
| CN114735673A (en) * | 2022-05-05 | 2022-07-12 | 贵州大学 | Preparation method and application of crosslinked mesoporous carbon composite material |
| CN114783787A (en) * | 2022-05-17 | 2022-07-22 | 晋江瑞碧科技有限公司 | Preparation method of carbon nanotube/nitrogen-doped graphene/porous carbon composite aerogel |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110052998A1 (en) * | 2009-09-02 | 2011-03-03 | Ut-Battelle, Llc | Sulfur-carbon nanocomposites and their application as cathode materials in lithium-sulfur batteries |
| CN101986443A (en) * | 2010-05-25 | 2011-03-16 | 耿世达 | Lithium sulfur battery anode material and preparation method thereof |
| CN103050669A (en) * | 2011-10-17 | 2013-04-17 | 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 |
-
2013
- 2013-12-30 CN CN201310743270.7A patent/CN103700859B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110052998A1 (en) * | 2009-09-02 | 2011-03-03 | Ut-Battelle, Llc | Sulfur-carbon nanocomposites and their application as cathode materials in lithium-sulfur batteries |
| CN101986443A (en) * | 2010-05-25 | 2011-03-16 | 耿世达 | Lithium sulfur battery anode material and preparation method thereof |
| CN103050669A (en) * | 2011-10-17 | 2013-04-17 | 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 |
Cited By (48)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3157080A4 (en) * | 2014-06-11 | 2017-10-25 | Suzhou Institute of Nano-tech and Nano-bionics (SINANO) Chinese Academy of Sciences | Nitrogen-doped graphene coated nano-sulfur anode composite material, and preparation method and application thereof |
| JP2017521847A (en) * | 2014-06-11 | 2017-08-03 | 中国科学院蘇州納米技術与納米倣生研究所Ｓｕｚｈｏｕ Ｉｎｓｔｉｔｕｔｅ Ｏｆ Ｎａｎｏ−Ｔｅｃｈ Ａｎｄ Ｎａｎｏ−Ｂｉｏｎｉｃｓ（Ｓｉｎａｎｏ），Ｃｈｉｎｅｓｅ Ａｃａｄｅｍｙ Ｏｆ Ｓｃｉｅｎｃｅ | Nano-sulfur cathode composite coated with nitrogen-doped graphene, its preparation method and application |
| CN105304958A (en) * | 2014-06-12 | 2016-02-03 | 清华大学 | Manufacturing method for long-life lithium sulfur battery positive electrode |
| CN105304958B (en) * | 2014-06-12 | 2018-06-26 | 清华大学 | A kind of production method of long-life lithium-sulphur cell positive electrode |
| CN104294584A (en) * | 2014-09-29 | 2015-01-21 | 黄勇 | Fabric with doped-type graphene coating and preparation process of fabric |
| CN104733695A (en) * | 2015-03-27 | 2015-06-24 | 浙江大学 | Carbon/sulfur composite material for lithium-sulfur battery cathode as well as preparation method and application |
| CN104882594A (en) * | 2015-04-16 | 2015-09-02 | 中国人民解放军国防科学技术大学 | Three-dimensional graphene-hollow carbon sphere nano composite and preparation method thereof |
| CN107615526B (en) * | 2015-06-05 | 2021-01-12 | 罗伯特·博世有限公司 | Sulfur-carbon composite material comprising microporous carbon nanoplatelets for lithium-sulfur batteries and method for preparing same |
| 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 |
| CN106848210B (en) * | 2015-12-03 | 2020-05-05 | 财团法人工业技术研究院 | Electrode, preparation method of electrode and battery |
| CN106848210A (en) * | 2015-12-03 | 2017-06-13 | 财团法人工业技术研究院 | Electrode, preparation method of electrode and battery |
| CN105514395A (en) * | 2016-02-04 | 2016-04-20 | 西安理工大学 | Method for preparing cathode material of graphene-doped lithium sulfur battery by adopting microwave liquid phase process |
| CN105958041A (en) * | 2016-07-18 | 2016-09-21 | 扬州大学 | Method for preparing hollow microporous carbon sphere coated nanometer sulfur molecular material |
| CN106450423A (en) * | 2016-09-30 | 2017-02-22 | 上海空间电源研究所 | High-specific-energy flexible integrated electrode and preparation method therefor |
| CN106450423B (en) * | 2016-09-30 | 2019-06-25 | 上海空间电源研究所 | A kind of high specific energy integrated flexible electrode and preparation method thereof |
| CN106744827A (en) * | 2016-11-22 | 2017-05-31 | 华中科技大学 | A kind of method for carrying out controllable pore-creating to Graphene using microwave burning |
| CN106744827B (en) * | 2016-11-22 | 2018-12-28 | 华中科技大学 | A method of controllable pore-creating being carried out to graphene using microwave burning |
| CN106602010A (en) * | 2016-12-12 | 2017-04-26 | 成都育芽科技有限公司 | Preparation method and application of graphene-coated sulfur-selenium co-impregnated porous carbon positive electrode material |
| CN106602010B (en) * | 2016-12-12 | 2019-05-10 | 江华中科能源科技有限公司 | The preparation method and application of graphene coated sulphur selenium co-impregnation porous carbon positive electrode |
| CN107546381A (en) * | 2017-08-29 | 2018-01-05 | 中国科学院福建物质结构研究所 | It is a kind of that lithium sulfur battery anode material is used as using ionomer derivative carbon material |
| CN107732202A (en) * | 2017-10-16 | 2018-02-23 | 河源广工大协同创新研究院 | A kind of preparation method of lithium sulfur battery anode material |
| CN108400343A (en) * | 2018-02-13 | 2018-08-14 | 山东大学 | A kind of nitrogen load carbon nanosheet lithium oxygen battery anode catalytic agent material and preparation method thereof that high-performance cobalt granule is modified |
| CN109360956A (en) * | 2018-09-30 | 2019-02-19 | 桑德集团有限公司 | A kind of positive electrode and preparation method thereof, lithium-sulfur cell |
| CN109860529B (en) * | 2018-12-06 | 2022-04-12 | 盐城工学院 | High-performance porous carbon-tin oxide monodisperse composite sphere negative electrode material and preparation method and application thereof |
| CN109860529A (en) * | 2018-12-06 | 2019-06-07 | 盐城工学院 | A kind of high-performance porous carbon-tin oxide monodisperse composite balls negative electrode material and its preparation method and application |
| CN109742338A (en) * | 2018-12-13 | 2019-05-10 | 温州大学 | Tetra- serobilas of G-/hemachrome enzyme/carbon nano tube compound material preparation method and its application in lithium-sulfur cell |
| CN109742338B (en) * | 2018-12-13 | 2021-04-20 | 温州大学 | Preparation method of G-quadruplex/heme enzyme/carbon nanotube composite material and application of G-quadruplex/heme enzyme/carbon nanotube composite material in lithium-sulfur battery |
| CN109592676B (en) * | 2018-12-14 | 2021-12-21 | 东华大学 | Preparation method of carbon nano composite material derived from carbon nanosheet matrix grown on graphene oxide |
| CN109592676A (en) * | 2018-12-14 | 2019-04-09 | 东华大学 | The preparation method of the derivative carbon nano-composite material of growth carbon nanosheet matrix on a kind of graphene oxide |
| CN109830683A (en) * | 2019-02-18 | 2019-05-31 | 山东星火科学技术研究院 | A kind of preparation method of the powerful nitrogen-doped graphene negative electrode material of high capacity |
| CN110034288A (en) * | 2019-04-15 | 2019-07-19 | 深圳市高能达电池有限公司 | A kind of lithium-sulphur cell positive electrode graphene grafted polypyrrole nanotube/sulphur composite material preparation method |
| CN110655060A (en) * | 2019-09-03 | 2020-01-07 | 中国农业科学院油料作物研究所 | Double-sided amphiphilic carrier and preparation method and application thereof |
| CN110655060B (en) * | 2019-09-03 | 2021-09-24 | 中国农业科学院油料作物研究所 | Double-sided amphiphilic carrier and preparation method and application thereof |
| WO2021048815A1 (en) * | 2019-09-12 | 2021-03-18 | Fondazione Istituto Italiano Di Tecnologia | Process for the production of a sulfur-carbon composite material, composite material thus obtained and electrode for lithium-sulfur batteries produced with the material |
| IT201900016178A1 (en) * | 2019-09-12 | 2021-03-12 | Fondazione St Italiano Tecnologia | PROCESS FOR THE PRODUCTION OF A SULFUR-CARBON COMPOSITE MATERIAL, COMPOSITE MATERIAL SO OBTAINED AND ELECTRODE FOR LITHIUM-SULFUR BATTERIES PRODUCED WITH THE MATERIAL |
| CN111211300A (en) * | 2020-01-10 | 2020-05-29 | 南昌大学 | Metallic nickel/nitrogen doped carbon nanotube and lithium-sulfur battery composite positive electrode material thereof |
| CN111211310A (en) * | 2020-01-16 | 2020-05-29 | 中南大学 | Nickel boride/boron-doped porous carbon material, preparation thereof and application thereof in lithium-sulfur battery |
| CN111211310B (en) * | 2020-01-16 | 2021-04-09 | 中南大学 | Nickel boride/boron-doped porous carbon material, preparation thereof and application thereof in lithium-sulfur battery |
| CN111834635A (en) * | 2020-07-02 | 2020-10-27 | 华中科技大学 | Monoatomic molybdenum-nitrogen-carbon nanosheet material with dispersed molybdenum, and preparation and application thereof |
| CN112201484A (en) * | 2020-08-24 | 2021-01-08 | 温州大学 | Two-dimensional ultrathin carbon nanosheet and preparation method and application thereof |
| CN112242547B (en) * | 2020-10-19 | 2021-07-09 | 苏州科技大学 | Preparation method of electronic skin biofuel cell and biofuel cell |
| CN112242547A (en) * | 2020-10-19 | 2021-01-19 | 苏州科技大学 | Preparation method of electronic skin biofuel cell and biofuel cell |
| CN112479176A (en) * | 2020-10-26 | 2021-03-12 | 温州大学 | 3D carbon foam material, preparation method and application thereof |
| CN114050266A (en) * | 2021-11-23 | 2022-02-15 | 珠海鹏辉能源有限公司 | Selenium disulfide composite nitrogen-doped reduced graphene oxide cathode material and preparation method thereof, lithium-selenium disulfide battery and electric equipment |
| CN114735673A (en) * | 2022-05-05 | 2022-07-12 | 贵州大学 | Preparation method and application of crosslinked mesoporous carbon composite material |
| CN114735673B (en) * | 2022-05-05 | 2024-03-01 | 贵州大学 | Preparation method and application of crosslinked micro-mesoporous carbon composite material |
| CN114783787A (en) * | 2022-05-17 | 2022-07-22 | 晋江瑞碧科技有限公司 | Preparation method of carbon nanotube/nitrogen-doped graphene/porous carbon composite aerogel |
| CN114783787B (en) * | 2022-05-17 | 2023-08-04 | 武夷学院 | Preparation method of carbon nano tube/nitrogen doped graphene/porous carbon composite aerogel |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103700859B (en) | 2016-01-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103700859B (en) | Lithium-sulphur cell positive electrode graphene-based N doping multi-stage porous carbon nanometer sheet/sulphur composite material and its preparation method and application | |
| Wang et al. | Zn-ion hybrid supercapacitors: achievements, challenges and future perspectives | |
| Wang et al. | Chemically activated hollow carbon nanospheres as a high-performance anode material for potassium ion batteries | |
| Zhou et al. | Confining small sulfur molecules in peanut shell-derived microporous graphitic carbon for advanced lithium sulfur battery | |
| EP3128585B1 (en) | Composite cathode material and preparation method thereof, cathode pole piece of lithium ion secondary battery, and lithium ion secondary battery | |
| CN102969487B (en) | Carbon-sulfur composite material used for positive pole of lithium-sulfur battery and preparation method of material | |
| Zhou et al. | Spin-coated silicon nanoparticle/graphene electrode as a binder-free anode for high-performance lithium-ion batteries | |
| CN109728246B (en) | Nitrogen-phosphorus co-doped ordered mesoporous carbon material and preparation method and application thereof | |
| Yang et al. | Sulfur impregnated in a mesoporous covalent organic framework for high performance lithium–sulfur batteries | |
| CN107221654B (en) | Three-dimensional porous nest-shaped silicon-carbon composite negative electrode material and preparation method thereof | |
| CN108155353B (en) | Graphitized carbon coated electrode material, preparation method thereof and application of graphitized carbon coated electrode material as energy storage device electrode material | |
| CN105314622A (en) | Method for preparing hetero-atom doped porous carbon material through carbonation of biomass under assistance of molten salt | |
| CN102820456B (en) | Porous carbon/sulfur composite material, its preparation method and application | |
| CN108666570B (en) | Porous carbon nanobelt lithium-sulfur battery positive electrode material and preparation method and application thereof | |
| Han et al. | High specific power/energy, ultralong life supercapacitors enabled by cross-cutting bamboo-derived porous carbons | |
| CN107732203B (en) | Preparation method of nano cerium dioxide/graphene/sulfur composite material | |
| CN104538207A (en) | Method for preparing titanium niobate and carbon nanotube composite material and lithium ion capacitor with material as negative electrode | |
| CN111900326A (en) | Preparation method and application of positive electrode-interlayer integrated membrane material for lithium-sulfur battery | |
| Yang et al. | Hollow MnO2 spheres/porous reduced graphene oxide as a cathode host for high-performance lithium-sulfur batteries | |
| Gong et al. | Anchoring high-mass iodine to nanoporous carbon with large-volume micropores and rich pyridine-N sites for high-energy-density and long-life Zn-I2 aqueous battery | |
| Zang et al. | Construction of high conductivity carbon-coated MoS2 on porous carbon nanofibers for synergistic potassium storage | |
| Lai et al. | Chemically tailoring porosity carbon foam with oxygen-containing functional groups to restrain polysulfide for lithium-sulfur batteries | |
| Sui et al. | Highly dispersive CoSe 2 nanoparticles encapsulated in carbon nanotube-grafted multichannel carbon fibers as advanced anodes for sodium-ion half/full batteries | |
| Shi et al. | Nitrogen-Doped nano-carbon onion rings for energy storage in Lithium-ion capacitors | |
| Meng et al. | Lightweight freestanding hollow carbon fiber interlayer for high‐performance lithium‐sulfur batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |