Submitted:
01 November 2023
Posted:
01 November 2023
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Abstract
Keywords:
1. Introduction
2. Brief Overview of Electrolysis and its Significance in Sustainable Energy Issues: A Careful Energy Analysis
3. Fundamentals of Electrolysis
3.1. Electrolytic Cell Physics
3.2. Electrolyser Analysis at Stack Level
4. Electrolysis: The Main Technologies and the Relevant Differences
4.1. ALK Electrolysis
4.2. PEM electrolysis
4.3. SO Electrolysis
4.4. The Operational Performance of Electrolysers
4.5. The Actual Problems Connected to Electrolysis and Electrolyser Development
5. Energy Analysis of Electrolysis: A Commercial State-of-the-Art and the Additional Problems Connected with Energy System Integration and scaling Up
5.1. System Level and Integration Problem
5.2. Electrolysers’ Scaling Up
5.3. Integration with Renewable Energy Sources in the Electrical Energy System
5.4. Integration of WE with Renewable Energy Sources in the Hard-to-Abate Industrial Context
6. Conclusions
Author Contributions
Funding
Data Availability Statement
Conflicts of Interest
Nomenclature
| ASEC | average specific electricity consumption, kWh/kgH2 |
| ∆G | Gibbs free-energy change, J/molH2 or kWh/kgH2 |
| ∆H | enthalpy change, J/molH2 or kWh/kgH2 |
| ∆S | entropy change, J/molH2/K |
| Ecell | cell voltage, V |
| η | efficiency, % or dimensionless |
| η˅ | overpotential, V |
| F | Faraday constant, C/mole− |
| I | electrical current, A |
| LHV | mass lower heating value, kWh/kg |
| m | mass, kg |
| ṁ | mass flow rate, kg/h |
| N | number of cells, dimensionless |
| n | number of moles, mol |
| P | power, kW |
| Q | thermal power, kW or W |
| T | temperature, °C or K |
| U | voltage, V |
| W | electrical power, kW or W |
| z | number of moles of electrons per mole of H2, mole−/molH2 |
| Subscripts, superscripts, acronyms and abbreviations | |
| AEM | anion exchange membrane |
| ALK | alkaline |
| (aq) | aqueous solution |
| CCUS | carbon capture, utilisation and storage |
| e− | electron |
| EAF | electric arc furnace |
| el | electrical |
| I | defined through the First Law of Thermodynamics |
| (g) | gaseous state |
| gen | generated |
| H2DRI | hydrogen-based direct reduced iron process |
| irr | irreversibilities |
| (l) | liquid state |
| MC | molten carbonate |
| Me | metal |
| ng | natural gas |
| NZE | net zero emissions by 2050 |
| PCC | proton conductive cell |
| PEM | proton exchange membrane |
| PV | photovoltaic |
| rem | removed |
| RES | renewable energy sources |
| rev | reversible |
| SO | solid oxide |
| ° | standard conditions (1 atm and 25 °C) |
| TRL | technology readiness level |
| WE | water electrolysis |
| YSZ | yttria-stabilized zirconia |
References
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| Electrical and thermal demands | Main variables of influence |
|---|---|
| Urev | liquid water/steam; operating temperature, pressure, water activity (Nerst Equation) |
| η˅act | half-reactions, catalysts, operating temperature, pressure, current density |
| η˅ohm | operating temperature, pressure, current density, components’ materials, morphology, and dimensions, thus electrical and ionic conductivity, gases’ bubbles, components’ assembly |
| η˅conc | operating temperature, pressure, current density, products’ removal rate, gases’ bubbles, electrolyte ion concentration/ionic conductivity, electrodes’ porosity and ionic conductivity |
| process heat, steam (only SO) |
operating temperature, thermal source of process heat, heat transfer mechanisms, components’ conductive, convective and radiative properties |
| steam properties (only high-temperature electrolysis) |
| ALK | PEM | SO | |
|---|---|---|---|
| Electrodes and catalysts | an: Ni, Fe, Me oxides cat: Ni/Ni-Co, Me oxides |
an: Ti + Ti/RuO2, IrO2 cat: graphite, Ti + Pt |
an: ceramic (Mn, La, Cr), Ni cat: Zr + Ni/CeOx |
| Separator | diaphragm (usually Zirfon) | polymeric membrane | ceramic membrane |
| Electrolyte | KOH or NaOH | usually Nafion | usually YSZ |
| Temperature (°C) | 60–80 | 50–80 | 800–1000 |
| Pressure (bar) | 2–35 | 15–40 | 1–10 |
| Current density (mA/cm2) | 200–600 | ≤ 2000 | ≤ 2000 |
| Cell voltage (V) | 2.1–2.3 | 2–2.2 | 1.5–1.6 |
| Main advantages | Well tested technology Lower costs Condensation recovery |
High current density Smaller volume Heat recovery from cooling |
Higher electrical efficiency RES- or industrial waste-heat usable Reversible devices |
| Main disadvantages | Corrosive liquid electrolyte H2 purification necessary Bigger volume |
Higher costs Greater water requirement Smaller application experience |
Steam and thermal source of high temperature needed Long warming up Limited lifetime |
| Properties | Reference data |
|---|---|
| Global hydrogen production | 0.1% of the world’s total |
| Electrolysis efficiency | 60–80% efficient depending on the technology |
| Electricity requirements | 55–60 kWh of electricity to produce 1 kilogram of hydrogen through low-temperature water electrolysis. High-temperature electrolysis can be more efficient: the objective is to request around 40 kWh/kg |
| Water requirement | To produce 1 kilogram of hydrogen gas through electrolysis 9–11 kg of water are required depending on the technological option |
| Electrolyser size | The power rating of an electrolyser indicates the amount of electrical power it consumes to produce hydrogen. Commercially available electrolysers vary widely in terms of power, ranging from a few kW to several MW |
| Hydrogen purity | Electrolysers can produce high-purity hydrogen, typically exceeding 99.5% purity. This makes it suitable for various industrial applications and fuel cell technologies |
| Costs of green hydrogen production | The estimated cost of hydrogen ranges from $3 to $6 per kilogram. Ongoing advancements aim to reduce it to $2 or lower |
| Electrolyser lifespan | 10,000 to 40,000 operational hours, depending on type and use |
| Research area | Problem | Solution | Objective |
|---|---|---|---|
| Electrode materials | Finding durable, efficient, and cost-effective electrode materials that can withstand the harsh electrolysis conditions is crucial. | Catalysts like platinum are effective but expensive, driving the need for alternative materials. | Advanced electrodes, catalyst development, material innovations. |
| Electrolyte stability | Electrolyte degradation directly impacts the efficiency and longevity of electrolysis cells. | Developing stable and conductive electrolytes, especially for high-temperature and high-pressure electrolysis. | Exploring coatings of bipolar plates and studying degradation mechanisms. |
| Membrane technology | Improving proton exchange membranes in PEM electrolysis and ceramic membranes in SO electrolysis is essential. | Enhanced durability, selectivity, and reduced cost of membranes can boost the efficiency of electrolysers. | Enhancing selectivity, durability, and ion conductivity. |
| Efficiency enhancement | Considering that hydrogen is still a carrier, the fact that the efficiency of production through electrolysis is far from theoretical limits is a significant barrier to development | Increase efficiency wll over 60%, will increase hydrogen’s decarbonization potential. | Identify configurations, materials and operating conditions that maximize hydrogen production while minimizing the energy consumption. |
| Thermal management | Accurate thermal management is essential to prevent overheating, ensure uniform temperature distribution across the electrolyzer cells, and avoid thermal stress on the materials | Developing effective thermal management systems is a key area of research and innovation minly in the field of SO electrolysis. | Accurate thermal management will enhance efficiency, durability, and overall performance of these devices |
| Scale-up and cost reduction | Scaling up electrolysis technology for industrial and commercial applications while simultaneously reducing production costs is a significant challenge. | Economies of scale and advancements in manufacturing processes | Achieve a global electrolysis capacity which can contribute to decarbonisation, with a competitive production cost. |
| Electrolyser lifespan | Current electrolysers have a lifespan of approximately 10,000 to 40,000 hours of operation, depending on the type and usage. | The lifespan of electrolysers to reduce replacement frequency and associated costs. | Studying degradation mechanisms, exploring durable materials, and enhancing system design. |
| Hydrogen purity | Ensuring the purity of the produced hydrogen is critical, especially for applications in fuel cells. | Developing efficient purification methods to remove impurities like oxygen and moisture is an ongoing challenge. | Achieve hydrogen purity necessary for various end uses sustainably. |
| Dynamic operation | Electrolysers must respond dynamically to varying energy supply to maintain stability and efficiency. | Electrolysers are highly affected by fluctuating conditions, posing a significant challenge when integrating with RES, hindering seamless operation. | Adapting electrolysis systems to handle fluctuating renewable energy inputs efficiently is essential. |
| Standardization | The lack of defined standards, both regarding performance measurement and other parameters, is a significant issue | Establishing International Standards and Regulations for electrolysis technologies, safety protocols, and quality | Create a system of Standards and Regulations which supports the diffusion of WE technology. |
| Life Cycle Analysis | Comprehensive life cycle assessments are necessary to understand the environmental impact of electrolysis technologies fully. | High life cycle cost of electrolysers due to instability, shortened lifespan, and high initial costs requires innovative, cost-effective solutions. | Evaluating the entire life cycle from raw material extraction to end-of-life disposal/recycling. |
| Technology | Nominal power [kW] | H2 rate [Nm3/h] |
ASEC of large sizes [kWh/kgH2] |
H2 production per MW [(kgH2/h)/MW] |
|---|---|---|---|---|
| ALK | 0.5–7000 | 0.1–1400 | 53–63 | 16–19 |
| PEM | 2.4–1250 | 0.5–250 | 52–58 | 17–19 |
| AEM | 2.4–1000 | 0.5–210 | 53–56 | 18–19 |
| SO | 150–2700 | 40–750 | 40–42 | 24–25 |
| Electrolysis technology |
Water state | ΔH° [kWh/kgH2] |
ΔG° [kWh/kgH2] |
U°rev [V] |
ASEC [kWh/kgH2] |
H2 per MW [(kgH2/h)/MW] | Average ηel (ΔG°) [%] |
|---|---|---|---|---|---|---|---|
| Low-T | liquid | 39.4 | 32.7 | 1.23 | 55–60 | 17–18 | 57 |
| High-T | gaseous | 33.3 | 31.5 | 1.18 | 40–42 | 24–25 | 77 |
| Site - Country |
Yearly value of solar energy [kWh/m2/y] |
Min PV surface for a kg of H2 [m2/(kgH2/y)] |
Min PV surface [m2/(tonnesteel/y)] |
|---|---|---|---|
| China - Shanghai | 1450 | 0.23 | 13.8 |
| India - Angul | 1930 | 0.17 | 10.4 |
| United States - Cleveland | 1580 | 0.21 | 12.6 |
| Germany - Dortmund | 1230 | 0.27 | 16.2 |
| Turkey - Payas | 1860 | 0.18 | 10.7 |
| Brazil – Belo Horizonte | 2060 | 0.16 | 9.7 |
| Italy - Taranto | 1870 | 0.18 | 10.7 |
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