EP3443152A1 - Fibre de graphite à base de polyacrylonitrile - Google Patents

Fibre de graphite à base de polyacrylonitrile

Info

Publication number
EP3443152A1
EP3443152A1 EP17720376.7A EP17720376A EP3443152A1 EP 3443152 A1 EP3443152 A1 EP 3443152A1 EP 17720376 A EP17720376 A EP 17720376A EP 3443152 A1 EP3443152 A1 EP 3443152A1
Authority
EP
European Patent Office
Prior art keywords
graphite fiber
fiber
polyacrylonitrile
graphite
particles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP17720376.7A
Other languages
German (de)
English (en)
Inventor
Oswin ÖTTINGER
Rainer Schmitt
Ana Paula VIDIGAL
Rui BARATA DIAS
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SGL Carbon SE
Original Assignee
SGL Carbon SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by SGL Carbon SE filed Critical SGL Carbon SE
Publication of EP3443152A1 publication Critical patent/EP3443152A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • 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
    • 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
    • D01F1/10—Other agents for modifying properties
    • 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
    • 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
    • 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
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
    • D01F11/12—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with inorganic substances ; Intercalation
    • D01F11/121—Halogen, halogenic acids or their salts

Definitions

  • the present invention relates to a polyacrylonitrile-based graphite fiber, a textile fabric containing the polyacrylonitrile-based graphite fiber, a method for the manufacture of the graphite fiber and the textile fabric and its use as battery felts used in redox-flow batteries or NaS batteries, for carbon fiber papers used as gas diffusion layers in fuel cells and electrolysis cells, in satellite structure parts, in heat spreaders in the area of thermal management, as electrode material or for current collectors in desalination units, batteries, preferably redox-flow batteries, LiS batteries and Li-ion batteries, preferably as anode material in lithium-ion battery applications, as conductive filler for polymers, as a catalyst carrier, as additive for friction materials, preferably in brake pads or brake discs typically for aircraft and racing cars, wet friction, preferably for clutches, and for deicing applications, as filter material, for electromagnetic shielding, for flash protection and as material for electrical contacts.
  • Graphite fibers compared to carbon fibers are characterized by their high grade of graphitization resulting in the molecular structure and microstructure of graphite.
  • the microstructure of graphite is defined by the crystallographic parameters (i) interlayer spacing (d002 distance) which is the distance between adjacent molecular layers of covalently bonded sp 2 -hybridized carbon and (ii) mean crystallite size (Lc) which is a measure of the extension of the perfect graphite structure within a material. In a perfect graphite single crystal the d002 distance is 0.3354 nm and Lc corresponds to the size of the macroscopic crystal.
  • d002 distance of a carbon fiber which is based on polyacrylonitrile is about 0.345 nm and Lc is about 3 nm after carbonization at 1400°C, one can talk about a graphite fiber, if the d002 distance is 0.344 or lower accompanied with an increase of Lc to 12 nm or higher.
  • Graphite fibers feature high electrical and thermal conductivity rather than, for example, high tensile strength as carbon fibers do. Thus, the focus of graphite fibers lies on applications requiring suitable thermo-electrical properties rather than good mechanical properties. Graphite fibers can, for example, be obtained by
  • mesophase pitch-based carbon fibers graphitization of mesophase pitch-based carbon fibers. That means, carbon fibers based on mesophase pitch are heated to a sufficiently high temperature, typically above 2,200°C, so that the apriori amorphous carbon converts into a graphitic structure.
  • Mesophase pitch-based carbon fibers are very expensive.
  • mesophase pitch-based carbon fibers cost about 100 times more.
  • Polyacrylonitrile-based carbon fibers do not graphitize as good as mesophase pitch-based carbon fibers even if they are heated up to 2,200°C or above.
  • the d002 distance and the Lc of a polyacrylonitrile-based carbon fiber which is carbonized at a temperature of 2,500°C are about 0.343 nm and 5 nm respectively.
  • JP2014167039 (A) a catalytic graphitization method is described, wherein the activation energy of the carbonization reaction can be lowered so that the respective carbon fiber carbonized at lower temperatures has the same crystallinity as a typical polyacrylonitrile-based carbon fiber carbonized at higher temperatures.
  • the method includes a copolymeri- zation of polyacrylonitrile with an organometallic compound of a group VIII metal. The so obtained copolymer is then used as a precursor polymer in the known carbon fiber production method. While the performance of a copolymerization method with an organometallic compound is a rather expensive method and the reached crystallinity of the resulting carbon fiber still not exceeds that of typical
  • the object of the present invention to provide a graphite fiber with a high grade of graphitization which can be manufactured by a simple and cost efficient method.
  • the present invention provides a polyacrylonitrile-based graphite fiber, wherein the material of the graphite fiber exhibits an interlayer spacing (d002 distance) of below 0.344 nm, preferably below 0.341 nm and a mean crystallite size (Lc) of at least 12 nm, preferably at least 20 nm.
  • d002 distance interlayer spacing
  • Lc mean crystallite size
  • the graphite fiber of the present invention has a high thermal conductivity of about 1 100 W/m-K.
  • the electrical conductivity is also very high compared to standard carbon fibers.
  • the graphite fiber of the present invention is less cost-intensive than mesophase-pitch based graphite fibers, since it is based on polyacrylonitrile.
  • polyacrylonitrile-based means that the graphite fiber is obtained by starting with polyacrylonitrile as the base material for the respective precursor fiber as it is analogously the case with polyacrylonitrile-based carbon fibers which are well known in the art.
  • polyacrylonitrile-based also includes co-polymers of polyacrylonitrile with other monomers.
  • the graphite fiber of the present invention is not limited with regard to any coatings or the like being present, for example, on the surface of the fiber. Any such additional material is not encompassed by the expression "the material of the graphite fiber".
  • the "material of the graphite fiber” rather refers to the graphitic material based on polyacrylonitrile. According to a preferred embodiment of the present invention the material of the polyacrylonitrile-based graphite fiber exhibits an interlayer spacing (d002 distance) of below 0.341 nm, preferably below 0.339 nm after being heated to a temperature of at least 2,500°C for 30 minutes.
  • the material of the graphite fiber exhibits an interlayer spacing (d002 distance) of below 0.339 nm, preferably below 0.337 nm after being heated to a temperature of at least 3,000°C for 30 minutes.
  • the material of the fiber is, thus, getting close to the ideal graphite structure featuring high thermal and electrical conductivity.
  • the frictional properties are advantageous, in particular for applications like as friction materials in clutches, wet-friction, brake discs and brake pads.
  • the material of the polyacrylonitrile-based graphite fiber exhibits a mean crystallite size (Lc) of at least 12 nm, preferably at least 20 nm after being heated to a temperature of at least 2,500°C for 30 minutes. Even more preferably, the material of the graphite fiber exhibits a mean crystallite size (Lc) of at least 20 nm, preferably at least 30 nm after being heated to a temperature of at least 3,000°C for 30 minutes.
  • This high grade of crystallinity also leads to high thermal and electrical conductivity and advantageous frictional properties.
  • the polyacrylonitrile-based graphite fiber according to the present invention is not limited with regard to any other ingredients within the fiber besides the graphitic polyacrylonitrile-based material.
  • the graphite fiber contains one or more elements selected from the group consisting of Ca, Ti, Si, B, V, Cr, Ni, Mn, Fe, W and Cu in the form of its carbides, oxides, borides and/or nitrides, wherein the carbides, oxides, borides or nitrides are embedded in the fiber in the form of particles having a mean particle size in the range of 5 nm to 1 ⁇ , preferably 10 nm to 0.35 ⁇ and more preferably 50 nm to 0.1 ⁇ .
  • such particles may have some advantageous functions depending on the final application of the fiber.
  • the mean particle size corresponds to the d50-value. This particle size can be measured by using the laser diffraction method according to ISO 13320. The main function of these particles lies in the catalysis of the graphitization reaction which leads to the high grade of crystallinity according to the present invention of the material of the graphite fiber.
  • the graphite fiber comprises one or more elements selected from the group consisting of Ti, Si and Ni in the form of its carbides and/or oxides, wherein the carbides or oxides are embedded in the fiber in the form of particles having a mean particle size in the range of 5 nm to 1 ⁇ , preferably 10 nm to 0.35 ⁇ and more preferably 50 nm to 0.1 ⁇ .
  • the particles are present in an amount of 0.01 to 3 weight-percent (wt.-%), preferably of 0.01 to 1 .5 wt-%, based on the total weight of the graphite fiber. Within these ranges the highest grades of graphitization can be observed. The amount can be measured simply by burning the graphite fiber in an oxygen-containing atmosphere, weighing the residual ashes and analyzing the ashes.
  • the total ash content of the graphite fiber of the present invention is not particularly limited.
  • the graphite fiber has an ash content in the range 0.01 to 3 wt-%, preferably of 0.01 to 1 .5 wt-%, based on the total weight of the graphite fiber, wherein at least 60% the ash consists of NiC, NiO, TiC, T1O2, SiC, S1O2 or mixtures thereof.
  • the graphite fiber has an ash content of below 0.1 wt-%, preferably below 0.05 wt-% and more preferably below 0.01 wt-% based on the total weight of the graphite fiber and that the fiber is porous and contains voids having a mean diameter in the range of 5 nm to 1 ⁇ .
  • a fiber can be obtained according to a preferred method described below, wherein the graphite fiber is subjected to a purification method, for example, with chlorine gas converting the particles mentioned above into volatile substances and, thus, removing them from the fiber.
  • the preferred graphite fiber of the present invention is of high purity and high crystallinity.
  • the residual pores resulting from the particles previously present in the graphite fiber preferably have mean diameter in the range of 5 nm to 1 ⁇ , preferably 10 nm to 0.35 ⁇ and more preferably 50 nm to 0.1 ⁇ . It is assumed that the particles mentioned above are completely removed during the purification process leaving pores having the corresponding size of the particles.
  • the pore volume of such a purified fiber is preferably in the range of 0.005 Vol.-% to 1 .5 Vol.-%.
  • the polyacrylonitrile-based graphite fiber of the present invention can be further processed into any textile.
  • the present invention relates to a textile fabric comprising the polyacrylonitrile-based graphite fiber of the present invention being in the form of a woven fabric, a nonwoven or a paper.
  • These textiles can be advantageously used as battery felts used in redox-flow batteries or NaS batteries, for carbon fiber papers used as gas diffusion layers in fuel cells and electrolysis cells, in satellite structure parts, in heat spreaders in the area of thermal
  • batteries as electrode material or for current collectors in desalination units, batteries, preferably redox-flow batteries, LiS batteries and Li-ion batteries, preferably as anode material in lithium-ion battery applications, as conductive filler for polymers, as a catalyst carrier, as additive for friction materials, preferably in brake pads or brake discs typically for aircraft and racing cars, wet friction, preferably for clutches, and for deicing applications, as filter material, for electromagnetic shielding, for flash protection and as material for electrical contacts.
  • batteries preferably redox-flow batteries, LiS batteries and Li-ion batteries, preferably as anode material in lithium-ion battery applications, as conductive filler for polymers, as a catalyst carrier, as additive for friction materials, preferably in brake pads or brake discs typically for aircraft and racing cars, wet friction, preferably for clutches, and for deicing applications, as filter material, for electromagnetic shielding, for flash protection and as material for electrical contacts.
  • the present invention relates to a method for the manufacture of a graphite fiber comprising the following steps:
  • the graphite fiber of the present invention is manufactured by the method of the present invention.
  • liquid polymer comprising polyacrylonitrile in the context of the present invention encompasses any liquid, including but not limited to solutions or melts, containing any polyacrylonitrile-containing polymer, including but not limited to a polyacrylonitrile polymer, a copolymer with polyacrylonitrile. Any known
  • polyacrylonitrile-based precursor compositions for carbon fiber production can be used as the liquid polymer.
  • step b) work as graphitization catalysts in the later
  • the particles added in step b) comprise carbide or oxide particles of Ti, Si or Ni and the particles have a mean particle size in the range of 5 nm to 1 ⁇ , preferably in the range of 10 nm to 0.35 ⁇ and more preferably in the range of 50 nm to 0.1 ⁇ .
  • Most preferred are T1O2 and SiC particles having the respective particle size. The preferred particles, in particular, show a high catalytic effect.
  • the particles are added in an amount of 0.05 to 1 .5 wt.-%, more preferably 0.1 to 1 wt.-% based on the total weight of the liquid polymer provided in step a). If the liquid polymer is a solution, then the amount of added particles refers to the proportion of polymer present in the solution.
  • the kind of spinning method in step c) is not particularly limited. Possible spinning methods are air gap spinning, dry spinning, melt spinning and wet spinning.
  • the spinning step c) is a wet spinning method, in particular solvent spinning, or air gap spinning.
  • the wet spinning and air gap spinning method are known in the art of polyacrylonitrile-based carbon fiber production.
  • the graphite fiber of the present invention can be further treated by various methods.
  • the graphite fiber is thermally treated at above 1000°C in the presence of chlorine gas or chlorofluorocarbon gas. This treatment leads to a leach out of the particles added in step b) and, thus, to a purification of the graphite fiber.
  • Preferred chlorofluorocarbon gases are dichlorodifluoromethane and 1 ,1 ,1 ,2-tetrafluorethane.
  • the present invention relates to a method for the manufacture of a textile fabric incorporating the method for the manufacture of a graphite fiber according to the present invention wherein additionally a textile fabric forming process step is performed either with the precursor fiber before step d), with the stabilized precursor fiber before step e), with the carbon fiber before step f) or with the graphite fiber after step f) and that the textile fabric forming process step is one of a woven fabric forming process step, a nonwoven forming process step or a paper forming process step.
  • the above described preferred purification step can be performed before or after the textile forming process step.
  • the present invention relates to the use of the graphite fiber according to the present invention as conductive filler for polymers or as additive for friction materials.
  • the fibers are preferably cut into a suitable length before use.
  • the present invention relates to the use of the textile fabric according to the present invention as an electrode material or a current collector in desalination units, batteries, preferably redox-flow batteries, LiS batteries and Li-ion batteries, as a gas diffusion layer in electrolysis or in fuel cells, as a catalyst carrier, as a friction material, preferably in the form of a composite material, preferably in brake pads or brake discs typically for aircraft and racing cars, wet friction, preferably for clutches or as a heat spreader in the area of thermal management, in particular for the distribution of heat.
  • batteries preferably redox-flow batteries, LiS batteries and Li-ion batteries
  • a gas diffusion layer in electrolysis or in fuel cells
  • a catalyst carrier as a friction material, preferably in the form of a composite material, preferably in brake pads or brake discs typically for aircraft and racing cars, wet friction, preferably for clutches or as a heat spreader in the area of thermal management, in particular for the distribution of heat.
  • Figure 1 A diagram showing the differences in d002 distance between mesophase pitch based carbon fibers and PAN-based carbon fibers in dependence on the temperature.
  • Figure 2 A diagram showing the differences in crystallite size (Lc) between mesophase pitch and PAN in dependence on the temperature. (Source: M.R.
  • Figure 3 A diagram showing measurement results. Examples
  • polyacrylonitrile fibers With each of the batches polyacrylonitrile fibers have been spun to precursor fibers by a solvent-spinning method.
  • the respective precursor fibers were further processed by a stabilization process which is heating the precursor fiber under tension in the presence of oxygen, followed by a carbonization step in which the fiber is heated up to 1400°C in the absence of oxygen.
  • the method steps of solvent- spinning, stabilization and carbonization are well known methods in the field of carbon fiber production.
  • mesophase pitch fibers For comparative purposes, mesophase pitch fibers have been heated as well up to 2800°C for 30 minutes. The crystallographic results are as well given in figure 3.

Abstract

La présente invention concerne une fibre de graphite à base de polyacrylonitrile, caractérisée en ce que le matériau de la fibre de graphite présente un espacement intercouche (distance d002) inférieur à 0,344 nm, de préférence inférieur à 0,341 nm, et une taille moyenne de cristallite (Lc) d'au moins 12 nm, de préférence d'au moins 20 nm.
EP17720376.7A 2016-04-11 2017-04-11 Fibre de graphite à base de polyacrylonitrile Withdrawn EP3443152A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102016205991 2016-04-11
PCT/EP2017/058695 WO2017178492A1 (fr) 2016-04-11 2017-04-11 Fibre de graphite à base de polyacrylonitrile

Publications (1)

Publication Number Publication Date
EP3443152A1 true EP3443152A1 (fr) 2019-02-20

Family

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EP17720376.7A Withdrawn EP3443152A1 (fr) 2016-04-11 2017-04-11 Fibre de graphite à base de polyacrylonitrile

Country Status (2)

Country Link
EP (1) EP3443152A1 (fr)
WO (1) WO2017178492A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018115177A1 (fr) 2016-12-23 2018-06-28 Sgl Carbon Se Matériau de graphite
CN110656403B (zh) * 2019-11-07 2022-04-05 武汉纺织大学 一种易导电掺金属聚丙烯腈碳纤维及其制备方法
CN110819064B (zh) * 2019-12-03 2022-05-20 株洲时代新材料科技股份有限公司 一种高导热耐磨自润滑衬垫及其制备方法
CN113417033B (zh) * 2021-06-09 2022-10-14 山西钢科碳材料有限公司 一种聚丙烯腈基纤维、聚丙烯腈基碳纤维及制备方法
CN113373554B (zh) * 2021-06-09 2022-10-14 山西钢科碳材料有限公司 低灰分聚丙烯腈基纤维、聚丙烯腈基碳纤维及其制备方法
CN115323825B (zh) * 2022-08-25 2023-08-25 易高碳材料控股(深圳)有限公司 一种高导电、高导热石墨纤维纸的制备方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0637724B2 (ja) * 1983-09-09 1994-05-18 東レ株式会社 炭素繊維の製造方法
JPH1092431A (ja) * 1996-09-17 1998-04-10 Petoca:Kk リチウムイオン２次電池用負極材及びその製造方法
JP4390608B2 (ja) * 2004-03-29 2009-12-24 帝人株式会社 炭素繊維およびその製造方法
WO2006101799A2 (fr) * 2005-03-16 2006-09-28 Honeywell International Inc. Fibre de carbone contenant des particules de ceramique
JP2014167039A (ja) 2013-02-28 2014-09-11 Toray Ind Inc ポリアクリロニトリル系重合体、炭素繊維前駆体繊維およびその製造方法、ならびに炭素繊維の製造方法

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Publication number Publication date
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