CN106159286B - A kind of modified electrode and preparation method thereof applied to zinc-bromine flow battery - Google Patents
A kind of modified electrode and preparation method thereof applied to zinc-bromine flow battery Download PDFInfo
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- CN106159286B CN106159286B CN201610817400.0A CN201610817400A CN106159286B CN 106159286 B CN106159286 B CN 106159286B CN 201610817400 A CN201610817400 A CN 201610817400A CN 106159286 B CN106159286 B CN 106159286B
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- zinc
- modified electrode
- flow battery
- carbon felt
- graphite flake
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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
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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
- H01M4/8846—Impregnation
- H01M4/885—Impregnation followed by reduction of the catalyst salt precursor
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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
- H01M4/90—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
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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
- H01M4/90—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
Abstract
The invention belongs to electrode material surface processing technology field, the more particularly to methods of a kind of modified electrode and its preparation applied to zinc-bromine flow battery.The modified electrode basis material can be that either carbon felt noble metal nano particles are attached to graphite flake surface or carbon felt fiber surface, such as platinum, gold, palladium, iridium noble metal nano particles to graphite flake.Modified electrode preparation method, it is characterized in that, precursor solution is prepared using the acid such as chloroplatinic acid, gold chloride, ammonium chloropalladate or iridous chloride and salt, and sonic oscillation 2 minutes, then graphite flake or carbon felt are immersed in precursor solution, adding ascorbic acid, either noble metal granule is restored to graphite flake or carbon felt fiber surface by the reducing agents such as hydrazine hydrate from its relevant precursor solution, completes the preparation of modified electrode.The present invention provides a kind of simple in structure, preparation method easily modified electrode after applying to zinc-bromine flow battery, can solve the problems, such as that zinc-bromine flow battery electrode activity is insufficient.
Description
Technical field
The invention belongs to electrode material surface processing technology field, more particularly to a kind of repairing applied to zinc-bromine flow battery
The method for adoring electrode and its preparation.
Background technology
Resource and environment will be the final determinants for restricting human social development.For the sustainable development of society, fill
Development and utilization regenerative resource is divided to have become the very urgent requirement of today's society.And develop large-scale energy storage device and technology
To being of great significance using new energy.In numerous energy storage devices and technology, redox flow batteries are because it is with cost
It is low, have extended cycle life, flexible design, it is environmentally protective the advantages that, thus be considered as most potential extensive electrochemical energy storage
One of device.Redox flow batteries include mainly following several types：Iron/chrome liquor galvanic battery, sodium polysulfide/bromine liquid stream electricity
Pond, all-vanadium flow battery, zinc/bromine flow battery etc..Wherein, zinc-bromine flow battery compare other type flow batteries have compared with
High energy density, convenient for Capacity design, life cycle is long and the advantages such as low cost.In extensive energy storage utilization, especially
It is the utilization of 100KW scales or more, zinc-bromine flow battery is more economically feasible.Thus in the U.S., largely based on zinc bromine liquid stream electricity
The extensive energy storage demonstrative project in pond is carried out.
In the application of extensive energy storage technology, although zinc-bromine flow battery compares other type flow batteries, more development is latent
Power, but in high power applications, still have the problems such as cell voltage is relatively low.In high-power equipment application, pile
More monocells are needed, to make its cost increase.
In zinc-bromine flow battery, electrode surface is the place that redox reaction carries out, and the activity on surface is to electricity
The performance in pond will generate tremendous influence, thus be to carry by being modified electrode surface to improve electrode electro Chemical performance
High zinc-bromine flow battery performance, the good method to solve the above problems.
Invention content
The purpose of the invention is to provide a kind of modified electrode and preparation method thereof applied to zinc-bromine flow battery, fortune
After zinc-bromine flow battery, its battery performance can be improved.
The modified electrode prepared by the method, the noble metal nano modified by basis material and substrate material surface
Particle forms, and basis material is that either carbon felt noble metal nano particles are attached to graphite flake surface to graphite flake or carbon felt is fine
Dimension table face, such as platinum, gold, palladium, iridium noble metal nano particles.Positive electrode of the modified electrode as zinc-bromine flow battery, table
The noble metal nano particles in face play the role of the reaction of catalytic cell anode, this modified electrode is assembled in zinc-bromine flow battery
Afterwards, zinc-bromine flow battery performance can be effectively improved.
Modified electrode of the present invention, the noble metal nano particles of substrate material surface modification, according to precursor solution
Difference, can be one kind in the noble metal nano particles such as platinum, gold, palladium, iridium, grain size is in 100nm hereinafter, in basis material
Surface is evenly distributed (Fig. 1).
Applied to the modified electrode of zinc-bromine flow battery, specific preparation method is as follows：
First, 0.0025M precursor solutions are prepared, (60 mesh sand paper are polished, and keep its surface thick processed graphite flake
It is rough) and carbon felt (deionized water cleaning) immerse precursor solution in 15-25 minutes, make precursor solution fully with graphite flake or
Carbon felt fiber surface contacts.Then, be added dropwise the reducing agent substance of 0.0025M, reducing agent substance be ascorbic acid solution or
85% hydrazine hydrate solution of person, the ratio between presoma and the amount of reducing agent substance are 1:2, stop standing 25- after reducing agent solution is added dropwise
It is set fully to react within 35 minutes, during this, noble metal granule is restored by ascorbic acid or hydrazine hydrate solution, and is adhered to
Graphite flake or carbon felt are further taken out in the surface of graphite flake either carbon felt fiber, 10-14 is dried in vacuo under 38-42 degrees Celsius
Hour, prepared by modified electrode completes.
The advantage of the invention is that：Provide a kind of simple in structure, preparation method easily modified electrode applies to zinc bromine
After flow battery, its battery performance (Fig. 1, Fig. 2) can be improved.
Description of the drawings
Fig. 1 is the modified electrode scanning electron microscope image that surface is attached with noble metal nano particles.
Fig. 2 is modified electrode compared with the cyclic voltammetry curve of basis material.
Fig. 3 is modified electrode compared with the zinc-bromine flow battery charging and discharging curve that basis material assembles.
Specific implementation mode
In order to make the present invention be more clearly understood, with reference to embodiments, the present invention is explained in further detail.This
Invention cover it is any be defined by the claims the present invention spirit and scope on make replacement, modification, equivalent method and
Scheme.
Embodiment 1
It weighs 32.37mg six and is hydrated chloroplatinic acid in 25ml deionized waters, sonic oscillation 2min makes precursor solution mix
Uniformly.1cm × 5cm graphite flakes are taken again, is polished with 60cw sand paper, makes its rough surface, after being used in combination deionized water to rinse well, are dried
It is dry.The graphite flake handled well is immersed in precursor solution, and stands 20min, keeps precursor solution and graphite flake surface abundant
Contact.Then, the ascorbic acid solution 25ml for preparing 0.0025M, is added dropwise ascorbic acid solution with rubber head dropper and is soaked with
In the precursor solution of graphite flake, stops standing 30min after reducing agent solution is added dropwise, keep reducing agent fully anti-with precursor solution
It answers.Graphite flake is further taken out, and is dried in vacuo 12 hours under 40 degrees Celsius, completing preparation surface modification has repairing for Pt nanoparticle
Adorn electrode.
Embodiment 2
22.20mg ammonium chloropalladates are weighed in 25ml deionized waters, sonic oscillation 2min keeps precursor solution mixing equal
It is even.1cm × 5cm graphite flakes are taken again, is polished with 60cw sand paper, makes its rough surface, after being used in combination deionized water to rinse well, are dried
It is dry.The graphite flake handled well is immersed in precursor solution, and stands 20min, keeps precursor solution and graphite flake surface abundant
Contact.Then, the hydrazine hydrate solution 7ml for taking 85% is added dropwise hydrazine hydrate solution with rubber head dropper before being soaked with graphite flake
It drives in liquid solution, stops standing 30min after reducing agent solution is added dropwise, reducing agent is made fully to be reacted with precursor solution.It further takes out
Graphite flake, and be dried in vacuo 12 hours under 40 degrees Celsius, completing preparation surface modification has the modified electrode of palladium nano-particles.
Embodiment 3
It weighs 25.74mg tetra- and is hydrated gold chloride in 25ml deionized waters, sonic oscillation 2min makes precursor solution mix
Uniformly.1cm × 5cm carbon felts are taken again, after being rinsed well with deionized water, are dried in vacuo under 40 degrees Celsius.Before carbon felt is immersed
It drives in liquid solution, and stands 20min, precursor solution is made to be come into full contact with carbon felt fiber surface.Then, prepare 0.0025M's
Ascorbic acid solution 25ml ascorbic acid solution is added dropwise in the precursor solution for being soaked with carbon felt with rubber head dropper, is stopped
30min is stood after reducing agent solution is added dropwise, reducing agent is made fully to be reacted with precursor solution.Carbon felt is further taken out, and Celsius in 40
The lower vacuum drying of degree 12 hours, completing preparation surface modification has the modified electrode of gold nano grain.
Embodiment 4
Tri- chloride hydrate iridium of 22.05mg is weighed in 25ml deionized waters, sonic oscillation 2min makes precursor solution mix
Uniformly.1cm × 5cm carbon felts are taken again, after being rinsed well with deionized water, are dried in vacuo under 40 degrees Celsius.Before carbon felt is immersed
It drives in liquid solution, and stands 20min, precursor solution is made to be come into full contact with carbon felt fiber surface.Then, 85% hydrazine hydrate is taken
Solution 7ml hydrazine hydrate solution is added dropwise in the precursor solution for being soaked with carbon felt with rubber head dropper, and it is molten to stop dropwise addition reducing agent
30min is stood after liquid, and reducing agent is made fully to be reacted with precursor solution.Carbon felt is further taken out, and is dried in vacuo under 40 degrees Celsius
12 hours, completing preparation surface modification had the modified electrode of iridium nano particle.
Embodiment 5
It weighs 32.37mg six and is hydrated chloroplatinic acid in 25ml deionized waters, sonic oscillation 2min makes precursor solution mix
Uniformly.1cm × 5cm graphite flakes are taken again, is polished with 60cw sand paper, makes its rough surface, after being used in combination deionized water to rinse well, are dried
It is dry.The graphite flake handled well is immersed in precursor solution, and stands 20min, keeps precursor solution and graphite flake surface abundant
Contact.Then, the hydrazine hydrate solution 7ml for taking 85% is added dropwise hydrazine hydrate solution with rubber head dropper before being soaked with graphite flake
It drives in liquid solution, stops standing 30min after reducing agent solution is added dropwise, reducing agent is made fully to be reacted with precursor solution.It further takes out
Graphite flake, and be dried in vacuo 12 hours under 40 degrees Celsius, completing preparation surface modification has the modified electrode of Pt nanoparticle.
Claims (3)
1. a kind of preparation method of the modified electrode of zinc-bromine flow battery, which is characterized in that modified electrode is by basis material and base
The noble metal nano particles composition of body material surface modification, basis material is graphite flake or carbon felt, and noble metal nano particles are
Platinum, gold, palladium or iridium；Noble metal nano particles are attached to graphite flake surface or Carbon felt surface, are reacted as zinc-bromine flow battery
Catalyst, for improving zinc-bromine flow battery performance；Specific preparation method is as follows：
First, 0.0025M precursor solutions, and sonic oscillation 1-3 minutes are prepared, keeps solution uniform, processed graphite flake
Or carbon felt immerses in precursor solution 15-25 minutes, then, 0.0025M reducing agent solutions is added dropwise, reducing agent solution is anti-
Bad hematic acid solution or 85% hydrazine hydrate solution, the ratio between presoma and the amount of reducing agent substance are 1:2, it is molten to stop dropwise addition reducing agent
Standing 25-35 minutes after liquid makes it fully react, and during this, noble metal nano particles are by ascorbic acid solution or hydrazine hydrate
Solution reduction comes out, and the surface for being attached to graphite flake either carbon felt further takes out graphite flake or carbon felt, at 38-42 degrees Celsius
Lower vacuum drying 10-14 hours, is made modified electrode.
2. the preparation method of the modified electrode of zinc-bromine flow battery according to claim 1, which is characterized in that the forerunner
Liquid solution is formulated by chloroplatinic acid, gold chloride, ammonium chloropalladate or iridous chloride.
3. the preparation method of the modified electrode of zinc-bromine flow battery according to claim 2, it is characterised in that the graphite
The processing mode of piece is：60 mesh sand paper are polished, its rough surface is made；The processing mode of the carbon felt is：Deionized water is cleaned.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610817400.0A CN106159286B (en) | 2016-09-12 | 2016-09-12 | A kind of modified electrode and preparation method thereof applied to zinc-bromine flow battery |
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| CN201610817400.0A CN106159286B (en) | 2016-09-12 | 2016-09-12 | A kind of modified electrode and preparation method thereof applied to zinc-bromine flow battery |
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| CN106159286B true CN106159286B (en) | 2018-10-19 |
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| 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 |
| 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 |
| 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 |
| 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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| CN102569832A (en) * | 2010-12-09 | 2012-07-11 | 中国科学院大连化学物理研究所 | Negative electrode of zinc-bromine flow battery for energy storage and manufacture method thereof |
| CN202905873U (en) * | 2012-04-25 | 2013-04-24 | 中国工程物理研究院电子工程研究所 | Integrated terminal pole plate for flow battery |
| TWI501455B (en) * | 2013-10-28 | 2015-09-21 | Inst Nuclear Energy Res Atomic Energy Council | Method of Fabricating Electrode for High-Power-Density Flow Cell |
| CN105140552B (en) * | 2015-06-29 | 2017-11-14 | 湖南科技大学 | A kind of alcohol/Fe (III) liquid stream fuel cells and its manufacture method |
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