CN116134188A - Method for producing porous carbon fibers and use thereof - Google Patents

Method for producing porous carbon fibers and use thereof Download PDF

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CN116134188A
CN116134188A CN202180059614.5A CN202180059614A CN116134188A CN 116134188 A CN116134188 A CN 116134188A CN 202180059614 A CN202180059614 A CN 202180059614A CN 116134188 A CN116134188 A CN 116134188A
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丹尼尔·塞巴斯蒂安·延斯·沃尔兹
本杰明·里希特
乌韦·戈斯
休伯特·耶格
罗伯特·伯姆
米尔科·里希特
汤姆·博恩克
斯蒂芬·卡斯克尔
乔克里·谢里夫
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Technische Universitaet Dresden
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    • D—TEXTILES; PAPER
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    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
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    • D—TEXTILES; PAPER
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    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/08—Addition of substances to the spinning solution or to the melt for forming hollow filaments
    • D—TEXTILES; PAPER
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    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
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    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • D—TEXTILES; PAPER
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    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/16—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate
    • D01F9/17—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate from lignin
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
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    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
    • D01F9/225—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles from stabilised polyacrylonitriles

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Abstract

The present invention relates to a method for producing porous carbon fibers from porous organic polymer precursor fibers by means of electronic treatment, thermal stabilization and carbonization, and to the use of porous carbon fibers as electrode materials or filter materials.

Description

Method for producing porous carbon fibers and use thereof
Technical Field
The present invention relates to a method for producing porous carbon fibers from porous organic polymer precursor fibers by carbonization, and to the use of porous carbon fibers as electrode material or as separator material.
Background
Carbon Fibers (CF) are produced from polymer precursor fibers in an energy and time consuming multi-stage thermal process consisting of air-assisted stabilization and inert carbonization as well as graphitization. The polymer precursor fibers are mostly composed of the polymer Polyacrylonitrile (PAN)
Figure BDA0004113681620000011
Et al, 2016).
In addition to being used as a reinforcement material, carbon fibers may also be used as carbon fiber-based electrodes, for example, in electrical energy storage for energy conversion or hydrogen storage.
Elazari et al describe the use of sulfur impregnated activated carbon fibers as the cathode material for rechargeable lithium sulfur batteries (Elazari et al, 2011).
US 7,510,626 B2 and EP 1,502,992 B1 disclose the use of porous carbon fibers with a surface ratio of greater than 1.05 in carbon fiber based electrodes of fuel cells. US 7,510,626 B2 and EP 1,502,992 B1 describe the production of porous carbon fibers by a wet spinning process, heat stabilization and carbonization.
Borchardt et al discuss the need to tailor the pore system in secondary electrical energy storage systems such as lithium sulfur batteries to achieve high energy densities (Borchardt et al 2016). Thus, the use of carbon fibers in energy storage systems, particularly with liquid electrolytes, requires uniform porosity throughout the filament cross-section, high specific surface area and large pore volume in order to significantly increase energy density and fully utilize energy storage potential.
Various process parameters such as atmosphere, temperature, residence time or fiber tension have an effect on the formation of pores, in particular the composition of the pores, the total porosity, the pore size (micropores, mesopores or macropores) and the pore distribution, and the specific surface area of the carbon fibers resulting therefrom; particularly in the stabilization or carbonization process (Bajaj and Dhawan, 1997).
To date, in order to increase the specific surface area, for example in the production of PAN-based or PAN-mixture-based carbon fibers, polymers (He et al, 2016; zhang et al, 2019) have been used which are additionally incorporated into the precursor fibers and which decompose during stabilization.
Alternatively, the increase in specific surface area is achieved by a significantly more than two hours of stabilization and/or carbonization process time of the polymer precursor fibers (Wang 1996; zhang et al 2019). Wang describes a very long stabilization process time exceeding 5 hours (Sun et al, 2007). Zhang et al disclose a long carbonization process time exceeding 2 hours (Zhang et al 2019).
In addition, porous carbon fibers are produced using cost-intensive processing aids, in particular using carbon dioxide instead of nitrogen or using alkali (Bajaj and Dhawan,1997; sun et al, 2007).
DE 698 27 6767 t2 and EP 1137476 B1 describe a carbon fiber composite for an electrically regenerable air filter medium comprising porous carbon fibers bonded in an open, permeable structure with a carbonizable organic binder, wherein the composite has a porosity in the range of about 82 to 86% and greater than 1000m before activation 2 Surface area per gram. The production of carbon fibers is performed by a melt spinning process or a melt blowing process.Activation of the carbon fibers is performed by steam, carbon dioxide, oxygen, or by chemical activation, thereby removing carbon and forming pores in the carbon fibers.
It is also known to increase the specific surface area by additional heat treatment with acids, bases or reactive gases after carbonization or graphitization, so-called activation (Trautwein et al 2016; chen et al 2019). The integrated treatment of activation of already porous polymer precursor fibers is described by Li et al (Li et al 2015). The textile semifinished product based on carbon fibres can reach about 2000m by a subsequent additional activation process 2 Specific surface area per gram.
In addition, polymer modification methods using high energy electrons are known, for example for crosslinking of polymers (e.g. thermoplastics, elastomers), curing of reactive resin systems for producing fiber-polymer matrix mouldings, functionalization (e.g. PTFE) or stabilization by PAN precursor fiber circulation (Yang et al 2018). These applications are based on spatially and temporally accurate energy input, by means of energetic electrons, to generate excited atoms or molecules and ions, which preferably form free radicals and initiate complex chemical reactions. The result is a polymer with altered chemical, electrical, mechanical and thermal properties (Charlesby 1952). The advantage of using high energy electron crosslinking is that large parts can be manufactured without using autoclaves, with energy efficiency up to 70% higher than in hot processes, low gas emissions, short curing times, elimination of additional free radical formers and the possibility of complete incorporation of the materials used into the network.
DE 10 2015120 377 A1 describes a production process for lignin-based compositions for producing carbon fibers with advantageous mechanical properties, wherein a reaction mixture containing lignin and/or lignin derivatives as reactive component a and formaldehyde releasing compounds as reactive component B is subjected to reactive extrusion. Paragraph [0042] describes the production of carbon fibers by melt spinning. DE 10 2015120 377 A1 also discloses thermal stabilization of precursor fibers, preferably by oxidative thermal stabilization and/or stabilization with high-energy radiation, in particular electron radiation.
KR 10 1 755 B1 describes a precursor fiber made of polyacrylonitrile which is crosslinked by electron beam and then stabilized by oxidation for at least 30 minutes for producing fibers with improved physical properties, in particular improved heat resistance. KR 10 1 755 267 B1 describes electron beam treatment at 50 to 3000kGy and at a temperature in the range of room temperature to 300 ℃.
DE 10 2015 106 348 B4 describes a process for producing carbon fibers with improved mechanical properties such as tensile strength, modulus and elongation at break using fibers based on modified polyolefins or modified polyamides. DE 10 2015 106 348 B4 describes the use of various spinning processes, typically melt spinning, and crosslinking during and/or after shaping, including chemical crosslinking with the addition of crosslinking additives and subsequent physical crosslinking by radiation treatment, in particular ultraviolet light or electron beams. Preferably, the electron beam treatment is carried out at a temperature in the range of 50 and 80 ℃ and at a dose of between 400 and 800 kGy. Followed by carbonization.
In addition, CN 103265010B discloses a three-dimensional carbon fiber-based aerogel material, which is prepared by binary polymer precursor material and dispersing carbon fibers in the matrix and crosslinking using ionizing radiation. The obtained three-dimensional carbon fiber-based aerogel material has a pore size in the range of 0.01 μm to 2,000 μm and a pore size of 0.2m 2 /g to 2,000m 2 Specific surface area in the range of/g.
In order to achieve porous carbon fibers, the methods known to date, including stabilization, carbonization and activation, disadvantageously resort to additional very energy-consuming processes, which have long residence times and/or additional thermal process steps, as well as sometimes toxic and unhealthy or additional, sometimes cost-intensive processing aids. These are also mostly energy intensive and require high personnel and technical safety during use.
Furthermore, the known methods do not maintain the interconnected porous structure morphology already present in the precursor fibers, while producing a mechanically loadable structural material.
Disclosure of Invention
It is therefore an object of the present invention to provide a method for producing porous carbon fibers which overcomes the disadvantages of the prior art.
According to the invention, this object is achieved by a method for producing a porous carbon fiber according to the invention, comprising the steps of
a) Providing a porous organic precursor fiber made of at least one polymer, wherein the porous organic precursor fiber has a thickness of 1m 2 /g to 500m 2 The internal surface area in the range of/g,
b) The porous organic precursor fibers are subjected to an electron treatment, preferably at a temperature in the range of 0 to 300 c,
c) Thermally stabilizing the porous organic precursor fiber,
d) Carbonizing the thermally stabilized porous organic precursor fiber to form a porous carbon fiber.
According to the invention, the process is carried out in the order of steps a), b), c) and d).
Advantageously, porous carbon fibers having interconnected pore systems and large internal surface areas are obtained by the method according to the invention. The term "interconnected pore system" refers to a pore system having a continuous web-forming space of a defined size.
The porous carbon fibers produced by the method according to the invention for the first time make it possible to produce tailored carbon fiber pore systems for structural materials which are also load-bearing, for example as fiber-based electrodes or conventional filter materials in electrical energy storage devices, in particular higher electrode capacities and more efficient batteries can be obtained with unchanged mechanical properties of the material.
Advantageously, by means of the method according to the invention, in particular the step of electronic treatment, the number of additional process steps and process auxiliaries (activation) and the process cycle time, in particular the time for stabilization and carbonization, are reduced, so that at least comparable, preferably increased process speeds are achieved compared to the production of porous carbon fibers without an activation step. In embodiments, the process according to the invention has a process cycle time of at most 230 minutes, preferably in the range from 2.1 minutes to 120 minutes, particularly preferably in the range from 7.1 minutes to 51 minutes. It is further advantageous that the stabilization temperature can be increased by the method according to the invention, in particular the step of electronic treatment.
It is further advantageous that the method according to the invention is simple and durable.
The process according to the invention greatly reduces the costs and the required facility size compared to the process for stabilization by proton irradiation. Advantageously, the method according to the invention can be carried out in existing facilities for producing carbon fibers by integrating the electron beam chamber, due to its small size.
The term "porous organic precursor fiber" refers to a fiber composed of carbon and hydrogen containing materials having an internal surface area of at least 1m 2 /g, preferably at 1m 2 /g to 500m 2 In the range of/g; particularly preferably at 50m 2 /g to 500m 2 In the range of/g. Such precursor fibers may be processed into carbon fibers by carbonization.
In embodiments, the porous organic precursor fiber is a continuous fiber. The term "continuous fibers" refers to fibers that have little restriction in length.
In embodiments, the porous organic precursor fiber is provided by a wet spinning process, preferably by a solvent wet spinning process. Advantageously, coagulation and diffusion may be affected during the solvent wet spinning process, thereby creating porosity of the precursor fiber.
The term "spinning process" refers to the spinning of polymer fibers, wherein the synthesis of the polymer and the melting or dissolution of the polymer are performed prior to the spinning process.
The term "internal surface area" or "specific surface area" refers to the total surface area contained in the fiber, including the surface area within the pores. The determination of the internal surface area is carried out by measurement methods known to the skilled worker, in particular by nitrogen adsorption and mercury porosimetry. Nitrogen adsorption refers to an analytical method in which the surface area is determined by gas adsorption, wherein the specific surface area related to mass is calculated from experimental data. Mercury porosimetry is an analytical method in which the surface area is determined by a non-wetting liquid such as mercury. The pore size is measured as a function of the external pressure required to force the liquid into the pores against the surface tension of the liquid.
According to the invention, the at least one polymer is an organic polymer. In embodiments, the at least one polymer is a synthetic polymer and/or a biopolymer.
The term "biopolymer" refers to a polymer synthesized in cells of a organism, in particular a polysaccharide, protein or nucleic acid, preferably a polysaccharide or phenolic biopolymer.
The term "polysaccharide" refers to a carbohydrate in which at least 11 monosaccharides are linked by glycosidic linkages.
The term "phenolic biopolymer" refers to a biopolymer having at least one phenyl group.
In a preferred embodiment, the at least one polymer is Polyacrylonitrile (PAN), polyolefin and/or lignin, particularly preferably the at least one polymer is PAN.
The term "polyolefin" refers to polymers polymerized from olefins, particularly ethylene, propylene, 1-butene or isobutylene.
In further embodiments, the porous organic precursor fiber comprises at least one additional polymer, wherein the at least one additional polymer is thermally degradable.
The term "thermally degradable" refers to the property of the polymer to decompose at a temperature of at least 500 ℃, in particular during carbonization in step d).
Advantageously, the porosity of the porous carbon fibers produced by the method according to the invention can be further increased, in particular in the micropore range, by adding a thermally degradable polymer which is decomposed during the carbonization of step d). The pores in the micropore range mean pores having an average pore diameter of at most 2nm, preferably in the range of 0.1nm to 2 nm.
In an embodiment, the additional polymer is cellulose or lignin, preferably Lignin Sulfonate (LS) or lignin acetate (LAc).
The term "lignosulfonate" refers to a salt of lignosulfonic acid, wherein the lignosulfonic acid is a water-soluble, anionic, polyelectrolyte, branched polymer. Lignosulfonates are obtained in cellulose production by the sulfite process.
The term "lignin acetate" refers to lignin derivatives having at least one acetyl group, which are obtained by modifying lignin with acetic acid.
In embodiments, the porous organic precursor fiber comprises PAN in an amount ranging from 50% (m/m) to 100% (m/m), preferably in an amount ranging from 70% to 100% (m/m).
In a further embodiment, the porous organic precursor fiber comprises at least one further component, wherein the further component is selected from the group comprising monomers, fillers and reinforcing materials and additives.
The term "monomer" refers to reactive molecules of low molecular weight which can be combined into unbranched or branched polymers by chain polymerization, polycondensation or polyaddition, in particular molecules having at least one c=c double bond per molecule or having at least two functional groups.
The term "fillers and reinforcing materials" refers to insoluble substances added to the porous organic precursor fibers, in particular in an amount in the range of 0.01% (m/m) to 10% (m/m), in order to improve, inter alia, mechanical properties or processability.
The term "additive" refers to substances that are preferably soluble and are added to the porous organic precursor fiber in small amounts, preferably in amounts in the range of 0.01% (m/m) to 7% (m/m), to achieve or improve certain properties. In embodiments, the additive is a dispersant, plasticizer or light stabilizer, in particular an ultraviolet absorber and/or a free radical scavenger. Advantageously, these additives are non-toxic and are produced based on renewable raw materials.
In an embodiment, the at least one additional ingredient is selected from the group comprising: metal oxides, preferably titanium oxide; nanocarbon, preferably Carbon Nanotubes (CNT); or graphene.
The term "electron treatment" refers to irradiation by energetic electrons to produce excited atoms or molecules and ions and secondary electrons in the porous organic precursor fibers, which preferably produce polymer radicals through specific intermolecular and intramolecular charge and energy transfer reactions. The polymer radicals induce complex chemical reactions in the polymer of the precursor fiber.
In an embodiment, the electron treatment of the porous organic precursor fiber in step b) is performed at an irradiation temperature in the range of 0 ℃ to 300 ℃, preferably in the range of 100 ℃ to 170 ℃. Advantageously, during the production of the porous organic precursor fiber, primary polymer radicals may be generated from at least one polymer, independent of temperature, depending on the requirements of the desired chemical reaction.
Advantageously, the electron treatment step may stabilize the pores in the porous organic precursor fiber. According to the invention, the porous structure of the precursor fiber is obtained by specifically crosslinking the polymer fraction during the electron treatment.
Preferably, the electron treatment in step b) is carried out at a temperature above the glass transition temperature. The term "glass transition temperature Tg" refers to the temperature at which a polymer transitions to a rubbery to viscous state.
In embodiments, the electron treatment in step b) is performed with a residence time in the range of 0.1 minutes to 20 minutes. The term "residence time" refers to the time that the porous organic precursor fibers remain in the electronic processing device and absorb the dose.
In embodiments, the electron treatment in step b) is performed in an oxygen-containing atmosphere, preferably air, or in an inert gas atmosphere, preferably nitrogen.
The term "oxygen-containing atmosphere" refers to an atmosphere having an oxygen content of at least 1% (v/v). Preferably, the oxygen-containing atmosphere comprises oxygen in an amount in the range of 1% (v/v) to 20.95% (v/v). Advantageously, the electronic treatment of step b) can also be carried out in air.
In an alternative embodiment, the electron treatment in step b) is performed under vacuum or at a low residual oxygen content (< 3000 ppm). The term "vacuum" refers to an atmosphere at a pressure below ambient pressure.
In embodiments, the electron treatment in step b) is carried out with an energy in the range of 70keV to 10MeV, preferably in the range of 100keV to 10MeV, particularly preferably in the range of 100keV to 300 keV.
In embodiments, the electron treatment in step b) is performed at a total dose in the range of 50kGy to 2,000kGy, preferably in the range of 50kGy to 1,000kGy, particularly preferably in the range of 200kGy to 500 kGy.
The term "dose" refers to the amount of energy absorbed per unit mass. Advantageously, the energy input, i.e. the dose, of the electronic treatment is selected according to the material composition of the porous organic precursor fibers.
In embodiments, the electron treatment in step b) is carried out chronologically, preferably with a partial dose in each case in the range from 25 kGy/time to 200 kGy/time, particularly preferably with a partial dose in each case in the range from 25 kGy/time to 150 kGy/time.
Advantageously, the heating of the porous organic precursor fibers and, if necessary, of the coil body is reduced by the chronological electronic treatment.
In an embodiment, the electron treatment in step b) is carried out at a fiber tension in the range from 0N/tex to 5,000cN/tex, preferably in each case in the range from 1cN/tex to 100 cN/tex.
Advantageously, the pore morphology and physical properties of the porous carbon fibers can be tuned by varying process parameters selected from the group consisting of dosage, dosage rate, dosage per fiber batch, atmosphere, temperature, and/or fiber tension.
The term "heat-stabilised" means that the porous organic precursor fibres are crosslinked by an increase in temperature, in particular by cyclisation, oxidation, intermolecular and intramolecular cross-linking, and dehydration and aromatisation.
In embodiments, the thermal stabilization of the porous organic precursor fiber in step c) is performed under stretching in the range of-3% to +8%.
The term "stretching" refers to a process of reinforcing fibers wherein the fibers are stretched, in particular 4 to 5 times, preferably 0.9 to 1.5 times, so that the polymer is increasingly oriented.
In an embodiment, the thermal stabilization in step c) is carried out at a temperature in the range of 100 ℃ to 400 ℃, preferably 240 to 300 ℃.
In embodiments, the thermal stabilization in step c) is carried out with a residence time in the range of 1 to 180 minutes, preferably in the range of 1 to 30 minutes, particularly preferably in the range of 5 to 16 minutes.
The term "residence time" refers to the time that the porous organic precursor fibers reside in the thermal stabilization device.
The term "carbonization" refers to the process of converting organic precursor fibers into carbon fibers, preferably with a carbon content in the range of 90% (m/m) to 100% (m/m), particularly preferably with a carbon content in the range of 96% (m/m) to 98% (m/m), in particular by reduction and heteroatom elimination. The term "heteroatom" refers to an atom other than carbon or hydrogen, in particular nitrogen, oxygen, sulfur or phosphorus.
Advantageously, the electrical conductivity of the fibers is increased by carbonization. Advantageously, the carbon fibers obtained with the process according to the invention have an electrical conductivity in the range of 200S/cm to 2,500S/cm, preferably in the range of 600S/cm to 2,500S/cm; and/or a tensile strength of at least 700MPa and an elastic modulus of at least 50GPa.
In embodiments, the carbonization in step d) is performed at a temperature in the range of 700 ℃ to 1,500 ℃, preferably in the range of 700 ℃ to 1,400 ℃, particularly preferably in the range of 700 ℃ to 900 ℃.
In embodiments, the carbonization in step d) is performed with a residence time in the range of 1 to 30 minutes, particularly preferably in the range of 2 to 15 minutes. The term "residence time" refers to the time that the porous organic precursor fibers reside in the carbonization device.
In embodiments, carbonization is performed in an inert gas atmosphere, preferably in a nitrogen atmosphere.
In a further embodiment, steps c) and d) are carried out continuously or discontinuously.
The method according to the invention is carried out by a system for producing porous carbon fibers, comprising
i. At least one of the spinning devices, the spinning device,
at least one electron beam chamber, at least one of which,
at least one heat treatment unit
At least one carbonization unit.
In an embodiment, the at least one spinning device and the at least one electron beam chamber or the at least one electron beam chamber and the at least one heat treatment unit are connected. Advantageously, the electron treatment in the at least one electron beam chamber may match the residence time of the fiber in the at least one spinning device or the at least one heat treatment unit.
Advantageously, carbon fiber production can be combined with modification with high-energy electron polymers by this system. It is also advantageous that the system has a compact facility structure including shielding, which can be implemented as a production line.
The invention also relates to the use of the porous carbon fibers produced by the method according to the invention as electrode material or as filter material.
The term "electrode material" refers to a conductive material.
The term "filter material" refers to a porous material that separates solid particles from a gas or liquid stream according to pore size.
In an embodiment, the porous carbon fibers produced by the method according to the invention are used in fiber-based electrodes in electrical energy storage, in particular supercapacitors or batteries, or in filtration materials, in particular filters or membranes.
Advantageously, the energy storage using the porous carbon fibers produced by the method according to the invention shows a higher electrode capacity and a more efficient battery with the same material mechanical properties.
For the realization of the invention it is also advantageous to combine the features of the previous embodiments and the claims.
Drawings
Examples
The invention will be explained in more detail below with reference to some embodiments and the related figures. These examples will describe the invention without limiting it. Wherein the method comprises the steps of
Fig. 1 shows the void size distribution of the porous organic Precursor Fiber (PF), the porous organic precursor fiber after electron treatment (EB) and the heat-Stabilized Fiber (SF) of example 1, and the carbonized Carbon Fiber (CF) without the previous electron treatment (a) and the previous electron treatment (b). Based on nitrogen physisorption measurements, the void size distribution of all fiber samples was calculated using density functional theory (QSFT) and the specific surface area was calculated using Brummauer-Emmett-Teller analysis (BET).
Fig. 2 shows the void size distribution of the porous organic Precursor Fiber (PF), the porous organic precursor fiber after electron treatment (EB) and the heat-Stabilized Fiber (SF) of example 2, and the carbonized Carbon Fiber (CF) without the previous electron treatment (a) and the previous electron treatment (b). Based on nitrogen physisorption measurements, the void size distribution of all fiber samples was calculated using density functional theory (QSFT) and the specific surface area was calculated using Brummauer-Emmett-Teller analysis (BET).
Detailed Description
Example 1:
porous organic Precursor Fibers (PF) were prepared from polyacrylonitrile (pPAN) by a wet spinning process, wherein 50.0m was obtained 2 Specific surface area per gram and 0.19cm 3 Void volume per gram.
Fibers that were not electronically treated had the characteristics in table 1. The specific surface area and pore volume are determined by nitrogen physisorption.
The fibers not subjected to the electron treatment of table 1 have the following characteristics.
Figure BDA0004113681620000141
After electron-free thermal stabilization and carbonization, the specific surface area and pore volume of the fibers indicate that the original pore structure is destroyed during thermal stabilization.
The fiber properties in table 2 are known after electronically treating (EB) porous organic precursor fibers composed of pPAN with 200kGy under nitrogen.
Table 2 the electronically treated fibers have the following characteristics.
Figure BDA0004113681620000142
The specific surface area and pore volume of the fibers treated with 200kGy of electrons showed that the original pores were partially stabilized by the electron treatment, and thus pores were present after the heat stabilization process. Thus, the electron treatment results in additional pore formation during carbonization.
Example 2:
porous organic Precursor Fibers (PF) were produced from Polyacrylonitrile (PAN) and Lignosulfonate (LS) in a ratio of 95:5 (m/m) by a wet spinning process, wherein 70.0m was obtained 2 Specific surface area per gram and 0.27cm 3 Void volume per gram.
The fibers that were not electronically treated had the characteristics in table 3.
Table 3 the fibers not treated electronically have the following characteristics.
Figure BDA0004113681620000151
The fiber properties in Table 4 were known after electronically treating porous organic precursor fibers composed of pPAN and LS under nitrogen at 200 kGy.
Table 4 electronically treated fibers have the following characteristics.
Figure BDA0004113681620000152
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Figure BDA0004113681620000162
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Figure BDA0004113681620000161
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Figure BDA0004113681620000163
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Claims (15)

1. A method for producing porous carbon fibers comprising the steps of
a) Providing porous organic precursor fibers made from at least one polymer,
wherein the porous organic precursor fiber has a thickness of 1m 2 /g to 500m 2 The internal surface area in the range of/g,
b) Electronically treating the porous organic precursor fiber,
c) Thermally stabilizing the porous organic precursor fiber,
d) Carbonizing the thermally stabilized porous organic precursor fiber to form a porous carbon fiber.
2. The method according to claim 1, wherein the at least one polymer is a synthetic polymer and/or a biopolymer.
3. The method according to claim 1 or 2, characterized in that the at least one polymer is Polyacrylonitrile (PAN), polyolefin and/or lignin.
4. A method according to any one of claims 1 to 3, wherein the porous organic precursor fiber comprises at least one further polymer, wherein the at least one further polymer is thermally degradable.
5. The method according to claim 4, characterized in that the further polymer is cellulose or lignin, preferably Lignin Sulfonate (LS) or lignin acetate (LAc).
6. The method according to any one of claims 1 to 5, wherein the porous organic precursor fiber comprises at least one further component, wherein the further component is selected from the group comprising monomers, fillers and reinforcing materials and additives.
7. The method according to any one of claims 1 to 6, wherein the electron treatment in step b) is performed at a temperature in the range of 0 ℃ to 300 ℃.
8. The method according to any one of claims 1 to 7, characterized in that the electron treatment in step b) is performed in an oxygen-containing atmosphere or an inert gas atmosphere.
9. The method according to any one of claims 1 to 8, characterized in that the electron treatment in step b) is performed with an energy in the range of 100keV to 10 MeV.
10. The method according to any one of claims 1 to 9, characterized in that the electron treatment in step b) is performed at a total dose of 50kGy to 2,000 kGy.
11. The method according to any one of claims 1 to 10, characterized in that the electron treatment in step b) is performed chronologically, preferably with a partial dose of 25 kGy/time to 150 kGy/time.
12. The method according to any one of claims 1 to 11, wherein the thermal stabilization of the porous organic precursor fiber in step c) is performed with a stretching in the range of-3% to +8%.
13. The process according to any one of claims 1 to 12, wherein the thermal stabilization in step c) is carried out at a temperature in the range of 100 ℃ to 400 ℃.
14. The method according to any one of claims 1 to 13, wherein carbonization in step d) is performed at a temperature in the range of 700 ℃ to 1500 ℃.
15. Use of the porous carbon fiber produced by the method according to any one of claims 1 to 14 as an electrode material or a filter material.
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