CN103387229B - 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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- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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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 materials synthesis and Application Areas, relate to a kind of preparation method of novel aluminium-air cell catalyzer, be specifically related to a kind of Graphene is incorporated into as catalyzer the novel method preparing air electrode in the middle of aluminium-air cell.
Background technology
Because aluminium-air cell has the features such as specific energy is high, raw material sources abundant, use safety, stability are good, get more and more people's extensive concerning.The aluminium-air cell making anode of metallic aluminium commercially occurs also there has been the time of two more than ten years as a kind of new battery.But aluminium-air electrode still exists many problems, the corrosion of aluminum anode and liberation of hydrogen effect, the polarization phenomena of air electrode are serious, and the expansion energy ability of oxygen is on the low side, and the utilization ratio of air electrode to oxygen is lower.
In recent years, for these shortcomings in aluminium-air electrode existing for air electrode, domestic and international researcher is more and more ripe to the research of aluminum anode, and cathode air electrode becomes another study hotspot of aluminium-air cell.When air electrode there is conduction, have catalytic activity, the feature such as air penetrability is high, liquid-tight time, the specific energy of battery can be greatly improved.The more aluminium-air cell cathod catalyst of current research mainly contains Manganse Dioxide class, perovskite, metal organic macrocycle inner complex class and precious metal, but these catalyzer all do not find broad application up to now.
Grapheme material is a kind of nano material be made up of mono-layer graphite sheet, has excellent electroconductibility, mechanical property and catalytic activity, has become the focus of attention of numerous disciplinary study personnel such as physics, chemistry and materialogy.Currently reportedly Graphene is applied to the metal-air battery such as lithium-air battery, sodium gas battery, but having not yet to see report applies in the middle of aluminium-air cell by Graphene, therefore, Graphene is applied in the middle of aluminium-air cell as cathod catalyst have very important significance.
Summary of the invention
In order to the cathodic polarization rate solving current aluminium-air cell is large, the problems such as cell discharge voltage is low, the present invention is low by cost, performance good, the simple Graphene of preparation process applies in the middle of aluminium-air cell, improves the discharge stability of battery while making the sparking voltage of raising aluminium-air cell.
An object of the present invention is to provide a kind of preparation method of porous graphene, and this preparation method adopts dilatometry to generate porous graphene material, and this Graphene is prepared into air electrode.Prepared Graphene is made up of single or multiple lift graphene-structured unit, and the projection Electronic Speculum figure of Graphene can observe obvious pore structure, and pore size distribution is at 3-100nm, and specific surface area is at 400-500m
2/ g.The preparation process of porous graphene mainly divides two processes: the preparation of graphite oxide and the expansion reduction of graphite oxide.General employing Hummer ' s method 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 graphite oxide that degree of oxidation is higher.Its concrete preparation process is as follows:
(1) in 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, stirring and refluxing at oil bath 40-180 DEG C;
(2) after it dissolves, 1.0-5g Graphite Powder 99 is slowly added in mixture, continue at the uniform velocity stirring reaction heating 2-10h, question response is complete, round-bottomed flask is mentioned inside oil bath pan, after naturally cooling to room temperature, reactant is poured in 1-2L large beaker, slowly add the dilution of 200-2000mL water, be placed in stink cupboard and leave standstill 12-48h;
(3), after the obvious layering of thing to be mixed, supernatant liquid is outwelled, uses Büchner funnel suction filtration, and with a large amount of distilled water wash to neutral, then product is transferred in culture dish, in Fume Hoods, place 12-48h, naturally dry, obtain the graphite processed;
(4) graphite will processed, puts into the 50-200g vitriol oil and stirs at ice bath, slowly add 8-30gKMnO
4after in ice bath, stir 1-10h;
(5) put into the oil bath pan of 35 ± 3 DEG C, stir 20-120min, then 100-300mL distilled water is slowly added drop-wise in said mixture;
(6) thing to be mixed is cool to room temperature, takes out and puts into 2-5L large beaker, add 500-1500mL distilled water and 5-60mLH
2o
2, continuing to be stirred to does not have bubble to produce, and mixed solution becomes golden yellow from atropurpureus;
(7) leave standstill 5-48h, abandoning supernatant, mixture volume ratio is HCl and the water centrifuge washing repeatedly of 0.1:10-2:10, obtains the gelatinoid of brown;
(8) gelatinoid vacuum-drying at 30-80 DEG C, grinding obtains dark brown solid, i.e. graphite oxide.
(9) take graphite oxide as presoma, in 800-1500 DEG C of retort furnace, high-temperature heat treatment is carried out to it, then be dispersed in ethanol, process 20-120min in ultra sonic bath, obtain black suspension, after washing with alcohol filtered several times, 20-80 DEG C of vacuum-drying 12-48h, obtain graphen catalyst, described high-temperature processing method is rapid thermal expansion method or Polyaniline-modified method, wherein:
Rapid thermal expansion legal system is as follows for the step of porous graphene:
First be ground into powder by the graphite oxide obtained by 50-500mg step 8, put into the reaction unit after deoxygenation process, then join in retort furnace, rapid expansion 30s obtains peelable graphite; To obtaining adding 50-500 mL dehydrated alcohol in peelable graphite, processing 20-120min, obtain black suspension in ultra sonic bath, after washing with alcohol filtered several times, 20-60 DEG C of vacuum-drying 12-48h, obtains the powder of Graphene.
It is as follows for the step of porous graphene that polyaniline (PANI) modifies legal system:
First PANI is modified graphite oxide to peel off again and obtain required Graphene.Get the GO fine powder (graphite oxide fine powder) obtained by 50-500mg step 8, 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; In solution, drip the aniline monomer of 50-200mg after stirring 20-120min, continue to stir 30min; Then (the NH of 0.1-0.5g is weighed
4) S
2o
8incorporate in the HCl of 5-50mL, 0.1-5mol/L, be added drop-wise in mixture, stirring at room temperature 12-48h; Use a large amount of distilled water wash, filter, 20-80 DEG C of vacuum drying obtains PANI-GO powder; Be ground into powder by dried PANI-GO, joining preheating is in the retort furnace of 600-1500 DEG C, and rapid expansion 10-60s obtains peelable PANI-graphite; To obtaining adding 50-500mL dehydrated alcohol in peelable graphite, processing 20-120min, obtain black suspension in ultra sonic bath, after washing with alcohol filtered several times, 20-80 DEG C of vacuum-drying 12-48h, obtains the powder of PANI-GNS.
Two of object 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 catalyst 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 after stir process at nickel foam both sides nip drum, 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 50-150mL beaker, then add 20-100mL dehydrated alcohol, cover preservative film, stir 1-10h;
2) add 0.5-2g acetylene black, continue fully to stir 6-12h, drip 1-5g tetrafluoroethylene in mixture, continue to stir 10-48h and make it be uniformly dispersed, period is covered with preservative film;
3) open preservative film, put into the process of 70-90 DEG C of water-bath stirring heating, removing ethanol, in time existing without obvious ethanol, by the both sides of its roll extrusion in nickel foam, puts into baking oven, 100-150 DEG C of dry 10-72h.
(2) preparation of porous graphene catalyzer:
Be presoma with graphite oxide, in retort furnace, carry out high-temperature heat treatment to it, be then dispersed in ethanol, ultrasonication prepares graphen catalyst.
(3) assembling of air electrode:
Take graphen catalyst 10-50mg and be placed in small beaker, add the n-2 methyl-2-pyrrolidone (NMP) of 0.1-1g, after ultrasonic disperse process 20-120min, drip 0.05-0.5g polyvinylidene difluoride (PVDF) (PVDF) class binding agent wherein, magnetic agitation 5-20h, until spread upon the side of diffusion layer after catalyzer is modulated into paste uniformly, its thickness is 0.5mm, prepare two air electrodes, and carry out the mark of Catalytic Layer, then to be placed in vacuum drying oven 25-80 DEG C of cooling after dry 10-48 hour to take out, under using tabletting machine 2-10MPa, pressure 2-10min, after electrode slice is compressed, obtain working electrode.
The graphite oxide that above-mentioned preparation method adopts adopts Hummer ' the s method improved to prepare.Wherein graphite former state adopts 325 object crystalline flake graphites.Crystalline flake graphite is prepared 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 about 400-500m
2/ g.
The graphene-supported amount of air electrode is few, is about 1.5mg/cm
2, the constant-current discharge voltage after being assembled into battery with the air electrode of preparation is higher, and can maintain higher discharge platform under high currents.
Experiment shows: utilize the preparation method provided in the present invention, 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, effectively can improve diffusibility and the oxygen reducing ability of oxygen, has larger potential using value.And the present invention adopts rapid expansion can realize the production in enormous quantities of the grapheme material of this porous high-specific surface area easily.And the graphite oxide after adopting Polyaniline-modified is through rapid thermal expansion, the grapheme material that performance is more excellent can be obtained.
In the middle of the present invention, after Graphene is applied to aluminium-air cell, its constant-current discharge voltage platform is than the height of the catalyzer such as uhligite, Manganse Dioxide, and the stability of battery also significantly improves.On the other hand, the preparation method of Graphene is simple, and excellent performance, therefore can produce in a large number, reduces the cost of manufacture of catalyzer, improves the catalytic effect of battery.
Accompanying drawing explanation
Fig. 1 is the schema of pre-treatment crystalline flake graphite;
Fig. 2 is the process flow sheet preparing graphite oxide;
Fig. 3 is air electrode front elevation;
Fig. 4 is air electrode side elevational view;
Fig. 5 is aluminium-air cell space model;
Fig. 6 is aluminium-air cell assembling flow path figure;
Fig. 7 is the XRD figure of crystalline flake graphite, GO, 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 embodiments are only for illustration of the present invention instead of for limiting the scope of the invention.
Embodiment one: in present embodiment, graphite oxide adopts the hummers method improved to prepare.The experimental technique of research preparation GO, and its individual process and process step are optimized, the experiment flow figure of pretreating graphite and preparation GO is as shown in 1 and 2, and specific experiment step is as follows:
(1) in 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, stirring and refluxing at oil bath 80 DEG C.
(2) after it dissolves, 3g Graphite Powder 99 is slowly added in mixture, continue at the uniform velocity stirring reaction and heat 4.5 hours, question response is complete, round-bottomed flask is mentioned inside oil bath pan, after naturally cooling to room temperature, reactant is poured in 1L large beaker, slowly add the dilution of 500mL water, be placed in stink cupboard and leave standstill an evening.
(3), after the obvious layering of thing to be mixed, supernatant liquid is outwelled, uses Büchner funnel suction filtration, and with a large amount of distilled water wash to neutral, then product is transferred in culture dish, in Fume Hoods, place an evening, naturally dry, obtain the graphite processed.
(4) graphite will processed, puts into the 120mL vitriol oil and stirs at ice bath, slowly add 15gKMnO
4after in ice bath, stir 4h.
(5) put into the oil bath pan of 35 ± 3 DEG C, stir 1h, then 200mL distilled water is slowly added drop-wise in said mixture.
(6) thing to be mixed is cool to room temperature, takes out and puts into 2L large beaker, add 700mL distilled water and 30mLH
2o
2(30%), continuing to be stirred to does not have bubble to produce, and mixed solution becomes golden yellow from atropurpureus.
(7) leave standstill 12h, abandoning supernatant, mixture volume ratio is HCl and the water centrifuge washing repeatedly of 1:10, obtains the gelatinoid of brown.
(8) vacuum-drying at 50 DEG C, grinding obtains dark brown 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 is made, and detailed process is as follows:
Take graphen catalyst 30mg and be placed in small beaker, add the n-2 methyl-2-pyrrolidone (NMP) of 0.2g, after ultrasonic disperse process 30min, add 0.1g polyvinylidene difluoride (PVDF) (PVDF) wherein, use magnetic stirrer 12h, until spread upon the side of diffusion layer after catalyzer is modulated into paste uniformly, prepare two air electrodes, and carry out the mark of Catalytic Layer, then be placed in 45 DEG C of dryings in vacuum drying oven to lower the temperature after 12 hours taking-up, under using tabletting machine 4MPa, pressure 5min, after being compressed by electrode slice, obtain working electrode.
Reserving the nickel foam collector of 1.0cm in the upside of air electrode, mainly to contact with test electrode clip for convenience of leaving for when test.Catalyzer to be noted when smearing all to be divided into two parts, to spread upon one deck of Catalytic Layer gently, after it be waited dry, just can carry out compressing tablet.The front of prepared working electrode and lateral effect figure are as shown in Figure 3-4.
Battery space model after being assembled into battery as shown in Figure 5.
Embodiment three: in present embodiment, selects Hummer ' the s legal system of improvement for graphite oxide.Graphite adopts natural flake graphite, uses P
2o
5, KMnO
4, K
2s
2o
8, dense H
2sO
4etc. several mixture, preoxidation (Fig. 1) is carried out to graphite and obtain expanded graphite.Then the graphite will processed, adds 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 exceed 4 DEG C, ice bath 1-4h, then the process of temperature (35 DEG C) in directly passing through, by 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 again, vacuum-drying, obtain graphite oxide (Fig. 2).
Embodiment four: present embodiment passes through rapid thermal expansion legal system for Graphene (T-GNS):
First being ground into powder by 200mg graphite oxide, putting into the reaction unit after deoxygenation process, is that in the retort furnace of 1100 DEG C, rapid expansion 30s obtains peelable graphite to preheating.To obtaining adding 100mL dehydrated alcohol in peelable graphite, processing 30min, obtain black suspension in ultra sonic bath, after washing with alcohol filtered several times, 40 DEG C of vacuum-drying 24h obtain the powder of Graphene.
Embodiment five: present embodiment modifies legal system for Graphene (PANI-GNS) by polyaniline (PANI):
First PANI is modified graphite oxide peel off again obtain need Graphene (first modify graphite oxide with PANI, and then by 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, adds a certain amount of concentrated hydrochloric acid, makes it be configured to the solution of 1mol/L.In solution, drip the aniline monomer of 100mg after stirring 30min, continue to stir 30min.Then (the NH of 0.17g is weighed
4) S
2o
8incorporate in the HCl of 10mL, 1mol/L, be added drop-wise in said mixture, stirring at room temperature 24h.Use a large amount of distilled water wash, filter, 40 DEG C of vacuum dryings obtain PANI-GO powder.Be ground into powder by dried PANI-GO, joining preheating is in the retort furnace of 1000 DEG C, and rapid expansion 30s obtains peelable PANI-graphite.To obtaining adding 100mL dehydrated alcohol in peelable graphite, processing 30min, obtain black suspension in ultra sonic bath, after washing with alcohol filtered several times, 40 DEG C of vacuum-drying 24h obtain the powder of PANI-GNS.
Embodiment six: diffusion layer has hydrophobic and ventilative function, it can prevent leaking outside of electrolytic solution on the one hand, and can promote that the oxygen in air is diffused into reaction interface layer better from air on the other hand, its preparation process is mainly as follows:
(1) ammonium oxalate is ground to form fine powder, get 2.0g and join in 150mL beaker, then add 50mL dehydrated alcohol, cover preservative film, stir 3h;
(2) add 1.0g acetylene black, continuation fully stirs 9h, drips 2.5g polytetrafluoroethylene (PTFE) in mixture, continues to stir 12h and makes it be uniformly dispersed, and period is covered with preservative film to prevent the rear ethanol volatilization of long-time stirring;
(3) open preservative film, put into the process of 80 DEG C of water-bath stirring heating, removing ethanol, in time existing without obvious ethanol, by the both sides (thickness 0.5nm) of its roll extrusion in the nickel foam of 2cm × 3cm, and upper end reserves 1.0cm.Put into baking oven, 130 DEG C of dry 12h.
Embodiment seven: 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, add the n-2 methyl-2-pyrrolidone (NMP) of 0.2g, after ultrasonic disperse process 30min, add 0.1g polyvinylidene difluoride (PVDF) (PVDF) wherein, use magnetic stirrer 12h, until spread upon the side of diffusion layer after catalyzer is modulated into paste uniformly, its thickness is 0.5mm, prepare two air electrodes, and carry out the mark of Catalytic Layer, then be placed in 45 DEG C of dryings in vacuum drying oven to lower the temperature after 12 hours taking-up, under using tabletting machine 4MPa, pressure 5min, after electrode slice is compressed, obtain working electrode (Fig. 3-4).
Embodiment eight: the aluminium/gas battery of the present invention's research all adopts the NaCl of the 3.5wt% of pH=11 as electrolytic solution, and be assembled into simulated battery (Fig. 5), the assembling flow path figure of whole battery as shown in Figure 6.
Fig. 7 gives the XRD figure of crystalline flake graphite to GO, 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 d002 value is about 0.3336nm.Known by the diffracting spectrum contrasting original crystalline flake graphite, be positioned at (002) crystallographic plane diffraction peak strength reduction of 26.70 °, peak shape from sharply becoming a steamed bun peak (GO, T-GNS and PANI-GNS), and offsets to Small angle.And learn from the XRD of GO, the characteristic peak of (001) appears at 9.37 °, and d001 value is about 0.9431nm, and this introducing having benefited from oxygen groups makes its interlamellar spacing be far longer than original crystalline flake graphite.2 θ angles are the diffraction peak that 42.6 ° of places correspond to C hexagonal structure.See the spectrogram of T-GNS, because product is thin graphene, diffraction peak corresponding to (002) crystal face disappears, and occur a steamed bun peak, structure becomes unordered, thus in lattice theory, explain the feature that this product meets thin graphene.According to (002) diffraction peak position, utilize formula (2.1) Bragg Equation for Calculating known, the 0.9431nm that the interplanar distance of T-GNS contrasts original graphite oxide becomes, have dropped 0.5741nm, illustrate that thermal expansion makes the oxygen-containing functional group decomposed of graphite oxide interlayer closely be micromolecular water and carbonic acid gas, thus exfoliated graphite layer, interlamellar spacing 0.3690nm after T-GNS peels off, but still it is larger than the interlamellar spacing 0.3336nm of original graphite, this illustrates between the accumulation horizon that institute obtains T-GNS sample or surface still exists a small amount of oxygen-containing functional group do not reduced completely.And comparatively speaking, PANI-GNS is more weak at the diffraction peak intensity at (002) place, its degree of disorder is larger, illustrates and peels off more complete.Calculate the interplanar distance 0.3559nm of PANI-GNS according to Bragg equation, be slightly less than the interplanar distance of T-GNS, illustrate that remaining oxygen-containing functional group is less.
Fig. 8 is the infrared spectrogram of GO, T-GNS and PANI-GNS, and carry out analysis to its interlayer and surperficial structure of functional groups known, after being strongly oxidized by oxygenant, GO sample is at 3390cm
-1occurred absorption peak, this belongs to 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 that the bound water molecule of sample room produces.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 be known, 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 Coating combination water molecules at place and the vibration absorption peak of saturated tert-hydroxyl then disappear substantially, and this absolutely proves that T-GNS and PANI-GNS there occurs reduction reaction.At the 1580cm of T-GNS
-1place and PANI-GNS are at 1612cm
-1the absorption peak at place is then the absorption peak of the skeletal vibration generation of graphene sheet layer.Sample T-GNS herein near absorption peak strength stronger than the absorption peak of PANI-GNS, illustrate that T-GNS has higher alignment degree, illustrate its be stripped and the degree of reducing high less than PANI-GNS.This and XRD above obtain a result and match.
The structure of Raman spectrometer to crystalline flake graphite, GO and T-GNS and PANI-GNS is utilized to analyze (as shown in Figure 9), due to graphite oxidized after, surface carbon key combination changes, and I (D)/I (G) increases, and shows the unordered increase of graphite oxide structure.Because oxy radical produces destruction to 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, the introducing of oxy radical causes the degree of disorder of graphite layers structure to increase.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 carries out observing (as shown in figures 10-13).Find very not little through snperoxiaized crystalline flake graphite interlamellar spacing, and the GO prepared after deep oxidation, there is fold silk structure.GO after high-temperature heat expansion there occurs obvious splitting phenomenon, and graphite layers is softened, is expanded to accordion structure by original tight laminate structure, and its interlayer structure is clearly demarcated, has absolutely proved the laminate structure that expansible black lead is almost separated.And it is better to add the expansible black lead extent of exfoliation that polyaniline N adulterates, most graphite flake separated and also laminated structure very complete.Absolutely prove that polyaniline serves good booster action in stripping process.
Figure 14 and 15 is the transmission electron microscope micro-structure diagram of T-GNS and PANI-GNS prepared by two kinds of methods.As can be seen from Figure 14, tulle shape texture can be seen from the TEM figure of T-GNS, show the spontaneous crimp of thin graphene thus occur fold in intrinsic contoured surface, being formed by the more nano pore of these folded structures and nanometer hole, thus increase the specific surface area of Graphene.And the duct can observed on graphene platelet caused by some thermal expansions.It is relatively more complete that Figure 15 then shows PANI-GNS laminated structure, graphene film does not have obvious duct, and surface folding obtains more severe, present 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 to the delayed circle of High Voltage partial adsorbates-desorption, known all nitrogen adsorption-desorption curve (Figure 16) all obey the IV type curve of IUPAC classification.According to calculating, BET area between variant material is as shown in table 2.It can thus be appreciated that the BET value of PANI-GNS and T-GNS is more than business VulcanXC-72 twice, and all reaches 400m
2/ more than g, PANI-GNS will exceed 66m than T-GNS
2/ g, has 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, graphene product has obvious pore distribution within the scope of 0.1-100nm, wherein 3-5nm position exists stronger pore distribution peak.Utilize famous BJH (Barrett-Joiner-Halenda) method to analyze the pore size distribution (Figure 17) of different sample.Classification according to pore size differs: micropore (<2nm), mesopore (2-50nm), macropore (>50nm).At the mainly central hole structure that VulcanXC-72, PANI-GNS and T-GNS occur, by the data in chart, by the Graphene after moditied processing, there is larger specific surface area, and larger void distribution, for providing more adsorption site in hydrogen reduction process.
T-GNS with PANI-GNS is become air electrode as catalyst preparing, 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 18-21 is assembled into aluminium-air cell again by after T-GNS and PANI-GNS catalyst preparing air electrode, the constant-current discharge test carried out.
From Figure 18-21, when 10mA discharges, the discharge voltage plateau of PANI-GNS electrode is 1.27V, exceeds more than 120mV, have overwhelming superiority than T-GNS electrode; When electric current is 20mA, the electrode discharge voltage of PANI-GNS is 0.85V, and the sparking voltage of T-GNS electrode is approximately down to 0.46V; When discharging current is 30mA, the sparking voltage of PANI-GNS is stabilized in 0.84V, exceeds about 40mV compared to T-GNS electrode discharge voltage; When discharging current is 40mA, PANI-GNS electrode still can have 0.81V, still exceeds about 40mV than the electrode of T-GNS.And T-GNS electrode electric current be 10mA and 40mA electric discharge be that a slight fluctuation has appearred in discharge platform, stability test does not have the good of PANI-GNS electrode relatively.To sum up, can show that the air electrode discharge performance prepared by PANI-GNS catalyzer is better.
Claims (1)
1. a preparation method for graphene-based aluminium-air cell, is characterized in that described method steps is as follows:
(1) preparation of air electrode diffusion layer:
A, ammonium oxalate is ground to form fine powder, get 0.5-5g and join in 50-150mL beaker, then add 20-100mL dehydrated alcohol, cover preservative film, stir 1-10h;
B, add 0.5-2g acetylene black, continue fully to stir 6-12h, drip 1-5g tetrafluoroethylene in mixture, continue to stir 10-48h and makes it be uniformly dispersed, period is covered with preservative film;
C, open preservative film, put into the process of 70-90 DEG C of water-bath stirring heating, removing ethanol, in time existing without obvious ethanol, by the both sides of its roll extrusion in nickel foam, puts into baking oven, 100-150 DEG C of dry 10-72h;
(2) preparation of porous graphene catalyzer:
Be presoma with graphite oxide, in retort furnace, high-temperature heat treatment carried out to it, be then dispersed in ethanol, 20-120min is processed in ultra sonic bath, obtain black suspension, after washing with alcohol filtered several times, 20-80 DEG C of vacuum-drying 12-48h obtains porous graphene catalyzer;
(3) assembling of air electrode:
Take porous graphene catalyzer 10-50mg and be placed in small beaker, add the n-2 methyl-2-pyrrolidone of 0.1-1g, after ultrasonic disperse process 20-120min, drip 0.05-0.5g polyvinylidene difluoride (PVDF) class binding agent wherein, magnetic agitation 5-20h, until spread upon the side of diffusion layer after catalyzer is modulated into paste uniformly, prepare two air electrodes, and carry out the mark of Catalytic Layer, then cooling taking-up after 25-80 DEG C of dry 10-48h in vacuum drying oven is placed in, under using tabletting machine 2-10MPa, pressure 2-10min, after electrode slice is compressed, obtain working electrode.
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