Vanadium And Lithium Batteries For Green Cars MODIFIED VERSION. AusIMM June Technical Session 2010

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1 Vanadium And Lithium Batteries For Green Cars MODIFIED VERSION AusIMM June Technical Session 2010 Click to edit Master subtitle style Presented by Dr Denis Yan, Consulting Metallurgist Mineral Engineering Technical Services

2 Who We Are Mineral Engineering Technical Services > 22 years in Mineral Processing > Global & Local Experience > Consulting > Studies > Detailed Design > Due Diligence, Ni, U, Pb-Zn, Au, Cu, Fe, Al > Laboratory Testwork

3 Overview > Introduction > Vanadium processing > Lithium processing > Lithium batteries > Vanadium batteries > Advantages and disadvantages of the V/Li batteries

4 Brief History Of Electric Cars > 1832 Scottish inventor Robert Anderson invents the first electric carriage powered by non-rechargeable primary cells > 1859 French physicist Gaston Planté invents the rechargeable leadacid storage battery > 1891 William Morrison builds the first successful electric automobile in the United States > 1899 Thomas Edison begins his mission to create a long-lasting, powerful battery for commercial automobiles (nickel-alkaline) He ultimately abandoned his quest a decade later Edison and 1912 Detroit Electric

5 Brief History Of Electric Cars > % of the 4,192 cars produced in the United States were powered by electricity > 1920 the electric car ceased to be viable due to lack of range, lack of horsepower, and ready availability of petroleum (gasoline) > 1970s Concerns about the soaring price of oil, eg. the Arab Oil Embargo of 1973, led to a renewed interests in electric vehicles. EPA clean air act (CAA) > 1972 Victor Wouk, builds the first full-powered, full-size hybrid vehicle out of a 1972 Buick Skylark. The Environmental Protection Association later kills the Clean Car Incentive program in > Vanguard-Sebring Citicar, 1974

6 Brief History Of Electric Cars > 1997 Toyota unveils the Prius - the world's first commercially massproduced and marketed hybrid car. Nearly 18,000 units are sold during the first production year. > A few thousand all-electric cars (such as Honda's EV Plus, G.M.'s EV1, Ford's Ranger pickup EV, Nissan's Altra EV, Chevy's S-10 EV, and Toyota's RAV4 EV) are produced by big car manufacturers, but most of them were available for lease only. All of the major automakers' advanced all-electric production programs were discontinued by the early 2000s > 2003 GM reclaims all EV1 vehicles and destroys them (Zero Emission Vehicle [ZEV] mandate ended) crushed EV1 electric cars

7 Electric Vehicles > UK electric milk float - Quiet, economic for constant stop-start operation - Top speed, km/h - Range, km per charge - Charge time, 8 hours + - Batteries replaced every 5-10 years - Batteries 48 v (small floats), 132 v (larger models) > Golf Cart (buggy) km/h speed V battery - First mass-produced electric vehicle for private use

8 Electric Vehicles > Fork Lift first electric fork lift truck - Cheaper to operate than other types - No emissions, can work indoors - Fewer moving parts, longer life, lower maintenance - Low noise > - Battery only lasts 6 hours - Recharging takes 8 hours with 8 hours cooling > - Battery weight ~1.5 tonnes > - Less torque and power, max load 6.8 tonnes > - Unsafe in wet weather > 1974 First Toyota Electric Fork Lift

9 Example Electric Car > The range is about 80 km > The 0-to-60 mph time is about 15 seconds. > It takes about 12 kilowatt-hours of electricity to charge the car after a 80 km trip. > The batteries weigh about 500 kg > The batteries last three to four years

10 Example Electric Car > To compare the cost per km of petrol cars to this electric car: Assuming electricity is about 10 cents per kilowatt-hour - for a full recharge, it costs $ The cost per km is therefore 1.5 cents per km If petrol costs $1.20 per litre and a car gets 10 L/100 km, then the cost is 12 cents per km for petrol > The "fuel" for electric vehicles costs a lot less per km than it does for petrol vehicles > The average person living in a city or suburb seldom drives more than 50 or 60 km per day

11 Battery Requirements > Large capacity batteries are required to achieve reasonable range > The battery must be capable of regular deep discharge (80% DOD) operation > It is designed to maximise energy content and deliver full power even with deep discharge to ensure long range > Must accept very high repetitive pulsed charging currents if regenerative braking required

12 Battery Requirements > Batteries are physically very large and heavy - the design layout and weight distribution of the pack must be integrated with the chassis design maximise the vehicle dynamics > The different types of electric car batteries including: Lead-acid batteries Nickel metal hydride batteries Lithium-ion batteries Zinc-air batteries Molten salt batteries Vanadium batteries

13 Vanadium > A refractory metal resistant to heat and wear (mp o C) > Uses High temperature applications Fusion reactor linings Jet engine components Chemical applications V2O5 catalysts in sulphuric acid manufacture Four common oxidation states Ceramics and glass coatings (blocks infra-red) High strength steel (~90% of V consumption) first large scale use was in construction of model T Ford

14 Vanadium Resources > World Resources 63,000,000 t

15 Vanadium Production

16 Vanadium Occurrence > 0.012% of earth s crust (more abundant that Cu, Pb, Zn) > Occurs in >65 different minerals Carnotite K 2 (UO 2 ) 2 (VO 4 ) 2,3(H 2 O) Vanadinite (Pb 5 (VO 4 ) 3 Cl ) Francevillite, (Ba,Pb)(UO 2 ) 2 [VO 4 ] 2 5H 2 O

17 Vanadium Occurrence > Vanadium also occurs in deposits of : Phosphate rock, Titaniferous magnetite, and Uraniferous sandstone and siltstone In which it constitutes less than 2% of the host rock > Significant amounts are also present in bauxite and carboniferous materials, such as coal, crude oil, oil shale, and tar sands, fly ash > Majority of world vanadium is produced from primary sources, including by-products from iron and uranium

18 Titaniferous Magnetite > Magnetite is an inverse spinel structure: A spinel is a mixture of two metal oxides with oxygen forming a close packed cubic structure with divalent cations occupying 1/8 of the tetrahedral sites and trivalent cations in half of the octahedral sites in the oxygen framework The general formula is A 2+ B 3+ 2O 4 In an inverse spinel, the A 2+ can occupy octahedral sites and B 3+ is displaced to tetrahedral sites In magnetite, Fe 3+ ions occupy the tetrahedral sites and Fe 2+ and Fe 3+ occupying the octahedral sites Titaniferous ores form by the substitution of titanium with iron in the magnetite structure

19 Titaniferous Magnetite > Vanadium as well as titanium is able to enter the magnetite structure, due to the similar sizes between Fe 3+, Ti 4+ and V 3+ ions > Ti 4+ can substitute for the Fe 3+ in the octahedral positions and the charge difference is compensated for by divalent ions > Complete substitution of Fe 3+ by titanium leads to the mineral ulvospinel (Fe 2+ 2TiO 4 ), one end of the ulvospinelmagnetite solid solution series referred to as titanomagnetites or titaniferous magnetites

20 Titaniferous Magnetite > Magnetite is an inverse spinel structure: Other tri-valent cations such as V 3+, Cr 3+, and Al 3+ can substitute for the Fe 3+ in the magnetite or titanomagnetite structure When the vanadium substitution is significant (>1%) the vanadiferous titanomagnetites is a viable ore resource for vanadium

21 Vanadium Extraction > Major sources of vanadiferous magnetite ores are Australia, China, Russia and South Africa > Vanadium is recovered from titaniferous magnetite by: > 1. Smelting vanadium pig iron oxygen blow V rich slag > 2. Salt roast water leach vanadium precipitation

22 Vanadium Processing > To extract the vanadium from titaniferous magnetite, the trivalent vanadium ion (V 3+ ) must be oxidised to the penta-valent ion and reacted with a sodium salt to form a water soluble sodium metavanadate > In general, high grade oxidized minerals can be directly sent to the smelters > Roasting is performed with a sodium salt such as sodium chloride

23 Vanadium Oxidation States

24 Vanadium Oxidation States > The oxidation state of vanadium will determine the relative solubility of its compound. Vanadium in its trivalent state (V 3+ ) will remain relatively insoluble in most conditions > Higher oxidation states such as pentavalent vanadium (V 5+ ) will exhibit higher solubilities than lower oxidation states > The salt roast extraction process oxidizes the vanadium to higher vanadium states to allow the leaching of vanadium compounds by aqueous solutions

25 Salt Roast Flowsheet Titaniferous Magnetite 0.3% V 2 O 5 Comminution Salt Magnetic Separation 1% V 2 O 5 Magnetic Concentrate Rotary Kiln Tails Ammonia Water Leach V 2 O 5 Calcination Precipitation Desilication Ammonium meta vanadate

26 Windimurra (1)

27 Batteries > Batteries are electrochemical energy converters that directly convert chemical into electrical energy > Energy is generally stored within electrodes, except for air-zinc system > There are two battery systems: Primary batteries: designed to convert chemical energy into electrical energy only once Secondary batteries: reversible energy converters and designed for many cycles, i.e., repeated discharges and charges

28 Batteries > Positive & negative electrodes immersed in electrolyte > Discharge: reduction at ve electrode, oxidation at +ve electrode > Charge: reverse reactions occur, and energy must be supplied Mass transport does not occur, exchange of charges is very fast energy per weight or volume is very small Each charge discharge cycle changes depending on the physical electrode structure

29 Vanadium > 87% V used in steel industry for high-strength low-alloy steel for pipelines, ship building, automotive, machinery and rail parts > 13% for batteries and glass products > Future for vanadium already is in batteries > Vanadium - highly powerful and efficient batteries - usage for large scale, power grid storage > Storage is the biggest, most significant issue we are facing this century > Alternative generation for electricity wind, solar, geothermal - is limited without an efficient way to store it

30 Vanadium Batteries >Vanadium is also an efficient and environmentally safe energy storage system in batteries > Can be seen as a green battery >Vanadium batteries have a practical energy efficiency of 90% >Currently, the only battery that can directly connect to the grid > Energy from wind turbines and solar cells can also be stored in vanadium redox batteries

31 Vanadium Battery Chemistry > Developed at the Univ of NSW as a vanadium flow-battery > In a flow-battery, the reactants are in solution instead of in solid plates (as in the lead-acid battery). On one side of the battery is a solution of vanadium (V) ions dissolved in sulphuric acid. The solution on the other side is vanadium (II) ions in sulphuric acid. > Oxidation half-reaction: V 2+ V 3+ + e - > > Reduction half-reaction: V 5+ + e - V 4+

32 Vanadium Battery Chemistry > The solutions are separated by a sheet of graphite > The graphite is chemically inert and conducts electrons well > A semi-permeable membrane serves to complete the circuit and functions as a salt bridge > The two fluid electrolytes containing the vanadium ions flow through the porous graphite electrodes > During this exchange of charge a current flows over the electrodes, which can be used by a battery-powered device

33 Vanadium Battery Chemistry > Oxidation half-reaction: V 2+ V 3+ + e - Reduction half-reaction: V 5+ + e - V 4+

34 Vanadium Battery Chemistry > During discharge the electrodes are continually supplied with the dissolved substances from the tanks Once they are converted the resulting product is removed to the same or another tank > The cell has a potential of 1.6 volts when fully charged > The vanadium-flow cell can be recharged in two ways: 1. A vanadium battery can be plugged into a charger and recharged over a period of hours 2. The discharged electrolyte solutions can simply be drained and replaced with fully charged electrolyte solutions

35 Vanadium Battery Chemistry > However, redox flow-batteries have had the disadvantage of storing significantly less energy than lithium-ion batteries > Vehicles would only be able to cover about a quarter of the distance around 25 kilometers > Recent research has increased the capacity four or fivefold, to approximately that of lithium-ion batteries

36 Large Scale In Use Power supply for remote locations > Ready for commercialisation in applications load leveling, uninterruptible power supply systems to meet base or peak load demand, renewable energy storage, electric vehicles (though currently restricted to vehicles of fixed driving ranges, i.e. vans and buses)

37 Large Scale Vanadium Batteries > Solar filling station for electric cars (Perugia, Italy)

38 Comparison Between The Two Vanadium Lithium Number of cycles (lifespan) 35,000+ (35-50 years) ~300 (3-5 years) Low self discharge (once charged, stays charged) Contains non toxic material Highly expandable Generate low levels of heat Charges and discharges simultaneously Suitable for connection to power grid Small footprint

39 Factors To Consider > For an electric vehicle to be successful, the cost of the battery should not override the vehicle cost > Commercial high energy cells with Li Co-oxide cathode, graphite anode, and a liquid salt electrode cost about US$45/kg to manufacture > At this price, a 300 kg battery would cost >US$13,500

40 Vanadium-Lithium Batteries > Development of hybrid batteries are emerging > Subaru recently revealed its G4E concept car. Unveiled a capability of storing two or three times more energy than conventional lithium-ion batteries. Subaru expects the car to be able to travel 200 kilometres on a single battery charge.

41 Vanadium-Lithium Batteries > These battery packs deliver instantaneous high-power, takes a quick recharge (eighty percent [80%] of charge in fifteen minutes) > Vanadium can be used with or without Lithium > Batteries with Vanadium increase the life of the battery, can be left completely uncharged for extended periods of time without damage, and allow the batteries to be charged as they are in use. e.g. vanadium batteries can be simultaneously discharged and charged

42 Vanadium-Lithium Batteries > Battery maker, Valence expects support for electric vehicles will be strong in Europe regardless of economy, to reduce dependence on oil > The official energy policy in China states 10% of cars will be emission-free electric vehicles by 2013, and 20% of power will come from renewable resources by 2020 > To support renewable energy, battery storage is necessary, and batteries require Lithium

43 Future > It is expected the future will hold a high demand for hybrid and electric vehicles, laptops, mobile phones > Even more so as technological development enhances and consumer demand increases globally > Hybrid electric vehicles and all-electric vehicles can reduce the dependence on oil and will contribute to battery demand in the future

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