JP2021012863A - Power generation system using oxygen extracted from water - Google Patents

Abstract

To provide the cogeneration of electrical and sterile water in an electrochemical cell including an oxygenation reaction (OER) anode and an oxygen reduction reaction (ORR) cathode, a method of electrolyzing water on the anode and converting oxygen into electricity on the cathode, and a self-contained water fuel facility that includes four subsystems for electricity and water cogeneration.SOLUTION: Both an anode and a cathode share an oxygen production reaction and an oxygen reduction reaction, the former consumes energy and the latter produces electricity. The cathode forms a load and the anode forms an electroforming circuit. The circuit requires clean water to supply oxygen as fuel. A built-in water purification device supplies clean water which is a raw material for all-water fuel cells.SELECTED DRAWING: Figure 1

Description

The present invention relates to the cogeneration of electrical and sterile water in an electrochemical cell containing an oxygenation reaction (OER) anode and an oxygen reduction reaction (ORR) cathode. More specifically, the present invention relates to a method of converting oxygen into hydrogen peroxide and electricity by electrolysis of water on the OER anode and ORR on the cathode. To facilitate oxygen production and the conversion of oxygen into electricity, the present invention provides a self-contained water fuel facility that includes four subsystems for electricity and water cogeneration.
The four subsystems include (1) energy and water production, (2) online water purification, (3) energy storage equipment, and (4) controllers that manage the flow of electricity, water and gas.

Energy and water are two important elements that support human life and activity. They also make up the majority of household spending, and supplying them is the primary responsibility of each government.
With increasing energy and water demands, global warming and water pollution, governments tend to increase their budgets to meet people's energy and water needs. Faced with El Nino, sporadic natural disasters, and environmental protection issues, the reality is that in many cases the government cannot resolve all situations. To solve energy demands without polluting the environment, people turn to renewable energies such as solar cells, wind turbines and ocean waves, but nevertheless, renewable energies are intermittent and geological. There are also restrictions. Other approaches to nature-dependent energy generation include fuel cells, waste heat utilization, and vibrational energy utilization. Fuel cells have existed for over 160 years, and five types of fuel cells have been developed. However, neither technology is widely adopted. Recently, microbial fuel cells are often found in US patents as the sixth fuel cell. U.S. Pat. Nos. 4,652,501,7,544,429, 9,450,437, 9,520,608, 9,776,897, 10,164,282, and the like. Research efforts in all fuel cells have focused primarily on the discovery of common metals to replace Pt, Pd, and Ru, increased power output, membranes used, and safety. The development of biofuel cells utilizes non-precious metals as claimed by US Pat. No. 608, but the brush electrodes of US Pat. No. 897, the multi-cell partition of US Pat. No. 282, and US Pat. No. 282. There is a No. 429 filmless cell. However, the involvement of microorganisms, sludge or wastewater impedes the commercial viability of biofuel cells. As far as the production of drinking water is concerned, conventional water treatment techniques including reverse osmosis (RO), membrane filtration, UV disinfection, Fenton reaction and microbial digestion are time consuming, expensive and with by-products.
Most recently, Haupt et al. Reported an electrochemically accelerated oxidation process (EAOP) as a new technique in the magazine of Electrical Chemistry Communications. Through energy consumption analysis for increased COD (Chemical Oxygen Demand), EAOP has been shown to be superior to conventional techniques. Our invention will prove that the Sb, Ni-SnO ₂ catalysts are more effective than the boron-added diamond (BOD) catalysts used in the cited papers. Besides cost, fuel cells have another serious drawback, low power density. In fact, fuel cells are priced based on their electricity. It is US $ 500-1,000 for an output of 1 KW. Almost all of the power density values reported in papers related to biofuel cells are less than 1 W /. Kodali et al. Published an excellent output density of 452 W / cm ² or 4.52 W / m ² in the biofuel cell of Electrochemica Acta. Obviously, the power density is far from the practical level required for many applications, including electric vehicles. Like many other generators, they all require a power storage device for long-term use. Supercapacitors, also known as ultracapacitors, pseudocapacitors, or double layer capacitors, are the best devices for storing the energy produced by fuel cells. A supercapacitor is a versatile power amplifier with high charging efficiency, and what is important in the present invention is that the main body can be used as a housing for storing and supporting a fuel cell and its components. It is in.

US Patent 4,652,501 3/1987 Bennetto et al. 6,512,667 B2 1/203 Shiue at al. 7,544,429 B2 1/209 Kim et al. 7,696,729 B2 4/2010 Shiue at al. 9,174,985 B2 11/2015 Shiue et al. 9,450,437 B2 9/2016 Kim et al. 9,520,608 B2 12/2016 Becker et al. 9,776,897 B2 10/2017 Silver et al. 10,164,282 B2 12/2018 Bahrebar et al. Japanese Patent Application No. 2006-348482 (P2006-348482) JP-A-2007-31284 (P2007-31284A) JP-A-2008-149302 (P2008-149302A JP-A-2008-161846 (P2008-161846A) JP-A-2008-132466 JP-A-2008- 54486 (P2008-54486A) Japanese Patent Application Laid-Open No. 2008-60208 (P2008-60208) Japanese Patent Application Laid-Open No. 2009-45608 (P2009-45608A) Japanese Patent Application Laid-Open No. 2009-190016 (P2009-190016A) Japanese Patent Application Laid-Open No. 2009-152513 (P2009-152513A) 33075 (P2009-33075A) Special Table 2010-528175 (P2010-528175A) Special Table 2010-524200 (P2010-524200A) Japanese Patent Application Laid-Open No. 2012-1806 (P2012-1806A)

Other D. Haupt et al. , Electrochem. Communications, Vol 101, pp115-19 (2019). Kodali et al. , Electrochemica Acta, Vol. 231 and pp115-124 (2017).

Efficient and economical generation of oxygen by electrolysis from water using low-voltage DC power on an anode board made of antimony-nickel-added tin oxide-treated titanium material (Sb, Ni-SnO ₂ / Ti) Can be achieved. At the same time as oxygen evolution, it is rapidly reduced to hydrogen peroxide (H ₂ O ₂ ) and electricity by the adjacent cobalt oxide-added carbon nanofilm (Co ₃ O _4- CNF / Ti). In this power generation, oxygen is first generated in an oxygen evolution reaction (OER), and then power generation is performed in an oxygen reduction reaction (ORR). Both the anode and the cathode share an oxygen production reaction and an oxygen reduction reaction, the former consuming energy and the latter producing electricity. The cathode forms the load and the anode forms the electroforming circuit. The circuit requires clean water to supply oxygen as fuel. In the present invention, the fuel cell is referred to as an all-water fuel cell (AWFC: all-water fuel cell). Here, the supercapacitor is adopted as the load of the all-water fuel cell. The built-in water purification device then supplies clean water, which is the raw material for all-water fuel cells.

To facilitate the production of oxygen and the electrical conversion of oxygen, the present invention provides self-contained equipment containing four subsystems for electrical and water cogeneration. The four subsystems include (1) energy and water production, (2) online water purification, (3) energy storage equipment, and (4) controllers that manage the flow of electricity, water and gas. The controller will be procured externally, but all other three subsystem materials will be homemade. A detailed description of embodiments of the disclosed devices and methods is presented herein by way of example with reference to the drawings. Although the particular embodiment has been described in detail, it should be understood that various changes and amendments can be made without departing from the appended claims. The scope of the present invention is not limited to the number of components, the material thereof, the shape thereof, the relative arrangement thereof, etc., but is merely disclosed as an example of an embodiment of the present invention. The present invention provides an AWFC containing four subsystems: (1) providing AWFC and sterilized water to generate electricity, (2) removing TDS and COD to supply clean water to the AWFC. An online water purifier consisting of equipment, (3) a supercapacitor as a housing and electric energy stored in it, (4) utilization and electricity of required energy, and a CPU that manages ozone gas and water. The system can be easily extended to meet various power applications and water demands in homes, communities, businesses, industries, military and remote areas. Oxygen, the fuel, is obtained from water in fluid form as a liquid or vapor by electrolyzing on the anode with a low cost catalyst and low power consumption. As a source of fuel, water is safe, universally and inexpensively available, but it is a valuable resource within the AWFC system. Therefore, the AWFC system has a high cost-effectiveness value (CP value). The next paragraph details the four subsystems.
All-water fuel cell (AWFC)
In the first place, this patent is based on 10 years of research and development of electrolytic ozone (electrolytic ozone generation) by the inventor. As represented by the following equations 1 and 2, the electrolysis of water always produces oxygen on the anode side and hydrogen on the cathode side.
Anode reaction: 2H ₂ O → O ₂ ↑ + 4H ⁺ + 4e ⁻ E ° = 1.23V (1)
Cathode reaction: 2H ₂ O + 2e ⁻ → H ₂ ↑ + OH ⁻ E ° = 0.0V (2)
E ° is the standard potential required to produce oxygen and hydrogen. If ozone (O ₃ ) is desired, it is necessary to raise the O ₂ generation potential (OEP) to the level at which O ₃ is formed, as described by equation (3).
Anode reaction: 3H ₂ O → O ₃ ↑ + 6H ⁺ + 6e ⁻ E ° = 1.60V (3)
(1) + (3) 5H ₂ O → O ₂ ↑ + O ₃ ↑ + 10H ⁺ + 10e ⁻ E ° = 1.60V (4)
Thus, effective economical and stable O ₃ formed catalyst must be available to the anode.
We have tried several precious metals such as platinum (Pt), gold (Au) and iridium (Ir), as well as glassy carbon and graphite. In the end, it proved that tin oxide (SnO ₂ ) doped with dimensional stability anode (DSA) -antimony (Sb) and nickel (Ni) meets the requirements.
SnO ₂ is an intrinsic n-type semiconductor, and when Sb is doped, SnO ₂ becomes transparent and conductive (this is called ATO). As a second dopant, nickel is involved in the rise of OEP. Titanium (Ti) is the most rational metal for the substrate of Sb / Ni-doped SnO ₂ because the oxidation environment of the electrolyzed ozone-producing anode is harsh. Although Sb, Ni-SnO ₂ / Ti are the anodes for electrolyzed ozone production that are widely discussed in the literature, we have selected non-chlorinated salts for Sn, Sb and Ni (of Sb, Ni-SnO ₂ ). To avoid the generation of HCl vapor during thermal preparation). This is for producing a catalyst membrane, which is novel unlike other literature reports. Table 1 lists the non-Cl precursors that can be selected for each of the three metal elements for Sb, Ni-SnO ₂ / Ti production:

The Sb, Ni-SnO ₂ catalyst film is made in air through multiple cycles of "coating-drying-sintering". The coating solution is water containing a mixture of stannous oxalate, antimony trioxide and nickel acetate in a molar ratio of three metals Sn: Sb: Ni = 500: 8: 1.
Sn ⁴⁺ concentration or ^{[sn 4+]} is set to 0.2 ^M,, if the Sb 3+ ^{-Ni 2+} is added in the ratio, the solution yields a catalyst film having a thickness of ¹⁶ ~ 17 nm on the Ti surface per cycle obtain. The ideal film thickness range is 2-4 μm. Multiple processes of 118 to 236 times with 0.2 M solution are required to reach the desired film thickness. To promote slow film deposition, the present invention has a ratio of [Sn ⁴⁺ ] of 0.8 ^to 1.2 M [Sn ⁴⁺ ], [Sn ⁴⁺ ] of 2.8 ^to 4.4% [Sb ³⁺ ], and. It is proposed that the ratio of [Sn ⁴⁺ ] is 0.8 ^to 1.8% [Ni ²⁺ ].
It was measured that the concentrated coating solution could produce a film of 60-65 nm per cycle.
A pair of electrodes in which the anode base of Sb, Ni-SnO ₂ / Ti is combined with a cathode board made of general SUS304 stainless steel is electrolyzed from tap water, purified water or steam using a minimum of 3 volt DC current. the oxygen and ozone in the anode, to produce water, the cathode to generate an H _2. More gaseous products are formed when higher voltages are applied. Regardless of the applied _voltage, H _2: O 2: production ratio of _{O 3} is 6: 2: 1. The current efficiency of ozone generation can be calculated to be 30-35% on the assumption that PEM (proton exchange membrane) and additives are not added to water. Accordingly O ₃ electrolytic process of the present invention, it is possible to produce a O _{2 /} O ₃ with low power consumption with high efficiency. However, the reaction on a stainless steel cathode causes two problems with respect to electrolyzed ozone production.
1) Adhesion-Ca ²⁺ / Mg ^{2+ in} water becomes a scale and strongly adheres to the cathode, resulting in passivation. Removing this is awkward.
2) H 2 _- that of H ₂ at the cathode is generated at high speed, there are safety concerns. In order to solve the above problems, an air cathode electrode capable of reacting with O ₂ from air has been developed by the present invention. Instead of stainless steel, titanium is used as the base material for the cathode to prevent corrosion. FIG. 1 shows the configuration of an Sb, Ni—SnO ₂ / Ti anode sandwiched between two cathodes fixed at regular intervals such as 1 to 2 mm without arranging a separator or a film between a pair of electrodes. In the stack, there are actually two cells connected in series with three electrodes assembled. As shown in FIG. 1, the electrolysis mechanism has two side-by-side circuits. One is the electrolysis of water on the anode induced by a DC power source, where the working voltage can be measured with a voltmeter in parallel with the anode and cathode. Another circuit is oxygen reduction with a cathode, load, ammeter and Sb, Ni-SnO ₂ / Ti anode configuration. As described in equation (4), a direct current causes an oxygen evolution reaction (OER) on the anode side.
5H ₂ O → O ₂ ↑ + O ₃ ↑ + 10H ⁺ + 10e ⁻ E ° = 1.60V (4)
Equation (4) is similar to the reaction of the anode of the electrolyzed ozone generation electrode. With the exception of O ₃ , the product of formula (4) is converted to H ₂ O ₂ by the catalyst of the cathode as in formula (5):
^{_{O 2 + 2H + + 2e -}} → H 2 O 2 (5)
Equation (5) is the movement of two electrons in the oxygen reduction reaction (ORR), without water intervention, and as a result neither H ₂ nor OH ⁻ is produced. Anions (OH ⁻ ) are believed to be responsible for Ca / Mg scaling on stainless steel cathodes. The problem of hydrogen formation and dirt adhesion is solved or minimized.
As soon as the OER is started, O _2, H ⁺ and electrons are generated, they are automatically and instantaneously flow from the anode to the cathode, to induce ORR correspondingly. The electricity generated by the ORR can be easily drawn by a register resistor or an empty supercapacitor, and the magnitude of the current can be measured by an ammeter. The circuit in which this electricity includes the air cathode, the load, and the Sb, Ni-SnO ₂ / Ti anode becomes the all-water fuel cell (AWFC). At the same time that O ₂ is reduced at the cathode, O ₃ binds to H ₂ O ₂ to form peroxone. This is a new form of AOP (Aspect Oriented Programming) that sterilizes water, groundwater and wastewater into drinking water. Peroxone can also decompose volatile organic compounds, chlorinated solvents, diesel waste oil, and PAHs (polynuclear aromatic hydrocarbons).
The unique and new features of this AWFC are:
1. 1. All reactions occur in water in a closed, pure environment.
2. 2. O ₂ is generated inside H ₂ O and automatically diffuses into the ORR area. Diffusion settings for O ₂ reduction, such as gas diffusion layer (GDL), are not required on the cathode.
3. 3. H ⁺ also diffuses freely on its own, eliminating the need for a PEM (proton exchange membrane).
4. ORR induces OER and vice versa. This interaction exists for a period of time without a DC power source for the OER. Without a DC power source, the power generated by the AWFC will decrease but will not disappear completely.
5. If the OER is constantly supplied with low power to produce enough O ₂ , the ORR will continuously generate large power.
6. Confinement of more ORR areas and O ₂ is the key to obtaining high power and high current of AWFC rather than the increase of DC energy supporting OER.
7. Energy and sterile water, these two essential and valuable resources are produced together.
8. O ₂ is the fuel for power generation in the AWFC, which is obtained from water in the fluid form of liquid or vapor. O ₂ can also be obtained from air.
FIG. 2 shows the scale-up of AWFC by stacking a plurality of anodes and cathodes as a component with a constant gap. Both electrodes use different catalysts, but they all have perforations for the easy generation of O ₂ as well as for a uniform distribution of O ₂ over the entire cathode surface. The cells are formed by one side of the anode facing one side of the cathode, and thus the drawing of FIG. 2 contains 10 cells. All anodes in FIG. 2 are placed in series to increase the voltage or in parallel to achieve higher current output. Similarly, all cathodes can have the same arrangement. Both the anode and the cathode can be manufactured in the form of flat plates, curved plates and other designs, tubes and meshes. In other words, the present invention can prepare electrodes in any shape as required.
FIG. 3 is a process known as hydrothermal synthesis for producing an air cathode. The first step is to prepare an aqueous solution of the carbon-rich precursor. Also, all necessary catalysts in the metal salt are dissolved to make a solution. The Ti plate is then immersed in this solution for a period of time to impregnate the precursor and catalyst. After removing the excess solution, the coated Ti is subjected to wood charcoal treatment at 200-400 ° C. in air to form added charcoal. This treatment also provides thermal stabilization of the precursor. Finally, wood carbide (charcoal) is carbonized by thermal decomposition at 600-900 ° C and in an oxygen-free environment. A conformal, monolithic layer of catalyst (M) -doped carbon nanofilm grows directly on the (M · CNF / Ti) Ti substrate to an AWFC-operated air cathode. Polyacrylonitrile (PAN), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyacrylic acid (PAA), polymethylmethacrylate (PMMA), cellulose, dextrin, lignin, apple salt, polysaccharides as carbon-rich precursors , Gelatin and polyimide. Cobalt oxide (Co ₃ O ₄ ) was selected by the present invention as the catalyst for ORR on the cathode. Choices of cobalt precursors include cobalt nitrate, cobalt sulfate, cobalt carbonate, cobalt hydroxide, cobalt bromide and cobalt chloride. For the production of improved activated carbon (MAC) of supercapacitor materials by using granular activated carbon (GAC) or SAE304 stainless steel (SS) foil instead of Ti, along with specific solutions of carbon-rich precursors and additives. Is also available, which allows online purification of water and storage of electricity from AWFC as shown in Fig. 3 for hydrothermal synthesis.
Purified water by the device is ubiquitous on earth, and even in the driest areas there is water underground. However, water from underground, ditches, rivers, lakes, streams, and the sea is often useless as it is. TDS and COD (including BOD) are the main pollutants to be removed from water. The present invention has developed a special-purpose adsorbent that uses GAC as a carrier. GAC is widely used in water treatment for adsorption, filtration and catalyst support of ions / dyes / organics / volatile organic compounds (VOCs). However, GAC has low conductivity and has micropores. This causes a problem that the GAC is saturated. In order to solve these problems, especially the recycling / reuse of materials, the present invention applied the hydrothermal synthesis of FIG. 3 to GAC. A monolithic layer of conductive carbon nanofilm (CNF) is coated on all GAC particles, resulting in a new core-shell composite. This new particle is called MAC-C, which is an improved GAC in the core, and the shell "C" not only imparts high conductivity to the MAC with CNF, but also seals the micropores. Experiments have shown that MAC-C can remove TDS in raw water with a TDS of 100 Kppm or higher. MAC-C is also a building block for producing the COD-removing adsorbent MAC-CX. "X" is a general term for catalytic oxides of the first transition metal in the periodic table. MAC-CX is produced by blending "X" according to the nature of wastewater, adding it to MAC-C, and heat-treating it. By using the correct combination of transition metals, it is possible to reduce COD of 10 Kppm or more from the wastewater of the MAC-CX adsorbent in a single passage of running water. Both MAC-C and MACX are manufactured using heat above 300 ° C. MAC-C and MAC-CX are robust and can withstand the stress of running water purification that operates 24 hours a day.
Taking advantage of the high conductivity of MAC, two stainless steel electrodes are placed on both sides of the tower-shaped components of MAC-C and MAC-CX. A low DC voltage of 3-5V is applied between the electrodes to create a weak electric field in the tower. The MAC-C and MAC-CX of this electric field are drawn into the positive electrode of the particle near the anode, and are drawn into the negative electrode by the particle near the cathode. In the case of MAC-C, the adsorption of ions from saltwater seawater on charged particles is promoted by static charge attraction and produces new desalination. On the other hand, MAC-CX, which is a COD adsorbent, can convert ozone gas supplied from AWFC into hydroxyl radicals (.OH). -OH is a stronger oxidant than ozone (see Table 2), and the decomposition rate of COD pollutants is several hundred times that of ozone.

With the help of a weak electric field, charged and polar COD contaminants are attracted to the MAC-CX particle electrodes. This forms on the surface of MAC-CX-OH also performs sterilization quickly and almost completely. -The aforementioned COD removal by OH is another new technique for water treatment, which is called low power AOP. When the application to the electric field is turned off, the ions of MAC-C and the residue adsorbed on MAC-CX by electrostatic attraction are automatically discharged. Rapid regeneration of the adsorbent can be achieved by flushing the filled bed with a small amount of in-situ clean water of about 10%.
The AWFC continuously generates electricity by continuously supplying O ₂ from the supercapacitors Sb and Ni-SnO ₂ anodes by the OER. The present invention utilizes supercapacitors to store continuously generated energy. As long as the voltage of the AWFC is higher than the voltage of the supercapacitor, the latter will always charge currents of any magnitude without waste. Once the capacitors are fully charged, AWFC power generation continues without harming any component of the system. Hydrothermal synthesis in FIG. 3 and using a stainless steel (SS) foil or plate as the substrate, a conformal conformal layer of monolithic carbon nanofilm (CNF) with a thickness of 50 to 70 μm is placed on the substrate in place. Can be grown with. As described in the protocol of FIG. 3, conductive CNFs are made from carbon-rich precursors to which additives have been added to increase the energy density of the supercapacitors produced thereby. Therefore, the electrode from thermal decomposition at 600-900 ° C. is an electrode with a gel polymer electrolyte (GPE) for making the desired supercapacitor. Electrodes manufactured at high temperatures are also described in the literature. This electrode has the unique features below:
1. 1. No organic binder is used, only the conductive nanocarbon matrix produced during the heat treatment and the dopant in the electrodes.
2. 2. Pore specifications and hierarchical structure can be prepared as desired.
3. 3. Metal oxides and dichalcogenides that can impart pseudo-capacity can be used as dopants for CNF.
4. Conversion of the precursor to activated carbon, graphite or graphene can be achieved by controlling the type of precursor, catalyst, pyrolysis temperature, atmosphere and heating time.
5. Stainless steel (SS), titanium (Ti) or titanium-attached copper foil can be used as the current collector.
6. The thickness of the foil is 10 to 20 μm, which is beneficial for the energy power density of the supercapacitors produced thereby.
7. Both stainless steel (SS) and Ti have stronger corrosion resistance than conventional Al or Cu, so supercapacitors manufactured by the former can have a longer life.
8. The adhesion between the carbon layer and the current collector is built by chemical bonds, which is also beneficial for the resistance of supercapacitors.
GPE is another unique feature of supercapacitors according to the present invention. It is a printable gel made of a polymer dissolved in an aprotic solvent containing one or more salts as a solute. Table 3 shows the materials that can be selected for the polymer, solvent, and solute.

GPE determines the electrochemical performance and life of supercapacitors. Each component of the GPE has its purpose within the device. Polymers are an important factor related to the ESR (equivalent series resistance) of capacitors. The solvent determines the target operating temperature in the range of -60 ° C to 150 ° C and the electrochemical potential stability of the capacitor. The solute provides ions to build capacitance and ion conduction to complete the electrical circuit. GPE provides supercapacitors with three functions.
a. Separator to prevent electrical short circuit b. Ion conductor for lowering ESR c. Adhesive for fixing electrodes As shown in FIG. 4ab, a unit cell of a supercapacitor includes two electrodes sandwiching a GPE. FIG. 4a shows two bent electrodes. FIG. 4b has two circular electrodes, or the roll shape can be formed by concentrically winding two pipes or two GPE-printed electrode pieces. The electrodes of FIGS. 4a and 4b are symmetrical and their polarity cannot be specified prior to charging. After charging, one electrode is positively charged and the other electrode is negatively charged. However, the polarities of the electrodes can be switched as desired and short-circuited without damaging each other. Unit cells such as those in FIGS. 4a and 4b have an operating voltage of 3V as the cell voltage. The cell voltage is 3V, but the operating range of a single cell supercapacitor is -3V to 3V. The potential range is 6V. Most power applications for supercapacitors require potential widths in excess of 6V. Instead of connecting a plurality of singular supercapacitors in series as shown in FIG. 5A, the present invention has developed a technique for arranging a plurality of electrodes vertically on a high voltage module. As shown in FIG. 5A, there are 10 rectangular electrodes, 2 terminal electrodes and 8 intermediate electrodes between the 2 terminal insulating plates. The eight electrodes inside are bipolar electrodes, which are indicated by dots (.). Only the electrodes at both ends have terminals for connecting to a charging source or load. When charged, both sides of each bipolar electrode will have different polarities.
As shown in FIG. 5A, assembly is started by installing a terminal plate on the bottom of the automatic stacker. The bottom terminal electrode is then placed on the end plate, followed by a predetermined amount of uniform GPE layer over the end electrode. The first bipolar electrode is then landed on the end electrode with the same amount of GPE coating for contact with another GPE layer on the lower electrode. After stacking the two electrodes and mixing the GPE, apply the GPE to the upper surface of the first bipolar electrode, and then put the second, third, fourth, ... 8th bipolar electrode on top. Stack until the electrodes and top insulating end plates are in order. GPE is applied to the electrodes before stacking. It is important to follow the following three stacking rules in this process:
A. The application of GPE is carried out by the machine to ensure the proper amount.
B. Stacking is done in vacuum so that the air trapped in each of the two electrodes can be eliminated.
C. The GPE is pressed to form a uniform layer without gaps, and the load is set to 10 kg as an example.
After application of GPE, the gel remains sticky until it comes into contact with the layer of GPE, then a porous structure is formed, which acts as a separator when adsorbed on the electrode and loses some of its solvent. The separator fixes the stacked electrodes in place. Excess GPE extruded from the edge of the stack for insulation needs to be removed. The edges are then sealed to protect the internal elements.
FIG. 5A shows three-dimensionally the assembly by internal series connection of a plurality of electrodes to a high voltage supercapacitor module. FIG. 5B shows the correlation between the capacitance, voltage, and stacking of the module using the three-axis coordinates. In FIG. 5B, the XY product represents the stacked electrode effective area. The cell is composed of two electrodes, and the capacitance of the cell can be obtained by multiplying the area of the electrodes by the capacitance density (F / cm2) of the electrodes. However, the overall capacitance of the module is smaller than that of the cells in the module. Equation (6) can be used to calculate the total capacitance of the stacked module:
Capacitance of the entire module = Capacitance of cells / Number of cells in the stack (6)
In equation 6,
The number of cells in the stack = the number of electrodes in the stack-1.
In FIG. 5B, the height of the Z axis is a measure of the overall voltage of the stacked module. The higher the Z-axis, the higher the operating voltage of the module. The total operating voltage of the module is calculated by equation (7):
Operating voltage of the entire module = number of cells in the stack x cell voltage (3V) (7)
Assembling the electrodes by stack is an internal series connection of multiple cells. There is no need for a protection circuit to balance the voltage distribution between the linked cells, as with internal series connections in lead-acid batteries.
Since all cells are in the same container (housing), they share the same environment of vapor pressure and temperature, resulting in self-equalization of voltage. Not only is the protection circuit saved, but it also eliminates the need for many connecting materials.
Management of energy and water generated by the AWFC system Management functions are required for the efficient operation and utilization of the energy and sterile water generated by the AWFC system. Managers need to maintain a reliable supply of clean water for energy production through the AWFC's OER and ORR. The purified water produced not only satisfies OER, but also meets the conditions for fresh water. Online purified water, MAC-C desalting for TDS reduction, as well (including BOD) COD depends on the AOP and MAC-CX by _{O 3} removal. It is also important for large-scale energy storage and high efficiency of energy use.
Power tank Figure 4 shows that supercapacitors can be configured in the form of cubes and cylinders. Although other shapes of the supercapacitor are not disclosed, the shape of the electrode produced by hydrothermal synthesis in FIG. 3 is not particularly limited. Thus, the supercapacitor can be built inside the AWFC system as a chassis and as an internal support, as a casing for accommodating system components. The internal series connection is as follows. As shown in FIG. 5A, the desired high voltage supercapacitor module can be manufactured in various dimensions. Many supercapacitors can be built in the AWFC system. These energy storage devices do not have a fixed physical connection, but can be managed in real time to form series, parallel or a combination of both. Such coupling can be performed via the X / Y busbar and electronic switch under the direction of the administrator, central processing unit (CPU), as revealed in FIG. The drawings are from US Pat. No. 7,696,729, a patent granted to one of the inventors. The CPU has the following functions:
"Remember the position of the supercapacitor. Monitor the energy state of the supercapacitor.
Identify the failed supercapacitor. Charge supercapacitors individually or collectively quickly. Calculate the number of supercapacitors required for power distribution. Connect the supercapacitors needed for power supply in series, regardless of their location. Calculate the number of supercapacitors needed for energy collection. Parallel connection of supercapacitors that require power generation. Perform a CD swing. Inverting the polarity of a supercapacitor in real time. Power supply for water purification and fresh water supply to AWFC or on-site water use. "
The power tank and its CPU controller can completely store all the energy generated by the AWFC. Moreover, the requirements of all power applications can be met by the large storage capacity of the power tank and its energy management system.
Charge / discharge switching system (CD swing)
Conventional supercapacitors are easily consumed during discharge due to their low energy density.
Powering by supercapacitors is always intermittent because it takes time to be fully charged before they can re-release energy. In addition, the voltage of the supercapacitor drops rapidly during discharge and becomes invalid as soon as the voltage drops below the drive voltage of the load.
For efficient use of energy, supercapacitors preferably emit only the energy of the first third of the rated voltage. Using two groups of supercapacitors for power supply, each group can only release the first 1/3 rated voltage. When the first group completes the set discharge, it goes into charge mode and the second group immediately takes on the role of discharge.
In the next cycle, the charge / discharge flow is alternated. The two groups will continue to charge and discharge each other until the power demand is met. Since only the active energy is released and refilled, the energy utilization efficiency of the CD swing is high. Supercapacitors can supply power continuously in this way, which is not found in conventional supercapacitors. The CPU directs the operation of the CD swing, which can also set the level of power supplied by controlling the switching frequency.
Reverse Charging Platform As shown in FIG. 5A, in the discharge of the supercapacitor module made by internal series connection, it is observed that one side of the bipolar electrode is discharged and the other pole is charged at the same time. Reverse charging is caused by the passage of a "return" current from the load back through the supercapacitor to the negative electrode of the power supply. The back side of the bipolar electrode bears a higher voltage (−V) than the residual (+ V) on the front side. Then, when the polarity of the terminal of the supercapacitor is inverted by the CPU, the empty supercapacitor is in the fully charged state again. This reverse charge belongs to a kind of energy recovery. It is similar to a vehicle mechanism with a braking mechanism in that it has the energy to recover. High energy efficiency and energy generation are just as important as power generation. Similarly, H ₂ O savings and H ₂ O regeneration are as important as H ₂ O production.
Finally, a self-contained AWFC system is shown in FIG. There are supercapacitors and water reservoirs (not shown) for operating the OER on the Sb, Ni-SnO ₂ / Ti anodes mounted on the system. Water can also be pumped on board to obtain water from sources such as rivers, lakes, streams, oceans, trenches and underground. In order to minimize the water sampling TDS, it is first treated with MAC-C by adsorption desalination. Thereafter, deionized water is fed to the low power consumption type AOP process for COD removal by _{O 3} and MAC-CX. If the treated water is less than the preset degree of purification, the CPU will instruct the water to be treated again. Clean water then enters the AWFC to cogenerate energy and sterile water. Energy acquisition and energy injection between the AWFC and the CPU are bidirectional operations.
When the Sb, Ni-SnO ₂ / Ti anode is activated, O ₂ is generated and reduced to H ₂ O ₂ and electricity by the Co ₃ O _4- CNF / Ti cathode. OER and ORR have different velocities, and OER seems to respond faster than ORR. It means that the generated O ₂ is more than the consumed O ₂ . Therefore, in order to generate a lot of electricity, a lot of cathode regions should be provided. The other power increase method, to increase the site of the reduction catalyst, there is a more powerful catalyst and efficient use of the generated O _2.
The first successful fuel cell was developed in 1932 by Francis Bacon in the United Kingdom. He used H ₂ and O ₂ , alkaline electrolyte, and Ni electrodes as fuel. In 1952, Bacon and its collaborators built a 5kW fuel cell system. In the late 1950s, NASA was using Apollo, Gemini, alkali in the manned spacecraft program of the space shuttle, PEM, a pure _{H 2} fuel cell. The present invention is, without a PEM, using only O ₂ fuel from the water by a good anode economically efficient with a simple design. In addition to safe O ₂ use without H ₂ , AWFC produces 1.2 V per cell.
This is significantly higher than 0.5V-0.8V per cell of fuel cells based on H ₂ and O ₂ as fuel.

In AWFC, O ₂ is directly converted into electricity, but in the case of alkaline fuel cells, H ₂ is used only as fuel. Furthermore the design of AWFC, much simpler than parts that are employed with H ₂ based fuel cells, requires less material consumption. So AWFCs are easy to scale up at an affordable price to generate high currents and high voltages to power communities, hospitals, factories, electric vehicles, electric buses, and even research submarines. ..

The present invention is well understood by reference to the following drawings and embodiments described in the text.
It is a schematic of the basic unit of AWFC composed by one anode sandwiched by two cathodes in a certain gap. Two electrical circuits are included. One is the power supply for the oxygen production reaction at the anode and the other is the oxygen reduction reaction at the cathode with electricity drawn by the load and measured by an ammeter. It is the schematic of the stack of a plurality of anodes and cathodes. In the figure, a cell is composed of an anode and a cathode, and 10 cells are formed. It is a flowchart of hydrothermal synthesis for producing a cathode of an air electrode using a titanium plate as a carrier. When granular activated carbon and stainless steel foil are used as carriers with the solution, the products are modified activated carbon (MAC) for supercapacitors and binder-free electrodes, respectively. It is a side view of a laminated supercapacitor assembled in a U shape and a conical shape by two electrodes and GPE, and these can function as a shell, a housing, a chassis, a frame, or an internal support for an AWFC system. These invisible supercapacitors store all the energy produced by the ORR on the cathode. This is an example of assembling supercapacitor electrodes by vertical juxtaposition. The stacked electrodes are fixed by GPE. The XY axes determine the overall capacitance of the supercapacitor, and the height of the Z axis indicates the operating voltage of the supercapacitor. It is a figure of the built-in supercapacitor in the AWFC system which forms the electric power tank managed and driven by the central processing unit (CPU). Four subsystems of the AWFC system. (1) AWFC, electricity and water generator, (2) online water purifier consisting of TDS / COD remover, (3) supercapacitor as housing, (4) CPU manages electricity flow, ozone gas and water ..

To facilitate oxygen production and electrical conversion of oxygen, the present invention provides a self-contained all-water fuel cell (AWFC) facility that includes four subsystems for electricity and water cogeneration. The four subsystems include (1) energy and water production, (2) online water purification, (3) energy storage equipment, and (4) controllers that manage the flow of electricity, water and gas. The controller will be procured externally, but all other three subsystem materials will be homemade. A detailed description of the four subsystems is as follows:
Energy and Water Generation The components of the all-water fuel cell of the invention include:
Anode: Titanium substrate treated with antimony and nickel-added tin oxide (Sb, Ni-SnO ₂ / Ti).
The anode is made from a non-chloride salt of Sn, Sband Ni prepared based on a formulation and protocol effective for forming a clear solution in clean water. The solution is coated on a titanium substrate, which is dried and sintered in a convection oven to form the desired catalyst film on the substrate.
Cathode: Titanium substrate treated with cobalt oxide-added carbon nanofilm (Co ₃ O _4- CNF / Ti).
As with the anode, the construction of the cathode begins with a clear solution containing a carbon-rich precursor containing additives and cobalt salts. A titanium plate is dipped in the solution to impregnate the mixture of precursor and cobalt. The coated titanium plate is semi-carbonized and carbonized as a two-step heat treatment to reach the desired air cathode. Using hydrothermal synthesis, special activated carbon (MAC) and supercapacitor electrodes are prepared as follows.
Electrode assembly: The anode is sandwiched between two cathodes at regular intervals. All electrodes should have the same dimensions and shape. The scale of the assembly is achieved by alternating the anode and cathode. No membrane is required between the anode and cathode.
Reaction medium: Clean water, including tap water and distilled water, that undergoes electrolysis on the anode to form oxygen and ozone. Oxygen is reduced directly and rapidly on the cathode to form hydrogen peroxide.
Some ozone mixes with hydrogen peroxide to form peroxone, but most ozone is used to purify water in the system.
By online water purifier hydrothermal synthesis, granular activated carbon (GAC) can be coated on an insulating protective layer of carbon nanofilm (CNF) to form a core-shell structural composite. The core-shell structure is an improved activated carbon (MAC), a fast and highly efficient adsorbent for water treatment. MAC can also be applied as a TDS (total dissolved solids) or COD (chemical oxygen demand) remover. By combining two or more types of removers, a total solution for water treatment will be provided.
Building Blocks: In core-shell composites, the GAC is the core and the shell is a thin conductive film synthesized from a carbon-rich precursor. For simplicity, the composite is labeled MAC-C, where C represents a conductive carbon nanofilm. Not only can C impart GAC conductivity, but it can also seal the micropores of the GAC to promote regeneration of the GAC. MAC-C is a central component of many MAC-C applications.
Electric field: Since MAC-C is more conductive than ordinary activated carbon, it is possible to promote the adsorption of ions and polar species on the surface of MAC-C or MAC-C applications even with a weak electric field.
Low power consumption TDS removal effect: By inserting two stainless steel (SS) substrates on both side surfaces of a cylinder filled with MAC-C particles, a running water type low power consumption TDS removal function is formed. When a DC current of 3-5 volts is applied to the SS substrate, a weak electric field transforms all MAC-C particles into positive or negative electrodes, depending on the distance from nearby stainless steel electrodes. When salt water flows, the water is absorbed by the particle electrodes via electrostatic attraction, and desalination is performed. When the power is turned off, most of the adsorbents are automatically discharged, and the residual adsorbents can also be washed away with clean water generated from the constituents of the invention in a volume corresponding to 10% of the target water.
Low power consumption COD removal effect: This effect is similar to that of the field effect TDS cylinder, except that the filler is MAC-CX. X here is a first-row transition metal oxide produced by hydrothermal synthesis on the carrier MAC-C. In addition to the voltage, ozone gas is injected from the AWFC into the COD tube to convert it to hydroxyl radicals (.OH). Quantitative and fast removal of COD is performed in running water mode. Regeneration of MAC-CX can be easier than regeneration of MAC-C, as this completely removes COD contaminants.
Incorporation of energy storage equipment:
Aside from energy density and leakage current, supercapacitors are superior to all batteries in terms of cost, life and performance for energy storage. In addition, supercapacitors can function as power amplifiers, voltage balancers, and battery boosters. The present invention also provides a unique supercapacitor with the following unique features:
Electrodes: Electrodes are grown directly by hydrothermal synthesis on monolithic carbon nanofilms (CNFs) with capacitance-enhancing elements added on stainless steel (SS) foil. In the manufacturing process, the carbon-rich precursor is converted into a CNF or graphene film by thermal decomposition at 600 to 900 ° C. The electrodes produced contain only carbon and metal oxides or chalcogenides. No binder for adhesion is used for the SS substrate in the electrode manufacturing process. The performance of the electrode is expressed by the capacitance density F / cm ² .
Gel Polymer Electrolyte (GPE): The polymer is selected to dissolve in an aprotic solvent mixture in the working temperature range of −60 ° C. to 150 ° C. or higher, together with at least the electrolyte for forming the GPE. Such GPEs have three functions for the supercapacitors produced therein: (1) separators, (2) ionic conductors, and (3) adhesives for adhering laminated electrodes in place. As. GPE is primarily evaluated for its potential stability as measured by cyclic voltammetry (CV). The test sample exhibits good cycle characteristics in the potential range of -3V ± 3V. This means that the cell voltage of the supercapacitor in this patent is 3V.
Electrode assembly: The required area of the electrode is determined based on the capacitance density of the electrode (F / cm2) and the target capacitance of the electrode product. The electrodes are prepared with desired dimensions. A layer of GPE is applied to the surface of each electrode, and then an automatic assembly facility is used to stack the two electrodes with the GPE coated surfaces facing each other facing each other. The top stacked electrode forms a GPE layer and is stacked with another treated electrode.
This stacking and layer forming process is repeated until the target operating voltage is achieved [number of electrodes required for stacking = (operating voltage / 3V) + 1]. Only the stacked electrodes on both sides are provided with leads for connecting to a charging source or load, and all other intermediate electrodes are bipolar electrodes. When the capacitor is charged, one side of the bipolar electrode is positively charged and the other side is negatively charged. It is called a bipolar electrode because the electrodes have different polarities on both sides.
Built-in supercapacitors: Two-sided SS plate electrodes can be stacked side by side and placed themselves as a shell or housing for AWFC. The supercapacitor incorporated as described above can function as a frame, chassis, and other supports for the internal structure of the AWFC. If the size of the AWFC is large, the supercapacitor shell can be turned into a container for a bank of multiple smaller capacitors in a series of power tanks, as described in US Pat. No. 7,696,729. You can. In reality, all supercapacitors built into the AWFC are integrated as a total power supply. Each supercapacitor member does not have a fixed physical connection. However, they can be assembled in real time to form series or parallel linkages via electronic switches and busbars under the command of a central processing unit (central processing unit (CPU)).
The AWFC of the present invention can be operated safely without continuous noise and generate electricity every second and every day. All supercapacitor components of the power tank can be fully charged before power demand arises. The central processing unit (CPU) acts as the brain, and the AWFC is the central device that produces energy and water at an affordable price. The central processing unit (CPU) functions and two unique operating platforms required to maximize energy savings are shown below.
Central Processing Unit (CPU) and Power Tank: The central processing unit (CPU) not only controls the movement of energy, but also the ozone gas needed to reduce COD and the running water between the AWFC and the water purifier. The central control circuit (CPU) stores the position of the supercapacitor, monitors its energy state, identifies the failed capacitor, charges the supercapacitor individually or collectively, and the number of supercapacitors required for power supply. Calculate and control the number of supercapacitors required to satisfy energy, connect supercapacitors to collect energy in parallel, and perform charge / discharge swing (CD swing) between two supercapacitors of the same group to generate energy. It reverse-charges the supercapacitor to save money, and controls the supply of ozone to improve the COD removal effect, the supply of clean water to the AWFC, the operation of the OER, and the closure of the OER.
CD swing platform: Due to the low energy density, the supercapacitor is discharged quickly, so the supercapacitor's power supply needs to be intermittently fully recharged before it can be repowered. .. Moreover, since the holding voltage is lower than the load drive voltage, the capacitor voltage quickly becomes invalid. In order to save energy, it is preferable that the supercapacitor uses only the energy stored at a voltage equal to or higher than the rated voltage of 2/3. With two groups of supercapacitors, each group releases only the first 1/3 rated voltage. When the first group discharges, it enters the charging mode, and the second group immediately takes on the role of discharging. In the next cycle, the order of charging and discharging is reversed. The two groups perform mutual charge and discharge until the power demand is met. Since only the active energy is released and replenished, the energy utilization efficiency of the CD swing is high. In addition, supercapacitors can be continuously powered.
This is not found in conventional capacitors. The central control circuit (CPU) can instruct the operation of the CD swing, and can also set the level of output power by adjusting the switching frequency.
Reverse Charging Platform: In the discharge of a supercapacitor containing at least one bipolar electrode, we have observed that one side of the bipolar electrode is engaged in the discharge while the other side is being charged at the same time. Reverse charging is caused by the passage of return current through the supercapacitor. Therefore, one side of the bipolar electrode generates an absolute voltage (−V) higher than that of the other side (+ V). Reversing the polarity of the terminals of the supercapacitor effectively recharges the supercapacitor of the depleted power supply device. Reverse charging belongs to a type of energy recovery, which is similar to vehicle regenerative braking in terms of the recoverable energy in it.

Example 1
Test samples of AWFC is, Sb, is formed by sandwiching Ni-SnO2 / Ti anode with two _Co 3 _O 4 -CNF / Ti cathode at a constant gap 2 or 1 mm. The dimensions of both the anode and the cathode are 7.5 cm wide x 25 cm long. For the test, a 20 cm long electrode set is immersed in a 15 liter tap water tank. For long-term testing, an OER was supplied to the anode using a 10 V DC power supply. Further, 9V is recorded in a voltmeter set in parallel with the electrodes to measure the operating voltage. As soon as bubbles were generated on the anode, no bubbles were observed on the cathode, and the ammeter in series with the cathode, the 500 Ω resistor and the anode showed a current of 20-25 mA. Since the current value is displayed on the ammeter regardless of the presence or absence of the DC power supply, the power generation at the cathode by the ORR can be seen. Table 4 shows the experimental conditions and the results.

In Table 4, the OER of the Sb, Ni-SnO ₂ / Ti anode is supported by a DC power supply set to 10 V, and the operating current is 3.5 A. It becomes warm under the influence of water evaporation (water level drop) and water temperature (water temperature). When the DC power is on, the current generated by the ORR is greater than that when the power is off. Since O ₂ is limited to the ORR, the ORR also uses the air cathode of the plate without holes to generate more current. When OER is off, the voltage generated by the ORR is 2.4V. This is the combined voltage of two cells connected in series. It was not expected that AWFC could reduce the hardness of water. Factors TDS reduction or softening of H ₂ O is Peruokison considered to be a combination of _{O 3} and _H 2 _{O 2.} Since the two-cell AWFC is left in still water for several hours, fluctuations in water such as changes in temperature, TDS and pH are negative factors for ORR power generation. Nevertheless, the normal operation of the AWFC system of FIG. 7 is performed by passing water through the AWFC, so that the power generation by the ORR is stable.
Example 2
Pharmaceutical wastewater from pharmaceutical companies of caffeine and antipyretic analgesics, have been processed by _O 3 + MAC-CX of low-voltage AOP. Electrolysis formula _{O 3} tank is used to produce the _{H 2 / O 2 / O 3} . The gaseous product is drawn into a cylinder filled with MAC-CX particles or steel wool balls coated with MAC-CX. COD removal, power, and in terms of conversion to benign products of H ₂ consumed it was intended to evaluate the performance of the wastewater treatment new system. Table 5 lists adopted _O 3 + MAC-CX systems, water supply condition, and the processing result.

As shown in Table 5, the ozone generated in the processing time of 2.38 hours is completely consumed, but the conversion rate of H ₂ is about 98%, which is the hydrogen reaction used in the oil refinery. Higher than the conversion rate of the vessel.
Wastewater containing TDS was also measured as high as 90.1 mS / cm (about 180,200 ppm, three times that of seawater). The concentration of TDS remained unchanged, which did not appear to be important for the removal of COD. One of the reasons for the unchanged TDS is that it does not affect the catalytic function of MAC-CX. The catalyst X in Table 5 is used for H ₂ conversion rather than COD removal. Table 5 shows that removal of 1 kg of COD by AOP consumes about 4 kWh of power and only 183 g of O ₃ to produce the "by-product" H ₂ .
Example 3
A major pharmaceutical company manufactures a number of antibiotics, painkillers, stomach acid suppressants, and blood pressure regulators. These drugs are polynuclear hydrocarbons (PHC), which are pharmaceutical and personal care products (PPCP). When PPPP enters various organisms, it can alter the endocrine pathways of vertebrate species and is therefore called Endocrine Disrupting Contaminants (EDCs). EDC is considered a poorly soluble pollutant that is hardly degraded by common methods. The COD content of the wastewater of the company is as high as 209,617 ppm. Such high COD-enriched water, is without dilution using H 2 _O, can not be processed in the general art of water treatment. However, the addition of water to the raw water by dilution, increasing the total amount of H _{2 O} to be processed exponentially. _O 3 + MAC-CX system to the processing of ultra-high-concentration COD wastewater is required.
Table 6 lists the components with a set of parameters in pretreatment equipment such as EC (Electrical Aggregation), EO ₃ (Electrolytic Ozone), and EO ₃ + MAC-CX systems, and COD measurements at each stage of processing. Is provided as well.

Table 6 shows that the reduction of the COD by the _O 3 + MAC-CX is caused by AOP. Each cylinder of A, B and C is filled with 500 g of MAC-CX granules, and a weak DC voltage for performing microelectrolysis is also applied to B and C. Gradually, the COD of raw water decreases from 209,617 ppm to 35,019 ppm. The removal rate by passing running water is 83.3%. If H ₂ is converted to OH by the MAC-CX incorporated in Table 6, the COD may be 100% removed. Adjusting the pH of the raw water by adding alkali removed a significant amount of 14,796 ppm COD, but the next continuous pretreatment with three consecutive electrocoagulation (EC) devices was so ineffective in removing COD. Looked. Perhaps EC operations may only help protect the MAC-CX adsorbent. The weak DC current and MAC-CX appear to have a synergistic effect via the conductive nanocarbon film C deposited on the MAC. Since C imparts conductivity to the MAC, the adsorption and desorption of the surface of the GAC granules is regulated by an electric field. In addition to the low adsorption and oxidation forces of MAC-CX, there is no sludge formed in the treatment with MAC-CX. Therefore, the EO ₃ + MAC-CX system is energy efficient and cost effective. In U.S. Patent No. 9,174,895, issued to one of the present inventors, the EO ₃ in combination with EC using iron (Fe) as the anode in the rapid removal of COD _species, ^FeO 4 2- or [ Fe (IV) O] Generates Fe (VI) ions in the form of ²⁺ . The disclosure of US Pat. No. '895 not only consumes much more power than the EO ₃ + MAC-CX system, but also results in sludge that requires costly post-processing. Sludge is also a cost-increasing factor in common treatment techniques for COD pollution such as the electric Fenton reaction. Oxygen is known as a combustion accelerator but is not flammable. No inventor has developed a fuel cell that uses O ₂ as fuel. However, this patent proves that O ₂ can be produced by electrolysis of water on the Sb, Ni-SnO ₂ / Ti anode, followed by reduction of O ₂ on the Co ₃ O _4- CNF / Ti cathode. Catalytic reduction of O ₂ to generate an _H 2 _{O 2} electricity. Each substance produced by cathodic reduction has its advantages.

The benefits provided by the present invention and the best use of electricity generated are outlined.
1. 1. Disinfectants: Microbial removal and pesticide decomposition without H ₂ generation by controlled online production of the right amounts of ozone (O ₃ ) and hydrogen peroxide (H ₂ O ₂ ) at the right time. Achieved.
2. 2. Water purification: Poorly soluble pollutants in water can be quantified by high concentrations of TDS and COD. The former can be greatly reduced by the MAC-C latter can completely removed by the combination of _{O 3} and MAC-CX. Both MAC-C and MAC-CX are capable of rapid recycling and regeneration.
3. 3. Supercapacitors: Using carbon nanofilms (CNFs) grown directly on stainless steel plates with GPEs to produce high voltage supercapacitor modules that store the electricity generated by the ORR and discharge it at high power. Can be done.
4. Energy utilization: A power tank is formed using multiple supercapacitor modules. With CD swing and reverse charge, the stored energy can be used in an effective and efficient way.
When the important technique of the present invention must be named, the answer is hydrothermal synthesis in FIG. After synthesis, the additive containing the selected precursor and catalyst is converted to SS, Ti, ceramic, honeycomb, etc. to become a ready-to-use electrode or immediate adsorbent. The ion plasma spray coating can also manufacture the electrode, but it has less freedom in material selection and manufacture for this purpose. It is considered that the above-mentioned examples and explanations have successfully explained the features and the whole picture of the present invention. More importantly, the invention is not limited to the embodiments described herein.
Those skilled in the art will readily appreciate that the teachings of the present invention can make numerous modifications and modifications to the device. Therefore, the above disclosure should be easily construed as not limited to the boundaries and scope of the appended claims.

Claims (12)

The next step, namely, the method of generating electricity using oxygen in water
Prepare a basic structural unit without using a separation membrane by Sb, Ni-SnO ₂ / Ti anode sandwiched between two Co ₃ O _4- CNF / Ti cathodes with a certain gap (CNF here is a carbon nanofilm). Is),
And to provide purification of water with TDS-removing adsorbents and COD-removing adsorbents, where water is in fluid form and water is selected from the following groups, which are tap water, fresh water,. Purified water and steam generated online,
Oxygen is generated from electrolyzed water on the Sb, Ni-SnO ₂ / Ti anode via an oxygen evolution reaction (OER), and Co ₃ O _4- CNF / via an oxygen reduction reaction (ORR) that uses low DC power. Generating by reducing oxygen on the Ti cathode,
Then, at least one supercapacitor draws out and stores the electricity generated from the cathode. In the method of claim 1, the basic unit comprises two cells connected in series. In the method of claim 1, the OER and ORR are treated in water, the OER producing oxygen and ozone gas, and the ORR producing hydrogen peroxide and electricity. In the method according to claim 1, the anode here has a catalyst containing Sb and Ni-added SnO ₂ deposited on a Ti plate represented as Sb, Ni-SnO ₂ / Ti, and has three metals. The precursors of the above are SnC ₂ O ₄ , Sb ₂ O ₃ and Ni (CH ₃ COO) ₂ , respectively, and the concentration of each metal ion in the aqueous coating solution is 0.8 ^to 1.2 M for [Sn ⁴⁺ ]. , [Sb ³⁺ ] is in the range of 2.8 ^to 4.4% with respect to [Sn ⁴⁺ ], and [Ni ²⁺ ] is in the range of 0.8 ^to 1.8% with respect to [Sn ⁴⁺ ]. In the method according to claim 1, the CNF is polyacrylonitrile (PAN), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyacrylic acid (PAA), polymethylmethacrylate (PMMA), cellulose, dextrin, lignin, and the like. Produced by hydrothermal synthesis using precursors selected from apple salt, polysaccharides, gelatin and polyimide. In the method of claim 1, Co ₃ O ₄ on the cathode is made from a cobalt salt selected from cobalt nitrate, cobalt sulfate, cobalt carbonate, cobalt hydroxide, cobalt bromide and cobalt chloride. In the method according to claim 1, the supercapacitor is constructed by assembling a plurality of electrodes by juxtaposed stacking. In the method according to claim 1, the COD removing adsorbent is represented by MAC-CX, where X is selected from transition metals containing Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn. It is a catalyst for metal oxides that uses the precursors to be produced. In the method of claim 1, a plurality of the supercapacitors are prepared and function as a chassis, a frame and an overall support for a power generation system. In the method of claim 9, the plurality of supercapacitors are instructed by a central processing unit to perform a charge / discharge swing in order to make the best use of the electricity generated by the ORR. In the method of claim 5, the hydrothermal synthesis comprises a two-step heat treatment involving wood carbonization at 200-400 ° C. and in air, and carbonization at 600-900 ° C. without oxygen. In the novel method of claim 1, the low power direct current power comprises 3-10 volts and 3-10 amps using pulse width modulation (PWM).