CN109870061A - A kind of phase-change energy storage device and preparation method thereof - Google Patents
A kind of phase-change energy storage device and preparation method thereof Download PDFInfo
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- CN109870061A CN109870061A CN201910235252.5A CN201910235252A CN109870061A CN 109870061 A CN109870061 A CN 109870061A CN 201910235252 A CN201910235252 A CN 201910235252A CN 109870061 A CN109870061 A CN 109870061A
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Abstract
The present invention relates to a kind of phase-change energy storage devices and preparation method thereof, including shell, energy storage ball, the shell is set as tubular structure, energy storage ball is filled in shell, the energy storage ball includes spherical shell, phase-changing energy storage material, the phase-changing energy storage material is placed in spherical shell, and the phase-changing energy storage material uses paraffin or its graphene composite phase-change material.The present invention can infiltrate organic phase change material into graphene aerogel, it is prepared into graphene composite phase-change material, and graphene composite phase-change material is prepared into spherical shape, it is put into the spherical shell of metal and forms energy storage ball, and by energy storage ball sealing in the shell of tubular, it is convenient to use, energy storage ball and the heat-conducting work medium contact area for passing through energy storage device are big, be conducive to going on smoothly for heat transfer, graphene aerogel in energy storage ball can also increase the capacity of heat transmission of paraffin, convenient for the heat conduction in paraffin.
Description
Technical field
The present invention relates to field of new energy technologies, and in particular to a kind of phase-change energy storage device and preparation method thereof.
Background technique
Important link of the accumulation of energy as therrmodynamic system, the attention by more and more researchers and company.According to master
The classification of stream, energy accumulating technique can be divided into: sensible heat accumulation of energy, latent heat accumulator and heat chemistry accumulation of energy.
Two fields are concentrated mainly on to the research of accumulation of energy both at home and abroad: being solar energy heating electricity first, visits the energy storage equipment that makes internal disorder or usurp
Performance and effect in solar thermal collection system；It secondly is energy accumulating technique in the application of building energy saving field, mostly concern accumulation of energy
Application of the technology in civilian or commercial building air-conditioning, refrigeration, heating and hot water supply system.Wherein, solar energy thermal-power-generating
Field mostly uses high temperature energy accumulating technique, and in building energy saving field, mainly low-temperature heat accumulating device is heated, is led in exploitation
Wind and air-conditioning.
Energy-accumulation material can be divided into inorganic cool storage material and organic cool storage material, crystalline hydrate salt, fuse salt according to composition
Class, metal or alloy belong to inorganic energy-accumulation material, and crystalline hydrate salt is to make salt dissolving and heat absorbing using abjection and the absorption crystallization water
Or heat release achievees the purpose that energy storage, melting range is middle low temperature energy storage phase transformation material from several degrees Celsius to more than 100 degrees Celsius
The Chinese medicine of material is a kind of, they the characteristics of be that thermal coefficient is larger, energy storage density is big, heat of fusion is high, cheap, widely used.
Usually use more is the halide salt etc. of phosphate, sulfate, nitrate, carbonate, alkali and alkaline earth metal ions.Organic phase
Becoming material mainly has paraffin class, fatty acid, alcohols etc..Paraffin class phase-change material for cold storage has been widely adopted.Paraffin is one
Kind mixture, is mainly mixed by linear paraffin, CnH2n+2.As phase-changing energy storage material, paraffin has lot of advantages, hair
When raw phase transformation steam force down, without surfusion, chemical property is stable, heat of fusion is high, crystallization when without spontaneous nucleation, nontoxic stingless is precipitated
It is low etc. to swash property smell, price.Melting point of paraffin wax and heat of fusion can increase with the growth of carbochain, so as to obtain a system
The energy storage material of different phase transition temperatures is arranged, and is increased to a certain extent in carbochain, the value added of fusing point becomes smaller, and finally tends to be certain
Value.But paraffin also has the problems such as his insufficient place, as poor such as heating conduction, non-paraffin class organic phase change material includes fat
Acid, vinegar, pure and mild certain polymer etc..There are many they the advantages of, and between melting range is, fusing heat is, supercooling and corrosivity compared with
It is small, be not susceptible to mutually to separate, solid forming it is good, similarly, disadvantage is also that thermal conductivity is poor.So solving organic phase-change energy storage material
The thermal conductivity problem of material, and increase the heat-conducting area of its energy storage device, it is the key that shorten its energy storage time.
Summary of the invention
To overcome the deficiency, the purpose of the present invention is to provide a kind of phase-change energy storage devices and preparation method thereof.
The technical solution adopted by the present invention to solve the technical problems is: a kind of phase-change energy storage device, including shell, energy storage
Ball, the shell are set as tubular structure, fill energy storage ball in shell, and the energy storage ball includes spherical shell, phase-changing energy storage material, described
Phase-changing energy storage material is placed in spherical shell.
Specifically, the shell includes internal layer and outer layer, internal layer and outer layer central filler thermal insulation material, the insulating layer material
Material selects polystyrene foam plastics and polyurethane foam plastics.
Specifically, one end of the shell is set as evaporator section, and the other end is set as condensation segment.
Specifically, the spherical shell using iron, copper at.
Specifically, the phase-changing energy storage material uses paraffin or its graphene composite phase-change material.
A kind of preparation method of phase-change energy storage device, comprising the following steps:
D1 prepares graphene composite phase-change material
Firstly, preparing graphene aerogel
Large scale graphene oxide is added into deionized water, ultrasonic disperse 1h prepares the graphite oxide that concentration is 5mg/mL
Aqueous solution, adds carbon nanotube, ultrasonic disperse 30min, and the mass ratio of graphene oxide and carbon nanotube is 1:1, obtains
Mixed liquor instills two drop ammonium hydroxide into mixed liquor, stirs 30min, obtain mixed dispersion liquid, mixed dispersion liquid is put into spherical die
It is interior, it is transferred into tube furnace, under hydrazine hydrate atmosphere, is heated to 80-90 DEG C, keep for 24 hours, carrying out hydro-thermal reaction, obtaining
Spherical hydrogel is dialysed 6h with 20% water-alcohol solution, after refrigerator freezing, then is freeze-dried with freeze dryer, is obtained graphene airsetting
Glue, when freeze-drying, freeze dryer keeps 10Pa vacuum degree below, freeze-drying process 24-48h；
Secondly, preparing graphene composite phase-change material
Graphene aerogel is placed in tube furnace and is annealed, gas displacement 3 is carried out in a manner of vacuumizing-fill the water nitrogen
It is secondary, it is warming up to 800-900 DEG C with the speed of 5 DEG C/min in a nitrogen atmosphere, and after keeping 5h, then drop with the speed of 5 DEG C/min
To room temperature, the graphene aerogel after annealing is impregnated in dissolved with paraffin by graphene aerogel after being annealed
It in methylene chloride, after fully absorbing, takes out, under atmospheric pressure at room, places 12-24h, after methylene chloride volatilization, then set
Drying for 24 hours, obtains spherical graphite alkene composite phase-change material in 30 DEG C of vacuum drying oven；
D2 prepares energy storage ball
The spherical composite phase-change material of preparation is put into spherical shell, and is sealed；
Energy storage ball is put into shell by D3, and phase-change energy storage device is made.
The invention has the following advantages: organic phase change material infiltration is prepared into graphite into graphene aerogel
Alkene composite phase-change material, and graphene composite phase-change material is prepared into spherical shape, it is put into the spherical shell of metal and forms storage
Energy ball, and by energy storage ball sealing in the shell of tubular, it is easy to use, energy storage ball is contacted with by the heat-conducting work medium of energy storage device
Area is big, is conducive to going on smoothly for heat transfer, and the graphene aerogel in energy storage ball can also increase the capacity of heat transmission of paraffin,
Convenient for the heat conduction in paraffin.
Detailed description of the invention
Fig. 1 is the structural diagram of the present invention.
Fig. 2 is energy storage spherical structure schematic diagram of the invention.
1 shell in figure, 11 evaporator sections, 12 condensation segments, 2 energy storage balls, 21 spherical shells, 22 graphene aerogels, 23 phase-change accumulation energies
Material.
Specific embodiment
In conjunction with the accompanying drawings, the present invention is further explained in detail.
Embodiment one
Tubular knot is set as according to Fig. 1, a kind of phase-change energy storage device shown in Fig. 2, including shell, energy storage ball, the shell
Structure, shell is interior to fill energy storage ball, and the energy storage ball includes spherical shell, phase-changing energy storage material, and the phase-changing energy storage material is placed on spherical shell
It is interior.
Specifically, the shell includes internal layer and outer layer, internal layer and outer layer central filler thermal insulation material, the insulating layer material
Material selects polystyrene foam plastics and polyurethane foam plastics.
Specifically, one end of the shell is set as evaporator section, and the other end is set as condensation segment.
Specifically, the spherical shell using iron, copper at.
Specifically, the phase-changing energy storage material uses paraffin or its graphene composite phase-change material.
A kind of preparation method of phase-change energy storage device, comprising the following steps:
D1 prepares graphene composite phase-change material
Firstly, preparing graphene aerogel
Large scale graphene oxide is added into deionized water, ultrasonic disperse 1h prepares the graphite oxide that concentration is 5mg/mL
Aqueous solution, adds carbon nanotube, ultrasonic disperse 30min, and the mass ratio of graphene oxide and carbon nanotube is 1:1, obtains
Mixed liquor instills two drop ammonium hydroxide into mixed liquor, stirs 30min, obtain mixed dispersion liquid, mixed dispersion liquid is put into spherical die
It is interior, it is transferred into tube furnace, under hydrazine hydrate atmosphere, is heated to 80 DEG C, keep for 24 hours, carrying out hydro-thermal reaction, obtaining spherical shape
Hydrogel is dialysed 6h with 20% water-alcohol solution, after refrigerator freezing, then is freeze-dried with freeze dryer, is obtained graphene aerogel, cold
When being lyophilized dry, freeze dryer keeps 10Pa vacuum degree below, freeze-drying process 24-48h；
Secondly, preparing graphene composite phase-change material
Graphene aerogel is placed in tube furnace and is annealed, gas displacement 3 is carried out in a manner of vacuumizing-fill the water nitrogen
It is secondary, 800 DEG C are warming up to the speed of 5 DEG C/min in a nitrogen atmosphere, and after keeping 5h, then room is down to the speed of 5 DEG C/min
Graphene aerogel after annealing is impregnated in the dichloro dissolved with paraffin by temperature, the graphene aerogel after being annealed
It in methane, after fully absorbing, takes out, under atmospheric pressure at room, places 12h, after methylene chloride volatilization, then place it in 30 DEG C
Drying for 24 hours, obtains spherical graphite alkene composite phase-change material in vacuum drying oven；
D2 prepares energy storage ball
The spherical composite phase-change material of preparation is put into spherical shell, and is sealed；
Energy storage ball is put into shell by D3, and phase-change energy storage device is made.
Embodiment two
A kind of phase-change energy storage device, including shell, energy storage ball, the shell are set as tubular structure, fill energy storage in shell
Ball, the energy storage ball include spherical shell, phase-changing energy storage material, and the phase-changing energy storage material is placed in spherical shell.
Specifically, the shell includes internal layer and outer layer, internal layer and outer layer central filler thermal insulation material, the insulating layer material
Material selects polystyrene foam plastics and polyurethane foam plastics.
Specifically, one end of the shell is set as evaporator section, and the other end is set as condensation segment.
Specifically, the spherical shell using iron, copper at.
Specifically, the phase-changing energy storage material uses paraffin or its graphene composite phase-change material.
A kind of preparation method of phase-change energy storage device, comprising the following steps:
D1 prepares graphene composite phase-change material
Firstly, preparing graphene aerogel
Large scale graphene oxide is added into deionized water, ultrasonic disperse 1h prepares the graphite oxide that concentration is 5mg/mL
Aqueous solution, adds carbon nanotube, ultrasonic disperse 30min, and the mass ratio of graphene oxide and carbon nanotube is 1:1, obtains
Mixed liquor instills two drop ammonium hydroxide into mixed liquor, stirs 30min, obtain mixed dispersion liquid, mixed dispersion liquid is put into spherical die
It is interior, it is transferred into tube furnace, under hydrazine hydrate atmosphere, is heated to 85 DEG C, keep for 24 hours, carrying out hydro-thermal reaction, obtaining spherical shape
Hydrogel is dialysed 6h with 20% water-alcohol solution, after refrigerator freezing, then is freeze-dried with freeze dryer, is obtained graphene aerogel, cold
When being lyophilized dry, freeze dryer keeps 10Pa vacuum degree below, freeze-drying process 30h；
Secondly, preparing graphene composite phase-change material
Graphene aerogel is placed in tube furnace and is annealed, gas displacement 3 is carried out in a manner of vacuumizing-fill the water nitrogen
It is secondary, 840 DEG C are warming up to the speed of 5 DEG C/min in a nitrogen atmosphere, and after keeping 5h, then room is down to the speed of 5 DEG C/min
Graphene aerogel after annealing is impregnated in the dichloro dissolved with paraffin by temperature, the graphene aerogel after being annealed
It in methane, after fully absorbing, takes out, under atmospheric pressure at room, places 18h, after methylene chloride volatilization, then place it in 30 DEG C
Drying for 24 hours, obtains spherical graphite alkene composite phase-change material in vacuum drying oven；
D2 prepares energy storage ball
The spherical composite phase-change material of preparation is put into spherical shell, and is sealed；
Energy storage ball is put into shell by D3, and phase-change energy storage device is made.
Embodiment three
A kind of phase-change energy storage device, including shell, energy storage ball, the shell are set as tubular structure, fill energy storage in shell
Ball, the energy storage ball include spherical shell, phase-changing energy storage material, and the phase-changing energy storage material is placed in spherical shell.
Specifically, the shell includes internal layer and outer layer, internal layer and outer layer central filler thermal insulation material, the insulating layer material
Material selects polystyrene foam plastics and polyurethane foam plastics.
Specifically, one end of the shell is set as evaporator section, and the other end is set as condensation segment.
Specifically, the spherical shell using iron, copper at.
Specifically, the phase-changing energy storage material uses paraffin or its graphene composite phase-change material.
A kind of preparation method of phase-change energy storage device, comprising the following steps:
D1 prepares graphene composite phase-change material
Firstly, preparing graphene aerogel
Large scale graphene oxide is added into deionized water, ultrasonic disperse 1h prepares the graphite oxide that concentration is 5mg/mL
Aqueous solution, adds carbon nanotube, ultrasonic disperse 30min, and the mass ratio of graphene oxide and carbon nanotube is 1:1, obtains
Mixed liquor instills two drop ammonium hydroxide into mixed liquor, stirs 30min, obtain mixed dispersion liquid, mixed dispersion liquid is put into spherical die
It is interior, it is transferred into tube furnace, under hydrazine hydrate atmosphere, is heated to 88 DEG C, keep for 24 hours, carrying out hydro-thermal reaction, obtaining spherical shape
Hydrogel is dialysed 6h with 20% water-alcohol solution, after refrigerator freezing, then is freeze-dried with freeze dryer, is obtained graphene aerogel, cold
When being lyophilized dry, freeze dryer keeps 10Pa vacuum degree below, freeze-drying process 40h；
Secondly, preparing graphene composite phase-change material
Graphene aerogel is placed in tube furnace and is annealed, gas displacement 3 is carried out in a manner of vacuumizing-fill the water nitrogen
It is secondary, 860 DEG C are warming up to the speed of 5 DEG C/min in a nitrogen atmosphere, and after keeping 5h, then room is down to the speed of 5 DEG C/min
Graphene aerogel after annealing is impregnated in the dichloro dissolved with paraffin by temperature, the graphene aerogel after being annealed
It in methane, after fully absorbing, takes out, under atmospheric pressure at room, places 20h, after methylene chloride volatilization, then place it in 30 DEG C
Drying for 24 hours, obtains spherical graphite alkene composite phase-change material in vacuum drying oven；
D2 prepares energy storage ball
The spherical composite phase-change material of preparation is put into spherical shell, and is sealed；
Energy storage ball is put into shell by D3, and phase-change energy storage device is made.
Example IV
A kind of phase-change energy storage device, including shell, energy storage ball, the shell are set as tubular structure, fill energy storage in shell
Ball, the energy storage ball include spherical shell, phase-changing energy storage material, and the phase-changing energy storage material is placed in spherical shell.
Specifically, the shell includes internal layer and outer layer, internal layer and outer layer central filler thermal insulation material, the insulating layer material
Material selects polystyrene foam plastics and polyurethane foam plastics.
Specifically, one end of the shell is set as evaporator section, and the other end is set as condensation segment.
Specifically, the spherical shell using iron, copper at.
Specifically, the phase-changing energy storage material uses paraffin or its graphene composite phase-change material.
A kind of preparation method of phase-change energy storage device, comprising the following steps:
D1 prepares graphene composite phase-change material
Firstly, preparing graphene aerogel
Large scale graphene oxide is added into deionized water, ultrasonic disperse 1h prepares the graphite oxide that concentration is 5mg/mL
Aqueous solution, adds carbon nanotube, ultrasonic disperse 30min, and the mass ratio of graphene oxide and carbon nanotube is 1:1, obtains
Mixed liquor instills two drop ammonium hydroxide into mixed liquor, stirs 30min, obtain mixed dispersion liquid, mixed dispersion liquid is put into spherical die
It is interior, it is transferred into tube furnace, under hydrazine hydrate atmosphere, is heated to 90 DEG C, keep for 24 hours, carrying out hydro-thermal reaction, obtaining spherical shape
Hydrogel is dialysed 6h with 20% water-alcohol solution, after refrigerator freezing, then is freeze-dried with freeze dryer, is obtained graphene aerogel, cold
When being lyophilized dry, freeze dryer keeps 10Pa vacuum degree below, freeze-drying process 48h；
Secondly, preparing graphene composite phase-change material
Graphene aerogel is placed in tube furnace and is annealed, gas displacement 3 is carried out in a manner of vacuumizing-fill the water nitrogen
It is secondary, 900 DEG C are warming up to the speed of 5 DEG C/min in a nitrogen atmosphere, and after keeping 5h, then room is down to the speed of 5 DEG C/min
Graphene aerogel after annealing is impregnated in the dichloro dissolved with paraffin by temperature, the graphene aerogel after being annealed
It in methane, after fully absorbing, takes out, under atmospheric pressure at room, places for 24 hours, after methylene chloride volatilization, then place it in 30 DEG C
Drying for 24 hours, obtains spherical graphite alkene composite phase-change material in vacuum drying oven；
D2 prepares energy storage ball
The spherical composite phase-change material of preparation is put into spherical shell, and is sealed；
Energy storage ball is put into shell by D3, and phase-change energy storage device is made.
The present invention is not limited to the embodiment, anyone should learn that the structure made under the inspiration of the present invention becomes
Change, the technical schemes that are same or similar to the present invention are fallen within the scope of protection of the present invention.
Technology not described in detail in the present invention, shape, construction portion are well-known technique.
Claims (8)
1. a kind of phase-change energy storage device, it is characterised in that: including shell, energy storage ball, the shell is set as tubular structure, in shell
Energy storage ball is filled, the energy storage ball includes spherical shell, phase-changing energy storage material, and the phase-changing energy storage material is placed in spherical shell.
2. a kind of phase-change energy storage device according to claim 1, it is characterised in that: the shell includes internal layer and outer layer,
Internal layer and outer layer central filler thermal insulation material, the insulating layer material selection polystyrene foam plastics and polyurethane foam modeling
Material.
3. a kind of phase-change energy storage device according to claim 1, it is characterised in that: one end of the shell is set as evaporating
Section, the other end are set as condensation segment.
4. a kind of phase-change energy storage device according to claim 1, it is characterised in that: the spherical shell using iron, copper at.
5. a kind of phase-change energy storage device according to claim 1, it is characterised in that: the phase-changing energy storage material uses paraffin
Or its graphene composite phase-change material.
6. a kind of preparation method of phase-change energy storage device, comprising the following steps:
D1 prepares graphene composite phase-change material
Firstly, preparing graphene aerogel；
Secondly, preparing graphene composite phase-change material；
D2 prepares energy storage ball
The spherical composite phase-change material of preparation is put into spherical shell, and is sealed；
Energy storage ball is put into shell by D3, and phase-change energy storage device is made.
7. a kind of preparation method of phase-change energy storage device according to claim 6, it is characterised in that: described to prepare graphene
The step of aeroge are as follows: prepare graphene composite phase-change material and large scale graphene oxide, ultrasound point are added into deionized water
The graphene oxide water solution that 1h preparation concentration is 5mg/mL is dissipated, carbon nanotube, ultrasonic disperse 30min, graphite oxide are added
Alkene and the mass ratio of carbon nanotube are 1:1, obtain mixed liquor, and two drop ammonium hydroxide are instilled into mixed liquor, 30min is stirred, must mix
Mixed dispersion liquid is put into spherical die by dispersion liquid, is transferred into tube furnace, under hydrazine hydrate atmosphere, is heated to 80-
It 90 DEG C, keeps for 24 hours, carrying out hydro-thermal reaction, obtaining spherical hydrogel, is dialysed 6h with 20% water-alcohol solution, after refrigerator freezing, then used
Freeze dryer freeze-drying, obtains graphene aerogel, and when freeze-drying, freeze dryer keeps 10Pa vacuum degree below, and freezing is dry
Dry processing 24-48h.
8. a kind of preparation method of phase-change energy storage device according to claim 6, it is characterised in that: described to prepare graphene
The step of composite phase-change material are as follows: graphene aerogel is placed in tube furnace and is annealed, in a manner of vacuumizing-fill the water nitrogen into
Row gas displacement 3 times, be warming up to 800-900 DEG C in a nitrogen atmosphere with the speed of 5 DEG C/min, and after keeping 5h, then with 5 DEG C/
The speed of min is down to room temperature, the graphene aerogel after being annealed, and the graphene aerogel after annealing is impregnated in molten
Solution has in the methylene chloride of paraffin, after fully absorbing, takes out, and under atmospheric pressure at room, places 12-24h, volatilizees to methylene chloride
Afterwards, then place it in 30 DEG C of vacuum drying oven it is dry for 24 hours, obtain spherical graphite alkene composite phase-change material.
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| WO2020253094A1 (en) * | 2019-06-17 | 2020-12-24 | 中国科学院深圳先进技术研究院 | Boron nitride nanotube aerogel/phase change heat conductive composite material and preparation method therefor |
| CN114136046A (en) * | 2021-11-10 | 2022-03-04 | 北京航天试验技术研究所 | Vehicle-mounted efficient heat-insulation Stirling deep low-temperature refrigerator |
| CN115881320A (en) * | 2022-11-08 | 2023-03-31 | 中国核动力研究设计院 | High-density phase-change heat storage system for buffering energy storage |
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