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Aerographite: Ultra Lightweight, Flexible Nanowall,


Carbon Microtube Material with Outstanding Mechanical
Performance
Matthias Mecklenburg, Arnim Schuchardt, Yogendra Kumar Mishra, Sren Kaps,
Rainer Adelung*, Andriy Lotnyk, Lorenz Kienle, and Karl Schulte
The utilization of carbon nanomaterials fascinating properties,
like carbon nanotubes (CNTs) tensile strength of 63 GPa[1] or
graphenes lowest electrical resistance[2] is typically limited by
the lack of advanced structural design. CNTs directly assembled as macroscopic rope deliver 3 GPa.[3] Only if individual
tubes get interconnected higher values can be achieved.[4] For
graphene the underlying substrate is often limiting the conductivity.[2] Although 3D interconnected graphene networks were
recently synthesized, they are only hypothetically free standing
and lightweight (2 mg cm3), without a second phase they are
not self-supporting and only stable as composite materials.[5]
Furthermore they tend to collapse even as single tubes.[6] Thus from the engineering point of view - real life applications desire
synthesis methods which enable tailoring of materials interconnections and morphological design, like recently presented by
the synthesis of nickel microlattices[7] (0.9 mg cm3). Here we
present a novel cellular material called Aerographite (density
< 200 g cm3), more than 4 times lighter than the Ni microlattices, which were up to now the most lightweight materials.
Despite its low density it can be fabricated in various macroscopic shapes in the order of several cubic centimeters.
Recently published results about graphene network structures indicate the importance of highly porous, electrical conductive, and mechanical stable foam like structures[5,8] for the
applications as electrode material for Li ion car batteries or
super capacitors. For those applications low specific weight, a
high penetrability, and accessibility of surfaces and especially
M. Mecklenburg, Prof. K. Schulte
Istitute of Polymers and Composites
Hamburg University of Technology
Denickestr. 15, D- 21073 Hamburg, Germany
A. Schuchardt, Dr. Y. K. Mishra, S. Kaps,
Prof. R. Adelung
Institute for Materials Science
Functional Nanomaterials
University of Kiel
Kaiserstr. 2, D-24143 Kiel, Germany
E-mail: ra@tf.uni-kiel.de
Dr. A. Lotnyk,[+] Prof. L. Kienle
Institute for Materials Science
Synthesis and Real Structure
University of Kiel
Kaiserstr. 2, D-24143 Kiel, Germany
[+] Present Address: Leibniz Institute of Surface Modification (IOM)
Permoserstr. 15, D-04318, Leipzig, Germany

DOI: 10.1002/adma.201200491
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high mechanical robustness are necessary. Cyclic loading


and unloading with Li ions easily leads to volume changes of
200400%.[9] Corresponding stresses are a major point of limited lifetime performance,[911] thus introduction of direct interconnections are advantageous.
Aerographite is designed to be most lightweight but extremely
robust to bear strong deformations. These challenging material properties are achived by Aerographites hirachical design
which is realized by a novel single-step cvd sythesis based on
freely adjustable ZnO networks. Figure 1 gives a small overview
over the variety of the Aerographite family. The photograph of
Figure 1a shows that the material is completely black and optically opaque despite its extreme low density. The open porous
structure of Aerographite is orders of magnitudes more light
adsorbing than, e.g., carbon nanotube sponges as confirmed in
Raman spectroscopy experiments. Figure 1bd show in different
magnifications the distinct levels of the material. A closer look
reveals that this variant of Aerographite consists of a seamless
interconnected network of closed shell micro tubes, a structure
that provides ultra-low densities of 2 mg cm3 already lower
than the lightest reported aerogels.[5,8,12,13] The walls possess
a similar nanoscopic thickness (15 nm) like thin multiwall
carbon nanotubes (MWCNTs) but have a microscale tube diameter. Other than MWCNTs, the relatively large graphite planes
exhibit orders of magnitude less curvature promoting the formation of manifold tube junctions over the sintering bridges
of vanished template (Supporting Information (SI), Figure S2,
S3) that are exceptions for CNT materials.[14] Furthermore,
depending on the growth conditions, the graphite surface can
be shaped in a wrinkled manner (surface in Figure 1d and SI,
Figure S4) to give a higher mechanical stability. The stabilizing
effect of wrinkled, e.g., non-hexagonal ring configurations, of
pure sp2-carbon structures is also known from glass-like carbons[15,16] (often called vitreous carbons), which have superior
mechanical properties and chemical resistance[17] but are still
electrically conductive as it would be required for an utilization as an electrode material. A super lightweight variant of
Aerographite is shown in Figure 1eh (SI, Figure S16). Here
the walls of the tubes introduce another hierarchy level; they are
formed from a hollow framework of ribbons which consists of
a transition state between amorphous carbon (with a very high
amount of sp2-hybridized bonds) and completely sp2-hybridized
vitreous carbon, as confirmed by the electrical conductance and
the electron energy loss spectroscopy (EELS) spectra.[18,19] This
hollow framework structure (network with sub network) material possesses the super low density of 180 g cm3 which is

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S16 ribbons, S13-S15 filled) are highly controllable by the CVD parameters respectively
by the design of the ZnO templates (SI,
Figure S6). Microscopy of an evolutionary
state (SI, Figures S7-10) and the results
of TEM (SI, Figures S4, S12), EFTEM (SI,
Figures S10,S12), XRD, Raman spectroscopy, and TGA measurements at different
Aerographite types are discussed in the supporting information where one can also find
suggested growth model (SI, Figure S1).
For mechanical testing distinct examples
of the Aerographite family were created and
loaded under cyclic compression and tensile
stress. Tests with different geometries showed
that cylindrical test specimens provided the
lowest experimental error (see Experimental
Section). SI, Figure S19 shows a viewgraph of
the Youngs modulus in compression versus
the density. This graph indicates the change
in the Youngs modulus in compression for
different densities and the corresponding
structure types. It must be pointed out that
Aerographite can carry significant tensile
loads as its network structure exhibits tube
junctions which originate from the ZnO temFigure 1. Overview of different Aerographite morphologies by controlled derivations of synplate. This robustness in tensile loading is
thesis. a) Photograph of macroscopic Aerographite. bd) 3D interconnected structure of
closed-shell graphitic Aerographite in different magnifications and TEM inset of wall. eh) Hier- an exception for foam like carbon structures
archical hollow framework configuration of Aerographite in different magnifications. il) Other which are usually kept together by entanglevariants of Aerographite. i) Aerographite network in low aspect bubble-like configuration. j-k) ments and Van der Waals forces. In fact this
Aerographite with nano porous graphite filling. l) Hollow corrugated pipe design of Aerographite structural deficiency is the reason why tensile
surface by detailed adoption of template shape.
measurements of CNT-assembled graphitic
structures and also silica aerogels are just
rarely reported and challenging to measure.[22] Just owing to the
one order of magnitude lighter than all known aerogels and
impressive low density of <200 g cm3 the hierarchical hollow
other lightweight materials. Many more variants can be syntheframework structure (Figure 1eg), fortified by sp3-bonds,
sized, e.g. the low aspect ratio variant of interconnected spheres
exhibits outstanding mechanical robustness, specific stiffness,
which is depicted in Figure 1i (SI, Figure S5). Furthermore,
and tensile strength and therefore superior merit indices.[23] The
the hollow tubes can be filled with several kinds of carbon speAerographite reacts with a viscoelastic deformation behavior on
cies, see Figure 1j-k (SI, Figures S13-S15). Due to the internal
unidirectional tensile and compression stresses with a reversgraphitic structure of these variants a much higher specific surible plastic deformation part, see Figure 3a (SI, Figure S21).
face-area is given but with the disadvantage that flexibility and
As a demonstration of this mechanical robust behavior, it is
damage tolerance are reduced to a level of conventional silica[13]
even possible to regain the full shape of an initial 3 mm high
or carbon aerogels.[8,12]
Aerographite bulk body after compression down to a few
The achieved structures of Aerographite adopt the network
100 micrometers, by subsequent expansion back to its original
and surface structure of the individual tailorable ZnO[20] temshape, indicating an extreme low Poisson ratio (SI, Video S1),
plate. Thus it is possible to tune the morphology of Aerographite
leading to marginal differences between true and engineering
in a broad manner with respect to its aspect ratios, diameters,
stress. These features allow the application of remarkable
and surface structures (SI, Figure S5). To give a glimpse of the
mechanical tensile loads without losing structural integrity, e.g.,
structural variety of the template material, Figure 2ad show
disentangling of CNTs or small flakes of graphite. The material
some of the templates, including the corrugated pipe structures
shows a sponge like behavior under compression, for 95% strain
(SI, Figures S7b, S11b).
the modulus increased to 160 kPa in a 8.5 mg cm3 sample,
The developed CVD process allows a single-step synthesis
see SI, Figure S20. A tensile and compression cycling introof various carbon species with a simultaneous and complete
duces a pronounced self-stiffening (inset Figure 3c). A mecharemoval of the whole template material. This is introduced
nism behind this could be a reorganization and alignment of
by a hydrogen gas flow, which reduces ZnO (SI, Figure S6)
the hollow amorphous carbon ribbon structure parallel to the
to metallic Zn, which is precipitated to the exhaust system
load direction. The hollow framework variant with a density of
(SI, Figures S7-S10). It is important to point out that the
= 0.180 mg cm3 exhibits a smooth fracture behavior at an
achieved carbon structures and degree of crystalline order
ultimate tensile strength (UTS) of 1 kPa what is superior to all
as well as the morphology (SI, Figures S2-S4 graphitic,

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the amount of the stored electrolyte, the ion


mobility and the volume of the individual
electrode, an electrolyte loaded Aerographite
electrode can be compressed till it has the
optimal balance between these parameters.
From CNT based electrodes[24] it is known
that increasing electrode length decreases
the capacity. CNT electrodes with 600 m
length show a power density of 2.3 Wh kg1
while 4000 m long Aerographite electrodes
still show 1.25 Wh kg1 which is a promising
starting point for the optimization. Besides
the structural properties, the application as
electrode material requires a good electrical
conductivity. Referring to this, Aerographite
reaches a conductivity of 0.2 S m1 at a density of 180 g cm3.
By increasing the density under compression in air, e.g., to reach optimal free volume
to surface ratios, the conductivity increases
to 0.8 S m1 (0.2 mg cm3), see inset of
Figure 3a. The increase for this light weight
material is mainly linear over a wide deformation range of at least 30% which gives
chance for easy electro-mechanical sensing
applications. However samples of the heavy
(50 mg cm3) closed shell modifications of
Figure 2. Growth process and analysis of Aerographite. a) Photograph of utilized ZnO tem- Aerographite family exhibit a much higher
plates with a volume of 1.77 cm3. b-d) SEM micrographs showing two examples for the strucconductivity of 37 S m1 at a mechanical comtural variety of ZnO crystal templates, here with a corrugated surface. e) Photograph of an
intermediate state of a sample on its way from ZnO to Aerographite. f-h) SEM revealing tem- pression of 24%. The cm-scaled Aerographite
plate removal and formation of carbon layers (Figures S7-S10). i-k) TEM micrograph, SAED samples are super hydrophobic (Figure 3b
pattern, and EELS spectrum revealing graphitic state and sp2-hybridization of closed shell inset) therefore their properties and high
Aerographite. l-n) TEM micrograph, SAED pattern, and EELS spectrum of hollow framework porosity enable an excellent wetting with
Aerographite revealing amorphous carbon with a high content of sp2-hybridization.[19]
epoxy systems for nanocomposite manufacturing (SI, Figure S22).
reported graphene or CNT based macroscopic bulk samples. In
We have here introduced the novel synthesis of an ultrarelation to its density Aerographite bears an at least 35 times
lightweight, electrically conductive, mechanical robust, and
higher force as compared to the best silica based aerogel, which
flexible graphite based material. In contrast to already estabdelivers an UTS of 16 kPa at density of 100 mg cm3.[13] Furtherlished synthesis for other carbon nanostructures like CNTs or
more, a Youngs modulus of 15 kPa (slope in Figure 3c) can be
graphene, the here used CVD process employs ZnO as temobtained. This modulus at such a low density brings a hypothetplate for the synthesis of bulk samples on the cm3-scale. It
ical Aerographite free bending bar (min. deflection if cross sechas been proved that this inorganic semiconductor is a suittion is variable by E/2 or if the height is variable by E/3) to the
able substrate/template material for sp2 hybridized carbons,
5

2
first place in every density selection map (0.463 106 m kg s
e.g., CNTs and graphene.[25,26] The common structural motive
resp. 2.572 106 m8 kg2 s2), see Figure 3b (SI, Figures S17,
of the Aerographite family is the completely interconnected
S18). While a straight forward free standing panel application
network of microstructures with a nanoscopic wall thickof Aerographite is more of academic interest, these numbers
ness. Variants come as filled and unfilled, corrugated walls,
are still very important in technological applications where
or as a super lightweight example of a hollow framework of
low densities lead to low acceleration induced forces. These
struts from amorphous carbon. The atomic structure can be
could be microelectromechanical systems (MEMS), electrical
tuned from graphitic to glass-like pyrolytic carbon, with the
shielding or conductive electrode applications that should withadvantage of remarkable mechanical properties. This most
stand high accelerations, e.g., caused by vibrations or impacts.
lightweight material reaches the highest merit indices for
First experiments with Aerographite electrodes in an electric
specific moduli observed until now. Further optimization of
double-layer capacitor (EDLC, also known as supercapacitor)
parameters like, e.g., pore size and volume density of sintering
confirmed the mechanical robustness in a real life application.
bridges keeps the opportunity for future improvements of the
An Aerographite electrode loaded with electrolyte even endures
mechanical performance of Aerographite. Further properties
the recrystallization of the salt, which occurs when the solvent
like conductivity, flexibility and compressibility without losing
is evaporated during drying. This procedure induced cracking
structural integrity, high optical adsorption and X-ray opacity, a
of the activated carbon reference electrode. In order to optimize
high temperature stability and chemical resistance, the bearing

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of tensile and compressive loads, and the super hydrophobicity making it a remarkable multifunctional material. Next
to others, potential applications might be electrode materials
for the increasing demand of batteries and high surface area
supercapacitor materials. Proper designed carbon materials
from the family of Aerographites could avoid typical problems
of electrode materials like low mechanical cycling stability,
degenerating electrical contacts, or non-optimized electrolyte
to surface ratio which might be tuned in by simple compression due to the negligible Poissons ratio of these sponge-like
structures.

Experimental Section
Templates preparation: The ZnO templates were produced in a recently
discovered method.[27] Zn powder (grain size 15 m) was mixed with
polyvinyl butyral powder (Kuraray Europe GmbH) in a mass ratio of
1 to 2. This mixture was heated in a muffle furnace with a heating
rate of 60 C min1 to 900 C. After 30 min a loose powder of
typically ZnO tetrapods was obtained. Further synthesis methods and
established recipes for the fabrication of ZnO structures can be found
in.[20] Compressed powder (densities ranging from 0.15 g cm3 to
0.8 g m3) was reheated for 3 to 4 h at 1200 C in ceramic rings (h =
10 mm, d = 15 mm) to form junctions.
CVD-Synthesis: Basic Aerographite configuration (hollow, with closed
graphitic shells) can be gained by placing ZnO templates in the maximum
temperature zone of a two zone split tube furnace (quartz tube; l = 1300

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Figure 3. Mechanical and electrical properties of Aerographite. a) Tensile and compression


test of the 180 g cm3 Aerographite variant (Figure 1e, SI, Figure S16), under tensile load the
maximum force and displacement was 31.1 mN and 0.4 mm. The inset shows the electrical
conductivity against compression. b) Material selection map, plotting the Youngs modulus/
density3 against the specific volume, parameters obtained from.[7,8,21] The inset shows a water
droplet on the surface of an Aerographite sample proving the superhydrophobicity of the
Aerographite. c) Tensile test of Aerographite (180 g cm3) until fracture. Inset: self-stiffening
effect at cycling tensile loading. d) Classical Ashby material selection map, plotting the Youngs
modulus against the density. The guidelines indicate the structural efficiency of the material.

mm; d = 110 mm): At a constant temperature profile


of 200 C in injection zone and 760 C in main
zone under Ar gas flow (0.02 L min1, atmosphere
pressure), injection of toluene (99% Alfa Aesar)
at 5.5 mL h1 is started. At start of the injection
by a syringe pump, gas flow rates are changed
to 0.2 L min1 Ar/0.02 L min1 H2 for 120 min. A
subsequent 45 min pure H2 (0.6 L min1) gas flow
without injection is followed by a 120 min mixed
atmosphere Ar/ H2 (0.2 L min1/ 0.02 L min1) with
injection of toluene. A final pure hydrogen treatment
with 0.6 L min1 was conducted for 20 min
until cooling down under pure Ar purge flow of
0.6 L min1. Synthesis depends on template surface
area and time depended variations of gas flow rates
or temperatures. For example, the parameters for
the ultra lightweight, hollow-framework variant are
given by a decreased 2 mL h1 toluene injection for
4 h with a 0.06 L min1 H2 and 0.2 mL min1 Ar
gas flow at 760 C and a 1 h post-treatment with
no injection and pure H2 flow of 0.09 L min1 at
800 C.
Capacitor setup: As electrolyte a 1 molar solution
of
tetraethylammonium-tetrafluoroborate
in
acetonitrile was used. The current collector was
made from aluminum and no separator membrane
was used. The capacitor setup was charged with
1.6 volts.

Supporting Information
Supporting Information is available from the Wiley
Online Library or from the author.

Acknowledgements
We gratefully acknowledge partial project funding DFG SFB 855-A5 and
Z1, R. A. DFG Heisenberg professorship, 183/5-2, Y. K. M. a Humboldt
grant and M. M. the Landesexzellenzinitiative Hamburg (LEXI) and the
Joachim Herz Stiftung.
Received: February 3, 2012
Revised: March 26, 2012
Published online: June 12, 2012

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