CN106654187B - A method of preparing lithium-air battery cobalt iron oxide/multi-walled carbon nanotube composite catalyst - Google Patents
A method of preparing lithium-air battery cobalt iron oxide/multi-walled carbon nanotube composite catalyst Download PDFInfo
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- CN106654187B CN106654187B CN201610911753.7A CN201610911753A CN106654187B CN 106654187 B CN106654187 B CN 106654187B CN 201610911753 A CN201610911753 A CN 201610911753A CN 106654187 B CN106654187 B CN 106654187B
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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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
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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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Lithium-air battery cobalt iron oxide/multi-walled carbon nanotube composite catalyst method is prepared the invention discloses a kind of.The active material of composite catalyst is cobalt iron oxide, and carrier is multi-walled carbon nanotube.Cobalt iron oxide mass percent in catalytic composite material is 4%~10%, and multi-walled carbon nanotube mass percent in catalytic composite material is 90%~96%.The cobalt iron oxide diameter is 30~80nm, and multi-wall carbon nano-tube pipe diameter is 20~100nm.The cobalt iron oxide/multi-wall carbon nano-tube composite material specific surface area is 1600~2200m2·g‑1.Compared with prior art, the preparation method of nano-composite catalyst material provided by the invention is simple, reproducible, raw material is cheap, the features such as haveing excellent performance, is environmental-friendly.
Description
Technical field
The present invention relates to lithium-air battery catalyst technical fields, and in particular to a kind of to prepare lithium-air battery ferro-cobalt
The method of oxide/multi-wall carbon nano-tube composite catalyst.
Background technique
Under the background that global conventional energy resource gradually moves towards that exhausted, environmentally friendly cry grows to even greater heights, clean energy resource is developed and used
Global common recognition is had become with renewable energy.Traditional lithium ion battery is limited by the limitation of positive electrode energy density,
It is difficult to meet the requirement of electric car high-energy density, and lithium-air battery has the energy density of traditional 10 times of lithium battery, because
And become research hotspot.Simultaneously because its just extremely oxygen, the substance for having pollution to environment will not be generated in reaction process, is one
The Green high-capacity energy switching device of kind great potential is expected to become the potentiality of next-generation electric car.
The structure of usual lithium-air battery is made of four parts: anode, electrolyte, diaphragm, cathode (air electrode).Battery
Reaction product and electrolyte decomposition product are deposited in the surface of catalyst and carbon material, block the hole of air electrode, influence oxygen
The diffusion of gas reduces the catalytic performance of catalyst, so that the cyclical stability and high rate performance of lithium-air battery are very poor.
Critical material one of of the elctro-catalyst as lithium-air battery, the electrocatalysis characteristic of material, stability, conduction
The factors such as property, specific surface area, appearance structure have a significant impact to the polarization of lithium-air battery, specific capacity and cycle performance.It is a kind of
Efficient elctro-catalyst can greatly improve the efficiency of lithium-air battery, inhibit the decomposition of electrolyte, to improve the circulation longevity
Life.Therefore, in order to reduce the polarization of lithium-air battery, the performance of battery is improved, the research and development of elctro-catalyst are essential.
Researcher is generally used as lithium air using single transition metal oxide, metal nitride, noble metal etc. at present
The elctro-catalyst of battery.In lithium-air battery, transition metal oxide is the elctro-catalyst of most study, at present to oxidation
Manganese, cobalt oxide, iron oxide, vanadium oxide, nickel oxide etc. are applied to lithium-air battery as the research of elctro-catalyst.Peter
G.Bruce (Journal of Power Sources 174,2007,1177-1182) etc. has studied different type transition metal
The electrocatalysis characteristic of oxide, electrolytic oxidation manganese and cobalt oxide possess preferable discharge capacity, but its specific surface area is smaller, circulation
Performance is not very ideal.Y. Liang (Nature Materials 10,2011,780-786) etc. has studied low temperature synthesis
NiCo2O4Nanocrystalline that there is preferable hydrogen reduction and oxygen performance is precipitated, discharge platform is higher, and charging voltage fails to be effectively reduced, and holds
Amount decaying is very fast.X.Zhang (Journal of Materials Chemistry A4,2016,9390-9393) etc. has studied
NiFe2O4- CNT composite catalyst, specific surface area are only 137.71m2·g-1, overpotential fails to obtain more compared with pure CNT
It is obviously improved, discharges under high current density, charge and discharge platform is shorter, and charging voltage is higher.L Y.Li(Journal of
Materials Chemistry A3,2015,24309-24314) etc. have studied NiCo2O4Nanotube is as lithium-air battery
Elctro-catalyst, specific surface area are only 30.2m2·g-1, pore-size is 3~30nm, and aperture is smaller, is unfavorable for electrochemical reaction
The deposition of the transmission of oxygen and discharging product in the process, discharge platform voltage are that 2.63V still has compared with theoretical voltage 2.96V
Many gaps, and discharge platform is shorter.S.Tansel (Journal of Power Sources 288,2015,36-41) etc. is ground
Nano Co Fe is studied carefully2O4Supported active powdered carbon is as lithium-air battery catalyst, wherein nano Co Fe2O4It is split using high temperature and pressure
Solution obtains, in 100mAg-1Discharge current density under discharge, charge and discharge overpotential is with CoFe in catalyst2O4Content
Increase and increase, and overpotential, in 1.0V or more, charge and discharge platform is very unobvious, and discharge capacity is not very high, performance
It remains to be further improved.
102240574 A of Chinese patent CN discloses a kind of catalysis being made of transient metal complex and carbon black support
Agent shows preferable catalytic activity and stability using the lithium-air battery that the catalyst assembles, but in high current density
The charge and discharge behavior of lower battery is less desirable, fails effectively to control the pattern of catalyst with structure using hydro-thermal method
System.102683726 A of Chinese patent CN discloses a kind of electrocatalysis material of core-shell structure, and stratum nucleare is hollow or solid mistake
Metal oxide is crossed, shell is transition metal nitride, is mainly prepared by nitridation sintered method, and preferable charge and discharge are shown
Performance, but amount and thickness due to failing accurately to control nuclear shell, so that the cycle performance of battery is less desirable.
Summary of the invention
Present invention aim to address existing lithium air battery positive electrode, that there are charge/discharge capacities is low, activation polarization degree is high
The technical problem low with porosity provides and a kind of prepares lithium-air battery cobalt iron oxide/multi-walled carbon nanotube composite catalyzing
The method of agent.The lithium-air battery of this method preparation is able to satisfy high property with cobalt iron oxide/multi-walled carbon nanotube composite catalyst
Low cost, the high-performance of the requirement of energy lithium-air battery industrialization, its carrier is multi-walled carbon nanotube, and active component is that have
The cobalt iron oxide of different structure form is nanocrystalline.
In order to solve the above technical problems, the technical solution adopted by the present invention are as follows:
A method of lithium-air battery cobalt iron oxide/multi-walled carbon nanotube composite catalyst is prepared, catalyst
Active material is cobalt iron oxide, and carrier is multi-walled carbon nanotube；The quality percentage of the cobalt iron oxide, multi-walled carbon nanotube
Content is respectively as follows: cobalt iron oxide: 4%~10%, multi-walled carbon nanotube: 90%~96%；The cobalt iron oxide diameter is
30~80nm, multi-wall carbon nano-tube pipe diameter are 20~100nm；Lithium-air battery cobalt iron oxide/multi-walled carbon nanotube
Composite catalyst specific surface area is 1600~2200m2·g-1；
Include the following steps:
(1) trishydroxymethylaminomethane hydrochloride and methanol are mixed and made into solution A with the volume ratio of 1:1~5, adjusted
Its pH value is 8.0~11.0, and controlling its concentration is 0.01~0.1mol/L；By dopamine and dimethylformamide with 1:7~
10 volume ratio is mixed and made into solution B；Solution A and solution B are mixed and made into solution C with the volume ratio of 1:1~5；
(2) multi-walled carbon nanotube is placed in solution C, prepares the suspension that mass percent concentration is 0.1~0.6%,
30~60min of ultrasonic disperse persistently stirs 4~8h, with deionized water and washes of absolute alcohol 3~5 then at 60~90 DEG C
It is secondary, the multi-walled carbon nanotube powder by surface preparation is obtained, is then added in multi-walled carbon nanotube powder after treatment
Deionized water, the suspension for preparing mass percent concentration 0.5~1.0% are spare；
(3) Co in molar ratio2+: Fe3+=1:1~3 weigh cobalt salt respectively, molysite is dissolved in deionized water, and it is total to prepare ion
Concentration contains Co for 0.05~0.5mol/L's2+、Fe3+Mixed solution；
(4) by Co2+、Fe3+Mixed solution to be slowly added dropwise to step (2) mass percent concentration be 0.5~1.0%
In suspension, at 60~90 DEG C, 8~12h is persistently stirred, obtains muddy reaction solution, the Co2+、Fe3+Mixed solution
1~the 5:1 of volume ratio for the suspension for being 0.5~1.0% with mass percent concentration；
(5) turbid obtained by step (4) is transferred in reaction kettle, at 150~200 DEG C, reacts 8~72h, natural cooling
To room temperature, sediment is obtained；
(6) sediment deionized water and dehydrated alcohol are washed 3~5 times repeatedly, until cleaning solution pH be maintained at 6.0~
7.0, then dry 12 at 60~80 DEG C~for 24 hours；
(7) step (6) resulting product is placed in Muffle furnace, inert atmosphere protection, with the heating speed of 3~12 DEG C/min
Rate is warming up to 300~650 DEG C, keeps the temperature 3~6h to get product.
Selected cobalt salt, molysite are one or more of sulfate, nitrate, chloride, acetate in the step (3)
With the mixture of any ratio.
The invention adopts the above technical scheme, compared with the prior art, the invention has the advantages that:
1) material used in lithium-air battery catalyst prepared by the present invention is cheap metallic salt etc.,
Compared with noble metal catalyst, production cost is greatly reduced；
2) multi-walled carbon nanotube used in the present invention has very high specific surface area and pore structure abundant, superpower power
Performance, the excellent characteristics such as conductive and thermally conductive are learned, the diffusion and transmission and electrode reaction and catalysis for being conducive to oxygen were reacted
Electron transmission in journey；
3) cobalt iron oxide/multi-walled carbon nanotube composite catalyst prepared by the present invention can provide a large amount of adsorption potential
Point and active site, are precipitated for oxygen and reduction reaction provides bigger reaction interface, reduce charge and discharge overpotential and charging voltage,
Lithium-air battery efficiency for charge-discharge and cycle performance are improved, and then improves service life and the safety of battery；
4) present invention selects cobalt iron oxide/multi-wall carbon nano-tube composite material to react difunctional as lithium-air battery
Anode catalyst, main component asepsis environment-protecting, cheap, preparation process is simple, easy to industrialized production.
Detailed description of the invention
Fig. 1 is 2 gained CoFe of the embodiment of the present invention2O4The XRD spectrum of/MWCNTs (multi-walled carbon nanotube)；
Fig. 2 and Fig. 3 is the resulting pure MWCNTs and CoFe of the embodiment of the present invention 22O4The TEM map of/MWCNTs；
Fig. 4 and Fig. 5 is the 2 pure MWCNTs and CoFe of gained of the embodiment of the present invention2O4Isothermal is desorbed in the nitrogen adsorption of/MWCNTs
Curve.
Specific embodiment
Embodiment 1
One of the present embodiment lithium-air battery cobalt iron oxide/multi-walled carbon nanotube composite catalyst, catalysis
The active material of agent is cobalt iron oxide, and carrier is multi-walled carbon nanotube；The quality percentage of cobalt iron oxide, multi-walled carbon nanotube
Content is respectively as follows: cobalt iron oxide: 4%~6%, multi-walled carbon nanotube: 94%~96%；Cobalt iron oxide diameter be 30~
50nm, multi-wall carbon nano-tube pipe diameter are 20~50nm；Lithium-air battery cobalt iron oxide/multi-walled carbon nanotube composite catalyst
Specific surface area is 1600~1750m2·g-1。
It is a kind of to prepare the cobalt iron oxide of lithium-air battery described in the present embodiment/multi-walled carbon nanotube composite catalyst
Method includes the following steps:
(1) trishydroxymethylaminomethane hydrochloride and methanol are mixed and made into solution A with the volume ratio of 1:1, adjust it
PH value is 8.0, and controlling its concentration is 0.01mol/L；Dopamine and dimethylformamide are mixed into system with the volume ratio of 1:7
At solution B；Solution A and solution B are mixed and made into solution C with the volume ratio of 1:1；
(2) multi-walled carbon nanotube is placed in solution C, prepares the suspension that mass percent concentration is 0.1%, ultrasound point
It dissipates 30min and persistently stirs 4h then at 60 DEG C, with deionized water and washes of absolute alcohol 3 times, obtain locating in advance by surface
Then deionized water is added in the multi-walled carbon nanotube powder of reason in multi-walled carbon nanotube powder after treatment, prepare quality hundred
Divide the suspension of specific concentration 0.5% spare；
(3) Co in molar ratio2+: Fe3+=1:1 weighs cobaltous sulfate, ferric sulfate solution in deionized water respectively, prepares ion
Total concentration contains Co for 0.05mol/L's2+、Fe3+Mixed solution；
(4) by Co2+、Fe3+Mixed solution be slowly added dropwise to step (2) mass percent concentration be 0.5% suspension
In, at 60 DEG C, 8h is persistently stirred, obtains muddy reaction solution, the Co2+、Fe3+Mixed solution and mass percent it is dense
The volume ratio 1:1 for the suspension that degree is 0.5%；
(5) turbid obtained by step (4) is transferred in reaction kettle, at 150 DEG C, reacts 8h, cooled to room temperature obtains
To sediment；
(6) sediment deionized water and dehydrated alcohol are washed 3 times repeatedly, until cleaning solution pH is maintained at 6.0, then
The dry 12h at 60 DEG C；
(7) step (6) resulting product is placed in Muffle furnace, inert atmosphere protection, with the heating rate liter of 3 DEG C/min
Temperature keeps the temperature 3h to 300 DEG C to get product.
Embodiment 2
One of the present embodiment lithium-air battery cobalt iron oxide/multi-walled carbon nanotube composite catalyst, catalysis
The active material of agent is cobalt iron oxide, and carrier is multi-walled carbon nanotube；The quality percentage of cobalt iron oxide, multi-walled carbon nanotube
Content is respectively as follows: cobalt iron oxide: 6%~8%, multi-walled carbon nanotube: 92%~94%；Cobalt iron oxide diameter be 50~
60nm, multi-wall carbon nano-tube pipe diameter are 50~80nm；Lithium-air battery cobalt iron oxide/multi-walled carbon nanotube composite catalyst
Specific surface area is 1750~1950m2·g-1。
It is a kind of to prepare the cobalt iron oxide of lithium-air battery described in the present embodiment/multi-walled carbon nanotube composite catalyst
Method includes the following steps:
(1) trishydroxymethylaminomethane hydrochloride and methanol are mixed and made into solution A with the volume ratio of 1:3, adjust it
PH value is 9.0, and controlling its concentration is 0.05mol/L；Dopamine and dimethylformamide are mixed into system with the volume ratio of 1:8
At solution B；Solution A and solution B are mixed and made into solution C with the volume ratio of 1:3；
(2) multi-walled carbon nanotube is placed in solution C, prepares the suspension that mass percent concentration is 0.3%, ultrasound point
It dissipates 45min and persistently stirs 6h then at 75 DEG C, with deionized water and washes of absolute alcohol 4 times, obtain locating in advance by surface
Then deionized water is added in the multi-walled carbon nanotube powder of reason in multi-walled carbon nanotube powder after treatment, prepare quality hundred
Divide the suspension of specific concentration 0.8% spare；
(3) Co in molar ratio2+: Fe3+=1:2 weighs cobaltous sulfate, ferric sulfate solution in deionized water respectively, prepares ion
Total concentration contains Co for 0.3mol/L's2+、Fe3+Mixed solution；
(4) by Co2+、Fe3+Mixed solution be slowly added dropwise to step (2) mass percent concentration be 0.7% suspension
In, at 75 DEG C, 10h is persistently stirred, obtains muddy reaction solution, the Co2+、Fe3+Mixed solution and mass percent
The volume ratio 3:1 for the suspension that concentration is 0.8%；
(5) turbid obtained by step (4) is transferred in reaction kettle, at 180 DEG C, reaction 48h, cooled to room temperature,
Obtain sediment；
(6) sediment deionized water and dehydrated alcohol are washed 4 times repeatedly, until cleaning solution pH is maintained at 6.5, then
The dry 18h at 70 DEG C；
(7) step (6) resulting product is placed in Muffle furnace, inert atmosphere protection, with the heating rate liter of 8 DEG C/min
Temperature keeps the temperature 5h to 450 DEG C to get product.
It is Co obtained in the present embodiment2+With Fe3+CoFe when for 1:22O4Nanometer rods and the compound production of multi-walled carbon nanotube
Object, Fig. 1 CoFe2O4The XRD spectra of/MWCNTs composite material, in figure other than the stronger characteristic diffraction peak of MWCNTs, also
There is CoFe2O4Characteristic diffraction peak, with CoFe2O4Standard spectrogram (PDF NO.22-01086) very coincide, illustrate carbon
Nanotube surface is coated with CoFe really2O4Nanocrystal.Fig. 2/3 are respectively pure MWCNTs and CoFe2O4/ MWCNTs composite wood
The TEM spectrogram of material, the caliber of uncoated pure MWCNTs in 60nm or so, it is compound after outer surface of tube wall become very coarse,
There are many similar caterpillar shape CoFe2O4Be attached to carbon nano tube surface, it is well dispersed, avoid be widely used at present it is coprecipitated
The shortcomings that larger easy agglomeration of the product grain that shallow lake method is formed is reunited.Fig. 4/5 are respectively pure MWCNTs and CoFe2O4/ MWCNTs is compound
Isothermal curve spectrogram, CoFe is desorbed in the nitrogen adsorption of material2O4Isothermal curve category is desorbed in the nitrogen adsorption of/MWCNTs composite material
It is larger in intermediate voltage terminal adsorbance in typical IV type adsorption/desorption curve, it is CoFe2O4The tribute in the hole that the accumulation of nanometer rods is formed
It offers, total specific surface is 1873m2·g-1, and the specific surface area of pure MWCNTs is 1309m2·g-1, with existing block or micro-
For meter level catalyst material, CoFe2O4The bigger serface of/MWCNTs nanocomposite, which provides, is largely conducive to oxygen
The active position with oxygen reduction reaction is precipitated, is conducive to the liquid-solid three phase region of gas-of oxygen reduction.
Embodiment 3
One of the present embodiment lithium-air battery cobalt iron oxide/multi-walled carbon nanotube composite catalyst, catalysis
The active material of agent is cobalt iron oxide, and carrier is multi-walled carbon nanotube；The quality percentage of cobalt iron oxide, multi-walled carbon nanotube
Content is respectively as follows: cobalt iron oxide: 8%~10%, multi-walled carbon nanotube: 90%~92%；Cobalt iron oxide diameter be 60~
80nm, multi-wall carbon nano-tube pipe diameter are 80~100nm；Lithium-air battery cobalt iron oxide/multi-walled carbon nanotube composite catalyzing
Agent specific surface area is 1950~2200m2·g-1。
It is a kind of to prepare the cobalt iron oxide of lithium-air battery described in the present embodiment/multi-walled carbon nanotube composite catalyst
Method includes the following steps:
(1) trishydroxymethylaminomethane hydrochloride and methanol are mixed and made into solution A with the volume ratio of 1:5, adjust it
PH value is 11.0, and controlling its concentration is 0.1mol/L；Dopamine and dimethylformamide are mixed into system with the volume ratio of 1:10
At solution B；Solution A and solution B are mixed and made into solution C with the volume ratio of 1:5；
(2) multi-walled carbon nanotube is placed in solution C, prepares the suspension that mass percent concentration is 0.6%, ultrasound point
It dissipates 60min and persistently stirs 8h then at 90 DEG C, with deionized water and washes of absolute alcohol 5 times, obtain locating in advance by surface
Then deionized water is added in the multi-walled carbon nanotube powder of reason in multi-walled carbon nanotube powder after treatment, prepare quality hundred
Divide the suspension of specific concentration 1.0% spare；
(3) Co in molar ratio2+: Fe3+=1:3 weighs cobaltous sulfate, ferric sulfate solution in deionized water respectively, prepares ion
Total concentration contains Co for 0.5mol/L's2+、Fe3+Mixed solution；
(4) by Co2+、Fe3+Mixed solution be slowly added dropwise to step (2) mass percent concentration be 1.0% suspension
In, at 90 DEG C, 12h is persistently stirred, obtains muddy reaction solution, the Co2+、Fe3+Mixed solution and mass percent
The volume ratio 5:1 for the suspension that concentration is 1.0%；
(5) turbid obtained by step (4) is transferred in reaction kettle, at 200 DEG C, reaction 72h, cooled to room temperature,
Obtain sediment；
(6) sediment deionized water and dehydrated alcohol are washed 5 times repeatedly, until cleaning solution pH is maintained at 7.0, then
It is dried for 24 hours at 80 DEG C；
(7) step (6) resulting product is placed in Muffle furnace, inert atmosphere protection, with the heating rate of 12 DEG C/min
650 DEG C are warming up to, keeps the temperature 6h to get product.
Cobaltous sulfate in above-described embodiment can also use one of cobalt nitrate, cobalt chloride, cobalt acetate or cobaltous sulfate, nitric acid
Cobalt, cobalt chloride, several mixtures with any ratio in cobalt acetate replace.
Ferric sulfate can also use one of ferric nitrate, iron chloride, ferric acetate or ferric sulfate, nitric acid in above-described embodiment
Iron, iron chloride, several mixtures with any ratio in ferric acetate replace.
The embodiments of the present invention described above are not intended to limit the scope of the present invention.It is any in the present invention
Spirit and principle within made modifications, equivalent substitutions and improvements etc., should be included in claim protection model of the invention
Within enclosing.
Claims (2)
1. a kind of prepare lithium-air battery cobalt iron oxide/multi-walled carbon nanotube composite catalyst method, it is characterised in that:
The active material of catalyst is cobalt iron oxide, and carrier is multi-walled carbon nanotube；The cobalt iron oxide, multi-walled carbon nanotube
Mass percentage is respectively as follows: cobalt iron oxide: 4%~10%, multi-walled carbon nanotube: 90%~96%；The ferro-cobalt oxidation
Object diameter is 30~80nm, and multi-wall carbon nano-tube pipe diameter is 20~100nm；Lithium-air battery cobalt iron oxide/multi wall
Carbon nano tube composite catalyst specific surface area is 1600~2200m2·g-1；
Include the following steps:
(1) trishydroxymethylaminomethane hydrochloride and methanol are mixed and made into solution A with the volume ratio of 1:1~5, adjust its pH
Value is 8.0~11.0, and controlling its concentration is 0.01~0.1mol/L；By dopamine and dimethylformamide with 1:7~10
Volume ratio is mixed and made into solution B；Solution A and solution B are mixed and made into solution C with the volume ratio of 1:1~5；
(2) multi-walled carbon nanotube is placed in solution C, prepares the suspension that mass percent concentration is 0.1~0.6%, ultrasound
Disperse 30~60min, then at 60~90 DEG C, persistently stirs 4~8h, with deionized water and washes of absolute alcohol 3~5 times,
Obtain the multi-walled carbon nanotube powder by surface preparation, then in multi-walled carbon nanotube powder after treatment be added go from
Sub- water, the suspension for preparing mass percent concentration 0.5~1.0% are spare；
(3) Co in molar ratio2+: Fe3+=1:1~3 weigh cobalt salt respectively, molysite is dissolved in deionized water, prepare total ion concentration
Contain Co for 0.05~0.5mol/L2+、Fe3+Mixed solution；
(4) by Co2+、Fe3+Mixed solution be slowly added dropwise to step (2) mass percent concentration be 0.5~1.0% suspension
In, at 60~90 DEG C, 8~12h is persistently stirred, obtains muddy reaction solution, the Co2+、Fe3+Mixed solution and quality
1~the 5:1 of volume ratio for the suspension that percent concentration is 0.5~1.0%；
(5) turbid obtained by step (4) is transferred in reaction kettle, at 150~200 DEG C, reacts 8~72h, naturally cool to room
Temperature obtains sediment；
(6) sediment deionized water and dehydrated alcohol are washed 3~5 times repeatedly, until cleaning solution pH is maintained at 6.0~7.0,
Then dry 12 at 60~80 DEG C~for 24 hours；
(7) step (6) resulting product is placed in Muffle furnace, inert atmosphere protection, with the heating rate liter of 3~12 DEG C/min
Temperature keeps the temperature 3~6h to 300~650 DEG C to get product.
2. a kind of lithium-air battery cobalt iron oxide/multi-walled carbon nanotube composite catalyzing is prepared according to claim 1
The method of agent, it is characterised in that: selected cobalt salt, molysite are sulfate, in nitrate, chloride, acetate in the step (3)
One or more of mixtures with any ratio.
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| CN108063263A (en) * | 2017-11-14 | 2018-05-22 | 兰州大学 | A kind of Prussian blue type aluminium-air cell material and its preparation method and application |
| CN109161923A (en) * | 2018-11-05 | 2019-01-08 | 青岛科技大学 | Carbon nanotube/ferro-cobalt acrylic/hydrotalcite-like nano piece compound preparation method and its electro-catalysis application |
| CN110350179B (en) * | 2019-07-17 | 2021-04-02 | 中国科学院福建物质结构研究所 | Fe2O3Nano carbon composite material and preparation method and application thereof |
| CN112382769B (en) * | 2020-11-04 | 2021-10-15 | 江苏科技大学 | High-performance metal-air battery anode catalyst and preparation method thereof |
| CN113548699A (en) * | 2021-07-20 | 2021-10-26 | 安徽昊源化工集团有限公司 | Cobalt oxide/carbon nanotube composite material, preparation method thereof and application thereof in lithium air battery |
| CN114446673B (en) * | 2022-01-14 | 2023-10-31 | 河北工业大学 | Three-dimensional net-shaped flake CoFe 2 O 4 @NiO composite material, preparation method and application |
| CN115197675B (en) * | 2022-08-30 | 2023-12-19 | 盐城工学院 | Preparation method of FeNi/MCNTs/NC wave-absorbing material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103613374A (en) * | 2013-11-26 | 2014-03-05 | 彭晓领 | Cobalt ferrite @ carbon nano tube composite material and preparation method thereof |
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| CN103613374A (en) * | 2013-11-26 | 2014-03-05 | 彭晓领 | Cobalt ferrite @ carbon nano tube composite material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Decoration of multi-walled carbon nanotubes(MWCNTs) with different ferrite nanoparticles and its use as an adsorbent;Ahmed A Farghali等;《Journal of Nanostructure in Chemistry》;20130715;第3卷(第1期);第1-12页 |
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