Molten salt battery
Molten salt batteries are a class of primary cell and secondary cell high-temperature electric battery that uses molten salts as an electrolyte. In most cases the salt used is a sodium salt and they are then often referred to as a liquid sodium battery. They offer both a high energy density through the proper selection of reactant pairs, as well as a high power density by means of a high-conductivity molten salt electrolyte.
There are two general types of molten salt batteries. Use-once (primary) thermal batteries are stored in a solid state and then heated to activate, providing very long shelf life and high power density in a compact package. These were widely used in guided weapon systems such as surface-to-air-missiles.
Rechargeable molten-salt batteries are a promising technology for powering electric vehicles, and especially energy storage to balance out environment-dependent power plants (solar, wind, etc.). With high operating temperatures of 400 °C (752 °F) to 700 °C (1,292 °F), they have problems of thermal management and safety, and they place stringent requirements on the rest of the battery components. Some newer designs, such as the ZEBRA battery, operate at a lower temperature range of 245 °C (473 °F) to 350 °C (662 °F).
Referred to as thermal batteries, the electrolyte is solid and inactive at normal ambient temperatures. The origin of the thermal battery dates back to WWII when German scientist Dr. Ing. Georg Otto Erb developed the first practical cells, using a salt mixture as an electrolyte. Erb developed batteries for several military applications, including the V-1 flying bomb and the V-2 rocket, and artillery fuzing systems. None of these batteries entered field use before the end of WWII. After the war, Erb was interrogated by British intelligence and his work was reported in a document titled "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.
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. These batteries have been used for ordnance applications (e.g., proximity fuzes) since WWII and later in nuclear weapons. They are the primary power source for many missiles such as the AIM-9 Sidewinder, 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.
There are two types of design. One uses a fuze strip (containing barium chromate and powdered zirconium metal in a ceramic paper) along the edge of the heat pellets to initiate burning. The fuze strip is typically fired by an electrical igniter or squib by application of electric current through it. The second design uses a center hole in the middle of the battery stack into which the high-energy electrical igniter fires a mixture of hot gases and incandescent particles. The center-hole design allows much faster activation times (tens of milliseconds) vs. hundreds of milliseconds for the edge-strip design. Battery activation can also be accomplished by a percussion primer, similar to a shotgun shell. It is desired that the pyrotechnic source be gasless. The standard heat source typically consist of mixtures of iron powder and potassium perchlorate in weight ratios of typically 88/12, 86/14, and 84/16. The higher the potassium perchlorate level, the higher the heat output (nominally 200, 259, and 297 calories/gram, 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. They can be stored indefinitely (over 50 years) yet provide full power in an instant when required. Once activated, they provide a high burst of power for a short period (a few tens of seconds) to 60 minutes or more, with output ranging from a few watts to several kilowatts. The high power capability is due to the very high ionic conductivity of the molten salt, which is three orders of magnitude (or more) greater than that of sulfuric acid in a lead-acid car battery. Older thermal batteries used calcium or magnesium anodes, with cathodes of calcium chromate or vanadium or tungsten oxides, but lithium-alloy anodes replaced these in the 1980s, with lithium-silicon alloys being favored over the older lithium-aluminium alloys. The corresponding cathode for use with the lithium-alloy anodes is mainly iron disulfide (pyrite) with cobalt disulfide being used 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.
These batteries are used almost exclusively for military applications, that is, "one-shot" weapons such as guided missiles. The same technology was also studied by Argonne National Laboratories in the 1980s for possible use in electric vehicles, since the technology is rechargeable.
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, non-toxic nature, relative abundance and ready availability and its low cost. In order to construct practical batteries, the sodium must be used in liquid form. Since the melting point of sodium is 98 °C (208 °F) this means that sodium based batteries must operate at high temperatures, typically in excess of 270 °C (518 °F).
The Sodium–sulfur battery (or NaS battery), along with the related lithium sulfur battery, comprises one of the more advanced systems of the molten salt batteries. The NaS battery is attractive since it employs cheap and abundant electrode materials. Thus the first alkali metal commercial battery produced was the sodium–sulfur battery which used liquid sulfur for the positive electrode and a ceramic tube of beta-alumina solid electrolyte (BASE) for the electrolyte. Corrosion of the insulators was found to be a problem in the harsh chemical environment as they gradually became conductive and the self-discharge rate increased. A further problem of dendritic-sodium growth in Na/S batteries led to the development of the ZEBRA battery.
Because of their high specific power, NaS batteries have been proposed for space applications. A test of a NaS battery for space use was successfully demonstrated on the space shuttle mission STS-87 in 1997, but the batteries have not been used operationally in space. NaS batteries have also been proposed for use in the high temperature environment of Venus.
The NaS battery has reached a more advanced developmental stage than its lithium counterpart. The possibility of construction of Potassium-ion battery by molten electrolyte has been recently patented.[when?]
|Specific energy||90 Wh/kg|
|Energy density||160 Wh/l|
|Specific power||155 W/kg, peak power 335 C |
|Time durability||>8 years|
|Cycle durability||~3000 cycles|
|Nominal cell voltage||2.58 V|
The ZEBRA battery operates at 245 °C (473 °F) and utilizes molten sodium aluminumchloride (NaAlCl
4), which has a melting point of 157 °C (315 °F), as the electrolyte. The negative electrode is molten sodium. The positive electrode is nickel in the discharged state and nickel chloride in the charged state. Because nickel and nickel chloride are nearly insoluble in neutral and basic melts, intimate contact is allowed, providing little resistance to charge transfer. Since both NaAlCl
4 and Na are liquid at the operating temperature, a sodium-conducting β-alumina ceramic is used to separate the liquid sodium from the molten NaAlCl
4. This battery was invented in 1985 by the Zeolite Battery Research Africa Project (ZEBRA) group led by Dr. Johan Coetzer at the Council for Scientific and Industrial Research (CSIR) in Pretoria, South Africa. In 2009, the battery had been under development for more than 20 years. The technical name for the battery is Na-NiCl2 battery.
The ZEBRA battery has a specific energy of 90 Wh/kg and a specific power of 150 W/kg. 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. Nano Lithium-Titanate Batteries store 72 Wh/kg energy and can provide a power of 760 W/kg . The ZEBRA's liquid electrolyte freezes at 157 °C (315 °F), and the normal operating temperature range is 270 °C (518 °F) to 350 °C (662 °F).
The β-alumina solid electrolyte that has been developed for this system is very stable, both to sodium metal and the sodium aluminumchloride. The primary elements used in the manufacture of ZEBRA batteries, Na, Cl and Al have much higher worldwide reserves and annual production than the Li used in Li-ion batteries. Lifetimes of over 1,500 cycles and five years have been demonstrated with full-sized batteries, and over 3,000 cycles and eight years with 10- and 20-cell modules. ZEBRA batteries are currently manufactured by FIAMM Sonick that acquired MES-DEA in 2011.
In 2011 FIAMM, one of the world’s largest battery manufacturers, acquired Switzerland-based company MES-DEA, creating a new company called FIAMM SONICK that manufactures and markets alternative energy storage solutions throughout the world. FIAMM SONICK, the leading global producer of sodium-nickel-chloride (Na-NiCl2) batteries, has been producing sodium-nickel batteries since 2000. This proven and highly reliable storage technology is available for immediate deployment in a wide area of applications like: Traction, Telecom, Industrial, Railways and Energy storage.
In 2010 General Electric announced a Na-NiCl
2 battery that it called a sodium-metal halide battery, with a 20-year lifetime. The cathode structure of a GE cell consists of a conductive Ni network, molten salt electrolyte, metal current collector, carbon felt electrolyte reservoir, and the active sodium-metal halide salts.
- gravimetric energy density: 115 Wh/kg
- volumetric energy density: 160 Wh/L
- operating temperature range: -20 °C to 60 °C
- Cycle Life: >3,000 operating cycles at 80 percent DOD on a two-hour rate
- Cathode Chemistry: NiCl2+NaAlCl4
- Anode Chemistry: Liquid Na
Low-temperature molten salts
Sumitomo developed a battery using a salt that is molten at 61 °C (142 °F) far lower than sodium based batteries. The operating temperature of the battery is 90 °C (194 °F) and a test battery has been shown to survive 100 - 1000 charge cycles. The battery offers energy densities as high as 290 Wh/L and 224 Wh/kg and charge/discharge rates of 1C. The battery employs only nonflammable materials and will not ignite on contact with air, nor is there thermal runaway. This eliminates waste-heat storage or fire- and explosion-proof equipment, and allows closer packing of cells. The company expects that the battery requires half the volume of lithium-ion batteries and one quarter that of sodium–sulfur batteries. 
Modec Electric Van uses ZEBRA batteries for the 2007 model and the IVECO daily 3.5 ton delivery vehicle was announced in mid-2010. Th!nk City was offering a ZEBRA battery option. In 2011, the US Postal Service began testing five delivery vans that had been converted to all-electric power, one of which uses a ZEBRA battery.
When not in use, ZEBRA batteries are typically continuously kept hot, so that they remain molten and ready for use. If shut down and allowed to solidify, reheating takes around 12 hours to restore the battery pack to the desired temperature and impart a full charge (starting from ambient temperature). 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 3–4 days.
In 2009, Donald Sadoway and his team proposed a very low cost molten salt battery originally based on magnesium and antimony separated by a salt that could be potentially used in Grid energy storage systems. Research on this concept is being funded by ARPA-E, Bill Gates, Khosla Ventures and Total S.A. Experimental data showed 69% storage efficiency, it had good storage capacity (over 1000mAh/cm2) and relatively low leakage (< 1 mA/cm2) and high maximum discharge capacity (over 200mA/cm2). They planned to have a commercial prototype built by 2014.
In 2014 the team discovered that replacing magnesium with lead lowered the battery's operating temperature by more than 200 °C (392 °F)and reduced materials costs. Tests showed that even after 10 years of regular use, the system would retain about 85% of its initial efficiency.
The batteries overall efficiency was approximately 70% at high charge/discharge rates (275mA/cm^2), similar to that of pumped hydro systems. At low currents, the efficiency rises significantly. The battery produced voltage as high as antimony alone, and a melting point between those of the two metals.
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