CN113481539B - High-efficiency low-cost proton exchange membrane water electrolysis hydrogen production control system and control method consistent with renewable energy source - Google Patents

High-efficiency low-cost proton exchange membrane water electrolysis hydrogen production control system and control method consistent with renewable energy source Download PDF

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CN113481539B
CN113481539B CN202110766704.XA CN202110766704A CN113481539B CN 113481539 B CN113481539 B CN 113481539B CN 202110766704 A CN202110766704 A CN 202110766704A CN 113481539 B CN113481539 B CN 113481539B
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iridium
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oxygen evolution
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邢巍
梁亮
刘长鹏
葛君杰
金钊
李晨阳
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Suzhou Longtai New Energy Technology Co ltd
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Abstract

The invention provides a high-efficiency and low-cost proton exchange membrane electrolyzed 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 PEM (proton exchange membrane) electrolysis units of the low iridium or iridium-free oxygen evolution catalysts, the upper voltage limit is set to enable the input voltage to be lower than the oxidation dissolution potential of the anode low iridium or iridium-free oxygen evolution catalysts, so that the stable voltage of the low iridium or iridium-free oxygen evolution catalysts can be ensured, the low iridium or iridium-free oxygen evolution catalysts cannot be excessively oxidized and dissolved, the catalysts can be quickly deactivated, the low iridium or iridium-free oxygen evolution catalysts are used for responding to the power supply response of low fluctuation stable operation, and the high iridium-content oxygen evolution catalysts can effectively reduce the cost of the electrolysis system and improve the comprehensive energy conversion efficiency of the electrolysis units.

Description

High-efficiency low-cost proton exchange membrane water electrolysis hydrogen production control system and control method consistent with renewable energy source
Technical Field
The invention relates to the technical field of Proton Exchange Membrane (PEM) water electrolysis hydrogen production, in particular to a high-efficiency and low-cost proton exchange membrane water electrolysis hydrogen production control system and a control method consistent with renewable energy sources.
Background
Hydrogen economy is a future energy economy structure mediated by hydrogen (storage, transportation and conversion) proposed in the 70 s of the 20 th century. At present, the China energy structure is gradually changed from the traditional fossil energy to the multi-element structure mainly comprising renewable energy. Hydrogen is a clean energy source and does not produce contaminants during application. Renewable energy sources such as solar energy, wind energy, potential energy of water and the like are converted into electric energy, and water is electrolyzed by an electrolytic cell to produce hydrogen, so that the method is an effective mode for sustainable energy utilization. The national development and reform committee and the national energy bureau are combined to develop a sentence, so that the exploration of the surplus power of renewable energy sources to be converted into heat energy, cold energy and hydrogen energy is supported, and the renewable energy sources are utilized in multiple ways nearby and efficiently.
The technology for producing hydrogen by water electrolysis of PEM is a new generation high-efficiency electrolysis technology, which relies on a membrane electrode complex composed of a cathode and an anode and a polymer electrolyte membrane, and combines an electrolytic cell shell to form an electrochemical electrolysis system, wherein water molecules are decomposed into oxygen and H at an anode + Under the action of electric field, H + Passes to the cathode where hydrogen is generated. The Solid Polymer Electrolyte (SPE) technology is beneficial to large-scale electrolytic hydrogen production by multi-cell serial connection, and the electrolytic tank has no liquid electrolyte, is safer and more reliable than an alkaline electrolytic tank, and has the advantages of good chemical stability, proton conductivity, gas separation and the like. Therefore, the SPE electrolysis technology has the advantages of high electrolysis efficiency, zero spacing, small internal resistance, simple gas separation process, excellent hydrogen quality, high safety and the like.
The water electrolysis equipment is very suitable for centralized, distributed and on-site production of hydrogen due to the modularized property. 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 used in combination with renewable energy sources such as photovoltaics, wind energy and the like. According to the national hydrogen energy and fuel cell industry innovation strategy alliance prediction, 70% hydrogen is derived from renewable energy by 2050, and it can be seen that renewable energy water electrolysis hydrogen production will become the mainstream in the future. Thus, PEM electrolyzed water hydrogen production technology is one of the key booster technologies to achieve "2060 carbon neutralization".
However, renewable energy sources have the problems of intermittence and instability, so that higher requirements are put forward on an anode oxygen-evolving catalyst which is a key material in the technology of producing hydrogen by electrolyzing water, namely, the anode oxygen-evolving catalyst is required to be capable of generating oxygen in a wider current density range (0.1-2A/cm) 2 ) Has high efficiency and stable performance. At present, the high iridium content can meet the two conditions simultaneously>30%) of iridium-based catalysts, in particular under high current density conditions (. Gtoreq.1A/cm) 2 ) And more particularly, to a method for manufacturing a semiconductor device. However, the iridium metal is one of the rarest elements in the earth crust, and as the demand of industrial production for Ir element is continuously increased, the prices of Ir-based oxides and Ir-based catalysts are continuously increased, and the cost of the electrolytic pile for producing hydrogen by water electrolysis is greatly increased, so that the iridium metal becomes a bottleneck for limiting the popularization and application of the technology. The low-cost low-iridium and non-iridium catalyst galvanic pile is adopted to reduce the cost and consume the renewable energy peak electric energy, so that the method is a feasible scheme.
Disclosure of Invention
The invention aims to solve the technical problems in the prior art and provides a high-efficiency and low-cost proton exchange membrane water electrolysis hydrogen production control system and a control method which are consistent with renewable energy sources.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the invention provides a high-efficiency low-cost proton exchange membrane water electrolysis hydrogen production control method consistent with renewable energy sources, which is applicable to an electrolysis cell stack consisting of two groups of PEM electrolysis units; wherein:
the anode oxygen-evolving catalyst of a group of PEM electrolytic units is oxygen-evolving catalyst with high iridium content, namely the oxygen-evolving catalyst with high iridium content is more than or equal to 30 percent;
the anode oxygen evolution catalyst of the other group of PEM electrolysis units adopts low iridium or iridium-free oxygen evolution catalyst, namely the low iridium or iridium-free oxygen evolution catalyst is that the iridium content 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 pile to be lower than the oxidation dissolution potential of an anode low iridium or iridium-free oxygen evolution catalyst;
step 2, monitoring renewable energy source output energy state indexes: the electrolysis voltage, current density or input electric energy at the two ends of the electrolysis electric pile reaches the percentage of the system design power;
step 3, when the electrolytic voltage at two ends of the electrolytic pile is lower than the upper limit of the protection voltage set in the step 1 or the electrolytic current density is smaller than 0.5A/cm 2 Or when the externally input electric energy is less than x percent (x=0-60) of the rated power of the electrolysis cell stack, starting a PEM electrolysis cell stack unit of the low iridium or iridium-free oxygen evolution catalyst system to work, and electrolyzing water to produce hydrogen; otherwise, starting a PEM electrolytic pile unit of the oxygen evolution catalyst system with high iridium content to work, and electrolyzing water to prepare hydrogen.
In the technical proposal, the low iridium or iridium-free oxygen evolution catalyst is monoatomic Ir doped MnO 2 The catalyst, wherein the atomic ratio of Ir is 0.87%, the upper voltage limit in step 1 is 1.75V.
In the above 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 proposal, the low iridium or iridium-free oxygen evolution catalyst is Ti doped RuO 2 The upper voltage limit in step 1 is 1.5V.
In the technical proposal, the oxygen evolution catalyst with low iridium or no iridium element is MnO 2 The upper voltage limit in step 1 is 1.5V.
The invention also provides a high-efficiency and low-cost proton exchange membrane water electrolysis hydrogen production control system consistent with renewable energy sources, which comprises: the hydrogen production system comprises a renewable energy power supply system, a hydrogen production integrated control unit and electrolysis hydrogen production equipment which are sequentially connected, and further comprises a monitoring unit which is respectively connected with the hydrogen production integrated control unit and the electrolysis electric pusher;
the electrolytic hydrogen production device is an electrolytic electric pusher consisting of two sets of PEM electrolysis cells, wherein:
the anode oxygen-evolving catalyst of a group of PEM electrolytic units is oxygen-evolving catalyst with high iridium content, namely the oxygen-evolving catalyst with high iridium content is more than or equal to 30 percent;
the anode oxygen evolution catalyst of the other group of PEM electrolysis units adopts low iridium or iridium-free oxygen evolution catalyst, namely the low iridium or iridium-free oxygen evolution catalyst is that the iridium content is more than or equal to 0 and less than 30 percent;
setting an upper voltage limit to enable the input voltage at two ends of the electrolytic pile to be lower than the oxidation dissolution potential of the anode low iridium or iridium-free oxygen evolution catalyst; the monitoring unit monitors the output energy state index of the renewable energy power supply system: the electrolysis voltage, current density or input electric energy at the two ends of the electrolysis electric pile reaches the percentage of the system design power; then the monitored energy state index data is fed back to the hydrogen production integrated control unit, and the hydrogen production integrated control unit accurately switches the operation states of the two electrolysis units 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 lower than 0.5A/cm 2 Or when the externally input electric energy is less than x percent (x=0-60) of the rated power of the electrolysis cell stack, starting a PEM electrolysis cell stack unit of the low iridium or iridium-free oxygen evolution catalyst system to work, and electrolyzing water to produce hydrogen; otherwise, starting a PEM electrolytic pile unit of the oxygen evolution catalyst system with high iridium content to work, and electrolyzing water to prepare hydrogen.
In the above technical solution, the monitoring unit includes current and voltage sensors.
In the above technical scheme, the hydrogen production integrated control unit includes: 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 above 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 proposal, the low iridium or iridium-free oxygen evolution catalyst is monoatomic Ir doped MnO 2 A catalyst wherein the atomic ratio of Ir is 0.87% and the upper voltage limit is 1.75V; or said lowThe iridium or iridium-free oxygen evolution catalyst is Ti doped RuO 2 A catalyst, in which the upper voltage limit is 1.5V; or the low iridium or iridium-free oxygen evolution catalyst is MnO 2 And a catalyst, wherein the upper voltage limit is 1.5V.
The beneficial effects of the invention are as follows:
the invention provides a high-efficiency and low-cost proton exchange membrane electrolyzed water hydrogen production control method and a control system which are consistent with renewable energy sources, aiming at the characteristics of a low iridium or iridium-free oxygen evolution catalyst, the input voltage is controlled in the actual operation process of a PEM (proton exchange membrane) electrolysis unit of the low iridium or iridium-free oxygen evolution catalyst, the upper voltage limit is set to enable the input voltage to be lower than the oxidation dissolution potential of the anode low iridium or iridium-free oxygen evolution catalyst, and the stable voltage of the low iridium or iridium-free oxygen evolution catalyst can be ensured, so that the catalyst cannot be deactivated rapidly due to excessive oxidation and dissolution of the low iridium or iridium-free oxygen evolution catalyst, and therefore, the control system or the method using the high-activity catalyst can effectively improve the energy conversion efficiency of the electrolysis unit under the low input voltage.
Drawings
The invention is described in further detail below with reference to the drawings and the detailed description.
FIG. 1 is a schematic diagram of a high efficiency, 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 is characterized in that: PEM electrolysers are more flexible and reactive in operation. PEM electrolyzed water technology provides a wider operating range and shorter response times. The operation flexibility is obviously improved, the overall economic benefit of electrolytic hydrogen production can be improved, particularly renewable energy sources can be well combined to generate electricity, so that benefits can be obtained from a plurality of electric markets, and the electrolytic hydrogen production system can adopt low iridium or iridium-free oxygen evolution catalysts to respond to a power supply with low fluctuation and smooth operation when new energy sources are output in a trough or low current density state, so that high-efficiency hydrogen production under low current density is realized, and a large amount of low fluctuation energy can be consumed by designing and modeling an electrolytic unit with larger regulation according to actual output energy of the trough or current density output state, so that the electrolytic hydrogen production efficiency of the whole electrolytic system is improved.
The anode catalysts of the electrolysis cell pile of the existing PEM water electrolysis hydrogen production system are all Ir-based catalysts, but the high current density working condition of the PEM system makes the system have strong dependence on the high Ir-loading catalyst; the non-iridium-based catalyst can greatly reduce the water electrolysis catalysis cost, but the performance of the catalyst is a certain gap compared with the Ir-based catalyst in the hydrogen production efficiency of electrolysis.
The Ir content in the crust is currently about 0.0006ppm, even below Pt. The extremely low reserves result in the high price of Ir, reaching about 220$/g, and price factors limit the wide application of PEM water electrolysis hydrogen production technology. In contrast, the higher abundance Ru price is relatively low, only about one tenth of the Ir price, and the non-noble metal Co, mn, cu, mo, W equivalent has a higher reserves and lower price. Therefore, the design of the low iridium or iridium-free oxygen evolution catalyst has remarkable promotion effect on the reduction of the use cost and popularization and application of the PEM water electrolysis hydrogen production technology.
Low-load iridium<30%) of a catalyst or a non-iridium based catalyst, such as ruthenium based catalysts, non-noble metal catalysts, etc., which at lower current densities [ ]<0.5A/cm 2 ) The catalyst can be used as an anodic Oxygen Evolution Reaction (OER) catalytic material, and can meet the two conditions of stability and high efficiency at the same time, however, at high current density, metal elements in the catalyst can become unstable, dissolution and loss of the metal elements occur, so that the catalyst is deactivated, and finally the electrolytic stack is completely deactivated.
The biggest problem faced by oxygen evolution catalysts with low or no iridium elements is poor stability at high current densities. According to the pH-potential diagram (Pourbaix phase diagram) of the material, ir and its oxide have an oxidative dissolution potential as high as 1.9v vs. rhe at ph=0, which is one of the most corrosion-resistant elements in the periodic table of elements, and thus it shows better stability in acidic OER environments. Dilution of Ir orAvoiding the use of Ir requires the introduction of a second component (e.g., ru, co, mo, etc.) with a lower oxidation-dissolution potential, which necessarily results in a decrease in the overall stability of the catalyst. However, when the applied potential is controlled, even the second component having a low oxidation-dissolution potential tends to be stable. For example MnO 2 The component is oxidized to soluble MnO at a vs. RHE potential above 1.75V 4- Thus when the applied potential reaches 1.8V vs. RHE, mnO 2 Rapid dissolution, a sharp drop in stability, almost complete deactivation within 100 h, and MnO when the control potential is below 1.75v vs. rhe 2 The components are able to maintain stability for up to 8000 hours 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 electrolytic unit of the low iridium or iridium-free oxygen evolution catalyst, the upper voltage limit is set to enable the input voltage to be lower than the oxidation dissolution potential of the anode 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, so that the low iridium or iridium-free oxygen evolution catalyst cannot be excessively oxidized and dissolved to enable the catalyst to be quickly deactivated, and the use of the high-activity catalyst can effectively improve the energy conversion efficiency of the electrolytic unit at the low input voltage.
According to the invention, according to the characteristics of intermittence and instability of renewable energy sources (wind energy, solar energy, tidal energy and the like), the designed system adopts two groups of electrolysis devices to realize the efficient hydrogen production by applying renewable energy power in a mutually matched way:
1) One group is the power supply response of hydrogen production galvanic pile with high iridium content oxygen evolution catalyst (iridium oxide, doped iridium oxide or solid solution thereof, simple substance iridium, iridium-containing alloy and iridium-containing high-load catalyst) to high fluctuation;
2) The other group is to adopt hydrogen production electric pile with low iridium or no iridium element oxygen evolution catalyst to cope with renewable energy power fluctuation, so as to realize power supply response of stable operation.
The other key point of the strategy provided by the invention is that the state indexes of the output energy of the new energy (such as the electrolysis voltage at the two ends of the electric pile, the current density, the percentage of the input electric energy reaching the design power of the system and the like) are monitored through the current or voltage sensor, 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 the power supply response of PEM electrolysis units with low iridium or without iridium element oxygen evolution catalyst to low fluctuation smooth operation, namely when the externally input electric energy is less than x% of the design load of the electrolysis system or the electrolysis voltage at two ends of the electrolysis electric pile is lower than the upper limit of the set protection voltage or the electrolysis current density is less than 0.5A/cm 2 When the value of x is in direct proportion to the scale of the part, the specific size can comprehensively consider two factors of the scale of new energy and the manufacturing cost of the new energy coupled with the hydrogen production system, and the value of x is preferably x=0-60; when the renewable energy source output is in the high fluctuation state of the wave crest, the renewable energy source output is dealt with by the oxygen evolution catalyst with high iridium content, and at the moment, the system is rapidly switched to the PEM electrolysis unit of the oxygen evolution catalyst with high iridium content so as to absorb the energy of the renewable energy source in the high fluctuation state, namely, high-efficiency hydrogen production under high current density, and the whole system can operate at the capacity higher than rated load (more than 100 percent and up to 200 percent) in a short time due to the self-consistency of the PEM system.
The strategy provided by the invention can effectively improve the storage capacity of the PEM system, greatly reduce the cost and improve the energy conversion efficiency.
In view of the above, the invention provides a high-efficiency stable and low-cost control method and a control system for producing hydrogen by electrolysis of water by proton exchange membrane, which are more suitable for coupling with renewable energy sources, and is characterized in that:
1. according to the characteristics of intermittent and unstable renewable energy sources (wind energy, solar energy, tidal energy and the like), the invention adopts two groups of electrolysis devices to realize the efficient hydrogen production by applying renewable energy power in a matched manner: 1) One group is the power supply response of hydrogen production galvanic pile with high iridium content oxygen evolution catalyst (iridium oxide, doped iridium oxide or solid solution thereof, simple substance iridium, iridium-containing alloy and iridium-containing high-load catalyst) to high fluctuation; 2) The other group is that the hydrogen production pile adopting the low iridium or the oxygen evolution catalyst without iridium element realizes high-efficiency hydrogen production under low current density, and the power supply response of stable operation is realized in response to renewable energy power fluctuation. The system can operate in a short time according to the capacity higher than rated load (more than 100 percent and up to 200 percent), and the electrolytic hydrogen production efficiency of the whole electrolytic system is improved.
2. Regulating and controlling the operation states of the two electrolytic units by monitoring the input voltage or the input current density;
3. the upper voltage limit is set to ensure that the input voltage at the two electrolytic ends of the electrolytic pile is lower than the oxidation dissolution potential of the low iridium or iridium-free oxygen evolution catalyst of the anode, so that the stable voltage of the low iridium or iridium-free oxygen evolution catalyst can be ensured;
4. the use of noble metal Ir is reduced or avoided, and the low iridium or iridium-free oxygen evolution catalyst has extremely strong cost advantage, and the catalyst can be used as an anode catalyst to effectively reduce the commercial cost of the PEM system electrolyte hydrogen production technology.
The following specifically describes the high-efficiency and low-cost proton exchange membrane water electrolysis hydrogen production control system consistent with renewable energy source with reference to fig. 1 and 2, comprising: the device comprises a renewable energy power supply system, a hydrogen production integrated control unit and an electrolysis electric pusher which are sequentially connected, and further comprises a monitoring unit which is respectively connected with the hydrogen production integrated control unit and the electrolysis electric pusher;
the renewable energy power supply system is a wind power plant power supply system;
the electrolytic hydrogen production device is an electrolytic electric pusher consisting of two sets of PEM electrolysis cells, wherein: the anode oxygen-evolving catalyst of a group of PEM electrolytic units is oxygen-evolving catalyst with high iridium content, namely the oxygen-evolving catalyst with high iridium content is more than or equal to 30 percent; the anode oxygen evolution catalyst of the other group of PEM electrolysis units adopts low iridium or iridium-free oxygen evolution catalyst, namely the low iridium or iridium-free oxygen evolution catalyst is that the iridium content is more than or equal to 0 and less than 30 percent;
the monitoring unit comprises a current and voltage sensor;
the hydrogen production integrated control unit 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 an upper voltage limit to enable the input voltage at two ends of the electrolytic pile to be lower than the oxidation dissolution potential of the anode low iridium or iridium-free oxygen evolution catalyst; the monitoring unit monitors the output energy state index of the renewable energy power supply system: the electrolysis voltage, current density or input electric energy at the two ends of the electrolysis electric pile reaches the percentage of the system design power; then the monitored energy state index data is fed back to the hydrogen production integrated control unit, and the hydrogen production integrated control unit accurately switches the operation states of the two electrolysis units 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 lower than 0.5A/cm 2 Or when the externally input electric energy is less than x percent (x=0-60) of the rated power of the electrolysis cell stack, starting a PEM electrolysis cell stack unit of the low iridium or iridium-free oxygen evolution catalyst system to work, and electrolyzing water to prepare hydrogen so as to realize the power supply response of stable operation; otherwise, starting the operation of the PEM electrolytic pile unit of the oxygen-separating catalyst system with high iridium content, and electrolyzing water to prepare hydrogen, so as to respond to the high fluctuation power supply.
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 pile to be lower than the oxidation dissolution potential of an anode low iridium or iridium-free oxygen evolution catalyst;
step 2, monitoring renewable energy source output energy state indexes through a current or voltage sensor: the electrolysis voltage, current density or input electric energy at the two ends of the electrolysis electric pile reaches the percentage of the system design power;
step 3, when the electrolytic voltage at two ends of the electrolytic pile is lower than the upper limit of the protection voltage set in the step 1 or the electrolytic current density is smaller than 0.5A/cm 2 Or when the externally input electric energy is less than x percent (x=0-60) of the rated power of the electrolysis cell stack, starting the PEM electrolysis cell stack unit of the low iridium or iridium-free oxygen evolution catalyst system to work, and preparing the electrolysis waterHydrogen, realizing a power supply response of smooth operation; otherwise, starting the operation of the PEM electrolytic pile unit of the oxygen-separating catalyst system with high iridium content, and electrolyzing water to prepare hydrogen, so as to respond to the high fluctuation power supply.
The high iridium content oxygen evolution catalysts in examples 1-3 below are all pure Ir based catalysts.
Example 1: monodisperse Ir-MnO 2 As PEMWEs anode catalyst operating at low voltage
MnO 2 The corrosion dissolution potential of the metal is 1.75V vs. RHE, and a single-atom Ir doped MnO is designed by taking the metal as a substrate 2 Catalyst (Ir-MnO) 2 ) Wherein the atomic ratio of Ir is 0.87%. With the catalyst as OER catalyst in an acidic environment, the catalyst can be used for preparing the catalyst at 10mA cm -2 Stable operation can be achieved for more than 600 hours at current density. By Ir-MnO 2 As anode catalytic material of PEMWEs, an electrolytic tank is assembled. Setting the system protection voltage as a monolithic electrolysis voltage of 1.75 and V, and when the monolithic input voltage is greater than 1.75V, operating the PEM electrolysis cell stack unit of the oxygen evolution catalyst system with high iridium content to produce hydrogen by electrolysis; when the single-chip input voltage is less than 1.75V, the Ir-MnO is monodisperse 2 The oxygen evolution catalyst system PEM electrolysis cell stack unit operates to electrolytically produce hydrogen.
Example 2: ti doped RuO 2 As PEMWEs anode catalyst operating at low voltage
RuO 2 The corrosion dissolution potential of the alloy is 1.5V vs. RHE, and Ti doping modification is carried out on the alloy to obtain the Ti doped RuO with high activity under low potential 2 Material (Ti-RuO) 2 ) The current density at a potential of 1.43V vs. RHE exceeds 100mA cm -2 . With the catalyst as OER catalyst in an acidic environment, the catalyst can be used for preparing the catalyst at 10mA cm -2 Stable operation can be achieved for more than 30 hours at current density. In the form of Ti-RuO 2 As anode catalytic material of PEMWEs, an electrolytic tank is assembled. Setting the system protection voltage as 1.5V of a monolithic electrolysis voltage, and when the monolithic input voltage is greater than 1.5V, operating the PEM electrolysis cell stack unit of the oxygen evolution catalyst system with high iridium content to produce hydrogen by electrolysis; when the monolithic input voltage is less than 1.5V, ti doped RuO 2 The oxygen evolution catalyst system PEM electrolysis cell stack unit operates to electrolytically produce hydrogen.
Example 3: mnO (MnO) 2 As a means ofPEMWEs anode catalyst operating at low voltage
MnO 2 The corrosion dissolution potential of (2) is 1.75V vs. RHE, and the (2) is directly used as an OER catalyst in an acidic environment, and is shown in 10mA cm -2 Stable operation can be achieved for more than 8000h at current density. In MnO form 2 As anode catalytic material of PEMWEs, an electrolytic tank is assembled. Setting the system protection voltage as a monolithic electrolysis voltage of 1.75 and V, and when the monolithic input voltage is greater than 1.75V, operating the PEM electrolysis cell stack unit of the oxygen evolution catalyst system with high iridium content to produce hydrogen by electrolysis; when the input voltage of the single chip is less than 1.75V, mnO 2 The oxygen evolution catalyst system PEM electrolysis cell stack unit operates to electrolytically produce hydrogen.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.

Claims (10)

1. An efficient, low cost control method for water electrolysis hydrogen production with a renewable energy source, characterized in that the control method is applicable to an electrolysis cell stack consisting of two sets of PEM electrolysis cells; wherein:
the anode oxygen-evolving catalyst of a group of PEM electrolytic units is oxygen-evolving catalyst with high iridium content, namely the oxygen-evolving catalyst with high iridium content is more than or equal to 30 percent;
the anode oxygen evolution catalyst of the other group of PEM electrolysis units adopts low iridium or iridium-free oxygen evolution catalyst, namely the low iridium or iridium-free oxygen evolution catalyst is that the iridium content 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 pile to be lower than the oxidation dissolution potential of an anode low iridium or iridium-free oxygen evolution catalyst;
step 2, monitoring renewable energy source output energy state indexes: the electrolysis voltage, current density or input electric energy at the two ends of the electrolysis electric pile reaches the percentage of the system design power;
step 3, when the electrolytic voltage at two ends of the electrolytic pile is lower than the upper limit of the protection voltage set in the step 1 or the electrolytic current density is smaller than 0.5A/cm 2 Or when the externally input electric energy is less than 0-60% of the rated power of the electrolysis cell stack, starting a PEM electrolysis cell stack unit of the low iridium or iridium-free oxygen evolution catalyst system to work, and electrolyzing water to prepare hydrogen; otherwise, starting a PEM electrolytic pile unit of the oxygen evolution catalyst system with high iridium content to work, and electrolyzing water to prepare hydrogen.
2. The control method according to claim 1, wherein the low iridium or iridium-free oxygen evolution catalyst is monoatomic Ir doped MnO 2 The catalyst, wherein the atomic ratio of Ir is 0.87%, the upper voltage limit in step 1 is 1.75V.
3. The control method according to claim 1, wherein the high iridium content oxygen evolution catalyst is iridium oxide, doped iridium oxide, iridium-containing alloy, or iridium-containing high-supported catalyst.
4. The control method according to claim 1, wherein the low iridium or iridium-free oxygen evolution catalyst is Ti-doped RuO 2 The upper voltage limit in step 1 is 1.5V.
5. The control method according to claim 1, wherein the low iridium or iridium-free oxygen evolution catalyst is MnO 2 The upper voltage limit in step 1 is 1.5V.
6. An efficient, low cost proton exchange membrane water electrolysis hydrogen production control system consistent with renewable energy sources, comprising: the hydrogen production system comprises a renewable energy power supply system, a hydrogen production integrated control unit and electrolysis hydrogen production equipment which are sequentially connected, and further comprises a monitoring unit which is respectively connected with the hydrogen production integrated control unit and the electrolysis electric pusher;
the electrolytic hydrogen production device is an electrolytic electric pusher consisting of two sets of PEM electrolysis cells, wherein:
the anode oxygen-evolving catalyst of a group of PEM electrolytic units is oxygen-evolving catalyst with high iridium content, namely the oxygen-evolving catalyst with high iridium content is more than or equal to 30 percent;
the anode oxygen evolution catalyst of the other group of PEM electrolysis units adopts low iridium or iridium-free oxygen evolution catalyst, namely the low iridium or iridium-free oxygen evolution catalyst is that the iridium content is more than or equal to 0 and less than 30 percent;
setting an upper voltage limit to enable the input voltage at two ends of the electrolytic pile to be lower than the oxidation dissolution potential of the anode low iridium or iridium-free oxygen evolution catalyst; the monitoring unit monitors the output energy state index of the renewable energy power supply system: the electrolysis voltage, current density or input electric energy at the two ends of the electrolysis electric pile reaches the percentage of the system design power; then the monitored energy state index data is fed back to the hydrogen production integrated control unit, and the hydrogen production integrated control unit accurately switches the operation states of the two electrolysis units 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 lower than 0.5A/cm 2 Or when the externally input electric energy is less than 0-60% of the rated power of the electrolysis cell stack, starting a PEM electrolysis cell stack unit of the low iridium or iridium-free oxygen evolution catalyst system to work, and electrolyzing water to prepare hydrogen; otherwise, starting a PEM electrolytic pile unit of the oxygen evolution catalyst system with high iridium content to work, and electrolyzing water to prepare 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: 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 high loading catalyst.
10. The control system of claim 6, wherein the low iridium or iridium-free oxygen evolution catalyst is a single atom Ir doped MnO 2 A catalyst wherein the atomic ratio of Ir is 0.87% and the upper voltage limit is 1.75V; or the low iridium or iridium-free oxygen evolution catalyst is Ti doped RuO 2 A catalyst, in which the upper voltage limit is 1.5V; or the low iridium or iridium-free oxygen evolution catalyst is MnO 2 And a catalyst, wherein the upper voltage limit is 1.5V.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN111118538A (en) * 2018-11-01 2020-05-08 中国科学院大连化学物理研究所 Preparation method of proton exchange membrane electrolyte water electrolysis membrane electrode with low iridium loading
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

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013136801A (en) * 2011-12-28 2013-07-11 Hitachi Ltd System for converting and storing renewable energy
US10337107B2 (en) * 2016-05-03 2019-07-02 University Of Louisville Research Foundation, Inc. Solar hydrogen production from ambient water vapor electrolysis

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN111118538A (en) * 2018-11-01 2020-05-08 中国科学院大连化学物理研究所 Preparation method of proton exchange membrane electrolyte water electrolysis membrane electrode with low iridium loading
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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