CN101901916A - Carbon-carried manganese tetraoxide composite catalytic material and preparation method thereof - Google Patents

Carbon-carried manganese tetraoxide composite catalytic material and preparation method thereof Download PDF

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CN101901916A
CN101901916A CN2010102550807A CN201010255080A CN101901916A CN 101901916 A CN101901916 A CN 101901916A CN 2010102550807 A CN2010102550807 A CN 2010102550807A CN 201010255080 A CN201010255080 A CN 201010255080A CN 101901916 A CN101901916 A CN 101901916A
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carbon
carbon black
manganese nitrate
catalytic material
vulcanxc
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CN101901916B (en
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周德壁
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TIANJIN JIUJU ENERGY TECHNOLOGY DEVELOPMENT Co Ltd
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TIANJIN JIUJU ENERGY TECHNOLOGY DEVELOPMENT Co Ltd
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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 carbon-carried manganese tetraoxide composite catalytic material and a preparation method thereof, and aims at providing an oxygen reduction reaction air electrode catalytic material with a wide range of raw material resources, low cost, excellent performances and good stability, and the preparation method thereof, the catalytic material takes carbon black as a carrier, the catalytic active component is Mn3O4, and the catalytic material comprises 50-93.7% by weight of carbon block and 6.3-50% by weight of Mn3O4. The preparation method comprises the following steps: adding manganese nitrate into distilled water for dissolution, and preparing manganese nitrate solution; adding the carbon black into the manganese nitrate solution, fully and uniformly stirring, standing, and then drying at the constant temperature of 80 DEG C; grinding powder obtained after drying in a mortar into fine powder, than placing in a muffle furnace, increasing the temperature to 400 DEG C, and keeping the temperature for 3h; and then taking out, grinding and obtaining the carbon-carried Mn3O4 composite catalytic material. The preparation process of the catalytic material is simple, reliable, low in cost and easy to realize the industrial production.

Description

Carbon-carried manganese tetraoxide composite catalytic material and preparation method
Technical field
The present invention relates to electrochemical field, in particular, relate to a kind of air electrode oxygen reduction reaction carbon-carried manganese tetraoxide composite catalytic material that is used for fuel cell and preparation method thereof.
Background technology
[0002] electrochemical reduction of oxygen is the cathode reaction of all types of fuel cells, and the oxygen reduction electrode kinetics is slow, for practical application, need add catalysis material during the preparation air electrode.At present the air electrode catalysis material mainly adopts platinum class noble metal or cobalt, nickel class transition metal, and is comparatively expensive.Be to realize the fuel cell commercialization, study that catalysis material is significant cheaply.
Manganese is a kind of aboundresources, cheap metallic element, and the oxide such as the manganese dioxide of manganese show catalytic performance to hydrogen reduction, has obtained research.Mangano-manganic oxide (Mn 3O 4) be a kind of important magnetic material, developed multiple preparation method and realized industrialization at the application of magnetic material, high price manganese oxidizing process, manganese carbonate method, manganese sulfate method, manganese ore method and manganese metal method etc. are arranged.In so many preparation methods, generally all can face cost problem, technological problems, granular size problem etc.
Summary of the invention
The present invention is applied to hydrogen reduction catalysis with the mangano-manganic oxide of cheapness, provides a kind of raw material resources extensive, and cost is low, and function admirable, the oxygen reduction reaction air electrode catalysis material of good stability.
Another object of the present invention provides a kind of simple, and the production efficiency height is suitable for the carbon-carried manganese tetraoxide composite catalytic preparation methods of suitability for industrialized production.
The present invention is achieved through the following technical solutions:
A kind of carbon-carried manganese tetraoxide composite catalytic material that is used for the fuel battery air electrode is characterized in that, this catalysis material is carrier with the carbon black, and catalytic active component is Mn 3O 4, in this catalysis material, carbon black is 50-93.7% by mass percentage, Mn 3O 4Be 6.3-50%.
Described carbon black is VulcanXC-72 or VulcanXC-72 and active carbon by mass ratio is that the mixture of 1:1 or VulcanXC-72 and acetylene black are the mixture of 1:1 by mass ratio.
A kind of carbon-carried manganese tetraoxide composite catalytic preparation methods that is used for the fuel battery air electrode is characterized in that, comprises the steps:
(1) manganese nitrate is added distilled water and make manganese nitrate solution;
(2) carbon black is joined in the above-mentioned manganese nitrate solution, after stirring, leave standstill manganese nitrate fully is adsorbed on the carbon black, generally need 0.5-1 hour; Dry down 80 ℃ of constant temperature afterwards;
(3) dried powder is ground in mortar, be warming up to 400 ℃ of constant temperature 3h afterwards; Take out then, grind, obtain carbon and carry Mn 3O 4Compound catalyze material, in this catalysis material, carbon black is 70-93.7% by mass percentage, Mn 3O 4Be 6.3-30%.
Wherein, carbon black is preferably selected sour preliminary treatment or the pretreated carbon black of alkali for use.
The pretreated process of described acid is: it is that 65% red fuming nitric acid (RFNA) soaks 24h that carbon black is put into concentration, filter and use a large amount of washed with de-ionized water after removing solution, then 80 ℃ of dryings, grind to form powdery and obtain pretreated carbon black.
The pretreated process of described alkali is: it is that 33% KOH solution soaks 24h that carbon black is put into concentration, filter and use a large amount of washed with de-ionized water after removing solution, then 80 ℃ of dryings, grind to form powdery and obtain pretreated carbon black.
The present invention has following technique effect:
(1) preparation method of catalysis material of the present invention is carrier with the carbon black, directly carbon black material is joined reactant system high temperature pyrolysis together, and a step has obtained carbon and carried Mn 3O 4Compound catalyze material, the preparation method is simple, and the production efficiency height is suitable for suitability for industrialized production.
(2) carbon that obtains of the present invention carries Mn 3O 4The hydrogen reduction catalytic performance excellence of compound catalyze material than under the high current density, can be exported big operating voltage, good stability.Through overtesting, in the alkaline medium air atmosphere, under-0.2V vs. Hg/HgO the current potential, the current density of hydrogen reduction reaches 115.8 mAcm -2
(3) the used raw material resources of production catalysis material of the present invention is extensive, cheap, can reduce production costs.
Description of drawings
Fig. 1, catalysis material content are that 15% carbon carries Mn 3O 4The TEM figure of compound catalyze material;
Fig. 2, catalysis material content are that 15% carbon carries Mn 3O 4The XRD figure of compound catalyze material;
The hydrogen reduction catalytic performance of Fig. 3, different catalysis material content electrodes relatively;
The content of the corresponding catalysis material of numbering among Fig. 3:
Curve (a) 6.3%
Curve (b) 15%
Curve (c) 30%
Curve (d) 50%
The VulcanXC-72 that Fig. 4, distinct methods are handled carries Mn as the carbon of carrier 3O 4Compound catalyze material is made the polarization of electrode curve;
The corresponding pretreated method of numbering is among Fig. 4:
The VulcanXC-72 of curve (a) alkali treatment
The heat treated VulcanXC-72 of curve (b)
The acid-treated VulcanXC-72 of curve (c)
The undressed VulcanXC-72 of curve (d)
Fig. 5, carry Mn with carbon 3O 4The discharge curve of after date when compound catalyze material is one section of the battery operation of electrode;
The size of numbering corresponding current density among Fig. 5
Curve (a) 40 mAcm -2
Curve (b) 60 mAcm -2
Curve (c) 80 mAcm -2
Curve (d) 100 mAcm -2
Fig. 6, different carbon carrier polarization of electrode curve;
The corresponding different carbon carrier of numbering among Fig. 6
Curve (a) VulcanXC-72 is 1:1 with the quality of activated carbon ratio
Curve (b) VulcanXC-72 and acetylene black mass ratio are 1:1.
Embodiment
The present invention is described in detail below in conjunction with specific embodiment.
Embodiment 1
(1) takes by weighing 0.44g manganese nitrate (making catalysis material content is 6.3%) and place beaker, add 31ml distilled water and be made into manganese nitrate solution.In manganese nitrate solution, add the VulcanXC-72 powder 2.81g that Cabot company produces, after stirring, left standstill 1 hour.
(2) beaker that fills mixture that step (1) is obtained is put into air dry oven, in 80 ℃ of dryings of constant temperature.
(3) the dried powder of step (2) is ground to form fine powder in mortar, be positioned in the crucible.Crucible is put into Muffle furnace, be warming up to 400 ℃ of constant temperature 3h, take out afterwards, grind to form powdery and obtain carbon and carry Mn 3O 4Compound catalyze material.
Embodiment 2
(1) takes by weighing 1.06g manganese nitrate (making catalysis material content is 15%) and place beaker, add 28ml distilled water and be made into manganese nitrate solution.In manganese nitrate solution, add the VulcanXC-72 powder 2.55g that Cabot company produces, after stirring, left standstill 1 hour.
(2) beaker that fills mixture that step (1) is obtained is put into air dry oven, in 80 ℃ of dryings of constant temperature;
(3) with the dried powder of step (2), in mortar, grind to form fine powder after, be positioned in the crucible.Crucible is put into Muffle furnace, be warming up to 400 ℃ of constant temperature 3h.Take out afterwards, grind to form powdery, obtain carbon and carry Mn 3O 4Compound catalyze material.
The carbon that makes is carried Mn 3O 4Compound catalyze material carries out TEM and XRD analysis as depicted in figs. 1 and 2.As can be seen from Figure 1, He Cheng carbon carries Mn 3O 4The composite material pattern is even, good dispersion.As can be seen from Figure 2, obtain Mn with this understanding 3O 4And be carried on VulcanXC-72 and go up a kind of composite material of formation.
Embodiment 3
(1) takes by weighing 2.1g manganese nitrate (making catalysis material content is 30%) and place beaker, add 23ml distilled water and be made into manganese nitrate solution.In manganese nitrate solution, add the VulcanXC-72 powder 2.1g that Cabot company produces, after stirring, left standstill 1 hour.
(2) beaker that fills mixture that step (1) is obtained is put into air dry oven, in 80 ℃ of dryings of constant temperature.
(3) the dried powder of step (2) is ground to form fine powder in mortar after, be positioned in the crucible.Crucible is put into Muffle furnace, be warming up to 400 ℃ of constant temperature 3h.Take out afterwards, grind to form powdery, obtain carbon and carry Mn 3O 4Compound catalyze material.
Embodiment 4
(1) takes by weighing 3.52g manganese nitrate (making catalysis material content is 50%) and place beaker, add 17ml distilled water and be made into manganese nitrate solution.In manganese nitrate solution, add the VulcanXC-72 powder 1.50g that Cabot company produces, after stirring, left standstill 1 hour.
(2) beaker that fills mixture that step (1) is obtained is put into air dry oven, in 80 ℃ of dryings of constant temperature.
(3) with dried powder, in mortar, grind to form fine powder after, be positioned in the crucible.Afterwards crucible is put into Muffle furnace, be warming up to 400 ℃ of constant temperature 3h.Take out afterwards, grind to form powdery, obtain carbon and carry Mn 3O 4Compound catalyze material.
Embodiment 1, embodiment 2, embodiment 3 and embodiment 4 gained carbon are carried Mn 3O 4Compound catalyze material is made air electrode according to conventional method respectively, and its effective area is 1 cm 2, with 4cm 2Platinized platinum do electrode, the Hg/HgO electrode is as reference electrode.
In air atmosphere, 7mol/L KOH electrolyte, test different metal content polarization of electrode curve as shown in Figure 3 under the room temperature.As can be seen from Figure 3, when tenor was increased to 15 wt% from 6.3wt%, the performance of catalytic oxidation-reduction obviously increased.When tenor in the electrode continued to be increased to 50 wt%, the catalytic activity of electrode did not improve, instead take place obviously to descend.
Embodiment 5
(1) VulcanXC-72 is carried out acid treatment: it is that 65% red fuming nitric acid (RFNA) soaks 24h that the VulcanXC-72 product of Cabot company is put into concentration, use a large amount of washed with de-ionized water after filter removing solution, then 80 ℃ of dryings, obtain pretreated VulcanXC-72 after grinding to form powdery.
(2) take by weighing 1.06g manganese nitrate (making catalysis material content is 15%) and place beaker, add 28ml distilled water and be made into manganese nitrate solution.In manganese nitrate solution, add through the pretreated VulcanXC-72 powder of step (1) 2.55g, after stirring, left standstill 1 hour.
(3) beaker that step (2) is filled mixture is put into air dry oven, in 80 ℃ of dryings of constant temperature.
(4) with dried powder, in mortar, grind to form fine powder after, be positioned in the crucible.Again crucible is put into Muffle furnace, be warming up to 400 ℃ of constant temperature 3h.Take out afterwards, grind to form powdery, obtain carbon and carry Mn 3O 4Compound catalyze material.
The gained catalysis material is made air electrode according to conventional method, and its effective area is 1 cm 2, with 4cm 2Platinized platinum do electrode, the Hg/HgO electrode is as reference electrode.
In air atmosphere, 7mol/L KOH electrolyte, the carbon that test obtains under the room temperature carries Mn 3O 4Compound catalyze material polarization of electrode curve as shown in Figure 4.As can be seen from Figure 4, be that the electrode of carrier and the carbon black that is untreated are that the electrode of carrier is compared with acid-treated VulcanXC-72, be that the carbon of carrier carries Mn with acid-treated VulcanXC-72 3O 4The catalytic performance of compound catalyze material hydrogen reduction significantly improves.
Embodiment 6
(1) VulcanXC-72 is carried out alkali treatment: it is that 33% KOH solution soaks 24h that the VulcanXC-72 product of Cabot company is put into concentration, use a large amount of washed with de-ionized water after filter removing solution, then 80 ℃ of dryings, obtain pretreated VulcanXC-72 after grinding to form powdery.
(2) take by weighing 1.06g manganese nitrate (making catalysis material content is 15%) and place beaker, add 28ml distilled water and be made into manganese nitrate solution.In manganese nitrate solution, add through the pretreated VulcanXC-72 powder of step (1) 2.55g, after stirring, left standstill 1 hour.
(3) beaker that fills mixture that step (2) is obtained is put into air dry oven, in 80 ℃ of dryings of constant temperature;
(4) with dried powder, in mortar, grind to form fine powder after, be positioned in the crucible, again crucible is put into Muffle furnace, be warming up to 400 ℃ of constant temperature 3h.Afterwards, take out, grind to form powdery, obtain carbon and carry Mn 3O 4Compound catalyze material.
The gained catalysis material is made air electrode according to conventional method, and its effective area is 1 cm 2, with 4cm 2Platinized platinum do electrode, the Hg/HgO electrode is as reference electrode.
In air atmosphere, 7mol/L KOH electrolyte, the carbon that test obtains under the room temperature carries Mn 3O 4Compound catalyze material polarization of electrode curve as shown in Figure 4.As can be seen from Figure 4, be that the electrode of carrier and the carbon black that is untreated are that the electrode of carrier is compared with the VulcanXC-72 of alkali treatment, be that the carbon of carrier carries Mn with the VulcanXC-72 of alkali treatment 3O 4The catalytic performance of compound catalyze material hydrogen reduction significantly improves.
Embodiment 7
(1) VulcanXC-72 is heat-treated: the VulcanXC-72 product of Cabot company is put into Muffle furnace, be warming up to 600 ℃ of constant temperature 2h.
(2) take by weighing 1.06g manganese nitrate (making catalysis material content is 15%) and place beaker, add 28ml distilled water and be made into manganese nitrate solution.In manganese nitrate solution, add through the pretreated VulcanXC-72 powder of step (1) 2.55g, after stirring, left standstill 1 hour.
(3) beaker that fills mixture that step (2) is obtained is put into air dry oven, in 80 ℃ of dryings of constant temperature;
(4) with dried powder, in mortar, grind to form fine powder after, be positioned in the crucible, again crucible is put into Muffle furnace, be warming up to 400 ℃ of constant temperature 3h, take out afterwards, grind to form powdery, obtain carbon and carry Mn 3O 4Compound catalyze material.
The gained catalysis material is made air electrode according to conventional method, and its effective area is 1 cm 2, with 4cm 2Platinized platinum do electrode, the Hg/HgO electrode is as reference electrode.
In air atmosphere, 7mol/L KOH electrolyte, the carbon that test obtains under the room temperature carries Mn 3O 4Compound compound catalyze material polarization of electrode curve as shown in Figure 4.As can be seen from Figure 4, be that the electrode of carrier and the carbon black that is untreated are that the electrode of carrier is compared with heat treated VulcanXC-72, be that the carbon of carrier carries Mn with heat treated VulcanXC-72 3O 4The catalytic performance of compound catalyze material hydrogen reduction improves not obvious.
Embodiment 8
(1) takes by weighing 1.06g manganese nitrate (making catalysis material content is 15%) and place beaker, add 28ml distilled water and be made into manganese nitrate solution.In manganese nitrate solution, add the VulcanXC-72 powder 2.55g of Cabot company, after stirring, left standstill 1 hour.
(2) beaker that fills mixture that step (1) is obtained is put into air dry oven, in 80 ℃ of dryings of constant temperature.
(3) with dried powder, in mortar, grind to form fine powder after, be positioned in the crucible, again crucible is put into Muffle furnace, be warming up to 400 ℃ of constant temperature 3h.Take out afterwards, grind to form powdery, obtain carbon and carry Mn 3O 4Compound catalyze material.
The gained catalysis material is made air electrode according to conventional method, and its effective area is 4cm 2, make anode with zinc metal sheet, be assembled into zinc-air cell.Test it under the room temperature at 40mA/cm 2, 60 mA/cm 2, 80 mA/cm 2, 100 mA/cm 2Discharge curve as shown in Figure 5.As can be seen from Figure 5, discharge time and discharge are pressed and are reduced along with the increase of current density.Discharging voltage balance has shown the catalytic performance that catalysis material is superior.
Embodiment 9
(1) takes by weighing 1.06g manganese nitrate (making catalysis material content is 15%) and place beaker, add 28ml distilled water and be made into manganese nitrate solution.In manganese nitrate solution, add VulcanXC-72 powder 1.275g, the active carbon 1.275g of Cabot company, after stirring, left standstill 1 hour.
(2) beaker that step (1) is filled mixture is put into air dry oven, in 80 ℃ of dryings of constant temperature.
(3) dried powder is ground to form fine powder in mortar after, be positioned in the crucible, again crucible is put into Muffle furnace, be warming up to 400 ℃ of constant temperature 3h, take out afterwards, grind to form powdery, obtain carbon and carry Mn 3O 4Compound catalyze material.
Embodiment 10
(1) takes by weighing 1.06g manganese nitrate (making catalysis material content is 15%) and place beaker, add 28ml distilled water and be made into manganese nitrate solution.In manganese nitrate solution, add VulcanXC-72 powder 1.275g, the acetylene black 1.275g of Cabot company, after stirring, left standstill 1 hour.
(2) beaker that step (1) is filled mixture is put into air dry oven, in 80 ℃ of dryings of constant temperature.
(3) dried powder is ground to form fine powder in mortar after, be positioned in the crucible, again crucible is put into Muffle furnace, be warming up to 400 ℃ of constant temperature 3h, take out afterwards, grind to form powdery, obtain carbon and carry Mn 3O 4Compound catalyze material.
Embodiment 9 and embodiment 10 gained carbon are carried Mn 3O 4Compound catalyze material is made air electrode according to conventional method respectively, and its effective area is 1 cm 2, with 4cm 2Platinized platinum do electrode, the Hg/HgO electrode is as reference electrode.
In air atmosphere, 7mol/L KOH electrolyte, the different carbon carrier polarization of electrode curves of test as shown in Figure 6 under the room temperature.As can be seen from Figure 6, VulcanXC-72 has good catalytic activity with the quality of activated carbon ratio for the electrode of 1:1; VulcanXC-72 and acetylene black mass ratio are that the electrode of 1:1 has catalytic activity preferably.

Claims (6)

1. a carbon-carried manganese tetraoxide composite catalytic material that is used for the fuel battery air electrode is characterized in that, this catalysis material is carrier with the carbon black, and catalytic active component is Mn 3O 4, in this catalysis material, carbon black is 70-93.7% by mass percentage, Mn 3O 4Be 6.3-30%.
2. the carbon-carried manganese tetraoxide composite catalytic material that is used for the fuel battery air electrode according to claim 1, it is characterized in that described carbon black is VulcanXC-72 or VulcanXC-72 and active carbon by mass ratio is that the mixture of 1:1 or VulcanXC-72 and acetylene black are the mixture of 1:1 by mass ratio.
3. the described carbon-carried manganese tetraoxide composite catalytic preparation methods that is used for the fuel battery air electrode of claim 1 is characterized in that, comprises the steps:
(1) manganese nitrate is added distilled water and make manganese nitrate solution;
(2) carbon black is joined in the above-mentioned manganese nitrate solution, after stirring, leave standstill and make manganese nitrate fully be adsorbed on the carbon black; Dry down 80 ℃ of constant temperature afterwards;
(3) dried powder is ground in mortar, be warming up to 400 ℃ of constant temperature 3h afterwards; Take out then, grind, obtain carbon and carry Mn 3O 4Compound catalyze material, in this catalysis material, carbon black is 50-93.7% by mass percentage, Mn 3O 4Be 6.3-50%.
4. the carbon-carried manganese tetraoxide composite catalytic preparation methods that is used for the fuel battery air electrode according to claim 3 is characterized in that, described carbon black is sour preliminary treatment or the pretreated carbon black of alkali.
5. the carbon-carried manganese tetraoxide composite catalytic preparation methods that is used for the fuel battery air electrode according to claim 4, it is characterized in that, the pretreated process of described acid is: it is that 65% red fuming nitric acid (RFNA) soaks 24h that carbon black is put into concentration, use a large amount of washed with de-ionized water after filter removing solution, then 80 ℃ of dryings, grind to form powdery and obtain pretreated carbon black.
6. the carbon-carried manganese tetraoxide composite catalytic preparation methods that is used for the fuel battery air electrode according to claim 4, it is characterized in that, the pretreated process of described alkali is: it is that 33% KOH solution soaks 24h that carbon black is put into concentration, use a large amount of washed with de-ionized water after filter removing solution, then 80 ℃ of dryings, grind to form powdery and obtain pretreated carbon black.
CN2010102550807A 2010-08-17 2010-08-17 Carbon-carried manganese tetraoxide composite catalytic material and preparation method thereof Expired - Fee Related CN101901916B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102504619A (en) * 2011-09-29 2012-06-20 牛晓璐 Purification process of pyrolysis carbon black of waste tire
CN103440996A (en) * 2013-08-30 2013-12-11 天津工业大学 Method for preparing nanometer manganous-manganic oxide/carbon composite energy storage material
CN114345322A (en) * 2022-01-13 2022-04-15 贵州民族大学 Carbon-supported manganese oxide catalyst and preparation method thereof

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CN1396308A (en) * 2002-06-17 2003-02-12 重庆大学 Air electrode catalyst and its preparing process

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CN1396308A (en) * 2002-06-17 2003-02-12 重庆大学 Air electrode catalyst and its preparing process

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102504619A (en) * 2011-09-29 2012-06-20 牛晓璐 Purification process of pyrolysis carbon black of waste tire
CN102504619B (en) * 2011-09-29 2014-04-02 牛晓璐 Purification process of pyrolysis carbon black of waste tire
CN103440996A (en) * 2013-08-30 2013-12-11 天津工业大学 Method for preparing nanometer manganous-manganic oxide/carbon composite energy storage material
CN114345322A (en) * 2022-01-13 2022-04-15 贵州民族大学 Carbon-supported manganese oxide catalyst and preparation method thereof

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