CN108808053B - Zinc-nickel liquid flow energy storage battery - Google Patents
Zinc-nickel liquid flow energy storage battery Download PDFInfo
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- CN108808053B CN108808053B CN201810649162.6A CN201810649162A CN108808053B CN 108808053 B CN108808053 B CN 108808053B CN 201810649162 A CN201810649162 A CN 201810649162A CN 108808053 B CN108808053 B CN 108808053B
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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
- 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
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- 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 discloses a zinc-nickel liquid flow energy storage battery, which comprises a shell with a hollow cavity, a galvanic pile arranged in the hollow cavity, electrolyte arranged in the hollow cavity and used for immersing the galvanic pile, a solution pushing assembly arranged in the hollow cavity and used for pushing the electrolyte to circularly flow in the galvanic pile, and a driving mechanism arranged outside the shell and used for driving the solution pushing assembly; the galvanic pile is composed of a nickel electrode as a positive electrode and an inert current collector as a negative electrode in turn, and the positive electrode and the negative electrode are separated by a grid as a flow passage; the electrolyte is an alkaline aqueous solution containing soluble zinc salt, and the electrolyte contains gallium. According to the zinc-nickel flow energy storage battery, the gallium element is added into the electrolyte, so that the self-corrosion of the zinc of the negative electrode in the deposition and dissolution processes can be inhibited, and the integral charge retention capacity of the battery is improved.
Description
Technical Field
The invention relates to a zinc-nickel liquid flow energy storage battery, and belongs to the technical field of chemical power sources.
Background
With the gradual exhaustion of fossil energy, people will develop and utilize renewable energy sources such as wind energy, water energy and solar energy more and more widely. In order to ensure stable power supply of renewable energy power generation systems such as solar energy, water energy, wind energy and the like, an energy storage technology which is efficient, cheap, less in pollution, safe and reliable must be developed, and a large-scale energy storage technology is urgently required to be developed for peak load regulation, valley filling, load balancing and the like of a power grid. Large-scale energy storage techniques include physical energy storage such as heat storage and pumped storage, and also include chemical storage battery energy storage. Throughout the various types of chemical storage battery energy storage technologies, flow batteries have become one of the most suitable batteries for large-scale energy storage due to their unique advantages.
The zinc-nickel flow energy storage battery belongs to a deposition type flow battery, is a novel flow energy storage battery with low price, excellent efficiency, safety and environmental protection, has the advantages of high energy density and current efficiency, simple and easy device operation, long service life, low cost and the like, and is mainly applied to the fields of power grid peak regulation, energy storage of renewable energy sources such as wind energy, solar energy and the like for power generation, electric vehicles and the like.
The positive electrode of the zinc-nickel flow energy storage battery is a solid nickel oxide electrode, the negative electrode is a deposition/dissolution type zinc electrode on an inert current collector, the electrolyte is a flowing zincate alkaline solution, an ion exchange membrane is not used in the battery, and the directional flow of the electrolyte in a battery cavity is driven by a circulating pump outside the battery; nickel hydroxide (Ni (OH)) in solid nickel oxide electrode upon charging2) Oxidized into nickel oxyhydroxide (NiOOH), and zincate ions in the solution are deposited into metal zinc on the negative electrode; during discharging, hydroxyl nickel oxide is reduced into nickel hydroxide, and meanwhile, metal zinc of the negative electrode is dissolved into zincate ions.
In the zinc-nickel flow energy storage battery, the concentration of zinc ions in a solution determines the energy storage capacity and the energy density of a battery system; the zinc deposited on the negative electrode is easy to generate self-corrosion hydrogen evolution, so that the self-discharge of the negative electrode is fast, and the integral charge retention capability of the battery is poor. Therefore, the zinc-nickel flow energy storage battery needs an optimized electrolyte, the overall charge retention capacity of the battery is improved, and the energy density of the battery is considered.
Disclosure of Invention
The invention aims to provide a zinc-nickel flow energy storage battery, which can inhibit the self-corrosion of negative zinc in the deposition and dissolution processes through an optimized electrolyte, improve the overall charge retention capacity of the battery and have higher energy density of the battery.
In order to achieve the purpose, the invention adopts the technical scheme that:
a zinc-nickel liquid flow energy storage battery comprises a shell with a hollow cavity, a galvanic pile arranged in the hollow cavity, electrolyte arranged in the hollow cavity and used for immersing the galvanic pile, a solution pushing assembly arranged in the hollow cavity and used for pushing the electrolyte to circularly flow in the hollow cavity, and a driving mechanism arranged outside the shell and used for driving the solution pushing assembly;
the galvanic pile consists of a nickel electrode as a positive electrode and an inert current collector as a negative electrode which are sequentially and alternately arranged;
the electrolyte is an alkaline aqueous solution containing soluble zinc salt, and the electrolyte contains gallium.
Preferably, in the electrolyte, the concentration of the gallium element is 0.005-0.5 mol/L; the concentration of the zinc element is 0.6-1.3 mol/L; the concentration of the alkali is 6.5-13.5 mol/L.
More preferably, in the electrolyte, the concentration of the gallium element is 0.05-0.3 mol/L; the concentration of the zinc element is 0.7-1.2 mol/L.
More preferably, the electrolyte further contains tin element, and the concentration of the tin element is 0.005-0.2 mol/L.
Still more preferably, the concentration of the tin element is 0.05 to 0.15 mol/L.
Still more preferably, the electrolyte further contains lead element, and the concentration of the lead element is 0.0001-0.0005 mol/L.
Preferably, the active material of the positive electrode includes one or more of nickel oxide, nickel hydroxide, and nickel oxyhydroxide.
Preferably, in the electrolyte, the alkaline aqueous solution is composed of one or more of barium hydroxide, sodium hydroxide, potassium hydroxide and lithium hydroxide.
Preferably, the inert current collector is a steel strip or a tin-plated steel strip or a punched nickel-plated and then tin-plated steel strip or a nickel foil or a tin-nickel foil.
Preferably, the zinc-nickel flow battery further comprises a positive electrode pole column which is arranged on the shell in a penetrating manner and electrically connected with the positive electrode, and a negative electrode pole column which is arranged on the shell in a penetrating manner and electrically connected with the negative electrode.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages: according to the zinc-nickel flow energy storage battery, the gallium element is added into the electrolyte, so that the self-corrosion of the zinc of the negative electrode in the deposition and dissolution processes can be inhibited, and the integral charge retention capacity of the battery is improved.
Detailed Description
The technical solution of the present invention is further explained below.
The zinc-nickel liquid flow energy storage battery comprises a shell with a hollow cavity, a galvanic pile arranged in the hollow cavity, electrolyte arranged in the hollow cavity and used for immersing the galvanic pile, a solution pushing assembly arranged in the hollow cavity and used for pushing the electrolyte to flow in the galvanic pile in a circulating manner, and a driving mechanism arranged outside the shell and used for driving the solution pushing assembly. The solution pushing assembly is used for pushing the electrolyte to flow between the anode and the cathode in a directional and circulating manner so as to ensure the density and concentration uniformity of the electrolyte and further ensure the reaction uniformity of the anode and the cathode during charging and discharging. In this embodiment, the driving mechanism is an electric motor disposed at the top of the housing, and the solution pushing assembly is a stirring paddle (the driving mechanism may also be a centrifugal pump, and the solution pushing assembly is a turbine).
The galvanic pile is composed of nickel oxide electrode as positive electrode and inert current collector as negative electrode in turn, which are separated by grid as flow channel. The active material of the positive electrode mainly includes nickel oxide (NiO), nickel hydroxide (Ni (OH)2) And nickel oxyhydroxide (NiOOH). The inert current collector is a steel strip or a tin-plated steel strip or a punched nickel-plated and then tin-plated steel strip or a nickel foil or a tin-nickel foil. The zinc-nickel flow energy storage battery also comprises an anode pole which is arranged on the shell in a penetrating way and is electrically connected with the anode, and a cathode pole which is arranged on the shell in a penetrating way and is electrically connected with the cathode.
The electrolyte of the zinc-nickel flow energy storage battery is an alkaline aqueous solution containing soluble zinc salt, and the electrolyte contains gallium. In the present embodiment, the gallium element is present in the electrolyte in the form of gallium hydroxide.
In this embodiment, the electrolyte may further contain tin element and lead element; the tin element exists in the electrolyte in the form of potassium stannate; the lead element is present in the electrolyte in the form of lead oxide.
Wherein, the concentration of the gallium element is 0.05-0.3 mol/L; the concentration of tin element is 0.05-0.15 mol/L; the concentration of lead is 0.0001-0.0005 mol/L; the concentration of the zinc element is 0.7-1.2 mol/L. The concentration of the alkali is 6.5-13.5 mol/L.
The alkaline aqueous solution was prepared from a barium hydroxide solution (Ba (OH)2) And one or more of sodium hydroxide solution (NaOH), potassium hydroxide solution (KOH) and lithium hydroxide solution (LiOH). In thatIn this embodiment, the alkaline aqueous solution includes a potassium hydroxide solution and a lithium hydroxide solution. Wherein the concentration of the potassium hydroxide is 8.0-11.5mol/L, and the concentration of the lithium hydroxide is 0.2-0.4 mol/L.
Referring to table 1, the results of the charge capacity test of the zinc-nickel flow battery after the base electrolyte (11.3mol/L KOH +0.2mol/L LiOH +1.0mol/L ZnO) and the gallium hydroxide with different concentrations added to the base electrolyte are shown.
Table 1: charging capacity of zinc-nickel flow energy storage battery after adding gallium hydroxide with different concentrations into basic electrolyte
In Table 1, B represents a base electrolyte (11.3mol/L KOH +0.2mol/L LiOH +1.0mol/L ZnO).
The test method is 10mA/cm2Fully charged and standing for different time, and then 10mA/cm2Discharge (electrolyte still flows during rest) divided by the amount of charge (coulombic efficiency,%); the discharge coulomb efficiency is above 95% when the device is not in static state.
As can be seen in table 1, the discharge capacity after 12h of rest gradually increased with increasing concentration of added gallium hydroxide. The coulombic efficiency is still 80.7 percent after 0.3mol/L of gallium hydroxide is added, fully charged and kept stand for 12 hours; and the coulomb efficiency of the basic electrolyte (11.3mol/L KOH +0.2mol/L LiOH +1.0mol/L ZnO) after being fully charged and standing for 12 hours is only 62.0%, compared with the prior art, the coulomb efficiency is obviously improved after the gallium element is added into the electrolyte, namely the integral charge retention capability of the zinc-nickel flow battery is improved.
Referring to Table 2, the results of the charge capacity test of the zinc-nickel flow battery are obtained for the basic electrolyte (11.3mol/L KOH +0.2mol/L LiOH +1.0mol/LZnO) and after different concentrations of potassium stannate are added into the basic electrolyte.
Table 2: zinc-nickel flow energy storage battery charging capacity after adding potassium stannate with different concentrations into basic electrolyte
In Table 2, B represents a base electrolyte (11.3mol/L KOH +0.2mol/L LiOH +1.0mol/L ZnO).
The test method is 10mA/cm2Fully charged and standing for different time, and then 10mA/cm2Discharge (electrolyte still flows during rest) divided by the amount of charge (coulombic efficiency,%); the discharge coulomb efficiency is above 95% when the device is not in static state.
As can be seen in Table 2, the discharge capacity after 12h at rest gradually increased with increasing concentration of potassium stannate added. The coulombic efficiency is still 81.1 percent after 0.1mol/L of potassium stannate is added, fully charged and kept stand for 12 hours; and the coulomb efficiency of the basic electrolyte (11.3mol/L KOH +0.2mol/L LiOH +1.0mol/L ZnO) after being fully charged and standing for 12 hours is only 62.0%, compared with the coulomb efficiency obviously improved after the tin element is added into the electrolyte, namely the integral charge retention capacity of the zinc-nickel flow battery is improved.
Referring to table 3, the results of the chargeability test of the zinc-nickel flow battery after the base electrolyte (11.3mol/L KOH +0.2mol/L LiOH +1.0mol/L ZnO) and the gallium hydroxide and potassium stannate with different concentrations added to the base electrolyte are shown.
Table 3: charging capacity of zinc-nickel flow energy storage battery after adding gallium hydroxide and potassium stannate with different concentrations into basic electrolyte
In Table 3, B represents a base electrolyte (11.3mol/L KOH +0.2mol/L LiOH +1.0mol/L ZnO).
The test method is 10mA/cm2Fully charged and standing for different time, and then 10mA/cm2Discharge (electrolyte still flows during rest) divided by the amount of charge (coulombic efficiency,%); the discharge coulomb efficiency is above 95% when the device is not in static state.
As can be seen in Table 3, the discharge capacity after 12 hours of rest gradually increased with increasing concentrations of gallium hydroxide and potassium stannate added. The coulombic efficiency is still 82.0 percent after 0.3mol/L of gallium hydroxide and 0.1mol/L of potassium stannate are added, the mixture is fully charged and stands for 12 hours; and the coulomb efficiency of the basic electrolyte (11.3mol/L KOH +0.2mol/L LiOH +1.0mol/L ZnO) after being fully charged and standing for 12 hours is only 62.0%, and compared with the coulomb efficiency, the coulomb efficiency is obviously improved after the gallium element and the tin element are added into the electrolyte, namely the integral charge holding capacity of the zinc-nickel flow battery is improved. Meanwhile, when the gallium and the tin are jointly used as additives and added into the electrolyte, the charge capacity of the zinc-nickel flow energy storage battery is improved compared with that when the gallium and the tin are added separately.
Referring to table 4, the results of the chargeability test of the zinc-nickel flow battery are obtained after the basic electrolyte (11.3mol/L KOH +0.2mol/L LiOH +1.0mol/L ZnO) and the zinc-nickel flow battery added with gallium hydroxide, potassium stannate and lead oxide with different concentrations in the basic electrolyte.
Table 4: after gallium hydroxide, potassium stannate and lead oxide with different concentrations are added into basic electrolyte, charging capacity of zinc-nickel flow energy storage battery is improved
In Table 4, B represents a base electrolyte (11.3mol/L KOH +0.2mol/L LiOH +1.0mol/L ZnO).
The test method is 10mA/cm2Fully charged and standing for different time, and then 10mA/cm2Discharge (electrolyte still flows during rest) divided by the amount of charge (coulombic efficiency,%); the discharge coulomb efficiency is above 95% when the device is not in static state.
As can be seen in Table 4, the discharge capacity after 12 hours of rest gradually increased with increasing concentrations of gallium hydroxide, potassium stannate and lead oxide added. The coulombic efficiency is still 84.2 percent after 0.3mol/L of gallium hydroxide, 0.1mol/L of potassium stannate and 0.0005mol/L of lead oxide are added, the capacitor is fully charged and stands for 12 hours; and the coulomb efficiency of the basic electrolyte (11.3mol/L KOH +0.2mol/L LiOH +1.0mol/L ZnO) after being fully charged and standing for 12 hours is only 62.0%, and in comparison, after the gallium element, the tin element and the lead element are added into the electrolyte, the coulomb efficiency is obviously improved, namely the integral charge holding capacity of the zinc-nickel flow battery is improved. Meanwhile, when gallium, tin and lead are jointly used as additives to be added into the electrolyte, the charge capacity of the zinc-nickel flow energy storage battery is obviously improved compared with that of the basic electrolyte along with the increase of the concentration of the additives; when the gallium, the tin and the lead are jointly used as additives and added into the electrolyte, the charge capacity of the zinc-nickel flow energy storage battery is also improved compared with that of a zinc-nickel flow energy storage battery when the gallium and the tin are added in a composite mode.
In terms of electrochemical deposition potential, lead will deposit preferentially in alkaline electrolyte, tin will deposit when the potential is reduced, gallium will deposit when the potential is again reduced, and zinc will deposit at a lower potential. Thus, lead may deposit primarily prior to and act as a deposition matrix for tin, gallium, and zinc; tin is deposited after lead, serves as a deposition matrix for zinc and may become a tin-zinc alloy to promote the dense deposition of zinc; the gallium deposition potential is close to that of zinc and can be used as an inclusion sediment and a gallium-zinc alloying crystal nucleus; lead, tin and gallium are all high hydrogen evolution overpotential metals, are deposited or doped in the zinc phase before zinc, improve the hydrogen evolution overpotential and inhibit the self-dissolution of zinc.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (7)
1. A zinc-nickel liquid flow energy storage battery is characterized in that: the electrolyte solution circulating device comprises a shell with a hollow cavity, an electric pile arranged in the hollow cavity, electrolyte arranged in the hollow cavity and used for immersing the electric pile, a solution pushing assembly arranged in the hollow cavity and used for pushing the electrolyte to circularly flow in the hollow cavity, and a driving mechanism arranged outside the shell and used for driving the solution pushing assembly;
the galvanic pile consists of a nickel electrode as a positive electrode and an inert current collector as a negative electrode which are sequentially and alternately arranged;
adding zinc oxide, gallium hydroxide and lead oxide into the electrolyte;
the electrolyte is an alkaline aqueous solution containing soluble zinc salt;
in the electrolyte, the concentration of the gallium element is 0.005-0.5 mol/L; the concentration of the zinc element is 0.6-1.3 mol/L; the concentration of alkali is 6.5-13.5 mol/L; the concentration of lead element is 0.0001-0.0005 mol/L;
the electrolyte also contains stannic acid radicals, and the concentration of the stannic acid radicals is 0.005-0.2 mol/L.
2. The zinc-nickel flow energy storage battery of claim 1, wherein: in the electrolyte, the concentration of the gallium element is 0.05-0.3 mol/L; the concentration of the zinc element is 0.7-1.2 mol/L.
3. The zinc-nickel flow energy storage battery of claim 1, wherein: the concentration of stannate is 0.05-0.15 mol/L.
4. The zinc-nickel flow energy storage battery of claim 1, wherein: the active material of the positive electrode includes at least one of nickel oxide, nickel hydroxide, and nickel oxyhydroxide.
5. The zinc-nickel flow energy storage battery of claim 1, wherein: in the electrolyte, the alkaline aqueous solution is composed of at least one of barium hydroxide, sodium hydroxide, potassium hydroxide and lithium hydroxide.
6. The zinc-nickel flow energy storage battery of claim 1, wherein: the inert current collector is a steel strip or a tin-plated steel strip or a punched nickel-plated and then tin-plated steel strip or a nickel foil or a tin-plated nickel foil.
7. The zinc-nickel flow energy storage battery of claim 1, wherein: the zinc-nickel liquid flow energy storage battery also comprises an anode pole column which is arranged on the shell in a penetrating way and electrically connected with the anode, and a cathode pole column which is arranged on the shell in a penetrating way and electrically connected with the cathode.
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111244516A (en) * | 2018-11-28 | 2020-06-05 | 中国科学院大连化学物理研究所 | Application of additive in alkaline zinc-nickel flow battery negative electrolyte |
| CN109980260B (en) * | 2019-04-16 | 2023-03-24 | 常州大学 | Flow battery |
| CN113036193B (en) * | 2019-12-06 | 2022-06-03 | 中国科学院大连化学物理研究所 | Liquid metal zinc-based battery |
| WO2021243774A1 (en) * | 2020-05-30 | 2021-12-09 | 苏州沃泰丰能电池科技有限公司 | High-specific-energy zinc-nickel flow battery having one negative electrode and multiple positive electrodes |
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Effective date of registration: 20230207 Address after: 313199 Pheasant Town Emerging Industrial Park, Changxing County, Huzhou City, Zhejiang Province Patentee after: Chaowei Power Group Co.,Ltd. Address before: 313100 floor 1, plant 4, National University Science Park, No. 669 Gaotie railway, Changxing County Development Zone, Huzhou City, Zhejiang Province Patentee before: ZHEJIANG YUYUAN ENERGY STORAGE TECHNOLOGY Co.,Ltd. |