RU2690464C1 - Method for synthesis of carbon-mineral composite for producing electrode material of devices storing electric energy - Google Patents

Abstract

FIELD: chemistry.SUBSTANCE: invention relates to chemistry and nanotechnology and can be used in making devices storing electric energy, namely supercondensers. First, temperature preparation of a flow reactor with a loading template in the form of powder of nanoscale particles of inorganic material to synthesis temperature of about 720 °C, when passing flow of inert gas, for example, argon. Then flow of gaseous mixture is passed from gas-diluent and carbon precursor, carbon is deposited on templates to obtain product containing carbon-mineral composite from particles of template with surface coated with graphene of controlled thickness. During synthesis of the product, the reactor is rotated relative to its longitudinal axis, selecting the value of rotation speed based on prevention of dense circular annular concentration of particles in the field of centrifugal forces at the wall of the reactor and their mixing. At that, the reactor is oriented in space so that its longitudinal axis is located horizontally or at an angle to the horizontal, setting the angle formed by the horizontal line and a longitudinal axis of the reactor, with a vertex in the outlet of the reactor, which provides a rate of movement of particles of the template through the reactor in a direction parallel to the axis of the reactor, sufficient to form no more than three monolayers of graphene. Carbon precursor is selected from hydrocarbons of alkanes. Obtained product is purified from formed by-products at temperature of 400 to 720 °C, including said values, for about 1 hour, passing argon or nitrogen at rate of 25 to 50 l/h, including said values, or washing the product in flow mode in acetone to achieve transparency of passing acetone, using a filter, followed by drying in air at temperature of 20–100 °C for about 2 hours.EFFECT: improves uniformity of carbon deposition and purity of the obtained product, reduces consumption of initial materials, increases amount of deposited carbon per unit of weight of the template, increases specific capacity and specific energy of devices with electrodes made using material obtained from said product.8 cl, 8 ex

Description

The technical solution relates to the field of chemistry, in particular, to the production of carbon material for devices that store electrical energy, namely, supercapacitors.

A known method for the synthesis of carbon-mineral composite for the production of electrode material devices that store electrical energy (patent RU 2480405 for the invention). The known method includes pyrolysis in a horizontal tubular reactor of hydrocarbons when heated on a catalyst, which is used as magnesium oxide powder, in a continuous or batch mode, with carbon deposited on the catalyst. Perform pyrolysis of natural gas / methane. The synthesis is carried out at a temperature of from 800 to 950 ° C. The catalyst is magnesium oxide (MgO) is obtained by decomposition of magnesium hydroxide (Mg (OH) ₂ ). The crystalline particles of the catalyst, magnesium oxide, as well as the starting magnesium hydroxide, are in the form of hexagons with a diameter of 100 to 1000 nm and a thickness of 50 to 300 nm. A composite is obtained with carbon deposition and the formation of graphene with a thickness of at least one monolayer.

The method does not solve the technical problem of improving the quality of the electrode material of the devices that store electrical energy, improve the operating parameters of the devices, reduce the cost of the technology for producing the electrode material and increase its performance.

The disadvantages that impede the solution of a technical problem include not quite high uniformity - uniformity over the surface, carbon deposition on the matrix, which is a catalyst, relatively high consumption of raw materials for the synthesis of materials, contamination of the resulting composite, insufficiently high capacitive characteristics of devices storing electrical energy, electrodes which are made using the material obtained from the composite synthesized by the above method, an insufficiently high amount carbon deposited per unit mass of the matrix - catalyst. The reasons for the shortcomings are as follows.

The method is characterized by incomplete conversion of the gas, which is the source of carbon, into precipitated carbon, the possibility of homogeneous reactions, which causes the formation of by-products, in particular polycyclic aromatic hydrocarbons, and their condensation, leading to contamination of the resulting composite.

The synthesis takes place at a fixed catalyst bed, formed by particles of magnesium oxide and located on a pallet of a tubular horizontal reactor. The supply of carbon-containing gas, carried out to a fixed bed of catalyst, with particles that are in a static state, does not ensure its equal effectiveness with respect to various catalyst particles, for example, located on the surface and in the bulk part of the layer. As a result, the efficiency and uniformity of carbon deposition on the catalyst matrix is low. The forming carbon layer is non-uniform - it is uneven over the matrix surface, the amount of carbon deposited is low per unit mass of the matrix, the costs of the initial materials for the synthesis of materials are high.

As the closest analogue, a method for synthesizing a carbon-mineral composite was chosen to produce an electrode material for devices that store electrical energy (patent RU 2641118 for an invention). When implementing the method, temperature preparation of the flow reactor with a loaded template in the form of a powder of nano-sized particles of inorganic material MgO is first carried out to the synthesis temperature by passing an inert gas stream. After preliminary temperature preparation, a stream of gaseous mixture from the diluent gas and carbon precursor is passed with a uniform distribution of the template in the carbon precursor medium. At the same time, carbon is deposited on the template and a product is obtained containing a carbon-mineral composite of template particles with a surface coated with graphene of a controlled thickness equal to 1-2 monolayers of graphene or more. Moreover, the carbon precursor is selected from hydrocarbons of a number of alkanes. Dilution of carbon precursor is controlled by the amount of carbon deposited on the template surface and the uniformity of its deposition. The choice of graphene thickness is combined with the choice of the specific surface of the template, thereby providing the required value of the specific surface of graphene.

The given closest analogue does not fully solve the technical problem of improving the quality of the electrode material of devices storing electrical energy, improving the operating parameters of devices, cheapening the technology for producing electrode material and increasing its performance.

The disadvantages of the closest analogue are not quite high homogeneity, uniformity, carbon deposition on the matrix, which is used as a template, relatively high consumption of raw materials for the synthesis of materials, pollution of the resulting composite, insufficiently high capacitive characteristics of devices that store electrical energy, the electrodes which are made using the material obtained from the composite synthesized by the above method is not a high enough amount of carbon to be deposited per unit m ssy matrix - template.

The nearest analogue is characterized by incomplete conversion of the gas, which is a carbon source, to precipitated carbon, the possibility of homogeneous reactions, which causes the formation of by-products, in particular polycyclic aromatic hydrocarbons, their condensation and leads to contamination of the resulting composite.

The synthesis takes place with a fixed layer of template in the form of a powder of nanoscale particles of inorganic material - MgO. The supply of carbon containing gas, carried out to a fixed template layer, with particles that are in a static state, even with a uniform distribution of the template in the carbon precursor environment, does not ensure its equal effectiveness with respect to various particles. As a result, the efficiency of carbon deposition on the template is not high enough. The carbon layer being formed is not homogeneous enough - it is uniform over the template surface, the amount of carbon being deposited is not high enough per unit mass of the matrix - template, the costs of starting materials for the synthesis of materials are relatively high.

The proposed method is aimed at solving the technical problem of improving the quality of the electrode material of devices storing electrical energy, improving the operating parameters of devices, reducing the cost of the technology for producing electrode material and increasing its performance.

The technical result is:

- improving the uniformity of carbon deposition;

- reducing the consumption of initial materials for the synthesis;

- improvement of the purity of the resulting composite;

- improvement of capacitive characteristics - specific capacity and specific energy - devices storing electrical energy, made on the basis of a two-electrode cell of a symmetrical design, with electrodes made of a material obtained from the synthesized composite;

- increase the amount of carbon deposited per unit mass of the matrix - template.

The technical result is achieved by the method of carbon-mineral composite synthesis for producing electrode material of devices storing electrical energy, including temperature preparation of a flow reactor with a loaded template in the form of a powder of nanoscale particles of an inorganic material to synthesis temperature by passing an inert gas stream, then passing a gaseous mixture stream from carbon diluent and carbon precursor, carbon deposition on the template and product preparation, containing its carbon-mineral composite of template particles with a surface coated with graphene of controlled thickness, the carbon precursor being chosen from hydrocarbons of a number of alkanes; diluting carbon precursor controls the amount of carbon deposited onto the template surface and its precipitation uniformity, and choosing the thickness of the template , thereby ensuring the required value of the specific surface of graphene, in the method after obtaining a product containing carbon-mineral composite from h Templates with a graphene coated surface of a controlled thickness carry out a cleansing treatment that removes polycyclic aromatic hydrocarbons formed during carbon deposition, and by passing a gaseous mixture stream from a diluent gas and carbon precursor, precipitating carbon on the template and obtaining the product, containing a carbon-mineral composite of template particles with a surface coated with graphene of controlled thickness, the reactor is rotated relative to its a rod axis, while the rotation speed value is selected based on preventing centrifugal forces in the field from tightly concentrating particles at the reactor wall and ensuring their mixing by rotating the reactor and sliding to the bottom under the action of gravity of the particles, in addition, the reactor is oriented in space its longitudinal axis horizontally, or oriented at an angle to the horizontal, while setting the value of the angle formed by the horizontal and the longitudinal axis of the reactor, with the top in the output tverstii reactor providing template particles moving speed through the reactor in a direction parallel to the axis of the reactor, which is deposited on carbon, sufficient for the formation of no more than three monolayers graphene.

The method uses a template in the form of a powder of nano-sized particles of an inorganic material — MgO, with a size in diameter of 10 to 15 nm, with a specific surface area of 60 to 70 m ² / g, including the indicated values, temperature preparation of the flow reactor with a loaded template, carried out at passing an inert gas stream until the synthesis temperature is established, which ensures decomposition of the carbon precursor and carbon deposition on the template, about 720 ° C, argon is used as an inert gas.

In the method, when passing a stream of gaseous mixture from a diluent gas and carbon precursor, choosing a hydrocarbon of a number of alkanes as a carbon precursor, a mixture of propane-butane with a composition by volume of 2% ethane, 18% butane and 80% propane, as a diluent gas is used Argon, carbon precursor dilution, controls the amount of carbon deposited on the template surface and its precipitation uniformity when blowing the mixture with an inert gas flow rate from 5 to 10 l / h, including the indicated values, with propane-b mixture consumption of from 20 to 40 l / h, including the specified values, and obtaining the amount of carbon deposited on the template about 9.5% by weight of the template.

In the method, the choice of graphene thickness is combined with the choice of the specific surface of the template, thereby providing the required value of the specific surface of graphene, namely, to form no more than three graphene monolayers, choose a specific surface of the template equal to 60-70 m ² / g, which ensures the required value The specific surface area of graphene is about 1000 m ² / g.

In the method, after receiving a product containing a carbon-mineral composite of template particles with a surface coated with graphene of controlled thickness, it is cleared by treatment, removing the by-products formed during carbon deposition — polycyclic aromatic hydrocarbons, namely, it is subjected to high-temperature cleansing treatment from 400 to 720 ° C, including the indicated values, for about 1 hour, while passing a stream of inert gas of argon or nitrogen with a flow rate from 25 l / h to 50 l / h, including I specified values, with high-temperature cleaning treatment, the reactor is rotated relative to its longitudinal axis, the value of the rotational speed is chosen based on preventing centrifugal forces in the field from densely concentrating particles at the reactor wall and ensuring their mixing by rotating the reactor and slipping to the bottom under the action of gravity of the particles, namely, about 1.4 revolutions per minute, in addition, the reactor is oriented in space with the location of its longitudinal axis horizontally, or oriented at an angle to the horizontal, while setting the value of the angle formed by the horizontal and the longitudinal axis of the reactor, with the top in the outlet of the reactor, providing the speed of movement of the product being cleaned through the reactor in a direction parallel to the axis of the reactor, corresponding to complete cleaning of the product, not more than 1 m / hour.

In the method, after receiving a product containing a carbon-mineral composite of template particles with a surface coated with graphene of controlled thickness, it is treated by cleansing, removing the by-products formed during carbon deposition — polycyclic aromatic hydrocarbons, namely, it is processed in acetone, using a filter, the product is washed in flow through mode in acetone, carrying out washing to achieve transparency of the passing acetone through the product being washed, followed by carbon eralny composite was dried in air at a temperature of from 20 to 100 ° C for about 2 hours.

In the method, by passing a stream of gaseous mixture from a diluent gas and carbon precursor, deposition of carbon on a template and obtaining a product containing a carbon-mineral composite of template particles with a surface covered with graphene of controlled thickness, the reactor is rotated relative to its longitudinal axis, with this value of the rotational speed is chosen based on the prevention in the field of centrifugal forces of dense ring concentration of particles at the reactor wall and ensuring their mixing due to rotation of the reactor and slipping to the bottom under the action of gravity of the particles, namely up to 1.4 revolutions per minute.

The method establishes the angle formed by the horizontal and the longitudinal axis of the reactor, with the top in the outlet of the reactor providing the speed of movement of the template particles through the reactor in a direction parallel to the axis of the reactor, on which carbon is deposited, sufficient to form no more than three monolayers of graphene, namely more than 15 degrees.

The essence of the technical solution is explained in the following description.

When implementing the proposed method, a heterogeneous process proceeds, followed by a chemical reaction at the interface between a solid (template) - gas (a stream of gaseous mixture from a diluent gas and a carbon precursor). It is known that there are two extreme regions of the flow of a heterogeneous process - kinetic and diffusion. During the process in the kinetic region, its speed is limited by the rate of chemical reactions. For a process occurring in the diffusion region, a small amount of the conditional activation energy is characteristic, the temperature has a small effect on the process rate, and the process rate is limited by the diffusion rate.

All heterogeneous processes are associated with the transfer of matter. In them, in particular, three stages can be distinguished: supply of the reagent to the surface; chemical reaction on the surface; removal of the reaction product from the surface. The first and last stage is carried out by diffusion. In many cases, a chemical reaction could proceed very quickly if the supply of the reagent to the surface would occur quickly enough. Such processes, which include the process occurring during the implementation of the proposed method, are diffusion controlled. The speed of the process is determined by the rate of substance transfer (diffusion). If the chemical reaction carried out in the second stage has a high activation energy, then this stage is the slowest. The process is not accelerated with a sufficiently fast supply of the reagent to the surface. Such a heterogeneous process is called kinetically controlled. To accelerate it is necessary to increase the temperature.

Changing the conditions of the deposition process, you can organize the desired course.

When implementing the proposed method, it is necessary to achieve a uniform, uniform deposition of carbon on the template. This means that the reactants supplied to the surface of the solid phase should be distributed evenly over its surface, since it is only under this condition that the reaction product is formed over the entire surface. Uniform deposition is achieved when the process of mass transfer is organized in such a way that the reagents are able to diffuse over long distances, getting to the surface and not immediately reacting to the formation of the product, that is, slowing down the chemical reaction. As you know, the rate of chemical reaction depends on the concentration of reagents on the surface. The lower the concentration of the reactants, the slower the course of the reaction and, as a result, the rate of product formation on the surface of the solid phase is reduced, and the reactants are allowed to diffuse, being distributed more evenly over the surface of the solid phase. Lowering the concentration of reagents and, as a consequence, preventing their premature entry into the reaction, before they are evenly distributed over the surface of the solid phase, is dilution, which is used both in the proposed method and in the closest analogue. Dilution of carbon precursor is a technique by which the uniformity and rate of carbon deposition on the matrix (template) is controlled. Since porous granules consisting of magnesium oxide crystallites are used as a template with a developed specific surface area, at high deposition rates, which is typical in the absence of dilution, carbon will be deposited only on the outer surface of the granules, with no deposition on the surfaces of the pores and folds. Achieving the desired specific surface area of the formed layer on the template will be impracticable. With a high deposition rate, diffusion does not have time to occur in the volume of the granule — folds and pores. The result is an uneven distribution of precipitated carbon over the template surface.

In view of the above, the following should also be noted. If the powdered template is evenly distributed in the carbon precursor environment, in the limiting case forming a layer of one particle thickness when the particles are in contact only with the supporting surface on which the template is located, but the template is stationary, only part of the template surface interacts with the carbon precursor which is washed by the flow of the gaseous mixture from the diluent gas and the carbon precursor. The part of the template surface that is in contact with the supporting surface remains passive. In this regard, the process of mass transfer, despite the implementation of the dilution of carbon precursor, is organized so that the reagents are not able to diffuse, falling on the entire surface of the template.

Therefore, in order to more efficient mass transfer (to the entire template surface) in the proposed solution, by passing a stream of gaseous mixture from the diluent gas and carbon precursor, carbon is deposited on the template, the reactor is rotated relative to its longitudinal axis, the rotation speed value is selected based on prevent in the field of centrifugal forces dense ring concentration of particles at the wall of the reactor and ensure mixing by sliding along the wall to the bottom under the action of gravity particles. Mixing when carrying out the synthesis in a tubular reactor of the horizontal type makes the passive part of the template's surface active, providing access to the reagent. Thus, the efficiency of the mass transfer process is increased.

As a rule, in rotating devices, when a centrifugal force acts on the dispersed phase, separation occurs. For example, a slurry introduced into a rotating drum is thrown against the wall by centrifugal force. Directly particles are concentrated on the wall, and the liquid occupies the central part of the drum. In the proposed method, the goal is to achieve effective mass transfer by mixing. In connection with this, the slow rotation of the reactor is used, during which it is not the separation process that takes place, but mixing.

Providing a more efficient mass transfer due to the rotation of the reactor and mixing with this template helps to improve the homogeneity of carbon deposition, making its deposition more uniform than in the nearest analogue. The consumption of initial materials for the synthesis of materials — a template and a gaseous mixture of a diluent gas and a carbon precursor — is reduced. Since the active area of the template increases with mixing, the smaller amount of template can be dispensed with while precipitating the required amount of carbon. In addition, due to more efficient mass transfer, the conversion of hydrocarbons used as a carbon source to carbon is improved, which means that a smaller amount of the gaseous mixture is required when precipitating the required amount of carbon. For the same reasons, an increase in the amount of carbon deposited per unit mass of the matrix - template is achieved. Also, due to the more complete conversion of hydrocarbons to carbon deposited on the template, the possibility of homogeneous reactions with the formation of polycyclic aromatic hydrocarbons, their condensation and contamination of the resulting composite by them is reduced.

The reactor during the deposition is oriented in space with the location of its longitudinal axis horizontally, or oriented at an angle to the horizontal, while setting the value of the angle formed by the horizontal and longitudinal axis of the reactor, with the top in the outlet of the reactor, providing the speed of movement of the template particles through the reactor in the direction parallel to the axis of the reactor, on which carbon is deposited, sufficient to form at least 1-2 graphene monolayers, but not more than three graphene monolayers. The angle can be set in order to achieve a different speed of movement, ensuring the formation of more than 1-2 graphene monolayers, depending on the amount of carbon that is required to be deposited on the template, on the value of the resulting specific surface of graphene and other parameters. Orientation in the space of the reactor at an angle to the horizontal, on the one hand, helps to improve mass transfer due to the additional components of the mixing motion. On the other hand, this ensures transportation of the loaded template along the reactor, transportation of the product obtained to the outlet of the reactor and its unloading into the receiver. When reaching the edge of the outlet, the intermediate product is poured into the receiver located under the opening. It should be noted that the slope of the reactor allows you to implement a continuous mode of obtaining the product, organizing the continuous loading of the template at the reactor inlet using, for example, screw feeders.

In the proposed method for the synthesis of carbon composite to obtain the electrode material of devices that store electrical energy, an additional step is introduced to purify the resulting product as a result of carbon deposition on the template. So, after receiving a product from template particles coated with graphene, which is an intermediate product containing impurities, it is subjected to its purification treatment, removing the by-products formed during carbon deposition - polycyclic aromatic hydrocarbons. This cleaning treatment is carried out either using high-temperature treatment in the reactor, or using flow rinsing with acetone.

Improvement of capacitive characteristics — specific capacity and specific energy — devices storing electrical energy, made on the basis of a two-electrode cell of a symmetrical design, with electrodes made of a material obtained from the synthesized composite, results from a reduction in the resulting polycyclic aromatic products in the resulting final product hydrocarbons, mainly naphthalene and anthracene. The content reduction is provided, firstly, due to a more complete conversion of hydrocarbons to carbon deposited on the template, achieved due to more efficient mass transfer to the template surface using rotation and tilting of the reactor and mixing with the template, and, accordingly, less formation of side products reaction. Secondly, as a result of the ongoing final purification treatment of the intermediate product, specially undertaken to clean it.

Thus, the above essential features in accordance with the disclosed mechanisms ensure the achievement of the aforementioned complex technical result, due to which the technical problem of improving the quality of the electrode material of devices storing electrical energy, improving the operating parameters of devices, reducing the cost of producing electrode material and increasing its performance is more fully resolved .

The implementation of the method is carried out in three stages.

The first stage is preparatory.

Receive the template. As such, choose, in particular, magnesium oxide or another. Magnesium oxide is obtained by calcining magnesium hydroxycarbonate at a temperature of about 720 ° C, including the indicated values, in air. Prodka spend about 4-6 hours. Prepare magnesium oxide with a particle size in the diameter of about 10-15 nm and a specific surface of the template of about 60-70 m ² / g.

At the second stage, an intermediate product is obtained, which is to be cleared of impurities after the implementation of this stage.

Conduct temperature training flow reactor with a loaded template in the form of a powder of nanoscale particles of inorganic material to the synthesis temperature by passing an inert gas stream. Then pass the flow of the gaseous mixture from the diluent gas and carbon precursor. Carbon is deposited on the template and the product is obtained from template particles coated with graphene of controlled thickness on the surface of the particles. The carbon precursor is selected from hydrocarbons of a number of alkanes. Dilution of carbon precursor is controlled by the amount of carbon deposited on the template surface and the uniformity of its deposition. The choice of graphene thickness is combined with the choice of the specific surface of the template, thereby providing the required value of the specific surface of graphene. By passing a stream of gaseous mixture from a diluent gas and a carbon precursor, carbon is deposited on a template and a product is obtained from particles of a template coated with graphene, the reactor is rotated relative to its longitudinal axis. The value of the rotational speed is chosen based on the prevention in the field of centrifugal forces of dense ring concentration of particles at the reactor wall and ensuring mixing by sliding to the bottom under the action of the force of gravity of the particles, respectively, of the template on which carbon is deposited, covered with graphene. Rotational speed set at 1.4 revolutions per minute. The reactor is oriented in space with the location of its longitudinal axis at an angle to the horizontal, or oriented at an angle to the horizontal, while setting the value of the angle formed by the horizontal and the longitudinal axis of the reactor, with the top in the outlet of the reactor providing the speed of movement of the template particles through the reactor in the direction parallel to the axis of the reactor, on which carbon is deposited, sufficient to form at least 1-2 graphene monolayers, but not more than three monolayers. The angle is set for these purposes not more than 15 degrees.

The template is used in the form of a powder of nano-sized particles of an inorganic material — for example, MgO, that is, a metal oxide of the second group, providing chemical and thermal stability, no modification of the structure and composition, chemical inertness with respect to carbon, good solubility in acidic solutions. The particle size of the template in diameter ranges from 10 to 15 nm. The template particles have a developed specific surface area - from 60 to 70 m ² / g, which provides the prerequisites for obtaining graphene during the deposition of carbon on the template with the required specific surface area. Temperature preparation of the flow reactor with a loaded template is carried out by passing an inert gas stream until the synthesis temperature is established. At temperature preparation of the reactor it is possible to bring it into rotation. The temperature should ensure the decomposition of the carbon precursor and the carbon deposition on the template. The temperature is chosen about 720 ° C. Argon is used as inert gas. Perhaps instead of argon use nitrogen. Pass the stream of inert gas with a flow rate of 20 l / h.

By passing a stream of gaseous mixture from the diluent gas and carbon precursor, for which carbon is chosen as a carbon alkane hydrocarbon precursor, for example, a propane-butane mixture with a composition by volume of 2% ethane, 18% butane and 80% propane is used. Argon is used as a diluent gas. Dilution of carbon precursor is controlled by the amount of carbon deposited on the template surface and the uniformity of its deposition. To precipitate carry out the blowing of the mixture with the supply of inert gas flow rate from 5 to 10 l / h, including the specified values, with the flow of a mixture of propane-butane flow rate from 20 to 40 l / h, including the specified values. The amount of carbon deposited per template is about 9.5% by weight of the template.

When carbon is deposited on a template and a product is obtained, from template particles coated with graphene of controlled thickness, in which the choice of graphene thickness is combined with the choice of the specific surface of the template, thereby providing the required specific surface area of graphene, namely for forming at least 1-2 monolayers graphene, but not more than three monolayers, choose a specific surface of the template equal to 60-70 m ² / g, which ensures the required value of the specific surface of graphene about 1000 m ² / g.

The resulting intermediate product contains, by volume, 0.2-0.6 mass% of polycyclic aromatic hydrocarbons — products of polymerization and condensation that were formed during the process of carbon deposition on the template. Therefore, after receiving the product from the particles of the template coated with graphene, it is necessary to remove the products of side reactions. For this purpose, a treatment is undertaken that removes the by-products formed during carbon deposition — polycyclic aromatic hydrocarbons.

At the third and final stage, the resulting intermediate product is purified. This stage can be done in two ways.

In the first embodiment, a high-temperature cleaning treatment in the reactor is used.

The intermediate product obtained and collected in the receiver is loaded into the reactor for purification and its high-temperature treatment is carried out at a temperature not lower than the boiling point of the aromatic compounds formed, mainly naphthalene, anthracene. The result is the volatilization of aromatic compounds, the synthesized product is purified. When implementing a high-temperature cleaning treatment, the reactor is also rotated relative to its longitudinal axis, while the rotation speed value is selected based on preventing centrifugal forces in the field from tightly concentrating particles at the reactor wall and ensuring mixing due to the product particles gravitating to the bottom from the template covered with graphene. Stirring facilitates diffusion and removal of the reaction by-product. The speed of rotation, in particular, is set at 1.4 revolutions per minute.

The reactor with high-temperature cleaning treatment is oriented in space with the location of its longitudinal axis horizontally, or oriented at an angle to the horizontal, while setting the value of the angle formed by the horizontal and the longitudinal axis of the reactor, with the apex in the outlet of the reactor, providing the speed of movement of the product being cleaned through the reactor in the direction parallel to the axis of the reactor, which corresponds to complete cleaning of the product, not more than 1 m / h. On the one hand, this measure helps to improve the diffusion of the side reaction product withdrawn due to an additional component of the mixing motion. On the other hand, this ensures transportation of the intermediate product being loaded along the reactor, transportation of the resulting final purified product to the outlet of the reactor and its unloading into the receiver.

The limitation on the angle prevents premature unloading of the product from the reactor and ensures complete cleaning.

A high-temperature purification treatment is carried out, which removes the by-products formed during carbon deposition — polycyclic aromatic hydrocarbons at a temperature of 400 to 720 ° C, including the indicated values, for about 1 hour. At the same time, an inert gas stream of argon or nitrogen is passed with a flow rate from 25 l / h to 50 l / h, including the indicated values.

In the second embodiment, using a cleansing treatment with acetone.

After obtaining a product containing a carbon-mineral composite of template particles with a surface coated with graphene of controlled thickness, it is subjected to a cleansing treatment in acetone that removes the by-products formed during carbon deposition — polycyclic aromatic hydrocarbons. In this case, using a filter, the product is washed under flow conditions. Carry out washing to achieve transparency of the passing acetone through the washed product. Then the carbon-mineral composite is dried in air at a temperature of from 20 to 100 ° C for about 2 hours.

For the implementation of the second stage and the high-temperature purification treatment of the third stage of the described synthesis, a flow tube reactor with a nominal diameter of about 100 mm, a length of about 1600 mm, and a heating zone length of about 1,100 mm can be used. The reactor is equipped with a three-zone electric oven, which, using heaters and thermocouples, maintains the temperature with an accuracy of 1 ° C.

During the development of the proposed method for synthesizing carbon composite to obtain an electrode material of devices storing electrical energy, an electrode material obtained from the intermediate and final synthesis products was tested.

In order to obtain the electrode material from the intermediate and final products, the template was removed. A two-electrode cell of a symmetrical design was formed, which was filled with an ionic liquid that performs the function of an electrolyte. When conducting testing measurements were obtained the following capacitive characteristics.

When using an electrode material obtained from an intermediate product, data were obtained: specific capacity 28 F / g at a discharge current of 0.2 A / g; specific energy 42 Wh / kg per operating voltage of 3 V.

When using the electrode material obtained from the final product, that is, having undergone a high-temperature purification treatment, the data were obtained: the specific capacity reached up to 47 F / g at a discharge current of 0.2 A / g; specific energy reached 57.5 Wh / kg in the calculation of the operating voltage of 3 V.

As information confirming the possibility of implementing the method with the achievement of the technical result, we give the following specific examples of implementation.

Example 1

The method of synthesis of carbon composite to obtain the electrode material of the device, storing electrical energy, is as follows.

Previously obtained template, which is used as a powder of nanoscale particles of an inorganic material - metal oxide of the second group, providing chemical and thermal stability, no modification of structure and composition, chemical inertness with respect to carbon, good solubility in acidic solutions of magnesium oxide, is loaded into the reactor . Template - magnesium oxide is characterized by a particle size in the diameter of about 10-15 nm and a specific surface of the template of about 60-70 m ² / g.

Conduct temperature training flow tube reactor with a loaded template to the synthesis temperature by passing an inert gas stream with a flow rate of 20 l / h. Argon is used as inert gas. The preparation is carried out until the temperature of the synthesis is established, which ensures decomposition of the carbon precursor and carbon deposition on the template, about 720 ° C.

Then pass a stream of gaseous mixture from the diluent gas and carbon precursor, feeding it through the inlet. Moreover, the carbon precursor is selected from hydrocarbons of a number of alkanes - using a mixture of propane-butane with a composition by volume of 2% ethane, 18% butane and 80% propane. Argon is used as a diluent gas. The carbon precursor dilution is controlled by the amount of carbon deposited on the template surface and its deposition uniformity when blowing the mixture with the supply of inert gas with a flow rate of 5 l / h and feeding the propane-butane mixture with a flow rate of 20 l / h. Get the amount of carbon deposited on the surface of the template, amounting to about 9.5% by weight of the template. At the same time, carbon is deposited on the template and the product is obtained from template particles coated with graphene of controlled thickness of 2-3 graphene monolayers. The choice of the thickness of graphene is combined with the choice of the specific surface of the template to obtain the specific surface of graphene of the required value of 1000 m ² / g. The deposition is carried out for about 60 minutes. When implementing the flow of a gaseous mixture from a diluent gas and carbon precursor, carbon is deposited on a template and a product is obtained from particles of a template covered with graphene, the reactor is rotated relative to its longitudinal axis, the value of the rotational speed is chosen based on prevention in the centrifugal field Forces of dense ring concentration of particles at the wall of the reactor and ensuring mixing by sliding to the bottom by the action of gravity of the particles of the template on which they are deposited glerod and the formed intermediate product - about 1.4 revolutions per minute. In addition, the reactor is oriented in space in such a way that the angle formed by the horizontal and the longitudinal axis of the reactor, with the top in the outlet of the reactor, is about 5 degrees. The value of the angle formed by the horizontal and the longitudinal axis of the reactor, with the top in the outlet of the reactor, provides the speed of movement of the template particles through the reactor in a direction parallel to the axis of the reactor, on which carbon is deposited, sufficient to form 2-3 monolayers.

After the deposition of carbon on the template, the resulting product from graphene-coated template particles is collected in a receiver located at the reactor outlet, it is loaded into the reactor and its high-temperature purification treatment is carried out, removing polycyclic aromatic hydrocarbons formed during carbon deposition. The treatment is carried out at a temperature of 700 ° C, for about 1 hour, by passing a stream of inert argon gas at a flow rate of 50 l / h. When processing, the reactor is rotated relative to its longitudinal axis, the rotational speed is chosen based on preventing centrifugal forces in the field from tightly concentrating particles at the reactor wall and ensuring mixing by sliding the particles from the template covered by the gravity to the bottom graphene - at a speed of 1.4 revolutions per minute. In addition, the reactor is oriented in space in such a way that the angle formed by the horizontal and the longitudinal axis of the reactor, with the top in the outlet of the reactor, is 5 degrees. Set the angle formed by the horizontal and the longitudinal axis of the reactor, with the top in the outlet of the reactor, providing the speed of movement of the product being cleaned through the reactor in a direction parallel to the axis of the reactor, corresponding to complete cleaning of the product, not more than 1 m / hour.

Conducted testing of the resulting electrode material from the carbon-mineral composite after removing the template. A two-electrode cell of a symmetrical design was formed, which was filled with an ionic liquid that performs the function of an electrolyte. When conducting test measurements, a specific capacity of 32 F / g was obtained at a discharge current of 0.2 A / g.

Example 2

The method of synthesis of carbon composite to obtain the electrode material of the device, storing electrical energy, is as follows.

Previously obtained template, which is used as a powder of nanoscale particles of an inorganic material - metal oxide of the second group, providing chemical and thermal stability, no modification of structure and composition, chemical inertness with respect to carbon, good solubility in acidic solutions of magnesium oxide, is loaded into the reactor . Template - magnesium oxide is characterized by a particle size in the diameter of about 10-15 nm and a specific surface of the template of about 60-70 m ² / g.

Conduct temperature training flow tube reactor with a loaded template to the synthesis temperature by passing an inert gas stream with a flow rate of 20 l / h. Argon is used as inert gas. The preparation is carried out until the temperature of the synthesis is established, which ensures the decomposition of the carbon precursor and the carbon deposition on the template, about 700 ° C.

Then pass a stream of gaseous mixture from the diluent gas and carbon precursor, feeding it through the inlet. Moreover, the carbon precursor is selected from hydrocarbons of a number of alkanes - using a mixture of propane-butane with a composition by volume of 2% ethane, 18% butane and 80% propane. Argon is used as a diluent gas. The carbon precursor dilution is controlled by the amount of carbon deposited on the template surface and its deposition uniformity when blowing the mixture with the supply of inert gas with a flow rate of 10 l / h and feeding the propane-butane mixture with a flow rate of 40 l / h. Get the amount of carbon deposited on the surface of the template, amounting to about 9.5% by weight of the template. At the same time, carbon is deposited on the template and the product is obtained from template particles coated with graphene of controlled thickness equal to 2-3 graphene monolayers. The choice of the thickness of graphene is combined with the choice of the specific surface of the template to obtain the specific surface of graphene of the required value of 1000 m ² / g. The precipitation is carried out for about 27 minutes. When implementing the flow of a gaseous mixture from a diluent gas and carbon precursor, carbon is deposited on a template and a product is obtained from particles of a template covered with graphene, the reactor is rotated relative to its longitudinal axis, the value of the rotational speed is chosen based on the prevention of centrifugal Forces of dense ring concentration of particles at the wall of the reactor and ensuring mixing by sliding to the bottom by the action of gravity of the particles of the template on which they are deposited glerod and the formed intermediate product - about 1.4 revolutions per minute. In addition, the reactor is oriented in space in such a way that the angle formed by the horizontal and the longitudinal axis of the reactor, with the top in the outlet of the reactor, is about 15 degrees. The value of the angle formed by the horizontal and the longitudinal axis of the reactor, with the top in the outlet of the reactor, provides the speed of movement of the template particles through the reactor in a direction parallel to the axis of the reactor, on which carbon is deposited, sufficient to form the specified number of graphene monolayers.

After the deposition of carbon on the template, the resulting product from graphene-coated template particles is collected in a receiver located at the reactor outlet, it is loaded into the reactor and its high-temperature purification treatment is carried out, removing polycyclic aromatic hydrocarbons formed during carbon deposition. The treatment is carried out at a temperature of 400 ° C, for about 1 hour, by passing an argon inert gas stream at a flow rate of 25 l / h. When processing, the reactor is rotated relative to its longitudinal axis, the rotational speed is chosen based on preventing centrifugal forces in the field from tightly concentrating particles at the reactor wall and ensuring mixing by sliding the particles from the template covered by the gravity to the bottom graphene - at a speed of 1.4 revolutions per minute. In addition, the reactor is oriented in space in such a way that the angle formed by the horizontal and the longitudinal axis of the reactor, with the top in the outlet of the reactor, is 15 degrees. Set the angle formed by the horizontal and the longitudinal axis of the reactor, with the top in the outlet of the reactor, providing the speed of movement of the product being cleaned through the reactor in a direction parallel to the axis of the reactor, corresponding to complete cleaning of the product, not more than 1 m / hour.

Conducted testing of the resulting electrode material from the carbon-mineral composite after removing the template. A two-electrode cell of a symmetrical design was formed, which was filled with an ionic liquid that performs the function of an electrolyte. When conducting test measurements, a specific capacitance of 46 F / g was obtained at a discharge current of 0.2 A / g.

Example 3

The method of synthesis of carbon composite to obtain the electrode material of the device, storing electrical energy, is as follows.

Previously obtained template, which is used as a powder of nanoscale particles of an inorganic material - metal oxide of the second group, providing chemical and thermal stability, no modification of structure and composition, chemical inertness with respect to carbon, good solubility in acidic solutions of magnesium oxide, is loaded into the reactor . Template - magnesium oxide is characterized by a particle size in the diameter of about 10-15 nm and a specific surface of the template of about 60-70 m ² / g.

Conduct temperature training flow tube reactor with a loaded template to the synthesis temperature by passing an inert gas stream with a flow rate of 25 l / h. Argon is used as inert gas. The preparation is carried out until the temperature of the synthesis is established, which ensures decomposition of the carbon precursor and carbon deposition on the template, about 730 ° C.

Then pass a stream of gaseous mixture from the diluent gas and carbon precursor, feeding it through the inlet. Moreover, the carbon precursor is selected from hydrocarbons of a number of alkanes - using a mixture of propane-butane with a composition by volume of 2% ethane, 18% butane and 80% propane. Argon is used as a diluent gas. The carbon precursor dilution is controlled by the amount of carbon deposited on the template surface and its deposition uniformity when blowing the mixture with the supply of inert gas with a flow rate of 7.5 l / h and feeding the propane-butane mixture with a flow rate of 30 l / h. Get the amount of carbon deposited on the surface of the template, amounting to about 9.5% by weight of the template. At the same time, carbon is deposited on the template and the product is obtained from template particles coated with graphene of controlled thickness of 2-3 graphene monolayers. The choice of the thickness of graphene is combined with the choice of the specific surface of the template to obtain the specific surface of graphene of the required value of 1000 m ² / g. The deposition is carried out for about 40 minutes. When implementing the flow of a gaseous mixture from a diluent gas and carbon precursor, carbon is deposited on a template and a product is obtained from particles of a template covered with graphene, the reactor is rotated relative to its longitudinal axis, the value of the rotational speed is chosen based on prevention in the centrifugal field Forces of dense ring concentration of particles at the wall of the reactor and ensuring mixing by sliding to the bottom by the action of gravity of the particles of the template on which they are deposited glerod and the formed intermediate product - about 1.4 revolutions per minute. In addition, the reactor is oriented in space in such a way that the angle formed by the horizontal and the longitudinal axis of the reactor, with the top in the outlet of the reactor, is about 11 degrees. The value of the angle formed by the horizontal and the longitudinal axis of the reactor, with the top in the outlet of the reactor, provides the speed of movement of the template particles through the reactor in a direction parallel to the axis of the reactor, on which carbon is deposited, sufficient to form a graphene thickness of 2-3 monolayers.

After the deposition of carbon on the template, the resulting product from graphene-coated template particles is collected in a receiver located at the reactor outlet, it is loaded into the reactor and its high-temperature purification treatment is carried out, removing polycyclic aromatic hydrocarbons formed during carbon deposition. The treatment is carried out at a temperature of 720 ° C, for about 1 hour, by passing an argon inert gas stream at a flow rate of 28 l / h. When processing, the reactor is rotated relative to its longitudinal axis, the rotational speed is chosen based on preventing centrifugal forces in the field from tightly concentrating particles at the reactor wall and ensuring mixing by sliding the particles from the template covered by the gravity to the bottom graphene - at a speed of 1.4 revolutions per minute. In addition, the reactor is oriented in space in such a way that the angle formed by the horizontal and the longitudinal axis of the reactor, with the top in the outlet of the reactor, is 14 degrees. Set the angle formed by the horizontal and the longitudinal axis of the reactor, with the top in the outlet of the reactor, providing the speed of movement of the product being cleaned through the reactor in a direction parallel to the axis of the reactor, corresponding to complete cleaning of the product, not more than 1 m / hour.

Conducted testing of the resulting electrode material from the carbon-mineral composite after removing the template. A two-electrode cell of a symmetrical design was formed, which was filled with an ionic liquid that performs the function of an electrolyte. When conducting test measurements, a specific capacity of 32 F / g was obtained at a discharge current of 0.2 A / g.

Example 4

The method of synthesis of carbon composite to obtain the electrode material of the device, storing electrical energy, is as follows.

Previously obtained template, which is used as a powder of nanoscale particles of an inorganic material - metal oxide of the second group, providing chemical and thermal stability, no modification of structure and composition, chemical inertness with respect to carbon, good solubility in acidic solutions of magnesium oxide, is loaded into the reactor . Template - magnesium oxide is characterized by a particle size in the diameter of about 10-15 nm and a specific surface of the template of about 60-70 m ² / g.

Conduct temperature training flow tube reactor with a loaded template to the synthesis temperature by passing an inert gas stream with a flow rate of 20 l / h. Argon is used as inert gas. The preparation is carried out until the temperature of the synthesis is established, which ensures the decomposition of the carbon precursor and the carbon deposition on the template, about 700 ° C.

Then pass a stream of gaseous mixture from the diluent gas and carbon precursor, feeding it through the inlet. Moreover, the carbon precursor is selected from hydrocarbons of a number of alkanes - using a mixture of propane-butane with a composition by volume of 2% ethane, 18% butane and 80% propane. Argon is used as a diluent gas. The carbon precursor dilution is controlled by the amount of carbon deposited on the template surface and its deposition uniformity when blowing the mixture with the supply of inert gas with a flow rate of 10 l / h and feeding the propane-butane mixture with a flow rate of 40 l / h. Get the amount of carbon deposited on the surface of the template, amounting to about 9.5% by weight of the template. At the same time, carbon is deposited on the template and a product is obtained from template particles coated with graphene of controlled thickness equal to 3 graphene monolayers. The choice of the thickness of graphene is combined with the choice of the specific surface of the template to obtain the specific surface of graphene of the required value of 1000 m ² / g. The precipitation is carried out for about 27 minutes. When implementing the flow of a gaseous mixture from a diluent gas and carbon precursor, carbon is deposited on a template and a product is obtained from particles of a template covered with graphene, the reactor is rotated relative to its longitudinal axis, the value of the rotational speed is chosen based on prevention in the centrifugal field Forces of dense ring concentration of particles at the wall of the reactor and ensuring mixing by sliding to the bottom by the action of gravity of the particles of the template on which they are deposited glerod and the formed intermediate product - about 1.4 revolutions per minute. In addition, the reactor is oriented in space in such a way that the angle formed by the horizontal and the longitudinal axis of the reactor, with the top in the outlet of the reactor, is about 15 degrees. The value of the angle formed by the horizontal and the longitudinal axis of the reactor, with the top in the outlet of the reactor, provides the speed of movement of the template particles through the reactor in a direction parallel to the axis of the reactor, on which carbon is deposited, sufficient to form the specified number of graphene monolayers.

After the deposition of carbon on the template, the resulting product from graphene-coated template particles is collected in a receiver located at the reactor outlet, it is loaded into the reactor and its high-temperature purification treatment is carried out, removing polycyclic aromatic hydrocarbons formed during carbon deposition. The treatment is carried out at a temperature of 500 ° C, for about 1 hour, by passing a stream of inert argon gas at a flow rate of 25 l / h. When processing, the reactor is rotated relative to its longitudinal axis, the rotational speed is chosen based on preventing centrifugal forces in the field from tightly concentrating particles at the reactor wall and ensuring mixing by sliding the particles from the template covered by the gravity to the bottom graphene - at a speed of 1.4 revolutions per minute. In addition, the reactor is oriented in space in such a way that the angle formed by the horizontal and the longitudinal axis of the reactor, with the top in the outlet of the reactor, is 15 degrees. Set the angle formed by the horizontal and the longitudinal axis of the reactor, with the top in the outlet of the reactor, providing the speed of movement of the product being cleaned through the reactor in a direction parallel to the axis of the reactor, corresponding to complete cleaning of the product, not more than 1 m / hour.

Conducted testing of the resulting electrode material from the carbon-mineral composite after removing the template. A two-electrode cell of a symmetrical design was formed, which was filled with an ionic liquid that performs the function of an electrolyte. When conducting test measurements, a specific capacity of 47 F / g was obtained at a discharge current of 0.2 A / g.

Example 5

The method of synthesis of carbon composite to obtain the electrode material of the device, storing electrical energy, is as follows.

Previously obtained template, which is used as a powder of nanoscale particles of an inorganic material - metal oxide of the second group, providing chemical and thermal stability, no modification of structure and composition, chemical inertness with respect to carbon, good solubility in acidic solutions of magnesium oxide, is loaded into the reactor . Template - magnesium oxide is characterized by a particle size in the diameter of about 10-15 nm and a specific surface of the template of about 60-70 m ² / g.

Conduct temperature training flow tube reactor with a loaded template to the synthesis temperature by passing an inert gas stream with a flow rate of 20 l / h. Argon is used as inert gas. The preparation is carried out until the temperature of the synthesis is established, which ensures the decomposition of the carbon precursor and the carbon deposition on the template, about 700 ° C.

Then pass a stream of gaseous mixture from the diluent gas and carbon precursor, feeding it through the inlet. Moreover, the carbon precursor is selected from hydrocarbons of a number of alkanes - using a mixture of propane-butane with a composition by volume of 2% ethane, 18% butane and 80% propane. Argon is used as a diluent gas. The carbon precursor dilution is controlled by the amount of carbon deposited on the template surface and its deposition uniformity when blowing the mixture with the supply of inert gas with a flow rate of 10 l / h and feeding the propane-butane mixture with a flow rate of 40 l / h. Get the amount of carbon deposited on the surface of the template, amounting to about 9.5% by weight of the template. At the same time, carbon is deposited on the template and a product is obtained from template particles coated with graphene of controlled thickness equal to 3 graphene monolayers. The choice of the thickness of graphene is combined with the choice of the specific surface of the template to obtain the specific surface of graphene of the required value of 1000 m ² / g. The precipitation is carried out for about 27 minutes. When implementing the flow of a gaseous mixture from a diluent gas and carbon precursor, carbon is deposited on a template and a product is obtained from particles of a template covered with graphene, the reactor is rotated relative to its longitudinal axis, the value of the rotational speed is chosen based on prevention in the centrifugal field Forces of dense ring concentration of particles at the wall of the reactor and ensuring mixing by sliding to the bottom by the action of gravity of the particles of the template on which they are deposited glerod and the formed intermediate product - about 1.4 revolutions per minute. In addition, the reactor is oriented in space in such a way that the angle formed by the horizontal and the longitudinal axis of the reactor, with the top in the outlet of the reactor, is about 15 degrees. The value of the angle formed by the horizontal and the longitudinal axis of the reactor, with the top in the outlet of the reactor, provides the speed of movement of the template particles through the reactor in a direction parallel to the axis of the reactor, on which carbon is deposited, sufficient to form the specified number of graphene monolayers.

After the deposition of carbon on the template, the resulting product from graphene-coated template particles is collected in a receiver located at the reactor outlet, it is loaded into the reactor and its high-temperature purification treatment is carried out, removing polycyclic aromatic hydrocarbons formed during carbon deposition. The treatment is carried out at a temperature of 600 ° C for about 1 hour, by passing a stream of inert argon gas at a flow rate of 25 l / h. When processing, the reactor is rotated relative to its longitudinal axis, the rotational speed is chosen based on preventing centrifugal forces in the field from tightly concentrating particles at the reactor wall and ensuring mixing by sliding the particles from the template covered by the gravity to the bottom graphene - at a speed of 1.4 revolutions per minute. In addition, the reactor is oriented in space in such a way that the angle formed by the horizontal and the longitudinal axis of the reactor, with the top in the outlet of the reactor, is 15 degrees. Set the angle formed by the horizontal and the longitudinal axis of the reactor, with the top in the outlet of the reactor, providing the speed of movement of the product being cleaned through the reactor in a direction parallel to the axis of the reactor, corresponding to complete cleaning of the product, not more than 1 m / hour.

Conducted testing of the resulting electrode material from the carbon-mineral composite after removing the template. A two-electrode cell of a symmetrical design was formed, which was filled with an ionic liquid that performs the function of an electrolyte. When conducting testing measurements, a specific capacity of 36 F / g was obtained at a discharge current of 0.2 A / g.

Example 6

The method of synthesis of carbon composite to obtain the electrode material of the device, storing electrical energy, is as follows.

Previously obtained template, which is used as a powder of nanoscale particles of an inorganic material - metal oxide of the second group, providing chemical and thermal stability, no modification of structure and composition, chemical inertness with respect to carbon, good solubility in acidic solutions of magnesium oxide, is loaded into the reactor . Template - magnesium oxide is characterized by a particle size in the diameter of about 10-15 nm and a specific surface of the template of about 60-70 m ² / g.

Conduct temperature training flow tube reactor with a loaded template to the synthesis temperature by passing an inert gas stream with a flow rate of 20 l / h. Argon is used as inert gas. The preparation is carried out until the temperature of the synthesis is established, which ensures the decomposition of the carbon precursor and the carbon deposition on the template, about 700 ° C.

Then pass a stream of gaseous mixture from the diluent gas and carbon precursor, feeding it through the inlet. Moreover, the carbon precursor is selected from hydrocarbons of a number of alkanes - using a mixture of propane-butane with a composition by volume of 2% ethane, 18% butane and 80% propane. Argon is used as a diluent gas. The carbon precursor dilution is controlled by the amount of carbon deposited on the template surface and its deposition uniformity when blowing the mixture with the supply of inert gas with a flow rate of 10 l / h and feeding the propane-butane mixture with a flow rate of 40 l / h. Get the amount of carbon deposited on the surface of the template, amounting to about 9.5% by weight of the template. At the same time, carbon is deposited on the template and the product is obtained from template particles coated with graphene of controlled thickness of 2-3 graphene monolayers. The choice of the thickness of graphene is combined with the choice of the specific surface of the template to obtain the specific surface of graphene of the required value of 1000 m ² / g. The precipitation is carried out for about 27 minutes. When implementing the flow of a gaseous mixture from a diluent gas and carbon precursor, carbon is deposited on a template and a product is obtained from particles of a template covered with graphene, the reactor is rotated relative to its longitudinal axis, the value of the rotational speed is chosen based on the prevention of centrifugal Forces of dense ring concentration of particles at the wall of the reactor and ensuring mixing by sliding to the bottom by the action of gravity of the particles of the template on which they are deposited glerod and the formed intermediate product - about 1.4 revolutions per minute. In addition, the reactor is oriented in space in such a way that the angle formed by the horizontal and the longitudinal axis of the reactor, with the top in the outlet of the reactor, is about 15 degrees. The value of the angle formed by the horizontal and the longitudinal axis of the reactor, with the top in the outlet of the reactor, provides the speed of movement of the template particles through the reactor in a direction parallel to the axis of the reactor, on which carbon is deposited, sufficient to form the specified number of graphene monolayers.

After the deposition of carbon on the template, the resulting product from graphene-coated template particles is collected in a receiver located at the reactor outlet, it is loaded into the reactor and its high-temperature purification treatment is carried out, removing polycyclic aromatic hydrocarbons formed during carbon deposition. The treatment is carried out at a temperature of 300 ° C, for about 1 hour, by passing a stream of inert argon gas at a flow rate of 25 l / h. When processing, the reactor is rotated relative to its longitudinal axis, the rotational speed is chosen based on preventing centrifugal forces in the field from tightly concentrating particles at the reactor wall and ensuring mixing by sliding the particles from the template covered by the gravity to the bottom graphene - at a speed of 1.4 revolutions per minute. In addition, the reactor is oriented in space in such a way that the angle formed by the horizontal and the longitudinal axis of the reactor, with the top in the outlet of the reactor, is 15 degrees. Set the angle formed by the horizontal and the longitudinal axis of the reactor, with the top in the outlet of the reactor, providing the speed of movement of the product being cleaned through the reactor in a direction parallel to the axis of the reactor, corresponding to complete cleaning of the product, not more than 1 m / hour.

Conducted testing of the resulting electrode material from the carbon-mineral composite after removing the template. A two-electrode cell of a symmetrical design was formed, which was filled with an ionic liquid that performs the function of an electrolyte. When conducting testing measurements, a specific capacity of 30 F / g was obtained at a discharge current of 0.2 A / g.

Example 7

The method of synthesis of carbon composite to obtain the electrode material of the device, storing electrical energy, is as follows.

Previously obtained template, which is used as a powder of nanoscale particles of an inorganic material - metal oxide of the second group, providing chemical and thermal stability, no modification of structure and composition, chemical inertness with respect to carbon, good solubility in acidic solutions of magnesium oxide, is loaded into the reactor . Template - magnesium oxide is characterized by a particle size in the diameter of about 10-15 nm and a specific surface of the template of about 60-70 m ² / g.

Conduct temperature training flow tube reactor with a loaded template to the synthesis temperature by passing an inert gas stream with a flow rate of 20 l / h. Argon is used as inert gas. The preparation is carried out until the temperature of the synthesis is established, which ensures decomposition of the carbon precursor and carbon deposition on the template, about 720 ° C.

Then pass a stream of gaseous mixture from the diluent gas and carbon precursor, feeding it through the inlet. Moreover, the carbon precursor is selected from hydrocarbons of a number of alkanes - using a mixture of propane-butane with a composition by volume of 2% ethane, 18% butane and 80% propane. Argon is used as a diluent gas. The carbon precursor dilution is controlled by the amount of carbon deposited on the template surface and its deposition uniformity when blowing the mixture with the supply of inert gas with a flow rate of 5 l / h and feeding the propane-butane mixture with a flow rate of 20 l / h. Get the amount of carbon deposited on the surface of the template, amounting to about 9.5% by weight of the template. At the same time, carbon is deposited on the template and the product is obtained from template particles coated with graphene of controlled thickness of 2-3 graphene monolayers. The choice of the thickness of graphene is combined with the choice of the specific surface of the template to obtain the specific surface of graphene of the required value of 1000 m ² / g. The deposition is carried out for about 60 minutes. When implementing the flow of a gaseous mixture from a diluent gas and carbon precursor, carbon is deposited on a template and a product is obtained from particles of a template covered with graphene, the reactor is rotated relative to its longitudinal axis, the value of the rotational speed is chosen based on the prevention of centrifugal Forces of dense ring concentration of particles at the wall of the reactor and ensuring mixing by sliding to the bottom by the action of gravity of the particles of the template on which they are deposited glerod and the formed intermediate product - about 1.4 revolutions per minute. In addition, the reactor is oriented in space in such a way that the angle formed by the horizontal and the longitudinal axis of the reactor, with the top in the outlet of the reactor, is about 5 degrees. The value of the angle formed by the horizontal and longitudinal axis of the reactor, with the top in the outlet of the reactor, provides the speed of movement of the template particles through the reactor in a direction parallel to the axis of the reactor, on which carbon is deposited, sufficient for the formation of 2-3 graphene monolayers.

After the deposition of carbon on the template, the resulting product from graphene-coated template particles is collected in a receiver located at the outlet of the reactor, and a purification treatment with acetone is carried out. Using a filter, the product is rinsed in flow through in acetone, rinsing until transparency of the passing acetone through the product being washed. Then the carbon-mineral composite is dried in air at a temperature of from 20 to 100 ° C for about 2 hours.

Conducted testing of the resulting electrode material from the carbon-mineral composite after removing the template. A two-electrode cell of a symmetrical design was formed, which was filled with an ionic liquid that performs the function of an electrolyte. When conducting testing measurements, a specific capacity of 45 F / g was obtained at a discharge current of 0.2 A / g.

Example 8

The method of synthesis of carbon composite to obtain the electrode material of the device, storing electrical energy, is as follows.

Previously obtained template, which is used as a powder of nanoscale particles of an inorganic material - metal oxide of the second group, providing chemical and thermal stability, no modification of structure and composition, chemical inertness with respect to carbon, good solubility in acidic solutions of magnesium oxide, is loaded into the reactor . Template - magnesium oxide is characterized by a particle size in the diameter of about 10-15 nm and a specific surface of the template of about 60-70 m ² / g.

Conduct temperature training flow tube reactor with a loaded template to the synthesis temperature by passing an inert gas stream with a flow rate of 20 l / h. Argon is used as inert gas. The preparation is carried out until the temperature of the synthesis is established, which ensures decomposition of the carbon precursor and carbon deposition on the template, about 720 ° C.

Then pass a stream of gaseous mixture from the diluent gas and carbon precursor, feeding it through the inlet. Moreover, the carbon precursor is selected from hydrocarbons of a number of alkanes - using a mixture of propane-butane with a composition by volume of 2% ethane, 18% butane and 80% propane. Argon is used as a diluent gas. The carbon precursor dilution is controlled by the amount of carbon deposited on the template surface and its deposition uniformity when blowing the mixture with an inert gas feed at a rate of 5 l / h and feeding a mixture of propane-butane at a flow rate of 20 l / h. Get the amount of carbon deposited on the surface of the template, amounting to about 9.5% by weight of the template. At the same time, carbon is deposited on the template and the product is obtained from template particles coated with graphene of controlled thickness of 2-3 graphene monolayers. The choice of the thickness of graphene is combined with the choice of the specific surface of the template to obtain the specific surface of graphene of the required value of 1000 m ² / g. The deposition is carried out for about 60 minutes. When implementing the flow of a gaseous mixture from a diluent gas and carbon precursor, carbon is deposited on a template and a product is obtained from particles of a template covered with graphene, the reactor is rotated relative to its longitudinal axis, the value of the rotational speed is chosen based on the prevention of centrifugal Forces of dense ring concentration of particles at the wall of the reactor and ensuring mixing by sliding to the bottom by the action of gravity of the particles of the template on which they are deposited glerod and the formed intermediate product - about 1.4 revolutions per minute. In addition, the reactor is oriented in space in such a way that the angle formed by the horizontal and the longitudinal axis of the reactor, with the top in the outlet of the reactor, is about 5 degrees. The value of the angle formed by the horizontal and longitudinal axis of the reactor, with the top in the outlet of the reactor, provides the speed of movement of the template particles through the reactor in a direction parallel to the axis of the reactor, on which carbon is deposited, sufficient for the formation of 2-3 graphene monolayers.

Subsequent cleaning is not carried out.

Conducted testing of the resulting electrode material from the intermediate product of the carbon-mineral composite after removing the template. A two-electrode cell of a symmetrical design was formed, which was filled with an ionic liquid that performs the function of an electrolyte. When conducting test measurements, a specific capacity of 28 F / g was obtained at a discharge current of 0.2 A / g.

Claims (8)

1. A method of synthesizing carbon-mineral composite for producing electrode material of devices storing electrical energy, including temperature preparation of a flow reactor with a loaded template in the form of a powder of nano-sized particles of an inorganic material to the synthesis temperature while passing an inert gas stream, subsequent passing of a gaseous mixture stream from a gas diluent and carbon precursor, carbon deposition on the template and obtaining a product containing a carbon-mineral composite and template particles with a surface coated with graphene of a controlled thickness, the carbon precursor being selected from hydrocarbons of a number of alkanes, diluting the carbon precursor to control the amount of carbon deposited on the template surface and its uniform deposition, and choosing the thickness of graphene with the choice of the specific surface of the template, thereby providing the required value graphene specific surface, characterized in that after obtaining a product containing a carbon-mineral composite of template particles with a surface A grating coated with graphene of a controlled thickness conducts its purification treatment, removing the by-products formed during carbon deposition — polycyclic aromatic hydrocarbons; while passing a gaseous mixture from a diluent gas and carbon precursor, precipitating carbon on a template and obtaining a product containing carbon a mineral composite of template particles with a surface coated with graphene of controlled thickness, the reactor is rotated relative to its longitudinal axis, while the rotation speed is chosen based on preventing centrifugal forces in the field from densely concentrating particles at the reactor wall and ensuring their mixing by rotating the reactor and sliding to the bottom under the force of gravity of the particles, in addition, the reactor is oriented in space with its longitudinal axis located horizontally or oriented at an angle to the horizontal, while setting the value of the angle formed by the horizontal and the longitudinal axis of the reactor, with the top in the outlet of the reactor, echivayuschuyu speed of the template particles through the reactor in a direction parallel to the axis of the reactor, which is deposited on carbon, sufficient for the formation of no more than three monolayers graphene. 2. The method according to p. 1, characterized in that the template is used in the form of a powder of nanoscale particles of inorganic material - MgO, with a size in the diameter from 10 to 15 nm, with a specific surface area from 60 to 70 m ² / g, including the specified values, Temperature preparation of the flow reactor with a loaded template is carried out by passing an inert gas stream until the synthesis temperature is established, which decomposes the carbon precursor and carbon is deposited on the template, about 720 ° C. Argon is used as the inert gas. 3. The method according to p. 1, characterized in that by passing a stream of gaseous mixture from the diluent gas and carbon precursor, choosing a hydrocarbon of a number of alkanes as a carbon precursor is a mixture of propane-butane with a composition by volume of 2% ethane, 18% butane and 80% propane, argon is used as a diluent gas, dilution of carbon precursor is controlled by the amount of carbon deposited on the template surface and its uniform deposition when blowing the mixture with an inert gas flow rate from 5 to 10 l / h, including the values indicated This is done by feeding the propane-butane mixture with a flow rate from 20 to 40 l / h, including the indicated values, and obtaining the amount of carbon deposited on the template at about 9.5% of the template mass. 4. The method according to p. 1, characterized in that the choice of graphene thickness is combined with the choice of the specific surface of the template, thereby providing the required value of the specific surface of graphene, namely, to form no more than three graphene monolayers, choose the specific surface of the template equal to 60-70 m ² / g, than provide the required value of the specific surface of graphene about 1000 m ² / g. 5. The method according to p. 1, characterized in that after receiving a product containing a carbon-mineral composite of template particles with a surface coated with graphene of a controlled thickness, it is cleaned by treatment, removing the by-products formed during carbon deposition - polycyclic aromatic hydrocarbons, namely, they conduct its high-temperature cleansing treatment, at a temperature of from 400 to 720 ° C, including the indicated values, for about 1 hour, while passing a stream of inert argon or nitrogen gas with a flow rate m from 25 l / h to 50 l / h, including the specified values, with a high-temperature cleaning treatment, the reactor is rotated relative to its longitudinal axis, the rotation speed is chosen based on preventing centrifugal forces in the field from densely concentrating particles at the reactor wall and ensure their mixing due to the rotation of the reactor and sliding down to the bottom under the action of gravity of the particles, namely about 1.4 revolutions per minute, in addition, the reactor is oriented in space with the location of its longitudinal The horizontal axis is either oriented at an angle to the horizontal, while setting the angle formed by the horizontal and longitudinal axis of the reactor, with the top in the outlet of the reactor providing the speed of movement of the product being cleaned through the reactor in a direction parallel to the axis of the reactor, corresponding to complete cleaning of the product, no more than 1 m / h. 6. The method according to p. 1, characterized in that after obtaining a product containing a carbon-mineral composite of template particles with a surface coated with graphene of a controlled thickness, it is cleaned by treatment, removing the by-products formed during carbon deposition - polycyclic aromatic hydrocarbons, namely, it is processed in acetone, while using a filter, the product is washed under flow conditions in acetone, carrying out washing to achieve transparency of the passing acetone through the washed through Duct, after which the carbon-mineral composite is dried in air at a temperature of from 20 to 100 ° C for about 2 hours. 7. A method according to claim 1, characterized in that by passing a stream of gaseous mixture from a diluent gas and a carbon precursor, precipitating carbon on a template and obtaining a product containing a carbon-mineral composite of template particles with a surface covered with graphene of a controlled thickness, the reactor bring into rotational motion relative to its longitudinal axis, while the value of the rotational speed is chosen based on the prevention in the field of centrifugal forces of dense ring concentration of particles at the wall of the reactor and provided their mixing by rotating the reactor and sliding to the bottom by the force of gravity of the particles, namely, up to 1.4 revolutions per minute. 8. A method according to claim 1, characterized in that the angle between the horizontal and the longitudinal axis of the reactor is established, with the top in the outlet of the reactor providing the speed of movement of the template particles through the reactor in a direction parallel to the axis of the reactor on which carbon is deposited, sufficient to form no more than three graphene monolayers, namely no more than 15 °.