CN113193179A - Liquid metal battery and preparation method thereof - Google Patents
Liquid metal battery and preparation method thereof Download PDFInfo
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- CN113193179A CN113193179A CN202110336544.5A CN202110336544A CN113193179A CN 113193179 A CN113193179 A CN 113193179A CN 202110336544 A CN202110336544 A CN 202110336544A CN 113193179 A CN113193179 A CN 113193179A
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- 229910001338 liquidmetal Inorganic materials 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 76
- 239000002184 metal Substances 0.000 claims abstract description 76
- 239000000654 additive Substances 0.000 claims abstract description 59
- 230000000996 additive effect Effects 0.000 claims abstract description 57
- 239000003792 electrolyte Substances 0.000 claims description 22
- 239000007774 positive electrode material Substances 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 7
- 239000000919 ceramic Substances 0.000 claims description 6
- 239000010963 304 stainless steel Substances 0.000 claims description 5
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 claims description 5
- 229910052793 cadmium Inorganic materials 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 229910052711 selenium Inorganic materials 0.000 claims description 5
- 229910052714 tellurium Inorganic materials 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- 229910052745 lead Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000006262 metallic foam Substances 0.000 claims 1
- 239000010405 anode material Substances 0.000 abstract description 10
- 150000003839 salts Chemical class 0.000 abstract description 10
- 239000010935 stainless steel Substances 0.000 abstract description 5
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 14
- 238000007599 discharging Methods 0.000 description 10
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- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 229910013493 LiCl-LiBr-LiF Inorganic materials 0.000 description 6
- 229910013644 LiCl—LiBr—LiF Inorganic materials 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
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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
- H01M4/368—Liquid depolarisers
-
- 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
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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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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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
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
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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
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Abstract
The invention discloses a liquid metal battery and a preparation method thereof, belonging to the field of liquid metal battery anode materials. The additive X is added into the positive electrode metal, so that the positive electrode metal can be uniformly paved with the stainless steel positive current collector, interface disturbance caused by nonuniform current density distribution can be avoided, micro short circuit is reduced, and stable operation of the battery is promoted; the addition of the additive X can also reduce the thickness of the positive metal layer and reduce the distance between the positive electrode and the negative electrode during the safe operation of the battery, thereby reducing the internal resistance of the battery and being beneficial to improving the energy efficiency; in addition, the anode metal can have a flat metal/molten salt interface after the additive X is added, so that the using amount of the anode metal is reduced, the utilization rate of the anode material is improved, and the cost of the single battery can be reduced.
Description
Technical Field
The invention belongs to the technical field of electrochemical energy storage, and particularly relates to a liquid metal battery and a preparation method thereof.
Background
In recent years, renewable energy is adopted, a smart power grid is constructed, and an energy structure is adjusted to relieve environmental pressure and solve the problems of distribution regulation and high-efficiency utilization of electric energy. However, due to the intermittency and fluctuation of wind energy and solar energy generation, the utilization rate is low, and a serious problem of wind and electricity abandonment occurs, so that large-scale energy storage technology is required to be incorporated into a power grid. In addition, the large-scale energy storage technology can effectively realize user side demand management, reduce day and night peak-valley difference, smooth load, reduce power supply cost and improve the quality and stability of power grid operation. Compared with the existing mature technologies such as pumped storage, the electrochemical energy storage technology is not limited by natural environment, has the advantages of high energy conversion efficiency, long service life and the like, and has great potential in future large-scale energy storage construction.
In a plurality of energy storage technologies, the liquid metal battery energy storage technology has wide raw material sources, and compared with a non-aqueous electrolyte (an ionic liquid and an organic electrolyte) with high price, inorganic salt with low price and easy processing is adopted as the electrolyte. When the electrolyte runs under the high-temperature condition, the inorganic molten salt electrolyte has a wider potential window and high ionic conductivity and is also used as a diaphragm, so that the electrochemical reaction rate in the liquid metal battery is high, the response time is short, and the battery structure is simple. In addition, under the high-temperature operation, the liquid interface in the battery is continuously updated, so that the change of an electrode structure and the growth of a negative active metal dendritic crystal can be avoided, and the ultra-long theoretical cycle life of the liquid metal battery is ensured. The liquid metal battery can meet the requirement of large-scale energy storage due to the characteristics.
However, in actual battery operation, the positive metal material and the stainless steel are subjected to current collectionThe wettability between the bodies is poor, the anode material is in a convex state as a whole and cannot be completely paved on the bottom of the shell, and the current density distribution of the battery on a liquid anode metal interface is uneven in the charging and discharging process, so that an intermetallic compound with a high melting point generated in the discharging process of the battery has an arch structure in an anode region, and the middle arch is contacted with a cathode current collector to easily cause short circuit of the battery; in the charging process of the battery, the solid intermetallic compound with low density floats on the liquid positive electrode metal, and the electrode interface fluctuates along with the charging of the battery, so that the intermetallic compound is in contact with the negative electrode current collector to cause short circuit. The short circuit occurs inside the battery, which results in deterioration of the battery stability. In order to obtain a stable positive electrode interface, when a 200Ah Li I Bi high-capacity single battery is assembled, the mass of positive electrode Bi needs to be 268g in excess (the capacity is about 100Ah in excess) to fully cover a battery shell (the area is 226.87 cm)2). Although the stability of the battery is improved, the cost of the single battery is increased, and the utilization rate of the positive electrode material is greatly reduced (66.6%). In addition, the amplification of the Li | | | Sb-Bi single battery is hindered by the reasons, when the Li | | Sb-Bi single battery is amplified to 50Ah, the charge-discharge curve of the battery is unstable, the charge-discharge capacity, the coulombic efficiency and the energy efficiency of the battery in different cycles are obviously fluctuated, and the battery is unstable and easy to be short-circuited and fail in operation.
Disclosure of Invention
The invention provides a positive electrode additive for improving the stability of a liquid metal battery aiming at the condition of unstable battery operation caused by poor wettability between a positive electrode metal interface and a positive electrode current collector in the liquid metal battery, and solves the problems of easy short circuit failure of the battery, unstable operation of a single battery after amplification, low positive electrode metal utilization rate and the like.
In order to achieve the purpose, the liquid metal battery comprises a shell, and a positive electrode, a negative electrode current collector and an electrolyte which are arranged in the shell, wherein the negative electrode metal is adsorbed in the negative electrode current collector, the positive electrode consists of a positive electrode metal and an additive X, the additive X is Cu, Cd, Se or Te, and the amount of the additive X is less than 10% of the amount of the positive electrode material.
Further, the amount of the additive X is 5-8% of the amount of the positive electrode material.
Further, the positive electrode metal is one or a combination of more of Sb, Bi, Sn, and Pb.
Further, the material of the shell is 304 stainless steel.
Further, the negative electrode metal is an alkali metal or an alkaline earth metal.
Further, the negative current collector is a porous foam metal material.
A preparation method of a liquid metal battery comprises the following steps:
adding positive electrode metal and an additive X into a shell, wherein the amount of the additive X is less than 10% of that of the positive electrode material, stirring to uniformly distribute the additive X in the positive electrode metal to obtain a mixture A, heating the mixture A to completely melt the positive electrode metal, and preserving heat to obtain a positive electrode material, wherein the additive X is Cu, Cd, Se or Te;
and sequentially adding electrolyte and a negative current collector into the shell, leading out a negative lead from the negative current collector, separating the shell from the negative lead by using a ceramic sealing member, and sealing the shell.
Further, the additive X is in the form of powder, and the positive electrode metal used is in the form of granules or powder.
Compared with the prior art, the invention has at least the following beneficial technical effects:
1) according to the invention, X is used as the liquid metal anode additive, so that the surface interfacial tension of the anode liquid metal can be effectively reduced, the surface wettability of the anode material is improved, the anode metal is fully paved on the shell used as the anode current collector, the interface disturbance caused by uneven current density distribution can be avoided, the occurrence of micro short circuit is reduced, and the stable operation of the battery is promoted; the smooth and uniform anode metal/molten salt electrolyte interface is obtained, uniform reaction of cathode metal and anode interface active substances is facilitated in battery operation, short circuit caused by poor wettability of anode metal and a current collector can be greatly avoided, and battery operation stability is improved. In addition, after the additive is added, the thickness of the positive electrode can be reduced, the safe distance of the positive electrode and the negative electrode during the operation of the battery is further reduced, the internal resistance of the battery is reduced, and the energy efficiency of the battery is improved; meanwhile, the utilization rate of the anode material can be improved, the cost of the high-capacity liquid metal single battery is reduced, and the marketization of the liquid metal battery is facilitated.
In addition, in the large-capacity liquid metal battery, in order to ensure the stable operation of the battery, the battery shell can be fully paved by excessive positive metal, and the positive metal can obtain a flat metal/molten salt interface after a small amount of X additive is added, so that the using amount of the positive metal is reduced, the utilization rate of a positive material is improved, the cost of a single battery can be reduced, and the large-capacity liquid metal battery has great significance for the practical application of energy storage of the liquid metal battery.
2) The additive X provided by the invention has low melting point, excellent electronic conductivity and higher electronegativity, has good binding property with a positive electrode metal material, and can greatly improve the interface wettability and improve the cycle stability of a battery only by a small amount.
3) The additive X provided by the invention has wide sources. The anode material is simple to prepare, does not need special equipment, and is very suitable for assembling large-scale large-capacity liquid metal batteries.
Furthermore, the shell is made of stainless steel, and the stainless steel has the property of high strength and good corrosion resistance and is suitable for being used as a high-temperature current collector.
Drawings
FIG. 1 is a schematic cross-sectional view of a liquid metal battery using the positive electrode material of the present invention;
FIG. 2 is a schematic diagram of the melting of the positive electrode metal before and after the addition of the positive electrode additive according to the present invention;
fig. 3 is a charge-discharge performance curve of a liquid metal battery employing example 1 of the present invention;
fig. 4 is a charge-discharge performance curve of a liquid metal battery employing example 2 of the present invention;
fig. 5 is a charge-discharge performance curve of a liquid metal battery employing example 3 of the present invention;
fig. 6 is a charge and discharge curve of a liquid metal battery using example 4 of the present invention and comparative example 1;
fig. 7 is a charge-discharge performance curve of the liquid metal battery according to example 5 of the present invention.
In the drawings: 1-negative electrode lead, 2-ceramic sealing element, 3-shell, 4-negative electrode current collector, 5-electrolyte, 6-positive electrode, 7-positive electrode metal and 8-additive X.
Detailed Description
In order to make the objects and technical solutions of the present invention clearer and easier to understand. The present invention will be described in further detail with reference to the following drawings and examples, wherein the specific examples are provided for illustrative purposes only and are not intended to limit the present invention.
In the description of the present invention, it is to be understood that the terms "center", "longitudinal", "lateral", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", and the like, indicate orientations or positional relationships based on those shown in the drawings, and are used only for convenience in describing the present invention and for simplicity in description, and do not indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and thus, are not to be construed as limiting the present invention. Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless otherwise specified. In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
Referring to fig. 1, a liquid metal battery includes a case 3, a negative electrode lead 1, and a ceramic sealing member 2, and a positive electrode 6, a negative electrode current collector 4, and an electrolyte 5 disposed in the case 3, the negative electrode metal being adsorbed in the negative electrode current collector 4, the positive electrode being composed of a positive electrode metal 7 and an additive X8, the amount of the substance of the additive X being less than 10% of the amount of the substance of the positive electrode 6, and when the amount of the additive exceeds 10%, it reacts with a battery active material, resulting in a decrease in the battery active material and a capacity loss. Wherein, the positive electrode metal is one or the combination of more of Sb, Bi, Sn and Pb.
The negative electrode metal is an alloy formed by one or more simple substances of alkali metals Li, Na and K or alkaline earth metals Mg and Ca, and the negative electrode current collector is a porous foam metal material.
The additive X is Cu, Cd, Se or Te, and has a lower melting point, excellent electronic conductivity and higher electronegativity. The low melting point can reduce the melting point of the positive electrode alloy, thereby reducing the operating temperature of the battery; the high electronic conductivity is beneficial to the transmission of electrons between the anode and the cathode in the operation of the battery; the high electronegativity gives the battery a high voltage and thus high energy efficiency.
Preferably, the amount of substance of the additive X is less than 5% to 8% of the amount of substance of the positive electrode.
Preferably, the material of the shell 3 is 304 stainless steel, and the 304 stainless steel has the properties of high strength and good corrosion resistance and is suitable for being used as a high-temperature current collector.
The anode material consists of one of metal Sb, Bi, Sn and Pb or alloy thereof and an additive X.
At the working temperature of the liquid metal battery, the cathode material, the electrolyte and the anode material are all in liquid state.
Referring to fig. 2, a method for preparing a liquid battery anode material comprises the steps of adding an additive X into a stainless steel shell according to the amount of an anode active material, stirring to enable solid powder of the additive X to be uniformly distributed in anode metal particles, heating to 50-100 ℃ above the melting point of anode metal under the protection of inert atmosphere or vacuum condition to enable an anode to be completely melted, preserving heat for 10 hours, and ensuring that the anode metal is uniformly mixed, so that the anode material with a smooth surface and no protrusions can be obtained. Then, the electrolyte 5 and the negative current collector 4 are sequentially added into the shell 3, the negative lead 1 is led out from the negative current collector 4, the shell 3 and the negative lead 1 are separated by the ceramic sealing piece 2, and then the whole shell is welded and sealed, so that the battery assembly is completed.
Example 1
A liquid metal battery comprises a shell 3, a negative lead 1, a ceramic sealing piece 2, and a positive electrode 6, a negative current collector 4 and an electrolyte 5 which are arranged in the shell 3, wherein the negative metal is absorbed in the negative current collector 4, and the positive electrode consists of the positive metal and an additive X; wherein the anode metal is 40:60 mol% Sb-Bi alloy, and the additive X is Cu. The material of the housing 3 is 304 stainless steel. The negative electrode metal is alkali metal Li, and the negative electrode current collector is a porous foam metal material.
In the embodiment, the additive Cu is used in a Li | | | Sb-Bi battery with a cathode made of metal Li, an electrolyte made of LiCl-LiBr-LiF ternary molten salt, an anode made of 40:60 mol% Sb-Bi alloy and an operating temperature of 500 ℃; the amount of Cu added was 3% of the total amount of the positive electrode material, the battery capacity was 1Ah, and the interfacial area of the positive electrode was 3.14cm2The thickness of the positive electrode metal layer is about 0.5 mm. At 200mA/cm2When the charge and discharge tests are carried out under the current density, the charge and discharge performance curve is shown in fig. 3, and the following can be seen from fig. 3: the battery normally runs, the charging and discharging process is stable, and the short circuit condition does not occur; the test result shows that the internal resistance is 45m omega, which is lower than the internal resistance of the battery without the additive, the polarization of the battery is reduced, the cycling stability of the battery is improved, the open-circuit voltage of the battery is 860mV, the average discharge voltage is 0.75V, the coulombic efficiency is 99%, the energy efficiency is 89%, the coulombic efficiency and the energy efficiency are both improved, and the cycling performance and the economic efficiency of the battery are promoted.
Example 2
In the embodiment, the additive Cd is used in a Li | | | Sb-Bi battery with a cathode made of metal Li, an electrolyte made of LiCl-LiBr-LiF ternary molten salt, an anode made of 40:60 mol% Sb-Bi alloy and an operating temperature of 500 ℃; the amount of Cd added is 1% of the total amount of positive electrode material, the obtained battery capacity is 0.5Ah, and the positive electrode interface area is 3.14cm2The thickness of the positive electrode metal layer is about 0.3mm. At 100mA/cm2When the charge and discharge tests are carried out under the current density, the charge and discharge performance curve is shown in fig. 4, and the following can be seen from fig. 4: the battery normally runs, the charging and discharging process is stable, and the short circuit condition does not occur; the test result shows that the internal resistance is 60m omega, which is lower than the internal resistance of the battery without the additive, the polarization of the battery is reduced, so that the open circuit voltage and the average discharge voltage of the battery are respectively 835mV and 600mV which are higher than those of the battery without the additive, the coulombic efficiency and the energy efficiency are finally improved, respectively 99 percent and 86 percent, the cycling stability of the battery is good, and the sustainability and the economic efficiency are improved.
Example 3
In the embodiment, the additive Te is used for a Li | | | Bi-Sb battery with a cathode made of metal Li, an electrolyte made of LiCl-LiBr-LiF ternary molten salt and an anode made of metal Bi-Sb alloy and an operating temperature of 500 ℃; the capacity of the obtained battery is 5Ah, and the interfacial area of the positive electrode is 28.26cm2(ii) a The amount of the substance added with the additive Te is 5 percent of the amount of the positive electrode material substance, and the thickness of the positive electrode metal layer is about 1.5-2.5 mm. The charge-discharge performance curve is shown in fig. 5, and it can be seen from fig. 5 that the average discharge voltage of the battery is 800mV, the polarization of the battery is small, the coulombic efficiency of the battery is 99%, and the energy efficiency can reach 92% at most. The internal resistance of the obtained battery is 5-6m omega at 100mA/cm2And (3) carrying out cycle performance test under the current density, stably operating the battery for 180 circles, and having excellent cycle stability without short circuit.
Example 4
In the embodiment, the additive Se is used in a high-capacity Li | | | Bi battery with a cathode of metal Li, an electrolyte of LiCl-LiBr-LiF ternary molten salt, an anode of metal Bi and an operating temperature of 500 ℃; the amount of Se added is 8 percent of the total amount of the positive electrode materials, the capacity of the obtained battery is 200Ah, and the interfacial area of the positive electrode is 226.87cm2The thickness of the positive electrode metal layer is about 2 mm. At 200mA/cm2When the charge and discharge tests are carried out under the current density, the charge and discharge performance curve is shown in fig. 6, and the following can be seen from fig. 6: the battery normally runs, the charging and discharging process is stable, and the short circuit condition does not occur; the test result shows that the internal resistance is 2m omega, the final coulombic efficiency and the energy efficiency are respectively 99.5 percent and 73 percent, the stability of the battery is greatly improved,sustainability and economic efficiency are improved.
Comparative example 1
The Li | | | Bi battery is directly assembled by taking pure Bi as the anode without adding additives, and other battery materials and test procedures are completely consistent with those in the embodiment 3. The thickness of the positive electrode metal layer was measured to be about 4 cm. The charge and discharge test was carried out, the obtained internal resistance of the battery was 2.4m Ω, which was higher than that of the battery in example 3, and the charge and discharge performance curve was as shown in fig. 5, as can be seen from fig. 5: compared with the battery in the embodiment 3, the polarization of the battery is increased, the voltage of a discharge platform is reduced to 600mV, and the coulombic efficiency and the energy efficiency are reduced, respectively: 98.7% and 68%, which are detrimental to the long-term cycling stability of the cell.
Example 5
In the embodiment, the additive Se is used for a Li | | | Sb-Bi battery with a cathode made of metal Li, an electrolyte made of LiCl-LiBr-LiF ternary molten salt, an anode made of metal 40:60 mol% Sb-Bi alloy and an operating temperature of 500 ℃; the capacity of the obtained battery is 50Ah, and the interfacial area of the positive electrode is 54.08cm2(ii) a When the amount of the substance to which the additive Se is added is only 10% of the amount of the substance of the positive electrode material, the thickness of the positive electrode metal layer is about 2 mm. At 200mA/cm2The charge and discharge performance curve is shown in fig. 7 when the charge and discharge test is performed under the current density, and it can be seen from fig. 7 that: the battery normally runs, the charging and discharging process is stable, and the short circuit condition does not occur; the test result shows that the internal resistance is 6m omega, the internal resistance is lower than the internal resistance of the battery without the additive, the polarization of the battery is reduced, so that the discharge voltage of the battery is 750mV, and the polarization of the battery is higher than that of the battery without the additive, the final coulombic efficiency and the energy efficiency are respectively improved by 99 percent and 90 percent, the cycling stability of the battery is improved, and the sustainability and the economic efficiency are more outstanding.
Comparative example 2
The Sb-Bi alloy is directly used as the anode to assemble the Li | | | | Sb-Bi battery, no additive is added, and other battery materials and the test flow are completely consistent with those in the embodiment 4. The thickness of the positive electrode metal layer is about 3.5mm, the internal resistance of the battery is 15m omega during operation, the voltage fluctuates, the micro short circuit phenomenon exists, and the battery is unstable in circulation.
Example 6
The true bookIn the embodiment, Cd is used for a high-capacity Li | | | Bi battery with a negative electrode of metal Li, an electrolyte of LiCl-LiBr-LiF ternary molten salt and a positive electrode of metal Bi at the operating temperature of 500 ℃; the capacity of the obtained battery is 200Ah, and the interfacial area of the positive electrode is 226.87cm2(ii) a The thickness of the positive electrode metal layer is about 5mm, and when the amount of the Cd added is 1% of the amount of the positive electrode material, the thickness of the positive electrode metal layer is about 3.5 mm. Through multiple experiments, the safe running distance of the Li | | | Bi battery can be reduced by 1.5-2mm, and the battery can stably run under the condition of ensuring high energy density.
Example 7
In the embodiment, Cd is used in a high-capacity liquid metal Li | | | Bi battery, a negative electrode is metal Li, an electrolyte is LiF-LiCl-LiBr, and a positive electrode is Bi; in order to ensure the safe operation of the battery, when in actual assembly, the required positive electrode metal is excessive for about 100Ah when no additive is added, the dosage of the positive electrode metal Bi can be reduced after the additive Cd is added, the utilization rate of the positive electrode can reach more than 80 percent, and the positive electrode metal cost of the single battery can be reduced by about 30 yuan.
Example 8
In the embodiment, the additive Te is used in a high-capacity liquid metal Li | | | Sb-Sn battery, the cathode is metal Li, the electrolyte is LiF-LiCl-LiBr, and the anode is 40:60 mol% Sb-Sn; the mass of the added additive is 3% of the mass of the positive electrode material; the capacity of the obtained battery is 200Ah, and the interfacial area of the positive electrode is 226.87cm2The thickness of the positive electrode metal layer is about 3 mm. At 200mA/cm2The charging and discharging test is carried out under the current density, the battery normally operates, the charging and discharging process is stable, and the short circuit condition does not occur; the test result shows that the internal resistance is 2m omega, the final coulombic efficiency and the energy efficiency are respectively 99 percent and 71 percent, the stability of the battery is greatly improved, and the sustainability and the economic efficiency are improved.
Example 9
In the embodiment, the additive Te is used in a high-capacity liquid metal Li | | | Sb-Pb battery, the negative electrode is metal Li, the electrolyte is LiF-LiCl-LiBr, and the positive electrode is 40:60 mol% Sb-Pb; the amount of the additive-added substance was 5% of the amount of the positive electrode material substance, the resulting battery capacity was 200Ah, and the positive electrode interfacial area was 226.87cm2The thickness of the positive electrode metal layer is about 3 mm. At 200mA/cm2The charging and discharging test is carried out under the current density, the battery normally operates, the charging and discharging process is stable, and the short circuit condition does not occur; the test result shows that the internal resistance is 3m omega, the final coulombic efficiency and the energy efficiency are 99% and 77% respectively, the stability of the battery is greatly improved, and the sustainability and the economic efficiency are improved.
The above results show that: the additive X can reduce the thickness of the positive electrode layer, reduce the safe positive and negative electrode distance of the battery operation, reduce the internal resistance of the battery and improve the energy efficiency of the battery; the positive metal does not have a bulge in the reaction process, so that micro short circuit is not easy to form, and the operation stability of the liquid metal battery is improved. In addition, the battery is also useful for the enlargement and the commercialization of the battery.
The foregoing examples are provided for the purpose of clarity only and are not intended to be limiting. It should be noted that similar alterations and modifications of the present invention based on the principles described herein will occur to those skilled in the art, and it is not intended to list all such embodiments, so that obvious modifications and variations of this invention are possible within the scope of the present invention.
Claims (8)
1. The liquid metal battery is characterized by comprising a shell (3) and a positive electrode (6), a negative current collector (4) and an electrolyte (5) which are arranged in the shell (3), wherein the negative metal is adsorbed in the negative current collector (4), the positive electrode consists of positive metal (7) and an additive X (8), the additive X is Cu, Cd, Se or Te, and the amount of substances of the additive X is less than 10% of the amount of substances of the positive electrode (6).
2. The liquid metal battery according to claim 1, wherein the amount of substance of the additive X is 5-8% of the amount of substance of the positive electrode (6).
3. The liquid metal battery of claim 1, wherein the positive electrode metal is a combination of one or more of Sb, Bi, Sn, and Pb.
4. A liquid metal battery according to claim 1, characterized in that the material of the casing (3) is 304 stainless steel.
5. The liquid metal battery of claim 1, wherein the negative electrode metal is an alkali metal or an alkaline earth metal.
6. The liquid metal battery according to claim 1, characterized in that the negative current collector (4) is a porous metal foam material.
7. A preparation method of a liquid metal battery is characterized by comprising the following steps:
adding positive electrode metal and an additive X into a shell (3), wherein the amount of the additive X is less than 10% of that of the positive electrode (6), stirring to enable the additive X (8) to be uniformly distributed in the positive electrode metal (7) to obtain a mixture A, heating the mixture A to enable the positive electrode metal to be completely melted, and preserving heat to obtain a positive electrode material, wherein the additive X is Cu, Cd, Se or Te;
an electrolyte (5) and a negative current collector (4) are sequentially added into a shell (3), a negative lead (1) is led out from the negative current collector (4), the shell (3) is separated from the negative lead (1) by a ceramic sealing piece (2), and the shell (3) is sealed.
8. The method of claim 7, wherein the additive X is used in a powder form, and the positive electrode metal is used in a granular or powder form.
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