IL261145A - A technique for activating sulfur-based electrode for an electrolyser - Google Patents
A technique for activating sulfur-based electrode for an electrolyserInfo
- Publication number
- IL261145A IL261145A IL261145A IL26114518A IL261145A IL 261145 A IL261145 A IL 261145A IL 261145 A IL261145 A IL 261145A IL 26114518 A IL26114518 A IL 26114518A IL 261145 A IL261145 A IL 261145A
- Authority
- IL
- Israel
- Prior art keywords
- sulfur
- electrolyte
- based electrode
- complexing agent
- container
- Prior art date
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B15/00—Operating or servicing cells
- C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
- C25B15/085—Removing impurities
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Description
WO 2017/148507 PCT/EP2016/054311
Description
A technique for activating Sulfur-based electrode for an
electrolyser
The present invention relates to techniques for activating
Sulfur-based electrode i.e. electrode comprising sulfur and
an electrically conducting non-Sulfur material.
In modern times, electrolysis is used for various purposes,
for example in Hydrogen and/or Oxygen generation which are
achieved by hydrogen evolution reaction (HER) and Oxygen evo-
lution reaction (OER) in an electrolyser by electrolysis of
electrolyte i.e. generally water. Usually, alkaline or acidic
water is used as the electrolyte. The electrolyser includes
electrodes that conduct electrical energy to the electrolyte
and thus decomposes the electrolyte.
Various types of electrodes are used in electrolysers. A com-
monly used electrode in electrolysers is Sulfur-based elec-
trode for example a metal-sulfur electrode such as a Nickel-
Sulfur electrode which is primarily employed as cathode in
the electrolyser. The metal-sulfur electrodes are produced by
various methods such as electrodeposition. One such method
for preparing metal-sulfur electrode is described in United
States Patent no. 4,171,247 titled 'Method for preparing ac-
five cathodes for electrochemical processes' which describes
preparation of electrodes of the nickel-sulfur type using an
electrodeposition bath.
Generally, such electrodeposition baths, including the bath
described in United States Patent no. 4,171,247, are typical-
ly composed of a nickel salt and a sulfur releasing compound.
The sulfur releasing compound is typically selected among
Thiourea, Potassium thiocyanate, Sodium thiocyanate, and So-
dium hydrosulfite.WO 2017/148507 PCT/EP2016/054311
2
During the electrodeposition procedure an electro-catalytic
coating is formed on surface of the electrode, usually the
electrode to be used as the cathode in the electrolyser. The
coating is usually formed on top of a metallic substrate and
it is characterized by its amorphous or nanocrystalline
structure. Such coatings have beneficial properties for the
HER and/or the OER especially in alkaline electrolysis and in
the chloralkali process.
The formed amorphous alloy formed by the electro-catalytic
coating generally includes one or more elements but the main
constituent is usually Nickel. Additionally, the electro-
catalytic coating includes sulfur. The amount of incorporated
sulfur usually varies between 10 and 30 wt%. Other elements
can be Cobalt, Molybdenum and Iron. The sulfur containing
electro-catalytic coating along with the underlying metallic
substrate together forms the electrode.
When such a Sulfur-based electrode, i.e. the electrode com-
prising sulfur and an electrically conducting non-sulfur ma-
terial such as Nickel, is used in the electrolyser for elec-
trolysis reaction it has been observed that during electroly-
sis in the electrolyser the sulfur from the electro-catalytic
coating formed as surface of the electrode is slowly and con-
tinuously removed from the electrode into the electrolyser
leaving thereby a nickel coating with high catalytic activity
compared to non-catalysed Nickel.
The removal of the sulfur from the Sulfur-based electrode is
typically a slow process and usually takes several days going
up to months. The sulfur that is slowly released by the Sul-
fur-based electrode accumulates in the electrolyser and the
electrolyser components introducing a contamination and cor-
rosion risk and further increases risk of stress corrosion
cracking of pressurized parts of the electrolyser, if any,
thereby decreasing lifetime of the electrolyser.WO 2017/148507 PCT/EP2016/054311
3
Thus the object of the present disclosure is to provide a
technique by which release and accumulation of sulfur within
the electrolyser is at least partially obviated when using in
the electrolyser an electrode that has sulfur and an electri-
cally conducting non-sulfur material. Furthermore, it is de-
sirable that the electrolyte in which the sulfur is released
is rendered at least partially free from the released sulfur
and may be reused in the electrolysis reaction in the elec-
trolyser.
The above object is achieved by a method for activating a
Sulfur-based electrode according to claim 1 and an arrange-
ment for activating a Sulfur-based electrode according to
claim 14 of the present technique. Advantageous embodiments
of the present technique are provided in dependent claims.
According to an aspect of the present technique a method for
activating a Sulfur-based electrode for an electrolyser is
provided. The Sulfur-based electrode is formed of sulfur and
an electrically conductive non-sulfur material. In the meth-
od, an electrolyte and a complexing agent are provided to a
container, either simultaneously or successively. The elec-
trolyte and the complexing agent are provided either sepa-
rately or as a mixed with each other. The Sulfur-based elec-
trode is positioned in the container. The electrolyte and the
complexing agent are contacted with at least a part of a sur-
face of the Sulfur-based electrode. The electrolyte reacts
with the Sulfur-based electrode to release at least a part of
the sulfur from the Sulfur-based electrode. The complexing
agent reacts with the released sulfur to form a coordination
complex with the released sulfur. Finally in the method, the
coordination complex is removed from the container.
The coordination complex formed by the chemical reaction be-
tween the released sulfur and the complexing agent is in sol-
id state, for example an amorphous state and thus can be re-
moved with ease from the electrolyte which is in liquid
state. The removal of the coordination complex may be perWO 2017/148507 PCT/EP2016/054311
4
formed for example by filtration. Thus by using the method
for activation of the Sulfur-based electrode according to the
present technique, either the sulfur content of the Sulfur-
based electrode is already decreased before electrolysis is
performed in the electrolyser using the activated electrode
or at least a part of the sulfur released from the Sulfur-
based electrode is filtered out from the electrolyser and
thus not deposited in the electrolyser.
In an embodiment of the method, the electrolyte is alkaline
water. Thus the method is applicable to alkaline water elec-
trolysis technique.
In another embodiment of the method, the complexing agent
comprises one of Barium hydroxide, Barium chloride, Barium
nitrate, Strontium hydroxide, Strontium chloride, Strontium
nitrate, Calcium hydroxide, Calcium chloride, Calcium ni-
trate, and a combination thereof. The aforementioned chemi-
cals are readily available or can be easily made and thus
provide a simple way of implementing the method of the pre-
sent technique. When performing the method of the present
technique on a Sulfur-based electrode that is already posi-
tioned in the electrolyser for alkaline water electrolysis,
using hydroxides of Barium, Strontium and/or Calcium in acti-
vating the Sulfur-based electrode is specially beneficial be-
cause after the removal of the coordination complex, only hy-
droxide ions from the complexing agent are left in the elec-
trolyte thereby maintaining the chemical integrity of the
electrolyte. To explain further, the Barium, Strontium and/or
Calcium from the hydroxides of Barium, Strontium and/or Cal-
cium used as the complexing agent is removed as part of the
coordination complex, leaving only the hydroxide ion in the
electrolyte, and thus does not interfere with the chemistry
of the electrolyte.
In another embodiment of the method, the container is a part
of the electrolyser in which the Sulfur-based electrode is
positioned for carrying out electrolysis of the electrolyte.WO 2017/148507 PCT/EP2016/054311
In a related embodiment of the method, the method is per-
formed simultaneously with the electrolysis of the electro-
lyte. Thus in situ activation of the Sulfur-based electrode
is performed i.e. the Sulfur-based electrode is activated
while positioned in the electrolyser. When the method is per-
formed simultaneously with the electrolysis of the electro-
lyte, the electrical energy applied to the Sulfur-based elec-
trode for the electrolysis of the electrolyte further in-
creases the rate of the release of the sulfur from the Sul-
fur-based electrode and thus increasing the rate at which the
method for activation of the Sulfur-based electrode according
to the present technique is performed.
In another embodiment of the method, the container is dis-
tinct from the electrolyser i.e. the container is not a part
of the electrolyser and the method is performed prior to
electrolysis of the electrolyte. Subsequently, the electroly-
sis of the electrolyte may be performed using the activated
electrode in the electrolyser. In a related embodiment of the
method, an electrical voltage is applied to the Sulfur-based
electrode while the electrolyte and the complexing agent are
contacted with the Sulfur-based electrode. Thus the Sulfur-
based electrode is activated prior to being integrated into
the electrolyser. This obviates requirement of modifying the
electrolyser to integrate a mechanism for removal of the co-
ordination complex. Furthermore, after the coordination com-
plex has been removed from the electrolyte, the electrolyte
subsequently may be used in the electrolyser for electrolysis
reaction or may be used back in the container for subsequent-
ly performing the method for activating the Sulfur-based
electrode.
In another embodiment of the method, the coordination complex
is removed by filtration. This provides a simple and cost ef-
fective way of removing the coordination complex from the
electrolyte.WO 2017/148507 PCT/EP2016/054311
6
According to another aspect of the present technique, an ar-
rangement for activating a Sulfur-based electrode is provid-
ed. The Sulfur-based electrode is for an electrolyser and
comprises sulfur and an electrically conductive non-sulfur
material. The arrangement includes a container, an electro-
lyte feed and a filtration unit. The container receives the
Sulfur-based electrode. At least a part of the Sulfur-based
electrode is positioned within the container such that elec-
trolysis of an electrolyte may be carried out using the Sul-
fur-based electrode positioned within the container. The
electrolyte feed provides the electrolyte and a complexing
agent to the container and the container receives the elec-
trolyte and the complexing agent. The electrolyte and the
complexing agent so received are contacted with at least a
part of a surface of the Sulfur-based electrode within the
container. At least a part of the sulfur is released from the
Sulfur-based electrode by a chemical action of the electro-
lyte and the part of the sulfur so released forms a coordina-
tion complex by a chemical action with the complexing agent.
The filtration unit is in fluid communication with the con-
tainer. The filtration unit receives the electrolyte from the
container after the electrolyte and the complexing agent are
contacted with the part of the Sulfur-based electrode within
the container. The filtration unit then removes, by filtra-
tion, at least a part of the coordination complex from the
electrolyte so received. Finally the filtration unit provides
the electrolyte so filtered to the container. The coordina-
tion complex formed by the chemical reaction between the re-
leased sulfur and the complexing agent is in solid state, for
example an amorphous state and thus can be removed by the
filtration unit with ease from the electrolyte which is in
liquid state. Thus with the arrangement for activating the
Sulfur-based electrode according to the present technique, at
least a part of the sulfur released from the Sulfur-based
electrode is filtered out from the electrolyser and thus not
deposited in the electrolyser.WO 2017/148507 PCT/EP2016/054311
7
In an embodiment of the arrangement, the electrolyte feed
comprises a mixer. The mixer mixes the electrolyte and the
complexing agent, for example the mixer by physical action
dissolves the complexing agent into the electrolyte, before
the electrolyte and the complexing agent are provided to the
container.
The present technique is further described hereinafter with
reference to illustrated embodiments shown in the accompany-
ing drawing, in which:
FIG 1 schematically illustrates an exemplary embodiment
of an arrangement of the present technique; and
FIG 2 depicts a flow chart showing an exemplary embodi-
ment of a method of the present technique.
Hereinafter, above-mentioned and other features of the pre-
sent technique are described in details. Various embodiments
are described with reference to the drawing, wherein like
reference numerals are used to refer to like elements
throughout. In the following description, for purpose of ex-
planation, numerous specific details are set forth in order
to provide a thorough understanding of one or more embodi-
ments. It may be noted that the illustrated embodiments are
intended to explain, and not to limit the invention. It may
be evident that such embodiments may be practiced without
these specific details.
The basic idea of the present technique is to provide a
complexing agent along with an electrolyte to a Sulfur-based
electrode, i.e. an electrode comprising sulfur and at least
one electrically conducting non-Sulfur material such as Nick-
el, such that the sulfur released into the electrolyte from
the Sulfur-based electrode chemically reacts with the
complexing agent to form a coordination complex having a sol-
id state. The coordination complex is then filtered out from
the electrolyte and rendering the electrolyte, and thus theWO 2017/148507 PCT/EP2016/054311
8
electrolyser when the electrolyte is in the electrolyser, at
least partially free from the sulfur released from the Sul-
fur-based electrode.
The Sulfur-based electrode (hereinafter also referred to as,
the electrode) may have sulfur limited to a coating formed on
top of a substrate or may have sulfur present in the entire
electrode material and not only limited to the coating, if
present. The at least one electrically conducting non-Sulfur
material may be, but not limited to, a metal such as Nickel,
Cobalt, Iron, Chromium, Aluminium, Molybdenum, and a combina-
tion thereof. In the present application, hereinafter, Nickel
(Ni) has been used as an example for the electrically con-
ducting non-Sulfur material; however, it is noteworthy that
the scope of the present technique is not limited to only Ni.
For the purpose of explanation, and without limiting the
scope of the present technique, in the present disclosure,
the Sulfur-based electrode may be understood as an electrode
having sulfur and Ni in a coating on a surface of an electri-
cally conducting substrate material such as, but not limited
to, a metallic substrate for example stainless steel, differ-
ent steel grades, and other electrically conducting metal al-
loys .
FIG 1 schematically illustrates an exemplary embodiment of an
arrangement 1 for activating a Sulfur-based electrode 10 of
the present technique. The electrode 10 has a surface coating
of Ni and Sulfur and may be used or intended to be used as a
cathode in an electrolyser (not shown). FIG 2 depicts a flow
chart showing an exemplary embodiment of a method 100 for ac-
tivating the electrode 10 of the present technique. Hereinaf-
ter, the method 100 of FIG 2 has been explained with help of
arrangement 1 of FIG 1.
The arrangement 1 includes a container 20, an electrolyte
feed 30 and a filtration unit 40. The container 20 receivesWO 2017/148507 PCT/EP2016/054311
9
the electrode 10. At least a part (not shown) of the elec-
trode 10 is positioned within the container 20.
In the method 100, in a step 110 an electrolyte 22 is provid-
ed to the container 20 and in a step 120 a complexing agent
(not shown) is provided to the container 20. In an exemplary
embodiment of the method 100, the step 110 and the step 120
are performed simultaneously. The electrolyte 22 is a liquid
for example alkaline water. The alkaline water may be formed
for example by adding Sodium or Potassium hydroxide to water
for example by adding between 30 and 50 wt% of Sodium or Po-
tassium hydroxide. In general complexing agent is a chemical
entity that is capable of forming a coordination complex with
Sulfur. The coordination complex formed with Sulfur is essen-
tially solid for example amorphous residue. The complexing
agent may include, but not limited to, one or more of Barium
hydroxide, Barium chloride, Barium nitrate, Strontium hydrox-
ide, Strontium chloride, Strontium nitrate, Calcium hydrox-
ide, Calcium chloride, and Calcium nitrate. Generally the
amount of complexing agent when provided to the electrolyte
22 in the container 20 is substantially equal to or less than
1 M (molar) concentration. For purpose of explanation and not
limitation, Barium hydroxide i.e. Ba(OH)2, has been used in
the present disclosure hereinafter as the complexing agent
with concentration between 10 and 200 gram per liter of the
electrolyte 22, and more particularly approximately 171 gram
per liter of the electrolyte 22.
When performing the steps 110 and 120 simultaneously, the
electrolyte 22 i.e. the alkaline water 22, and the complexing
agent i.e. Ba(OH)2 may be provided separately to the contain-
er 20 from the electrolyte feed 30. The complexing agent may
be provided as a solid to the container 20 where the
complexing agent gets dissolved in the electrolyte 22 or the
complexing agent is dissolved in a medium such as water to
form complexing agent solution and then provided to the con-
tainer 20 wherein the complexing agent solution mixes with
the electrolyte 22. Alternatively, the complexing agent mayWO 2017/148507 PCT/EP2016/054311
be mixed or dissolved in the electrolyte 22 before the
complexing agent and the electrolyte 22 are provided to the
container 20. The mixing of the complexing agent and the
electrolyte 22 may be performed by a mixer 35 of the electro-
lyte feed 30.
When performing the steps 110 and 120 successively, the elec-
trolyte 22 i.e. the alkaline water 22, and the complexing
agent i.e. Ba(OH)2 are provided separately to the container
20 from the electrolyte feed 30, preferably the step 120 is
performed after the step 110. The complexing agent may be
provided as a solid to the container 20 to the electrolyte 22
already provided to the container 20 where the complexing
agent gets dissolved in the electrolyte 22 in the container
20 or the complexing agent is dissolved in a medium such as
water to form complexing agent solution and then provided to
the container 20 wherein the complexing agent solution mixes
with the electrolyte 22.
In the method 100, in a step 130 performed subsequent to
steps 110 and 120, the electrolyte 22 and the complexing
agent are contacted with at least a part of a surface of the
electrode 10. The electrolyte 22 reacts with the electrode 10
to release at least a part of the sulfur from the electrode
10. In an exemplary embodiment of the method 100, when per-
forming the step 130, no electrical energy is provided to the
electrode 10. In an alternate exemplary embodiment of the
method 100, when performing the step 130, electrical energy
is provided to the electrode 10 in form of electrical current
and in this embodiment the electrode 10 is positioned to act
as a cathode for the electrolyte 22 and an additional elec-
trode (not shown) acting as anode is positioned in the ar-
rangement 1 to complete current flow path through the elec-
trolyte 22.
In the embodiment of the method 100 of open potential i.e.
when no electrical current is passed through the electrode
, the Sulfur-based electrode is not chemically stable inWO 2017/148507 PCT/EP2016/054311
11
the alkaline environment formed by the alkaline electrolyte
and Sulfur from the electrode is leached into the electrolyte
22 as schematically depicted in the following equation (i):
NiS + 2e —> Ni + S2 ... (i)
In equation (i) the Sulfur-based electrode is depicted by
chemical formulation NiS representing Nickel (Ni) and Sulfur
(S) in the electrode 10. The alkalinity of the electrolyte 22
is raised by presence of strong bases such as Potassium or
Sodium hydroxide used to prepare the alkaline water used as
the electrolyte 22. Thus Sulfur is released in the electro-
lyte 22 in the container 20 in form of sulfide ion.
In the embodiment of the method 100 where electric current is
passed through the electrolyte 22 in the container 20 and
where the additional electrode (not shown) is positioned as
anode to complete the current flow path through the electro-
lyte 22 in the container 20, the Sulfur from the electrode 10
leaches out of the electrode 10 as schematically depicted in
the following equations (ii), (iii) and (iv):
2 H+ + S + 2e —> H2S (g) ... (i i)
h2 (g)+s ־* h2s C90 ••• (iii)
H2S ((7) + 4 OH —> 3 H2 Q7) + 26 + SO% ... (iv)
The electrical current ranging approximately between 0.1 and
10 Ampere per square centimeter of the surface of the elec-
trode 10 may be used, and more particularly for the aforemen-
tioned reactions depicted by equations (ii), (iii) and (iv)
the electrical current with current densities of 0.2 - 1 Am-
pere per square centimeter of the surface of the electrode 10
was used. It may be noted that with an increase in current
density passing through the electrode 10 a rate of leaching
of sulfur from the electrode 10 is generally increased, how-
ever the allowable current density is dependent on structuralWO 2017/148507 PCT/EP2016/054311
12
and compositional parameters of the electrode 10 for example
the allowable current density is dependent on quality the de-
posited NiS layer in the electrode 10.
As a result of application of electrical current or external
electrical voltage, water in the electrolyte 22 is dissociat-
ed into hydrogen ion (H+) and hydroxide ion (OH-) . At the
electrode 10 acting as the cathode, water in the electrolyte
22 is reduced to form H2 gas and possibly H+ as an intermedi-
ate step during the formation of H2 gas. Sulfur from the
electrode 10 or the coating of the electrode 10, represented
by NiS or Ni-S, reacts with either H+ or H2 (g) to form Hydro-
gen sulfide gas i.e. H2S (g) by chemical reactions depicted
hereinabove represented by equations (ii) and (iii) respec-
tively. Subsequently, H2S (g) is reduced to H2 gas and sul-
fate ion i.e. S042־ by chemical reactions with hydroxide ion
i.e. OH“ as depicted hereinabove represented by equation
(iv). Thus Sulfur is released in the electrolyte 22 in the
container 20 in form of sulfate ion.
In one embodiment of the method 100, the step 130 is per-
formed at a temperature ranging between 20 degree Centigrade
and 200 degree Centigrade i.e. temperature within the con-
tainer 20. Furthermore, pressure ranging between 1 bar and
100 bar is maintained in the container 20 while performing
the step 130.
In the method 100, the complexing agent reacts with the re-
leased sulfur to form a coordination complex with the re-
leased sulfur for example as schematically depicted in the
following equations (v):
S0l~ + Ba(OH)2 ־־> BaSO4 (s) + 2 OH~ . . . (v)
Thus, as shown in equation (v) above, the released sulfur for
example the sulfate ion in equation (v) chemically reacts
with the complexing agent for example Barium hydroxide in
equation (v) to form coordination complex for example inWO 2017/148507 PCT/EP2016/054311
13
equation (v) Barium sulfate in solid state i.e. BaSCy (s) in
the electrolyte 22 in the container 20.
Finally in the method 100, in a step 140 subsequent to step
130, the coordination complex i.e. BaSCy (s) in equation (v)
is removed from the container 20. In arrangement 1, the step
140 is performed by a filtration unit 40. The filtration unit
40 is in fluid communication with the container 20. The fil-
tration unit 40 receives the electrolyte 22 from the contain-
er 20 after the step 130 has been performed and thus the
electrolyte 22 that is received by the filtration unit 40 in-
eludes the coordination complex. The filtration unit 40 then
removes for example by mechanical or physical filtration at
least a part of the coordination complex i.e. BaSCy (s) in
equation (v) from the electrolyte 22 so received. The elec-
trolyte 22 that is rendered at least partially free of some
of the coordination complex is provided back by the filtra-
tion unit 40 back to the container 20.
It may be noted that use of hydroxide as complexing agent for
example Barium hydroxide, Strontium hydroxide and/or Calcium
hydroxide is specially advantageous because after removal of
the coordination complex from the electrolyte 22 using the
filtration unit 40, the part of the complexing agent left be-
hind in the electrolyte 22 by the complexing agent is hydrox-
ide ion i.e. OH“ as depicted in equation (v) that shows that
hydroxide ions i.e. OH“ are generated in equation (v) along
with the coordination complex i.e. BaS04 (s) in equation (v),
and thus when the coordination complex i.e. BaS04 (s) in
equation (v) is removed in the step 140 only hydroxide ions
i.e. OH“ is left behind in the electrolyte 22 and thus the
chemical integrity of the electrolyte 22, specially when al-
kaline water is used as the electrolyte 22, is not compro-
mised or altered. Thus the electrolyte 22 that is provided
back by the filtration unit 40 to the container 20 may be
used for continuation of the method 100, or for subsequent
repetition of method 100 using another sulfur-based electrodeWO 2017/148507 PCT/EP2016/054311
14
, or for use as electrolyte in an electrolytic reaction in
an electrolyser.
The step 140 may be performed by a filter element for example
a filter paper, a fibrous filter such as a Nickel-fibrous
filter, and so on and so forth. For filtration of coordina-
tion complex in form of BaSCy (s) in equation (v) a filter
paper having a particle retention of approximately 1 ym was
used. In arrangement 1, the filtration unit 40 includes the
filter element (not shown). The filter may be replaceable or
regenerative.
The method 100 may be performed either prior to carrying out
the electrolysis of the electrolyte 22 in the electrolyser or
simultaneously along with the electrolysis of the electrolyte
22 in the electrolyser. It may be noted that in an exemplary
embodiment, where the method 100 is performed prior to carry-
ing out the electrolysis of the electrolyte 22 in the elec-
trolyser the container 20 is a distinct from the electrolyser
i.e. the container 20 is not part of the electrolyser. In
this embodiment of the method 100, the electrode 10 is acti-
vated i.e. at least a part of the sulfur from the electrode
is removed by the method 100, and then the electrode 10 in
its activated form is placed in an electrolyser and the elec-
trolyte 22 or some other electrolyte is provided in the elec-
trolyser and thereby electrolysis of the electrolyte 22 or of
the some other electrolyte in the electrolyser is performed.
The activation of the electrode 10 may be performed with or
without use of electrical energy.
However, in the embodiment where the method 100 is performed
simultaneously along with the electrolysis of the electrolyte
22 in the electrolyser, the container 20 is part of the elec-
trolyser i.e. the container 20 is the site or seat of elec-
trolysis of the electrolyte 22.
While the present technique has been described in detail with
reference to certain embodiments, it should be appreciatedWO 2017/148507 PCT/EP2016/054311
that the present technique is not limited to those precise
embodiments. Rather, in view of the present disclosure which
describes exemplary modes for practicing the invention, many
modifications and variations would present themselves, to
those skilled in the art without departing from the scope and
spirit of this invention. The scope of the invention is,
therefore, indicated by the following claims rather than by
the foregoing description. All changes, modifications, and
variations coming within the meaning and range of equivalency
of the claims are to be considered within their scope.16 261145/2
Claims (12)
1. A method (100) for activating a Sulfur-based electrode (10) for an electrolyser, the Sulfur-based electrode (10) comprising sulfur and an electrically conductive non-sulfur material, the method (100) comprising: - providing (110) an electrolyte (22) to a container (20), wherein the electrolyte (22) is adapted to release at least a part of the sulfur from the Sulfur-based electrode (10), - providing (120) a complexing agent to the container (20), wherein the complexing agent is adapted to form a coordination complex with the released sulfur and comprises one of Barium hydroxide, Barium chloride, Barium nitrate, Strontium hydroxide, Strontium chloride, Strontium nitrate, Calcium hydroxide, Calcium chloride, Calcium nitrate, and a combination thereof, - contacting (130) the electrolyte (22) and the complexing agent with at least a part of a surface of the Sulfur-based electrode (10), wherein the Sulfur-based electrode (10) is positioned in the container (20), and - removing the coordination complex from the container (20).
2. The method (100) according to claim 1, wherein the electrically conductive non-sulfur material comprises a metal.
3. The method (100) according to claim 2, wherein the metal is one of Nickel, Cobalt, Iron, Chromium, Aluminium, Molybdenum, and a combination thereof.
4. The method (100) according to any one of claims 1 to 3, wherein the electrolyte (22) is alkaline water.
5. The method (100) according to any one of claims 1 to 4, wherein the electrolyte (22) and the complexing agent are mixed prior to contacting (130) with the part of the surface of the Sulfur-based electrode (10).17 261145/2
6. The method (100) according to any one of claims 1 to 5, wherein the electrolyte (22) and the complexing agent are contacted (130) with the part of the surface of the Sulfur based electrode (22) at a temperature ranging between 20 degree centigrade and 200 degree centigrade.
7. The method (100) according to any one of claims 1 to 6, wherein the electrolyte (22) and the complexing agent are contacted (130) with the part of the surface of the Sulfur based electrode (22) at a pressure ranging between 1 bar and 100 bar.
8. The method (100) according to any one of claims 1 to 7, wherein the container (20) is a part of the electrolyser in which the Sulfur-based electrode (10) is positioned for carrying out electrolysis of the electrolyte (22).
9. The method (100) according to claim 8, wherein the method (100) is performed simultaneously with the electrolysis of the electrolyte (22).
10. The method (100) according to any one of claims 1 to 7, wherein the container (20) is distinct from the electrolyser and wherein the method (100) is performed prior to electrolysis of the electrolyte (22) in the electrolyser.
11. The method (100) according to claim 10, wherein in contacting (130) the electrolyte (22) and the complexing agent with the Sulfur-based electrode (10) an electrical voltage is applied to the Sulfur-based electrode (10).
12. The method (100) according to any one of claims 1 to 11, wherein the coordination complex is removed (140) by filtration.
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PCT/EP2016/054311 WO2017148507A1 (en) | 2016-03-01 | 2016-03-01 | A technique for activating sulfur-based electrode for an electrolyser |
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IL261145A true IL261145A (en) | 2018-10-31 |
IL261145B IL261145B (en) | 2022-06-01 |
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IL261145A IL261145B (en) | 2016-03-01 | 2018-08-14 | A technique for activating sulfur-based electrode for an electrolyser |
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EP (1) | EP3400322B1 (en) |
DK (1) | DK3400322T3 (en) |
IL (1) | IL261145B (en) |
WO (1) | WO2017148507A1 (en) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4171247A (en) * | 1977-02-24 | 1979-10-16 | Norsk Hydro A.S. | Method for preparing active cathodes for electrochemical processes |
US4888099A (en) * | 1986-02-10 | 1989-12-19 | Eka Nobel Ab | Process for the production of alkali metal chlorate |
US5482696A (en) * | 1993-08-04 | 1996-01-09 | Huels Aktiengesellschaft | Method for the purification and/or electrolysis of an aqueous potassium chloride solution |
US5858240A (en) * | 1995-04-17 | 1999-01-12 | Chemetics International Company Ltd. | Nanofiltration of concentrated aqueous salt solutions |
-
2016
- 2016-03-01 EP EP16707713.0A patent/EP3400322B1/en active Active
- 2016-03-01 WO PCT/EP2016/054311 patent/WO2017148507A1/en active Application Filing
- 2016-03-01 DK DK16707713.0T patent/DK3400322T3/en active
-
2018
- 2018-08-14 IL IL261145A patent/IL261145B/en unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4171247A (en) * | 1977-02-24 | 1979-10-16 | Norsk Hydro A.S. | Method for preparing active cathodes for electrochemical processes |
US4888099A (en) * | 1986-02-10 | 1989-12-19 | Eka Nobel Ab | Process for the production of alkali metal chlorate |
US5482696A (en) * | 1993-08-04 | 1996-01-09 | Huels Aktiengesellschaft | Method for the purification and/or electrolysis of an aqueous potassium chloride solution |
US5858240A (en) * | 1995-04-17 | 1999-01-12 | Chemetics International Company Ltd. | Nanofiltration of concentrated aqueous salt solutions |
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EP3400322A1 (en) | 2018-11-14 |
WO2017148507A1 (en) | 2017-09-08 |
DK3400322T3 (en) | 2022-08-01 |
IL261145B (en) | 2022-06-01 |
EP3400322B1 (en) | 2022-06-08 |
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