CN113809317B - Positive electrode material of liquid or semi-liquid metal battery and application thereof - Google Patents
Positive electrode material of liquid or semi-liquid metal battery and application thereof Download PDFInfo
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Abstract
A Zn-based positive electrode material of a liquid or semi-liquid metal battery and application thereof belong to the field of electrode materials of energy storage batteries. The anode material is metal Zn or Zn alloy formed by more than one simple substance of Zn and Sn, bi, sb, pb, te. The liquid Zn or Zn alloy has higher discharge voltage and higher matching property with the existing negative electrode material, is used for a liquid or semi-liquid metal battery, and can effectively reduce the charge and discharge of the battery on the basis of keeping excellent characteristics of high capacity, long service life, easy amplification and the like of the batteryPolarization in the process, the discharge voltage of the battery is improved, and then the energy density and the energy efficiency of the battery are improved. In addition, metallic Zn has a low melting point (419 ℃ C.) and a low resistivity (5.9X10) ‑4 Omega cm), the Zn alloy preparation process is simple, the cost is low, when Zn or Zn alloy is used as the positive electrode material of the liquid or semi-liquid metal battery, the conductivity of the positive electrode material can be improved, the multiplying power performance of the battery is improved, and the cost of 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 an anode 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 and solar energy have the advantages of abundant resources, cleanness, no pollution and the like, and the contradiction among the resources, the energy sources and the environment can be effectively relieved by the vigorous development and utilization of the renewable energy sources. The high-ratio renewable energy source is connected into the power grid, and the establishment of a novel energy source structure with high efficiency, low cost and environmental friendliness has become an inevitable choice for the development of the power grid. However, renewable energy power generation (such as wind energy, solar energy and the like) has the characteristics of intermittence and volatility, and is influenced by environmental factors such as climate, temperature and the like, and the direct integration of the renewable energy power generation into a power grid can cause great impact on the power grid, so that the safety and reliability of the power grid are seriously damaged.
The large-scale energy storage technology can stabilize the intermittence and fluctuation of renewable energy sources, obviously improve the grid-connected efficiency of the renewable energy sources, ensure the stability, the reliability and the safety of a power grid, and become a key technology for constructing a smart power grid and realizing energy interconnection. The liquid metal battery is an emerging large-scale energy storage technology, and is concerned by the energy storage field 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 at the working temperature, the anode, the cathode and the molten salt electrolyte are automatically layered. The electrode structure has high self-healing property in the charge and discharge process, and the problems of electrode deformation, dendrite growth and other electrode microstructure degradation and the like caused by repeated ion deintercalation can be avoided. In addition, the battery assembly has expandability, is easy to scale up, and can adapt to power grids with different scales. The characteristics lead the liquid metal battery to be widely focused in the field of electrochemical energy storage, and have wide application prospect in the field of energy storage of smart power grids in the future.
Since the professor team of the university of sesame-province university of america developed an "all-liquid-metal battery" (Liquid Metal Battery) concept, this technology has attracted widespread attention in the global community and industry, and many liquid-metal batteries have been reported in succession. Researchers have developed high-performance cathode materials such as Bi, sb, te successively, and through an effective alloying strategy, a second component such as Sn, pb, ga and the like is introduced into the cathode, so that the effects of reducing the melting point of the cathode, reducing the solubility of the cathode in molten salt electrolyte, improving the energy density and the rate capability of a battery and the like are realized (Advanced Energy Materials (2016) 1600483;Energy Storage Materials 14 (2018) 267-271;Journal of Power Sources 472 (2020) 228634). However, the second component such as Sn, pb, ga and the like added in the positive electrode does not provide capacity during the charge-discharge cycle of the battery, only plays a role of an inert solvent, which greatly reduces the energy density of the battery, so that 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 cathode materials, the discharge voltage is as high as 1.6V, so that the Te-based cathode material has 495Wh kg -1 However, the high solubility of Te in molten salt electrolyte causes the battery to suffer from the disadvantages of high self-discharge rate, low coulombic efficiency, poor cycling stability, etc. Based on the analysis, the currently reported positive electrode material is difficult to meet the requirement of large-scale energy storage in terms of energy density or cycle life, and severely restricts the development and the application of liquid or semi-liquid metal batteriesIs used. Therefore, the development of the novel anode 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 energy storage field.
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 above purpose, the present invention adopts the following technical scheme:
in one aspect, the present invention provides a positive electrode material for a liquid or semi-liquid metal battery, characterized in that:
the positive electrode material is metallic Zn or Zn alloy formed by Zn and one or more simple substances in Sn, bi, sb, pb, te.
Further, the above positive electrode material comprises the following components in mole percent: zn (zinc) 2-98 Sn 98-2 、Zn 2-98 Bi 98-2 、Zn 5- 95 Sb 95-5 、Zn 2-98 Pb 98-2 、Zn 5-95 Te 95-5 、Zn 2-98 Sn 98-2 Bi 0-80 、Zn 2-98 Sn 98-2 Sb 0-90 、Zn 2-98 Sn 98-2 Pb 0-60 、Zn 2- 98 Sn 98-2 Te 0-60 、Zn 2-98 Bi 98-2 Sb 0-80 、Zn 2-98 Bi 98-2 Pb 0-50 、Zn 2-98 Bi 98-2 Te 0-60 、Zn 5-95 Sb 95-5 Pb 0-60 、Zn 5- 95 Sb 95-5 Te 0-70 、Zn 2-98 Pb 98-2 Te 0-60 Wherein the lower right hand symbol in the formula indicates the mole percent of each component and the mole percentages of the components in each alloy add up to 100%.
Further, the preparation method of the positive electrode material is very simple, when preparing Zn alloy, metal Zn and other needed metal raw materials are weighed according to the mole percentage, are heated to 50-100 ℃ above the melting point of the proportional alloy under the inert atmosphere protection or vacuum condition after being simply mixed, and are kept for 2-24 hours, so that the mixed metal raw materials are fully alloyed, and the Zn alloy positive electrode material can be obtained.
In another aspect, the invention provides an energy storage battery using a liquid or semi-liquid metal battery positive electrode material, which 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 molten negative electrode liquid metal is adsorbed in the negative electrode current collector, and the positive electrode adopts the positive electrode material.
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 above energy storage battery, the negative electrode material is in a liquid state at the operating temperature, and the positive electrode and the electrolyte material are in a liquid state or semi-liquid state.
Specifically, the assembly method of the liquid or semi-liquid metal battery provided by the invention is very simple, the positive electrode current collector, the positive electrode, the molten salt electrolyte and the negative electrode are sequentially arranged in the shell from bottom to top under the protection of argon atmosphere at the working temperature, and the insulation between the negative electrode and the shell is realized through the ceramic sealing device. After the battery is assembled, the temperature is raised to the working temperature to test the performance of the battery.
The technical key points of the invention are as follows:
1. zn has a lower melting point and can reduce the melting point of the anode material after alloying with one or more simple substances in Sn, bi, sb, pb, te; when the zinc alloy is used as the positive electrode 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, te are adopted to replace the prior art that the added Sn, pb, ga and other second components are added into Bi, sb, te and other high-performance positive electrode materials, and in the initial stage of battery discharge, zinc can participate in electrode reaction to generate LiZnX (X is one of Bi, sb and Te) intermetallic compounds, so that the battery has higher discharge voltage; along with the progress of discharge, liZnX is gradually converted into Li-X solid intermetallic compound, and the regenerated Zn in the process is dispersed in the intermetallic compound layer, so that the Zn can be used as a rapid diffusion channel of lithium, the reaction of the lithium and a lower anode is accelerated, and the electrode reaction kinetics is further improved. After being applied to the 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 electrode active material can be effectively improved while the system temperature is reduced, and the capacity and the energy density of the battery are improved.
4. The liquid or semi-liquid metal battery prepared by adopting Zn or an alloy formed by Zn and Sn, bi, sb, pb, te and adopting molten salt electrolyte prepared by adopting LiF, liCl, liBr and other raw materials and foamed nickel as a negative electrode current collector has quite good performance, wherein the liquid or semi-liquid metal battery prepared by adopting 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 reduce the melting point of the anode material after alloying with one or more simple substances in Sn, bi, sb, pb, te; when the zinc alloy is used as the positive electrode 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, can ensure the utilization rate of the positive electrode active material while reducing the system temperature, and improves the capacity and energy density of the battery.
The metallic Zn in the invention has lower resistivity (5.9X10) -4 Omega cm), zn or Zn alloy is used as the positive electrode material of the liquid or semi-liquid metal battery, the conductivity of the positive electrode material can be improved, the multiplying power performance of the battery is improved, the polarization in the charge and discharge process of the battery is effectively reduced, and the discharge voltage of the battery is improved.
The metal Zn and Zn alloy has low cost, simple preparation process and no need of special equipment, and when the metal Zn and Zn alloy is used as the positive electrode material of the liquid or semi-liquid metal battery, the battery raw material and assembly cost can be reduced.
Drawings
Fig. 1 is a schematic view of a liquid or semi-liquid metal battery employing a positive electrode material according to the present invention;
FIG. 2 is a graph showing the charge and discharge performance of a liquid metal energy storage battery employing example 1 of the present invention;
FIG. 3 is a graph showing the charge and discharge performance of a liquid metal energy storage cell employing example 2 of the present invention;
fig. 4 is a graph showing the charge and discharge performance of a liquid metal energy storage battery employing example 3 of the present invention;
fig. 5 is a graph showing the cycle characteristics of a liquid metal energy storage cell employing example 3 of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the embodiments of the present invention will be described in further detail with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
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, the invention provides a positive electrode material for the liquid or semi-liquid metal battery, wherein the positive electrode material is metal Zn or Zn alloy formed by one or more simple substances in Zn and Sn, bi, sb, pb, te, and the chemical formula of the Zn alloy is as follows:
Zn 2-98 Sn 98-2 、Zn 2-98 Bi 98-2 、Zn 5-95 Sb 95-5 、Zn 2-98 Pb 98-2 、Zn 5-95 Te 95-5 、Zn 2-98 Sn 98-2 Bi 0-80 、Zn 2-98 Sn 98-2 Sb 0-90 、Zn 2-98 Sn 98-2 Pb 0-60 、Zn 2-98 Sn 98-2 Te 0-60 、Zn 2-98 Bi 98-2 Sb 0-80 、Zn 2-98 Bi 98-2 Pb 0-50 、Zn 2-98 Bi 98-2 Te 0-60 、Zn 5-95 Sb 95-5 Pb 0-60 、Zn 5-95 Sb 95-5 Te 0-70 、Zn 2-98 Pb 98-2 Te 0-60 wherein the lower right hand symbol in the formula indicates the mole percent of each component and the mole percentages of the components in each alloy add up to 100%.
When preparing Zn alloy, weighing metal Zn and other needed metal raw materials according to the mole percentage, putting the metal Zn and other needed metal raw materials into a graphite crucible, a ceramic crucible or a metal crucible for simple and uniform mixing, putting the crucible containing the mixed metal raw materials into a tubular furnace or other heating furnaces, heating to 50-100 ℃ above the melting point of the proportional alloy under the protection of inert atmosphere or 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, no special equipment is needed, the yield is high, and the preparation cost of the electrode material can be reduced.
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, and a schematic structural diagram of the liquid or semi-liquid metal energy storage battery is shown in fig. 1, and the battery comprises 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, wherein the casing 1 is made of a metal material, is a metal cylinder with a sealed bottom, the positive electrode current collector 2, the positive electrode 3, the molten salt electrolyte 4 and the negative electrode 5 are sequentially placed inside the casing from bottom to top, and the negative electrode 5 is formed by a foam current collector absorbing molten liquid negative electrode metal and is insulated from the casing 1 by the ceramic sealing device 6. Wherein the positive electrode adopts the positive electrode material as described above.
According to the liquid or semi-liquid metal battery energy storage battery using the positive electrode material, the molten negative electrode liquid metal is adsorbed in the negative electrode current collector, the positive electrode, the molten salt electrolyte and the negative electrode assembled battery are sequentially placed in the shell from bottom to top, and insulation between the negative electrode and the shell is realized through the ceramic sealing device. The negative current collector is made of a porous foam material, and the positive current collector is made of one of graphite and W, mo materials.
The invention provides a liquid or semi-liquid metal battery energy storage battery applying the positive electrode material, which comprises the following assembly processes: firstly, placing a negative foam metal current collector into molten negative metal, and enabling the negative foam metal current collector to adsorb the negative metal with a certain mass 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 the working temperature; and then sequentially placing the positive electrode and the molten salt electrolyte and 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, so as to finish battery sealing and battery assembling. The entire battery assembly process was completed in a glove box filled with an argon atmosphere.
Further, the present invention provides a series of embodiments, and the present invention is further described with reference to the accompanying drawings. The structure and assembly process of the liquid or semi-liquid metal energy storage battery employing the embodiments are the same, except for the composition and preparation process of the positive and negative electrode materials and molten salt electrolyte in each embodiment.
Example 1
In the embodiment, pure zinc is used as a positive electrode material, lithium metal 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 low-melting-point molten salt composed of LiF, liCl and LiBr is adopted as electrolyte, wherein the molar percentage of LiF, liCl and LiBr is 22:31:47. The metallic zinc has low raw material cost (0.15 $ mol) -1 ) Is far lower than other anode materials, so the raw material cost of the embodiment is greatly reduced.
In the embodiment, foam nickel is selected as a negative electrode current collector, and molten metal lithium with required mass is adsorbed in the foam nickel to complete preparation of the negative electrode. The positive current collector is a graphite crucible. In the assembly process, the distance between the negative electrode and the positive electrode is adjusted to be 16mm.
The cell of this example was operated at 550℃and the electrochemical window tested was 0.3-1.5V. FIG. 2 shows the production ofThe charge and discharge performance curves of the energy storage battery of example 1 of the present invention were used. The battery has good electrochemical performance, and can be used for preparing a battery with a current of 200mA cm -2 At current density, the median voltage of discharge is up to 0.54V, the coulomb efficiency is 90.3%, and the energy efficiency is 70%. Meanwhile, because the metallic zinc has lower relative atomic mass, the metallic zinc is used as a positive electrode material, the energy density of the battery can be greatly improved, and the energy density of the battery in the embodiment is as high as 193Wh kg -1 (calculated based on the positive and negative electrode materials).
Example 2
In the embodiment, zinc-antimony alloy is used as a positive electrode material, and the mole percentage of metal zinc and antimony is 70:30. Metallic lithium is the negative electrode material, and n Li ＝3*n Sb +0.6*n Zn . The electrolyte adopts low-melting-point molten salt composed of LiF, liCl and LiBr, wherein the mole percentage of LiF, liCl and LiBr is 22:31:47.
The preparation process of the zinc-antimony alloy in the embodiment comprises the following steps: weighing metals Zn and Sb according to the mole percentage, putting the metals Zn and Sb into a graphite crucible, simply and uniformly mixing, putting the crucible containing the mixed metal raw materials into a tube furnace, heating to 600 ℃ under the protection of inert atmosphere, and preserving heat for 5 hours to obtain the required zinc-antimony alloy.
In the embodiment, foam nickel is selected as a negative electrode current collector, and molten metal lithium with required mass is adsorbed in the foam nickel to complete preparation of the negative electrode. The positive current collector is a graphite crucible. In the assembly process, the distance between the negative electrode and the positive electrode is adjusted to be 12mm.
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 a battery employing example 2 of the present invention. As can be seen from FIG. 3, the temperature is 100mA cm -2 At current density, the cell has a short plateau at high voltage of 1V at the initial stage of discharge. In the whole discharging process, the discharge median voltage of the battery is up to 0.76V, and the energy density is up to 293Wh kg -1 (calculated based on the positive and negative electrode materials). In addition, at this current density, the coulombic efficiency of the cell was 82.3%, the energy efficiency was 75%, and the electrochemical performance was excellent.
Example 3
In the embodiment, zinc-bismuth alloy is used as a positive electrode material, and the mole percentage of metal zinc and bismuth is 30:70. Metallic lithium is the negative electrode material, and n Li ＝3*n Bi +0.6*n Zn . The electrolyte adopts low-melting-point molten salt composed of LiF, liCl and LiBr, wherein the mole percentage of LiF, liCl and LiBr is 22:31:47.
The preparation process of the zinc bismuth alloy in the embodiment comprises the following steps: weighing metals Zn and Bi according to the mole percentage, putting the metals into a graphite crucible, simply and uniformly mixing the metals, putting the crucible containing the mixed metal raw materials into a tube furnace, heating the crucible to 550 ℃ under the protection of inert atmosphere, and preserving the temperature for 3 hours to obtain the required zinc-bismuth alloy.
In the embodiment, foam ferronickel is selected as a negative electrode current collector, and molten metallic lithium with required mass is adsorbed in the foam nickel to complete preparation of the negative electrode. The positive current collector is a graphite crucible. In the assembly process, the distance between the negative electrode and the positive electrode is adjusted to be 15mm.
The cell of this example was operated at 500℃and the electrochemical window tested was 0.3-1.5V. Fig. 4 is a graph showing charge and discharge performance of a battery employing example 3 of the present invention. The battery of example 3 has excellent electrochemical properties at 200mA cm -2 At current density, discharge voltage was as high as 0.73V, coulomb efficiency was 91.3%, and energy efficiency was 78%. FIG. 5 is a graph of the cycle performance of a battery employing example 3 of the present invention at 800mAcm -2 The charge and discharge cycle is 50 circles under the current density, the coulomb efficiency is always kept above 98%, and the capacity attenuation rate is only 0.12% of each circle.
The test results above show that: the positive electrode material is applied to a liquid or semi-liquid metal battery, so that the working voltage of the liquid or semi-liquid metal battery is improved, higher coulomb efficiency and energy density are obtained, and the battery cycle performance is good; meanwhile, the successful application of low-cost Zn in the liquid or semi-liquid metal battery reduces the energy storage cost of the battery.
The foregoing is a preferred embodiment of the present invention and is not intended to limit the present invention. It should be noted that the present invention is well understood by those skilled in the art, and thus, several substitutions, modifications and variations based on the principle described in the present invention should be considered as the protection scope of the present invention.
Claims (5)
1. A Zn-based positive electrode for a liquid or semi-liquid metal battery characterized by: the anode is made of Zn alloy formed by more than one simple substance of Zn and Sn, bi, sb, pb, te;
the chemical formula of the Zn alloy is as follows: zn (zinc) 2-98 Bi 98-2 、Zn 2-98 Pb 98-2 、Zn 5-95 Te 95-5 、Zn 2-98 Sn 98-2 Bi 0-80 、Zn 2- 98 Sn 98-2 Pb 0-60 、Zn 2-98 Sn 98-2 Te 0-60 、Zn 2-98 Bi 98-2 Sb 0-80 、Zn 2-98 Bi 98-2 Pb 0-50 、Zn 2-98 Bi 98-2 Te 0-60 、Zn 5- 95 Sb 95-5 Pb 0-60 、Zn 5-95 Sb 95-5 Te 0-70 、Zn 2-98 Pb 98-2 Te 0-60 Wherein the lower right hand subscript in the formula indicates the mole percent of each component and the mole percent of each component in each alloy adds up to 100%, and the lower right hand subscript for all elements is not 0.
2. A liquid or semi-liquid metal energy storage battery prepared using the Zn-based anode of claim 1, characterized in that: 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.
3. A liquid or semi-liquid metal energy storage battery employing a Zn-based anode according to claim 2, wherein: the negative electrode current collector is made of porous foam materials.
4. A liquid or semi-liquid metal energy storage battery employing a Zn-based anode 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 employing a Zn-based anode according to claim 2, wherein: the negative electrode material is in a liquid state at the operating temperature, and the positive electrode and the electrolyte material are in a liquid or semi-liquid state.
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