CN111154457A - Inorganic composite phase change energy storage material and preparation method thereof - Google Patents
Inorganic composite phase change energy storage material and preparation method thereof Download PDFInfo
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- CN111154457A CN111154457A CN201910673197.8A CN201910673197A CN111154457A CN 111154457 A CN111154457 A CN 111154457A CN 201910673197 A CN201910673197 A CN 201910673197A CN 111154457 A CN111154457 A CN 111154457A
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- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
Abstract
The invention discloses an inorganic composite phase change energy storage material, a preparation method thereof and a phase change energy storage device comprising the inorganic composite phase change energy storage material, wherein the inorganic composite phase change energy storage material comprises the following components in parts by weight: 50-99 parts by weight of an energy storage main material; 0.1-20 parts by weight of a nucleating agent; 0.01-50 parts of buffering agent, wherein the energy storage main body material is an inorganic phase change material, and is preferably one or more selected from alkali hydrate and crystalline hydrated salt. The inorganic composite phase change energy storage material effectively improves the phenomena of supercooling and phase separation in the phase change process, and has high crystallization rate, short phase change time and good application prospect. The preparation method of the inorganic composite phase change energy storage material is simple in process and easy to implement, and the phase change energy storage device containing the phase change material is high in energy utilization rate and heat exchange efficiency.
Description
Technical Field
The invention belongs to the technical field of phase change energy storage, and particularly relates to an inorganic composite phase change energy storage material and a preparation method and application thereof.
Background
In recent years, the phase change energy storage technology has gained more and more attention and development in the fields of renewable energy utilization, energy conservation, consumption reduction and the like, and the application thereof in heating, ventilation and air conditioning systems is more and more. The medium-low temperature phase change energy storage material used in the field of air conditioners is developed, cheap electric energy in electricity consumption valleys can be converted into heat energy to be stored in the phase change material, the heat energy is released in electricity consumption peaks, the electricity consumption in the peak periods is reduced, and the effects of peak clipping and valley filling are achieved. In the currently known energy storage methods, the inorganic phase-change material has high heat storage density and stable phase-change temperature, so that the inorganic phase-change material is widely applied to heating, ventilating and air conditioning, solar heat storage, environment-friendly home furnishing and the like.
The inorganic phase change material has wide application range, and has relatively great phase change heat and fixed melting point. Compared with organic phase-change materials, the crystalline hydrated salt has the advantages of higher heat conductivity coefficient, high density, high heat storage density per unit volume and the like. However, crystalline hydrated salts have the disadvantages of large supercooling degree, phase separation, corrosiveness and the like during crystallization, and in order to reduce the supercooling degree and inhibit the occurrence of phase separation phenomenon, certain amounts of nucleating agents and thickening agents are required to be added for improvement in practical application, so that the methods of adding inorganic nucleating agents (for example, CN107011867A and CN107502299A) are more and the method of adding organic nucleating agents is still blank at present in the known patents, and particularly, the method of adding organic fibrous substances for improving the crystallization performance is not mentioned.
Therefore, it is highly desirable to develop a phase change energy storage material with low supercooling degree and a preparation method thereof.
Disclosure of Invention
In order to overcome the problems, the inventor of the invention carries out intensive research and designs an inorganic composite phase change energy storage material, the phase change energy storage material comprises an energy storage main body material, a nucleating agent and a buffering agent, the obtained phase change energy storage material improves the supercooling and phase separation phenomena in the phase change process, and has high crystallization rate, short phase change time and good application prospect, thereby completing the invention.
The invention aims to provide an inorganic composite phase change energy storage material, which comprises the following components in parts by weight:
50-99 parts by weight of an energy storage main material;
0.1-20 parts by weight of a nucleating agent;
0.01 to 50 parts by weight of a buffer.
The energy storage main body material is an inorganic phase change material, and is preferably selected from one or more of alkali hydrate and crystalline hydrated salt.
Wherein the alkali hydrate is selected from one or more of sodium hydroxide monohydrate, barium hydroxide octahydrate and strontium hydroxide octahydrate, and/or
The crystalline hydrated salt is selected from one or more of calcium chloride hexahydrate, aluminum potassium sulfate dodecahydrate, sodium sulfate decahydrate, potassium fluoride dihydrate, sodium acetate trihydrate, sodium thiosulfate pentahydrate, magnesium sulfate heptahydrate, sodium sulfate decahydrate, disodium hydrogen phosphate dodecahydrate, aluminum ammonium sulfate dodecahydrate and aluminum sulfate octadecahydrate.
The nucleating agent is an inorganic nucleating agent and/or an organic nucleating agent,
wherein the inorganic nucleating agent is selected from one or more of quartz, disodium hydrogen phosphate dodecahydrate, borax, calcium chloride dihydrate, potassium dihydrogen phosphate, sodium pyrophosphate, sodium acetate, sodium sulfate, barium chloride, calcium fluoride, barium hydroxide, nano silicon dioxide, nano titanium dioxide or inorganic fibers,
the organic nucleating agent is organic fiber.
The organic fiber is selected from one or more of aramid fiber, polypropylene fiber, acrylic fiber, polyimide, nylon, polyethylene fiber, polypropylene fiber, poly-p-phenylene benzobisoxazole fiber, poly-p-benzimidazole fiber and poly-phenylene pyridyldiimidazole fiber.
The buffer is a saturated solution of an inorganic hydrate, preferably a saturated solution of an alkali hydrate or a crystalline hydrated salt.
A second aspect of the present invention provides a method for preparing the phase change energy storage material according to the first aspect of the present invention, the method comprising the steps of:
and 4, cooling and forming to obtain the inorganic composite phase change energy storage material.
Wherein, in the step 2, a nucleating agent is added into the container, and then an energy storage main body material and a buffer agent are added,
in step 3, the mixture obtained in step 2 is heated to be molten.
A third aspect of the present invention provides a phase change energy storage device comprising a phase change energy storage material according to the first aspect of the present invention and/or according to the present invention.
The invention has the following beneficial effects:
(1) the invention takes an inorganic phase-change energy storage material as an energy storage main body material, takes a saturated solution of the energy storage main body material as a buffering agent, and takes a fiber material as a nucleating agent to prepare the inorganic composite phase-change energy storage material.
(2) The inorganic composite phase change energy storage material improves the supercooling and phase separation phenomena in the phase change process, improves the cycle times and the service life of the phase change energy storage material; and the nucleation rate of the phase-change material in the phase-change process can be improved, and the phase-change time is shortened, for example, when the percentage content of the fiber is 2.5-5%, the nucleation rate of the phase-change energy storage material can be improved by more than 15%, preferably by more than 17%, and even by 33%.
(3) The preparation method of the inorganic composite phase change energy storage material is simple, the raw materials are easy to obtain, the realization is easy, and the method is suitable for large-scale popularization and implementation;
(4) the phase change energy storage device comprising the inorganic composite phase change energy storage material provided by the invention has high energy utilization rate and high heat exchange efficiency, and can be applied to heating ventilation air conditioners, solar heat storage, floor heating systems, environment-friendly homes and the like.
Drawings
Fig. 1 shows a schematic structural view of a phase change energy storage device according to a preferred embodiment of the present invention;
FIG. 2 shows the cooling curve obtained in Experimental example 1 of the present invention.
The reference numbers illustrate:
1-water inlet pipe;
2-water outlet pipe;
3, heat exchange tubes;
4-an energy storage box body;
41-phase change energy storage material
5-a condenser pipe;
51-a pressure relief valve;
6-a heater;
7-pressure temperature controller;
8-an insulating layer;
9-a housing;
10-helical tube section.
Detailed Description
The invention is explained in more detail below with reference to the drawings and preferred embodiments. The features and advantages of the present invention will become more apparent from the description.
According to the invention, on one hand, the invention provides an inorganic phase change energy storage material, which comprises the following components in parts by weight:
50-99 parts by weight of an energy storage main material;
0.1-20 parts by weight of a nucleating agent;
0.01 to 50 parts by weight of a buffering agent,
according to the invention, the phase change energy storage material comprises 0.1-10 parts by weight of nucleating agent, preferably 1-8 parts by weight of nucleating agent, and more preferably 2.5-5 parts by weight of nucleating agent.
In the invention, the nucleation effect is not obviously enhanced in the adding process of the nucleating agent, the raw materials of the nucleating agent are wasted, the nucleation promotion effect cannot be realized when the adding amount of the nucleating agent is too small, and the nucleation of the obtained phase-change material cannot be realized when the adding amount of the nucleating agent is less than 0.1 part by weight.
According to the invention, the phase change energy storage material comprises 0.1-50 parts by weight, preferably 1-50 parts by weight, and more preferably 10-50 parts by weight of a buffering agent.
In the invention, the buffer cannot play a role in buffering when the addition amount of the buffer is too small, and the buffer accounts for a larger proportion in the phase-change material when the addition amount of the buffer is too large, so that the energy storage density of the phase-change material is reduced.
According to the invention, the energy storage main body material is an inorganic phase change material, and preferably one or more of alkali hydrate and crystalline hydrated salt inorganic phase change materials.
According to the invention, the alkali hydrate is selected from one or more of sodium hydroxide monohydrate, barium hydroxide octahydrate and strontium hydroxide octahydrate, preferably sodium hydroxide monohydrate or barium hydroxide octahydrate, such as barium hydroxide octahydrate.
According to the invention, the crystalline hydrated salt is selected from one or more of calcium chloride hexahydrate, potassium aluminium sulphate dodecahydrate, sodium sulphate decahydrate, potassium fluoride dihydrate, sodium acetate trihydrate, sodium thiosulphate pentahydrate, magnesium sulphate heptahydrate, sodium sulphate decahydrate, disodium hydrogen phosphate dodecahydrate, aluminium ammonium sulphate dodecahydrate and aluminium sulphate octadecahydrate.
According to the invention, the energy storage host material is selected from one or more of barium hydroxide octahydrate, calcium chloride hexahydrate, aluminum potassium sulfate dodecahydrate, sodium sulfate decahydrate, disodium hydrogen phosphate dodecahydrate and aluminum ammonium sulfate dodecahydrate, such as barium hydroxide octahydrate.
In the invention, the crystallized hydrated salt has larger phase transition heat and fixed melting point, when the temperature is increased, the crystallized hydrated salt loses the crystal water to dissolve and desorb the heat of the salt, and when the temperature is reduced, the reverse process is generated to absorb the crystal water to release the heat. The crystalline hydrated salt has the advantages of large heat conductivity coefficient, large density, high heat storage density per unit volume and the like. However, the crystallization of the crystalline hydrated salt has disadvantages such as a large supercooling degree, phase separation and corrosiveness, and it is necessary to improve the supercooling degree and the phase separation phenomenon by adding a certain amount of a nucleating agent and/or a thickener.
According to the invention, the nucleating agent is selected from inorganic nucleating agents and/or organic nucleating agents.
According to the invention, the inorganic nucleating agent is selected from one or more of quartz, disodium hydrogen phosphate dodecahydrate, borax, calcium chloride dihydrate, potassium dihydrogen phosphate, sodium pyrophosphate, sodium acetate, sodium sulfate, barium chloride, calcium fluoride, barium hydroxide, nano-silica, nano-titanium dioxide or inorganic fibers.
According to the invention, the organic nucleating agent is selected from organic fibres.
In the invention, the nucleating agent plays a role in promoting the crystallization of inorganic phase-change materials such as crystalline hydrated salt phase-change materials, and the fibrous materials are used as the nucleating agent and are not easy to settle, so that the crystallization rate is high, and the phase-change time of the phase-change energy storage material is shortened.
According to the present invention, the nucleating agent is a fibrous material, the form of the fiber is not particularly limited, and may be a filamentous and/or striped fibrous material, such as a filament or a fiber fabric. According to the invention, the nucleating agent is selected from inorganic fibres and/or organic fibres.
According to the invention, the inorganic fiber is preferably glass fiber, the organic fiber is one or more selected from aramid fiber, polypropylene fiber, acrylic fiber, polyimide, nylon, polyethylene fiber, polypropylene fiber, poly-p-phenylene benzobisoxazole fiber, poly-p-benzimidazole fiber and poly-p-phenylene pyridbisimidazole fiber, preferably one or more selected from aramid fiber, polypropylene fiber and nylon, such as polypropylene fiber.
In the invention, when the nucleating agent is organic fiber, in order to avoid the organic fiber floating on the liquid surface and influencing the nucleating efficiency, the organic fiber can be fixed on the bracket and then filled with the inorganic phase-change material.
In the invention, the alkali hydrate or crystalline hydrated salt and the like are cooled to cause crystallization and agglomeration, and the volume expansion is easy to cause extrusion damage to equipment pipelines and the like, so that the equipment cannot be normally used, the cycle life of the phase-change material is reduced, and therefore, a buffering agent for preventing the crystallization and agglomeration is required to be added.
According to the invention, the buffer is selected from saturated solutions of the energy storage host material, preferably of the inorganic phase change material, such as saturated solutions of alkali hydrates and crystalline hydrated salts, for example, if the energy storage host material is barium hydroxide octahydrate, the buffer is a saturated solution of barium hydroxide octahydrate; if the energy storage main body material is aluminum potassium sulfate dodecahydrate, the buffering agent is saturated solution of the aluminum potassium sulfate dodecahydrate.
According to the invention, the inorganic composite phase change energy storage material also comprises a thickening agent, wherein the thickening agent is selected from one or more of super absorbent resin, fumed silica, polyacrylamide, hydroxymethyl cellulose, bentonite, sodium polyacrylate, gelatin, xanthan gum, starch and guar gum.
In a second aspect, the present invention provides a method for preparing an inorganic composite phase change energy storage material, preferably a method for preparing the phase change energy storage material according to the first aspect of the present invention, the method comprising the following steps:
and 4, cooling and forming to obtain the inorganic composite phase change energy storage material.
According to the invention, in the step 1, 50-99 parts by weight of an energy storage main material, 50-99 parts by weight of a nucleating agent and 50-99 parts by weight of a buffer agent are weighed; 0.1-20 parts by weight of a nucleating agent; 0.01 to 50 parts by weight of a buffering agent,
wherein, the nucleating agent is preferably 0.1 to 10 parts by weight, more preferably 1 to 8 parts by weight, and still more preferably 2.5 to 5 parts by weight;
the buffer is preferably 0.1 to 50 parts by weight, more preferably 1 to 50 parts by weight, and still more preferably 10 to 50 parts by weight.
According to the invention, in the step 1, a thickening agent is also added, wherein the thickening agent is selected from one or more of super absorbent resin, fumed silica, polyacrylamide, hydroxymethyl cellulose, bentonite, sodium polyacrylate, gelatin, xanthan gum, starch and guar gum. The thickener is added in an amount of 0.01 to 5 parts by weight, preferably 0.01 to 1 part by weight, more preferably 0.01 to 0.05 part by weight, for example, 0.03 part by weight.
According to the invention, in step 2, when the nucleating agent is an organic fiber, the nucleating agent is firstly added into the container, and then the energy storage main body material and the buffer are added, preferably, the energy storage main body material and the buffer are uniformly mixed and then added into the container containing the nucleating agent.
According to the invention, in the step 2, when the nucleating agent is organic fiber, in order to prevent the organic fiber from floating on the upper layer of the solution to influence the nucleating effect, the organic fiber is fixed by adopting an anti-corrosion support, and then the energy storage main body material and the buffer are added to prevent the organic fiber from floating, so that the organic fiber can be fully contacted with the energy storage main body material and the buffer, thereby increasing the contact area of the organic fiber and the energy storage main body material and the buffer, promoting the nucleating, improving the crystallization rate and shortening the phase change time.
According to the invention, in step 3, the mixture obtained in step 2 is heated, preferably to melt, and the phase change material undergoes a phase change from a solid state to a liquid state.
According to the invention, in the step 3, the heating temperature is 70-100 ℃, preferably 80-95 ℃, more preferably 85-95 ℃, for example 92 ℃.
According to the invention, in step 4, the mixture is heated to melt and then cooled to be formed, preferably naturally cooled to room temperature (25 ℃) to obtain the inorganic composite phase change energy storage material.
According to the invention, in step 4, the mixture is cooled with stirring to promote crystallization and reduce or eliminate phase separation.
The inorganic composite phase change energy storage material according to the first aspect of the present invention or the inorganic composite phase change energy storage material prepared by the method according to the second aspect of the present invention improves supercooling and phase separation of inorganic salts during crystallization, and the addition of a nucleating agent of a fibrous material in the energy storage material increases crystallization rate (or nucleation rate) of the inorganic salts and shortens phase change time. For example, the nucleation rate can be increased by more than 15%, preferably more than 17%, even up to 33%.
In the present invention, the nucleation rate is inversely proportional to the phase transition time.
A third aspect of the invention provides a phase change energy storage device comprising an inorganic composite phase change energy storage material as described in the first aspect and/or as prepared by the method of the second aspect of the invention.
According to the invention, as shown in fig. 1, the phase change energy storage device comprises an energy storage box body 4 for containing phase change energy storage materials 41, the energy storage box body 4 is a closed container, preferably a closed container without welding spots, and the energy storage box body 4 is preferably made of a metal material, preferably a corrosion-resistant material such as a stainless steel material, an alloy material and the like.
According to the present invention, the phase change energy storage material 41 is an inorganic composite phase change energy storage material according to the first aspect of the present invention and/or prepared according to the second aspect of the present invention.
According to the invention, as shown in fig. 1, in order to further enhance the heat preservation and insulation effect of the phase change energy storage material 41 in the energy storage box 4 and prevent heat dissipation loss, it is preferable that a heat preservation layer 8 is arranged outside the energy storage box, the heat preservation layer 8 is made of a heat preservation material, and the heat preservation material is preferably selected from one or more of polyurethane foam materials, polyphenyl heat preservation materials, rock wool heat preservation materials, vacuum heat preservation materials and perlite heat preservation materials.
According to the invention, the heat-insulating layer 8 is also covered with the shell 9, so as to protect the heat-insulating layer and further enhance the heat-insulating effect.
According to the invention, in order to prevent the phase change energy storage material from corroding the energy storage box body 4, an anti-corrosion layer is arranged on the inner wall of the energy storage box body 4, the anti-corrosion layer is an integrally formed container formed by anti-corrosion materials, and a plate material is subjected to hot melting welding or anti-corrosion coating, and the anti-corrosion material is preferably selected from any one or more of natural rubber, chloroprene rubber, butyl rubber, ethylene propylene rubber, fluorine rubber, chlorosulfonated polyethylene rubber, epichlorohydrin rubber, chlorinated polyethylene rubber, polypropylene, polytetrafluoroethylene, polyamide plastic, polyvinyl chloride, ABS, polycarbonate plastic, fluoroplastic, glass fiber reinforced plastic and resin.
According to the invention, the phase change energy storage device is further provided with a heater 6 for heating the phase change energy storage material.
According to a preferred embodiment of the present invention, the heater 6 extends into the phase change energy storage material 41 of the energy storage tank 4 to heat it.
According to a further preferred embodiment of the invention, the heater 6 is electrically heated, for example by resistance wire heating.
According to another preferred embodiment of the present invention, the heater 6 includes a heating coil, the heating coil is spirally embedded in the phase change energy storage material 41, a heat medium is introduced into the coil, and the phase change energy storage material is heated by introducing the heat medium into the heating coil, so as to complete heat exchange.
According to the invention, the heating coil is formed by connecting a plurality of U-shaped tubes in parallel or in series, so that the contact area between the heating coil and the phase-change material is increased, the phase-change material can be rapidly and uniformly heated, and the phase-change material is uniformly heated.
According to another preferred embodiment of the present invention, the heater 6 is a microwave heating device (such as a microwave heating furnace), and the phase change energy storage material 41 is heated by microwave heating, so that the phase change energy storage material 41 is heated uniformly by the microwave heating, the temperature of the phase change energy storage material 41 is not too high or too low, the number of phase change cycles is greater, and the service life of the phase change material is longer.
According to the invention, the phase change energy storage device also comprises a pressure and temperature controller 7 for controlling the pressure and temperature of the energy storage box body 4, and the temperature and pressure of the phase change material in the energy storage box body are monitored and controlled at any time, so that the stable operation of heat exchange is ensured.
According to the invention, the phase change energy storage device comprises a heat exchanger, wherein the heat exchanger comprises a water inlet pipe 1, a heat exchange pipe 3 and a water outlet pipe 2.
According to the invention, the water inlet pipe 1, the heat exchange pipe 3 and the water outlet pipe 2 are integrally formed pipelines, or the water inlet pipe 1, the heat exchange pipe 3 and the water outlet pipe 2 are connected in a welding mode, and the welding position is outside the energy storage box body 4, so that the problems that welding spots welded by a plurality of sections of pipelines are contacted with a phase change material, the welding spots are corroded, and a working medium in the pipelines is contacted with the phase change energy storage material, so that the heat exchange process cannot be better carried out can be avoided.
According to the invention, the heat exchanger also comprises a working medium, and the working medium sequentially passes through the water inlet pipe 1, the heat exchange pipe 3 and the water outlet pipe 2.
According to the invention, the heat exchange tube 3 is embedded in the phase change energy storage material 41, when the working medium flows through the heat exchange tube 3, the phase change energy storage material 41 and the working medium perform heat exchange, preferably, the phase change energy storage material 41 transfers the heat stored in the phase change energy storage material to the working medium, and the working medium takes away the heat to complete the heat exchange.
In the present invention, in order to better exchange heat between the phase change material 41 and the working medium, the heat exchange tube 3 needs to contact the phase change material to the maximum extent so as to exchange heat.
According to a preferred embodiment of the present invention, the heat exchange tube 3 is composed of one to a plurality of straight tubes connected in parallel.
According to another preferred embodiment of the present invention, the heat exchange tube 3 is a spiral tube.
According to another preferred embodiment of the present invention, the heat exchange tube 3 is formed by one or more U-shaped tubes connected in parallel or in series, so that heat exchange can be performed more sufficiently, and the heat exchange efficiency can be improved.
According to the invention, in order to prevent the phase change material from corroding the water inlet pipe 1 and the water outlet pipe 2, especially the heat exchange pipe 3 in the heat exchanger, the water inlet pipe 1, the water outlet pipe 2 and the heat exchange pipe 3 are preferably made of carbon steel, stainless steel, aluminum and aluminum alloy, copper and copper alloy and the like, and more preferably, the water inlet pipe 1, the water outlet pipe 2 and the heat exchange pipe 3 need to be subjected to anti-corrosion treatment, for example, the outer wall of the pipe is coated with an anti-corrosion coating.
According to a preferred embodiment of the present invention, when the nucleating agent is an organic fiber in the phase change energy storage material 41, in order to prevent the organic fiber from floating on the upper layer of the liquid too lightly to affect the nucleation efficiency, it is preferable to first provide an anti-corrosion support in the energy storage tank of the phase change energy storage device, fix the organic fiber on the anti-corrosion support in a knotting and winding manner, preferably weave the organic fiber into a network structure on the anti-corrosion support, and then fill the inorganic hydrated salt phase change material and the buffer agent, thereby obtaining the phase change energy storage material of the present invention.
According to the invention, the anti-corrosion bracket is made of stainless steel materials, and preferably the surface of the stainless steel materials is coated with an anti-corrosion coating to prevent the phase change energy storage materials from corroding or damaging the anti-corrosion bracket.
According to the invention, the corrosion protection support has a frame structure, preferably a rectangular parallelepiped frame structure or a spiral frame structure, the rectangular parallelepiped frame structure being woven with organic fibers on at least one face into a network-like structure, more preferably with organic fibers on the upper and/or lower base of the frame structure.
According to the invention, one or more anti-corrosion support structures can be arranged to increase the contact area of the nucleating agent and the energy storage main body material, so that the nucleation rate is increased.
In the phase change energy storage material comprising the crystalline hydrated salt, the crystalline hydrated salt absorbs heat in the phase change process, the crystal water is evaporated, the crystalline hydrated salt needs to absorb the crystal water during heat release, and if the moisture removed by the crystalline hydrated salt cannot be combined with the crystalline hydrated salt in time, the crystalline hydrated salt cannot continue to undergo the phase change process, so that the cycle number of the phase change energy storage material is influenced. Therefore, there is a need to reduce evaporation of moisture from phase change energy storage materials during phase change.
According to the invention, a condensate return device is connected above the top of the energy storage tank 4, preferably the condensate return device is connected to the top of the energy storage tank 4.
According to the invention, the condensation reflux equipment comprises a condensation pipe 5, one end of the condensation pipe 5 is communicated with the top of the energy storage box body 4, preferably, the axis of the condensation pipe 5 is vertical to the upper surface of the top of the energy storage box body 4, water vapor generated after phase change of a phase change material in the energy storage box body 4 can enter the condensation pipe 5, the other end of the condensation pipe 5 is provided with a pressure release valve 51, the pressure release valve 51 can maintain the pressure of the energy storage box body 4, and when the vapor pressure in the energy storage box body 4 is too large, the pressure release valve 51 is opened to release the pressure, so that the pressure of the energy storage box body 4.
According to the invention, the water inlet pipe 1 is provided with a spiral pipe section 10, the spiral pipe section 10 is sleeved on the condensation pipe 5, namely the condensation pipe 5 penetrates through the spiral pipe section 10, and preferably the spiral pipe section 10 is wound on the condensation pipe 5.
In the invention, a heater 6 heats a phase change energy storage material 41 in an energy storage box body, such as a phase change energy storage material comprising crystalline hydrated salt, the crystalline hydrated salt absorbs heat to lose crystalline water, stores heat, the crystalline water is evaporated to enter a condenser pipe 5, after a working medium with a lower temperature is introduced into a heat exchanger, the working medium enters a heat exchange pipe 3 through a water inlet pipe 1, when the working medium flows through the water inlet pipe 1, the crystalline water in the condenser pipe 5 is condensed into liquid due to the lower temperature of the water inlet pipe 1, the liquid falls into the phase change energy storage material in the energy storage box body 4 through the condenser pipe 5, and when the working medium flows through the heat exchange pipe 3, the heat exchange is carried out between the heat exchange pipe 3 and the phase change energy storage material 41, the phase change energy storage material 41 releases heat, and.
In the invention, by utilizing the convection principle, water vapor evaporated from the energy storage box body 4 is evaporated and enters the condensation pipe 5, and the water vapor directly flows back to the energy storage box body 4 from the condensation pipe 5 after being condensed by the working medium of the spiral pipe section 10.
According to the invention, the volume occupied by the phase change energy storage material 41 in the energy storage box body 4 is not more than 3/4 of the volume of the energy storage box body 4, so that when the phase change occurs, the volume expansion is prevented from filling the energy storage box body 4, and the phase change cannot be continuously caused.
The method for storing energy and supplying heat by adopting the phase change energy storage device comprises the following steps:
and 3, introducing a working medium into the water inlet pipe 1, condensing and refluxing the crystal water in the condenser 5 into the phase change energy storage material 41, and allowing the working medium to flow through the heat exchange pipe 3 to finish heat exchange.
According to the present invention, step 1, a phase change energy storage device is prepared or installed, said phase change energy storage device being as described in the third aspect of the present invention.
According to the invention, in step 2, the energy storage process (heat storage process): the phase change energy storage material 41 is heated by the heater 6, the phase change energy storage material 41 is heated to a set temperature and then kept at the constant temperature for a certain time, wherein the constant temperature time is obtained according to energy required by heat storage, in the process, the phase change energy storage material 41 such as crystalline hydrated salt generates phase change, crystal water in the phase change energy storage material 41 is evaporated and enters the condenser pipe 5, for example, the crystalline hydrated salt loses the crystal water, the crystal water is evaporated and enters the condenser pipe 5, the phase change energy storage material 41 stores all phase change latent heat and partial sensible heat, and heating is stopped after the temperature reaches the set temperature.
According to the invention, in step 3, the energy supply process (exothermic process): the low-temperature working medium (such as cold water) is introduced into a water inlet pipe 1 of the heat exchanger, the working medium flows through a spiral pipe section 10 of the water inlet pipe 1, the spiral pipe section 10 is wound on a condensation pipe 5, the working medium in the spiral pipe section 10 can condense the water vapor in the condensation pipe 5, the water vapor is condensed, liquefied and released heat, the heat is transferred to the working medium, so that the utilization rate of energy is improved, the water vapor is liquefied and flows back to a phase change energy storage material 41 of an energy storage box body 4 through the condensation pipe 5, the working medium in the heat exchanger flows through a heat exchange pipe 3 through the water inlet pipe 1, the heat exchange is carried out between the working medium and the phase change energy storage material 41 through the heat exchange pipe 3, the phase change material of crystallized hydrated salt is combined with the crystallized water which flows back from the condensation pipe 5, phase change is carried out, the heat is released, the working medium which obtains the, the exothermic process is preferably stopped when the temperature is not higher than the temperature of the working medium entering through the inlet conduit 1.
The phase change energy storage device and the method for storing energy and supplying heat by using the phase change energy storage device can improve the energy utilization rate and prevent the temperature of the energy storage device from being overhigh, prevent the water from volatilizing, prevent the inorganic salt from being dehydrated and then being incapable of continuing the phase change process, improve the cycle times of the energy storage material and prolong the service life of the phase change material.
Examples
Example 1
Weighing 100g of barium hydroxide octahydrate, 5g of polypropylene fiber and 40g of saturated solution of barium hydroxide octahydrate;
weaving polypropylene fibers on an anti-corrosion support into a net shape, placing the net shape in a container, then adding saturated solution of barium hydroxide octahydrate and barium hydroxide octahydrate into the container, and uniformly mixing to obtain a mixture;
then heating the mixture in an oil bath at 85 ℃ until the barium hydroxide octahydrate is completely melted;
and naturally cooling and forming the melted mixture to obtain the inorganic composite phase change energy storage material.
Example 2
The procedure of example 1 was repeated except that 5g of aramid fiber was weighed and the other steps were the same as in example 1.
Example 3
The procedure of example 1 was repeated except that 5g of the glass fiber was weighed, and the other steps were the same as those of example.
Example 4
The procedure of example 1 was repeated except that 2.5g of glass fiber was used.
Example 5
The procedure of example 2 was repeated except that the aramid fiber was 2.5 g.
Example 6
The procedure of example 3 was repeated except that the polypropylene fiber was 2.5 g.
Example 7
The procedure of example 3 was repeated except that the polypropylene fiber in the form of a strand was 2.5 g.
Example 8
Weighing 100g of barium hydroxide octahydrate, 5g of polypropylene fiber and 45g of saturated solution of barium hydroxide octahydrate;
weaving polypropylene fibers on an anti-corrosion support into a net shape, placing the net shape in a container, then adding saturated solution of barium hydroxide octahydrate and barium hydroxide octahydrate into the container, and uniformly mixing to obtain a mixture;
heating the mixture in an oil bath at 89 ℃ until the barium hydroxide octahydrate is completely molten;
stopping heating, and naturally cooling and forming the melted mixture in an oil bath to obtain the inorganic composite phase change energy storage material.
Example 9
Weighing 100g of barium hydroxide octahydrate, 5g of polypropylene fiber and 30g of saturated solution of barium hydroxide octahydrate;
weaving polypropylene fibers on an anti-corrosion support into a net shape, placing the net shape in a container, then adding saturated solution of barium hydroxide octahydrate and barium hydroxide octahydrate into the container, and uniformly mixing to obtain a mixture;
heating the mixture in an oil bath at 82 ℃ until barium hydroxide octahydrate is completely molten;
stopping heating, and naturally cooling and forming the melted mixture in an oil bath to obtain the inorganic composite phase change energy storage material.
Example 10
The utility model provides a phase change energy memory, the device includes the energy storage box, the phase change energy memory material that embodiment 1 made is held in the energy storage box, the coating has the anticorrosion coating on the energy storage box inner wall, during heater and pressure temperature controller inserted the phase change energy memory material of energy storage box, phase change energy memory still includes the heat exchanger, the heat exchanger includes inlet tube, heat exchange tube and outlet pipe, the heat exchange tube is buried underground in phase change material, inlet tube, heat exchange tube and outlet pipe are stainless steel, the outer wall coating has the anticorrosion coating. Be equipped with the condensation reflux equipment at the top of energy storage box, the condensation reflux equipment includes the condenser pipe, and the one end and the energy storage box of condenser pipe are linked together. The water inlet pipe is provided with a spiral pipe section, and the condensation pipe penetrates through the spiral pipe section, namely the spiral pipe section is wound on the condensation pipe.
The phase-change material is heated by the heater, the phase-change material loses crystal water, the phase-change material stores heat, the crystal water enters the condenser pipe through the evaporation pipe, and the phase-change material stops heating when the temperature reaches the set temperature.
Let in cold water in the water inlet pipe, when cold water passed through the pipeline section that inlet tube and screwed pipe contacted, cold water can condense the crystal water in the screwed pipe, and the crystal water after the condensation flows back to the phase change material in the energy storage box by the condenser pipe in, and cold water passes through the heat exchange tube, takes place the heat exchange with phase change material, and phase change material obtains crystal water, gives out the heat, and cold water obtains the heat and becomes hot water and flow out from the outlet pipe for the use.
Comparative example
Comparative example 1
Weighing 100g of barium hydroxide octahydrate and 40g of saturated solution of barium hydroxide octahydrate, and uniformly mixing the two to obtain a mixture;
heating the mixture to 85 ℃ to completely melt barium hydroxide octahydrate;
and cooling and forming the melted mixture to obtain the inorganic composite phase change energy storage material.
Comparative example 2
Weighing 100g of barium hydroxide octahydrate, 0.05g of polypropylene fiber and 40g of saturated solution of barium hydroxide octahydrate;
weaving polypropylene fibers into a net structure on an anti-corrosion support, placing the net structure in a container, and then adding barium hydroxide octahydrate and a saturated solution thereof into the container to obtain a mixture; heating the mixture to 85 ℃ to completely melt the barium hydroxide octahydrate;
and cooling and forming the melted mixture to obtain the inorganic composite phase change energy storage material.
Comparative example 3
Weighing 100g of barium hydroxide octahydrate and 3g of polypropylene fiber, weaving the polypropylene fiber on an anti-corrosion support to form a net structure, putting the net structure into a container, adding the barium hydroxide octahydrate into the container to obtain a mixture,
heating the mixture to 85 ℃ to completely melt the barium hydroxide octahydrate;
and cooling and forming to obtain the inorganic composite phase change energy storage material.
Examples of the experiments
Experimental example 1
The inorganic composite phase change energy storage material obtained in the example 1 and the comparative example 1 and the reference glycerin are subjected to a phase change crystallization temperature test, the inorganic composite phase change energy storage material and the reference glycerin are cooled at the same temperature, the measured temperature change curve (namely, a cooling curve) of the phase change material in the cooling process is shown in fig. 2, the curve in the unoptimized case is the cooling curve of the phase change energy storage material obtained in the comparative example 1, the curve in the optimized case is the cooling curve of the phase change energy storage material obtained in the example 1, the curve in the optimized case is the cooling curve of the glycerin, and the curve in the unoptimized case and the curve in the optimized case can show that in the cooling process, the temperature jump occurs in the curve, which is caused by crystallization heat release of barium hydroxide in the cooling process, the supercooling crystallization temperature in the unoptimized case is 53 ℃, the supercooling crystallization temperature in the optimized case is 71 ℃, the addition of the polypropylene fiber nucleating agent improves the supercooling degree of the inorganic composite phase change energy storage material.
Experimental example 2
The inorganic composite phase change energy storage materials of examples 1 to 7 and comparative examples 1 to 3 were tested, the obtained inorganic composite phase change energy storage materials were heated to 85 ℃, melted, and then cooled under the same external environment and the same heat exchange rate, and the phase change temperature and the phase change time at which phase change occurred during cooling were tested, and the results are shown in table 1.
TABLE 1
| Sample (I) | Phase transition temperature/. degree.C | Phase transition time/h |
| Example 1 | 71 | 1 |
| Example 2 | 70 | 1.1 |
| Example 3 | 71 | 1.05 |
| Example 4 | 70.5 | 1 |
| Example 5 | 71 | 1 |
| Example 6 | 70 | 1.1 |
| Example 7 | 70.6 | 1 |
| Comparative example 1 | 53 | 1.4 |
| Comparative example 2 | 66 | 1.3 |
As can be seen from Table 1, the phase change temperature of the phase change material is low and the phase change time is long because the organic fiber is not added in comparative example 1 and the amount of the organic fiber added in comparative example 2 is too small, while the phase change time of the inorganic composite phase change energy storage material prepared as in examples 1-7 is shortened, i.e. the crystallization nucleation rate is increased after the organic fiber is added. It is observed that the phase change energy storage materials obtained in examples 1 to 7 have no phase separation phenomenon in the phase change process, while the phase change material obtained in comparative example 3 has a layering and caking phenomenon, i.e., a phase separation phenomenon, in the cooling and crystallization process, which indicates that the phase separation phenomenon of the phase change energy storage material can be improved by adding the saturated solution of barium hydroxide octahydrate.
In conclusion, the supercooling and phase separation phenomena of the phase change energy storage material can be improved by adding the organic fiber as the nucleating agent and adding the saturated solution of the inorganic salt as the buffering agent.
The invention has been described in detail with reference to the preferred embodiments and illustrative examples. It should be noted, however, that these specific embodiments are only illustrative of the present invention and do not limit the scope of the present invention in any way. Various modifications, equivalent substitutions and alterations can be made to the technical content and embodiments of the present invention without departing from the spirit and scope of the present invention, and these are within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. The inorganic composite phase change energy storage material is characterized by comprising the following components in parts by weight:
50-99 parts by weight of an energy storage main material;
0.1-20 parts by weight of a nucleating agent;
0.01 to 50 parts by weight of a buffer.
2. The phase change energy storage material according to claim 1, wherein the energy storage host material is an inorganic phase change material, preferably selected from one or more of alkali hydrates and crystalline hydrated salts.
3. The phase change energy storage material of claim 2,
the alkali hydrate is selected from one or more of sodium hydroxide monohydrate, barium hydroxide octahydrate and strontium hydroxide octahydrate, and/or
The crystalline hydrated salt is selected from one or more of calcium chloride hexahydrate, aluminum potassium sulfate dodecahydrate, sodium sulfate decahydrate, potassium fluoride dihydrate, sodium acetate trihydrate, sodium thiosulfate pentahydrate, magnesium sulfate heptahydrate, sodium sulfate decahydrate, disodium hydrogen phosphate dodecahydrate, aluminum ammonium sulfate dodecahydrate and aluminum sulfate octadecahydrate.
4. The phase change energy storage material according to claim 1, wherein the nucleating agent is an inorganic nucleating agent and/or an organic nucleating agent.
5. The phase change energy storage material of claim 4,
the inorganic nucleating agent is one or more of quartz, disodium hydrogen phosphate dodecahydrate, borax, calcium chloride dihydrate, potassium dihydrogen phosphate, sodium pyrophosphate, sodium acetate, sodium sulfate, barium chloride, calcium fluoride, barium hydroxide, nano silicon dioxide, nano titanium dioxide or inorganic fibers,
the organic nucleating agent is organic fiber.
6. The phase change energy storage material according to claim 5, wherein the organic fiber is selected from one or more of aramid fiber, polypropylene fiber, acrylic fiber, polyimide, nylon, polyethylene fiber, polypropylene fiber, poly-p-phenylene benzobisoxazole fiber, poly-p-benzimidazole fiber, poly-p-phenylene pyridobisimidazole fiber.
7. The phase change energy storage material according to claim 1, wherein the buffer is a saturated solution of an inorganic hydrate, preferably a saturated solution of an alkali hydrate or a crystalline hydrated salt.
8. A method of preparing a phase change energy storage material according to any one of claims 1 to 7, comprising the steps of:
step 1, weighing an energy storage main material, a nucleating agent and a buffer agent;
step 2, mixing the energy storage main body material, the nucleating agent and the buffering agent in the step 1 in a container to obtain a mixture;
step 3, heating the mixture obtained in the step 2;
and 4, cooling and forming to obtain the inorganic composite phase change energy storage material.
9. The method of claim 8,
in step 2, a nucleating agent is added into the container, and then an energy storage main body material and a buffer agent are added,
in step 3, the mixture obtained in step 2 is heated to be molten.
10. A phase change energy storage device, comprising a phase change energy storage material as claimed in any one of claims 1 to 7 and an energy storage tank containing the phase change energy storage material.
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