CN106281256A - Energy storage material modifying agent, its preparation method and application thereof - Google Patents
Energy storage material modifying agent, its preparation method and application thereof Download PDFInfo
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- CN106281256A CN106281256A CN201610617441.5A CN201610617441A CN106281256A CN 106281256 A CN106281256 A CN 106281256A CN 201610617441 A CN201610617441 A CN 201610617441A CN 106281256 A CN106281256 A CN 106281256A
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Abstract
The open a kind of energy storage material modifying agent of the present invention, material material modified by conduction of heat, expansion coefficient modifying, organic binding material, fibrous material, reinforcing material and water are formed, and the most each component is: conduction of heat is material modified includes the graphite and the metallic oxide crystal whisker of 0.5～15 part and/or metal nitride whisker that weight content is 1～10 part；Expansion coefficient modifying material includes the rare earth oxide of 1～8 part；The organic binding material being made up of the polypropylene of the polyethylene of 0.005～2 part and 0.005～3 part；Fibrous material includes the polyethylene fiber peacekeeping 0.005 of 0.005～2 part～3 parts of polypropylene fibres；The reinforcing material of 0.2～5 part；The water of 70～90 parts.Invention additionally discloses the preparation method and applications of this energy storage material modifying agent.Use energy storage module made by the modifier energy storage material of the present invention, have low cost, unit stored energy capacitance is big, energy storage temperature is high, the high premium properties with length in service life of energy grade, is more conducive to advance the popularization and application across memory technology in season of solar energy.
Description
Technical field
The present embodiments relate to solar energy storage technical field, particularly relate to a kind of energy storage material modifying agent, it prepares
Method and application thereof.
Background technology
Heat energy is one of principal mode of storage of solar energy, wideling popularize and applying along with heliotechnics, solar energy
Across season storing energy and supplying hot be increasingly becoming a hot issue of current utilization of new energy resources.The most common cross-season heat-storage is main
It is to use phase-change heat storage technology, i.e. utilizes Cucumber heat absorption in reversible reaction and exothermic process to reach the storage of heat energy
And extraction, there is storage density height, fill the advantages such as heat release temperature stabilization.So that phase-transition heat-storage is adjusted at electrical network daily load
The aspects such as joint, the air regulation of building, Solar use, industrial afterheat recovery have broad application prospects.
But phase-change thermal storage technology still has weak point, mainly shows themselves in that
One, the chemical stability of phase-change material is poor, and heat accumulation temperature is protected from environmental bigger；
Its two, all there is surfusion in various degree in many hydrated salts that in phase-change material, latent heat is bigger；
Its three, the heat conductivility of phase-change material is poor, is unfavorable for the release of energy storage heat；
Its four, owing to the heat storage capacity of phase-change material is big not, therefore have to use the energy storage module that volume is bigger to obtain
Take considerable storage energy；
Its five, during phase-change material phase transformation, it may occur that expand and cause the energy storage module made by phase-change material
There is non-reversible deformation, reduce the service life of energy storage module；
Its six, the cost of phase-change material is of a relatively high, is unfavorable for that what corresponding solar cross-season energy storage module applied pushes away
Extensively.
Technical problem is that what the present inventor was found in the practice of the invention it should be noted that, above.
Summary of the invention
It is an object of the invention to provide a kind of energy storage material modifying agent, in order to solve at least one in the problems referred to above.
Further object is that the preparation method providing above-mentioned energy storage material modifying agent.
A further object of the present invention there are provided the application of above-mentioned energy storage material modifying agent.
According to an aspect of the present invention, it is provided that a kind of energy storage material modifying agent, this energy storage material modifying agent is by conduction of heat
Material material modified, expansion coefficient modifying, organic binding material, fibrous material, reinforcing material and water are formed,
The most each component is:
Parts by weight of raw materials
(1) conduction of heat is material modified, and this conduction of heat is material modified to be included:
Graphite 1～10 parts
Metallic compound whisker 0.5～15 parts
(2) expansion coefficient modifying material, this expansion coefficient modifying material includes:
Rare earth oxide 1～8 parts
(3) organic binding material:
Polyethylene 0.005～2 parts
Polypropylene 0.005～3 parts
(4) fibrous material, this fibrous material includes:
Polyethylene fibre 0.005～2 parts
Polypropylene fibre 0.005～3 parts
(5) reinforcing material 0.2～5 parts
(6) water 70～90 parts.
Wherein, conduction of heat is material modified includes graphite and metallic oxide crystal whisker and/or metal nitride whisker, graphite
Accounting for the 1%～10% of energy storage material modifying agent gross weight, metallic compound whisker accounts for the 0.5% of energy storage material modifying agent gross weight
～15%；Expansion coefficient modifying material includes rare earth oxide, and rare earth oxide accounts for the 1% of energy storage material modifying agent gross weight
～8%,；Fibrous material includes polyethylene fiber peacekeeping polypropylene fibre, and polyethylene fibre accounts for energy storage material modifying agent gross weight
0.005%～2%, polypropylene fibre accounts for the 0.005%～3% of energy storage material modifying agent gross weight；Organic binding material by
Polyethylene and polypropylene are formed, and polyethylene accounts for the 0.005%～2% of energy storage material modifying agent gross weight, and polypropylene accounts for energy storage
The 0.005%～3% of material modification agent gross weight；Reinforcing material accounts for the 0.2%～2% of energy storage material modifying agent gross weight；Water
Account for the 70%～90% of energy storage material modifying agent gross weight.
In some specific embodiments, above-mentioned graphite be weight content be the flake graphite of 1～5 part and 1～5 part
Graphene microchip；Above-mentioned rare earth oxide is the cerium oxide of 0.5～3 part, the lanthana of 0.5～3 part and the oxidation of 0.1～2 part
Zirconium；Above-mentioned metallic compound whisker is metallic oxide crystal whisker and/or metal nitride whisker；Above-mentioned reinforcing agent is steel fibre.
In some specific embodiments, the material modified weight content that also includes of above-mentioned conduction of heat is 0.1～5 part
CNT.
In some specific embodiments, above-mentioned metallic compound whisker selected from magnesia crystal whisker, alumina whisker and
One or more in aluminium nitride whisker.
In some specific embodiments, above-mentioned expansion coefficient modifying material also includes aluminium nitride, magnesium oxide and oxygen
Change one or more in aluminum.
In some specific embodiments, above-mentioned fibrous material also include nylon fiber, lignin staple fibre and
One or more in natural plant fibre.
Energy storage material modifying agent provided by the present invention has the advantages that
(1) this energy storage material modifying agent has selected the graphite of respective components content and metallic oxide crystal whisker and/or metal
Nitride whisker is material modified as conduction of heat, uses this modifying agent that energy storage material to be modified can be made to have excellent heat conductivity
Energy.
(2) selected the rare earth oxide expansion coefficient modifying material as this modifying agent of respective components content, can adjust
Save the crystal lattice difference between different component in energy storage material to be modified, increase the coefficient of expansion of this energy storage material, and make this
Energy storage material has excellent toughness, compared to phase-changing energy storage material of the prior art, service life can be substantially improved.
The energy storage material modifying agent of the present invention is suitable to add to compound crystal energy storage material (such as, concrete), and can
This compound crystal energy storage material being added with this energy storage material modifying agent is made energy storage module, so that the storage after modification
Can have the advantages that by the energy storage module made by material
1. relative to molten salt energy-storage material of the prior art and phase-changing energy storage material, energy storage become instinct reduce by 90% with
On.
2. there is the highest unit stored energy capacitance, this energy storage material under comparing using water as energy-accumulating medium, same volume
Stored energy capacitance is more than 20～30 times of water stored energy capacitance.
3. there is the highest unit stored energy capacitance；In one case, store an equal amount of heat energy, make compared to water
For energy-accumulating medium, the volume taken required for this energy storage module is about the 1/10 of water, can effectively reduce energy storage facility
Facility cost and cost of floor space.
4. there is energy storage temperature high, the premium properties that energy grade is high；Specifically, energy storage and energy supply temperature can reach
350 DEG C, most industry can be met and produce the temperature requirement to heat energy.
According to a further aspect in the invention, the preparation method of above-mentioned energy storage material modifying agent is additionally provided, including following step
Rapid:
The first step, weighs each raw material according to said ratio: conduction of heat material material modified, expansion coefficient modifying, organic viscous
Knot material, fibrous material, reinforcing material and water；
Second step, puts into agitated kettle, stirring at low speed 2min, then 60～120r/min stirring at a high speed by the raw material weighed
2min, then stands.Thus, by the preparation method of this energy storage material modifying agent, obtained energy storage material can be made modified
The energy storage of agent is better.
According to another aspect of the invention, above-mentioned energy storage material modifying agent is additionally provided at solar cross-season energy storage module
On application, this solar cross-season energy storage module mixed by above-mentioned energy storage material modifying agent and composite crystal energy storage material and
Become.Thus, can realize solar energy across season high efficiency store.
The present invention also has more beneficial effect, illustrates hereinafter in conjunction with detailed description of the invention.
Accompanying drawing explanation
In order to be illustrated more clearly that the specific embodiment of the invention or technical scheme of the prior art, below will be to specifically
In embodiment or description of the prior art, the required accompanying drawing used is briefly described, it should be apparent that, in describing below
Accompanying drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not paying creative work
Put, it is also possible to obtain other accompanying drawing according to these accompanying drawings.
Fig. 1 is illustrated that the structural representation of the heat test device for heat amount test of the present invention experiment.
Reference:
10 heat test device 102 heat pipes
101 container 103 calorimeters
1011 vessel ports.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be further described in detail.
Table 1 lists component and the weight ratio of the embodiment of the present invention 1～8:
(table 1)
Energy storage material modifying agent made by the present invention be a kind of be suitable to new modified be combined that mixed crystal material mixes mutually
Reagent, so that relatively low cost can only be consumed just be capable of the long-time storage of energy.At this energy storage material modifying agent
Actual application during, can according to demand various for this energy storage material modifier compound mixed crystal materials be fabricated to not
Solar energy accumulation module with type, it is adaptable to for the every field energy storage heat supply such as commercial production, daily life, additionally it is possible to meet
The demand that heat stored across season.
In order to the effect making the present invention is more convincing, carrying out following controlled trial, wherein experimental group selects concrete to make
For composite energy storage crystalline material, and by corresponding logging in table 2:
Experimental group:
Each raw material is weighed according to the proportioning of table 1.
Selected raw material is put into agitated kettle, stirring at low speed 2min, and then agitated kettle is 60～120r/min to stir at a high speed
Mix 2min, then stand；It is derived from the energy storage material modifying agent of the present invention；
Adding appropriate concrete material, same stirring at low speed 2min in this agitated kettle, then agitated kettle is with at a high speed 60
～120r/min stirs 2min, then stand drying；
Wherein, this concrete material is the composite crystal mixture of Portland cement, basalt, fluvial sand, adds extremely
The total weight parts of the concrete material of agitated kettle should be 6～9 times of energy storage material modifying agent weight portion；
The component Portland cement of this concrete material should select the Portland cement of more than 25 labels, preferably
Can be selected for 42.5R ordinary cement to ensure more preferably effect.What deserves to be explained is, serve as expansion coefficient modifying dose aluminium nitride,
Magnesium oxide and aluminium oxide the most also have thermal conduction characteristic, therefore the interpolation of aluminium nitride, magnesium oxide and aluminium oxide also can be to a certain degree
The heat conductivility of upper increase energy storage material to be modified.
After completion of the reaction, stop stirring, obtain being mixed institute with concrete material by the energy storage material modifying agent of the present invention
The mixture obtained；
It should be noted that, the addition of each fibrous material in table 1 is for so that adding to coagulation at fibrous material
Time in soil, aqueous vapor is provided to discharge when merging for concrete and this energy storage material modifying agent and the passage of pressure release, and can be
The intensity at the mixture initial stage that raising concrete and energy storage material modifying agent mix to a certain extent.
Obtained by utilizing the heat test device 10 shown in Fig. 1 that this energy storage material modifying agent is mixed with concrete material
The thermal storage performance of mixture is tested:
This mixture is directed into by vessel port 1011 appearance of the square shape that receiving volume size is 1 cubic metre
In device 101, to fill up this container, and close vessel port 1011；This container 101 runs through one or more heat pipe 102, by
This can get one has fixed volume, runs through the accumulation of energy mould having one or more heat pipe 102 and being made up of this mixture
Block.It is understood that the outer surface of this container 101 scribbles adiabator layer to prevent the loss of heat, to ensure experiment number
According to reliability.
In above-mentioned heat pipe, circulation one has the high temperature heat conducting medium of 350～400 DEG C, it is to be appreciated that this heat conduction is situated between
Matter can be the mixture of biphenyl and Biphenyl Ether.
Treat that heat-conducting medium circulates a period of time in heat pipe, so that heat-conducting medium is by heat pipe and container 101
Energy storage module heat conduction abundant；
Above-mentioned heat conduction fully refers to that the duration that this high temperature heat conducting medium is circulated is enough saturated to allow this energy storage module absorb heat,
The duration that concrete high temperature heat conducting medium is circulated should be with the volume size of this shaper and heat pipe in energy storage module
It is distributed relevant.
Test maximum energy storage temperature T of current energy storage module, and by the value record of T in table 2.
In heat test device 10, the two ends of heat pipe 102 are connected and installed with calorimeter 103；From time t1Start past
With uninterrupted 0.1m in this heat pipe3/ s turns on water, thus can determine the water yield through this energy storage module by this calorimeter
And the heat conduction temperature difference, and by the maximum record of the heat conduction temperature difference in table 2；
When the heat conduction temperature difference is zero, determine that this time point is t2, according to t1And t2Difference determine that energy storage module persistently supplies
The time of heat, and by the value record of lasting heat supply duration in table 2, may determine that t by calorimeter1To t2Storage in container 101
Energy heat sum Q acquired in moduleAlways, by QAlwaysIt is defined as the stored energy capacitance Q of energy storage module, and is recorded in table 2.
Matched group:
Water and the different types of phase-change material of paraffin both is selected to carry out with reference to right with experimental group as a control group respectively
Than experiment, and corresponding experimental result is recorded in table 2 equally:
In container 101, fill up water by vessel port 1011, and close vessel port 1011；It is understood that water
Initial temperature with experimental group the initial temperature of each energy storage module essentially identical, all should be room temperature.
Circulation one high temperature heat conducting medium identical with experimental group in heat conductive pipes 102.
Treat that heat-conducting medium passes through heat pipe 102 abundant with water heat conduction, maximum energy storage temperature T of water in test current container,
And by the value record of T in table 2.
From time t1' start in heat pipe 102 with uninterrupted 0.1m3/ s turns on water, thus can be by this calorimeter
103 determine the water yield through heat pipe 102 and the heat conduction temperature difference, and by the maximum record of the heat conduction temperature difference in table 2.
When the heat conduction temperature difference is zero, determine that this time point is t2', according to t1' and t2' difference determine that reference container is held
The time of continuous heat supply, and by the value record of this lasting heat supply duration in table 2, may determine that t by calorimeter1To t2Container 101
The interior heat sum Q acquired in waterAlways', by QAlways' it is defined as the stored energy capacitance Q of water, and be recorded in table 2.
In like manner, container 101 is inserted paraffin, and uses identical method of testing to test, and will test accordingly
Result is inserted in table 2.
Table 2 (constituent content of embodiment 1～8 can refer to table one, therefore is not repeated here)
From above-mentioned data, the energy storage material modifying agent of the present invention mixture obtained by mixing with concrete material
The highest energy storage temperature range for can reach 350 DEG C, adapt to most industrial temperature requirements, compared to existing skill
Phase-change material in art, has the wider array of suitability.When in utilization life, modal phase-change material water is as energy storage material, water
Unit stored energy capacitance be 189MJ/m3；When utilizing the high-performance phase-change material with paraffin as representative, the unit energy storage of paraffin is held
Amount is 154MJ/m3；And the mixture obtained by utilizing the energy storage material modifying agent of the present invention to mix with concrete material carries out energy
During amount storage, the unit stored energy capacitance of mixture obtained by energy storage material modifying agent mixes with concrete material can reach 3GJ/
m3.Can be known by above-mentioned experimental data, all solid state energy storage module utilizing this energy storage mixture to be constituted carries out energy
Storage, compared with phase-change material of the prior art, has in terms of stored energy capacitance and is greatly improved.This mixture can also be applied
On solar cross-season energy storage module, can be guaranteed under the cost of relatively low energy-storage thermal-insulating, it is achieved depositing across season of solar energy
Storage.
The energy storage density of the mixture obtained by mixing with concrete material due to the energy storage material modifying agent of the present invention
Improve so that under the demand of equal stored energy capacitance, by the body of the energy storage module made by the energy storage material modifying agent of the present invention
Long-pending accounting is little, and the surface area of this energy storage module also will be greatly reduced accordingly.It is understood that the exchange of heat is mainly logical
Cross what the surface of object was carried out, due to the minimizing of surface area, corresponding also reduced by energy storage module surface dispersed heat, store
The temperature retention time of energy module greatly extends..
The energy storage material modifying agent of the present invention is applied on solar cross-season energy storage module so that at equal heat preservation strip
The energy storage module energy made by mixture under part, the energy storage material modifying agent of the present invention obtained by mixing with concrete material
Insulation duration is extended to the several months, it is achieved storing across season of solar energy.
More than conceiving is only one embodiment of the present invention.For the person of ordinary skill of the art, do not taking off
On the premise of the invention is conceived, it is also possible to make some deformation and improvement, such as, this energy storage material modifying agent is added
Energy storage mixture obtained in other materials to be modified in addition to concrete, all should belong to protection scope of the present invention.
Claims (8)
1. an energy storage material modifying agent, it is characterised in that described energy storage material modifying agent is material modified by conduction of heat, expand system
Number material modified, organic binding material, fibrous material, reinforcing material and water are formed,
The most each component is:
Parts by weight of raw materials
(1) conduction of heat is material modified, and described conduction of heat is material modified to be included:
Graphite 1～10 parts
Metallic compound whisker 0.5～15 parts
(2) expansion coefficient modifying material, described expansion coefficient modifying material includes:
Rare earth oxide 1～8 parts
(3) organic binding material:
Polyethylene 0.005～2 parts
Polypropylene 0.005～3 parts
(4) fibrous material, described fibrous material includes:
Energy storage material modifying agent the most according to claim 1, it is characterised in that:
Described graphite be weight content be the flake graphite of 1～5 part and the graphene microchip of 1～5 part；
Described rare earth oxide is the cerium oxide of 0.5～3 part, the lanthana of 0.5～3 part and the zirconium oxide of 0.1～2 part；
Described metallic compound whisker is metallic oxide crystal whisker and/or metal nitride whisker；
Described reinforcing agent is steel fibre.
Energy storage material modifying agent the most according to claim 1 and 2, it is characterised in that:
Described conduction of heat is material modified also includes the CNT that weight content is 0.1～5 part.
Energy storage material modifying agent the most according to claim 1 and 2, it is characterised in that:
One or more in magnesia crystal whisker, alumina whisker and aluminium nitride whisker of described metallic compound whisker.
Energy storage material modifying agent the most according to claim 1 and 2, it is characterised in that:
Described expansion coefficient modifying material also includes one or more in aluminium nitride, magnesium oxide and aluminium oxide.
Energy storage material modifying agent the most according to claim 1 and 2, it is characterised in that:
Described fibrous material also includes one or more in nylon fiber, lignin staple fibre and natural plant fibre.
7. the preparation method of an energy storage material modifying agent as claimed in claim 1, it is characterised in that including:
The first step, weighs each raw material according to proportioning: conduction of heat material material modified, expansion coefficient modifying, organic binding material, fibre
Dimension material, reinforcing material and water；
Second step, puts into agitated kettle, stirring at low speed 2min, then 60～120r/min stirring at a high speed by the raw material weighed
2min, then stands.
8. the application on solar cross-season energy storage module of the energy storage material modifying agent described in claim 7, described solar energy
Across season energy storage module mixed by described energy storage material modifying agent and composite crystal energy storage material.
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| CN201610617441.5A CN106281256A (en) | 2016-07-29 | 2016-07-29 | Energy storage material modifying agent, its preparation method and application thereof |
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| CN201610617441.5A CN106281256A (en) | 2016-07-29 | 2016-07-29 | Energy storage material modifying agent, its preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109777373A (en) * | 2019-03-06 | 2019-05-21 | 北京理工大学 | Across the season heat accumulating of medium temperature |
| CN110791257A (en) * | 2019-10-08 | 2020-02-14 | 鞍钢股份有限公司 | Preparation method and device of directional heat transfer phase change heat storage material |
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| CN101024763A (en) * | 2006-02-21 | 2007-08-29 | 高原 | Heat-exchanging material |
| US8465864B1 (en) * | 2012-02-07 | 2013-06-18 | Hyundai Motor Company | Heat dissipation plate for battery cell module and battery cell module having the same |
| CN104364900A (en) * | 2012-04-17 | 2015-02-18 | 莫门蒂夫性能材料股份有限公司 | Thermally conductive polymer compostions to reduce molding cycle time |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101024763A (en) * | 2006-02-21 | 2007-08-29 | 高原 | Heat-exchanging material |
| US8465864B1 (en) * | 2012-02-07 | 2013-06-18 | Hyundai Motor Company | Heat dissipation plate for battery cell module and battery cell module having the same |
| CN104364900A (en) * | 2012-04-17 | 2015-02-18 | 莫门蒂夫性能材料股份有限公司 | Thermally conductive polymer compostions to reduce molding cycle time |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109777373A (en) * | 2019-03-06 | 2019-05-21 | 北京理工大学 | Across the season heat accumulating of medium temperature |
| CN109777373B (en) * | 2019-03-06 | 2021-01-26 | 北京理工大学 | Intermediate-temperature seasonal heat storage material |
| CN110791257A (en) * | 2019-10-08 | 2020-02-14 | 鞍钢股份有限公司 | Preparation method and device of directional heat transfer phase change heat storage material |
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