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SCIENCE CHINA Chemistry, Volume 62 , Issue 9 : 1257-1262(2019) https://doi.org/10.1007/s11426-019-9487-0

Lead-free thermochromic perovskites with tunable transition temperatures for smart window applications

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  • ReceivedFeb 20, 2019
  • AcceptedApr 28, 2019
  • PublishedJul 11, 2019

Abstract


Funded by

the Ministry of Science and Technology of China(2017YFA0204502)

the National Natural Science Foundation of China(21873105)


Acknowledgment

This work was supported by the Ministry of Science and Technology of China (2017YFA0204502) and the National Natural Science Foundation of China (21873105). The authors appreciate the 1W1B and 1W2A stations in Beijing Synchrotron Radiation Facility.


Interest statement

The authors declare that they have no conflict of interest.


Supplement

The supporting information is available online at http://chem.scichina.com and http://link.springer.com/journal/11426. The supporting materials are published as submitted, without typesetting or editing. The responsibility for scientific accuracy and content remains entirely with the authors.


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  • Figure 1

    (a) Crystal structure of MA2CuCl4 (structural data taken from ICSD NO. 98-011-0695). The dashed Cu–Cl bonds are longer than the solid ones. (b) XRD patterns of MA2CuCl4, EA2CuCl4 and HA2CuCl4 spin-casting films. (c) Photograph images of color change in these copper-based perovskites upon temperature change (color online).

  • Figure 2

    Cu K-edge (a) EXAFS oscillations for Cu foil and hybrid perovskites (MA2CuCl4, EA2CuCl4, HA2CuCl4) measured at room temperature (RT) and 100 °C (HT). (b) Corresponding Fourier transforms for the curves in (a) (color online).

  • Figure 3

    (a) Raman spectra of the copper-based perovskites at room temperature in the spectral region of 50–300 cm−1; (b–d) Raman spectra of (MA)2CuCl4 (b), (EA)2CuCl4 (c) and (HA)2CuCl4 (d) at room temperature (RT) and high temperature (HT) within the same thermal cycle (color online).

  • Figure 4

    (a) Raman spectra of the copper-based perovskites at room temperature in the spectral region of 2800–3000 cm−1. (b–d) Raman spectra of (MA)2CuCl4 (b), (EA)2CuCl4 (c) and (HA)2CuCl4 (d) at room temperature (RT) and high temperature (HT) within the same thermal cycle (color online).

  • Figure 5

    (a–c) Differential thermal scanning (DSC) analysis of (MA)2CuCl4 (a), (EA)2CuCl4 (b) and (HA)2CuCl4 (c) within the thermal cycle between 300 and 390 K; (d) plots of phase transition temperature (determined by DSC results) versus organic cation in these copper-based perovskites (color online).

  • Figure 6

    (a) Thermochromic performance of PVDF drop-casting films on glass substrates containing (MA)2CuCl4, (EA)2CuCl4 and (HA)2CuCl4, respectively; (b) corresponding absorption spectra at room temperature (RT) and high temperatures (color online).

  • Table 1   Structural parameters of copper-based perovskites obtained from EXAFS spectra

    Sample

    Shell

    CN

    R (Å)

    σ22)×10−3

    R factor

    MA2CuCl4-RT

    Cu–Cl

    3.5

    2.329

    6.3

    0.0036

    MA2CuCl4-HT

    Cu–Cl

    3.4

    2.332

    6.8

    0.0032

    EA2CuCl4-RT

    Cu–Cl

    3.6

    2.343

    6.3

    0.0016

    EA2CuCl4-HT

    Cu–Cl

    3.5

    2.333

    6.8

    0.0014

    HA2CuCl4-RT

    Cu–Cl

    3.5

    2.333

    6.3

    0.0016

    HA2CuCl4-HT

    Cu–Cl

    3.4

    2.323

    7.3

    0.0016

    CN, coordination numbers; R, radial distance; σ2, Debye-Waller factors; R factor, goodness of fit. Fitting parameters were set according to the experimental data in Cu foil by fixing CN=12 from the known crystallographic value.

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