Electrode unit and an electrode system comprising the same

Abstract

An electrode unit and an electrode system comprising the same, wherein the electrode unit has an electrode catalyst layer consisting of a material comprising electrically conductive diamond particles; the electrode system having the above electrode unit includes an anode and a cathode, and the anode and/or cathode employs the electrode unit, the electrode system further including a PEM film; the anode and the cathode are respectively disposed on two sides of the PEM film. The use of electrically conductive diamond particles as the electrode catalyst layer does not require the use of base materials such as metals or semiconductors or ceramics, and machining problem and the problem relating to the difference in thermal expansion coefficient do not exist, thereby significantly reducing the manufacturing cost.

Claims

1. An electrode unit, comprising an electrode catalytic layer, a gas diffusion layer, and a porous electrode; wherein the electrode catalytic layer is composed of electrically conductive diamond particles; each of the electrically conductive diamond particles has a particle diameter of 4 nm to 1 mm, and the catalytic layer does not need to use a base material such as metal or semiconductor or ceramic; the gas diffusion layer is made of a porous material or an electrically conductive fiber material; the gas diffusion layer is sandwiched between the electrode catalyst layer and the porous electrode.

2. (canceled)

3. The electrode unit of claim 1, wherein the electrically conductive diamond particles are integral electrically conductive diamond particles or electrically conductive diamond particles of composite supported structures.

4. The electrode unit of claim 3, wherein the electrically conductive diamond particles are diamond particles that are entirely electrically conductive, or each of them being a composite diamond particle formed by a non-electrically conductive diamond core coated with an electrically conductive diamond coating; the composite supported structure of each of the electrically conductive diamond particles comprises carbon powder being a supporting core coated with electrically conductive diamond.

5. (canceled)

6. (canceled)

7. The electrode unit of claim 1, wherein the porous material is a corrosion-resistant porous metal and/or porous graphite, and the electrically conductive fiber material is an electrically conductive carbon fiber paper and/or a conductive carbon fiber cloth.

8. The electrode unit of claim 7, wherein the porous metal is more than one of porous titanium, porous nickel, porous platinum, porous gold, porous copper or porous aluminum.

9. An electrode system, comprising an anode and a cathode, wherein the anode and/or the cathode employing the electrode unit according to claim 1.

10. The electrode system of claim 9, wherein the electrode system further comprises a PEM film, the anode and the cathode are respectively disposed on two sides of the PEM film; the PEM film is a perfluorosulfonic acid ion polymer film or a non-perfluorosulfonic acid ion polymer film.

11. The electrode system of claim 10, wherein the perfluorosulfonic acid ion polymer is a Nafion series membrane, a Fumion series membrane, an Aciplex series membrane, a Flemion series membrane, a C membrane, a BAM membrane or a XUS-B204 membrane; the non-perfluorosulfonic acid ion polymer is a polytrifluorostyrenesulfonic acid film, a BAM3G film, a polytetrafluoroethylene-hexafluoropropylene film, a polyphenylenesulfonate siloxane or an aromatic high molecular hydrocarbon.

12. The electrode system of claim 9, wherein the anode comprises electrically conductive diamond particles; the cathode comprises either electrically conductive diamond particles or metal particles.

13. (canceled)

14. The electrode system of claim 12, wherein the metal particles are more than one of graphite, carbon, titanium, platinum, gold, titanium alloy, nickel, palladium, platinum-rhodium alloy or stainless steel.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0036] FIG. 1 is a concept diagram of electrolytic ozone.

[0037] FIG. 2 shows the electrically conductive diamond particles having composite supported structures according to embodiment 2 of the present invention.

[0038] FIG. 3 is an electrolytic unit including an electrode catalytic layer of electrically conductive diamond particles according to embodiment 9 of the present invention.

[0039] FIG. 4 is an electrolytic unit including an electrode catalytic layer of electrically conductive diamond particles according to embodiment 10 of the present invention.

[0040] FIG. 5 is an electrolytic unit including an electrode catalytic layer of electrically conductive diamond particles according to embodiment 11 of the present invention.

[0041] FIG. 6 is a primary battery including an electrode catalytic layer of electrically conductive diamond particles according to embodiment 12 of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

[0042] The present invention is further described in detail below with reference to some embodiments. However, the present invention should not be considered limited by the embodiments. Unless otherwise specified, the technical means disclosed in the embodiments are ordinary means known by a person skilled in this field of art. Unless otherwise specified, the reagents, methods and apparatus used by the present invention are known to a person skilled in this field of art.

[0043] The PEM membrane used in the embodiments is a perfluorosulfonic acid ionomer membrane or a non-perfluorosulfonic acid ionomer membrane. The perfluorosulfonic acid ionic polymer may be a Nafion series membrane, a Fumion series membrane, an Aciplex series membrane, a Flemion series membrane, a C membrane, a BAM membrane or a XUS-B204 membrane; the non-perfluorosulfonic acid ionic polymer may be a polytrifluorostyrenesulfonic acid film, a BAM3G film, a polytetrafluoroethylene-hexafluoropropylene film, a polyphenylenesulfonate siloxane or an aromatic high molecular hydrocarbon.

Embodiment 1: Preparation of Electrically Conductive Diamond Particles

[0044] Under high temperature and high pressure (above 500° C., more than 10 GPa), catalytic agent/graphite/boron source are made into electrically conductive diamond granules through a hydraulic press; the granules are then crushed by physical means to obtain small electrically conductive diamond particles; or the small electrically conductive diamond particles are directly made using high temperature and high pressure (above 500° C., more than 10 GPa) preparation method; the obtained diamond particles have a diameter of 4 nm to 1 mm.

Embodiment 2: Preparation of Electrically Conductive Diamond Particles

[0045] Deposit CVD electrically conductive diamond coating on diamond particles obtained from conventional high temperature and high pressure preparation method by hot wire chemical vapor deposition; in this process, common lib diamond particles each having a diameter of 4 nm-1 mm and which are not electrically conductive are selected to be first washed by hydrogen peroxide, nitric acid, pure water, or alcohol, and then being dried; next, grow the diamond particles in a hot wire chemical vapor deposition equipment, wherein the growth conditions are as follows: base temperature 500˜800° C., hot wire temperature 180˜2400° C., air pressure 1˜5 kPa, hydrogen gas being introduced 100˜1000 SCCM, methane 1˜20 SCCM, borane 1˜20 SCCM; grow the diamond particles for more than 10 minutes to form an electrically conductive diamond coating on the diamond particles, wherein a thickness of the coating layer is 4 nm˜10 μm; accordingly, diamond particles each having a composite supported structure and an electric conductive surface as illustrated in FIG. 2 is obtained.

Embodiment 3: Preparation of an Electrode System Having the Electrically Conductive Diamond Particles as an Anode

[0046] 1. Pretreating PEM membrane (DuPont Nafion 117 membrane): (1) Boiling the PEM membrane for 30 minutes in HNO.sub.3—H.sub.2O (volume ratio of 1:1) or in H.sub.2O.sub.2 with a mass concentration of 5%-10% to remove impurities on the membrane and organic matters on the surface of the membrane; (2) boiling again in 0.5 mol of H.sub.2SO.sub.4 for 30 minutes to remove metal impurities; (3) boiling the PEM membrane in boiling deionized water for 1 h to remove excess acid and to introduce a renewable amount of water to the membrane; (4) storing the pretreated PEM membrane in the deionized water for later use.

[0047] 2. Making an anode having electrically conductive diamond particles on one side of the pretreated PEM membrane: mixing the electrically conductive diamond particles obtained in embodiment 1, deionized water, ethanol, glycerin and Nafion solution in a weight ratio of 0.5:1:1:0.5:0.4 evenly to obtain a solution A by means of ultrasonic vibration; taking out the pretreated PEM membrane and placing the pretreated PEM membrane on a clean hollow quartz panel; then filling the solution A into a pneumatic spray gun and spraying the solution A on the PEM membrane for more than 10 seconds, wherein a working pressure of the spray gun is 0.1˜0.2 bar; then placing the quartz panel into an oven and baking the quartz panel at 80° C. for 30 minutes; repeating the above procedures until an anode layer of electrically conductive diamond particles is formed, wherein a tested mass density thereof is 2-4 mg/cm.sup.2.

[0048] 3. Making a metal cathode on another side of the pretreated PEM membrane: mixing pure titanium powder (diameter being 0.5˜2 μm), deionized water, ethanol, glycerin and Nafion solution in a weight ratio of 0.2:1:1:0.5:0.4 evenly to obtain a solution B by means of ultrasonic vibration; placing the PEM membrane on the hollow quartz panel with the anode facing down towards the hollow quartz panel; then filling the solution B into the pneumatic spray gun and spraying the solution B on the PEM membrane for more than 10 seconds, wherein a working pressure of the spray gun is 0.1˜0.2 bar; then placing the quartz panel in the oven and baking the quartz panel at 80° C. for 30 minutes; repeating the above procedures until a cathode layer having metal particles is formed, wherein a tested mass density thereof is 2-4 mg/cm.sup.2.

[0049] 4. Using two pieces of carbon paper (Japan Toray® carbon paper TGP-H-060) as a gas diffusion layer, sandwiching the PEM membrane having the cathode and anode between the two pieces of carbon paper and heat pressing at 135° C. for 1 minute to form an operable electrode system having a surface area of 20 cm.sup.2.

[0050] 5. Mounting porous titanium and its back electrode respectively; mounting a plastic cavity, and eventually obtaining an electrolytic unit.

Embodiment 4: Preparation of an Electrode System Having the Electrically Conductive Diamond Particles as an Anode/a Cathode

[0051] 1. Pretreating PEM membrane (DuPont Nafion 117 membrane available in the market): (1) Boiling the PEM membrane for 30 minutes in HNO.sub.3—H.sub.2O (volume ratio of 1:1) or in H.sub.2O.sub.2 with a mass concentration of 5%-10% to remove impurities on the membrane and organic matters on the surface of the membrane; (2) boiling again in 0.5 mol of H.sub.2SO.sub.4 for 30 minutes to remove metal impurities; (3) boiling the PEM membrane in boiling deionized water for 1 h to remove excess acid and to introduce a renewable amount of water to the membrane; (4) storing the pretreated PEM membrane in the deionized water for later use.

[0052] 2. Making an anode having electrically conductive diamond particles on one side of the pretreated PEM membrane: mixing the electrically conductive diamond particles obtained in embodiment 1, deionized water, ethanol, glycerin and Nafion solution in a weight ratio of 0.5:1:1:0.5:0.4 evenly to obtain a solution C by means of ultrasonic vibration; taking out the pretreated PEM membrane and placing the pretreated PEM membrane on a clean hollow quartz panel; then filling the solution C into a pneumatic spray gun and spraying the solution C on the PEM membrane for more than 10 seconds, wherein a working pressure of the spray gun is 0.1˜0.2 bar; then placing the quartz panel into an oven and baking the quartz panel at 80° C. for 30 minutes; repeating the above procedures until an anode layer of electrically conductive diamond particles is formed, wherein a tested mass density thereof is 2-4 mg/cm.sup.2.

[0053] 3. Repeating the above steps to prepare a cathode having electrically conductive diamond particles on another side of the pretreated PEM membrane.

[0054] 4. Using two pieces of carbon paper (Japan Toray® carbon paper TGP-H-060) as a gas diffusion layer, sandwiching the PEM membrane having the cathode and anode between the two pieces of carbon paper and heat pressing at 135° C. for 1 minute to form an operable electrode system having a surface area of 20 cm.sup.2.

[0055] 5. Mounting porous titanium and its back electrode respectively; mounting a plastic cavity, and eventually obtaining an electrolytic unit.

Comparative Example 1: Preparation of a Conventional Silicon-Based Electrically Conductive Diamond Film Electrolytic Unit

[0056] Depositing a CVD electrically conductive diamond coating on a 10 cm*10 cm*0.075 cm (100) single crystal silicon wafer by hot wire chemical vapor deposition; mechanically grinding a surface of the silicon wafer by diamond particles having a diameter of 1 to 3 μm, and then washing with acetone/alcohol and deionized water, each for 5 minutes respectively, and drying with nitrogen; after that, placing the silicon wafer on a growth platform of a CVD furnace, wherein the growth conditions are as follows: base temperature is 500˜800° C., hot wire temperature is 180˜2400° C., air pressure is 1˜5 kPa, and introduced with 100˜1000 SCCM hydrogen, 1˜20 SCCM methane and 1˜20 SCCM borane; growing for more than 120 minutes to form an electrically conductive diamond film with a thickness of 1˜4 μm.

[0057] Taking out the above specimen, punching holes on the specimen by a laser cutter, wherein the holes have hole diameter being 0.1-2 mm, distanced from one another by 0.5-3 mm, and having a hole density of around 20%-60% for air and water permeability; cutting the porous silicon wafer deposited with the electrically conductive diamond film prepared according to the present embodiment by laser into a 4×5 cm rectangular piece as an anode, and using a stainless steel mesh of the same size as a cathode; placing the PEM membrane between the anode and the cathode, and finally clamping this sandwiched structure, and connecting this sandwiched structure with electrical poles and placing the sandwiched structure in a reaction chamber to form an electrolytic ozone water unit.

Embodiment 5: Comparative Experiment of Electrolyzing Deionized Water

[0058] Introducing the electrolytic units prepared in embodiment 3, embodiment 4 and Comparative Example 1 into 3 L/min of deionized water respectively, and applying a constant voltage of DC 14 V between the cathode and the anode, wherein the current is 4-10 A. The water containing hydrogen output from the cathode and the water containing ozone output from the anode merge again at the water outlet to form ozone water having a certain ozone concentration. In embodiment 3, the cathode and the anode are periodically exchanged every 1 minute, and the time interval between an exchange is 0 s. All electrolytic units are configured to run continuously for 20 minutes and then continue to run after a 2-minute pause. The continuous running time and performance of different electrolytic units are shown in Table 1 below. As can be seen from Table 1, the ozone electrolytic unit made of electrically conductive diamond particles has an extremely long service life. Dissecting the silicon wafer of comparative example 1 and it is found that the diamond film on the silicon wafer has signs of detachment due to heat generated during operation of the electrode system, and the difference in thermal expansion coefficient between diamond and silicon (silicon is 2.6×10.sup.−6 K.sup.−1, diamond is 1.0×10.sup.−6 K.sup.−1) After the long period of operation, the diamond film is gradually peeled off from the silicon wafer. Embodiment 3 and embodiment 4 are prepared by the method of embodiment 1, that is, the electrically conductive diamond film is directly grown on undoped (non-electrically conductive) diamond particles, and there is no difference in thermal expansion coefficient between the two, and there is no thermal expansion and contraction problem.

TABLE-US-00001 TABLE 1 Continuous running time and performance of different electrolytic units when electrolyzing deionized water Comparative Embodiment 3 Embodiment 4 example 1 Voltage (V) DC14 DC ± 14 DC14 exchange periodically Steady current (Å) 9.4 9.5 7.9 Ozone concentration 2.0 2.1 1.2 in water (ppm) Time when current is >1000 >1000 575 reduced by 15% (h) Service life (h) >1000 >1000 575

Embodiment 6: Comparative Experiment of Electrolyzing Municipal Tap Water

[0059] Introducing the electrolytic units prepared in embodiment 3, embodiment 4 and Comparative Example 1 into 3 L/min of unfiltered municipal tap water respectively (Source of the municipal tap water: Huangpu district, Guangzhou, Guangdong, China), and applying a constant voltage of DC 14 V between the cathode and the anode, wherein the current is 4-12 A. The water containing hydrogen output from the cathode and the water containing ozone output from the anode merge again at the water outlet to form ozone water having a certain ozone concentration. In embodiment 3, the cathode and the anode are periodically exchanged every 1 minute, and the time interval between an exchange is 0 s. All electrolytic units are configured to run continuously for 20 minutes and then continue to run after a 2-minute pause. The continuous running time and performance of different electrolytic units are shown in Table 2 below. It can be seen from Table 2 that the ozone electrolytic unit which uses the electrically conductive diamond particles to make the two electrodes still has an extremely long service life in the case where municipal tap water is the source. Dissecting comparative example 1 and it is found that the holes punched on the silicon wafer that serves as the anode are substantially clogged by white calcified substances, and the diamond film is also covered with calcified substances, and has signs of falling off. No calcified substance is found in the cathode. The causes of these findings are the heat generated during operation of the electrode system, causing the calcified substances in the water to be deposited in the anode, and difference in thermal expansion coefficient between diamond and silicon (silicon: 2.6×10.sup.−6 K.sup.−1, diamond: 1.0×10.sup.−6K.sup.−1) that causes the diamond film to gradually peel off from the silicon wafer after a long period of operation. The anode of embodiment 2 is also deposited with calcified substances that result in a shorter operating life. In Example 3, due to periodic exchange between the cathode and the anode, it was found that there is almost no deposition of calcified substances after 1000 hours of operation, and the overall structure remains intact. A conventional electrolyzed ozone water unit usually uses lead dioxide as a catalyst to make an anode and platinum as the catalyst to make a cathode, therefore, the anode and cathode cannot be exchanged, and the problem of calcification still exists, so it is impossible to use municipal tap water as water source to make ozone water, thereby greatly increasing the operation cost. Also, due to instability of lead dioxide, not only the service life is short, but also toxic lead and lead compounds are continuously released in the water. By contrast, the present invention has a higher utility value.

TABLE-US-00002 TABLE 2 Continuous running time and performance of different electrolytic units when electrolyzing municipal tap water Comparative Embodiment 3 Embodiment 4 example 1 Voltage (V) DC14 DC ± 14 DC14 exchange periodically Steady current (Å) 11.2 11.7 8.3 Ozone concentration 1.5 1.5 1.0 in water (ppm) Time when current is 260 >1000 235 reduced by 15% (h) Service life (h) 260 >1000 235

Embodiment 7: Preparation of an Electrode System Having the Electrically Conductive Diamond Particles as an Anode

[0060] 1. Pretreating PEM membrane (DuPont Nafion 117 membrane): (1) Boiling the PEM membrane for 30 minutes in HNO.sub.3—H.sub.2O (volume ratio of 1:1) or in H.sub.2O.sub.2 with a mass concentration of 5%-10% to remove impurities on the membrane and organic matters on the surface of the membrane; (2) boiling again in 0.5 mol of H.sub.2SO.sub.4 for 30 minutes to remove metal impurities; (3) boiling the PEM membrane in boiling deionized water for 1 h to remove excess acid and to introduce a renewable amount of water to the membrane; (4) storing the pretreated PEM membrane in the deionized water for later use.

[0061] 2. Making an anode having electrically conductive diamond particles on one side of the pretreated PEM membrane: mixing the electrically conductive diamond particles obtained in embodiment 1, deionized water, ethanol, glycerin and Nafion solution in a weight ratio of 0.5:1:1:0.5:0.4 evenly to obtain a solution A by means of ultrasonic vibration; taking out the pretreated PEM membrane and placing the pretreated PEM membrane on a clean hollow quartz panel; then filling the solution A into a pneumatic spray gun and spraying the solution A on the PEM membrane for more than 10 seconds, wherein a working pressure of the spray gun is 0.1˜0.2 bar; then placing the quartz panel into an oven and baking the quartz panel at 80° C. for 30 minutes; repeating the above procedures until an anode layer of electrically conductive diamond particles is formed, wherein a tested mass density thereof is 2-4 mg/cm.sup.2.

[0062] 3. Making a metal cathode on another side of the pretreated PEM membrane: mixing carbon powder (diameter being 2-3 μm), deionized water, ethanol, glycerin and Nafion solution in a weight ratio of 0.2:1:1:0.5:0.4 evenly to obtain a solution B by means of ultrasonic vibration; placing the PEM membrane on the hollow quartz panel with the anode facing down towards the hollow quartz panel; then filling the solution B into the pneumatic spray gun and spraying the solution B on the PEM membrane for more than 10 seconds, wherein a working pressure of the spray gun is 0.1˜0.2 bar; then placing the quartz panel in the oven and baking the quartz panel at 80° C. for 30 minutes; repeating the above procedures until a cathode layer having metal particles is formed, wherein a tested mass density thereof is 2-4 mg/cm.sup.2.

[0063] 4. Using two pieces of carbon paper (Japan Toray® carbon paper TGP-H-060) as a gas diffusion layer, sandwiching the PEM membrane having the cathode and anode between the two pieces of carbon paper and heat pressing at 135° C. for 1 minute to form an operable electrode system having a super large surface area of 400 cm.sup.2.

[0064] 5. Mounting porous titanium and its back electrode respectively; mounting a plastic cavity, and eventually obtaining an electrolytic unit.

[0065] As shown above, the present invention uses electrically conductive diamond particles as the electrode catalytic layer without using base materials such as metals or semiconductors or ceramics, therefore the problems of machining and the difference in thermal expansion coefficient do not exist. Also, the present invention overcomes the limitation of the size of the deposition chamber in the prior art CVD diamond preparation technology to achieve preparation of a large surface area electrode by simply disposing the diamond particles.

Embodiment 8: Preparation of an Electrode System Having the Electrically Conductive Diamond Particles as an Anode

[0066] 1. Pretreating PEM membrane (DuPont Nafion 117 membrane): (1) Boiling the PEM membrane for 30 minutes in HNO.sub.3—H.sub.2O (volume ratio of 1:1) or in H.sub.2O.sub.2 with a mass concentration of 5%-10% to remove impurities on the membrane and organic matters on the surface of the membrane; (2) boiling again in 0.5 mol of H.sub.2SO.sub.4 for 30 minutes to remove metal impurities; (3) boiling the PEM membrane in boiling deionized water for 1 h to remove excess acid and to introduce a renewable amount of water to the membrane; (4) storing the pretreated PEM membrane in the deionized water for later use.

[0067] 2. Making an anode having electrically conductive diamond particles on one side of the pretreated PEM membrane: mixing the electrically conductive diamond particles obtained in embodiment 1, deionized water, ethanol, glycerin and Nafion solution in a weight ratio of 0.5:1:1:0.5:0.4 evenly to obtain a solution A by means of ultrasonic vibration; taking out the pretreated PEM membrane and placing the pretreated PEM membrane on a clean hollow quartz panel; then filling the solution A into a pneumatic spray gun and spraying the solution A on the PEM membrane for more than 10 seconds, wherein a working pressure of the spray gun is 0.1˜0.2 bar; then placing the quartz panel into an oven and baking the quartz panel at 80° C. for 30 minutes; repeating the above procedures until an anode layer of electrically conductive diamond particles is formed, wherein a tested mass density thereof is 2-4 mg/cm.sup.2.

[0068] 3. Making a metal cathode on another side of the pretreated PEM membrane: mixing carbon powder (diameter being 2-3 μm), deionized water, ethanol, glycerin and Nafion solution in a weight ratio of 0.2:1:1:0.5:0.4 evenly to obtain a solution B by means of ultrasonic vibration; placing the PEM membrane on the hollow quartz panel with the anode facing down towards the hollow quartz panel; then filling the solution B into the pneumatic spray gun and spraying the solution B on the PEM membrane for more than 10 seconds, wherein a working pressure of the spray gun is 0.1˜0.2 bar; then placing the quartz panel in the oven and baking the quartz panel at 80° C. for 30 minutes; repeating the above procedures until a cathode layer having metal particles is formed, wherein a tested mass density thereof is 2-4 mg/cm.sup.2.

[0069] 4. Using two pieces of porous titanium panels (pore diameter being 4-25 μm) as a gas diffusion layer, sandwiching the PEM membrane having the cathode and anode between the two pieces of porous titanium panels and heat pressing at 150° C. for 1 minute to form an operable electrode system having a surface area of 40 cm.sup.2.

[0070] 5. Mounting a metal back electrode respectively; mounting a plastic cavity, and eventually obtaining an electrolytic unit.

Embodiment 9

[0071] An electrolytic unit is shown in FIG. 3. The electrolytic unit comprises an anode, a PEM membrane composed of a perfluorosulfonic acid ionic polymer (a Nafion membrane manufactured by DuPont), and a cathode; the anode and the cathode are disposed on the PEM membrane, each of the anode and the cathode comprises sequentially a back electrode (corrosion-resistant metal such as titanium alloy, pure titanium, nickel, palladium, platinum or platinum-ruthenium alloy, etc.), porous electrode (porous graphite), gas diffusion layer (carbon fiber paper or carbon fiber cloth) and the electrode catalytic layer of embodiment 3; the back electrode is provided with a water path and a gas path for electrical conductivity.

[0072] FIG. 3 is an electrolytic unit including the electrode catalytic layer of electrically conductive diamond particles according to the present embodiment, wherein, 1 is an anode, 2 is a cathode, 3 is a porous electrode, 4 is a gas diffusion layer, 5 is an anode catalytic layer (electrically conductive diamond particles), 6 is a cathode catalytic layer (metal particles), and 7 is a PEM membrane. When the anode and the cathode are introduced into pure water, ozone water is produced at the anode, and water containing hydrogen is produced at the cathode.

Embodiment 10

[0073] An electrolytic unit is shown in FIG. 4. The electrolytic unit comprises an anode, a PEM membrane and a cathode; the anode and the cathode are disposed on the PEM membrane, each of the anode and the cathode comprises sequentially a back electrode (corrosion-resistant metal such as titanium alloy, pure titanium, nickel, palladium, platinum or platinum-ruthenium alloy, etc.), porous electrode (More than one kind of porous metals such as porous titanium, porous nickel, porous platinum, porous gold, porous copper or porous aluminum), gas diffusion layer (porous material or fibrous material) and the electrode catalytic layer of embodiment 4; the back electrode is provided with a water path and a gas path.

[0074] FIG. 4 is an electrolytic unit including the electrode catalytic layer of electrically conductive diamond particles according to the present embodiment, wherein, 1 is an anode/cathode, 2 is an cathode/anode, 3 is a porous electrode, 4 is a gas diffusion layer, 5 is an anode/cathode catalytic layer (electrically conductive diamond particles), and 6 is a PEM membrane. When the anode and the cathode are introduced into pure water, ozone water is produced at the anode, and water containing hydrogen is produced at the cathode.

Embodiment 11

[0075] An electrolytic unit is shown in FIG. 5. The electrolytic unit comprises an anode, a PEM membrane and a cathode; the anode and the cathode are disposed on the PEM membrane, each of the anode and the cathode comprises sequentially a back electrode (corrosion-resistant metal), porous electrode (More than one kind of porous metals such as porous titanium, porous nickel, porous platinum, porous gold, porous copper or porous aluminum), gas diffusion layer (porous material or fibrous material) and the electrode catalytic layer of embodiment 7; the back electrode is provided with a water path and a gas path.

[0076] FIG. 5 is an electrolytic unit including the electrode catalytic layer of electrically conductive diamond particles according to the present embodiment. When only the cathode is introduced into pure water, ozone gas is produced at the anode, and water containing hydrogen is produced at the cathode.

Embodiment 12

[0077] A primary battery as shown in FIG. 6, is a reverse process of the electrolysis unit of the above described embodiments 9 to 11. As an ozone generator, the electrically conductive diamond particles serve as an anode of an electrochemical ozone generator, and metals are used as a cathode of the electrochemical ozone generator. The metals may be in the form of meshes, panels or particles, or composite structures of metal powder and supported-type carbon powder (embodiment 3 or embodiment 8 has detailed the manufacturing method). When H.sub.2 and O.sub.2 reach the anode and cathode of the battery respectively through the gas guiding channels, they pass through the diffusion layers and the electrically conductive diamond particle catalytic layers on the electrodes and reach the proton exchange membrane, and on an anode side of the membrane, hydrogen is dissociated into H.sup.+ and e.sup.− under the action of the anode catalyst, H.sup.+ is transferred in the proton exchange membrane in the form of hydrated protons, and finally reaches the cathode to achieve proton conduction. The transfer of H.sup.+ causes the negatively charged electrons to accumulate at the anode, which then becomes a negatively charged terminal (negative electrode). At the same time, O.sub.2 of the cathode combines with the H.sup.+ from the anode under the action of the catalyst, causing the cathode to become a positively charged terminal (positive electrode) As a result, a voltage is formed between the negatively charged terminal of the anode and the positively charged terminal of the cathode. When the two terminals are connected by an external load circuit, electrons flow from the anode to the cathode through a loop to form a primary battery, thereby generating electricity.

[0078] The embodiments described above are the preferred embodiments of the present invention. However, the present invention should not be limited to the above embodiments. Any changes, modifications, replacements, combinations and simplifications without deviating from the principle and essence of the present invention should be considered equivalent alternatives that should also fall within the scope of protection of the present invention.