CN103170355A - Air electrode metal nitride catalyst applied to air battery - Google Patents
Air electrode metal nitride catalyst applied to air battery Download PDFInfo
- Publication number
- CN103170355A CN103170355A CN2012104297624A CN201210429762A CN103170355A CN 103170355 A CN103170355 A CN 103170355A CN 2012104297624 A CN2012104297624 A CN 2012104297624A CN 201210429762 A CN201210429762 A CN 201210429762A CN 103170355 A CN103170355 A CN 103170355A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- air
- metal nitride
- air electrode
- electrode metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Hybrid Cells (AREA)
- Inert Electrodes (AREA)
Abstract
The invention discloses a preparation method of an air electrode metal nitride catalyst applied to an air battery. The catalyst comprises a component AxByN, wherein X equals to 0.25-5, y equals to 1-5, A and B respectively represent a transition metal element, and N represents a nitrogen element. The catalyst is prepared by a sol gel-high-temperature sintering method including the following steps of: preparing metal salt into a water solution, adding carbon powder with a mass ratio of 1:2-4:1 to the catalyst as a carrier, and uniformly mixing the carbon powder with the solution by ultrasonic waves to form sol; drying the sol at a constant temperature of 90 DEG C to obtain dried gel; and processing the dried gel in presence of nitrogen sources at 500-1500 DEG C for 2-5 hours, thus obtaining the compound catalytic material. The compound catalytic material has good catalytic performance to oxygen reduction and can work under a relatively high electric current density with small loss of voltage; and besides, the preparation process of the catalyst is simple, and thus the industrial production of the catalyst can be realized.
Description
The preparation method
Technical field
The present invention relates to electrochemical field, be specifically related to a kind of air electrode metal nitride that is applied to air cell-carbon composite catalytic agent preparation method.Can be applicable to the catalysis material of the air electrode of zinc-air power battery, alkaline fuel cell, seawater battery.
Background technology
Metal-air battery is a kind of of fuel cell, acts as a fuel with metals such as zinc, aluminium, magnesium, and namely negative active core-shell material, obtain electric energy.Wherein zinc-air battery develops comparative maturity.Zinc-air battery is the cleanliness without any pollution electrochmical power source that truly can be recycled.Zinc oxide after being discharged becomes again metallic zinc after electrolytic regeneration, then makes battery.Zinc-air battery can not produce explosion accident, is stable electrochmical power source, only needs the stop supplies air oxygen, and it does not just react and does not discharge.In recent years, zinc-air battery is researched and developed, and is applied to power cell of vehicle.It is made of issuing the biochemical reaction of hair tonic and a kind of electrochmical power source of generation current at the catalyst of catalyst.
The important performance of battery (voltage of battery, power density) depends primarily on the performance of air electrode.The effect of air electrode is under the effect of catalyst, is that oxygen reduces, and this is dynamics complex process slowly.Catalyst is the key technology of air electrode, fuel cell.Seek catalyst cheap, efficient stable and become the key that improves the air performance.The progress of this technology directly affects zinc-air battery as the development of electrokinetic cell.According to the basic research to respiratory, in life entity, the structure that the material with catalytic action has metal ion and nitrogen Cheng Jian is separated out in hydrogen reduction and oxygen, as contained the porphyrin of metal and nitrogen-atoms.In these materials, M-N may be the catalytic activity position of oxygen reduction reaction.Infer that with this nitride of transition metal has the catalysis potentiality.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing catalyst that is applied to the air electrode metal nitride of air cell, this catalyst has good catalytic performance to hydrogen reduction, can work under high current density, the loss of voltage is little and comparatively stable.
To achieve the above object of the invention, the technical solution used in the present invention is as follows:
A kind of metal nitride catalyst agent of the air electrode for zinc-air battery.The composition general formula of described catalyst is A
xB
yN (x=0.25～5, y=1～5), wherein A, B are respectively a kind of transition metal, and N is the nitrogen element, and its transition metal is Fe, Ni, Mn, and this catalyst is take carbon black as carrier.
Metal nitride catalyst agent preparation method of the present invention.This catalyst adopts collosol and gel-high-temperature sintering process to make, adopt the aqueous solution of transition metal salt, adding with catalyst institute mass ratio is that the carbon dust of 2: 1 ~ 4: 1 is done carrier and made it mix formation colloidal sol with ultrasonic wave again, drying obtains xerogel under 90 ℃ of constant temperature, process 2～5h having under the condition of nitrogenous source in 500～1500 ℃, obtain described catalyst material.Described carbon black is one or more the mixture in VulcanXC72, acetylene black, graphite, active carbon.Described nitrogenous source is NH
3, urea, ethylenediamine, triethanolamine.
Its concrete steps:
1) base metal transition elements one or more mixture water soluble salts wherein such as Fe, Ni, Mn are water-soluble; Again material with carbon element is joined wherein, and after even with ultrasonic agitation, put into 90 ℃ of constant temperature oven constant temperature standing and drying, make it become xerogel.
2) take out the described xerogel of step 1, then be incorporated as therein NH
3, the nitrogenous source such as urea, ethylenediamine, and mix with ultrasonic.
3) the more described mixture of step 2 is put into Muffle furnace, temperature rise to 500～1500 ℃ process 2～5h again after, then allow it slowly naturally cool to room temperature, namely obtain described catalyst.
The invention has the advantages that:
A) catalyst of the present invention has good catalytic performance to hydrogen reduction, can be applied to zinc-air battery, comprises the application as electrokinetic cell.This catalyst also can be applied to the other types metal-air battery.
B) catalyst of the present invention is to be raw material by base metal transition elements one or more mixture water soluble salts wherein such as Fe, Ni, Mn, and such raw material resources is extensive, and is cheap, can reduce production costs.
C) this catalyst adopts the sol-gal process preparation, and the method can prepare the nano-particle material that particle diameter is little, be evenly distributed, and simultaneously, the time of the method sintering is short, and production technology is simple, can suitability for industrialized production.
Description of drawings
Fig. 1 is polarization curve of the present invention
Fig. 2 is constant-current discharge curve map of the present invention
The specific embodiment
Embodiment one:
Take the 4.04g ferric nitrate in beaker, add deionized water dissolving, make it to continue dissolving with ultrasonic wave, add 2.24gVulcanXC-72, ultrasonicly make it to mix processing, then obtain xerogel after putting into 90 ℃ of baking oven freeze-day with constant temperature, again with after 2.4g urea mixes, process 5h for 600 ℃ in Muffle furnace, obtain required nitride compound catalyze material, be labeled as FeN
4/ C, and be prepared into according to a conventional method electrode.This electrode shows good hydrogen reduction performance.Can find out from the polarization curve that records under air atmosphere, room temperature, alkaline electrolyte condition that Fig. 1 provides, at current potential be-the 0.2V condition under, electrode current density can reach 161mAcm
-2Can find out from the discharge curve that Fig. 2 shows, at discharge current density 130A.cm
-2Under, voltage reaches 0.98V, and voltage is very stable.
Embodiment two:
Take the 2.9g nickel nitrate in beaker, add deionized water dissolving, continuation dissolving with the ultrasonic wave skill, add 1.27g graphite and 1.27g VulcanXC-72, ultrasonicly make it to mix processing, then obtain xerogel after putting into 90 ℃ of baking oven freeze-day with constant temperature, again with after the 0.2g ethylenediamine mixes, process 4h for 800 ℃ in Muffle furnace, obtain required nitride compound catalyze material, be labeled as Ni
3N/C, and be prepared into according to a conventional method electrode.Can find out from the polarization curve that records under air atmosphere, room temperature, alkaline electrolyte condition that Fig. 1 provides, at current potential be-the 0.2V condition under, electrode current density can reach 150mA.cm
-2Can find out from the discharge curve that Fig. 2 shows, at discharge current density 130mA.cm
-2Under, voltage reaches 0.96V, and voltage is very stable.
Embodiment three:
Take 4.04g ferric nitrate and 2.9g nickel nitrate in beaker, add deionized water dissolving, make it to continue dissolving with ultrasonic wave, add 2.44g graphite and 2.44g active carbon, ultrasonicly make it to mix processing, then obtain xerogel after putting into 90 ℃ of baking oven freeze-day with constant temperature, again with after the 2.98g triethanolamine mixes, process 3h for 500 ℃ in Muffle furnace, obtain required nitride compound catalyze material, be labeled as Fe
2Ni
2N/C, and be prepared into according to a conventional method electrode.Can find out from the polarization curve that records under air atmosphere, room temperature, alkaline electrolyte condition that Fig. 1 provides, at current potential be-the 0.2V condition under, current density can reach 115mAcm
-2Can find out from the discharge curve that Fig. 2 shows, at current density 130mAcm
-2Under, voltage reaches 0.81V, and voltage is very stable.
Claims (4)
1. an air electrode metal nitride catalyst agent preparation method who is applied to air cell, is characterized in that the composition of this nitride can be expressed as A
xB
yN (x=0.25～5, y=1～5), A, B are respectively a kind of transition metal, and N is the nitrogen element, and wherein transition metal is Fe, Ni, Mn, and this catalyst is take carbon black as carrier.
2. a kind of air electrode metal nitride catalyst agent preparation method who is applied to air cell according to claim 1, it is characterized in that this catalyst adopts collosol and gel-high-temperature sintering process to make, adopt the aqueous solution of transition metal salt, adding with the catalyst quality ratio is that the carbon dust of 2: 1～4: 1 is done carrier and made it mix formation colloidal sol with ultrasonic wave again, drying obtains xerogel under 90 ℃ of constant temperature, process 2～5h having under the condition of nitrogenous source in 500～1500 ℃, obtain described compound catalyze material.
3. a kind of air electrode metal nitride catalyst agent preparation method that be applied to air cell described according to claims 1 is characterized in that described carbon black is one or more the mixture in VulcanXC-72, acetylene black, graphite, active carbon.
4. a kind of air electrode metal nitride catalyst agent preparation method that be applied to air cell described according to claims 1, is characterized in that, described nitrogenous source is NH
3, urea, ethylenediamine, triethanolamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210429762.4A CN103170355B (en) | 2012-11-01 | 2012-11-01 | A kind of air electrode metal nitride catalyst preparation method being applied to air cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210429762.4A CN103170355B (en) | 2012-11-01 | 2012-11-01 | A kind of air electrode metal nitride catalyst preparation method being applied to air cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103170355A true CN103170355A (en) | 2013-06-26 |
| CN103170355B CN103170355B (en) | 2015-10-21 |
Family
ID=48630801
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210429762.4A Active CN103170355B (en) | 2012-11-01 | 2012-11-01 | A kind of air electrode metal nitride catalyst preparation method being applied to air cell |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103170355B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103794806A (en) * | 2014-01-27 | 2014-05-14 | 中南大学 | Nano iron nitride-carbon composite catalyst for positive electrode of lithium-air battery and preparation method of composite catalyst |
| CN104415758A (en) * | 2013-09-06 | 2015-03-18 | 中国科学院大连化学物理研究所 | Preparation method and applications of non-noble metal electrocatalyst |
| CN105148971A (en) * | 2015-08-26 | 2015-12-16 | 中国科学院理化技术研究所 | High-performance ultrathin nitride electro-catalyst with functions of producing hydrogen and oxygen by means of electrochemically totally decomposing water, method for synthesizing high-performance ultrathin nitride electro-catalyst and application thereof |
| CN106252674A (en) * | 2016-10-12 | 2016-12-21 | 四川理工学院 | A kind of N doping charcoal carries non noble metal oxygen reduction/oxygen and separates out bifunctional catalyst |
| CN107742732A (en) * | 2017-09-30 | 2018-02-27 | 湖南工业大学 | A kind of iron content oxygen reduction catalyst and its preparation method and application |
| CN108767281A (en) * | 2018-06-28 | 2018-11-06 | 湖南工业大学 | A kind of oxygen reduction catalyst Fe-Mn/N-KB and its preparation method and application |
| CN109659567A (en) * | 2018-11-30 | 2019-04-19 | 天津大学 | The sugared cell anode catalyst and preparation method and application of nickel and cobalt containing nitrogen |
| CN111224114A (en) * | 2018-11-26 | 2020-06-02 | 中国科学院大连化学物理研究所 | Preparation and application of carbon-supported bimetallic nitride electrocatalyst |
| CN117276563A (en) * | 2023-09-29 | 2023-12-22 | 中国人民解放军国防科技大学 | Preparation method of metal monoatomic doped nitride-carbon composite aerogel electrocatalyst |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1960042A (en) * | 2006-10-13 | 2007-05-09 | 北京工业大学 | Non noble metal catalyst for cathode of direct methanol fuel cell, and preparation method |
| US20100048380A1 (en) * | 2008-08-21 | 2010-02-25 | Board Of Trustees Of Michigan State University | Novel catalyst for oxygen reduction reaction in fuel cells |
| CN101908628A (en) * | 2010-08-18 | 2010-12-08 | 天津久聚能源科技发展有限公司 | Transition metal composite oxide catalytic material and microwave preparation method thereof |
| CN102104154A (en) * | 2011-01-19 | 2011-06-22 | 清华大学 | Nitrogenous transition metal microbial fuel-cell catalyst and preparation method thereof |
| JP2011255336A (en) * | 2010-06-10 | 2011-12-22 | Toyota Motor Corp | Method for manufacturing catalyst support carrier, and method for manufacturing electrode catalyst |
| CN102299347A (en) * | 2010-06-25 | 2011-12-28 | 中国科学院大连化学物理研究所 | Application of catalyst in alkaline fuel cell |
| CN102324531A (en) * | 2011-05-26 | 2012-01-18 | 东华大学 | Carbon-supported CoN fuel-cell catalyst as well as preparation method and application thereof |
-
2012
- 2012-11-01 CN CN201210429762.4A patent/CN103170355B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1960042A (en) * | 2006-10-13 | 2007-05-09 | 北京工业大学 | Non noble metal catalyst for cathode of direct methanol fuel cell, and preparation method |
| US20100048380A1 (en) * | 2008-08-21 | 2010-02-25 | Board Of Trustees Of Michigan State University | Novel catalyst for oxygen reduction reaction in fuel cells |
| JP2011255336A (en) * | 2010-06-10 | 2011-12-22 | Toyota Motor Corp | Method for manufacturing catalyst support carrier, and method for manufacturing electrode catalyst |
| CN102299347A (en) * | 2010-06-25 | 2011-12-28 | 中国科学院大连化学物理研究所 | Application of catalyst in alkaline fuel cell |
| CN101908628A (en) * | 2010-08-18 | 2010-12-08 | 天津久聚能源科技发展有限公司 | Transition metal composite oxide catalytic material and microwave preparation method thereof |
| CN102104154A (en) * | 2011-01-19 | 2011-06-22 | 清华大学 | Nitrogenous transition metal microbial fuel-cell catalyst and preparation method thereof |
| CN102324531A (en) * | 2011-05-26 | 2012-01-18 | 东华大学 | Carbon-supported CoN fuel-cell catalyst as well as preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| 万术伟等: "燃料电池阴极非铂Fe/N/C和Co/N/C电催化剂的研究进展", 《电源技术》 * |
| 温美盛等: "溶胶-微波干燥法制备Nd0.6Ca0.4CoO3及其电化学性能", 《电源技术》 * |
| 赖渊等: "碱性燃料电池Co-N/C复合催化剂的电化学性能", 《化学学报》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104415758A (en) * | 2013-09-06 | 2015-03-18 | 中国科学院大连化学物理研究所 | Preparation method and applications of non-noble metal electrocatalyst |
| CN103794806A (en) * | 2014-01-27 | 2014-05-14 | 中南大学 | Nano iron nitride-carbon composite catalyst for positive electrode of lithium-air battery and preparation method of composite catalyst |
| CN105148971A (en) * | 2015-08-26 | 2015-12-16 | 中国科学院理化技术研究所 | High-performance ultrathin nitride electro-catalyst with functions of producing hydrogen and oxygen by means of electrochemically totally decomposing water, method for synthesizing high-performance ultrathin nitride electro-catalyst and application thereof |
| CN105148971B (en) * | 2015-08-26 | 2017-09-15 | 中国科学院理化技术研究所 | A kind of full ultra thin nitride elctro-catalyst for decomposing aquatic products hydrogen production oxygen of high-performance electric chemistry and its synthetic method and application |
| CN106252674A (en) * | 2016-10-12 | 2016-12-21 | 四川理工学院 | A kind of N doping charcoal carries non noble metal oxygen reduction/oxygen and separates out bifunctional catalyst |
| CN107742732A (en) * | 2017-09-30 | 2018-02-27 | 湖南工业大学 | A kind of iron content oxygen reduction catalyst and its preparation method and application |
| CN108767281A (en) * | 2018-06-28 | 2018-11-06 | 湖南工业大学 | A kind of oxygen reduction catalyst Fe-Mn/N-KB and its preparation method and application |
| CN111224114A (en) * | 2018-11-26 | 2020-06-02 | 中国科学院大连化学物理研究所 | Preparation and application of carbon-supported bimetallic nitride electrocatalyst |
| CN109659567A (en) * | 2018-11-30 | 2019-04-19 | 天津大学 | The sugared cell anode catalyst and preparation method and application of nickel and cobalt containing nitrogen |
| CN117276563A (en) * | 2023-09-29 | 2023-12-22 | 中国人民解放军国防科技大学 | Preparation method of metal monoatomic doped nitride-carbon composite aerogel electrocatalyst |
| CN117276563B (en) * | 2023-09-29 | 2024-02-27 | 中国人民解放军国防科技大学 | Preparation method of metal monoatomic doped nitride-carbon composite aerogel electrocatalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103170355B (en) | 2015-10-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103170355B (en) | A kind of air electrode metal nitride catalyst preparation method being applied to air cell | |
| CN101908628B (en) | Transition metal composite oxide catalytic material and microwave preparation method thereof | |
| CN112090441B (en) | Preparation method, product and application of cobalt-based carbon nanomaterial | |
| CN104289242B (en) | Preparation method for the high graphitization degree carbon base catalyst of fuel battery negative pole | |
| CN102101056B (en) | High-stability fuel-cell catalyst modified by oxide and preparation method thereof | |
| CN103977829B (en) | Composite and preparation and the application of carbon-nitrogen coated magnetic oxide nano-particles | |
| CN103495432A (en) | Method for preparing efficient stable fuel cell catalyst | |
| CN105186011B (en) | Ca-Ti ore type compound/graphene composite material and preparation method and application | |
| KR101352794B1 (en) | Manufacturing Method of Platinum-Manganese dioxide/Carbon Complex for Positive Electrode of Lithium-Air Battery | |
| CN110474050B (en) | Preparation method of doped carbon/manganese sulfide composite material | |
| CN102104157A (en) | Preparation method for carbon dry gel | |
| CN110492112A (en) | A kind of hydrogen reduction composite catalyst and preparation method thereof | |
| CN103326040B (en) | Double-function oxygen electrode catalyst of lithium air battery | |
| CN103545537A (en) | Double-perovskite structure catalyst material for cathode of lithium air battery and preparation method of catalyst material | |
| CN114447353A (en) | Fuel cell catalyst with high-density active sites and preparation method thereof | |
| CN103706389A (en) | Preparation method of lithium air battery catalyst with double catalytic activities | |
| CN111640953A (en) | Air electrode catalyst of aluminum-air battery and preparation method thereof | |
| CN108963388A (en) | A kind of method improving lithium-air battery energy density and output power and the lithium-air battery based on this method | |
| CN112142125B (en) | Method for preparing high-nickel ternary positive electrode material by secondary growth method | |
| CN113629256A (en) | Preparation method of Fe-doped PANI/MXene derived carbon-based Fe-N-C electrocatalyst | |
| CN110611079B (en) | Titanium-manganese bimetallic sodium phosphate @ carbon composite material, preparation thereof and application thereof in sodium-ion battery | |
| CN102658185B (en) | Catalyst for secondary reversible air electrode and preparation method thereof | |
| CN111584893A (en) | Air electrode catalyst of aluminum-air battery, air electrode and preparation method of air electrode catalyst | |
| CN115036520B (en) | Composite oxygen electrode catalyst of water system lithium air battery and preparation method of composite oxygen electrode | |
| CN103977812A (en) | Oxygen-reduction binary transition metal oxide catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |