CN1275344C - A catalyst material for hydrogen-oxygen fuel cell - Google Patents

A catalyst material for hydrogen-oxygen fuel cell Download PDF

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CN1275344C
CN1275344C CNB2004100863002A CN200410086300A CN1275344C CN 1275344 C CN1275344 C CN 1275344C CN B2004100863002 A CNB2004100863002 A CN B2004100863002A CN 200410086300 A CN200410086300 A CN 200410086300A CN 1275344 C CN1275344 C CN 1275344C
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fuel cell
oxygen fuel
battery electrode
catalysis material
hydrogen
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CN1604368A (en
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张涛
相艳
崔铮
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Beihang University
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Beihang University
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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

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Abstract

The present invention discloses material for katalyzing hydrogen-oxygen fuel cells, which is modified chitosan membrane load metal chloride material. In the technique, modified chitosan membrane load palladium chloride or nickel chloride material is coated on a cell electrode which is used as a cathode. Good catalytic capability is achieved in alkaline or alkalescent solution which is the reaction medium of a hydrogen-oxygen fuel cell, and the output current of the cell can be increased for 2 to 5 times. The chitosan membrane of the present invention has the advantages of good loading capacity and low material cost. Compared with hydrogen-oxygen fuel cells adopting platinum as the catalyst, the present invention has lower cost, and is an environmental protection type and conventional type hydrogen-oxygen fuel cell.

Description

A kind of catalysis material that is used for hydrogen oxygen fuel cell and preparation method thereof
Technical field
The present invention relates to a kind of fuel cell catalysis material, specifically, be meant a kind of muriatic hydrogen oxygen fuel cell catalysis material that is applicable to of modification of chitosan film carried metal that utilizes.
Background technology
Fuel cell is by means of the combustion reaction in the battery, directly transfers chemical energy the device of electric energy to, is a kind of novel efficient chemical power source, is the 4th kind of generation mode except that firepower, waterpower, nuclear energy.To fuel cell, well behaved catalyst is most important, the battery performance when it is determining high current density discharge, service life and cost.The catalyst of fuel cell should meet the following conditions: (1) has conductivity, or uses the good carrier of conductivity in the hope of obtaining high conductivity; (2) certain electrochemical stability can be under the condition that realizes goal response, and the eelctro-catalyst surface is reason electrochemical reaction and inactivation too early not; (3) catalytic performance preferably comprises the activity that realizes goal response and suppress side reaction.
At present to Proton Exchange Membrane Fuel Cells (proton exchange membrane fuel cell, PEMFC) research is more deep, it be meant a class with proton exchange membrane as electrolytical fuel cell system, this fuel cell also often be called as solid polymer fuel cells (polymer electrolyte fuel cell, PEFC).In PEMFC, generally use precious metals pt or its alloy to make catalyst, carbon is made carrier.Although proton exchange membrane has superior stability and proton conductive, it costs an arm and a leg, and selects permeability relatively poor.The present target of pursuing of people is exactly the highly efficient durable of developing, cheap catalyst, thereby popularizes the use of fuel cell.
Shitosan (chitosan) is a kind of natural cation activity polymer, contains two hydroxyls and a free amino in the molecular structure, is soluble in some organic solvents and film forming, and this film hot strength is big, good toughness, alkaline-resisting and organic solvent-resistant.Acidproof and thermal endurance is better than CAM after crosslinked, and is nontoxic simultaneously, hydrophily big, biological cell is had fabulous compatibility.It can be by the amino in the molecule and hydroxyl and many metal ions formation stable chelate.Therefore, shitosan is desirable environment-friendly type catalyst cupport material.
Summary of the invention
The objective of the invention is to disclose a kind of modification of chitosan film load palladium bichloride or nickel chloride material of utilizing as hydrogen oxidation catalyst, the negative pole of hydrogen oxygen fuel cell is carried out the chitosan film fuel cell of catalysis.In the present invention, utilizing chitosan modified film supported catalyst that hydrogen is had good catalytic effect, can reduce the cost of catalyst and loaded film greatly, is a kind of environment-friendly type fuel cell.
A kind of catalysis material that is used for hydrogen oxygen fuel cell of the present invention, catalysis material is the material of crosslinked chitosan film load palladium bichloride or nickel chloride.
The catalysis material of hydrogen oxygen fuel cell of the present invention is to be coated on the negative electrode of hydrogen oxygen fuel cell, and catalysis material can make the electric current of hydrogen oxygen fuel cell output increase 2～5 times.Its preparation technology is:
(A) preparation palladium bichloride or nickel chloride solution
Powdered palladium bichloride of 0.01g or nickel chloride material at room temperature are dissolved in the 40ml ethanolic solution, and it is standby to get supernatant liquor;
(B) on electrode, make chitosan film
Take by weighing 1g shitosan powder, and be dissolved in the acetic acid of 30ml 1%, stir, and it is applied on the battery electrode, hang 10～24h under the room temperature and dry;
Then, the battery electrode of loading with the shitosan powder that will dry is immersed in 10h in 10～40% sodium hydroxide solutions, takes out through being washed to neutrality;
Then, the battery electrode that will load with the shitosan powder again is immersed in 10h in the ethanol, takes out back dry 10～24h in vacuum desiccator;
(C) crosslinking curing
Above-mentioned battery electrode after (B) handles is immersed in the crosslinking agent glutaraldehyde solution its crosslinker concentration 0.1%～10%, at room temperature crosslinked 20～60min;
(D) supported catalyst material
Above-mentioned battery electrode after (C) handles is immersed in 3～12h in above-mentioned (A) solution, clean with distilled water, then, dry 10～24h in vacuum desiccator, take out, promptly obtain on battery electrode, soaking the catalysis material that crosslinked chitosan film load chloride material is arranged.
The present invention with the advantage of the hydrogen oxygen fuel cell of the catalysis material of cross-linked chitosan load palladium bichloride or nickel chloride is: (1) can make the output current of alkaline hydrogen oxygen fuel cell improve 2～5 times; (2) the chitosan modified film has good load capacity; (3) greatly reduce the cost of catalyst and loaded film.
Description of drawings
Fig. 1 is the reaction unit structural representation.
Fig. 2 is the test result of hydrogen oxygen fuel cell in 35%NaOH for preparing with the present invention.
Embodiment
The present invention is further illustrated below in conjunction with example and accompanying drawing.
At first introduce in present patent application " hydrogen oxygen fuel cell operation principle ", its reaction unit as shown in Figure 1.
Cell reaction: (-) C, H 2| NaOH (35%) | O 2, C (+)
Electrode reaction: negative pole:
Anodal:
Overall reaction:
With fuel H 2Constantly feed battery cathode, hydrogen generation oxidation reaction on battery cathode generates H +, discharging electronics simultaneously, electron stream is through circuit, promotes load and flows to positive pole.And oxidant O 2On positive pole, accept electronics, reduction reaction takes place generate anion OH -, again with reaction medium (solution of electrode) in from the H of negative pole +In conjunction with, generate compound H 2O need not describe in detail again.
The catalysis material that is used for hydrogen oxygen fuel cell of the present invention is in order to improve the electric current of battery output, simultaneously the catalyst that adopts on the fuel cell, the cost of loaded film to be reduced, thereby popularizes the use of fuel cell.
A kind of catalysis material that is used for hydrogen oxygen fuel cell of the present invention, its catalysis material are crosslinked chitosan film load palladium bichloride or nickel chloride material.Catalysis material is to be coated on the battery electrode, and its preparation technology is as follows:
(A) preparation palladium bichloride or nickel chloride solution
Powdered palladium bichloride of 0.01g or nickel chloride material at room temperature are dissolved in the 40ml ethanolic solution, and it is standby to get supernatant liquor;
(B) on electrode, make chitosan film
Take by weighing 1g shitosan powder, and be dissolved in the acetic acid of 30ml 1%, stir, and it is applied on the battery electrode, hang 10～24h under the room temperature and dry;
Then, the battery electrode of loading with the shitosan powder that will dry is immersed in 10h in 10～40% sodium hydroxide solutions, takes out through being washed to neutrality;
Then, the battery electrode that will load with the shitosan powder again is immersed in 10h in the ethanol, takes out back dry 10～24h in vacuum desiccator;
(C) crosslinking curing
Above-mentioned battery electrode after (B) handles is immersed in the crosslinking agent glutaraldehyde solution its crosslinker concentration 0.1%～10%, at room temperature crosslinked 20～60min;
(D) supported catalyst material
Above-mentioned battery electrode after (C) handles is immersed in 3～12h in above-mentioned (A) solution, clean with distilled water, then, dry 10～24h in vacuum desiccator, take out, promptly obtain on battery electrode, soaking the catalysis material that crosslinked chitosan film load palladium bichloride or nickel chloride material are arranged.
Embodiment 1: the metal dust nickel chloride is as catalysis material
(A) preparation nickel chloride solution
With being dissolved in the 40ml ethanolic solution under the Powdered nickel chloride room temperature of 0.01g, stir, it is standby to get supernatant liquor.
(B) on electrode, apply chitosan film
The 1g shitosan is dissolved in the acetic acid of 30ml 1%, it is applied on the graphite electrode rod that diameter is 1.5cm, thickness 1mm hangs 10h and dries under the room temperature; Soak this graphite electrode of 10h with 10% sodium hydroxide solution again,, take out and be washed to neutrality, with alcohol immersion 10h chitosan film is converted into neutrality again, at last dry 24h in vacuum desiccator the acetic acid neutralization that loads in the chitosan film.
(C) crosslinking curing is handled
The graphite electrode of chitosan film parcel is put into 3% glutaraldehyde solution, crosslinked 1h under the room temperature.
(D) supported catalyst material
The graphite electrode of the parcel of the chitosan film after crosslinked is put into saturated nickel chloride solution submergence 12h, make and be uniformly coated with the catalysis material nickel chloride on the chitosan film, taking-up is cleaned with distilled water, dry 24h in vacuum desiccator takes out and promptly gets the graphite electrode of loading with crosslinked chitosan film load nickel chloride.
Conclusion: the graphite electrode of the crosslinked chitosan film supported catalyst for preparing is put into simulation reaction device (as shown in Figure 1) carry out the output current test, can feed hydrogen in the road in hydrogen H type, aerating oxygen in oxygen H type energy road, battery electrode adopts pure graphite electrode.Check the air-tightness of each H type pipeline before the test.The simulation reaction cell apparatus adopts alkalescence or faintly alkaline reaction medium, and reaction medium is identical with the employed reaction solution of hydrogen oxygen fuel cell, can be saturated NaHCO 2Solution or 10%NaOH solution or 35%NaOH solution or saturated NaCl solution.In this simulation reaction device, adopt kipp gas generator hydrogen, oxygenerator system oxygen.Between two graphite electrodes that are coated with modification of chitosan film load nickel chloride catalyst material, connect last universal instrument, this universal instrument is used to check the electric current of generation, and the electric current of exporting through the electrode of sensing lead metal chloride catalysis material is respectively 0.12,0.19,0.27 (shown in the table 2).This explanation scribbles nickel chloride on pure graphite electrode battery has improved at least 1 times than the electrode output current that is not coated with catalysis material, perhaps more than 3 times.
Embodiment 2: the metal dust palladium bichloride is as catalysis material
(A) preparation palladium chloride solution
With being dissolved in the 40ml ethanolic solution under the Powdered palladium bichloride room temperature of 0.01g, stir, it is standby to get supernatant liquor.
(B) on electrode, apply chitosan film
The 1g shitosan is dissolved in the acetic acid of 30ml 1%, it is applied in diameter is respectively on the graphite electrode rod of 1cm or 1.5cm, hang 10h under the room temperature and dry; Soak this graphite electrode of 10h with 10% sodium hydroxide solution again,, take out and be washed to neutrality, with alcohol immersion 10h chitosan film is converted into neutrality again, at last dry 24h in vacuum desiccator the acetic acid neutralization that loads in the chitosan film.
(C) crosslinking curing is handled
The graphite electrode of chitosan film parcel is put into 3% glutaraldehyde solution, crosslinked 1h under the room temperature.
(D) supported catalyst material
The graphite electrode of the parcel of the chitosan film after crosslinked is put into saturated palladium chloride solution submergence 12h.Clean dry 24h in the vacuum desiccator with distilled water.
The graphite electrode for preparing is put into simulation reaction device (as shown in Figure 1) carry out the output current test, reaction medium is chosen 35%NaOH solution.The maximum current of electrode output is 0.30mA (as shown in Figure 2).
The shitosan powder is behind acetate dissolution, be coated in and form certain thickness chitosan film on the battery electrode, this chitosan film surface compact, smooth, because shitosan itself contains a large amount of amino and hydroxyl, can and metal ion between form more stable bonding action, so the chitosan film good carrier that is metallic catalyst.
Owing to contain a large amount of hydrophilic radicals in shitosan (1, the 4-2-amino-2-deoxidation-callose) powder, thereby therefore easy swelling causes the less stable of film, and application is affected, so crosslinked method commonly used is carried out modification to it.Glutaraldehyde as cross linker in the present invention.Stable in aqueous slkali through the chitosan film after the crosslinking Treatment, difficult drop-off is stronger to the adsorption capacity of metal ion.The chitosan film of Non-crosslinked is soluble in the reaction medium, makes the catalytic amount of institute's load on it reduce, thereby reduces catalytic effect.Crosslinked excessive chitosan film mechanical performance descends, and can occur peeling as crosslinked excessive meeting at electrode surface, defective phenomenons such as crackle (seeing Table 1).
The influence that table 1 crosslinker concentration, crosslinking time, electrode size adsorb catalysis material
Crosslinker concentration Crosslinking time Electrode diameter (cm) Phenomenon
5％ 5％ 5％ 5％ 1％ 1％ 12h 2h 2h 30min 2h 1h 1 1 1.5 1 1 1.5 The film fragmentation, can not fine crack appear the adsoption catalyst electrode surface, combine not closely film peeling with catalyst, catalyst easy dezidua in cell reaction combines with catalyst firmly, smooth, the difficult drop-off film combines with catalyst firmly, smooth, the difficult drop-off film combines with catalyst firmly, smooth, difficult drop-off
By data in the table 1 as can be known, chitosan film is to the adsorption effect of catalyst and concentration, the crosslinking time of crosslinking agent, and the size of graphite electrode is relevant.In order to reach the optimal adsorption effect of chitosan film to catalyst, along with the reduction of crosslinking agent glutaraldehyde concentration, best crosslinking time should increase accordingly.Diameter is the graphite electrode of the chitosan film parcel of 1cm, and when glutaraldehyde concentration was 5%, best crosslinking time was 30min; And glutaraldehyde concentration is 1% o'clock, and best crosslinking time is 2h.In addition, along with the increase of electrode diameter, crosslinking time should shorten accordingly.Adopt concentration to be 1% glutaraldehyde as cross linker, diameter is that the best crosslinking time of graphite electrode of the chitosan film parcel of 1cm is 2h, and diameter is that the best crosslinking time of graphite electrode of the chitosan film parcel of 1.5cm then is 1h.
The battery cathode that is coated with modification of chitosan film load palladium bichloride or nickel chloride for preparing is compared catalytic effect in the reactant liquor as hydrogen oxygen fuel cell.(as table 2)
Adopt mass percent concentration to be respectively 10%NaOH, 35%NaOH solution, and saturated NaHCO 3Solution is reaction medium, and the graphite electrode of cross-linking modified chitosan film load palladium bichloride, nickel chloride parcel reacts in the analog fuel cell apparatus, records result such as table 2.
Table 2 different medium is to the influence of fuel cell catalytic effect
Reaction medium Catalyst Produce electric current I (mA)
Saturated NaHCO 3 No PdCl 2 0.07 0.13
NiCl 2 0.12
10％NaOH No PdCl 2 NiCl 2 0.06 0.19 0.19
35％NaOH No PdCl 2 NiCl 2 0.10 0.30 0.27
According to the ionization situation of differential responses medium in solution, can draw saturated NaHCO 3OH in the solution -Ion concentration is 2.1 * 10 -6Mol/l, being converted into the pH value is 8.32.Saturated NaHCO 3The OH of solution and 10%NaOH solution, 35%NaOH solution -Ion concentration, pH value see Table 3.
OH in the solution of table 3 reaction medium -Ion concentration and pH value of solution value
Reaction medium OH in the solution -Ion concentration (mol/l) -lg(H +)
NaHCO 3 10％NaOH 35％NaOH 2.1×10 -6 2.8 12.8 8.32 14.44 15.08
Can draw kinetic current I with solution O H by table 2 and table 3 -The increase of ion concentration and increasing.At three kinds of different OH -In the solution of ion concentration, the electric current during catalyst-free is below 0.1mA, and it is less to fluctuate.Obviously increase and add the later kinetic current of catalyst, and OH -The high more electric current increase of ion concentration is big more.This shows with chitosan loaded catalyst P dCl 2, NiCl 2The hydrogen oxygen fuel cell system there is significant catalytic effect, along with OH -The increase of ion concentration, catalytic effect strengthens greatly.
On the other hand, in identical reaction medium, PdCl 2Catalytic performance compare NiCl 2High slightly.Consider PdCl 2Price higher, so select NiCl in actual applications for use 2Be advisable.Adopt air to originate the easy and airborne CO of NaOH solution as oxygen in the practical application 2In conjunction with, thereby battery performance is reduced.Use NaHCO 3Solution can avoid above-mentioned reaction to take place, but catalytic efficiency is lower.
Utilize the chitosan film supported catalyst PdCl of glutaraldehyde cross-linking 2, NiCl 2Oxidation to the hydrogen in the hydrogen oxygen fuel cell has good catalytic effect.The pH value of reaction solution is high more, and kinetic current is big more, and promptly catalytic effect is strong more.Utilizing the chitosan film supported catalyst of glutaraldehyde cross-linking can reduce the cost of catalyst and loaded film greatly, is the new direction of environment-friendly type fuel cell development.

Claims (5)

1, a kind of catalysis material that is used for hydrogen oxygen fuel cell is characterized in that: catalysis material is the material of crosslinked chitosan film load palladium bichloride or nickel chloride.
2, the catalysis material of hydrogen oxygen fuel cell according to claim 1 is characterized in that: scribble the negative pole of the battery electrode of catalysis material as hydrogen oxygen fuel cell.
3, the catalysis material of hydrogen oxygen fuel cell according to claim 1 is characterized in that: make the electric current of hydrogen oxygen fuel cell output increase 2～5 times.
4, a kind of preparation method who is used for the catalysis material of hydrogen oxygen fuel cell, it is characterized in that: catalysis material is coated on the battery electrode, and its preparation technology is:
(A) preparation palladium bichloride or nickel chloride solution
Powdered palladium bichloride of 0.01g or nickel chloride material at room temperature are dissolved in the 40ml ethanolic solution, and it is standby to get supernatant liquor;
(B) on electrode, make chitosan film
Take by weighing 1g shitosan powder, and be dissolved in the acetic acid of 30ml 1%, stir, and it is applied on the battery electrode, hang 10～24h under the room temperature and dry;
Then, the battery electrode of loading with the shitosan powder that will dry is immersed in 10h in 10～40% sodium hydroxide solutions, takes out through being washed to neutrality;
Then, the battery electrode that will load with the shitosan powder again is immersed in 10h in the ethanol, takes out back dry 10～24h in vacuum desiccator;
(C) crosslinking curing
Above-mentioned battery electrode after (B) handles is immersed in the crosslinking agent glutaraldehyde solution its crosslinker concentration 0.1%～10%, at room temperature crosslinked 20～60min;
(D) supported catalyst material
Above-mentioned battery electrode after (C) handles is immersed in 3～12h in above-mentioned (A) solution, clean with distilled water, then, dry 10～24h in vacuum desiccator, take out, promptly obtain on battery electrode, soaking the catalysis material that crosslinked chitosan film load palladium bichloride or nickel chloride material are arranged.
5, the preparation method of the catalysis material of hydrogen oxygen fuel cell according to claim 4 is characterized in that: the chitosan film thickness that spreads upon on the battery electrode is 0.1～2mm.
CNB2004100863002A 2004-11-01 2004-11-01 A catalyst material for hydrogen-oxygen fuel cell Expired - Fee Related CN1275344C (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022167458A1 (en) * 2021-02-05 2022-08-11 Universite Grenoble Alpes Composition for manufacturing an electrode, associated electrode and method

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CN100444941C (en) * 2007-03-27 2008-12-24 天津大学 Method for preparing chitosan and surface modified Y-type zeolite hybridization liquid separation film
CN101807701A (en) * 2010-04-23 2010-08-18 上海理工大学 Direct methanol fuel cell anodic nano-catalyst and preparation method thereof
CN105461968B (en) * 2015-12-08 2018-01-12 福州大学 A kind of preparation method of starch/chitosan solid electrolytic thin-membrane
CN105655603B (en) * 2015-12-31 2018-06-12 北京化工大学 A kind of fuel-cell catalyst and preparation method thereof
CN108232255A (en) * 2016-12-19 2018-06-29 天津艾博胜环保科技有限公司 The preparation method of Metal semi-fuel cells chitosan film electrode

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022167458A1 (en) * 2021-02-05 2022-08-11 Universite Grenoble Alpes Composition for manufacturing an electrode, associated electrode and method
FR3119713A1 (en) * 2021-02-05 2022-08-12 Universite Grenoble Alpes Composition for the manufacture of electrode, electrode and associated process

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