1

22PA0037DE

Kuhn / ON

Applicant: Carl Freudenberg KG, 69469 Weinheim

5

GAS DIFFUSION LAYER MADE OF WATER JET ENTANGLED NONWOVENS

Description

10 The present invention relates to a method for producing a gas diffusion layer, wherein
nonwovens made of carbon fibers or carbon fiber precursors are subjected to
entanglement with water-containing fluid jets of specific water-containing fluid jets of
a certain water quality. The invention also relates to the gas diffusion layer obtainable

15 according to the method and to a fuel cell that contains such a gas diffusion layer.

BACKGROUND OF THE INVENTION

Fuel cells use the chemical conversion of fuel, in particular hydrogen, with
20 oxygen to form water in order to generate electrical energy. In hydrogen-oxygen fuel
cells, hydrogen or a hydrogen-containing gas mixture is fed to the anode, where

electrochemical oxidation takes place with the release of electrons (H 2→ 2 H+ + 2 e- ).

The protons are transported from the anode chamber to the cathode chamber via a
membrane that separates the reaction chambers from
25 each other in a gas-tight manner and insulate them electrically. The electrons provided
at the anode are fed to the cathode via an outer conductor circuit. The cathode is supplied
with oxygen or a gas mixture containing oxygen, whereby the oxygen is reduced and the
30 electrons are absorbed. The oxygen anions formed react with the protons transported
across the membrane to form water (1/2 O2 + 2 H+ + 2 e- → H2 O).
 2

Low-temperature proton exchange membrane fuel cells (PEMFCs, also known as

5 polymer electrolyte membrane fuel cells) are used for many applications, especially in
the automotive powertrain. The core element is a polymer electrolyte membrane (PEM),

which is only permeable to protons (or oxonium ions H O3+ ) and water and spatially
10 separates the oxidizing agent, generally atmospheric oxygen, from the reducing agent. A
catalyst layer, which forms the electrodes and usually contains platinum as the
catalytically active metal, is applied to the gas-tight, electrically insulating, proton-
conducting membrane on the anode and cathode side. The actual redox reactions and
charge separations
take place in the catalyst layers. The membrane and catalyst layers form a unit, which is
15 also referred to as a CCM (catalyst-coated membrane). On both sides of the CCM, there
is a gas diffusion layer (GDL), which stabilizes the cell structure and performs transport
and distribution functions for reaction gases, water, heat, and electricity. The membrane,
electrodes, and gas diffusion layer
20 form the membrane electrode assembly (MEA). Flow distribution plates (so- called
bipolar plates) are arranged between the membrane electrode assemblies, which have
channels for supplying the adjacent cathode and anode with process gases and usually
also have internal cooling channels.

25
The gas diffusion layers between the flow distributor plates and the catalyst layers are
of key importance for the function and performance of the fuel cell. The process
components consumed and generated in the electrode reactions must be transported
30 through the gas diffusion layer and distributed homogeneously from the macroscopic
structure of the flow distributor plates/bipolar plates to the microscopic structure of the
catalyst layers. The electrons formed and consumed in the half-cell reactions must be
conducted to the flow distributor plates with the lowest possible voltage loss. The heat
generated during the reaction must be dissipated to the coolant in the flow distributor
plates so that the materials of the GDL must also have sufficient
5 thermal conductivity. In addition, the GDL must also act as a mechanical balance
between the macro-structured flow distributor plate and the catalyst layers.
 3

Gas diffusion layers for fuel cells typically consist of a carbon fiber substrate, which is
10 usually made hydrophobic with fluoropolymers (e.g. PTFE) and then coated with a
microporous layer (MPL). The MPL usually consists of a fluorine-containing polymer as
a binder (e.g. PTFE) and a porous and electrically conductive carbon material (e.g. carbon
black or graphite powder). The following three materials
15 are currently used as carbon fiber substrates for the GDL:

- Carbon fiber papers (wet laid and chemically bonded carbon fiber
nonwovens, with chemical binders that are carbonized),
20 - Carbon fiber fabrics (e.g. made from yarns of oxidized but not yet carbonized
polyacrylonitrile fibers, which are carbonized or graphitized after weaving),
- carbon fiber nonwovens (e.g. dry-laid, carded and jet entangled nonwovens
made of oxidized polyacrylonitrile, which are subsequently thickness
25 calibrated and carbonized).

It is known that fuel cells can be contaminated by the introduction of foreign ions
that are not involved in the electrode processes. For example, the influence of the
materials of the bipolar plates and the cations and anions introduced from these into the

30 MEA of the fuel cell on the cell performance was investigated. Other sources, especially
for metallic cations, are emissions from the other materials of the cell, the system
components such as the tank, heat exchanger, piping, etc., the air supply flow to the
cathode, and contamination of the hydrogen through production or transportation. One
possible problem with metallic ions is that they can be easily absorbed by the electrolyte

5 membrane. The reason for this is the strong affinity of the metal cations to the sulphonic
acid groups of the perfluorinated cation exchanger membrane, which is generally greater
than the affinity of the protons to the sulphonic acid groups.
 4

It has now been found that the GDL can also contribute to the loading of the MEA with
10 foreign ions. There is therefore a need for gas diffusion layers that only contain very low
concentrations of ions, especially metal cations, and for processes to produce them. In
particular, the GDL should have a low concentrations of cations, such as those normally
15 contained in water for technical applications, such as calcium, magnesium, sodium, and
potassium ions. The other mechanical properties of the GDL should not be adversely
affected.

For the production of carbon fiber nonwovens, nonwovens made of carbon

fibers or carbon fiber precursors can be subjected to bonding by the action of aqueous

20 fluid jets. Such spunlace processes for bonding nonwovens with fluid jets and streams,
including spunlacing with superheated steam jets, are known to those skilled in the art.
A special method for the mechanical bonding of nonwovens is hydroentanglement, in
which water at an increased pressure of
25 around 20 to over 400 bar is directed through a large number of nozzles onto the
nonwoven to be bonded. The impulse force of the water jets leads to a mechanical
anchoring of the fibers in the product. So-called nozzle strips, which can be arranged in
one or more rows, serve as a tool for this method. Each row has a large number of nozzles.
30 The maximum number of nozzles per strip can be up to 20,000, with typical nozzle
diameters ranging from 0.05 to 0.3 mm.

US 2003/182730 A1 describes a nonwoven fabric with a low content of ionic impurities,

which is achieved by washing with water with a low ion concentration. These
nonwovens are used, among other things, in cleaning
5 clothes and protective clothing for cleanrooms. An application for the production of a
gas diffusion layer for a fuel cell is not described.

WO 0231841 describes a conductive nonwoven fabric obtained from a fiber pile of pre-
10 oxidized fibers for carbon fibers by bonding the fiber pile with high-pressure fluid jets at
pressures of 100 to 300 bar, compacting the bonded fiber web and subsequent
carbonization and/or graphitization under an inert gas atmosphere at temperatures of 800
°C to 2500 °C.
 5

15
DE 10 2006 060 932 A1 describes temperature-stable structures comprising fibers and a
coating, whereby this coating is covalently bonded to the surface of the fibers. In
particular, these are conductive nonwovens that have been subjected to a plasma coating
20 with fluorinated hydrocarbons and are suitable as a gas diffusion layer for fuel cells. To
produce the conductive nonwoven, carbon fibers or carbon fiber precursors are laid to
form a fiber pile and bonded by exposure to high-pressure fluid jets and then pre-dried,
calendered, and carbonized.
25
US 2019/0165379 A1 describes a material for a gas diffusion layer based on a carbon
fiber nonwoven fabric which has areas with high and areas with low basis weights in the
plane and wherein at least one of the surfaces of the nonwoven fabric has an uneven
pattern with indentations and elevations which
30 is independent of the weight distribution of the fibers. The production of the
nonwoven comprises a water jet process.

None of the last four documents mentioned contain information on the quality of the
water used for water jet treatment.

The unpublished international application PCT/EP2021/085452 describes a gas diffusion

5 layer with high purity and a process for its production, in which nonwovens made of
carbon fibers or carbon fiber precursors are subjected to bonding with water-containing
fluid jets, the water having a conductivity of at most 250 microsiemens/cm at 25 °C.

10 Information on the pH value of the water used in the water jet treatment is not available.

It has now been found that high-quality and especially high-purity carbon fiber nonwovens can
be produced by subjecting dry-laid nonwovens made of carbon fibers or carbon fiber precursors
15 to bonding by exposure to water-containing fluid jets. The quality of the water used for bonding
is of critical importance here.
 6

The pH value of the water is a critical parameter here, e.g. in order to remove unwanted
20 web-accompanying substances during wet bonding without the aid of a washing agent.
At the same time, additives already added before this treatment step should essentially
be retained. By optimizing the pH value, it is also possible to reduce or avoid damage to
the nonwoven caused by the water treatment.

25 Another critical parameter is the ion concentration, i.e. the proportion of dissociated
substances dissolved in a certain amount of water. Surprisingly, a
hydroentanglement process makes it possible to produce high-purity nonwovens with
a very low ion concentration, which can be further processed into GDL with an equally
30 very low ion concentrations. Advantageously, the nonwovens obtained are
characterized by a very low number of so-called nozzle strip defects. These can occur
when individual nozzles of the jet strip become clogged.

SUMMARY OF THE INVENTION

5

The first object of the invention is a process for producing a gas diffusion layer for
a fuel cell, in which one

a) provides a fiber composition comprising carbon fibers and/or precursors of

10 carbon fibers,

b) subjecting the fiber composition provided in step a) to a process for

producing a fiber pile,

c) the fiber pile is bonded to form a nonwoven fabric by the action of aqueous
15 fluid jets, the water used having a pH value in the range from 5.5 to 8.0,
 7

d) if necessary, subjecting the nonwoven obtained in step c) to a thermal and/or

20 mechanical treatment for drying and/or further bonding,

e) if the fiber composition used in step a) comprises precursors of carbon

25 fibers, subjecting the nonwoven fabric to pyrolysis at a temperature of at least
1000°C.

In a particular embodiment, the water used in step c) has a conductance of at most 250
microsiemens/cm at 25 °C.

30 In a further specific embodiment, the nonwoven fabric from step c), d) or e) (i.e.
depending on which of these steps is carried out, following the last of these steps) is
finished with a hydrophobizing agent (= step f)).

In a further specific embodiment, the nonwoven fabric from step c), d), e) or f) (i.e.
5 depending on which of these steps is carried out, following the last of these steps) is
coated with a microporous layer (= step g)).

The invention also relates to a fiber pile (jet entangled nonwoven fabric) with
10 a very low ion concentration which is bonded by the action of aqueous fluid jets. The
invention therefore also relates to a nonwoven fabric obtainable by a process in which

a) provides a fiber composition comprising carbon fibers and/or precursors

15 of carbon fibers,

b) subjecting the fiber composition provided in step a) to a process for

producing a fiber pile,

20 c) the fiber pile is bonded to form a nonwoven fabric by the action of aqueous
fluid jets, the water used having a pH value in the range from
5.5 to 8.0.
 8

25 With regard to steps a), b) and c), full reference is made to the following explanations of
these steps.

A further object of the invention is a gas diffusion layer as defined above and below,
or obtainable by a method as defined above and below.

30
A further object of the invention is a fuel cell comprising at least one gas diffusion layer
as defined above and below, or obtainable by a process as defined above and below.

5 DESCRIPTION OF THE INVENTION

Unless otherwise specified below, the pH values given refer to a temperature of

25°C.

10 The pH value can be determined using conventional methods known to the skilled
person. Preferably, the determination is carried out using an electrometric method based
on measuring the chain voltage of an electrochemical cell, one of the two half-cells being
15 a measuring electrode and the second being a reference electrode. The potential of the
measuring electrode is a function of the pH value of the measuring solution.
Commercially available pH electrodes based on a pH electrode and a reference electrode,
for example in the form of a combination electrode, can be used to determine the pH
20 value. Suitable methods for determining the pH value are described in DIN EN ISO
10523-C5:2012-04.

Measuring devices for pH value measurement via proton activity, especially using an
electrometric method, such as the commercially available pH value measuring chains,
25 usually have automatic or manual temperature compensation to compensate for the
temperature dependence of the ion product of water.
 9

The gas diffusion layers obtained by the method according to the invention have the
following advantages:

30
- By optimizing the pH value of the water used for hydroentanglement, it is
possible to remove unwanted accompanying nonwoven materials during wet
bonding without the use of a washing agent. At the same time, additives already
added before this treatment step, such as stiff finishes, plasticizers, antistatic
agents,
5 hydrophobing agents, antibacterial, antimycotic or fungicidal finishes, flame
retardants and other additives, are essentially retained.
- By optimizing the pH value, it is also possible to reduce or prevent
damage to the nonwoven fabric caused by water treatment.
- The carbon fiber nonwovens obtained from dry carbon fibers by
10 hydroentanglement and the GDL based on them are characterized by a very low
ion concentration.

- The nonwovens obtained from dry carbon fiber precursors by

hydroentanglement and subsequent carbonization or graphitization and the GDL

15 based on them are also characterized by a very low ion concentration.

The nonwovens obtained by hydroentanglement according to the method of the

invention have a very low number of so-called jet streak defects.

- Compared to the GDLs previously used in the prior art, the GDLs according to

20 the invention has comparably good mechanical properties.

- Fuel cells based on the GDL according to the invention have a longer service
life than fuel cells based on conventional GDL.

25
The gas diffusion layer according to the invention and obtainable by the method
according to the invention comprises a carbon fiber nonwoven fabric as a flat electrically
conductive material. The carbon fiber nonwoven fabric and the gas diffusion layer are
30 sheet-like structures that have an essentially two- dimensional, planar extension and a
smaller thickness in comparison. The gas
 10

diffusion layer has a base area that generally corresponds essentially to the base area of
the adjacent membrane with the catalyst layers and the base area of the adjacent flow
distributor plate of the fuel cell. The shape of the base surface of the gas diffusion layer
can, for example, be polygonal (n-cornered
with n ≥ 3, e.g. triangular, square, pentagonal, hexagonal, etc.), circular, circular segment-
5 shaped (e.g. semi-circular), elliptical or elliptical segment-shaped. Preferably, the base
surface is rectangular or circular.

Production of the gas diffusion layer

10
Step a)

In step a) of the method according to the invention, a fiber composition comprising

15 carbon fibers and/or precursors of carbon fibers are provided.

Preferred carbon fibers consist of at least 90% by weight, preferably at least 92% by
weight, based on their total weight, of carbon. In a special embodiment, carbon fibers that

20 have undergone graphitization can be used. These carbon fibers have a higher carbon
content and then consist in particular of at least 95% by weight of carbon.

Suitable precursors for carbon fibers are fibers from synthetic or natural sources that can
25 be converted into carbon fibers by one or more treatment steps (carbonization). These
include for example, fibers made from polyacrylonitrile homo- and copolymers (PAN
fibers), phenolic resins, polyesters, polyolefins, cellulose, aramids, polyether ketones,
30 polyether ester ketones, polyethersulfones, polyvinyl alcohol, lignin, pitch and mixtures
thereof. Preferably, the fiber composition provided in step a) comprises PAN fibers as
precursor fibers or consists of PAN fibers as precursor fibers. In a first preferred
embodiment, the fiber composition provided in step a) comprises PAN fibers and fibers
different therefrom, preferably selected from fibers of phenolic resins, polyesters,
polyolefins, cellulose, aramids, polyether ketones, polyether ester
 11

5 ketones, polyethersulfones, polyvinyl alcohol, lignin, pitch and mixtures thereof. Such
additional polymers are preferably contained in the carbon fiber precursor in an amount
of up to 50% by weight, particularly preferably up to 25% by weight, based on the carbon
fiber precursor. In a second preferred embodiment, the fiber composition provided in step
a) consists exclusively of PAN fibers.

10
Suitable PAN fibers are selected from PAN homopolymers, PAN copolymers and
mixtures thereof. PAN copolymers contain at least one comonomer polymerized therein,
which is preferably selected from (meth)acrylamide, alkyl acrylates, hydroxyalkyl
15 acrylates, alkyl ether acrylates, polyether acrylates, alkyl vinyl ethers, vinyl halides, vinyl
aromatics, vinyl esters, ethylenically unsaturated dicarboxylic acids, their monoesters and
diesters, and mixtures thereof. For example, the comonomer is selected from acrylamide,
methyl acrylate, methyl methacrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate,
n-octyl acrylate,
20 lauryl acrylate, stearyl acrylate, 2-ethylhexyl acrylate, benzyl acrylate, 2- hydroxyethyl
acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2- methoxyethyl acrylate,
4-methoxybutyl acrylate, di-ethylene glycol ethyl ether acrylate, 2-butoxyethyl acrylate,
ethyl vinyl ether, acrylic acid, methacrylic acid, itaconic acid, itaconic acid monomethyl
ester, itaconic acid monolauryl ester,
25 fumaric acid dimethyl ester, styrene, vinyl acetate, vinyl bromide, vinyl chloride, etc. If
a polyacrylonitrile copolymer fiber is used as the carbon fiber precursor in step a), the
proportion of comonomers is at most 20% by weight, preferably at most 10% by weight,
based on the total weight of the monomers used for polymerization. Preferably,
30 polyacrylonitrile homopolymer fibers are used as the carbon fiber precursor in step a).

PAN polymers can, for example, be spun as a solution into filaments by wet spinning and
coagulation and combined into ropes (fiber bundles). PAN copolymers often have a lower
melting point than PAN homopolymers and are
5 therefore not only suitable for use in wet spinning processes, but also in melt spinning
processes. The PAN fibers obtained in this way are usually subjected to oxidative
cyclization (also known as oxidation or stabilization for short) in an
 12

oxygen-containing atmosphere at elevated temperatures of around 180 to

300 °C. The resulting chemical cross-linking causes the PAN fibers to become cross-

10 linked. The resulting chemical cross-linking improves the dimensional stability of the
fibers.

The fibers obtained during oxidative cyclization can be used as precursors of carbon
fibers in step a) without further processing. It is also possible to subject the fibers obtained

15 during oxidative cyclization to at least one processing step, preferably selected from
cleaning, coating with at least one sizing agent, drying
and combinations of at least two of these treatment steps. In order to clean the fibers
after electrochemical oxidation, they may be subjected to a washing process. Washing
20 is used specifically to remove fiber fragments. Washing is usually followed by a drying
step. To modify the surface properties, the fibers can be at least partially coated with at
least one sizing agent. The sizing agent can be used, for example, in the form of a
25 solution in a suitable solvent or in the form of a dispersion. The fibers can be passed
through a sizing bath, for example, to apply the coating. The coating can be at least
partially detached from the fibers during hydroentanglement in step c). If the water used
in step c) to consolidate the fiber pile is at least partially recycled, it may be
30 advantageous to subject the wastewater from the hydroentanglement process to a
treatment in which the sizing contained in the wastewater is partially or completely
removed.

After coating the fibers with at least one sizing agent, they are usually subjected
to (further) drying. Drying can be carried out for example using hot air, hot plates,

5 heated rollers, or radiant heaters.

The precursors of carbon fibers thus obtained can be used and further processed as a fiber
composition in step a) of the process according to the
10 invention. Alternatively, a fiber composition comprising PAN fibers or consisting of PAN
fibers can be subjected to pyrolysis at a temperature of at least 1000 °C, whereby the PAN
precursors are converted to carbon fibers. With regard to the
 13

pyrolysis conditions, reference is made to the following remarks on step e). The carbon
15 fibers thus obtained can also be used and further processed as a fiber composition in step
a) of the process according to the invention.

Step b)

20 In step b) of the method according to the invention, the fiber composition provided in
step a) is subjected to a process for producing a fiber pile (carbon fiber nonwoven or
carbon fiber precursor nonwoven). Suitable processes for the production of nonwovens
are known to the skilled person and are described, for example, in H. Fuchs, W. Albrecht,
25 Vliesstoffe, 2nd ed. 2012, p. 121 ff., Wiley- VCH. These include, for example, dry
processes, wet processes, extrusion processes and solvent processes. In a preferred
embodiment, the fiber composition provided in step a) is subjected to a dry laying process
30 in step b) to produce a fiber pile. The production of dry-laid nonwovens can in principle
be carried out using a carding process or an aerodynamic process. In the carding process,
a fiber pile is formed by carding or carding, whereas in aerodynamic processes,
nonwovens are formed from fibers with the aid of air. If desired, the fiber piles can be
stacked in several layers to form a nonwoven. The drying process in step b) can include
5 a modification of the properties, e.g. by stretching the nonwoven. This can be used, for
example, to calibrate the nonwoven thickness and/or pre-bond the fiber pile.

Step c)

In step c) of the process according to the invention, the fiber pile obtained in step b) is

10 bonded to form a nonwoven fabric by the action of aqueous fluid jets. Water-containing
fluid jets also include fluid streams and steam jets.

In principle, the mechanical bonding processes known for this purpose, also known as
15 spunlace processes, are suitable for hydroentanglement. In principle, the so-called steam
jet technology, in which superheated steam jets are used
 14

for web bonding, is also suitable. Such processes are known to those skilled in the art. In
a special method for the mechanical bonding of nonwovens, water is directed at an
20 increased pressure of around 20 to 500 bar through a large number of nozzles onto the
nonwoven to be bonded. The nozzles are arranged in one or more rows in so-called nozzle
strips. These nozzle strips have a large number of nozzles in each row. The maximum
number of nozzles can be up to 20,000 nozzles per strip, with typical nozzle diameters
25 ranging from 0.05 to 0.5 mm. The hole diameters of the nozzles generally have very small
tolerances of less than 2 mm, for example. In order to achieve defect-free nonwovens, it
is necessary that the hole diameters of the nozzles do not change during operation and, in
particular, that the nozzles do not become blocked.

30
It was found that the pH value of the water used for bonding the fiber pile (nonwoven) is
essential for the quality of the gas diffusion layers produced therefrom for use in fuel
cells. Therefore, it is a critical feature of the process according to the invention that the
water used for bonding the nonwoven fabric in step c) has a pH value (based on 25 °C)
in the range from 5.5 to 8.0, preferably in the range from 5.5 to 7.0, particularly
5 preferably in the range from 6.0 to 6.9.

It was also found that the conductivity of the water used to bind the fiber pile (nonwoven)
is essential for the quality of the gas diffusion layers produced from it for use in fuel cells.

10 Therefore, the water used for bonding the nonwoven in step c) preferably has a
conductivity of at most 250 microsiemens/cm (μS/cm) at 25 °C. Particularly preferably,
the water used in step c) has a conductivity of at most 200 microsiemens/cm at 25 °C, in
particular of at most 150 microsiemens/cm at 25 °C, especially of at most 100

15 microsiemens/cm at 25 °C.

Electrical conductivity is a sum indicator for the ion concentration, i.e. the proportion
of dissociated substances dissolved in a certain amount of water. The conductivity
20 depends, among other things, on the concentration of the
 15

dissolved substances, their degree of dissociation and the valence and mobility of the
cations and anions formed as well as the temperature. Conductivity measurement is
based on the determination of the ohmic resistance of the water sample to be analyzed
or the reciprocal of the resistance, the electrical

25 conductance (unit Siemens S = Ω−1 ). Commercially available conductivity meters

(conductometers) can be used to measure conductivity. The measured values are usually
given in S/cm (Siemens per centimeter) or in microsiemens per centimeter for water
samples with a low ionic load.

30 Process and service water for industrial processes usually comes from the public
drinking water network or is pumped from wells, rivers and lakes. Drinking water and
process water for processes that are critical in terms of water quality is usually checked
for its ingredients and, if necessary, subjected to water treatment processes. The
requirements for water purity are extremely
diverse depending on the respective area of application. For example, drinking water is
5 supplied as a clear, colorless liquid, free of odors and harmful microorganisms and
substances, but enriched with essential minerals and salts. This water is of food quality
but is not necessarily suitable for many technical applications. According to the Drinking
10 Water Ordinance (TrinkwV 2001, new version dated March 10, 2016), drinking water in
Germany must have a pH value of 6.5 to 9.0, usually in the range of 7.0 to 8.5. The limit
value for conductivity according to the Drinking Water Ordinance is 2790
microsiemens/cm at 25 °C. The tap water supplied by German waterworks has a
15 conductivity of 250 to 1000 microsiemens/cm at 25°C, depending on the hardness level.

Na+ , K+ , Ca2+ and Mg2+ make up the majority of the inorganic cations.

Preferably, the water used in step c) has a content of Na+ ions of at most 200 ppm by
20 weight, particularly preferably of at most 25 ppm by weight.

Preferably, the water used in step c) has a content of K+ ions of at most 200 ppm by
weight, particularly preferably of at most 10 ppm by weight.
 16

25
Preferably, the water used in step c) has a content of Mg2+ ions of at most 10 ppm by
weight.

Preferably, the water used in step c) has a content of Ca2+ ions of at most 200 ppm by
30 weight, particularly preferably of at most 40 ppm by weight.

To provide the water used in step c) according to the invention, an available drinking or
process water can be subjected to treatment to adjust the pH value and/or to reduce the
5 ion concentration. This includes ion exchange, electro-deionization, membrane processes
such as nanofiltration, reverse osmosis, and electrodialysis, thermal processes such as
distillation, flash evaporation, etc.

In a first preferred embodiment, nanofiltration, reverse osmosis, or a combination of

these
10 processes is used to reduce the ion concentration. Both nanofiltration and reverse
osmosis are based on the fact that the water to be treated is passed through a
semipermeable membrane under pressure that is higher than the osmotic pressure,
15 whereby a permeate with a reduced ion concentration is obtained. Nanofiltration takes
place at lower pressures than reverse osmosis and therefore has a lower purification
performance than reverse osmosis, but is sufficient in many cases. It is also possible to
pre-clean the water using nanofiltration and then further reduce the ion concentration
using reverse osmosis.
20
In a second preferred embodiment, an ion exchange process is used to reduce the ion
concentration. For this purpose, available drinking or processed water (raw water) is

25 generally brought into contact with at least one cation exchange resin and at least one
anion exchange resin. In a suitable embodiment, the raw water is first treated with at least
one strongly acidic cation exchanger, so that the cations present in the water are

exchanged for hydrogen ions (H+ ). The water thus obtained is then treated with at least
one strongly basic anion
 17

30 exchanger in order to exchange negatively charged ions for hydroxide ions

(OH- ). If necessary, the water obtained after being brought into contact with the cation
exchanger can also be brought into contact with at least one weakly basic anion
exchanger before the strongly basic exchanger. If necessary, the water can be subjected
to carbon dioxide degassing after the cation exchanger or, if present, between the weakly

5 basic and the strongly basic anion exchanger.

To adjust the properties of the water used in step c), it is also possible to mix two or more starting
10 waters of different compositions. These differ in at least one property, such as the pH value or the
content of a certain type of ion. In a particular embodiment, a mixture of at least one water with
a lower pH value and at least one water with a higher pH value than the target value is used to
15 adjust the pH value of the water used in step c). In a very particular embodiment, a mixture of at
least one water with a lower pH obtained by nanofiltration or reverse osmosis and at least one
water with a higher pH obtained by ion exchange is used to adjust the pH of the water used in
step c).

20
The pH value of the water used in step c) is determined by the content of CO2 and the dissociation
of the carbonic acid formed from it. The first dissociation stage from CO2 and water to form

hydrogen carbonate anions (HCO3- ) and oxonium ions (H3O+ ), which takes place in the range
25 between pH 4.3 and pH 8.2, is particularly relevant for the process according to the invention. In
drinking or processed water, the concentration of dissolved carbon dioxide can range from
a few milligrams per liter to over 20 mg/l, depending on the source. The concentration of
hydrogen carbonate anions in drinking or processed water can be several 100 g/l,
30 depending on the source. Due to the absorption of carbon dioxide from the ambient air,
pure water usually has a slightly acidic pH value and distilled water can reach acidic pH
values of around 5.8. Only freshly produced distilled water has a pH value of around 7,
but as soon as it comes into contact with carbon dioxide, a slightly acidic pH value is
reached within a few hours.
 18

5 The influence of dissolved carbon dioxide on the pH value depends on the process
selected to treat the raw water. Hydrogen carbonate anions, for example, can be
effectively separated from the raw water using processes such as ion exchange,
nanofiltration, and reverse osmosis. This is not the case for dissolved CO2, which is
10 essentially not retained by the membranes used for nanofiltration and reverse osmosis,
for example. As a result, the permeate from nanofiltration or reverse osmosis generally
has an acidic pH value due to the dissociation of the dissolved carbon dioxide, which may
well be less than pH 6.
15 In addition, hydrogen carbonate is formed from the dissolved CO2 and thus the
conductivity is increased accordingly. In a special embodiment, the raw water can
therefore be subjected to carbon dioxide degassing before treatment in a nanofiltration
or reverse osmosis system.

20 A CO2 trickler, for example, can be used for carbon dioxide degassing. In this process,
the water is trickled in a column, and strip air is fed in countercurrent, which leads to the
removal of CO2 from the water. Alternatively or additionally, a membrane degassing
process can be used for carbon dioxide degassing.

25
In a special embodiment of the process according to the invention, the water used in step
c) for consolidating the fiber pile is partially or completely recycled. The method
according to the invention thus makes it possible to reduce the amount of fresh water
30 required and the amount of wastewater to be disposed of for hydroentanglement. It is
ensured that the water used to treat the fiber pile always has a conductivity within the
range of the invention and contamination of the fiber pile with components contained in
the wastewater from the hydroentanglement process is also avoided. For this purpose,
the wastewater from the hydroentanglement process can be partially or completely
treated and/or exchanged.
5
The treatment and/or replacement of the wastewater from the hydroentanglement system
can be carried out continuously or at intervals.
 19

A preferred process is one in which a fiber pile is bonded to form a nonwoven fabric by
10 the action of aqueous fluid jets, a wastewater stream is discharged from the treatment of
the fiber pile, a setpoint value for the conductivity of the wastewater stream is determined,
the actual value of the conductivity of the wastewater stream is determined after a limit
value for the deviation of the actual value from the setpoint value has been reached, the
15 wastewater stream is at least partially subjected to reprocessing and/or exchange with
water of lower ionic concentration and the wastewater stream is at least partially
returned to the treatment of the fiber pile.

For processing, the wastewater stream can be subjected to a reduction in the ion
20 concentration as described above. In addition, the wastewater stream can be subjected
to further purification, e.g. to remove fibers and fiber fragments.

Step d)

25
If necessary, the nonwoven obtained in step c) can be subjected to a thermal and/or
mechanical treatment for drying and/or further bonding. Suitable drying processes are
30 convection drying, contact drying, radiation drying, and combinations thereof.

Preferably, the nonwovens obtained in step c) are subjected to a calendering treatment.

Calendering allows further thermal bonding of the nonwoven fabric and simultaneously
calibrates its thickness. Several nonwoven layers can also be bonded together. In a special
5 embodiment, the nonwoven obtained in step c) contains thermoplastic fibers that serve
as binding fibers and can usually be carbonized. In this case, thermal calender bonding
of the nonwoven can take place in step d), forming bonding points at which fibers are
10 plasticized and welded together (thermobonding).

Step e)
 20

If the fiber composition used in step a) comprises precursors of carbon fibers, the
15 nonwoven fabric is subjected to pyrolysis at a temperature of at least 1000 °C in step
e). Depending on the pyrolysis temperature, a distinction is made between
carbonization and graphitization. Carbonization refers to treatment at about 1000 to
1500 °C in an inert gas atmosphere, which leads to the separation of volatile products.
20 Graphitization, i.e. heating to around 2000 to 3000 °C in an inert gas atmosphere,
produces so-called high-modulus or graphite fibers. The carbon content increases
during pyrolysis, e.g. from approx.
67% by weight when treated at temperatures below 1000°C to approx. 99% by weight
25 when treated at temperatures above 2000°C. In particular, the fibers obtained by
graphitization have a high purity, are light, very strong, and very good conductors of
electricity and heat.

Step f)

30 Optionally, the nonwoven can be finished with at least one additive following steps c),
d), or e). The additives are preferably selected from hydrophobizing agents f1),
conductivity-improving additives f2), and other additives f3) different from f1) and f2)
and mixtures thereof.

5 Preferably, the nonwoven fabric is coated and/or impregnated (finished) with a

hydrophobizing agent f1) which contains at least one fluorine-containing polymer.
Preferably, the fluorine-containing polymer is selected from
polytetrafluoroethylenes (PTFE), tetrafluoroethylene-hexafluoropropylene copolymers
(FEP), perfluoroalkoxy polymers (PFA) and mixtures thereof. Perfluoroalkoxy polymers
10 are, for example, copolymers of tetrafluoroethylene (TFE) and perfluoroalkoxy vinyl
ethers, such as perfluorovinyl propyl ether. Preferably, a polytetrafluoroethylene is used
as the fluorine-containing polymer.

Preferably, the mass fraction of the fluorine-containing polymer f1) is 0.5 to 40 %,

particularly preferably 1 to 20 %, in particular 1 to 10 %, based on the
 21

15 mass of the nonwoven fabric. In a special embodiment, the fluorine-containing polymer

is PTFE and the mass fraction of the fluorine-containing polymer is 0.5 to 40 %,
preferably 1 to 20 %, in particular 1 to 10 %, based on the mass of the nonwoven fabric.

In many cases, the nonwoven already has good electrical and thermal conductivity due

20 to the carbon fibers used, even without conductivity-improving additives. However, to

improve the electrical and thermal conductivity, the nonwoven can be additionally
equipped with at least one conductivity-improving additive f2), preferably the nonwoven

25 is equipped with a conductivity-improving additive f2), which is selected from metal

particles, carbon black, graphite, graphene, carbon nanotubes (CNT), carbon nanofibers,
and mixtures thereof. Preferably, the conductivity-improving additive f2) comprises
carbon black or consists of carbon black. The nonwoven fabric can be finished with at
least one conductivity-improving additive f2), for example together with the polymer f1)

30 and/or other additives f3). Preferably, an aqueous dispersion is used to finish the
nonwoven fabric.

Preferably, the mass fraction of the conductivity-improving additive f2) is 0.5 to

45%, preferably 1 to 25%, based on the mass of the nonwoven fabric. In a particular
embodiment, the conductivity-improving additive f2) comprises carbon black or consists

5 of carbon black and the proportion by mass is 0.5 to 45%, preferably 1 to 25%, based on
the mass of the nonwoven fabric.

The nonwovens can also be equipped with at least one further additive f3). These
include, for example, various polymeric binders, surface-active substances, etc. from
10 components f1) and f2). Suitable binders f3) are, for example, furan resins, etc. In
particular, the nonwovens can be additionally equipped with at least one polymer
different from f1), with high-performance
polymers being preferred. The other polymers f3) are preferably selected from
polyaryletherketones, polyphenylene sulfides, polysulfones, polyethersulfones,
15 partially aromatic (co)polyamides, polyimides, polyamideimides,
 22

polyetherimides and mixtures thereof. The nonwoven fabric can be finished with at least
one additive f3), for example together with the polymer f1) and/or conductivity-
improving additives f2). The binders f3) can be subsequently cured if necessary. This
20 can, for example, take place together with the drying and/or sintering following the
finishing with the polymers f1) or also separately therefrom.

Preferably, the total mass fraction of further additives f3) is 0 to 80 %, preferably 0 to 50

%, based on the mass of the nonwoven fabric. If the nonwovens
25 additionally contain at least one further additive f3), the total mass fraction of further
additives f3) is 0.1 to 80 %, preferably 0.5 to 50 %, based on the mass of the nonwoven.

The nonwoven preferably has a thickness in the range from 50 to 500 µm,
30 particularly preferably from 100 to 400 µm. This thickness refers to the
unfinished, uncompressed state of the nonwoven, i.e. before the GDL is installed
in a fuel cell.

The nonwoven fabrics can be finished with the components f1), f2) and/or f3) by
5 application methods known to the skilled person, such as in particular coating and/or
impregnation. Preferably, a method selected from padding, doctoring, spraying,
patting, and combinations thereof is used to coat and/or impregnate the nonwoven
fabrics.

In the padder process, the nonwoven is passed through a padder (dip tank) with the
10 additive-containing solution or dispersion and then squeezed to the desired application
quantity of additive using a pair of rollers that can be adjusted for pressure and, if
necessary, gap.

A distinction is made between gravure printing and screen printing. In gravure printing,
for example, a knife-like ground steel band with or without a supporting doctor blade is
15 used as a doctor blade. It is used to wipe off the excess additives-
 23

containing solution or dispersion from the webs of the printing cylinder (doctor blade).
In screen printing, on the other hand, the squeegee is usually made of rubber or plastic
with a sharp or rounded edge.

20
During spray application, the additive-containing solution or dispersion is applied to
the nonwoven fabric to be finished by means of at least one nozzle, especially at least
one slotted nozzle.

25 The kiss-roll process is preferably used to coat the underside of horizontal

webs. The coating medium can be applied to the web in the opposite direction or in the
same direction. Transfer rollers can be used to achieve indirect coating with small
application quantities.

30
In a particular embodiment, the nonwoven fabric finished with components f1), f2), and/or f3) in
step f) of the process according to the invention is subjected to drying and/or thermal treatment.
Suitable processes for drying and/or heat treatment of nonwovens coated and/or impregnated with
additive-containing solutions or dispersions are known in principle. Preferably, the drying and/or
5 thermal treatment is carried out at a temperature in the range from 20 to 250 °C, particularly
preferably 40 to 200 °C. In addition, drying can take place at a reduced pressure.

Step g)

10
In a preferred embodiment, the gas diffusion layer according to the invention comprises
a two-layer laminate based on a nonwoven fabric and a microporous layer (MPL) on one
of the surfaces of the nonwoven fabric. To produce the gas diffusion layer, the nonwoven
15 obtained in step c), d), e) or f) can be coated with a microporous layer.

In contrast to the macroporous nonwoven, the MPL is microporous with pore diameters
that are generally well below one micrometer, preferably of no more
 24

20 than 900 nm, particularly preferably of no more than 500 nm, especially of no more than
300 nm. The average pore diameter of the MPL is preferably in the range from 5 to 200
nm, particularly preferably from 10 to 100 nm. The average pore diameter can be
determined by mercury porosimetry. The MPL contains conductive carbon particles,
25 preferably carbon black or graphite, in a matrix of a polymeric binder. Preferred binders
are the aforementioned fluorine-containing polymers, especially polytetrafluoroethylene
(PTFE).

The microporous layer preferably has a thickness in the range from 10 to 100
30 µm (micrometers), particularly preferably from 20 to 50 µm. This thickness refers to
the uncompressed state of the microporous layer B), i.e. before the GDL is installed
in a fuel cell.

The gas diffusion layer according to the invention preferably has a thickness
(total thickness of nonwoven fabric and MPL) in the range from 80 to 1000 µm,

5 particularly preferably from 100 to 500 µm. This thickness refers to the uncompressed
state of the GDL, i.e. before it is installed in a fuel cell.

A further object of the invention is a fuel cell comprising at least one gas
10 diffusion layer as defined above, or obtainable by a process as defined above. In
principle, the gas diffusion layer according to the invention is suitable for all
conventional fuel cell types, in particular low-temperature proton exchange membrane
fuel cells (PEMFC). Reference is made in full to the explanations given above on the
design of fuel cells.
15
FIGURE DESCRIPTION

Figure 1 shows the metal contents (Ca2+ , Na+ , Mg2+ and K+ ) of an untreated
20 nonwoven fabrics and a nonwoven fabric bonded with water of different conductivity.
 25

Figure 2 shows the content of Ca2+ and Na+ ions of a base nonwoven bonded with
water of varying conductivity, the carbon fiber nonwoven obtained from it by
25 carbonization, and a gas diffusion layer obtained after the application of an MPL.

Figure 3 shows the sum of the content of Ca2+ and Na+ ions, analogous to Figure
2.

30 The invention is explained with reference to the following examples, which are not to be
understood as limiting.

EXAMPLES

The metal contents (Ca2+ , Na+ , Mg2+ and K+ ) of the base nonwovens made from
5 oxidized polyacrylonitrile fibers, the resulting carbonized nonwovens, and GDL were
determined using an ICP-AES method (Inductively Coupled Argon Plasma - Atomic
Emission Spectrometry). The pretreatment of the samples (digestion) can be carried out
according to EPA Method 3050A for acid digestion of sediments, sludges, and soils. This
process includes the following steps:
10
1.) Nitric acid digestion at 95°C for 15 minutes.
2.) Further addition of nitric acid while continuing the digestion for 1h.
3) Remove from the hotplate; add deionized water and 20% hydrogen

15 peroxide solution.
4) Heat again on the hotplate for approx. 15 minutes and remove from the hotplate
once the bubbles have completely stopped forming.
5) Add concentrated hydrochloric acid and digest again for 1 hour.
20
Water with a conductivity according to the following Table 1 was used for hydroentanglement.
The reference water 1 corresponds to process water, as is usual for use in conventional processes
25 for web bonding with water jets. The ion concentration of water batches 2 and 3 was reduced by
nanofiltration.
 26

Table 1

Water batch Conductivity [microsiemens/cm] pH value#)

V1 290 -
(comparison)
2 100 6,1
3 22 6,1
#) determined according to DIN EN ISO 10523-C5:2012-04

Production example

5 To produce a basic nonwoven fabric, a dried fiber pile of 100% oxidized polyacrylonitrile
fibers was deposited on a carding machine. The fiber pile was fed to a bonding unit in
which the fibers are entangled and intertwined on both sides by means of high-energy
water jets at pressures of approx. 100 bar in the first stage and approx. 200 bar in the
10 second stage. The water qualities listed in Table 1 were used. The nonwoven was dried
and rolled up, with a basis weight of 150g/m² after hydroentanglement and drying. The
nonwoven was then subjected to a thickness calibration, whereby the thickness of the
jet-entangled nonwoven was reduced to 0.25 mm. The nonwoven was then fed into a
15 carbonization unit, in which carbonization took place under a nitrogen atmosphere at
around 1000 to 1400 °C.

An impregnating composition containing 70% carbon black and 30% PTFE in

20 relation to the solid material was used to finish the nonwoven. Finishing was carried out
by padding impregnation with an aqueous dispersion with a finishing weight of 15%
based on the mass of the GDL substrate (corresponding to 15 g/m²). This was followed
by drying at 180 °C and sintering at 400 °C. An MPL paste containing 2.0 wt.% PTFE

25 and 7.8 wt.% carbon in distilled water were then applied to the resulting substrate. The
nonwoven was then dried at 160°C and sintered at 400°C. The resulting MPL loading
was 24 g/m².
 27

22PA0037DE

Patent claims

1. Process for producing a gas diffusion layer for a fuel cell, in which one

5
a) provides a fiber composition comprising carbon fibers and/or
precursors of carbon fibers,

b) subjecting the fiber composition provided in step a) to a process for

10 producing a fiber pile,

c) the fiber pile is bonded to form a nonwoven fabric by the action of

aqueous fluid jets, the water used having a pH value in the range from
5.5 to 8.0,

15
d) if necessary, subjecting the nonwoven obtained in step c) to a thermal
and/or mechanical treatment for drying and/or further bonding,

e) if the fiber composition used in step a) comprises precursors of

20 carbon fibers, subjecting the nonwoven fabric to pyrolysis at a
temperature of at least 1000°C.

2. The method according to claim 1, wherein the water used in step c) to solidify
25 the fiber pile has a pH value in the range from 5.5 to 7.0, particularly preferably
in the range from 6.0 to 6.9.

3. Process according to claim 1 or 2, wherein the water used in step c) to solidify the
fiber pile has a conductivity of at most 250 microsiemens/cm at 25 °C, preferably
30 a conductivity of at most 200 microsiemens/cm at 25 °C, in particular a conductivity
of at most 150 microsiemens/cm at 25 °C.
 28

4. Process according to one of the preceding claims, in which the nonwoven obtained
5 in steps c), d) or e) is additionally finished with at least one additive (step f)),
preferably selected from hydrophobizing agents f1),
conductivity-improving additives f2), further additives f3), and mixtures
thereof.

5. A process according to any one of the preceding claims, wherein the

10 nonwoven obtained in steps c), d), e) or f) is additionally coated with a
microporous layer (step g)).

6. The method according to any one of the preceding claims, wherein the fiber
15 composition provided in step a) comprises precursors of carbon fibers selected from
unoxidized polyacrylonitrile fibers, oxidized polyacrylonitrile
fibers and mixtures thereof.

7. The method according to any one of claims 1 to 6, wherein the fiber composition
20 provided in step a) additionally comprises further fibers selected from fibers of
phenolic resins, polyesters, polyolefins, cellulose,
aramids, polyether ketones, polyether ester ketones, polyethersulfones,
polyvinyl alcohol, lignin, pitch and mixtures thereof.

25
8. The method according to any one of claims 1 to 6, wherein the fiber
composition provided in step a) consists of polyacrylonitrile fibers, in
25 particular polyacrylonitrile homopolymer fibers.

9. The method according to any one of the preceding claims, wherein the fiber

30 composition provided in step a) is subjected to a dry laying process in step b) to

produce a fiber pile.

10. The method according to any one of the preceding claims, wherein the water
used in step c) to solidify the fiber pile is at least partially recycled.
 29

5
11. Method according to claim 10, in which a fiber pile is bonded to form a nonwoven
fabric by the action of water-containing fluid jets, a wastewater stream is
discharged from the treatment of the fiber pile, a setpoint value the conductivity of
10 the wastewater stream is determined, the actual value of the conductivity of the wastewater
stream is determined after a limit value for the deviation of the actual value from the
setpoint value has been reached, the wastewater stream is at least partially subjected to
reprocessing and/or exchange with water of lower ion concentration and
15 the wastewater stream is at least partially returned to the treatment of the fiber pile.

12. A process according to any one of the preceding claims, wherein the
nonwoven obtained in step c) is subjected to further bonding by
calendering in step d).
20

13. The method according to any one of claims 4 to 12, wherein the
hydrophobizing agent f1) comprises at least one fluorine-containing
polymer.

14. The method according to any one of claims 4 to 13, wherein the conductivity-

25 improving additive f2) is selected from metal particles, carbon black, graphite,
graphene, carbon nanotubes (CNT), carbon nanofibers and mixtures thereof.

15. The method according to any one of claims 4 to 14, wherein the further additive

30 f3) is selected from polymeric binders, surfactants and mixtures thereof different
from components f1) and f2).

16. The method according to any one of claims 4 to 15, wherein the nonwoven fabric
is subjected to a thermal treatment during or after the coating and/or impregnation
5 with the hydrophobizing agent in step f1).
 30

17. Nonwoven fabric, obtainable by a process in which one

a) provides a fiber composition comprising carbon fibers and/or

10 precursors of carbon fibers,

b) subjecting the fiber composition provided in step a) to a process for

producing a fiber pile,

15 c) the fiber pile is bonded to form a nonwoven fabric by the action of aqueous
fluid jets, the water used having a pH value in the range from 5.5 to 8.0,
preferably a pH value in the range from 5.5 to 7.0, particularly preferably
a pH value in the range from 6.0 to 6.9.

20
18. The nonwoven fabric according to claim 17, wherein the water used in step c)
has a conductivity of at most 250 microsiemens/cm at 25 °C, preferably a
conductivity of at most 200 microsiemens/cm at 25 °C, in particular a
25 conductivity of at most 150 microsiemens/cm at 25 °C.

19. A gas diffusion layer obtainable by a process as defined in any one of claims
1 to 16.

19. A fuel cell comprising at least one gas diffusion layer obtainable by a process
30 as defined in any one of claims 1 to 16.
 31

Summary

The present invention relates to a process for producing a gas diffusion layer, in which
nonwovens made of carbon fibers or carbon fiber precursors are
5 subjected to bonding with water-containing fluid jets of specific water quality, to the gas
diffusion layer obtainable by this process and to a fuel cell containing such a gas
diffusion layer.
 32

Figures

Fig. 1

Contamination [ppm]
Water jet entangled
250 nonwoven
220
200 200 Water 1
200 180 180
160
Water 2
150 140
125
110 Water 3
100

50 40
30 30

0
Ca Na Mg K
Calcium Sodium Magnesium Potassium

5
 33

Fig. 2

Wasser - Water
Basis-Vliesstoff - basis nonwoven
Carbonfaser-Vliesstoff – Carbon Fiber Nonwoven
 34

Fig. 3

Summe – Sum of