CN103387229A - A preparation method for porous graphene and a preparation method for a graphene-based aluminium-air cell - Google Patents
A preparation method for porous graphene and a preparation method for a graphene-based aluminium-air cell Download PDFInfo
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Abstract
The invention relates to a preparation method for porous graphene and a preparation method for a graphene-based aluminium-air cell, and belongs to the fields of material synthesis and applications. The porous graphene is prepared by steps of subjecting graphite oxide which is used as a precursor to high-temperature heat treatment in a muffle furnace, then dispersing in ethanol, and performing ultrasonic treatment to prepare a graphene catalyst. The preparation method for the graphene-based aluminium-air cell comprises three steps comprising a step of preparing an air electrode diffusion layer, a step of preparing a graphene catalyst layer and a step of assembling an air electrode. After being applied in the aluminium-air cell, the graphene has a higher constant-current discharge voltage than platform perovskite, manganese dioxide, and other catalysts, and stability of the cell is significantly improved. In addition, the graphene has a simple preparation method and excellent performances, and therefore the graphene can be produced on a large scale, the production cost for the catalyst is reduced and catalytic effects for the cell are improved.
Description
Technical field
The invention belongs to the synthetic and Application Areas of material, relate to a kind of preparation method of novel aluminium-air cell catalyzer, be specifically related to a kind of novel method for preparing air electrode that Graphene is incorporated in the middle of aluminium-air cell as catalyzer.
Background technology
, because aluminium-air cell has the characteristics such as specific energy is high, the starting material source is abundant, use safety, stability is good, get more and more people's extensive concerning.The aluminium-air cell of making anode of metallic aluminium occurs that as a kind of new battery the time of two more than ten years has also been arranged on market.But still there are many problems in aluminium-air electrode, the corrosion of aluminum anode and liberation of hydrogen effect, and the polarization phenomena of air electrode are serious, and the expansion energy ability of oxygen is on the low side, and air electrode is lower to the utilization ratio of oxygen.
In recent years, for existing these shortcomings of aluminium-air electrode Air electrode, the researcher was more and more ripe to the research of aluminum anode both at home and abroad, and the cathode air electrode becomes another study hotspot of aluminium-air cell.When air electrode has conduction, catalytic activity is arranged, during the characteristics such as air penetrability is high, liquid-tight, the specific energy of battery can be greatly improved.The more aluminium-air cell cathod catalyst of research mainly contains Manganse Dioxide class, perovskite, metal organic macrocycle inner complex class and precious metal at present, but these catalyzer all do not find broad application up to now.
Grapheme material is a kind of nano material that is comprised of the mono-layer graphite sheet, has excellent electroconductibility, mechanical property and catalytic activity, has become numerous subject researchists' such as physics, chemistry and materialogy the focus of attention.The currently reported metal-air batteries such as lithium-air battery, sodium gas battery that Graphene is applied to, but having not yet to see report applies to Graphene in the middle of aluminium-air cell, therefore, in the middle of being applied to aluminium-air cell as cathod catalyst, Graphene has very important significance.
Summary of the invention
For the cathodic polarization rate that solves present aluminium-air cell large, the problems such as battery discharge voltage is low, the present invention is low with cost, performance good, the simple Graphene of preparation process applies in the middle of aluminium-air cell, improves the discharge stability of battery when making the sparking voltage that improves aluminium-air cell.
One of purpose of the present invention is to provide a kind of preparation method of porous graphene, and this preparation method adopts dilatometry to generate the porous graphene material, and this Graphene is prepared into air electrode.Prepared Graphene is comprised of single or multiple lift graphene-structured unit, can observe obvious pore structure on the projection Electronic Speculum figure of Graphene, and pore size distribution is at 3-100nm, and specific surface area is at 400-500m
2/ g.The preparation process of porous graphene is mainly divided two processes: the preparation of graphite oxide and the expansion of graphite oxide reduction.General Hummer ' the s method that adopts prepares graphite oxide.Adopt Graphite Powder 99, crystalline flake graphite, tetrachloromethane etc. as presoma., by adding pre-treatment step and extending the ice bath time, obtain the higher graphite oxide of degree of oxidation.Its concrete preparation process is as follows:
(1) in the 50-250mL round-bottomed flask, add the 12-48mL vitriol oil, take Potassium Persulphate and each 1.0-5g of Vanadium Pentoxide in FLAKES with electronic balance, join fast in flask oil bath 40-180 ℃ of lower stirring and refluxing;
(2) after it dissolves, slowly add the 1.0-5g Graphite Powder 99 in mixture, continue at the uniform velocity stirring reaction heating 2-10h, question response is complete, round-bottomed flask is mentioned from the oil bath pan the inside, after naturally cooling to room temperature, reactant is poured in the 1-2L large beaker, slowly add the dilution of 200-2000mL water, be placed on standing 12-48h in stink cupboard;
(3) after the obvious layering of thing to be mixed, supernatant liquid is outwelled, used the Büchner funnel suction filtration, and extremely neutral with a large amount of distilled water washs, then product is transferred in culture dish, place 12-48h in Fume Hoods, naturally dry the graphite that obtains processing;
(4) graphite that will process, put into the 50-200g vitriol oil and stir at ice bath, slowly adds 8-30gKMnO
4Stir afterwards 1-10h in ice bath;
(5) put into the oil bath pan of 35 ± 3 ℃, stir 20-120min, then slowly be added drop-wise to 100-300mL distilled water in said mixture;
(6) thing to be mixed is cool to room temperature, takes out and puts into the 2-5L large beaker, adds 500-1500mL distilled water and 5-60mLH
2O
2, continuing to be stirred to does not have Bubble formation, and mixed solution becomes golden yellow by atropurpureus;
(7) standing 5-48h, abandoning supernatant, mixture is the HCl of 0.1:10-2:10 and water centrifuge washing repeatedly with volume ratio, obtains the gelatinoid of brown;
(8) gelatinoid, 30-80 ℃ of lower vacuum-drying, grinds and obtains chocolate solid, i.e. graphite oxide.
(9) take graphite oxide as presoma, in 800-1500 ℃ of retort furnace, it is carried out high-temperature heat treatment, then be dispersed in ethanol, process 20-120min in ultra sonic bath, obtain black suspension, after the washing with alcohol filtered several times, 20-80 ℃ of vacuum-drying 12-48h, obtain graphen catalyst, described high-temperature processing method is Rapid Thermal plavini or Polyaniline-modified method, wherein:
The step that the Rapid Thermal plavini prepares porous graphene is as follows:
First the prepared graphite oxide of 50-500mg step 8 is ground into powder, puts into the reaction unit after deoxygenation is processed, then join in retort furnace, rapid expansion 30s obtains peelable graphite; To obtaining in peelable graphite adding 50-500 mL dehydrated alcohol, process 20-120min in ultra sonic bath, obtain black suspension, after the washing with alcohol filtered several times, 20-60 ℃ of vacuum-drying 12-48h, obtain the powder of Graphene.
The step that polyaniline (PANI) is modified the standby porous graphene of legal system is as follows:
First PANI being modified graphite oxide peels off and obtains needed Graphene.Get the prepared GO fine powder of 50-500mg step 8 (graphite oxide fine powder), ultrasonic 20-120min in the distilled water of 50-1000mL; Add a certain amount of concentrated hydrochloric acid, make it be configured to the solution of 0.1-5mol/L; Stir the aniline monomer that drips 50-200mg in the backward solution of 20-120min, continue to stir 30min; Then (the NH of weighing 0.1-0.5g
4) S
2O
8Incorporate in the HCl of 5-50mL, 0.1-5mol/L, be added drop-wise in mixture stirring at room 12-48h; Use a large amount of distilled water washs, filter, 20-80 ℃ of vacuum drying obtains the PANI-GO powder; Dried PANI-GO is ground into powder, joins preheating and be in the retort furnace of 600-1500 ℃, rapid expansion 10-60s obtains peelable PANI-graphite; To obtaining in peelable graphite adding the 50-500mL dehydrated alcohol, process 20-120min in ultra sonic bath, obtain black suspension, after the washing with alcohol filtered several times, 20-80 ℃ of vacuum-drying 12-48h, obtain the powder of PANI-GNS.
Two of purpose of the present invention is to provide a kind of preparation method of graphene-based aluminium-air cell, and the method comprises the preparation of air electrode diffusion layer, the preparation of Graphene Catalytic Layer, the assembling of air electrode, and its concrete steps are as follows:
(1) preparation of air electrode diffusion layer:
Utilize acetylene black to do conductive agent, polytetrafluoroethylene (PTFE), as binding agent, becomes the film of 0.5nm at nickel foam both sides nip drum after stir process, after high temperature sintering, forms the diffusion layer of porous.Concrete steps are as follows:
1) ammonium oxalate is ground to form fine powder, get 0.5-5g and join in the 50-150mL beaker, then add the 20-100mL dehydrated alcohol, cover preservative film, stir 1-10h;
2) add 0.5-2g acetylene black, continue fully to stir 6-12h, drip the 1-5g tetrafluoroethylene in mixture, continue to stir 10-48h it is uniformly dispersed, during be covered with preservative film;
3) open preservative film, put into 70-90 ℃ of water-bath stirring heating and process, remove ethanol, when without obvious ethanol, existing,, with the both sides of its roll extrusion in nickel foam, put into baking oven, 100-150 ℃ of dry 10-72h.
(2) preparation of porous graphene catalyzer:
Take graphite oxide as presoma, in retort furnace, it is carried out high-temperature heat treatment, then be dispersed in ethanol, ultrasonication prepares graphen catalyst.
(3) assembling of air electrode:
take graphen catalyst 10-50mg and be placed in small beaker, the n-2 methyl-2-pyrrolidone (NMP) that adds 0.1-1g, after ultra-sonic dispersion is processed 20-120min, drip wherein 0.05-0.5g polyvinylidene difluoride (PVDF) (PVDF) class binding agent, magnetic agitation 5-20h, until catalyzer is modulated into after paste a side that spreads upon uniformly diffusion layer, its thickness is 0.5mm, prepare two air electrodes, and carry out the mark of Catalytic Layer, then being placed in vacuum drying oven 25-80 ℃ of cooling after dry 10-48 hour takes out, use under tabletting machine 2-10MPa, press 2-10min, after electrode slice is compressed, obtain working electrode.
The graphite oxide that above-mentioned preparation method adopts is to adopt improved Hummer ' s method preparation.Wherein the graphite former state adopts 325 purpose crystalline flake graphites.Crystalline flake graphite prepares through the oxidation of oxidation pre-treatment and strong acid and strong oxidizer respectively.
The graphen catalyst that above-mentioned preparation method adopts has significant pore structure, and aperture is at 3-100nm, and specific surface area is 400-500m approximately
2/ g.
The graphene-supported amount of air electrode is few, is about 1.5mg/cm
2, be assembled into battery constant-current discharge voltage afterwards with the air electrode for preparing higher, and can keep higher discharge platform under high electric current.
Experiment shows: the preparation method who provides in the present invention is provided, can effectively porous graphene be applied in the middle of aluminium-air cell, this hole Graphene has significant pore structure and larger specific surface area, can effectively improve diffusibility and the oxygen reducing ability of oxygen, has larger potential using value.And the present invention adopts the rapid expansion method can realize easily the production in enormous quantities of the grapheme material of this porous high-specific surface area.And the graphite oxide after the employing Polyaniline-modified expands through Rapid Thermal, can obtain the more excellent grapheme material of performance.
In the middle of the present invention, after Graphene was applied to aluminium-air cell, its constant-current discharge voltage platform was than the height of the catalyzer such as uhligite, Manganse Dioxide, and the stability of battery also obviously improves.On the other hand, the preparation method of Graphene is simple, and therefore excellent performance can be produced in a large number, reduces the cost of manufacture of catalyzer, improves the catalytic effect of battery.
Description of drawings
Fig. 1 is the schema of pre-treatment crystalline flake graphite;
Fig. 2 is the process flow sheet for preparing graphite oxide;
Fig. 3 is the air electrode front elevation;
Fig. 4 is the air electrode side elevational view;
Fig. 5 is the aluminium-air cell space model;
Fig. 6 is aluminium-air cell assembling flow path figure;
Fig. 7 is crystalline flake graphite, GO, the XRD figure of T-GNS and PANI-GNS;
Fig. 8 is the infrared spectrum of GO, T-GNS and PANI-GNS;
Fig. 9 is the Raman spectrogram of crystalline flake graphite, GO, T-GNS and PANI-GNS;
Figure 10 is the SEM figure of crystalline flake graphite;
Figure 11 is the SEM figure of GO;
Figure 12 is the SEM figure of T-GNS;
Figure 13 is the SEM figure of PANI-GNS;
Figure 14 is the TEM figure of T-GNS;
Figure 15 is the TEM figure of PANI-GNS;
Figure 16 is the nitrogen adsorption-desorption curve of differing materials;
Figure 17 is the pore size distribution curve based on each material of BJH (Barrett-Joiner-Halenda) model;
Figure 18 is T-GNS and PANI-GNS electrode constant-current discharge curve under 10mA;
Figure 19 is T-GNS and PANI-GNS electrode constant-current discharge curve under 20mA;
Figure 20 is T-GNS and PANI-GNS electrode constant-current discharge curve under 30mA;
Figure 21 is T-GNS and PANI-GNS electrode constant-current discharge curve under 40mA.
Embodiment
, below in conjunction with accompanying drawing, by embodiment, cathod catalyst of the present invention and preparation method thereof is described further.These embodiment only are used for explanation the present invention rather than are used for the restriction scope of the invention.
Embodiment one: in present embodiment, graphite oxide adopts improved hummers method to prepare.The experimental technique of research preparation GO, and its individual processes and process step are optimized, the experiment flow figure of pre-treatment graphite and preparation GO is as shown in 1 and 2, and concrete experimental procedure is as follows:
(1) in the 50mL round-bottomed flask, add the 12mL vitriol oil, take Potassium Persulphate and each 2.5g of Vanadium Pentoxide in FLAKES with electronic balance, join fast in flask 80 ℃ of lower stirring and refluxing of oil bath.
(2) after it dissolves, slowly add the 3g Graphite Powder 99 in mixture, continue at the uniform velocity stirring reaction heating 4.5 hours, question response is complete, round-bottomed flask is mentioned from the oil bath pan the inside, after naturally cooling to room temperature, reactant is poured in the 1L large beaker, slowly add the dilution of 500mL water, be placed on a standing evening in stink cupboard.
(3) after the obvious layering of thing to be mixed, supernatant liquid is outwelled, used the Büchner funnel suction filtration, and extremely neutral with a large amount of distilled water washs, then product is transferred in culture dish, place an evening in Fume Hoods, naturally dry the graphite that obtains processing.
(4) graphite that will process, put into the 120mL vitriol oil and stir at ice bath, slowly adds 15gKMnO
4Stir afterwards 4h in ice bath.
(5) put into the oil bath pan of 35 ± 3 ℃, stir 1h, then 200mL distilled water slowly is added drop-wise in said mixture.
(6) thing to be mixed is cool to room temperature, takes out and puts into the 2L large beaker, adds 700mL distilled water and 30mLH
2O
2(30%), continuing to be stirred to does not have Bubble formation, and mixed solution becomes golden yellow by atropurpureus.
(7) standing 12h, abandoning supernatant, mixture is the HCl of 1:10 and water centrifuge washing repeatedly with volume ratio, obtains the gelatinoid of brown.
(8), 50 ℃ of lower vacuum-dryings, grind and obtain chocolate solid, i.e. graphite oxide.
Embodiment two: the Main Function of Catalytic Layer is the reduction reaction of oxygen in catalytic air.In present embodiment, the preparation process of air electrode all manually coating method be made, detailed process is as follows:
Take graphen catalyst 30mg and be placed in small beaker, the n-2 methyl-2-pyrrolidone (NMP) that adds 0.2g, after ultra-sonic dispersion is processed 30min, add wherein 0.1g polyvinylidene difluoride (PVDF) (PVDF), use magnetic stirrer 12h, until catalyzer is modulated into after paste a side that spreads upon uniformly diffusion layer, prepare two air electrodes, and carry out the mark of Catalytic Layer, then be placed in vacuum drying oven the taking-up of lowering the temperature after 12 hours of 45 ℃ of dryings, use under tabletting machine 4MPa, press 5min, after electrode slice is compressed, obtain working electrode.
Reserve the nickel foam collector of 1.0cm at the upside of air electrode, leave for the test electrode clip and contact when being mainly test for convenience.To note while smearing catalyzer all is divided into two parts, spread upon gently one deck of Catalytic Layer, just can carry out compressing tablet after waiting it to do.The front of prepared working electrode and side design sketch are as shown in Figure 3-4.
Be assembled into battery battery space model afterwards as shown in Figure 5.
Embodiment three: in present embodiment, select the standby graphite oxide of improved Hummer ' s legal system.Graphite adopts natural flake graphite, uses P
2O
5, KMnO
4, K
2S
2O
8, dense H
2SO
4Etc. several mixtures, graphite is carried out preoxidation (Fig. 1) and obtain expanded graphite.Then the graphite that will process, add a certain amount of SODIUMNITRATE and the vitriol oil, is uniformly mixed in ice bath, slowly add the strong oxidizers such as potassium permanganate, keep temperature not surpass 4 ℃, ice bath 1-4h, then the process of temperature (35 ℃) in directly passing through, with graphite oxidation.Add the dilution of a large amount of water, then add hydrogen peroxide, reduce remaining oxygenant.Use hydrochloric acid and distilled water wash product, vacuum-drying, obtain graphite oxide (Fig. 2) again.
Embodiment four: present embodiment prepares Graphene (T-GNS) by the Rapid Thermal plavini:
First the 200mg graphite oxide being ground into powder, putting into the reaction unit after deoxygenation is processed, is that in the retort furnace of 1100 ℃, rapid expansion 30s obtains peelable graphite to preheating.To obtaining in peelable graphite adding the 100mL dehydrated alcohol, process 30min in ultra sonic bath, obtain black suspension, after the washing with alcohol filtered several times, 40 ℃ of vacuum-drying 24h obtain the powder of Graphene.
Embodiment five: present embodiment is modified the standby Graphene (PANI-GNS) of legal system by polyaniline (PANI):
First PANI is modified graphite oxide peel off again obtain the Graphene that needs (first with PANI, modify graphite oxide, and then with the graphite oxide modified by hot soarfing from obtaining Graphene).Get the GO fine powder of 200mg, ultrasonic 30min in the distilled water of 400mL, add a certain amount of concentrated hydrochloric acid, makes it be configured to the solution of 1mol/L.Stir the aniline monomer that drips 100mg in the backward solution of 30min, continue to stir 30min.Then (the NH of weighing 0.17g
4) S
2O
8Incorporate in the HCl of 10mL, 1mol/L, be added drop-wise in said mixture stirring at room 24h.Use a large amount of distilled water washs, filter, 40 ℃ of vacuum dryings obtain the PANI-GO powder.Dried PANI-GO is ground into powder, joins preheating and be in the retort furnace of 1000 ℃, rapid expansion 30s obtains peelable PANI-graphite.To obtaining in peelable graphite adding the 100mL dehydrated alcohol, process 30min in ultra sonic bath, obtain black suspension, after the washing with alcohol filtered several times, 40 ℃ of vacuum-drying 24h obtain the powder of PANI-GNS.
Embodiment six: diffusion layer has hydrophobic and ventilative function, and it can prevent leaking outside of electrolytic solution on the one hand, can promote on the other hand airborne oxygen to be diffused into better the reaction interface layer from atmosphere, and its preparation process is mainly as follows:
(1) ammonium oxalate is ground to form fine powder, get 2.0g and join in the 150mL beaker, then add the 50mL dehydrated alcohol, cover preservative film, stir 3h;
(2) add 1.0g acetylene black, continue fully to stir 9h, drip the 2.5g polytetrafluoroethylene (PTFE) in mixture, continue to stir 12h it is uniformly dispersed, during be covered with preservative film to prevent ethanol volatilization after long-time the stirring;
(3) open preservative film, put into 80 ℃ of water-bath stirring heating and process, remove ethanol, until when obviously ethanol exists, in the both sides of the nickel foam of 2cm * 3cm (thickness 0.5nm), and upper end reserves 1.0cm with its roll extrusion.Put into baking oven, 130 ℃ of dry 12h.
Embodiment seven: the Main Function of Catalytic Layer is the reduction reaction of oxygen in catalytic air.The preparation process of present embodiment Air electrode all manually coating method be made.Detailed process is as follows:
take graphen catalyst 30mg and be placed in small beaker, the n-2 methyl-2-pyrrolidone (NMP) that adds 0.2g, after ultra-sonic dispersion is processed 30min, add wherein 0.1g polyvinylidene difluoride (PVDF) (PVDF), use magnetic stirrer 12h, until catalyzer is modulated into after paste a side that spreads upon uniformly diffusion layer, its thickness is 0.5mm, prepare two air electrodes, and carry out the mark of Catalytic Layer, then be placed in vacuum drying oven the taking-up of lowering the temperature after 12 hours of 45 ℃ of dryings, use under tabletting machine 4MPa, press 5min, after electrode slice is compressed, obtain working electrode (Fig. 3-4).
Embodiment eight: the aluminium/gas battery of the present invention research all adopts the NaCl of 3.5wt% of pH=11 as electrolytic solution, is assembled into simulated battery (Fig. 5), and the assembling flow path figure of whole battery as shown in Figure 6.
Fig. 7 has provided crystalline flake graphite to GO, the XRD figure of T-GNS and PANI-GNS.The 2 θ angles of (002) diffraction peak of crystalline flake graphite are 26.70 ° as we know from the figure, are typical graphite peaks, and peak shape is sharp-pointed and intensity is large, and the d002 value is about 0.3336nm.As can be known, (002) the crystal face diffraction peak intensity that is positioned at 26.70 ° weakens diffracting spectrum by contrasting original crystalline flake graphite, and peak shape is by sharply becoming a steamed bun peak (GO, T-GNS and PANI-GNS), and to Small angle, is offset.And learn from the XRD of GO, the characteristic peak of (001) appears at 9.37 °, and the d001 value is about 0.9431nm, and this introducing that has benefited from oxygen groups makes its interlamellar spacing be far longer than original crystalline flake graphite.2 θ angles are 42.6 ° of diffraction peaks of locating corresponding to the C hexagonal structure.Spectrogram to T-GNS sees, because product is thin layer graphite alkene, the corresponding diffraction peak of (002) crystal face disappears, and a steamed bun peak occurs, and it is unordered that structure becomes, thereby explained that on lattice theory this product meets the feature of thin layer graphite alkene.according to (002) diffraction peak position, utilize formula (2.1) Bragg Equation for Calculating as can be known, the 0.9431nm of the original graphite oxide of interplanar distance contrast of T-GNS becomes, 0.5741nm has descended, illustrate that it is micromolecular water and carbonic acid gas that thermal expansion makes the oxygen-containing functional group decomposed of graphite oxide interlayer closely, thereby exfoliated graphite layer, interlamellar spacing 0.3690nm after T-GNS peels off, but still larger than the interlamellar spacing 0.3336nm of original graphite, still there is a small amount of oxygen-containing functional group that does not reduce fully between the accumulation horizon of the resulting T-GNS sample of this explanation or surface.And comparatively speaking, the diffraction peak intensity that PANI-GNS locates in (002) is more weak, and its degree of disorder is larger, illustrates and peels off more fully.Calculate the interplanar distance 0.3559nm of PANI-GNS according to Bragg equation, be slightly less than the interplanar distance of T-GNS, remaining oxygen-containing functional group is described still less.
Fig. 8 is GO, and the infrared spectrogram of T-GNS and PANI-GNS is analyzed as can be known the structure of functional groups on its interlayer and surface, and after the strong oxidation of oxygenant, the GO sample is at 3390cm
-1Absorption peak occurred, this belongs to the O-H stretching vibration.At 1734cm
-1The absorption peak at place belongs to the stretching vibration of the C=O at graphite oxide edge.1605cm
-1It is the absorption peak of the bound water molecule generation of sample room.1400cm
-1The absorption peak at place is saturated tert-hydroxyl vibration peak.1240 and 1060cm
-1Asymmetric and the symmetrical stretching vibration that the absorption peak at place is respectively as graphite oxide interlayer epoxide group C-O-C produces.The infrared spectrum of contrast GO and T-GNS and PANI-GNS can know, 1240 and 1060cm
-1Place is the epoxide group stretching vibration peak of interlayer, and its absorption intensity obviously weakens, and is positioned at 1605 and 1400cm
-1The interlayer bound water molecule at place and the vibration absorption peak of saturated tert-hydroxyl disappear substantially, and this proves absolutely that reduction reaction has occurred for T-GNS and PANI-GNS.1580cm at T-GNS
-1Place and PANI-GNS are at 1612cm
-1The absorption peak at place is the absorption peak that the skeletal vibration of graphene sheet layer produces.Near the absorption peak strength of sample T-GNS herein is stronger than the absorption peak of PANI-GNS, illustrates that T-GNS has higher alignment degree, illustrate its be stripped from and the degree of reducing high less than PANI-GNS.This and front XRD obtain a result and match.
Utilize Raman spectrometer to analyze (as shown in Figure 9) to the structure of crystalline flake graphite, GO and T-GNS and PANI-GNS, due to graphite oxidized after, the surface carbon bond mode of closing changes, and I (D)/I (G) increases, and shows the unordered increase of graphite oxide structure.Because oxy radical produces destruction to the graphite symmetry, produce unordered result, this causes the enhancing of D frequency band, and the peak width at G peak also increases simultaneously, this further illustrates after peroxidation, and the introducing of oxy radical causes the degree of disorder of graphite layers structure to increase.The Raman spectrum analysis data are in Table 1.
Table 1 Raman spectrum analysis data
| Sample type | I(D)/I(G) | G Peak side-play amount (cm -1) | W F, D (cm -1) |
| graphite | 0.52 | 0 | 35 |
| GO4 | 1.69 | 14 | 164 |
| T-GNS | 1.98 | 24 | 102 |
| PANI-GNS | 2.14 | 16 | 80 |
Utilize scanning electronic microscope to original crystalline flake graphite, the microscopic appearance of the peelable graphite of the corresponding presoma of GO and T-GNS and PANI-GNS is observed (as shown in Figure 10-13).Discovery is very little through snperoxiaized crystalline flake graphite interlamellar spacing, and fold silk structure has appearred in the GO through preparing after deep oxidation.Obvious splitting phenomenon has occurred in the GO after the high temperature thermal expansion, and graphite layers is softened, by original tight laminate structure, is expanded to accordion structure, and its interlayer structure is clearly demarcated, has proved absolutely the laminate structure that expansible black lead almost separates.And add the expansible black lead extent of exfoliation of polyaniline N doping better, most graphite flakes separated and also laminated structure very complete.Proved absolutely that polyaniline has played good booster action in stripping process.
Figure 14 and 15 is the T-GNS of two kinds of method preparations and the transmission electron microscope micro-structure diagram of PANI-GNS.As can be seen from Figure 14, can see tulle shape texture from the TEM figure of T-GNS, thereby the spontaneous crimp that shows thin layer graphite alkene fold occurs in the intrinsic contoured surface, is formed by the more nano pore of these folded structures and nanometer hole, thereby has increased the specific surface area of Graphene.And can observe the duct due to some thermal expansions on graphene platelet.Figure 15 has shown that the PANI-GNS laminated structure is relatively more complete, there is no obvious duct on graphene film, and surface folding obtains more severely, presents larger specific surface area.
The specific surface area of PANI-GNS and T-GNS and business XC-72 is tested by the method for nitrogen adsorption desorption.By the observation of circle that High Voltage part adsorption-desorption is lagged behind, all nitrogen adsorption-desorption curve (Figure 16) is all obeyed the IV type curve of IUPAC classification as can be known.As shown in table 2 according to calculating between variant material the BET area.Hence one can see that, and the BET value of PANI-GNS and T-GNS is more than business VulcanXC-72 twice, and all reaches 400m
2More than/g, PANI-GNS will exceed 66m than T-GNS
2/ g, have maximum specific surface area.
The specific surface area of table 2 PANI-GNS, T-GNS and business XC-72 and aperture
As shown in figure 17, the Graphene product has obvious pore distribution in the 0.1-100nm scope, wherein has stronger pore distribution peak on the 3-5nm position.Utilize famous BJH (Barrett-Joiner-Halenda) method to analyze the pore size distribution (Figure 17) of different samples.The classification that differs according to pore size: micropore (＜2nm), mesopore (2-50nm), macropore (〉 50nm).In VulcanXC-72, PANI-GNS and T-GNS appearance is mainly central hole structure, by the data in chart, Graphene after processing by modification has larger specific surface area, and larger void distribution, for more adsorption site is provided in the hydrogen reduction process.
T-GNS and PANI-GNS are prepared into air electrode as catalyzer, during assembled battery, adopt 3.5%NaCl solution as electrolytic solution (pH=11), aluminium flake after polishing is to electrode, air electrode is Electrode, adopts the battery model of Fig. 5 and the schema of Fig. 6 to be assembled into simulated battery.Respectively to battery constant-current discharge under 10mA, 20mA, 30mA, 40mA.Figure 18-21st, be assembled into aluminium-air cell, the constant-current discharge test of carrying out after T-GNS and PANI-GNS catalyzer are prepared air electrode again.
By Figure 18-21 as can be known, when 10mA discharged, the discharge voltage plateau of PANI-GNS electrode was 1.27V, more than exceeding 120mV than T-GNS electrode, had overwhelming superiority; When electric current was 20mA, the electrode discharge voltage of PANI-GNS was 0.85V, and the sparking voltage of T-GNS electrode approximately is down to 0.46V; When discharging current was 30mA, the sparking voltage of PANI-GNS was stabilized in 0.84V, than T-GNS electrode discharge voltage, exceeded the 40mV left and right; When discharging current was 40mA, the PANI-GNS electrode still can have 0.81V, still than the electrode of T-GNS, exceeded the 40mV left and right.And the T-GNS electrode is that 10mA and 40mA discharge are at electric current, and a slight fluctuation has appearred in discharge platform, and stability test does not have the good of PANI-GNS electrode relatively.To sum up, can draw the prepared air electrode discharge performance of PANI-GNS catalyzer better.
Claims (10)
1. the preparation method of porous graphene, it is characterized in that described porous graphene is prepared in accordance with the following steps: take graphite oxide as presoma, in retort furnace, it is carried out high-temperature heat treatment, then be dispersed in ethanol, process 20-120min in ultra sonic bath, obtain black suspension, after the washing with alcohol filtered several times, 20-80 ℃ of vacuum-drying 12-48h obtains graphen catalyst.
2. the preparation method of porous graphene according to claim 1, is characterized in that the high-temperature heat treatment mode is Rapid Thermal plavini or Polyaniline-modified method.
3. the preparation method of porous graphene according to claim 2 is characterized in that the step that described Rapid Thermal plavini prepares porous graphene is as follows:
First the 50-500mg graphite oxide is ground into powder, puts into the reaction unit after deoxygenation is processed, then join preheating and be in the retort furnace of 800-1500 ℃, rapid expansion 30s obtains peelable graphite; To obtaining in peelable graphite adding 50-500 mL dehydrated alcohol, process 20-120min in ultra sonic bath, obtain black suspension, after the washing with alcohol filtered several times, 20-60 ℃ of vacuum-drying 12-48h, obtain the powder of Graphene.
4. the preparation method of porous graphene according to claim 2 is characterized in that the step of the standby porous graphene of described Polyaniline-modified legal system is as follows:
(1) get 50-500mg graphite oxide fine powder, ultrasonic 20-120min in the distilled water of 50-1000mL;
(2) add concentrated hydrochloric acid, make it be configured to the solution of 0.1-5mol/L;
(3) stir the aniline monomer that drips 50-200mg in the backward solution of 20-120min, continue to stir 30min;
(4) (the NH of weighing 0.1-0.5g then
4) S
2O
8Incorporate in the HCl of 5-50mL, 0.1-5mol/L, be added drop-wise in the mixture of step (3) stirring at room 12-48h;
(5) use a large amount of distilled water washs, filter, 20-80 ℃ of vacuum drying obtains the PANI-GO powder;
(6) dried PANI-GO is ground into powder, joins preheating and be in the retort furnace of 600-1500 ℃, rapid expansion 10-60s obtains peelable PANI-graphite;
(7), to obtaining in peelable graphite adding the 50-500mL dehydrated alcohol, process 20-120min in ultra sonic bath, obtain black suspension, after the washing with alcohol filtered several times, 20-80 ℃ of vacuum-drying 12-48h, obtain the powder of PANI-GNS.
5. according to claim 1, the preparation method of 2,3 or 4 described porous graphenes, it is characterized in that described graphite oxide adopts Hummer ' s method to be prepared.
6. the preparation method of porous graphene according to claim 5 is characterized in that described Hummer ' s method steps is as follows:
(1) in the 50-250mL round-bottomed flask, add the 12-48mL vitriol oil, take Potassium Persulphate and each 1.0-5g of Vanadium Pentoxide in FLAKES with electronic balance, join fast in flask oil bath 40-180 ℃ of lower stirring and refluxing;
(2) after it dissolves, slowly add the 1.0-5g Graphite Powder 99 in mixture, continue at the uniform velocity stirring reaction heating 2-10h, question response is complete, round-bottomed flask is mentioned from the oil bath pan the inside, after naturally cooling to room temperature, reactant is poured in the 1-2L large beaker, slowly add the dilution of 200-2000mL water, be placed on standing 12-48h in stink cupboard;
(3) after the obvious layering of thing to be mixed, supernatant liquid is outwelled, used the Büchner funnel suction filtration, and extremely neutral with a large amount of distilled water washs, then product is transferred in culture dish, place 12-48h in Fume Hoods, naturally dry the graphite that obtains processing;
(4) graphite that will process, put into the 50-200g vitriol oil and stir at ice bath, slowly adds 8-30gKMnO
4Stir afterwards 1-10h in ice bath;
(5) put into the oil bath pan of 35 ± 3 ℃, stir 20-120min, then slowly be added drop-wise to 100-300mL distilled water in said mixture;
(6) thing to be mixed is cool to room temperature, takes out and puts into the 2-5L large beaker, adds 500-1500mL distilled water and 5-60mLH
2O
2, continuing to be stirred to does not have Bubble formation, and mixed solution becomes golden yellow by atropurpureus;
(7) standing 5-48h, abandoning supernatant, mixture is the HCl of 0.1:10-2:10 and water centrifuge washing repeatedly with volume ratio, obtains the gelatinoid of brown;
(8) gelatinoid, 30-80 ℃ of lower vacuum-drying, grinds and obtains chocolate solid, i.e. graphite oxide.
7. the preparation method of porous graphene according to claim 6, is characterized in that described graphite adopts 325 purpose crystalline flake graphites.
8. the preparation method of porous graphene according to claim 1, is characterized in that the pore size distribution of described porous graphene at 3-100nm, and specific surface area is 400-500m
2/ g.
9. method of utilizing the described porous graphene of claim 1 to prepare graphene-based aluminium-air cell is characterized in that described method steps is as follows:
(1) preparation of air electrode diffusion layer:
Utilize acetylene black to do conductive agent, polytetrafluoroethylene (PTFE), as binding agent, becomes film at nickel foam both sides nip drum after stir process, after high temperature sintering, forms the diffusion layer of porous;
(2) preparation of porous graphene catalyzer:
Prepare the porous graphene catalyzer according to the described method of claim 1;
(3) assembling of air electrode:
take porous graphene catalyzer 10-50mg and be placed in small beaker, the n-2 methyl-2-pyrrolidone that adds 0.1-1g, after ultra-sonic dispersion is processed 20-120min, drip wherein 0.05-0.5g polyvinylidene difluoride (PVDF) class binding agent, magnetic agitation 5-20h, until catalyzer is modulated into after paste a side that spreads upon uniformly diffusion layer, prepare two air electrodes, and carry out the mark of Catalytic Layer, then after being placed in vacuum drying oven 25-80 ℃ of dry 10-48h, cooling is taken out, use under tabletting machine 2-10MPa, press 2-10min, after electrode slice is compressed, obtain working electrode.
10. the preparation method of graphene-based aluminium-air cell according to claim 9 is characterized in that the concrete preparation process of described air electrode diffusion layer is as follows:
1) ammonium oxalate is ground to form fine powder, get 0.5-5g and join in the 50-150mL beaker, then add the 20-100mL dehydrated alcohol, cover preservative film, stir 1-10h;
2) add 0.5-2g acetylene black, continue fully to stir 6-12h, drip the 1-5g tetrafluoroethylene in mixture, continue to stir 10-48h it is uniformly dispersed, during be covered with preservative film;
3) open preservative film, put into 70-90 ℃ of water-bath stirring heating and process, remove ethanol, when without obvious ethanol, existing,, with the both sides of its roll extrusion in nickel foam, put into baking oven, 100-150 ℃ of dry 10-72h.
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