Imran Shakir

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 ion transport (and storage) in active electrode materials.
electrical vehicles and portable electronics has motivated The essence of energy storage is, in fact, charge storage
intense research efforts in developing high-performance in the form of ions in the electrode material. In super-
electrochemical energy storage (EES) devices. At the capacitors (also called electrochemical capacitors), the
fundamental level, all EES devices involve the shuttling energy is stored as adsorbed ionic species at the interface
and storage of ions between two electrodes, coupled with between the porous carbon electrode and the electrolyte
the flow of electrons in an external circuit. As a result, the (Fig. 1b). The ions are rapidly delivered to the electrode
electrodes must efficiently deliver a sufficient number of surface through a liquid electrolyte, and the electrons
ions into the electrode and a sufficient number of elec- are rapidly transported through the highly conductive
trons to the external circuit. An ideal EES device has the carbon electrode to an external circuit. As a result, super-
ability to store a large amount of energy (that is, a high capacitors typically exhibit rapid charge or discharge
energy density) and be charged and discharged rapidly behaviour with a high power density (~10 kW kg−1).
(that is, a high power density)1–8. However, the total number of ions that can be stored on
There are four types of EES device — capacitors, the surface is limited and thus the overall energy density
supercapacitors, batteries and fuel cells — each with is low (≤15 Wh kg−1) (Fig. 1a).
merits and limitations (Fig. 1a). Among them, fuel cells In a battery, the ions are transported and inserted
promise ultrahigh energy density but are limited by slow into the electrode, where redox reactions occur within
kinetics (that is, low power density) and the need for the active component of the electrode at a given electro-
costly precious metal catalysts. Capacitors are limited by chemical potential. Therefore, the energy is stored in the
their extremely low energy density and are generally not bulk volume of the electrode (Fig. 1c) and enables high
suitable for mobile power supply applications. Therefore, energy densities (≥100 Wh kg−1). However, as a conse-
batteries and supercapacitors are the primary EES tech- quence of the slow kinetics of solid-state ion diffusion
nologies on the market today. Batteries offer high energy and low electronic conductivity of most electrode mate-
density but moderately low power density, while superca- rials, the charge or discharge rate is low, leading to a low
pacitors provide the opposite: superior power density but power density of ≤1 kW kg−1 (Fig. 1a). For many applica-
*e-mail: xduan@
chem.ucla.edu with limited energy density9–13. Despite the striking dif- tions, such as electric vehicles, a high-power device that
https://doi.org/10.1038/ ferences, batteries and supercapacitors share fundamen- can store and release energy quickly (quick charge and
s41578-018-0069-9 tal processes involving coupled electron transport and fast acceleration) without compromising high energy
NAtuRe RevIews | MATERiAlS volume 4 | JANUARY 2019 | 45

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

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

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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- design barriers by creating functional architectures with
cations81,82. In this approach, a printable ink consists well-controlled structural parameters by design. The
of GO and graphene nanoplatelets, which can pro- capability of designing and fabricating EES devices with
vide improved electrical conductivity for the printed improved charge transport opens up opportunities for
GO–graphene nanoplatelet composite without det- high-performance EES devices.
rimental loss of its surface area. With the specifically
engineered macro-porosity, extremely thick electrodes Holey graphene framework. Traditionally, the per-
(for example, 1 mm) with excellent ion transport can formance of a supercapacitor electrode is evaluated by
be produced. These electrodes deliver 90% capacitance its gravimetric performance, but its volumetric perfor-
retention when the current density is increased from mance is an important metric for applications in which
0.5 A g−1 to 10 A g−1 (ref.82). The high power densities volume is at a premium (for example, portable electron-
(>4 kW kg−1) of these ultrathick electrodes are equal to ics)95–101. For most electrodes, there is a trade-off rela-
or exceed those of thinner electrodes with thicknesses tionship between gravimetric (specific) capacitance and
10−100 times smaller. The excellent electrochemical volumetric capacitance. More specifically, highly porous
behaviour and rate capability can be attributed to the electrodes allow rapid ion diffusion and hence show high
3D-printed macro-architecture, which enables fast gravimetric capacitance, but the low packing density of
ion diffusion in the thick electrode. As such, this work the material causes a low volumetric capacitance. An
demonstrates how 3D printing can overcome traditional 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-
a Graphene framework b Holey graphene framework
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
c d F cm−3) because of their high density but show modest
2.5 GF GF gravimetric capacitance (<170 F g−1)100,103. This trade-off
Phase angle (degree)
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 model system for probing the susceptibility of the rate
at a practical level of mass loading is an important performance to the electrode design because the overall
step towards commercial applications owing to the rate capability is dictated not by ion transport inside the
reduced ratio of the mass of passive components to T-Nb2O5 nanoparticles but by insufficient delivery of
the mass of active materials34. ions to the T-Nb2O5 surface. Composites with differing
porosities were prepared (Nb2O5/GF for a Nb2O5 and
3D hybrid electrodes GF composite and Nb2O5/HGF-0.5, Nb2O5/HGF-1.0
3D porous structures are attractive scaffolds for active and Nb2O5/HGF-2.0 for Nb2O5 and HGF composites
electrode materials because of their excellent charge obtained by etching in H2O2 for 0.5, 1.0 and 2.0 hours,
transport kinetics9,70,79,86,104; more specifically, the scaf- respectively) to evaluate the impact of porosity on the
folds ensure efficient charge delivery to the active charge transport and energy storage performance9.
materials to fully utilize their charge (energy) storage Compared with the macroporous electrode without in-
capability and realize high-energy and high-power- plane nanopores (Nb2O5/GF), the 3D HGF composite
density energy storage (Table 1). Moreover, the mechan- with optimized nanopores (Nb2O5/HGF-2.0) shows
ically strong hierarchical porous architectures of carbon enhanced specific capacity at a given charge/discharge
networks can accommodate large volume changes and rate9. The difference widens with increasing charge/dis-
mitigate mechanical stress within the electrode, enabling charge rate (Fig. 5c). For example, at a high rate of 100 C
long-term cycling stability of EES systems36,67,105. (1 C corresponds to complete charge or discharge in
1 hour), the Nb2O5/HGF-2.0 electrode delivers a specific
HGF integrated with high-power-density materials. capacity (75 mAh g−1) 2 times higher than that of the
By incorporating orthorhombic-p hase niobia Nb2O5/GF electrode (35 mAh g−1). This enhanced rate
(T-Nb2O5) nanoparticles106 into 3D HGF or GF scaf- capability is attributed to the decrease in ionic resistance
folds, composite architectures with improved power in the HGF as the pore size increases. Specifically, an
capability can be fabricated9 (Fig. 5a–c). With an intrin- increase in pore size from 0 nm to 2.7 nm decreases the
sically high rate capability, T-Nb2O5 is an interesting 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.

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.

Reviews
Graphene-foam-based hybrid electrodes. 3D graphene In particular, the shear-thinning behaviour of aqueous

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

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

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
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

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

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

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

Hierarchical 3D electrodes for

NAtuRe RevIews | MATERiAlS volume 4 | JANUARY 2019 | 45

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Energy density (Wh kg–1)

NAtuRe RevIews | MATERiAlS volume 4 | JANUARY 2019 | 47

a Battery device b The impact of mass loading

material capacity (%)

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

48 | JANUARY 2019 | volume 4 www.nature.com/natrevmats

a with this deposition system80. Finally, the electrospun

3D printing of graphene microlattices. 3D printing

NAtuRe RevIews | MATERiAlS volume 4 | JANUARY 2019 | 49

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

1.5 itance and high volumetric capacitance while retaining

Specific capacitance (F g–1)

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

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

11 139 1.6 234

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

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

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

NAtuRe RevIews | MATERiAlS volume 4 | JANUARY 2019 | 51

Speciﬁc capacity (mAh g–1)

j k l Speciﬁc capacity (mAh g–1)

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Graphene-​foam-based hybrid electrodes. 3D graphene In particular, the shear-​thinning behaviour of aqueous

NAtuRe RevIews | MATERiAlS volume 4 | JANUARY 2019 | 53

becomes increasingly important. The composite elec-

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Specific capacity (mAh g–1)

Coulombic effiiciency (%)

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a Composite b Thin film c Interdigitated d 3D network

e 3D tri-continuous electrode assembly

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

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

Graphene-foam-based hybrid electrodes. 3D graphene In particular, the shear-thinning behaviour of aqueous