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Influence and use of gas bubbles for the reduction of stray currents in industrial alkaline water electrolysis

Author: Appelhaus, Simon; Chen, Xinming; Becker, Maik; Turek, Thomas
Publisher: Zenodo
DOI: 10.5281/zenodo.17244140
Source: https://zenodo.org/records/17244140/files/EFCF-2025_Paper_A1802_10871_10871_Stray-current-bubble-influence_Simon_A.pdf
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A1802
In luence and use o gas bubbles o he educ ion o
s ay cu en s in indus ial alkaline wa e elec olysis
Simon Appelhaus*, Xinming Chen, Maik Becke , Thomas Tu ek
Claus hal Uni e si y o Technology, Claus hal-Zelle eld/Ge many;
*Con ac co esponding au ho s: www.EFCF.com/Con ac Reques
Abs ac
Alkaline Wa e Elec olysis (AWE) is a key echnology o g een hyd ogen p oduc ion. I is
named a e he highly conduc i e alkaline elec oly e, ypically ~30 w .% KOH solu ion, ha
is pumped h ough he elec olysis cells du ing ope a ion. In indus ial applica ions, many
indi idual cells a e elec ically connec ed in se ies o o m a "s ack". Because he elec oly e
is conduc i e, a sho ci cui occu s and some cu en bypasses he cells h ough he
mani old, known as a s ay, leakage o shun cu en . This cu en has se e al undesi able
e ec s: a educ ion in cu en e iciency, a maldis ibu ion o load ac oss he cells and
co osion due o elec ochemical eac ions ou side o he elec olysis cells [1].
One app oach o inc ease he esis ance and lowe s ay cu en s in he elec oly e is o
in oduce gas bubbles in o he dis ibu ion ubes, dec easing he a ea o he conduc i e liquid.
This occu s na u ally a he ou le o he s ack, whe e he p oduced gas and he elec oly e
lea e he cells mixed. I is usually assumed ha his signi ican ly inc eases he esis ance,
especially when a plug low o annula low egime is eached. Howe e , no expe imen al
s udies ha e been ca ied ou o quan i y his esis ance inc ease. In his wo k, esis ance in
ci cula ubes a di e en gas and liquid low eloci ies is measu ed a indus ial AWE
condi ions. Fu he mo e, he ans e o his concep o he eed dis ibu ion ia he addi ion
o gas bubbles o he elec oly e is e alua ed.
Figu e 1: Example o liquid-gas low egimes wi h inc easing gas ac ion: a) dispe sed, b)
bubbly, c) slug, d) annula [2].
[1] A. T. Kuhn, J. S. Boo h, J Appl Elec ochem. 1980, 10 (2), 233–237. DOI:
h ps://doi.o g/10.1007/BF00726091.
[2] L. Chen, Y. S. Tian, T. G. Ka ayiannis, In e na ional Jou nal o Hea and Mass
T ans e . 2006, 49 (21–22), 4220–4230. DOI:
h ps://doi.o g/10.1016/j.ijhea mass ans e .2006.03.025.
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In oduc ion
Alkaline wa e elec olysis (AWE) is cu en ly ecei ing signi ican in e es in bo h esea ch
and indus ial de elopmen . I is one o wo elec olysis echnologies ha ha e eached
echnical ma u i y, and he e a e mul iple la ge-scale p oduc ion acili ies o AWE s acks in
ope a ion, unde cons uc ion, and in planning [3]. A key p oblem du ing he scale-up o
AWE sys ems is he occu ence o s ay, shun o leakage cu en s. These cu en s occu
only a an indus ial scale in s acks wi h many cells connec ed o a common elec oly e
dis ibu ion sys em, ypically a mani old connec ed o he cells wi h indi idual channels. Due
o he highe ol age di e ences ac oss he en i e s ack, signi ican cu en can sho -ci cui
h ough he elec oly e channels ou side he cells. The consequence o his s ay cu en is
a educ ion o Fa adaic e iciency, he p oduc ion o con aminan gas in he cells and
co osion on g ounded pa s in con ac wi h he elec oly e [1]. This wo k deals wi h he
impac gas bubbles in he connec ion channels ha e on he s ay cu en quan i y.
1. Scien i ic App oach
Since educing he elec oly e conduc i i y o he numbe o cells is no desi able o
indus ial ope a ion, minimizing s ay cu en s is ypically ealized by inc easing he channel
esis ance ou side he cells. The mos common app oach is using long and hin elec oly e
pa hs, o example, hin indi idually connec ed ubes, which also inc ease he sys em's
p essu e d op and equi e signi ican space and design comp omises [4–6]. In his wo k, he
in luence o bubbles blocking he elec oly e pa h and hei in luence on he esis ance a e
e alua ed as an al e na i e way o s ay cu en educ ion. Bubbles a e al eady p esen in
he wo-phase low o he ou le channels o he elec olyze , and i can be assumed ha
hey ha e a signi ican impac on he ou le esis ance. I may also be bene icial o add gas
in o he eed o he elec olyze o signi ican ly inc ease he esis ance in hese channels
wi hou simul aneously inc easing he p essu e d op. This app oach has been de ailed in
wo pa en s issued in 1970 [7, 8], bu he pa en s ha e elapsed, and he me hod has no
been es ed in scien i ic li e a u e.
While he impac o bubbles inside he elec olyze has been s udied ex ensi ely in ecen
yea s [9–16], he e is no esea ch on hei impac on s ay cu en s a ailable in he li e a u e.
The in luence o bubbles inside he small ube is hypo hesized o be di e en han in he
bulk o he elec olysis cell, as he bubble size is much la ge ela i e o he c oss-sec ional
a ea o he ube. Some s udies measu e s ay cu en s in a labo a o y se ing, bu hese
ypically ocus on he pu ely liquid inle side o he elec olyze [17–20]. Simila ly, simula ions
o s ay cu en s dis ega d he ou le ubes o he in luence o he bubbles [4, 21, 22] o use
he B uggeman wo-phase model [23, 24]. The B uggeman co ela ion o sphe ical dilu e
inclusions has been used success ully o p edic he wo-phase luid conduc i i y inside he
cell [25, 26]. Howe e , i has h ee condi ions which a e iola ed o a di e en ex en by he
bubble- ube sys em: (i) negligibly small pa icle size compa ed o he obse ed olume, (ii)
uno de ed pa icles and (iii) no inclusion o one subs ance in he o he . Especially
assump ion (i) is e iden ly no alid i la ge, agglome a ed gas bubbles a e inside he ube.
In his esea ch, he esis ance inc ease o he sys em a di e en gas- o-liquid a ios is
e alua ed o be e unde s and he impac o bubbles on he s ay cu en s in eal alkaline
wa e elec olysis sys ems. The signi ican a ia ions inhe en in hese measu emen s a e
analyzed, and a eliable da a p ocessing me hod is de eloped. In addi ion, he size o he
bubbles is a ied a he same gas low o in es iga e he in luence o he low egime on he
esis ance.
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2. Expe imen s
The expe imen al se up was designed wi h a di ec compa ison o an indus ial sys em in
mind, and he condi ions we e chosen acco dingly.
Figu e 2: Simpli ied p ocess low diag am o he expe imen al se up.
Figu e 2 depic s he en i e expe imen al se up. 30 ± 2 w .% KOH elec oly e is pumped om
he 1 L s o age ank (T01) by a pe is al ic pump a a cons an low a e o 500 mL/min h ough
a pulsa ion dampene (T02) and a hea ed ube. I is mixed wi h ni ogen om a gas bo le
and en e s a 30 cm long es ube made o Pe luo oalkoxy alkanes (PFA) wi h an inne
diame e (ID) o 8 mm. Behind he es ube, he gas is sepa a ed om he liquid (T03). The
gas low a e is se in h ee sepa a e o ame e s wi h di e en measu ing anges be ween
50 and 26,000 mL/min. The esis ance is measu ed be ween wo pla inum wi es subme ged
in he elec oly e low a ei he end o he es ube wi h a o al dis ance o 36 cm in be ween
(EI01).
All expe imen s we e conduc ed a a mosphe ic en p essu e and 75 ± 5 °C elec oly e
empe a u e. The gas is no p e-hea ed. Two me hods a e used o de e mine he esis ance
be ween he wi es: a po en ios a ic measu emen a 10 V o de e mine he o al sys em
esis ance 𝑅𝐷𝐶 including he elec ochemical eac ion, and a high equency measu emen
a 1 - 10 kHz o de e mine he eal pa o he sys em's impedance 𝑍𝑟𝑒𝑎𝑙 . Fo he
po en ios a ic measu emen , an assump ion is made ha he in luence on he esis ance o
he eac ion is small in compa ison o he long elec oly e channel. The po en ios a model
ZENNIUM PRO om Zahne was used o he expe imen s. To educe he in luence o he
la ge luc ua ions du ing he measu emen s, he shun esis o s o he po en ios a a e
limi ed o a minimum measu emen ange o 1.9 mA o a oid equen shun swi ching due
o bubble-induced measu emen ins abili y. In addi ion, o minimize he a iance induced by
he bubbles in he high- equency measu emen , he da a was educed o only measu emen
poin s wi h an absolu e phase shi angle |ϕ|<2° be o e a e aging o e he en i e
measu emen . Each measu emen was un a 17 poin s be ween 0 and 16,000 mL/min N2
low co esponding o a gas ac ion o 0 o 0.97 in he sys em. Fo all measu emen s, he
se inle gas ac ions 𝜀𝑖𝑛 a e lis ed.
In addi ion o mixing he gases in a T-piece wi h 6 mm ID, which c ea es la ge bubbles simila
in size o he ube diame e e en a low gas lows, expe imen s we e also ca ied ou wi h a
Y-mixe wi h 2 mm ID o s udy he in luence o bubble size on he esis ance.
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3. Resul s
Figu e 3: S anda d e e ence case wi h he 8 mm ID e ical ube. Le : Compa ison o he
calcula ed esis ance om he po en ios a ic measu emen , he impedance measu emen
and he il e ed impedance measu emen including absolu e e o depending on he inle
gas ac ion. Righ : Zoom on he compa ison o he po en ios a ic measu emen and he
il e ed impedance measu emen wi h linea y-axis.
Figu e 3 depic s he esul s o he e e ence case wi h he e ical 8 mm ID ube. On he le
side, he po en ios a ic measu emen esis ance calcula ed ia Ohm's law 𝑅𝐷𝐶 is compa ed
o he eal high- equency impedance 𝑍𝑟𝑒𝑎𝑙 wi h maximum e o s. The po en ios a ic
esis ance is calcula ed om he a e age cu en since he measu emen 's goal is o assess
s ay cu en s. In bo h cases, he maximum e o is eno mous, up o 7 o de s o magni ude
o he po en ios a ic measu emen . This a iance co esponds o cu en s be ween 120 mA
o 10 pA du ing he measu emen . E ec i ely, he cu en al e na es be ween 0 A and alues
in he 0.1-10 mA ange du ing high gas ac ion measu emen s. Fo he impedance
measu emen , he da a can be simila ly adjus ed owa ds he e ec i e cu en by emo ing
all da a poin s wi h high phase shi , which also make up he la ges a ia ions du ing he
measu emen s. The igh side o Figu e 3 shows he esul ing calcula ed esis ance and
il e ed eal impedance. They a e in good ag eemen wi h each o he , al hough he a iance
o he measu emen s inc eases a high gas ac ions. A he highes measu ed gas ac ion
o 𝜀 = 0.97, he measu ed impedance is 2444 Ω compa ed o 63 Ω in he pu e liquid. This
co esponds o a educ ion in cu en o 97 %. A 𝜀 = 0.5 he cu en educ ion is 86 %, and
a gas ac ion o 𝜀 = 0.13 al eady achie es 51 % educ ion.
In addi ion, he in luence o bubble size was in es iga ed by compa ing he s anda d case
la ge T-mixe wi h a Y-mixe ha p oduces signi ican ly smalle bubbles. Pic u es o he es
ube a di e en gas ac ions wi h a compa ison o he wo mixe s a e shown in Figu e 4.
The gas bubbles in he Y-mixe a e much smalle han he ube diame e a small gas
ac ions, while he T-mixe always p oduces bubbles wi h he same diame e as he ube.
In he Y-mixe , plug low s a s o ming abo e 𝜀 =0.5 and a highe gas ac ions, he
di e ence in low pa e n becomes indis inguishable. Abo e 𝜀 = 0.75, he low pa e n
ansi ions o chu n low, wi h he liquid becoming inc easingly less con inuous. An annula
low pa e n whe e he liquid comple ely coa s he ube su ace was ne e obse ed, possibly
due o he low ic ion o he PFA ube.
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Figu e 4: Compa ison o he low pa e ns o he la ge T-Mixe (le side o each pai ) and
he small Y-Mixe ( igh side o each pai ) wi h espec i e gas low a es and inle gas
ac ion.
5 cm
𝑉
𝑔𝑎𝑠
=0.05 𝐿/𝑚𝑖𝑛
𝜀𝑖𝑛 = 0.09
𝑉
𝑔𝑎𝑠
= 0.1 𝐿/𝑚𝑖𝑛
𝜀𝑖𝑛 = 0.17
𝑉
𝑔𝑎𝑠
= 0.3 𝐿/𝑚𝑖𝑛
𝜀𝑖𝑛 = 0.38
𝑉
𝑔𝑎𝑠
= 0.7 𝐿/𝑚𝑖𝑛
𝜀𝑖𝑛 = 0.58
𝑉
𝑔𝑎𝑠
= 1.5 𝐿/𝑚𝑖𝑛
𝜀𝑖𝑛 = 0.75
𝑉
𝑔𝑎𝑠
= 3.0 𝐿/𝑚𝑖𝑛
𝜀𝑖𝑛 = 0.86
𝑉
𝑔𝑎𝑠
= 7.0 𝐿/𝑚𝑖𝑛
𝜀𝑖𝑛 = 0.93
𝑉
𝑔𝑎𝑠
=13 𝐿/𝑚𝑖𝑛
𝜀𝑖𝑛 = 0.96
5 cm

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Figu e 5: Compa ison o he esis ance/ impedance o he e e ence T-mixe o he Y-mixe
and he esis ance calcula ed by he B uggeman co ela ion.
Figu e 5 compa es he measu ed esis ance and impedance o he wo mixe s. Small
bubbles lead o signi ican ly lowe esis ances a low gas ac ions han la ge bubbles. The
mos signi ican measu ed di e ence has he Y-mixe a 46 % o he impedance o he T-
mixe a a gas ac ion o 𝜀 =0.36. When he low pa e n ansi ions o a chu n low abo e
𝜀 ≈ 0.5, he di e ence in impedance becomes negligible again, sugges ing ha he bubble
size is he signi ican in luence in his case.
Fo compa ison, he B uggeman equa ion is exempla ily used as one o he common wo-
phase conduc i i y co ela ions. Equa ion 1 shows he simpli ied equa ion o a gas
conduc i i y o ze o. In his case, he e ec i e conduc i i y 𝜅e only depends on he gas
ac ion 𝜀 and he liquid o ma ix medium conduc i i y 𝜅m.
𝜅e =(1−3
2𝜀)𝜅m(1)
Fo he B uggeman co ela ion in Figu e 5, he ma ix medium conduc i i y is no malized o
he calcula ed conduc i i y in he pu e liquid e e ence measu emen . As expec ed, he
equa ion bes i s he Y-mixe conduc i i y wi h he bubbly low, as his low pa e n iola es
he small pa icle assump ion (i) o he co ela ion he leas . Fo he la ge bubbles, he
conduc i i y is o e es ima ed, and he equa ion is no useable o high gas ac ions.
Al hough his co ela ion and o he wo-phase conduc i i y models ha e been used o gas-
liquid sys ems in he pas , hey a e no sui able o he en i e ange o low pa e ns common
in alkaline wa e elec olysis sys ems.
The expe imen al esul s p esen ed in his wo k p o e he assump ion ha gas in elec oly e
channels in alkaline wa e elec olysis sys ems educes he channel conduc i i y and,
consequen ly, i s s ay cu en s. Howe e , he amoun o conduc i i y educ ion canno be
es ima ed ma hema ically wi h a ailable models and does no ollow any known co ela ions
ac oss low pa e ns. I depends no only on he gas ac ion and eloci y in he ube bu also
on he low pa e n a he inle and he ube's size, o ien a ion and su ace. Consequen ly, i
depends on he indi idual indus ial elec olyze 's speci ic design and ope a ing poin . Fo
example, i a highe liquid low a e in a design also dec eases he agglome a ion ime and
hus bubble size, he impac o his change may be la ge han expec ed.
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Addi ionally, while he expe imen s in his wo k we e only conduc ed a ambien p essu e,
p essu ized s acks will p oduce smalle bubbles and lowe gas ac ions a he same
hyd ogen p oduc ion a e as a mosphe ic s acks. Acco dingly, he passi e s ay cu en
educ ion e ec a he s ack ou le due o gas will be educed in hese sys ems. O e all, a
ecommenda ion can be made o use hin channels and la ge gas- o-liquid a ios in indus ial
sys ems o ake ad an age o his e ec , allowing o he educ ion o ou le channel leng h
and p essu e d op.
Du ing he p esen a ion gi en a his con e ence, an addi ional compa ison be ween a
smalle ube diame e and a ho izon ally o ien ed ube will be shown.
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Keywo ds: EFCF2025, H2, LowTemp. Fuel Cells & Elec olyse s, S ay Cu en , Shun
Cu en , S ack Design, Two-Phase Flow
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