WO2018114335A1

WO2018114335A1 - Apparatus and method for producing carbon fibres or textile fabrics formed from carbon fibres

Info

Publication number: WO2018114335A1
Application number: PCT/EP2017/081677
Authority: WO
Inventors: Eckhard Beyer; Beata Lehmann; Tilo KÖCKRITZ
Original assignee: Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V.; Technische Universität Dresden
Priority date: 2016-12-23
Filing date: 2017-12-06
Publication date: 2018-06-28
Also published as: DE102016015668A1

Abstract

The invention for producing carbon fibres or textile fabrics comprises a module with two nozzles guided one inside the other, having different internal diameters. A first nozzle is arranged inside the second nozzle and one of the nozzles is connected to a supply reservoir, in which a polymer is stored, and the other nozzle is connected to a supply reservoir, in which electrically conducting particles are held in a dispersion. The dispersion in which electrically conducting particles are held is supplied from the supply reservoir through the one nozzle and the polymer is supplied through the other nozzle from the second supply reservoir, so that a fibre is obtained which is formed with a core and a jacket on exit from the nozzles. The core is formed from the polymer and the jacket from electrically conducting particles, or vice versa. The fibres made in this way or a textile fabric are supplied to a thermal treatment in which carbonization is achieved.

Description

Apparatus and method for producing carbon fibers or textile structures formed with carbon fibers

The invention relates to an apparatus and a method for the production of carbon fibers or of textile structures which are formed with carbon fibers.

The electrical heating of Präcursorfasern based on an electrical resistance carbonization requires a minimum electrical conductivity. This is not present in the conventional spun Präcursormaterial, so that with other methods, this electrical conductivity must be prepared before by means of electrical method (resistance heating, possibly induction) can be carbonized. After stabilization (conventional oven or microwave stabilization after

DE 10 2015 205 809 AI), the not yet electrically conductive material (fibers, surfaces) in a first Karbonisierungsstufe up to a temperature of at least 600 ° C by a conventional kiln carbonation or Carbonization by means of a microwave obtained sufficient electrical resistance, which is based on PAN-based carbon fibers in the lower kOhm range. The use of higher temperatures during the

The pre-carbonization step further reduces the electrical output resistance, with PAN-based carbon fibers assuming a linear relationship between carbonation temperature and the natural logarithm of electrical resistance. The higher the temperature is set in the Vorkarbonisierungsstufe, the lower the possible energy savings during the Elektrokarbonisierung. There is always an optimum between pre-carbonization temperature, resulting energy savings during the further carbonization and the mechanical and electrical properties of the materials to be carbonized (fibers, surfaces) to adjust. Furthermore, the previous process is complicated by the at least three required process stages (stabilization, pre-carbonization, electric carbonization) and the production area and time are required to carry out the processes.

The stabilization and Vorkarbonisierung according to the conventional method or using microwaves can be circumvented by the fact that the precursor fibers have a minimum electrical conductivity directly after spinning. This can be achieved by the

Precursorfaser during the spinning process conductive particles are added, forming an electrically conductive network in the non-electrically conductive Preccursormaterial. Preferably, the particles with a high aspect ratio, such as in particular carbon nanotubes (CNT) or

Carbon nanofibers (nano-CF) and mixtures thereof or mixtures thereof with other carbon allotropes (eg carbon black (CB)

Fullerenes, carbon nanohorns (CNH), graphene). As a result, the minimum electrical conductivity can be achieved with a smaller amount of mass added than with spherical particles (e.g., CB). In addition, the isotropically distributed CNT or nano-CF additives result in higher thermal conductivity which facilitates thermal processes and prevents local overheating or burning of the precursor polymer (e.g., PAN) during stabilization.

The integration of CNTs in polymer fibers is known. For the efficiency of Effectiveness of CNT reinforcement in the respective fiber plays a crucial role in the CNT surface area and the homogeneity of the CNT distribution in the fiber. With a large CNT surface within the fiber (little to no CNT agglomerates) and a small number of graphite layers (single-wall rather than multi-walled CNTs), CNTs have the following advantages in stabilizing PAN fibers in particular, which also affect carbonization:

Improved polymer crystallinity and higher ordered polymer structures in the interface region between PAN and CNTs,

Higher degree of orientation of the stabilized polymer molecules,

Higher fiber tensile strength of the precursor material and thus the possibility of using a higher fiber pretension during stabilization,

• smaller stabilization time due to higher fiber preload,

Higher degree of conversion into an ordered graphite structure at smaller stabilization temperatures,

• less chemical and entropic shrinkage during the

Stabilization,

• Reduction of the formation of ß-amino nitrile groups and formation of longer conjugated nitrile segments during stabilization and

• Reduction of activation energy for cyclization, oxidation and crosslinking reactions.

CNTs may contribute to better mechanical, thermal and electrical properties of the carbon fibers made therefrom, suggesting that the possibility of defining the interface between CNTs and precursor fiber material provides additional opportunities to tailor carbon fibers. An improvement in electrical conductivity of> 25% at CNT contents of 0.5 to 1.0 mass% can be expected.

MWCNT-based PAN / CNT fibers (multi-walled CNTs) with a MWCNT content of 15% by mass to 20% by mass, which were prepared in a conventional spinning process using DMF (dimethylformamide), can be obtained by a thermal aftertreatment in the Oven (180 ° C, 2 Hours, oxygen) become electrically conductive, whereby the electrical conductivity increases by the furnace treatment from 10 ^"5 S / m to ~ 28 S / m (20% MWCNT content) An electrically conductive CNT network is formed in a PAN The warming begins first in the edge area of the CNTs (electrons migrate within the matrix in the CNTs) and the heat subsequently spreads out stepwise within the precursor matrix.

So thermally treated individual filaments or fiber bundles can then be heated electrically by resistance heating. When applying 7 mA PAN / CNT filaments, an electrical conductivity of 800 S / m can be achieved. At the same time, the filaments are stabilized, as can be detected by FTIR (Fourier transformed infrared) spectroscopy) and WAXD (Wide-angle X-ray diffraction).

WO2016 / 060929A2 and WO2016 / 060929A3 describe the preparation of CNT / PAN composite fibers and their stabilization and carbonization. The fibers are made by conventional spinning techniques such as e.g. Dry-Jet-Wet spinning produced and pretreated prior to the use of static electrical stabilization by furnace heating to 180 ° C in an additional step. The studies on heating the fibers with electric current refer exclusively to individual fibers or fiber bundles, the process of resistance heating takes place statically in air, the implementation in an industrial process is not described. The treatment of the fibers at higher temperatures than the stabilization temperature by an electrical resistance heating in an inert atmosphere is not shown.

Nanofibers:

There is also a difference between the production of conventional

Carbon fibers and carbon nanofibers known by electrospinning, where the fibers are usually deposited as a random web during spinning. During the thermal treatment, the fibers are not exposed to any defined distortion in the fiber axis direction, they therefore become very brittle.

In conventional manufacture, the minimum diameter of the carbon fibers are now at 5 μιη (T1000 ^® G (TORAY CARBON FIBERS AMERICA, INC.). It is assumed that the lower limit of the diameter of fibers ~ 2 μιη can not be fallen below. In the production of finer fibers, the fiber deposit takes place as a random web. By modifying the collector, it is also possible here to produce endless fiber bundles whose individual filaments are largely oriented in a preferred direction, so that they, like the conventional carbon fibers, are additionally subjected to a drafting process in air, water vapor or water bath and can be stabilized and carbonized under tension. Thus, the process of thermal treatment can be matched to that of conventional fibers. Due to the smaller fiber diameter (75 to 1500 nm) of, for example, PAN precursor filaments, fiber tensile strength, tensile modulus of elasticity and maximum elongation at break increase. Furthermore, it can be assumed that the better mechanical properties of the precursor fibers also lead to better mechanical properties of the nanocarbon fibers produced therefrom. This proof has not been provided so far, the studies on stabilization and carbonization were carried out on random webs.

To improve the electrical conductivity CNTs are added to the spinning solution as in the conventional precursor fibers. The fibers are usually spun by the electrospinning process. The influence of CNTs on conventional furnace stabilization and the following

Carbonation was investigated. The following advantages of the integration of CNTs could be determined:

Influence of integrated CNTs on PAN nanofibers and their

derivatives

SWCNT / MWCNT very good fiber-centered orientation

Unbundling of the SWCNT during the spinning process

Reduction of fiber diameter

increased crystallinity, orientation of the graphitic structures and crystal size in the carbon fibers

higher quality of stabilized fiber webs (less defects)

reduced reaction rate of stabilization

higher crystalline (graphitic) content in the carbonized fiber lower heat shrinkage during carbonization

higher electrical conductivity of the carbon fibers

The largest improvements in the graphitic structure were identified at low carbonization temperatures, with 1000 ° C being the optimal carbonization temperature. In situ pull-out experiments showed good adhesion between DWCNTs and carbon matrix.

CNT surface area size plays a crucial role in the effectiveness of the CNTs in terms of mechanical and electrical properties in each fiber.

A PAN output nanofiber with no addition of CNT has an electrical conductivity of 10 ¹⁰ S / m, with the addition of functionalized MWCNTs this improves to 1.9 ^χ 10 ^"5 S / m to 2.6xl0 ^{" 5} S / m, with the Type of functional groups (-COOH, -NH ₂ or -OH) has no significant influence on the electrical conductivity. Thus, the minimum electrical conductivity for the Elektrokarbonisierung can be achieved. Furthermore, by mixing CNTs with carbon nanofibers (CNF), the electrical conductivity can be further improved. It is also known that by rotation of a

Carbonnanofaserbündels the electrical conductivity can be improved to an optimum, which is probably also applicable to the precursor material.

The previous problem solutions relate to the integration of CNTs in polymer fibers and their static electrical resistance heating of single filaments / fiber bundles for the purpose of stabilization. A problem solution for an industrial process chain is missing.

It is therefore an object of the invention to provide possibilities for the production of carbon fibers or carbon fiber formed textile structures with improved properties, in particular an increased electrical conductivity and thereby be able to reduce the cost of manufacturing.

According to the invention, this object is achieved with a device having the features of claim 1, solved. The claim 8 relates to a method. Advantageous embodiments and further developments of the invention can be realized with features described in the subordinate claims. In the device according to the invention is a module with two nozzles guided into each other, each having a different inner diameter. A first nozzle is arranged inside the second nozzle. The first nozzle is connected to a first reservoir in which a polymer is contained. The other second nozzle is connected to a second reservoir in which electrically conductive particles, in particular carbon nanotubes (CNTs) and / or high-aspect ratio carbon nanofibers (nano-CF), are contained in a dispersion.

By means of conveying devices, the dispersion, in which preferably water, a surfactant, a polymer and / or a solvent for the polymer and the electrically conductive particles are contained, from the second reservoir through the one nozzle and the preferably highly viscous polymer or a polymer with a Solvent for the polymer from the first reservoir through the other nozzle, so that after the exit from the nozzle, a fiber, which is formed with a core and a sheath, is obtained.

The viscosity of the polymer and the dispersion should be suitable for the formation of fibers having a core and a cladding.

The core is then made of or with the polymer and the sheath with electrically conductive particles, in particular with carbon nanotubes and / or carbon nanofibers and / or noble metal nanowires, in particular silver nanocrystals, which preferably have a high aspect ratio in an alternative and in another alternative Core with electrically conductive particles, in particular carbon nanotubes and / or carbon nanofibers and / or Edelmetallnanodrähten, especially silver nanowires, which preferably have a high aspect ratio, and the jacket formed with the polymer.

The formed with a core and a sheath fiber or one with these Fibers formed textile structure is then a thermal treatment in which a stabilization and carbonization is achieved supplied.

Stabilization can be omitted when using high-end precursors, such as polyethylene or poly (p-phenylenebenzobisoxazole) (PBO), as a polymer.

As already stated, a core or shell may be formed with a polymer. Besides polyacrylonitrile (PAN), alternative precursors, such as e.g. Textile PAN, pitch, viscose, cellulose (eg viscose, lyocell, tire cord), lignin, lignin-based polymers and blends with other precursor polymers, polyvinyl alcohol, other synthetic high-end precursors for example polyethylene or poly (p-phenylenebenzobisoxazole) (PBO ) Polypropylene, polyalkenes, polybutadiene, polyethylene terephthalate (PET), polybutyltherephtalate, and chemically modified precursor material thereof are used to form core or sheath. The polymer used can also be polypropylene, polyalkenes,

Polybutadiene, polyethylene terephthalate (PET) or Polybutyltherephtalat (PBT) can be used.

With a dry spinning, wet spinning, gel spinning, melt spinning, dispersion spinning, electrospinning or centrifuge spinning process, the production of the fibers through the nozzles can then be achieved.

A polymer alone can fulfill the function of a binder and be completely expelled during the thermal treatment. As the polymer, polyolefins (polyethylene, polypropylene), polyvinyl alcohol or biodegradable polymers such as polylactide (PLA) may be used each alone or in a mixture. In this case, a suitable viscosity should be maintained, with which processing at the exit from the respective nozzles is possible.

Of the alternative precursors listed above, viscose in particular is of interest since, in comparison with the PAN-based C fiber, an even lower electrical resistance is to be expected (reduction to 43% depending on the process conditions). A textile structure may be, for example, a woven, scrim, knitted fabric or knit fabric.

A first nozzle may have an inner diameter in the range 0.3 mm to 1 mm, preferably about 0.5 mm, and a second nozzle may have a larger inner diameter from 1.2 mm.

The ends / outlet openings of the first and the second nozzle may be arranged at a distance from each other. Advantageously, the outlet opening of the second nozzle with the larger inner diameter in the feed direction of the components emerging from the nozzles should be arranged behind the outlet opening of the first nozzle with the smaller inner diameter. Thereby, a carbon fiber with increased electrical conductivity can be obtained.

In one of the storage containers carbon nanotubes and / or carbon nanofibers can be contained alone or with carbon allotropes, in particular carbon black (CB) in a dispersion with a viscosity suitable for forming the fiber. The dispersion with said carbon particles may contain a suitable polymer which can fulfill the function of a binder. This may be, for example, a solution of a suitable polymer which preferably also contains one with which a homogeneous distribution of carbon nanotubes, carbon nanofibers and optionally carbon allotrope particles can be achieved and agglomeration can be avoided. It can also be an aqueous solution

Be added surfactant.

Preferably, a stabilization and carbonization of the fibers can be carried out with a multistage electrical resistance heating, as has been described in DE 10 2015 221 701 A1. On a conventional carbonization in a continuous furnace can be dispensed with.

In cases where the percolation threshold has not been exceeded, neither in the core nor in the sheath of the fiber, it may be advantageous to obtain the electrical conductivity of the fiber emerging from the nozzles by means of inductive heating or thermal treatment by means of microwave plasma. pass. As a result, a thermal treatment, which leads to the formation of the finished carbonized carbon fibers, can then be carried out by means of electrical resistance heating.

In the production, the procedure is such that a first storage container in which a polymer and / or carbon nanotubes (CNTs) and / or carbon nanofibers (nano-CF) or noble metal nanowires, in particular high aspect ratio silver nanowires, is / are added to a first nozzle and from a second reservoir containing carbon nanotubes (CNTs) and / or carbon nanofibers (nano-CF) or noble metal nanowires, particularly high aspect ratio silver nanowires and / or a polymer, to a second nozzle.

With the emerging from the first and the second nozzle streams a fiber consisting of a core and a sheath is formed. The fiber or a textile formed with a plurality of these fibers is then subjected to a thermal treatment, in which first a stabilization and then a carbonization of the fiber (s) is performed.

A high aspect ratio should be understood to mean a length to diameter / width ratio of at least 5 to 1, preferably at least 10 to 1. With CNTs, for example, an aspect ratio of about 10,000 to 1 can be achieved. As a result, improved electrical conductivity can be achieved by the faster formation of a percolation network with low added proportions by weight (mass content: 0.5% to 1.0%), which can advantageously have an effect in electrical resistance heating.

The core or cladding of the fiber (s) should preferably be formed with a proportion of carbon nanotubes, carbon nanofibers and / or carbon allotropes above the percolation threshold.

The stabilization and carbonization should take place in several stages, which are carried out in succession. The temperature should be increased gradually. In particular, if neither the core nor the sheath of a fiber reaches or has only slightly exceeded the percolation threshold after exiting the nozzles, an inductive heating or a heating by means of a plasma generated with microwaves can take place before and / or during the stabilization the fiber (s) are performed. In an inductive heating, a fiber or a textile structure, which is formed with the fibers, at least one inductor, which is connected to an electrical AC voltage source, with a suitable frequency, are moved past.

Heating by means of a plasma generated with microwaves can be carried out as described in DE 10 2015 205 809 A1. In this case, the percolation threshold should have been exceeded or at least reached, however, either in the core or in the sheath.

A hollow fiber can be produced from a fiber whose core consists exclusively of a polymer, in particular of polymethyl methacrylate, and a sheath which is formed with carbon nanotubes, carbon nanofibers and / or carbon allotropes. Instead of polymethylmethacrylate, a polymer that is leachable or biodegradable by water or solvent can also be used for this purpose.

From a fiber whose core is formed of electrically conductive particles, in particular carbon nanotubes, carbon nanofibers, Edelmetallnanäden and / or carbon allotropes with or without polymer and their shells of a water or solvent washable or biodegradable polymer can be prepared by removing the sheath polymer from the thermal Treatment can be obtained a fiber containing only the core material and thus has a much smaller fiber diameter.

For stabilizing as well as for carbonizing filament strands or textile structures for conventional carbon fibers and carbon nanofibers, no upstream thermal treatment, such as a furnace process, is required. The electrical conductivity of the fibers or surfaces of a textile structure can be improved by the fact that in the spinning process zess be added with the respective nozzle of the dispersion flexible, electrically conductive particles with high aspect ratio (CNTs, nano-CF and mixtures of CNTs and nano-CFs or mixtures of these particles with carbon allotropes such as CB). The CNT content of the dispersion should be sufficient to allow the fibers to pass, or at least reach, the fibers, either directly or through a pre-stabilized, specially designed electrical resistance heating module operating in the air and operating in the same facility get the necessary minimum electrical conductivity. Subsequently, the stabilization and carbonization, which can preferably be carried out by means of electrical resistance heating, particularly preferably in several stages, can be achieved, as has been described in DE 10 2015 221 701 A1. The heating rates can be set specifically and gradually increased with increasing temperature.

In contrast to conventionally producible carbon fibers may be used to improve the electrical conductivity of the precursor fibers according to the invention in addition a core-shell structure: · carbonizable polymer, eg. As PAN, polyethylene, etc., can in one alternative a core and PAN with integrated flexible, conductive particles with high aspect ratio (CNTs or mixture of CNTs and CNF also in combination with CB or similar) can form a sheath .

· Flexible, high aspect ratio conductive particles can provide one

Core (CNTs or mixture of CNTs and CNF also in combination with CB or the like or noble metal nanowires, especially silver nanowires) and a carbonizable precursor polymer (PAN, polyethylene, or the like) may form a sheath. The core can consist of 100% CNTs or 100% CNF in this variant and also, if required, with CB or similar. be combined.

In the latter variant, it is not possible to directly contact the electrically conductive core material for electrical resistance stabilization. An inductive preheating or preheating means

However, microwave plasma can also be used in addition. The ratio of core and sheath diameter can be chosen freely, so that also influence on the properties of the finished carbon fibers or textile formed therewith can be taken.

Both the choice of the inner and outer diameters of the nozzles and the nozzle design (inner and outer nozzles should be flat, outer second nozzles should be shorter or longer than the inner first nozzle) determine fiber buildup and fiber properties. It can be a higher electrical

Conductivity can be achieved when the outer nozzle is shorter than the inner nozzle.

Furthermore, by special polymer combinations (eg PMMA in the core) hollow fibers can be produced after the carbonization, since this or a similar polymer can be at least almost completely expelled during the thermal treatment.

In addition, a water-soluble polymer (e.g., polyvinyl alcohol (PVAL)) can be used for the formation of the fiber core. This can be removed after the spinning process if necessary by a washing process. The lightweight construction efficiency can be further increased by such hollow fiber constructions. An inductive preheating can also be used advantageously in this embodiment.

The processes of stabilization and carbonization can be carried out exclusively by means of electrical resistance heating and continuous production, which leads to a simplification of the process management. It can be achieved a significant reduction in the process time by the significantly higher heating rates, especially in the carbonization. A gradual heating with defined heating rates is possible. The required length of a plant for the production of carbon fibers can be shortened. It is an adjustability of the electrical input resistance of the precursor material and a controllability of the stabilizing and

The degree of carbonation and thus the structural or mechanical properties in the defined, depending on the respective precursor temperature window through online process control (temperature measurements by pyrometer or thermal imaging camera) possible.

In the following, in particular, the thermal treatment will be explained in more detail by way of example.

Showing:

Figure 1 in schematic form an example with two heating zones and

Rollers for electrical resistance heating and feed movement and

Figure 2 in schematic form an example with rollers for realizing the feed movement of at least one fiber and terminals for electrical resistance heating in three stages.

Fig. 1 shows a possibility of electrical resistance heating in an example with two heating zones 1 and 2. This can be used for different CNT contents of the fibers 3 from 0.5 mass% to 20 mass%.

The addition of electrically conductive particles (CNTs, nano-CNTs, possibly CB) leads to better fiber properties.

To increase the energy efficiency of the plant, a reactor of a

Carbonization system with thermoelectric generators (TEGs) be lined in order to redistribute energy radiated during electrical resistance heating process to the carbonation process.

As can be seen in FIG. 1, in the example shown, two heating zones 1 and 2 are arranged one after the other in the advancing movement direction, so that a stepwise increase in temperature can be achieved. Since the fibers 3 are electrically conductive, an electrical resistance heating can be used. This leads to a simplification of the required system technology, since the same principle of action for several stages in heating zones 1 and 2 or even more than two heating zones can be applied to the heating. With the invention, therefore, the same principle of action in the thermal treatment for the stabilization and the carbonization can be used. Infeed rollers 1 can be designed so that fibers 3 or a textile structure formed therefrom runs as wide and flat as possible into the heating zones 1 and 2.

In order to improve the heat transfer to / in the fiber material to be treated, an auxiliary roll (not shown) may also be arranged on the upper side of the material in order to contact the material also from above and thus to improve the heat transfer. This is particularly advantageous in textile structures.

In the intermediate zones between the rollers 2 and 1 or 2 'and 1, the electrical resistance of the fibers 3, for example, with measuring rollers (not shown in Figure 1) measured and used for a control of the temperature to be reached in the subsequent heating in the feed direction heating zone , which can influence the properties of the heated fibers 3 in the subsequent heating zone.

The rollers 2 and 2 'are each connected to an electrical voltage source.

Typically, in the heating zone 1, for example, a core-sheath fiber 3, which has an electrical output resistance of 5 Ω / cm, with an electrical voltage of 13 V and an electric current of 2 A at the rollers 2 at a feed rate in the range 12th m / h to 36 m / h to a temperature of 700 ° C are heated.

In the heating zone 2 can be applied to the rollers 2 ', an electrical voltage which is greater than the respective voltage applied to the rollers 2 electrical voltage and, for example, is 16 V. This can cause an electric current to flow which is 9A.

Thus, in the heating zone 2, a heating of the fibers 3 to a temperature of about 1,500 ° C can be achieved.

In the example of a device for electrical resistance heating shown in FIG. 2, the fibers 3 are first in the advancing movement direction Measuring roller pair 5, which can be used in conjunction with the completely arranged at the end of the measuring roller pair 5 'for determining the electrical conductivity of the fibers 3, respectively.

After the front pair of measuring rollers 5 and in front of the rear pair of measuring rollers 5 'there are feed roller pairs 6 which serve to convey the fibers 3. Between the feed roller pairs 6 several heating element pairs 7 and 7 'are arranged one after the other in the advancing movement direction of the fibers 3 in the advancing movement direction. The heating element pairs 7 and 7 'each form a heating zone, which can each be operated individually regulated, so that each desired heating rates and temperature increases can be achieved on the fiber material. The heating elements 7 and 7 'are each at a pole of a DC electrical power source (not shown). The fibers 3 are thereby through or along the

Heating element pairs 7 and 7 'moves. In the example shown in FIG. 2, a feed roller pair 6 is optionally arranged between the two rear heating zones formed by heating element pairs 7 and 7 ', with which a uniform advancing movement of the fibers 3 can be achieved. The heating elements 7 and 7 'are rigidly secured. 2 also shows sectional views through heating elements 7 or 7 ', from which it becomes clear how the electrical contacting of the fibers 3 takes place and how the thermal insulation can be formed.

Claims

claims

An apparatus for producing carbon fibers or textile structures formed with carbon fibers, wherein a module with two nozzles, each of which has a different inner diameter, is present, and a first nozzle is arranged inside the second nozzle, one of the nozzles is connected to a first reservoir, in which a polymer and the respective other nozzle is connected to a second reservoir, are contained in the electrically conductive particles in a dispersion, wherein by means of two conveyors, the dispersion, are contained in the electrically conductive particles from the first reservoir through which one nozzle and the polymer are passed through the other nozzle from the second reservoir, so that after the exit from the nozzles, a fiber (3) is obtained, which is formed with a core and a jacket, wherein the core with the polymer and the M Antel is formed of electrically conductive particles in an alternative and in another alternative, the core with electrically conductive particles and the sheath of polymer, and formed with a core and a sheath fiber (3) or a textile formed therefrom with a thermal Treatment, in which stabilization and carbonization is achieved.

2. Apparatus according to claim 1, characterized in that a dispersion in the water, a surfactant, a polymer and / or a solvent for the polymer in one of the reservoir and / or in the respective other reservoir, a highly viscous polymer or a polymer solvent Mixture, wherein the highly viscous or the polymer having the solvent has a viscosity suitable for forming the clad and core fibers through the first and second nozzles, and the polymer is preferably a precursor polymer selected from polyacrylonitrile, textile Polyacrylonitrile, pitch, cellulose (eg, viscose, lyocell, tire cord), liginine, lignin-based polymer, and blends with others

Precursor polymers, polyvinyl alcohol, other synthetic high-end precursors such as polyethylene or poly (p-phenylenebenzobisoxazole) (PBO), polypropylene, polyalkenes,

Polybutadiene, polyethylene terephthalate (PET), polybutyl terephthalate (PBT) and chemically modified precursor material thereof, and processable by dry spinning, wet spinning, gel spinning, melt spinning, dispersion spinning, electrospinning or centrifuge spinning processes.

3. Device according to one of the preceding claims, characterized in that the electrically conductive particles with solvent (s), surfactant (s), water or polymer (s) form a dispersion, wherein the electrically conductive particles carbon nanotubes (CNTs), carbon na nano-fibers (nano-CF) or noble metal nanowires, in particular silver nanowires, and have a high aspect ratio,

4. Device according to the preceding claim, characterized in that additionally at least one carbon allotrope, in particular carbon black (CB), is contained in the dispersion.

5. The device according to claim 1, characterized in that the outlet opening of the second nozzle is arranged with the larger inner diameter in the feed direction of the emerging from the nozzle components behind the outlet opening of the first nozzle with the smaller inner diameter.

6. Device according to one of the preceding claims, characterized in that with a multi-stage electrical resistance heating stabilization and carbonization of the fibers (3) or textile tilen structures formed with carbon fibers, can be achieved.

7. Device according to one of claims 1 to 6, characterized in that the electrical conductivity of the emerging from the nozzle fiber (3) or textile structures which are formed with carbon fibers, by means of inductive heating or a thermal treatment by means of microwave plasma can be achieved.

8. A process for the production of carbon fibers or a textile structure formed with carbon fibers, comprising from a first reservoir, in which electrically conductive particles are contained in a dispersion, to a first nozzle and from a second reservoir, in which a polymer is conveyed to a second nozzle; in which

a fiber (3) formed with a core and a jacket is formed with the streams emerging from the first and second nozzles, and

the fiber (3) or a textile structure formed with a plurality of these fibers (3) is subjected to a thermal treatment in which stabilization is first achieved followed by carbonization of the fiber (s) (3).

9. The method according to the preceding claim, characterized in that the viscosity of the polymer contained in the second reservoir is adjusted by selecting the polymer, maintaining a suitable temperature or by a proportion of solvent such that one for forming a core or shell as a precursor suitable viscosity for a carbon fiber has been maintained.

10. The method according to the two preceding claims, characterized in that the core or the cladding of the fiber (3) with a a proportion of electrically conductive particles, in particular carbon nanotubes, carbon nanofibers, noble metal nanofabrics and / or carbon allotropes, which lies above the percolation threshold.

Method according to one of the three preceding claims, characterized in that the stabilization and carbonization are carried out in several stages in succession and thereby the temperature is successively increased, wherein the thermal treatment is preferably carried out by means of electrical resistance heating.

Method according to the preceding claim, characterized in that prior to and / or during the stabilization an inductive or heating by means of a microwave-generated plasma of the fiber (s) (3) or textile structures, which are formed with carbon fibers, is performed.

Method according to one of the four preceding claims, characterized in that consists of a fiber (3) whose core consists exclusively of a polymer, in particular of polymethyl methacrylate, or of a polymer which is leachable by water or solvent or biodegradable, and a jacket formed with carbon nanotubes, carbon nanofibers, noble metal nanofabrics and / or carbon allotropes, a hollow fiber is produced.

Method according to one of the five preceding claims, characterized in that from a fiber (3), the core of electrically conductive particles, in particular carbon nanotubes, carbon nanofibers, Edelmetallnanofäden and / or carbon allotropes with or without polymer and their jacket from a leachable by water or solvent or biodegradable polymer is formed by removal of the sheath polymer before the thermal treatment, a fiber is formed which contains only the core material and thus has a significantly lower fiber diameter.