CN110993944B - A kind of aqueous ion battery and its application - Google Patents

Abstract

The application discloses water system ion battery includes: an electrolyte, wherein the electrolyte is an aqueous solution containing electrolyte; a negative electrode containing a negative electrode active material; the negative electrode active material includes polyimide containing naphthalene ring; and a positive electrode containing a positive electrode active material; the positive electrode active material includes a sodium intercalation material. The method solves the problems: the existing negative electrode material and the positive electrode sodium intercalation material have the problem of poor matching (such as mass ratio of the positive electrode material to the negative electrode material, technological parameters of electrode preparation, potential voltage window and the like), so that the cycle life of the battery is low and the specific capacity is low; because the electrode preparation of the existing negative electrode material and the process of battery assembly are complex, the requirements on the conditions of an operation workshop are high, and the material preparation cost is high, so that the production and manufacturing cost of the whole battery is increased.

Description

A kind of aqueous ion battery and its application

technical field

The application relates to an aqueous ion battery, which belongs to the field of batteries.

Background technique

Aqueous ion batteries are battery systems that use water as the electrolyte. Compared with other non-aqueous ion batteries, aqueous ion batteries have the advantages of good safety performance, high ion conductivity, low price and easy availability. In addition, water-based batteries can complete battery production, assembly, sealing and other operations without an anhydrous and oxygen-free environment, which greatly reduces the production and manufacturing costs of batteries. Therefore, it has gradually attracted attention and is very suitable for the large-scale energy storage market. Currently commercially used energy storage batteries are mainly lead-acid batteries, lithium iron phosphate or ternary power batteries. Among them, lead-acid batteries have short service life and high pollution. Its negative electrode uses metallic lead (Pb), and a lead sulfate (PbSO ₄ ) passivation layer is formed during the reaction process, resulting in capacity fading, and the cycle life is only a few hundred cycles. Both lithium iron phosphate and ternary power batteries use organic electrolytes, which are flammable and explosive with low safety. At the same time, because of the use of metals such as nickel-cobalt-manganese-ferro, there is no advantage in cost. None of these types of batteries can meet the special needs in the field of energy storage (such as high safety, long cycle life, low cost, etc.).

In the progress of aqueous ion batteries, aqueous lithium ion batteries have been developed to a certain extent. However, the lithium resources on the earth are difficult to support the application requirements of large-scale energy storage systems. The basic reserves of lithium resources in the world are about 58M tons (calculated as lithium carbonate), and most of the lithium resources are concentrated in plateau salt lakes above 4,000 meters above sea level, making it difficult to develop and utilize them. The known recoverable reserves are about 25M tons. At present, the annual consumption of lithium carbonate in the world is about 70,000 to 80,000 tons, and the expected mining time is only more than 50 years. In contrast, sodium has similar chemical properties to lithium, so it is considered to be suitable for aqueous ion battery systems as a substitute for lithium. Sodium is abundant in the earth's crust, and the price of sodium salt is only one tenth of that of lithium salt. Therefore, combined with many advantages of aqueous batteries, aqueous sodium-ion batteries have broad application prospects in the fields of power generation and user-side energy storage.

However, the currently developed aqueous secondary batteries also have many problems. For example, the cycle life is low, the materials are difficult to scale up, and large-scale applications cannot be realized at the same time. The main bottleneck of the low cycle life of aqueous sodium-ion batteries lies in the anode materials. So far, sodium titanium phosphate and Prussian blue have been developed at home and abroad as negative electrode materials for aqueous sodium-ion batteries. However, when this material is in an aqueous solution, hydrogen evolution side reactions will occur during discharge, resulting in low battery cycle life; and the electrochemical capacity of this type of negative electrode material is low, and it is difficult to exert the capacity of the full battery.

In view of the above problems, the present application provides a new aqueous ion battery.

Contents of the invention

According to one aspect of the present application, a water-based ion battery is provided, which solves the problem that the existing negative electrode material has poor stability in the water-based electrolyte, and hydrogen evolution side reactions occur during discharge, resulting in low cycle life and low specific capacity of the water-based sodium-ion battery; the electrode preparation of the existing negative electrode material and the battery assembly process are complicated, the requirements for the operating workshop are high, and the cost of material preparation is high, resulting in an increase in the cost of the entire battery production; Preparation process parameters and potential voltage window, etc.) lead to low cycle life and low specific capacity of the battery.

The aqueous ion battery is characterized in that it comprises:

An electrolytic solution, which is an aqueous solution containing an electrolyte;

Negative electrode, the negative electrode contains negative electrode active material; the negative electrode active material includes polyimide containing naphthalene ring; and

A positive electrode, the positive electrode contains a positive electrode active material; the positive electrode active material includes a sodium-intercalating material, and the sodium-intercalating material is at least one selected from NaMnO ₂ , Na _x MnO ₂ , NaFeFe(CN) ₆ , Na ₂ CoFe(CN) ₆ , and Na ₂ NiFe(CN) ₆ .

Among them, NaMnO ₂ is λ-MnO ₂ embedded with sodium ions; x is 0.44-0.95;

NaMnO ₂ is λ-MnO ₂ intercalated with sodium ions, prepared according to the method in literature (1-2);

Document 1: Whitacre J F, Wiley T, Shanbhag S, et al. An aqueous electrolyte, sodium ion functional, large format energy storage device for stationary applications. J. Power Sources 2012, 213: 255-264.

Document 2: Komaba S, Ogata A, Tsuchikawa T. Enhanced supercapacitive behaviors of birthite. Electrochem. Commun., 2008, 10(10): 1435-1437.

NaFeFe(CN) ₆ , Na ₂ CoFe(CN) ₆ , Na ₂ NiFe(CN) ₆ were prepared according to the method in literature (3-7);

Document 3: C.D. Wessells, S.V.Peddada, R.A. Huggins and Y.Cui: ‘Nickelhexacyanoferrate nanoparticles electrodes for aqueous sodium and potassium ionbatteries’, Nano Lett., 2011, 11, 5421–5425.

Document 4: Yang You, Zhongsheng Sang&Jinping Liu.Recent developments onaqueous sodium ion batteries.Materials Technology:Advanced PerformanceMaterials 2016VOL.31NO.9.501-509.

Document 5: QIAN J, ZHOU M, CAO Y, et al. NaxMyFe(CN) ₆ (M=Fe, Co, Ni): A new class of cathode materials for sodium ion batteries[J].J.Electrochem., 2012, 18(2): 108-112.

Document 6: Pasta M, Wessells C D, Huggins R A, et al. A high-rate and longcycle life aqueous electrolyte battery for grid-scale energy storage. Nature Commun., 2012, 3: 1149.

Literature 7: WU X, Cao Y, AI X, ET Al. Et Al.Al. Cost and Environmentally Benignaqueous Rechargeable Sodium-ION BATTERY BASED on Nati ₂ (PO ₄ ) _{3 -} NIFE (CN) ₆ Internet Ion Chemistry.electrochem.commun., 2013,31 (0): 145-148.

NaxMnO ₂ is prepared according to the method of literature (8-10);

Literature 8: Whitacre J, Tevar A, Sharma S. Na ₄ Mn ₉ O ₁₈ as a positive electrode material for an aqueous electrolyte sodium-ion energy storage device. Electrochem. Commun., 2010,12(3):463-466.

Document 9: J.F.Whitacre, Electrochemistry Communication, 12(2010) 463-466.

Document 10: B. Zhang, Y. Liu, X. Wu, Y. Yang, Z. Chang, Z. Wen and Y. Wu: 'An aqueous rechargeable battery based on zinc anode and Na _0.95 MnO ₂ ', Chem. Commun., 2014, 50, 1209–1211.

Optionally, the mass ratio of the positive active material to the negative active material is 1-4;

Wherein, the mass of the negative electrode active material is calculated by the mass of the polyimide containing naphthalene ring contained therein, and the mass of the positive electrode active material is calculated by the mass of the lithium manganate contained therein.

Optionally, the chemical formula of the polyimide containing naphthalene ring is as shown in formula I:

Among them, n=1000～10000.

Optionally, the electrolyte is at least one selected from sodium sulfate, sodium nitrate, sodium phosphate, sodium carbonate, sodium permanganate, sodium chloride, sodium bromide, and sodium iodide.

Optionally, the electrolyte concentration in the electrolyte is 1.5M-2.5M.

Optionally, the aqueous ion battery further includes a separator, which separates the positive electrode from the negative electrode and passes electrolyte ions.

Optionally, the separator is selected from at least one of glass fiber filter paper, absorbent glass fiber membrane, and non-woven fabric.

Optionally, the preparation method of the negative electrode comprises the following steps:

The raw materials containing the negative electrode active material, the conductive agent, and the binder are mixed with a solvent to obtain a slurry, and the slurry is coated on a current collector and dried to obtain the negative electrode.

Optionally, the mass ratio of the negative electrode active material, conductive agent, and binder is 5.5-9.6:0.25-3:0.25-1.25.

Optionally, the mass ratio of the negative electrode active material, conductive agent, and binder is 6:3:1.

Optionally, the solvent is selected from at least one of absolute ethanol, N-methylpyrrolidone, and N-dimethylformamide;

Optionally, the binder is selected from at least one of polyvinylidene fluoride, carboxymethyl cellulose, polytetrafluoroethylene, and styrene-butadiene rubber;

Optionally, the conductive agent is selected from at least one of conductive carbon black, acetylene black, carbon nanotubes, superconducting carbon black, carbon fiber, and conductive graphite;

Optionally, the current collector is selected from at least one of stainless steel sheet, stainless steel mesh, and stainless steel foil.

Optionally, the areal density of the negative electrode active material in the current collector is 2-5 mg/cm ² .

Optionally, the preparation method of the positive electrode comprises the following steps:

The raw materials containing the positive electrode active material, conductive agent, and binder are mixed with a solvent to obtain a slurry, and the slurry is coated on a current collector and dried to obtain the positive electrode.

Optionally, the mass ratio of the positive active material, conductive agent and binder is 7.5-9.6:0.25-2.25:0.25-2.25.

Optionally, the mass ratio of the positive electrode active material, the conductive agent, and the binder is 8:1:1.

Optionally, the solvent is selected from at least one of absolute ethanol, N-methylpyrrolidone, and N-dimethylformamide;

The binder is selected from at least one of polyvinylidene fluoride, carboxymethyl cellulose, polytetrafluoroethylene, and styrene-butadiene rubber;

The conductive agent is selected from at least one of conductive carbon black, acetylene black, carbon nanotubes, superconducting carbon black, carbon fiber, and conductive graphite;

The current collector is selected from at least one of stainless steel sheet, stainless steel mesh, and stainless steel foil.

Optionally, the areal density of the positive electrode active material in the current collector is 3-8 mg/cm ² .

Optionally, the preparation method of the negative electrode active material comprises the following steps:

React the solution containing 1,4,5,8-naphthalene tetracarboxylic anhydride and ethylenediamine at 120-180°C for 4-18 hours in an inert atmosphere, and obtain a dry powder after separation, washing and drying;

The dry powder is sintered in an inert atmosphere to obtain the negative electrode active material.

Optionally, the inert atmosphere is at least one selected from nitrogen, helium, and argon.

Optionally, the solvent of the solution containing 1,4,5,8-naphthalene tetracarboxylic anhydride and ethylenediamine is at least one selected from N-methylpyrrolidone and N-dimethylformamide.

Optionally, the molar ratio of 1,4,5,8-naphthalene tetracarboxylic anhydride to ethylenediamine is 1:1-2.

Optionally, the sintering temperature is 200-350°C.

Optionally, the sintering time is 3-8 hours.

Specifically, the preparation method of the negative electrode active material includes the following steps:

Step A: Add 1,4,5,8-naphthalene tetracarboxylic anhydride powder and ethylenediamine solution in N-dimethylformamide (DMF) solution at a molar ratio of 1:1, and keep magnetic stirring. The reaction vessel is a glass flask. The flask was protected with argon. The flask was transferred to a 50°C oil bath, and the temperature was gradually raised to 150°C. The reaction is maintained at this temperature for 4 to 18 hours.

Step B: Collect the product, centrifuge, and remove the supernatant. For the centrifuged sediment below, it was diluted and washed with N-dimethylformamide, and a second centrifugation was performed. Wash and centrifuge with ethanol. The final material was dried in a vacuum oven to obtain a dry powder.

Step C: sintering the above dry powder in a tube furnace under the protection of argon atmosphere. The sintering time was 3 hours.

Specifically, the aqueous ion battery includes:

Electrolyte, 1.5-2.5M sodium sulfate (Na ₂ SO ₄ ) aqueous solution;

Diaphragm, glass fiber filter paper (porosity below 1 micron, thickness about 260 microns);

negative electrode, a polyimide electrode containing naphthalene rings; and

Positive electrode, sodium-based material electrode (NaMnO ₂ , Na _x MnO ₂ , NaFeFe(CN) ₆ , Na ₂ CoFe(CN) ₆ , Na ₂ NiFe(CN) ₆ ; wherein: x is 0.44-0.95).

Specifically, the negative electrode includes:

Negative electrode active material, polyimide organic material containing naphthalene ring;

Conductive agent, conductive carbon black (Super P carbon);

Binder, polytetrafluoroethylene (PTFE) emulsion; and

Collector, stainless steel mesh.

Specifically, the preparation method of the negative electrode comprises the following steps:

The negative electrode active material, conductive carbon black, and binder are mixed and stirred in an ethanol solution according to the mass ratio of 6:3:1 to form a slurry, coated on a stainless steel mesh, and then vacuum-dried. The electrode area is about 1.5 cm ² , and the surface density of the active material is 2-5 mg·cm ^-2 .

Specifically, the positive electrode includes:

Positive active material, sodium manganate (NaMnO ₂ , that is, λ-MnO ₂ embedded with sodium ions);

Conductive agent, conductive carbon black (Super P carbon);

Binder, polytetrafluoroethylene (PTFE) emulsion; and

Collector, stainless steel mesh.

Specifically, the preparation method of the positive electrode includes the following steps:

The positive electrode active material, conductive carbon black, and binder are mixed and stirred in ethanol to form a slurry according to the mass ratio of 8:1:1, coated on the stainless steel mesh, and then vacuum-dried. The electrode area is about 1.5 cm ² , and the surface density of the active material is 3-8 mg·cm ^-2 .

The working principle of the water system ion battery is:

When charging: the sodium manganate of the positive electrode is desodiumized, and the sodium ions are conducted to the surface of the polyimide carbonyl group of the negative electrode in the electrolyte, and are absorbed by the carbonyl functional group, and at the same time, the electrons obtained by the carbonyl group from the external circuit are reduced;

During discharge: the carbonyl group on the surface of the negative electrode material is free of sodium ions, and at the same time the carbonyl group loses electrons and is oxidized, and the sodium ions are conducted to the positive electrode sodium manganate in the electrolyte and embedded in the structure of sodium manganate.

Aqueous sodium-ion batteries use an aqueous solution containing sodium ions as the electrolyte, and the positive electrode is composed of different ion intercalation compounds. When charging, sodium ions come out of the positive electrode and diffuse to the negative electrode through the electrolyte, where adsorption or intercalation reactions occur at the negative electrode, and electrons are transferred from the positive electrode to the negative electrode. The discharge process is the opposite of the charge process.

According to another aspect of the present application, an application of the aqueous ion battery in energy storage is provided.

According to another aspect of the present application, an application of the aqueous ion battery in an aqueous energy storage battery is provided.

The beneficial effect that this application can produce comprises:

1) Polyimide-based organic materials containing naphthalene rings have been shown to work in non-aqueous (conventional) ion batteries, aqueous flow batteries, and aqueous lithium-ion batteries. In this work, this kind of material was used in aqueous sodium-ion secondary batteries for the first time, and excellent electrochemical performance was obtained by optimizing the formulation of positive and negative electrodes and the ratio of N/P. A polyimide organic material containing a naphthalene ring has a naphthalene ring in its repeating unit, two imide structures and four carbonyl functional groups. Among them, the carbonyl functional group is electrochemically active and can absorb and desorb lithium ions to contribute to the capacity. At the same time, it has high mechanical strength and thermal stability, and can undergo chemically and structurally highly reversible ion coordination reactions during charge and discharge. Compared with the currently used aqueous battery electrode materials, the energy and power indicators of this type of battery electrode materials are not inferior, and even better in terms of cost, low temperature performance, and overcharge performance. It will be a big breakthrough in the development of aqueous batteries. In addition, its price is cheap, and its raw material resources are almost unlimited. With the help of more optimized molecular structure design and cathode material matching, the specific energy of the battery can be more than doubled;

2) For the water-based ion battery provided by this application, the electrode preparation process of this type of organic negative electrode material is simple; the workshop requirements for battery assembly are low (no need for sealing, dry environment, etc.); the electrode material can exist stably in the water-based battery, and can suppress the side reaction of water molecules during the charging and discharging process of the battery to the greatest extent, thereby improving the capacity and cycle stability of the battery. life cycle requirements;

3) The aqueous ion battery provided by the present application, the polyimide organic electrode material containing naphthalene ring is used as the negative electrode for the aqueous sodium ion battery, and the positive electrode uses the metal oxide material of the sodium intercalation system. The water-based battery is absolutely safe (no fire or explosion), high cycle life (>1000 times), no precious metals, environmentally friendly, cost controllable, fast charging (good sodium ion conduction in the water system), and a large temperature range (low temperature under salt water, high temperature above). Very suitable for large-scale energy storage applications;

4) The large temperature range of the aqueous battery (-35°C to 40°C) can meet the needs of energy storage power stations in extreme environments. Its fast charging performance can meet the frequency regulation requirements in the energy storage system. In addition, it can also meet application scenarios such as renewable energy grid connection and ancillary services. Aqueous energy storage batteries also have good application prospects in the field of energy storage on the power generation side and the user side where peak-shaving and valley-filling, peak-shaving and frequency modulation, and improvement of power quality are the main demands.

Description of drawings

Fig. 1 is the charge-discharge curve diagram of the aqueous full battery based on polyimide negative electrode and sodium manganate positive electrode in embodiment 4 of the present application;

FIG. 2 is a graph showing the cycle performance of an aqueous full battery based on a polyimide negative electrode and a sodium manganate positive electrode in Example 4 of the present application.

Detailed ways

The present application is described in detail below in conjunction with the examples, but the present application is not limited to these examples.

Unless otherwise specified, the raw materials in the examples of the present application were purchased through commercial channels.

Analytic method is as follows in the embodiment of the application:

The electrochemical performance test was carried out by Xinwei battery tester (model: CT-4008-5V20mA-164, Shenzhen Xinwei Electronics Co., Ltd.). On the test instrument, set the following program: put it aside for 1min; charge to 1.9V with a constant current of 1.0C; rest for 1min; then discharge to 0.7V with a constant current of 1.0C; repeat the above charging and discharging steps 800 times.

Embodiment 1 synthesis of negative electrode active material

Step A: Add 52.08g of 1,4,5,8-naphthalenetetracarboxylic anhydride powder and 2.54mL of ethylenediamine monohydrate solution in 400mL of N-dimethylformamide (DMF) solution at a molar ratio of 1:1.01, and keep magnetic stirring. The reaction vessel is a glass flask. The flask was protected with argon. The flask was transferred to a 50°C oil bath, and the temperature was gradually raised to 150°C. The reaction was maintained at this temperature for 4 hours.

Step B: Collect the product, centrifuge, and remove the supernatant. For the centrifuged sediment below, it was diluted and washed with N-dimethylformamide, and a second centrifugation was performed. Wash and centrifuge with ethanol. The final material was dried in a vacuum oven to obtain a dry powder.

Step C: sintering the above dry powder in a tube furnace under the protection of argon atmosphere. The sintering temperature was 350° C. and the sintering time was 3 hours to obtain Sample 1 .

The preparation of embodiment 2 electrodes

negative electrode

Active material: polyimide organic material sample 1 containing naphthalene ring

Conductive agent: conductive carbon black (Super P carbon)

Binder: polytetrafluoroethylene (PTFE) emulsion

Current collector: stainless steel mesh

Preparation process: The active material, conductive carbon black, and binder are mixed and stirred in an ethanol solution according to the mass ratio of 6:3:1 to form a slurry, coated on a stainless steel mesh, and then vacuum-dried. The electrode area is about 1.5 cm ² , and the density of one side of the active material is 2 mg·cm ^-2 .

The preparation of embodiment 3 electrodes

positive electrode:

Active substance: Sodium manganate (NaMnO ₂ , i.e. λ-MnO ₂ intercalated with sodium ions)

Conductive agent: conductive carbon black (Super P carbon)

Binder: polytetrafluoroethylene (PTFE) emulsion

Current collector: stainless steel mesh

Process: The active material, conductive carbon black, and binder are mixed in ethanol at a mass ratio of 8:1:1 to form a slurry, coated on a stainless steel mesh, and then vacuum-dried. The electrode area is about 1.5 cm ² , and the density of one side of the active material is 5 mg·cm ^-2 .

The assembly of embodiment 4 battery

Structure and composition

Electrolyte: 2.5M sodium sulfate (Na ₂ SO ₄ ) aqueous solution

Diaphragm: glass fiber filter paper (porosity below 1 micron, thickness about 260 microns)

Negative electrode: polyimide electrode containing naphthalene ring

Positive electrode: sodium manganate electrode

Assembly process: place the negative electrode shell on the insulating platform, and place the negative electrode piece in the center of the negative electrode shell; then, place the diaphragm flat on the upper layer of the negative electrode plate, and use a pipette to take an appropriate amount of electrolyte and add it to the surface of the diaphragm to allow the electrolyte to fully infiltrate the diaphragm and the pole piece; then, use insulating tweezers to place the positive electrode piece, gasket, spring piece, and positive electrode case on the upper layer of the diaphragm in sequence; among them, the positive and negative pole pieces coated with electrode materials are facing and close to the diaphragm; finally, using insulating tweezers Place the battery on the mold of the battery sealing machine, adjust the pressure to 850Pa, and hold the pressure for 5 seconds; so far, the assembly of the entire battery is completed.

The assembly of embodiment 5 batteries

The structural composition is similar to that of Example 4, except that the electrolyte is a 2M sodium sulfate (Na ₂ SO ₄ ) aqueous solution.

The assembly of embodiment 6 batteries

The structural composition is similar to that of Example 4, except that the electrolyte is a 1.5M sodium sulfate (Na ₂ SO ₄ ) aqueous solution.

The assembly of embodiment 7 batteries

The structural composition is similar to that of Example 4, except that the positive electrode is Na ₂ CoFe(CN) ₆ .

The assembly of embodiment 8 batteries

The structural composition is similar to that of Example 4, except that the positive electrode is Na ₂ NiFe(CN) ₆ .

The assembly of embodiment 9 batteries

The structural composition is similar to that of Example 4, except that the positive electrode is Na _0.44 MnO ₂ .

The assembly of embodiment 10 battery

The structural composition is similar to that of Example 4, except that the positive electrode is NaFeFe(CN) ₆ .

The assembly of embodiment 11 batteries

The structural composition is similar to that of Example 4, except that the positive electrode is Na _0.95 MnO ₂ .

Embodiment 12 battery performance test

Test conditions: charge first when using, then discharge and charge repeatedly. Charge and discharge current: 1C=100mA/g.

The charge-discharge curve of the aqueous full battery based on the polyimide negative electrode and the sodium manganate positive electrode is shown in FIG. 1 , which corresponds to the battery assembled in Example 4. As shown in Figure 1, the reversible charge-discharge specific capacity of the first cycle is 117mAh/g.

The cycle performance curve of the aqueous full battery based on the polyimide negative electrode and the sodium manganate positive electrode is shown in FIG. 2 , which corresponds to the battery assembled in Example 4. Charge and discharge current: 1C=100mA/g. Figure 2 shows that after the third cycle, the charging and discharging Coulombic efficiency can reach more than 98%, and has been maintained. It shows that the discharge capacity and charge capacity are fully utilized, and there is almost no side reaction. After 800 cycles, the capacity is still 112mAh/g, and the capacity retention rate is as high as 96%.

The effect of positive and negative active mass ratio (P/N) on the cycle stability of full battery. The study found that when P/N=1.5, that is, when the mass of positive sodium manganate is less than twice the active mass of the negative organic matter, the battery capacity decays rapidly, and the charge and discharge capacity decays to 83% of the first cycle after 800 cycles;

Table 1

The performance of the battery assembled in Examples 5-11 is similar to that of the battery assembled in Example 4.

The above are only a few embodiments of the present application, and do not limit the present application in any form. Although the present application discloses the above with preferred embodiments, it is not intended to limit the present application. Any skilled person who is familiar with this profession, without departing from the scope of the technical solution of the present application, making some changes or modifications using the technical content disclosed above are equivalent to equivalent implementation cases, and all belong to the scope of the technical solution.

Claims (23)

1. An aqueous ion battery comprising:

an electrolyte, wherein the electrolyte is an aqueous solution containing an electrolyte;

a negative electrode containing a negative electrode active material; the negative electrode active material contains polyimide having naphthalene rings; and

a positive electrode containing a positive electrode active material; the positive electrode active material is embedded with sodium material, and the sodium material is Na _x MnO ₂ ；

Wherein:

NaMnO ₂ lambda-MnO for intercalation of sodium ions ₂ ；

x is 0.44-0.95;

the mass ratio of the positive electrode active material to the negative electrode active material is 2-4; wherein the mass of the negative electrode active material is calculated by the mass of polyimide containing naphthalene ring, and the mass of the positive electrode active material is calculated by the mass of sodium intercalation material.

2. The aqueous ion battery of claim 1, wherein the polyimide containing a naphthalene ring has a chemical formula as shown in formula I:

i is a kind of

Wherein n=1000 to 10000.

3. The aqueous ion battery according to claim 1, wherein the electrolyte is at least one selected from the group consisting of sodium sulfate, sodium nitrate, sodium phosphate, sodium carbonate, sodium permanganate, sodium chloride, sodium bromide, and sodium iodide.

4. The aqueous ion battery according to claim 1, wherein the concentration of the electrolyte in the electrolyte solution is 1.5m to 2.5m.

5. The aqueous ionic cell of claim 1, further comprising a separator separating the positive electrode and the negative electrode and passing electrolyte ions.

6. The aqueous ion battery according to claim 5, wherein the separator is at least one member selected from the group consisting of glass fiber filter paper, an adsorption type glass fiber film and a nonwoven fabric.

7. The aqueous ion battery according to claim 1, wherein the method for producing the negative electrode comprises the steps of:

mixing raw materials containing a negative electrode active material, a conductive agent and a binder with a solvent to obtain slurry, coating the slurry on a current collector, and drying to obtain the negative electrode.

8. The aqueous ion battery according to claim 7, wherein the mass ratio of the negative electrode active material, the conductive agent, and the binder is 5.5 to 9.6: 0.25-3: 0.25 to 1.25.

9. The aqueous ion battery according to claim 7, wherein the solvent is at least one selected from the group consisting of absolute ethyl alcohol, N-methylpyrrolidone, and N-dimethylformamide.

10. The aqueous ion battery according to claim 7, wherein the binder is at least one selected from polyvinylidene fluoride, carboxymethyl cellulose, polytetrafluoroethylene, and styrene-butadiene rubber.

11. The aqueous ion battery according to claim 7, wherein the conductive agent is at least one selected from the group consisting of conductive carbon black, acetylene black, carbon nanotubes, superconducting carbon black, carbon fibers, and conductive graphite.

12. The aqueous ion battery according to claim 7, wherein the current collector is at least one selected from the group consisting of a stainless steel sheet, a stainless steel mesh, and a stainless steel foil.

13. The aqueous ion battery according to claim 7, wherein the surface density of the negative electrode active material in the current collector is 2 to 5mg/cm ² 。

14. The aqueous ion battery according to claim 1, wherein the method for producing the positive electrode comprises the steps of:

mixing raw materials containing positive electrode active substances, a conductive agent and a binder with a solvent to obtain slurry, coating the slurry on a current collector, and drying to obtain the positive electrode.

15. The aqueous ion battery according to claim 14, wherein the mass ratio of the positive electrode active material, the conductive agent, and the binder is 7.5 to 9.6: 0.25-2.25: 0.25 to 2.25.

16. The aqueous ion battery according to claim 14, wherein the solvent is at least one selected from the group consisting of absolute ethyl alcohol, N-methylpyrrolidone, and N-dimethylformamide.

17. The aqueous ion battery according to claim 14, wherein the binder is at least one selected from polyvinylidene fluoride, carboxymethyl cellulose, polytetrafluoroethylene, and styrene-butadiene rubber.

18. The aqueous ion battery of claim 14, wherein the conductive agent is at least one selected from the group consisting of conductive carbon black, acetylene black, carbon nanotubes, superconducting carbon black, carbon fibers, and conductive graphite.

19. The aqueous ion battery of claim 14 wherein the current collector is selected from at least one of stainless steel sheet, stainless steel mesh, stainless steel foil.

20. The aqueous ion battery according to claim 14, wherein the positive electrode active material has an areal density of 3 to 8mg/cm in the current collector ² 。

21. The aqueous ion battery according to claim 1, wherein the method for producing the negative electrode active material comprises the steps of:

reacting a solution containing 1,4,5, 8-naphthalene tetracarboxylic anhydride and ethylenediamine for 4-18 hours at 120-180 ℃ in an inactive atmosphere, separating, washing and drying to obtain dry powder;

sintering the dry powder in an inactive atmosphere to obtain the anode active material;

the inactive atmosphere is at least one selected from nitrogen, helium and argon.

22. Use of the aqueous ion battery of any one of claims 1 to 21 for energy storage.

23. Use of the aqueous ion battery of any one of claims 1 to 21 in an aqueous energy storage battery.