CN110620271A - Low-temperature liquid and semi-liquid metal battery - Google Patents
Low-temperature liquid and semi-liquid metal battery Download PDFInfo
- Publication number
- CN110620271A CN110620271A CN201910724733.2A CN201910724733A CN110620271A CN 110620271 A CN110620271 A CN 110620271A CN 201910724733 A CN201910724733 A CN 201910724733A CN 110620271 A CN110620271 A CN 110620271A
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- Prior art keywords
- liquid
- semi
- zinc
- liquid metal
- shell
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
- H01M10/399—Cells with molten salts
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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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/387—Tin or alloys based on tin
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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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/42—Alloys based on zinc
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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
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a low-temperature liquid and semi-liquid metal battery, which comprises a negative current collector, a shell, an insulating crucible, a negative material, a positive material and an electrolyte, wherein the negative current collector is arranged on the shell; an anode material and an insulating crucible filled with a cathode material are placed at the bottom in the shell, and the anode material and the insulating crucible are covered with an electrolyte; the negative current collector extends into the negative material through a central hole in the top of the shell; and an insulating sealing material is arranged at the contact part of the negative current collector and the central hole at the top of the shell. The positive electrode material and the electrolyte of the liquid or semi-liquid battery provided by the invention have low melting points, so that the battery can operate at a lower working temperature, and meanwhile, the positive electrode material and the negative electrode material of the battery do not contain active metals, so that the requirement on the corrosion resistance of an insulating material is low, and the battery has a simple structure, high safety and low cost.
Description
Technical Field
The invention relates to the technical field of energy storage batteries, in particular to a low-temperature liquid and semi-liquid metal battery.
Background
The energy storage technology is one of key technologies for eliminating the bottleneck of large-scale development and utilization of renewable energy, can improve the utilization efficiency of wind power and photovoltaic power generation, and can also improve the contradiction between power supply and demand, stabilize the peak-valley difference of a power grid, improve the traditional power generation efficiency and improve the safety and stability of the power grid. The electrochemical energy storage has the characteristics of high energy density, quick response time, low maintenance cost, flexible and convenient installation and the like, and is one of the hot development directions of the energy storage technology. At present, the main electrochemical energy storage technologies include lead-acid batteries, sodium-sulfur batteries, flow batteries, lithium ion batteries, and the like. However, the lead-acid battery has a short cycle life, the sodium-sulfur battery has not yet solved the safety problem under high-temperature operating conditions and the high cost problem of the electrolyte, the lithium ion battery and the flow battery have high costs, and the flow battery also faces the key technical problems of the electrolyte, the diaphragm material and the like.
To improve the life of energy storage batteries and reduce costs, professor Donald r.sadoway proposes a new concept of applying liquid metal batteries to large-scale energy storage of power grids. The basic features of liquid metal batteries are: the battery operates at 300-700 ℃, the positive and negative electrode metals and the inorganic salt electrolyte are all in liquid state, the electrolyte, the positive electrode and the negative electrode have different densities and are not mutually soluble, and the liquid state substance is automatically divided into three layers.
In recent years, research on liquid metal batteries has been carried out to a certain extent, and all the batteries have the characteristics of long cycle life, excellent high-rate charge and discharge performance and the like, but the batteries have higher operating temperature which is above 450 ℃, are particularly active at high temperature of lithium metal used as a battery cathode material, have higher requirements on thermal shock resistance and corrosion resistance of a battery sealing part, and are easy to cause fire once active metal at high temperature leaks. Higher operating temperatures also result in higher operating costs, which are detrimental to large-scale application of liquid metal batteries.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a low-temperature liquid and semi-liquid metal battery, which solves the problems of high operation temperature, poor safety and the like of the conventional liquid metal battery.
The purpose of the invention is realized by adopting the following technical scheme:
the present invention provides a low temperature liquid and semi-liquid metal battery, the improvement wherein said low temperature liquid and semi-liquid metal battery comprises:
the device comprises a negative electrode current collector (1), a shell (3), an insulating crucible (4), a negative electrode material (5), a positive electrode material (6) and an electrolyte (7);
an anode material (6) and an insulating crucible (4) filled with a cathode material (5) are placed at the bottom in the shell (3), and the anode material (6) and the insulating crucible (4) are covered with an electrolyte (7);
the negative current collector (1) extends into the negative material (5) through a central hole at the top of the shell (3).
Preferably, an insulating sealing material (2) is arranged at a contact part of the negative current collector (1) and a central hole at the top of the shell (3).
Preferably, the negative current collector (1) and the shell (3) are made of metal materials; the insulating sealing material (2) and the insulating crucible (4) are both made of ceramic or glass.
Preferably, the negative electrode material (5) is zinc, a zinc-tin alloy or a zinc-lead alloy, wherein the molar percentage of zinc in the zinc-tin alloy is 0-95%, and the molar percentage of zinc in the zinc-lead alloy is 0-50%.
Preferably, the positive electrode material (6) is bismuth, a lead bismuth alloy or a tin bismuth alloy.
Preferably, the electrolyte (7) is an inorganic salt mixture, and the inorganic salt mixture is a mixture consisting of zinc chloride and one or more of lithium chloride, lithium bromide, sodium chloride, sodium bromide, potassium chloride and potassium bromide.
Preferably, the operating temperature of the low temperature liquid and semi-liquid metal cells is in the range of 200 degrees celsius to 380 degrees celsius.
Compared with the closest prior art, the invention has the following beneficial effects:
the low-temperature liquid and semi-liquid metal battery provided by the invention has the advantages that the source of the used anode and cathode raw materials is wide, the cost is low, and the melting point of the used electrolyte is low, so that the battery can operate in the temperature range of 200-380 ℃. The anode and cathode materials do not contain active metal, and basically have no corrosion effect on the insulating sealing material, so that the safety of the battery in the operation process is greatly improved. The lower operation temperature not only reduces the operation cost of the battery, but also weakens the corrosion action of the anode and cathode materials and the electrolyte on the current collector and the shell, and is beneficial to prolonging the service life of the battery. In addition, the partial semi-liquid battery system can effectively deal with the vibration of the external environment of the battery and prevent the short circuit of the battery.
Drawings
Fig. 1 is a schematic cross-sectional view of a low temperature liquid and semi-liquid metal cell according to the present invention;
fig. 2 is a graph showing the charge and discharge performance of the liquid metal battery of example 1 according to the present invention;
fig. 3 is a graph showing the cycle charge and discharge performance of the liquid metal battery of example 5 according to the present invention;
wherein: 1-negative electrode current collector, 2-insulating sealing material, 3-shell, 4-insulating crucible, 5-negative electrode material, 6-positive electrode material and 7-electrolyte.
Detailed Description
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The present invention provides a low temperature liquid and semi-liquid metal battery, as shown in fig. 1, comprising: a negative current collector 1, a shell 3, an insulating crucible 4, a negative material 5, a positive material 6 and an electrolyte 7;
a positive electrode material 6 and an insulating crucible 4 filled with a negative electrode material 5 are placed at the bottom in the shell 3, and the positive electrode material 6 and the insulating crucible 4 are covered with an electrolyte 7; the negative current collector 1 extends into the negative material 5 through a central hole at the top of the shell 3; and an insulating sealing material 2 is arranged at the contact part of the negative current collector 1 and the central hole at the top of the shell 3.
The negative current collector 1 and the shell 3 are made of metal materials; the insulating sealing material 2 and the insulating crucible 4 are both made of ceramic or glass.
The negative electrode material 5 is zinc, a zinc-tin alloy or a zinc-lead alloy, wherein the molar percentage of zinc in the zinc-tin alloy is 0-95%, and the molar percentage of zinc in the zinc-lead alloy is 0-50%.
The positive electrode material 6 is bismuth, lead bismuth alloy or tin bismuth alloy.
The electrolyte 7 is an inorganic salt mixture, and the inorganic salt mixture is a mixture composed of zinc chloride and one or more of lithium chloride, lithium bromide, sodium chloride, sodium bromide, potassium chloride and potassium bromide.
The operating temperature of the low temperature liquid and semi-liquid metal cells is in the range of 200 degrees celsius to 380 degrees celsius.
The invention also provides the anode and cathode materials, the electrolyte, the working temperature, the battery voltage and the battery state of 9 embodiments of the low-temperature liquid and semi-liquid metal battery, which are shown in the table 1;
TABLE 1
As shown in fig. 2, the semi-liquid metal battery of example 1 was operated at 300 deg.c, a discharge voltage of 0.75-0.85V, and a coulombic efficiency of 98%.
As shown in fig. 3, the liquid metal battery of example 5 had an operating temperature of 200 ℃, a discharge voltage of 0.66-0.78V, a coulombic efficiency of 96-99%, and no significant capacity fading over many charge-discharge cycles.
The test results of the above examples show that: the liquid and semi-liquid metal batteries can operate at a lower temperature of 200-380 ℃, and have good voltage performance and excellent cycle performance.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the above embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the embodiments of the invention without departing from the spirit and scope of the invention, which is to be covered by the claims.
Claims (7)
1. A low-temperature liquid and semi-liquid metal battery is characterized by comprising a negative current collector (1), a shell (3), an insulating crucible (4), a negative material (5), a positive material (6) and an electrolyte (7);
an anode material (6) and an insulating crucible (4) filled with a cathode material (5) are placed at the bottom in the shell (3), and the anode material (6) and the insulating crucible (4) are covered with an electrolyte (7);
the negative current collector (1) extends into the negative material (5) through a central hole at the top of the shell (3).
2. A cryogenic liquid and semi-liquid metal battery according to claim 1, characterized in that the contact of the negative current collector (1) with the central hole in the top of the case (3) is provided with an insulating sealing material (2).
3. A cryogenic liquid and semi-liquid metal battery according to claim 1, characterized in that the negative current collector (1) and the casing (3) are of metal; the insulating sealing material (2) and the insulating crucible (4) are both made of ceramic or glass.
4. The low temperature liquid and semi-liquid metal battery of claim 1, wherein the negative electrode material (5) is zinc, a zinc-tin alloy or a zinc-lead alloy, wherein the molar percentage of zinc in the zinc-tin alloy is 0-95%, and the molar percentage of zinc in the zinc-lead alloy is 0-50%.
5. A low temperature liquid and semi-liquid metal battery according to claim 1, characterized in that the positive electrode material (6) is bismuth, a lead bismuth alloy or a tin bismuth alloy.
6. A cryogenic liquid and semi-liquid metal battery according to claim 1, characterized in that the electrolyte (7) is a mixture of inorganic salts, the mixture of inorganic salts being a mixture of zinc chloride and one or more of lithium chloride, lithium bromide, sodium chloride, sodium bromide, potassium chloride, potassium bromide.
7. A cryogenic liquid and semi-liquid metal cell according to claim 1 wherein the operating temperature of the cryogenic liquid and semi-liquid metal cell is in the range of 200 ℃ to 380 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910724733.2A CN110620271A (en) | 2019-08-07 | 2019-08-07 | Low-temperature liquid and semi-liquid metal battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910724733.2A CN110620271A (en) | 2019-08-07 | 2019-08-07 | Low-temperature liquid and semi-liquid metal battery |
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| Publication Number | Publication Date |
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| CN110620271A true CN110620271A (en) | 2019-12-27 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201910724733.2A Pending CN110620271A (en) | 2019-08-07 | 2019-08-07 | Low-temperature liquid and semi-liquid metal battery |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113594558A (en) * | 2021-07-06 | 2021-11-02 | 华中科技大学 | Liquid metal battery and preparation method thereof |
| CN114792847A (en) * | 2022-05-05 | 2022-07-26 | 华中科技大学 | Low-temperature liquid metal battery and preparation method thereof |
| CN114792847B (en) * | 2022-05-05 | 2024-04-19 | 华中科技大学 | Low-temperature liquid metal battery and preparation method thereof |
-
2019
- 2019-08-07 CN CN201910724733.2A patent/CN110620271A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113594558A (en) * | 2021-07-06 | 2021-11-02 | 华中科技大学 | Liquid metal battery and preparation method thereof |
| CN113594558B (en) * | 2021-07-06 | 2023-01-06 | 华中科技大学 | Liquid metal battery and preparation method thereof |
| CN114792847A (en) * | 2022-05-05 | 2022-07-26 | 华中科技大学 | Low-temperature liquid metal battery and preparation method thereof |
| CN114792847B (en) * | 2022-05-05 | 2024-04-19 | 华中科技大学 | Low-temperature liquid metal battery and preparation method thereof |
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