CN110534847B - Rechargeable aluminum-air battery and preparation method thereof - Google Patents
Rechargeable aluminum-air battery and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a rechargeable aluminum-air battery and a preparation method thereof. The rechargeable aluminum-air battery includes: a negative electrode, a positive electrode, and an electrolyte. Wherein the negative electrode comprises an aerogel carrier and liquid metal nano-particles loaded on the aerogel carrier; the positive electrode comprises an aerogel carrier and a catalyst loaded on the aerogel carrier; the electrolyte includes an electrolyte salt and alumina. The negative electrode of the rechargeable aluminum-air battery can electrodeposit aluminum on a large scale at normal temperature, so that reversible charging at normal temperature is realized, the rechargeable aluminum-air battery has higher energy density, the problems of self-corrosion, passivation and grafting effects and the like of the conventional aluminum-air battery are solved, the safety performance is high, and the cycle life is long.
Description
Technical Field
The invention relates to the field of electrochemistry, in particular to a rechargeable aluminum-air battery and a preparation method thereof.
Background
An aluminum-air battery is a battery that can output electric energy by electrochemical reaction between chemical energy of metal aluminum or aluminum alloy and oxygen, and can reversely charge the electric energy. The electrochemical reaction found in aluminum-air batteries is carried out in an electrolyte, in primary batteries or mechanically rechargeable batteries, an aqueous electrolyte with high conductivity and low viscosity is generally used, and corrosion inhibitors for reducing the corrosion rate of hydrogen evolution are supplemented.
In some solid oxide electrolytes, reversible charge and discharge of an aluminum-air battery at normal temperature can be realized, but the system has low tolerance for discharge products, low self conductivity of the electrolyte, slow reaction rate and easy blockage of electrodes, and is not favorable for manufacturing a battery system with high energy density. In some high-temperature molten batteries, reversible charge and discharge of a high-rate metal-air battery can be realized, but the energy consumption is high, the equipment system for maintaining high temperature is complex, and the electrode material is easily oxidized and consumed. Some ionic liquids have been used as electrolytes in aluminum ion batteries and some primary batteries and have achieved good results, but it is difficult to maintain a long service life of the battery due to insufficient stability to air and water and inability to accommodate reaction products at high concentrations.
By virtue of the presence of an exchange of oxygen with the surrounding air, a metal-air battery is essentially a semi-open system, which requires a high stability of the electrolyte itself with respect to oxygen and moisture, and a high containment compatibility with respect to the discharge products of the battery. The air electrode has high-efficiency oxygen oxidation reduction catalysis performance, and generally, the air electrode with good oxygen reduction and oxygen evolution performances can be realized through the composition of a plurality of catalysts. However, the existing rechargeable aluminum-air battery still remains to be improved.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. To this end, an object of the present invention is to propose a rechargeable aluminum-air battery and a method for manufacturing the same. The negative electrode of the rechargeable aluminum-air battery can electrodeposit aluminum on a large scale at normal temperature, so that reversible charging at normal temperature is realized, the rechargeable aluminum-air battery has higher energy density, the problems of self-corrosion, passivation and grafting effects and the like of the conventional aluminum-air battery are solved, the safety performance is high, and the cycle life is long.
In one aspect of the invention, a rechargeable aluminum-air battery is presented. According to an embodiment of the present invention, the rechargeable aluminum-air battery includes: a negative electrode comprising an aerogel carrier and liquid metal nanoparticles supported on the aerogel carrier; a positive electrode including an aerogel carrier and a catalyst supported on the aerogel carrier; an electrolyte comprising an electrolyte salt and alumina.
A rechargeable aluminum-air battery according to an embodiment of the invention includes a catalyst-supported positive electrode and a porous negative electrode separated from the positive electrode by an electrolyte. The positive electrode and the negative electrode have good conductivity and mechanical property by adopting the aerogel carrier. The air anode can prevent the electrolyte from completely permeating while being fully soaked by the electrolyte, and is beneficial to constructing a gas/liquid/solid three-phase interface area. In the charging process of the battery, the anode consumes oxygen, and the aluminum oxide in the electrolyte is electrodeposited into aluminum or aluminum alloy at the cathode; during the discharge of the battery, oxygen is released from the positive electrode, and aluminum deposited from the negative electrode is oxidized and enters the electrolyte. The electrolyte has a wide electrochemical window, can completely cover the working potential of the anode and the cathode of the aluminum-air battery, is directly contacted with the atmosphere through the air electrode, is chemically stable to air and water, and has good dispersibility to alumina. Therefore, the negative electrode of the rechargeable aluminum-air battery provided by the embodiment of the invention can be used for electrodepositing aluminum on a large scale at normal temperature, so that reversible charging at normal temperature is realized, the rechargeable aluminum-air battery has higher energy density, and the problems of self-corrosion, passivation and grafting effects and the like of the existing aluminum-air battery are solved. The rechargeable aluminum-air battery has extremely high working robustness, can still keep higher charge and discharge performance after being pierced, has high safety performance and long cycle life.
In addition, the rechargeable aluminum-air battery according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the invention, the aerogel support comprises at least one of a carbon nanotube aerogel, a graphene aerogel, an ordered growth of carbon nanotubes, and a high pore inert metal foam.
In some embodiments of the present invention, the liquid metal nanoparticles are formed of at least one selected from Ga, Sn, In, and Hg.
In some embodiments of the invention, the liquid metal nanoparticles are GaSnIn alloy nanoparticles, and the mass ratio of Ga, Sn and In the GaSnIn alloy nanoparticles is 95 (0.01-3) to (0.01-2).
In some embodiments of the invention, the catalyst comprises at least one selected from the group consisting of platinum, ruthenium, palladium, platinum-nickel alloys, nitrogen-doped graphene, nitrogen-doped carbon nanotubes, cobalt oxide, manganese oxide, iron oxide, and nickel oxide.
In some embodiments of the invention, the catalyst comprises Co3O4And MnO2In said catalyst Co3O4And MnO2The mass ratio of (A) to (B) is 2 (1-3).
In some embodiments of the invention, the electrolyte salt comprises at least one selected from the group consisting of hydrophobic alkylphosphonium, alkylpiperidine, alkoxypiperidine, alkylmorpholine, alkoxymorpholine, alkylammonium, alkoxyammonium, alkylsulfonium, alkylpyrrolidine, alkylimidazolium fluorophosphate, fluoroacetate, fluoroborate, dicyanamide salt, and bis (trifluoromethanesulfonyl) imide salt.
In some embodiments of the invention, the electrolyte salt comprises aluminum trifluoromethanesulfonate, zinc dicyanamide (or zinc trifluoromethanesulfonate) and 1-butyl-1-methylpyrrolidine bis (trifluoromethanesulfonyl) imide salt, and the mass ratio of the aluminum trifluoromethanesulfonate, the zinc dicyanamide and the 1-butyl-1-methylpyrrolidine bis (trifluoromethanesulfonyl) imide salt is 1 (0.1-1): 1-1000.
In some embodiments of the invention, in the negative electrode, the mass ratio of the liquid metal nanoparticles to the aerogel carrier is 1 (0.1-1).
In some embodiments of the invention, in the positive electrode, the mass ratio of the catalyst to the aerogel carrier is 1 (0.05-1).
In some embodiments of the invention, the mass ratio of the electrolyte salt to the aluminum oxide in the electrolyte is (1-5): 1.
In another aspect of the present invention, the present invention provides a method of manufacturing the rechargeable aluminum-air battery of the above embodiment. According to an embodiment of the invention, the method comprises: preparing an aerogel carrier by using a carbon material; loading liquid metal nano particles on the aerogel carrier to obtain a negative electrode; loading a catalyst on the aerogel carrier to obtain a positive electrode; preparing electrolyte by using electrolyte salt and aluminum oxide; and packaging the negative electrode, the positive electrode and the electrolyte to obtain the rechargeable aluminum-air battery.
Therefore, the negative electrode of the rechargeable aluminum-air battery prepared by the method can be used for electrodepositing aluminum on a large scale at normal temperature, so that reversible charging at normal temperature is realized, the energy density is higher, and the problems of self-corrosion, passivation and grafting effects and the like of the conventional aluminum-air battery are solved. The rechargeable aluminum-air battery has extremely high working robustness, can still keep higher charge and discharge performance after being pierced, has high safety performance and long cycle life.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
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The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 is a graph of cycle test results of a rechargeable aluminum-air battery according to one embodiment of the present invention.
Detailed Description
The following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
In one aspect of the invention, a rechargeable aluminum-air battery is presented. According to an embodiment of the present invention, the rechargeable aluminum-air battery includes: a negative electrode, a positive electrode, and an electrolyte. The negative electrode comprises an aerogel carrier and liquid metal nanoparticles loaded on the aerogel carrier; the positive electrode comprises an aerogel carrier and a catalyst loaded on the aerogel carrier; the electrolyte includes an electrolyte salt and alumina.
A rechargeable aluminum-air battery according to an embodiment of the invention includes a catalyst-supported positive electrode and a porous negative electrode separated from the positive electrode by an electrolyte. The positive electrode and the negative electrode have good conductivity and mechanical property by adopting the aerogel carrier. The air anode can prevent the electrolyte from completely permeating while being fully soaked by the electrolyte, and is beneficial to constructing a gas/liquid/solid three-phase interface area. In the charging process of the battery, the anode releases oxygen, and aluminum ions in the electrolyte are electrodeposited into aluminum or aluminum alloy at the cathode; during the discharge of the cell, the anode consumes oxygen and the aluminum deposited on the cathode is oxidized and enters the electrolyte. The electrolyte has a wide electrochemical window, can completely cover the working potential of the anode and the cathode of the aluminum-air battery, is directly contacted with the atmosphere through the air electrode, is chemically stable to air and water, has good hydrophobicity, can keep the wide electrochemical window for a long time in air with certain humidity, and has good dispersibility to alumina. Therefore, the negative electrode of the rechargeable aluminum-air battery provided by the embodiment of the invention can be used for electrodepositing aluminum on a large scale at normal temperature, so that reversible charging at normal temperature is realized, the rechargeable aluminum-air battery has higher energy density, and the problems of self-corrosion, passivation and grafting effects and the like of the existing aluminum-air battery are solved. The rechargeable aluminum-air battery has extremely high working robustness, can still keep higher charge and discharge performance after being pierced, has high safety performance and long cycle life.
According to some embodiments of the present invention, the aerogel support may include at least one selected from the group consisting of a carbon nanotube aerogel, a graphene aerogel, an orderly grown carbon nanotube, and a high pore inert metal foam. Such aerogel carriers have higher porosity and stability, and by adopting the aerogel carriers, loading of an electrode active material and improvement of battery performance can be further facilitated. Meanwhile, the aerogel carrier is used as a carrier of the battery cathode active material, so that the problems of passivation, dendritic crystal growth and the like in the battery charging and discharging process can be further solved.
According to some embodiments of the present invention, the liquid metal nanoparticles are formed of at least one selected from Ga, Sn, In, and Hg. The metal can effectively break a passive film generated by the cathode Al in an electrochemical reaction. By loading the liquid metal nanoparticles on the negative electrode, passivation of the battery in the charging and discharging process can be further avoided.
According to some embodiments of the invention, the liquid metal nanoparticles are GaSnIn alloy nanoparticles, and the mass ratio of Ga, Sn, and In the GaSnIn alloy nanoparticles is 95 (0.01-3) to (0.01-2). Therefore, passivation of the battery in the charging and discharging process can be further avoided, conductivity of the negative electrode material is improved, and dendritic crystal growth of aluminum metal in the charging process can be effectively inhibited due to high dispersity of the negative electrode material. In addition, the inventors found that if the ratio of Ga is too low and the ratio of Sn and In is too high In the GaSnIn alloy nanoparticles, the melting point of the alloy particles is higher than room temperature, and it is difficult to form highly dispersed nanoparticles.
According to some embodiments of the invention, in the negative electrode, the mass ratio of the liquid metal nanoparticles to the aerogel carrier can be 1 (0.1-1), and the liquid metal nanoparticles are easy to agglomerate if the content of the liquid metal nanoparticles is too much.
According to the embodiment of the present invention, the specific kind of the catalyst applied to the positive electrode is not particularly limited, and one or more catalysts having single-function catalysis (catalytic oxygen reduction reaction) or dual-function catalysis (catalytic oxygen reduction reaction and oxygen precipitation reaction) such as manganese oxide, cobalt oxide, iron oxide, functionalized doped carbon, noble metal, etc. may be selected. According to some embodiments of the present invention, the catalyst applied to the positive electrode may include a material selected from Co3O4、MnO2At least one of (a). More preferably, the catalyst comprises Co3O4And MnO2And Co in the catalyst3O4And MnO2The mass ratio of (1-3) to (2).
According to some embodiments of the invention, the above comprises Co3O4And MnO2The bifunctional catalyst consists of Co with the average grain diameter of 10-100 nm3O4Particles and MnO2The particle preparation can further facilitate the loading of the catalyst particles on the aerogel carrier by controlling the particle size of the catalyst particles within the range, thereby further facilitating the exertion of the catalytic performance.
According to some embodiments of the invention, in the positive electrode, the mass ratio of the catalyst to the aerogel carrier may be 1 (0.05-1). Too much catalyst content will agglomerate on the electrode, and too little will reduce the catalytic activity of the electrode.
According to some embodiments of the present invention, the electrolyte salt may include at least one selected from the group consisting of hydrophobic alkyl phosphonium, alkyl piperidine, alkoxy piperidine, alkyl morpholine, alkoxy morpholine, alkyl ammonium, alkoxy ammonium, alkyl sulfonium, alkyl pyrrolidine, alkyl imidazole fluorophosphate, fluoroacetate, fluoroborate, dicyanamide salt, trifluoromethanesulfonate, and bis (trifluoromethanesulfonyl) imide salt. Therefore, the electrochemical window of the electrolyte can be further widened, and the working potential of the anode and the cathode of the aluminum-air battery can be completely covered. Meanwhile, the electrolyte salt is stable to air and water, and can still maintain a sufficiently wide electrochemical window in certain humid air. In some embodiments, the electrolyte region can be closed and limited in the battery or semi-open to adapt to small changes of density in the charging and discharging process, the electrolyte is separated from the atmosphere by the air electrode, and a breathable liquid separation film can be arranged according to actual needs to prevent the electrolyte from seeping out of the battery. In some embodiments, minor amounts of additives that activate the surface of the aluminum anode may be added to the electrolyte to inhibit passivation of the aluminum anode under high current density discharge conditions.
In addition, according to some embodiments of the present invention, the electrolyte may further include other metal oxides besides aluminum oxide, such as zinc oxide, etc., in which case the working potential of the electrode is still within the electrochemical window of the electrolyte, forming a zinc-air secondary battery with the dissolved zinc salt in the electrolyte.
According to some embodiments of the present invention, the electrolyte salt includes zinc trifluoromethanesulfonate and 1-butyl-1-methylpyrrolidine bis (trifluoromethanesulfonyl) imide salt, and the mass ratio of the zinc trifluoromethanesulfonate to the 1-butyl-1-methylpyrrolidine bis (trifluoromethanesulfonyl) imide salt in the electrolyte salt is 1 (1-1000). The zinc trifluoromethanesulfonate has the function of activating the surface of an aluminum anode, and the problem of electrode passivation in the charge and discharge process of the aluminum-air battery can be further solved by adding the zinc trifluoromethanesulfonate with the proportion into the 1-butyl-1-methylpyrrolidine bis (trifluoromethanesulfonyl) imide salt.
According to some embodiments of the invention, in the electrolyte, the mass ratio of the electrolyte salt to the alumina can be (1-5): 1. This makes it possible to reduce the internal resistance of the electrolyte of the battery, and if the alumina content is too high, the electrode may be clogged. According to a particular example of the invention, the above-mentioned alumina is provided in the form of a powder. The average particle diameter of the alumina powder may be 25 to 1000 nm.
The rechargeable aluminum-air battery according to the above embodiment of the present invention further includes a separator disposed between the anode and the cathode. The separator material can be selected from polyethylene, polypropylene, glass fiber and the like with high permeability, and is preferably glass fiber.
In addition, it should be noted that the rechargeable aluminum-air battery according to the above embodiment of the present invention may include one or more cells, that is, a plurality of cells may be combined in series and parallel to form a battery stack system.
In another aspect of the present invention, the present invention provides a method of manufacturing the rechargeable aluminum-air battery of the above embodiment. According to an embodiment of the invention, the method comprises: preparing an aerogel carrier by using a carbon material; loading liquid metal nano particles on an aerogel carrier to obtain a negative electrode; loading a catalyst on an aerogel carrier to obtain a positive electrode; preparing electrolyte by using electrolyte salt and aluminum oxide; and packaging the negative electrode, the positive electrode and the electrolyte to obtain the rechargeable aluminum-air battery.
Therefore, the negative electrode of the rechargeable aluminum-air battery prepared by the method can be used for electrodepositing aluminum on a large scale at normal temperature, so that reversible charging at normal temperature is realized, the energy density is higher, and the problems of self-corrosion, passivation and grafting effects and the like of the conventional aluminum-air battery are solved. The rechargeable aluminum-air battery has extremely high working robustness, can still keep higher charge and discharge performance after being pierced, has high safety performance and long cycle life.
A method of manufacturing a rechargeable aluminum-air battery according to an embodiment of the present invention will be described in detail below.
The specific method for preparing the aerogel carrier using the carbon material according to the embodiment of the present invention is not particularly limited, and those skilled in the art can select the method according to actual needs. According to the specific embodiment of the invention, the carbon material can be dispersed in deionized water to prepare a stable dispersion liquid, and the stable dispersion liquid is self-assembled by a solvothermal method to obtain the all-carbon hydrogel, and the aerogel carrier is obtained after freeze drying or supercritical drying.
According to the specific embodiment of the present invention, the highly conductive ultra-light carbon nanotube aerogel can be prepared by the following method: dispersing graphene oxide in deionized water to obtain 0.5-5 mg/mL stable dispersion liquid; acidizing a carbon nano tube, dispersing the acidized carbon nano tube into deionized water to obtain 0.5-2 mg/mL of stable dispersion liquid, uniformly mixing the graphene oxide dispersion liquid and the carbon nano tube dispersion liquid according to the mass ratio of 1 (2-5), then carrying out solvothermal self-assembly at 150-180 ℃ to obtain all-carbon hydrogel, carrying out freeze drying or supercritical drying at-60-30 ℃ for 20-60 h to obtain carbon nano tube aerogel, and carrying out reduction by a chemical reduction method or treatment at 200-1000 ℃ for 5-20 h by an inert high-temperature thermal reduction method to obtain the high-conductivity ultra-light elastic carbon nano tube aerogel.
According to an embodiment of the present invention, the liquid metal nanoparticles may be prepared by placing a metal in a solvent, liquid alloying by a water bath, and ultrasonic dispersion. And then putting the aerogel carrier into the liquid metal nanoparticle dispersion liquid, and treating by a solvothermal method to obtain the cathode uniformly loaded with the liquid metal nanoparticles.
According to the specific embodiment of the invention, the liquid GaSnIn alloy nanoparticles and the battery cathode can be prepared according to the following method: putting Ga, Sn and In into absolute ethyl alcohol according to the mass ratio of 95 (0.01-3) to 0.01-2, carrying out liquid alloying In a water bath at 50-80 ℃ for 0-24 h to obtain an alloy which is liquid at room temperature, and carrying out ultrasonic oscillation for 0-1 h to prepare a nanoparticle dispersion liquid. The method comprises the steps of diluting a liquid GaSnIn alloy nanoparticle dispersion liquid to 0.1-10 mg/mL by using absolute ethyl alcohol, putting 1 part by mass of carbon nanotube aerogel into 30-100 parts by mass of a diluent, and treating for 5-12 hours at 140-180 ℃ by a solvothermal method to obtain the carbon nanotube aerogel uniformly loaded with liquid metal nanoparticles, wherein the carbon nanotube aerogel can be directly used as a cathode.
According to the embodiment of the invention, the catalyst can be dispersed in a solvent, the uniform dispersion liquid is obtained through ultrasonic treatment, the aerogel carrier is placed in the catalyst dispersion liquid, and the anode of the uniformly-loaded catalyst is prepared through solvothermal treatment.
According to an embodiment of the invention, the supported bifunctional catalyst Co3O4And MnO2The granular battery positive electrode can be prepared according to the following method: mixing Co3O4And MnO2Directly dispersing particles (with the particle size of 10-100 nm) in absolute ethyl alcohol according to the mass ratio of (1-3) to 2, and performing ultrasonic dispersion for 0-1 h to obtain 5-20 mg/L uniform dispersion liquid. And (2) putting 1 part by mass of carbon nanotube aerogel into 20-40 parts by mass of catalyst dispersion liquid, and treating for 6-12 hours at 150-200 ℃ by a solvothermal method to prepare the carbon nanotube aerogel uniformly loaded with the catalyst nanoparticles, wherein the carbon nanotube aerogel can be directly used as an air anode.
According to an embodiment of the present invention, the packaging of the battery may be performed according to the following steps: the method comprises the steps of completely soaking a glass fiber diaphragm by using an electrolyte, respectively attaching a positive electrode and a negative electrode to two sides of the diaphragm, enabling the uncharged battery to have certain flexibility, packaging the positive electrode by using porous air-permeable materials such as foamed nickel and foamed copper, packaging the negative electrode by using materials such as copper foil and nickel foil, and performing edge pressing and sealing on the periphery by using high-molecular insulating polymer materials such as polyethylene and polypropylene.
In addition, it should be noted that all the features and advantages described above for the "rechargeable aluminum-air battery" are also applicable to the "method for preparing a rechargeable aluminum-air battery", and are not repeated herein.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.
Examples
Firstly, the preparation method of the porous carbon nanotube aerogel electrode of the aluminum-air battery comprises the following specific steps:
dispersing graphene oxide in deionized water to obtain 1.5mg/mL stable dispersion liquid; acidizing the carbon nano tube, dispersing the acidized carbon nano tube into deionized water to obtain 1mg/mL stable dispersion liquid, uniformly mixing the graphene oxide dispersion liquid and the carbon nano tube dispersion liquid according to the mass ratio of 1:2.5, then carrying out solvothermal method self-assembly at 180 ℃ to obtain all-carbon hydrogel, carrying out freeze drying at-50 ℃ or supercritical drying for 48h to obtain carbon nano tube aerogel, and then carrying out reduction by a chemical reduction method or treatment by an inert high-temperature thermal reduction method at 250 ℃ for 12h to obtain the high-conductivity ultralight elastic carbon nano tube aerogel.
Secondly, the specific preparation process of the aluminum-air battery cathode is as follows:
adding Ga, Sn and In into absolute ethyl alcohol according to the mass ratio of 95:1:0.5, performing liquid alloying In 70 ℃ water bath for 12h to obtain an alloy which is liquid at room temperature, and performing ultrasonic oscillation for 0.5h to prepare a nanoparticle dispersion liquid. Diluting the liquid GaSnIn alloy nanoparticle dispersion liquid to 1mg/mL by using absolute ethyl alcohol, putting 1 part by mass of carbon nanotube aerogel into 30 parts by mass of the diluent, and treating for 12 hours at 160 ℃ by a solvothermal method to prepare the carbon nanotube aerogel uniformly loaded with the liquid metal nanoparticles, wherein the carbon nanotube aerogel can be directly used as a cathode.
Thirdly, the preparation of the anode of the aluminum-air battery comprises the following specific steps:
mixing Co3O4And MnO2The particles (with the particle size of 50nm) are directly dispersed in absolute ethyl alcohol according to the mass ratio of 1:1, and the uniform dispersion liquid of 5mg/L is obtained after ultrasonic dispersion for 0.5 h. And (2) putting 1 part by mass of carbon nanotube aerogel into 20 parts by mass of catalyst dispersion liquid, and treating for 12 hours at 160 ℃ by a solvothermal method to obtain the carbon nanotube aerogel uniformly loaded with the catalyst nanoparticles, wherein the carbon nanotube aerogel can be directly used as an air anode.
Fourthly, the specific preparation process of the aluminum-air battery electrolyte is as follows:
(1) the fused 1-butyl-1-methylpyrrolidine bis (trifluoromethanesulfonyl) imide salt is dried in vacuum at 120 ℃ for 24 hours to remove water, and then aluminum trifluoromethanesulfonate is added into the dried salt in anhydrous inert atmosphere at normal temperature to oscillate for 6 hours, so that a transparent solution with the concentration of 100mM is obtained.
(2) And dissolving 1 part by mass of zinc dicyandiamide in 200 parts by mass of mixed liquor to obtain clear and transparent electrolyte.
(3) 1 part by mass of alumina powder was dispersed in 2 parts by mass of an electrolytic solution to obtain a suspension in which alumina particles were uniformly dispersed.
And fifthly, packaging the cathode, the anode and the mixed solution prepared in the steps to obtain a rechargeable aluminum-air battery product.
Sixthly, testing the cycle performance:
the battery is charged and discharged under air with certain humidity, and the specific capacity of the battery is based on the sum of the mass of the anode and the cathode, the electrolyte and the diaphragm. The loaded current multiplying power is 1C, after 500 times of stable cycles are completed, the test battery is punctured by a puncher, other test conditions are kept unchanged, the test is continued, and the test result is shown in figure 1. The result shows that the aluminum-air battery of the invention has the advantages that all components are stable to the atmosphere, the hydrophobicity is good, the combustion is difficult, and the mechanical property is good, after the puncture test, the battery only loses part of the capacity, the stable charge and discharge performance can be still kept, and the aluminum-air battery can stably run for at least 300 cycles and only loses a small amount of capacity.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (6)
1. A rechargeable aluminum-air battery, comprising:
a negative electrode comprising an aerogel carrier and liquid metal nanoparticles supported on the aerogel carrier;
a positive electrode including an aerogel carrier and a catalyst supported on the aerogel carrier;
an electrolytic solution including an electrolyte salt and alumina;
wherein the aerogel support comprises at least one of a carbon nanotube aerogel, a graphene aerogel, and a high pore inert metal foam, the liquid metal nanoparticles being formed from at least one selected from Ga, Sn, In, and Hg; the electrolyte salt comprises aluminum trifluoromethanesulfonate, zinc dicyanamide and 1-butyl-1-methylpyrrolidine bis (trifluoromethanesulfonyl) imide salt, wherein the mass ratio of the aluminum trifluoromethanesulfonate to the zinc dicyanamide to the 1-butyl-1-methylpyrrolidine bis (trifluoromethanesulfonyl) imide salt is 1 (0.1-1): 1-1000.
2. The rechargeable aluminum-air battery of claim 1, wherein the liquid metal nanoparticles are GaSnIn alloy nanoparticles, and the mass ratio of Ga, Sn, In the GaSnIn alloy nanoparticles is 95 (0.01-3) to (0.01-2).
3. The rechargeable aluminum-air battery of claim 1, wherein the catalyst comprises at least one selected from the group consisting of platinum, ruthenium, palladium, platinum-nickel alloys, nitrogen-doped graphene, nitrogen-doped carbon nanotubes, cobalt oxide, manganese oxide, iron oxide, and nickel oxide.
4. The rechargeable aluminum-air battery of claim 3, wherein the catalyst comprises Co3O4And MnO2In said catalyst Co3O4And MnO2The mass ratio of (A) to (B) is 2 (1-3).
5. The rechargeable aluminum-air battery according to any one of claims 1 to 4, wherein in the negative electrode, the mass ratio of the liquid metal nanoparticles to the aerogel carrier is 1 (0.1 to 1);
in the positive electrode, the mass ratio of the catalyst to the aerogel carrier is 1 (0.05-1);
in the electrolyte, the mass ratio of the electrolyte salt to the alumina is (1-5): 1.
6. A method of manufacturing the rechargeable aluminum-air battery of any one of claims 1 to 5, comprising:
preparing an aerogel carrier by using a carbon material;
loading liquid metal nano particles on the aerogel carrier to obtain a negative electrode; loading a catalyst on the aerogel carrier to obtain a positive electrode;
preparing electrolyte by using electrolyte salt and aluminum oxide;
and packaging the negative electrode, the positive electrode and the electrolyte to obtain the rechargeable aluminum-air battery.
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| CN111668450B (en) * | 2020-06-22 | 2022-11-11 | 吉林大学 | Paper-based aluminum air battery with liquid alloy modified anode and preparation method |
| CN111682182B (en) * | 2020-06-22 | 2021-09-21 | 吉林大学 | Printable's novel flexible paper base aluminium air battery |
| CN111769291A (en) * | 2020-06-24 | 2020-10-13 | 中南大学 | Sodium-carbon dioxide battery, anode used on sodium-based battery and preparation method thereof |
| CN112615013A (en) * | 2020-12-14 | 2021-04-06 | 桂林理工大学 | Liquid metal @ carbon nanotube lithium air battery anode and preparation method thereof |
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