CN105655670B - A kind of magnesium air battery manganese oxide overlong nanowire/graphene elctro-catalyst controllable method for preparing - Google Patents
A kind of magnesium air battery manganese oxide overlong nanowire/graphene elctro-catalyst controllable method for preparing Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
Abstract
The summary of the invention of this patent is to provide a kind of magnesium air battery manganese oxide overlong nanowire/graphene elctro-catalyst controllable method for preparing, three hexyl myristyl phosphonium chlorides are applied in preparation process, the structure directing agent that the ionic liquid of three normal-butyl myristyl phosphonium chlorides is monodimension nanometer material, for inducing with Mn3O4For the manganese oxide nanometer material of representative, lay the foundation for the performance of Effective Regulation nanometer electrical catalyst.The Mn for being clearly advantageous that experiment parameter is controllable, combined coefficient is high, being loaded on graphene of the novel ion liquid assisted microwave synthesis radiation method3O4The uniform content of electro-catalysis overlong nanowire, the synthetic method are Mn3O4Overlong nanowire/graphene elctro-catalyst provides experiment experience to improve the comprehensive electrochemical of magnesium air battery.
Description
[technical field]: the invention belongs to inorganic nano materials to synthesize field, use more particularly to a kind of magnesium air battery
Manganese oxide overlong nanowire/graphene elctro-catalyst controllable method for preparing.
[background technique]:
The demand that the energy is increasingly urgent to constantly motivates people to the dense of energy efficient storage and study on the transformation and application
Interest.It is the energy density height of metal-air battery, long service life, at low cost in numerous battery systems.Particularly, magnesium is empty
Pneumoelectric pond is one of high-energy chemistry power supply, is made of anode, cathode, diaphragm, battery case and electrolyte；The energy storage system
Distinguishing feature is that positive electrode active materials are oxygen in air, and negative electrode material uses high pure metal magnesium sheet or magnesium base alloy piece
([1] Xue, Yejian et al.J.Power Sources, 297,202-207,2015；[2] Chen, Leanne D.et
Al.J.Phys.Chem.C, 119 (34), 19660-19667,2015；[3] Akhtar, Naveed, et al.Int J.Energy
Res., 39 (3), 303-316,2015；[4] Dinesh, M.Mayilvel et al.J.Power Sources, 276,32-38,
2015；[5] Wang, Naiguang et al.Electrochim.Acta, 149,193-205,2014；[6] Yuasa,
Motohiro et al.Mater.Trans., 55 (8), 1202-1207,2014).The theoretical specific energy of magnesium air battery is up to
3910Wh/kg, capacity are significantly larger than lithium ion battery and zinc-air battery；Magnesium air battery possess high instantaneous output current,
Stable discharging platform and use power, continuous discharge condition are excellent, are suitble to the advantages that high current, high current density pulsed discharge,
Applied to fields such as radio relay station, navigation light, mine emergency power supply, disaster relief first aid illumination, mobile communication backup power sources
([7] Zhang, Tianran et al.Mater.Horizons, 1 (2), 196-206,2014；[8] Yan, Yajing et
Al.J.Electrochem.Soc., 161 (6), A974-A980,2014；[9] Xin, Gongbiao et al.Dalton
Trans., 42 (48), 16693-16696,2013；[10] Huang, Guangsheng et al.Mater.Lett., 113,46-
49,2013；[11] Inoishi, Atsushi et al.Chem.Comm., 49 (41), 4691-4693,2013；[12] Shu,
Chaozhu et al.Int.J.Hydrogen Energy, 38 (14), 5885-5893,2013；[13] Milusheva,
T.D.et al.Bulgarian Chem.Commun., 45,140-145,2013；[14] Khoo, Timothy et
Al.Electrochim.Acta, 87,701-708,2013；[15] Bayley, Paul M.et al.Aust.J.Chem., 65
(11), 1542-1547,2012；[16] Ma, Yibin et al.J.Power Sources, 196 (4), SI, 2346-2350,
2011；[17] Li, Weiyang et al.Angew.Chem.Int.Ed., 45 (36), 6009-6012,2006).It is more crucial
, positive electrocatalysis material be determine magnesium air battery an important factor for one of.
And electro catalytic electrode material is the key that promote magnesium air battery comprehensive electrochemical.Wherein, metal oxide
Mn3O4Have the characteristics that raw material is easy to get, price is low, nontoxic and environmental-friendly, is that one kind has light to answer in magnesium air battery
With the extraordinary electrocatalysis material of future.But the material needs the key scientific problems faced to be: how to improve regular pattern
Electron conduction.Mn3O4Basic reason be its extremely low conductivity (10-7~10-7S/cm), therefore Mn is strongly limited3O4?
Electron transfer number and open-circuit voltage in magnesium air battery.The good news is graphene is a kind of new function two of discovered in recent years
Dimension nano material possesses high-specific surface area, superior electrical conductivity and chemical stabilization property, and can be used as Mn3O4Nano material it is good
Good vector, and improve Mn3O4Electron conduction, and prevent agglomeration traits in application process.
For key scientific problems existing for magnesium air battery electro-catalysis nano material, it is empty that the invention patent provides a kind of magnesium
Pneumoelectric pond manganese oxide overlong nanowire/graphene elctro-catalyst controllable method for preparing, in particular to Mn3O4Overlong nanowire/stone
The design of black alkene elctro-catalyst synthesizes.It is that starting material efficiently prepares stone that wherein graphene, which is with mesocarbon microspheres (MCMB),
Black alkene ultrathin nanometer piece.Mesocarbon microspheres is to be heat-treated the multicore condensed-nuclei aromatics compound of coal tar asphalt in polymerization process
Then middle formation mesophasespherule uses hot centrifugal separation by the mesophasespherule for generating regular size by having in mother liquor
The mesocarbon microspheres of graphite laminate ordered structure is made in effect separation, then the last handling process through being commonly improved.And in Mn3O4It is super
In the composite material preparation system of long nano wire/graphene, by three hexyl myristyl phosphonium chlorides (No. CAS: 258864-54-
9, molecular formula is
) and three
(No. CAS: 81741-28-8, molecular formula is normal-butyl myristyl phosphonium chloride
) mixed ionic liquid as Mn3O4The structure directing agent of overlong nanowire growth, optimizes Mn3O4Electronic conduction
Property, improve graphene electrocatalysis characteristic.This ionic liquid assisted microwave synthesis radiation preparation Mn3O4Overlong nanowire/graphene electricity is urged
The remarkable advantage of agent method is: efficiently preparing, experiment condition is mild, reaction rate is controllable, reproducible, target yield is high
Deng, through rotating disk electrode (r.d.e) test show: the transfer electron number under different potentials of the material reach 3.5~3.9 electronics it
Between, show the electrode catalyst performance for being substantially better than simple graphene.The Mn of microwave irradiation preparation3O4Overlong nanowire/graphite
Alkene elctro-catalyst provides necessary theoretical basis and practical experience in terms of the optimization of oxygen catalytic performance in magnesium air battery.
[summary of the invention]: the summary of the invention of this patent be to provide a kind of magnesium air battery manganese oxide overlong nanowire/
Graphene elctro-catalyst controllable method for preparing applies three hexyl myristyl phosphonium chlorides, three normal-butyls 14 during the preparation process
Structure directing agent of the mixed ionic liquid of alkyl phosphonium chloride as monodimension nanometer material, effectively induction is with Mn3O4For the oxygen of representative
Change manganese nano material, provides Research foundation to regulate and control the performance of nanometer electrical catalyst.Novel ion liquid assisted microwave synthesis radiation
The Mn for being clearly advantageous that experiment parameter is controllable, combined coefficient is high, being loaded on graphene of method3O4The load of electro-catalysis overlong nanowire
Carrying capacity is uniform, which is Mn3O4Overlong nanowire/graphene elctro-catalyst comprehensive electrification in magnesium air battery
It learns performance optimization and provides invaluable experience.
[technical solution of the present invention]: the invention patent provides a kind of magnesium air battery manganese oxide overlong nanowire/stone
Black alkene elctro-catalyst controllable method for preparing, synthesis step are divided into the preparation of (A) graphene and (B) Mn3O4Overlong nanowire/graphene
Composite material synthesizes two parts.
(A) prepared by graphene: obtaining high catalysis after, heat treatment modified using hummers method using mesocarbon microspheres as raw material
Activated Graphite alkene provides necessary technology and supports.Specific experiment step is:
The first, 2.0000 grams of MCMB that average diameter is 15 microns are weighed to pour into 250 milliliters of round-bottomed flasks, is placed in 0 DEG C
Ice water mixes and is slowly added to 50 milliliters of concentrated sulfuric acids in bath, and magnetic agitation 1 hour；
The second, by 7.5000 grams of KMnO4Solid powder is slowly added into the material that the first step obtains, and continues 5 points of stirring
150mL distilled water is added dropwise in clock, and maintaining solution temperature is 95 DEG C；
Third, the reaction solution for obtaining second step, which are placed in, to be equipped in normal pressure microwave radiation reactor, equipped with reflux
Cooling device, the cooling water inlet temperature of cooling tube is 15 DEG C, outlet temperature is 20 DEG C, cooling water flow 2L/min, reaction
Power is 700 watts, and reaction temperature is 100 DEG C, sustained response 15 minutes；Then 32 milliliter 30% of H is added dropwise2O2Solution, then
It is fitted into microwave reactor and reacts 10 minutes for 700 watts；
4th, terminate, after solution is cooled to room temperature wait react, use supercentrifuge with 8000 gained black suspension
Rev/min revolving speed be centrifuged 10min, using distilled water rinse 8 times repeatedly, and dry 24 hours in 80 DEG C of baking ovens；Gained is dry
Graphene 800 DEG C heat preservation 10 hours in tube furnace under high-purity argon gas protection, obtain graphene nano sheet material, a diameter of
5~15 microns, with a thickness of 1~100nm.The radiation effects of microwave irradiation and chemical exfoliation interweave jointly in this method
In the graphite laminate structure of MCMB, to obtain the good graphene nano material of dispersibility.
(B)Mn3O4Overlong nanowire/graphene composite material synthesis, specific experiment scheme is: with above-mentioned (A) step institute
Graphene nano sheet material is negative carrier material, manganese salt is with 50% manganese nitrate Mn (NO3)2Solution, manganese sulfate monohydrate (MnSO4·
H2O) be raw material, three hexyl myristyl phosphonium chlorides, three normal-butyl myristyl phosphonium chlorides ionic liquid be 1-dimention nano material
The structure directing agent of material, for inducing with Mn3O4For the manganese oxide nanometer material of representative, it is solvent with distilled water, utilizes ionic liquid
Body assisted microwave synthesis radiation method prepares Mn3O4Overlong nanowire/grapheme material, specific synthetic method are as follows:
The first, 0.5000 gram of graphene is weighed, 50% manganese nitrate (Mn (NO is measured3)2) 10 milliliters of solution, manganese sulfate monohydrate
(MnSO4·H2O it) 0.1200 gram, is dissolved in 100 milliliters of distilled water, to prepare precursor solution；Weigh three hexyls 14
0.1000~1.0000 gram of ionic liquid mixture of alkyl phosphonium chloride and three normal-butyl myristyl phosphonium chlorides, three hexyls 14
Alkyl phosphonium chloride: the weight ratio of three normal-butyl myristyl phosphonium chlorides is 1: 1~10: 1；
The second, 0.3000 gram of potassium permanganate powder is weighed, is added 20 milliliters of distilled water, high-speed stirred 10 minutes is to completely molten
Solution obtains uniform solution；
The solution that first and second steps obtain is sufficiently mixed by third, and high-speed stirred 15 minutes on magnetic stirring apparatus；
4th, the reaction solution obtained third step, which is sufficiently mixed, to be placed in normal pressure microwave radiation reactor, is furnished with
Flow back cooling device, and the cooling water inlet temperature of cooling tube is 15 DEG C, outlet temperature is 20 DEG C, cooling water flow 2L/min,
Reaction power is 300~700 watts, and reaction temperature is 80~100 DEG C, sustained response 30~120 minutes；
5th, after reaction end and reaction solution are cooled to room temperature, by the distilled water rinse 10 of gained brownish black suspension
It~12 times, then uses ethyl alcohol rinse 1 time again, and 20 hours dry in 60 DEG C of drying boxes, i.e. Mn3O4Overlong nanowire/graphene
Elctro-catalyst nano material, wherein Mn3O4The JCPDS card number of overlong nanowire is 1-1127, space group I41/amd
(no.141),Show through sem analysis test: Mn3O4The surface of overlong nanowire
Smooth, size uniformity, diameter 100nm, length are 1~10 micron；Mn3O4Weight ratio with graphene is 2: 1.
A kind of magnesium air battery manganese oxide overlong nanowire/graphene elctro-catalyst controllable method for preparing, it is special
Sign is that the air electrode of magnesium air battery is assembled by waterproof ventilative layer, electro-catalysis conductive layer, order from outside to inside according to
Secondary is waterproof ventilated membrane, currect collecting net and elctro-catalyst conductive layer；Wherein, waterproof ventilated membrane is by ptfe emulsion, sulfuric acid
Sodium, high surface acetylene black uniformly mix, because ptfe emulsion have good adhesion due to so that raw material is sticked into paste, then
Waterproof ventilated membrane is obtained, after densification with a thickness of 100~550 microns；Electrocatalyst layers are Mn3O4Overlong nanowire/graphene electricity
Catalyst, ptfe emulsion, high-specific surface area acetylene black uniformly mix, weight ratio 5: 4: 1；And after mixing 20min,
Recycle tablet press machine in 2MPa pressure densification 1min, to obtain the hydrogen reduction efficient catalytic film that film surface is smooth, density is uniform, film
Between 100~550 microns thick.Electrolyte group becomes 2.6M Mg (NO3)2And 3.6MNaNO2Neutral compounding electrolyte, add simultaneously
Add three hexyl myristyl phosphonium chlorides of the molar ratio 1: 1 of 5~15wt%: the ionic liquid of three normal-butyl myristyl phosphonium chlorides
Auxiliary additive.Constant-current discharge curve of the magnesium air battery assembled under different electric current working conditions uses Land
CT2001A electro-chemical test work station carries out discharge capacity test, and test result shows: Mn3O4Overlong nanowire/graphene is multiple
Closing the magnesium air battery that nano material is assembled has good discharge capacity and cathode utilization rate.
[advantages of the present invention and effect]: the invention patent relates to a kind of magnesium air battery with manganese oxide overlong nanowire/
Graphene elctro-catalyst controllable method for preparing has the following advantages and beneficial effects: that 1, ionic liquid assisted microwave synthesis radiation method closes
At with Mn3O4For the manganese oxide nanometer material of representative, significant contribution is made for the performance of Effective Regulation nanometer electrical catalyst.2, should
The remarkable advantage of novel ion liquid assisted microwave synthesis radiation method is to prepare that experiment condition is quick, experiment parameter is controllable, combined coefficient
Mn that is high, being loaded on graphene3O4The uniform content of electro-catalysis overlong nanowire.3,Mn3O4Overlong nanowire/graphene electricity is urged
Agent oxygen catalysis synthetic chemistry performance in magnesium air battery provides necessary theoretical basis and practical experience.
[Detailed description of the invention]:
Fig. 1 is synthesis Mn3O4Overlong nanowire/graphene elctro-catalyst product X-ray diffraction analysis figure (XRD)
Fig. 2 is synthesis Mn3O4Overlong nanowire/graphene elctro-catalyst product low power scanning electron microscope diagram
Fig. 3 is synthesis Mn3O4Overlong nanowire/graphene elctro-catalyst product high power scanning electron microscope diagram
[specific embodiment]:
Embodiment 1:
A kind of magnesium air battery manganese oxide overlong nanowire/graphene elctro-catalyst controllable method for preparing, synthesis step
It is divided into the preparation of (A) graphene and (B) Mn3O4Overlong nanowire/graphene composite material synthesizes two parts.
(A) prepared by graphene: obtaining high catalysis after, heat treatment modified using hummers method using mesocarbon microspheres as raw material
Activated Graphite alkene provides necessary technology and supports.Specific experiment step is: the first, weighing average diameter is 2 grams of MCMB of 15 microns
It pours into 250 milliliters of round-bottomed flasks, round-bottomed flask is placed in 0 DEG C of ice water and is mixed in bath, and 50 milliliters of concentrated sulfuric acids are added, magnetic force stirs
It mixes 1 hour；The second, by 7.5000 grams of KMnO4Solid powder is slowly added into the material that the first step obtains, and continues 5 points of stirring
150mL distilled water is added dropwise in clock, and maintaining the temperature of reaction solution is 95 DEG C；Third, the reaction solution for obtaining second step are set
In being equipped in normal pressure microwave radiation reactor, equipped with reflux cooling device, the cooling water inlet temperature of cooling tube is 15 DEG C,
Outlet temperature is 20 DEG C, cooling water flow 2L/min, and reaction power is 700 watts, and reaction temperature is 100 DEG C, sustained response 15
Minute；Then 32 milliliter 30% of H is added dropwise2O2Solution is reloaded into microwave reactor and reacts 10 minutes；4th, wait react
After end, solution are cooled to room temperature, supercentrifuge is used to be centrifuged with 8000 revs/min of revolving speed gained black suspension
10min is 24 hours dry using distilled water rinse 8 times repeatedly, and in 80 DEG C of baking ovens；The dry graphene of gained is in high-purity argon gas
Under protection in tube furnace 800 DEG C keep the temperature 10 hours, obtain graphene nano sheet material, a diameter of 5~15 microns, thickness 1
~100nm.
(B)Mn3O4Overlong nanowire/graphene composite material preparation, specific experiment scheme is: obtained by above-mentioned (A) step
Graphene nano sheet material is negative carrier material, and manganese salt is with 50% manganese nitrate Mn (NO3)2Solution, manganese sulfate monohydrate (MnSO4·H2O)
For raw material, three hexyl myristyl phosphonium chlorides, three normal-butyl myristyl phosphonium chlorides ionic liquid be monodimension nanometer material
Structure directing agent, for inducing with Mn3O4It is solvent with distilled water for the manganese oxide nanometer material of representative, it is auxiliary using ionic liquid
Microwave irradiation is helped to prepare Mn3O4Overlong nanowire/grapheme material, specific synthetic method are as follows: first, weighing graphene
0.5000 gram, measure 50% manganese nitrate (Mn (NO3)2) 10 milliliters of solution, manganese sulfate monohydrate (MnSO4·H2It O) 0.1200 gram, will
It is dissolved in 100 milliliters of distilled water, to prepare precursor solution；Weigh three hexyl myristyl phosphonium chlorides and three normal-butyls ten
0.2000 gram of the ionic liquid mixture of tetraalkyl phosphonium chloride, three hexyl myristyl phosphonium chlorides: three normal-butyl myristyl chlorine
The weight ratio for changing phosphine is 2: 1.The second, 0.3000 gram of potassium permanganate powder is weighed, 20 milliliters of distilled water are added, high-speed stirred 10 is divided
Clock is to being completely dissolved to obtain uniform solution；The solution that first and second steps obtain is sufficiently mixed by third, and in magnetic stirring apparatus
Upper high-speed stirred 15 minutes；4th, the reaction solution obtained third step, which is sufficiently mixed, is placed on normal pressure microwave radiation reactor
In, equipped with reflux cooling device, the cooling water inlet temperature of cooling tube is 15 DEG C, outlet temperature is 20 DEG C, cooling water flow
For 2L/min, reaction power is 350 watts, and reaction temperature is 100 DEG C, sustained response 30 minutes；5th, reaction terminates and reacts molten
After liquid is cooled to room temperature, by gained brownish black suspension with distilled water rinse 10 times, then use ethyl alcohol rinse 1 time again, and in 60
It is 20 hours dry in DEG C drying box, i.e. Mn3O4Overlong nanowire/graphene elctro-catalyst nano material, wherein Mn3O4Overlength is received
The JCPDS card number of rice noodles is 1-1127, space group is I41/amd (no.141),
(such as Fig. 1)；5~35 degree steamed bun peak for graphene nano material of the measured XRD spectra at 2 angles θ.Show through SEM test:
Mn3O4The surface of overlong nanowire is smooth, size uniformity, a diameter of 100nm, and length is 1~10 micron (such as Fig. 2-3).
Mn3O4Weight ratio with graphene is 2: 1.The air electrode of magnesium air battery by waterproof ventilative layer, electro-catalysis conductive layer assembling and
At order from outside to inside is waterproof ventilated membrane, currect collecting net and elctro-catalyst conductive layer；Wherein, waterproof ventilated membrane is by poly- four
Vinyl fluoride lotion, sodium sulphate, high surface acetylene black uniformly mix, because ptfe emulsion have good adhesion due to make original
Material sticks into paste, then waterproof ventilated membrane is obtained after densification, with a thickness of 100~550 microns；Electrocatalyst layers are Mn3O4Overlength
Nano wire/graphene elctro-catalyst, ptfe emulsion, high-specific surface area acetylene black uniformly mix, weight ratio 5: 4:
1；And after mixing 20min, recycle tablet press machine in 2MPa pressure densification 1min, to obtain the oxygen that film surface is smooth, density is uniform
Efficient catalytic film is restored, film thickness is between 100~550 microns.Electrolyte group becomes 2.6M Mg (NO3)2And 3.6MNaNO2In
Property compounding electrolyte, while adding three hexyl myristyl phosphonium chlorides of the molar ratio 1: 1 of 5wt%: three normal-butyl myristyls
The ionic liquid auxiliary additive of phosphonium chloride.The magnesium air battery assembled is used in the constant-current discharge curve of different current densities
Land CT2001A electro-chemical test work station carries out discharge capacity test, and test result shows: Mn3O4Overlong nanowire/graphite
The magnesium air battery that alkene composite nano materials are assembled has good discharge capacity and cathode utilization rate.
Embodiment 2:
A kind of magnesium air battery manganese oxide overlong nanowire/graphene elctro-catalyst controllable method for preparing, synthesis step
It is divided into the preparation of (A) graphene and (B) Mn3O4Overlong nanowire/graphene composite material synthesizes two parts.
(A) prepared by graphene: with part (A) of embodiment 1；
(B)Mn3O4Overlong nanowire/graphene composite material preparation, specific experiment scheme is: obtained by above-mentioned (A) step
Graphene nano sheet material is negative carrier material, and manganese salt is with 50% manganese nitrate Mn (NO3)2Solution, manganese sulfate monohydrate (MnSO4·H2O)
For raw material, three hexyl myristyl phosphonium chlorides, three normal-butyl myristyl phosphonium chlorides ionic liquid be monodimension nanometer material
Structure directing agent, for inducing with Mn3O4It is solvent with distilled water for the manganese oxide nanometer material of representative, it is auxiliary using ionic liquid
Microwave irradiation is helped to prepare Mn3O4Overlong nanowire/grapheme material, specific synthetic method are as follows: first, weighing graphene
0.5000 gram, measure 50% manganese nitrate (Mn (NO3)2) 10 milliliters of solution, manganese sulfate monohydrate (MnSO4·H2It O) 0.1200 gram, will
It is dissolved in 100 milliliters of distilled water, to prepare precursor solution；Weigh three hexyl myristyl phosphonium chlorides and three normal-butyls ten
0.3000 gram of the ionic liquid mixture of tetraalkyl phosphonium chloride, wherein three hexyl myristyl phosphonium chlorides: the three normal-butyl tetradecanes
The weight ratio of base phosphonium chloride is 1: 1.The second, 0.3000 gram of potassium permanganate powder is weighed, 20 milliliters of distilled water, high-speed stirred is added
10 minutes to being completely dissolved to obtain uniform solution；The solution that first and second steps obtain is sufficiently mixed, and stirs in magnetic force by third
Mix high-speed stirred 15 minutes on device；4th, the reaction solution obtained third step, which is sufficiently mixed, is placed on normal pressure microwave radiation instead
It answers in device, equipped with reflux cooling device, the cooling water inlet temperature of cooling tube is 15 DEG C, outlet temperature is 20 DEG C, cooling water
Flow is 2L/min, and reaction power is 400 watts, and reaction temperature is 100 DEG C, sustained response 45 minutes；5th, reaction terminates and anti-
After answering solution to be cooled to room temperature, by gained brownish black suspension with distilled water rinse 10 times, then use ethyl alcohol rinse 1 time again, and
It is 20 hours dry in 60 DEG C of drying boxes, i.e. Mn3O4Overlong nanowire/graphene elctro-catalyst nano material, wherein Mn3O4It is super
The JCPDS card number of long nano wire is 1-1127, space group is I41/amd (no.141),
Mn3O4Overlong nanowire is uniformly distributed on the surface of graphene, and the pattern of nano wire is uniform, and diameter is distributed between 100~150nm,
Length is 1~10 micron.Magnesium air battery performance test obtains advantageous effects with embodiment 1, the material.
Embodiment 3:
A kind of magnesium air battery manganese oxide overlong nanowire/graphene elctro-catalyst controllable method for preparing, synthesis step
It is divided into the preparation of (A) graphene and (B) Mn3O4Overlong nanowire/graphene composite material synthesizes two parts.
(A) prepared by graphene: with part (A) of embodiment 1；
(B)Mn3O4Overlong nanowire/graphene composite material preparation, specific experiment scheme is: obtained by above-mentioned (A) step
Graphene nano sheet material is negative carrier material, and manganese salt is with 50% manganese nitrate Mn (NO3)2Solution, manganese sulfate monohydrate (MnSO4·H2O)
For raw material, three hexyl myristyl phosphonium chlorides, three normal-butyl myristyl phosphonium chlorides ionic liquid be monodimension nanometer material
Structure directing agent, for inducing with Mn3O4It is solvent with distilled water for the manganese oxide nanometer material of representative, it is auxiliary using ionic liquid
Microwave irradiation is helped to prepare Mn3O4Overlong nanowire/grapheme material, specific synthetic method are as follows: first, weighing graphene
0.5000 gram, measure 50% manganese nitrate (Mn (NO3)2) 10 milliliters of solution, manganese sulfate monohydrate (MnSO4·H2It O) 0.1200 gram, will
It is dissolved in 100 milliliters of distilled water, to prepare precursor solution；Weigh three hexyl myristyl phosphonium chlorides and three normal-butyls ten
0.3500 gram of the ionic liquid mixture of tetraalkyl phosphonium chloride, three hexyl myristyl phosphonium chlorides: three normal-butyl myristyl chlorine
The weight ratio for changing phosphine is 2: 1.The second, 0.3000 gram of potassium permanganate powder is weighed, 20 milliliters of distilled water are added, high-speed stirred 10 is divided
Clock is to being completely dissolved to obtain uniform solution；The solution that first and second steps obtain is sufficiently mixed by third, and in magnetic stirring apparatus
Upper high-speed stirred 15 minutes；4th, the reaction solution obtained third step, which is sufficiently mixed, is placed on normal pressure microwave radiation reactor
In, equipped with reflux cooling device, the cooling water inlet temperature of cooling tube is 15 DEG C, outlet temperature is 20 DEG C, cooling water flow
For 2L/min, reaction power is 700 watts, and reaction temperature is 100 DEG C, sustained response 120 minutes；5th, reaction terminates and reacts
After solution is cooled to room temperature, by gained brownish black suspension with distilled water rinse 12 times, then use ethyl alcohol rinse 1 time again, and in
It is 20 hours dry in 60 DEG C of drying boxes, i.e. Mn3O4Overlong nanowire/graphene elctro-catalyst nano material, wherein Mn3O4Overlength
The JCPDS card number of nano wire is 1-1127, space group is I41/amd (no.141),
Mn3O4Overlong nanowire is evenly distributed on graphene, and surface is smooth, size uniformity, diameter 100nm, and length is 2~10 micro-
Rice.Magnesium air battery performance test obtains advantageous effects with embodiment 1, the material.
Claims (1)
1. a kind of magnesium air battery manganese oxide nano wire/graphene elctro-catalyst controllable method for preparing, synthesis step are divided into
A, graphene preparation and B, Mn3O4Overlong nanowire/graphene composite material synthesizes two parts:
A, prepared by graphene: obtaining high catalytic activity stone after, heat treatment modified using hummers method using mesocarbon microspheres as raw material
Black alkene；Specific experiment step is:
The first, 2.0000 grams of MCMB that average diameter is 15 microns are weighed to pour into 250 milliliters of round-bottomed flasks, is placed in 0 DEG C of ice water
It mixes and is slowly added to 50 milliliters of concentrated sulfuric acids in bath, magnetic agitation 1 hour；
The second, by 7.5000 grams of KMnO4Solid powder is slowly added into the material that the first step obtains, and continues stirring 5 minutes, by
It is added dropwise to 150mL distilled water, maintaining solution temperature is 95 DEG C；
Third, the reaction solution for obtaining second step, which are placed in, to be equipped in normal pressure microwave radiation reactor, equipped with reflux cooling
Device, the cooling water inlet temperature of cooling tube is 15 DEG C, outlet temperature is 20 DEG C, cooling water flow 2L/min, reaction power
It is 700 watts, reaction temperature is 100 DEG C, sustained response 15 minutes；Then 32 milliliter 30% of H is added dropwise2O2Solution is reloaded into
It is reacted 10 minutes for 700 watts in microwave reactor；
4th, terminate, after solution is cooled to room temperature wait react, by gained black suspension use supercentrifuge with 8000 turns/
The revolving speed divided is centrifuged 10min, 24 hours dry using distilled water rinse 8 times repeatedly, and in 80 DEG C of baking ovens；Gained dries graphite
Alkene under high-purity argon gas protection in tube furnace 800 DEG C keep the temperature 10 hours, obtain graphene nano sheet material, a diameter of 5~
15 microns, with a thickness of 1~100nm；
It is characterized by: Mn3O4The synthesis of nano wire/graphene composite material, specific experiment scheme is: graphene nano sheet material
Material is support materials, and manganese salt is with 50% manganese nitrate Mn (NO3)2Solution, manganese sulfate monohydrate MnSO4·H2O is raw material, three hexyls ten
Tetraalkyl phosphonium chloride, three normal-butyl myristyl phosphonium chlorides ionic liquid be monodimension nanometer material structure directing agent, be used for
Induction is with Mn3O4It is solvent with distilled water for the manganese oxide nanometer material of representative, radiates legal system using ionic liquid assisted microwave synthesis
Standby Mn3O4Nano wire/graphene material, specific synthetic method are as follows:
The first, 0.5000 gram of graphene is weighed, 50% manganese nitrate Mn (NO is measured3)210 milliliters of solution, manganese sulfate monohydrate MnSO4·
H20.1200 gram of O is dissolved in 100 milliliters of distilled water, to prepare precursor solution；Weigh three hexyl myristyl chlorine
0.1000~1.0000 gram of ionic liquid mixture for changing phosphine and three normal-butyl myristyl phosphonium chlorides, three hexyl myristyl chlorine
Change phosphine: the weight ratio of three normal-butyl myristyl phosphonium chlorides is 1: 1~10: 1；
The second, 0.3000 gram of potassium permanganate powder is weighed, is added 20 milliliters of distilled water, high-speed stirred 10 minutes is to being completely dissolved
To uniform solution；
The solution that first and second steps obtain is sufficiently mixed by third, and high-speed stirred 15 minutes on magnetic stirring apparatus；
4th, the reaction solution obtained third step, which is sufficiently mixed, to be placed in normal pressure microwave radiation reactor, equipped with reflux
Cooling device, the cooling water inlet temperature of cooling tube is 15 DEG C, outlet temperature is 20 DEG C, cooling water flow 2L/min, reaction
Power is 300~700 watts, and reaction temperature is 80~100 DEG C, sustained response 30~120 minutes；
5th, after reaction end and reaction solution are cooled to room temperature, by the distilled water rinse 10~12 of gained brownish black suspension
It is secondary, it then uses ethyl alcohol rinse 1 time again, and 20 hours dry in 60 DEG C of drying boxes, i.e. Mn3O4Nano wire/graphene elctro-catalyst
Nano material, wherein Mn3O4The JCPDS card number of nano wire is 1-1127, space group is I41/amd (no.141),Show through sem analysis test: Mn3O4The surface of nano wire is smooth, size uniformity, diameter 100nm,
Length is 1~10 micron.
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| CN108520956B (en) * | 2018-05-29 | 2020-05-05 | 铜仁学院 | Preparation method of anode material of aqueous manganese-based ion battery, anode material, electrode and aqueous mixed ion battery |
| CN111933932B (en) * | 2020-08-10 | 2023-08-29 | 苏州科技大学 | In-situ composite specific crystal face growth ZnV in zinc ion battery 2 O 6 Method for preparing/GN-SWCNTS material |
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