CN103170355B - A kind of air electrode metal nitride catalyst preparation method being applied to air cell - Google Patents
A kind of air electrode metal nitride catalyst preparation method being applied to air cell Download PDFInfo
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- CN103170355B CN103170355B CN201210429762.4A CN201210429762A CN103170355B CN 103170355 B CN103170355 B CN 103170355B CN 201210429762 A CN201210429762 A CN 201210429762A CN 103170355 B CN103170355 B CN 103170355B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a kind of air electrode metal nitride catalyst preparation method being applied to air cell.The composition of this catalyst is A
xb
yn (x=0.25 ~ 5, y=1 ~ 5), A and B is respectively a kind of transition metal, and N is nitrogen element.Described catalyst adopts collosol and gel-high-temperature sintering process to make: slaine is made into the aqueous solution, then the carbon dust that to add with catalyst quality ratio be 2: 1 ~ 4: 1 does carrier and it mixes formation colloidal sol by ultrasonic wave skill; Under 90 DEG C of constant temperature, drying obtains xerogel; Xerogel is processed 2 ~ 5h in 500 ~ 1500 DEG C under the condition having nitrogenous source, obtains described compound catalyze material.This compound catalyze material has good catalytic performance to hydrogen reduction, can work under compared with large current density, the loss of voltage is little; In addition, the preparation technology of this catalyst is simple, can realize suitability for industrialized production.
Description
Technical field
The present invention relates to electrochemical field, be specifically related to a kind of air electrode metal nitride-carbon composite catalytic agent preparation method being applied to air cell.Can be applicable to the catalysis material of air electrode of zinc-air power battery, alkaline fuel cell, seawater battery.
Background technology
Metal-air battery is the one of fuel cell, and using metals such as zinc, aluminium, magnesium as fuel, i.e. negative active core-shell material, obtains electric energy.Wherein zinc-air battery development 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 metallic zinc again after electrolytic regeneration, then makes battery.Zinc-air battery can not produce explosion accident, is stable electrochmical power source, only need stop supplying 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 makees a kind of electrochmical power source with issuing the biochemical reaction of hair tonic and generation current at the catalyst of catalyst.
The important performance (voltage of battery, power density) of battery 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.Find catalyst that is cheap, efficient stable and become the key improving air performance.The progress of this technology directly affects the development of zinc-air battery as 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, as the porphyrin containing metal and nitrogen-atoms to hydrogen reduction and oxygen.In these materials, M-N may be the catalytic activity position of oxygen reduction reaction.Infer that the nitride of transition metal has catalysis potentiality with this.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing catalyst being applied to the air electrode metal nitride of air cell, this catalyst towards oxygen reduction has excellent catalytic performance, can work, the loss of voltage is little and comparatively stable under high current density.
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 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 nitrogen element, and its transition metal is Fe, Ni, Mn, and this catalyst take carbon black as carrier.
Metal nitride catalyst 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, add again with catalyst institute mass ratio be 2: 1 ~ 4: 1 carbon dust do carrier and make it mix formation colloidal sol with ultrasonic wave, under 90 DEG C of constant temperature, drying obtains xerogel, in 500 ~ 1500 DEG C of process 2 ~ 5h under the condition having nitrogenous source, 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 with ultrasonic agitation evenly after, put into 90 DEG C of constant temperature oven constant temperature standing and drying, make it become xerogel.
2) take out the xerogel described in step 1, then be incorporated as NH wherein
3, urea, the nitrogenous source such as ethylenediamine, and to mix with ultrasonic.
3) again the mixture described in step 2 is put into Muffle furnace, after temperature rises to 500 ~ 1500 DEG C of reprocessing 2 ~ 5h, then allow it slowly naturally cool to room temperature, namely obtain described catalyst.
The invention has the advantages that:
A) catalyst towards oxygen reduction of the present invention has good catalytic performance, can be applied to zinc-air battery, comprises the application as electrokinetic cell.This catalyst also can be applied to other types metal-air battery.
B) catalyst of the present invention is raw material by the base metal transition elements such as Fe, Ni, Mn one or more mixture water soluble salts wherein, and such raw material resources is extensive, cheap, can reduce production cost.
C) this catalyst adopts sol-gal process preparation, and the method can prepare the nano-particle material that particle diameter is little, be evenly distributed, and meanwhile, the time of the method sintering is short, and production technology is simple, can suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is polarization curve of the present invention
Fig. 2 is constant-current discharge curve map of the present invention
Detailed description of the invention
Embodiment one:
Take 4.04g ferric nitrate in beaker, add deionized water dissolving, make it to continue to dissolve with ultrasonic wave, add 2.24gVulcanXC-72, ultrasonic making it mixes process, then obtains xerogel after putting into 90 DEG C of baking oven freeze-day with constant temperature, after mixing with 2.4g urea again, in Muffle furnace, 600 DEG C of process 5h, obtain required nitride compound catalyze material, are labeled as FeN
4/ C, and be prepared into electrode according to a conventional method.This electrode shows excellent hydrogen reduction performance.As can be seen from the polarization curve recorded under air atmosphere, room temperature, alkaline electrolyte condition that Fig. 1 provides, under current potential is-0.2V condition, electrode current density can reach 161mAcm
-2.As can be seen from the discharge curve of Fig. 2 display, at discharge current density 130A.cm
-2under, voltage reaches 0.98V, and voltage is very stable.
Embodiment two:
Take 2.9g nickel nitrate in beaker, add deionized water dissolving, dissolve with the continuation of ultrasonic wave skill, add 1.27g graphite and 1.27g VulcanXC-72, ultrasonic making it mixes process, then obtains xerogel after putting into 90 DEG C of baking oven freeze-day with constant temperature, after mixing with 0.2g ethylenediamine again, in Muffle furnace, 800 DEG C of process 4h, obtain required nitride compound catalyze material, are labeled as Ni
3n/C, and be prepared into electrode according to a conventional method.As can be seen from the polarization curve recorded under air atmosphere, room temperature, alkaline electrolyte condition that Fig. 1 provides, under current potential is-0.2V condition, electrode current density can reach 150mA.cm
-2.As can be seen from the discharge curve of Fig. 2 display, 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 to dissolve with ultrasonic wave, add 2.44g graphite and 2.44g active carbon, ultrasonic making it mixes process, then obtains xerogel after putting into 90 DEG C of baking oven freeze-day with constant temperature, after mixing with 2.98g triethanolamine again, in Muffle furnace, 500 DEG C of process 3h, obtain required nitride compound catalyze material, are labeled as Fe
2ni
2n/C, and be prepared into electrode according to a conventional method.As can be seen from the polarization curve recorded under air atmosphere, room temperature, alkaline electrolyte condition that Fig. 1 provides, under current potential is-0.2V condition, current density can reach 115mAcm
-2.As can be seen from the discharge curve of Fig. 2 display, at current density 130mAcm
-2under, voltage reaches 0.81V, and voltage is very stable.
Claims (3)
1. for an air electrode metal nitride catalyst for air cell, it is characterized in that, the composition of this nitride is expressed as A
xb
yn, x=0.25 ~ 5, y=1 ~ 5, A, B are respectively a kind of transition metal, and N is nitrogen element, and wherein transition metal is Fe, Ni or Mn, and this catalyst take carbon black as carrier; This catalyst adopts collosol and gel-high-temperature sintering process to make, adopt the aqueous solution of transition metal salt, the carbon black powders that to add with catalyst quality ratio be again 2: 1 ~ 4: 1 is done carrier and makes it mix formation colloidal sol with ultrasonic wave, under 90 DEG C of constant temperature, drying obtains xerogel, in 500 ~ 1500 DEG C of process 2 ~ 5h under the condition having nitrogenous source, obtain this catalyst.
2. a kind of air electrode metal nitride catalyst for air cell according to claim 1, is characterized in that, described carbon black is one or more the mixture in VulcanXC-72, acetylene black, graphite, active carbon.
3. a kind of air electrode metal nitride catalyst for air cell according to claim 1, it is characterized in that, described nitrogenous source is urea, ethylenediamine or triethanolamine.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN103794806B (en) * | 2014-01-27 | 2016-02-03 | 中南大学 | A kind of lithium air battery positive electrode Nano-iron nitride-carbon composite catalytic agent and preparation method 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 |
| CN107742732B (en) * | 2017-09-30 | 2019-09-10 | 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 |
| 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 |
Citations (6)
| 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 |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100048380A1 (en) * | 2008-08-21 | 2010-02-25 | Board Of Trustees Of Michigan State University | Novel catalyst for oxygen reduction reaction in fuel cells |
-
2012
- 2012-11-01 CN CN201210429762.4A patent/CN103170355B/en active Active
Patent Citations (6)
| 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 |
| 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 |
|---|
| 溶胶-微波干燥法制备Nd0.6Ca0.4CoO3及其电化学性能;温美盛等;《电源技术》;20110620;第35卷(第06期);第643-647页 * |
| 燃料电池阴极非铂Fe/N/C和Co/N/C电催化剂的研究进展;万术伟等;《电源技术》;20101020;第34卷(第10期);第1087-1092页第1-4节 * |
| 碱性燃料电池Co-N/C复合催化剂的电化学性能;赖渊等;《化学学报》;20080514;第66卷(第09期);第1015-1020页第1.1、1.3、3节 * |
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