WO2018115177A1 - Graphite material - Google Patents
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- WO2018115177A1 WO2018115177A1 PCT/EP2017/083911 EP2017083911W WO2018115177A1 WO 2018115177 A1 WO2018115177 A1 WO 2018115177A1 EP 2017083911 W EP2017083911 W EP 2017083911W WO 2018115177 A1 WO2018115177 A1 WO 2018115177A1
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- WIPO (PCT)
- Prior art keywords
- graphite
- precursor
- fibers
- fiber
- graphite material
- Prior art date
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- 239000007770 graphite material Substances 0.000 title claims abstract description 40
- 239000000835 fiber Substances 0.000 claims abstract description 90
- 239000000463 material Substances 0.000 claims abstract description 53
- 239000002243 precursor Substances 0.000 claims abstract description 53
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 34
- 239000011248 coating agent Substances 0.000 claims abstract description 33
- 238000000576 coating method Methods 0.000 claims abstract description 33
- 239000010439 graphite Substances 0.000 claims abstract description 31
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 31
- 238000005087 graphitization Methods 0.000 claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 13
- 239000011347 resin Substances 0.000 claims abstract description 13
- 239000011295 pitch Substances 0.000 claims abstract description 11
- 229920000297 Rayon Polymers 0.000 claims abstract description 10
- 239000002964 rayon Substances 0.000 claims abstract description 10
- 239000011229 interlayer Substances 0.000 claims abstract description 9
- 239000007833 carbon precursor Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 30
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 29
- 239000004917 carbon fiber Substances 0.000 claims description 29
- 239000000843 powder Substances 0.000 claims description 22
- 229910052759 nickel Inorganic materials 0.000 claims description 17
- 229910052742 iron Inorganic materials 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 15
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 15
- 238000003763 carbonization Methods 0.000 claims description 12
- 230000006641 stabilisation Effects 0.000 claims description 12
- 238000011105 stabilization Methods 0.000 claims description 12
- 238000009987 spinning Methods 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000003575 carbonaceous material Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 229910001416 lithium ion Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 5
- 150000001247 metal acetylides Chemical class 0.000 claims description 5
- 150000004767 nitrides Chemical class 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 238000004513 sizing Methods 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000002783 friction material Substances 0.000 claims description 4
- 239000010410 layer Substances 0.000 claims description 4
- 239000012705 liquid precursor Substances 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 239000011231 conductive filler Substances 0.000 claims description 3
- 238000010612 desalination reaction Methods 0.000 claims description 3
- 238000009792 diffusion process Methods 0.000 claims description 3
- 239000007772 electrode material Substances 0.000 claims description 3
- 238000005868 electrolysis reaction Methods 0.000 claims description 3
- 239000000446 fuel Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 229910003465 moissanite Inorganic materials 0.000 claims description 2
- 239000005543 nano-size silicon particle Substances 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000004753 textile Substances 0.000 description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000011302 mesophase pitch Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 238000007380 fibre production Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229920005610 lignin Polymers 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000002166 wet spinning Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- -1 braidings Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000002074 melt spinning Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- XMIIGOLPHOKFCH-UHFFFAOYSA-N 3-phenylpropionic acid Chemical compound OC(=O)CCC1=CC=CC=C1 XMIIGOLPHOKFCH-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- ZEASXVYVFFXULL-UHFFFAOYSA-N amezinium metilsulfate Chemical compound COS([O-])(=O)=O.COC1=CC(N)=CN=[N+]1C1=CC=CC=C1 ZEASXVYVFFXULL-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009954 braiding Methods 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000000578 dry spinning Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- SDVHRXOTTYYKRY-UHFFFAOYSA-J tetrasodium;dioxido-oxo-phosphonato-$l^{5}-phosphane Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)P([O-])([O-])=O SDVHRXOTTYYKRY-UHFFFAOYSA-J 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 210000001170 unmyelinated nerve fiber Anatomy 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/205—Preparation
-
- 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
-
- 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
- D01F11/123—Oxides
-
- 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
- D01F11/124—Boron, borides, boron nitrides
-
- 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
- D01F11/126—Carbides
-
- 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
- D01F11/127—Metals
-
- 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
- D01F11/128—Nitrides, nitrogen carbides
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/60—Compounds characterised by their crystallite size
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/78—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by stacking-plane distances or stacking sequences
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/8807—Gas diffusion layers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- the present invention relates to graphite fibers and graphite powder, a method for the manu- facturing the same and its uses for 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 graphitiza- tion 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.
- 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
- Lc is about 3 nm after carbonization at 1400 °C
- a graphitic material such as a graphite fiber, features high electrical and thermal conductivity rather than, for example, high tensile strength as carbon fibers do.
- the focus of graphite materials lies on applications requiring suitable thermo-electrical properties rather than good mechanical properties.
- Graphite fibers can, for example, be obtained by graphitization of mesophase pitch-based carbon fibers. That means, carbon fibers based on mesophase pitch are heated to a sufficiently high temperature, typically above 2200 °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 can 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 2200 °C or above.
- the d002 distance and the Lc of a polyacrylonitrile-based carbon fiber which is carbonized at a temperature of 2500 °C are about 0.343 nm and 5 nm respectively (Sources: M. Inagaki, F. Kang, Materials Science and Engineering of Carbon: Fundamentals, Elsevier, 2nd Edition, 2014 and M.R. Buchmeister et al., Carbonfasern: Praadosor-Systeme, Switzerland, Struktur und compassion, Angewandte Chemie 2014, vol. 126, pages 5364-5403).
- a polyacrylnitrile based graphite fiber is produced by adding nano-additives to the polyacrylnitrile spinning process before conducting the steps of stabilization, carbonization and graphitization.
- the object of the present invention to provide a graphite fiber with a high grade of graphitization having improved mechanical properties and not being prone to oxidation.
- the solution of the present invention is based on the finding that precursor materials having small diameter, like fibers or powder, can be catalytically graphitized by applying a graphitization catalyst on the surface of the respective precursor material, like polyacrylonitrile fibers or powder, rayon fibers or powder, resin fibers or powder, pitch fibers or powder, or natural (or frequentlybio"-) precursor fibers or powder, like lignin fibers or powder.
- a graphitization catalyst on the surface of the respective precursor material, like polyacrylonitrile fibers or powder, rayon fibers or powder, resin fibers or powder, pitch fibers or powder, or natural (or staggeringbio"-) precursor fibers or powder, like lignin fibers or powder.
- the thus applied coating catalyzes the transformation of the precursor material via carbon to graphite at elevated temperatures somehow from the surface region of the material to the center, i.e., the inner region of the material.
- the prescribed catalytic graphitization via coating also works well when the respective stabilized (or chemically activated)
- the present invention provides as a first aspect a graphite material based on a precursor material comprising at least one of the group consisting of polyacrylonitrile, rayon, resin, pitch and natural carbon precursors, wherein the graphite material has an interlayer spacing (d002 distance) of below 0.344 nm, preferably below 0.341 nm, more preferably of below 0.340 nm and a mean crystallite size (Lc) of at least 12 nm, preferably at least 20 nm, wherein the graphite material is porous having voids with a mean diameter of not larger than 50 nm, preferably not larger than 30 nm, more preferably not larger than 20 nm, even more preferably not larger than 10 nm, most preferably not larger than 5 nm, and wherein the graphite material is in the form of either graphite fibers or graphite powder.
- the mean diameter of the voids can be determined using electron microscopy like scanning electron microscopy (SEM) or transmission electron micro
- the terms as accordance with the present invention are synonyms and refer to the substance itself, regardless of the form in which the substance is present.
- the graphite material of the present invention is in the form of fibers and powders.
- the fibers and powders of the present invention can, of course, be further processed to, for example, textiles and composites as described further below which are also encompassed by the present invention.
- Physical properties with respect to the graphite material of the present invention refer to the substance as such.
- the voids of the present invention for example, are present in the fibers or in the powder. Further voids may be present in a textile or composite between the fibers or between the powder particles, but such voids are not meant by the voids of the present invention.
- the material of the present invention is, thus, getting close to the ideal graphite structure featuring high thermal and electrical conductivity. Furthermore, also the frictional properties are advantageous, in particular for applications like as friction materials in clutches, wet-friction, brake discs and brake pads.
- One of the advantages of the graphite material of the present invention is that it has a high thermal conductivity of about 1 100 W/m-K (determined according to DIN 51908). The electrical conductivity is also very high compared to standard carbon materials, like carbon fibers.
- the graphite material of the present invention is less cost-intensive than mesophase- pitch based graphite materials, since it is based on the precursor materials polyacrylonitrile, rayon, resin, like phenolic resin, pitch or natural carbon precursors, like lignin.
- a preferred precursor material of the present invention is polyacrylonitrile.
- Polyacrylonitrile-based carbon fibers, for example, are well known in the art and exhibit a lot of advantageous properties while being relatively cost-effective at the same time.
- polyacrylonitrile-based means that the graphite material is obtained by starting with polyacrylonitrile as the base material for the respective precursor fiber or powder 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.
- Natural carbon precursors mean bio precursors for carbon materials like, for example, lignin.
- the graphite material contains at least one element selected from the group consisting of Ca, Si, B, Al, Ti, V, Cr, Ni, Mn, Fe, Mo, W and Cu.
- these elements originate from a coating which has been applied on the respective fibers or powder before graphitization. The elements may diffuse somehow into the material during graphitization and, thus, traces of the elements may still be present in the graphite material of the present invention and may have some advantageous functions depending on the final application of the graphite material.
- the graphite material can also contain nano-forms, oxides, carbides, nitrides, borides, inorganic salts and organic salts thereof.
- Graphite fibers are preferred forms of the graphite material of the present invention.
- the present invention thus, provides a graphite fiber comprising the graphite material of the present invention.
- the graphite fibers of the present invention can be present as single fibers, fiber bundles, stretch broken yarn and/or any kind of textile and in all of these forms, the fibers can be either staple fibers or continuous fibers. Textiles include woven fabrics, braidings, non- wovens, non-crimp fabrics and paper.
- the graphite fibers of the present invention are preferably present in the form of a woven fabric. In another embodiment, the graphite fibers of the present invention are preferably present in the form of a braided fabric. In another embodiment, the graphite fibers of the present invention are preferably present in the form of a non-woven. In another embodiment, the graphite fibers of the present invention are preferably present in the form of a non-crimp fabric. In another embodiment, the graphite fibers of the present invention are preferably present in the form of a graphite fiber paper. Furthermore, the graphite fibers of the present invention can also be present in the form of milled fibers.
- the milling grade of the milled fibers is not limited and, thus, the milled fibers according to an embodiment are preferably present in the form milled down to a powder. From all the preceding forms of the graphite fibers of the present invention, further products can be formed, like fiber composite materials, which are also encompassed by the present invention.
- a method for manufacturing a graphite material comprising the following steps:
- liquid precursor composition comprising polyacrylonitrile, rayon, resin, pitch or natural carbon precursors
- a precursor material selected from the group consisting of precursor fibers and precursor powder by either spinning the precursor composition in order to obtain precursor fibers or forming a precursor powder from the precursor composition, respectively, c) optionally subjecting the precursor material to stabilization in order to obtain a stabilized precursor material,
- step b) subjecting the carbon material to graphitization in order to obtain the graphite material, wherein either after step b), c) or d) the material obtained in the respective step is subjected to a coating step comprising applying a compound on the surface of the material, wherein the compound contains at least one of the group consisting of Ca, Si, B, Al, Ti, V, Cr, Ni, Mn, Fe, Mo, W and Cu as well as oxides, carbides, nitrides, borides, inorganic salts and organic salts thereof.
- a graphite fiber based on PAN precursor can be produced with a inter- layer distance of 0.336 nm; cf. the examples further below:
- the XRD (X-Ray diffraction) structure of the former Ni-coated fiber is more or less identical with a structure which can only be done for C-fibers with mesophase as a precursor or even better. If active material with a low vaporization temperature can be used (e.g. Ni), then the temperature for graphitization can be lowered to e.g. 2000 °C and even lower. This increases efficiency of the process and reduces energy costs.
- the respective Lc-value of the fiber is also very high close to maximum of the measurable level (> 250 nm).
- any carbonizable resin can be used, i.e., any resin which, under inert atmosphere and elevated temperatures, essentially transforms into carbon.
- exemplary resins are phenolic resins, epoxy resins or polyimide based resins, wherein phenolic resins are preferred due to the higher carbon yield after carbonization.
- Underjurielevated temperature in this regard, temperatures are to be understood which are sufficient for carbonizing organic matter, typical tem- peratures for carbonization (step d of the method) are above 900 °C, preferably 1 100 °C or above.
- the kind of spinning method in step b) is not particularly limited. Possible spinning methods are air gap spinning, dry spinning, melt spinning and wet spinning. Preferably, however, the spinning step b) 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. From the spinning method, a precursor fiber can be obtained. The fiber can be further processed according to the process of the invention as a continuous fiber. It is, however, also possible making any kind of textile fabric from the fiber before further pro- cessing. That is, a textile can be formed from the fiber either in the state of a precursor fiber or a stabilized precursor fiber or a carbon fiber.
- a textile is formed from the stabilized precursor fibers, then the textile is subjected to the coating step, to carbonization and finally to graphitization.
- a textile is formed from the coated stabilized precursorfibers, then the textile is subjected to carbonization and finally to graphitization.
- a textile is formed from the carbon fibers, then the textile is subjected to the coating step and finally to graphitization.
- a textile is formed from the coated carbon fibers, then the textile is subjected to graphitization.
- a textile is formed from the coated precursor fibers, then the textile is subjected to stabi- lization, to carbonization and finally to graphitization.
- a textile is formed from the precursor fibers, then the textile is subjected to the coating step, to stabilization, to carbonization and finally to graphitization.
- the present method can also be performed using polyacrylonitrile powder materials, leading to highly graphitized round-shaped powders which can be used e.g. as anode material with Lithium-ion Battery (LiB)-applications.
- LiB Lithium-ion Battery
- ..stabilization is to be understood generally as a kind of chemical activation step which can be carried out under a variety of conditions depending on the kind of precursor material chosen. Whether or not the step of stabilization is performed depends on the choice of the precursor material. Stabilization is highly preferred when the precursor material is of polyacrylonitrile. Stabilization of polyacrylonitrile typically is conducted under elevated temperatures in the presence of oxygen in the atmosphere which is well known in the art of carbon fiber production. Other materials like cellulose or rayon may be pyrolized at about 400 °C and then carbonized right away in one step. Polyethylene, for example, may be chemically activated before carbonization by a change of the C-H groups into C- hetero atom groups. Pitch fibers are typically oxidized between 200 °C and 400 °C before carbonization. These and other methods for stabilization/chemical activation are known in the art and any of them can be used in the process of the present invention, if suitable.
- Typical graphitization temperatures are within the range of 2400 °C to 3000 °C. Depending on the choice of the graphitization catalyst, the graphitization temperature can be lowered to about 800 °C. Thus, the preferred temperature range for the graphitization is from 800 °C to 3000 °C, more preferably from 800 °C to 2500 °C. According to a preferred embodiment of the present invention, step e) is conducted in an inert atmosphere.
- the compound applied in the method of the present invention is or contains a graphitization catalyst or its respective precursor.
- the compound applied in the coating step contains at least one of the group consisting of Ni, Fe, oxides of Ni and Fe, carbides of Ni and Fe, nitrides of Ni and Fe, borides of Ni and Fe, inorganic and organic salts of Ni and Fe, nano-silicon, S1O2, SiC, AI2O3, T1B2, T1O2 and TiC.
- Ni-acetate is more preferred. Due to variation of the additive content, i.e., the catalyst material, and high temperature treatment conditions interlayer spacing can be controlled and properties like elastic modules and conductivities can be designed.
- the coating step can be performed after step b). That is, the coating, i.e., the compound, is applied on the surface of the precursor fiber or precursor powder. Preferably, the coating is applied onto the carbon material, like a carbon fiber. If the optional stabilization step or, as explained above, the chemical activation step c) is carried out, it is preferred that the coating step is performed after the stabilization step.
- the compound is applied on the surface of the material either chemically, electrochemically or physically by contacting the material with the compound in the coating step.
- the compound to be applied is in the form of dry particles, in the form of suspended particles in a liquid medium, in the form of a solution in a liquid solvent or in gaseous form.
- a preferred coating step is performed by contacting the material to be coated with a liquid medium containing the compound, i.e., the graphitization catalyst, preferably a ⁇ 2 dispersion, a Si-based sizing or a Ni-salt solution for chemical deposition of Ni.
- the precursor material is a precursor fiber and the coating step comprises a fiber sizing step.
- the fiber sizing step can be similar to any sizing method known in carbon fiber production.
- the liquid precursor composition encompasses any liquid, including but not limited to solutions or melts, containing a polyacrylonitrile polymer, a rayon polymer, a resin polymer, pitch or natural carbon precursors. Preferred, however, is a polyacrylonitrile solution. Most preferably, the liquid precursor composition comprises a polyacrylonitrile precursor for carbon fiber production. Also preferred is pitch melt, being then subjected to melt spinning. According to a preferred embodiment of the present invention, after step e) the graphite material is thermally treated at above 1000 °C in the presence of chlorine gas or chlorofluorocarbon gas, preferably dichlorodifluoromethane and/or 1 ,1 ,1 ,2-tetrafluorethane.
- chlorine gas or chlorofluorocarbon gas preferably dichlorodifluoromethane and/or 1 ,1 ,1 ,2-tetrafluorethane.
- the present invention provides a use of the graphite material of the present invention or of the graphite material obtainable from the method of the present invention for 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 desalina- tion 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; and as additive for friction materials, preferably in brake pads or brake discs typically for aircraft and racing cars, wet friction, preferably for clutches; for deicing applica- tions; as filter material; for electromagnetic shielding; for flash protection and as material for electrical contacts.
- Ni-coating of a polyacrylonitrile (PAN)-based carbon fiber the following method can be exemplarily used (among other known Ni-Coating procedures): For cleaning the surface of the carbon fiber, the fiber is rinsed with water and sonicated afterwards in distilled water, acetone, NaOH, HCI and a second time with distilled water each for 15 minutes.
- the dried fiber is heated to 50 °C in a solution of SnC /HCI for 4 hours and afterwards in a solution of PdC /HCI for 15 minutes.
- a coating solution is prepared by mixing 30 g/l NiC , 10 g/l sodium hypophosphate, 12 g/l sodium citrate, 10 ml/l acetic acid in an aqueous solution.
- the ph was adjusted to 4-6 by adding NH4OH.
- Temperature of the solution was then heated to 90 °C and the fiber dipped in for coating.
- a dispersion with 2 g/l is prepared and treated with ultrasonic for 10 minutes for particle dispersion. Every 2 minutes the dispersion was allowed to cool down for 5 minutes at room tem- perature.
- the oxidized PAN-fiber was then dip coated in the prepared dispersion, that is, dipped in, taken out and shortly dripped of. Afterwards the fiber was dried for 3 hours at 120 °C. Based on this dip coating about 0,5 weight-% T1O2 based on the total weight of the oxidized PAN-fiber was applied on the oxidized PAN-fiber.
- the coated fiber was then heated up to 2800 °C in an inert atmosphere and XRD data was measured afterwards in comparison to the same oxidized PAN fiber without T1O2 coating.
- a nickel coated carbon fiber from Toho Tenax (PAN based), Tenax-J HTS40 A23 12K 1420 tex MC (diameter: 7,5 ⁇ ; incl. 0.25 ⁇ Ni) was graphitized in N2-atmosphere at 2000°C and in Lengthwise Graphitization at 2600°C.
- XRD analysis yields interlayer spacing of 0,336 nm and Lc of 320 nm.
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Abstract
The present invention relates to a graphite material based on a precursor material comprising at least one of the group consisting of polyacrylonitrile, rayon, resin, pitch and natural carbon precursors, wherein the graphite material has an interlayer spacing (d002 distance) of below 0.344 nm, preferably below 0.341 nm, more preferably of below 0,340 nm and a mean crystallite size (Lc) of at least 12 nm, preferably at least 20 nm, wherein the graphite material is porous having voids with a mean diameter of not larger than 50 nm, preferably not larger than 10 nm, more preferably not larger than 5 nm, and wherein the graphite material is in the form of either graphite fibers or graphite powder. The graphite material is produced by catalytic graphitization via coating.
Description
Graphite material
The present invention relates to graphite fibers and graphite powder, a method for the manu- facturing the same and its uses for 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 graphitiza- tion 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 sp2-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. While the 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.
A graphitic material, such as a graphite fiber, features high electrical and thermal conductivity rather than, for example, high tensile strength as carbon fibers do. Thus, the focus of graphite materials lies on applications requiring suitable thermo-electrical properties rather than good mechanical properties. Graphite fibers can, for example, be obtained by graphitization of mesophase pitch-based carbon fibers. That means, carbon fibers based on mesophase pitch are heated to a sufficiently high temperature, typically above 2200 °C, so that the apriori amorphous carbon converts into a graphitic structure. Mesophase pitch-based carbon fibers, however, are very expensive. Compared to typical polyacrylonitrile-based carbon fibers mesophase pitch-based carbon fibers can cost about 100 times more. Polyacrylonitrile-based
carbon fibers, however, do not graphitize as good as mesophase pitch-based carbon fibers even if they are heated up to 2200 °C or above.
The d002 distance and the Lc of a polyacrylonitrile-based carbon fiber which is carbonized at a temperature of 2500 °C are about 0.343 nm and 5 nm respectively (Sources: M. Inagaki, F. Kang, Materials Science and Engineering of Carbon: Fundamentals, Elsevier, 2nd Edition, 2014 and M.R. Buchmeister et al., Carbonfasern: Prakursor-Systeme, Verarbeitung, Struktur und Eigenschaften, Angewandte Chemie 2014, vol. 126, pages 5364-5403). According to WO2017/178492 a polyacrylnitrile based graphite fiber is produced by adding nano-additives to the polyacrylnitrile spinning process before conducting the steps of stabilization, carbonization and graphitization. However, this process has the disadvantage that an increased porosity or higher defect numbers or defect sizes of the graphite fibers is generated due to the nano- additives after their reaction in the catalytic process. Typically, a pore (defect) is introduced at the place where the additive was incorporated in the fiber. Consequently, the mechanical prop- erties of these graphite fibers are deteriorated and the surface of these graphite fibers is more prone to oxidation.
It is, therefore, the object of the present invention to provide a graphite fiber with a high grade of graphitization having improved mechanical properties and not being prone to oxidation.
The solution of the present invention is based on the finding that precursor materials having small diameter, like fibers or powder, can be catalytically graphitized by applying a graphitization catalyst on the surface of the respective precursor material, like polyacrylonitrile fibers or powder, rayon fibers or powder, resin fibers or powder, pitch fibers or powder, or natural (or „bio"-) precursor fibers or powder, like lignin fibers or powder. The thus applied coating catalyzes the transformation of the precursor material via carbon to graphite at elevated temperatures somehow from the surface region of the material to the center, i.e., the inner region of the material. The prescribed catalytic graphitization via coating also works well when the respective stabilized (or chemically activated) precursor material or carbon material is coated with the graphitization catalyst.
The present invention, thus, provides as a first aspect a graphite material based on a precursor material comprising at least one of the group consisting of polyacrylonitrile, rayon, resin, pitch and natural carbon precursors, wherein the graphite material has an interlayer spacing (d002 distance) of below 0.344 nm, preferably below 0.341 nm, more preferably of below 0.340 nm
and a mean crystallite size (Lc) of at least 12 nm, preferably at least 20 nm, wherein the graphite material is porous having voids with a mean diameter of not larger than 50 nm, preferably not larger than 30 nm, more preferably not larger than 20 nm, even more preferably not larger than 10 nm, most preferably not larger than 5 nm, and wherein the graphite material is in the form of either graphite fibers or graphite powder. The mean diameter of the voids can be determined using electron microscopy like scanning electron microscopy (SEM) or transmission electron microscopy (TEM).
In the framework of the present invention the terms„graphitic material" and„graphite material" are synonyms and refer to the substance itself, regardless of the form in which the substance is present. The graphite material of the present invention is in the form of fibers and powders. The fibers and powders of the present invention can, of course, be further processed to, for example, textiles and composites as described further below which are also encompassed by the present invention. Physical properties with respect to the graphite material of the present invention refer to the substance as such. The voids of the present invention, for example, are present in the fibers or in the powder. Further voids may be present in a textile or composite between the fibers or between the powder particles, but such voids are not meant by the voids of the present invention. In case that some features of the aspects and embodiments of the present invention including the corresponding advantages are described in connection with either fibers only or a powder only, this is not to be understood as limiting. Unless explicitly described otherwise or the occurrence of a logical contradiction, all features described herein can be combined with both forms, fibers and powder, of the graphitic material of the present invention, its respective production methods and its uses. The interlayer spacing (d002 distance) and mean crystallite size (Lc) are crystallographic standard parameters which can be easily measured by known methods, like X-ray diffraction, for example, according to the method described by J. Maire and J. Mehring in "Graphitization of soft carbons" in Chemistry and Physics of Carbon, Vol. 6, Marcel Dekker, P.L. Walker Jr. (Publisher), New York, 1970, pages 125-190.
The material of the present invention is, thus, getting close to the ideal graphite structure featuring high thermal and electrical conductivity. Furthermore, also the frictional properties are advantageous, in particular for applications like as friction materials in clutches, wet-friction, brake discs and brake pads.
One of the advantages of the graphite material of the present invention is that it has a high thermal conductivity of about 1 100 W/m-K (determined according to DIN 51908). The electrical conductivity is also very high compared to standard carbon materials, like carbon fibers. Furthermore, the graphite material of the present invention is less cost-intensive than mesophase- pitch based graphite materials, since it is based on the precursor materials polyacrylonitrile, rayon, resin, like phenolic resin, pitch or natural carbon precursors, like lignin. A preferred precursor material of the present invention is polyacrylonitrile. Polyacrylonitrile-based carbon fibers, for example, are well known in the art and exhibit a lot of advantageous properties while being relatively cost-effective at the same time.
The term "polyacrylonitrile-based" means that the graphite material is obtained by starting with polyacrylonitrile as the base material for the respective precursor fiber or powder as it is analogously the case with polyacrylonitrile-based carbon fibers which are well known in the art. The term "polyacrylonitrile-based" also includes co-polymers of polyacrylonitrile with other monomers.
Natural carbon precursors mean bio precursors for carbon materials like, for example, lignin.
According to a preferred embodiment of the present invention, the graphite material contains at least one element selected from the group consisting of Ca, Si, B, Al, Ti, V, Cr, Ni, Mn, Fe, Mo, W and Cu. As will become apparent further below with regard to the second aspect of the present invention, these elements originate from a coating which has been applied on the respective fibers or powder before graphitization. The elements may diffuse somehow into the material during graphitization and, thus, traces of the elements may still be present in the graphite material of the present invention and may have some advantageous functions depending on the final application of the graphite material. Besides the above pure elements, the graphite material can also contain nano-forms, oxides, carbides, nitrides, borides, inorganic salts and organic salts thereof. Graphite fibers are preferred forms of the graphite material of the present invention. The present invention, thus, provides a graphite fiber comprising the graphite material of the present invention. The graphite fibers of the present invention can be present as single fibers, fiber bundles, stretch broken yarn and/or any kind of textile and in all of these forms, the fibers can be either staple fibers or continuous fibers. Textiles include woven fabrics, braidings, non- wovens, non-crimp fabrics and paper. In an embodiment, the graphite fibers of the present
invention are preferably present in the form of a woven fabric. In another embodiment, the graphite fibers of the present invention are preferably present in the form of a braided fabric. In another embodiment, the graphite fibers of the present invention are preferably present in the form of a non-woven. In another embodiment, the graphite fibers of the present invention are preferably present in the form of a non-crimp fabric. In another embodiment, the graphite fibers of the present invention are preferably present in the form of a graphite fiber paper. Furthermore, the graphite fibers of the present invention can also be present in the form of milled fibers. The milling grade of the milled fibers is not limited and, thus, the milled fibers according to an embodiment are preferably present in the form milled down to a powder. From all the preceding forms of the graphite fibers of the present invention, further products can be formed, like fiber composite materials, which are also encompassed by the present invention.
According to a second aspect of the present invention, a method for manufacturing a graphite material is provided comprising the following steps:
a) providing a liquid precursor composition comprising polyacrylonitrile, rayon, resin, pitch or natural carbon precursors,
b) forming a precursor material selected from the group consisting of precursor fibers and precursor powder by either spinning the precursor composition in order to obtain precursor fibers or forming a precursor powder from the precursor composition, respectively, c) optionally subjecting the precursor material to stabilization in order to obtain a stabilized precursor material,
d) subjecting the precursor material or the stabilized precursor material to carbonization in order to obtain a carbon material and
e) subjecting the carbon material to graphitization in order to obtain the graphite material, wherein either after step b), c) or d) the material obtained in the respective step is subjected to a coating step comprising applying a compound on the surface of the material, wherein the compound contains at least one of the group consisting of Ca, Si, B, Al, Ti, V, Cr, Ni, Mn, Fe, Mo, W and Cu as well as oxides, carbides, nitrides, borides, inorganic salts and organic salts thereof.
By using this method, a graphite fiber based on PAN precursor can be produced with a inter- layer distance of 0.336 nm; cf. the examples further below: The XRD (X-Ray diffraction) structure of the former Ni-coated fiber is more or less identical with a structure which can only be done for C-fibers with mesophase as a precursor or even better. If active material with a low vaporization temperature can be used (e.g. Ni), then the temperature for graphitization can be
lowered to e.g. 2000 °C and even lower. This increases efficiency of the process and reduces energy costs. The respective Lc-value of the fiber is also very high close to maximum of the measurable level (> 250 nm). As a resin, any carbonizable resin can be used, i.e., any resin which, under inert atmosphere and elevated temperatures, essentially transforms into carbon. Exemplary resins are phenolic resins, epoxy resins or polyimide based resins, wherein phenolic resins are preferred due to the higher carbon yield after carbonization. Under„elevated temperature" in this regard, temperatures are to be understood which are sufficient for carbonizing organic matter, typical tem- peratures for carbonization (step d of the method) are above 900 °C, preferably 1 100 °C or above.
The kind of spinning method in step b) is not particularly limited. Possible spinning methods are air gap spinning, dry spinning, melt spinning and wet spinning. Preferably, however, the spinning step b) 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. From the spinning method, a precursor fiber can be obtained. The fiber can be further processed according to the process of the invention as a continuous fiber. It is, however, also possible making any kind of textile fabric from the fiber before further pro- cessing. That is, a textile can be formed from the fiber either in the state of a precursor fiber or a stabilized precursor fiber or a carbon fiber. As a preferred embodiment, thus, a textile is formed from the stabilized precursor fibers, then the textile is subjected to the coating step, to carbonization and finally to graphitization. As another preferred embodiment, thus, a textile is formed from the coated stabilized precursorfibers, then the textile is subjected to carbonization and finally to graphitization. As still another preferred embodiment, thus, a textile is formed from the carbon fibers, then the textile is subjected to the coating step and finally to graphitization. As still another preferred embodiment, thus, a textile is formed from the coated carbon fibers, then the textile is subjected to graphitization. As still another preferred embodiment, thus, a textile is formed from the coated precursor fibers, then the textile is subjected to stabi- lization, to carbonization and finally to graphitization. As still another preferred embodiment, thus, a textile is formed from the precursor fibers, then the textile is subjected to the coating step, to stabilization, to carbonization and finally to graphitization.
The present method can also be performed using polyacrylonitrile powder materials, leading to highly graphitized round-shaped powders which can be used e.g. as anode material with Lithium-ion Battery (LiB)-applications. The term ..stabilization" according to the optional method step c) is to be understood generally as a kind of chemical activation step which can be carried out under a variety of conditions depending on the kind of precursor material chosen. Whether or not the step of stabilization is performed depends on the choice of the precursor material. Stabilization is highly preferred when the precursor material is of polyacrylonitrile. Stabilization of polyacrylonitrile typically is conducted under elevated temperatures in the presence of oxygen in the atmosphere which is well known in the art of carbon fiber production. Other materials like cellulose or rayon may be pyrolized at about 400 °C and then carbonized right away in one step. Polyethylene, for example, may be chemically activated before carbonization by a change of the C-H groups into C- hetero atom groups. Pitch fibers are typically oxidized between 200 °C and 400 °C before carbonization. These and other methods for stabilization/chemical activation are known in the art and any of them can be used in the process of the present invention, if suitable.
Typical graphitization temperatures (step e of the method) are within the range of 2400 °C to 3000 °C. Depending on the choice of the graphitization catalyst, the graphitization temperature can be lowered to about 800 °C. Thus, the preferred temperature range for the graphitization is from 800 °C to 3000 °C, more preferably from 800 °C to 2500 °C. According to a preferred embodiment of the present invention, step e) is conducted in an inert atmosphere.
The compound applied in the method of the present invention is or contains a graphitization catalyst or its respective precursor. According to a preferred embodiment of the present invention, the compound applied in the coating step contains at least one of the group consisting of Ni, Fe, oxides of Ni and Fe, carbides of Ni and Fe, nitrides of Ni and Fe, borides of Ni and Fe, inorganic and organic salts of Ni and Fe, nano-silicon, S1O2, SiC, AI2O3, T1B2, T1O2 and TiC. Ni-acetate is more preferred. Due to variation of the additive content, i.e., the catalyst material, and high temperature treatment conditions interlayer spacing can be controlled and properties like elastic modules and conductivities can be designed.
The coating step can be performed after step b). That is, the coating, i.e., the compound, is applied on the surface of the precursor fiber or precursor powder. Preferably, the coating is applied onto the carbon material, like a carbon fiber. If the optional stabilization step or, as
explained above, the chemical activation step c) is carried out, it is preferred that the coating step is performed after the stabilization step.
According to a preferred embodiment of the present invention, the compound is applied on the surface of the material either chemically, electrochemically or physically by contacting the material with the compound in the coating step.
According to a preferred embodiment of the present invention, the compound to be applied is in the form of dry particles, in the form of suspended particles in a liquid medium, in the form of a solution in a liquid solvent or in gaseous form. A preferred coating step is performed by contacting the material to be coated with a liquid medium containing the compound, i.e., the graphitization catalyst, preferably a ΤΊΟ2 dispersion, a Si-based sizing or a Ni-salt solution for chemical deposition of Ni. According to a preferred embodiment of the present invention, the precursor material is a precursor fiber and the coating step comprises a fiber sizing step. The fiber sizing step can be similar to any sizing method known in carbon fiber production.
The liquid precursor composition encompasses any liquid, including but not limited to solutions or melts, containing a polyacrylonitrile polymer, a rayon polymer, a resin polymer, pitch or natural carbon precursors. Preferred, however, is a polyacrylonitrile solution. Most preferably, the liquid precursor composition comprises a polyacrylonitrile precursor for carbon fiber production. Also preferred is pitch melt, being then subjected to melt spinning. According to a preferred embodiment of the present invention, after step e) the graphite material is thermally treated at above 1000 °C in the presence of chlorine gas or chlorofluorocarbon gas, preferably dichlorodifluoromethane and/or 1 ,1 ,1 ,2-tetrafluorethane. This treatment is suitable to remove remaining graphitization catalyst and, thus, to purify the graphite product. In another aspect, the present invention provides a use of the graphite material of the present invention or of the graphite material obtainable from the method of the present invention for 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 desalina-
tion 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; and as additive for friction materials, preferably in brake pads or brake discs typically for aircraft and racing cars, wet friction, preferably for clutches; for deicing applica- tions; as filter material; for electromagnetic shielding; for flash protection and as material for electrical contacts.
EXAMPLES: Example 1 : Ni Coating
For Ni-coating of a polyacrylonitrile (PAN)-based carbon fiber the following method can be exemplarily used (among other known Ni-Coating procedures): For cleaning the surface of the carbon fiber, the fiber is rinsed with water and sonicated afterwards in distilled water, acetone, NaOH, HCI and a second time with distilled water each for 15 minutes.
Then the dried fiber is heated to 50 °C in a solution of SnC /HCI for 4 hours and afterwards in a solution of PdC /HCI for 15 minutes.
Then a coating solution is prepared by mixing 30 g/l NiC , 10 g/l sodium hypophosphate, 12 g/l sodium citrate, 10 ml/l acetic acid in an aqueous solution. The ph was adjusted to 4-6 by adding NH4OH. Temperature of the solution was then heated to 90 °C and the fiber dipped in for coating.
The coated fiber was then heated up to 1800°C in an inert atmosphere and XRD data was measured afterwards in comparison to the same PAN-based carbon fiber without Ni coating. Fiber without coating: d002 [nm] = 0,346; Lc [nm] = 4.
Fiber with Ni-coating: d002 [nm] = 0,336; Lc [nm] = 131 .
Example 2: T1O2 Coating
For coating of an oxidized PAN-fiber an aqueous dispersion of titanium dioxide is prepared using titanium dioxide with a primary particle size of d50 = 14 nm and d50 = 70 nm in aggregate state (available under the trade name AEROXIDE® ΤΊΟ2 P90 from Evonik).
A dispersion with 2 g/l is prepared and treated with ultrasonic for 10 minutes for particle dispersion. Every 2 minutes the dispersion was allowed to cool down for 5 minutes at room tem- perature.
The oxidized PAN-fiber was then dip coated in the prepared dispersion, that is, dipped in, taken out and shortly dripped of. Afterwards the fiber was dried for 3 hours at 120 °C. Based on this dip coating about 0,5 weight-% T1O2 based on the total weight of the oxidized PAN-fiber was applied on the oxidized PAN-fiber.
The coated fiber was then heated up to 2800 °C in an inert atmosphere and XRD data was measured afterwards in comparison to the same oxidized PAN fiber without T1O2 coating.
Fiber without coating: d002 [nm] = 0,341 ; Lc [nm] = 10.
Fiber with 0,5% Ti02 coating: d002 [nm] = 0,337; Lc [nm] = 24.
Example 3:
A nickel coated carbon fiber from Toho Tenax (PAN based), Tenax-J HTS40 A23 12K 1420 tex MC (diameter: 7,5 μηι; incl. 0.25 μηι Ni) was graphitized in N2-atmosphere at 2000°C and in Lengthwise Graphitization at 2600°C. XRD analysis yields interlayer spacing of 0,336 nm and Lc of 320 nm.
For comparison a pitch fiber from Mitsubishi Rayon (DIALEAD K63712) yields interlayer spacing of 0,337 nm (Lc of 58 nm) only and is therefore less graphitized.
Claims
Claims
A graphite material based on a precursor material comprising at least one of the group consisting of polyacrylonitrile, rayon, resin, pitch and natural carbon precursors, wherein the graphite material has an interlayer spacing (d002 distance) of below 0.344 nm, and a mean crystallite size (Lc) of at least 12 nm, wherein the graphite material is porous having voids with a mean diameter of not larger than 50 nm, wherein the graphite material is in the form of either graphite fibers or graphite powder.
The graphite material according to claim 1 , characterized in that the material is based on polyacrylonitrile.
The graphite material according to claim 1 or 2, characterized in that it contains at least one element selected from the group consisting of Ca, Si, B, Al, Ti, V, Cr, Ni, Mn, Fe, Mo, W and Cu.
A graphite fiber comprising the graphite material according to any of claims 1 to 3.
A method for manufacturing a graphite material according to any of claims 1 to 4 comprising the following steps:
a) Providing a liquid precursor composition comprising polyacrylonitrile, rayon, resin, pitch or natural carbon precursors,
b) forming a precursor material selected from the group consisting of precursor fibers and precursor powder by either spinning the precursor composition in order to obtain precursor fibers orforming a precursor powderfrom the precursor composition, respectively,
c) optionally subjecting the precursor material to stabilization in order to obtain a stabilized precursor material,
d) subjecting the precursor material or the stabilized precursor material to carbonization in order to obtain a carbon material and
e) subjecting the carbon material to graphitization in order to obtain the graphite material,
wherein either after step b), c) or d) the material obtained in the respective step is subjected to a coating step comprising applying a compound on the surface of the
material, wherein the compound contains at least one of the group consisting of Ca, Si, B, Al, Ti, V, Cr, Ni, Mn, Fe, Mo, W and Cu as well as oxides, carbides, nitrides, borides, inorganic salts and organic salts thereof.
The method according to claim 5, characterized in that the compound applied in the coating step contains at least one of the group consisting of Ni, Fe, oxides of Ni and Fe, carbides of Ni and Fe, nitrides of Ni and Fe, borides of Ni and Fe, inorganic and organic salts of Ni and Fe, nano-silicon, S1O2, SiC, AI2O3, T1B2, T1O2 and TiC.
The method according to claim 5, characterized in that the compound is applied on the surface of the material either chemically, electrochemically or physically by contacting the material with the compound in the coating step.
The method according to claim 5, characterized in that the compound to be applied is in the form of dry particles, in the form of suspended particles in a liquid medium, in the form of a solution in a liquid solvent or in gaseous form.
The method according to claim 5, characterized in that the precursor material is a precursor fiber and that the coating step comprises a fiber sizing step.
Use of the graphite material according to any of claims 1 to 4 for 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; as conductive filler for polymers; as a catalyst carrier; as additive for friction materials; for de- icing applications; as filter material; for electromagnetic shielding; for flash protection and as material for electrical contacts.
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CN110085863A (en) * | 2019-04-26 | 2019-08-02 | 桑顿新能源科技有限公司 | Graphite cathode material and preparation method thereof, battery |
CN112117455A (en) * | 2020-09-21 | 2020-12-22 | 贝特瑞新材料集团股份有限公司 | Negative electrode material, preparation method thereof and lithium ion battery |
CN112952115A (en) * | 2019-12-10 | 2021-06-11 | 中国科学院大连化学物理研究所 | Electrode material and application thereof in all-vanadium redox flow battery |
CN113443623A (en) * | 2021-07-18 | 2021-09-28 | 陕西则明未来科技有限公司 | Method for reducing graphitization temperature through composite catalysis |
CN117865710A (en) * | 2023-12-25 | 2024-04-12 | 深圳市佰斯倍新材料科技有限公司 | Preparation method of carbon ceramic brake disc and product thereof |
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CN110085863A (en) * | 2019-04-26 | 2019-08-02 | 桑顿新能源科技有限公司 | Graphite cathode material and preparation method thereof, battery |
CN110085863B (en) * | 2019-04-26 | 2024-03-12 | 桑顿新能源科技有限公司 | Graphite negative electrode material, preparation method thereof and battery |
CN112952115A (en) * | 2019-12-10 | 2021-06-11 | 中国科学院大连化学物理研究所 | Electrode material and application thereof in all-vanadium redox flow battery |
CN112117455A (en) * | 2020-09-21 | 2020-12-22 | 贝特瑞新材料集团股份有限公司 | Negative electrode material, preparation method thereof and lithium ion battery |
CN113443623A (en) * | 2021-07-18 | 2021-09-28 | 陕西则明未来科技有限公司 | Method for reducing graphitization temperature through composite catalysis |
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