FACETS OF GRAPHITE June 2017
1. INTRODUCTION What is Graphite? Why is Graphite Important? Current Demand & Prices for Selected High Purity Graphite Applications Contents 2. SELECTED APPLICATIONS Lithium Ion Batteries Vanadium Redox Batteries Other batteries PEM Fuel Cells Nuclear Reactors Lubricants 3. LITHIUM ION BATTERY MARKET Lithium Ion Battery Market Electric Vehicles (EVs) Stationary Energy Storage Systems
1. INTRODUCTION
What is Graphite? A non-metallic mineral and the most stable form of carbon. Graphite comprises parallel sheets of carbon atoms in a hexagonal arrangement. Chemically inert, corrosion resistant with a high melting point (3650 C). Is a good conductor of electricity. High natural lubricity that reduces wear and tear and one of the lightest reinforcing agents. Natural graphite forms: amorphous, flake vein and hydrothermal. Crystals comprise hexagonal plates or distorted clusters of flaky plates. Thin plates are flexible. Synthetic graphite forms: powder, blocks, anisotropic and isotropic. Graphite can be synthesized using petroleum byproducts, or in the case of CarbonScape, waste biomass.
Why is Graphite Important? A supply critical strategic mineral in the USA and Europe. The global market for graphite is currently ~4 million tons valued at USD15 billion p.a., CAGR 4% between 2015-20. Average price of high purity graphite ranges from USD4,000 35,000 per tonne, depending on purity, morphology and end use. There are over 200 applications of graphite. Major graphite applications include: batteries, powder metallurgy, fuel cells, lubricants, nuclear applications and electronics. Technology is driving demand for high purity graphite for Li-ion batteries. Energy storage systems: infrastructure, defence, telecom, finance and medical sectors. Transportation: electric and hybrid vehicles, buses, trucks and trains Electronics: smartphones, computers, tablets, robots, household and garden appliances etc.,
Current Demand & Prices for Selected High Purity Graphite Applications Market Segment 2017 Market Demand Estimate (Tonnes) Price Range (USD/Tonne) Average Price (USD/Tonne) Electronics 8,000 30,000-40,000 35,000 Nuclear 30,000 10,000-35,000 23,000 Batteries 160,000 4,000-20,000 12,000 Fuel cells 15,000 5,000-10,000 8,000 Powder metallurgy 20,000 3,000-12,000 7,000 Lubricants 80,000 3,000-5,000 4,000 Total 313,000 Source: Seekingalpha.com, 16 December 2015
2. SELECTED APPLICATIONS
APPLICATION 1: LITHIUM ION BATTERIES It is possible to insert other atoms between the sheets, a process that is called intercalation. Lithium ions are inserted to create graphite anodes for lithium ion batteries. Type of graphite required: High purity (>99.95% Cg) High crystallinity (that provides good intercalation capacity) Spherical particle shape and high packed density (to produce high energy density, smaller batteries) Treated surface and low surface area (for high stability and safety). Expanded graphite made by intercalating graphite with nitric and sulphuric acid is used as an electrically conductive additive to the positive electrode.
APPLICATION 2: VANADIUM REDOX BATTERIES Vanadium redox batteries were first demonstrated in the 1980s. They have several advantages over Lithium-ion batteries: long life with little maintenance, ease of scalability, safety, cost, convenience and low environmental impact. See http://www.vanadium-redox-battery.com/vanadiumbatteries-vs-lithium/ The primary reason for these advantages is that electrochemical reactions of these batteries occur at the surface of the graphite electrodes, and both oxidized and reduced species remain dissolved in the electrolyte, as such no forces are exerted on the graphite electrode. These batteries are most useful for stationary energy storage applications since they have relatively poor energy-to-volume ratio in comparison with Li-ion batteries and the aqueous electrolyte makes the batteries heavy. the bi polar plates in a vanadium redox battery are made out of graphite. It is estimated that 300 tonnes of graphite are required for every mw/hr of VRB capacity. See http://northerngraphite.com/vanadium-redox-batteries/
APPLICATION 3: OTHER BATTERIES Graphite is also used in the positive electrode of Zinc-Air batteries as an electrically conductive additive. Requires graphite of high purity, high crystallinity, defined particle morphology (expanded graphite), and particle size distribution. Graphite is used as a conductive additive, lubricant, and processing aid in cathode of primary alkaline batteries and in the cathode as an electrically conductive additive in rechargeable alkaline batteries. Requires graphite of high purity, high crystallinity, and defined particle morphology and particle size distribution. Graphite is also used in the electrodes of lead acid batteries as an electrically conductive additive. Requires graphite of high purity, high crystallinity, defined particle morphology and size distribution.
APPLICATION 4: PEM FUEL CELLS Graphite can be intercalated with sulfuric acid and nitric acid to produce expanded graphite that is used in Proton Exchange Membrane (or Polymer Electrolyte Membrane) fuel cells. Majority of the cell weight (80%) is graphite. Small quantities of graphite is used in other components. Requires graphite of high crystallinity, appropriate grain size, high purity (with minimal metallic impurities), appropriate particle shape, surface properties and size distribution. Fuel cells are used in transport and portable power systems. e.g. RVs, cabins and marine, hybrid vehicles, power for remote locations including gas/oil wellsites, communication towers, security, weather stations, UPS, aerospace and military applications, breathalyzers etc.
APPLICATION 5: NUCLEAR REACTORS Graphite is used as a moderator, reflector, shield and as a fuel coating for pebble bed nuclear reactors. Functionality provided: radiation moderation, thermal conductivity, structural integrity, stability and prevention of thermal shock. Requires graphite with isotropic properties, extremely low impurities, appropriate particle shape and size distribution, high density and strength and stable crystal structure. Difficult to achieve with most natural graphite materials. Nuclear grade synthetic graphite is made from specially produced isotropic coke. Must meet appropriate ASTM Standards e.g. D7301, D7219
APPLICATION 6: LUBRICANTS Graphite is used as a a high temperature and high friction lubricant in a variety of industrial and automotive applications. Used as a dry powder or is added to grease, oil, water or other solvents. Requires competitively priced graphite powder with high crystallinity, high purity, particle size distribution in the desired range, low moisture content and no abrasives. Major synthetic graphite producers dominate this market due to availability of secondary powder. Chemically inert, eco-friendly and cost-effective alternative to lead and molybdenum disulphidebased lubricants.
3. LITHIUM-ION BATTERY MARKET
Lithium Ion Battery Market Li-ion battery market is the main driver of future growth in the high purity graphite market. It takes 10-30 x more 99.95% purity graphite than lithium to make lithium-ion batteries. China controls 75% of global graphite production and 100% of CSPG production. These are industries hampered by serious environmental issues. It is not possible to have green cars with dirty batteries. Battery makers in USA, Europe, Taiwan, Japan and South Korea are seeking to diversify their sources of CSPG supplies. Several junior graphite companies (mainly from Australia and Canada) are looking to compete in the CSPG market. None of these companies have progressed to commercial production. In 2016, around 65% of all Li-ion battery anode material was sourced from natural spherical graphite and 33% from synthetic graphite material. (The remaining 2% from other alternatives such as lithium titanate, silicon and tin).
ELECTRIC VEHICLES Global sales of EVs is set to expand from 1.5 million units currently (<1% of new car sales) to 41 million units by 2040 (or 35% new car sales). Each electric car contains 45-100+ kg coated spherical graphite (CSPG). This will generate a Li-ion battery market worth a projected USD 250 billion by 2040. Panasonic forecasts EV Li-ion battery revenues to grow at CAGR 16.9% p.a. from USD 6 billion in 2014 to USD 30 billion in 2025. Countries such as China, Germany, Norway and Netherlands are driving the demand for EVs with Government incentives.
Stationary Energy Storage Systems The stationary energy storage market has the potential to be larger than the EV market. Growing market for PV solar/li-ion battery systems for those wishing to go off grid. Used in UPS, back-up and portable power solutions in infrastructure, defence, security, medical, telecom and finance sectors. Panasonic forecast Lithium ion battery revenue in the stationary energy storage sector to grow CAGR 74.9% from ~USD 2 billion in 2014 to ~USD 170 billion in 2025.
Battery Grade Graphite: Synthetic vs Natural # Property Synthetic Graphite Natural Graphite 1 Price USD20,000/tonne USD8,000-12,000/tonne for coated natural spherical graphite 2 Purity Can be engineered to >99.9% C Can be purified to >99.5% C by chemical or thermal means 3 Process time ~11 weeks Lengthy, multi-step 4 Flexibility and customizability High flexibility in processing, particle size and surface chemistry 5 Consistency and reliability of More consistent and more reliable performance Low flexibility and difficulties in incorporating in processes. Less consistent and less reliable 6 Electrical and thermal conductivity Inferior performance Superior performance 7 Energy density Low since synthetic graphite is brittle, cannot easily be spherodised. High - can be spherodised to maximize energy density. 8 Yield High Low (yield of spherical graphite from flake graphite is ~30-50%) 9 Environmental impact Negative Negative 10 Stage of technology development Advanced Emerging 11 Sustainability Low Low 12 Precursor to Graphene Limited application Yes