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Yi Ding · Zhonghua Zhang
Nanoporous
Metals for
Advanced
Energy
Technologies
Nanoporous Metals for Advanced Energy
Technologies
Yi Ding Zhonghua Zhang
•
Nanoporous Metals
for Advanced Energy
Technologies
123
Yi Ding Zhonghua Zhang
Institute for New Energy Materials and School of Materials Science and Engineering
Low-Carbon Technologies Shandong University
Tianjin University of Technology Jinan
Tianjin China
China
Advanced energy technologies have been and will continue to be one of the most
explored fields across the multidisciplines of: materials science, chemistry, applied
physics and engineering. The rapid progress of portable electronic devices and
electric vehicles in recent years has aroused tremendous research interests and
technological challenges for the development of higher energy and/or power den-
sity electrochemical power management devices such as fuel cells, supercapacitors,
and Li batteries.
Nanostructured carbon materials have traditionally been deemed as the most
suitable electrode materials in almost all above-mentioned energy technologies due
to their low price, high specific surface area, and chemical stability. However, recent
researches have revealed that dealloyed nanoporous metals can also function as an
alternative type of electrode materials that exhibit some very unique structural
properties not commonly expected from carbon-based electrodes. Amongst various
unique features of dealloyed nanoporous metals, the most appreciable ones are
(i) bicontinuous open framework structures tunable across the wide dimension scale;
(ii) clean surfaces with well-defined and tailorable interfacial structures; (iii) superior
electric conductivity; (iv) simple processing scalable for mass production.
This book aims to provide a comprehensive discussion of research in this new
field to date. Chapters 1 and 2 provide a general introduction of nanoporous metals,
in particular on how a historically unwanted process of alloy corrosion can be
tailored to generate functional nanoporous metals and composites with tunable
structural properties. Chapters 3–5 discuss the respective research advances of
dealloyed nanoporous metals for applications in fuel cells, supercapacitors, and Li
batteries. And finally Chap. 6 summarizes the current research activities and also
proposes future prospects of employing this new class of electrode materials for
other energy-related technologies.
Tianjin Yi Ding
Jinan Zhonghua Zhang
2016
v
Acknowledgments
We would like to thank our group members who have been devoting their energy
and interests into this fascinating research field during the past decade. Many
of them are also involved during the preparation and editing of this book, and our
particular acknowledgment should extend to Dr. Xizheng Liu, Dr. Cuihua An, Dr.
Huiming Yin, and Mr. Jian Li.
We also would like to acknowledge collaborations with many of our colleagues
over the years. They have been generously sharing with us their expertise, ideas,
research data and facilities. They are Mingwei Chen (Tohoku University), Jianguo
Liu (Nanjing University), Wenbin Cai (Fudan University), Jingdong Zhang and
Jens Ulstrup (Technical University of Denmark), Yan Wang (University of Jinan),
Xiaohong Xu, Houyi Ma and Pengchao Si (Shandong University).
We received substantial financial support in the past decade from various funding
agencies, without which our research and thus the contents of this book would not
have been possible. In particular, we wish to acknowledge the Ministry of Science
and the Technology of the People’s Republic of China (MOST), National Natural
Science Foundation of China (NSFC), Ministry of Education of the People’s
Republic of China (MOE), Tianjin University of Technology (TUT), Shandong
University (SDU), and the local government programs from Shandong Province and
Tianjin City. YD also thanks the Otto Mønsted Fond for providing a 3-month
visiting professorship at the Technical University of Denmark in 2014, where part of
this book was drafted.
Publishers and authors are thanked for their permission to reproduce or adapt the
illustrations, tables, and figure legends. We would also like to thank the Springer
publishing team, particularly to Editors Marta Moldvai, Merry Stuber, Lesley
Poliner, Brian Halm, and Zoe Kennedy, for their invaluable suggestions and sup-
port to the completion of this book.
Finally, we would like to thank our family members for their love and patience
whilst the book was composed.
vii
Contents
ix
x Contents
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223
About the Authors
xiii
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xiv About the Authors
Nanoporous metals (NPMs) are such a kind of metallic materials with intercon-
nected backbones (ligaments) and pores on the nanoscale, Fig. 1.1 [1]. Tappan et al.
[2] call them as “foam” and have defined a nanoporous metal foam as a
three-dimensional structure comprised of interconnected metallic particles or
Fig. 1.1 (a) Scanning electron microscopy, (b) transmission electron microscopy, and
(d) high-resolution transmission electron microscopy micrographs of nanoporous gold (NPG).
(c) Representative rotational-averaged fast Fourier transform (FFT) power spectrum and intensity
profile of NPG with a strong signal-to-noise ratio. The dotted arrow in the FFT spectrum
represents the integration direction of the intensity profile. The detectable peak in the profile
proves that the microstructure of NPG is quasiperiodic. (e) Three-dimensional structure of NPG
imaged by electron tomography. A part of the 3D image is shown as the skeletal network of gold
ligaments. The various colors of the skeletal network represent the deviation angles of the
skeletonized ligaments from the z-axis (the surface normal of the film) as indicated by the color bar
from 0° (purple) to 90° (red). (Reproduced from Ref [1]. Copyright 2004, Materials Research
Society)
1.1 What Are Nanoporous Metals 3
Fig. 1.2 The length scales of nanoporous metals and metal foams. Adapted from Ref. [7]
(a) (b)
Fig. 1.3 Photographs of traditional metal foams (left copper foam; right nickel foam)
Fig. 1.4 Top and cross-sectional SEM images of electroless-plated Cu and Ni nanofoams: (a,
d) PnP polymer template, (b, e) submicron Cu foams, and (c, f) submicron Ni foams. (Reproduced
from Ref. [8]. Copyright 2014, Elsevier)
1.1 What Are Nanoporous Metals 5
(a) (c)
(b) (d)
Fig. 1.5 Scanning electron microscope images showing: (a) a silica inverse opal template; (b) a
porous gold film obtained by electrodeposition without the use of an opal template; (c, d) low- and
high-magnification SEM images, respectively, of a porous gold opal template. (Reproduced from
Ref. [9]. Copyright 2012, American Chemical Society)
characteristics of the former two kinds of NPMs (Fig. 1.5, [9]). Normally, NPMs
with a bicontinuous interpenetrating ligament–channel structure can be fabricated
by the dealloying strategy, and template methods are frequently used to prepare
NPMs with more regular pore distribution. And the combination of dealloying with
template methods could produce NPMs with two kinds of nanopore features
(Fig. 1.5).
Many methods have been developed to fabricate nanoporous metallic materials,
such as dealloying, [4, 10] templating, [8] anodization, [11] laser etching, [12]
combustion synthesis, [2] sol–gel, [2] nanosmelting of hybrid polymer–metal oxide
aerogels, [2, 13] chemical reduction based upon a mathematical fractal model, [14]
thermal decomposition, [15] and so on. Tappan et al. [2] have believed that com-
bustion synthesis of MBTA complexes is a flexible, general approach for the for-
mation of a wide range of nanoporous metallic foams of a large number of metals
(including Fe, Co, Ni, Cu, Zn, Pd, Ag, Pt, Au), and has potentials for scalability.
Most recently, Avisar-Levy et al. [14] have shown that chemical reduction of metal
6 1 Introduction to Nanoporous Metals
(a) (b)
Fig. 1.6 Statistics on (a) published papers and (b) citations per year since 2000 (until Dec. 07,
2015), based upon Web of Science (subject words: “dealloying” and “*porous”)
Fig. 1.8 IUPAC periodic table of the elements (Copyright © 2012 IUPAC, the International
Union of Pure and Applied Chemistry). The metals which could be processed into a nanoporous
form have been highlighted by red or blue dashed rectangles
8 1 Introduction to Nanoporous Metals
Besides pure elements, numerous nanoporous binary, ternary, and even multi-
component alloys have also been reported, such as Au-based alloys, [32, 33]
Pt-based alloys, [34–41] Pd-based alloys, [42–46] Ru-based alloys, [14] and so
forth. For example, ultrafine nanoporous Au-based alloys (AuPt, AuPd, AuPdPt)
could be fabricated by dealloying Al2Au-type precursors doped with a proper
amount of Pt, Pd or Pt/Pd in HCl or NaOH solutions [32]. Further, the same group
has found that the addition of Ni and/or Co has no influence on phase constitution
of rapidly solidified Al–Au–M (M = Ni, Co, or Ni/Co) alloys and a single-phase
Al2(Au,M) intermetallic compound can be identified in these ternary and quar-
ternary precursor alloys. The Al–Au-based precursors can be fully dealloyed in an
alkaline solution under free corrosion conditions, and the dealloying results in the
formation of novel ultrafine nanoporous Au-based alloys (AuNi, AuCo and
AuNiCo) with ligaments/channels of *5 nm and extraordinarily high structural
stability against thermal annealing [33].
NPMs could be prepared into bulk forms with the shape size of up to centimeters.
Figure 1.9 shows the macrograph of nanoporous Cu ribbon, rod, and sheet which
were fabricated by a two-step dealloying of an Al-40 at.% Cu alloy [47].
Millimeter-sized nanoporous AuPt alloys were fabricated by potential-controlled
electrochemical dealloying of (Au1-xPtx)25Ag75 precursors in 1 M HClO4 solution
[48]. These bulk samples are good candidates for investigation of mechanical
properties of NPMs, as well as applications in electrochemical or chemical actuators.
Nanosized NPMs with diverse morphologies were also reported in the literature,
including zero-dimensional (0D), 1D, and 2D nanostructures. The Ag50Au50 (wt%,
white gold) alloy leaves are commercially available (Fig. 1.10a). After dealloying in
nitric acid, NPG films with thickness of *100 nm were obtained and the color
became dark red, Fig. 1.10b [49]. NPG films with thickness of several microns can
(a)
(b)
Fig. 1.9 a Macrograph showing the nanoporous Cu ribbon, rod, and sheet by the two-step
dealloying of Al-40 at.% Cu (from left to right). b SEM image showing the ligament–channel
structure of nanoporous Cu ribbon. (Reproduced from Ref. [47]. Copyright 2009, American
Chemical Society)
1.2 Microstructural Characteristics of Nanoporous Metals 9
(a) (b)
Fig. 1.10 Optical images of white gold leaf (a) before and (b) after dealloying in nitric acid for
30 min. Adapted from Ref. [49]
(a)
(b) (c)
Fig. 1.11 (a) Schematic illustration of the synthesis process of Au–Ag alloy NPNTs. (b, c) TEM
images of Au–Ag alloy NPNTs [52]
(a) (b)
(c) (d)
Fig. 1.12 Nanoalloys observed by TEM and HRTEM. a TEM image of Pt-Ni nanoparticles.
b HRTEM image of Pt-Ni nanoparticles. c TEM image of nanoporous Pt-Ni alloys. d HRTEM
image of nanoporous Pt-Ni alloys. (Reproduced from Ref. [53]. Copyright 2011, Nature
Publishing Group)
The ligaments/channels sizes are 10–20 nm in these NPG ribbons, but the grain size
may range from several microns to tens of microns. For other NPMs (like NP–Pd,
NP–Pt, etc.), however, the grain sizes are comparable or even smaller than the
length scale of ligaments [16]. For metallic glass precursors, there actually exist no
“grains” in their microstructures (composed of short-range and medium-range order
clusters). The ligaments were found to be comprised of nanocrystals with a grain
size of about 5 nm in nanoporous Pd dealloyed from Pd30Ni50P20 metallic glass
[56].
Various crystal defects, such as dislocations, twins, and stacking faults, have
been observed in dealloyed NPG samples. Figure 1.14 shows twins, dislocations,
and stacking faults in NPG obtained by chemical dealloying of rapidly solidified
Al80Au20 alloy in the 20 wt% NaOH aqueous solution [57]. Generally, the
12 1 Introduction to Nanoporous Metals
(a) (b)
(c) (d)
Au [110]
Au [112]
Fig. 1.13 a Section-view SEM image of the NPG ribbons by dealloying of the rapidly solidified
Al66.6Au33.4 alloy in the 20 wt% NaOH solution. Scale bar, 10 μm. b Plan-view SEM image of the
surface of the NPG ribbons, Scale bar, 1 μm. c TEM image showing the nanoporous structure of
the NPG ribbons. The selected area is highlighted by a white circle. (Insert) SAED pattern of the f.
c.c. Au [112] zone axis from the selected area in (c). Scale bar, 100 nm. d HRTEM image of the
NPG ribbons. (Insert) Corresponding FFT pattern of the f.c.c. Au [110] zone axis. Scale bar, 5 nm.
(Reproduced from Ref. [16]. Copyright 2009, American Chemical Society)
chemically dealloyed samples (free corrosion) have a low density of crystal defects
in comparison with the NPG samples prepared by electrochemical dealloying. This
is probably because the fast formation of nanoporosity with the assistance of
applied potentials produces large residual stresses and resultant plastic deformation
during dealloying [1].
In some cases, we need nanoporous metallic materials with homogeneous
nanopore/ligament distributions, as shown in Fig. 1.1. At the same time, we can
also tune the structures/compositions of the precursor alloys and the dealloying
parameters, and obtain NPMs with diverse nanopore/ligament distributions. We
will briefly summarize NPMs with multiscale or multilevel porous structures.
Multimodal pore size distribution (hierarchically porous nanostructures).
Ding and Erlebacher [58] have developed a two-step dealloying strategy
(dealloying/annealing/plating/annealing/redealloying) to create multimodal pore
1.2 Microstructural Characteristics of Nanoporous Metals 13
(a) (c)
(b) (d)
Fig. 1.14 a TEM and b–d HRTEM images showing the nanoporous structure and lattice defects
(stacking faults, twins, and dislocations) of NPG by dealloying the rapidly solidified Al80Au20
alloy in the 20 wt% NaOH aqueous solution. The inserts show the corresponding a SAED and
b–d FFT patterns. (Reproduced from Ref. [57]. Copyright 2009, American Chemical Society)
size in NPG, Fig. 1.15a, b. And they have argued that some of the general charac-
teristics of the proposed method that are worthy of immediate exploration include
(1) applicability to any system that exhibits porosity evolution upon dealloying (not
just Au/Ag alloys), (2) fabrication of trimodal and higher order porous architectures
by additional annealing/plating/redealloying cycles, and (3) independent tunability
of pore sizes, and even pore topology. Zhang et al. [57] presented a simple one-step
dealloying strategy to synthesize NPG ribbons with bimodal channel size distribu-
tions through design of the Al–Au precursor alloys. The Al80Au20 precursor is
composed of two phases (Al and Al2Au), and the complete etching of the Al phase
leaves the large-sized channels (hundreds of nanometers) while the dealloying of the
Al2Au phase leads to the formation of highly porous channel walls (tens of
nanometers), Fig. 1.15c, d. Recently, Qi and Weissmüller developed a dealloying–
annealing–dealloying strategy to fabricate a hierarchical nested network nanos-
tructure in NPG, starting from a dilute solid solution of AgAu [59]. They controlled
electrochemical corrosion of the dilute AgAu precursor yielding nanoporous Ag–Au
14 1 Introduction to Nanoporous Metals
(a) (b)
(c) (d)
Fig. 1.15 (a, b) A 2D/3D hybrid NPG structure, where the dimension of unit structure in 2D
(1–2 μm) is 2 orders of magnitude larger than that in 3D substructure (*8 nm). Here, 100 nm
thick gold leaf was used, and the second stage annealing was carried out at 500 °C for 8 h.
(Reproduced from Ref. [58]. Copyright 2003, American Chemical Society) (c, d) SEM images of
NPG by dealloying the rapidly solidified Al80Au20 alloy in the 5 wt% HCl aqueous solution.
(Reproduced from Ref. [57]. Copyright 2009, American Chemical Society)
alloy as an intermediate product, and coarsening of the porous alloy created the large
ligaments of the upper hierarchy level. Most recently, a modified dealloying–an-
nealing–dealloying strategy was developed by the same group for monolithic
samples of NPG with a hierarchical structure comprising two nested networks of
solid “ligaments” on distinctly different structural length scales, starting from a
ternary AgAuPt precursor [60]. The beneficial impact of adding Pt to the Ag–Au
master alloys is to reduce the lower hierarchy level ligament size (*6 nm).
Furthermore, Pt favors the retention of Ag during the first dealloying step even when
the master alloy has a high Au content. Lee et al. [61] developed a straightforward
and flexible materials synthesis platform for hierarchically porous gold materials
using bijels as templates. They have believed that a synergistic combination of
nanocasting and chemical dealloying allows for the benchtop fabrication of mono-
lithic gold with hierarchical bicontinuity on widely separated length scales. Besides
monolithic samples (films, ribbons, bulk sheets), hierarchically nanoporous nanos-
tructures have also been reported. For example, Sattayasamitsathit et al. [62]
reported tailor-made highly ordered macro/mesoporous hierarchical metal archi-
tectures by combining sphere lithography, membrane template electrodeposition,
and alloy-etching processes. The new double-template preparation route involves
the electrodeposition of Au/Ag alloy within the interstitial (void) spaces of
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CHAPITRE V