CN106981666A - A kind of high voltage platform Co Mn Cu compound oxygen reduction catalyst materials and preparation method thereof - Google Patents
A kind of high voltage platform Co Mn Cu compound oxygen reduction catalyst materials and preparation method thereof Download PDFInfo
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- CN106981666A CN106981666A CN201710303388.6A CN201710303388A CN106981666A CN 106981666 A CN106981666 A CN 106981666A CN 201710303388 A CN201710303388 A CN 201710303388A CN 106981666 A CN106981666 A CN 106981666A
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- H—ELECTRICITY
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- 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
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
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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
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
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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
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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
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
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- 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
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Abstract
The present invention relates to a kind of high voltage platform Co Mn Cu compound oxygen reduction catalyst materials and preparation method thereof, it is characterised in that its specific preparation method, comprises the following steps that：Potassium permanganate is dissolved in deionized water first, solution one is formed；Cobalt acetate is dissolved in deionized water again, acetic acid cobalt liquor and manganese nitrate solution are then configured to mixed solution two；Mixed solution two is slowly added to formation mixed solution three in solution one under agitation afterwards；Copper nitrate solution is mixed with mixed solution three, mixed solution four is made；The pH value of mixed solution four is adjusted to 10 ~ 12, is placed in stirring in water bath with thermostatic control；Suction filtration, washing 3 times after dry, dry after sinter.It possesses that preparation technology is simple, the cost of raw material is low, be easy to large-scale production; and many advantages, such as oxygen reduction catalytic activity is high, stability is high, service life is long, the problem of further application is limited to metal-air battery in current material and system can be improved well.
Description
Technical field
The present invention relates to a kind of high voltage platform Co-Mn-Cu compound oxygen reduction catalyst materials and preparation method thereof, it can answer
With the air cathode of metal-air battery, belong to power battery technology field.
Background technology
With increasingly sharpening for environmental problem, development new-energy automobile especially electric automobile turns into trend of the times.At present,
Lithium ion battery and Ni-MH battery acquisition cost at initial stage that electric car power supply is mainly used are high, energy density is low, the charging interval
Grow and course continuation mileage is short, it is impossible to meet the demand in market.Aluminium-air cell has lot of advantages compared to both batteries：Negative pole
Materials of aluminum is content highest metallic element in the earth's crust, cheap；And positive active material is the oxygen in air, wiper ring
Protect, energy density is high.The theoretical energy density of aluminium-air cell is up to 8140Wh/kg, and therefore, in electric automobile field, application is latent
Power is huge.By the way of the report such as X. Zhang in 2004 is using the replacing once electrolytic liquid per 400km, aluminium-air cell EV continuation of the journey
Mileage is up to 1600km.
However, aluminium-air cell also faces many technical barriers in application aspect, it is exactly it that wherein power output is relatively low
One of.It is reported that the power density of generally aluminium-air cell is only capable of reaching 33W/kg.This just makes it be difficult to as electrokinetic cell
Popularization and application are carried out on electric automobile.In each critical component of aluminium-air cell, restrict its overall output power it is main because
Element is that air cathode is low to the transformation efficiency of oxygen.The usual factor is main to be determined by water proofing property, gas permeability, catalyst activity etc.
It is fixed.Common air cathode catalyst mainly has the precious metal materials such as Pt, Ag and manganese dioxide etc..The catalyst of precious metal material
Cost is higher, does not utilize large-scale application, and MnO2Material, its catalytic performance or stability can not all reach at this stage
The level of popularization and application.Therefore, developing new catalyst material turns into the emphasis of current research.And develop high-performance non-noble gold
Metal catalyst also turns into the emphasis that current research mechanism is paid close attention to.
And composite is by two or more material of different nature, by method physically or chemically, grand
See or microcosmic upper material of the composition with new capability.Various materials make up for each other's deficiencies and learn from each other in performance, produce cooperative effect, make multiple
The combination property of condensation material is better than former composition material and meets a variety of requirements.This patent is prepared for one using chemical method
Co-Mn-Cu composite oxide materials are planted, the progress that two kinds of materials can be on nanoscale is merged, can reached a kind of mutual
Promotion, the mutually stable, effect of concerted catalysis.
Find that the patent family related to the keyword such as " oxygen reduction catalyst ", " cobalt ", " manganese ", " copper " there are about 32 by retrieval
It is individual.For example, number of patent application discloses one for CN201280066888.8 patent " oxygen reduction catalyst and its manufacture method "
Oxygen reduction catalyst is planted, its primary particle comprising titanium compound is dispersed in the compound particle in the structure of carbon, its feature exists
In being used as constitution element with titanium, carbon, nitrogen and oxygen, and define the atomic quantity ratio of each element；Number of patent application is
A kind of CN201410408484.3 patent " preparation of the aerogel carried non noble metal oxygen reduction catalyst of nitrogen-doped graphene "
A kind of preparation method of non-precious metal catalyst is disclosed, is comprised the following steps, by the mixed solution of organic amine and aldehyde 50 ~ 90
0.5 ~ 2h is stirred at DEG C, graphene oxide and base metal salting liquid is then added, persistently stirs 1 ~ 24h at 60 ~ 99 DEG C, obtain
To organogel, 500 ~ 1000 DEG C are warming up to after freezing or supercritical drying under inert gas shielding, 1 ~ 6h is incubated, it is naturally cold
But to room temperature." a kind of carbon carries many metal multi-metal polypyrrole hydrogen reduction catalysis to the patent that number of patent application is CN201210289457.X
Agent and preparation method thereof " discloses a kind of multi-metal polypyrrole oxygen reduction catalyst and preparation method, specially using a kind of or a kind of
Other metal parts above replace existing carbon to carry monometallic multi-metal polypyrrole oxygen reduction catalyst Co-PPy/C or Fe-PPy/C
In metal Co or Fe, obtain carbon containing two or more metal and carry many metal multi-metal polypyrrole oxygen reduction catalysts；Deng
Deng.However, and find no by chemical method prepare Co-Mn-Cu composite oxide catalysts materials patent or with this specially
Sharp identical patent is present.
To sum up, traditional noble metal catalyst and emerging non-precious metal catalyst, or cost is high or activity is low, shows
So all it is difficult to the practical application for meeting metal-air battery, therefore, this patent has very high practical value.
The content of the invention
It is an object of the invention to provide a kind of high voltage platform Co-Mn-Cu compound oxygen reductions catalyst material and its preparation
Method, it possesses, and preparation technology is simple, the cost of raw material is low, be easy to large-scale production, and oxygen reduction catalytic activity is high, stability
It is high, many advantages, such as service life is long, can well improve in current material and system and metal-air battery further should
The problem of with limitation.
The technical proposal of the invention is realized in this way：A kind of high voltage platform Co-Mn-Cu compound oxygen reduction catalyst materials
Material and preparation method thereof, it is characterised in that its specific preparation method, is comprised the following steps that：
Potassium permanganate is dissolved in deionized water first, solution one is formed；Cobalt acetate is dissolved in deionized water again, then
The mass fraction that acetic acid cobalt liquor and manganese nitrate solution are configured into manganese nitrate in mixed solution two, manganese nitrate solution is 50%；It
It is stirred afterwards using magnetic stirring apparatus, mixing speed is 400 ~ 600 rpms, under agitation delays mixed solution two
Slow add forms mixed solution three in solution one；Copper nitrate is dissolved in deionized water again, then by copper nitrate solution with mixing
Close solution three to be mixed, mixed solution four is made；The pH value of mixed solution four is finally adjusted to 10 ~ 12 using KOH solution,
It is placed in being stirred continuously in water bath with thermostatic control, mixing time is 1-4h, bath temperature is 50 ~ 80 DEG C；Suction filtration, washing 3 times after dry,
Dry environment is vacuum environment, and drying temperature is 80 ~ 120 DEG C, and dried material is put into alumina crucible, places into high temperature furnace
Sintered under middle certain temperature, sintering temperature is 300-600 DEG C in high temperature furnace, and sintering time is 2-6h, is finally given with micro-nano
The high voltage platform Co-Mn-Cu compound oxygen reduction catalyst materials of compound pattern, its particle diameter is between 0.01 ~ 5um.
Potassium permanganate mass fraction is 20 ~ 40% in described solution one.
Cobalt acetate mass fraction is 20 ~ 40% in described acetic acid cobalt liquor.
The mol ratio of manganese nitrate and potassium permanganate is 1 in described mixed solution three:3~2:3, cobalt acetate and manganese salt are rubbed
You are than being 5:95~40:60.
Nitric acid Copper mass fraction is 20 ~ 40% in described copper nitrate solution.
Copper nitrate and manganese salt mol ratio are 2 in described mixed solution four:98~30:70.
The positive effect of the present invention is：（1）Compared with the existing pure noble metal catalyst, it is possible to reduce noble metal makes
With reducing the cost of catalyst material, and then reduce the cost of metal-air battery；（2）With MnO2Catalyst is compared, Co
With the addition of Cu oxides, its catalytic activity is improved first, is obviously improved its voltage platform, chemical property can reach
100mA/cm2More than；Next improves its electrochemical stability, and the presence of Co elements can suppress MnO2The composition of material and crystalline substance
Type convert, its activity is kept for the more long time, so reached one can be with the degree of utilization and extention；（3）Make work
Skill is simple, it is easy to large-scale production；Therefore, this kind of catalytic composite material has very high use value.
Brief description of the drawings
Fig. 1 is the polarization curve test result of catalyst material prepared by embodiment.
Fig. 2 is the constant-current discharge Dependence Results of the catalyst material prepared in embodiment using this patent method.
Embodiment
The present invention is further described with embodiment below in conjunction with the accompanying drawings, embodiment is the spy that the present invention is furture elucidated
Point, is not equal to the limitation present invention, and the change carried out for those skilled in the art according to the present invention should be included in this hair
Within bright protection domain.
Embodiment 1
Potassium permanganate 5.69g is dissolved in deionized water first, solution 1 is formed；17.9g cobalt acetates are dissolved in deionization again
With 38.4g manganese nitrate solutions in water（Mass fraction is 50%）It is configured to mixed solution 2；It will mix under agitation afterwards molten
Liquid 2 is slowly added in solution 1 form mixed solution 3；Again 10.10g copper nitrates are dissolved in deionized water to enter with mixed solution 3
Row mixing, is made mixed solution 4；The pH value of mixed solution 4 is finally adjusted to 10 using KOH solution, 60 DEG C of constant temperature are placed in
It is stirred continuously in water-bath；Suction filtration, washing 5 times after in 100 DEG C of vacuum drying ovens dry, be put into afterwards in high temperature furnace with 350 DEG C burning
4h is tied, a kind of high voltage platform Co-Mn-Cu compound oxygen reduction catalyst materials CMC-1 is obtained.
Embodiment 2
Potassium permanganate 8.54g is dissolved in deionized water first, solution 1 is formed；4.48g cobalt acetates are dissolved in deionization again
With 38.4g manganese nitrate solutions in water（Mass fraction is 50%）It is configured to mixed solution 2；It will mix under agitation afterwards molten
Liquid 2 is slowly added in solution 1 form mixed solution 3；Again 3.37g copper nitrates are dissolved in deionized water to enter with mixed solution 3
Row mixing, is made mixed solution 4；The pH value of mixed solution 4 is finally adjusted to 11 using KOH solution, 70 DEG C of constant temperature are placed in
It is stirred continuously in water-bath；Suction filtration, washing 4 times after in 120 DEG C of vacuum drying ovens dry, be put into afterwards in high temperature furnace with 550 DEG C burning
2h is tied, a kind of high voltage platform Co-Mn-Cu compound oxygen reduction catalyst materials are obtained.
Embodiment 3
Potassium permanganate 11.38g is dissolved in deionized water first, solution 1 is formed；Again by 8.96g cobalt acetates be dissolved in from
With 38.4g manganese nitrate solutions in sub- water（Mass fraction is 50%）It is configured to mixed solution 2；Afterwards under agitation will mixing
Solution 2 is slowly added in solution 1 form mixed solution 3；6.75g copper nitrates are dissolved in deionized water and mixed solution 3 again
Mixed, mixed solution 4 is made；The pH value of mixed solution 4 is finally adjusted to 12 using KOH solution, 80 DEG C of perseverances are placed in
It is stirred continuously in tepidarium；Suction filtration, washing 6 times after in 90 DEG C of vacuum drying ovens dry, be put into afterwards in high temperature furnace with 450 DEG C burning
5h is tied, a kind of high voltage platform Co-Mn-Cu compound oxygen reduction catalyst materials are obtained.
Embodiment 4
Air cathode sample is made using the catalyst material prepared in above-described embodiment 1 and it is polarized, the property such as constant-current discharge
It can be tested, test result is as shown in drawings, it can be seen that the catalyst material current density is up to 100mA/cm2, open circuit
Reachable-the 18mV of voltage, the reachable -0.42V of discharge voltage, with outstanding chemical property.
Claims (6)
1. a kind of high voltage platform Co-Mn-Cu compound oxygen reduction catalyst materials and preparation method thereof, it is characterised in that its is specific
Preparation method, is comprised the following steps that：
Potassium permanganate is dissolved in deionized water first, solution one is formed；Cobalt acetate is dissolved in deionized water again, then
The mass fraction that acetic acid cobalt liquor and manganese nitrate solution are configured into manganese nitrate in mixed solution two, manganese nitrate solution is 50%；It
It is stirred afterwards using magnetic stirring apparatus, mixing speed is 400 ~ 600 rpms, under agitation delays mixed solution two
Slow add forms mixed solution three in solution one；Copper nitrate is dissolved in deionized water again, then by copper nitrate solution with mixing
Close solution three to be mixed, mixed solution four is made；The pH value of mixed solution four is finally adjusted to 10 ~ 12 using KOH solution,
It is placed in being stirred continuously in water bath with thermostatic control, mixing time is 1-4h, bath temperature is 50 ~ 80 DEG C；Suction filtration, washing 3 times after dry,
Dry environment is vacuum environment, and drying temperature is 80 ~ 120 DEG C, and dried material is put into alumina crucible, places into high temperature furnace
Sintered under middle certain temperature, sintering temperature is 300-600 DEG C in high temperature furnace, and sintering time is 2-6h, is finally given with micro-nano
The high voltage platform Co-Mn-Cu compound oxygen reduction catalyst materials of compound pattern, its particle diameter is between 0.01 ~ 5um.
2. a kind of high voltage platform Co-Mn-Cu compound oxygen reductions catalyst material and its preparation according to claim 1
Method, it is characterised in that potassium permanganate mass fraction is 20 ~ 40% in described solution one.
3. a kind of high voltage platform Co-Mn-Cu compound oxygen reductions catalyst material and its preparation according to claim 1
Method, it is characterised in that cobalt acetate mass fraction is 20 ~ 40% in described acetic acid cobalt liquor.
4. a kind of high voltage platform Co-Mn-Cu compound oxygen reductions catalyst material and its preparation according to claim 1
Method, it is characterised in that the mol ratio of manganese nitrate and potassium permanganate is 1 in described mixed solution three:3~2:3, cobalt acetate and manganese
The mol ratio of salt is 5:95~40:60.
5. a kind of high voltage platform Co-Mn-Cu compound oxygen reductions catalyst material and its preparation according to claim 1
Method, it is characterised in that nitric acid Copper mass fraction is 20 ~ 40% in described copper nitrate solution.
6. a kind of high voltage platform Co-Mn-Cu compound oxygen reductions catalyst material and its preparation according to claim 1
Method, it is characterised in that copper nitrate and manganese salt mol ratio are 2 in described mixed solution four:98~30:70.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103050701A (en) * | 2011-10-17 | 2013-04-17 | 中国科学院大连化学物理研究所 | Electrode material for lithium-air battery and preparation method of electrode material |
| CN103346334A (en) * | 2013-07-05 | 2013-10-09 | 中南大学 | Application method of MnxCe(1-x)O2 nanoparticles |
| CN103346333A (en) * | 2013-06-28 | 2013-10-09 | 苏州大学 | Secondary lithium-air battery cathode catalyst and application thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103050701A (en) * | 2011-10-17 | 2013-04-17 | 中国科学院大连化学物理研究所 | Electrode material for lithium-air battery and preparation method of electrode material |
| CN103346333A (en) * | 2013-06-28 | 2013-10-09 | 苏州大学 | Secondary lithium-air battery cathode catalyst and application thereof |
| CN103346334A (en) * | 2013-07-05 | 2013-10-09 | 中南大学 | Application method of MnxCe(1-x)O2 nanoparticles |
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