CN102683726A - Core-shell structure electric catalyst material for lithium air batteries and preparation method thereof - Google Patents
Core-shell structure electric catalyst material for lithium air batteries and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a core-shell structure electric catalyst material for lithium air batteries and a preparation method thereof. The electric catalyst material comprises a core layer formed by a transition metal oxide and a shell layer formed by a transition metal nitride, the core layer is a hollow or solid core, the inner diameter of the core layer is 0-50nm, the outer diameter of the core layer is 30-500nm, the thickness of the shell layer is 10-200nm, and the mass of the shell layer accounts for 10-40% of the mass of the electric catalyst material. The preparation method includes that the hollow or solid transition metal oxide is prepared by adopting a liquid phase method. On the basis, transition metal salt is nitrogenized directly to be covered on the surface of the transition metal oxide by adopting a nitriding sintering method, and the core-shell material is prepared by covering the transition metal nitride on the transition metal oxide. The core-shell material has good electrical conductivity and stability, can effectively reduce charging and discharging polarization of the lithium air batteries, reduces internal resistance of the batteries, has good discharging capacity simultaneously, is simple in preparation process method, convenient to operate and low in cost, and achieves large-scale production easily.
Description
Technical field
The invention belongs to electrochemical field, relate to a kind of lithium-air battery with nucleocapsid structure electrocatalyst materials and preparation method thereof.
Background technology
Because environmental problem becomes increasingly conspicuous, oil crisis is increasingly serious, and energy-conservation and new energy technology becomes human focus and research focus gradually.As everyone knows, lithium ion battery is the battery system of extremely representative and competitiveness in the new energy field, has been widely used in mobile phone and notebook computer etc., also has been the important choosing of PHEV of future generation and pure electric vehicle at present.Yet conventional lithium ion battery is the congenital restriction that is limited by it to a great extent; The lithium ion battery of low energy densities is difficult to satisfy the requirement of fields such as electric automobile to high-energy-density; And existing battery system is limited at the room for promotion of aspects such as energy density and power density, presses for the secondary cell new system of development based on new design, new material and new technology.
Lithium-air battery has caused widely and has paid close attention to as one of leading battery system of current field of batteries.It adopts the negative pole of lithium metal as battery; Positive pole generally is made up of eelctro-catalyst, material with carbon element, bonding agent; Airborne oxygen is as active material; Oxygen diffuses into battery through the external world and under the eelctro-catalyst effect, reacts, and anodal in theory capacity density is unlimited, is much better than conventional lithium ion battery.In addition; Lithium metal has good electronic conductance in all cell negative electrode materials, and its electrochemistry capacitance 3860mAh/g does not simultaneously consider that oxygen does active amount of substance; Its theoretical specific capacity approaches traditional fuel system (about 13000Wh/Kg) up to 11680Wh/Kg.Therefore, lithium-air battery is with its high specific capacity and specific energy and characteristic such as environmentally friendly and become the power conversion system that receives much concern at present, is expected to replace existing lithium ion battery and is used widely.
Lithium-air battery is not new ideas, just proposes the seventies as far back as twentieth century.Is not yet why lithium-air battery all popularized so far? Reason is that it exists critical defect, and wherein, serious polarization phenomena are the key factors that influence the performance of lithium-air battery performance.Eelctro-catalyst is as one of critical material of lithium-air battery, and factors such as the electrocatalysis characteristic of its material, stability, conductivity, specific area, appearance structure have very big influence to the polarization that reduces lithium-air battery, high specific capacity and cycle performance.A kind of eelctro-catalyst efficiently can greatly improve the efficient of lithium-air battery, suppresses the decomposition of electrolyte, thereby improves cycle life.Therefore, in order to reduce the polarization of lithium-air battery, improve battery performance, the research and development of eelctro-catalyst are essential.
The general eelctro-catalyst that adopts single transition metal oxide, metal nitride, noble metal etc. as lithium-air battery of present researcher.In lithium-air battery, transition metal oxide is the maximum eelctro-catalyst of research, at present to manganese oxide; Cobalt oxide, iron oxide, vanadium oxide; In lithium-air battery, wherein the performance of manganese oxide and cobalt oxide is the most outstanding as the Application Research of eelctro-catalyst for nickel oxide etc.(Journal of Power Sources 174,2007 1177-1182) waits the electrocatalysis characteristic of having studied dissimilar transition metal oxides, EMD (electrolytic oxidation manganese) and Co to Peter G.Bruce
3O
4Having discharge capacity, cycle performance and electrocatalysis characteristic preferably; Jiaxin Li (Electrochemistry Communications, 13,2011; 698-700) etc. the employing redox has been prepared carbon and has been carried the manganese oxide electrocatalysis material, and its discharge capacity surpasses 1800mAh/g, and discharge platform is higher than 2.8V; Charging platform is lower than 3.8V, and battery polarization reduces significantly; Yanming Cui employing hard template method such as (Solid State Ionics, 2012, in press) has been prepared the mesoporous Co of different model
3O
4, the charging platform of battery can be reduced to about 3.5V, and electrocatalysis characteristic is excellent.When using transition metal oxide as eelctro-catalyst; Its lithium-air battery has discharge capacity height, good cycle, the characteristic of electrocatalysis characteristic preferably; But the conductivity of transition metal oxide is bad, and reaction is terminated easily, can not give play to stable electrocatalysis characteristic.Shanmu Dong (Chemical Communications, 2011,47,11291-11293) wait to adopt the ammonia reducing process with MoO
3Being reduced into MoN is eelctro-catalyst, because the MoN good electrical conductivity, it is high that it puts discharge platform, but its charging voltage does not reduce effectively, and catalytic performance also needs further to improve.Yi-Chun Lu (Journal of the American Chemical Society, 2010,132; 12170-12171) wait and to have prepared noble metal nano eelctro-catalyst PtAu/C and be applied in the lithium-air battery, result of study shows, the discharge voltage of battery have significantly improved (than about the high 0.2V of pure carbon); Charging voltage significantly reduces (than about the low 0.6V of pure carbon); Significantly promoted battery efficiency, but be to use noble metal electrocatalyst, its expensive raw material price; The specific capacity of battery and the performance of cycle performance are not very desirable, are difficult for large-scale commercial applicationsization.
Chinese patent CN 102240574 A disclose a kind of catalyst of being made up of transient metal complex and carbon black support; The lithium-air battery that uses this Preparation of Catalyst to become shows fine catalytic activity and stability; But the behavior that discharges and recharges of battery is undesirable under high current density, and the hydro thermal method of employing can not be controlled the catalyst pattern; Chinese patent CN 102306808 A disclose a kind of air electrode and have used catalyst to be raw material with manganese salt, silver salt, are carrier with the material with carbon element, and preparation carbon carries manganese oxide and carbon carries silver catalyst; With two kinds of carbon carrier material ball mill mixing; Obtain electrode material, preparation method's process is simple, but the ball mill mixing of two kinds of eelctro-catalysts; The skewness of catalyst causes catalytic effect not obvious.
In sum, a kind of eelctro-catalyst efficiently of exploitation is badly in need of in this area, has that electrocatalysis characteristic is good, good conductivity, good stability, a performance such as cheap, is applied to lithium-air battery.Transition metal oxide is as the extremely promising eelctro-catalyst of lithium-air battery; It is extensive to have material source; Electrocatalysis characteristic, battery discharge specific capacity and the good advantage of capability retention, however the conductivity of transition metal oxide is bad; Reaction is terminated easily, can not give play to stable electrocatalysis characteristic; Transition metal nitride; Have high chemical stability and conductivity, and can greatly improve the discharge voltage of battery, transition metal nitride is coated on the transition metal oxide surface; Can form the strong core-shell structure particles of conductivity good chemical stability; This type of composite electrocatalyst helps improving transition metal oxide in defectives such as poorly conductives, and its material source is extensive, and production and use cost are low.
Summary of the invention
The object of the present invention is to provide a kind of lithium-air battery to use the nucleocapsid electrocatalyst materials, this catalyst is the base metal eelctro-catalyst, can reduce cost significantly, compares with the transition metal oxide eelctro-catalyst, has higher conductivity.
To achieve these goals, a kind of lithium-air battery provided by the invention is used the nucleocapsid electrocatalyst materials, and said electrocatalyst materials comprises stratum nucleare that is made up of transition metal oxide and the shell that is made up of transition metal nitride.
Said stratum nucleare is hollow or solid core, and the stratum nucleare internal diameter is 0～50nm, and external diameter is 30～500nm, and shell thickness is 10nm～200nm.
Shell accounts for 10～40% of electrocatalyst materials quality among the present invention.
Said stratum nucleare transition metal oxide is one or more in iron oxide, cobalt oxide, manganese oxide, molybdenum oxide, nickel oxide, the vanadium oxide; The shell transition metal nitride is one or more in cobalt nitride, nitrided iron, nitrogenized manganese, molybdenum nitride, nickel oxide, the vanadium nitride.
Another object of the present invention also is to provide the electrocatalyst materials preparation method of a kind of hollow or solid core/shell structure, and its preparation method is following:
The first step: with emulsifiers dissolve in organic solvent; Under the mixing speed of 200～1000rpm; Add deionized water, formations mass ratio is an emulsifying agent: organic solvent: water=0～40: 10～80: 20～80 transparent micro emulsion, and to account for the microemulsion mass percent concentration be 0.5%～10% stratum nucleare transition metal salt presoma in adding then; Behind sonic oscillation, obtain the stratum nucleare precursor liquid.
Second step: under the mixing speed of 600～1200rpm; Adding concentration in the stratum nucleare precursor liquid is the ammoniacal liquor of 0.5～2.0mol/L; Until PH is neutral; At 30～70 ℃ of temperature reaction 1～10h down, filter then, washing, vacuumize make hollow or solid transition metal hydroxide, makes hollow or solid transition metal oxide through 300～700 ℃ of heat treatments;
The 3rd step: shell transition metal salt presoma is evenly mixed with nitrogen-containing compound; Be scattered in the solvent of water, methyl alcohol or ethanol; Add the transition metal oxide that second step obtained, after fully stirring, vacuumize; With desciccate under protective atmosphere through 500～1000 ℃ heat treatment, obtain the core-shell material that transition metal nitride coats transition metal oxide.
In second step of the present invention, heat treated temperature retention time is 2h～6h.The heating rate that reaches required heat treatment temperature is 1 ℃/min～10 ℃/min.
In the 3rd step of the present invention, heat treated temperature retention time is 1h～5h.The heating rate that reaches required heat treatment temperature is 1 ℃/min～10 ℃/min, and protective atmosphere is for being argon gas or nitrogen.
Sonic oscillation 0.5～2h in the said first step.
Said vacuum drying temperature is 60～120 ℃.
Add the transition metal oxide that second step obtained in described the 3rd step, fully stir 1～10h.
In the first step of the present invention, described emulsifying agent is one or more in APES, benzylphenol APEO, phenethyl phenol polyethenoxy ether or the phenethyl naphthols APEO.
In the first step of the present invention, described organic solvent is one or more in normal heptane, cyclohexane, kerosene, hydrogenated kerosene, diesel oil, toluene, the xylenes.
The present invention prepares in the process, and described stratum nucleare transition metal salt presoma is one or more in nitrate, acetate, sulfate, oxalates, villaumite, the carbonate.
The present invention prepares in the process, and described shell transition metal salt presoma is one or more in nitrate, acetate, sulfate, oxalates, villaumite, carbonate, the ammonium salt.
The present invention prepares in the process, and described nitrogen compound is one or more in urea, ammonium nitrate, melamine, ethylenediamine, pyridine, pyrroles, aniline, phthalocyanine, the porphyrin.
The present invention has following effect:
1, prepared material is that transition metal nitride is that shell coats the nucleocapsid structure of transition metal oxide for nuclear, and prepared material has good stable property.
2, prepared material is that transition metal nitride is that shell coats transition metal oxide for examining nucleocapsid structure; The transition metal metal nitride has good electrical conductivity; Remedied the shortcoming of transition metal oxide poorly conductive; Improve the electric conductivity of eelctro-catalyst, promoted the stable of electrocatalysis characteristic.
3, transition metal oxide is the stratum nucleare material, and its lithium-air battery has discharge capacity height, good cycle, the characteristic of electrocatalysis characteristic preferably; Transition metal nitride is the shell material, and the discharge platform of its lithium-air battery is high, can further reduce polarization.
4, adopt base metal as eelctro-catalyst, material source is extensive, has reduced the eelctro-catalyst cost.
5, adopt liquid phase method directly to obtain the hollow or the solid stratum nucleare of particle size, controllable thickness, adopt sintering process that the direct nitrogenize of transition metal salt is coated on the stratum nucleare material, form controlled core-shell material; Need at first synthetic micro polymer ball template through hard template method when having avoided preparation stratum nucleare material, save simultaneously polymer template need through the method for solvent or calcination remove loaded down with trivial details; The coating of shell material; With will prepare metal nitride through methods such as magnetron sputterings in advance and coat; Handle methods such as the nitridation sintered or plasma gas phase deposition coating in back through sol-gal process and compare, sintering process is coated to the direct nitrogenize of transition metal salt that preparation process on hollow or the solid transition metal oxide stratum nucleare is simple, controllability strong, can easily carry out continued operation, be convenient to large-scale production, easy to utilize.
6, the nucleocapsid structure electrocatalyst materials even particle distribution of the present invention's preparation, pattern is controlled.
In sum, a kind of lithium-air battery of the present invention is with nucleocapsid structure electrocatalyst materials and preparation method thereof, and described material is a nucleocapsid structure, and Dispersion of Particles is even, and the pattern of electrocatalyst materials is controlled, has satisfactory electrical conductivity, stability; Can reduce lithium-air battery effectively and discharge and recharge polarization, reduce the internal resistance of cell, have good discharge capacity concurrently; Preparation technology's method is simple, easy to operate simultaneously, cost is low, is prone to accomplish scale production; The catalyst with core-casing structure material of preparation is a kind of desirable eelctro-catalyst.
Description of drawings
Fig. 1 is the SEM figure that obtains material by embodiment 1.
Fig. 2 is the TEM figure that obtains material by embodiment 1.
Fig. 3 is the XRD figure that obtains material by embodiment 1.
Fig. 4 is the SEM figure that obtains material by embodiment 2.
Fig. 5 is the lithium-air battery AC impedance figure that obtains material by embodiment 3.
Fig. 6 is the lithium-air battery first charge-discharge curve chart that obtains material by embodiment 3.
Embodiment
Below in conjunction with embodiment, the present invention is done further explain, but be not restricted to the protection range of invention.
Embodiment 1
1) stratum nucleare material preparation: under the mixing speed of 400rpm, in 10 parts toluene, drip 60 parts distilled water, obtain transparent microemulsion, dropwise add iron nitrate solution, sonic oscillation is 1 hour then, and the acquisition weight concentration is 5% stratum nucleare precursor liquid; Under the mixing speed of 1200rpm; Slowly dripping concentration in the stratum nucleare precursor liquid is the ammoniacal liquor of 1.0mol/L; Until PH is neutral, reacts 4h down for 40 ℃ in temperature, and filtration, washing, vacuumize make the iron hydroxide medicine ball of diameter 40nm; 350 ℃ of sintering 3h then make the iron oxide medicine ball of diameter 40nm.
2) shell material preparation: urea and ferric nitrate are dispersed in the deionized water, add the iron oxide medicine ball, the mol ratio of iron oxide medicine ball, urea and ferric nitrate is 3: 2: 1, stirs 2h, then 80 ℃ of following vacuumizes; With the product of drying, under nitrogen environment, 800 ℃ of nitrogenize 4h obtain the electrocatalyst materials of medicine ball/shell structure of nitrided iron shell of iron oxide medicine ball stratum nucleare, the shell thickness 5nm of diameter 50nm.
3) pole piece preparation, battery assembling and test: the material of conductive carbon and preparation and bonding agent are by being mixed and made into positive pole at 80: 10: 10; Pole piece strikes out the electrode slice that diameter is 10mm; With the metal lithium sheet is negative pole; At electrolyte is 1MLiTFSI/PC:EC (1: 1), in being full of the glove box of argon gas, is assembled into the CR2025 button cell.(25 ℃) are with 0.1mA/cm under room temperature
2In pure oxygen environment, carry out the constant current charge-discharge test, discharging and recharging cut-ff voltage is 2～4.5V.
Can know that by SEM figure prepared electrocatalyst materials is the solid sphere of nanometer, particle diameter is about 65nm, and is as shown in Figure 1.Can know that by TEM figure prepared electrocatalyst materials is a nucleocapsid structure, outer field paler colour is being represented the shell material, and is as shown in Figure 2.Can be known that by XRD figure two kinds of materials of prepared electrocatalyst materials nitrogen iron and iron oxide explain that stratum nucleare is an iron oxide, shell is nitrided iron, and is as shown in Figure 3.First discharge specific capacity is 5000mAh/g, and discharge voltage plateau is increased to 2.8V, and charging platform is 3.4V, and electrocatalysis characteristic is good.
1) stratum nucleare material preparation: 5 parts APESs are dissolved in 50 parts the toluene; The distilled water of 0 part of Dropwise 5 under the mixing speed of 400rpm; Obtain transparent microemulsion; Dropwise add iron nitrate solution, sonic oscillation is 0.5 hour then, and the acquisition weight concentration is 2% stratum nucleare precursor liquid; Under the mixing speed of 1000rpm, slowly dripping concentration in the stratum nucleare precursor liquid is the ammoniacal liquor of 1.0mol/L, be neutrality until PH; React 5h down for 30 ℃ in temperature; Filtration, washing, vacuumize make internal diameter 20nm, the iron hydroxide hollow ball of external diameter 60nm, 500 ℃ of sintering 4h then; Obtain internal diameter 20nm, the iron oxide hollow ball of external diameter 60nm.
2) shell material preparation: urea and ferric nitrate are dispersed in the deionized water, add Fe
2O
3Hollow ball, Fe
2O
3The mol ratio of hollow ball, urea and ferric nitrate is 2: 2: 1, stirs 2h, then 80 ℃ of following vacuumizes; With the product of drying, under nitrogen atmosphere, 800 ℃ of sintering 5h obtain internal diameter 20nm, the electrocatalyst materials of the hollow ball/shell structure of the iron oxide hollow ball stratum nucleare of external diameter 60nm, the nitrided iron shell of shell thickness 10nm.
3) pole piece preparation, battery assembling are identical with embodiment 1 with test.
During prepared electrocatalyst materials is
Can find out that by SEM figure prepared material is the particle of hollow, particle diameter is about 70nm, and is as shown in Figure 4.Battery has good catalytic action, good discharge capacity.
Embodiment 3
1) stratum nucleare material preparation: 5 parts APESs are dissolved in 50 parts the toluene; The distilled water of 0 part of Dropwise 5 under the mixing speed of 400rpm; Obtain transparent microemulsion; Dropwise add cobalt nitrate solution, sonic oscillation is 0.5 hour then, and the acquisition weight concentration is 2% stratum nucleare precursor liquid; Under the mixing speed of 1000rpm, slowly dripping concentration in the stratum nucleare precursor liquid is the ammoniacal liquor of 1.0mol/L, be neutral until PH, reacts 5h down for 30 ℃ in temperature, and filtration, washing, vacuumize make internal diameter 20nm, the cobalt hydroxide hollow ball of external diameter 60nm., 350 ℃ of sintering 3h make internal diameter 20nm then, the cobaltosic oxide hollow ball of external diameter 60nm.
2) shell material preparation: urea and ammonium molybdate are dispersed in the deionized water, add the cobaltosic oxide hollow ball, the mol ratio of cobaltosic oxide hollow ball, ethylenediamine and ammonium molybdate is 5: 3: 3, stirs 3h, then 80 ℃ of following vacuumizes; With the product of drying, under ar gas environment, 900 ℃ of sintering 4h obtain internal diameter 20nm, the electrocatalyst materials of the hollow ball/shell structure of the cobaltosic oxide hollow ball stratum nucleare of external diameter 60nm, the molybdenum nitride shell of shell thickness 10nm.
3) pole piece preparation, battery assembling are identical with embodiment 1 with test.
Can find out that from AC impedance figure prepared material impedance reduces, and is as shown in Figure 5; At 0.1mA/cm
2Under the current density, the first discharge specific capacity of battery is that discharge platform reaches 3.0V about 6200mAh/g; Charging platform is 3.4V, polarizing voltage Δ V ≈ 0.4V, and when not containing prepared material in the electrode material; Its polarizing voltage Δ of battery V ≈ 1.65V explains and uses this electrocatalyst materials that polarizing voltage significantly reduces; The good results are evident in electro-catalysis, as shown in Figure 6.
Embodiment 4
1) stratum nucleare material preparation: 20 parts phenethyl phenol polyethenoxy ethers are dissolved in 60 parts the toluene; Under the mixing speed of 400rpm, drip 60 parts distilled water; Obtain transparent microemulsion; Dropwise add manganese acetate solution, sonic oscillation is 1 hour then, and the acquisition weight concentration is 4% stratum nucleare precursor liquid; Under the mixing speed of 1000rpm, slowly dripping concentration in the stratum nucleare precursor liquid is the ammoniacal liquor of 0.5mol/L, be neutrality until PH; React 6h down for 40 ℃ in temperature; Filtration, washing, vacuumize make internal diameter 40nm, the manganous hydroxide hollow ball of external diameter 200nm, 350 ℃ of sintering 3h then; Obtain internal diameter 40nm, the manganese oxide hollow ball of external diameter 200nm.
2) shell material preparation: aniline and ammonium metavanadate are dispersed in the ethanolic solution, add the manganese oxide hollow ball, the mol ratio of manganese oxide hollow ball, aniline and ammonium metavanadate is 10: 8: 5, stirs 4h, then 80 ℃ of following vacuumizes; With the product of drying, under argon gas atmosphere, 900 ℃ of sintering 4h obtain internal diameter 40nm, the electrocatalyst materials of the hollow ball/shell structure of the manganese oxide hollow ball stratum nucleare of external diameter 200nm, the vanadium nitride shell of shell thickness 80nm.
3) pole piece preparation, battery assembling are identical with embodiment 1 with test, and battery has good catalytic action.
Embodiment 5
1) stratum nucleare material preparation: 30 parts phenethyl phenol polyethenoxy ethers are dissolved in 80 parts the toluene; Under the mixing speed of 600rpm, drip 60 parts distilled water; Obtain transparent microemulsion; Dropwise add molybdenum chloride solution, sonic oscillation is 1 hour then, and the acquisition weight concentration is 6% stratum nucleare precursor liquid; Under the mixing speed of 1000rpm, slowly dripping concentration in the stratum nucleare precursor liquid is the ammoniacal liquor of 0.5mol/L, be neutrality until PH; React 6h down for 40 ℃ in temperature; Filtration, washing, vacuumize make internal diameter 40nm, the molybdenum hydroxide hollow ball of external diameter 300nm, 500 ℃ of sintering 5h then; Obtain internal diameter 40nm, the molybdenum oxide hollow ball of external diameter 300nm.
2) shell material preparation: aniline and ammonium metavanadate are dispersed in the ethanolic solution, add the molybdenum oxide hollow ball, the mol ratio of molybdenum oxide hollow ball, aniline and ammonium metavanadate is 9: 8: 5, stirs 4h, then 80 ℃ of following vacuumizes; With the product of drying, under argon gas atmosphere, 900 ℃ of sintering 4h obtain internal diameter 40nm, the electrocatalyst materials of the hollow ball/shell structure of the molybdenum oxide hollow ball stratum nucleare of external diameter 300nm, the vanadium nitride shell of shell thickness 80nm.
3) pole piece preparation, battery assembling are identical with embodiment 1 with test, and battery has good catalytic action, good discharge capacity.
Claims (10)
1. a lithium-air battery is used the nucleocapsid structure electrocatalyst materials, it is characterized in that, said electrocatalyst materials comprises stratum nucleare that is made up of transition metal oxide and the shell that is made up of transition metal nitride.
2. electrocatalyst materials according to claim 1 is characterized in that, said stratum nucleare is hollow or solid core, and the stratum nucleare internal diameter is 0～50nm, and external diameter is 30～500nm, and shell thickness is 10～200nm.
3. electrocatalyst materials according to claim 1 is characterized in that said shell accounts for 10～40% of electrocatalyst materials quality
4. according to claim 1 or 2 or 3 described electrocatalyst materials, it is characterized in that the stratum nucleare transition metal oxide is one or more in iron oxide, cobalt oxide, manganese oxide, molybdenum oxide, nickel oxide, the vanadium oxide; The shell transition metal nitride is one or more in cobalt nitride, nitrided iron, nitrogenized manganese, molybdenum nitride, nickel oxide, the vanadium nitride.
5. claim 1 or 2 or 3 described a kind of lithium-air batteries is characterized in that with the preparation method of nucleocapsid structure electrocatalyst materials, comprise the steps:
(1) with emulsifiers dissolve in organic solvent; Under the mixing speed of 200～1000rpm; Add deionized water, formations mass ratio is an emulsifying agent: organic solvent: water=0～40: 10～80: 20～80 transparent micro emulsion, and to account for the microemulsion mass percent concentration be 0.5%～10% stratum nucleare transition metal salt presoma in adding then; Behind sonic oscillation, obtain the stratum nucleare precursor liquid;
(2) under the mixing speed of 600～1200rpm; Adding concentration in the stratum nucleare precursor liquid is the ammoniacal liquor of 0.5～2.0mol/L; Until PH is neutral; At 30～70 ℃ of temperature reaction 1～10h down, filter then, washing, vacuumize make hollow or solid transition metal hydroxide, makes hollow or solid transition metal oxide through 300～700 ℃ of heat treatments;
(3) shell transition metal salt presoma is evenly mixed with nitrogen-containing compound; Be scattered in the solvent of water, methyl alcohol or ethanol; Add the transition metal oxide that step (2) obtains, after fully stirring, vacuumize; With desciccate under protective atmosphere through 500～1000 ℃ heat treatment, obtain the core-shell material that transition metal nitride coats transition metal oxide.
6. preparation method according to claim 5 is characterized in that, the heating rate that reaches required heat treatment temperature in the said step (2) is 1 ℃/min～10 ℃/min, and temperature retention time is 2～6h; The heating rate that reaches required heat treatment temperature in the said step (3) is 1 ℃/min～10 ℃/min, and temperature retention time is 1～5h, and protective atmosphere is argon gas or nitrogen.
7. preparation method according to claim 5 is characterized in that, sonic oscillation 0.5～2h in said (1) step; Said vacuum drying temperature is 60～120 ℃; Add the transition metal oxide that step (2) obtains in the described step (3), fully stir 1～10h.
8. preparation method according to claim 5 is characterized in that, described emulsifying agent is one or more in APES, benzylphenol APEO, phenethyl phenol polyethenoxy ether or the phenethyl naphthols APEO; Described organic solvent is one or more in normal heptane, cyclohexane, kerosene, hydrogenated kerosene, diesel oil, toluene, the xylenes.
9. preparation method according to claim 5: it is characterized in that described stratum nucleare transition metal salt presoma is one or more in nitrate, acetate, sulfate, oxalates, villaumite, the carbonate; Shell transition metal salt presoma is one or more in nitrate, acetate, sulfate, oxalates, villaumite, carbonate, the ammonium salt.
10. preparation method according to claim 5: it is characterized in that described nitrogen-containing compound is one or more in urea, ammonium nitrate, melamine, ethylenediamine, pyridine, pyrroles, aniline, phthalocyanine, the porphyrin.
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106669738B (en) * | 2016-12-19 | 2019-06-28 | 中国科学院深圳先进技术研究院 | Multielement hollow metal sulfide liberation of hydrogen catalyst and preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000048833A (en) * | 1998-07-29 | 2000-02-18 | Toyota Motor Corp | Fuel cell |
| CN101492576A (en) * | 2008-01-22 | 2009-07-29 | 中国科学院化学研究所 | Carbon nano-complex particle, preparation and uses thereof |
| EP2410079A2 (en) * | 2010-07-20 | 2012-01-25 | Bayer MaterialScience AG | Oxygen-consuming electrode |
-
2012
- 2012-04-28 CN CN201210131834.7A patent/CN102683726B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000048833A (en) * | 1998-07-29 | 2000-02-18 | Toyota Motor Corp | Fuel cell |
| CN101492576A (en) * | 2008-01-22 | 2009-07-29 | 中国科学院化学研究所 | Carbon nano-complex particle, preparation and uses thereof |
| EP2410079A2 (en) * | 2010-07-20 | 2012-01-25 | Bayer MaterialScience AG | Oxygen-consuming electrode |
Non-Patent Citations (2)
| Title |
|---|
| AURÉLIE DÉBART等: "An O2 cathode for rechargeable lithium batteries: The effect of a catalyst", 《JOURNAL OF POWER SOURCES》, vol. 174, no. 2, 6 December 2007 (2007-12-06), pages 1177 - 1182 * |
| SHANMU DONG等: "Molybdenum nitride based hybrid cathode for rechargeable lithium-O2 batteries", 《CHEMICAL COMMUNICATIONS》, vol. 47, no. 40, 19 September 2011 (2011-09-19), pages 11291 - 11293 * |
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