A membrane-free dual-phase battery electrolyte and a membrane-free dual-phase battery

Abstract

This invention belongs to the field of membrane-free battery technology, specifically relating to a membrane-free two-phase battery electrolyte and a membrane-free two-phase battery. The membrane-free two-phase battery of this invention uses a low-temperature stable organic solvent and water as solvents for the two-phase electrolytes, uses zinc ion salt as the negative electrode electrolyte, adds a certain proportion of antifreeze material, and uses an organic solvent containing alkane additives to complex halogen monomers as the positive electrode electrolyte. This invention avoids the high cost and short lifespan problems associated with using ion exchange membranes in liquid batteries, while ensuring that the battery electrolyte remains liquid at low temperatures. This significantly expands the temperature range of the liquid energy storage battery system, avoids the use of external heat sources in winter conditions, and prevents severe zinc corrosion at room temperature, further reducing the cost of the energy storage system.

Description

Technical Field

[0001] This invention belongs to the field of membrane-free battery technology, specifically relating to a membrane-free dual-phase battery electrolyte and a membrane-free dual-phase battery. Background Technology

[0002] Unlike lithium-based batteries, liquid active material batteries, such as flow batteries, are considered one of the most promising electrochemical technologies for large-scale energy storage. They achieve safe, grid-scale energy storage by dissolving active materials in an electrolyte. However, aqueous electrolytes suffer from freezing, slow kinetics, and limited solubility, making stable and high-power operation impossible in extremely cold climates. The presence of costly separators further hinders battery performance at low temperatures. The advent of membrane-free batteries offers an effective solution to these problems. By storing the positive and negative electrode active materials in two immiscible solvents, cross-contamination between the active materials is avoided. Furthermore, the elimination of ion exchange membranes significantly reduces battery costs and extends battery life.

[0003] Currently, in terms of wide-temperature adaptability, most applications of membrane-free batteries are usually limited to environments above 0 degrees Celsius. When the temperature continues to drop and the electrolyte freezes, the battery can only operate with the assistance of an external heat source, resulting in high cost and low performance. Summary of the Invention

[0004] To address the shortcomings of the existing technology, the present invention aims to provide a membrane-free biphase battery electrolyte and a membrane-free biphase battery. The purpose of the present invention is to develop a novel battery system to address the problems of electrolyte freezing, limited solubility, and slow kinetics in batteries when the ambient temperature decreases due to seasons or weather, or even in extremely cold weather.

[0005] To solve the above-mentioned technical problems, the present invention adopts the following technical solution:

[0006] A membrane-free dual-phase battery electrolyte and a membrane-free dual-phase battery, wherein the dual-phase electrolyte comprises an aqueous phase negative electrode electrolyte with a volume ratio of 1:1 to 5 and a non-aqueous phase positive electrode electrolyte.

[0007] The aqueous phase negative electrode electrolyte includes water, negative electrode active material, and aqueous phase antifreeze material, wherein the aqueous phase antifreeze material is one or more of ethylene glycol, bis(2-hydroxyethyl) ether, or diethylene glycol monomethyl ether.

[0008] When the aqueous antifreeze material is ethylene glycol, the volume ratio of the aqueous antifreeze material to water is 60% to 99%; when the aqueous antifreeze material is bis(2-hydroxyethyl) ether, the volume ratio of the aqueous antifreeze material to water is 80% to 200%; when the aqueous antifreeze material is diethylene glycol monomethyl ether, the volume ratio of the aqueous antifreeze material to water is 10% to 30%.

[0009] The non-aqueous positive electrode electrolyte includes a non-aqueous solvent, a positive electrode supporting electrolyte salt, and a positive electrode antifreeze material. The positive electrode supporting electrolyte salt is an alkane ammonium bromide salt, and the concentration of the alkane ammonium bromide salt is 0.5 mol / L to 5.0 mol / L.

[0010] The membrane-free dual-phase battery electrolyte and membrane-free dual-phase battery provided by this invention use an aqueous negative electrode electrolyte and a non-aqueous positive electrode electrolyte as the dual-phase electrolyte, and low-temperature stable organic solvent and water as the solvents for the dual-phase electrolyte. An aqueous antifreeze material is added, and an organic solvent containing alkane additives to complex halogen elements is used as the positive electrode electrolyte. This avoids the high cost and short lifespan issues associated with using ion exchange membranes in liquid batteries, while ensuring that the battery electrolyte remains liquid at low temperatures. This significantly expands the temperature range of the liquid energy storage battery system, avoids the use of external heat sources in winter conditions, and prevents severe zinc corrosion at room temperature, further reducing the cost of the energy storage system.

[0011] In a preferred embodiment of the present invention, the volume ratio of the aqueous negative electrode electrolyte to the non-aqueous positive electrode electrolyte is 1:1.

[0012] In a preferred embodiment of the present invention, the alkane ammonium bromide salt is one or more of dodecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide, or octadecyltrimethylammonium bromide.

[0013] In a preferred embodiment of the present invention, the negative electrode active material is a zinc ion salt.

[0014] In a preferred embodiment of the present invention, the zinc ion salt is one or more of zinc oxalate, zinc tetrafluoromethanesulfonate, zinc dodecyl sulfate, zinc benzenesulfonate, or zinc tetrafluoroborate.

[0015] In a preferred embodiment of the present invention, the zinc ion salt concentration is 0.1 mol / L to 10 mol / L, and more preferably 0.1 mol / L to 3 mol / L.

[0016] In a preferred embodiment of the present invention, the non-aqueous solvent is an organic solvent.

[0017] In a preferred embodiment of the present invention, the organic solvent is dichloromethane, bromonaphthalene, bromobenzene, ethyl acetate, or tetrahydrofuran.

[0018] In a preferred embodiment of the present invention, the concentration of the positive electrode supporting electrolyte salt is further preferably 2.5 mol / L to 4.3 mol / L.

[0019] Another object of the present invention is to provide a membrane-free dual-phase battery, comprising a battery body and the membrane-free dual-phase battery electrolyte described in any of the above claims.

[0020] In a preferred embodiment of the present invention, the battery body includes a positive current collector, a negative current collector, and a battery container. The positive current collector and the negative current collector are disposed on both sides of the battery container, and the battery container is filled with a membrane-free dual-phase battery electrolyte.

[0021] In a preferred embodiment of the present invention, the positive electrode material is aluminum foil or titanium plate.

[0022] In a preferred embodiment of the present invention, the negative electrode material is carbon felt, graphite felt, glassy carbon electrode or carbon cloth.

[0023] In a preferred embodiment of the present invention, a positive electrode plate and a negative electrode plate are provided on both sides of the battery container, and the battery container is filled with a biphase electrolyte. The biphase electrolyte needs to be left to stand for 12 to 20 hours to allow the electrolyte phases to stabilize.

[0024] The use of antifreeze materials in the aqueous phase keeps the active electrolyte substances in a liquid state between -35 and 35 degrees Celsius. In the membrane-free battery of the present invention, the organic phase is confined to halogen bromine by a long-chain complexing agent. The organic phase remains liquid at -35 to 35 degrees Celsius and can prevent charging products from diffusing into the aqueous phase and causing battery failure even without a separator.

[0025] Compared with the prior art, the beneficial effects of the present invention are:

[0026] 1. The membrane-free dual-phase battery of the present invention uses an aqueous negative electrode electrolyte and a non-aqueous positive electrode electrolyte as the dual-phase electrolyte, and low-temperature stable organic solvent and water as solvents for the two-phase electrolyte. Low-freezing-point low-temperature additives such as ethylene glycol, bis(2-hydroxyethyl) ether, or diethylene glycol monomethyl ether, which are miscible with water, are added as antifreeze materials for the aqueous phase. Furthermore, an organic solvent that complexes halogen monomers with alkane ammonium bromide salt additives is used as the positive electrode electrolyte. This avoids the high cost and short lifespan problems associated with using ion exchange membranes in liquid batteries, while ensuring that the battery electrolyte remains liquid at low temperatures. This significantly expands the temperature range of the liquid energy storage battery system, avoids the use of external heat sources in winter conditions, and prevents severe corrosion of zinc at room temperature, further reducing the cost of the energy storage system.

[0027] 2. This invention designs a membrane-free dual-phase liquid active material battery system that does not suffer performance degradation or freezing due to low temperatures. It selects a low-freezing-point additive miscible with water as the aqueous phase antifreeze material, keeping the electrolyte in a liquid state between -35°C and +35°C. The battery can cope with seasonal or weather-related failures. Furthermore, the organic system design avoids the use of high-cost, low-performance separators. The organic phase uses long-chain alkane complexing additives to confine the halogen elemental positive electrode active material within the organic phase, preventing self-discharge caused by cross-contamination of active materials. The organic phase remains liquid between -35°C and +35°C and can prevent charging products from diffusing into the aqueous phase and causing battery failure even without a separator. This results in lower-temperature corrosion resistance than at room temperature, further improving battery cycle performance.

[0028] 3. Based on the electrolyte designed in this invention, the battery can achieve stable cycling for more than 50 cycles at a low temperature of -20 degrees Celsius, with a coulombic efficiency of over 99.99% and an energy efficiency of up to 73.7%, which is close to the performance of a room temperature battery. Attached Figure Description

[0029] Figure 1 The diagram shows the liquid state of the aqueous electrolyte in the water-organic membrane-free biphase battery of the present invention at a low temperature of -20°C; (a) the aqueous electrolyte container is upright at low temperature; (b) the aqueous electrolyte container is inverted at low temperature.

[0030] Figure 2 The following are examples of the membrane-free biphase electrolyte of the present invention at a low temperature of -20°C: (a) aqueous phase electrolyte; (b) organic phase electrolyte; and (c) biphase electrolyte.

[0031] Figure 3 These are SEM images of zinc sheet corrosion in the aqueous phase at room temperature (a) and -20℃ (b) according to the present invention.

[0032] Figure 4 This is a comparison of the charge-discharge cycle performance of the membrane-free dual-phase battery of the present invention at room temperature (b) and -20℃ (a).

[0033] Figure 5 This is a comparison diagram of the aqueous electrolyte of the present invention at a low temperature of -20℃, showing (a) frozen and (b) unfrozen.

[0034] Figure 6 This is a comparison diagram of (a) diffusion and (b) non-diffusion of the halogen active material of the present invention at a low temperature of -20℃.

[0035] Figure 7 This is a comparison diagram of the organic phase active material of the present invention at a low temperature of -20℃, showing (a) unfrozen and (b) frozen. Detailed Implementation

[0036] The following detailed description, in conjunction with embodiments of the present invention and accompanying drawings, provides a clear and complete illustration of the technical solutions in these embodiments. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0037] It should be noted that all technical terms used in this invention are for the purpose of describing specific embodiments only and are not intended to limit the scope of protection of this invention. Unless otherwise specified, all raw materials, reagents, instruments and equipment used in the following embodiments of this invention can be purchased from the market or prepared by existing methods.

[0038] Example 1

[0039] A membrane-free two-phase battery electrolyte: 2 mol / L zinc dodecyl sulfate and 70% ethylene glycol in deionized water are used as the aqueous phase electrolyte. 3.5 mol / L ammonium octadecyl bromide is added to dichloromethane and complexed with bromine to form the organic phase electrolyte. The aqueous phase electrolyte and the organic phase electrolyte are mixed together at a 1:1 volume ratio to form the membrane-free two-phase battery electrolyte.

[0040] A water-based organic membrane-free dual-phase battery suitable for low-temperature environments is provided. The positive electrode is a graphite felt electrode, the negative electrode is a carbon cloth negative electrode, and the electrolyte is the same as the above-mentioned membrane-free dual-phase battery electrolyte. After the electrolyte naturally separates into layers, the battery is assembled into a membrane-free dual-phase battery in a battery container and left to stand for 15 hours.

[0041] Example 2

[0042] A membrane-free two-phase battery electrolyte: 0.1 mol / L zinc dodecyl sulfate and 60% ethylene glycol in deionized water are used as the aqueous phase electrolyte. 0.5 mol / L octadecyl ammonium bromide is added to dichloromethane and complexed with bromine to form the organic phase electrolyte. The aqueous phase electrolyte and the organic phase electrolyte are mixed together at a volume ratio of 1:3 to form the membrane-free two-phase battery electrolyte.

[0043] A water-based organic membrane-free dual-phase battery suitable for low-temperature environments is provided. The positive electrode is a graphite felt electrode, the negative electrode is a carbon cloth negative electrode, and the electrolyte is the same as the above-mentioned membrane-free dual-phase battery electrolyte. After the electrolyte naturally separates into layers, the battery is assembled into a membrane-free dual-phase battery in a battery container and left to stand for 12 hours.

[0044] Example 3

[0045] A membrane-free two-phase battery electrolyte: 1.5 mol / L zinc dodecyl sulfate and 99% ethylene glycol in deionized water are used as the aqueous phase electrolyte. 5 mol / L octadecyl ammonium bromide is added to dichloromethane and complexed with bromine to form the organic phase electrolyte. The aqueous phase electrolyte and the organic phase electrolyte are mixed together at a volume ratio of 1:5 to form the membrane-free two-phase battery electrolyte.

[0046] A water-based organic membrane-free dual-phase battery suitable for low-temperature environments is provided. The positive electrode is a graphite felt electrode, the negative electrode is a carbon cloth negative electrode, and the electrolyte is the same as the above-mentioned membrane-free dual-phase battery electrolyte. After the electrolyte naturally separates into layers, the battery is assembled into a membrane-free dual-phase battery in a battery container and left to stand for 20 hours.

[0047] Example 4

[0048] A membrane-free two-phase battery electrolyte: 2 mol / L zinc dodecyl sulfate and 100% bis(2-hydroxyethyl) ether in deionized water are used as the aqueous phase electrolyte. 3.5 mol / L octadecyl ammonium bromide is added to dichloromethane and complexed with bromine to form the organic phase electrolyte. The aqueous phase electrolyte and the organic phase electrolyte are mixed together at a 1:1 volume ratio to form the membrane-free two-phase battery electrolyte.

[0049] A water-based organic membrane-free dual-phase battery suitable for low-temperature environments is provided. The positive electrode is a graphite felt electrode, the negative electrode is a carbon cloth negative electrode, and the electrolyte is the same as the above-mentioned membrane-free dual-phase battery electrolyte. After the electrolyte naturally separates into layers, the battery is assembled into a membrane-free dual-phase battery in a battery container and left to stand for 15 hours.

[0050] Example 5

[0051] A membrane-free two-phase battery electrolyte: 2 mol / L zinc dodecyl sulfate and 20% diethylene glycol monomethyl ether in deionized water are used as the aqueous phase electrolyte. 3.5 mol / L octadecyl ammonium bromide is added to dichloromethane and complexes with bromine to form the organic phase electrolyte. The aqueous phase electrolyte and the organic phase electrolyte are mixed together at a 1:1 volume ratio to form the membrane-free two-phase battery electrolyte.

[0052] A water-based organic membrane-free dual-phase battery suitable for low-temperature environments is provided. The positive electrode is a graphite felt electrode, the negative electrode is a carbon cloth negative electrode, and the electrolyte is the same as the above-mentioned membrane-free dual-phase battery electrolyte. After the electrolyte naturally separates into layers, the battery is assembled into a membrane-free dual-phase battery in a battery container and left to stand for 15 hours.

[0053] Comparative Example 1

[0054] A membrane-free two-phase battery electrolyte is prepared by dissolving 2 mol / L zinc dodecyl sulfate and 15% ethylene glycol in deionized water as an aqueous phase electrolyte, adding 2 mol / L ammonium octadecyl bromide to dichloromethane and complexing it with bromine to form an organic phase electrolyte, and mixing the aqueous phase electrolyte and the organic phase electrolyte together at a 1:1 volume ratio to form the membrane-free two-phase battery electrolyte.

[0055] A membrane-free two-phase battery is provided, with a graphite felt electrode as the positive electrode and a carbon cloth negative electrode as the negative electrode. The electrolyte is the aforementioned membrane-free two-phase electrolyte. The battery is assembled in a battery container and left to stand for 15 hours.

[0056] Figure 5 This is a comparison of (a) the aqueous electrolyte of the present invention frozen at -20℃ and (b) not frozen. In Comparative Example 1, the volume of the aqueous antifreeze material in the negative electrode electrolyte is small, causing the aqueous phase to freeze and the battery to malfunction. The freezing result of the aqueous electrolyte at -20℃ is shown below. Figure 5 As shown.

[0057] Comparative Example 2

[0058] A membrane-free two-phase battery electrolyte comprises an aqueous electrolyte consisting of 1 mol / L methyl-ethyl pyrrolidine bromide and 65% ethylene glycol in deionized water, and an organic electrolyte consisting of 1 mol / L methyl-ethyl pyrrolidine bromide added to dichloromethane and complexing with bromine. The aqueous electrolyte and the organic electrolyte are mixed together in a 1:1 volume ratio to form the membrane-free two-phase battery electrolyte.

[0059] A membrane-free two-phase battery is provided, with a graphite felt electrode as the positive electrode and a carbon cloth negative electrode as the negative electrode. The electrolyte is the aforementioned membrane-free two-phase electrolyte. The battery is assembled in a capacitor and left to stand for 15 hours.

[0060] Figure 6 This is a comparison of (a) diffusion and (b) non-diffusion of the halogen active material at -20°C. In Comparative Example 2, the weak interaction between the antifreeze material, the aqueous active material, and the methyl-ethyl pyrrolidine bromide additive causes the halogen active material to diffuse into the aqueous phase during charging and undergo self-discharge, leading to rapid battery failure. The diffusion results of the halogen active material at -20°C are shown below. Figure 6 As shown.

[0061] Comparative Example 3

[0062] A membrane-free two-phase battery electrolyte is provided, comprising 1.5 mol / L tetrabutylammonium bromide and 37.5% ethylene glycol in deionized water as the aqueous electrolyte, and 1.5 mol / L tetrabutylammonium bromide additive added to dichloromethane and complexed with bromine to form an organic electrolyte. The aqueous electrolyte and the organic electrolyte are mixed together in a 1:1 volume ratio to form the membrane-free two-phase battery electrolyte.

[0063] A membrane-free two-phase battery is provided, with a graphite felt electrode as the positive electrode and a carbon cloth negative electrode as the negative electrode. The electrolyte is the aforementioned membrane-free two-phase electrolyte. The battery is assembled in a battery container and left to stand for 15 hours.

[0064] Figure 7 This is a comparison diagram of (a) unfrozen and (b) frozen organic phase active material at -20℃. In Comparative Example 3, the excessively strong interaction between the tetrabutylammonium bromide organic complexing agent and the antifreeze additive leads to low-temperature freezing of the organic phase active material, resulting in solid formation at the positive electrode and battery malfunction. The freezing results of the organic phase active material are shown below. Figure 7 As shown.

[0065] Results Analysis

[0066] The aqueous organic membrane-free two-phase battery prepared in Example 1 uses a graphite felt electrode as the positive electrode and a carbon cloth electrode as the negative electrode. The aqueous phase consists of 2 mol / L zinc dodecyl sulfate and 70% ethylene glycol in deionized water. Figure 1 These are liquid state diagrams of the aqueous electrolyte in the water-organic membrane-free dual-phase battery of the present invention at a low temperature of -20°C; (a) aqueous electrolyte container upright at low temperature; (b) aqueous electrolyte container inverted at low temperature. Figure 1 As shown, at -20 degrees Celsius, the aqueous electrolyte remains liquid after 48 hours of freezing due to the presence of water-soluble ethylene glycol material with an ultra-low freezing point. When the container is inverted, the electrolyte flows to the cap instead of freezing and remaining at the bottom.

[0067] 3.5 mol / L octadecylammonium bromide was added to dichloromethane and complexed with the bromine generated by oxidation to form an organic phase. Dichloromethane, as an organic solvent, is liquid at -20 degrees Celsius. At the same time, octadecylammonium bromide serves as a supporting salt for the positive electrode electrolyte, complexing the active materials of the battery and preventing them from contacting the aqueous active materials, which would cause the battery to self-discharge, thus ensuring the low-temperature performance and long-term stability of the battery.

[0068] Figure 2 The following are examples of the membrane-free two-phase electrolyte of the present invention at a low temperature of -20°C: (a) aqueous phase electrolyte; (b) organic phase electrolyte; and (c) two-phase electrolyte. Figure 2 As shown, when the aqueous electrolyte and organic electrolyte are mixed together in a 1:1 volume ratio and naturally separated into layers, they are assembled into a membrane-free biphase battery and left to stand for 15 hours. The halogens in the organic phase do not diffuse into the aqueous phase, causing the battery to deactivate.

[0069] Figure 3SEM images of the upper aqueous phase zinc sheet after 24 hours at room temperature (b) and -20°C (a) show that the corrosion of the zinc sheet is significantly improved at -20°C, proving that the electrolyte of this battery can better suppress the diffusion of positive electrode active material at low temperature, thereby improving the battery's long-term range and performance at low temperature.

[0070] Figure 4 This study compares the cycle performance of membrane-free two-phase cells at room temperature and -20°C. The test conditions were: current density 1 mA / cm². 2 The cutoff voltage range is 0.1V to 2V, and the single-cycle capacity is 20mAh. As shown in the figure, this battery design can stably cycle for more than 50 cycles in a low-temperature environment, with a coulombic efficiency of over 99.99% and an energy efficiency of up to 73.7%, which is close to the performance of a room-temperature battery.

[0071] The mechanism of action and challenges of the antifreeze material in this invention: In the zinc-halogen dual-phase membrane-free battery system, unlike other traditional battery designs, the active material is liquid and soluble in more than one solvent, and there is no separator. Therefore, multiple factors must be considered when selecting antifreeze materials, rather than simply choosing conventional antifreeze additives: 1. Stability of the water-oil interface, as the water and oil phases are immiscible; 2. Preventing the aqueous electrolyte from freezing by combining the aqueous active material and additives; 3. Preventing the organic electrolyte from freezing by combining the organic halogen complexing agent additives; 4. Preventing the oil-phase halogen active material from diffusing into the aqueous phase during charging; 5. Maintaining battery performance comparable to that at room temperature. Therefore, the selection of antifreeze materials is entirely based on the design of the zinc-halogen dual-phase membrane-free battery system, and the interaction forces between solute and solvent within the system need to be within a specific range. This significantly limits the selection of antifreeze materials and requires precise control of various parameters, including the formulation.

[0072] In summary, this invention designs a membrane-free, two-phase liquid active material battery system that does not suffer performance degradation or freezing due to low temperatures. A low-freezing-point additive miscible with water is selected as the aqueous phase antifreeze material, maintaining the electrolyte in a liquid state between -35°C and +35°C. This allows the battery to cope with seasonal or weather-related failures. Furthermore, the organic system design avoids the use of high-cost, low-performance separators. The organic phase confines the positive electrode active material, preventing self-discharge caused by cross-contamination of active materials, resulting in higher low-temperature corrosion resistance than at room temperature, further improving battery cycle performance.

[0073] It should be noted that when numerical ranges are involved in this invention, it should be understood that both endpoints of each numerical range, as well as any value between the two endpoints, can be selected. Since the steps and methods used are the same as in the embodiments, preferred embodiments are described here to avoid redundancy. Although preferred embodiments of this invention have been described, those skilled in the art, once they understand the basic inventive concept, can make other changes and modifications to these embodiments. Therefore, the appended scope of protection is intended to be interpreted as including the preferred embodiments and all changes and modifications falling within the scope of this invention.

[0074] Obviously, those skilled in the art can make various modifications and variations to this invention without departing from its spirit and scope. Therefore, if these modifications and variations fall within the scope of protection of this invention and its equivalents, this invention also intends to include these modifications and variations.

Claims

1. A membrane-free two-phase battery electrolyte, characterized in that, The electrolyte includes an aqueous negative electrode electrolyte with a volume ratio of 1:1 to 5 and a non-aqueous positive electrode electrolyte. The aqueous phase negative electrode electrolyte includes water, negative electrode active material and aqueous phase antifreeze material, wherein the aqueous phase antifreeze material is bis(2-hydroxyethyl) ether or diethylene glycol monomethyl ether. When the aqueous antifreeze material is bis(2-hydroxyethyl) ether, the volume ratio of the aqueous antifreeze material to water is 80% to 200%. When the aqueous antifreeze material is diethylene glycol monomethyl ether, the volume ratio of the aqueous antifreeze material to water is 10% to 30%. The non-aqueous positive electrode electrolyte includes a non-aqueous solvent and a positive electrode supporting electrolyte salt, wherein the positive electrode supporting electrolyte salt is an alkane ammonium bromide salt, and the concentration of the alkane ammonium bromide salt is 0.5 mol / L to 5.0 mol / L; the electrolyte of the membraneless two-phase battery naturally separates into layers. The alkane-based ammonium bromide salt is one or more of dodecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide, or octadecyltrimethylammonium bromide.

2. The membrane-free dual-phase battery electrolyte according to claim 1, characterized in that, The negative electrode active material is a zinc ion salt.

3. The membrane-free dual-phase battery electrolyte according to claim 2, characterized in that, The zinc ion salt is one or more of zinc oxalate, zinc tetrafluoromethanesulfonate, zinc dodecyl sulfate, zinc benzenesulfonate, or zinc tetrafluoroborate.

4. The membrane-free dual-phase battery electrolyte according to claim 2, characterized in that, The concentration of zinc ion salt is 0.1 mol / L to 10 mol / L.

5. The membrane-free dual-phase battery electrolyte according to claim 1, characterized in that, The non-aqueous solvent is an organic solvent.

6. The membrane-free dual-phase battery electrolyte according to claim 5, characterized in that, The organic solvent is dichloromethane, bromonaphthalene, bromobenzene, ethyl acetate, or tetrahydrofuran.

7. A membrane-free dual-phase battery, characterized in that, It includes the battery body and the membrane-free two-phase battery electrolyte as described in any one of claims 1-6.

8. The membrane-free dual-phase battery according to claim 7, characterized in that, The battery body includes a positive current collector, a negative current collector, and a battery container. The positive current collector and the negative current collector are disposed on both sides of the battery container, and the battery container is filled with the membraneless dual-phase battery electrolyte.

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