Carbon and coal based materials of high added value - research at CMPW PAN. Andrzej Dworak

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1 Carbon and coal based materials of high added value - research at CMPW PAN Andrzej Dworak

CMPW PAN (previously Institute of Coal Chemistry PAS) Structure and properties of coals and basic methods of their processing 1986-2002 - Brown coals - Hard coals 1997-2008 - Anthracites - Cokes -

2 CMPW PAN (previously Institute of Coal Chemistry PAS) Structure and properties of coals and basic methods of their processing Brown coals - Hard coals Anthracites - Cokes - Pyrolysed vascular plants Cross-links Molecular phase Acceptor-donor bonds Two-phase model of coal structure /A. Marzec, 1985/ Development of the basis of technology for obtaining carbon materials with specific properties 2006 currently non-energetic application of natural carbon materials (carbon fillers of polymer composites, catalyst carriers, sorbents) synthetic carbon materials from various precursors (natural and others) preparation and application

3 Natural carbon materials Turbostratic structure High rank bituminous coal Anthracite Graphite-like and graphitic structure Diamond Semi-graphite Graphite

4 Natural carbon materials Bituminous coal Raw anthracite HTT, graphite-like anthracite HTT 2000 o C C~83% C~93% C~95,5% 3 mm 5 mm 5 mm Increasing structural order Increase of XY dimensions of carbon planes Decrease of interlayer spacing Increase of true density Appearance of electrical conductivity S. Pusz et al. Fuel Proc. Tech., (2002) 77-78, M. Krzesinska et al. Energy Fuels (2005) 19, M. Krzesinska et al. Energy Fuels (2006) 20, M. Krzesinska et al. IJCG (2009) 77, S. Pusz et al. IJCG (2014), 131, pp

5 Functionalization of anthracite H H H H H Anthracite oxide H H H H H H H H H Thermal reductio n HTT anthracite CH 3 N H H Reduced anthracite oxide N CH 3 H Nanoplatelets XY: mm (AFM) Z: 6-30 nm H H Functionalized anthracite B. Kumanek, et al. Fullerenes, Nanotubes and Carbon Nanostructures, 2018, DI: / X H N H CH 3 Nanoplatelets XY: < 200 nm (AFM) Z: 2-3 nm

Polymer/carbon composites Polymer/carbon composites = polymer matrix + different kinds of carbon fillers Fillers: Carbon fibres Carbon black Graphite Carbon nanotubes Graphene Fulerenes ther carbon

6 Polymer/carbon composites Polymer/carbon composites = polymer matrix + different kinds of carbon fillers Fillers: Carbon fibres Carbon black Graphite Carbon nanotubes Graphene Fulerenes ther carbon materials Carbon nanofillers Matrices: Thermosetting polymers Termoplastic polymers Elastomers Potential benefits of application of carbon fillers to polimer composites: better stiffness better thermal resistance better chemical resistance better mechnical strength low density Hybrid polimer composite with two different carbon fillers

Mechanical strength [MPa] Matrix Epoxy composites with natural carbon

+ HTT anthracite (A2000) Microcomposites 20% mas.

after cycloaddition (AF2) 120 100 Raw fillers Functionalized fillers 0,5%

Journal of Thermal Analysis and Calorimetry, 92 (2008) 813 U.

7 Mechanical strength [MPa] Matrix Epoxy composites with natural carbon fillers Epoxy Matrix EP/TETA + bituminous coal (BC) + raw anthracite (RA) + HTT anthracite (A2000) Microcomposites 20% mas. + reduced anthracite oxide (AF1) Functionalized fillers + HTT anthracite after cycloaddition (AF2) Raw fillers Functionalized fillers 0,5% mm 0,5% mas. U. Szeluga et al. Journal of Thermal Analysis and Calorimetry, 92 (2008) 813 U. Szeluga et al. Polymer Bulletin 60 (2008) 555 S. Pusz et al. Polymer Composites, (2015), 36, pp mm EP BC WK RA Awyj A2000 AF1 AF2

8 Synthetic carbon materials

9 Synthetic carbon materials Graphene sheet variously arranged Graphene sheets and multi-layered nanoplatellets Synthetic graphite Carbon nanotubes Fulerenes Weakly ordered or amorphous structure, nongraphitized Heterogeneous structure, partly graphitized Carbon foam Glassy carbon Carbon black

] ] Glassy carbon Pyrolysis of phenol-formaldehyde

2 x 10-6 Ω mm Structural model Morphology T

10 Intensity [a.u.] Transmitance[a.u.] Intensity [a.u.] Glassy carbon Pyrolysis of phenol-formaldehyde resin to 1000 C, heating rate 0.5 C/h. GC: content C 92%, 7%; true density 1.45 g/cm 3 ; electrical resistance 4.2 x 10-6 Ω mm Structural model Morphology T tetrahedral domains sp 3 G graphitic domains sp 2 Functional groups XPS Structural order IR I D /I G = 1,4 Binding energy [ev] Raman shift [cm -1 ] Wavenumber [cm -1 ]

Epoxy composites with glassy carbon Binary cmposite with GC Hybrid composites with GC and MWCNT Epoxy

matrix Good mechanical strength Good electrical conductivity Big hardness and wear-resistance Thermal

77 GPa 72.92 MPa 4.82 x 10 14 C H A N G ES EP-MWCNT (0.25%) +5% -8% -11% 4.

11 Epoxy composites with glassy carbon Binary cmposite with GC Hybrid composites with GC and MWCNT Epoxy Matrix EP/TETA Properties of hybrid composites: Good dispersion of GC i MWCNT Perfect adhesion of GC to matrix Good mechanical strength Good electrical conductivity Big hardness and wear-resistance Thermal resistance Density comparable to pure epoxy matrix CMPSITE s y E f s f r (Ω cm) 3 mm EP MPa 2.77 GPa MPa 4.82 x C H A N G ES EP-MWCNT (0.25%) +5% -8% -11% 4.05 x 10 4 EP-GC (10%) +29% +16% +30% 3.02 x 10 7 EP-GC10-MWCNT +32% +19% +33% 1.68 x 10 3 U. Szeluga et al. Composites Science and Technology, (2016) 134, 72-80

for composites with anthracite filler randomly distributed system Percolation threshold of a segregated system much lower than for

12 Segregated vs random anthracite composites Collaboration with IMC National Academy of Sciences of Ukraine Matrix: UHMWPE; Filler: HTT Antracite Filler distribution segregated system randomly oriented in segregated system Percolation treshold of electrical conductivity for composites with anthracite filler randomly distributed system Percolation threshold of a segregated system much lower than for randomly distributed High local concentration of filler in a segregated system.v. Maruzhenko et al. Polymer Journal (Ukraine) (2018) 39,

Mass [mg] Carbon foams Collaboration with IC Bulgarian Academy of Sciences Carbon foams are porous carbon products containing regularly shaped, homogeneously dispersed cells,

Klett, 2005/ Preparation: Pyrolysis at 900 o C, 2 o C/min Precursors: - carbon materials (pitch, tar, coals) - thermosetting and thermoplastic polymers - by-products in

5 2 g/cm 3 Porosity: 82 95 % Young modulus: 30-100 MPa Compression strength: ~4 MPa Electric conductivity: 2 10-3 [S cm] Thermal stability of carbon foams Carbon foam Polymer

13 Mass [mg] Carbon foams Collaboration with IC Bulgarian Academy of Sciences Carbon foams are porous carbon products containing regularly shaped, homogeneously dispersed cells, which interact to form a three-dimensional array throughout a continuum material of carbon, predominantly in the nongraphitic state. /J. Klett, 2005/ Preparation: Pyrolysis at 900 o C, 2 o C/min Precursors: - carbon materials (pitch, tar, coals) - thermosetting and thermoplastic polymers - by-products in production of polymers and polymer waste Graphitization > 2000 o C Properties: Carbon content: 70 - > 95% Bulk density: g/cm 3 True (helium) density: g/cm 3 Porosity: % Young modulus: MPa Compression strength: ~4 MPa Electric conductivity: [S cm] Thermal stability of carbon foams Carbon foam Polymer precursor B. Tsyntsarski et al. Carbon, (2010) B. Nagel et al. Journal of Materials Sciences, (2014) 49 (1), 1-17 U. Szeluga et al. Journal of Thermal Analysis and Calorimetry, (2015) 122, Temperature [ o C]

Epopxy composites with carbon foam particles Epoxy

CF particles (<300mm) + epoxy CF particles distribution

Hardness 159% 181% Plots of heat release rate (a) and

epoxy composites with 5, 10 and 20 % of CF.

+5CF 0% 5% 10% 20% CF filler content U. Szeluga et al.

14 Epopxy composites with carbon foam particles Epoxy matrix EP/TETA CF particles adhesion Thermal properties CF particles (<300mm) + epoxy CF particles distribution (a) (b) Thermo-mechanical properties 48% 68% 107% Hardness 159% 181% Plots of heat release rate (a) and total heat release (b) of: (1) pure epoxy matrix, (2-4) epoxy composites with 5, 10 and 20 % of CF. 100 mm 218% Friction coefficient EP/TETA +20CF +10CF +5CF 0% 5% 10% 20% CF filler content U. Szeluga et al. Composites Part A, (2018) 105, % 5% 10% 20% CF filler content Track [m] 500 mm

15 Graphene studies at CMPW PAN 2D graphene structures Control of graphene layers order Graphene as a suport for 2D metalic layers 3D graphene structures Graphene in batteries

16 Graphene synthesis in 2D form Chemical vapor deposition (CVD) Methane, Ethanol, Acetylene Metallic substrates (Cu, Ni) xide substrates (Si x y, Mg, Al 2 3, Sr) LM and Raman SEM AFM TEM Collaboration with IFW Dresden

synthesis Large area High quality Homogenous Stacking controllable Low cost,

17 Graphene synthesis in 2D form Important parameters Precursors Substrates, catalysts Temperature Reaction time Scheme of an APCVD system for graphene synthesis Large area High quality Homogenous Stacking controllable Low cost, simple Scheme of the graphene growth mechanism over Cu substrate ACS Nano, 2012, 6 (10), pp

18 Stacking order control of graphene layers Twisted bilayer 3L 2L 1L 3L 2L 1L Seed 3s Stranski Krastanov(SK) growth 2L 1L 3L 2L1L 5s AB- stacked bilayer 40s Volmer Weber(VW) growth 60s Thermal CVD synthesis Stacking control through optimized CH 4 :H 2 Two growth modes Homogeneous over large areas Twisted Bi-layer: - for chemical reactivity enhancement AB stacked Bi-layer : - for transistor applications etc. Huy Q. Ta, et al. Nano Letters 2016, 16, SK VW

19 In situ freestanding Fe membrane formation A variety of e-beam reactions between graphene and Fe atoms can be explored in situ Zhao, Science, 343 (2014) 1228

20 Electron beam driven in situ chemistry over graphene Formation of mono-layer Zn in graphene pore under electron beam irradiation Huy Q. Ta et al., ACS Nano, 2015, 9 (11), All scale bars = 1nm

Electron beam driven in situ chemistry over graphene Single Cr atom catalytic synthesis of graphene Cr SYNTHESIS: Cr from decomposing chromium (III) acetylacetonate Electron

21 Electron beam driven in situ chemistry over graphene Single Cr atom catalytic synthesis of graphene Cr SYNTHESIS: Cr from decomposing chromium (III) acetylacetonate Electron irradiation Cr atoms Electron irradiation leads to Cr atom diffusion at graphene edges New graphene forms after Cr atom movement (always growth) Synthesis at room temperature

3D graphene synthesis over oxides via CVD Graphene

nanoparticles: - batteries, - functionalization, -

22 3D graphene synthesis over oxides via CVD Graphene coated oxide nanoparticles: a) alumina, b) titania, c) magnesia, d) carbon shells after magnesia removal Potential use of graphene coated oxide nanoparticles: - batteries, - functionalization, - bioapplications Bachmatiuk, et al., ACS Nano, 7 (2013)

Batteries studies using carbon materials

23 Batteries studies using carbon materials 3D graphene potential for electrochemical storage Graphene coated nanoparticles Equipment for coin cells preparation Cycling rates studies Racks for coin batteries cycling Collaboration with IFW Dresden

24 Carbon and coal based materials of high added value - research at CMPW PAN For closer data, see our papers in Science, ACS Nano, Nano Letters, Composites, Carbon, J. Material Science, other

25 Carbon and coal based materials of high added value - research at CMPW PAN Contributions from CMPW PAN: Prof. Barbara Trzebicka, head of the laboratory Composites Prof. Sławomira Pusz Dr. Urszula Szeluga Dr. Bogumiła Kumanek Graphene structures Prof. Mark Rummeli Prof. Alicja Bachmatiuk Ph.D. students

26 Carbon and coal based materials of high added value - research at CMPW PAN Cooperation: Quang-Zhou University, China Leibniz-Institute for Solid State Research and Material Studies Institute of Macromolecular Chemistry, National Academy of Science of Ukraina Institute of rganic Chemistry, Bulgarian Academy of Sciences

Graphene Fundamentals and Emergent Applications

Graphene Fundamentals and Emergent Applications Jamie H. Warner Department of Materials University of Oxford Oxford, UK Franziska Schaffel Department of Materials University of Oxford Oxford, UK Alicja