CN105441033B - A kind of ionic liquid-aqueous systems phase-changing energy storage material and preparation method thereof - Google Patents
A kind of ionic liquid-aqueous systems phase-changing energy storage material and preparation method thereof Download PDFInfo
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- CN105441033B CN105441033B CN201510861168.6A CN201510861168A CN105441033B CN 105441033 B CN105441033 B CN 105441033B CN 201510861168 A CN201510861168 A CN 201510861168A CN 105441033 B CN105441033 B CN 105441033B
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Abstract
The present invention provides a kind of ionic liquid-aqueous systems phase-changing energy storage material, including following component: ionic liquid and water；Wherein, the quality of the water accounts for the ionic liquid-aqueous systems phase-changing energy storage material gross mass mass percent no more than 20%；The ionic liquid is met water and is not chemically reacted.The present invention also provides this ionic liquid-aqueous systems phase-changing energy storage material preparation methods.Ionic liquid of the invention-aqueous systems phase-changing energy storage material thermal coefficient with higher and enthalpy of phase change, and it is cheap, it is environmentally friendly.
Description
Technical field
The invention belongs to the applications of field of material synthesis technology, especially phase-changing energy storage material.
Background technique
Phase-changing energy storage material can get up temporary unused energy storage, be discharged again to when needing, this can delay
The contradiction between energy supply and demand is solved, it is energy saving.Using this characteristic of phase-changing energy storage material, air-conditioning section can be used in
Energy field, field of solar energy, aerospace field and electric power etc..Due to single phase-change material property in use
Can be unstable, it can not meet the requirement of practical application, the improvement to phase-change material, and in terms of composite phase-change energy storage material
Research at research emphasis in recent years.
Energy storage material is broadly divided into the way of energy storage: sensible heat energy storage, chemical reaction energy storage and hidden heat energy storage three categories.
Sensible heat energy storage is that thermal energy is stored by the temperature change of substance, and heat-storage medium must have biggish specific heat capacity.Sensible heat storage
Although fairly simple convenience, the temperature of its material itself are constantly changing energy material in use, it is unable to reach control temperature
The purpose of degree, and such material energy storage density is low, to keep corresponding device volume huge, therefore its application value is not high.
Hidden heat energy storage be using phase-change material in phase transformation neither endothermic nor exothermic come energy storage or release can, this energy storage mode
The energy density that not only stores is high, and equipment therefor is simple, small in size, flexible design, easy to use and be easily managed.Also
Have the advantages that one very big: i.e. this kind of material material proximate constant temperature during phase-change accumulation energy, therefore most before practical application
Scape, and at present using most and most important energy storage mode.Phase-change material is in field of solar energy, heat-storage and cold-storage field, air-conditioning
There is tempting prospect in building field and aerospace field.
Phase change energy storage technology is to absorb or discharge a large amount of thermal energy during phase transformation using material, to play control
The effect of mild energy storage, can solve energy supply and demand and distributes unbalanced contradiction over time and space, be to improve using energy source
The effective means of efficiency.In aerospace, Solar use, industrial afterheat recovery, heating and air-conditioning, engineering in medicine, military work
The various fields such as journey, accumulation of heat building and extreme environment clothes have important application value and wide application prospect.
Phase-changing energy storage material generally can be divided into Inorganic phase change energy storage material, organic phase change energy storage material and composite phase-change storage
It can material.There are problem of phase separation, poor resistances for Inorganic phase change energy storage material, it is difficult to be recycled for a long time；Organic phase-change storage
Energy material is easily oxidised, and thermal stability is poor, and unit volume energy storage density is lower, poor thermal conductivity；Composite phase-change energy storage material
The shortcomings that single organic or inorganic phase-change material can partially be overcome, but inorganic material and organic material having in recombination process
Effect combines problem that solution is not yet received.
Ionic liquid has many advantages, such as that steam forces down, thermal stability is good, setting property is strong, is a kind of completely new phase-change accumulation energy
Material, compared with existing phase-changing energy storage material: 1. lower vapour pressure can be controlled in ionic liquid volatilization loss lower
Degree；2. good thermal stability adapts it to various harsh application environments；3. ionic liquid is in storage, heat release circulation
Remain identical solid-liquid composition, no phenomenon of phase separation.
Currently, the ionic liquids ionic liquids for being used as phase-changing energy storage material are expensive, reach 3000 yuan -5000 yuan/thousand
Gram, marketing application difficulty is very big.In addition, the problems such as generally existing viscosity of ionic liquid is big, heating conduction is bad, reduces
A possibility that its application.
Summary of the invention
In order to overcome the deficiencies of the prior art, the present invention provides a kind of ionic liquid-aqueous systems phase-changing energy storage material, comprising:
Ionic liquid and water；Wherein, the quality of the water accounts for the mass percent of the phase-changing energy storage material gross mass not
More than 20%；The ionic liquid is met water and is not chemically reacted.
Further, the ionic liquid is bromination 1- cetyl -3- methylimidazole, the bis- caprolactam butane of Isosorbide-5-Nitrae -
Any one in chloro salt, 1- ethyl-3-methylimidazole tetrafluoroborate.
Further, the mass ratio of the ionic liquid and water is 8~95:1~5.
It further, further include nucleating agent, the quality of the nucleating agent accounts for the quality of the phase-changing energy storage material gross mass
Percentage is not higher than 5%.
The present invention also provides this ionic liquid-aqueous systems phase-changing energy storage material preparation methods, include the following steps:
Ionic liquid and water are mixed to form the first mixture；Wherein, the quality of the water accounts for the phase-changing energy storage material
The mass percent of gross mass is no more than 20%；The ionic liquid is met water and is not chemically reacted；
First mixture is placed in reactor, controlled at being no more than 90 DEG C, adds first mixture
Heat fusing forms homogeneous and transparent first liquid；Cooling first liquid obtains the phase-changing energy storage material.
Further, the ionic liquid is bromination 1- cetyl -3- methylimidazole, the bis- caprolactam butane of Isosorbide-5-Nitrae -
Any one in chloro salt, 1- ethyl-3-methylimidazole tetrafluoroborate.
Further, the mass ratio of the ionic liquid and water is 8~95:1~5.
It further, further include nucleating agent, the quality of the nucleating agent accounts for the quality of the phase-changing energy storage material gross mass
Percentage is not higher than 5%
The utility model has the advantages that
Compared with existing ionic liquid-aqueous systems phase-changing energy storage material, ionic liquid of the invention-aqueous systems phase transformation
Energy storage material has the advantages that
1, ionic liquid-water mixed system phase-changing energy storage material can effectively reduce production cost, the phase transformation material of unit mass
Material production cost highest can reduce by 20%.
2, ionic liquid-water mixed system phase-changing energy storage material thermal conductivity is good.Common alkyl imidazole ionic liquid phase
Change energy-storage material thermal coefficient is generally below 0.35Wm-1·K-1, ionic liquid-water mixed system phase-change material thermal coefficient
Up to 0.50Wm-1·K-1。
Specific embodiment
In the following, will be described in detail to the embodiment of the present invention.
Step 1: prepare raw material.Raw material of the invention include:
1, ionic liquid, the ionic liquid of the invention ionic liquid insensitive to air and water, the i.e. ionic liquid connect
Stabilization is able to maintain when contacting air, moisture, reaction of not decomposing.For example, the ionic liquid is, for example, bromination 1- 16
Alkyl -3- methylimidazole ([C16mim] Br), the bis- caprolactam butane chloro salt of 1,4- ([DCB] Cl), 1- ethyl -3- methyl
Tetrafluoroborate ([EMIM] BF4) in any one.
2, water.That is distilled water, deionized water.Water is not dissolved in ionic liquid, and continuous phase is not present.Water with
Ionic liquid separation, forms discrete nanoscale aggregate.
3, nucleating agent can be selected from expanded graphite or metal nanoparticle.
For different ionic liquid bases, the nucleating agent of addition is determined after need to screening.The nucleating agent of addition needs
Ability with surface tension when reducing system liquid phase, and then nucleation and crystallization is made it easier to, the degree of supercooling of system is reduced, simultaneously
The energy storage density of phase-change material system is not caused to decline excessive, energy storage density, which reduces degree, in principle must not exceed system originally
The 10% of energy storage density.
Above-mentioned raw material are ready, then the estimated ionic liquid-aqueous systems phase-changing energy storage material gross mass that need to be prepared
Then M accounts for the mass percent of the gross mass M according to each raw material, calculate each raw material quality actually required
mx。
Implement in operation, the proportion relation of each raw material operates as follows:
Step 1: ionic liquid and water are mixed to form the first mixture；Wherein, the quality of the water accounts for the ion
Liquid-aqueous systems phase-changing energy storage material gross mass mass percent is no more than 20%；The ionic liquid is met water and is not changed
Learn reaction.
Preferably, the mass ratio of the ionic liquid and water is 8~95:1~5.
Step 2: first mixture is placed in reactor, control temperature from room temperature to 90 DEG C, constant temperature stirring or
1~2h is shaken, the first mixture heating melting is made to form homogeneous and transparent first liquid.Water is not dissolved in ionic liquid
Continuous phase is not present in body.So water is separated with ionic liquid in first liquid, discrete nanometer is formed
Grade aggregate.
First liquid described in natural cooling after first liquid crystalization solidification, is crushed to room temperature, obtain it is described from
Sub- liquid-aqueous systems phase-changing energy storage material, product are not necessarily to purifies and separates.
The method of the present invention is introduced below with reference to Examples 1 to 3.The response parameter and phase-change accumulation energy material of each embodiment
Expect parameter as shown in table 1, table 2.
The response parameter of each embodiment of table 1
Ionic liquid-aqueous systems phase-changing energy storage material physical parameter that each embodiment of table 2 obtains
Viscosity and be to reflect whether phase-changing energy storage material has the important indicator of application value with thermal conductivity, viscosity is got over
Low, thermal coefficient is higher, and application value is bigger, and the kinematic viscosity majority of existing ionic liquid phase-changing energy storage material exists
100mm2·s-1Left and right, partially up to hundreds of or even thousands of mm2·s-1, but thermal coefficient is generally below 0.35 Wm-1·K-1.As can be known from Table 2,1,2,3 product obtained its viscosity of embodiment is very low, but thermal coefficient is above 0.35 W
m-1·K-1, illustrate it with huge application prospect.
Phase-change material of the present invention is a kind of ionic liquid-water mixed system, mainly solves existing ionic liquid phase
The problem that change energy-storage material price is high, viscosity is big and heating conduction is poor.Such phase-change material only needs ionic liquid is uniform with water
Mixing, can effectively reduce the viscosity of ionic liquid phase-change material, improves its heating conduction, compare pure phase ionic liquid phase transformation material
Material, cost can at most reduce by 20%, while unit mass energy storage density can be improved to some extent.
Claims (4)
1. a kind of ionic liquid-aqueous systems phase-changing energy storage material characterized by comprising
Ionic liquid and water；Wherein, the quality of the water accounts for the ionic liquid-aqueous systems phase-changing energy storage material gross mass matter
It measures percentage and is no more than 20%；The mass ratio of the ionic liquid and water is 8:2 ~ 9:1；The ionic liquid is met water and is not changed
Learn reaction；The water is separated with the ionic liquid, forms discrete nanoscale aggregate；The ionic liquid is bromination
Any one in the bis- caprolactam butane chloro salt of 1- cetyl -3- methylimidazole, 1,4-.
2. ionic liquid-aqueous systems phase-changing energy storage material according to claim 1, which is characterized in that it further include nucleating agent, institute
The quality for stating nucleating agent accounts for the ionic liquid-aqueous systems phase-changing energy storage material gross mass mass percent not higher than 5%.
3. a kind of ionic liquid-aqueous systems phase-changing energy storage material preparation method, which comprises the steps of:
Ionic liquid and water are mixed to form the first mixture；Wherein, the quality of the water accounts for the ionic liquid-aqueous systems phase
The mass percent of change energy-storage material gross mass is no more than 20%；The mass ratio of the ionic liquid and water is 8:2 ~ 9:1；It is described
Ionic liquid is met water and is not chemically reacted；The ionic liquid be bromination 1- cetyl -3- methylimidazole, 1,4- it is bis- oneself
Any one in lactams butane chloro salt；
First mixture is placed in reactor, controlled at being no more than 90 DEG C, keeps the first mixture heating molten
Melt to form homogeneous and transparent first liquid；Cooling first liquid obtains the ionic liquid-aqueous systems phase-changing energy storage material.
4. ionic liquid-aqueous systems phase-changing energy storage material preparation method according to claim 3, which is characterized in that also wrap
Nucleating agent is included, the quality of the nucleating agent accounts for the ionic liquid-aqueous systems phase-changing energy storage material gross mass mass percent
Not higher than 5%.
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| CN107163917A (en) * | 2017-06-20 | 2017-09-15 | 大连理工大学 | Ionic liquid solution base nano-fluid directly absorbs solar airconditioning/heat pump method and apparatus |
| CN110017491A (en) * | 2018-01-09 | 2019-07-16 | 中国石油化工股份有限公司 | Catalysed oxidation processes based on ionic liquid phase-transition heat-storage |
| CN113174806B (en) * | 2020-05-22 | 2023-03-14 | 中国科学院青海盐湖研究所 | Road snow melting device and using method thereof |
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| CN101395128A (en) * | 2006-03-03 | 2009-03-25 | 考格尼斯知识产权管理有限责任公司 | Compounds that are liquid at ambient temperature |
| CN101805592A (en) * | 2010-04-20 | 2010-08-18 | 北京化工大学 | Ionic liquid base composite phase-change heat accumulation material and preparation method thereof |
| CN102443378A (en) * | 2011-11-02 | 2012-05-09 | 中山大学 | Hydrophilic ionic liquid/water cycle working fluid pair applicable to absorption refrigeration and heat pump system |
| CN103275675A (en) * | 2013-06-08 | 2013-09-04 | 山西潞安矿业(集团)有限责任公司 | Application of ionic liquid material serving as cross-seasonal phase change heat storage material |
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2015
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101395128A (en) * | 2006-03-03 | 2009-03-25 | 考格尼斯知识产权管理有限责任公司 | Compounds that are liquid at ambient temperature |
| CN101805592A (en) * | 2010-04-20 | 2010-08-18 | 北京化工大学 | Ionic liquid base composite phase-change heat accumulation material and preparation method thereof |
| CN102443378A (en) * | 2011-11-02 | 2012-05-09 | 中山大学 | Hydrophilic ionic liquid/water cycle working fluid pair applicable to absorption refrigeration and heat pump system |
| CN103275675A (en) * | 2013-06-08 | 2013-09-04 | 山西潞安矿业(集团)有限责任公司 | Application of ionic liquid material serving as cross-seasonal phase change heat storage material |
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| Thermochemistry of ionic liquid heat-transfer fluids;Michael E.Van Valkenburg等;《Thermochimica Acta》;20041215;第425卷;第181-188页 * |
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