REVIEWS

Hierarchical 3D electrodes for

electrochemical energy storage
Hongtao Sun   1,2, Jian Zhu3, Daniel Baumann1, Lele Peng1, Yuxi Xu4, Imran Shakir5,
Yu Huang6,7 and Xiangfeng Duan   1,7*
Abstract | The discovery and development of electrode materials promise superior energy or
power density. However, good performance is typically achieved only in ultrathin electrodes with
low mass loadings (≤1 mg cm−2) and is difficult to realize in commercial electrodes with higher
mass loadings (>10 mg cm−2). To realize the full potential of these electrode materials, new
electrode architectures are required that can allow more efficient charge transport beyond the
limits of traditional electrodes. In this Review , we summarize the design and synthesis of 3D
electrodes to address charge transport limitations in thick electrodes. Specifically , we discuss the
role of charge transport in electrochemical systems and focus on the design of 3D porous
structures with a continuous conductive network for electron transport and a fully
interconnected hierarchical porosity for ion transport. We also discuss the application of 3D
porous architectures as conductive scaffolds for various electrode materials to enable composite
electrodes with an unprecedented combination of energy and power densities and then
conclude with a perspective on future opportunities and challenges.

The increasing demand for mobile power supplies in
electrical vehicles and portable electronics has motivated
intense research efforts in developing high-​performance
electrochemical energy storage (EES) devices. At the
fundamental level, all EES devices involve the shuttling
and storage of ions between two electrodes, coupled with
the flow of electrons in an external circuit. As a result, the
electrodes must efficiently deliver a sufficient number of
ions into the electrode and a sufficient number of elec-
trons to the external circuit. An ideal EES device has the
ability to store a large amount of energy (that is, a high
energy density) and be charged and discharged rapidly
(that is, a high power density)1–8.
There are four types of EES device — capacitors,
supercapacitors, batteries and fuel cells — each with
merits and limitations (Fig. 1a). Among them, fuel cells
promise ultrahigh energy density but are limited by slow
kinetics (that is, low power density) and the need for
costly precious metal catalysts. Capacitors are limited by
their extremely low energy density and are generally not
suitable for mobile power supply applications. Therefore,
batteries and supercapacitors are the primary EES tech-
nologies on the market today. Batteries offer high energy
density but moderately low power density, while superca-
pacitors provide the opposite: superior power density but
*e-​mail: xduan@
chem.ucla.edu with limited energy density9–13. Despite the striking dif-
https://doi.org/10.1038/ ferences, batteries and supercapacitors share fundamen-
s41578-018-0069-9 tal processes involving coupled electron transport and
ion transport (and storage) in active electrode materials.
The essence of energy storage is, in fact, charge storage
in the form of ions in the electrode material. In super-
capacitors (also called electrochemical capacitors), the
energy is stored as adsorbed ionic species at the interface
between the porous carbon electrode and the electrolyte
(Fig. 1b). The ions are rapidly delivered to the electrode
surface through a liquid electrolyte, and the electrons
are rapidly transported through the highly conductive
carbon electrode to an external circuit. As a result, super-
capacitors typically exhibit rapid charge or discharge
behaviour with a high power density (~10 kW kg−1).
However, the total number of ions that can be stored on
the surface is limited and thus the overall energy density
is low (≤15 Wh kg−1) (Fig. 1a).
In a battery, the ions are transported and inserted
into the electrode, where redox reactions occur within
the active component of the electrode at a given electro-
chemical potential. Therefore, the energy is stored in the
bulk volume of the electrode (Fig. 1c) and enables high
energy densities (≥100 Wh kg−1). However, as a conse-
quence of the slow kinetics of solid-​state ion diffusion
and low electronic conductivity of most electrode mate-
rials, the charge or discharge rate is low, leading to a low
power density of ≤1 kW kg−1 (Fig. 1a). For many applica-
tions, such as electric vehicles, a high-​power device that
can store and release energy quickly (quick charge and
fast acceleration) without compromising high energy

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Reviews
density (driving distance per charge) is ideal (see elec-
tric vehicle goal in Fig. 1a). Hence, research efforts have
been devoted to discovering and developing electrode
materials with higher energy density or higher power
density than those of EES devices of today5,9,10,14–23.
Nanostructured electrode materials show promise
in high-​p erformance EES devices1,7,24–30. For exam-
ple, compared with conventional electrode materials,
nanostructured silicon has a 10-fold increase in specific
capacity26,27, and nanostructured niobia (Nb2O5) pro-
duces a 10–100-fold increase in rate performance7,28.
However, the exceptional performance of these mate-
rials is typically limited to laboratory devices using
ultrathin electrodes with very low mass loadings (≤1 mg
cm−2)15,26,27,31,32. The performance is attributed solely to
the active electrode materials and represents the intrinsic
materials performance, but the actual device also con-
sists of many passive components (considered as a device
overhead). These components include current collectors
at each electrode (copper for anodes and aluminium for
cathodes), a separator (electronic insulator) between the
two electrodes, electrolyte between the anode and cath-
ode that facilitates ion transport, and packaging (Fig. 2a).
Unlike the active materials, which actively participate in
charge storage, these passive components do not contrib-
ute to charge (energy) storage and represent a nearly con-
stant overhead indispensable for device functionality33.
Thus, when the areal mass loading of the active material
is low compared with that of the passive components,
the device performance is dictated by the mass of the
passive components and could be orders of magnitude
lower than the intrinsic material performance9,34.
If we define the specific material capacity as the
capacity normalized by the mass of the electrode mate-
rials and the specific electrode capacity as the capac-
ity normalized by the combined mass of the electrode
materials and the current collector (~5–10 mg cm−2 for
metal current collectors), it is apparent that the electrode
capacity is only ∼10% of the material capacity for most
laboratory devices using thin-​film electrodes with a low
mass loading around 1 mg cm−2 (ref.33) (Fig. 2b). However,
to realize the potential of an active material in a com-
mercial device, its mass loading must be no less than ~10
mg cm−2. This gap between laboratory and commercial
devices has been noted34 but has unfortunately received
insufficient attention in the research community.
Author addresses
1
Department of Chemistry and Biochemistry, University of California, Los Angeles,
CA, USA.
2
Department of Mechanical and Industrial Engineering, New Jersey Institute of
Technology, Newark, NJ, USA.
3
Hunan Key Laboratory of Two-​Dimensional Materials and State Key Laboratory for
Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering,
Hunan University, Changsha, China.
4
State Key Laboratory of Molecular Engineering of Polymers, Department of
Macromolecular Science, Fudan University, Shanghai, China.
5
Sustainable Energy Technologies Centre, College of Engineering, King Saud University,
Riyadh, Saudi Arabia.
6
Department of Materials Science and Engineering, University of California, Los Angeles,
CA, USA.
7
California Nanosystems Institute, University of California, Los Angeles, CA, USA.
46 | JANUARY 2019 | volume 4 www.nature.com/natrevmats
To meet the requirements of commercial cells with a
mass loading of ~10 mg cm−2 or higher, sufficient charge
(in the form of ions and electrons) must be delivered to
fully use the charge storage capacity of a thick electrode
(~50–100 μm). In general, sustaining the same specific
material capacity and current density in a high-​mass-
loaded electrode (>10 mg cm−2) as those in a lower
mass-​loaded electrode (for example, 1 mg cm−2) requires
proportionally larger ion and electron currents across a
proportionally longer charge transport distance. To sat-
isfy this requirement is challenging for nanostructured
electrode materials with an intrinsically higher capacity
or higher rate capability, which require a much larger
number of charges to be delivered in a given time than
conventional electrode materials33. Therefore, the mass
transport limit for ions and the resistance for electron
transport become critical with increasing mass load-
ing26,33,35,36. These factors considerably raise the over-
potential of the device and degrade the capacity during
cycling37. This capacity degradation issue becomes more
apparent at higher current densities (power) because of
the need for more rapid delivery of sufficient charge in
a given time.
These considerations suggest that to attain high per-
formance of nanostructured electrode materials at high
mass loadings in devices is not a simple engineering
scaling matter but a fundamental scientific challenge.
Studies exploring the impact of mass loading on mate-
rial capacity suggest that the ratio of achievable capacity
to theoretical capacity decreases rapidly with increasing
mass loadings, particularly for high-​capacity electrodes
such as silicon33. As a result, the scaled energy density
or power density achieved in a device made from these
electrode materials rarely exceeds those of today’s Li-​ion
batteries by a large extent35,38.
As a consequence of the charge transport limit, a
typical 2D electrode with a planar current collector can
provide sufficient charge to satisfy the charge require-
ment of the electrode material but at a limited depth
(Fig. 2c). For a thicker electrode with high mass loading
beyond such depth limits, only a portion of the active
material is actively used for energy (charge) storage
because of insufficient charge delivery35,37. By contrast,
a 3D electrode architecture contains a 3D conductive
scaffold acting as a 3D current collector and a 3D porous
network for efficient ion transport. This structure
ensures efficient charge delivery throughout the bulk
volume of a thick electrode (Fig. 2d), which is desirable
for the utilization of all electrode materials regardless of
the electrode thickness and for the realization of high-​
rate and high-​capacity energy storage. In this regard,
3D carbon frameworks are attractive scaffolds for the
efficient loading of active materials because of their
high surface area, low density, excellent conductivity
and superior electrochemical stability compared with
other conductive materials.
In this Review, we focus on the syntheses, struc-
tures and electrochemical properties of 3D scaffolds
comprising hierarchically porous carbon materials and
their composites and discuss the optimization of charge
transport in these materials for use in EES devices. First,
we summarize the synthesis of 3D carbon frameworks
 Reviews

(for example, graphene aerogels, carbon fibre foams, a The energy–power conundrum
Fuel cells
graphite foams and 3D-​printed graphene microlat- 103
Batteries
tices) and their composites, with tailored porosity for Supercapacitors
optimized charge transport. The storage performance 102 Capacitors

Energy density (Wh kg–1)

Electric
of the materials, which is dependent on the mass load- vehicle goal
ing, is discussed to illustrate the merits of these 3D 101
structures compared with conventional 2D electrodes.
Second, we discuss the use of natural, or biological, 100
templates (for example, butterfly wings, crab shells and
plant stems) in the fabrication of 3D hierarchical car- 10–1
bon structures and composites39–43. Last, we describe
a 3D battery composed of nanoscale tri-​continuous
10–2
anode–electrolyte–cathode layers that greatly decrease 100 101 102 103 104 105 106
the charge diffusion lengths and increase the rate Power density (W kg–1)
capability44.
b Supercapacitors
3D carbon frameworks Carbon Separator Carbon
Compared with conventional 2D electrodes (for exam- + – + –
+ – – –
ple, copper foil or aluminium foil current collectors), + – + +
+ – + –
3D electrode architectures offer highly efficient charge + –
+ –– + –
+ –
delivery, even in thick electrodes with practical levels of + +
Current – + – – Current
mass loading9,20,36,45–51. More specifically, 3D networks collector – + collector
+ – – +
+ –
made from graphene, carbon fibres and/or carbon nano- + – + –
+ – –
tubes (CNTs) are ideal conductive scaffolds because of + –– – +
their high electrical conductivity, low density, high sur- + + + + ––
+
– – + ––
face area and tailorable porous structures52–55. The con- – – + + –
+ – +
ductive scaffold does not actively participate in charge + – + + ––
+ – –
storage, and, therefore, it must have a low mass and a +
high specific surface area to ensure sufficient loading of c Batteries
active electrode materials. There are several strategies for Discharge
the fabrication of these 3D carbon networks. e–
Charge
e–
Self-​assembly of graphene sheets. Graphene, a single
layer of carbon atoms bonded in a honeycomb lattice,
Anode Separator Cathode
represents an attractive conductive additive for EES
devices because of its single-​atom thickness, high sur- Charge +
face area, excellent electrical conductivity, mechanical Li
flexibility and extraordinary chemical and electrochem- Cu current Al current
collector collector
ical stability56,57. However, the strong van der Waals and Discharge
π−π stacking interactions between graphene sheets cause Li+
them to readily restack to form graphite-​like powders
with compact structures when processed into bulk forms Li+ + e– + C6→LiC6 LiCoO2→Li+ + e– + CoO2
(required for thick electrodes).
Fig. 1 | Electrochemical energy storage technologies.
To translate the remarkable properties of single-​layer
a | A Ragone plot of energy storage technologies.
graphene into macroscopic structures, it is necessary b | The basic configuration and working mechanism of a
to assemble individual graphene sheets such that their super­capacitor. An electric double-​layer capacitor, also
physical features are retained. A simple vacuum filtra- called a supercapacitor, consists of symmetric porous
tion approach has enabled the isolation of macroscopic carbon electrode films sandwiched between two current
graphene papers from well-​dispersed colloidal aqueous collectors and isolated by an insulating separator. c | The
solutions of reduced graphene oxide (rGO)58,59. Such basic configuration and working mechanism of a battery.
graphene papers consist of stacked graphene sheets with A typical battery device consists of an anode and cathode
limited porosity and thus are not ideal for fast ion deliv- film sandwiched between two current collectors and
ery, particularly at large thicknesses. However, if nano­ isolated by an insulating separator.
scale spacers (for example, carbon black nanoparticles)59
are introduced between graphene sheets, then restacking (>2 mg ml−1) of dispersed GO nanosheets that are sepa-
is partially prevented, leading to improved porosity and rated from each other because of electrostatic repulsion
ion transport characteristics. In addition, the introduc- of the negative charges on the GO surface. Following
tion of nanoscale pores in the graphene sheet facilitates a hydrothermal or chemical reduction process, the
ion transport across the graphene papers58. negatively charged oxygenic groups on GO are largely
Alternatively, 3D graphene macrostructures can be removed to partially restore π-​conjugation and form
fabricated via solution reduction of GO56,58,60,61. This rGO. Hydrophobic interactions and π−π stacking
self-​assembly approach starts with a high concentration result in partial overlapping and coalescing of rGO

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a Battery device b The impact of mass loading

100
Anode
Al

material capacity (%)

Electrode capacity/
50

Cu 0
0 10 20 30
Separator Cathode Mass loading (mg cm–2)

c 2D electrode d 3D electrode
Li +
Li +
Li +
Li +
Li +
Li+ Li+ Li+ Li+
Electrolyte

Electrode
material

Current
e– e– e– e– e– e– collector e– e– e– e– e–

Fig. 2 | The role of areal mass loading and structure in battery electrodes. a | The typical configuration of a commercial
battery device. b | The capacity of an electrode is positively proportional to the mass loading of active materials on the
electrode. Higher loadings mean a higher fraction of the electrode stores charge and less is devoted to current collectors.
c | The charge transport pathways in a conventional electrode with a 2D current collector show a limited charge
penetration depth. d | The charge transport pathways in a 3D thick electrode show efficient charge delivery throughout
the entire electrode thickness. Panel b redrawn from ref.33.

sheets to form hierarchical porous 3D frameworks56,60,61 hydrothermal or chemical reduction methods.

(Fig. 3a). The porosity provides fast mass (ion) transport,
and the interconnected 3D porous network offers high
electrical conductivity. The macroscopic shape and size
of the 3D graphene framework are controlled by chang-
ing the geometry of the reaction vessel. The framework
consists of an interconnected 3D graphene network
filled with ∼98 wt% water60,61, namely, a hydrogel. This
one-​step assembly approach is the most direct route to
produce graphene and graphene-​based hybrid hydro-
gels integrated with other components, including other
types of carbon, metal, metal oxide and polymer62–67.
These hydrogels can be transformed into aerogels by
freeze-​drying or supercritical dying while maintaining
the 3D hierarchical porous structure9,58,60,61.
Templated growth of graphene foams. Graphene
frameworks can also be fabricated using a metallic
template (for example, Ni foam) coupled with chemical
vapour deposition (CVD)68–70 (Fig. 3b). First, graphene
films are grown onto the Ni foam template via the ther-
mal decomposition of CH4 at high temperature, followed
by the chemical etching of the Ni template. A layer of
poly(methyl methacrylate) (PMMA) is typically used as
a support to prevent the graphene foam from collaps-
ing during removal of the Ni template. These graphene
foams show superior electrical conductivity compared
with 3D graphene hydrogels or aerogels derived from
Furthermore, because of their high porosity (Fig. 3b),
these graphene foams are of ultralow density and have
an ultrahigh specific surface area.
Copper foams71, Cu–Ni alloy foams72 and anodized
aluminium oxide (AAO) wires73 have also been explored
as templates for synthesizing graphene foams. For exam-
ple, porous Ni–Cu alloy foams with reduced pore sizes
can dramatically increase the specific surface area and
conductivity of the graphene foams. To further reduce
pore sizes (for example, nanopores or mesopores), col-
loidal silica spheres or hierarchical oxides have been
employed as hard templates for synthesizing 3D porous
graphene structures74–77. This hard-​template approach
offers a facile route for generating mesopores in carbon-​
based materials to increase the specific surface area.
Compared with the self-​assembly method, template-​
assisted synthesis is complex and requires processing to
remove the templates. However, the synthetic route can
provide higher quality graphene typically with higher
conductivity than solution-​reduced graphene.
Electrospinning of 3D fibres. Networks of carbon
fibres, for example, non-​woven mats, are another type
of 3D conductive scaffold78–80. Electrospinning is an
inexpensive and scalable technique for the continu-
ous production of large quantities of fibres and fibre
networks (Fig. 3c). In this technique, a high voltage is

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 Reviews

a with this deposition system80. Finally, the electrospun

material is carbonized to produce a conductive carbon
Self-assembly network with hierarchical structure and tunable porosity.

3D printing of graphene microlattices. 3D printing

5 µm builds objects by adding material layer by layer under
2D building blocks 3D graphene aerogel
computer control81. This approach enables the design
b and fabrication of macrostructures with tailored porosity
and specific hierarchical architectures for optimal per-
formance82–89. Using other methods, such as solution-​
CVD growth processable self-​assembly, template-​assisted growth or
electrospinning deposition, the final structure cannot be
Ni etching
precisely predicted despite having some control over the
Ni foam 3D graphene foam
200 µm porous architecture, which could limit the mass transport
behaviour within the 3D network.
c
An extrusion-​b ased 3D printing technique 90,91,
known as direct ink writing, can fabricate highly com-
pressible graphene aerogel microlattices83 (Fig.  3d).
V Carbonization
These structures have good mechanical strength and
large surface areas similar to those of single graphene
2 µm
sheets. In the direct ink writing technique, a three-​axis
Electrospinning 3D carbon fibres motion stage assembles 3D structures by robotically
d extruding a continuous ink filament through a micro-​
nozzle in a layer-​by-layer process92. These gel-​based
viscoelastic inks produce shear-​thinning behaviour
Gelation supercritical
drying to facilitate extrusion flow under pressure. The inks
undergo a drying-​induced transition from pseudoplas-
Carbonization
HF etching
tic to dilatant after deposition to rapidly retain shape82,93.
200 µm To improve the physical and electrochemical proper-
ties of 3D printed structures, functional fillers, such
Direct ink writing 3D graphene microlattice
as conductive nanoparticles, nanotubes, nanowires or
Fig. 3 | Manufacturing of various 3D carbon architectures. a | Solution-​processable nanofibres, can be incorporated into the inks82 to tailor
assembly of 2D graphene sheets into a 3D graphene aerogel. b | Chemical vapour the electrical conductivity or mechanical strength of the
deposition (CVD) growth of a graphene foam on a Ni foam template, followed by removal resulting electrodes.
of the template by etching methods. c | Electrospinning of a 3D carbon fibre network.
d | Direct ink writing (3D printing) of a 3D graphene microlattice. Panel b is adapted 3D graphene for supercapacitors
with permission from ref.69, RSC. Panel c is adapted with permission from ref.79, American Commercial supercapacitors mainly rely on activated
Chemical Society. Panel d (left) is adapted with permission from ref.82, American Chemical
carbons, which are limited by their low specific capac-
Society ; panel d (right) is adapted from ref.83, Springer Nature Limited.
itance (<120 F g−1) and low charge/discharge rate (<10
A g−1). Because the energy storage in supercapacitors
applied between a nozzle of a spinneret and a grounded relies on surface charge absorption, a high-​performance
substrate, and, subsequently, a polymer solution in the supercapacitor electrode requires a large ion-​accessible
syringe is elongated to form a Taylor cone at the nozzle surface area, high electrical conductivity, high ionic
tip. At a critical voltage, electrostatic forces overcome the transport rate and sufficient electrochemical stabil-
surface tension of the polymer solution and eject a liquid ity. To this end, graphene is an ideal material because
jet from the nozzle. The electrically charged jet under- of its single atomic thickness, exceptionally large the-
goes a stretching-​and-whipping process that results in oretical specific surface area (2,630 m2 g−1), high theo-
the formation of a long, thin thread. This stretching-​ retical specific capacitance (550 F g−1)94, high intrinsic
and-whipping process is accompanied by rapid evapo- electrical conductivity, excellent mechanical flexibility
ration of the solvent, which reduces the diameter of the and exceptional electrochemical stability. However,
jet from hundreds of micrometres to as small as tens of driven by strong π–π interactions, 2D graphene sheets
nanometres. Dry fibres are accumulated on the surface restack when they are processed into bulk electrodes,
of the collector, forming a non-​woven mat consisting of which reduces the accessible surface area and ion diffu-
polymer fibres. The diameter, length and uniformity sion rate and thus degrades the specific capacitance and
of the fibres can be adjusted by varying the applied volt- charge/discharge rate. The creation of macroscopic 3D
age and polymer solution concentration (or viscosity). graphene structures with tailored hierarchical porosity
The duration of the electrospinning procedure con- could address this challenge.
trols the thickness of the fibre deposition. Through
careful control of processing parameters, electrospun 3D graphene microlattice. Direct ink writing is an
fibre mats can be produced with a wide range of porosity effective strategy for fabricating 3D graphene aero-
values. For high-​throughput production, multi-​nozzle gels with periodic macroscale pores82 (Fig.  3d). This
spinnerets and a roll-​to-roll process can be integrated 3D-​printed graphene microlattice with a designed

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architecture shows promise for supercapacitor appli-
cations81,82. In this approach, a printable ink consists
of GO and graphene nanoplatelets, which can pro-
vide improved electrical conductivity for the printed
GO–graphene nanoplatelet composite without det-
rimental loss of its surface area. With the specifically
engineered macro-​porosity, extremely thick electrodes
(for example, 1 mm) with excellent ion transport can
be produced. These electrodes deliver 90% capacitance
retention when the current density is increased from
0.5 A g−1 to 10 A g−1 (ref.82). The high power densities
(>4 kW kg−1) of these ultrathick electrodes are equal to
or exceed those of thinner electrodes with thicknesses
10−100 times smaller. The excellent electrochemical
behaviour and rate capability can be attributed to the
3D-​printed macro-​architecture, which enables fast
ion diffusion in the thick electrode. As such, this work
demonstrates how 3D printing can overcome traditional
a Graphene framework b Holey graphene framework
c d
2.5 GF
Phase angle (degree)
design barriers by creating functional architectures with
well-​controlled structural parameters by design. The
capability of designing and fabricating EES devices with
improved charge transport opens up opportunities for
high-​performance EES devices.
Holey graphene framework. Traditionally, the per-
formance of a supercapacitor electrode is evaluated by
its gravimetric performance, but its volumetric perfor-
mance is an important metric for applications in which
volume is at a premium (for example, portable electron-
ics)95–101. For most electrodes, there is a trade-​off rela-
tionship between gravimetric (specific) capacitance and
volumetric capacitance. More specifically, highly porous
electrodes allow rapid ion diffusion and hence show high
gravimetric capacitance, but the low packing density of
the material causes a low volumetric capacitance. An
electrode with higher packing density may have higher
volumetric capacitance but decreased ion diffusion rate
and ion-​accessible surface area, leading to a low gravi-
metric capacitance and poor rate performance. For
example, supercapacitor electrodes made from laser-​
scribed porous graphene show exceptional gravimetric
capacitance (276 F g−1) but a low volumetric capacitance
(13 F cm−3) because of the very low packing density
(~0.05 g cm−3)102. Highly compact graphene papers or
other carbon-​based composite papers obtained by vac-
uum filtration deliver high volumetric capacitance (>200
F cm−3) because of their high density but show modest
GF gravimetric capacitance (<170 F g−1)100,103. This trade-​off

HGF –80 HGF makes it challenging to design a supercapacitor electrode

2.0
–60 that can simultaneously deliver high gravimetric capac-
τ0 = 0.17 s
–Z′′ (Ω)

1.5 itance and high volumetric capacitance while retaining

–40 excellent rate capability.
1.0 τ0 = 0.49 s
–20 A 3D holey graphene framework (HGF) can address
0.5
this trade-​off issue61. By mechanically compressing a 3D
0
0.0 HGF into a thin film, the packing density of the HGF is
0.0 0.5 1.0 1.5 2.0 2.5 10–2 10–1 100 101 102 103
increased by nearly two orders of magnitude (from ~0.01
Z′ (Ω) Frequency (Hz)
e f g cm−3 to ~0.71 g cm−3), while the interlocked graphene
Volumetric capacitance (F cm–3)

350 sheets in the HGF prevent the sheets from restacking dur-
Specific capacitance (F g–1)

Specific capacitance (F g–1)

300 300
300 ing compression to retain the high specific surface area.
250
250 250 In addition, the tailored pores in HGFs are larger and well
200 200 200 integrated compared with those in non-​holey GFs (Fig. 4a).
150 These pores function as shortcuts for rapid ion diffusion
150 150
100 between graphene layers and increase the speed of ion
GF 100 1 mg cm–2 100 transport across the compressed film (Fig. 4b). This ability
50 HGF 10 mg cm–2
0 50 50
to optimize charge transport is shown by Nyquist plots
0 20 40 60 80 100 0 5 10 15 20 and Bode plots (Fig. 4c,d). More specifically, HGF elec-
Current density (A g )–1
Current density (A g ) –1
trodes show a smaller equivalent series resistance (0.65 Ω)
Fig. 4 | Electrochemical characterization of 3D electrodes. a | Illustration of a and a shorter time constant (0.17 s) than non-​holey GF
compressed film of a solvated graphene framework (GF) with arrows depicting the ion electrodes (1.25 Ω and 0.49 s), suggesting enhanced ion
transport pathways. b | Illustration of a compressed film of a solvated holey graphene transport rates in the HGF electrodes61. As a result, HGF
framework (HGF) with arrows depicting the ion transport pathways. The ions in the GF film electrodes show considerably higher capacitance than
must travel long distances to find the broken edge of the graphene sheet and, hence, to GF electrodes, particularly at high current densities
cross into another graphene sheet, while the nanopores in the HGF function as shortcuts (Fig. 4e). These compressed HGFs can deliver ultrahigh
between neighbouring graphene sheets to greatly increase the speed of ion transport
gravimetric and volumetric capacitances of 298 F g−1
across the HGF film. c | Nyquist plots of GF and HGF electrodes in 6 M KOH electrolyte. d |
and 212 F cm−3 at a mass loading of 1 mg cm−2 (ref.61)
Bode plots of phase angle as a function of frequency for GF and HGF electrodes. e |
(Fig. 4f). More importantly, the gravimetric and volumet-
Specific capacitances as a function of current density for GF and HGF electrodes in 6 M
KOH electrolyte. f | Gravimetric and volumetric capacitances of HGF electrodes as a ric capacitances of the HGF electrodes decrease by only
function of current density in pure ionic liquid electrolyte with mass loadings of 1 and 12% when the mass loading is increased from 1 mg cm−2
10 mg cm−2. τ0, time constant; Zʹ and Z” represent the real and imaginary parts of the to 10 mg cm−2, because of the sustained high electri-
complex impedance, respectively. Figure adapted from ref.61, Springer Nature Limited. cal conductivity and rapid ion diffusion within the

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whole electrodes (Fig. 4f). Such sustained performance
at a practical level of mass loading is an important
step towards commercial applications owing to the
reduced ratio of the mass of passive components to
the mass of active materials34.
3D hybrid electrodes
3D porous structures are attractive scaffolds for active
electrode materials because of their excellent charge
transport kinetics9,70,79,86,104; more specifically, the scaf-
folds ensure efficient charge delivery to the active
materials to fully utilize their charge (energy) storage
capability and realize high-​energy and high-​power-
density energy storage (Table 1). Moreover, the mechan-
ically strong hierarchical porous architectures of carbon
networks can accommodate large volume changes and
mitigate mechanical stress within the electrode, enabling
long-​term cycling stability of EES systems36,67,105.
HGF integrated with high-​power-density materials.
By incorporating orthorhombic-​p hase niobia
(T-​Nb2O5) nanoparticles106 into 3D HGF or GF scaf-
folds, composite architectures with improved power
capability can be fabricated9 (Fig. 5a–c). With an intrin-
sically high rate capability, T-​Nb2O5 is an interesting
model system for probing the susceptibility of the rate
performance to the electrode design because the overall
rate capability is dictated not by ion transport inside the
T-​Nb2O5 nanoparticles but by insufficient delivery of
ions to the T-​Nb2O5 surface. Composites with differing
porosities were prepared (Nb2O5/GF for a Nb2O5 and
GF composite and Nb2O5/HGF-0.5, Nb2O5/HGF-1.0
and Nb2O5/HGF-2.0 for Nb2O5 and HGF composites
obtained by etching in H2O2 for 0.5, 1.0 and 2.0 hours,
respectively) to evaluate the impact of porosity on the
charge transport and energy storage performance9.
Compared with the macroporous electrode without in-​
plane nanopores (Nb2O5/GF), the 3D HGF composite
with optimized nanopores (Nb2O5/HGF-2.0) shows
enhanced specific capacity at a given charge/discharge
rate9. The difference widens with increasing charge/dis-
charge rate (Fig. 5c). For example, at a high rate of 100 C
(1 C corresponds to complete charge or discharge in
1 hour), the Nb2O5/HGF-2.0 electrode delivers a specific
capacity (75 mAh g−1) 2 times higher than that of the
Nb2O5/GF electrode (35 mAh g−1). This enhanced rate
capability is attributed to the decrease in ionic resistance
in the HGF as the pore size increases. Specifically, an
increase in pore size from 0 nm to 2.7 nm decreases the
ionic resistance by more than three times. In particular,

Table 1 | Summary of characteristics and performance metrics of representative 3D electrodes

3D electrodes Areal mass Packing Active Fabrication method Gravimetric Areal Volumetric Refs
loading density material performance performance performance
(mg cm−2) (g cm−3) (%) (mAh g−1) (mAh cm−2) (mAh cm−3)
HGF 1 0.7 100 Solution self-​assembly 298 (F g−1) 0.3 (F cm−2) 212 (F cm−3) 61

10 262 (F g−1) 2.6 (F cm−2) 186 (F cm−3)

HGF/Nb2O5 1 1.5 100 Two-​step self-​assembly 184 0.2 283 9

11 139 1.6 234

22 177 3.9 272
GF/sulfur 4.3 – 90 Solution self-​assembly 969 4.2 – 67

Carbon fibre foam/sulfur 10.8 1.0 64 Natural template and 935 10.1 935 36

coating
21.2 1.7 74 698 14.8 1,215
LTO/GF//LFP/GF – – 88 CVD, hydrothermal 117 – – 70

GF/NiMoO4 1 – – CVD, hydrothermal 868 0.9 – 69

FeS2@carbon fibre 2 – 76 Electrospinning 530 1.1 – 79

TiO2@carbon fibre 22 – 40 Electrospinning 73 1.5 – 115

Graphene aerogel 6.5 0.1 100 3D printing −1

64 (F g ) −2
0.4 (F cm ) 4 (F cm−3) 82

HG mesh 3.4 – 100 3D printing 3,879 13.3 – 86

CNT/Si 8 (Si) 0.1 – CVD 1,100 8.8 138 52

CNT/Co3O4 7.3 0.3 60 Hydrothermal 1,050 7.7 279 53

CNT/Sn(O)2 9.2 0.1 73 Hydrothermal 810 7.4 50 54

CNT/graphene – – – CVD (AAO) – 3.3 (mF cm ) −2

– 73

CNT/MnO2 8.3 – – Electrodeposition 337 (F g−1) 2.8 (F cm−2) – 55

N-​doped GF 1 0.2 80 Freeze-​drying, CVD 1,057 1.1 235 51

Polyaniline/Si 0.3 0.7 75 In situ polymerization 550 0.2 371 132

Polypyrrole/Fe3O4 – – 85 Co-​precipitation 1,100 – – 127

Polypyrrole/LFP – – 86 In situ polymerization 133 – – 128

AAO, anodized aluminium oxide; CNT, carbon nanotube; CVD, chemical vapour deposition; GF, graphene framework; HG, holey graphene; HGF, HG framework;
LFP, LiFePO4; LTO, Li4Ti5O12.

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Reviews

the in-​plane pores function as shortcuts for ion transport strategy for introducing in-​plane pores to improve the
in the hierarchical porous structure to facilitate rapid ion ion transport kinetics in electrochemical systems has
transport throughout the entire 3D electrode and also been reported in other 2D nanomaterials, for
improve ion access to the surface of T-​Nb2O5. A similar example, 2D transition metal dichalcogenides107–110.

a b c

Specific capacity (mAh g–1)

200 1 C 1
2
5
10
150 20
30 Nb2O5/GF
50
100 100 Nb2O5/HGF-0.5
Nb2O5/HGF-1.0
50 Nb2O5/HGF-2.0

20 µm 20 nm 0 20 40 60 80
Cycle number
d e f
2.5 1C

Potential (V vs Li+/Li)
30 C
2.0 50 C
100 C
1.5 200 C

1.0

0.5
200 µm 200 nm 0 25 50 75 100 125 150 175
Specific capacity (mAh g–1)
g h i 800 120
700 100
Specific capacity 600

efficiency (%)
Coulombic
(mAh g–1) 500 80
400 60
300 40
200
100 20
0 0
0 20 40 60 80 100
2 µm 100 nm
Cycle number

j k l Specific capacity (mAh g–1)

0 1,000 2,000 3,000 4,000
3.5
HG mesh
Voltage (V)

3.0 HG film

2.5

500 µm 5 µm 2.0
0 2 4 6 8 10 12 14
Areal capacity (mAh cm–2)

Fig. 5 | 3D hierarchically porous carbon scaffolds for electrochemical energy storage systems.
a–c | Self-​assembled Nb2O5/holey graphene framework (HGF) composite electrodes. Scanning electron microscopy
(SEM) image of the cross section of the Nb2O5/HGF composite (panel a). Transmission electron microscopy (TEM) image
of graphene sheets uniformly decorated with T-​Nb2O5 nanoparticles (panel b). Specific capacity at different charge/
discharge rates (1–100 C), where 1 C corresponds to complete charge or discharge in 1 hour, for a Nb2O5/graphene
framework (GF) electrode and Nb2O5/HGF composite electrodes etched in H2O2 for 0.5, 1.0 and 2.0 hours with tailored
in-​plane nanopores (panel c). d–f | Images of template-​assisted graphene foams loaded with the active material,
Li4Ti5O12 (LTO), to form an LTO/graphene foam hybrid anode. SEM (panel d) and TEM (panel e) images of the 3D LTO/
graphene foam anode. Discharge voltage curves of the LTO/graphene foam electrode with different discharge rates
(panel f). g–i | Electrospun FeS2@carbon fibres for use as high-​energy-density cathodes in rechargeable lithium
batteries. SEM (panel g) and TEM (panel h) images of FeS2@carbon fibres, and cycling characteristics of FeS2@carbon
fibre electrodes (panel i). j–l | Extrusion-​based 3D-​printed hierarchically porous architectures for use as cathodes in
Li–O2 batteries. An optical image showing a top-​down view of the freeze-​dried HG oxide (HGO) mesh structure (panel
j). SEM image of disassembled HG mesh cathodes in the discharge state (panel k). Comparison of the deep discharge
performance between the 3D HG mesh cathode and the 2D vacuum-​filtrated HG film cathode (panel l). Panels a–c
are adapted with permission from ref.9, AAAS. Panels d–f are adapted with permission from ref.70, Proceedings of the
National Academy of Sciences. Panels g–i are adapted with permission from ref.79, American Chemical Society.
Panels j–l are adapted with permission from ref.86, Wiley-​VCH.

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Graphene-​foam-based hybrid electrodes. 3D graphene
foams can function as ultralight current collectors with-
out using conductive carbon additives, binding agents or
metal current collectors69,70,111,112. For instance, Li4Ti5O12
(LTO)/graphene foam electrodes show ultrafast charge/
discharge performance for Li-​ion batteries because the
high electrical conductivity and optimized pore structure
(Fig. 5d) of the hybrid electrodes enable rapid electron
and ion transport70. The LTO nanosheets were directly
grown on the graphene foam with conformal contacts
and large interfacial area (Fig. 5e), thus ensuring a short
solid-​state diffusion length and fast lithium insertion
into and extraction from the LTO. With these unique
features, the LTO/graphene foam hybrid material deliv-
ers extremely high charge/discharge rate. At rates of 1
C and 30 C, the LTO/graphene foam electrode shows
a specific capacity of approximately 170 mAh g−1 and
160 mAh g−1, respectively. Even at a high rate of 200 C
(~18 s full discharge), the material retains a specific capa­
city of 135 mAh g−1, corresponding to ~80% of the spe-
cific capacity at 1 C (Fig. 5f). By contrast, the reference LTO
electrode prepared using the same process but without the
presence of a 3D GF shows a nearly zero capacity at
the rate of 200 C (ref.70). This difference highlights the
critical role of the 3D structure in facilitating rapid charge
transport to ensure high rate performance. In addition to
Li-​ion batteries, these hybrid graphene foams have been
incorporated in lithium–air batteries (for example, 3D
MnO2/graphene foam electrode for Li–O2 batteries)113 and
other metal-​ion batteries (for example, 3D VO2/graphene
foam electrode for Na-​ion batteries)114, showing increased
energy storage performance and lower cost.
Carbon-​fibre-network-​based hybrid electrodes.
A freestanding carbon fibre network is an alternative
binder-​free and metal-​current-collector-​free conductive
scaffold to load active materials36,78,79,105,115,116. These fibres
have shorter diffusion distances and faster intercalation
kinetics (because of their higher surface area to mass
ratio) than commonly used powder materials. Thus,
these non-​woven fibrous mats can reduce charge trans-
fer resistance at the interface between the electrolyte and
active electrode materials to ensure excellent rate capa-
bility. A variety of carbon fibre composites containing
nanoscale active materials (for example, FeS2, FeF3 or Si
nanoparticles) have been fabricated as high-​performance
anodes or cathodes79,105,117 (Fig. 5g,h). For example, a FeS2@
carbon fibre composite delivers a stable capacity of 530
mAh g−1 for 100 cycles with a low decay rate of 0.12%
per cycle79 (Fig. 5i). When needed, additional porosity can
be introduced into the fibre composite. In a Si@carbon
fibre composite electrode, the pores in the fibre compos-
ite matrix offer abundant space to accommodate large
volume changes during charge/discharge process. More
importantly, a static solid-​electrolyte interphase can be
formed on the outer surface of the fibres instead of on
the surface of the Si nanoparticles, thus ensuring a stable
energy capacity for over 1,000 cycles105.
3D-​printed porous electrodes. A 3D hierarchically
porous architecture can be specifically designed by using
controllable and scalable 3D printing techniques82–89.
NAtuRe RevIews | MATERiAlS
Reviews
In particular, the shear-​thinning behaviour of aqueous
HG oxide (HGO) ink enables extrusion-​based printing
of fine filaments into complex 3D architectures86. The
freestanding 3D-​printed HGO meshes exhibit hier-
archical porosity, for example, nanosized mesopores
(4–25 nm) on individual HGO sheets, microsized pores
(~10–20 μm) introduced by lyophilization and macro-
sized pores (<500 μm2) introduced by the 3D printing
process (Fig. 5j). These hierarchical pores increase the
accessible surface area, provide less tortuous ion trans-
port pathways and ensure efficient use of the active
materials86.
Studies show that these 3D printed HG meshes
reduced from HGO are ideal electrodes for Li–O2 bat-
teries, in which surface reactions with gas-​phase oxy-
gen facilitate reversible oxygen reduction reactions
and oxygen evolution reactions8,86,118. Because of the
efficient oxygen diffusion in the meshes, the spherical
Li2O2 particles are uniformly distributed throughout
the electrode thickness during discharge (Fig. 5k). The
hierarchical structure of the HG mesh offers efficient
mass and ion transport pathways within the 3D printed
electrode, ensuring oxygen and electrolyte accessibility
to the entire printed electrode. The deep discharge per-
formance of the 3D-​printed HG mesh displays a high
areal capacity of 13.3 mAh cm−2 (~4.8 mAh in total
capacity or 3,879 mAh g−1) at 0.1 mA cm−2 (ref.86) (Fig. 5l).
By contrast, the control vacuum-​f iltrated HG film
shows only 0.21 mAh cm−2 (<0.03 mAh in total capacity
or ~92 mAh g−1) because the 2D structure of the film
severely limits the surface reactions required for Li–O2
batteries. This large capacity difference highlights the
advantage of the 3D HG mesh architecture fabricated by
extrusion-based 3D printing.
Mitigating mass-​induced degradation
Compared with planar electrodes, 3D electrodes ensure
more efficient charge delivery and better utilization of
electrode material in thick electrodes (for example,
>100 μm) with practical levels of mass loading (for
example, >10 mg cm−2) (Fig. 2c,d). Studies have shown
that 3D composite electrodes improve the charge
transport and lead to more efficient utilization of the
electrode materials at high mass loading36,67, resulting
in substantially higher areal capacity than their pla-
nar counterparts at the same mass loading36,48,67,119,120.
For example, the 3D Nb2O5/HGF-2.0 electrode with a
hierarchically porous structure sustains high perfor-
mance as mass loading increases, while the conven-
tional Nb2O5/graphene composite with a randomly
stacked conductive network shows rapidly degrading
capacity with increasing mass loading9 (Fig. 6a–c). The
voltage–capacity curves of Nb2O5/graphene composite
electrodes with increasing mass loading show increas-
ingly steeper slopes and larger voltage drops (Fig. 6b),
which are attributed to the larger internal resistance in
the thicker electrode. This larger internal resistance is
caused by a larger ionic resistance, leading to higher
overpotentials and thus lower capacities37. In addition,
the charge storage capacity is dramatically altered at
different mass loadings, with the capacity decreasing
from 85 mAh g−1 to 25 mAh g−1 as the mass loading
volume 4 | JANUARY 2019 | 53
 Reviews

a Nb2O5/graphene electrodes Nb2O5/HGF-2.0 electrodes increasing mass loading because of the optimized
charge transport kinetics9.
As evidenced by the plot of areal capacity as a func-
tion of current density (Fig. 6e), the optimized 3D Nb2O5/
HGF-2.0 composite electrode (red circles) compares
favourably with commercial graphite anodes (black sym-
bols)35,38,121 and representative research anodes (includ-
ing high-​rate Nb2O5 electrodes (green symbols) and
high-​capacity Si electrodes (blue symbols))7,26–28,32,122–125.
With increasing current density, the Nb2O5/HGF-2.0
b Nb2O5/graphene c Nb2O5/HGF-2.0 electrode exhibits a smaller decay in areal capacity than
commercial and most laboratory devices, and it delivers
3.0 3.0
1 mg cm–2 a higher areal capacity at high current densities (above
6 mg cm–2 5 mA cm−2), at which the charge delivery capability
2.5 2.5 11 mg cm–2
Voltage (V)

Voltage (V)

becomes increasingly important. The composite elec-

2.0 2.0
trodes continue to provide energy storage at current
1 mg cm–2 densities exceeding 20 mA cm−2, whereas other elec-
6 mg cm–2 trodes can barely perform at such high current densi-
1.5 11 mg cm–2 1.5
ties. These studies highlight that charge transport in the
1.0 1.0 composites can be optimized by tailoring the porosity
0 50 100 0 50 100 150 of the HGF to deliver high areal capacity and high rate
Specific capacity (mAh g ) –1
Specific capacity (mAh g–1) capability at high mass loading, which is essential for
d e Nb2O5/HGF-2.0
commercial EES devices.
Synthetic graphite
1 mg cm –2
Commercial graphite Biological templates for scaffolds
6 mg cm–2 Aligned graphite
11 mg cm–2 Si secondary structure Efficient ion transport in battery electrodes resembles
Si@graphene cages nutrient and electrolyte transport in biological sys-
6 Double-walled Si nanotubes
1C 1 tems. Thus, biological structures with interconnected
Specific capacity (mAh g–1)

200
Areal capacity (mAh cm–2)

2 Nb2O5 nanowires
5 5
10
150 20 4
30
50
3
100 100
2 for the fabrication of intricate 3D structures42,126 (Fig. 7a).
50
1
0 0
0 20 40 60 80
Cycle number
Fig. 6 | The effect of mass loading on electrochemical characterization of Nb2O5/HGF
composite electrodes. a | Schematics comparing the structures of the slurry-​based
Nb2O5/graphene composite and the 3D hierarchically porous Nb2O5/HGF-2.0 composite
etched in H2O2 for 2.0 hours with tailored in-​plane nanopores for improved charge
transport kinetics. b | Galvanostatic charge/discharge curve for the Nb2O5/graphene
control electrode at a rate of 10 C for mass loadings of 1, 6 and 11 mg cm−2.
c | Galvanostatic charge/discharge curve for the Nb2O5/HGF-2.0 electrode at a rate of 10 C
for mass loadings of 1, 6 and 11 mg cm−2. d | Comparison of the rate performance (1–100 C) of
the Nb2O5/HGF-2.0 (squares) and Nb2O5/graphene (circles) electrodes at mass loadings
of 1, 6 and 11 mg cm−2, where 1 C corresponds to complete charge or discharge in 1 hour.
e | Comparison of the areal performance metrics of the Nb2O5/HGF-2.0 electrode with
various commercial and research anodes, including graphite anodes, high-​capacity Si
anodes and high-​rate Nb2O5 anodes. Figure adapted with permission from ref.9, AAAS.
increases from 1 mg cm −2 to 11 mg cm −2 (Fig.  6b) .
This capacity degradation highlights the difficulty in
delivering sufficient ionic current to retain the same
gravimetric capacity in thicker electrodes. Notably,
the optimized Nb2O5/HGF-2.0 electrodes show only a
small voltage drop and capacity loss with increasing
mass loading in the charge/discharge curve (Fig. 6c)
and in the rate performance (squares in Fig. 6d). As
a result, the 3D hierarchically porous Nb2O5/HGF-
2.0 electrodes exhibit less capacity degradation with
Nb2O5 films channels over multiple length scales provide a natural
Mesoporous Nb2O5 template for 3D porous scaffolds for EES systems39,41–43.
For instance, the wings of a Morpho butterfly have bio-​
organic, chitin-​based scales that can act as a template
The butterfly scales are rectangular with pointed tips,
and each scale has parallel ridges decorated with nano-
scale ribs spaced several microns apart and aligned
0 10 20 30 40 50
along the length of the scale. Such intricate chitin scales
Areal current density (mA cm–2)
can function as templates for conformal deposition of
other materials using various approaches (for example,
the sol–gel process) to make hierarchical structures126.
Similarly, crab exoskeletons feature highly mineral-
ized chitin–protein nanofibres arranged in a twisted
plywood or Bouligand pattern, which can be used as
a template to form hollow carbon nanofibres41 (Fig. 7b).
With such 3D structures, high-​capacity active electrode
materials, such as sulfur and silicon, can be encap-
sulated into the hollow carbon nanofibres to create
efficient battery electrodes.
Furthermore, natural wood (Fig. 7c) and other plants
(Fig. 7d) have interconnected hierarchical channels that
can be converted into a conductive scaffold via a car-
bonization process43. Halophytic plants (that grow
in high-​salinity water), which absorb a large amount
of metal ions through their roots and accumulate selected
metal ions in their tissue by a hyperaccumulation effect,
can be used as template to create 3D composite elec-
trode architectures. For example, the calcination of Sn-​
enriched Suaeda glauca produces hierarchically porous
3D carbon/SnOx composites (Fig. 7d–g). Specifically,
the composites comprise a high-​density array of par-
allel channels (diameters of ~50 μm) surrounded by
microsized pores (~5 μm) derived from parenchymal

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 Reviews

a b c d

1 µm 2 µm 200 µm 200 µm

e f g h

10 µm 2 µm 30 nm 5 nm

i j
Specific capacity (mAh g–1)

Specific capacity (mAh g–1)

Coulombic effiiciency (%)

1,500 700 100
0.125 600
1,200 80
A g–1 0.125 500
0.25
0.625 400 60
900
1.25 300 40
2.5 200
600 6.25
12.5 20
100
300 0 0
0 20 40 60 80 100 120 140 160 0 2,000 4,000 6,000 8,000 10,000
Cycle number Cycle number

Fig. 7 | The use of biological materials as templates to fabricate 3D hierarchically porous architectures for
energy storage systems. a | The wings of a Morpho butterfly with chitin-​based scales, which are rectangular with
pointed tips; each scale has parallel ridges decorated with nanoscale ribs. b | A stone crab shell with highly
mineralized chitin–protein nanofibres arranged in a twisted plywood or Bouligand pattern. c | Wood with numerous
channels perpendicular to its surface. d–g | Scanning electron microscopy (SEM) images of the cross section of a
calcined 3D hierarchical porous carbon/SnOx composite derived from medulla of Sn-​enriched Suaeda glauca stems.
A high-​density array of parallel channels (diameters of ~50 μm) (panel d) surrounded by microsized pores (~5 μm)
derived from parenchymal cells (panel e). There are abundant transverse pores (~1–5 μm) on the sidewalls of these
channels (panel f) and a high density of ultrafine pores (~1–10 nm) in the calcined cell wall structure (panel g).
h | High-​resolution transmission electron microscopy (TEM) image of the 3D carbon/SnOx composite shows ultrafine
SnOx nanoparticles embedded in the carbon matrix. i | The rate performance of the 3D carbon/SnOx composite
electrode derived from the epidermis of stems at different current densities. j | Cycling performance of a 3D carbon/
SnOx electrode at a high current density of 12.5 A g−1. Panel a is adapted with permission from ref.42, The Royal
Society ; sample made at Karlsruher Institut für Technologie. Panel b is adapted with permission from ref.41,
American Chemical Society. Panel c is adapted with permission from ref.40, Wiley-​VCH. Panels d–j are adapted
from ref.43, Springer Nature Limited.

cells (Fig.  7d,e). There are also abundant transverse 3D conductive polymer gels
pores (~1–5 μm) on the sidewalls of these channels 3D conductive polymer gels offer alternative scaffolds
(Fig. 7f) and a high density of ultrafine pores (~1–10 to tailor charge transport for improved electrochemi-
nm) in the calcined cell wall structure (Fig. 7g). High-​ cal performance of the active electrode materials127–132.
resolution transmission electron microscopy (TEM) These hybrid polymer gels can be prepared by in situ
images show ultrafine SnOx nanoparticles embedded polymerization, in which the active electrode materi-
in the carbon matrix (Fig. 7h). This hierarchical porous als are conformably coated by the conductive polymer
structure favours the rapid diffusion of electrolyte ions layer127,129,132. Within the electrode, the embedded active
into the pores across the entire structure and accom- materials are interconnected and immobilized within
modates the excessive volume expansion during the the conductive gels127. Therefore, these polymer gels
charge process to ensure robust cycling behaviour. As function as both the binder and the conductive additive.
a result, the 3D carbon/SnOx anode derived from the These 3D polymeric scaffolds are typically formed by
halophytic plant delivers an impressive rate capability crosslinking the conductive polymer chains. The chem-
at variable current densities from 0.125 A g−1 to 12.5 ical and physical properties of the crosslinked polymer
A g−1 (Fig. 7i) and a high reversible capacity (341 mAh gels vary depending on the crosslinker. The microstruc-
g−1) for over 10,000 cycles at a high current density tures of 3D conductive polymer gels can be tuned by
of 12.5 A g−1 (Fig. 7j). using different organic solvents and varying the ratio of

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Reviews

the polymer monomers to the crosslinkers127,129. These
3D polymer gels form a uniform and ductile coating
on the active electrode materials and prevent material
aggregation. By controlling the synthetic conditions,
an interconnected conductive polymer network is
formed with efficient pathways for rapid electron trans-
port and a hierarchically porous structure for efficient
ion and electrolyte diffusion. This porous structure can
also accommodate volume changes in high-​capacity,
conversion-​type electrode materials during cycling127,132.
These combined features make conductive polymer gels
an attractive scaffold for supporting active materials
with efficient charge transport kinetics and excellent
mechanical robustness.
For example, a conductive polymer gel acts as a
binder and a conductive scaffold in nanoparticle-​based
Li-​ion batteries. The conductive polymeric scaffold con-
tains polypyrrole and high-​capacity Fe3O4 nanoparti-
cles as the active materials. These 3D polymer hybrid
electrodes show higher capacity at elevated charge/
discharge rates than 2D electrodes127. This improve-
ment in performance is attributed to the high electrical
conductivity of the polypyrrole scaffold, the uniform
dispersity of the active nanoparticles and the robust-
ness of the scaffold to withstand mechanical stresses
during cycling. Additionally, the incorporation of a 3D
conductive polymer framework into Si-​based anodes
improves cycling stability132. Moreover, the 3D conduc-
tive polymer gel has been used as a scaffold for cathode
materials (for example, LiFePO4 (ref.128)) and 3D con-
ductive ternary systems incorporated with CNTs can
act as mechanically robust hybrid anode materials for
Li-​ion batteries133.
3D tri-​continuous batteries
Batteries typically consist of a composite anode and
cathode with a porous membrane separator dividing
the two electrodes and the separator infiltrated with
liquid electrolyte12 (Fig. 8a). In the device, ions must
travel across the entire bulk thickness of the stacked
anode–electrolyte–cathode layers to fully use their
energy storage capacity. In this regard, thin-​film elec-
trodes with stacked anode–electrolyte–cathode layers
of micrometre thickness are attractive for reducing the
ion diffusion length and enabling rapid charge delivery
for high-​power applications134 (Fig. 8b). The thinner the
films are, the shorter the ion diffusion distances and
the higher the output power densities. However, such
stacked thin-​film devices require additional layers of
current collectors and separators, which increases the
mass of the passive components and reduces the overall
energy stored when the total mass of the device is taken
into account34. In general, a thick electrode with a high
mass loading of active materials is essential for reducing

a Composite b Thin film c Interdigitated d 3D network

e – e–
e–
e–
Anode
Li+

Current
collector 50 nm
Porous Liquid Solid Cathode
separator electrolyte electrolyte

e 3D tri-continuous electrode assembly

Anode network Electrolyte coating Cathode network
e–

50 nm
50 nm

Fig. 8 | A 3D tri-​continuous nanolayer battery. a–d | Illustrations of different battery architectures. The commonly used
composite design (panel a), a thin-​film design (panel b), an interdigitated thin-​film design (panel c) and a 3D network
tri-​continuous nanolayer design (panel d). e | Illustration of a 3D tri-​continuous nanolayer battery assembly. A redox-​active
and conductive carbon anode with gyroidal 3D structure and finite wall thickness (black) is conformally coated with a
polymer electrolyte (blue), for example, poly(phenylene oxide). The remaining interpenetrating network mesopore
channels are back-​filled with a redox-​active and conductive cathode (red), for example, a composite of sulfur and
poly(3,4-ethylenedioxythiophene). Figure adapted with permission from ref.44, RSC.

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the mass ratio of the passive components to the active
materials and increasing the overall energy density in the
device135. The trade-​off between the power density and
energy density is difficult to reconcile with traditional
planar electrodes. The improvement of one parameter
is often achieved at the sacrifice of the another parame-
ter4,11,34,136. For example, although nanostructured elec-
trodes with reduced feature sizes and increased porosity
improve charge transport and delivery for high power
density9,35,137,138, such high performance can be achieved
only in ultrathin electrodes with a low mass loading of
active materials, which limits the overall energy density
of the entire device.
Alternatively, by interdigitating 1D and 2D electrodes
to form 3D structures, the charge transport distances
between the anodes and cathodes become shorter, while
ensuring sufficient loading of the active material in a
given footprint area88,135,139–141 (Fig. 8c). However, such
interdigitated structures are stable only at low aspect
ratios (height:width) and become structurally unstable,
especially in the nanometre regime142. To this end, tri-​
continuous nanoscale layers of anode, electrolyte and
cathode folded in 3D space may help to retain structural
stability while providing benefits such as short ion diffu-
sion distance and 3D connectivity for fast electron trans-
port44,135,141 (Fig. 8d). In such 3D tri-​continuous devices,
energy density and power density are decoupled from
each other at the device level, depending independently
on the intrinsic storage capacity and on the separation dis-
tance between the cathodes and anodes, respectively135,141.
However, combining the active electrode materials, cur-
rent collector and electrolyte into a tri-​continuous bat-
tery is a formidable task143,144. A battery requires strict
separation of the anode and cathode networks to avoid
short circuits. The electrode materials must also be simul-
taneously redox active and electronically conductive. The
electrolyte has to provide sufficient ionic conductivity
while being electronically insulating enough to prevent
a short circuit between the interpenetrating anodes and
cathodes, as well as minimize self-​discharge.
However, a bottom-​up fabrication method takes
advantage of phase separation in block copolymers to
create a spatially precise tri-​continuous battery44 (Fig. 8d).
More specifically, the electrode assembly includes an
active cathode and current collector composite network
(for example, sulfur/poly(3,4-ethylenedioxythiophene),
represented by the red core in Fig. 8d) and a carbon
anode network (for example, a triblock terpolymer-​
derived core–shell double gyroidal mesoporous carbon
monolith, represented by the grey shell in Fig. 8d) sep-
arated by an ultrathin, pinhole-​free polymer electrolyte
layer145 (for example, poly(phenylene oxide), represented
by the blue shell in Fig. 8d). This structure allows for
separate electrical connections to the carbon and sulfur
interpenetrating electrode networks, which are essential
for 3D layered anode–electrolyte–cathode structures to
find use in EES systems (Fig. 8e). By folding and inte-
grating the nanoscale electrochemical components into
interpenetrating networks, the resultant 3D architecture
has a substantially decreased footprint area with more
efficient volume packing than conventional EES devices
using planar stacked layers. EES devices formed from
NAtuRe RevIews | MATERiAlS
Reviews
these 3D tri-​continuous networks can deliver capacities
about three orders of magnitude higher than those of
2D planar architectures with the same dimensions and
footprint area44,143. Despite proof-​of-concept demon-
strations, such 3D tri-​continuous architectures are still
in the early stage of research. Considerable challenges
remain in the efficient production of such elaborate
tri-​continuous network architectures.
Outlook
3D hierarchical porous conductive scaffolds offer inter-
penetrating transport pathways for electrons and ions,
which ensure highly efficient charge delivery to and
from the electrodes. These transport routes are neces-
sary to translate the extraordinary performance achieved
by nanoscale materials into macroscopic electrodes
with high mass loading. The ability to increase the mass
loading of the active materials without compromising
the charge (energy) storage performance is essential
not only for capturing the merits of new generations
of high-​performance electrode materials in practical
devices but also for pushing the limit of traditional
electrode materials by reducing the relative ratio of the
passive overhead. These improvements will increase
the overall energy density and power density of the
device, regardless of the type of active material. In
addition to the rapid charge transport kinetics, these
3D structures often feature ductile frameworks with
compliant mechanical properties, which are required
to withstand the large volume changes and stresses in
high-​c apacity, conversion-​t ype electrode materials
during charge/discharge processes to ensure long-​term
cycling stability. Alternatively, a rational design of a 3D
battery with tri-​continuous anode–electrolyte–cathode
layers can further reduce the macroscopic diffusion dis-
tance between the electrodes to ensure ultrahigh rate
capability without compromising their capacity.
Despite intensive research efforts and considerable
progress to date, challenges remain to be addressed to
advance the EES technologies beyond the limits of the
current systems. First and foremost, to simultaneously
achieve high-​energy and high-​power requires the dis-
covery of new materials, chemistries and storage mech-
anisms, such as interfacial ion storage or intercalation
pseudocapacitance. Second, improvements in electrical
and ionic conductivities are essential to capitalize on the
potential of new generations of electrode materials in
commercial devices with high mass loading. The afore-
mentioned 3D electrodes could provide a pathway for
high specific capacity and power at high mass loading,
breaking the energy–power limit of current EES systems.
Additionally, decoupling the transport and accommoda-
tion of ions from that of electrons in separate phases of
a composite could promise a unique interfacial storage
mechanism that may overcome the intrinsic limitation of
traditional electrode materials and mitigate the trade-​off
between the energy density and power density146. Third,
many high-​capacity electrode materials (including Si,
S and Li) are plagued by large volume changes and struc-
tural disintegration, leading to the loss of physical or
electrical contacts and rapidly degrading capacity over
repeated charge/discharge cycles. With the integration of
volume 4 | JANUARY 2019 | 57
Reviews

these materials with 3D porous architectures, abundant
empty space and a compliant backbone could mitigate
the volume change problem. To this end, characteri-
zation techniques (for example, in situ high-​resolution
TEM, in situ atomic force microscopy, in situ X-​ray
spectroscopy, in situ NMR spectroscopy, cryo-​electron
microscopy and transmission X-​ray microscopy)32,147–153
could visualize electrochemical processes in real time
and unravel the electrochemical mechanisms to help
formulate guiding principles for material development
and electrode design. Fourth, with the development of
high-​capacity EES devices that can store an increas-
ing amount of energy, safety is a matter of increasing
concern. When energy is released unintentionally, the
cascading thermal runaway may lead to rapid energy
release and catastrophic consequences154,155. To this end,
solid-​state electrolytes and separators with high thermal
stability may combat overheating, internal shorting, fires
and explosions154.
Last but not least, the scalable and cost-​effective pro-
duction of EES devices with elaborate 3D architectures
is challenging. New processes and approaches need to
be developed for the fabrication of high-​mass-loaded
and dense electrodes with favourable 3D architectures.
Fabrication technologies such as 3D printing and holo-
graphic patterning offer a fast, scalable and low-​cost
method for production by design. In another strategy,
biological materials can be used as templates for the
production of ultrathick electrodes with 3D hierarchical
porosity156. To further improve the volumetric perfor-
mance of electrodes, mechanical-​compression-assisted
processes (for example, cold isostatic pressing or spark
plasma sintering) may be applied to increase the packing
density (1.5–1.8 g cm−3) of the thick electrode (thickness
up to 1.0 mm)157,158. The development of manufacturing
processes to fabricate semi-​solid Li-​ion batteries using
ultrathick electrodes that can remove more than 80% of
the inactive material will also provide an effective way to
enhance device performance159. Together, innovations in
active material discovery, electrode architecture design
and manufacturing technologies will be necessary to
realize EES systems with superior energy and power
density and to meet the insatiable demand for more
energy and power.
Published online 17 December 2018

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Acknowledgements
X.D. acknowledges the partial financial support from the
National Science Foundation DMR1508144. Y.H. acknowl-
edges the financial support from the National Science
Foundation EFRI-1433541. H.S. and I.S. thank the Deanship
of Scientific Research at King Saud University for its funding of
this research through grant PEJP-17-01. J.Z. acknowledges
the Fundamental Research Funds of the Central Universities
(no. 531107051078) and the Double First-​Class University
Initiative of Hunan University (no. 531109100004).
Author contributions
X.D., H.S. and J.Z. co-​w rote the article. H.S. and J.Z.
researched data for the article. All authors made substantial
contributions to the discussion of the content and reviewed
and edited the manuscript before submission.
Competing interests
The authors declare no competing financial interests.
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