CN109802150A - A kind of base metal bi-functional oxygen electrode catalyst and preparation method and a kind of zinc-air battery anode and zinc-air battery - Google Patents
A kind of base metal bi-functional oxygen electrode catalyst and preparation method and a kind of zinc-air battery anode and zinc-air battery Download PDFInfo
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- CN109802150A CN109802150A CN201910053202.5A CN201910053202A CN109802150A CN 109802150 A CN109802150 A CN 109802150A CN 201910053202 A CN201910053202 A CN 201910053202A CN 109802150 A CN109802150 A CN 109802150A
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Abstract
The present invention provides a kind of base metal bi-functional oxygen electrode catalyst, which is characterized in that is nanometer Fe Co8S8With the compound of redox graphene.FeCo of the present invention8S8@rGO catalyst has the synergistic effect between multi-element metal, can promote its catalysis latent active, while FeCo by regulating and controlling the electronic structure of metal8S8The In-situ reaction structure formed with redox graphene, can promote the electric conductivity and stability of catalyst entirety, electro-catalysis oxygen reduction and water oxygenization can show excellent performance in alkaline solution.Based on the zinc and air cell of catalyst assembling, the charge and discharge potential difference to compare favourably with business noble metal (platinum carbon+ruthenic oxide) combination catalyst and stability are shown.Therefore FeCo provided by the invention8S8@rGO catalyst has advantage at low cost, performance is good, can be used as efficient Oxygen Electrode Material applied to zinc and air cell.
Description
Technical field
The invention belongs to elctro-catalyst synthetic technologys and energy conversion device arts, and in particular to a kind of base metal
Bi-functional oxygen electrode catalyst and preparation method.
Background technique
The Efficient Conversion of clean energy resource and utilization have become the hot spot of global concern, and in recent years, novel chargeable metal is empty
Pneumoelectric pond, especially zinc-air battery, because its theoretical capacity (1084Wh/kg) with higher, high performance-price ratio, it is safe and non-toxic and
Advantages of environment protection, it is considered to be have the new energy reforming unit having great prospects for development.(Wang,Zhong-Li,et
al."Oxygen electrocatalysts in metal-air batteries:from aqueous to nonaqueous
Electrolytes. " Chemical Society Reviews.43.22 (2014): 7746-7786.) but its air electrode
The energy barrier of upper oxygen reduction (ORR) and water oxygen (OER) two reactions is very high, needs to reduce by efficient catalyst anti-
It should be able to build, the progress for promoting these to react considers from catalytic performance angle, and most the catalyst of advantage is precious metal catalyst at present
Agent (platinum carbon+ruthenic oxide), but the high price of noble metal and low reserves seriously limit its large-scale commercial application.Therefore
It can be significantly as the substitute of noble metal catalyst if a kind of efficient base metal bifunctional catalyst can be developed
Reduce the production and operating cost of zinc and air cell.
Co9S8Compound shows excellent ORR catalytic activity, but its OER catalytic performance because of its unique electronic structure
Undesirable (Sidik R A, Anderson A B.Co9S8 as a catalyst for electroreduction of O2:
quantum chemistry predictions[J].The journal of physical chemistry b,2006,110
(2):936-941.)。
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of base metal bi-functional oxygen electrode catalysis
Agent, base metal bi-functional oxygen electrode catalyst provided by the invention also have while with good ORR catalytic activity
Good OER catalytic performance.
The present invention provides a kind of base metal bi-functional oxygen electrode catalyst, are nanometer Fe Co8S8With reduction-oxidation graphite
The compound of alkene.
It preferably, is compound by FeCo by substrate of redox graphene and in the substrate surface8S8Nanometer sheet
The nanometer bouquet of composition.
Preferably, the diameter of the nanometer bouquet is 50~300nm；
The mass percentage that the redox graphene accounts for the base metal bi-functional oxygen electrode catalyst is
20%~60%.
The present invention also provides a kind of preparation methods of above-mentioned base metal bi-functional oxygen electrode catalyst, including following step
It is rapid:
A) using ferric acetyl acetonade and acetylacetone cobalt as metal precursor, by the metal precursor, graphene oxide, sulphur
Alcohol compound, surfactant and high boiling organic solvent mixing, under the conditions of protective atmosphere, are warming up to 220~260 DEG C,
15~60min is reacted, reaction product is obtained；
B) containing NH3Ar oxygen mixture in, it is cooling after the reaction product is annealed, obtain base metal
Bi-functional oxygen electrode catalyst Fe Co8S8@rGO。
Preferably, the sulfur alcohol compound is selected from spicy thioalcohol；
The surfactant is selected from oleic acid；
The high boiling organic solvent is selected from oleyl amine and octadecylene mixed solvent, and the volume ratio of the oleyl amine and octadecylene is
1:(2~5)；
The protective atmosphere condition is selected from nitrogen；
The molar ratio of the ferric acetyl acetonade and acetylacetone cobalt is 1:8；
The additional amount of the graphene oxide is 10~50mg/mmol metal precursor；
The additional amount of the high boiling organic solvent is 20~50mL/mmol metal precursor；
The additional amount of the sulfur alcohol compound is greater than 0.25mL/mmol metal precursor；
The additional amount of the surfactant is 0.5~2mL/mmol metal precursor.
Preferably, step A) heating program are as follows:
120~150 DEG C are risen in 10~30min from room temperature, and retention time is 30~60min, then setting heating
Rate is 5~10 DEG C/min, reaches 220~260 DEG C of reaction temperature, the reaction time is 15~60min；
Step B) in, the heating rate of the annealing is 2.5~10 DEG C/min, and the temperature of the annealing is 400~450
DEG C, the time of the annealing is 2~4h；
It is described to contain NH3Ar oxygen mixture in NH3Volume content be 5~15%.
It is positive that the present invention also provides a kind of zinc-air batterys, including above-mentioned base metal bi-functional oxygen electrode catalyst,
Or the base metal bi-functional oxygen electrode catalyst that above-mentioned preparation method is prepared.
Preferably, catalyst layer, nickel foam support frame and air diffusion layer including being sequentially compounding.
The present invention also provides a kind of zinc-air battery, including anode, cathode, electrolyte and battery case, the anodes
For above-mentioned zinc-air battery anode.
Preferably, the battery case uses PMMA material, and negative electrode material is the zinc metal sheet of sanding and polishing, electrolyte KOH
With Zn (Ac)2Mixed solution.
Compared with prior art, the present invention provides a kind of base metal bi-functional oxygen electrode catalyst, which is characterized in that
For nanometer Fe Co8S8With the compound of redox graphene.FeCo of the present invention8S8@rGO catalyst has polynary gold
Synergistic effect between category can promote its catalysis latent active, while FeCo by regulating and controlling the electronic structure of metal8S8With reduction
The In-situ reaction structure that graphene oxide is formed, can promote the electric conductivity and stability of catalyst entirety, in alkaline solution
Electro-catalysis oxygen reduction and water oxygenization can show excellent performance.Based on the zinc and air cell of catalyst assembling, show
The charge and discharge potential difference and stability to compare favourably with business noble metal (platinum carbon+ruthenic oxide) combination catalyst.Therefore the present invention mentions
The FeCo of confession8S8@rGO catalyst has advantage at low cost, performance is good, and it is empty applied to zinc to can be used as efficient Oxygen Electrode Material
Battery.
Detailed description of the invention
Fig. 1 is synthesis FeCo8S8The preparation flow figure of@rGO；
Fig. 2 is the FeCo by oily phase reaction one pot process8S8The electron scanning micrograph of@GO；Scale is in figure
1 μm, it can be seen that gained FeCo in figure8S8The bouquet being made of nanometer sheet is dispersed in the surface of GO substrate；
Fig. 3 is the Co by oily phase reaction one pot process9S8The electron scanning micrograph of@GO；Scale is 1 μ in figure
M, it can be seen that gained Co in figure9S8And the bouquet being made of nanometer sheet, and it is dispersed in the surface of GO substrate；
Fig. 4 is the FeCo by oily phase reaction one pot process8S8The transmission electron microscope photo of@GO；Scale is in figure
500nm, it can be seen that the sharp-edged laminated structure of bouquet shows that bouquet is made of two-dimensional nano piece, in addition drawout
GO substrate can be also observed, and bouquet is closely linked with GO, illustrates FeCo8S8Growth in situ is on the surface GO；
Fig. 5 is the Co by oily phase reaction one pot process9S8The transmission electron microscope photo of@GO；Scale is in figure
500nm, Co9S8The pattern and FeCo of@GO8S8@GO is closely similar, and bouquet is made of two-dimensional nano piece, and bouquet and GO are tight
Close combination；
Fig. 6 is the FeCo by oily phase reaction one pot process8S8@GO and Co9S8The X-ray diffractogram of@GO, gained produce
Object respectively with FeCo8S8Standard card JCPDS#290484 and Co9S8Standard card JCPDS#190364 it is corresponding, it is strongest
Two peaks both correspond to crystal face (311) and (440)；
Fig. 7 is the FeCo by oily phase reaction one pot process8S8The high resolution transmission electron microscopy photo of@GO, to this
Region carries out lattice analysis shows that FeCo8S8The crystal face of@GO exposure is mainly (311) crystal face, corresponding with the result of XRD；
Fig. 8 is the FeCo by oily phase reaction one pot process8S8@GO and Co9S8The raman spectrum of@GO；Positioned at 187,
464,510 and 662cm-1The peak at place is FeCo8S8And Co9S8Characteristic peak, and be located at 1349 and 1585cm-1Two strong peaks at place
Then correspond respectively to the peak feature D and the peak G of GO；
Fig. 9 is the FeCo obtained after annealing8S8@rGO and Co9S8@rGO is in the KOH solution of 0.1mol/L
The getable LSV curve of ORR is tested with three-electrode system；Abscissa is normal hydrogen electrode voltage (V), ordinate in the figure
For current density (mA cm-2), in three curves ,-▲-represents FeCo8S8The oxygen reduction LSV curve of@rGO ,-●-represent quotient
The oxygen reduction LSV curve of industry Pt/C (20%wt) ,-■-represent Co9S8The oxygen reduction LSV curve of@rGO；
Figure 10 is the FeCo obtained after annealing8S8@rGO and Co9S8KOH solution of the@rGO in 0.1mol/L
It is middle to test the getable LSV curve of OER with three-electrode system；Abscissa is normal hydrogen electrode voltage (V) in the figure, indulges and sits
It is designated as current density (mA cm-2), in three curves ,-▲-represents FeCo8S8The water oxidation reaction LSV curve of@rGO ,-●-generation
Table business RuO2Water oxidation reaction LSV curve ,-■-represents Co9S8The water oxidation reaction LSV curve of@rGO；
Figure 11 is the FeCo that annealing obtains later8S8@rGO carries out zinc air as the positive electrode of zinc-air battery
The LSV curve of battery performance test, contrast material are respectively Pt/C and Pt/C and RuO2Mixture；Abscissa in the figure
For current density (mA cm-2), ordinate is, using zinc as the electrode voltage (V) of reference, in three curves ,-▲-is represented
FeCo8S8The charge and discharge LSV curve of@rGO ,-◆-the charge and discharge LSV curve of Pt/C is represented ,-●-represent Pt/C and RuO2It is mixed
Close the charge and discharge LSV curve of object；
Figure 12 is the FeCo that annealing obtains later8S8@rGO carries out zinc air as the positive electrode of zinc-air battery
The curve of the charge and discharge cycles stability test of battery, contrast material are respectively Pt/C and Pt/C and RuO2Mixture；It surveys
Examination current density is 10mA cm-2, charge 400s, and electric discharge 400s is a circulation, tests the circulation by 200 circles, arrow in figure
It has been directed toward the charge and discharge cycles curve of each electrode of load different materials；
Figure 13 is the zinc-air battery sterogram that assembling obtains, and is tested using three-electrode system, wherein working electrode
It is all zinc metal sheet for the anode electrode piece of supported catalyst, reference electrode and to electrode, charging process generates oxygen when reaction, therefore
There is on electrode and bubble in solution.
Specific embodiment
The present invention provides a kind of base metal bi-functional oxygen electrode catalyst, are nanometer Fe Co8S8With reduction-oxidation graphite
The compound of alkene.
The catalyst is compounded in the substrate surface by FeCo using redox graphene as substrate8S8Nanometer sheet composition
Nanometer bouquet.The diameter of the nanometer bouquet is 50~300nm.
The mass percentage that the redox graphene accounts for the base metal bi-functional oxygen electrode catalyst is
20%~60%, preferably 30%~40%, further preferably 35%.
The present invention also provides a kind of preparation methods of above-mentioned base metal bi-functional oxygen electrode catalyst, including following step
It is rapid:
A) using ferric acetyl acetonade and acetylacetone cobalt as metal precursor, by the metal precursor, graphene oxide, sulphur
Alcohol compound, surfactant and high boiling organic solvent mixing, under the conditions of protective atmosphere, are warming up to 220~260 DEG C,
15~60min is reacted, reaction product is obtained；
B) containing NH3Ar oxygen mixture in, it is cooling after the reaction product is annealed, obtain base metal
Bi-functional oxygen electrode catalyst Fe Co8S8@rGO。
The present invention is using ferric acetyl acetonade and acetylacetone cobalt as metal precursor, wherein the ferric acetyl acetonade and acetyl
The molar ratio of acetone cobalt is 1:8.
Using graphene oxide as substrate, the graphene oxide is prepared the present invention by improving hummers method.The present invention
The specific method for improving hummers method is not particularly limited, well known to a person skilled in the art methods.The oxygen
The additional amount of graphite alkene is 10~50mg/mmol metal precursor, preferably 20~40mg/mmol metal precursor.
The present invention is using high boiling organic solvent as solvent, wherein the high boiling organic solvent is selected from oleyl amine and 18
The volume ratio of alkene mixed solvent, the oleyl amine and octadecylene is 1:(2~5), preferably 1:(3~4).The higher boiling is organic molten
The additional amount of agent is 20~50mL/mmol metal precursor, preferably 30~40mL/mmol metal precursor.
The sulfur alcohol compound is selected from spicy thioalcohol, and the additional amount of the sulfur alcohol compound is greater than 0.25mL/mmol gold
Belong to presoma, preferably 1~2mL/mmol metal precursor, further preferably 1mL/mmol metal precursor.
The surfactant is selected from oleic acid；The dosage of the surfactant can control the pattern and performance of product,
In the present invention, the additional amount of the surfactant is preferably 0.5~2mL/mmol metal precursor, further preferably
1mL/mmol metal precursor.
The present invention there is no specifically limited, can mix the order by merging of the raw material as follows:
Ferric acetyl acetonade and acetylacetone cobalt are placed in reaction vessel, the oleyl amine dispersion liquid of graphene oxide is added,
Then octadecylene, surfactant and sulfur alcohol compound is added.
After all raw materials are placed in reaction vessel, under the conditions of protective atmosphere, it is warming up to 220~260 DEG C, reaction 15~
60min obtains reaction product.
The program of the heating are as follows:
120~150 DEG C are risen in 10~30min from room temperature, and retention time is 30~60min, then setting heating
Rate is 5~10 DEG C/min, reaches 220~260 DEG C of reaction temperature, the reaction time is 15~60min；
In the present invention, the room temperature is defined as 20 ± 10 DEG C.
In certain specific embodiments of the invention, the temperature program are as follows:
Reaction system is warming up to 150 DEG C in 20min, and keeps 30min, then with the heating rate liter of 10 DEG C/min
Temperature keeps reaction 30min to 260 DEG C.
The reaction of above-mentioned heat temperature raising carries out under conditions of magnetic stirring apparatus is stirred, and magneton revolving speed is 300~
800rpm。
The protective atmosphere condition is selected from nitrogen.
After reaction, natually cooled to room temperature obtains reaction product.
Then, it by the alternately washing centrifugation of the reaction product ethyl alcohol and n-hexane, is then dried under the conditions of 40~100 DEG C
It is dry.
It is centrifuged 1~3 time specifically, carrying out supersound washing to product with ethanol solution first after reaction, then with just
Hexane carries out supersound washing to product and is centrifuged 2~4 times, and the product that centrifugation obtains finally is placed in 40~100 DEG C of vacuum drying
It is dry in case, obtain FeCo8S8@GO。
Containing NH3Ar oxygen mixture in, it is cooling after the reaction product is annealed, it is double to obtain base metal
Function oxygen electrode catalyst FeCo8S8@rGO。
Wherein, the heating rate of the annealing is 2.5~10 DEG C/min, and the temperature of the annealing is 400~450 DEG C, institute
The time for stating annealing is 2~4h；
It is described to contain NH3Ar oxygen mixture in NH3Volume content be 5~15%.
Specifically, the gas being passed through in tube furnace is NH3The Ar mixed gas that content is 5~15%, and temperature-rise period
Rate is 2.5~10 DEG C/min, and 2~4h is kept after being warming up to 400~450 DEG C, and last natural cooling cooling obtains
FeCo8S8@rGO。
The step can remove the solvent and surfactant on powder product surface, be translated into hydrophily product, and
And GO is reduced to the rGO of part N doping, to improve its electric conductivity.
It is synthesis FeCo referring to Fig. 1, Fig. 18S8The preparation flow figure of@rGO.
The present invention successfully prepares the ternary of GO In-situ reaction by easy one kettle way using improved oily phase reaction
FeCo8S8Nanometer sheet is then calcined in ammonia atmosphere, is restored GO, is obtained FeCo8S8@rGO catalyst.The present invention is to have
There is the Co of excellent ORR performance9S8For starting point, appropriate Fe element is introduced, two kinds of gold are optimized by the synergistic effect between multi-element metal
The electronic structure of category improves the latent active of catalyst, makes it while having excellent OER and ORR double-function catalyzing performance.
Meanwhile GO being added in the synthesis process as substrate, product can be made to be dispersed in the surface GO, product is avoided to reunite；It is another
A benefit, which is GO, is becoming the rGO for adulterating N element in part after ammonia reduction, has benefited from its special two-dimensional structure and good
Good electric conductivity, can be enhanced the electronic conductivity of compound in the reaction, so as to improve the performance of catalyst.This is difunctional
Catalyst is applied to practical zinc-air battery system, the results showed that the catalyst has good stabilization in actual battery reaction
Property and cyclicity, have the potentiality of commercial applications.
The present invention also provides a kind of zinc-air battery anode, including be sequentially compounding catalyst layer, nickel foam branch
Support bone frame and air diffusion layer.
Wherein, the air diffusion layer is prepared as follows:
Acetylene black, carbon black and PTFE solution are mixed and are scattered in ethyl alcohol, is mixed, after then removing ethyl alcohol,
The film of 250~300nm thickness is rolled under roll squeezer.
The PTFE solution is the polytetrafluoroethylsolution solution that mass concentration is 60wt%, the polytetrafluoroethylsolution solution be containing
The polytetrafluoroethylene (PTFE) aqueous dispersion liquid of non-ionic surface active stabilizer.
The mass ratio of the acetylene black, carbon black and PTFE solution is 1:(2~3): (7~8).
The time of the mixing is 30~90min.
The method for the removal solvent that the method for the removal ethyl alcohol is known to the skilled person in the present invention can
Ethyl alcohol is removed to be placed in 50~80 DEG C of baking oven.
After removing ethyl alcohol, mixture becomes dough, carries out being rolled into film after taking-up.
The catalyst layer is prepared as follows:
By carbon black, FeCo8S8@rGO is scattered in ethyl alcohol, adds PTFE solution, is mixed, after then removing ethyl alcohol,
Roll-in film forming.
Wherein, the carbon black, FeCo8S8The mass ratio of@rGO and PTFE solution is 1:(3~4): (3~4).
The FeCo8S8@rGO is base metal bi-functional oxygen electrode catalyst described above, or as described above
The base metal bi-functional oxygen electrode catalyst that is prepared of preparation method.
The time of the mixing is 30~90min.
The method for the removal solvent that the method for the removal ethyl alcohol is known to the skilled person in the present invention can
Ethyl alcohol is removed to be placed in 50~80 DEG C of baking oven.
After removing ethyl alcohol, mixture becomes dough, takes out roll-in film forming, guarantees catalyst in roll-in film forming procedure
FeCo8S8The load capacity of@rGO is 2~5mg/cm2。
After completing above-mentioned steps, air diffusion layer and Catalytic Layer are attached to the nickel foam two sides with a thickness of 1.5mm respectively, pass through
The electrode slice for becoming 0.4~0.5mm of thickness after roll-in, finally places it in Muffle furnace, makes its solidification by heat treatment
Stablize, preferably heating temperature is 300~360 DEG C, and heating time is 20~60min, and taking out after cooling becomes final electrode slice.
The present invention also provides a kind of zinc-air battery, including anode, cathode, electrolyte and battery case, the anodes
For zinc-air battery anode described above.
The present invention is to the specific type of the zinc-air battery there is no specifically limited, and well known to a person skilled in the art zinc
Air cell, the present invention is not limited to rechargeable type or non-charging type zinc-air batteries.
Wherein, the battery case uses PMMA material, and battery case consists of three parts: lower layer, middle layer and upper layer.
The size of PMMA plate is (5~7) cm* (4~6) cm* (1~2) cm, wherein middle layer with that area is cut among top plate is identical
Circular hole, area be 1~3cm2, middle plate side reserves the circular hole that diameter is 0.3~0.5cm, the big hole phase with plate center
It is logical, for injecting electrolyte.
Negative electrode material is the zinc metal sheet of sanding and polishing, and electrolyte is KOH and Zn (Ac)2Mixed solution, it is preferred that electrolyte is
Concentration is 4~6mol/L KOH and 0.2mol/L Zn (Ac)2Mixed solution.
The present invention is to the structure of the zinc-air battery battery there is no specifically limited, and well known to a person skilled in the art zinc
Air cell battery structure.
In the present invention, the assembling sequence of the zinc-air battery battery is as follows: lower plywood, the zinc metal sheet after polishing, there are
With the pellosil of middle plate circular hole circular hole in the same size, with a thickness of 0.8mm, middle plate, there are in the same size with middle plate circular hole
The pellosil of circular hole, with a thickness of 0.8mm, anode electrode piece, top plate, then entire component is screwed in quadrangle.Electrolysis
Liquid is blocked after excluding bubble with rubber stopper by injecting in the aperture of side.
FeCo of the present invention8S8@rGO catalyst has the synergistic effect between multi-element metal, can be by regulating and controlling metal
Electronic structure promote its and be catalyzed latent active, while FeCo8S8The In-situ reaction structure formed with redox graphene, can
To promote the electric conductivity and stability of catalyst entirety, electro-catalysis oxygen reduction and water oxygenization can be shown in alkaline solution
Excellent performance.Based on the zinc and air cell of catalyst assembling, show to combine and urge with business noble metal (platinum carbon+ruthenic oxide)
The charge and discharge potential difference and stability that agent compares favourably.Therefore FeCo provided by the invention8S8@rGO catalyst has at low cost, property
The good advantage of energy can be used as efficient Oxygen Electrode Material applied to zinc and air cell.
As without particularly pointing out, the raw materials used in the present invention and reagent are commercial product.
For a further understanding of the present invention, below with reference to embodiment to base metal bi-functional oxygen electrode provided by the invention
Catalyst and preparation method and zinc-air battery anode and zinc-air battery are illustrated, protection scope of the present invention not by with
The limitation of lower embodiment.
1 FeCo of embodiment8S8The preparation of@GO
In a clean 50mL three neck round bottom, 0.0078g ferric acetyl acetonade and 0.0458g acetylacetone,2,4-pentanedione is added
Cobalt, the GO after then weighing 5mg freeze-drying are placed in 1mL oleyl amine, and ultrasonic disperse is added in flask, adds 5mL 18
Alkene, 0.2mL oleic acid and 0.2mL spicy thioalcohol.In N2Under protection, reaction system is warming up to 150 DEG C in 20min, and keep
Then 30min is warming up to 260 DEG C with the heating rate of 10 DEG C/min, keep natually cooled to room temperature after reaction 30min.It takes
Centrifugation obtains black product out, then washs centrifugation 2 times with EtOH Sonicate, then be centrifuged 2 times with n-hexane supersound washing, last
Before centrifugation, takes out a small amount of sample drop and shot in clean copper on piece for scanning electron microscope, drop is used on 300 mesh copper mesh
In transmission electron microscope shooting and high resolution transmission electron microscopy shooting, the product obtained after being finally centrifuged is placed in 80 DEG C very
It is taken out after empty drying box 8h.Referring to fig. 2 and Fig. 4, Fig. 2 are by the FeCo of oily phase reaction one pot process8S8The scanning electricity of@GO
Sub- microscope photo.Scale is 1 μm in figure.It can be seen that gained FeCo in figure8S8The bouquet being made of nanometer sheet uniformly divides
It is dispersed in the surface of GO substrate.Fig. 4 is the FeCo by oily phase reaction one pot process8S8The transmission electron microscope photo of@GO.
Scale is 500nm in figure, it can be seen that the sharp-edged laminated structure of bouquet shows that bouquet is made of two-dimensional nano piece, separately
The GO substrate of outer drawout can be also observed, and bouquet is closely linked with GO, illustrates FeCo8S8Growth in situ exists
The surface GO.
2 FeCo of embodiment8S8@GO is in NH3Annealing steps in/Ar atmosphere
Product after drying in embodiment 1 is placed in corundum porcelain boat, tube furnace is put into, is passed through NH3/ Ar gaseous mixture (ammonia
The percentage by volume that gas accounts for gaseous mixture is 10%), to be warming up to 400 DEG C with the rate of 5 DEG C/min, keep 2h at such a temperature, with
Temperature fall is cooling afterwards.The step can remove the solvent and surfactant on powder product surface, be translated into hydrophily
Product, and GO is reduced to the rGO that part N is adulterated, to improve its electric conductivity.
Comparative example 1
It in the above-described embodiments, is embodiment FeCo8S8@rGO in bi-functional energy, especially in OER performance relative to
Co9S8@rGO advantageously, using same method and step synthesizes Co9S8@rGO compound simultaneously carries out every characterization and survey to it
Examination is distinguished only in embodiment 1, all 0.0478g acetylacetone cobalts of metal front.
Obtained Co9S8@GO compound is scanned electron microscope and transmission electron microscope observation, as a result see Fig. 3 and
Fig. 5.Fig. 3 is the Co by oily phase reaction one pot process9S8The electron scanning micrograph [email protected] is 1 μm in figure.Figure
In it can be seen that gained Co9S8And the bouquet being made of nanometer sheet, and it is dispersed in the surface of GO substrate.Fig. 5 is to pass through oil
The Co of phase reaction one pot process9S8The transmission electron microscope photo [email protected] is 500nm, Co in figure9S8The pattern of@GO
With FeCo8S8@GO is closely similar, and bouquet is made of two-dimensional nano piece, and bouquet is combined closely with GO.
According to the method for embodiment 2 by above-mentioned Co9S8@GO compound is in NH3Annealing in/Ar atmosphere, obtains Co9S8@rGO
Compound.
3 FeCo of embodiment8S8The XRD and Raman of@rGO is characterized
Product after drying in embodiment 1 is taken out, with mortar grinder, then taking-up is a part of for analyzing and characterizing,
Its phase structure is analyzed with sample water flat pattern high power x-ray diffractometer (Rigaku TTRIII), occurs comparing clearly diffraction
Peak, and and FeCo8S8Standard card JCPDS#290484 it is corresponding, wherein three strongest peak correspond respectively to crystal face (311), (440) and
(222).It is characterized with Raman test, is located at 187,464,510 and 662cm-1The peak at place is FeCo8S8Characteristic peak,
And it is located at 1349 and 1585cm-1The two strong peak at place then corresponds respectively to the peak feature D and the peak G of GO.Concrete outcome is referring to Fig. 6,7
With 8.
4 FeCo of embodiment8S8The electrocatalysis characteristic of@rGO is tested
The product FeCo that will be annealed in embodiment 28S8@rGO is tested for electrocatalysis characteristic, weighs 3mg in centrifuge tube
In, 1mg conductive black is added, the mixed solvent (V of 0.5mL water and isopropanol is then addedWater/VIsopropanol=3:1), ultrasonic 20min
Homogeneous mixture is formed, 10 μ L nafion coating solutions (perfluorinated sulfonic acid-teflon-copolymers solution) are then added, then
Ultrasonic 60min forms prepared Chinese ink shape black mixture.10 μ L mixtures drop is pipetted in glassy carbon electrode surface (load using liquid-transfering gun
Amount is 0.3mg/cm2), after to be dried, electrode is placed in the KOH solution of 0.1mol/L, using three-electrode system, glass-carbon electrode
As working electrode, as reference electrode, platinum filament is used as to electrode Ag/AgCl, utilizes rotating circular disk device and CHI 760d electricity
ORR the and OER performance of chem workstation test material.In ORR test, sweeping speed is 5mV/s, and reverse scanning, voltage range is
0.2-1.0V (Fig. 9).In OER test, sweeping speed is 5mV/s, and forward scan, voltage range is 1.2-1.7V (Figure 10).Pt/C
And RuO2Slurry preparation process and test process method it is same as described above.The Co that comparative example 1 obtains9S8@rGO is also according to above-mentioned
Method is tested.As a result referring to Fig. 9 and Figure 10.
The preparation of 5 zinc-air battery of embodiment
To air diffusion layer, 0.1g acetylene black, 0.2g carbon black are first mixed into dispersion in ethanol, ultrasonic 10min then adds
Enter 0.7g PTFE solution (polytetrafluoroethylsolution solution), then uniform stirring 60min, stirring to be placed on removal in 80 DEG C of baking ovens more
Remaining ethyl alcohol is rolled into the film of 300nm thickness until mixture becomes to take out after dough under roll squeezer.For catalyst
Layer, the 15mg FeCo obtained after first being handled through embodiment 28S8@rGO catalyst and 5mg carbon black are mixed and dispersed in ethyl alcohol
In, 15mg PTFE solution is then added in same ultrasound 10min, and after stirring 60min, it is extra to be placed in removal in 80 DEG C of baking ovens
Ethyl alcohol take out until mixture becomes dough and roll-in form a film and guarantees the load capacity of catalyst for 5mg/cm2.It completes
After aforesaid operations, by after roll-in air diffusion layer and Catalytic Layer be fitted in the two sides of nickel foam respectively, using roll-in,
Make air diffusion layer and Catalytic Layer that nickel foam be completely covered and be pressed into the gap of foam nickel skeleton, after roll-in with a thickness of
0.4mm.Finally electrode slice is placed in Muffle furnace, in air 320 DEG C of heating 20min, is taken out after cooling stand-by.It is finally electricity
The assembling (Figure 13) in pond, battery case use PMMA material, and negative electrode material is the zinc metal sheet of sanding and polishing, and anode is the above process
The electrode of preparation, electrolyte are concentration 6mol/L KOH and 0.2mol/L Zn (Ac)2Mixed solution.Positive side battery case has
Area 3cm2Round hole, convenient for anode contacted with air, make oxygen participate in react.
Similarly, corresponding load business Pt/C and Pt/C+RuO2Mixture electrode preparation zinc-air battery also according to
Prepared by the above method, difference is only that FeCo8S8@rGO catalyst replaces with the Pt/C or Pt/C+ of equal quality
RuO2Mixture (Pt/C+RuO2Pt/C and RuO in mixture250%) mass fraction respectively accounts for.
The test of 6 zinc-air battery performance of embodiment
During battery testing, using three-electrode system, working electrode is the anode electrode piece of supported catalyst, reference
Electrode and be all zinc metal sheet to electrode, is tested using CHI 760d electrochemical workstation.Charge and discharge LSV is tested, speed is swept
For 5mV/s, forward scan, voltage range is 0.6-2.2V (Figure 11).From interpretation of result, FeCo is loaded8S8The battery of/rGO electrode
In discharge regime, overpotential is than load business Pt/C and supporting Pt/C+RuO2The electrode overpotential of mixture is bigger, but
Charging stage loads FeCo8S8The electrode of/rGO has apparent advantage.For charge and discharge cycles stability test, test electricity
Current density is 10mA cm-2, charge 400s, and electric discharge 400s is a circulation, and test obtains the cyclic curve of 200 circles.Analysis knot
Fruit: being 10mA cm in current density-2In the case where, it is corresponding to load FeCo8S8/ rGO, business Pt/C and Pt/C+RuO2It is mixed
The electrode of conjunction object is respectively 0.86V, 0.95V and 0.75V as the battery charging and discharging potential difference of anode.After the circle of circulation 200, electricity
Pond performance is decayed, and FeCo is loaded8S8The battery charging and discharging potential difference of/rGO is 0.97V, loads business Pt/C and load
Pt/C+RuO2The battery charging and discharging potential difference of mixture is respectively 1.58V and 0.90V, therefore the corresponding potential difference of three increases
Long value is 0.11V, 0.63V and 0.15V, can be seen that load FeCo from the data8S8The battery of/rGO has in stability
Bigger advantage
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of base metal bi-functional oxygen electrode catalyst, which is characterized in that be nanometer Fe Co8S8With redox graphene
Compound.
2. catalyst according to claim 1, which is characterized in that be using redox graphene as substrate and described
Substrate surface is compound by FeCo8S8The nanometer bouquet of nanometer sheet composition.
3. catalyst according to claim 2, which is characterized in that the diameter of the nanometer bouquet is 50~300nm；
The redox graphene account for the base metal bi-functional oxygen electrode catalyst mass percentage be 20%~
60%.
4. a kind of preparation method of the base metal bi-functional oxygen electrode catalyst as described in claims 1 to 3 any one,
It is characterized in that, comprising the following steps:
A) using ferric acetyl acetonade and acetylacetone cobalt as metal precursor, by the metal precursor, graphene oxide, thio-alcohol
Compound, surfactant and high boiling organic solvent mixing are warming up to 220~260 DEG C, reaction under the conditions of protective atmosphere
15~60min obtains reaction product；
B) containing NH3Ar oxygen mixture in, it is cooling after the reaction product is annealed, obtain the double function of base metal
It can oxygen electrode catalyst FeCo8S8@rGO。
5. according to the method described in claim 4, it is characterized in that, the sulfur alcohol compound is selected from spicy thioalcohol；
The surfactant is selected from oleic acid；
The high boiling organic solvent is selected from oleyl amine and octadecylene mixed solvent, and the volume ratio of the oleyl amine and octadecylene is 1:(2
~5)；
The protective atmosphere condition is selected from nitrogen；
The molar ratio of the ferric acetyl acetonade and acetylacetone cobalt is 1:8；
The additional amount of the graphene oxide is 10~50mg/mmol metal precursor；
The additional amount of the high boiling organic solvent is 20~50mL/mmol metal precursor；
The additional amount of the sulfur alcohol compound is greater than 0.25mL/mmol metal precursor；
The additional amount of the surfactant is 0.5~2mL/mmol metal precursor.
6. according to the method described in claim 4, it is characterized in that, step A) program of the heating are as follows:
120~150 DEG C are risen in 10~30min from room temperature, and retention time is 30~60min, then sets heating rate
For 5~10 DEG C/min, reach 220~260 DEG C of reaction temperature, the reaction time is 15~60min；
Step B) in, the heating rate of the annealing is 2.5~10 DEG C/min, and the temperature of the annealing is 400~450 DEG C, institute
The time for stating annealing is 2~4h；
It is described to contain NH3Ar oxygen mixture in NH3Volume content be 5~15%.
7. a kind of zinc-air battery anode, which is characterized in that including the base metal as described in claims 1 to 3 any one
Bi-functional oxygen electrode catalyst, or the base metal that preparation method as described in claim 4~6 any one is prepared
Bi-functional oxygen electrode catalyst.
8. zinc-air battery anode according to claim 7, which is characterized in that including the catalyst being sequentially compounding
Layer, nickel foam support frame and air diffusion layer.
9. a kind of zinc-air battery, which is characterized in that including anode, cathode, electrolyte and battery case, the just extremely right
It is required that zinc-air battery described in 7 or 8 is positive.
10. zinc-air battery according to claim 9, which is characterized in that the battery case uses PMMA material, cathode
Material is the zinc metal sheet of sanding and polishing, and electrolyte is KOH and Zn (Ac)2Mixed solution.
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| CN116417625A (en) * | 2023-06-09 | 2023-07-11 | 超威电源集团有限公司 | Preparation method of air electrode and high-power zinc-air battery |
| CN116417625B (en) * | 2023-06-09 | 2023-09-19 | 超威电源集团有限公司 | Preparation method of air electrode and high-power zinc-air battery |
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