Research Progress and Application Prospects of Solid-State Hydrogen Storage Technology
Abstract
:1. Introductions
2. Hydrogen Storage Technologies
2.1. Compressed Gaseous Hydrogen Storage
2.2. Cryogenic Liquid Hydrogen Storage
2.3. Solid-State Hydrogen Storage
2.3.1. Hydrogen Storage Principles
2.3.2. Hydrogen Storage Materials
- (1)
- AB5-type metal hydrides such as LaNi5 [51], CaNi5 [52] (Figure 2a,b), etc., with a mass hydrogen storage density of 1.4–1.8 wt.% and a volumetric hydrogen storage density of up to 115 kg/m3. The dehydrogenation plateau pressure is 0.1–0.3 MPa, and the dehydrogenation temperature is 25–100 °C. These materials have good activation properties and moderate absorption/desorption pressure, but they are expensive (USD >1428.6/ton) and are mainly used as negative electrodes for nickel–metal hydride batteries.
- (2)
- AB2-type metal hydrides such as ZrMn2 [53], TiCr2 [54] (Figure 2c,d), etc., with a mass hydrogen storage density of 1.8–2.2 wt.% and a volumetric hydrogen storage density of up to 130 kg/m3. The dehydrogenation plateau pressure is 0.1–1 MPa, and the dehydrogenation temperature is 25–150 °C. These materials have a high hydrogen storage capacity and good cyclic stability, but they are costly and difficult to activate. They are currently mainly used for large-scale stationary hydrogen storage.
- (3)
- AB-type metal hydrides such as TiFe [55], ZrNi [56] (Figure 3a,b), etc., with a mass hydrogen storage density of 1.5–2.0 wt.% and a volumetric hydrogen storage density of 105–115 kg/m3. The dehydrogenation pressure is 1–3 MPa, and the dehydrogenation temperature is 25–100 °C. These materials have a moderate hydrogen storage capacity and good cycling performance, but they require high hydrogen purity (>99.99%) and are mainly used for hydrogen purification and separation.
- (4)
- A2B-type metal hydrides such as Mg2Ni [57] (Figure 3c), etc., with a high mass hydrogen storage density of 3–5 wt.% and a volumetric hydrogen storage density of up to 110 kg/m3. The dehydrogenation pressure is 0.1–0.3 MPa, but the dehydrogenation temperature is high (250–400 °C). The notable feature of these materials is their high mass hydrogen storage density, but their dehydrogenation kinetics are poor and they are prone to pulverization, so their practical performance needs to be improved.
- (5)
- Complex hydrides such as NaAlH4 [58], LiNH2 [59] (Figure 3d,e), etc., with a mass hydrogen storage density of up to 5–10 wt.%, but a dehydrogenation temperature generally above 150 °C. The advantage of these materials is their high hydrogen storage capacity, but the dehydrogenation process is often accompanied by by-products (such as NH3), causing the reversible hydrogen storage capacity to decrease rapidly. They are currently still in the research stage.
- (1)
- High energy density. The volumetric hydrogen storage density of metal hydrides can reach 100–130 kg/m3, which is three times that of 70 MPa gaseous hydrogen and two times that of liquid hydrogen.
- (2)
- Good safety. Hydrogen storage materials can exist stably at room temperature and atmospheric pressure, and even if damaged, they will not cause a large amount of hydrogen leakage.
- (3)
- Simple system. Solid-state hydrogen storage does not require gas cylinders or compressors, let alone ultra-low-temperature insulation devices, greatly reducing the complexity of the system.
- (4)
- Good economy. Atmospheric storage can significantly reduce equipment costs, and there is no liquefaction power consumption, with operating costs that are only 1/3 of liquid hydrogen.
3. Advancements in Solid-State Hydrogen Storage Systems
3.1. Solid-State Hydrogen Storage System Architecture
- (1)
- Select materials with good thermal and hydrogen conductivity, such as metal materials such as stainless steel and aluminum alloy, or light-weight composite materials such as carbon fiber and glass fiber.
- (2)
- Optimize the size and shape parameters of the container to balance the hydrogen storage capacity, heat dissipation, and layout convenience. Commonly used shapes include cylinders, annuli, corrugated pipe, etc.
- (3)
- Set up porous baffles or fillers in the container, which can fix the hydrogen storage material particles, prevent stress concentration, and promote hydrogen diffusion and heat transfer.
- (4)
- Set up the fin and other enhanced heat transfer elements on the outside of the container to increase the heat transfer area. The fins can be arranged axially, radially or spirally.
- (5)
- When necessary, set up a skeleton, porous matrix, etc., in the container to guide hydrogen transport by capillary force and provide mechanical support.
- (1)
- AB5-type metal hydrides, such as LaNi5 [65,66]. Their hydrogen absorption platform pressure is moderate (0.1–0.3 MPa), and they can release hydrogen at room temperature, but they are expensive and the cost is too high for large-scale hydrogen storage. They are mostly used in small devices such as nickel–metal hydride batteries.
- (2)
- (3)
- Low-temperature AB2-type metal hydrides, such as Ti-Zr-V series [69,70,71]. Their hydrogen storage capacity is relatively high (≥2 wt.%), their dehydrogenation pressure is moderate (0.1–1 MPa), and their price is relatively cheap, but they are difficult to activate and require high-temperature treatment above 400 °C. They are currently mainly used in large-scale stationary hydrogen storage devices.
- (4)
- High-temperature Mg-based metal hydrides, such as Mg2Ni [72]. Their biggest feature are their high mass hydrogen storage density (≥3 wt.%), but their dehydrogenation temperature is also high (300–400 °C), which places high requirements on the heat and mass transfer process, and they are prone to pulverization, so their practical performance needs to be improved.
3.2. Solid-State Hydrogen Storage Device Integration
3.3. Key Technologies for Solid-State Hydrogen Storage
4. Application Scenarios and Market Prospects of Solid-State Hydrogen Storage Technology
4.1. On-Board Vehicular Applications
4.2. Hydrogen Refueling Stations
- (1)
- Atmospheric pressure storage, no need for compressors, saving electricity;
- (2)
- Adsorption at room temperature, no need for low-temperature insulation, simpler steel cylinders or tanks can be used;
- (3)
- Safe and environmentally friendly, even if the hydrogen storage container is damaged, it will not cause a large amount of hydrogen leakage;
- (4)
- Modular design, which can realize the integration of “storage–transportation–refueling”.
4.3. Backup Power Supply
4.4. Power Grid Peak Shaving
5. Challenges and Countermeasures for the Industrialization of Solid-State Hydrogen Storage
5.1. Key Materials and Equipment
- (1)
- High preparation cost. Take AB5-type hydrogen storage alloys as an example. The high-purity powder materials prepared by vacuum induction melting + hydrogen decrepitation treatment have a price as high as USD 11,428–14,285/ton, which is more than four times that of ordinary nickel–metal hydride battery negative electrode materials. Magnesium-based materials have similar problems. Due to the need for an oxygen-free and moisture-free environment in the preparation process, the production cost remains high and it is difficult to achieve large-scale application.
- (2)
- Difficult batch preparation. From laboratory small-scale to industrial scale-up, hydrogen storage materials often face many process bottlenecks. For example, the AB2 type has difficulty obtaining a uniform multi-element solid solution, and Mg2Ni has difficultly avoiding pulverization and sintering. As a result, the performance of materials produced in batches is difficult to guarantee, with rapid decay and a short service life.
- (3)
- Lack of equipment. A high preparation temperature (≥1000 °C), strict atmosphere requirements (high vacuum, high purity hydrogen), and long cycle (several days or even weeks) place very high requirements on the parameter control and air tightness of key equipment, such as melting and hydrogenation. At present, there is still a large gap between the technical level of domestic equipment and foreign equipment, especially large vacuum induction furnaces, plasma spheroidization machines, etc., and core components mostly rely on imports.
- (1)
- Explore new processes for preparing AB2 and AB5-type materials in non-vacuum and atmospheric environments, such as induction suspension melting, electromagnetic stirring heat treatment, etc., and strive to reduce production costs by more than 50%.
- (2)
- Develop new methods for the low-temperature preparation of magnesium-based hydrogen storage materials, such as reaction ball milling, plasma pyrolysis, etc., while reducing the sintering temperature (≤400 °C), suppressing material pulverization, and improving cyclic stability.
- (3)
- Implement the “Solid-State Hydrogen Storage Material Manufacturing Equipment Innovation Project” to focus on the development of ton-level vacuum induction furnaces, rapid hydrogen absorption/desorption systems, high-efficiency powder sorting systems, etc., to break through the industrialization bottlenecks of material preparation and system integration.
5.2. Testing Standards and Specifications
- (1)
- Non-uniform material testing methods. Common testing methods such as PCT and TDS are cumbersome to operate and have poor repeatability, and the test results from different laboratories often vary greatly. And there are a lack of evaluation standards for material aging, life, etc., making it difficult to comprehensively reflect the use performance of materials.
- (2)
- Lack of a system certification system. At present, there are no safety and reliability testing specifications for solid-state hydrogen storage systems in China, and no third-party certification bodies have been established. This not only restricts the promotion and application of solid-state hydrogen storage technology, but also sets obstacles for enterprises to participate in international market competition.
- (3)
- Establish rapid testing methods and testing specifications for the evaluation of hydrogen storage materials, formulate industry standards for key indicators such as PCT performance, thermal stability, anti-pulverization performance, and cycle life, and provide criteria for material selection.
- (4)
- Refer to testing specifications for fuel cells, lithium batteries, etc., and formulate safety testing standards for solid-state hydrogen storage systems as soon as possible, including high and low-temperature cycling, drop, vibration, electromagnetic compatibility, etc., to provide a basis for product safety performance evaluation.
- (5)
- Encourage scientific research institutes and testing institutions with strength to carry out the third-party certification of solid-state hydrogen storage systems, establish a scientific, standardized, and efficient testing and evaluation system, and provide a “pass” for products to enter the market.
5.3. Construction of Innovation Platforms
- (1)
- Relying on innovative carriers such as national key laboratories and manufacturing innovation centers, focusing on basic research and common technologies for solid-state hydrogen storage, and organizing and implementing the “Solid-State Hydrogen Storage Frontier Technology Research Special Project” to provide a continuous technology supply for industrial development.
- (2)
- Actively strive for the support of the national key R&D plan, organize leading enterprises, universities, and research institutes to carry out collaborative research on various links of the industrial chain, and focus on breakthroughs in key technologies, such as the large-scale preparation of hydrogen storage materials, system integration and optimization, and batch assembly.
- (3)
- Support the creation of “Solid-State Hydrogen Storage Industry Innovation Centers” in qualified regions, build public technology R&D platforms, pilot scale-up bases, and testing and certification centers, open up the innovation chain from materials and components to complete vehicles, and accelerate the transformation of scientific and technological achievements into real productivity.
- (4)
- Give full play to the guiding role of venture capital and industrial investment funds, promote the gathering of various innovative resources to key links of the industrial chain by setting up “Solid-State Hydrogen Storage Special Funds” and implementing “Solicitation for Solutions”, and accelerate the industrialization process of scientific and technological achievements.
- (5)
- Encourage local governments and industry associations to take the lead in regularly holding “Solid-State Hydrogen Storage Industry Development Forums”, inviting upstream and downstream enterprises, universities and research institutes, financial institutions, third-party service organizations, etc., to jointly “diagnose and treat” industrial development and form a joint force.
6. Conclusions and Outlook
Author Contributions
Funding
Conflicts of Interest
References
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Type | Type I | Type II | Type III | Type IV |
---|---|---|---|---|
Pressure (MPa) | 17.5–20 | 20–30 | 30–45 | 45–70 |
Volumetric density (kg/m3) | 10–20 | 20–25 | 30–40 | 30–40 |
Gravimetric density (wt.%) | 1.6–1.8 | 3.6–4.2 | 6.2–7.0 | 9.0–10.0 |
Cycle (years) | 15 | 15 | 15–20 | 15–20 |
Technologies | Cryogenic Liquid Hydrogen Storage | Liquid Organic Hydrogen Carriers (LOHC) |
---|---|---|
Volumetric density (kg/m3) | 70 | 70 |
Gravimetric density (wt.%) | 5.7 | 6 |
Pressure (MPa) | 2–4 | 0.5–2 |
Temperature (°C) | −235 | 25 |
Safety | High | Middle |
Materials | LaNi5 | CaNi5 | ZrMn2 | TiCr2 | TiFe | ZrNi | Mg2Ni | NaAlH4 | LiNH2 |
---|---|---|---|---|---|---|---|---|---|
Capacity (wt.%) | 1.8 | 1.4 | 1.5–2.0 | 2 | 1.8 | 1.6 | 3.6 | 5.6 | 10.5 |
Temperature (°C) | 25 | 25 | 25–100 | 25–100 | 100 | 25–100 | 250–350 | 150 | 150 |
Pressure (MPa) | 0.1–0.3 | 0.1 | 0.1–1 | 0.1–1 | 1–2 | 1–3 | 0.1–0.3 | 0.1–1 | 0.1–1 |
Years | Sales Volume of Fuel Cell Vehicles (Units) | Stock of Fuel Cell Vehicles (Units) | ||
---|---|---|---|---|
China | World | China | World | |
2016 | 629 | 2755 | 639 | 2312 |
2017 | 1272 | 4575 | 1911 | 6475 |
2018 | 1527 | 5523 | 3438 | 12,900 |
2019 | 2737 | 10,409 | 6175 | 24,132 |
2020 | 1177 | 9006 | 7352 | 32,535 |
2021 | 1587 | 17,027 | 8939 | 49,562 |
2022 | 3367 | 18,631 | 12,306 | 67,488 |
2023 | 5805 | 14,451 | 12,682 | - |
Years | China | World |
---|---|---|
2016 | 10 | 274 |
2017 | 14 | 328 |
2018 | 31 | 369 |
2019 | 61 | 434 |
2020 | 128 | 560 |
2021 | 218 | 685 |
2022 | 274 | 815 |
2023 | 428 | 1089 |
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Xu, Y.; Zhou, Y.; Li, Y.; Ding, Z. Research Progress and Application Prospects of Solid-State Hydrogen Storage Technology. Molecules 2024, 29, 1767. https://doi.org/10.3390/molecules29081767
Xu Y, Zhou Y, Li Y, Ding Z. Research Progress and Application Prospects of Solid-State Hydrogen Storage Technology. Molecules. 2024; 29(8):1767. https://doi.org/10.3390/molecules29081767
Chicago/Turabian StyleXu, Yaohui, Yang Zhou, Yuting Li, and Zhao Ding. 2024. "Research Progress and Application Prospects of Solid-State Hydrogen Storage Technology" Molecules 29, no. 8: 1767. https://doi.org/10.3390/molecules29081767
APA StyleXu, Y., Zhou, Y., Li, Y., & Ding, Z. (2024). Research Progress and Application Prospects of Solid-State Hydrogen Storage Technology. Molecules, 29(8), 1767. https://doi.org/10.3390/molecules29081767