Hydrogen Production by Pulsed Water Electrolysis：Principle，Current Technology Status and Future Trends

Pengxiang Zhao; Lijie Wang; Shaoguang Feng; Xuewei Zhang; Hongfei Zhu; Kunyuan Sun; Yang Yu; Miaoting Sun; Xiaoxiao Meng; Jihui Gao; Guangbo Zhao; Wei Zhou

doi:10.7536/PC20250517

Progress in Chemistry >

2026 , Vol. 38 >Issue 2: 194 - 209

DOI: https://doi.org/10.7536/PC20250517

Review

Hydrogen Production by Pulsed Water Electrolysis：Principle，Current Technology Status and Future Trends

Pengxiang Zhao ¹ ,
Lijie Wang ² ,
Shaoguang Feng ² ,
Xuewei Zhang ¹ ,
Hongfei Zhu ² ,
Kunyuan Sun ² ,
Yang Yu ¹ ,
Miaoting Sun ¹ ,
Xiaoxiao Meng ¹ ,
Jihui Gao ¹ ,
Guangbo Zhao ¹ ,
Wei Zhou ^,¹^,^*

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¹ School of Energy Science and Engineering， Harbin Institute of Technology， Harbin 150001， China
² China Datang Technology Innovation Co.， Ltd.， Xiong’an 071799， China

^*hitzhouw@hit.edu.cn

Received date: 2025-05-21

Revised date: 2025-07-10

Online published: 2026-01-31

Supported by

National Natural Science Foundation of China(52476192)

Key Research and Development Program of Heilongjiang Province(2024ZXJ03C06)

Science and Technology Project of China Datang Technology Innovation Co.，Ltd(10002552D24KJZB00017)

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Abstract

Hydrogen energy，as a pivotal clean energy carrier under the carbon neutrality goal，urgently demands breakthroughs in its efficient preparation technology. This paper focuses on pulsed electrolysis for hydrogen production，systematically elucidating the mechanisms of reducing the diffusion layer thickness，accelerating bubble detachment，and enhancing electrode stability through periodic modulation of current/voltage. It reveals the optimization mechanisms of suppressing the bubble shielding effect via pulse modulation and shortening the ion relaxation time using high-frequency pulses. The paper summarizes the influence laws of pulse parameters （waveform，frequency，duty cycle，etc.） on hydrogen production characteristics，compares the application potential of inductive pulses，voltage/current pulses，and fluctuating power electrolysis technologies，and highlights their advantages in adapting to the fluctuating power sources of wind and solar energy （wide power regulation range，suppression of voltage flicker）. Despite demonstrating high energy efficiency and robust performance，pulsed electrolysis still encounters bottlenecks such as insufficient electrode impact resistance and unclear multi-parameter coupling mechanisms. Future research should integrate intelligent algorithms for dynamic regulation optimization，develop integrated wind-solar-storage-hydrogen systems，promote the application of high-frequency resonance and low ripple filtering technologies，and accelerate the large-scale production of green hydrogen. This paper provides theoretical support for the advancement of pulsed electrolysis technology and its potential engineering applications.

Contents

1 Introduction

2 Principle of hydrogen production by pulse electrolysis of water

2.1 Introduction to hydrogen production technology through water electrolysis

2.2 Analysis of the mechanism for enhancing hydrogen production performance through pulse electroly

3 The influence of pulse parameters on hydrogen production characteristics

3.1 Impact of pulse waveform

3.2 Impact of pulse period，frequency，and duty cycle

3.3 Impact of pulse potential

4 Classification of hydrogen production technology through pulsed electrolysis of water

4.1 Hydrogen production through induced pulse electrolysis of water

4.2 Hydrogen production through electrolysis of water using voltage pulse

4.3 Hydrogen production by electrolysis of water using current pulse

4.4 Power fluctuation in hydrogen production through water electrolysis

5 Wide-power hydrogen production technology through water electrolysis，adaptable to fluctuating wind and solar inputs

5.1 Impact of fluctuation in wind and solar power sources

5.2 Hydrogen production technology based on wind fluctuation power generation

5.3 Photovoltaic fluctuation power generation and hydrogen production technology

5.4 Hydrogen production technology through wind-solar hybrid fluctuating power generation

6 Summary and future outlook

Key words： pulsed electrolysis; hydrogen production by electrolysis of water; energy efficiency optimization; wind and solar volatility; parameter control

Cite this article

Pengxiang Zhao , Lijie Wang , Shaoguang Feng , Xuewei Zhang , Hongfei Zhu , Kunyuan Sun , Yang Yu , Miaoting Sun , Xiaoxiao Meng , Jihui Gao , Guangbo Zhao , Wei Zhou . Hydrogen Production by Pulsed Water Electrolysis：Principle，Current Technology Status and Future Trends[J]. Progress in Chemistry, 2026 , 38(2) : 194 -209 . DOI: 10.7536/PC20250517

1 Introduction

People's living standards and quality are closely linked to energy, yet currently, the reserves of humanity's primary energy sources—coal, oil, natural gas, etc.—can only supply approximately 156 years, 40 years, and 60 years respectively^[1]. Meanwhile, the combustion of carbon-based fossil fuels leads to the release of greenhouse gases into the atmosphere, thereby becoming the cause of widespread problems such as global warming, environmental pollution, and climate change^[2-4]. Although China's economy has grown rapidly, its energy structure is relatively singular, relying long-term on fossil resources dominated by coal (Table 1). Therefore, people are constantly seeking new alternative energy sources, and hydrogen energy has gradually stepped onto the historical stage.

表1 2023年我国主要能源产品产量及增长率

Table 1 The output and growth rate of China’s major energy products in 2023

Product name	Unit	Production	Growth/%
Raw coal	Gt	4.71	3.4
Crude oil	Mt	209.026	2.1
Natural gas	Gm³	232.43	5.6
Electricity generation	10⁸ kWh	94564.4	6.9
Among them：thermal power	10⁸ kWh	62657.4	6.4
Hydropower	10⁸ kWh	12858.5	-4.9
nuclear power	10⁸ kWh	4347.2	4.1
Wind power	10⁸ kWh	8858.7	16.2
Solar power	10⁸ kWh	5841.5	36.7

Hydrogen energy has advantages such as safety, high utilization efficiency, and renewability, and is considered an effective way to solve the energy crisis and alleviate environmental pollution^[5-6]. At the same time, hydrogen energy has extremely high calorific value and energy per unit volume, making it highly valuable for utilization. Furthermore, due to its wide distribution and advantages in storage and transportation^[7], it has broad prospects for application. In addition, hydrogen itself is also an important chemical raw material, such as using H₂ and CO₂ to produce methanol^[8] and using H₂, H₂O and CO₂ to manufacture polymers^[9].

Currently, most hydrogen is produced via steam methane reforming (SMR), with an efficiency of approximately 45%~65%^[10-14]. This process is a mature industrial method that extracts hydrogen from natural gas using a catalytic reaction with steam. However, due to the carbon-intensive nature of SMR and the carbon dioxide it produces, concerns have arisen regarding its environmental sustainability^[15-16].

Water electrolysis for hydrogen production, as a key technology for large-scale green hydrogen production, has become an important part of sustainable and clean energy technologies, and its development is of great significance for achieving carbon neutrality goals^[17]. Essentially, water electrolysis for hydrogen production is a process that uses electrical energy to separate water into its constituent elements (i.e., hydrogen and oxygen). Although current mainstream technologies such as Alkaline Electrolysis (ALK), Proton Exchange Membrane Electrolysis (PEM), and Solid Oxide Electrolysis (SOEC) each have their advantages, they all face multiple constraints regarding efficiency, cost, and material stability^[18-19]. In this context, pulsed water electrolysis for hydrogen production technology demonstrates potential advantages in optimizing energy efficiency, extending lifespan, and enhancing flexibility through periodic current/voltage regulation^[20].

Against the backdrop of an accelerating global energy revolution, water electrolysis for hydrogen production is not only a critical link in the transition of energy carriers but also the core hub for realizing the closed loop of "renewable energy-green hydrogen-end-use decarbonization." The innovation of pulsed water electrolysis for hydrogen production precisely approaches this from the perspective of holistic optimization of energy systems, offering new ideas for future technological breakthroughs.^[21]. From the perspective of energy system integration, pulsed electrolysis technology provides a new paradigm for integrated models such as "offshore wind power-seawater hydrogen production." It holds the potential to deeply integrate with integrated wind-solar-storage systems, promoting the large-scale substitution of green hydrogen in high-carbon emission sectors like steel and chemicals, thereby accelerating the process of low-carbon transformation of the global energy structure.^[22].

Although existing reviews have summarized the mechanisms of pulsed electrolysis, this paper, for the first time, systematically elucidates the dynamic response mechanism by which pulsed technology mitigates wind and solar fluctuations, explicitly proposing a synergistic optimization pathway for pulsed parameters (waveform, frequency, duty cycle) and wide-range wind-solar power inputs. Furthermore, this study systematically compares the application potential of inductive pulses, voltage/current pulses, and fluctuating power electrolysis under fluctuating scenarios, and further proposes integrating intelligent algorithms to optimize dynamic control efficiency and developing integrated wind-solar-storage-hydrogen systems. Approaching from the perspective of energy system integration, this paper provides theoretical support distinct from traditional reviews for the deep integration of variable renewable energy and electrolytic hydrogen production systems.

2 Principle of Pulsed Electrolysis for Hydrogen Production

2.1 Introduction to Water Electrolysis Hydrogen Production Technology

In 1800, British chemists Nicholson and Carlisle constructed a battery based on Volta's explanation of "contact electricity" and applied it to water electrolysis experiments, successfully producing hydrogen and oxygen. This proved that water is not an element but a compound, causing a sensation in the scientific community at the time and advancing the formation and development of the discipline of electrochemistry.^[23].

The principle of hydrogen production via water electrolysis involves applying a potential difference externally to water. Once the voltage energy barrier for the water electrolysis reaction is reached, water, acting as one of the carriers in the circuit, completes the electrical loop. Electrical energy breaks the chemical bonds of water molecules; depending on the type of electrolyzer, water molecules decompose into hydrogen and oxygen atoms before undergoing reactive recombination, ultimately producing oxygen at the anode and hydrogen at the cathode.^[24].

The overall chemical reaction expression for hydrogen production by water electrolysis is: 2H₂O→2H₂↑+O₂↑. The actual process varies with different electrolytes, but it can generally be divided into two parts: the hydrogen evolution reaction involving the cathode, which is the reduction of water or H⁺ via a two-electron reaction (HER), and the oxidation of water or OH^- at the anode via a four-electron reaction (OER) (Figure 1)^[25]. The main steps for H₂ formation in an alkaline environment:

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图1 酸性（蓝线）和碱性（红线）体系中的OER机理，黑线表示中间体的反应路径

Fig.1 OER mechanisms in acidic （blue line） and alkaline （red line） systems，with black indicating the reaction pathways of intermediates

(1) Initial dissociation of water and formation of hydrogen intermediates (Had) via the Volmer step: H₂O+e^-→H_ad+OH^-; This step was proposed by Volmer in 1925, where water molecules adsorb on the cathode surface (M) and consume electrons to generate adsorbed hydrogen atoms (H_ad) and hydroxide ions (OH^-).

(2) Electrochemical Heyrovsky step: H₂O+H_ad+e^-→H₂+OH^-, this step was proposed by Heyrovsky in 1925 and involves the electrochemical desorption of adsorbed hydrogen atoms, combining with water molecules and electrons to produce molecular hydrogen and hydroxide ions.

(3) Tafel composite step: 2H_ad→H₂. This step was proposed by Tafel in 1905; it requires adsorbed hydrogen atoms to combine on adjacent active sites to produce molecular hydrogen.

Main steps of O formation in alkaline environment:₂

(1) Hydroxyl adsorption: OH⁻(aq) + * → HO* + e^-, hydroxide ions adsorb onto active sites, lose an electron, and form adsorbed hydroxyl groups HO*; this step is typically fast.

(2) Oxygen adsorption: HO* + OH^-(aq) → O* + H₂O(l) + e^-, the adsorbed hydroxyl HO* combines with an OH^-releasing H₂O and an electron to form an adsorbed oxygen atom O*.

(3) Peroxide adsorption: O* + OH⁻(aq) → HOO* + e^-. The adsorbed oxygen atom O* reacts with a hydroxide ion, losing an electron to form the adsorbed peroxo species HOO*. This step is generally considered the rate-determining step of the entire OER process, as it involves the formation of the O—O bond, which requires high activation energy. One of the core functions of the catalyst is to effectively promote the formation of the O—O bond.

(4) Desorption: HOO* + OH^-(aq) → O₂(g) + H₂O(l) + e^- + *, the adsorbed hydroperoxy group HOO* combines with an OH^-releasing H₂O and an electron, desorbing to form an oxygen molecule O₂, while the catalyst active site is released.

Water electrolysis hydrogen production technology is mainly divided into four categories based on different electrolyzers: Alkaline Water Electrolysis (ALK), Proton Exchange Membrane Water Electrolysis (PEM), Anion Exchange Membrane Water Electrolysis (AEM), and Solid Oxide Electrolysis Cell (SOEC).^[26-27]The main technical parameters and characteristics of the four types of water electrolysis hydrogen production technologies are asshown in Table 2.

表2 不同电解槽电解水制氢技术对比

Table 2 Comparison of water electrolysis technologies for hydrogen production in different electrolyzers

Parameter	ALK	PEM	AEM	SOEC
Electrolyzer
current density/（A/cm²）	0.2~0.8	1.5~4	0.8~2	0.2~0.4
Operating temperature/℃	70~90	65~80	40~60	500~850
Pressure/10⁵Pa	1~32	1~35	1~32	—
Relative volume	1	~1/3	—	—
Dynamic response time	5~30 min	<10 s	10 s~1 min	up to thermal management
Volatility tolerance range	30%~110%	10%~100%	25%~110%	50%~100%
Operational Requirements	pressure difference needs control	start and stop quickly	start and stop quickly	start and stop difficultly
Electrolyte membrane	Asbestos film，PPS cloth	Perfluorosulfonic acid membrane	anion exchange membrane	solid oxide
anode	Nickel alloy，transition metal oxides and their compounds	Ir、Ru	Nickel-iron alloys	LSM、LSCF
cathode	Nickel alloy，transition metal oxides and their compounds	Pt/C	Ni	Ni-YSZ
pollution	The asbestos film is contaminated	pollution-free	pollution-free	—
technology maturity	TRL9	TRL8	TRL2~3	TRL5~6

2.1.1 Alkaline Water Electrolysis for Hydrogen Production (ALK)

Alkaline water electrolysis for hydrogen production is the oldest electrolysis technology, with a global commercialization level reaching the megawatt scale. Its core feature is the use of high-concentration alkaline solutions (such as KOH or NaOH) as the electrolyte^[28-29], achieving water decomposition through catalysts such as platinum and nickel-based materials. Alkaline water electrolysis for hydrogen production generally uses polysulfone, nickel oxide, asbestos, and other materials as diaphragms. This technology features high maturity and low cost, making it suitable for large-scale hydrogen production scenarios. However, its dynamic response speed is relatively slow, and the electrolyzer volume is bulky; it relies on a liquid electrolyte circulation system, which limits hydrogen purity (usually requiring subsequent purification). Additionally, alkaline electrolyzers operate at low pressures, making it difficult to directly match renewable energy sources. Furthermore, alkaline water electrolysis technology has poor adaptability to pulse techniques; although system design can improve the wide-load dynamic response of alkaline electrolyzers to 0%~100%^[29], its performance improvement direction still relies on upgrading electrolysis equipment rather than pulse control methods.

2.1.2 Proton Exchange Membrane Water Electrolysis for Hydrogen Production (PEM)

Proton exchange membrane water electrolysis technology uses a perfluorosulfonic acid proton exchange membrane as a solid electrolyte, offering excellent proton conductivity, and employs noble metal catalysts such as platinum and iridium coated on the electrode surface^[30-31]. Its advantages include high current density (>2 A/cm²), fast start-stop response (on the order of seconds), and high-pressure hydrogen output (up to tens of megapascals), making it suitable for distributed high-purity hydrogen production. However, high cost remains its primary bottleneck: noble metal catalysts and perfluorosulfonic acid membrane materials are expensive, and the membrane electrode assembly fabrication process is complex. Furthermore, the acidic operating environment imposes extremely high requirements on equipment corrosion resistance, further limiting commercial deployment.

Pulse technology is best suited for PEMWE and has entered the experimental verification stage. Zhang et al.^[32]proposed an innovative pulsed dynamic water electrolysis system, increasing the hydrogen production rate from 51.6 mL/h under constant voltage electrolysis to 66 mL/h, an improvement of approximately 27%; while energy consumption decreased from 5.37 kWh/m³to 3.83 kWh/m³, a reduction of approximately 28%. In situ characterization and finite element analysis results revealed the performance enhancement mechanism: pulsed dynamic electrolysis significantly accelerates proton enrichment at the electrode/solution interface and promotes bubble release on the electrode surface, which not only elucidates the intensification mechanism of the pulse method but also demonstrates the excellent compatibility between pulse technology and PEMWE.

2.1.3 Anion Exchange Membrane Water Electrolysis for Hydrogen Production (AEM)

Anion exchange membrane water electrolysis technology combines the advantages of ALK and PEM, using an anion exchange membrane as the electrolyte to conduct hydroxide ions (OH^-) in an alkaline environment with non-precious metal catalysts (such as nickel and iron-based materials). This technology offers advantages including high efficiency, low cost, and the use of non-precious metal catalysts; current challenges focus on optimizing the long-term stability and ionic conductivity of membrane materials. For instance, researchers at East China University of Science and Technology significantly improved the stability of oxygen evolution catalysts by regulating Co-O-Fe structural units (operating for 250 h at industrial current densities without degradation)^[33-34].

Due to its superior response capability, AEMWE demonstrates good adaptability to pulsed inputs and the fluctuations of wind and solar power generation. However, one of the main challenges currently faced by this technology when coupled with fluctuating inputs is the phenomenon of reverse current occurring after shutdown.^[35], which adversely affects the service life of the catalyst, necessitating the design of catalysts and system control methods capable of resisting reverse current.

2.1.4 Solid Oxide Electrolysis Cell (SOEC) for Hydrogen Production from Water

SOEC uses ceramic electrolytes (such as zirconia) to electrolyze water vapor into hydrogen and oxygen at high temperatures (700–1000 °C). It has the highest theoretical efficiency (>90%) and can utilize industrial waste heat or nuclear energy for heating, making it suitable for large-scale centralized hydrogen production. However, high temperatures lead to poor material durability (such as electrode delamination and electrolyte aging), startup times lasting several hours, and high system complexity. Currently, this technology is still in the transition stage from laboratory to pilot scale, with limited commercial applications. Research by Sichuan University on photoelectrode materials (such as iron oxide stacked structures) provides new ideas for high-temperature electrolysis but has not yet been directly applied to SOEC systems.^[36-38].

Pulse technology has the lowest adaptability to SOECs, primarily due to limitations imposed by their high-temperature environment. In conditions with significant fluctuations in input power and frequent changes in operating parameters, issues such as performance degradation, efficiency decline, and even structural damage are prone to occur.^[39]. SOECs operate at temperatures between 700~900 ℃; thermal stress cycles induced by pulses may accelerate crack propagation in ceramic electrolytes, leading to seal failure. At high temperatures, ionic conduction relies on oxygen vacancy migration, which is minimally affected by pulse modulation, leaving limited room for energy efficiency improvement.

2.2 Analysis of the Mechanism for Enhancing Pulsed Electrolytic Hydrogen Production Performance

The concept of pulses was first proposed by Bowden and Rideal in 1928 for short-term electrochemical measurements^[40]. Subsequently, Butler and Armstrong expanded the application conditions of pulses and demonstrated their unique advantages over traditional methods in kinetic measurements in 1933^[41].

Pulse electrolysis is an alternating electrolysis method that applies pulsed direct current to stimulate non-spontaneous chemical reactions; it is also known as pulsed DC electrolysis. Its electrolysis process can periodically change the current applied to the electrodes and regulate the transport patterns of bubbles on the electrode surface. In contrast, traditional direct current (DC) electrolysis allows variation in only one parameter: the applied voltage. By adopting the pulse electrolysis method, multiple variables can be controlled, including pulse waveform, frequency, and duty cycle. These adjustments can produce different electrolysis effects to meet specific requirements. There are two types of pulse operations: pulse voltage and pulse current. The definitions of square wave pulse parameters are as follows: the voltage changes from an initial value of 0 V (referred to as the off-voltage) to a peak value (referred to as the on-voltage); the on-time (t_on) and the off-time (t_off) sum to define the pulse period; the ratio of the on-time to the pulse period defines the duty cycle; the frequency is the reciprocal of the pulse period; and the amplitude is the difference between the off-voltage and the on-voltage^[42].

2.2.1 Suppress the formation of the electrical double layer and the diffusion layer

When voltage is applied to the electrolytic cell, an electric double layer (EDL) and a diffusion layer are theoretically formed immediately, which increases the required theoretical voltage of 1.23 V to the so-called thermoneutral voltage of 1.48 V^[43]. However, during pulsed electrolysis, the formation of the EDL can be minimized. This is because, in the pulsed power mode, electrolysis is carried out using an alternating "on-off" approach; within the on-time, once the diffusion layer forms, it is difficult for it to thicken rapidly, and it subsequently disappears due to the current interruption. This prevents both the EDL and the diffusion layer from having sufficient time to fully form, thereby reducing the theoretical voltage required for electrolysis and significantly improving energy efficiency^[44].

Rocha et al.^[45]found that after voltage is applied, ions are immediately attracted to the opposite side of the electrode. However, the ions surrounding these ions require some time to rearrange. This delay is called relaxation time. When ions move while the surrounding ions remain stationary, an asymmetric electric field is generated, which slows down the movement of the ions and consumes part of the energy provided by the electric field. When the pulse width is shorter than the relaxation time, the rearrangement energy of the ions surrounding the moving ions is not consumed; this is another reason why pulsed electrolysis has higher efficiency, thus requiring higher pulse frequencies and smaller pulse periods.

Vanags et al.^[46]investigated the current response curve after applying pulsed voltage and found that the charging effect of the electric double layer (EDL) manifests as follows: during the pulse-off period, the charge stored within it dissipates through resistance, but the electrolysis process continues. The authors thus pointed out that the pulse interval must be greater than the relaxation time of the Faradaic process; otherwise, residual reaction accumulation will occur, leading to reduced efficiency and control precision. A beneficial calculation method is to compare the gas expected to be produced by the latter effect with reported energy efficiencies to evaluate whether the pulses cause significant differences. It should be noted that in this study, the duty cycle was as low as 0.5%. This means that to achieve a time-averaged current density greater than that of an equivalent steady-state process, the applied peak current must be at least 200 times the average value.

2.2.2 Accelerate the detachment of bubbles from the electrode surface

Pulsed current significantly improves the dynamic behavior of bubbles on the electrode surface through intermittent power supply. Studies show that in DC electrolysis, continuously generated H₂ and O₂ bubbles tend to accumulate on the electrode surface, forming a gas coverage layer that leads to increased ohmic resistance (i.e., the "bubble shielding effect"). In contrast, the off-time intervals of pulsed current provide a time window for bubble detachment, effectively reducing the gas coverage on the electrode surface.

Trinke et al.^[47]Using high-speed imaging technology, Trinke et al. demonstrated that pulsed current can increase the bubble detachment rate by 40% and enhance the effective active area of the electrode by more than 25%. This is because rapid bubble detachment reduces electrode polarization, lowering the overpotential of the hydrogen evolution reaction (HER) by 50–100 mV, thereby improving energy efficiency. This mechanism is particularly significant in alkaline electrolytes, where high surface tension relies more heavily on optimized bubble management.

Yang et al.^[48]investigated the effects of pulsed electrolysis on bubble removal and electrolysis performance in porous electrodes. They first applied a current density of 500 mA/cm²pulsed current to three types of porous nickel electrodes, with each pulse lasting 5 minutes followed by a 5-minute current off period, repeating cyclically. The results showed that low-frequency pulses effectively improve bubble removal efficiency, thereby increasing the active surface area of the electrodes. This is because the voltage off period provides time for bubble clearance and recovery of the surface area blocked by bubbles. However, if bubbles are confined within the electrode, the voltage drop across the electrode also increases because the bubbles reduce the pathways for liquid flow.

2.2.3 Improvement of electrode material stability

Pulsed electrolysis is expected to extend material life by reducing the time electrodes are continuously exposed to high electrochemical stress. Carmo et al.^[49]Studies show that after operating for 1000 h in pulsed mode, the IrO₂anode experienced a catalyst mass loss of only one-third of that in DC mode. Schalenbach et al.^[50]Comparative experiments indicate that, for the same hydrogen production, the corrosion rate of the IrO₂anode driven by pulsed electricity is reduced by 50% compared to direct current. This is attributed to the relaxation of oxidative erosion on the catalyst by the oxygen evolution reaction (OER) during off-periods. This stability advantage is more significant at high temperatures (>80 °C) or in high-concentration electrolytes.

2.2.4 Thermal Management Optimization

Pulse electrolysis significantly improves the system's thermal distribution and heat dissipation efficiency through periodic cycles of intermittent heat generation and dissipation. Studies indicate that during continuous direct current electrolysis, high-temperature hotspots may form on the electrode surface and in localized regions of the electrolyte due to sustained heat generation, which not only accelerates material degradation but may also trigger electrolyte decomposition.

Kocha et al.^[51]Through experiments and numerical simulations, it was found that in DC mode, the surface temperature of nickel-based electrodes can reach above 85 °C, whereas after adopting pulsed current (30% duty cycle, 1 kHz frequency), the peak temperature drops below 65 °C, effectively reducing thermal stress damage to the electrode structure. Furthermore, the cooling window during the pulse interval reduces overall energy consumption by approximately 12% while delaying the evaporation rate of the electrolyte (such as 30% KOH); this mechanism is particularly important under high-temperature operating conditions.

Although pulsed electrolysis improves energy efficiency and stability through the aforementioned mechanisms, high-amplitude pulses may induce mechanical stress on the electrodes^[52]and reverse current corrosion^[53], and the coupling mechanism between ultra-short pulses (e.g., nanosecond-scale) and electrode dynamic response still requires in-depth analysis using in-situ characterization techniques.

3 Influence of pulse parameters on pulse electrolysis

Compared to steady-state electrocatalysis, pulsed electrocatalysis provides effective and adjustable parameters. In production applications, we can regulate these parameters to achieve better preparation results. In this section, the application of key pulsed parameters in electrocatalysis will be discussed, along with a brief overview of their impact on overall outcomes and their optimization.Table 3also summarizes the relevant content.

表3 不同脉冲参数对比

Table 3 Comparison of different pulse parameters

Parameter type	Parameter selection	Effect on hydrogen production characteristics
Waveform	Square wave	Prevents bubble aggregation effectively；High hydrogen production rate
	Triangle waves	Optimizes reaction kinetics；Low hydrogen production rate
	Sinusoid	Lowest hydrogen production rate
Frequency	-	With the increase of frequency，hydrogen production rate first increases then decreases；Low frequency causes insufficient reactant supply；High frequency impedes sufficient bubble detachment
Duty cycle	Low duty cycle	Accelerates bubble removal，improves energy efficiency
Duty cycle	High duty cycle	Close to DC electrolysis，energy consumption increases
Pulse potential	Low	Energy-saving but yield limitations
Pulse potential	High	Accelerates the reaction but exacerbates corrosion

3.1 Impact of Pulse Waveform

As the core characteristic parameter of pulse electrolysis technology, selecting a specific waveform is a crucial step in researching pulse curves that meet production needs. By choosing different waveforms, the charge distribution state on the electrode surface and ion migration behavior can be altered, significantly impacting the kinetic processes of the electrolytic reaction. These waveforms can be constructed according to the current intensity required at different stages of electrochemical catalysis. Typical waveforms currently under study include square waves, sine waves, sawtooth waves, and stepped waves.

Asshown in Figure 2a, due to their steep rising/falling edge characteristics, square wave pulses form strong transient electric field gradients on the electrode surface, which can effectively penetrate the bubble adsorption layer and prevent bubble accumulation. The square wave pulse curve differs from other waveforms because it is associated with constant potential cycles at the extrema; maintaining the voltage at these extrema for a period of time can improve product selectivity and FE. Considering this characteristic, the square wave has always been the most widely used form in pulsed electrocatalysis.^[54-56].

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图2 脉冲参数：（a）方形波，（b）三角波，（c）正弦波，（d） E_on：导通电压，E_off：关断电压，T_on：开启时间，T_off：关闭时间，E_a：幅值

Fig.2 Pulse parameters. （a） Square wave，（b） triangular wave，（c） sine wave，（d） E_on：On-voltage，E_off：Off-voltage，T_on：On-time，T_off：Off-time，E_a：Amplitude

Dobó et al.^[57]found that, compared to other waveforms, square waves have lower current, are easier to control in applications, and exhibit reproducibility; however, square waves may have a higher ripple factor at fixed average current offset and frequency, which in turn leads to increased power consumption and dissipation in FE.

Zhang et al.^[58]By comparing the potential curves of square waves at a pulsed potential of 1.5 V and frequencies of 0.025, 0.1, 0.2, and 0.5 Hz, low-frequency triangular waves, and sinusoidal pulse waveforms, along with their corresponding current response curves at a peak potential of 1.5 V vs. RHE, this study investigates the impact of pulse waveforms on the hydrogen generation rate in PSWE systems. Experimental results reveal that at the same electrode potential of 1.5 V, the hydrogen production rates for triangular and sinusoidal pulses are significantly lower compared to constant potential and square wave pulses. This indicates that in triangular and sinusoidal pulse waveforms, the duration of electrocatalytic reactions occurring at high potentials is relatively short.

Asshown in Figure 2b, triangular wave pulses can also be used for pulsed electrocatalysis because they enable the study of the impact of varying potentials on reaction kinetics. By linearly increasing the potential during the pulse, sawtooth wave pulses allow us to investigate the response of electrochemical systems to potential changes, determine the optimal potential for specific reactions, and help examine the influence of the slope on reaction kinetics, thereby optimizing reaction conditions.^[59-61]. Asshown in Figure 2c, sine waves are typically used to study the frequency response and impedance of electrochemical systems. Sine waves oscillate between two extremes over time, and the resulting impedance provides information regarding the reactivity and stability of the electrocatalyst.^[62-65].

3.2 Impact of pulse period, frequency, and duty cycle

After selecting the desired pulse shape, the pulse parameters need to be optimized, such asFigure 2dshown, including pulse period, frequency, and duty cycle. As the most commonly used waveform, the discussion on the impact of the following parameters mostly uses square pulses as an example.

The pulse period is the sum of the on-time and off-time (T=T_on+T_off), which is an important parameter in pulsed electrocatalysis. When the pulse period is too short (in the microsecond range), capacitive processes dominate, making it difficult to realize the significant advantage of pulsing to bypass the capacitive current cycle and expand the Faradaic current cycle to improve electrocatalytic efficiency.^[66]. However, T_on and T_off exceeding 60 s or a duty cycle higher than 75% in ultra-long pulses can easily lead to problems such as increased energy consumption, catalyst poisoning, and poor catalyst stability.^[67-68].

Kim et al.^[69]By using a Cu catalyst,T_onandT_offwere each 10 s, at a current density of approximately 14 mA/cm², the FE for C₂₊products was 89%, whereas in the work of Timoshenko et al.^[70], under the same voltage conditions, usingT_on=0.5 s andT_off=4 s pulses resulted in a twofold increase in ethanol production. Therefore, the pulse period should be optimized within a specific range to dynamically adjust the pulse period based on the desired outcomes in terms of product selectivity.

The pulse frequency is the reciprocal of the pulse period (f=1/T), and is a key parameter for selecting the pulse curve; high-frequency pulse electrolysis increases hydrogen production.

Zhang et al.^[32]selected a minimum voltage of 1.95 V to achieve 100% Faradaic efficiency for hydrogen production under pulsed voltage, with a fixed duty cycle of 50% (T_on =T_off), and investigated the effect of pulse frequency on PEMWE hydrogen production by adjusting the pulse period T. It was found that when pulsed voltage was applied, as the pulse frequency increased (f= 0.0125–0.2 Hz), the hydrogen production rate generally showed a trend of first increasing and then decreasing; too low a frequency may lead to insufficient reactant replenishment, while too high a frequency may result in inadequate escape of hydrogen bubbles.

Demir et al.^[71]When investigating the effect of pulsed potential on alkaline water electrolysis performance, it was found that as the frequency increased from 100 kHz to 1200 kHz, the hydrogen flow rate increased from approximately 0.063 mL/s to 0.09 mL/s, asshown in Figure 3a. This is attributed to the immediate removal of trapped bubbles by the pulses; otherwise, such bubbles would hinder the transport of species to the electrode, thereby delaying the entire electrocatalytic process. Furthermore, higher frequencies also lead to an increase in the current density of the electrode, which ultimately promotes electrocatalysis. However, to limit energy consumption, extremely high frequencies should be avoided in practical applications.

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图3 （a） H₂流速对占空比为50%的脉冲频率的依赖性^[71]；（b）各种占空比对法拉第电流和平均电流的影响^[72]；（c）对称和非对称脉冲对C₂₊产物选择性的影响^[66]

Fig.3 （a） The dependence of H₂ flow velocity on pulse frequency with a duty cycle of 50%^[71]；（b） the effect of various duty cycles on Faraday/average currents^[72]；（c） effect of symmetric and asymmetric pulses on the selectivity of C₂₊ products^[66]

The pulse duty cycle is the ratio of the on-time to the pulse period (T_on/T). In pulsed electrocatalysis, the duty cycle is a decisive parameter for Faradaic current and EDL discharge behavior.

Puippe et al.^[72,73]investigated the effect of duty cycle on double-layer charging and discharging in pulse plating,Figure 3bshows the overall effect of different duty cycles on the current waveform.Figure 3b(i) shows a clear distinction between the peak current (the maximum amount of current obtained within a pulse period) and the average current value (the average of the current obtained through the pulse curve).Figure 3b(ii, iii) it can be seen that the anodic pulse width is sufficient for the Faradaic current to reach the total current value. However,Figure 3b(iv) the curve used has a relatively short pulse width and does not allow the Faradaic current value to reach the total current value, so the entire process will be suppressed. Furthermore, fromFigure 3b(v) it can be noted that if the voltage drop during the cathodic width is lower than the anodic width of the pulse, an increase in the average current value will be observed during the application of each pulse period. Therefore, the design of anodic and cathodic widths should be able to identify these trends.

Rocha et al.^[74]investigated the effects of applying voltage and current pulses during alkaline water electrolysis using 3-D Ni-based electrodes. The experimental results showed that using a short duty cycle accelerates bubble removal and reduces the diffusion layer thickness, thereby decreasing the overpotential.

Didomenico et al.^[66]conducted pulsed CO₂reduction at different duty cycles and found that selecting symmetric pulses (50% duty cycle) favors selective C₂₊product formation. Asshown in Figure 3c, the highest selectivity for C₂₊products was observed using symmetric pulses, with a total FE of approximately 80%. This enhanced selectivity is attributed to an optimized microenvironment near the electrode, which promotes C—C coupling.

3.3 Effect of pulse potential

Pulsed potential consists of anodic potential and cathodic potential. Typically, cathodic potential refers to the reduction process, while anodic potential refers to the oxidation process. For selective hydrogen generation, a high potential is usually selected to efficiently produce hydrogen while maintaining a potential difference greater than 1.23 V.^[75]. Additionally, the amplitude of the pulse should be kept at a low level to avoid negative impacts on the water splitting reaction.^[57].

Bui et al.^[76]simulated pulsed CO₂R and designed experiments to summarize the potentials in the pulse waveform, asshown in Figure 4. The results indicate that to effectively convert CO₂into C₂₊ products, a negative cathode potential (approximately -1.55 V vs. RHE) and a pulse range of -0.85 to -1.55 V vs. RHE are relatively ideal. Under these conditions, the pulse increases the current density from 7.20 mA/cm² to 8.10 mA/cm², increasing the total FE of C₂₊ products from 48% to 80%. Compared with the constant voltage mode, the selectivity of C₂H₄ is doubled. This is attributed to the simultaneous increase in pH value and the rise in local CO₂ concentration caused by the increase in current density.

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图4 （a）脉冲幅度、（b）脉冲周期、（c）阴极电位和（d）阳极电位对各种产品的电流密度和法拉第效率的影响^[72]

Fig.4 Effect of （a） pulse amplitude，（b） pulse period，（c） cathode potential，and （d） anode potential on current density and Faraday efficiency of various products^[72]

In summary, these pulse parameters provide continuous opportunities for adjustment to achieve the desired electrocatalytic effect. Appropriately tuning these experimental conditions according to specific goals ultimately facilitates the pulsed electrocatalysis process.

4 Classification of Pulsed Electrolysis Water Hydrogen Production Technology

4.1 Inductive pulse electrolysis for hydrogen production

Inductive pulse electrolysis of water involves applying an inductive voltage significantly higher than the equilibrium voltage to the electrolytic cell. During pulse operation, the double layer stores and releases energy, which affects bubble behavior and alters the effective electrolyte resistance. The current and voltage generated by this method are no longer constant but can be controlled by selecting the pulse frequency and amplitude in the primary circuit. Therefore, this method can be classified as a power control method.

Shimizu^[77]et al. investigated the effects of inductive pulses with a period of 300 ns during alkaline water electrolysis. Ultra-short pulses with a voltage pulse width of approximately 300 ns and a secondary peak voltage range of 7.9~140 V were applied to the electrochemical system at frequencies of 2~25 kHz. The input power was varied by increasing the pulse frequency, asFigure 5ashows. In the experiment, the electrolyte was a 1 mol/L KOH solution, the electrodes were platinum electrodes, and a diode was installed in the secondary circuit to prevent current reversal. The time for diffusion layer formation is given by Equation (1).

（1）

$t=\frac{1}{4{D}_{\mathrm{O}}}{\left(\frac{{X}_{ad}}{X}\right)}^{2}=\frac{{\delta }_{\mathrm{m}\mathrm{a}\mathrm{x}}^{2}}{4{D}_{O}}$

where:D_Ois the diffusion coefficient;X_adis the density of hydrogen ions on the cathode (cm^-2);Xis the concentration of hydrogen ions in the bulk (cm^-3);δ_maxis the thickness of the diffusion layer. Bard and Faulkner previously proposed the same equation. For proton diffusion (D_O=2.3×10^-5 cm²/s), 1 mol/L KOH (X=6.10²⁰ cm^-3), and platinum electrodes (X_ad=10¹⁵ cm^-2), the authors achieved a diffusion layer formation time of approximately 3 μs.

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图5 （a）使用感应脉冲的碱性水电解过程中的电压-时间和电流-时间行为^[77]；（b）感应反冲脉冲的示例以及产生的电压和电流；（c）产生感应反向电压脉冲的实验电路^[46]

Fig.5 （a） Voltage-time and current-time behavior during alkaline water electrolysis using inductive pulses^[77]；（b） examples of inductive recoil pulses and the voltages and currents generated；（c） experimental circuits that generate induced reverse voltage pulses^[46]

In contrast to direct current, under pulsed power conditions, productivity decreases as the voltage in the secondary circuit increases. At relatively low voltages (7.9 and 9.7 V), efficiency improves when the pulse frequency is increased (keeping the pulse width at 300 ns). For pulses with a voltage of 7.9 V and a frequency of 17 kHz, at the same input power (2.6 V at 0.5 A), the hydrogen production rate is 0.07 cm³/s, which is greater than the 0.05 cm of direct current³/s; correspondingly, its hydrogen production efficiency is 44%, greater than the 36% of direct current.

Vanags et al.^[46]Using tungsten and platinum microelectrodes and an alkaline electrolyte, they investigated the hydrogen evolution reaction during pulse electrolysis driven by inductive kickback voltage. The experimental results indicate that square pulses generated in the primary circuit induce extremely intense and high-kickback pulses in the secondary circuit of the transformer. The setup for this experiment and subsequent experiments by the research team is as shown in Figure 5c. The pulses applied to the electrolytic cell feature a high voltage of 60 V, a short width of 1 μs, and an on-time of approximately several hundred microseconds. Microsensors were used to measure the dissolved hydrogen concentration near the cathode. After applying the pulses, a tail-shaped voltage decay was observed, as shown in Figure 5b. Due to the diode in the circuit, the circuit voltage remains greater than zero.

4.2 Voltage pulse electrolysis for hydrogen production

Voltage pulse electrolysis is a water electrolysis technology that periodically changes the voltage across the electrolytic cell. High-voltage pulses (>2.5 V) can accelerate the water decomposition reaction but may exacerbate electrode corrosion; low-voltage pulses (<1.8 V) can extend equipment life but limit the hydrogen production rate.

Lin et al.^[78]investigated the effect of pulsed voltage on water electrolysis. The electrodes were nickel plates, and a proton exchange membrane was used. The catholyte was 30% (by mass) sulfuric acid, and the anolyte was 30% potassium hydroxide. The experiment employed two types of 100 Hz square wave voltage pulses. In the first pulse circuit, the voltage dropped to zero during the off-time, whereas in the second pulse circuit, a base voltage higher than the reversible voltage was applied, ensuring the voltage never reached zero. The tested duty cycles ranged from 10% to 50% in steps of 10%. The results indicated that pulsed voltage led to an increase in current during the on-time but a decrease in average current. For instance, with an on-voltage of 2 V and a duty cycle of 10%, the current during the off-period was 2.4 A, while the current under a constant potential of 2 V was 1.5 A. Therefore, with other variables held constant, pulsed voltage increased the on-current by 60%. However, due to the influence of the duty cycle, even though the current during the on-time was higher, the overall production efficiency remained lower than that of constant current. In summary, pulsed water electrolysis can enhance the on-current, but this benefit comes at the cost of reduced production efficiency because production halts during part of the time (the off-time); nevertheless, the decline in average current suggests that energy savings were achieved.

Radiguès et al.^[79]investigated the application of DC pulsed voltage in hydrogen production. The authors used 3-D porous electrodes made of pure nickel, an anion exchange membrane, and a 1 mol/L KOH solution. The pulse duty cycle was 50%, with frequencies ranging from 2.5 to 250 Hz and on-voltages between 1.3 and 3 V. A baseline voltage of 1.2 V was applied during the off-time. Negative currents were observed during the off-time due to transient electrical effects or reverse reactions. The results showed that for a frequency of 250 Hz, the pulses caused the average current to increase from 0.02 A/cm² to 0.05 A/cm². Furthermore, the authors concluded that there is a synergistic effect among three-dimensional electrodes, forced electrolyte flow, and pulsed voltage, which increased the current by a factor of five compared to two-dimensional electrodes under DC operation and natural convection conditions.

4.3 Hydrogen production from water electrolysis using current pulses

Current pulse electrolysis optimizes the charge distribution on the electrode surface and reduces concentration polarization by periodically switching the current direction or intensity. Its typical applications include reverse pulses (reverse current to remove electrode carbon deposits) and stepped pulses (gradually increasing current density to activate the catalyst).

Vilasmongkolchai et al.^[80]studied the behavior of bubbles during the off-time in pulse electrolysis. The electrolyte used was a 20% (by mass) KOH solution, and the electrodes were made of stainless steel. Current pulses were generated by switching an IGBT transistor circuit on and off, with frequencies ranging from 1 to 100 Hz and current pulses varying from 30 A to 50 A. Experimental results revealed that the time required for bubble rise primarily depends on bubble size and void fraction; a smaller radius or a higher void fraction leads to a longer rise time. Since void fraction is proportional to current density, higher current implies a longer rise time. However, due to the off-time inherent in pulsing, the average production rate of this process is lower than that of conventional processes. Furthermore, when the duty cycle remains constant, the production rate gradually increases as the frequency decreases. This is because the longer stationary time results in fewer bubbles on the electrode when the voltage is turned on.

Tzvetkoff et al.^[81-83]conducted several studies on the use of pulsed current during water electrolysis, aiming to investigate pulse-induced changes on the surface films formed on AISI 316L stainless steel electrodes. The electrolyte was a 6 mol/L KOH solution, with applied pulsed current amplitudes ranging from 12 to 250 mA, frequencies from 0.5 to 10 kHz, and duty cycles from 1% to 99%. After 24 hours of pulsed electrolysis, the samples were analyzed using electrochemical impedance spectroscopy, cyclic voltammetry, scanning electron microscopy, and X-ray photoelectron spectroscopy. Experimental results revealed the formation of Cr(OH)₃thin layers at the cathode, which reduced electronic conductivity; a decrease in Cr content was observed at the anode, leading to reduced electronic and ionic conductivity, attributed to the dissolution of Cr at the anode and its subsequent deposition at the cathode. They concluded that pulsed water electrolysis causes drastic changes on the electrode surfaces, which are closely related to the pulse duty cycle and frequency. At the cathode, these modifications were more pronounced, and the observed number of crystals per unit surface area increased with increasing pulse duty cycle and frequency.

4.4 Power fluctuation water electrolysis for hydrogen production

In scenarios facing renewable energy fluctuations (such as wind and solar variability), the system must possess adaptability across a wide power range (20%~150% of rated power). Ursúa et al.^[84]investigated the impact of power fluctuations on commercial alkaline (30% KOH) electrolyzers. Experimental results revealed that these electrolyzers have a narrow operational range, typically between 25% and 40% of the rated current. Below this current level, gas diffusion through the membrane becomes more pronounced, leading to mixing of hydrogen and oxygen, reduced product purity, and certain safety hazards.

Dobó et al.^[85]investigated the impact of DC power fluctuations in alkaline water electrolysis. In the experiments, the electrolyte used was 30% KOH, the electrodes were made of stainless steel, and the pulse waveform selected was a sine wave. The average voltage ranged from 1.4 to 2.8 V, while the ripple amplitude varied from 0 to 2 V, with pulse frequencies between 1 and 5000 Hz. The experimental results indicated that voltage fluctuations do not alter the gas production rate but increase power consumption, thereby reducing efficiency. Furthermore, fluctuations with high amplitude and low frequency lead to increases in both gas flow rate and power. Taking an average voltage of 2.2 V as an example, under pulse conditions with an amplitude of 2 V and a frequency of 1 Hz, the gas flow rate increased from 0.11 mL/s to 0.45 mL/s, while the power rose from 1 W to 5 W. Consequently, since productivity increased by a factor of 4 while electrical power increased by a factor of 5, the energy efficiency decreased.

5 Wide-power water electrolysis hydrogen production technology adaptable to wind and solar fluctuations

The core of wide-power water electrolysis hydrogen production technology adaptable to wind and solar fluctuations lies in resolving the contradiction between the intermittency of new energy power generation and the power quality requirements of water electrolysis hydrogen production equipment. Its key technologies include the following aspects.

5.1 Impact of wind and solar power volatility

Renewable power sources characterized by wind and solar energy exhibit strong volatility and uncertainty. The resulting power fluctuations reduce voltage stability and power quality; if directly connected to the grid, they adversely affect the grid's regulation capabilities and the durability of water electrolysis hydrogen production equipment. The underlying causes include geographical location, altitude, and topographical variations of power plants, which lead to disparities in wind and solar resource distribution, while diurnal cycles and seasonal periods cause complex fluctuation characteristics in generation output. To mitigate such fluctuations, conventional solutions require configuring large-scale energy storage systems or peak-shaving units. However, these installations may trigger reduced accommodation capacity and insufficient reactive power support for the system, leading to a further decrease in usable wind and solar energy. This necessitates establishing a regulatory framework at the grid planning level that encompasses elements such as grid connection standards, connection methods, and harmonic governance.^[86].

Unstable power input significantly affects the performance and lifespan of electrolysis equipment. Taking wind power-coupled hydrogen production systems as an example, frequent start-stop cycles of the unit not only reduce hydrogen output but also accelerate the aging of power electronic components. Even in highly adaptable PEMWE technology, current fluctuations still cause pressure difference oscillations across the membrane electrode assembly, inducing mechanical stress accumulation and ultimately shortening the device's lifespan. Experimental data shows that under an initial constant current condition of 50 A, the stack efficiency can reach 91%; however, after operating for hundreds of hours with frequent start-stop switching, the electrolysis efficiency drops to around 75%.^[87]. Therefore, the input current and voltage must be limited within a certain range to suppress power fluctuations.

5.2 Fluctuating wind power hydrogen production technology

The global wind power industry is in a phase of rapid development, with China demonstrating a leading trend in this field. According to the national energy strategy deployment, there is an ambitious goal to achieve a total installed wind power capacity exceeding 1000 GW by the mid-21st century. As the scale of wind power continues to expand, posing new challenges to the power system, when wind power penetration exceeds the critical threshold of grid capacity, system frequency stability and inertia support capabilities will face severe tests.^[88]. Against this backdrop, wind-to-hydrogen technology has become an important solution through a multi-level energy conversion mechanism: first, wind turbines capture wind energy and convert it into electrical energy; then, electrolysis devices convert the electrical energy into hydrogen energy, ultimately forming a complete "wind energy-electrical energy-hydrogen energy" chain.

Based on the differences in operation modes and structures of wind power-to-hydrogen power generation systems, wind power-to-hydrogen technology can be classified into two types: grid-connected wind power-to-hydrogen and off-grid wind power-to-hydrogen.^[89], the two systems are as shown in Figure 6.

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图6 两类种风电制氢基本类型。（a）并网型风电制氢；（b）离网型风电制氢^[89]

Fig.6 Two basic types of wind power-driven hydrogen production. （a） Hydrogen production from grid-connected wind power；（b） off-grid wind power hydrogen production

5.2.1 Grid-connected wind power hydrogen production

Grid-connected wind power systems must meet grid stability requirements, but the inherent intermittency and randomness of wind power cause high-frequency fluctuations in its power output. To reduce the impact of these fluctuations on the grid, improve power quality, and achieve efficient synergy with water electrolysis for hydrogen production, it is necessary to optimize system operation by combining advanced control strategies with energy storage technologies.

The volatility of wind power mainly stems from the spatiotemporal variation characteristics of wind speed, including second-level turbulent fluctuations, minute-level gust changes, and hour-level weather system impacts. Such fluctuations can cause grid-connected power to deviate from planned values, leading to issues such as voltage flicker and frequency deviation, and even exacerbating peak shaving pressure on the power grid. For instance, sudden wind speed changes may cause wind power output to vary by more than 20% of the rated power within seconds, exceeding the regulation capacity range of traditional thermal power units, thus requiring dynamic compensation relying on energy storage or hydrogen production systems.

During wind power generation, the grid can utilize a Hybrid Energy Storage System (HESS) combining power-type storage (such as supercapacitors) and energy-type storage (such as lithium-ion batteries and flow batteries) to achieve hierarchical smoothing of fluctuations across different time scales, thereby ensuring the electrolyzer operates at its rated voltage. Hossain et al.^[90]developed an adaptive dynamic regulation mechanism for hydrogen production via electrolysis systems. This strategy achieves wideband power oscillation suppression by real-time control of the electrolyzer's operating modes and innovatively introduces supercapacitor energy storage units for transient energy buffering. Experimental data shows that this solution can reduce the start-stop frequency of the electrolysis device, significantly extending the service life of core components. Huang Dawei et al.^[91]constructed a combined operation system of doubly-fed induction generator (DFIG) wind turbines and electrolyzers, designing a switching control algorithm based on time-series optimization. By generating predictive operation instruction queues, this method ensures the absorption rate of wind power fluctuations while compressing the required configuration capacity of energy storage devices, simultaneously maintaining the system voltage fluctuation rate at a relatively low level. Dinh et al.^[92]Proposed a hydrogen production capacity configuration method utilizing hydrogen production systems to absorb curtailed wind power. An interval estimation method was adopted to establish a statistical model of annual curtailed wind power; with maximum economic benefit as the objective, interval optimization theory was applied to determine the optimal capacity configuration interval for the hydrogen production system. Furthermore, by establishing a multi-attribute decision-making model, the optimal electrolyzer configuration scheme for the hydrogen production system was determined.

5.2.2 Off-grid wind power hydrogen production

Off-grid systems lack grid support and require local energy storage and load management to achieve dynamic balance among wind, storage, and hydrogen. Their technical core lies in enhancing system self-consistency and multi-energy complementarity efficiency. The power balance of off-grid systems highly depends on matching real-time wind speed with load demand. If wind power output falls below load demand, backup power sources (such as diesel generators) must be activated or energy storage released; if output exceeds demand, hydrogen production or wind curtailment is required to prevent equipment overload. In such scenarios, volatility may cause frequent charging and discharging of energy storage, accelerating equipment aging and increasing operation and maintenance costs. To ensure the safe operation of large-scale renewable energy grids, it is necessary to introduce energy storage systems for peak shaving and valley filling, thereby mitigating volatility.

The islanded wind power coupled hydrogen production system demonstrates unique engineering value by avoiding the complexity of grid-connected synchronous regulation. This system eliminates the phase compensation devices and frequency regulation modules required for AC grid connection, allowing the hydrogen production unit to connect directly to the DC bus, thereby reducing system construction costs. Khan et al.^[93]Addressing the challenge of power fluctuation suppression, they constructed a dynamic coupling model of the wind turbine and electrolyzer based on direct torque control. By establishing a multi-physics simulation framework for the electrolyzer under low-voltage and high-current conditions (covering electrochemical polarization, ohmic losses, and heat transfer effects), experiments demonstrated that this scheme can suppress the amplitude of power fluctuations and extend the service life of the electrolyzer. Dixon et al.^[94]Addressing the challenge of power fluctuation suppression, a new power regulation architecture was proposed. Through highly efficient power conversion circuits and hybrid chopper converters, the maximum power point tracking efficiency was significantly improved.

With the gradual maturity of off-grid operation technology, it is believed that in the near future, breakthroughs will be made in the technology for free connection between off-grid power plants and the grid, achieving flexible switching between grid-connected and off-grid operations. Hydrogen production technology using wind power with fluctuating generation will then usher in a new spring.

5.3 Fluctuating photovoltaic hydrogen production technology

The inherent intermittent and fluctuating characteristics of photovoltaic power generation make its large-scale grid integration prone to causing grid frequency instability and power oscillations, whereas shifting towards water electrolysis for hydrogen production can effectively avoid such system risks.^[95]. Current technological evolution focuses on optimizing energy transfer pathways: the direct-coupling mode drives electrolyzers through concentrator arrays to achieve synchronous photoelectric conversion; the indirect-coupling architecture utilizes DC conversion devices to realize maximum power point tracking; and the photothermal synergistic electrolysis process integrates dual pathways of solar thermal collection and photoelectric conversion. These innovative methods elevate overall system efficiency to new levels by reducing energy conversion stages and enhancing thermal energy utilization. Indirect coupling is currently the mainstream approach; compared to direct coupling, it involves additional power electronic equipment, leading to increased costs and reduced efficiency, whereas the direct coupling method imposes higher requirements on the input power adaptability of the electrolyzer.

Xu Lijun et al.^[96]developed a dynamic duty cycle optimization algorithm, effectively improving the efficiency and safety of hydrogen production systems through DC/DC variable topology control; Zhou Hongfei et al.^[97]constructed a fuzzy adaptive MPPT controller, increasing the power tracking response speed to the millisecond level. However, such algorithm-driven optimizations face constraints at the underlying principle level; to break through this bottleneck, one must start from the principles. Khelfaoui et al.^[98]'s outdoor empirical study indicates that system energy efficiency is modulated by both irradiance and temperature, exhibiting wide-range fluctuation characteristics of 18%~40%; Kemppainen et al.^[99]further quantified environmental sensitivity, confirming that the magnitude of efficiency degradation caused by temperature changes is 37% higher than that caused by light fluctuations. Although these experimental conclusions are limited by specific boundary conditions, they provide key parameter benchmarks for modeling. Salari et al.^[100]investigated the impact on system efficiency by establishing a mathematical model to simulate the photovoltaic hydrogen production system and adjusting conditions such as light intensity and temperature. The research results show that while an increase in light intensity enhances hydrogen production capacity, it also reduces system efficiency, whereas temperature reduces the operating voltage of the electrolyzer.

In summary, although DC/DC converters offer definitive advantages in enhancing the efficiency of hydrogen production systems, issues such as conduction and switching losses in power devices, as well as intensified electrolyzer polarization caused by current ripple components, still require systematic solutions. Addressing the characteristics of fluctuating power sources, technological evolution must focus on breaking through high-frequency resonant soft-switching topologies (such as LLC and CLLC), while improving voltage conversion efficiency through variable-mode modulation. In terms of ripple suppression, a composite filtering architecture must be designed based on the electrolyzer's polarization characteristic curve, prioritizing combinations of capacitors with low equivalent series resistance and metallized film types, alongside optimized parameters for magnetically integrated inductors. Notably, core losses and leakage inductance suppression in high-frequency transformers have become key bottlenecks restricting the engineering application of high-frequency soft-switching technologies, requiring multi-objective optimization in the selection of magnetic materials between nanocrystalline alloys and ferrites.

5.4 Wind-solar hybrid power generation for hydrogen production technology

The intermittent nature of renewable energy generation has spurred technological innovations in multi-energy coupling systems. By constructing an energy gradient conversion chain linking electricity, heat, and hydrogen, the temporal fluctuations of wind and solar resources can be effectively smoothed.^[101]. Hou Hui's team^[102]developed an innovative electricity-heat-hydrogen coordinated control model that introduces a multi-scenario robust optimization mechanism. This approach employs probability box methods to quantify the uncertainty of wind and solar output and establishes planning strategies considering extreme weather conditions. While ensuring system safety margins, it exhibits limitations due to optimization conservatism. As a critical buffering component, the lifespan degradation of energy storage units primarily stems from electrode damage caused by deep charging and discharging cycles. Zhang Kun et al.^[103]proposed a fuzzy adaptive control algorithm that dynamically constrains the state-of-charge threshold range. This method achieves power fluctuation suppression while preventing the energy storage system from entering extreme charging or discharging states.

The current adaptability assessment system for water electrolysis hydrogen production suffers from the limitation of single-dimensional metrics, overly relying on the static indicator of hydrogen content in oxygen, and lacking a systematic evaluation of electrolyzer stress responses under dynamic operating conditions. To address this, a multi-stress coupled testing platform can be constructed: detecting mechanical fatigue characteristics of membrane electrode assemblies through stepwise ripple current loading; extrapolating material performance degradation boundaries using accelerated aging experiments; and designing variable-condition interference tests to quantify the nonlinear relationship between overpotential and current density. While these methods provide new insights for dynamic adaptability characterization, their engineering applicability still requires validation through long-term empirical studies.

The construction of integrated energy systems faces multiple spatiotemporal complexity challenges: in the time dimension, it is necessary to coordinate the cross-scale coupling between instantaneous power fluctuations and long-term load changes; in the spatial dimension, it is required to balance the multi-objective conflicts between regional energy complementarity and large-scale grid dispatching; in the behavioral dimension, it is essential to resolve the adaptation contradiction between the strong randomness of volatile power sources and the rigid architecture of traditional energy networks^[104]. To solve these problems, it is necessary to rely on the wide-area measurement and fast control capabilities of smart grids to develop multi-energy flow collaborative dispatching technology based on digital twins^[105], while simultaneously achieving spatiotemporal shifting of wind and solar resources through hydrogen energy storage, ultimately constructing a new energy internet architecture with multi-energy joint storage to provide a systematic solution for the high-proportion accommodation of renewable energy^[106].

6 Conclusion and Outlook

As the global energy structure accelerates its transition towards low-carbonization, pulsed electrolysis for hydrogen production, as an innovative pathway for large-scale green hydrogen generation, demonstrates broad development prospects. However, current research still faces numerous challenges, requiring exploration across dimensions such as material innovation, system optimization, multi-energy coupling, and industrial application to drive technological breakthroughs.

Pulsed electrolysis water hydrogen production technology significantly reduces diffusion layer thickness and accelerates bubble detachment by periodically regulating current/voltage, thereby improving energy efficiency. For instance, high-frequency pulses can inhibit the complete formation of the electric double layer, reducing ion migration relaxation losses, while the transient electric field gradient of square wave pulses can mitigate the bubble shielding effect, among other mechanisms. However, the coupling mechanism between ultra-short pulses and electrode dynamic responses still requires in-depth analysis using in-situ characterization techniques. Regarding electrode stability, although intermittent pulsed power supply alleviates catalyst oxidation, high-amplitude pulses may induce mechanical stress; future efforts need to focus on developing composite electrode materials resistant to pulse impact and quantifying the effects of pulse-induced heating on electrolyte evaporation, etc. While the performance enhancement mechanisms of pulsed technology have been preliminarily clarified, the multi-parameter coupling effects require further decoupling to advance its transition from laboratory scale to industrial-level green hydrogen production.

Intelligent control of pulse parameters will become a key direction for technological upgrades. Existing research indicates that parameters such as pulse waveform, frequency, and duty cycle significantly affect hydrogen production efficiency, electrode lifespan, and energy consumption; however, parameter optimization still relies on empirical experiments. In the future, it is necessary to combine artificial intelligence and machine learning algorithms to establish multi-physics coupling models, achieving dynamic adaptive matching of pulse parameters. For instance, by real-time monitoring of bubble behavior, temperature distribution, and ion concentration gradients within the electrolyzer, pulse waveforms and duty cycles can be dynamically adjusted to maximize energy utilization efficiency. Furthermore, research into the synergistic effects of high-frequency pulses (MHz level) and ultra-short pulses (nanosecond level) is still in its infancy, and the correlation mechanisms with the dynamic response of the electrical double layer on electrode surfaces urgently need to be deeply elucidated.

The deep integration of fluctuating wind and solar power sources with pulsed electrolysis systems is central to the large-scale production of green hydrogen. Although current research has verified the adaptability of pulsed technology to wide-range power inputs, the strong randomness of wind and solar resources still poses a severe challenge to the dynamic response speed and durability of electrolyzers. Future efforts need to optimize multi-energy coupling architectures at the system level, such as developing integrated wind-solar-storage-hydrogen systems. By employing hybrid energy storage (e.g., supercapacitors and hydrogen storage), layered smoothing of fluctuations ranging from seconds to hours can be achieved. Simultaneously, it is necessary to explore direct coupling modes between pulsed electrolysis and off-grid renewable energy sources to reduce intermediate energy conversion stages and improve overall energy efficiency. Notably, innovations in high-frequency resonant soft-switching topologies and low-ripple composite filtering technologies are expected to resolve the contradiction between power device losses and intensified electrolyzer polarization, providing new insights for the efficient utilization of fluctuating power sources.

In the process of industrialization, the long-term operational stability and cost control of large-scale hydrogen production devices remain key bottlenecks. Current laboratory research mostly focuses on short-term performance optimization, lacking long-term empirical data on material aging, mechanical fatigue of membrane electrode assemblies, and system degradation mechanisms. In the future, it is necessary to build a multi-stress coupled testing platform to simulate dynamic loads under actual operating conditions, predicting system lifespan through accelerated aging experiments and digital twin technology. Furthermore, improving the green hydrogen industry chain requires policy guidance and cross-sector collaboration, such as establishing a hydrogen energy standard system, refining carbon trading mechanisms, and promoting demonstration projects like "offshore wind power-seawater hydrogen production" and "desert photovoltaics-green hydrogen chemical engineering" to achieve a closed-loop connection between technological R&D and market demands.

In summary, the future development of pulsed electrolysis for hydrogen production relies on collaborative innovation in materials, systems, algorithms, and policies, seeking a balance among fundamental research, engineering translation, and business models. Only by breaking through technological silos and building an innovation ecosystem with deep integration of industry, academia, research, and application can we accelerate the globalization of the hydrogen economy and provide solid support for the "dual carbon" goals.

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Abstract

Cite this article

1 Introduction

表1 2023年我国主要能源产品产量及增长率

2 Principle of Pulsed Electrolysis for Hydrogen Production

2.1 Introduction to Water Electrolysis Hydrogen Production Technology

图1 酸性（蓝线）和碱性（红线）体系中的OER机理，黑线表示中间体的反应路径

表2 不同电解槽电解水制氢技术对比

2.1.1 Alkaline Water Electrolysis for Hydrogen Production (ALK)

2.1.2 Proton Exchange Membrane Water Electrolysis for Hydrogen Production (PEM)

2.1.3 Anion Exchange Membrane Water Electrolysis for Hydrogen Production (AEM)

2.1.4 Solid Oxide Electrolysis Cell (SOEC) for Hydrogen Production from Water

2.2 Analysis of the Mechanism for Enhancing Pulsed Electrolytic Hydrogen Production Performance

2.2.1 Suppress the formation of the electrical double layer and the diffusion layer

2.2.2 Accelerate the detachment of bubbles from the electrode surface

2.2.3 Improvement of electrode material stability

2.2.4 Thermal Management Optimization

3 Influence of pulse parameters on pulse electrolysis

表3 不同脉冲参数对比

3.1 Impact of Pulse Waveform

图2 脉冲参数：（a） 方形波，（b） 三角波，（c） 正弦波，（d） Eon：导通电压，Eoff：关断电压，Ton：开启时间，Toff：关闭时间，Ea：幅值

3.2 Impact of pulse period, frequency, and duty cycle

图3 （a） H2流速对占空比为50%的脉冲频率的依赖性[71]；（b） 各种占空比对法拉第电流和平均电流的影响[72]；（c） 对称和非对称脉冲对C2+产物选择性的影响[66]

3.3 Effect of pulse potential

图4 （a） 脉冲幅度、（b） 脉冲周期、（c） 阴极电位和（d） 阳极电位对各种产品的电流密度和法拉第效率的影响[72]

4 Classification of Pulsed Electrolysis Water Hydrogen Production Technology

4.1 Inductive pulse electrolysis for hydrogen production

图5 （a） 使用感应脉冲的碱性水电解过程中的电压-时间和电流-时间行为[77]；（b） 感应反冲脉冲的示例以及产生的电压和电流；（c） 产生感应反向电压脉冲的实验电路[46]

4.2 Voltage pulse electrolysis for hydrogen production

4.3 Hydrogen production from water electrolysis using current pulses

4.4 Power fluctuation water electrolysis for hydrogen production

5 Wide-power water electrolysis hydrogen production technology adaptable to wind and solar fluctuations

5.1 Impact of wind and solar power volatility

5.2 Fluctuating wind power hydrogen production technology

图6 两类种风电制氢基本类型。（a） 并网型风电制氢；（b） 离网型风电制氢[89]

5.2.1 Grid-connected wind power hydrogen production

5.2.2 Off-grid wind power hydrogen production

5.3 Fluctuating photovoltaic hydrogen production technology

5.4 Wind-solar hybrid power generation for hydrogen production technology

6 Conclusion and Outlook

References

图2 脉冲参数：（a）方形波，（b）三角波，（c）正弦波，（d） E_on：导通电压，E_off：关断电压，T_on：开启时间，T_off：关闭时间，E_a：幅值

图3 （a） H₂流速对占空比为50%的脉冲频率的依赖性^[71]；（b）各种占空比对法拉第电流和平均电流的影响^[72]；（c）对称和非对称脉冲对C₂₊产物选择性的影响^[66]

图4 （a）脉冲幅度、（b）脉冲周期、（c）阴极电位和（d）阳极电位对各种产品的电流密度和法拉第效率的影响^[72]

图5 （a）使用感应脉冲的碱性水电解过程中的电压-时间和电流-时间行为^[77]；（b）感应反冲脉冲的示例以及产生的电压和电流；（c）产生感应反向电压脉冲的实验电路^[46]

图6 两类种风电制氢基本类型。（a）并网型风电制氢；（b）离网型风电制氢^[89]