CN111816890A - Fluid seawater battery and preparation method thereof - Google Patents
Fluid seawater battery and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a fluid seawater battery and a preparation method thereof, belonging to the technical field of hybrid battery manufacture. The method comprises the following aspects: 1) the cathode material which takes the fluid coordination crystal as the main part and provides a storage site for ions in the seawater shows the reversible charge-discharge characteristic of the secondary battery; 2) the anode material mainly comprises magnesium and aluminum with low oxidation-reduction potential and is used for providing electrons until the metal is consumed. This is a typical primary battery feature; 3) the seawater solution with dissolved oxygen of at least 1ppm and sodium chloride of at least 0.35% is used as electrolyte to balance the polarization of ion concentration in the electrode brought in the power generation process and stabilize the environment of the power generation device. When the ion storage sites in the coordination crystal are completely occupied, ions in the storage sites are released by using dissolved oxygen in seawater to react with the coordination crystal, so that the cyclic use of the coordination crystal is realized. The method has the advantages of simple operation, environment-friendly material, recycling and meeting the requirement of common use.
Description
Technical Field
The invention relates to the technical field of hybrid batteries and manufacturing thereof, in particular to a fluid seawater battery and a preparation method thereof.
Background
With the proposal of the strong national strategy of oceans in China, the problems of ocean power utilization and island power supply need to be solved urgently. The existing power supply modes mainly comprise networking and off-network; the networking type power grid mainly adopts a submarine cable mode, although networking engineering can ensure the reliability of island power supply, the island off-grid power supply becomes the core technology of the island power supply due to the defects of the incredible manufacturing cost, the difficulty in later maintenance and the like. Renewable energy sources such as photovoltaic power generation and wind energy are utilized in the island off-grid power supply system, but the island environment is high in temperature, humidity and salt fog, and devices for photovoltaic power generation need special treatment under the conditions, so that the economic applicability is still to be improved. In response to the above series of problems, researchers at home and abroad have shifted the visual angle to seawater, the most abundant resource in islands in the sea in recent years. Power generation is attempted using natural seawater as an electrolyte, and a seawater battery is therefore produced. The seawater battery has the outstanding characteristics that the seawater battery does not need to carry electrolyte and can work in the environment of all sea conditions. The seawater battery adopts the working principle of a primary battery, the anode is active metal, and the cathode is an electrode of silver chloride, cuprous chloride and lead chloride, and the seawater battery has the characteristics of high energy density and high power, but in the discharging process, the positive anode material is consumed, so the seawater battery belongs to a primary battery and has poor economy, and is mainly applied to military and used as a power supply of torpedoes; the other type of metal-air seawater battery which is researched more still adopts active metal as the anode, and the cathode directly reduces the electrode by the dissolved oxygen in the seawater. Compared with the former battery, the anode of the seawater battery still consumes active metal, and the cathode consumes dissolved oxygen in seawater to generate oxidation-reduction reaction. Such cells have the characteristics of both primary cells and fuel cells. However, due to the limitation of the working principle, namely the limitation of the concentration of dissolved oxygen of the cathode material, the power of the battery has a great problem all the time, and the existing battery system can only be suitable for small-power electrical appliances on the sea, such as buoys, lighthouses and the like. Therefore, a cathode material with better efficiency and higher efficiency is sought, and a seawater battery with better comprehensive performance can be manufactured.
The coordination crystal is a three-dimensional periodic porous framework material formed by taking metal ions or clusters as nodes and organic ligands as frameworks. The coordination crystal has the advantages of high porosity, low density, large specific surface area, adjustable pore diameter, diversity and tailorability of topological structure and the like, so that the coordination crystal can be used for reversible storage of metal ions (such as potassium ions, sodium ions and the like). In addition, the crystal structure can be kept stable during the process of embedding and extracting the guest ions. In recent years, the coordination crystal has shown great potential in lithium, sodium, potassium, and other ion secondary batteries as typified by prussian blue-based compounds.
Disclosure of Invention
The invention aims to provide a fluid seawater battery and a preparation method thereof aiming at the problem of continuous energy supply in specific marine environment.
The specific technical scheme for realizing the purpose of the invention is as follows:
a fluid seawater battery and a preparation method thereof are disclosed, the method comprises the following steps:
step 1: selection and preparation of cathode
A1: selection of coordination crystals
Selecting Prussian blue crystals and crystals with sodium ion storage sites as coordination crystals, wherein the molecular general formula of the Prussian blue crystals is AaMⅠ bMⅡ c[MⅢ(CN)6]d·nH2O; wherein A is an alkali metal element, a hydrogen ion or an ammonium ion; mⅠ、MⅡ、MⅢAre the same or different transition metal elements; a. b, c, d are [0,2 ]]The value of (a); n is [0,20 ]]The value of (a); the alkali metal element is Li, Na, K, Rb or Cs; the transition metal element is Fe, Co, Ni, Mn, Ti, Zn, Cr, Cu or In;
the crystal with sodium ion storage sites is: na (Na)2C6O6、Na4Fe3(PO4)2(P2O7)、NaVO2、NaCrO2、NaMnFe2(PO4)3、Na3Fe2(PO4)3、C24H8O6、C6Cl4O2、NaFePO4、Na2FeP2O7Or NaMnO2；
A2: preparation of cathode fluids
Preparing the cathode fluid by adopting a manual stirring, magnetic stirring or ultrasonic dispersion mode;
i) manual stirring: mixing the coordination crystals and the seawater in a container according to a mass ratio of 1: 10-8: 10, and stirring for 5-50 minutes by using a tool to form uniform and continuous slurry, so as to obtain the cathode fluid; wherein the content of the first and second substances,
the tool is as follows: glass rods, iron rods, aluminum alloy rods, magnesium alloy rods, scrapers or electric mixers;
the seawater is natural seawater with dissolved oxygen of at least 1ppm and sodium chloride of at least 0.35%, seawater prepared from sea salt, and simulated seawater prepared from sodium chloride or potassium chloride;
ii) magnetic stirring: mixing the coordination crystals and the seawater in a container according to a mass ratio of 1: 10-8: 10, adding a magnetic stirrer, and driving the magnetic stirrer to stir for 5-50 minutes by using a magnetic stirrer to form uniform and continuous slurry, thus obtaining the cathode fluid; wherein the content of the first and second substances,
the magnetic stirrer is cylindrical, elliptical, cross-shaped, double-ended, triangular or octagonal and has the size of 5mm multiplied by 5 mm-500 mm multiplied by 500 mm;
the magnetic stirrer is an electric heating magnetic stirring sleeve or a flat plate type magnetic stirrer;
iii) ultrasonic dispersion: mixing the coordination crystals and seawater in a container according to a mass ratio of 1: 10-8: 10, and performing ultrasonic dispersion for 5-50 minutes by using an ultrasonic disperser to obtain uniform and continuous slurry, so as to obtain the cathode fluid; wherein the content of the first and second substances,
the ultrasonic dispersion instrument is an inserted ultrasonic dispersion instrument, an ultrasonic vibrator, an ultrasonic cleaning instrument or an ultrasonic vibration plate;
a3: preparation of the cathode
Guiding the prepared cathode fluid by a pump, flowing the cathode fluid through a current collector, and then circularly flowing the cathode fluid back to a container of the cathode fluid to obtain a fluid seawater battery cathode; wherein the content of the first and second substances,
the pump is a centrifugal pump, a mixed flow pump, an axial flow pump, a vortex pump, a piston pump, a plunger pump, a diaphragm pump, a gear pump, a screw pump, a scribing pump, an injection pump, a hydraulic ram or a vacuum pump;
the current collector is carbon cloth, carbon felt, metal titanium, metal copper or metal nickel;
the manner of flow through the current collector: flow from outside the current collector or from inside the current collector.
Step 2: selection of anodes
Selecting metal magnesium, metal aluminum, metal zinc, mercury and calcium doped magnesium alloy, mercury and calcium doped aluminum alloy, mercury and calcium doped zinc alloy or mercury and calcium doped magnesium aluminum alloy as an anode;
and step 3: electrolyte solution
Seawater is selected as electrolyte for providing metal ions required in the power generation process and balancing electrode polarization effect; the seawater is natural seawater with dissolved oxygen of at least 1ppm and sodium chloride of at least 0.35%, seawater prepared from sea salt, and simulated seawater prepared from sodium chloride or potassium chloride;
and 4, step 4: generation of constant current
Respectively putting the cathode current collector and the anode into two containers separated by a diaphragm, connecting the cathode current collector by a lead, and connecting the anode by the lead; immersing the anode with an electrolyte; opening the pump to flow the cathode fluid through the cathode current collector; constant direct current can be generated;
and 5: cyclic regeneration of cathode-coordination crystals
When the metal ion storage sites in the cathode coordination crystal are completely occupied, the process of generating current is stopped; stirring the cathode fluid, and contacting the cathode fluid with seawater or air to oxidize the coordination crystals by using dissolved oxygen in the seawater or oxygen in the air, so that the coordination crystals lose electrons and release metal ions in the storage sites; then the cathode current collector is led in by a pump to continuously generate constant direct current.
The prussian blue compound in the step 1 is as follows: fe4[Fe(CN)6]3(iron ferrocyanide Prussian blue, CAS number 14038-43-8), Ni3[Fe(CN)6]2(Nickel ferricyanide), Na2Co[Fe(CN)6](cobalt ferrocyanide), Ti [ Fe (CN)6](titanium ferrocyanide), Na2Cu[Fe(CN)6](copper ferrocyanide), Na2Zn[Fe(CN)6](Zinc ferrocyanide).
The invention has simple operation, environment-friendly material and cyclic utilization. Wherein the metal is mainly used for providing electrons in the power generation process and finally becomes an ionic state to be dissolved in seawater; coordination crystals are primarily used to provide a storable site for metal ions. Compared with the prior art, the invention can realize the improvement of energy density and the recycling of the seawater battery on the premise of ensuring simple process and environmental protection.
Drawings
FIG. 1 is a schematic structural diagram of a fluid seawater battery of the present invention;
FIG. 2 is a schematic side view of the recycling of the cathode material-coordination crystals of the fluid seawater cell of the present invention;
FIG. 3 is a constant current discharge diagram of a seawater battery prepared in example 1 of the present invention;
FIG. 4 is a constant current discharge diagram of a seawater battery prepared in example 2 of the present invention;
fig. 5 is a constant current discharge diagram of a seawater battery prepared in example 3 of the present invention.
Detailed Description
The invention is described in detail below with reference to the figures and examples.
Referring to fig. 1, the structure of the seawater battery of the present invention is shown in the figure, and prepared coordination crystals 1 are mixed with natural seawater 2 to form a cathode fluid, which is placed in a 1L beaker. The other side is placed in another beaker by using natural seawater 2 as electrolyte. In the flow cell 5, a carbon felt 7 was used as the cathode current collector, a metallic aluminum sheet 8 with a commercial designation of 1a99 was used as the anode electrode, and separated by a cation exchange membrane 6 with a model of CMI 7000. The carbon felt 7 was led out by a copper wire to be connected to the cathode of a load 10 such as a small bulb, and the aluminum metal sheet 8 having an industrial designation of 1a99 was connected to the anode of the load 10 by a copper wire. Then the pump 3 is used for introducing cathode fluid from the liquid inlet and outlet 4 through the silicone tube 9 and then the cathode fluid flows back to the beaker through the other liquid inlet and outlet on the same side to form circulation. The pump 3 is used for introducing the anolyte from the liquid inlet and outlet through the silicone tube and then flowing back to the beaker through the other liquid inlet and outlet on the same side to form circulation. The seawater battery is formed.
Referring to fig. 2, the principle diagram of the cyclic regeneration of the cathode coordination crystal of the seawater battery according to the present invention, when the metal ion storage sites of the coordination crystal 1 are fully occupied, the process of generating current is stopped. In a beaker for storing cathode fluid, utilizing dissolved oxygen in seawater 2 or oxygen in air to oxidize the coordination crystal 1, so that the coordination crystal 1 loses electrons and releases metal ions in a storage site; the oxygen is reduced to hydroxide and dissolved into the seawater, and the process is generally 1 day.
Example 1
Hand stirring
The cathode material selected in this example was a Prussian blue coordination crystal, the molecular formula of which is Fe4[Fe(CN)6]3(ii) a The anode material is industrial pure aluminum with the license plate of 1A 99; the electrolyte is natural seawater.
Step 1: preparation of Prussian blue coordination crystal
16.7 g of ferrous chloride hydrate (FeCl)2·6H2O) and 20 g of sodium citrate dihydrate (HOC (COOH) (CH)2COONa)2·1.5H2O) dissolved in 2.5L deionized water to form a transparent clear solution A; 14.5 g of sodium ferrocyanide (Na)4[Fe(CN)6]) Dissolving in 2.5L deionized water to obtain transparent clear solution B, and mixing solution A and solution B at room temperature to obtainReacting the solution for 24 hours at room temperature (25 ℃) to obtain a dark blue Prussian blue coordination crystal solution, and centrifugally separating the obtained Prussian blue coordination crystal solution at the speed of 10000rpm to obtain Prussian blue coordination crystal solid; a. putting the obtained Prussian blue coordination crystal solid into 20ml of industrial alcohol, performing ultrasonic dispersion for 10min, and performing centrifugal separation at a speed of 8000 rpm to obtain the Prussian blue coordination crystal solid; b. b, placing the Prussian blue coordination crystal solid obtained in the step a into 20ml of deionized water, performing ultrasonic dispersion for 10min, and performing centrifugal separation at a speed of 10000rpm to obtain the Prussian blue coordination crystal solid; repeating the steps a and b for 3 times. Putting the finally obtained solid at room temperature, and drying for 20 hours in vacuum, wherein the vacuum degree is less than 0.1 Pa;
step 2: preparation of cathode fluid of seawater battery
50 g of the Prussian blue coordination crystal solid 500 ml of natural seawater in the step 1 are placed in a beaker with the volume of 1L, and stirred for 15 minutes by an electric stirrer to form uniform and continuous slurry. The obtained product can be used as the cathode fluid of a seawater battery;
and step 3: preparation of cathode current collector of seawater battery
The carbon felt is cut into blocks of 1.5 cm multiplied by 1 cm, and the carbon felt can be used as a cathode current collector of the seawater battery.
And 4, step 4: preparation of anode of seawater battery
The industrial pure aluminum with the license plate of 1A99 is selected and divided into aluminum sheets with the size of 2.5 cm multiplied by 0.5 cm, and the aluminum sheets can be used as the anode of the seawater battery.
And 5: assembly of seawater cells and constant current generation
And (3) respectively placing the carbon felt obtained in the step (3) and the aluminum metal sheet obtained in the step (4) into two electrolytic cells separated by a cation exchange membrane with the model of CMI 7000. The seawater electrolyte and the cathode fluid are respectively placed in two 1L beakers, and the seawater electrolyte and the cathode fluid are respectively introduced into an anode electrolytic cell and a cathode electrolytic cell by a peristaltic pump and a silicone tube. The cathode and the anode are respectively led out by copper wires and connected with two poles of an electric appliance, and then stable direct current can be output.
Fig. 3 is a constant current discharge diagram of the fluid seawater cell of this example, under test conditions in which the carbon felt obtained in step 3 and the aluminum metal sheet obtained in step 4 were placed in two electrolytic cells separated by a cation exchange membrane model CMI 7000, respectively. The seawater electrolyte and the cathode fluid are respectively placed in two 1L beakers, and the seawater electrolyte and the cathode fluid are respectively introduced into an anode electrolytic cell and a cathode electrolytic cell by a peristaltic pump and a silicone tube. The cathode and the anode are respectively led out by copper wires and are connected to a constant current mode of the blue battery testing system to discharge at 5 mA current, and a voltage-time relation graph shown in figure 3 can be obtained.
In this embodiment, when the seawater electrolyte and the cathode fluid are respectively introduced into two electrolytic cells separated by a cation exchange membrane of CMI 7000 and aluminum sheets and carbon felt current collectors are immersed, due to the low redox potential of the 1a99 aluminum alloy, electrons are driven to move to the carbon felt end and finally transferred to the cathode fluid, the prussian blue coordination crystal receives electrons and absorbs cations in seawater at the same time to form prussian white coordination crystal, the metal aluminum is changed into an ionic form and dissolved in seawater, and current is generated due to the flow of electrons. When the cathode fluid is led out of the electrolytic bath and contacts with dissolved oxygen in seawater or oxygen in the air, the Prussian white coordination crystal is oxidized, a cation is released at the same time, and the Prussian blue coordination crystal is recovered, and the process is the recycling regeneration of the coordination crystal. Reciprocating in this way, stable current can be provided. The whole process is simple and easy to implement, and is environment-friendly and pollution-free to seawater.
Example 2
Magnetic stirring
The cathode material selected in this example was a Prussian blue coordination crystal, the molecular formula of which is Fe4[Fe(CN)6]3(ii) a The anode material is industrial pure aluminum with the license plate of 1A 99; the electrolyte is seawater prepared from sea salt.
Step 1: preparation of Prussian blue coordination crystal
16.7 g of ferrous chloride hydrate (FeCl)2·6H2O) and 20 g of sodium citrate dihydrate (HOC (COOH) (CH)2COONa)2·1.5H2O) dissolved in 2.5L deionized water to form a transparent clear solution A; 14.5 g of sodium ferrocyanide (Na)4[Fe(CN)6]) Dissolving the solution A and the solution B in 2.5L of deionized water to form a transparent clear solution B, uniformly mixing the solution A and the solution B at room temperature to obtain an off-white turbid liquid, reacting at room temperature (25 ℃) for 24 hours to obtain a dark blue Prussian blue coordination crystal solution, and centrifugally separating the obtained Prussian blue coordination crystal solution at the speed of 10000rpm to obtain a Prussian blue coordination crystal solid; a. putting the obtained Prussian blue coordination crystal solid into 20ml of industrial alcohol, performing ultrasonic dispersion for 10min, and performing centrifugal separation at a speed of 8000 rpm to obtain the Prussian blue coordination crystal solid; b. b, placing the Prussian blue coordination crystal solid obtained in the step a into 20ml of deionized water, performing ultrasonic dispersion for 10min, and performing centrifugal separation at a speed of 10000rpm to obtain the Prussian blue coordination crystal solid; repeating the steps a and b for 3 times. Putting the finally obtained solid at room temperature, and drying for 20 hours in vacuum, wherein the vacuum degree is less than 0.1 Pa;
step 2: preparation of cathode fluid of seawater battery
Taking 50 g of the Prussian blue coordination crystal solid 500 ml of natural seawater in the step 1, putting the natural seawater into a beaker with the volume of 1L, putting a cylindrical magnetic stirrer with the size of 120 mm multiplied by 10 mm, and stirring the mixture for 30 minutes at the speed of 400 revolutions per minute by using a magnetic stirrer to form uniform and continuous slurry. The obtained product can be used as the cathode fluid of a seawater battery;
and step 3: preparation of cathode current collector of seawater battery
The carbon felt is cut into blocks of 2 cm multiplied by 1 cm, and the carbon felt can be used as a cathode current collector of the seawater battery.
And 4, step 4: preparation of anode of seawater battery
The industrial pure aluminum with the license plate of 1A99 is selected and divided into aluminum sheets with the size of 1 cm multiplied by 0.5 cm, and the aluminum sheets can be used as the anode of the seawater battery.
And 5: assembly of seawater cells and constant current generation
And (3) respectively placing the carbon felt obtained in the step (3) and the aluminum metal sheet obtained in the step (4) into two electrolytic cells separated by a cation exchange membrane with the model of CMI 7000. The seawater electrolyte and the cathode fluid are respectively placed in two 1L beakers, and the seawater electrolyte and the cathode fluid are respectively introduced into an anode electrolytic cell and a cathode electrolytic cell by a peristaltic pump and a silicone tube. The cathode and the anode are respectively led out by copper wires and connected with two poles of an electric appliance, and then stable direct current can be output.
Fig. 4 is a constant current discharge diagram of the fluid seawater cell of this example, under test conditions in which the carbon felt obtained in step 3 and the aluminum metal sheet obtained in step 4 were placed in two electrolytic cells separated by a cation exchange membrane model CMI 7000, respectively. The seawater electrolyte and the cathode fluid are respectively placed in two 1L beakers, and the seawater electrolyte and the cathode fluid are respectively introduced into an anode electrolytic cell and a cathode electrolytic cell by a peristaltic pump and a silicone tube. The cathode and the anode are respectively led out by copper wires and are connected to a constant current mode of the blue battery testing system to discharge at 5 mA current, and a voltage-time relation graph shown in figure 4 can be obtained.
In this embodiment, when the seawater electrolyte and the cathode fluid are respectively introduced into two electrolytic cells separated by a cation exchange membrane of CMI 7000 and aluminum sheets and carbon felt current collectors are immersed, due to the low redox potential of the 1a99 aluminum alloy, electrons are driven to move to the carbon felt end and finally transferred to the cathode fluid, the prussian blue coordination crystal receives electrons and absorbs cations in seawater at the same time to form prussian white coordination crystal, the metal aluminum is changed into an ionic form and dissolved in seawater, and current is generated due to the flow of electrons. When the cathode fluid is led out of the electrolytic bath and contacts with dissolved oxygen in seawater or oxygen in the air, the Prussian white coordination crystal is oxidized, a cation is released at the same time, and the Prussian blue coordination crystal is recovered, and the process is the recycling regeneration of the coordination crystal. Reciprocating in this way, stable current can be provided. The whole process is simple and easy to implement, and is environment-friendly and pollution-free to seawater.
Example 3
Ultrasonic dispersion
The cathode material selected in this example was a Prussian blue coordination crystal, the molecular formula of which is Fe4[Fe(CN)6]3(ii) a The anode material is industrial pure aluminum with the license plate of 1A 99; electrolyteSeawater prepared for sea salt.
Step 1: preparation of Prussian blue coordination crystal
16.7 g of ferrous chloride hydrate (FeCl)2·6H2O) and 20 g of sodium citrate dihydrate (HOC (COOH) (CH)2COONa)2·1.5H2O) dissolved in 2.5L deionized water to form a transparent clear solution A; 14.5 g of sodium ferrocyanide (Na)4[Fe(CN)6]) Dissolving the solution A and the solution B in 2.5L of deionized water to form a transparent clear solution B, uniformly mixing the solution A and the solution B at room temperature to obtain an off-white turbid liquid, reacting at room temperature (25 ℃) for 24 hours to obtain a dark blue Prussian blue coordination crystal solution, and centrifugally separating the obtained Prussian blue coordination crystal solution at the speed of 10000rpm to obtain a Prussian blue coordination crystal solid; a. putting the obtained Prussian blue coordination crystal solid into 20ml of industrial alcohol, performing ultrasonic dispersion for 10min, and performing centrifugal separation at a speed of 8000 rpm to obtain the Prussian blue coordination crystal solid; b. b, placing the Prussian blue coordination crystal solid obtained in the step a into 20ml of deionized water, performing ultrasonic dispersion for 10min, and performing centrifugal separation at a speed of 10000rpm to obtain the Prussian blue coordination crystal solid; repeating the steps a and b for 3 times. Putting the finally obtained solid at room temperature, and drying for 20 hours in vacuum, wherein the vacuum degree is less than 0.1 Pa;
step 2: preparation of cathode fluid of seawater battery
And (3) taking 50 g of the prussian blue coordination crystal solid 500 ml of natural seawater in the step (1), placing the natural seawater into a beaker with the volume of 1L, placing the beaker into an ultrasonic cleaning instrument with the power of 50 kHz, and continuously carrying out ultrasonic treatment for 30 minutes to obtain uniform and continuous slurry. The obtained product can be used as the cathode fluid of a seawater battery;
and step 3: preparation of cathode current collector of seawater battery
The carbon felt is cut into blocks of 1.5 cm multiplied by 1 cm, and the carbon felt can be used as a cathode current collector of the seawater battery.
And 4, step 4: preparation of anode of seawater battery
The industrial pure aluminum with the license plate of 1A99 is selected and divided into aluminum sheets with the size of 3 cm multiplied by 0.5 cm, and the aluminum sheets can be used as the anode of the seawater battery.
And 5: assembly of seawater cells and constant current generation
And (3) respectively placing the carbon felt obtained in the step (3) and the aluminum metal sheet obtained in the step (4) into two electrolytic cells separated by a cation exchange membrane with the model of CMI 7000. The seawater electrolyte and the cathode fluid are respectively placed in two 1L beakers, and the seawater electrolyte and the cathode fluid are respectively introduced into an anode electrolytic cell and a cathode electrolytic cell by a peristaltic pump and a silicone tube. The cathode and the anode are respectively led out by copper wires and connected with two poles of an electric appliance, and then stable direct current can be output.
Fig. 5 is a constant current discharge diagram of the fluid seawater cell of this example, under test conditions in which the carbon felt obtained in step 3 and the aluminum metal sheet obtained in step 4 were placed in two electrolytic cells separated by a cation exchange membrane model CMI 7000, respectively. The seawater electrolyte and the cathode fluid are respectively placed in two 1L beakers, and the seawater electrolyte and the cathode fluid are respectively introduced into an anode electrolytic cell and a cathode electrolytic cell by a peristaltic pump and a silicone tube. The cathode and the anode are respectively led out by copper wires and are connected to a constant current mode of the blue battery test system to discharge at 5 mA current, and a voltage-time relation graph shown in figure 5 can be obtained.
In this embodiment, when the seawater electrolyte and the cathode fluid are respectively introduced into two electrolytic cells separated by a cation exchange membrane of CMI 7000 and aluminum sheets and carbon felt current collectors are immersed, due to the low redox potential of the 1a99 aluminum alloy, electrons are driven to move to the carbon felt end and finally transferred to the cathode fluid, the prussian blue coordination crystal receives electrons and absorbs cations in seawater at the same time to form prussian white coordination crystal, the metal aluminum is changed into an ionic form and dissolved in seawater, and current is generated due to the flow of electrons. When the cathode fluid is led out of the electrolytic bath and contacts with dissolved oxygen in seawater or oxygen in the air, the Prussian white coordination crystal is oxidized, a cation is released at the same time, and the Prussian blue coordination crystal is recovered, and the process is the recycling regeneration of the coordination crystal. Reciprocating in this way, stable current can be provided. The whole process is simple and easy to implement, and is environment-friendly and pollution-free to seawater.
Claims (3)
1. The preparation method of the fluid seawater battery is characterized by comprising the following specific steps of:
step 1: selection and preparation of cathode
A1: selection of coordination crystals
Selecting Prussian blue crystals and crystals with sodium ion storage sites as coordination crystals, wherein the molecular general formula of the Prussian blue crystals is AaMⅠ bMⅡ c[MⅢ(CN)6]d·nH2O; wherein A is an alkali metal element, a hydrogen ion or an ammonium ion; mⅠ、MⅡ、MⅢAre the same or different transition metal elements; a. b, c, d are [0,2 ]]The value of (a); n is [0,20 ]]The value of (a); the alkali metal element is Li, Na, K, Rb or Cs; the transition metal element is Fe, Co, Ni, Mn, Ti, Zn, Cr, Cu or In;
the crystal with sodium ion storage sites is: na (Na)2C6O6、Na4Fe3(PO4)2(P2O7)、NaVO2、NaCrO2、NaMnFe2(PO4)3、Na3Fe2(PO4)3、C24H8O6、C6Cl4O2、NaFePO4、Na2FeP2O7Or NaMnO2；
A2: preparation of cathode fluids
Preparing the cathode fluid by adopting a manual stirring, magnetic stirring or ultrasonic dispersion mode;
i) manual stirring: mixing the coordination crystals and the seawater in a container according to a mass ratio of 1: 10-8: 10, and stirring for 5-50 minutes by using a tool to form uniform and continuous slurry, so as to obtain the cathode fluid; wherein the content of the first and second substances,
the tool is as follows: glass rods, iron rods, aluminum alloy rods, magnesium alloy rods, scrapers or electric mixers;
the seawater is natural seawater with dissolved oxygen of at least 1ppm and sodium chloride of at least 0.35%, seawater prepared from sea salt or simulated seawater prepared from sodium chloride or potassium chloride;
ii) magnetic stirring: mixing the coordination crystals and the seawater in a container according to a mass ratio of 1: 10-8: 10, adding a magnetic stirrer, and driving the magnetic stirrer to stir for 5-50 minutes by using a magnetic stirrer to form uniform and continuous slurry, thus obtaining the cathode fluid; wherein the content of the first and second substances,
the magnetic stirrer is cylindrical, elliptical, cross-shaped, double-ended, triangular or octagonal and has the size of 5mm multiplied by 5 mm-500 mm multiplied by 500 mm;
the magnetic stirrer is an electric heating magnetic stirring sleeve or a flat plate type magnetic stirrer;
iii) ultrasonic dispersion: mixing the coordination crystals and seawater in a container according to a mass ratio of 1: 10-8: 10, and performing ultrasonic dispersion for 5-50 minutes by using an ultrasonic disperser to obtain uniform and continuous slurry, so as to obtain the cathode fluid; wherein the content of the first and second substances,
the ultrasonic dispersion instrument is an inserted ultrasonic dispersion instrument, an ultrasonic vibrator, an ultrasonic cleaning instrument or an ultrasonic vibration plate;
a3: preparation of the cathode
Guiding the prepared cathode fluid by a pump, flowing the cathode fluid through a current collector, and then circularly flowing the cathode fluid back to a container of the cathode fluid to obtain a fluid seawater battery cathode; wherein the content of the first and second substances,
the pump is a centrifugal pump, a mixed flow pump, an axial flow pump, a vortex pump, a piston pump, a plunger pump, a diaphragm pump, a gear pump, a screw pump, a scribing pump, an injection pump, a hydraulic ram or a vacuum pump;
the current collector is carbon cloth, carbon felt, metal titanium, metal copper or metal nickel;
the manner of flow through the current collector: flow from the outside of the current collector or from the inside of the current collector;
step 2: selection of anodes
Selecting metal magnesium, metal aluminum, metal zinc, mercury and calcium doped magnesium alloy, mercury and calcium doped aluminum alloy, mercury and calcium doped zinc alloy or mercury and calcium doped magnesium aluminum alloy as an anode;
and step 3: electrolyte solution
Seawater is selected as electrolyte for providing metal ions required in the power generation process and balancing electrode polarization effect; the seawater is natural seawater with dissolved oxygen of at least 1ppm and sodium chloride of at least 0.35%, seawater prepared from sea salt or simulated seawater prepared from sodium chloride or potassium chloride;
and 4, step 4: generation of constant current
Respectively putting the cathode current collector and the anode into two containers separated by a diaphragm, connecting the cathode current collector by a lead, and connecting the anode by the lead; immersing the anode with an electrolyte; opening the pump to flow the cathode fluid through the cathode current collector; constant direct current can be generated;
the diaphragm is: a cation exchange membrane, an anion exchange membrane, or a nonwoven fabric diaphragm;
and 5: cyclic regeneration of cathode-coordination crystals
When the metal ion storage sites in the cathode coordination crystal are completely occupied, the process of generating current is stopped; stirring the cathode fluid, and contacting the cathode fluid with seawater or air to oxidize the coordination crystals by using dissolved oxygen in the seawater or oxygen in the air, so that the coordination crystals lose electrons and release metal ions in the storage sites; then the cathode current collector is led in by a pump to continuously generate constant direct current.
2. The method for manufacturing a fluid seawater battery according to claim 1, wherein the prussian blue-based crystal is: fe4[Fe(CN)6]3、NaFe[Fe(CN)6]、Fe[Fe(CN)6]、NaMn[Fe(CN)6]、Na2Mn[Fe(CN)6]、NaMn[Fe(CN)6]、 Ni3[Fe(CN)6]2、Na2Ni[Fe(CN)6]、Na2Co[Fe(CN)6]、NaTi[Fe(CN)6]、Na2Cu[Fe(CN)6]Or Na2Zn[Fe(CN)6]。
3. A fluid seawater battery made by the method of claim 1.
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| CN117534089A (en) * | 2024-01-09 | 2024-02-09 | 太原理工大学 | Preparation of high-crystallization Fe [ Fe (CN) ] without additive 6 ]Method for producing electrode material and use thereof |
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