CN113745492B - Liquid metal battery with prefabricated multi-pore structure positive electrode and preparation method thereof - Google Patents
Liquid metal battery with prefabricated multi-pore structure positive electrode and preparation method thereof Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 72
- 239000002184 metal Substances 0.000 claims abstract description 72
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 28
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- 238000000034 method Methods 0.000 claims abstract description 13
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- 239000007774 positive electrode material Substances 0.000 claims description 45
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- 239000007788 liquid Substances 0.000 claims description 14
- 229910052744 lithium Inorganic materials 0.000 claims description 14
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
- H01M10/399—Cells with molten salts
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/38—Construction or manufacture
-
- 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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- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a liquid metal battery with a prefabricated porous structure positive electrode and a preparation method thereof. During the discharge process of the battery, the negative electrode metal X is firstly combined with Z to form a solid intermetallic compound XZ, and then the solid intermetallic compound is generated by reaction with the rest materials according to the electronegativity. Therefore, by controlling the charge cut-off voltage of the battery to be lower than the voltage of Z dealloying, the intermetallic compound XZ in the solid phase is not converted into Z and is present in the solid phase at all times in the cycle after the battery. The XZ solid phase intermetallic compound suspended in the liquid phase anode metal forms an in-situ prefabricated porous channel structure, and the structure can provide more ion transmission channels during high-current charging and discharging, so that the rate capability of the battery can be improved.
Description
Technical Field
The invention belongs to the technical field of electrochemical energy storage, and particularly relates to a positive electrode material of a liquid metal battery and a preparation method thereof, which can be used for improving the performance of the battery under the operation of high current density.
Background
Along with the rapid development of social economy, the electricity consumption is increased year by year, the electricity consumption of the whole society is increased by 3.1% in 2020 compared with that of 2019, and the construction of a power grid system mainly based on new energy power generation is the key for realizing the targets of carbon peak reaching and carbon neutralization by energy structure adjustment in China. New energy sources such as wind energy and solar energy are influenced by natural environment, climate and the like, and the power generation has discontinuity, so that the operation quality of a power grid can be seriously influenced when the new energy sources are incorporated into a main power grid. Therefore, a long-life and low-cost energy storage system is urgently needed, new energy power generation is merged into a power grid, the phenomenon of wind and electricity abandonment is reduced, and the maximum utilization of energy is realized. The novel liquid metal energy storage battery technology adopts metal materials with abundant reserves as electrodes and inorganic fused salt with lower price as electrolyte, and the electrode materials and the electrolyte are both in liquid state at the operating temperature, so that the electrochemical reaction is fast, and metal dendritic crystal growth cannot be formed to cause short circuit.
The negative electrode of the liquid metal battery is generally alkali metal or alkaline earth metal with lower electronegativity, and the positive electrode material is generally one or more of metals such as Sb, bi, sn, zn and the like with higher electronegativity. The positive electrode material can be classified into the following types: (1) Shan Huoxing positive electrode, such as Li | | Bi liquid metal battery; (2) Single active-inert solvent anodes, such as Li | | Sb (active component) -Sn (inert solvent) cells; (3) A dual active positive electrode, such as a Li Sb-Bi battery, and (4) a triple active electrode, such as a Li Sb-Bi-Sn battery. When the single-component anode metal is used as an anode material of a battery, the problems of high melting point (the melting point of Sb metal is 603 ℃), low voltage (the average discharge voltage of a Li | | | Bi battery is 0.62V) and the like exist; an inert element is added into the single-component anode, so that the melting point of anode metal can be reduced, but the inert component does not contribute to the battery capacity, so that the energy density of the battery is reduced, and the material utilization rate is low; the double-active anode material can improve the overall energy density of the battery and the utilization rate of the material, but because the discharge product is a solid-phase intermetallic compound with different densities, the transmission of ions can be hindered during high-current density discharge, and the rate capability of the battery is poor. Therefore, it is of great significance to further develop liquid metal batteries to develop a novel positive electrode material which can maintain excellent performance and can not reduce the utilization rate of the positive electrode material and the energy density of the batteries.
Disclosure of Invention
The invention discloses a liquid metal battery with a prefabricated multi-pore structure anode and a preparation method thereof, aiming at the problem that the performance of the battery is deteriorated under high current density due to the fact that the solid-phase intermetallic compound blocks the transmission of ions when a double-activity or multi-activity liquid metal battery discharges at high current, the multi-pore structure can be prefabricated in situ by controlling the charge-discharge cut-off voltage of the battery, more channels are provided for the transmission of ions, and the rate capability of the battery is improved.
In order to achieve the above purpose, the liquid metal battery with the prefabricated porous structure positive electrode comprises a positive electrode material, a negative electrode metal, an electrolyte, a battery shell, a battery upper cover and a negative electrode current collector; the positive electrode material and the negative electrode current collector are positioned in a battery shell, and the battery shell is fixedly connected with an upper cover of the battery to form a positive electrode current collector; the negative electrode metal is absorbed in a negative electrode current collector; the first end of the negative lead is connected with a negative current collector, the other end of the negative lead extends out of the battery shell, and the positive lead is connected with the upper cover of the battery; the positive electrode material is composed of metal Y and a substance Z, the potential difference between the metal Y and the negative electrode metal is larger than 0V, the melting point is lower than 650 ℃, and the electronegativity of the substance Z is larger than that of Y.
Further, the metal Y is one or more of Sb, bi, sn, pb and Zn, the substance Z is B, ge, as, S or Te, and the content of the substance Z is 3% -10% of the total substance amount of the positive electrode material.
Further, the negative electrode metal is alkali metal or alkaline earth metal X, and X is Li, na, K, ca or Mg.
Further, the electrolyte is mixed molten salt of alkali metal or alkaline earth metal halide and/or hydroxide of the negative electrode.
Furthermore, the battery shell, the battery upper cover, the positive electrode lead and the negative electrode lead are all made of 304 stainless steel.
Further, the battery shell and the battery upper cover are sealed through a sealing member, and the sealing member is a ceramic gasket.
Further, the negative current collector is a porous foam metal material.
Furthermore, the anode lead and the cathode lead are higher than the upper cover 5 cm-6 cm.
A preparation method of a liquid metal battery with a prefabricated porous structure positive electrode comprises the following steps:
adding a positive electrode metal Y and a high electronegativity substance Z into a battery shell, wherein the amount of the substance Z is 3% -10% of that of the positive electrode material, heating the positive electrode metal Y and the substance Z to completely melt the positive electrode metal Y and the substance Z, and uniformly mixing the positive electrode metal Y and the substance Z to obtain the positive electrode material; the potential difference between the metal Y and the negative electrode metal is greater than 0V, the melting point is lower than 650 ℃, and the electronegativity of the substance Z is greater than Y;
connecting a negative current collector with a negative lead, and immersing the negative current collector into molten negative metal to enable the liquid negative metal to be adsorbed into the negative current collector to obtain a negative material;
and adding electrolyte and a negative electrode current collector into the battery shell, covering the upper cover of the battery, separating the upper cover of the battery from the negative electrode lead, sealing the battery, and connecting the upper cover of the battery with the positive electrode lead.
Compared with the prior art, the invention has at least the following beneficial technical effects:
because the content of the Z substance in the positive electrode material is 3% -10% of the total amount of the positive electrode, the Z substance exists in the positive electrode as the intermetallic compound XZ in the battery cycle process, does not contribute to the battery capacity, and only plays a role of prefabricating cracks, the problems of battery capacity attenuation and performance degradation caused by high solubility of the Z substance in molten salt due to poor conductivity can be avoided, and the method is beneficial to the practical application of the liquid metal battery. The mechanism of crack initiation during battery discharge is as follows: the Z material has the highest electronegativity, so during the discharge process of the battery, the negative electrode metal X is firstly combined with Z to form a solid-phase intermetallic compound XZ, and then the solid-phase intermetallic compound is generated by reaction with the rest material according to the electronegativity. Therefore, it is possible to make the intermetallic compound XZ of the solid phase not converted into Z and always exist as a solid phase in the cycle after the cell by controlling the charge cut-off voltage of the cell to be lower than the voltage at which XZ dealloyes. The XZ solid-phase intermetallic compound suspended in the liquid-phase anode metal forms an in-situ prefabricated porous channel structure, and the structure can provide more ion transmission channels during high-current charging and discharging, so that the rate capability of the battery can be improved.
(1) The novel positive electrode material of the mixture of the metal and the high electronegativity substance can improve the rate capability of the battery. For example, in the Li | | | Sb-Bi liquid metal battery, a high electronegativity substance S is added, and the S is alloyed with Li in the discharging process of the second cycle and is converted into Li 2 S, during the subsequent cyclic charge and discharge with Li 2 The S solid phase intermetallic compound exists in the anode to form a porous anode structure of Li + Provides more channels. The capacity retention rate of the battery under high current density is favorably improved.
(2) The liquid metal provided by the invention does not relate to the structural collapse of the electrolyte, and the volatilization of the electrolyte, so that the capacity of the battery is easy to amplify, and the liquid metal has high energy density and low cost. If the battery capacity of the Li | | | Sb-Bi-S battery of 0.5 Ah is amplified to 3.7Ah, the battery can still stably operate and is at 100 mA.cm -2 The battery runs for 133 cycles under the current density, and the capacity decay rate of the battery is only 0.02 percent cycle -1 The coulomb efficiency can reach 99.5%, the utilization rate of the anode material is 97%, the energy efficiency of the battery reaches 91%, and the energy cost is as low as 290.71 RMB kWh -1 The energy density is as high as 313.27 Wh kg -1 The method has great significance for the practical application of liquid metal battery energy storage.
(3) The liquid metal battery provided by the invention has the operation temperature of 500 ℃. At the temperature, the anode metal, the electrolyte and the cathode are in liquid states, compared with the traditional solid battery, the interface between the electrode and the electrolyte is smooth due to the full liquid state structure, and the battery is not short-circuited due to the fact that solid lithium dendrites are not generated in the charging and discharging process of the battery, so that the failure of the battery can be avoided; in addition, as the circulation proceeds, the liquid electrode and the electrolyte do not undergo structural collapse and leakage of the active material, thus theoretically having an ultra-long life and being capable of preventing ignition, explosion, etc. of the battery, with high safety.
Furthermore, the negative current collector is a porous foam metal material, and the porous foam material can adsorb negative metal and is suitable for being used as a negative current collector.
Furthermore, the positive and negative electrode leads are 5-6 cm higher than the upper cover of the battery, so that the positive and negative electrode leads are conveniently connected with a battery test lead.
Drawings
FIG. 1 is a schematic cross-sectional view of a liquid metal battery employing the positive electrode material of the present invention;
fig. 2 is a schematic diagram of the first four cycle voltage-time curves of a liquid metal battery employing the novel positive electrode material of the present invention;
FIG. 3 is a cycle performance diagram of a 3.7Ah grade battery assembled with the novel positive electrode material of the invention;
fig. 4 is a charge-discharge voltage-time curve of a liquid metal battery employing example 1 of the present invention;
FIG. 5 is a charge-discharge curve for a liquid metal battery of comparative example 1 using the present invention at different current densities;
fig. 6 is a charge-discharge voltage-time curve for a liquid metal battery employing example 2 of the present invention;
fig. 7 is a charge-discharge curve for a liquid metal battery of example 3 of the present invention at different current densities;
FIG. 8 is a schematic phase evolution diagram of a discharge positive electrode region of a liquid metal battery employing embodiment 4 of the present invention;
fig. 9 is a charge-discharge voltage-time curve of a liquid metal battery employing example 5 of the present invention;
fig. 10 is a graph of the cycling performance of a liquid metal battery employing example 6 of the present invention;
fig. 11 is a charge-discharge curve of a liquid metal battery according to example 7 of the present invention.
In the drawings: 1-negative electrode lead, 2-positive electrode lead, 3-battery upper cover, 4-sealing member, 5-electrolyte, 6-battery shell, 7-negative electrode current collector and 8-positive electrode material.
Detailed Description
Referring to fig. 1, a liquid metal battery with a prefabricated porous structure positive electrode includes a positive electrode material 8, a negative electrode material, an electrolyte 5, a battery case 6, a battery upper cover 3, a sealing member 4, and a negative electrode current collector 7. The positive electrode material 8 and the electrolyte 5 are both arranged in the battery shell 6, and the battery shell 6 is connected with the battery upper cover 3 through threads to serve as a positive electrode current collector; the negative electrode material is adsorbed in the negative electrode current collector 7. The anode lead 2 is connected with the battery upper cover 3 in a welding mode, the cathode lead 1 is connected with the cathode current collector 7 through a stud nut, and the anode lead and the cathode lead are 5-6 cm higher than the battery upper cover and are conveniently connected with a battery test lead. The sealing element 4 is a ceramic gasket, corrosion-resistant and insulating.
The positive electrode material consists of metal Y and high electronegativity Z, wherein Y is one or more of Sb, bi, sn, pb and Zn, and Z is B, ge, as, S or Te. The negative electrode material is an alkali metal or alkaline earth metal Li, na, K, ca or Mg with a lower density and a lower electronegativity, which is absorbed in the negative electrode current collector 7. The negative electrode current collector 7 is a porous metal material. The mixed molten salt of the negative electrode metal corresponding to the halide or the hydroxide is used as an electrolyte. The novel positive electrode material formed by combining metal and high electronegativity substances enables the battery to still operate at the temperature of 500 ℃. Secondly, the substance Z having high electronegativity can increase the discharge voltage of the battery, thereby contributing to an increase in energy efficiency of the battery.
Preferably, the content of the substance Z is 3 to 10 percent of the total substance amount of the positive electrode.
Preferably, 304 stainless steel is used for the battery case 6, the battery upper cover 3, the negative electrode lead 1, and the positive electrode lead 2. 304 stainless steel is easy to machine and form and is resistant to corrosion at high temperatures.
The anode metal, the cathode material and the molten salt electrolyte are all in liquid state at the working temperature of the battery.
A liquid metal battery with a prefabricated porous structure positive electrode comprises the following steps:
adding a positive electrode metal Y and a high electronegativity substance Z into a battery shell, wherein the amount of the substance Z with electronegativity higher than 2.0 is 3-10% of that of the positive electrode material, heating the positive electrode metal Y and the positive electrode material Z to completely melt the positive electrode metal Y and the positive electrode material Z, and preserving heat to uniformly mix the positive electrode material to obtain a positive electrode material 8;
connecting a negative current collector 7 with a negative lead 1, immersing the negative current collector into molten negative metal, adsorbing the liquid negative metal into the negative current collector 7 to obtain a negative material, wherein the quality difference of the negative current collectors before and after the immersion of the negative metal is the quality of the negative metal;
Referring to fig. 2, when the cathode of the battery is made of Li metal, and high electronegativity Te which is 5% of the total substance amount of the cathode material is added into the Sb-Bi alloy of the cathode metal,the open circuit voltage of the cell after assembly is about 1.5V. Discharging the battery, wherein the voltage platform of the Li and Te alloy of the cathode metal is about 1.5V, so that other intermetallic compounds such as Li and Te are generated at the anode in the order of high electronegativity and low electronegativity in the first discharging process 3 Sb、Li 3 Bi and the like, do not generate Li 2 Te intermetallic compound or generation of small amount of Li 2 A Te intermetallic compound. Therefore, the first-time cyclic discharge cutoff voltage is set to be 0.4V, and the charge cutoff is set to be 2.0V; in the second cycle, the discharge cutoff voltage was set to 0.4V, and Li was generated in order from high to low in accordance with the electronegativity during the discharge 2 Te、Li 3 Sb、Li 3 And an intermetallic compound such as Bi. To obtain the positive electrode multi-channel structure, the charge cut-off voltage of the second cycle was set to 1.5V, lower than Li 2 Te dealloying voltage (1.7V), therefore the positive electrode is liquid metal and solid Li in the second cycle fully charged state 2 A Te intermetallic compound. In the following cycle, setting the cutoff voltage to 0.4-1.5V, there will always be Li present in the cell positive electrode 2 The Te solid intermetallic compound has a solid phase structure suspended in liquid phase metal, so that a porous anode structure is manufactured for the anode of the battery, and more channels are provided for the transmission of ions.
Example 1
A liquid metal battery with a prefabricated multi-pore structure positive electrode comprises a positive electrode material 8, a negative electrode material, an electrolyte 5, a battery shell 6, a battery upper cover 3, a sealing piece 4 and a negative electrode current collector 7. The positive electrode material 8 and the electrolyte 5 are both positioned in the battery shell 6, and the battery shell 6 is connected with the battery upper cover 3 through threads and is a positive electrode current collector; the battery case 6, the battery upper cover 3, the positive electrode lead 2, and the negative electrode lead 1 are all made of 304 stainless steel. The negative metal is adsorbed in the negative current collector 7. The positive electrode material consists of Sb-Bi alloy and Te, wherein the mole ratio of Sb to Te in the Sb-Bi alloy is Sb: bi =4:6. The cathode material is metal Li, the cathode current collector is foam nickel iron, and the electrolyte is LiCl-LiBr-LiF mixed molten salt.
In this embodiment, sb is 40 Bi 60 Te is added into the alloy to form a positive electrode material, a negative electrode material is metallic Li, and the alloy is chargedThe electrolyte is LiCl-LiBr-LiF ternary molten salt. The amount of the Te added substance is 3 percent of the total substance amount of the anode material, and the obtained battery capacity is about 0.4 Ah. Cm at 100, 200, 600, 800, 1000mA, respectively -2 The current density of the battery is measured, the coulombic efficiency of the battery is 99 percent, and the coulombic efficiency is 1000mA -2 The discharge capacity at current density was able to maintain 65% of the initial capacity. The charge and discharge curves are shown in fig. 4, and it can be seen from fig. 4 that: in the process of charging and discharging the battery, two voltage platforms are provided, the discharging voltage platforms are respectively about 0.75V and 0.7V and respectively correspond to the alloying voltage of Sb and Bi, so that the addition of Te element can not influence the operation stability of the battery.
Comparative example 1
The Sb-Bi alloy is directly used as the anode to assemble the Li | | | Sb-Bi battery, no Te is added, and other battery materials and test procedures are completely consistent with those in the embodiment 1. Constant current charge and discharge tests were performed at current densities of 100, 200, 600, 800, 1000mA, respectively, at 100 and 1000ma -2 The following charge and discharge curves are shown in fig. 5. It can be seen that at 1000mA.cm -2 The discharge capacity of the battery can keep 63% of the initial capacity under the current density, and the capacity retention rate of the battery is lower than that of a Li | | | Sb-Bi battery containing a Te additive under the same current density.
Example 2
In the embodiment, ge is added into pure Bi metal to form a positive electrode material, a negative electrode material is metal Li, and an electrolyte is LiCl-LiBr-LiF ternary molten salt. The amount of the Ge added substance is 5 percent of the total amount of the anode material, and the capacity of the obtained battery is about 0.5 Ah. Cm at 100, 200, 600, 800, 1000mA, respectively -2 The current density of the battery is measured, the coulombic efficiency of the battery is 99 percent, and the coulombic efficiency is 1000mA -2 The discharge capacity at the current density was maintained at 76% of the initial capacity, and the charge and discharge curves are shown in FIG. 6.
Example 3
In this embodiment, sb is 60 Pb 40 And adding an additive B into the alloy to form a positive electrode material, wherein the negative electrode material is metal Li, and the electrolyte is LiCl-LiBr-LiF ternary molten salt. AddingThe amount of the substances entering the B is 10 percent of the total substance amount of the positive electrode material, and the obtained battery capacity is about 0.5 Ah. Cm at 100, 200, 600, 800, 1000mA, respectively -2 Under a current density of 100 and 1000mA.cm, and performing constant current charge and discharge test -2 The charge and discharge curves at the current density of (2) are shown in fig. 7. It can be seen that the coulombic efficiency of the cell is 99% at 1000ma -2 The discharge capacity at the current density was able to maintain 81.6% of the initial capacity.
Example 4
In the present embodiment, a Li | | | Sb-Bi-As battery is assembled. The amount of As substance is 5% of the total amount of positive electrode material, phase composition of each state is determined by X-ray diffractometer under initial full charge state, 60% depth of discharge, 100% depth of discharge and second cycle full charge state, the result shows that only alloy formed by positive electrode material under full charge state produces Li in sequence As battery discharges 3 As、Li 3 Sb、Li 3 Bi solid phase intermetallic compound. Setting the second cycle charge cutoff voltage to 1.5V, it can be seen that in the fully charged state of the second cycle, the positive electrode is made of metals Sb, bi and the intermetallic compound Li 3 As. It can be stated that Li, in the subsequent cycles of the cell, sets the cutoff voltage at 0.4-1.5V 3 As always exists in a solid phase in the positive electrode area, namely a multi-channel structure is manufactured, which is beneficial to ion transmission in the electrochemical reaction process of the battery, and the fact that compared with a Li | | Sb-Bi battery, the multiplying power performance of the battery is better due to the addition of high electronegativity substances is further verified, and the evolution process of the positive electrode structure of the battery in the discharging process is shown in figure 8. As can be seen from fig. 8 (a): during the second cycle of full charge of the battery, the irregular solid intermetallic compound is suspended in the liquid phase of the Sb-Bi alloy, and as the battery continues to discharge, the positive electrode region gradually has solid phase Li as shown in FIG. 8 (b) 3 Sb and Li 3 Bi is generated, and the solid-phase intermetallic compounds in the positive electrode area are accumulated more along with the larger discharge depth of the battery. If there is no solid phase of Li 3 As at the positive electrode forms a solid phase structure which is not favorable for ion transport at the late stage of discharge, and As shown in (c) of FIG. 8In discharge state, the lower part of the positive electrode region is Li 3 Sb and Li 3 Mixture of Bi with preformed Li on top 3 Sb and Li 3 The crack structure of Bi further indicates that the novel prefabricated crack structure anode obviously improves the battery performance.
Example 5
In this example, sb is 40 Bi 60 And adding S into the alloy to form a positive electrode material, wherein the negative electrode material is metal Na, and the electrolyte is NaOH-NaI molten salt. The amount of the substance to which S is added is 5% of the total substance amount of the positive electrode material. At 100 mA.cm -2 The battery was operated at a current density of (1) and the charge and discharge curves of the battery were as shown in fig. 9. The battery can stably run for more than 100 cycles, the coulomb efficiency of the battery can reach 99.5%, and the utilization rate of the anode material is 97%.
Example 6
In this example, sb is 40 Bi 60 S is added into the alloy to form a positive electrode material, a negative electrode material is metal Li, an electrolyte is LiCl-LiBr-LiF mixed molten salt, and the battery capacity is about 3.6 Ah. The amount of the substance to which S is added is 10% of the total substance amount of the positive electrode material. At 100 mA.cm -2 The current density of (a) was measured, and the cell cycle performance was as shown in fig. 10. It can be seen that: the battery can stably run for more than 200 cycles, the coulomb efficiency of the battery is more than 99.2, and the energy efficiency is close to 90%.
Example 7
In this embodiment, sb is 20 Bi 20 Sn 20 Pb 20 Zn 20 S is added into the alloy to form a positive electrode material, a negative electrode material is metal Li, an electrolyte is LiCl-LiBr-LiF mixed molten salt, and the battery capacity is about 0.4 Ah. The amount of the substance to which S was added was 8% of the total substance amount of the positive electrode material. At 100 mA.cm -2 The battery was operated at a current density of (1) and the charge and discharge curves of the battery were as shown in fig. 11. It can be seen that: under the cut-off voltage of 0.2-1.2V, the practical discharge capacity of the battery is about 3.6 Ah, and the material utilization rate can reach about 90%.
The above results show that: the novel anode material can form a multi-channel anode structure by forming a solid-phase intermetallic compound on the anode, so that ion transmission channels are increased, and the rate capability of the battery is improved. In addition, the system has high energy efficiency, low cost and easy amplification, and is favorable for the practicability of the liquid metal battery.
The above examples are provided for clarity of illustration 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 (6)
1. A liquid metal battery with a prefabricated porous structure anode is characterized by comprising a prefabricated porous structure anode, a prefabricated porous structure cathode, an electrolyte (5), a battery shell (6) and a battery upper cover (3); the negative electrode comprises a negative electrode current collector (7) and liquid negative electrode metal X absorbed in the negative electrode current collector (7), the positive electrode and the negative electrode with the prefabricated porous structure are positioned in the battery shell (6), the positive electrode with the prefabricated porous structure is in contact with the battery shell (6), and the battery shell (6) is fixedly connected with the upper battery cover (3) to form a positive electrode current collector;
one end of the negative lead (1) is connected with the negative current collector (7), the other end of the negative lead extends out of the battery shell (6), and the battery upper cover (3) is connected with the positive lead (2);
the method comprises the following steps of preparing a positive electrode with a prefabricated porous structure by taking a positive electrode material (8) and a negative electrode metal X as raw materials, wherein the positive electrode material (8) consists of a positive electrode metal Y and a substance Z, and the positive electrode with the prefabricated porous structure comprises a liquid positive electrode metal Y and a solid-phase intermetallic compound XZ suspended in the liquid positive electrode metal Y;
the potential difference between the anode metal Y and the cathode metal X is greater than 0V, the melting point is lower than 650 ℃, and the electronegativity of the substance Z is greater than that of the anode metal Y;
the positive metal Y is one or more of Sb, bi, sn, pb and Zn, and the substance Z is S or Te;
the negative electrode metal X is Li or Na;
the preparation method of the liquid metal battery with the prefabricated porous structure positive electrode comprises the following steps:
adding a positive electrode metal Y and a substance Z into a battery shell (6), heating the positive electrode metal Y and the substance Z to be completely molten, and uniformly mixing the positive electrode metal Y and the substance Z to obtain a positive electrode material (8), wherein the amount of the substance Z is 3% -10% of that of the positive electrode material (8); the potential difference between the positive electrode metal Y and the negative electrode metal X is greater than 0V, and the melting point is lower than 650 ℃;
connecting a negative current collector (7) with a negative lead (1), and immersing the negative current collector into molten negative metal X to enable the liquid negative metal X to be absorbed into the negative current collector (7) to obtain a negative electrode;
adding an electrolyte (5) and a negative electrode into a battery shell (6), covering an upper battery cover (3), separating the upper battery cover (3) from a negative electrode lead (1), sealing the battery, and connecting the upper battery cover (3) with a positive electrode lead (2) to obtain the battery;
and setting a charge cut-off voltage to be higher than the dealloying potential of the negative electrode metal X and the substance Z during the first cycle of the battery, alloying the liquid negative electrode metal X and the liquid substance Z to generate a solid-phase intermetallic compound XZ in the second cycle and the subsequent cycle according to the electronegativity, setting the charge cut-off voltage to be lower than the dealloying potential of the solid-phase intermetallic compound XZ during the second cycle and the subsequent cycle, so that the solid-phase intermetallic compound XZ cannot be dealloyed during charging, suspending the solid-phase intermetallic compound XZ in the liquid positive electrode metal Y in the full-charge state of the second cycle and the subsequent cycle, and obtaining the positive electrode with the prefabricated porous channel structure in situ.
2. The liquid metal battery with the prefabricated porous structure positive electrode as claimed in claim 1, wherein the electrolyte is a mixed molten salt of a halide or a hydroxide of a negative electrode metal.
3. The liquid metal battery with the prefabricated porous structure positive electrode as claimed in claim 1, wherein the battery case (6), the battery top cover (3), the positive electrode lead (2) and the negative electrode lead (1) are all made of 304 stainless steel.
4. The liquid metal battery with the prefabricated multi-pore structure positive electrode as claimed in claim 1, wherein the battery shell (6) and the battery upper cover (3) are sealed by a sealing member (4), and the sealing member (4) is a ceramic gasket.
5. The liquid metal battery with the prefabricated porous structure positive electrode as claimed in claim 1, wherein the negative current collector (7) is a porous foam metal material.
6. The liquid metal battery with the prefabricated porous structure anode as claimed in claim 1, wherein the anode lead (2) and the cathode lead (1) are higher than the battery upper cover (3) by 5 cm-6 cm.
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Citations (10)
| 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 |
| CN103280604A (en) * | 2013-05-14 | 2013-09-04 | 清华大学 | Liquid energy storage battery monomer structure with floating body electrolytes |
| CN104112865A (en) * | 2014-07-22 | 2014-10-22 | 西安交通大学 | Liquid metal battery device and assembly method thereof |
| CN204289603U (en) * | 2014-12-12 | 2015-04-22 | 芶富均 | A kind of liquid metal cell device |
| CN106025249A (en) * | 2016-07-20 | 2016-10-12 | 云南科威液态金属谷研发有限公司 | Room-temperature liquid metal battery |
| CN107221677A (en) * | 2017-07-05 | 2017-09-29 | 北京科技大学 | A kind of liquid metal cell of high-energy-density |
| CN107403887A (en) * | 2017-07-20 | 2017-11-28 | 北京科技大学 | A kind of liquid metal cell device and its assembly method |
| CN107482209A (en) * | 2017-07-17 | 2017-12-15 | 华中科技大学 | A kind of positive electrode for being used for liquid and semi-liquid metal battery |
| US10270139B1 (en) * | 2013-03-14 | 2019-04-23 | Ambri Inc. | Systems and methods for recycling electrochemical energy storage devices |
| CN113193179A (en) * | 2021-03-29 | 2021-07-30 | 西安交通大学 | Liquid metal battery and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10170799B2 (en) * | 2014-12-15 | 2019-01-01 | Massachusetts Institute Of Technology | Multi-element liquid metal battery |
| CN110729470B (en) * | 2019-10-22 | 2021-06-01 | 北京科技大学 | Positive electrode material of liquid or semi-liquid metal battery, preparation method and application |
-
2021
- 2021-08-26 CN CN202110991397.5A patent/CN113745492B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10270139B1 (en) * | 2013-03-14 | 2019-04-23 | Ambri Inc. | Systems and methods for recycling electrochemical energy storage devices |
| 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 |
| CN103280604A (en) * | 2013-05-14 | 2013-09-04 | 清华大学 | Liquid energy storage battery monomer structure with floating body electrolytes |
| CN104112865A (en) * | 2014-07-22 | 2014-10-22 | 西安交通大学 | Liquid metal battery device and assembly method thereof |
| CN204289603U (en) * | 2014-12-12 | 2015-04-22 | 芶富均 | A kind of liquid metal cell device |
| CN106025249A (en) * | 2016-07-20 | 2016-10-12 | 云南科威液态金属谷研发有限公司 | Room-temperature liquid metal battery |
| CN107221677A (en) * | 2017-07-05 | 2017-09-29 | 北京科技大学 | A kind of liquid metal cell of high-energy-density |
| CN107482209A (en) * | 2017-07-17 | 2017-12-15 | 华中科技大学 | A kind of positive electrode for being used for liquid and semi-liquid metal battery |
| CN107403887A (en) * | 2017-07-20 | 2017-11-28 | 北京科技大学 | A kind of liquid metal cell device and its assembly method |
| CN113193179A (en) * | 2021-03-29 | 2021-07-30 | 西安交通大学 | Liquid metal battery and preparation method thereof |
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