A Closed Loop Recycling Process for the End-of-Life Electric Vehicle Li-ion Batteries Public

Downloadable Content

Download PDF

Lithium-ion batteries (LIBs) play a significant role in our highly electrified world and will continue to lead technology innovations. Millions of vehicles are equipped with or directly powered by LIBs, mitigating environmental pollution and reducing energy use. This rapidly increasing use of LIBs in vehicles will introduce a large quantity of spent LIBs within an 8- to10-year span and proper handling of end-of-life (EOL) vehicle LIBs is required. Over the last several years, the Worcester Polytechnic Institute (WPI) team in the Department of Mechanical Engineering has developed a closed-loop lithium ion battery recycling process and it has been demonstrated that the recovered NMC 111 has similar or better electrochemical properties than the commercial control powder with both coin cells and pouch cells, which have been independently tested by A123 Systems and Argonne National Laboratory. In addition, the different chemical compositions of the incoming recycling streams were shown to have little observed effects on the recovered precursor and resultant cathode material. Therefore, the WPI-developed process applies to different spent Li-ion battery waste streams and is, therefore, general.\n\nDuring the last few years, industry has the tendency to employ higher-nickel and lower-cobalt cathode material since it can provide higher capacity and energy density and lower cost. However, higher-nickel cathode material has the intrinsic unstable properties and surface modifications can be applied to slow down its degradation. Here, two facile scalable Al2O3 coating methods (dry coating and wet coating) were applied to recycled NMC 622 and the resultants were systematically studied. The Al-rich layer from the dry coating process imparted improved structural and thermal stability in accelerated cycling performed at 45 °C between 3.0 and 4.3 V, and the capacity retention of pouch cells with dry coated NMC 622 (D-NMC) cathode increased from 83% to 91% compared to Al-free NMC 622 after 300 cycles. However, for wet coated NMC 622 (W-NMC), the increased surface area accompanying by formation of NiO rock-salt like structure could have negative impacts on the cycling performance.\n\nThere exist three challenges for current LIBs’ recycling research. First of all, most of the research is done in lab-scale and the scale-up ability needs to be proven. The scale-up ability of our recycling process has been verified by our scale-up experiments. The second challenge resides in the flexibility, here once again, with our intentionally designed experiments that having various incoming chemistries, the flexibility is validated. The last challenge is the lack of reliable testing because most of the testing is conducted with coin cells. Coin cells are relatively simple format and lacks persuasion. Here, with various industrial-level cell formats that ranging from coin cell, single layer pouch cell, 1Ah cell and 11Ah cell, a reliable and trustworthy testing is established. With this validation, the hesitation of recruiting recycled materials into industry shouldn’t exist.\nThe industrial sector is one of the largest emitters of CO2 and a great potential for retrofitting with carbon capture systems. In this work the performance of a palladium-based membrane reactor at 400°C and operating pressures between 100-400 kPa have been studied in terms of methane conversion, hydrogen recovery, hydrogen purity, and CO2 emission. It is found that the MR has the potential to produce high purity hydrogen while the methane conversion values could be as high as 40% at very moderate operating conditions and without using any sweep gases. \n\nThe H2 permeation and separation properties of two Pd-based composite membranes were evaluated and compared at 400 °C and at a pressure range of 150 kPa to 600 kPa. One membrane was characterized by an approximately 8 μm-thick palladium (Pd)-gold (Au) layer deposited on an asymmetric microporous Al2O3 substrate; the other membrane consisted of an approximately 11 μm-thick pure palladium layer deposited on a yttria-stabilized zirconia (YSZ) support. At 400 °C and with a trans-membrane pressure of 50 kPa, the membranes showed a H2 permeance of 8.42 × 10−4 mol/m2·s·Pa0.5 and 2.54 × 10−5 mol/m2·s·Pa0.7 for Pd-Au and Pd membranes, respectively. Pd-Au membrane showed infinite ideal selectivity to H2 with respect to He and Ar at 400 °C and a trans-membrane pressure of 50 kPa, while the ideal selectivities for the Pd membrane under the same operating conditions were much lower. Furthermore, the permeation tests for ternary and quaternary mixtures of H2, CO, CO2, CH4, and H2O were conducted on the Pd/YSZ membrane. The H2 permeating flux decreased at the conclusion of the permeation tests for all mixtures. This decline however, was not permanent, i.e., H2 permeation was restored to its initial value after treating the membrane with H2 for a maximum of 7 h. The effects of gas hourly space velocity (GHSV) and the steam-to-carbon (S/C) ratio on H2 permeation were also investigated using simulated steam methane reforming mixtures. It was found that H2 permeation is highest at the greatest GHSV, due to a decline in the concentration polarization effect. Variations in S/C ratio however, showed no significant effect on the H2 permeation. The permeation characteristics for the Pd/YSZ membrane were also investigated at temperatures ranging from 350 to 400 °C. The pre-exponential factor and apparent activation energy were found to be 5.66 × 10−4 mol/m2·s·Pa0.7 and 12.8 kJ/mol, respectively. Scanning Electron Microscope (SEM) and X-ray diffraction (XRD) analyses were performed on both pristine and used membranes, and no strong evidence of the formation of Pd-O or any other undesirable phases was observed.\n\nThe permeation tests with pure hydrogen and inert gases indicate that the MR is highly selective toward hydrogen and the produced hydrogen is an ultrahigh purity grade. The carbon capture experiments in the work consists of dehydrating the retentate stream and redirecting it to a 13X packed bed before analyzing the stream via mass spectrometry. The carbon capture studies reveal that approximately 5.96 mmole CO2 (or 262.25 mg of CO2)can be captured per g of 13X. \n\nIn this study, SEM-EDS, and XRD technics have been used to characterize the crystallography and morphology of the membrane surface. These material characterization techniques reveal that the surface of the membrane has gone through significant oxidation during the steam methane reforming reaction, although this oxidation is only limited to the few nanometers of depth through the surface of the palladium membrane.

  • etd-3761
Defense date
  • 2020
Date created
  • 2020-05-12
Resource type
Rights statement


In Collection:


Permanent link to this page: