Technology Overview

Argonne’s has developed a suite of surface structures, treatments and coatings for a range of high-voltage lithium metal oxide electrodes, including advanced nickel- manganese- and lithium-rich cathode materials. 
See Low-Cobalt, Manganese-Rich Cathodes for Lithium-ion Batteries for Argonne’s complementary portfolio of Li- and Mn-rich cathode structure technologies.

Benefits 

• Surface-stabilizing structure, treatment and coating technologies offer customizable approaches for a range of high-voltage lithium metal oxides electrode materials.
• Enhance the surface stability, rate capability and cycling stability of electrodes, which leads to increased electrode energy capacity.
• Specifically address surface-related stability for enabling the use of next generation Mn- and Li-rich cathode structure types in lithium-ion batteries.

Applications and Industries

Electrodes used in batteries for: 

• Electric and plug-in hybrid electric vehicles, 
• Stationary energy storage systems,
• Portable electronic devices, 
• Medical devices, and 
• Space, aeronautical, and defense-related devices. 

Developmental Stage

Ready for commercialization.

Technology Overview 

Argonne’s family of manganese and lithium rich materials includes a range of cathode structures, including layered-type structures, spinel-type structures, rocksalt-type structures, and combinations thereof. For example, ​“layered-layered-spinel” materials with high-rate and stable voltage that are composed of lithium manganese nickel oxides have been discovered and can be used to replace high-energy multi- component ​“layered-layered” type or single-phase high-rate spinel-type structures for lithium cells and batteries. 
See Surface structures, treatments and coatings for high-voltage lithium metal oxide electrodes for complementary surface treatment and coating technologies. 

Benefits 

• These new material compositions provide substantially higher capacities than state-of-the-art layered lithium/cobalt/nickel/oxide materials, such as nickel-manganese-cobalt (NMC).
• Due to the spinel component, these cathodes are endowed with high power where they can be charged and discharged rapidly. 
• The multi-component nature of these materials can be optimized in the phase space in the figure according to the manufacturer’s needs. 
• Manganese is less expensive to use and more chemically benign than cobalt or nickel. Either low-cost elements and/or other elements may be doped into the structure to provide better performance, at a lower cost, as needed.

Applications and Industries 

Electrodes used in batteries for: 

• Electric and plug-in hybrid electric vehicles,
• Stationary energy storage systems,
• Portable electronic devices, 
• Medical devices, and 
• Space, aeronautical, and defense-related devices. 

Developmental Stage 

Ready for commercialization. 

The Invention 

High-capacity, rechargeable cathodes made of stable di-lithium layered compounds (Li₂MO₂) (M=Li, Ni, Mn) for use in Li batteries. The electrode capacities exceed 500 mAhg-1 when two lithium cations are cycled, giving this material very high energy. Li₂MO₂ is a good chemical precursor to fabricate cathodes with new composite layered LiMO₂ or LiM₂O₄ spinel structures that possess excellent cycling reversibility. Li₂MO₂ can also be used as a reversible anode when cycled below 1.5 V.

Benefits 

• Li₂MO₂, as a layered precursor chemical, can be used to create LiMO₂ composite cathodes with high-capacity and high energy which are superior to state-of-the-art layered lithium/cobalt/nickel/oxide cathodes. 
• Layered Li₂MO₂ cathodes possess capacities of 500 mAhg-1 which are much higher than current Li-ion batteries. Because of this, the voltage of the electrochemical reactions can be raised to produce batteries with high energy densities. 
• Manganese, nickel and lithium are used in the compounds, avoiding the use of cobalt, which is expensive and toxic. 
• Low-cost synthesis of Li₂MO₂ by chemical or electrochemical lithiation is a new approach to make cathodes that last longer with low energy losses. 

Applications and Industries 

Electrodes used in batteries for 

• Electric and plug-in hybrid electric vehicles; 
• Portable electronic devices; 
• Medical devices; and 
• Space, aeronautical, and defense-related devices. 

The Invention 

This invention relates to positive electrode materials (cathodes) for electrochemical cells and batteries. It relates, in particular, to electrode precursor materials comprising manganese ions, such as Li2MnO3, and to methods for fabricating lithium-metal-oxide electrode materials and structures using the precursor materials, notably for lithium cells and batteries. More specifically, the invention relates to improved or novel lithium-metal-oxide electrode materials with layered-type structures, spinel-type structures, rocksalt-type structures, combinations thereof and modifications thereof, notably those with imperfections, such as stacking faults and dislocations. The invention extends to include lithium-metal-oxide electrode materials with modified surfaces to protect the electrode materials from highly oxidizing potentials in the cells and from other undesirable effects, such as electrolyte oxidation, oxygen loss and/or dissolution. 

Applications 

Electrodes used in lithium batteries for 

• Electric and plug-in hybrid electric vehicles; 
• Portable electronic devices; 
• Medical devices; and 
• Space, aeronautical, and defense-related devices.

Developmental Stage 

Reduced to practice 

The Invention 

New high-energy cathode materials for use in rechargeable Li-ion cells and batteries synthesized using a novel alternative approach. These Li-ion cathode materials consist of layered transition metal containing oxides that have a unique bi-layered domain structure produced by the synthesis method. This new material allows for rapid Li intercalation/de-intercalation within the crystal, resulting in a cathode with very high rate and high-power capability. Argonne’s invention provides for new, Mn-rich compositions in these cathodes and their associated synthetic route. This layered cathode material containing low-cost Mn operates at high-rate and high-voltage, resulting in high-energy-density batteries with improved stability. These cathodes therefore offer improvements in all aspects of battery performance. 

Since the performance of Li-ion batteries is largely predicated on the cathode performance in the cell, improvements to lower the irreversibility capacity loss on the first cycle, increase the rate capability, and improve structural stability at high voltages in the cathode are needed. The objective is to synthesize and make new materials to address these issues. High-energy density Li-ion batteries available in the market today have low power and progressively lose their energy due to voltage fade during cycling. This new cathode material from new synthesis methods solves problems that are associated with conventional Li-ion high-capacity (energy) batteries. 

Benefits 

• Higher-performance, more cost-effective batteries for PHEVs and HEVs. 
• Reduced costs by lowering the number of cells needed in the battery pack and their associated hardware 
• Argonne’s preparation process is simple for this new class of high-energy materials and involves only two steps so that the manufacturing cost is easier, faster, and more cost-effective. 

Applications and Industries 

• Electrodes used in batteries for 
• Electric and plug-in hybrid electric vehicles; 
• Portable electronic devices; 
• Medical devices; and 
• Space, aeronautical, and defense-related devices. 

Developmental Stage

Baseline materials are patented and have been implemented in full cells.

The Invention 

Electrodes having composite xLi₂M’O₃·(1-x)LiMO₂ structures in which an electrochemically inactive Li₂M’O₃ component is integrated with an electrochemically active LiMO₂ component to provide improved structural and electrochemical stability. The preferred M’ ions are manganese, titanium and zirconium, whereas the preferred M ions are manganese and nickel, which can be used in combination with other metals such as cobalt. For example, the composite electrode ^0.10Li₂MnO₃·0.90LiMn_0.26Ni_0.37Co_0.37O₂, which can also be represented in conventional layered notation as Li[Li_0.0475Mn_0.3175Ni_0.3175Co_0.3175]O₂, shows outstanding electrochemical properties. The structural compatibility between the two components, both of which have layered configurations (Fig. 1), allows integration to occur at the atomic level. 

During charge and discharge of a lithium-ion cell, Li+ ions are electrochemically removed from and reinserted into the LiMO₂ component, respectively, as shown schematically in a compositional phase diagram of a Li₂M’O₃ - LiMO₂ - MO₂ - Li₂MO₂ electrode system (Fig. 2). An additional advantage of using electrode structures with manganese and nickel ions in the LiMO₂ component is that these structures can accommodate additional lithium; they form layered Li₂MO₂ structures without compromising the reversibility of the reaction, thereby providing additional capacity to the electrode. The Li₂M’O₃ component not only provides structural stability but also ensures, with its high lithium content, that the lithium layers in the composite electrodes are not contaminated by small amounts of transition metal ions, such as Ni₂₊ ions. 

Benefits 

• Superior cost and safety features over state-of-the-art LiCoO₂ electrodes 
• Can be charged and discharged at high rates 

Applications and Industries 

Electrodes used in batteries for 

• Electric and plug-in hybrid electric vehicles; 
• Portable electronic devices; 
• Medical devices; and 
• Space, aeronautical, and defense-related devices. 

Developmental Stage 

Ready for commercialization 

The new materials have potential application in lithium-ion batteries with anodes such as graphite, graphene, and silicon. There is also potential application in batteries utilizing lithium metal anodes.

In this invention, cathode precursors that contain a large amount of lithium can be extracted electrochemically at high potentials to load metal or metal alloy substrates with lithium. In one example, lithium and oxygen ions are released from the cathode during an initial preconditioning charge of the cell. This process leaves a structurally modified compound in the charged cathode that can react with lithium on a subsequent discharge. In principle, the preconditioning step (i.e., the initial charge reaction) is largely irreversible, whereas the second step (the initial charge reaction) can be either reversible or irreversible. This technology is available for license.

Applications

High capacity electrodes used in lithium batteries for:

• Electric and plug-in hybrid electric vehicles;
• Stationary energy storage devices;
• Portable electronic devices;
• Medical devices; and
• Space, aeronautical, and defense-related devices.