TWI530004B - Process for manufacturing a nitrogen-containing porous carbonaceous material - Google Patents

Description

Method for producing nitrogen-containing porous carbonaceous material

The present invention relates to a method of producing a nitrogen-containing porous carbonaceous material having an inorganic salt content of up to 50 ppm by weight, which comprises the following steps:

(A) by

(a) at least one heterocyclic hydrocarbon having at least two NH ₂ - groups per molecule and

(b) at least one aromatic compound having at least two aldehyde groups per molecule for conversion reaction

(B) Heating to a temperature in the range of 700 to 1200 ° C in the absence of oxygen.

Moreover, the present invention relates to a carbonaceous material that is highly suitable for use in capacitors.

Electrochemical energy as a source of clean power has caused extreme base and industrial interest. Capacitors, such as electrochemical double layer capacitors (EDLC), also referred to herein as capacitors, are electrical devices that store and release energy by nanometer range charge separation at high surface area electrodes and electrolyte interfaces, see for example R. K. Tz et al., Electrochim. Acta 2000, 45, 2843 and D. Hulicova-Jurcakova et al., Adv. Funct. Mater. 2009, 19, 1800.

Compared to batteries, capacitors can release and replenish energy in a short period of time. One obstacle to the current application is its low energy density, see for example B.E. Conway, Electrochemical Supercapacitors: scientific fundamentals and technological aspects. Kluwer Academic/Plenum Publishers: New York (1999). The energy density of capacitors, batteries, and other energy storage devices can be seen, for example, in a Ragone plot.

Many of today's capacitors are based on activated carbon or tantalum materials. However, the generally undefined activated carbon pore structure does not produce optimal electrochemical kinetics during energy absorption and release. In addition, high-priced materials are not beneficial. Accordingly, it is an object to provide materials for capacitors that have better electrochemical kinetics or are less expensive during energy absorption and release.

Other challenges for capacitors are:

- Simple manufacturing method

- Higher energy density

- Long-term stability.

One goal is to provide capacitors that overcome previous capacitor technology. One purpose is to provide materials that can be used in capacitors and thereby overcome the deficiencies of previous capacitor technology. Another object is to provide a method for making such materials. A further object is to discover other applications of novel materials.

Therefore, methods and materials as defined above have been discovered.

The method according to the invention (also referred to hereinafter as the method of the invention) is a process for producing a nitrogen-containing porous carbonaceous material.

The term "nitrogen-containing" means a carbonaceous material comprising a chemically bonded nitrogen atom. The nitrogen can be trivalent or tetravalent. Without being bound by any theory, in the context of the present invention, the nitrogen chemically bonded to the carbonaceous material may be, for example, part of the following structural elements:

In the case of a quaternary nitrogen atom, suitable counterions are hydroxide ions and halide ions, especially chloride ions.

In one embodiment of the invention, the nitrogen content is in the range of from 1 to 8% by weight, preferably from 5 to 7% by weight.

The term porous means a carbonaceous material having a BET surface area of from 50 to 3000 m ² /g, preferably from 50 to 1500 m ² /g.

The method of the invention comprises at least two steps.

In step A,

by

(a) at least one heterocyclic hydrocarbon having at least two NH ₂ - groups per molecule (this compound is hereinafter also referred to as compound (a)) and

(b) at least one aromatic compound having at least two aldehyde groups per molecule (this compound is hereinafter also referred to as compound (b)) is subjected to a conversion reaction.

The compound (a) may have at least two, preferably two to four NH ₂ - groups per molecule and preferably two or three NH ₂ - groups. When a mixture of the compounds (a) is used, the content of the NH ₂ - group of the compound (a) is in the range of 2 to 3 / mol.

Compound (a) may have in addition to NH ₂ - one or more functional groups outside the group. Suitable functional groups other than the NH ₂ - group are the second or third amine group, the ketone group and the hydroxyl group.

In a preferred embodiment, compound (a) does not have a functional group other than the NH ₂ - group.

In the step (A), the compound (a) may be provided in the form of a protonated form having a free NH ₂ - group or, for example, having one or two NH ₃ ⁺ groups per molecule instead of the NH ₂ - group. If the compound (a) is modified to have one or more NH ₃ ⁺ - groups in place of the NH ₂ - group, the suitable counter ion is selected from the group consisting of organic and inorganic anions such as acetate, formate and benzoate, and In particular inorganic anions such as chloride ions and inorganic anions free of halide ions such as phosphate, hydrogen phosphate, sulfate and hydrogen sulfate. For the sake of simplicity, in the case of the compound (a), the NH ₃ ⁺ - group is also included in the NH ₂ - group.

The compound (a) is selected from heterocyclic hydrocarbons. Compound (a) may have one or more atoms other than carbon in the heterocyclic backbone, such as nitrogen, oxygen, sulfur, preferably nitrogen. Compound (a) may have a different atom other than carbon in the heterocyclic backbone, such as a nitrogen atom and an oxygen atom. Preferably, compound (a) has only a carbon atom and one or more nitrogen atoms in the heterocyclic backbone.

In one embodiment of the invention, compound (a) has from 3 to 20 carbon atoms, preferably from 3 to 10 carbon atoms per molecule.

Group is directly attached to the heterocyclic compound (a) of the main chain - embodiment, (a) one or more NH ₂ Compound In one embodiment of the present invention. Group is directly attached to the heterocyclic compound (a) of the main chain - for example, all the NH ₂ Compound (a) of the present invention in a particular embodiment.

In one embodiment of the present invention, one or more NH ₂ - group through a spacer group connecting line having one or more carbon atoms to the heterocyclic backbone of the compound (a) of such -CH ₂ -, - C(O)-, -CH(CH ₃ )-, -CH ₂ CH ₂ -, -(CH ₂ ) ₃ -, -NH-(CH ₂ ) ₃ - or C(O)-CH ₂ -CH ₂ - . In one particular embodiment of the present invention, all the NH ₂ - group through a line having one or more carbon atoms, may be the same or different spacer group is attached to the heterocyclic compound (a) of the main chain. For example, after an embodiment of an example embodiment having two NH ₂ - group (such as _{CH (NH 2) -CH 2 -NH} 2) group of the spacer.

In one embodiment of the invention, one or more NH ₂ - groups of compound (a) are directly attached to the heterocyclic backbone of compound (a), and one or more NH ₂ - groups of compound (a) The group is attached to the heterocyclic backbone of compound (a) via a spacer group, which is as defined above.

Compound (a) may have a non-aromatic or aromatic backbone. Suitable non-aromatic backbone

The main chain of the compound (a) may be substituted per molecule by at least one, preferably at least two spacer groups selected from the group consisting of NH ₂ - groups and having one or more NH ₂ - groups.

The main chain of the compound (a) may include one or more substituents other than those listed above, such as an OH group, a C ₁ -C ₆ -alkyl group or a C ₆ H ₅ group. However, compound (a) of the main chain of the preferred lines other NH ₂ - group and having one or more NH ₂ - group of the spacer group outside, not including other substituents.

The compound (a) is preferably selected from heteroaromatic hydrocarbons having at least two NH ₂ - groups per molecule, which means that the main chain is aromatic. The preferred aromatic backbone is

Particularly preferred is an aromatic backbone selected from

In one embodiment of the invention, compound (a) is selected from the group consisting of compounds of formula (III),

Wherein X ² is selected from the group consisting of hydrogen, methyl, phenyl, n-hexyl, OH and NH ₂ , preferably hydrogen and NH ₂ .

In the step (A), the compound (a) is subjected to a conversion reaction with at least one compound (b). Compound (b) carries at least two aldehyde groups per molecule, preferably at least two to three aldehyde groups per molecule. When a mixture of the compound (b) is used, the average aldehyde group content of the compound (b) is in the range of 2 to 3 aldehyde groups of 1 mole.

Compound (b) may have one or more functional groups other than the aldehyde group. Suitable functional groups other than the aldehyde group are a ketone group, a chlorine group and a hydroxyl group.

In a preferred embodiment, compound (b) does not have a functional group other than an aldehyde group.

In the step (A), the compound (b) may be provided in the form of a free aldehyde group or in a protected form (for example, an acetal moiety, acyclic or cyclic). For the sake of simplicity, the protective aldehyde group of the compound (b) such as an acetal moiety is also included in the aldehyde group.

However, the compound (b) is preferably used in the form of a free aldehyde group.

The compound (b) is aromatic, and it means that the compound (b) has a main chain selected from a carbocyclic aromatic ring and a heterocyclic aromatic ring. The aldehyde group is directly attached to the main chain or its system is linked through a spacer group. Suitable spacer groups are -C (CH _{3) 2} - and -CH ₂ CH ₂ -.

In one embodiment of the present invention, the compound (b) may have 4 to 30 carbon atoms per molecule, preferably 8 to 20 carbon atoms.

The preferred heteroaromatic backbone is

In one embodiment of the present invention, at least one compound (b) is selected from the group consisting of heteroaromatic dialdehydes, heteroaromatic trialdehydes, and carbocyclic aromatic dialdehydes and trialdehydes, the aromatic backbone of which is selected from the group consisting of benzene. a group such as an phenyl group, an exophenyl group, and preferably a phenyl group; an anthranyl group, such as a 1,7-anthranyl group, a 1,8-anthranyl group, a 1,5-anthranyl group, 2,6-Extenylene, exophenyl, such as 2,4'-biphenyl, 2,2'-biphenyl, and especially 4,4'-biphenyl, thiol, Stretching base, stretching base, stretching base, stretching base, 1,1':4',1"-extension of triphenyl, 1,1'-extension double [茚] base and 9,9' - Stretching double [茀] base.

In one embodiment of the invention, the carbocyclic aromatic dialdehyde and the trialdehyde are selected from the group consisting of those in which the aromatic backbone is selected from the group consisting of phenylene, naphthyl and phenyl.

In one embodiment of the invention, the heteroaromatic dialdehyde is selected from the group consisting of molecules of formula (I) and (II)

Wherein the code is defined as follows: R ¹ is selected from C ₁ -C ₆ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, third Butyl, n-pentyl, iso-pentyl, iso-Amyl, and n-hexyl, preferably methyl, benzyl, C ₆ -C ₁₄ -aryl, unsubstituted Or substituted by one to three C ₁ -C ₄ -alkyl groups per molecule, preferably a phenyl group, more preferably an unsubstituted phenyl group, and even more preferably a hydrogen group, the X ¹ group being selected from the group consisting of oxygen, sulfur and NH. It is preferably NH.

In one embodiment of the present invention, in the step (A), at least one compound (a) selected from the group consisting of heterocyclic dialdehydes is selected from the group consisting of

And a carbocyclic aromatic dialdehyde selected from the group consisting of

Or a carbocyclic aromatic trialdehyde selected from the group consisting of

Conversion reaction with at least one compound (b) selected from the group consisting of

In one embodiment of the present invention, the compound (a) and the compound (b) are converted in the step (A) such that the molar ratio of the aldehyde group to the NH ₂ - group is from 2:1 to 1:2. It is preferably in the range of 1.5:1 to 1:1.5 and particularly preferably 1:1.

In one embodiment of the invention, the conversion of compound (a) and compound (b) in step (A) is carried out at a temperature in the range of from 150 to 250 ° C, preferably from 170 to 200 ° C.

In one embodiment of the present invention, the conversion of the compound (a) and the compound (b) in the step (A) is in the range of 0.5 to 10 bar, preferably under normal pressure.

In one embodiment of the present invention, the conversion of the compound (a) and the compound (b) in the step (A) is carried out under an inert atmosphere such as a nitrogen atmosphere or a rare gas atmosphere. Alternatively, step (A) can be carried out in air.

In one embodiment of the present invention, the conversion of the compound (a) and the compound (b) in the step (A) is carried out for 1 hour to 7 days, preferably for 1 day to 5 days.

In one embodiment of the invention, compound (a) and compound (b) are converted in bulk in step (A).

In a preferred embodiment of the invention, the conversion of compound (a) and compound (b) is carried out in step (A) in the presence of a solvent. A particularly preferred solvent is dimethyl hydrazine (DMSO).

The conversion according to step (A) is preferably carried out without any solid inorganic substance such as an inorganic catalyst or an inorganic template such as zeolite or mica.

The conversion according to step (A) is preferably carried out without any natural or synthetic organic polymer such as seaweed or silk.

In one embodiment of the invention, the conversion according to step (A) can be accelerated using an organic catalyst such as a C ₁ -C ₃ -carboxylic acid.

In a preferred embodiment of the invention, the conversion according to step (A) is carried out without the use of any catalyst.

During step (A), water is produced. Water can be left in the reaction mixture or it can be removed by distillation. It is preferred to distill off the water formed.

In one embodiment of the invention, the conversion according to step (A) can be carried out to a percentage of 10 to 99 mol%, which represents a decrease in the content of the group (aldehyde group or NH ₂ - group). Preferably, the conversion according to step (A) is in the range of from 60 to 90 mol%, and more preferably in the range of up to 70 mol%.

By performing the step (A), the formed macromolecular substance may comprise an aminal structural element and a Schiff base structural element. Preferred are acetal structural elements.

Before the substance produced in the step (A) is supplied, if a solvent has been used, the solvent should be excluded first. This exclusion can be carried out by distillation, filtration or by a centrifuge.

In many cases, the material produced in step (A) can be used without further purification unless it is necessary to exclude (as needed) the solvent.

However, in some embodiments, it is preferred to further purify the material produced by step (A), for example to exclude any solvent or catalyst that may be used. Suitable methods for purification are, for example, washing, vacuum drying and extraction (for example by Soxhlet extraction).

In the step (B) of the present invention, the substance obtained from the step (A) is heated to a temperature in the range of from 700 to 1200 ° C, preferably from 800 to 1000 ° C, in the absence of oxygen.

In the case of step (B), the absence of oxygen means that the heating is carried out in a vacuum or in an inert atmosphere having an oxygen content of less than 0.1% by volume. A suitable inert atmosphere can be provided in step (B) by means of nitrogen or a noble gas (for example in an argon atmosphere).

In one embodiment of the invention, the heating according to step (B) can be carried out for a period of from 5 minutes to 48 hours, preferably from 30 minutes to 24 hours.

In one embodiment of the invention, the heating method can be carried out rapidly, for example, by exposing the substance according to step (A) to a hot surface of 1000 to 2000 °C.

However, it is preferred to heat the material according to step (A) in a slower manner, for example at a rate of from 1 to 10 min/°C, preferably from 90 seconds to 5 minutes/°C. When calculating the duration of the reaction according to step (B), the time to reach a temperature of 700 ° C, preferably 800 ° C, should be considered.

After the heating is complete, the material obtained can be cooled to room temperature or any other temperature suitable for analysis or further processing.

Without being bound by any theory, it is envisaged that several reactions occur during step (B). Among them, ammonia and/or other amines can be cracked. Open loop and closed loop reactions may occur, such as in the selection

In the case of the compound (b) of the step (A), a six-membered triazine ring is opened.

In one embodiment of the invention, the volatile portion of the material obtained in step (A) may be excluded during step (B). In the scope of the present invention, the volatile substance means a substance having a boiling point lower than the heating temperature of the step (B). Such volatile part may be water, an organic amine, HCN, CH ₃ CN, NH ₃ and volatile starting material from step (A) of unreacted.

The carbonaceous material of the present invention applied to, for example, a capacitor can be used without further purification.

By the method of the present invention, a nitrogen-containing carbonaceous material which is porous and which utilizes a nitrogen density of 1.25‧10 ^-3 g/cm ³ (gaseous state) and 8.10 ‧10 ^-1 g/cm ³ (liquid) can be obtained. When the volume of the adsorbed gas at a relative pressure of p/p ₀ = 0.8 is converted into the corresponding liquid volume, it has a total pore volume in the range of 0.1 to 3.0 cm ³ /g. The nitrogen adsorption isotherm can be obtained according to the procedure described in DIN 66135. The total pore volume refers to pores having an average pore diameter in the range of 2 to 50 nm, preferably 2 to 10 nm.

In one embodiment of the invention, the carbonaceous material obtained by the process of the invention has an average pore diameter in the range of 2 to 50 nm, preferably 2 to 10 nm, in accordance with BJH (Barret-Joyner-Halenda) The method is determined by a nitrogen adsorption method, see, for example, EP J Barrett et al., J. Am. Chem. Soc. 1951, 73, 373.

In one embodiment of the invention, the carbonaceous material from the process of the invention has a steep pore diameter distribution. The steep pore diameter distribution according to the present invention can be expressed in a graph showing a peak derivative of the cumulative pore volume dV(d) as a function of the pore diameter d _BJH , and the peak width measured at half height is in the range of 2 to 3 nm. in. In another embodiment, the peak width measured at the bottom of the peak is in the range of 7 to 8 nm in a graph showing the derivative of the cumulative pore volume dV(d) as a function of pore diameter d _BJH .

By the method of the present invention, a nitrogen-containing carbonaceous material which can have an inorganic salt content of from 1 to 50 ppm, preferably up to 20 ppm, can be obtained, and in the scope of the present invention, ppm means ppm based on the total weight of the carbonaceous material. In a particularly preferred embodiment, the nitrogen-containing carbonaceous material obtained by the process of the invention does not comprise any detectable amount of inorganic salt. The inorganic salt content can be determined by, for example, an atomic absorption spectrometer or an inductively coupled plasma mass spectrometer (ICP-MS).

The nitrogen-containing carbonaceous material obtained by the process of the invention is extremely suitable as an electrode of a capacitor and as a catalyst or as a carrier for the catalyst.

Another aspect of the invention is a carbonaceous material having a nitrogen content in the range of 1 to 8, preferably 5 to 7% by weight, and optionally an inorganic salt in the range of 50 ppm, preferably 1 to 20 ppm. The carbonaceous material has a BET area in the range of 500 to 700 m ² /g and a capacitance in the range of 5 to 100 μF/cm ² , preferably 6 to 90 μF/cm ² . The carbonaceous material may also be referred to as the carbonaceous material of the present invention. For example, according to JR Miller and AF Burke, Electric Vehicle Capacitor Test, Procedures Manual, Idaho National Engineering Laboratory, report number: DOE/ID-10491, 1994 and/or according to RB Wright and C. Motloch, Freedom CAR Ultracapacitor Test, Manual, Idaho National Engineering Laboratory, report number: DOE/NE ID-11173, 2004 determination.

The nitrogen content can be determined by elemental analysis.

In one embodiment of the invention, the carbonaceous material of the present invention does not comprise any amount of inorganic salt detectable according to the above process.

In one embodiment of the invention, the carbonaceous material of the present invention may comprise a fused carbocyclic aromatic and a nitrogen-containing heteroaromatic ring.

In one embodiment of the invention, the carbonaceous material of the invention has a total pore volume in the range from 0.1 to 3.0 cm ³ /g, preferably from 0.5 to 1.0 cm ³ /g, which is determined primarily by nitrogen adsorption according to DIN 66135 . The method comprises converting the volume of adsorbed gas at a relative pressure of p/p ₀ = 0.8 using a nitrogen density of 1.25‧10 ^-3 g/cm ³ (gaseous) and 8.10‧10 ^-1 g/cm ³ (liquid). Into the corresponding liquid volume. The nitrogen adsorption isotherm can be obtained according to the procedure described in DIN 66135.

In one embodiment of the present invention, the carbonaceous material of the present invention has an average pore diameter in the range of 2 to 50 nm, preferably 2 to 10 nm, in accordance with the BJH (Barret-Joyner-Halenda) method. Determination by nitrogen adsorption method.

In one embodiment of the invention, the carbonaceous material of the present invention has a steep pore diameter distribution. The steep pore diameter distribution according to the present invention can be expressed in a graph showing a derivative of the cumulative pore volume dV(d) as a function of the pore diameter d _BJH , and the peak width measured at half height is in the range of 2 to 3 nm. . In another embodiment, in a graph showing a derivative of the cumulative pore volume dV(d) as a function of pore diameter d _BJH , the peak width measured at the bottom of the peak is in the range of 7 to 8 nm.

In one embodiment of the invention, the carbonaceous material of the invention has a total sulfur content in the range of from 0.1 to 1.0% by weight. The sulfur content can be determined by combustion analysis. If only sulfur-free compounds (a) and (b) are converted in step (A), the sulfur content can be achieved.

In one embodiment of the invention, the carbonaceous material of the invention has a total sulfur content in the range of from 0.1 to 1.0% by weight. This sulphur content can be achieved if at least one sulfur-containing compound (a) or (b) is converted in step (A).

In one embodiment of the invention, the carbonaceous material of the present invention has a steep void diameter distribution.

The carbonaceous material of the present invention can be advantageously used as an electrode of a capacitor. The capacitor may, for example, comprise an electrode comprising a carbonaceous material of the invention. The capacitor according to the invention may additionally comprise a counter electrode. The counter electrode may be made of, for example, palladium or carbon, such as carbon including a binder, which is also referred to simply as a binder.

Another aspect of the invention is an electrode comprising at least one carbonaceous material of the invention and at least one binder.

In one embodiment of the invention, the carbonaceous material of the present invention can be mixed with a binder to form an electrode of a capacitor in accordance with the present invention. Suitable binders are selected from the group consisting of organic polymers, especially water-insoluble organic polymers, wherein the polymers may also encompass copolymers. Preferred water-insoluble polymers are fluorinated polymers such as polyvinylidene fluoride, polyvinyl fluoride, polytetrafluoroethylene, copolymers from tetrafluoroethylene and hexafluoropropylene, copolymers derived from vinylidene fluoride and hexafluoropropylene. Or a copolymer of vinylidene fluoride and tetrafluoroethylene. For the purposes of the present invention, vinylidene fluoride may also be referred to as vinylidene fluoride, and polyvinylidene fluoride may also be referred to as polyvinylidene fluoride.

In one embodiment of the invention, the electrode of the present invention further comprises at least one carbonaceous material of the invention and at least one binder.

In one embodiment of the invention, the carbonaceous material of the present invention may be mixed with a binder and at least one additive to form an electrode of a capacitor according to the present invention. Suitable additives are soot, carbon black and activated carbon.

The electrodes of the present invention are coupled to at least one other component of the capacitor through one or more current collectors. The current collector is not considered to be an assembly of the electrodes of the present invention within the scope of the present invention.

The electrode of the present invention may further comprise a skeleton such as a metal foil or a metal mesh. Suitable metal foils can be made, for example, of nickel. Suitable metal meshes can be made, for example, of steel, especially stainless steel. The current skeleton is not considered to be an assembly of the electrodes of the present invention within the scope of the present invention.

In one embodiment of the invention, the electrode of the present invention comprises from 50 to 90% by weight of the carbonaceous material of the invention, preferably from 75 to 85% by weight, and from 1 to 20% by weight of binder, preferably 7.5. To 15% by weight, the total amount of the additive (group) in the range of 0 to 20% by weight, preferably 7.5 to 15% by weight, based on the total of the electrode component of the present invention.

The electrode of the present invention may further comprise or be soaked through the electrolyte. Examples of the electrolyte are sulfuric acid, aqueous potassium hydroxide solution and so-called ionic liquids such as 1,3-disubstituted imidazolium salts. Preferred 1,3-disubstituted imidazolium salts correspond to formula (IV)

Wherein R ² , R ³ , R ⁴ and R ⁵ independently of each other are carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic, araliphatic groups having from 1 to 30 One carbon atom may comprise one or more heteroatoms and/or may be substituted by one or more functional groups or halogens, wherein adjacent groups R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ may also The groups R ³ and R ^{4 which} are linked together and independently of each other may also be hydrogen, halogen or a functional group, and A ^a- is selected from the group consisting of fluoride ion; hexafluorophosphate; hexafluoroarsenate; hexafluoroantimonate; Trifluoroarsenate;nitrite;nitrate;sulfate;hydrogen sulfate;carbonate;bicarbonate;phosphate;hydrogen phosphate;dihydrogen phosphate;vinyl phosphonate; dicyanamide; Fluoroethyl)phosphinate; tris(pentafluoroethyl)trifluorophosphate; tris(heptafluoropropyl)trifluorophosphate; bis[oxalate (2-)]borate; bis[salicylate] 2-)]borate; bis[1,2-benzenediolate (2-)O,O']borate;tetracyanoborate;tetracarbonylcobaltate; formula (Va)[BR ^a R ^b R ^c R ^d ] ^- a tetra-substituted borate in which R ^a to R are independent of each other Each ^d is a fluoro or carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic group having from 1 to 30 carbon atoms and may include one or more heteroatoms And/or may be substituted by one or more functional groups or halogens; an organic sulfonate of the formula (Vb)[R ^e -SO ₃ ] ^- , wherein R ^e is a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, An aliphatic, aromatic or araliphatic group having from 1 to 30 carbon atoms and which may include one or more heteroatoms and/or may be substituted by one or more functional groups or halogens; formula (Vc)[R ^f - COO] ^- of carboxylate, wherein R ^f is hydrogen or a carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic or araliphatic radical having from 1 to 30 carbon atoms and It may include one or more heteroatoms and/or may be substituted by one or more functional groups or halogens; (Vd)[PF _x (C _y F _2y+1-z H _z ) _6-x ] ^- (fluoroalkyl ) fluorophosphate, of which 1 x 6, 1 y 8 and 0 z 2y+1;Formula (Ve)[R ^g -SO ₂ -N-SO ₂ -R ^h ]-, (Vf)[R ⁱ -SO ₂ -N-CO-R ^j ]- or (Vg)[R ^k -CO-N-CO-R ^l ]- oxime imine group, wherein R ^g to R ^l independently of each other are hydrogen or carbon-containing organic, saturated or unsaturated, acyclic or cyclic, aliphatic, aromatic a group or araliphatic group having from 1 to 30 carbon atoms and which may include one or more heteroatoms and/or may be substituted by one or more functional groups or halogens; another aspect of the invention is the use of the invention A method of producing an electrode (preferably a capacitor electrode) from a carbonaceous material. This method can be referred to as the process of the present invention.

In one embodiment of the invention, the process of the invention comprises the step of mixing at least one carbonaceous material of the invention with at least one binder and optionally at least one additive in the presence of water. By this mixing, an aqueous formulation, such as an aqueous paste or slurry, will be formed. The paste or slurry can be used to apply the mixture thus obtained, for example, by coating the material with the paste or slurry and then drying. The coating method can be carried out, for example, by using a squeegee, a roller blade or a cutter.

The drying method can be carried out, for example, in a drying chamber or a drying oven. A suitable temperature is 50 to 150 °C. The drying method can be carried out under normal pressure or reduced pressure, for example, at a pressure in the range of 1 to 500 mbar.

Another aspect of the invention is the use of the carbonaceous material of the invention as a catalyst or catalyst support. The carbonaceous material of the present invention can, for example, serve as a catalyst for the reaction.

Another aspect of the invention is a catalyst comprising the carbonaceous material of the invention. Such catalysts of the invention may comprise a material of the invention as a catalytically active material or as a carrier for a catalytically active material.

In a particular embodiment of the invention, the carbonaceous material of the invention is used as a support for 2,2'-bipyridyl di-glycolized platinum to catalyze the oxidation of methane to methanol.

The invention will now be further described by way of examples.

I. Conversion reaction of compound (b) with compound (a) I.1 Conversion reaction of melamine (b.1) with terephthalaldehyde (a.1): preparation of substance (A1.1)

Add melamine (b.1) (313 mg, 2.49 mmol), terephthalaldehyde (a.1) (500 mg) to a flame-dried pumping reaction flask (Schlenk flask) equipped with a condenser and a magnetic stir bar. , 3.73 mmol) and dimethyl hydrazine (15.5 ml). After degassing by blowing in argon gas, the resulting mixture was heated to 180 ° C in an argon atmosphere for 72 hours. After cooling to room temperature, pass through a Buchner funnel (B Chner funnel) The precipitate (A1.1) was separated by filtration and subjected to Soxhlet extraction using tetrahydrofuran (THF). The solvent was removed in vacuo at room temperature to afford a white powdery material (A1.1) of 61% yield.

I.2 Conversion reaction of melamine (b.1) with biphenyl-4,4'-dicarbaldehyde (a.2): preparation of substance (A2.1)

Add melamine (b.1) (200 mg, 1.59 mmol) and biphenyl 4,4'-dicarbaldehyde (a.2) to a flame-dried gassing reaction flask equipped with a condenser and a magnetic stir bar. 500 mg, 2.38 mmol) and dimethyl hydrazine (11.0 ml). After degassing by blowing in argon gas, the resulting mixture was heated to 180 ° C in an argon atmosphere for 72 hours. After cooling to room temperature, the precipitate (A2.1) was separated by filtration through a Buchner funnel and subjected to Soxhlet extraction using THF. The solvent was removed in vacuo at room temperature to afford a white powdery material (A2.1).

I.3 Conversion reaction of melamine (b.1) with isophthalaldehyde (a.3): preparation of substance (A3.1)

To a flame-dried pumping reaction flask equipped with a condenser and a magnetic stir bar, melamine (b.1) (313 mg, 2.49 mmol) and isophthalaldehyde (a.3) (500 mg, 3.73 mmol) were added. And dimethyl hydrazine (15.5 ml). After degassing by blowing in argon gas, the resulting mixture was heated to 180 ° C in an argon atmosphere for 72 hours. After cooling to room temperature, the precipitate (A3.1) was separated by filtration through a Buchner funnel and subjected to Soxhlet extraction using THF. The solvent was removed in vacuo at room temperature to afford a white powdery material (A3.1) of 62% yield.

I.4 Conversion reaction of melamine (b.1) with 1,3,5-gin(4-methylnonylphenyl)benzene (a.4): preparation of substance (A4.1)

Add melamine (b.1) (124 mg, 0.98 mmol) and 1,3,5-gin (4-methylnonylphenyl) to a flame-dried pumping reaction flask equipped with a condenser and a magnetic stir bar. Benzene (a.4) (383 mg, 0.98 mmol) and dimethyl hydrazine (4.9 ml). After degassing by blowing in argon gas, the resulting mixture was heated to 180 ° C in an argon atmosphere for 72 hours. After cooling to room temperature, the precipitate (A4.1) was separated by filtration through a Buchner funnel and subjected to Soxhlet extraction using THF. The solvent was removed in vacuo at rt to afford 66% yield of off white powder (A4.1).

I.5 Conversion reaction of melamine (b.1) with naphthalene-2,6-diformaldehyde (a.5): preparation of substance (A5.1)

Add melamine (b.1) (231 mg, 1.81 mmol) and naphthalene-2,6-diformaldehyde (a.5) to a flame-dried pumping reaction flask equipped with a condenser and a magnetic stir bar (500 mg) , 2.715 mmol) and dimethyl hydrazine (11.3 ml). After degassing by blowing in argon gas, the resulting mixture was heated to 180 ° C in an argon atmosphere for 72 hours. After cooling to room temperature, the precipitate (A5.1) was separated by filtration through a Buchner funnel and subjected to Soxhlet extraction using THF. The solvent was removed in vacuo at rt to afford 66% yield of off white powder (A5.1).

I.6 Conversion reaction of melamine (b.1) with benzene-1,3,5-triformaldehyde (a.6): preparation of substance (A6.1)

Melt (b.1) (389 mg, 3.08 mmol) and benzene-1,3,5-tricarbaldehyde (a.6) were added to a flame-dried gassing reaction flask equipped with a condenser and a magnetic stir bar ( 500 mg, 3.083 mmol) and dimethyl hydrazine (15.0 ml). After degassing by blowing in argon gas, the resulting mixture was heated to 180 ° C in an argon atmosphere for 72 hours. After cooling to room temperature, the precipitate (A6.1) was separated by filtration through a Buchner funnel and subjected to Soxhlet extraction using THF. The solvent was removed in vacuo at rt to afford 68% yield of off white powder (A6.1).

I.7 Conversion reaction of melamine (b.1) with pyridine-2,6-diformaldehyde (a.7): preparation of substance (A7.1)

Add melamine (b.1) (311 mg, 2.467 mmol) and pyridine-2,6-diformaldehyde (a.7) to a flame-dried pumping reaction flask equipped with a condenser and a magnetic stir bar (500 mg) , 3.700 mmol) and dimethyl hydrazine (15.4 ml). After degassing by blowing in argon gas, the resulting mixture was heated to 180 ° C in an argon atmosphere for 72 hours. After cooling to room temperature, the precipitate (A7.1) was separated by filtration through a Buchner funnel and subjected to Soxhlet extraction using THF. The solvent was removed under vacuum at room temperature to afford a white powdery material (A7.1) of 75% yield.

I.8 Conversion reaction of melamine (b.1) with 2,2'-bipyridyl-5,5'-dicarbaldehyde (a.8): preparation of substance (A8.1)

To the flame-dried pumping reaction flask equipped with a condenser and a magnetic stir bar, melamine (b.1) (198 mg, 1.571 mmol), 2,2'-bipyridyl-5,5'-diformaldehyde ( A.8) (500 mg, 2.357 mmol) and dimethyl hydrazine (9.8 ml). After degassing by blowing argon gas, the resulting mixture was heated to 180 ° C in an argon atmosphere for 72 hours. After cooling to room temperature, the precipitate (A8.1) was separated by filtration through a Buchner funnel and subjected to Soxhlet extraction using THF. The solvent was removed under vacuum at room temperature to afford an off-white powder material (A 8.1).

I.9 Conversion reaction of melamine (b.1) with thiophene-2,5-diformaldehyde (a.9): preparation of substance (A9.1)

Add melamine (b.1) (300 mg, 2.378 mmol) and thiophene-2,5-diformaldehyde (a.9) to a flame-dried pumping reaction flask equipped with a condenser and a magnetic stir bar (500 mg) , 3.567 mmol) and dimethyl hydrazine (14.9 ml). After degassing by blowing argon gas, the resulting mixture was heated to 180 ° C in an argon atmosphere for 72 hours. After cooling to room temperature, the precipitate (A9.1) was separated by filtration through a Buchner funnel and subjected to Soxhlet extraction using THF. The solvent was removed under vacuum at room temperature to afford a brown powder material (A9.1) of 62% yield.

I.10 Conversion reaction of melamine (b.1) with furan-2,5-diformaldehyde (a.10): preparation of substance (A10.1)

Add melamine (b.1) (339 mg, 2.686 mmol) and furan-2,5-diformaldehyde (a.10) (500 mg) to a flame-dried pumping reaction flask equipped with a condenser and a magnetic stir bar. , 4.029 mmol) and dimethyl hydrazine (16.8 ml). After degassing by blowing argon gas, the resulting mixture was heated to 180 ° C in an argon atmosphere for 72 hours. After cooling to room temperature, the precipitate (A10.1) was separated by filtration through a Buchner funnel and subjected to Soxhlet extraction using THF. The solvent was removed under vacuum at rt to afford a brown powder material (A10.1).

I.11 Conversion reaction of 2,4-diaminotriazine (b.2) with 1,3,5-gin(4-methylnonylphenyl)benzene (a.4): substance (A4.2) Preparation

Add 2,4-diaminotriazine (b.2) (250 mg, 2.250 mmol) and 1,3,5-gin to the flame-dried pumping reaction flask equipped with a condenser and a magnetic stir bar. 4-Methylphenylphenyl)benzene (a.4) (878 mg, 2.250 mmol) and dimethylhydrazine (11.2 ml). After degassing by blowing argon gas, the resulting mixture was heated to 180 ° C in an argon atmosphere for 72 hours. After cooling to room temperature, the precipitate (A4.2) was separated by filtration through a Buchner funnel and subjected to Soxhlet extraction using THF. The solvent was removed under vacuum at room temperature to afford an off-white powder material (A4.2).

I.12 Conversion reaction of 2,4-diaminotriazine (b.2) with benzene-1,3,5-trialdehyde (a.6): preparation of substance (A6.2)

To the flame-dried pumping reaction flask equipped with a condenser and a magnetic stir bar, 2,4-diaminotriazine (b.2) (250 mg, 2.250 mmol) and benzene-1,3,5- Triformaldehyde (a.6) (365 mg, 2.250 mmol) and dimethyl hydrazine (11.2 ml). After degassing by blowing argon gas, the resulting mixture was heated to 180 ° C in an argon atmosphere for 72 hours. After cooling to room temperature, the precipitate (A6.2) was separated by filtration through a Buchner funnel and subjected to Soxhlet extraction using THF. The solvent was removed under vacuum at room temperature to afford a white powdery material (A6.2) of 59% yield.

Table 1: Analytical data of the material from step (A)

The contents of carbon, hydrogen, sulfur and nitrogen and the C/H and C/N ratios were determined by combustion analysis. The C/H and C/N ratios refer to the ratio by weight.

S _BET : BET surface area, determined according to DIN 66135 (measured value) and DIN 66131 (evaluation, calculated value) using nitrogen.

MPV _(0.1) : medium pore volume, determined by nitrogen adsorption method, measured at a relative pressure of p/p ₀ = 0.1. The adsorbed gas can be converted to a liquid amount which corresponds to the pore volume at the respective relative pressures.

PV _(0.8) : pore volume, which uses a nitrogen density of 1.25‧10 ^-3 g/cm ³ (gaseous) and 8.10‧10 ^-1 g/cm ³ (liquid), with p/p ₀ =0.8 The volume of the adsorbed gas under the relative pressure is converted into the corresponding liquid volume to be measured.

d _BJH : average pore diameter as determined by the BJH method, DIN 66134.

PV _BJH : Pore volume as determined by the BJH method, DIN 66134.

II. Step (B) Heating method according to step (A)

General Procedure: A sample of the material according to step (A) (120 mg) was placed on a quartz boat and heated to a temperature according to Table 2 under a stream of argon at a heating rate of 2 ° C/min. The samples were kept at their respective temperatures for 1 hour. After cooling, each of the materials of the present invention was recovered as a black powder.

Table 2: Synthesis and analytical data of the materials of the present invention

III. Electrochemical testing

The electrode preparation method of the present invention is as follows. The carbonaceous material of the present invention and carbon black (Mitsubishi Chemicals, Inc., carbon content > 99.9%) were mixed in an agate mortar at a weight ratio of 8:1 until a homogeneous black powder was obtained. An aqueous PTFE binder emulsion (60% solids, available from Sigma) was added to the mixture together with a few drops of ethanol, the PTFE content being 10% by weight of the solids content of the binder, and the carbonaceous material of the present invention: carbon Black: The weight ratio of the binder is 8:1:1. After briefly evaporating in air, the resulting paste was compressed at 5 MPa to a nickel wire mesh (for testing with 1 M KOH electrolyte) or stainless steel wire mesh (for testing with 1 MH ₂ SO ₄ electrolyte) Each nickel wire mesh and stainless steel wire mesh are connected to the stainless steel wire for connection, and each has a size of 1 cm‧1 cm. The electrode of the present invention is obtained. The electrode of the present invention was dried in air at 80 ° C for 16 h. Each electrode contains from 3 to 5 mg of the carbonaceous material of the present invention and has a geometric surface area of about 1 cm ² . Then, a palladium foil was used as a counter electrode, and a standard calomel electrode (SCE) or an Ag/AgCl electrode was used as a reference electrode.

Table 3: Electrochemical data of the substance of the present invention, using a 1 MH ₂ SO ₄ aqueous solution as an electrolyte, and the carbonaceous material of the present invention is applied to a nickel foil

Table 4: Electrochemical data of the substance of the present invention, using a 1 M KOH aqueous solution as an electrolyte, and the carbonaceous material of the present invention is applied to a stainless steel wire mesh for measurement

The electrochemical characterization method was performed in an EG&G potentiostat/galvanostat model 2273 advanced electrochemical system. A conventional battery having a three-electrode structure is used.

A palladium foil was used as the counter electrode, and a standard calomel electrode (SCE) or an Ag/AgCl electrode was used as a reference electrode. This type of test is carried out in a solution of 1 MH ₂ SO ₄ or 1 M KOH saturated with nitrogen. The potential range is -1.00 to 0.00 V (SCE) or -0.05 to +0.95 V (Ag/AgCl) at different scan rates. All measurements were taken at room temperature.

The normalized mass capacitance value C _g is measured in a three-electrode cell and is calculated from the constant current discharge curve using the following formula (1):

C _g =(I‧t)/(m‧ΔV) (1)

Wherein I is the specific discharge current density, t is the total discharge time, ΔV is the potential range, and m is the mass of the electrode material. The corresponding volume C _s value can be obtained by dividing C _g by the BET surface area of each carbonaceous material.

Claims (21)

A method for producing a nitrogen-containing porous carbonaceous material having a BET surface area of 50 to 3000 m ² /g, wherein the nitrogen content is in the range of 1 to 8 wt%, and having a weight of up to 50 ppm inorganic salt content of the present case, comprising the steps of: (A) (a) with the conversion reaction (a) and (b) at least one per molecule, at least two NH ₂ - group of a heterocyclic hydrocarbon; (b) At least one aromatic compound having at least two aldehyde groups per molecule, wherein the aromatic compound has a main chain selected from the group consisting of a carbocyclic aromatic ring and a heterocyclic aromatic ring and wherein the aldehyde group is directly bonded to the main chain, (B) Heating to a temperature in the range of 700 to 1200 ° C in the absence of oxygen, wherein the heterocyclic hydrocarbon having at least two NH ₂ - groups per molecule (a) is selected from the group consisting of compounds of formula (III) Wherein X ² is selected from the group consisting of hydrogen, methyl, phenyl, n-hexyl, OH and NH ₂ . The method of claim 1, wherein the at least one aromatic compound (b) having at least two aldehyde groups per molecule is selected from the group consisting of heteroaromatic dialdehydes, heteroaromatic trialdehydes, and carbocyclic aromatic dialdehydes and trialdehydes. , whose aromatic backbone is selected from Phenyl, naphthyl, phenyl, exfoliation, exfoliation, exudation, exfoliation, exfoliation, 1,1':4',1"-extension of triphenyl, 1,1'-extension snail [茚] group and 9,9'-extension snail [茀] group. The method of claim 1 or 2, wherein the heteroaromatic dialdehyde is selected from the group consisting of the molecules of the formulae (I) and (II) Wherein the code is defined as follows: R ¹ is selected from the group consisting of hydrogen, C ₁ -C ₆ -alkyl, benzyl, unsubstituted or C ₆ -C substituted with one to three C ₁ -C ₄ -alkyl groups per molecule _{The 14} -aryl group and the X ¹ group are selected from the group consisting of oxygen, sulfur and NH. The method of claim 1 or 2, wherein the conversion reaction (A) is carried out in DMSO as a solvent. The method of claim 1 or 2, wherein the conversion reaction (A) does not use a catalyst containing a metal or a metal ion. The method of claim 1 or 2, wherein the carbonaceous material has an average pore diameter in the range of 2 to 50 nm, which is determined by a nitrogen adsorption method according to the BJH (Barret-Joyner-Halenda) method. The method of claim 1 or 2, wherein the carbonaceous material has a steep pore diameter distribution, wherein the one-step derivative dV(d) showing a cumulative pore volume as a function of pore diameter d _BJH is measured at half height The peak width is in the range of 2 to 3 nm. The method of claim 1 or 2, wherein the conversion of the compound (a) and the compound (b) in the step (A) is carried out at a temperature ranging from 150 to 250 °C. A carbonaceous material having a nitrogen content in the range of 1 to 8 wt% and an optionally present inorganic salt content of 50 ppm, the carbonaceous material having a BET surface in the range of 500 to 700 m ² /g and 5 to 100 μF/ cm ² in a range of capacitors, wherein substantially measured according to DIN 66135 by the nitrogen adsorption method, the total pore volume having / g range of 0.1 to 1.0cm ^3. The carbonaceous material of claim 9, which comprises a fused aromatic and a nitrogen-containing heteroaromatic ring. The carbonaceous material of claim 9 or 10, wherein the carbonaceous material has an average pore diameter in the range of 2 to 50 nm, which is determined by a nitrogen adsorption method according to the BJH (Barret-Joyner-Halenda) method. The requested item carbonaceous material 9, or 10 of, wherein the carbonaceous material has a steep of the pore diameter distribution, which displays the cumulative pore volume of one of the first derivative dV (d) a pore diameter d _BJH function figures, to half the height The peak width measured at the time was in the range of 2 to 3 nm. A carbonaceous material according to claim 9 or 10, which has a total sulfur content in the range of 0.1 to 1.0% by weight. A carbonaceous material according to claim 9 or 10, wherein it can be produced according to the method of at least one of claims 1 to 8. A use of a carbonaceous material according to any one of claims 9 to 14 as a component of a capacitor. A use of a carbonaceous material according to any one of claims 9 to 14 as a catalyst or as a carrier for the catalyst. A catalyst comprising the carbonaceous material of any one of claims 9 to 14. An electrode comprising at least one carbonaceous material of any one of claims 9 to 14 and at least one binder. The electrode of claim 18, further comprising at least one additive. A method of producing an electrode according to claim 18 or 19, comprising the step of mixing at least one carbonaceous material according to any one of claims 9 to 14 with at least one binder in the presence of water, the mixture thus obtained Apply to the metal film and dry. The method of claim 20, wherein the carbonaceous material is mixed with the binder and at least one additive.