CN107324318A - The method of the preparation of porous graphene and manganese oxide porous graphene composite - Google Patents
The method of the preparation of porous graphene and manganese oxide porous graphene composite Download PDFInfo
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Abstract
The invention discloses a kind of method of prepare with scale manganese oxide porous graphene composite and porous graphene, it the described method comprises the following steps：A the graphene oxide powder purified in advance) is prepared；B) high temperature sintering prepares manganese oxide porous graphene composite powder；And C) the step of prepare porous graphene powder.Preparation in accordance with the present invention directly prepares porous graphene using the graphene oxide slurry purified in advance, avoid the cleaning frequency of graphene oxide in itself long, the problems such as water resource waste, using the remaining impurity of surface of graphene oxide, the preparation of manganese oxide porous graphene composite is realized at high temperature.The Mn oxide porous graphene of preparation, the product shows excellent performance in lithium-air battery, and the method cycle of the invention is short, and technological process is simple, prepares cost low, it is possible to achieve industrialization amplification.
Description
Technical field
The present invention relates to a kind of technology of preparing of porous graphene, more particularly to a kind of prepare with scale manganese oxide-porous
The method of graphene composite material and porous graphene.
Background technology
The fast development and the active demand of energy source and power resource of national economy, necessarily cause oil and natural gas etc. can not
Increasingly exhausted, the continuous deterioration of the global environmental problem such as increase air pollution of regenerated resources.Therefore, in order to which balanced economy increases
Long, environmental protection and energy supply relation, find the energy technology of environmentally friendly sustainable development has turned into scientist's
One of top priority.High-efficiency cleaning energy storage carrier develops into the important directions for leading energy-conserving and environment-protective technology, lithium/air cell
It is made up of cathode of lithium, electrolyte and air cathode, wherein air cathode is with the oxygen (O in air2) as active material, due to
O2Can continuously be obtained from surrounding environment, be not take up the weight of battery in itself, thus lithium/air cell have it is high
Theoretical specific capacity and advantages of environment protection, show good application prospect.Theoretical specific energy up to 11140Wh/kg, with
Internal combustion engine petroleum system quite, is promoted, by energy storage field if lithium/air cell can be researched and developed successfully and obtain commercialization
The great progradation of development generation [L.Grande, E.Paillard, J.Hassoun, J.B.Park, Y.J.Lee,
Y.K.Sun,S.Passerini,B.Scrosati.The lithium/air battery:still an emerging
system or a practical reality.Adv.Mater.,2015,27,784-800.].However, lithium/air cell will
Think practical, also many obstacles needs to overcome, also in the presence of some urgent need to resolve the problem of.From organic system lithium/air cell
Structural analysis, the O in positive electrode surface and air2Contact, reaction generation is insoluble in the Li of organic electrolyte2O2With Li2O,
It is caused constantly to be deposited in positive electrode surface, so as to increase O2The diffusion internal resistance and electro transfer impedance of electrochemical reaction, cause
Final battery capacity decay and the shortening of cycle life, so that terminating reaction [J.J.Xu, Z.L.Wang, D.Xu,
L.L.Zhang,X.B.Zhang.Tailoring deposition and morphology of discharge products
towards high-rate and long-life lithium-oxygen batteries.Nat.Commun.,2013,4,
2438.].Therefore, positive pole reaction decides most of transmission of the energy content of battery, assume responsibility for the voltage drop of whole battery, lithium/air
The structure and properties of cell positive material are the key factors for determining battery performance.Positive electrode answer it is conductive it is good, be easy to
The features such as pore-creating, low cost, good oxygen reduction activity and strong oxygen absorption affinity.
Not only surface has abundant pore structure to porous graphite alkenes product, and possesses light weight, specific surface area height, leads
The features such as electrically excellent and abundant boundary effect, be lithium/optimal structure of O for cathode of air battery material, and such a material can be with
Electrode material is met for the demand in terms of the deposition of the diffusion of gas, the infiltration of electrolyte and discharging product simultaneously, and
And by metal oxide-loaded lifting fake capacitance capacity so as to increase the capacity of lithium-air battery.The boring method master of graphene
There are two kinds of Physical and chemical method, Physical is often controllable in outputing for graphenic surface small range using high precision apparatus
Hole.But Physical is expensive to be unfavorable for industrialized production, and utilize the defect of the surface of graphene oxide of chemical method production
Pore-creating, prepares porous graphene and has maked it possible prepare with scale.Peng new lives of Zhejiang University et al.
(CN104743548A) porous graphite is prepared it is also proposed that soluble metal saline solution and graphene oxide water solution are mixed with
The method of alkene.
However, the root problem that the prepare with scale of graphene oxide is present is, surface of graphene oxide carries hydroxyl, carboxylic
The hydrophilic functional groups such as base and epoxy radicals, show strong hydrophily.Using aoxidize graphite oxide that stripping method prepares with
Going deep into for purification, with water formation water-setting (molten) glue, it is difficult to scattered precipitation.No matter the technology of suction filtration or centrifugation is used, all very
Hardly possible separation graphite oxide and the aqueous solution, ultimately causing product impurity can not obtain preparing high-purity in basic removal, industry
Graphene oxide then needs the equipment of costliness and macrocyclic dialysis work.
The content of the invention
According to an aspect of the invention, there is provided a kind of directly prepare oxidation using the graphene oxide slurry purified in advance
The method of manganese-porous graphene composite and porous graphene, this method has the advantages that cost is low, short preparation period,
The preparation method of the manganese oxide-porous graphene composite comprises the following steps：
A the graphene oxide powder purified in advance) is prepared：Using graphite, the concentrated sulfuric acid and potassium permanganate as raw material, routine is utilized
The method of chemical oxidation prepares graphite oxide, needs to reach after multiple natural subsidence in the chemical oxidization method viscous
Being dried to powder after degree, ultrasound or stirring can be as subsequent treatment sample.
B) high temperature sintering prepares manganese oxide-porous graphene composite powder：Using high temperature sintering furnace, inert gas is protected
Protect to step A) in prepare pre- purification graphene oxide powder carry out high-temperature calcination processing, during calcining, the oxygen purified in advance
Potassium ion, sulphion gasification in graphite alkene powder are deviate from waste gas, leave behind manganese ion and are deposited on surface of graphene oxide,
Prepare manganese oxide-porous graphene powder.
According to an aspect of the invention, there is provided it is a kind of directly prepared using the graphene oxide slurry that purifies in advance it is porous
The method of graphene, this method is including the above-mentioned step A for preparing manganese oxide-porous graphene composite) and basis B)
On further comprise the following steps：
C porous graphene powder) is prepared：By step B) in the obtained manganese oxide-porous graphene of high-temperature calcination for preparing
Powder carries out room temperature watery hydrochloric acid soaking and stirring a few hours, removes the oxide on surface, and PH=7 is cleaned multiple times in suction filtration afterwards, very
Sky drying prepares porous graphene powder.
Wherein, the step A) in, the graphite raw material size is 45~180 μm, and purity is mass fraction 80~99%,
The sulfuric acid concentration of selection is 98%, and the mass ratio for adding graphite, potassium permanganate and sulfuric acid is 1:3:30~1:6:70.
Preferably, the step A) prepare the graphene oxide slurry that purifies in advance and can take existing oxygen in the prior art
Change stripping method, graphite oxide slurry is prepared for example with hummer methods, acid waste liquid, Posterior circle profit to be concentrated are reclaimed in centrifugation
With, lower floor's graphite oxide slurry is collected, deionized water is added in the graphite oxide slurry of highly acidity and is stirred, stone to be oxidized
After ink is separated from the water, upper strata aqueous phase is removed, the weight of standing separation aqueous phase, repeatedly 4~10 times after deionized water stirring is added
Multiple natural subsidence process, is separated except upper strata aqueous phase, until realizing that what graphite oxide slurry can be well disperses, viscosity is controlled 1
~100cSt, is used as the graphene oxide slurry purified in advance.Then ultrasonic disperse prepares the graphene oxide slurry of pre- purification
Material, cold dry-cure obtains the graphene oxide powder of pre- purification.
Preferably, the step A) in prepare pre- purification graphene oxide slurry viscosity be 10~50cSt.
Preferably, the step A) described in natural subsidence cleaning when solution cleans to pH=1.5~2.5, and slurry
When the volume of material increases to original 4~8 times, the early stage product that can be prepared as porous graphene purifies graphite oxide in advance
Collect, then using ultrasound 400 or stirring 350r/min, time 30min~3h, the oxidation stone for preparing and purifying in advance is peeled off in separation
Black alkene solution, is finally freeze-dried, and prepares the graphene oxide powder of pre- purification.
Preferably, the step B) temperature of high temperature sintering furnace is set in 800~1200 DEG C, is used as the lazy of protective gas
Property gas be selected from argon gas or nitrogen, high temperature sintering 30min~4h.
Preferably, the step C) in watery hydrochloric acid concentration be 5~15%, stirring dip time be 30min~2h, suction filtration
Cleaning-drying prepares porous graphene.
According to an aspect of the invention, there is provided a kind of manganese oxide-porous graphene composite, the manganese oxide-
Porous graphene composite is prepared by the above method.
According to an aspect of the invention, there is provided a kind of porous graphene, the porous graphene is by above method system
It is standby.
Beneficial effect
1st, the present invention directly prepares porous graphene using the graphene oxide slurry that purifies in advance, it is to avoid graphene oxide
The cleaning frequency of itself is long, the problems such as water resource waste, and impurity cleverly remaining using surface of graphene oxide, in high temperature
The lower preparation for realizing manganese oxide-porous graphene composite.
2nd, present invention optimizes the raw material introducing that graphite prepares graphene oxide, only with graphite, potassium permanganate and sulphur
Sour three kinds of preparing raw materials, in high temperature environments, potassium element sulphur overflows, prepared by the etching for cleverly realizing a kind of residual impurity,
Etching prepares Mn oxide porous graphene in high temperature environments, and the product shows excellent property in lithium-air battery
Energy.
3rd, short preparation period of the present invention, and all preparation processes can realize industrialization amplification, technological process is simple, system
Standby cost is low, it is possible to achieve the prepare with scale of porous graphene.
Brief description of the drawings
Fig. 1 is the stereoscan photograph according to the manganese oxide prepared in embodiment 1-porous graphene powder.
Fig. 2 is the XRD data according to the manganese oxide-porous graphene prepared in embodiment 1.
Fig. 3 is according to the porous graphene powder stereoscan photograph prepared in embodiment 1.
Fig. 4 is the lithium-air battery according to manganese oxide-porous graphene, porous graphene, graphene powder in embodiment 1
Performance picture.
Fig. 5 shines for the ESEM of the manganese oxide not being successfully prepared-porous graphene powder in comparative example 1
Piece.
Fig. 6 be comparative example 2 in manganese oxide load rare hole porous graphene powder stereoscan photograph.
Fig. 7 is the stereoscan photograph of the manganese oxide not being successfully prepared-porous graphene powder of comparative example 3.
Fig. 8 is the stereoscan photograph of manganese oxide-porous graphene powder of the overetch of comparative example 4.
Embodiment
Hereinafter, it will be described in detail the present invention.Before doing so, it should be appreciated that in this specification and appended
Claims in the term that uses should not be construed as being limited to general sense and dictionary meanings, and inventor should allowed
On the basis of the appropriate principle for defining term to carry out best interpretations, according to implication corresponding with the technical elements of the present invention and generally
Thought is explained.Therefore, description presented herein is not intended to limitation originally merely for the sake of the preferred embodiment for illustrating purpose
The scope of invention, it will thus be appreciated that without departing from the spirit and scope of the present invention, it can be obtained by it
His equivalents or improved procedure.
The invention provides the preparation side of a kind of manganese oxide-porous graphene composite and porous graphene product
Method, this method prepares graphite oxide raw material using the hummers methods of modified technique, and this method aoxidizes the original of stripping method by limiting
Material introduces species, can control to be deposited on the impurity component of graphenic surface in follow-up preparation process.It is prepared by redox
Graphite oxide primary product be raw material, by controlling washing degree, simple and quick prepares what favorable dispersibility viscosity was adapted to
The controllable graphene oxide dispersion of impurity ion content, wherein manganese ion in preparation process because form manganese oxide precipitation
It is difficult to removed by natural subsidence solid liquid phase, and potassium ion is free in aqueous phase, can be removed with substantial amounts of, the oxidation stone purified in advance
Contain manganese ion sulphion and a small amount of potassium ion in black alkene slurry.After freeze-drying, high temperature sintering, and protecting under an inert gas
Temperature control oxygenerating manganese etch and motion time so as to control etch pore volume, synchronous high temperature reduction graphene oxide, and other
Impurity sulphion can be excluded with waste gas, potassium ion is due to inherently pore-creating reagent (ACS Nano, 2013,7,6899-
6905.), and content is less, it also can under the high temperature conditions gasify and be discharged with gas, potassium ion and sulphion be not in graphite oxide
Alkene surface is deposited, and prepares manganese oxide-porous graphene product of one-component.Then by simple acid treatment, prepare
Porous graphene product is obtained, the advantages of this method technological process is simple, manpower consumption is low, equipment investment is few, therefore can conduct
A kind of Perfected process that manganese oxide-porous graphene and porous graphene are prepared suitable for magnanimity.
Specifically, step A according to the present invention) in synthesis graphite oxide method be with graphite, the concentrated sulfuric acid and height
Potassium manganate is raw material, and graphite oxide is prepared using the method for chemical oxidation, and this method equipment is simple, with low cost, and oxygen can be achieved
Prepared by the magnanimity of graphite, and the raw material type introduced in preparation process is less, therefore miscellaneous in obtained pre- purified product
The species of matter is single；Using the hydrophobicity of the graphite oxide slurry of highly acidity, pre- carry is obtained by the cleaning of simple natural subsidence
Pure graphene oxide powder.The natural subsidence stage needs the viscosity for realizing solution after cleaning to control in 10~50cSt as pre-
Solution good dispersiveness and phase after the graphene oxide slurry of purification, the pre- purification graphite oxide satisfaction ultrasound under the conditions of being somebody's turn to do
To low acidity, and ensure that cold dry rear pre- purification graphene oxide layer is not reunited, lamellar spacing is controllable, to be convenient to high temperature
Etch pore-creating.
Process in accordance with the present invention A) in by reach after repeated multiple times natural subsidence suitable viscosity (10~
50cSt) can as subsequent treatment sample.If the viscosity of sample is not reaching to the standard of above range restriction, can not
Obtain lamellar spacing and the controllable pre- purification graphene oxide slurry of surface impurity so that subsequent step performance difficulty, excessive
Clean graphene oxide and retain few foreign ion, cause too high viscosity, step B can be caused) high temperature calcining when, be used for
The manganese oxide negligible amounts that subsequent etching graphenic surface prepares hole are formed, surface holes rare numbers are caused, the product of formation is not
Possesses the feature of porous graphene.And less cleaning graphene oxide retains more foreign ion, too low viscosity then can
Cause graphene oxide acidity too high, hydrophobicity is strong, lamella high degree of agglomeration, after drying, form the thicker pre- purification oxidation of lamella
Graphene powder, during high-temperature calcination, thicker graphenic surface is difficult to be oxidized manganese etching, it is impossible to pore-creating.
Process in accordance with the present invention B) in step A) prepare pre- purification graphene oxide powder high-temperature calcination and
Strict control calcination condition, obtains manganese oxide-porous graphene powder.Wherein described calcining heat is 800~1200 DEG C, is protected
The warm time is in 30min~4h.If step B) sintering temperature, the time not within the above range, manganese oxide can be caused without foot
Enough motion growth times and etching power, prepare porous graphene and pre- purification surface of graphene oxide other impurities ion
Potassium ion and sulphion depart from not thorough, and manganese oxide-porous graphene purity of preparation is relatively low.And excessive sintered heat insulating,
Surface of graphene oxide pore-forming can be caused serious, porous graphene pattern destruction prepared by etching obtains graphene fragment, and
It is likely to occur that manganese oxide particle is oversized, the manganese oxide prepared-porous graphene lithium-air battery poor-performing.
Following examples are enumerated only as the example of embodiment of the present invention, do not constitute any limit to the present invention
System, it will be appreciated by those skilled in the art that the modification in the range of without departing from the essence of the present invention and design each falls within the present invention
Protection domain.Unless stated otherwise, the reagent and instrument used in following examples is commercially available product.
Embodiment 1
Using improved Hummers methods, it is 90wt% 45um natural flake graphites in 3000ml to use 100g purity
The 98wt% concentrated sulfuric acid and 300g KMnO4Middle reaction prepares graphite oxide, and suction filtration removes acid pickle excessive in reaction, collects
Graphite oxide slurry, 10 times up to graphite oxide slurry PH=2.5 repeatedly and color is changed into dark-brown from glassy yellow, now aoxidizes
Aquadag volume increases to original 8 times or so, and 3h is stirred under 350rpm/min mechanical stirring device, peels off and prepares in advance
The graphene oxide slurry of purification, viscosity 50cSt.The graphene oxide powder of pre- purification is then prepared by freeze-drying
End.
By the graphene oxide powder purified in advance in high temperature sintering furnace, under argon gas protection, 1200 are warming up to 5 DEG C/min
DEG C, manganese oxide-porous graphene powder is prepared after insulation 30min, Fig. 1 is the manganese oxide-porous graphene powder prepared
Stereoscan photograph, as can be seen from the figure pore size distribution is uniform, and sample topography is excellent.Fig. 2 is the manganese oxide-porous stone prepared
The XRD data of black alkene, the structure that can be prepared by data analysis is manganese monoxide and the compound of graphene, and high temperature is forged
Without others elemental characteristic peak after burning.Additionally it will be seen that by EDS elementary analyses：After high-temperature calcination, it is prepared into
To manganese oxide-porous graphene purity can reach more than 99%, be shown in Table 1.
Then manganese monoxide is removed with 15% watery hydrochloric acid immersion 30min, so as to prepare porous graphene material.Figure
The 3 porous graphene powder stereoscan photograph to prepare.In addition, also to manganese oxide-porous graphene, porous graphene, stone
Black alkene is (according to document J Am Chem Soc 2008；130:5856-7 is prepared) lithium-air battery performance tested,
Fig. 4 can be seen that the addition of manganese oxide and the construction of graphenic surface pore structure so that the lithium-air battery of grapheme material
Performance is significantly improved.
Table 1：
| Element | Element number percentage (%) |
| C | 93.84 |
| O | 3.10 |
| S | 0.04 |
| K | 0.00 |
| Mn | 3.02 |
Comparative example 1
Using improved Hummers methods, it is 90wt% 45um natural flake graphites in 3000ml to use 100g purity
The 98wt% concentrated sulfuric acid and 300g KMnO4Middle reaction prepares graphite oxide, and suction filtration removes acid pickle excessive in reaction, collects
Graphite oxide slurry, 2 graphite oxide slurries are cleaned with high purity water repeatedly, and now the color of sample is glassy yellow pH=0.5, oxygen
Graphite precipitation volume increases to original 2 times or so, and 3h is stirred under 350rpm/min mechanical stirring device, peels off and prepares
The graphene oxide slurry dispersiveness purified in advance is poor, viscosity 0.5cSt.The sample is freeze-dried, burnt using high temperature sintering furnace
Tie described in sample condition be the same as Example 1, obtained sample such as Fig. 5, as can be seen from the figure because the dispersiveness of sample is not good, glue
Degree control is not good, and manganese oxide particle grows with the increase of temperature, but graphene sheet layer is thicker, it is impossible to which etching obtains porous
Grapheme material.
Comparative example 2
Using improved Hummers methods, it is 90wt% 45um natural flake graphites in 3000ml to use 100g purity
The 98wt% concentrated sulfuric acid and 300g KMnO4Middle reaction prepares graphite oxide, and suction filtration removes acid pickle excessive in reaction, collects
Graphite oxide slurry, 30 graphite oxide slurries are cleaned with high purity water repeatedly, until placing no liquid-solid phase layering naturally, now
The color of sample is dark-brown PH=3.5, and now graphite oxide precipitation volume increases to original 15 times or so, the process due to
Manufacturing cycle is up to 1 month as long as, and 3h is stirred under 350rpm/min mechanical stirring device, after stripping, pre- carry is prepared
Pure graphene oxide slurry dispersiveness is very good, and tested viscosity reaches 200cSt.The sample is freeze-dried, burnt using high temperature
Described in freezing of a furnace sintered sample condition be the same as Example 1, obtained sample such as Fig. 6, the as can be seen from the figure manganese oxide particle on surface
It is considerably less, therefore during high temperature sintering, seldom, the porous graphene prepared does not possess typicalness in the hole of surface etch.We
Also it will be seen that by EDS elementary analyses：After high-temperature calcination, the content of impurity manganese element is less, is shown in Table 2.
Table 2：
| Element | Element number percentage (%) |
| C | 85.63 |
| O | 13.45 |
| S | 0.35 |
| K | 0.01 |
| Mn | 0.56 |
Comparative example 3
In addition to sintering temperature control is 500 DEG C, porous graphene is prepared in the way of embodiment 1.Fig. 7 is preparation
The stereoscan photograph of sample, as can be seen from the figure because the temperature of sintering is too low, the manganese oxide particle size of formation is less,
The scarce capacity of growing movement obtains porous graphene to etch.
Comparative example 4
In addition to sintering time control is 7 hours, porous graphene is prepared in the way of embodiment 1.Fig. 7 is preparation
The stereoscan photograph of sample, as can be seen from the figure because sintering time is long, the manganese oxide particle of formation is seriously etched
Graphenic surface, the lamella integrality of graphene is by destruction.
Comparative example 5
In addition to direct opening sintering furnace lid fast cooling obtains sample after the completion of sintering process, according to embodiment 1
Mode prepare porous graphene, will be seen that by EDS elementary analyses：High-temperature calcination soaking time is not enough, causes potassium and sulphur
Element abjection is not thorough, is shown in Table 3.
Table 3：
| Element | Element number percentage (%) |
| C | 92.8 |
| O | 2.73 |
| S | 2.34 |
| K | 1.01 |
| Mn | 1.12 |
Embodiment 2
Using improved Hummers methods, it is 90wt% 45um natural flake graphites in 3000ml to use 100g purity
The 98wt% concentrated sulfuric acid and 300g KMnO4Middle reaction prepares graphite oxide, and suction filtration removes acid pickle excessive in reaction, collects
Graphite oxide slurry, 9 times up to graphite oxide slurry PH=2.0 repeatedly and color is changed into dark-brown from glassy yellow, now aoxidizes
Aquadag volume increases to original 7 times or so, in 400w ultrasound 30min, peels off the graphene oxide slurry for preparing and purifying in advance
Material, viscosity 20cSt.The graphene oxide powder of pre- purification is then prepared by freeze-drying, by the oxidation stone purified in advance
Black alkene powder is in high temperature sintering furnace, under nitrogen protection, and an oxygen is prepared after being warming up to 1000 DEG C, insulation 2h with 5 DEG C/min
Change manganese-porous graphene powder.Manganese monoxide is removed with 5% watery hydrochloric acid immersion 2h, so as to prepare porous graphene material
Material.
Embodiment 3
Using improved Hummers methods, it is 90wt% 45um natural flake graphites in 3000ml to use 100g purity
The 98wt% concentrated sulfuric acid and 300g KMnO4Middle reaction prepares graphite oxide, and suction filtration removes acid pickle excessive in reaction, collects
Graphite oxide slurry, 6 times up to graphite oxide slurry PH=1.5 repeatedly and color is changed into dark-brown from glassy yellow, now aoxidizes
Aquadag volume increases to original 4 times or so, in 400w ultrasound 1h, peels off the graphene oxide slurry for preparing and purifying in advance,
Viscosity 10cSt..The graphene oxide powder of pre- purification is then prepared by freeze-drying, by the graphite oxide purified in advance
Alkene powder is in high temperature sintering furnace, under argon gas protection, and an oxidation is prepared after being warming up to 900 DEG C, insulation 1h with 5 DEG C/min
Manganese-porous graphene powder.Manganese monoxide is removed with 15% watery hydrochloric acid immersion 30min, so as to prepare porous graphene
Material.
Claims (10)
1. a kind of method for directly preparing manganese oxide-porous graphene composite using the graphene oxide slurry purified in advance,
It the described method comprises the following steps：
A the graphene oxide powder purified in advance) is prepared：Using graphite, the concentrated sulfuric acid and potassium permanganate as raw material, conventional chemistry is utilized
The method of oxidation prepares graphite oxide, needs to reach viscosity after multiple natural subsidence in the chemical oxidization method, surpasses
Being dried to powder after sound or stirring can be as subsequent treatment sample；
B) high temperature sintering prepares manganese oxide-porous graphene composite powder：Utilize high temperature sintering furnace, inert gas shielding pair
Step A) in prepare pre- purification graphene oxide powder carry out high-temperature calcination processing, during calcining, the oxidation stone purified in advance
Potassium ion, sulphion gasification in black alkene powder are deviate from waste gas, leave behind manganese ion and are deposited on surface of graphene oxide, prepare
Obtain manganese oxide-porous graphene powder.
2. a kind of method for directly preparing porous graphene using the graphene oxide slurry purified in advance, methods described is including root
According to the step A described in claim 1) and B) on the basis of further comprise following steps：
C porous graphene powder) is prepared：By step B) in the obtained manganese oxide-porous graphene powder of high-temperature calcination for preparing
Room temperature watery hydrochloric acid soaking and stirring a few hours are carried out, the oxide on surface is removed, PH=7 is cleaned multiple times in suction filtration afterwards, vacuum is done
It is dry to prepare porous graphene powder.
3. preparation method according to claim 1 or 2, it is characterised in that the step A) in, the graphite raw material size
For 45~180 μm, purity is mass fraction 80~99%, and the sulfuric acid concentration of selection is 98%, adds graphite, potassium permanganate and sulphur
The mass ratio of acid is 1:3:30~1:6:70.
4. preparation method according to claim 1 or 2, it is characterised in that the step A) middle repetition natural subsidence process 4
~10 times, separate except upper strata aqueous phase, until realizing that what graphite oxide slurry can be well disperses, viscosity is controlled in 1~100cSt,
It is used as the graphene oxide slurry purified in advance.
5. preparation method according to claim 4, it is characterised in that the step A) in the oxidation stone of pre- purification for preparing
The viscosity of black alkene slurry is 10~50cSt.
6. preparation method according to claim 1 or 2, it is characterised in that the step A) described in natural subsidence cleaning
In when solution cleans to pH=1.5~2.5, and the volume of slurry is when increasing to original 4~8 times, can be used as porous stone
Early stage product prepared by black alkene purifies the collection of graphite oxide in advance, then utilizes ultrasound 400 or stirring 350r/min, time
The graphene oxide solution for preparing and purifying in advance is peeled off in 30min~3h, separation, is finally freeze-dried, is prepared the oxygen of pre- purification
Graphite alkene powder.
7. preparation method according to claim 1 or 2, it is characterised in that the step B) temperature of high temperature sintering furnace
800~1200 DEG C are set in, argon gas or nitrogen, high temperature sintering 30min~4h are selected from as the inert gas of protective gas.
8. preparation method according to claim 1 or 2, it is characterised in that the step C) in watery hydrochloric acid concentration for 5~
15%, stirring dip time is 30min~2h, and suction filtration is cleaned and dried and prepares porous graphene.
9. a kind of manganese oxide-porous graphene composite, the manganese oxide-porous graphene composite is according to claim
It is prepared by 1 methods described.
10. a kind of porous graphene, according to claim 2 prepared by method for the porous graphene.
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