Journal of The Electrochemical

Society

Connection of Bipolar Plate with Graphite Felt Electrode for Vanadium

Flow Battery Using a Powder Thermal Unification Method
To cite this article: N. Nambi Krishnan et al 2022 J. Electrochem. Soc. 169 100517

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 Journal of The Electrochemical Society, 2022 169 100517
1945-7111/2022/169(10)/100517/10/$40.00 © 2022 The Electrochemical Society (“ECS”). Published on behalf of ECS by IOP Publishing Limited

Connection of Bipolar Plate with Graphite Felt Electrode for

Vanadium Flow Battery Using a Powder Thermal Unification
Method
N. Nambi Krishnan,1,z Gaurav Gupta,2 Barbara Satola,2 Lisa M. Uhlig,1
Wiebke Germer,1 and Marco Zobel2
1
Institute of Engineering Thermodynamics, German Aerospace Center (DLR), Carl-von-Ossietzky-Str. 15, 26129,
Oldenburg, Germany
2
Institute of Networked Energy Systems, German Aerospace Center (DLR), Carl-von-Ossietzky-Str. 15, 26129, Oldenburg,
Germany

Carbon felt electrodes are usually compressed against the bipolar plates in order to decrease the contact resistance, but it leads to
high pressure drop and consumption of pumping energy in conventional vanadium redox flow battery stacks. This paper describes
the fabrication of an effective way to unify the bipolar plate and graphite felt electrode in order to improve the battery efficiency at
lower felt compression pressure. The unification process involves a thermal fusion technique with a component design consisting of
bipolar plate, graphite felt electrode and connecting powder. The powder comprises either polyvinylidene difluoride or a mixture of
polyvinylidene difluoride and conductive carbon black. The interfacial bonding substance determines the electrical resistance of the
resultant fabricated unified assembly. The electrical resistance results prove that the carbon black proportion in the bonding element
substantially reduces the electrical resistance. The optimum quantity of carbon black in the powder is found to be 40 wt%. Micro-
computed tomography analysis findings indicate that thermally unified assembly interfacial contact electrode porosity is slightly
lower than that of an unbonded sample. A two-cell vanadium redox flow battery stack with integrated unified assembly achieves a
rather constant energy efficiency of 76% during 100 cycles with 5% electrode compression at a current density of 80 mA cm−2.
© 2022 The Electrochemical Society (“ECS”). Published on behalf of ECS by IOP Publishing Limited. [DOI: 10.1149/1945-7111/
ac96a7]

Manuscript submitted May 19, 2022; revised manuscript received July 26, 2022. Published October 12, 2022.

As the world’s population expand day-to-day, the future uni-
versal energy demand will also increase significantly. German
Renewable Energy Act policies emphasize the energy transition
from the use of fossil fuels and nuclear energy to a sustainable
energy which originates from renewable sources. German Federal
Ministry for Economic Affairs and Climate Action declared that the
share of renewable energy for electric power in Germany was 41.1%
in the year of 2021.1 Many renewable energy sources such as wind
and solar power have a wavering energy performance by nature.
Therefore, energy storage systems are urgently needed in renewable
energy exploitation, grid management, load leveling and peak
shaving, backup power systems and the utilization and integration
of renewable energy sources.2–7 Among different energy storage
systems, the all-vanadium redox flow battery (VFB) has received
much attention due to its long cycle life, easy scale development,
quick response time and unrestricted location selection.8,9 This redox
flow battery type was first proposed as an electrochemical storage
system by Skyllas-Kazacos and co-workers in the mid 1980s.10,11
Recently, the use of VFB systems for large scale energy storage has
been demonstrated in different application areas.12–14
Generally, the VFB system is composed of several unit cells
connected in series, two pumps and two tanks for the half-cell
electrolyte solutions. The unit cell consists of an ion exchange
membrane, graphite felt electrodes (GFE), flow frames and bipolar
plates (BPPs). The VFB stack is assembled by using ′n′ number of
unit cell under specific compact force applied through endplates.
This compact force and the thickness of the frames determine the
percentage of porous GFE compression. The percentage compres-
sion of the GFE reduces the internal ohmic resistance of VFB which
improves the VFB efficiency. However, at the same time, high
compression of the GFE leads to a higher electrolyte pressure drop
and an increase in pumping energy consumption.15 From literature,
VFB test results reveal that both ohmic and activation polarization
are the key factors which affect the performance. The effective way
to reduce the activation polarization is to increase the electroche-
mical reactivity of electrode materials. By optimizing the VFB stack
z
E-mail: nambikrishnan.nagappan@dlr.de
design, reducing the internal resistance of the stack, enhancing the
conductivity of electrodes, bipolar plates (BPP) and ion-conducting
membranes, the ohmic polarization can be significantly
decreased.16,17 The compression rate determines the porosity and
contact area of the GFE to the BPP and thus effects electron transfer.
Recently, the influence of GFE compression and its effect on VFB
was reported in literature.18–21 Park et al. found that a VFB with a
20% GFE compression showed the highest energy efficiency. When
the GFE compression exceeded above 20%, the energy efficiency
was decreased.17 The porosity of the GFE affects the electron
transfer in GFE. Zhang et al. reported that the area specific resistance
of 20% compression ratio of polyarylonitrile based graphite felt
(PAN-GF) was lower than that of rayon based graphite felt (R-GF)
with an increase of current density.22 Therefore, the compression as
well as the choice of GFE material plays an important role in charge/
discharge properties of the VFB cell.
To overcome the adverse effects of compression, few studies
have been dedicated to combine the graphite felt and BPP for VFB
applications so far. Qian et al. described an adhesive conducting
layer (ACL) method in which thermoplastic phenol formaldehyde
resin, hexamethylene tetraamine, graphite powder and Vulcan® XC-
72R were used with a weight ratio of 2:0.2:1:1 as a connecting and
conducting adhesive material. This method provided high electrical
conductivity, low area resistivity, zero electrolyte permeation, and
high energy efficiency.23 Lim and Lee discussed a carbon fiber/
polyethylene composite assembly to decrease the electrical contact
resistance between the BPP and electrode by thermoplastic welding
process.24 The integrated assembly based VFB achieved an energy
efficiency of 84% which was higher than that of an unbonded
assembly (82%). Most recently, Dongjiang et al. investigated a high-
temperature conductive binder to prepare an integrated electrode
BPP assembly. The author found that the VFB with the assembly
had better performance than those with no binder and it operated
well without electrode compression at a high current density up to
150 mA cm−2.25
Although the integration methods have been studied to some
extent in literature, there is a lack of knowledge regarding the
selection of binding material composition and its influence in
VFB performance. The research findings from the authors23–27
 Journal of The Electrochemical Society, 2022 169 100517
encouraged to propose a simple connecting powder based thermal
unification method to combine the components and to reduce the
contact resistance between the GFE and the BPP. Consequently, it is
expected that this technique could decrease both the electrolyte
pressure drop and the pumping energy consumption in VFB. In
particular, the presence of carbon black within the connecting
powder and its implications for possible improvements was inves-
tigated in this study. The effect of carbon black amount and type
(Super P conductive carbon black, Vulcan-XC72R and Black Pearl
2000) was studied. Micro-computed tomography (CT) technique
was used to determine the structural morphology of the thermally
unified interface and the results are reported. Charge/discharge
behavior, the stack resistance, coulombic, voltage and energy
efficiency at a low GFE compression of 5% were evaluated in a
two cell VFB stack. The conventional unbonded assembly based
VFB stack performance was also examined and reported at 5% and
20% GFE compression for comparison.
Experimental
Fabrication of unified graphite felt electrode and bipolar plate
assembly.—A polyacrylonitrile (PAN) based GFE (SIGRACELL
GFD 4.6 EA; thickness 4.6 mm, area weight 465 g m−2, open
porosity 94%, SGL Carbon SE, Germany) and graphite PVDF
composite BPP (SIGRACELL PV15, SGL Carbon SE, Germany)
were used for this study. In order to prepare thermally unified
samples, first the BPP and GFE were cut in the required dimensions.
For electrical resistance measurements, BPP and GFE discs of
2.5 cm diameter were punched out. Similarly, BPP with 1.6 cm
diameter and GFE with 1 cm diameter disc samples were prepared
for CT analysis. For VFB cell cycling the BPP was cut with respect
to the frame dimension of 8.5 cm × 7.4 cm and the felt to 6 cm ×
4 cm.
The BPPs were cleaned with deionized water followed by ethanol
and they were dried at room temperature. Thermally activated GFEs
were received from SGL and they were used without further thermal
activation. The connecting powder was manually prepared by
mixing Super P conductive carbon black (⩾99%, abcr GmbH,
Germany) and thermoplastic fluoropolymer (PVDF, Solef® 6010/
1001: powder, particle size <300 μm, density 1.7–1.8 g cm−3,
melting temperature 170 °C–175 °C, decomposition temperature
>290 °C, Germany) at different ratios. Each individual connection
powder was used for single side thermally unified assembly (GFE-
BPP) fabrication. The PVDF content was kept constant with an
amount of 2.08 mg cm−2. The amount was found to be satisfactory
for unification of BPP-GFE interface surface without any delamina-
tion. However, Super P conductive carbon black content was varied
from 0 to 50 wt% in the connecting powder. The sample code was
named as HP_N; where the “N” represented the weight percentage
of carbon black. The connection powder HP_50 was prepared by
weighing PVDF:Super P conductive carbon black with an amount of
2.08 mg cm−2: 2.08 mg cm−2 and it was physically mixed by
stainless steel spatula for 10 min Similarly, other connecting powder
was made by changing the amount of Super P conductive carbon
black 1.39, 0.90, 0.53, and 0.24 mg cm−2 for HP_40, HP_30,
HP_20, and HP_10, respectively. The connecting powders were
freshly prepared for the binding process between BPP and GFE.
A hot-press device (P/O/WEBER GmbH, PW 20H, Germany)
was applied for thermal fusion. Thermoplastic engineering material
based both circular as well as rectangular distance plates were
designed (Solid edge 2020, Siemens; desktop 3D printer, formlabs,
Form 2, United States) with appropriate BPP and GFE thickness
dimensions for the fabrication of GFE-BPP assembly and double
side thermally unified (GFE-BPP-GFE) assembly separately. The
schematic procedure of the thermal unification for VFB performance
study is shown in Fig. 1. The fabrication of unified GFE-BPP
consists of four main steps (Fig. 1a). The BPP was fixed in a distance
plate which has the accessible active GFE area of 24 cm2 and this
set-up was placed on a stainless steel plate. The thickness of the plate
is ∼600 μm. Then, the mixed connecting powder (e.g. HP_40;
50 mg PVDF and 33.4 mg carbon black) was manually distributed in
the open area of the bipolar plate. A GFE was arranged above the
connecting powder. This sandwich was closed with another stainless
steel plate. The systematic arrangement was positioned in between
the hot press discs. The hot press temperature was kept at 170 °C
which is very close to the PVDF melt process temperature of 177 °C.
The hot press pressure was fixed at 1 kN for both thermally unified
assemblies, GFE-BPP (Fig. 1a) and GFE-BPP-GFE (Fig. 1b). But,
thermal unification time duration was varied from 2 min to 12 min
with an increment of 2 min. After thermal unification time duration,
the pressure was released. The assembly was gently removed from
the hot press device and it was stored inside the fume hood to attain
room temperature.
Finally, the thermally unified assembly was carefully detached
from the distance plate. The hot press duration has been optimized in
order to obtain non-detachable thermally unified assembly. A stable
GFE-BPP assembly needs 10 min to achieve perfect adhesion
whereas GFE-BPP-GFE assembly requires 12 min under same
temperature and pressure. The similar fabrication method was used
to fabricate disc samples for electrical resistance measurement
(GFE-BPP-GFE assembly disc sample with area of 4.9 cm2) and
CT analysis (GFE-BPP assembly disc sample with area of
0.785 cm2) with their corresponding connecting powder as well as
disc type distance plate. Both BPP-GFE as well as GFE-BPP-GFE
were also fabricated with 40 wt% of other type of carbon materials
mixed with PVDF in the connecting powder such as Vulcan-XC72R
(VC) (sample named as HP_40-VC) and Black Pearl 2000 (BP)
(sample named as HP_40-BP) for VFB two-cell stack performance
evaluation.
Electrical resistance.—The electrical through-plane resistance
measurement of thermally unified GFE-BPP-GFE disc samples were
evaluated by four-point-probe method using a Zwick/Roell Z1.0
instrument which was connected with Tektronix DMM 4050 6–1/2
Digit Precision Multimeter. The sandwiched samples were placed
between two gold plated copper stamps (d = 2.5 cm) (Fig. 2).
During the measurement, the GFE was subjected to 5% as well as
20% compression by adjusting the force in the measurement
machine. The total electrical resistance of a GFE-BPP-GFE as-
sembly includes the contribution of the contact resistances in
addition to the bulk resistance of the individual components.
Therefore, the total electrical resistance can be estimated as shown in
Eq. 1:
R (E) = 2RAu(Cu)− GF + 2R GF + 2R GF − BPP + RBPP [ 1]
Where, R(E) is total electrical through-plane resistance, RAu(Cu)-GF is
interfacial contact resistance between the gold plated copper stamp
and the GFE, RGF is bulk resistance of the GFE, RGF-BPP is
interfacial contact resistance between the GFE and the BPP and
RBPP is bulk resistance of the BPP. The electrical resistance of
conventional unbonded GFE-BPP-GFE assembly was also measured
for comparison.
Computed tomography sample preparation, imaging and ana-
lysis.—CT (SkyScan 1172, Bruker, Belgium) was employed to
produce high resolution images of unbonded GFE-BPP and ther-
mally unified GFE-BPP sample (HP_40). The samples were held in
a 3D printing polypropylene housing to achieve a 5% GFE
compression. The scan resolution was set at 1.64 μm per pixel
with a source voltage of 80 kV. The rotation angle was rotated from
0° to 180° with rotation step of 0.18°. The generated data consists of
a set of cross-section images in gray scale with each image as an
average of 6 frames. The recorded gray scale image data was loaded
onto the NRecon software (SkyScan, Bruker, Belgium) were 3D
images were reconstructed. The range of the histogram from the gray
scale, value of ring artefact reduction and beam hardening were kept
the same for both samples. A 2D axial plane image of the interface
 Journal of The Electrochemical Society, 2022 169 100517

Figure 1. Schematic representation of fabrication method for unified BPP and GFE for VFB a) single side thermally unified assembly (GFE-BPP) and b) double
side thermally unified assembly (GFE-BPP-GFE).

was chosen as region of interest (ROI) (3000 μm × 3000 μm) to
visualize the properties of the bonding. The average thickness of the
connecting interface of the unified BPP-GFE assembly was deter-
mined by measuring the thickness of the PVDF layer at 20 random
points. Two volumes of interest (VOI) of the reconstructed data were
chosen to analyze the porosity. VOI1 consists of the interface
between the BPP and GFE (3000 μm × 3000 μm × 130 μm) and
VOI2 contains part of the GFE bulk at 5% compression including
VOI1 (3000 μm × 3000 μm × 2000 μm). The analysis of the two
VOIs was performed in the following order (a) filtering and
despeckling operation were done to eliminate the background noise,
(b) bitmap operation (black as background/white as matter) (c) 3D
analysis operation was done to determine the porosity of the VOIs.
VFB assembly and testing.—A two-cell VFB short-stack
(SCHMID Group, Germany) with exchangeable flow frame thick-
ness for applying the respective compression forces of 5% and 20%
compression on the GFE was designed. Two thermally unified GFE-
BPP and one GFE-BPP-GFE assembly were prepared for a two-cell
VFB. The performance evaluation with unified assemblies of
samples HP_40 and HP_0 was conducted in this VFB study with
5% compression. The conventional unbonded assembly based VFB
was also studied for comparison at 5% and 20% compression. The
active GFE area for a cell was 24 cm2. The proton exchange
membrane (Nafion 117, QUINTECH, Germany) was cleaned with
10% H2O2 for 30 min at 80 °C and it was used as the separator. The
copper plates and steel frames were employed as current collectors
 Journal of The Electrochemical Society, 2022 169 100517
Figure 2. Experimental set-up for electrical resistance measurement with
thermally unified GFE-BPP-GFE sample.
and end plates, respectively. A volume of 100 ml solution consisting
of 1.6 M V3+/4+ (50%:50%; V3+:V4+)/4 M SO42− (GFE, Germany)
was used as positive and negative electrolyte. The electrolyte was
cyclically pumped (KNF, Germany) at a flow rate of 60 ml min−1.
Charge-discharge cycling tests were recorded using a potentiostat
(Solartron Analytical 2100 A, Ametek scientific instruments, USA).
To avoid corrosion of GFE and BPP, the cut-off voltages for charge
and discharge were set to 3.2 V and 1.6 V respectively. All tests
were done at room temperature and the electrolyte was purged with
nitrogen gas throughout the measurement to prevent the oxidation of
vanadium species. The charge/discharge of the cell was executed for
100 cycles at a constant current density of 80 mA cm−2. The
coulombic efficiency (CE), voltage efficiency (VE) and energy
efficiency (EE) of the cell were calculated.28 Electrochemical
impedance (EIS) was performed from start frequency of 100 kHz
to end frequency of 0.25 Hz. The two-cell VFB stack initial ohmic
resistance values were obtained from the high-frequency intercept of
the Nyquist plot.
Results and Discussion
Electrical resistance analysis.—Super P conductive carbon
black and PVDF polymer based connecting powder has been
employed in between BPP and GFE. PVDF polymer has been
chosen due to the presence of PVDF in the composite BPP as binder
material. Therefore, it is expected that the interaction between the
homogeneous polymers enhances adhesion between the BPP and the
GFE during thermal unification technique. The fabrication of unified
GFE-BPP consists of four main steps as described in section 2.1. In
the present investigation, the required amounts of PVDF powder and
thermal unification time duration have been optimized to unify GFE-
BPP assembly respective to its unification area at constant tempera-
ture and pressure. The optimized content of PVDF powder is
2.08 mg cm−2 for BPP-GFE interface surface assembly. It is
noteworthy to mention that a stable GFE-BPP and GFE-BPP-GFE
assembly could be achieved with unification time duration of 10 min
and 12 min, respectively. In all cases, less than the time duration
leads only to partial unification between the GFE and the BPP. In the
next step, the connecting powder’s carbon black ratios were varied
from 10 to 50 wt% with respect to the PVDF polymer amount and
were applied in the assembly unification process. Since the different
fusion layers at the interface between the GFE-BPP-GFE can add to
the electrical through-plane resistance of the assembly and thus to
the performance of the VFB, electrical resistance measurements
have been performed and compared with the unbonded GFE-BPP-
Figure 3. Electrical resistance test results for thermally unified GFE-BPP-
GFE disc samples and unbonded GFE-BPP-GFE sample with area of 4.9 cm2
at (a) 5% GFE compression and (b) 20% GFE compression.
GFE assembly. The obtained electrical resistance results are shown
in Figs. 3a and 3b for all samples with GFE compression value of
5% and 20%, respectively.
In general, the electrical resistance is decreasing with higher GFE
compression since the contact resistance between the BPP and GFE is
reduced. In both compression, HP_0 sample provides a relative high
resistance value. It is due to the absence of conductive carbon black
and formation of a rather insulating polymer layer at the interface of
both components. In both compression investigations, it is clearly
observed that the electrical resistance value is decreasing with
increasing the content of Super P conductive carbon black up to 40
wt% in the connecting powder. Compared to HP_0 sample, the
presence of 40 wt% Super P conductive carbon black in the connecting
powder not only sustain the adhesion between the GFE and BPP but
also decreases the resistance value to about 30% with 5% compression,
and to about 35% with 20% compression. The high resistance of the
isolating PVDF is completely compensated by the addition of carbon
filler. Both HP_40 and unbonded GFE-BPP-GFE sample have a
resistance of 0.39 ohm cm2 at 5% compression. However, the electrical
resistance value is again increasing compared to HP_40 when the
carbon black content rises to 50 wt%. From the material point of view,
the interaction between the amount of carbon black with PVDF
influences the thermal fusion behavior between GFE and BPP during
the fusion process. Most interestingly, when the carbon black content
is 50 wt% or above 50 wt% in the connecting powder severe
 Journal of The Electrochemical Society, 2022 169 100517
delamination occurs between GFE and BPP. Additionally, HP_50 does
not provide reproducible thermally fused samples during the same
thermal fusion conditions. In general, the properties of the connecting
layer depend on the PVDF particle size, and its distribution with the
presence of carbon content, which play a major role in the adhesion
between GFE and BPP and also in the resultant electrical resistance
value. Since HP_0 and HP_40 showed the worst and best electrical
through-plane resistance values compared to all other unified assem-
blies, they were chosen for further investigation.
Structural analysis.—In the next step, morphological CT ana-
lysis was performed to investigate the interface structural character-
istics of thermally unified HP_40 and unbonded GFE-BPP assembly.
CT characterization was already reported by other research groups
for GFE properties such as surface area, porosity, fiber diameter,
volume and corrosion of GFE structure.29–31 As far as we know,
there is no CT characterization literature report on unified GFE-BPP
assembly, yet. The nature of the 2D axial plane images of GFE and
the interface of unbonded GFE-BPP assembly and HP_40 are shown
in Fig. 4. The embedded PVDF of HP_40 is clearly visible as white
spots in the coronal and axial plane images at the interface between
unified GFE-BPP. The PVDF did not spread out to the interior of the
GFE, but remained at the interface during unification. The average
thickness of the connecting interface was determined as 87 ± 43 μm.
Thus, for analysis of the interface porosity, a VOI thickness of
130 μm was chosen. At 5% GFE compression, the 3D CT analysis
of the interface (VOI1) provides a porosity of 87% and of 75% for
the conventional unbonded assembly and HP_40, respectively. The
key reason for the interface porosity reduction of HP_40 may be
attributed to the additional presence of Super P conductive carbon
black and PVDF in the connecting layer. However, by unifying the
GFE and BPP the total GFE porosity with 86% did not change
significantly compared to the unbonded sample with 88% (VOI2).
Thus, by introducing a connecting layer, the total porosity of the
GFE is rather unaffected.
VFB two-cell stack performance analysis.—Thermally unified
HP_0 and HP_40 samples have been selected for two-cell VFB test
Figure 4. Micro computed tomography 2D coronal plane images (middle) of samples at 5% GFE compression for unbonded BPP-GFE assembly (top) and
HP_40 (bottom) and their corresponding 2D axial plane of GFE (left) and interface between GFE and BPP (right). The scan resolution is 1.64 μm/pixel. The ROI
of the 2D axial plane images is 3000 μm × 3000 μm.
in order to assert charge/discharge behavior in battery operation
environment with 5% GFE compression. For comparison study, the
conventional method with unbonded assembly has also been studied.
At a current density of 80 mA cm−2, a charge/discharge test using a
VFB two-cell stack with Nafion 117 as ion exchange membrane was
performed. The typical charge/discharge curves for HP_0, HP_40
and conventional unbonded assemblies are shown in Fig. 5. The
higher potential during charge and lower potential during discharge
illustrate the V4+/V5+ vs V2+/V3+ redox reactions.16 The longest
cycling durations could be achieved when using the HP_40
thermally unified assembly (Fig. 5b) in VFB stack compared to
the HP_0 (Fig. 5a) and the conventional unbonded assembly
(Fig. 5c), as indicated by the extension of the charging and
discharging cycle time. It implies that HP_40 thermally unified
assembly based VFB stack can convert or store more energy,
respectively, and works more efficiently probably due to a lower
starting charge overpotential owing to lower activation polarization.
At the same time, higher starting discharge potential of HP_40 paves
way to higher VFB performance. The capacity fade from cycle 11 to
cycle 100 develops due to crossover effects and side reactions which
are typical for VFB. The total time duration for 100 charge/discharge
cycles for different VFB two-cell stack systems is shown in Table I.
The average cycle duration of HP_40 powder based thermal
unification assembly VFB stack test is 24% (7412 min) higher
than that of conventional unbonded BPP-GFE assembly
(5977 min) which leads to increase in exploitable storage capacity.
Since the cycle durations of HP_40 are longer compared to the other
samples, the absolute capacity fade after 100 cycles is higher owing
to more probability of crossover of vanadium species through the
membrane.
Most commonly, CE, VE, EE and discharge capacity are the
general standards to estimate the performance of VFBs. These
values can be obtained from evaluation of the charge/discharge
curves.32 The efficiencies and discharge capacity retention develop-
ment for 100 cycles of VFB two-cell stack with HP_0, HP_40 and
conventional unbonded assembly are displayed in Table I. In
addition, the obtained results of each 100th cycle are presented in
Fig. 6.
 Journal of The Electrochemical Society, 2022 169 100517
Figure 5. Charge/discharge curves of VFB two-cell stack at a current
density of 80 mA cm−2 with unified GFE-BPP assembly (a) HP_0, (b)
HP_40 and (c) conventional unbonded GFE-BPP assembly. The flow rate is
60 ml min−1. The GFE compression inside the stack is 5%.
At constant current density of 80 mA cm−2 and GFE compres-
sion of 5%, the VFB stack CE is determined by the ratio of the
charge output to the charge input. The CE value is decreasing with
cycle number owing to electrolyte crossover and side reactions. The
CE value for HP_40 based assembly is slightly lower than that of
HP_0 and unbonded conventional based assembly (Table I and
Fig. 6). It may be attributed to the longer charge/discharge time of
each cycle and thus to more probability of electrolyte crossover
Figure 6. Discharge capacity retention and efficiencies of VFB two-cell
stack at a current density of 80 mA cm−2 for (a) HP_0, (b) HP_40 and (c)
conventional unbonded BPP-GFE assembly. The flow rate is 60 ml min−1.
The GFE compression inside the stack is 5%.
(Fig. 5). This assumption is also confirmed by the discharge capacity
retention development. The discharge capacity is decreasing during
cycling in all cases. However, the discharge capacity retention in [%]
of HP_40 is the highest (Fig. 6) followed by the unbonded
conventional assembly and HP_0 assembly. Nevertheless, HP_40
shows the highest absolute discharge capacity in [mA h] when
comparing cycle number 100 between the different assemblies at 5%
compression (Table I) which gives evidence that the VFB two-cell
stack with HP_40 works the most effective and provides best
exploitation of the electrolyte storage capacity.
The VE is measured by the potential difference between the
charge and discharge processes. Mainly, VE value is affected by the
ionic conductivity of the membrane, bulk and contact resistances of
 Journal of The Electrochemical Society, 2022 169 100517
Table I. Results of electrochemical characterization of the 100th cycle of different VFB two-cell stack arrangements at current density of 80 mA cm−2, their ohmic resistances after 1st and 100th
charge/discharge operation, and total cycle time.

Ohmic resistance (Ω.cm2)

Two-cell VFB stack Discharge capacity (mA h) Energy density (Wh/L) CE (%) VE (%) EE (%) Time (min.)c)
1st 100th

HP_0a) 1524 8.4 99 70 70 9 9.1 5667

HP_40a) 1855 11.2 95 80 76 5.7 5.6 7413
Conventional assemblya) 1507 8.9 96 78 74 8.2 5.7 5977
HP_40-VCa) 1880 11.1 97 77 75 6.5 6.6 7306
HP_40-BPa) 1558 8.6 97 71 69 8.4 8.5 5840
Conventional assemblyb) 1879 11.2 97 79 77 6.1 5.9 7317

a) 5% GFE compression, b) 20% GFE compression, c) total time of 100 charge/discharge cycles, VC-Vulcan-XC72R; BP-Black Pearl 2000.
 Journal of The Electrochemical Society, 2022 169 100517

Figure 7. Impedance analyses of different two-cell VFB stack arrangements (a5% GFE compression; b20% GFE compression) after an interval of charge/
discharge process.

GFEs and BPPs.33 The HP_40 based VFB shows higher VE value
(80%) compared to that of the other tested samples in the two-cell
VFB stack. The VE value of HP_0 is 70% only. The ohmic
resistance results from EIS of the VFB two-cell stack measurements
after 1st and 100th charge/discharge cycle is displayed in Table I.
The Nyquist curves for all the tested VFB two cell stack have shown
in Fig. 7. Generally, ohmic resistance is associated with the sum of
resistances from the membrane, GFE, BPP, liquid electrolyte, and
electronic contact resistance. In this study, the ohmic resistance
values after 1st charge/discharge cycle is observed in the order
HP_40a (5.7 Ω.cm2) < Conventional assemblya (8.2 Ω.cm2) <
HP_0a (9 Ω.cm2) for the assembled two cell VFB stack with 5%
GFE compression. The initial ohmic resistance (after 1st charge/
discharge cycle) value is reduced from 8.2 (conventional assemblya)
to 6.1 Ω.cm2 (conventional assemblyb) when the GFE compression
is increased from 5 to 20%. It proves that conventional assembly
based two-cell stack VFB’s initial ohmic resistance of the cell
depends on the electrode compression strongly. Even though
unbonded GFE-BPP-GFE assembly and HP_40 assembly shows a
very close ex situ resistance value ((∼0.39 Ω.cm2; Fig. 3a), the
in situ impedance resistance value is not same. The reason is ex situ
electrical through-plane resistance was only measured on dry
assemblies influenced by the contact and bulk resistances of the
BPP and GFEs. But, the in situ impedance ohmic resistance arises
from an interaction of more components, such as the membrane, the
electrolyte, the GFE compression, contact resistances, etc and
influences the total performance of the VFB. It is also interesting
to note that the low and high frequency resistance value in EIS is
almost same for conventional assemblya and HP_40a after100th
charge/discharge cycle (Fig. 7). It is due to the maximum wettability
and activation of the electrode surface during charge-discharge
cycles. Thermally fused HP_0 based two-cell VFB assembly
 Journal of The Electrochemical Society, 2022 169 100517
Figure 8. Energy efficiency comparison of thermally unified assembly (HP)
with different carbon filler in the connecting powder and unbonded GFE-
BPP assembly (UB) based VFB two-cell stack at current density of
80 mA cm−2. The flow rate is 60 ml min−1. GFE compression value for
VFB stack is specified in brackets.
Figure 9. Simplified schematic interpretation of different conductive fillers
with PVDF at the interface between unified GFE-BPP.
displays high ohmic resistance value (9 Ω.cm2) which is also
observed in the electrical through-plane resistance value of HP_0
(1.3 Ω.cm2) assembly in Fig. 3a. The main reason for the lower VE
value of HP_0a (70%) may be attributed to resistance resulting from
ohmic, charge transfer and diffusion processes during charge-
discharge operation. In contrast, the high VE value of HP_40a
(80%) could arise from better electrical connection of the unified
GFE-BPP via the HP_40 layer. The lower value in both high and low
frequency resistance for HP_40a ensure the better VFB performance
than that of other thermally unified assemblies (Fig. 7.).
The product of CE and VE provides EE which represents the
overall efficiency of VFBs.34,35 The VFB performance depends on
several elements such as vanadium ion precipitation, change in GFE
polarization, change in electrolyte/membrane/GFE resistance etc
The two-cell VFB stack with thermally unified HP_40 assembly
exhibits an EE value of 76% in cycle 100. It is higher than that of
unbonded conventional assembly (74%) under the same GFE
compression conditions. The VFB with HP_0 GFE-BPP assembly
with no carbon black within the connecting powder has the lowest
EE with 70%.
In order to determine the effect of conductive filler in the
connection powder, commercially available carbon fillers BP and
VC were considered in comparison to Super P conductive carbon
black. The above mentioned alternative carbon filler based thermally
unified HP_40-BP and HP_40-VC samples were prepared with an
amount of 40 wt% carbon filler—analogous to the best performing
HP_40 sample—and their VFB two-cell stack performance was
evaluated (Table I). The obtained VFB EE results are compared and
displayed in Fig. 8. It is important to mention that in Fig. 8 the EE of
the unbonded GFE-BPP assembly at 5% GFE compression is taken
from Fig. 6c for comparison. However, fresh HP_40 thermally unified
samples based on Super P conductive carbon black are used to
assemble the VFB two-cell stack and the VFB performance is shown
in Fig. 8. The EE value for HP_40 based assembly did not change
greatly and it clearly proves that the proposed thermally unified GFE-
BPP with connecting powder in this study is reproducible. As already
mentioned above, the EE of HP_40 at 5% compression and the
unbonded GFE-BPP at 20% compression show similar values.
The VFB stack performance as a function of carbon filler within
the connecting powder is in the order of HP_40 > HP_40-VC >
HP_40-BP. HP_40 with Super P conductive carbon black offers
energy efficiency of 76% from initial to final cycle without any
significant fluctuations. Super P conductive carbon black has the
lowest surface area (62 m2 g−1) compared to VC (241 m2 g−1) and
BP (1485 m2 g−1).36 This could indicate that Super P conductive
carbon black might contain the largest particles followed by VC and
BP. Large particles might contribute better to the electrical con-
nectivity between GFE and BPP since they can be arranged with a
higher likelihood into a conductive network (Fig. 9). In contrast, the
electrical connection path of smaller particles might be disrupted
more likely and the particles might be electrically separated more
easily within the PVDF binder. In addition to the particle sizes and
their distribution, also the shape, porosity, surface chemistry,
electrical conductivity and arrangement of particles might have an
influence on the electrical connectivity and thus the performance of
the unified GFE-BPP assemblies. The results show that the carbon
black type needs to be properly selected for the unification process in
order to receive good VFB efficiencies.
In all cases where 40 wt% or less carbon black was added to the
connecting powder, the thermally unified BPP-GFE and GFE-BPP-
GFE assemblies show satisfying bonding properties since they do
not undergo any delamination during 100 cycles of the VFB stack
measurements. The present study implies that the proposed thermal
unification method can offer a beneficial effect in mitigating the
interfacial contact resistance between the BPP and GFE while
reducing the GFE compression at the same time. Eventually, this
thermal unification technique is also a suitable way to decrease VFB
assembly duration in industry as the number of single parts handled
during stack manufacturing is reduced. Further research should focus
on pressure drop measurements to give evidence for expected
reduction of pumping energy consumption. In addition, scaling up
the unified components would allow to investigate the effects in
large scale VFB systems.
Conclusions
In this study, a thermal unification method of BPP with GFE has
been considered in order to maintain a low contact resistance between
both components while reducing GFE compression within VFB
stacks. The proposed objective of thermally assembling unified
BBP-GFE components was successfully achieved with connecting
powder containing PVDF and carbon filler. After thermal unification
process, the thermally unified assembly with PVDF and carbon filler
provided lower electrical through-plane resistance value than that of
the connecting powder containing PVDF only. Thermal unification
conditions as well as connecting powder composition were optimized
 Journal of The Electrochemical Society, 2022 169 100517

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