CN104078689A - Preparation method for graphene-adhered plastic loaded PdNi hydrogen peroxide electric reduction catalyst - Google Patents

Preparation method for graphene-adhered plastic loaded PdNi hydrogen peroxide electric reduction catalyst Download PDF

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Publication number
CN104078689A
CN104078689A CN201410323848.8A CN201410323848A CN104078689A CN 104078689 A CN104078689 A CN 104078689A CN 201410323848 A CN201410323848 A CN 201410323848A CN 104078689 A CN104078689 A CN 104078689A
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graphene
plastics
hydrogen peroxide
preparation
pdni
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CN201410323848.8A
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CN104078689B (en
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王贵领
张栋铭
李一举
曹殿学
闫鹏
王滨
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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
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • 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
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8853—Electrodeposition
    • 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
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/921—Alloys or mixtures with metallic elements
    • 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
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • 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)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Inert Electrodes (AREA)
  • Catalysts (AREA)

Abstract

The invention provides a preparation method for a graphene-adhered plastic loaded PdNi hydrogen peroxide electric reduction catalyst. The preparation method comprises the following steps: adhering one face of an alkali-resisting double-sided adhesive tape on the surface of plastic; coating the other face of the double-sided adhesive tape by graphene according to the density of 15-20mg/cm<2>; compacting the graphene by pressure of 6-10MPa; placing the plastic adhered with the graphene into each liter of a water solution containing 5g of NiCl2 and 1g of NH4Cl; activating under the voltage of 1.0V for 5 minutes and keeping electrolytic deposition of nickel under -1V for 1-1.5 hours; and putting a prepared plastic nickel body adhered with the graphene into a solution containing 1mmol/mL of PdCl2 for 3-5 minutes. The essence of the invention is that battery structures including hydrogen peroxide based fuel batteries and the like are adopted and graphene-adhered plastic loaded PdNi is used as a catalyst to form a cathode of the fuel battery, the problem that the cathode activity of the hydrogen peroxide based fuel batteries is poor is solved.

Description

Graphene attaches the preparation method of plastics load P dNi hydrogen peroxide electric reduction catalyst
Technical field
The present invention relates to a kind of preparation method of hydrogen peroxide electric reduction catalyst.
Background technology
Traditional fuel cell needs O 2for oxidant, but because volume energy density is low, range of application is restricted.Use liquid oxidizer to be considered to improve the effective way of energy density.US National Aeronautics and Space Administration, U.S. University of Illinois, limejuicer research department and defence science and technology experiment chamber etc. start emphasis support in recent years with H 2o 2for the research of the fuel cell of oxidant, first this be because H 2o 2for liquid, that whole battery system can seem is compacter, convenient and easy operating; Secondly, with H 2o 2for theoretical voltage and the specific energy of the fuel cell of oxidant are high, can solve the low density problem of the current all kinds of energy content of battery; The 3rd, with H 2o 2for the fuel cell of oxidant can be used as the power supply under oxygen free condition.These outstanding advantages can make with H 2o 2for the fuel cell of oxidant becomes the portable and portable power source of space power system of new generation, underwater power source, anaerobic power supply and high-energy-density of future generation.
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 shortcomings such as low catalyst utilization and low conductivity.In addition, due to H 2o 2directly electroreduction moves under alkali condition, and metal collector may react with alkali, forms metal oxide layer, causes electric conductivity to decline, and long-play can cause the dissolving of metal collector, even can cause and come off.Thereby affect the performance of electrode.Metal collector also can catalysis H 2o 2decompose, reduced H 2o 2utilance.H 2o 2also there is H in electroreduction directly 2o 2the problem that electroreduction activity is not high, directly electro-reduction reaction is as shown in (1) formula:
HO 2 -+H 2O+2e→2OH ads -+OH - (1)
Can consult Kui Cheng, Fan Yang, Guiling Wang, Jinling Yin and Dianxue Cao.Facile synthesis of porous (Co, Mn) 3o 4nanowires free-standing on a Ni foam and their catalytic performance for H 2o 2electroreduction.Journal of Materials Chemistry A, 2013,1,1669-1676; Cao Dianxue, Yang Fan, Guo Fen, Xiao Xue, Liu Ran, Wang Guiling, the three-dimensional porous H of all-metal of carbon-free binder free 2o 2the preparation method of electro-oxidizing-catalyzing electrode [P]. Chinese patent literature: CN103346332A, 2013-10-09 and Yan Peng, Tian Yongmei, Bao Yanyan, Cao Dianxue, Wang Gui leads .La 0.6sr 0.4coO 3catalysis H 2o 2the performance study of electroreduction. power technology, 2013,37 (9): 1544-1545,1598.
Summary of the invention
The object of the present invention is to provide a kind of Graphene that can improve hydrogen peroxide Electrochemical Properties to attach the preparation method of plastics load P dNi hydrogen peroxide electric reduction catalyst.
The object of the present invention is achieved like this:
The one side of alkali resistance two-sided tape is affixed on to frosting; Graphene is pressed to 15-20mgcm -2be coated on the another side of two-sided tape; Adopt 6-10MPa pressure by Graphene compacting; The plastics that attach Graphene are placed in to every liter containing 5gNiCl 2and 1gNH 4in the aqueous solution of Cl, first 5min under activation under 1.0V voltage, and then under-1V, carry out keeping 1～1.5 hour under the electro-deposition of nickel; The plastics Ni substrate that attaches Graphene preparing is placed in containing 1mmolmL -1pdCl 23-5min in solution, obtains Graphene and attaches plastics load P dNi catalyst.
Described plastics are vinyon, polystyrene plastics, polypropylene plastics or Maranyl and their derivative plastics.
The present invention be a kind of by Ni electro-deposition in conductive graphene surface, then with Pd replacing section Ni, prepare Graphene and attach plastics load P dNi catalyst, improve the method for hydrogen peroxide Electrochemical Properties.It is unstable in alkaline solution that the present invention has overcome collector, 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., and it is catalyst that the Graphene of take attaches plastics load P dNi, forms the negative electrode of fuel cell.
The invention has the advantages that and utilize Graphene to attach plastics load P dNi catalyst as the catalyst of the direct electroreduction of hydrogen peroxide, first be under electric field action, PdNi nano particle can be positioned between graphene layer, cross-linking compounds with PdNi formation plastics-Graphene-PdNi, not only specific surface is large, good conductivity, and PdNi nano particle do not reunite, and improved electro catalytic activity.Secondly, it is strong that Graphene attaches plastics load P dNi catalyst stability in alkaline medium, do not dissolve, and catalytic decomposition hydrogen peroxide not, has overcome metal collector unstable and weakness that hydrogen peroxide decomposes in alkaline solution, has improved H 2o 2utilance.The 3rd, do not use binding agent and conductive agent, reduced Ohmic resistance, solved the problem of hydrogen peroxide-based fuel battery negative pole poor activity.The 4th, plastics are good compared with metal flexible, can, with electrolyte stream dynamic deformation, reduce the resistance of electrolyte flow.
Embodiment
For example the present invention is described in more detail below.
(1). get one of common plastic paper (waste and old plastics Instant noodle bag, food-packaging bag etc. all can); (2). get alkali resistance two-sided tape, one side is affixed on to plastic bag surface; (3). Graphene is pressed to 15-20mgcm -2be coated on the another side of two-sided tape; (4). adopt 6-10MPa pressure by Graphene compacting; (5). the plastics that attach Graphene are placed in to every liter containing 5gNiCl 2and 1gNH 4in the aqueous solution of Cl, first at 1.0V voltage by 5min under electrode activation, and then under-1V, carry out keeping 1～1.5 hour under the electro-deposition of nickel; (6). the plastics nickel electrode matrix that attaches Graphene preparing is placed in containing 1mmolmL -1pdCl 23-5min in solution, obtains Graphene and attaches plastics load P dNi catalyst.
For the effect of technique of the present invention is described better, with instantiation, be illustrated below.
Application Example 1
It is work electrode that the Graphene of take attaches plastics load P dNi, and 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 380mA/cm 2.
Application Example 2
Utilize Graphene to attach plastics load P dNi as H 2o 2the direct negative electrode of electroreduction, usings the KOH of 3mol/L as catholyte; Nafin-115 proton exchange is touched as barrier film; The nanometer Pt of load in nickel foam of take is anode, and the KOH of 3mol/L of take is anodolyte solution, and 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 572mW/cm -2.
Application Example 3
Utilize Graphene to attach plastics load P dNi as H 2o 2the direct negative electrode of electroreduction, usings the KOH of 3mol/L as catholyte; Nafin-115 proton exchange is touched as barrier film; With the metal A l sheet utmost point, the KOH of 6mol/L of take is 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 689mW/cm 2.

Claims (2)

1. Graphene attaches a preparation method for plastics load P dNi hydrogen peroxide electric reduction catalyst, it is characterized in that: the one side of alkali resistance two-sided tape is affixed on to frosting; Graphene is pressed to 15-20mgcm -2be coated on the another side of two-sided tape; Adopt 6-10MPa pressure by Graphene compacting; The plastics that attach Graphene are placed in to every liter containing 5gNiCl 2and 1gNH 4in the aqueous solution of Cl, first 5min under activation under 1.0V voltage, and then under-1V, carry out keeping 1～1.5 hour under the electro-deposition of nickel; The plastics Ni substrate that attaches Graphene preparing is placed in containing 1mmolmL -1pdCl 23-5min in solution.
2. Graphene according to claim 1 attaches the preparation method of plastics load P dNi hydrogen peroxide electric reduction catalyst, it is characterized in that: described plastics are vinyon, polystyrene plastics, polypropylene plastics or Maranyl and their derivative plastics.
CN201410323848.8A 2014-07-09 2014-07-09 Graphene attaches the preparation method of plastics load P dNi hydrogen peroxide electric reduction catalyst Active CN104078689B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104505497A (en) * 2014-12-12 2015-04-08 盐城市新能源化学储能与动力电源研究中心 Graphene nickel composite material and graphene nickel carbon electrode prepared by using same
CN112886025A (en) * 2019-11-29 2021-06-01 大连大学 Fructose fuel cell and construction method thereof
CN113130916A (en) * 2019-12-30 2021-07-16 大连大学 Preparation method of lactose fuel cell based on PdNPs/NiNPs/ITO electrode

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103427087A (en) * 2012-05-17 2013-12-04 清华大学 Current collector, electrochemical cell electrode, and electrochemical cell
CN103904337A (en) * 2014-03-04 2014-07-02 哈尔滨工程大学 Preparation method of paper-graphite-CoPd thin film electrode

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103427087A (en) * 2012-05-17 2013-12-04 清华大学 Current collector, electrochemical cell electrode, and electrochemical cell
CN103904337A (en) * 2014-03-04 2014-07-02 哈尔滨工程大学 Preparation method of paper-graphite-CoPd thin film electrode

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104505497A (en) * 2014-12-12 2015-04-08 盐城市新能源化学储能与动力电源研究中心 Graphene nickel composite material and graphene nickel carbon electrode prepared by using same
CN112886025A (en) * 2019-11-29 2021-06-01 大连大学 Fructose fuel cell and construction method thereof
CN113130916A (en) * 2019-12-30 2021-07-16 大连大学 Preparation method of lactose fuel cell based on PdNPs/NiNPs/ITO electrode
CN113130916B (en) * 2019-12-30 2022-06-14 大连大学 Method for constructing lactose fuel cell based on PdNPs/NiNPs/ITO electrode

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