A multi-analytical methodology for the characterization of industrial samples of spent Ni-MH battery powders.

A multi-analytical methodology is implemented to characterize several sieving fractions of industrial samples of Black Mass (BM) powders originating from the thermo-mechanical treatment of cylindrical and prismatic-type spent nickel metal-hydride (Ni-MH) batteries. Elemental analyses of 17 elements (including C and O) indicate that the elemental composition of the powders (greater than93 %wt) does not depend on the battery type nor on the sieving fraction. XRD analyses evidence several phases (including Ni, NiO, CeO2 and C) but their quantification is not possible. Beyond these standard characterisations, magnetic susceptibility measurements demonstrate that the amount of metallic nickel versus nickel oxide increases with the sieving fraction, and that powders from prismatic-type batteries contain twice as much metallic nickel than cylindrical ones. Thanks to statistical analysis (based on clustering algorithms) of an electron probe µ-analysis (EPMA) compositional map, the complete methodology allows us to propose a full phase distribution for the BM particles. Three types of particles are identified and quantified. They originate from the partial oxidation of the battery components (anode active mass, anode current collector, cathode active mass and cathode current collector). The whole picture highlights the joint importance of battery ageing mechanisms, thermal deactivation and BM sieving steps on powder composition.

Leaching Mechanisms of Industrial Powders of Spent Nickel Metal Hydride Batteries in a Pilot-Scale Reactor.

In view of a sustainable recycling process, the leaching mechanisms of nickel and rare-earth elements (REEs) contained within industrial samples of spent nickel metal hydride battery powders were investigated in HCl and H2 SO4 , under mild temperature (25-60 °C) and pH (3-5.5). First, in-depth characterization of the heterogeneous battery powder was carried out with powder XRD, SEM, electron probe microanalyzer wavelength-dispersive spectroscopy (EPMA-WDS) quantitative analyses of individual particles, and inductively coupled plasma optical emission spectrometry (ICP-OES) elemental analysis. An unusual result is the identification of particles that exhibit a core-shell structure, which is related to anode active mass aging mechanisms. Then, a leaching study in a 10 L pilot-scale reactor demonstrated the selective dissolution of REEs, with respect to nickel, at pH 3, which is attributed to 1) the kinetic inhibition of nickel metal dissolution, and 2) the specific core-shell structure of aged mischmetal particles. Furthermore, the use of H2 SO4 led to coprecipitation of lanthanide-alkali double sulfates and nickel salts.