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Colossal barocaloric effects in plastic crystals

Nature volume 567, pages 506–510 (2019)Cite this article

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Abstract

Refrigeration is of vital importance for modern society—for example, for food storage and air conditioning—and 25 to 30 per cent of the world’s electricity is consumed for refrigeration1. Current refrigeration technology mostly involves the conventional vapour compression cycle, but the materials used in this technology are of growing environmental concern because of their large global warming potential2. As a promising alternative, refrigeration technologies based on solid-state caloric effects have been attracting attention in recent decades3,4,5. However, their application is restricted by the limited performance of current caloric materials, owing to small isothermal entropy changes and large driving magnetic fields. Here we report colossal barocaloric effects (CBCEs) (barocaloric effects are cooling effects of pressure-induced phase transitions) in a class of disordered solids called plastic crystals. The obtained entropy changes in a representative plastic crystal, neopentylglycol, are about 389 joules per kilogram per kelvin near room temperature. Pressure-dependent neutron scattering measurements reveal that CBCEs in plastic crystals can be attributed to the combination of extensive molecular orientational disorder, giant compressibility and highly anharmonic lattice dynamics of these materials. Our study establishes the microscopic mechanism of CBCEs in plastic crystals and paves the way to next-generation solid-state refrigeration technologies.

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Fig. 1: Plastic crystals with CBCE for next-generation solid-state refrigeration technology.
Fig. 2: Reorientational dynamics of NPG molecules.
Fig. 3: Anharmonic lattice dynamics of NPG.
Fig. 4: Pressure-dependent phase transition and dynamics of NPG.

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Data availability

The data that support the findings of this study are available from the corresponding author upon reasonable request.

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Acknowledgements

We acknowledge beam time awarded by J-PARC (proposals 2018AU1401 and 2018B0014), SPring-8 (proposals 2018B1095 and 2018A2061) and from ANSTO. B.L., Zhao Zhang, Zhe Zhang, W.R. and Zhidong Zhang were supported by the Hundred Talents Project of CAS and the National Natural Science Foundation of China (grants 11804346, 51671192 and 51531008). T.S. was supported by JSPS KAKENHI (grant number JP18K05032). S.L. and J.W. acknowledge financial support from the US National Science Foundation (grant number CBET-1708968) and the Florida State University through the Energy and Materials Initiative. H.W. acknowledges support from the National Natural Science Foundation of China (grant number 11874429) and the High-Level Talents Project of Hunan Province (grant number 2018RS3021). We also thank W. Zhang, A. Chen and H. Zeng of Setaram for testing the sample using a μDSC 7 EVO.

Reviewer information

Nature thanks Thomas Brueckel, Claudio Cazorla and the other anonymous reviewer(s) for their contribution to the peer review of this work.

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Authors and Affiliations

  1. Shenyang National Laboratory (SYNL) for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang, China

    Bing Li, Zhao Zhang, Zhe Zhang, Weijun Ren & Zhidong Zhang

  2. J-PARC Center, Japan Atomic Energy Agency, Tokai, Japan

    Yukinobu Kawakita, Seiko Ohira-Kawamura, Takanori Hattori, Tatsuya Kikuchi & Kenji Nakajima

  3. Division of Chemical Engineering, Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Osaka, Japan

    Takeshi Sugahara

  4. Department of Physics and Astronomy, University of California, Irvine, CA, USA

    Hui Wang

  5. Hunan Key Laboratory of Super Microstructure and Ultrafast Process, School of Physics and Electronics, Central South University, Changsha, China

    Hui Wang

  6. Department of Mechanical Engineering, Materials Science and Engineering Program, FAMU-FSU College of Engineering, Florida State University, Tallahassee, FL, USA

    Jingfan Wang & Shangchao Lin

  7. Synchrotron X-ray Group, Research Center for Advanced Measurement and Characterization, National Institute for Materials Science (NIMS), Sayo, Japan

    Yanna Chen & Osami Sakata

  8. SPring-8, Japan Synchrotron Radiation Research Institute, Sayo, Japan

    Saori I. Kawaguchi, Shogo Kawaguchi & Koji Ohara

  9. Center for High Pressure Science and Technology Advanced Research, Beijing, China

    Kuo Li

  10. Australian Nuclear Science and Technology Organization (ANSTO), Lucas Heights, New South Wales, Australia

    Dehong Yu & Richard Mole

  11. National Synchrotron Radiation Research Center, Hsinchu, Taiwan

    Shin-ichiro Yano

  12. School of Materials Science and Engineering, University of Science and Technology of China, Hefei, China

    Zhao Zhang & Zhe Zhang

  13. School of Mechanical and Power Engineering, Shanghai Jiao Tong University, Shanghai, China

    Shangchao Lin

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  1. Bing Li
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Contributions

B.L. and Zhidong Zhang conceived the idea. B.L., Y.K., T.K., S.O.-K., T.H. and K.N. performed the neutron scattering experiments at AMATERAS. T.H. calibrated the pressures at PLANET. S.-i.Y. collected the elastic data at SIKA. D.Y. and R.M. conducted the INS measurements at PELICAN. B.L., Y.C., S.I.K., K.O., S.K. and O.S. carried out synchrotron XRD measurements. K.L. analysed the XRD data. T.S. performed pressure-dependent DSC characterizations. H.W. calculated the vibrational spectra. J.W. and S.L. conducted the molecular dynamics simulations. Zhao Zhang, Zhe Zhang and W.R. carried out the in-house XRD and DSC measurements under ambient pressure for testing the samples. B.L. analysed neutron data and wrote the manuscript with discussion and input from all coauthors.

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Correspondence to Bing Li.

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Extended data figures and tables

Extended Data Fig. 1 Diffraction data and crystal structures of NPG.

a, Integrated intensity at −0.1 meV ≤ E ≤ 0.1 meV across Tt ≈ 314 K, obtained at AMATERAS. b, Elastic incoherent scattering intensity as a function of temperature at Q = 2.1 Å−1, measured at SIKA. The inset shows the crystal structure of the monoclinic phase. c, Synchrotron XRD patterns of NPG in the temperature region 273–353 K, obtained at BL02B2 with a wavelength of 0.9994 Å. d, Rietveld refinement of the data at 303 K. Expt, experimental data; Fit, simulated pattern; Diff, difference between experimental and simulated results; Bragg, position of Bragg peaks; Goodness, χ2. e, Temperature dependence of the lattice dimensions across the phase transition.

Extended Data Fig. 2 QENS analysis.

a–c, Energy resolution at different incident energies Ei. d, Activation energy (Ea) of the isotropic reorientational mode, obtained by fitting the temperature dependence of the experimental linewidth Γ. e, f, Simplified reorientational models. Brown, red and pink spheres represent carbon, oxygen and hydrogen atoms, respectively. Distances are given in ångströms. e, Triangles with side length of 1.57 Å indicate the configuration of hydrogen atoms in the methyl groups. The rotational radius of about 0.9 Å corresponds to the distance from the centre of the triangles to the hydrogen atoms. f, The distances between carbon atoms are labelled. The distance between the central carbon atom and C(CH3)–C(CH3), which links the two carbon atoms of the methyl groups, is about 0.84 Å, and that between the central carbon atom and C(CH2OH)–C(CH2OH), which links the two carbon atoms of the hydroxymethyl groups, is about 0.87 Å. These two distances are shown schematically on the right, and their average value is 0.855 Å. This isotropic reorientation model with a rotational radius of 0.855 Å describes a complex reorientational mode consisting of a free rotational reorientation of the whole molecule with respect to an axis perpendicular to C(CH3)–C(CH3) and C(CH2OH)–C(CH2OH), and an isotropic rotational reorientation of this axis.

Extended Data Fig. 3 INS data with higher Ei.

a, b, S(Q, E) obtained at AMATERAS with Ei = 23.72 meV (a) and Ei = 5.93 meV (b). c, d, Multi-component fit of S(Q, E) data at 2 Å−1 ≤ Q ≤ 3 Å−1 with Ei = 5.93 meV at 300 K (c) and 320 K (d). e, General density of state (GDOS), measured at PELICAN. The arrows indicate the peak positions of the mode around 12.7 meV.

Extended Data Fig. 4 QENS data.

a–e, Data obtained with Ei = 2.64 meV at 300 K for an empty cell (a), the pressure-transmitting medium (KBr; b, c) and the sample (d, e). It can be seen that the inelastic signal at Q = 1.3 Å−1 originates from Teflon, whereas the pressure-transmitting medium KBr does not contribute much to the background.

Extended Data Fig. 5 INS data.

a–e, Data obtained with Ei = 23.72 meV at 300 K for the empty cell (a), the pressure-transmitting medium (b, c) and the sample (d, e). The inelastic signals at about 2.7, 4.4 and 5.2 Å−1 are contributed by phonons from Teflon.

Extended Data Fig. 6 Additional pressure-dependence data.

a, S(Q, E) at Ei = 2.64 meV, 178 MPa and 325 K. b, S(Q, E) at Ei = 23.72 meV, 178 MPa and 325 K. c, Elastic incoherent scattering intensity integrated in 0.2 Å−1 ≤ Q ≤ 0.8 Å−1 with a ramping rate of 0.1 K min−1 at 178 MPa. The blue and red arrows indicate the cooling and warming processes, respectively. d, Entropy changes in NPG during heating for pressure changes from the ambient pressure (P0) to the applied pressure (P = 50, 80 and 100 MPa), obtained using μDSC 7 EVO at Setaram, France.

Extended Data Fig. 7 Theoretical modelling.

a, Atomic structure of the NPG molecule and its orientation, defined in three-dimensional space using angles α and θ in molecular dynamics simulations. Vector L points from the central carbon atom to a corner carbon atom of the molecule. b, Simulation results showing the distribution of the orientations of the molecules as a function of pressure at 340 K. It can be seen that a pressure of 100 MPa already effectively suppresses disorder. c, Full vibrational spectrum of NPG calculated by DFT. We note that there is a gap between 200 and 350 meV.

Extended Data Table 1 Evaluation of entropy changes using the Clausius–Clapeyron relation on a few plastic crystals12,13,14,20
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Extended Data Table 2 Entropy changes of systems shown in Fig. 1c
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Extended Data Table 3 Crystal structure information, determined by XRD measurements at 303 K and by DFT calculations
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Li, B., Kawakita, Y., Ohira-Kawamura, S. et al. Colossal barocaloric effects in plastic crystals. Nature 567, 506–510 (2019). https://doi.org/10.1038/s41586-019-1042-5

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