Thermal Energy Storage Using Phase Change Materials in High-Temperature Industrial Applications: Multi-Criteria Selection of the Adequate Material
Abstract
:1. Introduction
- Temperature range of operation: 400 °C to 600 °C.
- High latent heat storage capacity: high phase change enthalpy.
- Easiness in handling and not imposing health hazard.
- Thermal cycling stability: thermal properties need to remain almost constant during a certain number of thermal cycles.
- Thermal stability: maximum working temperature of at least 50 °C over the range of operation.
- Compatibility with the metal selected for the metal wool and the storage container that will contain the PCM.
- Suitable price.
- Atmospheric stability: PCM should be stable in the atmospheric conditions of the storage container.
2. Methodology
2.1. Selection Methodology
- Materials screeningThe screening was three-fold. First, the scientific literature was thoughtfully scanned to find identified candidates and their disclosed properties. Then, commercially available PCMs were listed. The companies considered were Rubitherm (Germany), PCM Products (United Kingdom), and PLUSS (India). And third, the software FactSage Education 8.3 was used to find potential new candidates.
- Listing of materials’ propertiesWhen reported, different properties were listed. The properties were collected from the literature from the materials’ data sheets. The considered properties were melting temperature, melting enthalpy, specific heat in solid and liquid state, density in solid and liquid state, thermal conductivity, degradation temperature, hygroscopicity, corrosion with potential container materials, and hazardousness of the material (following the standard NFPA 704 [21]).
- Development of a color mapTo facilitate the selection, a color map was developed. For the different key parameters, acceptable and non-acceptable levels were defined, and a color classification was developed. Some examples of such parameters and levels are shown in Figure 4.
- Preliminary tests for materials characterizationTo disregard materials that did not comply with the requirements settled, two tests were carried out. First, a hygroscopic analysis was applied to potential PCMs, such as inorganic salts, identified as hygroscopic or deliquescent in their data sheets. If a salt was pointed out as not adequate, all PCMs with that salt would be disregarded. Second, a one-week corrosion test was performed with the identified PCMs with the pre-selected metals to be used in contact with the PCM.
- Final selection of adequate PCMs to be used.
2.2. Analytical Methods
3. Results
- Melting enthalpy: This property is the one that is directly related to the final energy density of the storage system, therefore the higher the melting enthalpy the better. Keeping this in mind, in this case, materials with melting enthalpies between 889 and 430 J/g were considered very high (dark green), materials with melting enthalpies between 430 and 160 J/g were considered high (light green), materials with melting enthalpies between 160 and 125 J/g were considered medium (yellow), materials with melting enthalpies between 125 and 70 J/g were considered low (orange), and materials with melting enthalpies lower than 70 J/g were considered very low (red).
- Price: Although the price of the storage media is only a part of the total cost of the system, it is clear that the lower the price of the PCM the better. It should be highlighted that the price considered here was not the cost per kg of material, which is the usual purchase cost, but the cost per energy unit, so the comparison between materials would be fairer. Here also five levels were defined, with PCMs with a price higher than 4.07 EUR /kJ were considered very high (red), PCMs with a price between 4.07 and 2.20 EUR /kJ were considered high (orange), PCMs with a price between 2.20 and 0.41 EUR /kJ were considered medium (yellow), PCMs with a price between 0.41 and 0.10 EUR /kJ were considered low (light green), and those with a cost between 0.10 and 0.02 EUR /kJ were considered very low (dark green)
- Hazard level: The standard NFPA 704 was used to label the hazard level of the materials. Here four levels were identified, from non-hazardous (dark green), hazardous (light green), extreme danger (red), and hazardous for transport (dark red).
- Within the material properties, in the first stage the hygroscopicity, deliquescence, and photosensitivity were identified as properties that would jeopardize the materials handling, especially during charging of the storage tanks. Therefore, this information was listed for all materials. Here, five levels were considered, marking photosensitive materials (red), deliquescence materials (orange), hygroscopic materials (yellow), materials where none of these properties would appear (green) or were not reported (grey). This category was not used to discharge materials at this stage, but for further testing in the next step of the methodology.
4. Conclusions
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Temperature Range [°C] | Enthalpy [kJ/kg] | Availability | Price [EUR /kg] | Maximum Working Temperature [°C] | |||||
---|---|---|---|---|---|---|---|---|---|
Criteria | Value for Decision | Criteria | Value for Decision | Criteria | Value for Decision | Criteria | Value for Decision | Criteria | Value for Decision |
T < 2 | 3 | h > 250 | 3 | Yes | 3 | P < 2.5 | 3 | Tmax > 120 | 3 |
2 < T < 3 | 2 | 200 < h < 250 | 2 | No | 0 | 2.5 < P < 5 | 2 | Tmax < 120 or n.a. | 0 |
3 < T < 4 | 1 | 150 < h < 200 | 1 | --- | --- | 5 < P < 10 | 1 | --- | --- |
T > 4 or n.a. | 0 | h < 150 or n.a. | 0 | --- | --- | P > 10 or n.a. | 0 | --- | --- |
# | Materials | Tmelting (°C) | ∆Hmelting (J/g) | Cp solid (J/g·K) | Cp liquid (J/g·K) | ρ solid (kg/m3) | ρ liquid (kg/m3) | k liquid (W/m·K) | Corrosion (mm/Year) | Tdegradation (°C) | NFPA 704 | Ref. |
---|---|---|---|---|---|---|---|---|---|---|---|---|
1 | H 425 | 425 [23] | 220 [23] | 1.54 [23] | - | 2100 [23] | - | 0.57 | - | 1400 [23] | N.H. | [23] |
2 | MnCl2-NaCl (64.33-35.67 wt.%) | 426 [24] | 230 [24] | - | - | - | - | - | - | - | [24] | |
3 | LiF-LiOH (20-80 mol%) | 427 [25] | 869 [25] | 0.80 [25] | 1.00 [25] | 1600 [25] | - | - | - | - | [25] | |
4 | LiF-LiOH (21.33-78.67 wt.%) | 431 [24] | 889 [24] | - | - | - | - | - | - | - | [24] | |
5 | H 430 | 430 [23] | 125 [23] | 1.54 [23] | - | 2160 [23] | - | 0.57 [23] | - | 1400 [23] | N.H. | [23] |
6 | MgCl2-KCl (39-61 wt.%) | 435 [26] | 351 [26] | 0.80 [26] | 0.96 [26] | 2110 [26] | - | 0.81 [26] | 1.00 [27] | 700 [28] | [26,27,28] | |
7 | MgCl2-RbCl (21.65-78.35 wt.%) | 446 [24] | 135.7 [24] | - | - | -- | - | - | - | - | [24] | |
8 | LiCl-MgCl2 (49.65-50.35 wt.%) | 447 [24] | 401 [24] | - | - | -- | - | - | - | - | [24] | |
9 | LiF-LiBr (8.62-91.38 wt.%) | 450 [24] | 275 [24] | - | - | - | - | - | - | - | [24] | |
10 | NaCl-MgCl2 (48-52 wt.%) | 450 [25] | 430 [25] | 0.92 [25] | 1.00 [25] | 2230 [25] | - | 0.95 [25] | - | [25] | ||
11 | CaCl2-KCl-MgCl2-NaCl (55.06-1.95-9.97-33.02 wt.%) | 460 [25] | 245 [25] | - | - | - | - | - | - | -- | [25] | |
12 | LiOH | 462 [29] | 873 [29] | - | - | 1460 [29] | - | - | - | - | [29] | |
13 | CaCl2-KCl-NaCl (64.63-6.29-29.08 wt.%) | 465 [25] | 245 [25] | - | - | - | - | - | - | - | [25] | |
14 | H 485 | 483 [23] | 200 [23] | 1.55 [23] | - | 2220 [23] | - | 0.57 [23] | - | 800 [23] | N.H. | [23] |
15 | KCl-CaCl2-MgCl2 (25-27-48 wt.%) | 487 [25] | 342 [25] | 0.80 [25] | - | 2530 [25] | - | 0.88 [29] | - | - | [25,29] | |
16 | Li2CO3-K2CO3 (47-53 wt.%) | 488 [25] | 342 [25] | 1.03 [25] | 1.34 [25] | 2220 [25] | - | 1.99 [25] | - | 530 [30] | [25] | |
17 | Li2CO3-Na2CO3 (44-56 wt.%) | 496 [25] | 370 [25] | 1.80 [25] | 2.09 [25] | 2320 [25] | - | 2.09 [25] | - | 530 [30] | [25] | |
18 | H 500 | 500 [23] | 300 [23] | 1.55 [23] | - | 2200 [23] | - | 0.57 [23] | - | 800 [23] | N.H. | [23] |
19 | NaCl-CaCl2 (33-67 wt.%) | 500 [25] | 393 [25] | 0.84 [25] | 1.00 [29] | 2160 [25] | - | 1.20 [25] | - | - | [25,29] | |
20 | CaCl2-KCl-NaCl (66-5-29 wt.%) | 504 [29] | 279 [29] | 1.17 [29] | 1.00 [29] | 2150 [29] | - | 1.00 [29] | - | - | [29] | |
21 | H 525 | 525 [23] | 155 [23] | 1.56 [23] | - | 2350 [23] | - | 0.57 [23] | - | 1000 [23] | N.H. | [23] |
22 | H 535 | 535 [23] | 130 [23] | 1.57 [23] | - | 2320 [23] | - | 0.56 [23] | - | 1000 [23] | N.H. | [23] |
23 | Ca(NO3)2 | 560 [29] | 145 [29] | - | - | 2113 [29] | - | - | - | 500 [31] | [29] | |
24 | NaCl-KCl-Na2CO3 (25-33-42 wt.%) | 569 [7] | 249 [7] | 1.34 [7] | 1.41 [7] | 1700 [7] | 2000 [7] | 0.50 [7] | - | [7] | ||
25 | NaCl-Na2CO3 (48-52 wt.%) | 580 [7] | 339 [7] | 1.3 [7] | - | 2000 [7] | - | 0.60 [7] | - | [7] | ||
26 | Li2CO3-Na2CO3-K2CO3 (22-16-62 wt.%) | 580 [25] | 288 [25] | 1.80 [25] | 2.90 [25] | 2340 [25] | - | 1.95 [25] | - | 827 [30] | [25] | |
27 | NaCl-Na2SO4-Na2CO3 (31-30-39 wt.%) | 597 [7] | 221 [7] | 1.20 [7] | 1.30 [7] | 2000 [7] | - | 0.50 [7] | - | [7] |
# | Materials | Tmelting (°C) | ∆Hmelting (J/g) | Hazard Level | Comments | Price (EUR /kJ) |
---|---|---|---|---|---|---|
1 | H 425 | 425 | 220 | 0 | -- | 1.30 |
2 | MnCl2-NaCl (64.33-35.67 wt.%) | 426 | 230 | 3 | photosensitive | 0.24 |
3 | LiF-LiOH (20-80 mol%) | 427 | 869 | 3 | hygroscopic | 352.12 |
4 | LiF-LiOH (21.33-78.67 wt.%) | 431 | 889 | 3 | hygroscopic | 0.35 |
5 | H 430 | 430 | 125 | 0 | -- | 2.28 |
6 | MgCl2-KCl (39-61 wt.%) | 435 | 351 | 3 | hygroscopic | 0.28 |
7 | MgCl2-RbCl (21.65-78.35 wt.%) | 446 | 136 | 3 | hygroscopic | -- |
8 | LiCl-MgCl2 (49.65-50.35 wt.%) | 447 | 401 | 3 | hygroscopic | -- |
9 | LiF-LiBr (8.62-91.38 wt.%) | 450 | 275 | 3 | deliquescent | -- |
10 | NaCl-MgCl2 (48-52 wt.%) | 450 | 430 | 3 | hygroscopic | 0.25 |
11 | CaCl2-KCl-MgCl2-NaCl (55.06-1.95-9.97-33.02 wt.%) | 460 | 245 | 2 | hygroscopic | 1.00 |
12 | LiOH | 462 | 873 | 3 | deliquescent | 0.38 |
13 | CaCl2-KCl-NaCl (64.63-6.29-29.08 wt.%) | 465 | 245 | 2 | hygroscopic | 1.00 |
14 | H 485 | 483 | 200 | 0 | -- | 1.43 |
15 | KCl-CaCl2-MgCl2 (25-27-48 wt.%) | 487 | 342 | 2 | hygroscopic | 0.72 |
16 | Li2CO3-K2CO3 (47-53 wt.%) | 488 | 342 | 3 | hygroscopic | 0.99 |
17 | Li2CO3-Na2CO3 (44-56 wt.%) | 496 | 370 | 3 | hygroscopic | 0.21 |
18 | H 500 | 500 | 300 | 0 | -- | 0.95 |
19 | NaCl-CaCl2 (33-67 wt.%) | 500 | 393 | 2 | hygroscopic | 0.90 |
20 | CaCl2-KCl-NaCl (66-5-29 wt.%) | 504 | 279 | 2 | hygroscopic | 1.26 |
21 | H 525 | 525 | 155 | 0 | -- | 1.84 |
22 | H 535 | 535 | 130 | 0 | -- | 2.19 |
23 | Ca(NO3)2 | 560 | 145 | 3 | deliquescent | 0.12 |
24 | NaCl-KCl-Na2CO3 (25-33-42 wt.%) | 569 | 249 | 2 | hygroscopic | 0.16 |
25 | NaCl-Na2CO3 (48-52 wt.%) | 580 | 339 | 2 | hygroscopic | 0.11 |
26 | Li2CO3-Na2CO3-K2CO3 (22-16-62 wt.%) | 580 | 288 | 3 | hygroscopic | 0.22 |
27 | NaCl-Na2SO4-Na2CO3 (31-30-39 wt.%) | 597 | 221 | 2 | hygroscopic | 0.15 |
PCM | Stainless Steel 314 | Stainless Steel 434 | Alloy 20 | |||
---|---|---|---|---|---|---|
Before tests | ||||||
NaOH | n.a. | n.a. | ||||
Comments (Test temperature) | Failed (T = 450 °C) | Failed (T = 450 °C) | Passed (T = 340 °C) |
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Cabeza, L.F.; Martínez, F.R.; Borri, E.; Ushak, S.; Prieto, C. Thermal Energy Storage Using Phase Change Materials in High-Temperature Industrial Applications: Multi-Criteria Selection of the Adequate Material. Materials 2024, 17, 1878. https://doi.org/10.3390/ma17081878
Cabeza LF, Martínez FR, Borri E, Ushak S, Prieto C. Thermal Energy Storage Using Phase Change Materials in High-Temperature Industrial Applications: Multi-Criteria Selection of the Adequate Material. Materials. 2024; 17(8):1878. https://doi.org/10.3390/ma17081878
Chicago/Turabian StyleCabeza, Luisa F., Franklin R. Martínez, Emiliano Borri, Svetlana Ushak, and Cristina Prieto. 2024. "Thermal Energy Storage Using Phase Change Materials in High-Temperature Industrial Applications: Multi-Criteria Selection of the Adequate Material" Materials 17, no. 8: 1878. https://doi.org/10.3390/ma17081878
APA StyleCabeza, L. F., Martínez, F. R., Borri, E., Ushak, S., & Prieto, C. (2024). Thermal Energy Storage Using Phase Change Materials in High-Temperature Industrial Applications: Multi-Criteria Selection of the Adequate Material. Materials, 17(8), 1878. https://doi.org/10.3390/ma17081878