CN105289600B - A kind of preparation method of magnesium air battery carbon supporting Pt-Mo alloy catalyst - Google Patents
A kind of preparation method of magnesium air battery carbon supporting Pt-Mo alloy catalyst Download PDFInfo
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- CN105289600B CN105289600B CN201510817783.7A CN201510817783A CN105289600B CN 105289600 B CN105289600 B CN 105289600B CN 201510817783 A CN201510817783 A CN 201510817783A CN 105289600 B CN105289600 B CN 105289600B
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Abstract
The invention discloses a kind of preparation method of carbon supporting Pt-Mo alloy catalyst and its applications in magnesium air battery.In an inert atmosphere, using immersion reduction method, for water as solvent, sodium borohydride restores the presoma containing Pt, Mo as reducing agent at normal temperature, carbon supporting Pt-Mo alloy catalyst is synthesized, products therefrom has good alloying level, the regular appearance of nano-metal particle, compared with the carbon loaded Pt catalyst of the same metal loading prepared under the same terms, with excellent oxygen reduction catalytic activity, there is higher voltage platform and specific capacity in magnesium air battery system.The present invention provides a kind of simple processes, carbon supporting Pt-Mo alloy catalyst preparation method at low cost, have a good application prospect.
Description
Technical field
The invention belongs to catalyst and air cell technical field, are related to a kind of magnesium air battery carbon supporting Pt-Mo conjunction
The preparation method of Au catalyst.
Background technique
Metal-air battery has that high theoretical specific energy, low cost, structure be simple, advantages of environment protection, is a kind of reason
The electrochemical energy storage and conversion equipment thought.Magnesium rich reserves, cheap on earth, reactivity is high, theoretical specific volume
Amount is up to 2.2Ah/g, and relative safety is higher, therefore magnesium air battery is a kind of chemical-electrical with broad prospect of application
Source.
Magnesium air battery is made of magnesium anode, electrolyte and air cathode.During magnesium air battery discharge, anode
Magnesium metal is oxidized to magnesium ion, O2Across air cathode, OH is reduced into gas-solid body-liquid three phase boundary-.Magnesium air electricity at present
There are still many problems, real work voltages to be usually less than 1.2 volts in pond, not as good as theoretical value half, practical specific energy also with reason
It differs greatly by value.One of the main reason for causing the above problem is the slow dynamics of air cathode oxygen reduction reaction, and oxygen
The dynamic process of reduction and air cathode catalyst are closely related.
Pt is the highest air cathode catalyst of oxygen reduction catalytic activity, however Pt's is expensive, and stability is inadequate
It is good.By Pt and other cheap transition metal alloys, manufactured Pt based alloy catalyst not only reduces cost, has simultaneously
There are higher oxygen reduction activity and stability；It, can also by the Pt particulate load of nanoscale on the carbon material of high-specific surface area
To reduce Pt dosage under the premise of guaranteeing oxygen reduction activity.
The electronic structure of Mo is 4d55s1, d electron number is less than Pt, and when forming alloy with Pt, the part d electronics transfer of Pt is arrived
The d track of Mo increases the d orbital vacancy quantity of Pt, makes the d orbital vacancy and O of Pt2O -- O bond effect it is more strong, thus
The progress for promoting O -- O bond fracture process improves the hydrogen reduction efficiency of Pt.The price of Mo is far below Pt simultaneously, therefore Mo is a kind of
The alloy element of ideal Pt based alloy catalyst.However due to the miscibility of Pt and Mo difference and Mon+/Mo0Reduction electricity
Potential difference is big, and the technique for preparing Pt-Mo alloy catalyst still has many problems.The preparation side of Pt-Mo alloy catalyst at present
Method mainly has vacuum melting pure metal, is pyrolyzed organic matter and immersion reduction method.Vacuum melting pure metal is to prepare Pt-Mo conjunction
Au catalyst most directly, the highest method of alloying level, but high smelting temperature necessarily leads to high cost, and vacuum melting
The Pt-Mo alloy of preparation is difficult to realize carbon load and nanosizing.The method of pyrolysis organic matter needs to heat, and product alloying level
It is very low, contain a large amount of Mo oxide in product, needs to be heat-treated by subsequent in inert gas high temperature, it could oxygen reduction
Compound forms alloy, it may have higher cost.And be commonly used to prepare the immersion reduction method of carbon supporting Pt alloy at present, for making
When standby Pt-Mo alloy, organic solvent is commonly used as reaction medium, not only to environment, human body nocuousness, also needs to pass through subsequent heat treatment
Organic matter is removed, while the product alloying level of immersion reduction method is not also high, include a large amount of Mo oxides, it need to be in indifferent gas
High-temperature heat treatment is carried out in body with reduced oxide, formation alloy.If can realize at normal temperature through immersion reduction method, with water
For solvent, the good carbon supporting Pt-Mo catalyst of alloying level is prepared, it will make the preparation cost of Pt-Mo alloy catalyst
It reduces.
Summary of the invention
It is an object of the invention to be directed to the deficiency of above-mentioned existing preparation method, a kind of simple magnesium air battery use is provided
The preparation method of carbon supporting Pt-Mo alloy catalyst carries out altogether also in inert atmosphere by reducing agent of sodium borohydride at normal temperature
Original, to prepare the good carbon supporting Pt-Mo alloy catalyst with high catalytic activity of alloying level.
To achieve the above object, the invention adopts the following technical scheme:
A kind of preparation method of magnesium air battery carbon supporting Pt-Mo alloy catalyst, comprising the following steps:
A. water, carbon support material, Pt presoma, Mo presoma are mixed, ultrasound obtains suspension in 15 minutes；
B. suspension is moved on in the glove box with inert atmosphere；
C. sodium borohydride aqueous solution is added in suspension, magnetic agitation is reacted 3-6 hours；
D. the suspension after reaction is removed into glove box, is cleaned several times with deionized water, centrifugation, drying obtain black
Powder.
Preferably, in step a, carbon carrier is selected from one of nano-carbon material carbon black, carbon gel, carbon nanotube, graphene.Pt
Presoma is made into the Pt precursor water solution that concentration is 50mM, and Mo presoma is made into the Mo precursor water solution that concentration is 50mM,
Pt precursor water solution, Mo precursor water solution are mixed with water, carbon carrier again.Pt presoma is chloroplatinic acid.Mo presoma is
The villaumite or molybdate of molybdenum.
Preferably, in step b, the oxygen content in glove box is less than 10ppm, and suspension is before being put into glove box, first in hand
Deoxygenation in the transitional storehouse of casing.
Preferably, in step c, the additional amount of sodium borohydride be it is excessive, it is water-soluble that sodium borohydride is first made into sodium borohydride
Liquid, then sodium borohydride aqueous solution is added in the suspension in stirring.
Preferably, in step d, drying refers to vacuum drying 3 hours at 40 DEG C.
It is 1-10nm according to the metal particle size in the carbon supporting Pt-Mo alloy catalyst of above-mentioned preparation method preparation.
Method of the above-mentioned carbon supporting Pt-Mo alloy catalyst for magnesium air battery is as follows:
It is added to after obtained powder is carefully ground in the mixed solution of binder and ethyl alcohol, sonic oscillation is uniform, applies
It overlays on glass-carbon electrode, carries out cyclic voltammetry in oxygen saturation 3.5wt% sodium-chloride water solution.By after grinding powder with
Band is coated in after binder, water, alcohol mixing and fills and leads up the air cathode on the carbon paper of layer as magnesium air battery, with 3.5wt%
NaCl aqueous solution as electrolyte, pure magnesium is as anode assembling air cell.
It is closed the method have the characteristics that directly having synthesized carbon load Pt nano particle-Mo at normal temperature using sodium borohydride reduction
Au catalyst, resulting materials are not required to subsequent heat treatment i.e. and can reach good alloying level, and metallic particles partial size is small and particle
It is evenly distributed.The carbon loads Pt nano particle-Mo alloy catalyst in oxygen saturation sodium-chloride water solution, shows to be higher than equal conditions
The oxygen reduction catalytic activity of the carbon loaded Pt catalyst of the same percentage of metal of lower preparation；Voltage in magnesium air battery is flat
The carbon loaded Pt catalyst of platform and specific capacity also above the same percentage of metal prepared under equal conditions.
It is described further below with reference to technical effect of the attached drawing to design of the invention, specific example and generation, with
It is fully understood from the present invention.The purpose for providing these explanations, which is only that, helps explain the present invention, should not be taken to limit the present invention
The scope of the claims.
Detailed description of the invention
Fig. 1 is the XRD spectrum for the Pt-Mo/C catalyst that embodiment 1 is prepared；
Fig. 2 is the TEM pattern for the Pt-Mo/C catalyst that embodiment 1 is prepared；
Fig. 3 is that cyclic voltammetric of the Pt-Mo/C catalyst that is prepared of embodiment 1 in oxygen saturation sodium chloride solution is bent
Line；
Fig. 4 is the Pt-Mo/C catalyst that is prepared of embodiment 1 5mA/cm in magnesium air battery2Current density under
Specific discharge capacity-voltage curve.
Fig. 5 is the XRD spectrum for the Pt-Mo/C catalyst that embodiment 2 is prepared；
Fig. 6 is the TEM pattern for the Pt-Mo/C catalyst that embodiment 2 is prepared；
Fig. 7 is that cyclic voltammetric of the Pt-Mo/C catalyst that is prepared of embodiment 2 in oxygen saturation sodium chloride solution is bent
Line；
Fig. 8 is the Pt-Mo/C catalyst that is prepared of embodiment 2 5mA/cm in magnesium air battery2Current density under
Specific discharge capacity-voltage curve.
Specific embodiment
Technical solution of the present invention is described in further detail below by way of specific embodiment.Following embodiment is pair
Further explanation of the invention, but do not limit the scope of the invention.
The obtained Pt-Mo/C catalyst prepared in following embodiment is applied with test method such as in magnesium air battery
Under:
Be Pt-Mo/C alloy catalyst with the nanometer powder that the present embodiment is prepared, by 5mg catalyst, 1mL ethyl alcohol and
The Nafion membrane solution of 50 μ L is mixed in weighing bottle and sonic oscillation 20min, and the mixed liquor for pipetting 10 μ L is slowly dropped to glass
On carbon electrode, cyclic voltammetry is carried out after it is dried in air.Cyclic voltammetry uses three-electrode system, is coated with and urges
The glass-carbon electrode of agent is working electrode, and platinum electrode is to electrode, and calomel electrode is reference electrode, and electrolyte is 3.5wt%'s
Sodium chloride solution, logical half an hour high pure oxygen is before testing to reach oxygen saturation, and scanning range is 0.7 to -1V, and scanning speed is
50mV/s.Constant-current discharge test in air cell is enterprising in LAND cell tester (Wuhan Lan electricity Electronics Co., Ltd.)
Row, current density 5mA/cm2, electrolyte is 3.5wt%NaCl solution, and air cathode is the carbon paper for coating a certain amount of catalyst,
Anode is pure magnesium.
The synthesis of embodiment 1 Pt-Mo/C (3:1) catalyst
1, with carbon gel, it is Pt:Mo=3:1 according to carbon content 80%, mole atom ratio that chloroplatinic acid, sodium molybdate, which are raw material,
Ratio carbon gel, chloroplatinic acid aqueous solution and sodium molybdate aqueous solution are add to deionized water, after sonic oscillation 20min, will
Reaction vessel moves into the glove box of interior filling with inert gas.
2, sodium borohydride solids and soluble in water are weighed in glove box, and sodium borohydride aqueous solution is slowly added into and is contained
Carbon, Pt, Mo suspension in, by above-mentioned suspension magnetic agitation 4 hours in an inert atmosphere.
3, the suspension after reaction is removed into glove box, pours out supernatant liquor, gained grey black solid deionized water
After washing for several times, 40 DEG C of vacuum drying obtain the catalyst fines of black.
Carbon supporting Pt/Mo alloy catalyst that the present embodiment is prepared, EDS measure the nearly 3:1 of atomic ratio of Pt and Mo,
XRD diffraction maximum is displaced compared with the Pt-C catalyst that same process is prepared to high angle, shows there is Lattice Contraction phenomenon, alloying journey
Degree is good.The metallic particles size of gained catalyst is about 4.9nm, is uniformly distributed on the carbon carrier.
The carbon supporting Pt that the present embodiment is prepared/hydrogen reduction electric current of the Mo alloy catalyst in saturated sodium chloride solution
Peak value is 21.1mA/cm2, it is 2.65 times of the Pt-C catalyst that same process is prepared, the discharge platform in magnesium air battery
Voltage is 1.34V, improves 7.49%, discharge capacity 1311mAh/g compared to the Pt-C catalyst that same process is prepared,
13.41% is improved compared to the Pt-C catalyst that same process is prepared.
The synthesis of embodiment 2Pt-Mo/C (1:1) catalyst:
1, with carbon gel, it is Pt:Mo=1:1 according to carbon content 80%, mole atom ratio that chloroplatinic acid, sodium molybdate, which are raw material,
Ratio carbon gel, chloroplatinic acid aqueous solution and sodium molybdate aqueous solution are add to deionized water, after sonic oscillation 20min, will
Reaction vessel moves into glove box.
2, sodium borohydride solids and soluble in water are weighed in glove box, and sodium borohydride aqueous solution is slowly added into
In carbon containing, Pt, Mo suspension, by above-mentioned suspension magnetic agitation 4 hours in an inert atmosphere.
3, the suspension after reaction is removed into glove box, pours out supernatant liquor, gained grey black solid deionized water
After washing for several times, 40 DEG C of vacuum drying obtain the catalyst fines of black.
Carbon supporting Pt/Mo alloy catalyst that the present embodiment is prepared, EDS measure the nearly 1:1 of atomic ratio of Pt and Mo,
XRD diffraction maximum is displaced compared with the Pt-C catalyst that same process is prepared to high angle, shows there is Lattice Contraction phenomenon, alloying journey
Degree is good.The metallic particles size of gained catalyst is about 5.3nm, is uniformly distributed on the carbon carrier.
The carbon supporting Pt that the present embodiment is prepared/hydrogen reduction electric current of the Mo alloy catalyst in saturated sodium chloride solution
Peak value is 10.3mA/cm2, it is 1.29 times of the Pt-C catalyst that same process is prepared, the discharge platform in magnesium air battery
Voltage is 1.32V, improves 5.42%, discharge capacity 1210mAh/g compared to the Pt-C catalyst that same process is prepared,
4.67% is improved compared to the Pt-C catalyst that same process is prepared.
The preferred embodiment of the present invention has been described in detail above.It should be appreciated that those skilled in the art without
It needs creative work according to the present invention can conceive and makes many modifications and variations.Therefore, all technologies in the art
Personnel are available by logical analysis, reasoning, or a limited experiment on the basis of existing technology under this invention's idea
Technical solution, all should be within the scope of protection determined by the claims.
Claims (6)
1. a kind of preparation method of magnesium air battery, which is characterized in that first prepare carbon supporting Pt-Mo alloy catalyst, including with
Lower step:
A. Pt presoma is made into the Pt precursor water solution that concentration is 50mM, Mo presoma is made into the Mo forerunner that concentration is 50mM
Body aqueous solution, according to carbon content 80%, mole atom than the ratio for Pt:Mo=3:1 or Pt:Mo=1:1, by the Pt forerunner
Body aqueous solution, the Mo precursor water solution, water, carbon support material mixing, ultrasound obtain suspension in 15 minutes；
B. the suspension is moved on in the glove box with inert atmosphere；Oxygen content in the glove box is less than 10ppm, institute
Suspension is stated before being put into glove box, the first deoxygenation in the transitional storehouse of glove box；
C. sodium borohydride aqueous solution is added in the suspension, magnetic agitation is reacted 3-6 hours；
D. the suspension after reaction is removed into the glove box, is cleaned several times with deionized water, centrifugation, drying obtain black
Powder, the drying refer to vacuum drying 3 hours at 40 DEG C；
It is added to after obtained powder is carefully ground in the mixed solution of binder and ethyl alcohol, sonic oscillation is uniform, is coated in
On glass-carbon electrode, cyclic voltammetry is carried out in oxygen saturation 3.5wt% sodium-chloride water solution；By the powder and bonding after grinding
Band is coated in after agent, water, alcohol mixing and fills and leads up the air cathode on the carbon paper of layer as magnesium air battery, with 3.5wt%'s
NaCl aqueous solution is as electrolyte, and pure magnesium is as anode assembling air cell.
2. preparation method according to claim 1, which is characterized in that in step a, the carbon carrier is selected from nano-carbon material
One of carbon black, carbon gel, carbon nanotube, graphene.
3. preparation method according to claim 1, which is characterized in that in step a, the Pt presoma is chloroplatinic acid.
4. preparation method according to claim 1, which is characterized in that in step a, the Mo presoma be molybdenum villaumite or
Molybdate.
5. preparation method according to claim 1, which is characterized in that in step c, the additional amount of sodium borohydride is excessive
, sodium borohydride is first made into the sodium borohydride aqueous solution, then the sodium borohydride aqueous solution is added to the institute in stirring
It states in suspension.
6. the carbon supporting Pt-Mo alloy catalyst of any one of -5 preparation method preparations, feature exist according to claim 1
In the metal particle size in the carbon supporting Pt-Mo alloy catalyst is 1-10nm.
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| Title |
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| "Carbon supported Pt，Ru and Mo catalysts for methanol Electrooxidation";Teliz Erika et al.;《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》;20120109;第37卷(第19期);第14762页2.1. Electrode preparation and pretreatments，Table 1 |
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