Materials recovery from NMC batteries with water as the sole solvent.

We report an environmentally benign recycling approach for large-capacity nickel manganese cobalt (NMC) batteries through the electrochemical concentration of lithium on the anode and subsequent recovery with only water. Cycling of the NMC pouch cells indicated the potential for maximum lithium recovery at a 5C charging rate. The anodes extracted from discharged and disassembled cells were submerged in deionized water, resulting in lithium dissolution and graphite recovery from the copper foils. A maximum of 13 mg of lithium salts per 100 mg of the anode, copper current collector, and separator was obtained from NMC pouch cell cycled at a 4C charging rate. The lithium salts extracted from batteries cycled at low C-rates were richer in lithium carbonate, while the salts from batteries cycled at high C-rates were richer in lithium oxides and peroxides, as determined by X-Ray photoelectron spectroscopy. The present method can be successfully used to recover all the pouch cell components: lithium, graphite, copper, and aluminum current collectors, separator, and the cathode active material.

Packing bimodal magnetic particles to fabricate highly dense anisotropic rare earth bonded permanent magnets.

Highly dense and magnetically anisotropic rare earth bonded magnets have been fabricated via packing bimodal magnetic particles using a batch extrusion process followed by compression molding technology. The bimodal feedstock was a 96 wt% magnet powder mixture, with 40% being anisotropic Sm-Fe-N (3 µm) and 60% being anisotropic Nd-Fe-B (100 µm) as fine and coarse particles, respectively; these were blended with a 4 wt% polyphenylene sulfide (PPS) polymer binder to fabricate the bonded magnets. The hybrid bonded magnet with an 81 vol% magnet loading yielded a density of 6.15 g cm-3 and a maximum energy product (BH)m of 20.0 MGOe at 300 K. Scanning electron microscopy (SEM) indicated that the fine-sized Sm-Fe-N particles filled the gap between the large Nd-Fe-B particles. Rietveld analysis of the X-ray diffraction data showed that the relative contents of the Nd2Fe14B and Sm2Fe17N3 phases were 61% and 39%, respectively, in the hybrid bonded magnet. The PPS binder coated most of the magnetic particles homogeneously. Compared with the magnetic properties of the initial Nd-Fe-B and Sm-Fe-N powders, the reduction in the remanence, from the demagnetization curve, is ascribed to the dilution effect of the binder, the non-perfect alignment, and the internal magnetic stray field.

Solvent-driven fractional crystallization for atom-efficient separation of metal salts from permanent magnet leachates.

This work reports a dimethyl ether-driven fractional crystallization process for separating rare earth elements and transition metals. The process has been successfully applied in the treatment of rare earth element-bearing permanent magnet leachates as an atom-efficient, reagent-free separation method. Using ~5 bar pressure, the solvent was dissolved into the aqueous system to displace the contained metal salts as solid precipitates. Treatments at distinct temperatures ranging from 20-31 °C enable crystallization of either lanthanide-rich or transition metal-rich products, with single-stage solute recovery of up to 95.9% and a separation factor as high as 704. Separation factors increase with solution purity, suggesting feasibility for eco-friendly solution treatments in series and parallel to purify aqueous material streams. Staged treatments are demonstrated as capable of further improving the separation factor and purity of crystallized products. Upon completion of a crystallization, the solvent can be recovered with high efficiency at ambient pressure. This separation process involves low energy and reagent requirements and does not contribute to waste generation.

Electrochemical-driven green recovery of lithium, graphite and cathode from lithium-ion batteries using water.

The expected exponential increase in consumption of lithium-ion batteries (LIBs) would pose a unique challenge to the availability of near-critical resources like lithium and graphite in the upcoming decade. We present a lithium recovery process that utilizes a degradation mechanism, i.e., lithium plating, as a tool to concentrate metallic lithium at the anode/separator interface for convenient extraction at room temperature - using only water. Electrochemical characterization of fast charged (1-6 C) LIBs yielded a maximum capacity fade of 50% over ten cycles. The lithium plating was confirmed via voltage plateau analysis, coulombic efficiency, and DC resistance measurements. A maximum lithium plating condition was observed to exist between 4C and 5C, thereby limiting the energy consumption in the extraction process. Post-mortem film thickness measurement showed an incrementing film deposition with a maximum of 35 µm thickness. SEM and XPS analysis confirmed increasing concentration of a dense dendritic metallic lithium deposition on the anode/separator interface with C-rate. A green recovery process was adopted to extract the concentrated metallic lithium using distilled water. The lithium from the plated film, solid/electrolyte interface (SEI), electrolyte, anode, and cathode, was extracted as salts. A 37% improvement in lithium recoverability was achieved with fast charging under ambient conditions. XPS analysis showed ∼92% of lithium yield with no residual lithium in the graphite. In addition, the battery-grade graphite was recovered with 97% purity after heat treatment of the washed anode film, and concentrated transition metals oxides in the cathode to 93% purity for convenient extraction.

Magnetohydrodynamic Control of Interfacial Degradation in Lithium-Ion Batteries for Fast Charging Applications.

Interfacial anodic degradation in graphitic materials under fast charging conditions causes severe performance loss and safety hazard in lithium ion batteries. We present a novel method for minimizing the growth of these aging mechanism by application of an external magnetic field. Under magnetic field, paramagnetic lithium ions experience a magnetohydrodynamic force, which rotates the perpendicularly diffusing species and homogenizes the ionic transport. This phenomenon minimizes the overpotential hotspots at the anode/separator interface, consequently reducing SEI growth, lithium plating, and interfacial fracture. In situ electrochemical measurements indicate an improvement in capacity for lithium cobalt oxide/graphite pouch cell (20 mAh) charged from 1-5 C under an applied field of 1.8 kG, with a maximum capacity gain of 22% at 5C. Post-mortem FE-SEM and EDS mapping shows that samples charged with magnetic field have a reduced lithium deposition at 3C and a complete suppression of interfacial fracture at 5C. At 5C, a 24% reduction in the lithium content is observed by performing XPS on the anodic interfacial film. Finally, fast charging performance under variable magnetic field strengths indicate a saturation behavior in capacity at high fields (>2 kG), thereby limiting the field and consequent energy requirements to obtain maximum capacity gain under extreme conditions.

Rationally designed rare earth separation by selective oxalate solubilization.

A simple, environmentally benign, and efficient chemical separation of rare earth oxalates (CSEREOX) within two rare earth element (REE) subgroups has been developed. The protocol allows for selective solubilization of water-insoluble oxalates of rare earth elements, and results in efficient REE extraction even at low initial concentrations (<5%) from processed magnet wastes.

Additive Manufacturing of Isotropic NdFeB PPS Bonded Permanent Magnets.

Extrusion based additive manufacturing of polymer composite magnets can increase the solid loading volume fraction with greater mechanical force through the printing nozzle as compared to traditional injection molding process. About 63 vol% of isotropic NdFeB magnet powders were compounded with 37 vol% of polyphenylene sulfide and bonded permanent magnets were fabricated while using Big Area Additive Manufacturing without any degradation in magnetic properties. The polyphenylene sulfide bonded magnets have a tensile stress of 20 MPa, almost double than that of nylon bonded permanent magnets. Additively manufactured and surface-protective-resin coated bonded magnets meet the industrial stability criterion of up to 175 °C with a flux-loss of 2.35% over 1000 h. They also exhibit better corrosion resistance behavior when exposed to acidic (pH = 1.35) solution for 24 h and also annealed at 80 °C over 100 h (at 95% relative humidity) over without coated magnets. Thus, polyphenylene sulfide bonded, additively manufactured, protective resin coated bonded permanent magnets provide better thermal, mechanical, and magnetic properties.

Development of Mischmetal-Fe-Co-B Permanent Magnet Alloys via High-Throughput Methods.

Additive manufacturing synthesis using laser engineered net shaping (LENS) is utilized to rapidly print libraries of mischmetal (MM = La, Ce, Nd, and Pr) containing R2TM14B alloys (R = MM + separated Nd and TM = Fe and Co) enabling robust evaluation of physical properties over a wide composition range. High-throughput characterization of the magnetic and thermal properties are used to identify compositions for potential high-temperature, high-performance permanent magnets with reduced critical rare-earth elements. Improved Curie temperature (Tc ∼ 450 °C) is obtained with substitution of Fe by Co in pseudoternary R2TM14B alloys. Furthermore, a 4-fold decrease in the Nd content can be achieved through substitution with less critical Ce- and La-rich MM, while retaining high Tc. Guided by the properties of the LENS printed samples, selected compositions with and without TiC additions are synthesized via melt-spinning techniques to produce nanostructured ribbons. The maximum room temperature coercivity (Hc) and energy product ((BH)max) without TiC are found to be 5.8 kOe, 8.5 MGOe, respectively, while TiC additions as a grain refiner gave Hc and (BH)max of 4.9 kOe, 9.8 MGOe, respectively. Structural characterization of the melt-spun ribbons shows homogeneous grain refinement with TiC additions, which leads to an increase in the energy product.

Recycling of additively printed rare-earth bonded magnets.

In this work, we describe an efficient and environmentally benign method of recycling of additive printed Nd-Fe-B polymer bonded magnets. Rapid pulverization of bonded magnets into composite powder containing Nd-Fe-B particles and polymer binder was achieved by milling at cryogenic temperatures. The recycled bonded magnets fabricated by warm compaction of ground cryomilled coarse composite powders and nylon particles showed improved magnetic properties and density. Remanent magnetization and saturation magnetization increased by 4% and 6.5% respectively, due to enhanced density while coercivity and energy product were retained from the original additive printed bonded magnets. This study presents a facile method that enables the direct reuse of end-of-life bonded magnets for remaking new bonded magnets. In addition to magnetic properties, mechanical properties comparable to commercial products have been achieved. This research advances efforts to ensure sustainability in critical materials by forming close loop supply chain.