CN113809409A - Low-melting-point molten salt electrolyte of liquid or semi-liquid metal battery, preparation and application - Google Patents
Low-melting-point molten salt electrolyte of liquid or semi-liquid metal battery, preparation and application Download PDFInfo
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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
- H01M10/38—Construction or manufacture
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0048—Molten electrolytes used at high temperature
- H01M2300/0054—Halogenides
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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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using 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
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- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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Abstract
The invention discloses a low-melting-point molten salt electrolyte of a liquid or semi-liquid metal battery, and preparation and application thereof, and belongs to the field of energy storage batteries. The invention takes two or more metal halide salts of LiCl, LiBr, KCl and KBr as raw materials to prepare the low-melting-point liquid or semi-liquid metal battery molten salt electrolyte. Based on composition design and optimization, the melting point of the molten salt electrolyte system prepared by the invention is as low as 270-400 ℃, and the molten salt electrolyte system is applied to a liquid or semi-liquid metal battery, so that the working temperature of the battery can be greatly reduced, and the problems of difficult battery sealing, serious battery part corrosion, large energy consumption and the like caused by high working temperature of the existing liquid metal battery are further solved. In addition, the liquid or semi-liquid metal battery using the low-melting-point molten salt electrolyte has good electrochemical performance and long cycle life at a lower working temperature, and the coulomb efficiency is as high as 99%.
Description
Technical Field
The invention belongs to the field of energy storage batteries, and particularly relates to a low-melting-point molten salt electrolyte and a preparation method thereof.
Background
With the rapid development of global economy, the social demand for energy is increasing. The direct use of fossil energy such as coal, oil and natural gas can emit a large amount of CO2And the like, which causes serious environmental pollution problems. For reducing CO2The renewable energy sources such as wind energy, solar energy and the like are rapidly developed and utilized, but the renewable energy sources cannot be directly merged into a power grid due to the intermittent and fluctuating characteristics of the renewable energy sources, otherwise, the safety, stability and reliability of the work of a power system are influenced. The large-scale energy storage technology can store the electric power generated by the renewable energy sources and then match the electric power grid, so that the grid connection efficiency and reliability of the renewable energy sources are greatly improved. Therefore, the development of a novel low-cost and high-stability large-scale energy storage technology is an important guarantee for the development of renewable energy.
The liquid metal battery is a novel high-temperature molten salt battery, the anode and the cathode of the liquid metal battery and the electrolyte are in liquid states at working temperature, and the electrolyte is between the liquid anode and the liquid cathode due to density difference and mutual immiscibility, so that the three are automatically layered. The interfaces between the anode and the cathode and the electrolyte are liquid-liquid interfaces, which are beneficial to the rapid migration and charge transfer of reactants and products in the charge-discharge process. Meanwhile, the conductivity of the molten salt electrolyte is relatively high and is generally two orders of magnitude higher than that of the electrolyte of the lithium ion battery, so that the liquid metal battery has ultrafast charge transfer dynamics, and thus has excellent rate performance. In addition, the full-liquid battery structure can not cause the degradation of electrode microstructure such as electrode deformation, dendrite growth and the like in the circulating process, and the liquid metal battery has an ultra-long circulating life. Comprehensively considered, the liquid metal battery is a large-scale energy storage technology with great potential.
However, the working temperature of the liquid metal battery system reported at present is higher, generally above 450 ℃, and the higher working temperature causes the problems of difficult sealing of the battery, large energy consumption required for maintaining the battery to work and the like, and aggravates the high-temperature corrosion of the battery components in the long-cycle process. In the existing research, the melting point of bismuth-based and tin-based positive electrode Materials is low, below 300 ℃, the melting point of the negative electrode is generally 180.5 ℃, the melting point of the electrolyte system is high, generally above 430 ℃, and the main reason for maintaining the molten state of the electrolyte is high working temperature of the liquid metal battery (Nature Energy 3(2018) 732-. Therefore, on the basis of ensuring the required characteristics of electrolytes such as high conductivity, low metal solubility, wide electrochemical window, proper density and the like, the molten salt electrolyte with a lower melting point is developed to be an effective means for reducing the working temperature of the liquid metal battery, further reducing the operation cost of the battery and promoting the long-acting stable operation of the battery. Research and development of low-melting-point molten salt electrolyte and low-temperature liquid metal batteries are important subjects of research in the field of liquid metal batteries, and have important scientific and practical significance for promoting application of liquid metal batteries in the field of smart grid energy storage.
Disclosure of Invention
The invention provides a low-melting-point molten salt electrolyte and a preparation method thereof, which are applied to a liquid or semi-liquid metal battery, can effectively reduce the working temperature of the battery, and further solve the problems of difficult battery sealing, serious high-temperature corrosion of battery components and large energy consumption required for maintaining the working temperature of the battery caused by high working temperature of the existing liquid metal battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the present invention provides a low melting point molten salt electrolyte for a liquid or semi-liquid metal battery, characterized in that: the molten salt electrolyte is prepared by taking two or more metal halide salts of LiCl, LiBr, KCl and KBr as raw materials.
The molten salt electrolyte consists of LiCl40-80-KCl60-20、LiBr30-90-KBr70-10、LiCl40-80-KCl60-20-KBr0-60Or LiCl0-60-LiBr30-90-KBr70-10Wherein the lower right hand corner of the formula indicates the mole percent of each component and the mole percent of each component in each molten salt electrolyte adds up to 100%.
The invention also provides a preparation method of the low-melting-point liquid or semi-liquid metal battery molten salt electrolyte, which comprises the steps of weighing the required metal halide salt according to the mole percentage, fully mixing and grinding for 10-60min, and then sequentially drying and melting to obtain the required molten salt electrolyte.
Further, the drying step is mainly divided into the following two processes: firstly, heating the uniformly mixed metal halide salt to the temperature of 100 ℃ and 180 ℃ under the vacuum condition, and preserving the heat for 2-30 h; secondly, the temperature is continuously raised to 200-350 ℃, and the temperature is kept for 2-50 h. The purpose of the drying step is to remove moisture that may be present in the metal halide salt.
Further, the melting steps are as follows: heating the dried and uniformly mixed metal halide salt to 280-600 ℃ in an inert atmosphere or under vacuum, preserving the heat for 2-20h, and then cooling to room temperature for later use.
The invention also provides an energy storage battery applying the low-melting-point molten salt electrolyte material of the liquid or semi-liquid metal battery, which comprises a stainless steel shell, a ceramic sealing device, a molten salt electrolyte, a positive electrode material and a negative electrode material, wherein the molten negative electrode material is adsorbed in a negative electrode current collector. Wherein the molten salt electrolyte adopts LiCl40-80-KCl60-20、LiBr30-90-KBr70-10、LiCl40-80-KCl60-20-KBr0-60Or LiCl0-60-LiBr30-90-KBr70-10An electrolyte material.
Further, the negative electrode current collector is a porous foam metal material.
Further, in the energy storage battery, the positive electrode material and the molten salt electrolyte are in a liquid state or a semi-liquid state at the working temperature, and the negative electrode material is in a liquid state.
The test results of the liquid or semi-liquid metal battery prepared according to the invention show that compared with the existing electrolyte and liquid metal battery, the liquid or semi-liquid metal battery has the following advantages and beneficial effects:
firstly, the molten salt electrolyte provided by the invention has a lower melting point, the melting point of components such as LiCl, LiBr, KCl, KBr and the like in the component proportion can be as low as 270-400 ℃, and the working temperature of the liquid metal battery can be greatly reduced by matching with the positive electrode material and the negative electrode material with low melting points. Secondly, the molten salt electrolyte provided by the invention can effectively reduce the solubility of the cathode material in the molten salt electrolyte, so that the liquid metal battery has higher coulombic efficiency. Thirdly, the liquid metal battery assembled by the molten salt electrolyte provided by the invention has lower working temperature, effectively solves the problems of difficult battery sealing and large energy consumption required for maintaining the working temperature of the battery caused by high working temperature of the existing liquid metal battery, and simultaneously relieves the high-temperature corrosion of battery components, so that the liquid metal battery is more stable in the operation process and has longer cycle life. Fourthly, the molten salt electrolyte provided by the invention has wide raw materials and low price, and can reduce the production cost of the liquid metal battery. Fifth, the molten salt electrolyte provided by the invention has simple preparation process, no need of special equipment, high yield and suitability for assembly of large-capacity and large-scale liquid metal batteries.
In conclusion, the low-melting-point liquid or semi-liquid metal battery molten salt electrolyte provided by the invention has good electrochemical performance when being assembled with the existing positive electrode material and negative electrode material with lower melting points to form a battery for testing. The molten salt electrolyte provided by the invention has very wide raw materials and low price, greatly reduces the melting point of the existing electrolyte on the basis of ensuring the required characteristics of the liquid metal battery electrolyte, such as high conductivity, low metal solubility, wide electrochemical window, proper density and the like, further reduces the working temperature of the battery, solves the problems of difficult high-temperature sealing of the liquid metal battery, large energy consumption required for maintaining the working temperature of the battery, serious high-temperature corrosion in the long-time circulating process of battery parts and the like, and enables the liquid or semi-liquid metal battery to have wider application prospect.
Drawings
FIG. 1 is a flow diagram of the preparation of a low melting point molten salt electrolyte according to the present invention;
fig. 2 is a schematic diagram of the structure of an assembled cryogenic liquid or semi-liquid metal cell of the present invention;
fig. 3 is a charging and discharging curve of the low-temperature liquid metal energy storage battery according to embodiment 1 of the invention;
fig. 4 is a charging and discharging curve of the low-temperature liquid metal energy storage battery according to embodiment 2 of the invention;
fig. 5 is a charging and discharging curve of the low-temperature liquid metal energy storage battery of embodiment 2 of the invention under different current densities;
fig. 6 is a cycle performance curve of the low-temperature liquid metal energy storage battery according to embodiment 2 of the invention.
Detailed Description
The invention provides a low-melting-point liquid or semi-liquid metal battery molten salt electrolyte and a preparation method thereof, aiming at the problems of difficult high-temperature sealing, high energy consumption required for maintaining the working temperature of the battery, serious high-temperature corrosion in the long-time circulating process of battery components and the like of the existing liquid metal battery.
The invention provides a low-melting-point molten salt electrolyte for a liquid or semi-liquid metal battery, and the preparation process is shown in figure 1. The molten salt electrolyte prepared by the invention is prepared by taking two or more metal halide salts of LiCl, LiBr, KCl and KBr as raw materials. The molten salt electrolyte consists of LiCl40-80-KCl60-20、LiBr30-90-KBr70-10、LiCl40-80-KCl60-20-KBr0-60And LiCl0-60-LiBr30-90-KBr70-10Wherein the lower right hand corner of the formula indicates the mole percent of each component and the mole percent of each component in each molten salt electrolyte adds up to 100%.
When the molten salt electrolyte is prepared, the required metal halide salt is weighed according to the mole percentage, fully ground for 10-60min, and then dried and melted to obtain the required molten salt electrolyte.
The electrolyte drying step provided by the invention mainly comprises two processes, firstly, uniformly mixed metal halide salt is heated to 180 ℃ under the vacuum condition, and the temperature is kept for 2-30 h; secondly, the temperature is continuously raised to 200-350 ℃, and the temperature is kept for 2-50 h. The purpose of the drying step is to remove moisture that may be present in the metal halide salt.
The melting steps of the electrolyte provided by the invention are as follows: heating the dried and uniformly mixed metal halide salt to 280-600 ℃ in an inert atmosphere or under vacuum, preserving the heat for 2-20h, and then cooling to room temperature for later use.
In the present invention, it is preferable that the drying process and the melting process are performed by putting the uniformly ground metal halide raw material into an alumina crucible or a magnesia crucible.
The invention also provides a low-temperature liquid or semi-liquid metal energy storage battery, which takes metal or alloy with lower melting point and higher electronegativity as a positive electrode material, takes metal lithium as a negative electrode material, adopts the low-melting-point molten salt electrolyte provided by the invention as the electrolyte, and adopts a porous foam metal material, preferably a porous foam iron-nickel material as a negative electrode current collector.
In the present invention, the source of the positive and negative electrode materials and the electrolyte raw material is not particularly limited, and a supplier well known to those skilled in the art may be used, but it should be noted that the purity of all the raw materials should be 99% or more, and the purity of the metal raw material is preferably 99.99% or more.
The invention provides a low-temperature liquid metal battery which comprises a stainless steel shell, a ceramic sealing device, a molten salt electrolyte, a positive electrode material and a negative electrode material.
The preparation method of the low-temperature liquid metal battery provided by the invention comprises the following steps:
and placing the negative current collector in the molten negative material, and preserving heat for 0.5-5h to ensure that the negative metal with the proportion is adsorbed in the current collector, thereby completing the preparation of the negative electrode.
And heating the stainless steel shell to the working temperature of the battery, adding the anode material with required quality, and preserving heat for 2-10h to finish the preparation of the low-temperature liquid metal battery anode.
And then, putting the prepared molten salt electrolyte into a stainless steel shell containing the positive electrode, slowly melting the electrolyte into a liquid state, keeping the electrolyte above the positive electrode layer due to density difference and immiscibility of the electrolyte and the positive electrode, and preserving heat for 0.5-2h to ensure that the added electrolyte is completely melted.
And inserting the negative current collector adsorbing the negative material into the electrolyte, cooling to room temperature, and sealing the battery to finish the assembly of the battery.
In the present invention, the negative current collector is insulated from the case by a ceramic sealing device when the battery is assembled.
In the invention, the distance between the positive electrode material and the negative electrode current collector is 8-20cm when the battery is assembled, so that the positive electrode material and the negative electrode current collector are prevented from contacting with each other due to volume expansion of a discharge product in the charge and discharge processes of the liquid metal battery, and the short circuit of the battery is prevented.
In order to make the technical problems, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the respective embodiments described below may be combined with each other as long as they do not conflict with each other.
The structural schematic diagram of the low-temperature liquid metal battery adopting each embodiment is shown in fig. 2, and the low-temperature liquid metal battery comprises a stainless steel shell 1, an anode 2, an electrolyte 3, a cathode 4 and a ceramic sealing device 5, wherein the anode 2, the electrolyte 3 and the cathode 4 are sequentially placed in the stainless steel shell 1 from bottom to top, the cathode 4 is formed by a cathode current collector adsorbing cathode liquid metal, and the cathode current collector is insulated from the stainless steel shell 1 through the ceramic sealing device 5.
Example 1
The molten salt electrolyte of this example was prepared from LiBr and KBr in a molar ratio of 60:40, which had a low melting point of 334 ℃.
The electrolyte of this example was prepared as follows: firstly, weighing raw materials of LiBr and KBr according to the required mass, and putting the raw materials into an agate mortar for grinding for 30 min. And then putting the mixture into an alumina crucible and placing the alumina crucible into a heating furnace, heating to 150 ℃ and preserving heat for 20 hours under the vacuum condition, then heating to 300 ℃ and preserving heat for 40 hours to remove possible residual moisture in the electrolyte raw material, and finishing the drying of the electrolyte. And then, continuously raising the temperature of the heating furnace to 450 ℃, preserving the temperature for 5 hours, fully melting the electrolyte, and then cooling to room temperature for later use.
In the embodiment, lithium is selected as a negative electrode material, nickel foam is selected as a negative electrode current collector, and molten metal lithium with required mass is absorbed in the nickel foam to complete the preparation of the negative electrode. The method adopts metal bismuth with low melting point as a positive electrode material, and the molar ratio of the negative electrode material to the positive electrode material is 3: 1. The positive current collector is a graphite crucible. In the assembly process, the distance between the cathode and the anode is adjusted to be 15 mm. The whole assembly process is completed in a glove box filled with argon.
Fig. 3 is a charging and discharging curve of the low-temperature liquid metal energy storage battery according to embodiment 1 of the invention. The battery can stably run at low temperature of 420 ℃ earlier, and compared with the existing mature liquid metal battery system, the battery reduces 80-130 ℃, and the effect of the invention is very obvious. The reduction of the working temperature greatly improves the corrosion and the sealing performance of the key parts of the battery, and more choices of battery insulating devices and sealing materials are provided. In addition, the cell has excellent electrochemical performance during operation, 200mA cm-2Under the current density, the discharge median voltage of the battery is up to 0.58V, and the energy efficiency is 58.76%. Meanwhile, the battery of the present embodiment is at 200mA cm, owing to the low self-discharge rate of the battery at low temperature-2Exhibit a coulomb efficiency of up to 97% at low current densities.
Example 2
The molten salt electrolyte of the present example was prepared from three halide salts, LiCl, LiBr and KBr, in a molar ratio of 33:29:38, having a low melting point of 310 ℃.
The electrolyte of this example was prepared as follows: firstly, LiCl, LiBr and KBr raw materials are weighed according to the required mass and put into an agate mortar for grinding for 30 min. And then putting the mixture into an alumina crucible and placing the alumina crucible into a heating furnace, heating to 120 ℃ and preserving heat for 15 hours under the vacuum condition, then heating to 280 ℃ and preserving heat for 30 hours to remove possible residual moisture in the electrolyte raw material, and finishing the electrolyte drying. And then, continuously raising the temperature of the heating furnace to 400 ℃, preserving the temperature for 5 hours, fully melting the electrolyte, and then cooling to room temperature for later use.
In the embodiment, lithium is selected as a negative electrode material, nickel foam is selected as a negative electrode current collector, and molten metal lithium with required mass is absorbed in the nickel foam to complete the preparation of the negative electrode. The method adopts metal bismuth with low melting point as a positive electrode material, and the molar ratio of the negative electrode material to the positive electrode material is 3: 1. The positive current collector is a graphite crucible. In the assembly process, the distance between the cathode and the anode is adjusted to be 15 mm. The whole assembly process is completed in a glove box filled with argon.
Fig. 4 is a charging and discharging curve of the low-temperature liquid metal energy storage battery according to embodiment 2 of the invention. The battery also achieves a low operating temperature of 420 c due to the lower melting point of the electrolyte. At 200mA cm-2At current density, the cell had a higher discharge voltage than example 1, with a median discharge voltage of up to 0.65V. Furthermore, at this current density, the coulombic efficiency of the cell was 98% and the energy efficiency was 66.58%.
Fig. 5 is a charging and discharging curve of the low-temperature liquid metal energy storage battery of embodiment 2 of the invention under different current densities, and the operating temperature is 420 ℃. As the current density increases, the charging voltage increases and the discharging voltage decreases. This is mainly caused by the increasing charge and discharge polarization of the battery during the process. Notably, at 400mA cm-2The discharge median voltage of the battery is still as high as about 0.54V at high current density, about 75 percent of the theoretical electromotive force of the battery, and the energy efficiency is 58.85 percent.
Fig. 6 is a cycle performance curve of the low temperature liquid metal energy storage battery of example 2 of the present invention, with an operating temperature of 420 ℃. Thanks to the all-liquid battery structure of the liquid metal battery, there is no degradation of the electrode microstructure during the operation of the battery, and thus the battery of this example 2 has excellent cycle characteristics. At 400mA cm-2The coulomb efficiency is always kept above 99% under the current density for 56 cycles of charge and discharge, and the charge and discharge cycle is very stable.
Example 3
In this embodiment, a bismuth-tin alloy is used as the positive electrode material, wherein the molar percentage of bismuth to tin is 70: 30.
Except for the cathode material, the selection and preparation processes of the cathode and the electrolyte, the battery assembly and the working temperature are the same as those of the embodiment 2. The test result shows that the battery is 200mA cm-2The discharge median voltage of about 0.63V at a high current density of (2).
Example 4
The molten salt electrolyte of this example was prepared from two halide salts, LiCl and KCl, in a molar ratio of 60:40, and had a low melting point of 355 ℃. The procedure for preparing this electrolyte was the same as in example 1.
In this embodiment, metal tin is used as a positive electrode material, metal lithium is used as a negative electrode material, and a negative electrode preparation process and a battery assembly process are also the same as those in embodiment 1.
The battery of the embodiment operates at 450 ℃ and the discharge voltage is about 0.5V.
Example 5
In the embodiment, bismuth-lead alloy is adopted as the positive electrode material, wherein the molar percentage of bismuth to tin is 60: 40.
Except for the cathode material, the selection and preparation processes of the cathode and the electrolyte, the battery assembly and the working temperature are the same as those of the embodiment 2.
The test results show that: the electrolyte material of the invention effectively reduces the melting point of the electrolyte material of the existing liquid metal battery, obtains better voltage performance and higher energy efficiency, and has good long cycle performance of the battery.
The above description is of the preferred embodiment of the invention and is not intended to limit the invention. It should be noted that the present invention is well understood by those skilled in the art, and therefore, many alternatives, modifications, and improvements based on the principles of the present invention are also considered to be within the scope of the present invention.
Claims (7)
1. A low melting point molten salt electrolyte for a liquid or semi-liquid metal battery, comprising: the molten salt electrolyte is prepared by taking two or more metal halide salts of LiCl, LiBr, KCl and KBr as raw materials;
the molten saltThe composition of the electrolyte is LiCl40-80-KCl60-20、LiBr30-90-KBr70-10、LiCl40-80-KCl60-20-KBr0-60Or LiCl0-60-LiBr30-90-KBr70-10Wherein the lower right hand corner of the formula indicates the mole percent of each component and the mole percent of each component in each molten salt electrolyte adds up to 100%.
2. A method of preparing a low melting point molten salt electrolyte for a liquid or semi-liquid metal battery as claimed in claim 1, wherein: according to LiCl40-80-KCl60-20、LiBr30-90-KBr70-10、LiCl40-80-KCl60-20-KBr0-60Or LiCl0-60-LiBr30-90-KBr70-10And weighing the required metal halide salt according to the molar percentage, grinding for 10-60min in a dry inert atmosphere, and then sequentially performing drying and melting to obtain the required molten salt electrolyte.
3. A method of preparing a low melting point molten salt electrolyte for a liquid or semi-liquid metal battery as claimed in claim 2, wherein: the drying step is as follows: firstly, heating the uniformly mixed metal halide salt to the temperature of 100 ℃ and 180 ℃ under the vacuum condition, and preserving the heat for 2-30 h; secondly, continuously raising the temperature to 200-350 ℃, and preserving the temperature for 2-50 h; the purpose of the drying step is to remove moisture that may be present in the metal halide salt.
4. A method of preparing a low melting point molten salt electrolyte for a liquid or semi-liquid metal battery as claimed in claim 2, wherein: in the melting step, the dried metal halide salt is heated to 280-600 ℃ in an inert atmosphere or under vacuum condition, the temperature is kept for 2-20h, and then the metal halide salt is cooled to room temperature for standby.
5. A method of making a low temperature liquid or semi-liquid metal battery using the low melting point molten salt electrolyte of claims 1-4, characterized by: the battery comprises a stainless steel casing and a ceramic sealThe device comprises a device body, a molten salt electrolyte, a positive electrode material and a negative electrode material, wherein the molten salt electrolyte consists of LiCl40-80-KCl60-20、LiBr30-90-KBr70-10、LiCl40-80-KCl60-20-KBr0-60Or LiCl0-60-LiBr30-90-KBr70-10The molten negative electrode material is adsorbed in a negative electrode current collector.
6. The method of making a low temperature liquid or semi-liquid metal cell of claim 5, wherein: the negative current collector is made of a porous foam metal material.
7. The method of making a low temperature liquid or semi-liquid metal cell of claim 5, wherein: the positive electrode material and the molten salt electrolyte are in a liquid or semi-liquid state at the operating temperature, and the negative electrode material is in a liquid state.
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| CN114703511A (en) * | 2022-05-10 | 2022-07-05 | 有研资源环境技术研究院(北京)有限公司 | Low-melting-point chloride composite electrolyte, preparation method and application 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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| CN101355176A (en) * | 2008-09-05 | 2009-01-28 | 北京有色金属研究总院 | Method for preparing molten electrolyte |
| CN103715466A (en) * | 2013-12-11 | 2014-04-09 | 中国铝业股份有限公司 | Molten salt battery electrolyte |
| CN107221677A (en) * | 2017-07-05 | 2017-09-29 | 北京科技大学 | A kind of liquid metal cell of high-energy-density |
| CN110148779A (en) * | 2019-06-04 | 2019-08-20 | 北京航空航天大学 | Application, low temperature liquid molten salt lithium battery and preparation method of the LiI-KI eutectic salts in low temperature liquid molten salt lithium battery |
| CN110729470A (en) * | 2019-10-22 | 2020-01-24 | 北京科技大学 | Positive electrode material of liquid or semi-liquid metal battery, preparation method and application |
| CN111490261A (en) * | 2020-04-15 | 2020-08-04 | 中国工程物理研究院电子工程研究所 | Thermal battery electrolyte with low melting point and high conductivity and preparation method thereof |
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| 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 |
| CN114703511A (en) * | 2022-05-10 | 2022-07-05 | 有研资源环境技术研究院(北京)有限公司 | Low-melting-point chloride composite electrolyte, preparation method and application thereof |
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