WO2016019765A1 - Liquid metal cathode material and room-temperature liquid metal battery, and preparation method thereof and usage thereof - Google Patents

Abstract

Disclosed are a liquid metal cathode material and a room-temperature liquid metal battery, and a preparation method therefor and usage thereof. The cathode material is dark green liquid generated by mixing alkali metal, an aromatic compound and an ether solvent. The alkali metal is any one of metallic sodium, metallic lithium or metallic potassium. The aromatic compound is any one of biphenyl, derivatives of biphenyl, naphthaline, derivatives of naphthaline, anthracene or derivatives of the anthracene. The ether solvent comprises one or more of glycol dimethyl ether, diethylene glycol dimethyl ether or tetraethylene glycol dimethyl ether, etc.

Description

Liquid metal anode material and room temperature liquid metal battery, preparation method and use thereof Technical field

The invention relates to the technical field of materials, in particular to a liquid metal anode material and a room temperature liquid metal battery, a preparation method and a use thereof.

Background technique

With the depletion of traditional fossil energy sources and the increasing environmental problems, the development and utilization of renewable energy such as solar energy and wind energy is imminent. However, due to the volatility and intermittent nature of solar energy and wind energy, the instability of the power grid is required, so it is necessary to vigorously develop large-scale energy storage technologies. Large-scale energy storage technology can effectively solve the problem of intermittent power supply of renewable energy such as solar energy and wind energy, realize demand management, eliminate diurnal peaks and valleys, and smooth load.

At present, the main large-scale energy storage technologies include pumped storage, compressed air storage, flywheel energy storage, and electrochemical energy storage. Various energy storage technologies have their own use conditions and advantages, and are in the active stage of research and development and demonstration. Among them, chemical energy sources such as sodium-sulfur batteries, all-vanadium flow batteries, and lithium-ion batteries have been demonstrated as energy storage devices for large-scale energy storage.

However, sodium-sulfur batteries need to operate at a high temperature of 300 degrees. The direct use of molten metal sodium and sulfur has led to serious corrosion problems and safety hazards. The vanadium ion used in the all-vanadium flow battery is highly toxic and has limited resources. In addition, there is a problem of interdiffusion of positive and negative active materials during operation, and the energy density of the energy storage battery is not high. Lithium-ion batteries have better performance as large-scale energy storage batteries, but lithium ion energy storage batteries have high manufacturing costs. Therefore, there is currently no energy storage battery that can meet the comprehensive requirements of low cost, good safety, and abundant raw materials.

Summary of the invention

Embodiments of the present invention provide a liquid metal anode material and a room temperature liquid metal battery, a preparation method, and a use thereof. The liquid metal anode material has liquid fluidity, good electronic and ionic conductivity, low potential, high safety and good wetting property, and the battery prepared by using the material as a negative electrode has high specific energy, The characteristics of long cycle life can be used for storage of power output from power stations such as solar energy and wind energy.

In a first aspect, an embodiment of the present invention provides a dark green liquid obtained by mixing an alkali metal, an aromatic compound, and an ether solvent;

Wherein the alkali metal is any one or more of sodium metal, lithium metal or potassium metal;

The aromatic compound is any one or more of biphenyl, a derivative of biphenyl, a derivative of naphthalene, naphthalene, or a derivative of ruthenium or osmium;

The ether solvent includes diethyl ether, methyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dipropyl ether, diisopropyl ether, ethyl butyl ether, two Butyl ether, dipentyl ether, diisoamyl ether, dihexyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxocyclopentane, 4-methyl-1,3-dioxolane, two Methoxymethane, 1,2-dimethoxypropane, dioxolane, 1,4-dioxane, ethylene oxide, propylene oxide, 1,1-diethoxyethane, two Any one or more of methyl sulfoxide, sulfolane or dimethyl sulfone.

In a second aspect, the embodiment of the present invention provides a method for preparing a liquid metal anode material according to the above first aspect, the method comprising:

The alkali metal and the aromatic compound are added to the ether solvent in a certain molar ratio in a protective atmosphere of argon, and left to stand to obtain the liquid metal negative electrode material;

Wherein the alkali metal is any one or more of sodium metal, lithium metal or potassium metal;

The aromatic compound is any one or more of biphenyl, a derivative of biphenyl, a derivative of naphthalene, naphthalene, or a derivative of ruthenium or osmium;

The ether solvent includes diethyl ether, methyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dipropyl ether, diisopropyl ether, ethyl butyl ether, two Dibutyl ether, diamyl ether, diisoamyl ether, Dihexyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxocyclopentane, 4-methyl-1,3-dioxolane, dimethoxymethane, 1,2-dimethoxy Propane, dioxolane, 1,4-dioxane, ethylene oxide, propylene oxide, 1,1-diethoxyethane, dimethyl sulfoxide, sulfolane or dimethyl sulfone Any one or more of them.

In a third aspect, an embodiment of the present invention provides a chargeable room temperature liquid metal battery comprising the liquid metal anode material according to the above first aspect.

Preferably, the chargeable room temperature liquid metal battery further comprises:

One of a liquid positive electrode material or a slurry positive electrode material, and an ion conductive, electronically insulating solid electrolyte membrane;

Wherein the solid electrolyte comprises Na ₃ Zr ₂ Si ₂ PO ₁₂ ceramic, Na-β′′-Al ₂ O ₃ ceramic, K-β′′-Al ₂ O ₃ ceramic for conducting sodium ions, lithium ions or potassium ions Any of Li ₇ La ₃ Zr ₂ O ₁₂ ceramics or Li ₁₀ GeP ₂ S ₁₂ ceramics.

Preferably, the preparation method of the slurry positive electrode material comprises:

The solid powder and the carbon powder of the positive electrode active material are uniformly mixed in a certain mass ratio, and a certain amount of the supporting electrolyte is added and stirred to obtain the liquid positive electrode material;

Wherein, the positive active material includes: Na _0.44 MnO ₂ , NaTi ₂ (PO ₄ ) ₃ , Na ₃ V ₂ (PO _{4) 3} , Na _0.8 Li _0.1 Ni _0.25 Mn _0.65 O ₂ , NaMg _0.1 Ni _0.4 Mn _0.2 Ti Any one or more of _0.3 O ₂ , S, K ₃ Fe(CN) ₆ , Na ₄ Fe(CN) ₆ , and FePO ₄ .

Preferably, the preparation method of the slurry positive electrode material comprises:

The liquid positive electrode material and the carbon powder are uniformly mixed in a certain mass ratio, and a certain amount of the supporting electrolyte is added and stirred to obtain the liquid positive electrode material.

Further preferably, the liquid positive electrode material is:

Mixing one or more of p-benzoquinone, a derivative of p-benzoquinone, a derivative of hydrazine, hydrazine, a derivative of hydrazine, hydrazine, a phenanthrenequinone or a phenanthrenequinone as a solute, A liquid composed of one or more of ethylene glycol dimethyl ether, propylene carbonate, tetraethylene glycol dimethyl ether, dimethylformamide or N-methylpyrrolidone mixed as a solvent.

Further preferably, the preparation method of the liquid positive electrode material comprises:

Mixed with any one or more of 0.1 to 5 mol of p-benzoquinone, a derivative of p-benzoquinone, a derivative of hydrazine, hydrazine, a derivative of hydrazine, hydrazine, a derivative of phenanthrenequinone or phenanthrenequinone Is a solute, dissolved in 1L of any one or more mixed solvents of ethylene glycol dimethyl ether, propylene carbonate, tetraethylene glycol dimethyl ether, dimethylformamide or N-methylpyrrolidone, added A quantity of supporting electrolyte is obtained to obtain the liquid positive electrode material.

Further preferably, the liquid positive electrode material is:

Solvent with benzophenone, hydrazine, tetracene, pentacene or hydrazine, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dimethyl A liquid composed of one or more of formamide or N-methylpyrrolidone mixed as a solvent.

Further preferably, the preparation method of the liquid positive electrode material comprises:

0.1 to 5 mol of benzophenone, hydrazine, tetracene, pentacene or hydrazine mixed as a solute, dissolved in 1 L of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether In a mixed solvent of one or more of tetraethylene glycol dimethyl ether, dimethylformamide or N-methylpyrrolidone, a certain amount of alkali metal is added and allowed to stand to obtain the liquid positive electrode material.

Further preferably, the liquid positive electrode material is:

Na ₂ S _x as a solute, one or more of dimethyl sulfoxide, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dimethylformamide, N-methylpyrrolidone or water A solution composed of a solvent; wherein 3 ≤ x ≤ 12.

Further preferably, the preparation method of the liquid positive electrode material comprises:

Add Na ₂ S and S to dimethyl sulfoxide, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether or dimethyl ketone according to the molar ratio of Na ₂ S/S=1/(x-1) Any one of the amide or N-methylpyrrolidone or water, and adding a certain amount of supporting electrolyte to stir to completely dissolve, thereby obtaining the liquid positive electrode material;

Where 3≤x≤12.

Further preferably, the chargeable room temperature liquid metal battery is a cylindrical battery, comprising:

Stainless steel housing and solid electrolyte tube;

The solid electrolyte tube is nested in the stainless steel casing without contact, and a sealed space between the inner wall of the stainless steel casing and the outer wall of the solid electrolyte tube is used for accommodating the liquid positive electrode material; For accommodating the liquid metal anode material.

Further preferably, the chargeable room temperature liquid metal battery is a dual flow battery, comprising:

a battery case, a solid electrolyte membrane, a positive electrode reservoir, a negative reservoir, and two pumps;

The solid electrolyte membrane partitions the battery case into a sealed positive electrode space and a negative electrode space, wherein the positive electrode space is connected to the positive electrode liquid storage tank, and the liquid contained in the positive electrode liquid storage tank is connected by a pump The positive electrode material is pumped into the positive electrode space, and the negative electrode space is connected to the negative electrode storage tank, and the liquid metal negative electrode material accommodated in the negative electrode storage tank is pumped into the negative electrode space by a pump.

Further preferably, the chargeable room temperature liquid metal battery is a single flow battery, comprising:

a battery case, a solid electrolyte membrane, a positive electrode reservoir, and a pump;

The solid electrolyte membrane partitions the battery case into a sealed positive electrode space and a negative electrode space, wherein the positive electrode space is connected to the positive electrode liquid storage tank, and the pump is used to accommodate the positive electrode liquid storage tank A liquid positive electrode material is pumped into the positive electrode space, and the negative electrode space is for accommodating the liquid metal negative electrode material.

Further preferably, the chargeable room temperature liquid metal battery is a flat metal battery, comprising:

a battery case and a solid electrolyte membrane;

The solid electrolyte membrane divides the battery case into a sealed positive electrode space for accommodating the liquid positive electrode material, and a negative electrode space for accommodating the liquid metal negative electrode material.

In a fourth aspect, the embodiment of the present invention provides the use of the room temperature liquid metal battery according to the above third aspect, wherein the chargeable room temperature liquid metal battery is used for solar power generation, wind power generation, and smart grid adjustment. Large-scale energy storage equipment for peaks, distributed power stations, backup power sources or communication base stations.

The liquid metal anode material provided by the embodiment of the invention has liquid fluidity, good electronic and ionic conductivity, low potential, high safety and good wetting performance, and low cost. The material is abundant, and the battery prepared by using this material as a negative electrode has the characteristics of high specific energy and long cycle life, and can be used for storage of electric energy output of power stations such as solar energy and wind energy.

DRAWINGS

The technical solutions of the embodiments of the present invention are further described in detail below through the accompanying drawings and embodiments.

1 is an electrochemical impedance spectroscopy chart of a biphenyl-DME-metal sodium liquid metal negative electrode according to Embodiment 2 of the present invention;

2 is a graph showing changes with time of a solution of a biphenyl-DME-metal sodium solution supplied with deionized water according to Example 2 of the present invention;

3 is a schematic view showing the solubility of a biphenyl-DME-metal sodium liquid negative electrode according to Embodiment 2 of the present invention;

4 is a schematic structural diagram of a cylindrical battery according to an embodiment of the present invention;

FIG. 5 is a schematic structural diagram of a dual flow battery according to an embodiment of the present invention; FIG.

6 is a schematic structural diagram of a single-flow battery according to an embodiment of the present invention;

FIG. 7 is a schematic structural diagram of a flat metal battery according to an embodiment of the present invention; FIG.

8 is a graph showing a charge and discharge performance curve of a battery constructed by a liquid anode material and a ruthenium liquid cathode material according to Embodiment 9 of the present invention;

9 is a cycle performance curve of a battery constructed by a liquid metal negative electrode material and a ruthenium liquid positive electrode material according to Embodiment 9 of the present invention;

10 is a graph showing charge and discharge performance of a battery constructed of a liquid metal anode material and a tantalum-carbon black slurry cathode according to Embodiment 10 of the present invention;

11 is a graph showing a charge-discharge performance curve of a battery constructed in a liquid metal anode material and a benzoquinone liquid cathode material according to Embodiment 11 of the present invention;

12 is a graph showing a charge and discharge performance of a battery constructed by a liquid metal anode material and a ruthenium liquid cathode material according to Embodiment 12 of the present invention;

Figure 13 is a bismuth-PC-sodium perchlorate, benzoquinone-PC-sodium perchlorate, according to Example 12 of the present invention, 苊醌-PC-sodium perchlorate is the first week charge and discharge comparison chart of liquid positive electrode material;

14 is a graph showing charge and discharge performance of a liquid metal negative electrode material and a battery constructed of NaTi ₂ (PO ₄ ) _{3 according} to Embodiment 13 of the present invention;

15 is a cycle performance curve of a liquid metal negative electrode material and a battery constructed of NaTi ₂ (PO ₄ ) _{3 according} to Embodiment 13 of the present invention;

16 is a graph showing the charge and discharge performance of a liquid metal negative electrode material and a battery constructed of Na ₃ V ₂ (PO ₄ ) _{3 according} to Example 14 of the present invention;

17 is a graph showing the charge and discharge performance of a liquid metal negative electrode material and a Na _0.44 MnO ₂ battery according to Embodiment 15 of the present invention;

18 is a graph showing a charge and discharge performance of a battery composed of a liquid metal negative electrode material and a ruthenium-DME liquid positive electrode according to Embodiment 16 of the present invention;

19 is a graph showing a charge and discharge performance of a battery composed of a liquid metal negative electrode material and a tetracene-DME liquid positive electrode according to Embodiment 17 of the present invention;

20 is a graph showing a charge and discharge performance of a battery composed of a liquid metal negative electrode material and a Na ₂ S ₈ liquid positive electrode according to Embodiment 18 of the present invention;

Figure 21 is a graph showing the change of the biphenyl-DME-metal sodium solution with time after the addition of polysulfide ions according to Example 18 of the present invention;

22 is a graph showing a charge and discharge performance of a battery composed of a liquid metal negative electrode material and a Na ₂ S ₁₂ liquid positive electrode according to Embodiment 19 of the present invention;

23 is a graph showing the charge-discharge performance of a liquid metal negative electrode material and a S-carbon black slurry positive electrode provided in Example 20 of the present invention between 1.5 and 2.7 V;

24 is a graph showing the charge and discharge performance of a battery constructed of a liquid metal anode material and a S-carbon black slurry cathode according to Embodiment 20 of the present invention at 1.7 to 2.8 V;

Figure 25 is a graph showing the charge and discharge performance of a battery constructed of a liquid metal negative electrode material and a tetramethoxypiperidine liquid positive electrode according to Example 21 of the present invention;

Figure 26 is a graph showing the charge and discharge performance of a battery constructed of a liquid metal negative electrode material and a K ₃ Fe(CN) ₆ aqueous solution according to Example 22 of the present invention;

Figure 27 is a graph showing the charge and discharge performance of a battery constructed of a liquid metal anode material and a benzophenone provided in Example 23 of the present invention;

28 is a graph showing charge and discharge performance of a battery constructed of a liquid metal negative electrode material and an iodine liquid positive electrode according to Embodiment 24 of the present invention;

29 is a graph showing charge and discharge performance of a battery constructed of a liquid metal negative electrode material and a ferrocene liquid positive electrode according to Embodiment 25 of the present invention;

Figure 30 is a graph showing the charge and discharge performance of a battery constructed of a liquid metal negative electrode material and a liquid positive electrode provided in Example 26 of the present invention;

Figure 31 is a graph showing the charge and discharge performance of a battery constructed of a liquid metal negative electrode material and a quinoxaline liquid positive electrode according to Example 27 of the present invention;

Figure 32 is a graph showing the charge and discharge performance of a battery composed of a naphthalene-DME-metal sodium liquid negative electrode and a ruthenium-PC-sodium perchlorate liquid positive electrode according to Example 28 of the present invention;

33 is a charge and discharge curve of a battery composed of biphenyl-DME-metal sodium and an excess hydrazine solution according to Example 29 of the present invention;

FIG. 34 is a physical diagram of a cylindrical battery according to an embodiment of the present invention.

detailed description

The invention is further described in detail below with reference to the embodiments, but is not intended to limit the scope of the invention.

Example 1

Embodiment 1 of the present invention provides a liquid metal negative electrode material.

Wherein the anode material is a dark green liquid formed by mixing an alkali metal, an aromatic compound and an ether solvent;

Specifically, the alkali metal may be any one or more of sodium metal (Na), lithium metal (Li) or potassium (K);

The aromatic compound may be any one or more of biphenyl (BP), a derivative of biphenyl, naphthalene (NP), a derivative of naphthalene, a derivative of ruthenium or osmium;

Wherein; the derivative of biphenyl may specifically be: biphenyl, dichlorobiphenyl, tetrachlorobiphenyl, terphenyl, x-methylbiphenyl, x-ethylbiphenyl, etc.;

The derivative of naphthalene may specifically be: phenanthrene, dichloronaphthalene, tetrachloronaphthalene, x-methylnaphthalene, 1,4-dimethylnaphthalene or x-ethylnaphthalene.

The ether solvent includes diethyl ether, methyl ether, ethylene glycol dimethyl ether (DME), diethylene glycol dimethyl ether (DEGDME), tetraethylene glycol dimethyl ether (TEGDME), dipropyl ether, diisopropyl ether. Ether, ethyl butyl ether, dibutyl ether, diamyl ether, diisoamyl ether, dihexyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxocyclopentane, 4-methyl-1, 3-dioxolane, dimethoxymethane, 1,2-dimethoxypropane, dioxolane, 1,4-dioxane, ethylene oxide, propylene oxide, 1,1 Mixing any one or more of diethoxyethane, dimethyl sulfoxide, sulfolane or dimethyl sulfone. Among them, preferred is one of DME, DEGDME or TEGDME.

The reaction of the alkali metal or the aromatic compound in an ether solvent is carried out, and the following description will be made by mixing sodium, biphenyl and DME solvent as an example.

The reaction process is as shown in the following formula 1:

The characteristics of the liquid metal negative electrode materials formed by different aromatic compounds and metallic sodium in DME solvent are given in Table 1 below.

Table 1

The liquid metal anode material provided by the embodiment of the invention has liquid fluidity, good electronic and ionic conductivity, low potential, high safety and good wetting property, low cost and abundant material resources, and the material is rich. The battery negative electrode has high specific energy and long cycle life.

Example 2

Embodiment 2 of the present invention provides a method for preparing a liquid metal anode material as described in Embodiment 1 above. The method comprises: adding an alkali metal and an aromatic compound to an ether solvent in a protective atmosphere of argon at a certain molar ratio, and allowing to stand to obtain the liquid metal negative electrode material.

Specifically, the alkali metal may be any one or more of sodium metal (Na), lithium metal (Li) or potassium (K);

The aromatic compound may be any one or more of biphenyl (BP), a derivative of biphenyl, naphthalene (NP), a derivative of naphthalene, a derivative of ruthenium or osmium;

Wherein; the derivative of biphenyl may specifically be: biphenyl, dichlorobiphenyl, tetrachlorobiphenyl, terphenyl, x-methylbiphenyl, x-ethylbiphenyl, etc.;

The derivative of naphthalene may specifically be: phenanthrene, dichloronaphthalene, tetrachloronaphthalene, x-methylnaphthalene, 1,4-dimethylnaphthalene or x-ethylnaphthalene.

The ether solvent includes diethyl ether, methyl ether, ethylene glycol dimethyl ether (DME), diethylene glycol dimethyl ether (DEGDME), tetraethylene glycol dimethyl ether (TEGDME), dipropyl ether, diisopropyl ether. Ether, ethyl butyl ether, dibutyl ether, diamyl ether, diisoamyl ether, dihexyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxocyclopentane, 4-methyl-1, 3-dioxolane, dimethoxymethane, 1,2-dimethoxypropane, dioxolane, 1,4-dioxane, ethylene oxide, propylene oxide, 1,1 Mixing any one or more of diethoxyethane, dimethyl sulfoxide, sulfolane or dimethyl sulfone. Among them, preferred is one of DME, DEGDME or TEGDME.

Hereinafter, the preparation process of the biphenyl-DME-metal sodium liquid metal negative electrode will be specifically described as an example.

In a glove box filled with Ar gas, a ratio of 0.13 g of metallic sodium and 1.54 g of biphenyl were weighed into the same 20 ml weighing bottle for use. Then, 10 mL of ethylene glycol dimethyl ether (DME) liquid was injected into a weighing bottle containing sodium metal and biphenyl using a 10 ml pipette, and the solution quickly turned dark green. The obtained dark green solution was allowed to stand for 2 hours to obtain a liquid metal negative electrode of biphenyl-DME-metal sodium. Fig. 1 is an electrochemical impedance spectrum of the above biphenyl-DME-metal sodium liquid metal negative electrode. It can be seen from the figure that the resistance is 86 ohms when the concentration is 1 mol/l. From the conductivity formula σ=k/R, σ _1mol/l =1.2x10 ^-2 S/cm can be calculated, and we can test the conductivity of 1mol/l biphenyl-DME-metal lithium σ _1mol/l =1.1x10 ^{- 2} S/cm. The above biphenyl-DME-metal sodium liquid metal negative electrode safety test is shown in Fig. 2, which shows a graph of the solution of the biphenyl-DME-metal sodium solution dropwise with deionized water as a function of time. It can be seen from the figure that the reaction of the biphenyl-DME-metal sodium solution with water is not as intense as the reaction of the metal sodium with water, indicating that the safety performance of the biphenyl-DME-metal sodium solution as the negative electrode is higher than that of the metal sodium negative electrode. The solubility test of the above biphenyl-DME-metal sodium liquid negative electrode is shown in Fig. 3. It can be seen from the figure that the solubility of biphenyl-DME-metal sodium is more than 5 mol/l, according to the specific capacity of biphenyl-DME-metal sodium. Calculated at 151 mAh/g, the volume specific capacity of biphenyl-DME-metal sodium was 1.4 x 10 ² Ah/L, and high solubility gave high volume energy density. It should be noted that the concentrations described in the present invention are all calculated according to the concentration of biphenyl, wherein the molar ratio of biphenyl to alkali metal is 1:1, but the ratio is only used to illustrate the invention in the examples, and The scale of the invention is not limited to this ratio.

Example 3

The embodiment of the invention further provides a chargeable room temperature liquid metal battery of a liquid metal anode material. The negative electrode material of the battery is the liquid metal negative electrode material described in the above Embodiment 1, and can be obtained by the method described in the above Example 2.

In addition, the chargeable room temperature liquid metal battery provided in this embodiment further includes:

One of a liquid positive electrode material or a slurry positive electrode material, and an ion conductive, electronically insulating solid electrolyte membrane;

Wherein the solid electrolyte comprises Na ₃ Zr ₂ Si ₂ PO ₁₂ ceramic, Na-β′′-Al ₂ O ₃ ceramic, K-β′′-Al ₂ O ₃ ceramic for conducting sodium ions, lithium ions or potassium ions Any of Li ₇ La ₃ Zr ₂ O ₁₂ ceramics or Li ₁₀ GeP ₂ S ₁₂ ceramics.

Hereinafter, the liquid positive electrode material or the slurry positive electrode material will be separately described in each of Examples 4-8.

Example 4

Embodiment 4 of the present invention is for explaining a liquid positive electrode material described in the above Embodiment 3, and a preparation method thereof.

The liquid positive electrode material is:

Any one of phthalone, a derivative of p-benzoquinone, a derivative of hydrazine, hydrazine, a derivative of hydrazine, hydrazine, a derivative of phenanthrenequinone or phenanthrenequinone, a solute, Any of ether, propylene carbonate or tetraethylene glycol dimethyl ether as a solvent.

The preparation method can be:

0.1 to 5 mol of p-benzoquinone, a derivative of p-benzoquinone, a derivative of hydrazine, hydrazine, a derivative of hydrazine, hydrazine, a derivative of phenanthrenequinone or phenanthrenequinone, a solute, dissolved in A liquid auxiliary material is obtained by adding a certain amount of a supporting electrolyte to 1 L of any solvent such as ethylene glycol dimethyl ether, propylene carbonate or tetraethylene glycol dimethyl ether.

For example, in a specific example, taking 蒽醌-PC-sodium perchlorate liquid cathode material as an example, the specific preparation steps are as follows:

2.08 g of hydrazine was dissolved in 10 mL of PC solvent, and 1.4 g of sodium trifluoromethanesulfonate was added as a supporting electrolyte, and stirred until completely dissolved to obtain a desired liquid positive electrode material.

Example 5

Embodiment 5 of the present invention is for explaining a liquid positive electrode material described in the above Embodiment 3, and another preparation method thereof.

The liquid positive electrode material is:

Solving any of benzophenone, anthracene, tetracene, pentacene or hydrazine, and using ethylene glycol dimethyl ether, diethylene glycol dimethyl ether or tetraethylene glycol dimethyl ether as solvent , the composition of the liquid.

The preparation method can be:

0.1 to 5 mol of benzophenone, hydrazine, tetracene, pentacene or hydrazine as a solute, dissolved in 1 L of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether or tetraethylene glycol In any solvent of dimethyl ether, a certain amount of alkali metal is added and allowed to stand to obtain the liquid positive electrode material.

For example, in a specific example, taking a tetracene-DME-metal sodium liquid cathode material as an example, the specific preparation steps are as follows:

2.20 g of tetraphenylene was weighed and dissolved in 10 mL of DME solvent, and 160 mg of sodium metal was added as an additive, and stirred until completely dissolved to obtain a desired liquid positive electrode material.

Example 6

Embodiment 6 of the present invention is for explaining a liquid positive electrode material described in the above Embodiment 3, and a further preparation method thereof.

The liquid positive electrode material is:

A solution comprising Na ₂ S _x as a solute and using dimethyl sulfoxide, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether or water as a solvent; wherein 3 ≤ x ≤ 12.

The preparation method comprises the following:

Adding Na ₂ S and S to dimethyl sulfoxide, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether or water according to the molar ratio of Na ₂ S/S=1/(x-1) And adding a certain amount of supporting electrolyte to stir to completely dissolve, that is, obtaining the liquid positive electrode material; wherein, 3≤x≤12.

For example, in a specific example, the Na ₂ S _x -DMSO liquid positive electrode material is taken as an example, and the specific preparation steps are as follows:

According to the molar ratio of Na ₂ S / S = 1 / (x-1), weigh the appropriate amount of Na ₂ S and S into dimethyl sulfoxide (DMSO) solution, while adding a certain amount of trifluoromethanesulfonic acid Sodium is stirred as a supporting electrolyte until it is completely dissolved to obtain the desired liquid positive electrode material. The liquid positive electrode material has good solubility. For example, the solubility of Na ₂ S ₈ and Na ₂ S ₄ prepared by this method is more than 1 mol/L.

Example 7

Embodiment 7 of the present invention is for explaining a preparation method of the slurry positive electrode material described in the above Embodiment 3.

Na _0.44 MnO ₂ , NaTi ₂ (PO ₄ ) ₃ , Na ₃ V ₂ (PO _{4) 3} , Na _0.8 Li _0.1 Ni _0.25 Mn _0.65 O ₂ , NaMg _0.1 Ni _0.4 Mn _0.2 Ti _0.3 O ₂ , S, K ₃ Solid powder and carbon powder of any one or more kinds of positive electrode active materials of Fe(CN) ₆ , Na ₄ Fe(CN) ₆ , FePO _{4 ,} etc. are uniformly mixed in a certain mass ratio, and a certain amount of supporting electrolyte is added and stirred. That is, the liquid positive electrode material is obtained.

Example 8

Embodiment 8 of the present invention is for explaining another preparation method of the slurry positive electrode material described in the above Embodiment 3.

Any of the liquid positive electrode materials and carbon powders provided in the above Example 4 or Example 5 or Example 6 are uniformly mixed in a certain mass ratio, and a certain amount of supporting electrolyte is added and stirred to obtain the liquid positive electrode material.

The preparation method and performance of the chargeable room temperature liquid metal battery provided by the present invention are further described in detail below through some specific embodiments.

Example 9

The present embodiment is for explaining the preparation method of the biphenyl-DME-metal sodium liquid metal negative electrode material provided by the present invention and the 蒽醌-PC-sodium perchlorate liquid positive electrode material for charging and discharging the room temperature liquid metal battery. And its charge and discharge performance.

The specific preparation method is as follows:

1. 10 mL of the prepared ruthenium-PC-sodium perchlorate liquid positive electrode material was injected into the stainless steel case shown in Fig. 4 as a positive electrode.

2. The prepared Na-β"-Al ₂ O ₃ ceramic tube was inserted into a stainless steel case containing a liquid positive electrode material as an electrolyte and a separator.

3. Take the prepared liquid metal anode material, for example, 10 mL of a biphenyl-DME-metal sodium solution into the above Na-β"-Al ₂ O ₃ ceramic tube as a negative electrode, and insert the prepared aluminum mesh into the negative electrode liquid as a negative electrode. Current collector.

4. The obtained monomer battery port is completely sealed to obtain the chargeable room temperature liquid metal battery of the present invention.

The battery test was carried out in a constant current charge and discharge mode with a discharge cut-off voltage of 1.5 V, a charge cut-off voltage of 2.6 V, and a charge and discharge current of 0.4 mA. The test results are shown in Fig. 8. The discharge capacity in the first week is up to 300 mAh/g, the charging capacity is 250 mAh/g, the first week Coulomb efficiency is about 84%, and the discharge potential platform is about 1.75V. The cycle performance test results are shown in Figure 9. The test results show that the discharge capacity is maintained at 88% after 400 cycles.

Example 10

The present embodiment is for explaining the preparation method of the biphenyl-DME-metal sodium liquid metal anode material provided by the present invention and the chargeable room temperature liquid metal battery constructed by the tantalum-carbon black slurry cathode material, and the charging method thereof Discharge performance.

The specific preparation method is as follows:

1. Weigh 10 mg of hydrazine and 2 mg of carbon black and add a certain amount of PC-sodium perchlorate solution to form a slurry, which is then injected into a stainless steel case shown in Fig. 4 as a positive electrode.

2. The prepared Na-β"-Al ₂ O ₃ ceramic tube was inserted into a stainless steel shell containing the slurry positive electrode material as an electrolyte and a separator.

3. Take the prepared liquid anode material, for example, 10 mL of a biphenyl-DME-metal sodium solution into the above Na-β"-Al ₂ O ₃ ceramic tube as a negative electrode, and insert the prepared aluminum mesh into the negative electrode liquid as a set. fluid.

4. The obtained monomer battery port is completely sealed to obtain the chargeable room temperature liquid metal battery of the present invention.

The battery test was carried out in a constant current charge and discharge mode with a discharge cut-off voltage of 1.2 V, a charge cut-off voltage of 2.6 V, and a charge and discharge current of 1 mA. The test results are shown in Fig. 10. The discharge capacity in the first week is up to 320 mAh/g, the charging capacity is 260 mAh/g, and the first week coulombic efficiency is about 81%.

Example 11

The present embodiment is for explaining the preparation method of the biphenyl-DME-metal sodium liquid metal anode material provided by the present invention and the benzoquinone-PC-sodium perchlorate liquid cathode material for charging and discharging the room temperature liquid metal battery. And its charge and discharge performance.

The specific preparation method is as follows:

1. 10 mL of the prepared benzoquinone-PC-sodium perchlorate liquid positive electrode material was injected into the stainless steel case shown in Fig. 4 as a positive electrode.

2. The prepared Na ₃ Zr ₂ Si ₂ PO ₁₂ ceramic tube was inserted into a stainless steel case containing a liquid positive electrode material as an electrolyte and a separator.

3. Take the prepared liquid anode material, for example, 10 mL of a biphenyl-DME-metal sodium solution into the above Na ₃ Zr ₂ Si ₂ PO ₁₂ ceramic tube as a negative electrode, and insert the prepared aluminum mesh into the negative electrode liquid as a current collector. .

4. The obtained monomer battery port is completely sealed to obtain the chargeable room temperature liquid metal battery of the present invention.

The battery test was carried out in a constant current charge and discharge mode with a discharge cut-off voltage of 1.5 V, a charge cut-off voltage of 2.6 V, and a charge and discharge current of 0.4 mA. The test results are shown in Figure 11. It can be seen that the first week discharge capacity can reach 260mAh/g, the charge capacity is 300mAh/g, the first week Coulomb efficiency is about 86%, and the charge and discharge potential platform is about 2.4V.

Example 12

The present embodiment is for explaining the preparation method of the biphenyl-DME-metal sodium liquid metal negative electrode material provided by the present invention and the 苊醌-PC-sodium perchlorate liquid positive electrode material for charging and discharging the room temperature liquid metal battery. And its charge and discharge performance.

The specific preparation method is as follows:

1. 10 mL of the prepared ruthenium-PC-sodium perchlorate liquid positive electrode material was injected into the stainless steel case shown in Fig. 4 as a positive electrode.

2. Insert the prepared Na ₃ Zr ₂ Si ₂ PO ₁₂ ceramic tube into the stainless steel case containing the liquid positive electrode material as the electrolyte and the separator.

3. Take the prepared liquid anode material, for example, 10 mL of a biphenyl-DME-metal sodium solution into the above Na ₃ Zr ₂ Si ₂ PO ₁₂ ceramic tube as a negative electrode, and insert the prepared aluminum mesh into the negative electrode liquid as a current collector. .

4. The obtained monomer battery port is completely sealed to obtain the chargeable room temperature liquid metal battery of the present invention.

The battery test was carried out in a constant current charge and discharge mode with a discharge cut-off voltage of 1.5 V, a charge cut-off voltage of 3 V, and a charge and discharge current of 0.4 mA. The test results are shown in Fig. 12. It can be seen that the first week discharge capacity can reach 180mAh/g, the charging capacity is 160mAh/g, the first week coulombic efficiency is about 88%, and the charge and discharge potential platform is about 1.9~2.1V. Figure 13 is a comparison diagram of the first week charge and discharge based on the above method, using 蒽醌-PC-sodium perchlorate, benzoquinone-PC-sodium perchlorate, and strontium-PC-sodium perchlorate as liquid positive electrode materials, respectively. It can be seen from the figure that benzoquinone-PC-sodium perchlorate has a higher potential and 蒽醌-PC-sodium perchlorate has a lower potential, but it can be seen from the above test that 蒽醌-PC-high The cycle stability of sodium chlorate is the best and has good prospects.

Example 13

The present embodiment is for explaining the preparation method of the biphenyl-DME-metal sodium liquid metal anode material provided by the present invention and the chargeable room temperature liquid metal battery constructed by using NaTi ₂ (PO ₄ ) ₃ , and the charge and discharge performance thereof. .

The specific preparation method is as follows:

1. Mix NaTi ₂ (PO ₄ ) ₃ powder with acetylene black and binder polyvinylidene fluoride (PVDF) in a weight ratio of 80:10:10, and add an appropriate amount of N-methylpyrrolidone (NMP) solvent. Grinding to form a slurry in a dry environment at room temperature, and then uniformly coating the slurry on a current collector aluminum foil, drying and then cutting a 60×20 mm pole piece onto the outer wall of the Na-β”-Al ₂ O ₃ ceramic tube. Thereafter, the inside of the stainless steel case shown in Fig. 4 was inserted, and 400 mL of sodium perchlorate and propylene carbonate electrolyte were added dropwise as a positive electrode.

2. 10 mL of the prepared biphenyl, DME, and metal sodium liquid anode material was injected into the above Na-β"-Al ₂ O ₃ ceramic tube as a negative electrode, and the prepared aluminum mesh was inserted into the negative electrode liquid as a current collector.

3. The obtained monomer battery port is completely sealed to obtain the chargeable room temperature liquid metal battery of the present invention.

The battery test was carried out in a constant current charge and discharge mode with a discharge cut-off voltage of 1.5 V, a charge cut-off voltage of 2.6 V, and a charge and discharge current of 0.04 mA. The test results are shown in Figure 14. It can be seen that the first week discharge capacity can reach 110mAh/g, the charge capacity is 109mAh/g, the first week Coulomb efficiency is about 99%, and the charge and discharge potential platform is about 1.9~2.1V. The cycle performance test results are shown in Figure 15. After 60 weeks of cycling, the capacity was maintained at 87%.

Example 14

The present embodiment is for explaining a biphenyl-DME-metal sodium liquid metal anode material provided by the present invention, and a preparation method of a chargeable room temperature liquid metal battery constructed by using Na ₃ V ₂ (PO ₄ ) ₃ , and a charging method thereof Discharge performance.

The specific preparation method is as follows:

1. Mix Na ₃ V ₂ (PO ₄ ) ₃ powder with acetylene black and binder PVDF in a weight ratio of 80:10:10, add an appropriate amount of NMP solvent, and grind to form a slurry in a dry environment at room temperature, and then The slurry was uniformly coated on the current collector aluminum foil, dried and cut into 60 x 20 mm pole pieces wound on the outer wall of the Na ₃ Zr ₂ Si ₂ PO ₁₂ tube, and then inserted into the stainless steel shell shown in Fig. 4. At the same time, 400 mL of sodium perchlorate and propylene carbonate electrolyte were added dropwise as a positive electrode.

2. 10 mL of the prepared biphenyl, DME, and metal sodium liquid anode material was injected into the above Na ₃ Zr ₂ Si ₂ PO ₁₂ ceramic tube as a negative electrode, and the prepared aluminum mesh was inserted into the negative electrode liquid as a current collector.

3. The obtained monomer battery port is completely sealed to obtain the chargeable room temperature liquid metal battery of the present invention.

The battery was tested in a constant current charge and discharge mode with a discharge cut-off voltage of 2.8V, a charge cut-off voltage of 3.6V, and a charge and discharge current of 0.04mA. The test results are shown in Figure 16. It can be seen that the first week is charged. The capacitance can reach 115mAh/g, the discharge capacity is 109mAh/g, the first week Coulomb efficiency is about 95%, and the charge and discharge potential platform is about 3.1~3.3V.

Example 15

This embodiment is for explaining the preparation method of the biphenyl-DME-metal sodium liquid metal anode material provided by the present invention and the Na _0.44 MnO ₂ structure and the chargeable and dischargeable liquid metal battery, and the charge and discharge performance thereof.

The specific preparation method is as follows:

1. The Na _0.44 MnO ₂ powder and the carbon black are mixed in a weight ratio of 80:10, and an appropriate amount of sodium trifluoromethanesulfonate and propylene carbonate are added to support the electrolyte to form a slurry, and then the slurry is injected into FIG. 4 The inside of the stainless steel shell was shown as a positive electrode, and then the prepared Na-β"-Al2O3 ceramic tube was inserted into the stainless steel shell.

2. 10 mL of the prepared biphenyl, DME, and metal sodium liquid anode material was injected into the above Na-β"-Al ₂ O ₃ ceramic tube as a negative electrode, and the prepared aluminum mesh was inserted into the negative electrode liquid as a current collector.

3. The obtained monomer battery port is completely sealed to obtain the chargeable room temperature liquid metal battery of the present invention.

The battery was tested in a constant current charge and discharge mode with a discharge cut-off voltage of 2V, a charge cut-off voltage of 3.8V, and a charge and discharge current of 0.1mA. The test results are shown in Fig. 17. It can be seen that the first week discharge capacity can reach 110 mAh/g, the charge capacity is 109 mAh/g, the first week coulombic efficiency is about 99%, and the charge and discharge potential ranges from 2 to 3.8V.

Example 16

The present embodiment is for explaining the preparation method of the biphenyl-DME-metal sodium liquid metal anode material provided by the present invention and the 芘-DME-metal sodium liquid cathode material, and the preparation method thereof Discharge performance.

The specific preparation method is as follows:

1. Take 10 mL of prepared yttrium-DME-metal sodium liquid cathode material into the stainless steel shown in Figure 4. The inside of the steel casing serves as a positive electrode.

2. The prepared Na-β"-Al ₂ O ₃ ceramic tube was inserted into a stainless steel case containing a liquid positive electrode material as an electrolyte and a separator.

3. Take the prepared liquid anode material, such as 10 mL of biphenyl-DME-metal sodium solution, into the above Na-β"-Al ₂ O ₃ ceramic tube as a negative electrode, and insert the prepared aluminum mesh into the negative liquid as Current collector.

4. The obtained monomer battery port is completely sealed to obtain the chargeable room temperature liquid metal battery of the present invention.

The battery was tested in a charge-discharge mode with a limited capacity. The discharge voltage was 0.45 V, the charge was 0.6 V, and the charge and discharge current was 0.04 mA. The test results are shown in Fig. 18. It can be seen that the discharge capacity is up to 120 mAh/g, the charging capacity is 120 mAh/g, and the voltage is not significantly attenuated after ten cycles.

Example 17

The present embodiment is for explaining the preparation method of the biphenyl-DME-metal sodium liquid metal negative electrode material provided by the present invention and the tetraphenyl-DME-metal sodium liquid positive electrode material, and the preparation method of the chargeable room temperature liquid metal battery, and Its charge and discharge performance.

The specific preparation method is as follows:

1. 10 mL of the prepared tetraphenyl-DME-metal sodium liquid positive electrode material was injected into the stainless steel case shown in Fig. 2 as a positive electrode.

2. The prepared Na ₃ Zr ₂ Si ₂ PO ₁₂ tube was inserted into a stainless steel case containing a liquid positive electrode material as an electrolyte and a separator.

3. A prepared liquid negative electrode material, for example, 10 mL of a biphenyl-DME-metal sodium solution is injected into the above Na ₃ Zr ₂ Si ₂ PO ₁₂ tube as a negative electrode, and the prepared aluminum mesh is inserted into the negative electrode liquid as a current collector.

4. The obtained monomer battery port is completely sealed to obtain the chargeable room temperature liquid metal battery of the present invention.

The battery test is carried out in a constant current charge and discharge mode, and the discharge cutoff voltage is 0.6V. The voltage is 1.3V, and the charge and discharge current is 0.04mA. The test results are shown in Fig. 19. It can be seen that the discharge specific capacity is up to 120 mAh/g, and the charge specific capacity is 105 mAh/g.

Example 18

The present embodiment is for explaining the preparation method of the biphenyl-DME-metal sodium liquid metal negative electrode material provided by the present invention and the Na ₂ S ₈ -DMSO liquid positive electrode material, and the charging method thereof Discharge performance.

The specific preparation method is as follows:

1. 10 mL of the prepared Na ₂ S ₈ -DMSO liquid positive electrode material was injected into the stainless steel case shown in Fig. 4 as a positive electrode.

2. The Na-β"-Al ₂ O ₃ ceramic tube was inserted into a stainless steel case containing a liquid positive electrode material as an electrolyte and a separator.

3. Take the prepared liquid metal anode material, for example, 10 mL of a biphenyl-DME-metal sodium solution into the above Na-β"-Al ₂ O ₃ ceramic tube as a negative electrode, and insert the prepared aluminum mesh into the negative liquid as Current collector.

4. The obtained monomer battery port is completely sealed to obtain the chargeable room temperature liquid metal battery of the present invention.

The battery was tested in a constant current charge and discharge mode with a discharge cutoff voltage of 1.5V, a charge cutoff voltage of 2.1V, and a charge and discharge current of 0.1mA. The test results are shown in Fig. 20. It can be seen that the first cycle discharge capacity is up to 160 mAh/g, the charge specific capacity is 159 mAh/g, and the charge and discharge efficiency is 99%. The safety test of biphenyl-DME-metal sodium liquid metal anode is carried out. Figure 21 shows the change of biphenyl-DME-metal sodium solution over time after adding polysulfide ion. The biphenyl-DME-metal can be seen from the figure. The reaction between sodium and polysulfide ions is mild, which further demonstrates that the battery composed of biphenyl-DME-metal sodium solution anode and polysulfide ion has higher safety performance.

Example 19

The present embodiment is for explaining a biphenyl-DME-metal sodium liquid metal negative electrode material provided by the present invention, and a preparation method of a chargeable room temperature liquid metal battery constructed by using a Na ₂ S ₁₂ -DMSO liquid positive electrode material, and charging thereof Discharge performance.

The specific preparation method is as follows:

1. 10 mL of the prepared Na ₂ S ₁₂ -DMSO liquid positive electrode material was injected into the stainless steel case shown in Fig. 4 as a positive electrode.

2. The Na-β"-Al ₂ O ₃ ceramic tube was inserted into a stainless steel case containing a liquid positive electrode material as an electrolyte and a separator.

3. Take the prepared liquid metal anode material, for example, 10 mL of a biphenyl-DME-metal sodium solution into the above Na-β"-Al ₂ O ₃ ceramic tube as a negative electrode, and insert the prepared aluminum mesh into the negative liquid as Current collector.

4. The obtained monomer battery port is completely sealed to obtain the chargeable room temperature liquid metal battery of the present invention.

The battery was tested in a constant current charge and discharge mode with a discharge cutoff voltage of 1.6V, a charge cutoff voltage of 2.5V, and a charge and discharge current of 0.1mA. The test results are shown in Fig. 22. It can be seen that the first cycle discharge capacity is up to 250 mAh/g, the charge specific capacity is 250 mAh/g, and the charge and discharge efficiency is 99%.

Example 20

The present embodiment is for explaining the preparation method of the biphenyl-DME-metal sodium liquid metal negative electrode material provided by the present invention and the S-carbon black slurry positive electrode material, and the charging and discharging thereof performance.

The specific preparation method is as follows:

1. Weigh 6 mg of sulfur and 1 mg of carbon black and add a certain amount of NaSO ₃ CF ₃ -DOL-DME solution to form a slurry and inject it into the stainless steel shell shown in Fig. 4 as a positive electrode.

2. The prepared Na ₃ Zr ₂ Si ₂ PO ₁₂ tube was inserted into a stainless steel case containing a liquid positive electrode material as an electrolyte and a separator.

3. 10 mL of the prepared biphenyl-DME-metal sodium liquid metal negative electrode material was injected into the above Na ₃ Zr ₂ Si ₂ PO ₁₂ ceramic tube as a negative electrode, and the prepared aluminum mesh was inserted into the negative electrode liquid as a current collector.

4. The obtained monomer battery port is completely sealed to obtain the chargeable room temperature liquid metal battery of the present invention.

The battery test was carried out in a constant current charge and discharge mode with a discharge cut-off voltage of 1.5 V, a charge cut-off voltage of 2.6 V, and a charge and discharge current of 0.2 mA. The test results are shown in Fig. 23. It can be seen that the discharge capacity in the first week can reach 700 mAh/g, the charging capacity is 550 mAh/g, the coulombic efficiency in the first week is about 79%, and the discharge potential platform is about 1.7 to 1.9V. When the charge and discharge range is 1.7 to 2.8 V, the test results are shown in Fig. 24, and the first week discharge capacity is 360 mAh/g, the charge capacity is 340 mAh/g, and the coulombic efficiency is 94%.

Example 21

The present embodiment is for explaining the biphenyl-DME-metal sodium liquid metal anode material provided by the present invention, and the room temperature liquid metal battery constructed by the tetramethoxypiperidine-PC-sodium perchlorate liquid cathode material. Preparation method, and its charge and discharge performance.

The specific preparation method is as follows:

1. 10 mL of the prepared tetramethoxypiperidine-PC-sodium perchlorate liquid positive electrode material was injected into the stainless steel case shown in Fig. 4 as a positive electrode.

2. The prepared Na-β"-Al ₂ O ₃ ceramic tube is inserted into a stainless steel case containing a liquid positive electrode material as an electrolyte and a separator.

3. 10 mL of the prepared biphenyl-DME-metal sodium liquid metal anode material was injected into the above Na-β"-Al ₂ O ₃ ceramic tube as a negative electrode, and the prepared aluminum mesh was inserted into the negative electrode liquid as a current collector. .

4. The obtained monomer battery port is completely sealed to obtain the chargeable room temperature liquid metal battery of the present invention.

The battery test was carried out in a constant current charge and discharge mode with a discharge cut-off voltage of 2.5 V, a charge cut-off voltage of 3.6 V, and a charge and discharge current of 0.04 mA. The test results are shown in Fig. 25. It can be seen that the first week charging capacity can reach 205mAh/g, the discharge capacity is 200mAh/g, the first week coulombic efficiency is about 97%, and the charge and discharge potential platform is about 3.1~3.4V.

Example 22

This embodiment is for explaining the specific preparation method and the charge and discharge performance of the biphenyl-DME-metal sodium liquid metal anode material provided by the present invention and the K ₃ Fe(CN) ₆ aqueous solution.

The specific preparation method is as follows:

1. 10 mL of the prepared positive electrode material of K ₃ Fe(CN) ₆ aqueous solution was injected into the stainless steel case shown in FIG. 4 as a positive electrode.

2. The prepared Na ₃ Zr ₂ Si ₂ PO ₁₂ ceramic tube was inserted into a stainless steel case containing a liquid positive electrode material as an electrolyte and a separator.

3. 10 mL of the prepared biphenyl-DME-metal sodium liquid metal negative electrode material was injected into the above Na ₃ Zr ₂ Si ₂ PO ₁₂ ceramic tube as a negative electrode, and the prepared aluminum mesh was inserted into the negative electrode liquid as a current collector.

4. The sealed battery cell of the present invention can be obtained by completely sealing the obtained single battery port.

The battery test was carried out in a constant current charge and discharge mode with a discharge cut-off voltage of 2.5 V, a charge cut-off voltage of 3.8 V, and a charge and discharge current of 0.04 mA. The test results are shown in Fig. 26. It can be seen that the first week charging capacity can reach 68mAh/g, the discharge capacity is 74mAh/g, the first week Coulomb efficiency is about 91%, and the charge and discharge potential platform is about 3.1~3.3V.

Example 23

The present embodiment is for explaining the preparation method of the biphenyl-DME-metal sodium liquid metal negative electrode material provided by the present invention and the benzophenone-DME-metal sodium liquid positive electrode material, and the preparation method of the chargeable room temperature liquid metal battery. And its charge and discharge performance.

The specific preparation method is as follows:

1. 10 mL of the prepared positive electrode material of benzophenone-DME-metal sodium solution was injected into the stainless steel case shown in FIG. 4 as a positive electrode.

2. The prepared Na-β"-Al ₂ O ₃ ceramic tube was inserted into a stainless steel case containing a liquid positive electrode material as an electrolyte and a separator.

3. 10 mL of the prepared biphenyl-DME-metal sodium liquid metal anode material was injected into the above Na-β"-Al ₂ O ₃ ceramic tube as a negative electrode, and the prepared aluminum mesh was inserted into the negative electrode liquid as a current collector. .

4. The sealed battery cell of the present invention can be obtained by completely sealing the obtained single battery port.

The battery test was carried out in a constant current charge and discharge mode with a discharge cut-off voltage of 0.8 V, a charge cut-off voltage of 1.5 V, and a charge and discharge current of 0.04 mA. The test results are shown in Fig. 27. It can be seen that the first week discharge capacity can reach 300 mAh/g, the charging capacity is 250 mAh/g, the first week coulombic efficiency is about 83%, and the discharge potential platform is about 0.8-1V.

Example 24

The present embodiment is for explaining the preparation method of the biphenyl-DME-metal sodium liquid metal negative electrode material provided by the present invention and the iodine-PC-sodium perchlorate liquid positive electrode material, and the preparation method of the chargeable room temperature liquid metal battery, and Its charge and discharge performance.

The specific preparation method is as follows:

1. 10 mL of the prepared positive electrode material of iodine-PC-sodium perchlorate solution was injected into the stainless steel case shown in Fig. 4 as a positive electrode.

2. The prepared Na ₃ Zr ₂ Si ₂ PO ₁₂ ceramic tube was inserted into a stainless steel case containing a liquid positive electrode material as an electrolyte and a separator.

3. 10 mL of the prepared biphenyl-DME-metal sodium liquid metal negative electrode material was injected into the above Na ₃ Zr ₂ Si ₂ PO ₁₂ ceramic tube as a negative electrode, and the prepared aluminum mesh was inserted into the negative electrode liquid as a current collector.

4. The obtained monomer battery port is completely sealed to obtain the chargeable room temperature liquid metal battery of the present invention.

The battery test was carried out in a constant current charge and discharge mode. The discharge cut-off voltage was 2V, the charge cut-off voltage was 3V, and the charge and discharge current was 0.1mA. The test results are shown in Fig. 28. It can be seen that the first week discharge capacity can reach 200 mAh/g, the charging capacity is 210 mAh/g, the first week coulombic efficiency is about 95%, and the charge and discharge potential platform is about 2.8-3.0V.

Example 25

The present embodiment is for explaining the biphenyl-DME-metal sodium liquid metal anode material provided by the present invention, and the preparation method of the chargeable room temperature liquid metal battery constructed by the ferrocene-PC-sodium perchlorate liquid cathode material , and its charge and discharge performance.

The specific preparation method is as follows:

1. 10 mL of the prepared ferrocene-PC-sodium perchlorate solution cathode material was injected into the stainless steel shell shown in FIG. 4 as a positive electrode.

2. The prepared Na ₃ Zr ₂ Si ₂ PO ₁₂ ceramic tube was inserted into a stainless steel case containing a liquid positive electrode material as an electrolyte and a separator.

3. 10 mL of the prepared biphenyl-DME-metal sodium liquid metal negative electrode material was injected into the above Na ₃ Zr ₂ Si ₂ PO ₁₂ ceramic tube as a negative electrode, and the prepared aluminum mesh was inserted into the negative electrode liquid as a current collector.

4. The obtained monomer battery port is completely sealed to obtain the chargeable room temperature liquid metal battery of the present invention.

The battery test was carried out in a constant current charge and discharge mode with a discharge cut-off voltage of 2.5 V, a charge cut-off voltage of 3.1 V, and a charge and discharge current of 0.1 mA. The test results are shown in Fig. 29. It can be seen that the first week charging capacity can reach 200mAh/g, the discharge capacity is 210mAh/g, the first week Coulomb efficiency is about 95%, and the charge and discharge potential platform is about 2.7~3.0V.

Example 26

The present embodiment is for explaining the preparation method of the biphenyl-DME-metal sodium liquid metal anode material provided by the present invention and the 苊-DME-metal sodium liquid cathode material, and the preparation method thereof Discharge performance.

The specific preparation method is as follows:

1. 10 mL of the prepared cesium-DME-metal sodium solution was injected into the stainless steel case shown in Fig. 4 as a positive electrode.

2. The prepared Na-β"-Al ₂ O ₃ ceramic tube was inserted into a stainless steel case containing a liquid positive electrode material as an electrolyte and a separator.

3. 10 mL of the prepared biphenyl-DME-metal sodium liquid metal anode material was injected into the above Na-β"-Al ₂ O ₃ ceramic tube as a negative electrode, and the prepared aluminum mesh was inserted into the negative electrode liquid as a current collector. .

4. The obtained monomer battery port is completely sealed to obtain the chargeable room temperature liquid metal battery of the present invention.

The battery test was carried out in a constant current charge and discharge mode with a discharge cut-off voltage of 0 V, a charge cut-off voltage of 0.65 V, and a charge and discharge current of 0.02 mA. The test results are shown in Fig. 30. It can be seen that the first week charging capacity can reach 150 mAh/g, the charging capacity is 130 mAh/g, the first week coulombic efficiency is about 86%, and the discharge potential platform is about 0.2-0.3V.

Example 27

The present embodiment is for explaining the biphenyl-DME-metal sodium liquid metal anode material provided by the present invention, and the preparation method of the chargeable room temperature liquid metal battery constructed by the quinoline-PC-sodium perchlorate liquid cathode material , and its charge and discharge performance.

The specific preparation method is as follows:

1. 10 mL of the prepared quinoxaline-PC-sodium perchlorate solution was injected into the stainless steel shell shown in Fig. 4 as a positive electrode.

2. The prepared Na ₃ Zr ₂ Si ₂ PO ₁₂ ceramic tube was inserted into a stainless steel case containing a liquid positive electrode material as an electrolyte and a separator.

3. 10 mL of the prepared biphenyl-DME-metal sodium liquid metal negative electrode material was injected into the above Na ₃ Zr ₂ Si ₂ PO ₁₂ ceramic tube as a negative electrode, and the prepared aluminum mesh was inserted into the negative electrode liquid as a current collector.

4. The obtained monomer battery port is completely sealed to obtain the chargeable room temperature liquid metal battery of the present invention.

The battery test was carried out in a constant current charge and discharge mode with a discharge cut-off voltage of 1.5 V, a charge cut-off voltage of 2.6 V, and a charge and discharge current of 0.1 mA. The test results are shown in Figure 31, and it can be seen that the first week of discharge capacitance The amount can reach 120mAh/g, the charging capacity is 80mAh/g, and the first week Coulomb efficiency is about 67%.

Example 28

The present embodiment is for explaining the preparation method of the biphenyl-DME-metal sodium liquid metal negative electrode material provided by the present invention and the 蒽醌-PC-sodium perchlorate liquid positive electrode material for charging and discharging the room temperature liquid metal battery. And its charge and discharge performance.

The specific preparation method is as follows:

1. 10 mL of the prepared cesium-PC-sodium perchlorate solution was injected into the stainless steel case shown in Fig. 4 as a positive electrode.

2. The prepared Na-β"-Al ₂ O ₃ ceramic tube was inserted into a stainless steel case containing a liquid positive electrode material as an electrolyte and a separator.

3. 10 mL of the prepared naphthalene-DME-metal sodium liquid metal negative electrode material was injected into the above Na-β"-Al ₂ O ₃ ceramic tube as a negative electrode, and the prepared aluminum mesh was inserted into the negative electrode liquid as a current collector.

4. The obtained monomer battery port is completely sealed to obtain the chargeable room temperature liquid metal battery of the present invention.

The battery test was carried out in a constant current charge and discharge mode with a discharge cut-off voltage of 1.5 V, a charge cut-off voltage of 2.6 V, and a charge and discharge current of 0.2 mA. The test results are shown in Fig. 32. It can be seen that the discharge capacity in the first week can reach 215 mAh/g, the charging capacity is 209 mAh/g, the first week coulombic efficiency is about 97%, and the discharge potential is 1.6 to 1.8V.

Example 29

This example is intended to illustrate the reversibility of the electrochemical reaction of the biphenyl-DME-metal sodium liquid metal anode material provided by the present invention.

The specific method is:

1. Mix excess 5 mg of ruthenium and polyethylene oxide in a ratio of 5:1 and add a certain amount of PC-sodium perchlorate support electrolyte to the Na-β"-Al ₂ O ₃ ceramic sheet. .

2. A liquid metal negative electrode containing 4.1 mg of NaBP was dropped on the bottom of the button cell case.

3. The Na-β"-Al ₂ O ₃ ceramic sheet coated with ruthenium was pressed against the liquid metal negative electrode, and the back cover was buckled and tested.

The battery test was carried out in a constant current charge and discharge mode with a discharge cut-off voltage of 1.0 V, a charge cut-off voltage of 2.7 V, and a charge and discharge current of 0.1 mA. The test results are shown in Fig. 33. The specific capacity is calculated according to the mass of NaBP. It can be seen that the first week discharge capacity is 76 mAh/g and the charge capacity is 65 mAh/g, which indicates the high reversibility of NaBP storage.

In the above embodiments, the preparation method and performance of the chargeable room temperature liquid metal battery provided by the present invention are described, although in various embodiments, the biphenyl-DME-metal sodium is exemplified as the liquid metal negative electrode material. However, the scope of protection of the present invention is not limited thereby. The negative electrode material of the chargeable room temperature liquid metal battery of the present invention may comprise any one of the liquid metal negative electrode materials provided in Embodiment 1 of the present invention.

The liquid metal anode material provided in the above embodiments of the present invention has liquid fluidity, good electronic and ionic conductivity, low potential, high safety and good wetting property, and is prepared by using the material as a negative electrode. The battery has the characteristics of high specific energy and long cycle life, and can be used for storage of power output of power stations such as solar energy and wind energy.

The structure of the room temperature liquid metal battery which can be charged and discharged according to the embodiment of the present invention may be a cylindrical battery as shown in FIG. 4 as described in the above embodiments, or a double flow battery as shown in FIG. 5 . Or a single flow battery as shown in Fig. 6, or a flat metal battery as shown in Fig. 7. Hereinafter, the structure of the chargeable and dischargeable room temperature liquid metal battery provided by the embodiment of the present invention will be further described in detail with reference to Embodiment 30 to Embodiment 33, respectively.

Example 30

This embodiment is for explaining the structure of a cylindrical chargeable room temperature liquid metal battery provided by an embodiment of the present invention.

As shown in FIG. 4, FIG. 4 is a schematic structural view of a cylindrical battery. The physical map of the cylindrical battery can be as shown in FIG. As shown in FIG. 4, the cylindrical battery may include: a stainless steel case and a solid electrolyte tube;

The solid electrolyte tube is nested in the stainless steel casing without contact, and a sealed space between the inner wall of the stainless steel casing and the outer wall of the solid electrolyte tube is used for accommodating the liquid positive electrode material; For accommodating the liquid metal anode material.

At the time of discharge, electrons are reduced from the negative electrode to the positive electrode through an external circuit to reduce the positive electrode active material, while sodium ions pass from the negative electrode to the positive electrode through the solid electrolyte. The charging process is such that electrons reach the negative electrode from the positive electrode, and ions also pass from the positive electrode to the negative electrode through the solid electrolyte.

Example 31

This embodiment is for explaining the structure of the two-liquid flow-fillable room temperature liquid metal battery provided by the embodiment of the present invention.

As shown in FIG. 5, a battery case, a solid electrolyte membrane, a positive electrode storage tank, a negative liquid storage tank, and two pumps;

The solid electrolyte membrane partitions the battery case into a sealed positive electrode space and a negative electrode space, wherein the positive electrode space is connected to the positive electrode liquid storage tank, and the liquid contained in the positive electrode liquid storage tank is connected by a pump The positive electrode material is pumped into the positive electrode space, and the negative electrode space is connected to the negative electrode storage tank, and the liquid metal negative electrode material accommodated in the negative electrode storage tank is pumped into the negative electrode space by a pump. The working principle is similar to that of a cylindrical liquid metal battery that can be charged and discharged at room temperature, and will not be described again.

Example 32

This embodiment is for explaining the structure of a single-liquid flow-fillable room temperature liquid metal battery provided by an embodiment of the present invention.

As shown in FIG. 6, the battery case, the solid electrolyte membrane, the positive electrode reservoir and the pump;

The solid electrolyte membrane partitions the battery case into a sealed positive electrode space and a negative electrode space, wherein the positive electrode space is connected to the positive electrode liquid storage tank, and the pump is used to accommodate the positive electrode liquid storage tank A liquid positive electrode material is pumped into the positive electrode space, and the negative electrode space is for accommodating the liquid metal negative electrode material. The working principle is similar to that of a cylindrical liquid metal battery that can be charged and discharged at room temperature, and will not be described again.

Example 33

The embodiment is used for the junction of the flat panel chargeable liquid metal battery provided by the embodiment of the present invention. The structure is explained.

As shown in Figure 7, the battery case and the solid electrolyte membrane;

The solid electrolyte membrane divides the battery case into a sealed positive electrode space for accommodating the liquid positive electrode material, and a negative electrode space for accommodating the liquid metal negative electrode material. The working principle is similar to that of a cylindrical liquid metal battery that can be charged and discharged at room temperature, and will not be described again.

The specific embodiments of the present invention have been described in detail with reference to the preferred embodiments of the present invention. All modifications, equivalent substitutions, improvements, etc., made within the spirit and scope of the invention are intended to be included within the scope of the invention.

Claims (17)

1. A liquid metal anode material, characterized in that the anode material is a dark green liquid formed by mixing an alkali metal, an aromatic compound and an ether solvent;

   Wherein the alkali metal is any one or more of sodium metal, lithium metal or potassium metal;

   The aromatic compound is any one or more of biphenyl, a derivative of biphenyl, a derivative of naphthalene, naphthalene, or a derivative of ruthenium or osmium;

   The ether solvent includes diethyl ether, methyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dipropyl ether, diisopropyl ether, ethyl butyl ether, two Butyl ether, dipentyl ether, diisoamyl ether, dihexyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxocyclopentane, 4-methyl-1,3-dioxolane, two Methoxymethane, 1,2-dimethoxypropane, dioxolane, 1,4-dioxane, ethylene oxide, propylene oxide, 1,1-diethoxyethane, two Any one or more of methyl sulfoxide, sulfolane or dimethyl sulfone.
2. A method of preparing a liquid metal anode material according to claim 1, wherein the method comprises:

   The alkali metal and the aromatic compound are added to the ether solvent in a certain molar ratio in a protective atmosphere of argon, and left to stand to obtain the liquid metal negative electrode material;

   Wherein the alkali metal is any one or more of sodium metal, lithium metal or potassium metal;

   The aromatic compound is any one or more of biphenyl, a derivative of biphenyl, a derivative of naphthalene, naphthalene, or a derivative of ruthenium or osmium;

   The ether solvent includes diethyl ether, methyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dipropyl ether, diisopropyl ether, ethyl butyl ether, two Butyl ether, dipentyl ether, diisoamyl ether, dihexyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxocyclopentane, 4-methyl-1,3-dioxolane, two Methoxymethane, 1,2-dimethoxypropane, dioxolane, 1,4-dioxane, ethylene oxide, propylene oxide, 1,1-diethoxyethane, two Any one or more of methyl sulfoxide, sulfolane or dimethyl sulfone.
3. A chargeable room temperature comprising the liquid metal anode material according to claim 1 Liquid metal battery.
4. The chargeable room temperature liquid metal battery according to claim 3, wherein the chargeable room temperature liquid metal battery further comprises:

   One of a liquid positive electrode material or a slurry positive electrode material, and an ion conductive, electronically insulating solid electrolyte membrane;

   Wherein the solid electrolyte comprises Na ₃ Zr ₂ Si ₂ PO ₁₂ ceramic, Na-β′′-Al ₂ O ₃ ceramic, K-β′′-Al ₂ O ₃ ceramic for conducting sodium ions, lithium ions or potassium ions Any of Li ₇ La ₃ Zr ₂ O ₁₂ ceramics or Li ₁₀ GeP ₂ S ₁₂ ceramics.
5. The chargeable room temperature liquid metal battery according to claim 4, wherein the preparation method of the slurry positive electrode material comprises:

   The solid powder and the carbon powder of the positive electrode active material are uniformly mixed in a certain mass ratio, and a certain amount of the supporting electrolyte is added and stirred to obtain the liquid positive electrode material;

   Wherein, the positive active material includes: Na _0.44 MnO ₂ , NaTi ₂ (PO ₄ ) ₃ , Na ₃ V ₂ (PO ₄ ) ₃ , Na _0.8 Li _0.1 Ni _0.25 Mn _0.65 O ₂ , NaMg _0.1 Ni _0.4 Mn _0.2 Ti Any one or more of _0.3 O ₂ , S, K ₃ Fe(CN) ₆ , Na ₄ Fe(CN) ₆ , and FePO ₄ .
6. The chargeable room temperature liquid metal battery according to claim 4, wherein the preparation method of the slurry positive electrode material comprises:

   The liquid positive electrode material and the carbon powder are uniformly mixed in a certain mass ratio, and a certain amount of the supporting electrolyte is added and stirred to obtain the liquid positive electrode material.
7. The chargeable room temperature liquid metal battery according to claim 4 or 6, wherein the liquid positive electrode material is:

   Mixing one or more of p-benzoquinone, a derivative of p-benzoquinone, a derivative of hydrazine, hydrazine, a derivative of hydrazine, hydrazine, a phenanthrenequinone or a phenanthrenequinone as a solute, A liquid composed of one or more of ethylene glycol dimethyl ether, propylene carbonate or tetraethylene glycol dimethyl ether, dimethylformamide or N-methylpyrrolidone.
8. The chargeable room temperature liquid metal battery according to any one of claims 4 or 6 or 7, The method for preparing the liquid cathode material comprises:

   Mixed with any one or more of 0.1 to 5 mol of p-benzoquinone, a derivative of p-benzoquinone, a derivative of hydrazine, hydrazine, a derivative of hydrazine, hydrazine, a derivative of phenanthrenequinone or phenanthrenequinone Is a solute, dissolved in 1L of any one or more mixed solvents of ethylene glycol dimethyl ether, propylene carbonate, tetraethylene glycol dimethyl ether, dimethylformamide or N-methylpyrrolidone, added A quantity of supporting electrolyte is obtained to obtain the liquid positive electrode material.
9. The chargeable room temperature liquid metal battery according to claim 4 or 6, wherein the liquid positive electrode material is:

   Solvent with benzophenone, hydrazine, tetracene, pentacene or hydrazine, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dimethyl A liquid composed of one or more of formamide or N-methylpyrrolidone mixed as a solvent.
10. The chargeable room temperature liquid metal battery according to any one of claims 4 or 6 or 9, wherein the liquid cathode material preparation method comprises:

    0.1 to 5 mol of benzophenone, hydrazine, tetracene, pentacene or hydrazine mixed as a solute, dissolved in 1 L of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether In a solvent mixture of one or more of tetraethylene glycol dimethyl ether, dimethylformamide or N-methylpyrrolidone, a certain amount of alkali metal is added and allowed to stand to obtain the liquid positive electrode material.
11. The chargeable room temperature liquid metal battery according to claim 4 or 6, wherein the liquid positive electrode material is:

    Na ₂ S _x as a solute, one or more of dimethyl sulfoxide, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dimethylformamide, N-methylpyrrolidone or water A solution composed of a solvent; wherein 3 ≤ x ≤ 12.
12. The chargeable room temperature liquid metal battery according to claim 4 or claim 6 or claim 11, wherein the preparation method of the liquid positive electrode material comprises:

    Add Na ₂ S and S to dimethyl sulfoxide, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dimethyl ketone according to the molar ratio of Na ₂ S/S=1/(x-1) Any one or more mixed solvents of amide, N-methylpyrrolidone or water, and adding a certain amount of supporting electrolyte to stir to completely dissolve, thereby obtaining the liquid positive electrode material;

    Where 3≤x≤12.
13. The chargeable room temperature liquid metal battery according to claim 4, wherein the chargeable room temperature liquid metal battery is a cylindrical battery, comprising:

    Stainless steel housing and solid electrolyte tube;

    The solid electrolyte tube is nested in the stainless steel casing without contact, and a sealed space between the inner wall of the stainless steel casing and the outer wall of the solid electrolyte tube is used for accommodating the liquid positive electrode material; For accommodating the liquid metal anode material.
14. The chargeable room temperature liquid metal battery according to claim 4, wherein the chargeable room temperature liquid metal battery is a two-flow battery, comprising:

    a battery case, a solid electrolyte membrane, a positive electrode reservoir, a negative reservoir, and two pumps;

    The solid electrolyte membrane partitions the battery case into a sealed positive electrode space and a negative electrode space, wherein the positive electrode space is connected to the positive electrode liquid storage tank, and the liquid contained in the positive electrode liquid storage tank is connected by a pump The positive electrode material is pumped into the positive electrode space, and the negative electrode space is connected to the negative electrode storage tank, and the liquid metal negative electrode material accommodated in the negative electrode storage tank is pumped into the negative electrode space by a pump.
15. The chargeable room temperature liquid metal battery according to claim 4, wherein the chargeable room temperature liquid metal battery is a single flow battery, comprising:

    a battery case, a solid electrolyte membrane, a positive electrode reservoir, and a pump;

    The solid electrolyte membrane partitions the battery case into a sealed positive electrode space and a negative electrode space, wherein the positive electrode space is connected to the positive electrode liquid storage tank, and the pump is used to accommodate the positive electrode liquid storage tank A liquid positive electrode material is pumped into the positive electrode space, and the negative electrode space is for accommodating the liquid metal negative electrode material.
16. The chargeable room temperature liquid metal battery according to claim 4, wherein the chargeable room temperature liquid metal battery is a flat metal battery, comprising:

    a battery case and a solid electrolyte membrane;

    The solid electrolyte membrane divides the battery case into a sealed positive electrode space for accommodating the liquid positive electrode material, and a negative electrode space for accommodating the liquid metal negative electrode material.
17. The use of a chargeable room temperature liquid metal battery according to any of claims 3-16, wherein the chargeable room temperature liquid metal battery is used for solar power generation, wind power generation, smart grid adjustment Large-scale energy storage equipment for peaks, distributed power stations, backup power sources or communication base stations.

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