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Nature-Inspired Electrochemical Energy-Storage Materials

Review
and Devices
Hua Wang, Yun Yang, and Lin Guo*

Nature-inspired strategies have been

Currently, tremendous efforts are being devoted to develop high-performance proposed recently as novel and effective
electrochemical energy-storage materials and devices. Conventional elec- routines to address these challenges.
trochemical energy-storage systems are confronted with great challenges to (1) Specifically, the limited availability
of mineral resources could hardly sat-
achieve high energy density, long cycle-life, excellent biocompatibility and
isfy the booming requirement and sub-
environmental friendliness. The biological energy metabolism and storage sequent production quantity of energy-
systems have appealing merits of high efficiency, sophisticated regulation, storage devices for long time, and will
clean and renewability, and the rational design and fabrication of advanced necessarily lead to their increasing
electrochemical energy-storage materials and smart devices inspired by price.[15,16] Moreover, the non-biodeg-
nature have made some breakthrough progresses, recently. In this review, radability of current energy-storage
devices after their service lifetime will
we summarize the latest developments in the field of nature-inspired elec- bring about tremendous electronic gar-
trochemical energy-storage materials and devices. Specifically, the nature- bage. Thus, renewable, cheap and envi-
inspired exploration, preparation and modification of electrochemical ronment-friendly energy-storage related
energy-storage related materials including the active materials, binders, and materials are greatly desired to substitute
separators are introduced. Furthermore, nature-inspired design and fabrica- current components.[12,17–26] In nature, its
energy conversion and storage systems
tion of smart energy-storage devices such as self-healing supercapacitors,
have been evolved for billions of years,
supercapacitors with ultrahigh operating voltage, and self-rechargeable bat- and spawned highly efficient and well
teries are also discussed. The review aims to provide insights and expanded suited cellular respiration machineries
research perspectives for further study in this exciting field based on our in living organisms for external energy
comprehensive discussions. assimilation, metabolism and distribu-
tion.[27] In recent years, inspirations have
been taken from nature to fabricate bio-
molecule-based electrode materials from
1. Introduction renewable biomass.[28–32] For example, inspired by the elec-
tron shuttles functioning in extracellular electron transfer via
Rechargeable batteries and supercapacitors, as promising reversible redox-cycling, man-made electrode materials with
energy storage devices, are drawing much attention due to their similar active functional groups have been explored.[33,34] In
long cycle life, high energy density and columbic efficiency, as our newly reported work, supercapacitor employing redox-
well as low maintenance.[1–8] As they are being considered as active biomolecule as the faradic-type active material could
a dominant energy-storage technology to sustainably power even obtain a higher energy density than those of previous
various potable electronics and large electric vehicles in our transition-metal-based supercapacitors.[35] (2) Another issue
modern society, higher requirements are raised for current encountered by current energy-storage system arises from
state-of-the-art rechargeable batteries and supercapacitors in the laborious preparation processes of their energy-storage
the aspects of electrochemical performance, fabrication cost, materials which usually adopt extreme conditions. In bio-
sustainability, environmental friendliness and intelligent appli- logical systems, assembly of complicated micro-organelles
cation, and solving these issues has become a crucial research are precisely controlled with the aid of biotemplates. By mim-
subject.[9–14] icking the bio-assembly processes or utilizing appropriate
biotemplates, facile preparation of energy-storage materials
in mild conditions has been achieved.[36–44] (3) In recharge-
able batteries and supercapacitors, the architecture of active
Dr. H. Wang, Dr. Y. Yang, Prof. L. Guo
School of Chemistry and Environment materials always determines their cycle life and rate per-
Key Laboratory of Bio-Inspired Smart Interfacial formance.[45–48] While the abundant examples of natural
Science and Technology of Ministry of Education structures with known stableness, geometry configuration,
Beihang University surface wettability and mechanical property provide clues
Beijing 100191, P. R. China
E-mail: guolin@buaa.edu.cn
for rational design of nanostructured active materials with
desired performance.[49–63] (4) What’s more, nature-inspired
DOI: 10.1002/aenm.201601709 routines are also useful for rational design of ideal binders

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and separators with enhanced electrochemical performance.

Review

(5) Further, exploitation of versatile smart energy-storage sys- Hua Wang is an associate
tems with artificial intelligence is of great scientific and tech- professor in the School of
nical significance in meeting the advanced demands in wide Chemistry and Environment
applications.[64–73] By mimicking some natural features, e.g., at Beihang University. He
self-healing ability of skin, self-rechargeable capability, some received his Ph.D. degree
advanced energy-storage devices with similar features have in Materials Science and
been obtained.[74–80] Engineering from Beihang
In this review, we mainly focus on the typical progress in University under the super-
this emerging field of nature-inspired design and fabrication vision of Prof. Lin Guo in
of energy-storage related materials and devices. Firstly, nature- 2012. Then, he worked as a
inspired exploration, preparation and modification of active research fellow at Nanyang
materials are introduced. Secondly, novel and modified binders Technological University
and separators with enhanced performance by taking the inspi- (NTU) for 2 years. His research interest is development
ration from nature are also introduced. Then, nature-inspired of advanced nanomaterials for energy conversion and
design and fabrication of smart energy-storage devices are dis- storage, including lithium/sodium ion batteries, photo­
cussed. Finally, insights and expanded research perspectives for catalytic water splitting and water purification.
further study are also suggested.
Yun Yang received her Ph.D.
degree in Chemical and
Biomedical Engineering
2. Nature-Inspired Energy-Storage
from Nanyang Technological
Related Materials University in 2015. She is
Functional materials are the fundamental components within currently a postdoctor in
the rechargeable devices, which determine the characteristic Prof. Lin Guo’s group in
performances of rechargeable devices, i.e., the specific capaci- Beihang University. Her
tance, rate performance, coulombic efficiency, cycle life.[81–88] research interests focus
In a standard rechargeable battery, energy-storage relevant on microbial fuel cells and
materials including electrochemically active materials, binder nature-inspired energy-
and separator are usually adopted.[89–92] Inspired by natural sys- storage systems.
tems, scientists have made great progress in the development
of these materials in recent years.[93–96] More specifically, some Lin Guo is a professor
redox-active molecules and electron shuttles belonging to the and vice dean of School of
biological extracellular electron transfer chains for active respi- Chemistry and Environment
ration have inspired the construction of active electrode mate- in Beihang University.
rials containing identical redox-active groups.[93] Additionally, He received his Ph.D. in
by mimicking some natural architectures and unique biological Materials Science and
processes, e.g., biomineralization and biotemplate-directed Engineering from Beijing
self-assembly, novel strategies to prepare and modify the active University of Institute of
materials have been developed and proved to be effective.[94] Technology (BIT) in 1997. He
Besides the active materials, some natural intrinsically adhesive worked as a visiting scholar
materials or their artificial derivatives have been employed as in Hong Kong University
binders in the energy-storage systems and displayed extraor- of Science and Technology
dinary properties.[95] Moreover, the poor wetting capabili- (HKUST) in 1999. He worked in Dresden Technology
ties of conventional separators have been improved by some University with Humboldt Fellowship for 2 years. His
nature-inspired approaches and achieved high-performance research interests include synthesis and characterization of
batteries.[96] sophisticated nanomaterials, high-strength nanomaterials
with light weight, and functional nanomaterials for energy
storage.
2.1. Electrochemically Active Materials

Active electrode materials are the most important components

in batteries or supercapacitors by dominating the electrochem-
ical properties of these energy-storage devices.[97–101] Thus, the
energy density, sustainability, biocompatibility and cost of active
materials have been taken intensive attention, recently.[81,102–104]
The development of novel active materials, as well as their
synthesis methods and modification strategies are widely
pursued.[76,100,105–111]
2.1.1. Nature Inspired the Exploration of Electrochemically
Active Materials for Energy Storage
Recently, requests for green and naturally abundant materials
in energy storage have been escalating in society.[112] In this
respect, inspired by the metabolic process resided in organisms
relying on ions transport and energy exchanges of biomolecule

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with specific functional groups, some natural biomass and juglone/polypyrrole (PPy) biocomposite, which could realize

their derivatives enable the desirable design of more sustain-
able energy-storage devices.[28,113] Organic electrode mate-
rials such as carbonyl, carboxy, quinone, or pteridine-based
compounds have been demonstrated to be bio-inspired active
materials.[114,115]
For example, the electro-active carbonyl compounds mim-
icking biological quinone cofactors which can be obtained from
biomass through eco-friendly processes are intriguing can-
didates for such electrode materials.[13] In our recent work, a
biomolecule, named juglone which can be extracted from waste
walnut epicarp, with redox-active quinone carbonyl groups
has been proved to be capable of reversible electron trans-
porting and sodium ion insertion/desertion (Figure 1a–c).[116]
A rationally designed juglone/reduced graphene oxide (rGO)
hybrid electrode without binder and additional conduc-
tive agent was fabricated through a scalable and facile self-
assembly approach. Non-covalent immobilization of juglone
molecules on rGO via π–π interactions was revealed by optical
and photoelectron spectra, which could suppress the dissolu-
tion of organic materials in the electrolyte and elevate both the
sodium ion accessibility and the conductivity of the electrode
(Figure 1b).[116] Extraordinary energy-storage performances,
e.g., high specific capacity (gravimetric capacity density up to
305 mA h g−1), excellent cyclic stability (retains 280 mA h g−1
after 100 cycles) and rate capability were achieved with this sus-
tainable biomolecule-based electrodes (Figure 1c).[116] Moreover,
facilitated by integrated electronic circuit design, an integrated
energy-storage cable was also succesfully fabricated based on
Review
simutaneous energy transmission and storage, and enable
stable electricity supply against occasional power interupp-
tion.[71] Another redox-active biomolecule, named lawsone
(2-hydroxy-1,4-naphthoquinone) originating from henna, has
the same molecular weight but dinstinct chemical structure
with juglone, hence possesses a much lower redox potential.[35]
The vesatility in redox potentials of biomolecules is benefical
to rational design of composite electrode with desired electro-
chemical property. An transition-metal-free asymmetric super-
capacitor (ASC) is successfully fabricated with a PPy deposited
carbon fiber being the capacitor-type positive electrode, and a
conjugated lawsone/PPy biocomposite deposited carbon fiber
as the faradic-type negative electrode.[35] This biomolecule/
polymer composite based ASC shows comparable or even
higher energy densities compared to those of reported transi-
tion-metal-based ASCs.[35]
Other series of progresses have been made by the coopera-
tion of Park and Kang’s groups.[117–119] By carrying out in-depth
studies regarding the redox unit of pteridine derivatives, which
are essential components of ubiquitous electron transfer pro-
teins in cells, they demonstrated the possibility of applying
the pteridine systems with alloxazinic structure into lithium/
sodium ion rechargeable batteries. Heterocyclic molecules pro-
cessing a pteridine nucleus (1,3,5,8-tetraazanaphthalene, fused
complex of pyrimidine and pyrazine rings) are common redox
components in living organisms.[117–119] Among them, flavins
including flavin adenine dinucleotide (FAD), flavin mono­
nucleotide (FMN) and riboflavin are integral cofactors in cellular

Figure 1. a) Chemical structure of the Juglone molecule that can be derived from waste walnut epicarp. b) Schematic illustration showing the π–π
conjugation of the Juglone molecule with rGO nanosheets and the reversible sodium-ion insertion/extraction mechanism of the hybridized electrodes.
c) Capacity retention of Juglone/rGO electrode compared with rGO and Juglone electrodes at a current density of 0.1 A g−1. Reproduced with permis-
sion.[116] Copyright 2015, Wiley. d) In the left, flavins work as a redox cofactor to facilitate energy storage from nutrients into high-energy ATP in organ-
isms. In the right panel, inspired by biological energy transduction, flavins are proposed to serve as an active material for electrochemical lithium ions
storage. Reproduced with permission.[117] Copyright 2013, Wiley. e) The electrochemical redox reaction of flavin molecule with reversible lithium ion
insertion/extraction. Reproduced with permission.[119] Copyright 2014, Nature Publishing Group.

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redox reaction chains for energy metabolism (Figure 1d). The
Review
functionality of flavins relies on their redox-cycling occurring at
the diazabutadiene of the isoalloxazine moiety. Based on these
analysis of the electrochemical energy-storage mechanism
of cellular metabolism, the flavin-based electrodes were used
to fabricate sustainable lithium ion batteries, and they could
reversibly store and release two lithium ions and two electrons
per formula unit revealed by ex-situ characterization and den-
sity functional theory (DFT) calculations (Figure 1e). Further-
more, they found that a relatively simple molecule with shorter
side chain than flavins, called lumiflavine (7,8,10-Trimethyl-
isoalloxazine), had a theoretical capacity as high as 209.18
mA h g−1, and its actually tested gravimetric capacity was
174.32 mA h g−1, which was much higher than 105.88 mA h
g−1 of riboflavin with enhanced stability.[117–119] Then, through
the further molecular tailoring, the optimized pteridine-based
active materials immobilized onto conductive scaffolds through
non-covalent bonding showed excellent electrochemical perfor-
mance, could deliver a gravimetric energy density up to 533 W
h kg−1 within 1 h and 348 W h kg−1 within 1 min, as well as
high cyclability retaining 96% of the initial capacity after 500
cycles at 10 A g−1.[117–119] Clearly, these reports have shown
that the biological energy metabolism and storage machin-
eries can provide guidelines for the rational design of novel
sustainable energy-storage systems beyond the conventional
electrode materials. In addition, various unexplored redox mol-
ecules from biological energy transduction systems can provide
unlimited opportunities to explore sustainable active materials
with superior performances.
Furthermore, the rational design of active materials by
taking the combined consideration of the nature-derived pre-
cursor and nature-inspired function should be paid attention
to.[120] In particular, biomass-derived macroporous carbon
networks are appealing due to their superior electrochem-
ical performances, which were fabricated via carbonizing/
activiting the nature-derived precursors to perserve or tailor
their instrinsic structrues and compositions.[121] The unique
architecture and composition of natrual precursor, which
support well the physiological functions in their living organ-
isms, favored the energy-storage activities when used in an
energy storage device with or without modification.[120–123]
For example, the chicken eggshell membrane possesses a
uniform microporous structure to allow oxgen exchange
for respiration of baby chicks, and contains rich nitrogen
element, making it a promising energy-storage material
precursor.[124] Mitlin’s group carbonized the eggshell mem-
brane and obtained a 3D macroporous carbon film com-
posed of interwoven connected carbon fibers containing over
8% nitrogen.[124] This film showed an exceptional specific
capacitance of 297 F g−1 and excellent cycling stability, which
should be ascribed to their unique structure and chemistry
of the material. In another typical case, bacterial cellulose,
having 3D interconnected nanofibrous networks, was utilized
as both precursor and template to synthesize N-doped acti-
vated carbon and carbon/MnO2 composite as negative and
positive electrode materials for asymmetric supercapacitor,
respectively.[125] The as-assembled device obtained a consid-
erably high energy density of 63 W h Kg−1 and maximum
power density of 227 KW Kg−1.
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2.1.2. Nature Inspired the Preparation of Electrochemically Active
Materials for Energy Storage
Biomineralization and biotemplate-directed self-assembly are
natural processes that usually work together to produce intri-
cately structured inorganic materials in biological systems.[126]
By mimicking these biological processes, novel strategies have
been developed to prepare the active materials.[127–131] It has
been known that genetically engineered molecules can interact
with metallic precursors under mild conditions and create inor-
ganic nanostructures with precise shape, size, and phase con-
trol.[132] Thus, biological molecules and organisms including
polysaccharides, proteins, viruses, DNA, peptides have been
employed to prepare nanomaterials for energy storage applica-
tion.[133–135] Among many different kinds of organic templates
for nanomaterial fabrications, M13 viruses have been paid spe-
cial attention because of their unique properties such as a high
aspect ratio of geometry with diameter around 6 nm and length
about 880 nm, genetic tunability of surface protein, and easy
replicability.[136]
Belcher and co-workers carried out some pioneered research
work by using M13 viruses as biotemplate for fabrication of dif-
ferent electrode materials. In 2006, they reported the successful
synthesis of self-assembled Co3O4 nanowires and hybrid Au-
Co3O4 nanowires by using M13 virus as templates under benign
conditions (Figure 2a).[136] Owing to their large surface areas,
structural integrity and dense packing, the Co3O4-based elec-
trodes exhibit superior electrochemical properties when used
in lithium ion batteries.[136] Moveover, by combining this bio-
templated synthesis at the peptide level and controllable two-
dimensional (2D) assembly of viruses on polyelectrolyte films,
they produced assembled monolayer of Co3O4 nanowires on a
free-standing and flexible film of poly(ethylene imine)(LPEI)/
poly(acrylic acid) (PAA).[136] The thin and flexible lithium ion
batteries based on this self-assembled Co3O4monolayer/ poly-
electrolyte/Li foil could deliver 94% of its theoretical capacity at
a rate of 1.12 C.[136]
Then, in 2008, they extended this synergistic method of bio-
templated synthesis and self-assembly to fabricate microbattery
electrodes (Figure 2b). In this microelectrode configuration, the
virus-templated Co3O4 layer serving as active materials was syn-
thesized on top of microscale islands of polyelectrolyte multi-
layers comprising LPEI/PAA on polydimethylsiloxane (PDMS)
stamp.[134] These microelectrodes could be easily stamped onto
various rigid or flexible substrates to fabricate microbatteries
with interdigitated or 3D architectures.[134] After stamping them
onto platinum microband current collectors, the assembled
sample was tested against a Li foil counter electrode and exhib-
ited full electrochemical functionality.[134] Further, other anode
materials such as gold and silver noble metals as well as their
alloy nanowires have been successfully fabricated by similar
bio-templated method for lithium ion batteries.[137]
Belcher and co-workers also applied this approach of biotem-
plate-directed self-assembly and biomineralization in the prepa-
ration of cathode materials for rechargeable batteries.[133,138]
They utilized genetically engineered M13 virus for single-
walled carbon nanotube (SWCNT) binding and amorphous
FePO4 nucleation, and the resulted bio-FePO4-CNT composite
exhibited excellent electrochemical performance comparable to
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Figure 2. a) Schematic illumination of the virus-templated synthesis and self-assembly of Co3O4 and Au-Co3O4 nanowires for Lithium ions batteries.
Reproduced with permission.[136] Copyright 2006, American Association for the Advancement of Science. b) The design and manufacturing process
flow of virus-based microbattery electrodes. Reproduced with permission.[134] Copyright 2008, National Academy of Sciences.

conventional crystalline LiFePO4 and Na0.9FePO4 for lithium
ion batteries and sodium ion battery, respectively.[133,138]
Further, they utilized this virus-directed self-assembly
method in lithium-oxygen (Li-O2) batteries.[139] Typically, they
prepared three kinds of spinel oxide nanowires with different
compositions, MnxCo3–xO4 (x = 0, 1, 2) by using M13 viruses
as biotemplates (Figure 3a).[139] These nanowires had similar
geometrical scale and high aspect ratio with diameter around
50 nm and length about 1 µm (Figure 3b). When used these
MnxCo3−xO4 nanowires in Li−O2 batteries, they showed higher
specific capacities than those of carbon electrodes. After further
engineering Co3O4 nanowires through thermal treatments and
modification with Ni nanoparticles, the round-trip efficiency of
Li−O2 battery was improved from 68.5% to 75.1% (Figure 3c).
Moreover, the cycle life of such heat-treated Ni-Co3O4 nano­
wires could also be prolonged from 27 cycles to 48 cycles with
a fixed capacity of 2000 mA h g−1 at 1 A g−1 (Figure 3d). These
biologically formed nanowires demonstrated a simple and mild
route to prepare cost-effective nanostructured electrodes for
high performance energy-storage devices.[139]
Besides the rechargeable batteries, the nature-inspired
strategies have also been used to prepare active materials in
supercapacitors. In a typical case, E. coli cells were employed
as the template and starting material for fabrication of hierar-
chical carbon materials with nanoscale to microscale porous
structures and rich foreign atoms.[140] Firstly, the E. coli cell
suspension was mixed with a FeCl3 aqueous solution to form
the bacteria/Fe3+ complexes. After adding GO solution into the
bacteria/Fe3+ complexes, the GO/bacteria hybrids were gradu-
ally obtained. Then, with the freeze-casting and pyrolysis steps,
a hierarchical carbon electrode material was prepared, which
showed a desirable capacitance of 327 F g−1, large power den-
sity and good cycle stability benefitted from its structural and
compositional features.
In addition to virus and bacteria, other biological molecules
which can interact with metallic precursors under mild condi-
tion have also been used to synthesize electrode activemate-
rials, demonstrating that the basic biological principles can be
applied in the rational design and fabricate of nanoscale battery
components.[132]
2.1.3. Nature Inspired the Modification of Electrochemically Active
Materials for Energy Storage
Using appropriate strategies to modify the active materials is
a useful way to improve their electrochemical performance.[141]
Typically, alloy-type anode materials such as Si, Sn and Ge, etc.
are usually considered as promising substitutes of the con-
ventional graphite anode in lithium ion batteries due to their
several times higher theoretical gravimetric capacity than its
carbonaceous counterpart, and lower potential of lithium ions
intercalation.[142,143] However, the practical application of these
active materials for lithium ion batteries is still hampered by

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Figure 3. a) Schematic showing the M13 virus-directed synthesis of multicomponents transition metal (Co, Mn) oxide nanowires. b1-b3) TEM images
of M13 virus-templated MnxCo3–xO4 (x = 0, 1, 2) nanowires. b4) STEM image of Ni−Co3O4/Co(OH)x nanowires overlapped with a corresponding ele-
mental mapping of Co and Ni. c) The first galvanostatic cycle of Li−O2 batteries with Co3O4/Co(OH)x (orange dash line), heat-treated Co3O4 nanowires
(orange straight line), and heat-treated Ni−Co3O4 nanowires (violet line) conducted with a fixed discharge capacity (2000 mA h g−1c, “c” represents for
bare carbon electrode; 200 mAh g−1c+NWs, “c+NWs” stands for electrode made of MnxCo3–xO4 nanowires) at 1 A g−1c (100 mA g−1c+NWs). d) The cycle
life (fixed discharge capacity of 2000 mA h g−1c, 200 mA h g−1c+NWs) of heat-treated Co3O4 NWs (orange circles) and heat-treated Ni−Co3O4 NWs (violet
triangles) performed at 1 A g−1c (100 mA g−1c+NWs) under 1 atm of O2. The electrodes were composed of 8 wt% of carbon and 72 wt% of biotemplated
NWs. Reproduced with permission.[139] Copyright 2014, American Chemical Society.

their poor cyclabilities owing to the particle fracture and loss of
electrical contact caused by the drastic volume change during
lithiation/delithiation process.[144,145] Constructing unique
nano-architectures of these materials, and hybridizing them
with flexible carbon materials have been proved to be effec-
tive strategies to resolve the capacity fading problem.[47] In this
respect, by mimicking the structure of natural products with
fine-tuned allocations of embedded components, rationally
designing the nano-architectures of composite electrodes is an
effective route to improve their structure stabilities and long
electrochemical cycling life.[146]
For example, inspired by the structure of a pomegranate,
Cui’s group fabricated a hierarchically structured silicon
anode.[147] Inside this uniquely designed electrode, every sil-
icon nanoparticle was encapsulated by a conductive carbon
layer, hence enough interval spaces were reserved to allow the
lithiation/delithiation associated expansion and contraction
(Figure 4a). A relatively thick carbon layer then enclosed all the
hybrid nanoparticles in micrometer-size pouches. Such smart
electrode was superior in the following ways. (1) The primary
particle with nano-size was stable against fracture. (2) The
optimal space arrangement inside the electrode prevented
the conformation damage induced by lithium ions insertion/
desertion. (3) The carbon layer as the interconnection bridge
ensured the fast electron transfer inside the complex and sup-
ported the designed architecture. (4) It greatly restrained the
formation of solid-electrolyte-interphase (SEI) film on the outer
surface, thus decreased the total amount of SEI, and retained
the internal void space for silicon expansion. (5) It achieved the
high surface area and high tap density simultaneously. Just as
expected, this pomegranate-inspired electrode exhibited excel-
lent electrochemical performance. It could deliver an excellent
specific capacity of 1160 mA h g−1 even after 1000 cycles with
0.003% decay per cycle and a coulombic efficiency of over 99%.
For comparison, the bare silicon particles with carbon coating
but no internal void space showed large decay after 200 cycles
(Figure 4b).
In another study case, inspired by the geometry of bamboos
with periodic distribution of interior holes along the length and
graded pore structure at the cross section, Sun et al. reported

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Figure 4. Schematic of the pomegranate-inspired electrode for lithium ion battery. Three-dimensional view (top images) and simplified two-dimen-
sional cross-section view (bottom images) of one pomegranate microparticle before and after electrochemical cycling (in the lithiated state). b) Com-
parative capacity retention of the lithium ion batteries with silicon pomegranate-inspired electrode or other electrodes without void space tested under
the same conditions. Reproduced with permission.[147] Copyright 2014, Nature Publishing Group.

a bamboo-like multiscale, hierarchical carbon nanofiber
(Figure 5a,b).[148] As shown in Figure 5c, the as-prepared carbon
nanofibers were consisted of uniform discontinuous hollow
interiors and graded nanopores. Benefited from this unique
structure, the nanofiber exhibited superior mechanical dura-
bility and flexibility, and could provide a high surface area
accessible to the electrolyte and low ion-transport resistance.
An all-solid-state supercapacitor based on these nanofibers
achieved a high power and energy densities of 61.3 kW kg−1 and
2.37 W h kg−1, respectively, which were larger than or compa-
rable to those typical carbon-based active materials. In addition,
the supercapacitor was robust enough to work under different
mechanical deformation conditions without performance decay
(Figure 5d).
Besides mimicking the natural architectures, the nature-
derived materials with preserved intrinsic features is also used
to modify the active materials and improve their electrochem-
ical performance.[149–151] For example, Chung et al. developed
a free-standing carbonized sucrose-coated eggshell film with
microporous architecture, and used it to modify the sulfur
cathode. It could effectively suppress the polysulfide shuttling
in lithium-sulfur batteries, and stabilized the electrochemical
reaction within the cathode region, endowing the cells with a
high capacity of 1327 mA h g−1 and long-term stability.[150] In
another study, the wood fibers were harnessed for electrode
preparation, which are intrinsically soft, porous and multi-
channel structured. Hu’s group prepared a binder-free anode
consisting of electrodeposited Sn film on CNT-coated wood

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Figure 5. a) The graded structure of bamboos. b) Schematic of the bamboo-inspired nanostructure design. c) TEM image of bamboo-like carbon
nanofibers. d) CV curves and capacity retention of the all-solid-state supercapacitor under different mechanical deformations. Inserts are the photos of
the supercapacitor under four different deformations. Reproduced with permission.[148] Copyright 2015, American Chemical Society.

fiber for sodium-ion batteries, and achieved an initial capacity
of 339 mA h g−1 as well as superior cyclability.[151] The soft wood
fiber could effectively alleviate the mechanical stress during the
sodiation/desodiation process, and its porosity acted as an elec-
trolyte reservoir, facilitating efficient ion and electron transport.
2.2. Binders
With relatively low mass fractions, binder endows structural
integrity among the active materials, conductive additive and cur-
rent collector.[152] Compared with the abundant progress achieved
in developing active materials, binders has not attracted extensive
interests due to its intrinsic inactivity.[153] However, it has a signifi-
cant influence on the electrochemical performance of the energy-
storage devices, especially for the alloy-type anode materials with
high capacitance but large volume change during charge/dis-
charge.[76,154,155] An ideal binder should usually meet the following
prerequisites: (i) containing polar groups to provide strong adhe-
sion and high tensile strength at the interfaces between the active
materials, conducive additive and the current collector; (ii) acting
as dispersant to uniformly distribute the active materials and con-
ductive additive; (iii) don’t deteriorate the electrons transfer and
ions diffusion; (iv) physically and chemically stable in the electro-
lyte, as well as electrochemically stable under charge/discharge
cycles; (v) low-cost, safe and environmental-friendly.[95,156–158]
Polyvinylidene fluoride (PVDF) is the most widely used
commercial binder with superior electrochemical stability.[159]
However, its relatively weak adhesion capability and mechan-
ical stretchability restrain its wide applications, especially for
alloy-type anodes. Some natural polymers and their derivatives,
such as carboxymethyl cellulose (CMC), carbonyl-β-cyclodextrin
(C-β-CD), polyacrylic acid (PAA), amylopectin, gelatin and algi-
nate have been investigated as robust and green binders, and
exhibited great potential to substitute the conventional PVDF
binder.[152,160,161]
In a typical case, alginate, a major constituent of brown
algae and many aquatic microorganisms, is a copolymer of
many aquatic sumannuronic acid and L-guluronic acid resi-
dues (Figure 6a).[162] Containing carboxylic groups in each of
the polymer’s monomeric units makes it a promising binder
candidate especially for silicon based anode. Yushin et al. found
that the dry film made of alginate (commonly in a Na salt form)
exhibited ≈6.7 times higher stiffness than that of PVDF, and
the stiffness of alginate did not show obvious variation when
immersed into the electrolyte solvent, while the PVDF film
became nearly 50 times softer.[162] This strong stiffness of algi-
nate was supposed to be favourable for the electrochemical sta-
bilities of silicon anode by alleviating its large volume change
during the charge/discharge cycles. Moreover, the ellipsometry
studies showed that Na-alginate films exhibited no detectable
swelling in the electrolyte solvent vapors, while PVDF films

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Review
Figure 6. a) Photographs of giant kelp forest, from which the alginate can be derived. The insets are the chemical structure of mannuronic (left) and
guluronic (right) acids. b) Capacitance retention of the nano-silicon electrodes with Li insertion level fixed to 1200 mA h g−1. c) Cycling performance
of nano-silicon electrodes with alginate, CMC, and PVDF as binders at a current density of 4200 mA g−1. Reproduced with permission.[162] Copyright
2011, American Association for the Advancement of Science. d) Mussel; the inset is the chemical structure of dopamine inspired from the adhesive
mussel root protein. e) Structural formula of the polymer binders with catechol functional groups conjugated to well-known PAA, and alginate back-
bones. f) A graphical illustration of the silicon nanoparticles based anode. g) The cycle life of the silicon electrodes with Alg-C, Alg and PVDF binders
measured at a C/2 rate (2100 mA g−1). Silicon NPs: Super P: binder (by weight) = 60:20:20. Reproduced with permission.[167] Copyright 2013, Wiley.

attracted substantial amounts of carbonates from the vapor,
with a thicknesses change of ≈20%. The negligibly swellability
of the alginate film suggested a low level of polymer/electro-
lyte interaction, which might prevent undesirable access of the
electrolyte liquid to the binder/silicon interface. Owing to these
benefiting properties of alginate, the silicon/alginate electrode
exhibited excellent electrochemical energy storage proper-
ties. With lithium insertion capacity limited to 1200 mA h g−1,
it showed stable performance over 1300 cycles (Figure 6b).
At a small current density of 140 mA g−1, it delivered a spe-
cific capacity as high as 3040 mA h g−1, which was more than
8 times higher than the theoretical specific capacity of graphite
based electrode. More importantly, just as expected, it exhibited
largely enhanced stabilities compared with CMC and conven-
tional PVDF binders (Figure 6c).[162]
Some other polysaccharide binders with various chemical
structures were also studied to reveal the key factors determining
their performances. Three kinds of polysaccharides with dif-
ferent extent of structure branching were investigated as binders
in silicon/graphite-based lithium ion batteries, and amylopectin
with moderate branching outperformed amylose (straight
chains) and glycogen (highly branched chains).[163] The authors
speculated that amylopectin probably formed an optimal thick-
ness of polymer layer onto the electrode materials to allow suf-
ficient adhesion strength as well as unimpaired transportation of
Li+ throughout the electrode.[163] Later, Liu et al. proved that the
large number of polar hydroxyl groups in the biopolymer guar
gum (GG) could even effectively assist Li+ transfer to/from the
Si surface, when GG was applied as the binder for a Si nanopar-
ticle anode in lithium ion battery.[164] In a systematic study on
polysaccharide binders in Si anodes carried out by Jeong et al.,
superstructure and noncovalent interactions (including hydrogen
bonding and ion-dipole interactions) between binder and elec-
trode were summarized to be the crucial factors for promoting
the cycling capability of batteries.[165] Among a series of poly-
saccharide binders, xanthan gum showed superb function ben-
efitted from its double helical superstructure with trisaccharide
side chains as well as being electrostatically charged to allow ion-
dipole interactions.[165] Interestingly, such chemical structure of
xanthan gum resembles millipedes that have excellent adhesion
onto rough surfaces due to their numerous small legs attached
to the main trunk, which indicates the usefulness of bio-inspired
approach in exploration of binders. Polysaccharide binder like
gum arabic (GA) was also effective as binder for sulfur cathode in
lithium-sulfur batteries, which could buffer the volume change
and inhibit the shuttling effect of polysulfide during cycling.[166]
Furthermore, inspired by the mussel with adhesion proper-
ties even on wet surfaces, researchers found that a certain func-
tional group, namely catechol, worked as a decisive role in such
exceptional wetness-resistant adhesion (Figure 6d).[167] The wet-
ness-resistant adhesion can be very helpful for battery opera-
tions, because the battery components are bound with each
other in liquid environments. In view of this consideration,
Choi’s group conjugated adhesive catechol functional groups to
PAA, and copolymerized alginate backbones with high Young’s
moduli (Figure 6e). Due to the synergetic effects of the cat-
echol functional group with wetness-resistant adhesion and
the rigidity of polymer backbone with high mechanical stiff-
ness, the mussel-inspired binders endow silicon nanoparticles
electrodes with markedly improved battery performance com-
pared to bare PAA, alginate, as well as conventional PVDF
binders (Figure 6f,g).[167]

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Figure 7. Schematic illustrations of the silicon electrodes during the lithiation process employing the a) conventional and b) self-healing binders.
c) Surface morphology of the binder layer in the lithiated state (left) and selfhealed state after being left for five hours (right), especially the small cracks
indicated by the white arrows. Reproduced with permission.[168] Copyright 2013 Nature Publishing Group.

In another work, Bao’s group demonstrated that the self-
healing materials serving as binders had exciting performance
in rechargeable batteries.[168] Inspired by the biological sys-
tems with intrinsic self-repairing ability, a class of artificial
smart materials, called self-healing materials, which can repair
internal or external damages have been developed over the past
decade. As mentioned before, silicon anode materials with con-
ventional binders usually suffer from fast capacity decay and
short cycle-life owing to the extreme volumetric changes during
charge and discharge processes, which can cause cracking and
pulverization in the electrode (Figure 7a).[168] Compared with
conventional polymer binders, the self-healing material based
binder was stretchable and enabled spontaneous repair of the
mechanical damage and cracks in the electrode, which resulted
in more stably mechanical and electrical connections among
the silicon particles, and thus could increase its electrochemical
cycle life (Figure 7b,c). Just as expected, at a current density
of 0.4 A g−1, the silicon microparticle electrode based on this
self-healing binder could deliver a specific capacity as high as
2,617 mA h g−1 for the first cycle, which was about six times
higher than the theoretical capacity of graphite.[168] Moreover,
the electrode showed good cycling stability with the capacity
retention about 100% of their initial capacities after 20 cycles
compared with 14%, 27% and 47% of PVDF, CMC and alginate
based binders.[168]
Although binder is intrinsic inactive, it has remarkable influ-
ence on the electrochemical performance of the energy-storage
devices, especially for the cyclabilities of alloy-type anode mate-
rials. The exploring and designing of novel binders inspired by
the natural materials with intrinsic adhesiveness should be paid
special attention.
2.3. Separators
Separator, as a critical component of rechargeable batteries, is a
porous membrane placed between anode and cathode to prevent
the physical contact between the two electrodes while allowing
ion diffusion across it.[17,169,170] An ideal separator generally
requires excellent chemical and electrochemical stabilities,

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thermal stability, wettability, proper mechanical strength and polydopamine modified PE separator exhibited fast and fully

pore structure as well as low cost.[171] Among a number of sepa-
rators developed thus far, polyethylene (PE), polypropylene (PP)
and their copolymers are the most dominant ones for commer-
cial lithium ion batteries over the decades.[172] However, the
intrinsic hydrophobic property of these separators make them
suffer from a severe challenge of insufficient wettability in elec-
trolyte, which could directly suppress ionic transport through
the separators and shorten the cycle lifes of batteries.[173]
Inspired by some intense interfacial interactions mediated by
highly adhesive mussels, researchers identified that dopamine
molecule containing both catechol and amine groups can func-
tion in strong, versatile and wet-resistant adhesion, and they
employed polydopamine coatings for various applications.[96] In
a work reported by Choi’s group, a simple dipping of the PE
separator to modify it with polydopamine is proved to be effec-
tive to dramatically improve its compatibility with the liquid
electrolyte (Figure 8a).[174] Such one-step modification approach
in mild condition specifically increases the wettability without
side-effects appeared in previous coating strategies, e.g., pore
blocking of modified separator and subsequent impaired power
output, increased environmental burden due to the use of toxic
organic treating agents, elevated fabrication cost arising from
expensive modification process, additional demand of com-
plex instruments and manipulations for complicated modifica-
tion procedures. Mechanism studies revealed that the porous
morphology of the PE separator was intact after modification
with polydopamine, whereas the surface hydrophilicity was
significantly enhanced, i.e., the contact angle decreased from
108 ± 1.4° of bare sample to 39 ± 1.7° of modified one. The
Review
wetting in a variety of liquid electrolytes, and enabled one fold
higher ionic conductivity than that of bared PE film. Interest-
ingly, in the assembled half-cells (LiMn2O4/separator/lithium
metal) with modified PE separator, much higher rate perfor-
mance (84.1% capacity retention for modified film and 46.1%
capacity retention for bare film when the charge/discharge
current density increased from 1 C to 15 C) was obtained
(Figure 8b).
In addition, mussel-inspired polydopamine-coated separa-
tors have also been demonstrated to prolong the cycle life of
lithium metal anodes in lithium ion batteries by Choi’s group
(Figure 8c,d).[175] Lithium metal is one of the best anode mate-
rials, on account of its unprecedented theoretical capacity
(3860 mA h g−1) and electrochemical potential (–3.04 V vs
standard hydrogen electrode). However, it is less likely to form
a stable SEI layer on the surface of lithium metal, resulting in
the growth of lithium dendrites in an uncontrollable manner
during high-rate charging processes. The continual growth of
lithium dendrites can exhaust the lithium ions as well as the
electrolyte, which will cause poor cycling performance of the
batteries. Even worse, when lithium dendrites grow to a certain
extent, they often break away from the surface of lithium metal
and thereby induce a security threat. After using the mussel-
inspired polydopamine-coated separators, their enhanced elec-
trolyte uptake facilitate the uniform generation of lithium ionic
flux, together with enhanced adhesion between the separa-
tors and the lithium metal surface, which could suppress the
lithium-dendrite growth, and thus improve the capacity reten-
tion and safety of lithium metal based anodes (Figure 8c,d).

Figure 8. a) Schematic illustration of the mussel-inspired polydopamine surface treatment of PE using a simple dip-coating method. Dopamine
polymerizes in the aqueous solution at pH 8.5 and the resultant polydopamine-modified PE surface becomes hydrophilic. b) Rate capability of the bat-
teries with the PE separators before and after polydopamine surface treatment. Reproduced with permission.[174] Copyright 2011, Wiley. c) The cycling
performance of batteries with different separators. d) SEM images of lithium-metal electrodes disassembled from batteries using PE separators with
and without polydopamine treatment after the first cycle and 20 cycles. Reproduced with permission.[175] Copyright 2012, Wiley.

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Beside the modification of conventional separators, some during charge/discharge processes, and the polymeric flexible
Review

advanced biomass-based separators such as cellulose and its
composites with superior wettability and thermal stability, are
demonstrated as promising alternatives to polyolefin sepa-
rators for high-performance electrochemical energy-storage
devices.[91,176]
3. Nature Inspired Energy-Storage Devices
Besides electrochemical performance, rechargeble devices with
other smart functionalities are favaorable.[72,73] In this part,
some interesting energy-storage devices with add-on biomi-
metic features will be introduced. Inspired by the human skin
with the self-healing function, the mechanically and electrically
self-healing supercapacitors have been successfully fabricated.
In addition, a supercapacitor with ultrahigh working voltage as
well as self-rechargeable batteries have also been highlighted.
3.1. Self-Healing Energy-Storage Devices
Currently, to meet the requirements of growing development
of portable electronic devices, great efforts have been devoted
to the fabrication of flexible, lightweight, and miniaturized
energy-storage devices. However, when these devices are sub-
jected to practical applications, the inside electrode materials
become susceptible to structure fractures under bending or
components of these devices may possibly undergo mechanical
damage caused by deformation over time or accidental cutting.
Both of these failures would seriously impair the reliability and
lifetime of the devices, resulting in the failure of the electronic
devices, and generating abundant electronic waste, inconven-
ience as well as safety hazards.[177] Referring to the living organ-
isms, injuries could often be healed via regeneration systems.
Motivated by the great advantages of self-healing property in
durable operation against external destructions, advanced elec-
tronic devices equipped with self-healing functionality is highly
pursued and a promising route to expand the serve time of
future energy-storage devices and address the challenge of elec-
tronic hazard.
In one work conducted by Wang et al., a robust superca-
pacitor with self-healing capability in both structure integrity
and electrochemical energy-storage function against complete
cutting was successfully fabricated.[177] In this sandwiched
supercapacitor, the electrodes were fabricated by spreading
single-walled carbon nanotube (SWCNT) films on a supporting
substrate made of self-healing material, which was composed
of hierarchical flower-like TiO2 nanostructures and a supra-
molecular network. The supramolecular network achieved
its self-healing attribute through a large amount of hydrogen
bond acceptors and donors, while the incorporation of TiO2
nanospheres can enhance its mechanical strength, which
is favorable to hold its shape (Figure 9a). After damage, the
healable scaffold layer mediated the configuration restore and

Figure 9. a) The self-healing composite is composed of a supramolecular network and hierarchical flower-like TiO2 nanostructures. b) Schematic
representation of the configuration and self-healing capabilities of the supercapacitor. c) Specific capacitances of the original device and after healing
for different times. Reproduced with permission.[177] Copyright 2014, Wiley. d) Schematic illustrations of the self-healing process of as-prepared
supercapacitors. The magnetic alignment could assist the restoration of the yarn electrodes’ configuration and conductivity when they are brought
together. Photographs of two yarn-based supercapacitors connected in series to power a LED bulb: e1) after cutting; e2) after healing. Reproduced with
permission.[180] Copyright 2015, American Chemical Society.

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brought separate areas of the SWCNT together to recover its
conductivity, hence enabled the self-healing supercapacitor per-
formance (Figure 9b). The specific capacitance of as-prepared
supercapacitor was able to restore up to 85.7% even after 5th
complete cutting (Figure 9c).
In addition, Peng’s group reported a wire-shaped self-
healable supercapacitor by coating aligned carbon nano-
tubes on the surface of self-healing polymer fibers.[178] After
broken up, these conducting fibers can efficiently recover its
high electrical conductivity by the reestablished physical con-
tact of aligned carbon nanotubes in the sheath, and restored
mechanical strength by the self-healing of the polymer in the
core, respectively. The as-prepared wire-shaped supercapaci-
tors could deliver a high specific capacitance of 140.0 F g−1 or
1.34 mF cm−1, and could restored 92% of the initial capaci-
tance after breaking and self-healing. Based on the concept
of self-healing supercapacitor, the same group developed
a type of fusible energy devices by designing CNT film and
self-healing polymer layer into a ladder structure and stand-
ardized module.[179] Benefiting from this rational design, the
energy devices could be connected in series or parallel by
simply stacking and gently pressing them. They demonstrated
that the supercapacitors could be fused into various patterns
with tunable capacitances and operating voltage, and superca-
pacitors and perovskite solar cells could be easily fused into an
integrated device to simultaneously realize energy harvesting
and storage.
Moreover, another yarn-shaped self-healable supercapac-
itor facilitated by megnetifc force was developed by covering
magnetic material around a self-repairing polymer shell. The
magnetic attracting force between the broken electrodes con-
tributed to the recovery of electric conductivity, while the
polymer shell benefited the regeneration of configuration
integrity and mechanical strength (Figure 9d).[180] With the syn-
ergistic effects, its specific capacitance could be retored up to
71.8% after 4th breaking (Figure 9e).
Figure 10. a) Schematic of the electrocyte arranged in series in an electric eel, and b) the design and manufacturing process flow of a tandem fiber-
shaped electrochemical capacitor. c) Dependence of the charging voltage on time for fiber-shaped electrochemical capacitors with different numbers
of units in series. d) Dependence of the maximal output voltage on the unit number. Reproduced with permission.[181] Copyright 2016, Wiley.
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These work of successful fabrication of self-healing superca-
Review
pacitors contribute remarkably to prolong the lifetime of future
energy-storage devices with desirable economic and operation
safety attributes.
3.2. Other Energy-Storage Devices
The working voltage of current energy-storage devices are
usually limited to several volts and capable of powering small
apparatus, while higher voltage is desired to power large instru-
ments. Inspired by the unique arrangement in electric eels
which are able to produce voltages as high as 600 V via in-series
organization of thousands of electrocytes (Figure 10a), Sun et al.
developed a novel high-voltage wearable electrochemical capaci-
tors.[181] Water-based electrolytes are safer than organic-based
electrolytes for wearable applications, however limited the oper-
ating voltages of electrochemical devices due to the relatively
low thermodynamic decomposition potential of water (1.23 V).
Taking inspiration from electric eels, novel fiber-shaped elec-
trochemical capacitors with built-in in-series units connected
in a simple way was created (Figure 10b). An elastic fiber with
a diameter of 500 µm served as a stretchable and flexible sub-
strate, multiwalled carbon nanotube (MWCNT) sheets with cer-
tain length were wrapped onto the fiber along its length with
space intervals among very adjacent MWCNT sheets. Then,
small portions of adjacent MWCNT sheet segments and the
space interval were covered with poly(vinyl alcohol)/H3PO4 gel
electrolyte, and constituted one unit of symmetric electrochem-
ical capacitor. The middle of each uncovered MWCNT segments
functioned as the electric wires and connected these capacitor
units on the fiber in series. The maximal working voltages
of such electrochemical capacitor is proportional to the unit
number, when the capacitor was fabricated with 1000 units, it
was able to offer remarkably high output voltages up to 1000 V,
the highest records among reported energy storage devices to
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Figure 11. a) Schematic illustration of a self-powered capacitor. This integrated biocapacitor was composed of polyaniline/CNTs depositing on one
side of the electrodes and gold nanoparticle immobilized enzymes on the other side of the electrodes. b) Charge/discharge curves of the capacitor
without enzymes at a current density of 50 mA g−1 (curve 1), the integrated biocapacitor in 50 mM glucose/air-saturated solution for 4 h (curve 2) or
1 h (curve 3). Reproduced with permission.[182] Copyright 2016, Wiley.
date (Figure 10c,d). Eighteen fiber-shaped electrochemical
capacitors with 120 in-series units individually were woven into
a T-shirt and could power 57 red light-emitting diodes inte-
grated within the T-shirt. Additionally, with the similar inte-
gration strategy, solar cells could also be incorporated into the
electrochemical capacitors to achieve self-powered high output
voltage capacitors. These high-performance, flexible electro-
chemical capacitors with built-in in-series units are promising
for powering a variety of portable and wearable electronics.
By mimicking the self-powered biological processes which
employ a series of enzymes to extract electrons from organic
matter, Pankratov et al. fabricated another kind of self-charging
energy-storage device. It worked as an integrated device with
double-layer capacitor module and enzymatic fuel cell module
(Figure 11a).[182,183] Graphite foil (GF) with a thickness of ca.
2 mm was adopted as the conducting substrate, capacitive and
charging materials were located on different sides of the sub-
strate to form a singular electrode. For the anode, polyaniline/
carbon nanotubes (CNTs) were coated on one side of GF, and
Corynascus thermophiles cellobiose dehydrogenase (Glucose/
Gluconolactone) was immobilized on the other side via gold
nanoparticles (Au NPs) which was modified with thiol mono­
layer to aid the protein immobilization. For the cathode,
polyaniline/CNTs were also coated on one side of GF, and
Myrothecium verrucaria bilirubin oxidase was directly immobi-
lized on the other side of the electrode which was modified with
Au NPs. This device was able to be charged by incubation in
glucose/air-saturated solution (Figure 11b). Such self-charging
strategy is attractive, because harnessing the earth abundant
organic matter is a low-cost and sustainable charging strategy.
Virtually, the studies of nature-inspired energy-storage
devices are just in their primary stages. More smart and intelli-
gent energy-storage devices would be designed, and the perfor-
mance of these conceptual devices should be largely enhanced
before the practical application.
4. Conclusions and Outlook
This review summarizes the pioneering and representative
progress in the development of nature-inspired energy-storage
related materials and devices. Taking inspirations from natural
energy metabolism and storage systems, diverse approaches
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have been developed to rationally and effectively improve the
performance of active electrode materials, binders and sepa-
rators as well as to fabricate advanced energy-storage device
with the following design clues. (1) The active electrode mate-
rials are desired to obtain high energy storage density, stable
structure to support long cycle life, and robust architecture
against fracture induced by ion insertion/desertion. Inspired
by nature, promising routes have been paved towards ideal
active electrode materials. For instance, exploiting the biomol-
ecules acting as redox cofactors or electron shuttles within cells
is significant to fabricate green and highly efficient electrode
materials. Furthermore, unique structures of active materials to
ensure high cycling performance could be rationally designed
and prepared by mimicking some biological process and nat-
ural architectures, e.g., biomineralization and biotemplate
guided self-assembly, pomegranate-like hierarchically nano-
structured electrode with void space to allow the lithiation/del-
ithiation associated volume change. (2) Adhesion is a common
requirement for binder materials. By exploring the natural
materials with intrinsic adhesiveness or their derivatives with
similar adhesive groups, novel binders with extraordinary prop-
erties could be developed. (3) The wettability of separator is a
key factor determining its performance in rechargeable bat-
teries. Modification of the separator with strategies inspired by
natural process is effective to improve the hydrophilicity and
subsequent ion diffusion across it. (4) Add-on functionalities of
high-performance energy-storage devices could facilitate their
sophisticated applications. Inspired by the natural processes
with interesting features, advanced energy-storage devices
with self-healing, self-powered and other merits have been
obtained.[184–186]
Based on the breaking through progresses which have been
achieved until now, the following research directions are recom-
mended. Firstly, the energy density of the state-of-the-art active
materials inspired by nature still need further improvement.
Exploration and in-depth studies of more redox-activie biomol-
ecules with distinct redox centers should help identify a class
of active material candidates with high electrochemical perfor-
mance.[187] Novel architechture designs of electrodes could be
investigated by mimicking other well-organized natural prod-
ucts, which should emphasize the optimal balance between
ovall energy density, electron flux and enough void space for
ion insertion/desertion. Moreover, exploration of new adhesive
Adv. Energy Mater. 2016, 1601709

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materials or their artificial derivatives deserves to be continued
to obtain versatile highly adhesive binders to be applied with
different active materials.[30] In addition, smart energy-storage
devices inspired by nature are newly-emerged, and the current
ones have been developed in prototypes for concept demon-
stration. Progress in their performance improvement should
be made before the practical applications.[188] By learning the
wise strategies of natural systems in sophisticated regulation
for rational energy transformation and distribution, fine-tuned
configuration and adapted functionalities to their habitat, tre-
mendous artificial energy-storage systems with surprising
features could be developed. For example, biological systems
capable of sensing and responding to external stimuli provide
clues for envisioned self-powered sensing devices in response
to temperature, gas, humidity, mechanical forces, etc. Further-
more, advanced energy-storage devices being able to react after
sensing a specific signal could be realized in the near future
and lead to a series of self-management, self-adaptive and self-
protectable energy-storage devices. Undoubtedly, nature is
a rich source of inspirations and provides us a wise route to
explore and fabricate more efficient and interesting energy-
storage related materials and devices.
Acknowledgements
H.W. and Y.Y. contributed equally to this work. The authors acknowledge
the financial support of the National Key Basic Research Program of
China (2014CB31802), National Natural Science Foundation of China
(51532001, 51502009), and the Scientific Research Foundation for
the Returned Overseas Chinese Scholars, State Education Ministry
(37728802).
Received: August 2, 2016
Revised: September 8, 2016
Published online:
[1] N. Ding, S. F. Chen, D. S. Geng, S. W. Chien, T. An, T. S. A. Hor,
Z. L. Liu, S. H. Yu, Y. Zong, Adv. Energy Mater. 2015, 5, 1401999.
[2] N. Nitta, F. X. Wu, J. T. Lee, G. Yushin, Mater. Today 2015, 18, 252.
[3] S. M. Xu, C. M. Hessel, H. Ren, R. B. Yu, Q. Jin, M. Yang,
H. J. Zhao, D. Wang, Energy Environ. Sci. 2014, 7, 632.
[4] Y. Jiang, Z. Z. Yang, W. H. Li, L. C. Zeng, F. S. Pan, M. Wang,
X. Wei, G. T. Hu, L. Gu, Y. Yu, Adv. Energy Mater. 2015, 5, 1402104.
[5] M. R. Arcila-Velez, M. E. Roberts, Chem. Mater. 2014, 26, 1601.
[6] H. Yang, Z. Y. Liu, B. K. Chandran, J. Y. Deng, J. C. Yu, D. P. Qi,
W. L. Li, Y. X. Tang, C. G. Zhang, X. D. Chen, Adv. Mater. 2015, 27,
5593.
[7] L. Peng, Y. Zhu, D. Chen, R. S. Ruoff, G. Yu, Adv. Energy Mater.
2016, doi: 10.1002/aenm.201600025.
[8] L. L. Peng, X. Peng, B. R. Liu, C. Z. Wu, Y. Xie, G. H. Yu, Nano Lett.
2013, 13, 2151.
[9] Y. Zhang, Y. Zhao, J. Ren, W. Weng, H. S. Peng, Adv. Mater. 2016,
28, 4524.
[10] X. Fang, W. Weng, J. Ren, H. S. Peng, Adv. Mater. 2016, 28, 491.
[11] W. Weng, Q. Sun, Y. Zhang, S. S. He, Q. Q. Wu, J. Deng, X. Fang,
G. Z. Guan, J. Ren, H. S. Peng, Adv. Mater. 2015, 27, 1363.
[12] M. Armand, J. M. Tarascon, Nature 2008, 451, 652.
[13] Z. P. Song, H. S. Zhou, Energy Environ. Sci. 2013, 6, 2280.
[14] J. M. Tarascon, ChemSusChem 2008, 1, 777.
Adv. Energy Mater. 2016, 1601709 © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advenergymat.de
[15] D. Larcher, J. M. Tarascon, Nat. Chem. 2015, 7, 19.
Review
[16] W. W. Deng, X. M. Liang, X. Y. Wu, J. F. Qian, Y. L. Cao, X. P. Ai,
J. W. Feng, H. X. Yang, Sci. Rep. 2013, 3, 2671.
[17] J. J. Zhang, Z. H. Liu, Q. S. Kong, C. J. Zhang, S. P. Pang, L. P. Yue,
X. J. Wang, J. H. Yao, G. L. Cui, ACS Appl. Mater. Inter. 2013, 5, 128.
[18] G. Milczarek, M. Nowicki, Mater. Res. Bull. 2013, 48, 4032.
[19] L. M. Zhu, Y. F. Shen, M. Y. Sun, J. F. Qian, Y. L. Cao, X. P. Ai,
H. X. Yang, Chem. Commun. 2013, 49, 11370.
[20] E. M. Lotfabad, J. Ding, K. Cui, A. Kohandehghan, W. P. Kalisvaart,
M. Hazelton, D. Mitlin, ACS Nano 2014, 8, 7115.
[21] S. Admassie, A. Elfwing, E. W. H. Jager, Q. Y. Bao, O. Inganas,
J. Mater. Chem. A 2014, 2, 1974.
[22] K. Jost, D. P. Durkin, L. M. Haverhals, E. K. Brown, M. Langenstein,
H. C. De Long, P. C. Trulove, Y. Gogotsi, G. Dion, Adv. Energy
Mater. 2015, 5, 1401286.
[23] D. H. Nagaraju, T. Rebis, R. Gabrielsson, A. Elfwing, G. Milczarek,
O. Inganas, Adv. Energy Mater. 2014, 4, 1300443.
[24] Y. Ding, G. Yu, Angew. Chem.Int. Ed. 2016, 55, 4772.
[25] B. Dyatkin, V. Presser, M. Heon, M. R. Lukatskaya, M. Beidaghi,
Y. Gogotsi, ChemSusChem 2013, 6, 2269.
[26] J. L. Tang, V. G. Pol, Sci. Rep. 2016, 6, 20290.
[27] J. H. Lee, J. H. Lee, Y. J. Lee, K. T. Nam, Curr. Opin. Biotechnol.
2013, 24, 599.
[28] W. E. Tenhaeff, O. Rios, K. More, M. A. McGuire, Adv. Funct. Mater.
2014, 24, 86.
[29] S. K. Kim, Y. K. Kim, H. Lee, S. B. Lee, H. S. Park, ChemSusChem
2014, 7, 1094.
[30] S. D. P. Flores, G. C. Martin-Noble, R. L. Phillips, J. Schrier, J. Phys.
Chem. C 2015, 119, 21800.
[31] P. Hu, H. Wang, Y. Yang, J. Yang, J. Lin, L. Guo, Adv. Mater. 2016,
28, 3486.
[32] Y. S. Yun, D. H. Kim, S. J. Hong, M. H. Park, Y. W. Park, B. H. Kim,
H. J. Jin, K. Kang, Nanoscale 2015, 7, 15051.
[33] H. Y. Chen, M. Armand, M. Courty, M. Jiang, C. P. Grey, F. Dolhem,
J. M. Tarascon, P. Poizot, J. Am. Chem. Soc. 2009, 131, 8984.
[34] P. Poizot, F. Dolhem, Energy Environ. Sci. 2011, 4, 2003.
[35] Y. Yang, H. Wang, R. Hao, L. Guo, Small 2016, doi: 10.1002/
smll.201503924.
[36] S. Sotiropoulou, Y. Sierra-Sastre, S. S. Mark, C. A. Batt, Chem.
Mater. 2008, 20, 821.
[37] Y. J. Lee, A. M. Belcher, J. Mater. Chem. 2011, 21, 1033.
[38] Y. N. Li, J. Su, X. Y. Lv, Y. F. Long, Y. X. Wen, Electrochim. Acta 2015,
182, 596.
[39] S. N. Beznosov, P. S. Veluri, M. G. Pyatibratov, A. Chatterjee,
D. R. MacFarlane, O. V. Fedorov, S. Mitra, Sci. Rep. 2015, 5, 7736.
[40] C. X. Guo, Y. Q. Shen, Z. L. Dong, X. D. Chen, X. W. Lou, C. M. Li,
Energy Environ. Sci. 2012, 5, 6919.
[41] E. Royston, A. Ghosh, P. Kofinas, M. T. Harris, J. N. Culver, Lang-
muir 2008, 24, 906.
[42] H. M. Sun, L. Y. Cao, L. H. Lu, Energy Environ. Sci. 2012, 5, 6206.
[43] H. L. Tang, M. Xiong, D. Y. Qu, D. Liu, Z. J. Zhang, Z. Z. Xie,
X. Wei, W. M. Tu, D. Y. Qu, Nano Energy 2015, 15, 75.
[44] Y. Zhou, W. Sun, X. Rui, Y. Zhou, W. J. Ng, Q. Yan, E. Fong, Nano
Energy 2016, 21, 71.
[45] Z. Q. Niu, L. L. Liu, L. Zhang, W. Y. Zhou, X. D. Chen, S. S. Xie,
Adv. Energy Mater. 2015, 5, 1500677.
[46] Y. Xu, M. Zhou, Y. Lei, Adv. Energy Mater. 2016, doi: 10.1002/
aenm.201502514.
[47] B. Wang, X. L. Li, X. F. Zhang, B. Luo, Y. B. Zhang, L. J. Zhi, Adv.
Mater. 2013, 25, 3560.
[48] C. Zhu, T. Liu, F. Qian, T. Y. Han, E. B. Duoss, J. D. Kuntz,
C. M. Spadaccini, M. A. Worsley, Y. Li, Nano Lett. 2016, 16,
3448.
[49] J. W. Liang, X. N. Li, Z. G. Hou, T. W. Zhang, Y. C. Zhu, X. D. Yan,
Y. T. Qian, Chem. Mater. 2015, 27, 4156.
wileyonlinelibrary.com (15 of 18) 1601709
 www.advenergymat.de
Review
[50] S. X. Wang, S. L. Chen, Q. L. Wei, X. K. Zhang, S. Y. Wong,
S. H. Sun, X. Li, Chem. Mater. 2015, 27, 336.
[51] J. Chang, S. Adhikari, T. H. Lee, B. Li, F. Yao, D. T. Pham, V. T. Le,
Y. H. Lee, Adv. Energy Mater. 2015, 5, 1500003.
[52] K. S. Liu, X. Yao, L. Jiang, Chem. Soc. Rev. 2010, 39, 3240.
[53] X. Hou, W. Guo, L. Jiang, Chem. Soc. Rev. 2011, 40, 2385.
[54] T. L. Sun, G. Y. Qing, B. L. Su, L. Jiang, Chem. Soc. Rev. 2011, 40,
2909.
[55] D. Y. Chung, K. J. Lee, S. H. Yu, M. Kim, S. Y. Lee, O. H. Kim,
H. J. Park, Y. E. Sung, Adv. Energy Mater. 2015, 5, 1401309.
[56] D. Esrafilzadeh, R. Jalili, E. M. Stewart, S. H. Aboutalebi,
J. M. Razal, S. E. Moulton, G. G. Wallace, Adv. Funct. Mater. 2016,
26, 3105.
[57] Y. C. Wang, S. Y. Tao, Y. L. An, S. Wu, C. G. Meng, J. Mater. Chem.
A 2013, 1, 8876.
[58] Q. B. Xia, X. F. Zhao, M. Q. Xu, Z. P. Ding, J. T. Liu, L. B. Chen,
D. G. Ivey, W. F. Wei, J. Mater. Chem. A 2015, 3, 3995.
[59] J. Yu, S. M. Chen, W. J. Hao, S. J. Zhang, ACS Nano 2016, 10, 2500.
[60] J. X. Wu, X. Y. Qin, C. Miao, Y. B. He, G. M. Liang, D. Zhou, M. Liu,
C. P. Han, B. H. Li, F. Y. Kang, Carbon 2016, 98, 582.
[61] Y. Zhao, L. L. Peng, Y. Ding, G. H. Yu, Chem. Commun. 2014, 50,
12959.
[62] W. Liu, Z. Chen, G. Zhou, Y. Sun, H. R. Lee, C. Liu, H. Yao, Z. Bao,
Y. Cui, Adv. Mater. 2016, 28, 3578.
[63] J. Deng, J. F. Li, P. N. Chen, X. Fang, X. M. Sun, Y. S. Jiang,
W. Weng, B. J. Wang, H. S. Peng, J. Am. Chem. Soc. 2016, 138, 225.
[64] A. Vlad, N. Singh, C. Galande, P. M. Ajayan, Adv. Energy Mater.
2015, 5, 1402115.
[65] H. Zhou, T. X. Fan, D. Zhang, ChemCatChem 2011, 3, 513.
[66] B. C. Kim, J. Y. Hong, G. G. Wallace, H. S. Park, Adv. Energy Mater.
2015, 5.
[67] W. Weng, P. Chen, S. He, X. Sun, H. Peng, Angew. Chem. Int. Ed.
2016, 55, 6140.
[68] E. Kim, Y. Liu, W. E. Bentley, G. F. Payne, Adv. Funct. Mater. 2012,
22, 1409.
[69] Z. D. Li, H. Liu, C. Ouyang, W. H. Wee, X. Y. Cui, T. J. Lu,
B. Pingguan-Murphy, F. Li, F. Xu, Adv. Funct. Mater. 2016, 26, 165.
[70] J. M. Wang, L. Zhang, L. Yu, Z. H. Jiao, H. Q. Xie, X. W. Lou,
X. W. Sun, Nat. Commun. 2014, 5, 4921.
[71] H. Wang, F. Li, B. Zhu, L. Guo, Y. Yang, R. Hao, H. Wang, Y. Liu,
W. Wang, X. Guo, X. Chen, Adv. Funct. Mater. 2016, 26, 3472.
[72] S. W. Pan, J. Ren, X. Fang, H. S. Peng, Adv. Energy Mater. 2016, 6,
1501867.
[73] J. E. Deng, Y. Zhang, Y. Zhao, P. N. Chen, X. L. Cheng, H. S. Peng,
Angew. Chem. Int. Ed. 2015, 54, 15419.
[74] K. Kalyanasundaram, M. Graetzel, Curr. Opin. Biotechnol. 2010, 21,
298.
[75] X. L. Fan, J. F. Mao, Y. J. Zhu, C. Luo, L. M. Suo, T. Gao, F. D. Han,
S. C. Liou, C. S. Wang, Adv. Energy Mater. 2015, 5, 1500174.
[76] Z. Chen, C. Wang, J. Lopez, Z. D. Lu, Y. Cui, Z. A. Bao, Adv. Energy
Mater. 2015, 5, 1401826.
[77] X. Xiao, T. Q. Li, P. H. Yang, Y. Gao, H. Y. Jin, W. J. Ni, W. H. Zhan,
X. H. Zhang, Y. Z. Cao, J. W. Zhong, L. Gong, W. C. Yen, W. J. Mai,
J. Chen, K. F. Huo, Y. L. Chueh, Z. L. Wang, J. Zhou, ACS Nano
2012, 6, 9200.
[78] P. H. Yang, X. Xiao, Y. Z. Li, Y. Ding, P. F. Qiang, X. H. Tan,
W. J. Mai, Z. Y. Lin, W. Z. Wu, T. Q. Li, H. Y. Jin, P. Y. Liu, J. Zhou,
C. P. Wong, Z. L. Wang, ACS Nano 2013, 7, 2617.
[79] J. Mao, X. Fan, C. Luo, C. Wang, ACS Appl. Mater. Interfaces 2016,
8, 7147.
[80] Y. M. Sun, J. Lopez, H. W. Lee, N. Liu, G. Y. Zheng, C. L. Wu,
J. Sun, W. Liu, J. W. Chung, Z. N. Bao, Y. Cui, Adv. Mater. 2016, 28,
2455.
[81] Y. Zhao, X. Li, B. Yan, D. Xiong, D. Li, S. Lawes, X. Sun, Adv. Energy
Mater. 2016, 6, 1502175.
1601709 (16 of 18) wileyonlinelibrary.com © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.MaterialsViews.com
[82] J. J. Zhang, J. H. Zhao, L. P. Yue, Q. F. Wang, J. C. Chai, Z. H. Liu,
X. H. Zhou, H. Li, Y. G. Guo, G. L. Cui, L. Q. Chen, Adv. Energy
Mater. 2015, 5, 1501082.
[83] X. D. Xiang, K. Zhang, J. Chen, Adv. Mater. 2015, 27, 5343.
[84] R. B. Wu, X. K. Qian, K. Zhou, J. Wei, J. Lou, P. M. Ajayan, ACS
Nano 2014, 8, 6297.
[85] H. P. Wu, S. A. Shevlin, Q. H. Meng, W. Guo, Y. N. Meng, K. Lu,
Z. X. Wei, Z. X. Guo, Adv. Mater. 2014, 26, 3338.
[86] C. Fang, Y. H. Huang, W. X. Zhang, J. T. Han, Z. Deng, Y. L. Cao,
H. X. Yang, Adv. Energy Mater. 2016, 6, 1501727.
[87] M. S. Balogun, W. T. Qiu, W. Wang, P. P. Fang, X. H. Lu, Y. X. Tong,
J. Mater. Chem. A 2015, 3, 1364.
[88] N. Mahmood, C. Z. Zhang, F. Liu, J. H. Zhu, Y. L. Hou, ACS Nano
2013, 7, 10307.
[89] X. L. Hu, W. Zhang, X. X. Liu, Y. N. Mei, Y. Huang, Chem. Soc. Rev.
2015, 44, 2376.
[90] H. Gao, W. Zhou, J.-H. Jang, J. B. Goodenough, Adv. Energy Mater.
2016, 6, 1502130.
[91] S. J. Chun, E. S. Choi, E. H. Lee, J. H. Kim, S. Y. Lee, S. Y. Lee, J.
Mater. Chem. 2012, 22, 16618.
[92] H. J. Tang, J. Y. Wang, H. J. Yin, H. J. Zhao, D. Wang, Z. Y. Tang,
Adv. Mater. 2015, 27, 1117.
[93] Y. J. Kim, W. Wu, S. E. Chun, J. F. Whitacre, C. J. Bettinger, Proc.
Natl. Acad. Sci. U.S.A. 2013, 110, 20912.
[94] M. Oba, Y. Oaki, H. Imai, Adv. Funct. Mater. 2010, 20, 4279.
[95] N. Bockenfeld, S. S. Jeong, M. Winter, S. Passerini, A. Balducci,
J. Power Sources 2013, 221, 14.
[96] Y. L. Liu, K. L. Ai, L. H. Lu, Chem. Rev. 2014, 114, 5057.
[97] H. Wang, H. B. Feng, J. H. Li, Small 2014, 10, 2165.
[98] Y. L. Liang, Z. L. Tao, J. Chen, Adv. Energy Mater. 2012, 2, 742.
[99] R. Yi, M. L. Gordin, D. H. Wang, Nanoscale 2016, 8, 1834.
[100] X. P. Wang, C. J. Niu, J. S. Meng, P. Hu, X. M. Xu, X. J. Wei,
L. Zhou, K. N. Zhao, W. Luo, M. Y. Yan, L. Q. Mai, Adv. Energy
Mater. 2015, 5, 1500716.
[101] Y. Dou, J. Xu, B. Ruan, Q. Liu, Y. Pan, Z. Sun, S. X. Dou, Adv.
Energy Mater. 2016, 6, 1501835.
[102] D. W. Su, S. X. Dou, G. X. Wang, Adv. Energy Mater. 2015, 5,
1401205.
[103] J. B. Cook, H.-S. Kim, Y. Yan, J. S. Ko, S. Robbennolt, B. Dunn,
S. H. Tolbert, Adv. Energy Mater. 2016, 6, 1501937.
[104] J. Ni, S. Fu, C. Wu, Y. Zhao, J. Maier, Y. Yu, L. Li, Adv. Energy Mater.
2016, doi: 10.1002/aenm.201502568.
[105] X. Q. Xie, T. Makaryan, M. Q. Zhao, K. L. Van Aken, Y. Gogotsi,
G. X. Wang, Adv. Energy Mater. 2016, 6, 1502161.
[106] X. L. Wu, Y. G. Guo, J. Su, J. W. Xiong, Y. L. Zhang, L. J. Wan, Adv.
Energy Mater. 2013, 3, 1155.
[107] W. H. Li, Z. Z. Yang, M. S. Li, Y. Jiang, X. Wei, X. W. Zhong, L. Gu,
Y. Yu, Nano Lett. 2016, 16, 1546.
[108] D. L. Chao, C. R. Zhu, X. H. Xia, J. L. Liu, X. Zhang, J. Wang,
P. Liang, J. Y. Lin, H. Zhang, Z. X. Shen, H. J. Fan, Nano Lett. 2015,
15, 565.
[109] Z. P. Song, Y. M. Qian, T. Zhang, M. Otani, H. S. Zhou, Adv. Sci.
2015, 2, 1500124.
[110] J. W. Chen, X. Wang, J. X. Wang, P. S. Lee, Adv. Energy Mater. 2016,
6, 1501745.
[111] J. Wang, N. Yang, H. Tang, Z. Dong, Q. Jin, M. Yang, D. Kisailus,
H. Zhao, Z. Tang, D. Wang, Angew. Chem. Int. Ed. 2013, 52,
6417.
[112] O. Inganas, S. Admassie, Adv. Mater. 2014, 26, 830.
[113] Y. J. Kim, W. Wu, S. E. Chun, J. F. Whitacre, C. J. Bettinger, Adv.
Mater. 2014, 26, 6572.
[114] L. X. Zhang, Z. H. Liu, G. L. Cui, L. Q. Chen, Prog. Polym. Sci.
2015, 43, 136.
[115] B. Haupler, A. Wild, U. S. Schubert, Adv. Energy Mater. 2015, 5,
1402034.
Adv. Energy Mater. 2016, 1601709

www.MaterialsViews.com
[116] H. Wang, P. F. Hu, J. Yang, G. M. Gong, L. Guo, X. D. Chen, Adv.
Mater. 2015, 27, 2348.
[117] M. Lee, J. Hong, D. H. Seo, D. H. Nam, K. T. Nam, K. Kang,
C. B. Park, Angew. Chem. Int. Ed. 2013, 52, 8322.
[118] M. Lee, J. Hong, H. Kim, H. D. Lim, S. B. Cho, K. Kang, C. B. Park,
Adv. Mater. 2014, 26, 2558.
[119] J. Hong, M. Lee, B. Lee, D. H. Seo, C. B. Park, K. Kang, Nat.
Commun. 2014, 5, 5335.
[120] H. L. Wang, Z. Li, D. Mitlin, ChemElectroChem 2014, 1, 332.
[121] W. Q. Tian, Q. M. Gao, Y. L. Tan, K. Yang, L. H. Zhu, C. X. Yang,
H. Zhang, J. Mater. Chem. A 2015, 3, 5656.
[122] E. M. Lotfabad, P. Kalisvaart, A. Kohandehghan, D. Karpuzov,
D. Mitlin, J. Mater. Chem. A 2014, 2, 19685.
[123] Q. Wang, Q. Cao, X. Y. Wang, B. Jing, H. Kuang, L. Zhou, J. Power
Sources 2013, 225, 101.
[124] Z. Li, L. Zhang, B. S. Amirkhiz, X. H. Tan, Z. W. Xu, H. L. Wang,
B. C. Olsen, C. M. B. Holt, D. Mitlin, Adv. Energy Mater. 2012, 2, 431.
[125] C. L. Long, D. P. Qi, T. Wei, J. Yan, L. L. Jiang, Z. J. Fan, Adv. Funct.
Mater. 2014, 24, 3953.
[126] H. Zhou, T. X. Fan, D. Zhang, ChemSusChem 2011, 4, 1344.
[127] S. Kim, C. B. Park, Adv. Funct. Mater. 2013, 23, 10.
[128] W. Q. Tian, Q. M. Gao, Y. L. Tan, K. Yang, L. H. Zhu, C. X. Yang,
H. Zhang, J. Mater. Chem. A 2015, 3, 5656.
[129] X. L. Chen, K. Gerasopoulos, J. C. Guo, A. Brown, C. S. Wang,
R. Ghodssi, J. N. Culver, ACS Nano 2010, 4, 5366.
[130] J. Miot, N. Recham, D. Larcher, F. Guyot, J. Brest, J. M. Tarascon,
Energy Environ. Sci. 2014, 7, 451.
[131] Y. Lu, Y. P. Zhou, Q. Y. Yan, E. Fong, J. Mater. Chem. A 2016, 4,
2691.
[132] Y. Zhou, X. Rui, W. Sun, Z. Xu, Y. Zhou, W. J. Ng, Q. Yan, E. Fong,
ACS Nano 2015, 9, 4628.
[133] Y. J. Lee, H. Yi, W. J. Kim, K. Kang, D. S. Yun, M. S. Strano,
G. Ceder, A. M. Belcher, Science 2009, 324, 1051.
[134] K. T. Nam, R. Wartena, P. J. Yoo, F. W. Liau, Y. J. Lee, Y. M. Chiang,
P. T. Hammond, A. M. Belcher, Proc. Natl. Acad. Sci. U.S.A. 2008,
105, 17227.
[135] J. Ryu, S. W. Kim, K. Kang, C. B. Park, Adv. Mater. 2010, 22,
5537.
[136] K. T. Nam, D. W. Kim, P. J. Yoo, C. Y. Chiang, N. Meethong,
P. T. Hammond, Y. M. Chiang, A. M. Belcher, Science 2006, 312,
885.
[137] Y. J. Lee, Y. Lee, D. Oh, T. Chen, G. Ceder, A. M. Belcher, Nano Lett.
2010, 10, 2433.
[138] M. Moradi, Z. Li, J. Qi, W. Xing, K. Xiang, Y. M. Chiang,
A. M. Belcher, Nano Lett. 2015, 15, 2917.
[139] D. Oh, J. F. Qi, B. H. Han, G. R. Zhang, T. J. Carney, J. Ohmura,
Y. Zhang, Y. Shao-Horn, A. M. Belcher, Nano Lett. 2014, 14, 4837.
[140] H. M. Sun, L. Y. Cao, L. H. Lu, Energy Environ. Sci. 2012, 5, 6206.
[141] J. H. Kong, S. I. S. Shahabadi, X. H. Lu, Nanoscale 2016, 8, 1770.
[142] Y. C. Liu, N. Zhang, L. F. Jiao, J. Chen, Adv. Mater. 2015, 27, 6702.
[143] H. C. Song, H. X. Wang, Z. X. Lin, X. F. Jiang, L. W. Yu, J. Xu,
Z. W. Yu, X. W. Zhang, Y. J. Liu, P. He, L. J. Pan, Y. Shi, H. S. Zhou,
K. J. Chen, Adv. Funct. Mater. 2016, 26, 524.
[144] B. Wang, X. L. Li, T. F. Qiu, B. Luo, J. Ning, J. Li, X. F. Zhang,
M. H. Liang, L. J. Zhi, Nano Lett. 2013, 13, 5578.
[145] R. Y. Wang, B. Shyam, K. H. Stone, J. N. Weker, M. Pasta,
H. W. Lee, M. F. Toney, Y. Cui, Adv. Energy Mater. 2015, 5, 1401869.
[146] J. Y. Lee, K. H. Lee, Y. J. Kim, J. S. Ha, S. S. Lee, J. G. Son, Adv.
Funct. Mater. 2015, 25, 3606.
[147] N. Liu, Z. D. Lu, J. Zhao, M. T. McDowell, H. W. Lee, W. T. Zhao,
Y. Cui, Nat. Nanotechnol. 2014, 9, 187.
[148] Y. Sun, R. B. Sills, X. Hu, Z. W. Seh, X. Xiao, H. Xu, W. Luo, H. Jin,
Y. Xin, T. Li, Z. Zhang, J. Zhou, W. Cai, Y. Huang, Y. Cui, Nano Lett.
2015, 15, 3899.
Adv. Energy Mater. 2016, 1601709 © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advenergymat.de
[149] S. H. Chung, A. Manthiram, ChemSusChem 2014, 7, 1655.
Review
[150] S. H. Chung, A. Manthiram, Adv. Mater. 2014, 26, 1360.
[151] H. L. Zhu, Z. Jia, Y. C. Chen, N. Weadock, J. Y. Wan, O. Vaaland,
X. G. Han, T. Li, L. B. Hu, Nano Lett. 2013, 13, 3093.
[152] J. Liu, Q. Zhang, T. Zhang, J. T. Li, L. Huang, S. G. Sun, Adv. Funct.
Mater. 2015, 25, 3599.
[153] G. R. Li, M. Ling, Y. F. Ye, Z. P. Li, J. H. Guo, Y. F. Yao,
J. F. Zhu, Z. Lin, S. Q. Zhang, Adv. Energy Mater. 2015, 5,
1500878.
[154] B. Koo, H. Kim, Y. Cho, K. T. Lee, N. S. Choi, J. Cho, Angew. Chem.
Int. Ed. 2012, 51, 8762.
[155] T. W. Kwon, Y. K. Jeong, E. Deniz, S. Y. AlQaradawi, J. W. Choi,
A. Coskun, ACS Nano 2015, 9, 11317.
[156] M. Y. Wu, X. C. Xiao, N. Vukmirovic, S. D. Xun, P. K. Das,
X. Y. Song, P. Olalde-Velasco, D. D. Wang, A. Z. Weber, L. W. Wang,
V. S. Battaglia, W. L. Yang, G. Liu, J. Am. Chem. Soc. 2013, 135,
12048.
[157] J. X. Song, M. J. Zhou, R. Yi, T. Xu, M. L. Gordin, D. H. Tang,
Z. X. Yu, M. Regula, D. H. Wang, Adv. Funct. Mater. 2014, 24,
5904.
[158] M. Aslan, D. Weingarth, N. Jackel, J. S. Atchison, I. Grobelsek,
V. Presser, J. Power Sources 2014, 266, 374.
[159] G. N. Qian, L. Wang, Y. M. Shang, X. M. He, S. F. Tang, M. Liu,
T. W. Li, G. Q. Zhang, J. L. Wang, Electrochim. Acta 2016, 187,
113.
[160] C. Heinzmann, C. Weder, L. M. de Espinosa, Chem. Soc. Rev. 2015,
45, 342.
[161] L. L. Chai, Q. T. Qu, L. F. Zhang, M. Shen, L. Zhang, H. H. Zheng,
Electrochim. Acta 2013, 105, 378.
[162] I. Kovalenko, B. Zdyrko, A. Magasinski, B. Hertzberg,
Z. Milicev, R. Burtovyy, I. Luzinov, G. Yushin, Science 2011,
334, 75.
[163] M. Murase, N. Yabuuchi, Z. J. Han, J. Y. Son, Y. T. Cui, H. Oji,
S. Komaba, ChemSusChem 2012, 5, 2307.
[164] J. Liu, Q. Zhang, T. Zhang, J. T. Li, L. Huang, S. G. Sun, Adv. Funct.
Mater. 2015, 25, 3599.
[165] Y. K. Jeong, T. W. Kwon, I. Lee, T. S. Kim, A. Coskun, J. W. Choi,
Energy Environ. Sci. 2015, 8, 1224.
[166] G. R. Li, M. Ling, Y. F. Ye, Z. P. Li, J. H. Guo, Y. F. Yao, J. F. Zhu,
Z. Lin, S. Q. Zhang, Adv. Energy Mater. 2015, 5, 1500878.
[167] M. H. Ryou, J. Kim, I. Lee, S. Kim, Y. K. Jeong, S. Hong, J. H. Ryu,
T. S. Kim, J. K. Park, H. Lee, J. W. Choi, Adv. Mater. 2013, 25,
1571.
[168] C. Wang, H. Wu, Z. Chen, M. T. McDowell, Y. Cui, Z. A. Bao, Nat.
Chem. 2013, 5, 1042.
[169] H. Lee, M. Yanilmaz, O. Toprakci, K. Fu, X. W. Zhang, Energy
Environ. Sci. 2014, 7, 3857.
[170] J. D. Zhu, C. Chen, Y. Lu, J. Zang, M. J. Jiang, D. Kim, X. W. Zhang,
Carbon 2016, 101, 272.
[171] J. J. Woo, Z. C. Zhang, K. Amine, Adv. Energy Mater. 2014, 4,
1301208.
[172] J. H. Kim, J. H. Kim, K. H. Choi, H. K. Yu, J. H. Kim, J. S. Lee,
S. Y. Lee, Nano Lett. 2014, 14, 4438.
[173] J. J. Yan, Y. P. Huang, Y. E. Miao, W. W. Tjiu, T. X. Liu, J. Hazard
Mater. 2015, 283, 730.
[174] M. H. Ryou, Y. M. Lee, J. K. Park, J. W. Choi, Adv. Mater. 2011, 23,
3066.
[175] M. H. Ryou, D. J. Lee, J. N. Lee, Y. M. Lee, J. K. Park, J. W. Choi,
Adv. Energy Mater. 2012, 2, 645.
[176] J. H. Kim, J. H. Kim, E. S. Choi, H. K. Yu, J. H. Kim, Q. L. Wu,
S. J. Chun, S. Y. Lee, S. Y. Lee, J. Power Sources 2013, 242,
533.
[177] H. Wang, B. W. Zhu, W. C. Jiang, Y. Yang, W. R. Leow, H. Wang,
X. D. Chen, Adv. Mater. 2014, 26, 3638.
wileyonlinelibrary.com (17 of 18) 1601709
 www.advenergymat.de
www.MaterialsViews.com
Review

[178] H. Sun, X. You, Y. S. Jiang, G. Z. Guan, X. Fang, J. Deng, P. N. Chen,
Y. F. Luo, H. S. Peng, Angew. Chem. Int. Ed. 2014, 53, 9526.
[179] H. Sun, Y. S. Jiang, L. B. Qiu, X. You, J. H. Yang, X. M. Fu,
P. N. Chen, G. Z. Guan, Z. B. Yang, X. M. Sun, H. S. Peng,
J. Mater. Chem. A 2015, 3, 14977.
[180] Y. Huang, Y. Huang, M. Zhu, W. Meng, Z. Pei, C. Liu, H. Hu,
C. Zhi, ACS Nano 2015, 9, 6242.
[181] H. Sun, X. M. Fu, S. L. Xie, Y. S. Jiang, H. S. Peng, Adv. Mater.
2016, 28, 2070.
[182] D. Pankratov, Z. Blum, D. B. Suyatin, V. O. Popov, S. Shleev,
ChemElectroChem 2014, 1, 343.
[183] B. D. Liba, E. Kim, A. N. Martin, Y. Liu, W. E. Bentley, G. F. Payne,
Biofabrication 2013, 5, 015008.
[184] S. Y. Rao, Z. B. Guo, D. W. Liang, D. L. Chen, Y. Li, Y. Xiang, Adv.
Mater. 2015, 27, 2668.
[185] S. Y. Rao, S. F. Lu, Z. B. Guo, Y. Li, D. L. Chen, Y. Xiang, Adv. Mater.
2014, 26, 5846.
[186] H. Ren, H. Tian, H. S. Lee, T. Park, F. C. Leung, T. L. Ren, J. Chae,
Nano Energy 2015, 15, 697.
[187] G. Milczarek, O. Inganas, Science 2012, 335, 1468.
[188] L. Yin, X. Huang, H. X. Xu, Y. F. Zhang, J. Lam, J. J. Cheng,
J. A. Rogers, Adv. Mater. 2014, 26, 3879.

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