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Review
Design and Manufacture of 3D-Printed Batteries
Zhiyang Lyu,1,2,* Gwendolyn J.H. Lim,3 J. Justin Koh,3 Yi Li,4 Yanwen Ma,4 Jun Ding,3 Jinlan Wang,5
Zheng Hu,6 John Wang,3 Wei Chen,2,7 and Yunfei Chen1,*

SUMMARY Context & Scale

3D-printed batteries have emerged as a class of unique energy stor- In the era of customized and
age devices with outstanding features of microscale dimensions and miniaturized electronics, it is
aesthetic diversity, which are vital to miniaturized and customized crucial to develop the required
electronics. Understanding 3D printing designs in battery materials power sources, such as batteries,
and architectures is key to optimize performance and realize the with microscale and aesthetic
customization of 3D-printed batteries. In this Review, we summarize diversity. However, the currently
the latest advances in 3D-printed batteries with respect to the available commercial batteries are
connection between printable materials and printing techniques regulated in large sizes and
as well as the rational design considerations. We first introduce restricted in the usual form factors
unique features of 3D printing techniques, subsequently focusing because of the conventional tape-
on the printable battery modules and general approaches to making casting manufacturing process.
them printable. Thereafter, we examine the prominent roles of 3D 3D printing technology offers
printing designs in the module architectures, battery configura- unique advantages with its ability
tions, and effective solutions that help resolve issues that hamper to produce geometrically
batteries’ performance. We conclude by discussing further research complex shape or configuration
directions in terms of functional materials, advanced printing tech- designs and high-aspect-ratio 3D
nologies, and new device designs. architectures. Such technological
superiority endows the batteries
manufactured by 3D printing with
INTRODUCTION
outstanding features of tunable
Electrochemical energy storage devices are designed to store and release electricity dimensions, high shape
through chemical reactions, which are the power sources for portables and electric conformability, as well as
vehicles, as well as the key components of renewable energy utilization and the po- enhanced areal energy densities
wer grid.1 Rechargeable lithium-ion batteries (LIBs) are the most common energy and power densities. To optimize
storage devices that help create a rechargeable world nowadays. These ‘‘award-win- the performance of 3D-printed
ning Nobel Prize’’ batteries are powering daily lives, being used in devices such as batteries and realize their full
mobile phones and laptops to electric vehicles, and serve as energy storage devices technological potentials, it would
from renewable energy sources, such as solar and wind energy. With technological be essential to properly
advances, a variety of new miniaturized electronics have emerged, such as implant- understand the 3D printing
able medical devices, remote microsensors and transmitters, smart cards, wireless designs with respect to materials
sensor networks, and the Internet of Things (IoT).2 It is therefore crucial to further used, architectures, and devices.
develop the unique miniaturized power sources for these newly emerging technol-
ogies. In general, such power sources are endowed with the features of microscale This review provides a critical
dimensions and aesthetic diversity, as well as the high energy densities to provide overview of 3D-printed batteries,
long mission durations since the replacement is cost prohibitive in most of these focusing on the close connection
microscale electronic systems.3 However, the currently available commercial batte- between printable materials and
ries are regulated in large sizes and restricted in the usual form factors, e.g., cylindri- printing techniques, as well as the
cal-, rectangular-, coin-, and prismatic-shaped types. rational design considerations at
all levels. We will briefly visit the
As schematically shown in Figure 1A, conventional batteries are generally fabricated unique features of 3D printing
by preparing electrode slurries, then tape casting onto current collectors, winding or techniques and then focus on the
stacking cell components, and subsequently packaging components into metallic printable battery modules as well
canisters or pouch films, followed by the liquid-electrolyte injection.4 During this

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manufacturing process, the electrode slurries are coated using a slot die, reverse
roll, or doctor blade equipment, calendared for thickness control, and then cut to as the approaches to make them
the width specified for battery construction.5 However, with such a manufacturing and full cells printable. The
process, it is difficult to meet the special requirements of miniaturization and cus- prominent roles of 3D printing
tomization. Therefore, developing advanced manufacturing technology for micro- designs in module architectures,
batteries is essentially required to meet these criteria. Microbatteries are generally battery configurations, and
classified into 2D (or planar) and 3D (or nonplanar) types based on the electrode ar- effective solutions to resolve
chitectures. Compared with the 2D type, the 3D microbatteries can achieve higher several issues affecting the
energy densities and higher power densities because the 3D electrode architectures batteries’ performance are
can maximize the mass loading of active materials and enhance the surface-to-vol- examined. The upcoming
ume ratios by shortening ion transport distances.6,7 In addition, the 3D microbat- challenges associated with 3D-
teries have great potentials to serve as integrated power sources for autonomous printed batteries are then
microsized devices. In the manufacturing process of 3D microbatteries, the key discussed, together with further
step would be to fabricate the 3D architectures of electrodes, such as vertically research directions in terms of
aligned nanowires, nanorods, nanoporous monoliths, and multi-layered stacks.8 In novel functional materials,
the past two decades, substantially advanced techniques have been utilized to advanced printing technology,
build individual 3D electrodes or microbatteries,9 such as wet or dry etching,10–12 and new device designs. This
photopatterning,13,14 sputtering,15–17 electrodeposition,18–21 chemical vapor depo- review is aimed at raising new
sition (CVD),22,23 atomic layer deposition (ALD),24,25 physical vapor deposition inspirations in the design and
(PVD),26 and other combinations thereof. Although some of these relatively new ap- manufacturing of new-generation
proaches have demonstrated potential exciting paths, the commercialization of mi- 3D-printed batteries.
crobatteries is however still in the early and formative stage.27 There is still a lack of a
simple and economic approach to construct the 3D architectures of electrodes and
batteries.

3D printing technology, i.e., additive manufacturing (AM), is a completely bottom-

up manufacturing technology capable of rapidly fabricating geometrically complex
architectures with minimal material wastage and low cost.28–33 Over the past few
years, 3D printing technology has successfully been employed to fabricate various 1JiangsuKey Laboratory for Design and
batteries and microbatteries with outstanding features such as being form-factor- Manufacture of Micro-Nano Biomedical
free and having high shape conformability.34–47 In the 3D-printing manufacturing Instruments, School of Mechanical Engineering,
Southeast University, Nanjing 211189, China
process, the printable inks (or filaments) of electrode materials are first prepared 2Department of Chemistry, National University of
and then directly printed according to the predetermined electrode and cell designs Singapore, 3 Science Drive 3, Singapore 117543,
including the sizes, shapes, and architectures, and finally packaged with or without Singapore
3Department of Materials Science and
electrolyte filling (Figure 1A). This 3D printing process is more convenient, custom-
Engineering, National University of Singapore, 9
izable, and intelligent in comparison to the conventional tape casting and deposi- Engineering Drive 1, Singapore 117575,
tion techniques. As depicted in Figure 1B, the 3D-printed batteries possess the Singapore
following advantages: (1) much-enhanced design freedom in the micron-sized di- 4Key Laboratory for Organic Electronics and
mensions, with option of almost any desired shapes due to the ability to fabricate Information Displays & Jiangsu Key Laboratory
for Biosensors, Institute of Advanced Materials
complex architectures; (2 and 3) both higher areal and volumetric energy densities (IAM), Jiangsu National Synergetic Innovation
due to the higher areal-loading densities and the larger high-aspect ratio of the Center for Advanced Materials (SICAM), Nanjing
University of Posts & Telecommunications,
3D electrodes; (4) a higher power density due to the shorter ion or electron diffusion Nanjing 210023, China
pathways of the 3D-structural electrodes; (5) relatively lower manufacturing costs 5School of Physics, Southeast University, Nanjing
because 3D printing can dramatically reduce material wastage and save potential 211189, China
production time, as well as have the capability of eliminating the assembly and pack- 6Key Laboratory of Mesoscopic Chemistry of
MOE, Jiangsu Provincial Lab for
aging steps through direct integration of batteries and microscale electronics.40
Nanotechnology, School of Chemistry and
Chemical Engineering, Nanjing University,
Moreover, 3D printing can design any architecture and pore structures based on Nanjing 210023, China
7Department of Physics, National University of
what is needed. Such unique designs can competently solve some specific scientific
Singapore, 2 Science Drive 3, Singapore 117542,
or technological problems in both existing and new battery systems, such as the Singapore
solid-state Li-metal,48–50 lithium-sulfur (Li-S),51–55 lithium-oxygen (Li-O2),56,57 and *Correspondence: zhiyanglyu@seu.edu.cn (Z.L.),
Zn-air batteries.58 Overall, 3D printing technology opens a set of new avenues for yunfeichen@seu.edu.cn (Y.C.)
the rapid fabrication of batteries or microbatteries with distinctive architectures https://doi.org/10.1016/j.joule.2020.11.010

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Figure 1. Schematic Showing the Manufacturing Processes for Conventional Batteries (I), 3D Microbatteries (II), and 3D-Printed Batteries (III)
(A) Schematic illustration of the manufacturing processes.
(B) Radar charts grading the parameters of battery performance.

and high performance. In a timely response to overviewing the progress, this article
reviews significant progress in 3D-printed batteries, focusing on the connection be-
tween printing techniques and printable battery materials as well as the rational
design considerations. We present unique features of different 3D printing tech-
niques for battery manufacturing and summarize the current various building mod-
ules of printable batteries, including the cathode, anode, electrolyte, current collec-
tor, separator, and packaging, as well as the general approaches to make them
printable. Special emphasis on 3D printing designs in module architectures, battery
configurations, and typical problem-oriented cases are then examined. Finally, the
remaining challenges and future perspectives for 3D-printed batteries are outlined.

3D PRINTING TECHNIQUES FOR BATTERY MANUFACTURING

3D printing technologies can be divided into seven categories according to their
technical processes: (1) material extrusion (e.g., direct ink writing [DIW], fused depo-
sition modeling [FDM]), (2) powder bed fusion (e.g., selective laser sintering [SLS],
direct metal laser sintering [DMLS]), (3) vat photopolymerization (e.g., stereolithog-
raphy [SLA], digital light processing [DLP], two-photon lithography [TPL]), (4) mate-
rial jetting (e.g., inkjet printing [IJP], aerosol jet printing [AJP]), (5) sheet lamination
(e.g., laminated object manufacturing [LOM]), (6) binder jetting, and (7) directed en-
ergy deposition [DED].59 There have been several high-quality reviews on 3D print-
ing technologies that each give a comprehensive description of their characteristic
properties.28–32,45 In this review article, we focus on describing four representative

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Figure 2. Schematic Principles and Features of the Main 3D Printing Techniques for Battery Manufacturing
(A) Direct ink writing (DIW).
(B) Fused deposition modeling (FDM).
(C) Inkjet printing (IJP).
(D) Stereolithography (SLA).

technologies that can print the currently available battery modules so far, including
DIW, FDM, IJP, and SLA. Depending on the desired materials of battery modules, a
suitable printing technique is chosen based on the feature size of the final products
and processability to meet the specific architecture and performance requirements.
Hence, it is highly essential to understand the printing process, and characteristics of
different techniques for further material design and technique development. Fig-
ure 2 shows the schematic printing principles and the benefits and drawbacks of
the four printing techniques, in terms of the material range, ink requirement, resolu-
tion, design versatility, throughput, size capability, multi-material capability, and
cost.

DIW Printing
DIW printing (i.e., robocasting) is a representative extrusion-type deposition tech-
nique that begins with the preparation of a viscoelastic ink with the characteristic
rheology including yield stress behavior containing the raw material(s) (Figure 2A).
The designed 3D architecture is then produced by extruding continuous filaments
stacked on a building platform through a nozzle under controlled pressure. The
nozzle can move horizontally on a 2-axis plane, and the platform can move vertically
downwards after each new layer is deposited with the help of computer-aided
manufacturing or computer-aided design (CAM or CAD) software. The printed reso-
lution is usually determined by a combination of the nozzle diameter, applied pres-
sure, and characteristics of the extrusion ink. The ability of object molding is deter-
mined by certain key rheology properties of the ink, which include the yield stress
(sy), elastic or storage (G0 ) modulus, viscous or loss (G00 ) modulus, and viscosity (ƞ).

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Foremost, the yield stress behavior is the most important characteristic in controlling
the volumetric flow rate and recovery behavior of the ink after deposition and deter-
mining the printing ability after yielding. A yield stress ink behaves as a solid under
low applied stress and starts to flow like a liquid above a certain level of stress. Viscos-
ity is a common rheological parameter to describe the intermolecular interactions in
the ink. It is calculated as a ratio of the shear stress to shear rate and thus can be easily
quantified and manipulated.29 Inks with low viscosities can easily form droplets and
will not have enough yield stress to support the entire 3D architecture after the ink
extrusion, whereas those inks with extremely high viscosities can easily block the
nozzle and require higher printing pressures. Therefore, an ink with suitably high vis-
cosity and elastic behavior (determined by G0 and G00 ) is favorable for the DIW pro-
cess, especially those that exhibit shear-thinning behavior, whereby the viscosity de-
creases with increasing shear rates.42,43 The shear-thinning ink would flow like a liquid
and thus be easily extruded through the dispensing nozzle at a high shear rate under
the applied printing pressure, and it would behave like a solid at low shear rates or at
rest either due to gelation. Hence, the preparation of a printable ink with specific yield
stress behavior is critical for the success of the DIW printing process.

DIW printing is most widely used in the fabrication of battery modules among the four
printing techniques due to several remarkable printing advantages, which can be
summarized as follows (Figure 2A)60–62: (1) DIW is applicable to an almost infinite
number of printable materials, ranging from metals, plastics, ceramics, hydrogels,
food, and living cells, to novel functional nanomaterials (e.g., graphene, 2D MXene,
perovskite, metal-organic frameworks, covalent organic frameworks),28 which pro-
vide numerous possibilities for printing active materials of batteries; (2) DIW has
been demonstrated to be able to achieve a high printing resolution with minimum
feature size down to 1 mm by using microcapillary nozzles63; (3) DIW is capable of
fabricating complex 3D multi-scale architectures, offering considerable design
versatility; (4) DIW proceeds with a high printing throughput, especially when using
microvascular multinozzle arrays, and owns large-size capability64; (5) DIW is able
to deliver a high multi-material capability with a high degree of spatial and composi-
tional precision either by using multiple or coaxial printheads filled with different ink
compositions or by using microfluidic printheads allowed for switching, mixing, or
core-shell printing65; and (6) varying grade DIW machines are available at low costs
with a simple controlled process. Therefore, these outstanding features make DIW
a good choice for a variety of applications, such as energy storage devices, microflui-
dic networks, tissue-engineering scaffolds, photonic band-gap materials, sensors,
and biomedical devices. Indeed, DIW printing has explored a great deal for high-
quality 3D active materials in battery modules. Nevertheless, one of the major chal-
lenges for DIW lies in the preparation of printable inks with the desired battery mate-
rials. It requires a set of technical specifications for the printable inks, which include
yield stress behavior with high viscosities (106–108 cP), well-controlled viscoelasticity,
and requirement of being extruded smoothly under printing pressures.29

FDM Printing
FDM is another common extrusion-type printing process working by layer-by-layer
deposition of thermoplastic filaments that are heated to their semi-molten state at
the fine nozzle tip before extrusion (Figure 2B).66 The extruded materials will then
be solidified quickly on the build-platform (at a lower temperature) to form a uniform
hardened layer and then be built into a 3D object by moving the platform and nozzle,
designed by CAM or CAD software. FDM is the most prevalent 3D printing technol-
ogy and is widely employed in daily use in training aids, stationeries, toys, and cre-
ative gifts due to its simple operation and low cost.

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In comparison with DIW, FDM has a narrower printable materials range and usually
requires thermoplastic materials, mainly including the polylactic acid (PLA), acryloni-
trile butadiene styrene (ABS), polycarbonate (PC), polyamide (PA), and thermo-
plastic urethane (TPU).67 The materials for FDM must also be in the form of a solid
filament with a specific width, which limits its applicability for fabricating battery
electrodes because the required specific active materials that have high electrical
conductive properties usually do not come in a filamentary form. As such, modified
filament composites with active materials being embedded within the thermoplastic
polymer matrix are usually fabricated first before printing of the battery materials.
One other possible use of FDM is for printing substrate, which has to be further
modified via additional post-treatments, such as electrodepositing electrode or
electrolyte materials. In addition, FDM has a lower printing resolution of about
50–200 mm, a lower printing throughput, and lower flexibility of multi-material capa-
bility in comparison with DIW (Figure 2B). Nevertheless, FDM is independent of the
preparation of printable inks, which is a critical factor for DIW printing but is depen-
dent on the fabrication of the composite thermoplastic filaments instead.

Inkjet Printing
IJP printing is a representative deposition technique that can directly propel drop-
lets of ink through a nozzle onto a paper or plastic substrate (Figure 2C).68 Similar
to the case of DIW, the printable ink is first prepared, and the patterns are built by
moving the printhead with nozzles across the platforms through the printer.
Currently, there are two main contemporary inkjet technologies based on the gen-
eration of droplets: continuous (CIJ) and drop-on-demand (DOD). In CIJ, a stream
of fluid is passed through a tip and breaks up into small droplets through Plateau-
Rayleigh instability. DOD technology can generate individual drops when required,
and create patterns as designed by programming the position of the printhead,
which is more economical in ink delivery and more flexible in pattern design than
CIJ. DOD technology can be further subdivided into thermal and piezoelectric
DOD, on the basis of distinguishing the mechanism by which a drop is ejected.69

IJP has been explored to print a wide range of materials including metals, conduc-
tive polymers, carbon-based, proteins, and nanoparticle materials. In recent years,
IJP is becoming a standard fabrication tool in a number of technological areas,
including electronics, displays, rapid prototyping, sensors, tissue engineering, and
ceramic component manufacturing. The same as the DIW, IJP also has specific re-
quirements for the printable ink in surface tension, density, and dynamic viscosity,
but the difference comes from the ink of IJP that requires a lower viscosity
(40–100 cP). There’s a need to understand and control the ink behavior, such as
the generation and flight of droplets, the interaction of droplets on the substrate,
and the solidification behavior of the droplets after printing. Considering the sub-
stantial number of printable materials available, IJP has also the high flexibility of
multi-material capability and can directly print active materials of battery electrodes,
although most of them tend to be presented in the form of a thin film because of the
low-dimension design versatility and lack of self-standing ability (low viscosity of the
ink). Moreover, drop generation can produce fluid drops with diameters in the range
of 10–150 mm, a smaller printing resolution, a lower printing throughput, and lower
size capability than those of DIW.

SLA Printing
SLA is a representative photopolymerization printing process that operates by
focusing a beam of ultraviolet (UV) laser onto a vat of UV-curable photopolymer resin
(Figure 2D).70,71 First, the resin of the vat surface where the UV laser hits is

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photochemically cured and solidified to form a pre-programmed single layer by the

UV light with the use of motor-controlled mirrors. Then, the build platform lowers
one layer (layer height predetermined), and a moving blade recoats the top of the
resin tank. The 3D object is finally completed after each new layer is cured according
to the model designed. Completed parts must be washed with a suitable solvent to
clean the wet uncured resin off their surfaces before post-processing. The photopo-
lymerization process involves a proper photoinitiation process and a fast crosslinking
reaction so that the solidification of liquid resin into highly cross-linked networks
quickly occurs upon light exposure.70,71 Therefore, it is necessary to have a set of
compatible photoinitiators and prepolymer materials (monomers, oligomers, and
mixtures) in the right ratio in the liquid resin.

Based on the principle of SLA, the preparation of printable resins, consisting of

active materials, photoinitiators, and prepolymers, is the prior and critical step.71
The formulation of the desired resin can be very rather challenging due to the spe-
cific requirements that include both optical and rheological properties. For example,
poor flowability of the ink will cause difficulties in the refilling of the SLA tank, and an
unsuitable refractive index of the embedded material will scatter UV light, leading to
processing defects, incomplete curing, reduction in mechanical properties, and
inaccurate alterations. Therefore, they limit the available printable materials, espe-
cially for the direct printing of the highly conductive battery electrodes. Similar to
the case of FDM, some battery modules can be built from the printed templates
by SLA technology. SLA also has low flexibility of multi-material capability because
of its working principles and being limited to only suitable materials that can meet
the above requirements. Nevertheless, SLA can print objects with designs for high
resolution with minimum feature size down to 0.5 mm. Hence SLA is employed in a
wide variety of applications from automotive, aerospace, electronic devices to living
tissues. Different from DIW, FDM, and IJP printing techniques, SLA is a nozzle-free
technique at which the issue of nozzle clogging is avoided. Despite these advan-
tages, practical industrial applications have been limited due to the high cost and
the difficulty of handling photopolymers, which are generally sticky and messy.
Possible residual photoinitiator and uncured resin are also among other concerns,
which may result in issues such as impurities and toxicity.

TPL is another state-of-the-art photopolymerization-based technique.72,73 Due to its

mechanism that relies on nonlinear two-photon absorption, TPL is able to create fea-
tures smaller than the diffraction-limited spot using a focused, femtosecond laser
operating in infrared. This allows TPL to generate 3D structures with features in
the scale of 200 nm and have a faster production rate than high-resolution 2D tech-
niques.74 Hence TPL has been used as an effective tool to design and fabricate the
micro and nanoscale structural electrodes that can be transformed to reconfigurable
architected materials based on electrochemically driven cooperative beam buck-
ling.75 Recently, Oakdale and co-workers managed to increase the throughput by
spatially and temporally focusing an ultrafast laser to implement a projection-based
layer-by-layer parallelization, achieving a high volumetric processing rate between
33 and 131 mm3/h.72 Despite this, it still would take several hours to print a 1 cm3
electrode using the TPL technique, which would seriously limit its use in efficient bat-
tery manufacturing.

PRINTABLE BATTERY MODULES

Batteries are classified into two types: primary (non-rechargeable) batteries and sec-
ondary (rechargeable) batteries. Of these two, secondary batteries dominate the

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Figure 3. Summary of Current 3D-Printed Battery Modules

(A) Schematic illustration of the battery architecture and the lists of printable modules including a cathode, electrolyte, and anode. The cathode and
anode materials are classified based on the battery systems and the values of practical capacities.
(B) Roadmap for the printable cathode, electrolyte, and anode. The full names of the abbreviations are listed as follows: LiFePO 4 (LFP), LiMn 1-x Fe x PO 4
(LMFP), LiCoO 2 (LCO), LiMn 2 O4 (LMO), Na 3 V 2 (PO 4 ) 3 (NVPO), NaMnO 2 (NMO), LiNi 0.8 Co 0.15 Al0.05 O 2 (NCA), sulfur and carbon (S/C), carbon (C),
poly(ethylene glycol) (PEG), Li 7 La 3 Zr 2 O12 (LLZO), and Li 4 Ti 5 O 12 (LTO). Different used printing techniques are represented by different symbols: C for
DIW, - for FDM, : for IJP, and + for SLA.
(C) The proportion of the printable cathode materials and the employed printing techniques for the printable cathode and anode, which are based on
numbers of the corresponding citations in this review.

battery market as they can be electrically recharged after discharge, and they
include lead-acid, nickel-cadmium, nickel-metal hydride, lithium-ion, and flow batte-
ries, and so on. There have been several high-quality reviews on battery technolo-
gies that give a comprehensive introduction of their characteristics.1,76 In this review,
the focus is on 3D-printed batteries, which mainly include LIBs and new beyond Li-
ion systems, such as Na-ion, solid-state Li-metal, Li-S, and Li-O2 batteries.

The design and fabrication of various battery modules, such as cathodes, anodes,
electrolytes, and separators (Figure 3A), play an important role in enhancing the
overall performance of batteries, which includes key parameters such as the energy
density, volume energy density, power density, cycle life, and safety. Therefore, in
this section, we will examine currently known printable battery modules from an
architectural point of view. Individual battery modules require several specific prop-
erties, such as mechanical strength, high electronic, and ionic conductivity. There-
fore, it is necessary to select and combine suitable 3D printing techniques and ma-
terials such that they can together meet the specific requirements. With the rapid
increase in the number of novel functional nanomaterials for electrochemical energy
storage,77 developing them into printable materials for suitable 3D printing tech-
niques is undoubtedly of great significance with respect to advances in batteries
and other energy storage technologies.

In 2013, Lewis and co-workers printed a Li-ion microbattery that consisted of the
commonly used anode and cathode of LIBs with an interdigitated architecture
through DIW for the first time.78 It is a creative effort of utilizing the 3D interdigitated
design and combining it with DIW as well as making the stacking and arrangement of

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the battery modules a smoother process. From then on, researchers have been
constantly developing new electrode materials and 3D module architectures, using
different printing techniques to assemble them. Efforts were made to create 3D-ar-
chitectured electrodes or batteries by IJP even before 2013; however, most of them
were presented in thin-film 2D architectures with low design versatility.79,80 In this
review, we will focus on the progress made in constructing printable battery modules
with 3D architectures from 2013 onward, as shown in Figure 3B.

Cathode
To date, several of the most commonly used cathode materials for LIBs have been
successfully printed (Figure 3B), such as olivine-type lithium iron phosphate
(LiFePO4),78,81–93 lithium transition-metal phosphates (LiMn1-xFexPO4),94 lithium co-
balt oxides (LiCoO2),82 lithium manganese oxides (LiMn2O4),95–97 and LiNi0.8-
Co0.15Al0.05O2 (NCA).98 Therein, LiFePO4 is the most developed among them,
and it has been printed by many different techniques including DIW,78,82–88,94
FDM,91,92 and IJP.81,89,90 In addition, the printable cathodes of Na-ion batteries, a
low-cost alternative battery to LIBs, also have been fabricated, for instance,
Na3V2(PO4)3 with a mesh structure via DIW99 and NaMnO2 with a cylinder structure
via FDM.100 According to the roadmap of printable cathode development (Fig-
ure 3B), over the past 3 years, researchers have been on course constantly printing
the cathodes with high specific capacities for new battery systems with higher en-
ergy densities, e.g., sulfur and carbon composites for Li-S batteries51–55,101,102
and carbon-based catalyst composites for Li-O2 batteries.56,57 Besides the common
Li-S and Li-O2 cathodes, there are also a variety of 3D-printed cathodes for other
battery systems, for example, the reduced graphene oxide (rGO) with a hierarchical
porous structure for Na-O2 batteries,103 rGO framework with nickel nanoparticles for
Li-CO2 batteries,104 rGO and carbon nanotube (CNT) framework with catalyst nano-
particles for Zn-air batteries,58,105 MnO2/CNT films for Al-air batteries,106 Ag2O films
for Zn-Ag2O batteries,107 and MnO2 film for Zn-MnO2 microbattery,108 and so on.

The summary of printable cathode materials and the corresponding 3D printing

techniques employed for them are illustrated in Figure 3C. Printable phosphate
cathodes make up the largest proportion of 42.1%, followed by sulfur-based cath-
odes for Li-S batteries, carbon-based cathodes for metal-air batteries, and cathodes
made up of metal oxides (LiCoO2, LiMn2O4, NCA, Ag2O, and MnO2). It appears that
sulfur and carbon cathodes have been developed vigorously only in the past 5 years.
In the long term, one would foresee a surge of research and development on these
advanced higher specific-energy batteries. In addition, DIW is undoubtedly the most
adopted techniques with the largest proportion of 76.3%, followed by IJP and FDM.
This is because of the outstanding printing advantages, in particular the vast possi-
bilities of printable material precursors with regard to DIW, as described in the pre-
vious section.

Anode
From Figure 3B, one can see that the most commonly printed anode of LIBs is lithium tita-
nate (Li4Ti5O12), which can be developed by DIW109,110 and FDM.91,92,111 In addition,
other LIBs anode materials with higher specific capacities have been successfully printed,
such as carbon (graphite and graphene),98,112–114 SnO2 quantum dots,115 and silicon
(Si).116 For example, a printable graphite anode with a high graphite loading of 49.2 wt
% was successfully fabricated using the FDM technique by optimizing the weight ratios
of graphite/PLA/plasticizer when processing the filaments.114 Similar to the printed cath-
odes of Na-ion batteries, the corresponding Na-ion anodes also have been fabricated,
such as graphene,99 TiO2,100 and MoS2-graphene composite.117 Moreover, recent

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studies appear to focus on the next-generation Li metal anodes based on the designed
3D-printed structure, which has an extremely high theoretical capacity of 3,860 mAh/g
and low redox potential of 3.04 V versus standard hydrogen electrode.118 For instance,
3D-printed porous frameworks based on the carbon, 2D MXenes (Ti3C2Tx), and copper
metal, have been constructed as the current collectors for hosting the Li metal
anode.50,118–120 More importantly, the 3D-printed porous architecture is highly used to
solve the problems faced by Li metal anodes, for example, the uncontrollable Li dendrite
growth and the large volume interface change, which will be further discussed in detail in
the next section. Similarly, DIW is the most adopted technique for the fabrication of an-
odes, occupying the largest proportion, 60.9% of the research papers (Figure 3C).

Electrolyte
Most of the reported batteries made using 3D-printed electrodes have employed
the liquid or sol-gel electrolytes that are common electrolytes for the LIBs, Li-S, or
Li-O2 batteries. Recently several 3D-printable electrolytes have been developed
for (hybrid) solid-state batteries (Figure 3B), which include polymers,121,122 poly-
mer-ceramic hybrids,49,123–126 and ceramic types.48 Among them, the hybrid type
electrolyte is the most fabricated, since the easy adjustment of the ratio between
the polymer and ceramic components can be used to tune the rheology of the
inks or filaments to meet printing conditions and also to regulate the ion conductiv-
ity, mechanical stability, and thermal property of the electrolyte. For instance, Dur-
stock and co-workers devised an approach to fabricate the hybrid electrolytes with
controlled porosity by printing the ink composed of poly(vinyldene fluoride) (PVDF),
glycerol, and nanosized Al2O3 filler, which was shown to exhibit a higher rate perfor-
mance, better wetting characteristics, and enhanced thermal stability in comparison
to commercial polyolefin separators.123 Bruce and co-workers developed a hybrid
electrolyte based on the ceramic Li-ion conductor Li1.4Al0.4Ge1.6(PO4)3 (LAGP) and
epoxy, which was capable of 3D bicontinuous order microchannels for solid-state
batteries via the SLA technique, demonstrating the optimal combination of ion con-
ductivity and mechanical properties.49 Another high ionic conductivity hybrid elec-
trolyte was fabricated by the DIW technique, which consisted of the poly(vinylidene-
fluoride-co-hexafluoropropylene) (PVDF-co-HFP) matrices, Li+-conducting ionic
liquid (Pyr13TFSI and LiTFSI salt), and TiO2 nanoparticle filler.124 Kim et al. reported
a flexible, non-flammable, and UV-curable hybrid electrolyte for the flexible, shape-
versatile, and bipolar all-solid-state LIBs.125 Golodnitsky and co-workers employed
the FDM technique to develop a hybrid electrolyte composed of LiTFSI, polyeth-
ylene oxide (PEO), and PLA with SiO2 or Al2O3 filler for enhanced mechanical prop-
erties and high-temperature durability.126 For polymer types, Pan and co-workers
printed a gel polymer electrolyte with a 3D architecture based on poly(ethylene gly-
col) (PEG) by the SLA method, and active electrodes were then subsequently filled
into the 3D structure to assemble a 3D microbattery.121 Another solid polymer elec-
trolyte based on PEO polymer with LiTFSI salt was developed via an FDM printer,
achieving a high ion conductivity of 2.18 3 103 S/cm at 90 C after optimizing the
O/Li+ molar ratio.122 For ceramic types, Wachsman and co-workers fabricated a
full ceramic Li7La3Zr2O12 electrolyte with a variety of surface patterns aiming to
enhance the interface contact with the electrodes.48 Apart from the above-
mentioned three types of electrolytes, Dunn and co-workers developed a photopat-
ternable electrolyte through a Li+-conducting ionogel, which could be employed in
the SLA technique.127

Current Collector, Separator, and Packaging

To realize the ultimate goal of fully printed batteries with design diversity, other
printable battery modules such as current collector, separator, and packaging

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substances should also be developed. Unfortunately, there are generally fewer

studies in this respect and more efforts are needed. The conductive current collec-
tors along with electrodes are important components to enable electrochemical re-
actions in batteries. Lewis and co-workers fabricated a gold (Au) current collector
through a combination of lithographic patterning and e-beam deposition before
printing LIBs electrodes directly on it.78 There are also printable metallic current col-
lectors (e.g., Ni, Cu, Ag/Zn) of supercapacitors that could be used as references in
the battery field.62,128,129 For example, a printable Ni current collector was success-
fully made by synthesizing a Ni paste comprising Ni flakes, Ni nanoparticles, and a
photoreactive polymeric binder, polyvinylpyrrolidone (PVP) in terpineol, followed
by DIW and flash-light sintering processes.128 In terms of the separator module,
Hu and co-workers reported a safe separator for Li metal batteries by integrating bo-
ron nitride (BN) nanosheets into PVDF-co-HFP for thermal management purposes
via extrusion-based 3D printing.130 The printed BN-separator not only offered a uni-
form thermal distribution interface but also favored the desired homogeneous Li
nucleation, which suppressed Li dendrite growth and ultimately enhanced the over-
all electrochemical performance. Lewis and co-workers used a UV-curable pack-
aging and separator inks and fabricated fully 3D-printed packaged batteries,
including printing of semisolid cathode and anode inks.87 The separator ink is a com-
posite of LiTFSI/propylene carbonate (PC) electrolyte, photocured acrylate resin, a
photoinitiator, and Al2O3 particles fillers. The packaging ink consists of epoxy and
fumed SiO2, crosslinks, and bonds with the current collector simultaneously during
the printing process. Kim et al. printed cans and lids in different packaging shapes
and sizes by SLA, for the customized aqueous zinc-ion batteries.131 A 3D-printed
ABS casing was developed to accommodate replaceable electrodes and electro-
lytes by FDM printing, achieving a high-capacity periodate reserve battery.132

General Approaches to Make Battery Materials Printable

Overall, tremendous efforts have been made in the fabrication of various battery ma-
terials in the past 7 years, and the general approaches to make battery modules
printable can be summarized according to the different printing techniques. For
the DIW and IJP techniques, preparing the printable inks is the most crucial step
for the printing process. The inks generally contain the active materials and the poly-
meric binders or additives in a suitable solvent, which can be formulated into an
appropriate proportion to meet the shear-reversible and viscosity requirements. In
this process, the physicochemical properties of active materials, binders, and sol-
vents, such as density, particle size, hydrophilicity, miscibility, viscosity, and surface
chemistry, also have an important influence on the formulation of the inks. Hence,
the success of printable inks is usually by more of a trial-and-error process with a sys-
tematic approach rather than a fully deliberate attempt; hence, the formulation may
vary in different studies. As a typical example, the LiFePO4 inks can be prepared by
using the different binders and solvents systems, for instance, ethylene glycol (EG) in
water,78 PVDF and carbon black in N-methyl-2-pyrrolidine (NMP),83 cellulose nano-
fibers in water,50 and Pluronic F127 and black carbon in water.118 In addition, the
commonly seen carbon-based ink can be either simply prepared by only using wa-
ter104 or in contrast, through a complex formulation containing phenol-formalde-
hyde (PF) resin and SiO2 filler followed by high-temperature annealing.55

In comparison with the preparation of printable inks for DIW and IJP, designing
printable active materials using the FDM and SLA techniques is more difficult and
complex. For the FDM technique, the feedstock composite that has a thermoplastic
matrix embedded with active materials must first be blended and then extruded to
form a filament with suitable dimensions through an extruder. For example, the

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LiFePO4 filament was prepared by dissolving PLA pellets in dichloromethane91 or

1,3-dioxolane92 with graphite to form LiFePO4/PLA/carbon composites. Even
when using the same thermoplastic as the matrix for the composite filament, the vis-
cosity may be different at the same elevated temperature. For example, the viscosity
of PLA at 190 C is different from that of PLA/carbon. In general, complications may
arise if it is a new filament, either matrix or filler. For the SLA technique, the curable
ink containing the active materials, photoinitiators, and prepolymers should be first
prepared in a suitable amount that can fill the printing tank. 133 Unfortunately, there
are currently no proper studies showing direct printing of the active materials using
SLA, although some battery modules were indirectly built from the printed tem-
plates with the help of the SLA technology.131 On the whole, regardless of choices
in the 3D printing techniques, a systematic optimization starting from powders of
the active materials to the preparations for the printable slurry, ink, and filament
needs to be done, in order to make a printed battery with the best electrochemical
performance.

PRINTING DESIGNS IN BATTERY MANUFACTURING

In the last section, a general overview is provided for currently known printable ma-
terials for batteries. It should be pointed out that most of these studies have focused
on the development of printable materials but less on fully utilizing the advantages
of 3D printing design customizability. The unique advantage of 3D printing technol-
ogies for battery fabrication is the flexible architecture manufacturing and control-
lable printing design, which can significantly influence the batteries’ performance
and applications. In this section, we will discuss the 3D printing designs for batteries
applications, focusing on the electrode architectures, battery configurations, and
problem-oriented design considerations.

Construction Strategies of Electrodes

3D-printed electrodes are constructed by either printing directly or requiring post-
treatment processes, such as solvent evaporation, freeze-drying, annealing, physico-
chemical treatments, and photo-/thermo-curing. These post-treatment procedures
are commonly used since the printed active materials shall have a combination of
high electrically conductive properties, electrochemical activity, and mechanical sta-
bility. It should be pointed out that some of these post-treatment processes may lead
to shrinkage and/or distortion of the printed architectures and manufacturing
complexity, thereby decreasing the printing repeatability and reproducibility.
Hence, the compatibility between post-treatment methods and printed materials is
an important consideration in practical manufacturing. As schematically shown in Fig-
ure 4A, the four typical construction strategies of electrodes are summarized: direct
printing, conversion, deposition, and filling. It should be noted that several different
combinations of these strategies can satisfy the performance objectives. The distinct
features of these four construction strategies are described as follows:

(1) In the direct printing strategy, printable materials are the functioning active
materials for electrode, and the fabrication process requires no further
post-treatments after 3D printing. Classic examples are the fabrication of car-
bon-based electrodes via DIW,134 e.g., the holey graphene oxide (GO)56 and
the ultralight GO aerogel.135 In this process, the used solvent for the ink is
usually volatile or easily removed by vacuum or freeze drying. Besides, the
active materials are directly fabricated by a unique FDM method through
simultaneously degrading PLA at a high nozzle temperature when extruded,
yielding graphene anodes112 and LiFePO4 cathodes.91,92

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Figure 4. Schematic Illustration of 3D Printing Designs on Battery Structures

(A) Construction strategies of electrodes.
(B) Typical architectures of battery modules.
(C) Configurations of printed batteries.

(2) In the conversion strategy, the active materials are developed by an extra phys-
icochemical post-treatment to achieve greater functionality after printing. For
example, the annealing treatment can remove the solvent or/and convert the
polymeric binders to carbon, thereby increasing the conductivity of the ultimate
electrodes and enhancing the porosity for electrolyte penetration. This is the
most commonly used strategy to construct the electrodes, as developing inks
with 3D printable behavior will usually be easier upon the addition of binders
and then subsequently removing them. Examples include LiFePO4,78 LiCoO2,82
LiMn1-xFexPO4,94 and Li4Ti5O12,83 as well as the carbon-based electrodes such
as metal-organic-framework (MOF)-derived carbon framework and closely
stacked and aligned active carbon/CNT/rGO composite.136
(3) In the deposition strategy, the electrodes are constructed by depositing active
materials on the 3D-printed substrates, for example, LiFePO4 and Li4Ti5O12 on
perforated polymer substrates,137 palladium on SLA-based polymers,138 polypyr-
roles electrodeposited on the graphene-based conductive filament,139 and high
mass loading of MnO2 on a porous carbon aerogel scaffold.140
(4) In the filling strategy, the battery modules are constructed by filling active mate-
rials into the 3D-printed porous substrates or templates, for example, the elec-
trode materials ink filled into 3D porous gel polymer electrolyte,121 and the
ceramic Li+ conductor LAGP filled into the polymer template as the electrolyte.49

In both (3) and (4), whether the 3D printed substrates or the templates shall be
removed ultimately will depend on the objective(s) of the functional active material.

Module Architectures and Battery Configurations

The architectures of 3D-printed modules largely determine the battery configura-
tions and have a significant influence on the electrochemical performance. As sche-
matically shown in Figure 4B, the four types of 3D-printed module architectures are

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thin films, porous frameworks, surface patterns, and fibers. The fabrication tech-
niques and application of these different architectures are briefly listed as follows:

(1) Thin films are the most common and commercially available architectures for
electrodes, which are usually constructed by the IJP among the various 3D
printing techniques.51,81,89,90,101 3D-printed thin films can be custom-de-
signed with a wide range of shapes and sizes as compared with conventional
tape casting manufacturing techniques. They are usually assembled into 2D
stacked batteries and microbatteries.
(2) 3D porous frameworks are another common type of architecture for 3D-
printed electrodes, which can be constructed by DIW,52–57,85–88,94,96
FDM,92 and SLA printing techniques.49,121 A properly engineered porous
framework has abundant porous structures from micro-, meso-, to macro-
size pore, which is advantageous for medium (ion and gas) transport, thereby
increasing the rate capability of the electrodes. Such electrode architectures
would be useful to build different types of 3D battery configuration, such as
sandwich-type, in-plane type, and concentric tube type.
(3) By comparison, surface patterns are less common architectures for elec-
trodes, but they can act as a modification enhancement for other battery
modules, for example, the solid-state electrolyte with surface patterns.48
The structural pattern can be designed into any shape and would play an
additional functional role in the special applications, as it forms a 3D surface
modification. This will be discussed in detail in the following section.
(4) Fibers are among the common architectures and can be easily fabricated by
3D printing, which is applied to the fiber-typed battery configuration. For
example, Hu and co-workers printed the LiFePO4 and Li4Ti5O12 fibers sepa-
rately by DIW using the highly viscous inks containing CNT, active materials,
and PVDF dissolved or suspended in NMP, before weaving them together in a
cathode-anode configuration to fit into flexible electronic devices.84 In
another case, Zhang et al. designed core-sheath fiber using CNT as a conduc-
tive core and silk fibroin as a dielectric sheath via coaxial DIW.141

The configurations of 3D-printed batteries significantly affect their device perfor-

mance and their applications. In general, these 3D-printed batteries can be classi-
fied into four types of configuration designs according to the geometrical character-
istics, including the sandwich-type, in-plane type, concentric tube type, and fiber-
type (Figure 4C). The details are as follows:

(1) The sandwich-type configuration is a classic design for cost-effective mass

production, where every module is placed in a different plane and assembled
through layer-by-layer stacking.57,94 The printable batteries are designed
with customized arbitrary shapes, such as round, square, triangle, and
pentagon. However, this design is usually larger in dimension, limiting the
miniature applications.
(2) The in-plane type design is a classic 3D-printed battery configuration, where
microscale electrodes are arranged in parallel and the same plane on a sub-
strate. It can integrate the microelectrodes in a very limited footprint while the
dimension of the microelectrodes and the distance between the microelec-
trodes can be accurately controlled by the 3D printing program. This design
also serves to facilitate ion transfer due to the microscale architecture of high-
aspect-ratio electrodes. For example, the first 3D-printed Li-ion microbattery
was designed with an in-plane type and interdigitated with sub-millimeter

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scale, which exhibited among the highest areal energy and power densities
reported at that time.78
(3) The concentric tube type is a unique battery configuration, where an array of
evenly spaced and vertical electrode posts is uniformly covered by a layer of
the solid electrolyte, and the regions between the posts are filled with the counter
electrode materials. Such configuration is common and popular in 3D microbat-
teries, which are usually built up by the etched 3D electrodes, especially for the
common 3D silicon anodes. With the help of SLA printing, a concentric-tube-
type microbattery was fabricated by using the printed perforated polymer sub-
strate that was coated layer-by-layer by thin-film electrodes and polymer-in-
ceramic electrolyte via the electrophoretic deposition.137
(4) The fiber-type configuration is another unique battery configuration, where a ca-
ble-type electrode (anode) core is surrounded by a tubular outer electrode (cath-
ode), or two wire-shaped electrodes are twisted together. The fiber configuration
has been extensively studied in recent years as flexible and wearable energy stor-
age devices for the emerging smart garments and electronic textiles applica-
tions.142 For instance, all-fiber quasi-solid-state LIBs were fabricated using the
DIW technique for the first time by deliberately designing the 3D-printed fiber
cathodes and anodes that intertwine and twist together, followed by coating
the polymer gel electrolyte on the twisted electrodes.84

It should be noted that achieving mechanical robustness for 3D-printed electrodes

and batteries is largely challenging as compared with 2D-structured compact elec-
trodes and batteries. Moreover, the 3D-structured electrodes would have a large
volumetric expansion and contraction during lithiation and delithiation reactions,
leading to poor mechanical stability. Currently, adding fillers into the inks or fila-
ments is the commonly used strategy to improve the mechanical properties of elec-
trodes, such as silica,91 cellulose,78 and carbon fillers.111 Another strategy is building
a soft polymer scaffold, coated by active materials where the mechanically robust
polymer scaffold can withstand the mechanical forces.75 However, these non-active
fillers or polymer scaffolds will reduce the specific weight ratio of active materials
and thus, decrease the energy density of batteries. Indeed, further research is
needed to improve the mechanical properties of the 3D-printed electrodes while
maintaining high electrochemical performance.

Role of Printing Designs on Battery Performance

Evaluation criteria of performance based on the gravimetric, areal, or volumetric pa-
rameters are discussed first. The gravimetric performance is traditionally used as the
figure-of-merit to assess an electrode material in basic research, while the areal and
volumetric performances are key parameters for evaluating the practical potentials
for applications, especially for the 3D-printed batteries that pursue ‘‘small and
powerful’’ performance. In the published literature, the areal and volumetric param-
eters are also commonly employed to evaluate the microscale battery performance.
However, there is a lack of unified standards to benchmark the performance in pub-
lished reports. Hence, it is critical to define one parameter to make rational compar-
isons of performance, for example, selecting the volumetric performance based on
the volume of the electrode or batteries.

As shown in Figure 5 and Table 1, 3D printing of batteries offers two unique advan-
tages in general: enhancing the design freedom of batteries as well as increasing
their areal energy and power densities. As has been mentioned previously, the
currently available commercial batteries are regulated in large sizes and restricted
in the usual form factors via the conventional tape casting manufacturing process.

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Figure 5. Role of 3D Printing Designs on Battery Performance

(A) Typical examples of the enhancement of batteries’ design freedom from microscale dimensions
to customized shapes. Reprinted with permissions from Sun et al.78 Copyright 2013, Wiley-VCH;
Kim et al. 131 and Reyes et al. 111 Copyright 2018, American Chemical Society.
(B–E) Summary of improvements in areal energy density and power density of batteries. (B)
Schematic illustration of 3D-printed electrodes with increased thickness and short ion distance that
can increase the energy density and power density, respectively. (C) Effect of the thickness of
printed electrodes on the areal energy density. Reprinted with permission from Wei et al. 87
Copyright 2018, Wiley-VCH. (D) Comparison of the effects of 3D-printed and traditional cathodes
on the rate capability. Reprinted with permission from Hu et al. 94 Copyright 2016, Wiley-VCH. (E)
Ragone plots of typical 3D-printed LIBs, and the state-of-art 3D Li-ion microbatteries for
comparison. Reprinted with permissions from Um et al.143 Copyright 2018, Royal Society of
Chemistry; Sun et al. 78 Copyright 2013, Wiley-VCH; Wei et al. 87 Copyright 2018, Wiley-VCH; Hur
et al. 27 and Zheng et al. 144 Copyright 2018, Elsevier; and Pearse et al. 145 Copyright 2018, American
Chemical Society.

3D printing technology can unlock the form factor limitation and promise to print any
sizes and shapes, because of its unique advantage in geometrically complex shape
or configuration designs. Figure 5A shows that 3D printing can easily create micro-
batteries78 and design customized batteries in any desired shapes such as miniatur-
ized rectangular, cylindrical, and H shapes as well as ring-shapes131 and large-scale
bangle shape.111 These battery designs with arbitrary form factors can be widely

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Table 1. Comparison of Battery Performance Fabricated by 3D Printing, Conventional Tape

Casting, and Deposition Techniques
Manufacturing Process Design Areal Areal Volumetric Manufacturing
Freedom Energy Power Energy Cost
Density Density Density
3D printing of batteries high high high high middle
Tape casting for low low low low low
conventional batteries
Deposition techniques middle middle middle low high
for 3D microbatteries

applied in customized electronics, wearable devices, Bluetooth beacon, and smart

sensors in the future.

The electrode architectures built by 3D printing are propitious to increase their ca-
pacity and energy density and power density of batteries due to the high areal-
loading density and the large high aspect ratio of the 3D electrodes. Moreover, a se-
lective pursuit of areal energy densities or power densities can be easily achieved by
accurately designing the tailorable thickness and porosity of 3D-printed electrodes,
as schematically shown in Figure 5B. For example, Wei et al. designed a gradual in-
crease of electrode thickness from 0.05 mm (i.e., commercial LIBs) to 1 mm (Fig-
ure 5C) by controlling the numbers of printed layers.87 As a result, the printed LIBs
composed of ultrathick electrodes (1 mm) exhibited an areal energy density of up
to 20 mWh/cm2, which was much higher than that of thin electrodes (1 mWh/
cm2). Moreover, compared with the traditional 2D planar electrodes, the printed
electrode owns a 3D and high-aspect-ratio architecture, which can shorten the Li-
ion and electron transport pathways and then increase the rate capability and power
density of batteries. For instance, the printed LiMn1-xFexPO4 cathode can deliver
high capacities of 108.8 and 88 mAh/g at the rates of 50 and 100 C, respectively,
higher than those of the traditional electrodes by a coating method (Figure 5D).94
As shown in the Ragone plot (Figure 5E), the 3D-printed LIBs offer high areal energy
densities of >30 mWh/cm2 and areal power densities of >1,000 mW/cm2.78,87,143
Such performances are much better than those of the state-of-the-art 3D Li-ion mi-
crobatteries that are fabricated by other advanced techniques or methods, such as
dry etching,140 mask-assisted interdigital patterns,144 and conformal vapor-phase
chemistry.145 Apart from 3D-printed LIBs, a printed mm2-scale Zn-Ag2O battery
can operate at high current densities (1–12 mA/cm2) and achieve an extremely
high areal capacity of 11 mAh/cm.2107 In terms of volumetric performance, a
screen-printed planar Zn/MnO2 microbattery achieved a high volumetric energy
density of 17.3 mWh/cm3, outperforming lithium thin-film batteries (%10 mWh/
cm3).146 Another printed flexible dual-ion microbattery can deliver an ultrahigh volu-
metric energy density of 291 mWh/cm3 at 1 C and an ultrahigh volumetric power
density of 1,756 mW/cm3 at 5 C.147 In general, 3D printing technology is suitable
for microbatteries that often need to achieve high areal or volumetric energy and po-
wer densities in a narrow space. Moreover, the arbitrary architectures of microbat-
teries are more difficult to be fabricated by conventional tape coasting methods.
Nevertheless, 3D-printed batteries are in the research and development stage,
and manufacturing costs, throughput, product repeatability, and reproducibility
would require further optimization.

Problem-Oriented Designs
The advantages of 3D printing designs not only lie in the arbitrary battery con-
figurations and enhanced performance but also are reflected in the solutions of

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Figure 6. Typical Problem-Oriented Designs via 3D Printing

(A and B) Dealing with the problems in solid-state electrolytes that have poor ionic conductivity and mechanical properties (A) 49 and the poor
electrolyte-electrode interfacial contact (B). 48 Reprinted with permissions from Zekoll et al. 49 Copyright 2018, Royal Society of Chemistry; McOwen
et al. 48 Copyright 2018, Wiley-VCH.
(C and D) Solving the problems in Li metal anodes that have high oxidation stability (C) 148 and serious safety issues (D). 118 Reprinted with permissions
from Cho et al. 148 Copyright 2020, Wiley-VCH; Lyu et al.118 Copyright 2020, Elsevier.
(E) Handling the problem in Li-O2 batteries that have a low practical energy density. Reprinted with permission from Lyu et al. 57 Copyright 2019, Wiley-
VCH.

solving special scientific and technological problems in batteries. Herein, some

of the typical problem-oriented designs in different battery research topics are
briefly introduced, including solid-state batteries, Li-metal batteries, and redox
flow batteries, with the emphasis on how 3D printing can help mitigate some
of the outstanding issues. However, few studies have been conducted from
this perspective in general. Nonetheless, more studies that focus on utilizing
3D printing to resolve targeted problems faced by conventional manufacturing
processes are expected, rather than studies focusing on simply preparing printed
battery materials.

Solid-state batteries are among a class of promising next-generation safe batteries

without the use of organic-based flammable liquid. However, one of the greatest
challenges is the development of solid-state electrolytes that have high ionic conduc-
tivity and suitable mechanical properties. Polymer electrolytes often suffer from low
ionic conductivity, whereas the ceramic ones suffer from poor mechanical properties.
To address this problem, Bruce and co-workers reported a hybrid solid electrolyte
composed of 3D ordered bicontinuous conducting ceramic and insulating polymer
microchannels by using a 3D-printed polymer template.49 As shown in Figure 6A,
the printed template was first filled with the ceramic Li+ ion conductor LAGP and sub-
sequently sintered to form 3D-structured LAGP scaffolds with empty channels by
removing the polymer template. Finally, the LAGP scaffolds were filled with non-con-
ducting polypropylene or epoxy polymer to obtain the structured hybrid electrolytes.

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The ceramic channels provided continuous pathways to maintain high ionic conduc-
tivity, while the polymer channels permitted improvement of mechanical properties
to mitigate the ceramic brittleness. Moreover, the ceramic to polymer ratio and the
microarchitecture (such as cubic, gyroidal, diamond, and spinodal structures) can
be precisely controlled by modifying the printed template. The optimized hybrid
electrolytes with gyroid microarchitecture were demonstrated to have superior me-
chanical properties and high ionic conductivity of 1.6 3 104 S/cm at room temper-
ature, addressing the poor ionic conductivity and mechanical property of the solid-
state electrolytes. 3D printing addressed this issue by providing a sacrificial template
that cannot be easily fabricated via conventional processing techniques, enabling the
creation of this unique hybrid architecture. Another challenge faced by solid-state
batteries is the high cell resistance caused by poor electrolyte-electrode interfacial
contact. To solve this, Wachsman and co-workers prepared a ceramic Li7La3Zr2O12
solid electrolyte with a variety of surface-patterned microstructures (including line,
grid, and column patterns) by extrusion-based 3D printing, as schematically shown
in Figure 6B.48 The pattern structure thus can significantly enhance the interfacial
contact area, dramatically lowering the full cell resistance and increasing the energy
and power densities. The 3D patterned architecture is once again customizable and
can be optimized to obtain good adherence to the electrode, which is beyond the
capabilities of conventional processing methods.

As aforementioned, Li metal is the anode of choice for the next-generation batteries.

However, the practical applications are plagued by its high oxidation stability and
the serious safety issue due to the uncontrollable Li dendrite growth. Very recently,
Lee and co-workers developed an antioxidative Li anode by solvent-free, UV poly-
merization-assisted printing of a new class of solid electrolyte interphase mimic
(pSEI) on the Li surfaces (Figure 6C).148 The thus-designed pSEI comprised organic
and inorganic components, where the organic mimic acted as a moisture-repellent
structural framework and the inorganic mimic allowed facile Li+ transport. Owing to
the chemical and architectural features of pSEI, the Li metal anode showed excellent
antioxidation stability and a reliable full cell performance after exposure to humid
environments (inset in Figure 6C). The fast in situ nature of the UV polymerization
during the printing process effectively prevented the Li anode itself from oxidizing
and was therefore proven to be more efficient than conventional methods to pro-
duce an additional SEI layer for Li anodes. Lyu et al. developed a safe Li anode
with high areal capacity and high-rate capability by employing a novel N-doped car-
bon framework made by extrusion-based 3D printing of zinc-based MOF precursor
(Figure 6D).118 The framework possessed a hierarchically porous structure and a
large specific surface area, which simultaneously suppressed Li dendrite growth,
accommodated massive Li deposition, stabilized Li/electrolyte interface, and dissi-
pated high current densities. As a result, the 3D-printed anode delivered an ultra-
high areal capacity of 30 mAh/cm2 at a high rate of 10 mA/cm2. Lyu et al. also fabri-
cated a self-standing and hierarchically porous carbon framework embedded with
Co nanoparticles by extrusion-based 3D printing of cobalt-based MOF precursor,
as schematically shown in Figure 6E.57 As cathodes of aprotic Li-O2 batteries, the de-
signed framework with the unique structural features well addressed the key bottle-
neck problem, i.e., the much lower practically achievable specific energy density
compared to the high theoretical energy density. Specifically, (1) the self-standing
framework possesses good conductivity and necessary mechanical stability so that
it can act as a porous conducting matrix; and (2) the framework with abundant
micron-sized pores favors the efficient accumulation of Li2O2 particles to prevent
surface passivation and facilitates their decomposition due to the confinement of
insulating Li2O2 within the pores and the presence of Co-based catalysis. Therefore,

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this self-standing porous catalyst architecture significantly enhances the cell’s spe-
cific energy, achieving a high value of 798 Wh/kg. In both cases, the unique self-
standing architectures can be produced by extrusion-based 3D printing and the
component of the framework can be adjusted by choosing different MOF precur-
sors, whereas conventional techniques will be too cumbersome and mechanically
frail and would not be able to achieve the targeted electrochemical performance.

In another typical example, Poulikakos and co-workers designed interdigitated,

tapered microfluidic networks in miniaturized redox flow cells (RFCs), made of 3D-
printed polymers and subsequently sputtered with Ni/C, and micro-engineered spe-
cifically tailored fluidic networks.149 These designed fluidic networks followed an
interdigitated layout of tapered microchannels, which ensured to guide the electro-
lytes in multiple-passes effectively through the porous electrode while balancing the
pressure drops to maximize net power densities. The optimized RFCs were demon-
strated to achieve a maximum power density of up to 1.4 W/cm2 and a net power
density of up to 0.99 W/cm2 at room temperature. This study shows that rational
tailoring of fluidic networks in RFCs is key for the development of devices by effec-
tively combining power delivery and thermal management, with tailoring efficiently
achieved through 3D printing. In addition, Yang and co-workers achieved safer LIBs
by depositing CNT-wrapped thermoresponsive polyethylene microspheres on the
electrodes via FDM, which can form an insulating PE film to prevent ionic flow at
high temperatures, thereby rapidly causing a shutdown in the LIBs.150 Most impor-
tantly, FDM enables the precise deposition of a minimal amount of CNT-coated PE
microspheres onto electrodes, which simultaneously perform the function as a bat-
tery shutdown additive.

CONCLUSION AND PERSPECTIVE

3D printing of advanced batteries has drawn considerable attention as an innovative
technology that can disruptively change the design and architecture at all levels of
materials, modules, and devices. In this review, we examined the recent progress
in 3D-printed batteries from the angles of printing techniques, printable materials,
and design considerations at both modules and full cell device levels, aiming at
providing readers with a comprehensive understanding of the 3D-printed batteries
and their great application potentials. The rapid development over the past several
years has witnessed a set of technological advances in optimizing a suitable printing
technique for a targeted 3D battery product, tuning at achieving printable materials,
battery modules of both electrodes and electrolytes, the architectures and configu-
rations at full cell levels. Together with these technological advancements, there
have been pursuits for in-depth understanding of the governing principles involved
in 3D printable materials, components, and printing techniques and the resultant
battery performance. There is no doubt that such pursuits will continue in the coming
years. Next, we present the four points of development directions and outlook along
the manufacturing route of 3D-printed batteries (Figure 7).

First, in terms of printable materials, among the most successful printable battery
materials so far are the cathodes and anodes of LIBs. To achieve an even higher en-
ergy density for 3D-printed batteries, there shall be novel active materials devel-
oped for these battery systems, which will be made and printable, including those
for Li metal anode, sulfur cathodes, and Zn metal anode for Li-S and Zn-air batteries.
Low cost and effective ink-preparation (for DIW, IJP, and SLA) or filament-fabrication
(for FDM) method should be developed with these new functional materials, which
would ultimately be essential for eventual applications at a commercial scale.

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Figure 7. Perspectives on Future Developments and Remaining Challenges in 3D-Printed

Batteries

Ideally, direct printing of active materials without the use of any polymeric binders or
thermoplastic polymer additives would be preferred, as they would inevitably hinder
electrochemical performance. In ink or filament fabrication, there would be different
demands for the characteristics of active material powders, such as density, particle
size, hydrophilicity, miscibility, and surface chemistry. Large-scale production of
high-quality material powders with desired properties at low cost is fundamental
to achieve printed batteries. In addition, most of the known printed electrodes
tend to have poor mechanical robustness, which could crack during the subsequent
assembly of the batteries. Hence, further research would be needed to enhance the
mechanical properties of 3D-printed electrodes while maintaining high electro-
chemical performance, for instance, by optimizing the printing techniques and
active materials to obtain alignment structure, or by re-evaluating both post-printing
treatment processes and starting materials, such as additional thermal sintering or
adding appropriate reinforcing additives.

Second, among the printing technologies, DIW is the most used while the printing
resolution is usually lower, at only dozens or hundreds of microns. To make the
printed batteries more compact and refined in feature sizes, developing printing
techniques with high resolution of minimum feature size down to 1 mm would there-
fore be necessary. Although DIW printing with micro-capillary nozzles can achieve a
high resolution, the fabrication of a compatible printable ink with the desired yield
stress behavior along with the active materials is a prerequisite, requiring it to not
clog the fine nozzles. Besides DIW, other newly emerging 3D printing technologies
should be further explored for battery module manufacturing, such as rapid and
continuous SLA,151 aerosol jet printing (AJP),152 electrohydrodynamic (EHD) print-
ing, and even nanoimprinting. Thus, a complete 3D-printed battery library based
on conformal printing techniques can be built, providing key directions and data-
bases to optimize performance, reduce cost, and apply batch and customized pro-
duction. In addition, avoiding or optimizing the post-treatment processes is
required for the scalability, reproducibility, and repeatability of printed modules
and batteries in practical manufacturing. In addition, new 4D printing technology
will be emerging, which will allow a 3D-printed structure to change its architecture
or function with time in response to an external stimulus such as temperature, mag-
netic, light, and water.153–156 With the help of the architecture or functional change,
the printed battery performance could be further enhanced, battery failure could be
further reduced, or smart battery configuration could be built.

Third, in terms of printing designs, more rational designs in the electrode architec-
tures and battery configurations are necessary in order to further improve the battery
performance, as well as for customized design and production. This would require

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guidance from the market demands. Unique features of 3D printing designs would
help solve specific applications and technological problems in both the existing and
newly emerging fields of electronics and consumer products. In addition, they can
be extended to other environments and even water technologies.157–160 There is
no doubt that more problem-oriented solutions are needed, rather than the simple
preparation of printed materials.

Fourth, there are still considerable challenges in several printed battery types to be
addressed at the current stage. For example, there are few studies on the fully
printed batteries, integrated with printed current collector and packaging materials,
and thus more relevant research shall be needed. Monolithic-integrated batteries
with electronic devices (e.g., circuit board) shall be further developed, which can
widen the advantage of 3D printing as an efficient and versatile platform technology
far beyond than that of conventional batteries. However, mass production still poses
a great challenge for commercialization at this stage, which requires efficient 3D
printing to increase production rates and ensure product quality and consistency,
but at low production costs.

3D-printed batteries will be further explored for multifunctional applications, such as

wearables, miniaturized micro-robots, implantable medical devices, or even micro-elec-
tronic storage devices with unique designs. With further optimization in manufacturing
costs, throughput, product repeatability, and reproducibility, 3D printing of batteries
can be used on a large scale for electric cars and smart grid applications. One would envi-
sion that the demand for ultrahigh performance and customized batteries due to both
niche and a wide spectrum of applications will lead to a rapid rise in the development
of 3D-printed batteries and eventually a promising market for them.

ACKNOWLEDGMENTS
Z.L. and Y.C. gratefully acknowledge the financial support from the National Key
Research and Development Program of China, China (grant no. 2018YFB1105400),
the Natural Science Foundation of Jiangsu Province, China (grant no. BK20200375),
and the Fundamental Research Funds for the Central Universities, China (grant no.
2242020K40220). W.C. acknowledges the support from the Singapore MOE grant of
MOE2017-T2-2-052. J.W. acknowledges the support of Singapore MOE (Tier 1, R284-
000-193-114) for research conducted at the National University of Singapore. Y.L. and
Y.M. acknowledge the support from Keypoint Research and Invention Program of
Jiangsu Province, China (BE2018010-3). The authors would like to thank Professor X. Re-
nshaw Wang from the Nanyang Technological University for valuable discussions.

AUTHOR CONTRIBUTIONS
Z.L. and Y.C. conceived and supervised the project. Z.L. conducted the literature
search and wrote the manuscript. G.J.H.L. and J.J.K. assisted in the literature review
and revised the manuscript. Y.L., Y.M., J.D., Jinlan Wang, Z.H., John Wang, and
W.C. provided input for discussions and participated in the writing of the
manuscript.

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