Barker's Battery Blog: Li and Na Active Materials Review

Wednesday, 27 March 2019

Li and Na Active Materials Review

Hi Everyone,

Apologies for not posting for a while - but things have been very busy!

Anyway, I decided to update my active materials summary - with a table showing some of the materials I have studied, patented and commercialised for Li and Na-ion battery applications. So here goes, and I hope it is useful (table below).

In addition, the carbothermal reduction (CTR) synthesis method (see other posts in this blog; patented by JB while working at Valence Technology Inc.) remains the industry-standard manufacturing method for making e.g. LiFePO4 as well as many other Li-ion and Na-ion active materials.

Li-ion and Na-ion Cathode Active Methods

Active Material	Common Name/Type	US Patent#	Commercialization Status
LiFe_1-xM_xPO₄ (M = Mg, Ca, Zn etc.)	Substituted Olivines	US 6884544 + others	Commercialized 2002
(ss)-LiMn₂O₄	Surface-stabilized manganese spinel	US 6183718 + others	Commercialized 1996
Li₃M₂(PO₄)₃ (M = V, Cr, Mn, Fe, Al etc.)	Li Nasicons	US 6387568	Prototype Scale
Li₃M_2-xM’x(PO₄)₃ (M = V, Cr, Mn, Fe, etc.)	Substituted Li Nasicons	US 6387568	Experimental
LiMPO₄F (M = V, Cr, Mn, Fe, Al etc.)	Li Tavorites (-F)	US 6387568 + others	Prototype Scale
LiMPO₄.OH (M = V, Cr, Mn, Fe, Al etc.)	Li Tavorites (-OH)	US 6387568 + others	Experimental
LiMP₂O₇ (M = V, Cr, Mn, Fe, Al etc.)	Lithium diphosphates	US 7008566	Experimental
Li₂MP₂O₇ (M = Fe, Mn, Co, Ni etc.)	Lithium diphosphates	US 7008566	Experimental
Li₂M(SO₄)₃ (M = V, Cr, Mn, Fe, Al etc.)	Lithium sulfates	US 5908716	Experimental
LiMSO₄F (M = Fe, Mn, Co, Ni etc.)	Lithium fluorosulfates (Tavorite structure)	US 2005/0163699	Experimental
NaMSO₄F (M = Fe, Mn, Co, Ni etc.)	Sodium fluorosulfates	US 2005/0163699	Experimental
Li₂MPO₄F (M = Fe, Mn, Co, Ni etc.)	Lithium fluorophosphates	US 6890686 + others	Experimental
Li₄M₂(SiO₄)(PO₄)₂(M = V, Cr, Mn, Fe, Al etc.)	Lithium silicophosphates	US 6136472	Experimental
β-LiVOPO₄	Lithium vanadyl phosphate	US 6645452	Experimental
NaMPO₄F (M = V, Cr, Mn, Fe, Al etc.)	Sodium fluorophosphates	US 6872492 + others	Experimental
Na₃M₂(PO₄)₂F₃ (M = V, Cr, Mn, Fe, Al etc.)	Sodium fluorophosphates	US 6872492 + others	Pre-production
LiMTiO₄, LiMZrO₄ (M = V, Cr, Mn, Fe, Al etc.)	Lithium titanates, Lithium zirconates	US 6720112	Experimental
Li₂MTiO₄, Li₂MZrO₄ (M = Fe, Mn, Co, Ni etc.)	Lithium titanates, Lithium zirconates	US 6103419	Experimental
Li₂CuO₂	Lithium copper oxide	US 5670277	Experimental
Li_xMoO₂	Lithium molybdenum oxide(s)	US 6908710	Experimental
γ-LiV₂O₅, NaV₂O₅	Lithium (sodium) vanadium oxide	US 6645452	Experimental
Na₃MP₃O₉N (M = V, Cr, Mn, Fe, Al etc.) Na₂M₂P₃O₉N (M = Fe, Mn, Co, Ni etc.)	Sodium nitrido-phosphates	US 2008/0187831	Experimental
Na₇M₄(P₂O₇)₄PO₄ Na₇M₃(P₂O₇)₄	Na condensed diphosphate-phosphates	US 9608269	Experimental
LiMXO₄ Li₄MXO₆ Li₃MXO₆ Li₂M₂XO₆	Li oxo-metallates	US 10115966	Experimental
NaMXO₄ Na₄MXO₆ Na₃MXO₆ Na₂M₂XO₆	Na oxo-metallates	US 10115966	Experimental
O3-NaNi_1-x-y-zM1_xM2_yM3_zO₂	Substituted O3 Na nickelates	US 9761863 US 9774035 US 9917307	Pre-production
O3-NaNi_1-x-y-zM1_xM2_yM3_zO₂ + P2- NaNiyM1_xM2_yM3_yO₂	Na mixed phase (O3/P2) cathodes	US 2017/0190595	Pre-production
Na₂MSiO₄	Na orthosilicates	US 10115966	Experimental
Na_4-xLi_xM₃(PO₄)₂P₂O₇	Na phosphate-diphosphates (4321)	US 9608269	Pre-production
Na₂M_b(SO₄)_c	Na sulfates	US 2015/0024269	Experimental

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Barker's Battery Blog

Jerry Barker is currently co-founder and Chief Scientist of Faradion Limited, a UK-based start-up company specializing in next generation Na-ion battery technology. The company has state-of-the-art R&D labs and prototype manufacturing facilities in the UK. Check out the company website here:

http://www.faradion.co.uk/

In May 2019, Jerry was appointed Honorary Professor within the School of Chemistry at the University of St. Andrews.

Jerry Barker also runs an independent technology consultant, specializing in the energy storage sector. He may be contacted here:

jerrybarker@gmail.com

Jerry has worked in the UK, Denmark and the US and has managed materials research labs in Europe and North America. He is currently located in the UK where he has consulted for, and advised a number of battery R&D companies, varying in size from small university startup to global multinational. He has also consulted and advised on solar photovoltaics (PV) where he is widely regarded as a world expert on the electrodeposition of thin film semiconductors for PV and other applications. In his early career Jerry spent time at UCSB where he collaborated with the Nobel prize winners Alan Heeger and Hideki Shirakawa on alkali metal doped polyacetylene.

Jerry has published extensively in the energy storage area (h-index = 56, total number of citations >11,000) and is a named inventor on more than 120 issued US patents. He has appeared as a patent litigation expert witness in Europe and in North America. He has also acted as the due diligence technical expert for a number of VC-backed startup companies. Additional information on Jerry's background may be found at the website:

http://www.jerrybarker.co.uk/

Jerry currently acts as an Expert Panel member for the UK's Faraday Institution and as a Board Member of the UK LiBATT consortium.

The articles and comments posted on this blog will simply be Jerry's own personal opinions. Much of the emphasis will be placed on the recent news stories involving Energy Storage Systems - especially Lithium metal anode, Lithium-ion and Sodium-ion Batteries - and Thin-film Photovoltaics.

Please feel free to add useful comments and suggestions - these will help to keep the discussions alive. I will try to respond to these postings as they are made.

Jerry