CN103390745B - The preparation method of graphene-based composite - Google Patents
The preparation method of graphene-based composite Download PDFInfo
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- CN103390745B CN103390745B CN201310283526.0A CN201310283526A CN103390745B CN 103390745 B CN103390745 B CN 103390745B CN 201310283526 A CN201310283526 A CN 201310283526A CN 103390745 B CN103390745 B CN 103390745B
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- 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 present invention provides the preparation method of a kind of graphene-based composite, and it comprises the following steps: provide a graphene oxide dispersion；It is passed through hydrogen sulfide gas, described graphene oxide is reduced to Graphene, and obtains the graphene dispersing solution of a sulfur loaded；And it is dried the graphene dispersing solution of described sulfur loaded.The present invention also provides for the preparation method of another kind of graphene-based composite, and it comprises the following steps: provide a graphene oxide dispersion；It is passed through hydrogen sulfide gas, described graphene oxide is reduced to Graphene, and obtains the graphene dispersing solution of a sulfur loaded；The graphene dispersing solution of described sulfur loaded is filtered, to obtain a thin-film material；And it is dried this thin-film material.The preparation method that the present invention provides is simple, and preparation condition is gentle, can solve again the removing of industrial waste gas hydrogen sulfide and effective recycling problem of sulfur simultaneously.
Description
Technical field
The present invention relates to the preparation method of a kind of graphene-based composite, particularly relate to the preparation method of a kind of graphene-based composite in lithium sulfur battery anode material.
Background technology
Society, energy shortage and environmental pollution are that the two of facing mankind is challenged greatly.
On the one hand, being found so far from 2004, Graphene gets more and more people's extensive concerning because of structure and the physico-chemical property of its uniqueness.The two dimensional crystal of the monoatomic thickness that perfect Graphene is made up of according to alveolate texture hexatomic ring is it is considered to be build the basic structural unit of other carbonaceous materials.Graphene has the strongest chemical stability；Its intensity is the highest in known test material, is more than 100 times of steel；There is big specific surface area, be real superficiality solid；There is fabulous electric conductivity and heat conductivity, there is special electrical properties, such as quantum hall effect etc..These characteristics make people actively study Graphene to make it move towards actual application, and wherein, graphene-based composite is one of Graphene important channel of moving towards actual application.
On the other hand, lithium-sulfur cell is the high-energy secondary Green Chemistry power supply received much attention in recent years.But lithium-sulfur cell there is also some problems, hinder its business-like process.Ionic conductivity and the electron conduction of elemental sulfur are the lowest, if under room temperature, the lithium-sulfur cell of the most extremely 100% sulfur cannot discharge and recharge；Secondly, in charge and discharge process, the many lithium sulfides produced are soluble in organic electrolyte, the active substance making positive pole gradually decreases, and there is " shuttle reaction ", and many lithium sulfides of dissolving can arrive on the negative pole lithium sheet of battery through barrier film, and react, causing internal self discharge, 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.
For the modification of sulfur positive electrode, mainly include compound, the nano-metal-oxide cladding etc. to sulfur simple substance of sulfur and conductive material, to reach the purpose improving the electrical conductivity of sulfur positive pole, suppression polysulfide dissolves.Owing to the fusing point of sulfur is relatively low, easily distilling, adding heat fusing or sublimed method so using the preparation of composite sulfur positive electrode more.But this type of method need at high temperature synthesize, the material property that different batches synthesizes is variant, and is difficult to carry out industrialization production.
Another further aspect, hydrogen sulfide is that one of major pollutants of air are not only detrimental to health also can severe corrosion equipment etc..Therefore, the innoxious governance of hydrogen sulfide and effectively utilization are always one of problem the most urgently to be resolved hurrily.The improvement of hydrogen sulfide starts relatively early, and Britain Ke Laige use lime cream depurator desulfurization in 1809 Britain orchid peace Xi Ersi in 1849 obtains the dry oxidation iron processes patent U.S. in 1870 and developed ferrum oxide preparation method this dry oxidation iron processes as long as desulfuration field continues to use 100 years.Occur 20th century 30～the forties that hydrated ferric oxide. is suspended in alkali liquor by solwution method and carry out desulfurization.Play the commonly used Ammonia Process in West Europe the fifties.There is that catalyst made by arsenic alkaline process arsenide the sixties.Because arsenide has severe toxicity gradually to be replaced by non-toxic catalyst.Non-toxic catalyst is all used such as hydroquinone method A.D.A. this method of Fa Fumakesifadake Haake etc..These methods are all developed recently technology faster.On the other hand the liquid waste disposal technique also development that absorbs of solwution method defines different sulfur removal technologies.
But, these technology existing only achieve the purpose of desulfurization, and the most really realize effective recycling of sulfur, thus cause the waste of resource.
Summary of the invention
In view of this, a kind of method preparing graphene-based composite of necessary offer, utilize the method can remove simultaneously and effectively utilize hydrogen sulfide gas.
The preparation method of a kind of graphene-based composite, it comprises the following steps: provide a graphene oxide dispersion；It is passed through hydrogen sulfide gas, described graphene oxide is reduced to Graphene, and obtains the graphene dispersing solution of a sulfur loaded；And it is dried the graphene dispersing solution of described sulfur loaded, it is thus achieved that a powder body material.
Further, the reaction temperature of described hydrogen sulfide and graphene oxide is between 5 DEG C-260 DEG C.
Further, described dry mode is lyophilization, and its baking temperature is between 0 DEG C-subzero 196 DEG C.
The preparation method of a kind of graphene-based composite, it comprises the following steps: provide a graphene oxide dispersion；It is passed through hydrogen sulfide gas, described graphene oxide is reduced to Graphene, and obtains the graphene dispersing solution of a sulfur loaded；The graphene dispersing solution of described sulfur loaded is filtered, to obtain a thin-film material；And it is dried this thin-film material.
Compared with prior art, the preparation method of graphene-based composite provided by the present invention, its preparation temperature is relatively low, and method is simple, it is easy to accomplish industrialization produces；It addition, this preparation method can solve the removing of hydrogen sulfide gas and effective recycling problem of sulfur simultaneously.Utilize the graphene-based composite that the inventive method prepares, there is good electric conductivity and stability, the positive electrode being especially suitable for use as in lithium-sulfur cell.
Accompanying drawing explanation
The flow chart of the preparation method of the powdered graphite thiazolinyl composite that Fig. 1 provides for the embodiment of the present invention one.
The flow chart of the preparation method of the membranaceous graphene-based composite that Fig. 2 provides for the embodiment of the present invention two.
Following detailed description of the invention will further illustrate the present invention in conjunction with above-mentioned accompanying drawing.
Detailed description of the invention
Below in conjunction with the accompanying drawings and the specific embodiments the preparation method of the graphene-based composite that the present invention provides is described in further detail.
Embodiment one
Referring to Fig. 1, the embodiment of the present invention one provides the preparation method of a kind of powdered graphite thiazolinyl composite, and the method comprises the following steps:
S1 a: graphene oxide dispersion is provided；
S2: be passed through hydrogen sulfide gas, is reduced to described graphene oxide Graphene, and obtains the graphene dispersing solution of a sulfur loaded；And
S3: the graphene dispersing solution of described sulfur loaded is dried process.
In step S1, the solvent in described graphene oxide dispersion can be water, it is also possible to for one or several in ethanol, isopropanol, ethylene glycol, DMF (DMF), N-Methyl pyrrolidone (NMP), oxolane.Certainly, the selection of described solvent be not limited to above-mentioned enumerate several, as long as described graphene oxide can be disperseed well.The mass percentage concentration of described graphene oxide dispersion is 0.05-30 mg/mL, it is preferable that its concentration is 1-5 mg/mL.
The preparation method of described graphene oxide dispersion is: weigh a certain amount of graphite oxide pulverulent material；This graphite oxide pulverulent material is added to a solvent；The mode such as ultrasonic disperse, stirring of employing makes graphite oxide pulverulent material be uniformly dispersed, and obtains this graphene oxide dispersion.In the present embodiment, 300 milligrams of graphite oxides are added to 100 ml deionized water, after the ultrasonic agitation 2.5 hours of 200 watts of power, obtain the graphene oxide dispersion that a concentration is 3 mg/mL.
In step S2, using hydrogen sulfide gas as reducing agent, the graphene oxide in described dispersion liquid is reduced to Graphene, obtains elemental sulfur and water simultaneously.The mode that is passed through of described hydrogen sulfide gas does not limits.The intake of described hydrogen sulfide gas can be adjusted according to the component of the graphene-based composite that the concentration of graphene oxide dispersion, quality and expection obtain.Owing to the graphene oxide in graphene oxide dispersion is uniformly dispersed, therefore, the elemental sulfur finally given is also evenly distributed in graphenic surface, combines with Graphene, forms composite.
The reaction temperature of the redox reaction in step S2 should be less than the boiling point of described solvent, and should be less than the burning-point of hydrogen sulfide, to prevent or to reduce described solvent and hydrogen sulfide is lost in this step.Specifically, described reaction temperature is between 5-260 DEG C.When described solvent is water, this reaction temperature is between 5-100 DEG C.In the present embodiment, described reaction temperature is 75 DEG C.
It is of course also possible to continue graphene oxide dispersion described in ultrasonic agitation in this step, to obtain the graphene dispersing solution of a sulfur loaded being more uniformly distributed.
In step S3, described dry purpose is the solvent in the graphene dispersing solution removing described sulfur loaded.But in order to prevent the distillation of sulfur, described being dried should be carried out at a lower temperature.Specifically, the drying means of described graphene dispersing solution can be that lyophilization, drying at room temperature, supercritical drying, vacuum and heating drying, normal heating are dried or heat drying under protective gas.In the present embodiment, cryodesiccated method is used to remove the solvent in described graphene dispersing solution, to obtain described powdered graphite thiazolinyl composite.Specifically, gained graphene dispersing solution is placed in a freeze dryer it is dried.Described lyophilization can remove rapidly the solvent in graphene dispersing solution, keeps its microstructure simultaneously.Described cryodesiccated temperature is between 0 DEG C-subzero 196 DEG C.Preferably, described cryodesiccated temperature is between 0 DEG C-subzero 60 DEG C.Specifically, in the present embodiment, described cryodesiccated temperature is subzero 56 DEG C.This powdered graphite thiazolinyl composite can be directly used in lithium-sulfur cell as positive electrode.
Embodiment two
Referring to Fig. 2, the embodiment of the present invention two provides the preparation method of a kind of membranaceous positive electrode, and the method comprises the following steps:
S1 a: graphene oxide dispersion is provided；
S2: be passed through hydrogen sulfide gas, is reduced to described graphene oxide Graphene, and obtains the graphene dispersing solution of a sulfur loaded；
S3: the graphene dispersing solution of described sulfur loaded is filtered, to obtain a thin-film material；And
S4: be dried this thin-film material.
In step S1, the solvent in described graphene oxide dispersion can be water, it is also possible to for one or several in ethanol, isopropanol, ethylene glycol, DMF (DMF), N-Methyl pyrrolidone (NMP), oxolane.Certainly, the selection of described solvent be not limited to above-mentioned enumerate several, as long as described graphene oxide can be disperseed well.The mass percentage concentration of described graphene oxide dispersion is 0.05-30 mg/mL, it is preferable that its concentration is 1-5 mg/mL.
The preparation method of described graphene oxide dispersion is: weigh a certain amount of graphite oxide pulverulent material；This graphite oxide pulverulent material is added to a solvent；The mode such as ultrasonic disperse, stirring of employing makes graphite oxide pulverulent material be uniformly dispersed, and obtains this graphene oxide dispersion.In the present embodiment, 200 milligrams of graphite oxides are added to 100 ml deionized water, after the ultrasonic agitation 2 hours of 150 watts of power, obtain the graphene oxide dispersion that a concentration is 2 mg/mL.
In step S2, using hydrogen sulfide gas as reducing agent, the graphene oxide in described dispersion liquid is reduced to Graphene, obtains elemental sulfur and water simultaneously.The mode that is passed through of described hydrogen sulfide gas does not limits.The intake of described hydrogen sulfide gas can be adjusted according to the component of the graphene-based composite that the concentration of graphene oxide dispersion, quality and expection obtain.Owing to the graphene oxide in graphene oxide dispersion is uniformly dispersed, therefore, the elemental sulfur finally given is also evenly distributed in graphenic surface, combines with Graphene, forms composite.
The reaction temperature of the redox reaction in step S2 should be less than the boiling point of described solvent, and should be less than the burning-point of hydrogen sulfide, to prevent or to reduce described solvent and hydrogen sulfide is lost in this step.Specifically, described reaction temperature is between 5-260 DEG C.When described solvent is water, this reaction temperature is between 5-100 DEG C.In the present embodiment, described reaction temperature is 50 DEG C.
It is of course also possible to continue graphene oxide dispersion described in ultrasonic agitation in this step, to obtain the graphene dispersing solution of a sulfur loaded being more uniformly distributed.
In step S3, described filtration can be ordinary filtration, it is also possible to be vacuum filtration method.The thickness of described thin-film material can be controlled by the time filtered according to actual needs.In the present embodiment, use the method for vacuum filtration by the graphene dispersing solution filtering coating of described sulfur loaded.
In step S4, described dry purpose is to remove solvent remaining in described thin-film material.But in order to prevent the distillation of sulfur, described being dried should be carried out at a lower temperature.Specifically, the drying means of described graphene dispersing solution can be that lyophilization, drying at room temperature, supercritical drying, vacuum and heating drying, normal heating are dried or heat drying under protective gas.In the present embodiment, cryodesiccated method is used to remove solvent remaining in described thin-film material, to obtain described membranaceous graphene-based composite.Specifically, gained thin-film material is placed in a freeze dryer it is dried.Described lyophilization can remove rapidly solvent remaining in described thin-film material, keeps its microstructure simultaneously.Described cryodesiccated temperature is between 0 DEG C-subzero 196 DEG C.Preferably, described cryodesiccated temperature is between 0 DEG C-subzero 60 DEG C.Specifically, in the present embodiment, described cryodesiccated temperature is subzero 57 DEG C.This membranaceous graphene-based composite can be directly used in lithium-sulfur cell as positive electrode.
Compared with prior art, the preparation method of graphene-based composite provided by the present invention, its preparation temperature is relatively low, and method is simple, it is easy to accomplish industrialization produces；It addition, this preparation method can solve the removing of hydrogen sulfide gas and effective recycling problem of sulfur simultaneously.The graphene-based composite utilizing the inventive method to prepare has good electric conductivity and stability, is especially suitable for use as the positive electrode of lithium-sulfur cell.
It addition, those skilled in the art also can do other changes, certainly, these changes done according to present invention spirit in spirit of the present invention, within all should being included in scope of the present invention.
Claims (10)
1. a preparation method for graphene-based composite, comprises the following steps:
One graphene oxide dispersion is provided；
It is passed through hydrogen sulfide gas, as reducing agent, described graphene oxide is reduced to stone using hydrogen sulfide gas
Ink alkene, and generate sulfur simple substance and be dispersed in graphenic surface, the Graphene thus obtaining a sulfur loaded divides
Dissipate liquid；And
It is dried the graphene dispersing solution of described sulfur loaded thus obtains sulfur simple substance uniform load at Graphene table
The graphene-based composite in face.
The preparation method of graphene-based composite the most as claimed in claim 1, it is characterised in that be passed through
The reaction temperature controlling redox graphene during hydrogen sulfide gas is 5-260 DEG C.
The preparation method of graphene-based composite the most as claimed in claim 1, it is characterised in that described dry
Dry mode is lyophilization, drying at room temperature, supercritical drying, vacuum and heating drying, normal heating
It is dried and the one in the heat drying under protective gas.
The preparation method of graphene-based composite the most as claimed in claim 1, it is characterised in that described dry
Dry mode is lyophilization.
The preparation method of graphene-based composite the most as claimed in claim 4, it is characterised in that described dry
Temperature time dry is 0 DEG C-subzero 196 DEG C.
The preparation method of graphene-based composite the most as claimed in claim 1, it is characterised in that described oxygen
The mass percentage concentration of functionalized graphene dispersion liquid is 0.05-30mg/mL.
The preparation method of graphene-based composite the most as claimed in claim 1, it is characterised in that described oxygen
Solvent in functionalized graphene dispersion liquid is water, ethanol, isopropanol, ethylene glycol, N, N-dimethyl formyl
One or several in amine, N-Methyl pyrrolidone and oxolane.
The preparation method of graphene-based composite the most as claimed in claim 1, it is characterised in that be dried
Being filtered by the graphene dispersing solution of described sulfur loaded, to form a thin-film material, and it is thin to be dried this before
Membrane material.
9. a preparation method for graphene-based composite, comprises the following steps:
One graphene oxide dispersion is provided；
It is passed through hydrogen sulfide gas, as reducing agent, described graphene oxide is reduced to stone using hydrogen sulfide gas
Ink alkene, and generate sulfur simple substance uniform load and divide at graphenic surface, the Graphene thus obtaining a sulfur loaded
Dissipate liquid；
The graphene dispersing solution of described sulfur loaded is filtered, to obtain a thin-film material；And
Use cryodesiccated mode to be dried this thin-film material thus obtain sulfur simple substance uniform load at graphite
The graphene-based composite on alkene surface.
The preparation method of graphene-based composite the most as claimed in claim 9, it is characterised in that described cold
The dry temperature of lyophilizing is between 0 DEG C-subzero 60 DEG C.
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| CN201310283526.0A CN103390745B (en) | 2013-07-05 | 2013-07-05 | The preparation method of graphene-based composite |
| US14/315,327 US20150010825A1 (en) | 2013-07-05 | 2014-06-26 | Graphene composite material, methods for making graphene and graphene composite material, and lithium sulfur battery using the same |
| US15/907,290 US10193146B2 (en) | 2013-07-05 | 2018-02-28 | Methods for manufacturing graphene based material |
| US15/907,294 US10186707B2 (en) | 2013-07-05 | 2018-02-28 | Methods of manufacturing graphene based material |
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| CN106252642A (en) * | 2016-09-22 | 2016-12-21 | 清华大学深圳研究生院 | The preparation method and applications of sulfur nanoparticulate dispersion |
| CN108385403B (en) * | 2018-02-06 | 2019-07-09 | 温州薪然鞋业有限公司 | A kind of antistatic antibiotic microfiber leather and preparation method thereof |
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