Report Activities

November 8, 2017
 CONTENTS

Electrode (16 cm2)

• Oven Influence
• Plasma Treatment

VRFB Modeling

• Results

02-02-2022
 OVEN INFLUENCE: Cycling Tests
Operating conditions:
i = 80 mA·cm-2 Direction
Area = 16 cm2  Oven
Flowrate/ UP DOWN
E: 0.8 – 1.6 V mL·min-1 CE VE EE VE EE
CE (%)
Compression = 25 % (%) (%) (%) (%) (%)
E202 10 98; 98 70; 69 69; 67 99; 98 80; 83 79; 81
E202: with air k feeding
E101: with exhaustion E202 no air k 10 97 72 70 99 80 79
E003: no air k feeding
and no exhaustion E202 no air k,
no ramp
10 98 68 66 - - -
UP: side up during the E202, 425ºC,
thermal treatment
no air K, no 10 - - - 99 82 81
ramp
turned to the bipolar
98; 98; 75; 74; 73; 72;
plate E101A 10 98; 98 71; 70 70; 69
99 73 72
DOWN: side up during
the thermal treatment E003 10 98; 98 82; 83 80; 81 98; 98 82; 81 80; 79
turned to the membrane
02-02-2022 3
PLASMA TREATMENT: Cycling Tests
Operating conditions:
i = 80 mA·cm-2 Gas: air
Area = 16 cm2 Pressure: 1.2 mbar
E: 0.8 – 1.6 V Power: 100 W
Compression = 25 %
Flowrate/
 Treatment # cycles CE (%) VE (%) EE (%)
mL·min-1
2 minutes 10 3 99 62 62

3 minutes 10 3 98 70 69

4 minutes 10 3 99 69 68

10 minutes 10 3 99 73 73

20 minutes 10
02-02-2022 4
 FUTURE

 Electrodes (16 cm2)

 Continue the oven influence study;
 Continue the plasma treatment study;
 Study the effect of the deposition of carbon nanoparticles on the electrode.

 5-cell stack assembly (1250 cm2)

02-02-2022
VRFB MODELING

02-02-2022 6
 VRFB MODELING: Inputs
Electrode (GFD 4.6 EA, Operation conditions
SGL) • Steady state
• Compression: 20% • Inlet flow per cell: 0.2 L·min-1
• Porosity: 0.889 • Outlet pressure: 101 kPa
• Pore diameter: 17.6 µm • Iteration number: 5 000
• Active area: 300 cm2
• Thickness: 3.68 mm
• Kck = 4.28
Electrolyte
• Incompressible fluid
• Laminar flow
• Vanadium concentration:
0.75 M V3+ and 0.75 M V4+
• Density: 1360 kg·m-3
• Viscosity @ 25 ºC: 3.04 cP
02-02-2022 7
 VRFB MODELING: Inputs

Permeability
• Fluent generic equation • Carman-Kozeny equation
𝐷𝑃 2 𝜀 3 𝐷 𝑃2 𝜀
3
𝛼= 𝛼=
1 50 (1 − 𝜀 )2 16 𝐾 𝑐𝑘 (1 − 𝜀 )2

Fitting parameter
Darcy’s Law
• Laminar flow
𝜇
𝛻 𝑝=− ⃗
𝑢
𝛼

02-02-2022 8
 VRFB MODELING: Inputs

Viscosity µ

2− 0.61 2 − 2.05
+ 𝐶 ∙ [ SO ] ∙ [ SO ] +𝐺 ∙ [ SO
3.13 0.74 2.02
[V T ] 4 T + 𝐷 ∙𝑇
0.73
+𝐸 ∙ [V T] 4 T +𝐹 ∙ [V T ] ∙𝑇
1.99

- Total vanadium concentration in molL-1

- Total sulfate ion concentration in molL-1
– Temperature in ºC

A, B, C, D, E, F and G – Empirical constants

Source: M. Skyllas-Kazacos, L. Cao, M. Kazacos, N. Kausar, and A. Mousa, “Vanadium Electrolyte Studies for the Vanadium Redox Battery-A Review” (ChemSusChem). 2016.

02-02-2022 9
VRFB MODELING: Results

Results
• Δ = 186 mbar
• Highest residual convergency: 9x10-14
• Δ = -2x10-16 kg·s-1

02-02-2022 10
 VRFB MODELING: Inputs
Electrode (GFD 4.6 EA,
Operation conditions
SGL) • Steady state
• Compression: 10% • Inlet flow per cell: 0.4 L·min-1
• Porosity: 0.90 • Outlet pressure: 101 kPa
• Pore diameter: 17.6 µm • Iteration number: 5 000
• Active area: 1250 cm2
• Thickness: 4.17 mm
• Kck = 4.28
Electrolyte
• Incompressible fluid
• Laminar flow
• Vanadium concentration:
0.75 M V3+ and 0.75 M V4+
• Density: 1360 kg·m-3
• Viscosity @ 25ºC: 3.04 cP

02-02-2022 11
VRFB MODELING: Results

Results
• Δ = 89 mbar
• Highest residual convergency:
6x10-4
• Δ = 7x10-6 kg·s-1

02-02-2022 12
 VRFB MODELING: Viscosity
f(x) = NaN x + NaN
R² = 0
ΔP vs µ, const porosity
1300
f(x) = 243.736693629888 x + 7.87420761893145
Analysis
1200 R² = 0.999999994481445 • The lower the porosity, the
1100
1000
more important viscosity
900 becomes to determine pressure
800 drop.
ΔP /mbar

700
600
500
400
300
Determine porosity of
200 electrode and
100
viscosity of electrolyte
0
1 1.5 2 2.5 3 3.5 4 4.5 5 5.5

µ /cP

02-02-2022 13
 VRFB MODELING: Porosity

ΔP vs Porosity, const µ
1300
Analysis
1200 • The lower the viscosity, the less
f(x) = 81866.6666666674 x² − 157846.666666668 x + 76230.0000000007
1100 R² = 1 important porosity becomes to
1000
900
determine pressure drop;
800 f(x) = 57866.6666666856 x² − 111606.6666667 x + 53917.000000015 • Non-linear behaviour
R² = 1
demonstrates how importante
ΔP /mbar

700
600
500
porosity is to determine
400
f(x) = 32266.6666666773 x² − 62286.6666666855 x + 30119.0000000084
R² = 1 pressure drop.
300
200
100
0
0.84 0.85 0.86 0.87 0.88 0.89 0.9 0.91 0.92 0.93 0.94

Porosity /au

02-02-2022 14
 VRFB MODELING: Pressure drop

Darcy’s Law (DL) Darcy-Weisbach

(DW) µ electrolyte ∙ 𝑙 chan ∙ 𝑄
𝜇 ∙𝑙 el ∙ 𝑄 Δ 𝑃 chan=3 2
Δ 𝑃 el = 3
𝛼 ∙ 𝑤 el ∙h el 𝑁 chan ∙ 𝑤chan ∙ hchan
Δ 𝑃 ely =𝜌 electrolyte ∙ 𝑔 ∙𝑙 el Δ 𝑃 chan
y =𝜌 electrolyte ∙ 𝑔 ∙ 𝑙 y ,chan

Δ 𝑃 eltotal= Δ 𝑃 el + Δ 𝑃 ely Δ 𝑃 chan

total = Δ 𝑃 chan +Δ 𝑃 chan
y

Δ 𝑃𝑡𝑜𝑡𝑎𝑙 = Δ 𝑃 eltotal +2 ∙ Δ 𝑃 chan

total

Source: A. Tang, J. Bao, and M. Skyllas-Kazacos, "Studies on pressure losses and flow rate optimization in vanadium redox flow battery," Journal of Power
Sources, vol. 248, no. Supplement C, pp. 154-162, 2014.

02-02-2022 15
VRFB MODELING: Pressure drop

Pressure drop (mbar)

Location/method Electrode (el) Flow channels (chan) Total
DL+DW 169 34 202
Fluent 160 26 186

Pressure drop (mbar)

Location/method Electrode (el) Flow channels (chan) Total
DL+DW 74 32 106
Fluent 57 32 89

02-02-2022 16
 VRFB MODELING: Pressure drop

Variables that affect pressure drop

Geometry Electrode properties
• Flow channels dimensions • Pore diameter
• Length(x,y) x width x thickness • Porosity
• Electrode dimensions • Compression
• Length x width x thickness

Operation conditions Electrolyte properties

• Inlet flow rate • Viscosity
• Temperature • Density

Increase will cause higher pressure drop

Increase will cause lower pressure drop

02-02-2022 17