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Applied Materials Today

journal homepage: www.elsevier.com/locate/apmt

3D-printed self-standing electrodes for flexible Li-ion batteries

Sekar Praveen a, Gyu Sang Sim a, Nitheesha Shaji a, Murugan Nanthagopal a,
Chang Woo Lee a,b,∗
a
Department of Chemical Engineering (Integrated Engineering), College of Engineering, Kyung Hee University, 1732 Deogyeong-daero, Giheung, Yongin,
Gyeonggi 17104, South Korea
b
Center for the SMART Energy Platform, College of Engineering, Kyung Hee University, 1732 Deogyeong-daero, Giheung, Yongin, Gyeonggi 17104, South
Korea

a r t i c l e i n f o a b s t r a c t

Article history: Sizable demand for flexible electronics has resulted in the need for a flexible energy storage device with
Received 16 December 2020 high performance and unique architectures. Currently, Li-ion batteries (LIBs) are the most desired choice
Revised 27 January 2021
for achieving higher capacity. However, obtaining a high capacity without sacrificing flexibility at the
Accepted 12 February 2021
same time is quite tricky using the conventional electrode preparation process, which employs rigid metal
current collectors. Herein, we adopt a 3D-printing technology to fabricate flexible self-standing electrodes
Keywords: by incorporating vapour grown carbon fibers (VGCFs) in electrode inks to functionalize a current collector
3D-printing integrated electrode. A fine balance between the electrochemical performance and flexibility has been
Self-standing electrode achieved by varying the ink component ratios. The influences of each component on the mechanical
Flexible
property, conductive nature, and electrochemical performance have been thoroughly investigated. The
Rheological properties
battery performance is evaluated in coin-type of half and full-cell assemblies. Further, a prototype pouch
Li-ion battery
cell is fabricated using self-standing electrodes to show its flexibility crucial for real time applications.
© 2021 Elsevier Ltd. All rights reserved.

1. Introduction ible energy storage sources. One such issue is that the electrodes
in existing Li-ion batteries are fragile and rigid [15]. The rigidity
Personal digital assistant technology has transformed our daily arises mainly due to the presence of metallic aluminium (Al) and
lives, making it easier to communicate and share data with each copper (Cu) foils, which serve as a support layer for the electrodes
other on the go. This technology has attained maturity in the re- and also a current collector to draw the current to the external
cent past and it has been gaining attention due to their higher circuit. Moreover, the use of Al and Cu as current collectors makes
degree of freedom and comfortability in the form of flexible elec- them more vulnerable when they are subjected to bending which
tronics. Although there have been several flexible devices emerging can lead to the loss of contacts within the electrode materials and
in the market in recent years, there are still unresolved challenges thereby, failure of the device [16-18]. Therefore, the use of metal
for this technology. Therefore, the surge in the demand for these current collectors is not considered as a suitable choice for flexible
flexible devices has prompted significant research interests to find device applications.
a suitable energy storage source to power these devices [1–7]. In Several modification techniques have been adopted to provide
pursuit of these flexible devices, the desired energy storage source flexibility to the electrodes of Li-ion batteries where the most
needs to be extremely flexible, such that it can withstand repeated prevalent techniques are structure and material design. Structure
mechanical stress without sacrificing device performance. Li-ion design was initially adopted by bending the entire device in a par-
batteries (LIBs) are undoubtedly considered as a choice for pow- ticular predefined manner without degradation of the structure.
ering these flexible devices due to their high energy density, high Some of the designs reported are neutral plane design, [19] serpen-
operating voltage, long term cyclability, and no memory effects [8- tine patterning, [20] island architecture, [21] origami, and kirigami
14]. However, they are still facing several challenges which need folding [17, 22]. In contrast, material design is considered as a
to be resolved in addition to the challenges put forward by flex- more convenient and widely adopted technique, which utilizes the
physical properties of the materials such that it has intrinsically
good flexibility to form a film. This could be achieved by coating a
∗
Corresponding author at: Department of Chemical Engineering (Integrated Engi-
conductive layer over a flexible non-conducting polymer, paper, or
neering), College of Engineering, Kyung Hee University, 1732 Deogyeong-daero, Gi-
heung, Yongin, Gyeonggi 17104, South Korea.
plastic substrate [23–26]. However, the above-mentioned technique
E-mail address: [email protected] (C.W. Lee). may limit the volumetric performance as well as the electrical

https://doi.org/10.1016/j.apmt.2021.100980
2352-9407/© 2021 Elsevier Ltd. All rights reserved.

Please cite this article as: S. Praveen, G.S. Sim, N. Shaji et al., 3D-printed self-standing electrodes for flexible Li-ion batteries, Applied
Materials Today, https://doi.org/10.1016/j.apmt.2021.100980
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conductivity and cause undesirable reaction with the corrosive sample notation according to the ratios of composition and elec-
electrolyte solution [27]. Considering these ambiguities, a more trical, mechanical, and electrochemical properties of self-standing
suitable alternative would be needed to develop a self-standing electrodes. Each of the electrode inks for the self-standing elec-
electrode by embedding a material that imparts the electrode with trodes constitutes a specific ratio of the active material, conductive
the property of a current collector as well as conducting matrix agent (VGCFs), and polymer binder (PVdF), which were dissolved
that is immune to corrosive environments. in 5 mL of NMP solvent. Typically, for the preparation of electrode
Additionally, the batteries required for flexible devices often ink formulations, PVdF was dissolved in NMP followed by the ad-
come in diverse form factors and complex architectures, which are dition of the VGCFs and active material sequentially followed by
designed to fit a specific surface [28]. Therefore, a robust, eco- homogenization for about 30 min. The desired electrode inks were
nomic, and template-free technique is necessary to achieve such filled in a syringe barrel for use in 3D-printing. Importantly, the
architectures. 3D-printing technology has started gaining attention solid mass ratio of each of the inks was maintained at about 80 mg
and has the potential to revolutionize battery industries with their mL−1 to achieve a viscosity compatible with the 3D-printer nozzle.
capability to build custom structures [29–31]. Although printed
batteries have been fabricated and demonstrated on the micro-
scale level, they often require complex ink formulation steps with 2.3. Printing procedure
the inclusion of specific additives to tune the ink properties and in-
dividual digital design models which are required to achieve high The electrode inks were printed with the help of an extrusion
resolution patterns. Moreover, the addition of external additives type desktop printer (E2, Nordson EFD). The electrode inks were
might compromise the overall electrochemical performance of the loaded on a fluid body seat using a 30 mL syringe barrel and a flat
printed battery. tappet nozzle with a diameter of 0.8 mm was used to print the
In this study, we report an approach to fabricate self-standing electrodes. The extrusion rate and barrel pressure were controlled
electrodes, i.e., anode and cathode by an extrusion-based 3D- with the help of a CCNT-25S Pro-compressor and a constant pres-
printing technology. We have chosen a matured and commer- sure of 80 psi was maintained throughout the experiment with a
cialised material like lithium nickel cobalt aluminium oxide printing speed of 50 mm s − 1 . The electrode inks were printed
(LiNi0.8 Co0.15 Al0.05 O2 ) as a cathode active material due to its high on the top of a pre-treated and cleaned glass substrate to facili-
energy density, low cost and better cycle life [32]. vapour grown tate easy removal of the electrodes after proper drying. Upon coat-
carbon fibers (VGCFs) are employed as an elementary conductive ing the electrodes, the printed electrodes along with the glass sub-
building block to act as a current collector embedded with the self- strate were dried initially on a hotplate for about 15 min at 110 °C
standing electrode. The VGCFs are preferred because of their high to remove the excess solvent followed by drying in a vacuum oven
surface area and electric conductivity, which enables a short elec- at 120 °C overnight. After the electrodes were properly dried, they
tron transfer route for the active materials, as well as their porous were peeled off gently with the help of a razor blade to obtain the
structure, which facilitates faster ion transportation [33, 34]. Along self-standing electrodes.
with the above-mentioned advantages, the VGCFs have a graphitic
structure but in a coiled form which makes them a potential anode
active material. The fabricated self-standing electrodes have a fine 2.4. Sample characterisation
balance between electrochemical performance and flexibility along
with print compatibility. These were achieved by preparing a series The morphologies of the samples were analysed using a high-
of ink formulations, which possess various ratios of an active mate- resolution field-emission scanning electron microscope (HR FE-
rial, a conductive agent, and a binder. The rheological, mechanical, SEM, Merlin, Carl Zeiss) and the elemental composition of the sam-
and electrochemical behaviours of the obtained self-standing elec- ples was measured using an energy dispersive X-ray spectrome-
trodes were systematically investigated. The ratio of each compo- ter (EDS, Oxford Instruments). The crystalline nature and phase
nent in the formulated electrode ink has an inherent property in purity were studied by X-ray diffraction (XRD, M18XHF-SRA, Mac
influencing the entire performance of the self-standing electrode. Science Ltd.) using Cu Kα irradiation (60 kV, 55 mA, λ= 1.54 Å).
Finally, the flexible nature and endurance of the self-standing elec- The low frequency vibrational and rotational modes of the carbon
trodes were evaluated by physical bending followed by fabricating nanofibers were detected by high-resolution Raman spectroscopy
a full-cell assembly. (HR-Raman, inViaTM, Renishaw, Plc.) using an argon ion laser
beam (50 mW, 514 nm). The rheological behaviour of the respec-
tive inks were analysed by a stress controlled rheometer (VT550
2. Materials and methods
Thermo Electron, Haake Mars). A rotational ramp was performed
at room temperature to measure the apparent viscosity at vari-
2.1. Materials
ous shear rates. The inks were loaded in a 20 mm diameter steel
plate with a gap of ~0.95 mm between the two parallel plates. The
Cathode active material, lithium nickel cobalt aluminium ox-
electrical conductivity was measured using a four-point probe in-
ide (LiNi0.8 Co0.15 Al0.05 O2 , denoted by NCA, 3–8 μm) was purchased
strument (MCP T610, Mitsubishi), where the samples were cut into
from EcoPro BM, Ltd. vapour grown carbon fibers (VGCFs) were
a square shape with dimensions of 2 cm (W) × 2 cm (L) with
purchased from Showa Denko and used as both an anode active
a thickness of around 50 μm. Each sample was measured three
material and a conductive agent. Polyvinylidene difluoride (PVdF,
times at various points to obtain a uniform reading. The electri-
Mw 602,0 0 0) was purchased from Solvay Chemicals and was used
cal conductivity of self-standing electrodes as a function of bend-
as a binder. N-Methyl-2-pyrrolidone (NMP, 99.5%) was purchased
ing was measured using Hewlett-Packard LCR metre, the samples
from Daejung Chemical and Metals Co. and was used as a solvent
with varying ratios are cut into 5 cm (L) × 1 cm (W) dimension
for the preparation of the electrode slurry.
and are bended at a radius of 1 cm with their ends pasted with
a copper tape prior measuring. The tensile testing was conducted
2.2. Preparation of electrode inks using an universal testing machine (UTM, 5844, Instron) at scan
rate of 2 mm min−1 at room temperature. The self-standing elec-
The electrode inks for the self-standing electrodes were formu- trode samples for UTM analysis were cut using a sharp razor with
lated according to the ratios of the composition. Table 1 shows the dimensions of 2 cm (W) × 6 cm (L) with a thickness of 50 μm.

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Table 1
Sample notation according to the ratios of composition and electrical, mechanical, and electrochemical proper-
ties of self-standing electrodes.

Discharge Capacity at 0.1 C

Sample Composition Ratio  (S cm−1 ) TS (MPa) (mAh g−1 )

C 522 NCA:VGCF:PVdF 50:25:25 3.74 4.03 197

C 442 NCA:VGCF:PVdF 40:40:20 3.95 1.11 176
C 433 NCA:VGCF:PVdF 40:30:30 1.10 8.91 170
C 424 NCA:VGCF:PVdF 40:20:40 1.79 11.40 180
C 622 NCA:VGCF:PVdF 60:20:20 2.40 4.23 187
A 505 VGCF:PVdF 50:50 4.59 3.53 150
A 604 VGCF:PVdF 60:40 5.18 3.24 220

2.5. Assembly of battery and electrochemical tests work formation, high wettability, and good homogeneity with the
inks [33]. In addition, the VGCFs being a carbon allotrope possess
The electrochemical performance of the self-standing electrodes a coiled and stacked arrangement of graphene sheets, which could
was individually evaluated using a CR2032-type coin cell configu- be utilised as a viable anode material for Li-ion batteries.
ration with lithium metal as a reference electrode in the case of In order to arrive at an optimum balance between the con-
half-cells and Celgard 2340 as a separator. The electrolytic solu- ductivity, electrochemical performance, printing compatibility, and
tion was comprised of 1.0 M lithium hexa-fluorophosphate (LiPF6 ) flexibility, several experiments were performed by varying the ra-
dissolved in a 1:1 volumetric solution of ethylene carbonate (EC) tios of each of the constituents of the electrode ink. The detailed
and diethyl carbonate (DEC) and 60 μL of electrolyte was added analysis of the constituent ratios and the influence on their me-
while fabricating each coin cell. All of the cells were assembled chanical, electrical, and electrochemical behaviour are elucidated in
inside an Ar-filled glove box with moisture and oxygen contents Table 1. Since we fabricated self-standing electrodes with different
below 1.0 ppm. The galvanostatic charge-discharge tests were con- ratios, we segregated them into cathode represented as C and an-
ducted using a multi-channel battery measurement system (ETH ode represented as A with the ratio of each component for active
Cycler). The fixed potential windows for the NCA-VGCFs-based self- material:conductive agent:binder indicated next to the designated
standing cathodes were 3.0–4.3 V and 0.01–3 V for VGCFs-based electrode material in the specified order. The same sample notation
self-standing anodes. In the case of full-cell configurations employ- will be followed throughout to eliminate confusion. However, the
ing NCA-VGCFs as the cathode and VGCFs as an anode, the poten- number of the ratio for the anode has been given to the active ma-
tial window was fixed in the range of 2.7–4.3 V. The rate capability terial and the binder with zero of conductive agent because VGCFs
studies for various cathode ratios were performed in a same man- are used as both an anode active material and a conductive agent.
ner where each half-cell was successively cycled at different cur-
rent rates of 0.1, 0.2, 0.5, 1, 2, and finally recovered at 0.1 C with 5
3.2. Rheological behaviour of the electrode inks
cycles at each current rate.
Fine-tuning of the electrode inks to a desired rheology is neces-
3. Results and discussions
sary for obtaining a desired print pattern with high resolution. It is
worth mentioning that the rheological behaviour of the ink differs
3.1. Adhesive nature of the electrodes with the substrate
when the desired constituents including an active material, a con-
ductive agent, and a binder are varied, as shown in Table 1. The in-
The self-standing electrodes were fabricated by printing the
fluence of each component on the rheological behaviour was stud-
modulated electrode inks on a glass substrate by using an
ied using a rheometer by plotting the apparent viscosity vs. shear
extrusion-based 3D-printer followed by peeling them after they
rate for the cathode and anode inks, as shown in Fig. 1(f & g). The
were sufficiently dried. A key aspect that is necessary for obtaining
solid loading concentration of each of the cathode and anode ink
damage-free self-standing electrodes is to choose a proper binder
ratios was kept constant at 80 mg mL−1 . All of the inks displayed
and substrate material. The amount of PVdF as a binder determines
good shear thinning behaviour at high shear rates, which is suit-
the adhesive nature of the self-standing electrodes with the sub-
able for uniform printing through the nozzle. A common observa-
strate material [35]. An amount in excess of the optimum level ac-
tion is that the viscosity increases with an increase of the VGCFs
tually leads to weak adhesion between the substrate and printed
loading, where the C 442 possesses the maximum VGCFs loading
electrode [35, 36]. In our study, glass was used as the preferred
of 40%, as displayed in Fig. 1(f), and the lowest apparent viscosity
substrate material since it would be more favourable to detach the
was observed for the C 622. From Fig. 1(g), a similar trend was ob-
electrodes without causing any physical damage to the electrodes.
served for the two anode ink ratios as well with the highest appar-
Moreover, the presence of hydroxyl groups on the surface of the
ent viscosity being achieved for A 604 with the maximum VGCFs
glass makes them hydrophilic in nature and the presence of fluo-
loading and a slightly lower viscosity was achieved for the A 505
ride groups in PVdF makes them hydrophobic, resulting in easier
with a lower VGCFs loading.
detachment of the electrode due to the discrepancy of the surface
groups [37]. The final thickness of the printed self-standing elec-
trodes can be controlled by increasing or decreasing the number of 3.3. Mechanical behaviour of the electrodes
layers printed on top of each printed layer as shown in Fig. S1. The
schematic of the ink preparation, printing of the electrode inks, The tensile strengths of the self-standing anode and cathode
and fabrication of self-standing batteries is shown in Fig. 1(a–e). In electrodes were studied by plotting the stress strain curve, as
order to obtain optimised printing parameters for analysing the na- shown in Fig. 2. The tensile stress is the force exerted by the ma-
ture of the electrode we chose NCA, a mature and commercialised terial itself to oppose the external force to restore its shape and
cathode active material throughout the entire work. VGCFs are pre- tensile strain is the degree to which an object can deform when
ferred as the conductive reinforcing material for the self-standing a force is being applied externally. Similar trends as the rheolog-
electrodes mainly because of their high conductivity, pervasive net- ical studies were observed in all of the stress strain curves. The

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Fig. 1. Schematics of printing process of self-standing electrodes. (a) Main components of electrode inks. (b) Printing of the NCA-VGCFs cathode electrode over glass substrate.
(c) Printing of VGCFs anode electrode over a glass substrate. (d) 3D-printed full cell having current collector free self-standing printed electrodes. (e) The rheologically
modulated anode and cathode inks compatabile for 3D-printing. (f) Apparent viscosity vs. shear rate for different ratios of NCA-VGCFs cathode inks. (g) Apparent viscosity
vs. shear rate for different ratios of VGCFs anode inks.

stationary phase does not exert any stress at the start of the ex- because the VGCFs can interfere with the binder and disconnect
periment, as shown in Fig. 2(a). It follows quasi linear behaviour the polymer matric chain.
when the material finally begins to yield under tension, which is
followed by an irreversible deformation of the electrode. Once the 3.4. Electrical conductivity of the electrodes
fracture point is reached, the material tears apart as in the case of
Fig. 2(b). From the stress strain curves of various cathode and an- However, the VGCFs are mainly adopted to increase the conduc-
ode ratios shown in Fig. 2(c & d), the increase of the polymer load- tivity of the self-standing electrode along with their high wettabil-
ing to the electrode causes an increase of the mechanical proper- ity and homogeneity in ink suspensions. The influence of VGCFs
ties with a maximum tensile stress being achieved for C 424 with on conductivity enhancement in self-standing electrodes was stud-
a tensile stress of 11.4 MPa at 1.6% and the lowest being achieved ied using a four-point probe conductivity tester and the results are
at 1.11 MPa at a 0.3% strain to failure for the C 442 sample which summarised in Table 1 and the bar chart in Fig. 3(a). All of the
possesses the lowest polymer loading content. Moreover, a simi- electrode ratios displayed reasonably good electrical conductivity
lar trend was also observed for the anode material, as shown in ranging between 1.1 and 5.1 S cm−1 , which is considered suitable
Fig. 2(d), with the mechanical properties being enhanced for the for self-standing Li-ion battery electrodes [39-41]. In general, the
sample with the highest polymer loading. These results are similar conductivity of self-standing electrodes tends to increase with an
or comparable to those of other reported self-standing composite increase of the VGCFs loading content. However, C 433 displayed
electrodes [38]. The influence of the mechanical properties upon a lower conductivity level despite having a high VGCFs loading.
excess addition of the VGCFs was also investigated, where the C This phenomenon may be due to the high polymer loading, which
424 exhibited a tensile stress of 11.4 MPa at 1.59% strain and the A could occupy most of the interconnected spaces between the par-
604 showed a degraded tensile stress of 3.2 MPa at 0.6% strain de- ticles rather than allowing the electrolyte to percolate, causing a
spite having the same polymer loading of 40 wt.%. This might be decrease in the overall electrical conductivity [42,43]. Additionally,

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Fig. 2. Stress-strain profiles of self-standing electrodes. (a) Photograph showing the set-up used for stress strain measurements with electrode being attached to the grippers
in normal state and (b) After complete electrode failure. (c) Stress-strain curve of the various ratios of NCA-VGCFs cathode electrodes. (d) Stress-strain curves for various
ratios of VGCFs anode electrodes.

Fig. 3. (a) Electronic conductivity of various ratios of NCA-VGCFs cathode and VGCFs anode electrode. (b) Rate performances of various ratios of NCA-VGCFs self-standing
electrodes.

we have carried out the conductivity testing of the self-standing these electrodes were evaluated by constructing half-cells for the
electrode as a function of bending as shown in Fig. S2. The elec- rate capability studies, as shown in Fig. 3(b). At a lower current
trical conductivity values for the relaxed state and bended state rate of 0.1 C, all of these ratios delivered an acceptable theoreti-
are summarised in Table S1. When comparing the results obtained cal utilization of NCA active material of >62.00% (0.1 C). A direct
from the LCR metre no significant difference in the electrical con- consequence of degraded performance upon increasing the poly-
ductivity values could be observed between the self-standing elec- mer loading can be observed in the rate capability studies. The C
trodes which are at rest and when being subjected to bending, this 522 and C 622 materials possessing lower polymer loadings deliv-
conveys that the self-standing electrodes remain intact when they ered specific discharge capacities of 197 mAh g−1 and 187 mAh g-1
are bended and no crack or breakage of interconnected VGCFs net- at 0.1 C and 147 mAh g−1 and 142 mAh g−1 at 2 C current rates,
work occurs during the bending process. respectively. The materials with the highest polymer loading ratios
such as C 433 and C 424 displayed inferior results. Comparing the
3.5. Rate capability of various cathode ink ratios electrochemical performances, mechanical stability, and electrical
conductivity for all of the ratios, the C 522 and C 622 cathode ex-
After estimating the mechanical and conductivity properties of hibited more favourable results for the fabrication of self-standing
the self-standing electrodes, the electrochemical performances of electrodes with decent mechanical properties, electrical conductiv-

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Fig. 4. HR FE-SEM images at various magnifications for a selected ratio of NCA-VGCFs cathode and VGCFs anode self-standing electrodes. (a)(i) Cross-sectional view of NCA-
VGCFs cathode electrode. (a)(ii&iii) The high maginfication image of the same. (b)(i) Cross-sectional view of VGCFs anode electrode. (b)(ii&iii) The high maginfication image
of the same.

ities, and good electrochemical performances. amongst all of the galvanostatic charge and discharge curves of NCA-VGCFs cathodic
ratios, C 522 was considered as the best cathode of choice for half-cells with Li as the reference electrode. Initial specific charge
achieving better performance compared to the other contenders. and discharge capacities of 227 and 200 mAh g−1 were attained
with a coulombic efficiency of 88.10% at a current rate of 0.1 C
3.6. Physiochemical characterisation of the electrodes and a potential window of 3.0–4.3 V. With increasing number of
cycles, the coulombic efficiency increased to 98%. Fig. 5(b) shows
In order to validate the optimal mechanical stability and elec- the cyclic performance for 50 cycles at a current rate of 0.1 C,
trochemical performance of the self-standing electrodes like C 522 where the capacity retention achieved at the end of 50 cycles was
NCA-VGCFs cathode and A 604 VGCFs anode, cross-sectional HR about 84%. Up to now, VGCFs have been mainly used as a con-
FE-SEM studies were performed and the images are displayed in ductive agent or a dopant to increase the electrochemical perfor-
Fig. 4. The HR FE-SEM images observed at low magnification show mance. Since VGCFs possess a stacked-cup like graphitic structure,
that both samples possess a homogeneous dispersion of all of the as shown in the HR FE-SEM image of Fig. S4(a), they could dis-
constituents throughout the electrode surfaces, which is necessary play electrochemical performance similar to that of graphite when
for proper functioning of the electrode. Moreover, the C 522 mate- they are cycled below 0.5 V [50]. The electrochemical performance
rial in Fig. 4(a)(i–iii) which has a 50:25:25 ratio of NCA:VGCF:PVdF of the self-standing A 604 anode was studied and is shown in
showed a good porous nature throughout its surface, which would Fig. 5(d), where the galvanostatic charge and discharge curves de-
help in providing better electrochemical performance by providing livered an initial specific discharge capacity of 187 mAh g−1 with
high diffusion pathways for ion movement. However, the presence an initial coulombic efficiency of 79.23% at a current rate of 0.1 C
of pores could compromise the mechanical properties of the self- when cycled between 0.01–3.0 V. After a few cycles, the coulom-
standing electrode. Similarly, the HR FE-SEM images of A 604 in bic efficiency increased to 100%. Fig. 5(e) shows the cyclic perfor-
Fig. 4(b)(i–iii), which has a 60:40 ratio of VGCF:PVdF, also display mance of the anodic half-cell electrode cycled for 50 cycles at a
a porous structure but with comparatively more dense packing and current rate of 0.1 C, where it shows a gradual increase of the
a highly interconnected network structure, as observed throughout charge discharge capacity from 220 mAh g−1 after 10 cycles to 249
the electrode. The HR FE-SEM images of pure NCA and VGCFs mi- mAh g−1 after 50 cycles. This phenomenon is mainly caused due
cro and nano particles are displayed in Fig. S3(a) and Fig. S4(a), re- to the irreversible microstructural transition of the graphitic lay-
spectively. The phase purity, crystallinity and compositions of the ers form a disorder to an ordered structure which generally occurs
NCA and VGCFs samples were confirmed through X-ray diffraction during the initial cycles [42]. A similar increasing trend was also
as shown in Fig. S3(d) and Fig. S4(d) and EDS studies as shown observed in the literature [43,44]. The galvanostatic charge and dis-
in Figs. S3(b)(i–iv) and S4(b), respectively. The EDS spectra of the charge curves for the self-standing anode electrode with a 50:50
same are shown in Fig. S3(c) and S4(c) which matched with stan- ratio of VGCF:PVdF (A 505) were evaluated for 5 cycles and are
dard pattern for both active materials [44–47]. Figure S4(e) shows displayed in Fig. S5(a & b), where they show inferior results when
the HR-Raman spectrum of VGCFs which displays two character- compared with those of the A 604 material. The decay of the elec-
istic peaks at 1578 and 1351 cm−1 . representing the D band (de- trochemical performance was mainly caused by the increase of the
fective band) and G band [48]. The degree of graphitisation can be polymer loading, which may fill the voids and could block the dif-
analysed by calculating the ID /IG value which was found to be ~ fusion pathways in the electrode. Fig. 5(c & f) shows the dQ/dV dif-
0.01, representing a high degree of graphitisation [49]. ferential capacity analysis of the self-standing electrodes to under-
stand the cell degradation mechanism and phase transition of elec-
3.7. Electrochemical performance of the electrodes trode material. The NCA-VGCFs half-cell in Fig. 5(c) displays an ox-
idation plateau above 4.0 V, which corresponds to oxygen removal
The electrochemical performances of the self-standing elec- from the lattice sites along with further delithiation. Phase tran-
trodes were studied individually using a half-cell configuration sition from hexagonal H2 to H3 is observed from the voltage pro-
starting with the C 522 cathode electrode. Fig. 5(a) shows the files [51]. In the 2nd cycle, the oxidation peak at 4.2 V corresponds

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Fig. 5. Electrochemical performance of the self-standing electrodes in half-cell assemblies. NCA-VGCFs cathode (a) Galvanostatic charge-discharge curves at 0.1 C. (b) Cyclic
performance and coulombic efficiency for first 50 cycles at 0.1 C. (c) Differential capacity vs. voltage profile at 0.1 C. VGCFs anode (d) Galvanostatic charge-discharge curves
at 0.1 C. (e) Cyclic performance and coulombic efficiency for first 50 cycles at 0.1 C. (f) Differential capacity vs. voltage profile at 0.1 C.

to Li-ion extraction from the lattice structure and the reduction chemical performance of the NCA-VGCFs/VGCFs full-cell is shown
peak at 4.17 V corresponds to Li-ion insertion into the lattice struc- in Fig. 6(b & c) and from their galvanostatic charge and discharge
ture. Further, at the 50th cycle, a decrease in the peak intensity curves, the initial specific charge and discharge capacities attained
of the oxidation peak was observed, whereas the reduction peak 218 and 197 mAh g−1 , respectively, at a current rate of 0.1 C in
was shifted to 4.08 V. The shift of the reduction peak to a lower the potential window of 2.7–4.3 V. The coulombic efficiency of
potential range is mainly caused by the migration of the transi- the initial cycle was 90.3% and it increased to 98% upon succes-
tional metal ions from the transition metal layer to lithium, re- sive cycles. Fig. 6(c) shows the cyclic performance of the full-cells
sulting in a decay of the operating voltage with consecutive cycles cycled for 50 cycles at a current rate of 0.1 C, where the capac-
[52]. Similarly, Fig. 5(f) shows the dQ/dV plot for the VGCFs self- ity retention was 76.14%. Interestingly, the fabricated self-standing
standing anodes, which display a similar trend as the graphite’s electrodes-constructed full-cells were initially charged and used to
peaks [53, 54]. The reduction peaks are observed at 90 and 60 mV illuminate light emitting diodes (LEDs), as shown in Fig. 6(d). Fur-
and the corresponding oxidation peaks at 203, 143, and 103 mV thermore, real time applications of these self-standing electrodes
are attributed, respectively, to the intercalation and deintercalation were carried out to evaluate their flexibility and durability. Ini-
mechanism of Li-ions between the graphene layers. Moreover, we tially, the individual self-standing electrodes were twisted, bended,
have also carried out the HR FE-SEM analysis of the self-standing and rolled over a glass rod to evaluate their flexibility. The elec-
electrodes post cycling as shown in Fig. S6(a & b) to investigate trodes exhibit flexible nature upon bending without producing any
their structural stability under different magnifications. The self- tear, as shown in Fig. 6(a). Furthermore, a prototype pouch cell has
standing electrodes remained intact with no structural defects or been fabricated using the self-standing electrodes with the injec-
morphological disruption even after 50 cycles at 0.1C current rate tion of 0.4 ml of 1.0 M LiPF6 in EC/DEC (1:1 v/v) electrolyte, fol-
indicating its superior stability. lowed by sealing in a PET polymer casing eventually in order to
The satisfactory electrochemical performances exhibited by the perform the electrochemical analysis and other real time applica-
self-standing electrodes in the half-cell configuration, i.e., NCA as a tions. The electrochemical performance of the prototype pouch cell
cathode and VGCF as an anode prompted to investigate their per- is shown in Fig. 6(e & f) and from their galvanostatic charge and
formances in their full-cell chemistries, that are much required for discharge curves, the initial specific charge and discharge capaci-
the real-time applications. Prior fabricating a full cell the mass bal- ties reached 219 and 191 mAh g−1 , respectively, at a current rate
ancing should be carried out for achieving a better electrochemical of 0.1 C in the potential window of 2.7–4.3 V. The coulombic effi-
performance. The capacity attained by the individual NCA cathode ciency of the initial cycle was 87.1% and it increased to above 99%
and VGCF anode in half cell configuration from the above experi- upon successive cycles. Fig. 6(f) shows the cyclic performance of
ments was used for calculating the areal capacities which in turn the prototype pouch cell cycled for 20 cycles at a current rate of
are used to determine the capacity (n/p) ratio for full cell. The n/p 0.1 C, where the capacity retention was 87.5%. For real time appli-
ratio was found to be 1.2:1. Full-cells comprising of self-standing cations the fabricated transparent prototype pouch battery made
NCA as a cathode with a mass loading of 3.66 mg cm−2 and VGCF of self-standing electrodes is charged and are illuminated with a
as an anode with a mass loading of 3.33 mg cm−2 were assem- red LED. Further, upon subjecting the transparent pouch battery to
bled in the similar protocol as followed for the half-cells, except physical disturbances, they could maintain their functionality upon
the Li anode, instead VGCF is employed as an anode. The electro- flexing them in adverse angles, as shown in Fig. 6(g) suggesting

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Fig. 6. (a)(i-iv) The investigation of the flexibility of the self-standing electrodes upon bending, twisting, double folding and rolling respectively. Electrochemical performance
of the self-standing electrodes in full-cell assemblies with NCA-VGCFs cathode and VGCFs anode (b) Galvanostatic charge-discharge curves at 0.1 C. (c) Cyclic performance and
coulombic efficiency for first 50 cycles at 0.1 C. (d)(i–iii) Illumination of a full-cell assembly with red, green and blue (RGB) light emitting diodes. Electrochemical performance
of the self-standing electrodes in prototype pouch cell assembly (e) Galvanostatic charge-discharge curves at 0.1 C. (f) Cyclic performance and coulombic efficiency for first
20 cycles at 0.1 C. (g)(i–v) Illumination of a prototype full-cell pouch with red light emitting diode at various flexing states.

that these 3D-printed self-standing electrodes could be used as a were also successfully achieved. Therefore, we suggest that this
viable method to bridge the need of flexible batteries for commer- strategy of using 3D-printing to fabricate self-standing electrodes
cial flexible electronics. would provide an unprecedented opportunity for developing LIB
power sources with reliable electrochemical properties for diverse
4. Conclusion wearable electronics and other flexible device applications.

Declaration of Competing Interest

Flexible self-standing electrodes were fabricated by an
extrusion-based 3D-printing technology preparing a homoge-
The authors declare no competing interests.
neous suspension of the commercial battery components for the
electrode ink formulation. The VGCFs were used as a conductive Acknowledgments
agent for cathode whereas they were used as a conductive agent as
well as an active material for anode due to their highly conducting This research was supported by the Next Generation Engi-
nature, graphite-like electrochemical behaviour. Furthermore, they neering Researcher Program of National Research Foundation of
can also be used as a replacement for metal current collectors, Korea (NRF) funded by the Ministry of Science and ICT (No.
which might help in enhancing their flexible nature. The influence 2017H1D8A2031138). The authors also thank Dr. Chenrayan Senthil
of each component of the electrode inks was analysed and a ratio for his valuable comments and suggestions during the manuscript
containing a fine balance between the electrochemical perfor- preparation.
mance and flexible nature was identified for both self-standing
cathode and anode electrodes. The electrochemical performance Supplementary materials
of these self-standing electrodes in a coin cell configuration
delivers a reasonable discharge capacity. The flexible nature of Supplementary material associated with this article can be
the self-standing electrodes and their endurance to bending found, in the online version, at doi:10.1016/j.apmt.2021.100980.

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S. Praveen, G.S. Sim, N. Shaji et al. Applied Materials Today xxx (xxxx) xxx

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