## Argonne Licenses New Lithium-Ion Cathode Technology to Toda Kogyo

##### 20 March 2008

The US Department of Energy’s (DOE) Argonne National Laboratory and Toda Kogyo Corp. (Toda) of Japan have reached a world-wide, non-exclusive licensing agreement for the commercial production and sales of Argonne’s patented composite lithiated nickel-manganese-cobalt (NMC) oxide cathode materials for lithium-ion batteries.

The family of structurally integrated composite cathode materials being licensed utilizes a new combination of lithium/manganese mixed metal oxides in a new materials-design approach that can deliver a much higher capacity than current cathode materials, while also providing structural and thermal stability. This leads, in practice, to extending the time between charges, increasing calendar life and improving lithium-ion cell safety in applications ranging from cell phones to hybrid-electric vehicles.

In some formulations, the Argonne NMC materials can provide an initial capacity of > 250 mAh g-1 when discharged between 5 and 2.0V and a rechargeable capacity of up to 250 mAh g-1 over the same window. By contrast, the practical capacity of conventional cobalt oxide electrodes is approximately 140 mAh g-1. Spinel LiMn2O4 and olivine LiFePO4, while more thermally and structurally stable than the cobalt oxides, deliver relatively low practical capacities above 3V in a lithium cell—typically 100-120 mAh g-1.

We believe the high-capacity NMC (lithiated nickel-manganese-cobalt oxide) technology we are commercializing are the materials of the future, that will solve many of the performance issues we see today in lithium-ion batteries.

—President of Toda Kogyo’s internal Energy Solutions Company

Our agreement with Toda Kogyo is an important step toward bringing to market key advanced lithium-ion battery technologies that are being developed here at Argonne with funding from the US Department of Energy. The technologies being licensed will enhance the performance, life and inherent safety of lithium-ion cells compared to those that employ the cobalt-based cathode technology that has dominated the market since the introduction of lithium-ion batteries in 1990.

—Gary Henriksen, Manager of the Electrochemical Energy Storage Department at Argonne

Argonne’s work on this particular family of materials, which stretches back five or six years, was led by Dr. Michael Thackeray.

Lithium-ion batteries operate by transporting lithium ions electrochemically between the two electrodes, with oxidation of the anode and reduction of the cathode during discharge, and the reverse during charge.

Approximately one-half of the lithium can be extracted from LiCoO2, without compromising the structural and chemical stability of the electrode; on this basis, LiCoO2 offers a practical electrode capacity of 130–140 mAh g-1. Substituted LiCo1-xNixO2 electrodes offer slightly higher capacities but also tend to suffer from structural and thermal instability when charged.

—“Advances in manganese-oxide ‘composite’ electrodes for lithium-ion batteries”

The battery industry has thus been in search of alternative cathode materials that allow lithium-ion cells to reach closer to their theoretical capacities, combined with safety and cycle life. One approach being taken to improve the electrochemical properties and structural stability of electrode materials is to use structural units, such as a layered structure or a spinel-type configuration.

Argonne started work on synthesizing structurally integrated layered-layered and layered-spinel compounds. The layered-layered (i.e., comprising two layered components) electrodes showed greater promise, and that led to further development and the licensing agreement with Toda Kogyo.

The new cathode materials—xLi2MnO3·(1-x)LiMO2 (M = Mn, Ni, Co)—are based on a composite matrix using an inherently stable inactive lithium-metal oxide that is integrated with a highly active form of another lithium-metal oxide component. This composite allows for greater levels of lithium to be utilized, while reducing oxygen-induced side reactions at the electrode surface that limit cell life and safety. The enhanced stability of these materials allows the system to be charged to higher voltages, leading to a significantly higher energy storage capacity than currently available materials through both the higher voltage and higher capacity per unit weight of active material.

In the work that we’ve done, the lithium-rich version of the material has some properties that differentiate it from the stoichiometric in terms of the characteristics of the material—it’s a better high-rate material and has enhanced stability because of the integrated structure where it has the electrochemically inactive component integrated with the active component. If we use certain combinations of materials, metal oxides, within the family, we can get stability up to higher voltages, and when we do that, we can increase the specific capacity to up to 250 mAh g-1.

The license to Toda includes materials of the type just described and processing technology. It also includes some of the work done to take the higher capacity material that operates at higher voltage, and make it more dense in terms of particle density, and to improve its rate capability.

One of our targets is to make this usable in PHEVs, so we can use the same size Li-ion system but give increased range capability.

—Gary Henriksen

This cathode technology is part of a large and diverse ongoing portfolio of lithium-ion battery research and development at Argonne that began in 1994 and spans a range from applied development to long-term fundamental materials research. Funded primarily by DOE’s Office of Vehicle Technologies, the scientists and engineers at Argonne have developed numerous technologies for improving the life, safety and performance of lithium-ion batteries, including several types of more stable advanced cathode and anode materials for higher power or higher energy storage applications and electrolyte systems that further stabilize the electrode/electrolyte interfaces.

I think there will be more licenses on this same technology, and those will probably happen fairly quickly. Some of the other people we’re talking to are interested in making a deal. We also have electrolyte additive technology which forms more stable passivation films on both positive and negative electrode. That technology is also being sought.

—Gary Henriksen

With more than 180 years of experience manufacturing and supplying high-performance materials in various markets, Toda Kogyo Corp. has established itself as a supplier of materials in the lithium-ion and nickel-metal hydride battery markets.

In addition to plants in Japan, Toda recently acquired a plant in the Detroit area that will help Toda serve US automobile manufacturers. Toda Advanced Materials Inc. in Sarnia, Ontario, Canada produces cathode materials and their precursors for lithium-ion and nickel-metal hydride batteries with a combined annual production capacity of 4,000 metric tons.

Resources

• Michael M. Thackeray, Christopher S. Johnson, John T. Vaughey, N. Li and Stephen A. Hackney, Advances in manganese-oxide ‘composite’ electrodes for lithium-ion batteries, J. Mater. Chem., 2005, 15, 2257 - 2267, DOI: 10.1039/b417616m

• Michael M. Thackeray, Sun-Ho Kang, Christopher S. Johnson, John T. Vaughey, Roy Benedek and S. A. Hackney, Li2MnO3-stabilized LiMO2 (M = Mn, Ni, Co) electrodes for lithium-ion batteries, J. Mater. Chem., 2007, 17, 3112 - 3125, DOI: 10.1039/b702425h

• Energy Storage Research and Development 2007 Annual Progress Report (Vehicle Technologies Program)

250mA/hg under 3.5 average volt leads to the outsanding specific power of 870 Whrs/Kg that is 3 time the best value reported for Li-ion battery. A 100Kg battery would store 87KWhrs, so at 0.2Kwh/Kms that is 430Kms.

If their claim happen to be true (and some seem convince of it) we will be fully electrified 20 years from now and nobody will ever put a dime in Hydrogen.

This seems to be legitimate. Argonne is a national lab after all. The coining of this deal should lead to deployment of their technology. Department of Energy should put more money into this line of research, particularly when their value has been validated by a commercial deal.

Only a fraction of theoretical energy density is normally achieved with the commercial product. Still optimistic that this has potential though....

Treehugger:

Yes, this would be a great leap forward in energy density.

There is no doubt that this will be improved in the near future. Within 5 to 10 years we will most likely see batteries with energy density approaching 1000 Wh/Kg.

Electrification of most of our ground transportation vehicles will certainly get a major boost with higher energy density batteries, if the price is right.

Another US lab trying to look green with disingenuous PR. The only reason they made this deal is because Bob Lutz told 'em to do it. More vaporware from the feds.

I'm glad Ronald Reagan didn't follow through on his campaign promise to disban the Dept. of Energy.

"campaign promise to disban the Dept. of Energy."

Not that anyone here nitpicks Mick, but "disban" would mean to lift a ban on DOE. I tend to think this is not your point.

250mA/hg under 3.5 average volt leads to the outsanding specific power of 870 Whrs/Kg that is 3 time the best value reported for Li-ion battery.

Treehugger, I believe 250mAh/g is for the cathode alone, not the entire battery. Still, it'd be a big deal to have a long-life, safe battery with higher energy density than plain vanilla Li-ion (LiCoO2). Today's long-life, safe batteries from A123 and so forth give away a lot in energy density.

The continued use of cobalt is a bit worrying, since it's currently rather expensive ($30/lb at the beginning of the year, rising to the$50/lb level soon after.) This is one strong motivation to look for alternate cathode chemistries using cheaper materials.

Ultimately cobalt can be obtained from seabed manganese nodules, but that's likely to be too expensive to depress the price very much.

dis·band /dɪsˈbænd/
–verb (used with object)
1. to break up or dissolve (an organization): They disbanded the corporation.
–verb (used without object)
2. to disperse.

All politicians have said rhetoric that is ridiculous. You probably did not know that the department of energy increased in size while Reagan was in office. Please do some research before making one line rhetoric the cornerstone of your message.

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