WO2016195854A1 - Formation topochimique de nanocomposites de graphite-polymère ordonnés - Google Patents

Formation topochimique de nanocomposites de graphite-polymère ordonnés Download PDF

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Publication number
WO2016195854A1
WO2016195854A1 PCT/US2016/029590 US2016029590W WO2016195854A1 WO 2016195854 A1 WO2016195854 A1 WO 2016195854A1 US 2016029590 W US2016029590 W US 2016029590W WO 2016195854 A1 WO2016195854 A1 WO 2016195854A1
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WIPO (PCT)
Prior art keywords
polymer
graphite
molecular weight
average molecular
nanocomposites
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PCT/US2016/029590
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English (en)
Inventor
Michael L. LERNER
Hanyang ZHANG
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Oregon State University
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Publication of WO2016195854A1 publication Critical patent/WO2016195854A1/fr

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    • 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
    • C01B32/21—After-treatment
    • C01B32/22—Intercalation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Definitions

  • the present invention relates to the field of
  • nanocomposites and, more particularly, to a method for
  • Layered host - polymer nanocomposites have been prepared from many materials combinations - the hosts include the layered smectite clays, M02, MS2, Mo03 and MPS3 and the polymers include polylactide, poly (vinyl pyrrolidone) , linear polyethylenimine, poly(vinyl alcohol), and poly ( ethylene oxide) .
  • the nanocomposites may be ordered, retaining co-planarity of inorganic host layers with intercalate galleries opened for the polymers, or they may be disordered, with delaminated inorganic nanosheets dispersed into a polymer matrix. Because nanoscale materials combinations often display significant property changes from their native constituents, nanoscale materials are currently used as, or are candidates for, applications such as enhanced structural materials, gas barriers, and thermal or fire resistant components.
  • nanocomposites include the in situ polymerization of vinyl co- intercalates. However, the products were highly disordered, precluding strong evidence for the nanocomposite structure.
  • Nanocomposites containing graphite or graphene sheets are of interest for electrochemical applications where graphitic or other carbons are presently employed. Even though solvent co-intercalation into graphite will require large volume changes on charge/discharge, the chemistry has recently been shown to be highly reversible. Graphite-polymer nanocomposites, with higher molecular weight polymers retained in galleries, could undergo similar redox chemistry without the associated volume or phase changes. Graphite-polymer nanocomposites, with higher molecular weight polymers retained in galleries may also display other attractive properties, such as high conductivity for intercalate ions .
  • the present invention includes a composition of matter comprising a nanocomposite including individual graphene sheets and a polymer separating the graphene sheets.
  • the graphene sheets retain stacking coherence.
  • the present invention includes a method of separating the graphene sheets in graphite with polymer intercalate by providing graphite, providing a polymer, providing an electropositive metal, combining the graphite, polymer, and electropositive metal with an electrocatalyst in a sealed container, and maintaining the sealed container at an elevated temperature.
  • the present invention includes a method of separating the graphene sheets with polymer
  • ethylenediamine providing an electropositive metal, combining the graphite, polymer, electropositive metal, and ethylenediamine with an electrocatalyst in a sealed container, and maintaining the sealed container at an elevated temperature.
  • FIGs. la-lb illustrate ex situ powder X-ray
  • PXRD diffraction
  • FIGs. 2a-2b illustrate structures and data relating to the bilayer structure
  • FIGs. 3a-3b illustrate a thermal analysis plots of nanocomposite products
  • FIGs. 4a-4b illustrate additional data relating to nanocomposite products
  • FIG. 5 illustrates Raman spectra showing the G band shift in various GICs
  • FIGs. 6a-6c illustrate additional thermal analysis plots of nanocomposite products
  • FIG. 7 illustrates additional Raman spectra showing the low D/G band intensity, or no discernible D-band, in various
  • Layered host-polymer nanocomposites comprising an ordered nanoscale combination of layered host sheets with polymeric guest galleries have been prepared with many different inorganic hosts, but no such materials have previously been obtained from graphite.
  • Graphite oxide does not have the remarkable electronic properties of graphene, but is far more amenable to solution-phase processing, hence one strategy has been to first employ GO as the host during nanocomposite preparation, and to then reduce the GO layers back to graphene. For example, GO can be dispersed into polar solvents and thus undergo solution-phase processing.
  • the present disclosure provides methods for generating ordered graphite-polyether nanocomposites with polymer
  • Graphite-polyether nanocomposites may be used for electrochemical applications where graphite is
  • Graphite-polyether nanocomposites may be used for electronic applications where graphite is currently used. For example, as a conducting additive in composites.
  • Graphite-polyether nanocomposites may be used for applications where other layered sheet nanocomposites are used. For example, in packaging, or as a structural component. Graphite has the advantage of being electrically conductive and resistant to oxidation or reduction.
  • the present disclosure explores the co-intercalation of linear and branched amine co-intercalation and the formation of new GICs with expanded and unusual intercalate conformations and arrangements. Subsequent ion exchange rapidly and
  • the present disclosure teaches the incorporation of oligomeric or polymeric constituents via similar topochemical reactions using a direct or ion-exchange approach.
  • the present disclosure also teaches that direct reductive intercalation of oligo and polyethers can lead to similar products. As reported below, both methods generate ordered graphite-polymer nanocomposites.
  • Polymer candidates for GIC co-intercalation are reductively stable to ⁇ 0.7-1.0 V vs Li/Li+. Polymer candidates should also be strong Lewis bases so to provide favorable energetics for co-intercalation by strongly solvate alkali metal cations as opposed to ion desolvation (as occurs when charging Li-ion batteries anodes to form binary LiC6) .
  • Poly (ethylene glycol) (PEG), and poly (ethylene oxide) (PEO) are ether-group abundant candidates with Na+ binding constants linearly
  • PEGDME ethylene glycol dimethyl ethers
  • the present invention provides a method of formulating GICs using either (1) the direct reaction of graphite, polymer, Na (m) and electrocatalyst above the polymer melting point, or (2) graphite, polymer, and Na (m) in ethylenediamine (en) .
  • the latter combination without polymer rapidly generates
  • D-GIC-1,000 is an ordered graphite-polyether nanocomposites with polymer nanolayers contained between graphene sheets with an average polymer molecular weight of 1,000 formed from the direct
  • E-GIC-2,000 is an ordered graphite- polyether nanocomposites with polymer nanolayers contained between graphene sheets with an average polymer molecular weight of 2,000 formed from a solution of graphite, polymer, and Na (m) in en .
  • FIGs. la-lb illustrate ex situ PXRD patterns from products of direct, as shown in FIG. la, and exchange, as shown in FIG. lb, reactions.
  • FIG. la shows from bottom to top, reactions using
  • D-GIC-1000 shows a nanocomposite phase with Miller indices indicated.
  • E-GIC-2000 products with
  • FIG. 2a is a schematic diagram of M-PEG (DME) -GIC bilayer structure.
  • FIG. 2b is a ID-electron density map generated from Na-PEGDMElk- GIC diffraction data showing the gallery bilayers.
  • FIGs. 3a-3b show dTGA curves with calculated peaks.
  • FIG. 3a shows Na-PEGDMElk-GIC .
  • FIG. 3b shows Na-PEG6k- GIC.
  • the dTGA plots of reaction products of FIGs. 3a-3b show two overlapping peaks. The lower temperature peak is attributed to polymer in the GIC phase, and the higher temperature peak is attributed to excess unreacted polymer.
  • FIGs. 3a-3b show
  • Gaussian simulation of the subject dTGA peaks with a coefficient of determination R2 equal to 0.988.
  • the sodium mass % in the GIC products was obtained by ascribing the residual mass at 800°C under 02 flow as Na20.
  • the product after the subject processing was colorless or white, indicating that the graphitic carbons or polymer residues had been volatilized by oxidation.
  • the sodium mass contents thus derived were 2.82 and 3.16 mass % for samples Na-PEGDMElk-GIC and Na-PEG6k-GIC, respectively.
  • the graphite mass % in the products was obtained from the mass residual at 650°C under N2 flow, Ar for Li products. From the experimentally determined mass %, the mass of Na
  • the graphitic contents were calculated as 21.3 and 18.9 mass % for Na-PEGDMElk-GIC and Na- PEG6k-GIC, respectively.
  • the domain size indicates a well-ordered stacking structure with about 30 coherent units per domain.
  • Products D- GIC-2,000 and those with higher molecular weight polymer do not indicate nanocomposite formation with SP-1 graphite.
  • D-GIC-n and E-GIC-n possess a number of graphene sheet polymer pairs, or coherent units per domain, of greater than two, the products are said to possess stacking coherence.
  • FIG. 4a shows ex situ PXRD patterns of direct reaction products using Li, Na or K metal and PEGDME-lk.
  • FIG. 4b shows gallery expansion for these GICs vs. ionic radii of the alkali cations.
  • Li, Na, and K reactions using the direct method with PEGDME-lk all generate new single phase GICs with a linear response of gallery expansion vs. alkali metal ionic radius.
  • the slope of the plot, 3 ⁇ 41.3 confirms that more than a single cation-containing layer contributes to the gallery expansion.
  • Raman spectra are sensitive to graphene layer charge; donor-type GICs display an E2g (G band) peak shift to higher wavenumber due to occupancy of in-plane antibonding orbitals. For example, a 12-14 cm-1 shift has been reported for LiC6.
  • FIG. 5 illustrates Raman spectra showing the G band shift in obtained GICs.
  • Native graphite in the bottom spectrum, shows a peak at 1576 cm-1.
  • FIG. 5 shows a blue shift to 1596-1601 cm-1 for GICs with PEGDMEs.
  • FIG. 5 shows the G band peak for
  • FIGs. 6a-6c show thermal analysis, including TGA and derivative TGA, plots of nanocomposite products under N2 flow.
  • FIGs. 6a-6c include a trace for the starting polymer for comparison.
  • FIG. 6a shows PEGDME-lk.
  • FIG. 6b shows PEGDME-2 k .
  • FIG. 6c shows PEG-6k. The curves are compared with those for the PEGDME reagent used.
  • TGA and dTGA show two loss features in all GIC products, a loss at temperature close to that with the native polymer, plus a lower-temperature loss at approximately 250- 320°C ascribed to degradation of the polymer co-intercalate in the GIC.
  • Previous studies have similarly shown a catalytic effect for graphite compounds where intercalates and co- intercalates thermally degrade at lower temperature.
  • the low- temperature peak areas were evaluated to determine co- intercalate contents in the GIC phase.
  • Metal cation content was determined by thermolysis under oxygen flow, where at 800°C the carbon is volatilized as C02 leaving only Li20, Na20 or K20. From the above referenced data, nanocomposite compositions are derived, as shown in Table 1, above.
  • Table 2 shows the data for one sample: ⁇ (rad) ⁇ (rad) Ln (l/cos9) ⁇
  • ⁇ is full width at half maximum (FWHM) .
  • ⁇ is the peak position
  • Nanocomposite products exhibit very low Raman D/G band intensity ratios (ID/IG) .
  • FIG. 7 shows spectra for selected products and synthetic graphite.
  • No discernible D-band intensity was found for Na- PEGDMElk-GIC spectra which was obtained from SP-1 graphite.
  • the D-band peak at 3 ⁇ 41,350 cm-1 indicates sp3 carbon whereas the G- band peak at 3 ⁇ 41,580 cm-1 indicates sp2 carbon.
  • the subject disclosure confirms that the graphene sheets in the
  • FIG. 7 shows Raman spectra of synthetic graphite and nanocomposite samples. D/G band intensity ratios (ID/IG) are calculated for synthetic graphite and Na-PEG6k-GIC sample, while the Na-PEGDMElk-GIC shows no discernible D-band peak.
  • Example 1 direct reaction method for generating ordered graphite-polyether nanocomposites with polymer nanolayers contained between graphene sheets :
  • Example 2 ion-exchange reactions method for generating ordered graphite-polyether nanocomposites with polymer nanolayers contained between graphene sheets :
  • the subject disclosure supports the creation of ordered graphite-polyether nanocomposites with polymer nanolayers contained between graphene sheets with significantly higher average polymer molecular weight than 6,000 as discussed above. Average polymer molecular weights of 96,000 and up to 10 million are envisioned without departing from the scope of the present invention.
  • nanocomposites comprising graphite and oligo or polyethers.
  • the GIC products are first-stage and have intercalate bilayers and metal cations between reduced graphene sheets. If these GICs are applied as electrode materials, these large Mw ether
  • bilayers remain within galleries and thus reduce the gallery volume changes required during charge/discharge cycling.
  • temperatures and times are changed to generate nanocomposites over reaction or degradation
  • different electrocatalysts are utilized, including polyaromatic hydrocarbons and derivatives and fullerene and derivatives.
  • alkali metals or other reductants are utilized, including, but not limited to, Na (m) Li (m) , K (m) , other electropositive metals such as Ba, Ca, Mg and electrochemical reduction.
  • polymers including polyamines and functionalized vinyl polymers.
  • the polymer nanolayers may be organized as monolayers, bilayers, multilayers or disordered structures that retain planarity in the encasing graphene sheets .

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  • Chemical & Material Sciences (AREA)
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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
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  • Carbon And Carbon Compounds (AREA)
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Abstract

L'invention concerne des nanocomposites de polymère à hôte stratifié qui comprennent une combinaison ordonnée à l'échelle nanométrique de feuilles hôtes stratifiées avec des galeries polymères invitées, et qui ont été préparés avec de nombreux hôtes inorganiques différents, mais aucun de ces matériaux n'ont été précédemment obtenus du graphite. La présente invention concerne un procédé pour la génération de nanocomposites de graphite-polyéther ordonnés ayant des nanocouches de polymère contenues entre des feuilles de graphène grâce à une approche topochimique. La présente invention concerne en outre un procédé pour intercaler de manière réductive des complexes de cation de métal alcalin-polyéther dans du graphite par réaction directe du graphite, du métal alcalin ou du polyéther (poids moléculaire jusqu'à 6000) avec un électrocatalyseur ou à l'aide d'un solvant qui prend en charge la formation d'électrure. Une caractérisation structurelle des produits par diffraction des rayons X sur poudre, spectroscopie Raman et analyses thermiques fournissent la première preuve claire de nanocomposites de graphite-polymère ordonnés qui contiennent des feuilles de graphène réduit séparées par des nanocouches de polymère.
PCT/US2016/029590 2015-06-05 2016-04-27 Formation topochimique de nanocomposites de graphite-polymère ordonnés WO2016195854A1 (fr)

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US201562171910P 2015-06-05 2015-06-05
US62/171,910 2015-06-05

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110133132A1 (en) * 2009-12-07 2011-06-09 Aruna Zhamu Chemically functionalized submicron graphitic fibrils, methods for producing same and compositions containing same
WO2012116293A2 (fr) * 2011-02-25 2012-08-30 Henkel Corporation Nanocomposites de graphène-polymère auto-alignés
WO2014144139A1 (fr) * 2013-03-15 2014-09-18 Xolve, Inc. Nanocomposites de polymère-graphène

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110133132A1 (en) * 2009-12-07 2011-06-09 Aruna Zhamu Chemically functionalized submicron graphitic fibrils, methods for producing same and compositions containing same
WO2012116293A2 (fr) * 2011-02-25 2012-08-30 Henkel Corporation Nanocomposites de graphène-polymère auto-alignés
WO2014144139A1 (fr) * 2013-03-15 2014-09-18 Xolve, Inc. Nanocomposites de polymère-graphène

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