Near-room-temperature reversible giant barocaloric effects in [(CH3)4N]Mn[N3]3 hybrid perovskite

Salgado-Beceiro, Jorge; Nonato, A.; Silva, Rosivaldo Xavier; García‐Fernández, Alberto; Andújar, Manuel; Castro‐García, Socorro; Stern‐Taulats, Enric; Señarı́s-Rodrı́guez, M. A.; Moya, Xavier; Bermúdez‐García, Juan Manuel

doi:10.1039/d0ma00652a

Cited by 35 publications

(25 citation statements)

References 32 publications

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“…In particular, typical dT/dp values lie in the range 100-200 K GPa −1 (despite values of up to ~400 K GPa -1 have been reached [51]) that may lead to large ∆T at very low pressure changes, which may result in very good cooling performance. Examples include hybrid organic-inorganic perovskites (HOIPs) [51][52][53][54][55] and spin-crossover (SCO) transitions [56][57][58][59]. In HOIPs, giant transition entropy changes emerge basically due to positional and rotational disorder.…”

Section: Discussionmentioning

confidence: 99%

Advances and obstacles in pressure-driven solid-state cooling: A review of barocaloric materials

Lloveras

Tamarit

2021

MRS Energy & Sustainability

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Solid-state caloric effects promise since decades a disruptive cooling technology that should be more efficient and cleaner than current vapor compression. However, despite relevant achievements have been made, it is still difficult to foresee the time left for the development and wide implementation of competitive devices. Recent progress in the response of materials under hydrostatic pressure offers hope for overcoming some of the shortcomings posed by other solid-state methods and augurs a good outlook for barocaloric cooling, but there are still many struggles ahead to address in order to demonstrate its viability as a commercial cooling technique. Here we briefly review the milestones achieved in terms of barocaloric materials and discuss the pending challenges and expectations for the oncoming years.

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Section: Discussionmentioning

confidence: 99%

Advances and obstacles in pressure-driven solid-state cooling: A review of barocaloric materials

Lloveras

Tamarit

2021

MRS Energy & Sustainability

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“…(b)Reversible adiabatic temperature changes upon 0 → ~1 kbar pressure increase as a function of temperature. Literature data taken from: PG:[12]; C60:[13];[TPrA][Mn(dca)3]:[44]; [(CH3)4N]Mn[N3]3:[45]; MnCoGeB0.03 (asterisk):[46]; (MiNiSi)0.60(FeCoGe)0.40 (diamond) and (MiNiSi)0.61(FeCoGe)0.39 (triangle):[47]; Ni50Mn31.5Ti18.5 (circle):[48].…”

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confidence: 99%

Reversible colossal barocaloric effects near room temperature in 1-X-adamantane (X=Cl, Br) plastic crystals

Aznar

Négrier

Planes

et al. 2021

Applied Materials Today

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Plastic crystals undergo phase transitions with unusually large volume and entropy changes related to strong molecular orientational disordering. These features have led to a resurgent interest in these materials because recently they have shown great potential in solid-state cooling applications driven by pressure. Here we demonstrate that two plastic crystals derived from adamantane -1-Br-adamantane and 1-Cl-adamantane-undergo colossal reversible barocaloric effects under moderate pressure changes in a wide temperature span near room temperature thanks to a relatively small hysteresis and very high sensitivity of the transition temperature to pressure. In particular, 1-Cl-adamantane displays an optimal operational temperature range covering from ~40 K below and up to room temperature, and under a pressure change of 1 kbar this compound outperforms any other barocaloric material known so far. Our work gives strong support to plastic crystals as best candidates for barocaloric cooling. We also provide insight into the physical origin of the entropy changes through the analysis of the disorder on the involved phases.

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“…[6][7][8] For a solid-state compound to be considered a good barocaloric, it should fulfill certain characteristics, specially: near-room-temperature phase transition, associated extremely large entropy changes, and easy-achievable operating pressures to avoid irreversible thermal losses. [9][10][11][12] In a first approximation, the ideal barocaloric material for commercial refrigeration would display colossal thermal changes (barocaloric effects of ΔS > 100 J K -1 kg -1 ) near ambient temperature (from ~315 K down to ~273 K, or even lower in the case of freezing devices), and under the application of pressures well-below 1000 bar. 1 Thus, it is primordial to find materials with colossal and reversible isothermal entropy changes, ΔSrev, (and adiabatic temperature changes, ΔTrev), large barocaloric coefficient (dTt/dp) and strength (ΔSrev/Δp) 13 (sensitivity to pressure) and appropiate operating temperature (Top) 14 , which is the thermal region where the barocaloric effect can be reversibly induced.…”

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confidence: 99%

Hybrid ionic plastic crystals in the race for enhanced low-pressure barocaloric materials

Salgado-Beceiro

Bermúdez‐García

Stern‐Taulats

et al. 2021

Preprint

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In this work, we introduce a new family of barocaloric hybrid organic-inorganic compounds with colossal barocaloric effects. The here reported hybrid materials, [(CH3)3(CH2Cl)N]FeCl4 and [(CH3)3S]FeCl4, exhibit a molecular structure composed by discrete inorganic anions and organic cations with weak elestrostatic interactions. Our calorimetric studies reveal colossal barocaloric effects of similar magnitude than organic plastic crystals (ΔS > 100 J K-1 kg-1) near room temperature and under smaller pressures (p ≤ 1000 bar), which leads to higher barocaloric strengths. Furthermore, these materials exhibit densities similar to barocaloric hybrid perovskites enhancing the volumetric barocaloric effects (ΔS ~ 200 J K-1 l-1), which could provide more compact cooling devices. Therefore, the colossal values of the mass and volumetric barocaloric effects and large barocaloric strength, in addition to the low working pressure and near-room-temperature operation, offer a new family of compounds to further explore in the search for improved barocaloric materials.

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Near-room-temperature reversible giant barocaloric effects in [(CH₃)₄N]Mn[N₃]₃ hybrid perovskite

Abstract: We report giant reversible barocaloric effects in [(CH3)4N]Mn[N3]3 hybrid organic-inorganic perovskite, near its first-order cubic-monoclinic structural phase transition at T0 ~ 305 K. When driving the transition thermally at atmospheric...

Cited by 35 publications

References 32 publications

Advances and obstacles in pressure-driven solid-state cooling: A review of barocaloric materials

Advances and obstacles in pressure-driven solid-state cooling: A review of barocaloric materials

Reversible colossal barocaloric effects near room temperature in 1-X-adamantane (X=Cl, Br) plastic crystals

Hybrid ionic plastic crystals in the race for enhanced low-pressure barocaloric materials

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