CN111769278A - Water system rechargeable zinc ion battery based on aromatic organic matter positive electrode material and application thereof - Google Patents
Water system rechargeable zinc ion battery based on aromatic organic matter positive electrode material and application thereof Download PDFInfo
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Abstract
The invention discloses a water system rechargeable zinc ion battery based on an aromatic organic matter positive electrode material and application thereof. The water system rechargeable zinc ion battery based on the aromatic organic matter anode material comprises an anode, a zinc cathode, a diaphragm and a zinc-containing electrolyte or a zinc-containing electrolyte; the positive electrode is an aromatic organic compound electrode; the aromatic organic compound electrode is prepared by electrochemically depositing at least two amino-containing and/or hydroxyl-containing aromatic micromolecules on a conductive carbon material substrate. According to the invention, multiple aromatic polymers are grown in situ on porous activated carbon particles as anodes by a step-by-step electrochemical polymerization method, so that the problems of poor rate capability and capacity attenuation of inorganic electrode are solved, and the battery with multiple discharge platforms, high load, high specific capacity, excellent rate capability and excellent cycling stability is obtained by assembly. The preparation method is green and simple, optimizes electrochemical polymerization parameters and raw materials, has controllable structure and low cost, and is applied to power grid energy storage and portable energy storage systems.
Description
Technical Field
The invention relates to a water system rechargeable zinc ion battery based on an aromatic organic matter positive electrode material and application thereof, belonging to the field of rechargeable batteries.
Background
With the increasing demand for sustainable and safe and efficient energy storage devices, traditional fossil fuels are destined to be replaced by renewable energy sources and energy storage technologies. Compared with the lithium ion battery with toxicity, flammability, slow charging and lithium metal resource shortage, the rechargeable water system zinc ion battery is concerned due to the advantages of green safety, excellent theoretical capacity of metal zinc, low oxidation-reduction potential, abundant reserves and the like. Therefore, it is important to develop a new type of positive electrode material so that the aqueous rechargeable zinc ion battery has environmental protection, low cost, and energy density and cycle life exceeding those of lead-acid batteries. The energy storage of the water-based zinc ion battery depends on the anode material to a great extent, and the most studied anode material is transition metal oxide (MnO)2、V2O5) And prussian blue analogs (CuHCF, ZnHCF).
Most inorganic electrode materials have the problems of low conductivity, poor rate performance, serious capacity attenuation and the like. For example, Zn// MnO2And Zn// V2O5The battery is charged and discharged within the voltage ranges of 1.0-1.8V and 0.5-1.4V respectively, and the rate performance and the output power of the water system zinc ion battery are severely limited by high internal resistance and a voltage window not exceeding 1V. Zn2+/Mn2+Co-inserted Zn// MnO2The cell has a wide voltage window and good cycling performance, but it is at 3mAcm-2The capacity retention at (c) was only 33%. The Prussian blue analogue has a higher discharge platform, but the actual specific capacity is far lower than the theoretical value. In addition, the low conductivity of inorganic substances makes it difficult to prepare highly loaded positive electrode materials.
Compared with inorganic matters, the organic matter anode with wide sources, light weight, environmental protection and various molecular species provides more possibility for the development of the water system rechargeable zinc ion battery. Different from the electron conduction, ion storage and space structure of inorganic substances, organic substancesThe positive electrode can store both electrons and zinc ions. Polyaniline, polypyrrole and partial quinone organic matters which are reported recently are used for constructing a water-based zinc ion battery with a zinc negative electrode, but the discharge medium voltage and specific capacity of the polyaniline, polypyrrole and partial quinone organic matters are not obviously superior to those of inorganic electrodes. In addition, organic-inorganic hybrid electrodes have become a research hotspot due to many advantages of organic substances. For example, polypyrrole (PPy) is used for LiVPO4F-CNTs are coated, so that LiVPO is remarkably improved4And the conductivity, rate capability and cycle performance of the F-CNTs anode. Further, in Mn2O3PPy is polymerized in situ on the surface to obtain Mn with excellent conductivity and structural stability2O3@ PPy cathode material. However, polymers only serve as a backbone or cladding material in these organic-inorganic hybrid electrodes to improve the conductivity and structural integrity of the inorganic, and little capacity is provided. Currently, research on energy storage of organic anodes is very limited, and therefore, organic anode materials still have great development space and necessity.
Disclosure of Invention
The invention aims to provide an aqueous rechargeable zinc ion battery based on an aromatic organic positive electrode material and application thereof.
The invention electrochemically polymerizes a plurality of aromatic micromolecule monomers on the nano porous carbon simultaneously to prepare the carbon-supported polymer composite anode, and assembles the carbon-supported polymer composite anode with the zinc cathode to obtain the water system rechargeable zinc ion battery.
The invention provides a water system rechargeable zinc ion battery based on an aromatic organic matter anode material, which comprises an anode, a zinc cathode, a diaphragm and a zinc-containing electrolyte or a zinc-containing electrolyte;
the positive electrode is an aromatic organic compound electrode;
the aromatic organic compound electrode is prepared by electrochemically depositing at least two amino-containing and/or hydroxyl-containing aromatic micromolecules on a conductive carbon material substrate.
In the above-mentioned aqueous rechargeable zinc ion battery, the zinc negative electrode is selected from a group consisting of a pure zinc negative electrode, a surface-treated zinc negative electrode, a three-dimensional zinc negative electrode formed by electrochemical deposition on a current collector, or a zinc-containing metal alloy negative electrode, wherein a current collector is formed by mixing and rolling zinc powder and a binder; wherein the binder is selected from at least one of polyvinylidene fluoride, polytetrafluoroethylene and sodium alginate; the current collector is selected from at least one of carbon fiber cloth, carbon paper and carbon felt; the zinc negative electrode is prepared by a method known in the field;
the conductive material in the conductive carbon material substrate comprises at least one of graphene, carbon nano tubes, activated carbon, hard carbon, acetylene black, conductive carbon black, carbon microspheres and conductive graphite.
In the above-described aqueous rechargeable zinc-ion battery, the amino group-containing and/or hydroxyl group-containing aromatic small molecules include amino group-containing aromatic small molecules, hydroxyl group-containing aromatic small molecules, and aromatic small molecules containing both amino groups and hydroxyl groups;
the amino group-containing aromatic small molecule is selected from at least one of aniline, p-phenylenediamine, benzene-1, 2, 3-triamine, 2,4, 6-trimethylbenzene-1, 3, 5-triamine, 1, 5-naphthalenediamine, 3 '-diaminobenzidine, 4' -diaminodiphenyl ether, 2, 6-diaminoanthracene, 1-aminoanthracene, and isomers of the above molecules;
the aromatic micromolecules containing hydroxyl groups are selected from at least one of phenol, hydroquinone, phloroglucinol, 2,4, 6-triacyl phloroglucinol, 1, 5-naphthalenediol, parachlorophenol, m-cresol, 2, 5-dimethylphenol, p-hydroxybiphenyl and isomers of the molecules;
the aromatic small molecule containing both amino and hydroxyl is selected from at least one of 4,4 '-dihydroxydiphenyl ether, 3' -dihydroxybenzidine, 4-aminophenol, 1-amino-5-naphthol, 4, 6-dichloro-2-aminophenol, 3-methoxy-4-aminophenol, 2-amino-4-bromophenol, 2-amino-5-nitrophenol, dopamine, 6-hydroxydopamine and isomers of the molecules.
In the above-mentioned aqueous rechargeable zinc-ion battery, the separator may be at least one of an aqueous filter paper, a proton exchange membrane, a glass fiber filter paper, and a composite membrane made of polyethylene and polypropylene.
In the present invention, the polyethylene and polypropylene composite film is prepared by a conventional method in the art.
In the above-described aqueous rechargeable zinc ion battery, the zinc-containing electrolyte is an aqueous solution containing a zinc salt;
the zinc-containing electrolyte is PVA gel containing zinc salt;
wherein the zinc salt comprises at least one of zinc sulfate, trifluoromethanesulfonic acid, zinc chloride, zinc acetate and zinc nitrate;
the concentration of the zinc salt in the aqueous solution containing the zinc salt or the PVA gel containing the zinc salt can be 1M-20M, and specifically can be 2M, 1M-10M or 1M-15M.
The invention also provides an electrode which is the aromatic organic compound electrode.
The preparation method of the electrode comprises the following steps: 1) mixing the conductive material with a conductive agent and a binder, adding a solvent for mixing, grinding and stirring to obtain slurry, coating the slurry on a current collector, and drying to obtain nano porous carbon @ current collector;
2) and sequentially carrying out in-situ growth of at least two amino-containing and/or hydroxyl-containing aromatic micromolecules on the nanoporous carbon @ current collector by adopting an electrochemical deposition method to obtain the electrode.
In the above preparation method, in step 1), the conductive agent is acetylene black and/or conductive carbon black;
the binder is selected from at least one of polyvinylidene fluoride (PVDF for short in English), polytetrafluoroethylene (PTFE for short in English) and sodium alginate (SAA for short in English);
the solvent is at least one of water, ethanol and N-methylpyrrolidone (NMP for short);
the current collector is selected from at least one of carbon fiber cloth, carbon paper and carbon felt.
In the preparation method, step 1) further includes the steps of soaking the current collector in dilute hydrochloric acid or dilute nitric acid and performing ultrasonic treatment before coating the slurry, then sequentially cleaning the current collector with ethanol, acetone and water (specifically, deionized water), and drying the current collector.
In the above preparation method, the slurry may contain, by mass, 100%, 5% to 20% of the conductive agent, 5% to 20% of the binder, and the balance of the conductive carbon material;
the drying temperature can be 60-100 ℃, specifically 100 ℃, 70-100 ℃, 80-100 ℃ or 90-100 ℃, and the time can be 6-12 hours, specifically 12 hours, 10-12 hours, 8-12 hours or 7-12 hours.
In the invention, the slurry comprises, by mass, 100%, specifically 10% of the conductive agent, 10% of the binder, and the balance 80% of the conductive carbon material;
the conductive carbon material is a material with high specific surface area, such as 2260m2Per gram of activated carbon.
In the above preparation method, the carbon paper is Dongli carbon paper and/or graphite paper.
In the invention, the carbon material substrates with different mass loads can be obtained by selecting current collectors with different thicknesses and pore structures and controlling the volume of the coating slurry.
In the preparation method, when the current collector is carbon fiber cloth, the amount of the conductive material after the slurry in the step 1) is coated on the current collector is 1-10 mg/cm2。
In the preparation method, when the current collector is carbon paper, the amount of the conductive material loaded on the current collector after the slurry is coated on the current collector is 0.5-6 mg/cm2。
In the preparation method, when the current collector is a carbon felt, the amount of the conductive material loaded on the current collector after the slurry is coated on the current collector is 10-30 mg/cm2。
In the above preparation method, the electrochemical deposition method comprises the following steps:
the nano porous carbon @ current collector is a working electrode, the Pt net is used as a counter electrode, the Ag/AgCl or calomel electrode is used as a reference electrode to form a three-electrode system, the three-electrode system is placed in a solution of the amino-containing and/or hydroxyl-containing aromatic micromolecules, and the amino-containing and/or hydroxyl-containing aromatic micromolecules are subjected to in-situ electrochemical polymerization on the nano porous carbon @ current collector through a cyclic voltammetry method or a potentiostatic method.
According to the invention, the working electrode is subjected to repeated deionized water cleaning after the polymerization of one amino-containing and/or hydroxyl-containing aromatic micromolecule is finished each time by the electrochemical deposition method, and the carbon-supported aromatic organic composite anode with a wide voltage window and a plurality of oxidation-reduction potentials is obtained after multiple times of polymerization.
In the above preparation method, the solution of the amino group-containing and/or hydroxyl group-containing aromatic micromolecules is prepared by dissolving the amino group-containing and/or hydroxyl group-containing aromatic micromolecules in an acidic solution or an aqueous solution of an alkaline solution; wherein the acid solution comprises aqueous solution of sulfuric acid and hydrochloric acid, and the alkaline solution comprises aqueous solution of potassium hydroxide and sodium hydroxide;
the concentration of the solution of the amino-containing and/or hydroxyl-containing aromatic micromolecules can be 0.005M-0.1M, specifically 0.02M and 0.03M;
in the above preparation method, when the cyclic voltammetry is adopted, the scanning rate may be 2 to 50mV/s, specifically 15mV/s, 15 to 50mV/s, 2 to 15mV/s or 10 to 40mV/s, the potential may be-0.5 to 1.2V, specifically-0.3 to 0.9V or-0.5 to 1.2V, specifically, the potential during polymerization of the 1, 5-naphthalene diamine is-0.3 to 0.9V, the potential during polymerization of the p-phenylene diamine is-0.5 to 1.2V, and the overpotential caused by the electrochemically active aromatic monomer molecules may make the voltage range of the aqueous electrolyte greater than the theoretical decomposition voltage of water by 1.23V; the number of cycles can be 5-300 cycles, specifically 15 cycles, 20 cycles, 60 cycles, 120 cycles, 15-120 cycles, 10-200 cycles, or 20-250 cycles.
In the preparation method, when the potentiostatic method is adopted, the potential can be 0.2-1.0V, and the polymerization time can be 1-60 minutes;
the cyclic voltammetry conditions or the potentiostatic conditions described above depend on the electrochemical activity of the small aromatic molecules;
the invention also provides a preparation method of the water system rechargeable zinc ion battery based on the aromatic organic matter anode, which comprises the following steps: preparing the aromatic organic compound electrode as a positive electrode, and packaging the aromatic organic compound electrode, the zinc negative electrode, the diaphragm and the zinc-containing electrolyte or the zinc-containing electrolyte into a soft package battery, a cable type flexible zinc ion battery or a carbon felt current collector zinc ion battery to obtain the aqueous rechargeable zinc ion battery based on the aromatic organic compound positive electrode.
According to the invention, the soft package battery, the cable type flexible zinc ion battery or the carbon felt current collector zinc ion battery can be packaged by adopting a method known in the art.
The invention also provides a preparation method of the water system rechargeable zinc ion battery based on the aromatic organic matter anode, which specifically comprises the following steps: firstly, placing a negative electrode shell and a gasket, placing the zinc negative electrode on the gasket, and then adding the zinc-containing electrolyte or the zinc-containing electrolyte separator; and the aromatic organic compound electrode is arranged above the diaphragm, covered with the gasket, the elastic sheet and the positive electrode shell and packaged by a battery packaging machine to obtain the water system rechargeable zinc ion battery based on the aromatic organic compound positive electrode, specifically a button battery.
The water system rechargeable zinc ion battery is applied to the preparation of power grid energy storage and portable energy storage systems.
The invention has the following advantages:
the invention provides a water system zinc ion battery which is different from an inorganic substance and inorganic-organic mixture positive electrode, is based on an aromatic organic substance positive electrode material, and has high capacity, long service life and excellent multiplying power. The selection of the porous carbon substrate with excellent conductivity can obviously improve the conductivity and stability of the polymer and can also improve the loading capacity of the polymer. The selection of current collectors such as carbon cloth and carbon felt also has a significant impact on the area capacity of the polymer composite positive electrode. Particularly, the composite electrode capable of simultaneously polymerizing two or more aromatic micromolecules and in-situ heterogeneous polymers can simultaneously have the energy storage characteristics of a plurality of polymers, a plurality of discharge platforms exist in a discharge interval, and the novel heterostructure polymer @ carbon-supported composite anode material with high specific capacity is provided so as to improve the specific capacity and prolong the service life of the composite electrode. The aromatic small molecules involved include, but are not limited to, the above volumes of organic molecules containing amino and hydroxyl groups, the polymers of which are capable of undergoing a de-intercalation reaction with zinc ions. By optimizing electrochemical polymerization parameters, including selection of different aromatic micromolecules, adjustment of micromolecule concentration in electrolyte, electropolymerization turn number, voltage window and the like, the median voltage, specific capacity and stability of the polymer composite electrode can be regulated, and theoretical guidance is improved for later-stage preparation of high-performance polymer composite electrodes and application of the high-performance polymer composite electrodes in other water system energy storage devices. The invention enriches the research range and the development of the organic positive electrode material, the specific capacity of the polymer composite positive electrode can reach 300mAh/g, and the polymer composite positive electrode has excellent area specific capacity, rate capability and long service life.
Drawings
Fig. 1 (a) is an electron scanning microscope image of a porous nanocarbon electrode based on a carbon cloth current collector; (b) is an electron scanning microscope picture of the porous nano carbon electrode based on the carbon felt current collector.
FIG. 2 shows the linear cyclic voltammetry polymerization process of the aromatic organic positive electrode of the present invention: (a) poly (p-phenylenediamine) @ poly (1, 5-naphthalenediamine)/activated carbon electrode; (b) poly (p-phenylenediamine) @ poly (p-phenol)/activated carbon electrode; (c) poly (p-phenylenediamine) @ poly (4, 4-diaminodiphenyl ether)/activated carbon electrode; (d) poly (1, 5-naphthalene diamine) @ poly (p-phenol)/activated carbon electrode.
FIG. 3(a) is a linear cyclic voltammogram of poly (1, 5-naphthylenediamine) @ poly (p-phenol)/activated carbon// zinc based on carbon cloth current collector; (b) linear cyclic voltammetry curves for poly (p-phenylenediamine) @ poly (p-phenol)/activated carbon// zinc based on carbon cloth current collectors; (c) the charge-discharge curve is the charge-discharge curve of poly (p-phenylenediamine) @ poly (p-phenol)/activated carbon// zinc based on a carbon cloth current collector; (d) the charge and discharge curve is based on poly (p-phenylenediamine) @ poly (1, 5-naphthalene diamine)/activated carbon// zinc of a carbon felt current collector.
FIG. 4(a) is a graph of the cycling stability of poly (p-phenylenediamine) @ poly (p-phenol)/activated carbon// zinc based carbon cloth current collectors; (b) the cycle stability of poly (1, 5-naphthalene diamine) @ poly (p-phenol)/activated carbon// zinc is shown.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1 preparation of aromatic organic Positive electrode and Assembly of aqueous Zinc ion Battery
The aromatic micromolecule 1, 5-naphthalene diamine, 4, 4-diaminodiphenyl ether, p-aniline, p-phenol and p-aminophenol can be directly purchased.
And sequentially cleaning the rectangular flexible conductive carbon cloth by dilute nitric acid, acetone and deionized water, drying and weighing. Will have a high specific surface area (-2260 m)2Per g) active carbon, acetylene black and PVDF according to the mass ratio of 8: 1: 1, uniformly grinding, dispersing in NMP solvent, and uniformly stirring to obtain activated carbon slurry with the mass concentration of 20 mg/mL. Coating the mixed activated carbon slurry on carbon fiber cloth (wherein the amount of the loaded activated carbon can be 5mg/cm specifically)2) Then, the activated carbon electrode is placed in an oven at 100 ℃ to be thoroughly dried for 12 hours and weighed, so as to obtain the activated carbon @ carbon cloth electrode for electrochemical polymerization, as shown in fig. 1 a. The activated carbon coated carbon cloth was then used as the working electrode and placed in 2M H containing 0.02M 1, 5-naphthalenediamine2SO4In a three-electrode system of electrolyte. Pt and Ag/AgCl as counter and reference electrodes, respectively, at 15mV s-1And (3) carrying out electropolymerization for 100 times at a scanning speed (-0.3-0.9V), thereby growing the poly (1, 5-naphthalene diamine) on the activated carbon substrate in situ. After the polymerization is finished, the mixture is repeatedly washed and placed in sulfuric acid electrolyte containing 0.03M p-phenylenediamine and the concentration of the sulfuric acid electrolyte is 15mV s-1Performing electropolymerization for 20 times (-0.5-1.2V) to grow poly (p-phenylenediamine) on the activated carbon substrate in situ, taking out, washing with deionized water repeatedly, and drying, wherein the polymerization process is shown in figure 2 (a). A 0.01mg resolution balance was used to measure poly (p-phenylenediamine) @ poly (1,5-naphthalene diamine)/activated carbon electrode. Fig. 2(a) clearly shows that different oxidation-reduction peaks are shown in the polymerization process of different aromatic molecules, which illustrates that a method for constructing a composite positive electrode with multiple discharge platforms and a high-capacity carbon-supported polymer by using multiple electrochemically active aromatic organic molecular monomers is feasible.
And assembling the button water system zinc battery of the aromatic organic matter anode based on the carbon cloth current collector and testing. The assembly process comprises the following steps of firstly placing a negative electrode shell and a gasket, placing a zinc negative electrode with the diameter of 12mm on the gasket, then adding a glass fiber diaphragm soaked with 2M zinc sulfate electrolyte, then placing a prepared poly (p-phenylenediamine) @ poly (1, 5-NAPD)/activated carbon electrode plate (with the diameter of 10mm) above the diaphragm, covering the gasket, the shrapnel and a positive electrode shell, and packaging by using a battery packaging machine to obtain the zinc ion button battery based on the carbon-loaded aromatic organic matter positive electrode. After standing for 6 hours, a series of electrochemical performance tests were performed.
Examples 2,
The aromatic small molecules for electrochemical polymerization in example 1 of the present invention were replaced with 0.03M of p-aniline and 0.05M of p-phenol, and electrochemically polymerized for 5 and 15 cycles, respectively, as shown in fig. 2 (b). Finally obtaining the poly (p-phenylenediamine) @ poly (p-phenol)/active carbon anode. And assembling the battery into a button battery, and then carrying out electrochemical performance test. FIG. 3(b) shows the linear cyclic voltammograms of zinc-poly (p-phenylenediamine) @ poly (p-phenol)/activated carbon at different scan rates. As can be seen from the figure, the carbon-supported polymer composite positive electrode has obvious redox peaks at 0.6V, 1.0V and 1.3V, which indicates that the carbon-supported polymer composite positive electrode reacts with zinc ions at the potentials and stores energy. Fig. 3(c) shows charge and discharge performance of poly (p-phenylenediamine) @ poly (p-phenol)/activated carbon positive electrode based on carbon cloth current collector under different current density. As can be seen from the figure, the positive electrode has discharge platforms at 0.6V, 1.0V and 1.3V, and the zinc storage capacity is obviously increased compared with that of a pure activated carbon electrode. In particular at 3mA/cm2When the specific capacity is up to 302 mAh/g. Furthermore, it increased to 50mA/cm in current density2The specific capacity is still 135 mAh/g. FIG. 4(a) shows the positive electrode of poly (p-phenylenediamine) @ poly (p-phenol)/activated carbon at 20mA/cm2(3.8Cycle performance test under A/g). As shown in the figure, the capacity retention rate of the lithium ion battery still remains 86% after 2000 circles of charge and discharge. The polymer composite positive electrode has excellent zinc storage performance due to high specific capacity, excellent rate capability and capacity retention rate, and is an ideal positive electrode material of a water system zinc ion battery.
Examples 3,
The same preparation method as in example 1 of the present invention was conducted except that the aromatic small molecule used for electrochemical polymerization was replaced with 0.03M of p-aniline and 0.03M of 4, 4-diaminodiphenyl ether, and electrochemically polymerized for 3 and 12 cycles, respectively, as shown in FIG. 2 (c). Finally obtaining poly (p-phenylenediamine) @ poly (4, 4-diaminodiphenyl ether)/active carbon anode. And assembling the battery into a button battery, and then carrying out electrochemical performance test.
Examples 4,
The same preparation method as in example 1 of the present invention was conducted except that the small aromatic molecules used for electrochemical polymerization were replaced with 0.03M of 1, 5-naphthalenediamine and 0.03M of p-phenol, and electrochemically polymerized for 50 and 10 cycles, respectively, as shown in FIG. 2 (d). Finally, the poly (1, 5-naphthalene diamine) @ poly (p-phenol)/active carbon anode is obtained. And assembling the battery into a button battery, and then carrying out electrochemical performance test. Fig. 3(a) shows the linear cyclic voltammogram j of zinc-poly (1, 5-naphthalenediamine) @ poly (p-phenol)/activated carbon at different scan rates and the area specific capacity calculated therefrom. As can be seen from the figure, the carbon-supported polymer composite positive electrode has obvious redox peaks at 0.6V, 1.0V and 1.3V, which indicates that the carbon-supported polymer composite positive electrode reacts with zinc ions at the potentials and stores energy. Similar linear cyclic voltammetry curves at different scanning rates show that the polymer anode has excellent conductivity and rate performance at the same time. The existence of the activated carbon enables the specific area capacity of the carbon-supported polymer anode to exceed 1mAh/cm2The maximum 1.0V discharge capacity of the material reaches 1.7mAh/cm2. Fig. 4(b) shows that the initial specific capacity of the positive electrode is still about 87% after 2000 cycles of charge and discharge. The excellent area specific capacity, rate capability and cycle life enable poly (1, 5-naphthalene diamine) @ poly (p-phenol)/activated carbon to become an excellent anode material of the water system zinc ion battery.
Examples 5,
In order to prepare a carbon-supported polymer positive electrode material with higher mass load and area specific capacity, the carbon cloth current collector in embodiment 1 of the present invention is changed into a carbon felt current collector, and activated carbon slurry is coated on both sides of the carbon felt to obtain an activated carbon @ carbon felt current collector electrode, as shown in fig. 1 (b). And then putting the activated carbon @ carbon felt serving as a working electrode in a three-electrode device in which organic molecules of 1, 5-naphthalenediamine and p-phenylenediamine are dissolved, and carrying out in-situ electrochemical polymerization to obtain a poly (p-phenylenediamine) @ poly (1, 5-naphthalenediamine)/activated carbon positive electrode based on a carbon felt current collector. The battery is assembled by adopting a repeated mode of zinc foil, a glass fiber diaphragm, a positive electrode, a glass fiber diaphragm and zinc foil, and 2M zinc sulfate solution is dripped into the battery. And (3) placing the assembled battery in an aluminum-plastic film for vacuum packaging, sticking a nickel tab on the battery by using conductive silver adhesive to lead out the nickel tab to obtain a soft package battery, and then carrying out electrochemical test on the soft package battery. Fig. 3(d) is a charge and discharge curve of poly (p-phenylenediamine) @ poly (1, 5-naphthalenediamine)/activated carbon positive electrode based on a carbon felt current collector. As can be seen from the figure, the maximum specific capacity of the anode can reach 8mAh/cm2At 140mA/cm2The specific capacity still has 2mAh/cm2And the specific capacity and rate capability of the lithium ion battery are superior to those of most of currently reported positive electrodes. The three-dimensional pore structure of the carbon felt current collector can improve the specific capacity and the conductivity of the area of the polymer positive electrode and promote the practical application of the carbon-supported polymer composite positive electrode in a water system zinc ion battery.
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. An aqueous rechargeable zinc ion battery based on an aromatic organic matter positive electrode material comprises a positive electrode, a zinc negative electrode, a diaphragm and a zinc-containing electrolyte or a zinc-containing electrolyte;
the positive electrode is an aromatic organic compound electrode;
the aromatic organic compound electrode is prepared by electrochemically depositing at least two amino-containing and/or hydroxyl-containing aromatic micromolecules on a conductive carbon material substrate.
2. The aqueous rechargeable zinc-ion battery of claim 1, wherein: the zinc cathode is selected from a three-dimensional zinc cathode formed by mixing, rolling and forming a film on a current collector by using zinc powder and a binder, a pure zinc cathode, a zinc cathode with surface treatment, and an electrochemical deposition on the current collector or a zinc-containing metal alloy cathode; wherein the binder is selected from at least one of polyvinylidene fluoride, polytetrafluoroethylene and sodium alginate; the current collector is selected from at least one of carbon fiber cloth, carbon paper and carbon felt;
the conductive material in the conductive carbon material substrate comprises at least one of graphene, carbon nano tubes, activated carbon, hard carbon, acetylene black, conductive carbon black, carbon microspheres and conductive graphite.
3. The aqueous rechargeable zinc-ion battery according to claim 1 or 2, characterized in that: the amino-containing and/or hydroxyl-containing aromatic micromolecules comprise amino-containing aromatic micromolecules, hydroxyl-containing aromatic micromolecules and aromatic micromolecules containing both amino and hydroxyl;
the amino group-containing aromatic small molecule is selected from at least one of aniline, p-phenylenediamine, benzene-1, 2, 3-triamine, 2,4, 6-trimethylbenzene-1, 3, 5-triamine, 1, 5-naphthalenediamine, 3 '-diaminobenzidine, 4' -diaminodiphenyl ether, 2, 6-diaminoanthracene, 1-aminoanthracene, and isomers of the above molecules;
the aromatic micromolecules containing hydroxyl groups are selected from at least one of phenol, hydroquinone, phloroglucinol, 2,4, 6-triacyl phloroglucinol, 1, 5-naphthalenediol, parachlorophenol, m-cresol, 2, 5-dimethylphenol, p-hydroxybiphenyl and isomers of the molecules;
the aromatic small molecule containing both amino and hydroxyl is selected from at least one of 4,4 '-dihydroxydiphenyl ether, 3' -dihydroxybenzidine, 4-aminophenol, 1-amino-5-naphthol, 4, 6-dichloro-2-aminophenol, 3-methoxy-4-aminophenol, 2-amino-4-bromophenol, 2-amino-5-nitrophenol, dopamine, 6-hydroxydopamine and isomers of the molecules.
4. The aqueous rechargeable zinc-ion battery of any one of claims 1-3, wherein: the diaphragm is at least one of water system filter paper, a proton exchange membrane, glass fiber filter paper and a composite membrane prepared from polyethylene and polypropylene.
5. The aqueous rechargeable zinc-ion battery of any one of claims 1-4, wherein: the zinc-containing electrolyte is an aqueous solution containing zinc salt;
the zinc-containing electrolyte is PVA gel containing zinc salt;
wherein the zinc salt comprises at least one of zinc sulfate, trifluoromethanesulfonic acid, zinc chloride, zinc acetate and zinc nitrate;
the concentration of the zinc salt in the aqueous solution containing the zinc salt or the PVA gel containing the zinc salt is 1M-20M.
6. An electrode, characterized by: the electrode is the aromatic organic compound electrode according to any one of claims 1 to 5.
7. A method of making the electrode of claim 6, comprising the steps of: 1) mixing the conductive material with a conductive agent and a binder, adding a solvent, mixing to obtain a slurry, coating the slurry on a current collector, and drying to obtain a nano porous carbon @ current collector;
2) and sequentially carrying out in-situ growth of at least two amino-containing and/or hydroxyl-containing aromatic micromolecules on the nanoporous carbon @ current collector by adopting an electrochemical deposition method to obtain the electrode.
8. The method of claim 7, wherein: in the step 1), the conductive agent is acetylene black and/or conductive carbon black;
the binder is selected from at least one of polyvinylidene fluoride, polytetrafluoroethylene and sodium alginate;
the solvent is at least one of water, ethanol and N-methyl pyrrolidone dispersant;
the current collector is selected from at least one of carbon fiber cloth, carbon paper and carbon felt; and/or
In the method, the step 1) also comprises the steps of soaking the current collector in dilute hydrochloric acid or dilute nitric acid and performing ultrasonic treatment before coating the slurry, then sequentially washing the current collector with ethanol, acetone and water, and drying the current collector; and/or
In the slurry, the mass percentage of the conductive agent is 5-20%, the mass percentage of the adhesive is 5-20%, and the balance is the conductive material, wherein the mass percentage of the conductive agent is 100%; and/or
The drying temperature is 60-100 ℃, and the drying time is 6-12 hours.
9. The method of claim 8, wherein: the carbon paper comprises Dongli carbon paper and/or graphite paper;
when the current collector is carbon fiber cloth, the amount of the conductive material loaded after the slurry is coated on the current collector is 1-10 mg/cm2(ii) a And/or
When the current collector is carbon paper, the amount of the conductive material loaded after the slurry is coated on the current collector is 0.5-6 mg/cm2(ii) a And/or
When the current collector is a carbon felt, the amount of the conductive material loaded on the current collector after the slurry is coated on the current collector is 10-30 mg/cm2(ii) a And/or
The electrochemical deposition method comprises the following processes:
the nano porous carbon @ current collector is a working electrode, the Pt net is used as a counter electrode, the Ag/AgCl or calomel electrode is used as a reference electrode to form a three-electrode system, the three-electrode system is placed in a solution of the amino-containing and/or hydroxyl-containing aromatic micromolecules, and the amino-containing and/or hydroxyl-containing aromatic micromolecules are subjected to in-situ electrochemical polymerization on the nano porous carbon @ current collector through a cyclic voltammetry method or a potentiostatic method; and/or
The solution of the amino-containing and/or hydroxyl-containing aromatic micromolecules is prepared by dissolving the amino-containing and/or hydroxyl-containing aromatic micromolecules in an acid solution or an aqueous solution of an alkaline solution; wherein the acid solution comprises aqueous solution of sulfuric acid and hydrochloric acid, and the alkaline solution comprises aqueous solution of potassium hydroxide and sodium hydroxide;
the concentration of the solution of the amino-containing and/or hydroxyl-containing aromatic micromolecules is 0.005-0.1M;
when the cyclic voltammetry is adopted, the scanning rate is 2-50 mV/s, the potential is-0.5-1.2V, and the number of cyclic cycles is 5-300 cycles; and/or
When the potentiostatic method is used, the potential is 0.2-1.0V, and the number of cycles is 5-300.
10. Use of the aqueous rechargeable zinc-ion battery of any one of claims 1 to 5 for the preparation of mains energy storage and portable energy storage systems.
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