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
LiFe1-xMxPO4 (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
Li3M2-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
LixMoO2	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-NaNi1-x-y-zM1xM2yM3zO2	Substituted O3 Na nickelates	US 9761863 US 9774035 US 9917307	Pre-production
O3-NaNi1-x-y-zM1xM2yM3zO2 + P2- NaNiyM1xM2yM3yO2	Na mixed phase (O3/P2) cathodes	US 2017/0190595	Pre-production
Na2MSiO4	Na orthosilicates	US 10115966	Experimental
Na4-xLixM3(PO4)2P2O7	Na phosphate-diphosphates (4321)	US 9608269	Pre-production
Na2Mb(SO4)c	Na sulfates	US 2015/0024269	Experimental

Faradion Press Articles - C&EN and C&I

Hiya-

Moving on from our company profile paper in BEST magazine (see post below), Faradion has also featured in recent battery review articles in Chemical & Engineering News (C&EN, the news journal from the American Chemical Society) and Chemistry & Industry (C&I, the news journal from the Society of the Chemical Industry, SCI).

The C&EN article may be found here:

http://cen.acs.org/articles/92/i28/Chemistrys-Electric-Opportunity.html

This feature also includes a short video that shows a little more information about our company (plus something by Elon Musk on Tesla)

The C&I feature is here:

http://www.soci.org/Chemistry-and-Industry/CnI-Data/2014/10/A-salt-ion-battery

Jerry

Faradion Article - BEST

A recent review article on Faradion has appeared in BEST - Batteries and Energy Storage - magazine:

http://www.faradion.co.uk/about/news/2014/11/faradion-appears-in-best-magazine/

Thanks go to Tim Probert at Best Magazine for the excellent review - even including the mention of our 'Dickensian Incentive Scheme'.

http://www.bestmag.co.uk/

Ultra Low-cost LiFePO4 Synthesis

We all understand that Li-ion batteries based on the LiFePO4 active material offer outstanding cycle life and beneficial safety properties. So what has been holding it back?

One of the major obstacles to the major commercial roll-out of LiFePO4 Li-ion batteries is the cost of the active material itself. In terms of $/kWh (i.e. the cost per energy unit) the lithium iron phosphate is relatively expensive when compared directly to traditional layered oxide materials such as LiCoO2, NCA and NMC. But why is this? Surely the nature and availability of the constituent elements would mean that LiFePO4 should be really inexpensive. That statement is basically true, but the preparation methods used commercially - often complicated and multi-step - mean that the overall manufacturing cost of the LiFePO4 is actually very high, typically around $20/kg. That's not good.

What the industry really needs is a ultra low cost manufacturing method that is easily scalable. Perhaps approaching <$10/kg. That would really make a substantial difference.

So what can one do? During the development of its proprietary Na-ion technology, Faradion Limited has also discovered some ultra low cost methods of preparation for LiFePO4 (as well as other polyanion based active materials). We anticipate that the LiFePO4 made this way will be substantially cheaper that any other currently-available commercial approach.

For more information about our LiFePO4 synthesis method please refer to our website:

www.faradion.co.uk

or directly from me:

jerry.barker@faradion.co.uk

I'm Back!!

Hiya everyone.....my apologies for failing to update my blog regularly, but after a long delay I am back. For the last 3 years I have been working as the co-founder and CTO of Faradion Limited, a UK-based start-up company promoting a new Na-ion battery technology. As you will probably know I have been researching Na-ion technology for many years now and have maintained that this cell chemistry is the logical and sustainable replacement for Li-ion batteries in a number of low cost applications.

More information about Faradion may be found at our website:

www.faradion.co.uk

or directly from me:

jerry.barker@faradion.co.uk

Faradion Limited...JB Appointed CTO

Just to let everyone know.....I was recently appointed CTO of Faradion Limited. I will take on this role while also maintaining my independent energy storage consultancy (www.jerrybarker.co.uk). Should be a busy time!!

Faradion is a high-tech start-up company based in the UK which is engaged in the development of next generation energy storage devices. The Faradion HQ is located in Sheffield, Yorkshire. The company will target the consumer, automotive and utility markets. The technical objectives will not follow the well-trodden Li-ion path, but will be investigating new, non-lithium based battery opportunities.

Additional information about Faradion may be found at the company website:

Faradion Limited website

Exciting times lie ahead for the team.

Jerry

IBA - Technology Award 2012

Great News and a Big Surprise!!

The International Battery Materials Association (IBA) has decided to award me the Technology Award for 2012. Apparently the award is granted for "contributions made to identifying new secondary battery cathode materials and related materials research field, which has been recognized internationally".

Many thanks to the board of the IBA for the award ....which, as I say, was a complete surprise. The list of previous winners is extremely impressive, so I am more then happy to be included.

Jerry

Phostech Lithium Inc. appeals LiFePO4 Carbothermal Reduction Decision

Further to the news below regarding the LiFePO4 carbothermal reduction litigation case involving Valence Technology Inc. and Phostech Lithium Inc., Phostech has decided to appeal the decision.

The latest Phostech press release may be found here:

Phostech Press Release

Based on this appeal, Phostech has resumed the production and sale of its P1 grade LiFePO4 material.

Jerry

Valence Technology wins Carbothermal Reduction Patent Infringement Lawsuit

Valence Technology Inc. has won its Canadian patent infringement lawsuit (Tuesday February 17, 2011) regarding its proprietary carbothermal reduction technology (CTR), which Valences uses to make lithium iron (magnesium) phosphate as well as other lithium-based active materials for Li-ion batteries. The Canadian patent in question is number 2,395,115. The link to this patent may be found here:

Canadian Patent 2,395,115 (Inventors: J. Barker et al.)

The lawsuit was filed against Phostech Lithium Inc. and the judgment entitles Valence to an injunction, an election of either an accounting of profits or damages, reasonable compensation and costs. The Valence press release for this announcement may be found here:

Valence Technology Victorious in Patent Infringement Lawsuit

The CTR invention was invented and developed by Jerry Barker and co-workers as the most economical process for the manufacturing of lithium metal phosphates for battery applications. Valence has been using this technology for several years to make its lithium iron magnesium phosphate material.

Interestingly, the Phostech PR team have been working overtime to put the best spin on the announcement:

Phostech Lithium Inc. Press Release

In summary, however this judgement must be seen as a serious blow to both Phostech Lithium and its parent company, Sud-Chemie. More information on the judgement from the website, Green Car Congress, may be found here:

Green Car Congress: Valence wins Patent Infringement Lawsuit

Jerry

Vanadium-based Li-ion Batteries

If you spend any significant amount of time reviewing the scientific literature concerning new active materials for Li-ion batteries, you quickly notice something rather interesting…..the number of vanadium containing phases appears extremely high. Was is this? Why is vanadium such a useful transition metal in these materials? Here is my short summary:

1. Atomic Mass. Vanadium is a first row transition metal, meaning that it has relatively low atomic mass (50.94). It follows that, all things being equal, active materials containing V should have relatively low formula mass, resulting in a high theoretical specific capacity (mAh/g).

2. Voltage Range. The operating voltage of vanadium-containing phases is typically in the range 3.0 -4.5 V vs. lithium. Why is this voltage range so important? For at least three good reasons: (i) the higher the operating voltage the higher the specific energy, Wh/kg (which is the product of the specific capacity and the operating voltage). High Specfic Energy is what us battery scientists are striving to achieve; (ii) If the operating voltage is too low (typically < 3.0 V vs. Li) the active material will be air/moisture sensitive, which creates problems during cell manufacture; (iii) Above 4.5 V and we run into stability issues with the electrolyte. Simply stated, the operating voltage is just too oxidative for most common, non-aqueous electrolyte solvents.

3. Multiple Oxidation States. Vanadium has 5 stable oxidation states: 0 (metal), +2, +3, +4 and +5. Why is this important? It means that in active materials containing one vanadium ion we have the possibility of reversibly cycling more than 1 lithium (or sodium) ion per formula unit. This means we can expect very high specific capacities. With most other transition metals this is not the case.

4. Energy Levels. The energy levels of the common vanadium oxidation states, viz. +3, +4 and +5, are quite close. This means that while accessing these oxidation states during the charge and discharge of a Li-ion cell there are not large steps (fluctuation) in the operating voltage. Why is this important? Well battery designers are not too keen on voltage excursions or steps during the normal operation of the Li-ion cell since this causes major complications in the control electronics.

5. Inexpensive. Compared to many other transition metals, vanadium is actually relatively cheap and abundant. It is not as inexpensive as Fe and Mn, but it is significantly cheaper than either Co or Ni. Vanadium is currently mined in Australia, China, South Africa and Russia. New mines are coming on stream all the time – typically to satisfy the growing demand in the steel industry – but this also means there should be plenty for the battery market.

6. Polyanions. Vanadium is particularly suitable for incorporation into polyanion phases (sulfates, phosphates etc). Polyanion phases are expected to become the next generation of Li-ion active materials offering high specific energy, excellent safety performance and good cycling stability.

7. Redox Batteries. Vanadium finds application in Vanadium Redox flow Batteries (VRB), which also take advantage of the multiple V oxidation states.

So there are many reasons to think positively about the future of vanadium in Li-ion (or Na-ion) battery applications. I have worked on a number of these materials myself……for example, Li3V2(PO4)3, LiVPO4F, LiVOPO4, LiVP2O7, Na3V2(PO4)2F, LiV2O5 etc.

In my opinion, the (battery) future looks bright….the future looks like Vanadium.

Jerry