SmartMat - 2020 - Kong - Advanced energy materials for flexible batteries in energy storage A review

Received: 2 October 2020 | Revised: 14 October 2020 | Accepted: 18 October 2020
DOI: 10.1002/smm2.1007
REVIEW
Advanced energy materials for flexible batteries in energy

storage: A review
Long Kong1,2 | Cheng Tang3 | Hong‐Jie Peng4 | Jia‐Qi Huang5 |

Qiang Zhang1
1
Department of Chemical Engineering,
Beijing Key Laboratory of Green Chemical Abstract
Reaction Engineering and Technology, Smart energy storage has revolutionized portable electronics and electrical
Tsinghua University, Beijing, China
2
vehicles. The current smart energy storage devices have penetrated into flex-
Academy for Advanced Interdisciplinary
Studies, Southern University of Science ible electronic markets at an unprecedented rate. Flexible batteries are key
and Technology, Shenzhen, China power sources to enable vast flexible devices, which put forward additional
3
School of Chemical Engineering and requirements, such as bendable, twistable, stretchable, and ultrathin, to adapt
Advanced Materials, The University of
mechanical deformation under the working conditions. This review sum-
Adelaide, Adelaide, South Australia,
Australia marizes the recent advances in construction and configuration of flexible
4
Department of Chemical Engineering, batteries and discusses the general metrics to benchmark various flexible
Stanford University, Stanford, batteries with different materials and chemistries. Moreover, we present ad-
California, USA
5
vanced prototype flexible batteries developed by some companies to afford
Advanced Research Institute of
Multidisciplinary Science, School of general envision of the technological status. Lastly, the critical points are
Materials Science and Engineering, Beijing summarized in the development of flexible batteries and remaining challenges
Institute of Technology, Beijing, China
are also presented for the future design of flexible batteries in practical
Correspondence perspectives.
Qiang Zhang, Department of Chemical
Engineering, Beijing Key Laboratory of KEYWORDS
Green Chemical Reaction Engineering composite electrode, flexible batteries, smart energy storage, ultrathin batteries, wearable
and Technology, Tsinghua University, electronics
100084 Beijing, China.
Email: zhang-qiang@mails.tsinghua.
edu.cn
Funding information
National Natural Science Foundation of
China, Grant/Award Numbers: 21805162,
21825501, and U1801257
1 | INTRODUCTION great success has been witnessed in the application of

lithium‐ion (Li‐ion) batteries in electrified transportation
Rechargeable batteries have popularized in smart elec- and portable electronics, and non‐lithium battery che-
trical energy storage in view of energy density, power mistries emerge as alternatives in special applications
density, cyclability, and technical maturity.1–5 A from cost and safety views.6–10 While energy/power
This is an open access article under the terms of the Creative Commons Attribution License, which permits use, dstribution and reproduction in any medium, provided
the original work is properly cited.
© 2020 The Authors. SmartMatpublished by Tianjin University and John Wiley & Sons Australia, Ltd
SmartMat. 2020;1:e1007. wileyonlinelibrary.com/journal/smm2 | 1 of 35

https://doi.org/10.1002/smm2.1007
2688819x, 2020, 1, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/smm2.1007 by CAPES, Wiley Online Library on [24/04/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
2 of 35 | KONG ET AL.
density and safety are still kernel for battery technologies

to make devices perform longer, faster, and safer, emer-
ging demands of functionalities, such as comfort,
smartness, and flexibility, have been weighted in the
market at an unprecedented rate.11–16 Such a paradigm
shift arises from the breakthroughs in materials and
processing techniques, rendering and creating diverse
opportunities to integrate electrochemical energy into
flexible devices.17–20
Flexible batteries have been the research of interest
due to their potential to enable electronic products more
bendable, adaptable, and comfortable.21–25 These versatile
functionalities stimulate the development of Internet of FIGURE 1 The scheme of flexible batteries
things (IoT), roll‐up displays, implantable medical robots,
wearable electronics.26,27 Most of well‐performing Li‐ion
batteries with rigid and brittle features cannot be directly high safety and power density also gain growing atten-
implanted to flexible devices that experience demanding tion in flexible batteries.74–81 Besides, multielectron me-
operating conditions, such as flexing, stretching, bending, tal ion batteries such as aluminum and magnesium ion
twisting, and folding.28–30 Accordingly, flexibility‐oriented batteries come into the eyes of the academic community
material and system designs have to be fully considered to by virtue of high energy and/or abundant resources.82–86
make devices durable, which call for exploring a range of For these battery systems, electrodes have attracted in-
carbon,31–36 metal,37–39 and polymer40–42 materials with tensive interests of researchers due to their major role in
soft features, as well as novel manufacturing methods to the determination of energy density and cyclability, while
fabricate full cells.43 inactive components, including separators, electrolytes,
Applications of flexible batteries most likely seek for current collectors, binders, and packaging, also exert
materials/structures that can achieve trade‐offs in per- critical effects on the final energy/power outputs and
formance and flexibility. Conventional Li‐ion batteries flexibility.42,87–93 Comprehensively and fairly comparing
deploy porous electrodes soaking in nonaqueous elec- the reported data of these flexible batteries requires si-
trolytes to establish ion and electron transport path- multaneous consideration of geometric, mechanical, and
ways.44 The porous electrodes are normally fabricated by energy chemistry parameters.
active materials and conductive fillers, both of which are In this contribution, the recent advances in various
bonded by polymeric binders to ensure electrode in- flexible batteries are presented. The article is organized as
tegration during working conditions. To achieve desired following (Figure 1). In Section 2, a range of widely used
energy density in the large format cells, thick electrode, parameters that characterize flexible batteries are in-
lean electrolyte, low porosity, and minimum inactive troduced for quantitative demonstration of battery flex-
materials are pursued.45–48 However, flexible cells need ibility, providing a benchmark to report and compare
to bear significant geometric deformation, which leads to electrochemical performance, and mechanical flexibility
component sliding and moving. Therefore, rational de- of batteries. In Section 3, critical components (current
sign of the flexible battery components and structures is collectors, electrolytes, and separators) in the construction
prerequisite for flexible batteries to withstand acceptable of flexible batteries are highlighted based on the recent
deformation. For instance, a high porosity needs to be achievements in these fields, leading to guidelines on the
preserved in the flexible electrodes to release strain, rational design of effective flexible components to fulfill
while it will inevitably diminish the energy density of the emerging requirements. To bridge the gap between aca-
entire cell.49,50 How to optimize materials, structures, demic and industrial communities, prototype flexible
and cell configurations comprehensively affects the per- batteries with potential to be integrated into commercial
formance and functionality of working batteries. products are presented, highlighting the key industrial
To extend utilization in smart energy storage, considerations in the design of flexible devices. Finally, the
various battery chemistries have been explored.51–56 review will outlook on key challenges and new
Lithium–sulfur/oxygen (Li–S/O2) batteries exhibit over- opportunities to fuel the further development of
whelming energy density than conventional lithium/ energy‐dense, cost‐effective, safety‐enhanced, and
sodium‐ion (Li/Na‐ion) batteries.57–65 A technical leap in cyclability‐prolonged flexible batteries. A brief chronology
the lithium metal anode has a promise to significantly of critical achievements in the field of flexible batteries are
increase energy density.66–73 Zinc‐based batteries with outlined based on this Review (Figure 2). Flexible batteries
KONG ET AL. | 3 of 35
F I G U R E 2 A brief chronology of critical achievements of flexible batteries for smart energy storage systems. Images reproduced with
permission as follows: “Coaxial fiber batteries”: reproduced with permission.94 Copyright © 2012, WILEY‐VCH. “Full batteries with SPE”:
reproduced with permission.95 Copyright © 2014, WILEY‐VCH. “Flexible CNT/S cathode”: reproduced with permission.96 Copyright ©
2014, WILEY‐VCH. “Origami Li‐ion batteries”: reproduced with permission.97 Copyright © 2014, Macmillan Publishers Limited. “Twisted
Li metal batteries”: reproduced with permission.98 Copyright © 2013, WILEY‐VCH. “3D printed all‐fiber batteries”: reproduced with
permission.99 Copyright © 2017, WILEY‐VCH. “Organic/inorganic electrolyte separator”: reproduced with permission.100 “Spine‐inspired
batteries”: reproduced with permission.101 Copyright © 2018, WILEY‐VCH. “Polymer/polymer separator”: reproduced with permission.102
Copyright © 2019, Springer Nature Limited. “Polar gel polymer electrolyte”: reproduced with permission.103 Copyright © 2019, The Royal
Society of Chemistry. CNT, carbon nanotube
with various chemistries are not specifically discussed combinations. The flexible batteries should maintain or, at
herein, as many insightful review articles have detailly least, not significantly sacrifice their electrochemical char-
introduced their working mechanisms, recent advances, acteristics in such deformations. The robust flexibility of
and remaining challenges.104–110 batteries can be implemented into flexible and wearable
electronics to enable diverse functionalities. A direct reflec-
tion of flexibility is the bending radius of curvature (r) ac-
2 | CRITICAL PARAMETERS TO cording to Equation (1), and a smaller r means more
ASSESS FLEXIBLE BATTERIES flexible.111 However, r alone cannot fully describe the flex-
ibility of devices. The flexibility is also intimately related to
Fairly evaluating electrochemical performance and flex- the device length (l) and bending angle (θ).112 For instance,
ibility of flexible batteries are critical yet under‐ the bending‐induced strain is most likely localized in the
appreciated in the most of references. To this end, this high bending area, while the region relatively far away from
review starts with the discussion of important assess- the deformable area remains unchanged, indicating that the
ments that are categorized into geometric, mechanical, devices with a long length remains intact in most of regions
and energy density items, providing a benchmark to (Figure 3). Besides, the greater θ with the same r implies
analyze reported results. expanded strain region. It is noted that the r is calculated
from the deformation of the inner side instead of mechanical
neutral plane, due to the easy measurement of r.
2.1 | Geometric parameters
f = 1/ r . (1)
The flexibility (f) of batteries refers to the ability that batteries
can withstand the battery deformation induced by external
force.111,112 The flexibility can be manifested as various for- The thickness (h) is another essential parameter to
mats, such as stretching, twisting, folding, bending, and their determine and characterize the battery flexibility.
F I G U R E 3 Schematics of three key

parameters (l, θ, and r) and strain distribution to
describe the flexibility of working devices.
Reproduced with permission.112 Copyright ©
2019, Elsevier Inc
Theoretically, any material that is thin enough will be bending radius and yield strain of typical flexible devices
flexible, since the bending strains linearly decreased with and materials are listed in Table 1. To preserve long‐term
thickness.113 For example, the brittle and rigid silicon flexibility and battery performances during operations,
wafer turns to flexible wires when the thickness is re- the designed materials are required to be performed in
duced to 100 nm, leading to a r of 1 cm and tensile strain the elastic region, which indicates that the tensile stress
(ε) of 0.0005%.114 These four geometric parameters (r, l, θ, (σ) should be less than the yield stress (σy). According to
and h) generally describe the key physical and geometric the definition of elastic Young's modulus (E), it refers to
features that determine the flexibility of batteries. the ratio of a stress to a strain (Equation 3).
E = σ /ε. (3)
2.2 | Mechanical parameters
Correlation of geometric parameters to mechanical Considering Equation (1), the material flexibility is
properties will benefit understanding the extent of de- proportion to the ratio of εy/E, while inverse proportional
formation, predicting devices fatigue, and probably more to the h based on the following equation111:
importantly, establishing a fundamental to theoretically
figure out stress/strain that take places in any region, f = 1/ r = (2/ h) ε y = (2/ h)(ε y / E ). (4)
thereby encouraging and targeted approaches to boost
electrochemical and mechanical performances. Assuming a fixed material thickness, the flexibility is
The tensile/compressive strain (ε) perfectly in- principally dictated by the mechanical property (εy/E),
corporates r and thickness (h) in the evaluation of flex- which is defined as a figure of merit (fFoM) to clarify
ibility through Equation (2).111 The h significantly materials flexibility, as presented in Figure 4.111 The fFoM
impacts strain that occurs in the curvature area. In this
equation, the r is based on the deformation of a me-
chanical neutral plane. In a flexible material, the outer T A B L E 1 Bending radius and yield strain of flexible devices
surface experiences the largest tensile strain while the and materials43,116–118
inner surface suffers the greatest compressive strain. Flexible devices and Bending Yield
There is a mechanical neutral plane that maintains materials radius (mm) strain (%)
unstrained. Foldable phone 3 50
Bendable phone 30 5
ε = [2π (r + h/2)– 2πr ]/2πr = h/2r . (2)
Watch belt 10 5
Roll‐up display 25 5
A material with a given thickness has to be flexed Al foil / 0.9
within a yield strain (εy), beyond which the material
Cu foil / 1.2
deforms plastically and cannot recover its shape.115 The
reveals that the compliant (small elastic modulus) yet flexible batteries with planar and wire/fiber configura-
strong (high yield strength) attributes promise a high tions, respectively. Energy density with any form can be
flexibility. directly calculated from Equation (5).
The flexible battery is commonly not very thick at the
device level predominately attributed to the fact that E n = V × Q/(m , v , A, L), (5)
bendable, yet thick devices suffer from electrochemical
performance penalty. For example, the thickness of a
flexible battery in smart phone is around 3 mm.43 wherein, En is the energy density, V is the nominal
Thereby, the flexibility of a cell with a similar thickness voltage, Q is the capacity, and m, v, A, and L are the mass,
level is ruled by fFoM. The figure of metric affords an volume, area, and length of material or device,
opportunity to rationally select desired materials, espe- respectively.
cially in the flexibility demanding applications. As materials determine the cell voltage, specific capacity,
and yield strain in principle, the optimization of energy
density and flexibility highly relies on the rational selection
2.3 | Energy density parameters of key materials. Chang et al.116 summarized the industrial
requirements of flexible batteries in term of volumetric en-
Energy density is a critical metric of a power source to ergy density and strain. The energy density of flexible bat-
characterize amount of energy per unit that can be stored teries varies depending on the battery shape and size. For
and released. “Gravimetric” and “volumetric” attributes example, the volumetric energy densities of medical patch,
are two forms of energy density in the measurement of watch belt, bendable phone, and roll‐up display are in the
battery devices depending on what is the most weighted level of 80, 400, 450, 550, and 700 Wh/L, respectively, as
in the applications.119 The gravimetric energy density, indicated in Figure 5A. The rigid commercial Li‐ion batteries
manifested as a Wh/kg, is preferred in the academic can afford an energy density of ~700 Wh/L, having a po-
community since most researches to improve battery tential to power most of flexible devices once the flexibility
performances only focus on materials chemistry, seldom and durability of batteries are well‐addressed. However, the
considering battery sealing, packaging, and other aux- minimum strain of 5% proposed by Institute for Printed
iliary components. The volumetric energy density with Circuits for flexible electronics actually exceeds the yield
an expression of Wh/L is majorly adopted by the in- strain of commonly used battery components (0.9% for Al
dustrial community because in most cases, the reserved foil and 1.2% Cu foil).117,118 The paper or fabric‐based bat-
volume of devices for power sources is constrained, teries have potential to meet with the necessary strains for
thereby requiring the materials, structures, and safety device deformation in spite of the sacrifice of volumetric
systems to be well matched for the maximize volumetric energy density.
energy density. Both areal energy density and length The comprehensive characterization of flexible bat-
energy density are also important indicators to evaluate teries by both mechanical and energy density attributes
F I G U R E 4 Flexibility figure of merit (fFoM)

for different materials. Reproduced with
permission.111 Copyright © 2019, American
Association for the Advancement of
Science, 2019
F I G U R E 5 (A) Volumetric energy density

versus strain of various electrode materials and
batteries. (B) A figure of metric for different
batteries (fbFoM). Reproduced with
permission.116 Copyright © 2020, Elsevier Inc
represents broad concepts to quantitatively compare interconnections, the fbFoM is capable of considering all
available data and afford a baseline to screen desirable fabricated cell areas, enabling fair projection of flexibility,
systems. The overall properties of flexible batteries (fb) and battery energy density.116
can be evaluated through multiplying strain by volu-
metric energy density, as Equation (6),116 obtaining a
figure of metric for flexible batteries (fbFoM) (Figure 5B) 3 | C O N S T R U C T IO N A N D
with respect to the ratio of areal energy density (Ea) and C O N F I G URA T I O N OF F L E X I B LE
bending radius of curvature (Equation 7): BATTERIES
fb = εE v = (h/2r )(QV / Ah) = (QV / A)/2r Designing well‐performing flexible batteries centers on
= 1/2(Ea/ r ). (6) materials selection, structure engineering, and config-
uration construction. Development of high‐energy active
materials, multifunctional auxiliary components (e.g.,
fbFoM = Ea/ r . (7)
current collectors, separators, electrolytes, and packa-
ging) and desired configurations contributes to the opti-
For planar flexible batteries, the areal energy density mization of electrochemical performance, mechanical
is more facilely available and preferred than the volu- stability, cost, and safety of flexible batteries. In this
metric energy density. For those with particular designed section, we first discuss how flexible components,
especially inactive materials used in batteries, impact porosity, and conductivity, aiming at a trade‐off among
mechanical properties, and battery performances. The them to construct advanced flexible batteries.
popular flexible configurations with planar and fiber Electrode materials peeling‐off from current collec-
structures are overviewed to illustrate their functions and tors occasionally take places in the slurry‐coating elec-
remaining challenges. trodes attributing to volume changes of active materials
and binder aging in the battery operation. Flexible bat-
tery electrodes experience much harder geometric de-
3.1 | Flexible battery components formation than rigid cells, which advocate to enhance the
current collector adhesion and composite cohesion to
3.1.1 | Flexible current collectors tightly hold electrode components, especially in thick
electrodes. Punching pores and coating functional layers
The current collectors serve as a substrate to collect and (e.g., carbon layer) on metal foils to enhance two‐layer
transfer electrons from active materials and external frictions are effective methods to keep thick electrode
circuits, as well as support active materials in the battery integration and boost battery energy density. Comparing
fabrication.38,93,120,121 Commercial Li‐ion batteries em- with conventional current collectors with a smooth sur-
ploy Al and Cu as cathode and anode current collectors, face, porous Al current collectors are reported to increase
respectively, due to their high electrochemical stability ~3 times in thickness and areal capacity (Figure 6A).122
toward oxidation and reduction, low cost, and excellent The combination of strong holding of active materials
electrical conductivity. Flexible batteries demand for ex- and express supply of lithium ions from electrolyte in a
tra features such as high mechanical stability under de- three‐dimensional (3D) porous structure is rationalized
formation and improved adhesion between current to enable excellent rate capability and cycle performance.
collectors and electrode materials. Direct implanting Al Besides, the integration of 3D porous Al foam and one‐
and Cu foils into flexible batteries encounters mechanical dimensional (1D) interconnected carbon nanotubes
failure or even safety hazards. The yield strain of Al and (CNTs) renders long‐ and short‐range electron pathways
Cu foil are 0.9% and 1.2%, respectively, much lower than for sulfur redox reactions (Figure 6B).123 Such hybrid
the requirement of flexible cells (5%).43 The continuous current collectors result in a high sulfur loading of
flex of working batteries causes failure of current col- 12.5 mg/cm2. Beyond punching pore in current collec-
lectors and active materials, which are responsible for tors, coating functional layers is highly expected to re-
battery performance decay and thermal runaway. inforce the interfaces of current collectors and active
Two possible strategies are accepted to render flexible materials, between which the corrosion of Al foil and
Cu and Al current collectors. The first one is the sig- weak adhesion deteriorate charge transfer and capacity
nificant reduction of thickness, by which the tensile delivery.124 A scrape test indicates that the active mate-
strain can be significantly decreased to a level that is rial layer attaches firmly on the Al/carbon layer current
below tensile fracture strain and yield strain. Any matter collectors, and that the active coating near the blades
in a thin enough format becomes flexible.113 However, break apart and exfoliates from the routine Al foil
preparing thinner metal foil not only brings processing (Figure 6C).124
challenges in commercialization scenarios, but also suf- Current collectors can be also made from carbonac-
fers an insufficient mechanical strength to support active eous and polymeric materials with various dimensions.125
materials, resulting in technique hindrances to integrate Typical building blocks includes CNTs,126–128 carbon
the current roll‐to‐roll method into fabricating full flex- fibers,129–133 carbon cloth (CC),134,135 graphene,136–139
ible batteries. Another strategy to diminish strain lies in polyacrylonitrile (PAN),140,141 cellulose,142–144 and their
the engineering the porous structure of metal foils. Nu- hybrids.145 These current collectors are featured with high
merical analysis reveals that the flexibility increases ex- flexibility, extraordinary conductivity, light weight and
ponentially with the increase of structural porosity.49 For large surface area, favoring mass/charge transport, active
example, the stress in a material with a porosity of 0.5 material supports, and volume change accommodation.
can be reduced by 88% compared with the solid coun- CNTs are constituted by the covalently bonded
terpart in the same bending radius. However, the porous sp ‐carbon, endowing it with super mechanical, electro-
2
structure has an adverse effect on the electrical con- chemical, and thermal stability.146 The interlaced CNTs
ductivity of current collectors. The porous foam with a can be easily assembled into films,147,148 sponges,149,150
porosity of 0.5 is estimated to exhibit only 40% con- and fibers,151,152 as promising platforms for flexible cur-
ductivity of the solid one.50 Therefore, the development rent collectors. Zhou et al.153 described a template‐
of flexible current collectors based on Cu and Al foils assisted synthesis of S–CNT composite film for a binder‐
need to decently consider mechanical stress, thickness, free, and flexible high‐rate Li–S batteries (Figure 7A,B).
F I G U R E 6 Flexible metal foil current collectors with surface and structure modifications. (A) Schematics of thick electrodes with
porous Al foils. Reproduced with permission.122 Copyright © Elsevier B.V. 2016. (B) SEM images of pristine porous Al foil and cross‐
sectional view of porous Al foil supported CNT/S layers. Reproduced with permission.123 Copyright © Elsevier B.V. 2014. (C) Schematics of
functions of the nanocarbon coating layers between the Al foil and sulfur cathodes. Reproduced with permission.124 Copyright © 2016,
Science China Press. CNT, CNT, carbon nanotube; SEM, scanning electron microscope
This film can withstand a strain of 9% and remain un- discourages their potential in the practical battery
changed in 12,000 bending cycles (Figure 7C). In- systems.158–160 On the other hand, the CC or carbon
trinsically high‐capacity metal oxides that exert textile have been widely adopted as flexible current col-
conversion reaction chemistry are of great interests, lectors to support active materials. For instance, a flexible
whereas their low ionic and electrical conduction leads to solid‐state Ni/Fe battery is developed using needle‐like
inferior capacity and rate delivery. Therefore, the con- Fe3O4 and flake‐like NiO directly grown on CC/carbon
formal deposition of metal oxide on high‐surface‐area fiber (CC–CF) matrices as the anode and cathode, re-
CNT is anticipated to expose more active surface for spectively (Figure 7F).155 The hierarchical and flexible
electrochemical redox, rendering high capacity and rate CC–CF substrate bearing nanocrystalline Fe3O4 and NiO
performance. Wu et al.154 reported a Fe3O4–CNT film by buffers the volume change, facilitates charge transport,
magnetron sputtering F3O4 on CNT scaffolds, forming a and tolerates mechanical deformation. The solid‐state
uniform coating of metal oxides with controllable sizes Ni/Fe full cells can be bent and twisted at different states
and mass fractions (Figure 7D,E). The free‐standing without sacrificing the battery performance (>97% re-
Fe3O4−CNT electrode exhibits a specific capacity of tention; Figure 7G). The CC can be also decorated by
800 mAh/g based on the total electrode mass. The CNT other mediators to extend their applications. For ex-
film can be further functionalized by nitrogen/oxygen ample, Yu et al.161 incorporated CoP nanoparticle cata-
codoped porous carbon for the fabrication of flexible lysts on the CC, imparting electron conduction, physical
electrodes for Na‐Se and K‐Se batteries.156 As most of encapsulation, and chemical entrapment effects to reg-
CNT‐based films are prepared by solution‐mediated ulate polysulfide migration and conversion, leading to
processes that impedes large‐scale and uniform fabrica- superb rate capability and cyclability of Li–S batteries.
tion of targeted free‐standing current collectors, mas- The CC with low cost and mature fabrication technology
sively, uniformly, and cost‐effectively incorporating represents superior attributes to flexible devices. Addi-
active materials in CNT films remains an unsettled tional advantages of excellent electrical conductivity and
problem. high mechanical strength further accelerate their appli-
Analogous to CNT‐based films, commercially CC or cations in flexible batteries. The remaining challenges lie
carbon textile, which is woven by carbon fibers, also at- in their low surface area and limited adhesion to uptake
tracts wide attention due to its low cost, reasonable and anchor more actively materials.
conductivity, strong mechanical strength, and high Two‐dimensional (2D) graphene is a theoretically
flexibility.157 The carbon textile and carbon fibers have single‐atom carbon film. The thickness of graphene
been tested as lithium and sodium ion storage materials prepared by the solution process actually ranges from
in Li‐ion batteries, whereas the large voltage hysteresis several to more than ten atom layers.162,163 Graphene can
F I G U R E 7 1D CNT and carbon cloth for flexible current collectors. (A) AOO assisted formation of S‐CNTs electrode. (B) Photograph of
the flexible S‐CNT membrane. (C) Stress–strain curve of a typical flexible S‐CNT cathode and inset displays a bendable characteristic.
Reproduced with permission.153 Copyright © 2012, The Royal Society of Chemistry. (D) Schematics of the sputtering synthesis of
Fe3O4−CNT electrode and inset is the photograph of the Cu cylinder wrapped with Fe3O4−CNT. (E) TEM image of Fe3O4−CNT composite
anode. Reproduced with permission.154 Copyright © 2013, American Chemical Society. (F) Schematics of structure and attributes of flexible
Ni/Fe cell with enhanced electrochemical performance. (G) Charge–discharge profiles of the flexible cell under bending and twisting
conditions as shown in the insert. Reproduced with permission.155 Copyright © 2016, WILEY‐VCH. AOO, anodic aluminum oxide; S‐CNT,
sulfur‐carbon nanotube; TEM, transmission electron microscopy
be processed into foams,3,164 sheets,165,166 and fibers,167 concept of interlinked all‐carbon scaffolds for sulfur
as substrates to support electrode materials in flexible cathode, in which CNTs were employed to form highly
batteries. Li et al.168 proposed a sandwich structure by efficient conductive networks and MgO‐derived
laminating a sulfur/carbon slurry between two pieces of graphene nanocages to accommodate sulfur powders
graphene sheets. In this structure, one piece of a gra- (Figure 8C,D). The flexible sulfur cathode exhibited ex-
phene current correct supported sulfur powders and the cellent capacity of 750 mAh/g at a high current density of
other one coated on PP separators (G‐separator), thus 8.35 A/g. 3D porous scaffolds based on CNT and gra-
constructing a binder‐free and flexible sulfur electrode phene can be also prepared by a vacuum freeze‐drying
(Figure 8A). The proposed structure was compatible with method.170 The sandwich‐like architecture loaded with
industrial process, presenting a feasibility to scale up the MnO2 nanoparticles could provide vast accessible active
fabrication of flexible Li–S batteries (Figure 8B). sites, and facile electrolyte percolation (Figure 8E), which
Integration of 1D CNTs and 2D graphene to fabricate are jointly responsible for a high capacity, excellent rate
flexible current collectors can take advantage of both performance, and superior cycling stability (1344.2 mAh/g
merits of 1D and 2D building blocks for emerging flexible over 630 cycles at 2 A/g, 608.5 mAh/g over 1000 cycles at
batteries. CNTs work as a pillar to prevent graphene from 7.5 A/g).
stacking together, while the graphene facilitates uniform Besides the sp2‐carbon families, carbonization of
dispersion of CNTs. This hybrid nanoarchitecture can polymer and natural cellulose is also an effective and
expose more supporting surface to distribute active eco‐friendly method to produce soft and free‐standing
materials and preserve better mechanical integration in current collectors for flexible battery applications. For
bending and twisting. Huang et al.169 demonstrated a example, Wu et al.171 described a free‐standing sulfur
F I G U R E 8 Graphene and CNT/

graphene hybrids for flexible current
collectors. (A) Schematics of a Li–S battery
with graphene‐based electrode and
separator. (B) Photographs of large‐scale
GCC strips. Reproduced with permission.168
Copyright © 2013, WILEY‐VCH. (C)
Schematic of hybrids of CNT/carbon
nanocage for flexible sulfur cathode. (D)
Photographs of the flexible sulfur cathode
membrane. Reproduced with permission.169
Copyright © 2013, The Royal Society of
Chemistry. (E) Schematics to illustrate 3D
porous CNT/graphene derived freestanding
film electrodes. Reproduced with
permission.170 Copyright © 2018,
WILEY‐VCH. CNT, carbon nanotube;
GCC, graphene current correct
cathode by carbonization of porous cellulose sheets, the contact of conductive scaffold and active materials,
which supported Li2S nanoparticles through infiltrating a Wang et al.173 developed a strategy that concurrently
Li2S solution under vacuum (Figure 9A). The spatially electrosprays active materials and electrospins a PAN
homogeneous Li2S distribution and high conductivity solution to form PAN‐coated nano‐Si clusters into a PAN
and connectivity of cellulose‐derived porous polymer nanofiber paper (Figure 9C). The subsequent carboniza-
sheets contributed to stable operation of Li–S batteries tion imparts high conductivity to electrodes while re-
with a high sulfur loading. Electrospinning of polymers mains flexible (Figure 9D). These advantages render
followed by carbonization to prepare 1D cellulose na- superior electrochemical performances, evidenced by a
nofibers has been widely applied. This approach provides high capacity of 840 mAh/g after 600 cycles.
a direct and low‐cost way to fabricate flexible electrodes. 1D CNTs, 2D graphene, polymer‐/cellulose‐derived
Deng et al.172 reported a PAN‐derived carbon nanofiber substrates, and their hybrids constitute major building
(CNF) matrix by a two‐step electrospinning and anneal- blocks to fabricate flexible current collectors. These
ing method to host Nb2O5@MoS2@C composite building blocks can be modified by heterogeneous
(Figure 9B). The high conductivity of CNF layers, atoms or external mediators for multielectron battery
structurally stable Nb2O5/C, and high‐capacity MoS2 sy- chemistries.174 These current collectors share common
nergistically contributed to the rate and cycling char- features of high electrical conductivity, robust me-
acters of electrode that exhibit adsorption‐intercalation‐ chanical strength, and hierarchical pore structure,
conversion mechanisms in Na‐ion batteries. To increase which comprehensively take responsibility for facile
F I G U R E 9 Carbonization of polymer and natural cellulose for flexible current collectors. (A) Synthesis flows for the flexible sulfur
electrodes with carbonized porous cellulose sheets. Reproduced with permission.171 Copyright © 2018, WILEY‐VCH. (B) Schematics of the
nanostructure of Nb2O5@MoS2@C CNFs films and its corresponding photographs. Adapted with permission.172 Copyright © 2020,
WILEY‐VCH. (c) Synthesis process of the flexible 3D Si/C fiber paper electrode. (D) Photographs of fiber paper electrodes. Reproduced with
permission.173 Copyright © 2014, WILEY‐VCH. CNF, carbon nanofiber
electrochemical redox kinetics, uniform active materials efficient batteries. Liquid electrolytes are still the primary
distribution, and high electrode deformation. CNTs and option for flexible Li‐ion batteries due to their facile
graphene are regarded as star materials in free‐standing percolation, rapid ion mobility, good wetting ability, and
current collectors, while their cost‐effective production stable solid‐electrolyte interphase (SEI) property. How-
of CNTs and graphene, as well as scale‐up fabrication of ever, liquid electrolytes intrinsically suffer from in-
flexible current collectors by the solution‐mediated trinsically safety issues and battery aging ascribed to
processes are still challenging. Electrospinning is a lithium dendrite growth and electrolyte leakage. Alter-
mature technology to prepare fiber‐shaped building natively, solid‐state electrolytes emerge as promising
blocks from polymers, which are easier to be woven into charge carriers to couple with lithium metal anodes to-
textile art than CNTs and graphene. These advantages wards safe and high‐energy flexible batteries.177,178 Solid
are favorable for the development of device‐level flex- electrolytes have advantages of negligible electrolyte
ible batteries. leakage to avoid cell failure or fire, high Young's modulus
to inhibit lithium dendrites, wide electrochemical win-
dow to enable high‐voltage cathode applications, and
3.1.2 | Flexible electrolytes easy cell patterning to reduce inert components and
fabrication cost.179–182
The electrolyte is a key component that serves as an ionic Solid electrolytes can be divided into polymer‐based,
conductor yet an electronic insulator to keep facile ion gel‐type, inorganic‐type, and organic/inorganic compo-
transport and minimized self‐discharge.87,175,176 Selec- site electrolytes. The complete solid electrolytes without
tion of a suitable electrolyte that can be compatible with any rubber‐like additive cannot be deformable due to
other cell components is a prerequisite task to enable their brittle and rigid natures. This subsection mainly
describes attributes of polymer‐based, gel‐type, and or- plasticizers to promote the formation of amorphous seg-
ganic/inorganic composite electrolytes in working flex- ments, which further expedite lithium transport kinetics.
ible batteries. The application of solid polymer electrolytes in flex-
Solid state polymer electrolytes (SPEs) are commonly ible full batteries was demonstrated by the rational de-
composed of coordinating polymer scaffolds, lithium salts, sign of plastic crystal polymer electrolytes (N‐PCPEs)
and plasticizers (liquid or solid), thereby combining ionic laminated in a LiCoO2 cathode and a Li4Ti5O12 anode
conductivity with solid yet flexible mechanical properties (Figure 10B).95 The compliant yet porous polyethylene
for flexible batteries.183–185 The coordinating polymers terephthalate strengthens the skeleton to support poly-
commonly used in solid electrolytes include poly(ethylene mers that are derived from ethoxylated trimethylolpro-
oxide) (PEO),186,187 PAN,188,189 and poly(vinylidene fluor- pane triacrylate monomers. The structural robustness
ide) (PVDF).190,191 Lithium salts with relatively high dis- and electrochemical superiorities of proposed polymer
sociation capability are employed in view of their high Li+ electrolytes render stable cycling (99% retention within
mobilities. The lithium conduction is facilitated by the local 50 cycles), high rate (~120 mAh/g at 2.0 C), and negli-
segmental motion of the polymer chains.192,193 The dis- gible voltage fading in the bending radius of 5.0 mm. The
sociated lithium ions from counterions coordinate with polymer nanoarchitectures in such design replace the
electron‐donor groups of polymers, and move to neigh- routine separators and liquid electrolytes and remain
boring electron‐donor sites through ion hoppings under sufficient ion transport, demonstrating a possibility to
electric fields (Figure 10A).179,194 To increase the local development of solid yet flexible Li‐ion batteries at a high
motion of polymer chains, solid particles (e.g., SiO2, rate capability without a necessity of flammable and toxic
Al2O3)196,197 and solvents (e.g., EC, PC)198 are functioned as nonaqueous electrolyte.
F I G U R E 10 Solid state polymer electrolytes for flexible batteries. (A) Lithium ion transport mechanism in PEO‐based polymer
electrolytes. Reproduced with permission.194 Copyright © 2014, Elsevier Inc. (B) Schematics of bifunctional polymer membrane as both
electrolyte and separator for of LiCoO2/Li4Ti5O12 full cell. Reproduced with permission.95 Copyright © 2014, WILEY‐VCH. (C) Schematics
of preparing electrode membrane with an intimate electrolyte film by a 3D printing process. (D) Schematics of the polymer electrolyte
composition and corresponding dried film after casting ink. (E) Thermal properties of polymer electrolytes and routine separator at 140°C.
Reproduced with permission.195 Copyright © 2017, WILEY‐VCH. PEO, poly(ethylene oxide)
Integration of advanced processing technologies, such The impressive ionic conductivity is ascribed to the in-
as 3D printing, into solid electrolytes preparation has terfacial effect at the polymer/LLZTO boundaries.205 Aside
been reported to further promote flexible solid Li‐ion from improved ionic conductivity, a critical attribute of
batteries in terms of safety, rate capability, and proces- composite electrolytes is the immobilization of lithium salt
sing simplification.199 Blake et al.195 reported a 3D anions that favors fast lithium ion conduction. A PEO‐
printable polymer electrolyte for flexible batteries by LiTFSI‐LLZTO ternary flexible electrolyte membrane is
diligently selecting ingredients. A high‐quality proposed to simultaneously reduce crystallization of PEO
ceramic–polymer electrolytes prepared by phase inver- and pin anions of LiTFSI, resulting in well‐distributed Li
sion was directed coated on a LiFePO4 composite cathode ions and dendrite‐free deposition (Figure 11A).100 The
(Figure 10C), forming a tight interface between electro- prepared membrane is highly flexible and has a thickness
des and electrolytes to reduce interfacial resistances. The of only 30 μm (Figure 11B), which is comparable with a
combination of NMP/glycerol solvents and nanoceramic thickness of commercial separator. These merits have the
Al2O3 fillers facilitates the formation of a controlled pore potential to enable batteries with a flexible and high vo-
structure, resulting in a highly flexible composite film lumetric energy density.
(Figure 10D). The as‐prepared solid electrolytes can re- Different kinds of organic and inorganic components
tard fire‐induced damage at an elevated temperature have been used in inorganic/organic composite electrolytes
(Figure 10E). It promises a safe operation of batteries, to explore possibilities of enhancing ionic conductivity,
which is hardly achievable by combustible liquid elec- broadening voltage window, and improving electrode/
trolytes and polyolefin separators. The optimal pore electrolyte interfacial compatibility.18,208–214 However, the
structure and improved interfacial wetting ability con- flexible batteries with composite electrolytes under com-
tribute to impressive rate performance (5 C) that is mercially required tests are rather limited, since the mate-
comparable with commercial separator based cells. It is rials, structure, and configuration design still cannot
noted that the prepared cells were aged in liquid elec- withstand significant deformation, especially taking energy
trolytes to curtail interface resistances before cell opera- density and safety into considerations.
tion. Interface resistance and bulk ionic conductivity in In spite of the above advantages, polymer‐based and
polymer electrolytes still hamper the performance of inorganic/organic composite electrolytes cannot easily
flexible batteries, especially the high areal capacity and achieve rapid ionic transport at room temperature and
rate capability at the room temperature. To enhance favorable interfacial contact.215,216 Alternatively, the gel
contact of electrolyte–electrode interface, Yu et al.200 polymer electrolytes (GPEs) trap liquid organic compo-
demonstrated a possibility to penetrate the liquid nents in polymeric scaffolds, which uniquely combine
monomer precursor into the sodium cathode layer and advantages of polymer electrolytes (leakage‐proof) and
then initiate the electrolyte polymerization to form in- liquid electrolytes (highly ion‐conductive), being of re-
timate and compliant electrode/electrolyte film. This search interests in solid‐state batteries.217–219 The extra-
synthetic route presents a general concept to reduce the ordinary solvating power for lithium salts and excellent
interfacial resistance, benefiting the ionic transfer be- compatibility with metallic lithium endow PEO as at-
tween the solid electrolyte/electrode interface. Polymer tractive skeleton of GPEs, while its mechanical strength
solid electrolytes with PAN,201,202 and PVDF203,204 ma- is compromised by the solvent plasticizers.220 In-
trices have also been investigated to enrich the materials corporation of rigid polymer segments, such as PVDF,221
options for the high‐performance flexible batteries. PAN,222 and poly(dimethylsiloxane),223 into PEO has
Inorganic/organic electrolytes in this review refer to been proposed to reinforce the electrolyte film. The bal-
polymer electrolyte systems with the incorporation of ance of rigidity and flexibility for GPEs can be also tai-
solid fast ionic conductors. The ionic conductors them- lored by co‐block polymers. For instance, Chen et al.206
selves are inorganic solid‐state electrolytes with intrinsic employed a poly(vinylidene‐co‐hexafluoropropylene)
safe nature and fast ionic conductivity, which are widely (PVDF‐HFP) framework to host ionic liquid and TiO2
used in all‐solid‐state batteries. Besides influencing the plasticizer, forming an ionically conductive and me-
crystallization of polymer chains and favoring the for- chanically robust GPEs (Figure 11C). This hybrid ionogel
mation of local amorphous regions, the inorganic solid‐ enables nonliquid‐electrolyte Li‐ion batteries with long‐
state electrolytes also afford extra ionic transport path- term cyclability and high‐rate performance.
ways in the polymer matrix. A Li‐salt‐free PEO and The adjustable ingredients of GPE composition and
LLZTO membrane with 40 μm thickness has been fab- its soft nature also afford fresh concepts to address cur-
ricated to exert a high ionic conductivity (10−4 S/cm at rent bottlenecks of lithium metal anodes.224 The PVDF‐
30°C), which is hardly achieved in conventional PEO HFP film can be further functionalized by SEI‐forming
based electrolytes due to crystallization below 60°C. additives. For instance, an effective artificial protective
F I G U R E 11 Composite electrolytes and gel polymer electrolytes for flexible batteries. (A) Schematics of the immobilized anions
anchored to polymer chains and LLZTO ceramic particles. (B) Photographs and cross‐sectional SEM images of the composite electrolytes.
Reproduced with permission.100 (C) Preparation process of hybrid gel polymer electrolytes with PVDF‐HFP. Reproduced with permission.206
Copyright © 2018, Elsevier Ltd. (D) Functionalities of artificial protective layers with organic PVDF‐HFP and inorganic LiF on lithium metal
anodes. Reproduced with permission.207 Copyright © 2018, WILEY‐VCH. (E) Schematics of the synthesis of PPN electrolytes. (F)
Schematics of the possible effects of PAN–EC interaction on the SEI layer. Reproduced with permission.103 Copyright © 2019, The Royal
Society of Chemistry. PPN, polar polymer network; PVDF‐HFP, poly(vinylidene‐co‐hexafluoropropylene); SEI, solid‐electrolyte interphase;
SEM, scanning electron microscope
layer is proposed by adding LiF into PVDF‐HFP to In spite of featuring both solid and liquid character-
achieve attributes of high mechanical modulus, high io- istics to deal with interfacial resistance, low bulk ionic
nic conductivity, superb shape compliance, and good conductivity, and liquid electrolyte leakages, the GPEs
compatibility with Li metal anodes, enabling uniform Li still encounters safety issues in the event of thermal
deposition (Figure 11D) in the corrosive carbonate elec- runaway due to trapped liquid electrolytes. Some liquid
trolytes.207 Recently, Yu's group proposed the tailor of the electrolytes with fire‐retarding properties may facilitate
reactivity between carbonate electrolytes and lithium the extended application of GPEs in flexible batteries.225
metal anodes through GPEs. A polar polymer network
(PPN) was fabricated based on cross‐linkable poly-
ethylene glycol diacrylate (PEGDA) oligomers, PAN 3.1.3 | Flexible separators
polymers, and EC solvents, in which PAN mitigated the
solvent decomposition on the surface of the lithium The separator is inserted between the cathode and anode,
metal, and PEGDA provided a 3D polymer network to allowing working ions to transport and preventing elec-
accommodate liquid solvent and PAN (Figure 11E).103 trons to migrate in inner circuits.88,226 The pore struc-
The reversible lithium plating/stripping processes are ture, material constitution, and processing technology
rationalized by cooperative functions of PPN. The dominantly determine battery performance, reliability,
dipole–dipole interaction between C═O (from EC) and and safety.227,228 The routine separator is usually made
C≡N (from PAN) reduces both reactivity of EC and PAN by microporous polyolefin membranes, such as poly-
toward lithium anode. In addition, the PPN facilitates the ethylene, polypropylene (PP), and their blends, with a
decomposition of lithium salt anions, forming inorganic thickness of 20–40 μm.88 However, polyolefin mem-
lithium salts dominated SEI to protect lithium metal branes have low thermal stability and insufficient elec-
anodes (Figure 11F). trolyte wettability. Therefore, separator materials with
F I G U R E 12 Separators for flexible batteries. (A) Schematic of hierarchical assembly of hydroxyapatite nanowire networks and Cellulose
fibers. (B) Fabricating the layered separator by the filtration process. Reproduced with permission.229 Copyright © 2017, WILEY‐VCH.
(C) Schematics of cation permselective membrane enabled by the Nafion film. (D) Morphologies of the routine and Nafion coated
membranes. Reproduced with permission.230 Copyright © 2014, The Royal Society of Chemistry. (E) Schematics of the design principles of
polymer–polymer composite electrolytes. (F) Cross‐sectional SEM images of a nanoporous PI film (bottom) with zoomed‐in image of the
aligned nanopores (top). (G) Photographs of a large‐scale porous PI film. Reproduced with permission.102 Copyright © 2019, Springer Nature
Limited. PI, polyimide; SEM, scanning electron microscope
better fire resistance, thermal stability, and wettability (Figure 12B). The finely design separators can safely
are weighted in some special flexible batteries. work at 150°C in a routine liquid electrolyte.
Li et al.229 reported a flexible and porous separator The eco‐materials derived separators for flexible batteries
based on hydroxyapatite nanowires and cellulose fibers. present a critical trend to integrate electrochemical energy
The hydroxyapatite nanowires possess high thermal into global clean energy scheme.231–233 To meet with special
stability and excellent fire resistance, while cellulose targets of flexible batteries, some other polymeric materials
fibers have plenty of active groups (–OH and –COOH) of PVDF, PAN, and polymethyl methacrylate (PMMA) can
to enhance substantially interfacial interactions be also processed to form microporous separators due to
through hydrogen bonds and van der Waals forces, greater conductivity and flexibility.88,227 As polyolefin mem-
which are beneficial for self‐assembling into hier- branes exhibit poor wettability and solvation in Na+/K+/
archically cross‐linked hybrid fibers (Figure 12A). Zn2+/Al3+‐containing electrolytes, the battery chemistries
The flexible separators can be further prepared by beyond lithium, however, prefer glass fiber separators despite
filtrating hydroxyapatite nanowires and hybrid fibers sacrificing thickness (around 300–500 mm) and flexibility.234
Polyolefin separators are intrinsically flexible and electrolytes, appropriate porosity for ion transportation,
mechanically robust enough, which allows direct appli- and strong mechanical strength to prevent splitting, the
cation in the flexible batteries coupled with liquid elec- separators in flexible batteries with conversion reaction
trolytes. Emerging battery chemistries that exert mechanisms require additional features to enable effi-
dissolution/deposition mechanisms set new require- cient operation under flexing, such as ionic shield, large
ments to regulate mass/charge transportation.235,236 mechanical durability, and adaptivity, as well as fast io-
Taking Li–S batteries, for example, the lithium poly- nic conductivity. The separator setup in flexible batteries
sulfide (LiPS) intermediate migration induces lithium is actually challenging, especially in 1D fiber‐shaped
anode instability and Columbic efficiency reduc- format.239,240 The preparation of an adaptive separator to
tion.237,238 Anchoring LiPSs in the cathode side is a electrode layer or fiber requires emerging materials
paramount task to prolong cycling life, and separator innovation and related processing.
modifications are representative strategies to enable ef-
ficient operation of Li–S batteries. Huang et al.230 first
proposed an ion‐selective membrane by coating Nafion 3.2 | Configuration of flexible batteries
film on Celgard 2400. The sulfonate‐ended perfluoroalkyl
ether groups on the Nafion film allow ion hopping of Conventional rigid battery configurations are generally
positively charged species (Li+) but reject hopping of based on planar sheets, which are sequentially packed
negative ions (Sn2−) due to the Coulombic interactions with intimate contacts to enlarge energy density and di-
(Figure 12C). The slit‐pores on routine separators can minish peeling off active materials from substrates. The
be completely and uniformly covered by Nafion film planar structure is also popular in the design of flexible
(Figure 12D). The chemical and structural uniqueness of batteries, ascribing to easy and mature fabrication tech-
the cation permselective separator enabled an ultralow niques. However, materials and structure design, such as
decay rate of 0.08% per cycle within 500 cycles. porosity, composition, and building blocks, in the planar
Liquid electrolytes are flammable and are prone to configurations need to be particularly constructed to
leak under abnormal conditions, unless strict packaging enable a balance of flexibility and electrochemistry. Fiber
technology is applied to seal cells. Therefore, replacing shaped structures recently gain growing attention by
liquid electrolytes with solid‐state electrolytes is an alter- taking advantages of miniaturization, adaptability, and
native to tackle safety and sealing issues. This paradigm weavability.22 In the following subsections, recent ad-
shift relies on the rational design of separators from two vances in flexible battery configurations with 2D planar
aspects: (i) eliminating the routine separators and ren- and 1D fiber and their assemblies are introduced.
dering solid‐state electrolytes to be bifunctional to si-
multaneously separate electrodes and transport ions; and
(ii) constructing favorable channels in separators to permit 3.2.1 | Planar structures
solid electrolyte infusion into separator pores. Conse-
quently, mechanically flexible and ionically conductive Planar structure design in flexible batteries covers diverse
separators can enable Li‐ion storage performance in formats of paper, thin‐film, and origami and spinel‐like
working batteries. The first strategy has been widely used structures. Any of them encompasses electrode layers
for the development of GPEs in flexible batteries. How- (including current collectors and their supported cath-
ever, soft GPEs cannot avoid internal short circuit during ode/anode materials), electrolytes, separators, and
repeated deformation, and their thickness is commonly packaging, which are assembled layer by layer
much larger than conventional separators, reducing vo- (Figure 13A).119
lumetric energy density. Wan et al.102 recently proposed Paper‐based flexible batteries are commonly fabri-
an ultrathin, high‐performance, and flexible separator that cated with continuous conductive networks that are as-
integrates polymer electrolytes into polymer membrane sembled by graphene, CNTs, CNFs, and their hybrid
for all‐solid‐state Li batteries. (Figure 12E). The functional derivatives. Enabled by high flexibility, light weight, su-
membrane is made of a robust, nonflammable polyimide per chemical/electrochemical stability, and large surface
host with vertically aligned nanochannels and Li‐ion area, paper‐based electrodes integrate current collectors
conductive PEO–LiTFSI electrolytes (Figure 12F). The and active materials to achieve high areal capacity and
nanoporous polyimide is flexible and commercially avail- flexibility. CNTs are featured with an extremely high
able, promising a scalability of such separator systems electrical conductivity and fatigue resistance,244 endow-
(Figure 12G). ing them with significant advantages to build up flexible
In addition to chemical and electrochemical stability electrodes. The porous networks of CNTs construct im-
to electrolytes and electrodes, excellent wettability with pressive long/short mixed electron/ion transport
F I G U R E 13 Planar flexible batteries. (A) Schematics of planar configuration flexible batteries. Reproduced with permission.119 Copyright
© 2020, Elsevier B.V. (B) 3D CNT film for planar sulfur electrodes. Reproduced with permission.241 Copyright © 2016, WILEY‐VCH.
(C) Planar sulfur electrodes with stacked CNT/S layers for high areal capacity. Reproduced with permission.96 Copyright © 2014, WILEY‐VCH.
(D) Photographs of belt‐shaped aqueous sodium‐ion batteries. Reproduced with permission.242 Copyright © 2020, Elsevier Inc. (E) Capacity
retention of high‐voltage solid‐state and liquid‐electrolyte lithium batteries. Reproduced with permission.243 Copyright © 2014, WILEY‐VCH.
CNT, carbon nanotube
pathways in hierarchical structures. CNT paper‐based (Figure 13D).242 Guo et al.242 reported flexible aqueous
current collectors have been used to support various ac- sodium‐ion batteries based on a Na0.44MnO2 cathode
tive materials, such as V2O5,245 LiFePO4,246 Li4Ti5O12,247 and a nano‐sized NaTi2(PO4)3@C anode. Such belt‐
and NCM.248 The recent arise of interests in high‐energy shaped batteries can achieve a high mass loading of
Li–S batteries have triggered tremendous efforts to the 10 mg/cm2 while preserving excellent volumetric en-
development of sulfur cathodes,249,250 electrolytes,45 and ergy density and high flexibility. Other belt batteries
lithium metal anodes.251 Peng et al.241 demonstrated a with the electrodes configuration of Li1.1Mn2O4/Li-
flexible CNT‐based sulfur electrodes to increase sulfur Ti2(PO4)3,257 Li/O2,258 and pyrene‐4,5,9,10‐tetraone/
contents, curtail passivation layers, as well as promote Zn259 batteries were also explored to tap the potential
redox kinetics of sulfur interconversions (Figure 13B). A of belt‐shaped flexible batteries.
high‐areal‐capacity sulfur cathode was realized by Thin‐film battery strategies markedly reduce the ion/
straightforwardly stacking free‐standing CNT paper electron conduction distance, and thus enable the suc-
electrodes, which reached to an ultrahigh sulfur loading cessful employment of relatively resistive electrolytes
of 17.3 mg/cm2 (Figure 13C).96 The paper substrates as- (e.g., polymer electrolytes and even ceramic solid‐state
sembled by 2D graphene and MXene nanosheets present electrolytes), which faces up with a variety of challenges
a popular choice to wrap active materials.252,253 For in- in the slurry‐coating batteries. The high flexibility of
stance, graphene and MXene paper are selected as a thin‐film batteries is rooted in the significant reduction of
scaffold to load V2O5,254 LiFePO4,255 and silicon,256 strains at small thickness, as discussed in the previous
leading to improved battery performances. section. For instance, Dudney's group demonstrated
The thin‐film batteries with a lamination structure a thin‐film solid state cell with a high‐voltage
have a super bending capability, and therefore can be LiNi0.5Mn1.5O4 cathode, a LiPON electrolyte, and a
adapted in wearable devices. A typical fabrication lithium metal anode.243 This thin‐film cell delivered a
process of belt‐shaped batteries includes pressing ac- superb cycling stability (10,000 cycles) and ultrahigh rate
tive materials film on soft film substrates, stacking a performance (10 C), affording a fascinating possibility to
separator between them, filling electrolytes, and push thin‐film solid‐state batteries forward (Figure 13E).
sealing the cell through a vacuum sealing process Multiple challenges seem to be drastically mitigated in
F I G U R E 14 Battery configuration design for flexible batteries. (A) Schematics of bioinspired highly flexible cell design. (B) Schematics
of the fabrication process of a spine‐like battery. Reproduced with permission.101 Copyright © 2018, WILEY‐VCH. (C) Schematics of the
exploded multilayer structure of conventional LIBs in the planar state. (D) Two examples of folding origami LIBs using Miura. Reproduced
with permission.97 Copyright © 2014, Macmillan Publishers Limited
thin‐film batteries, such as lithium dendrite growth, li- stores/releases energy, while a thin and flexible inter-
thium pulverization, parasitic reactions between lithium connection serving as marrow withstand deformable
and LiPON, as well as progressive resistance build‐up strains (Figure 14B).101 The “vertebra” electrode can be
that restrain performances of the conventional coin‐type made thick and massively prepared by slurry coating
cells or pouch cells. Such impressive battery perfor- technique, ensuring high active materials loading. The
mances encourage more efforts to realize high‐ “marrow” interconnections enable a harsh dynamic me-
performance solid‐state batteries that can concurrently chanical load, endowing batteries with excellent flexibility.
take advantage of the current battery fabrication Such spine‐inspired flexible batteries decouple the flex-
technology. ibility and energy density, which are promising for broad
While elastomeric materials selection and thickness applications in flexible and wearable electronics.
reduction are both effective approaches to render rigid
batteries flexible, ingenious battery configuration design
represents a trend to simultaneously impart energy 3.2.2 | Fiber structures
density and flexibility to devices. Origami patterned
flexible batteries allows to incorporate commercially The fiber‐shaped flexible batteries featuring 1D structure
standard packaging technologies into deformable elec- can be performed in stringent conditions and processed
tronic devices, leading to potentially practical applica- into textiles. Fiber batteries are ubiquitously classified
tions.97 Origami batteries fold slurry‐coated cathode and into coaxial and twisted formats, considering a relative
anode layers, separators, and packaging into specific position of the two electrodes (Figure 15).260 A unique
origami patterns of Miura‐ori. The identical parallelo- attribute of fiber batteries is their processability that can
gram faces are connected by creases, allowing either be adapted into smart clothes, wrist bands, and gloves.
almost complete compression in one direction or col- The coaxial structure is an art of the multiple core‐shell
lapsing in two directions along creases, whereas paral- assembly, which is achieved through layer‐by‐layer
lelogram faces themselves remain unstrained. This wrapping of anodes, separators, cathodes, and packa-
strategy intimately combines origami art, materials ging. The twisted structure interwinds two fiber electro-
science, and energy storage devices, affording a fresh des with a certain twisting angle to form a double‐helix
concept to create flexible devices with much‐improved structure. The electrodes in twisted fiber batteries require
energy/power densities. to be coated by separators or solid‐state electrolytes to
Another inspiring example of flexible battery design is prevent an internal short circuit.
the spine‐like Li‐ion batteries (Figure 14A), in which a The coaxial fiber batteries are pioneeringly developed
thick, rigid segment mimicking vertebra of animals by Kim et al.,94 and exhibit extreme levels of mechanical
aligned CNT/Si composite fiber electrodes.98 The higher

length capacity can be directly realized by twisted more
CNT/Si composite bunches, by which the volume chan-
ges of Si with a high content can be effectively accom-
modated (Figure 17A). To simultaneously obtain high
energy and power densities in a device, a fiber‐shaped
hybrid energy‐storage device are formed by twisting
CNT/ordered mesoporous carbon (OMC), CNT/LTO,
and CNT/LiMn2O4 (LMO) hybrid fibers together
(Figure 17B).263 The rationally designed hybrid energy‐
storage device delivered an excellent energy density
(50 mWh/cm3 or 90 Wh/kg) and power density (1 W/cm3
or 5970 W/kg), which were superior to corresponding
thin‐film Li‐ion batteries and supercapacitors, respec-
tively (Figure 17C).
A fascinating attribute of 1D fiber‐shaped compo-
F I G U R E 15 Fiber‐shaped flexible batteries. Schematics of (A) nents is the capability of being woven into 2D deformable
coaxial and (B) twisted 1D flexible batteries. Reproduced with
and breathable textiles through the well‐established tex-
permission.260 Copyright © 2018, The Royal Society of Chemistry
tile technologies. Battery textiles integrate energy storage
into wearable devices, representing an ultimate target of
flexibility necessary in various flexible electronics. This wearable electronics. Zhang et al. fabricated an emerging
design breaks the deformation constrains, and greatly fiber‐shaped aqueous Li‐ion battery with a polyimide/
extends the possibility in the applications of wearable CNT hybrid fiber as the anode and LiMn2O4/CNT hybrid
electronics (Figure 16A). The design principle of fiber as the cathode. This 1D fiber shape allowed the
the coaxial fiber batteries is that the pre‐formed anode flexible batteries to be deformable in diverse directions,
strands are coiled into a hollow spiral core and then and was subsequently woven into a flexible battery tex-
are surrounded by tubular outer cathodes. This design tile, which delivered an operating voltage of 2.5 V for a
innovation allows easy electrolyte wetting and stress re- single cell and reached to 5, 7.5, and 10 V after connec-
lease, without appreciably compromising battery perfor- tion of two, three, and four cells in series, respectively.264
mances in the harsh deformation (Figure 16B). Despite The 3D printing technology with high manufacturing
the high electrical conductivity and mechanical strength efficiency, scalability, and compositional uniformity has
of metal substrates, carbon‐based substitutions promise been introduced to fabricate twisted and quasi‐solid‐state
lightweight and better flexibility. Weng et al.254 reported fiber Li‐ion batteries.99 The cathode and anode fibers
a CNT based substrate to deposit lithium manganate were prepared by inks are composed of LFP and LTO in
cathode and silicon anode materials, respectively, which PVDF solutions with CNT additives, respectively. The
were then winded on cotton fibers in sequence to form a electrode fibers were coated by PVDF‐HFP polymer to
coaxial fiber‐shaped battery with a diameter of 2 mm avoid short circuit, and then are soaked in liquid
(Figure 16C). The energy density of coaxial fiber batteries electrolytes to maintain a sufficient ion mobility
can be significantly improved by loading ultrahigh‐tap‐ (Figure 17D). The integrated fibers by twisting cathode
density LiCoO2 cathode and Li4Ti5O12 (LTO) anode and anode fibers were subsequently protected by an
on CNT macrofilms, which wrapped on CNT macrorope outer heat shrink tube. The twisted fiber with high
to connect electronics (Figure 16D,E).262 The active flexibility and strength can be processed into textiles for
materials loading can reach to 10 mg/cm2, leading to wearable electronics (Figure 17E).
extremely high‐energy density of 215 mWh/cm3. The quality of wearable electronics depends majorly
The twisted batteries are featured in an easily tunable on the materials design and textile processing technol-
diameter to balance flexibility and energy delivery. The ogy. Materials used in fiber‐shaped batteries with a tex-
electrodes of twisted batteries can be bundled together, tile format should concurrently consider energy/power
affording intimated contacts among bunches to facilitate densities and safety. The textile batteries under deform-
high mass loading per length unit. Peng's group reported able conditions are prone to liquid electrolyte leakage,
a twisted cell that was fabricated by depositing cell failure, or even short circuit. How to keep textile
silicon (Si) nanoparticles on CNT scaffolds, forming batteries working safely and efficiently is still a grand
F I G U R E 16 Coaxial fiber‐shaped flexible batteries. (A) Schematics of the cable battery with hollow‐helix anode having multiple‐helix
structure. (B) Circuit voltage of the cable battery with variations in bending strain every 20 min. Reproduced with permission.94 Copyright ©
2012, WILEY‐VCH. (C) Schematics of the fabrication of the coaxial LMO/Si fiber cell. Reproduced with permission.261 (D) Schematics of the
cable LCO/LTO cell. (D) Photographs of the as‐prepared cable cell. Reproduced with permission.262 Copyright © 2018, WILEY‐VCH. LCO,
lithium cobalt oxide; LMO, LiMn2O4; LTO, Li4Ti5O12
challenge yet seldom considered in literatures. For- address these challenges. The construction, configuration,
tunately, the commercialization of smart clothes in- performance, and flexibility of representative flexible bat-
dicates the possible settling of the dilemma of safety and teries are summarized in Table 2.
performance.
While the arising interests in wearable electronics are
the driving force to trigger enormous efforts in the devel- 4 | FLEXIBLE BATTERIES F OR
opment of fiber‐shaped batteries, the existing obstacles in PRACTICAL A PPLICATIONS
the practical applications remain to be fully considered.
One of the issues is their battery performances that are still The emerging demand and technology advancement
far from the requirements of realistic scenarios. For in- push the battery market to continuously seek new ap-
stance, the electrochemical performances of fiber‐shaped plications. While researchers and manufacturers are
batteries decay with the increase of battery length due to struggling for developing high‐energy‐density and low‐
the resistance build‐up or heterogeneous distribution of cost batteries to address the large‐sized electric vehicle
mass/charge in the long range.240 Another critical problem and grid applications, batteries are designed and devel-
is the efficient scalable textile technique to scale up fiber‐ oped into new arts, becoming flexible, rollable, ultra‐thin,
shaped batteries.239 The textile batteries require fiber cells and stretchable. The latter affords vast opportunities to
to be long and flexible enough for easy processing. advance IoT, roll‐up displays, implantable medical ro-
Achieving high metrics simultaneously in safety and sta- bots, and wearable electronics.
bility are key steps toward commercialization. Poisonous Although some companies have released their
electrolytes are the main concerns for devices with high “flexible” electronic products such as Mate Xs pro-
requirements in safety. Abandoning such hazard electro- duced by HUAWEI, and Galaxy Z Flip produced by
lytes and seeking for body‐friendly electrolytes, or exploring SAMSUNG, these “foldable” electronics do not actu-
revolutionary sealing techniques are emerging avenues to ally employ flexible parts, such as chips, circuit
F I G U R E 17 Twisted fiber‐shaped batteries and their textile. (A) Schematics of Li‐ion batteries with a MWCNT/Si composite fiber
cathode and a lithium wire anode. Reproduced with permission.98 Copyright © 2013, WILEY‐VCH. (B) Schematic structures of a
fiber‐shaped hybrid energy‐storage device formed by twisting three CNT hybrid fibers. (C) Comparison of energy and power densities of the
current work and reported energy storage systems. Reproduced with permission.263 Copyright © 2015, WILEY‐VCH. (D) Schematics of
the fabrication process of 3D printed fiber flexible Li‐ion batteries. (E) The potential application of as‐prepared fiber batteries for wearable
applications. Reproduced with permission.99 Copyright © 2017, WILEY‐VCH. MWCNT, multiwalled carbon nanotube multiwalled carbon
nanotube
boards, and batteries because of a variety of issues 4.1 | Li‐ion flexible batteries
that basically cause battery or product failure. For
example, two separated polymer batteries (2250 mAh Li‐based flexible batteries are considered as the major
for each one) are used in each plate of HUAWEI Mate power sources for wearable electronics and flexible
Xs. Although most battery companies have developed smartphones due to attributes of high voltage (>3.5 V),
their own flexible batteries, the end‐user products are high energy density, long life span, and nonmemory ef-
rather limited. Only several types of real flexible fect, which open the door to innovations in the design of
products are available that use flexible batteries. flexible products. The current mission falls into the
Flexible products with dimensional diversity and minimizing of the gap between lab scale technologies
functional versatility are fast evolving and setting differ- and industrial product requirements.
ent requirements for flexible batteries. Table 3 generally Jenax developed a so‐called J.Flex battery with flex-
lists diverse flexible product requirements that need to be ible, solid‐state, fast charging features. J.Flex can be fully
fulfilled, as well as technological status that help aca- bent without apparently sacrificing power capability,
demic and industrial communities to forecast the ad- which have the potential to support a range of industries
vancement of flexible batteries and related products. This that are using advanced technologies to add new design,
section discusses commercial flexible batteries that some comfort, and efficiency to their devices (Figure 18A,B).
companies have developed, and presents representative Surprisingly, the belt‐like batteries can attain more than
applications of flexible batteries in on‐going or up‐ 80% capacity retention after 1000 cycles at 1 C. The de-
coming fields by taking commercially available products tailed working battery characteristics and dimensions are
as examples. It is expected to afford a general envision of listed in Table 4. As flexible batteries have still a long way
the technological status of flexible batteries in market to enable diverse flexible products, the standards of safety
scenarios. and performance tests for flexible batteries are in debate.
| 22 of 35
TABLE 2 Construction, configuration, performance, and flexibility of representative flexible batteries

Shape Cathode/current collector Anode/current collector Electrolyte Energy density Flexibility
Planar LCO/CNT LTO/CNT 1 M LiPF6 in EC/DEC (1:1, v/v) 108 Wh/kg 6 mm bending radius, 50 cycles265
LFP/GF LTO/GF 1 M LiPF6 in EC/DMC (1:1, v/v) 110 Wh/kg 5 mm bending radius, 20 cycles266
LNMO/MWCNT–CNF Graphite/MWCNT–CNF 1 M LiPF6 in EC/DEC (1:1, v/v) 226 Wh/kg Bending267
LCO/Al Graphite/Cu 1 M LiPF6 in EC/DEC (1:1, v/v) 242 Wh/L Bending and twisting, cycles times101
LMO/PTFE LTPO/PTFE 2 M LiNO3 in H2O 124 Wh/L Bending, 100 cycles263
NMO/SS NTP/SS 1 M Na2SO4 in H2O 23.8 Wh/L Bending, 100 cycles242
Polyaniline/Carbon Felts Zn foil PVA gel and 1 M Zn(CF3SO3)2 in H2O NA Bending, 200 cycles268
Fiber LCO/Al wire Sn–Ni/Cu wire 1 M LiPF6 in EC/PC (1:1, v/v) with 3 wt.% VC NA Bending and knotting, 10 cycles for bending94
LMO/MWCNT LTO/MWCNT 1 M LiPF6 in EC/DEC/DMC, (1:1:1, wt/wt/wt) 17.7 Wh/L Bending (1000 cycles) and stretching (200 cycles)269
LMO/MWCNT LTO/MWCNT PEO/SCN/LiTFSI (1:1:0.86 wt/wt/wt) 10.6 Wh/L Stretching, 100 cycles270
LMO/CNT LTO/CNT PEO/SCN/LiTFSI (1:1:0.86 wt/wt/wt) 50 Wh/L Bending, 1000 cycles263
LMO/CNT Polyimide/CNT 0.5 M Li2SO4 in H2O 14.30 Wh/L Bending, twisting264
NiS2/CF Na foil 1 M NaClO4 in EC:PC (1:1 v/v) with 2% FEC NA Bending, 60 cycles271
TiO2/rGO–CNTs Na foil 1 M NaClO4 in EC/PC (1:1, v/v) 58 Wh/L Bending, 2000 cycles272
MnO2/CNT Zn foil 2 M ZnCl2−0.4 M MnCl2 in H2O 195 Wh/L Bending and twisting, 300 cycles273
Abbreviations: CNT, carbon nanotube; LCO, LiCoO2; LTO, Li4Ti5O12; LFP, LiFePO4; LMO, LiMn2O4; LNMO, LiNi0.5Mn1.5O4; GF, graphene foam; PTFE, polytetrafluorethylene; LTPO, LiTi2(PO4)3; MWCNT,
multiwalled carbon nanotube; NMO, Na0.44MnO2; NTP, NaTi2(PO4)3; SS, stainless steel.
KONG
ET AL.
TABLE 3 Electrochemical energy powered flexible applications with different requirements

IoT, medical implantable, Wearables,
micro‐electro‐mechanical electrical textile,
Applications system Smart card, skin patch, RFID medical devices Foldable smartphone
Capacity range 1 mAh 10 mAh 100 mAh 1 Ah
Important • Rechargeable • Can be both rechargeable • High energy • High energy density
features • High power density and disposable density • High power density
• Long life span • Thin • High power • High capacity
• Small footprint • Mild power density density
• Rechargeable • Cost sensitive • Versatile
• Rechargeable shapes
Technological Small volume production Commercially available Prototype Exploring prototype
status available
Product photos
Abbreviation: IoT, Internet of thing; RFID, radio frequency identification.
Herein these tests reported by Jenax are considered as a charging capability to their flexible batteries was added to
typical example to assess the safety requirements of other the battery system. This type of flexible batteries can be
flexible batteries (Table 5). bent up to a radius of 25 mm, and twisted by up ±25°/
Integration of wireless charging system into flexible 100 mm. According to Panasonic, the laminated outer
batteries omits the universal serial bus port, which may layers of batteries and its stacked electrode internal
have adverse effects on the fabrication of thin and flex- construction contributes to reliable charging and dis-
ible batteries. Panasonic showcased flexible batteries in charging characteristics, maintaining 99% of its initial
2017, with a 0.55 mm thickness and a range of capacities capacity after 1000 twists and bending radius of 25 mm in
of 18, 42, and 65 mAh (Figure 18C). The wireless tests. These flexible batteries have reached the
F I G U R E 18 Prototypes of flexible Li‐ion batteries released by some companies. (A) Jenax released J.Flex battery and (B) its application
in headphones. (C) Integration of wireless charging system into flexible batteries produced by Panasonic. (D) Highly flexible belt batteries
produced by Samsung. (E) Wire battery produced by LG Chem. (F) High safety flexible batteries produced by Prologium and (G) its safety
test by cutting
TABLE 4 Battery performance test specifications of J. Flex 15 mm radius and exhibit great tolerance to mechanical
batteries deformation, as indicated in Figure 18E. Such small
Category Contents bending radius indicates that it can bend back on itself
and fit inside a watch band perfectly.
Type Li‐ion polymer
Safety is one of the core indicators to assess the
Dimension 27 × 48 mm flexible batteries. Large capacity (at Ah level) and ex-
Nominal voltage 3.8 V cellent flexible batteries are demonstrated by Prologium
Capacity 30 mAh < 0.1 C Technology Co., Ltd. by printing technology and flexible
circuit board packaging technology, exhibiting extra-
Operation temperature −20°C~60°C
ordinary tolerance to high temperature, and destructive
Cycle 80%@1.0 C/1000 cycles testing. The cells can be as large as 182 × 230 × 0.4 mm3,
Standard current Charge 1.0 C CC/CV to delivering a capacity of 1000~1400 mAh (Figure 18F).
4.25 V, 0.1 C cutoff Unlike lithium polymer batteries, this battery can with-
Discharge 0.2 C to 3.0 V stand high temperatures, and will not catch on fire or
Max current Charge 1.0 C (30 mA) explode if it is burned by a high‐temperature spray gun at
Discharge 2.0 C (60 mA) 1300°C. The cell still stays safe under stringent safety
tests, like punctures, tears, impact, and even gunshots
(Figure 18G). The flexible battery also shows an exciting
capability to resist overcharging, which can withstand a
commercial level, the capacity is too small to be used in high voltage of up to 110 V without any hot or short
smartphones or smart watches. circuit problems.
Highly flexible batteries with small bending radius of
curvature attract significant attentions. Samsung dis-
played a prototype of thin and flexible batteries with 4.2 | Other flexible batteries
band‐shaped format at the InterBattery 2015 exhibition
in Seoul (Figure 18D). The band‐shaped batteries can In addition to Li‐ion batteries, other chemistry‐based
withstand 50,000 bends with the curvature of the human flexible batteries are also well developed due to their
wrist or being wrapped around two fingers. They are unique features, such as zinc‐manganese dioxide
expected to be applied in handhelds and wearables, with (Zn–MnO2) batteries, lithium‐manganese dioxide
increased battery life by up to 50%. However, the detailed (Li–MnO2) batteries, and silver–zinc (Ag–Zn) batteries.
battery characteristics are not available. LG Chem de- Zn–MnO2 batteries, which are comprised of a MnO2
veloped a flexible wire battery, which can be bent into a cathode, a Zn anode, and an ammonium chloride
TABLE 5 Safety test specifications of J.Flex batteries

Category Content
Electrical abuse test Short circuit test At 55°C ± 5°C, with a 100 mΩ until 20% reduction from the highest temperature
Over charge test DC 10 V (20°C ± 5°C)
1. Charge current: 1 C
2. Charge time > 2.5 h
Over discharge test 1 C discharge for 90 min
Over current test 4.2 V CC/CV charge with max.
3 C (20°C ± 5°C)
Environmental abuse test High temperature test Storage 70°C ± 2°C for 7 h
Low pressure test Storage at 11.6 kPa for 6 h
Heating test Increase 5°C ± 2°C/min till 130°C ± 2°C and keep 130°C ± 2°C for 10 min
Mechanical abuse test Impact test Drop 9.1 ± 0.1 kg weight at a height of 61 ± 2.5 cm from the cells
Drop test Drop cells on to hardwood from 1 m height three times (20°C ± 5°C)
Nail penetration test Penetration of fully charged battery pack
1. Nail radius = 3 mm
2. Penetration rate = 80 mm/s
F I G U R E 19 Prototypes of other types of flexible batteries. (A) Zn–MnO2 batteries produced by Blue Spark. (B) Li–MnO2 batteries
produced by Brightvolt. (C) Ag–Zn batteries produced by Imprint Energy
aqueous solution electrolyte, have popularized the pri- Commercial Li‐ion batteries have witnessed almost
mary battery market due to low cost, high safety, and 30‐year success in electronics and vehicle markets and
easy manufacturing.44 The liquid electrolytes are nor- have developed a set of standards to benchmark a variety
mally replaced by inactive gel electrolytes to simplified of batteries in terms of energy density, power density,
fabrication process. The Zn–MnO2 batteries display a working temperature, C‐rate, safety. However, flexible
nominal voltage of 1.5 V and exhibit their best battery batteries are still underdeveloped and lack of a standards
performances with a temperature range of 15°C–30°C. to test and evaluate commercially available flexible bat-
This type of flexible battery is widely used in smart cards, teries. In spite of a showcase of prototype flexible bat-
music greeting cards, and radio frequency identification teries with various chemistries, only ultrathin batteries
electronic tags. Blue Spark created flexible Zn–MnO2 with mild flexibility and low energy densities are em-
batteries by printing technology, with a thickness of ployed in limited fields, including smart cards, micro‐
625 μm (Figure 19A). Typical flexible batteries can de- electro‐mechanical system, and RFID. The predominant
liver capacities of 10~37 mAh, with peak drain currents challenge in such a dilemma is how to keep high energy
of 1~2 mA and working temperature of −30°C–65°C. The density and stability under dynamically flexing.
application fields of the flexible batteries include smart
cards, transit tickets, RFID smart labels, tags, cards, and
retail merchandising. 5 | S UM M A RY A N D OUT L O OK
The Li–MnO2 batteries adopt lithium metal as an
anode and MnO2 as a cathode, which output a nominal The Li‐ion batteries have achieved great success to power
voltage of ~3.0 V. High power density is an attractive portable electronics and electrical vehicles. However,
advantage in this battery. Brightvolt company developed they are limited in their functionality and versatility
a Li–MnO2 flexible battery, with a thickness of 0.45 mm under dynamic bend, twist, and stretch. Flexible batteries
and a capacity of 10~48 mAh (Figure 19B). This flexible are emerging as a powerful platform due to the rise of
battery selected a nontoxic polymer electrolyte and IoT, and wearable electronics, which cannot be powered
printed lithium metal paste to ensure the required by rigid Li‐ion batteries. These flexible applications re-
safety. quire the rational design of battery materials, structures,
Ag–Zn batteries, consisting a silver oxide cathode and and configurations to adapt their shape‐changing
a zinc anode, possess high energy/power density and conditions.
working stability. Ag–Zn batteries have been used in Flexible batteries are still in their infancy and lack of
military equipment such as spacecrafts, satellites, and test standards to benchmark the performance among the
rockets, in which cost are not major considerations. intense amount of data. Geometric parameters, such as
Imprint Energy company showed prototype Ag–Zn flex- bending radius of curvature, thickness, length, and
ible batteries with solid polymer electrolytes, which were bending angle, are straightforward descriptors to basi-
claimed to provide a variety of functions integrated into a cally figure out the flexibility of batteries. However,
flexible, wrist‐worn device that combined wireless com- geometric parameters cannot correlate materials prop-
munication (Figure 19C). The fabricated batteries can be erties to flexibility, and thus are inefficient to guide the
flexed thousands of times without performance de- rational selection of desired materials. Mechanical para-
gradation in the minimum 25 mm bend radius. meters (e.g., strain and Young's modulus) linked to the
critical thickness of batteries afford an effective way to room for separators to be customized in the conversion
fairly compare and report flexibility among different reaction battery chemistries, such as Li–S and Li–O2
materials. A figure of merit (fFoM) related to mechanical batteries, which require regulation of both ion and mass
property (εy/E) principally reveal how stress and Young's transport in the redox reactions. The polymeric materi-
modulus rule the battery flexibility. Energy density als, like PVDF, PAN, and PMMA, as well as integration
parameters determine how long devices can work at the of polymer solid electrolyte into polymer membranes can
limited volume. It is noted that a well trade‐off between simultaneously favor ion transport and preserve me-
energy density and flexibility is kernel to enable devices chanical strength to avoid dendrite growth.
work better, since batteries have to release strain/stress The combination of battery processing techniques
under mechanical deformation without apparently sa- and flexible battery requirements favoring the rapid and
crifice of electrochemical characteristics. massive production of flexible batteries will be realized
Designing flexible components of batteries are central once breakthrough occurs in bottleneck challenges.
tasks to fulfill growing demands on energy density, Flexible batteries with a planar configuration can seam-
safety, and cyclability. Current collectors need to keep lessly acquire the fabrication technique of conventional
electrode materials integration under mechanical de- Li‐ion batteries that laminate the planar sheets sequen-
formation and withstand electrochemical corrosion. Al tially. The innovations in planar configurations, such as
and Cu foils that have widely used in commercial cath- paper‐like, thin‐film, origami, and spinel‐like concepts
ode and anode current collectors, respectively, are not have effectively rendered battery flexible. The new pro-
ideal option for flexible batteries due to their low yield cessing methods, like 3D printing technology, enable
strains. Alternatively, carbonaceous and polymeric ma- precise structure regulation, high material utilization
terials with various dimensions can be also processed efficiency, and simple cell patterning, thus affording an
into flexible current collectors, which are featured in opportunity to further advance flexible planar batteries.
high flexibility, extraordinary conductivity, light weight, 1D fiber‐shaped flexible batteries have advantages of
and large surface area. CNTs, graphene, and their hy- miniaturization, adaptability, and weavability, and can
brids are star materials to render flexibility and versatility be processed into textile to form wearable electronics.
of current collectors. Incorporation of electrochemical Comparing with planar flexible batteries, fiber‐shaped
active materials into such current collectors with high batteries can withstand much more stringent deforma-
content/loading to entail energy‐dense batteries still en- tion to adapt working conditions. The remaining chal-
counters several limitations. The first one is the technical lenges include further improving energy density and
difficulties to stably weld tabs to connect carbon and scalable weave cells into electric textile while preserving
polymer matrices, and repeated shape changes of devices safety and stability.
cause disconnection between electrode and external cir- Thanks to the rise of flexible electronics market and
cuits, as well as a nonuniform current distribution IoT, various flexible batteries have been commercially
around tab regions. The second one lies in the reliability available, and flexible device prototypes are shooting out.
of adhesion between active materials and current col- Most flexible prototype flexible batteries are based on Li‐
lectors due to much increased hierarchical pores in ion polymer batteries due to high voltage, large energy
comparison with slurry‐coating electrode. The active density, long cycle life, and sufficient flexibility, thereby
materials breaking away from scaffolds limit electron and being strongly considered in flexible smartphones and
ion accessibility, resulting capacity fading. Besides, the computers that have demands on energy output. Other
increased porosity of electrode demands more electro- flexible batteries based on Li–MnO2, Zn–MnO2, and
lytes to establish continuous ionic pathways. These Ag–Zn chemistries have respective attributes to be used
challenges need to be considered in the design of well‐ in special fields, which enrich flexible battery choices.
performing electrodes in flexible batteries. While flexible batteries have achieved great advances
The electrolyte is the only component to contact all in recent years, they are not as mature as rigid Li‐ion
cell parts, which require enough compatibility with bat- batteries in terms of fabrication technology, test stan-
tery components and efficient ionic transport properties. dard, and cost competitivity. The future development of
Solid‐state electrolytes emerge as promising substitutes to flexible batteries includes the following aspects.
liquid counterparts in the flexible batteries, in view of (1) Improving battery characteristics. Energy density,
negligible electrolyte leakage, high Yong's modulus, wide power density, and cycle life are still unsatisfied con-
electrochemical window, and easy cell patterning. Espe- sidering the level of conventional Li‐ion batteries. Energy
cially, SPEs featuring a balance of ionic conductivity, and power densities are limited by the active material
flexibility, and wettability has become the electrolyte of loading and electrode porosity. Thick and dense elec-
choice in commercial ultrathin batteries. There are large trodes inevitably cause crack and resistance build‐up
under dynamic shape changes, which contribute to cell underlying difficulties and hindrances would be well
performance decay or cell death. Flexible batteries with acknowledged and thus benefiting more effective
more than 1000 cycles have been reported by companies. strategies to tackle with corresponding issues. The
However, most cases do not mention energy density and advances in flexible batteries rely on sharing experi-
power densities. Lightweight and soft materials and in- ence and knowledge between academic researchers
novative cell structures that cut down inactive materials and industrial engineers.
portion, release flexing‐induced strain, and keep battery The success of flexible batteries in smart energy de-
integration could afford solutions for this issue. vices requires rational design of battery components and
(2) Enhancing components compatibility. Flexible structures, and cooperative efforts among scientists and
batteries work under electrochemical environment and engineers in related fields. The advent of flexible era will
mechanical force, which require compatible battery benefit smart energy storage, enable diverse device
components, electrochemically, and mechanically. For functionalities, and even create new demands to push
electrochemical compatibility, the electrolytes need to forward the landscape of green energy.
withstand oxidation and reduction in cathodes and an-
odes simultaneously. Thereby, electrolytes that possess AC KNOW LEDGEM ENTS
wide electrochemical window and stable interface‐film‐ We thank Prof. Chunyi Zhi for helpful discussions. This
forming capability are regarded as key properties to keep study was supported by the National Natural Science
battery working well. Other side reactions between Foundation of China (21805162, 21825501, and
electrolytes/current collectors, current collectors/active U1801257), National Key Research and Development
materials should also be suppressed. The mechanical Program (2016YFA0202500), China Postdoctoral Science
compatibility dictates whether batteries can be flexed as Foundation (2018M630165), Natural Science Foundation
expected. Battery components made from different ma- of Beijing (Z200011), Beijing Key Research and Devel-
terials exhibit a wide variation of Young's modulus and opment Plan (Z181100004518001), the Tsinghua Uni-
yield strains. The level of battery flexibility is principally versity Initiative Scientific Research Program.
determined by the most fragile components, analogous to
the Cannikin law. The less flexible component has to be CONFLI CT OF I NTER EST
particularly designed in battery fabrication. The authors declare no conflict of interest.
(3) Reducing battery costs. Materials cost and fabri-
ORC ID
cation cost constitute a large portion in the whole bat-
Qiang Zhang https://orcid.org/0000-0002-3929-1541
tery costs. The fabrication of flexible batteries is not
mature enough to be scaled up. For example, fiber‐ REFER ENCES
shaped batteries cannot remain enough mechanical 1. Liang Y, Zhao CZ, Yuan H, et al. A review of rechargeable
strength for automatic integration processes and suffer batteries for portable electronic devices. InfoMat. 2019;1:6‐32.
from damages in weaving processes. Hand‐made textiles 2. Zhang C, Wei Y‐L, Cao P‐F, Lin M‐C. Energy storage system:
current studies on batteries and power condition system.
are ubiquitously used in the proof‐of‐concept stage,
Renew Sust Energy Rev. 2018;82:3091‐3106.
which is not acceptable in large‐scale applications due 3. Yang Y, Yu D, Wang H, Guo L. Smart electrochemical energy
to high cost and low efficiency. Besides, battery com- storage devices with self‐protection and self‐adaptation abil-
ponents that have multiple functions are very expensive. ities. Adv Mater. 2017;29:1703040.
Polymer electrolytes sometimes serve as both media to 4. Zhang X, Cheng X, Zhang Q. Nanostructured energy mate-
transport ions and separate cathode/anode. Optimiza- rials for electrochemical energy conversion and storage: a
tion of electrochemical and mechanical properties of review. J Energy Chem. 2016;25:967‐984.
5. Armand M, Tarascon J‐M. Building better batteries. Nature.
polymer electrolytes and assembly technologies in the
2008;451:652‐657.
cathode–electrolyte–anode structures rise the battery
6. Cao WZ, Zhang JN, Li H. Batteries with high theoretical
cost. Technological maturity and material development energy densities. Energy Storage Mater. 2020;26:46‐55.
can reduce battery costs and in turn stimulate massive 7. Gao RM, Zheng ZJ, Wang PF, Wang CY, Ye H, Cao FF.
production. Recent advances and prospects of layered transition metal
(4) Minimizing the gap between academic re- oxide cathodes for sodium‐ion batteries. Energy Storage
searches and industrial requirements. Fundamental Mater. 2020;30:9‐26.
researches reveal basic chemical and structural me- 8. Lu K, Zhang H, Ye FL, Luo W, Ma HY, Huang YH. Re-
chargeable potassium‐ion batteries enabled by potassium‐
chanisms and provide guidelines to select desired
iodine conversion chemistry. Energy Storage Mater. 2019;16:
materials among tremendous candidates. Exceptional 1‐5.
performances and innovative concepts reported by 9. Jamesh M‐I. Recent advances on flexible electrodes for Na‐
academic research are suggested to be further ion batteries and Li–S batteries. J Energy Chem. 2019;32:
evaluated in more realistic conditions, by which the 15‐44.
10. Wen L, Liang J, Chen J, Chu ZY, Cheng HM, Li F. Smart 31. Fang B, Chang D, Xu Z, Gao C. A review on graphene fibers:
materials and design toward safe and durable lithium ion expectations, advances, and prospects. Adv Mater. 2020;32:
batteries. Small Methods. 2019;3:1900323. 1902664.
11. Yang YY. A mini‐review: emerging all‐solid‐state energy 32. Zhou G, Xu L, Hu G, Mai L, Cui Y. Nanowires for electro-
storage electrode materials for flexible devices. Nanoscale. chemical energy storage. Chem Rev. 2019;119:11042‐11109.
2020;12:3560‐3573. 33. Zhao F, Zhao X, Peng B, et al. Polyimide‐derived carbon
12. Zhao Y, Guo J. Development of flexible Li‐ion batteries for nanofiber membranes as anodes for high‐performance flex-
flexible electronics. InfoMat. 2020;2:866‐878. ible lithium ion batteries. Chin Chem Lett. 2018;29:1692‐1697.
13. Chen K, Wang Q, Niu Z, Chen J. Graphene‐based materials for 34. Fu J, Kang W, Guo X, et al. 3D hierarchically porous NiO/
flexible energy storage devices. J Energy Chem. 2018;27:12‐24. Graphene hybrid paper anode for long‐life and high rate
14. Ye L, Hong Y, Liao M, et al. Recent advances in flexible fiber‐ cycling flexible Li‐ion batteries. J Energy Chem. 2020;47:
shaped metal‐air batteries. Energy Storage Mater. 2020;28: 172‐179.
364‐374. 35. Liu J, Li D, Zhang S, et al. Hierarchical N‐doped carbon
15. Zeng L, Qiu L, Cheng H‐M. Towards the practical use of nanocages/carbon textiles as a flexible O2 electrode for Li–O2
flexible lithium ion batteries. Energy Storage Mater. 2019;23: batteries. J Energy Chem. 2020;46:94‐98.
434‐438. 36. Peng HJ, Wang DW, Huang JQ, et al. Janus separator of
16. Wen L, Chen J, Liang J, Li F, Cheng H‐M. Flexible batteries polypropylene‐supported cellular graphene framework for
ahead. Nati Sci Rev. 2017;4:20‐23. sulfur cathodes with high utilization in lithium–sulfur bat-
17. Shi Q, Dong B, He T, et al. Progress in wearable electronics/ teries. Adv Sci. 2016;3:1500268.
photonics—moving toward the era of artificial intelligence 37. Sannicolo T, Lagrange M, Cabos A, Celle C, Simonato J‐P,
and Internet of things. InfoMat. 2020;2:1131‐1162. Bellet D. Metallic nanowire‐based transparent electrodes for
18. Liu L, Lyu J, Mo J, et al. Flexible, high‐voltage, ion‐ next generation flexible devices: a review. Small. 2016;12:
conducting composite membranes with 3D aramid nanofiber 6052‐6075.
frameworks for stable all‐solid‐state lithium metal batteries. 38. Kong L, Peng H‐J, Huang J‐Q, Zhang Q. Review of nanos-
China Mater. 2020;63:703‐718. tructured current collectors in lithium–sulfur batteries. Nano
19. Silambarasan K, Joseph J. Flexible anion microbatteries: to- Res. 2017;10:4027‐4054.
wards construction of a hybrid battery‐capacitor device. 39. Li Y, Zhou J, Zhang T, et al. Highly surface‐wrinkled and N‐
ChemSusChem. 2018;11:3081‐3086. doped CNTs anchored on metal wire: a novel fiber‐shaped
20. Yang Q, Wang Y, Li X, et al. Recent progress of MXene‐based cathode toward high‐performance flexible Li–CO2 batteries.
nanomaterials in flexible energy storage and electronic de- Adv Funct Mater. 2019;29:1808117.
vices. Energy Environ Mater. 2018;1:183‐195. 40. Zhang ZT, Liao M, Lou HQ, Hu YJ, Sun XM, Peng HS.
21. Dai C, Sun G, Hu L, Xiao Y, Zhang Z, Qu L. Recent progress Conjugated polymers for flexible energy harvesting and sto-
in graphene‐based electrodes for flexible batteries. InfoMat. rage. Adv Mater. 2018;30:1704261.
2020;2:509‐526. 41. Nyholm L, Nyström G, Mihranyan A, Strømme M. Toward
22. Zhu Y‐H, Yang X‐Y, Liu T, Zhang X‐B. Flexible 1D batteries: flexible polymer and paper‐based energy storage devices. Adv
recent progress and prospects. Adv Mater. 2020;32:1901961. Mater. 2011;23:3751‐3769.
23. Fu KK, Cheng J, Li T, Hu L. Flexible batteries: from me- 42. Foreman E, Zakri W, Sanatimoghaddam MH, et al. A review
chanics to devices. ACS Energy Lett. 2016;1:1065‐1079. of inactive materials and components of flexible lithium‐ion
24. Zhai S, Karahan HE, Wei L, et al. Textile energy storage: batteries. Adv Sustain Syst 2017;1:1700061.
structural design concepts, material selection and future 43. Qian G, Liao X, Zhu Y, Pan F, Chen X, Yang Y. Designing
perspectives. Energy Storage Mater. 2016;3:123‐139. flexible lithium‐ion batteries by structural engineering. ACS
25. Park J, Hwang JC, Kim GG, Park J‐U. Flexible electronics Energy Lett. 2019;4:690‐701.
based on one‐dimensional and two‐dimensional hybrid na- 44. Winter M, Brodd RJ. What are batteries, fuel cells, and su-
nomaterials. InfoMat. 2020;2:33‐56. percapacitors. Chem Rev. 2004;104:4245‐4270.
26. Cha H, Kim J, Lee Y, Cho J, Park M. Issues and challenges 45. Kong L, Yin L, Xu F, et al. Electrolyte solvation chemistry for
facing flexible lithium‐ion batteries for practical application. lithium–sulfur batteries with electrolyte‐lean conditions.
Small. 2018;14:1702989. J Energy Chem. 2021;55:80‐91.
27. Chen D, Lou Z, Jiang K, Shen G. Device configurations and 46. Zhao M, Li B‐Q, Zhang X‐Q, Huang J‐Q, Zhang Q. A per-
future prospects of flexible/stretchable lithium‐ion batteries. spective toward practical lithium–sulfur batteries. ACS Cent
Adv Funct Mater. 2018;28:1805596. Sci. 2020;6:1095‐1104.
28. Wu Z, Wang Y, Liu X, et al. Carbon‐nanomaterial‐based 47. Liu J, Bao ZN, Cui Y, et al. Pathways for practical high‐
flexible batteries for wearable electronics. Adv Mater. 2019; energy long‐cycling lithium metal batteries. Nat Energy.
31:1800716. 2019;4:180‐186.
29. Mackanic DG, Chang T‐H, Huang Z, Cui Y, Bao Z. Stretch- 48. Chung SH, Chang CH, Manthiram A. Progress on the critical
able electrochemical energy storage devices. Chem Soc Rev. parameters for lithium‐sulfur batteries to be practically vi-
2020;49:4466‐4495. able. Adv Funct Mater. 2018;28:1801188.
30. Liu W, Song M‐S, Kong B, Cui Y. Flexible and stretchable 49. Hedayati R, Sadighi M, Mohammadi‐Aghdam M,
energy storage: recent advances and future perspectives. Adv Zadpoor AA. Mechanical properties of regular porous bio-
Mater. 2017;29:1603436. materials made from truncated cube repeating unit cells:
analytical solutions and computational models. Mater Sci 69. Chen X‐R, Li B‐Q, Zhu C, et al. A coaxial‐interweaved hybrid
Eng C. 2016;60:163‐183. lithium metal anode for long‐lifespan lithium metal batteries.
50. Cuevas FG, Montes JM, Cintas J, Urban P. Electrical con- Adv Energy Mater. 2019;9:1901932.
ductivity and porosity relationship in metal foams. J Porous 70. Ghazi ZA, Sun Z, Sun C, et al. Key aspects of lithium metal
Mater. 2009;16:675‐681. anodes for lithium metal batteries. Small. 2019;15:1900687.
51. Kong L, Yan C, Huang J‐Q, et al. A review of advanced 71. Lu Z, Li W, Long Y, et al. Constructing a high‐strength solid
energy materials for magnesium‐sulfur batteries. Energy electrolyte layer by in vivo alloying with aluminum for an
Environ Mater. 2018;1:100‐112. ultrahigh‐rate lithium metal anode. Adv Funct Mater. 2020;
52. Liu F, Wang T, Liu X, Fan L‐Z. Challenges and recent pro- 30:1907343.
gress on key materials for rechargeable magnesium batteries. 72. Zhao SQ, Zhang L, Zhang GN, Sun HB, Yang JY, Lu SG.
Adv Energy Mater. 2020;2000787. https://doi.org/10.1002/ Failure analysis of pouch‐type Li–O2 batteries with superior
aenm.202000787 energy density. J Energy Chem. 2020;45:74‐82.
53. Jung J‐W, Cho S‐H, Nam JS, Kim I‐D. Current and future 73. Liu H, Cheng X‐B, Jin Z, et al. Recent advances in under-
cathode materials for non‐aqueous Li‐air (O2) battery standing dendrite growth on alkali metal anodes.
technology—a focused review. Energy Storage Mater. 2020; EnergyChem. 2019;1:100003.
24:512‐528. 74. Lv B, Zeng S, Yang W, et al. In‐situ embedding zeolitic
54. Li M, Du Z, Khaleel MA, Belharouak I. Materials and en- imidazolate framework derived Co–N–C bifunctional cata-
gineering endeavors towards practical sodium‐ion batteries. lysts in carbon nanotube networks for flexible Zn–air bat-
Energy Storage Mater. 2020;25:520‐536. teries. J Energy Chem. 2019;38:170‐176.
55. Liu T, Cheng X, Yu H, et al. An overview and future per- 75. Li X, Tang Y, Lv H, et al. Recent advances in flexible
spectives of aqueous rechargeable polyvalent ion batteries. aqueous zinc‐based rechargeable batteries. Nanoscale.
Energy Storage Mater. 2019;18:68‐91. 2019;11:17992‐18008.
56. Yang H, Li H, Li J, et al. The rechargeable aluminum battery: 76. Mo F, Liang G, Meng Q, et al. A flexible rechargeable aqu-
opportunities and challenges. Angew Chem Int Ed. 2019;58: eous zinc manganese‐dioxide battery working at −20°C.
11978‐11996. Energy Environ Sci. 2019;12:706‐715.
57. Dong Y, Li S, Hong S, Wang L, Wang B. Metal‐organic fra- 77. An L, Li Y, Luo M, et al. Atomic‐level coupled interfaces and
meworks and their derivatives for Li–air batteries. Chin lattice distortion on CuS/NiS2 nanocrystals boost oxygen
Chem Lett. 2020;31:635‐642. catalysis for flexible Zn‐air batteries. Adv Funct Mater. 2017;
58. Fang R, Chen K, Yin L, Sun Z, Li F, Cheng HM. The reg- 27:1703779.
ulating role of carbon nanotubes and graphene in lithium‐ion 78. Liu L, Wang Y, Yan F, et al. Cobalt‐encapsulated nitrogen‐
and lithium‐sulfur batteries. Adv Mater. 2019;31:1800863. doped carbon nanotube arrays for flexible zinc–air batteries.
59. Tang X, Xu Z, Sun Z, et al. Factors of kinetics processes in Small Methods. 2020;4:1900571.
lithium–sulfur reactions. Energy Technol. 2019;7:1900574. 79. Li B‐Q, Zhang S‐Y, Wang B, Xia Z‐J, Tang C, Zhang Q. A
60. Yan M, Wang W‐P, Yin Y‐X, Wan L‐J, Guo Y‐G. Interfacial porphyrin covalent organic framework cathode for flexible
design for lithium–sulfur batteries: from liquid to solid. Zn–air batteries. Energy Environ Sci. 2018;11:1723‐1729.
EnergyChem. 2019;1:100002. 80. Zhang Y, Ouyang B, Long G, et al. Enhancing bifunctionality
61. Yuan H, Peng H‐J, Huang J‐Q, Zhang Q. Sulfur redox reac- of CoN nanowires by Mn doping for long‐lasting Zn‐air
tions at working interfaces in lithium‐sulfur batteries: a batteries. China Chem. 2020;63:890‐896.
perspective. Adv Mater Interfaces. 2019;6:1802046. 81. He P, Chen Q, Yan M, et al. Building better zinc‐ion bat-
62. Zhang P, Zhao Y, Zhang X. Functional and stability or- teries: a materials perspective. EnergyChem. 2019;1:100022.
ientation synthesis of materials and structures in aprotic 82. Chen R, Luo R, Huang Y, Wu F, Li L. Advanced high energy
Li–O2batteries. Chem Soc Rev. 2018;47:2921‐3004. density secondary batteries with multi‐electron reaction
63. Bhargav A, He J, Gupta A, Manthiram A. Lithium‐sulfur materials. Adv Sci. 2016;3:1600051.
batteries: attaining the critical metrics. Joule. 2020;4:285‐291. 83. Gao X‐P, Yang H‐X. Multi‐electron reaction materials for high
64. Li Y, Zhou P, Li H, et al. A freestanding flexible single‐atom energy density batteries. Energy Environ Sci. 2010;3:174‐189.
cobalt‐based multifunctional interlayer toward reversible and 84. Muldoon J, Bucur CB, Gregory T. Quest for nonaqueous
durable lithium‐sulfur batteries. Small Methods. 2020;4(3): multivalent secondary batteries: magnesium and beyond.
1900701. Chem Rev. 2014;114:11683‐11720.
65. Liu B, Fang R, Xie D, et al. Revisiting scientific issues for 85. Ponrouch A, Bitenc J, Dominko R, Lindahl N, Johansson P,
industrial applications of lithium‐sulfur batteries. Energy Palacin MR. Multivalent rechargeable batteries. Energy
Environ Mater. 2018;1:196‐208. Storage Mater. 2019;20:253‐262.
66. Du Y, Gao X, Li S, Wang L, Wang B. Recent advances in 86. Li M, Lu J, Ji X, et al. Design strategies for nonaqueous
metal‐organic frameworks for lithium metal anode protec- multivalent‐ion and monovalent‐ion battery anodes. Nat Rev
tion. Chin Chem Lett. 2020;31:609‐616. Mater. 2020;5:294‐276.
67. Cheng X‐B, Zhang R, Zhao C‐Z, Zhang Q. Toward safe li- 87. Xu K. Nonaqueous liquid electrolytes for lithium‐based re-
thium metal anode in rechargeable batteries: a review. Chem chargeable batteries. Chem Rev. 2004;104:4303‐4418.
Rev. 2017;117:10403‐10473. 88. Deimede V, Elmasides C. Separators for lithium‐ion bat-
68. Liu B, Zhang J‐G, Xu W. Advancing lithium metal batteries. teries: a review on the production processes and recent de-
Joule. 2018;2:833‐845. velopments. Energy Technol. 2015;3:453‐468.
89. Chen X, Zhang X‐Q, Li H‐R, Zhang Q. Cation−solvent, ca- 107. Zhao C, Lu Y, Chen L, Hu Y‐S. Flexible Na batteries.
tion−anion, and solvent−solvent interactions with electro- InfoMat. 2020;2:126‐138.
lyte solvation in lithium batteries. Batteries Supercaps. 2019; 108. Wang Z, Meng X, Wu Z, Mitra S. Development of flexible
2:128‐131. zinc–air battery with nanocomposite electrodes and a novel
90. Chen X, Shen X, Hou T‐Z, Zhang R, Peng H‐J, Zhang Q. Ion‐ separator. J Energy Chem. 2017;26:129‐138.
solvent chemistry‐inspired cation‐additive strategy to stabi- 109. Li H, Zhang X, Zhao Z, Hu Z, Liu X, Yu G. Flexible sodium‐
lize electrolytes for sodium‐metal batteries. Chem. 2020;6: ion based energy storage devices: recent progress and chal-
2242‐2256. lenges. Energy Storage Mater. 2020;26:83‐104.
91. Huang L, Zhang Z, Wang Z, Zhang L, Zhu X, Dorrell DD. 110. Li Y, Fu J, Zhong C, et al. Recent advances in flexible zinc‐
Thermal runaway behavior during overcharge for large‐ based rechargeable batteries. Adv Energy Mater. 2019;9:
format Lithium‐ion batteries with different packaging pat- 1802605.
terns. J. Energy Storage. 2019;25:100811. 111. Peng J, Snyder GJ. A figure of merit for flexibility. Science.
92. Yuan H, Huang JQ, Peng HJ, et al. A review of functional 2019;366:690‐691.
binders in lithium‐sulfur batteries. Adv Energy Mater. 2018;8: 112. Li H, Tang Z, Liu Z, Zhi C. Evaluating flexibility and wear-
1802107. ability of flexible energy storage devices. Joule. 2019;3:
93. Yue Y, Liang H. 3D current collectors for lithium‐ion bat- 613‐619.
teries: a topical review. Small Methods. 2018;2:1800056. 113. Rogers JA, Someya T, Huang Y. Materials and mechanics for
94. Kwon YH, Woo S‐W, Jung H‐R, et al. Cable‐type flexible stretchable electronics. Science. 2010;327:1603‐1607.
lithium ion battery based on hollow multi‐helix electrodes. 114. Park SI, Ahn JH, Feng X, Wang S, Huang Y, Rogers JA.
Adv Mater. 2012;24:5192‐5197. Theoretical and experimental studies of bending of inorganic
95. Choi K‐H, Cho S‐J, Kim S‐H, Kwon YH, Kim JY, Lee S‐Y. electronic materials on plastic substrates. Adv Funct Mater.
Thin, deformable, and safety‐reinforced plastic crystal poly- 2008;18:2673‐2684.
mer electrolytes for high‐performance flexible lithium‐ion 115. Ashby M. The deformation of plastically non‐homogeneous
batteries. Adv Funct Mater. 2014;24:44‐52. materials. Philos Mag: J Theor Exp Appl Phys. 1970;21:
96. Yuan Z, Peng H‐J, Huang J‐Q, et al. Hierarchical free‐ 399‐424.
standing carbon‐nanotube paper electrodes with ultrahigh 116. Chang J, Huang QY, Zheng ZJ. A figure of merit for flexible
sulfur‐loading for lithium‐sulfur batteries. Adv Funct Mater. batteries. Joule. 2020;4:1346‐1349.
2014;24:6105‐6112. 117. Bonatti C, Mohr D. Anisotropic viscoplasticity and fracture of
97. Song Z, Ma T, Tang R, et al. Origami lithium‐ion batteries. fine grained metallic aluminum foil used in Li‐ion batteries.
Nat Commun. 2014;5:3140. Mater Sci Eng, A. 2016;654:329‐343.
98. Lin H, Weng W, Ren J, et al. Twisted aligned carbon nano- 118. Zhu J, Feng J, Guo Z. Mechanical properties of commercial
tube/silicon composite fiber anode for flexible wire‐shaped copper current‐collector foils. RSC Adv. 2014;4:57671‐57678.
lithium‐ion battery. Adv Mater. 2014;26:1217‐1222. 119. Wang D, Han C, Mo F, et al. Energy density issues of flexible
99. Wang Y, Chen C, Xie H, et al. 3D‐printed all‐fiber li‐ion energy storage devices. Energy Storage Mater. 2020;28:
battery toward wearable energy storage. Adv Funct Mater. 264‐292.
2017;27:1703140. 120. Ning F, Shen Y, Bai C, et al. Critical importance of current
100. Zhao C‐Z, Zhang X‐Q, Cheng X‐B, et al. An anion‐immobilized collector property to the performance of flexible electro-
composite electrolyte for dendrite‐free lithium metal anodes. Proc chemical power sources. Chin Chem Lett. 2019;30:1282‐1288.
Natl Acad Sci USA. 2017;114:11069‐11074. 121. Yang Y, Yuan W, Zhang X, et al. A review on structuralized
101. Qian G, Zhu B, Liao X, et al. Bioinspired, spine‐like, flexible, current collectors for high‐performance lithium‐ion battery
rechargeable lithium‐ion batteries with high energy density. anodes. Appl Energy. 2020;276:115464.
Adv Mater. 2018;30:1704947. 122. Abe H, Kubota M, Nemoto M, et al. High‐capacity thick
102. Wan J, Xie J, Kong X, et al. Ultrathin, flexible, solid polymer cathode with a porous aluminum current collector for li-
composite electrolyte enabled with aligned nanoporous host thium secondary batteries. J Power Sources. 2016;334:
for lithium batteries. Nat Nanotechnol. 2019;14:705‐711. 78‐85.
103. Bae J, Qian Y, Li Y, Zhou X, Goodenough JB, Yu G. Polar 123. Cheng X‐B, Peng H‐J, Huang J‐Q, et al. Three‐dimensional
polymer–solvent interaction derived favorable interphase for aluminum foam/carbon nanotube scaffolds as long‐ and
stable lithium metal batteries. Energy Environ Sci. 2019;12: short‐range electron pathways with improved sulfur loading
3319‐3327. for high energy density lithium–sulfur batteries. J Power
104. Zhou J, Cheng J, Wang B, Peng H, Lu J. Flexible metal–gas Sources. 2014;261:264‐270.
batteries: a potential option for next‐generation power ac- 124. Huang J‐Q, Zhai P‐Y, Peng H‐J, Zhu W‐C, Zhang Q. Metal/
cessories for wearable electronics. Energy Environ Sci. 2020; nanocarbon layer current collectors enhanced energy effi-
13:1933‐1970. ciency in lithium‐sulfur batteries. Sci Bull. 2017;62:
105. Peng H‐J, Huang J‐Q, Zhang Q. A review of flexible 1267‐1274.
lithium–sulfur and analogous alkali metal–chalcogen re- 125. Das CM, Kang L, Ouyang Q, Yong K‐T. Advanced low‐
chargeable batteries. Chem Soc Rev. 2017;46:5237‐5288. dimensional carbon materials for flexible devices. InfoMat.
106. Yu P, Zeng Y, Zhang H, Yu M, Tong Y, Lu X. Flexible zn‐ion 2020;2:698‐714.
batteries: recent progresses and challenges. Small. 2019;15: 126. Fang R, Li G, Zhao S, et al. Single‐wall carbon nanotube
1804760. network enabled ultrahigh sulfur‐content electrodes for high‐
performance lithium‐sulfur batteries. Nano Energy. 2017;42: 144. Cao S, Feng X, Song Y, et al. In Situ carbonized cellulose‐
205‐214. based hybrid film as flexible paper anode for lithium‐ion
127. Zhang C, Huang Z, Lv W, Yun Q, Kang F, Yang Q‐H. Carbon batteries. ACS Appl Mater Interfaces. 2016;8:1073‐1079.
enables the practical use of lithium metal in a battery. 145. Hou R, Gund GS, Qi K, et al. Hybridization design of ma-
Carbon. 2017;123:744‐755. terials and devices for flexible electrochemical energy sto-
128. Li L, Wu ZP, Sun H, et al. A foldable lithium–sulfur battery. rage. Energy Storage Mater. 2019;19:212‐241.
ACS Nano. 2015;9:11342‐11350. 146. Zhang Q, Huang JQ, Qian WZ, Zhang YY, Wei F. The road
129. Moyer K, Meng C, Marshall B, et al. Carbon fiber reinforced for nanomaterials industry: a review of carbon nanotube
structural lithium‐ion battery composite: multifunctional production, post‐treatment, and bulk applications for com-
power integration for CubeSats. Energy Storage Mater. 2020; posites and energy storage. Small. 2013;9:1237‐1265.
24:676‐681. 147. Zhou Z, Si W, Lu P, et al. A flexible CNT@nickel silicate
130. Kalimuldina G, Taniguchi I. High performance stoichio- composite film for high‐performance sodium storage.
metric Cu2S cathode on carbon fiber current collector for J Energy Chem. 2020;47:29‐37.
lithium batteries. Electrochim Acta. 2017;224:329‐336. 148. Ding X, Pan Z, Liu N, et al. Freestanding carbon nanotube
131. Wang Y, Chen K. Low‐cost, lightweight electrodes based on film for flexible straplike lithium/sulfur batteries. Chem Eur
carbon fibers as current collectors for aluminum‐ion bat- J. 2019;25:3775‐3780.
teries. J Electroanal Chem. 2019;849:113374. 149. Wang Y, Ma Z, Chen Y, et al. Controlled synthesis of core‐
132. Yu J, Li BQ, Zhao CX, Liu JN, Zhang Q. Asymmetric air shell carbon@MoS2 nanotube sponges as high‐performance
cathode design for enhanced interfacial electrocatalytic re- battery electrodes. Adv Mater. 2016;28:10175‐10181.
actions in high‐performance zinc–air batteries. Adv Mater. 150. Lin Z, Zeng Z, Gui X, Tang Z, Zou M, Cao A. Carbon na-
2020;32:1908488. notube sponges, aerogels, and hierarchical composites:
133. Kim J‐H, Lee Y‐H, Cho S‐J, et al. Nanomat Li–S batteries synthesis, properties, and energy applications. Adv Energy
based on all‐fibrous cathode/separator assemblies and re- Mater. 2016;6:1600554.
inforced Li metal anodes: towards ultrahigh energy density 151. Ren J, Li L, Chen C, et al. Twisting carbon nanotube fibers
and flexibility. Energy Environ Sci. 2019;12:177‐186. for both wire‐shaped micro‐supercapacitor and micro‐
134. Zhou Z, Li N, Wang P, et al. All‐carbon positive electrodes for battery. Adv Mater. 2013;25:1155‐1159.
stable aluminium batteries. J Energy Chem. 2020;42:17‐26. 152. Zhang T, Han S, Guo W, et al. Continuous carbon nanotube
135. Kumar A, Ghosh A, Roy A, et al. High‐energy density room composite fibers for flexible aqueous lithium‐ion batteries.
temperature sodium‐sulfur battery enabled by sodium polysulfide Sustain Mater Technol. 2019;20:e00096.
catholyte and carbon cloth current collector decorated with 153. Zhou G, Wang D‐W, Li F, et al. A flexible nanostructured
MnO2 nanoarrays. Energy Storage Mater. 2019;20:196‐202. sulphur–carbon nanotube cathode with high rate performance
136. Fang R, Zhao S, Pei S, et al. Toward more reliable for Li‐S batteries. Energy Environ Sci. 2012;5:8901‐8906.
lithium–sulfur batteries: an all‐graphene cathode structure. 154. Wu Y, Wei Y, Wang J, Jiang K, Fan S. Conformal Fe3O4
ACS Nano. 2016;10:8676‐8682. sheath on aligned carbon nanotube scaffolds as high‐
137. Chu H, Pei Y, Cui Z, et al. A 3D graphene current collector performance anodes for lithium ion batteries. Nano Lett.
boosts ultrahigh specific capacity in a highly uniform Prus- 2013;13:818‐823.
sian blue@graphene composite as a freestanding cathode for 155. Guan C, Zhao W, Hu Y, et al. High‐performance flexible
sodium ion batteries. Nanoscale. 2018;10:14697‐14704. solid‐state Ni/Fe battery consisting of metal oxides coated
138. Shelke MV, Gullapalli H, Kalaga K, et al. Facile synthesis of carbon cloth/carbon nanofiber electrodes. Adv Energy Mater.
3D anode assembly with Si nanoparticles sealed in highly 2016;6:1601034.
pure few layer graphene deposited on porous current col- 156. Yao Y, Chen M, Xu R, et al. CNT interwoven nitrogen and
lector for long life Li‐ion battery. Adv Mater Interfaces. 2017; oxygen dual‐doped porous carbon nanosheets as free‐
4:1601043. standing electrodes for high‐performance Na‐Se and K‐Se
139. Liu Y, Yao M, Zhang L, Niu Z. Large‐scale fabrication of flexible batteries. Adv Mater. 2018;30:1805234.
reduced graphene oxide‐sulfur composite films for flexible 157. Koutavarapu R, Reddy CV, Babu B, Reddy KR, Cho M, Shim J.
lithium‐sulfur batteries. J Energy Chem. 2019;38:199‐206. Carbon cloth/transition metals‐based hybrids with controllable
140. Fei H, Saha N, Kazantseva N, et al. Polyaniline/reduced architectures for electrocatalytic hydrogen evolution—a review.
graphene oxide hydrogel film with attached graphite current Int J Hydrogen Energy. 2020;45:7716‐7740.
collector for flexible supercapacitors. J Mater Sci: Mater 158. Sun X, Wang C, Gong Y, Gu L, Chen Q, Yu Y. A flexible
Electron. 2018;29:3025‐3034. sulfur‐enriched nitrogen doped multichannel hollow carbon
141. Luo Y, Guo R, Li T, et al. Application of polyaniline for Li‐ion nanofibers film for high performance sodium storage. Small.
batteries, lithium–sulfur batteries, and supercapacitors. 2018;14:1802218.
ChemSusChem. 2019;12:1591‐1611. 159. Fu L, Tang K, Song K, van Aken PA, Yu Y, Maier J. Nitrogen
142. Kim PJ, Kim K, Pol VG. A comparative study of cellulose derived doped porous carbon fibres as anode materials for sodium
structured carbons on the electrochemical behavior of lithium ion batteries with excellent rate performance. Nanoscale.
metal‐based batteries. Energy Storage Mater. 2019;19:179‐185. 2014;6:1384‐1389.
143. Jabbour L, Bongiovanni R, Chaussy D, Gerbaldi C, 160. Balogun M‐S, Qiu W, Lyu F, et al. All‐flexible lithium ion
Beneventi D. Cellulose‐based Li‐ion batteries: a review. battery based on thermally‐etched porous carbon cloth anode
Cellulose. 2013;20:1523‐1545. and cathode. Nano Energy. 2016;26:446‐455.
161. Wang Z, Shen J, Liu J, et al. Self‐supported and flexible sulfur 179. Chen R, Qu W, Guo X, Li L, Wu F. The pursuit of solid‐state
cathode enabled via synergistic confinement for high‐energy‐ electrolytes for lithium batteries: from comprehensive insight
density lithium–sulfur batteries. Adv Mater. 2019;31:1902228. to emerging horizons. Mater Horiz. 2016;3:487‐516.
162. Huang X, Qi X, Boey F, Zhang H. Graphene‐based compo- 180. Zhou Y, Zhang F, He P, et al. Quasi‐solid‐state polymer
sites. Chem Soc Rev. 2012;41:666‐686. plastic crystal electrolyte for subzero lithium‐ion batteries.
163. Castro Neto AH, Guinea F, Peres NMR, Novoselov KS, J Energy Chem. 2020;46:87‐93.
Geim AK. The electronic properties of graphene. Rev Mod 181. Liu H, Cheng X‐B, Huang J‐Q, et al. Controlling dendrite
Phys. 2009;81:109‐162. growth in solid‐state electrolytes. ACS Energy Lett. 2020;5:
164. Hu G, Xu C, Sun Z, et al. 3D graphene‐foam‐reduced‐ 833‐843.
graphene‐oxide hybrid nested hierarchical networks for 182. Zheng F, Kotobuki M, Song S, Lai MO, Lu L. Review on solid
high‐performance Li‐S batteries. Adv Mater. 2016;28: electrolytes for all‐solid‐state lithium‐ion batteries. J Power
1603‐1609. Sources. 2018;389:198‐213.
165. Reddy ALM, Srivastava A, Gowda SR, Gullapalli H, 183. Agrawal R, Pandey G. Solid polymer electrolytes: materials
Dubey M, Ajayan PM. Synthesis of nitrogen‐doped graphene designing and all‐solid‐state battery applications: an over-
films for lithium battery application. ACS Nano. 2010;4: view. J Phys D: Appl Phys. 2008;41:223001.
6337‐6342. 184. Yue L, Ma J, Zhang J, et al. All solid‐state polymer electro-
166. Wang J‐G, Jin D, Zhou R, et al. Highly flexible graphene/ lytes for high‐performance lithium ion batteries. Energy
Mn3O4 nanocomposite membrane as advanced anodes for Li‐ Storage Mater. 2016;5:139‐164.
ion batteries. ACS Nano. 2016;10:6227‐6234. 185. Zhang Q, Liu K, Ding F, Liu X. Recent advances in solid
167. Chong WG, Xiao F, Yao S, et al. Nitrogen‐doped graphene polymer electrolytes for lithium batteries. Nano Res. 2017;10:
fiber webs for multi‐battery energy storage. Nanoscale. 2019; 4139‐4174.
11:6334‐6342. 186. Xue Z, He D, Xie X. Poly(ethylene oxide)‐based electrolytes
168. Zhou G, Pei S, Li L, et al. A graphene‐pure‐sulfur sandwich for lithium‐ion batteries. J Mater Chem A. 2015;3:
structure for ultrafast, long‐life lithium‐sulfur batteries. Adv 19218‐19253.
Mater. 2014;26:625‐631. 187. Jiang Y, Yan X, Ma Z, et al. Development of the PEO based
169. Huang J‐Q, Peng H‐J, Liu X‐Y, et al. Flexible all‐carbon in- solid polymer electrolytes for all‐solid state lithium ion bat-
terlinked nanoarchitectures as cathode scaffolds for high‐rate teries. Polym. 2018;10:1237.
lithium–sulfur batteries. J Mater Chem A. 2014;2: 188. Perera K, Dissanayake M, Skaarup S, West K. Application of
10869‐10875. polyacrylonitrile‐based polymer electrolytes in rechargeable
170. Li S, Zhao Y, Liu Z, et al. Flexible graphene‐wrapped carbon lithium batteries. J Solid State Electrochem. 2008;12:873‐877.
nanotube/graphene@MnO2 3D multilevel porous film for 189. Huang B, Wang Z, Chen L, Xue R, Wang F. The mechanism
high‐performance lithium‐ion batteries. Small. 2018;14: of lithium ion transport in polyacrylonitrile‐based polymer
1801007. electrolytes. Solid State Ionics. 1996;91:279‐284.
171. Wu F, Zhao E, Gordon D, Xiao Y, Hu C, Yushin G. Infiltrated 190. Wang F, Li L, Yang X, et al. Influence of additives in a PVDF‐
porous polymer sheets as free‐standing flexible lithium‐ based solid polymer electrolyte on conductivity and Li‐ion
sulfur battery electrodes. Adv Mater. 2016;28:6365‐6371. battery performance. Sustain. Energy Fuels. 2018;2:492‐498.
172. Deng Q, Chen F, Liu S, et al. Advantageous functional in- 191. Yao P, Zhu B, Zhai H, et al. PVDF/palygorskite nanowire
tegration of adsorption‐intercalation‐conversion hybrid me- composite electrolyte for 4 V rechargeable lithium batteries
chanisms in 3D flexible Nb2O5@hard carbon@MoS2@soft with high energy density. Nano Lett. 2018;18:6113‐6120.
carbon fiber paper anodes for ultrafast and super‐stable so- 192. Berthier C, Gorecki W, Minier M, Armand M, Chabagno J,
dium storage. Adv Funct Mater. 2020;30:1908665. Rigaud P. Microscopic investigation of ionic conductivity in
173. Xu Y, Zhu Y, Han F, Luo C, Wang C. 3D Si/C fiber paper alkali metal salts‐poly(ethylene oxide) adducts. Solid State
electrodes fabricated using a combined electrospray/electro- Ionics. 1983;11:91‐95.
spinning technique for Li‐ion batteries. Adv Energy Mater. 193. Zhang C, Gamble S, Ainsworth D, Slawin AM, Andreev YG,
2015;5:1400753. Bruce PG. Alkali metal crystalline polymer electrolytes. Nat
174. Lu R, Cheng M, Mao L, et al. Potassium‐sulfur batteries: Mater. 2009;8:580‐584.
status and perspectives. EcoMat. 2020;2:e12010. 194. Zhou D, Shanmukaraj D, Tkacheva A, Armand M, Wang G.
175. Moreno M, Simonetti E, Appetecchi G, et al. Ionic liquid Polymer electrolytes for lithium‐based batteries: advances
electrolytes for safer lithium batteries: I. Investigation around and prospects. Chem. 2019;5:2326‐2352.
optimal formulation. J Electrochem Soc. 2016;164: 195. Blake AJ, Kohlmeyer RR, Hardin JO, et al. 3D printable
A6026‐A6031. ceramic‐polymer electrolytes for flexible high‐performance
176. Roth EP, Orendorff CJ. How electrolytes influence battery Li‐ion batteries with enhanced thermal stability. Adv Energy
safety. Electrochem Soc Interface. 2012;21:45‐49. Mater. 2017;7:1602920.
177. Cheng X‐B, Zhao C‐Z, Yao Y‐X, Liu H, Zhang Q. Recent 196. Yap Y, You A, Teo L, Hanapei H. Inorganic filler sizes effect
advances in energy chemistry between solid‐state electrolyte on ionic conductivity in polyethylene oxide (PEO) composite
and safe lithium‐metal anodes. Chem. 2019;5:74‐96. polymer electrolyte. Int J Electrochem Sci. 2013;8:2154‐2163.
178. Zhao C‐Z, Zhao B‐C, Yan C, et al. Liquid phase therapy to 197. Hema M, Tamilselvi P. Lithium ion conducting PVA:PVdF
solid electrolyte–electrode interface in solid‐state Li metal polymer electrolytes doped with nano SiO2 and TiO2 filler.
batteries: a review. Energy Storage Mater. 2020;24:75‐84. J Phys Chem Solids. 2016;96:42‐48.
198. Ihrner N, Johansson M. Improved performance of solid 216. Liang S, Yan W, Wu X, et al. Gel polymer electrolytes for
polymer electrolytes for structural batteries utilizing plasti- lithium ion batteries: fabrication, characterization and per-
cizing co‐solvents. J Appl Polym Sci. 2017;134(23):44917. formance. Solid State Ionics. 2018;318:2‐18.
199. Costa CM, Goncalves R, Lanceros‐Mendez S. Recent ad- 217. Chen S, Chen S, Zhang J. Thermal sugar bubbling prepara-
vances and future challenges in printed batteries. Energy tion of N‐doped porous carbon for high‐performance solid‐
Storage Mater. 2020;28:216‐234. state Zn‐air batteries. Batteries Supercaps. 2019;2:373‐379.
200. Yao Y, Wei Z, Wang H, et al. Toward high energy density all 218. Stephan AM. Review on gel polymer electrolytes for lithium
solid‐state sodium batteries with excellent flexibility. Adv batteries. Eur Polym J. 2006;42:21‐42.
Energy Mater. 2020;10:1903698. 219. Tang S, Guo W, Fu Y. Advances in composite polymer
201. Hu P, Chai J, Duan Y, Liu Z, Cui G, Chen L. Progress in electrolytes for lithium batteries and beyond. Adv Energy
nitrile‐based polymer electrolytes for high performance li- Mater. 2020;10: 2000802.
thium batteries. J Mater Chem A. 2016;4:10070‐10083. 220. Zhu M, Wu J, Wang Y, et al. Recent advances in gel polymer
202. Jia W, Li Z, Wu Z, et al. Graphene oxide as a filler to improve electrolyte for high‐performance lithium batteries. J Energy
the performance of PAN‐LiClO4 flexible solid polymer elec- Chem. 2019;37:126‐142.
trolyte. Solid State Ionics. 2018;315:7‐13. 221. Li W, Wu Y, Wang J, Huang D, Chen L, Yang G. Hybrid gel
203. Patla SK, Ray R, Asokan K, Karmakar S. Investigation of polymer electrolyte fabricated by electrospinning technology
ionic conduction in PEO–PVDF based blend polymer elec- for polymer lithium‐ion battery. Eur Polym J. 2015;67:
trolytes. J Appl Phys. 2018;123:125102. 365‐372.
204. Rathika R, Padmaraj O, Suthanthiraraj SA. Electrical con- 222. Kuo P‐L, Wu C‐A, Lu C‐Y, Tsao C‐H, Hsu C‐H, Hou S‐S. High
ductivity and dielectric relaxation behaviour of PEO/PVDF‐ performance of transferring lithium ion for polyacrylonitrile‐
based solid polymer blend electrolytes for zinc battery ap- interpenetrating crosslinked polyoxyethylene network as gel
plications. Ionics. 2018;24:243‐255. polymer electrolyte. ACS Appl Mater Interfaces. 2014;6:3156‐3162.
205. Zhang J, Zhao N, Zhang M, et al. Flexible and ion‐conducting 223. Tsao C‐H, Kuo P‐L. Poly(dimethylsiloxane) hybrid gel poly-
membrane electrolytes for solid‐state lithium batteries: dis- mer electrolytes of a porous structure for lithium ion battery.
persion of garnet nanoparticles in insulating polyethylene J Membr Sci. 2015;489:36‐42.
oxide. Nano Energy. 2016;28:447‐454. 224. Jie J, Liu Y, Cong L, et al. High‐performance PVDF‐HFP
206. Chen N, Xing Y, Wang L, et al. “Tai Chi” philosophy driven based gel polymer electrolyte with a safe solvent in Li metal
rigid‐flexible hybrid ionogel electrolyte for high‐performance polymer battery. J Energy Chem. 2020;49:80‐88.
lithium battery. Nano Energy. 2018;47:35‐42. 225. Wang J, Yamada Y, Sodeyama K, et al. Fire‐extinguishing
207. Xu R, Zhang X‐Q, Cheng X‐B, et al. Artificial soft‐rigid pro- organic electrolytes for safe batteries. Nat Energy. 2018;3:
tective layer for dendrite‐free lithium metal anode. Adv Funct 22‐29.
Mater. 2018;28:1705838. 226. Zhang SS. A review on the separators of liquid electrolyte Li‐
208. Wang TR, Zhang RQ, Wu YM, et al. Engineering a flexible ion batteries. J Power Sources. 2007;164:351‐364.
and mechanically strong composite electrolyte for solid‐state 227. Lee H, Yanilmaz M, Toprakci O, Fu K, Zhang X. A review of
lithium batteries. J Energy Chem. 2020;46:187‐190. recent developments in membrane separators for recharge-
209. Yi J, Zhou D, Liang Y, Liu H, Ni H, Fan L‐Z. Enabling high‐ able lithium‐ion batteries. Energy Environ Sci. 2014;7:
performance all‐solid‐state lithium batteries with high ionic 3857‐3886.
conductive sulfide‐based composite solid electrolyte and ex‐ 228. Huang X. Separator technologies for lithium‐ion batteries.
situ artificial SEI film. J Energy Chem. 2020. https://doi.org/ J Solid State Electrochem. 2011;15:649‐662.
10.1016/j.jechem.2020.09.038 229. Li H, Wu D, Wu J, Dong L‐Y, Zhu Y‐J, Hu X. Flexible, high‐
210. Hu J, He P, Zhang B, Wang B, Fan L‐Z. Porous film host‐derived wettability and fire‐resistant separators based on hydro-
3D composite polymer electrolyte for high‐voltage solid state li- xyapatite nanowires for advanced lithium‐ion batteries. Adv
thium batteries. Energy Storage Mater. 2020;26:283‐289. Mater. 2017;29:1703548.
211. Yue J, Xin S, Guo Y‐G. Recent progress and design principles 230. Huang J‐Q, Zhang Q, Peng H‐J, Liu X‐Y, Qian W‐Z, Wei F.
of nanocomposite solid electrolytes. Curr Opin Electrochem. Ionic shield for polysulfides towards highly‐stable
2020;22:195‐202. lithium–sulfur batteries. Energy Environ Sci. 2014;7:347‐353.
212. Li L, Deng Y, Chen G. Status and prospect of garnet/polymer 231. Liu Y, He K, Chen G, Leow WR, Chen X. Nature‐inspired
solid composite electrolytes for all‐solid‐state lithium bat- structural materials for flexible electronic devices. Chem Rev.
teries. J Energy Chem. 2020;50:154‐177. 2017;117:12893‐12941.
213. Ding J, Xu R, Yan C, et al. Integrated lithium metal anode 232. Wang Z, Lee YH, Kim SW, Seo JY, Lee SY, Nyholm L. Why
protected by composite solid electrolyte film enables stable cellulose‐based electrochemical energy storage devices. Adv
quasi‐solid‐state lithium metal batteries. Chin Chem Lett. Mater. 2020:2000892.
2020;31:2339‐2342. 233. Liu J, Yuan H, Tao X, et al. Recent progress of two‐
214. Wang S, Xiong P, Zhang J, Wang G. Recent progress on flexible dimensional lead halide perovskite single crystals: crystal
lithium metal batteries: composite lithium metal anodes and growth, physical properties, and device applications. EcoMat.
solid‐state electrolytes. Energy Storage Mater. 2020;29:310‐331. 2020;2:e12019.
215. Cheng X, Pan J, Zhao Y, Liao M, Peng H. Gel Polymer 234. Liu Y, Sun Z, Tan K, et al. Recent progress in flexible non‐
electrolytes for electrochemical energy storage. Adv Energy lithium based rechargeable batteries. J Mater Chem A. 2019;
Mater. 2018;8:1702184. 7:4353‐4382.
235. Qin JL, Peng HJ, Huang JQ, et al. Solvent‐engineered scal- 253. Gwon H, Kim H‐S, Lee KU, et al. Flexible energy storage
able production of polysulfide‐blocking shields to enhance devices based on graphene paper. Energy Environ Sci. 2011;4:
practical lithium‐sulfur batteries. Small Methods. 2018;2: 1277‐1283.
1800100. 254. Qian Y, Vu A, Smyrl W, Stein A. Facile preparation and
236. Kong L, Li BQ, Peng HJ, et al. Porphyrin‐derived graphene‐ electrochemical properties of V2O5‐graphene composite films
based nanosheets enabling strong polysulfide chemisorption as free‐standing cathodes for rechargeable lithium batteries.
and rapid kinetics in lithium‐sulfur batteries. Adv Energy J Electrochem Soc. 2012;159:A1135‐A1140.
Mater. 2018;8:1800849. 255. Ding Y, Ren H, Huang Y, Chang F, Zhang P. Three‐
237. Peng H‐J, Huang J‐Q, Liu X‐Y, et al. Healing high‐loading dimensional graphene/LiFePO4 nanostructures as cathode
sulfur electrodes with unprecedented long cycling life: spatial materials for flexible lithium‐ion batteries. Mater Res Bull.
heterogeneity control. J Am Chem Soc. 2017;139:8458‐8466. 2013;48:3713‐3716.
238. Liu D, Zhang C, Zhou G, et al. Catalytic effects in lithium‐ 256. Tian Y, An Y, Feng J. Flexible and freestanding silicon/
sulfur batteries: promoted sulfur transformation and reduced MXene composite papers for high‐performance lithium‐ion
shuttle effect. Adv Sci. 2018;5:1700270. batteries. ACS Appl Mater Interfaces. 2019;11:10004‐10011.
239. Wang L, Fu X, He J, et al. Application challenges in fiber and 257. Dong X, Chen L, Su X, Wang Y, Xia Y. Flexible aqueous
textile electronics. Adv Mater. 2020;32:1901971. lithium‐ion battery with high safety and large volumetric
240. Mo F, Liang G, Huang Z, Li H, Wang D, Zhi C. An overview energy density. Angew Chem Int Ed. 2016;55:7474‐7477.
of fiber‐shaped batteries with a focus on multifunctionality, 258. Guo Z, Li J, Xia Y, et al. A flexible polymer‐based Li–air
scalability, and technical difficulties. Adv Mater. 2020;32: battery using a reduced graphene oxide/Li composite anode.
1902151. J Mater Chem A. 2018;6:6022‐6032.
241. Peng H‐J, Xu W‐T, Zhu L, et al. 3D carbonaceous current 259. Guo Z, Ma Y, Dong X, Huang J, Wang Y, Xia Y. An en-
collectors: the origin of enhanced cycling stability for high‐ vironmentally friendly and flexible aqueous zinc battery
sulfur‐loading lithium‐sulfur batteries. Adv Funct Mater. using an organic cathode. Angew Chem Int Ed. 2018;57:
2016;26:6351‐6358. 11737‐11741.
242. Guo Z, Zhao Y, Ding Y, et al. Multi‐functional flexible aqu- 260. Sumboja A, Liu J, Zheng WG, Zong Y, Zhang H, Liu Z.
eous sodium‐ion batteries with high safety. Chem. 2017;3: Electrochemical energy storage devices for wearable tech-
348‐362. nology: a rationale for materials selection and cell design.
243. Li J, Ma C, Chi M, Liang C, Dudney NJ. Solid electrolyte: the Chem Soc Rev. 2018;47:5919‐5945.
key for high‐voltage lithium batteries. Adv Energy Mater. 261. Weng W, Sun Q, Zhang Y, et al. Winding aligned carbon
2015;5:1401408. nanotube composite yarns into coaxial fiber full batteries
244. Bai Y, Yue H, Wang J, et al. Super‐durable ultralong carbon with high performances. Nano Lett. 2014;14:3432‐3438.
nanotubes. Science. 2020;369:1104‐1106. 262. Wu Z, Liu K, Lv C, et al. Ultrahigh‐energy density lithium‐
245. Xie M, Sun X, Sun H, et al. Stabilizing an amorphous V2O5/ ion cable battery based on the carbon‐nanotube woven
carbon nanotube paper electrode with conformal TiO2 coat- macrofilms. Small. 2018;14:1800414.
ing by atomic layer deposition for lithium ion batteries. 263. Zhang Y, Zhao Y, Cheng X, et al. Realizing both high energy
J Mater Chem A. 2016;4:537‐544. and high power densities by twisting three carbon‐nanotube‐
246. Sun X, Li J, Shi C, et al. Enhanced electrochemical perfor- based hybrid fibers. Angew Chem Int Ed. 2015;54:
mance of LiFePO4 cathode with in‐situ chemical vapor de- 11177‐11182.
position synthesized carbon nanotubes as conductor. J Power 264. Zhang Y, Wang Y, Wang L, et al. A fiber‐shaped aqueous
Sources. 2012;220:264‐268. lithium ion battery with high power density. J Mater Chem A.
247. Lu H, Hagberg J, Lindbergh G, Cornell A. Li4Ti5O12 flexible, 2016;4:9002‐9008.
lightweight electrodes based on cellulose nanofibrils as bin- 265. Hu LB, Wu H, La Mantia F, Yang YA, Cui Y. Thin, flexible
der and carbon fibers as current collectors for Li‐ion bat- secondary Li‐ion paper batteries. Nano ACS. 2010;4:
teries. Nano Energy. 2017;39:140‐150. 5843‐5848.
248. Kim S‐J, Lee A‐Y, Park H‐C, et al. Carbon nanotube web‐ 266. Li N, Chen Z, Ren W, Li F, Cheng H‐M. Flexible graphene‐
based current collectors for high‐performance lithium ion based lithium ion batteries with ultrafast charge and dis-
batteries. Mater Today Commun. 2015;4:149‐155. charge rates. Proc Natl Acad Sci USA. 2012;109:17360‐17365.
249. Li B‐Q, Peng H‐J, Chen X, et al. Polysulfide electrocatalysis 267. Cho S‐J, Choi K‐H, Yoo J‐T, et al. Hetero‐nanonet re-
on framework porphyrin in high‐capacity and high‐stable chargeable paper batteries: toward ultrahigh energy density
lithium–sulfur batteries. CCS Chem. 2019;1:128‐137. and origami foldability. Adv Funct Mater. 2015;25:6029‐6040.
250. Bian Z, Xu Y, Yuan T, et al. Hierarchically designed CNF/S 268. Wan F, Zhang L, Wang X, Bi S, Niu Z, Chen J. An aqueous
−Cu/CNF nonwoven electrode as free‐standing cathode for rechargeable zinc‐organic battery with hybrid mechanism.
lithium−sulfur batteries. Batteries Supercaps. 2019;2:560‐567. Adv Funct Mater. 2018;28:1804975.
251. Li B‐Q, Chen X‐R, Chen X, et al. Tuning superhydrophobic 269. Ren J, Zhang Y, Bai W, et al. Elastic and wearable wire‐
materials with negative surface energy domains. Research. shaped lithium‐ion battery with high electrochemical per-
2019;2019:4608940‐4608947. formance. Angew Chem Int Ed. 2014;53:7864‐7869.
252. Zhang C, Cui L, Abdolhosseinzadeh S, Heier J. Two‐ 270. Zhang Y, Bai W, Ren J, et al. Super‐stretchy lithium‐ion
dimensional MXenes for lithium‐sulfur batteries. InfoMat. battery based on carbon nanotube fiber. J Mater Chem A.
2020;2:613‐638. 2014;2:11054‐11059.
271. Chen Q, Sun S, Zhai T, Yang M, Zhao X, Xia H. Yolk‐shell

Center. His research interests focus on nanocarbon
NiS2 nanoparticle‐embedded carbon fibers for flexible fiber‐
shaped sodium battery. Adv Energy Mater. 2018;8:1800054. materials, advanced energy storage/conversion,
272. Zhou Y, Jiang K, Zhao Z, et al. Giant two‐dimensional titania lithium–sulfur (Li–S) batteries, and computational
sheets for constructing a flexible fiber sodium‐ion battery catalysis.
with long‐term cycling stability. Energy Storage Mater. 2020;
24:504‐511.
Jia‐Qi Huang is a professor in the
273. Wang K, Zhang X, Han J, et al. High‐performance cable‐type
flexible rechargeable Zn battery based on MnO2@CNT fiber
Advanced Research Institute for Multi-
microelectrode. ACS Appl Mater Interfaces. 2018;10:24573‐24582. disciplinary Science at Beijing Institute
of Technology. He received his bachelor
AUTH OR BI OGRAPH IES and Ph.D. degree in chemical engineer-
ing from Tsinghua University. His research focuses
Long Kong received his B.S. and M.S. on interface electrochemistry and advanced energy
from Central South University in 2010 materials design in high‐energy‐density rechargeable
and 2013, respectively. He obtained his batteries, especially for lithium‐sulfur batteries and
Ph.D. in 2016 from Tokyo Institute of lithium metal anode.
Technology. After 2‐year postdoc in
Tsinghua University, he is currently a Qiang Zhang is a full professor at
research assistant professor in South University of Tsinghua University. He obtained his
Science and Technology. His research interests involve Ph.D. in chemical engineering (2009)
Li–ion/Li–S batteries and electrolyte materials. from Tsinghua University, China, and
subsequently held Research Associate/
Cheng Tang received his B.Eng. and Postdoc Research Fellow positions in the Case
Ph.D. from the Department of Chemical Western Reserve University, USA, and Fritz Haber
Engineering, Tsinghua University in Institute of the Max Planck Society, Germany. His
2013 and 2018, respectively, under the current research interests are advanced energy
supervision of Prof. Qiang Zhang and materials, including dendrite‐free lithium metal
Prof. Fei Wei. Currently, he is a postdoctoral anode, lithium sulfur batteries, and electrocatalysis,
researcher at The University of Adelaide working especially the structure design and full demonstration
with Prof. Shi‐Zhang Qiao. His research focuses on of advanced energy materials in working devices. The
nanomaterials and energy electrochemistry, including very recent progress on the Li metal protection is
3D graphene, hierarchical nanomaterials, single‐atom quite effective and have potentials for next‐generation
materials, next‐generation batteries, electrosynthesis high‐energy‐density batteries.
of chemicals and fuels, and so forth.
Hong‐Jie Peng obtained his B.Eng. and How to cite this article: Kong L, Tang C, Peng
Ph.D. from the Department of Chemical H‐J, Huang J‐Q, Zhang Q. Advanced energy
Engineering at Tsinghua University in materials for flexible batteries in energy storage: A
2013 and 2018, respectively. He is review. SmartMat. 2020;1:e1007.
currently a postdoctoral researcher at https://doi.org/10.1002/smm2.1007
Stanford University and Stanford Linear Accelerator

SmartMat - 2020 - Kong - Advanced energy materials for flexible batteries in energy storage A review

Uploaded by

Copyright:

Available Formats

You might also like

SmartMat - 2020 - Kong - Advanced energy materials for flexible batteries in energy storage A review

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

SmartMat - 2020 - Kong - Advanced energy materials for flexible batteries in energy storage A review

Uploaded by

Copyright:

Available Formats

Received: 2 October 2020 | Revised: 14 October 2020 | Accepted: 18 October 2020

Advanced energy materials for flexible batteries in energy

Long Kong1,2 | Cheng Tang3 | Hong‐Jie Peng4 | Jia‐Qi Huang5 |

1 | INTRODUCTION great success has been witnessed in the application of

SmartMat. 2020;1:e1007. wileyonlinelibrary.com/journal/smm2 | 1 of 35

density and safety are still kernel for battery technologies

F I G U R E 3 Schematics of three key

F I G U R E 4 Flexibility figure of merit (fFoM)

F I G U R E 5 (A) Volumetric energy density

F I G U R E 8 Graphene and CNT/

aligned CNT/Si composite fiber electrodes.98 The higher

TABLE 2 Construction, configuration, performance, and flexibility of representative flexible batteries

TABLE 3 Electrochemical energy powered flexible applications with different requirements

Abbreviation: IoT, Internet of thing; RFID, radio frequency identification.

TABLE 5 Safety test specifications of J.Flex batteries

271. Chen Q, Sun S, Zhai T, Yang M, Zhao X, Xia H. Yolk‐shell

You might also like