CN106207198A - Prepare the method for manganese oxide catalyst, manganese oxide catalyst and application thereof - Google Patents
Prepare the method for manganese oxide catalyst, manganese oxide catalyst and application thereof Download PDFInfo
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- CN106207198A CN106207198A CN201610554943.8A CN201610554943A CN106207198A CN 106207198 A CN106207198 A CN 106207198A CN 201610554943 A CN201610554943 A CN 201610554943A CN 106207198 A CN106207198 A CN 106207198A
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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
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
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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
- 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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- 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
- H01M4/9091—Unsupported catalytic particles; loose particulate catalytic materials, e.g. in fluidised state
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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
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Abstract
The present invention proposes and prepares the method for manganese oxide catalyst, manganese oxide catalyst and application thereof.The method includes: the aqueous solution containing manganese salt, metal dopant and potassium permanganate is carried out hydro-thermal reaction process by (1), the temperature of described hydro-thermal reaction is 100～200 degrees Celsius, mixing speed is 100～500r/min, and the response time is 5～30 hours；(2) the hydro-thermal reaction product obtained in step (1) is carried out filtration treatment, and collect filtering residue；(3) described filtering residue is dried process, milled processed and calcination process successively, in order to obtain described manganese oxide catalyst.The method can effectively make the pattern micro-nano of manganese oxide catalyst, prepares the diameter thread manganese oxide catalyst of less micro-nano, such that it is able to be effectively improved the specific surface area of catalyst, and then obtains preferable catalytic effect.The method step is simple, low production cost, be easily enlarged production scale, is conducive to the large-scale application of this catalyst.
Description
Technical field
The present invention relates to battery material technical field, in particular it relates to prepare the method for manganese oxide catalyst,
Manganese oxide catalyst and application thereof.
Background technology
Metal fuel battery, is also called metal-air battery, is a kind of will to be stored in metal under the effect of catalyst
Chemical energy be converted directly into the electrochmical power source of electric energy, there is specific power and specific energy height, life-span length, Quick mechanical charging, just
In advantages such as synthetical recovery, it is a kind of environmental protection and energy saving, high efficiency electricity generation system.Cathodic oxygen reduction catalyst decides air electricity
The polarization property of pole electrochemical reaction, has conclusive impact to electrode potential, operating potential.The material of cathodic oxygen reduction catalysis at present
Material mainly has: platinum and other noble metal catalyst, perovskite composite oxide, manganese series oxides, transition metal large circle chela
Compound four kinds.
But, current oxygen reduction catalyst and preparation method thereof still haves much room for improvement.
Summary of the invention
The present invention be based on inventor on the fact that and the discovery of problem and understanding make:
Due in current oxygen reduction catalyst, generally there is catalytic performance and problem that preparation cost is difficult to take into account.
Inventor finds through further investigation and great many of experiments, and this is due in above-mentioned catalyst, platinum and other precious metal catalyst
Agent catalytic performance is optimal, but it contains noble metal, expensive and be difficult to by the improvement of technique, composition is significantly reduced production
Cost；Perovskite composite oxide and transition metal large circle chelate, owing to catalytic performance is unstable, complicated process of preparation
And it is relatively costly；Manganese oxide catalyst has a good hydrogen reduction catalytic performance, and aboundresources, with low cost, be prone to city
Fieldization is applied, but its catalytic performance is difficult to compare favourably with above-mentioned noble metal catalyst.
It is contemplated that at least solve one of technical problem present in prior art.To this end, the present invention proposes one
The method preparing manganese oxide catalyst.The method under the high temperature conditions, utilizes hydro-thermal reaction preparation containing metal-doped manganese
Oxide catalyst, it is possible to effectively realize the control of manganese oxide catalyst pattern and carried out micro-nano, it is thus achieved that have micro-
Receive the manganese oxide catalyst of thread pattern, such that it is able to be effectively improved the specific surface area of catalyst, and then obtain and preferably urge
Change effect.
In one aspect of the invention, the present invention proposes a kind of method preparing manganese oxide catalyst.According to this
Bright embodiment, the method includes: it is anti-that the aqueous solution containing manganese salt, metal dopant and potassium permanganate is carried out hydro-thermal by (1)
Should process, the temperature of described hydro-thermal reaction is 100～200 degrees Celsius, and mixing speed is 100～500r/min, and the response time is 5
～30 hours；(2) the hydro-thermal reaction product obtained in step (1) is carried out filtration treatment, and collect filtering residue；(3) by described filter
Slag is dried process, milled processed and calcination process successively, in order to obtain described manganese oxide catalyst.It is being added with metal
While adulterant, (100～200 degrees Celsius) carry out hydro-thermal reaction under the high temperature conditions, it is possible to effectively make Mn oxide be catalyzed
The pattern micro-nano of agent, prepares the diameter thread manganese oxide catalyst of less micro-nano, such that it is able to be effectively improved catalyst
Specific surface area, and then obtain preferable catalytic effect.The method step is simple, low production cost, be easily enlarged production scale,
Be conducive to the large-scale application of this catalyst.
According to embodiments of the invention, described manganese salt is bivalent manganese hydrochlorate.Above-mentioned bivalent manganese hydrochlorate can be at water-heat process
In be effectively converted to the Mn oxide with preferable catalytic performance, such that it is able to improve the catalysis utilizing the method to prepare further
The catalytic effect of agent.
According to embodiments of the invention, in described aqueous solution, described manganese salt is 1 with the mol ratio of described potassium permanganate:
(1～3).When manganese salt and described potassium permanganate mol ratio within the above range time, it is possible to make manganese salt be oxidized to catalytic performance
The preferably oxide of manganese, and the catalyst of acquisition can be made to have the pattern that micro-nano is thread.
According to embodiments of the invention, described metal dopant contains ferrum, cobalt, nickel, stannum, cerium, lanthanum, silver and platinum at least
One of；Described manganese salt is 1:(0.01～0.3 with the mol ratio of described metal dopant).Thus, it is possible to utilize above-mentioned metal to mix
Metallic element in miscellaneous dose interacts with Mn oxide, such that it is able to improve the catalytic effect of this catalyst further.
According to embodiments of the invention, in step (1), the described response time is 12～24 hours.Thus, it is possible to enter one
Step improves the catalytic performance of the catalyst obtained, it is ensured that it has the thread pattern of preferable micro-nano, and prevents due to the response time
Long and cause the production cycle long, affect the yield of the method.
According to embodiments of the invention, in step (3), the temperature of described dried is 50～115 degrees Celsius, the time
It it is 3～24 hours.Thus, it is possible to effectively remove the moisture of residual in filtering residue.
According to embodiments of the invention, in step (3), the temperature of described calcination process is 150～450 degrees Celsius, time
Between be 0.5～5 hour.Thus, it is possible to remove the moisture of residual in filtering residue further.
In another aspect of this invention, the present invention proposes a kind of manganese oxide catalyst.It is by foregoing
Prepared by method.Generally speaking, this manganese oxide catalyst has that with low cost, excellent catalytic effect, preparation method are simple, is prone to
At least one the advantages such as large-scale promotion application.
In still another aspect of the invention, the present invention proposes a kind of metal fuel battery.According to embodiments of the invention, should
Metal fuel battery contains foregoing manganese oxide catalyst.Thus, this metal fuel battery has previously described manganese
Whole features that oxide catalyst is had and advantage, generally speaking, this metal fuel battery is owing to having catalytic effect
Good catalyst, and then be obtained in that preferable battery efficiency, and this metal fuel battery have with low cost, preparation method is simple
Single, be prone to the advantages such as large-scale promotion application at least one.
Accompanying drawing explanation
Fig. 1 shows the flow chart preparing manganese oxide catalyst method according to embodiments of the present invention；And
Fig. 2 shows the manganese oxide catalyst of according to embodiments of the present invention 1 scanning electron under different amplification
Microscope figure.
Detailed description of the invention
Embodiments of the invention are described below in detail, and the example of described embodiment is shown in the drawings, the most from start to finish
Same or similar label represents same or similar element or has the element of same or like function.Below with reference to attached
The embodiment that figure describes is exemplary, is only used for explaining the present invention, and is not considered as limiting the invention.
In one aspect of the invention, the present invention proposes a kind of method preparing manganese oxide catalyst.According to this
Bright embodiment, with reference to Fig. 1, the method includes:
S100 hydro-thermal reaction
According to embodiments of the invention, in this step, water-soluble by containing manganese salt, metal dopant and potassium permanganate
Liquid carries out hydro-thermal reaction process.Concrete, according to embodiments of the invention, the temperature of hydro-thermal reaction is 100～200 degrees Celsius,
Mixing speed is 100～500r/min, and the response time is 5～30 hours.Thus, it is possible to the Mn oxide being effectively improved acquisition is urged
The specific surface area of agent, and then obtain preferable catalytic effect.
According to embodiments of the invention, manganese salt can be bivalent manganese hydrochlorate.Concrete, can be manganese sulfate, manganese nitrate etc..
Above-mentioned bivalent manganese hydrochlorate can effectively be converted to the Mn oxide with preferable catalytic performance in water-heat process, such that it is able to enter
One step improves the catalytic effect of the catalyst utilizing the method to prepare.In the aqueous solution containing manganese salt and potassium permanganate, manganese
Salt can be 1:(1～3 with the mol ratio of potassium permanganate), wherein, manganese salt is as the criterion with the molal quantity of manganese ion.Inventor is through excessive
Amount experiment finds, when manganese salt and described potassium permanganate mol ratio within the above range time, it is possible to make manganese salt be oxidized to catalysis
The oxide of the manganese of better performances, and the catalyst of acquisition can be made to have the pattern that micro-nano is thread.
According to embodiments of the invention, in this step, by the way of adding metal dopant in aqueous, will remove
Outside manganese element, have improve catalyst redox catalytic performance doped with metal elements water inlet thermal response obtain manganese oxygen
In compound.Thus, it is possible to by metal-doped, improve the catalytic effect of this catalyst further.Concrete, metal dopant can
With containing ferrum, cobalt, nickel, stannum, cerium, lanthanum, silver and platinum at least one.Such as, according to embodiments of the invention, metal dopant
Silver ion or cerium ion can be contained.Specifically, the soluble-salt containing above-mentioned metal ion can be used to mix as metal
Miscellaneous dose, thus, it is possible to easily the salt containing above-mentioned metal ion is added to the solution containing manganese salt and potassium permanganate.
In the aqueous solution configured, manganese salt can be 1:(0.01～0.3 with the mol ratio of metal dopant).Wherein, the rubbing of manganese salt
That number is in terms of manganese ion, and the molal quantity of metal dopant is in terms of the molal quantity of doped metal ion.Thus, it is possible to utilize above-mentioned gold
The metallic element belonged in adulterant interacts with Mn oxide, such that it is able to improve the catalytic effect of this catalyst further.
Inventor finds have the adulterant of above-mentioned metallic element through great many of experiments, can be under less doping content, it is achieved manganese
The raising of oxide catalyst catalytic performance.
Inventor, through further investigation, by regulating the actual conditions of hydro-thermal reaction, and adds in hydro-thermal reaction solution
Add metal dopant, can effectively control surface topography and the composition of the Mn oxide of acquisition.Concrete, properly increase hydro-thermal
The temperature of reaction, can make the pressure in hydrothermal reaction kettle (i.e. autoclave) raise, advantageously form specific surface area bigger
Mn oxide.Concrete, inventor is found by great many of experiments, when the temperature controlling hydro-thermal reaction is above-mentioned scope, and can
To obtain the Mn oxide with the thread pattern of micro-nano.Such as, according to a particular embodiment of the invention, the temperature of hydro-thermal reaction can
Think 100～150 degrees Celsius.It will be appreciated to those of skill in the art that the temperature of the pressure in reactor and hydro-thermal reaction
And the volume of reactor is relevant.According to embodiments of the invention, by the control to hydrothermal temperature, can be anti-by hydro-thermal
The pressure in still is answered to regulate in the range of 0～2MPa.According to embodiments of the invention, in this step, hydro-thermal reaction is improved
Temperature and reactor in pressure, advantageously form that specific surface area is bigger, the Mn oxide of good catalytic activity.So
And, too high temperature or pressure will improve the hydrothermal treatment process requirement to reaction vessel, thus cause the rising of production cost,
And reaction condition excessively harshness will cause potential safety hazard in actual large-scale production.Therefore, by the temperature of hydro-thermal reaction and
Stress control, within the scope of above-mentioned, be conducive to, on the premise of the catalytic effect ensureing catalyst, reducing production cost, improve
The safety of hydrothermal treatment consists.Further, when the aqueous solution of hydro-thermal reaction contains the metal-doped element outside demanganization element, shape
The manganese oxide catalyst become also is more prone to form the micro-nano pattern with large specific surface area.Specifically, with the addition of metal
After doped chemical, the manganese oxidant of formation has the diameter thread pattern of less micro-nano, so that this manganese oxide catalyst
Can have bigger specific surface area, and then preferable catalytic effect can be obtained.
In the present invention, term " micro-nano silk " refers in particular to diameter micron or the filament of Nano grade.Such as, according to this
Manganese oxide catalyst prepared by the method for bright embodiment, the diameter of its filament can be 0.1～2 micron.According to the present invention
Specific embodiment, it is thus achieved that manganese oxide catalyst in, the diameter of single micro-nano silk can be less than 200nm.
According to embodiments of the invention, the response time can also be 12～24 hours.Inventor finds through great many of experiments,
The proper extension hydro-thermal reaction time, the aqueous solution in reactor can be made fully to react, and be conducive to the Mn oxide tool obtained
There are bigger specific surface area and preferable catalytic performance.Thus, it is possible to improve the catalytic performance of the catalyst obtained further,
Ensureing that it has a thread pattern of preferable micro-nano, and prevent owing to the response time is long and cause the production cycle long, impact should
The yield of method.
According to embodiments of the invention, in hydrothermal reaction process, mechanical agitation can be used, raw to improve hydro-thermal reaction
Become the catalytic performance of thing.Concrete, mixing speed can be controlled 100～500r/min.Preferably stir thus, it is possible to obtain
Mix effect, it is possible to prevent from stirring fast too fast and generation and the growth of Mn oxide nucleus in hydrothermal reaction process being caused negatively
Impact.
S200 filters
According to embodiments of the invention, in this step, the product of hydro-thermal reaction is carried out filtration treatment, retains filtering residue.
It should be noted that in this step, the actual conditions of filtration treatment is not particularly limited, as long as can be anti-with hydro-thermal by filtering residue
The solvent in product is answered to separate.Such as, according to embodiments of the invention, filter membrane can be utilized to incite somebody to action in the way of using sucking filtration
Filtering residue separates with solvent.It should be noted that in this step, particular type and the aperture of filter membrane are not particularly limited, this
Skilled person can select according to the concrete condition of the actual conditions of hydro-thermal reaction and product.
S300 is dried, grinds and calcination process
According to embodiments of the invention, in this step, previously obtained filtering residue is dried successively, grinds and roasts
Burning processes.Thus, it is possible to the moisture fully gone out in filtering residue, the thread Mn oxide of micro-nano obtained after alleviation hydro-thermal reaction
Agglomeration, thus obtain the preferable manganese oxide catalyst of catalytic performance.
Concrete, according to embodiments of the invention, the temperature of dried can be 50～115 degrees Celsius, and the time is permissible
It it is 3～24 hours.Thus, it is possible to effectively remove the moisture of residual in filtering residue.Subsequently, the filtering residue through dried is ground
Mill processes, such that it is able to alleviate the reunion of the thread filtering residue of micro-nano that dried causes, in order to obtain dispersibility the driest
Powder.Subsequently, the powder through grinding is carried out calcination process.According to embodiments of the invention, the temperature of calcination process can
Thinking 150～450 degrees Celsius, the time is 0.5～5 hour.Thus, it is possible to remove the moisture of residual in filtering residue further.According to
Embodiments of the invention, the manganese oxide catalyst utilizing said method to prepare has the diameter thread pattern of less micro-nano, obtains
In the manganese oxide catalyst obtained, the diameter of single micro-nano silk can be less than 100nm, so that this manganese oxide catalyst energy
Enough there is bigger specific surface area, and then preferable catalytic effect can be obtained.
In sum, the above-mentioned method preparing manganese oxide catalyst have following advantages at least one:
1, with low cost, operating process is simple.The method can be real by simple hydro-thermal and minority post-processing step
The preparation of existing manganese oxide catalyst, advantageously reduces production cost.
2, the method condition is the gentleest, requires relatively low to the instrument and equipment needed for producing, advantageously reduces and utilize the party
Method carries out the equipment cost produced, and safe and reliable.
3, the method be obtained in that specific surface area compared with big, the thread manganese oxide catalyst of the preferable micro-nano of catalytic performance, its
In the diameter of single micro-nano silk can reach below 200nm.
4, the manganese oxide catalyst morphology controllable that the method obtains is high, and different batches product gap is little, can realize big
Large-scale production.
In another aspect of this invention, the present invention proposes a kind of manganese oxide catalyst.According to embodiments of the invention,
It is prepared by foregoing method.Thus, this manganese oxide catalyst has urging of previously described method acquisition
Whole features that agent is had and advantage, do not repeat them here.Generally speaking, this manganese oxide catalyst has low cost
Honest and clean, excellent catalytic effect, preparation method are simple, be prone to the advantages such as large-scale promotion application at least one.
In still another aspect of the invention, the present invention proposes a kind of metal fuel battery.According to embodiments of the invention, should
Metal fuel battery contains foregoing manganese oxide catalyst.Thus, this metal fuel battery has previously described manganese
Whole features that oxide catalyst is had and advantage, generally speaking, this metal fuel battery is owing to having catalytic effect
Good catalyst, and then be obtained in that preferable battery efficiency, and this metal fuel battery have with low cost, preparation method is simple
Single, be prone to the advantages such as large-scale promotion application at least one.
It should be noted that this metal fuel battery can also have to realize metal fuel battery uses its of function
His parts or structure.Such as, this metal fuel battery has battery container further, in order to limit reaction compartment；Positive pole with
And negative pole, in order to realize the redox reaction of fuel, thus the chemical energy in fuel is converted into electric energy.Wherein, on negative pole
Having previously described manganese oxide catalyst, in other words, previously described manganese oxide catalyst is supported on battery cathode
On, in order to there is chemical reaction on catalysis negative pole.Thus, it is possible to utilize the previously described manganese oxygen with preferable catalytic performance
Compound catalyst, improves the reaction efficiency of electrode, and then can improve the battery efficiency of this metal fuel battery.
Below by specific embodiment, the present invention will be described, it will be appreciated to those of skill in the art that following
The purpose that is merely to illustrate that of specific embodiment, and limit the scope of the present invention never in any form.It addition, below
Embodiment in, unless stated otherwise, the material and facility used is all commercially available.If in embodiment below
In, concrete treatment conditions and processing method are not expressly recited, then can use condition as known in the art and side
Method processes.
Embodiment 1
Weigh manganese sulfate 21.84g, 6 nitric hydrate cerium 5.0g, potassium permanganate 35g respectively, respectively that it is the most molten
Solution is in the deionized water of 1L.The solution of above-mentioned preparation is joined in the autoclave of 5l, be 100 DEG C, mixing speed in temperature
It is to react 10 hours under conditions of 0MPa for 300r/min, pressure；Carry out sucking filtration after having reacted, then filtering residue is placed in 80 DEG C
In drying baker dry, to be dried complete after pulverize.The pattern of the catalyst obtained is as shown in Figure 2.Understand with reference to Fig. 2, should
The manganese oxide catalyst that method obtains has the thread pattern of micro-nano, and micro-nano silk degree of scatter is preferable, and single micro-nano silk is straight
Footpath is less than 200nm.Patent (104505520A) is used to be prepared as aluminium-air cell air electrode the grained catalyst prepared,
Catalytic efficiency during-1.0V is 110mA/cm at normal temperatures2。
Embodiment 2
Weigh manganese nitrate 17g, 6 nitric hydrate cerium 3.0g, potassium permanganate 40g respectively, dissolved the most respectively
In the deionized water of 1L.The solution of above-mentioned preparation is joined in the autoclave of 5l, temperature be 120 DEG C, mixing speed be
400r/min, pressure are to react 14 hours under conditions of 0.5MPa；Carry out sucking filtration after having reacted, then filtering residue is placed in 80 DEG C
In drying baker dry, to be dried complete after pulverize.The grained catalyst prepared is used patent (104505520A) system
Standby one-tenth aluminium-air cell air electrode, catalytic efficiency during-1.0V is 125mA/cm at normal temperatures2。
Embodiment 3:
Weigh manganese sulfate 21.84g, 6 nitric hydrate cerium 2.0g, potassium permanganate 40g respectively, respectively that it is the most molten
Solution is in the deionized water of 1L.The solution of above-mentioned preparation is joined in the autoclave of 5l, be 140 DEG C, mixing speed in temperature
It is to react 18 hours under conditions of 0.65MPa for 500r/min, pressure；Carry out sucking filtration after having reacted, then filtering residue is placed in
In 80 DEG C of drying baker dry, to be dried complete after pulverize.The grained catalyst prepared is used patent
(104505520A) being prepared as aluminium-air cell air electrode, catalytic efficiency during-1.0V is 120mA/cm at normal temperatures2。
Embodiment 4
Weigh manganese sulfate 21.84g, silver nitrate 1.0g, potassium permanganate 40g respectively, be dissolved in the most respectively
In the deionized water of 1L.The solution of above-mentioned preparation is joined in the autoclave of 5l, temperature be 100 DEG C, mixing speed be
300r/min, pressure are to react 10 hours under conditions of 0MPa；Carry out sucking filtration after having reacted, then filtering residue is placed in 80 DEG C and does
In dry case dry, to be dried complete after pulverize.Patent (104505520A) is used to prepare the grained catalyst prepared
Becoming aluminium-air cell air electrode, catalytic efficiency during-1.0V is 120mA/cm at normal temperatures2。
Embodiment 5
Weigh manganese nitrate 17g, silver nitrate 0.5g, potassium permanganate 35g respectively, be dissolved in 1L's the most respectively
In deionized water.The solution of above-mentioned preparation is joined in the autoclave of 5l, temperature be 120 DEG C, mixing speed be 400r/
Min, pressure are to react 14 hours under conditions of 0.5MPa；Carry out sucking filtration after having reacted, then filtering residue is placed in 80 DEG C and is dried
In case dry, to be dried complete after pulverize.Patent (104505520A) is used to be prepared as the grained catalyst prepared
Aluminium-air cell air electrode, catalytic efficiency during-1.0V is 145mA/cm at normal temperatures2。
Embodiment 6
Weigh manganese nitrate 17g, silver nitrate 1.2g, potassium permanganate 35g respectively, be dissolved in 1L's the most respectively
In deionized water.The solution of above-mentioned preparation is joined in the autoclave of 5l, temperature be 140 DEG C, mixing speed be 500r/
Min, pressure are to react 18 hours under conditions of 0.65MPa；Carry out sucking filtration after having reacted, then filtering residue is placed in 80 DEG C and is dried
In case dry, to be dried complete after pulverize.Patent (104505520A) is used to be prepared as the grained catalyst prepared
Aluminium-air cell air electrode, catalytic efficiency during-1.0V is 130mA/cm at normal temperatures2。
In the description of this specification, reference term " embodiment ", " some embodiments ", " specific embodiment ", " show
Example " or the description of " some examples " etc. means to combine this embodiment or example describes specific features, structure, material or feature
It is contained at least one embodiment or the example of the present invention.In this manual, the schematic representation of above-mentioned term is differed
Surely identical embodiment or example are referred to.And, the specific features of description, structure, material or feature can be any
One or more embodiments or example combine in an appropriate manner.
Although an embodiment of the present invention has been shown and described, it will be understood by those skilled in the art that: not
These embodiments can be carried out multiple change in the case of departing from the principle of the present invention and objective, revise, replace and modification, this
The scope of invention is limited by claim and equivalent thereof.
Claims (10)
1. the method preparing manganese oxide catalyst, it is characterised in that including:
(1) aqueous solution containing manganese salt, metal dopant and potassium permanganate is carried out hydro-thermal reaction process, described hydro-thermal reaction
Temperature be 100～200 degrees Celsius, mixing speed is 100～500r/min, and the response time is 5～30 hours；
(2) the hydro-thermal reaction product obtained in step (1) is carried out filtration treatment, and collect filtering residue；
(3) described filtering residue is dried process, milled processed and calcination process successively, in order to obtain the catalysis of described Mn oxide
Agent.
Method the most according to claim 1, it is characterised in that described manganese salt is bivalent manganese hydrochlorate.
Method the most according to claim 1, it is characterised in that in described aqueous solution, described manganese salt and described permanganic acid
The mol ratio of potassium is 1:(1～3).
Method the most according to claim 1, it is characterised in that described metal dopant contain ferrum, cobalt, nickel, stannum, cerium, lanthanum,
Silver and platinum at least one.
Method the most according to claim 1, it is characterised in that described manganese salt is 1 with the mol ratio of described metal dopant:
(0.01～0.3).
Method the most according to claim 1, it is characterised in that in step (1), the described response time is 12～24 little
Time.
Method the most according to claim 1, it is characterised in that in step (3), the temperature of described dried be 50～
115 degrees Celsius, the time is 3～24 hours.
Method the most according to claim 1, it is characterised in that in step (3), the temperature of described calcination process is 150
～450 degrees Celsius, the time is 0.5～5 hour.
9. a manganese oxide catalyst, it is to be prepared by the method described in any one of claim 1～8.
10. a metal fuel battery, it is characterised in that containing the manganese oxide catalyst described in claim 9.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107170996A (en) * | 2017-05-17 | 2017-09-15 | 中国第汽车股份有限公司 | A kind of La Mn compound oxygen reduction catalyst materials and preparation method thereof |
| CN107469821A (en) * | 2017-08-11 | 2017-12-15 | 中国科学院城市环境研究所 | A kind of preparation method of load Ag manganese oxide catalysts and application |
| CN108246290A (en) * | 2017-12-29 | 2018-07-06 | 厦门大学 | A kind of catalyst of room temperature efficient removal air or formaldehyde in waste water and preparation method thereof |
| CN110292936A (en) * | 2019-07-23 | 2019-10-01 | 福建龙新三维阵列科技有限公司 | Metal oxide catalyst and its preparation with high stability energy |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102698770A (en) * | 2012-03-20 | 2012-10-03 | 郑远 | Manganese dioxide composite metal oxide catalyst, preparation method and application |
| CN103055847A (en) * | 2012-12-25 | 2013-04-24 | 中国科学院生态环境研究中心 | Manganese-based oxide catalyst used for catalytic oxidation of ethanol, and preparation method and application thereof |
| CN104001502A (en) * | 2014-05-29 | 2014-08-27 | 中国科学院生态环境研究中心 | Cerium-manganese catalyst for decomposing ozone at room temperature in high humidity as well as preparation method and application of cerium-manganese catalyst |
| CN105576260A (en) * | 2015-11-26 | 2016-05-11 | 中国第一汽车股份有限公司 | Preparation method of Beta-manganese oxide and carbon composite battery cathode catalyst |
-
2016
- 2016-07-14 CN CN201610554943.8A patent/CN106207198A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102698770A (en) * | 2012-03-20 | 2012-10-03 | 郑远 | Manganese dioxide composite metal oxide catalyst, preparation method and application |
| CN103055847A (en) * | 2012-12-25 | 2013-04-24 | 中国科学院生态环境研究中心 | Manganese-based oxide catalyst used for catalytic oxidation of ethanol, and preparation method and application thereof |
| CN104001502A (en) * | 2014-05-29 | 2014-08-27 | 中国科学院生态环境研究中心 | Cerium-manganese catalyst for decomposing ozone at room temperature in high humidity as well as preparation method and application of cerium-manganese catalyst |
| CN105576260A (en) * | 2015-11-26 | 2016-05-11 | 中国第一汽车股份有限公司 | Preparation method of Beta-manganese oxide and carbon composite battery cathode catalyst |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107170996A (en) * | 2017-05-17 | 2017-09-15 | 中国第汽车股份有限公司 | A kind of La Mn compound oxygen reduction catalyst materials and preparation method thereof |
| CN107469821A (en) * | 2017-08-11 | 2017-12-15 | 中国科学院城市环境研究所 | A kind of preparation method of load Ag manganese oxide catalysts and application |
| CN108246290A (en) * | 2017-12-29 | 2018-07-06 | 厦门大学 | A kind of catalyst of room temperature efficient removal air or formaldehyde in waste water and preparation method thereof |
| CN110292936A (en) * | 2019-07-23 | 2019-10-01 | 福建龙新三维阵列科技有限公司 | Metal oxide catalyst and its preparation with high stability energy |
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