CN109181649A - High thermal conductivity optical and thermal conversion composite phase-change heat-storage material and preparation method thereof for solar water heater - Google Patents
High thermal conductivity optical and thermal conversion composite phase-change heat-storage material and preparation method thereof for solar water heater Download PDFInfo
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- CN109181649A CN109181649A CN201810784406.1A CN201810784406A CN109181649A CN 109181649 A CN109181649 A CN 109181649A CN 201810784406 A CN201810784406 A CN 201810784406A CN 109181649 A CN109181649 A CN 109181649A
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Abstract
The invention discloses the high thermal conductivity optical and thermal conversion composite phase-change heat-storage materials and preparation method thereof for solar water heater；The preparation method is to mix sodium acetate trihydrate and nucleating agent, is heated to 60-80 DEG C and keeps the temperature 1-3h；Expanded graphite is added, stirs evenly, obtains uniform sodium acetate trihydrate/expanded graphite mixture；Under the conditions of temperature is 60-80 DEG C, nanometer photo-thermal converting material is added while stirring, continues to stir 2-4h, after being cooled to room temperature, it is 0.5-2g/cm that the mixing material after stirring, which is pressed into density,3Bulk, obtain high thermal conductivity optical and thermal conversion composite phase-change heat-storage material；The material not only has ideal storage density and heating conduction, but also can efficiently convert light energy into thermal energy, and thermal coefficient is 2.27-3.52W/ (mK), and optical and thermal transformation efficiency is 86.6-91.0%.
Description
Technical field
The present invention relates to phase-change heat-storage material fields, more particularly to a kind of high thermal conductivity light-for solar water heater
Thermal transition composite phase-change heat-storage material and preparation method thereof.
Background technique
Solar water heater is the device for converting solar energy into thermal energy, by water from low-temperature heat to high temperature, meets people
Demand in life production to hot water.Solar water heater currently on the market mainly has heat collector, insulated water tank, control system
The part such as system, connecting pipe is constituted.The heat that heat collector generates is stored in water by heat exchange.However the storage density of water
It is low, it usually needs biggish water tank is with meet demand.Meanwhile there is also foulings for this water heater, leaving water temperature is non-constant, pushes up water
The disadvantages of water quality is stale.
Phase-change material absorbs or discharges heat and undergoing phase transition, the phase transition temperature model for having storage density high, narrow
It the advantages such as encloses, plays key player in field of thermal energy storage.Sodium acetate trihydrate is a kind of phase-change material haveing excellent performance, phase transformation
Temperature is 58 DEG C, and good flame resistance is nontoxic corrosion-free, cheap and easy to get.The 1kg substance, which is undergone phase transition, can be absorbed or discharge 280KJ
Heat, and discharge or absorb same heat, need 3.3kg coolant-temperature gage to change 20 DEG C.Therefore, using sodium acetate trihydrate heat accumulation,
With apparent advantage.
However, sodium acetate trihydrate as phase-change material in use, face three problems: supercooling, heating conduction be poor,
Leakage.In general, nucleating agent is added to reduce degree of supercooling, Sodium acetate trihydrate crystal property is improved.By preparing answering for dimensionally stable
Close phase-change material and solve leakage problem, this kind of phase-change material is heated undergo phase transition after be still macroscopically solid, microcosmic shape only occurs
The phase transformation of state.Its thermal conductivity is improved by the way that heat filling is added, but the addition of heat filling will necessarily reduce effective phase-change material
Content, influence its storage density.
In the phase-change material of solar water heater field application, the most ideal situation is that phase-change heat-storage material has both heat collector
Function, i.e. phase-change material itself can absorb luminous energy, and converts light energy into thermal energy.It is integrated that water heater not only can be improved in this
Degree reduces volume, and the technology complexity for producing and installing substantially reduces.However, common phase-change material does not have
Convert light energy into the ability of thermal energy.
Chinese invention patent 201610437361.1 discloses a kind of phase-changing energy storage material for solar energy heat-storage, the material
For material using sodium acetate trihydrate as solar energy heat-storage material, expanded graphite is sizing carrier, the mixture of ethyl alcohol and fluoric acid sylvite
As nucleating agent, the phase-changing energy storage material heat enthalpy value is high, and performance is stablized.However, the material does not have optical and thermal conversion capability,
Only play the role of heat accumulation in solar water heater.
Chinese invention patent application 2015103988760 discloses one kind can be efficiently compound using the fixed phase change of solar energy
Material, by inorganic carrier backing material and the Organic phase change thermal storage material being filled in the inorganic carrier backing material and photo-thermal
Conversion nano material.The present invention also provides it is above-mentioned can efficiently using solar energy stable phase change composite material preparation method,
The following steps are included: (1) prepares CuS nano-powder, (2) prepare paraffin-SiO2- CuS stable phase change composite material.Institute of the present invention
Stable phase change composite material is stated, not only in heat storage capacity and phase transition process with higher the characteristics of dimensionally stable, the phase transformation is multiple
Condensation material also has significant photothermal conversion ability, sunlight more efficiently can be converted into thermal energy storage, to realize
Efficient utilize of solar energy provides a new way.It is obtained using the preparation method of the above-mentioned stable phase change composite material of the present invention
Composite material in each component good dispersion, composite effect be good, stable structure of material.However, the SiO that the invention uses2It leads
Hot property is poor, and the prior art is usually by SiO2As thermal insulating filling and heat-insulating material, such as Chinese invention patent application
201711167363.4 200810226164 and 200810042735.5 are directed to SiO2As thermal insulating filling and heat-insulating material.
And the thermal coefficient of paraffin is also only the left and right 0.25W/ (mK), therefore, the composite phase-change material of invention preparation is due to thermally conductive
Performance is poor, is unable to satisfy requirement of the phase-change material to high heat exchange rate.
Summary of the invention
In view of the deficiencies of the prior art, the object of the present invention is to provide a kind of conversion composite phase-change storages of high thermal conductivity optical and thermal
Hot material and preparation method thereof；Not only storage density is high for the material, is integrated with the heat collector and water tank of current solar water heater
Function, and have high thermal coefficient, can efficiently convert light energy into thermal energy, optical and thermal transformation efficiency is up to 86%
More than.
In order to realize the above technical purpose, the invention adopts the following technical scheme:
The preparation method of high thermal conductivity optical and thermal conversion composite phase-change heat-storage material for solar water heater, comprising following
Step:
1) sodium acetate trihydrate and nucleating agent are mixed, is heated to 60-80 DEG C and keeps the temperature 1-3h；Expanded graphite, stirring is added
Uniformly, uniform sodium acetate trihydrate/expanded graphite mixture is obtained；
2) under the conditions of temperature is 60-80 DEG C, nanometer photo-thermal converting material is added while stirring, continues to stir 2-4h, it is cold
But to after room temperature, it is 0.5-2g/cm that the mixing material after stirring, which is pressed into density,3Bulk, obtain high thermal conductivity optical and thermal conversion
Composite phase-change heat-storage material；
In terms of mass fraction, raw material components composition are as follows:
Sodium acetate trihydrate: 65-80%
Nucleating agent: 0.3-5%
Expanded graphite: 10-30%
Nanometer photo-thermal converting material: 5-10%.
To further realize the object of the invention, it is preferable that the nucleating agent is aluminium nitride, disodium hydrogen phosphate, silver nanoparticle
One of particle, two water sodium bromides and anhydrous sodium acetate are a variety of.
Preferably, the nanometer photo-thermal converting material is CuS, Cu2S、CuSe、Bi2S3、TiS2, carbon nanotube, nanometer
One of graphite powder and nano carbon black are a variety of.
Preferably, step 1) and stirring described in step 2) are all mechanical stirring.
Preferably, the churned mechanically time is 1-2h.
Preferably, the churned mechanically speed is 100-600r/min.
Preferably, mixing material density described after compacting is 1-1.5g/cm3。
A kind of high thermal conductivity optical and thermal conversion composite phase-change heat-storage material for solar water heater, by above-mentioned preparation side
Method is made；The phase transition temperature of composite phase-change heat-storage material is 55-58 DEG C, latent heat of phase change 176.7-216J/g, and thermal coefficient is
2.27-3.52W/ (mK), for degree of supercooling less than 4 DEG C, optical and thermal transformation efficiency is 86.6-91.0%.
Compared with the existing technology, the advantages and positive effects of the present invention are:
1) composite phase-change heat-storage material provided by the invention does heat accumulation agent using sodium acetate trihydrate, compares organic matter heat accumulation agent
Have the advantages that latent heat of phase change height, good heat conductivity, price are low etc..
2) composite phase-change heat-storage material provided by the invention not only overcomes three water using expanded graphite as backing material
Fluid leakage problems in sodium acetate phase transition process, and pass through compression forming, it forms between expanded graphite particles and effectively leads
Ther mal network improves the heating conduction (highest thermal coefficient is 3.52W/ (mK)) of phase-change material, is conducive in phase-change material
The heat exchange in portion.
3) composite phase-change heat-storage material provided by the invention not only has high storage density, can also be efficiently by luminous energy
It is converted into thermal energy, optical and thermal transformation efficiency is up to 86% or more.It applies on solar water heater, has both heat collector and water tank
Dual function reduces solar water heater volume, reduces the technology complexity of water heater production and installation.
Specific embodiment
In order to better understand the present invention, below with reference to embodiment, the present invention will be further described, but reality of the invention
Applying method is without being limited thereto.
The present invention converts the raw material of composite phase-change heat-storage material mainly by three for the high thermal conductivity optical and thermal of solar water heater
Water sodium acetate, nucleating agent, expanded graphite and nanometer photo-thermal converting material composition, but nanometer photo-thermal is simply not converted into material
Material is added in phase-changing energy storage material.But inventor has found that expanded graphite acts not only as backing material and overcomes three water acetic acid
Fluid leakage problems in sodium phase transition process, and pass through compression forming, effective thermal conductive network is formd between expanded graphite particles
Network improves the heating conduction (highest thermal coefficient is 3.52W/ (mK)) of phase-change material, is conducive to inside phase-change material
Heat exchange.It is 0.5-2g/cm that the mixture that raw material forms is pressed into density by the present invention3Bulk, inventors have found that working as density
Lower than 0.5g/cm3, phase-change heat-storage material heating conduction is bad, and when density is higher than 2g/cm3, the molding cost of material is very high.
General solar water heater includes the parts such as heat collector, insulated water tank, pipeline, control system.The work of heat collector
With being to utilize solar radiation, thermal energy is converted solar energy into, and the storage of thermal energy will then be realized by insulated water tank.For general
Logical solar water heater, thermal-arrest and heat accumulation are completed by different components.Material prepared by the present invention both can be by solar energy
It is converted into thermal energy, and the thermal energy can be stored, has both the function of heat collector and water tank.Since material prepared by the present invention has simultaneously
There is the function of thermal-arrest and heat accumulation, is equivalent to the function of the heat collector and water tank that combine general solar water heater.System of the present invention
After standby material package, guarantee that the front (face i.e. on the sunny side) of material is glass-encapsulated, material directly irradiates in sunlight
Solar energy can be absorbed and be converted into thermal energy, and directly stored；Thermal energy storage of the present invention is in phase-change material, and indirect storage
It deposits in water.When hot water is needed, cold water and the phase-change material of heat accumulation is made to carry out heat exchange, heat is transferred in water, water
Temperature increases.Such advantage is: first, solar energy is stored without a large amount of water, therefore the volume of system can be saved.The
Two, water is not being slowly heated always, but is reheated when needed, this can reduce water long-time heating or repeatedly heating pair
It is influenced caused by health.And existing water heater, the effect of heat collector are only to collect heat, do not store heat.
Embodiment 1
A kind of high thermal conductivity optical and thermal for solar water heater converts the preparation method of composite phase-change heat-storage material, includes
Following steps: weighing 75g sodium acetate trihydrate and mixes with 0.3g disodium hydrogen phosphate, is heated to 75 DEG C and keeps the temperature 3h.Then it is added
14g expanded graphite, mechanical stirring 1h, revolving speed 100r/min obtain uniform Sodium acetate trihydrate/expanded graphite mixture.Control
10g CuS nanoparticles are added in mixing speed processed and temperature-resistant while stirring, continue to stir 2h, after being cooled to room temperature, using mold
It is 1g/cm that the mixture, which is pressed into density,3Block, obtain high thermal conductivity optical and thermal conversion composite phase-change heat-storage material.
Embodiment 2
A kind of high thermal conductivity optical and thermal for solar water heater converts the preparation method of composite phase-change heat-storage material, includes
Following steps: weighing 65g sodium acetate trihydrate and mixes with 2g aluminium nitride, is heated to 60 DEG C and keeps the temperature 2h.24g expansion is then added
Graphite, mechanical stirring 2h, revolving speed 300r/min obtain uniform Sodium acetate trihydrate/expanded graphite mixture.Control stirring speed
It spends and temperature-resistant, 8g nano graphite powder is added while stirring, continue to stir 3h, after being cooled to room temperature, be mixed this using mold
Closing object and being pressed into density is 2g/cm3Block, obtain high thermal conductivity optical and thermal conversion composite phase-change heat-storage material.
Embodiment 3
A kind of high thermal conductivity optical and thermal for solar water heater converts the preparation method of composite phase-change heat-storage material, includes
Following steps: weighing 80g sodium acetate trihydrate and mixes with bis- water sodium bromide of 5g, is heated to 80 DEG C and keeps the temperature 1h.9g is then added
Expanded graphite, mechanical stirring 3h, revolving speed 600r/min obtain uniform Sodium acetate trihydrate/expanded graphite mixture.Control is stirred
Speed and temperature-resistant is mixed, 5g carbon nanotube is added while stirring, continuing to stir 4h should using mold after being cooled to room temperature
It is 0.5g/cm that mixture, which is pressed into density,3Block, obtain high thermal conductivity optical and thermal conversion composite phase-change heat-storage material.
Comparative example 1
A kind of preparation method of high thermal conductivity optical and thermal conversion composite phase-change heat-storage material comprising the steps of: weigh 75g tri-
Water sodium acetate and with 1g disodium hydrogen phosphate mix, be heated to 75 DEG C and keep the temperature 2h.14g expanded graphite, mechanical stirring is then added
1h, revolving speed 100r/min obtain uniform Sodium acetate trihydrate/expanded graphite mixture.It, will using mold after being cooled to room temperature
It is 1g/cm that the mixture, which is pressed into density,3Block, obtain comparative example phase-change heat-storage material.
Embodiment and comparative example testing of materials result such as table 1, optical and thermal transformation efficiency are calculated by following formula:(Y.Wang,B.Tang and S.Zhang,J.Mater.Chem.,2012,22,18145-18150)。
1 embodiment of table and comparative example testing of materials result
High thermal conductivity optical and thermal conversion composite phase-change material prepared by the present invention for solar water heater uses three water acetic acid
Sodium is as heat accumulation agent, and composite phase-change material disclosed in Chinese invention patent 2015103988760 does heat accumulation agent using paraffin, preceding
Person in heating conduction, latent heat of phase change, in price have a clear superiority.
It is expanded graphite that the present invention, which maintains the backing material of phase-change material shape, is not only because expanded graphite compared to dioxy
SiClx height has more high thermal conductivity coefficient, it is often more important that since expanded graphite has mechanical chain effect under pressure can
To be compressed into the block of the higher density of arbitrary shape, therefore optical and thermal prepared by the present invention converts leading for composite phase-change material
Hot property is higher than composite phase-change material disclosed in patent 2015103988760 (using silica as backing material).It is thermally conductive
Performance directly affects the transformation rate of phase-change material and the exchange rate with other substances.
In addition, high thermal conductivity optical and thermal of the present invention preparation for solar water heater converts composite phase-change material, have both at present
The heat collector of solar water heater and the dual function of water tank efficiently can directly turn solar energy while realizing heat accumulation
It turns to thermal energy and stores, optical and thermal transformation efficiency is 86.6-91.0%.Chinese invention patent 201610437361.1 discloses use
Only there is heat storage function in the phase-changing energy storage material of solar energy heat-storage, thermal energy can not be converted solar energy into.
The phase transition temperature of phase-change material prepared by the present invention is 57 DEG C or so, this temperature is slightly above the temperature of domestic hot water
Degree.When hot water is needed, the heat exchange between phase-change material and cold water is opened to prepare hot water, without big insulated water tank
To store heat.
Above embodiments are not intended to limit the invention, done within the spirit and principles of the present invention any to repair
Change, equivalent replacement and improvement etc., should all be included in the scope of protection of the claims of the present invention.
Claims (8)
1. the preparation method of the high thermal conductivity optical and thermal conversion composite phase-change heat-storage material for solar water heater, it is characterised in that
It comprises the steps of:
1) sodium acetate trihydrate and nucleating agent are mixed, is heated to 60-80 DEG C and keeps the temperature 1-3h；Expanded graphite is added, stirs evenly,
Obtain uniform sodium acetate trihydrate/expanded graphite mixture；
2) under the conditions of temperature is 60-80 DEG C, nanometer photo-thermal converting material is added while stirring, continues to stir 2-4h, be cooled to
After room temperature, it is 0.5-2g/cm that the mixing material after stirring, which is pressed into density,3Bulk, obtain high thermal conductivity optical and thermal conversion it is compound
Phase-change heat-storage material；
In terms of mass fraction, raw material components composition are as follows:
Sodium acetate trihydrate: 65-80%
Nucleating agent: 0.3-5%
Expanded graphite: 10-30%
Nanometer photo-thermal converting material: 5-10%.
2. the high thermal conductivity optical and thermal conversion composite phase-change heat-storage material according to claim 1 for solar water heater
Preparation method, which is characterized in that the nucleating agent is aluminium nitride, disodium hydrogen phosphate, Nano silver grain, two water sodium bromides and nothing
One of water sodium acetate is a variety of.
3. the high thermal conductivity optical and thermal conversion composite phase-change heat-storage material according to claim 1 for solar water heater
Preparation method, which is characterized in that the nanometer photo-thermal converting material is CuS, Cu2S、CuSe、Bi2S3、TiS2, carbon nanometer
One of pipe, nano graphite powder and nano carbon black are a variety of.
4. the high thermal conductivity optical and thermal conversion composite phase-change heat-storage material according to claim 1 for solar water heater
Preparation method, which is characterized in that stirring described in step 1) and step 2) is all mechanical stirring.
5. the high thermal conductivity optical and thermal conversion composite phase-change heat-storage material according to claim 4 for solar water heater
Preparation method, which is characterized in that the churned mechanically time is 1-2h.
6. the high thermal conductivity optical and thermal conversion composite phase-change heat-storage material according to claim 4 for solar water heater
Preparation method, which is characterized in that the churned mechanically speed is 100-600r/min.
7. the high thermal conductivity optical and thermal conversion composite phase-change heat-storage material according to claim 1 for solar water heater
Preparation method, which is characterized in that the mixing material density is 1-1.5g/cm after compacting3。
8. a kind of high thermal conductivity optical and thermal for solar water heater converts composite phase-change heat-storage material, which is characterized in that it is by weighing
Benefit requires the described in any item preparation methods of 1-7 to be made；The phase transition temperature of composite phase-change heat-storage material is 55-58 DEG C, and phase transformation is latent
Heat is 176.7-216J/g, and thermal coefficient is 2.27-3.52W/ (mK), and less than 4 DEG C, optical and thermal transformation efficiency is degree of supercooling
86.6-91.0%.
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| CN109705816A (en) * | 2019-02-18 | 2019-05-03 | 西南交通大学 | Multifunction flexible phase-change material, preparation method and construction material |
| CN109735310A (en) * | 2019-01-16 | 2019-05-10 | 南京航空航天大学 | A kind of full spectrum light hot-cast socket heat accumulating and preparation method thereof |
| CN110591654A (en) * | 2019-09-29 | 2019-12-20 | 新奥石墨烯技术有限公司 | Phase-change heat storage composite material and preparation method thereof |
| US10914293B2 (en) | 2018-06-20 | 2021-02-09 | David Alan McBay | Method, system and apparatus for extracting heat energy from geothermal briny fluid |
| CN112968657A (en) * | 2021-02-05 | 2021-06-15 | 浙江工商大学 | Photo-thermal coupling system and application |
| CN113429941A (en) * | 2021-07-14 | 2021-09-24 | 东南大学 | Composite phase-change material and preparation method thereof |
| CN113621349A (en) * | 2021-08-17 | 2021-11-09 | 广东工业大学 | Phase-change gel for sunlight photo-thermal conversion and preparation method thereof |
| CN114656939A (en) * | 2022-05-10 | 2022-06-24 | 华南理工大学 | Expanded graphite-based composite phase-change material with anisotropic thermal conductivity and preparation method thereof |
| CN114763465A (en) * | 2021-01-14 | 2022-07-19 | 国电南瑞科技股份有限公司 | Phase-change heat storage material composite nucleating agent and preparation method thereof |
| CN115287043A (en) * | 2021-01-21 | 2022-11-04 | 青岛大学 | Composite phase-change heat storage material with sludge hydropyrolysis residue as carrier and preparation method thereof |
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| US11692530B2 (en) | 2018-06-20 | 2023-07-04 | David Alan McBay | Method, system and apparatus for extracting heat energy from geothermal briny fluid |
| US10914293B2 (en) | 2018-06-20 | 2021-02-09 | David Alan McBay | Method, system and apparatus for extracting heat energy from geothermal briny fluid |
| US11225951B2 (en) | 2018-06-20 | 2022-01-18 | David Alan McBay | Method, system and apparatus for extracting heat energy from geothermal briny fluid |
| CN109735310A (en) * | 2019-01-16 | 2019-05-10 | 南京航空航天大学 | A kind of full spectrum light hot-cast socket heat accumulating and preparation method thereof |
| CN109735310B (en) * | 2019-01-16 | 2021-04-16 | 南京航空航天大学 | Full-spectrum photo-thermal conversion heat storage material and preparation method thereof |
| CN109705816A (en) * | 2019-02-18 | 2019-05-03 | 西南交通大学 | Multifunction flexible phase-change material, preparation method and construction material |
| CN110591654A (en) * | 2019-09-29 | 2019-12-20 | 新奥石墨烯技术有限公司 | Phase-change heat storage composite material and preparation method thereof |
| CN114763465B (en) * | 2021-01-14 | 2024-02-13 | 国电南瑞科技股份有限公司 | Phase-change heat storage material composite nucleating agent and preparation method thereof |
| CN114763465A (en) * | 2021-01-14 | 2022-07-19 | 国电南瑞科技股份有限公司 | Phase-change heat storage material composite nucleating agent and preparation method thereof |
| CN115287043B (en) * | 2021-01-21 | 2023-12-05 | 青岛大学 | Composite phase-change heat storage material taking sludge water pyrolysis residues as carriers and preparation method thereof |
| CN115287043A (en) * | 2021-01-21 | 2022-11-04 | 青岛大学 | Composite phase-change heat storage material with sludge hydropyrolysis residue as carrier and preparation method thereof |
| CN112968657A (en) * | 2021-02-05 | 2021-06-15 | 浙江工商大学 | Photo-thermal coupling system and application |
| CN113429941A (en) * | 2021-07-14 | 2021-09-24 | 东南大学 | Composite phase-change material and preparation method thereof |
| CN113621349A (en) * | 2021-08-17 | 2021-11-09 | 广东工业大学 | Phase-change gel for sunlight photo-thermal conversion and preparation method thereof |
| CN114656939A (en) * | 2022-05-10 | 2022-06-24 | 华南理工大学 | Expanded graphite-based composite phase-change material with anisotropic thermal conductivity and preparation method thereof |
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