CN102888209A - Medium-high temperature composite structural heat storage material, preparation method and application thereof - Google Patents
Medium-high temperature composite structural heat storage material, preparation method and application thereof Download PDFInfo
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- CN102888209A CN102888209A CN 201210361007 CN201210361007A CN102888209A CN 102888209 A CN102888209 A CN 102888209A CN 201210361007 CN201210361007 CN 201210361007 CN 201210361007 A CN201210361007 A CN 201210361007A CN 102888209 A CN102888209 A CN 102888209A
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Abstract
The invention relates to a medium-high temperature (120-1000 DEG C or higher) composite structural heat storage material. The medium-high temperature composite structural heat storage material comprises an inorganic salt phase change latent heat material, a sensitive heat storage material and a heat conduction reinforcing material, wherein the mass ratio of the inorganic salt phase change latent heat material to the sensitive heat storage material is of 1: (0.1-10); and the heat conduction reinforcing material is of 0.0001-1kg/ (kg heat storage material) based on mass ratio. The preparation method comprises steps as follows: uniformly mixing the inorganic salt phase change latent heat material with the sensitive heat storage material and the heat conduction reinforcing material; pressurizing to form green blank; and then heating and sintering, so as to obtain the medium-high temperature composite structural heat storage material. The medium-high temperature composite structural heat storage material provided by the invention is capable of obviously reducing the corrosion resistance of the sensitive heat storage material; meanwhile, the thermal conductivity of the composite heat storage material is markedly improved by virtue of the micro-nano doping of the heat conduction reinforcing material; and moreover, high heat storage density is achieved, and wide application prospect is provided.
Description
Technical field
The present invention relates to produce with the chemical method technical field and the energy and material science and technology field of heat accumulating, particularly, the present invention relates to the composite structure heat accumulating of a kind of inorganic salt latent heat of phase change heat accumulating, researching of sensible heat storage material, heat conduction strengthening material and the preparation method and application field of composite structure heat accumulating.
Background technology
The dispersiveness of industrial exhaust heat and large energy level span, and the intermittence of renewable energy source etc. needs heat-storage technology.Middle high-temperature heat-storage technology refers to middle high-temperature residual heat or tow taste heat be stored with heat accumulating 120～1000 ℃ or higher temperature scope, in needs, discharge, try hard to solve owing to not mating the problem of bringing with ununiformity between the heat energy Supply and Demand on time, space or the intensity, a kind of technology that grows up with the thermo-efficiency that improves whole system.The high-temperature heat-storage technology not only can improve the utilization ratio of renewable energy source but also can effectively avoid energy dissipation in the development, and is all significant for Application Areass such as solar energy thermal-power-generating, space solar thermal power system, building energy conservation and industrial afterheat recovery.
The core of heat-storage technology is high-performance heat accumulating and associated heat storage and exchange system, and wherein the high-performance heat accumulating is the emphasis of studying at present.Heat accumulating can be divided into researching of sensible heat storage material, thermochemistry heat accumulating, latent heat heat accumulating (Phase Change Material, PCM) according to heat accumulation mode difference.Researching of sensible heat storage material is to utilize the temperature variation of material itself to carry out storage and the release of heat, and storage density is low, and equipment volume is huge, has limited its development in middle high-temperature heat-storage field; The thermochemistry heat accumulating is to utilize the reversible suction heat-producing chemical reaction of material to carry out storage and the release of heat, storage density is large, can satisfy in theory the requirement in middle high-temperature heat-storage field, but because the thermochemistry heat-storage technology is just based on theoretical analysis and previous experiments research at present, the application in high-temperature heat-storage field still has a lot of problems in real the realization; The latent heat heat accumulating is to utilize material self phase transformation to carry out storage and the release of heat, storage density is high, and apparatus structure is compact, and suction/exothermic process can be similar to isothermal, easily move control and management, utilizing phase change material to carry out heat accumulation is a kind of efficient heat accumulation mode.Chinese scholars is more to the research of phase-change heat-storage material, and the low temperature field mainly comprises inorganic hydrated salt, organism (paraffin, fatty acid) etc., and middle high-temperature phase-change heat storage material mainly comprises the systems such as fused salt, Metal and Alloy.Although the research of middle high-temperature heat-storage material has obtained a lot of great achievements, realize that its sizable application still faces many difficulties:
1) fused salt phase change material storage density is large, and temperature range is adjustable, but poor heat conduction, and so that the storage/heat release rate of heat accumulating is restricted, fused salt liquid phase corrodibility is stronger, requires high to heat accumulation equipment.
2) metal and alloy phase change material good heat conductivity, storage density large (unit volume), but cost is high, and oxidation and corrodibility during high temperature are stronger, and is harsh to equipment requirements.
The application bottleneck of high-temperature phase-change heat storage material during exploitation composite structure heat accumulating is expected to solve.There has been at present patent to propose some solutions for the problem that occurs in the middle high temperature phase change material (pcm) application.Adopt ceramic base directly to mix high temperature sintering with inorganic salt latent heat of phase change material among the patent CN1328107A and prepare thermal energy storage material, the capillary force that the porous of dependence ceramic matrix sintering or reticulated structure produce is kept the shaping material of complex body.Although this composite preparation technology is simple, easy to operate, be fit to sizable application, but be difficult to the relation between balance basal body structure and the phase change material physical property, the fusing point of matrix porous or cancellated sintering temperature and phase change material differs larger, phase change material loses the phenomenons such as serious when easily high temperature sintering occurring, and the heat conductivility of matrix material is poor in addition.Patent CN1803965A, CN1357591A, all adopt precast body melting Infiltration Technics to be called again secondary among the CN1390911A and make the standby thermal energy storage material of legal system, the method is a kind of a kind of technique of utilizing precast body porous or reticulated structure and phase change material melting infiltration preparation typing heat accumulating.Although the method has well been avoided the high temperature loss of inorganic fused salt phase change material among the composite preparation technology, adopt simultaneously foamed metal as the precast body Effective Raise heat conductivility of complex body, it is harsh that but Infiltration Technics requires precursor structure, the infiltration rate is low, storage density is low, complicated operation, cost is higher, unsuitable scale production.Be that housing coated phase-change material prepares ceramic heat-storing sphere with SiC among the patent CN101788239A, effectively alleviated leaking outside and the high-temperature liquid-phase corrosion phenomenon of inorganic salt latent heat of phase change material, but the preparation of housing and packaging process are complicated, often need manual operations, reserving space has increased thermal resistance in the housing, and product performance and sizable application still need be done further discussion.Patent CN102585775A discloses a kind of high temperature composite phase-change heat-storage material, comprise inorganic salt, ceramic substrate and high thermal conductivity materials, wherein, inorganic salt and ceramic substrate volume ratio are 1:5～25:1, and high thermal conductivity materials is 0.0001～1g/ (g inorganic salt-ceramic substrate system).This high temperature composite phase-change heat-storage material thermal conductivity is high, increases substantially heat accumulating storage/heat release rate, but wherein the interior storage density of high temperature range can not be satisfied the demand.
Therefore,, the problems such as heat conductivility poor, high temperature corrosion not high for the storage density of heat accumulating in the middle high-temperature heat-storage Application Areas are developed a kind of high performance middle high temperature composite structure heat accumulating and preparation method thereof significant.
Summary of the invention
For the deficiencies in the prior art, one of purpose of the present invention is to provide a kind of middle high temperature composite structure heat accumulating.Described middle high temperature composite structure heat accumulating comprises inorganic salt latent heat of phase change material, researching of sensible heat storage material and heat conduction strengthening material, wherein, the mass ratio of inorganic salt latent heat of phase change material and researching of sensible heat storage material is 1:0.1～1:10, and the heat conduction strengthening material is 0.0001～1kg/ (kg heat accumulating).
The mass ratio of described inorganic salt latent heat of phase change material and researching of sensible heat storage material can be such as 1:0.11,1:0.12,1:0.5,1:1.1,1:1.6,1:2.1,1:2.8,1:3.6,1:4.8,1:5,1:6.1,1:8,1:8.2,1:9,1:9.6,1:9.8,1:9.9 etc.
Kg/ of the present invention (kg heat accumulating) refers to the kg number of the heat conduction strengthening material that adds in every kg inorganic salt latent heat of phase change material of the present invention-researching of sensible heat storage material system, refer to such as 1kg/ (kg heat accumulating), when the total mass of inorganic salt latent heat of phase change material and researching of sensible heat storage material is 1kg, the heat conduction strengthening material is 1kg, by that analogy; Hereinafter if no special instructions, all adopt this definition.
Described heat conduction strengthening material can be 0.0002kg/kg heat accumulating, 0.0003kg/kg heat accumulating, 0.0009kg/kg heat accumulating, 0.01kg/kg heat accumulating, 0.099kg/kg heat accumulating, 0.11kg/kg heat accumulating, 0.18kg/kg heat accumulating, 0.3kg/kg heat accumulating, 0.5kg/kg heat accumulating, 0.7kg/kg heat accumulating, 0.9kg/kg heat accumulating, 0.95kg/kg heat accumulating, 0.98kg/kg heat accumulating, 0.99kg/kg heat accumulating etc.
Gu inorganic salt latent heat of phase change material is divided into solid-liquid inorganic salt latent heat of phase change material and solid-inorganic salt latent heat of phase change material.Described solid-liquid inorganic salt latent heat of phase change material refers to when temperature is higher than transformation temperature, and phase becomes liquid phase by solid phase and absorbs heat, and phase becomes the exothermic class phase change material of solid phase by liquid phase again when drop in temperature.A few days ago, solid-liquid inorganic salt high temperature phase change material (pcm) is mainly high-temperature fusion salt, part alkali, mixing salt.High-temperature fusion salt mainly contains carbonate, fluorochemical, muriate, nitrate, vitriol etc.They have higher transformation temperature, and from hundreds of degree centigrade to several thousand degrees centigrade, thereby latent heat of phase change is larger.Described solid-Gu inorganic salt latent heat of phase change material is to utilize the crystal phase transition of material to carry out storage and the release of heat.At present, this type of inorganic salt latent heat of phase change material mainly contains NH
4SCN, KHF
2Deng material.
Preferably, Gu described inorganic salt latent heat of phase change material is solid-liquid inorganic salt latent heat of phase change material and/or solid-inorganic salt latent heat of phase change material, solid-liquid inorganic salt latent heat of phase change material more preferably, more preferably basic metal is or/and the carbonate of alkaline-earth metal, vitriol, nitrate, fluorochemical, 1 kind or the combination of at least 2 kinds of similar salt in the muriate, it is alkaline carbonate, alkali metal sulfates, base metal nitrate, alkaline metal fluoride cpd, alkali metal chloride, alkaline earth metal carbonate, alkaline earth metal sulphate, alkine earth metal nitrate, alkaline-earth metal fluoride, 1 kind or the combination of at least 2 kinds of similar salt in the alkaline earth metal chloride, the typical but non-limiting example of described combination has: the combination of the carbonate of alkali-metal carbonate and alkaline-earth metal, the combination of the nitrate of alkali-metal nitrate and alkaline-earth metal, the combination of the fluorochemical of alkali-metal fluorochemical and alkaline-earth metal, the combination of the vitriol of alkali-metal vitriol and alkaline-earth metal, the muriatic combination of alkali-metal muriate and alkaline-earth metal etc.; Described basic metal is a kind or at least 2 kinds combination in lithium (Li), sodium (Na), potassium (K), rubidium (Rb), caesium (Cs), the francium (Fr); Described alkaline-earth metal is a kind or at least 2 kinds combination in beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), the radium (Ra); That is, the typical but non-limiting example of described inorganic salt latent heat of phase change material is nitric acid radium, lithium fluoride, calcium sulfate, salt of wormwood, sodium-chlor, strontium fluoride, cesium sulfate, rubidium nitrate, the combination of Quilonum Retard and yellow soda ash, the combination of sulphate of potash and magesium, the combination of calcium chloride and bariumchloride, the combination of rubidium fluoride, magnesium fluoride and Calcium Fluoride (Fluorspan), the combination of cesium nitrate, beryllium nitrate and strontium nitrate, the combination of calcium chloride, sodium-chlor and Repone K etc.; Be particularly preferably a kind or the combination of at least 2 kinds of similar salt in alkali-metal carbonate, vitriol, nitrate, the muriate, for example the carbonic acid fused salt is particularly preferably mass ratio Na as the latent heat material
2CO
3: Li
2CO
3System for 1:0.5～0.8.Described similar salt refers to the salt that negatively charged ion is identical, for example SODIUMNITRATE and nitrocalcite, vitriolate of tartar and sodium sulfate, magnesiumcarbonate and salt of wormwood, sodium-chlor and calcium chloride etc.In actual applications, the ratio of described each component of inorganic salt latent heat of phase change material can be regulated according to the knowledge of grasping and concrete needs by one of ordinary skill in the art.
Thereby in fact the sensible heat heat accumulation is exactly to utilize the high heat capacity of material self and thermal conductivity to reach the purpose of heat accumulation by the rising of self temperature.The main researching of sensible heat storage material of using has siliceous, magnesia fire-protecting wall at present, nitrate, and cast iron and cast steel, the larger material of former wet goods thermal capacitance all can be used as researching of sensible heat storage material of the present invention.
Preferably, described researching of sensible heat storage material is SiC, SiO
2, MgO, Al
2O
3, a kind or at least 2 kinds combination in the mullite, zircon stone, cordierite, described combination typical case but the example of non-limit have: SiC and SiO
2Combination, the combination of MgO and mullite, Al
2O
3, zircon stone and cordierite combination, SiO
2, mullite and cordierite combination, SiO
2, MgO and Al
2O
3Combination, SiO
2, MgO, mullite and zircon stone combination, SiC, MgO, Al
2The combination of O and zircon stone etc., more preferably SiC, SiO
2, MgO, Al
2O
3In a kind or at least 2 kinds combination, for example be particularly preferably MgO with carbonic acid fused salt latent heat of phase change Material cladding.
Preferably, described heat conduction strengthening material is high heat conduction carbon material or/and metal, such as corrosion resistant metal silks such as copper, aluminium, silver, Stainless Steel Wire, surface-treated aluminium wire, copper wire, filamentary silvers.Also has in addition the combination of copper and diamond-like carbon film, the combination of aluminium and silver, the combination of aluminium and high oriented graphite, the combination of silver, doped graphite and high thermal conductivity flexible graphite, the combination of copper, silver and highly-conductive hot carbon fiber, the combination of aluminium, carbon nanotube and high thermal conductivity flexible graphite, the combination of carbon nanotube, high heat-conductive carbon foam, expanded graphite and Graphene, the combination of diamond-like carbon film, doped graphite, high thermal conductivity flexible graphite and high heat-conductive carbon foam, the combination of aluminium, high thermal conductivity flexible graphite, highly-conductive hot carbon fiber, carbon nanotube and high heat-conductive carbon foam etc.; More preferably a kind or at least 2 kinds combination in diamond and diamond-like carbon film, high oriented graphite, doped graphite, high thermal conductivity flexible graphite, highly-conductive hot carbon fiber and matrix material, carbon nanotube and matrix material thereof, high heat-conductive carbon foam, expanded graphite, the Graphene, described combination typical case but the example of non-limit have: the combination of high oriented graphite, doped graphite, the combination of expanded graphite, Graphene, high thermal conductivity flexible graphite, the combinations of highly-conductive hot carbon fiber, carbon nanotube etc. are particularly preferably carbon nanotube.
Preferably, the mass ratio of described inorganic salt latent heat of phase change material and researching of sensible heat storage material is 1:0.17～1:5.7, is particularly preferably 1:0.25～1:3.6.
Preferably, preferably, described heat conduction strengthening material content is 0.0005～0.5kg/ (kg heat accumulating), is particularly preferably 0.001～0.1kg/ (kg heat accumulating).
One of purpose of the present invention also is to provide a kind of preparation method of described middle high temperature composite structure heat accumulating.The present invention takes into account the advantage of inorganic salt latent heat of phase change material and researching of sensible heat storage material, and storage density is high; Strengthen heat accumulating structure properties and corrosion-and high-temp-resistant performance by material mixing ratio, grain graininess regulation and control, forming pressure, dwell time and sintering process; Adopt lqiuid phase sintering method, reduce the loss of fused salt high temperature sintering; By the micro-nano doping of heat conduction strengthening material, strengthen the complex body heat conductivility, increase substantially heat accumulating storage/heat release rate; The preparation method is simple, is easy to sizable application.
The preparation method of described middle high temperature composite structure heat accumulating may further comprise the steps:
(1) with after the grinding of formula ratio inorganic salt latent heat of phase change material, mix with researching of sensible heat storage material and heat conduction strengthening material, green compact are made in extrusion forming.
(2) with step (1) gained green compact intensification sintering, make middle high temperature composite structure heat accumulating.
Preferably, in the step (1) inorganic salt latent heat of phase change material is ground, then mix with researching of sensible heat storage material and heat conduction strengthening material.
Preferably, in the step (1) inorganic salt latent heat of phase change material is ground rear at least 100 mesh sieves of crossing, then mix further preferred mistake 120 mesh sieves with researching of sensible heat storage material and heat conduction strengthening material.
Preferably, be ground to ball milling described in the step (1).
Preferably, described being mixed into by ball milling of inorganic salt latent heat of phase change material and researching of sensible heat storage material and heat conduction strengthening material mixes described in the step (1).
Preferably, extrusion forming pressure is more than the 2MPa described in the step (1), such as 2.1Mpa, 2.2Mpa, 2.3Mpa, 3Mpa, 4Mpa, 6Mpa, 10Mpa, 14Mpa, 26Mpa, 28Mpa, 29Mpa, 31Mpa, 35Mpa, 40Mpa etc., more preferably 2～30MPa is particularly preferably 5～15Mpa.
Preferably, the extrusion forming time described in the step (1) is more than the 0.3min, such as 0.31min, 0.32min, 0.33min, 0.39min, 0.46min, 0.58min, 0.9min, 1min, 5min, 9min, 16min, 18min, 19min, 21min, 26min, 29min, 34min etc., more preferably 0.4～20min is particularly preferably 0.5～10min.
Preferably, the intensification described in the step (2) such as is sintered at static pressure (isopressing sintering) sintering, two-step sintering (two step sintering) or the liquid phase sintering (liquid phase sintering), is particularly preferably liquid phase sintering.
Preferably, heat up described in the step (2) and be sintered to below temperature rise rate with 0.1～8 ℃/min rises to inorganic salt latent heat of phase change material by room temperature the latent heat of phase change temperature 80～120 ℃, then be warming up to above 40～70 ℃ of the latent heat of phase change temperature of inorganic salt latent heat of phase change material with the temperature rise rate of 0.01～2 ℃/min, be incubated at least 60min, such as 61min, 62min, 65min, 70min, 80min, 89min, 91min, 100min etc. is with stage same rate cooling; Further preferred, heat up described in the step (2) and be sintered to below temperature rise rate with 2～7 ℃/min rises to inorganic salt latent heat of phase change material by room temperature the latent heat of phase change temperature 90～110 ℃, then be warming up to above 45～55 ℃ of the latent heat of phase change temperature of inorganic salt latent heat of phase change material with the temperature rise rate of 0.1～1.5 ℃/min, be incubated at least 80min, with stage same rate cooling; Particularly preferably, heat up described in the step (2) to be sintered to 4～6 ℃/min of temperature rise rate and risen to below the latent heat of phase change temperature of inorganic salt latent heat of phase change material 100 ℃ by room temperature, then be warming up to above 50 ℃ of the latent heat of phase change temperature of inorganic salt latent heat of phase change material with the temperature rise rate of 0.8～1.2 ℃/min, be incubated at least 90min, with stage same rate cooling; The described cooling with the stage same rate refers to that in above-mentioned stages, the rate of cooling in same stage is identical with temperature rise rate.
Preferably, the preparation method of described middle high temperature composite structure heat accumulating may further comprise the steps:
(1) inorganic salt latent heat of phase change material is mixed with researching of sensible heat storage material by prescription, then the heat conduction strengthening material is added into this compound system, more than the above extrusion forming 0.3min of 2MPa, obtain composite structure heat accumulating green compact;
(2) green compact that step (1) obtained make middle high temperature composite structure heat accumulating through liquid phase sintering, wherein said liquid phase sintering is below the latent heat of phase change temperature that is risen to inorganic salt latent heat of phase change material with the temperature rise rate of 0.1～8 ℃/min by room temperature 80～120 ℃, then be warming up to above 40～70 ℃ of the latent heat of phase change temperature of inorganic salt latent heat of phase change material with the temperature rise rate of 0.01～2 ℃/min, be incubated at least 60min, with stage same rate cooling.
Middle each component of high temperature composite structure heat accumulating by the method for the invention preparation mixes, and has excellent heat conductivility and large storage density, can satisfy existing demand.
One of purpose of the present invention also is to provide the purposes of described middle high temperature composite structure heat accumulating.Described middle high temperature composite structure heat accumulating can be used for the synthetic field of industrial afterheat recovery, solar energy thermal utilization, high-temperature flue gas recovery, cold-hot-Electricity Federation usefulness system, mixed power electric car or matrix material.
" comprising " of the present invention, mean it except described component, can also comprise other components, these other components give described middle high temperature composite structure heat accumulating different characteristics.In addition, " comprising " of the present invention, can also replace with enclosed " being " or " by ... form ".
Compared with prior art, remarkable advantage of the present invention is:
(1) the phase transformation enthalpy of inorganic salt latent heat of phase change material is large, and the inorganic salt latent heat of phase change heat accumulating of proper formulation and researching of sensible heat storage material chemical compatibility, thermal stability are good;
(2) the compound system storage density is large, and storage density reaches 350～750kJ/kg above (300 ℃ of temperature difference) in the middle high temperature range; By the micro-nano heat conduction strengthening material that mixes, the good heat conductivity of matrix material;
(3) composite structure need not prefabricated matrix, with sintering process (such as lqiuid phase sintering method) step preparation composite structure heat accumulating, has reduced the phase change material loss, and method is simply efficient, and cost is lower, and proper scale is used.
Description of drawings
Fig. 1 is the thermogram of the synthetic middle high temperature composite structure heat accumulating of embodiment 1.
Fig. 2 is the XRD analysis collection of illustrative plates of the synthetic middle high temperature composite structure heat accumulating of embodiment 1.
Fig. 3 is middle high temperature composite structure heat accumulating number and the scanning electron microscope picture that embodiment 1 synthesizes.
Fig. 4 is the thermogram of the synthetic middle high temperature composite structure heat accumulating of embodiment 2.
Fig. 5 is the compound XRD analysis collection of illustrative plates of the researching of sensible heat storage material of embodiment 2 and Repone K sodium-chlor.
Fig. 6 is the thermogram of the synthetic middle high temperature composite structure heat accumulating of embodiment 3.
Fig. 7 is the compound XRD analysis collection of illustrative plates of the researching of sensible heat storage material of embodiment 3 and Repone K lithium chloride.
Fig. 8 is the thermogram of the synthetic middle high temperature composite structure heat accumulating of embodiment 4.
Fig. 9 is the XRD analysis collection of illustrative plates of the synthetic middle high temperature composite structure heat accumulating of embodiment 4.
Figure 10 is the process flow sheet of one embodiment of the invention.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment helps to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment 1
Get mass ratio Na
2CO
3: Li
2CO
3Molten salt system 5kg for 1:0.75, ground 120 orders, add 5kg magnesium oxide, 0.05kg the carbon nanotube mixed grinding is abundant, is that Φ 15mm steel grinding tool 5MPa 5min of lower dwell time of constant pressure prepares briquetting with diameter, the sample that the demoulding is taken out after the compacting is inserted crucible, temperature rise rate is that 5 ℃/min rises to 400 ℃ by room temperature, 1 ℃/min rises to 550 ℃ by 400 ℃, and 550 ℃ of insulation 90min are with stage same rate cooling.The thermal analysis curve of resulting materials can find out that therefrom the heat physical properties of compound system is better as shown in Figure 1, and storage density is more than 525kJ/kg in 300～600 ℃ of temperature ranges.The XRD figure spectrum of thermal energy storage material as shown in Figure 2, the result show magnesium oxide as in researching of sensible heat storage material and the carbonic acid fused salt phase change material compound tense system except Quilonum Retard sodium eutectic salts, magnesium oxide phase exist, produce without other cenotypes, since the XRD peak value of carbon nanotube weak in compound system phase and not obvious, the XRD test shows that the chemical compatibility between the each component is better in this composite structure heat accumulating.The digital electric photo of composite structure heat accumulating and scanning electron microscope picture as shown in Figure 3, the result shows distributed components in the composite structure heat accumulating.Heat conductivility to the composite structure heat accumulating is measured, and found that, the heat conductivility of compound system is improved significantly, and its thermal conductivity is not for adding 3～4 times before the heat conduction strengthening material.
Getting mass ratio NaCl:KCl is the molten salt system 5kg of 1:1.3, grinds 120 orders, adds the 5kg silicon oxide, mixed grinding is abundant, add the 0.05kg Graphite Powder 99, mix thoroughly, getting an amount of mixed powder length and width is to prepare briquetting under 50 * 20mm steel grinding tool 5MPa constant pressure, its dwell time 5min, the sample that the demoulding is taken out after the compacting is inserted crucible, and temperature rise rate is that 5 ℃/min rises to 550 ℃ by room temperature, and 1 ℃/min rises to 700 ℃ by 550 ℃, 700 ℃ of insulation 90min are with stage same rate cooling.The hot analytical results of resulting materials as shown in Figure 4, the storage density of muriate and silicon oxide thermal energy storage material is large, chemical compatibility is (Fig. 5) better, the heat conductivility of matrix material is improved significantly.
Getting mass ratio KCl:LiCl is the molten salt system 5kg of 1:0.85, grinds 120 orders, adds 5kg silicon carbide, mixed grinding is abundant, add the 0.2kg Stainless Steel Wire, mix thoroughly, getting an amount of mixed powder length and width is to prepare briquetting under 50 * 20mm steel grinding tool 5MPa constant pressure, its dwell time 5min, the sample that the demoulding is taken out after the compacting is inserted crucible, and temperature rise rate is that 5 ℃/min rises to 250 ℃ by room temperature, and 1 ℃/min rises to 400 ℃ by 250 ℃, 400 ℃ of insulation 90min are with stage same rate cooling.The total storage density of KCl+LiCl fused salt higher (Fig. 6), with silicon carbide compound chemical compatibility better (Fig. 7), the muriate heat accumulating heat conductivility of silicon carbide compound is better.
Embodiment 4
Get Na
2SO
4Fused salt 5kg, ground 120 orders, add 5.5kg silicon oxide and 0.25kg Stainless Steel Wire, mix and fully mix thoroughly, getting an amount of mixed powder length and width is to prepare briquetting under 50 * 20mm steel grinding tool 5MPa constant pressure, its dwell time 5min, the sample that the demoulding is taken out after the compacting is inserted crucible, and temperature rise rate is that 5 ℃/min rises to 800 ℃ by room temperature, and 1 ℃/min rises to 950 ℃ by 800 ℃, 950 ℃ of insulation 90min are with stage same rate cooling.The thermal characteristics of gained composite structure heat accumulating superior (Fig. 8), the chemical compatibility between the complex body each component good (Fig. 9), heat conductivility is significantly improved.
Get mass ratio K
2CO
3: Li
2CO
3Molten salt system 10kg for 1:0.88, ground 100 orders, add 100kg magnesium oxide, mixed grinding is abundant, add the 1kg Graphite Powder 99, mix thoroughly, getting an amount of mixed powder length and width is to prepare briquetting under 50 * 20mm steel grinding tool 2MPa constant pressure, its dwell time 20min, the sample that the demoulding is taken out after the compacting is inserted crucible, and to be 0.1 ℃/min rise to below the molten salt system latent heat of phase change temperature 120 ℃ by room temperature to temperature rise rate, and then 0.01 ℃/min is warming up to above 40 ℃ of molten salt system latent heat of phase change temperature, insulation 120min is with stage same rate cooling.K
2CO
3+ Li
2CO
3Storage density is more than 520kJ/kg in 300～600 ℃ of temperature ranges for fused salt, and better with magnesium oxide composite chemical consistency, the compound heat accumulating heat conductivility of magnesium oxide is better.
Get mass ratio KNO
3: NaNO
3Molten salt system 20kg for 1:0.81 ground 110 orders, added 2kgAl
2O
3Mixed grinding is abundant, add the 22g Graphite Powder 99, mix thoroughly, getting an amount of mixed powder length and width is to prepare briquetting under 50 * 20mm steel grinding tool 30MPa constant pressure, its dwell time 0.3min, the sample that the demoulding is taken out after the compacting is inserted crucible, and to be 8 ℃/min rise to below the molten salt system latent heat of phase change temperature 80 ℃ by room temperature to temperature rise rate, and then 2 ℃/min is warming up to above 70 ℃ of molten salt system latent heat of phase change temperature, insulation 60min is with stage same rate cooling.KNO
3+ NaNO
3Storage density is more than 430kJ/kg in 200～400 ℃ of temperature ranges for fused salt, and better with the alumina composite chemical compatibility, the heat accumulating heat conductivility of alumina composite is better.
Get mass ratio NaCl:MgCl
2Molten salt system 10kg for 1:1.08, ground 130 orders, add the 100kg mullite, mixed grinding is abundant, add the 0.011kg Graphene, mix thoroughly, getting an amount of mixed powder length and width is to prepare briquetting under 50 * 20mm steel grinding tool 15MPa constant pressure, its dwell time 0.4min, the sample that the demoulding is taken out after the compacting is inserted crucible, and to be 7 ℃/min rise to below the molten salt system latent heat of phase change temperature 90 ℃ by room temperature to temperature rise rate, and then 0.1 ℃/min is warming up to above 50 ℃ of molten salt system latent heat of phase change temperature, insulation 100min is with stage same rate cooling.NaCl+MgCl
2Storage density is more than 535kJ/kg in 300～600 ℃ of temperature ranges for fused salt, and better with mullite composite chemical consistency, the compound heat accumulating heat conductivility of mullite is better.
Embodiment 8
Get mass ratio NaF:MgF
2Molten salt system 10kg for 1:0.49, ground 130 orders, add the 100kg silicon oxide, mixed grinding is abundant, add 1kg highly-conductive hot carbon fiber, mix thoroughly, getting an amount of mixed powder length and width is to prepare briquetting under 50 * 20mm steel grinding tool 15MPa constant pressure, its dwell time 1min, the sample that the demoulding is taken out after the compacting is inserted crucible, and to be 4 ℃/min rise to below the molten salt system latent heat of phase change temperature 85 ℃ by room temperature to temperature rise rate, and then 0.5 ℃/min is warming up to above 50 ℃ of molten salt system latent heat of phase change temperature, insulation 110min is with stage same rate cooling.NaF+MgF
2Storage density is more than 700kJ/kg in 600～1000 ℃ of temperature ranges for fused salt, and better with silicon oxide composite chemical consistency, the compound heat accumulating heat conductivility of silicon oxide is better.
Applicant's statement, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, does not mean that namely the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.The person of ordinary skill in the field should understand, any improvement in the present invention to the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (10)
1. high temperature composite structure heat accumulating in a kind, comprise inorganic salt latent heat of phase change material, researching of sensible heat storage material and heat conduction strengthening material, wherein, the mass ratio of inorganic salt latent heat of phase change material and researching of sensible heat storage material is 1:0.1～1:10, and the heat conduction strengthening material is 0.0001～1kg/ (kg heat accumulating).
2. middle high temperature composite structure heat accumulating as claimed in claim 1, it is characterized in that, Gu described inorganic salt latent heat of phase change material is solid-liquid inorganic salt latent heat of phase change material and/or solid-inorganic salt latent heat of phase change material, solid-liquid inorganic salt latent heat of phase change material more preferably, more preferably basic metal is or/and a kind or the combination of at least 2 kinds of similar salt in the carbonate of alkaline-earth metal, vitriol, nitrate, fluorochemical, muriate is particularly preferably a kind or the combination of at least 2 kinds of similar salt in alkali-metal carbonate, vitriol, nitrate, the muriate.
3. middle high temperature composite structure heat accumulating as claimed in claim 1 or 2 is characterized in that, described researching of sensible heat storage material is SiC, SiO
2, MgO, Al
2O
3, a kind or at least 2 kinds combination in the mullite, zircon stone, cordierite, more preferably SiC, SiO
2, MgO, Al
2O
3In a kind or at least 2 kinds combination.
4. such as each described middle high temperature composite structure heat accumulating of claim 1-3, it is characterized in that, described heat conduction strengthening material is that high heat conduction carbon material is or/and metal, more preferably a kind or at least 2 kinds combination in diamond and diamond-like carbon film, high oriented graphite, doped graphite, high thermal conductivity flexible graphite, highly-conductive hot carbon fiber and matrix material, carbon nanotube and matrix material thereof, high heat-conductive carbon foam, expanded graphite, the Graphene is particularly preferably carbon nanotube;
Preferably, the mass ratio of described inorganic salt latent heat of phase change material and researching of sensible heat storage material is 1:0.17～1:5.7, is particularly preferably 1:0.25～1:3.6;
Preferably, described heat conduction strengthening material content is 0.0005～0.5kg/ (kg heat accumulating), is particularly preferably 0.001～0.1kg/ (kg heat accumulating).
5. such as the preparation method of each described middle high temperature composite structure heat accumulating of claim 1-4, may further comprise the steps:
(1) inorganic salt latent heat of phase change material and researching of sensible heat storage material and heat conduction strengthening material are mixed, green compact are made in extrusion forming;
(2) with step (1) gained green compact intensification sintering, make middle high temperature composite structure heat accumulating.
6. method as claimed in claim 5 is characterized in that, in the step (1) inorganic salt latent heat of phase change material is ground, and then mixes with researching of sensible heat storage material and heat conduction strengthening material;
Preferably, in the step (1) inorganic salt latent heat of phase change material is ground rear at least 100 mesh sieves of crossing, then mix further preferred mistake 120 mesh sieves with researching of sensible heat storage material and heat conduction strengthening material;
Preferably, be ground to ball milling described in the step (1);
Preferably, described being mixed into by ball milling of inorganic salt latent heat of phase change material and researching of sensible heat storage material and heat conduction strengthening material mixes described in the step (1).
7. such as claim 5 or 6 described methods, it is characterized in that, extrusion forming pressure is more than the 2MPa described in the step (1), and more preferably 2～30MPa is particularly preferably 5～15Mpa;
Preferably, the extrusion forming time described in the step (1) is more than the 0.3min, and more preferably 0.4～20min is particularly preferably 0.5～10min;
Preferably, the intensification described in the step (2) is sintered to isostatic sintering, two-step sintering or liquid phase sintering, is particularly preferably liquid phase sintering.
8. such as each described method of claim 5-7, it is characterized in that, heat up described in the step (2) and be sintered to below temperature rise rate with 0.1～8 ℃/min rises to inorganic salt latent heat of phase change material by room temperature the latent heat of phase change temperature 80～120 ℃, then be warming up to above 40～70 ℃ of the latent heat of phase change temperature of inorganic salt latent heat of phase change material with the temperature rise rate of 0.01～2 ℃/min, be incubated at least 60min, with stage same rate cooling;
Preferably, heat up described in the step (2) and be sintered to below temperature rise rate with 2～7 ℃/min rises to inorganic salt latent heat of phase change material by room temperature the latent heat of phase change temperature 90～110 ℃, then be warming up to above 45～55 ℃ of the latent heat of phase change temperature of inorganic salt latent heat of phase change material with the temperature rise rate of 0.1～1.5 ℃/min, be incubated at least 80min, with stage same rate cooling;
Preferably, heat up described in the step (2) to be sintered to 4～6 ℃/min of temperature rise rate and risen to below the latent heat of phase change temperature of inorganic salt latent heat of phase change material 100 ℃ by room temperature, then be warming up to above 50 ℃ of the latent heat of phase change temperature of inorganic salt latent heat of phase change material with the temperature rise rate of 0.8～1.2 ℃/min, be incubated at least 90min, with stage same rate cooling.
9. such as the preparation method of each described middle high temperature composite structure heat accumulating of claim 1-4, may further comprise the steps:
(1) inorganic salt latent heat of phase change material is mixed with researching of sensible heat storage material by prescription, then the heat conduction strengthening material is added into this compound system, more than the above extrusion forming 0.3min of 2MPa, obtain composite structure heat accumulating green compact;
(2) green compact that step (1) obtained make middle high temperature composite structure heat accumulating through liquid phase sintering, wherein said liquid phase sintering is below the latent heat of phase change temperature that is risen to inorganic salt latent heat of phase change material with the temperature rise rate of 0.1～8 ℃/min by room temperature 80～120 ℃, then be warming up to above 40～70 ℃ of the latent heat of phase change temperature of inorganic salt latent heat of phase change material with the temperature rise rate of 0.01～2 ℃/min, be incubated at least 60min, with stage same rate cooling.
10. such as the purposes of each described middle high temperature composite structure heat accumulating of claim 1-4, it is characterized in that, described middle high temperature composite structure heat accumulating is used the synthetic field of system, mixed power electric car or matrix material for industrial afterheat recovery, solar energy thermal utilization, high-temperature flue gas recovery, cold-hot-Electricity Federation.
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