United States Patent (19)

Divisek et al.
11
45)
4,445,994
May 1, 1984
54 ELECTROLYZER FOR ALKALINE WATER (56) References Cited
ELECTROLYSIS U.S. PATENT DOCUMENTS
75 Inventors: Jiri Divisek; Heinz Schmitz, both of 1,388,754 8/1921 Pechkranz ...... ... 204/295 X
Julich, Fed. Rep. of Germany 3,471,336 10/1969 Sturm et al. ... 204/2.1
3,554,812 1/1971 Sturm et al. ...................... 429/44X
73) Assignee: Kernforschungsanlage Julich GmbH, 3,607,411 9/1971 Brownrigg ...... ... 204/290 RX
Fed. Rep. of Germany 4,225,411 9/1980 Grine ................................. 204/286
4,312,736 1/1982 Menth et al. ........................ 204/255
4,331,523 5/1982 Kawasaki ........................ 204/283 X
21 Appl. No.: 351,408
FOREIGN PATENT DOCUMENTS
22) Filed: Feb. 23, 1982 2927566 1/1981 Fed. Rep. of Germany ...... 204/295
(30) Foreign Application Priority Data Primary Examiner-Donald R. Valentine
Mar. 5, 1981 DE Fed. Rep. of Germany ....... 31082.55 Attorney, Agent, or Firm-Omri M. Behr
57 ABSTRACT
51) Int, C. ........................ C25B 9/00; C25B 11/03;
C25B 11/06; C25B 13/04 The invention concerns an electrolyzer for alkaline
52 U.S. C. .................................... 204/258; 204/266; water electrolysis whose cells are formed by a dia
204/283; 204/284; 204/286; 204/290 R; phragm provided with electrodes between 2 bi-polar
204/292; 204/295 separator plates as well as a process for the construction
58 Field of Search ........ 204/283, 282,252, 255–258, thereof.
204/263-266, 286-288, 2.1, 284, 290 R, 292,
295; 429/41, 44 11 Claims, 5 Drawing Figures

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 4,445,994
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lem has been well described in the work entitled “Im
ELECTROLYZER FOR ALKALINE WATER provements in Electrolysis Technology in Alkaline
ELECTROLYSS Solutions” by Appleby and Crepy (Proceedings of the
Second World Hydrogen Energy Conference, Zurich
BACKGROUND OF THE INVENTION 5 1978, pages 227-240 in particular section 5).
A well developed technology exists for the purpose In this case the problem may be avoided by the intro
of hydrogen formation by means of the electrolysis of duction of the so called pre-electrodes which are
water, which is a useful and commercially viable ap formed out of electro-catalytically surfaced perforated
proach investigated throughout the World. metal, for example, expanded metal (see with Kreb
The electrolyzers used therefor are generally con 10 skosmo Information No. 5-Water Electrolysis-FIG. 4
structed in the form of bi-polar units. The working and text). There pre-electrodes made of expanded
potential of such cells generally speaking lies in the area metal, are rigidly connected to the bi-polar plates by
of 1.8 to 2 volts having a relatively low current density spot welding so that no contact losses can occur. How
of between 200 to 300 mA/cm2. The efficiency of such ever, even in this case there are substantial potential
cells is therefore very poor calculated on the reaction 15 losses caused by solution resistance.
enthalpy. For achievement of a 100% yield at economi A complete solution to both problems would be of
cally feasible current densities the total cell potential fered by an activated porous electrode which is rigidly
should be of the order of 1.5 volts. The achievement of connected, without pressure contact with the bi-polar
this goal is the stated purpose of all commercially viable plate said electrodes lying sandwich like upon the sepa
developments in the field of alkaline water electrolysis. 20 rator without any space there between. Heretofore this
The greatest problems standing in the way of the idea has not been technically realized since no simple
achievement of this goal are as follows: and commercially viable made of reducing this theory
1. An excessively low working temperature for the to practice had yet been found.
water electrolyzer. This temperature requirement is
determined by the use of the generally employed asbes 25 SUMMARY OF THE INVENTION
tos diaphragm which is only stable at low temperatures. The purpose of the present invention is to provide an
2. An insufficient activity of the electrodes and, electrolyzer for alkaline water electrolysis which may
3. An unsatisfactory cell construction mode which
does not employ the advantages of individual, newly be readily produced and which has commercial viabil
developed, cell components (i.e. active electrodes, dia 30 ity combined with a long working life.
phrams and the like) to an optimal extent. The invention provides an electrolyzer constituting
Heretofore two principal types of electrolysis cells an improvement over the known technology character
were known. The most frequently utilized cell con ized thereby that it comprises electrodes, lying sand
struction is based on the concept of Zdansky Lobza (see wich like upon the diaphragm, which are formed by a
Lurgi Express Information T1084/6.73) which com 35 fine metallic net filled with active porous nickel which
prises a cell of the following construction elements: coats its entire surface. These electrode nets are along
There are provided two electrodes of nickel netting the whole surface area repeatingly electrically con
or perforated sheet placed in a sandwich like manner nected with, especially welded to, structurally support
around a central asbestos diaphragm. This sandwich is ing, electrically conductive, support elements which
placed between a pair of bi-poplar plates in the form of 40 permit not only the evolution of gas, but its removal
a waffle sheet metal plates whose egg shaped protru from the vicinity of the electrode as well.
sions stand in pressure contact with the electrodes. The The fine metal mesh utilized for the anode is suitably
sandwich like construction of the electrodes minimizes a nickel or nickel plated mesh while at the cathode side
the electrode distances so that the ohmic potential drop an iron or steel mesh can suitably be used as well.
in the electroyltes can be substantially eliminated. 45 In such an arrangement the electrically conductive
This substantially optimal cell concept does not how support elements, which are electrically connected with
ever, meet the criteria of points 1 and 2 above that is to the electrode net, serve to provide a uniform distribu
say, that the net electrodes do not possess a sufficiently
satisfactory electro-chemical activity and the asbestos tion of potential over the entire electrode, while the
filling of the lattice with active porous nickel, prevents
diaphragms prohibit higher working temperatures. 50
Practically all of the known suggestions for raising ciency could be Inobtained
over-potentials. this manner production scale effi
the electrode activity are based upon an increase in the be achieved in laboratory which scale
otherwise could only
arrangements.
surface area of the electrodes by means of a catalytically
active porous layer having an increased internal surface BRIEF DESCRIPTION OF THE DRAWINGS
area. When such porous electrodes prepared in accor 55 FIG. 1a is an elevational cross sectional view of an
dance with the above described construction principles, electrolysis cell of the present invention.
are combined with bi-polar plates through pressure
contact, oxide layer formation particularly on the anode as FIG. 1b is an exploded view of a portion of FIG. 1a
indicated.
side, gives rise to such high contact resistance that the FIG. 1c is a partial side elevational view of a portion
gains achieved by activation are lost by reduction of the 60 of the cell of FIG. 1a viewed at c-c, namely the mesh,
potential through ohmic potential drop at these contact support elements, the support plates, and the ingress and
points.
On the other hand, another form of cell construction egress tubes.
which comprises an active electrode layer on the bi obtained FIG.2 shows plots of current density against voltage
polar plates themselves in order to avoid these losses, 65 tion by utilizing the apparatus of the present inven
gives rise to new ohmic potential drops in the electro and utilizing two apparatuses of the prior art.
lyte space between the electrodes and the diaphragm FIG. 3 shows the plot of current density against volt
which is filled by the gas produced. This serious prob age for an apparatus in accordance with the present
 4,445,994 4.
3
invention as compared to four other plots taken from possibility of ready replacement of individual cells
the published literature. without the need for sacrificing the operative unity of
DETAILED DESCRIPTION OF THE
the various component units of the electrolyzer during
DRAWINGS
this exchange.
It is preferred that the supporting elements 22 and 23
The basic cell unit 10 is illustrated in FIG. 1a . The are formed either by a lattice of rods oriented parallel to
unit comprises a diaphragm 12 having a fine first mesh the gas evolution direction and which, are spot welded
14 disposed on one side thereof and a fine metallic mesh to the metallic electrode mesh 14 and 16 over their
16 disposed on the other side thereof, said meshes 14 entire surface or by a correspondingly welded ex
and 16 being in intimate contact with diaphragm 12 but 10 panded metal element. Preferably the lattice rods have
not in contact with each other. The intersticies of said a diameter of the order of 1 to 3 mm and a mutual spac
meshes are filled with porous active nickel. On the side ing of the order of 4 to 8 mm.
of meshes 14 and 16 respectively not in contact with It is particularly desirable to provide an optimal ori
diaphragm 12 is, each case, welded a lattice comprising entation of the individual elements of the cell to each
support elements 22 which are not only in physical 15 other. This may be provided by the use of the finest
connection with said meshes but in view of said welds in possible electrode layer comprising an iron or nickel
electrical contact therewith as well. The support ele mesh and a porous nickel layer as well as the selection
ments are so disposed that when the cell is in operation of appropriate diameters for the rod formed support
said elements are parallel to the direction of flow of the elements and the predetermined separation between
gas generated from each said respective mesh. Electri 20 these as well as the appropriate sequence of spot welds
cally conductive support plate 24 is provided to the side to provide the physical and electrical connection be
of diaphragm 12 covered by mesh 14 and support ele tween the metal mesh net and the support elements. It is
ments 22 and similarly electrically conductive support especially preferred to provide a metal mesh net of wire
plate 25 are provided to the side of the diaphragm 12 thickness of from about 0.1 to about 0.2 millimeters, and
carrying mesh 16 and support elements 23. The size of 25 a mesh width of between about 0.2 and about 0.3 milli
the two meshes is provided to be somewhat less than the meters. The coating of this metal mesh with active
size of the diaphragm. Insulating segments 26 and 28 nickel, which may desirably be achieved through flame
surround that portion of the diaphragm not in contact or plasma spraying of a Raney nickel layer, which, if
with the meshes thus no short-circuit between the two desired may be additionally consolidated by galvanic
bi-polar plates is possible. Support plate 24 is disposed 30
to be in physical contact with insulating segment 28 and nickel/zinc precipitation followed by activation by
treatment with an alkaline leaching, has, suitably, a
in physical and electrical contact with mesh 14 and layer thickness of about 0.2 millimeters. The separation
support elements 22. Similarly support plate 25 is in
physical contact with separating element 26 and in of the spot welds lies suitably between about 0.1 and
physical and electrical contact with mesh 16 and sup about 21 millimeters.
35 about centimeters, preferably between about 1 and
Modifications and further individ
port elements 23. Means are provided to hold all ele ual aspects of the formation of suitable electrode layers
ments in close contact. Electrical contact means (not may be found in German published
shown) are provided to support plates 24 and 25 respec No. 2914094 of applicants assignee. application DE-OS
tively. Ingress tube 36 for the ingress of fresh electro Particularly suitable as diaphragms may be men
lyte and egress tube 32 for the egress of electrolyte and tioned
gaseous product are provided through support plate 24, oped bynickel oxide diaphragms which have been devel
similarly ingress tube 38 and egress tube 34 for the same published applicationassignee
applicants
DE-OS
and disclosed in German
No. 3031064.
purpose are provided through support plate 25.
In operation of the device where a positive potential nickel/zinc, in particular upongalvanic
Electrode layers formed by
a
precipitation of
porous sinter layer
is applied to support plate 24 and a negative potential to 45
support plate 25, oxygen is generated by mesh 14 and followed by removal of the zinc by dissolution, have
passes through egress tube 32 and similarly hydrogen is particularly desirable qualities because their galvani
cally consolidated structure comprise macropores and
generated at mesh 16 and passes through tube 34 when micropores.
a suitable alkaline electrolyte is supplied to ingress tubes determined byThus, the macropores are substantially
36 and 38 respectively. In spite of these tubes (32, 34, 36, 50 the formation ofthetheparticle
body
sizes of the powders used for
of the sinter while the micro
38) channels traversing the series of cells could be pro porosity is achieved by the dissolution of the zinc from
vided in a known manner.
The separator plates 25 illustrated on the left side of the nickel/zinc precipitate.
FIG. 1a as subdivided between adjacent cells could be gasThe macroporosity should be related to the rate of
evolution of the electrode. Thus, the pore size
provided alternatively undivided in one piece belonging 55 should be generally speaking lie in the area of between
to both cells as shown on the right side of FIG. 1a.
When realizing large Electrolysors having electrodes 10 to 100 micrometers.
pressed against the diaphragm spring elements 9 as porosity The diaphragm on the other hand ought to have a
shown at the left bottom side of FIG. 1a should be which is less than the foregoing by a factor of
provided distributed over the area between the separa 60 stancesat least one order of magnitude but under no circum
tor plates 24, 25 and the support elements 14, 16. should it be greater than 10 micrometers. It has
The diaphragm 12 for the passage there through of been found suitable to employ a diaphragm with a mean
ions is relatively thin, suitably of the order of about 0.5 porosity of about 2 micrometers whose individual pore
millimeters and thus provides relatively small resis diameters lies between about 0.7 and about 3 to about 4
tance. 65 micrometers. Preferably diaphragms are employed
The illustrated cell construction is complete in itself, which have a mean pore size in the area of from about
but may if desired be mechanically and/or electrically 0.5 to about 5 micrometers, preferably having pores of
connected with neighboring separate cells provide the between about 1 and about 2 micrometers.
 4,445,994 6
5 s
As carrier for the porous electrode layer a metal COMPARATIVE EXAMPLES
mesh may be utilized as mentioned. A nickel mesh or an
iron or steel mesh is suitably used on the cathode side A nickel oxide diaphragm was coated on both sides
whereas on the anode side a nickel or nickel plated net with activated electrodes and, in accordance with ex
may be utilized. Similarly, in the conventional manner ample I provided between end plates wherein current
the porous electrode layer may contain, in addition to contact with the electrodes is obtained by pressure
nickel, catalytically acting other material in particular contact with a laminar expanded metal element which
cobalt, lanthanum or strontium. . was pressed between the end plates and the coated
In accordance with yet a further embodiment of the diaphragm. In this arrangement during the process of
method of forming the electrode layers it is possible to 10 electrolysis, oxide layers are formed between the
compress a mixture of Raney nickel powder mixed with contact on the anode side which give rise to a substan
methyl cellulose into a carrier mesh, and to activate this tial ohmic potential drop which requires a raising of the
precursor after a sintering treatment by treatment with cell potential for the same current density. The poten
alkali. tial/current density line is shown as curve 1 on FIG. 2.
The production of the diaphragms provided with 15 Electrodes of known structure are prepared by the
electrodes and support elements is set forth in the fol catalytic coating by deposit of Ni/Zn and leaching of
lowing examples. Zn of expanded metal elements as electrodes welded to
a bi-polar end plate. These are used for the construction
EXAMPLES of a cell in a sandwich arrangement. Even with this
EXAMPLE I 20 arrangement, in gas filled electrolytes, potential losses
occur which require the increase of the cell potential.
A nickel oxide diaphragm is prepared in accordance The curve obtained from this arrangement is shown as
with the procedures set forth in German published ap curve 2 in FIG. 2.
plication DE-OS 3031064. A fine nickel mesh is layed A third curve is provided by an arrangement pro
upon both sides of the diaphragm, having a rod lattice 25 duced in accordance with example II for water electrol
spot welded on the side thereof away from the dia ysis at 100° C. in a 30% aqueous potassium hydroxide
phragm. This arrangement is then provided with a solution (conditions similar to those utilized in curves 1
Raney nickel layer by flame spraying. During this depo and 2). In all three cases a catalytic coating of compara
sition an appropriate coating behind the lattice rods is ble quality is provided on the electrode and this quality
aimed at. According an even more prefered variation 30 determined by potential free measurements. It will be
the diaphragm is additionally provided at first with a seen from FIG. 2 that curve 3 represents a substantial
slight coating of flame sprayed porous nickel layer (of improvement over the situation in curves 1 and 2.
about 10 to 50 um thickness. The Raney nickel layer is In FIG. 3 a comparison was made of the results ob
reinforced by electrochemical deposition of nickel/zinc tained utilizing apparatus in accordance with the pres
and the arrangement is activated in the usual manner by 35 ent invention in comparison with other cells of other
treatment with an alkaline solution. The bi-polar end known types. All curves resulted from experiments run
plates are then electro conductively connected with the under substantially similar conditions of electrolysis
lattice rods. that is to say, at a temperature of approximately 100 C.
EXAMPLE II moderate pressure, and similar electrode size. The ac
tual basis of these experiments found by various authors
One side of the rod lattice, similar to that in Example and the reaction conditions are set forth below.
I, is spot welded to a nickel mesh, the other side of said Curve 1: N. Wakabayashietal, Proc. 3rd World Hydro
lattice is rigidly welded to a half-cell forming bi-polar gen Energy Conf, Tokyo, 23-26.1980,S.58 (Temp.
end plate. The mesh is coated with Raney nickel layer 118' C., Electrode 50 cm2).
by flame spray and provided with a nickel/zinc coating 45 Curve 2: H. Vandenborre et al, Seminar Hydrogen,
by electrochemical deposition. After activation by Commission Europ. Comm., Brussels, 12.14.2, 1980,
aqueous alkali in the known manner this arrangement is S.143 (Temp. 100° C., Electrode 40 cm2, 3 bar).
placed on both sides of a central nickel oxide dia Curve 3: J. N. Murray, M. R. Yaffe, Proc. [Link],
phragm. Tikyo, 23-26.6.1980, S.15 (Temp. 100° C., Electrode
In place of the nickel oxide diaphragm in accordance 50 300 cm2)
with this example, there may be similarly used other Curve 4: L. J. Nuttall, J. H. Russell, Int. [Link]
separators such as ion exchanging membranes. Among Energy, 5,75 (1980). (SPE-Electrolysis Temp. 83 C,
these separators may be named a polyantimony acid Electrode 45 cm2, 7 bar)
separator as disclosed by Vandenborre etal in "Seminar Curve 5: Electrolysis cell in accordance with the pres
on hydrogen as an Energy Vector' EEC report 55 ent invention Identical with mit Curve 3, FIG. 2
EUR6085 Brussels 1978 page 161. (Temp. 100; Electrode 30 cm2; atmospheric pressure
In both cases, that is to say, example I as well as It will thus be seen that a considerable improvement
example 2 there may be utilized as an activating layer is shown by Curve 5.
for the metal mesh, in place of the combined Raney We claim:
1. An electrolysis cell component unit for alkaline
nickel/nickel-zinc precipitation either only raney nickel 60 water
deposited by flame or plasma spray or only nickel/zinc electrolysis to generate hydrogen and oxygen
by galvanic means. It is also possible to deposit carbonyl gases comprising:
(a) A cathodeportion and an anode portion, compris
nickel by flame or plasma spray or else by rolling in and
sintering, and additionally deposit galvanic nickel/zinc 65 ing a pair of electrically conductive separator
plates,
thereon. The most desirable (i.e. lowest) potential val (b) insulating means, said insulating means being lo
ues are nevertheless obtained by the combined use of cated between said separator plates to prevent
Raney nickel with nickel/zinc precipitation (and activa direct electrical contact therebetween,
tion) as described in examples I and II.
 4,445,994
7 8
(c) a porous diaphragm of electrically nonconductive (c) means for applying a positive potential to the
material, electrically conductive separator plates designated
(d) a first metallic mesh and a second metallic mesh, for the anode side of the cell,
said first metallic mesh being placed upon and in (d) means for applying a negative electro potential to
intimate contact with one side of said diaphragm 5 the electrically conductive separator plates desig
nated for the cathode side of the cell.
and said second mesh being similarly placed upon 3. An electrolysis cell of claim 2 wherein the support
the other side of said diaphragm, the interstices of elements of the lattice are oriented to be parallel to the
both said meshes being filled with porous activated direction of gas flow when the unit is in operation.
nickel, 10 4. A composite electrolysis device comprising a series
(e) a first and a second lattice of rigid electrically of self contained electrolysis cells of claim 2.
conductive support elements said first lattice 5. An electrolysis cell component unit of claim 1
placed upon and over its whole surface being in wherein the support elements of the lattice are oriented
repeating welded electro-conductive connection to be parallel to the direction of gas flow when the unit
with said first metallic mesh, and said second lattice 15 is in operation.
being similarly welded to and in electrically con 6. A cell component unit of claim 1 wherein the dia
ductive relation with said second mesh, phragm is nickel oxide diaphragm.
said cathode portion comprising one of said separator 7. A cell component unit of claim 1 wherein said
plates being in physical contact with a portion of support elements have a diameter of from about 1 to
about 3 millimeters and are separated from each other
said first mesh and a portion of said first lattice, said by a distance from about 4 to about 8 millimeters.
physical contact providing electrically conductive 8. A cell component unit in accordance with claims 2
connection between the components of said cath or 7 wherein the welded connection between said re
ode portion, said second lattice, said second mesh spective meshes and their respective support elements
and said other separator plate comprising the 25 are located at a mutal distance of between 1 and 10
anode portion being similarly in physical and elec millimeters.
trically conductive contact with each other. 9. A cell component unit in accordance with claim 8
2. An electrolysis cell comprising at least one compo wherein the distance between said welded connections
is between about 1 and about 2 millimeters.
nent unit of claim 1 and further comprising 30 10. A cell component unit of claim 1 wherein the
(a) at least one ingress means on each side of the material of said metallic meshes selected from the group
diaphragm of each of said component units for the consisting of nickel, nickel plated metals, iron, and steel.
provision of solution to be electrolyzed, 11. An electrolysis cell component unit according to
(b) at least one egress means for each side of the claim 1 comprising spring elements between the support
diaphragm of each of said component units for the 35 member and the separator plate inside the cell space.
egress of the gaseous product of the electrolysis, k

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