CN114957800B - Graphene nano silicon dioxide composite material and in-situ method for preparing same - Google Patents

Graphene nano silicon dioxide composite material and in-situ method for preparing same Download PDF

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CN114957800B
CN114957800B CN202210676848.0A CN202210676848A CN114957800B CN 114957800 B CN114957800 B CN 114957800B CN 202210676848 A CN202210676848 A CN 202210676848A CN 114957800 B CN114957800 B CN 114957800B
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graphene
silicon dioxide
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nano silicon
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CN114957800A (en
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刘雨蒙
蔡维琪
王卉卉
耿赛
孟祥伟
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Qingdao University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
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    • C09K5/14—Solid materials, e.g. powdery or granular
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • 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
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    • 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

Abstract

The invention discloses a graphene nano silicon dioxide composite material and an in-situ method thereof, wherein (1) 100 parts of graphene dry powder is uniformly dispersed in 1000 parts of deionized water, and then 1-5 parts of dispersing agent is added, and the dispersing agent is stirred to be dissolved and adsorbed on the surface of graphene; (2) Adding 10-100 parts of 10% by mass of concentrated saline solution, adding sodium silicate, stirring and dissolving uniformly, heating, and then rapidly adding 5-10 parts of acidulant; (3) Maintaining the temperature unchanged, reacting sodium silicate with an acidulant to generate silicic acid, and then rapidly performing polycondensation reaction on the silicic acid to obtain nano silicon dioxide which is adsorbed on the surface of graphene through hydroxyl; (4) And (3) after curing the obtained suspension, performing press filtration by using a plate frame, washing and drying to obtain the graphene nano silicon dioxide composite material. The invention effectively solves the problem of aggregation of graphene, and can greatly improve the mechanical strength, thermal conductivity and wear resistance of the material when used in the polymer field.

Description

Graphene nano silicon dioxide composite material and in-situ method for preparing same
Technical Field
The invention provides a graphene nano silicon dioxide composite material and an in-situ method for preparing the same, and particularly relates to the technical field of nano materials.
Background
Graphene is used as a two-dimensional material with high heat conductivity, high electric conductivity and high specific surface area, and various properties of the graphene are closely related to the sheet diameter, the layer number and the dispersibility of the graphene in the material. In particular, in the processing process of the high polymer material, the huge specific surface area of the graphene leads to the processes of mixing the graphene in a pair roller, mixing the graphene in a double screw, mixing the graphene in an internal mixer, mixing the graphene in a high-speed dispersion shearing mode and the like, and the graphene powder is inevitably extruded mutually to fold the graphene into graphite so as to lose the original performance. Therefore, the nano silicon dioxide with proper thickness is wrapped on the surface of the graphene by the in-situ precipitation method, so that the graphene is effectively separated, agglomeration is prevented, and meanwhile, the original performance of the graphene is not affected because the wrapping layer is very thin. Meanwhile, the nano silicon dioxide has good compatibility with various polymers, is also a good polymer reinforcing material, and can realize the effect of 1+1>2 by compounding the nano silicon dioxide and various polymers in the field of polymer reinforcement.
The graphene nano silicon dioxide composite material can well solve the problems. Firstly, the nano silicon dioxide is used as an amorphous nano powder material, and the compatibility with a polymer is very good originally; the nano silicon dioxide/graphene composite material can well solve the problem of compatibility between graphene and a high polymer material; the excellent dispersibility of the graphene can greatly reduce the dosage of the graphene and greatly reduce the cost. The next nanometer silicon dioxide is coated on the surface of the graphene, so that the possibility of contact with oxygen is reduced, meanwhile, the stacking density is improved, dust flying of the graphene is greatly reduced, and the risk of dust explosion is effectively avoided.
The preparation method of the graphene nano silicon dioxide composite material has a very simple principle, and comprises the steps of dispersing graphene in a sodium silicate aqueous solution, adding an acidulant to generate silicic acid, and then carrying out polycondensation to obtain silicon dioxide precipitate which is coated on the surface of the graphene
Firstly, because the surface of graphene is a highly inert benzene ring structure, graphene must be uniformly dispersed in an aqueous solution, and the surface of graphene is required to be provided with hydroxyl functional groups; this ensures that the nano-silica can chemisorb on its surface to form a dense coating; the dispersant chosen must be soluble in water, which requires that the dispersant have both functionalities, with six-membered ring functionalities like polyethylene functionalities or carbon ensuring adsorption on the graphene surface, and hydroxyl functionalities (water-soluble and nano-silica adsorbed). Cellulose, glucose and graphene oxide are selected in the present invention. Wherein graphene oxide has a large number of graphite pendant groups capable of forming a large pi bond association with graphene, and a large number of hydroxyl and carboxyl functional groups ensures that it can be uniformly dispersed in water while adsorbing nano silica.
And secondly, slowly forming a nano silicon dioxide coating layer, if the reaction speed is too high, the rapidly generated nano silicon dioxide particles can be agglomerated to form micron-sized silicon dioxide, which can lead to the graphene surface being coated with a thick layer of silicon dioxide, thereby affecting the electric conductivity and the heat conductivity of the graphene.
Disclosure of Invention
Aiming at the technical problems, the invention provides a graphene nano silicon dioxide composite material and an in-situ method for preparing the same,
the specific technical scheme is as follows:
the graphene nano silicon dioxide composite material is obtained by an in-situ method, and the preparation method specifically comprises the following steps:
(1) Uniformly dispersing 100 parts of graphene dry powder into 1000 parts of deionized water, adding 1-5 parts of dispersing agent, stirring to dissolve and adsorb on the surface of graphene;
(2) Adding 10-100 parts of 10% by mass of concentrated saline solution, adding sodium silicate, stirring and dissolving uniformly, heating, and then rapidly adding 5-10 parts of acidulant;
(3) Maintaining the temperature unchanged, reacting sodium silicate with an acidulant to generate silicic acid, and then rapidly performing polycondensation reaction on the silicic acid to obtain nano silicon dioxide which is adsorbed on the surface of graphene through hydroxyl;
(4) And curing the obtained suspension, press-filtering through a plate frame, washing and drying to obtain the graphene nano silicon dioxide composite material.
Further, the thickness of the graphene sheet is 0.6-50nm, and the average sheet diameter is 10-50um.
The dispersing agent is a water-soluble polymer containing polyhydroxy.
The dosage of the sodium silicate is 100-400 parts.
The strong brine is an inorganic salt solution.
The acidulant is inorganic acid and is used in an amount of 5-10 parts.
The temperature in the step (2) is increased to 40-80 ℃.
And (3) curing in the step (4) for 4-12 hours.
The drying in the step (4) is spray drying, the spray pressure is 3-10bar, the drying temperature is 150-450 ℃, and the spray speed is 200-1200kg/h.
The invention is achieved by first adding a large amount of inorganic salts, such as sodium chloride and sodium sulfate, to the aqueous solution. The homoionic effect rejection effect of sodium ions, the dissolution ionization reaction of sodium silicate in aqueous solution, the equilibrium reaction can control the concentration of sodium silicate in a lower range; meanwhile, chloride ions and sulfate ions can well associate hydrogen ions, and the concentration of silicate ions and hydrogen ions in the solution is well controlled within a very low and very narrow range by the cooperation of the chloride ions and the sulfate ions. As the reaction proceeds, the silicate in the solution reacts with hydrogen ions to form orthosilicic acid, which is then separated to obtain silica. Because of the ion exclusion and absorption, the concentration of orthosilicic acid produced is very low, so that the silica particles obtained by decomposition are very small up to the nanometer scale. Along with the consumption of silicate radical and hydrogen ions in the solution, sodium silicate is continuously ionized to supply silicate radical to react with the hydrogen ions to continuously generate orthosilicic acid, so that nano silicon dioxide is generated. By the process for controlling the silicate ionization reaction and the chemical reaction for generating the orthosilicic acid, the silicate in the solution can be controlled to have a relatively stable concentration, so that the concentration of the silicate is relatively low, and the silicate can be continuously supplemented, thereby reducing manpower and ensuring the quality of products. In addition, in the process of forming silicon dioxide by condensation polymerization of the orthosilicic acid, a large amount of ions in the solution can be adsorbed on the surface of the solution, so that the agglomeration of nano silicon dioxide is effectively prevented.
Graphene with abundant hydroxyl groups on the surface also exists in the solution, and because the surfactant selected by the graphene has high hydroxyl reaction activity, part of silicate groups and hydroxyl groups on the graphene can be subjected to dehydration reaction in the polycondensation and dehydration process of the orthosilicic acid, so that the nano silicon dioxide graphene composite material is formed.
The choice of the acidifying agent is mainly determined by the consistency of the salts added to the reaction solution, for example sodium chloride is added, the corresponding acidifying agent is hydrogen chloride and sodium sulfate is sulfuric acid. This difference is significant, and is most obvious to be green. For a sodium chloride system, if the acidulant is concentrated hydrochloric acid, sodium silicate in the solution and the concentrated hydrochloric acid react to generate orthosilicic acid and sodium chloride, and the orthosilicic acid is condensed to form nano silicon dioxide for separation and collection. No impurity is additionally introduced into the solution, so that the filtered solution after the reaction can be recycled, thereby realizing zero-emission environment-friendly, and the like sulfuric acid system. The choice of acidulant appears to be simple but significant. Thus, like nitric acid, phosphoric acid, perchloric acid, etc., although all can provide hydrogen ions required for the reaction, are not suitable for the present invention.
The selection of graphene is very important, and the selection of high-end high-quality single-layer graphene is good in effect, but the high price of the single-layer graphene is not used in the high-molecular field. On the contrary, the low-end multilayer graphene and even the nano graphite sheet are not easy to agglomerate because the number of layers is very thick, the specific surface area is small, the performance is relatively poor, nano silicon dioxide is not needed to be used for protection, and the traditional micron silicon dioxide is adopted. However, too coarse micron silica encapsulates graphene, which can severely deteriorate the electrical and thermal conductivity and enhance the polymer properties of graphene. Therefore, the thickness of the graphene sheets selected by the invention is 0.6-50nm, the average sheet diameter is 10-50um, wherein the preferable sheet thickness is 5-20nm, and the sheet diameter is 20-30um.
The nano silicon dioxide graphene composite material is carried out in a liquid phase, so that a drying process is important. In order to prevent the nano silicon dioxide graphene composite material from agglomerating in the drying process, a spray drying process is selected. This is a conventional drying process, but is more suitable for the present invention, but the use of the nano-silica graphene composite material is not a precedent. This is because the parameters of the spray drying process adopted in the invention are very special, the spray pressure is 4-10bar, the drying temperature is 150-450 ℃, the spray speed is 200-1200kg/h, wherein the spray pressure is preferably 8-10bar, the drying temperature is 370-420 ℃, and the spray speed is 300-400kg/h; the corresponding device needs to be customized. In order to prevent the drying process of the nano-silica graphene composite material, the agglomeration of nano-silica is caused by the drying shrinkage and the dehydration of hydroxyl groups due to the volatilization of moisture. In order to solve the problem well, the invention adopts special drying conditions. Firstly, the spray pressure is higher, so that the particle size of atomized liquid drops is small, the content of nano silicon dioxide graphene composite materials in the liquid drops is small, and the agglomeration probability is reduced; secondly, the drying temperature is very high and the spraying speed is relatively low, so that the drying speed of the liquid drops is very high, and the agglomeration caused by incomplete drying of the liquid drops can be well avoided. This particular spray drying has the advantage of preventing agglomeration of the silica graphene composite.
Detailed Description
The specific technical scheme of the invention is described by combining the embodiments.
Example 1
Uniformly dispersing 100kg of graphene dry powder with an average particle size of 22um in 1 ton of 10% deionized water solution, and stirring and dissolving 80kg of graphene oxide slurry (the effective content of graphene oxide is 5 percent);
then 250kg of sodium silicate is added, after stirring and dissolving uniformly, the temperature is raised to 50 ℃, then 70kg of 10% sodium chloride aqueous solution is added, then 8.5kg of concentrated hydrochloric acid is rapidly added, and the temperature is maintained unchanged;
after 8 hours of reaction, the obtained suspension is subjected to plate and frame filter pressing, is washed clean, is added with a large amount of water and is stirred into slurry, and is subjected to spray drying, wherein the spray pressure is 6bar, the drying temperature is 400 ℃, and the spray speed is 300kg/h; and obtaining the graphene nano silicon dioxide composite material.
The obtained graphene nano silicon dioxide composite material is added into nylon 66, 5% (wt) is added, and after double-screw extrusion granulation, injection molding is carried out, and the resistivity of the nylon is from 10 -14 Ωcm -3 Up to 8.1 x 10 -7 Ωcm -3 The thermal conductivity increases from 0.271W/(m×k) to 0.511W/(m×k). Conductivity to nylon 66 is improved by 10 8 The heat conducting property is improved by 88.6 percent.
Example 2
Uniformly dispersing 100kg of graphene dry powder with an average particle size of 22um in 1 ton of 10% deionized water solution, adding 80kg of graphene oxide slurry (the effective content of graphene oxide is 5%), and stirring for dissolution;
then 270kg of sodium silicate is added, after stirring and dissolving uniformly, the temperature is raised to 50 ℃, then 70kg of 10% sodium chloride aqueous solution is added, then 8.5kg of concentrated hydrochloric acid is rapidly added, and the temperature is maintained unchanged;
after 8h of reaction, the obtained suspension is subjected to plate and frame filter pressing, is washed clean, is added with a large amount of water and is stirred into slurry, and is subjected to spray drying, wherein the spray pressure is 6bar, the drying temperature is 400 ℃, and the spray speed is 300kg/h, so that the graphene nano silicon dioxide composite material is obtained.
The obtained graphene nano silicon dioxide composite material is added into nylon 66, 5% (wt) is added, and after double-screw extrusion granulation, injection molding is carried out, and the resistivity of the nylon is from 10 -14 Ωcm -3 To 1.3 x 10 -6 Ωcm -3 The thermal conductivity increases from 0.271W/(m×k) to 0.629W/(m×k). Conductivity to nylon 66 is improved by 10 8 The heat conducting property is improved by 132.1 percent.
Example 3
Uniformly dispersing 100kg of graphene dry powder with an average particle size of 22um in 1 ton of 10% deionized water solution, adding 3kg of glucose, and stirring for dissolution;
then 300kg of sodium silicate is added, after stirring and dissolving uniformly, the temperature is raised to 50 ℃, then 50kg of 8% sodium sulfate aqueous solution is added, then 8.4kg of sulfuric acid (50%) is rapidly added, and the temperature is kept unchanged;
after 8h of reaction, the obtained suspension is subjected to plate and frame filter pressing, is washed clean, is added with a large amount of water and is stirred into slurry, and is subjected to spray drying, wherein the spray pressure is 6bar, the drying temperature is 400 ℃, and the spray speed is 300kg/h, so that the graphene nano silicon dioxide composite material is obtained.
The obtained graphene nano silicon dioxide composite material is added into nylon 66, 5% (wt) is added, and after double-screw extrusion granulation, injection molding is carried out, and the resistivity of the nylon is from 10 -14 Ωcm -3 Up to 8.3 x 10 -6 Ωcm -3 The thermal conductivity increases from 0.271W/(m×k) to 0.561W/(m×k). Conductivity to nylon 66 is improved by 10 7 The heat conducting property is improved by 70.1 percent. By using sulphates asThe graphene nano silicon dioxide composite material can be obtained as a control agent.
Example 4
Uniformly dispersing 100kg of graphene dry powder with an average particle size of 22um in 1 ton of 10% deionized water solution, adding 3kg of glucose, and stirring for dissolution;
then 250kg of sodium silicate is added, after stirring and dissolving uniformly, the temperature is raised to 50 ℃, then 70kg of 10% sodium chloride aqueous solution is added, then 8.5kg of concentrated hydrochloric acid is rapidly added, and the temperature is maintained unchanged;
after 8h of reaction, the obtained suspension is subjected to plate and frame filter pressing, is washed clean, is added with a large amount of water and is stirred into slurry, spray drying is carried out, the spray pressure is 3bar, the drying temperature is 200 ℃, and the spray speed is 500kg/h, so that the graphene nano silicon dioxide composite material is obtained.
The obtained graphene nano silicon dioxide composite material is added into nylon 66, 5% (wt) is added, and after double-screw extrusion granulation, injection molding is carried out, and the resistivity of the nylon is from 10 -14 Ωcm -3 To 5.7 x 10 -6 Ωcm -3 The thermal conductivity increases from 0.271W/(m×k) to 0.511W/(m×k). Conductivity to nylon 66 is improved by 10 6 The heat conducting property is improved by 70.1 percent. The enhancement performance of the graphene nano silicon dioxide composite material is deteriorated due to the fact that the spraying pressure is reduced, the drying temperature is reduced and the spraying speed is increased.
Example 5
Uniformly dispersing 100kg of graphene dry powder with an average particle size of 22um in 1 ton of 10% deionized water solution, adding 0.8kg of glucose, and stirring for dissolution;
then 270kg of sodium silicate is added, after stirring and dissolving uniformly, the temperature is raised to 50 ℃, then 70kg of 10% sodium chloride aqueous solution is added, then 8.5kg of concentrated hydrochloric acid is rapidly added, and the temperature is maintained unchanged;
after 8h of reaction, the obtained suspension is subjected to plate and frame filter pressing, is washed clean, is added with a large amount of water and is stirred into slurry, and is subjected to spray drying, wherein the spray pressure is 6bar, the drying temperature is 400 ℃, and the spray speed is 300kg/h, so that the graphene nano silicon dioxide composite material is obtained.
The obtained graphene nano silicon dioxide composite material is added into nylon 66, 5% (wt) is added, and after double-screw extrusion granulation, injection molding is carried out, and the resistivity of the nylon is from 10 -14 Ωcm -3 To 1.3 x 10 -11 Ωcm -3 The thermal conductivity increases from 0.271W/(m×k) to 0.322W/(m×k). Because the nano silicon dioxide cannot be uniformly wrapped on the surface of the graphene due to insufficient consumption of the dispersing agent, when nylon 66 is processed, the graphene is seriously agglomerated and overlapped, so that the conductivity is only improved by 10 3 The heat conduction performance is improved by 18.8 percent; the lifting amplitude is similar to that of adding the traditional graphite and silicon dioxide.
Example 6
Uniformly dispersing 100kg of graphene dry powder with an average particle size of 22um in 1 ton of 10% deionized water solution, adding 3kg of glucose, and stirring for dissolution;
then 270kg of sodium silicate is added, after stirring and dissolving uniformly, the temperature is raised to 50 ℃, then 9kg of 10% sodium chloride aqueous solution is added, then 8.5kg of concentrated hydrochloric acid is rapidly added, and the temperature is maintained unchanged;
after 8h of reaction, the obtained suspension is subjected to plate and frame filter pressing, is washed clean, is added with a large amount of water and is stirred into slurry, and is subjected to spray drying, wherein the spray pressure is 6bar, the drying temperature is 400 ℃, and the spray speed is 300kg/h, so that the graphene nano silicon dioxide composite material is obtained.
The obtained graphene nano silicon dioxide composite material is added into nylon 66, 5% (wt) is added, and after double-screw extrusion granulation, injection molding is carried out, and the resistivity of the nylon is from 10 -14 Ωcm -3 To 4.1 x 10 -3 Ωcm -3 The thermal conductivity increases from 0.271W/(m×k) to 0.330W/(m×k). Conductivity to nylon 66 is improved by 10 3 The heat conducting performance is improved by 21.8 percent; as much as adding conventional graphite and silica.

Claims (7)

1. The in-situ method for preparing the graphene nano silicon dioxide composite material is characterized by comprising the following steps of:
(1) Uniformly dispersing 100 parts of graphene dry powder into 1000 parts of deionized water, and adding 1-5 parts of dispersing agent, wherein the dispersing agent is cellulose, glucose or graphene oxide; stirring to dissolve and adsorb on the surface of graphene;
(2) 10-100 parts of 10% strong brine solution by mass is added, wherein the strong brine is sodium chloride aqueous solution or sodium sulfate aqueous solution; then adding sodium silicate, stirring and dissolving uniformly, heating, and then adding 5-10 parts of acidulant rapidly;
(3) Maintaining the temperature unchanged, reacting sodium silicate with an acidulant to generate silicic acid, and then rapidly performing polycondensation reaction on the silicic acid to obtain nano silicon dioxide which is adsorbed on the surface of graphene through silicon hydroxyl;
(4) Curing the obtained suspension, press-filtering by using a plate frame, washing and drying to obtain the graphene nano silicon dioxide composite material;
the drying is spray drying, the spray pressure is 3-10bar, the drying temperature is 150-450 ℃, and the spray speed is 200-1200kg/h.
2. The method for preparing the graphene nano silicon dioxide composite material by the in-situ method according to claim 1, wherein the graphene has a lamellar thickness of 0.6-50nm and an average lamellar diameter of 10-50um.
3. The method for preparing the graphene nano silicon dioxide composite material by the in-situ method according to claim 1, wherein the dosage of the sodium silicate is 100-400 parts.
4. The method for preparing the graphene nano silicon dioxide composite material by the in-situ method according to claim 1, wherein the acidulant is inorganic acid and is used in an amount of 5-10 parts.
5. The method for preparing the graphene/nano-silica composite material according to claim 1, wherein the temperature in the step (2) is increased to 40-80 ℃.
6. The method for preparing the graphene/nano-silica composite material according to claim 1, wherein the curing is performed for 4-12 hours in the step (4).
7. A graphene nano-silica composite material, characterized in that it is obtained by the in situ process according to any one of claims 1 to 6.
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CN111320970A (en) * 2018-12-13 2020-06-23 山东欧铂新材料有限公司 Nano-silica composite graphene cooling liquid and preparation method thereof

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