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

ARPA-E Program

Last month the U.S. Department of Energy announced it is awarding $106 million in federal funding through the Advanced Research Projects Agency – Energy (ARPA-E) for 37 ambitious research projects that could fundamentally change the way the US uses and produces energy. Within the Batteries for Electrical Energy Storage in Transportation (BEEST) sector there were some important awards.

The BEEST program seeks to create a portfolio of high-risk, high-reward R&D projects focused on developing ultra-high energy density, low cost battery technologies that is complimentary to the DOE Office of Vehicle Technologies’ (OVT) strong existing R&D portfolio in state-of-the-art Lithium-ion batteries. It is a high-risk, high reward strategy that will invest and support novel energy storage technologies.

More information on the objectives of BEEST may be found here:

The ARPA-E BEEST Program

Of particular interest to me are the awards given to Pellion Technologies Inc. and ReVolt Technology LLC.

Pellion Technologies is an MIT spin-out that will develop a low cost magnesium ion battery technology using high throughput computational methods in combination with accelerated material synthesis techniques.

ReVolt Technology will develop a novel large format Zn-air battery concept based on a closed loop system in which the zinc anode is suspended as a slurry within a storage tank.

Further information on these concepts and the other ARPA-E projects may be found here:

APRA-E - Recovery Act Funding

This blog will keep you posted on key developments within the ARPA-E program.

Jerry

New LiVPO4F Paper: Confirms Excellent Li-ion Performance

A recent publication by M.V. Reddy and co-workers (NSU, Singapore) has confirmed the outstanding lithium insertion behavior of the lithium vanadium fluorophosphate phase, LiVPO4F.

The abstract for this study may be found here:

Long-term cycling studies on 4V cathode, lithium vanadium fluorophosphate

In particular, the long term cycle life (1260 cycles) and associated low capacity fade behavior indicate the acceptability of the LiVPO4F material for next generation Li-ion batteries. When this electrochemical performance is considered in combination with its outstanding thermal stability (see entry below - ARC measurements on the charged, de-lithiated LiVPO4F material by Jeff Dahn's group) it suggests strongly that this material could replace current cathode technology to enable the commercial production of low cost, high energy density and safe Li -ion batteries for next generation applications (for example, EV and PHEV).

In addition, the rate perforamnce indicates that LiVPO4F may alos be a candidate cathode material for high rate Li applications.

Jerry

Surion Energy Limited

Surion Energy - a new company developing electrode materials for next generation Li-ion batteries - has recently launched its new website. A link to the Surion site may be found here:

Surion Energy Limited

Surion Energy is located at the Culham Science Centre, close to Oxford in the UK. The company is attempting to exploit its proprietary Li2FeS2 cathode technology to meet the growing demand for large format Li-ion batteries for electric vehicle applications.

Jerry

IMLB-2010

Jerry will be presenting at the up-coming 15th International Meeting on Lithium Batteries (IMLB-2010) to be held in Montreal, Canada during June 27 and July 2.

More information on this important conference may be found here:

15th International Meeting on Lithium Batteries (IMLB-2010)

Jerry

Li-ion Rechargeable Batteries: Novel Materials

The review article entitled 'Lithium-ion Rechargeable Batteries: Novel Materials' by Jerry Barker has now been published in the 'Encyclopedia of Materials: Science and Technology' (Elsevier, January 2010). The review gives an overview and summary of the present status of anode and cathode materials.

The abstract for the article may be found here:

Lithium-ion Rechargeable Batteries: Novel Materials

The encyclopedia contains several other articles in the energy storage sector that you may find useful.

Jerry

Li2FePO4F - A Fluorophosphate active material for Li-ion Applications

Following on from our previous discussions regarding the LiMPO4F (M = Fe, Mn, V, Cr etc.) and Li2MPO4F (M = Fe, Mn, Co, Ni etc.) active materials for Li-ion applications, a recent paper by Linda Nazar et al. describes the electrochemistry of the LiFePO4F- Li2FePO4F insertion system. The abstract to this manuscript may be found here:

Tavorite Lithium Iron Fluorophosphate Cathode Materials, ESL 13, A43, 2010

The use of these materials in Li-ion batteries is covered in several US patents and patent applications (inventors J. Barker and co-workers).

Jerry

LiV2O5 - An under-rated active material for Li-ion applications

Gamma-LiV2O5 may represent an inexpensive and safe cathode alternate to LiFePO4 for large format Li-ion applications. Preliminary analysis suggests that this active material should cost less than $20/kg to mass produce.

Further information may be found here:

Perfomance Evaluation of LiV2O5 - J. Barker et al. (2003)

In summary, the electrochemical evaluation of Gamma-LiV2O5 indicates that the active material is capable of cycling at a specific capacity of 130 mAh/g - a performance that compares favorably with the theoretical figure of 142 mAh/g. This material utilization corresponds to the reversible cycling of x = 0.92 in Gamma-LixV2O5 – a remarkably high charge efficiency. The average discharge voltage is around 3.4 V vs Li. High-resolution electrochemical evaluation indicates the lithium insertion reactions may be characterized in two separate but highly reversible processes.

The long-term electrochemical stability of the active material has been demonstrated clearly by lifetime cycling experiments in a graphite based Li-ion configuration. The cells show low first cycle charge inefficiency as well as demonstrating two hundred charge-discharge cycles with relatively low capacity fade behavior.

Jerry