45 research outputs found
The Growth Mechanism of Lithium Dendrites and its Coupling to Mechanical Stress
Operando high-resolution light microscopy with extended depth of field is used to observe large regions of an electrode during electrodeposition of lithium. The analysis of the morphology of the evolving deposit reveals that besides electrochemistry, mechanics and crystalline defects play a major role in the growth mechanism. Based on the findings, a growth mechanism is proposed that involves the diffusion of lithium atoms from the lithium surface into grain boundaries and the insertion into crystalline defects in the metal. Crystalline defects are a result of plastic deformation and hence mechanical stimulation augments the insertion of lithium
Similarities in Lithium Growth at Vastly Different Rates
Lithium electrodeposition is important for lithium metal batteries and is presently a safety and reliability concern for the lithium-ion technology. In the literature, many models for the growth of dendrites can be found and a strong dependence on deposition rate is expected. To elucidate the process of the lithium deposition, operando light microscopy at the physical resolution limit of light was performed at rates varying by more than three orders of magnitude. The results show different growth regimes depending on the rate, and where needles, bushes, or accelerated bushes dominate the deposition. All these deposits are based on small crystalline needles and flakes. Little evidence for concentration gradient driven deposition was found. At the highest rate, the electrolyte ionically depletes, but the deposition continues by non-directional bush growth mainly from their insides. An important step at all rates is the insertion into defects in the crystalline lithium
The growth mechanism of lithium dendrites and its coupling to mechanical stress
Operando high-resolution light microscopy with extended depth of field is used to observe large regions of an electrode during electrodeposition of lithium. The analysis of the morphology of the evolving deposit reveals that besides electrochemistry, mechanics and crystalline defects play a major role in the growth mechanism. Based on the findings, a growth mechanism is proposed that involves the diffusion of lithium atoms from the lithium surface into grain boundaries and the insertion into crystalline defects in the metal. Crystalline defects are a result of plastic deformation and hence mechanical stimulation augments the insertion of lithium
Switching from Lithium to Sodium—an Operando Investigation of an FePO Electrode by Mechanical Measurements and Electron Microscopy
Many physical and chemical properties of Na are very similar to those of Li, and therefore, some electrode materials for lithium-ion batteries can also work with sodium ions. As the Na ion is larger than Li, the strains in the host lattice are larger, which can cause deviations in the electrochemical reactions. Herein, mechanical stresses are compared, which are measured by the in situ substrate curvature method during (de)lithiation/(de)sodiation of an FePO electrode. The (de)lithiation and (de)sodiation experiments are performed on the same electrode. According to the change of the lattice parameters, during electrode operation, NaxFePO particles experience a volume change that is 2.6 times larger than that of LixFePO. In the measurements, the composite electrode exhibits a change of the stress amplitude between operation with Li and Na by roughly one order of magnitude for 0 < x < 1. Compared with Li, the mechanical stress evolution during extraction and insertion of Na is highly asymmetric. The observed asymmetry in the electrochemical and the mechanical data may be explained by the different energies that are required to move an intermediary amorphous phase away from or toward the crystalline sodium-rich regions during the (de)sodiation of NaFePO
Aluminum Foil Anodes for Li-ion Rechargeable Batteries: The Role of Li Solubility within β-LiAl
Li-ion battery (LIB) electrodes contain a substantial amount of electrochemically inactive materials, including binder, conductive agent, and current collectors. These extra components significantly dilute the specific capacity of whole electrodes, and thus have led to efforts to utilize foils, e.g., Al, as the sole anode material. Interestingly, the literature has many reports of fast degradation of Al electrodes, where less than a dozen cycles can be achieved. However, in some studies, Al anodes demonstrate stable cycling life with several hundred cycles. In this work, we present a successful pathway for enabling long-term cycling of simple Al foil anodes: β-LiAl phase grown from Al foil (α-Al) exhibits a cycling life of 500 cycles with a ~96% capacity retention when paired with a commercial cathode. The excellent performance stems from strategic utilization of the Li solubility range of β-LiAl that can be (de-)lithiated without altering its crystal structure. This solubility range at room temperature is determined to be ~6 at%. Consequently, this design circumvents the critical issues associated with the α/β/α phase transformations, such as volume change, mechanical strain, and nanopore formation. Application-wise, the maturity of aluminum industry, combined with excellent sustainability prospects, makes this anode an important option for future devices
Aluminum Foil Anodes for Li-Ion Rechargeable Batteries: the Role of Li Solubility within β-LiAl
Lithium-ion battery electrodes contain a substantial amount of electrochemically inactive materials, including binders, conductive agents, and current collectors. These extra components significantly dilute the specific capacity of whole electrodes and thus have led to efforts to utilize foils, for example, Al, as the sole anode material. Interestingly, the literature has many reports of fast degradation of Al electrodes, where less than a dozen cycles can be achieved. However, in some studies, Al anodes demonstrate stable cycling life with several hundred cycles. In this work, we present a successful pathway for enabling long-term cycling of simple Al foil anodes: the β-LiAl phase grown from Al foil (α-Al) exhibits a cycling life of 500 cycles with a ∼96% capacity retention when paired with a commercial cathode. The excellent performance stems from strategic utilization of the Li solubility range of β-LiAl that can be (de-)lithiated without altering its crystal structure. This solubility range at room temperature is determined to be ∼6 at %. Consequently, this design circumvents the critical issues associated with the α/β/α phase transformations, such as volume change, mechanical strain, and formation of nanopores. Application-wise, the maturity of the aluminum industry, combined with excellent sustainability prospects, makes this anode an important option for future devices
A multipurpose laboratory diffractometer for operando powder X-ray diffraction investigations of energy materials
Laboratory X-ray diffractometers are among the most widespread instruments in research laboratories around the world and are commercially available in different configurations and setups from various manufacturers. Advances in detector technology and X-ray sources push the data quality of in-house diffractometers and enable the collection of time-resolved scattering data during operando experiments. Here, the design and installation of a custom-built multipurpose laboratory diffractometer for the crystallographic characterization of battery materials are reported. The instrument is based on a Huber six-circle diffractometer equipped with a molybdenum microfocus rotating anode with 2D collimated parallel-beam X-ray optics and an optional two-bounce crystal monochromator. Scattered X-rays are detected with a hybrid single-photon-counting area detector (PILATUS 300K-W). An overview of the different diffraction setups together with the main features of the beam characteristics is given. Example case studies illustrate the flexibility of the research instrument for time-resolved operando powder X-ray diffraction experiments as well as the possibility to collect higher-resolution data suitable for diffraction line-profile analysis
\u3cem\u3eIn Situ\u3c/em\u3e Nanomechanical Testing in Focused Ion Beam and Scanning Electron Microscopes
The recent interest in size-dependent deformation of micro- and nanoscale materials has paralleled both technological miniaturization and advancements in imaging and small-scale mechanical testing methods. Here we describe a quantitative in situ nanomechanical testing approach adapted to a dualbeam focused ion beam and scanning electron microscope. A transducer based on a three-plate capacitor system is used for high-fidelity force and displacement measurements. Specimen manipulation, transfer, and alignment are performed using a manipulator, independently controlled positioners, and the focused ion beam. Gripping of specimens is achieved using electron-beam assisted Pt-organic deposition. Local strain measurements are obtained using digital image correlation of electron images taken during testing. Examples showing results for tensile testing of single-crystalline metallic nanowires and compression of nanoporous Au pillars will be presented in the context of size effects on mechanical behavior and highlight some of the challenges of conducting nanomechanical testing in vacuum environments
Search for dark matter produced in association with bottom or top quarks in √s = 13 TeV pp collisions with the ATLAS detector
A search for weakly interacting massive particle dark matter produced in association with bottom or top quarks is presented. Final states containing third-generation quarks and miss- ing transverse momentum are considered. The analysis uses 36.1 fb−1 of proton–proton collision data recorded by the ATLAS experiment at √s = 13 TeV in 2015 and 2016. No significant excess of events above the estimated backgrounds is observed. The results are in- terpreted in the framework of simplified models of spin-0 dark-matter mediators. For colour- neutral spin-0 mediators produced in association with top quarks and decaying into a pair of dark-matter particles, mediator masses below 50 GeV are excluded assuming a dark-matter candidate mass of 1 GeV and unitary couplings. For scalar and pseudoscalar mediators produced in association with bottom quarks, the search sets limits on the production cross- section of 300 times the predicted rate for mediators with masses between 10 and 50 GeV and assuming a dark-matter mass of 1 GeV and unitary coupling. Constraints on colour- charged scalar simplified models are also presented. Assuming a dark-matter particle mass of 35 GeV, mediator particles with mass below 1.1 TeV are excluded for couplings yielding a dark-matter relic density consistent with measurements