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Development of new inorganic shape stabilized phase change materials with LiNO3 and LiCl salts by sol-gel method

  • Original Paper: Sol-gel and hybrid materials for energy, environment and building applications
  • Published:
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Abstract

Latent heat storage with inorganic salts as phase change materials (PCM) is very attractive as these compounds can store a large amount of heat within a small temperature range in a small volume. However, subcooling, phase segregation, and low cycling stability are present in these materials, affecting its applications. One of the ways to reduce or eliminate these disadvantages is to encapsulate or stabilize the inorganic salts. In this work, one-step sol–gel technique was used to create new shape stabilized PCM (SS-PCM) with SiO2 as support material. Four pure salts, LiCl, LiNO3, LiCO3, and CH3COOLi·2H2O, were investigated to evaluate the potential of this sol–gel method, usually used with organic PCM, to obtain inorganic SS-PCM. IR spectroscopy confirmed the polymerization process during the sol–gel process, and show that no chemical reaction occurs between PCM and SiO2 support material, except for Li2CO3. XRD patterns for high salt content (60%) samples show occurrence of salt agglomerations. In addition, the water molecules loss for CH3COOLi·H2O during sol–gel process was observed in SS-PCM. The thermophysical characterization by DSC show that LiCl and LiNO3 properties were improved due to sol gel process, exhibiting higher cycling stability and lower subcooling value than the pure salts. The LiNO3 and LiCl SS-PCM present potential thermal energy storage applications. However, CH3COOLi·H2O and Li2CO3 did not demonstrate potential to be used as PCM under the studied condition.

Highlights

  • Latent heat storage with inorganic salts as phase change materials is attractive.

  • Phase change materials present subcooling and phase segregation.

  • Encapsulating or stabilizing of inorganic salts avoid these disadvantages.

  • One-step sol-gel technique was successfully used to create new shape stabilized PCM.

  • SiO2 was a support material with LiCl, LiNO3, Li2CO3, CH3COOLi·2H2O as PCM.

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Abbreviations

PCM:

Phase c hange materials

SS-PCM:

Shape stabilized phase change materials

TG/DSC:

Thermogravimetry and differential scanning calorimetry

SEM-EDX:

Scanning electron microscopy and energy‐dispersive X‐ray

FT-IR:

Fourier transform infrared

IR:

Infrared

XRD:

X-ray diffraction

TES:

Thermal energy storage

LHS:

Latent heat storage

CSP:

Concentrating solar power plants

SM:

Support material

Li SS-PCM:

Lithium based shape stabilized phase change materials

TEOS:

Tetraethyl ortosilicate

No. cycles:

Number of cycles

Tonset and Tendset :

Initial and final temperature of phase change, respectively

R L :

Latent storage range

ΔH :

Latent heat enthalpy

% ΔH :

Reduction of latent heat enthalpy

ΔHPCM :

PCM latent heats

ΔHSS-PCM :

SS-PCM latent heats

Tm [°C]:

Melting point in Celsius degree

Ts [°C]:

Solidification point in Celsius degree

ΔHm :

Melting latent heat

ΔHs :

Solidification latent heat

Q total :

Total involved heat (sensible and latent)

Cps and Cpl:

Heat capacities of solid and liquid materials, respectively

ΔT :

A range of 100 °C with the melting point of each material in the middle

E density :

Energy density

ρ :

density

References

  1. Dominique L, Tezel FH (2017) A review of energy storage technologies with a focus on adsorption thermal energy storage processes for heating applications. Renew Sust Energ Rev 67:116–125

    Article  Google Scholar 

  2. Chandel SS, Agarwal T (2017) Review of current state of research on energy storage, toxicity, health hazards and commercialization of phase changing materials. Renew Sust Energ Rev 67:581–596

    Article  CAS  Google Scholar 

  3. Mohamed SA, Al-Sulaiman FA, Ibrahim NI, Zahir MH, Al-Ahmed A, Saidur R et al. (2017) A review on current status and challenges of inorganic phase change materials for thermal energy storage systems. Renew Sust Energ Rev 70:1072–1089

    Article  CAS  Google Scholar 

  4. Ye R, Lin W, Yuan K, Fang X, Zhang Z (2017) Experimental and numerical investigations on the thermal performance of building plane containing CaCl2·6H2O/expanded graphite composite phase change material. Appl Energy 193:325–335

    Article  CAS  Google Scholar 

  5. Cabeza LF, Gutierrez A, Barreneche C, Ushak S, Fernandez A, Fernández AI, Grageda M (2015) Lithium in thermal energy storage: a state-of-the-art review. Renew Sust Energ Rev 42:1106–1112

    Article  CAS  Google Scholar 

  6. Fernández A, Ushak S, Galleguillos H, Pérez F (2015) Thermal characterization of an innovative quaternary molten nitrate mixture for energy storage in CSP plants. Sol Energ Mat Sol C 132:172–177

    Article  Google Scholar 

  7. Fernández AG, Ushak S, Galleguillos H, Pérez FJ (2014) Development of new molten salts with LiNO3 and Ca(NO3)2 for energy storage in CSP plants. Appl Energ 119:131–140

    Article  Google Scholar 

  8. Javadian P, Sheppard DA, Jensen TR, Buckley CE (2016) Destabilization of lithium hydride and the thermodynamic assessment of the Li–Al–H system for solar thermal energy storage. RSC Adv 6(97):94927–94933

    Article  CAS  Google Scholar 

  9. Kenisarin M, Mahkamov K (2016) Salt hydrates as latent heat storage materials: thermophysical properties and costs. Sol Energ Mat Sol C 145:255–286

    Article  CAS  Google Scholar 

  10. Lachheb M, Adili A, Albouchi F, Mzali F, Nasrallah SB (2016) Thermal properties improvement of lithium nitrate/graphite composite phase change materials. Appl Therm Eng 102:922–931

    Article  CAS  Google Scholar 

  11. Xu T, Li Y, Chen J, Liu J (2017) Preparation and thermal energy storage properties of LiNO3-KCl-NaNO3/expanded graphite composite phase change material. Sol Energ Mat Sol C 169:215–221

    Article  CAS  Google Scholar 

  12. Zhou D, Eames P (2017) A study of a eutectic salt of lithium nitrate and sodium chloride (87–13%) for latent heat storage. Sol Energ Mat Sol C 167:157–161

    Article  CAS  Google Scholar 

  13. Huang Z, Gao X, Xu T, Fang Y, Zhang Z (2014) Thermal property measurement and heat storage analysis of LiNO3/KCl–expanded graphite composite phase change material. Appl Energy 115:265–271

    Article  CAS  Google Scholar 

  14. Huang Z, Luo Z, Gao X, Fang X, Fang Y, Zhang Z (2017) Investigations on the thermal stability, long-term reliability of LiNO3/KCl–expanded graphite composite as industrial waste heat storage material and its corrosion properties with metals. Appl Energy 188:521–528

    Article  CAS  Google Scholar 

  15. Milián YE, Gutiérrez A, Grágeda M, Ushak S (2017) A review on encapsulation techniques for inorganic phase change materials and the influence on their thermophysical properties. Renew Sust Energ Rev 73:983–999

    Article  Google Scholar 

  16. Wen R, Zhang X, Huang Y, Yin Z, Huang Z, Fang M, Wu X (2017) Preparation and properties of fatty acid eutectics/expanded perlite and expanded vermiculite shape-stabilized materials for thermal energy storage in buildings. Energy Build 139:197–204

    Article  Google Scholar 

  17. da Cunha JP, Eames P (2016) Thermal energy storage for low and medium temperature applications using phase change materials—a review. Appl Energy 177:227–238

    Article  Google Scholar 

  18. Jiang Y, Sun Y, Bruno F, Li S (2017) Thermal stability of Na2CO3-Li2CO3 as a high temperature phase change material for thermal energy storage. Thermochim Acta 650:88–94

    Article  CAS  Google Scholar 

  19. Huang X, Liu Z, Xia W, Zou R, Han RP (2015) Alkylated phase change composites for thermal energy storage based on surface-modified silica aerogels. J Mater Chem A 3:1935–1940

    Article  CAS  Google Scholar 

  20. Wang CL, Yeh KL, Chen CW, Lee Y, Lee HL, Lee T (2017) A quick-fix design of phase change material by particle blending and spherical agglomeration. Appl Energy 191:239–250

    Article  CAS  Google Scholar 

  21. Wu Y, Wang T (2014) Preparation and characterization of hydrated salts/silica composite as shape-stabilized phase change material via sol-gel process. Thermochim Acta 591:10–15

    Article  CAS  Google Scholar 

  22. Qiang G, Tao W (2014) Preparation and characterization of sodium sulfate/silica composite as a shape-stabilized phase change material by sol-gel method. Chin J Chem Eng 22:360–364

    Article  Google Scholar 

  23. Qiang G, Tao W (2015) Study on preparation and thermal properties of sodium nitrate/silica composite as shape-stabilized phase change material. Thermochim Acta 613:66–70

    Article  Google Scholar 

  24. Fan S, Gao H, Dong W, Tang J, Wang J, Yang M, Wang Ge. (2017) Shape‐stabilized phase change materials based on stearic acid and mesoporous hollow SiO2 microspheres (SA/SiO2) for thermal energy storage. Eur J Inorg Chem 14:2138–2143

    Article  Google Scholar 

  25. Serrano A, Martín del Campo J, Peco N, Rodriguez JF, Carmona M (2019) Influence of gelation step for preparing PEG–SiO2 shape-stabilized phase change materials by sol–gel method. J Sol-Gel Sci Technol 89:731–742

    Article  CAS  Google Scholar 

  26. Kamali AR, Fray DJ, Schwandt C (2011) Thermokinetic characteristics of lithium chloride. J Therm Anal Calorim 104:619–626

    Article  CAS  Google Scholar 

  27. Roget F, Favotto C, Rogez J (2013) Study of the KNO3–LiNO3 and KNO3–NaNO3–LiNO3 eutectics as phase change materials for thermal storage in a low-temperature solar power plant. Sol Energy 95:155–169

    Article  CAS  Google Scholar 

  28. Qian T, Li J, Min X, Deng Y, Guan W, Ning L (2015) Diatomite: a promising natural candidate as carrier material for low, middle and high temperature phase change material. Energ Convers Manag 98:34–45

    Article  CAS  Google Scholar 

  29. Kenisarin (2010) High-temperature phase change materials for thermal energy storage. Renew Sust Energy Rev 14:955–970

  30. RUBUTHERM, Phase Change Materials (2017) Remarks subcooling, hysteresis other properties of the SP Products, Ser 2 2:2017

  31. Schoth A, Wagner C, Hecht LL, Winzen S, Muñoz-Espí R, Schuchmann HP, Landfester K (2014) Structure control in PMMA/silica hybrid nanoparticles by surface functionalization. Colloid Polym Sci 292:2427–2437

    Article  CAS  Google Scholar 

  32. Jabbari-Hichri A, Bennici S, Auroux A (2015) Enhancing the heat storage density of silica–alumina by addition of hygroscopic salts (CaCl2, Ba(OH)2, and LiNO3. Sol Energ Mat Sol C 140:351–360

    Article  CAS  Google Scholar 

Download references

Acknowledgements

The authors acknowledge CONICYT/FONDAP No. 15110019 and CONICYT/FONDECYT/REGULAR/ No. 1170675. Y.E. Milián also wants to thank for his CONICYT 2015 No. 21150240 doctorate scholarship and ANT1885 and INGENIERIA2030 CORFO 16ENI2-71940 projects.

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Correspondence to Svetlana Ushak.

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Milián, Y.E., Reinaga, N., Grágeda, M. et al. Development of new inorganic shape stabilized phase change materials with LiNO3 and LiCl salts by sol-gel method. J Sol-Gel Sci Technol 94, 22–33 (2020). https://doi.org/10.1007/s10971-019-05090-4

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  • DOI: https://doi.org/10.1007/s10971-019-05090-4

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