CN110993944B - Water-based ion battery and application thereof - Google Patents
Water-based ion battery and application thereof Download PDFInfo
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
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- H01M4/608—Polymers containing aromatic main chain polymers containing heterocyclic rings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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
Technical Field
The application relates to a water system ion battery, belongs to the battery field.
Background
Aqueous ion batteries are battery systems that use water as the electrolyte. Compared with other non-aqueous ion batteries, the aqueous ion battery has the advantages of good safety performance, high ion conductivity, low price, easy obtainment and the like. The water-based battery can finish operations such as battery production, assembly, sealing and the like without a water-free and oxygen-free environment, and the production and manufacturing cost of the battery are greatly reduced, so that the water-based battery is gradually valued, and is very suitable for a large-scale energy storage market. The energy storage batteries used commercially at present are mainly lead-acid batteries, lithium iron phosphate or ternary power batteries. Among them, lead-acid batteries have short life and high pollution. The negative electrode uses metallic lead (Pb), and lead sulfate (PbSO) is generated in the reaction process 4 ) The passivation layer causes capacity fade with a cycle life of only a few hundred turns. Lithium iron phosphate or ternary power batteries all use organic electrolyte and are inflammableThe explosion safety is low. Meanwhile, the nickel, cobalt, manganese, iron and other metals are used, so that the cost is not advantageous. All of the batteries cannot meet the special requirements (such as high safety, ultra-long cycle life, low cost and the like) in the energy storage field.
In the development of aqueous ion batteries, aqueous lithium ion batteries have been developed to some extent. However, lithium resources on earth are difficult to support for the application needs of large energy storage systems. The basic reserve of the global lithium resource is about 58M tons (calculated by lithium carbonate), and most lithium resources are concentrated in the plateau salt lake with the altitude of 4000 meters or more, so that the development and the utilization are difficult. The presently known recoverable reserves are about 25M tons. The current annual consumption of global lithium carbonate is about 7 to 8 ten thousand tons, with estimated recovery times of over 50 years. In contrast, sodium has similar chemical properties to lithium and is thus considered to be able to replace lithium for use in aqueous ion battery systems. Sodium is abundant in the crust, and the price of sodium salt is only one tenth of that of lithium salt. Therefore, the water-based sodium ion battery has wide application prospects in the power generation side and the user side energy storage fields by combining various advantages of the water-based battery.
However, the aqueous secondary battery which has been developed at present has various problems. If the cycle life is low, the materials are difficult to amplify, and meanwhile, the problems of large-scale application and the like cannot be realized. The main bottleneck of the low cycle life of aqueous sodium ion batteries is the negative electrode material. Up to now, titanium sodium phosphate and Prussian blue have been developed as negative electrode materials for aqueous sodium ion batteries at home and abroad, but in aqueous solution, the materials can generate hydrogen evolution side reaction when discharged, so that the cycle life of the battery is low; and the electrochemical capacity of the cathode material is low, so that the capacity of the full battery is difficult to develop.
In view of the above, the present application provides a novel aqueous ion battery.
Disclosure of Invention
According to one aspect of the application, the water-based ion battery is provided, and the problems that the existing negative electrode material is poor in stability in water-based electrolyte, and a hydrogen evolution side reaction occurs during discharging, so that the cycle life of the water-based sodium ion battery is low and the specific capacity is low are solved; the existing cathode electrode material has complex electrode preparation and battery assembly process, high requirements on conditions of an operation workshop and high material preparation cost, so that the production and manufacturing cost of the whole battery is increased; the existing anode material and anode sodium-embedded material have the problem of poor matching (such as mass ratio of anode and cathode electrode materials, 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.
The aqueous ion battery is characterized by 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 includes polyimide containing naphthalene ring; and
a positive electrode containing a positive electrode active material; the positive electrode active material comprises a sodium intercalation material selected from NaMnO 2 、Na x MnO 2 、NaFeFe(CN) 6 、Na 2 CoFe(CN) 6 、Na 2 NiFe(CN) 6 At least one of them.
Wherein NaMnO 2 lambda-MnO for intercalation of sodium ions 2 The method comprises the steps of carrying out a first treatment on the surface of the x is 0.44-0.95;
NaMnO 2 lambda-MnO for intercalation of sodium ions 2 Prepared according to the method of document (1-2);
document 1: whitare 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, tsuhikawa T.enhanced supercapacitive behaviors of birnesite. Electric. Commun.,2008,10 (10): 1435-1437.
NaFeFe(CN) 6 、Na 2 CoFe(CN) 6 、Na 2 NiFe(CN) 6 Prepared according to the method of literature (3-7);
document 3: C.D.Wessells, S.V.Peddada, R.A.Huggins and Y.Cui, 'Nickel hexacyanoferrate nanoparticle electrodes for aqueous sodium and potassium ion batteries', nano Lett.,2011,11,5421-5425.
Document 4: yang young, zhongsheng Sang & Jinning Liu. Recent developments on aqueous sodiumion materials Technology Advanced Performance Materials 2016:2016 VOL.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 long cycle life aqueous electrolyte battery for grid-scale energy storage, nature Commun, 2012,3:1149.
Document 7: wu X, cao Y, ai X, et al A Low-cost and environmentally benign aqueous rechargeable sodium-ion battery based on NaTi 2 (PO 4 ) 3 -Na 2 NiFe(CN) 6 intercalation chemistry.Electrochem.Commun.,2013,31(0):145-148.
NaxMnO 2 Prepared according to the method of literature (8-10);
document 8: whitare J, tevar A, shamma S.Na 4 Mn 9 O 18 as a positive electrodematerial for an aqueous electrolyte sodium-ion energy storage device.Electrochem.Commun.,2010,12(3):463-466.
Document 9: 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 electrode active material to the negative electrode active material is 1-4;
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 lithium manganate.
Optionally, the chemical formula of the polyimide containing naphthalene ring is shown as formula I:
wherein n=1000 to 10000.
Optionally, the electrolyte is selected from at least one of sodium sulfate, sodium nitrate, sodium phosphate, sodium carbonate, sodium permanganate, sodium chloride, sodium bromide, and sodium iodide.
Optionally, the concentration of the electrolyte in the electrolyte is 1.5M to 2.5M.
Optionally, the aqueous ion battery further comprises a separator separating the positive electrode and the negative electrode and passing electrolyte ions.
Optionally, the membrane is at least one selected from glass fiber filter paper, adsorption type glass fiber membrane and non-woven fabric.
Optionally, the preparation method of the negative electrode comprises the following steps:
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.
Optionally, the mass ratio of the anode active material, the conductive agent and the binder is 5.5-9.6: 0.25 to 3:0.25 to 1.25.
Optionally, the mass ratio of the negative electrode active material, the conductive agent and the binder is 6:3:1.
optionally, the solvent is at least one selected from absolute ethyl alcohol, N-methyl pyrrolidone and N-dimethylformamide;
optionally, the binder is at least one selected from polyvinylidene fluoride, carboxymethyl cellulose, polytetrafluoroethylene and styrene-butadiene rubber;
optionally, the conductive agent is at least one selected from conductive carbon black, acetylene black, carbon nanotubes, superconductive carbon black, carbon fibers and conductive graphite;
optionally, the current collector is at least one selected from stainless steel sheet, stainless steel mesh, stainless steel foil.
Optionally, the surface density of the negative electrode active material on the current collector is 2-5 mg/cm 2 。
Optionally, the preparation method of the positive electrode comprises the following steps:
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.
Optionally, the mass ratio of the positive electrode active material, the conductive agent and the binder is 7.5-9.6: 0.25 to 2.25:0.25 to 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 at least one selected from absolute ethyl alcohol, N-methyl pyrrolidone and N-dimethylformamide;
the binder is at least one selected from polyvinylidene fluoride, carboxymethyl cellulose, polytetrafluoroethylene and styrene-butadiene rubber;
the conductive agent is at least one selected from conductive carbon black, acetylene black, carbon nanotubes, superconductive carbon black, carbon fibers and conductive graphite;
the current collector is at least one selected from stainless steel sheet, stainless steel net and stainless steel foil.
Optionally, the positive electrode active material has an areal density of 3 to 8mg/cm in the current collector 2 。
Optionally, the preparation method of the anode active material includes the following steps:
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;
and sintering the dry powder in an inactive atmosphere to obtain the anode active material.
Optionally, the inert atmosphere is selected from at least one of 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.
Alternatively, the molar ratio of 1,4,5, 8-naphthalene tetracarboxylic anhydride to ethylenediamine is 1:1 to 2.
Optionally, the sintering temperature is 200-350 ℃.
Optionally, the sintering time is 3-8 hours.
Specifically, the preparation method of the negative electrode active material comprises the following steps:
step A: in a solution of N-Dimethylformamide (DMF) according to a molar ratio of 1:1 adding 1,4,5, 8-naphthalene tetracarboxylic anhydride powder and ethylenediamine solution, and keeping magnetic stirring. The reaction vessel was a glass flask. The flask was argon shielded. The flask was transferred to a 50 ℃ oil bath and gradually warmed to 150 ℃. The reaction was maintained at this temperature for 4 to 18 hours.
And (B) step (B): the resultant was collected, centrifuged, and the supernatant was removed. The lower centrifuged precipitate was washed with N-dimethylformamide for dilution and subjected to a second centrifugation. And then washing and centrifuging by using ethanol. And (5) drying the final substance in a vacuum oven to obtain dry powder.
Step C: sintering the dry powder in a tube furnace, and protecting the 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 ) An aqueous solution;
a membrane, glass fiber filter paper (porosity of 1 micron or less, thickness of 260 microns or so);
a negative electrode, a polyimide electrode containing naphthalene rings; and
positive electrode, sodium material electrode (NaMnO) 2 、Na x MnO 2 、NaFeFe(CN) 6 、Na 2 CoFe(CN) 6 、Na 2 NiFe(CN) 6 The method comprises the steps of carrying out a first treatment on the surface of the Wherein: x is 0.44 to 0.95).
Specifically, the negative electrode includes:
a negative electrode active material, a polyimide organic material containing naphthalene rings;
a conductive agent, conductive carbon black (Super P carbon);
a binder, polytetrafluoroethylene (PTFE) emulsion; and
current collector, stainless steel mesh.
Specifically, the preparation method of the negative electrode comprises the following steps:
mixing and stirring the anode active material, the conductive carbon black and the binder in a mass ratio of 6:3:1 in ethanol solution to form slurry, coating the slurry on a stainless steel net, and then drying in vacuum. The electrode area was about 1.5cm 2 The surface density of the active substance is 2-5 mg cm -2 。
Specifically, the positive electrode includes:
positive electrode active material, sodium manganate (NaMnO) 2 I.e. lambda-MnO intercalated with sodium ions 2 )；
A conductive agent, conductive carbon black (Super P carbon);
a binder, polytetrafluoroethylene (PTFE) emulsion; and
current collector, stainless steel mesh.
Specifically, the preparation method of the positive electrode comprises the following steps:
mixing and stirring the anode active material, the conductive carbon black and the binder according to the mass ratio of 8:1:1 in ethanol to form slurry, coating the slurry on a stainless steel net, and then drying in vacuum. The electrode area was about 1.5cm 2 The surface density of the active substance is 3-8mg.cm -2 。
The working principle of the water system ion battery is as follows:
when in charging: the positive electrode sodium manganate is used for removing sodium, sodium ions are conducted to the surface of the negative electrode polyimide carbonyl in the electrolyte and adsorbed by carbonyl functional groups, and electrons of an external circuit obtained by carbonyl are reduced;
when discharging, the following steps are carried out: the carbonyl on the surface of the negative electrode material removes sodium ions, and simultaneously the carbonyl loses electrons to be oxidized, and the sodium ions are conducted to positive electrode sodium manganate in electrolyte and are embedded into a sodium manganate structure.
The aqueous sodium ion battery adopts aqueous solution containing sodium ions as electrolyte, and the positive electrode is composed of different ion intercalation compounds. During charging, sodium ions are separated from the positive electrode and are diffused to the negative electrode through electrolyte, adsorption or intercalation reaction occurs in the negative electrode, and electrons are transferred from the positive electrode to the negative electrode. The discharging process is opposite to the charging process.
According to another aspect of the present application, there is provided a use of the aqueous ion battery in energy storage.
According to another aspect of the application, the application of the water-based ion battery in the water-based energy storage battery is provided.
The beneficial effects that this application can produce include:
1) Polyimide-based organic materials containing naphthalene rings have been demonstrated to be capable of operating in nonaqueous (conventional) ion batteries, aqueous flow batteries, and aqueous lithium ion batteries. The material is firstly used in the water-based sodium ion secondary battery, and excellent electrochemical performance is obtained by optimizing the formula of the positive electrode and the negative electrode and the N/P ratio. Polyimide-based organic materials containing naphthalene rings, which have one naphthalene ring in the repeating unit, and two imide structures with four carbonyl functions. Wherein the carbonyl functionality is electrochemically active and can adsorb and desorb lithium ions thereby contributing to capacity. Meanwhile, the lithium ion battery has high mechanical strength and thermal stability, can generate ion coordination reaction with high reversibility in chemical and structural aspects in the charge and discharge process, has high reaction rate and wide ion selection, and is matched with mature electrode materials to form a stable water system battery. Compared with the existing water-based battery electrode materials, the energy and power indexes of the battery electrode materials are not inferior, even the battery electrode materials are superior in the aspects of cost, low-temperature performance, overcharge performance and the like, and the battery electrode materials are a great breakthrough in the development of water-based batteries. In addition, the price is low, the raw material resources are almost unlimited, and the specific energy of the battery can be improved by more than a multiple by means of more optimized molecular structural design and positive electrode material collocation;
2) The water-based ion battery provided by the application has the advantages that the electrode preparation process of the organic anode material is simple; the requirements on the workshops for battery assembly are low (no sealing is needed, the drying environment is needed, etc.); the electrode material can exist stably in the water system battery, and can inhibit side reaction of water molecules in the battery in the charging and discharging process to the greatest extent, so that the capacity and the circulation stability of the battery are improved, the circulation times can reach more than 1000 times, and the cycle times are higher than those of a lead-acid battery (400 times) and an organic lithium/sodium ion battery (500-1000 times), and the life cycle requirement of an energy storage power station can be met;
3) The aqueous ion battery provided by the application comprises a polyimide organic electrode material containing naphthalene rings, wherein the polyimide organic electrode material is used as a negative electrode for an aqueous sodium ion battery, and a metal oxide material of a sodium intercalation system is used as a positive electrode. The water system battery has the advantages of absolute safety (no fire or explosion), high cycle life (> 1000 times), no noble metal, environment friendliness, controllable cost, quick charge (good sodium ion conduction in the water system), wide temperature application range (low temperature under salt water, high temperature on salt water) and the like. The device is very suitable for large-scale energy storage application;
4) The large temperature application range (-35 ℃ to 40 ℃) of the water system battery can meet the application requirements of the energy storage power station in extreme environments. The fast charging performance can meet the frequency modulation requirement in the energy storage system. In addition, the method can also meet the application scenes such as renewable energy grid connection and auxiliary service fields. In the power generation side and user side energy storage fields with main requirements of peak clipping, valley filling, peak regulation, frequency modulation and improvement of electric energy quality, the water system energy storage battery also has good application prospects.
Drawings
Fig. 1 is a charge-discharge curve diagram of a full-cell aqueous system based on a polyimide negative electrode and a sodium manganate positive electrode according to example 4 of the present application;
fig. 2 is a graph of the cycle performance of the aqueous full cell based on polyimide negative electrode and sodium manganate positive electrode of example 4 of the present application.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially.
The analytical method in the examples of the present application is as follows:
electrochemical performance was tested using a New Will cell tester (model: CT-4008-5V20mA-164, new Will electronics Inc. of Shenzhen City). On the test instrument, the following procedure was set: standing for 1min; constant current charging to 1.9V at 1.0C current; then the mixture is placed for 1min; then discharging to 0.7V at a constant current of 1.0C; the above charge and discharge steps were repeated 800 times.
Example 1 Synthesis of negative electrode active material
Step A: in 400mL of a solution of N-Dimethylformamide (DMF) in a molar ratio of 1:1.01 52.08g of 1,4,5, 8-naphthacene anhydride powder and 2.54mL of ethylenediamine monohydrate solution were added with magnetic stirring. The reaction vessel was a glass flask. The flask was argon shielded. The flask was transferred to a 50 ℃ oil bath and gradually warmed to 150 ℃. The reaction was kept at this temperature for 4 hours.
And (B) step (B): the resultant was collected, centrifuged, and the supernatant was removed. The lower centrifuged precipitate was washed with N-dimethylformamide for dilution and subjected to a second centrifugation. And then washing and centrifuging by using ethanol. And (5) drying the final substance in a vacuum oven to obtain dry powder.
Step C: sintering the dry powder in a tube furnace, and protecting the argon atmosphere. The sintering temperature was 350℃and the sintering time was 3 hours, giving sample 1.
Example 2 preparation of electrode
Negative electrode
Active material: polyimide organic Material sample 1 containing naphthalene Ring
Conductive agent: conductive carbon black (Super P carbon)
And (2) a binder: polytetrafluoroethylene (PTFE) emulsion
Current collector: stainless steel net
The preparation process comprises the following steps: mixing and stirring active substances, conductive carbon black and a binder in a mass ratio of 6:3:1 in an ethanol solution to form slurry, coating the slurry on a stainless steel net, and then drying in vacuum. The electrode area was about 1.5cm 2 The active material has a single-sided surface density of 2mg.cm -2 。
Example 3 preparation of electrode
And (3) a positive electrode:
active material: sodium manganate (NaMnO) 2 I.e. lambda-MnO intercalated with sodium ions 2 )
Conductive agent: conductive carbon black (Super P carbon)
And (2) a binder: polytetrafluoroethylene (PTFE) emulsion
Current collector: stainless steel net
The flow is as follows: mixing and stirring active substances, conductive carbon black and a binder according to the mass ratio of 8:1:1 in ethanol to form slurry, coating the slurry on a stainless steel net, and then drying in vacuum. The electrode area was about 1.5cm 2 The active material has a single-sided surface density of 5mg cm -2 。
Example 4 Assembly of Battery
Structural composition
Electrolyte solution: 2.5M sodium sulfate (Na 2 SO 4 ) Aqueous solution
A diaphragm: glass fiber filter paper (porosity below 1 micron, thickness about 260 micron)
And (3) a negative electrode: polyimide electrode containing naphthalene ring
And (3) a positive electrode: sodium manganate electrode
The assembly process comprises the following steps: placing the negative electrode shell on an insulation platform surface, and placing a negative electrode plate in the center of the negative electrode shell; then, putting the diaphragm on the upper layer of the negative pole piece, taking a proper amount of electrolyte drops by a liquid transfer device, and adding the electrolyte drops on the surface of the diaphragm to fully infiltrate the diaphragm and the pole piece; then, sequentially placing the positive pole piece, the gasket, the spring piece and the positive shell on the upper layer of the diaphragm by using an insulating tweezers; wherein, one surface of the positive and negative pole piece coated with the electrode material faces towards and is close to the diaphragm; finally, placing the battery on a battery sealing machine die by using insulating tweezers, adjusting the pressure to 850Pa, and keeping the pressure for 5 seconds; thus, the entire battery is assembled.
Example 5 Assembly of Battery
The structural composition was similar to example 4, except that the electrolyte was 2M sodium sulfate (Na 2 SO 4 ) An aqueous solution.
Example 6 Battery Assembly
The structural composition was similar to example 4, except that the electrolyte was 1.5M sodium sulfate (Na 2 SO 4 ) An aqueous solution.
Example 7 Assembly of Battery
The structural composition was similar to that of example 4, except that the positive electrode was Na 2 CoFe(CN) 6 。
Example 8 Assembly of Battery
The structural composition was similar to that of example 4, except that the positive electrode was Na 2 NiFe(CN) 6 。
Example 9 Battery Assembly
The structural composition was similar to that of example 4, except that the positive electrode was Na 0.44 MnO 2 。
Example 10 Assembly of Battery
The structural composition was similar to example 4, except that the positive electrode was NaFeFe (CN) 6 。
Example 11 Assembly of Battery
The structural composition was similar to that of example 4, except that the positive electrode was Na 0.95 MnO 2 。
Example 12 Battery Performance test
Test conditions: when in use, the battery is charged firstly, and then discharge and charge cycle are carried out. Charge-discharge current: 1 c=100 mA/g.
The charge-discharge curve of the aqueous full cell based on the polyimide negative electrode and the sodium manganate positive electrode corresponds to the assembled cell in example 4 as shown in fig. 1. The reversible charge-discharge specific capacity of the first turn is shown in FIG. 1 to be 117mAh/g.
The cycle performance graph of the aqueous full cell based on the polyimide negative electrode and the sodium manganate positive electrode corresponds to the assembled cell in example 4, as shown in fig. 2. Charge-discharge current: 1 c=100 mA/g. FIG. 2 shows that after the 3 rd turn, the charge-discharge coulomb efficiency can reach more than 98%, and can be maintained all the time. The discharge capacity and the charge capacity are fully utilized, and almost no side reaction is caused. After 800 circles of circulation, the capacity still has 112mAh/g, and the capacity retention rate is as high as more than 96%.
Effect of positive-negative electrode active mass ratio (P/N) on full cell cycling stability. The research shows that when P/N=1.5, namely the mass of positive electrode sodium manganate is 2 times less than the active mass of negative electrode organic matter, the battery capacity decays rapidly, and the charge-discharge capacity decays to 83% of the 1 st circle after 800 circles; when P/n=2.5, that is, when the mass of positive sodium manganate is greatly excessive than the active mass of negative organic matter by 2 times, the battery capacity keeps higher stability, the specific charge-discharge capacity retention rate after 800 circles is up to more than 96%, and experimental data are shown in table 1.
TABLE 1
The performance of the assembled batteries of examples 5-11 was similar to that of the assembled battery of example 4.
The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.
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.
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| CN111477853B (en) * | 2020-04-17 | 2022-06-10 | 北京恩力动力科技有限公司 | Aqueous sodium-based mixed ion secondary battery |
| CN111584867B (en) * | 2020-05-15 | 2021-07-13 | 宁波锋成纳米科技有限公司 | Electrode and preparation method and application thereof |
| CN111900387B (en) * | 2020-07-28 | 2022-05-17 | 宁波锋成先进能源材料研究院 | Water-based battery pole piece material, water-based battery pole piece, preparation method and application thereof |
| CN113381097B (en) * | 2021-06-03 | 2022-07-15 | 中国科学技术大学 | Aqueous prussian blue derivative-hydrogen secondary battery |
| CN114927686A (en) * | 2022-05-27 | 2022-08-19 | 哈尔滨工程大学 | Preparation method and application of novel aqueous magnesium-sodium mixed ion battery cathode material |
| CN115275208B (en) * | 2022-09-27 | 2023-02-07 | 宇恒电池股份有限公司 | High-specific-energy aqueous lithium ion battery and preparation method thereof |
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