Low-cobalt, high-performance lithium-ion batteries achieved by rational design
SCIENCE CHINA PRESS
IMAGE:
SCHEMATIC ILLUSTRATION OF THE DYNAMICS AND STABILITY EVOLUTION MECHANISMS FOR LINI0.6CO0.2MN0.2O2 (NCM622) (A), LINI0.6MN0.4O2 (NM64) (B) AND CO-MODIFIED LINI0.6MN0.4O2 (CO-NM64) (C).
view moreCREDIT: ©SCIENCE CHINA PRESS
Researchers from Hunan University have designed a layered oxide cathode for rechargeable lithium-ion batteries that achieves fast-charging performance, long life, and high safety using only an ultra-low amount of cobalt. The study was published in the journal National Science Open.
In recent years, lithium-ion secondary batteries have played a crucial role in the rapid increase of electric vehicles worldwide. Typically, lithium-ion battery cathodes contain cobalt to ensure fast-charging capabilities. However, the surging demand for cobalt and its limited supply have significantly increased the cost of lithium-ion battery materials. The primary challenge has been to reduce cobalt usage while maintaining fast-charging performance.
To address this issue, the researchers synthesized a rational structure composed of a robust conductive protective layer, gradient Li+ ions conductive layer and stable bulk phase by optimizing the distribution of cobalt in high-nickel layered oxide cathode particles. Analysis showed that the robust conductive protective layer, gradient Li+ ions conductive layer significantly enhanced the ionic and electronic conductivity of the material. Consequently, this structure exhibited excellent rate performance (fast-charging) even with an ultra-low amount of cobalt. Additionally, the bulk phase with moderate cation mixing and the surface conductive protective layer effectively ensured material stability, achieving outstanding cycling stability and safety. In terms of battery performance, the designed cathode has doubled in rate performance (5 C) and retained 90.4% capacity after 300 cycles at high voltage in the full cell. These advantages suggest that the designed cathode has great potential for practical applications.
“Our study provides strong evidence that rational structural design can significantly reduce cobalt content while maintaining high rate performance and long life in batteries,” said Professor Lu of Hunan University, the study’s senior author. “This offers new insights for developing low-cost, high-performance lithium-ion battery materials.”
Furthermore, for cathode materials with good structural stability but poor kinetic performance, the study demonstrates that simultaneously designing surface crystal structure and bulk phase is an effective way to ensure excellent electrochemical performance at a lower cost.
This work was financially supported by the National Natural Science Foundation of China. For more details, please refer to the latest issue of National Science Open.
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See the article:
Surface Cobaltization for Boosted Kinetics and Excellent Stability of Nickel-rich Layered Cathodes
http://engine.scichina.com/doi/10.1360/nso/20240010
JOURNAL
National Science Open
A breakthrough in inexpensive, clean, fast-charging batteries
UChicago Prof. Shirley Meng’s Laboratory for Energy Storage and Conversion creates world’s first anode-free sodium solid-state battery
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A NEW FORM OF BATTERY FROM PROF. Y. SHIRLEY MENG’S LABORATORY FOR ENERGY STORAGE AND CONVERSION - A COLLABORATION BETWEEN THE UCHICAGO PRITZKER SCHOOL OF MOLECULAR ENGINEERING AND THE UNIVERSITY OF CALIFORNIA SAN DIEGO’S AIISO YUFENG LI FAMILY DEPARTMENT OF CHEMICAL AND NANO ENGINEERING - BRINGS INEXPENSIVE, FAST-CHARGING, HIGH-CAPACITY BATTERIES FOR ELECTRIC VEHICLES AND GRID STORAGE CLOSER THAN EVER.
view moreCREDIT: PHOTO BY UCHICAGO PRITZKER SCHOOL OF MOLECULAR ENGINEERING / JOHN ZICH
UChicago Pritzker Molecular Engineering Prof. Y. Shirley Meng’s Laboratory for Energy Storage and Conversion has created the world’s first anode-free sodium solid-state battery.
With this research, the LESC – a collaboration between the UChicago Pritzker School of Molecular Engineering and the University of California San Diego’s Aiiso Yufeng Li Family Department of Chemical and Nano Engineering – has brought the reality of inexpensive, fast-charging, high-capacity batteries for electric vehicles and grid storage closer than ever.
“Although there have been previous sodium, solid-state, and anode-free batteries, no one has been able to successfully combine these three ideas until now,” said UC San Diego PhD candidate Grayson Deysher, first author of a new paper outlining the team’s work.
The paper, published today in Nature Energy, demonstrates a new sodium battery architecture with stable cycling for several hundred cycles. By removing the anode and using inexpensive, abundant sodium instead of lithium, this new form of battery will be more affordable and environmentally friendly to produce. Through its innovative solid-state design, the battery also will be safe and powerful.
This work is both an advance in the science and a necessary step to fill the battery scaling gap needed to transition the world economy off of fossil fuels.
“To keep the United States running for one hour, we must produce one terawatt hour of energy,” Meng said. “To accomplish our mission of decarbonizing our economy, we need several hundred terawatt hours of batteries. We need more batteries, and we need them fast.”
Sustainability and sodium
The lithium commonly used for batteries isn’t that common. It makes up about 20 parts per million of the Earth’s crust, compared to sodium, which makes up 20,000 parts per million.
This scarcity, combined with the surge in demand for the lithium-ion batteries for laptops, phones and EVs, have sent prices skyrocketing, putting the needed batteries further out of reach.
Lithium deposits are also concentrated. The “Lithium Triangle” of Chile, Argentina and Bolivia holds more than 75% of the world’s lithium supply, with other deposits in Australia, North Carolina and Nevada. This benefits some nations over others in the decarbonization needed to fight climate change.
“Global action requires working together to access critically important materials,” Meng said.
Lithium extraction is also environmentally damaging, whether from the industrial acids used to break down mining ore or the more common brine extraction that pumps massive amounts of water to the surface to dry.
Sodium, common in ocean water and soda ash mining, is an inherently more environmentally friendly battery material. The LESC research has made it a powerful one as well.
Innovative architecture
To create a sodium battery with the energy density of a lithium battery, the team needed to invent a new sodium battery architecture.
Traditional batteries have an anode to store the ions while a battery is charging. While the battery is in use, the ions flow from the anode through an electrolyte to a current collector (cathode), powering devices and cars along the way.
Anode-free batteries remove the anode and store the ions on an electrochemical deposition of alkali metal directly on the current collector. This approach enables higher cell voltage, lower cell cost, and increased energy density, but brings its own challenges.
“In any anode-free battery there needs to be good contact between the electrolyte and the current collector,” Deysher said. “This is typically very easy when using a liquid electrolyte, as the liquid can flow everywhere and wet every surface. A solid electrolyte cannot do this.”
However, those liquid electrolytes create a buildup called solid electrolyte interphase while steadily consuming the active materials, reducing the battery’s usefulness over time.
A solid that flows
The team took a novel, innovative approach to this problem. Rather than using an electrolyte that surrounds the current collector, they created a current collector that surrounds the electrolyte.
They created their current collector out of aluminum powder, a solid that can flow like a liquid.
During battery assembly the powder was densified under high pressure to form a solid current collector while maintaining a liquid-like contact with the electrolyte, enabling the low-cost and high-efficiency cycling that can push this game-changing technology forward.
“Sodium solid-state batteries are usually seen as a far-off-in-the-future technology, but we hope that this paper can invigorate more push into the sodium area by demonstrating that it can indeed work well, even better than the lithium version in some cases,” Deysher said.
The ultimate goal? Meng envisions an energy future with a variety of clean, inexpensive battery options that store renewable energy, scaled to fit society’s needs.
Meng and Deysher have filed a patent application for their work through UC San Diego’s Office of Innovation and Commercialization.
Citation: “Design principles for enabling an anode-free sodium all-solid-state battery,” Deysher et al, Nature Energy, July 3, 2024. DOI: 10.1038/s41560-024-01569-9
Funding: Funding to support this work was provided by the National Science Foundation through the Partnerships for Innovation (PFI) grant no. 2044465
Anode-free schematics and energy density calculations
a) Cell schematic for carbon anodes, alloy anodes, and an anode-free configuration. b) Theoretical energy density comparison for various sodium anode materials. c) Schematic illustrating the requirements for enabling an anode-free all-solid-state battery.
CREDIT
Laboratory for Energy Storage and Conversion
Nature Energy
ARTICLE TITLE
Design principles for enabling an anode-free sodium all-solid-state battery
ARTICLE PUBLICATION DATE
3-Jul-2024
COI STATEMENT
A patent application for this work has been filed by G.D. and Y.S.M. through UC San Diego’s Office of Innovation and Commercialization.
Eco-friendly solution for battery waste: new study unveils novel metal extraction technique
SOCIETY OF CHEMICAL INDUSTRY
A new study led by researchers in Canada introduces a novel process for the extraction and separation of metals from spent alkaline batteries, offering a promising solution for efficient recycling of critical materials.
As global energy demands continue to rise, the role of batteries is becoming increasingly critical. However, the improper disposal of spent batteries poses significant environmental hazards due to their metal content. Recycling these metals not only mitigates environmental risks but also provides a sustainable source of valuable materials.
The paper, published in the Journal of Chemical Technology and Biotechnology, presents a technique for the extraction of potassium, zinc and manganese that is cheaper and more energy efficient than other existing methods.
Noelia Muñoz García, a Researcher at the Université de Sherbrooke in Canada, and lead author of the study, explained the significance of the research. ‘We focused on the extraction of the main minerals present in alkaline batteries because they represent more than 70% of the volume of spent batteries in North America. This research supports the principles of the circular economy, where materials are reused and recycled, creating a closed-loop system. This reduces waste and can lead to long-term economic sustainability by maximising the utility of resources, which is one of the main objectives in current treaties such as the Paris Agreement.’
Importantly, efficient recycling of battery materials is critical to mitigating harmful environmental impacts. ‘The main problem of improper disposal of spent alkaline batteries is that compounds of potassium, zinc and manganese can leach into the soil and pollute groundwater, posing threats to the environment and human health, such as ecotoxicity and abiotic depletion,’ noted García.
The technique hinges on a process called hydrometallurgy, which uses aqueous solutions to extract the metals – known as ‘leaching’. Hydrometallurgy can be carried out at room temperature, making it more energy-efficient than methods that require high temperatures.
The novelty of the process developed in this study lies in the use of three separate steps for the extraction of the metals. In other hydrometallurgical processes, all metals can be extracted in one leaching step producing a complex leachate composition that is costly to separate out into its components.
By removing the metals in three phases using different leaching agents, the researchers were able to produce higher quality leachates, lowering the costs of downstream purification. Overall, the process resulted in a total extraction efficiency of 99.6% for zinc and 86.1% for manganese. Antonio Avalos Ramirez, a Researcher at the Université de Sherbrooke in Canada and corresponding author of the study commented on these high extraction efficiencies. ‘The most important factor was to find a suitable leaching agent (in this case sulfuric acid) and a reducing agent (hydrogen peroxide), which increased the extraction of these minerals.’
The researchers are now looking ahead to scaling up their extraction technique. Ramirez noted, ‘the next steps will be to develop separation and purification units for obtaining zinc and manganese at a quality good enough to introduce them to the market and use them in the production of new goods. Further research is needed to address the scalability of the process at an industrial/commercial scale.’
JOURNAL
Journal of Chemical Technology and Biotechnology
ARTICLE TITLE
Extraction and separation of potassium, zinc and manganese issued from spent alkaline batteries by a three-unit hydrometallurgical process
KIER develops 'viologen redox flow battery'
to replace vanadium’
Large-capacity ESS redox flow battery without fire risk... 'viologen' active material applied to replace expensive vanadium. Like fitting assembly blocks, inserting functional groups into viologen molecules to enhance stability and solubility
NATIONAL RESEARCH COUNCIL OF SCIENCE & TECHNOLOGY
A RESEARCHER IS ASSEMBLING AN ORGANIC MATERIAL-BASED FLOW BATTERY
A technology has been developed to replace the active material in large-capacity ESS 'redox flow batteries' with a more affordable substance.
*Redox Flow Battery: A term synthesized from Reduction, Oxidation, and Flow. It is a battery that stores electrical energy as chemical energy through oxidation and reduction reactions of active materials in the electrolyte at the electrode surface and converts it back to electrical energy when needed. It is capable of large-scale storage, can be used long-term through periodic replacement of the electrolyte, and its major advantage is the absence of fire risk.
Dr. Seunghae Hwang’s research team from the Energy Storage Research Department at the Korea Institute of Energy Research has successfully enhanced the performance and cycle life of redox flow batteries, a prominent large-capacity energy storage device, by introducing functional groups* that replace the active materials and improve solubility and stability.
*Functional group: A group of atoms within an organic compound that determines the properties of the compound and plays a role in defining its characteristics.
To expand the use of renewable energies such as solar and wind power, a long-term energy storage system is needed that can store electricity generated during favorable weather conditions for more than 8 hours and reuse it when necessary. Among these, redox flow batteries, which have a lower fire risk and a long cycle life of over 20 years compared to commonly used lithium-ion batteries, are being actively researched globally. The Republic of Korea is also focusing on developing* low-cost, high-efficiency technologies for widespread adoption around 2030.
*Energy Storage Industry Development Strategy (October 2023), Ministry of Trade, Industry and Energy
Although vanadium is currently commercialized as the active material in redox flow batteries, its limited reserves have spurred recent research into alternatives. Organic compounds such as viologens, made from naturally occurring elements like carbon and oxygen, are particularly notable for their affordability and potential to replace vanadium. However, viologens have the disadvantage of low solubility, which reduces the overall energy density, and their instability when they repeat charging and discharging, necessitating the development of technologies to overcome these issues.
To address these issues, researchers have introduced functional groups into viologens. These functional groups fit into the viologens like assembly blocks, enhancing their solubility and stability.
To increase the solubility of viologens, researchers introduced sulfonate and ester functional groups, which have water-friendly properties. These two functional groups generate attractive forces between molecules through interactions with water (electrolyte) molecules on the surface of the viologens, facilitating the dispersion of viologens in water.
Viologens are structured like a sandwich, consisting of two molecular layers. During charging, these layers frequently combine, changing into a structure that can no longer store energy. To address this, researchers introduced alpha-methyl functional groups that act as obstacles. These functional groups introduce a twist into the layered structure and generate repulsion between molecules, suppressing side-reactions and thereby enhancing the efficiency and stability of energy storage.
As a result of applying the active material developed by the researchers to redox flow batteries, it was confirmed that the energy density improved by more than twice compared to vanadium redox flow batteries. Additionally, after 200 cycles of charging and discharging, the batteries demonstrated 99.4% coulombic efficiency (discharge capacity relative to charge capacity) and 92.4% capacity retention, indicating enhanced performance and stability.
Dr. Seunghae Hwang, the first author of the paper containing the research results, stated, 'In response to climate change and to expand the use of renewable energy, it is necessary to facilitate energy storage through the development of redox flow batteries that have both price competitiveness and long cycle life.' She added, 'This research enables the design of active materials that achieve both affordability and longevity, contributing to the early commercialization of redox flow batteries.
The research results were published in the prestigious materials science journal 'ACS Applied Materials and Interfaces (IF 9.5)', and the study was conducted with the support from the KIER.
A researcher is assembling an organic material-based flow battery-2
The researchers are holding the organic active material they developed.
JOURNAL
ACS Applied Materials & Interfaces
DOI
10.1021/acsami.4c04528
ARTICLE TITLE
Integration of Functional Groups to Enhance the Solubility and Stability of Viologen in Aqueous Organic Redox Flow Batteries
