CN104520231A - Method for preparing sulfur-containing carbon material and sulfur-containing carbon material prepared therewith - Google Patents
Method for preparing sulfur-containing carbon material and sulfur-containing carbon material prepared therewith Download PDFInfo
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- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- C—CHEMISTRY; METALLURGY
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/44—Carbon
Abstract
A method for preparing a sulfur-containing carbon material is provided, which comprises: using a carbon material and sulfate and/or sulfite as raw materials; performing solid phase mixing or liquid phase dip method to obtain a compound of the carbon material and the sulfate and/or sulfite; and calcining the compound to obtain a sulfur-containing carbon material. By means of the method, post processing may be performed on the existing carbon material to implement sulfur doping, so as to prepare different types of sulfur-containing carbon materials.
Description
A kind of method for preparing sulfur-bearing carbon material and its sulfur-bearing carbon material technical field of preparation
The invention belongs to new carbon preparing technical field, it is related to the preparation method of sulfur-bearing carbon material, specifically, is related to the sulfur-bearing carbon material of a kind of method for preparing sulfur-bearing carbon material and its preparation.Background technology
Carbon material is human research and applies a class common materials, including the graphite and diamond found earliest earlier, also activated carbon, porous carbon etc., and newfound fullerene, CNT and graphene in recent decades.Because carbon material has its outstanding feature on physical and chemical performance, had a wide range of applications in many fields such as electricity, mechanics and chemistry.
In recent years, increasing scientific worker conducted in-depth research to being entrained in for carbon material.By taking the doping of graphene as an example, the major reason that graphene can be applied to microelectronic component is exactly the adjustability of its carrier concentration and carrier polarity, and chemical doping exactly realizes the important way of this regulation and control.Wei et al.（Nano Letters 9(5):1752-1758) use CH4And NH3For raw material using CVD under the conditions of 800 °C in a small number of layer graphenes that N doping is grown on Copper thin film surface, electrical measurement shows that the graphene of N doping shows n-type semiconductor behavior.In addition, the preparation and application of the CNT of nitrating or boron also have more report（Inorganica Chimica Acta 363(15): 4163-4174) .
Except nitrogen-doping, the carbon material of element sulphur doping is also paid close attention to.Yang et al.（Acs Nano 2012;6(1):A kind of method for 205-211) reporting use chemical synthesis prepares the method for mixing sulfur graphite alkene.The research shows：Mix after sulphur, graphene has higher catalytic performance in a fuel cell.Paraknowitsch et al.（Chem. Commun., 2011,47,8283-8285) it is prepared for mixing the porous charcoal of sulphur.Research is more prepares carbon material as presoma using the compound of sulfur-bearing for these, need further raising in material morphology control, and mixes sulphur carbon material without what any one prior art can be used for preparing various species.Therefore, carrying out the method that sulphur is mixed in post processing realization to existing carbon material the invention provides a kind of, different types of sulfur-bearing carbon material can be prepared, is a kind of universal method.The content of the invention
It is an object of the present invention to provide a kind of method for preparing sulfur-bearing carbon material.
Another object of the present invention is to provide the sulfur-bearing carbon material of the method for the invention preparation.
For up to above-mentioned purpose, on the one hand, the invention provides a kind of method for preparing sulfur-bearing carbon material, methods described includes being used as raw material with sulfate and/or sulphite using carbon material, carbon material and sulfate and/or the compound of sulphite are obtained using solid phase mixing or liquid impregnation method, the compound is calcined, sulfur-bearing carbon material is obtained.
The present invention can mix carbon material with sulfate or sulphite, then obtain carbon material and sulfate or the compound of sulphite using solid phase mixing or liquid impregnation method；
The present invention can also mix carbon material with sulfate and sulphite, then obtain carbon material and sulfate and the compound of sulphite using solid phase mixing or liquid impregnation method.
Wherein when using sulfate and sulphite mixture, sulfate and sulphite can be any mass ratio.According to method of the present invention, preferably described carbon material and sulfate and/or sulphite mass ratio are 1: 0.01-100.
It is understood that wherein carbon material and sulfate or sulphite mass ratio are 1: 0.01-100；Or when using sulfate and sulphite mixture, the mass ratio of carbon material and sulfate and sulphite mixture is 1： 0.01-100.
Wherein it is preferred that the carbon material and sulfate and/or sulphite mass ratio are 1: 0.1-20.
According to method of the present invention, the carbon material can prepare any carbon material of sulfur-bearing carbon material for this area, those skilled in the art can select suitable carbon material in the range of this area, and the present invention is preferably one or more than one kinds of mixtures among graphite, graphite flake, CNT, carbon fiber, graphene, porous graphene, fullerene, activated carbon, porous charcoal, Carbon foam, petroleum coke, coal coke and carbon black.
According to method of the present invention, the sulfate includes one or more than one kinds of mixtures among ferric sulfate, cobaltous sulfate, nickel sulfate, manganese sulfate, aluminum sulfate, zinc sulfate, titanium sulfate, magnesium sulfate, alkali magnesium sulfate, copper sulphate, basic copper sulfate, lead sulfate, basic lead sulphate, calcium sulfate, potassium sulfate, sulfate of ammoniac, ammonium hydrogen sulfate, dihydrogen sulfate ammonium, and sulphite includes one or more than one kinds of mixtures among sodium sulfite, potassium sulfite, sodium hydrogensulfite, potassium bisulfite, calcium sulfite.
According to method of the present invention, the calcining heat is 500 1000 °C, and the time is 5-600 minutes.Wherein preferred calcination temperature is 500-900 °C;
The wherein further preferred time is 30-300 minutes.
According to method of the present invention, the calcination processing comprises the following steps：The mixture of sulfate and/or sulphite and carbon material is put into reactor, carrier gas, heating calcining is passed through；
Wherein described carrier gas can prepare any carrier gas of sulfur-bearing carbon material for this area, and those skilled in the art can select suitable carrier gas in the range of this area, and the present invention preferably carrier gas is one kind among nitrogen, argon gas, helium
Or more than one mixture.
Wherein the present invention has no particular/special requirement to carrier gas consumption, is for example the mL/min of 10- 5000 using prior art conventional ventilation amount.
According to method of the present invention, the step of also including being cleaned with acid solution after calcining.
Wherein described acid solution can be the aqueous solution of the sour aqueous solution, for example hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid commonly used in the art；
The sour concentration of aqueous solution can be concentration commonly used in the art, and its specific concentration has no influence for the realization of the object of the invention, and the water of 0.5-5 times of volume can be for example added for the above-mentioned acid of 1 times of volume.
The pickling removes sulfate and/or sulphite template to be washed till；Those skilled in the art can determine according to prior art experience and practical operation situation, pay more creative works for this without those skilled in the art, for example can be 0.5-2 hours for pickling, then can be for example 1 hour.
If producing metal oxide during wherein, it is also preferred that removing in the lump.
According to method of the present invention, the liquid-phase impregnation process comprises the following steps：
(1) carbon material is immersed in the water and/or alcoholic solution of sulfate and/or sulphite, ultrasonic disperse obtains suspension；
(2) by step（1) gained suspension is dried, and obtains the compound of sulfate or sulphite and carbon material.According to method of the present invention, wherein step（2) drying is drying as commonly understood in the art, rather than adiabatic drying.
The present invention has no particular requirement to the ratio and consumption of described water and/or ethanol solution, as long as meeting carbon material to scatter wherein, those skilled in the art need readily determine its consumption and ratio according to prior art routine operation and practical operation.For example water and/or volumes of aqueous ethanol are 1-80 times of carbon material volume.
The preferably alcohol of the invention is the alcohol that carbon number is 1-4, wherein more preferably ethanol or methanol；The present invention can also use toluene, ether, N-methyl pyrrolidones to substitute alcohol.
Wherein described solid phase mixing is this area routine operation, for example the carbon material is well mixed with sulfate and/or sulphite using physical method, then for example uses the devices such as ball mill, the container with agitating device or three-dimensional mixer to be well mixed mentioned component.
On the other hand, present invention also offers sulfur-bearing carbon material prepared by methods described.
In summary, the invention provides a kind of method for preparing sulfur-bearing carbon material and its sulfur-bearing carbon material of preparation.The method of the present invention has the following advantages that：Compared with preparing the technology of sulfur-bearing carbon material at present, this method can carry out mixing sulphur by the method for post-processing existing carbon material, can obtain various sulfur-bearing carbon materials by simple and easy to do step
Material, the sulfur content and shape characteristic in product can be adjusted by control process parameter.Brief description of the drawings
Fig. 1 is the X-ray diffractogram analysis of spectrum of the reaction product without pickling purifying in embodiment 1.
Fig. 2 is the X-ray diffractogram analysis of spectrum of the reaction product without pickling purifying in embodiment 2.
Fig. 3 is the X-ray photoelectron spectroscopic analysis of sulfur-bearing CNT in embodiment 2（XPS) .
Fig. 4 is the transmission electron microscope photo of sulfur-bearing CNT in embodiment 2.
Fig. 5 is the transmission electron microscope photo of sulfur-bearing CNT in embodiment 3.
Fig. 6 is the X-ray photoelectron spectroscopic analysis of sulfur-bearing CNT in embodiment 4（XPS) .
Fig. 7 is the transmission electron microscope photo of sulfur-bearing graphite flake in embodiment 7.Embodiment
Technical scheme is described in detail below in conjunction with drawings and Examples, but protection scope of the present invention includes but is not limited to this.
Embodiment 1
Sulfur-bearing multi-walled carbon nanotube, MgS0 are prepared using liquid-phase impregnation process4Mass ratio with CNT is 5: 1.Weigh 10.25 g MgS04.7H20,20 ml deionized waters and 20 ml ethanol are added, solution is configured to, weighs 1 g multi-walled carbon nanotube, CNT is placed in MgS04Normal temperature ultrasonic disperse 30-60 min in solution, obtain carbon nano tube suspension, this suspension is placed in 80 °C of baking ovens and dries 48 h, block gray mixture is ground to fine powder, fine powder is placed in porcelain boat, is put into after horizontal pipe furnace and Ar is passed through into stove, while horizontal stove rises to 800 V with 15 °C/min heating rates, and 30 min are kept, take out Off-white product after furnace temperature naturally cools to room temperature.This product is placed in excessive watery hydrochloric acid, water boils the backflow h of pickling 1, removes MgS04Template and during may generation metal oxide, be finally washed with deionized water to neutrality and be placed in being dried to obtain the g of sulfur-bearing CNT 0.54 under the conditions of 80 °C.
Fig. 1 is the X-ray diffractogram analysis of spectrum of the reaction product purified without pickling, the characteristic peak containing MgO and and contains a small amount of MgS0 in collection of illustrative plates4Characteristic peak, illustrates under this process conditions, CNT and part MgS04Reaction generation MgO and sulfur-bearing CNT.Embodiment 2
Sulfur-bearing multi-walled carbon nanotube, MgS0 are prepared using liquid-phase impregnation process4Mass ratio with CNT is 8: 1.
Weigh 16.40g MgS04.7H20,20 ml deionized waters and 20 ml ethanol are added, solution is configured to, 1 g multi-walled carbon nanotube, CNT dipping MgS0 is weighed4Solution, calcining, pickling purifying and drying steps are same as Example 1, and the g of sulfur-bearing CNT 0.48 is obtained after drying.
Fig. 2 is the X-ray diffractogram analysis of spectrum of the reaction product purified without pickling, the characteristic peak containing MgO and and contains a small amount of MgS0 in collection of illustrative plates4Characteristic peak, but relative to example 1, MgS04Characteristic peak it is relatively more, illustrate unreacted MgS04It is relatively more.According to X-ray photoelectron spectroscopic analysis（XPS, Fig. 3), (mass fraction of sulfur-bearing 1.42% in sulfur-bearing CNT made from this kind of process conditions）.Fig. 4 is the transmission electron microscope photo of obtained sulfur-bearing CNT under the process conditions.Embodiment 3
Sulfur-bearing multi-walled carbon nanotube, MgS0 are prepared using liquid-phase impregnation process4Mass ratio with CNT is 15: 1.Weigh 30.75 g MgS04.7H20,40 ml deionized waters and 10 ml ethanol are added, solution is configured to, 1 g multi-walled carbon nanotube, CNT dipping MgS0 is weighed4Solution step is same as Example 1, and horizontal stove rises to 700 V with 15 °C/min heating rates, and keeps 30 min, and pickling purifying and drying steps are same as Example 1, and the g o of sulfur-bearing CNT 0.31 are obtained after drying
According to X-ray photoelectron spectroscopic analysis（XPS, Fig. 5), (mass fraction of sulfur-bearing 0.24% in sulfur-bearing CNT made from this kind of process conditions）.Products collection efficiency is low compared with example 1 and example 2.Fig. 6 is the transmission electron microscope photo of obtained sulfur-bearing CNT under the process conditions.Embodiment 4
Sulfur-bearing multi-walled carbon nanotube, MgS0 are prepared using liquid-phase impregnation process4Mass ratio with CNT is 20: 1.Weigh 41.00g MgS04.7H20,50 ml deionized waters and 20 ml ethanol are added, solution is configured to, lg multi-walled carbon nanotube, CNT dipping MgS0 is weighed4Solution, calcining, pickling purifying and drying steps are same as Example 1, and the g of sulfur-bearing CNT 0.29 is obtained after drying.
According to X-ray photoelectron spectroscopic analysis（XPS, Fig. 6), (mass fraction of sulfur-bearing 0.34% in sulfur-bearing CNT made from this kind of process conditions）.Embodiment 5
Prepared using liquid-phase impregnation process and contain sulfur graphite, the mass ratio of FeS04 and graphite is 15: 1.
Weigh 27.43 g FeS04.7 0,40 ml deionized waters and 20 ml ethanol are added, solution is configured to, weighs 1 g
Graphite, CNT dipping MgS04Solution, calcining, pickling purifying and drying steps are same as Example 1, and the g containing sulfur graphite 0.12 is obtained after drying.
According to X-ray photoelectron spectroscopic analysis, (the mass fraction of sulfur-bearing sulfur in graphite 0.98% made from this kind of process conditions）.Embodiment 6
Sulfur-bearing activated carbon, ZnS0 are prepared using solid phase direct mixing method4Mass ratio with activated carbon is 8: 1.
Weigh the ZnS0 after 8 g, 300 °C of 30 min of calcining4.7H20 crystal, weighs lg activated carbon, and the two is put into progress solid phase in spherical grinder directly mixes, and fine powder is placed in porcelain boat, calcining, pickling purifying and drying steps are identical with example 1, the g of sulfur-bearing activated carbon 0.1 is obtained after drying.
According to X-ray photoelectron spectroscopic analysis（XPS), sulfur-bearing in sulfur-bearing activated carbon made from this kind of process conditions
1.00% (mass fraction).Embodiment 7
Sulfur-bearing graphite flake, NiS0 are prepared using liquid-phase impregnation process4Mass ratio with graphite flake is 5: 1.
Weigh 8.48 g NiS04.6H20,40 ml deionized waters and 20 ml ethanol are added, solution is configured to, 1 g graphite flake, graphite flake dipping NiS0 is weighed4Solution, calcining, pickling purifying and drying steps are same as Example 1, and sulfur-bearing graphite flake 0.36g is dried to obtain under part.
Fig. 7 gives under the process conditions transmission electron microscope picture of obtained sulfur-bearing graphite flake, according to X-ray photoelectron spectroscopic analysis, (the mass fraction of sulfur-bearing 1.55% in the sulfur-bearing graphite flake）.Embodiment 8
Sulfur-bearing porous graphene, MgS0 are prepared using liquid-phase impregnation process4Mass ratio with porous graphene is 2: 1.Weigh 4.1 g MgS04.7H20,40 ml deionized waters are added, the aqueous solution is configured to, weighs 1 g porous graphenes（Preparation method is by document Chemical Communications 47 (21):5976-5978 is provided）, graphene dipping MgS04 solution, calcining, pickling purifying and drying steps are same as Example 3, and the g of sulfur-bearing porous graphene 0.56 is obtained after drying.
According to X-ray photoelectron spectroscopic analysis, (the mass fraction of sulfur-bearing 2.98% in sulfur-bearing graphene made from this kind of process conditions）.Embodiment 9
Sulfur-bearing porous graphene, MgS0 are prepared using solid phase direct mixing method4Mass ratio with porous graphene is 5: 1.Weigh the MgS0 after 5 g, 350 °C of 30 min of calcining4.7H20, weigh 1 g porous graphene（Preparation method is by document Chemical Communications 47 (21):5976-5978 is provided）, the two is put into progress solid phase in spherical grinder and directly mixed, fine powder is placed in porcelain boat, calcining, pickling purifying and drying steps are same as Example 3, sulfur-bearing porous graphene 0.77 is obtained after drying
According to X-ray photoelectron spectroscopic analysis（XPS), (mass fraction of sulfur-bearing 2.36% in sulfur-bearing graphene made from this kind of process conditions）.Embodiment 10
Sulfur-bearing carbon black, ZnS0 are prepared using solid phase direct mixing method4Mass ratio with carbon black is 3: 1.
Weigh the ZnS0 after 3.00 g, 300 °C of 30 min of calcining4.7H20 crystal, weighs 1 g carbon black, and the two is put into progress solid phase in spherical grinder directly mixes, and fine powder is placed in porcelain boat, calcining, pickling purifying and drying steps are same as Example 3, the g of sulfur-bearing carbon black 0.71 is obtained after drying.
According to X-ray photoelectron spectroscopic analysis（XPS), sulfur-bearing 1.54% in sulfur-bearing carbon black made from this kind of process conditions
(mass fraction）.Embodiment 11
Sulfur-bearing fullerene, MgS0 are prepared using liquid-phase impregnation process4Mass ratio with fullerene is 10: 1.
Weigh 20.50 g MgS04.7H20,40 ml deionized waters are added, the aqueous solution is configured to, 1 g fullerenes, fullerene dipping MgS0 is weighed4Solution, calcining, pickling purifying and drying steps are same as Example 3, and sulfur-bearing fuller olefinic carbon 60 .70 g are obtained after drying.
According to X-ray photoelectron spectroscopic analysis（XPS), sulfur-bearing in sulfur-bearing fullerene made from this kind of process conditions
2.03% (mass fraction）.Embodiment 12
Sulfur-bearing carbon black, MgS0 are prepared using liquid-phase impregnation process4Mass ratio with carbon black is 15: 1.
Weigh 30.75 g MgS04.7H20,50 ml deionized waters are added, the aqueous solution is configured to, 1 g carbon blacks, carbon black dipping MgS0 is weighed4Solution, calcining, pickling purifying and drying steps are same as Example 1, and sulfur-bearing carbon black 0.77 is obtained after drying
According to X-ray photoelectron spectroscopic analysis（XPS), sulfur-bearing 1.39% in sulfur-bearing carbon black made from this kind of process conditions
(mass fraction）.Embodiment 13
Sulfur-bearing graphite flake, CoS0 are prepared using liquid-phase impregnation process4Mass ratio with graphite flake is 20: 1.
Weigh 36.23 g CoS04.7H20, add 70 ml deionized waters, it is configured to the aqueous solution, weigh lg graphite flake, graphite flake dipping CoS04 solution steps are same as Example 1, and horizontal stove rises to 900 °C with 15 °C/min heating rates, and keeps 30 min, pickling purifying and drying steps are same as Example 1, and graphitiferous piece 0.51g is obtained after drying.
According to X-ray photoelectron spectroscopic analysis（XPS), (mass fraction of sulfur-bearing graphite flake sulfur-bearing 0.60% made from this kind of process conditions）.
In addition, the sulfur-bearing graphite flake-Co before purifying304Compound can be directly used as cell negative electrode material.Embodiment 14
Sulfur-bearing oil Jiao, MgS0 are prepared using liquid-phase impregnation process4Mass ratio with powder petroleum coke is 10: 1.
Weigh 20.50 g MgS04.7H20,60 ml deionized waters are added, the aqueous solution is configured to, lg powder petroleum coke, petroleum coke dipping MgS0 is weighed4Solution step is same as Example 1, and horizontal stove rises to 500 V with 15 °C/min heating rates, and keeps 30 min, and pickling purifying and drying steps are same as Example 1, and 0.67g containing petroleum coke is obtained after drying.
According to X-ray photoelectron spectroscopic analysis（XPS), sulfur-bearing oil Jiao sulfur-bearing 0.53% made from this kind of process conditions
(mass fraction）.Embodiment 15
Sulfur-bearing activated carbon, MgS0 are prepared using liquid-phase impregnation process4Mass ratio with activated carbon is 15: 1.
Weigh 30.75 g MgS04.7H20,80 ml deionized waters are added, the aqueous solution is configured to, lg Powdered Activated Carbon, activated carbon dipping MgS0 is weighed4Solution step is same as Example 1, and horizontal stove is risen to 15 °C/min heating rates
1000 V, and 30 min are kept, pickling purifying and drying steps are same as Example 1, and sulfur-bearing activated carbon is obtained after drying
0.42g。
According to X-ray photoelectron spectroscopic analysis（XPS), sulfur-bearing activated carbon sulfur-bearing 0.46% made from this kind of process conditions
(mass fraction）.Embodiment 16
Sulfur-bearing activated carbon, MnS0 are prepared using liquid-phase impregnation process4Mass ratio with activated carbon is 0.1: 1.
Weigh 0.1 g MnS04, 50 ml deionized waters are added, the aqueous solution is configured to, weighs lg Powdered Activated Carbon,
Activated carbon impregnates MnS04Solution step is same as Example 1, and horizontal stove rises to 900 with 15 °C/min heating rates, and keeps 30 min, and pickling purifying and drying steps are same as Example 1, and the g of sulfur-bearing activated carbon 0.9 is obtained after drying.
According to X-ray photoelectron spectroscopic analysis（XPS), sulfur-bearing activated carbon sulfur-bearing 0.03% made from this kind of process conditions
(mass fraction）.
Claims (1)
- Claims1st, a kind of method for preparing sulfur-bearing carbon material, it is characterized in that, methods described includes being used as raw material with sulfate and/or sulphite using carbon material, carbon material and sulfate and/or the compound of sulphite are obtained using solid phase mixing or liquid impregnation method, the compound is calcined, sulfur-bearing carbon material is obtained.2nd, according to the method described in claim 1, it is characterised in that the carbon material is 1 with sulfate and/or sulphite mass ratio： 0.01-100.3rd, according to the method described in claim 1, characterized in that, the carbon material is one or more than one kinds of mixtures among graphite, graphite flake, CNT, carbon fiber, graphene, porous graphene, fullerene, activated carbon, porous charcoal, Carbon foam, petroleum coke, coal coke and carbon black.4, according to the method described in claim 1, it is characterized in that, the sulfate includes ferric sulfate, cobaltous sulfate, nickel sulfate, manganese sulfate, aluminum sulfate, zinc sulfate, titanium sulfate, magnesium sulfate, alkali magnesium sulfate, copper sulphate, basic copper sulfate, lead sulfate, basic lead sulphate, calcium sulfate, potassium sulfate, sulfate of ammoniac, ammonium hydrogen sulfate, one or more than one kinds of mixtures among dihydrogen sulfate ammonium, sulphite includes sodium sulfite, potassium sulfite, sodium hydrogensulfite, potassium bisulfite, one or more than one kinds of mixtures among calcium sulfite.5th, according to the method described in claim 1, it is characterised in that the calcining heat is 500 1000 °C, the time is 5-600 minutes；6th, the method according to claim 5, it is characterised in that the calcining heat is 600-900 °C;Time is 30-300 minutes.7th, method according to claim 5, it is characterised in that the calcination processing comprises the following steps：The compound of carbon material and sulfate and/or sulphite is put into reactor, carrier gas, heating calcining is passed through；8th, method according to claim 7, it is characterised in that the carrier gas is one or more than one kinds of mixtures among nitrogen, argon gas, helium.9th, the method according to any one of claim 18, it is characterised in that the step of also including being cleaned with acid solution after calcining.10th, the method according to claim 1 ~ 8 any one, it is characterised in that the liquid-phase impregnation process includes Following steps：(1) carbon material is immersed in the water and/or alcoholic solution of sulfate and/or sulphite, ultrasonic disperse obtains suspension；(2) by step（1) gained suspension is dried, and obtains the compound of sulfate and/or sulphite and carbon material.11st, the method according to claim 10, it is characterised in that described alcohol is the alcohol that carbon number is 1- 4.12nd, method according to claim 11, it is characterised in that described alcohol is ethanol or methanol.13rd, sulfur-bearing carbon material prepared by claim 1 ~ 12 any one methods described.
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| WO2023137840A1 (en) * | 2022-01-19 | 2023-07-27 | 苏州大学 | Preparation method for co, n, and s co-doped carbon nano-bead composite material and use thereof |
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| CN106517172A (en) * | 2016-10-27 | 2017-03-22 | 中国石油大学(北京) | Preparation method of water-soluble sulfur-doped graphene and sulfur-doped graphene prepared by same |
| CN106602013B (en) * | 2016-12-19 | 2020-11-27 | 中国科学院山西煤炭化学研究所 | Preparation method of sulfur-activated carbon/graphene composite material |
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| CN108598378A (en) * | 2018-01-29 | 2018-09-28 | 齐鲁工业大学 | A kind of lithium/anode material of lithium-ion battery Fe1-xThe preparation method of S/C |
| CN108598378B (en) * | 2018-01-29 | 2020-10-02 | 齐鲁工业大学 | Lithium/sodium ion battery negative electrode material Fe1-xPreparation method of S/C |
| WO2023137840A1 (en) * | 2022-01-19 | 2023-07-27 | 苏州大学 | Preparation method for co, n, and s co-doped carbon nano-bead composite material and use thereof |
| CN115286034A (en) * | 2022-07-07 | 2022-11-04 | 中国科学院福建物质结构研究所 | Preparation method of basic lead sulfate material, basic lead sulfate material and application |
| CN115286034B (en) * | 2022-07-07 | 2023-11-17 | 中国科学院福建物质结构研究所 | Preparation method of basic lead sulfate material, basic lead sulfate material and application |
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| WO2015010299A1 (en) | 2015-01-29 |
| CN104520231B (en) | 2016-04-13 |
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