WO2012051973A1 - Composite c/c à larges pores ouverts présentant une grande surface interne, procédé de production correspondant et utilisation - Google Patents

Composite c/c à larges pores ouverts présentant une grande surface interne, procédé de production correspondant et utilisation Download PDF

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Publication number
WO2012051973A1
WO2012051973A1 PCT/DE2011/001535 DE2011001535W WO2012051973A1 WO 2012051973 A1 WO2012051973 A1 WO 2012051973A1 DE 2011001535 W DE2011001535 W DE 2011001535W WO 2012051973 A1 WO2012051973 A1 WO 2012051973A1
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Prior art keywords
composite
carbon
surface area
composite according
carrier material
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PCT/DE2011/001535
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German (de)
English (en)
Inventor
Gudrun Reichenauer
Christian Scherdel
Matthias Wiener
Stephan Braxmeier
Holger Fink
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Bayerisches Zentrum Für Angewandte Energieforschung E.V. Zae Bayern
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Priority claimed from DE102010033380A external-priority patent/DE102010033380A1/de
Priority claimed from DE102011108435A external-priority patent/DE102011108435A1/de
Application filed by Bayerisches Zentrum Für Angewandte Energieforschung E.V. Zae Bayern filed Critical Bayerisches Zentrum Für Angewandte Energieforschung E.V. Zae Bayern
Publication of WO2012051973A1 publication Critical patent/WO2012051973A1/fr

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    • C04B35/624—Sol-gel processing
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    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
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    • B01J20/28078—Pore diameter
    • B01J20/2808—Pore diameter being less than 2 nm, i.e. micropores or nanopores
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    • C04B38/0045—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by a process involving the formation of a sol or a gel, e.g. sol-gel or precipitation processes
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    • H01—ELECTRIC ELEMENTS
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    • H01M12/00—Hybrid cells; Manufacture thereof
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    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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Definitions

  • the invention relates to a carbon-carbon ⁇ C / C) composite characterized in that a carrier material made of carbon is coated with a nanoporous carbon material having a high specific surface area, in which case pores smaller than 1 ⁇ m are to be understood as nanopores.
  • a carbon support material e.g., charcoal, graphite, carbon and graphite felts, carbon foams, or the organic precursors of these types of materials
  • the coating of the carrier material takes place via a liquid precursor in a sol-gel process, the coating initially being present as organic precursor (for example, porous duromer). Since the precursor of the C / C composite still contains organic components, the C / C composite is produced by carbonation in a pyrolysis step.
  • Carbon-carbon (C / C) composite materials consisting of a carrier material of carbon and a pyrolytic carbon coating are known from various sources and state of the art.
  • the pyrocarbon layer is characterized by a high structural order of the carbon atoms (graphitic) and an increased oxidation resistance.
  • the specific surface of the coating is well below 10 m 2 / g and the Pyrokohlenstoffbeschich- tion has no significant Nanostruktu réelle and no nanoporosity (structures ⁇ 1 ⁇ ) on.
  • the coating with pyrocarbon leads via chemical vapor deposition (CVD) to a C / C composite of very low specific surface area.
  • CVD chemical vapor deposition
  • the coating with pyrolytic carbon leads to a significant reduction specific surface area, whereby there are no micropore (definition of micropores in- Sing KSW, Everett DH, Haul RAW, Moscou L, Pierotti RA, Rouquerol J, et al. Reporting physisorption data for gas / solid Systems with special refer- ence to the determination of surface area and porosity. Pure and Applied Chemistry 1985; 57: 603) are detected more.
  • JP10045473AA and JP10045474AA a carbon fiber-reinforced carbon or graphite-based shaped body is subjected to a CVD treatment, wherein a coating with pyrocarbon takes place, which has a thickness of 10 pm - 150 ⁇ .
  • the dense Pyrokohlenstoff für has low impurities and is increased oxidation resistant.
  • JP61219708A describes the preparation of a graphite-based material which is coated with pyrolytic carbon via a CVD process. The coating is deposited with hydrocarbons or halogenated hydrocarbons as precursors at temperatures of 600 ° C to 2400 ° C on the base material.
  • a macromolecular polymer is dissolved in a corresponding organic solvent whose boiling point is below the softening point of the macromolecular Polymers lies.
  • the solution is mixed with graphite particles and the graphite coated by distillation and curing of the macromolecular polymer. Subsequently, a carbonization is carried out. The coating is smooth and the coated graphite particles do not agglomerate.
  • an electrode for redox flow batteries which consists of conductive carbon fabric with homogeneously distributed activated carbon and is introduced into the cavity of a graphite plate.
  • the carbon coating is exclusively smooth, highly graphitic carbon layers of low specific surface area without nanoporosity, usually referred to as pyrocarbon.
  • pyrocarbon coatings serve as protection against thermal and oxidative influences and are unsuitable for use, for example, as an electrode material due to their low specific surface area.
  • the object of the invention is, in a large and porous material made of carbon and its organic precursor while maintaining the large pores, the specific surface of the total material significantly, i. by at least an order of magnitude.
  • an open-pore carrier material made of carbon or of an organic precursor, in particular charcoal, porous graphite plates or flakes, carbon or graphite fiber felts, carbon foams or their organic precursors, via the infiltration of a liquid phase in a sol-gel process with a carbon Precursor coated.
  • the coating can be carried out, for example, by infiltrating the support material with a solution containing polymer constituents, the polymer constituents depositing on the support material in the wet-chemical reaction or during the subsequent removal of the solvent by drying and forming a polymeric precursor of the carbon coating.
  • Decisive here is the formation of a polymeric nanostructured ⁇ e.g. nanoporous) layer via the sol-gel process on the inner surface of the support material.
  • the resulting coated material remains open-pored.
  • the carrier material While in the pyrocarbon deposition by thermal see decomposition of a carbonaceous gas on the surface of the carrier material directly a non-porous carbon layer is generated, in contrast, in the present invention, the carrier material is infiltrated or impregnated with a liquid.
  • the fluid contains molecular carbonaceous constituents which, by polymerization at the surface or in the pores of the carrier material, result in a coating thereof.
  • the polymer coating already exhibits essential structural properties which are characteristic of the C / C composite according to the invention, eg spherical components of the coating see Figure 1 (right) and Figure 3, as well as structural units in the range ⁇ 1 ⁇ (eg pores).
  • furfuryl alcohol polyacrylonitrile (PAN), and combinations of hydroxybenzenes (e.g., phenol, resorcinol) with aldehydes ⁇ e.g. Formaldehyde, furfural) or melamine aldehydes which are dissolved in a solvent (e.g., water, alcohols, ketones) and mixed to accelerate the polymerization with a catalyst (base or acid) or a hardener (e.g., hexamethylenetetramine HMTA).
  • a solvent e.g., water, alcohols, ketones
  • a catalyst base or acid
  • a hardener e.g., hexamethylenetetramine HMTA
  • the remaining solvent is removed by drying from the coated omposit.
  • the coating takes place via the attachment of the polymer building blocks to the inner surface of the support material.
  • the decisive factor here is that in the composite actually comes exclusively to a coating of the carrier material, and the usual sol-gel process, which would lead to a filling of the interstices of the carrier material is prevented by a suitable choice of the process parameters.
  • the carbon conversion takes place by thermal decomposition of the organic constituents at temperatures between 500 ° C. and 1100 ° C. under an oxygen-free atmosphere (pyrolysis ), producing the C / C composite.
  • an activation step at 500 ° C - 1500 ° C (physically, eg with C0 2 or H 2 0 or chemically eg with alkali hydroxides / carbonates) can follow.
  • a high-temperature treatment at temperatures above 1100 ° C offers.
  • a combination of activation and high-temperature treatment may be required.
  • the specific surface of the C / C composite would first be enlarged by an activation and then the electrical conductivity increased by a high-temperature treatment of the C / C composite. This is also possible in reverse order.
  • This can be done by gas phase reactions at temperatures of 100-1000 ° C or from 100-700 ° C in air or under gas flow of defined composition (eg ammonia, oxygen, C0 2 , H 2 0 with or without chemically inert carrier gas ⁇ z.
  • defined composition eg ammonia, oxygen, C0 2 , H 2 0 with or without chemically inert carrier gas ⁇ z.
  • a corresponding treatment is the formation of polar surface groups, which on the one hand improve the wettability / hydrophilicity of the surface of the electrode and increase the contact area between an electrolyte or another liquid and the electrode surface.
  • the reaction kinetics ie the exchange current density of the corresponding reaction at the electrode (eg for V + + 2 , V + 5 / + 4 , Fe + 3 / + 2 ) can be supported by the reaction process / the redox reaction by the functional surface groups increase.
  • the large pore C / C composite of the invention has the entire inner surface of the original support material as a nanoporous carbon coating. If the pure support itself has only a small specific surface area (e.g., charcoal, compressed expanded graphite, graphite fiber felt or carbon foam), the C / C composite has a significantly increased specific surface area, the difference being several orders of magnitude. In addition to the increase in the specific surface area, which is mainly due to the microporosity (pores ⁇ 2 nm) of the carbon coating, the inner surface of the C / C composite also increases due to the spherical components of the carbon layer, as can be seen from RE images (see Figure 1, right and Figure 3).
  • a small specific surface area e.g., charcoal, compressed expanded graphite, graphite fiber felt or carbon foam
  • the large-pore C / C composite is characterized by low density, an open-pore superstructure with pores larger than 1 micrometer, a low flow resistance, a carrier carbon material with high electrical conductivity ⁇ > 0.1 S / cm, in particular> 1.0 S / cm) and a nanosized carbon coating with a high specific surface area.
  • the inventive C / C composite for various applications, preferably as electrode material in electrochemical storage, especially in Redoxpound- batteries (eg in the systems vanadium / vanadium, vanadium / bromine, bromine / polysulfide and cerium / zinc, zinc / Bromine, etc.).
  • a C / C composite made of an electrically highly conductive carbon high, easily accessible porosity, with large pores simultaneously in the range of 1 pm - 5 mm (eg graphite, pressed expanded graphite, carbon or graphite felt, carbon foam ) as carrier material important to allow high flow rates of the electrolyte through the electrode even at low pressure differences.
  • ⁇ is the viscosity of the liquid.
  • the materials used heretofore have a low mass and volume specific surface area, and thus also an electrolyte (e.g., vanadium ion) to low active surface area, which limits cell performance per volume.
  • an electrolyte e.g., vanadium ion
  • the nanoporous carbon coating which has a high specific surface area, increases over that Electrolyte active electrode surface significantly without significantly affecting the flow rate of the electrolyte through the electrode. Overall, this results in an increased power density per volume compared to an uncoated carbon electrode.
  • the C / C composite also lends itself to use as electrode material in other electrochemical applications and other battery forms, for which a coarse and open porous electrode material with high conductivity and high surface area is advantageous, e.g. in metal-air batteries (Zn-air, Li-air).
  • the C / C composite with its high specific surface area and large pores, which enable a good flow rate, is also ideal as an adsorber for filtration.
  • aqueous 37% - formaldehyde solution stabilized with about 10% methanol
  • deionized water deionized water
  • 0, lN-Na 2 C0 3 solution mixed together in a beaker on a magnetic stirrer.
  • the mass of resorcinol and formaldehyde in the total mass of the solution is 20%.
  • the graphite compact is infiltrated in a desiccator with the resorcinol-formaldehyde solution by means of vacuum pressure infiltration.
  • the sample is heated to 90 ° C. for 24 hours in order to achieve a coating of the carbonaceous material with resorcinol-formaldehyde polymers.
  • the liquid is removed by convective drying.
  • the sample is pyrolyzed under non-oxidizing atmosphere (argon) for one hour at S00 ° C.
  • Figure 1 shows an SEM image of the pressed expanded graphite (left) with the coated sample, the C / C composite (right). The deposited nanoporous carbon material on the graphite surface can be clearly seen.
  • the C / C composite has a density of 0.08 g / cm 3 .
  • the specific surface determined by nitrogen sorption in accordance with DIN ISO 9277: 2003-05 has increased by about a factor of 10 to S BET - 458 m 2 / g.
  • the microporous volume according to the t-plot method (DIN 66135-2) is 0.16 cm 3 / g, the external surface 39 m 2 / g.
  • the significantly increased specific surface area of the carbon-coated C / C composite is evident also clearly in the adsorbed gas quantities of the nitrogen sorption isotherms at 77 K of pure carbon support aterial (pressed expanded graphite) and the C / C composite in Figure 2.
  • Embodiment 2 is a diagrammatic representation of Embodiment 1:
  • a graphite hard felt of density 0.1 g / cm 3 and a specific surface S BBT of 0.4 m 2 / g determined from nitrogen sorption according to DIN ISO 9277: 2003-05 with the dimensions 10 cm ⁇ 10 cm ⁇ 1 , 5 cm is soaked at room temperature and atmospheric pressure with a dilute polymer solution.
  • This solution consists of 27.2 g of resorcinol, 39.5 g of an aqueous 7% formaldehyde solution (stabilized with about 10% methanol), 82.7 g of deionized water and 0.6 g of a 0, lN-Na 2 CO 3 - solution.
  • the sample is heated to 85 ° C for 24 hours to coat the carbon support material with resorcin-formaldehyde polymers. Subsequently, the gel is dried convectively at 40 ° C in air at atmospheric pressure for 36 hours.
  • the organic precursor of the C / C composite thus obtained has a density of 0.355 g / cm 3 .
  • the organic precursor of the C / C composite is then pyrolyzed for 3 hours at 800 ° C under non-oxidizing atmosphere (argon).
  • the C / C composite thus obtained has a density of 0.226 g / cm 3 and a BET surface area according to DIN ISO 9277: 2003-05 of 389 m 2 / g.
  • micropore volume by t-plot method (DIN 66135-2) is 0.15 cm 3 / g, the external surface 2 m 2 / g.
  • Figure 3 shows an SEM image of the coated C / C composite. The spherical structures of the nanoporous carbon coating with a high specific surface can be clearly seen.
  • the permeability coefficient k is 7-10 "11 m 2 .
  • the carbon carrier material used is pressed expanded graphite having a density of 0.03 g / cm 3 and a specific surface S BET of 45 m 2 / g determined from nitrogen sorption to DIN ISO 9277: 2003-05.
  • Formaldehyde solution (stabilized with about 10% methanol), n-propanol and 37% HCl mixed together in a beaker on a magnetic stirrer.
  • the mass of phenol and formaldehyde in the total mass of the solution is 15%.
  • the graphite compact is placed in a desiccator with the phenolic Formaldehyde solution infiltrated.
  • the sample is heated for 24 hours at 90 ° C to achieve a coating of the carbon support material with phenol-formaldehyde polymers. Subsequently, the liquid is removed by convective drying.
  • the sample was pyrolysed under a non-oxidizing atmosphere (argon) for one hour at 800 ° C.
  • the C / C composite has a density of 0.09 g / cm 3 .
  • the specific surface determined by nitrogen sorption according to DIN ISO 9277: 2003-05 is S BET - 267 m 2 / g.
  • graphite felt consisting of a predominantly amorphous carbon fibers (viscose-based) and partly from predominantly graphitic carbon fibers (PA-based).
  • the felts are activated in hot concentrated sulfuric acid over 30 minutes. Both activation and beyond as a C / C composite increase the power density as measured in a vanadium redox battery test cell.
  • the power density of the felts improved by the said treatment by 38% or 19% compared to the unactivated felt at a voltage efficiency of 90%.
  • the corresponding C / C composite achieves an increase in power density of 25% from 0.086 W / cm 2 to 0.0108 W / cm 2 with a 90% voltage efficiency.
  • Carrier material made of carbon

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Abstract

L'invention concerne un composite carbone/carbone (C/C), la surface interne du matériau support en carbone étant revêtue d'un matériau de carbone nanoporeux de surface spécifique élevée. Le composite C/C a de larges pores ouverts et présente, grâce à son revêtement, une surface spécifique élevée. Le procédé de production se caractérise par l'infiltration du matériau support en carbone ou d'un précurseur organique avec une solution polymère diluée. Selon l'invention, une couche polymère est d'abord disposée sur la surface interne du matériau support par un procédé sol-gel suivi d'une étape de séchage, puis le composite C/C est obtenu par pyrolyse. Le composite selon l'invention peut être utilisé pour des électrodes, notamment dans des batteries redox, en tant que support de catalyseur ou pour la filtration.
PCT/DE2011/001535 2010-08-04 2011-07-28 Composite c/c à larges pores ouverts présentant une grande surface interne, procédé de production correspondant et utilisation WO2012051973A1 (fr)

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DE102010033380.8 2010-08-04
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DE102011108435A DE102011108435A1 (de) 2011-07-26 2011-07-26 Groß- und offenporiges C/C-Komposit mit hoher innerer Oberfläche, sowie Verfahren zur Herstellung desselben und dessen Anwendung

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8785023B2 (en) 2008-07-07 2014-07-22 Enervault Corparation Cascade redox flow battery systems
US8906529B2 (en) 2008-07-07 2014-12-09 Enervault Corporation Redox flow battery system for distributed energy storage
US8916281B2 (en) 2011-03-29 2014-12-23 Enervault Corporation Rebalancing electrolytes in redox flow battery systems
US8980484B2 (en) 2011-03-29 2015-03-17 Enervault Corporation Monitoring electrolyte concentrations in redox flow battery systems
CN105272330A (zh) * 2015-10-22 2016-01-27 苏州泛珉复合材料科技有限公司 一种快速制备高热导率炭/炭复合材料的方法
WO2017083439A1 (fr) 2015-11-13 2017-05-18 Avalon Battery (Canada) Corporation Électrode améliorée pour batterie rédox
CN107379660A (zh) * 2016-05-16 2017-11-24 张跃 一种碳基体复合材料空心结构板及制造方法
CN108840698A (zh) * 2018-07-19 2018-11-20 航天特种材料及工艺技术研究所 一种多孔c/c复合材料及制备方法
CN109817994A (zh) * 2019-01-23 2019-05-28 成都新柯力化工科技有限公司 一种多层挤出制备燃料电池梯度气体扩散层碳膜的方法
CN111715209A (zh) * 2020-05-18 2020-09-29 浙江工业大学 一种三氧化钨/石墨毡复合材料的气相制备方法
CN112919922A (zh) * 2021-04-13 2021-06-08 西北工业大学 一种外置生物质催化剂的热解碳制备用化学气相渗透方法
CN113522262A (zh) * 2021-07-15 2021-10-22 陕西科技大学 一种可回收柔性二氧化钛/热解碳/碳纤维毡复合光催化材料及其制备方法和应用

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6025163A (ja) 1983-07-20 1985-02-07 Sumitomo Electric Ind Ltd レドツクスフロ−電池の電極
JPS61219708A (ja) 1985-03-22 1986-09-30 Hitachi Chem Co Ltd 熱分解炭素被覆黒鉛製品の製造法
JPH06143469A (ja) 1992-11-11 1994-05-24 Japan Atom Energy Res Inst 炭素複合材料断熱材及びその製造方法
US5626977A (en) 1995-02-21 1997-05-06 Regents Of The University Of California Composite carbon foam electrode
JPH1045473A (ja) 1996-08-01 1998-02-17 Toyo Tanso Kk 耐酸化性に優れた熱分解炭素被覆黒鉛材
JPH1045474A (ja) 1996-08-01 1998-02-17 Toyo Tanso Kk 熱分解炭素被覆黒鉛材の製造方法
US5744510A (en) * 1995-04-25 1998-04-28 Regents Of The University Of California Organic carbon aerogels from the sol-gel polymerization of phenolic-furfural mixtures
US5827355A (en) * 1997-01-31 1998-10-27 Lockheed Martin Energy Research Corporation Carbon fiber composite molecular sieve electrically regenerable air filter media
US5945084A (en) * 1997-07-05 1999-08-31 Ocellus, Inc. Low density open cell organic foams, low density open cell carbon foams, and methods for preparing same
CN101209837A (zh) 2006-12-27 2008-07-02 宁波杉杉新材料科技有限公司 石墨的改性方法及制得的改性石墨
EP1961701A1 (fr) 2005-12-14 2008-08-27 Mitsui Mining Co., Ltd. Particule de graphite, particule composite carbone-graphite et procedes pour les produire

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6025163A (ja) 1983-07-20 1985-02-07 Sumitomo Electric Ind Ltd レドツクスフロ−電池の電極
JPS61219708A (ja) 1985-03-22 1986-09-30 Hitachi Chem Co Ltd 熱分解炭素被覆黒鉛製品の製造法
JPH06143469A (ja) 1992-11-11 1994-05-24 Japan Atom Energy Res Inst 炭素複合材料断熱材及びその製造方法
US5626977A (en) 1995-02-21 1997-05-06 Regents Of The University Of California Composite carbon foam electrode
US5744510A (en) * 1995-04-25 1998-04-28 Regents Of The University Of California Organic carbon aerogels from the sol-gel polymerization of phenolic-furfural mixtures
JPH1045473A (ja) 1996-08-01 1998-02-17 Toyo Tanso Kk 耐酸化性に優れた熱分解炭素被覆黒鉛材
JPH1045474A (ja) 1996-08-01 1998-02-17 Toyo Tanso Kk 熱分解炭素被覆黒鉛材の製造方法
US5827355A (en) * 1997-01-31 1998-10-27 Lockheed Martin Energy Research Corporation Carbon fiber composite molecular sieve electrically regenerable air filter media
US5945084A (en) * 1997-07-05 1999-08-31 Ocellus, Inc. Low density open cell organic foams, low density open cell carbon foams, and methods for preparing same
EP1961701A1 (fr) 2005-12-14 2008-08-27 Mitsui Mining Co., Ltd. Particule de graphite, particule composite carbone-graphite et procedes pour les produire
CN101209837A (zh) 2006-12-27 2008-07-02 宁波杉杉新材料科技有限公司 石墨的改性方法及制得的改性石墨

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
MOSCOU L; PIEROTTI RA; ROUQUEROL J ET AL.: "Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity", PURE AND APPLIED CHEMISTRY, vol. 57, 1985, pages 603, XP001181366
SING KSW; EVERETT DH; HAUL RAW; MOSCOU L; PIEROTTI RA; ROUQUEROL J ET AL.: "Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity", PURE AND APPLIED CHEMISTRY, vol. 57, 1985, pages 603, XP001181366

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* Cited by examiner, † Cited by third party
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US8906529B2 (en) 2008-07-07 2014-12-09 Enervault Corporation Redox flow battery system for distributed energy storage
US8785023B2 (en) 2008-07-07 2014-07-22 Enervault Corparation Cascade redox flow battery systems
US8916281B2 (en) 2011-03-29 2014-12-23 Enervault Corporation Rebalancing electrolytes in redox flow battery systems
US8980484B2 (en) 2011-03-29 2015-03-17 Enervault Corporation Monitoring electrolyte concentrations in redox flow battery systems
CN105272330A (zh) * 2015-10-22 2016-01-27 苏州泛珉复合材料科技有限公司 一种快速制备高热导率炭/炭复合材料的方法
AU2016352909B2 (en) * 2015-11-13 2021-09-23 Invinity Energy Systems (Canada) Corporation Improved electrode for redox flow battery
WO2017083439A1 (fr) 2015-11-13 2017-05-18 Avalon Battery (Canada) Corporation Électrode améliorée pour batterie rédox
CN108352507A (zh) * 2015-11-13 2018-07-31 阿瓦隆电池（加拿大）公司 用于氧化还原液流电池的改进电极
EP3375030A4 (fr) * 2015-11-13 2019-05-08 Avalon Battery (Canada) Corporation Électrode améliorée pour batterie rédox
CN107379660A (zh) * 2016-05-16 2017-11-24 张跃 一种碳基体复合材料空心结构板及制造方法
CN108840698A (zh) * 2018-07-19 2018-11-20 航天特种材料及工艺技术研究所 一种多孔c/c复合材料及制备方法
CN109817994B (zh) * 2019-01-23 2021-02-26 成都新柯力化工科技有限公司 一种多层挤出制备燃料电池梯度气体扩散层碳膜的方法
CN109817994A (zh) * 2019-01-23 2019-05-28 成都新柯力化工科技有限公司 一种多层挤出制备燃料电池梯度气体扩散层碳膜的方法
CN111715209A (zh) * 2020-05-18 2020-09-29 浙江工业大学 一种三氧化钨/石墨毡复合材料的气相制备方法
CN111715209B (zh) * 2020-05-18 2023-04-07 浙江工业大学 一种三氧化钨/石墨毡复合材料的气相制备方法
CN112919922A (zh) * 2021-04-13 2021-06-08 西北工业大学 一种外置生物质催化剂的热解碳制备用化学气相渗透方法
CN113522262A (zh) * 2021-07-15 2021-10-22 陕西科技大学 一种可回收柔性二氧化钛/热解碳/碳纤维毡复合光催化材料及其制备方法和应用

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