CN106159286A - A kind of modified electrode being applied to zinc-bromine flow battery and preparation method thereof - Google Patents

A kind of modified electrode being applied to zinc-bromine flow battery and preparation method thereof Download PDF

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Publication number
CN106159286A
CN106159286A CN201610817400.0A CN201610817400A CN106159286A CN 106159286 A CN106159286 A CN 106159286A CN 201610817400 A CN201610817400 A CN 201610817400A CN 106159286 A CN106159286 A CN 106159286A
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zinc
carbon felt
graphite flake
modified electrode
flow battery
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CN106159286B (en
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王德仁
冯彪
孟琳
张祺
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University of Science and Technology Beijing USTB
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University of Science and Technology Beijing USTB
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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
    • H01M4/96—Carbon-based electrodes
    • 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
    • H01M4/8846—Impregnation
    • H01M4/885—Impregnation followed by reduction of the catalyst salt precursor
    • 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
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184—Regeneration by electrochemical means
    • H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
    • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Inert Electrodes (AREA)
  • Hybrid Cells (AREA)

Abstract

The invention belongs to electrode material surface processing technology field, particularly to a kind of modified electrode being applied to zinc-bromine flow battery and the method for preparation thereof.This modified electrode matrix material can be graphite flake or carbon felt, and noble metal nano particles is attached to graphite flake surface or carbon felt fiber surface, such as noble metal nano particles such as platinum, gold, palladium, iridium.Modified electrode preparation method, it is characterized in that, utilize the acid such as chloroplatinic acid, gold chloride, ammonium chloropalladate or iridous chloride and salt preparation precursor solution, and sonic oscillation 2 minutes, then graphite flake or carbon felt are immersed in precursor solution, add the reducing agent such as ascorbic acid or hydrazine hydrate, noble metal granule is reduced to graphite flake or carbon felt fiber surface from the precursor solution that it is relevant, completes the preparation of modified electrode.The invention provides a kind of simple in construction, preparation method modified electrode easily, after applying to zinc-bromine flow battery, the problem that zinc-bromine flow battery electrode activity is not enough can be solved.

Description

A kind of modified electrode being applied to zinc-bromine flow battery and preparation method thereof
Technical field
The invention belongs to electrode material surface processing technology field, be applied to repairing of zinc-bromine flow battery particularly to a kind of Decorations electrode and the method for preparation thereof.
Background technology
Resource and environment will be the determiners finally restricting human social development.For the sustainable development of society, fill Development and utilization regenerative resource is divided to become the requirement that society is the most urgent.And develop large-scale energy storage device and technology Significant to utilizing new forms of energy.In numerous energy storage devices with technology, redox flow batteries has cost because of it Low, have extended cycle life, flexible design, the advantage such as environmental protection, thus be considered as most potential extensive electrochemical energy storage One of device.Redox flow batteries mainly comprises following several types: ferrum/chrome liquor galvanic battery, sodium polysulfide/bromine liquid stream are electric Pond, all-vanadium flow battery, zinc/bromine flow battery etc..Wherein, zinc-bromine flow battery is compared other type flow battery and is had relatively High energy density, it is easy to the advantages such as Capacity design, life cycle length and low cost.In the middle of extensive energy storage is used, especially Being the utilization of more than 100KW scale, zinc-bromine flow battery is the most feasible.Thus in the U.S., in a large number based on zinc bromine liquid stream electricity The extensive energy storage demonstrative project in pond is carried out.
In extensive energy storage technology is applied, although zinc-bromine flow battery is compared other type flow battery and more developed latent Power, but in the middle of high power applications, it yet suffers from the problems such as cell voltage is relatively low.In high-power equipment is applied, its pile Need more monocell, so that its cost increases.
In the middle of zinc-bromine flow battery, electrode surface is the place that redox reaction is carried out, and the activity on its surface is to electricity The performance in pond will produce tremendous influence, thereby through modifying electrode surface to improve electrode electro Chemical performance, be to carry High zinc-bromine flow battery performance, the good method of solution the problems referred to above.
Summary of the invention
The invention aims to provide a kind of modified electrode being applied to zinc-bromine flow battery and preparation method thereof, fortune After zinc-bromine flow battery, it is possible to increase its battery performance.
The modified electrode prepared by the method, matrix material and substrate material surface the noble metal nano modified Granule forms, and its matrix material is graphite flake or carbon felt, and noble metal nano particles is attached to graphite flake surface or carbon felt is fine Dimension table face, such as noble metal nano particles such as platinum, gold, palladium, iridium.Modified electrode as the positive electrode of zinc-bromine flow battery, its table The noble metal nano particles in face plays the effect of catalytic cell positive pole reaction, assembles this modified electrode in the middle of zinc-bromine flow battery After, it is possible to it is effectively improved zinc-bromine flow battery performance.
Modified electrode of the present invention, the noble metal nano particles that substrate material surface is modified, according to precursor solution Difference, can be the one in the noble metal nano particles such as platinum, gold, palladium, iridium, its particle diameter is at below 100nm, at matrix material Surface distributed is uniformly (Fig. 1).
Being applied to the modified electrode of zinc-bromine flow battery, its concrete preparation method is as follows:
First, 0.0025M precursor solution is prepared, graphite flake (the 60 mesh sand paperings so that it is surface is thick processed Rough) and carbon felt (deionized water cleaning) immerse in precursor solution 15-25 minute, make precursor solution fully and graphite flake or Carbon felt fiber surface contacts.Then, be added dropwise over the reducing agent material of 0.0025M, reducing agent material be ascorbic acid solution or Person 85% hydrazine hydrate solution, presoma is 1:2 with the ratio of the amount of reducing agent material, stands 25-after stopping dropping reductant solution Within 35 minutes, making it fully react, during this, noble metal granule is restored by ascorbic acid or hydrazine hydrate solution, and adheres to In graphite flake or the surface of carbon felt fiber, further take out graphite flake or carbon felt, under 38-42 degree Celsius, be vacuum dried 10-14 Hour, prepared by modified electrode.
It is an advantage of the current invention that: provide a kind of simple in construction, preparation method modified electrode easily, apply to zinc bromine After flow battery, it is possible to increase its battery performance (Fig. 1, Fig. 2).
Accompanying drawing explanation
Fig. 1 is the modified electrode scanning electron microscope image that surface attachment has noble metal nano particles.
Fig. 2 is that modified electrode compares with the cyclic voltammetry curve of matrix material.
Fig. 3 is that the zinc-bromine flow battery charging and discharging curve that modified electrode assembles with matrix material compares.
Detailed description of the invention
In order to make the present invention clearer, below in conjunction with embodiment, the present invention is explained in further detail.This Invention contain any be defined by the claims the replacement made in the spirit and scope of the present invention, amendment, equivalent method and Scheme.
Embodiment 1
Weigh 32.37mg six and be hydrated chloroplatinic acid in 25ml deionized water, sonic oscillation 2min, make precursor solution mix Uniformly.Take 1cm × 5cm graphite flake again, use 60cw sand papering so that it is rough surface, and after rinsing well with deionized water, dry Dry.The graphite flake handled well is immersed in precursor solution, and stands 20min, make precursor solution abundant with graphite flake surface Contact.Then, the ascorbic acid solution 25ml of preparation 0.0025M, with glue head dropper, ascorbic acid solution is added dropwise over being soaked with In the precursor solution of graphite flake, stand 30min after stopping dropping reductant solution, make reducing agent the most anti-with precursor solution Should.Further take out graphite flake, and be vacuum dried 12 hours under 40 degrees Celsius, complete to prepare surface and be modified with repairing of Pt nanoparticle Decorations electrode.
Embodiment 2
Weigh 22.20mg ammonium chloropalladate in 25ml deionized water, sonic oscillation 2min, make precursor solution mixing all Even.Take 1cm × 5cm graphite flake again, use 60cw sand papering so that it is rough surface, and after rinsing well with deionized water, dry Dry.The graphite flake handled well is immersed in precursor solution, and stands 20min, make precursor solution abundant with graphite flake surface Contact.Then, take the hydrazine hydrate solution 7ml of 85%, before hydrazine hydrate solution being added dropwise over being soaked with graphite flake with glue head dropper Drive in liquid solution, stand 30min after stopping dropping reductant solution, make reducing agent fully react with precursor solution.Further take out Graphite flake, and be vacuum dried 12 hours under 40 degrees Celsius, complete to prepare surface and be modified with the modified electrode of palladium nano-particles.
Embodiment 3
Weigh 25.74mg tetra-and be hydrated gold chloride in 25ml deionized water, sonic oscillation 2min, make precursor solution mix Uniformly.Take 1cm × 5cm carbon felt again, after rinsing well with deionized water, be vacuum dried under 40 degrees Celsius.Before carbon felt is immersed Drive in liquid solution, and stand 20min, make precursor solution be fully contacted with carbon felt fiber surface.Then, prepare 0.0025M's Ascorbic acid solution 25ml, is added dropwise over ascorbic acid solution to be soaked with in the precursor solution of carbon felt with glue head dropper, stops Stand 30min after dropping reductant solution, make reducing agent fully react with precursor solution.Further take out carbon felt, and Celsius in 40 The lower vacuum drying of degree 12 hours, completes to prepare surface and is modified with the modified electrode of gold nano grain.
Embodiment 4
Weigh 22.05mg tri-chloride hydrate iridium in 25ml deionized water, sonic oscillation 2min, make precursor solution mix Uniformly.Take 1cm × 5cm carbon felt again, after rinsing well with deionized water, be vacuum dried under 40 degrees Celsius.Before carbon felt is immersed Drive in liquid solution, and stand 20min, make precursor solution be fully contacted with carbon felt fiber surface.Then, the hydrazine hydrate of 85% is taken Solution 7ml, is added dropwise over hydrazine hydrate solution to be soaked with in the precursor solution of carbon felt with glue head dropper, stops dropping reducing agent molten Stand 30min after liquid, make reducing agent fully react with precursor solution.Further take out carbon felt, and be vacuum dried under 40 degrees Celsius 12 hours, complete to prepare surface and be modified with the modified electrode of iridium nano-particle.
Embodiment 5
Weigh 32.37mg six and be hydrated chloroplatinic acid in 25ml deionized water, sonic oscillation 2min, make precursor solution mix Uniformly.Take 1cm × 5cm graphite flake again, use 60cw sand papering so that it is rough surface, and after rinsing well with deionized water, dry Dry.The graphite flake handled well is immersed in precursor solution, and stands 20min, make precursor solution abundant with graphite flake surface Contact.Then, take the hydrazine hydrate solution 7ml of 85%, before hydrazine hydrate solution being added dropwise over being soaked with graphite flake with glue head dropper Drive in liquid solution, stand 30min after stopping dropping reductant solution, make reducing agent fully react with precursor solution.Further take out Graphite flake, and be vacuum dried 12 hours under 40 degrees Celsius, complete to prepare surface and be modified with the modified electrode of Pt nanoparticle.

Claims (4)

1. the modified electrode of a zinc-bromine flow battery, it is characterised in that modified electrode is by matrix material and substrate material surface Modify noble metal nano particles composition, matrix material is graphite flake or carbon felt, noble metal nano particles be platinum, gold, palladium, Iridium；Noble metal nano particles is attached to graphite flake surface or carbon felt fiber surface, as the catalysis of zinc-bromine flow battery reaction Agent, is used for improving zinc-bromine flow battery performance.
The preparation method of the modified electrode being applied to zinc-bromine flow battery the most according to claim 1, it is characterised in that profit Precursor solution, and sonic oscillation 1-3 minute is prepared, then stone with chloroplatinic acid, gold chloride, ammonium chloropalladate or iridous chloride Ink sheet or carbon felt immerse in precursor solution, add ascorbic acid or hydrazine hydrate reduction agent, noble metal granule from it Relevant precursor solution is reduced to graphite flake or carbon felt fiber surface.
The preparation method of the modified electrode being applied to zinc-bromine flow battery the most according to claim 2, it is characterised in that tool Preparation is as follows:
First, prepare 0.0025M precursor solution, and sonic oscillation 1-3 minute, make solution uniform, the graphite flake processed Immersing in precursor solution 15-25 minute with carbon felt, then, be added dropwise over 0.0025M reducing agent material, reducing agent material is anti- Bad hematic acid solution or 85% hydrazine hydrate solution, presoma is 1:2 with the ratio of the amount of reducing agent material, stops dropping reducing agent molten Standing after liquid makes it fully react, and stands and within 25-35 minute, make it fully react after stopping dropping reductant solution, during this, Noble metal granule is restored by ascorbic acid or hydrazine hydrate solution, and is attached to graphite flake or the surface of carbon felt fiber, Further take out graphite flake or carbon felt, be vacuum dried 10-14 hour under 38-42 degree Celsius, make modified electrode.
The preparation method of the modified electrode being applied to zinc-bromine flow battery the most according to claim 2, it is characterised in that institute The processing mode stating graphite flake is: 60 mesh sand paperings so that it is rough surface；The process of carbon felt is intended to deionized water and cleans.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106159234A (en) * 2016-08-25 2016-11-23 广东工业大学 Manganese dioxide carbon coated sulfur composite and preparation method thereof, lithium-sulfur cell
CN109786761A (en) * 2017-11-10 2019-05-21 中国科学院大连化学物理研究所 A kind of zinc-bromine flow battery positive electrode and preparation and application
CN111822727A (en) * 2020-06-28 2020-10-27 合肥百诺金科技股份有限公司 Method for synthesizing metal nano-particles by liquid-phase discharge of rough electrode surface structure
CN114551935A (en) * 2020-11-25 2022-05-27 中国科学院大连化学物理研究所 Performance recovery method of zinc-bromine single flow battery

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106159234A (en) * 2016-08-25 2016-11-23 广东工业大学 Manganese dioxide carbon coated sulfur composite and preparation method thereof, lithium-sulfur cell
CN106159234B (en) * 2016-08-25 2018-11-02 广东工业大学 Manganese dioxide carbon coated sulphur composite material and preparation method, lithium-sulfur cell
CN109786761A (en) * 2017-11-10 2019-05-21 中国科学院大连化学物理研究所 A kind of zinc-bromine flow battery positive electrode and preparation and application
CN109786761B (en) * 2017-11-10 2022-07-05 中国科学院大连化学物理研究所 Positive electrode material for zinc-bromine flow battery, preparation and application
CN111822727A (en) * 2020-06-28 2020-10-27 合肥百诺金科技股份有限公司 Method for synthesizing metal nano-particles by liquid-phase discharge of rough electrode surface structure
CN111822727B (en) * 2020-06-28 2023-11-03 合肥百诺金科技股份有限公司 Method for synthesizing metal nano particles by liquid phase discharge of rough electrode surface structure
CN114551935A (en) * 2020-11-25 2022-05-27 中国科学院大连化学物理研究所 Performance recovery method of zinc-bromine single flow battery
CN114551935B (en) * 2020-11-25 2023-09-15 中国科学院大连化学物理研究所 Performance recovery method of zinc-bromine single flow battery

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