High-efficiency and stable alloyed nickel-

based electrodes for hydrogen evolution

by seawater splitting
Hydrogen is regarded as a highly efficient and clean source of energy. We use Hydrogen
evolution reactions to produce hydrogen. Platinum is the desired metal to act as a catalyst, but
due to the high economic factor is advised to have a cheaper alternative to commercialize the
process. Here Ni-metal catalyst is considered an alternative, and experiments are done to
synthesize the catalyst by using Ti foil as a substrate for the electrodeposition method.
Pt is used due to its high-electron conducting ability, charge transfer capacity, low impedance
and extraordinary stability. By Brewel-Engel valance bond theory, electrocatalysts towards HER
can be made by alloying the transition metals on the left half having empty or half-filled d
orbitals with the metals on the right half featuring internally paired d-electrons.
According to volcano plots for HER, Ni shows better catalytic activity along with its alloys like
NiMo, NiSe, NiFe, NiGa, NiCo etc.
Ti foil is used as substrate due it has extraordinary corrosion resistance during water splitting.
By etching Ti foil to remove oxide on the surface, electron-conducting ability and specific
surface area are increased.

Experimental Section
Pre-treatment of Ti foil
Before electrodeposition, the TiOx species on the Ti foil surface were removed according to the
following procedures. In detail, Ti foil with a thickness of 1 mm was rinsed with deionized water,
soaked in acetone under ultrasound for 30 min, and subsequently thoroughly washed with
deionized water to remove acetone. Finally, the freshly cleaned Ti foil was immersed in 1 M
oxalic acid aqueous solution, heated in a water bath at 95 _C for 2 h, then rinsed with deionized
water and dried in air.
Fabrication of Ti/NiM alloy electrode
The feasibility of this strategy was confirmed by the following experimental procedures: A mixing
aqueous solution consisting of 50 mL of 5 mM metal salt precursors (H2PtCl6, CoCl2, CuCl2,
(NH4)6Mo7O24, or AuCl3) and 5 mM NiCl2 aqueous solution was mixed by ultrasonic
irradiation for 30 min. The electrodeposition processes of binary NiM alloys on Ti foils were
carried out in a standard three-electrode electrochemical cell with Ti foil as a working electrode,
a parallel positioned Pt foil as a counter electrode, and Ag/AgCl as a reference electrode. The
electrodeposition was conduct at a potential of _0.8 V for 1800 s. The as-prepared electrodes
were thoroughly rinsed with deionized water and dried at atmosphere.

Electrochemical Characterization
HER polarisation curves were obtained in a three-electrode electrochemical cell with Ti/NiM as
the working electrode and Pt as the counter electrode, and Ag/AgCl as a reference with 0.6M
NaCl solution. Tafel slopes and EIS measurements were obtained.
The morphology of the catalyst was characterized by scanning electron microscopes.

Results and Discussions

The morphology of the catalyst provided abundant active sites. The unusual morphology of
NiCu, NiAu and NiPt or the loose structures of NiMo and NiCo could increase the specific
surface area to expose active sites supporting the electrolyte. This is beneficial for HER.
By studying the HER polarization curve and the Tafel slopes, it is found that Ti/NiPt alloy
electrode has higher catalytic activity towards the HER process. However, besides excellent
catalytic activity, good durability is also significant for real-world applications. To test this, the
long-term stability is tested using a chronoamperometric test at a constant potential for over 10
hours. This suggested that Ti/NiCo is a promising electrode.
A high-specific energy magnesium/water
battery for complete depth ocean
applications.

For full-depth ocean applications, batteries must tackle the high pressure at a depth of the sea
and need high specific energy. It is found that Mg is an excellent electrode material due to its
high specific capacity, low cost, and good electrochemical activity in seawater. Among the
tested batteries, Mg/dissolved oxygen battery is the only one that takes oxidant from the
seawater. However, the uneven and low distribution of dissolved oxygen in the ocean limits the
battery performance. Mg/water battery is a promising technology due to its high theoretic
specific energy.
To increase its performance, it is essential to decrease the cathode polarization of HER and
increase the anode current efficiency. Mg/water battery, we use Mg or AZ alloys as anode and
modified Pt-NF as the cathode. Furthermore, the performance is evaluated using different
anode and cathode.

Experimental Section
Preparation and characterization of electrodes.
The cathode (PteNF) was prepared by a simple chemical deposition method, and the anode is
Mg and AZ alloys.

Electrochemical measurements of electrodes and Mg/water batteries

The electrodes are tested in the three-electrode electrochemical cell setup with a saturated
calomel electrode as a reference electrode, a stainless steel sheet as the counter electrode and
3.5% NaCl solution as an electrolyte. The working electrode was the cathode with a working
area of 1cm*1cm or the anode with 0.5cm*0.5cm. The geometrical area of the electrode
normalizes the current density. The pressure test was also done. Under each pressure, the
polarization and discharge performances were tested.

Results and Discussion

Performance of electrode materials
The polarization curves and corresponding power density plots were obtained. It is observed
that the Pt-NF cathode exhibits better performance compared to the rest of the c. When we
observe Discharge performance, anode efficiency and specific energy of different anode
materials, AZ91 shows high anode efficiency and specific energy.

Influence of Pressure
By the Nernst equation, the theoretical equilibrium voltage of the Mg/water battery will decrease
with an increase in pressure. However, the real scenario might be different. To test the above
statement, two identical evaluations are done with and without applying pressure. The voltage
difference is minimal in the low current density region, but the battery showed a remarkable
increase in the high current density region at a higher pressure of 1100 bar. This can be
explained by the effect of the volume change of the hydrogen bubble formed. Further, the
voltage difference in the high current density region, the anode and the cathode potentials were
tested individually before and after the pressure treatment, and the effect is not so pronounced.
Influence of temperature
The temperature in the deep ocean is 0-4 Celsius which will decrease the battery's performance
due to thermodynamic and kinetic reasons. At high current density, the battery shows a
significant decrease in performance which indicates the battery should be operated at low
current density.

Stability of Mg/water battery

The stability is evaluated under galvanostatic discharge for 100 days. The results from this
indicate that the Mg/water battery is remarkably stable.

Grgur 2021, A novel method of preparing the

silver chloride cathode for the magnesium
seawater activated primary cell
Seawater-activated batteries, which use seawater as an electrolyte, have been used in multiple
applications for many years. In such cells, a magnesium alloy, AZ63, is used as an anode
instead of pure magnesium which is prone to corrosion as a consequence of the Hydrogen
Evolution Reaction. Different cathodic materials like AgCl , CuCl, PbCl2 etc. are investigated as
cathodes. In this research paper AgCl is used as cathodic material and is prepared on carbon
felt using a simple SILAR method.

Experimental Setup
The SILAR method is used for preparing the AgCl cathode. Carbon felt attached to a PVC slide
is used as a substrate on which the AgCl will be adsorbed. The SILAR cycle for the experiment
is as follows, immersion in AgNO3, followed by immersion in HCl. The rinsing of the carbon felt
with distilled water is omitted for increased accumulation of AgCl on it. After multiple cycles of
SILAR and the desired mass of AgCl is loaded, the substrate is placed in a drying oven
overnight. The AZ63 magnesium alloy is obtained and rubbed with sandstone to expose the
pure surface. As a substitute for seawater, 3.5% NaCl solution is used as an electrolyte.
These components are fixed in a glass cell and tests are performed in a potentiostat-
galvanostat to calculate the cell voltage. The optical micrograph is also obtained.
Results & Conclusions
It is concluded that for an increasing number of cycles of SILAR, an increasing mass loading of AgCl
was obtained. The highest discharge current of 15 mA is observed for the cathode with loading of 3 mg
cm− 2 (30 mg total) of AgCl and magnesium alloy AZ63 anode, from the galvanodynamic measurements.
Depending on discharge current, voltage plateau is in
the range of 1.2 V–0.8 V.

Xu, 2022 Anderson-Type Polyoxometalate-

Assisted Synthesis of Defect-Rich Doped 1T/2H-
MoSe2 Nanosheets for Efficient Seawater
Splitting and Mg/Seawater Batteries
The electrocatalytic production of hydrogen from water through the Hydrogen Evolution
Reaction is a very useful method to harness clean energy from the oceans. Pt-catalysts have
proven to be the most effective catalysts towards HER but their scarce availability makes for low
feasibility. Instead, Transition Metal Dichalcogenides (TMDs) are being investigated for their
properties that can promote HER performance by tuning compositions, morphologies, defects,
and surface characteristics. To integrate the multiple positive factors in one TMD catalyst,
MoSe2 is taken as a model material to carry out demonstrations.

Experimental Setup
Defect-rich doped 1T/2H-MoSe2 nanosheets were synthesized using XMo6 precursors
(Anderson type) through a simple hydrothermal selenization process to promote heteroatom
doping and in turn HER performance. Briefly, the as-prepared XMo6 (X = Fe, Co, and Ni), Se
powder, NaBH4 were first added into deionized (DI) water to obtain a homogeneous solution
after stirring for 1 h. The above mixture was then transferred to a Teflon autoclave and placed in
a drying oven under 180 °C for 24 h. After washing and centrifuging by using DI water and
absolute ethanol, black powder products were obtained. The obtained product was denoted as
X-MoSe2 (X = Fe, Co, and Ni).

Results & Conclusions

After integrating multiple positive factors, including doping, defects, and phase transformation in
MoSe2 nanosheets. Due to the abundant active sites and promoted intrinsic activity with
effective activation of water, the experimental and theoretical investigations reveal that the
resultant defect-rich doped 1T/2H-MoSe2 nanosheets show promising application
in Mg/seawater batteries. The as-assembled Mg/seawater battery with the Co-MoSe2 cathode displays a
maximum power density of 7.69 mW cm−2 and excellent galvanostatic
discharging stability for at least 24 h. This study offers an intriguing modulation strategy for
TMD-based catalysts and paves an avenue for applications in seawater splitting and Mg/
seawater batteries

Development of a sea water battery for deep- water

applications
Objective

The objective is to evaluate the feasibility of a sea water battery to be used in deep oceans
using cheap, readily available materials.

Necessity of a sea water battery

Although lithium cells have high power density, they require high cost for the pressure casing.
Seawater batteries is an alternative power source for long term low power instruments. They
rely on the corrosion of a reactive metal anode in sea water and the reduction of oxygen or
water at an inert cathode to generate a potential of 1V. Sea water as an electrolyte, gives high
power density. Although high power density is desirable because they minimize instrument bulk,
extra care must be taken with respect to the cost.

Electrochemistry

Oxidation occurs at cathode and reduction at anode. If M is a reactive metal of valence n,

It is also possible that anode undergoes hydrogen evolving corrosion or self discharge reaction.
This reaction can be minimized by reducing the surface area of the anode. If DO reduction is at
cathode, high potential is obtained but maximum current is limited as oxygen has low solubility
in sea water. In case of HER, they operate at high voltage and support high current densities.
Also, very small electrode separation must be maintained to minimize internal resistance. One
major problem is that alkalinity generated by cathodic reactions leads to precipitation of Mg salts
and affects the performance of the battery.

Electrode materials and analysis

Electrode plates of 30cm x 15 cm was placed 4cm apart and connected by a 50 ohm resistor.
Mg anodes generated higher potentials than aluminium for DO battery. The only drawback of
Mg is low faradic efficiency, because of higher rates of self discharge. Magnesium- graphite
battery gave a good performance. The faradic efficiency of pure magnesium anodes increased
from 13% to 70% as current density increased from 0.2 to 5 W/m2. Pure graphite cathodes
operate at a high OCP than Cu or SS, but they are too brittle and cannot be used for large scale
purposes. A seawater battery could be constructed cheaply and because the mechanical
configuration is simple and the electronic components in the power inverter need operate at only
small fraction of their capacity, it should also be very reliable.
Metal-Organic Powder Thermochemical Solid- Vapor
Architectonics toward Gradient Hybrid Monolith with
Combined Structure-Function Features

The ideal cathode for metal-based sea water batteries should exhibit many characteristics
including high catalytic activity, high electrical conductivity, good corrosion resistance, excellent
mechanical properties and low fabrication cost. The gradient carbon monolith exhibits good
mechanical strength and high catalytic activity and thus can be used as an electrode for a
Mg/H2O battery. The non uniformly distributed carbonaceous vapor and uniformly dispersed Co
nano particles are used for generating gradient carbon monolith. The conversion of metal
powders into gradient components is achieved with a non uniform electric or pressure field.
Here, the metal nano particles and non uniformly distributed reactive gases are generated
during thermo-pyrolysis of metal-organic powder to generate gradient metal carbon monolith via
combined chemical vapor deposition and solid state welding. Co/C hybrid electrode enhances
the power density of Mg/H20 sea water battery.

A unique approach known as ‘metal-organic powder thermo-chemical solid vapor

architechtonics’ is used to directly process powder into a gradient hybrid electrode. This
electrode showed high mechanical strength, good catalytic activity for hydrogen evolution
reaction( HER), high electrical conductivity and good corrosion resistance.

Performance of gradient hybrid monolith

The mechanically stable monolith-800 is a free standing electrode for HER analysis. HER test
was performed in 1M KOH solution. The monolith-800 is directly used as a working electrode.
All the potentials obtained are in reference to Reversible Hydrogen electrode( RHE). The
electrode showed a very low over potential of 84mV at a current density of 10mA/cm2. This over
potential is comparable with that of 20% Pt/C , indicating the remarkable HER catalytic activity
of monolith-800. The tafel slope is measured as 79mV/dec. Chronopotentiometric measurement
was done at a constant over potential of 200 mV for 5hrs. The electrode does not show
significant shape change after testing, indicating the good mechanical stability of electrode
during catalysis.

Further, the HER activity was tested in sea water electrolyte. As expected, the monolith-800
showed the highest activity while graphite the lowest. Monolith-800 exhibited an over potential
of 147 mV at a current density of 10 mA/cm2, which is significantly lower than other samples.

To demonstrate the practical application of the prepared gradient hybrid monolith, we

assembled a Mg/H20 sea water battery by employing the gradient hybrid monolith as cathode,
Mg plate as anode and sea water directly taken from the Donghai sea as the electrolyte. The
output power densities are 0.60, 2.55, 4.33, 4.99, 6.14, 3.89, and 2.53mW/cm2 at current
densities of 1, 5, 10, 15, 20, 25, and 30 mA cm2, respectively.

In conclusion, we have demonstrated a one-pot strategy to convert powder to

component through metal-organic powder thermochemical solid-vapor architectonics. The as-
prepared gradient hybrid monolith exhibits N-doping, Co nanoparticle- encapsulated nanotube
networks, and ceramic-like graphitic body. Therefore, the whole solid hybrid monolith can be
used as a robust cathode for a Mg/H2O seawater battery with high output power densities.