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WO2024085831A1 - A system and method for increasing hydrogen production in electrolyzers - Google Patents

A system and method for increasing hydrogen production in electrolyzers Download PDF

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Publication number
WO2024085831A1
WO2024085831A1 PCT/TR2023/050497 TR2023050497W WO2024085831A1 WO 2024085831 A1 WO2024085831 A1 WO 2024085831A1 TR 2023050497 W TR2023050497 W TR 2023050497W WO 2024085831 A1 WO2024085831 A1 WO 2024085831A1
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WO
WIPO (PCT)
Prior art keywords
square wave
mosfet
control circuit
electrolyzer
circuit according
Prior art date
Application number
PCT/TR2023/050497
Other languages
French (fr)
Inventor
Mehmet Fatih KAYA
Nesrin Kayataş DEMİR
Nafi Can ERELİ
Tayyar EŞİYOK
Emre ÖZDOĞAN
Bulut HÜNER
Murat KISTI
Original Assignee
T.C. Erciyes Universitesi
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from TR2022/015892 external-priority patent/TR2022015892A2/en
Application filed by T.C. Erciyes Universitesi filed Critical T.C. Erciyes Universitesi
Priority to JP2024564922A priority Critical patent/JP2025520258A/en
Publication of WO2024085831A1 publication Critical patent/WO2024085831A1/en

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/50—Processes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells

Definitions

  • the invention relates to Polymer Electrolyte Membrane (PEM) or alkali electrolyzers with a compact structure that produces high-purity hydrogen and a device and method for increasing the hydrogen production efficiency of these devices.
  • PEM Polymer Electrolyte Membrane
  • alkali electrolyzers with a compact structure that produces high-purity hydrogen and a device and method for increasing the hydrogen production efficiency of these devices.
  • Hydrogen production can be realized from fossil fuels, solar energy, biomass, natural gas, and electrolysis of water.
  • the method of electrolysis of water is the cleanest and simplest method.
  • the electrolysis of the water takes place by separating the water into hydrogen and oxygen ions by applying direct current (DC) potential to the anode and cathode electrodes immersed in the electrolyte through the external circuit.
  • the method of electrolysis of water is divided into two: alkaline water electrolysis at low temperature and PEM water electrolysis.
  • FIG. 1 Simple structured pulse width modulation (PWM) circuit
  • Figure 2 Algorithm used to examine cell performance
  • Figure 3 Representation of the wave applied to the electrolyzer cell at a frequency of 25 kHz
  • Figure 4 Graph of energy consumed to produce 1 mL of hydrogen produced in 50% duty cycle
  • Adjustable direct current power supply for integrated circuits
  • Adjustable direct current power supply for electrolyzer cell
  • the solution provided by the invention is a system developed both to prevent corrosion of the electrodes and to reduce the problems of decreasing the active surface area in contact with the electrode and electrolyte interface, causing the electrodes to consume more energy and decreasing the cell efficiency, and to produce more hydrogen with long life and unit power value.
  • PWM is known as the method of controlling logic 1 and logic 0 levels by switching the DC potential at certain times.
  • One of the biggest advantages of the PWM method is that the average power of the constant voltage applied to the load is divided into parts.
  • oxygen gas bubbles formed on the anode side of pulse voltage application reduced the energy required for hydrogen production during electrolysis with the duration of adhesion to the electrode surface.
  • Voltage pulses applied to PEM or alkaline electrolyzers decreased concentration losses by increasing the cell's energy consumption and mass transfer. However, it was ensured that the O2 gases formed during the decomposition of H2O were separated from the electrode surface in the dead time zone and cell efficiency was increased.
  • the device of the invention includes a square wave oscillator integration (1) used to control mosfet transmission or cutting states, a Potentiometer (2, 3) to be used in adjusting the duty cycle value of the square wave signal (duty cycle means the ratio of the period when the system is active to the total time (Period)), a mosfet driver integration (4) to increase the performance of the mosfet transmission and cutting states, a Resistance-1 (5) to ensure the stable operation of the mosfet, a Resistance-2 (6) to ensure that the square wave signal is transmitted to the mosfet door pin, a mosfet (7) to act as an electronic switching element used to provide a square wave signal to the PEM electrolyzer, and a PEM or alkali electrolysis cell (8) used for hydrogen production.
  • a square wave oscillator integration used to control mosfet transmission or cutting states
  • a Potentiometer (2, 3) to be used in adjusting the duty cycle value of the square wave signal (duty cycle means the
  • the adjustable direct current power supply (9) is preferably used for operating the +15V, square wave oscillator integration, and mosfet drive integration.
  • the other direct current power source (10), preferably +2V or +2.5V, is connected to the electrodes of the electrolyzer.
  • Oscilloscope (11) is used to monitor and control the change of duty cycle, frequency, and amplitude values from the parameters of the square wave signal applied to the PEM electrolyzer.
  • Pulse width modulation is performed using mosfet, an electronic switching element of the direct current potential applied to PEM or alkaline electrolyzers.
  • the control of the transmission and cutting states of the mosfet is carried out with a square wave oscillator integration (1), preferably TL-type, even more preferably TL494 integrated circuit.
  • the square wave signal at the output pin of the TL494 integrated circuit is applied to the gate pin of the mosfet by amplifying a mosfet driver integration circuit (4), preferably with TC4420 so that it can transmit the mosfet.
  • the anode electrode of the PEM or alkaline electrolyzer depends on the direct current potential located in the drain pin of the mosfet.
  • the mosfet acts as a short-circuit when it is in the transmission zone and no voltage is generated on the electrodes; it acts as an open switch when it is in the cutting zone and the voltage at the drain end is generated on the electrodes.
  • pulse width modulation is carried out and the pulse potential is obtained on the PEM or alkali electrolyzer.
  • the amplitude value of the pulse potential is determined by the amplitude value of the direct current potential used, the frequency and duty cycle can be adjusted with the potentiometers used in the square wave oscillator.
  • the amount of hydrogen produced, and the energy spent by the PEM or alkaline electrolyzer are controlled.
  • the desired amount of hydrogen production and control of the energy expended by the PEM or alkaline electrolyzer is accomplished by changing the values of the potentiometers in the square wave oscillator or by changing the voltage provided by the adjustable direct current power supply used to determine the amplitude of the square wave.
  • the optimum value of the frequency and duty cycle is determined to achieve the desired hydrogen production amount values.
  • the duty cycle and the amplitude value are used to determine the amount of energy the cell expands, while the frequency value is used to determine the frequency of the signal to be applied to the PEM or alkaline electrolyzer.
  • Figure 1 shows the application of the square wave signal obtained by the PWM to the electrodes of the PEM or alkaline electrolyzer.
  • the square wave oscillator integration (1) controls the transmission and cutting states of the mosfet (7).
  • the output current of this integration is amplified by the mosfet drive integration (4) as it is not sufficient to change the state of the mosfet.
  • the anode (+) electrode of the PEM or alkali electrolyzer is connected to the drain pin of the mosfet.
  • the cathode (-) electrode has been grounded and the PEM electrolyzer circuit has been completed.
  • Figure 2 shows the control algorithm of the frequency and duty cycle of the square wave signal for the optimum amount of hydrogen production and the energy value spent.
  • Preparation of the electrolyte as initial values, application of the adjustable direct current potential to the circuit in order for the TL494 square wave oscillator integration (1) to operate, and application of the adjustable direct current power supply (7) to the drain end of the mosfet to determine the amplitude value of the square wave signal to be applied to the PEM or alkali electrolyzer are performed.
  • a square wave signal is obtained at the electrodes of the PEM electrolyzer. Hydrogen production is observed with the start of electrolysis.
  • the performance of the PEM or alkaline electrolyzer can be compared with the amount of hydrogen produced at a different duty cycle, frequency, and amplitude values.
  • the duty cycle of the square wave signal is maintained at a constant value between 0% and 100%.
  • the frequency of the signal is selected at a value between 0 Hz and 1 MHz.
  • the amplitude value is set from the adjustable direct current power source to the cell operating voltage and the hydrogen amount values produced are recorded. The same process continues with changing the duty cycle, frequency, and amplitude value of the square wave signal. We conclude by comparing the recorded hydrogen amounts.
  • Hydrogen is produced as a result of ion transport in the electrolyzer where electrochemical reactions occur.
  • the electric current applied between the anode and cathode electrodes attracts opposite charges.
  • the H+ ion is carried to the electrode by an ionic conductive electrolyte. Hydrogen gas occurs in the cathode with the electron passing through the external circuit. This situation occurs similarly in PEM and alkaline electrolyzers.
  • the electronic control board provides control of the electrical current applied to the electrolysis cell and connects to the anode current collector. This system switches the positive (+) pole of the resource.
  • the cathode current collector of the cell is directly connected to the ground (GND).
  • Hydrogen has become quite popular as it is an energy carrier with a high gravimetric density.
  • Today hydrogen production methods are still not a widely used method due to their high cost.
  • research is being conducted to reduce production costs and to improve the performance of hydrogen production systems.
  • the amount of hydrogen produced in the present invention is shown in Figure 4 and Figure 5, where the same amount of hydrogen is produced as the lower energy requirement compared to the previous art.
  • the cost of hydrogen production is reduced depending on the energy consumed, while the hydrogen production performance of the system is increased.
  • the use of hydrogen energy is expected to increase in areas such as the defense industry, space, automotive industry, and portable and fixed large-scale systems.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

The invention relates to Polymer Electrolysis Membrane (PEM) or alkali electrolyzers having a compact structure that produces high-purity hydrogen and a device and method for increasing the hydrogen production efficiency of these devices.

Description

A SYSTEM AND METHOD FOR INCREASING HYDROGEN PRODUCTION IN ELECTROLYZERS
Technical Field
The invention relates to Polymer Electrolyte Membrane (PEM) or alkali electrolyzers with a compact structure that produces high-purity hydrogen and a device and method for increasing the hydrogen production efficiency of these devices.
State of the Art
Hydrogen production can be realized from fossil fuels, solar energy, biomass, natural gas, and electrolysis of water. Among these methods, the method of electrolysis of water is the cleanest and simplest method. The electrolysis of the water takes place by separating the water into hydrogen and oxygen ions by applying direct current (DC) potential to the anode and cathode electrodes immersed in the electrolyte through the external circuit. The method of electrolysis of water is divided into two: alkaline water electrolysis at low temperature and PEM water electrolysis.
In the prior art, hydrogen and oxygen production was performed in the cell with constant voltage. During electrolysis, oxygen gas bubbles formed in the reaction at the anode are attached to the electrode surface. This causes both corrosion of the electrodes and reduction of the active surface area in contact with the electrode and electrolyte interface, causing the electrodes to consume more energy and decrease cell efficiency.
The article "Pulsed water electrolysis: A review" by Rocha et al. discloses possible reasons for the increase in efficiency, including an increase in the concentration of reactants on the electrode surface, improvement of bubble separation from the electrode, and degradation of the electrical double layer.
In the prior art, no operation reduces the impact voltage to 0 volts. In the invention, the fact that the voltage value decreases to 0 volts stops the production of hydrogen and allows time for the gas bubbles to separate from the electrode surface. This reduces the corrosive effects of oxygen on the anode side.
Descriptions of the Figures
Figure 1 : Simple structured pulse width modulation (PWM) circuit
Figure 2: Algorithm used to examine cell performance Figure 3: Representation of the wave applied to the electrolyzer cell at a frequency of 25 kHz Figure 4: Graph of energy consumed to produce 1 mL of hydrogen produced in 50% duty cycle
Figure 5: Graph of energy consumed to produce 1 mL of hydrogen produced in 75% duty cycle
Elements in Figures
1. Square wave oscillator integration
2. Potentiometer- 1
3. Potentiometer-2
4. Mosfet driver integration
5. Resistance- 1
6. Resistance-2
7. Mosfet
8. Electrolysis cell
9. Adjustable direct current power supply (for integrated circuits)
10. Adjustable direct current power supply (for electrolyzer cell)
11. Oscilloscope
Detailed Description of the Invention
The solution provided by the invention is a system developed both to prevent corrosion of the electrodes and to reduce the problems of decreasing the active surface area in contact with the electrode and electrolyte interface, causing the electrodes to consume more energy and decreasing the cell efficiency, and to produce more hydrogen with long life and unit power value.
Although there are electrolysis systems in the prior art where pulse voltage is applied, the method of hydrogen production by applying a pulse voltage to PEM or alkaline electrolyzers is not included in the state of the art.
The use of hydrogen or oxygen, which will be obtained by applying the square wave signal obtained by PWM to PEM or alkali electrolyzers, in medical and biomedical applications in the food industry and health, from space research, especially in the defense industry, to the energy and automotive industry, is of great importance.
With this invention, the overvoltage caused by gas accumulations in the cell is reduced with the pulse voltage, and the hydrogen production potential at the unit power value is increased. PWM is known as the method of controlling logic 1 and logic 0 levels by switching the DC potential at certain times. One of the biggest advantages of the PWM method is that the average power of the constant voltage applied to the load is divided into parts. In this context, instead of applying DC potential to PEM or alkaline electrolysis cells, oxygen gas bubbles formed on the anode side of pulse voltage application reduced the energy required for hydrogen production during electrolysis with the duration of adhesion to the electrode surface.
Voltage pulses applied to PEM or alkaline electrolyzers decreased concentration losses by increasing the cell's energy consumption and mass transfer. However, it was ensured that the O2 gases formed during the decomposition of H2O were separated from the electrode surface in the dead time zone and cell efficiency was increased.
The device of the invention includes a square wave oscillator integration (1) used to control mosfet transmission or cutting states, a Potentiometer (2, 3) to be used in adjusting the duty cycle value of the square wave signal (duty cycle means the ratio of the period when the system is active to the total time (Period)), a mosfet driver integration (4) to increase the performance of the mosfet transmission and cutting states, a Resistance-1 (5) to ensure the stable operation of the mosfet, a Resistance-2 (6) to ensure that the square wave signal is transmitted to the mosfet door pin, a mosfet (7) to act as an electronic switching element used to provide a square wave signal to the PEM electrolyzer, and a PEM or alkali electrolysis cell (8) used for hydrogen production. The adjustable direct current power supply (9) is preferably used for operating the +15V, square wave oscillator integration, and mosfet drive integration. The other direct current power source (10), preferably +2V or +2.5V, is connected to the electrodes of the electrolyzer. Oscilloscope (11) is used to monitor and control the change of duty cycle, frequency, and amplitude values from the parameters of the square wave signal applied to the PEM electrolyzer.
The steps followed for the pulsed voltage and hydrogen production method in the PEM Electrolyzer are as follows.
Electronic Circuit Board
Pulse width modulation is performed using mosfet, an electronic switching element of the direct current potential applied to PEM or alkaline electrolyzers. The control of the transmission and cutting states of the mosfet is carried out with a square wave oscillator integration (1), preferably TL-type, even more preferably TL494 integrated circuit. The square wave signal at the output pin of the TL494 integrated circuit is applied to the gate pin of the mosfet by amplifying a mosfet driver integration circuit (4), preferably with TC4420 so that it can transmit the mosfet. The anode electrode of the PEM or alkaline electrolyzer depends on the direct current potential located in the drain pin of the mosfet. The mosfet acts as a short-circuit when it is in the transmission zone and no voltage is generated on the electrodes; it acts as an open switch when it is in the cutting zone and the voltage at the drain end is generated on the electrodes. Thus, pulse width modulation is carried out and the pulse potential is obtained on the PEM or alkali electrolyzer. While the amplitude value of the pulse potential is determined by the amplitude value of the direct current potential used, the frequency and duty cycle can be adjusted with the potentiometers used in the square wave oscillator. Thus, the amount of hydrogen produced, and the energy spent by the PEM or alkaline electrolyzer are controlled.
Control Card Algorithm
The desired amount of hydrogen production and control of the energy expended by the PEM or alkaline electrolyzer is accomplished by changing the values of the potentiometers in the square wave oscillator or by changing the voltage provided by the adjustable direct current power supply used to determine the amplitude of the square wave. The optimum value of the frequency and duty cycle is determined to achieve the desired hydrogen production amount values. The duty cycle and the amplitude value are used to determine the amount of energy the cell expands, while the frequency value is used to determine the frequency of the signal to be applied to the PEM or alkaline electrolyzer.
Figure 1 shows the application of the square wave signal obtained by the PWM to the electrodes of the PEM or alkaline electrolyzer. The square wave oscillator integration (1) controls the transmission and cutting states of the mosfet (7). The output current of this integration is amplified by the mosfet drive integration (4) as it is not sufficient to change the state of the mosfet. The anode (+) electrode of the PEM or alkali electrolyzer is connected to the drain pin of the mosfet. The cathode (-) electrode has been grounded and the PEM electrolyzer circuit has been completed.
Figure 2 shows the control algorithm of the frequency and duty cycle of the square wave signal for the optimum amount of hydrogen production and the energy value spent. Preparation of the electrolyte as initial values, application of the adjustable direct current potential to the circuit in order for the TL494 square wave oscillator integration (1) to operate, and application of the adjustable direct current power supply (7) to the drain end of the mosfet to determine the amplitude value of the square wave signal to be applied to the PEM or alkali electrolyzer are performed. After adjusting the initial values, a square wave signal is obtained at the electrodes of the PEM electrolyzer. Hydrogen production is observed with the start of electrolysis. The performance of the PEM or alkaline electrolyzer can be compared with the amount of hydrogen produced at a different duty cycle, frequency, and amplitude values. For comparison of the amount of hydrogen, the duty cycle of the square wave signal is maintained at a constant value between 0% and 100%. The frequency of the signal is selected at a value between 0 Hz and 1 MHz. The amplitude value is set from the adjustable direct current power source to the cell operating voltage and the hydrogen amount values produced are recorded. The same process continues with changing the duty cycle, frequency, and amplitude value of the square wave signal. We conclude by comparing the recorded hydrogen amounts.
In the prior art, no operation reduces the impact voltage to 0 volts. In the invention, the fact that the voltage value decreases to 0 volts stops the production of hydrogen and allows time for the gas bubbles to separate from the electrode surface. This reduces the corrosive effects of oxygen on the anode side.
The method applied for the electrolysis to be performed with the system subject to the invention is described below.
• Hydrogen is produced as a result of ion transport in the electrolyzer where electrochemical reactions occur. The electric current applied between the anode and cathode electrodes attracts opposite charges.
• The H+ ion is carried to the electrode by an ionic conductive electrolyte. Hydrogen gas occurs in the cathode with the electron passing through the external circuit. This situation occurs similarly in PEM and alkaline electrolyzers.
• The electronic control board provides control of the electrical current applied to the electrolysis cell and connects to the anode current collector. This system switches the positive (+) pole of the resource. The cathode current collector of the cell is directly connected to the ground (GND).
Hydrogen has become quite popular as it is an energy carrier with a high gravimetric density. Today, hydrogen production methods are still not a widely used method due to their high cost. However, research is being conducted to reduce production costs and to improve the performance of hydrogen production systems. The amount of hydrogen produced in the present invention is shown in Figure 4 and Figure 5, where the same amount of hydrogen is produced as the lower energy requirement compared to the previous art. Thus, the cost of hydrogen production is reduced depending on the energy consumed, while the hydrogen production performance of the system is increased. As a result, the use of hydrogen energy is expected to increase in areas such as the defense industry, space, automotive industry, and portable and fixed large-scale systems.

Claims

CLAIMS An Electrolyzer Control Circuit, characterized in that it comprises:
• electrolysis cell (8)
• mosfet (7) acting as an electronic switching element for providing a square wave signal to the electrolysis cell (8),
• square wave oscillator integration (1) for controlling mosfet transmission or cutting states,
• potentiometer (2, 3) for adjusting the duty cycle value of the square wave signal,
• mosfet driver integration (4) for increasing the performance of mosfet transmission and cutting states,
• Resistance- 1 (5) ensuring the stable operation of the mosfet (7),
• Resistance-2 (6) ensuring the square wave signal is transmitted to the door pin of the mosfet (7),
• adjustable direct current power supply (9) for operating square wave oscillator integration (1) and mosfet drive integration (4)
• adjustable direct current power supply (10) connected to the electrodes of the electrolyzer
• oscilloscope (11) for monitoring the duty cycle, frequency, and amplitude values of the square wave signal applied to the electrolyzer. A control circuit according to Claim 1, characterized in that said electrolysis cell is a Polymer Electrolyte Membrane (PEM) electrolysis cell. A control circuit according to Claim 1, characterized in that said electrolysis cell is an Alkaline electrolysis cell. A control circuit according to Claim 1, characterized in that the direct current power supply (9) used for the operation of the integrators (4) is +15V. A control circuit according to Claim 1, characterized in that the adjustable direct current power supply (10) connected to the electrodes of the electrolyzer is +2Vf. A control circuit according to Claim 1, characterized in that said square wave oscillator integration (1) is of the TL-type. A control circuit according to Claim 6, characterized in that the square wave oscillator integration (1) is TL494. An electrolyzer, characterized in that it comprises a control circuit according to Claim 1.
PCT/TR2023/050497 2022-10-19 2023-05-31 A system and method for increasing hydrogen production in electrolyzers WO2024085831A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2024564922A JP2025520258A (en) 2022-10-19 2023-05-31 Systems and methods for increasing hydrogen production in electrolyzers

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
TR2022/015892 TR2022015892A2 (en) 2022-10-19 System and Method to Increase Hydrogen Production in Electrolyzers.
TR2022015892 2022-10-19

Publications (1)

Publication Number Publication Date
WO2024085831A1 true WO2024085831A1 (en) 2024-04-25

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2295829A (en) * 1994-12-05 1996-06-12 Motorola Inc Control of charging and discharging of the electrochemical diffusion layer in electroplating to achieve uniform deposit characteristics
US6797134B2 (en) * 1989-10-10 2004-09-28 Lectro Press, Inc. Pulsed power supply for electrochemical cell
EP3649276A2 (en) * 2017-07-03 2020-05-13 Sintef TTO AS A method for producing hydrogen in a pem water electrolyser system, pem water electrolyser cell, stack and system

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6797134B2 (en) * 1989-10-10 2004-09-28 Lectro Press, Inc. Pulsed power supply for electrochemical cell
GB2295829A (en) * 1994-12-05 1996-06-12 Motorola Inc Control of charging and discharging of the electrochemical diffusion layer in electroplating to achieve uniform deposit characteristics
EP3649276A2 (en) * 2017-07-03 2020-05-13 Sintef TTO AS A method for producing hydrogen in a pem water electrolyser system, pem water electrolyser cell, stack and system

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