Lithium-ion recycling is challenged by cost and safety related to reactivity of lithium and electrolytes. OnTo’s deactivation eliminates flammability and residual reactivity enabling a roadmap for safe, low-cost end-of-life battery services essential to the industry. Deactivation coupled with Cathode-healing provides safety and efficiency in material recycling that can be applied all along the manufacturing value chain. Dr. Sloop will present recent developments in application and scale of these innovative technologies.

The objective of this project was based upon the FOA request to demonstrate replication of results of the innovation to different locations. The project demonstrated battery deactivation innovations on different battery formats, chemistries, and within various industrial settings. The successful deactivation process was demonstrated on mainstream applications as well as safety-outliers, such as batteries that may have a residual charge. Success of deactivation was shown through repeated observations that various treated batteries do not exhibit thermal runaway with exposure to excessive heating or nail penetration. Deactivation processing was successfully demonstrated on batteries from private industry, public transit authorities, and military formats accessed with support of the Defense Logistics Agency (DLA). Third party analysis of deactivated batteries is ongoing through use of voucher programs available through OnTo’s Made in America Phase II Battery Recycling Prize, and OnTo’s CalTestBed award; these activities support the future special permit or declassification of deactivation treated material that has a firm foundation in results from this project. The project demonstrated the potential for a service business to perform the activities of electrolyte removal and reactivity elimination from large electric vehicle batteries in a relevant environment such as a battery testing and repackaging, or public-transit electric bus service shop. This successful project provided the first description, demonstration, and basis to teach quality control and assurance of successful battery deactivation.

(1) Executive Summary: End of life batteries (EOLBs) present a cost and safety liability for their owners and stakeholders. This is due flammability, energy, and power with EOLBs. Current approaches include cumbersome, expensive packaging, specialized shipping, regulated storage, and they are responsible for over half of the cost of recycling. They all expensively and inadequately address symptoms. OnTo has developed and proven a simple way to resolve the problem systemically, through depowering of lithium-ion batteries (and most any battery other than lead). The low-cost process removes flammability, power, and energy in EOLBs through non-toxic chemical processing. The opportunity for commerce of inert scrap is at least $5 billion greater than the commerce in hazardous scrap, all made possible through OnTo’s technology for efficiency and safety. (2) Depowering Improves Safety and Decreases Cost of Battery Ownership: OnTo’s depowering technology will remove half of the cost of EOLB management and recycling. Without this technology, EOLB recycling will always be a liability. EOLB is hazardous due to inherent flammability of electrolyte and lithium. The shipping and commerce of EOLBs is costly and dangerous all along the chain of custody from owner, dealership/shop, shipper, second-life sorter, (shipper again), and finally to the destination facility recycler. OnTo’s depowering service renders inert most any EOLB packs, modules, and cells. The technology uses a brief, non-toxic treatment applicable to most any chemistry. The industry needs a safe, simple, modular, and inexpensive method to render EOLBs as inert scrap. OnTo’s deactivation system is scalable to the needs of any customer along the EOLB chain of custody. (3) Evidence of Successful Depowering: Untreated batteries will catch fire and explode under abuse conditions such as heat or crush. Slide 2 below shows that untreated batteries will blow-up and expel their internal components with heating, after OnTo’s depowering treatment, the same battery is inert with the same heat treatment (Fig. 7 in the slide). Depowering also removes electrolyte reactivity, eliminating the production of HF and other toxins (Fig 6. in the slide) The depowering process is applicable to large, 26 Ah cells. Fig. 5 in the slide shows the removal of all the electrolyte from whole cells. Removal of flammable material from an EOLB contributes to the inert behavior. OnTo developed this technology through a project supported by the US Department of Energy EERE program, with partners including Seattle King County Metro Transit. While OnTo has generated evidence of successful depowering of batteries, in 2020, a follow-on voucher opportunity for third party analysis of depowered cells and materials was approved through CalTestBed. The expertise of the battery and materials research groups at Lawrence Berkeley National Laboratory will characterize these depowered cells to provide better understanding of the materials level changes in depowering. (4) Pilot Plant for Depowering EOLBs: Making the spoke work in hub-and-spoke While other companies are marketing the hub-and-spoke approach for recycling EOLBs, they rely on dangerous, expensive shredding methods with flimsy IP protection. OnTo offers the only patented, proven ability to depower EOLBs from most any chemistry – at half of the capital cost required for shredding, while eliminating the liability, danger, and waste streams inherent with shredding. The proposed commercial pilot facility is (5) OnTo Technology LLC Company: OnTo develops advanced battery recycling innovations that produce manufacturing quality electrode materials from recycled batteries. Their patented Cathode-healing™ and Deactivation/Depowering processes improve safety and reduce the cost of recycling. OnTo’s breakthrough technologies produce advanced materials for manufacturing batteries useful in applications from portable power to electric vehicles. Contact: Steve Sloop OnTo Technology LLC, 63221 Service Road, STE F, Bend, OR 97703, ssloop@onto-technology.com , 541-389-7897

This presentation will address three parts: (1) Elimination of hazards to make batteries safe for transport, which addresses half of the end-of-life liability (2) Reclamation of candidate materials with cathode-healingTM for less than $10/kg, and reclamation of the remaining materials to (3) make clean-precursors with a value opportunity of $2-10/kg. For such a developed industry, the realities of a wholistic approach for sustainable (economic and otherwise) lithium-ion battery manufacturing are largely untapped. These approaches offer unique, scalable, patented methods to address it.

Nickel rich electrodes are of interest for use in next generation electric vehicle applications. Both new-scrap from original manufacturing and old-scrap from end of life batteries may require fees for processing because such "cobalt-lite" formulations have a low value of recoverable elements. For these materials, direct recycling technologies for recovery of electrode particles are not constrained by cobalt content. Coating of cathodes with molecular barriers is a strategy to improve the safety and life for of these electrodes. Coated cathodes can be adopted not only to improve 'first-life' cell performance, but also, when coupled with direct recycling technologies, facilitate the `next-life' of low cost lithium-ion cathodes from scrap material. This paper demonstrates direct recycling of bare NMC 622 from used cells, and direct recycling of a similar, coated material.

This paper describes performance capabilities of refurbished LiNixMnyCozO2 lithium-ion chemistries with x:y:z from 1:1:1 to 6:2:2. The process to refurbish these electrodes from spent batteries is known as “Direct Recycling”. The vertical integration of advanced battery recycling into battery manufacturing will significantly reduce material costs and address long term economic sustainability for the battery industry. Figure 1

LiCoO2 is the positive electrode in 75% of the market. In response to cost pressure, electrodes that dilute or eliminate expensive cobalt have been developed such as LiCoNiMnO2, LiMn2O2 or LiFePO4. The new chemistries expand lithium-ion battery use into high-power niches such as tools and prototype electric vehicles (EVs) [1].

Rechargeable batteries used in consumer and hybrid electric vehicle applications rely on lithium-ion and nickel–metal hydride chemistries (so-called ‘advanced batteries’). In its current state, the advanced battery industry does not typically manufacture batteries utilizing recycled material. Pyrometallurgy and hydrometallurgy are the basis of today’s technology for end-of-life battery decommissioning and materials reclamation; these processes essentially burn, melt, or dissolve advanced materials to recover metals for high-strength alloys, and other cobalt market segments. Diversification of the battery chemistry market may decrease the recoverable value of metals in recycling processes utilized today. Soft-chemical- or green-chemical-based processing is available, which allows for recovery of advanced materials useful in the manufacture of battery materials. The establishment of recycled material specifications is identified as a way to improve the use of recycled material by the advanced battery manufacturing market.

Lead manufactured in North America utilizes 88% recycled metal, which is the highest of all industrial base metals. The technology used for modern lead–acid battery recycling is designed to meet the economic and environmental needs of an industrialized economy; the main processes use thermal methods with a reducing agent to produce lead from spent batteries. Electrochemical methods have been explored to replace thermal methods, including electrowinning lead from a number of solutions of lead derived from acidic media and a reducing agent. Similar electrochemical methods may work in parallel with pyrometallurgical processing as fly ash treatment methods or for eventual environmental remediation procedures.

This abstract introduces results from OnTo Technology's innovative recycling process to produce new materials for new batteries from materials from spent batteries. Recycling spent batteries is a growing problem for the consumer electronics electric vehicle industries.

Poly[oxymethylene-oligo(oxyethylene)] (PEM) cross-linked by UV radiation will solvate LiClO4 and demonstrates ionic conductivities similar to those with linear PEM, as well as improved dimensional stability. The PEM24LiClO4Li interface has an impedance of 1000 Ω cm2; and demonstrates behavior consistent with the formation of a solid electrolyte interface (SEI). Cross-linked films of PEM do not form a stable interface with lithium; however, upon treatment with methyl iodide Ri, stabilizes at 2000 Ω cm2.

The formation and stabilities of interfaces between poly[oxymethylene oligo-(oxyethylene)] (PEM)-salt polymer electrolytes and lithium metal or LiCx are investigated. The Li/PEM(25)LiClO(4) interface (where x in PEM(x)LiAn indicates the mole ratio of O/Li in the electrolyte) demonstrates behavior consistent with the formation of a solid electrolyte interface: with a stable interfacial resistance of 900 Omega cm(2) at 50 degrees C. UV-cross-linked films do not form a stable interface, R(int) rapidly increases to greater than 10(5) Omega cm(2). When cross-linked samples are treated with methyl iodide, hexamethyldisilazane/trimethylchlorosilane or upon addition of the plasticizer polyethylene glycol dimethyl ether, R(int) at 50 degrees C stabilizes at approximately 2000 Omega cm(2). The polymer electrolytes require a plasticizer to form a low impedance interface with LIC(x).

approved: Michael M. Lerner A general introduction, and review of materials investigated for use in solid state batteries is provided in chapters 1 and 2. These include descriptions of cathode, anode and electrolyte materials, fundamental properties of polymer electrolytes (PEs), and electrode / electrolyte interfaces, as well as an outline of the mechanical, and electrochemical requirements of polymer electrolytes. Chapter 3 describes the experimental techniques utilized in these investigations. Chapter 4 reports the results of an investigation into crosslinking poly(ethylene oxide) and poly[oxymethylene-oligo(oxyethylene)] with ultraviolet radiation. The ionic conductivity of the UV crosslinked PE is shown to be similar to PEs derived from the linear electrolytes. Polymer rheology demonstrates an increase in dynamic modulus with the exposure of PEO or PEM to 254nm radiation. The crosslink density decreases with depth into these disks, and a relatively high concentration of hydroxyl resides on the surface of the crosslinked polymers. A GCMS investigation of the degradation products of crosslinked PEO in HBr/Acetic acid reveals a possible reaction mechanism for crosslink formation, which is proposed. Chapter 5 investigates Li/PE interfacial characteristics of PEs derived from UV crosslinked PEO, and PEM. Redacted for Privacy Cross linked films develop interfacial resistance in the mega-S2 cm2 range, upon addition of polyethylene glycol dimethyl ether (PEGDME), or treatment with a methylating, or silylating agent, these PEs maintain interfacial. resistances (350 1000 Qcm2) similar to their linear PEs. In Chapter 6, PE/electrode interfaces of cathodesderived from LiAPEOYMoO3 have resistances near 250 S2 cm2, while those derived from Li0 25MoO3 have resistances near 20,000 ü cm2 at 60° C, and suggest that incorporation of PEO within layered cathode materials lowers the PE interfacial resistance. Chapter 7 describes the incorporation of polyethylene imine (PEI) into HTINbO5 and HxTi2_,,,40,404120. The products of aqueous reactions show maximum layer expansions of -28 A in both solids. The HTINbO5 PEI reaction progresses through phases with layer expansions of 4, 10, 14 and 28 A, the reaction rate is influenced by the pH of the solution, and slows progressively below pH-10. Synthesis and Characterization of Polymer Electrolytes and Related Nanocomposites by Steven E. Sloop A THESIS submitted to Oregon State University in partial fulfillment of the requirements for the degree of Doctor of Philosophy Completed May 2, 1996 Commencement June 1996 Doctor of Philosophy thesis of Steven E. Sloop presented on May 2, 1996