CN103904337A - Preparation method of paper-graphite-CoPd thin film electrode - Google Patents

Preparation method of paper-graphite-CoPd thin film electrode Download PDF

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Publication number
CN103904337A
CN103904337A CN201410075796.7A CN201410075796A CN103904337A CN 103904337 A CN103904337 A CN 103904337A CN 201410075796 A CN201410075796 A CN 201410075796A CN 103904337 A CN103904337 A CN 103904337A
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paper
graphite
copd
preparation
membrane electrode
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CN201410075796.7A
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CN103904337B (en
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王贵领
张栋铭
潘越
曹殿学
徐阳
闫鹏
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Harbin Engineering University
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Harbin Engineering University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8817—Treatment of supports before application of the catalytic active composition
    • 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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  • Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inert Electrodes (AREA)

Abstract

The invention provides a preparation method of a paper-graphite-CoPd thin film electrode. The preparation method comprises the following steps: (1) uniformly coating ordinary paper with a mixture of graphite and clay; (2) retaining the paper coated with the graphite for 20-30 min under the voltage of 1.0V, activating the coating graphite, and then performing electro-deposition on Co for 120-150 min under the voltage of -0.8V to obtain a paper-graphite-Co thin film electrode; and (3) enabling the paper-graphite-Co thin film electrode to stand in 0.8 mmol/L<-1> of PbC12 solution for 1-3 min to obtain the paper-graphite-CoPd thin film electrode, namely a graphite coated paper loading CoPd catalyst. According to the method, with pencil coated paper, Co is subjected to electro-deposition on the surface of conducting paper coated with graphite, and then partial Co is replaced with Pd to prepare the graphite coated paper loading CoPd catalyst, so that the electroreduction performance of hydrogen peroxide is improved. The preparation method overcomes the defects of high current collector cost, hydrogen peroxide decomposition and the like, and solves the problem that hydrogen peroxide based full cells are bad in cathode activity.

Description

The preparation method of paper-graphite-CoPd membrane electrode
Technical field
That the present invention relates to is the preparation method of a kind of paper-graphite-CoPd membrane electrode, is a kind of method with coated with graphite paper load C oPd catalyzing hydrogen peroxide Electrochemical Properties.
Background technology
Traditional fuel cell mainly with airborne oxygen as oxidant, but in the situation that some is special, as in water, space is medium, the source of oxygen is but subject to great restriction, and (in seawater, dissolved oxygen concentration is low, is difficult to reach the requirement as power supply power; In space, oxygen is thin, is difficult to equally utilize).If therefore use oxygen as oxidant in these environment, must be self-contained.In recent years, H 2o 2studied widely as oxidant.As the oxidant of underwater power source, H 2o 2there are a lot of outstanding advantages, (1) H 2o 2be the liquid under normal temperature, compared with the oxygen of gaseous state, volume energy density is high, store, transportation and all more convenient to carrying in battery, and potential safety hazard is less.H simultaneously 2o 2the product decomposing is water and oxygen, also can not cause problem of environmental pollution; (2) H 2o 2direct-reduction is 2 electron reaction processes, and compared with the process of 4 electron reactions in oxygen reduction, what activation energy will be low is many, H 2o 2the exchange current density of direct-reduction, than large 6 orders of magnitude of oxygen electric reduction, therefore, uses H 2o 2more easily obtain good battery performance as oxidant than oxygen; (3) H 2o 2electroreduction is solid-liquid two phase reaction, and the electroreduction of oxygen is solid-liquid-gas phase reaction, two phase reaction boundary zone is than the easy foundation in three phase boundary district and stable, and without gas diffusion layers, therefore, whole battery system can more stablize, simply, compact, convenient and easy operating.In addition, H 2o 2produce so that several hundred million pounds are a large amount of every year, its low price, and overcome because using airborne oxygen to make the shortcomings such as alkaline electrolyte carbonation.
H 2o 2the catalytic performance of electroreduction is an important factor in order that is directly connected to the performance of fuel cell.So preparing high performance catalyst is to improve with H 2o 2for the key of the fuel battery performance of oxidant.Conventionally, the electrode of fuel cell is to form pasty state by catalyst fines mixed polymer binding agent, conductive carbon mix and blend, is then coated in dry obtaining in metal collector.The mode of this traditional making electrode, owing to introducing polymeric binder, causes some catalyst well not contact with electrolyte, thereby causes the low shortcoming such as catalyst utilization and low conductivity.In addition, conductive carbon powder and polymeric binder in long-time test or unstable under heavy-current discharge, can cause and come off, thereby affect the performance of electrode.H 2o 2the subject matter that directly electroreduction exists is H 2o 2electroreduction activity is not high, and directly electro-reduction reaction is as shown in (1) formula:
HO 2 -+H 2O+2e→2OH ads -+OH - (1)
Can consult Fan Yang, Kui Cheng, Tianhao Wu, Ying Zhang, Jinling Yin, Guiling Wang, Dianxue Cao.Au – Pd nanoparticles supported on carbon fiber cloth as the electrocatalyst for H 2o 2electroreduction in acid medium.Journal of Power Sources, 2013,233:252-258, and Kui Cheng, Fan Yang, Yang Xu, Lin Cheng, Yanyan Bao, Dianxue Cao, Guiling Wang.Pd doped Co 3o 4nanowire array as the H 2o 2electroreduction catalyst.Journal of Power Sources, 2013,240:442-447.
Summary of the invention
The object of the invention is to propose a kind of preparation method of paper-graphite-CoPd membrane electrode that can solve hydrogen peroxide-based fuel battery negative pole poor activity problem.
The object of the present invention is achieved like this:
(1) graphite and clay mixture are evenly coated on plain paper;
(2) paper that scribbles graphite is kept to 20～30min under 1.0V voltage, the graphite that activation applies, then electro-deposition Co120～150min under-0.8V, obtains paper-graphite-Co membrane electrode;
(3) by paper-graphite-Co membrane electrode at 0.8mmol L -1pbCl 2in solution, leave standstill 1～3 minute, obtain paper-graphite-CoPd membrane electrode, i.e. coated with graphite paper load C oPd catalyst.
The present invention can also comprise:
1, the electrodeposit liquid of described electro-deposition Co is by 5～5.5g NH 4cl and 1～1.5g CoCl 2be dissolved in the electrodeposit liquid obtaining in 50mL water.
2, described graphite and clay mixture are pencil-lead.
3, described plain paper is the one in writing paper, wrapping paper, newsprint, printing paper, technical paper, base paper or converted paper.
The present invention's pencil coated paper, in the surface of paper of the coating graphite of conduction, then prepares coated with graphite paper load C oPd catalyst with Pd replacing section Co by Co electro-deposition, improves the method for hydrogen peroxide Electrochemical Properties.Overcome collector price high, and the shortcoming such as hydrogen peroxide decomposition, solved the problem of hydrogen peroxide-based fuel battery negative pole poor activity.
Essence of the present invention is the battery structure that adopts hydrogen peroxide base fuel battery etc., take coated with graphite paper load C oPd as catalyst, forms the negative electrode of fuel cell.CoPd wherein comprises the CoPd alloy of Co, Pd and various ratios thereof.
The invention has the advantages that and utilize the catalyst of coated with graphite paper load C oPd catalyst as the direct electroreduction of hydrogen peroxide, solved hydrogen peroxide electroreduction discharging current little and be easy to the problems such as hydrolysis.In this electrode production process, do not use binding agent and conductive agent, the more important thing is that under electric field action graphite and clay can form with Co and Pd the cross-linking compounds of paper-graphite-clay-CoPd, not only good conductivity, and also electro catalytic activity is high.The pencil coated paper load C oPd catalyst not only reserves of graphite, clay, Co is extremely rich and easy to get, cheap, greatly reduces electrode preparation cost, and its catalytic activity is high, stable performance, preparation process is easy, be applicable to suitability for industrialized production, there is prospects for commercial application and market value.
Embodiment
For example the present invention is described in more detail below.
(1) graphite and clay mixture are evenly coated on plain paper.Graphite and clay mixture can directly be selected pencil-lead; Plain paper can be selected from writing paper, wrapping paper, newsprint, printing paper, technical paper, base paper or converted paper.
(2) paper that scribbles graphite is kept to 20～30min under 1.0V voltage, the graphite that activation applies.Then in electrodeposit liquid, electro-deposition Co120～150min under-0.8V, obtain paper-graphite-Co membrane electrode.The electrodeposit liquid of described electro-deposition Co is by 5～5.5g NH 4cl and 1～1.5g CoCl 2be dissolved in the electrodeposit liquid obtaining in 50mL water.
(3) by paper-graphite-Co membrane electrode at 0.8mmol L -1pbCl 2in solution, leave standstill 1～3 minute, obtain paper-graphite-CoPd membrane electrode, i.e. coated with graphite paper load C oPd catalyst.
For the effect of technique of the present invention is described better, be illustrated with instantiation below
1, take paper-graphite-CoPd film as work electrode, carbon-point is to electrode, take Ag/AgCl as reference electrode, at the NaOH of 2mol/L and the H of 0.40mol/L 2o 2solution in, under the voltage of-0.4V vs.Ag/AgCl, timing current density reaches 180mA/cm 2.
2, utilize paper-graphite-CoPd film as H 2o 2the directly negative electrode of electroreduction, using the KOH of 3mol/L as catholyte; Nafin-115 proton exchange is touched as barrier film; Take the nanometer Pt of load in nickel foam as anode, take the KOH of 3mol/L as anodolyte solution, the sodium borohydride of 1mol/L is fuel; Work as H 2o 2concentration is 0.6mol/L -1, KOH concentration is 3mol/L -1time battery maximum power density be 356mW/cm -2.
3, utilize paper-graphite-CoPd film as H 2o 2the directly negative electrode of electroreduction, using the KOH of 3mol/L as catholyte; Nafin-115 proton exchange is touched as barrier film; With the metal A l sheet utmost point, take the KOH of 6mol/L as anodolyte solution; Work as H 2o 2concentration is 0.6mol/L 1, KOH concentration while being 3mol/L the maximum power density of battery be 523mW/cm 2.

Claims (5)

1. a preparation method for paper-graphite-CoPd membrane electrode, is characterized in that:
(1) graphite and clay mixture are evenly coated on plain paper;
(2) paper that scribbles graphite is kept to 20～30min under 1.0V voltage, the graphite that activation applies, then electro-deposition Co120～150min under-0.8V, obtains paper-graphite-Co membrane electrode;
(3) by paper-graphite-Co membrane electrode at 0.8mmol L -1pbCl 2in solution, leave standstill 1～3 minute, obtain paper-graphite-CoPd membrane electrode, i.e. coated with graphite paper load C oPd catalyst.
2. the preparation method of paper-graphite according to claim 1-CoPd membrane electrode, is characterized in that: the electrodeposit liquid of described electro-deposition Co is by 5～5.5g NH 4cl and 1～1.5g CoCl 2be dissolved in the electrodeposit liquid obtaining in 50mL water.
3. the preparation method of paper-graphite according to claim 1 and 2-CoPd membrane electrode, is characterized in that: described graphite and clay mixture are pencil-lead.
4. the preparation method of paper-graphite according to claim 1 and 2-CoPd membrane electrode, is characterized in that: described plain paper is the one in writing paper, wrapping paper, newsprint, printing paper, technical paper, base paper or converted paper.
5. the preparation method of paper-graphite according to claim 3-CoPd membrane electrode, is characterized in that: described plain paper is the one in writing paper, wrapping paper, newsprint, printing paper, technical paper, base paper or converted paper.
CN201410075796.7A 2014-03-04 2014-03-04 The preparation method of paper-graphite-CoPd membrane electrode Expired - Fee Related CN103904337B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104078689A (en) * 2014-07-09 2014-10-01 哈尔滨工程大学 Preparation method for graphene-adhered plastic loaded PdNi hydrogen peroxide electric reduction catalyst
CN104091958A (en) * 2014-07-09 2014-10-08 哈尔滨工程大学 Preparation method of graphene-attached plastic supported AuCo sodium borohydride electro-oxidation catalyst
CN114094122A (en) * 2021-11-12 2022-02-25 徐州工程学院 Preparation method and application of PdRu/graphene/foamed nickel composite cathode

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102088089A (en) * 2010-12-27 2011-06-08 浙江大学 Preparation method of combined electrode of fuel cell and test device thereof
US20110135966A1 (en) * 2009-12-05 2011-06-09 Vishnu Jayaprakash Novel cow-dung based microbial fuel cell

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110135966A1 (en) * 2009-12-05 2011-06-09 Vishnu Jayaprakash Novel cow-dung based microbial fuel cell
CN102088089A (en) * 2010-12-27 2011-06-08 浙江大学 Preparation method of combined electrode of fuel cell and test device thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
BIN YAO ET AL: ""Paper-basedsolid-statesupercapacitors"", 《NANO ENERGY》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104078689A (en) * 2014-07-09 2014-10-01 哈尔滨工程大学 Preparation method for graphene-adhered plastic loaded PdNi hydrogen peroxide electric reduction catalyst
CN104091958A (en) * 2014-07-09 2014-10-08 哈尔滨工程大学 Preparation method of graphene-attached plastic supported AuCo sodium borohydride electro-oxidation catalyst
CN114094122A (en) * 2021-11-12 2022-02-25 徐州工程学院 Preparation method and application of PdRu/graphene/foamed nickel composite cathode
CN114094122B (en) * 2021-11-12 2022-12-27 徐州工程学院 Preparation method and application of PdRu/graphene/foamed nickel composite cathode

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