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

Symmetrical Li-ion Cells based on LiVPO4F

The fabrication and electrochemical properties of novel LiVPO4F//LiVPO4F symmetrical Li-ion cells were described in a paper in ESSL by my group in 2005. A link to the abstract may be found here:

A Symmetrical Lithium-ion Cell based on LiVPO4F

This preliminary work indicated that the fluorophosphate may function successfully as both the positive and negative electrode material in high rate Li-ion cells. At the positive electrode the LiVPO4F uses the V3+/V4+ redox transition while at the negative pole the V3+/V2+ redox couple is operational. Advantageously, the reversible specific capacity for these two reactions is roughly equivalent meaning that the same electrode coating can be used for both electrodes. This simplifies the overall manufacturing process and consequently makes a big difference to the production costs.

Recent work by Okada and co-workers has extended this approach to study the LiVPO4F//LiVPO4F system using an Ionic Liquid electrolyte. This new investigation confirms that the symmetrical cell design demonstrates good rate, safety and cycling performance. The abstract to this work may be found here:

Symmetric Li-ion cell based on LiVPO4F with Ionic Liquid Electrolyte

In summary, the excellent lithium insertion properties of the LiVPO4F active material have again been clearly demonstrated.

Jerry

Lithium and Sodium Active Materials

As some of you will know, over the past few years I have been involved in the discovery and development of many new active materials for both lithium and sodium battery applications. I was asked at a meeting recently if I had compiled a list of these inventions. The short answer is "No", but there is a limited summary of some of these materials on my website (www.jerrybarker.co.uk) although this is certainly not an exhaustive list.

So below is a list of the different active materials in which I am the inventor or co-inventor. In each case, I have also included one of the associated US patents, but in most instances there will be multiple issued patents and patent applications and the one shown here may not be the earliest filing. It is simply listed as an example. Please also note that I have probably missed out a few materials, so I will no doubt need to amend this table in the near future (i.e. when my memory is fully functional!).

I have not added hyperlinks to all these patents, so if you need additional information I suggest you use:

Free Patents Online


Anyway, here is the list:


LiFe1-xMxPO4 Substituted Olivines (M = Mg, Ca, Zn etc.) US 6884544

Li3M2(PO4)3 Nasicons (M = Fe, V, Mn etc.) US 5871866

LiMPO4F Fluorophosphates (M = Fe, V, Mn etc.) US 6387568

LiMPO4.OH Hydroxy-phosphates (M = Fe, V, Mn etc.) US 6777132

Li2MP2O7 Dilithium diphosphates (M = Fe, Mn, Co, Ni etc.) US 7008566

Li3M(SO4)3 Lithium sulfates (M = Fe, V, Mn etc.) US 5908716

LiMSO4F Lithium Fluorosulfates (M = Fe, Mn, Co, Ni etc.) US 2005/0163699

NaMSO4F Sodium Fluorosulfates (M = Fe, Mn, Co, Ni etc.) US 2005/0163699

Li2MPO4F Lithium Fluorophosphates (M = Fe, Mn, Co, Ni etc.) US 6890686

Na2MPO4F Sodium Fluorophosphates (M = Fe, Mn, Co, Ni etc.) US 6890686

Li4M2(SiO4)(PO4)2 Silicophosphates (M = Fe, V, Mn etc.) US 6136472

Li3M1.5Al0.5(PO4)3 Substituted Nasicons (M = Fe, V, Mn etc.) US 5871866

β-LiVOPO4 Vanadyl Phosphate US 6645452 (method-of-making)

NaMPO4F Sodium Fluorophosphates (M = Fe, V, Mn etc.) US 6872492

Na3M2(PO4)2F3 Sodium Fluorophosphates (M = Fe, V, Mn etc.) US 6872492

LiMTiO4, LiMZrO4 Titanates, Zirconates (M = Fe, V, Mn etc.) US 6720112

Li2MTiO4, Li2MZrO4 Titanates, Zirconates (M = Fe, Mn, Co, Ni etc.) US 6103419

Li2CuO2 Lithium Copper Oxide US 5670277

LixMoO2 Lithium Molybdenum Oxides US 6908710

LiV2O5 Lithium Vanadium Oxide

Novel Phase A US Pending

Novel Phase B US Pending

Novel Phase C US Pending


Jerry

Faradion - a new Energy Storage Company

A new UK-based energy storage company, Faradion, has been established in Sheffield, Yorkshire. The company is named after chemist and physicist Michael Faraday – who was pivotal in developing the science of electrochemistry – Faradion plans to use a number of technologies which can potentially halve the costs of storing electrical energy.

Jerry

Lithium Vanadium Phosphate

I noticed recent press releases from GS Yuasa describing its efforts in developing lithium vanadium phosphate cathode materials for next generation Li-ion applications. A good link to this may be found at the Green Car Congress website:

GS Yuasa Prototypes Li-ion Batteries with Vanadium Phosphate Cathode Material

Nothing is disclosed by GS Yuasa about the precise chemical nature of this vanadium phosphate active material. The best known phase in this area is the monoclinic Nasison phase, Li3V2(PO4)3. This material promises to deliver safe, large format Li-ion batteries with improved energy density and rate performance over LiFePO4. Clearly the use of this material in Li-ion applications has been covered in numerous issued patents assigned to Valence Technology Inc., so it will be interesting to find out more about the GS Yuasa chemistry.

It will be intriguing to see how this progresses.

Jerry

Li2FeP2O7: A Potential New Active Material for Lithium-ion Batteries?

A article in JACS by Nishimura and co-workers recently caught my eye. The paper describes the promising electrochemical lithium insertion characteristics of the lithium iron diphosphate material, Li2FeP2O7. The link to the paper may be found here:

New Lithium Iron Pyrophosphate as 3.5 V Class Cathode for Lithium Ion Battery

The iron diphosphate demonstrates a reversible specific capacity of around 110 mAh/g at an operating voltage of about 3.5 V vs Li. These are encouraging characteristcs and when combined with the anticipated low cost and good thermal safety, this cathode material may represent an excellent choice for incorporation into large format Li-ion devices. I guess it could even challenge LiFePO4 in some limited applications.

The Li2FeP2O7 material actually represents just one example of a class of lithium metal diphosphates, Li2MP2O7 (where M = Fe, Co, Ni, Mn etc.). The use and preparation of these materials was first recognized in the following issued US patent (Inventors: Barker and Saidi, filed April 2003):

US#7008566: Oligo Phosphate-based Electrode Active Materials

I will wait with great interest to see the developments in this field. Clearly some of the analog materials such as Li2MnP2O7 may offer improved electrochemical behavior over the Fe phase. Will it be possible to extract both lithium ions from the structure?

Jerry

Pellion Technologies Inc.

Pellion Technologies Inc., an MIT spin-out company researching new magnesium-based energy storage systems has recently launched its website:

Pellion Technologies Inc.

The company is an early-stage company developing an innovative energy storage solution with the potential to deliver substantially lower cost and higher energy density than current lithium ion systems. Pellion, based in the Boston, MA area, is backed by top-tier venture capital and a recent award from the U.S. Department of Energy to develop next-generation batteries.

Jerry

AMSO4F: Fluorosulfates - New Active Materials for Advanced Battery Applications

Alkali metal fluorosulfate materials (AMSO4F, A = Li or Na; M = transition metal in oxidation state +2) are currently receiving significant attention as potentially valuable cathode active materials for advanced battery applications. The lithium-based materials all possess the triclinic, tavorite structure - so are isostructural with the lithium vanadium fluorophosphate phase, LiVPO4F.

Of particular note are the iron and manganese phases, LiFeSO4F and LiMnSO4F, which may represent important and new electroactive materials for Li-ion batteries. These materials offer a theoretical specific capacity of around 150 mAh/g (assuming the reversible cycling of 1 Li ion per formula unit). The Fe analog operates at around 3.5-3.6 V vs. Li - meaning that it generates a specific energy comparable with LiFePO4. When combined with its superior electronic conductivity, this performance suggests that LiFeSO4F could challenge the iron olivine, LiFePO4 as a low-cost active material for future large format Li-ion battery applications.

The challenges ahead will no doubt involve the development of a inexpensive and scalable synthesis method. Recent publications and presentations at the IMLB-2010 conference in Montreal suggest that the preparative approach adopted will be of critical importance in determining the electrochemical performance.

The use of these materials in energy storage applications is covered in the following US Patent application (US 2005/0163699 - Inventors: Jerry Barker and co-workers; Assignee: Valence Technology Inc.). The link to this patent application may be found here:

Fluorosulfate-based electrode active materials and methods of making the same

It should also be stressed that earlier US patent and US patent applications (involving the same inventors) also exist.

Jerry