Membrane-free dual-phase battery electrolyte and membrane-free dual-phase battery

Abstract

The invention belongs to the technical field of membrane-free batteries, and particularly relates to a membrane-free dual-phase battery electrolyte and a membrane-free dual-phase battery. According to the membrane-free dual-phase battery, a low-temperature stable organic solvent and water are used as solvents of a two-phase electrolyte, and zinc ion salt is used as a negative electrode electrolyte; a certain proportion of anti-freezing material is added, and an alkane additive is complexed with an organic solvent of a halogen monomer to serve as a positive electrode electrolyte. The problems of high cost and short service life caused by the use of an ion exchange membrane in a liquid battery are avoided, the battery electrolyte is still in a liquid state at low temperature, the temperature working condition of a liquid energy storage battery system is greatly widened, the use of an external heat source under the working condition in winter and the condition that zinc is seriously corroded at normal temperature are avoided, and the service life of the battery is prolonged. The cost of the energy storage system is further reduced.

Description

Technical Field

[0001] The invention belongs to the technical field of membraneless batteries, and in particular relates to a membraneless two-phase battery electrolyte and a membraneless two-phase battery. Background Art

[0002] Unlike lithium-based power batteries, liquid active material batteries, such as flow batteries, are considered one of the most promising electrochemical technologies that can be stored on a large scale. By dissolving the active material in the electrolyte, safe, grid-level energy storage can be achieved. Due to the freezing, slow kinetics and limited solubility of aqueous electrolytes, they cannot operate stably and at high power in extremely cold climates, and the presence of high-cost diaphragms further hinders the performance of the battery at low temperatures. The advent of the membraneless battery concept provides an effective solution to such problems. By storing the positive and negative active materials separately in two incompatible solvents, the crossover of the active materials at the two poles is avoided. In addition, the use of ion exchange membranes is eliminated, which greatly reduces battery costs and improves battery life.

[0003] Currently, in terms of adaptability to wide temperature conditions, most application scenarios of membraneless batteries are usually limited to environments above 0 degrees Celsius. When the temperature continues to drop, the electrolyte freezes and the battery can only operate with the assistance of an external heat source, which is costly and has low performance. Summary of the invention

[0004] In view of the above-mentioned deficiencies in the prior art, the object of the present invention is to provide a membraneless biphase battery electrolyte and a membraneless biphase battery. The purpose of the present invention is to develop a new battery system to deal with the problems of electrolyte freezing, limited solubility and slow kinetics when the ambient temperature drops due to season or weather, or even in extremely cold weather.

[0005] In order to solve the above technical problems, the present invention adopts the following technical solutions:

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

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

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

[0009] The non-aqueous positive electrolyte comprises a non-aqueous solvent, a positive supporting electrolyte salt and a positive antifreeze material. The positive 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 membraneless two-phase battery electrolyte and the membraneless two-phase battery provided by the present invention use an aqueous negative electrode electrolyte and a non-aqueous positive electrode electrolyte as the two-phase electrolyte, use a low-temperature stable organic solvent and water as the solvents of the two-phase electrolyte, add an aqueous antifreeze material and use an organic solvent with an alkane additive complexing a halogen element as the positive electrode electrolyte. While avoiding the high cost and short life problems caused by the use of ion exchange membranes in liquid batteries, the battery electrolyte remains in a liquid state at low temperatures, greatly broadens the temperature operating conditions of the liquid energy storage battery system, avoids the use of an external heat source under winter conditions and the severe corrosion of zinc at room temperature, and further reduces the cost of the energy storage system.

[0011] In a preferred embodiment of the present invention, the volume ratio of the aqueous phase negative electrode electrolyte to the non-aqueous phase 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, 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 more preferably 2.5 mol / L to 4.3 mol / L.

[0019] Another object of the present invention is to provide a membraneless biphase battery, comprising a battery body and any one of the membraneless biphase battery electrolytes described above.

[0020] In a preferred embodiment of the present invention, the battery body comprises a positive electrode current collector, a negative electrode current collector and a battery container, a positive electrode current collector and a negative electrode current collector are arranged on both sides of the battery container, and the battery container is filled with a membraneless 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, positive plates and negative plates are arranged on both sides of the battery container, and the battery container is filled with a biphasic electrolyte, which needs to be left to stand for 12 to 20 hours to stabilize the phase separation of the electrolyte.

[0024] Antifreeze materials are used in the water phase to keep the active substances in the electrolyte in a liquid state between minus 35 and plus 35 degrees Celsius. The organic phase in the membraneless battery of the present invention restricts the halogen bromine in the organic phase through a long-chain complexing agent. The organic phase remains liquid at minus 35 and plus 35 degrees Celsius and can prevent the charging products from diffusing into the water phase and causing battery failure in the absence of a diaphragm.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] 1. The membraneless biphasic battery of the present invention uses an aqueous negative electrode electrolyte and a non-aqueous positive electrode electrolyte as biphasic electrolytes, uses a low-temperature stable organic solvent and water as solvents for the two-phase electrolyte, selects low-freezing point low-temperature additives such as ethylene glycol, bis(2-hydroxyethyl) ether or diethylene glycol monomethyl ether that are miscible with water as aqueous antifreeze materials, and uses an organic solvent of a halogen monomer complexed with an alkane ammonium bromide salt additive as a positive electrode electrolyte. While avoiding the high cost and short life problems caused by the use of ion exchange membranes in liquid batteries, the battery electrolyte remains in a liquid state at low temperatures, greatly broadening the temperature operating conditions of the liquid energy storage battery system, avoiding the use of an external heat source under winter conditions and the severe corrosion of zinc at room temperature, and further reducing the cost of the energy storage system.

[0027] 2. The present invention designs a membraneless two-phase liquid active material battery system that does not suffer performance degradation or freezing due to low temperature. A low-temperature additive with a low freezing point that is miscible with water is selected as an antifreeze material for the water phase, so that the electrolyte remains in a liquid state between minus 35 and plus 35 degrees Celsius. The battery can cope with seasonal or weather-related failures, and avoids the use of high-cost, low-performance diaphragms through the design of an organic system. The organic phase confines the halogen element, the positive electrode active material, to the organic phase through long-chain alkane complexing agent additives, thereby avoiding self-discharge caused by cross-active material. The organic phase remains liquid between minus 35 and plus 35 degrees Celsius and can prevent charging products from diffusing to the water phase to cause battery failure in the absence of a diaphragm, so that the low-temperature corrosion resistance effect is higher than that at room temperature, further improving the battery cycle performance.

[0028] 3. Based on the electrolyte designed by the present invention, the battery can achieve stable cycling for more than 50 cycles at a low temperature of minus 20 degrees Celsius, with a coulombic efficiency of more than 99.99% and an energy efficiency of up to 73.7%, which is close to the performance of batteries at room temperature. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 1. The liquid state diagram of the aqueous electrolyte of the aqueous-organic membraneless dual-phase battery of the present invention at a low temperature of -20°C; (a) the aqueous electrolyte container is placed upright at low temperature; (b) the aqueous electrolyte container is placed inverted at low temperature.

[0030] Figure 2 The membraneless two-phase electrolyte of the present invention is (a) an aqueous phase electrolyte at a low temperature of -20°C; (b) an organic phase electrolyte; and (c) a two-phase electrolyte.

[0031] Figure 3 The SEM images of the zinc sheet corrosion in the water phase at room temperature (a) and -20°C (b) of the present invention.

[0032] Figure 4 Comparison of the charge and discharge cycle performance of the membraneless two-phase battery of the present invention at room temperature (b) and -20°C (a).

[0033] Figure 5 1 is a comparison diagram of the aqueous electrolyte of the present invention when (a) frozen and (b) not frozen at a low temperature of -20°C.

[0034] Figure 6 1 is a comparison diagram of the halogen active material of the present invention at a low temperature of -20°C (a) diffused and (b) non-diffused.

[0035] Figure 7 The figures are comparison diagrams of the organic phase active substance of the present invention at a low temperature of -20°C when (a) it is not frozen and (b) it is frozen. DETAILED DESCRIPTION

[0036] The following is a detailed description of the technical solutions in the embodiments of the present invention in combination with the preferred embodiments and the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

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

[0038] Example 1

[0039] A membraneless biphasic battery electrolyte: 2 mol / L dodecyl zinc sulfate and 70% ethylene glycol in a volume ratio are used as an aqueous electrolyte in deionized water, 3.5 mol / L octadecyl ammonium bromide is added to dichloromethane and complexed with bromine to form an organic electrolyte, and the aqueous electrolyte and the organic electrolyte are mixed together in a volume ratio of 1:1 to form a membraneless biphasic battery electrolyte.

[0040] A water-based organic membraneless two-phase battery suitable for low-temperature environments, wherein the positive electrode is a graphite felt electrode, the negative electrode is a carbon cloth negative electrode, and the electrolyte is the above-mentioned membraneless two-phase battery electrolyte. After the electrolyte is naturally stratified, it is assembled into a membraneless two-phase battery in a battery container and left to stand for 15 hours.

[0041] Example 2

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

[0043] A water-based organic membraneless two-phase battery suitable for low-temperature environments, wherein the positive electrode is a graphite felt electrode, the negative electrode is a carbon cloth negative electrode, and the electrolyte is the above-mentioned membraneless two-phase battery electrolyte. After the electrolyte is naturally stratified, it is assembled into a membraneless two-phase battery in a battery container and left to stand for 12 hours.

[0044] Example 3

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

[0046] A water-based organic membraneless two-phase battery suitable for low-temperature environments, wherein the positive electrode is a graphite felt electrode, the negative electrode is a carbon cloth negative electrode, and the electrolyte is the above-mentioned membraneless two-phase battery electrolyte. After the electrolyte is naturally stratified, it is assembled into a membraneless two-phase battery in a battery container and left to stand for 20 hours.

[0047] Example 4

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

[0049] A water-based organic membraneless two-phase battery suitable for low-temperature environments, wherein the positive electrode is a graphite felt electrode, the negative electrode is a carbon cloth negative electrode, and the electrolyte is the above-mentioned membraneless two-phase battery electrolyte. After the electrolyte is naturally stratified, it is assembled into a membraneless two-phase battery in a battery container and left to stand for 15 hours.

[0050] Example 5

[0051] A membraneless biphasic battery electrolyte: 2 mol / L dodecyl zinc sulfate and 20% by volume of diethylene glycol monomethyl ether are used as an aqueous electrolyte in deionized water, 3.5 mol / L octadecyl ammonium bromide is added to dichloromethane and complexed with bromine to form an organic electrolyte, and the aqueous electrolyte and the organic electrolyte are mixed together in a volume ratio of 1:1 to form a membraneless biphasic battery electrolyte.

[0052] A water-based organic membraneless two-phase battery suitable for low-temperature environments, wherein the positive electrode is a graphite felt electrode, the negative electrode is a carbon cloth negative electrode, and the electrolyte is the above-mentioned membraneless two-phase battery electrolyte. After the electrolyte is naturally stratified, it is assembled into a membraneless two-phase battery in a battery container and left to stand for 15 hours.

[0053] Comparative Example 1

[0054] A membraneless biphasic battery electrolyte comprises 2 mol / L dodecyl zinc sulfate and 15% by volume ethylene glycol dissolved in deionized water as an aqueous electrolyte, 2 mol / L octadecyl ammonium bromide is added to dichloromethane and complexed with bromine to form an organic electrolyte, and the aqueous electrolyte and the organic electrolyte are mixed together in a volume ratio of 1:1 to form a membraneless biphasic battery electrolyte.

[0055] A membraneless two-phase battery, wherein the positive electrode is a graphite felt electrode, the negative electrode is a carbon cloth negative electrode, and the electrolyte is the above-mentioned membraneless two-phase electrolyte. The membraneless two-phase battery is assembled in a battery container and left to stand for 15 hours.

[0056] Figure 5 The comparison diagram of the aqueous electrolyte of the present invention at -20°C is (a) frozen and (b) not frozen. Comparative Example 1 The volume of the aqueous antifreeze material in the negative electrode electrolyte is small, the aqueous phase will freeze, and the battery cannot operate. The aqueous electrolyte freezes at -20°C. Figure 5 shown.

[0057] Comparative Example 2

[0058] A membraneless biphasic battery electrolyte comprises 1 mol / L methyl-ethylpyrrolidone bromide and 65% by volume ethylene glycol in deionized water as an aqueous phase electrolyte, 1 mol / L methyl-ethylpyrrolidone bromide is added to dichloromethane and complexed with bromine to form an organic phase electrolyte, and the aqueous phase electrolyte and the organic phase electrolyte are mixed together in a volume ratio of 1:1 to form a membraneless biphasic battery electrolyte.

[0059] A membraneless two-phase battery, wherein the positive electrode is a graphite felt electrode, the negative electrode is a carbon cloth negative electrode, and the electrolyte is the above-mentioned membraneless two-phase electrolyte. The membraneless battery is assembled in a capacitor and left to stand for 15 hours.

[0060] Figure 6 The following is a comparison of the halogen active material of the present invention at a low temperature of -20°C (a) diffused and (b) not diffused. In Comparative Example 2, the interaction between the antifreeze material, the water phase active material and the methyl-ethylpyrrolidine bromide additive is too weak, which will cause the halogen active material to diffuse into the water phase during charging and self-discharge, causing the battery to fail quickly. The diffusion results of the halogen active material at -20°C are shown in FIG. Figure 6 shown.

[0061] Comparative Example 3

[0062] A membraneless biphasic battery electrolyte comprises 1.5 mol / L tetrabutylammonium bromide and 37.5% by volume ethylene glycol in deionized water as an aqueous electrolyte, 1.5 mol / L tetrabutylammonium bromide additive is added to dichloromethane and complexed with bromine to form an organic electrolyte, and the aqueous electrolyte and the organic electrolyte are mixed together in a volume ratio of 1:1 to form a membraneless biphasic battery electrolyte.

[0063] A membraneless two-phase battery, wherein the positive electrode is a graphite felt electrode, the negative electrode is a carbon cloth negative electrode, and the electrolyte is the above-mentioned membraneless two-phase electrolyte. The membraneless two-phase battery is assembled in a battery container and left to stand for 15 hours.

[0064] Figure 7 The following is a comparison of the organic phase active material of the present invention at -20°C (a) not frozen and (b) frozen. In Comparative Example 3, the strong interaction between the tetrabutylammonium bromide organic complexing agent and the antifreeze additive will cause the organic phase active material to freeze at low temperature, solids will be produced at the positive electrode, and the battery will not operate. The freezing results of the organic phase active material are shown in Figure 2. Figure 7 shown.

[0065] Results Analysis

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

[0067] 3.5 mol / L octadecyl ammonium bromide is added to dichloromethane and complexed with the bromine generated by oxidation to form an organic phase. Dichloromethane as an organic solvent itself can be in a liquid state at minus 20 degrees Celsius. At the same time, octadecyl ammonium bromide is used as a supporting salt for the positive electrode electrolyte to complex the battery active substances to avoid contact with the aqueous phase active substances to cause battery self-discharge, thereby ensuring the low temperature performance and long-term stability of the battery.

[0068] Figure 2 The membraneless two-phase electrolyte of the present invention is (a) an aqueous electrolyte; (b) an organic electrolyte; (c) a two-phase electrolyte at a low temperature of -20°C. Figure 2 As shown, the aqueous electrolyte and the organic electrolyte were mixed together in a volume ratio of 1:1, assembled into a membraneless biphasic battery after natural stratification and left to stand for 15 hours. The halogen elements in the organic phase did not diffuse into the aqueous phase, causing the battery to deactivate.

[0069] Figure 3The SEM of the upper aqueous phase zinc sheet kept at room temperature (b) and -20℃ (a) for 24 hours shows that the corrosion of the zinc sheet is greatly improved at -20℃, proving that the battery electrolyte can better inhibit the diffusion of positive electrode active materials at low temperatures, thereby improving the long-term endurance and performance of the battery at low temperatures.

[0070] Figure 4 Comparison of the cycling performance of membraneless biphasic batteries at room temperature and -20°C. The test conditions are: current density 1mA / cm 2 , cut-off voltage range 0.1V~2V, 20mAh single cycle capacity. As can be seen from the figure, the battery design can stably cycle for more than 50 cycles in a low temperature environment, the coulomb efficiency exceeds 99.99%, and the energy efficiency is as high as 73.7%, which is close to the performance of the battery at room temperature.

[0071] The mechanism of action and difficulties of the antifreeze material of the present invention: In the zinc-halogen two-phase membraneless battery system, unlike other traditional battery designs, because the active material is a liquid active material and is soluble in more than one solvent and has no diaphragm, multiple factors need to be considered when selecting antifreeze materials, rather than simply selecting conventional antifreeze additives: 1. The stability of the water-oil two-phase interface, the water-oil two-phase itself is not miscible; 2. Cooperate with the water-phase active material and additives to keep the water-phase electrolyte from freezing; 3. Cooperate with the organic phase halogen complexing agent additive to keep the organic phase electrolyte from freezing; 4. The oil-phase halogen active material does not diffuse to the water phase in the charging state; 5. How to maintain the battery performance at the same level as at room temperature. Therefore, the selection of antifreeze materials is completely based on the design of the zinc-halogen two-phase membraneless battery system, and the interaction force between the solute and the solvent in the system needs to be within a specific range. The selection of antifreeze materials is greatly limited and various parameters including the ratio need to be precisely controlled.

[0072] In summary, the present invention designs a membrane-free two-phase liquid active material battery system that does not suffer from performance degradation or freezing due to low temperature, selects a low-freezing-point low-temperature additive that is miscible with water as an aqueous antifreeze material, keeps the electrolyte in a liquid state between minus 35 and plus 35 degrees Celsius, and the battery can cope with seasonal or weather-related failures, and avoids the use of high-cost, low-performance diaphragms through the design of an organic system. The organic phase confines the positive active material to the organic phase, avoiding self-discharge caused by crossover of the active material, making the low-temperature corrosion resistance effect higher than that at room temperature, and further improving the battery cycle performance.

[0073] It should be noted that when the present invention relates to a numerical range, it should be understood that the two endpoints of each numerical range and any value between the two endpoints can be selected. Since the steps and methods used are the same as those in the embodiment, in order to avoid redundant description, the present invention describes a preferred embodiment. Although the preferred embodiments of the present invention have been described, once those skilled in the art know the basic creative concept, they can make other changes and modifications to these embodiments. Therefore, the attached protection scope is intended to be interpreted as including the preferred embodiment and all changes and modifications that fall within the scope of the present invention.

[0074] Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of the present invention fall within the scope of the protection scope of the present invention and its equivalent technology, the present invention is also intended to include these changes and variations.

Claims

1. A membraneless two-phase battery electrolyte, characterized in that: The electrolyte includes an aqueous negative electrode electrolyte and a non-aqueous positive electrode electrolyte in a volume ratio of 1:1 to 5; The aqueous negative electrode electrolyte comprises water, negative electrode active material and aqueous antifreeze material, wherein the aqueous antifreeze material is one or more of ethylene glycol, bis(2-hydroxyethyl) ether or diethylene glycol monomethyl ether; When the water-phase antifreeze material is ethylene glycol, the volume ratio of the water-phase antifreeze material to water is 60% to 99%, when the water-phase antifreeze material is bis(2-hydroxyethyl) ether, the volume ratio of the water-phase antifreeze material to water is 80% to 200%, and when the water-phase antifreeze material is diethylene glycol monomethyl ether, the volume ratio of the water-phase antifreeze material to water is 10% to 30%; The non-aqueous positive electrolyte solution comprises a non-aqueous solvent and a positive supporting electrolyte salt. The positive supporting electrolyte salt is an alkane ammonium bromide salt. The concentration of the alkane ammonium bromide salt is 0.5 mol / L to 5.0 mol / L.

2. The membraneless biphasic battery electrolyte according to claim 1, characterized in that: The alkane ammonium bromide salt is one or more of dodecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide or octadecyltrimethylammonium bromide.

3. The membraneless biphasic battery electrolyte according to claim 1, characterized in that: The negative electrode active material is a zinc ion salt.

4. The membraneless biphasic battery electrolyte according to claim 3, characterized in that: The zinc ion salt is one or more of zinc oxalate, zinc tetrafluoromethanesulfonate, zinc dodecyl sulfate, zinc benzenesulfonate or zinc tetrafluoroborate.

5. The membraneless biphasic battery electrolyte according to claim 3, characterized in that: The zinc ion salt concentration is 0.1 mol / L to 10 mol / L.

6. The membraneless biphasic battery electrolyte according to claim 1, characterized in that: The non-aqueous solvent is an organic solvent.

7. The membraneless biphasic battery electrolyte according to claim 6, characterized in that: The organic solvent is dichloromethane, bromonaphthalene, bromobenzene, ethyl acetate or tetrahydrofuran.

8. A membraneless two-phase battery, characterized in that: It comprises a battery body and the membraneless biphasic battery electrolyte according to any one of claims 1 to 7.

9. The membraneless biphase battery according to claim 8, characterized in that: The battery body comprises a positive electrode current collector, a negative electrode current collector and a battery container. The positive electrode current collector and the negative electrode current collector are arranged on both sides of the battery container. The battery container is filled with the membraneless dual-phase battery electrolyte.

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