CN113809317A - Positive electrode material of liquid or semi-liquid metal battery and application - Google Patents
Positive electrode material of liquid or semi-liquid metal battery and application Download PDFInfo
- Publication number
- CN113809317A CN113809317A CN202110939562.2A CN202110939562A CN113809317A CN 113809317 A CN113809317 A CN 113809317A CN 202110939562 A CN202110939562 A CN 202110939562A CN 113809317 A CN113809317 A CN 113809317A
- Authority
- CN
- China
- Prior art keywords
- liquid
- battery
- positive electrode
- semi
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/02—Elemental selenium or tellurium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C11/00—Alloys based on lead
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C11/00—Alloys based on lead
- C22C11/06—Alloys based on lead with tin as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C11/00—Alloys based on lead
- C22C11/08—Alloys based on lead with antimony or bismuth as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C12/00—Alloys based on antimony or bismuth
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C13/00—Alloys based on tin
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C13/00—Alloys based on tin
- C22C13/02—Alloys based on tin with antimony or bismuth as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Liquid or semi-liquidA Zn-based positive electrode material of a state metal battery and application thereof belong to the field of electrode materials of energy storage batteries. The anode material is Zn alloy formed by metal Zn or Zn and more than one simple substance of Sn, Bi, Sb, Pb and Te. The liquid Zn or Zn alloy has higher discharge voltage, has higher matching property with the existing cathode material, is used for a liquid or semi-liquid metal battery, and can effectively reduce polarization in the battery charging and discharging process, improve the discharge voltage of the battery and further improve the energy density and energy efficiency of the battery on the basis of keeping the excellent characteristics of high capacity, long service life, easy amplification and the like of the battery. In addition, metallic Zn has a lower melting point (419.5 ℃), a lower resistivity (5.9X 10)‑4Omega cm), the Zn alloy has simple preparation process and low cost, and when Zn or the Zn alloy is used as the anode material of the liquid or semi-liquid metal battery, the conductivity of the anode material can be improved, the rate capability of the battery is improved, and the cost of the raw materials of the battery is reduced.
Description
Technical Field
The invention belongs to an electrode material of an energy storage battery, and particularly relates to a positive electrode material for a liquid or semi-liquid metal battery, which can be used for solving the problems of low working voltage, low energy density and high raw material cost of the liquid or semi-liquid metal battery.
Background
Renewable energy sources such as wind energy, solar energy and the like have the advantages of rich resources, cleanness, no pollution and the like, and the contradiction among the resources, the energy sources and the environment can be effectively relieved by vigorously developing and utilizing the renewable energy sources. The high proportion of renewable energy sources are connected into a power grid, and the establishment of a novel energy source structure with high efficiency, low cost and environmental friendliness becomes a necessary choice for power grid development. However, renewable energy power generation (such as wind energy, solar energy, etc.) has characteristics of intermittency and volatility, and is affected by environmental factors such as climate and temperature, and direct incorporation into the power grid causes great impact to the power grid, seriously harming the safety and reliability of the power grid.
The large-scale energy storage technology can stabilize the intermittency and fluctuation of the renewable energy, remarkably improve the grid-connected efficiency of the renewable energy, ensure the stability, reliability and safety of a power grid, and become a key technology for building a smart power grid and realizing energy interconnection. The liquid metal battery is a new large-scale energy storage technology, and is paid much attention to the field of energy storage due to the advantages of low cost, long cycle life, high working stability and the like. The essence of the liquid metal battery is a high-temperature molten salt battery, and the positive electrode, the negative electrode and the molten salt electrolyte are automatically layered at the working temperature. The electrode structure has high self-healing property in the charging and discharging process, and the problems of electrode deformation, dendrite growth and other electrode microscopic structure degradation and the like caused by repeated ion deintercalation are solved. In addition, the battery assembly has expandability and is easy to scale up, and the battery assembly can be adapted to power grids of different scales. Due to the characteristics, the liquid metal battery is widely concerned by the field of electrochemical energy storage, and has wide application prospects in the field of intelligent power grid energy storage in the future.
Since the society of professor Sadoway of the national academy of labor of the Massachusetts, 2012 proposed the concept of "all Liquid Metal batteries" (Liquid Metal batteries), the technology has attracted extensive attention in the global community and industry, and many research results of Liquid Metal batteries have been reported in succession. Researchers successively develop high-performance positive electrode Materials such as Bi, Sb and Te, and introduce second components such as Sn, Pb and Ga into the positive electrode through an effective alloying strategy, thereby achieving the effects of reducing the melting point of the positive electrode, reducing the solubility of the positive electrode in molten salt electrolyte, improving the Energy density and rate performance of the battery (Advanced Energy Materials 6(2016) 1600483; Energy Storage Materials 14(2018) 267-271; Journal of Power Sources (2020) 228634). However, the second component of Sn, Pb, Ga and the like added in the positive electrode does not provide capacity in the charge-discharge cycle process of the battery and only plays the role of an inert solvent, so that the energy density of the battery is greatly reduced, and the energy density of the battery using the Sb-based and Bi-based positive electrode materials is lower than 260Wh kg-1(based on the positive and negative electrode materials). For Te-based positive electrode material, the discharge voltage is up to 1.6V, so that it has 495Wh kg-1The high energy density of (2), but the high solubility of Te in molten salt electrolyte causes the battery to have the defects of large self-discharge rate, low coulombic efficiency, poor cycle stability and the like. Based on the aboveAnalysis shows that the currently reported anode material is difficult to meet the requirement of large-scale energy storage in terms of energy density or cycle life, and the development and application of a liquid or semi-liquid metal battery are severely restricted. Therefore, the development of a novel positive electrode material with high voltage, high energy density and excellent cycle performance has very important significance for the practical application of the liquid or semi-liquid metal battery in the field of energy storage.
Disclosure of Invention
The invention provides a positive electrode material for a liquid or semi-liquid metal battery, which can solve the problems of low working voltage, low energy density, high raw material cost and the like of the existing liquid or semi-liquid metal battery after being applied to an energy storage battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a positive electrode material for a liquid or semi-liquid metal battery, which is characterized in that:
the anode material is metal Zn or Zn alloy formed by Zn and one or more simple substances of Sn, Bi, Sb, Pb and Te.
Further, the mole percentage of the positive electrode material is as follows: zn2-98Sn98-2、Zn2-98Bi98-2、Zn5- 95Sb95-5、Zn2-98Pb98-2、Zn5-95Te95-5、Zn2-98Sn98-2Bi0-80、Zn2-98Sn98-2Sb0-90、Zn2-98Sn98-2Pb0-60、Zn2- 98Sn98-2Te0-60、Zn2-98Bi98-2Sb0-80、Zn2-98Bi98-2Pb0-50、Zn2-98Bi98-2Te0-60、Zn5-95Sb95-5Pb0-60、Zn5- 95Sb95-5Te0-70、Zn2-98Pb98-2Te0-60Wherein the lower right hand corner in the formula indicates the mole percent of each component, and the mole percent of each component in each alloy adds up to 100%。
Furthermore, the preparation method of the cathode material is very simple, when the Zn alloy is prepared, the metal Zn and other required metal raw materials are weighed according to the mole percentage, the metal Zn and other required metal raw materials are simply mixed and heated to 50-100 ℃ above the melting point of the alloy in the proportion under the protection of inert atmosphere or vacuum, and the temperature is kept for 2-24 hours, so that the mixed metal raw materials are fully alloyed, and the Zn alloy cathode material can be obtained.
Another aspect of the present invention provides an energy storage battery using a liquid or semi-liquid metal battery positive electrode material, which comprises a housing, a negative electrode current collector, a negative electrode, a molten salt electrolyte, a positive electrode current collector and a ceramic sealing device, wherein the molten negative electrode liquid metal is absorbed in the negative electrode current collector, and the positive electrode uses the positive electrode material as described above.
Further, the negative electrode current collector is a porous foam material.
Further, the positive electrode current collector is one of graphite and W, Mo materials.
Further, in the energy storage battery, the negative electrode material is in a liquid state, and the positive electrode material and the electrolyte material are in a liquid state or a semi-liquid state at the working temperature.
Specifically, the assembly method of the liquid or semi-liquid metal battery provided by the invention is very simple, under the protection of argon atmosphere and at the working temperature, the battery is assembled by sequentially placing the positive current collector, the positive electrode, the molten salt electrolyte and the negative electrode in the shell from bottom to top, and the insulation between the negative electrode and the shell is realized through the ceramic sealing device. After the battery assembly is finished, the temperature is raised to the working temperature for battery performance test.
The key points of the technology of the invention are as follows:
1. zn has a lower melting point, and can also reduce the melting point of the anode material after being alloyed with one or more simple substances of Sn, Bi, Sb, Pb and Te; when the zinc alloy is used as the anode material of the liquid or semi-liquid metal battery, the working temperature of the battery can be effectively reduced.
2. Zn or Zn and Sn, Bi, Sb, Pb and Te are adopted to replace the second component of Sn, Pb, Ga and the like added in high-performance positive electrode materials such as Bi, Sb and Te in the prior art, and at the initial discharge stage of the battery, the zinc can participate in electrode reaction to generate LiZnX (X is one of Bi, Sb and Te) intermetallic compounds with higher discharge voltage; with the progress of discharge, LiZnX is gradually converted into a Li-X solid intermetallic compound, and Zn regenerated in the process is dispersed in an intermetallic compound layer and can be used as a lithium rapid diffusion channel to accelerate the reaction of lithium and a lower positive electrode, so that the electrode reaction kinetics is further improved. After the metal battery is applied to an energy storage battery, the problems of low working voltage, low energy density, high raw material cost and the like of the existing liquid or semi-liquid metal battery are solved.
3. By utilizing the characteristic that Zn has better lithium storage capacity, the utilization rate of the positive active material can be effectively improved and the capacity and the energy density of the battery can be improved while the system temperature is reduced.
4. The liquid or semi-liquid metal battery prepared by matching Zn or an alloy formed by Zn and Sn, Bi, Sb, Pb and Te with a molten salt electrolyte and foamed nickel prepared by LiF, LiCl, LiBr and other raw materials as a negative current collector has excellent performance, wherein the liquid or semi-liquid metal battery prepared by taking the zinc-antimony alloy as a positive electrode material has the best performance.
The battery test result prepared based on the invention shows that compared with the prior art, the technical scheme of the invention has the following beneficial effects or technical advantages:
zn has a lower melting point, and can also reduce the melting point of the anode material after being alloyed with one or more simple substances of Sn, Bi, Sb, Pb and Te; when the zinc alloy is used as the anode material of the liquid or semi-liquid metal battery, the working temperature of the battery can be effectively reduced.
Zn has better lithium storage capacity, and can ensure the utilization rate of the positive active material and improve the capacity and energy density of the battery while reducing the system temperature.
The metal Zn in the invention has lower resistivity (5.9 multiplied by 10)-4Omega cm), when Zn or Zn alloy is used as the anode material of the liquid or semi-liquid metal battery, the conductivity of the anode material can be improved, and the rate capability of the battery can be improvedThe polarization of the battery in the charging and discharging process is effectively reduced, and the discharging voltage of the battery is improved.
The metal Zn and the Zn alloy have low cost and simple preparation process, do not need special equipment, and can reduce the raw material and assembly cost of the battery when being used as the anode material of the liquid or semi-liquid metal battery.
Drawings
Fig. 1 is a schematic view of a liquid or semi-liquid metal battery using the positive electrode material of the present invention;
FIG. 2 is a graph of the charge and discharge performance of a liquid metal energy storage battery according to example 1 of the present invention;
FIG. 3 is a graph of the charge and discharge performance of a liquid metal energy storage battery according to example 2 of the present invention;
FIG. 4 is a graph of the charge and discharge performance of a liquid metal energy storage battery according to example 3 of the present invention;
fig. 5 is a cycle characteristic curve of a liquid metal energy storage battery using example 3 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in further detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not limiting of the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The invention provides a positive electrode material for a liquid or semi-liquid metal battery, aiming at the problems of low working voltage, low energy density, high raw material cost, high assembly cost and the like of the existing liquid or semi-liquid metal battery, wherein the positive electrode material is metal Zn or a Zn alloy formed by Zn and one or more simple substances of Sn, Bi, Sb, Pb and Te, and the Zn alloy has the chemical formula as follows:
Zn2-98Sn98-2、Zn2-98Bi98-2、Zn5-95Sb95-5、Zn2-98Pb98-2、Zn5-95Te95-5、Zn2-98Sn98-2Bi0-80、Zn2-98Sn98-2Sb0-90、Zn2-98Sn98-2Pb0-60、Zn2-98Sn98-2Te0-60、Zn2-98Bi98-2Sb0-80、Zn2-98Bi98-2Pb0-50、Zn2-98Bi98-2Te0-60、Zn5-95Sb95-5Pb0-60、Zn5-95Sb95-5Te0-70、Zn2-98Pb98-2Te0-60wherein the lower right hand corner of the formula indicates the mole percent of each component and the mole percent of each component in each alloy add up to 100%.
When preparing the Zn alloy, weighing metal Zn and other required metal raw materials according to the mole percentage, simply and uniformly mixing the metal Zn and other required metal raw materials in a graphite crucible, a ceramic crucible or a metal crucible, then putting the crucible containing the mixed metal raw materials in a tube furnace or other heating furnaces, heating the crucible to 50-100 ℃ above the melting point of the proportional alloy under the protection of inert atmosphere or under the vacuum condition, and preserving heat for 2-24 hours to fully alloy the mixed metal raw materials, thus obtaining the anode alloy material. The preparation method of the anode material is very simple, does not need special equipment, has high yield, and can reduce the preparation cost of the electrode material.
According to another aspect of the present invention, the present invention further provides a liquid or semi-liquid metal energy storage battery using the positive electrode material, the structural schematic diagram of which is shown in fig. 1, the liquid or semi-liquid metal energy storage battery includes a casing 1, a positive electrode current collector 2, a positive electrode 3, a molten salt electrolyte 4, a negative electrode 5 and a ceramic sealing device 6, the casing 1 is made of a metal material, is a metal cylinder with a sealed bottom end, and is internally provided with the positive electrode current collector 2, the positive electrode 3, the molten salt electrolyte 4 and the negative electrode 5 in sequence from bottom to top, and the negative electrode 5 is composed of a foam current collector adsorbing molten liquid negative electrode metal and is insulated from the casing 1 through the ceramic sealing device 6. Wherein the positive electrode adopts the positive electrode material.
In the liquid or semi-liquid metal battery energy storage battery applying the anode material, molten cathode liquid metal is absorbed in the cathode current collector, the anode, the molten salt electrolyte and the cathode are sequentially arranged in the shell from bottom to top, and the insulation between the cathode and the shell is realized through the ceramic sealing device. The negative electrode current collector is made of porous foam material, and the positive electrode current collector is made of one of graphite and W, Mo material.
The invention provides a liquid or semi-liquid metal battery energy storage battery applying the anode material, which comprises the following assembly processes: firstly, placing a negative foam metal current collector in molten negative metal, and enabling the negative current collector to adsorb certain mass of negative metal according to a required proportion to finish the preparation of a negative electrode; then, placing the positive current collector into a battery shell, placing the battery shell into a heating furnace, and heating to a working temperature; and then sequentially putting the positive electrode and the molten salt electrolyte, preserving heat for 0.5-2h, immersing the prepared negative electrode into the electrolyte after the positive electrode and the molten salt electrolyte are completely melted, adjusting the distance between the negative electrode and the positive electrode to be 10-20mm, and finally cooling the battery to room temperature to finish the sealing of the battery, thereby finishing the assembly process of the battery. The whole battery assembling process is completed in a glove box filled with argon atmosphere.
Further, the present invention is illustrated in a series of embodiments and further described in conjunction with the accompanying drawings. The liquid or semi-liquid metal energy storage batteries of the embodiments have the same structure and assembly process, but the compositions and preparation processes of the positive and negative electrode materials and the molten salt electrolyte are different in each embodiment.
Example 1
In the embodiment, pure zinc is used as a positive electrode material, metal lithium is used as a negative electrode material, the molar ratio of the positive electrode material to the negative electrode material is 1:1.05, and the electrolyte is low-melting-point molten salt consisting of LiF, LiCl and LiBr, wherein the molar percentage of LiF, LiCl and LiBr is 22:31: 47. The zinc metal has low raw material cost (0.15 mol)-1) And the material is far lower than other anode materials, so the raw material cost of the embodiment is greatly reduced.
In this embodiment, the nickel foam is used as a negative current collector, and molten metal lithium with a required mass is absorbed in the nickel foam to complete the preparation of the negative electrode. The positive current collector is a graphite crucible. In the assembly process, the distance between the cathode and the anode is adjusted to be 16 mm.
The cell of this example was operated at 550 ℃ and the electrochemical window tested was 0.3-1.5V. Fig. 2 is a charge-discharge performance curve of the energy storage battery in example 1 of the present invention. The battery has good electrochemical performance at 200mA cm-2At current density, the discharge median voltage was up to 0.54V, the coulombic efficiency was 90.3%, and the energy efficiency was 70%. Meanwhile, because the metal zinc has lower relative atomic mass, the energy density of the battery can be greatly improved by using the metal zinc as a positive electrode material, and the energy density of the battery of the embodiment is as high as 193Wh kg-1(calculated based on the positive and negative electrode materials).
Example 2
In the embodiment, a zinc-antimony alloy is used as a positive electrode material, and the molar percentage of the metal zinc and antimony is 70: 30. Metallic lithium is a negative electrode material, and nLi＝3*nSb+0.6*nZn. The electrolyte adopts low-melting-point molten salt consisting of LiF, LiCl and LiBr, wherein the mol percentage of LiF, LiCl and LiBr is 22:31: 47.
The preparation process of the zinc-antimony alloy in the embodiment is as follows: weighing metal Zn and metal Sb according to the mol percentage, putting the metal Zn and the metal Sb into a graphite crucible, simply and uniformly mixing, putting the crucible containing the mixed metal raw materials into a tubular furnace, heating to 600 ℃ under the protection of inert atmosphere, and preserving heat for 5 hours to obtain the required zinc-antimony alloy.
In this embodiment, the nickel foam is used as a negative current collector, and molten metal lithium with a required mass is absorbed in the nickel foam to complete the preparation of the negative electrode. The positive current collector is a graphite crucible. In the assembly process, the distance between the cathode and the anode is adjusted to be 12 mm.
The cell of this example was operated at 550 ℃ and the electrochemical window tested was 0.3-1.5V. Fig. 3 is a charge-discharge performance curve of the battery of example 2 using the present invention. As can be seen from FIG. 3, at 100mA cm-2At current density, the cell has a transient plateau at a high voltage of 1V during the initial discharge. The discharge median voltage of the battery is up to 0.76V, and the energy density is up to 293Wh kg in the whole discharge process-1(calculated based on the positive and negative electrode materials). In addition to this, the present invention is,under the current density, the coulomb efficiency of the battery is 82.3%, the energy efficiency is 75%, and the electrochemical performance is excellent.
Example 3
In the embodiment, a zinc bismuth alloy is used as a positive electrode material, and the molar percentage of the metal zinc and the metal bismuth is 30: 70. Metallic lithium is a negative electrode material, and nLi＝3*nBi+0.6*nZn. The electrolyte adopts low-melting-point molten salt consisting of LiF, LiCl and LiBr, wherein the mol percentage of LiF, LiCl and LiBr is 22:31: 47.
The preparation process of the zinc-bismuth alloy of the embodiment is as follows: weighing metal Zn and metal Bi according to the mol percentage, placing the metal Zn and the metal Bi into a graphite crucible, simply and uniformly mixing, placing the crucible containing the mixed metal raw materials into a tubular furnace, heating to 550 ℃ under the protection of inert atmosphere, and preserving heat for 3 hours to obtain the required zinc-bismuth alloy.
The embodiment selects the foam nickel-iron as the negative current collector, and molten metal lithium with required mass is absorbed in the foam nickel to complete the preparation of the negative electrode. 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 cell of this example was operated at 500 ℃ and the electrochemical window tested was 0.3-1.5V. Fig. 4 is a charge/discharge performance curve of a battery according to example 3 of the present invention. The battery of the embodiment 3 has excellent electrochemical performance at 200mA cm-2Under the current density, the discharge voltage is up to 0.73V, the coulombic efficiency is 91.3 percent, and the energy efficiency is 78 percent. FIG. 5 is a graph of the cycle performance at 800mAcm for a battery using example 3 of the present invention-2The coulomb efficiency is always kept above 98% when the charge-discharge cycle is 50 circles under the current density, and the capacity decay rate is only 0.12% per circle.
The test results show that: the anode material is applied to the liquid or semi-liquid metal battery, so that the working voltage of the liquid or semi-liquid metal battery is improved, higher coulombic efficiency and energy density are obtained, and the battery has good cycle performance; meanwhile, the successful application of the low-cost Zn in the liquid or semi-liquid metal battery reduces the energy storage cost 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 (5)
1. A Zn-based positive electrode material for a liquid or semi-liquid metal battery, characterized in that: the positive electrode material is Zn alloy formed by metal Zn or Zn and more than one simple substance of Sn, Bi, Sb, Pb and Te;
the chemical formula of the Zn alloy is as follows: zn2-98Sn98-2、Zn2-98Bi98-2、Zn5-95Sb95-5、Zn2-98Pb98-2、Zn5-95Te95-5、Zn2-98Sn98-2Bi0-80、Zn2-98Sn98-2Sb0-90、Zn2-98Sn98-2Pb0-60、Zn2-98Sn98-2Te0-60、Zn2-98Bi98-2Sb0-80、Zn2-98Bi98-2Pb0-50、Zn2-98Bi98-2Te0-60、Zn5-95Sb95-5Pb0-60、Zn5-95Sb95-5Te0-70、Zn2-98Pb98-2Te0-60Wherein the lower right hand corner of the formula indicates the mole percent of each component and the mole percent of each component in each alloy add up to 100%.
2. A liquid or semi-liquid metal energy storage battery prepared by applying the Zn-based positive electrode material of claim 1, wherein: the liquid or semi-liquid metal energy storage battery comprises a shell, a negative electrode current collector, a negative electrode, a molten salt electrolyte, a positive electrode current collector and a ceramic sealing device, wherein the negative electrode liquid metal is adsorbed in the negative electrode current collector, and the positive electrode is made of the positive electrode material of claim 1.
3. A liquid or semi-liquid metal energy storage battery using a Zn-based positive electrode material according to claim 2, wherein: the negative current collector is made of porous foam material.
4. A liquid or semi-liquid metal energy storage battery using a Zn-based positive electrode material according to claim 2, wherein: the positive electrode current collector is one of graphite and W, Mo materials.
5. A liquid or semi-liquid metal energy storage battery using a Zn-based positive electrode material according to claim 2, wherein: the cathode material is in a liquid state and the anode and electrolyte materials are in a liquid or semi-liquid state at the operating temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110939562.2A CN113809317B (en) | 2021-08-16 | 2021-08-16 | Positive electrode material of liquid or semi-liquid metal battery and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110939562.2A CN113809317B (en) | 2021-08-16 | 2021-08-16 | Positive electrode material of liquid or semi-liquid metal battery and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113809317A true CN113809317A (en) | 2021-12-17 |
| CN113809317B CN113809317B (en) | 2023-09-26 |
Family
ID=78893808
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110939562.2A Active CN113809317B (en) | 2021-08-16 | 2021-08-16 | Positive electrode material of liquid or semi-liquid metal battery and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113809317B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114597371A (en) * | 2022-03-18 | 2022-06-07 | 昆明理工大学 | Liquid metal @ rGO nano-droplet room-temperature liquid metal battery positive electrode material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103259004A (en) * | 2013-04-16 | 2013-08-21 | 华中科技大学 | Anode material for liquid-state and semi-liquid-state metal energy-storing batteries |
| CN104124459A (en) * | 2014-07-22 | 2014-10-29 | 西安交通大学 | Square liquid metal battery device and assembling method thereof |
| US20150015210A1 (en) * | 2013-05-23 | 2015-01-15 | Ambri, Inc. | Voltage-enhanced energy storage devices |
| 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 |
-
2021
- 2021-08-16 CN CN202110939562.2A patent/CN113809317B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103259004A (en) * | 2013-04-16 | 2013-08-21 | 华中科技大学 | Anode material for liquid-state and semi-liquid-state metal energy-storing batteries |
| US20150015210A1 (en) * | 2013-05-23 | 2015-01-15 | Ambri, Inc. | Voltage-enhanced energy storage devices |
| CN104124459A (en) * | 2014-07-22 | 2014-10-29 | 西安交通大学 | Square liquid metal battery device and assembling method thereof |
| 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 |
Non-Patent Citations (7)
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114597371A (en) * | 2022-03-18 | 2022-06-07 | 昆明理工大学 | Liquid metal @ rGO nano-droplet room-temperature liquid metal battery positive electrode material and preparation method thereof |
| CN114597371B (en) * | 2022-03-18 | 2023-12-22 | 昆明理工大学 | Liquid metal@rGO nano droplet room-temperature liquid metal battery anode material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113809317B (en) | 2023-09-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Bullock | Lead/acid batteries | |
| CN107221677B (en) | Liquid metal battery with high energy density | |
| CN110729470B (en) | Positive electrode material of liquid or semi-liquid metal battery, preparation method and application | |
| CN107482209B (en) | Positive electrode material for liquid and semi-liquid metal batteries | |
| CN110752360B (en) | S-Ni3Preparation method of C/NiO composite lithium-sulfur battery positive electrode material | |
| CN113258070B (en) | Metal zinc cathode interface modification method for water-based zinc ion battery | |
| CN102694156A (en) | Silicon-carbon composite negative pole material, preparation method thereof and lithium ion battery using foamed metal as negative pole current collector | |
| CN112768766B (en) | Lithium-sulfur battery electrolyte and application thereof | |
| CN118335931A (en) | Lithium metal composite electrode material, preparation method thereof, electrode containing lithium metal composite electrode material, battery module, battery pack and device | |
| CN114122332A (en) | Method for preparing three-dimensional metal lithium cathode by using MOFs (metal-organic frameworks) derivatives | |
| CN112952211A (en) | Liquid metal battery and preparation method thereof | |
| CN113809317B (en) | Positive electrode material of liquid or semi-liquid metal battery and application thereof | |
| CN113809409A (en) | Low-melting-point molten salt electrolyte of liquid or semi-liquid metal battery, preparation and application | |
| CN115911263B (en) | Lithium metal composite pole piece and preparation method and application thereof | |
| CN114094084A (en) | Preparation method and application of metal oxalate-graphite composite electrode material | |
| CN108682859B (en) | Preparation method of graphene modified lithium ion battery negative electrode material | |
| CN110808365A (en) | High-performance transition metal oxide negative electrode material and battery assembling method | |
| CN114171808B (en) | High-energy-density liquid metal battery and preparation method thereof | |
| CN105826542B (en) | A kind of copper-antimony alloy-antimony nucleocapsid structure material and its application | |
| CN113745492B (en) | Liquid metal battery with prefabricated multi-pore structure positive electrode and preparation method thereof | |
| CN117175016B (en) | Negative-electrode-free sodium ion secondary battery, electrolyte and application thereof | |
| CN102064316A (en) | Method for making negative electrode of lithium ion battery and lithium ion battery | |
| CN113851723B (en) | Electrolyte and metal-sulfur battery | |
| CN113410451B (en) | Lithium metal negative electrode flexible protection material and preparation method thereof | |
| CN114094065A (en) | High-voltage positive electrode material of liquid or semi-liquid metal battery and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |