CN111816890B - Fluid seawater battery and preparation method thereof - Google Patents
Fluid seawater battery and preparation method thereof Download PDFInfo
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- CN111816890B CN111816890B CN202010693731.4A CN202010693731A CN111816890B CN 111816890 B CN111816890 B CN 111816890B CN 202010693731 A CN202010693731 A CN 202010693731A CN 111816890 B CN111816890 B CN 111816890B
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- 239000013535 sea water Substances 0.000 title claims abstract description 123
- 239000012530 fluid Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000013078 crystal Substances 0.000 claims abstract description 88
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 29
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000003792 electrolyte Substances 0.000 claims abstract description 26
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 22
- 239000001301 oxygen Substances 0.000 claims abstract description 22
- 230000008569 process Effects 0.000 claims abstract description 15
- 239000011780 sodium chloride Substances 0.000 claims abstract description 15
- 238000003860 storage Methods 0.000 claims abstract description 12
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 8
- 238000010248 power generation Methods 0.000 claims abstract description 8
- 238000004064 recycling Methods 0.000 claims abstract description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011777 magnesium Substances 0.000 claims abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 3
- 230000010287 polarization Effects 0.000 claims abstract description 3
- 239000013225 prussian blue Substances 0.000 claims description 45
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 claims description 44
- 229960003351 prussian blue Drugs 0.000 claims description 42
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- 229910052799 carbon Inorganic materials 0.000 claims description 24
- 239000011734 sodium Substances 0.000 claims description 17
- 235000002639 sodium chloride Nutrition 0.000 claims description 15
- 239000012528 membrane Substances 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 238000005341 cation exchange Methods 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 10
- 229910000838 Al alloy Inorganic materials 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 8
- 239000011575 calcium Substances 0.000 claims description 8
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 8
- 229910052753 mercury Inorganic materials 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 8
- 238000003760 magnetic stirring Methods 0.000 claims description 7
- 230000008929 regeneration Effects 0.000 claims description 7
- 238000011069 regeneration method Methods 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910001415 sodium ion Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 4
- 235000011164 potassium chloride Nutrition 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 230000021148 sequestering of metal ion Effects 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 2
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 238000005485 electric heating Methods 0.000 claims description 2
- 239000008151 electrolyte solution Substances 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- JOUIQRNQJGXQDC-AXTSPUMRSA-N namn Chemical compound O1[C@@H](COP(O)([O-])=O)[C@H](O)[C@@H](O)[C@@H]1[N+]1=CC=CC(C(O)=O)=C1 JOUIQRNQJGXQDC-AXTSPUMRSA-N 0.000 claims 2
- 229910021260 NaFe Inorganic materials 0.000 claims 1
- 239000003011 anion exchange membrane Substances 0.000 claims 1
- 239000010406 cathode material Substances 0.000 abstract description 6
- 239000010405 anode material Substances 0.000 abstract description 5
- 150000002500 ions Chemical class 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000002441 reversible effect Effects 0.000 abstract description 2
- 239000007787 solid Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 17
- 238000010586 diagram Methods 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000007788 liquid Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 6
- 230000002572 peristaltic effect Effects 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- WQKHTJFZNMYFQC-UHFFFAOYSA-L dichloroiron;hydrate Chemical compound O.Cl[Fe]Cl WQKHTJFZNMYFQC-UHFFFAOYSA-L 0.000 description 3
- 229960002089 ferrous chloride Drugs 0.000 description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 3
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 3
- 230000006855 networking Effects 0.000 description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 3
- 229960000999 sodium citrate dihydrate Drugs 0.000 description 3
- 239000000264 sodium ferrocyanide Substances 0.000 description 3
- GTSHREYGKSITGK-UHFFFAOYSA-N sodium ferrocyanide Chemical compound [Na+].[Na+].[Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] GTSHREYGKSITGK-UHFFFAOYSA-N 0.000 description 3
- 235000012247 sodium ferrocyanide Nutrition 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- HXXADHBCFWNQNP-UHFFFAOYSA-N [Fe](C#N)C#N.[Ni] Chemical compound [Fe](C#N)C#N.[Ni] HXXADHBCFWNQNP-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000013354 porous framework Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/30—Deferred-action cells
- H01M6/32—Deferred-action cells activated through external addition of electrolyte or of electrolyte components
- H01M6/34—Immersion cells, e.g. sea-water cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Hybrid Cells (AREA)
Abstract
The invention discloses a fluid seawater battery and a preparation method thereof, and belongs to the technical field of hybrid battery manufacturing. The method comprises the following aspects: 1) The fluid coordination crystal is taken as a main material, and a cathode material for providing storage sites for ions in seawater is provided, so that the reversible charge-discharge characteristic of the secondary battery is shown; 2) The anode material with magnesium and aluminum as main materials and with low redox potential is used for providing electrons until the metal is consumed. This is a typical primary battery feature; 3) The seawater solution with at least 1ppm of dissolved oxygen and at least 0.35% of sodium chloride is used as electrolyte to balance the polarization of the ion concentration in the electrode brought in the power generation process, so as to stabilize the environment of the power generation device. After the ion storage sites in the coordination crystal are fully occupied, dissolved oxygen in seawater is used for reacting with the coordination crystal to release ions in the storage sites, so that the cyclic use of the coordination crystal is realized. The method has the advantages of simple and convenient operation, environment-friendly materials, recycling and capability of meeting the general 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
Along with the proposal of the national ocean strategy, the problems of ocean power consumption and island power supply are to be solved. The existing power supply modes mainly comprise networking and off-network; the networking type power grid mainly uses a submarine cable mode, and although networking engineering can ensure island power supply reliability, the island power supply is a core technology of island power supply due to the remarkable cost, difficulty in 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, high in humidity and high in salt fog, and the photovoltaic power generation device needs special treatment under the conditions, so that the economic applicability is still to be improved. In order to solve the series of problems, researchers at home and abroad in recent years shift the viewing angle to the most abundant resource in islands-sea water. Attempts have been made to use natural seawater as an electrolyte for power generation, and seawater batteries have therefore been developed. The seawater battery has the outstanding characteristic that electrolyte is not needed to be carried, and can work in an all-sea environment. The seawater battery adopts the working principle of a primary battery, the anode is an active metal, and the cathode is an electrode of silver chloride, cuprous chloride and lead chloride, and the seawater battery is characterized by high energy density and high power, but in the discharging process, the seawater battery belongs to a primary battery due to the consumption of positive anode materials, has poor economy, and is mainly applied to military aspects as a power supply of torpedo; another type of metal-air seawater cell, the anode, is still active metal, while the cathode directly reduces the electrode with dissolved oxygen in the seawater. Compared with the former batteries, the anode still needs to consume active metal, and the cathode generates oxidation-reduction reaction by consuming dissolved oxygen in the seawater. The battery has the characteristics of a primary battery and the characteristics of a fuel battery. However, due to the limitation of the working principle, namely the limitation of the concentration of the dissolved oxygen of the cathode material, the power of the battery always has a great problem, and the existing battery system can only be suitable for low-power electrical appliances at sea, such as buoys, lighthouses and the like. Therefore, a cathode material with better efficacy 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, various topological structures, tailorability 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 intercalation and deintercalation of the guest ions. In recent years, coordination crystals typically represent Prussian blue compounds and have great potential in lithium, sodium, potassium plasma secondary batteries.
Disclosure of Invention
The invention aims to optimize the fluid seawater battery and the preparation method aiming at the problem of continuous energy supply in a specific marine environment.
The specific technical scheme for realizing the aim of the invention is as follows:
a fluid sea water battery and a preparation method thereof, the method comprises the following specific steps:
step 1: selection and preparation of cathode
A1: selection of coordination crystals
Prussian blue crystals and crystals with sodium ion storage sites are selected as coordination crystals, wherein the molecular general formula of the Prussian blue crystals is A a M Ⅰ b M Ⅱ c [M Ⅲ (CN) 6 ] d ·nH 2 O; wherein A is alkali metal element, hydrogen ion or ammonium ion; m is M Ⅰ 、M Ⅱ 、M Ⅲ Are the same or different transition metal elements; a. b, c and d are [0,2 ]]The values in (a); n is [0,20 ]]The values in (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) 2 C 6 O 6 、Na 4 Fe 3 (PO 4 ) 2 (P 2 O 7 )、NaVO 2 、NaCrO 2 、NaMnFe 2 (PO 4 ) 3 、Na 3 Fe 2 (PO 4 ) 3 、C 24 H 8 O 6 、C 6 Cl 4 O 2 、NaFePO 4 、Na 2 FeP 2 O 7 Or NaMnO 2 ；
A2: preparation of cathode fluid
The preparation of the cathode fluid adopts a manual stirring, magnetic stirring or ultrasonic dispersion mode;
i) manually stirring: mixing coordination crystals and 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 obtain uniform and continuous slurry, thereby obtaining the cathode fluid; wherein,,
the tool is as follows: glass rod, iron rod, aluminum alloy rod, magnesium alloy rod, scraper or electric stirrer;
the seawater is natural seawater with at least 1ppm of dissolved oxygen and at least 0.35% of sodium chloride, seawater prepared by sea salt, simulated seawater prepared by sodium chloride or potassium chloride;
ii) magnetic stirring: mixing coordination crystals and 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 obtain uniform and continuous slurry, thereby obtaining the cathode fluid; wherein,,
the magnetic stirrer is in a cylindrical shape, an elliptic shape, a cross shape, a double-head shape, a triangular column shape or an octagonal column shape, and the size is 5mm multiplied by 5mm to 500mm multiplied by 500 mm;
the magnetic stirrer is an electric heating magnetic stirring sleeve or a flat plate magnetic stirrer;
iii) ultrasonic dispersion: mixing 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 dispersing instrument to obtain uniform and continuous slurry, thereby obtaining the cathode fluid; wherein,,
the ultrasonic dispersing instrument is an inserted ultrasonic dispersing instrument, an ultrasonic vibrator, an ultrasonic cleaning instrument or an ultrasonic vibration plate;
a3: preparation of cathode
Guiding the prepared cathode fluid by a pump, flowing through a current collector, and recycling the current collector back to a container of the cathode fluid to obtain the cathode of the fluid seawater battery; wherein,,
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, a jet pump, a water hammer pump or a vacuum pump;
the current collector is carbon cloth, carbon felt, metallic titanium, metallic copper or metallic nickel;
the flow-through current collector is as follows: through the outside of the current collector or through the inside of the current collector.
Step 2: selection of anode
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;
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 at least 1ppm of dissolved oxygen and at least 0.35% of sodium chloride, seawater prepared by sea salt, simulated seawater prepared by sodium chloride or potassium chloride;
step 4: constant current generation
Respectively placing a cathode current collector and an anode into two containers separated by a diaphragm, connecting the cathode current collector by a wire, and connecting the anode by the wire; immersing the anode with an electrolyte; turning on the pump to enable the cathode fluid to flow through the cathode current collector; a constant direct current can be generated;
step 5: cyclic regeneration of cathode-coordinating crystals
When the metal ion storage sites in the cathode coordination crystal are fully occupied, the current generation process is stopped; stirring the cathode fluid, and oxidizing the coordination crystal by using oxygen of dissolved oxygen or air in the seawater by contacting the cathode fluid with the seawater or the air, so that the coordination crystal loses electrons and simultaneously releases metal ions in a storage site; and then the constant direct current is continuously generated by introducing the cathode current collector through a pump.
The Prussian blue compounds in the step 1 are as follows: fe (Fe) 4 [Fe(CN) 6 ] 3 (iron ferrocyanide, prussian blue, CAS number 14038-43-8), ni 3 [Fe(CN) 6 ] 2 (Nickel iron cyanide), na 2 Co[Fe(CN) 6 ](cobalt ferrocyanide), ti [ Fe (CN) 6 ](titanium ferrocyanide, na) 2 Cu[Fe(CN) 6 ](copper ferrocyanide), na 2 Zn[Fe(CN) 6 ](zinc ferrocyanide).
The invention has simple operation, environment-friendly material and recycling. Wherein the metal is mainly used for providing electrons in the power generation process and finally becomes ionic state to be dissolved in seawater; coordination crystals are used primarily to provide a site for the storage of 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 friendliness.
Drawings
FIG. 1 is a schematic diagram of a fluid seawater cell of the present invention;
FIG. 2 is a schematic side view of the cyclic regeneration of a cathode material-coordinating crystal of a fluid seawater cell of the present invention;
FIG. 3 is a constant current discharge diagram of the seawater battery prepared in example 1 of the present invention;
FIG. 4 is a constant current discharge diagram of the seawater battery prepared in example 2 of the present invention;
fig. 5 is a constant current discharge diagram of the seawater battery prepared in example 3 of the present invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and examples.
Referring to fig. 1, the seawater cell structure of the present invention is shown, wherein a prepared coordination crystal 1 is mixed with natural seawater 2 to form a cathode fluid, and placed in a beaker of 1L. The other side was placed in another beaker with natural seawater 2 as electrolyte. In the flow cell 5, a carbon felt 7 was used as a cathode current collector, an aluminum sheet 8 of metal, trade name 1a99, was used as an anode electrode, and was separated by a cation exchange membrane 6, model number CMI 7000. The carbon felt 7 is led out with copper wire to connect to the cathode of a load 10, for example a small bulb, and the aluminum sheet 8 of metal with the trade designation 1a99 is connected with copper wire to the anode of the load 10. The cathode fluid is introduced from the liquid inlet and outlet 4 through the silicone tube 9 by the pump 3 and flows back into the beaker through the other liquid inlet and outlet on the same side to form a circulation. The anolyte is introduced from the liquid inlet and outlet through the silicone tube by a pump 3 and then flows back into the beaker through the other liquid inlet and outlet on the same side to form a circulation. The seawater battery is formed.
Referring to fig. 2, a cyclic regeneration schematic diagram of a cathode coordination crystal of a seawater battery according to the present invention is shown, and when the metal ion storage sites of the coordination crystal 1 are fully occupied, the current generation process is stopped. Oxidizing the coordination crystal 1 by using dissolved oxygen in the seawater 2 or oxygen of air in a beaker for storing cathode fluid, so that the coordination crystal 1 loses electrons and simultaneously releases metal ions in a storage site; the oxygen is reduced to hydroxyl groups and is incorporated into the seawater, typically for 1 day.
Example 1
Manual stirring
The cathode material selected in this example is Prussian blue coordination crystal with molecular formula Fe 4 [Fe(CN) 6 ] 3 The method comprises the steps of carrying out a first treatment on the surface of the The anode material is industrial pure aluminum with license plate of 1A 99; the electrolyte is natural seawater.
Step 1: preparation of Prussian blue coordination crystals
16.7. 16.7 g ferrous chloride hydrate (FeCl) 2 ·6H 2 O) and 20 g sodium citrate dihydrate (HOC (COOH) (CH) 2 COONa) 2 ·1.5H 2 O) is dissolved in 2.5L deionized water to form transparent clear solution A; 14.5 g sodium ferrocyanide (Na 4 [Fe(CN) 6 ]) Dissolving in 2.5L 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 deep blue Prussian blue coordination crystal solution, and centrifugally separating the obtained Prussian blue coordination crystal solution at a speed of 10000rpm to obtain Prussian blue coordination crystal solid; a. putting the obtained Prussian blue coordination crystal solid into 20ml 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. putting the Prussian blue coordination crystal solid obtained in the step a into 20ml of deionized water, carrying out ultrasonic treatment for 10min for dispersion, and carrying out centrifugal separation at a speed of 10000rpm to obtain the Prussian blue coordination crystal solid; repeating the steps a and b for 3 times. The finally obtained solid is placed at room temperature, dried in vacuum for 20 h, and the vacuum degree is less than 0.1 Pa;
step 2: preparation of seawater battery cathode fluid
The Prussian blue coordination crystal solid 500 ml natural seawater in the step 1 of 50 g is 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 cathode fluid of a seawater battery;
step 3: preparation of cathode current collector of seawater battery
The carbon felt is cut into blocks of 1.5 cm multiplied by 1.5 cm multiplied by 1 cm, and the carbon felt can be used as a cathode current collector of a seawater battery.
Step 4: preparation of anode of sea water battery
The industrial pure aluminum with license plate 1A99 is selected and divided into aluminum sheets with the size of 2.5 cm multiplied by 2.5 cm multiplied by 0.5 cm, and the aluminum sheets can be used as the anode of the seawater battery.
Step 5: assembly of seawater cells and constant current generation
The carbon felt obtained in step 3 and the metal aluminum sheet obtained in step 4 were placed in two electrolytic cells separated by a cation exchange membrane of model CMI 7000, respectively. The seawater electrolyte and the cathode fluid are respectively placed in two beakers of 1L, and the seawater electrolyte and the cathode fluid are respectively introduced into an anode electrolytic tank and a cathode electrolytic tank by peristaltic pumps and silica gel tubes. The cathode and the anode are respectively led out by copper wires and connected with the two poles of an electric appliance, so that stable direct current can be output.
Fig. 3 is a constant current discharge diagram of the fluid seawater cell of the present example under the test condition that the carbon felt obtained in step 3 and the metal aluminum sheet obtained in step 4 were placed in two electrolytic tanks separated by a cation exchange membrane of model CMI 7000, respectively. The seawater electrolyte and the cathode fluid are respectively placed in two beakers of 1L, and the seawater electrolyte and the cathode fluid are respectively introduced into an anode electrolytic tank and a cathode electrolytic tank by peristaltic pumps and silica gel tubes. The cathode and anode are led out by copper wires respectively, and are discharged by 5 mA current in constant current mode of the blue battery test system, so that the voltage-time relation diagram shown in fig. 3 can be obtained.
In this embodiment, when the seawater electrolyte and the cathode fluid are respectively introduced into two electrolytic tanks separated by a cation exchange membrane with the model CMI 7000 and immersed in an aluminum sheet and a carbon felt current collector, electrons are driven to move to the carbon felt end due to the low redox potential of the 1a99 aluminum alloy and finally transferred to the cathode fluid, the Prussian blue coordination crystal accepts electrons and absorbs cations in seawater to form Prussian white coordination crystals, and metal aluminum becomes an ionic form and dissolves in the seawater, so that current is generated due to the flow of electrons. When cathode fluid is contacted with dissolved oxygen in seawater or oxygen of air after being led out of the electrolytic tank, prussian white coordination crystals are oxidized, and meanwhile, a cation is released, so that Prussian blue coordination crystals are recovered, and the process is cyclic regeneration of the coordination crystals. Thus, a stable current can be supplied. 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 is Prussian blue coordination crystal with molecular formula Fe 4 [Fe(CN) 6 ] 3 The method comprises the steps of carrying out a first treatment on the surface of the The anode material is industrial pure aluminum with license plate of 1A 99; the electrolyte is sea water prepared from sea salt.
Step 1: preparation of Prussian blue coordination crystals
16.7. 16.7 g ferrous chloride hydrate (FeCl) 2 ·6H 2 O) and 20 g sodium citrate dihydrate (HOC (COOH) (CH) 2 COONa) 2 ·1.5H 2 O) is dissolved in 2.5L deionized water to form transparent clear solution A; 14.5 g sodium ferrocyanide (Na 4 [Fe(CN) 6 ]) Dissolving in 2.5L 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 deep blue Prussian blue coordination crystal solution, and centrifugally separating the obtained Prussian blue coordination crystal solution at a speed of 10000rpm to obtain Prussian blue coordination crystal solid; a. putting the obtained Prussian blue coordination crystal solid into 20ml 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. putting the Prussian blue coordination crystal solid obtained in the step a into 20ml deionized water for ultrasonic treatmentDispersing for 10min, and centrifugally separating at 10000rpm to obtain Prussian blue coordination crystal solid; repeating the steps a and b for 3 times. The finally obtained solid is placed at room temperature, dried in vacuum for 20 h, and the vacuum degree is less than 0.1 Pa;
step 2: preparation of seawater battery cathode fluid
The Prussian blue coordination crystal solid 500 ml of 50 g step 1 is placed in a beaker with the volume of 1L, a cylindrical magnetic stirrer with the size of 120 mm multiplied by 10 mm is placed, and the mixture is stirred by a magnetic stirrer for 30 minutes at the speed of 400 revolutions per minute, so that uniform and continuous slurry is obtained. The obtained product can be used as cathode fluid of a seawater battery;
step 3: preparation of cathode current collector of seawater battery
The carbon felt is cut into blocks of 2 cm multiplied by 2 cm multiplied by 1 cm, and the carbon felt can be used as a cathode current collector of the seawater battery.
Step 4: preparation of anode of sea water battery
The industrial pure aluminum with license plate 1A99 is selected and divided into aluminum sheets with the size of 1 cm multiplied by 1 cm multiplied by 0.5 cm, and the aluminum sheets can be used as the anode of the seawater battery.
Step 5: assembly of seawater cells and constant current generation
The carbon felt obtained in step 3 and the metal aluminum sheet obtained in step 4 were placed in two electrolytic cells separated by a cation exchange membrane of model CMI 7000, respectively. The seawater electrolyte and the cathode fluid are respectively placed in two beakers of 1L, and the seawater electrolyte and the cathode fluid are respectively introduced into an anode electrolytic tank and a cathode electrolytic tank by peristaltic pumps and silica gel tubes. The cathode and the anode are respectively led out by copper wires and connected with the two poles of an electric appliance, so that stable direct current can be output.
Fig. 4 is a constant current discharge diagram of the fluid seawater cell of the present example under the test condition that the carbon felt obtained in step 3 and the metal aluminum sheet obtained in step 4 were placed in two electrolytic tanks separated by a cation exchange membrane of model CMI 7000, respectively. The seawater electrolyte and the cathode fluid are respectively placed in two beakers of 1L, and the seawater electrolyte and the cathode fluid are respectively introduced into an anode electrolytic tank and a cathode electrolytic tank by peristaltic pumps and silica gel tubes. The cathode and anode are led out by copper wires respectively, and are discharged by 5 mA current in constant current mode of the blue battery test system, so that the voltage-time relation diagram shown in fig. 4 can be obtained.
In this embodiment, when the seawater electrolyte and the cathode fluid are respectively introduced into two electrolytic tanks separated by a cation exchange membrane with the model CMI 7000 and immersed in an aluminum sheet and a carbon felt current collector, electrons are driven to move to the carbon felt end due to the low redox potential of the 1a99 aluminum alloy and finally transferred to the cathode fluid, the Prussian blue coordination crystal accepts electrons and absorbs cations in seawater to form Prussian white coordination crystals, and metal aluminum becomes an ionic form and dissolves in the seawater, so that current is generated due to the flow of electrons. When cathode fluid is contacted with dissolved oxygen in seawater or oxygen of air after being led out of the electrolytic tank, prussian white coordination crystals are oxidized, and meanwhile, a cation is released, so that Prussian blue coordination crystals are recovered, and the process is cyclic regeneration of the coordination crystals. Thus, a stable current can be supplied. 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 is Prussian blue coordination crystal with molecular formula Fe 4 [Fe(CN) 6 ] 3 The method comprises the steps of carrying out a first treatment on the surface of the The anode material is industrial pure aluminum with license plate of 1A 99; the electrolyte is sea water prepared from sea salt.
Step 1: preparation of Prussian blue coordination crystals
16.7. 16.7 g ferrous chloride hydrate (FeCl) 2 ·6H 2 O) and 20 g sodium citrate dihydrate (HOC (COOH) (CH) 2 COONa) 2 ·1.5H 2 O) is dissolved in 2.5L deionized water to form transparent clear solution A; 14.5 g sodium ferrocyanide (Na 4 [Fe(CN) 6 ]) Dissolving in 2.5L deionized water to form 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 deep blue Prussian blue coordination crystal solution, and using 10000r to obtain the Prussian blue coordination crystal solutionCentrifugal separation is carried out at the speed pm to obtain Prussian blue coordination crystal solid; a. putting the obtained Prussian blue coordination crystal solid into 20ml 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. putting the Prussian blue coordination crystal solid obtained in the step a into 20ml of deionized water, carrying out ultrasonic treatment for 10min for dispersion, and carrying out centrifugal separation at a speed of 10000rpm to obtain the Prussian blue coordination crystal solid; repeating the steps a and b for 3 times. The finally obtained solid is placed at room temperature, dried in vacuum for 20 h, and the vacuum degree is less than 0.1 Pa;
step 2: preparation of seawater battery cathode fluid
The Prussian blue coordination crystal solid 500 ml natural seawater in the step 1 of 50 g is placed in a beaker with the volume of 1L, and is placed in an ultrasonic cleaner with the power of 50 kHz, and is continuously and ultrasonically treated for 30 minutes to form uniform and continuous slurry. The obtained product can be used as cathode fluid of a seawater battery;
step 3: preparation of cathode current collector of seawater battery
The carbon felt is cut into blocks of 1.5 cm multiplied by 1.5 cm multiplied by 1 cm, and the carbon felt can be used as a cathode current collector of a seawater battery.
Step 4: preparation of anode of sea water battery
The industrial pure aluminum with license plate 1A99 is selected and divided into aluminum sheets with the size of 3 cm multiplied by 3 multiplied by cm multiplied by 0.5 multiplied by cm, and the aluminum sheets can be used as the anode of the seawater battery.
Step 5: assembly of seawater cells and constant current generation
The carbon felt obtained in step 3 and the metal aluminum sheet obtained in step 4 were placed in two electrolytic cells separated by a cation exchange membrane of model CMI 7000, respectively. The seawater electrolyte and the cathode fluid are respectively placed in two beakers of 1L, and the seawater electrolyte and the cathode fluid are respectively introduced into an anode electrolytic tank and a cathode electrolytic tank by peristaltic pumps and silica gel tubes. The cathode and the anode are respectively led out by copper wires and connected with the two poles of an electric appliance, so that stable direct current can be output.
Fig. 5 is a constant current discharge diagram of the fluid seawater cell of the present example under the test condition that the carbon felt obtained in step 3 and the metal aluminum sheet obtained in step 4 were placed in two electrolytic tanks separated by a cation exchange membrane of model CMI 7000, respectively. The seawater electrolyte and the cathode fluid are respectively placed in two beakers of 1L, and the seawater electrolyte and the cathode fluid are respectively introduced into an anode electrolytic tank and a cathode electrolytic tank by peristaltic pumps and silica gel tubes. The cathode and anode are led out by copper wires respectively, and are discharged by 5 mA current in constant current mode of the blue battery test system, so that the voltage-time relation diagram shown in fig. 5 can be obtained.
In this embodiment, when the seawater electrolyte and the cathode fluid are respectively introduced into two electrolytic tanks separated by a cation exchange membrane with the model CMI 7000 and immersed in an aluminum sheet and a carbon felt current collector, electrons are driven to move to the carbon felt end due to the low redox potential of the 1a99 aluminum alloy and finally transferred to the cathode fluid, the Prussian blue coordination crystal accepts electrons and absorbs cations in seawater to form Prussian white coordination crystals, and metal aluminum becomes an ionic form and dissolves in the seawater, so that current is generated due to the flow of electrons. When cathode fluid is contacted with dissolved oxygen in seawater or oxygen of air after being led out of the electrolytic tank, prussian white coordination crystals are oxidized, and meanwhile, a cation is released, so that Prussian blue coordination crystals are recovered, and the process is cyclic regeneration of the coordination crystals. Thus, a stable current can be supplied. 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
Prussian blue crystals and crystals with sodium ion storage sites are selected as coordination crystals, wherein the molecular general formula of the Prussian blue crystals is A a M Ⅰ b M Ⅱ c [M Ⅲ (CN) 6 ] d ·nH 2 O; wherein A is alkali metal element, hydrogen ion or ammonium ion; m is M Ⅰ 、M Ⅱ 、M Ⅲ Is the same or differentA transition metal element of (2); a. b, c and d are [0,2 ]]The values in (a); n is [0,20 ]]The values in (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) 2 C 6 O 6 、Na 4 Fe 3 (PO 4 ) 2 (P 2 O 7 )、NaVO 2 、NaCrO 2 、NaMnFe 2 (PO 4 ) 3 、Na 3 Fe 2 (PO 4 ) 3 、C 24 H 8 O 6 、C 6 Cl 4 O 2 、NaFePO 4 、Na 2 FeP 2 O 7 Or NaMnO 2 ；
A2: preparation of cathode fluid
The preparation of the cathode fluid adopts a manual stirring, magnetic stirring or ultrasonic dispersion mode;
i) manually stirring: mixing coordination crystals and 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 obtain uniform and continuous slurry, thereby obtaining the cathode fluid; wherein,,
the tool is as follows: glass rod, iron rod, aluminum alloy rod, magnesium alloy rod, scraper or electric stirrer;
the seawater is natural seawater with at least 1ppm of dissolved oxygen and at least 0.35% of sodium chloride, seawater prepared by sea salt or simulated seawater prepared by sodium chloride or potassium chloride;
ii) magnetic stirring: mixing coordination crystals and 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 obtain uniform and continuous slurry, thereby obtaining the cathode fluid; wherein,,
the magnetic stirrer is in a cylindrical shape, an elliptic shape, a cross shape, a double-head shape, a triangular column shape or an octagonal column shape, and the size is 5mm multiplied by 5mm to 500mm multiplied by 500 mm;
the magnetic stirrer is an electric heating magnetic stirring sleeve or a flat plate magnetic stirrer;
iii) ultrasonic dispersion: mixing 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 dispersing instrument to obtain uniform and continuous slurry, thereby obtaining the cathode fluid; wherein,,
the ultrasonic dispersing instrument is an inserted ultrasonic dispersing instrument, an ultrasonic vibrator, an ultrasonic cleaning instrument or an ultrasonic vibration plate;
a3: preparation of cathode
Guiding the prepared cathode fluid by a pump, flowing through a current collector, and recycling the current collector back to a container of the cathode fluid to obtain the cathode of the fluid seawater battery; wherein,,
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, a jet pump, a water hammer pump or a vacuum pump;
the current collector is carbon cloth, carbon felt, metallic titanium, metallic copper or metallic nickel;
the flow-through current collector is as follows: flow from outside the current collector or flow from inside the current collector;
step 2: selection of anode
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;
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 at least 1ppm of dissolved oxygen and at least 0.35% of sodium chloride, seawater prepared by sea salt or simulated seawater prepared by sodium chloride or potassium chloride;
step 4: constant current generation
Respectively placing a cathode current collector and an anode into two containers separated by a diaphragm, connecting the cathode current collector by a wire, and connecting the anode by the wire; immersing the anode with an electrolyte; turning on the pump to enable the cathode fluid to flow through the cathode current collector; a constant direct current can be generated;
the diaphragm is: cation exchange membranes, anion exchange membranes or nonwoven membranes;
step 5: cyclic regeneration of cathode-coordinating crystals
When the metal ion storage sites in the cathode coordination crystal are fully occupied, the current generation process is stopped; stirring the cathode fluid, and oxidizing the coordination crystal by using oxygen of dissolved oxygen or air in the seawater by contacting the cathode fluid with the seawater or the air, so that the coordination crystal loses electrons and simultaneously releases metal ions in a storage site; and then the constant direct current is continuously generated by introducing the cathode current collector through a pump.
2. The method for preparing a fluid seawater cell according to claim 1, wherein the prussian blue type crystal is: fe (Fe) 4 [Fe(CN) 6 ] 3 、NaFe[Fe(CN) 6 ] 、Fe[Fe(CN) 6 ] 、NaMn[Fe(CN) 6 ] 、Na 2 Mn[Fe(CN) 6 ] 、NaMn[Fe(CN) 6 ] 、 Ni 3 [Fe(CN) 6 ] 2 、Na 2 Ni[Fe(CN) 6 ] 、Na 2 Co[Fe(CN) 6 ]、NaTi[Fe(CN) 6 ]、Na 2 Cu[Fe(CN) 6 ]Or Na (or) 2 Zn[Fe(CN) 6 ]。
3. A fluid seawater cell made by the method of claim 1.
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