Molten-salt battery - Wikipedia https://en.wikipedia.

org/wiki/Molten-salt_battery

Molten-salt battery
Molten-salt batteries are a class of battery that uses molten
salts as an electrolyte and offers both a high energy density and
a high power density. Traditional non-rechargeable thermal
batteries can be stored in their solid state at room
temperature for long periods of time before being activated by
heating. Rechargeable liquid-metal batteries are used for
industrial power backup, special electric vehicles and for grid
energy storage, to balance out intermittent renewable power
sources such as solar panels and wind turbines. FZSoNick 48TL200: sodium–nickel
battery with welding-sealed cells
History and heat insulation

Thermal batteries originated during World War II when

German scientist Georg Otto Erb developed the first practical cells using a salt mixture as an
electrolyte. Erb developed batteries for military applications, including the V-1 flying bomb and the
V-2 rocket, and artillery fuzing systems. None of these batteries entered field use during the war.
Afterwards, Erb was interrogated by British intelligence. His work was reported in "The Theory
and Practice of Thermal Cells". This information was subsequently passed on to the United States
Ordnance Development Division of the National Bureau of Standards.[1] When the technology
reached the United States in 1946, it was immediately applied to replacing the troublesome liquid-
based systems that had previously been used to power artillery proximity fuzes. They were used for
ordnance applications (e.g., proximity fuzes) since WWII and later in nuclear weapons. The same
technology was studied by Argonne National Laboratories[2] and other researchers in the 1980s for
use in electric vehicles.[3]

A 2021 study reported stable operation of a cell operating at 230 °F (110 °C) over 400 cycles. The
cell operated at 3.6 volts. Liquid sodium metal crosses a ceramic separator, reaching a mixture of
liquid sodium iodide and gallium chloride, termed a "catholyte". The high price of gallium chloride
was expected to keep the design from commercial use.[4]

Rechargeable configurations
Since the mid-1960s much development work has been undertaken on rechargeable batteries using
sodium (Na) for the negative electrodes. Sodium is attractive because of its high reduction
potential of −2.71 volts, low weight, relative abundance, and low cost. In order to construct
practical batteries, the sodium must be in liquid form. The melting point of sodium is 98 °C
(208 °F). This means that sodium-based batteries operate at temperatures between 245 and 350 °C
(470 and 660 °F).[5] Research has investigated metal combinations with operating temperatures at
200 °C (390 °F) and room temperature.[6]

Sodium–sulfur

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The sodium–sulfur battery (NaS battery), along with the related lithium–sulfur battery employs
cheap and abundant electrode materials. It was the first alkali-metal commercial battery. It used
liquid sulfur for the positive electrode and a ceramic tube of beta-alumina solid electrolyte (BASE).
Insulator corrosion was a problem because they gradually became conductive, and the self-
discharge rate increased.

Because of their high specific power, NaS batteries have been proposed for space applications.[7][8]
An NaS battery for space use was successfully tested on the Space Shuttle mission STS-87 in
1997,[9] but the batteries have not been used operationally in space. NaS batteries have been
proposed for use in the high-temperature environment of Venus.[9]

A consortium formed by Tokyo Electric Power Co. (TEPCO) and NGK Insulators Ltd. declared
their interest in researching the NaS battery in 1983, and became the primary drivers behind the
development of this type ever since. TEPCO chose the NaS battery because its component elements
(sodium, sulfur and ceramics) are abundant in Japan. The first large-scale field testing took place
at TEPCO's Tsunashima substation between 1993 and 1996, using 3 × 2 MW, 6.6 kV battery banks.
Based on the findings from this trial, improved battery modules were developed and were made
commercially available in 2000. The commercial NaS battery bank offers:

Capacity : 25–250 kWh per bank

Efficiency of 87%
Lifetime of 2,500 cycles at 100% depth of discharge (DOD), or 4,500 cycles at 80% DOD

Sodium–nickel chloride (Zebra) battery

A lower-temperature[10] variant of molten-salt batteries was the

development of the ZEBRA (originally, "Zeolite Battery
Research Africa"; later, the "Zero Emissions Batteries Research
Activity") battery in 1985, originally developed for electric
vehicle applications.[11][12] The battery uses NaNiCl2 with Na+-
beta-alumina ceramic electrolyte.[13]

The NaNiCl2 battery operates at 245 °C (473 °F) and uses The Citroën Berlingo First Electric
molten sodium tetrachloroaluminate (NaAlCl4), which has a "Powered by Venturi" used a
melting point of 157 °C (315 °F), as the electrolyte. The negative ZEBRA storage battery; a specially-
electrode is molten sodium. The positive electrode is nickel in prepared version was driven from
the discharged state and nickel chloride in the charged state. Shanghai to Paris in 2010.
Because nickel and nickel chloride are nearly insoluble in
neutral and basic melts, contact is allowed, providing little
resistance to charge transfer. Since both NaAlCl4 and Na are liquid at the operating temperature, a
sodium-conducting β-alumina ceramic is used to separate the liquid sodium from the molten
NaAlCl4. The primary elements used in the manufacture of these batteries have much higher
worldwide reserves and annual production than lithium.[14]

It was invented in 1985 by the Zeolite Battery Research Africa Project (ZEBRA) group at the
Council for Scientific and Industrial Research (CSIR) in Pretoria, South Africa. It can be assembled
in the discharged state, using NaCl, Al, nickel and iron powder. The positive electrode is composed
mostly of materials in the solid state, which reduces the likelihood of corrosion, improving

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safety.[15] Its specific energy is 100 Wh/kg; specific power is 150 W/kg. The β-alumina solid
ceramic is unreactive to sodium metal and sodium aluminum chloride. Lifetimes of over 2,000
cycles and twenty years have been demonstrated with full-sized batteries, and over 4,500 cycles
and fifteen years with 10- and 20-cell modules. For comparison, LiFePO4 lithium iron phosphate
batteries store 90–110 Wh/kg, and the more common LiCoO2 lithium-ion batteries store
150–200 Wh/kg. A nano lithium-titanate battery stores 72 Wh/kg and can provide power of
760 W/kg.[16]

The ZEBRA's liquid electrolyte freezes at 157 °C (315 °F), and the normal operating temperature
range is 270–350 °C (520–660 °F). Adding iron to the cell increases its power response.[15] ZEBRA
batteries are currently manufactured by FZSoNick[17] and used as a power backup in the
telecommunication industries, Oil&Gas and Railways. It is also used in special electric vehicles
used in mining. In the past it was adopted in the Modec Electric Van, the Iveco Daily 3.5-ton
delivery vehicle, the prototype Smart ED, and the Th!nk City.[18] In 2011 the US Postal Service
began testing all-electric delivery vans, one powered by a ZEBRA battery.[19]

In 2010 General Electric announced a Na-NiCl2 battery that it called a sodium–metal halide
battery, with a 20-year lifetime. Its cathode structure consists of a conductive nickel network,
molten salt electrolyte, metal current collector, carbon felt electrolyte reservoir and the active
sodium–metal halide salts.[20][21] In 2015, as a result of a global restructuring, the company
abandoned the project.[22] In 2017 Chinese battery maker Chilwee Group (also known as Chaowei)
created a new company with General Electric (GE) to bring to market a Na-NiCl battery for
industrial and energy storage applications.[23]

When not in use, Na-NiCl2 batteries are typically kept molten and ready for use because if allowed
to solidify they typically take twelve hours to reheat and charge.[24] This reheating time varies
depending on the battery-pack temperature, and power available for reheating. After shutdown a
fully charged battery pack loses enough energy to cool and solidify in five-to-seven days depending
on the amount of insulation.

Sodium metal chloride batteries are very safe; a thermal runaway can be activated only by piercing
the battery and also, in this unlikely event, no fire or explosion will be generated. For this reason
and also for the possibility to be installed outdoor without cooling systems, make the sodium metal
chloride batteries very suitable for the industrial and commercial energy storage installations.

Sumitomo studied a battery using a salt that is molten at 61 °C (142 °F), far lower than sodium
based batteries, and operational at 90 °C (194 °F). It offers energy densities as high as 290 Wh/L
and 224 Wh/kg and charge/discharge rates of 1C with a lifetime of 100–1000 charge cycles. The
battery employs only nonflammable materials and neither ignites on contact with air nor risks
thermal runaway. This eliminates waste-heat storage or fire- and explosion-proof equipment, and
allows closer cell packing. The company claimed that the battery required half the volume of
lithium-ion batteries and one quarter that of sodium–sulfur batteries.[25] The cell used a nickel
cathode and a glassy carbon anode.[26]

In 2014 researchers identified a liquid sodium–cesium alloy that operates at 50 °C (122 °F) and
produced 420 milliampere-hours per gram. The new material was able to fully coat, or "wet," the
electrolyte. After 100 charge/discharge cycles, a test battery maintained about 97% of its initial
storage capacity. The lower operating temperature allowed the use of a less-expensive polymer
external casing instead of steel, offsetting some of the increased cost of cesium.[27]

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Innovenergy in Meiringen, Switzerland has further optimised this technology with the use of
domestically sourced raw materials, except for the nickel powder component. Despite the reduced
capacity compared with lithium-ion batteries, the ZEBRA technology is applicable for stationary
energy storage from solar power. In 2022, the company operated a 540 kWh storage facility for
solar cells on the roof of a shopping center, and currently produces over a million battery units per
year from sustainable, non-toxic materials (table salt).[28]

Liquid-metal batteries

Professor Donald Sadoway at the Massachusetts Institute of Technology has pioneered the
research of liquid-metal rechargeable batteries, using both magnesium–antimony and more
recently lead–antimony. The electrode and electrolyte layers are heated until they are liquid and
self-segregate due to density and immiscibility. Such batteries may have longer lifetimes than
conventional batteries, as the electrodes go through a cycle of creation and destruction during the
charge–discharge cycle, which makes them immune to the degradation that afflicts conventional
battery electrodes.[29]

The technology was proposed in 2009 based on magnesium and antimony separated by a molten
salt.[30][31][32] Magnesium was chosen as the negative electrode for its low cost and low solubility
in the molten-salt electrolyte. Antimony was selected as the positive electrode due to its low cost
and higher anticipated discharge voltage.

In 2011, the researchers demonstrated a cell with a lithium anode and a lead–antimony cathode,
which had higher ionic conductivity and lower melting points (350–430 °C).[29] The drawback of
the Li chemistry is higher cost. A Li/LiF + LiCl + LiI/Pb-Sb cell with about 0.9 V open-circuit
potential operating at 450 °C had electroactive material costs of US$100/kWh and US$100/kW
and a projected 25-year lifetime. Its discharge power at 1.1 A/cm2 is only 44% (and 88% at
0.14 A/cm2).

Experimental data shows 69% storage efficiency, with good storage capacity (over
1000 mAh/cm2), low leakage (< 1 mA/cm2) and high maximal discharge capacity (over
200 mA/cm2).[33] By October 2014 the MIT team achieved an operational efficiency of
approximately 70% at high charge/discharge rates (275 mA/cm2), similar to that of pumped-
storage hydroelectricity and higher efficiencies at lower currents. Tests showed that after 10 years
of regular use, the system would retain about 85% of its initial capacity.[34] In September 2014, a
study described an arrangement using a molten alloy of lead and antimony for the positive
electrode, liquid lithium for the negative electrode; and a molten mixture of lithium salts as the
electrolyte.

A recent innovation is the PbBi alloy which enables lower melting point lithium-based battery. It
uses a molten salt electrolyte based on LiCl-LiI and operates at 410 °C.[35]

Ionic liquids have been shown to have prowess for use in rechargeable batteries. The electrolyte is
pure molten salt with no added solvent, which is accomplished by using a salt having a room
temperature liquid phase. This causes a highly viscous solution, and is typically made with
structurally large salts with malleable lattice structures.[36]

Thermal batteries (non-rechargeable)

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Technologies

Thermal batteries use an electrolyte that is solid and inactive at ambient temperatures. They can be
stored indefinitely (over 50 years) yet provide full power in an instant when required. Once
activated, they provide a burst of high power for a short period (a few tens of seconds to 60
minutes or more), with output ranging from watts to kilowatts. The high power is due to the high
ionic conductivity of the molten salt (resulting in a low internal resistance), which is three orders of
magnitude (or more) greater than that of the sulfuric acid in a lead–acid car battery.

One design uses a fuze strip (containing barium chromate and powdered zirconium metal in a
ceramic paper) along the edge of the heat pellets to initiate the electrochemical reaction. The fuze
strip is typically fired by an electrical igniter or squib which is activated with an electric current.

Another design uses a central hole in the middle of the battery stack, into which the high-energy
electrical igniter fires a mixture of hot gases and incandescent particles. This allows much shorter
activation times (tens of milliseconds) vs. hundreds of milliseconds for the edge-strip design.
Battery activation can be accomplished by a percussion primer, similar to a shotgun shell. The heat
source should be gasless. The standard heat source typically consists of mixtures of iron powder
and potassium perchlorate in weight ratios of 88/12, 86/14, or 84/16.[37] The higher the potassium
perchlorate level, the higher the heat output (nominally 200, 259, and 297 cal/g respectively). This
property of unactivated storage has the double benefit of avoiding deterioration of the active
materials during storage and eliminating capacity loss due to self-discharge until the battery is
activated.

In the 1980s lithium-alloy anodes replaced calcium or magnesium anodes, with cathodes of
calcium chromate, vanadium or tungsten oxides. Lithium–silicon alloys are favored over the earlier
lithium–aluminium alloys. The corresponding cathode for use with the lithium-alloy anodes is
mainly iron disulfide (pyrite) replaced by cobalt disulfide for high-power applications. The
electrolyte is normally a eutectic mixture of lithium chloride and potassium chloride.

More recently, other lower-melting, eutectic electrolytes based on lithium bromide, potassium
bromide, and lithium chloride or lithium fluoride have also been used to provide longer
operational lifetimes; they are also better conductors. The so-called "all-lithium" electrolyte based
on lithium chloride, lithium bromide, and lithium fluoride (no potassium salts) is also used for
high-power applications, because of its high ionic conductivity. A radioisotope thermal generator,
such as in the form of pellets of 90SrTiO4, can be used for long-term delivery of heat for the battery
after activation, keeping it in a molten state.[38]

Uses

Thermal batteries are used almost exclusively for military applications, notably for nuclear
weapons[39] and guided missiles.[40][41] They are the primary power source for many missiles such
as the AIM-9 Sidewinder, AIM-54 Phoenix, MIM-104 Patriot, BGM-71 TOW, BGM-109 Tomahawk
and others. In these batteries the electrolyte is immobilized when molten by a special grade of
magnesium oxide that holds it in place by capillary action. This powdered mixture is pressed into
pellets to form a separator between the anode and cathode of each cell in the battery stack. As long
as the electrolyte (salt) is solid, the battery is inert and remains inactive. Each cell also contains a
pyrotechnic heat source, which is used to heat the cell to the typical operating temperature of
400–550 °C.

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See also
Primary cell
Secondary cell
Smart grid
Flow battery
Carnot battery
List of battery types

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External links
Sadoway Group - Liquid Metal Batteries (http://sadoway.mit.edu/research/liquid-metal-batterie
s)

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