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Application Note

Vanadium Redox Flow battery - Key Features
General Information
The University of Uppsala, Sweden invented the vanadium redox battery it was further developed in Universität Luzern, formerly Fachhochschule Zentralschweiz" (FHZ) Switzerland. However at the University of New South Wales, Australia it was Prof Maria Skyllas-Kazacos Australia, whose scientific achievement was the stabilization of 4 different valencies of Vanadium in a liquid solution within the acidic pH-regim. A regim. After such further research produced an all all-vanadium redox flow battery with unique features and the real potential for low cost stationary applications. The University reached a level of design enabling them to licence Mitsubishi the technology for large largescale stationary applications in Japan in 1989. Mitsubishi and others since has proven the basic chemistry for large-scale load levelling, storage and similar mains utility applications in the order scale of 200MW.

A redox battery resembles a fuel cell, except that a liquid oxidant is used instead of air to oxidise the fuel. Redox battery technology therefore comprises two storage tanks for the fuel and oxidant, a fuel cell where the reactants combine electrochemically to give electricity, and two storage tanks for the spent reactants. The electrochemical energy conversion is simil to a fuel similar cell in requiring a membrane to separate the fuel and oxidant while allowing completion of the electrical circuit via ionic conduction. Another important difference is that unlike a conventional fuel cell, the redox battery is able to regenerate the original reactants by operating the fuel cell regenerate in reverse, or electrolysis, mode. The advantage over a conventional rechargeable battery is that the energy stored depends on the tank size and is therefore independent of size of the electrochemical energy converter. nergy The vanadium redox flow battery is unique because both reactants are derived from the same elements, albeit in different oxidation states, and are dissolved in the same electrolyte, sulphuric acid. Therefore, the consequences of cross cross-contamination are far less serious. This advantage tamination has contributed to a proven track record of indifference to deep cycling and very high charge and discharge rates, it has a long operational life greater than 15 years.

explosion or health risks and very has little environmental impact. Clearly. energy efficient. This allows for maximizing overall system efficiency and can reduce infrastructure costs. The Vanadium Redox Battery has several unique technical advantages over most of its rivals in nadium addition to the potential low installed cost and recharge per unit kilowatt costs. this also reduces self discharge. There is therefore no corrosion or shedding of the active material. Robust Rugged indifference to rapid charge and discharge rates. Self cooling and ambient temperature operation. The power module has an eight to ten thousand hour (ten year) design life. Vanadium REDOX does not operate at high temperature and does not present a fire threat. membranes. Convenience with three to five (3 hree (3-5) minute refuel-ability The handling of the vanadium electrolyte is somewhat similar to that of pumped diesel except that it can be either conventionally recharged from the electrical supply in situ or should the need arise. The circulation of the electrolyte allows for automatic self cooling. very clean with no known hazards to personnel or the environment and the product can and will be recycled. The "stack" is a vibration proof rugged assembly with permanently connected plumbing. with an unlimited electrolyte life. The Vanadium electrolyte can be housed in tanks of any reasonable shape and does not have to housed within a building thereby allowing for greater design and infrastructure thereby flexibility (and lower building costs) in comparison with "black box" type battery systems. These features can be summarised in the list given overleaf. The industrial processes involved are quiet. Potential long life The battery's reactive agents remain in liquid form at all times and the electrodes. 2 3 4 5 6 7 . are made of conductive plastic which does not take part in the electrochemical reaction. rapidly changed for “new” electrolyte in changed which case the replaced electrolyte can be recharged at a dedicated electrical charge point elsewhere. irculation Low self discharge Both the positive and negatively charged electrolyte are the same Vanadium based chemical mixture but with a charge valance differential. Flexible Ability to charge at one voltage and discharge at another The voltage system may discharge at one voltage and recharge at another. Therefore there is not the degradation of electrolyte as with most other battery systems. The Key Features 1 Potential very low whole whole-of-life costs Low purchase costs AND low operational costs per installed kilowatt. a life limiting factor in most conventional batteries.Vanadium redox does not give rise to fire.

26 V V 2 + ⇔ V 3+ + e − The electrolyte used in the cell is: 2 2–3 mol/l H2SO4. The initial species V3+ and V4+ (VO2+) are regenerated in the reverse reactions proceeding in the discharge process. .0 V + VO2 + 2 H + + e − ⇔ VO 2+ + H 2 O Negative electrode: Eo+ = . Ability to charge at one voltage and discharge at another The system output voltage maybe at one voltage and the recharging system voltage maybe can be at another. two electric pumps and the battery stack. 2+ reduced forming V whereas anodic oxidation of V4+ (VO2+) to V5+ (VO2+) occurs. 11 The Basic Chemistry The redox flow cell consists of two electrolyte container.0. one positive and one negative. 1 mol/l V-species. This allows for maximizing overall system efficiency and can reduce infrastructure costs Wide application Range Vanadium is a viable commercial choice for systems from circa 20kW to utility size in applications ranging from UPS and load levelling in distributed power systems particularly incorporating renewables (wind – solar – micro hydro etc.8 9 10 Positive environmental impact Vanadium does not present a toxic threat. with the electrolytes of V2+/ V3+ and V4+ / V5+ in a sulphuric acid solution. The electron exchange takes place according to the following reaction (discharge in the right direction): Positive electrode: Eo= 1.) to mass storage for wave power Modular System The battery stacks can be connected in parallel to increase the output power of the battery and furthermore the electrolyte is stored in tanks which can be replaced by larger tanks or more tanks added to increase the stored energy. During charge V3+ is species.

HILTech and others have research programs to overcome challenge. Vanadium and vanadium compounds can be found in the earth's crust and in rocks. Applications Platform What is Vanadium? Vanadium was discovered twice. petroleum . some iron ores. pure vanadium has no smell. the relatively low specific energy of 25 25–35Wh/kg and power density have limited its use in smaller scale applications.The attainable open circuit voltage (OCV) is approximately 1. and in crude petroleum deposits. Given its performance characteristics the all all-vanadium redox flow battery is well suited to stationary applications but. sodium. from vanadium dichloride. Vanadium is a natural element in the earth it has the chemical symbol V and is number 23 in the Table of Elements.6 V per cell at 100% state of charge. sulphur or chloride. It usually combines with other elements such as oxygen. Henry Enfield Roscoe first isolated the metal in 1867. and named it after the Scandinavian goddess of beauty and youth the metal's compounds provide beautiful colours in solution. to date. but then decided he merely had found an impure form of chromium and later in 1830 Nils Gabriel Sefstrom found it separately. In 1801. Andres Manuel del Rio named it erythronium. however it wasn't until 1925 that relatively pure vanadium was obtained by reducing vanadium pentoxide with calcium metal. and is often found as crystals. Vanadium as a compound occurs in nature as a white white-to-grey metal.

make steel. Vanadium pentoxide is the most common state in which vanadium is found. This substance is therefore considered to have inadequate odour warning properties. it forms when cooled from the molten state to yellowish-red form long red needles as a dust it is also odourless. South Africa produces 40% of the world's vanadium. The resulting product includes a slag. Most of the vanadium used in the world is used to gs. and vanadium from carnotite. and pig iron. dark-grey flakes. plastics. containing vanadium pentoxide. Sources and Production Vanadium is traditionally obtained in the production of iron. A leachate is obtained in the early stage of production of uranium product. grey Vanadium is also mixed with iron to make important parts for aircraft engines. This can be further processed to obtain um forms of the compound in various purities. Vanadium in the form of vanadium oxide is a component in special kinds of steel that is used for automobile parts. containing titanium. The pig iron is then blown with oxygen.8% purity. Currently. which is then fed into a solvent. A second solvent process and a soda ash solution with ammonium sulfate eventually yield vanadium pentoxide. and ball bearings. springs. yielding a uranium compound and m a separate raffinate containing the vanadium. ceramics. . unts Vanadium Pentoxide Vanadium pentoxide is a yellowish red powder. and other chemicals. and a new slag rich in vanadium pentoxide is obtained. or yellow crystals. Small amounts of vanadium are used in making rubber. Vanadium is relatively abundant in the earth's crust (it is the 22nd most abundant element). the USA and elsewhere. with the remaining 60% split ntly. Each of these bearing traditional methods can yield a compound of somewhat better than 99.Vanadium is mostly combined with other metals to make special metal mixtures called alloys. Uranium production also provides vanadium pentoxide as a by-product. the Far East (mostly China). however economic deposits are available in Western Australia but otherwise somewhat rare. Titaniferous magnetite ore is partially reduced with coal. but significantly better purity can only be obtained by atomically produced combination combinations. and then melted. Other vanadium-bearing ores also yield significant amounts of the compound. Vanadium oxide is a yellow yellow-orange powder. It is slightly soluble in water. among Russia.

Environmental Impact The environmental impact of both vanadium redox and lead acid batteries for use in stationary lead-acid applications has been assessed using a life-cycle assessment approach. Vanadium (added in amounts between 0. most people are exposed mainly from food. Everyone is exposed to low levels of vanadium in air. with improved resistance to shock. About 80% of the Vanadium now produced is used as ferrovanadium or as a steel additive. This chemical has been found in at least 385 of 1.416 National Priorities List sites identified by the US Federal Environmental Protection Agency. vanadium steel is especially strong and hard. and other effects. It is also used to produce a super conductive levelling magnet with a field of 175. however. Medical implants often contain Vanadium alloys which contribute to their long life. (Source: Offer by cycle Federation Resources for Pinnacle . Vanadium foil is used as a bonding agent in cladding titanium to steel and generally by the titanium aerospace industry in Titanium alloys. Vanadium has catalytic properties that make it useful in many industrial application. The Vanadium Redox battery is a recent development intended for large scale load levelling applications. water and food.BIDDER'S STATEMENT October 2000) The assessment indicates that the Vanadium Redox Battery (VRB) contributes between 7 7-25% of emissions of lead-acid batteries in the key environmental pollutants namely: acid carbon dioxide sulphur dioxide carbon monoxide methane nitrous oxides dinitrous oxide during the whole-of-life cycle.0 percent) has two effects upon steel: it refines the grain of the two steel matrix. coughing. chest pain. Vanadium plays an important role in battery technology where it is used as an additive in the manufacture of Lithium Ion batteries. CO2 SO2 CO CH4 NOX N2O . Breathing high levels of vanadium may cause lung irritation.The Market for Vanadium Vanadium is used in producing rust resistant and high speed tools steels. Another important catalytic use is in the manufacture of maleic anhydride a chemical needed to make polyester resins and to fibreglass. Thus. and with the carbon present it forms carbides. Vanadium Pentoxide is used as a catalyst in the production of Sulphuric acid where Sulphur dioxide is passed over a V2O5 catalyst bed and oxidized to Sulphur trixoxide.1 and 5.000 gauss.

including a self self-contained breathing apparatus. . when fighting fires involving vanadium pentoxide dust. Flash point Auto-ignition temperature Flammable limits in air Extinguishant Not applicable Not applicable Not applicable Use an extinguishant that is suitable for the materials involved in the surrounding fire Firefighters should wear a full set of protective clothing. the following comments apply when vanadium enters the environment: vanadium enters the environment from natural erosion of rocks and soil and also from the natural burning of fuel oils vanadium stays in the air. vanadium can combine with ground and surface water and soil. The estimated residence of these particles vary due to particle size. It is believed that the released vanadium is derived from the burning of organic fuels and is in the form of airborne particles which are simple or complex o oxides. when rock and soil containing vanadium are broken down the resultant dust can be wind borne. Despite the fact that some seventy per cent of all atmospheric releases of vanadium are of anthropogenic origin corresponding releases to inland waters. Generally. oxides Flammability There is no National Fire Protection Association (US) fire hazard rating for vanadium pentoxide dust. soil and marine environments are orresponding considered very low when compared with natural sources. On entering aquatic environments vanadium is likely to form a more soluble pentavalent state. fine particles are thought to have a residence time of one day. Risk factors for exposure to vanadium compounds in the environment are considered very low. water and soil as particles for a long time vanadium does not readily dissolve in water vanadium naturally combines with other elements vanadium sticks to soil particles low levels of vanadium are found in plants and thereby eaten by animals vanadium is unlikely to build up in animal tissue No known authenticated levels of the annual release of vanadium into the environment are available. Further such action including natural erosion of rock by rain. the best estimates from US industrial sources vary from ten to thirty thousand tonnes per annum. Vanadium does not dissolve easily in water but can be carried by water as particulates. also. In sea water vanadium is continuously precipitated by the presence of ferric hydroxides or other organic matter and is deposited as seabed sediment.Vanadium in Air and Water The most likely way for vanadium to pollute the air is by burning organic fuel. In which state the vanadium is absorbed by organic compounds and hence becomes incorporated in sediment systems. this substance is not combustible.

Table Z weighted Z-1-A]. but still high levels of vanadium in the water of pregnant animals resulted in minor birth defects.1000. and lung effects associated with exposure to this substance. and eyes. however.05 milligram per cubic metre of air as an ure eight (8) hour time-weighted average concentration [29 CFR 1910.05 mg/cubic metre as a 15 15minute ceiling [American Conference of Governmental Industrial Hygienists. pulmonary. y Slightly higher levels but generally safe levels occur under the following circumstances: certain foods polluted air near the burning of organic fuels working with vanadium or near it in large quantities Exposure to vanadium pentoxide dust can occur via inhalation and eye or skin contact. and the NIOSH limit is based on the risk of eye. The American Conference of Governmental Industrial Hygienists (ACGIH) has assigned vanadium compounds (measured as vanadium) a threshold limit value of 0.05 mg/m3 as a fifteen (15) minute ceiling [National Institute for Occupational Safety and Health Recommendations. and systemic effects GIH associated with exposure to vanadium pentoxide dust. The OSHA and ACGIH limits are based on the risk of irritation. The health effects in people ingesting significant quantities of vanadium are unknown since no cases are known to be reported. water and food. The amounts of vanadium given in these animal studies that resulted in harmful effects are much higher than those likely to occur in the environment. The major effects from breathing high levels of vanadium are on the lungs. Heavy Exposure to Vanadium Exposure to high levels of vanadium can cause harmful health effects. Some animals that breathed or ingested vanadium over a long term had minor kidney and liver changes. Handbook 1989. throat. skin. Animals that ingested very large doses have died. Workers who breathed it for short and long periods sometimes had the following effects: short and long lung irritation coughing and wheezing chest pains runny nose sore throat . The current Occupational Safety and Health Administration (OSHA) in the US permissible exposure limit (PEL) for vanadium pentoxide dust is 0. 1988]. page 42]. nadium vanadium is not readily absorbed by the body either by ingestion or skin contact. The National Institute for Occupational Safety and Health (NIOSH) in the US re recommended exposure limit (REL) for vanadium compounds (measured as vanadium) is 0.Health and Safety Natural Exposure to Vanadium Natural exposure to vanadium at very low levels which are not considered harmful occur in air. Lower.

Vanadium is not classed as a carcinogenic. exposure to a concentration of 0. and kidney damage in laboratory animals. Summary of toxicology Effects on Animals: Vanadium pentoxide dust irritates the eyes. cholesterol. lungs. no human studies are available on the carcinogenic. adrenal glands. vascular congestion of the liver. and Hodge 1984. the source: II-148 pathologic lesions seen in these animals included desquamative enteritis. diarrhea. Eye irritation properties. hind limb paralysis. however no other significant health effects have been found in people Similar effects have been observed in animals. Smith. and seizures [source: Gosselin. labored respiration. kidneys. Acutely poisoned animals develop nose bleeds. and bone marrow. and Hodge 1984. brain. No increase in tumors was noted in a long long-term animal study where the animals were exposed to vanadium in the drinking water. In the event of a spill or leak of vanadium. II 148]. the lowest lethal concentration by inhalati inhalation in the same species is seventy (70) mg/m3 for two (2) hours [source RTECS 1989 source 1989]. No other significant health effects of vanadium have been found in people.Similar effects have been observed in animal studies. gastrointestinal tract.018 mg/m3 vanadium pentoxide is known to have caused eye irritation. non-contaminated The effects are known to stop when non contaminated air become available. The oral LD(50) for rats is ten (10) mg/kg. At autopsy. however. liver. and fatty degenera-tion of the liver and kidneys [source: Gosselin. mucous membranes and respiratory tract and may cause nervous system. p. it is highly recommended that persons should wear protective equipment and clothing in contaminated areas until cleanup has been completed. Smith. . p. carcinogenicity of vanadium. No human death (or a recorded one of an animal) has been recorded as a result of heavy animal) exposure to vanadium. II tion II149]. oxaloacetic trans transferases. No quantitative data are available on the eye irritation threshold for vanadium pentoxide dust. however. spinal cord. Spills and Leaks. Vanadium does not appear to effect enzyme activity or bilirubin levels. A human study showed no changes in serum glutamic. triglyceride or phospholipid levels or any haematological abnormalities following significant oral exposure to vanadium.

The American Conference of Governmental Industrial Hygienists (ACGIH) has recommended an occupational exposure limit of 0. programs. and referral of workers for diagnosis and treatment. The National Institute for Occupational Safety and Health (NIOSH) has recommended that 35 mg/m³ of vanadium be considered immediately dangerous to life and health. early detection of adverse health effects. Notes . or E. The EPA requires discharges or spills of five hundred (500) killograms or more of vanadium into killograms the environment to be reported.05 milligrams per cubic metre for vanadium pentoxide dust and 0. placement of work-related workers in jobs that do not jeopardize their safety or health. and O. industrial hygienists.05 mg/m³ for vanadium pentoxide. forty (40) hour work oxide workweek. This is the exposure level of a chemical that is likely to cause permanent health problems o death. Workers who may be exposed to chemical hazards should be monitored in a systematic program of medical surveillance that is intended to prevent occupational injury and disease.and other occupational safety and health professionals who may need such information to conduct effective occupational safety and health programs.NIOSH / OSHA Health Guideline. Summarizes pertinent information about for workers and employers as well as for physicians.E. The Occupational Safety and Health Administration (OSHA) has set an exposure limit of 0. The program should include education of employers and workers about wor related hazards.1 mg per cubic metre for vanadium pentoxide fumes in workplace air for an eight (8) hour workday.