CN105810812B - A kind of assemble method of spherical high-temperature phase transition heat storage element and the heat accumulation element being consequently formed - Google Patents
A kind of assemble method of spherical high-temperature phase transition heat storage element and the heat accumulation element being consequently formed Download PDFInfo
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- CN105810812B CN105810812B CN201610290089.9A CN201610290089A CN105810812B CN 105810812 B CN105810812 B CN 105810812B CN 201610290089 A CN201610290089 A CN 201610290089A CN 105810812 B CN105810812 B CN 105810812B
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- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
Abstract
The present invention relates to a kind of assemble method of spherical high-temperature phase transition heat storage element, comprise the following steps：Phase-change material microballoon is provided；Graphitization presoma is provided；It is put into after phase-change material microballoon is mixed with graphitization presoma in quasi-iso static pressing silica gel mould, with 50 100MPa precompressed so that the disperse of phase-change material microballoon obtains pre- pressure ball base in graphitization presoma；Pre- pressure ball base is put into quasi-iso static pressing silica gel mould, suppressed with 120 300MPa so that multiple phase-change material microspheroidals turn into core, and graphitization presoma forms the matrix graphite layer for surrounding the core, obtains final pressure ball base；Final pressure ball base is carried out being thermally treated resulting in heat accumulation element.The present invention also provides a kind of spherical high-temperature phase transition heat storage element.Graphite material can be preferably compatible and has good thermal circulation performance than metal more resistant to high temperature, corrosion-resistant used by spherical high-temperature phase transition heat storage element provided by the invention, there is provided a kind of component for effectively encapsulating high temperature phase change material (pcm).
Description
Technical field
The present invention relates to phase-change heat-storage material, relates more specifically to a kind of assemble method of spherical high-temperature phase transition heat storage element
With the heat accumulation element being consequently formed.
Background technology
Phase-changing energy storage material has unique latent heat performance, and when being undergone phase transition near phase transition temperature, it can be from environment
Heat is absorbed or to Environment release heat, so as to the purpose for reaching the storage of heat and utilizing, when can effectively solve energy supply and demand
Empty unmatched contradiction.Therefore, phase change energy storage technology is widely used in discontinuity or instable field of heat management.
Intermittence, nuclear energy heat utilization, industrial afterheat recovery, building heat preservation refrigeration, the peak-valley difference of electric load, periodicity such as solar energy
The problems such as radiating of the high-power electronic device of work.
All the time, the assembling of phase-changing energy storage material (referred to as phase-change material) and device are that to limit its wide variety of
Major issue.At present, metal material is the package carrier of known middle low-temperature phase-change material, and it has thermal conductivity high and easy processing
The advantages of, specifically, middle low-temperature phase-change material and stainless steel etc. form component using traditional packed bed heat reservoir.
But it can not meet the requirement of temperature, thermal expansion and compatibility for high temperature phase change material (pcm), metal material, exist
The shortcomings of density is big, perishable and high high-temp stability is poor.Moreover, traditional packed bed heat reservoir is mainly used in low temperature field
(phase transition temperature is less than 120 DEG C), the encapsulation requirement of high-temperature field (phase transition temperature is higher than 300 DEG C) can not be met.
The content of the invention
In order to solve the problems, such as that metal material existing for above-mentioned prior art can not encapsulate high temperature phase change material (pcm), purport of the present invention
In the heat accumulation element for providing a kind of assemble method of spherical high-temperature phase transition heat storage element and being consequently formed.
The present invention provides a kind of assemble method of spherical high-temperature phase transition heat storage element, comprises the following steps：S1, provide phase transformation
Material microballoon；S2, provide graphitization presoma；S3, that standard etc. is put into after phase-change material microballoon is mixed with graphitization presoma is quiet
Press in silica gel mould, with 50-100MPa precompressed so that the disperse of phase-change material microballoon obtains pre- pressure ball in graphitization presoma
Base；S4, pre- pressure ball base is put into quasi-iso static pressing silica gel mould, suppressed with 120-300MPa so that multiple phase-change material microballoons
Be formed as core, and graphitization presoma forms the matrix graphite layer for surrounding the core, obtains final pressure ball base；S5, by final pressure ball
Base carries out being thermally treated resulting in heat accumulation element.
In step sl, the phase-change material microballoon is metal heat accumulation microcapsules, passes through high temperature fluidized bed chemical vapor deposition
Method is prepared.In a preferred embodiment, the phase transition temperature of the metal heat accumulation microcapsules is 1083 DEG C.Except storage metal
Outside hot microcapsules, the phase-change material microballoon can also be the heat accumulating that other method obtains, as organic matter heat accumulation microcapsules,
Metal microcapsules, salt phase-change material or the pure phase-change material without capsule cladding and its mixing that galvanoplastic obtain
Thing.
Step S2 is specially by graphite powder and adhesive kneading, broken and be sieved into matrix graphite powder.Wherein, the graphite
Powder in the group being made up of petroleum coke, pitch coke, anthracite, native graphite, carbon black and metallurgical coke etc., the adhesive be selected from by
In the group of the compositions such as phenolic resin, coal tar pitch, coal tar.In addition to matrix graphite powder, the graphitization presoma can also be
Other carbon graphite material presomas, such as MCMB or other be applied to ceramic powder etc. of this method.It is real
On border, graphitization presoma can graphitization can occur in lower temperature and in the short period, while prevent phase-change material
Any material of microballoon melting leakage.Preferably, the particle diameter of the graphitization presoma is 3-50 μm.
Step S3 is specially：S31, phase-change material microballoon and graphitization presoma are premixed so that each phase-change material is micro-
The outer surface of ball coats one layer of graphitization presoma, the phase-change material microballoon coated；S32, the phase-change material of cladding is micro-
Ball is put into after being mixed with graphitization presoma in quasi-iso static pressing silica gel mould.In step S31, phase-change material microballoon is coated on
The thickness of the graphitization presoma of outer surface is 100-800 μm, prevents from extruding between phase-change material microballoon in follow-up pressing process
It is damaged.Specifically, phase-change material microballoon is put into seed-coating machine and rotated, spray alcohol dampening, while spray graphite powder and wrapped
Cover.In step s 32, by controlling the phase-change material microballoon of cladding and the mixed proportion of graphitization presoma, can adjust most
End form into heat accumulation element heat accumulation efficiency.For example, on the premise of capsule in ensureing follow-up pressing process is not damaged, suitably carry
Ratio shared by high metal heat accumulation microcapsules can improve its heat accumulation efficiency.Preferably, graphitization presoma and the phase transformation of cladding
The mixing quality ratio of material microballoon is 5%-15%.
In step s 4, graphitization presoma forms the matrix graphite layer of densification, and its density is 1.7-2.0g/cm3。
The loading chamber of quasi-iso static pressing silica gel mould in step S4 is more than the dress of the quasi-iso static pressing silica gel mould in step S3
Expect chamber.In step s 4, matrix graphite layer can also be multi-layer compound structure, play a part of encapsulating and conduct heat, now, step
The loading chamber of quasi-iso static pressing silica gel mould in S4 should be designed bigger.Wherein, quasi-iso static pressing technology is compacting spherical
A kind of known technology, the specific setting for the quasi-iso static pressing silica gel mould that will not be repeated here.
In step s 5, heat treatment, which is included at 800-1200 DEG C, carries out charing process and is carried out at 1800-2000 DEG C
Graphitization processing.In a preferred embodiment, the capsule layer of metal heat accumulation microcapsules is the metal material of relative non-refractory,
Maximum heat treatment temperature now can be controlled in 1500-1800 DEG C, wherein, carbonization temperature is 800-1000 DEG C, and graphitization temperature
Degree is selected below the fusing point of capsule layer metal.
The present invention also provides a kind of spherical high-temperature phase transition heat storage element, including：The core formed by multiple phase-change material microballoons
The heart；Surround the matrix graphite layer of the core.
A diameter of 500~2000 μm of phase-change material microballoon.
The thickness of matrix graphite layer is 2-8mm.
The overall diameter of spherical high-temperature phase transition heat storage element is 30-80mm.
Graphite material (3000 DEG C of fusing point, thermal conductivity 50- used by spherical high-temperature phase transition heat storage element provided by the invention
200W/mK) than metal (2000 DEG C or so of fusing point, thermal conductivity 100-200W/mK) more resistant to high temperature, corrosion-resistant, so that heat accumulation
The encapsulating material and high temperature phase change material (pcm) of element can be preferably compatible and have good thermal circulation performance, moreover, graphite material
Material is higher than the thermal conductivity of metal, so that spherical high-temperature phase transition heat storage element provided by the invention has high heat exchange efficiency,
In addition, the core of spherical high-temperature phase transition heat storage element provided by the invention is formed by multiple phase-change material microballoons, the phase transformation of loading
Material is more, so that spherical high-temperature phase transition heat storage element provided by the invention has high storage density, so as to finally carry
For a kind of component of effective encapsulation high temperature phase change material (pcm).In addition, the present invention obtains high-temperature-phase by quasi-iso static pressing technology
Become heat accumulation element, high yield rate, steady quality, be adapted to industrialized production.Preferably, the preload pressure in rate-determining steps S3 is passed through
With the pressing pressure in step S4, the density of spherical high-temperature phase transition heat storage element provided by the invention can be regulated and controled.
Brief description of the drawings
Fig. 1 is the structural representation according to the spherical high-temperature phase transition heat storage element of the present invention；
Fig. 2 is the x-ray imaging figure according to the spherical high-temperature phase transition heat storage element of the present invention.
Embodiment
Below in conjunction with the accompanying drawings, presently preferred embodiments of the present invention is provided, and is described in detail.
Embodiment 1 (internal microcapsules are Cu/PyC/SiC, and outer shell is graphite powder and adhesive)
S1, provide phase-change material microballoon：It is prepared from the inside to the outside successively by high temperature fluidized bed chemical vapour deposition technique
For Cu/PyC/SiC metal heat accumulation microcapsules；
S2, there is provided graphitization presoma, the raw material of outermost shell graphite is used as, and as the bag of phase transformation capsule particle
Cover the premix material before material and compacting：By graphite powder and phenolic resin in mass ratio 4:It is 1 ratio kneading, extrusion pelletizing, broken
It is broken, to be sieved into average grain diameter be 20 μm of matrix graphite powder.；
S31, microcapsules premix with graphite powder：Load 1Kg metal heat accumulation microcapsules in seed-coating machine, with 150r/min rotating speeds
Rotate, spray alcohol dampening capsule from top, while spray graphite powder made from step S2, a layer thickness is coated in capsule surface
About 200 μm of above-mentioned matrix graphite powder；S32, the microcapsules after graphite powder and coated graphite layer are pressed into quality percentage 1：9 ratio
Premix, for disperse discrete particles, prevent that particle directly contacts during compacting, extruding mutually causes breakage, obtains premix, then
Premix is put into quasi-iso static pressing silica gel mould, with 100MPa forming pressure precompressed globulate；
S4, final pressure shaping：One layer of dense substrate graphite is pressed in above-mentioned pre- pressure ball base outsourcing using quasi-iso static pressing technique again,
Graphite powder is matrix graphite powder made from step S2, forming pressure 300MPa, obtains high-temperature phase-change heat storage element sphere base；
S5, heat treatment：Including charing process and graphitization processing.For the capsule layer that fusing point is higher, thermal coefficient of expansion is low
Pyrolytic carbon and SiC, carbonization temperature are 800 DEG C, and graphitization temperature is 2000 DEG C.Obtain final high-temperature phase-change heat storage element.
The high-temperature phase-change heat storage element of assembling as shown in figure 1, including：The core 2 formed by multiple phase-change material microballoons；Bag
Enclose the matrix graphite layer 1 of the core.Its x-ray imaging result is as shown in Figure 2.
Embodiment 2 (internal microcapsules are Cu/PyC/SiC, and outer shell is MCMB powders)
S1, provide phase-change material microballoon：It is prepared from the inside to the outside successively by high temperature fluidized bed chemical vapour deposition technique
For Cu/PyC/SiC metal heat accumulation microcapsules；
S2, there is provided graphitization presoma, the raw material of outermost shell graphite is used as, and as the bag of phase transformation capsule particle
Cover the premix material before material and compacting：It is standby after the MCMB water removal that average grain diameter is 20 μm is dried；
S31, microcapsules premix with MCMB：Load 1Kg metal heat accumulation microcapsules in seed-coating machine, with 150r/
Min rotational speeds, alcohol dampening capsule is sprayed from top, while spray MCMB powder made from step S2, in glue
The above-mentioned MCMB powder of about 200 μm of capsule Surface coating a layer thickness；S32, by MCMB and coated graphite
Microcapsules after layer press quality percentage 1：9 ratio premix, for disperse discrete particles, prevent that particle directly contacts during compacting,
Extruding causes breakage mutually, obtains premix, then premix is put into quasi-iso static pressing silica gel mould, with 100MPa shaping
Pressure precompressed globulate；
S4, final pressure shaping：One layer of dense substrate graphite is pressed in above-mentioned pre- pressure ball base outsourcing using quasi-iso static pressing technique again,
Presoma is MCMB made from step S2, forming pressure 300MPa, obtains high-temperature phase-change heat storage element sphere base；
S5, heat treatment：Including charing process and graphitization processing.For the capsule layer that fusing point is higher, thermal coefficient of expansion is low
Pyrolytic carbon and SiC, carbonization temperature are 800 DEG C, and graphitization temperature is 2000 DEG C.Obtain final high-temperature phase-change heat storage element.
Above-described, only presently preferred embodiments of the present invention is not limited to the scope of the present invention, of the invention is upper
Stating embodiment can also make a variety of changes.What i.e. every claims and description according to the present patent application were made
Simply, equivalent changes and modifications, the claims of patent of the present invention are fallen within.The not detailed description of the present invention is
Routine techniques content.
Claims (11)
1. a kind of assemble method of spherical high-temperature phase transition heat storage element, comprises the following steps：
S1, provide phase-change material microballoon；
S2, provide graphitization presoma；
S3, it is put into after phase-change material microballoon is mixed with graphitization presoma in quasi-iso static pressing silica gel mould, it is pre- with 50-100MPa
Pressure so that the disperse of phase-change material microballoon obtains pre- pressure ball base in graphitization presoma；
S4, pre- pressure ball base is put into quasi-iso static pressing silica gel mould, suppressed with 120-300MPa so that multiple phase-change material microballoons
Be formed as core, and graphitization presoma forms the matrix graphite layer for surrounding the core, obtains final pressure ball base；
S5, final pressure ball base carried out being thermally treated resulting in heat accumulation element.
2. assemble method according to claim 1, it is characterised in that in step sl, the phase-change material microballoon is metal
Heat accumulation microcapsules, it is prepared by high temperature fluidized bed chemical vapour deposition technique.
3. assemble method according to claim 1, it is characterised in that step S2 is specially to mix graphite powder and adhesive
Pinch, be extrusion pelletizing, broken and be sieved into matrix graphite powder.
4. assemble method according to claim 1, it is characterised in that step S3 is specially：
S31, phase-change material microballoon and graphitization presoma are premixed so that the outer surface of each phase-change material microballoon coats one layer
Graphitization presoma, the phase-change material microballoon coated；
S32, it is put into after the phase-change material microballoon of cladding is mixed with graphitization presoma in quasi-iso static pressing silica gel mould.
5. assemble method according to claim 1, it is characterised in that in step s 4, graphitization presoma forms densification
Matrix graphite layer, its density is 1.7-2.0g/cm3。
6. assemble method according to claim 1, it is characterised in that the charging of the quasi-iso static pressing silica gel mould in step S4
Chamber is more than the loading chamber of the quasi-iso static pressing silica gel mould in step S3.
7. assemble method according to claim 1, it is characterised in that in step s 5, heat treatment is included in 800-1200
Charing process is carried out at DEG C and graphitization processing is carried out at 1800-2000 DEG C.
A kind of 8. spherical high-temperature phase-change thermal storage member that assemble method according to any one of the claims 1-7 is formed
Part, including：
The core formed by multiple phase-change material microballoons；
Surround the matrix graphite layer of the core.
9. spherical high-temperature phase transition heat storage element according to claim 8, it is characterised in that phase-change material microballoon it is a diameter of
500~2000 μm.
10. spherical high-temperature phase transition heat storage element according to claim 8, it is characterised in that the thickness of matrix graphite layer (2)
For 2-8mm.
11. spherical high-temperature phase transition heat storage element according to claim 8, it is characterised in that spherical high-temperature phase-change thermal storage member
The overall diameter of part is 30-80mm.
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| CN109321210B (en) * | 2018-10-15 | 2021-03-12 | 中国科学院上海应用物理研究所 | Method for preparing metal-clad high-temperature phase-change heat storage microcapsule and heat storage microcapsule obtained by method |
| CN112047755B (en) * | 2020-07-31 | 2021-09-17 | 华北电力大学 | Method for packaging magnesium oxide-based phase-change heat storage material by adopting gas phase technology |
| CN112111251A (en) * | 2020-10-29 | 2020-12-22 | 中国科学院上海应用物理研究所 | Assembling method of high-temperature inorganic salt phase change heat storage element with enhanced heat conduction of graphite foam and heat storage element formed by assembling method |
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