CN109473682A - A supported dual-core perovskite-type oxide carbon nano-microsphere catalyst, its preparation method and application - Google Patents
A supported dual-core perovskite-type oxide carbon nano-microsphere catalyst, its preparation method and application Download PDFInfo
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Abstract
本发明涉及金属空气电池催化剂领域，尤其涉及一种负载双核钙钛矿型氧化物碳纳米微球催化剂，其制备方法及应用。所述制备方法包括：将A、B、D三种金属的水溶性盐按照摩尔比溶解于去离子水中，加入碳球原料，混合搅拌制备混合溶液；将超临界水与混合溶液混合并反应，冷却，冷却后的样品经洗涤，干燥，得到催化剂粉末；将催化剂粉末进行热处理，冷却，得到负载双核钙钛矿型氧化物碳纳米微球催化剂；所述负载双核钙钛矿型氧化物碳纳米微球催化剂的通式为ABxD1‑xO3@C纳米球。制得的负载双核钙钛矿型氧化物碳纳米微球催化剂尺寸均匀细小，催化活性高，可提高ORR和OER反应的催化性能，进而大大提高金属空气电池的电化学性能。The invention relates to the field of metal-air battery catalysts, in particular to a supported bi-nuclear perovskite-type oxide carbon nano-microsphere catalyst, a preparation method and applications thereof. The preparation method includes: dissolving water-soluble salts of three metals A, B and D in deionized water according to the molar ratio, adding carbon ball raw materials, mixing and stirring to prepare a mixed solution; mixing and reacting supercritical water with the mixed solution, Cooling, the cooled sample is washed and dried to obtain catalyst powder; the catalyst powder is heat-treated and cooled to obtain a supported bi-nuclear perovskite-type oxide carbon nano-microsphere catalyst; the supported bi-nuclear perovskite-type oxide carbon nano-particles The general formula of the microsphere catalyst is AB x D 1‑x O 3 @C nanospheres. The prepared supported binuclear perovskite-type oxide carbon nano-microsphere catalyst has uniform and small size and high catalytic activity, which can improve the catalytic performance of ORR and OER reactions, thereby greatly improving the electrochemical performance of metal-air batteries.
Description
Technical field
The present invention relates to metal-air battery catalyst field more particularly to a kind of load double-core perofskite type oxide carbon
Nanosphere catalyst, preparation method and application.
Background technique
Metal-air battery is " half fuel " battery for integrating primary battery and fuel cell feature, it is by positive, negative
Pole, electrolyte composition.As a positive electrode active material, aluminium, magnesium, zinc are as negative electrode active material, electrolyte KOH for oxygen in air
Solution, NaOH solution, NaCl aqueous solution or seawater etc..Metal-air battery is high by its distinctive energy density, capacity is big, valence
Lattice are cheap, advantages of environment protection, are widely paid close attention to by domestic and international researcher in recent years.Wherein, only zinc-air battery is
Can charge and discharge, in addition two kinds of air cells can not charge and discharge, it is necessary to realized by replacement anode plate " mechanical " can charge and discharge,
This allows for metal-air battery and there are many inconvenience in practical applications.If want realize can charge and discharge, develop bifunctional catalyst
Oxygen reduction reaction (ORR) occurs simultaneously and oxygen evolution reaction (OER) is the basis of research.The performance of air cathode directly affects gold
Belong to the chemical property of air cell, therefore the catalyst of catalytic air cathode oxidation and reduction reaction is metal-air battery reality
Existing commercialized key factor.Wherein, the limited performance of air cathode is poor in the dynamic performance of oxygen reduction reaction, overpotential
It is higher, to directly result in the power decline of battery.Specific reaction process, the oxygen in air pass through gas by nickel screen
Diffusion layer enters the Catalytic Layer of air cathode, and oxygen reduction reaction occurs under the double action of Catalytic Layer and electric current.Therefore, it urges
Effect of the activity of agent played in air cathode is most important.
In numerous catalyst, perofskite type oxide makes it have very because of the features such as tool conductivity is high, rich reserves
Big potentiality to be exploited.The general formula structure of perofskite type oxide is ABO3, A cations are mostly the biggish alkali gold of ionic radius
Belong to, alkaline-earth metal or rare earth metal, such as La, Ca, Sr, Ba, B cations for the lesser high valence transition metal of ionic radius from
Son, such as Ni, Co, Fe, Mn, Cr.B is that key element plays catalytic action in perovskite oxide, and A bit element primarily serves whole
The stability of a material crystalline structure.Also, A, B cations can be by other metal substitutes, and the selectivity of element is more
It is more, the available bigger promotion of catalytic performance.
The preparation method of perofskite type oxide has very much, for solid-phase synthesis, although yield is high, and particle size
It is larger.And coprecipitation is suitable for preparing the catalyst powder of fine uniform, but complex process, be difficult to control.Meanwhile merely
Perofskite type oxide, due to the disadvantages such as the larger uniformity of powder granule is poor, oxygen adsorption capacity is poor, specific surface area is low,
As metal-air battery catalyst, catalytic activity is lower, improves the power density of metal-air battery smaller, together
When constant-current discharge stability also reduce.
In addition, the carbon materials such as metal oxide and carbon nanotube, graphene, Nano carbon balls is compound, dipping is generallyd use
The method of reduction or mechanical mixture.The uniformity of the composite catalyst that these preparation methods obtain and the size of partial size without
Method control.For the Metal Supported of the Nano carbon balls of core-shell structure, template and multiple hydro-thermal reaction is mostly used to obtain, the method
The technique of preparation is more complicated, is unfavorable for being mass produced, and by multiple hydro-thermal method by metal composite oxide coat or
It is carried on the surface of Nano carbon balls, load capacity is uncontrollable, and covered effect is poor, and obtained catalyst particle size size is inhomogenous, carbon ball
Between it is easy to reunite.Existing these problems seriously hinder the commercial applications of metal-air battery.
The information disclosed in the background technology section is intended only to increase the understanding to general background of the invention, without answering
When being considered as recognizing or imply that the information constitutes the prior art already known to those of ordinary skill in the art in any form.
Summary of the invention
In order to solve the above technical problems, the purpose of the present invention is to provide a kind of load double-core perofskite type oxide carbon to receive
Rice microspherical catalyst, preparation method and application.This method faces various metals salting liquid and carbon ball raw material using continous way is super
Boundary's hydrothermal synthesis method and heat treatment technics will have general formula structure ABxD1-xO3Perofskite type oxide is embedded into Nano carbon balls in situ
(with ABxD1-xO3@C nano spherical shape formula indicates), obtain load double-core perofskite type oxide carbon nanometer micro ball catalyst.It is obtained
Load double-core perofskite type oxide carbon nanometer micro ball catalyst size uniformly tiny (300-500nm), perovskite type metal oxygen
The purity of compound is higher.Be embedded into Nano carbon balls difunctional perovskite type metal oxide can show it is efficient, stable
Catalytic activity, can be improved the catalytic performance of ORR and OER reaction, and then greatly improve the chemical property of metal-air battery.
Purpose to realize the present invention, the embodiment of the invention provides a kind of load double-core perofskite type oxide carbon nanometer is micro-
The preparation method of sphere catalyst, includes the following steps:
The water soluble salt of tri- kinds of metals of A, B, D is dissolved in deionized water according to molar ratio, carbon ball raw material, mixing is added
Stirring prepares mixed solution；
Supercritical water is mixed and reacted with mixed solution, cooling, sample after cooling is washed, and it is dry, it is catalyzed
Agent powder；Wherein, reaction temperature is 400-550 DEG C, is optionally 430-510 DEG C；Reaction pressure is 20-50MPa, is optionally
28-38MPa；Reaction time is 30-200s, is optionally 45-120s；
Catalyst fines are heat-treated, it is cooling, obtain load double-core perofskite type oxide carbon nanometer micro ball catalysis
Agent；Wherein, heat treatment temperature is 300-500 DEG C, is optionally 300-400 DEG C；
The general formula of the load double-core perofskite type oxide carbon nanometer micro ball catalyst is ABxD1-xO3@C nano ball；A packet
Include at least one of La, Sr, Ca, Ba；B or D separately includes at least one of Fe, Cr, Co, Mn, Ni；0 < x <
1。
According to the common knowledge of this field, in practical operation, the additional amount of the water soluble salt of three kinds of metal salts can be according to rubbing
You are than adjustment up and down.
The preparation method of above-mentioned load double-core perofskite type oxide carbon nanometer micro ball catalyst is in a kind of possible realization
In mode, the water soluble salt of tri- kinds of metals of A, B, D and the mass ratio of carbon ball raw material are 0.9-1.5, are optionally 1.1-1.35；
The additional amount of deionized water are as follows: deionized water 80-110ml is added in every 1g carbon ball raw material.
The preparation method of above-mentioned load double-core perofskite type oxide carbon nanometer micro ball catalyst is in a kind of possible realization
In mode, the preparation method of supercritical water includes: that deionized water is heated to supercriticality, wherein heating temperature 350-
550 DEG C, it is optionally 400-480 DEG C.
The preparation method of above-mentioned load double-core perofskite type oxide carbon nanometer micro ball catalyst is in a kind of possible realization
In mode, carbon ball raw material is added, after mixing prepares mixed solution, 30% H is added2O2Solution, additional amount are that mixing is molten
The 1%-4% of liquid total volume.H2O2The oxidisability of supercritical water can be improved in the addition of solution.
The preparation method of above-mentioned load double-core perofskite type oxide carbon nanometer micro ball catalyst is in a kind of possible realization
In mode, carbon ball raw material includes at least one of starch, glucose, maltose or cellulose.
The preparation method of above-mentioned load double-core perofskite type oxide carbon nanometer micro ball catalyst is in a kind of possible realization
In mode, the step of supercritical water and mixed solution are mixed and reacted includes: that mixed solution is pumped into reactor using pump,
The range of flow of the pump is 5-16ml/min；Deionized water is pumped into reactor by another pump, and heater is passed through in centre, will be gone
Ionized water is heated to supercriticality, and the range of flow of the pump is 20-30ml/min；The reactor is injection-type reactor；
Fluid after reaction passes through cooling system and filtration system；
Optionally, the pump is efficient liquid-phase chromatographic pump；It is by the range of flow of pump that mixed solution is pumped into reactor
8-12ml/min；The range of flow of another pump is 22-27ml/min.
Supercritical water and mixed solution are mixed in injection-type reactor, temperature and pressure needed for reaction can be reached moment
Power is reacted rapidly, and the reaction time is short, since solubility is very low in supercritical water for perovskite type metal oxide, may make production
Object is precipitated rapidly, into cooling device, it is therefore prevented that the growth of particle becomes larger and reunites.
The preparation method of above-mentioned load double-core perofskite type oxide carbon nanometer micro ball catalyst is in a kind of possible realization
In mode, the step of catalyst fines are heat-treated includes being placed in catalyst fines in crucible, the N in tube furnace2Or
It is heat-treated in Ar atmosphere.
The preparation method of above-mentioned load double-core perofskite type oxide carbon nanometer micro ball catalyst is in a kind of possible realization
In mode, after catalyst fines are heat-treated, the type of cooling is natural cooling.
The embodiment of the invention also provides a kind of load double-core perofskite type oxide carbon nanometer micro ball catalyst, general formulas
For ABxD1-xO3@C nano ball；Wherein, A includes at least one of La, Sr, Ca, Ba；B or D separately include Fe, Cr,
At least one of Co, Mn, Ni；0 < x < 1.
Above-mentioned load double-core perofskite type oxide carbon nanometer micro ball catalyst in one possible implementation, calcium titanium
Mine type oxide ABxD1-xO3It is embedded in the two sides of Nano carbon balls；The load double-core perofskite type oxide nanosphere catalysis
The size of agent is 300-500nm.
Above-mentioned load double-core perofskite type oxide carbon nanometer micro ball catalyst in one possible implementation, leads to
Formula is LaFe0.5Cr0.5O3@C nano ball or general formula are LaFe0.5Mn0.5O3@C nano ball or general formula are BaNi0.5Cr0.5O3@C receives
Rice ball or general formula are BaNi0.5Co0.5O3@C nano ball.
The embodiment of the invention also provides a kind of preparation methods of the cathode inks of metal-air battery, including under
State step:
By above-mentioned load double-core perofskite type oxide carbon nanometer micro ball catalyst, conductive carbon black, polytetrafluoroethylene (PTFE)
(PTFE) it is mixed with dehydrated alcohol to obtain the final product.
The embodiment of the invention also provides a kind of cathode inks of metal-air battery comprising above-mentioned load is double
Core perofskite type oxide carbon nanometer micro ball catalyst, conductive carbon black, PTFE and dehydrated alcohol.
The embodiment of the invention also provides above-mentioned load double-core perofskite type oxide carbon nanometer micro ball catalyst or above-mentioned
Application of the cathode inks in metal air battery cathodes piece.
The utility model has the advantages that
(1) the preparation side of load double-core perofskite type oxide carbon nanometer micro ball catalyst provided in an embodiment of the present invention
Method is obtained in the perofskite type oxide insertion Nano carbon balls of dual-core architecture by continuous supercritical water thermal method and heat treatment
Catalyst.The special physicochemical property of supercritical water (dielectric constant is low, saturation degree is high etc.) prepares nano-metal-oxide
Ideal response medium, and being heat-treated may make carbon ball surface to have more defects and active site.This method by supercritical water and
Metal salt solution mix simultaneously react rapidly, the reaction time is short, due to perovskite type metal oxide in supercritical water solubility
It is very low, it may make product to be precipitated rapidly, and pass through cooling, it is therefore prevented that the growth of particle becomes larger and reunites.Load double-core obtained
Perofskite type oxide carbon nanometer micro ball catalyst size is uniform tiny (300-500nm), and soilless sticking phenomenon occurs.
(2) the preparation side of load double-core perofskite type oxide carbon nanometer micro ball catalyst provided in an embodiment of the present invention
Method can control the load of titanium ore type oxide in carbon nanometer micro ball by controlling the additional amount ratio of metal salt and carbon ball raw material
The perofskite type oxide carbon nanometer micro ball catalyst of dual-core architecture is made in amount.
(3) the preparation side of load double-core perofskite type oxide carbon nanometer micro ball catalyst provided in an embodiment of the present invention
Method, H2O2The oxidisability of supercritical water can be improved in the addition of solution.
(4) the preparation side of load double-core perofskite type oxide carbon nanometer micro ball catalyst provided in an embodiment of the present invention
Method mixes supercritical water and metal salt solution in reactor, temperature and pressure needed for can reaching reaction moment, the reaction time
It is short.
Also, by further control reaction flow velocity, heating temperature and pressure and other parameters, single stepping can will be high
Pure perofskite type oxide is embedded into Nano carbon balls in situ.Entire reaction process can effectively prevent various metals salt to occur
Cross contamination generates other impurities (oxide such as containing only a kind of metal or the oxide containing only two kinds of metals), and what is obtained is double
The purity is high of function perovskite type metal oxide.
(5) the preparation side of load double-core perofskite type oxide carbon nanometer micro ball catalyst provided in an embodiment of the present invention
Method is conducive to promote industrialization using continuous production technology.
(6) load double-core perofskite type oxide carbon nanometer micro ball catalyst provided in an embodiment of the present invention, conductivity are high.
In later period cathode sheets preparation process, perovskite oxide had both played the effect of the bifunctional catalyst of hydrogen reduction and oxygen catalysis reaction
Fruit, while combining between carrier Nano carbon balls and conductive carbon black and more consolidating, the Adhering capacity of the catalyst is improved, is solved
The problems such as obscission existing for metal oxide catalyst and poorly conductive.And the catalyst is mixed with conductive carbon black
It is more uniform, and then it is coated to the cathode sheets catalyst dispersion being sintered on nickel screen more evenly.Therefore, it is embedded into Nano carbon balls
Difunctional perovskite type metal oxide can show efficient, stable catalytic activity, improve urging for ORR and OER reaction
Change performance, and then greatly improves the chemical property of metal-air battery.The catalytic performance of catalyst OER reaction mentions
Height, accelerate metal-air battery realize can charge and discharge paces.
Detailed description of the invention
One or more embodiments are illustrated by the picture in corresponding attached drawing, these exemplary theorys
The bright restriction not constituted to embodiment.Dedicated word " exemplary " means " being used as example, embodiment or illustrative " herein.
Here as any embodiment illustrated by " exemplary " should not necessarily be construed as preferred or advantageous over other embodiments.
Fig. 1 is the La of dual-core architecture prepared by the embodiment of the present invention 10.5Fe0.5Cr0.5O3The TEM of@C nano ball schemes.
Fig. 2 is the La of the dual-core architecture prepared in the embodiment of the present invention 10.5Fe0.5Cr0.5O3@C nano sphere catalyst application
To the constant-current discharge curve of aluminium-air cell.
Fig. 3 is the La of the dual-core architecture prepared in the embodiment of the present invention 10.5Fe0.5Cr0.5O3@C nano sphere catalyst application
To the charging and discharging curve of zinc-air battery.
Fig. 4 is the LaFe of the dual-core architecture prepared in the embodiment of the present invention 20.5Mn0.5O3@C nano sphere catalyst is applied to
The charging and discharging curve of zinc-air battery.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described, it is clear that described embodiments are some of the embodiments of the present invention, rather than
Whole embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creative work premise
Under every other embodiment obtained, shall fall within the protection scope of the present invention.Unless otherwise explicitly stated, otherwise whole
In a specification and claims, it is to include that the term " include " or its transformations will be understood as
The element or component stated, and do not exclude other elements or other components.
In addition, in order to better illustrate the present invention, numerous details is given in specific embodiment below.
It will be appreciated by those skilled in the art that without certain details, the present invention equally be can be implemented.In some embodiments, right
It is not described in detail in raw material well known to those skilled in the art, element, method, means etc., in order to highlight master of the invention
Purport.
Embodiment 1
A kind of load double-core perofskite type oxide carbon nanometer micro ball catalyst LaFe0.5Cr0.5O3@C nano ball, size
Size is 500nm.
Above-mentioned load double-core perofskite type oxide carbon nanometer micro ball catalyst LaFe0.5Cr0.5O3The preparation side of@C nano ball
Method includes the following steps:
By La (NO3)3·6H2O、Fe(NO3)3·9H2O、Cr(NO3)3·9H2O is according to molar ratio weighing (three kinds of metal salts
Take 3.3643g, 1.5694g and 1.5543g respectively), be added 600ml deionized water magnetic agitation obtain various metals salting liquid,
It weighs 6g starch to be repeatedly added in more metal salt solutions on a small quantity, 50 DEG C of heating water baths stir 1h, and H is added2O2Solution (30%,
12ml), continue to stir 30min, improve the oxidisability of supercritical water, finally obtain the mixed solution of various metals salt and starch；
The LaFe of dual-core architecture is prepared in situ using continuous supercritical water thermal synthesis method0.5Cr0.5O3@C nano ball: firstly,
Various metals salt and starch mixed solution are pumped into reactor by efficient liquid-phase chromatographic pump, flow 8ml/min；Together
When, another efficient liquid-phase chromatographic pump by deionized water pass through heater, 400 DEG C of heating temperature so that deionized water is heated to
Then supercriticality is pumped into reactor, flow 22ml/min；Reactor is designed using injecting type, so that supercritical water
It is uniformly mixed in the reactor with the mixed solution of various metals salt and starch and reacts the 45s (temperature of reactor: 400 rapidly
DEG C, reaction pressure are as follows: 30MPa)；Fluid after reaction successively passes through cooling system, filtration system, counterbalance valve, then spend from
Sub- water and dehydrated alcohol are washed repeatedly to neutrality, are centrifuged 2h using centrifuge (revolving speed: 600r/min), are put into refrigerator and freeze
For 24 hours, 80 DEG C of freeze-drying 10h obtain catalyst fines；
Catalyst fines after freeze-drying are placed in crucible, the N in tube furnace2Room temperature 40min is warming up under atmosphere
300 DEG C of annealing 1.5h, are cooled to room temperature, obtain LaFe0.5Cr0.5O3@C catalyst.
A kind of preparation method of the cathode inks of metal-air battery, includes the following steps:
Take LaFe obtained above0.5Cr0.5O3@C nano sphere catalyst 2.4g, conductive carbon black VXC-72R powder 4.7g,
60% (quality of PTFE powder account for gross mass 60%) PTFE solution 7.320g, 100ml dehydrated alcohol, is mixed
2.6h obtains cathode for metal-air battery catalyst pulp.
Using nickel screen as collector conductive network, above-mentioned cathode slurry is coated on the nickel screen of collector, at 300 DEG C
It is sintered 60min, the air cathode of metal-air battery can be obtained.
The assembled battery in self-control test device by above-mentioned air cathode and anode aluminium sheet, electrolyte is the potassium hydroxide of 4M
Aqueous solution carries out discharge performance test, the results showed that, aluminium-air cell is assembled using catalyst of the present invention, is tested
It is 293.64mW/cm to maximum power density2, corresponding to discharge voltage at this time is 1.0213V, current density 287.50mA/cm2。
Then constant-current discharge test, current density 250mA/cm are carried out to the aluminium-air cell of preparation2, it is 25 DEG C of left sides in environment temperature
Under conditions of the right side, discharge 2000min, and voltage is still able to maintain in 1.32V, and test results are shown in figure 2.
The air cathode piece and anode (zine plate) of preparation are assembled into zinc-air battery, in KOH (the addition acetic acid of electrolyte 6M
Zinc) in test charge-discharge performance, test result is, by the charge and discharge cycles of 100 circles, there is no decaying, charging electricity for battery
Pressure is stablized in 2.03V or so, and discharge voltage is stablized in 1.21V or so, and test results are shown in figure 3.
Embodiment 2
A kind of load double-core perofskite type oxide carbon nanometer micro ball catalyst LaFe0.5Mn0.5O3@C nano ball, size
Size is 470nm.
Above-mentioned load double-core perofskite type oxide carbon nanometer micro ball catalyst LaFe0.5Mn0.5O3The preparation of@C nano ball
Method includes the following steps:
By La (NO3)3·6H2O、Fe(NO3)3·9H2O、Mn(NO3)2·4H2O is according to molar ratio weighing (three kinds of metal salts
Take 3.1314g, 1.4608g and 0.9076g respectively), be added 450ml deionized water magnetic agitation obtain various metals salting liquid,
It weighs 5g glucose to be repeatedly added in more metal salt solutions on a small quantity, 50 DEG C of heating water baths stir 1h, and H is added2O2Solution (30%,
9ml), continue to stir 30min, improve the oxidisability of supercritical water, finally obtain the mixed solution of various metals salt and starch；
Remaining step and technological parameter are same as Example 1.
A kind of preparation method of the cathode inks of metal-air battery, includes the following steps:
Take the LaFe of above-mentioned preparation0.5Mn0.5O3@C nano sphere catalyst 2.3g, conductive carbon black VXC-72R powder 5.32g,
60% (quality of PTFE powder account for gross mass 60%) PTFE solution 6.820g, 100ml dehydrated alcohol, is mixed
2.4h obtains cathode for metal-air battery catalyst pulp；Using nickel screen as collector conductive network, by above-mentioned cathode slurry
It is coated on the nickel screen of collector, is sintered 45min at 320 DEG C, the air cathode of metal-air battery can be obtained.
The assembled battery in self-control test device by above-mentioned air cathode and anode aluminium sheet, electrolyte is the potassium hydroxide of 4M
Aqueous solution carries out discharge performance test, the results showed that, aluminium-air cell is assembled using catalyst of the present invention, is tested
It is 296.87mW/cm to maximum power density2, corresponding to discharge voltage at this time is 0.9896V, current density 300.00mA/cm2。
Then constant-current discharge test, current density 245mA/cm are carried out to the aluminium-air cell of preparation2, it is 24 DEG C of left sides in environment temperature
Under conditions of the right side, discharge 2000min, and voltage is still able to maintain in 1.30V.The air cathode piece and anode (zine plate) of preparation assemble
At zinc-air battery, charge-discharge performance is tested in the KOH (addition zinc acetate) of electrolyte 6M, test result is, by 100 circles
Charge and discharge cycles, battery there is no decaying, stablize in 2.02V or so by charging voltage, and discharge voltage is stablized on the left side 1.19V
The right side, test results are shown in figure 4.
Embodiment 3
A kind of load double-core perofskite type oxide carbon nanometer micro ball catalyst BaNi0.5Cr0.5O3@C nano ball, size
Size is 360nm.
Above-mentioned load double-core perofskite type oxide carbon nanometer micro ball catalyst BaNi0.5Cr0.5O3The preparation of@C nano ball
Method includes the following steps:
By Ba (NO3)2、Ni(NO3)2·6H2O、Cr(NO3)3·9H2According to molar ratio weighing, (three kinds of metal salts take O respectively
3.6177g, 2.0127g and 2.7696g), 665ml deionized water magnetic agitation is added and obtains various metals salting liquid, weigh 7g
Maltose is repeatedly added in more metal salt solutions on a small quantity, and 50 DEG C of heating water baths stir 1h, and H is added2O2Solution (30%,
16.63ml), continue to stir 30min, improve the oxidisability of supercritical water, the mixing for finally obtaining various metals salt and starch is molten
Liquid；
Remaining step and technological parameter are same as Example 1.
A kind of preparation method of the cathode inks of metal-air battery, includes the following steps:
Take the BaNi of above-mentioned preparation0.5Cr0.5O3@C catalyst 1.9g, conductive carbon black VXC-72R powder 3.2g, 60%
(quality of PTFE powder account for gross mass 60%) PTFE solution 4.520g, 100ml dehydrated alcohol, carries out mixing 2.3h,
Obtain cathode for metal-air battery catalyst pulp；Using nickel screen as collector conductive network, above-mentioned cathode slurry is coated
Onto the nickel screen of collector, it is sintered 40min at 350 DEG C, the air cathode of metal-air battery can be obtained.
The assembled battery in self-control test device by above-mentioned air cathode and anode aluminium sheet, electrolyte is the potassium hydroxide of 4M
Aqueous solution carries out discharge performance test, the results showed that, aluminium-air cell is assembled using catalyst of the present invention, is tested
It is 316.05mW/cm to maximum power density2, corresponding to discharge voltage at this time is 1.0535V, current density 300.00mA/cm2。
Constant-current discharge test display, current density 262.5mA/cm are carried out to aluminium-air cell2, it is 26 in environment temperature
DEG C or so under conditions of, discharge 2000min, and voltage is still able to maintain in 1.33V.
Embodiment 4
A kind of load double-core perofskite type oxide carbon nanometer micro ball catalyst BaNi0.5Co0.5O3@C nano ball, size
Size is 420nm.
Above-mentioned load double-core perofskite type oxide carbon nanometer micro ball catalyst BaNi0.5Co0.5O3The preparation of@C nano ball
Method includes the following steps:
By Ba (NO3)2、Ni(NO3)2·6H2O、Co(NO3)2·6H2According to molar ratio weighing, (three kinds of metal salts take O respectively
5.1110g, 2.8431g and 2.8459g), 900ml deionized water magnetic agitation is added and obtains various metals salting liquid, weigh 9g
Cellulose is repeatedly added in more metal salt solutions on a small quantity, and 50 DEG C of heating water baths stir 1h, and H is added2O2Solution (30%,
26.5ml), continue to stir 30min, improve the oxidisability of supercritical water, the mixing for finally obtaining various metals salt and starch is molten
Liquid；
Remaining step and technological parameter are same as Example 1.
A kind of preparation method of the cathode inks of metal-air battery, includes the following steps:
Take the BaNi of above-mentioned preparation0.5Co0.5O3@C catalyst 2.9g, conductive carbon black VXC-72R powder 4.29g, 60%
(quality of PTFE powder account for gross mass 60%) PTFE solution 7.370g, 100ml dehydrated alcohol, carries out mixing 2.7h,
Obtain cathode for metal-air battery catalyst pulp；Using nickel screen as collector conductive network, above-mentioned cathode slurry is coated
Onto the nickel screen of collector, it is sintered 25min at 380 DEG C, the air cathode of metal-air battery can be obtained.
The assembled battery in self-control test device by above-mentioned air cathode and anode aluminium sheet, electrolyte is the potassium hydroxide of 4M
Aqueous solution carries out discharge performance test, the results showed that, aluminium-air cell is assembled using catalyst of the present invention, is tested
It is 304.10mW/cm to maximum power density2, corresponding to discharge voltage at this time is 1.0137V, current density 300.00mA/cm2。
Constant-current discharge test display, current density 275mA/cm are carried out to aluminium-air cell2, it is 24.5 in environment temperature
DEG C or so under conditions of, discharge 2000min, and voltage is still able to maintain in 1.35V.
Comparative example
LaFe is prepared using conventional hydrothermal method0.5Cr0.5O3Perofskite type oxide, whole preparation process are added without carbon source,
LaFe obtained0.5Cr0.5O3Catalyst size size is 800nm-1 μm, and granular size is uneven.
Take the LaFe of preparation0.5Cr0.5O3Catalyst 2.4g, conductive carbon black VXC-72R powder 4.7g, 60% (PTFE powder
Quality account for the 60% of gross mass) PTFE solution 7.320g, 100ml dehydrated alcohol, carry out mixing 2.6h, obtain metal sky
Pneumoelectric pond cathode inks；Using nickel screen as collector conductive network, above-mentioned cathode slurry is coated to collector
On nickel screen, it is sintered 60min at 300 DEG C, the air cathode of metal-air battery can be obtained.
The assembled battery in self-control test device by above-mentioned air cathode and anode aluminium sheet, electrolyte is the potassium hydroxide of 4M
Aqueous solution carries out discharge performance test, the results showed that, aluminium-air cell is assembled into using the catalyst that this comparative example synthesizes, is surveyed
It is 202.75mW/cm that examination, which obtains maximum power density,2, corresponding to discharge voltage at this time is 0.6758V, and current density is
300.00mA/cm2。
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features；
And these are modified or replaceed, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (15)
1. a kind of preparation method for loading double-core perofskite type oxide carbon nanometer micro ball catalyst, includes the following steps:
The water soluble salt of tri- kinds of metals of A, B, D is dissolved in deionized water according to molar ratio, carbon ball raw material is added, is mixed
Prepare mixed solution；
Supercritical water is mixed and reacted with mixed solution, cooling, sample after cooling is washed, and it is dry, obtain catalyst powder
End；Wherein, reaction temperature is 400-550 DEG C；Reaction pressure is 20-50MPa；Reaction time is 30-200s；By catalyst fines
It is heat-treated, it is cooling, obtain load double-core perofskite type oxide carbon nanometer micro ball catalyst；Wherein, heat treatment temperature is
300-500 DEG C, it is optionally 300-400 DEG C；
The general formula of the load double-core perofskite type oxide carbon nanometer micro ball catalyst is ABxD1-xO3@C nano ball；A includes
At least one of La, Sr, Ca, Ba；B or D separately includes at least one of Fe, Cr, Co, Mn, Ni；0 < x < 1.
2. preparation method according to claim 1, it is characterised in that: reaction temperature is 430-510 DEG C；Reaction pressure is
28-38MPa；Reaction time is 45-120s；Heat treatment temperature is 300-400 DEG C.
3. preparation method according to claim 1, it is characterised in that: the water soluble salt and carbon ball of tri- kinds of metals of A, B, D are former
The mass ratio of material is 0.9-1.5, is optionally 1.1-1.35.
4. preparation method according to claim 1, it is characterised in that: carbon ball raw material is added, it is molten that preparation mixing is mixed
After liquid, 30% H is added2O2Solution, additional amount are the 1%-4% of mixed solution total volume.
5. preparation method according to claim 1, it is characterised in that: mix and react supercritical water with mixed solution
Step includes: that mixed solution is pumped into reactor using pump, and the range of flow of the pump is 5-16ml/min；Another pump will be gone
Ionized water is pumped into reactor, and heater is passed through in centre, deionized water is heated to supercriticality, the range of flow of the pump is
20-30ml/min；The reactor is injection-type reactor；Fluid after reaction passes through cooling system and filtration system.
6. preparation method according to claim 5, it is characterised in that: the pump is efficient liquid-phase chromatographic pump；It will mix molten
The range of flow that liquid is pumped into the pump in reactor is 8-12ml/min；The range of flow of another pump is 22-27ml/min.
7. preparation method according to claim 1, it is characterised in that: carbon ball raw material include starch, glucose, maltose or
At least one of cellulose.
8. preparation method according to claim 1, it is characterised in that: the additional amount of deionized water are as follows: every 1g carbon ball raw material
Deionized water 80-110ml is added.
9. preparation method according to claim 1, it is characterised in that: the preparation method of supercritical water includes: by deionization
Water is heated to supercriticality；Wherein, heating temperature is 350-550 DEG C, and optionally, heating temperature is 400-480 DEG C.
10. preparation method according to claim 1, it is characterised in that: the step of being heat-treated catalyst fines packet
It includes and catalyst fines is placed in crucible, the N in tube furnace2Or it is heat-treated in Ar atmosphere.
11. a kind of load double-core perofskite type oxide carbon nanometer micro ball catalyst, general formula ABxD1-xO3@C nano ball；Its
In, A includes at least one of La, Sr, Ca, Ba；B or D separately includes at least one of Fe, Cr, Co, Mn, Ni；
0 < x < 1.
12. load double-core perofskite type oxide carbon nanometer micro ball catalyst according to claim 11, it is characterised in that:
Perofskite type oxide ABxD1-xO3It is embedded in the two sides of Nano carbon balls；The load double-core perofskite type oxide carbon nanometer is micro-
The size of sphere catalyst is 300-500nm.
13. a kind of preparation method of the cathode inks of metal-air battery includes the following steps: claim 11 institute
The load double-core perofskite type oxide carbon nanometer micro ball catalyst stated, conductive carbon black, polytetrafluoroethylene (PTFE) and dehydrated alcohol mixing
To obtain the final product.
14. a kind of cathode inks of metal-air battery comprising load double-core perovskite described in claim 11
Type oxide carbon nanometer micro ball catalyst, conductive carbon black, polytetrafluoroethylene (PTFE) and dehydrated alcohol.
15. described in load double-core perofskite type oxide carbon nanometer micro ball catalyst or claim 14 described in claim 11
Application of the cathode inks in metal air battery cathodes piece.
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