Methods, apparatus, and applications of heat storage and release by solid phase transition of glassy crystals and their actively controllable pressure-caloric effect materials

Abstract

The present invention discloses a method, device and application of solid-state phase transition heat storage and dissipation based on glassy crystals, which belongs to the technical field of solid-state phase transition energy storage. The glassy crystal phase is an intermediate metastable state formed during the transition from a high-temperature plastic crystal phase to an ordered crystal phase, and can be obtained by rapidly cooling the disordered state of the high-temperature plastic crystals of a pressure caloric effect material. Rapid cooling freezes the disordered state of the material at high temperatures with supercooling, thus avoiding the complete orientation order that usually occurs at low temperatures. When a slight pressure is applied to it, the transformation from the glassy crystal phase to an ordered crystal phase is achieved, thereby releasing heat. This glassy crystal phase has excellent thermal stability, allowing for long-term storage, long-distance transportation and controlled release of thermal energy.

Description

[Technical Field] 【0001】 This invention relates to the technical field of solid phase transition energy storage. In particular, it relates to methods, apparatus, and applications of heat storage and release by solid phase transition of glassy crystals and their actively controllable pressure caloric (barocaloric) materials. [Background technology] 【0002】 Climate change is a global problem facing humanity, and as countries emit carbon dioxide, greenhouse gases continue to increase, threatening ecosystems. Against this backdrop, countries around the world have adopted global agreements to reduce greenhouse gas emissions, and China has also advocated strategic goals of "carbon peaking" and "carbon neutrality." The use of clean energy and improved energy efficiency are effective ways to achieve the goal of carbon neutrality. However, current data shows that 72% of energy is wasted in energy conversion processes worldwide. Because it is mainly dissipated in the form of thermal energy, it cannot be effectively utilized, leading to decreased energy use efficiency and the problem of fossil fuel waste. The recovery and utilization of thermal energy plays a broad and important role in achieving sustainable energy use. Thermal energy storage technology is a technology that has been gradually developed with the aim of solving problems caused by the mismatch between the supply and demand of thermal energy in terms of time, space, or intensity, and maximizing the energy use of the entire system by storing thermal energy such as solar heat, geothermal heat, industrial waste heat, and low-grade waste heat using thermal storage materials as a medium and releasing it when needed. Therefore, the development of high-performance heat storage materials is an important approach to improving energy utilization, reducing energy consumption, and ultimately solving the carbon emission problem. 【0003】 Latent heat storage technology based on phase transition materials utilizes the phase transition process of the material itself to absorb and release heat, thereby achieving heat storage and utilization. Phase transition latent heat storage materials have more stable energy output compared to sensible heat storage technology, and the amount of heat stored per unit volume is several times that of sensible heat storage materials. Among these, solid-solid phase transition heat storage materials do not generate a liquid phase during the phase transition process, and the volume change before and after the phase transition is relatively small. They are non-toxic and non-corrosive, have low requirements for container material and processing technology, have a low degree of supercooling, and have a long service life, making them considered the most ideal heat storage method. However, conventional solid-solid phase transition materials have a small latent heat of phase transition and limited heat storage capacity. At the same time, the phase transition behavior of conventional solid-solid phase transition materials is entirely dependent on changes in ambient temperature. As the ambient temperature gradually decreases, a spontaneous phase transition occurs, resulting in uncontrollable heat release. It is impossible to precisely control the time of heat release, and one lacks control over heat quantity control. As a result, such materials cannot be transported over long distances or used in low-temperature environments with a wide temperature range, severely limiting the recovery and utilization of thermal energy. Amidst the growing demand for thermal energy storage technology, the development of solid phase transition thermal energy storage materials that possess high thermal energy storage performance and can actively control heat release has become a new challenge. 【0004】 Solid-to-solid phase transition materials involve three phase structures: crystalline phase, viscous crystalline (plastic crystal) phase, and glassy crystalline phase. The crystalline phase is a completely ordered and regular state, including the orientation of the crystal lattice and structural units. The viscous crystalline phase is a highly disordered state, where the orientation of the organic molecules or inorganic structural units constituting the material is completely disordered, but the center of mass is still long-range and maintains an orderly crystal lattice. The degree of order of the glassy crystalline phase is intermediate between the crystalline and viscous crystalline phases, where the center of mass is ordered but the orientation is disordered (a frozen state). Not all solid-state phase transition materials simultaneously possess all three phase structures; only some materials simultaneously have the viscous crystalline phase, and only a small fraction of viscous crystalline materials have the glassy crystalline phase. 【0005】 The barocaloric effect refers to the phenomenon in which a phase transition occurs due to pressure, resulting in a caloric effect. In recent years, the applicant's team has made groundbreaking progress in the study of barocaloric materials, and the entropy change of some barocaloric materials is several hundred Jkg. -1 K -1 It is possible to reach this point. In pressure caloric effect refrigeration technology, a reversible pressure caloric effect is a prerequisite for realizing the application of efficient solid-state refrigeration technology. However, the applicant's team discovered that the pressure caloric effect is irreversible during their research on pressure caloric effect materials having a glassy crystalline phase. That is, while this type of material having a glassy crystalline phase can change from a regular crystalline phase to a viscous crystalline phase during the heating process, a reversible phase transition still does not occur during the cooling process, even at temperatures far below the phase transition point. As described above, the viscous crystalline phase does not undergo a phase change to the crystalline phase upon cooling, but rather becomes a supercooled state of the viscous crystalline phase. The applicant of this application refers to this supercooled state of the viscous crystalline phase as the glassy crystalline phase, which is a solid state (metastable state) resulting from the supercooling of the viscous crystalline phase. As explained above, the glassy crystalline phase is a state in which the mass centers of the organic molecules or inorganic structural units constituting the material are ordered but their orientation is disordered (frozen state) (Figure 1). Therefore, although pressure-calorific materials with such irreversible pressure-calorific effects exhibit very large entropy changes, they cannot actually be used as pressure-calorific refrigeration materials. Surprisingly, based on the irreversible phase transition of this type of pressure-calorific material having a glassy crystalline phase, it is expected that long-term, wide-temperature, and cross-regional heat storage will be realized. This is because this type of material with a glassy crystalline phase does not spontaneously undergo a phase transition even when the temperature decreases. One reason for this result is that this type of pressure-calorific material freezes under supercooling during the rapid cooling process, forming a glassy crystalline phase. It does not directly change into a completely ordered, regular low-temperature ordered phase. Because a large amount of disordered state is preserved and frozen, the material in the glassy crystalline phase still has a large entropy, ensuring sufficient heat storage. 【0006】 Furthermore, similar to the pressure-driven phase transition of pressure-caloric effect materials, a phase transition from the glassy crystalline phase to the low-temperature ordered crystalline phase can be achieved by rapidly cooling the viscous crystalline phase to form a glassy crystalline phase, and then applying hydrostatic pressure, thereby achieving the objective of releasing latent heat. Since the glassy crystalline phase can be pressure-controlled, when this type of pressure-caloric effect material is used as a heat storage material, a means is provided to precisely control the heat release time. According to this, the effective bonding of the viscous crystalline phase and the glassy crystalline phase of this type of pressure-caloric effect material is expected to overcome the limitations of current phase transition heat storage materials in solid-solid pressure-caloric effect materials, enabling heat storage across temperature ranges, over long distances and long periods, and precise control of heat release time. [Overview of the Initiative] 【0007】 To overcome the above-mentioned problems in heat storage and release by solid phase transitions, the object of the present invention is to provide a pressure-driven solid heat storage and release method, apparatus, and application that can actively control heat dissipation. 【0008】 To achieve the above objectives, the technical solutions employed by the present invention are as follows. 【0009】 A controllable solid phase transition heat storage and release method for pressure calorific material, comprising the following three steps: Step 1 is heating a pressure calorific material sample to a high-temperature viscous crystalline phase state. Step 2 is rapidly cooling the high-temperature viscous crystalline phase of the pressure calorific material to a glassy crystalline phase state. (Supercooled state of the viscous crystalline phase, the same applies hereafter) Step 3 provides a pressure-caloric effect material. Long-term thermal energy storage is achieved within the pressure-caloric effect material in a glassy crystalline phase state. Step 3 enables controllable storage, transfer, and utilization of thermal energy by suppressing heat dissipation by applying pressure as a driving method when heat dissipation is required. 【0010】 Among these, in Step 2, the rapid cooling method for obtaining a glassy crystalline phase includes cooling at a cooling rate of ≧2 K / min or instantaneously cooling a high-temperature soft viscous crystalline phase sample with ice water or liquid nitrogen. In Step 3, the method of applying pressure includes applying hydrostatic pressure or pressure by needle piercing. As the pressure-caloric effect material, among the soft viscous crystalline materials, 2-amino-2-methyl-1,3-propanediol (CH3)C(CH2)(CH2OH)2 (AMP), m-carborane C2B 10 H 12 , 1-cyanoadamantane C 11 H 15 N (CAN), adamantanone C 10 H 14 O (AON), and pentachloronitrobenzene C6C l5 NO2 (PCNB) are one or more soft viscous crystalline materials selected therefrom. 【0011】 When the pressure-caloric effect material is 2-amino-2-methyl-1,3-propanediol (AMP), a phase transition occurs at 355 K, absorbing heat and changing to a high-temperature soft viscous crystalline phase state, and the corresponding enthalpy change is 215 Jg -1 , and the entropy change is 606 Jkg -1 K -1 . When 2-amino-2-methyl-1,3-propanediol (AMP) in the high-temperature soft viscous crystalline phase is rapidly cooled to a low temperature state of 273 K, a glassy crystalline phase is obtained. The obtained glassy crystalline phase of 2-amino-2-methyl-1,3-propanediol (AMP) can be stored at 273 K or heated to store heat for a long time at a temperature below room temperature. 2-amino-2-methyl-1,3-propanediol (AMP) does not spontaneously undergo a phase transition and release heat. When a pressure of 67 bar or more is applied to 2-amino-2-methyl-1,3-propanediol (AMP) in a holding state at a temperature of 273 K, a significant heat release peak occurs. The corresponding enthalpy change is 133 Jg -1 , and the entropy change is 487 Jkg -1 K -1 . 【0012】 A heat storage and heat exchange device comprising a pressure calorific material, the device comprising a heating unit, a rapid cooling unit, and a pressurizing unit. The heating unit is used to bring the pressure calorific material to a high-temperature, viscous crystalline phase. The rapid cooling unit is used to rapidly cool the high-temperature, viscous crystalline phase of the pressure calorific material to obtain a glassy crystalline phase of the pressure calorific material. The pressurizing unit controls heat release by applying hydrostatic pressure or needle-piercing pressure to the pressure calorific material when heat release is necessary, thereby achieving controllable storage, transfer, and utilization of thermal energy. The pressure calorific material is preferably a pressure calorific material having a glassy crystalline phase, and further preferably 2-amino-2-methyl-1,3-propanediol (CH3)C(CH2)(CH2OH)2(AMP), m-carborane C2B 10 H 12 , 1-Cyanoadamantane C 11 H 15 N (CAN), Adamantanone C 10 H 14 O (AON), and pentachloronitrobenzene C6C l5 One or more types are selected from NO2(PCNB). 【0013】 This invention provides a method for reusing waste heat from a thermal power plant. Using the pressure-caloric effect material having a glassy crystalline phase, the material absorbs heat from equipment such as cooling tower pipelines, boiler blowdown components, and deaerator exhaust components of the power plant, causing the material to undergo a phase transition to a high-temperature viscous crystalline phase, and further transforming the material from the high-temperature viscous crystalline phase to a glassy crystalline phase. By maintaining the glassy crystalline phase state of the material, heat storage at low temperatures is achieved, and ultimately, the heat is released and utilized by applying pressure. 【0014】 A method for storing solar energy, which utilizes the pressure-caloric effect material having a glassy crystalline phase of the present invention to absorb the heat generated by a solar heat collector, phase-transforms the material into a high-temperature soft-viscous crystalline phase, and further transforms the material from the high-temperature soft-viscous crystalline phase into a glassy crystalline phase. And by maintaining the glassy crystalline phase state of the material, heat storage at a low temperature is realized, and finally, heat is released and utilized by applying pressure. 【0015】 A method for recycling and utilizing waste heat in the computer room of a data center, which uses the pressure-caloric effect material having a glassy crystalline phase of the present invention to absorb the heat generated in the data center, as a result, phase-transforms the material into a high-temperature soft-viscous crystalline phase, and further transforms the material from the high-temperature soft-viscous crystalline phase into a glassy crystalline phase. And by maintaining the glassy crystalline phase state of the material, heat storage at a low temperature is realized, and finally, heat is released and utilized by applying pressure. 【0016】 The advantages and beneficial effects of the present invention are as follows. 1. Conventional phase change heat storage materials cannot accurately control the heat release time. The heat release time depends only on the temperature of the surrounding environment, and long-distance transportation and utilization cannot be realized. For example, people can only heat a solar cooker when the sun is rising, but by the time they try to make dinner, the solar cooker may have dissipated all the stored heat into the cool night air. The present invention organically combines the soft-viscous crystalline phase and the glassy crystalline phase of the pressure-caloric effect material, and by utilizing the characteristics and advantages of these two phases respectively, it can solve the limitations of conventional solid-solid phase change heat storage materials, such as having a small latent heat of phase change, a small heat storage capacity, being unable to realize long-distance transportation, and being unable to accurately control the heat release time. 【0017】 2. The solution of the present invention can be used to absorb waste heat in multiple scenarios. Based on the large entropy change characteristics of the viscous crystal phase transition process, an efficient cooling effect of the heat source is achieved. Compared with conventional solid-to-solid phase transition heat storage materials, the viscous crystal phase transition process can generate huge latent heat and entropy changes. Because the viscous crystal phase is in a highly disordered state, the orientation of the structural unit molecules of the material is completely disordered, but the center of mass forms a regular lattice over long distances. Due to the remarkably large disorder of molecular orientation, the entropy change during the solid phase transition is greater than the fusion entropy, and the proportion of disordered degrees of freedom in the total degrees of freedom of the system approaches the limit that maintains the rigidity of the solid. Due to the huge phase change entropy change, a large amount of heat generated from the heat source is absorbed, effectively lowering the temperature of the heat source and achieving an efficient cooling effect. 【0018】 3. The solution of the present invention achieves long-term storage and long-distance transport of heat by making maximum use of the properties of the glassy crystalline phase of a pressure-caloric effect material. The glassy crystalline phase is an intermediate metastable state formed when a material transforms from a high-temperature viscous crystalline phase to a low-temperature regular crystalline phase. Rapid cooling causes the disordered state of the material at high temperatures to freeze due to supercooling. This avoids the complete orientation ordering that normally occurs at low temperatures. The presence of a disordered state in the glassy crystalline phase results in a large entropy change. At the same time, because there is an energy barrier between the glassy crystalline phase and the low-temperature regular crystalline phase, this state does not spontaneously transition to the low-temperature crystalline phase even when stored at low temperatures for a long time unless influenced by an external field, enabling long-distance heat transport. 【0019】 4. Similar to other pressure-caloric materials, the phase transition from a glassy crystalline phase to a regular crystalline phase can be achieved by methods such as applying hydrostatic pressure, thereby releasing a large amount of latent heat of phase transition. This process is simple to operate, economically inexpensive, and does not require harsh or complex equipment or working environments. This makes it possible to control heat dissipation and utilization in pressure-caloric materials with a glassy crystalline phase by applying hydrostatic pressure or needle puncture, in low-temperature environments such as near freezing points or in situations where heat utilization is required. 【0020】 5. The phase transition behavior according to the present invention is entirely solid-solid phase transition, offering advantages such as small volume change, no phase separation, no leakage, low corrosiveness, and simple equipment. Taking 2-amino-2-methyl-1,3-propanediol (CH3)C(CH2)(CH2OH)2(AMP) as an example, it has a significant advantage in heat storage capacity compared to other solid-solid phase transition materials. The entropy change is 487 J / kg. -1 K -1 It can reach that level. 【0021】 6. The solution of the present invention can be applied to the recycling of waste heat in thermal power plants, where waste heat is transferred to a pressure-calorific material for storage, and the recovered waste heat can be transported over long distances to low-temperature environments where heating is required. When heat is needed, the objective of releasing heat at lower pressure for heating is achieved. The present invention can also be applied to the long-term storage and utilization of solar energy, the recycling of waste heat in computer rooms of data centers, and other applications, and has a wide range of potential applications. [Brief explanation of the drawing] 【0022】 [Figure 1] This is a schematic diagram illustrating the phase transition process and heat absorption and release of a pressure-caloric effect material having a glassy crystalline phase. [Figure 2] This is a heat flow curve of the heating process of AMP from a low-temperature regular crystalline phase to a high-temperature viscous crystalline phase. [Figure 3] This is a heat flow curve of the cooling process of AMP from a high-temperature viscous crystalline phase to a glassy crystalline phase. [Figure 4] The heat flow curve is shown when pressure is applied to an AMP glassy crystalline phase in an adiabatic state at 273K to achieve heat dissipation. [Figure 5] This is the temperature change curve when pressure is applied to an AMP glassy crystalline phase at room temperature to achieve heat dissipation. [Figure 6] This is the cyclic heat flow curve of AMP between the high-temperature viscous crystalline phase and the glassy crystalline phase. [Figure 7]This shows the heat flow curve of the glassy crystalline phase of AMP maintained at 273K for 24 hours. [Modes for carrying out the invention] 【0023】 To further illustrate the present invention, examples are provided below to illustrate the features and advantages of the present invention, and are not intended to limit the scope of the claims. 【0024】 The solution of the present invention is a controllable solid phase transition heat storage and heat release method for pressure calorific effect materials, and includes the following: 【0025】 Step 1: Heat the pressure caloric effect material sample to a high-temperature viscous crystalline phase. Heating methods include, but are not limited to, raising the temperature using a sample chamber of a microcalorimeter or directly heating the sample using a heating stage. 【0026】 Step 2: The pressure-caloric effect material of the high-temperature viscous crystalline phase is rapidly cooled to obtain the pressure-caloric effect material of the glassy crystalline phase. This achieves long-term thermal energy storage in the pressure-caloric effect material. The glassy crystalline phase is an intermediate metastable state formed during the transformation of the pressure-caloric effect material into an ordered crystal, and is obtained by rapidly cooling the high-temperature disordered state of the viscous crystalline phase. Rapid cooling causes the high-temperature disordered state of the viscous crystalline phase to freeze under supercooling, thereby avoiding the complete orientation ordering that normally occurs at low temperatures. The presence of a disordered state in the glassy crystalline phase means that the material in that state still retains a large amount of entropy change. This state, unless subjected to the influence of an external field, can be stored at low temperatures for a long time without spontaneously transitioning to the low-temperature crystalline phase, enabling long-distance heat transport. Rapid cooling methods include, but are not limited to, rapid cooling at a cooling rate of ≥2K / min, or instantaneous cooling of the high-temperature viscous phase sample with ice water or liquid nitrogen. 【0027】 Step 3: When a small external pressure is applied to a glassy crystalline phase material at a low temperature, a phase transition from glassy to ordered crystal is achieved, and the disordered state of the molecules undergoes a complete orientation and order transformation, accompanied by a large entropy change and heat release. When heat release is required, hydrostatic pressure or needle-puncture pressurization is used as the driving method to control heat release and achieve controllable heat storage, transfer, and utilization. 【0028】 The solutions of the present invention also relate to a heat storage and heat exchange device that includes a pressure calorific value material. The device includes a heating unit, a rapid cooling unit, and a pressurizing unit. The heating unit is used to bring the pressure calorific value material to a high-temperature, viscous crystalline phase. The rapid cooling unit is used to rapidly cool the high-temperature, viscous crystalline phase of the pressure calorific value material to obtain a glassy crystalline phase. The pressurizing unit controls heat release by applying hydrostatic pressure or needle-piercing pressure to the pressure calorific value material when heat release is necessary, thereby achieving controllable storage, transfer, and utilization of thermal energy. Figure 1 shows the cycle process. The pressure calorific value material is used as an energy transfer material in a heat storage and heat exchange device, and a solid-state refrigeration function is realized by utilizing the endothermic process of transitioning from a low-temperature, regular crystalline phase to a high-temperature, viscous crystalline phase. Phase transition from the glassy crystalline phase to a low-temperature, regular crystalline phase is achieved by a driving method such as hydrostatic pressure, realizing the heat storage and utilization function of the solid phase transition. 【0029】 The pressure-caloric effect material of the present invention is a pressure-caloric effect material having a glassy crystalline phase, and preferably a viscous crystalline material having a glassy crystalline phase. Since viscous crystalline materials are a type of highly disordered solid material, the orientation of structural unit molecules is completely disordered, but the center of gravity forms a long-range, regular lattice, and is therefore also called a rotationally disordered crystal. Because the disorder of molecular orientation is remarkably large, the entropy change during the solid phase transition is greater than the fusion entropy, and the proportion of disordered degrees of freedom in the total degrees of freedom of the system approaches the limit that maintains the rigidity of the solid. Weak intermolecular interactions result in a very large compressibility, and even minute pressures can be used to adjust intermolecular interactions, causing a phase transition between the ordered phase and the disordered phase, which results in a change of entropy. In the case of the glassy crystalline phase, compared to the viscous crystalline phase, the center of gravity maintains a long-range ordered state, but the disordered orientation state of organic molecules and inorganic structural units is frozen by supercooling, and is no longer a completely disordered rotational state. Nevertheless, the glassy crystalline phase still exhibits a high degree of disorder compared to conventional crystalline phases. Table 1 shows the specific differences between various phase structures and states. Therefore, viscous crystalline pressure-caloric effect materials having a glassy crystalline phase possess characteristics such as large phase transition entropy changes, pressure-adjustable phase transitions and controllability of entropy changes, and these features are fully applicable to the methods, apparatus, and applications of the present invention. The pressure-caloric effect material used in embodiments of the present invention is a pressure-caloric effect material having a glassy crystalline phase, preferably 2-amino-2-methyl-1,3-propanediol ((CH3)C(CH2)(CH2OH)2(AMP), m-carborane C2B in a viscous crystalline material. 10 H 12 , 1-Cyanoadamantane C 11 H 15 N (CAN), Adamantanone C 10 H 14 O (AON), and pentachloronitrobenzene C6C l5 One or more of the NO2(PCNB) compounds are selected. Among these, 2-amino-2-methyl-1,3-propanediol (CH3)C(CH2)(CH2OH)2(AMP) or m-carborane C2B are selected.10 H 12 More preferably, 2-amino-2-methyl-1,3-propanediol (CH3)C(CH2)(CH2OH)2(AMP) is even more preferred. 【0030】 [Table 1] 【0031】 Applications of the present invention include the recycling of waste heat in thermal power plants. In one embodiment, a pressure-caloric effect material with a low-temperature, regular crystalline phase having a glassy crystalline phase is placed in the cooling tower of the power plant. When circulating cooling water heated by waste heat flows through the pressure-caloric effect material, the material changes from a low-temperature phase to a high-temperature, viscous crystalline phase, and waste heat is transferred to and stored in the material. At the same time, the circulating water is cooled and continues to circulate to recover waste heat from the power plant. The high-temperature, viscous crystalline phase material is rapidly cooled and then changed to a glassy crystalline phase. This enables long-distance transport of waste heat collection material to low-temperature environments where heating is required. When heat is needed, applying less pressure causes the material to change from a glassy crystalline phase to a low-temperature, regular crystalline phase, achieving the objective of releasing heat for heating. 【0032】 Applications of the present invention also include the use of pressure-caloric effect materials having a glassy crystalline phase for storing solar energy. In one embodiment, a pressure-caloric effect material is used to absorb heat generated by a solar thermal collector. For example, the pressure-caloric effect material is placed in a solar thermal collector or heat storage component, and the material undergoes a phase transition to a high-temperature viscous crystal. Subsequently, the material changes from the high-temperature viscous crystalline phase to a glassy crystalline phase, and by maintaining this glassy crystalline state, heat storage at low temperatures is achieved, and finally, the heat is released and utilized by applying pressure. 【0033】 Applications of the present invention include the recycling of waste heat in computer rooms of data centers. In one embodiment, a pressure-caloric effect material having a glassy crystalline phase is used to absorb heat generated in a data center. For example, the pressure-caloric effect material is placed at the heat dissipation end of a data center host, and the material receives heat and undergoes a phase transition to a high-temperature viscous crystalline phase state. Subsequently, the material changes from the high-temperature viscous crystalline phase to a glassy crystalline phase. By maintaining the glassy crystalline phase state of the material, heat storage at low temperatures is achieved, and finally, the heat is released and utilized by applying pressure. 【0034】 In the following, preferred embodiments of the present invention will be described in detail using 2-amino-2-methyl-1,3-propanediol (CH3)C(CH2)(CH2OH)2(AMP) as an example. 【0035】 First embodiment for obtaining a glassy crystalline phase: A bulk sample of AMP in a low-temperature, regularly crystalline phase was placed in an airtight, high-pressure sample cell, while an empty comparison sample cell was placed in the sample chamber of a μDSC7 (Setalam, France) microcalorimeter. Nitrogen was flowed through both sample cells using a booster device, maintaining atmospheric pressure (0.1 MPa), and the cells were heated from 228 K to 383 K at a heating rate of 2 K / min. The heat flow data of the samples was recorded and shown in the curve in Figure 2. A phase transition occurred in AMP at 355 K, with a corresponding enthalpy change value of 215 Jg. -1 The value of the entropy change is 606 Jkg. -1 K -1 It can be seen that this is the case. Using this process, a cooling effect can be obtained by absorbing heat from the heat source. Also, the endothermic peak that appears around 381K corresponds to the melting point of AMP. In this way, the high-temperature viscous crystalline phase of AMP is obtained. 【0036】 Next, the sample in the high-temperature viscous crystalline phase is rapidly cooled to a low temperature of 273K at a cooling rate of 2K / min or more, freezing the sample's high-temperature disordered state through supercooling. This avoids the complete orientation ordering that normally occurs at low temperatures. Ultimately, AMP transitions to a glassy crystalline phase. The recorded heat flow data of the sample is shown in the curve in Figure 3. A heat dissipation peak can be seen at 378K, which corresponds to the freezing point of AMP. Unlike the heating process, no clear heat dissipation peak was observed during the cooling process below this point. This characteristic can be used to store and transport heat without being affected by spontaneous phase transitions due to cooling. 【0037】 Second embodiment for obtaining a glassy crystalline phase: When a sample of AMP powder in a regular crystalline phase is placed in a glass container at room temperature and heated using a heating device such as a heating stand, the temperature exceeds the heating phase transition temperature of AMP (the transition from a low-temperature regular crystalline phase to a high-temperature viscous crystalline phase), resulting in AMP in a high-temperature viscous crystalline phase. By rapidly cooling this AMP with ice water or liquid nitrogen, the high-temperature disordered state is instantly supercooled and frozen, yielding a glassy crystalline phase state. 【0038】 Storage of thermal energy: By continuously storing the obtained glassy crystalline phase at 273K, or by raising the temperature to below room temperature, AMP can be retained in the glassy crystalline phase for a long period of time without spontaneously changing to a low-temperature regular crystalline phase. This function allows AMP materials in the glassy crystalline phase to be used in a variety of low-temperature environments, and since spontaneous phase transitions due to temperature changes are avoided, long-distance transport becomes possible without spontaneous phase transitions or heat dissipation. 【0039】 Controllable heat dissipation: The glassy crystalline phase AMP material obtained in the first embodiment was continuously stored at a temperature of 273 K. After maintaining this temperature for 2 hours, nitrogen was flowed through two sample cells using a booster device, and the gas pressure was instantaneously increased to 67 bar. The heat flow data of the sample was recorded and shown in the curve in Figure 4. When a pressure of 67 bar was applied to the AMP glassy crystalline phase under maintenance at 273 K, a clear heat dissipation peak appeared in the sample, which corresponds to the exothermic process of the phase transition from the AMP glassy crystalline phase to the low-temperature phase under pressurization. The corresponding enthalpy change value was 133 Jg. -1 The entropy change value is 487 J kg. -1 K -1 This result demonstrates that the heat stored in the glassy crystalline phase of AMP can be controlled with low pressure to achieve active heat release. The transformation of AMP from the glassy crystalline phase to the regular crystalline phase can be achieved by pressure. This phase transition is accompanied by the release of a large amount of latent heat, thereby achieving controlled release and controllable utilization of the heat stored within the AMP material. 【0040】 For the sample obtained according to the second embodiment, the temperature of the AMP material in the glassy crystalline phase state, stored at room temperature, is measured and monitored in real time using a K-type thermocouple. When the temperature is constant at room temperature, a sharp object such as a needle is used to puncture the sample and apply pressure to induce a phase transition from the glassy crystalline phase to a low-temperature regular crystalline phase, while simultaneously monitoring the sample temperature in real time. The results are shown in the curve in Figure 5. Simultaneously with the phase transition, the sample temperature rises instantaneously, and it is shown that under imperfect adiabatic conditions, the temperature change reaches 32.5K, thereby achieving active release and controllable utilization of the accumulated heat. 【0041】 The heating / cooling cycle process of AMP from a high-temperature phase to a glassy crystal: A low-temperature, regularly ordered crystalline AMP sample was placed in an airtight, high-pressure sample cell, while an empty comparison sample cell was placed in the sample chamber of a μDSC7 (Setalam, France) microcalorimeter. Nitrogen was flowed through both sample cells using a booster device, maintaining atmospheric pressure (0.1 MPa), and the cells were heated from 273 K to 383 K at a heating rate of 2 K / min, followed by cooling to 273 K at a cooling rate of 2 K / min. The above process was repeated six times, and the heat flow data of the samples was recorded and shown as curves in Figure 6. The results show that, in the temperature range from high temperature to 273 K, no transition from the glassy crystalline phase to the low-temperature ordered phase was observed during the heating or cooling process, indicating that the AMP is recyclable. 【0042】 Temporal stability of the AMP glassy crystalline phase: A low-temperature, regularly crystalline AMP sample was placed in an airtight, high-pressure sample cell, while an empty comparison sample cell was placed in the sample chamber of a μDSC7 (Setalam, France) microcalorimeter. Nitrogen was introduced into both sample cells using a booster device, and the cells were heated from 273K to 383K at a heating rate of 2K / min while maintaining atmospheric pressure (0.1 MPa). They were then cooled to 273K at a cooling rate of 2K / min. The cells were then incubated at 273K for 24 hours, and the heat flow data of the samples was recorded and shown in the curve in Figure 7. These results demonstrate that the glassy crystalline phase of AMP can be stably stored under ambient temperature conditions of 273K and exhibits temporal stability. This characteristic ensures the storage of thermal energy in low-temperature environments for this type of material. 【0043】 Application Example 1 of the Method and Materials of the Present Invention in Solid Phase Transition Heat Storage: Typically, the actual thermal efficiency of thermal power plants is low, with approximately 60% of the heat being lost to the circulating cooling water in the condenser and released into the environment. The cooling water circulating in the power plant is low-grade thermal energy, and its direct utilization is limited; in the past, direct discharge methods using cooling towers were used. On the other hand, various waste heats are generated during the production process of thermal power plants, such as steam leaks from shaft seals, boiler blowdown, and exhaust from deaerators, all of which are processes that carry waste heat. Until now, this heat has not been utilized and has been directly released into the environment. The released heat not only causes thermal pollution in the environment but also reduces the energy efficiency of the thermal power plant. In the above processes of heat generation and dissipation, by placing low-temperature, regular crystalline AMP in the pipelines of the power plant's cooling towers, boiler blowdown components, deaerator exhaust components, and other equipment, when the temperature of the above pipelines or components exceeds 355K, the AMP changes from a low-temperature phase to a high-temperature, viscous crystalline phase, thereby transferring and storing waste heat in the AMP, while simultaneously achieving cooling of the pipelines or components. After recovering waste heat, as the ambient temperature decreases, AMP gradually transforms from the high-temperature phase to a glassy crystalline phase without changing to a low-temperature regular crystalline phase, achieving heat storage without energy loss. Spontaneous phase transitions and heat release do not occur due to the decrease in ambient temperature. Therefore, AMP in the glassy crystalline phase can be transported over long distances and can be transported to remote low-temperature environments (e.g., below 273K). Finally, in scenarios where heat utilization is required, applying a small pressure can convert AMP from the glassy crystalline phase to a low-temperature regular crystalline phase, a process accompanied by the release of a large amount of latent heat. The goal is to control the phase transition and actively control heat release using pressure stimulation. 【0044】 Application Example 2 of the Method and Materials of the Present Invention in Solid Phase Transition Heat Storage: Solar energy is a clean, renewable energy source, and among renewable energy sources, it is the most widely distributed and readily available. However, solar energy is highly intermittent and unstable. To stably utilize solar energy, a thermal storage device is necessary to store solar energy. Based on the above solar thermal storage scenario, a low-temperature, regular crystalline phase AMP can be placed in a solar thermal collector or thermal storage component. Once the heat is collected and the AMP temperature exceeds 355K, the AMP changes from a low-temperature phase to a high-temperature, viscous crystalline phase, and the thermal energy generated by solar energy is transferred to the AMP and stored. After collecting a large amount of heat, if the ambient temperature drops rapidly, the AMP gradually transforms from the high-temperature phase to a glassy crystalline phase without changing back to a low-temperature, regular crystalline phase, thus achieving thermal storage. The decrease in ambient temperature does not cause spontaneous phase transitions or heat release. Therefore, the glassy crystalline phase AMP can be transported over long distances and can be transported to remote low-temperature environments (e.g., below 273K). Finally, in scenarios where heat is required, applying a small amount of pressure can convert AMP from a glassy crystalline phase to a low-temperature, regular crystalline phase. This process involves the release of a large amount of latent heat. The goal is to control the phase transition and actively control heat release using pressure stimulation. 【0045】 Application Example 3 of the Method and Materials of the Present Invention in Solid Phase Transition Heat Storage: Data centers are becoming increasingly popular worldwide. Meanwhile, 5G is gradually moving towards large-scale commercial use, and data centers are facing enormous business needs as carriers of information processing equipment. On the other hand, data centers are included in the national "new infrastructure" strategic category, becoming an important part of building national information infrastructure and providing crucial support for creating a "dual circulation of the economy" pattern. However, a rapid increase in the power consumption of a single machine within a data center directly leads to a significant rise in the temperature of equipment in the computer room, not only impairing equipment performance but also consuming a large amount of electricity to operate refrigeration equipment such as air conditioners. For example, an AMP with a low-temperature regular crystalline phase can be installed at the heat dissipation end of a data center host. When the heat dissipation temperature exceeds 355K, the AMP undergoes a phase transition from the low-temperature phase to a high-temperature viscous crystalline phase, thereby transferring and storing heat in the AMP. After collecting a large amount of heat, when the ambient temperature drops rapidly, the AMP does not change back to the low-temperature regular crystalline phase but gradually transforms from the high-temperature phase to a glassy crystalline phase, achieving heat storage. The decrease in ambient temperature prevents spontaneous phase transitions and heat release. Therefore, AMP in the glassy crystalline phase can be transported over long distances and can be transported to remote low-temperature environments (e.g., below 273K). Finally, in scenarios where heat utilization is required, applying a small amount of pressure can convert AMP from the glassy crystalline phase to a low-temperature regular crystalline phase. This process involves the release of a large amount of latent heat. The goal is to control the phase transition and actively control heat release using pressure stimulation. 【0046】 The embodiments described above are merely for illustrative purposes to illustrate the technical concepts and features of the present invention. The purpose is to enable those skilled in the art to understand and implement the present invention accordingly, and not to limit the scope of protection. Conversely, any effective modifications or alterations made in accordance with the spirit of the present invention shall be included within the scope of protection.

Claims

[Claim 1] A controllable solid phase change heat storage and heat release method for pressure calorific effect materials, Step 1 involves heating the pressure-caloric effect material to create a flexible crystalline phase, Step 2 involves rapidly cooling the aforementioned viscous crystalline phase of the pressure-calorific effect material to obtain a glassy crystalline phase of the pressure-calorific effect material, thereby achieving long-term thermal energy storage in the glassy crystalline phase of the pressure-calorific effect material. Step 3 includes storing the glassy crystalline phase of the pressure-caloric effect material at 273 K or maintaining it at a temperature below room temperature without spontaneous phase transition and heat release, wherein the phase transition does not occur with external temperature changes, and the phase transition is induced by applying pressure only by hydrostatic pressure to the glassy crystalline phase of the pressure-caloric effect material, thereby controlling heat release and achieving controllable storage, transfer, and utilization of thermal energy. The aforementioned pressure-caloric effect material is 2-amino-2-methyl-1,3-propanediol (AMP), In step 1, the pressure-caloric material is heated to 355 K (82°C), causing a phase transition in the pressure-caloric material. The material absorbs heat and changes to the viscous crystalline phase, and the corresponding enthalpy change is 215 Jg. －１ The value of the entropy change is 606 J kg. －１ K －１ And, In step 2, the method for rapidly cooling the pressure-caloric material of the viscous crystalline phase includes a method of cooling at a cooling rate of 2 K / min or more, or a method of cooling with ice water or liquid nitrogen, wherein the pressure-caloric material of the viscous crystalline phase is rapidly cooled to 273 K to obtain the glassy crystalline phase. In step 3, the value of the hydrostatic pressure is 67 bar or more. A method for heat storage and release by solid phase transition of a pressure-caloric effect material, characterized by the features described above.

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