• 专利附录
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  • 权利要求
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    • 专利摘要:
    The invention relates to a method for manufacturing a structure (30) for forming an interface (44) between an electrode (41, 42) and an electrolyte (43) of a supercapacitor (40), comprising at least a sheet of oxidized graphene doped with nitrogen and groups (31) based on phosphorus and oxygen. First, an aqueous suspension (1) of a graphene oxide is prepared in water, to which a nitrogen-based compound (2) is added. The aqueous suspension is heated and then filtered to obtain a solid compound (20) comprising oxidized nitrogen-doped graphene. An acid suspension (3) comprising the solid compound and a phosphoric acid (4) is then prepared, then heated and filtered in order to obtain a structure comprising at least one sheet of nitrogen-doped oxidized graphene and comprising groups based on phosphorus and oxygen.
    公开号:FR3061350A1
    申请号:FR1663259
    申请日:2016-12-22
    公开日:2018-06-29
    发明作者:Philippe Stevens；Gwenaelle Toussaint；Aurelien-Louis Habrioux；Clement-Aime Comminges；Ismael Abidat；Teko-Wilhelmin Napporn
    申请人:Electricite de France SA；Centre National de la Recherche Scientifique CNRS；Universite de Poitiers；
    IPC主号:
    专利说明:

    © Agent (s): CABINET PLASSERAUD.
    FR 3 061 350 - A1 (54) PROCESS FOR MANUFACTURING A STRUCTURE OF SAID PROCESS.
    ©) The invention relates to a method of manufacturing a structure (30) intended to form an interface (44) between an electrode (41, 42) and an electrolyte (43) of a supercapacitor (40), comprising at least one sheet of oxidized graphene doped with nitrogen and groups (31) based on phosphorus and oxygen. First, an aqueous suspension (1) of a graphene oxide is prepared in water, to which a nitrogen-based compound (2) is added. The aqueous suspension is heated, then filtered in order to obtain a solid compound (20) comprising oxidized graphene doped with nitrogen. An acid suspension (3) comprising the solid compound and a phosphoric acid (4) is then prepared, then heated and filtered in order to obtain a structure comprising at least one sheet of oxidized graphene doped with nitrogen and comprising groups based on phosphorus and oxygen.
    '' A SUPERCAPACITOR AND STRUCTURE

    i
    Method for manufacturing a structure of a supercapacitor and structure resulting from said method
    TECHNICAL AREA
    The invention relates to the field of energy storage in the form of an accumulation of ions at an interface between an electrode and an electrolyte in a supercapacitor. More particularly, the invention relates to a method for manufacturing such an interface, the interface possibly constituting a charge accumulation layer in the charged supercapacitor. The invention also relates to the structure obtained by this process.
    TECHNOLOGICAL BACKGROUND
    There are many ways to store electrical energy. In particular, it is possible to store electrical energy in chemical form in batteries. The electrical energy of a battery can be restored for a duration greater than 30 minutes, with power densities typically less than 1000 W / kg. Batteries are electrical energy storage devices suitable for moderate power delivery over time. The life of these devices is also limited to approximately one thousand charge and discharge cycles.
    Although batteries are a central element in supplying electrical energy in a circuit, they cannot meet certain specific needs for high power. Generally, it is possible to compensate for this power deficit by adding, to a circuit, components capable of locally storing a small amount of electrical energy and of restoring it in a short lapse of time. Electrostatic capacitors therefore constitute local sources of high power density, generally greater than 10 000 W / kg, but which can only be restored during a lapse of short time typically between 1 ms and 1 s. Unlike batteries, electrostatic capacitors can have a long lifespan of more than 1 million charge and discharge cycles. The electrostatic capacitors are based on an accumulation of charges in the vicinity of the armatures (called electrodes), separated by a dielectric insulator preferably having a high dielectric permittivity. Electrostatic capacitors are generally used to stabilize a power supply.
    Other devices are provided to provide a punctual power supply of intermediate duration between 1 s and 5 min typically. Supercapacitors, also called electrolytic capacitors, constitute as such devices capable of storing electrical energy and restoring it with power densities typically between 500 W / kg and 10,000 W / kg. A supercapacitor consists of two electrodes separated by an electrolyte. When charged, ions accumulate at the interface between the electrodes and the electrolyte to form a "double layer". Supercapacitors can also have a hybrid structure allowing them to store electrical energy both in the form of ion accumulation and charge accumulation by faradic reaction, as for example in asymmetric supercapacitors which have an electrode positive capacity typically three times greater than the capacity of the negative electrode.
    Since supercapacitors are capable of providing a high power density from time to time for a few seconds, they can be used in combination with a battery to occasionally respond to a high demand for power in a circuit.
    The choice of electrolyte used in a supercapacitor allows certain electrical properties of these devices to be adjusted. In particular, it is possible to classify electrolytes into three groups: aqueous electrolytes, organic electrolytes and electrolytes with ionic liquid.
    The aqueous electrolytes are safe and clean and offer a satisfactory conductivity of about 0.8 S / cm. However, they can only be used in a restricted range of potentials not exceeding 1 V.
    Organic electrolytes often use a toxic and flammable solvent, and have a conductivity about 50 times lower than aqueous electrolytes. However, they can be used in a wider range of potentials up to 2.7 V.
    Ionic liquid electrolytes are safer, but also expensive to produce. Although they offer the widest range of operating potentials (up to 4 V), they offer a low conductivity of around 0.001 S / cm.
    In addition to the choice of electrolyte, the electrical properties of a supercapacitor depend on the capacity of the interfaces between the electrodes and the electrolyte to store ions to form a double layer. This storage capacity depends in particular on the surface A of the interface. In addition, the double layer Cdi capacity can be expressed in the form:
    Cdi = (e 0 8 r A) / d
    Where d denotes the approach distance (typically equal to a few angstroms), and εο ε Γ denote the dielectric permittivity of the vacuum and the electrolyte respectively.
    It follows from this expression that the surface of the electrolyte electrode interface represents an adjustable parameter to increase the capacity of a supercapacitor and make it more efficient.
    It is common to use carbon as the electrode because of its electrochemical stability with respect to the electrolyte and its ability to form, by oxidation of a carbon powder in a humid atmosphere, a rough interface with numerous micro and macro pores, thus increasing the surface A. The use of carbon can lead to supercapacitors whose Cdi capacity reaches a value of 100 F / g. This limit value cannot be increased due to an inability to store ions when the pores are less than 2 nm in size. Thus, for surfaces greater than 1000 m 2 / g, the performance of the carbon electrodes is no longer increased but potentially decreased by the presence of inactive pores.
    In order to increase the surface A, it has been proposed to use carbon nanotubes, which also have the advantage of having a high electronic conductivity. However, the reduced dimensions of the nanotubes are not suitable for an accumulation of charges in the tubes. Functionalization of the carbon nanotubes by adding organic matter capable of storing the ions does not make it possible to reach capacities greater than 120 F / g.
    Graphene is a carbon-based material with an extended two-dimensional surface that can reach a theoretical value of 2620 m 2 / g. The use of graphene as an interface between an electrode and an electrolyte in a supercapacitor has advantages: graphene does not rely on the storage of ions in pores likely to vary in size, the atomic thickness of graphene allows diffusing ions and charges over very short distances with great efficiency, graphene is a good electrical conductor and is chemically stable in the electrolytes of the supercondensors.
    However, graphene sheets tend to stack on top of each other and overlap so that they can only be used on one side facing the electrolyte. Van der Waals forces bind the graphene sheets together and block access to the ions to the sandwiched sheets.
    A process is therefore sought for manufacturing a structure capable of storing ions and usable as an electrode-electrolyte interface in a supercapacitor which offers a high surface area A and makes it possible to reach a capacity of value greater than the values obtained. by traditional manufacturing methods.
    STATEMENT OF THE INVENTION
    To respond to the problems set out above, the present invention provides a method of manufacturing a structure intended to form an interface between an electrode and an electrolyte of a supercapacitor, said structure comprising at least one sheet of oxidized graphene doped with l nitrogen and comprising groups based on phosphorus and oxygen, said process comprising:
    - prepare an aqueous suspension of a graphene oxide in water;
    - add a nitrogen-based compound to the aqueous suspension;
    - heating the aqueous suspension;
    - Filter the aqueous suspension in order to obtain a solid compound comprising oxidized graphene doped with nitrogen;
    - Prepare an acid suspension comprising the solid compound and a phosphoric acid;
    - heat the acid suspension;
    - Filter the acid suspension to obtain a structure comprising at least one sheet of oxidized graphene doped with nitrogen and comprising groups based on phosphorus and oxygen.
    This process makes it possible to produce at least one functionalized graphene sheet so that the Van der Waals forces between sheets are reduced, making it possible to increase the surface of graphene which can be used to receive ions in a supercapacitor. In addition, the proposed process is simple to carry out because it uses a graphene oxide in an aqueous suspension to replace certain carbonaceous sites with nitrogen with a controlled chemical environment obtained by the implementation of the process of the invention. Indeed, by heating an aqueous suspension comprising a nitrogen-based compound and graphene oxide, the invention makes it possible to obtain a doping having a distribution between graphitic, pyrrolic and pyrinidic sites adapted to a reduction of the forces of Van der Waals between sheets. The subsequent addition of phosphorus and oxygen-based groups to this nitrogen-doped graphene oxide further reduces the risk of stacking graphene sheets on top of each other, and further contributes to providing greater stability of the sheet within the supercapacitor. In fact, the phosphorus and oxygen-based groups can be linked to graphene by carbon-oxygen covalent bonds which are more resistant than the carbon-metal bonds in the case of the use of metallic functional groups. Due to the absence of metallic compounds among the heteroatoms added to the sheet, the structure produced maintains its mechanical integrity for a longer time within a supercapacitor, which contributes to increasing the number of charge / discharge cycles that can be envisaged for the supercapacitor comprising this structure.
    The method of the present invention thus makes it possible to obtain a structure intended to form an interface between an electrode and an electrolyte of a supercapacitor having a Cdi capacity of approximately 400 F / g. In addition, the manufacturing process is simple to implement, and makes it possible to obtain a structure increasing the number of charge / discharge cycles of a supercapacitor.
    According to one embodiment, the structure comprising sheets of oxidized graphene doped with nitrogen and comprising groups based on phosphorus and oxygen can be deposited on a supercapacitor electrode to form a double layer.
    This deposition can for example be carried out by mixing one or more graphene sheets with an ink which is poured onto the external surface of an electrode of a supercapacitor, for example a carbon electrode.
    According to one embodiment, the nitrogen-based compound can be chosen from urea, melanin and ammonia.
    These compounds have the advantage of being simple and not very bulky compounds, which can react easily in solution under the effect of heat to release nitrogen which replaces carbon atoms in graphene oxide. In addition, these compounds make it possible to obtain a distribution in pyrrolic and pyrinidic graphitic sites for the nitrogen atoms typically verifying the following proportions: between 15% and 25% of graphitic sites, between 45% and 55% of pyrrolic sites and between 25% and 35% of pyrinidine sites in a graphene oxide sheet. These proportions are suitable for reducing Van der Waals forces without altering the electrical properties and the solution stability of the sheet.
    According to one embodiment, the aqueous suspension can comprise a concentration of nitrogen-based compound 20 to 50 times greater than a concentration of graphene oxide.
    According to one embodiment, the concentration of graphene oxide can be between 0.5 mg / ml and 5 mg / ml in the aqueous solution, and that the concentration of solid compound is between 0.5 mg / ml and 5 mg / mL in the acid solution.
    These proportions favor the appearance of graphitic, pyrrolic and pyrinidic sites in the proportions defined above.
    According to one embodiment, the aqueous suspension can be heated to a temperature between 100 ° C and 200 ° C for a time between 2 hours and 10 hours.
    According to one embodiment, the acid suspension can be heated to a temperature between 50 ° C and 200 ° C for a time between 12 hours and 48 hours.
    According to one embodiment, the method can also comprise:
    - doping the solid compound with heteroatoms chosen from cobalt and ruthenium.
    The addition of these metallic heteroatoms makes it possible to add a faradaic pseudocapacity to a supercapacitor, thus increasing these energy performances.
    The invention also relates to a structure forming an interface between an electrode and an electrolyte of a supercapacitor, obtained by implementing the method described above, the structure comprising at least one sheet of oxidized graphene, said sheet being doped with nitrogen heteroatoms and further comprising phosphorus and oxygen groups.
    In particular, the structure can be arranged on an electrode of the supercapacitor.
    According to one embodiment, nitrogen represents a proportion of less than 10 atomic% in the sheet, while the groups based on phosphorus and oxygen represent a proportion of less than 5 atomic% in the sheet.
    These proportions make it possible to maintain good electrical properties in a graphene sheet, not to reduce the surface A available to receive ions in a supercapacitor, and lead to an effective reduction in the stacking of the sheets on each other.
    According to one embodiment, the nitrogen can occupy graphitic, pyrrolic and pyrinidic sites in the sheet in the following proportions: between 15% and 25% of graphitic sites, between 45% and 55% of pyrrolic sites and between 25% and 35% of pyrinidine sites.
    According to one embodiment, the groups based on phosphorus and oxygen comprise phosphates linked to the sheet by a carbon-oxygen or phosphorus-oxygen bond.
    The use of phosphate groups linked specifically to nitrogen-doped graphene oxide via bonds involving oxygen leads to greater stability of the structure within a supercapacitor. Indeed, the carbon-phosphate bonds are less stable and more likely to be damaged during the cycling of a supercapacitor.
    According to one embodiment, the phosphorus and oxygen-based groups comprise phosphorus heteroatoms linked to the sheet by at least one phosphorus-oxygen bond with an oxygen atom of graphene oxide.
    The use of the oxygen atoms present in the sheet makes it possible to avoid agglomeration of phosphorus-based groups on the edges of the sheet.
    The invention also relates to a supercapacitor comprising a structure as described above.
    DESCRIPTION OF THE FIGURES
    The process which is the subject of the invention will be better understood on reading the following description of examples of embodiments presented by way of illustration, in no way limiting, and by observing the drawings below in which:
    - Figure 1 is a flowchart representing seven stages of the manufacturing process of a structure intended to form an interface between an electrode and an electrolyte of a supercapacitor;
    - Figure 2 is a schematic representation of a graphene sheet doped with nitrogen, integrated in the following sheet so as to occupy different sites in the sheet comprising graphitic, pyrrolic and pyrinidic sites;
    - Figure 3 is a schematic representation of a graphene oxide sheet identifying different possible configurations for binding oxygen to the carbon of the sheet;
    - Figure 4 is a schematic representation of a supercapacitor.
    For reasons of clarity, the dimensions of the different elements shown in these figures are not necessarily in proportion to their actual dimensions. In the figures, identical references correspond to identical elements.
    DETAILED DESCRIPTION
    The present invention provides a method for synthesizing a structure comprising at least one graphene sheet functionalized so that the structure can be used as an interface between an electrode and an electrolyte of an electrolyte capacitor, also called a supercapacitor. The graphene sheet structure obtained by the process of the invention makes it possible to confer a capacity of up to 400 F / g on a supercapacitor equipped with such a structure.
    The process of the invention involves simple steps making it possible, from a graphene oxide (obtained according to known and well-controlled methods), to add a proportion of nitrogen heteroatoms and groups based on phosphorus and d 'oxygen. Doping with nitrogen in the process makes it possible to distribute a proportion of nitrogen atoms of less than 10 atomic% in the sheet, and serves to reduce the Van der Waals forces which usually retain graphene sheets stacked one on top of the other. on the others. Doping with nitrogen, by means of the process of the present invention, limits this stacking and confers a larger surface of graphene accessible to the ions of the electrolyte of the supercapacitor coming to form a double layer starting from the structure of the invention. . The use of phosphorus and oxygen-based groups also promotes the reduction of these Van der Waals forces, and also makes it possible to increase the stability of the structure within a cycling supercapacitor (phase alternations of charge and discharge of the supercapacitor). This property is notably conferred by the absence of metals forming carbon-metal bonds which are less resistant than the phosphorus oxygen bonds obtained by the synthesis process of the present invention.
    FIG. 1 represents a flowchart summarizing certain steps of the method of the present invention.
    During a first step SI, an aqueous suspension 1 is prepared. This suspension typically comprises water and a graphene oxide 10. It is preferred to use a concentration of graphene oxide of between 0.5 mg / L and 5 mg / L in the aqueous suspension 1.
    Graphene oxide can typically be obtained by a known process such as the "Hummer method", as set forth for example in the document Hummers, William S .; Offeman, Richard E. (March 20, 1958). Preparation of Graphitic Oxide, Journal of the American Chemical Society. 80 (6): 1339.
    This method makes it possible to obtain a graphite oxide which can then be exfoliated in an ultrasonic bath to prepare the graphene oxide used in step SI.
    FIG. 3 schematically represents a graphene oxide sheet 10 comprising carbon atoms 12, oxygen atoms 11 and hydrogen atoms 13.
    Oxygen can typically form three different chemical bonds in graphene.
    A first type of bond 101 consists in forming an epoxy group. A second type of bond 102 consists in forming a hydroxyl group. A third type of bond consists in forming a carboxyl group.
    In a second step S2, a nitrogen-based compound 2 is added to the aqueous suspension 1. This compound can for example be chosen from urea, melanin or ammonia. Other simple compounds the size of which does not exceed that of inorganic compounds commonly used in chemistry are preferred. Thus, organic nitrogen compounds and in particular polymerized compounds are not preferred in the process of the invention.
    The nitrogen-based compound 2 has a concentration in the aqueous suspension 1 typically 20 to 50 times greater than the concentration of graphene oxide. Thus typical concentrations can be between 10 mg / mL and 50 mg / mL.
    During a step S3 which follows, the aqueous suspension 1 is heated, to temperatures typically between 100 ° C. and 200 ° C. for a period of between 2 hours and 10 hours. This step allows the nitrogen in the nitrogen-based compound 2 to be integrated into the graphene oxide 10.
    The aqueous suspension 10 is then filtered during a step S4 in order to obtain a solid compound 20 comprising at least one sheet of graphene oxide doped with nitrogen 21.
    The process of the present invention naturally leads to the formation of a solid compound 20 in which nitrogen 21 occupies up to 10 atomic% of the sheet, and occupies different sites in the sheet. In particular, it has been observed that at the end of steps S4, nitrogen 21 occupies between 15% and 25% of graphitic sites, between 45% and 55% of pyrrolic sites and between 25% and 35% of pyrinidic sites in the solid compound 20. It should be noted that doping with nitrogen 21 can lead to a distribution of the nitrogen either on the edges of the graphene oxide sheet, or in replacement of carbon atoms in the sheet himself.
    FIG. 2 schematically represents a two-dimensional plane of graphene 200 doped with nitrogen. This figure illustrates an example of a graphitic site 201, an example of a pyrrolic site 202 and an example of a pyrinidic site 203. The so-called “pyrinidic” sites are sites in accordance with the representation of FIG. 2. In addition, doping with graphene nitrogen can also give rise to the appearance of quaternary sites and nitrogen oxides, although these configurations are not predominant in the solid compound obtained by the process of the present invention.
    The distribution in graphitic, pyrrolic and pyrinidic sites obtained in the solid compound at the end of step S4 seems to confer particularly advantageous properties on the sheet in terms of limitation of the Van der Waals forces at the origin of the stacking of the sheets, without however affecting the electrical conduction performance of the sheet.
    The process continues in step S5 with the preparation of an acid suspension 3 in which a certain amount of solid compound 20 is added in phosphoric acid 4. The concentration of solid compound 20 in the acid suspension 3 is typically between 0.5 mg / mL and 5 mg / mL.
    The acid suspension 3 is then heated during a step S6. This step can typically be carried out at temperatures between 50 ° C and 200 ° C for a period between 12 hours and 48 hours. This step makes it possible to incorporate into the solid compound 20 groups 31 based on phosphorus and oxygen. These groupings are formed either at the edge of the sheet, or directly on the sheet.
    Furthermore, the incorporation of these groups is carried out in such a way that the phosphate atoms do not create chemical bonds directly with the carbon atoms 12 of the solid compound 20, but with the oxygen atoms. 11 of the solid compound 20. It is for example possible that phosphorus is grafted onto an oxygen atom 11 available. It is also for example possible that a phosphorus-based group such as phosphate creates a covalent bond via an oxygen atom of the phosphate with a carbon 12 atom of the solid compound.
    These phosphate oxygen or carbon oxygen bonds are more resistant than the carbon phosphorus bonds, which makes it possible to give structure 30 better properties in cycling in a supercapacitor, and to increase the lifetime of the supercapacitor.
    At the end of this step S6, a filtering of the acid suspension 3 is carried out during a step S7 to obtain a structure 30 comprising at least one sheet of graphene oxide doped with nitrogen 21 and comprising groups with phosphorus and oxygen base 31.
    The phosphorus and oxygen groups obtained at the end of step S7 typically occupy less than 5 atomic% of the structure 30. This low proportion of phosphorus and oxygen groups makes it possible to preserve the properties of electrical conduction of the structure without degrading them.
    In addition, it is possible to add other functional groups to the structure 30. For example, it is possible to carry out doping with metal atoms of cobalt or ruthenium. The presence of metals implies the formation of less resistant chemical bonds with structure 30, but makes it possible to increase the capacity of a supercapacitor equipped with such a structure by adding a term of additional faradaic capacity.
    The structure 30 obtained at the end of step S7 of the process can then be deposited in the form of a layer on an electrode of a supercapacitor.
    FIG. 4 schematically represents a circuit comprising a direct current source 5, a resistor 6 and a supercapacitor 40. This supercapacitor 40 comprises two electrodes 41, 42 separated by an electrolyte 43. An interface 44 between an electrode 41, 42, and the electrolyte 43 can benefit from the structure 30 obtained by the process described above. FIG. 4 represents a supercapacitor in operation, in which the interface 44 exists as a "double layer" comprising an accumulation of ions on the interface 44.
    The structure 30 can in particular be deposited on an electrode via an ink. Such an ink spread over the surface of an electrode makes it possible to deposit several sheets on the electrode. The sheets, functionalized so that the Van der Waals forces tending to cause a stacking of the sheets on top of each other are greatly reduced, are arranged naturally leaving spaces between sheets allowing the ions to access a larger surface in the interface 44. Thus the electrical performance of the supercapacitor 40 is improved.
    Example of realization
    H is now described an embodiment of a structure 30 as described above.
    A graphite oxide is synthesized by the Hummer method, as indicated in the referenced above. 3g of a commercial graphite powder are dispersed in a concentrated sulfuric acid solution (69 mL, 96%) with magnetic stirring for about 10 min. 1.5 g of sodium nitrate are added to the suspension. The mixture is mechanically stirred for approximately 10 min. The whole process is carried out at 20 ° C. The suspension is then cooled using an ice bath. 9 g of potassium permanganate are then added to the suspension which is still maintained under magnetic stirring. The whole mixture is then brought to a temperature of 35 ° C for about 30 min using an oil bath. About 138 mL of pure water is added to the mixture. The temperature of the oil bath is then brought to 98 ° C for approximately 15 min. The mixture is then cooled using an ice bath. 420 ml of water, then 5 ml of hydrogen peroxide are then added to the reaction mixture. The entire suspension is kept under magnetic stirring for approximately 30 min.
    The material thus obtained then undergoes a recovery and washing protocol. The entire suspension is subjected to centrifugation at 7000 rpm for approximately 15 min. Following a mechanical separation step, the supernatant is removed. The remaining gel is resuspended in a hydrochloric acid solution. The suspension is again subjected to centrifugation at 7000 rpm for approximately 15 min. This washing / separation operation is repeated 2 times. The same washing operation is repeated 5 times by replacing the hydrochloric acid with pure water. Following the washing step, the solid is dried in an oven (at about 40 ° C) for about 48 h. The powder is then manually ground in a mortar.
    The material thus obtained is first exfoliated by ultrasound applications to obtain a graphene oxide. An aqueous suspension containing a concentration of 1 mg / ml of the solid previously obtained is first produced with pure water. The suspension is placed in an ultrasonic bath (800 W) for approximately 1 h.
    Subsequently, the nitrogen doping is carried out using graphene oxide.
    In the suspension obtained in the previous step, urea is added at a concentration of 30 mg / mL. The suspension is stirred using a magnetic bar for about 30 min at a temperature of 20 ° C. The suspension obtained is placed in a steel autoclave fitted with a Teflon® tank. The filling rate is 80%. The autoclave is placed under static conditions in an oven previously brought to the temperature of 170 ° C. for 6 h. At the end of the synthesis, the temperature of the oven drops to room temperature without applying a temperature ramp. The suspension is then filtered through a millipore filter having a pore size of about 0.45 microns. The solid compound thus obtained is then filtered 4 times in the presence of pure water. The solid is then recovered and then dried in an oven at 40 ° C for about 12 h.
    The solid compound thus obtained undergoes a second doping step with the aim of including phosphorus-containing species in the solid. A suspension at a concentration of 1 mg / ml is prepared using the solid compound. The suspension is produced using orthophosphoric acid. The suspension is then placed in an ultrasonic bath (800 W) for approximately 1 h. Once the suspension is stable, it is placed under reflux in an oil bath brought to the temperature of 120 ° C. The duration of the treatment can be between and 48 h, and preferably lasts about 24 h. The material is then recovered by centrifugation at 7000 rpm for approximately 15 min. The supernatant is then removed. The structure obtained is then washed with pure water by filtration. This last step is repeated 5 times. The structure obtained is then dried in the study for approximately 12 hours at a temperature of 40 ° C., taking care not to exceed a temperature of 80 ° C.
    权利要求:
    Claims (15)
    [1" id="c-fr-0001]
    Claims
    1. Method for manufacturing a structure (30) intended to form an interface (44) between an electrode (41, 42) and an electrolyte (43) of a supercapacitor (40), said structure comprising at least one sheet of oxidized graphene doped with nitrogen and comprising groups based on phosphorus and oxygen, said process comprising:
    - prepare an aqueous suspension (1) of a graphene oxide (10) in water;
    - add a nitrogen-based compound (2) to the aqueous suspension;
    - heating the aqueous suspension;
    - Filter the aqueous suspension in order to obtain a solid compound (20) comprising oxidized graphene doped with nitrogen;
    - Prepare an acid suspension (3) comprising the solid compound and a phosphoric acid (4);
    - heat the acid suspension;
    - Filter the acid suspension in order to obtain a structure (30) comprising at least one sheet of oxidized graphene doped with nitrogen and comprising groups (31) based on phosphorus and oxygen.
    [2" id="c-fr-0002]
    2. Method according to claim 1, characterized in that the structure comprising sheets of oxidized graphene doped with nitrogen and comprising groups based on phosphorus and oxygen is deposited on a supercapacitor electrode to form a double layer .
    [3" id="c-fr-0003]
    3. Method according to any one of claims 1 to 2, characterized in that the nitrogen-based compound is chosen from urea, melanin and ammonia.
    [4" id="c-fr-0004]
    4. Method according to any one of claims 1 to 3, characterized in that the aqueous suspension comprises a concentration of nitrogen-based compound 20 to 50 times greater than a concentration of graphene oxide.
    [5" id="c-fr-0005]
    5. Method according to any one of claims 1 to 4, characterized in that the concentration of graphene oxide is between 0.5 mg / ml and 5 mg / ml in the aqueous solution, and that the concentration of solid compound is between 0.5 mg / mL and 5 mg / mL in the acid solution.
    [6" id="c-fr-0006]
    6. Method according to any one of claims 1 to 5, characterized in that the aqueous suspension is heated to a temperature between 100 ° C and 200 ° C for a period between 2 hours and 10 hours.
    [7" id="c-fr-0007]
    7. Method according to any one of claims 1 to 6, characterized in that the acid suspension is heated to a temperature between 50 ° C and 200 ° C for a period between 12 hours and 48 hours.
    [8" id="c-fr-0008]
    8. Method according to any one of claims 1 to 7, characterized in that it further comprises:
    - doping the solid compound with heteroatoms chosen from cobalt and ruthenium.
    [9" id="c-fr-0009]
    9. Structure (30) forming an interface (44) between an electrode (41, 42) and an electrolyte of a supercapacitor (40), obtained by the implementation of the method according to one of claims 1 to 8, the structure comprising at least one sheet of oxidized graphene, said sheet being doped with nitrogen heteroatoms and further comprising groups (31) based on phosphorus and oxygen.
    [10" id="c-fr-0010]
    10. Structure according to claim 9, characterized in that it is arranged on an electrode of the supercapacitor.
    [11" id="c-fr-0011]
    11. Structure according to any one of claims 9 or 10, characterized in that the nitrogen represents a proportion of less than 10 atomic% in the sheet, while the groups based on phosphorus and oxygen represent a proportion of less than 5 atomic% in the sheet.
    [12" id="c-fr-0012]
    12. Structure according to any one of claims 9 to 11, characterized in that the nitrogen occupies graphitic, pyrrolic and pyrinidic sites in the sheet in the following proportions: between 15% and 25% of graphitic sites, between 45% and 55% of pyrolytic sites and between 25% and 35% of pyrinidic sites.
    [13" id="c-fr-0013]
    13. Structure according to any one of claims 9 to 12, characterized in that the groups based on phosphorus and oxygen comprise phosphates linked to the sheet by a carbon-oxygen or phosphorus-oxygen bond.
    [14" id="c-fr-0014]
    14. Structure according to any one of claims 9 to 13, characterized in that the phosphorus and oxygen-based groups comprise phosphorus heteroatoms linked to the sheet by at least one phosphorus-oxygen bond with an oxygen atom graphene oxide.
    [15" id="c-fr-0015]
    15. Supercapacitor (40) comprising a structure (30) according to any one of claims 9 to 14.
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    同族专利:
    公开号 | 公开日
    FR3061350B1|2019-05-31|
    WO2018115208A1|2018-06-28|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    CN103723716A|2013-12-23|2014-04-16|北京化工大学|Nitrogen-doped carbon-coated graphene oxide two-dimensional porous composite material and preparation method thereof|
    CN105621393A|2014-11-28|2016-06-01|中国科学院大连化学物理研究所|Functionalized graphene material, and preparation method and application thereof|
    KR20150020156A|2014-12-29|2015-02-25|성균관대학교산학협력단|Preparing method of doped reduced graphene oxide using ionic liquid, and doped reduced graphene oxide prepared by the same|
    CN104817063B|2015-05-07|2016-08-17|常州大学|A kind of preparation method of two dimension nitrogen phosphorus doping Graphene|
    CN109612177B|2018-12-25|2020-02-21|吉林大学|Two-dimensional limited ice and preparation method thereof|
    CN111362251B|2020-03-20|2021-08-03|山东大学|High-phosphorus-nitrogen co-doped three-dimensional porous carbon block and preparation method and application thereof|
    CN112079351A|2020-09-01|2020-12-15|深圳市超导新材料有限公司|Preparation method of nitrogen-containing few-layer graphene|
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1663259|2016-12-22|
    FR1663259A|FR3061350B1|2016-12-22|2016-12-22|METHOD FOR MANUFACTURING A STRUCTURE OF A SUPERCONDENSOR AND STRUCTURE THEREFROM|FR1663259A| FR3061350B1|2016-12-22|2016-12-22|METHOD FOR MANUFACTURING A STRUCTURE OF A SUPERCONDENSOR AND STRUCTURE THEREFROM|
    PCT/EP2017/083958| WO2018115208A1|2016-12-22|2017-12-20|Method for doping oxidised graphene with nitrogen and phosphorus in order to obtain a supercapacitor electrode material|
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