communications engineering Article

https://doi.org/10.1038/s44172-025-00344-2

A catalyst-coated diaphragm assembly to

improve the performance and energy
efficiency of alkaline water electrolysers
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Zhuang Xu, Yanying Liu, Xiaobo Cheng, Yunshan Shang, Yongtao Wang, Jing Wang, Wenshi Li &
Guangli He

Alkaline water electrolysers are ideal for gigawatt-scale hydrogen production due to the usage of non-
precious metal and low-cost raw materials. However, their performances are modest with the
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separated electrode and diaphragm structure which can date back to more than 100 years ago. Here
we report a catalyst-coated diaphragm assembly to improve the performance of alkaline water
electrolysers. The transport resistance of OH- ions is reduced and the electrochemical surface area of
catalysts is enlarged by more than forty fold, representing more than 40% increase in hydrogen
production rate or as much as 16% reduction in energy consumption. The electrolyser with our
catalyst-coated diaphragm assembly delivers current densities as high as 1 A cm−2 at 1.8 V or 2 A cm−2
at 2 V and shows good stability after more than 1000 hours of operation. Therefore, the catalyst-
coated diaphragm assembly route is promising for the development of high-performance and efficient
alkaline water electrolysers.

Hydrogen is a key factor for future sustainability, acting as clean energy encounters additional bubble overpotential, due to the reduction of fresh
medium for transportation, industry and stationary power, as well as green electrocatalytic sites caused by the bubble coverage. The HER bubble
feed-stocks for chemicals and materials1. Hydrogen production using water overpotential is estimated to be about 45 mV, with bubble coverage at about
electrolysis is projected to reach 550 million tones by 2050, contributing to 90% and Tafel slop of 45 mV dec-1 for cathode electrocatalysts8,9. Moreover,
about 20% of CO2 abatement2. To reach this scale in its production, alkaline the mobility of OH- is nearly half of that of H+, resulting in higher ionic
water electrolysers (AWEs) will play a critical role because the component resistance in an AWE than that in a PEME10,11. The proton conductivity of
materials used in AWEs are abundant and less costly for hundreds of the state-of-the-art Nafion membrane for PEMEs is measured at higher
gigawatts implementations. To the contrary, the proton exchange mem- than 21.5 S m-1, while the ion conductivity of Zirfon diaphragm for AWEs is
brane electrolyser (PEME) with a similar technical readiness uses scarce and about 15 S m-1, adding to about 40 mV of ohmic overpotential for an AEW
costly platinum group metal electrocatalysts3,4. However, the AWE has its at a current density of 1 A cm−2 compared with a PEME with identical
own drawbacks to be solved, i.e., the efficiency loss due to the high electrode membrane thickness12,13. Considering the more favorable oxygen evolution
overpotential and ohmic resistance, primarily caused by the large gap reaction (OER) in AWEs than in PEMEs14, the performance of AWEs
between cathode and anode. This gap leads to low utilization of electro- should be close to that of PEMEs, with no more than 100 mV higher in cell
catalyst and long OH- transport distance5. Therefore, electrolyser structures voltage. Nevertheless, the state-of-the-art AWEs usually require a single cell
with zero-gap of electrode and diaphragm were developed6 and thin dia- voltage of almost 2 V at a current density below 0.5 A cm−2 15–17, quite a
phragm of ZrO2 coated polyphenylene sulfide mesh, e.g., Zirfon with a drawback in performance compared with that of a PEME, i.e., cell voltage of
thickness of 220 μm, was used to improve the performance of AWEs7. Thus about 2 V at a current density of 2 A cm−2 18,19.
far, the overvoltage of AWEs is still about 200 mV higher than that of We postulate that the primary reason in the suppressed efficiency of an
PEMEs, and AWE’s current density is less than 25% of that of a PEME7. industrial AWE is in the hundred years old cell structure itself with sepa-
These translate into about 10% lower in efficiency and more than 4 times rated electrode and diaphragm (SED) as shown in Fig. 1a, b. Even though the
larger in the electrolyser’s volume. electrode is physically pressed onto the diaphragm for the zero-gap AWE,
The performance difference between AWE and PEME stems from the there is still micro gap between the electroctalyst and the ion transport
different electrolytes used. Unlike PEME, the AWE cathode is immersed in interface. As a result, the bubbles in the gap disturb the electric field and
liquid alkali solutions and the hydrogen evolution reaction (HER) block the OH- transport in the electrolyte20,21, exhibiting rather high ohmic

Hydrogen and Ammonium Energy R&D Center, National Institute of Clean-and-Low-Carbon Energy, Beijing, China. e-mail: [email protected]

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Fig. 1 | The catalyst-coated diaphragm concept compared with the state-of-the- diaphragm electrolyser. c, d Scheme (a) and structure illustration (b) of the catalyst-
art separated electrode and diaphragm structure for an alkaline water electro- coated diaphragm electrolyser.
lyser. a, b Scheme (a) and structure illustration (b) of the separated electrode and

resistance and hindering the electrochemical reaction. On the contrast, the bindered agglomerates of Raney Ni particles, which is attributed to the
concept of membrane electrode assembly is widely used in PEMEs ever since uneven distribution of the catalyst particles during the blade coating process.
1950s22,23, with nanostructured catalyst coated on the membrane using Cross section image (Fig. 2d) and elemental mapping (Fig. 2e) of the CCD
proton exchange ionomer as the binder, leading to improved electrolysis show that catalyst layers are directly bound to each side of the diaphragm,
performance by enlarged electrochemical reaction area and reduced H+ and stacking pores are formed among the Raney Ni particles, which makes
transport distance. The membrane electrode assembly route is also intro- the transport channel for the electrolyte as well as the gases produced. The
duced to the development of anion exchange membrane electrolyser, which statistical porosity of the CCD is further measured using mercury intrusion
is considered as a new type of alkaline electrolyser24. However, the mem- method, with results shown in Fig. 2f. For pristine Zirfon 220 diaphragm,
brane electrode assembly route is seldom experimented for AWEs by dominant pores are located between the diameter of 50 nm and 500 nm,
coating electrocatalysts onto the porous diaphragm, and only marginally with minor pores located around 10 μm. The pore volume peaks are
SED-comparable performance was reported by very few works25. detected at pore diameters of 60 nm, 150 nm and 10 μm, showing meso-
Here, we demonstrated a substantial performance improvement of an porous nature of the Zirfon 220 diaphragm. As for the fresh Raney Ni
industrial AWE, i.e., single cell voltage of 2 V at a current density of catalsyt, most of the pores are located around the diameter of 2 μm. When
2 A cm−2, comparable with that of the state-of-the-art PEME, by introdu- Nafion-bindered Raney Ni particles are coated onto both sides of the Zirfon
cing the catalyst-coated diaphragm (CCD) assembly concept to fabricate the 220 diaphragm to form the CCD, the pores with diameters of between
electrolyser as shown in Fig. 1c, d. We achieved a 40-fold electrocatalyst 100 nm and 400 nm are reduced, and the pore volume peak located at 10 μm
utilization and a 40% reduction in ohmic resistance compared with the also declined. The particle size of Raney Ni catalyst is larger than 2 μm, and
conventional SED AWEs, due to the realization of direct electrocatalyst- the catalyst loading is only 2 mg cm−2, much lower than the areal density of
diaphragm contact at micro scale level. Most of the raw materials used for Zirfon 220 diaphragm (~22 mg cm−2). As a result, the slightly increased
this CCD route AWE are the same as those used in the state-of-the-art porosity of the CCD at 0.64 over Zirfon 220 diaphragm’s 0.60 is ascribed to
AWEs, making it possible in its quick implementation to industrial appli- the formation of pores with the diameter located between 11 and 13 μm
cations. We believe that the transition from SED to CCD would benefit the which are probably caused by the packing of Raney Ni particles and Nafion
development of high-performance and efficient AWEs, contributing to ionomer aggregates27.
large scale production of green hydrogen for future sustainability. The microstructure of the traditional SED was also investigated by
characterizing the Raney Ni catalyst coated Ni mesh electrode (CCE) and its
Results interface with the diaphragm. As shown in Fig. 2g, typical CCE exhibits a
Structural differences between the CCD and SED woven mesh morphology with a rough surface. The cross section SEM
The microstructure of the CCD was characterized for the catalyst layer and image in Fig. 2h reveals that the porous Raney Ni catalyst is distributed
the cross section. The scanning electron microscope (SEM) image in Fig. 2a around the Ni fibers with a diameter of about 150 μm, and the thickness of
shows that the CCD catalyst layer exhibits random agglomerates of Raney the catalyst phase ranges from 100 μm to 150 μm. The surface roughness of
Ni particles with featured size of between sub-10 and 30 μm. The high the CCE is estimated to be about 50 μm, much bigger than that of the
resolution transmission electron microscope (HR-TEM) image shown in catalyst layer of CCD. Consequently, when the SED is fabricated, an obvious
Fig. 2b indicates that the Nafion binder is spread on the surface of the Raney gap is formed between most part of the catalyst in CCE and the diaphragm
Ni particle, and the Nafion layer thickness is measured at about 5 nm, which surface. In particular, only few catalysts were positioned favorably between
is similar to the case of typical fuel cell catalyst layer using carbon supported the Ni fibers of the CCE and the diaphragm for short transport length of OH-
Pt (Pt/C) as the catalyst26. Ultra-depth optical microscope image in Fig. 2c ions, while most of the catalysts were positioned rather unfavorably causing
reveals the rough nature of the CCD surface, with catalyst layer thickness long distance for OH- to transport due to poor contact with the diaphragm.
ranging from 5 to 10 μm. Vacancies are also created among the Nafion- Therefore, it is expected that the CCD with catalyst layer directly deposited

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Fig. 2 | Microstructure analysis of the catalyst-coated diaphragm in comparison electron microscope image (d) and elemental mapping (e) of the catalyst-coated
with catalyst-coated mesh electrode. a Representative scanning electron micro- diaphragm. f Pore diameter distributions of Zirfon 220 diaphragm, Raney Ni
scope image of the Raney Ni catalyst layer. b High resolution transmission electron catalyst and the catalyst-coated diaphragm. The pore volume is normalized to the
microscope image of typical Raney Ni particle in the catalyst-coated diaphragm. sample mass of the catalyst-coated diaphragm. g, h Scanning electron microscope
c Representative ultra-depth optical microscope image of the catalyst-coated images of surface (g) and cross section (h) for the Raney Ni catalyst-coated Ni mesh
diaphragm with Raney Ni catalyst layer. d, e Typical cross-section scanning electrode.

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Fig. 3 | Electrochemical stability evaluation. a Single electrolysis cell voltage recorded with current density switch between 0.4 mA cm−2 and 2 A cm−2. The duration for each
current density hold was set at 30 s. b Single electrolysis cell voltage profiles collected with switched current density operation at 0.4 and 0.8 A cm−2 for more than 1000 h.

onto the diaphragm could exhibit much lower ionic resistance than the SED, CCD exhibits an improved electrochemical durability over the conventional
and at the same time, higher utilization of the catalyst. SED. This is a very important feature for CCD’s industrial applications.
The chemical and physical change of the CCD was further analyzed
Durability of the CCD after more than 300 h of operation. In order to demonstrate the reprodu-
The physical stability of the CCD was evaluated by measuring the bond cibility, two CCD samples with Raney Ni catalysts were tested with constant
strength of the catalyst layer and the Zirfon 220 diaphragm. The mean current density of 0.5 A cm−2 at 80 ± 2 oC. The voltages of both CCDs are
adhesive strength measured is in the range of 0.179–0.519 MPa. After between 1.71 V and 1.73 V within the testing duration as shown in Fig. 4a.
pulling apart the catalyst layer from the CCD, it was observed that the ZrO2 Occasional voltage rise is due to the addition of water into electrolyte. For
nanoparticles were also peeled from the surface of Zirfon 220 diaphragm, one of the CCDs, its polarization curve almost unchanged after the 300 h of
indicating strong adhesion of the catalyst layer. This feature is critical for the operation (Fig. 4b). The fresh and operated CCDs were characterized with
structural stability of the CCD. the X-ray photoelectron spectroscopy (XPS) and the spectra are displayed in
The electrochemical stability of the CCD was also investigated under Fig. 4c. Due to the Nafion coverage on the catalyst, very limited signal of Ni
both dynamic and constant current conditions in the electrolyser according was detected for the fresh CCD. After about 8 h of activation, featured peak
to the recommended method for degradation rate assessment proposed in of Ni (II) 2p was observed at ~855.5 eV. It shifts to higher binding energy by
the EU harmonized protocols28. After 10000 cycles of load current density about 0.2 eV for the CCD anode operated by 300 h, indicating the presence
switches between 0.4 mA cm−2 (close to open circuit) and 2 A cm−2, the of Ni (III) species. For the Nafion binder, the F 1 s peak slightly shifts to
voltage degradation rate measured at 2 A cm−2 was 18.5 μV h-1 for the CCD lower binding energy after operation, due possibly to the swelling and
electrolyser, which is about 30% of that for an SED electrolyser (65.6 μV h-1), rearrangement of the polymer chain. The S 2p peak for the CCD anode shifts
as shown in Fig. 3a. After more than 1000 h of operation at constant current negatively after activation due to the de-protonization of -SO3H in alkaline
density between 0.4 A cm−2 and 0.8 A cm−2 (Fig. 3b), the voltage degrada- electrolyte. For CCD operated by 300 h, the S 2p peak shows no obvious
tion rate was estimated at 2.5 μV h-1 for the CCD electrolyser, which is also change, indicating relatively stable chemistry of the Nafion side chain. The
lower than that of a comparable SED electrolyser (3.6–4.0 μV h-1). Thus, the porosity of the CCD is decreased by more than 50% after the operation of

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Fig. 4 | Constant current operation and post analysis of the catalyst-coated dia- operation. c X-ray photoelectron spectroscopy signals for fresh and operated
phragm. a Single electrolysis cell voltages operated at constant current density of catalyst-coated diaphragms. Regions of Ni 2p, F 1 s and S 2p were recorded.
0.5 A cm−2. b Polarization curves measured after 8 h of activation and 300 h of

300 h, which can be attributed to the shrinkage of diaphragm pores due to high temperature thermal spraying9 or electrochemical/chemical deposition
the pressurization under cell assembling force. methods29,30 to immobilize catalyst onto woven-mesh or porous metal
substrate. Furthermore, a variety of powder catalysts are available for the
Water electrolysis performance CCD, creating more possibilities for electrode iteration for even better
A substantial performance improvement was achieved for the CCD elec- performance in a CCD electrolyser. Typical precious metal catalysts of Pt/C
trolyser. The polarization curves in Fig. 5a show that the CCD voltage is and RuO2 were chosen first for the cathode and anode, respectively, which
about 200 mV lower at 2 A cm−2 than that of a traditional SED, which are considered among the most active catalysts for HER and OER in alkaline
translates into more than 16% increase in efficiency. At voltage of 2 V, media. The obtained CCD denoted as Pt/C(-)|RuO2(+) reaches rather high
usually the maximum allowable operating voltage for an industrial AWE as current density of 1 A cm−2 at 1.8 V and 2 A cm−2 at 2 V with Pt loading of
electrochemical corrosion management dictates so, the CCD reaches a 0.1 mg cm−2 and RuO2 loading of 2 mg cm−2, as shown in Fig. 5c. These
current density as high as 1.8 A cm−2, surpassing the SED (1.3 A cm−2) by results outperform most of the reported anion exchange membrane elec-
more than 40%. As a result, the hydrogen production rate per cell area can be trolysers with a current density of 1 A cm−2 at 1.85 V24, and they are com-
enhanced, leading to a cost reduction in AWEs. What is noteworthy is that, parable to those of an PEME using Nafion 117 membrane with similar
the Raney Ni catalyst loading in a CCD (2 mg cm−2) is less than 10% of that thickness to Zirfon 220 diaphragm (185 μm vs. 220 μm)31, indicating the
used in an SED (26–30 mg cm−2), while the CCD voltage in the electro- feasibility to develop high-rate AWEs. Subsequently, the anode catalyst was
chemical reaction control region (current density <0.1 A cm−2) is slightly substituted with the Ni-Fe layered double hydroxide (NiFe-LDH), which
lower than that in the SED. At voltage of 1.8 V, the calculated mass activity of has been reported as one of the most active non-precious metal catalyst for
catalyst with the CCD is about 20-fold that with the SED. Thus, it can be OER in alkaline media32,33. Indeed, the prepared CCD (denoted as Pt/C(-)|
inferred that enlarged electrochemically active surface area has been NiFe-LDH(+)) exhibits much lower voltage at a current density below
achieved with the CCD. The electrochemical impedance spectra (EIS) in 1 A cm−2, with a voltage drop of more than 50 mV at 0.5 A cm−2. However,
Fig. 5b reveal that the electrochemical surface area of CCD is 4 times larger, worsened performance was observed at a current density above 1 A cm−2,
indicating more than forty fold increased catalyst utilization over the SED. which is ascribed to the poor electronic conductivity of NiFe-LDH34. In
Furthermore, the ohmic resistance (Rs) of the CCD cell is more than 30% addition, the electrochemical stability of NiFe-LDH for OER is yet to be
lower, demonstrating more efficient transport of the OH- ions. As shown in overcome in concentrated KOH electrolyte of AWE due to oxidation and
Fig. 1, this is attributed to the shortened travel distance of OH- from cathode leaching of Ni(II) and Fe(II) species35. Finally, commercial Raney Ni was
to anode, due to the direct contact between the Raney Ni catalyst layer and used as the non-precious metal catalyst for both cathode and anode of the
the diaphragm. CCD (denoted as RNi(-)|RNi(+)), for the corrosion resistance of Ni in
The advantage of the CCD is further explored by using various types of AWE conditions is more than 2 magnitude better than Fe, Pt, and Ru36.
catalysts, including precious metal and non-precious metal ones. It is worth With the same catalyst loading at 2 mg cm−2, the performance of RNi(-)|
noting that the preparation of CCD is a physical coating process at sub- RNi(+) CCD surpassed the one with RuO2 as the anode catalyst (denoted as
100 °C temperatures, a drastically different fabrication process than that RNi(-)|RuO2(+)) at a current density below 1.5 A cm−2, inferring that the
used for SED electrode. An SED electrode usually involves sophisticated OER activity of Raney Ni is higher than RuO2. By fitting the polarization

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Fig. 5 | Performance in alkaline water electrolyser. a, b Polarization curve, mass activity was calculated with the current density at voltage of 1.8 V. The electro-
activity (a) and electrochemical impedance spectra (b) for catalyst-coated dia- chemical impedance spectra were profiled at current density of 0.5 A cm-2.
phragm electrolyser compared with separated electrode and diaphragm electrolyser. c, d Polarization curves (c) and their Tafel equation fitting (d) for catalyst-coated
Raney Ni was used as catalyst with loadings of 2 mg cm−2 and 26–30 mg cm−2 for the diaphragms with various catalysts. The catalyst loading was controlled at 2 mg cm-2
catalyst-coated diaphragm and mesh electrode, respectively. All polarization curves for RuO2, Ni-Fe layered double hydroxide (NiFe-LDH) and Raney Ni. For carbon
are without iR correction. Error bars in the polarization curve of the catalyst-coated supported Pt (Pt/C), the Pt loading was 0.1 mg cm-2. For Tafel equation fitting, the
diaphragm electrolyser is obtained by evaluation of four samples, and the average cell voltage was corrected by subtracting the voltage drop caused by the ohmic
voltage at each current density is presented with standard deviation indicated. Mass resistance (iR).

curve with Tafel equation (Fig. 5d), it was revealed that the OER exchange AWEs, performance of the CCD is among the best. Therefore, the CCD
current density was enhanced by at least 3 times for Raney Ni. Because of its could be a potential route for the development of high-rate AWEs.
better electronic conductivity for RuO2, the voltage of RNi(-)|RuO2(+)
CCD gradually caught up with the RNi(-)|RNi(+) at a current density near Discussion
2 A cm−2. On the other hand, however, a performance gap was found In summary, the CCD concept was proposed as an alternative route for the
between the RNi(-)|RuO2(+) and Pt/C(-)|RuO2(+) CCDs, implying lower development of high-rate AWEs. Direct coating of catalyst layers on the
HER activity of Raney Ni than Pt/C. According to the linear-fitted polar- porous diaphragm has shortened the OH- transport distance and enlarged
ization curve in Fig. 5d, it was deduced that the HER exchange current the electrochemical surface area by over forty fold, demonstrating more than
density for Raney Ni was only a third of that of Pt/C. Thus, Raney Ni catalyst 40% improvement of hydrogen production rate or as high as 16% reduction
exhibits a pretty good OER activity, while the electronic conductivity and the in energy consumption than conventional SED AWEs. With commercial
HER activity need to be improved. Further measurements show that the catalysts and diaphragm, the CCD AWE was capable of delivering a current
Raney Ni catalyst layer possesses an electronic conductivity at about 1 S m-1, density as high as 1 A cm−2 at 1.8 V and 2 A cm−2 at 2 V, outperforming
over a magnitude lower than that of Pt/C and even close to that of IrO2 in most of the anion exchange membrane electrolysers reported. The results
PEME37,38, which are areas for further improvements. Considering the fact are even close to those of the performance of a medium level PEME. Unlike
that Raney Ni catalyst is produced from abundant and low-cost raw the SED electrode prepared from sophisticated high-temperature thermal
materials through large scale metallurgy process, higher loading of Raney Ni spraying or electrochemical/chemical deposition, the fabrication of CCD is a
in CCD is expected to enhance the electrolysis performance with a negligible low-temperature physical coating process and can use powder catalysts
cost increase in AWEs. received. The simplified fabrication of CCD is user friendly to conduct in
The performance of our CCDs is further compared with recent works ether academic labs or industrial batch production lines. This is in turn,
and summarized in Table 1. It shows that the CCD route achieves sub- expected to dramatically accelerate the technology iteration of CCD AWEs.
stantially high performance. In particular, for the non-precious metal based Preliminary results also show that the CCD structure is relatively solid and

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Table 1 | Performance of the CCDs in comparison with recently reported results

# Performance Electrolyte and Electrodes and diaphragm Reference

temperature
1 1.78 V @ 0.5 A cm−2 30 wt% KOH at 90 oC Raney Ni-Mo sprayed perforated Ni sheet anode/cathode and Dapozol membrane 9
1.98 V @ 1.0 A cm−2
2 1.7–1.73 V @ 0.5 A cm-2 30 wt% KOH at 80 oC Raney Ni foam cathode, Ni-Fe-LDH decorated Fe foam anode, and Al2O3:ZrO2/PSU 41
1.83–1.90 V @ 1.0 A cm-2 composite diaphragm
3 1.8 V @ 0.5 A cm-2 28 wt% KOH at 80 oC Ni–Mo-coated expanded Nickel grids cathode, NiCo2O4-coated expanded Nickel grids 17
anode, and PSU/PVP/TiO2 composite diaphragm
4 1.65 V @ 0.5 A cm−2 30 wt% KOH at 80 oC Raney Ni foam cathode, Ni-Fe-LDH decorated Fe foam anode, and cellulose nanocrystals 42
1.78 V @ 1.0 A cm-2 blended ZrO2/PSU diaphragm
5 1.74 V @ 0.5 A cm-2 30 wt% KOH at 80 oC Raney Ni foam cathode, Ni-Fe-LDH decorated Fe foam anode, and Zirfon diaphragm 42
1.98 V @ 1.0 A cm-2
6 1.83 V @ 0.3 A cm-2 6 M KOH at 75 oC Raney Ni plate cathode, stainless steel 316 L plate anode, and Zirfon 500 diaphragm 43
-2
7 1.68 V @ 0.5 A cm 30 wt% KOH at 80 oC Raney Ni foam cathode, Ni-Fe-LDH decorated Ni foam anode, and ZrO2/PSU composite 13
1.80 V @ 1.0 A cm-2 300 μm diaphragm
8 1.78 V @ 0.5 A cm-2 30 wt% KOH at 80 oC Raney Ni foam cathode, Ni-Fe-LDH decorated Ni foam anode, and Zirfon diaphragm 13
1.98 V @ 1.0 A cm-2
9 1.86 V @ 0.5 A cm−2 30 wt% KOH at 80 oC Raney Ni mesh cathode, CoMnO@CoFe-LDH decorated Ni foam anode, and Zirfon 500 44
2.1 V @ 1.0 A cm−2 diaphragm
10 1.95 V @ 1.0 A cm-2 30 wt% KOH at 80 oC Raney Ni mesh cathode, CoMnO@CoFe-LDH decorated Ni foam anode, and 44
diethanolamine functionalized ZrO2/PSU diaphragm
11 1.85 V @ 0.5 A cm-2 32.5 wt% KOH at 80 oC Raney Ni coated Zirfon diaphragm with per-oxidized Ni foam anode 25
2.1 V @ 1.0 A cm-2
12 1.72 V @ 0.5 A cm-2 30 wt% KOH at 80 oC Raney Ni coated Zirfon 220 diaphragm This work
1.83 V @ 1.0 A cm-2
13 1.64 V @ 0.5 A cm−2 30 wt% KOH at 80 oC Pt/C and Ni-Fe LDH coated Zirfon 220 diaphragm This work
1.8 V @ 1.0 A cm-2
All voltages are non-iR corrected to demonstrate practical electrolysis performance.

durable under harsh alkali and electrochemical conditions of AWEs, vacuum for 1 h. The precious metal loading were controlled at 0.1 mg cm−2
meeting the prerequisites for its industrial applications. We believe that the for Pt/C cathode and 2 mg cm−2 for RuO2 anode, respectively. For com-
transition from SED to CCD would benefit the development of high- parison, the catalyst loading of NiFe-LDH anode and Raney Ni electrodes
performance AWEs, contributing to large scale production of green was also controlled at 2 mg cm−2. All the CCDs were hot-pressed at 150 oC
hydrogen for future sustainability. and 5 MPa for 5 min before electrolysis performance evaluation.

Methods Physical characterizations

Materials The morphology was observed by a field emission scanning electron
Commercial Pt/C (20 wt%, Shanghai Hesen Electric Co., Ltd), RuO2 microscope (SEM, FEI Nova Nano 450) with energy dispersive X-ray
powder (Beijing InnoChem Science & Technology Co., Ltd), Nafion spectroscopy (EDS, Oxford X-maxN 50) mapping and a high resolution
solution (10 wt%, DuPont), Zirfon 220 diaphragm (AGFA) and Raney Ni transmission electron microscope (HR-TEM, JEM-ARM200F NEOARM).
coated mesh electrode (Baoshilai New Material Technology Co., Ltd.) The CCD or CCE samples were cut into 1 cm × 1 cm sections and dipped
were used as received without any further treatment. Analytical grade into a mixture of epoxy resin and hardener (G1, Beijing XXBR Technology
KOH (85 wt%), Ni(NO3)2•6H2O, Fe(NO3)3 •9H2O and Na2CO3 were Co.,Ltd.) for 20 min. Then, the excess resin mixture was wiped off, and the
purchased from Shanghai Aladdin Biochemical Technology Co., Ltd. samples were cured at ambient temperature for at least 24 h. The embedded
Fresh Raney Ni catalyst (Jiangsu Raney Metal Technology Co., Ltd) was samples were deposited on mounts and covered with shield plates, and an
carefully passivized in ambient air for at least 12 h and sieved through argon ion beam cross-section polisher (ArBlade 5000, Hitachi High-Tech
mesh to obtain desirable particle size of less than 30 μm. The NiFe-LDH Co., Ltd.) was used to obtain cross-sections. The three dimensional image of
catalyst was prepared by one-step co-precipitation method. Typically, the CCD was taken on a ultra-depth optical microscopes (Leica DM6 M
1 mol of Ni(NO3)2•6H2O and 0.5 mol of Fe(NO3)3 •9H2O were dissolved LIBS Wetzlar, Germany) and the surface roughness was calculate by the
to obtain aqueous solution and kept at 85 oC. The aqueous solution with LeicaMap Premium V9 software. The porosity of Raney Ni catalyst, Zirfon
1.75 mol of Na2CO3 was then added under mechanical stirring. After 220 diaphragm and the CCD were measured on a Quantachrome Pore-
precipitation, the resulting suspension was stirred for another 5 h, and master GT60 mercury intrusion analyzer. The intrusion and extrusion
subsequently filtered, washed with deionized water until the pH was pressure was set in the range of 0 to 30,000 psi. The adhesion strength
measured at 7. Finally, the NiFe-LDH catalyst was collected after dried at measurement of the catalyst layer in CCD was conducted on a LUMiFrac
90 oC for 12 h. adhesion analyzer according to the standard of ISO 462439. A CCD sample
with a diameter of 10 mm was firmly stuck onto the test pedestal with super
Preparation of CCD glue. The rotating speed of the pedestal was gradually increased until the
Catalyst ink was prepared by mixing the catalyst powder with Nafion peeling of catalyst layer. The adhesive strength is obtained according to the
solution and water. To obtain homogeneous dispersion, the mixture was centrifugal force. The through-plane electronic conductivity of the CCD
sonicated for at least 2 min. The mass ratio of catalyst to dry Nafion ionomer catalyst layer was measured according to the reference37. The catalyst layer
was optimized and controlled at 1: 10 for Pt/C cathode and 1: 1 for RuO2 was sprayed onto the aluminum foil and allowed to dried at 80 oC for 3 h.
anode, NiFe-LDH anode, and Raney Ni electrodes. The catalyst ink was After hot-pressed at 150 oC and 5 MPa for 5 min, the catalyst coated foil was
blade-coated onto the Zirfon 220 diaphragm and allowed to dry at 80 oC in sandwiched between carbon papers to measure the electronic resistance

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using the four-point probe micro-ohm meter (Rooko, FT-541SJB-341). 9. Razmjooei, F. et al. Improving plasma sprayed Raney-type
X-ray photoelectron spectroscopy (XPS, Thermo Scientific ESCALAB nickel–molybdenum electrodes towards high-performance hydrogen
250Xi) was profiled with a 150 W Al Kα X-ray source gun and the spot size is evolution in alkaline medium. Sci. Rep. 10, 10948 (2020).
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33. Magnier, L. et al. Fe–Ni-based alloys as highly active and low-cost Competing interests
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Acknowledgements nc-nd/4.0/.
We acknowledge financial support from National Key Research and
Development Program of China (No. 2023YFB4005000) and CHN Energy © The Author(s) 2025
Investment Group Co., LTD (No. GJNY−23-95).

Author contributions
Z.X. designed the research and wrote the manuscript. Y.L., X.C., and Y.S.
conducted the experiments. Y.W, J.W., and W.L. performed the
characterizations. G.H. conceptualized the project.

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