Co-existing electronic chemical-electric energy CO2-emission-free fuel cell and preparation method and application thereof

Abstract

The invention relates to the technical field of fuel cells, and discloses an electronic chemical-electric energy symbiotic CO2-emission-free fuel cell and a preparation method and application thereof, and the CO2-emission-free fuel cell comprises a first Ti metal pole plate, a second Ti metal pole plate, a third Ti metal pole plate, a fourth Ti metal pole plate and a fifth Ti metal pole plate, the device comprises a first Ti metal pole plate, a first gold-plated current collector, a first graphite flow field plate with a snakelike flow channel, an anode electrode, an anion exchange membrane cathode, a cathode electrode, a second graphite flow field plate with a snakelike flow channel, a second gold-plated current collector and a second Ti metal pole plate, the first graphite flow field plate conveys anolyte through a peristaltic pump, and the second graphite flow field plate controls conveying of cathode fuel through a flow meter; the anode electrode material is Pt, Pt alloy and a compound, and the cathode electrode material is Pt / C or Pd / C; the anode electrolyte is composed of potassium hydroxide and methanol, and the cathode fuel is oxygen. The fuel cell disclosed by the invention realizes simultaneous continuous production of electronic chemicals and electric energy under mild conditions without consuming energy and supplying electric energy and without toxic raw materials.

Description

Technical Field

[0001] The present invention belongs to the technical field of fuel cells, and in particular relates to a CO2-free symbiotic electronic chemical-electricity 2 Emission fuel cell and preparation method and application thereof. Background Art

[0002] With the rapid development of the economy and society, electronic products are constantly developing towards lighter, thinner, faster and more portable directions. The size of electronic copper materials is getting narrower and narrower, which puts higher requirements on the corrosion resistance of electronic copper materials. The anti-corrosion protection of electronic copper materials is more important. Using electronic chemicals to surface treat electronic copper materials to achieve the effect of protection is the most feasible strategy. However, the synthesis method of traditional electronic chemicals is complex, the conditions are harsh, the energy consumption is high and the raw materials are toxic. Therefore, it is very urgent to develop a technology that can synthesize electronic chemicals under mild conditions, non-toxic raw materials and no energy consumption. The existing technology still needs to be improved and developed. Summary of the invention

[0003] In view of the above-mentioned deficiencies in the prior art, the object of the present invention is to provide a CO2-free 2 The emission fuel cell and its preparation method and application are aimed at solving the problems of complex synthesis process, toxic raw materials and high energy consumption of existing electronic chemical formate.

[0004] The technical solution of the present invention is as follows:

[0005] A symbiotic electrochemical - CO2-free electricity 2 exhaust fuel cell, wherein the CO 2 The discharge fuel cell comprises: a first Ti metal plate, a first gold-plated current collector, a first graphite flow field plate with a serpentine flow channel, an anode electrode, an anion exchange membrane cathode, a cathode electrode, a second graphite flow field plate with a serpentine flow channel, a second gold-plated current collector and a second Ti metal plate, which are stacked in sequence; the first graphite flow field plate transports the anode electrolyte through a peristaltic pump, and the second graphite flow field plate controls the transport of the cathode fuel through a flow meter; the anode electrode material is Pt, Pt alloy and composite, and the cathode electrode material is Pt / C or Pd / C; the anode electrolyte is composed of potassium hydroxide and methanol, and the cathode fuel is oxygen.

[0006] The symbiotic electrochemicals - CO2-free electricity 2 Discharging a fuel cell, wherein the concentration of potassium hydroxide is 0.5-5.0 mol / L and the concentration of methanol is 1-10 mol / L.

[0007] The symbiotic electrochemicals - CO2-free electricity 2Discharging the fuel cell, wherein the peristaltic pump has a flow rate of 10-50 rpm.

[0008] The symbiotic electrochemicals - CO2-free electricity 2 Exhausting the fuel cell, wherein the flow meter flow rate is 50-150 sccm.

[0009] The symbiotic electrochemicals - CO2-free electricity 2 Discharging a fuel cell, wherein the fuel cell is temperature controlled by a PID temperature controller, and the temperature control range is 40-80°C.

[0010] The symbiotic electrochemicals - CO2-free electricity 2 The fuel cell is discharged, wherein the anion exchange membrane is of the model FAA-3-20, FAA-3-50 or FAAM-20.

[0011] The symbiotic electrochemicals - CO2-free electricity 2 Discharging a fuel cell, wherein the purity of the oxygen is greater than or equal to 99.9%.

[0012] A symbiotic electrochemical - CO2-free electricity 2 A method for preparing a fuel cell for discharge, comprising the steps of:

[0013] The first Ti metal plate, the first gold-plated current collector, the first graphite flow field plate with a serpentine flow channel, the anode electrode, the anion exchange membrane cathode electrode, the second graphite flow field plate with a serpentine flow channel, the second gold-plated current collector and the second Ti metal plate are stacked and installed in sequence to obtain the CO2-free 2 Exhaust the fuel cell.

[0014] A symbiotic electrochemical - CO2-free electricity 2 emission fuel cell applications, where the CO 2 The exhaust fuel cell is used to produce the electronic chemical formate and export electrical energy.

[0015] Beneficial effect: The present invention provides a CO2-free symbiotic electronic chemical-electricity 2 Emission fuel cell and its preparation method and application, based on CO2-free 2 The direct methanol fuel cell achieves the continuous production of electronic chemicals and electricity without consuming energy and providing electricity with non-toxic raw materials and mild conditions. The formate electronic chemicals produced can be used to protect electronic copper materials such as copper RF antennas, copper conductive interconnects on printed circuit boards, and electromagnetic shielding copper materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1This is a schematic diagram of the direct methanol fuel cell model prepared by the present invention.

[0017] Figure 2 This is a discharge power density curve of the fuel cell tested by an electrochemical workstation in Example 1.

[0018] Figure 3 The Faraday efficiency of formate, a product of methanol oxidation at the anode of a fuel cell, was measured by ion chromatography.

[0019] Figure 4 The figure is a bar graph comparing the concentration of carbonate in the anode electrolyte of a fuel cell tested by ion chromatography before and after constant potential testing. DETAILED DESCRIPTION

[0020] The present invention provides a CO2-free symbiotic electronic chemical-electricity 2 Emission fuel cell and its preparation method and application, in order to make the purpose, technical solution and effect of the present invention clearer and more specific, the present invention is further described in detail below. It should be understood that the specific embodiments described here are only used to explain the present invention, and are not used to limit the present invention.

[0021] Direct methanol fuel cell is a technology that uses methanol obtained from renewable technology as fuel. It has the advantages of high energy density, easy storage and transportation, and high fuel solubility. Direct methanol fuel cell can not only realize external power output, but also the selective oxidation product formate of the anode methanol oxidation reaction is an important electronic chemical. It can be used as a protective agent in the corrosion protection of electronic copper materials of various sizes. The protective effect of formate has also been reported by researchers. More importantly, direct methanol fuel cell can realize CO2-free 2 The technology of symbiosis of electronic chemicals and electricity without emission can be carried out without consuming energy and providing electricity, with non-toxic raw materials and mild conditions. This technology is in line with the future development direction of the electronic chemical synthesis industry, and is conducive to achieving energy conservation and emission reduction in actual production, simplifying processes, improving production efficiency and reducing production costs.

[0022] Based on this, the present invention provides a CO2-free 2 Exhaust fuel cells, such as Figure 1 As shown, it includes a first Ti metal plate, a first gold-plated current collector, a first graphite flow field plate with a serpentine flow channel, an anode electrode 10, an anion exchange membrane cathode 20, a cathode electrode 30, a second graphite flow field plate with a serpentine flow channel, a second gold-plated current collector and a second Ti metal plate, wherein the first Ti metal plate, the first gold-plated current collector, and the first graphite flow field plate with a serpentine flow channel are stacked in sequence. Figure 1The first electrode 100 shown in FIG. 1 , the second graphite flow field plate with serpentine flow channel, the second gold-plated current collector and the second Ti metal electrode plate are formed as shown in FIG. Figure 1 In the second electrode 200 shown, the first graphite flow field plate transports the anode electrolyte through a peristaltic pump, and the second graphite flow field plate controls the transport of the cathode fuel through a flow meter; the anode electrode material is Pt, Pt alloy and composite, and the cathode electrode material is Pt / C or Pd / C; the anode electrolyte is composed of potassium hydroxide and methanol, and the cathode fuel is oxygen.

[0023] The fuel cell designed by the present invention can produce electronic chemical formate without consuming energy and supplying electricity, using non-toxic raw materials and under mild conditions. The formate electronic chemical produced by the anode of the fuel cell prepared by the present invention can be used for the protection of electronic conductive copper materials. The fuel cell provided by the present invention realizes a mild, safe and CO2-free process. 2 The symbiosis of electronic chemicals and electric energy under emission conditions can effectively promote the development of the synthesis field of electronic conductive copper protection chemicals.

[0024] The electronic chemicals symbiotically produced in the fuel cell provided by the present invention can be applied to the protection of electronic conductive copper materials. The formate generated by the oxidation reaction of methanol at the anode of the fuel cell serves as a corrosion protection agent for the copper material. After the protective agent is used on the surface of the copper material, the copper surface has corrosion resistance and is applied to electronic copper materials including but not limited to copper radio frequency antennas, copper conductive interconnects on printed circuit boards, and electromagnetic shielding copper materials.

[0025] The anode electrode of the present invention loses electrons to generate methanol oxidation reaction to generate formate electronic chemicals, and the cathode electrode obtains electrons to generate oxygen reduction reaction. The electrons in the external circuit are conducted from the anode to the cathode, and the current is conducted from the cathode to the anode to output electrical energy externally.

[0026] In some embodiments, the oxidation reaction occurring at the anode electrode is a methanol oxidation reaction, which is a reaction path in which methanol molecules lose electrons to generate formate, and methanol molecules do not undergo a complete oxidation reaction to generate CO. 2 , the reduction reaction occurring at the cathode electrode is an oxygen reduction reaction.

[0027] In some embodiments, the concentration of potassium hydroxide is 0.5-5.0 mol / L, and the concentration of methanol is 1-10 mol / L, but not limited thereto; the flow rate of the peristaltic pump is 10-50 rpm, and the flow rate of the flowmeter is 50-150 sccm, but not limited thereto.

[0028] In some embodiments, the fuel cell is temperature-controlled by a PID temperature controller, and the temperature control range is 40-80°C, but not limited to this. The methanol raw material used in this embodiment is green and non-toxic, the operating temperature of the fuel cell is lower than 80 degrees Celsius, the reaction conditions are mild, the fuel cell does not require electrical energy input, and can achieve spontaneous electrical energy output.

[0029] In some embodiments, the anion exchange membrane is of model FAA-3-20, FAA-3-50 or FAAM-20, but is not limited thereto.

[0030] In some embodiments, the purity of the oxygen is greater than or equal to 99.9%, but is not limited thereto.

[0031] In some embodiments, a CO2-free electrochemical-electrical energy source is also provided. 2 The preparation method of the emission fuel cell comprises the steps of: stacking and installing the first Ti metal plate, the first gold-plated current collector, the first graphite flow field plate with a serpentine flow channel, the anode electrode, the anion exchange membrane cathode electrode, the second graphite flow field plate with a serpentine flow channel, the second gold-plated current collector and the second Ti metal plate in sequence to obtain the CO2-free fuel cell. 2 Exhaust the fuel cell.

[0032] In some embodiments, a CO2-free electrochemical-electrical energy source is also provided. 2 emission fuel cell applications, where the CO 2 The exhaust fuel cell is used to produce the electronic chemical formate and export electrical energy.

[0033] The present invention will be further explained below by means of specific embodiments:

[0034] Example 1

[0035] A symbiotic electrochemical - CO2-free electricity 2The application of the discharge fuel cell is a direct methanol fuel cell of the present invention, which includes a first Ti metal plate stacked in sequence, a first gold-plated current collector, a first graphite flow field plate with a serpentine flow channel, an anode electrode, an anion exchange membrane cathode, a cathode electrode, a second graphite flow field plate with a serpentine flow channel, a second gold-plated current collector and a second Ti metal plate, wherein the anode electrode material is an electrode (Pt-CoOOH / NF) with platinum nanoparticles supported by CoOOH (cobalt oxyhydroxide) nanosheet arrays grown on the surface of a foam nickel substrate, the cathode electrode is a carbon paper-supported Pt / C catalyst, and the ion membrane is an anion exchange membrane of model FAA-3-20. The anode electrolyte is a mixed aqueous solution of 2mol / L potassium hydroxide and 2mol / L methanol, which is transported by a peristaltic pump at a flow rate of 20rpm. The cathode fuel transports oxygen at a flow rate of 100sccm through a flow meter, and the fuel cell is temperature-controlled by a PID thermostat, and the operating temperature is controlled at 80 degrees Celsius.

[0036] Figure 2 The discharge power density curve of the fuel cell of this embodiment tested by the electrochemical workstation shows that the peak current density of the fuel cell is 49.5 mW / cm 2 .

[0037] Figure 3 The Faraday efficiency of formate, a product of methanol oxidation at the anode of the fuel cell of this embodiment, is measured by ion chromatography, that is, the conversion rate of methanol to formate. It can be seen that the selectivity of formate is higher than 96%.

[0038] Figure 4 The concentration of carbonate in the anode electrolyte of the fuel cell of this embodiment before and after the constant potential test is shown by ion chromatography. It can be seen that the concentration of carbonate remains stable before and after the test without obvious increase, indicating that the anode methanol of the fuel cell is highly selectively oxidized to form formate, without excessive oxidation to form CO 2 This indicates that the direct methanol fuel cell prepared by the present invention can achieve CO 2 Co-production of formate electronic chemicals and electricity under emission conditions.

[0039] Example 2

[0040] A method for preparing a CO2-free fuel cell with symbiotic electronic chemicals and electric energy, wherein the fuel cell is a direct methanol fuel cell of the present invention, and comprises a first Ti metal plate stacked in sequence, a first gold-plated current collector, a first graphite flow field plate with a serpentine flow channel, an anode electrode, an anion exchange membrane cathode, a cathode electrode, a second graphite flow field plate with a serpentine flow channel, a second gold-plated current collector, and a second Ti metal plate, wherein the anode electrode material is a nickel mesh-supported Pt-Au catalyst (Pt-Au / NM), the cathode electrode is a carbon paper-supported Pt / C catalyst, and the ion membrane is a FAA-3-20 anion exchange membrane. The anode electrolyte is a 2mol / L potassium hydroxide and 2mol / L methanol mixed aqueous solution, which is transported by a peristaltic pump at a flow rate of 20rpm. The cathode fuel transports oxygen at a flow rate of 100sccm through a flow meter. The fuel cell is temperature-controlled by a PID thermostat, and the operating temperature is controlled at 80 degrees Celsius.

[0041] Example 3

[0042] A method for preparing a CO2-free fuel cell with symbiotic electronic chemicals and electric energy, wherein the fuel cell is a direct methanol fuel cell of the present invention, and comprises a first Ti metal plate stacked in sequence, a first gold-plated current collector, a first graphite flow field plate with a serpentine flow channel, an anode electrode, an anion exchange membrane cathode, a cathode electrode, a second graphite flow field plate with a serpentine flow channel, a second gold-plated current collector, and a second Ti metal plate, wherein the anode electrode material is an electrode (Pt-CoOOH / NF) with platinum nanoparticles supported by a CoOOH nanosheet array grown on the surface of a foam nickel substrate, the cathode electrode is a carbon paper-supported Pt / C catalyst, and the ion membrane is an anion exchange membrane of model FAA-3-50. The anode electrolyte is a mixed aqueous solution of 4 mol / L potassium hydroxide and 4 mol / L methanol, which is transported at a flow rate of 50 rpm by a peristaltic pump. The cathode fuel transports oxygen at a flow rate of 120 sccm through a flow meter. The fuel cell is temperature-controlled by a PID thermostat, and the operating temperature is controlled at 80 degrees Celsius.

[0043] Example 4

[0044] A method for preparing a CO2-free fuel cell with symbiotic electronic chemicals and electric energy, wherein the fuel cell is a direct methanol fuel cell of the present invention, and comprises a first Ti metal plate stacked in sequence, a first gold-plated current collector, a first graphite flow field plate with a serpentine flow channel, an anode electrode, an anion exchange membrane cathode, a cathode electrode, a second graphite flow field plate with a serpentine flow channel, a second gold-plated current collector, and a second Ti metal plate, wherein the anode electrode material is a nickel mesh-supported Pt-Au catalyst (Pt-Au / NM), the cathode electrode is a carbon paper-supported Pt / C catalyst, and the ion membrane is an anion exchange membrane of model FAA-3-50. The anode electrolyte is a mixed aqueous solution of 4 mol / L potassium hydroxide and 4 mol / L methanol, which is transported at a flow rate of 50 rpm by a peristaltic pump. The cathode fuel transports oxygen at a flow rate of 120 sccm through a flow meter. The fuel cell is temperature-controlled by a PID thermostat, and the operating temperature is controlled at 80 degrees Celsius.

[0045] Example 5

[0046] A method for preparing a CO2-free fuel cell with symbiotic electronic chemicals and electric energy, wherein the fuel cell is a direct methanol fuel cell of the present invention, and comprises a first Ti metal plate stacked in sequence, a first gold-plated current collector, a first graphite flow field plate with a serpentine flow channel, an anode electrode, an anion exchange membrane cathode, a cathode electrode, a second graphite flow field plate with a serpentine flow channel, a second gold-plated current collector, and a second Ti metal plate, wherein the anode electrode material is an electrode (Pt-CoOOH / NF) on the surface of a foam nickel substrate with platinum nanoparticles supported by a CoOOH nanosheet array, the cathode electrode is a carbon paper-supported Pd / C catalyst, and the ion membrane is an anion exchange membrane of model FAA-3-20. The anode electrolyte is a mixed aqueous solution of 2 mol / L potassium hydroxide and 2 mol / L methanol, which is transported by a peristaltic pump at a flow rate of 20 rpm. The cathode fuel transports oxygen at a flow rate of 100 sccm through a flow meter. The fuel cell is temperature-controlled by a PID thermostat, and the operating temperature is controlled at 80 degrees Celsius.

[0047] Example 6

[0048] A method for preparing a CO2-free fuel cell with symbiotic electronic chemicals and electric energy, wherein the fuel cell is a direct methanol fuel cell of the present invention, which comprises a first Ti metal plate stacked in sequence, a first gold-plated current collector, a first graphite flow field plate with a serpentine flow channel, an anode electrode, an anion exchange membrane cathode, a cathode electrode, a second graphite flow field plate with a serpentine flow channel, a second gold-plated current collector, and a second Ti metal plate, wherein the anode electrode material is a nickel mesh loaded Pt-Au catalyst (Pt-Au / NM), the cathode electrode is a carbon paper supported Pd / C catalyst, and the ion membrane is an anion exchange membrane of model FAA-3-20. The anode electrolyte is a mixed aqueous solution of 2 mol / L potassium hydroxide and 2 mol / L methanol, which is transported by a peristaltic pump at a flow rate of 20 rpm. The cathode fuel transports oxygen at a flow rate of 100 sccm through a flow meter. The fuel cell is temperature-controlled by a PID thermostat, and the operating temperature is controlled at 80 degrees Celsius.

[0049] It should be understood that the application of the present invention is not limited to the above examples. For ordinary technicians in this field, improvements or changes can be made based on the above description. All these improvements and changes should fall within the scope of protection of the claims attached to the present invention.

Claims

1. A CO2-free fuel cell that produces electronic chemicals and electricity, characterized in that: The CO2 emission-free fuel cell includes: a first Ti metal plate, a first gold-plated current collector, a first graphite flow field plate with a serpentine flow channel, an anode electrode, an anion exchange membrane cathode, a cathode electrode, a second graphite flow field plate with a serpentine flow channel, a second gold-plated current collector and a second Ti metal plate, which are stacked in sequence; the first graphite flow field plate transports the anode electrolyte through a peristaltic pump, and the second graphite flow field plate controls the transportation of the cathode fuel through a flow meter; the anode electrode material is Pt, Pt alloy and composite, and the cathode electrode material is Pt / C or Pd / C; the anode electrolyte is composed of potassium hydroxide and methanol, and the cathode fuel is oxygen.

2. The CO2-free fuel cell for symbiotic electronic chemicals and electrical energy according to claim 1, characterized in that: The concentration of potassium hydroxide is 0.5-5.0 mol / L, and the concentration of methanol is 1-10 mol / L.

3. The CO2-free fuel cell for symbiotic electronic chemicals and electrical energy according to claim 1, characterized in that: The peristaltic pump flow rate is 10-50 rpm.

4. The CO2-free fuel cell for symbiotic electronic chemicals and electrical energy according to claim 1, characterized in that: The flow meter flow rate is 50-150 sccm.

5. The CO2-free fuel cell for symbiotic electronic chemicals and electrical energy according to claim 1, characterized in that: The fuel cell is temperature controlled by a PID temperature controller, and the temperature control range is 40-80°C.

6. The CO2-free fuel cell for symbiotic electronic chemicals and electrical energy according to claim 1, characterized in that: The model of the anion exchange membrane is FAA-3-20, FAA-3-50 or FAAM-20.

7. The CO2-free fuel cell for symbiotic electronic chemicals and electrical energy according to claim 1, characterized in that: The purity of the oxygen is greater than or equal to 99.9%.

8. A method for preparing a CO2-free fuel cell that symbiotically produces electronic chemicals and electric energy as claimed in any one of claims 1 to 7, characterized in that: Includes steps: The first Ti metal plate, the first gold-plated current collector, the first graphite flow field plate with a serpentine flow channel, the anode electrode, the anion exchange membrane cathode electrode, the second graphite flow field plate with a serpentine flow channel, the second gold-plated current collector and the second Ti metal plate are stacked and installed in sequence to obtain the CO2 emission-free fuel cell.

9. An application of a CO2-free fuel cell for symbiotic electronic chemicals and electric energy as claimed in any one of claims 1 to 7, characterized in that: The CO2 emission-free fuel cell is used to produce electronic chemical formate and output electrical energy.

Images