CN111416096B - Graphene oxide/polyaniline/manganese dioxide composite electrode, preparation method thereof and application thereof in seawater battery - Google Patents
Graphene oxide/polyaniline/manganese dioxide composite electrode, preparation method thereof and application thereof in seawater battery Download PDFInfo
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Abstract
The invention discloses a graphene oxide/polyaniline/manganese dioxide composite electrode, a preparation method thereof and application thereof in a seawater battery. The preparation method of the composite electrode comprises the steps of taking graphite paper as an anode, taking a stainless steel plate as a cathode, taking an inorganic acid solution as an electrolyte, carrying out electrooxidation treatment on the graphite paper, taking oxidized graphite paper as the anode, taking the stainless steel plate as the cathode, taking an aniline-organic acid-inorganic acid-divalent manganese salt mixed solution as the electrolyte, and electrodepositing polyaniline and manganese dioxide on the oxidized graphite paper simultaneously to obtain the composite electrode which is high in energy density, small in polarization, large in specific surface area and good in stability.
Description
Technical Field
The invention relates to a seawater battery anode, in particular to a composite anode prepared by in-situ polymerization by taking graphite oxide paper as a matrix and a conductive agent, manganese dioxide as a stabilizer and conductive polyaniline as an active substance, and also relates to application of the composite anode in a seawater battery, belonging to the technical field of seawater battery preparation.
Background
Polyaniline is used as a conductive polymer with excellent performances such as light weight, low price, large specific surface area, good stability, simple and convenient synthesis method, adjustable and controllable conductive capacity and the like, and the theoretical energy density is more than 500 Wh/kg -1 It is expected to replace high cost, large specific gravity and high conductivityTraditional positive electrode materials such as noble metals, noble metal salts, metal oxides and the like with poor electrical property and long activation time are applied to high-performance seawater batteries.
Polyaniline is insoluble in various solvents and poor in thermal processing performance, and related electrodes are generally pressed under high pressure, but the method can cause electrolyte to be difficult to permeate into the electrodes, so that active substances in the electrodes are difficult to participate in reaction, and the utilization rate of the active substances is reduced. In a magnesium/polyaniline seawater battery system, in the discharging process, the polyaniline has a de-doping phenomenon, the conductivity of the polyaniline is reduced, so that the internal resistance of the battery is increased, the electrode reaction is difficult to go deep into the battery, and the utilization rate of active substances is low.
The positive electrode of the polyaniline seawater battery mentioned in the Chinese patent application number 201810052098.3 is a polyaniline electrode prepared by compression molding, and in order to maintain the stable structure of the electrode during use and the compact electrode pressure, electrolyte is difficult to enter during reaction, and only can react with polyaniline on the surface of the electrode, so that the utilization rate is limited. In addition, the outer polyaniline layer of the pressed polyaniline electrode causes the dedoping of materials after reaction, the conductivity is poor, the internal resistance is obviously increased, and the dedoping of materials and the internal resistance seriously affect the reaction of the polyaniline in the inner layer, so that only the polyaniline on the surface participates in the reaction when the polyaniline electrode is subjected to electrochemical reaction, the discharge capacity of the polyaniline electrode is not high enough, and the excellent battery performance of the polyaniline cannot be shown.
Disclosure of Invention
Aiming at the defects of insufficient utilization rate of active substances and serious electrode polarization in the preparation process of the polyaniline positive electrode of the existing seawater battery, the first purpose of the invention is to provide a method for preparing a graphene oxide/polyaniline/manganese dioxide composite electrode by electrochemical in-situ polymerization.
The second purpose of the invention is to provide a seawater battery anode which has the advantages of light weight, low price, environmental protection, high energy density, small polarization, large specific surface area and good stability.
The third purpose of the invention is to provide an application of the graphene oxide/polyaniline/manganese dioxide composite electrode, which is used as a seawater battery anode to obtain a seawater battery with large specific capacity and high specific energy.
In order to achieve the technical purpose, the invention provides a method for preparing a graphite oxide paper/polyaniline/manganese dioxide composite electrode by electrochemical in-situ polymerization, which comprises the steps of carrying out electrooxidation treatment on graphite paper by taking the graphite paper as an anode, a stainless steel plate as a cathode and an inorganic acid solution as an electrolyte to obtain graphene oxide paper; and simultaneously electrodepositing polyaniline and manganese dioxide on the graphite oxide paper by taking the graphite oxide paper as an anode, a stainless steel plate as a cathode and the aniline-organic acid-inorganic acid-divalent manganese salt mixed solution as an electrolyte.
According to the technical scheme, graphene paper is oxidized in situ by an electrochemical method, and then the graphene oxide paper is used as an anode to compound a polyaniline active material and a manganese dioxide stabilizer in situ by the electrochemical method, the graphene oxide has a large specific surface area and is rich in polar groups on the surface, so that the generated polyaniline can be completely spread on the surface of the graphene oxide paper to generate a uniform polyaniline film layer, and the full contact between the active polyaniline and an electrolyte is facilitated.
The technical scheme of the invention utilizes the fact that graphite paper is formed by electrochemical surface oxidation, the graphite paper has large specific surface area and rich oxygen-containing functional groups such as carboxyl, epoxy, hydroxyl and the like on the surface, and physical and chemical bonding effects of polyaniline and the surface of graphene oxide are utilized, thereby being beneficial to realizing the effect of the graphene oxide paper and the polyanilineIn-situ compounding, and the utilization rate of the electrode can be improved to the maximum extent by improving the specific surface area of the polyaniline. Therefore, the polyaniline composite material prepared by taking the graphene oxide paper as the substrate is directly used as an electrode, the graphite paper is used as an electrode support, the effect of improving the specific surface area of the electrode is also achieved, and the polyaniline composite can be completely spread on the electrode support, so that the utilization rate of active substances is improved. The composite of polyaniline and manganese dioxide is used as the active material of positive electrode of battery, and because the main reaction on the polyaniline electrode is the dedoping of polyaniline and the reduction of oxygen, the side reaction separates out H 2 ，H 2 The manganese dioxide is used as an effective electrode depolarizer and stabilizer, can reduce the hydrogen precipitation and can absorb H 2 The polarization effect is reduced; the structure of the electrode can be improved, and the stability of the electrode can be improved.
In a preferred embodiment, the conditions of the electrooxidation treatment are as follows: the temperature is 10-50 ℃, and the current density is 5-50 mA-cm -2 The oxidation time is 5-100 min. More preferred conditions for the electrooxidation treatment are: the temperature is 35-45 ℃, and the current density is 10-20 mA-cm -2 The oxidation time is 50-100 min.
In a preferable scheme, a direct current power supply or a pulse power supply is adopted in the electro-oxidation treatment process; the direct current power supply is a constant voltage or constant current direct current power supply; the pulse period of the pulse power supply is 1-200 ms, and the duty ratio is 0.1-0.95.
Preferably, the concentration of the inorganic acid solution is 0.1-3 mol/L, and the inorganic acid solution is at least one selected from nitric acid, sulfuric acid, hydrochloric acid and phosphoric acid. The concentration of the inorganic acid solution is preferably 1 to 2mol/L.
Preferably, the thickness of the graphite paper is 0.01-5 mm. The thickness of the graphite paper is preferably 1-3 mm, and the electrodeposition conditions are as follows: the current density is 10-60 mA cm -2 The electrodeposition time is 10-50 min, and the temperature is 10-60 ℃. Preferred electrodeposition conditions are: the current density is 10-30 mA-cm -2 The electro-deposition time is 10-30 min,the temperature is 40-50 ℃.
In a preferable scheme, a direct current power supply or a pulse power supply is adopted in the electrodeposition process; the direct current power supply is a constant voltage or constant current direct current power supply; the pulse period of the pulse power supply is 1-200 ms, and the duty ratio is 0.1-0.95.
Preferably, the aniline-organic acid-inorganic acid-divalent manganese salt mixed solution has aniline concentration of 0.1-3 mol/L, divalent manganese salt concentration of 1-5 mol/L, inorganic acid concentration of 0.3-3 mol/L, and organic acid concentration of 10-50 g/L. The preferred aniline concentration is 0.5 to 1.5mol/L. The concentration of the divalent manganese salt is preferably 2 to 4mol/L. The concentration of the inorganic acid is preferably 1 to 3mol/L and the concentration of the organic acid is preferably 20 to 40g/L.
Preferably, the inorganic acid is an inorganic acid commonly used in the art, such as at least one selected from sulfuric acid, hydrochloric acid, and perchloric acid.
Preferably, the organic acid is an organic carboxylic acid commonly used in the art, such as at least one selected from sulfosalicylic acid, sodium dodecylbenzene sulfonate, camphorsulfonic acid, and p-methyl benzene sulfonic acid.
Preferably, the manganous salt is common manganous salt in the field, such as at least one selected from manganese chloride, manganese sulfate, manganese acetate and manganese perchlorate.
According to the technical scheme, the graphite paper is oxidized in situ through electrochemistry, then polyaniline is polymerized in situ, the oxidized graphene paper is large in specific area and contains more active functional groups, in-situ compounding of polyaniline and manganese dioxide is facilitated, a large number of reaction active points are provided for aniline polymerization, polyaniline active materials can be in full contact with electrolyte, and the utilization rate of active substances is improved.
The invention also provides a graphene oxide/polyaniline/manganese dioxide composite electrode which is prepared by the method. In the composite electrode, polyaniline is used as an active substance, graphene oxide is used as a conductive agent, and manganese dioxide is used as a stabilizer. H is precipitated by side reaction on polyaniline which is an active material of a composite electrode 2 ，H 2 Will adhere to the electrodeThe reaction on the positive electrode is hindered, so that the internal resistance of the battery is increased, the voltage is reduced, the introduction of manganese dioxide can effectively depolarize, mnO 2 Can absorb H 2 And the polarization effect is reduced, so that the structure of the electrode is improved, and the stability of the electrode is improved. The graphene oxide paper is introduced, and a large amount of oxygen-containing functional groups such as carboxyl, epoxy group and hydroxyl on the surface of the graphene oxide paper are utilized, so that not only is the in-situ combination of polyaniline and manganese dioxide with the graphene oxide facilitated, but also the graphene oxide can be used as a conductive agent of polyaniline, particularly a large amount of active groups on the surface of the graphene oxide provide a large amount of reaction active points for polyaniline monomers in a solution, the specific surface area of a polyaniline electrode is facilitated to be increased, the polyaniline active material can be in full contact with an electrolyte, and the utilization rate of active substances is increased.
The invention also provides an application of the graphene oxide/polyaniline/manganese dioxide composite electrode, which is applied to a seawater battery.
In the preferred scheme, the graphene oxide/polyaniline/manganese dioxide composite electrode is used as a positive electrode, the magnesium alloy is used as a negative electrode, and seawater is used as an electrolyte to form the seawater battery. Magnesium alloys are common alloy systems in the art, such as magnesium aluminum alloys or magnesium zinc alloys.
The seawater battery prepared by the invention uses the composite positive electrode and the magnesium alloy negative electrode to form the seawater battery, the seawater battery is discharged in 3.5 percent by weight of sodium chloride solution, and the constant current discharge current is 6.25mA/cm -2 And cutoff voltage 1.0V. The open-circuit voltage of the seawater battery is 1.8V-2.2V, 6.25mA/cm -2 Constant current discharge, average discharge voltage of 1.35V to 1.6V, specific capacity of 172 to 300mAh/g and specific energy of 230 to 450mWh/g.
The process for preparing the graphite oxide paper/polyaniline/manganese dioxide composite electrode comprises the following specific steps:
the method comprises the following steps: oxidation treatment of graphite paper
The process of oxidizing graphite paper by an electrochemical method comprises the following steps: the electrolyte is inorganic acid, the concentration of the inorganic acid is 0.1-3 mol/L, and the electrolyte is selected from at least one of nitric acid and sulfuric acid; the cathode is stainless steel plate, the anode is graphite paper, and the thickness is thickThe temperature is 0.01-5 mm, the temperature of the electrolyte is maintained at 10-60 ℃, electrochemical oxidation is adopted, wherein the current density is 5-50 mA-cm -2 The oxidation time is 5-100 min;
step two: preparation of the electrodes
The process of preparing the graphite oxide paper/polyaniline/manganese dioxide composite electrode by electrochemical in-situ polymerization comprises the following steps: the concentration of inorganic acid in the electrolyte is 0.3-3 mol/L, the concentration of organic acid is 10-50 g/L, the concentration of aniline is 0.1-3 mol/L, the concentration of manganese sulfate is 1-5 mol/L, the anode is graphite oxide paper, the cathode is a stainless steel plate, the temperature of the electrolyte is maintained at 10-60 ℃, and the graphite oxide paper/polyaniline/manganese dioxide composite electrode is prepared by adopting an electrochemical in-situ polymerization method, wherein the current density is 10-60 mA-cm -2 The deposition time is 10-50 min;
step three: battery discharge test
Discharging the obtained positive electrode and magnesium alloy composed seawater battery in 3.5 wt% sodium chloride solution, 6.25mA/cm -2 Constant current discharge, cut-off voltage 1.0V; the open circuit voltage of the battery is 1.8V-2.2V, the average discharge voltage is 1.35V-1.6V, and the specific capacity of the battery is 172-300 mAh/g, and the specific energy is 230-450 mWh/g.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
the invention provides a composite polyaniline electrode which is prepared by oxidizing graphene paper electrochemically and realizing in-situ compounding of graphene oxide, polyaniline and manganese dioxide, can realize uniform loading of a polyaniline active material on the surface of conductive graphene, greatly improves the contact area of a polyaniline electrode material and an electrolyte, and improves the utilization rate of active substances.
The graphite oxide paper/polyaniline/manganese dioxide composite electrode provided by the invention has the advantages of light weight, low price, environmental friendliness, high energy density, small polarization effect, large specific surface area and good stability.
The graphene oxide/polyaniline/manganese dioxide composite electrode provided by the invention is applied to the anode of a seawater battery, and has the characteristics of large specific capacity and high specific energy, for example, the open-circuit voltage of the seawater battery is 1.8V-2.2V, the average discharge voltage is 1.35V-1.6V, and the specific energy of the battery is 172-300 mAh/g and is 230-450 mWh/g.
The invention adopts an electrochemical in-situ polymerization method to prepare the graphite oxide paper/polyaniline/manganese dioxide composite electrode for the first time, has obvious technical advantages compared with the anode prepared by the existing direct pressing, and mainly has the advantages of simple preparation (only an electrochemical mode and one-step forming) and environmental protection (no heavy metal pollution such as lead and the like).
Detailed Description
The following detailed description of embodiments of the present invention is provided for illustrative purposes and is intended to be merely illustrative of the invention and not limiting of the scope of the invention as claimed. Of course, a person skilled in the art may propose corresponding modifications or variations on the basis of the following description, which are intended to be included within the scope of the present invention.
Performance characterization of the electrodes:
the prepared polyaniline electrode and magnesium alloy are combined to form a seawater battery, the battery is subjected to discharge performance test by using a battery capacity tester, and 6.25mA/cm is set -2 Constant current discharge, cutoff voltage 1.0V, and summary and calculation of open circuit voltage, discharge time, battery capacity and specific energy of charged battery.
In the embodiments 1-7, the polyaniline/carbon fiber composite electrode is dried for 12-36 h at 40-80 ℃ and then taken out to form the seawater battery with magnesium alloy.
Comparative example 1
Grinding the prepared and dried sulfuric acid/sulfosalicylic acid co-doped conductive polyaniline powder for half an hour, then adding other additives, wherein the polyaniline, manganese dioxide, carbon nano tube, polytetrafluoroethylene =8, 0.4. The prepared polyaniline is obtainedThe electrodes and the magnesium-aluminum alloy form a seawater battery, the battery is subjected to discharge performance test by using a battery capacity tester, and the discharge current is set to be 12.5mA/cm -2 The cut-off voltage is 1.0V, and the test result is as follows: the open-circuit voltage of the battery is 2.21V, the constant current discharge time is 70min, the average discharge voltage is 1.5V, the battery capacity is 146mAh/g, and the specific energy is 219mWh/g.
Example 1
The anode is graphite paper, the cathode is a stainless steel plate with the thickness of 0.02mm, the concentration of nitric acid in electrolyte is 0.5mol/L, the temperature of the electrolyte is maintained at 25 ℃, a direct current power supply is adopted, and the graphite paper is subjected to oxidation pretreatment by an electrochemical method, wherein the current density is 12mA/cm 2 The oxidation time was 15min. Taking the oxidized graphite paper as an anode, taking a stainless steel plate as a cathode, taking perchloric acid in electrolyte at a concentration of 0.5mol/L, p-toluenesulfonic acid at a concentration of 20g/L, aniline at a concentration of 1mol/L, manganese sulfate at a concentration of 1mol/L, maintaining the temperature of the electrolyte at 20 ℃, and preparing the oxidized graphite paper/polyaniline/manganese dioxide composite electrode by adopting a direct-current power supply and an electrochemical in-situ polymerization method, wherein the current density is 25mA/cm 2 The deposition time was 15min. Drying the graphite oxide paper/polyaniline/manganese dioxide composite electrode at 70 ℃ for 24h, taking out, mixing with a seawater battery composed of magnesium-aluminum alloy, testing the discharge performance of the battery by using a battery capacity tester, and setting the discharge current to be 6.25mA/cm -2 The cut-off voltage is 1.0V, and the test result is as follows: the open circuit voltage of the battery is 1.9V, the average discharge voltage is 1.35V, the battery capacity is 175mAh/g, and the specific energy is 236mWh/g.
Example 2
The anode is graphite paper, the cathode is a stainless steel plate with the thickness of 0.1mm, the concentration of nitric acid in the electrolyte is 1mol/L, the temperature of the electrolyte is maintained at 40 ℃, a direct current power supply is adopted, and the graphite paper is subjected to oxidation pretreatment by an electrochemical method, wherein the current density is 15mA/cm 2 The oxidation time was 60min. Taking the oxidized graphite paper as an anode, taking a stainless steel plate as a cathode, wherein the concentration of hydrochloric acid in electrolyte is 1mol/L, the concentration of sodium dodecylbenzenesulfonate is 30g/L, the concentration of aniline is 2mol/L, and the concentration of manganese sulfate is2mol/L, maintaining the temperature of the electrolyte at 40 ℃, adopting a direct current power supply and an electrochemical in-situ polymerization method to prepare the graphite oxide paper/polyaniline/manganese dioxide composite electrode, wherein the current density is 40mA/cm 2 The deposition time was 20min. Drying the graphite oxide paper/polyaniline/manganese dioxide composite electrode at 60 ℃ for 36h, taking out, mixing with the magnesium-aluminum alloy formed seawater battery, testing the discharge performance of the battery by using a battery capacity tester, and setting the discharge current to be 6.25mA/cm -2 The cut-off voltage is 1.0V, and the test result is as follows: the open circuit voltage of the battery is 2.0V, the average discharge voltage is 1.45V, the battery capacity is 210mAh/g, and the specific energy is 305mWh/g.
Example 3
The anode is graphite paper, the cathode is a stainless steel plate with the thickness of 2mm, the concentration of nitric acid in electrolyte is 1.5mol/L, the temperature of the electrolyte is maintained at 40 ℃, a direct current power supply is adopted, and the graphite paper is subjected to oxidation pretreatment by an electrochemical method, wherein the current density is 14mA/cm 2 The oxidation time is 100min. Taking the oxidized graphite paper as an anode, taking a stainless steel plate as a cathode, keeping the concentration of sulfuric acid in electrolyte at 2mol/L, the concentration of sulfosalicylic acid at 35g/L, the concentration of aniline at 1mol/L and the concentration of manganese sulfate at 3mol/L, keeping the temperature of the electrolyte at 50 ℃, and preparing the oxidized graphite paper/polyaniline/manganese dioxide composite electrode by adopting a pulse power supply, a period of 10ms, a duty ratio of 0.75 and an electrochemical in-situ polymerization method, wherein the current density is 20mA/cm 2 The deposition time was 16min. Drying the graphite oxide paper/polyaniline/manganese dioxide composite electrode at 60 ℃ for 24h, taking out, mixing with a seawater battery composed of magnesium-aluminum alloy, testing the discharge performance of the battery by using a battery capacity tester, and setting the discharge current to be 6.25mA/cm -2 The cut-off voltage is 1.0V, and the test result is as follows: the open circuit voltage of the battery is 2.2V, the average discharge voltage is 1.51V, the battery capacity is 278mAh/g, and the specific energy is 420mWh/g.
Example 4
The anode is graphite paper, the cathode is a stainless steel plate with the thickness of 1mm, the concentration of nitric acid in the electrolyte is 0.8mol/L, the temperature of the electrolyte is maintained at 35 ℃, a pulse power supply is adopted, the period is 10ms, and the duty ratio is 0.5Carrying out oxidation pretreatment on the graphite paper by adopting an electrochemical method, wherein the current density is 30mA/cm 2 The oxidation time was 40min. Taking the oxidized graphite paper as an anode, taking a stainless steel plate as a cathode, taking the sulfuric acid concentration in the electrolyte as 2mol/L, the sodium dodecyl benzene sulfonate concentration as 10g/L, the aniline concentration as 0.5mol/L and the manganese sulfate concentration as 2.5mol/L, maintaining the temperature of the electrolyte at 10 ℃, and adopting a direct-current power supply to prepare the graphite oxide paper/polyaniline/manganese dioxide composite electrode by an electrochemical in-situ polymerization method, wherein the current density is 40mA/cm 2 The deposition time was 30min. Drying the graphite oxide paper/polyaniline/manganese dioxide composite electrode at 50 ℃ for 24h, taking out, mixing with a seawater battery composed of magnesium-aluminum alloy, testing the discharge performance of the battery by using a battery capacity tester, and setting the discharge current to be 6.25mA/cm -2 The cut-off voltage is 1.0V, and the test result is as follows: the open circuit voltage of the battery is 1.9V, the average discharge voltage is 1.46V, the battery capacity is 226mAh/g, and the specific energy is 330mWh/g.
Example 5
The anode is graphite paper, the cathode is a stainless steel plate with the thickness of 3mm, the concentration of nitric acid in the electrolyte is 2mol/L, the temperature of the electrolyte is maintained at 40 ℃, a direct current power supply is adopted, and the graphite paper is subjected to oxidation pretreatment by an electrochemical method, wherein the current density is 10mA/cm 2 The oxidation time was 50min. Taking the oxidized graphite paper as an anode, taking a stainless steel plate as a cathode, keeping the concentration of perchloric acid in electrolyte at 1.5mol/L, the concentration of camphorsulfonic acid at 40g/L, the concentration of aniline at 2mol/L and the concentration of manganese chloride at 3mol/L, maintaining the temperature of the electrolyte at 30 ℃, and preparing the oxidized graphite paper/polyaniline/manganese dioxide composite electrode by adopting a direct-current power supply and an electrochemical in-situ polymerization method, wherein the current density is 20mA/cm 2 The deposition time was 40min. Drying the graphite oxide paper/polyaniline/manganese dioxide composite electrode at 60 ℃ for 24h, taking out, mixing with a seawater battery composed of magnesium-aluminum alloy, testing the discharge performance of the battery by using a battery capacity tester, and setting the discharge current to be 6.25mA/cm -2 The cut-off voltage is 1.0V, and the test result is as follows: the open circuit voltage of the battery is 1.95V, the average discharge voltage is 1.46V, and the batteryThe capacity is 204mAh/g, and the specific energy is 299mWh/g.
Example 6
The anode is graphite paper, the cathode is a stainless steel plate with the thickness of 0.5mm, the concentration of nitric acid in electrolyte is 3mol/L, the temperature of the electrolyte is maintained at 35 ℃, a direct current power supply is adopted, and an electrochemical method is adopted to carry out oxidation pretreatment on the graphite paper, wherein the current density is 30mA/cm 2 The oxidation time is 20min. Taking the oxidized graphite paper as an anode, taking a stainless steel plate as a cathode, keeping the concentration of sulfuric acid in electrolyte at 1mol/L, the concentration of p-toluenesulfonic acid at 15g/L, the concentration of aniline at 1.5mol/L and the concentration of manganese perchlorate at 4mol/L, maintaining the temperature of the electrolyte at 55 ℃, and preparing the oxidized graphite paper/polyaniline/manganese dioxide composite electrode by adopting a pulse power supply, a cycle of 10ms and a duty ratio of 0.75 electrochemical in-situ polymerization method, wherein the current density is 25mA/cm 2 The deposition time was 18min. Drying the graphite oxide paper/polyaniline/manganese dioxide composite electrode at 70 ℃ for 36h, taking out, testing the discharge performance of the seawater battery formed by the graphite oxide paper/polyaniline/manganese dioxide composite electrode and the magnesium-aluminum alloy by using a battery capacity tester, and setting the discharge current to be 6.25mA/cm -2 The cut-off voltage is 1.0V, and the test result is as follows: the open circuit voltage of the battery is 2.05V, the average discharge voltage is 1.5V, the battery capacity is 215mAh/g, and the specific energy is 323mWh/g.
Example 7
The anode is graphite paper, the cathode is a stainless steel plate with the thickness of 0.1mm, the concentration of nitric acid in electrolyte is 1.2mol/L, the temperature of the electrolyte is maintained at 30 ℃, a pulse power supply is adopted, the period is 100ms, the duty ratio is 0.9, and the graphite paper is subjected to oxidation pretreatment by an electrochemical method, wherein the current density is 24mA/cm 2 The oxidation time was 60min. Taking the oxidized graphite paper as an anode, taking a stainless steel plate as a cathode, keeping the concentration of hydrochloric acid in electrolyte at 1.5mol/L, the concentration of sulfosalicylic acid at 35g/L, the concentration of aniline at 3mol/L and the concentration of manganese sulfate at 2mol/L, maintaining the temperature of the electrolyte at 48 ℃, and preparing the oxidized graphite paper/polyaniline/manganese dioxide composite electrode by adopting a pulse power supply, a period of 10ms, a duty ratio of 0.75 and an electrochemical in-situ polymerization method, wherein the current density is 22mA/cm 2 Deposition time 25And (5) min. Drying the graphite oxide paper/polyaniline/manganese dioxide composite electrode at 60 ℃ for 36h, taking out, mixing with a seawater battery composed of magnesium-aluminum alloy, testing the discharge performance of the battery by using a battery capacity tester, and setting the discharge current to be 6.25mA/cm -2 The cut-off voltage is 1.0V, and the test result is as follows: the open circuit voltage of the battery is 2.1V, the average discharge voltage is 1.53V, the battery capacity is 235mAh/g, and the specific energy is 356mWh/g.
Claims (7)
1. A method for preparing a graphene oxide/polyaniline/manganese dioxide composite electrode by electrochemical in-situ polymerization is characterized by comprising the following steps: carrying out electrooxidation treatment on graphite paper by taking the graphite paper as an anode, a stainless steel plate as a cathode and an inorganic acid solution as electrolyte to obtain graphene oxide paper; then, graphite oxide paper is used as an anode, a stainless steel plate is used as a cathode, the aniline-organic acid-inorganic acid-divalent manganese salt mixed solution is used as an electrolyte, and polyaniline and manganese dioxide are electrodeposited on the graphite oxide paper at the same time, so that the composite material is obtained;
the conditions of the electro-oxidation treatment are as follows: the temperature is 10-50 ℃, and the current density is 5-50 mA/cm -2 The electrooxidation time is 5 to 100min; the electro-oxidation adopts a direct current power supply or a pulse power supply; the direct current power supply is a constant voltage or constant current direct current power supply; the pulse period of the pulse power supply is 1 to 200ms, and the duty ratio is 0.1 to 0.8;
the inorganic acid solution is nitric acid with the concentration of 0.1 to 3mol/L;
the concentration of aniline in the aniline-organic acid-inorganic acid-divalent manganese salt mixed solution is 0.1 to 3mol/L, the concentration of divalent manganese salt is 1 to 5mol/L, the concentration of inorganic acid is 0.3 to 3mol/L, the concentration of organic acid is 10 to 50g/L, and the inorganic acid is selected from at least one of sulfuric acid, hydrochloric acid and perchloric acid; the organic acid is at least one selected from sulfosalicylic acid, sodium dodecyl benzene sulfonate, camphorsulfonic acid and p-methyl benzene sulfonic acid; the divalent manganese salt is selected from at least one of manganese chloride, manganese sulfate, manganese acetate and manganese perchlorate.
2. The method for preparing the graphene oxide/polyaniline/manganese dioxide composite electrode by electrochemical in-situ polymerization according to claim 1, wherein the method comprises the following steps: the thickness of the graphite paper is 0.01 to 5mm.
3. The method for preparing the graphene oxide/polyaniline/manganese dioxide composite electrode by electrochemical in-situ polymerization according to claim 1, wherein the method comprises the following steps: the conditions of the electrodeposition are as follows: the current density is 10 to 60 mA/cm -2 The electrodeposition time is 10 to 50min, and the temperature is 10 to 60 ℃.
4. The method for preparing the graphene oxide/polyaniline/manganese dioxide composite electrode by electrochemical in-situ polymerization according to claim 1 or 3, wherein the graphene oxide/polyaniline/manganese dioxide composite electrode comprises the following steps: the electrodeposition adopts a direct current power supply or a pulse power supply; the direct current power supply is a constant voltage or constant current direct current power supply; the pulse period of the pulse power supply is 1 to 200ms, and the duty ratio is 0.1 to 0.8.
5. A graphene oxide/polyaniline/manganese dioxide composite electrode is characterized in that: prepared by the method of any one of claims 1 to 4.
6. The application of the graphene oxide/polyaniline/manganese dioxide composite electrode as claimed in claim 5, wherein: the method is applied to seawater batteries.
7. The application of the graphene oxide/polyaniline/manganese dioxide composite electrode according to claim 6, wherein the graphene oxide/polyaniline/manganese dioxide composite electrode comprises: the graphene oxide/polyaniline/manganese dioxide composite electrode is used as a positive electrode, the magnesium alloy is used as a negative electrode, and seawater is used as an electrolyte to form the seawater battery.
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