CN112259912A - Safe rechargeable potassium polyaniline battery and preparation method thereof - Google Patents

Safe rechargeable potassium polyaniline battery and preparation method thereof Download PDF

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CN112259912A
CN112259912A CN202011125062.7A CN202011125062A CN112259912A CN 112259912 A CN112259912 A CN 112259912A CN 202011125062 A CN202011125062 A CN 202011125062A CN 112259912 A CN112259912 A CN 112259912A
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potassium
polyaniline
battery
electrolyte
metal
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韩家军
徐鹏
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Weihai Tiankun New Energy Technology Co ltd
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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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/137—Electrodes based on electro-active polymers
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses a safe rechargeable potassium polyaniline battery and a preparation method thereof, which solve the technical problems of high raw material cost, complex operation, poor safety, incapability of being widely applied to energy storage equipment economically due to rare metal lithium, serious volume expansion of a potassium metal negative electrode and serious dendritic crystal growth of the existing rechargeable battery; meanwhile, the preparation method is also provided, and the preparation method can be widely applied to the technical field of new materials and new energy.

Description

Safe rechargeable potassium polyaniline battery and preparation method thereof
Technical Field
The invention belongs to the technical field of new materials and new energy, and particularly relates to a safe rechargeable potassium polyaniline battery and a preparation method thereof.
Background
Modern society is unsustainable of relying on energy stored in fossil fuels. The burned fossil fuel is not recyclable and the gaseous exhaust gases from its combustion contribute to the greenhouse effect. Solar and wind energy are sustainable and can be converted to electricity, but this electricity can only be used through energy storage devices. With the progress of lithium ion battery technology, solid polymer lithium ion batteries with ultra-thin, ultra-light and high energy density and ferrous phosphate lithium ion batteries capable of being rapidly charged and discharged have been developed in succession, and the lithium ion batteries are widely applied to the fields of electronic information, new energy, power vehicles, environmental protection and the like. Lithium ion batteries cannot be economically applied to energy storage devices due to the scarcity of metallic lithium. It is now widely accepted that wireless leather-oriented lithium ion batteries are not economically competitive with the energy stored in fossil fuels in terms of large-scale energy storage.
The lithium ion battery takes a carbon material as a negative electrode and a lithium-containing compound as a positive electrode, no metal lithium exists, and only lithium ions exist, so that the lithium ion battery is formed. The lithium ion battery mainly comprises four parts: positive, negative, electrolyte and separator. A lithium ion battery is a secondary battery (rechargeable battery) that mainly operates by movement of lithium ions between a positive electrode and a negative electrode. During charging and discharging, Li + is inserted and extracted back and forth between two electrodes: during charging, Li + is extracted from the positive electrode and is inserted into the negative electrode through the electrolyte, and the negative electrode is in a lithium-rich state; the opposite is true during discharge. Lithium ions are inserted/extracted and inserted/extracted back and forth between the positive and negative electrodes during charge and discharge, and are figuratively referred to as "rocking chair batteries".
However, the cost is the primary consideration of the stationary battery, and the lithium element in the lithium ion battery has a limited storage capacity on the earth, only accounts for 0.002 wt.% of the earth crust, and is difficult to recycle, resulting in high cost. In contrast, sodium and potassium are abundant in 2.36 wt.% and 2.09 wt.%, respectively. It is therefore of great interest to develop sodium or potassium batteries for the stationary storage of electricity. However, the size of lithium ions is small, and lithium ions can be inserted and extracted back and forth between two electrodes in a lithium ion battery, while the large size of Na + and K + ions limits the selectivity of reversible Na + or K + insertion back and forth between two electrodes, thereby further limiting the application of the lithium ion battery in the field of metal ion batteries.
In addition, although the potassium ion reserves are abundant, the fermi energy of potassium is higher than that of sodium, and has a lower reduction potential than that of sodium ions, and theoretically potassium has a better performance than sodium in the field of metal ion batteries, studies on lithium ion batteries and sodium ion batteries actually studied at present have been reported and matured, but studies on the maturity of potassium ion batteries are still rare. To date, negative electrode materials for potassium ion batteries have been studied to some extent, including carbon-based materials, alloy materials, organic compounds, etc., but the problems of low reversible specific capacity and poor cycle stability of these negative electrode materials have seriously hindered the research and development of potassium ion batteries. In practical application, because the electrochemical activity of the potassium metal is higher, repeated electrochemical deposition and separation processes can cause serious volume expansion and uncontrollable dendritic crystal growth, and lead to an unstable solid electrolyte membrane (sei) on the surface of the negative electrode, so that the coulombic efficiency is reduced, the electrochemical stability is poor, even internal short circuit is caused, the potential safety hazard of ignition exists, and the problems seriously hinder the large-scale application of the potassium metal negative electrode. These problems are exacerbated under high current operating conditions in practical applications. In the past, researchers have proposed that the electrolyte components and concentration regulation are included to construct artificial sei and composite potassium metal cathodes aiming at designing stable potassium metal cathodes, but the goals of restraining dendritic crystal growth and relieving volume expansion cannot be achieved.
The traditional preparation method of electrochemical deposition is difficult to obtain the composite potassium metal cathode with high stability and high safety because the morphology of the metal potassium is difficult to control and the growth of dendritic crystals cannot be controlled. Therefore, it is important to find a potassium metal negative electrode which is easy to operate, has stable performance and can effectively inhibit dendrites.
Disclosure of Invention
Aiming at the defects and shortcomings in the prior art, the invention provides the rechargeable potassium polyaniline battery which has low manufacturing cost, good safety, good cycling stability, higher coulombic efficiency, obvious dendritic crystal inhibition effect, capability of meeting the requirements of most of potassium battery anode materials, less manufacturing equipment, simple process and safety and the preparation method thereof.
Therefore, the invention provides a safe rechargeable potassium polyaniline battery, which comprises a battery anode, a battery cathode, a diaphragm and an electrolyte, wherein the battery anode is a potassium polyaniline anode, the battery cathode is a potassium metal cathode, the electrolyte is an organic liquid electrolyte potassium hexafluorophosphate solution, and the electrolyte is a polymer-gel electrolyte formed by polymer gel of crosslinked polymethyl methacrylate;
the diaphragm adopts a double-layer diaphragm, wherein a glass fiber diaphragm is tightly attached to the potassium metal negative electrode, and a polymer gel electrolyte of crosslinked polymethyl methacrylate is filled between the glass fiber diaphragm and the potassium metal negative electrode.
Preferably, a polyethylene microporous diaphragm clings to the surface of the potassium polyaniline positive electrode; the thickness of the glass fiber diaphragm is 0.02-0.3mm, and the thickness of the polyethylene microporous diaphragm is 0.01-0.03 mm.
Preferably, the polyaniline is polyaniline composed of nanofibers with a length of several micrometers and a diameter of about 80nm, which are prepared by a chemical oxidative polymerization method; and after ammonia de-doping, washing until ammonium ions are not contained, soaking the mixture into potassium hexafluorophosphate solution for doping, washing, and drying in vacuum at normal temperature to obtain the potassium polyaniline material.
Preferably, the preparation process of the potassium polyaniline positive electrode material is as follows: filling polyaniline powder doped with potassium hexafluorophosphate solution at the bottom of a female die, descending a male die, pre-pressing, ascending the male die, adding expanded graphite powder into the female die, descending the male die again, and pressing and molding the expanded graphite powder and the polyaniline powder together to obtain the potassium polyaniline anode.
Preferably, the preparation process of the potassium metal negative electrode is as follows: preparing a composite network electrode of MXene nanosheets DN-MXene and carbon nano tubes with titanium defects and rich nitrogen in a suction filtration mode, and melting potassium metal into a network framework to obtain a potassium metal negative electrode material K @ DN-MXene/CNT; and wetting the potassium metal cathode material by using a polymer-gel electrolyte to obtain the potassium metal cathode.
Preferably, the preparation process of the electrolyte is as follows: in a vacuum glove box, under the protection of argon, mixing and stirring propylene carbonate, ethylene carbonate and dimethylformamide uniformly, adding potassium hexafluorophosphate, anisole and dimethyl methylphosphate in sequence, and stirring until the mixture is clear to obtain the electrolyte.
The preparation method of the safe rechargeable potassium polyaniline cell comprises the following steps: the prepared potassium polyaniline positive electrode, the prepared potassium metal negative electrode, the prepared diaphragm and the prepared electrolyte are matched according to the required weight and quantity, then the obtained mixture is sent into a vacuum glove box, the potassium metal negative electrodes which are wetted and wrapped by the polymer gel of the crosslinked polymethyl methacrylate are sequentially stacked according to the potassium polyaniline positive electrode, the polyethylene microporous diaphragm and the prepared glass fiber diaphragm, then the obtained stack is pressurized, the obtained battery cell is placed into a metal box, and the electrolyte is added and then the obtained stack is sealed.
Preferably, the positive and negative matching mode of the assembled battery is a positive-negative matching mode or a two-positive-negative matching mode.
Preferably, the metal box is made of any one of aluminum, aluminum alloy, steel, nickel and copper.
Preferably, in the metal box, the metal sheet contacting with the positive electrode of the battery cell and the metal sheet contacting with the negative electrode of the battery cell are not directly connected, but are connected by plastic in the middle.
The invention has the beneficial effects that:
(1) the safe rechargeable potassium polyaniline battery and the preparation method thereof have the advantages of low manufacturing cost, good safety, good cycling stability, higher coulombic efficiency, obvious dendritic crystal inhibition effect, less manufacturing equipment and simple process, and meet the requirements of most of potassium battery anode materials. Compared with the prior art, the invention integrates the polyaniline anode and the polymer-gel electrolyte, so that the low-cost potassium metal battery has higher energy density and excellent cycle stability, and enhances the safety of the battery.
(2) Firstly, the p-type polymer anode used by the potassium polyaniline anode can increase the voltage of the battery; and the polymer-gel electrolyte formed by the polymer gel of the crosslinked polymethyl methacrylate replaces the traditional organic liquid electrolyte in the glass fiber diaphragm, so that the electrode/electrolyte interface can be maintained to be very stable, and the potassium ion dendritic-free insertion/extraction of the potassium metal cathode is realized.
(3) The potassium metal cathode material wets the potassium metal cathode through the polymer gel electrolyte, and a crosslinking structure in the polymer-gel electrolyte provides a pore with adjustable size in the charge-discharge process, so that a solid electrolyte interface formed at the potassium metal cathode/electrolyte interface is further stabilized. This alternative electrolyte/cathode strategy provides a promising new approach for low cost potassium metal batteries that store electricity on a stationary basis. The electrolyte is enhanced through the polymer-gel, the growth of dendritic crystals is effectively inhibited, the service life of the potassium metal negative electrode is prolonged, and the use cost of the potassium metal battery is obviously saved.
Detailed Description
The following specific examples further illustrate the invention to aid in understanding the contents of the invention. The method used in the invention is a conventional method if no special provisions are made; the raw materials and the apparatus used are, unless otherwise specified, conventional commercially available products.
Example 1
The invention provides a safe rechargeable potassium polyaniline battery which comprises a battery anode, a battery cathode, a diaphragm and an electrolyte, wherein the battery cathode is a potassium metal cathode, the battery anode is a potassium polyaniline anode, the electrolyte is an organic liquid electrolyte potassium hexafluorophosphate solution, and the electrolyte is a polymer-gel electrolyte formed by polymer gel of crosslinked polymethyl methacrylate (PMMA).
The diaphragm of the battery adopts a double-layer diaphragm, wherein the diaphragm clings to the potassium metal cathode is a glass fiber diaphragm, and the polymer gel electrolyte of the crosslinked polymethyl methacrylate is filled between the glass fiber diaphragm and the potassium metal cathode; the polymer-gel electrolyte wets the potassium metal negative electrode and its crosslinked structure provides pores of adjustable size to stabilize the solid electrolyte interface formed at the potassium metal negative electrode/polymer-gel electrolyte interface.
The safe rechargeable potassium polyaniline battery provided by the invention has the following specific principle in the charge and discharge process: during discharging, the anion PF 6-of the electrolyte salt is inserted into the potassium polyaniline anode material, the external circuit electrons move from the potassium polyaniline anode to the potassium metal cathode, and meanwhile, K + of KPF6 salt is embedded into the potassium metal cathode; in the discharging process, PF6 & lt- & gt is extracted from a potassium polyaniline positive electrode material, external circuit electrons move from a potassium metal negative electrode to a potassium polyaniline positive electrode, and K & lt + & gt is extracted from the potassium metal negative electrode.
The diaphragm of the potassium-polyaniline battery adopts a double-layer diaphragm, wherein the diaphragm clinging to the negative electrode is a glass fiber diaphragm, the liquid absorption performance is very good, but the mechanical performance and the isolation performance are poor, but the diaphragm clinging to the positive electrode is a polyethylene microporous diaphragm, the excellent isolation effect is utilized, but the absorption of electrolyte is less; wherein the thickness of the glass fiber diaphragm is 0.02-0.3mm, the thickness of the polyethylene microporous diaphragm is 0.01-0.03mm, the thickness of the glass fiber diaphragm is 0.1-0.15mm, the thickness of the polyethylene microporous diaphragm is 0.010-0.012mm, and the diaphragm has the best liquid absorption, conductivity and dendritic crystal penetration inhibiting effect.
The reason that the negative electrode is made of the glass fiber paper diaphragm is that the potassium-polyaniline battery is high in unit area capacity and needs more electrolyte, so that the thickness of the diaphragm is thicker, and more electrolyte is adsorbed. As the positive electrode material polyaniline is in a porous structure, and the gaps can absorb enough electrolyte, the polyethylene diaphragm clings to the positive electrode and is required to provide isolation performance and mechanical performance,
the negative electrode is a potassium metal negative electrode, and a polymer-gel electrolyte formed by polymer gel of crosslinked polymethyl methacrylate replaces the traditional organic liquid electrolyte in the glass fiber diaphragm, so that the glass fiber diaphragm is required to provide electrolyte required by charging and discharging for the glass fiber diaphragm; a stable electrode/electrolyte interface is established by the polymer gel electrolyte, so that the potassium metal battery of the present invention has excellent cycle stability. Although the diaphragm of the potassium-polyaniline battery is much thicker than that of the traditional lithium ion battery, the total resistance of the diaphragm is not increased too much because the composite diaphragm is adopted, the liquid absorption amount of the glass fiber paper diaphragm is large, the pores are large, the solution resistance is low, and the thickness of the polyethylene diaphragm is lower than that of the traditional lithium ion battery, so that the resistance of the diaphragm is not increased too much.
The specific preparation method of the safe rechargeable potassium polyaniline battery comprises the following steps:
(1) polyaniline in the potassium-polyaniline anode material is prepared by a chemical oxidation polymerization method and is composed of nanofibers with the length of several micrometers and the diameter of about 80 nm; and (3) after 5% (mass) ammonia water is used for dedoping for 4 hours, washing until ammonium ions are not contained, soaking the mixture into potassium hexafluorophosphate solution for doping, washing for 3 times, and performing vacuum drying at normal temperature for 24 hours to obtain the potassium polyaniline material. The concentration of the adopted potassium hexafluorophosphate solution is 0.1-3mol/L, and the doping temperature is 10-70
Figure BDA0002733339580000062
The doping time is 2-6 h. Wherein the concentration of potassium hexafluorophosphate solution is 0.5-1.2mol/L, and the doping temperature is 20-50
Figure BDA0002733339580000061
The effect of doping time 3-4h is best.
The polyaniline doped with potassium hexafluorophosphate is conductive, and the conductivity of the polyaniline is far higher than that of the anode material of the traditional lithium ion battery, so the thickness of the polyaniline can be very thick and even can exceed 3 mm. The thickness of the polyaniline of the positive electrode current collector with the same weight is 20-30 times that of the polyaniline of the traditional lithium ion battery, so that the using amount of the positive electrode current collector is greatly saved, and the coating process is reduced. Secondly, polyaniline is a porous organic matter, has excellent affinity with organic solvent electrolyte, and the porous structure enables the electrolyte to permeate into pores, thereby greatly improving the reaction area, and positive and negative ions required by charge and discharge can be provided by the electrolyte in the pores. Finally, polyaniline is an organic polymer, and the molecular structure of the polyaniline has a large number of carbon-hydrogen bonds and nitrogen-hydrogen bonds, so that strong van der waals force exists among polyaniline molecules, and the polyaniline can be directly pressed and molded under high pressure without adding any binder, which is similar to a common plastic powder pressing and molding mechanism. The polyaniline obtained by compression molding does not use a binder, so that the conductivity of the polyaniline is improved, the cost is saved, the process is simplified, the polyaniline obtained by compression molding can be used without vacuum drying, and the pollution of the binder (styrene butadiene rubber emulsion) to the environment is reduced.
In the process of charging and discharging of the secondary battery, the falling of the positive and negative active substances from the current collector is the main reason of reducing the battery capacity, and the improvement of the cohesiveness between the positive and negative electrode materials of the battery and the current collector is always a contradiction problem in the battery field. The increase of the binder inevitably causes the poor conductivity of the anode and cathode materials of the battery, the increase of the internal resistance of the battery and the reduction of the performance of the battery. Therefore, the polyaniline positive plate is obtained by adopting expanded graphite as a current collector and adopting a one-step compression molding method. Expanded graphite has a certain cohesiveness, and graphite paper prepared by compression molding of expanded graphite has been widely used in various fields. The expanded graphite as a carbon material has excellent compatibility with organic polyaniline (similar compatibility principle); therefore, the polyaniline powder and the expanded graphite are pressed and molded together, not only a binder is not used, but also the cohesiveness between the polyaniline powder and the expanded graphite is ensured, and the process for preparing the positive plate is simplified.
(2) The preparation process of the potassium polyaniline anode material comprises the following steps: filling polyaniline powder doped with potassium hexafluorophosphate solution at the bottom of the female die, then making the male die move downwards, and then making the polyaniline powder enter the female diePrepressing, then ascending a convex die, adding expanded graphite powder into the concave die, descending the convex die again, pressing and molding the expanded graphite powder and the polyaniline powder together, wherein the prepressing pressure is 50-800kg/cm2The pressure for press forming is 600-4000kg/cm2And after the pressure intensity is uniformly distributed, taking out the expanded graphite and the polyaniline block material which are subjected to compression molding to obtain the potassium polyaniline anode with the thickness of 2-3 mm. Wherein the pre-pressing pressure is 100-300kg/cm2The pressure for press forming is 1400-3000kg/cm2And maintaining the pressure for 10-60 seconds, wherein the obtained potassium polyaniline positive plate has moderate density and best structural strength, and the thickness, shape and size of the polyaniline material can be properly adjusted by adjusting a mould in the pressing process according to the requirements of assembling the battery, and the tabs are reserved.
In the process of compression molding, the mass ratio of the expanded graphite powder to the polyaniline powder is required, if the consumption of the expanded graphite is too small, the thickness of an expanded graphite layer in a compression-molded positive plate is small, the subsequent assembly of a battery is not facilitated, and the structural strength of a thin tab is unacceptable. And too much expanded graphite is not needed, so that the cost is increased and the specific energy of the whole battery is reduced due to excessive expanded graphite. The mass ratio of the expanded graphite powder to the polyaniline powder is 1:10-1:1, wherein the effect is best at 1:8-1: 5.
In the pressing process, pre-pressing polyaniline is necessary, because when polyaniline powder is filled into a female die, the polyaniline powder is difficult to ensure even filling, and the polyaniline powder can be uniformly distributed in the die by pre-pressing. The pressure for pre-pressing is 50-800kg/cm2, the pressure cannot be too large, otherwise, polyaniline can be formed into a hard block material after being pressed and formed, and then expanded graphite is added, so that the polyaniline and the expanded graphite cannot be formed by mutual bonding of powder; in the case where both are "soft", the polyaniline and the expanded graphite powder are diffused into each other and bonded during the pressing. The pressure is too small and not good, at the moment, the polyaniline powder is fluffy, and the lubricity of the expanded graphite powder is good, so that a large amount of graphite powder can slide into the polyaniline powder, the expanded graphite which permeates into the deep part of the polyaniline powder cannot be utilized, and the waste of the expanded graphite is caused, so that the pre-pressing pressure is 100 plus 300kg/cm 2. Finally, the pressure intensity of the compression molding is 600-; meanwhile, the density of the anode is low, the volume is large, and the volumetric specific energy of the top layer is reduced. The molding pressure is too large and not good, energy waste is caused, the obtained polyaniline has few pores and less adsorbed electrolyte, and when the polyaniline is serious, a large amount of closed pores are formed in the polyaniline, the electrolyte cannot permeate into the polyaniline in the closed pores, so that the polyaniline in the region cannot be applied, and the utilization rate of active substances is reduced.
Therefore, the density of the positive plate obtained by the pressure of the polyaniline in the press forming process is 1400-3000kg/cm2 is moderate, and the structural strength can also meet the use requirement. The proton acid doped polyaniline is converted into potassium hexafluorophosphate doped polyaniline, and the polyaniline and expanded graphite are subjected to one-step compression molding to obtain the material which is applied to the positive electrode material of the potassium ion battery.
(3) The preparation process of the potassium metal cathode comprises the following steps: preparing a composite network electrode of MXene nanosheets DN-MXene and carbon nano tubes with titanium defects and rich nitrogen in a suction filtration mode, and melting potassium metal into a network framework to obtain a potassium metal negative electrode material K @ DN-MXene/CNT; and wetting the potassium metal cathode material by using a polymer-gel electrolyte to obtain the potassium metal cathode.
In the structure of the potassium metal cathode, the in-line carbon nano tubes are used as a deposition framework of the potassium metal to construct an ion-electron mixed conductive network, so that the two problems of growth of metal dendrites and volume effect are solved, and the high-performance potassium metal composite cathode material is prepared; the high-conductivity three-dimensional skeleton reduces the local current density, and the DN-MXene nanosheet has the potassium affinity characteristic, so that the nucleation growth of potassium is induced, and the uniform distribution of potassium metal in the network is realized. Therefore, the structure of the potassium metal negative electrode has a remarkable dendritic crystal inhibiting effect in the charge and discharge processes, and meets the requirements of most potassium battery positive electrode materials.
Thicker positive and negative electrode film layers are very beneficial to lithium ion batteries, and have 2 main advantages: 1. the thicker film layer can greatly reduce the using amount of the positive and negative current collectors, the same current collector has thicker film layer and increased battery capacity, and under the premise of unchanged rated capacity, the using amount of the current collector is reduced, thereby saving the cost and improving the specific energy of the whole battery. 2. The thicker anode and cathode film layers can reduce the film coating times, correspondingly reduce the subsequent operation procedures of cutting, coating and the like, and improve the utilization rate of all equipment. The thickness of the anode and cathode film layers of the potassium-polyaniline secondary battery is several times or even tens times of that of the traditional lithium ion battery, because the conductivity of the anode active material potassium polyaniline is far higher than that of the anode of the traditional lithium ion battery, and the high-conductivity three-dimensional framework reduces the local current density corresponding to the cathode carbon nanotube composite network electrode, and the thickness of the high-conductivity three-dimensional framework can be correspondingly increased.
(4) The preparation process of the electrolyte comprises the following steps: placing the reagent and a stirrer in a vacuum glove box, vacuumizing the vacuum glove box until the vacuum degree exceeds 0.9MPa, injecting dry argon, mixing and stirring propylene carbonate, ethylene carbonate and dimethylformamide uniformly under the protection of argon, sequentially adding potassium hexafluorophosphate, anisole and dimethyl methylphosphate, stirring the mixture to be clear, standing and curing the mixture for 24 hours, and then using the mixture. Because the potential of potassium or potassium-embedded graphite is very low (-about 3V), the potassium or potassium-embedded graphite can be oxidized by oxygen and nitrogen in the air or reacts with water to form hydrogen, the whole preparation process needs to be carried out in vacuum, and argon is filled for protection, otherwise, a carbonate solvent in the electrolyte can absorb moisture and oxygen.
The mass ratio of the propylene carbonate, the ethylene carbonate and the dimethyl formamide is 1:0.2-0.7:0.05-0.2, and when the ratio is 1:0.4-0.5:0.1-0.12, the indexes of the obtained solvent such as viscosity, boiling point and solubility are the best. The concentration of potassium hexafluorophosphate in the electrolyte is 0.2-2.5mol/L, the concentration of anisole is 0.2-1g/L, the concentration of dimethyl methylphosphate is 6-30g/L, wherein the concentration of potassium hexafluorophosphate is 1-1.25mol/L, the concentration of anisole is 0.7-0.8g/L, and the concentration of dimethyl methylphosphate is 15-20g/L, so that the electrolyte has the highest conductivity, film forming performance and flame retardant performance.
(5) The preparation method of the safe rechargeable potassium polyaniline battery comprises the following steps: the prepared potassium polyaniline positive electrode, the prepared potassium metal negative electrode, the prepared diaphragm and the prepared electrolyte are matched according to the required weight and quantity, then are sent into a vacuum glove box, the potassium metal negative electrodes which are wetted and wrapped by the polymer gel of the crosslinked polymethyl methacrylate are sequentially stacked according to the potassium polyaniline positive electrode, the prepared polyethylene microporous diaphragm and the prepared glass fiber diaphragm, then are pressurized for 10-20 seconds, the pressure intensity is 20-100kPa, the battery cell is placed into a metal box, then the battery cell is sent into the vacuum glove box, and after the battery cell is kept stand for 12 hours, the electrolyte is added, and then the battery cell is kept stand for 12 hours and then is sealed and taken out. The polyethylene diaphragm and the glass fiber diaphragm have certain elasticity, after the batteries are laminated, proper pressure intensity is applied, so that the positive and negative electrodes of the batteries are in closer contact with the diaphragms, and after the batteries are arranged in the battery box, the batteries can be tightly assembled, so that the internal resistance of the batteries is reduced, the cycle life is prolonged, and the structural strength of the positive and negative electrodes of the batteries is improved.
The electrolyte needs to be strictly protected from contamination by moisture, oxygen and nitrogen, so the electrolyte needs to be injected in a vacuum glove box. Because the battery is assembled in the atmosphere, a small amount of moisture, oxygen and nitrogen are inevitably absorbed, and therefore when the battery enters the vacuum glove box, the battery needs to be kept still for a period of time, and after the moisture, the oxygen and the nitrogen in the battery are discharged through the vacuum glove box, the electrolyte is injected. And after the electrolyte is fully permeated, sealing the battery and taking out the battery.
The positive and negative matching of the assembled battery can select a positive-negative or two positive-negative matching mode. The positive and negative matching mode which adopts a positive and negative mode is a more common mode, and has the advantages of simple structure, convenient assembly and low internal resistance of the battery; the defects are that the utilization rate of the current collector is low, the utilization rate is only the area with the common utilization rate, the unit area capacity of the battery is small, and the assembly of a large-capacity battery is difficult.
The structure is simple in a two-positive-one-negative mode, the utilization rate of a negative current collector is doubled, the positive current collector is unchanged, the unit area capacity of the battery is doubled, and the large-capacity battery can be assembled. The appropriate positive and negative matching modes are properly selected according to the application of the battery, the small-capacity battery can adopt a positive-negative matching mode, and the large-capacity battery adopts a structure with two positive electrodes and one negative electrode, which is more reasonable.
The metal box is made of aluminum alloy or nickel plated on the surface of steel; in the metal box, the metal sheet contacted with the positive electrode of the battery core and the metal sheet contacted with the negative electrode of the battery core are not directly connected, and the middle of the metal box is connected through plastic, so that the metal box plays a role of a current collector besides a packaging role.
The invention integrates the polyaniline anode and the polymer-gel electrolyte, so that the low-cost potassium metal battery has higher energy density and excellent cycle stability, and enhances the safety of the battery. Firstly, the p-type polymer anode used by the potassium polyaniline anode can increase the voltage of the battery; and the polymer-gel electrolyte formed by the polymer gel of the crosslinked polymethyl methacrylate replaces the traditional organic liquid electrolyte in the glass fiber diaphragm, so that the electrode/electrolyte interface can be maintained to be very stable, and the potassium ion dendritic-free insertion/extraction of the potassium metal cathode is realized. The potassium metal cathode material wets the potassium metal cathode through the polymer gel electrolyte, and a crosslinking structure in the polymer-gel electrolyte provides a pore with adjustable size in the charge-discharge process, so that a solid electrolyte interface formed at the potassium metal cathode/electrolyte interface is further stabilized. This alternative electrolyte/cathode strategy provides a promising new approach for low cost potassium metal batteries that store electricity on a stationary basis. The electrolyte is enhanced through the polymer-gel, the growth of dendritic crystals is effectively inhibited, the service life of the potassium metal negative electrode is prolonged, and the use cost of the potassium metal battery is obviously saved. The stable electrode/electrolyte interface is established by the polymer gel electrolyte, so that the potassium metal battery of the invention has excellent cycle stability, and provides possibility for the application of the potassium metal battery in power grid scale electric energy storage.
For example, the positive and negative electrode matching of the assembled battery can be selected in a positive-negative or two positive-negative matching manner according to actual requirements; the material of the metal box can be any one of aluminum, aluminum alloy, steel, nickel and copper, and the safe rechargeable potassium polyaniline battery and the preparation method thereof can be realized.
Example 2
The preparation method of the potassium hexafluorophosphate doped polyaniline comprises the following specific steps:
polyaniline in the potassium-polyaniline anode material is prepared by a chemical oxidation polymerization method and is composed of nanofibers with the length of several micrometers and the diameter of about 80 nm; and (3) performing de-doping for 4 hours by 5% (mass) ammonia water, washing until ammonium ions are not contained, soaking the mixture into potassium hexafluorophosphate solution for doping, wherein the concentration of the adopted potassium hexafluorophosphate solution is 2mol/L, the doping temperature is 50 ℃, the doping time is 4 hours, washing is performed for 3 times, vacuum drying is performed for 24 hours at normal temperature, the potassium polyaniline material doped with potassium hexafluorophosphate polyaniline is obtained, and the electrical conductivity is measured to be 6.5S/cm after compression molding under the pressure of 2t/cm 2.
Example 3
The preparation process of the potassium polyaniline positive electrode material comprises the following specific steps:
the tablet pressing mold comprises a male mold, a female mold and a baffle, wherein the female mold is fixed on a working table surface of a pressure intensity machine, and the male mold is fixed on a pressure head of a hydraulic pressure intensity machine. Firstly, a baffle is arranged in a female die, then 15g of potassium hexafluorophosphate doped polyaniline powder is arranged in the female die, then the male die goes downwards, and 150kg/cm is adopted2Pre-pressing the polyaniline powder, and uniformly distributing the polyaniline powder in the female die; then the male die ascends, 2g of expanded graphite is filled into the female die, the male die descends again, and the pressure intensity is 2500kg/cm2Maintaining the pressure for 50 seconds, moving the male die upwards for 3-5mm, withdrawing the baffle at the bottom of the female die, slowly moving the male die downwards again, extruding the polyaniline and the expanded graphite tablet out of the female die, loading the baffle into the female die again, and simultaneously pushing the obtained plate-shaped positive electrode out of the dieCollecting; and then the male die ascends to leave the female die, and polyaniline powder is filled again, and tabletting is carried out as above. The resulting potassium polyaniline/expanded graphite pellet was weighed to give a weight of 12.65g, a size of 45.5X 85.5X 2.38mm, and a density of the whole positive electrode of 1.326g/cm3(ii) a The thickness of the graphite layer was 0.294mm and the thickness of polyaniline was 2.086mm as measured by a stereomicroscope.
Example 4
The preparation process of the potassium metal cathode comprises the following specific steps: preparing a composite network electrode of MXene nanosheets DN-MXene and carbon nano tubes with titanium defects and rich nitrogen in a suction filtration mode, and melting potassium metal into a network framework to obtain a potassium metal negative electrode material K @ DN-MXene/CNT; and wetting the potassium metal cathode material by using a polymer-gel electrolyte to obtain a potassium metal cathode with the thickness of 0.73 mm.
Example 5
The preparation of the electrolyte comprises the following specific steps:
taking preparation of 1L of electrolyte as an example, weighing each component of the electrolyte, placing the reagent and the stirrer in a vacuum glove box, vacuumizing the vacuum glove box until the vacuum degree exceeds 0.9MPa, injecting dry argon, and carrying out argon protection. Firstly, 600ml of propylene carbonate is added into a stirring tank, 184.06g of potassium hexafluorophosphate is added for a plurality of times under the stirring condition and is completely dissolved, then 180ml of dimethyl carbonate is added, the mixture is stirred until the solution is clear and transparent, then 100ml of dimethylformamide is added, and the mixture is stirred for 30 minutes after the solution is clear. Then adding 16g of methyl dimethyl phosphate and 0.75g of anisole, stirring until the solution is completely clear, fixing the volume to 1L by adopting propylene carbonate, and then sealing and curing for 24 h. Because the potential of potassium or potassium-embedded graphite is very low (-about 3V), the potassium or potassium-embedded graphite can be oxidized by oxygen and nitrogen in the air or reacts with water to form hydrogen, the whole preparation process needs to be carried out in vacuum, and argon is filled for protection, otherwise, a carbonate solvent in the electrolyte can absorb moisture and oxygen. The density of the electrolyte at this time was 1.18g/cm3The conductivity was 14.8mS/cm, and the water content was 14.7 ppm.
Example 6
The preparation method of the safe rechargeable potassium polyaniline battery comprises the following steps: the prepared potassium polyaniline positive electrode, the prepared potassium metal negative electrode, the prepared diaphragm and the prepared electrolyte are matched according to the required weight and quantity, then are sent into a vacuum glove box, and according to the potassium polyaniline positive electrode, the prepared polyethylene microporous diaphragm and the prepared glass fiber diaphragm, the prepared potassium metal negative electrodes which are wetted and wrapped by the polymer gel of the crosslinked polymethyl methacrylate are sequentially stacked, then are pressurized for 20 seconds, the pressure is 80kPa, the battery cell is placed into a metal box, then is sent into the vacuum glove box, is kept still for 12 hours, is added with the prepared electrolyte, is kept still for 12 hours, and is sealed and taken out. The polyethylene diaphragm and the glass fiber diaphragm have certain elasticity, after the batteries are laminated, proper pressure intensity is applied, so that the positive and negative electrodes of the batteries are in closer contact with the diaphragms, and after the batteries are arranged in the battery box, the batteries can be tightly assembled, so that the internal resistance of the batteries is reduced, the cycle life is prolonged, and the structural strength of the positive and negative electrodes of the batteries is improved.
The electrolyte needs to be strictly protected from contamination by moisture, oxygen and nitrogen, so the electrolyte needs to be injected in a vacuum glove box. Because the battery is assembled in the atmosphere, a small amount of moisture, oxygen and nitrogen are inevitably absorbed, and therefore when the battery enters the vacuum glove box, the battery needs to be kept still for a period of time, and after the moisture, the oxygen and the nitrogen in the battery are discharged through the vacuum glove box, the electrolyte is injected. And after the electrolyte is fully permeated, sealing the battery and taking out the battery.
The positive and negative matching of the assembled battery can select a positive-negative or two positive-negative matching mode. The positive and negative matching mode which adopts a positive and negative mode is a more common mode, and has the advantages of simple structure, convenient assembly and low internal resistance of the battery; the defects are that the utilization rate of the current collector is low, the utilization rate is only the area with the common utilization rate, the unit area capacity of the battery is small, and the assembly of a large-capacity battery is difficult.
The structure is simple in a two-positive-one-negative mode, the utilization rate of a negative current collector is doubled, the positive current collector is unchanged, the unit area capacity of the battery is doubled, and the large-capacity battery can be assembled. The appropriate positive and negative matching modes are properly selected according to the application of the battery, the small-capacity battery can adopt a positive-negative matching mode, and the large-capacity battery adopts a structure with two positive electrodes and one negative electrode, which is more reasonable.
The metal box is made of aluminum alloy or nickel plated on the surface of steel; in the metal box, the metal sheet contacted with the positive electrode of the battery core and the metal sheet contacted with the negative electrode of the battery core are not directly connected, and the middle of the metal box is connected through plastic, so that the metal box plays a role of a current collector besides a packaging role.
The invention integrates the polyaniline anode and the polymer-gel electrolyte, so that the low-cost potassium metal battery has higher energy density and excellent cycle stability, and enhances the safety of the battery. Firstly, the p-type polymer anode used by the potassium polyaniline anode can increase the voltage of the battery; and the polymer-gel electrolyte formed by the polymer gel of the crosslinked polymethyl methacrylate replaces the traditional organic liquid electrolyte in the glass fiber diaphragm, so that the electrode/electrolyte interface can be maintained to be very stable, and the potassium ion dendritic-free insertion/extraction of the potassium metal cathode is realized. The potassium metal cathode material wets the potassium metal cathode through the polymer gel electrolyte, and a crosslinking structure in the polymer-gel electrolyte provides a pore with adjustable size in the charge-discharge process, so that a solid electrolyte interface formed at the potassium metal cathode/electrolyte interface is further stabilized. This alternative electrolyte/cathode strategy provides a promising new approach for low cost potassium metal batteries that store electricity on a stationary basis. The electrolyte is enhanced through the polymer-gel, the growth of dendritic crystals is effectively inhibited, the service life of the potassium metal negative electrode is prolonged, and the use cost of the potassium metal battery is obviously saved. A stable electrode/electrolyte interface is established by the polymer gel electrolyte, so that the potassium metal battery of the present invention has excellent cycle stability, which provides a possibility for the application of the potassium metal battery to grid-scale electrical energy storage.
The performance of the potassium polyaniline cell in the above example was further examined and analyzed as follows:
the assembled battery, namely the potassium polyaniline battery, prepared in example 6 by a positive-negative matching manner was subjected to charge and discharge detection. The results of detecting the charge-discharge cycle capacity and the coulombic efficiency are specifically as follows, and the initial capacity can reach 108.7mAhg-1After 10 cycles, the sample decays to 97.3mAhg-1Decay to 94.2mAhg after 50 cycles-1Decay to 93.5mAhg after 100 cycles-1The hundred-cycle decay rate is 14.0%. In the whole discharging process, the coulombic efficiency is 96.3-99.1%, and the potassium polyaniline battery provided by the invention is fully proved to have good circulation stability and higher coulombic efficiency, has a remarkable dendritic crystal inhibition effect, and meets the requirements of most of potassium battery anode materials.
In conclusion, the safe rechargeable potassium polyaniline battery and the preparation method thereof have the advantages of low manufacturing cost, good safety, less manufacturing equipment and simple process. Compared with the prior art, the invention integrates the polyaniline anode and the polymer-gel electrolyte, so that the low-cost potassium metal battery has higher energy density and excellent cycle stability, and enhances the safety of the battery. A stable electrode/electrolyte interface is established by the polymer gel electrolyte, so that the potassium metal battery of the present invention has excellent cycle stability, which provides a possibility for the application of the potassium metal battery to grid-scale electrical energy storage.
However, the above description is only exemplary of the present invention, and the scope of the present invention should not be limited thereby, and the replacement of the equivalent components or the equivalent changes and modifications made according to the protection scope of the present invention should be covered by the claims of the present invention.

Claims (10)

1. A safe rechargeable potassium polyaniline battery comprises a battery anode, a battery cathode, a diaphragm and an electrolyte, and is characterized in that the battery anode is a potassium polyaniline anode, the battery cathode is a potassium metal cathode, the electrolyte is an organic liquid electrolyte potassium hexafluorophosphate solution, and the electrolyte is a polymer-gel electrolyte formed by polymer gel of crosslinked polymethyl methacrylate;
the diaphragm adopts a double-layer diaphragm, wherein a glass fiber diaphragm is tightly attached to the potassium metal cathode, and the crosslinked polymethyl methacrylate polymer gel electrolyte is filled between the glass fiber diaphragm and the potassium metal cathode.
2. The safe rechargeable potassium polyaniline cell as claimed in claim 1, wherein a polyethylene microporous membrane is closely attached to the surface of the potassium polyaniline positive electrode; the thickness of the glass fiber diaphragm is 0.02-0.3mm, and the thickness of the polyethylene microporous diaphragm is 0.01-0.03 mm.
3. A safe rechargeable potassium polyaniline cell as claimed in claim 2, wherein the polyaniline is a polyaniline composed of nanofibers with a length of several micrometers and a diameter of about 80nm prepared by chemical oxidative polymerization; and after ammonia de-doping, washing until ammonium ions are not contained, soaking the mixture into potassium hexafluorophosphate solution for doping, washing, and drying in vacuum at normal temperature to obtain the potassium polyaniline material.
4. The safe rechargeable potassium polyaniline cell as claimed in claim 3, wherein the preparation process of the potassium polyaniline positive electrode material is as follows: filling polyaniline powder doped with potassium hexafluorophosphate solution at the bottom of a female die, descending a male die, pre-pressing, ascending the male die, adding expanded graphite powder into the female die, descending the male die again, and pressing and molding the expanded graphite powder and the polyaniline powder together to obtain the potassium polyaniline anode.
5. The safe rechargeable potassium polyaniline cell as claimed in claim 2, wherein the preparation process of the potassium metal negative electrode is as follows: preparing a composite network electrode of MXene nanosheets DN-MXene and carbon nano tubes with titanium defects and rich nitrogen in a suction filtration mode, and melting potassium metal into a network framework to obtain a potassium metal negative electrode material K @ DN-MXene/CNT; and wetting the potassium metal cathode material by using a polymer-gel electrolyte to obtain the potassium metal cathode.
6. A safe rechargeable potassium polyaniline cell as claimed in claim 3, wherein the electrolyte is formulated as follows: in a vacuum glove box, under the protection of argon, mixing and stirring propylene carbonate, ethylene carbonate and dimethylformamide uniformly, adding potassium hexafluorophosphate, anisole and dimethyl methylphosphate in sequence, and stirring until the mixture is clear, thus obtaining the electrolyte.
7. The method for preparing a safe rechargeable potassium polyaniline cell as claimed in any one of claims 1 to 6, which comprises the steps of: the prepared potassium polyaniline positive electrode, the prepared potassium metal negative electrode, the prepared diaphragm and the prepared electrolyte are matched according to the required weight and quantity, then the obtained mixture is sent into a vacuum glove box, the potassium metal negative electrodes which are wetted and wrapped by the polymer gel of the crosslinked polymethyl methacrylate are sequentially stacked according to the potassium polyaniline positive electrode, the polyethylene microporous diaphragm and the prepared glass fiber diaphragm, then the obtained stack is pressed, the obtained cell is placed into a metal box, and the obtained stack is sealed after the electrolyte is added.
8. The method according to claim 7, wherein the assembled positive and negative electrode matching manner of the battery is a positive-negative matching manner, or a positive-negative matching manner.
9. The method for preparing a safe rechargeable potassium polyaniline cell as claimed in claim 7, wherein the metal box is made of any one of aluminum, aluminum alloy, steel, nickel and copper.
10. The method of claim 7, wherein the metal sheet in contact with the positive electrode and the metal sheet in contact with the negative electrode of the cell in the metal case are not directly connected, but are connected through plastic.
CN202011125062.7A 2020-10-20 2020-10-20 Safe rechargeable potassium polyaniline battery and preparation method thereof Pending CN112259912A (en)

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CN107293749A (en) * 2017-08-04 2017-10-24 威海天鲲新能源科技有限公司 Graphene Polyaniline Secondary Battery and preparation method thereof
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