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    • 专利摘要:
    Process and cooling device induced by an external stimulus on an organic-inorganic caloric hybrid material. Cooling process induced by an external stimulus that involves applying an external stimulus selected between hydrostatic pressure, uniaxial pressure, electric field and illumination with light, to an organic-inorganic hybrid material of crystal structure with hexagonal packing, of formula ABX3 (I), where: A is a particular monovalent organic cation or a certain mixture of monovalent organic cations or a certain mixture of monovalent organic cations and monovalent inorganic cations, B is a particular divalent metal cation, a certain mixture of divalent metal cations, or a certain 50/50 atomic mixture of a monovalent cation and a trivalent cation, and X is a halide anion or a mixture thereof. Device with refrigeration capacity induced by an external stimulus, comprising the previous organic-inorganic hybrid material, as well as hybrid organic-inorganic material of formula [(CH3)2 NH2 ] PbCI3 (Ia) and its preparation procedure. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2711048A1
    申请号:ES201731260
    申请日:2017-10-27
    公开日:2019-04-29
    发明作者:Garcia Juan Manuel Bermudez；Rodriguez Maria Antonia Senaris；Andujar Manuel Sanchez；Garcia Socorro Castro；Fernandez Alberto Garcia；Diaz Ramon Pedro Artiaga；Beceiro Jorge Jose Lopez
    申请人:Universidade da Coruna；
    IPC主号:
    专利说明:

    [0001]
    [0002] Process and device of refrigeration induced by an external stimulus on a hybrid material organic-inorganic caloric
    [0003]
    [0004] The present invention is related to a refrigeration system based on the use of an organic-inorganic caloric hybrid material that is sensitive to an external stimulus, with a device comprising said heat materials and means for applying said stimulus, as well as with a new organic-organic-calorie hybrid material.
    [0005]
    [0006] STATE OF THE ART
    [0007]
    [0008] Currently, more than 20% of the world's energy consumption is dedicated to the refrigeration of food, beverages, medicines, electronic devices, machines, vehicles and / or homes. Conventional refrigeration technologies are based on compression / expansion of gases at relatively low pressures, P <70 bar. However, most of these machines work with toxic and / or polluting refrigerant gases, dangerous chemical compounds (ammonia, NH3), or greenhouse gases, such as hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs), for example the R- 134a (CH2FCF3) having a GWP global warming index of 1300 with 1 being that of CO2. So any leakage, breakage or inadequate management of waste at the end of the useful life of the machine is a danger to the environment.
    [0009]
    [0010] In this context, the European Union will restrict in 2020 (EU Regulation No 517/2014) the use of greenhouse gases that contribute to global warming, HCFCs and HFCs among others, although it can be said that today there is no alternative for replace them that is viable and ecological.
    [0011]
    [0012] A promising alternative to refrigeration gases are the so-called heat materials. Heat materials are solid substances that undergo great thermal changes (isothermal changes of entropy or adiabatic temperature changes) through the application of external stimuli. The Stimuli that induce these caloric effects include hydrostatic pressure, uniaxial pressure, the magnetic field, or the electric field. Thus, the known heat materials are divided into: (i) barocaloric materials (when the heat effect is induced by a hydrostatic pressure), (ii) elastocaloric materials (when the heat effect is induced by uniaxial pressure), (iii) materials magnetocaloric (when the heat effect is induced by a magnetic field) and (iv) electrocaloric materials (when the heat effect is induced by an electric field).
    [0013]
    [0014] The first solid state refrigerator at room temperature was proposed by Gerald Brown in J. Appl. Phys., 1976, vol. 47, pp. 3673-3680 taking advantage of the magnetocaloric effect of gadolinium. Currently, solid heat materials for refrigeration are based on expensive metals or alloys, usually rare earth, mainly with magnetocaloric effects. In addition, the known heat materials present a series of drawbacks that hinder their implementation in commercial technologies. In particular, magnetocaloric materials, in addition to being composed mostly of expensive metals or rare earth alloys, need relatively high magnetic fields (greater than 2 T). As for the electrocaloric materials, these heat effects induced by electric field have been observed in thin sheets with a very small thermal mass, since known electrocaloric materials tend to degrade rapidly in working conditions. On the other hand, the baro and elastocaloric materials have the advantage that the hydrostatic and uniaxial pressure are simple to apply and do not lead to the rapid decomposition of the material under working conditions. However, very few materials with a baro- and elastocaloric effect are currently known, which are also generally expensive materials and show a limited response to pressure and require relatively high pressures (P> 1000 bar). (see X. Moya et al., Nature Materials, 2014, vol.13, pp. 439-450).
    [0015]
    [0016] The organic-inorganic hybrid materials have undergone a rapid development in recent years. These organic-inorganic hybrid materials integrate inorganic cations linked by organic or inorganic anions and form a mono-, bi- or three-dimensional network that can house organic species (both molecular, cationic or anionic) and sometimes mixtures of organic species with cations inorganic
    [0017]
    [0018] An organo-inorganic solid material with barocaloric effect is known for refrigeration applications, in particular, the compound [(CH3CH2CH2) 4N] [Mn (N (CN) 2) 3] with crystal structure with cubic packing based on octahedrons [Mn ( (N (CN) 2) 3) 6] that share their vertices forming cavities where the cations [(CH3CH2CH2) 4N] + are lodged (see JM Bermudez-Garda et al., Nature Communications, 2017, 8, 15715). It has also been theoretically predicted 16 other materials that could show barocaloric effect, however this effect has not been demonstrated experimentally. (see J. M. Bermudez-Garda et al., in J. Phys. Chem. Lett., 2017, vol.8, pp. 4419-4423). In particular, among the materials cited is the family of materials [CH3NH3] PbX3 (X = I-, Cl-, Br-) with crystal structure with cubic packing based on octahedrons [PbX6] that share their vertices forming cavities where they are housed the [CH3NH3] + cations that are predicted to have a relatively poor barocaloric effect for refrigeration applications due to low sensitivity to pressure and / or to a very low transition temperature of the materials (parameter that marks the working temperature of said material). Thus, the fact that the heat effect occurs at very low temperatures will make any practical application as a refrigeration material difficult.
    [0019]
    [0020] In view of the state of the art, there is still a need to find new solid heat materials useful in refrigeration applications that are more efficient and result in economic technological solutions that are respectful of the environment.
    [0021]
    [0022] EXPLANATION OF THE INVENTION
    [0023]
    [0024] The inventors have noticed that organic-inorganic hybrid materials of general formula ABX3 (I), where A are organic cations of medium size (those cations with a volume comprised between 13 A3 - 275 A3) or mixtures of these organic cations with cations inorganic, B are metal cations and X are halides, they present a crystal structure with hexagonal packing based on octahedra [BX6] that share vertices and faces forming cavities where they house the cations A, and undergo a solid-solid phase transition induced by an external stimulus such as hydrostatic pressure, which gives rise to an improved barocaloric effect that can be used more efficiently for refrigeration applications. The cooling capacity of these materials is associated with isothermal changes of entrop ^ a or adiabatic temperature changes induced by external stimuli in the fence of the solid-solid transition temperature which is the one that marks the working temperature of said material, ie , the temperature at which the material itself must be to function as a refrigerator.
    [0025]
    [0026] An advantage of using organic-inorganic hybrid materials such as those of the present invention in a refrigeration process is that they are solid materials, which avoids the use of dangerous gases and contaminants, allows having a compact refrigeration system, they are easy to manipulate and in the case of an accidental leak are easier to contain than a gas or a liquid. The organic-inorganic hybrid materials of the present invention are much cheaper materials than rare earth metals and alloys that are being used as heat materials, are sensitive to hydrostatic pressure and uniaxial pressure, and integrate elements sensitive to the magnetic field, field electrical and light, being able to induce a heat effect by one or several of these stimuli. Additionally these materials are lightweight, which lightens the weight of the cooling device. They are also more flexible than the known heat materials based on the metals and rare earth alloys that are being used, and can be included in flexible devices such as shoe insoles, textiles, the new generation of flexible telephones, etc.
    [0027]
    [0028] Unlike [(CH3CH2CH2) 4N] [Mn (N (CN) 2) 3] that presents crystal structure with cubic packing or the family of materials [CH3NH3] PbX3 (X = I ", Cl", Br ") that also present Crystalline structure with cubic packing, the organic-inorganic hybrid materials with general formula ABX3 of the present invention have crystal structure with hexagonal packing, said structure allows these compounds to have a sensitivity to pressure much greater than materials with crystalline structure with cubic packing (see FIGs 1-3).
    [0029]
    [0030] The barocaloric effect of the compounds of the present invention is considerably higher than the predicted for the compounds [CH3NH3] PbX3 (X = I-, Cl-, Br-), which would be the closest, and also have the additional advantage that they have a better working temperature, much closer at room temperature, which greatly facilitates its application as a refrigeration material.
    [0031]
    [0032] The compounds of the present invention exhibit a barocaloric effect similar to the compound [(CH3CH2CH2) 4N] [Mn (N (CN) 2) 3] although they have additional advantages since they can be manufactured more simply, ecologically and economically than the material [(CH3CH2CH2) 4N] [Mn (N (CN) 2) 3].
    [0033]
    [0034] For the purposes of the invention, not only the hydrostatic pressure can be used as a stimulus but also other stimuli that give rise to the solid-solid phase transition such as uniaxial pressure, electric field or light illumination. These effects are derived according to theoretical calculations obtained from the structural data of the compounds of the present invention. According to the knowledge of the inventors, no organic-inorganic hybrid material has been described with elastocaloric, electrocaloric or photocaloric effect for refrigeration applications.
    [0035]
    [0036] The barocaloric effect and the elastocaloric effect are both induced by pressure, the former by hydrostatic pressure (pressure exerted equally on the entire surface of the material) and the latter by uniaxial pressure (pressure exerted only along an axis). Large thermal changes (isothermal changes of entropy or adiabatic temperature changes) are produced by the application of a hydrostatic or uniaxial pressure. The elastocaloric effect is advantageous in those cases in which the material deforms more in one axis than in another, but in principle both effects can be considered similar. In the case of the photocaloric effect and the electrocaloric effect, great thermal changes are also produced (isothermal changes of entropy or adiabatic temperature changes) by means of the application of lighting (light, laser, etc.) or the application of an electric field, respectively.
    [0037]
    [0038] Finally, the compounds of the present invention have the additional advantage over other known organic-inorganic hybrid materials which is that they are thermally stable and / or in light conditions even under a humidity of up to 65% for a prolonged period of time.
    [0039]
    [0040] Thus, a first aspect of the present invention is related to a cooling process induced by an external stimulus which comprises applying an external stimulus selected from hydrostatic pressure, uniaxial pressure, electric field and lighting with light, to an organic-inorganic hybrid material of crystal structure with hexagonal packing, of general formula: ABX3 (I), where: A is selected from the group consisting of a monovalent organic cation, a mixture of monovalent organic cations, and a mixture of monovalent organic cations and monovalent inorganic cations; the monovalent organic cation is selected from the group consisting of hydrazinium ([NH3NH2] +), hydroxylammonium ([NH3OH] +), formamidinium ([CH (NH2) 2] +), guanidinium ([C (NH2) 3] +) , azetidinium ([C3NH8] +), dimethylammonium ([(CH3) 2NH2] +), ethylammonium ([CH3CH2NH3] +), azetididiminium ([CH3C (NH2) 2] +), tetramethylammonium ([(CH3) 4N] +) , imidazolium ([C3N2H5] +), trimethylammonium ([(CH3) 3NH] +), isopropylammonium ([(CH3) 2CNH3] +), pyrrolidinium ([(C4H4) NH2] +), isobutylammonium ([(CH3) 2CH3) 2N] +), diethylammonium ([(CH3CH2) 2NH2] +), and phenylammonium ([(C6H5) NH3] +); the mixture of monovalent organic cations is a mixture of any of the aforementioned organic cations, including also [CH3NH3] +; and the mixture of organic cations and monovalent inorganic cations is a mixture of any of the aforementioned organic cations with one or more inorganic cations selected from the group consisting of Cs +, Rb +, NH4 +; B is selected from the group consisting of: a divalent metal cation, a mixture of divalent metal cations, and a 50/50% atomic mixture of a monovalent cation and a trivalent cation, wherein: the divalent metal cation is selected from the group consisting of: Mg + 2, Ca + 2, Sr + 2, Mn + 2, Fe + 2, Co + 2, Ni + 2, Cu + 2, Zn + 2, Cd + 2, Pb + 2 , Sn + 2, and Sb + 2; the monovalent metal cation is selected from the group consisting: Ag +, Na +, K +, Tl +, and Cu +; and the trivalent cation is selected from the group consisting of: Cr + 3, Fe + 3, Bi + 3, In + 3; Y + 3, Lu + 3, La + 3, Ce + 3, Pr + 3, Nd + 3, Pm + 3, Sm + 3, Eu + 3, Gd + 3, Tb + 3, Dy + 3, Ho + 3, Er + 3, Tm + 3, and Yb + 3; and X is a halide anion selected from the group consisting of F ", Cl-, Br", I ', and a mixture thereof.
    [0041]
    [0042] By monovalent organic cation is meant herein an organic loading cation 1. The monovalent organic cation A of the present invention has a medium size with a volume between 13 A3 - 275 A3. By "divalent organic cation" is meant a cation with charge 2. By "trivalent organic cation" is meant a charge cation 3.
    [0043]
    [0044] In a particular embodiment, the refrigeration process is that where in the organophosphorus organic material, A is a monovalent organic cation selected from the group consisting of dimethylammonium ([(CH3) 2NH2] +), ethylammonium ([CH3CH2NH3] +), tetramethylammonium ([(CH3) 4N] +), trimethylammonium ([(CH3) 3NH] +), isopropylammonium ([(CH3) 2CNH3] +), isobutylammonium ([(CH3) 2CH3) 2N] +), and diethylammonium ([(C ^ C ^ ^ NH ^).
    [0045]
    [0046] In another particular embodiment, the cooling process is that where in the organophosphorus-organic material A is [(CH3) 2NH2] +.
    [0047]
    [0048] In another particular embodiment, the refrigeration process is that wherein in the organic-inorganic hybrid material, A is a monovalent organic cation which is selected from the group consisting of hydrazinium ([NH3NH2] +), hydroxylammonium ([NH3OH] +), formamidinium ([CH (NH2) 2] +), and guanidinium ([C (NH2) 3] +).
    [0049]
    [0050] In another particular embodiment, the refrigeration process is that wherein in the organic-inorganic hybrid material, A is a monovalent organic cation which is selected from the group consisting of, imidazolium ([C3N2H5] +), pyrrolidinium ([(C4H4) NH2 ] +), and phenylammonium ([(C6H5) NH3] +).
    [0051]
    [0052] In another particular embodiment, the refrigeration process is that wherein in the organic and inorganic hybrid material, A is the mixture of monovalent organic cations including also [CH 3 NH 3] + defined above. In another particular embodiment, the cooling process is that in which the organic-inorganic hybrid material A is a 60/40% atomic mixture of [(CH3) 2NH2] + / [(CH3) 2CH3) 2N] +.
    [0053]
    [0054] In another particular embodiment, the refrigeration process is that wherein in the organic and inorganic hybrid material, A is the mixture of monovalent organic cations and monovalent inorganic cations. In another particular embodiment, the cooling process is that where in the organic-inorganic hybrid material A is a mixture of [(CH3) 2NH2] + / Cs +.
    [0055] In another particular embodiment the refrigeration process is that where in the organic-inorganic acidic material A is a 60/40% atomic mixture of [(CH3) 2NH2] + / [(CH3) 2CH3) 2N] +, or a mixture 75 / 25% atomic of [(CH3) 2NH2] + / Cs +.
    [0056]
    [0057] In a particular embodiment, the cooling process is that where the trivalent cation in B is selected from the group consisting of: Cr + 3, Fe + 3, Bi + 3, In + 3, and Y + 3.
    [0058]
    [0059] In a particular embodiment, the refrigeration process is that where the trivalent cation in B is selected from the group consisting of: Lu + 3, La + 3, Ce + 3, Pr + 3, Nd + 3, Pm + 3, Sm +3, Eu + 3, Gd + 3, Tb + 3, Dy + 3, Ho + 3, Er + 3, Tm + 3, and Yb + 3.
    [0060]
    [0061] In another particular embodiment, the cooling process is that in which the organic-inorganic buphoric material B is a divalent metal cation.
    [0062]
    [0063] In another particular embodiment, the cooling process is that in which the organic-inorganic hybrid material B is a divalent metal cation which is selected from the group consisting of: Pb + 2, Mn + 2
    [0064]
    [0065] In another particular embodiment, the cooling process is that wherein in the organic-inorganic hybrid material B is a mixture of divalent metal cations or a 50/50% atomic mixture of a monovalent cation and a trivalent cation.
    [0066]
    [0067] In another particular embodiment, the cooling process is that in which the organic-inorganic hybrid material B is selected from the group consisting of: a mixture of Mn + 2 / Co + 2, and a mixture of Ag + / Bi + 3.
    [0068]
    [0069] In another particular embodiment, the refrigeration process is that in which the organic-inorganic hybrid material B is selected from the group consisting of: Pb + 2, Mn + 2, a 60/40% atomic mixture of Mn + 2 / Co + 2, and a 50/50% atomic mixture of Ag + / Bi + 3.
    [0070]
    [0071] In another particular embodiment, the cooling process is that where in the organic-inorganic hybrid material, X is Cl ".
    [0072] In another particular embodiment, the cooling process is that where in the organic-inorganic debride material, X is a mixture of Cl- / I-, or a mixture of I- / Cl- / Br ".
    [0073]
    [0074] In another particular embodiment, the cooling process is that where in the organic-inorganic debride material, X is a 60/40% atomic mixture of Cl- / I-, or a 30/50/20% atomic mixture of I- / Cl- / Br-.
    [0075]
    [0076] Unless otherwise indicated, all percentages mentioned in this document with respect to the elements of the organophosphorus organic material are expressed as an atomic percentage. The atomic percentage means the number of atoms of an element in 100 atoms representative of a substance.
    [0077]
    [0078] In a preferred embodiment, the cooling process is that where the organic-inorganic hybrid material is [(CH3) 2NH2] PbCl3.
    [0079]
    [0080] The refrigeration process is carried out inside a device by means of the repeated and repetitive application of an external stimulus on the organicoinorganic material in a process that generally comprises the following stages: a) Apply an external stimulus with which the material is heats up; b) Keep the stimulus for a certain period of time with which it gives off heat that is conducted towards the outside of the device; c) Remove the stimulus with which the material is cooled; and d) Use the cooled material to absorb heat from the interior of the device to be cooled.
    [0081]
    [0082] By way of example, in the first stage an external stimulus such as hydrostatic pressure is applied causing the organic-inorganic material to heat up. In the second stage, the applied external stimulus is kept constant for a time so that the excess heat generated is directed towards a heat sink, for example, this can be a heat sink. This excess heat can be conducted to the heat sink either by direct contact of the material with this sink or by a heat transfer fluid such as air, water, alcohols, etc. In the third stage, once the organic-inorganic hybrid material has released that excess heat, the applied stimulus is removed, which produces a cooling of the organic-inorganic hybrid material. In the fourth stage, keeping the stimulus removed for a certain time, the organic-inorganic hybrid material that has Once it has been cooled in the previous stage, it absorbs the heat of the chamber that it is desired to cool, for example the inside of a refrigerator. This heat from the interior of the chamber is absorbed either by direct contact of the material with this chamber or by a heat transfer fluid such as air, water, alcohols, etc. This four-stage process is repeated in a specific and predetermined time in which the actuator of the stimulus, for example a piston, exerts and removes the pressure automatically and infinitely.
    [0083]
    [0084] In a preferred embodiment, the refrigeration process is that where the external stimulus is hydrostatic or uniaxial pressure. In a particular embodiment, the hydrostatic or uniaxial pressure that is applied in the case of barocaloric or elastocaloric materials respectively is between 20 and 1000 bar (2-100 MPa). In a more preferred embodiment, the hydrostatic / uniaxial pressure that is applied is 20-100 bar (2-10 MPa). In a more preferred embodiment, the hydrostatic / uniaxial pressure that is applied is between 40-70 bar (4-7 MPa). In a still more preferred embodiment the hydrostatic pressure is 69 bar (6.9 MPa).
    [0085]
    [0086] In a particular embodiment, the cooling process is that where the external stimulus is light. In a particular embodiment, the light intensity applied in the case of using photocaloric materials is between 0.1-1000 mW cm-2. In another particular embodiment, the intensity of the applied light is 1-100 mW cm-2: In another particular embodiment, the intensity of the applied light is approximately 10 mW cm-2. In another particular embodiment, the wavelength of the applied light is between 200-1000 nm. In another particular embodiment, the wavelength of the applied light is about 450 nm.
    [0087]
    [0088] In a particular embodiment, the cooling process is that where the external stimulus is an electric field. In another particular embodiment, the electric field applied in the case of using electrocaloric materials is a voltage between 1-500 V.
    [0089]
    [0090] In another particular embodiment, the electric field applied in the case of using electrocaloric materials is a voltage between 10-100 V. In another particular embodiment, the electric field applied is a voltage of approximately 40 V.
    [0091] Generally, the time the stimulus is maintained applied in the case of barocaloric or elastocaloric materials as well as photocaloric or electrocaloric materials is between 0.05-60 seconds. Preferably, the time the stimulus is applied is between 1-10 seconds. More preferably, the time the stimulus is applied is about 1 second.
    [0092]
    [0093] Generally, the time that the stimulus is maintained in the case of barocaloric or elastocaloric materials as well as photocaloric or electrocaloric materials is between 0.05 - 60 seconds. Preferably, the time the stimulus is applied is between 1-10 seconds. More preferably, the time that the withdrawn stimulus is maintained is approximately 1 second.
    [0094]
    [0095] The term "approximately" in this document means the value indicated in the corresponding unit ± 5%.
    [0096]
    [0097] The organic-inorganic hybrid materials used in the cooling process of the present invention allow to work in a temperature range between 0 ° C and 120 ° C. Preferably, the working temperature range is between 7 ° C and 70 ° C. More preferably, the working temperature range is between 40-65 ° C.
    [0098]
    [0099] In a particular embodiment of the cooling process, the organo-organic hybrid material is [(CH3) 2NH2] PbCl3 and the working temperature is between 42 and 65 ° C, preferably between 42 and 54 ° C.
    [0100]
    [0101] Also part of the invention is the use of the organic-inorganic hybrid material of crystal structure with hexagonal packing, of general formula: ABX3 (I) as defined above as a heat material for cooling devices. The embodiments are particular and preferred of the refrigeration process described above with respect to the materials also are particular and preferred embodiments for this aspect of the invention.
    [0102]
    [0103] These materials can be incorporated into a cooling device. The device can be used in different sectors such as the refrigeration sector of air conditioning, refrigerators, refrigeration of electronic devices, automobiles, fabrics, clothes, slippers, etc.
    [0104]
    [0105] Thus, another aspect of the present invention is related to a device with refrigeration capacity induced by an external stimulus, comprising: (1) An organic-inorganic hupido material of general formula ABX3 (I) and crystal structure with hexagonal packing such as it has been previously defined; (2) means for practically exercising the stimulus for a certain period of time on the organic-inorganic solid material and then removing it, where the external stimulus is selected from the group consisting of hydrostatic pressure, uniaxial pressure, electric field and illumination with light.
    [0106]
    [0107] In a particular embodiment, the device of the invention is one that has means to apply a hydrostatic pressure as an external stimulus. In another particular embodiment, the device of the invention is one that has means to apply a uniaxial pressure, an electric field or light illumination. The particular / preferred values of hydrostatic pressure, uniaxial pressure, electric field or illumination with light indicated above for the cooling process are also particular / preferred values for the device means.
    [0108]
    [0109] By way of example, the means for exerting and withdrawing an externally selected external stimulus between hydrostatic pressure, uniaxial pressure, electric field and lighting with light can be the following: for the pressure a piston: a fluid or the hand or finger of a person on a screen (or any actuator that exerts hydrostatic or uniaxial pressure); for the electric field: an electric circuit that transmits electrical current to the material; and for light: a light bulb, lamp, led, laser, flashlight, etc.
    [0110]
    [0111] In a particular embodiment, the device of the invention further comprises: (3) a heat sink that is responsible for removing the heat to the outside; (4) optionally a heat exchanger fluid; and (5) a chamber or enclosure that needs to be cooled. The sump could for example be a fan, a heat sink, etc. The heat exchanger fluid is optional and if present it could be selected between air, water, alcohols, etc. As an example, the camera or enclosure that needs to be cooled in the case of a refrigerator, would be the inside of the refrigerator, in the case of a mobile phone would be the inside of the mobile phone, in the case of a pair of sneakers, would be the inside of the shoe.
    [0112]
    [0113] Furthermore, in this cooling device, the molten material can be contained in a powder form, suspended in a fluid (or in a solid matrix) which acts as a heat exchanger and / or improves the thermal conductivity or in the form of a thin sheet (thin layer). ) in the case of screens of electronic devices. Thus, in a particular embodiment of the device, the organic-inorganic hybrid material of general formula ABX3 is in powder form, suspended in a heat exchanger fluid such as an oil, silicone, water, alcohols, etc. suspended in a solid heat-conducting matrix (for example a composite of the heat-formed material and a polymer, metal alloy, or heat-conducting steel), or in the form of a thin sheet on top of an electrically conductive substrate (for example a coated glass) of tin oxide doped with fluorine or with indium).
    [0114]
    [0115] Another aspect of the present invention is related to an organic-inorganic hybrid material of formula [(CH3) 2NH2] PbCl3 (la), ie a compound of formula ABX3 (I) where A is dimethylammonium ([(CH3) 2NH2] + ), B is Pb + 2 and X is Cl-. This compound exhibits the crystal structure obtained by monocrystal X-ray diffraction which is illustrated in FIG. 3.
    [0116]
    [0117] In order to obtain the monocrystal crystal structure of the organic-inorganic hybrid material of formula [(CH3) 2NH2] PbCl3 (la), a suitable monocrystal was selected from the sample of [(CH3) 2NH2] PbCl3 to collect diffraction data at room temperature in a Bruker Kappa diffractometer equipped with an APEX II CCD detector and using MoKa monochromatic radiation (A = 0.71073 A). The glass was mounted on a MiTeGen MicroMountTM using Paratone® (Chevron Corporation). To carry out this experiment, the crystal was measured at room temperature. The data collection, integration and reduction were carried out with the software package APEX2 V2015.9-0 (Bruker AXS, 2015), which includes the programs that are detailed below. The intensity integration was performed with SAINT 8.34A and corrected for Lorentz and the polarization effects and also for the absorption by means of multiple exploration methods on the basis of equivalent data from symmetry using SADABS 2008/1 or TWINABS 2012/1 depending on the presence of twins. A single network was found for the crystal collected at room temperature (T = 20-25 ° C).
    [0118]
    [0119] The structure was solved by means of the direct method using the SHELXT2014 program and refined by means of the square-mm method in SHELXL2014 / 7. The presence of twins was clear from the visual inspection of diffraction images collected. The data set was indexed using CELL_NOW 2008/4 obtaining three orientation matrices that interpret all diffraction maxima. The integration of the reflections was made taking into account the matrices of orientation of the three domains twinned simultaneously. To refine the structure, anisotropic thermal factors were used for the non-H atoms. For the hydrogen atoms of the cation [(CH3) 2NH2] + they could not be found in the Fourier map due to the disordered disposition of this cation. All the hydrogen atoms were refined using the conduction model implemented in SHELXL2014 / 7.
    [0120]
    [0121] The diffraction of monocrystal X-rays at room temperature reveals that the compound [(CH3) 2NH2] PbCl3 has a crystal structure with hexagonal packing and shows the bond distances indicated in Table 1.
    [0122]
    [0123] Table 1: Bonding distances for the compound [(CH3) 2NH2] PbCl3 at room temperature
    [0124]
    [0125]
    [0126] The crystalline structures with cubic packing of the organic-inorganic phthalic materials of the comparative compounds [(CH3CH2CH2) 4N] [Mn (N (CN) 2) 3] and [CH3NH3] PbCl3 can also be elucidated by monocrystal X-ray diffraction carried out in an analogous manner as for the material hforido [(CH3) 2NH2] PbCl3.
    [0127]
    [0128] The compound [(CH3) 2NH2] PbCl3 is thermally stable up to 190 ° C. The stability of this compound is similar to that which is predicted for the comparative compounds of formula [CH3NH3] PbX3. Advantageously, the compound [(CH3) 2NH2] PbCl3 remains stable under ambient temperature and lighting conditions under a humidity of up to 65% for at least one year, while the compounds [CH3NH3] PbX3 in less than 24 hours absorb water which they modify its properties and structure.
    [0129]
    [0130] Another aspect of the present invention is related to a preparation process of the organic-inorganic hybrid material of formula [(CH3) 2NH2] PbCl3 which comprises carrying out a reaction in solid state activated by mechanical means between [(CH3) 2NH2] Cl and PbCl2. The process is simple and uses mild conditions. It does not need solvent and is, therefore, ecological.
    [0131]
    [0132] In a particular embodiment, the above reaction is carried out at room temperature. The term ambient temperature means a temperature between 20 and 25 ° C. In another particular embodiment, the mechanical means are means for carrying out a grinding. In another particular embodiment, the mechanical mixture is carried out with equimolar amounts of the starting compounds.
    [0133]
    [0134] The organic-inorganic hybrid materials used in the process and device of the present invention can be obtained analogously to the organic-inorganic hybrid material of formula [(CH3) 2NH2] PbCl3 from the corresponding halides of organic cations and cation halides starting metals. Other methods known in the literature, such as those described in MG Kanatzidis et al., Inorganic Chemistry, 2017, vol. 56, pp. 56-73 and the articles that are referred to here The expert in the matter would know how to adapt the teaching of these documents from the common and general knowledge for the preparation of the organic-inorganic hforidos materials.
    [0135]
    [0136] Throughout the description and the claims the word "comprises" and its variants do not intend to exclude other technical characteristics, additives, components or steps. In addition, the word "comprises" includes the case "consists of". For those skilled in the art, other objects, advantages and characteristics of the invention will emerge partly from the description and partly from the practice of the invention. The following examples and drawings are provided by way of illustration, and are not intended to be limiting of the present invention. In addition, the present invention covers all possible combinations of particular and preferred embodiments herein indicated.
    [0137]
    [0138] BRIEF DESCRIPTION OF THE DRAWINGS
    [0139]
    [0140] FIG. 1: Crystal structure of the comparative compound [(CH3CH2CH2) 4N] [Mn (N (CN) 2) 3] obtained by single-crystal X-ray diffraction.
    [0141]
    [0142] FIG. 2: Crystal structure of the comparative compound [CH3NH3] PbCl3 obtained by single-crystal X-ray diffraction.
    [0143]
    [0144] FIG. 3: Crystal structure of the compound [(CH3) 2NH2] PbCl3 obtained by single-crystal X-ray diffraction.
    [0145]
    [0146] FIG. 4: Barocaloric effect of the comparative compound [(CH3CH2CH2) 4N] [Mn (N (CN) 2) 3].
    [0147]
    [0148] FIG. 5: Barocaloric effect of the compound [(CH3) 2NH2] PbCl3.
    [0149]
    [0150] EXAMPLES
    [0151]
    [0152] Example 1: Preparation of [(CH3) 2NH2] PbCl3
    [0153]
    [0154] The material [(CH3) 2NH2] PbCl3 was obtained by mechano-chemical synthesis at room temperature of the compounds [(CH3) 2NH2] Cl and PbCl2. For this, equimolar amounts of [(CH3) 2NH2] Cl and PbCl2 were used and ground in a mortar for 15 minutes until a homogenous powder was visually obtained.
    [0155] The compound [(CH 3 ) 2 NH 2 ] Cl was previously synthesized by reacting equimolar amounts of dimethylamine in aqueous solution (40% weight of (CH 3 ) 2 NH in H 2 O) and hydrochloric acid in aqueous solution (37% weight of HCl in H 2 O). This mixture of solutions was stirred for 15 minutes in an ice bath. The crystallization of the dimethylammonium chloride was carried out by evaporating the solvent in a rotary evaporator until the appearance of a white solid composed of microcrystals. This solid is filtered and washed with absolute diethylether several times and dried in vacuo overnight.
    [0156]
    [0157] The compound PbCl 2 is synthesized by reacting equimolar amounts of sodium chloride (or potassium chloride) in saturated aqueous solution and lead nitrate in aqueous solution. This mixture of solutions was stirred for 15 minutes in an ice bath. The crystallization of PbCl 2 was carried out by evaporating the solvent in a rotary evaporator until the appearance of a white solid composed of microcrystals. This solid is filtered and washed with absolute diethylether several times and dried in vacuo overnight.
    [0158]
    [0159] The compounds [(CH 3 ) 2 NH 2 ] Cl and PbCl 2 can also be obtained commercially.
    [0160]
    [0161] To obtain monocrystals of the compound and to obtain a higher purity, said compound was dissolved in an organic solvent (see N, N-dimethylformamide or dimethylsulfoxide) in concentrations between 15% -45% by weight. Subsequently, said solvent was allowed to evaporate at room temperature for one week for obtaining monocrystals or for purification of the compound. The material obtained was characterized by single-crystal X-ray diffraction (see FIG 3).
    [0162]
    [0163] Example 2: Depositing a thin sheet on a substrate of the compound [(CH 3 ) 2 NH 2 lPbCl 3
    [0164]
    [0165] To deposit a thin sheet on a substrate of the compound [(CH3) 2NH2] PbCl3, said compound was dissolved in an organic solvent (or N, N-dimethylformamide or dimethylsulfoxide) in concentrations between 15% -45% by weight. Subsequently, said solvent was allowed to evaporate on a substrate by means of rotation at 2000 rpm for 60 seconds to obtain a thin sheet.
    [0166] Example 3: Barocaloric effect
    [0167]
    [0168] To study the heat effect of the material, the technique of differential scanning calorimetry was used. For this, samples of around 5 mg of the material were analyzed in a TA Instruments MDSC Q2000 equipment equipped with a pressure cell. The samples were typically heated and cooled at speeds between 1 oC min-1 and 20 oC min-1, from room temperature to 150 oC, under a nitrogen atmosphere. These heating and cooling cycles were carried out at different nitrogen pressures from 1 bar to 69 bar, with a constant nitrogen flow of 50 ml min-1. The pressure cell was calibrated for each of these pressures using a standard of indium. The barocaloric effect was obtained as the difference of change of isobaric entropy at the pressure of 69 bar and of change of isobaric entropy at the pressure of 1 bar, in units of J kg-1 K-1.
    [0169]
    [0170]
    [0171]
    [0172]
    [0173] The barocaloric effect of the compound of comparative example 1 and of example 1 of the invention are illustrated in FIGS. 4 and 5 respectively.
    [0174]
    [0175] The barocaloric effect of the compound [(CH3) 2NH2] PbCl3 is considerably higher than predicted for the compounds of comparative examples 2-4 which are the Physically, they are closer, in particular with respect to the compound of example 2. Likewise, the compound [(CH3) 2NH2] PbCl3 has a better working temperature, much closer to room temperature than that of the comparative compounds, in particular the comparative compounds 3 and 4, which greatly facilitates its application as refrigeration material.
    [0176]
    [0177] LIST OF APPOINTMENTS
    [0178]
    [0179] Non-patent literature
    [0180]
    [0181] - Regulation EU No 517/2014
    [0182]
    [0183] - Gerald Brown in J.Appl. Phys., 1976, vol.47, pp. 3673-3680
    [0184]
    [0185] - J. M. Bermudez-Garda et al., Nature Communications, 2017, 8, 15715
    [0186]
    [0187] - J. M. Bermudez-Garda et al., J. Phys. Chem. Lett., 2017, vol. 8, pp. 4419-4423
    [0188]
    [0189] - X. Moya et al., Nature Materials, 2014, vol. 13, pp. 439-450
    [0190]
    [0191] - M. G. Kanatzidis et al., Inorganic Chemistry, 2017, vol. 56, pp. 56-73
    权利要求:
    Claims (19)
    [1]
    1. Refrigeration process that involves applying an external stimulus selected between hydrostatic pressure, uniaxial pressure, electric field and illumination with light, to an organic-inorganic hybrid material of crystal structure with hexagonal packing, of general formula:
    ABX3 (I)
    where:
    A is selected from the group consisting of a monovalent organic cation, a mixture of monovalent organic cations, and a mixture of monovalent organic cations and monovalent inorganic cations;
    the monovalent organic cation is selected from the group consisting of [NH3NH2] +, [NH3OH] +, [CH (NH2) 2] +, [C (NH2) 3] +, ([C3NH8] +), [(CH3) 2NH2] +, [CH3CH2NH3] +, [CH3C (NH2) 2] +, [(CH3) 4N] +, [C3N2H5] +, [(CH3) 3NH] +, [(CH ^ CNH ^, [(C4H4)] NH2] +, [(CH3) 2CH3) 2N] +, [(CH3CH2) 2NH2] +, and [(CaH5) NH3] +; Y
    the mixture of monovalent organic cations is a mixture of any of the organic cations mentioned, including also [CH3NH3] +;
    and the mixture of organic cations and monovalent inorganic cations is a mixture of any of the aforementioned organic cations with one or more inorganic cations selected from the group consisting of Cs +, Rb +, NH4 +;
    B is selected from the group consisting of: a divalent metal cation, a mixture of divalent metal cations, and a 50/50% atomic mixture of a monovalent cation and a trivalent cation, where:
    the divalent metal cation is selected from the group consisting of: Mg + 2, Ca + 2, Sr + 2, Mn + 2, Fe + 2, Co + 2, Ni + 2, Cu + 2, Zn + 2, Cd +2, Pb + 2, Sn + 2, and Sb + 2;
    the monovalent metal cation is selected from the group consisting: Ag +, Na +, K +, Tl +, and Cu +;
    the trivalent cation is selected from the group consisting of: Cr + 3, Fe + 3, Bi + 3, In + 3; Y + 3,
    X is a halide anion selected from the group consisting of F-, Cl-, Br-, I-, and a mixture thereof.
    [2]
    2. The refrigeration process according to claim 1, wherein A is a monovalent organic cation selected from the group consisting of: [(CH3) 2NH2] +, [CH3CH2NH3] +, [(CH3) 4N] +, [(CH3 ) 3NH] +, [(CH3) 2CNH3] +, [(CH3) 2CH3) 2N] +, and [(CH3CH2) 2NH2] +.
    [3]
    3. The refrigeration process according to claim 2, wherein A is [(CH3) 2NH2] +.
    [4]
    4. The refrigeration process according to claim 1, wherein A is a 60/40% atomic mixture of [(CH3) 2NH2] + / [(CH3) 2CH3) 2N] + or a 75/25% atomic mixture of [(CH3 2NH2] + / Cs +.
    [5]
    5. The refrigeration process according to any of claims 1-4, wherein the trivalent cation is selected from the group consisting of: Cr + 3, Fe + 3, Bi + 3, In + 3, and Y + 3.
    [6]
    6. The refrigeration process according to any of claims 1-4, wherein the trivalent cation is selected from the group consisting of: Lu + 3, La + 3, Ce + 3, Pr + 3, Nd + 3, Pm + 3, Sm + 3, Eu + 3, Gd + 3, Tb + 3, Dy + 3, Ho + 3, Er + 3, Tm + 3, and Yb + 3.
    [7]
    7. The refrigeration process according to any of claims 1-4, wherein B is selected from the group consisting of a divalent metal cation.
    [8]
    8. The refrigeration process according to any of claims 1-4, wherein B is selected from the group consisting of: Pb + 2, Mn + 2, a 60/40% atomic mixture of Mn + 2 / Co + 2, and a 50/50% atomic mixture of Ag + / Bi + 3.
    [9]
    9. The refrigeration process according to any of claims 1-8, wherein X is Cl-.
    [10]
    10. The refrigeration process according to any of claims 1-8, wherein X is a 60/40% atomic mixture of Cl- / I-, or a 30/50/20% atomic mixture of I- / Cl- / Br- .
    [11]
    11. The refrigeration process according to claim 1, wherein the organic-inorganic acid material is [(CH3) 2NH2] PbCl3.
    [12]
    12. The refrigeration process according to any of claims 1-11, wherein the external stimulus is hydrostatic pressure.
    [13]
    13. The refrigeration process according to any of claims 1-12, which is a continuous process and where each cycle comprises:
    a) Apply and maintain the stimulus for a certain period of time with which the material releases heat that is conducted towards the outside of the device; b) Remove the stimulus with which the material is cooled; Y
    c) Use the cooled material to absorb heat from the interior of the device to be cooled.
    [14]
    14. Use of the organic-inorganic hybrid material of crystal structure with hexagonal packing of the general formula: ABX3 (I) as defined in any of claims 1-11 as a heat material for cooling devices.
    [15]
    15. Device with cooling capacity induced by an external stimulus, comprising:
    (1) An organic-inorganic hybrid material of general formula ABX3 (I) and crystal structure with hexagonal packing as defined in any of claims 1-11,
    (2) means to specifically exercise the stimulus during a certain period of time on the organic-inorganic hforido material and then remove it, where the external stimulus is selected from the group consisting of hydrostatic pressure, uniaxial pressure, electric field and illumination with light.
    [16]
    16. Device according to claim 15, wherein the organo-organic hybrid material is in powder form, suspended in a fluid, suspended in a solid matrix, or in the form of a thin sheet.
    [17]
    17. Organic-inorganic hybrid material of formula [(CH 3 ) 2 NH 2 ] PbCl 3 (la).
    [18]
    18. Process for preparing the organic-inorganic hybrid material of formula [(CH 3 ) 2 NH 2 ] PbCl 3 comprising carrying out a reaction in solid state activated by mechanical means between [(CH 3 ) 2 NH 2 ] Cl and PbCl 2
    [19]
    19. Process according to claim 18, wherein the mechanical mixture is carried out with equimolar amounts of [(CH 3 ) 2 NH 2 ] Cl and PbCl 2 .
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    同族专利:
    公开号 | 公开日
    ES2711048B2|2019-10-22|
    US20200332167A1|2020-10-22|
    EP3702431A1|2020-09-02|
    EP3702431A4|2021-07-21|
    WO2019081799A1|2019-05-02|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    CN104927840A|2015-06-02|2015-09-23|南开大学|Organic-inorganic hybrid perovskite phase-change material with adjustable emitted light, and preparation method|
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