CN111261882A - Zinc-nickel flow battery cathode, application thereof and zinc-nickel flow battery - Google Patents
Zinc-nickel flow battery cathode, application thereof and zinc-nickel flow battery Download PDFInfo
- Publication number
- CN111261882A CN111261882A CN201811451231.9A CN201811451231A CN111261882A CN 111261882 A CN111261882 A CN 111261882A CN 201811451231 A CN201811451231 A CN 201811451231A CN 111261882 A CN111261882 A CN 111261882A
- Authority
- CN
- China
- Prior art keywords
- zinc
- flow battery
- nickel
- negative electrode
- substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
-
- 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
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
- H01M4/8885—Sintering or firing
-
- 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
- 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
-
- 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
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8684—Negative electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/002—Inorganic electrolyte
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to a zinc-nickel flow battery, in particular to a zinc-nickel flow battery cathode, wherein zinc oxide is attached to the surface of a substrate; the preparation method comprises soaking the substrate in soluble zinc salt solution at 30-50 deg.C for 10-60 min; drying at 60-80 ℃, transferring into a tubular furnace, and burning for 1-5h at 300-400 ℃ in an oxygen atmosphere; the required negative electrode is obtained. The invention solves the problem of zinc accumulation of the zinc cathode.
Description
Technical Field
The invention relates to the field of zinc-nickel flow batteries, in particular to a zinc-nickel flow battery cathode.
Technical Field
The zinc-nickel flow battery is a novel low-cost, high-efficiency and environment-friendly flow energy storage battery, has the advantages of high energy density and current efficiency, simple and easy operation of the device, long service life, low cost and the like, and is mainly applied to the fields of power grid peak shaving, power generation of renewable energy sources such as wind energy and solar energy, electric vehicles and the like.
The zinc/nickel flow battery is provided with only one electrolyte storage tank, the electrolyte is flowing zincate alkaline solution, an ion exchange membrane is not used in the battery, and a current loop is formed by the free flow of ions in a battery cavity and the directional movement of external circuit electrons. During charging, Ni (OH)2 of the positive electrode is oxidized into NiOOH, and zincate ions of the negative electrode are deposited into metal zinc; the reverse process occurs upon discharge. The cell does not use an ion exchange membrane, and a current loop is formed by the free movement of ions in the cell cavity and the directional flow of electrons of an external circuit.
The zinc-nickel flow battery applied to the field of large-scale energy storage needs to have higher energy storage capacity, which puts requirements on a high-capacity positive electrode. However, with the increase of capacity, the electrolyte transmission of the anode is increasingly difficult, so that the electrode is very easy to generate oxygen evolution side reaction, and a longer activation process is needed so as to construct a smooth ion transmission channel. However, the negative electrode itself undergoes a normal charge-discharge reaction in the positive electrode activation stage. And the current efficiency of the anode is far lower than that of the cathode due to oxygen evolution of the anode. So that more zinc can be accumulated in the negative electrode after the activation is finished. The solution causes the blockage of the flow channel and the short circuit of the anode and the cathode, and has serious harm to the stability of the system.
Disclosure of Invention
The invention provides a zinc-nickel flow battery cathode aiming at the problems, and solves the problem of zinc accumulation of a zinc cathode.
The cathode of the zinc-nickel flow battery comprises a substrate, wherein zinc oxide is attached to the surface of the substrate;
the preparation method comprises soaking the substrate in soluble zinc salt solution at 30-50 deg.C for 10-60 min; drying at 60-80 ℃, transferring into a tubular furnace, and burning for 1-5h at 300-400 ℃ in an oxygen atmosphere; the required negative electrode is obtained.
The soluble zinc salt is one or more than two of zinc acetate, zinc sulfate or zinc nitrate, and the concentration is 0.1-2.0 mol/L.
The substrate is a porous conductive carbon material of carbon felt, graphite felt, carbon paper or carbon cloth.
The cathode is applied to a zinc-nickel flow battery.
A zinc-nickel flow battery comprises single batteries or battery modules, electrolyte, a liquid storage tank, a circulating pump and a circulating pipeline, wherein the battery modules are formed by connecting more than two single batteries; the single cell is a zinc-nickel flow battery assembled by adopting the negative electrode of any one of claims 1-2; the single cell comprises a positive electrode end plate, a negative electrode end plate, a positive electrode and a negative electrode.
The positive electrode is a carbon felt, a graphite felt, carbon paper, carbon cloth or a foam metal electrode loaded with nickel hydroxide.
The current efficiency of the anode is far lower than that of the cathode due to oxygen evolution of the anode, so that more zinc simple substances can be accumulated on the zinc cathode after activation is completed. The solution causes the blockage of the flow channel and the short circuit of the anode and the cathode, and has serious harm to the stability of the system. The invention solves the problem of zinc accumulation of the zinc cathode.
Drawings
FIG. 1 is a graph of the cycle performance of the battery of example 1;
fig. 2 is a graph showing the cycle performance of the battery of comparative example 1.
Detailed Description
The present invention is further explained with reference to the following examples, which are not intended to limit the present invention in any way.
Example 1
Preparing a negative electrode: using a substrate of 36cm2The carbon felt is soaked in 1.0mol/L zinc acetate solution and is soaked for 30min at the temperature of 30 ℃; and (3) drying at 60 ℃, transferring into a tubular furnace, and burning for 3h at 400 ℃ in an oxygen atmosphere to obtain the required cathode.
The positive electrode is loaded with 5mg/cm2Carbon felt of nickel hydroxide.
The battery is assembled by using the battery pack,the electrolyte of the negative electrode is 6L of 4mol/L potassium hydroxide alkaline solution containing 0.5 mol/L zinc ions; the positive electrode electrolyte is 6L of potassium hydroxide alkaline solution containing 0.5 mol/L of zinc ions; using 10mA/cm2Current density of 40mA/cm2The current density of (2) is subjected to discharge cycling, and the charge cutoff condition of the battery is a voltage of not higher than 2.0V, and the discharge cutoff condition is a voltage of not lower than 2V. As can be seen from fig. 1, the prepared negative electrode shows good cycle performance when applied to a zinc-nickel single flow battery.
Example 2
The substrate is 36cm2Soaking a carbon felt in a 2.0mol/L zinc sulfate solution at the temperature of 50 ℃ for 60 min; after drying at 80 ℃, transferring the mixture into a tube furnace, and burning the mixture for 5 hours at 300 ℃ in an oxygen atmosphere. Obtaining the required sample.
Example 3
The substrate is 36cm2The carbon felt is immersed in 1.5mol/L zinc nitrate solution and is immersed for 40min at the temperature of 40 ℃; after drying at 70 ℃, transferring the mixture into a tube furnace, and burning the mixture for 4 hours at 350 ℃ in an oxygen atmosphere. Obtaining the required sample.
Comparative example 1
Negative electrode: 36cm2A carbon felt; the positive electrode is loaded with 5mg/cm2Carbon felt of nickel hydroxide.
The battery is assembled by using the electrolyte, and the electrolyte of the negative electrode is 6L of 4mol/L potassium hydroxide alkaline solution containing 0.5 mol/L zinc ions; the positive electrode electrolyte is 6L of potassium hydroxide alkaline solution containing 0.5 mol/L of zinc ions; using 10mA/cm2Current density of 40mA/cm2The current density of (2) is subjected to discharge cycling, and the charge cutoff condition of the battery is a voltage of not higher than 2.0V, and the discharge cutoff condition is a voltage of not lower than 2V. As can be seen from fig. 2, the cycle performance is poor.
After the batteries after operation were disassembled, it was found that the negative electrodes of the batteries of examples 1 to 3 had smooth surfaces and no large amount of zinc deposition occurred, and that a large amount of unreacted zinc simple substance remained on the surface of comparative example 1.
Claims (6)
1. The zinc-nickel flow battery cathode is characterized in that: comprises a substrate, wherein zinc oxide is attached to the surface of the substrate;
the preparation method comprises soaking the substrate in soluble zinc salt solution at 30-50 deg.C for 10-60 min; drying at 60-80 ℃, transferring into a tubular furnace, and burning for 1-5h at 300-400 ℃ in an oxygen atmosphere; the required negative electrode is obtained.
2. The anode of claim 1, wherein: the soluble zinc salt is one or more than two of zinc acetate, zinc sulfate or zinc nitrate, and the concentration is 0.1-2.0 mol/L.
3. The anode of claim 1, wherein: the substrate is a porous conductive carbon material of carbon felt, graphite felt, carbon paper or carbon cloth.
4. Use of the negative electrode of claim 1 or 2 in a zinc-nickel flow battery.
5. The utility model provides a zinc-nickel redox flow battery, includes monocell or battery module, electrolyte, liquid storage pot, circulating pump, circulating line, its characterized in that: the battery module is formed by connecting more than two monocells; the single cell is a zinc-nickel flow battery assembled by adopting the negative electrode of any one of claims 1-2; the single cell comprises a positive electrode end plate, a negative electrode end plate, a positive electrode and a negative electrode.
6. The zinc-nickel flow battery of claim 5, wherein: the positive electrode is a carbon felt, a graphite felt, carbon paper, carbon cloth or a foam metal electrode loaded with nickel hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811451231.9A CN111261882B (en) | 2018-11-30 | 2018-11-30 | Zinc-nickel flow battery cathode, application thereof and zinc-nickel flow battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811451231.9A CN111261882B (en) | 2018-11-30 | 2018-11-30 | Zinc-nickel flow battery cathode, application thereof and zinc-nickel flow battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111261882A true CN111261882A (en) | 2020-06-09 |
| CN111261882B CN111261882B (en) | 2021-05-04 |
Family
ID=70950148
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811451231.9A Active CN111261882B (en) | 2018-11-30 | 2018-11-30 | Zinc-nickel flow battery cathode, application thereof and zinc-nickel flow battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111261882B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112234215A (en) * | 2020-12-17 | 2021-01-15 | 中海储能科技(北京)有限公司 | Preparation method and application of modified carbon cloth |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130113431A1 (en) * | 2009-10-14 | 2013-05-09 | Research Foundation Of The City University Of New York | Nickel-Zinc Flow Battery |
| CN103579628A (en) * | 2012-07-25 | 2014-02-12 | 中国科学院大连化学物理研究所 | Zinc-nickel single-fluid cell anode, preparation method of zinc-nickel single-fluid cell anode, and zinc-nickel single-fluid cell |
| CN106463782A (en) * | 2014-07-09 | 2017-02-22 | 日本碍子株式会社 | Nickel-zinc battery |
| CN107221681A (en) * | 2017-06-14 | 2017-09-29 | 北京航空航天大学 | It is a kind of applied to modified electrode of all-vanadium flow battery and preparation method thereof |
-
2018
- 2018-11-30 CN CN201811451231.9A patent/CN111261882B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130113431A1 (en) * | 2009-10-14 | 2013-05-09 | Research Foundation Of The City University Of New York | Nickel-Zinc Flow Battery |
| CN103579628A (en) * | 2012-07-25 | 2014-02-12 | 中国科学院大连化学物理研究所 | Zinc-nickel single-fluid cell anode, preparation method of zinc-nickel single-fluid cell anode, and zinc-nickel single-fluid cell |
| CN106463782A (en) * | 2014-07-09 | 2017-02-22 | 日本碍子株式会社 | Nickel-zinc battery |
| CN107221681A (en) * | 2017-06-14 | 2017-09-29 | 北京航空航天大学 | It is a kind of applied to modified electrode of all-vanadium flow battery and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112234215A (en) * | 2020-12-17 | 2021-01-15 | 中海储能科技(北京)有限公司 | Preparation method and application of modified carbon cloth |
| CN112234215B (en) * | 2020-12-17 | 2021-03-09 | 中海储能科技(北京)有限公司 | Preparation method and application of modified carbon cloth |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111261882B (en) | 2021-05-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105958131B (en) | Rechargeable aqueous zinc ion battery with long cycle life and high energy density | |
| CN107863536B (en) | Multi-scale porous electrode applied to flow battery and preparation method and application thereof | |
| CN207587857U (en) | A kind of zinc-nickel single flow battery | |
| CN103579628B (en) | Zinc-nickel single flow battery positive pole and preparation and zinc-nickel single flow battery | |
| CN110767906A (en) | Chargeable water system ion battery based on phenazine negative electrode material and preparation method thereof | |
| CN102723518A (en) | All-lead liquid flow battery | |
| CN103618094A (en) | High-capacity lithium sulfur flow cell, and preparation method of electrode thereof | |
| CN113678218B (en) | Water system mixed super capacitor | |
| CN108390110B (en) | Lead-manganese secondary battery | |
| CN111261882B (en) | Zinc-nickel flow battery cathode, application thereof and zinc-nickel flow battery | |
| CN111244516A (en) | Application of additive in alkaline zinc-nickel flow battery negative electrolyte | |
| CN112687930B (en) | Application of additive in zinc-bromine flow battery electrolyte | |
| CN112952172A (en) | Alkaline iron-nickel flow battery | |
| CN104300169A (en) | Alkaline zinc vanadium flow battery | |
| CN109786798B (en) | Mixed type zinc-nickel flow battery | |
| CN115881915A (en) | Large-scale preparation method for in-situ construction of zinc cathode metal composite protective layer by ultrafast microwave technology and application thereof | |
| CN109786797B (en) | Activation method for positive electrode of zinc-nickel single flow battery | |
| CN111106397B (en) | Zinc-nickel accumulator | |
| CN111193033B (en) | Alkaline zinc-iron single flow battery | |
| CN111261876B (en) | Application of sodium sulfonated polyether ether ketone as binder in zinc-nickel flow battery electrode | |
| CN109326454B (en) | Crossed metal nanowire array supercapacitor electrode material and preparation method thereof | |
| CN109786799B (en) | Zinc-nickel flow battery | |
| CN111261917B (en) | Application of soluble manganate as additive in positive electrolyte of zinc-nickel flow battery | |
| CN113903963A (en) | Neutral zinc-iron flow battery and application thereof | |
| CN111525170A (en) | Tin-iron alkaline flow battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |