WO2019105356A1 - 一种复合材料及其制备方法 - Google Patents
一种复合材料及其制备方法 Download PDFInfo
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- WO2019105356A1 WO2019105356A1 PCT/CN2018/117792 CN2018117792W WO2019105356A1 WO 2019105356 A1 WO2019105356 A1 WO 2019105356A1 CN 2018117792 W CN2018117792 W CN 2018117792W WO 2019105356 A1 WO2019105356 A1 WO 2019105356A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01J20/22—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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- 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
- H01M4/362—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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/62—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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the invention belongs to the technical field of battery, environmental protection, adsorption dehumidification, air conditioning, refrigeration, heat pump, pressure swing separation and purification and hydrogen storage, and particularly relates to a composite material and a preparation method thereof.
- Composite porous materials have many applications in the fields of adsorption, catalysis, environmental protection, and batteries.
- the porous material is loaded with adsorbent, catalyst and battery electrode material to form a composite porous material with good performance, which improves the dispersion, utilization and activity of the supported material, delays the attenuation of its key properties, and strengthens its heat and mass transfer.
- Conductivity At present, the composite porous material mostly adopts a simple mixing or impregnation method, and the process is relatively simple. It is difficult to achieve high dispersion of the load material by simple mixing. The micro-layered load material and the porous support skeleton material are not closely fitted, and the heat transfer mass transfer or conductivity improvement at the microscopic level is limited.
- the impregnation method is limited by the specific surface area of the substrate, and the unit mass or volume load is limited.
- the composite porous material obtained by the two methods is limited in working conditions, such as periodic hot and cold alternating, long-term high temperature and other working conditions, the load material will gradually deactivate, lose the ability of adsorption, catalysis, and anti-attenuation ability. Poor, life cycle is short.
- the present invention provides a composite porous material capable of realizing a specific surface area increase, an increased load amount, a fine microscopic dispersion, a compact fit, and a strong anti-attenuation capability, and a preparation method thereof.
- a high-temperature calcination method is generally used to load a material on a porous support skeleton material by a simple mixing or impregnation method, and agglomeration of a load material is likely to occur.
- an anti-caking agent and an anti-caking agent may be added during the preparation process.
- the dispersant increases the dispersion of the load material.
- the loading is low, and the microscopic layer of the supporting material and the porous supporting framework material are not tightly fitted, and the agglomeration agglomeration is inactivated and the anti-attenuation ability is easy to use during use. Weak.
- the present invention systematically analyzes the "dispersion mechanism of the supported material on the surface of the porous support skeleton material and the change of the microscopic morphology during the carbonization process of the mixed carbonaceous precursor material", and proposes to add sugar to the impregnation solution of the supporting material.
- the sugar and the supporting material are firstly solidified in a film-like structure on the pore wall surface of the supporting skeleton material, and then subjected to a suitable high-temperature activation treatment to form a microsphere or a membrane structure, which is embedded in the pore by molecular and carbon atom forces. Supporting the pore wall surface of the skeleton material to enhance heat exchange or electrical conductivity between the framework material and the load material.
- the experimental results show that the supported materials are interlaced with carbon atoms obtained by carbonization of carbon, which effectively inhibits the agglomeration of the supported materials during adsorption, catalytic reaction and alternating hot and cold processes, and has strong anti-attenuation ability; distribution of load materials in carbon film and/or carbon microspheres It is uniform and has a three-dimensional distribution on the porous skeleton wall surface. Under the premise of maintaining the dispersion strength, the load is increased, the specific surface area of the composite material is increased, and the utilization ratio and energy efficiency of the load material are effectively improved.
- Carbon microspheres and/or carbon film on the support skeleton Carbon microspheres and/or carbon film on the support skeleton
- a load material dispersed in the carbon microspheres and/or carbon film is provided.
- the "support skeleton” as used in the present invention means: having the following four functional porous skeleton materials: first, providing a support skeleton structure rich in microscopic pore structure, maintaining good mass transfer ability; second, higher specific surface area , providing higher load area, increasing load and dispersion uniformity; third, higher thermal conductivity, achieving good heat transfer capability of composite materials; fourth, strong electrical conductivity, achieving good electron transfer capability of composite materials .
- composite materials that do not require high thermal conductivity or electrical conductivity may not use high thermal conductivity or strong conductive support skeleton materials such as vermiculite or silica gel.
- the "carbon microsphere” to which the present invention pertains refers to a micro-sugar ball formed by a carbon film formed by carbonization after the sugar film is heated and melted, the surface tension of the porous medium is smaller than the surface tension of the molten sugar.
- the "carbon film” as used in the present invention means a carbon film structure obtained by directly carbonizing a sugar film during a temperature-melting melting process, a surface tension of the porous medium being greater than a surface tension of the molten sugar.
- the "supporting material” as used in the present invention means: a salt, a compound in which a metal ion or an ammonium ion (NH 4+ ) is combined with an acid ion or a non-metal ion; an electrode material, a positive and negative electrode material of a battery; Adsorbent, a type of material that adsorbs gases or ions by van der Waals forces.
- a salt a compound in which a metal ion or an ammonium ion (NH 4+ ) is combined with an acid ion or a non-metal ion
- an electrode material a positive and negative electrode material of a battery
- Adsorbent a type of material that adsorbs gases or ions by van der Waals forces.
- the "sugar” as used in the present invention means a polyhydroxy (2 or more) aldehyde (Aldehyde) or ketone (Ketone) compound which can be converted into an organic compound of either of them after hydrolysis.
- the average thickness of the support skeleton pore wall thickness is 0.3 nm to 1 mm;
- the carbon microspheres have an average particle diameter of 10 nm to 0.05 mm;
- the carbon film has an average thickness of 1 nm to 0.05 mm;
- the supported material has an average particle diameter of less than 10 ⁇ m;
- the material of the support skeleton is at least one of expandable graphite, alumina, porous graphite, porous fiber, activated carbon fiber, foamed carbon, activated carbon, graphite fiber, porous metal, porous ceramic, vermiculite, and silica gel;
- the salt is LiCl, BaCl 2 , CaBr 2 , NaBr, KBr, LiBr, PbCl 2 , LiCl, CaCl 2 , MnCl 2 , BaCl 2 , SrCl 2 , CoCl 2 , MgCl 2 , PbCl 2 , NiCl 2 , a combination of one or more of FeCl 3 , CuCl 2 , CuCl 2 , ZnCl 2 , AgNO 3 or Na 2 SO 4 ;
- the electrode material is capable of withstanding high temperature calcination at 400 ° C and above without decomposition and/or denaturation, such as TiO.
- the physical adsorbent is a hydrogen storage alloy, a zeolite molecular sieve and an organometallic framework material.
- the mass ratio of the porous support skeleton and the supporting material is 1:0.5-9.
- the ratio of the molar amount of carbon in the sugar to the molar amount of the supporting material is 0.5 to 6.
- the present invention also provides a composite material having a contact thermal resistance of 10 -6 to 10 -4 m 2 ⁇ K/W.
- the invention also provides a preparation method of a composite material, comprising:
- the pretreated porous support skeleton is immersed in a mixed solution of sugar and a supporting material, dried to form a film, and activated, and the porous support skeleton wall surface forms carbon microspheres and/or carbon film, thereby obtaining a composite material.
- the mass ratio of the porous support skeleton and the supporting material is 1:0.5-9.
- the ratio of the molar amount of carbon in the sugar to the molar amount of the supporting material is 0.5 to 6.
- the material of the support skeleton is at least at least one of expandable graphite, alumina, porous graphite, porous fiber, activated carbon fiber, foamed carbon, activated carbon, graphite fiber, porous metal, porous ceramic, vermiculite, graphene, and silica gel.
- expandable graphite alumina
- porous graphite porous fiber
- activated carbon fiber foamed carbon
- activated carbon graphite fiber
- porous metal porous ceramic
- vermiculite graphene
- silica gel silica gel
- the salt is LiCl, BaCl 2 , CaBr 2 , NaBr, KBr, LiBr, PbCl 2 , LiCl, CaCl 2 , MnCl 2 , BaCl 2 , SrCl 2 , CoCl 2 , MgCl 2 , PbCl 2 , NiCl 2 , a combination of one or more of FeCl 3 , CuCl 2 , CuCl 2 , ZnCl 2 , AgNO 3 or Na 2 SO 4 ;
- the electrode material is capable of withstanding high temperature calcination at 400 ° C and above without decomposition and/or denaturation.
- the physical adsorbent is a hydrogen storage alloy, a zeolite molecular sieve and an organometallic framework material.
- the sugar is at least one of a monosaccharide, a disaccharide, and a polysaccharide, preferably a combination of one or more of glucose, fructose, galactose, sucrose, lactose, maltose, trehalose or starch;
- the mixed solution of the sugar and the supporting material further comprises an anti-caking agent and/or a dispersing agent of the supporting material.
- the "anti-caking agent for supporting materials” in the present invention mainly refers to an auxiliary agent which inhibits a possible agglomeration phenomenon of a high-temperature activation process of a supporting material and/or suppresses long-term attenuation of a supporting material, such as silica, tricalcium phosphate, etc. .
- the "dispersant for supporting materials” mainly refers to an auxiliary agent for improving the dispersion degree of the supporting material and the uniformity of impregnation.
- an auxiliary agent for improving the dispersion degree of the supporting material and the uniformity of impregnation for example, the addition of ammonium citrate to the supporting material CuCl 2 can improve the dispersion degree.
- the specific operation step of the pretreatment is: expanding the support skeleton in an oxygen-free or low-oxygen environment at 200 to 1000 ° C;
- the mixed solution of the sugar and the supporting material is prepared by uniformly mixing the sugar and the supporting material at a normal temperature to 120 ° C;
- the conditions of the immersion treatment are: immersion at 20 to 120 ° C for 1 min to 48 h;
- the drying treatment condition is: drying at 20 to 180 ° C for 1 h to 10 d;
- the conditions of the activation treatment are: at 400 to 1000 ° C, activation for 30 min to 12 h;
- the immersion treatment may also be replaced by a shower treatment.
- the "immersion treatment" described in the present invention may be one of a normal pressure excess impregnation method, a normal pressure equal volume impregnation method, a negative pressure excess impregnation method, and a negative pressure equal volume impregnation method.
- the atmospheric excess and equal volume impregnation method is to impregnate the framework material into the impregnation liquid under atmospheric pressure; the negative pressure excess and the equal volume impregnation method are to place the support skeleton material in a sealed container, firstly extract the gas inside the sealed container to form a vacuum. Or approximate the vacuum environment, then inject the immersion liquid.
- the atmospheric pressure impregnation process is simple and easy to implement; the negative pressure impregnation process is more complicated, but it is beneficial to discharge the gas in the micropores of the support skeleton material, facilitating the impregnation liquid to enter the ultrafine pores of the support skeleton material, and increasing the microporosity utilization of the support skeleton material. Increase the payload of the load material.
- Excessive impregnation method means that the amount of the impregnation liquid exceeds the amount required for the complete wetting of the supporting framework material, and the dip material needs to be removed from the solution after the impregnation is completed;
- the equal volume impregnation method means that the amount of the impregnation liquid is equal to the amount of the liquid absorption of the supporting framework material, and the two are impregnated After that, the impregnating material is directly formed.
- the process of excessive impregnation is relatively simple, and the process control parameters are less required, but the production efficiency is lower; the equal volume impregnation method has higher requirements on the proportioning parameters, but it is convenient to realize continuous industrial production, and the composite material which is favorable for production has stable performance.
- the invention also provides a superior composite material preparation method, comprising the following steps:
- the porous framework material has four main functions: first, providing a support skeleton structure rich in microscopic pore structure, maintaining good mass transfer capability; second, higher specific surface area, providing higher load area, increasing load and dispersion Uniformity; third, higher thermal conductivity, to achieve good heat transfer capacity of the composite adsorbent; Fourth, strong conductivity, to achieve good electron transfer ability of the composite.
- the adsorbent which does not require high thermal conductivity and electrical conductivity may not use a high thermal conductivity or strong conductive porous skeleton material such as vermiculite or silica gel.
- the sugar, the supporting material and the auxiliary material are dissolved in a solvent at a normal temperature of 120 ° C and stirred uniformly.
- the process mainly determines the temperature of the immersion liquid in consideration of the solubility of the supporting material and the sugar. This step primarily achieves a high degree of dispersion of the loading material and sugar, primarily to provide a carbon source for activation.
- the supporting skeleton material is placed in the immersion liquid, the immersion time is between 1 min and 48 h, the immersion temperature is from normal temperature to 120 ° C, and then the immersion material is formed. This step mainly realizes that the sugar and the supporting material are uniformly dispersed on the pore wall surface of the supporting skeleton material.
- the dipping material is dried, the drying temperature is normal temperature ⁇ 220 ° C, and the drying time is 1 h to 10 days; the process mainly removes most or all of the solvent, and the sugar and the supporting material are uniformly solidified in the film structure to the pore wall surface of the supporting skeleton material.
- the heat exchange between the skeletal material and the load material is enhanced, and the micro heat exchange is enhanced.
- the pore wall surface of the supported framework material interacts with the surface tension of the molten sugar.
- the sugar film forms carbon microspheres and/or carbon membranes, and the carbon atoms intercalate the supporting materials to form a composite material.
- the specific surface area of the restricted porous framework material is overcome, the load of the monomolecular layer dispersion method is small, and the high-density load has poor anti-attenuation capability.
- the high temperature environment of this step can be provided by a high temperature furnace, a microwave oven or the like.
- the composite material is composed of a support skeleton material, carbon microspheres and/or a carbon film and a composite material, and the composite particles and/or molecules are embedded in the carbon atoms in the carbon microspheres and the carbon film, and the average particle size and/or
- the thickness of the composite material is generally less than 10 ⁇ m, with a thickness of 1 nm to 0.1 mm.
- the composite material may also include excipients that are uniformly dispersed in the carbon microspheres and/or carbon film, but the final composite material does not have added excipients when no excipients are added or the excipients are decomposed during the preparation process.
- the composition of the composite material is distributed as follows: based on the mass of the supported material, the solvent is 0.1 to 100 times its mass, the supporting framework material is 0.1 to 100 times its mass, the sugar is 0.01 to 100 times its mass, and the auxiliary material is The mass is 0 to 2 times; the molar amount of carbon in the sugar is 0.5-6 times based on the molar amount of the supporting material; the solvent is at least one of water and alcohol; the supporting material must be soluble In a solvent, a uniform suspension such as LiCl, BaCl 2 , CaBr 2 , NaBr, KBr, LiBr, PbCl 2 , LiCl, CaCl 2 , MnCl 2 , BaCl 2 , SrCl 2 , CoCl 2 , MgCl 2 , PbCl 2 , NiCl 2 , FeCl 3 , CuCl 2 , CuCl 2 , AgNO 3 , ZnCl 2 , Na 2 SO 4
- the supporting framework material is expandable graphite, alumina, porous graphite, porous fiber, activated carbon fiber, foamed carbon, activated carbon, graphite fiber , porous metal, porous ceramics, molecular sieves,
- At least one of the silica gels provides a thermally conductive mass transfer skeleton structure;
- the excipients include an anti-caking agent and a dispersing agent for the load material.
- the anti-caking agent of the load material mainly inhibits the possible agglomeration of the composite material during the high-temperature activation process, and also inhibits the long-term decay of the composite material, such as silica, tricalcium phosphate, and the like.
- the dispersant mainly improves the dispersion degree and impregnation uniformity of the composite material. For example, the addition of ammonium citrate to CuCl 2 can improve the dispersion degree. Excipients are only added as needed, and it is not necessary to add raw materials.
- the composite material preparation step (3) of the present invention may also be carried out by spraying the support skeleton material with an immersion liquid, the spraying time is between 1 minute and 24 hours, and the immersion temperature is from normal temperature to 120 ° C.
- the spraying process is more suitable for industrial production, and can be accompanied by a mechanical agitation process to make the impregnation process more uniform.
- the impregnation process according to the present invention may be one of a normal pressure excess impregnation method, a normal pressure equal volume impregnation method, a negative pressure excess impregnation method, and a negative pressure equal volume impregnation method.
- the atmospheric excess and equal volume impregnation method is to impregnate the framework material into the impregnation liquid under atmospheric pressure; the negative pressure excess and the equal volume impregnation method are to place the support skeleton material in a sealed container, firstly extract the gas inside the sealed container to form a vacuum. Or approximate the vacuum environment, then inject the immersion liquid.
- the atmospheric pressure impregnation process is simple and easy to implement; the negative pressure impregnation process is more complicated, but it is beneficial to discharge the gas in the micropores of the support skeleton material, facilitating the impregnation liquid to enter the ultrafine pores of the support skeleton material, and increasing the microporosity utilization of the support skeleton material. Increase the payload of the load material.
- Excessive impregnation method means that the amount of the impregnation liquid exceeds the amount required for the complete wetting of the supporting framework material, and the dip material needs to be removed from the solution after the impregnation is completed;
- the equal volume impregnation method means that the amount of the impregnation liquid is equal to the amount of the liquid absorption of the supporting framework material, and the two are impregnated After that, the impregnating material is directly formed.
- the excess impregnation process is relatively simple, requires less process control parameters, but has lower production efficiency; the equal volume impregnation method requires higher ratio parameters, but is convenient for continuous industrial production, and the composite material for production can be stabilized.
- the method for preparing a composite material according to the present invention is characterized in that the supporting skeleton material, the dipping material or the composite material can be processed by at least one method of bonding, pressing and cutting before and after any step, wherein the bonding and pressing can be simultaneously performed.
- bonding can also be applied to the connection of bulk materials, cutting mainly for processing bulk materials, the purpose of this step is to make the composite material to the desired shape, can be used One, two or three of the three methods.
- the formed composite material can be fixed to the heat exchange interface by at least one bonding and brazing method to enhance heat transfer.
- the binder used for bonding is preferably made of a thermal conductive adhesive having a better thermal conductivity in order to obtain a better heat transfer effect.
- a heat conductive material may be added to a supporting skeleton material, a dipping material or a composite material, and then formed to further strengthen the internal heat transfer of the adsorbent.
- the heat conductive material is mainly a powder or a wire mesh material added with graphite, copper, iron, aluminum, silicon carbide, aluminum oxide, aluminum nitride or the like.
- the support skeleton material, the dipping material or the composite material can be directly formed on the heat exchange wall surface, and at least one of the heat exchange surfaces is compacted by extrusion, bonding and brazing methods. contact.
- the requirements for the thermal conductive adhesive or the solder are higher here, and the heat resistant temperature of the thermal conductive adhesive and the soldering temperature of the solder must be lower than the activation temperature. temperature.
- the invention also provides a composite material prepared by any of the above methods.
- the present invention also provides an adsorption refrigeration apparatus comprising any of the above composite materials.
- the present invention also provides a pressure swing separator comprising any of the composite materials described above.
- the invention also provides a heat pump comprising any of the composite materials described above.
- the present invention also provides an adsorptive dehumidification apparatus comprising any of the above composite materials.
- the present invention also provides a battery device comprising any of the above composite materials.
- the invention also provides a hydrogen storage device comprising any of the composite materials described above.
- the above composite materials can be used in the fields of battery, environmental protection, adsorption dehumidification, air conditioning, refrigeration, heat pump, pressure swing separation and purification, and hydrogen storage manufacturing, etc., all of which have obtained superior effects, and are superior or superior to the industry. International or national standards.
- the preparation process of the invention is simple, convenient for molding, easy to obtain raw materials and wide sources, flexible and controllable production mode, and convenient for industrial production;
- the composite material prepared by the invention comprises a support skeleton material, carbon microspheres and/or carbon film and
- the composition of the supporting material comprises a salt, an electrode material and a physical adsorbent.
- the carbon microspheres and/or the carbon film are firmly attached to the pore wall surface of the supporting skeleton material, and the average particle diameter of the carbon sphere is 10 nm to 0.05 mm, and the average thickness of the carbon film is 1nm ⁇ 0.1mm, the load material is evenly distributed in the carbon microspheres and/or carbon film, and the average particle diameter is at least less than 10 ⁇ m, so that the load material is directly embedded between the carbon atoms, and the anti-agglomeration deactivation ability is obviously enhanced.
- the composite material breaks the specific surface area limitation of the original skeleton material, can effectively increase the specific surface area of the composite material, enhance the adsorption, reaction or electron migration rate under the premise of increasing the load; the composite material is easy to be squeezed
- the bonding or brazing method achieves close contact between the adsorbent and the heat exchange wall surface, thereby effectively reducing the contact thermal resistance between the two.
- the preparation method is simple in process, easy to form, and convenient for industrial production.
- the composite material obtained by the invention realizes uniform dispersion of the load material in the carbon microspheres and/or the carbon film, and the load is large, and the macroscopic and microscopic heat and mass transfer are obviously strengthened.
- the composite material obtained by the invention breaks the specific surface area limitation of the original skeleton material, and can effectively increase the specific surface area of the composite material and enhance the adsorption, reaction or electron migration rate under the premise of increasing the load.
- the composite material obtained by the invention realizes that the supporting material is directly embedded between the carbon atoms, the anti-agglomeration deactivation ability is obviously enhanced, and the service life is effectively improved.
- the composite material of the invention can be extruded, bonded or brazed to the heat exchange wall of the heat exchanger before and after activation, and the method is flexible and convenient, and can effectively reduce the contact thermal resistance between the adsorbent and the heat exchanger.
- the composite material of the invention has the advantages of simple structure, high heat conduction and electron migration efficiency, strong practicability and easy promotion.
- FIG. 3 SEM of graphite-carbon film-calcium chloride composite material and calcium chloride adsorption cycle 1000 times; wherein A is graphite-carbon film-calcium chloride composite material adsorption cycle 1000 times after SEM; B is calcium chloride adsorption SEM after 10 cycles;
- Figure 4 is a comparison of the graphite-carbon microsphere-calcium chloride composite and the adsorption/deamination kinetics of pure calcium chloride.
- the supporting material is 24 g of calcium chloride
- the supporting framework material is 6 g of expandable graphite
- the solvent is 100 ml of water
- the sugar is 6.16 g of sucrose
- the expandable graphite is treated by heating at 700 ° C for 2 minutes in an oxygen-free environment.
- Expanded graphite dissolve calcium chloride and sucrose in water at 50 ° C and stir evenly to obtain an immersion liquid; impregnate the graphite in the immersion liquid for 1 h at a normal pressure equal volume dipping method, the immersion temperature is 55 ° C, and then form an immersion material
- the dough was dried at 120 ° C for 12 h; at 550 ° C, the dipping was activated in a carbon dioxide atmosphere for 2.5 h, and then taken out and cooled to room temperature in a drying dish to obtain a powdery composite material.
- the composite can be used to adsorb methanol, ethanol, ammonia and water.
- the support skeleton of the composite material is expanded graphite. As shown in Fig.
- the SEM shows that the wall surface forms carbon microspheres having an average particle diameter of about 100 nm, and the calcium chloride is uniformly supported on the carbon microspheres.
- XRD analysis showed no diffraction peak of calcium chloride.
- the calcium chloride content is about 80%.
- the powder adsorbent can also be extruded in a mold with a density of 520 kg/m 3 and bonded to the heat exchange wall by a thermally conductive curing adhesive, and the contact thermal resistance is on the order of 10 -4 m 2 ⁇ K/W.
- the adsorption/desorption time for completing the 80% maximum adsorption amount was only 1/5 of that of pure calcium chloride.
- the supporting material is 24 g of calcium chloride
- the supporting framework material is 6 g of expandable graphite
- the solvent is 100 ml of water
- the sugar is 12 g of glucose
- the expandable graphite is heated to an expansion in an oxygen-free environment at 800 ° C for 2 minutes.
- Graphite dissolving calcium chloride and sucrose in water at 50 ° C and stirring uniformly to obtain an immersion liquid; immersing the graphite in the immersion liquid for 1 hour by an ordinary pressure equal volume dipping method, the immersion temperature is 55 ° C, and then forming an immersion material; The dip was dried by air at 120 ° C for 12 h; at 650 ° C, the impregnated material was activated in a nitrogen atmosphere for 1.5 h, and then taken out and cooled to room temperature in a drying dish to obtain a powdery composite material.
- the composite can be used to adsorb methanol, ethanol, ammonia and water.
- the supporting skeleton of the composite material is expanded graphite. As shown in Fig.
- SEM shows that the secondary expanded wall surface of the expanded graphite forms a carbon film with an average thickness of about 50 nm, and the calcium chloride content is about 75%.
- EDS analysis indicates chlorine. Calcium is uniformly embedded in carbon atoms. It can be seen from Fig. 3 that after 1000 adsorptions, the microstructure of the composite has not changed significantly, and the anti-attenuation ability is superior, while the pure calcium chloride has agglomeration agglomeration only after ten adsorptions.
- the supporting material is 60 g of lithium bromide
- the supporting framework material is 50 g of foamed copper
- the solvent is 50 ml of water
- the sugar is 20 g of amylopectin
- the foamed copper is cut to a desired shape, and the oxide layer is removed; the lithium bromide and the starch are dissolved.
- the impregnation temperature is 80 ° C, the temperature is such that the starch is gelatinized, the copper foam is immersed in the impregnation liquid for 1 hour, and then removed to form an impregnating material; at normal temperature Ventilation and drying 2d; the dipping material and the heat exchange wall are coated with a melting point of 350 ° C solder, and compacted, placed in a vacuum furnace at 450 ° C for 1 h, at the same time complete the activation and vacuum brazing process to form a composite material -
- the heat exchanger is integrally prepared, and its contact thermal resistance is on the order of 10 -5 ⁇ 10 -6 m 2 ⁇ K/W. This type of composite material is mainly used for dehumidification.
- the supporting material is 30 g of silicon monoxide
- the supporting framework material is graphite
- the solvent is 100 ml of water
- the sugar is 10 g of glucose
- the silicon monoxide and glucose are dissolved in 50 ° C water, and stirred uniformly to obtain a suspension impregnation liquid.
- the composite material can be used as a negative electrode for lithium batteries.
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Abstract
Description
Claims (10)
- 一种复合材料,其特征在于,包括:支撑骨架;位于所述支撑骨架上的碳微球和/或碳膜;分散在所述碳微球和/或碳膜中的负载材料。
- 如权利要求1所述的复合材料,其特征在于,所述支撑骨架孔隙壁厚的平均厚度为0.3nm~1mm;或所述碳微球的平均粒径为10nm~0.05mm;或所述膜的平均厚度为1nm~0.05mm;或所述负载材料平均粒径低于10μm;或所述支撑骨架的材料为可膨胀石墨、氧化铝、多孔石墨、多孔纤维、活性炭纤维、泡沫碳、活性炭、石墨纤维、多孔金属、多孔陶瓷、蛭石、石墨烯或硅胶中的至少一种;或所述负载材料:盐为LiCl、BaCl 2、CaBr 2、NaBr、KBr、LiBr、PbCl 2、LiCl、CaCl 2、MnCl 2、BaCl 2、SrCl 2、CoCl 2、MgCl 2、PbCl 2、NiCl 2、FeCl 3、CuCl 2、ZnCl 2、CuCl 2、AgNO 3或Na 2SO 4中一种或多种的组合,电极材料为TiO、氮化物、锡基氧化物、锡合金、金属间化合物、钴酸锂、锰酸锂或磷酸铁锂中一种或多种的组合,物理吸附材料为储氢合金、沸石分子筛及有机金属骨架材料;或所述的多孔支撑骨架、负载材料的质量比为0.5~9;或所述的碳微球和/或碳膜中碳摩尔量与负载材料摩尔量比为0.05~6。
- 如权利要求1所述的复合材料,其特征在于,所述复合材料的接触热阻为10 -6~10 -4m 2·K/W。
- 一种吸附式制冷装置,其特征在于,包括权利要求1-3任一项所述的复合材料。
- 一种变压分离器,其特征在于,包括权利要求1-3任一项所述的复合材料。
- 一种热泵,其特征在于,包括权利要求1-3任一项所述的复合材料。
- 一种复合材料的制备方法,其特征在于,包括:将预处理后的支撑骨架浸渍于糖、负载材料的混合溶液中,干燥、形成膜;活化,膜碳化为碳微球和/或碳膜即得复合材料。
- 如权利要求7所述的方法,其特征在于,所述多孔支撑骨架、负载材料的质量比为1:0.5~9;或所述的糖中的碳摩尔量与负载材料摩尔量比为0.5~6。或所述支撑骨架的材料为可膨胀石墨、氧化铝、多孔石墨、多孔纤维、活性炭纤维、泡沫碳、活性炭、石墨纤维、多孔金属、多孔陶瓷、蛭石、石墨烯或硅胶中的至少一种;或所述负载材料:盐为LiCl、BaCl 2、CaBr 2、NaBr、KBr、LiBr、PbCl 2、LiCl、CaCl 2、MnCl 2、BaCl 2、SrCl 2、CoCl 2、MgCl 2、PbCl 2、NiCl 2、FeCl 3、CuCl 2、ZnCl 2、CuCl 2、AgNO 3或Na 2SO 4中一种或多种的组合,电极材料为TiO、氮化物、锡基氧化物、锡合金、金属间化合物、钴酸锂、锰酸锂或磷酸铁锂中一种或多种的组合,物理吸附材料为储氢合金、沸石分子筛及有机金属骨架材料;或所述糖为单糖、二糖、多糖的至少一种,优选的为葡萄糖、果糖、半乳糖、蔗糖、乳糖、麦芽糖、海藻糖或淀粉中的一种或多种的组合;或所述糖、负载材料的混合溶液还包括负载材料的抗结剂和/或分散剂;或所述预处理的具体操作步骤为:在200~1000℃下、无氧或低氧环境中对支撑骨架进行膨胀;或所述糖、负载材料的混合溶液的配制方法为:于20~120℃下,将糖、负载材料混合均匀;或所述浸渍处理的条件为:于20~120℃下,浸渍1min~48h;或所述干燥处理的条件为:于20~220℃下,干燥1h~10d;或所述活化处理的条件为:于100~1000℃,活化30min~12h;或所述浸渍处理还可采用喷淋处理代替。
- 权利要求7或8所述的方法制备的复合材料。
- 权利要求1-3、9任一项所述的复合材料在电池、环保、除湿、制冷、变压分离提纯、储氢,或空调、热泵制造中的应用。
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