2012 R&D 100 Award Winner

The Invention 

A unique method to control the composition gradient of materials in lithium-ion cathodes. The material particles created using this method are nickel-rich on the inside for a high capacity battery, and manganese-rich on the exterior surface for increased safety and stability. 

The process includes combining a first transition metal compound with a second transition metal compound to form a transition metal source solution, and combining that solution with a precipitating agent to form a precursor solution. The radius of precipitating particles consists of a transition metal oxide core and at least two layers of transition metal oxide. The particles have a transition metal concentration gradient in which the ratio of the first transition metal to the second transition metal is inversely proportional to the radius of the particle over at least a portion of the radius. The transition metal used in the first and second transition metal compounds include manganese, cobalt, nickel, chromium, vanadium, aluminum, zinc, sodium, titanium or iron. The first and second transition metal compounds can also include, but are not limited to, metal sulfates, nitrates, halides, acetates or citrates. 

Benefits 

• Creates a gradient of different materials for increased safety and stability; 
• Gradient runs throughout the entire radius of the particle; 
• Particles are ideally small, 10-20 microns in size; and 
• Leads to high-capacity batteries. 

Applications and Industries 

The particles can be used to create composite cathodes in 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 

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 

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 

An advanced gas phase deposition method to make silicon/carbon composite anodes that offer five times the specific energy of those currently used in lithium-ion batteries. The process embeds nanoscale silicon particles into the graphene layers, a key to longer cycle life and improved capacity. 

This approach overcomes the traditional problems associated with high energy density anodes, such as massive volume expansion, high first cycle inefficiency and severe capacity fade. 

Benefits 

• Anodes made with this process have five times the specific energy of those made with carbon. 
• When these new anodes are combined with high-energy composite cathodes, resulting batteries have more than double the energy density. 
• The new process allows seamless integration with polycrystalline silicon manufacturing. 
• The process allows low-cost silicon/carbon composite production. 

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 

Proof of Concept 

Lithium metal is an attractive anode material for rechargeable batteries in terms of its extremely high theoretical capacity (3860 mAh/g) and the lowest negative potential (-3.040 V, versus the standard hydrogen electrode). However, lithium dendrite formations during electrochemical cycling cause severe capacity fade and cell failure due to electrical shorting or electrolyte consumption. This tricky problem has prevented the incorporation of lithium anodes in commercial rechargeable cells due to potential safety issues and limited cycling life. 

This patent technology uses a protective coating that can greatly suppress the dendrite formation of lithium anodes and improve the lithium cycling stability. The protective coating is synthesized using a chemical vapor process that yields uniform and conformal films. The films are composed of a proprietary material that is mechanically robust to suppress lithium dendrites and has a high lithium ion conductivity and low electrical conductivity. The applications of rechargeable batteries with lithium anodes include portable devices and electric vehicles. 

Divisional patent application 16/741,434

A composite anode material with general formula (1-x)J-(x)Q wherein: J is a silicon-containing metal carbon alloy; and Q is a metal oxide.

Benefit

• High reversible capacity and improved cyclability with minimal volume change with cycling 

View the Patent Details

Anode materials for lithium ion batteries (US 9,054,373 B2)
Anode materials for lithium ion batteries (US 9,620,773 B2)

The Invention 

A series of novel redox shuttle additives for lithium ion batteries for the purpose of overcharge protection and increased battery safety. 

The additives not only can provide excellent overcharge protection in lithium-ion batteries but are also compatible with conventional carbonate-based electrolytes. These novel shuttle additives also provide improved solubility in carbonate based electrolyte. 

As the demand for hybrid and electric vehicles continues to grow, so does the demand for lithium-ion batteries that are safer, more powerful, and less expensive. These Argonne additives will help meet that demand. 

Benefits 

• Prevent overcharge and improves safety, 
• Balance cell in a battery pack, 
• Reduce cost, and 
• Increase battery reliability. 

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 

The various redox shuttle technologies are at several stages of development. 

Intellectual Property 

• ANL-IN-05-012, ​“Novel Redox Shuttles for Overcharge Protection of Lithium Ion Batteries”, U.S. Patent 7,851,092, GB issued patent 2,437,902; Inventors: Khalil Amine, Qingzheng Wang and Zonghai Chen 
• ANL-IN-08-024, ​“Electrolyte Salts for Lithium Batteries”, combined with ANL- IN-08-033, ​“Ionic Metal Complex Redox Shuttle for Lithium Ion Batteries”, U.S. Published Application 12/192,452; Inventors: Khalil Amine, Zhengcheng Zhang and Zonghai Chen 
• ANL-IN-09-082, ​“Polyether-Functionalized Redox Shuttles for Lithium Ion Batteries”, U.S. Published Application 13/114,452; Inventors: Zhengcheng Zhang, Lu Zhang and Khalil Amine 
• ANL-IN-09-084, ​“Redox Shuttle Additives for High Voltage Cathodes”, U.S. Published Application 13/114,468; Inventors: Lu Zhang, Zhengcheng Zhang, and Khalil Amine 
• ANL-IN-09-086, ​“Redox Shuttle for Overcharge Protection of Lithium Ion Batteries”, U.S. Published Application 13/113,499; Inventors: Wei Weng, Zhengcheng Zhang and Khalil Amine 
• ANL-IN-10-076, ​“Redox Shuttles for Overcharge Protection of Lithium Batteries”, U.S. Provisional Application 61,529,413; Inventors: Zhengcheng Zhang, Lu Zhang, and Khalil Amine 
• ANL-IN-11-128, ​“Redox Shuttle for Overcharge Protection of Lithium Ion Batteries,” U.S. Patent Pending 13/457,239; Inventors: Wei Weng, Zhengcheng Zhang and Khalil Amine