CN110217774A - A kind of starch base hollow carbon micro-sphere material and preparation method thereof and heat accumulation application - Google Patents
A kind of starch base hollow carbon micro-sphere material and preparation method thereof and heat accumulation application Download PDFInfo
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Abstract
The present invention provides a kind of starch base hollow carbon micro-sphere material, using soluble starch as carbon source, the polystyrene of carboxyl-functional is template, after hydro-thermal reaction and high temperature cabonization, without activation process, can be obtained with hollow carbon microballoon pattern, specific surface area is 1300-1350 m2The carbon material of/g.Preparation method includes: 1) polystyrene/soluble starch complex microsphere preparation；2) preparation of the hollow carbosphere of starch base.Adsorbent support material as n-octadecane phase-change material, the phase transition temperature of gained composite phase-change material are 23.9-29.8 DEG C, and latent heat of phase change is 129.3-170.5 J/g.The present invention has following advantages: having the continuous hollow structure of height, is effectively prevented the leakage of phase-change material；Consistency is good, and repeatability is high；Preparation method is simple, is not necessarily to activation process；The features such as latent heat of phase change is high, and thermal stability is excellent, and have the characteristics that nontoxic, it is had a vast market foreground in fields such as building, energy storage materials.
Description
Technical field
The present invention relates to phase-changing energy storage material fields, and in particular to a kind of starch base hollow carbon micro-sphere material and its preparation side
Method and heat accumulation application.
Background technique
In recent years, being continuously increased with Fossil fuel consumption, thermal energy storage have obtained extensive concern, and are also demonstrate,proved
Bright is a kind of up-and-coming high efficiency of energy utilization technology.Phase-change material refers in certain temperature range, physical state or point
Minor structure occurs the heat of environment to can be absorbed, and go out heat to Environment release when needed, to reach control in transition process
The purpose of ambient temperature processed, therefore be considered as the good selection of energy storage.At the same time, phase-change material is in solar energy benefit
It is played an important role with, building energy conservation, Electron Heat management, waste heat recycling etc..
Phase-change material can be divided into solid-solid phase transition material, solid-liquid phase change material, solid-gas phase-change material according to phase transition process
With liquid-gas phase-change material.Solid-liquid phase change material is most study and most widely used a kind of material in phase-change material, main to wrap
Include crystalline hydrate salt, fused salt class, paraffin class, fatty acid etc., many kinds of, different properties.But either inorganic solid-liquid
Phase-change material or organic solid-liquid phase change material, liquid are lost the problem of always practical application to flow.
Common carbon material includes porous carbon, carbon nanotube, graphene, different carbon materials, due to its different shape and
Microstructure, the physics having and chemical property difference are huge.Wherein, porous carbon is due to suitable with high-specific surface area, heat of adsorption
In, the advantages that thermal conductivity is good, mechanical stability is high, and porous carbon materials preparation cost is cheap, simple process, is composite phase-change
The most common material in material support.Porous carbon utilizes the capillary action and surface tension of internal microcellular structure, by liquid
Phase-change material physical absorption in the duct of porous carbon materials, formed composite phase-change material.
The prior art of porous carbon materials, Chinese patent (application number 201610557581.8) provide a kind of 3D porous carbon
The preparation method of skeleton base composite phase-change material, raw material use organic ketone or aldehyde for carbon source, obtain the microscopic appearance of porous carbon.
The technology, as carbon source, has the advantages that raw material consistency, still, this method using common basal industrial chemicals organic ketone or aldehyde
Reaction raw materials there are problems that environmental pollution, and lead to the application scenarios of final products there are certain limitations.
Using biomass material as carbon source, can solve the above problem.Prior art China patent (application number
201810722827.1) provide a kind of preparation method of porous carbon-based hydrated inorganic salt composite phase-change material of high heat storage.It is former
Material, as carbon source, obtains the microscopic appearance of porous carbon using coconut husk, shell or other biological material.But the technology is deposited
In the FAQs of biological material --- not can guarantee the consistency of raw material to not can guarantee product pattern, performance it is consistent
Property；And this technology prepares carbon material and needs to be activated by nitric acid solution, and nitric acid solution has the skin and mucous membrane of human body
Strong stimulation and corrosiveness, equally exist the limited problem of environmental pollution and application scenarios.
Using starch as carbon source, above-mentioned technical problem can be effectively solved simultaneously --- have environmental-friendly spy
Point also has the characteristics of raw material consistency, and has significant advantage on cost of material, and analysis level soluble starch price is only
It is 45.89 yuan/500 g(http: //www.zhaoshiji.com/goods_18670.html).
The prior art for using starch to prepare porous carbon materials for carbon source has 2 pertinent literatures at present:
1, Bo Tan et al. (B. Tan, Z. Huang, Z. Yin, X. Min, Y.g. Liu, X. Wu, M. Fang,
Preparation and thermal properties of shape-stabilized composite phase change
materials based on polyethylene glycol and porous carbon prepared from
Potato, RSC Advances 6 (19) (2016) 15821-15830.) using fresh potato as carbon source, although obtaining
The microscopic appearance of porous carbon, but its specific surface area only has 42.6 m2/ g, and there are pore-size distributions that there is part in uneven, duct
The case where collapsing；
2, Fengyue Suo et al. (F. Suo, X. Liu, C. Li, M. Yuan, B. Zhang, J. Wang, Y.
Ma, Z. Lai, M. Ji, Mesoporous activated carbon from starch for superior rapid
121 (2019) 806-813. of pesticides removal, Int J Biol Macromol) using starch as carbon source, although
The microscopic appearance of porous carbon is also obtained, still, in order to improve the specific surface area of material, using the method for impregnating active to carbon
Material is handled, and carbon material surface pattern is caused seriously to be destroyed, and specific surface area also only increases to 160.6 m2/g；
Preceding solution, although consistency, safety and cheap cost can be taken into account to a certain degree, due to gained
Carbon material is open porous carbon structure, after physical absorption phase-change material, can not necessarily solve leakage from the root and ask
Topic.
Separately there are the prior art, Ouyang Haibo et al. (O. Haibo, L. Cuiyan, H. JianFeng, F.
Jie, Synthesis of carbon/carbon composites by hydrothermal carbonization
Using starch as carbon source, RSC Adv. 4 (24) (2014) 12586-12589.) using starch as carbon
Source, obtaining diameter is 10 micron-sized carbon fiber structurals.Because being equally the carbon fiber of open structure, can not solve
The above problem, but the technology shows that the carbon material of different-shape can be obtained by preparation method appropriate, to solve
Leakage problem.
In numerous carbon materials, the carbosphere with hollow structure, on the basis of having both porous carbon materials whole feature,
Also have the characteristics that height is continuous, therefore can effectively solve the leakage problem of above-mentioned phase-change material.
Prior art Wei Han et al. (W. Han, S. Dong, B. Li, L. Ge, Preparation of
polyacrylonitrile- based porous hollow carbon microspheres, Colloids and
520 (2017) 467-476. of Surfaces A:Physicochemical and Engineering Aspects) with poly-
Acrylonitrile emulsion is presoma, is prepared for polyphenyl by sequence of operations such as solidification, washing, supercritical drying, pre-oxidation, carbonizations
The hollow carbosphere of amido.Although the hollow carbosphere of the method preparation has certain application in terms of energy storage and absorption, should
The preparation method of technology is cumbersome, is not suitable for being mass produced；And it needs to use n,N dimethylformamide in preparation process,
It even burns with allergy, eczema easily occur after human contact, equally limits the application range of phase-change material.
Therefore, use is from a wealth of sources, cheap, and degradable, non-environmental-pollution starch is prepared into tool as carbon source
There is the hollow carbon micro-sphere structure of high-specific surface area, can effectively solve the above problems.
Summary of the invention
Goal of the invention of the invention is to form sediment for of the existing technology only with environmental-friendly, cheap solubility
Powder prepares open porous carbon structure, can not solve the leakage problem of phase-change material, and it is micro- to provide a kind of starch base hollow carbon
Ball material and preparation method thereof.
By hydro-thermal reaction and high temperature cabonization, it is not necessarily to activation process, it is micro- that the hollow carbon with high-specific surface area can be prepared
The simple and convenient process for preparing of ball obtains the excellent carbon material of absorption property；Then phase-change material is adsorbed again, to solve phase
Become the leakage problem of material.
In order to achieve the above-mentioned object of the invention, the technical solution adopted by the present invention are as follows:
A kind of starch base hollow carbon micro-sphere material, it is characterised in that: using soluble starch as carbon source, carboxyl-functional gathers
Styrene is template, and the polystyrene of carboxyl-functional and the mass ratio of soluble starch are 1:3, through hydro-thermal reaction and high temperature
After carbonization, it is not necessarily to activation process, the carbon material with hollow carbon microballoon pattern can be obtained.
Wherein, the specific surface area of gained starch base hollow carbon micro-sphere material is 1300-1350 m2/g。
A kind of preparation method of starch base hollow carbon micro-sphere material, it is characterised in that the following steps are included:
Step 1) polystyrene/soluble starch complex microsphere preparation, by the polystyrene of carboxyl-functional and soluble shallow lake
Powder is put into beaker after mixing, is carried out hydro-thermal reaction, is obtained polystyrene/soluble starch complex microsphere, further wash
It washs, dry；
The preparation of the hollow carbosphere of step 2 starch base, the polystyrene that step 1) is obtained/soluble starch complex microsphere into
The hollow carbosphere of starch base can be obtained in row high temperature cabonization.
Wherein, the polystyrene of the step 1) carboxyl-functional and the condition of soluble starch mixing are first 30 DEG C of perseverances
Temperature stirs 0.5-1 h, then ultrasound 0.5-2 h.
Wherein, the condition of the step 1) hydro-thermal reaction is, control hydrothermal temperature is 170-190 DEG C, and the time of hydro-thermal reaction is
10-15h。
Wherein, the condition of the step 2 high temperature carbonization is that heating rate is 1-5 DEG C/min, carburizing temperature 500-
600 DEG C, carbonization time is 12 h.
Heat accumulation application of the starch base hollow carbon micro-sphere material as absorption phase-change material, it is characterised in that including following step
It is rapid:
The hollow carbosphere of starch base and phase-change material are mixed, under certain condition using vacuum impregnation technology with certain adsorbance
It is adsorbed, the hollow carbosphere composite phase-change material of starch base can be obtained.
Wherein, the adsorbance is 50%-70%, and vacuum impregnation temperature is 50-70 DEG C, and the time is 12-24 h.
Wherein, the phase-change material is n-octadecane.
Heat accumulation application of the starch base hollow carbon micro-sphere material as phase-change material, it is characterised in that: starch base hollow carbon is micro-
The phase transition temperature of ball composite phase-change material is 23.9-29.8 DEG C, and latent heat of phase change is 129.3-170.5 J/g.
The laboratory test results of gained starch base hollow carbon micro-sphere material of the invention are as follows:
Through SEM test it is found that the sphere for the rough surface shape that starch base hollow carbon micro-sphere material of the present invention is evenly distributed, size
It is in the same size, there is not the phenomenon that collapsing or rupturing, partial size is between 3.47 μm -4.38 μm.
Through TEM test it is found that starch base hollow carbon micro-sphere material of the present invention is spherical hollow structure, outer shell thickness
About 130 nm.
It tests through FT-IR it is found that starch base hollow carbon micro-sphere material of the present invention has been successfully synthesized, it can be seen that carboxyl
The polystyrene of functionalization and the Partial Feature overlap of peaks of soluble starch, but the polystyrene of actually carboxyl-functional is
By carbonization；The characteristic peak of soluble starch remains substantially on hollow carbosphere obtained, but also has part solvable
Property starch characteristic peak disappear.
Through N2Adsorption-desorption test and BET are calculated it is found that the specific surface area of starch base hollow carbon micro-sphere material of the present invention is
1300-1350 m2/g.It is analyzed through BJH pore-size distribution it is found that the pore-size distribution of starch base hollow carbon micro-sphere material of the present invention exists
1.8-6.2 nm。
Starch base hollow carbon micro-sphere material of the present invention as absorption phase-change material heat accumulation in application, gained starch base is hollow
The laboratory test results of carbosphere composite phase-change material performance are as follows:
Through FT-IR test it is found that starch base hollow carbon micro-sphere material of the present invention has successfully adsorbed n-octadecane, starch base is formd
Hollow carbosphere composite phase-change material.
Through SEM test it is found that the hollow carbosphere composite phase-change material of starch base of the present invention to maintain starch base hollow carbon micro-
The spherical structure of ball material, material surface is coarse, almost the same with the particle diameter distribution of the hollow carbosphere of starch base.
Through DSC test it is found that the phase transition temperature of the hollow carbosphere composite phase-change material of starch base is 23.9-29.8 DEG C, phase
Change latent heat is 129.3-170.5 J/g, higher than the theoretical value 118.2-165.5 J/g of 50%-70% adsorbance.
Through 100 DSC loop tests it is found that the good thermal stability of the hollow carbosphere composite phase-change material of starch base.
Therefore, the present invention compared with the existing technology, has following advantages:
1, phase-change material is adsorbed by high successional hollow structure, the leakage of phase-change material can be effectively prevented；
2, it can guarantee the source consistency of carbon source as carbon source using soluble starch, the component of material is effectively guaranteed
It is identical, so that the pattern of the hollow carbosphere of the starch base prepared is consistent with performance, guarantee that present invention repeatability is high；
3, preparation method of the invention is simple, it is only necessary to which hydro-thermal reaction and high temperature cabonization are not necessarily to activation process, can obtain Gao Bibiao
The hollow carbosphere of starch base of area, high absorption property；
4, heat accumulation application of the hollow carbosphere of starch base that the present invention prepares as absorption phase-change material, gained starch base are hollow
Carbosphere composite phase-change material latent heat of phase change is high, and thermal stability is excellent.
In conclusion compared with prior art, the present invention not only low raw-material cost, preparation method are simple, it is only necessary to hydro-thermal
Reaction and high temperature cabonization are not necessarily to activation process；The hollow carbosphere specific surface area of the starch base of preparation is larger, and adsorption capacity is excellent,
The hollow carbosphere composite phase-change material of starch base possesses higher latent heat of phase change and excellent thermal stability, also can at the same time
Prevent leakage during solid-liquid phase change；Final products are nontoxic, have in fields such as building, energy storage materials wide
Market prospects.
Detailed description of the invention
Fig. 1 is the polystyrene of 1 carboxyl-functional of the embodiment of the present invention and soluble starch ratio is starch that 1:3 is obtained
The microsphere supported SEM spectrum of base hollow carbon；
Fig. 2 is the polystyrene of 1 carboxyl-functional of the embodiment of the present invention and soluble starch ratio is in starch base that 1:3 is obtained
The TEM map of empty carbosphere carrier；
Fig. 3 is the polystyrene of 1 carboxyl-functional of the embodiment of the present invention and soluble starch ratio is in starch base that 1:3 is obtained
The FT-IR map of empty carbosphere carrier；
Fig. 4 is the polystyrene of 1 carboxyl-functional of the embodiment of the present invention and soluble starch ratio is in starch base that 1:3 is obtained
The N of empty carbosphere carrier2Adsorption-desorption figure；
Fig. 5 is the polystyrene of 1 carboxyl-functional of the embodiment of the present invention and soluble starch ratio is in starch base that 1:3 is obtained
The graph of pore diameter distribution of empty carbosphere carrier；
Fig. 6 is the polystyrene of 1 carboxyl-functional of the embodiment of the present invention and soluble starch ratio is in starch base that 1:3 is obtained
The FT-IR map of empty 70% n-octadecane of carbosphere carrier adsorption；
Fig. 7 is the polystyrene of 1 carboxyl-functional of the embodiment of the present invention and soluble starch ratio is in starch base that 1:3 is obtained
The SEM spectrum of empty 70% n-octadecane of carbosphere carrier adsorption；
Fig. 8 is the polystyrene of 1 carboxyl-functional of the embodiment of the present invention and soluble starch ratio is in starch base that 1:3 is obtained
The DSC map of empty 70% n-octadecane of carbosphere carrier adsorption；
Fig. 9 is the polystyrene of 1 carboxyl-functional of the embodiment of the present invention and soluble starch ratio is in starch base that 1:3 is obtained
100 DSC of empty 70% n-octadecane of carbosphere carrier adsorption recycle map；
Figure 10 is the polystyrene of 1 carboxyl-functional of comparative example of the present invention and soluble starch ratio is starch base that 1:2 is obtained
The microsphere supported SEM spectrum of hollow carbon；
Figure 11 is the polystyrene of 2 carboxyl-functional of comparative example of the present invention and soluble starch ratio is starch base that 1:5 is obtained
The microsphere supported SEM spectrum of hollow carbon；
Figure 12 is the polystyrene of 1 carboxyl-functional of comparative example of the present invention and soluble starch ratio is hollow carbon that 1:2 is obtained
Microsphere supported N2Adsorption-desorption figure；
Figure 13 is the polystyrene of 1 carboxyl-functional of comparative example of the present invention and soluble starch ratio is hollow carbon that 1:2 is obtained
Microsphere supported graph of pore diameter distribution；
Figure 14 is the polystyrene of 2 carboxyl-functional of comparative example of the present invention and soluble starch ratio is hollow carbon that 1:5 is obtained
Microsphere supported N2Adsorption-desorption figure；
Figure 15 is the polystyrene of 2 carboxyl-functional of comparative example of the present invention and soluble starch ratio is hollow carbon that 1:5 is obtained
Microsphere supported graph of pore diameter distribution；
Figure 16 is the polystyrene of 3 carboxyl-functional of comparative example of the present invention and soluble starch ratio is starch base that 1:3 is obtained
The SEM spectrum of hollow carbon 80% n-octadecane of microsphere supported absorption；
Figure 17 is the polystyrene of 2 carboxyl-functional of the embodiment of the present invention and soluble starch ratio is starch base that 1:3 is obtained
The DSC map of hollow carbon 50% n-octadecane of microsphere supported absorption；
Figure 18 is the polystyrene of 3 carboxyl-functional of the embodiment of the present invention and soluble starch ratio is starch base that 1:3 is obtained
The DSC map of hollow carbon 60% n-octadecane of microsphere supported absorption.
Specific embodiment
The present invention is described in further detail the content of present invention in conjunction with Figure of description, but be not pair by embodiment
Limitation of the invention.
Embodiment 1
When the polystyrene and soluble starch ratio of a kind of carboxyl-functional are 1:3, the system of starch base hollow carbon micro-sphere material
Preparation Method:
The preparation of step 1) polystyrene/soluble starch complex microsphere,
The polystyrene of 1 g carboxyl-functional and 3 g soluble starches are mixed and are put into beaker, it is permanent in 35 DEG C of water-baths
Being put into temperature after temperature stirring 0.5 h, 1 h of ultrasound is 12 h of hydro-thermal reaction in 180 DEG C of high-temperature high-pressure reaction kettles, is obtained to after hydro-thermal
To product carry out suction filtration cleaning, be then placed in 60 DEG C of baking ovens, dry 24 h；
The preparation of step 2 starch base hollow carbon micro-sphere material,
Polystyrene/soluble starch complex microsphere that step 1) obtains is put into tube furnace, with the heating speed of 5 DEG C/min
Degree is warming up to 550 DEG C, and 12 h that are carbonized under the atmosphere of nitrogen.
In order to prove that the starch base hollow carbon micro-sphere material of this method preparation has spherical microscopic appearance, SEM has been carried out
Test.Test results are shown in figure 1, and the sphere for the rough surface shape that material of the present invention is evenly distributed, topographic profile is uniform, ruler
It is very little in the same size, there is not the phenomenon that collapsing or rupturing, partial size is between 3.47 μm -4.38 μm.
In order to prove that the starch base hollow carbon micro-sphere material of this method preparation has hollow structure, TEM test has been carried out.It surveys
Test result is as shown in Fig. 2, material of the present invention is spherical shape, and external darker, inside is more bright, shows material of the present invention in spherical shape
Hollow structure；Its outer shell thickness is about 130 nm.
In order to determine the structure of functional groups of starch base hollow carbon micro-sphere material, FT-IR test has been carried out.As a result such as Fig. 3 institute
Show, starch base hollow carbon micro-sphere material of the present invention has been successfully synthesized, it can be seen that the polystyrene of carboxyl-functional and can
The Partial Feature overlap of peaks of soluble starch, but the polystyrene of actually carboxyl-functional is by carbonization；Solubility is formed sediment
The characteristic peak of powder remains substantially on hollow carbosphere obtained, but also has the characteristic peak of part soluble starch to disappear.
In order to prove the specific surface area of starch base hollow carbon micro-sphere material, N is carried out to hollow carbosphere2Adsorption-desorption is surveyed
Examination and pore-size distribution analysis.As a result as shown in Figure 4 and Figure 5, the N of the hollow carbosphere of starch base2Adsorption-desorption curve belongs to IV type
Thermoisopleth can be calculated by BET and know, the specific surface area of the present embodiment starch base hollow carbon micro-sphere material is 1312 m2/ g, hole
Diameter is distributed in 1.8-6.2 nm.
When a kind of adsorbance is 70%, the preparation method of the hollow carbosphere composite phase-change material of starch base:
It takes hollow 1 g of carbosphere of starch base to be placed in vial, and the n-octadecane of 2.33 g is added, it then will be mixed
Sample is placed in vacuum oven, and using vacuum impregnation technology, starch has been made in 12 h of constant temperature under conditions of temperature is 60 DEG C
The hollow carbosphere composite phase-change material of base.
In order to prove that starch base hollow carbon micro-sphere material successfully adsorbs phase-change material, FT-IR test has been carried out.Test result
As shown in fig. 6, the infrared spectroscopy of the hollow carbosphere composite phase-change material of starch base is identical as the spectrum of n-octadecane, show starch
Base hollow carbon micro-sphere material successfully adsorbs n-octadecane, has synthesized the hollow carbosphere composite phase-change material of starch base.
In order to prove that the starch base hollow carbon micro-sphere material of this method preparation has spherical microscopic appearance, SEM has been carried out
Test.Test results are shown in figure 7, and the hollow carbosphere composite phase-change material of starch base maintains starch base hollow carbon micro-sphere material
Spherical structure, material surface is coarse, almost the same with the particle diameter distribution of the hollow carbosphere of starch base.
In order to prove the performance of the hollow carbosphere composite phase-change material of starch base, DSC test has been carried out.Test result is as schemed
Shown in 8, the melt temperature of the hollow carbosphere composite phase-change material of starch base is 29.8 DEG C, and crystallization temperature is 24.2 DEG C；Actual measurement
Latent heat of phase change is 170.5 J/g and 169.0 J/g, more than 165.5 J/g of theoretical value of 70% adsorbance.This phenomenon is in phase transformation
Material Field has correlative study, and reason is that phase-change material n-octadecane is uniformly distributed to the structure of hollow carbosphere
In, continuous heat conduction network is formd, so that n-octadecane changes its phase, therefore, adsorbance completely in phase transition process
Enthalpy when being 70% can be greater than the theoretical value of 70% adsorbance.Above-mentioned phenomenon also turns out hollow carbosphere of the invention as phase
Change composite material carrier has the characteristics that not available for general porous carbon materials.
In order to prove the thermal stability of the hollow carbosphere composite phase-change material of starch base in practical applications, 100 have been carried out
Secondary DSC loop test.Test results are shown in figure 9, after 100 thermal cycles, the hollow carbosphere composite phase-change material of starch base
The phase transition temperature and latent heat of phase change of material are basically unchanged, and good thermal circulation performance is shown in phase transition process, can be answered extensively
For heat accumulation field.
In order to study carboxyl-functional polystyrene and starch proportion to starch base hollow carbon micro-sphere material pattern, compare table
The influence of area and pore-size distribution, i.e. influence of the experiment component ratio to material property, control raw material components are identical, only change
Become the ratio between experimental group point, the hollow carbosphere of the starch base of the polystyrene and starch proportion that prepare different carboxyl-functionals
Material, i.e. comparative example 1 and comparative example 2.
Comparative example 1
When the polystyrene and soluble starch ratio of a kind of carboxyl-functional are 1:2, the system of starch base hollow carbon micro-sphere material
Preparation Method: not specified step is identical as 1 preparation method of above-described embodiment in specific steps, the difference is that: it is described
The polystyrene and soluble starch ratio of carboxyl-functional in step 1) are 1:2.
Comparative example 2
When the polystyrene and soluble starch ratio of a kind of carboxyl-functional are 1:5, the system of starch base hollow carbon micro-sphere material
Preparation Method: not specified step is identical as 1 preparation method of above-described embodiment in specific steps, the difference is that: it is described
The polystyrene and soluble starch ratio of carboxyl-functional in step 1) are 1:5.
In order to study carboxyl-functional polystyrene and starch proportion to the shadow of starch base hollow carbon micro-sphere material pattern
It rings, SEM test is carried out to the above-mentioned resulting materials of comparative example 1 and 2.
Test results are shown in figure 10 when adding proportion is 1:2, although having obtained spherical structure, due to starch
Additive amount is lower, is formed by that carbon shell is very thin, leads to structure collapses due to that can not resist convergent force in cooling procedure.
Therefore, there is fracture phenomena in the hollow carbosphere of many starch bases.
Test result when adding proportion is 1:5 is as shown in figure 11, since the additive amount of starch increases, so that carbon thickness of the shell
Increase, but due to the excess of starch, causes the property uniform in size of the hollow carbosphere of starch base to decline, also result in much starch
The rupture of the hollow carbosphere of base.
In summary it tests it is found that the polystyrene and soluble starch ratio of carboxyl-functional are to the hollow carbosphere of acquisition
Microscopic appearance have decisive impact.
In order to study carboxyl-functional polystyrene and starch proportion to starch base hollow carbon micro-sphere material specific surface area
With the influence of pore-size distribution, N is carried out to the above-mentioned resulting materials of comparative example 1 and 22Adsorption-desorption test and pore-size distribution analysis.
Test result when adding proportion is 1:2 is as shown in Figure 12 and Figure 13, and specific surface area is only 427 m2/ g, aperture point
Cloth is in 3.2-5.3 nm.
Test result when adding proportion is 1:5 is as shown in Figure 14 and Figure 15, and specific surface area is only 345 m2/g；Aperture point
Cloth is in 3.6-4.6 nm.
It is 1:3 when institute prepared material by the polystyrene and soluble starch ratio with carboxyl-functional in embodiment 1
Specific surface area compares it is found that specific surface area when ratio is 1:3 is 1312 m2/ g, be respectively ratio be 3 times of 1:2 and 1:5 and
3.8 again.
By the way that the experiment of embodiment 1 and comparative example 1, comparative example 2 is compared and analyzed the polyphenyl it is found that carboxyl-functional
The ratio of ethylene and soluble starch, which has pattern, specific surface area and the pore-size distribution of starch base hollow carbon micro-sphere material, to be determined
The influence of property.Therefore, the starch base hollow carbon micro-sphere material of the technology preparation only provided through the invention, is just able to achieve
Excellent specific surface area and stronger absorption property.
In order to study influence of the adsorbance to the hollow carbosphere composite phase-change material performance of starch base, control n-octadecane and
Starch base hollow carbon micro-sphere material is identical, only changes the ratio between experimental group point, prepares the starch base of different adsorbances
Hollow carbosphere composite phase-change material, i.e. embodiment 2, embodiment 3 and comparative example 2.
Embodiment 2
When a kind of adsorbance is 50%, the preparation method of the hollow carbosphere composite phase-change material of starch base: in specific steps not especially
The step of illustrating is identical as 1 preparation method of above-described embodiment, the difference is that: the quality of the n-octadecane is 1 g.
Embodiment 3
When a kind of adsorbance is 60%, the preparation method of the hollow carbosphere composite phase-change material of starch base: in specific steps not especially
The step of illustrating is identical as 1 preparation method of above-described embodiment, the difference is that: the quality of the n-octadecane is 1.5 g.
Comparative example 3
When a kind of adsorbance is 80%, the preparation method of the hollow carbosphere composite phase-change material of starch base: in specific steps not especially
The step of illustrating is identical as 1 preparation method of above-described embodiment, the difference is that: the quality of the n-octadecane is 4 g.
In order to study the maximal absorptive capacity of the hollow carbosphere composite phase-change material of starch base, by 3 gained compound phase of comparative example
Become material and carries out SEM test.Test result is as shown in figure 16, and serious accumulation occurs for most of composite phase-change material, and surface becomes
It must reunite coarse, huge difference also occurs for size.These experimental phenomenas have shown the adsorbance of n-octadecane at this time
It is n-octadecane that is excessive, i.e., being only adsorbed in originally inside hollow carbosphere, starts to be adsorbed outside hollow carbosphere.This
A part of n-octadecane can be revealed inevitably in cyclic process, cannot achieve the purpose of the present invention.
In order to study influence of the adsorbance to the hollow carbosphere composite phase-change material performance of starch base, to above-described embodiment 2
DSC test is carried out with 3 resulting materials.
Test result when adsorbance is 50% is as shown in figure 17, and melting temperature is 29.3 DEG C, crystallization temperature 24.0
DEG C, phase transformation enthalpy is 130.1 J/g and 129.3 J/g.
Test result when adsorbance is 60% is as shown in figure 18, and melting temperature is 29.5 DEG C, crystallization temperature 23.9
DEG C, phase transformation enthalpy is 140.6 J/g and 139.9 J/g.
By comparing and analyzing the experiment of embodiment 1,2 and 3 it is found that when adsorbance is between 50-70%, phase transformation is latent
Heat is in increase tendency, also, can efficiently solve positive ten without departing from the maximal absorptive capacity of starch base hollow carbon micro-sphere material
Eight alkane leakage problems.
Claims (10)
1. a kind of starch base hollow carbon micro-sphere material, it is characterised in that: using soluble starch as carbon source, carboxyl-functional
Polystyrene is template, and the polystyrene of carboxyl-functional and the mass ratio of soluble starch are 1:3, through hydro-thermal reaction and height
After temperature carbonization, it is not necessarily to activation process, the carbon material with hollow carbon microballoon pattern can be obtained.
2. starch base hollow carbon micro-sphere material according to claim 1, it is characterised in that: the hollow carbosphere of gained starch base
The specific surface area of material is 1300-1350 m2/g。
3. the preparation method of starch base hollow carbon micro-sphere material according to claim 1, it is characterised in that the following steps are included:
Step 1) polystyrene/soluble starch complex microsphere preparation, by the polystyrene of carboxyl-functional and soluble shallow lake
Powder is put into beaker after mixing, is carried out hydro-thermal reaction, is obtained polystyrene/soluble starch complex microsphere, further wash
It washs, dry；
The preparation of the hollow carbosphere of step 2 starch base, the polystyrene that step 1) is obtained/soluble starch complex microsphere are high
Temperature carbonization, can be obtained the hollow carbosphere of starch base.
4. preparation method according to claim 3, it is characterised in that: the polystyrene of the step 1) carboxyl-functional and
The condition of soluble starch mixing is that first 30 DEG C of constant temperature stir 0.5-1 h, then ultrasound 0.5-2 h.
5. preparation method according to claim 3, it is characterised in that: the condition of the step 1) hydro-thermal reaction is to control
Hydrothermal temperature is 170-190 DEG C, and the time of hydro-thermal reaction is 10-15 h.
6. preparation method according to claim 3, it is characterised in that: the condition of the step 2 high temperature carbonization is to rise
Warm rate is 1-5 DEG C/min, and carburizing temperature is 500-600 DEG C, and carbonization time is 12 h.
7. heat accumulation application of the starch base hollow carbon micro-sphere material as absorption phase-change material according to claim 1, feature
It is: is mixed the hollow carbosphere of starch base and phase-change material, with certain adsorbance in certain condition using vacuum impregnation technology
Under adsorbed, the hollow carbosphere composite phase-change material of starch base can be obtained.
8. heat accumulation application according to claim 7, it is characterised in that: the adsorbance is 50%-70%, vacuum impregnation temperature
It is 50-70 DEG C, the time is 12-24 h.
9. heat accumulation application according to claim 7, it is characterised in that: the phase-change material is n-octadecane.
10. heat accumulation application according to claim 7, it is characterised in that: the hollow carbosphere composite phase-change material of starch base
The phase transition temperature of material is 23.9-29.8 DEG C, and latent heat of phase change is 129.3-170.5 J/g.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111394067A (en) * | 2020-05-09 | 2020-07-10 | 中国科学院化学研究所 | Metal fluoride high-temperature phase change energy storage microcapsule and preparation method and application thereof |
| CN112266770A (en) * | 2020-11-25 | 2021-01-26 | 甘肃烟草工业有限责任公司 | Beeswax/polystyrene composite phase change energy storage material and preparation method and application thereof |
| CN112794302A (en) * | 2019-11-14 | 2021-05-14 | 中国科学院大连化学物理研究所 | Spherical carbon material and preparation method thereof |
| CN113443625A (en) * | 2021-06-30 | 2021-09-28 | 华东理工大学 | Preparation method of polystyrene resin-based spherical activated carbon |
| CN114380289A (en) * | 2021-12-13 | 2022-04-22 | 北方奥钛纳米技术有限公司 | Preparation method and application of carbonized particle material and activated carbon electrode material |
-
2019
- 2019-06-25 CN CN201910553652.0A patent/CN110217774B/en active Active
Non-Patent Citations (2)
| Title |
|---|
| ROBIN J. WHITE等: "Functional Hollow Carbon Nanospheres by Latex Templating", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| 王国建: "《功能高分子材料（第2版）》", 30 June 2014, 同济大学出版社 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112794302A (en) * | 2019-11-14 | 2021-05-14 | 中国科学院大连化学物理研究所 | Spherical carbon material and preparation method thereof |
| CN111394067A (en) * | 2020-05-09 | 2020-07-10 | 中国科学院化学研究所 | Metal fluoride high-temperature phase change energy storage microcapsule and preparation method and application thereof |
| CN111394067B (en) * | 2020-05-09 | 2021-02-09 | 中国科学院化学研究所 | Metal fluoride high-temperature phase change energy storage microcapsule and preparation method and application thereof |
| CN112266770A (en) * | 2020-11-25 | 2021-01-26 | 甘肃烟草工业有限责任公司 | Beeswax/polystyrene composite phase change energy storage material and preparation method and application thereof |
| CN112266770B (en) * | 2020-11-25 | 2022-02-01 | 甘肃烟草工业有限责任公司 | Beeswax/polystyrene composite phase change energy storage material and preparation method and application thereof |
| CN113443625A (en) * | 2021-06-30 | 2021-09-28 | 华东理工大学 | Preparation method of polystyrene resin-based spherical activated carbon |
| CN114380289A (en) * | 2021-12-13 | 2022-04-22 | 北方奥钛纳米技术有限公司 | Preparation method and application of carbonized particle material and activated carbon electrode material |
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