CN108079934B - A kind of composite material and preparation method - Google Patents
A kind of composite material and preparation method Download PDFInfo
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- CN108079934B CN108079934B CN201711241859.1A CN201711241859A CN108079934B CN 108079934 B CN108079934 B CN 108079934B CN 201711241859 A CN201711241859 A CN 201711241859A CN 108079934 B CN108079934 B CN 108079934B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The present invention relates to a kind of composite material and preparation methods, can be widely used for the fields such as battery, environmental protection, absorption type dehumidifying, air-conditioning, refrigeration, heat pump, transformation separating-purifying and hydrogen storage manufacture.Composite material is made of support frame material, carbosphere and/or carbon film and support materials, support materials include salt, electrode material and physical absorbent, carbosphere and/or carbon film are firmly attached to support frame material hole wall, support materials are evenly distributed in carbosphere and/or carbon film, support materials are realized directly to be entrenched between charcoal atom, anti-agglomeration deactivation is remarkably reinforced, and effectively improves service life；Composite material has broken the specific surface area limitation of original framework material, can effectively improve the specific surface area of composite material under the premise of improving load capacity, strengthen absorption, reaction or electron transfer rate；Composite material is convenient for realizing the close contact of adsorbent and the wall surface that exchanges heat by extruding, bonding or method for welding, and thermal contact resistance between the two is effectively reduced.
Description
Technical field
The invention belongs to battery, environmental protection, absorption type dehumidifying, air-conditioning, refrigeration, heat pump, transformation separating-purifying and hydrogen storage technologies
Field, in particular to a kind of composite material and preparation method.
Background technique
Composite porous material has many applications in fields such as absorption, catalysis, environmental protection, batteries.Porous material as substrate,
Supported sorbents, catalyst and battery electrode material, the good composite porous material of forming properties, improve the dispersion of support materials
Degree, utilization rate and activity delay its key performance to decay, while strengthening its heat and mass or even conductive capability.It is compound more at present
Porous materials, which mostly use, the methods of to be simply mixed or impregnates, and technique is relatively easy.The height of support materials difficult to realize is simply mixed
Dispersion, microcosmic level support materials and open support framework material be not chimeric close, the heat and mass or conduction of microcosmic level
Performance improvement is limited.For infusion process under the premise of realizing monolayer dispersion, load capacity is then limited to the specific surface area of substrate, unit
Quality or volume load capacity are limited.And the composite porous material that two methods obtain is limited to work operating condition, such as in use process
The operating conditions such as periodical hot and cold alternation, long term high temperature, support materials can be inactivated gradually, lose the abilities such as absorption, catalysis, anti-attenuation energy
Power is poor, and life cycle is partially short.
Summary of the invention
In order to overcome the above deficiency, the present invention provides one kind can be realized specific surface area promotion, load capacity increases, is microcosmic
It is uniformly dispersed and chimeric close, the strong composite porous material and preparation method thereof of anti-attenuation ability.
The prior art generally passes through the method for being simply mixed or impregnating, using high-temperature calcination means, material load more
Above the support frame material of hole, it is easy to appear support materials agglomeration, in order to overcome the problems, such as this, can be added during the preparation process
Enter anticaking agent and dispersing agent improves the dispersion degree of support materials.But it is limited to porous material specific surface area, in monolayer dispersion
In the case of, load capacity is relatively low, and microcosmic level support materials are not chimeric with open support framework material tight, easily tie in use process
Block, which is reunited, to be inactivated, and anti-attenuation ability is weaker.For this purpose, the present invention is in network analysis, " support materials are in open support framework material table
On the basis of microscopic appearance transition rule in face dispersal mechanism, and mixing carbonaceous persursor material carbonisation ", it is provided that
In support materials dipping solution be added sugar, by be dried make sugar and support materials equably with membrane structure primary solidification in
The hole wall of support frame material is handled using suitable high-temperature activation, forms microballoon or membrane structure, former with molecule and carbon
Sub- active force is embedded in open support framework material hole wall, strengthens the heat exchange between framework material and support materials or conductive energy
Power.The results showed that the charcoal atom that obtains with sugar charcoalization of support materials is staggeredly inlayed, effectively inhibit support materials absorption,
Catalysis reaction and the reunion of hot and cold alternation process, anti-attenuation ability are strong；Support materials are evenly distributed in carbon film and/or carbosphere,
It is spatially distributed in stephanoporate framework wall surface, improves load capacity under the premise of keeping dispersing intensity, increase the ratio table of composite material
Area effectively improves support materials utilization rate and efficiency.
To achieve the goals above, the present invention adopts the following technical scheme:
A kind of composite material, comprising:
Support frame；
Carbosphere and/or carbon film on the support frame；
The support materials being dispersed in the carbosphere and/or carbon film.
Heretofore described " support frame " refers to: have the function of following four stephanoporate framework material: first, and it provides micro-
View hole gap structure support framework structure abundant maintains good mass transfer ability；Second, higher specific surface area provides higher
Load area, increase load capacity and dispersion uniformity；Third, higher thermal coefficient realize the good biography of composite material
Thermal energy power；4th, strong electric conductivity realizes the good electron transfer capabilities of composite material.
Certainly to thermally conductive or of less demanding conductive capability composite material, high thermal conductivity or strong conductive support can not also be used
Framework material, such as vermiculite, silica gel.
" carbosphere " belonging to the present invention refers to: sugared film is less than melting in heating melting process, porous media surface tension
Micro- sugar ball that the surface tension of sugar is formed, the carbosphere formed after carbonization.
Heretofore described " carbon film " refers to: sugared film is greater than melting in heating melting process, porous media surface tension
The surface tension of sugar, the carbon film structure that direct carbonization obtains.
Heretofore described " support materials " refer to: salt, a kind of metal ion or ammonium ion (NH4+) and acid ion
Or the compound that nonmetallic ion combines；Electrode material, the positive and negative pole material of battery；Physical absorbent, one kind pass through Van der Waals
Material of the power to gas or ionic adsorption.
Heretofore described " sugar " refers to: the aldehydes (Aldehyde) or ketone of polyhydroxy (2 or more)
(Ketone) compound can become the organic compound of one of both of the above after hydrolyzing.
Preferably, the average thickness of the support frame hole wall thickness is 0.3nm~1mm；
Preferably, the average grain diameter of the carbosphere is 10nm~0.05mm；
Preferably, the average thickness of the carbon film is 1nm~0.05mm；
Preferably, the support materials average grain diameter is lower than 10 μm；
Preferably, the material of the support frame is expansible graphite, aluminium oxide, porous graphite, porous fibre, active carbon
At least one of fiber, foamy carbon, active carbon, graphite fibre, porous metals, porous ceramics, vermiculite, silica gel；
Preferably, the salt is LiCl, BaCl2、CaBr2、NaBr、KBr、LiBr、PbCl2、LiCl、CaCl2、MnCl2、
BaCl2、SrCl2、CoCl2、MgCl2、PbCl2、NiCl2、FeCl3、CuCl2、CuCl2、ZnCl2、AgNO3Or Na2SO4It is middle a kind of or
A variety of combinations；
Preferably, the electrode material, which is enough subjected to 400 DEG C and the above high-temperature calcination, will not decompose and/or be denaturalized, such as
TiO。
Preferably, the physical absorbent is hydrogen bearing alloy, zeolite molecular sieve and Organometallic framework material.
Preferably, the open support skeleton, support materials mass ratio be 1:0.5~9.
Preferably, the ratio between carbon containing mole and support materials mole are 0.5~6 in the sugar.
The present invention also provides a kind of composite material, the thermal contact resistance of the composite material is 10-6~10-4㎡·K/W。
The present invention also provides a kind of preparation methods of composite material, comprising:
Pretreated open support skeleton is impregnated in sugared, support materials mixed solutions, dry, formation film；It is living
Change, open support skeleton wall surface forms carbosphere and/or carbon film to get composite material.
Preferably, the open support skeleton, support materials mass ratio be 1:0.5~9.
Preferably, the ratio between carbon containing mole and support materials mole are 0.5~6 in the sugar.
Preferably, the material of the support frame is expansible graphite, aluminium oxide, porous graphite, porous fibre, active carbon
At least one of fiber, foamy carbon, active carbon, graphite fibre, porous metals, porous ceramics, vermiculite, graphene, silica gel；
Preferably, the salt is LiCl, BaCl2、CaBr2、NaBr、KBr、LiBr、PbCl2、LiCl、CaCl2、MnCl2、
BaCl2、SrCl2、CoCl2、MgCl2、PbCl2、NiCl2、FeCl3、CuCl2、CuCl2、ZnCl2、AgNO3Or Na2SO4It is middle a kind of or
A variety of combinations；
Preferably, the electrode material, which is enough subjected to 400 DEG C and the above high-temperature calcination, will not decompose and/or be denaturalized.
Preferably, the physical absorbent is hydrogen bearing alloy, zeolite molecular sieve and Organometallic framework material.
Preferably, the sugar is at least one of monosaccharide, disaccharides, polysaccharide, preferably glucose, fructose, galactolipin, sugarcane
One of sugar, lactose, maltose, trehalose or starch or a variety of combinations；
Preferably, sugared, support materials the mixed solution further includes the anticaking agent and/or dispersing agent of support materials.
" anticaking agents of support materials " are primarily referred to as in the present invention: inhibiting being likely to occur for support materials high-temperature activation process
Agglomeration and/or inhibit support materials the auxiliary agent, such as silica, tricalcium phosphate of long-term Decay Rate etc..
" dispersing agents of support materials " are primarily referred to as: the dispersion degree of support materials and the auxiliary agent of the dipping uniformity are improved, than
Such as support materials CuCl2In add ammonium citrate, its dispersion degree can be improved.
Above-mentioned auxiliary material is only added as needed, it is not necessary to adding raw materials.
Preferably, the pretreated concrete operation step are as follows: at 200~1000 DEG C, right in anaerobic or low-oxygen environment
Support frame is expanded；
Preferably, the preparation method of sugared, support materials the mixed solution are as follows:, will be sugared, negative at room temperature~120 DEG C
Carrier material is uniformly mixed；
Preferably, the condition of the impregnation are as follows: at 20~120 DEG C, impregnate 1min~48h；
Preferably, the condition of the drying process are as follows: at 20~180 DEG C, dry 1h~10d；
Preferably, the condition of the activation processing are as follows: in 400~1000 DEG C, activate 30min~12h；
Preferably, spray process replacement also can be used in the impregnation.
Normal pressure excess infusion process, normal pressure equi-volume impregnating, negative pressure mistake can be used in heretofore described " impregnation "
Measure one of infusion process and negative pressure equi-volume impregnating.Normal pressure is excessive and equi-volume impregnating is the branch under atmospheric pressure environment
Support bone frame material immerses in maceration extract；Negative pressure is excessive and equi-volume impregnating is that support frame material is placed in sealing container,
Sealed container interior gas is extracted first, is formed vacuum or near vacuum environment, is then injected into maceration extract.Normal pressure impregnation technology letter
It is single, it is easy to implement；Negative pressure impregnation technique is more complex, but gas in support frame material micropore is conducive to be discharged, and is convenient for maceration extract
Into in the ultrafine micropore of support frame material, increase support frame material micropore utilization rate, improves the effective negative of support materials
Carrying capacity.Excessive infusion process refers to that maceration extract dosage is more than support frame material complete wetting aequum, and impregnant needs after the completion of dipping
It to be pulled out from solution；Equi-volume impregnating refers to that maceration extract dosage is equal with support frame material liquid absorption amount, and the two is mixed with dipping
Afterwards, impregnant is directly formed.Excessive infusion process technique is relatively easy, to process control parameter require it is less, but production efficiency compared with
It is low；Equi-volume impregnating is higher to matching parameter requirement, but is easy to implement continuous industry production, conducive to the composite material of production
It can stablize.
The present invention also provides a kind of preferably composite material and preparation method thereofs, comprising the following steps:
(1) support frame pretreatment
When support frame material is expansible graphite, it is necessary at a temperature of 200~1000 DEG C in anaerobic or low-oxygen environment into
Row expansion pretreatment, to realize the porous of graphite；When support frame material is porous metals, metal oxide layer can be carried out
Removal pretreatment, improves the intensity of load of maceration extract.Mainly there are four functions for stephanoporate framework material: first, microscopic void is provided
The support framework structure of structure-rich maintains good mass transfer ability；Second, higher specific surface area provides higher load
Area increases the uniformity of load capacity and dispersion；Third, higher thermal coefficient realize the good heat transfer energy of compound adsorbent
Power；4th, strong electric conductivity realizes the good electron transfer capabilities of composite material.Certainly of less demanding to thermally conductive and conductive capability
Adsorbent, high thermal conductivity or strong conductive porous framework material, such as vermiculite, silica gel can not also be used.
(2) prepared by maceration extract
At room temperature~120 DEG C, the sugar, support materials and auxiliary material are dissolved in solvent, and stirs evenly, the process
The main solubility for considering support materials and sugar determines that maceration extract configures temperature.This step mainly realizes the height of support materials and sugar
Degree dispersion, sugar is primarily to provide the carbon source for activation.
(3) it impregnates
Support frame material is placed in maceration extract, and for dip time between 1min~48h, dipping temperature is room temperature~120
DEG C, then form impregnant.This step mainly realizes that sugar and support materials are evenly dispersed in the hole wall of support frame material.
(4) dry
Impregnant is dry, drying temperature room temperature~220 DEG C, and drying time is 1h~10 day；This process mainly removes big portion
Point or whole solvent, realize sugar and support materials uniformly with membrane structure primary solidification in the pore wall of support frame material
Face, strengthens the heat exchange between framework material and support materials, and microcosmic heat exchange is enhanced.
(5) it activates
It is activated in anaerobic or low-oxygen environment, activation temperature is 400~1000 DEG C, and activation time is 30min~12h, is obtained
Obtain composite material；This process utilizes fractional load material dehydration, sugared high temperature cabonization mechanism and part atmosphere such as vapor, two
Carbonoxide completes carbohydrate breakdown carbonization to carbon activation, can be with the surface of molten state sugar by support frame material hole wall
Power interaction, sugared film form carbosphere and/or carbon film, are fitted into support materials between charcoal atom, form composite material, overcome by
Stephanoporate framework material specific surface area is limited, monolayer dispersion method load capacity is less than normal, the disadvantages such as high density load anti-attenuation ability difference
End.This step hot environment can be provided by high temperature furnace, micro-wave oven etc..
Wherein, the composite material is made of support frame material, carbosphere and/or carbon film and composite material, and carbon is micro-
Preparation particles of material and/or molecule in charcoal atom in ball and carbon film, average grain diameter and/or thickness 1nm~0.1mm, it is compound
Material average grain diameter is generally below 10 μm.Composite material may also include auxiliary material, be dispersed in carbosphere and/or carbon film, still
Auxiliary material or auxiliary material are being not added with when preparation process is decomposed, simultaneously added auxiliary material is not present in final composite material.
The composite material feed components proportion is as follows: on the basis of support materials quality, solvent is its quality 0.1
~100 times, support frame material is 0.1~100 times of its quality, and sugar is 0.01~100 times of its quality, and auxiliary material is its quality 0~2
Times；On the basis of support materials mole, carbon containing mole is its 0.5-6 times in sugar；The solvent be water and alcohols extremely
Few one kind；The support materials must be soluble in solvent, or can form uniform suspension, such as LiCl, BaCl2、CaBr2、
NaBr、KBr、LiBr、PbCl2、LiCl、CaCl2、MnCl2、BaCl2、SrCl2、CoCl2、MgCl2、PbCl2、NiCl2、FeCl3、
CuCl2、CuCl2、AgNO3、ZnCl2、Na2SO4Deng；The sugar be monosaccharide, disaccharides, polysaccharide at least one, such as glucose,
Fructose, galactolipin, sucrose, lactose, maltose, trehalose, starch etc., it is necessary to dissolve in solvent；The support frame material
For expansible graphite, aluminium oxide, porous graphite, porous fibre, activated carbon fibre, foamy carbon, active carbon, graphite fibre, porous
At least one of metal, porous ceramics, molecular sieve, silica gel provides the skeleton structure of a thermally conductive mass transfer；The auxiliary material includes
Anticaking agent, the dispersing agent of support materials.The anticaking agent of support materials is mainly the possibility for inhibiting composite material high-temperature activation process
The agglomeration of appearance also can inhibit long-term Decay Rate, such as silica, tricalcium phosphate of composite material etc..Dispersing agent master
Improve the dispersion degree and the dipping uniformity of composite material, such as CuCl2In add ammonium citrate, its dispersion degree can be improved.
Auxiliary material is only added as needed, it is not necessary to adding raw materials.
Maceration extract spray support frame material can also be used in composite material preparation (3) dipping process of the present invention
Realize the process, spray time is between 1 minute~24 hours, and dipping temperature is room temperature~120 DEG C, more using spray process
It is suitble to industrialized production, it can be with mechanical agitation process, so that dipping process is more evenly.
Dipping process of the present invention can be used normal pressure excess infusion process, normal pressure equi-volume impregnating, negative pressure and excessively soak
One of stain method and negative pressure equi-volume impregnating.Normal pressure is excessive and equi-volume impregnating is the support rib under atmospheric pressure environment
Frame material immerses in maceration extract；Negative pressure is excessive and equi-volume impregnating is that support frame material is placed in sealing container, first
Sealed container interior gas is extracted, vacuum or near vacuum environment is formed, is then injected into maceration extract.Normal pressure impregnation technology is simple,
It is easy to implement；Negative pressure impregnation technique is more complex, but gas in support frame material micropore is conducive to be discharged, and enters convenient for maceration extract
In the ultrafine micropore of support frame material, increases support frame material micropore utilization rate, improve the payload amount of support materials.
Excessive infusion process refers to that maceration extract dosage is more than support frame material complete wetting aequum, and impregnant is needed from molten after the completion of dipping
It is pulled out in liquid；Equi-volume impregnating refers to that maceration extract dosage is equal with support frame material liquid absorption amount, after the two is mixed with dipping, directly
Form impregnant.Excessive infusion process technique is relatively easy, less to process control parameter requirement, but production efficiency is lower；Equal bodies
Product infusion process is higher to matching parameter requirement, but is easy to implement continuous industry production, can stablize conducive to the composite material of production.
Composite material and preparation method thereof of the present invention, it is further characterized in that support frame material, impregnant or composite wood
Material by bonding, compacting, can cut at least one method machine-shaping before and after any step, wherein bonding and compacting can be with
It is applied to powder or short grained support frame material, impregnant or composite material simultaneously, bonding can also be applied to block-shaped material
Material connection, cuts main processing massive material, and the purpose of the step can be used so that composite material reaches the shape of demand
One of three kinds of methods, two or three.
Composite material and preparation method thereof of the present invention, composite material after molding can be by bonding, method for welding extremely
It is few a kind of fixed to heat exchange interface, augmentation of heat transfer.Here it bonds binder used and uses the preferable heat-conducting glue of the capacity of heat transmission as far as possible,
To obtain preferable heat-transfer effect.Furthermore, it is necessary to take into account the operating temperature of composite material work temperature and heat-conducting glue, solder
Match and influence of the vacuum brazing temperature to compound adsorbent, to prevent excessively high welding temperature to composite material microstructure
Destruction.
Composite material and preparation method thereof of the present invention can first add Heat Conduction Material and arrive in bonding or compression moulding process
Support frame material, impregnant or composite material, then form, and further strengthen absorbent interior heat transfer.The heat conduction material
Powder or the web materials such as material mainly addition graphite, copper, iron, aluminium, silicon carbide, aluminium oxide, aluminium nitride.
In the forming process of composite material and preparation method thereof of the present invention, support frame material, impregnant or composite wood
Material can be directly molded on heat exchange wall surface, pass through extruding, bonding, at least one close contact for realizing heat-transfer surface of method for welding.
Compared with mentioned-above adsorbent bonding after molding or being brazed in heat exchange interface, the requirement to heat-conducting glue or solder here is more
Height, the heat resisting temperature of heat-conducting glue, the welding temperature of solder have to be lower than activation temperature.
The present invention also provides the composite materials using any above-mentioned method preparation.
The present invention also provides a kind of adsorption refrigerating devices, including any above-mentioned composite material.
The present invention also provides a kind of transformation separators, including any above-mentioned composite material.
The present invention also provides a kind of heat pumps, including any above-mentioned composite material.
The present invention also provides a kind of absorption type dehumidification devices, including any above-mentioned composite material.
The present invention also provides a kind of cell apparatus, including any above-mentioned composite material.
The present invention also provides a kind of hydrogen-storing devices, including any above-mentioned composite material.
Above-mentioned composite material all can be used for battery, environmental protection, absorption type dehumidifying, air-conditioning, refrigeration, heat pump, change in the present invention
The fields such as separating-purifying and hydrogen storage manufacture are pressed, preferably effect is all obtained, reach or be better than the relevant international or state of the sector
Family's standard.
Beneficial effects of the present invention
(1) preparation process of the present invention is relatively simple, and convenient for molding, raw material is easy to get and from a wealth of sources, and production method flexibly may be used
Control is conducive to industrialized production；Composite material prepared by the present invention is by support frame material, carbosphere and/or carbon film and load material
Material composition, support materials include salt, electrode material and physical absorbent, and carbosphere and/or carbon film are firmly attached to support frame
Material hole wall, carbon ball average grain diameter are 10nm~0.05mm, and for the average thickness of carbon film in 1nm~0.1mm, support materials are equal
Even to be distributed in carbosphere and/or carbon film, average grain diameter realizes support materials and is directly entrenched in charcoal original at least below 10 μm
Between son, anti-agglomeration deactivation is remarkably reinforced, and effectively improves service life；Composite material has broken the ratio of original framework material
Surface area limitation can effectively improve the specific surface area of composite material under the premise of improving load capacity, strengthen absorption, reaction
Or electron transfer rate；Composite material is convenient for by squeezing, bonding or method for welding realize adsorbent and the close of wall surface that exchange heat
Contact, is effectively reduced thermal contact resistance between the two.The preparation method technique is simpler, easily molded, is convenient for industrialized production.
(2) the obtained composite material of the present invention, the load capacity evenly dispersed in carbosphere and/or carbon film that realize support materials
Greatly, macroscopical and microcosmic heat and mass all obtains obvious reinforcing.
(3) the obtained composite material of the present invention has broken the specific surface area limitation of original framework material, can load improving
Under the premise of amount, the specific surface area of composite material is effectively improved, strengthens absorption, reaction or electron transfer rate.
(4) the obtained composite material of the present invention realizes support materials and is directly entrenched between charcoal atom, and anti-agglomeration inactivates energy
Power is remarkably reinforced, and effectively improves service life.
(5) composite material of the invention can activate the heat exchange wall surface that front and back squeezes, bonds or be soldered to heat exchanger, mode
Flexibly and easily, it can be effectively reduced thermal contact resistance between adsorbent and heat exchanger.
(6) composite structure of the invention is simple, thermally conductive and electron transfer is high-efficient, practical, easy to spread.
Detailed description of the invention
Fig. 1 graphite-carbosphere-calcium chloride composite material SEM；
Fig. 2 graphite-carbon film-calcium chloride composite material SEM picture and EDS analysis；
SEM after Fig. 3 graphite-carbon film-calcium chloride composite material and calcium chloride sorption cycle 1000 times；Wherein, A is stone
SEM after ink-carbon film-calcium chloride composite material sorption cycle 1000 times；B is SEM after calcium chloride sorption cycle 10 times；
Fig. 4 graphite-carbosphere-calcium chloride composite material and pure calcium chloride suction/deamination dynamics comparison.
Specific embodiment
Feature of present invention and other correlated characteristics are described in further detail by the following examples, in order to the same industry
The understanding of technical staff:
Embodiment 1
In the present embodiment, support materials are 24g calcium chloride, and support frame material is 6g expansible graphite, solvent 100ml
Water, sugar are 6.16g sucrose；It is heated 2 minutes under 700 DEG C of oxygen-free environments, expansible graphite is handled as expanded graphite；Chlorination
Calcium and sucrose are dissolved in 50 DEG C of water, and are stirred evenly, and maceration extract is obtained；Using normal pressure equi-volume impregnating, graphite is soaked
For stain in maceration extract 1h, dipping temperature is 55 DEG C, then forms impregnant；At 120 DEG C, forced air drying impregnant 12h；550℃
At a temperature of, impregnant activates 2.5h in carbon dioxide atmosphere, then takes out and is cooled to room temperature in drying basin, is i.e. acquisition powder
Last shape composite material.The composite material can be used to adsorb methanol, ethyl alcohol, ammonia and water.The support frame of the type composite material is
Expanded graphite, as shown in Fig. 1, SEM show that wall surface forms average grain diameter about 100nm carbosphere, and calcium chloride uniform load is in carbon
Microballoon.XRD analysis does not see the diffraction maximum of calcium chloride.Calcium chloride content is about 80%.The powder sorbent can also be in a mold
Extrusion forming, density 520kg/m3 are bonded on heat exchange wall surface, thermal contact resistance 10 by heat conductive curing glue-4㎡ K/W amount
Grade.As shown in Fig. 4, under same test state, the absorption/desorption time for completing 80% maximal absorptive capacity is only pure calcium chloride
1/5.
Embodiment 2
In the present embodiment, support materials are 24g calcium chloride, and support frame material is 6g expansible graphite, solvent 100ml
Water, sugar are 12g glucose；It is heated 2 minutes under 800 DEG C of oxygen-free environments, expansible graphite is handled as expanded graphite；Chlorination
Calcium and sucrose are dissolved in 50 DEG C of water, and are stirred evenly, and maceration extract is obtained；Using normal pressure equi-volume impregnating, graphite is soaked
For stain in maceration extract 1h, dipping temperature is 55 DEG C, then forms impregnant；At 120 DEG C, forced air drying impregnant 12h；650℃
At a temperature of, impregnant activates 1.5h in nitrogen atmosphere, then takes out and is cooled to room temperature in drying basin, that is, obtains powdered
Composite material.The composite material can be used to adsorb methanol, ethyl alcohol, ammonia and water.The support frame of the type composite material is expansion
Graphite, as shown in Fig. 2, SEM show that its internal expansion graphite secondary hole wall forms the carbon film of average thickness about 50nm, chlorine
Changing calcium content is about 75%, EDS analysis shows calcium chloride is uniformly embedded into carbon atom.From attached drawing 3 as can be seen that passing through 1000 times
After absorption, which there is not significant change, anti-attenuation excellent ability, and pure calcium chloride is only inhaled for ten times
It is attached to occur as soon as reunion agglomeration.
Embodiment 3
In the present embodiment, support materials are 60g lithium bromide, and support frame material is 50g foam copper, and solvent is 50ml water,
Sugar is 20g amylopectin；Foam copper is cut to need shape, and removing oxide layer is gone to handle；Lithium bromide and starch dissolution in
It in normal-temperature water, and stirs evenly, obtains maceration extract；Using normal pressure excess infusion process, 80 DEG C of dipping temperature, which makes starch
Gelatinization, is impregnated in maceration extract 1h for foam copper, then pulls out to form impregnant；At normal temperature, aeration-drying 2d；Impregnant with change
350 DEG C of solders of fusing point are coated in hot wall face, and are compressed, 450 DEG C at a temperature of, be placed in vacuum drying oven in 1h, be completed at the same time activation and
Process of Vacuum Brazing, formation composite material-heat exchanger integration system is standby, thermal contact resistance 10-5~10-6㎡ K/W magnitude.
The type composite material is mainly used for dehumidifying.
Embodiment 4
In the present embodiment, support materials are 30g silicon monoxide, and support frame material is graphite, and solvent is 100ml water, sugar
For 10g glucose；Silicon monoxide and glucose are dissolved in 50 DEG C of water, and stirred evenly, suspended maceration extract is obtained；Using negative
Equi-volume impregnating is pressed, 60 DEG C of dipping temperature, then dip time 2h forms impregnant；120 DEG C of impregnant vacuum drying are for 24 hours；
Under 500w power, impregnant activates 12min in micro-wave oven nitrogen atmosphere, and temperature is lower than 1000 DEG C, then takes out in drying basin
It is cooled to room temperature, direct oxygen-free environment compression moulding.The composite material can be used to do cathode of lithium battery.
Finally it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not limited to this hair
It is bright, although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still
It can modify to technical solution documented by previous embodiment, or part is equivalently replaced.It is all in this hair
Within bright spirit and principle, any modification, equivalent replacement, improvement and so on should be included in protection scope of the present invention
Within.Above-mentioned, although the foregoing specific embodiments of the present invention is described with reference to the accompanying drawings, not to the scope of the present invention
Limitation, those skilled in the art should understand that, based on the technical solutions of the present invention, those skilled in the art are not required to
Make the creative labor the various modifications or changes that can be made still within protection scope of the present invention.
Claims (24)
1. a kind of composite material characterized by comprising
Support frame；
Carbosphere and/or carbon film on the support frame；
The support materials being dispersed in the carbosphere and/or carbon film；
The composite material specific the preparation method comprises the following steps:
Pretreated support frame is impregnated in sugared, support materials mixed solutions, dry, formation film；Activation, film carbonization
It is carbosphere and/or carbon film up to composite material.
2. composite material as described in claim 1, which is characterized in that the average thickness of the support frame hole wall thickness is
0.3nm~1mm.
3. composite material as described in claim 1, which is characterized in that the average grain diameter of the carbosphere be 10nm~
0.05mm。
4. composite material as described in claim 1, which is characterized in that the average thickness of the film is 1nm~0.05mm.
5. composite material as described in claim 1, which is characterized in that the support materials average grain diameter is lower than 10 μm.
6. composite material as described in claim 1, which is characterized in that the material of the support frame is aluminium oxide, porous stone
At least one of ink, porous fibre, foamy carbon, active carbon, porous metals, porous ceramics, vermiculite, graphene or silica gel.
7. composite material as described in claim 1, which is characterized in that the support materials: salt BaCl2、CaBr2、NaBr、
KBr、LiBr、LiCl、CaCl2、MnCl2、BaCl2、SrCl2、CoCl2、MgCl2、PbCl2、NiCl2、FeCl3、CuCl2、ZnCl2、
AgNO3Or Na2SO4In one or more combination, between electrode material TiO, nitride, tin-based oxide, tin alloy, metal
One or more combination in compound, cobalt acid lithium, LiMn2O4 or LiFePO4, physisorption material are hydrogen bearing alloy, zeolite
Molecular sieve or Organometallic framework material.
8. composite material as described in claim 1, which is characterized in that the quality of the open support skeleton, support materials
Than for 0.5~9:1.
9. composite material as described in claim 1, which is characterized in that in the carbosphere and/or carbon film carbon mole with
Support materials mole ratio is 0.05~6:1.
10. composite material as described in claim 1, which is characterized in that the thermal contact resistance of the composite material is 10-6~10- 4m2·K/W。
11. composite material as described in claim 1, which is characterized in that the carbon mole in the sugar is rubbed with support materials
Your amount ratio is 0.5~6:1.
12. composite material as described in claim 1, which is characterized in that the sugar is at least one of monosaccharide, disaccharides, polysaccharide.
13. composite material as claimed in claim 12, which is characterized in that it is described sugar be glucose, fructose, galactolipin, sucrose,
One of lactose, maltose, trehalose or starch or a variety of combinations.
14. composite material as described in claim 1, which is characterized in that sugared, support materials the mixed solution further includes bearing
The anticaking agent and/or dispersing agent of carrier material.
15. composite material as described in claim 1, which is characterized in that the pretreated concrete operation step are as follows: 200
Support frame is expanded at~1000 DEG C, in anaerobic or low-oxygen environment.
16. composite material as described in claim 1, which is characterized in that the preparation side of sugared, support materials the mixed solution
Method are as follows: at 20~120 DEG C, sugar, support materials are uniformly mixed.
17. composite material as described in claim 1, which is characterized in that the condition of the impregnation are as follows: in 20~120 DEG C
Under, impregnate 1min~48h.
18. composite material as described in claim 1, which is characterized in that the condition of the drying process are as follows: in 20~220 DEG C
Under, dry 1h~10d.
19. composite material as described in claim 1, which is characterized in that the condition of the activation processing are as follows: in 100~1000
DEG C, activate 30min~12h.
20. composite material as described in claim 1, which is characterized in that spray process replacement also can be used in the impregnation.
21. a kind of adsorption refrigerating device, which is characterized in that including the described in any item composite materials of claim 1-20.
22. a kind of transformation separator, which is characterized in that including the described in any item composite materials of claim 1-20.
23. a kind of heat pump, which is characterized in that including the described in any item composite materials of claim 1-20.
24. the described in any item composite materials of claim 1-20 are in battery, environmental protection, dehumidifying, refrigeration, transformation separating-purifying, storage
Application in hydrogen or air-conditioning, heat pump manufacture.
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| CN108079934B (en) * | 2017-11-30 | 2019-02-22 | 山东大学 | A kind of composite material and preparation method |
| CN108704453A (en) * | 2018-05-31 | 2018-10-26 | 佛山市高明区爪和新材料科技有限公司 | A kind of preparation method of air dewetting agent |
| CN109851858B (en) * | 2018-06-18 | 2020-12-08 | 浙江大学 | Molecular sieve/fiber composite material and preparation method thereof |
| CN111099943B (en) * | 2018-10-29 | 2021-07-02 | 中国石油化工股份有限公司 | Method for microwave pyrolysis of biomass |
| CN109225145A (en) * | 2018-11-25 | 2019-01-18 | 中国科学院合肥物质科学研究院 | A kind of preparation method and application of zirconium-based metallic organic coordination compound UiO-66/ Foam carbon composite material |
| CN110102271B (en) * | 2019-05-15 | 2024-02-13 | 天津清科环保科技有限公司 | Porous section bar containing nano adsorbent for VOCs treatment and method and equipment thereof |
| CN110957477B (en) * | 2019-10-30 | 2021-04-27 | 苏州大学 | Porous ceramic composite lithium metal cathode and preparation method thereof |
| CN110890530B (en) * | 2019-10-30 | 2021-04-13 | 苏州大学 | Lithium metal secondary battery based on porous ceramic composite lithium metal cathode and preparation method thereof |
| CN112892517B (en) * | 2019-12-04 | 2022-07-01 | 中国科学院大连化学物理研究所 | Hybrid carbon material and preparation method thereof, catalyst containing hybrid carbon material and preparation method thereof |
| CN113013385A (en) * | 2019-12-19 | 2021-06-22 | 山西沃特海默新材料科技股份有限公司 | Coating agent, silicon-carbon material and preparation process |
| CN111686478B (en) * | 2020-06-30 | 2022-05-24 | 成都大学 | Carbon foam membrane material for oil-water emulsion separation, preparation method and application |
| CN114432870B (en) * | 2020-10-31 | 2023-05-05 | 中国石油化工股份有限公司 | FCC regenerated flue gas treatment method and device |
| CN114149056A (en) * | 2021-11-22 | 2022-03-08 | 青岛农业大学 | Preparation and application of heteroatom-containing carbon microsphere particle electrode |
| CN113990415A (en) * | 2021-12-30 | 2022-01-28 | 南京师范大学 | Three-dimensional catalytic material catalytic characteristic screening system based on neural network |
| CN114573372B (en) * | 2022-03-31 | 2024-02-23 | 浙江华熔科技有限公司 | High-temperature-resistant and oxidation-resistant graphite microporous plugging agent and preparation method thereof |
| CN115117327B (en) * | 2022-08-25 | 2022-11-22 | 溧阳天目先导电池材料科技有限公司 | Low-expansion silicon-based composite material and preparation method and application thereof |
| CN115739027A (en) * | 2022-10-21 | 2023-03-07 | 合肥工业大学 | NH 2 -MIL-101 (Fe) @ BC composite material, application and preparation method |
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