Beneficiation and Chemical Processing of Minerals Professor Aleks Nikoloski Murdoch University 23 June 2021 Context: Why lithium?

• It is the lightest metal • Has a single valence electron that easily forms a cation • Efficient conductor of electricity • A vital ingredient to drive the green energy quest • It’s unique and we will need much more of it!

PAGE 2 Murdoch University How did we get here?

• ca 6000 BC – Stone Age – discovery of gold and copper in native form

• ca 4,000 BC – Copper Age

• ca 2800 BC – Bronze Age

• ca 1500 BC – Iron Age

• ca AD 1800 – Industrial Revolution, the development of the first processes for production of large volumes of high-grade smelted iron (the Age of Coal and Oil)

PAGE 3 Murdoch University AD 1800 to 1950 – Use of physical properties and discovery of new metals and intrinsic properties

• 95 different new metals found • Each with different physicochemical properties and potential uses • Discovery of electricity… • More technological and scientific progress and changes in the 20th century than ever imagined possible – more than in all the other centuries before that, since the dawn of civilization, combined.

PAGE 4 Murdoch University Electrochemistry and the development of rechargeable batteries

• In 1901 Thomas Edison patented and commercialized a NiFe rechargeable battery • It was promoted for use as the energy source for electric vehicles • An aqueous solution of potassium hydroxide was used as the electrolyte charge carrier

PAGE 5 Murdoch University Thomas Edison and the electric car in 1913

PAGE 6 Murdoch University The development of the lithium ion battery

• In 1917 Turnock L. C. published an abstract reporting research findings on the effect of lithium ions on the capacity of the Edison battery • Tested the addition of lithium to the alkaline potassium electrolyte • Reported significant improvement in the battery charge capacity • The chemical mechanism was not understood at the time

PAGE 7 Murdoch University The rise of lithium

• 1800’s – discovered in , and • 1855 – first isolated • Initially used for soaps and then for lubricating greases for aircraft engines • 1950’s to 1990’s – used to decrease melting temperature of glass, increase conductivity of cryolite in the Hall-Héroult cells and for the production of nuclear fusion weapons • 1970’s to 1980’s – Whittingham and Goodenough separately developed rechargeable batteries with electrodes made capable of storing lithium ions • 1980’s – Yoshino made changes to the electrodes that dramatically improved safety and enabled commercial production of the lithium ion batteries • 2007 – the lithium ion batteries became dominant.

PAGE 8 Murdoch University The development of the lithium ion battery

• 2019 Nobel Prize in Chemistry awarded to Whittingham, Goodenough and Yoshino "for the development of lithium-ion batteries“ – by many “overdue” • The lithium ions are so small that they fit into holes within the crystal lattice of solids (intercalate) and effectively transfer charge

PAGE 9 Murdoch University Today – the Green Energy Revolution

• The Green Energy Revolution is the primary driver for the lithium demand and will fuel its production in the decades to come

• Renewables require batteries and with its special conductive properties' lithium has become the most sought-after ingredient for building the world’s modern batteries

• A major increase is required in the production of high purity lithium to enable the transition to a society powered by clean and renewable energy

PAGE 10 Murdoch University Where will the lithium come from?

• Lithium is sourced from either brine lakes or hard rock minerals

• However, the brine sources are being exhausted and harder to purify

• Meanwhile, increased focus is placed on hard rock lithium minerals processing

PAGE 11 Murdoch University How much lithium are we talking about?

• In 2018, the production ramped up to 85,000 tons (an increase of 23% compared to 2017 and of 123% compared to 2016) • Lithium will be critical in a world running on renewable energy and dependent on batteries • We need to greatly increase production to meet the demand for the low carbon technologies. There will be no Green Energy Revolution

PAGE 12 without more mining! Murdoch University Research Environment

Battery Value Chain Current research of my group at Murdoch is focussed on the beneficiation and refining of lithium from hard rock minerals & brines

PAGE 13 Murdoch University Beneficiation and Chemical Processing of Lithium Minerals

Conventional hard rock processing - Sulfuric acid roasting technology

PAGE 14 Murdoch University Beneficiation and Chemical Processing of Lithium Minerals

Lithium recovery rates versus feed grade during spodumene processing

• The graph illustrates the currently achieved plant recoveries versus the design recoveries. • Operations are struggling to meet or maintain design production rates. • Many projects currently under development expect recovery rates above 75%, which is optimistic. • Without improvement in the technology and understanding of the optimal ways to solve arising processing issues, some of the new projects may not reach design recovery rates.

PAGE 15 Murdoch University Beneficiation and Chemical Processing of Lithium Minerals

Immediate Research Needs

• To help industry establishment and growth and enable a move up the production leader to battery grade precursor chemicals by developing improved extraction & refining solutions • There is a significant need for additional study to improve the understanding of the current processing technology limitations and a number or technical challenges to solve to enable the downstream processing of this emerging commodity to be firmly established in Australia. • Specific needs to: i. Improve understanding of current technology limitations and solve technical challenges ii. Enable downstream processing to be firmly established in Australia iii. Develop better alternative processing options.

PAGE 16 Murdoch University Research and Development Goals

Improved technology for the extraction of lithium minerals and refining of battery grade lithium chemicals in Australia

• Research aims to deliver integrated processing solutions that will allow lower cost production of battery grade lithium which would greatly the profit margin • Also to optimising technology such as to produce with lower environmental impact, to increase ability to create jobs and to generate growth for the local communities. • To achieve this, a 4-year project is underway under the Future Batter Industries Cooperative Research Centre (FBICRC) to test new and improved processing options in the key areas of lithium extraction, recovery and purification, as well as processes to manage waste streams that generate by-products.

PAGE 17 Murdoch University Research Project Title

Beneficiation and Chemical Processing of Lithium Minerals

• The FBICRC project is multi-institutional and led by Murdoch University • The research program comprises 12 sub-project topics under four themes across the lithium processing flowsheet: I. Comminution and beneficiation II. Extraction III. Impurity separation and purification IV. Reagent recovery from liquors.

PAGE 18 Murdoch University Research Partners

Current participating organisations • IGO • BASF • Calix • Galaxy • Lycopodium • HEC Group • JordProxa • Mineral Carbonation International (MCi) • OneAtom12 • MRIWA • Murdoch University • University of Technology Sydney • Curtin University • Deakin University • University of Melbourne • University of Western Australia

PAGE 19 Murdoch University Project Lead + Prof Aleks Nikoloski • Longstanding Academic Chair of Extractive Metallurgy at Murdoch University • PhD in hydrometallurgy (Murdoch) with 24 years of teaching and research plus several years processing experience in industry • Expert in the electrochemistry of leaching & reduction processes for treatment of metals and minerals • Interest in kinetics and thermodynamics of metallurgical processes for the treatment of non-ferrous metals, in particular lithium, nickel, cobalt, copper, vanadium, gold and the platinum group metals • Significant experience in pilot scale process development and validation. _ PAGE 20 Murdoch University Theme I sub-projects

Mineral beneficiation 1. Crushing (CU led) The impact of hard rock breakage mechanism on liberation characteristics of lithium minerals and tantalum minerals by using various crushing techniques (Bogale Tadesse, Boris Albijanic, George Franks, Mark Aylmore) 2. Grinding (UTS led) Development of energy efficient grinding technology and grinding additives to effectively break and grind lithium ore to fine powders with desired size and optimised size distribution (Guoxia Wang at UTS and JdLT at CU) 3. Coarse particle processing (CU led) Optimization by wet and dry separation including (i) gravity (jigs and dense media separation techniques), (ii) magnetic and (iii) coarse particle flotation (HydroFloat technology) for lithium ores (Boris Albijanic, Bogale Tadesse, George Franks, Laurence Dyer, Mark Aylmore) 4. Flotation reagents (CU led) Development and optimization of collectors for fresh and saline water flotation of hard rock minerals (i) spodumene, (ii) petalite and (iii) lepidolite (George Franks, Boris Albijanic, Postdoc, Bogale Tadesse, Chris Aldrich, Laurence Dyer, Richard Alorro, Aleks Nikoloski)

PAGE 21 Murdoch University Theme II sub-projects

Lithium extraction 5. Calcination/leach (CU and UTS led) Development of (i) alternative roasting processes for spodumene and petalite and (ii) optimisation of the parameters for the conventional production process by calcination and roasting (Postdocs at CU/MU and Guoxia Wang at UTS) 6. Direct leaching (MU led) Development of alternative fully hydrometallurgical processes for the extraction of lithium from hard rock minerals (high temp/pressure and alkaline) (Aleks Nikoloski, Postdocs at Murdoch and Curtin) 7. Mechanochemical (CU led) Mechanochemical processing of hard rock lithium bearing minerals (Richard Alorro at Curtin)

PAGE 22 Murdoch University α-spodumene (monoclinic) β-spodumene (tetragonal) Theme III sub-projects Electrodialysis cell at Murdoch University

Impurity separation and purification

8. Precipitation and ion exchange (MU led) Impurity separation lithium leach solutions by (i) precipitation and (ii) IX for product and by‐product recovery (Post Doc at Murdoch, Richard Alorro and Postdoc at Curtin) 9. Crystallisation (UTS led) Exploration and establishing of crystallisation technologies using new chemicals and reagents for production with maximum rate of high purity battery grade lithium containing chemicals (including monohydrate) obtained from the lithium ore (Guoxia Wang and Postdoc at UTS) 10. Electrodialysis (MU led) Electrodialysis for production of LiOH.H2O from different product liquors direct rather by metathetic process with reagent addition (Aleks Nikoloski, Post Doc and MPhil student at Murdoch and Post Doc at Deakin)

PAGE 23 Murdoch University Theme IV sub-projects

Reagent recovery and project integration

11. Caustic and acid recovery (MU led)

Salt splitting of Na2SO4 by membrane separation for reagent regeneration and waste treatment (Aleks Nikoloski, Post Doc at Murdoch) 12. Technoeconomic evaluation of sub- project deliverables (MU led) The technoeconomic impact of the research outcomes from each of the individual subprojects will be evaluated on ongoing basis (Parisa Bahri and Postdoc at Murdoch)

Salt splitting in a two-compartment cell configuration using ion selective and bipolar membranes PAGE 24 Murdoch University Outcomes

Benefits • The main expected benefit is improved technology for the entire flow sheet used in the production of high grade lithium chemicals • This will be done by focusing on the key project objectives as outlined on the previous slides, where each objective will be studied as a separate sub-project topic • Each sub-project will deliver a series of regular interim progress reports of the experimental findings, a literature review and final project report (or PhD/MPhil thesis) at the end of the overall project.

PAGE 25 Murdoch University Impacts

Benefit impacts • The beneficial impacts will include: • lowering of production costs • lowering the environmental impacts • lower lithium losses • increasing recovery of yield of the process • ability to utilise previously uneconomic or marginal resources • creating sovereign capability • accelerating time to market • enhancing market preference • value-adding • market growth • employment opportunities in Australia • risk mitigation.

PAGE 26 Murdoch University The Present Status

Currently, Australia exports the main commodities (Li, Ni, Mn, Co, C) used in the lithium battery production in the form of mineral concentrates and very little of the value incorporated into manufacturing of lithium ion battery materials is retained in the country

PAGE 27 Murdoch University The Constraints

Constraints to Australia in developing a cathode precursor industry that is competitive on the world market include: • Lack of production infrastructure for synthesising quality (both chemical quality and physical properties) of Precursor Cathode Active Material (PCAM and CAM) on a pilot scale • Access to standardised testing protocols critical for PCAM and CAM development and optimisation • Cost effective, environmental, social governance (ESG) sensitive processing route that includes minimising and utilising waste material as a by-product.

PAGE 28 Murdoch University The Opportunity

• Production of lithium to a high purity and other battery precursor minerals can add significant value to the Australian battery industry and currently there are no facilities for this in Australia • Roskill’s1 predicts that metals markets, electrification and growth in electric vehicles (EVs) will not fundamentally change as a result of COVID-19

• Increased adoption of EV’s is expected to be a key driver of the Lithium-ion Battery (LIB) demand in the first wave technological transformation. PAGE 29 Murdoch University EMAIL [email protected]

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