Adfm 201906244

Review
www.afm-journal.de
Additive Manufacturing of Batteries

Yaokun Pang, Yunteng Cao, Yihang Chu, Minghong Liu, Kent Snyder, Devin MacKenzie,
and Changyong Cao*
cost-effective energy storage devices to

Additive manufacturing, i.e., 3D printing, is being increasingly utilized to build power-independent electronics
fabricate a variety of complex-shaped electronics and energy devices (e.g., systems.[1] Batteries, as one of the most
batteries, supercapacitors, and solar cells) due to its excellent process flex- important and widely used electrical
ibility, good geometry controllability, as well as cost and material waste reduc- energy devices, have attracted signifi-
cant attention and have been extensively
tion. In this review, the recent advances in 3D printing of emerging batteries
studied due to their ability to stably store
are emphasized and discussed. The recent progress in fabricating 3D-printed and source electrical energy as well as
batteries through the major 3D-printing methods, including lithography- their availability for a wide range of forms,
based 3D printing, template-assisted electrodeposition-based 3D printing, capacities, and power densities.[2,3] For
inkjet printing, direct ink writing, fused deposition modeling, and aerosol jet instance, lithium-ion (Li-ion) batteries
printing, are first summarized. Then, the significant achievements made in in large form factors exhibit high energy
density, low self-discharging rate, and
the development and printing of battery electrodes and electrolytes are high-
high current charge/discharge cycling
lighted. Finally, major challenges are discussed and potential research fron- capability.[2,4] Over the years, much effort
tiers in developing 3D-printed batteries are proposed. It is expected that with has been put into exploring new elec-
the continuous development of printing techniques and materials, 3D-printed trode materials, electrolytes, cell struc-
batteries with long-term durability, favorable safety as well as high energy and tures, and novel fabrication approaches
so as to improve the electrochemical per-
power density will eventually be widely used in many fields.
formance of batteries, to reduce the cost,
and to expand their application. Currently,
most electrode materials have relatively low electronic conduc-
1. Introduction
tivity and slow diffusion speeds of lithium ions, resulting in
Given the rapid development and extensive use of mobile low charge/discharge rate and power density of batteries. In
electronics, there is an increasing demand for reliable and addition, the high cost of Li-ion batteries is also a concern; for
example, Li-ion batteries based on nickel and cobalt oxides are
Dr. Y. Pang, Y. Cao, Y. Chu, Prof. C. Cao quite expensive. Due to their advantages of low cost but high
Laboratory for Soft Machines & Electronics energy, lithium–air (Li–air)[5] and lithium–sulfur (Li–S) bat-
School of Packaging teries[6] have been extensively studied to develop new lithium-
Michigan State University
East Lansing, MI 48824, USA based batteries. In addition, new rechargeable battery systems
E-mail: [email protected] based on abundant resources, such as zinc-,[7,8] calcium-,[9] alu-
Dr. M. Liu, K. Snyder minum-,[10] and sodium-based batteries,[11] are being explored
Ford Energy Storage Research Group and have captured increasing attention.
Ford Motor Company To generate high capacity, traditional 2D-structured bat-
Dearborn, MI 48121, USA
teries require a large footprint area, which hampers their inte-
Prof. D. MacKenzie
Departments of Mechanical Engineering and Materials
gration into portable microelectronics. Another method for
Science and Engineering enhancing the energy density and areal capacitance is to fab-
University of Washington ricate thicker electrodes that can significantly raise the active
Seattle, WA 98105, USA material loading while preserving rapid ion diffusion.[12] With
Prof. D. MacKenzie increasing electrode thickness, however, the electron transport
Washington Clean Energy Testbeds distances and overall electrical impedance of the electrode will
Clean Energy Institute
Seattle, WA 98105, USA inevitably increase, resulting in reductions of power density
Prof. C. Cao and rate capability.[12,13] Compared with conventional 2D planar
Departments of Mechanical Engineering, structures, 3D structures can yield shorter diffusion pathways
Electrical and Computer Engineering and lower resistance during the ion-transport process, as well
Michigan State University as providing increased energy density by creating porous struc-
East Lansing, MI 48824, USA
tures with larger surface areas that can improve electrode reac-
The ORCID identification number(s) for the author(s) of this article tion and ion transfer while efficiently using the limited space
can be found under https://doi.org/10.1002/adfm.201906244.
in a compact battery.[12,13] To date, several methods such as
DOI: 10.1002/adfm.201906244 templating and chemical activation[14] have been developed to
Adv. Funct. Mater. 2019, 1906244 1906244 (1 of 22) © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.afm-journal.de
control electrode microstructure and device assembly, but little

work has been done to design, optimize, and fabricate micro- Yaokun Pang received his
devices possessing engineered porous architectures. Thus, B.S. (2013) in polymer
the manufacturing of devices possessing complex hierarchical materials and engineering
nanoarchitectures via a scalable and controllable method from Qingdao University and
remains a significant challenge.[12] Ph.D. (2018) in condensed
As an advanced fabrication technique, 3D printing, i.e., matter physics from Beijing
additive manufacturing (AM), has been increasingly utilized Institute of Nanoenergy
to fabricate complex 3D objects via digitally controlled deposi- and Nanosystems, Chinese
tion of phase change and reactive materials and solvent-based Academy of Sciences. He is
inks.[15,16] It generally begins with the design of a 3D virtual now a postdoctoral fellow
model that is sliced into several 2D horizontal cross sections in the Laboratory for Soft
using special software. By successively printing new 2D layers Machines and Electronics
on top of previous layers, a coherent 3D object can be finally under the supervision of Professor Changyong Cao at
fabricated.[17,18] A few major types of 3D printing technologies Michigan State University, MI, USA. His research interests
have been invented and widely utilized: 1) material extrusion, are triboelectric nanogenerator, tribotronics, flexible elec-
2) powder bed fusion, 3) vat photopolymerization, 4) material tronic, self-powered sensors, and printed electronics.
jetting, 5) binder jetting, 6) sheet lamination, and 7) directed
energy deposition.[13] 3D printing has demonstrated superior Devin MacKenzie is the
advantages in the rapid prototyping of complex structures and Washington Research
devices with high control accuracy. This has significantly sim- Foundation Professor
plified the fabrication process and reduced the design period of Clean Energy and an
to avoid the troublesome trial-and-error process.[15,19,20] Due Associate Professor of
to the unique advantages, it has been extensively applied in Materials Science and
many fields such as food,[21] medical,[22] electronics,[23] and Engineering and Mechanical
aerospace.[24] In recent years, 3D printing has also been uti- Engineering at the University
lized to manufacture energy devices such as batteries and of Washington. He obtained
supercapacitors for specific applications in laboratories.[17,19,25] his B.S. degree in materials
Compared with conventional battery fabrication technologies, science and engineering from
3D printing has several significant advantages: 1) enabling MIT and his master’s and
the fabrication of desired complex architectures; 2) precise PhD degrees in the same discipline from the University
controlling of the shape and thickness of the electrodes; of Florida. He worked as a postdoc in the Department of
3) printing solid-state electrolyte with high structure stability Physics at the University of Cambridge. Devin’s work is
and safer operation; 4) potential for low-cost, environmental centered around the development of new materials, device
friendliness, and ease of operation; and 5) possibility of elimi- structures and integrated processes that enable highly
nating the steps of device assembly and packaging via direct efficient roll-to-roll (R2R) processing of devices for energy
integration of batteries and other electronics.[17] 3D printing storage, sensing, and integrated medical systems.
is able to fabricate novel 3D-architectured electrodes with
larger surface area and higher areal-loading density, providing Changyong Cao is currently
shorter diffusion pathways and smaller resistance during the an Assistant Professor in
ion-transport process so as to improve battery energy density the School of Packaging,
and power density. Additionally, 3D printing can dramati- Departments of Mechanical
cally reduce material waste and may enable potential time Engineering and Electrical &
saving due to the less complex fabrication procedures. Overall, Computer Engineering (by
3D printing opens new avenues for the rapid fabrication of courtesy) at Michigan State
3D-structured batteries with complex architectures and high University (MSU), where he
performance. is directing the Laboratory
Due to the advantages mentioned above, a large amount of for Soft Machines and
research has been dedicated to this field and multiple reviews Electronics. He received his
on 3D-printed energy storage devices have been published, Ph.D. degree in mechanical
with a focus on the development of electrode materials and a engineering and materials science from the Australian
very limited discussion on 3D-printed techniques and elec- National University in 2014, and then worked as a postdoc-
trolyte.[12,13,17,25] Up to now, there lacks a thorough review on toral research associate at Duke University. His research
summarizing all available 3D-printed techniques for battery
interests include the mechanics and physics of soft mate-
manufacturing. More importantly, much of the latest progress rials, soft robotics, smart materials and structure, printed
and many breakthroughs for 3D-printed batteries have not been electronics, flexible/stretchable electronics, smart pack-
discussed in previous reviews. Thus, we provide a comprehen- aging system as well as the 3D/4D printing of advanced
sive review of the latest advances and progress in the manu- functional materials.
facturing and materials development for 3D-printed batteries
However, considering the compatibility among the preparation

conditions, materials, and processes, not all of the 3D printing
technologies and current materials used in conventional bat-
teries are appropriate for manufacturing printed batteries. A
qualitative comparison of different 3D printing techniques for
printed batteries is shown in Table 2. There are many chal-
lenging issues that have to be addressed in the manufacturing
of 3D-printed batteries. In this section, we summarize the
major 3D-printed batteries that have been demonstrated via
advanced 3D printing technologies in recent years.
2.1. Lithography-Based Printing
Holographic lithography (HL) is based on the multibeam

interference phenomenon without using complex photomasks
or optical systems.[26] It is a simple and low-cost technique
to fabricate 1D, 2D, and 3D periodic geometries via a single
laser exposure. Ning and co-workers used the combination of
HL and conventional photolithography to fabricate high-per-
formance Li-ion batteries (Figure 2a).[27] In their experiments,
a SU-8 3D lattice was fabricated on the surface of indium–tin
oxide (ITO)-coated glass via several interfering laser beams
Figure 1. Outline illustration of the review for printed batteries: 3D
printing technologies, printed electrode materials, and electrolyte mate-
arranged in an umbrella geometry. Then, another photore-
rials. The major 3D printing techniques for manufacturing batteries sist (AZ9260) was infiltrated into the SU-8 lattice and formed
include lithography-based 3D printing, template-assisted electrodepo- solid straight walls after solidification within the 3D lattice
sition (TAE)-based 3D printing, inkjet printing (IJP), direct ink writing (Figure 2b). Next, Ni was partially electrodeposited onto the
(DIW), fused deposition modeling (FDM), and aerosol jet printing (AJP). porous SU-8 lattice, followed by the removal of the photoresist
Printed electrode materials include graphene, carbon nanotube, carbon template by oxygen reactive ion etching. The final current col-
nanofiber, and LTO/LFP, and electrolyte materials include Li7La3Zr2O12,
lectors composed of an interdigitated 3D porous Ni scaffold
N-Propyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide
(Pyr13TFSI)/lithium bis(trifluoromethanesulfonyl)imide(LiTFSI) salt, and were obtained (Figure 2c) for further electroplating active mate-
gel composite electrolyte. rials, MnO2 (≈100 nm thick) and Ni–Sn (90% tin, ≈70 nm thick)
as cathode and anode, respectively (Figure 2d). The resultant
(Figure 1). The content of the review is organized as follows: cell showed impressive power and energy densities up to
In Section 2, we discuss the 3D-printed batteries via different 3600 µW cm−2 µm−1 and 6.5 µWh cm−2 µm−1. It was demon-
kinds of printing techniques, including lithography-based 3D strated that at least 80% of the initial capacity of the cell was
printing, template-assisted electrodeposition (TAE)-based 3D retained after 100 cycles at various rates and that the cell could
printing, inkjet printing (IJP), direct ink writing (DIW), fused drive a light-emitting diode (LED) over 200 charge/discharge
deposition modeling (FDM), and aerosol jet printing (AJP). The cycles with only 12% capacity loss.
working principles, printing process, advantages, and limita- As a novel 3D fabrication technology, projection micro-stere-
tions for each method are then discussed. Afterward, we high- olithography (PµSL) has been developed to fabricate high-reso-
light the printing materials for electrodes and electrolytes of the lution 3D polymer structures and devices.[28] In PµSL, a digital
printed batteries in Sections 3 and 4, respectively. Finally, con- microdisplay technology is used as a dynamic mask generator
clusions and future opportunities for 3D printing of batteries to produce a virtual photomask, and a focused ultraviolet (UV)
are discussed in Section 5. light spot scans over the surface of photocurable resin. Chen
et al. utilized the PµSL technology to directly print a 3D micro-
battery.[29] As shown in Figure 2e, a microstructured UV-curable
2. Major Printing Methods for 3D-Printed poly(ethylene glycol) (PEG)-based gel polymer electrolyte (GPE)
was fabricated, which contained two parts: the trench used to
Batteries
contain current collectors and electrode materials, and the center
As an innovative manufacturing approach, 3D printing tech- membrane with a zigzag shape acting as the gel electrolyte of
nologies are able to facilitate the fabrication of batteries, enable the battery. In photopolymerization, there are self-assembled
versatile and miniature batteries ranging from microscale to sub-micrometer scale channels formed on the surface of the
macroscale, and improve the electrochemical performance of GPE membrane (Figure 2f). Similar to the porous structures in
batteries.[13] Table 1 presents the representative printed bat- conventional battery separators, the improvement of ion trans-
teries by various methods and materials. The geometry (e.g., port brought by the sub-micrometer scale channels can further
porosity, dimensioning, and morphology) and the structure reduce interfacial scattering.[29] Thanks to the large ionic con-
of electrodes and electrolytes of printed batteries can be accu- ductivity of GPE, the microbattery showed a charge and a dis-
rately controlled by greatly simplified and low-cost processes. charge plateau around 3.4 and 3.5 V (Li/Li+), respectively, which
Table 1. Summary and comparison of the 3D-printed batteries with various kinds of methods and materials.
Printing method Anode/Cathode Electrolyte Specific capacity Ref.

Lithography-based 3D printing (NiSn/LMO) 0.06 m NiCl2, 0.2 m SnCl2, 1 m K4P2O7, 0.04 m ≈2.9 µAh cm−2 µm−1 at 1 C [27]
potassium sodium tartrate, 0.04 m glycine
LiTiO2/LFP LAGP LiTFSI-PYR14TFSI 500 mAh cm−2 at 0.1 C [31]
−2
LTO/LFP Poly(ethylene glycol) gel polymer 1.4 µAh cm at 2 C [29]
Template-assisted NiSn/LMO 1 m LiClO4 – [35]
electrodeposition
(Pt Foil)/NiOOH 1 m LiClO4 286 mAh g−1 at 385 C [34]
Inkjet printing (Li Foil)/LiMn0.21Fe0.79PO4@C 1 m LiPF6 150.21 mAh g−1 at 10 C [45]
(Li Foil)/LFP Composite (CSP, 1 m LiPF6, 0.5 M LiTFSI 150 mAh g−1 at 1 C [40]
TX100, poly-acrylic-co-maleic acid,
carboxymethyl cellulose)
(Hybrid MoS2–graphene aerogel)/(Na 1 m NaClO4 429 mAh g−1 at 3.3 C [44]
disk)
SnO2/Li 1 m LiPF6 812.7 mAh g−1 at 1 C [39]
(Li foil)/LFP 1 m LiPF6 134.7 mAh g−1 at 0.1 C [41]
(Li foil)/MWCNT – 1260 mAh g−1 at 0.5 C [76]
Ag/Ag 10 m KOH/ZnO – [96]
(Li foil)/LiCoO2 1 m LiPF6 105 mAh g−1 at 394 µA cm−2 [42]
(Li foil)/Li–S/S@SWNT 1 m LiCF3SO3 ≈850 mAh g−1 at 0.5 C [77]
(Si NPs/PEDOT:PSS)/Li Foil 1 m LiPF6 2500 mAh g−1 at 0.1 C [43]
(Li foil)/Li1.2+xMn0.54Ni0.13Co0.13O2 TC-E918 (Tinci) >250 mAh g−1 at 0.1 C [97]
Li4Ti5O12/LFP Ion-gel solid 60 mAh g−1 at 0.1 C [89]
Aerosol jet printing (Li foil)/LFP LiPF6 151 mAh g−1 at 0.067 C [98]
Direct ink writing (Na3V2(PO4)3 graphene oxide)/ 1 m NaClO4, ethylene carbonate (EC)/ 1.26 mAh cm−2 at 0.2 C [38]
(Na3V2(PO4)3 graphene oxide) propylene carbonate (PC)
(CNF/Li)/(CNF/LFP) 1 m LiTFSI, 1,2-dimethoxymethane (DME)/ 140 mA h g−1 at 0.2 C [82]
1, 3-dioxolane (DOL)
LTO/LFP 1 m LiTFSI/PC 133 mAh g−1 at 0.2 mA cm−2 [46]
LTO/LFP 1 m LiClO4, EC/DMC 1.5 mAh cm−2 at 5 C [47]
(Li foil)/(S/GO/DIB) 1 m LiTFSI, DOL/DMC 812.8 mAh g−1 [70]
(Li Foil)/(Ni/rGO) – 1000 mA h g−1 at 100 mA g−1 [99]
LTO/LFP 1 m LiPF6, EC/DEC 10 mAh g−1 at 50 mA g−1 [48]
Li/Li Li7La3Zr2O12 – [94]
(LTO/CNF/PVDF)/(LFP/CNF/PVDF) Al2O3, PVDF, NMP/glycerol 154 mAh g−1 at 0.2 C [93]
(LTO/CNF/PVDF)/(LFP/LiCoO2) 1 m LiPF6, EC/PC 150 mAh g−1 at 0.2 C [85]
Zn/MnO2 PVDF–HFP, 1-butyl-3-methylimidazolium 0.98 mAh cm−2 [100]
trifluoromethanesulfonat (BMIM+Tf−)
(Li foil)/MnO2 PVDF-co-HFP/Pyr13TFSI/LiTFSI/TiO2 127.3 mAh g−1 [49]
(Li foil)/hGO – 13.3 mAh cm−2 at 0.1 mA cm−2 [71]
(LTO/GO)/(LTO/GO) 1 m LiPF6, EC/PC 185 mAh g−1 at 10 mA g−1 [69]
(Li foil)/(S/BP2000) 1 m LiTFSI, DOL/DME 1009 mAh g−1 at 5.5 mg cm−2 [78]
(LFP/AB/CNT)/(LFP/AB/CNT) LiPF6, EC/DMC/DEC 150 mAh g−1 at 0.1 C [79]
LTO/LFP LiPF6, EC/ethylmethyl carbonate (EMC)/ 128 mAh g−1 at 0.2 C [50]
DEC/vinylene carbonate (VC)
(Li foil)/(NC-Co) 0.5 m LiClO4/dimethyl sulfoxide (DMSO) 525 mAh g−1 at 0.8 mA cm−2 [51]
Zn/(carbon black/MnCo2O4/rGO/CNT) polyvinyl alcohol/[BMIM]OH 142.8 Ah L−1 at 0.1 mA cm−2 [7]
Fused deposition modeling (Graphene/PLA)/Li foil 1 m LiPF6 40 mAh g−1 at 120 C [101]
Graphene/Pt 1 m LiCl 248 mAh g−1 at 40 mA g−1 [102]
(Graphite/PLA)/Li 1 m LiPF6 215 mAh g−1 at 18.6 mA g−1 [58]
(Lithium titanate, graphene nano- 1 m LiClO4 7.48 mAh cm−3 at 1 C [59]
platelets)/(lithium manganese oxide/
MWNTs)
(LTO/carbon/polyester polylactic acid)/ 1 m LiPF6 80 mAh g−1 at 2 C [87]
(LFP/graphite/functionalized MWNTs/
C65/polyester polylactic acid)
Table 2. Comparison of different 3D printing techniques for batteries.
3D printing method Available materials Printing Advantage Disadvantage

resolution
FDM Thermoplastic 50–200 µm User-friendly, low cost, high speed, large size Limited resolution on the z-axis, weak
capabilities and lack of necessity for chemical mechanical properties, high viscosity of
post-processing the molten materials, and low surface
quality
DIW Plastic, metal, ceramic, and 1 µm Affordable cost, easy operation, large material Weak mechanical properties, high
food diversity, and no mask requirement requirement of ink.
TAE Polymers, metals, oxides, and 50 nm to Highly ordered macroporous structure, low Weak mechanical properties and strong
hydroxides 10 µm cost, high efficiency, simplicity, versatility, and limitation in materials
controllability
IJP Sol–gel, metal, conductive 20 µm Low cost, multimaterial printing capability, Low printing speed, not good for high-
polymers, and carbon-based able to print large areas volume printing, and print head is less
and protein materials durable
AJP Nanoparticles, nanowires, 10 µm High-resolution, high efficiency, compactable Overspray, printing quality is not stable,
CNTs, 2D materials, dielectric with inks in different viscosities. high-cost of equipment
materials
SLA Photopolymers 0.25–10 µm High resolution, high surface finish, and high Strong limitation in multimaterial
efficiency deposition
were close to the theoretical plateau values for LiFePO4 (LFP).[29] In conclusion, the aforementioned lithography-based
Despite the many advantages of PµSL, the 3D microbattery printing techniques utilize photocurable materials, and 3D
manufactured via this method exhibited poor cycle performance structures are built after a polymerization process via the appli-
and low capacity, which should be improved in the future. cation of visible light and UV light. These technologies have
Stereolithography (SLA) is another promising 3D printing been widely utilized to print complex 3D structures with high
technique that is suitable for manufacturing porous 3D bat- resolution and surface finish. However, some of them require
tery electrodes due to its high spatial resolution.[30] In the the use of masks, which will increase the production cost.
SLA system, the photosensitized monomer resin or photo-
sensitized monomer solution (mainly acrylic or epoxy based)
is selectively converted into a solidified polymer via the appli- 2.2. Template-Assisted Electrodeposition
cation of visible light and UV light. A 3D structure is built
layer by layer according to predesigned CAD patterns, and a Highly ordered macroporous materials have swiftly become
postprocess treatment such as heat treating or photocuring competitive candidates for electrode fabrication owing to their
has to be done for solidifying the remnant monomers within large specific surface areas. The TAE technique exists as the
the structure. Recently, Cohen et al. employed SLA to prepare most typical approach in the synthesis of macroporous mate-
perforated spherical, cylindrical, and cubic polymer substrates rials with tunable pore sizes and structures.[32] It is low cost,
with high surface area (Figure 2g).[31] By integrating these versatile, and convenient to control the shape and size of the
substrates with a simple and cost-effective electrophoretic- structure by just changing the electrodeposition parameters
deposition (EPD) method, a trilayered structure consisting and choosing templates with different characteristics.[33]
of LiTiO2-based anode, polyethylene oxide (PEO)–LiAlO2 or The Braun group first fabricated high-performance batteries
Li1.5Al0.5Ge1.5P3O12 (LAGP)-polyethylenimine (PEI) mem- using a TAE technique.[34] They designed a self-assembled 3D
brane, and LiFePO4 cathode was developed on the surface of bicontinuous bulk cathode, which consisted of conductive
graphene-filled conducting substrates (Figure 2h). The 3D LFP pathways for ion and electron transport by sandwiching an elec-
cell with perforated polymer substrate can undergo cycling trolytically active material (Figure 3a). Compared with conven-
with different C-rates to yield a decent areal discharge capacity tional electrodes, the designed bicontinuous electrodes showed
of 400–500 µAh cm−2 (Figure 2i), which can be additionally superior advantages in four aspects: i) fast ion transport ena-
improved by raising the thickness and surface area gain of bled by an interconnected electrolyte-filled pore network in
the cathode and substrate, respectively.[31] Additionally, these these electrodes, ii) minimal effect of sluggish solid-state ion
3D microbatteries showed great electrochemical performance, transport due to a short ion diffusion distance, iii) high elec-
comparable with that of microbatteries from perforated silicon trode surface area, and iv) excellent electron conductivity in the
chips. Under the same power capability per battery footprint, electrode assembly (Figure 3b).[34] In the fabrication process,
the areal energy densities of the 3D microbattery on the per- self-assembled opal templates were prepared by deposition of
forated silicon chip and printed perforated polymer substrate polystyrene (PS) spheres (Figure 3c) and a thin layer of Ni was
was, respectively, ten and three times that of the commercially then electrodeposited through the void space of the opal tem-
available thin-film battery (Figure 2j), in accordance with the plate. The electrolytically active materials were finally deposited
geometrical area gain.[31] onto the highly porous nickel scaffold (Figure 3d). The obtained
Figure 2. Lithography-based printing of 3D-printed batteries. a) Schematic illustration of the printing fabrication process for a 3D microbattery. b) SEM
image of the cross section of a fabricated AZ9260 structure. c) SEM image of the cross section of a nickel scaffold. Inset: Optical image (right) and
microscopic image (left) of the interdigitated nickel current collector. d) SEM image of the 3D microbattery. Inset: Enlarged view of LMO cathode (left)
and Ni–Sn anode (right). Reproduced with permission.[27] Copyright 2014, National Academy of Sciences. e) Schematic of the 3D structure for GPE.
f) SEM image of PEG membrane with self-assembled sub-micrometer scale channels. Reproduced with permission.[29] Copyright 2018, Elsevier.
g) Optical images of 3D-printed perforated spherical, cylindrical, and cubic substrates. h) Energy disperse spectroscopy (EDS) image of the cross sec-
tion of LFP-LAGP:PEI-LTO. i) Discharge voltage profiles of 3D-LFP cell at different C-rates. j) Ragone plot comparing electrochemical performance of
three kinds of batteries. Reproduced with permission.[31] Copyright 2017, Electrochemical Society.
battery possessed ultrahigh charge/discharge rate capability Following this pioneering work, the same group further
with minimal capacity loss, such that the rates for nickel-metal reported a high-power Li-ion microbattery made of interdigitated
hydride chemistries and Li ion could reach up to 1000 and 3D bicontinuous nanoporous electrodes (Figure 3f).[35] In
400 C, respectively, and it could be charged to 75% after 60 s or this microbattery, a thin coating of lithiated manganese oxide
90% after 120 s (Figure 3e). (LMO) or nickel–tin was applied upon interdigitated highly
Figure 3. Template-assisted electrodeposition of printed batteries. a) Schematic of a battery structure with a bicontinuous cathode. b) Schematic
illustration of four primary resistances in a battery electrode. c) Schematic illustration of the fabrication process for bicontinuous electrode. d) SEM
and schematic images (inset) of the lithiated MnO2/nickel composite cathode. e) The charging/discharge curves of a prototype lithium-ion battery.
Reproduced with permission.[34] Copyright 2011, Springer Nature Group. f) Schematic of a microbattery design. g) SEM image of the interdigitated
electrodes. Inset: NiSn anode (left) and LiMnO2 cathode (right). h) A top-view SEM image of the interdigitated electrodes. Reproduced with permis-
sion.[35] Copyright 2013, Springer Nature Group.
porous metallic scaffolds to form the electrode (Figure 3g,h), of the printed battery electrodes are poor due to their high
which can decrease electron transport lengths and electrical porosity.
resistance while sustaining a high volume of active mate-
rial. Thanks to the 3D bicontinuous nanoporous electrodes,
the microbattery exhibited a maximum energy density of 2.3. Inkjet Printing
15 µWh cm−2 µm−1 and a maximum power density of
7.4 mW cm−2 µm−1. This work illustrated the potential of inte- Inkjet printing is a representative droplet-based deposition
grating materials and microengineered architecture to improve technique that can directly deposit materials through nozzles
battery performance for broad applications in sensor networks onto plastic, paper, or other substrates to create complex pat-
and medical implants.[35] terns with high resolution and tunable thickness in accordance
In conclusion, TAE is one of the few 3D printing tech- with the number of droplets discharged.[36] It has been explored
niques that can fabricate nanostructured electrodes. It has been to print sol–gel, metal, conductive polymers, carbon-based, and
proven to be an attractive method to fabricate microbatteries protein materials.[37] The ink for IJP usually has specific require-
with supercapacitor-like charge/discharge rate while retaining ments in surface tension, density, and dynamic viscosity. In the
comparable battery-like storage capacity. However, large-scale past decade, IJP has also been adopted to fabricate electrochem-
production is yet to be verified and the mechanical properties ical storage devices.[38–42] For example, Lawes et al. fabricated
Figure 4. Inkjet printing of microbatteries. a) Fabrication process for SiNP anodes on a copper foil. Reproduced with permission.[43] Copyright 2017,
Elsevier. b) Schematic of the 3D “drop-on-demand” ink jet printer. c) Schematic illustration of ice template formation. d) SEM image of MoS2–rGO
printed on Ni foam. Reproduced with permission.[44] Copyright 2019, Elsevier. e) Schematic illustration of a battery with 3D-printed electrodes. f) Cycling
performance of 3D-printed and traditional electrodes at 10 and 20 C rates for 1000 cycles. Reproduced with permission.[45] Copyright 2016, Wiley-VCH.
thin-film silicon anodes for Li-ion batteries via a desktop inkjet porous sodium-ion battery anodes.[44] Graphene oxide (GO)
printer.[43] The ink was uniformly mixed by conducting agent and ammonium thiomolybdate (ATM) were dispersed in
(carbon black), electrochemically active material (silicon nano- deionized (DI) water and served as the precursor ink, fol-
particles, SiNPs), and polymer binder in water through soni- lowed by printing onto a porous Ni foam as the current
cation (Figure 4a). Their results showed that poly(3,4-ethylen collector at −30 °C (Figure 4b). The ATM–GO droplets were
edioxythiophene):polystyrene sulfonate (PEDOT:PSS) was the frozen into ice crystals to produce a continuous matrix
most effective binder for battery electrodes, possessing large (Figure 4c). The MoS2– reduced graphene oxide (rGO) hybrid
initial and reversible capacity due to its conductive nature. The aerogel was finally prepared by thermally annealing the pre-
inkjet-printed anodes demonstrated excellent electrochemical cursor aerogel at 600 °C for 2 h. The scanning electron micros-
performance with a capacity of >1700 mAh g−1 for 100 cycles. copy (SEM) image of the printed hybrid MoS2–rGO aerogel
Furthermore, when a limited depth of discharge measurement revealed that many micrometer-sized pores formed in wrinkled
of 1000 mAh g−1 was carried out, the battery exhibited a very rGO flakes (Figure 4d), which were notably different from those
stable cycling performance of over 1000 successful cycles. This obtained via traditional 3D-printed/freeze-dried materials. Exper-
work shows that inkjet printing can fabricate thin-film SiNP imental testing showed that the electrical energy storage capa-
electrodes of high capacity, and can be extended to print other bility of the sodium-ion battery with hybrid MoS2–rGO aerogel
electrode materials.[43] anodes was reasonable and a specific capacity of 800 mAh g−1
Significant progress has also been made to improve the could be achieved in the first cycle at 100 mA g−1 current den-
specific surface area of printed electrodes. For instance, the sity. However, the specific capacity value dramatically reduced
Li group developed a 3D freeze-printing method to fabricate to 429 mAh g−1 in the first ten cycles due to irreversible
conversion of MoS2 into Mo and reversible two Na+ insertion. obtain the desired properties of shear-thinning and viscoelastic
When the current density was enhanced in following cycles, the response required for DIW (Figure 5b). To assess the effect
conversion reaction became noticeably lower and the stability of electrode thickness, they studied the areal energy density
also significantly increased.[44] and areal power density of the battery with different electrode
Recently, Hu et al. studied 3D inkjet printing of Li-ion batteries thicknesses ranging from 50 µm to 1 mm, exhibiting that full
based on LiMn0.21Fe0.79PO4@C (LMFP) nanocrystal cathodes.[45] LFP/Li4Ti5O12 (LTO) cells with ultrathick electrodes had higher
In their printing, a slurry made of carbon black, LMFP, and areal energy density and could retain the areal power density of
poly(vinylidene fluoride) (PVDF) dissolved in N-methylpyro- thin electrodes (Figure 5c). Furthermore, the areal capacity of
lidone (NMP) was prepared and extruded by a micronozzle the fully 3D-printed battery could reach up to 4.45 mAh cm−2 at
onto an aluminum foil, with well-controlled width and height a current density of 0.14 mA cm−2. The ability to develop high-
of the printed LMFP lines (Figure 4e). The Li-ion battery was performance Li-ion batteries in customized forms should have
then assembled together with lithium foil, LMFP cathode, tremendous potential to directly integrate batteries with other
and electrolyte. Compared with the batteries with electrodes 3D-printed devices.
coated the same materials, the printed battery demonstrated Most recently, Zhang et al. employed DIW to print 3D elec-
excellent electrochemical performance. For example, at rates trodes with SnO2 quantum dot (QD) inks.[52] A sol–gel approach
of 1–100 C, the gravimetric discharge capacity of a 3D-printed was used to prepare a mass of monodispersed and ultrafine
electrode varied from 161.36 to 108.45 mAh g−1, while that of a SnO2 QDs of 2–4 nm size, which were then mixed with gra-
traditionally coated electrode changed from 141 to 70 mAh g−1, phene oxide and water to yield ink for DIW. Various complex
respectively, demonstrating an improved discharge rate via architectures such as zigzag lines, spiral rectangles, periodic
3D printing of the electrode. In addition, after 1000 cycles microlattices and mosquito coils were printed without clogging
with current rates of 10 and 20 C, the specific capacities of issues (Figure 5d), confirming the capability of the ink to print
the 3D-printed electrode were 150.21 and 140.67 mAh g−1, 3D features. The filaments possessed substantial micropores
respectively. In contrast, under the same conditions, the formed in the freeze-drying process (Figure 5e), and the
specific capacities of the coated electrode only reached 3D-printed SnO2 QDs/graphene electrodes exhibited an ultra-
103.38 and 90.64 mAh g−1, respectively (Figure 4f). This research high charge capacity of 991.6 mAh g−1 at 50 mA g−1 in the first
clearly demonstrates the advantages of the 3D-printed battery cycle and the reversible capacity extended up to 1004.9 mAh g−1
over the traditionally battery with coated electrodes and provides after 50 cycles (Figure 5f), indicating an excellent cycling sta-
helpful guidance for the future design of Li-ion batteries. bility and superior performance over pure SnO2 QDs.
In summary, IJP is a relatively new technology for producing Intensifying attention has also been directed to Li–O2 bat-
low-cost printed batteries and has the potential for broader teries in recent years due to their remarkable theoretical specific
applications at an industrial scale. Furthermore, IJP has good energy (3505 Wh kg−1).[54] However, the practical specific energy
multimaterial capability, high material utilization, and excep- density and electrode capacity of Li–O2 batteries are not meeting
tional resolution, which are a great merit in printing various the application requirements. To address this issue, Lyu et al.
designed patterns, beneficial to improving the performance employed DIW to fabricate a novel metal–organic framework
of batteries. The major limitations of IJP are its relatively low (MOF)-derived hierarchically porous framework for Li–O2 bat-
printing speed and high requirements for the formulation of teries.[51] The printed hierarchically porous network was com-
inks. Moreover, the printing head is less durable and prone to posed of the micrometer-scale pores generated among Co-MOF-
clogging and damage. derived carbon flakes and the meso- and micropores within the
flakes.[51] The novel structure allowed the deposition of Li2O2
particles inside the framework and promoted the decomposition
2.4. Direct Ink Writing of these insulating Li2O2 particles to improve the electrochem-
ical performance of a Li–O2 battery (Figure 5g). At a current den-
Direct ink writing has been the most widely used 3D printing sity of 0.05 mA cm−2, the discharge capacity of the 3D-printed
method to fabricate batteries due to its advantages of affordable cathode reached up to 1124 mAh g−1. From the Ragone plot
prices, easy operation, material diversity, and maskless pro- for the cells with the 3D printing Co nanoparticles assembled
cess.[46–52] This method is based on the extrusion of ink mate- in nitrogen-doped mesoporous carbon flake (3DP-NC-Co)
rials at room temperature, and its resolution is determined by cathode, the specific energy of the Li–O2 battery was as high as
the nozzle diameter.[53] The printing process begins with prepa- 798 Wh kg−1, far beyond that of the well-established Li–S batteries
ration of the gel-based viscoelastic inks with the shear-thinning (<500 Wh kg−1) and Li-ion batteries (<300 Wh kg−1) (Figure 5h),
property. Then, the designed pattern is produced by extruding albeit at a lower maximum in specific power.[51] Li et al. pro-
a continuous filament of the ink material on the platform. By posed a novel multiscale process to fabricate high-performance
moving down the stage or up the nozzle, the next layer is then Li-ion batteries via DIW combined with an applied electric field
printed on the former layer. This process is repeated in accord- treatment.[55] They studied the physical properties and battery
ance with the model design until the required pattern is com- performance of the paste with different solid loadings (SLs).
pleted. In the recent work by the Lewis group, printed Li-ion The as-printed electrode was further cured by applying an elec-
batteries with thick electrodes were fabricated using the DIW tric field to regulate its internal structure for achieving the so-
technique.[46] All components in the battery, including the pack- called “chain effect,” leading to the improvement of electrode
aging, anode, separator, and cathode, were printed by the DIW surface (200%) and battery performance (7%). Finally, a macro–
method (Figure 5a). The four printing inks were tailored to microcontrolled 3D structure was fabricated and demonstrated
Figure 5. Direct ink writing of microbatteries. a) Optical (left) and schematic (right) images for printing the four kinds of functional inks. b) Apparent
viscosity behavior of these four functional inks. c) Areal energy density as a function of areal power density for the batteries with different electrode
thicknesses. Reproduced with permission.[46] Copyright 2018, Wiley-VCH. d) Optical image of the different patterns printed with the SnO2 QDs/GO
ink. e) SEM image of the 3DP-SnO2 QDs/G porous structure. f) Cycling stability of 3DP-SnO2 QDs/G, SnO2 QDs/G, and SnO2 QDs’ architectures.
Reproduced with permission.[52] Copyright 2018, Royal Society of Chemistry. g) Schematic illustration of a novel designed cathode. h) Specific power
as a function of specific energy of conventional supercapacitors, Li-ion, Li–S batteries, and the fabricated 3D-printed Li–O2 battery. Reproduced with
permission.[51] Copyright 2018, Wiley-VCH.
superior properties and advantages than those structures with with almost no material waste. During the printing process,
randomly distributed materials. the thin filaments of thermoplastic materials are first heated at
In summary, DIW is a commonly used technique in the the nozzle head with resistive heaters to reach their semiliquid
fabrication of 3D-printed batteries. By optimizing printing state, after which they are extruded and solidified immediately
parameters, its resolution can reach down to 1 µm.[56] However, onto the build platform to get a cross section according to the
DIW has high requirements for the gel-based viscoelastic inks, sliced model design. The thermoplastic materials used by FDM
requiring sufficiently high yield stress and storage modulus. include polylactic acid (PLA), polycarbonate (PC), PS, acryloni-
Moreover, the weak mechanical strength between the layers is trile butadiene styrene (ABS), polyphenylsulfone (PPSF), and
a burning problem needing to be solved. Thus, greater efforts polyamide (PA). The main advantages of FDM are its user
need to be taken to improve the application of the DIW tech- friendliness, affordable prices, high speed, large size capabili-
nique in battery manufacturing. ties, and avoidance of chemical postprocessing. Wei et al. used
this method to print graphene composite structures for the first
time.[57] In their work, graphite was first oxidized and exfoliated
2.5. Fused Deposition Modeling into GO sheets, then dissolved in NMP with ABS polymer and
mixed using a homogenizer. This formulation was then fol-
Fused deposition modeling has been one of the most widely lowed by the chemical reduction of GO to form G–ABS disper-
used 3D printing technologies to manufacture complex objects sion.[57] To enable compatibility with FDM printing heads, the
Figure 6. Fused deposition modeling (FDM) manufacturing of Li-ion batteries. a) Schematic illustration for the printing process of FDM. Inset: The
graphene-based filament used in FDM. b) 3D objects printed via FDM. Reproduced with permission.[57] Copyright 2015, Springer Nature Group.
c) Optical image and d) SEM image of a homogeneous filament with 40% PEGDME500. e) Optical image of a high-resolution complex “3DBenchy”
boat. Reproduced with permission.[58] Copyright 2018, American Chemical Society. f) Decomposed assembly of a 3D-printed coin cell. g) 3D-printed
glasses with an electronic darkening LCD lens and 3D-printed batteries integrated into the side temples. h) 3D-printed bangle battery lighting up an
LED. Reproduced with permission.[59] Copyright 2018, American Chemical Society.
graphene–polymer composites were generally extruded into fil- reversible capacity of 200 mAh g−1 after six cycles at a current
aments. As demonstrated in Figure 6a, the graphene–polymer density of 18.6 mA g−1 (C/20) was obtained from a printed
composite filaments were first melted in the FDM 3D printer negative electrode disk.[58] The printability of the filament was
nozzle and then extruded onto a heated platform (80 °C) layer verified by printing a high-resolution complex 3DBenchy boat
by layer to fabricate conducting 3D objects.[57] Owing to the (Figure 6e).
high accuracy and controllability, the filaments can be printed The integration of different 3D-printed electronics with
with an FDM printer to manufacture various conductive various shapes and volumes together with conventional bat-
3D models (Figure 6b), which have potential applications in teries is a challenging task and has limited the development
printed batteries. of new power-independent electronic systems. The direct 3D
Maurel et al. reported a 3D-printable graphite/PLA fila- printing approach for batteries is able to facilitate the crea-
ment, which can be used to print negative electrodes for tion of such kinds of systems. For example, Reyes et al. devel-
Li-ion batteries through an FDM 3D printer.[58] In this oped a fully printed and customized Li-ion battery with an
work, a homogeneous negative electrode disk was printed FDM 3D printer to accommodate a given product design.[59]
at a thickness of ≈250 µm (Figure 6c). They found that 40% By screening nine combinations of carbonate solvents and
plasticizer (PEGDME500) mixed into the PLA matrix can three electrolytes for commercial lithium-ion batteries,
effectively improve the ductility and reduce the stiffness of they successfully improved the ionic conductivity of PLA
the filament. The graphite grains were homogeneously dis- to 0.085 mS cm−1, about four times higher than the previ-
persed within the PLA polymer matrix (Figure 6d).[58] With ously reported values.[60] Remarkably, they also fabricated a
a high graphite and carbon black loading, an unprecedented 3D-printed full cell including anodes, cathodes, separators,
current collectors, and cases (Figure 6f). Furthermore, they including aerogel microlattices,[65] nanowires,[66] periodic scaf-
integrated the full printed batteries with a pair of 3D-printed folds,[67] and complex networks.[68] Recently, Fu et al. utilized
liquid crystal display (LCD) sunglasses (Figure 6g) and an GO to 3D-print Li-ion batteries (Figure 7a).[69] In their design,
LED bangle (Figure 6h) to demonstrate the capability of 3D highly concentrated GO was uniformly mixed with LFP and
printing to produce customizable wearable electronics. LTO nanoparticles to act as cathode and anode inks. To achieve
At present, FDM has become the most common 3D printing good performance, the mass ratio of active materials to GO
technique and has been widely used in many fields. However, was set to be 7:3, and the inks exhibited non-Newtonian fluid
there are still many problems for its application in the fabrica- behavior. After freeze-drying and annealing, pores were gen-
tion of batteries. Different from other techniques, the electro- erated in the printed electrodes (Figure 7b), which could both
chemical active materials must be mixed with thermoplastics promote liquid electrolyte penetration and act as chambers to
and extruded to be a filament for subsequent printing, which store the electrolyte. The 3D-printed full cell exhibited good
severely increases the overall procedural complexity and manu- cycling stability with an initial charge capacity of 117 mAh g−1
facturing time. Moreover, the thermoplastic filaments need to and a discharge capacity of 91 mAh g−1, respectively.[69] Addi-
be heated to their glass transit state with high temperature. tionally, a cell array composed of several pairs of miniaturized
In addition, the printing resolution of FDM is usually low, interdigitated electrodes with the size of 3 mm × 2 mm was
especially along the Z-axis, remaining typically in the range created, which could serve as an energy supply to power var-
of 50–200 µm,[13] which will affect the printing accuracy and ious microelectronics operating at various voltage or current
controllability. levels (Figure 7c).
More recently, Shen et al. presented a composite ink con-
sisting of condensed graphene oxide, 1,3-diisopropenylben-
2.6. Aerosol Jet Printing zene (DIB), and sulfur particles to print well-designed periodic
microlattices used as cathodes in Li–S batteries (Figure 7d).[70]
Aerosol jet printing is a relatively new deposition method—an With increased shear rates, the apparent viscosity of S/DIB/GO
emerging contactless direct write approach. In this process, ink decreases linearly, demonstrating an excellent shear-thin-
the functional ink is aerosolized into small droplets of 1–5 µm ning behavior well suited for extrusion-type 3D printing. Fur-
in diameter and then delivered to the substrate by a carrier thermore, the S/DIB/GO ink exhibited high shear yield stress
gas and focused by an annular sheath gas flow.[61] A wide (>102 Pa) and elastic modulus (>104 Pa), making it possible to
range of functional materials such as dielectrics, conductors, produce continuous filaments and retain design shapes. Using
semiconductors, and encapsulation materials can be printed a simple thermal treatment, a facile copolymerization between
with AJP technology.[62] Due to its features of noncontact, elemental sulfur and DIB allowed the formation of sulfur
no mask required, and high resolution, AJP has been exten- copolymer upon the surface of rGO. As shown in Figure 7e,
sively used for printing 2D electronic circuits and devices,[63] the 3D-printed sulfur copolymer–graphene electrode (3DP-
as well as for 3D electronics on the surface of 3D objects with pSG) had a higher reversible capacity of 812.8 mAh g−1 than
an advanced Aerosol Jet 5× model. However, there were no the 3D-printed sulfur–graphene electrode (3DP-SG), resulting
studies in manufacturing batteries with this technology until from the sulfur copolymer that could partially restrain the poly-
recent work reported by Saleh et al.[64] They developed a hier- sulfides from dispersing into electrolyte because of the strong
archically porous microlattice electrode through aerosol jet CS covalent bonds.
printing of silver nanoparticles. Compared with the thin solid The 3D printing technique was applied to create 3D-printed
Ag block electrode, the fabricated microlattice electrode with Li–O2 cathodes based on a GO ink developed by the Hu
hierarchical porosity can significantly improve the battery per- group.[71] They derived an extremely porous nanomaterial-
formance, such that the specific capacity and areal capacity holey graphene (hG) from commercial graphene powder via
have increased by 400% and 100%, respectively.[64] In addition, a one-step oxidation treatment. The density and size of the
the microlattice electrode demonstrated excellent mechanical pores can be manipulated by changing the synthesis condi-
robustness, retaining morphologies well after 40 electrochem- tions. The hG was used as the carbon precursor to synthe-
ical cycles. size an extremely porous GO material (hGO) via the modi-
fied Hummer’s method (Figure 7f). Remarkably, owing to
the oxidation of defective sites, the size of the defect pores
increased substantially to 4–25 nm (Figure 7g). The hGO
3. Electrode Materials for 3D-Printed Batteries ink with a high concentration (about 100 mg mL−1) was dis-
persed into water without adding any binder or other additive
3.1. Graphene or Reduced Graphene Oxide as ink for extruding hierarchical 3D architectures. The fab-
ricated mesh architectures possessed macrosize, microsize,
GO has demonstrated superior ink-formation ability, unique and nanosize pores, which were caused by the macroscale
viscoelastic properties, and functional properties that are suit- 3D mesh design, the freeze-drying-induced microscale pores,
able for 3D printing. With a thermal annealing process, GO and the inherently nanoporous hGO material, respectively.
can be easily reduced to conductive graphene (i.e., rGO), which The printed hierarchically porous and additive-free hGO
possesses good electrical conductivity and can serve as a prom- mesh structures were then thermally reduced for serving as
ising material for battery electrodes. A majority of 3D-printed 3D-printed Li–O2 cathodes. Compared with other 2D nano-
structures have been developed based on graphene oxide, porous vacuum-filtrated films and non-nanoporous GO-based
Figure 7. Graphene or graphene oxide–based electrodes for 3D-printed batteries. a) Digital image for the printing process of a multilayered electrode.
b) SEM image of a cross section of printed electrodes. c) Digital image of a 3D-printed small electrode array. Reproduced with permission.[69] Copyright
2016, Wiley-VCH. d) Schematic illustration for the fabrication process of 3D sulfur copolymer–graphene architectures. e) Cycle performances of 3DP-
pSG and 3DP-SG. Reproduced with permission.[70] Copyright 2017, Wiley-VCH. f) Schematic illustration for the fabrication process of hierarchically
porous architectures. g) SEM image of microscale-sized hGO sheets. Reproduced with permission.[71] Copyright 2018, Wiley-VCH.
mesh cathodes, the hierarchically nanoporous r-hGO mesh and polyvinyl pyrrolidone (PVP) that could be removed via
cathodes demonstrated better capacity retention and stability. subsequent thermal treatment. The acid treatment can signifi-
Notably, the hGO and the 3D-printed hierarchically porous cantly improve the dispersion of MWNTs in a solvent while
architectures can be applied for other electronics, catalysis the PVP can serve as a stabilizer for improving CNT ink
structures, batteries, and beyond. printability. When the PVP content exceeded 17 wt%, the ink
gave high flow stability and thus led to uniform printed lines.
The concatenated MWNT microbridge-line architectures
3.2. Carbon Nanotubes could also be printed on a curved glass surface (Figure 8b).
As shown in Figure 8c, a cross-shaped structure possessing
Carbon nanotubes (CNTs) have been widely used to manufac- elliptical hollow features was created, with a wall thickness
ture different devices such as sensors,[72] transistors,[73] super- of 10 µm and a height of 40 µm. This work has provided a
capacitors,[74] and especially 3D-printed batteries,[75–79] due to simple and low-cost method to print MWNT structures of
their high mechanical strength, high chemical stability, large high conductivity and resolution, which have great prospects
specific surface area, as well as excellent electrical and thermal in 3D-printed batteries.
properties. For instance, Kim et al. reported a printed highly To create a new pathway of printing Li–S batteries with CNT
conductive CNT microarchitecture (Figure 8a).[80] Their ink material, Milroy and Manthiram developed an MWCNT-based
was prepared by adding acid-treated multiwall CNT (MWNT) microelectrode for a Li–S battery via a dispenser printing
Figure 8. Carbon nanotube–based electrodes for 3D-printed batteries. a) Schematic illustration and SEM image of the 3D-printing process for carbon
nanotube ink. b) SEM image of a concatenated MWNT bridge-line structure printed on curved glass substrate. c) SEM and higher-magnification
(bottom) images of the 3D elliptical hollow architectures. Reproduced with permission.[80] Copyright 2016, American Chemical Society. d) SEM image
of the pristine aligned MWNTs and the optical images of the printed electrode as well as glass reservoir filtration assembly. Reproduced with permis-
sion.[76] Copyright 2016, Royal Society of Chemistry. e) Optical image of the printed 200 µm square on a Pt-patterned, SiO2-capped silicon wafer. f) The
image shows the flexibility of the printed electrode. g) SEM image of printed electrodes (scale = 300 nm). Reproduced with permission.[77] Copyright
2017, Wiley-VCH.
technique.[76] They dispersed MWCNTs into deionized water novel Li–S cathodes were directly printed on an aluminum
and isopropyl alcohol via bath sonication and then printed foil (Figure 8f) via inkjet-printing, exhibiting robust adherence
rounded freestanding MWCNT microelectrodes with dif- and crack resistance by a formed tightly interspersed SWNT
ferent diameters on a nylon membrane using a glass tube as network (Figure 8g). The printed S@SWNT electrodes gave a
a mask (Figure 8d). The MWCNT electrodes had the advan- stable discharge capacity, which only decreased from an initial
tages of high conductivity and ultrahigh porosity, which ben- value of ≈800 mAh g−1 to a final value of ≈700 mAh g−1 after
efit the electronic and ionic transport and electrolyte permea- 100 charge/discharge cycles at a rate of C/2.
tion inside a battery. The printed microbattery exhibited a high
areal discharge capacity of ≈7 mAh cm−2 with a printed elec-
trode of 3 mm diameter, ≈50 wt% sulfur content, and ≈7 mg 3.3. Carbon Nanofiber
cm−2 sulfur loading. Additionally, the printed microbattery
also demonstrated high stability with an excellent current den- Metal and fossil oil–derived plastics are among the most
sity up to 11.5 mA cm−2 and a Coulombic efficiency of >95% widely used ink materials in printing, but are nonrenewable,
over 200 cycles. Although a planar lithium foil was used as an scarce, and harmful to the environment.[81] Additionally, these
anode, the printed MWCNT-based cathodes have demonstrated materials possess a relatively high molten state temperature,
the capability of powering next-generation microelectronics. increasing the complexity of the manufacturing process and
More recently, the same group reported an inkjet-printed energy consumption. In a recent study, Cao et al. reported
Li–S cathode for integrated nanomanufacturing.[77] Different lithium-metal microbatteries based on cellulose nanofibers
from previous research, electronically conductive sulfur infused (CNFs).[82] CNF possesses high solubility in water owing to the
within single-walled carbon nanotubes (S@SWNT) was applied rich presence of hydroxyl groups on the cellulose molecules.[83]
as an integrated current-collector/active-material composite. On the other hand, the negative zeta potential of the CNF is as
S@SWNT was successfully printed on a Pt-patterned SiO2 high as 60 mV, enabling CNF to be utilized as a surfactant to
wafer, showing good adhesion between the printed SWNT ink enhance the dispersibility of other materials in aqueous solu-
and semiconductor substrates (Figure 8e). To demonstrate the tion.[84] Following a oxidation treatment procedure, the carbon-
printability of the S@SWNT ink on a flexible substrate, the ized CNFs mixed with LFP and Li metal can be used to print 3D
Figure 9. Carbon nanofiber–based electrodes for 3D-printed batteries. a) Schematic illustrations of the fabrication of CNF ink and a printed 3D lithium
microbattery. b) Digital images of different ink with various viscosity. c) Layer-by-layer printing of a CNF/LFP electrode. d) SEM image showing the
inside morphology of the electrode. e) SEM image of the top view of the electrode. The carbon fiber linking with the LFP particles is highlighted.
f) Optical image of a packaged battery to power an LED. Reproduced with permission.[82] Copyright 2019, Wiley-VCH. g) Schematic illustration of a
flexible composite ink. h) Schematic illustration of the fabrication process of a printed electrode. i) Digital image of a printed flexible pattern on a
transparency paper. Reproduced with permission.[85] Copyright 2016, Royal Society of Chemistry.
interdigitated cathode and anode, respectively (Figure 9a). All could provide a working voltage higher than 3.0 V to easily
the ink containing CNF exhibited high viscosity and adhered on lighten an LED (Figure 9f).
the bottom of the inverted vial (Figure 9b). Using a 3D printer, Kohlmeyer et al. also applied CNF as a conductive additive,
these inks were extruded from a 150 µm nozzle with a speed of charge collector, and porous scaffold in 3D-printed lithium-ion
2 mm s−1 layer by layer on glass slides (Figure 9c). After freeze- batteries.[85] The active material, CNFs, and PVDF were first
drying, a 3D cross-linked porous structure would form inside dispersed in a polymer solution and then coated on a poly
the electrode (Figure 9d,e), with the nanoscale LFP particles tetrafluoroethylene (PTFE) dish to form a freestanding and flex-
homogeneously distributed and tightly linked with carbonized ible battery electrode (Figure 9g). To obtain the optimal ink with
fibers. A full cell with the 3D-printed electrodes demonstrated excellent electrochemical, mechanical, and rheological properties,
a high discharge capacity of 80 mAh g−1 at the first cycle under a series of inks were developed with different parameters. In the
a high rate of 10 C, and a capacity retention of 85% after components, the active material primarily determined the elec-
3000 cycles. A packaged planar battery with printed electrodes tric storage capacity of the cell, while CNFs provided a porous
Figure 10. LTO/LFP-based electrodes for 3D-printed batteries. a) Digital images of the as-prepared LTO and LFP inks. b) SEM image of a printed
interdigitated LTO–LFP electrode. c) Digital image of a packaged 3D-IMA. Reproduced with permission.[47] Copyright 2013, Wiley-VCH. d) Schematic
illustration for the fabrication of a 3D-printed all-fiber battery. e,f) SEM images of the printed LFP fiber and the coated gel electrolyte layer. g) Demon-
stration of an all-fiber device lighting up an LED in a bent state. h) Demonstration of the integration of fiber electrodes into textile fabrics. i) Charge
and discharge curves of the same all-fiber battery. Reproduced with permission.[48] Copyright 2017, Wiley-VCH.
microstructure for excellent charging rate and improved con- printing of LTO/LFP-based electrodes have been reported.[47,48,86,87]
ductivity and PVDF tuned the mechanical properties. The ratio The first 3D-interdigitated microbattery architectures (3D-IMA)
of solvent, CNFs, and polymer affected the rheological proper- with LTO/LFP materials were developed by the Lewis Group.[47]
ties. They identified an optimal ratio of active/CNF/PVDF (i.e., The composition and rheology of their inks were the most impor-
40/40/20) to print best performance electrodes with the DIW tant elements in fabricating 3D-IMA, i.e., ensuring a reliable
(Figure 9h).[85] In extension, a LiFePO4 cathode consisting of flow through printing nozzles and providing structural integrity.
the same material ratios was printed on a transparent poly To get such inks, LTO (50 nm) and LFP (300 nm) nanoparticles
ethylene glycol terephthalate (PET) film with a complex pattern were dispersed in a complex solution composed of DI water,
and could be easily bent or deformed without obvious damage glycerol, ethylene glycol, and cellulose-based viscosifiers. The
(Figure 9i). optimized inks with 57 wt% LTO and 60 wt% LFP were made to
achieve the best rheological and printing behaviors (Figure 10a), in
which the viscosity changed from 103 to 104 Pa s at 1 s−1, while
3.4. Li4Ti5O12/LiFePO4 the plateau modulus was about 106 Pa and the shear yield stress
ranged from 102 to 103 Pa. To explore its electrochemical perfor-
Li4Ti5O12 and LiFePO4 are the most commonly used anode and mance, a 3D-IMA was printed on a glass substrate, followed by
cathode materials in 3D-printed batteries, exhibiting a minimal a drying and sintering step (Figure 10b). The as-printed 3D-IMA
volumetric expansion, high rate capability, high stability, and secu- and liquid electrolyte were then packaged in a small plastic
rity. In recent years, an increasing number of studies on the 3D case (Figure 10c). The final packaged microbattery yielded a
high areal energy density at 9.7 J cm−2 with a power density photograph of the printed GCE. Due to the semi-IPN skeleton
of 2.7 mW cm−2, as well as an areal capacity ≈1.2 mAh cm−2 component, the GCE film exhibited excellent mechanical flexi-
at 0.5 C. However, the packaged battery had lower long-term bility (Figure 11b), and there was no structural damage detected
cyclability owing to the poor hermeticity of the device, which after 10 000 bending cycles. More importantly, the GCE had
suggested that more effective packaging should be required for superior thermal stability and nonflammability. As shown in
broad applications of 3D-printed batteries. Figure 11c, compared with the traditional carbonate-based elec-
The growing demand for wearable electronics has promoted trolyte, the GCE exhibited a very good flame retardance, indi-
the development of flexible and wearable energy devices. The cating its potential as an electrolyte to improve battery safety.
fabrication of wearable batteries using 3D printing approaches Using the GCE and printed electrodes, a bipolar all-solid-state
is highly desired because of their capability of printing arbitrary Li-ion battery demonstrated outstanding mechanical flexibility
shapes and sizes and configuring multiple materials at different and thermal stability. Remarkably, different from the previous
positions as needed. In 2017, Hu and co-workers presented a inorganic electrolyte-based bipolar all-solid-state Li-ion bat-
3D-printed wearable Li-ion battery with excellent mechanical teries, no high-pressure/high-temperature sintering process
strength and high flexibility.[48] The active electrode materials was needed in this work.
of LTO and LFP, PVDF, and CNT conductive additive were A well-controlled porosity is essential for battery membranes
dissolved in NMP solution to serve as printing inks. PVDF-co- to obtain high rate capability, long-term cyclability, and den-
HFP soaked with limited LiPF6 in ethylene carbonate (EC)/ drite suppression.[92] However, it is challenging to fabricate a
diethyl carbonate (DEC) solution was coated on the surface of high-performance membrane with a controlled pore size using
printed fibers as quasi-solid-state electrolyte. Then, the coated the traditional methods. Recently, Blake et al. developed a new
anode and cathode fibers were twisted together and packaged method to 3D print high-performance and flexible ceramic–
with an outer heat shrink tube (Figure 10d,e). The surface polymer electrolytes (CPEs).[93] In their work, PVDF and glycerol
of the PVDF-co-HFP coated yarn contained lots of pores that were dissolved by NMP, and then mixed with a high loading of
could absorb and contain liquid electrolyte locally (Figure 10f). Al2O3. Owing to the higher boiling point of glycerol, the solid
In the bending state, the all-fiber battery could power an LED PVDF and liquid-like glycerol were phase-separated after drying,
lightening for several minutes, exhibiting excellent flexibility forming a microstructure with many sub-micrometer pores
and stability of the structure (Figure 10g). Furthermore, thanks (Figure 11d). Compared with commercialized separators, the
to its superior flexibility, the printed fibers can be woven into polymer electrolyte (CPE-PI) exhibited a better wettability with
fabrics for wearable energy devices (Figure 10h). The all- nearly complete wet out within 30 min (Figure 11e), which was
fiber battery displayed a discharge specific capacity of about important to abbreviate the electrolyte-filling step and increase
110 mAh g−1 at 50 mA g−1 and a Coulombic efficiency of 93%, the battery lifetime. As shown in Figure 11f, the thermal prop-
respectively (Figure 10i). This work provides an effective way erties of CPE–PI and Celgard 2325 were tested. Clearly, with
to manufacture all-fiber Li-ion batteries and opens up new the increase of temperature, Celgard 2325 continued to shrink,
chances for future wearable electronic applications. while CPE–PI showed excellent thermal stability and only 3–5%
shrinkage was observed at 190–200 °C.
Different from Blake et al.’s work, Cheng et al. believed that
4. Electrolyte Materials for 3D-Printed Batteries the additional processing of solvent evaporation obstructed the
synchronous production of electrolyte and electrodes in all-
The electrolyte is one of the most important components for 3D-printed batteries.[49] Thus, they developed a novel method
Li-ion batteries, and it plays an extraordinary, even determining, to manufacture hybrid solid-state electrolytes without any
role in electrochemical performance, cycle life, and safety of the post-treatment procedure,[49] in which solid poly(vinylidene
battery. Recently, increasing attention has focused upon the fluoride-hexafluoropropylene) (PVDF-HFP) matrices were
fabrication of high-performance electrolytes with the merits employed to improve Li-ion diffusion and to provide mechan-
of high ionic conductivity, low electronic conductivity, and ical support while Li ionic liquid was selected as ionic electro-
low activation energy.[88] With the continuing advances of 3D lyte (Figure 11g). The molten electrolyte ink was stored in the
printing technologies, the electrolyte of the batteries can also heating chamber at 120 °C and could be directly printed on a
be directly printed so as to reduce the fabrication procedures, MnO2 cathode substrate. A dense layer was formed between
fabrication time, and manufacturing cost.[7,89,90] electrolyte layer and electrode layer (Figure 11h), which can
To date, inorganic electrolytes have been extensively studied. effectively increase the adhesion between electrolyte and elec-
However, their poor chemical/electrochemical stability and trode in order to avoid short-circuits and maintain the structural
low mechanical flexibility hinder their practical applications in integrity. In contrast to the batteries created via traditional fab-
printed batteries. To resolve this issue, Kim et al. designed a rication methods, the printed batteries exhibited higher charge/
novel all-solid-state Li-ion battery with gel composite electro- discharge capacity and better rate performance, as well as high
lytes via printing.[91] In their experiments, the gel electrolyte cycling stability. Figure 11i shows a 3D Hilbert curved structure
precursor was composed of a semi-interpenetrating polymer cell that was printed on a polydimethylsiloxane (PDMS) sub-
network (semi-IPN) skeleton precursor and (1 m LiBF4 in seba- strate, indicating the capability for 3D printing batteries of any
conitrile) electrolyte with the ratio of 15/85 (w/w). The GCE ink shape.
(gel electrolyte precursor/Al2O3 nanoparticles) was then printed Garnet-type Li7La3Zr2O12 (LLZO) has also attracted more
on the surface of the LTO anode using the stencil printing attention as an electrolyte for solid-state lithium batteries due
method, followed by a UV-curing process. Figure 11a shows the to its nonflammability and high electrochemical stability with
Figure 11. Electrolyte materials for 3D-printed batteries. a) Optical image of a fabricated GCE sample. b) Optical image showing the mechanical
flexibility of the printed GCE upon the bending cycles. c) The nonflammability behavior of the GCE (top) and the carbonate-based control electro-
lyte (bottom). Reproduced with permission.[91] Copyright 2018, Royal Society of Chemistry. d) SEM image and schematic illustration of the polymer
electrolyte. e) Wettability testing for the electrolyte CPE–PI and Celgard 2325. f) Shrinkage of CPE–PI and Celgard 2325 as a function of temperature.
Reproduced with permission.[93] Copyright 2017, Wiley-VCH. g) Schematic image of a hybrid solid-state electrolyte ink. h) SEM image of the dense
layer between the MnO2 electrode and the porous layer. i) Digital image of a full battery cell printed on a 3D Hilbert curved structure. Reproduced with
permission.[49] Copyright 2018, Wiley-VCH.
lithium metal. However, the high impedance of the thick elec- Newtonian behavior was exploited to print LLZO film elec-
trolyte itself and the associated interfacial impedance hinder trolyte with a thickness of <10 µm (Figure 12c), which would
the commercialization of LLZO materials in Li-ion batteries. contribute to solving the high impedance issue of solid-
To solve this problem, McOwen et al. developed multiple solid state batteries. In contrast, the self-supporting ink showed
electrolyte inks using LLZO garnet.[94] Figure 12a shows the a Bingham-type plastic behavior, which was appropriate for
detailed 3D-printing process to manufacture 3D solid elec- printing complex 3D structures with a high aspect ratio. In
trolyte structures. In this work, LLZO film or LLZO tape was the end, a symmetric cell consisting of a 3D-printed LLZO
used as a printing substrate and the ink was printed on both stacked array and lithium electrodes was fabricated, with a
sides of the substrate. After sintering, the 3D-printed LZZO current density varying from 0.1 to 0.33 mA cm−2. A low area-
scaffold was assembled with electrodes to form the com- specific resistance (ASR) of ≈20 Ω cm−2 of the cell remained
plete battery. Two types of inks with different binders were steady in the measurements, demonstrating the high conduc-
designed, one referred to as self-supporting ink and the other tivity of the 3D-printed LLZO.[94] The low lithium metal–LLZO
as conformal ink, which exhibited dramatically different rheo- electrolyte interfacial impedance is attributed to the enlarged
logical properties and could be used to form different types contact area generated by the 3D-printed LLZO pattern and
of printed structures (Figure 12b). The conformal ink with the intimate contact of the lithium and LLZO.
Figure 12. Electrolyte materials for 3D-printed batteries. a) Schematic illustration of the fabrication for 3D-print solid electrolyte structures. b) Optical
image of the self-supporting and conformal inks deposited on a bevel. c) SEM images of a layer sintered ink with a thickness of 5–10 µm. Reproduced
with permission.[94] Copyright 2018, Wiley-VCH. d) Schematic illustration of the fabrication for cube hybrid electrolytes. e) SEM images of the 3D-printed
templates fabricated by stereolithography. Reproduced with permission.[95] Copyright 2018, Royal Society of Chemistry.
Zekoll et al. reported a novel hybrid electrolyte with 3D this approach, different microarchitectures can be created by
ceramic and polymer microchannels.[95] Figure 12d shows the stereolithography (Figure 12e). One major advantage of the
fabrication process for the hybrid electrolytes with 3D bicon- 3D-printed templates was their high porosity of ≈85% that
tinuous microarchitectures. In brief, stereolithography was first allowed most of the volume filled by ion-conducting ceramic,
employed to fabricate the cube designed polymer templates resulting in an excellent ionic conductivity of the hybrid elec-
with many empty channels. Then, the inner empty portions of trolytes. After optimization, the gyroid LAGP–epoxy electrolyte
the polymer templates were filled with the ceramic lithium-ion exhibited both improved conductivity (1.6 × 10−4 S cm−1) and
conductor Li1.4Al0.4Ge1.6(PO4)3 (LAGP) powder. Next, the filled enhanced mechanical properties, resolving a key challenge in
template was burned in air to remove the polymer template and all-solid-state batteries. The 3D-printing of solid electrolytes
sinter the LAGP phase, creating a structured LAGP scaffold. makes the fabrication of uniquely structured electrodes and
The original space of the polymer template was finally occu- electrolytes possible, whereas traditional die-pressing and tape-
pied by an insulating polymer, forming hybrid electrolytes with casting methods are limited to random porosities and planar
3D bicontinuous ceramic and polymer microchannels. With geometries.
5. Summary and Outlook for 3D-printed Li-ion batteries is also essential to protect them
from damage by oxygen/water molecules and other chemicals.
In this review, we have introduced the recent advances in Thus, new techniques and materials for printed packaging or
3D-printed batteries based on a variety of advanced printing encapsulation are also worthy of being developed in the future.
techniques as well as with regard to different electrodes and Finally, most of the current research regarding 3D-printed
electrolyte materials. Some significant progress and achieve- batteries focuses on the materials of the electrodes and elec-
ments have been emphasized. However, it should be noted trolytes. However, despite being important components in bat-
that although much progress has been made in manufacturing teries, current collectors have rarely been investigated for 3D
3D-printed batteries, there are still numerous challenges that printing fabrication. Additionally, for fully 3D-printed batteries,
must be addressed before they can be widely used commer- the compatibility of the inks for each component to be printed
cially. First, there are only a few printable materials, especially sequentially and successfully remains a big challenge. Never-
active materials, that can be used as inks for 3D printing bat- theless, thanks to its ability of printing arbitrary shapes and
teries. As an essential element in 3D printing, inks should have sizes, 3D printing may be expected to offer great chances for
appropriate surface tension, density, and dynamic viscosity. efficiently integrating printed batteries and electronic devices.
However, most active materials used in 3D-printed batteries For example, self-powered energy systems can be developed
are conventional inorganic materials. To obtain highest elec- by integrating printed batteries and energy harvesters such as
trochemical performance, it is inevitable to develop new elec- solar cells, and triboelectric and piezoelectric nanogenerators to
trochemically active materials. In addition, the inks generally achieve the functions of harvesting and storing human kinetic
contain other additives to tune the rheological properties of the and environmental mechanical energy. It is expected that with
active electrode materials, which may affect the physical prop- the continuous development of printing techniques and mate-
erties of the active materials and the electrochemical perfor- rials, 3D-printed batteries with long-term durability, favorable
mance of the batteries. Therefore, greater efforts will be needed safety, as well as high energy and power densities will eventu-
to explore more appropriate additive components for printing ally be widely used in many fields.
batteries.
Second, 3D-printed electrodes are expected to have a larger
specific surface area than those electrodes fabricated with tra- Acknowledgements
ditional methods due to the porous structures introduced in
the fabrication process. These porous structures increase the This work was supported by the start-up fund from Michigan State
power and energy density of the battery at a cost of mechanical University and the Hatch Project (1016788) from the USDA-NIFA, as well
as the University of Washington, the Washington Research Foundation,
strength. Furthermore, the 3D-printed structures are produced and the Clean Energy Institute’s Washington Clean Energy Testbeds.
layer by layer, leading to weakly bonded interfaces between
layers. Thus, further research to improve the mechanical prop-
erties of 3D-printed batteries should be done, especially for
robustness requirements in certain applications such as flexible Conflict of Interest
and wearable electronics. The authors declare no conflict of interest.
Third, although highly ordered pores can be printed by most
3D printing techniques, their sizes are usually at the microm-
eter scale. Orderly distributed hierarchical pore systems at both
micro- and nanoscales are particularly important for improving
Keywords
energy storage capacity and rate ability. Additionally, same as 3D printing, additive manufacturing, energy storage devices, printed
other manufacturing methods for electrodes, high-temperature battery, wearable devices
postprocessing is typically required for 3D printing fabrication
Received: July 31, 2019
of batteries, a time-consuming and inconvenient procedure that
Revised: September 27, 2019
may also sacrifice some electrochemical performance of the Published online:
battery. In comparison to the traditional manufacturing tech-
niques, current 3D printing also suffers from low efficiency
and is challenging to be utilized for low-cost and large-scale
manufacturing needed in commercial applications. To solve
these issues, more advanced 3D printing techniques or a com- [1] a) L. Xu, S. R. Gutbrod, A. P. Bonifas, Y. Su, M. S. Sulkin, N. Lu,
bined technique with higher resolution, higher efficiency, and H. J. Chung, K. I. Jang, Z. Liu, M. Ying, C. Lu, R. C. Webb, J. S. Kim,
non-postprocessing should be developed. J. I. Laughner, H. Cheng, Y. Liu, A. Ameen, J. W. Jeong, G. T. Kim,
Fourth, water vapor and oxygen in the air have significant Y. Huang, I. R. Efimov, J. A. Rogers, Nat. Commun. 2014, 5, 3329;
b) M. Amjadi, K.-U. Kyung, I. Park, M. Sitti, Adv. Funct. Mater.
effects on the performance of active electrode and electrolyte
2016, 26, 1678; c) M. Stoppa, A. Chiolerio, Sensors 2014, 14, 11957;
materials. The chemical reactions triggered upon contact will
d) A. Chortos, Z. Bao, Mater. Today 2014, 17, 321.
dramatically reduce the performance and service life as well as [2] X. B. Cheng, R. Zhang, C. Z. Zhao, Q. Zhang, Chem. Rev. 2017,
safety of batteries. To obtain highly efficient batteries, the prepa- 117, 10403.
ration and assembly procedures have to be performed in argon- [3] a) C. Cao, Y. Chu, Y. Zhou, C. Zhang, S. Qu, Small 2018, 14,
filled gloveboxes with <0.1 ppm oxygen or water vapor, leading 1803976; b) G. Zhou, F. Li, H.-M. Cheng, Energy Environ. Sci. 2014,
to high cost and greater difficulties. Effective encapsulation 7, 1307; c) T. M. Gür, Energy Environ. Sci. 2018, 11, 2696.
[4] a) J.-M. Tarascon, M. Armand, Nature 2001, 414, 359; b) S.-J. Tan, J. Macromol. Sci., Part C: Polym. Rev. 2005, 45, 351; c) T. Jeon,
X.-X. Zeng, Q. Ma, X.-W. Wu, Y.-G. Guo, Electrochem. Energy Rev. D.-H. Kim, S.-G. Park, Adv. Mater. Interfaces 2018, 5, 1800330.
2018, 1, 113. [27] H. Ning, J. H. Pikul, R. Zhang, X. Li, S. Xu, J. Wang, J. A. Rogers,
[5] a) B. M. G. Girishkumar, A. C. Luntz, S. Swanson, W. Wilcke, J. Phys. W. P. King, P. V. Braun, Proc. Natl. Acad. Sci. USA 2015, 112,
Chem. Lett. 2010, 1, 2193; b) Z. Peng, S. A. Freunberger, Y. Chen, 6573.
P. G. Bruce, Science 2012, 337, 563; c) P. G. Bruce, [28] a) J.-W. Choi, R. Wicker, S.-H. Lee, K.-H. Choi, C.-S. Ha, I. Chung,
S. A. Freunberger, L. J. Hardwick, J. M. Tarascon, Nat. Mater. 2012, J. Mater. Process. Technol. 2009, 209, 5494; b) I. B. Park, Y. M. Ha,
11, 19; d) T. Zhang, H. Zhou, Nat. Commun. 2013, 4, 1817. S. H. Lee, Int. J. Adv. Manuf. Technol. 2010, 46, 151; c) Y. Wu,
[6] a) A. Rosenman, E. Markevich, G. Salitra, D. Aurbach, Y. X. Chen, J. Yan, S. Yang, P. Dong, P. Soman, J. Mater. Chem. B
A. Garsuch, F. F. Chesneau, Adv. Energy Mater. 2015, 5, 1500212; 2015, 3, 5352; d) X. Zheng, J. Deotte, M. P. Alonso, G. R. Farquar,
b) N. Jayaprakash, J. Shen, S. S. Moganty, A. Corona, L. A. Archer, T. H. Weisgraber, S. Gemberling, H. Lee, F. Nicholas, Rev. Sci.
Angew. Chem., Int. Ed. 2011, 50, 5904; c) A. Manthirm, Y. Fu, Instrum. 2012, 83, 125001.
Y.-S. Su, Acc. Chem. Res. 2013, 46, 1125; d) X. Ji, L. F. Nazar, [29] Q. Chen, R. Xu, Z. He, K. Zhao, L. Pan, J. Electrochem. Soc. 2017,
J. Mater. Chem. 2010, 20, 9821. 164, A1852.
[7] T. Ma, J. Devin MacKenzie, Flexible Printed Electron. 2019, 4, [30] J. Z. Manapat, Q. Chen, P. Ye, R. C. Advincula, Macromol. Mater.
015010. Eng. 2017, 302, 1600553.
[8] a) J. D. MacKenzie, C. Ho, Proc. IEEE 2015, 103, 535; b) A. Somov, [31] E. Cohen, S. Menkin, M. Lifshits, Y. Kamir, A. Gladkich, G. Kosa,
C. C. Ho, R. Passerone, J. W. Evans, P. K. Wright, in Wireless Sensor D. Golodnitsky, Electrochim. Acta 2018, 265, 690.
Networks, EWSN 2012 (Eds: G. P. Picco, W. Heinzelman), Lecture [32] a) Y. F. Yuan, X. H. Xia, J. B. Wu, Y. B. Chen, J. L. Yang,
Notes in Computer Science, Vol. 7158, Springer, Berlin, 2012, S. Y. Guo, Electrochim. Acta 2011, 56, 1208; b) Z. Liu, A. Prowald,
pp. 212–227. S. Zein El Abedin, F. Endres, J. Solid State Electrochem. 2013, 17,
[9] a) A. Ponrouch, M. R. Palacin, Curr. Opin. Electrochem. 2018, 9, 1185.
1; b) A. L. Lipson, B. Pan, S. H. Lapidus, C. Liao, J. T. Vaughey, [33] S. I. Cho, S. B. Lee, Acc. Chem. Res. 2008, 41, 699.
B. J. Ingram, Chem. Mater. 2015, 27, 8442; c) A. Ponrouch, [34] H. Zhang, X. Yu, P. V. Braun, Nat. Nanotechnol. 2011, 6, 277.
C. Frontera, F. Barde, M. R. Palacin, Nat. Mater. 2016, 15, 169. [35] J. H. Pikul, H. G. Zhang, J. Cho, P. V. Braun, W. P. King, Nat.
[10] a) Z. Zhang, C. Zuo, Z. Liu, Y. Yu, Y. Zuo, Y. Song, J. Power Commun. 2013, 4, 1732.
Sources 2014, 251, 470; b) X. Zhang, Y. Tang, F. Zhang, C.-S. Lee, [36] a) K.-H. Choi, D. B. Ahn, S.-Y. Lee, ACS Energy Lett. 2018, 3, 220;
Adv. Energy Mater. 2016, 6, 1502588; c) H. Sun, W. Wang, Z. Yu, b) Y. Chu, C. Qian, P. Chahal, C. Cao, Adv. Sci. 2019, 6, 1801653;
Y. Yuan, S. Wang, S. Jiao, Chem. Commun. 2015, 51, 11892. c) B. Yoon, D. Y. Ham, O. Yarimaga, H. An, C. W. Lee, J. M. Kim,
[11] a) M. D. Slater, D. Kim, E. Lee, C. S. Johnson, Adv. Funct. Mater. Adv. Mater. 2011, 23, 5492.
2013, 23, 947; b) B. L. Ellis, L. F. Nazar, Curr. Opin. Solid State [37] a) Z. Zhan, J. An, Y. Wei, V. T. Tran, H. Du, Nanoscale 2017, 9,
Mater. Sci. 2012, 16, 168; c) H. Hou, Q. Xu, Y. Pang, L. Li, J. Wang, 965; b) R. P. Tortorich, J. W. Choi, Nanomaterials 2013, 3, 453;
C. Zhang, C. Sun, Adv. Sci. 2017, 4, 1700072. c) B. Derby, J. Mater. Chem. 2008, 18, 5717; d) S. Sumaiya,
[12] C. Zhu, T. Liu, F. Qian, W. Chen, S. Chandrasekaran, B. Yao, K. Kardel, A. El-Shahat, Technologies 2017, 5, 53.
Y. Song, E. B. Duoss, J. D. Kuntz, C. M. Spadaccini, M. A. Worsley, [38] J. Ding, K. Shen, Z. Du, B. Li, S. Yang, ACS Appl. Mater. Interfaces
Y. Li, Nano Today 2017, 15, 107. 2017, 9, 41871.
[13] P. Chang, H. Mei, S. Zhou, K. G. Dassios, L. Cheng, J. Mater. [39] Y. Zhao, Q. Zhou, L. Liu, J. Xu, M. Yan, Z. Jiang, Electrochim. Acta
Chem. A 2019, 7, 4230. 2006, 51, 2639.
[14] a) Z. Yang, S. Chabi, Y. Xia, Y. Zhu, Prog. Nat. Sci.: Mater. Int. [40] P. E. Delannoy, B. Riou, T. Brousse, J. Le Bideau, D. Guyomard,
2015, 25, 554; b) D. P. Singh, F. M. Mulder, A. M. Abdelkader, B. Lestriez, J. Power Sources 2015, 287, 261.
M. Wagemaker, Adv. Energy Mater. 2013, 3, 572; c) N. Hedayat, [41] Y. Gu, A. Wu, H. Sohn, C. Nicoletti, Z. Iqbal, J. F. Federici,
Y. Du, H. Ilkhani, Renewable Sustainable Energy Rev. 2017, 77, 1221. J. Manuf. Processes 2015, 20, 198.
[15] K. V. Wong, A. Hernandez, ISRN Mech. Eng. 2012, 2012, 208760. [42] J. Huang, J. Yang, W. Li, W. Cai, Z. Jiang, Thin Solid Films 2008,
[16] a) J. C. Ruiz-Morales, A. Tarancón, J. Canales-Vázquez, 516, 3314.
J. Méndez-Ramos, L. Hernández-Afonso, P. Acosta-Mora, [43] S. Lawes, Q. Sun, A. Lushington, B. Xiao, Y. Liu, X. Sun, Nano
J. R. Marín Rueda, R. Fernández-González, Energy Environ. Sci. Energy 2017, 36, 313.
2017, 10, 846; b) T. D. Ngo, A. Kashani, G. Imbalzano, K. T. [44] E. Brown, P. Yan, H. Tekik, A. Elangovan, J. Wang, D. Lin, J. Li,
Q. Nguyen, D. Hui, Composites, Part B 2018, 143, 172. Mater. Des. 2019, 170, 107689.
[17] X. Tian, J. Jin, S. Yuan, C. K. Chua, S. B. Tor, K. Zhou, Adv. Energy [45] J. Hu, Y. Jiang, S. Cui, Y. Duan, T. Liu, H. Guo, L. Lin, Y. Lin,
Mater. 2017, 7, 1700127. J. Zheng, K. Amine, F. Pan, Adv. Energy Mater. 2016, 6, 1600856.
[18] T. A. Campbell, O. S. Ivanova, Nano Today 2013, 8, 119. [46] T. S. Wei, B. Y. Ahn, J. Grotto, J. A. Lewis, Adv. Mater. 2018, 30,
[19] A. Ambrosi, M. Pumera, Chem. Soc. Rev. 2016, 45, 2740. 1703027.
[20] a) C. Liu, N. Huang, F. Xu, J. Tong, Z. Chen, X. Gui, Y. Fu, C. Lao, [47] K. Sun, T. S. Wei, B. Y. Ahn, J. Y. Seo, S. J. Dillon, J. A. Lewis, Adv.
Polymers 2018, 10, 629; b) B. C. Gross, J. L. Erkal, S. Y. Lockwood, Mater. 2013, 25, 4539.
C. Chen, D. M. Spence, Anal. Chem. 2014, 86, 3240. [48] Y. Wang, C. Chen, H. Xie, T. Gao, Y. Yao, G. Pastel, X. Han, Y. Li,
[21] F. C. Godoi, S. Prakash, B. R. Bhandari, J. Food Eng. 2016, 179, 44. J. Zhao, K. K. Fu, L. Hu, Adv. Funct. Mater. 2017, 27, 1703140.
[22] F. Rengier, A. Mehndiratta, H. von Tengg-Kobligk, [49] M. Cheng, Y. Jiang, W. Yao, Y. Yuan, R. Deivanayagam, T. Foroozan,
C. M. Zechmann, R. Unterhinninghofen, H. U. Kauczor, Z. Huang, B. Song, R. Rojaee, T. Shokuhfar, Y. Pan, J. Lu,
F. L. Giesel, Int. J. Comput. Assist. Radiol. Surg. 2010, 5, 335. R. Shahbazian-Yassar, Adv. Mater. 2018, 30, 1800615.
[23] J. A. Lewis, B. Y. Ahn, Nature 2015, 518, 42. [50] L. Zhou, W. Ning, C. Wu, D. Zhang, W. Wei, J. Ma, C. Li, L. Chen,
[24] S. C. Joshi, A. A. Sheikh, Virtual Phys. Prototyping 2015, 10, 175. Adv. Mater. Technol. 2018, 4, 1800402.
[25] F. Zhang, M. Wei, V. V. Viswanathan, B. Swart, Y. Shao, G. Wu, [51] Z. Lyu, G. J. H. Lim, R. Guo, Z. Kou, T. Wang, C. Guan, J. Ding,
C. Zhou, Nano Energy 2017, 40, 418. W. Chen, J. Wang, Adv. Funct. Mater. 2019, 29, 1806658.
[26] a) E. Stankevičius, M. Gedvilas, B. Voisiat, M. Malinauskas, [52] C. Zhang, K. Shen, B. Li, S. Li, S. Yang, J. Mater. Chem. A 2018, 6,
G. Račiukaitis, Lith. J. Phys. 2013, 53, 227; b) J. H. Moon, S. Yang, 19960.
[53] a) J. A. Lewis, Adv. Funct. Mater. 2006, 16, 2193; b) J. A. Lewis, [79] J. Wang, Q. Sun, X. Gao, C. Wang, W. Li, F. B. Holness, M. Zheng,
G. M. Gratson, Mater. Today 2004, 7, 32. R. Li, A. D. Price, X. Sun, T. K. Sham, X. Sun, ACS Appl. Mater.
[54] D. J. Lee, H. Lee, J. Song, M.-H. Ryou, Y. M. Lee, H.-T. Kim, Interfaces 2018, 10, 39794.
J.-K. Park, Electrochem. Commun. 2014, 40, 45. [80] J. H. Kim, S. Lee, M. Wajahat, H. Jeong, W. S. Chang, H. J. Jeong,
[55] J. Li, X. Liang, F. Liou, J. Park, Sci. Rep. 2018, 8, 1846. J. R. Yang, J. T. Kim, S. K. Seol, ACS Nano 2016, 10, 8879.
[56] G. M. Gratson, F. García-Santamaría, V. Lousse, M. Xu, [81] K. M. O. Håkansson, I. C. Henriksson, C. de la Peña Vázquez,
S. Fan, J. A. Lewis, P. V. Braun, Adv. Mater. 2016, 18, 461. V. Kuzmenko, K. Markstedt, P. Enoksson, P. Gatenholm, Adv.
[57] X. Wei, D. Li, W. Jiang, Z. Gu, X. Wang, Z. Zhang, Z. Sun, Sci. Rep. Mater. Technol. 2016, 1, 1600096.
2015, 5, 11181. [82] D. Cao, Y. Xing, K. Tantratian, X. Wang, Y. Ma, A. Mukhopadhyay,
[58] A. Maurel, M. Courty, B. Fleutot, H. Tortajada, K. Prashantha, Z. Cheng, Q. Zhang, Y. Jiao, L. Chen, H. Zhu, Adv. Mater. 2019, 31,
M. Armand, S. Grugeon, S. Panier, L. Dupont, Chem. Mater. 2018, 1807313.
30, 7484. [83] H. Zhu, S. Zhu, Z. Jia, S. Parvinian, Y. Li, O. Vaaland, L. Hu, T. Li,
[59] C. Reyes, R. Somogyi, S. Niu, M. A. Cruz, F. Yang, M. J. Catenacci, Proc. Natl. Acad. Sci. USA 2015, 112, 8971.
C. P. Rhodes, B. J. Wiley, ACS Appl. Energy Mater. 2018, 1, 5268. [84] Y. Li, H. Zhu, F. Shen, J. Wan, S. Lacey, Z. Fang, H. Dai, L. Hu,
[60] K. W. Chew, Adv. Mater. Res. 2013, 853, 270. Nano Energy 2015, 13, 346.
[61] A. Mahajan, C. D. Frisbie, L. F. Francis, ACS Appl. Mater. Interfaces [85] R. R. Kohlmeyer, A. J. Blake, J. O. Hardin, E. A. Carmona,
2013, 5, 4856; J. Carpena-Núñez, B. Maruyama, J. Daniel Berrigan, H. Huang,
[62] a) M. Ha, J. W. Seo, P. L. Prabhumirashi, W. Zhang, M. L. Geier, M. F. Durstock, J. Mater. Chem. A 2016, 4, 16856.
M. J. Renn, C. H. Kim, M. C. Hersam, C. D. Frisbie, Nano Lett. [86] C. Liu, X. Cheng, B. Li, Z. Chen, S. Mi, C. Lao, Materials 2017, 10,
2013, 13, 954; b) C. Cao, J. B. Andrews, A. D. Franklin, Adv. Elec- 934.
tron. Mater. 2017, 3, 1700057; c) A. Mette, P. L. Richter, M. Hörteis, [87] H. Ragones, S. Menkin, Y. Kamir, A. Gladkikh, T. Mukra, G. Kosa,
S. W. Glunz, Prog. Photovoltaics 2007, 15, 621; d) M. J. Catenacci, D. Golodnitsky, Sustainable Energy Fuels 2018, 2, 1542.
P. F. Flowers, C. Cao, J. B. Andrews, A. D. Franklin, B. J. Wiley, [88] M. Marcinek, J. Syzdek, M. Marczewski, M. Piszcz, L. Niedzicki,
J. Electron. Mater. 2017, 46, 4596; e) C. Cao, J. B. Andrews, M. Kalita, A. Plewa-Marczewska, A. Bitner, P. Wieczorek,
A. Kumar, A. D. Franklin, ACS Nano 2016, 10, 5221. T. Trzeciak, M. Kasprzyk, P. Łężak, Z. Zukowska, A. Zalewska,
[63] a) E. B. Secor, Flexible Printed Electron. 2018, 3, 035002; W. Wieczorek, Solid State Ionics 2015, 276, 107.
b) J. M. Hoey, A. Lutfurakhmanov, D. L. Schulz, I. S. Akhatov, [89] P. E. Delannoy, B. Riou, B. Lestriez, D. Guyomard, T. Brousse,
J. Nanotechnol. 2012, 2012, 324380. J. Le Bideau, J. Power Sources 2015, 274, 1085.
[64] M. S. Saleh, J. Li, J. Park, R. Panat, Addit. Manuf. 2018, 23, 70. [90] M. Kotobuki, Y. Suzuki, H. Munakata, K. Kanamura, Y. Sato,
[65] Y. Jiang, Z. Xu, T. Huang, Y. Liu, F. Guo, J. Xi, W. Gao, C. Gao, Adv. K. Yamamoto, T. Yoshida, J. Electrochem. Soc. 2010, 157, A493.
Funct. Mater. 2018, 28, 1707024. [91] S.-H. Kim, K.-H. Choi, S.-J. Cho, J. Yoo, S.-S. Lee, S.-Y. Lee, Energy
[66] J. H. Kim, W. S. Chang, D. Kim, J. R. Yang, J. T. Han, G. W. Lee, Environ. Sci. 2018, 11, 321.
J. T. Kim, S. K. Seol, Adv. Mater. 2015, 27, 157. [92] J. M. Ganesh Venugopal, J. Howard, S. Pendalwar, J. Power Sources
[67] E. B. S. Adam, E. Jakus, A. L. Rutz, S. W. Jordan, M. C. Hersam, 1999, 77, 34.
R. N. Shah, ACS Nano 2015, 9, 4636. [93] A. J. Blake, R. R. Kohlmeyer, J. O. Hardin, E. A. Carmona,
[68] Q. Zhang, F. Zhang, S. P. Medarametla, H. Li, C. Zhou, D. Lin, B. Maruyama, J. D. Berrigan, H. Huang, M. F. Durstock, Adv.
Small 2016, 12, 1702. Energy Mater. 2017, 7, 1602920.
[69] K. Fu, Y. Wang, C. Yan, Y. Yao, Y. Chen, J. Dai, S. Lacey, Y. Wang, [94] D. W. McOwen, S. Xu, Y. Gong, Y. Wen, G. L. Godbey, J. E. Gritton,
J. Wan, T. Li, Z. Wang, Y. Xu, L. Hu, Adv. Mater. 2016, 28, 2587. T. R. Hamann, J. Dai, G. T. Hitz, L. Hu, E. D. Wachsman, Adv.
[70] K. Shen, H. Mei, B. Li, J. Ding, S. Yang, Adv. Energy Mater. 2018, Mater. 2018, 30, 1707132.
8, 1701527. [95] S. Zekoll, C. Marriner-Edwards, A. K. O. Hekselman,
[71] S. D. Lacey, D. J. Kirsch, Y. Li, J. T. Morgenstern, B. C. Zarket, J. Kasemchainan, C. Kuss, D. E. J. Armstrong, D. Cai, R. J. Wallace,
Y. Yao, J. Dai, L. Q. Garcia, B. Liu, T. Gao, S. Xu, S. R. Raghavan, F. H. Richter, J. H. J. Thijssen, P. G. Bruce, Energy Environ. Sci.
J. W. Connell, Y. Lin, L. Hu, Adv. Mater. 2018, 30, 1705651. 2018, 11, 185.
[72] Y. L. Jing Li, Q. Ye, M. Cinke, J. Han, M. Meyyappan, Nano Lett. [96] C. C. Ho, K. Murata, D. A. Steingart, J. W. Evans, P. K. Wright,
2003, 3, 923. J. Micromech. Microeng. 2009, 19, 094013.
[73] A. Javey, J. Guo, Q. Wang, M. Lundstrom, H. Dai, Nature 2003, [97] M. Maximov, D. Kolchanov, I. Mitrofanov, A. Vinogradov,
424, 654. Y. Koshtyal, A. Rymyantsev, A. Popovich, Proceedings 2018, 3, 7.
[74] K. H. An, W. S. Kim, Y. S. Park, J.-M. Moon, D. J. Bae, S. C. Lim, [98] L. J. Deiner, T. Jenkins, A. Powell, T. Howell, M. Rottmayer, Adv.
Y. S. Lee, Y. H. Lee, Adv. Funct. Mater. 2001, 11, 387. Eng. Mater. 2019, 21, 1801281.
[75] Z. X. Huang, G. J. Sim, J. C. Tan, H. Y. Low, H. Y. Yang, Energy [99] Y. Qiao, Y. Liu, C. Chen, H. Xie, Y. Yao, S. He, W. Ping, B. Liu,
Technol. 2018, 6, 1715. L. Hu, Adv. Funct. Mater. 2018, 28, 1805899.
[76] C. Milroy, A. Manthiram, Chem. Commun. 2016, 52, 4282. [100] C. C. Ho, J. W. Evans, P. K. Wright, J. Micromech. Microeng. 2010,
[77] C. A. Milroy, S. Jang, T. Fujimori, A. Dodabalapur, A. Manthiram, 20, 104009.
Small 2017, 13, 1603786. [101] C. W. Foster, M. P. Down, Y. Zhang, X. Ji, S. J. Rowley-Neale,
[78] X. Gao, Q. Sun, X. Yang, J. Liang, A. Koo, W. Li, J. Liang, J. Wang, G. C. Smith, P. J. Kelly, C. E. Banks, Sci. Rep. 2017, 7, 42233.
R. Li, F. B. Holness, A. D. Price, S. Yang, T.-K. Sham, X. Sun, Nano [102] D. Vernardou, K. C. Vasilopoulos, G. Kenanakis, Appl. Phys. A
Energy 2019, 56, 595. 2017, 123, 623.

Adfm 201906244

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Review

Additive Manufacturing of Batteries

cost-effective energy storage devices to

control electrode microstructure and device assembly, but little

However, considering the compatibility among the preparation

2.1. Lithography-Based Printing

Holographic lithography (HL) is based on the multibeam

Printing method Anode/Cathode Electrolyte Specific capacity Ref.

Table 2. Comparison of different 3D printing techniques for batteries.

3D printing method Available materials Printing Advantage Disadvantage

You might also like

Adfm 201906244

Uploaded by

Copyright:

Available Formats

Adfm 201906244

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

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Adfm 201906244

Uploaded by

Copyright:

Available Formats

Review

Additive Manufacturing of Batteries

c­ost-effective energy storage devices to

control electrode microstructure and device assembly, but little

However, considering the compatibility among the preparation

2.1. Lithography-Based Printing

Holographic lithography (HL) is based on the multibeam

Printing method Anode/Cathode Electrolyte Specific capacity Ref.

Table 2. Comparison of different 3D printing techniques for batteries.

3D printing method Available materials Printing Advantage Disadvantage

You might also like

cost-effective energy storage devices to