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JANUARY 17, 2023

Green hydrogen: alkaline versus

PEM electrolysers?

The key difference between an alkaline

electrolyser and a proton exchange
membrane electrolyser (PEM) is what ion
diffuses between the anode and cathode side
of the cell. In an alkaline electrolyser,
alkaline OH- ions diffuse. In a PEM
electrolyser, protons, H+ ions, diffuse. Ten
fundamental differences follow.

The lowest cost green hydrogen will

come from alkaline electrolysers run at high
utilizations, powered by clean, stable grids
with excess power (e.g., nuclear, hydro).

PEMFCs are more suited for

backstopping renewables, although there is
still some debate over the costs, longevity,
efficiency and whether intermittent
wind/solar can be put to better use
elsewhere.

(1) In an alkaline electrolyser, water is

broken down at the cathode. 4 x H2O
molecules gains 4 x e- and become 2 x H2 +
4 x OH- ions. The OH- ions then diffuse
across the cell to the anode. To complete the
electrical circuit, 4 x OH- ion surrender 4 x e-
at the cathode and become 2 x H2O
molecules + 1 x O2 molecule. A schematic is
below.

(2) In a PEM electrolyser, the chemistry

is very different. Water is broken down at the
anode. 2 x H2O molecules surrender 4 x e-
and become an O2 molecule + 4 H+ ions
(protons). The H+ ions then diffuse across
the cell to the cathode. To complete the
electrical circuit, at the cathode, 4 x H+ ions
gain 4 x e- and become 2 x H2 molecules.

(3) PEMs have Membranes. H+ ions are

the smallest ions in the Universe, measuring
0.0008 pico-meters (comparable with other
ionic radiuses below). This means protons
can diffuse through solid polymers like
Nafion, which otherwise resist electricity and
resist the flow of almost all other materials;
totally isolating the anode and cathode sides
of the cell in a PEMFC.

Ionic radius: comparing cation

chemistry?

(4) Alkaline Electrolysers have

Diaphragms. OH- ions are larger, at 153
pm (which is actually quite large, per the
chart above). Thus they will not diffuse
through a solid polymer membrane.
Consequently, the anode and cathode are
separated by a porous diaphragm, bathed in
an electrolyte solution of potassium
hydroxide, produced via a variant of the
chlor-alkali process. This (alkaline)
electrolyte also contains OH- ions. This
helps, because more OH- ions makes it faster
for excess OH- ions to diffuse from high
concentration on the cathode side of the cell
to low concentration on the anode side of the
cell (see (2)).

Chlor-alkali process: the

economics?

(5) Safety implications. Alkaline

electrolysers are said to be less safe than
PEMs. The reason is the porous diaphragm.
Instead of bubbling out as a gas on the anode
side, very small amounts of oxygen may
dissolve, diffuse ‘in the wrong direction’
across the porous diaphragm, and bubble out
alongside the hydrogen gas at the cathode
side. This is bad. H2 + O2 make an explosive
mixture.

(6) Footprint implications. One way to

deal with the safety issue above is to place
the anode and cathode ‘further apart’ for an
alkaline electrolyser. This lowers the chances
of oxygen diffusing across the diaphragm.
But it also means that alkaline electrolysers
are less power-dense.

(7) Efficiency implications. Small

amount of current can leak through the KOH
solution in an alkaline electrolyser, especially
at very large current densities. When a direct
current (e-) is added to the cell, we want it to
reduce 2 x H+ into H2. However, a small
amount of the current may be wasted,
converting K+ into K; and a small amount of
‘shunt current’ may flow through the KOH
solution directly from cathode to anode. We
think real-world PEMs will be around 65%
efficient (chart below, write-up here) and
alkaline electrolysers will be multiple
percentage points lower.

(8) Cost implications. An alkaline

electrolyser may be a few $100/kW cheaper
than a PEM electrolyser. Because the
diaphragm is cheaper than the membrane.
The electrodes are cheaper too. Our overview
of electrolyser costs is below.

Electrolysers: how much

deflation ahead for hydrogen?

(9) Longevity implications. Today’s

PEMs degrade 2x faster than alkaline
electrolysers (40,000 hours versus 90,000
hours, as general rules of thumb). This is
primarily because the membranes are fragile.
And H+ ions are, by definition, acidic. But as
with all power-electronics, the rate of
degradation is also a function of the input
signal and operating conditions.

Battery degradation: causes,

effects & implications?

(10) Flexibility implications. Alkaline

electrolysers are not seen to be a good fit for
backstopping renewables (chart above).
According to one technical paper, “It is well
known that alkaline water electrolysers
must be operated with a so-called protective
current in stand-by/idle conditions (i.e.,
when no power is provided by renewable
energy sources) in order to avoid a
substantial performance degradation”.
When ion flow stops, there is nothing driving
OH- ions across the cell, and pushing the H2
and O2 out of the cell. In turn, this means O2
and H2 bubbles can form. They may
accumulate around electrode catalysts. Then
when the cell starts up again, the gas bubbles
block current flow. In turn, overly large
resistance or current densities can then
degrade the catalysts.

Green hydrogen: can

electrolysers run off
renewables?

COMMENTARY, CUTTING EDGE

HYDROGEN

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