CN113481539A - Efficient and low-cost proton exchange membrane water electrolysis hydrogen production control system and control method consistent with renewable energy sources - Google Patents
Efficient and low-cost proton exchange membrane water electrolysis hydrogen production control system and control method consistent with renewable energy sources Download PDFInfo
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Abstract
The invention provides a high-efficiency and low-cost proton exchange membrane water electrolysis hydrogen production control method and a control system which are consistent with renewable energy sources, aiming at the characteristics of oxygen evolution catalysts with low iridium or without iridium, controlling the input voltage in the actual operation process of the PEM electrolysis unit with low iridium or no iridium oxygen evolution catalyst, setting the upper limit of the voltage to ensure that the input voltage is lower than the oxidation dissolution potential of the anode low iridium or no iridium oxygen evolution catalyst, namely, the stable voltage of the oxygen evolution catalyst with low iridium or without iridium can be ensured, so as to ensure that the catalyst is not rapidly deactivated by over oxidation and dissolution of the oxygen evolution catalyst with low iridium or without iridium, therefore, the low-iridium or iridium-free oxygen evolution catalyst is used for responding to the power supply response of low-fluctuation stable operation, the high-iridium oxygen evolution catalyst can effectively reduce the cost of the electrolysis system, and the comprehensive energy conversion efficiency of the electrolysis unit is improved.
Description
Technical Field
The invention relates to the technical field of hydrogen production by water electrolysis through a Proton Exchange Membrane (PEM), in particular to a high-efficiency and low-cost hydrogen production control system and a control method by water electrolysis through a proton exchange membrane, which are consistent with renewable energy sources.
Background
Hydrogen economy is a future energy economy structure in the 70's of the 20 th century that has been proposed as a medium for hydrogen (storage, transportation and conversion). At present, the Chinese energy structure is gradually turning from the traditional fossil energy to the diversified pattern based on the renewable energy. Hydrogen is a clean energy source and does not produce contaminants during use. Renewable energy sources such as solar energy, wind energy, water potential energy and the like are converted into electric energy, and hydrogen is produced by electrolyzing water by using an electrolytic cell, so that the method is an effective mode for sustainable energy utilization. The national development and reform committee combines with the national energy agency to issue a text, supports exploring surplus electric power of renewable energy sources to convert the surplus electric power into heat energy, cold energy and hydrogen energy, and realizes the multi-way near-to-high-efficiency utilization of the renewable energy sources.
The PEM water electrolysis hydrogen production technology is a new generation of high-efficiency electrolysis technology, and the technology relies on a membrane electrode complex consisting of a cathode and an anode and a polymer electrolyte membrane and combines an electrolytic cell shell to form an electrochemical electrolysis system, and water molecules are decomposed into oxygen and H at an anode+Under the action of an electric field, H+Passes to the cathode where hydrogen is generated. Solid polymerThe electrolyte (SPE) technology is beneficial to large-scale electrolytic hydrogen production by multi-cell series connection, and the electrolytic cell has no liquid electrolyte, is safer and more reliable than an alkaline electrolytic cell, and has the advantages of good chemical stability, proton conductivity, gas separability and the like. Therefore, the SPE electrolysis technology has the advantages of high electrolysis efficiency, zero spacing, small internal resistance, simple and convenient gas separation process, excellent hydrogen quality, high safety and the like.
The water electrolysis equipment is very suitable for centralized, distributed and field production of hydrogen due to the modular property of the equipment. Meanwhile, the PEM water electrolysis hydrogen production has the advantages of high efficiency, excellent hydrogen quality, safety, reliability, adaptability to wide power range fluctuation and the like, and is particularly suitable for being combined with renewable energy sources such as photovoltaic energy, wind energy and the like. According to the prediction of the Chinese alliance of innovation strategies of hydrogen energy and fuel cell industry, 70% of hydrogen comes from renewable energy sources in 2050, and hydrogen production by water electrolysis of the renewable energy sources becomes mainstream in the future. Therefore, the PEM water electrolysis hydrogen production technology is one of the key boosting technologies for realizing '2060 carbon neutralization'.
However, renewable energy sources have the problems of intermittency and instability, so that higher requirements are put on an anode oxygen evolution catalyst which is a key material in the water electrolysis hydrogen production technology, namely the anode oxygen evolution catalyst is required to be capable of being in a wider current density interval (0.1-2A/cm)2) Has high efficiency and stable performance. The only thing that can now satisfy both of these conditions is a high iridium content>30 percent) of iridium-based catalyst, especially under the condition of high current density (more than or equal to 1A/cm)2) Even more so. However, metal iridium is one of the rarest elements in the earth crust, and as the demand of industrial production for Ir element increases, the prices of Ir-based oxide and Ir-based catalyst also increase, which also causes the cost of the electrolytic water hydrogen production electrolytic cell to increase greatly, and becomes a bottleneck limiting the popularization and application of the technology. And the adoption of the low-cost iridium-free non-iridium catalyst galvanic pile reduces the cost and consumes the peak value electric energy of renewable energy sources, thereby being a feasible scheme.
Disclosure of Invention
The invention aims to solve the technical problems in the prior art and provides a control system and a control method for hydrogen production by water electrolysis through a proton exchange membrane, which are consistent with renewable energy sources and have high efficiency and low cost.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the invention provides a high-efficiency and low-cost proton exchange membrane water electrolysis hydrogen production control method which is consistent with renewable energy sources, and the control method is suitable for an electrolysis galvanic pile consisting of two groups of PEM electrolysis units; wherein:
the anode oxygen evolution catalyst of a group of PEM electrolysis units is a high-iridium-content oxygen evolution catalyst, namely the iridium content is more than or equal to 30 percent;
the anode oxygen evolution catalyst of the other group of PEM electrolysis units adopts a low-iridium or iridium-free oxygen evolution catalyst, namely the content of iridium is more than or equal to 0 and less than 30 percent;
the control method comprises the following steps:
step 1, setting an upper voltage limit to enable the input voltage at two ends of an electrolytic cell stack to be lower than the oxidation dissolution potential of an iridium-low anode or iridium-free oxygen evolution catalyst;
step 2, monitoring the output energy state index of the renewable energy source: the electrolytic voltage, current density or input electric energy at two ends of the electrolytic cell stack reach the percentage of the designed power of the system;
step 3, when the electrolytic voltage at two ends of the electrolytic cell stack is lower than the upper limit of the protection voltage set in the step 1 or the electrolytic current density is less than 0.5A/cm2Or when the external input electric energy is less than x% (x is 0-60) of the rated power of the electrolysis galvanic pile, starting a PEM electrolysis galvanic pile unit of a low-iridium or iridium-free oxygen evolution catalyst system to work, and electrolyzing water to produce hydrogen; otherwise, starting the PEM electrolysis galvanic pile unit of the high iridium content oxygen evolution catalyst system to work, and electrolyzing water to produce hydrogen.
In the technical scheme, the oxygen evolution catalyst with low iridium content or without iridium element is a single atom Ir doped MnO2A catalyst, wherein Ir has an atomic ratio of 0.87%, when the upper voltage limit in step 1 is 1.75V.
In the technical scheme, the oxygen evolution catalyst with high iridium content is iridium oxide, doped iridium oxide, iridium-containing alloy or iridium-containing high-load catalyst.
In the technical scheme, the low-iridium or iridium-free oxygen evolution catalyst is Ti-doped RuO2Catalyst, the upper voltage limit in step 1 at this time was 1.5V.
In the technical scheme, the oxygen evolution catalyst with low iridium content or without iridium element is MnO2Catalyst, the upper voltage limit in step 1 at this time was 1.5V.
The invention also provides a high-efficiency and low-cost proton exchange membrane water electrolysis hydrogen production control system which is consistent with the renewable energy source, comprising: the system comprises a renewable energy power supply system, a hydrogen production comprehensive control unit, electrolytic hydrogen production equipment and a monitoring unit, wherein the renewable energy power supply system, the hydrogen production comprehensive control unit and the electrolytic hydrogen production equipment are sequentially connected;
the electrolytic hydrogen production equipment is an electrolytic electric thruster consisting of two groups of PEM electrolytic units, wherein:
the anode oxygen evolution catalyst of a group of PEM electrolysis units is a high-iridium-content oxygen evolution catalyst, namely the iridium content is more than or equal to 30 percent;
the anode oxygen evolution catalyst of the other group of PEM electrolysis units adopts a low-iridium or iridium-free oxygen evolution catalyst, namely the content of iridium is more than or equal to 0 and less than 30 percent;
setting the upper limit of voltage to make the input voltage at two ends of the electrolysis pile lower than the oxidation dissolution potential of the iridium-free oxygen evolution catalyst; the monitoring unit monitors the output energy state index of the renewable energy power supply system: the electrolytic voltage, current density or input electric energy at two ends of the electrolytic cell stack reach the percentage of the designed power of the system; then feeding back the monitored energy state index data to the hydrogen production comprehensive control unit, and accurately switching the operating states of the two electrolysis units by the hydrogen production comprehensive control unit according to the data; when the electrolytic voltage at two ends of the electrolytic pile is lower than the set upper limit of the protective voltage or the electrolytic current density is less than 0.5A/cm2Or when the external input electric energy is less than x% (x is 0-60) of the rated power of the electrolysis galvanic pile, starting a PEM electrolysis galvanic pile unit of a low-iridium or iridium-free oxygen evolution catalyst system to work, and electrolyzing water to prepareHydrogen; otherwise, starting the PEM electrolysis galvanic pile unit of the high iridium content oxygen evolution catalyst system to work, and electrolyzing water to produce hydrogen.
In the above technical solution, the monitoring unit includes current and voltage sensors.
In the above technical solution, the integrated hydrogen production control unit includes: the power supply comprises a voltage monitoring unit for monitoring voltage, a current monitoring unit for monitoring current and an input power monitoring unit for monitoring power.
In the technical scheme, the oxygen evolution catalyst with high iridium content is iridium oxide, doped iridium oxide, iridium-containing alloy or iridium-containing high-load catalyst.
In the technical scheme, the oxygen evolution catalyst with low iridium content or without iridium element is a single atom Ir doped MnO2A catalyst, wherein the atomic ratio of Ir is 0.87%, at which the upper voltage limit is 1.75V; or the low-iridium or iridium-free oxygen evolution catalyst is Ti-doped RuO2Catalyst, at which the upper voltage limit is 1.5V; or the oxygen evolution catalyst with low iridium or no iridium element is MnO2Catalyst, the upper voltage limit is 1.5V.
The invention has the beneficial effects that:
the invention provides a high-efficiency and low-cost proton exchange membrane electrolytic water hydrogen production control method and a control system which are consistent with renewable energy sources, aiming at the characteristics of low-iridium or iridium-free oxygen evolution catalysts, the input voltage is controlled in the actual operation process of a PEM (proton exchange membrane) electrolysis unit with a low-iridium or iridium-free oxygen evolution catalyst, the upper limit of the voltage is set to enable the input voltage to be lower than the oxidation dissolution potential of the low-iridium or iridium-free oxygen evolution catalyst, namely, the stable voltage of the low-iridium or iridium-free oxygen evolution catalyst can be ensured, the catalyst can be rapidly inactivated due to the fact that the low-iridium or iridium-free oxygen evolution catalyst is not excessively oxidized and dissolved, and therefore the energy conversion efficiency of the electrolysis unit at the low input voltage can be effectively improved by using the control system or the control method of the high-activity catalysts.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is a schematic diagram of a high-efficiency and low-cost proton exchange membrane water electrolysis hydrogen production control system consistent with renewable energy sources of the present invention.
Fig. 2 is a schematic diagram of the operation of the control unit in the control system of the present invention.
Detailed Description
The invention idea of the invention is as follows: PEM electrolyzers offer increased flexibility and reactivity in operation. PEM electrolyzed water technology provides a wider operating range and shorter response times. The obviously improved operation flexibility can improve the overall economic benefit of electrolytic hydrogen production, especially can be well combined with renewable energy sources for power generation, thereby obtaining benefits from a plurality of power markets, because the electric energy of the new energy sources is output at a wave trough or a low current density, namely in a low fluctuation state, at the moment, the electrolytic water hydrogen production system can adopt a low iridium or iridium-free oxygen evolution catalyst to respond to a power supply which stably runs at low fluctuation, thereby realizing efficient hydrogen production at low current density, and a large-scale electrolysis unit can be designed according to the actual output energy of the wave trough or the current density output state to absorb a large amount of low fluctuation energy, thereby improving the electrolytic hydrogen production efficiency of the whole electrolysis system.
The anode catalysts of the electrolysis galvanic pile of the existing PEM water electrolysis hydrogen production system all adopt Ir-based catalysts, but the dependence of the system on the high Ir-loaded catalyst is strong due to the large current density working condition of the PEM system; the non-iridium-based catalyst can greatly reduce the cost of water electrolysis catalysis, but has certain difference in performance compared with Ir-based catalyst in the efficiency of hydrogen production by electrolysis.
The current Ir content in the crust is about 0.0006ppm, even lower than Pt. The extremely low reserves lead to the high price of Ir, which reaches about $ 220/g, and the price factor limits the wide application of PEM water electrolysis hydrogen production technology. In contrast, Ru, which is relatively abundant, is relatively inexpensive, about one tenth of Ir, and non-noble metals Co, Mn, Cu, Mo, W, etc., have similarly higher reserves and lower prices. Therefore, the designed oxygen evolution catalyst with low iridium or without iridium has a remarkable promotion effect on the reduction of the use cost, the popularization and the application of the PEM water electrolysis hydrogen production technology.
Low loading of iridium (<30%) catalyst or non-iridium based, e.g., ruthenium based catalyst, non-noble metal catalyst, etc., at lower current density<0.5A/cm2) The catalyst can be used as an anode Oxygen Evolution Reaction (OER) catalytic material, can simultaneously meet the two conditions of stability and high efficiency, and can be used for inactivating the catalyst due to the fact that metal elements in the catalyst are not stable and dissolved and run off when the current density is high, and finally the electrolytic cell stack is completely failed.
The biggest problem faced by oxygen evolution catalysts with low or no iridium is poor stability at high current densities. According to the pH-potential diagram (Pourbaix phase diagram) of the material, the oxidation dissolution potential of Ir and its oxide at pH 0 is as high as 1.9V vs. RHE, which is one of the most corrosion-resistant elements in the periodic table of elements, so that it shows better stability in an acidic OER environment. Dilution of Ir or avoidance of Ir requires introduction of a second component (e.g., Ru, Co, Mo, etc.) having a lower oxidative dissolution potential, necessarily resulting in a decrease in overall catalyst stability. However, even the second component having a lower oxidative dissolution potential tends to be stable when the applied potential is controlled. E.g. MnO2The components are oxidized to soluble MnO at a potential higher than 1.75V vs. RHE4-Thus MnO is added when the applied potential reaches 1.8V vs. RHE2Rapid dissolution, sharp drop in stability, almost complete deactivation within 100 h, MnO when control potential is lower than 1.75V vs. RHE2The components are able to maintain stability for up to 8000h without dissolution.
Therefore, aiming at the characteristics of the low-iridium or iridium-free oxygen evolution catalyst, the input voltage is controlled in the actual operation process of the PEM electrolysis unit with the low-iridium or iridium-free oxygen evolution catalyst, and the upper limit of the voltage is set to ensure that the input voltage is lower than the oxidation dissolution potential of the anode low-iridium or iridium-free oxygen evolution catalyst, so that the stable voltage of the low-iridium or iridium-free oxygen evolution catalyst can be ensured, the catalyst can not be rapidly deactivated due to excessive oxidation and dissolution of the low-iridium or iridium-free oxygen evolution catalyst, and the use of the high-activity catalyst can effectively improve the energy conversion efficiency of the electrolysis unit at low input voltage.
The invention provides that according to the characteristics of intermittency and instability of renewable energy sources (wind energy, solar energy, tidal energy and the like), a designed system adopts two groups of electrolysis devices to be matched with each other to realize the efficient hydrogen production by applying renewable energy source power:
1) one group is that hydrogen-making galvanic pile adopting oxygen-separating catalyst with high iridium content (iridium oxide, doped iridium oxide or its solid solution, simple substance iridium, iridium-containing alloy, iridium-containing high-load catalyst) responds to power supply with high fluctuation;
2) and the other group is a hydrogen production galvanic pile adopting the oxygen evolution catalyst with low iridium or without iridium element to respond to the power fluctuation of renewable energy sources and realize the power supply response of stable operation.
Another key point of the strategy provided by the invention is that the current or voltage sensor is used for monitoring the output energy state indexes of the new energy (such as the electrolytic voltage, the current density and the percentage of the input electric energy at two ends of the galvanic pile to reach the design power of the system) and then the input state data of the new energy is fed back to the control system, and the control system accurately switches the operation states of the two electrolysis units according to the data, so that the high-efficiency operation of the whole electrolysis system is ensured.
Therefore, the core of the strategy provided by the invention is that the electrolytic hydrogen production system can adopt a PEM electrolysis unit with low iridium or no iridium oxygen evolution catalyst to respond to a power supply with low fluctuation and smooth operation, namely when the external input electric energy is less than x percent of the design load of the electrolysis system or the electrolysis voltage at the two ends of the electrolysis pile is lower than the set upper limit of the protection voltage or the electrolysis current density is less than 0.5A/cm2The value of x is in direct proportion to the scale of the part, two factors of the scale of the new energy coupled with the hydrogen production system and the manufacturing cost can be comprehensively considered, and the value of x is preferably 0-60; when the renewable energy output is in a high fluctuation state of wave crest, the renewable energy output is responded by the oxygen evolution catalyst with high iridium content, and then the system is quickly switched to the PEM electrolysis unit of the oxygen evolution catalyst with high iridium content to consume the energy of the renewable energy in the high fluctuation state, namely, the high-efficiency hydrogen production under high current densityThe system can be operated at a capacity higher than the rated load (more than 100%, up to 200%) for a short time.
The strategy provided by the invention can effectively improve the capacity and storage of the PEM system, greatly reduce the cost and improve the energy conversion efficiency.
In view of the above, the control method and the control system for hydrogen production by water electrolysis with proton exchange membrane, which are provided by the invention, are efficient, stable and low in cost, and are more suitable for coupling with renewable energy sources, and are characterized in that:
1. according to the characteristics of intermittency and instability of renewable energy sources (wind energy, solar energy, tidal energy and the like), the invention adopts two groups of electrolysis devices to be matched with each other to realize the high-efficiency hydrogen production by applying the electricity of the renewable energy sources: 1) One group is that hydrogen-making galvanic pile adopting oxygen-separating catalyst with high iridium content (iridium oxide, doped iridium oxide or its solid solution, simple substance iridium, iridium-containing alloy, iridium-containing high-load catalyst) responds to power supply with high fluctuation; 2) and the other group is a hydrogen production pile which adopts low-iridium or does not contain iridium element oxygen evolution catalyst to realize high-efficiency hydrogen production under low current density, and the hydrogen production pile can respond to the power fluctuation of renewable energy sources and realize power supply response of stable operation. The system can operate under the capacity higher than the rated load (more than 100 percent and as high as 200 percent) in a short time, and the electrolytic hydrogen production efficiency of the whole electrolytic system is improved.
2. The operating states of the two electrolysis units are regulated and controlled by monitoring input voltage or input current density;
3. the input voltage at two electrolytic ends of the electrolytic galvanic pile is lower than the oxidation dissolution potential of the iridium-low or iridium-free oxygen evolution catalyst by setting the upper limit of the voltage, so that the stable voltage of the iridium-low or iridium-free oxygen evolution catalyst can be ensured;
4. the use of noble metal Ir is reduced or avoided, the oxygen evolution catalyst with low iridium or without iridium has extremely strong cost advantage, and the commercial cost of the PEM system electrolyte hydrogen production technology can be effectively reduced by using the oxygen evolution catalyst as an anode catalyst.
The following describes in detail a control system for producing hydrogen by electrolyzing water with a proton exchange membrane, which is consistent with renewable energy sources, and has high efficiency and low cost, with reference to fig. 1 and 2, and comprises: the system comprises a renewable energy power supply system, a hydrogen production comprehensive control unit and an electrolysis electric thruster which are sequentially connected, and further comprises a monitoring unit, wherein the monitoring unit is respectively connected with the hydrogen production comprehensive control unit and the electrolysis electric thruster;
the renewable energy power supply system is a wind power plant power supply system;
the electrolytic hydrogen production equipment is an electrolytic electric thruster consisting of two groups of PEM electrolytic units, wherein: the anode oxygen evolution catalyst of a group of PEM electrolysis units is a high-iridium-content oxygen evolution catalyst, namely the iridium content is more than or equal to 30 percent; the anode oxygen evolution catalyst of the other group of PEM electrolysis units adopts a low-iridium or iridium-free oxygen evolution catalyst, namely the content of iridium is more than or equal to 0 and less than 30 percent;
the monitoring unit comprises current and voltage sensors;
the hydrogen production integrated control unit comprises: the power monitoring device comprises a voltage monitoring unit for monitoring voltage, a current monitoring unit for monitoring current and an input power monitoring unit for monitoring power;
setting the upper limit of voltage to make the input voltage at two ends of the electrolysis pile lower than the oxidation dissolution potential of the iridium-free oxygen evolution catalyst; the monitoring unit monitors the output energy state index of the renewable energy power supply system: the electrolytic voltage, current density or input electric energy at two ends of the electrolytic cell stack reach the percentage of the designed power of the system; then feeding back the monitored energy state index data to the hydrogen production comprehensive control unit, and accurately switching the operating states of the two electrolysis units by the hydrogen production comprehensive control unit according to the data; when the electrolytic voltage at two ends of the electrolytic pile is lower than the set upper limit of the protective voltage or the electrolytic current density is less than 0.5A/cm2Or when the external input electric energy is less than x% (x is 0-60) of the rated power of the electrolysis galvanic pile, starting a PEM electrolysis galvanic pile unit of a low-iridium or iridium-free oxygen evolution catalyst system to work, electrolyzing water to produce hydrogen, and realizing power supply response of stable operation; otherwise, starting a PEM electrolysis galvanic pile unit of the high-iridium-content oxygen evolution catalyst system to work, electrolyzing water to produce hydrogen, and responding to high-fluctuation power supply response.
The invention provides a high-efficiency and low-cost proton exchange membrane water electrolysis hydrogen production control method which is suitable for the control system and is consistent with renewable energy sources, and the method comprises the following steps:
step 1, setting an upper voltage limit to enable the input voltage at two ends of an electrolytic cell stack to be lower than the oxidation dissolution potential of an iridium-low anode or iridium-free oxygen evolution catalyst;
step 2, monitoring the state index of the renewable energy output energy through a current or voltage sensor: the electrolytic voltage, current density or input electric energy at two ends of the electrolytic cell stack reach the percentage of the designed power of the system;
step 3, when the electrolytic voltage at two ends of the electrolytic cell stack is lower than the upper limit of the protection voltage set in the step 1 or the electrolytic current density is less than 0.5A/cm2Or when the external input electric energy is less than x% (x is 0-60) of the rated power of the electrolysis galvanic pile, starting a PEM electrolysis galvanic pile unit of a low-iridium or iridium-free oxygen evolution catalyst system to work, electrolyzing water to produce hydrogen, and realizing power supply response of stable operation; otherwise, starting a PEM electrolysis galvanic pile unit of the high-iridium-content oxygen evolution catalyst system to work, electrolyzing water to produce hydrogen, and responding to high-fluctuation power supply response.
The high iridium content oxygen evolution catalysts of examples 1-3 below are all pure Ir based catalysts.
Example 1: monodisperse Ir-MnO2As PEMMWEs anode catalysts operating at low voltages
MnO2The corrosion dissolution potential of the alloy is 1.75V vs. RHE, and the single-atom Ir doped MnO is designed by using the alloy as a substrate2Catalyst (Ir-MnO)2) Wherein the atomic ratio of Ir is 0.87%. The catalyst is used as an OER catalyst in an acid environment and is added at 10mA cm-2The current density can be stably operated for more than 600 h. With Ir-MnO2As the PEMWs anode catalytic material, an electrolytic water tank is assembled. Setting the system protection voltage as a single-chip electrolysis voltage of 1.75V, and when the single-chip input voltage is more than 1.75V, operating a PEM electrolysis galvanic pile unit of a high iridium content oxygen evolution catalyst system to electrolyze and produce hydrogen; when the monolithic input voltage is less than 1.75V, the monodisperse Ir-MnO2The oxygen evolution catalyst system PEM electrolysis pile unit operates to electrolyze hydrogen.
Example 2: ti doped RuO2As PEMMWEs anode catalysts operating at low voltages
RuO2The corrosion dissolution potential of the titanium oxide is 1.5V vs. RHE, and Ti-doped modification is carried out on the titanium oxide to obtain Ti-doped RuO with high activity at low potential2Material (Ti-RuO)2) Current density at 1.43V vs. RHE potential exceeds 100mA cm-2. The catalyst is used as an OER catalyst in an acid environment and is added at 10mA cm-2The current density can be stably operated for more than 30 h. With Ti-RuO2As the PEMWs anode catalytic material, an electrolytic water tank is assembled. Setting the system protection voltage as a single-chip electrolysis voltage of 1.5V, and when the single-chip input voltage is more than 1.5V, operating a PEM electrolysis galvanic pile unit of a high iridium content oxygen evolution catalyst system to electrolyze and produce hydrogen; when the monolithic input voltage is less than 1.5V, the Ti is doped with RuO2The oxygen evolution catalyst system PEM electrolysis pile unit operates to electrolyze hydrogen.
Example 3: MnO2As PEMMWEs anode catalysts operating at low voltages
MnO2The corrosion dissolution potential of (1.75V vs. RHE) was directly used as an OER catalyst in an acidic environment at 10mA cm-2The stable operation can be carried out for more than 8000h under the current density. In MnO2As the PEMWs anode catalytic material, an electrolytic water tank is assembled. Setting the system protection voltage as a single-chip electrolysis voltage of 1.75V, and when the single-chip input voltage is more than 1.75V, operating a PEM electrolysis galvanic pile unit of a high iridium content oxygen evolution catalyst system to electrolyze and produce hydrogen; MnO when monolithic input voltage is less than 1.75V2The oxygen evolution catalyst system PEM electrolysis pile unit operates to electrolyze hydrogen.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. A control method for hydrogen production by water electrolysis through a proton exchange membrane with high efficiency and low cost, which is consistent with renewable energy sources, is characterized in that the control method is suitable for an electrolysis galvanic pile consisting of two groups of PEM electrolysis units; wherein:
the anode oxygen evolution catalyst of a group of PEM electrolysis units is a high-iridium-content oxygen evolution catalyst, namely the iridium content is more than or equal to 30 percent;
the anode oxygen evolution catalyst of the other group of PEM electrolysis units adopts a low-iridium or iridium-free oxygen evolution catalyst, namely the content of iridium is more than or equal to 0 and less than 30 percent;
the control method comprises the following steps:
step 1, setting an upper voltage limit to enable the input voltage at two ends of an electrolytic cell stack to be lower than the oxidation dissolution potential of an iridium-low anode or iridium-free oxygen evolution catalyst;
step 2, monitoring the output energy state index of the renewable energy source: the electrolytic voltage, current density or input electric energy at two ends of the electrolytic cell stack reach the percentage of the designed power of the system;
step 3, when the electrolytic voltage at two ends of the electrolytic cell stack is lower than the upper limit of the protection voltage set in the step 1 or the electrolytic current density is less than 0.5A/cm2Or when the external input electric energy is less than 0-60% of the rated power of the electrolysis galvanic pile, starting a PEM electrolysis galvanic pile unit with low iridium or no iridium element oxygen evolution catalyst system to work, and electrolyzing water to produce hydrogen; otherwise, starting the PEM electrolysis galvanic pile unit of the high iridium content oxygen evolution catalyst system to work, and electrolyzing water to produce hydrogen.
2. The control method of claim 1, wherein the low iridium or iridium-free oxygen evolution catalyst is a single atom Ir doped MnO2A catalyst, wherein Ir has an atomic ratio of 0.87%, when the upper voltage limit in step 1 is 1.75V.
3. The control method according to claim 1, characterized in that the high iridium content oxygen evolution catalyst is iridium oxide, doped iridium oxide, an iridium containing alloy or an iridium containing highly supported catalyst.
4. The control method according to claim 1, characterized in that the low iridium or iridium-free oxygen evolution catalyst is Ti doped RuO2Catalyst, the upper voltage limit in step 1 at this time was 1.5V.
5. The control method of claim 1, wherein the low iridium or iridium-free oxygen evolution catalyst is MnO2Catalyst, the upper voltage limit in step 1 at this time was 1.5V.
6. A control system for producing hydrogen by electrolyzing water with a proton exchange membrane, which is consistent with renewable energy sources and has high efficiency and low cost, is characterized by comprising: the system comprises a renewable energy power supply system, a hydrogen production comprehensive control unit, electrolytic hydrogen production equipment and a monitoring unit, wherein the renewable energy power supply system, the hydrogen production comprehensive control unit and the electrolytic hydrogen production equipment are sequentially connected;
the electrolytic hydrogen production equipment is an electrolytic electric thruster consisting of two groups of PEM electrolytic units, wherein:
the anode oxygen evolution catalyst of a group of PEM electrolysis units is a high-iridium-content oxygen evolution catalyst, namely the iridium content is more than or equal to 30 percent;
the anode oxygen evolution catalyst of the other group of PEM electrolysis units adopts a low-iridium or iridium-free oxygen evolution catalyst, namely the content of iridium is more than or equal to 0 and less than 30 percent;
setting the upper limit of voltage to make the input voltage at two ends of the electrolysis pile lower than the oxidation dissolution potential of the iridium-free oxygen evolution catalyst; the monitoring unit monitors the output energy state index of the renewable energy power supply system: the electrolytic voltage, current density or input electric energy at two ends of the electrolytic cell stack reach the percentage of the designed power of the system; then feeding back the monitored energy state index data to the hydrogen production comprehensive control unit, and accurately switching the operating states of the two electrolysis units by the hydrogen production comprehensive control unit according to the data; when the electrolytic voltage at two ends of the electrolytic pile is lower than the set upper limit of the protective voltage or the electrolytic current density is less than 0.5A/cm2Or the external input electric energy is less than 0 of the rated power of the electrolytic cell stackWhen the concentration is 60 percent, starting a PEM electrolysis galvanic pile unit with low iridium or no iridium element oxygen evolution catalyst system to work, and electrolyzing water to produce hydrogen; otherwise, starting the PEM electrolysis galvanic pile unit of the high iridium content oxygen evolution catalyst system to work, and electrolyzing water to produce hydrogen.
7. The control system of claim 6, wherein the monitoring unit comprises current and voltage sensors.
8. The control system of claim 6, wherein the integrated hydrogen production control unit comprises: the power supply comprises a voltage monitoring unit for monitoring voltage, a current monitoring unit for monitoring current and an input power monitoring unit for monitoring power.
9. The control system of claim 6, wherein the high iridium content oxygen evolution catalyst is iridium oxide, doped iridium oxide, an iridium containing alloy, or an iridium containing highly supported catalyst.
10. The control system of claim 6, wherein the low iridium or iridium-free oxygen evolution catalyst is a single atom Ir doped MnO2A catalyst, wherein the atomic ratio of Ir is 0.87%, at which the upper voltage limit is 1.75V; or the low-iridium or iridium-free oxygen evolution catalyst is Ti-doped RuO2Catalyst, at which the upper voltage limit is 1.5V; or the oxygen evolution catalyst with low iridium or no iridium element is MnO2Catalyst, the upper voltage limit is 1.5V.
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| WO2021098172A1 (en) * | 2019-11-19 | 2021-05-27 | 阳光电源股份有限公司 | New energy composite hydrogen production system and control method therefor |
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| US4289591A (en) * | 1980-05-02 | 1981-09-15 | General Electric Company | Oxygen evolution with improved Mn stabilized catalyst |
| CN101565832A (en) * | 2008-04-25 | 2009-10-28 | 清华大学 | Water electrolysis hydrogen production system for solar battery |
| US20140363351A1 (en) * | 2011-12-28 | 2014-12-11 | Hitachi, Ltd. | Renewable energy conversion and storage equipment |
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