Filament-Induced Failure in Lithium-Reservoir-Free Solid-State Batteries
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Lithium-Ion (Li-Ion) batteries have yielded significant performance advantages for many industries, including the aerospace industry, and have been selected to replace nickel hydrogen (Ni-H2) batteries for the International Space Station (ISS) program to meet the energy storage demands. As the ISS uses its vast solar arrays to generate its power, the solar ar-rays meet their sunlit power demands and supply excess power to battery packs for power de-livery on the sun obscured phase of the approximate 90 minute low Earth orbit. These large battery packs are located on the exterior of the ISS, and as such, the battery packs are ex-posed to external environment threats like naturally occurring meteoroids and artificial orbital debris (MMOD). While the risks from these solid particle environments has been known and addressed to an acceptable risk of failure through shield design, it is not possible to completely eliminate the risk of loss of these assets on orbit due to MMOD, and as such, failure consequences to the ISS have been considered.
Improved analytical tools are urgently required to identify degradation and failure mechanisms in Li-ion batteries. However, understanding and ultimately avoiding these detrimental mechanisms requires continuous tracking of complex electrochemical processes in different battery components. Here, we report an operando spectroscopy method that enables monitoring the chemistry of a carbonate-based liquid electrolyte during electrochemical cycling in Li-ion batteries with a graphite anode and a LiNi 0.8 Mn 0.1 Co 0.1 O 2 cathode. By embedding a hollow-core optical fibre probe inside a lab-scale pouch cell, we demonstrate the effective evolution of the liquid electrolyte species by background-free Raman spectroscopy. The analysis of the spectroscopy measurements reveals changes in the ratio of carbonate solvents and electrolyte additives as a function of the cell voltage and show the potential to track the lithium-ion solvation dynamics. The proposed operando methodology contributes to understanding better the current Li-ion battery limitations and paves the way for studies of the degradation mechanisms in different electrochemical energy storage systems.
Redistribution of zinc over the electrode surface, also known as shape change, is a major problem and a cause of failure in alkaline zinc anode batteries. To mitigate this phenomenon, we propose a scalable approach based on an in situ formed, highly porous electrochemically synthesized ZnO matrix with uniformly electrodeposited zinc particles. This results in ∼70% improvement in cycle life performance at a rate of 10 mA cm −2 compared to control Zn anodes, which have not gone through the formation process. A quantitative electrolyte analysis revealed under-saturated zincate ion concentration in the electrochemically synthesized ZnO/Zn cells indicating reduced zincate movement. Post mortem analysis of the anodes indicated higher retention of both Zn and ZnO on the electrochemically synthesized ZnO anodes signifying reduced redistribution of active material. Image analysis of the cycled anodes revealed a narrower Zn particle size distribution (62−79 μ m) in contrast to a wider particle size distribution of 51–96 μ m observed in the control anodes. The formation approach results in electrochemically synthesized ZnO/Zn anodes providing a stable ZnO matrix in which Zn particles retain their localized distribution on cycling better than control electrodes conventionally made by pasting zinc particles together with a binder.
Highly popular due to their high energy density lithium-ion battery cells have increased in energy density approximately 2.5 times since their commercial debut in 1991. As a result, the hazard severity of a sudden inadvertent release of stored energy has greatly increased. The high energy density of lithium-ion battery cells coupled with the flammable toxic electrolytes they contain and unique failure modes can lead to a potentially catastrophic thermal runaway. This can result in spewing flames even while setting on a shelf unused. The metal oxide cathodes in lithium-ion battery cells can release their oxygen into the cells when they overheat. There is enough oxygen contained in the metal oxide cathodes to combust up to 20 percent of the electrolytes in the cells without any outside oxygen sources. These cells can therefore be viewed as miniature rocket motors capable of venting a considerable blow-torch type flame and up to 2.5 liters of hot flammable toxic gases per cell. This presents special challenges for spaceflight safety. In this paper we will examine roots causes of 18650 lithium-ion battery cell failures and how to best mitigate them at the cell and battery assembly levels. We will also look at some promising future trends that could yield both much greater stored energy and safety.
A safe and reliable battery operation needs effective diagnostic tools. A quantitative failure analysis (FA) to enable cell qualification and quantify its effectiveness for reliable and safe operation of rechargeable Li batteries (RLB) is shown here. The method can identify and quantify potential failure based on the state of charge (SOC) under any operating conditions. A precise and accurate electrochemical analytic diagnosis (eCAD) of 14 rechargeable Li || NMC622 cells of the same build are used as an example. The FA by eCAD can quantitatively decipher good, bad and ugly cells in cycle aging. The cell qualification is based on thermodynamic SOC, not experimental conditions. The method provides a quantitative failure mode and effect analysis (FMEA) to reveal diverse “dead Li” formation that affects the reversibility of the Li anode and charge retention in the cell. This cell qualification method highlights the potential to improve cell quality for safe operation, with strong implications for early fault detection, FA, risk mitigation, state estimation and life prediction for reliable and safe RLB operations
Predictive failure models for nickel cadmium batteries are discussed. Emphasis is given to the McDermott model, the Lander model, and the JPL failure model.
Ni-rich layered oxides are the most promising cathodes for Li-ion batteries, but chemo-mechanical failures during cycling and large first-cycle capacity loss hinder their applications in high-energy batteries. Herein, by introducing spinel-like mortise-tenon structures into the layered phase of LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811), the adverse volume variations in cathode materials can be significantly suppressed. Meanwhile, these mortise-tenon structures play the role of the expressway for fast lithium-ion transport, which is substantiated by experiments and calculations. Moreover, the particles with mortise-tenon structures usually terminate with the most stable (003) facet. The new cathode exhibits a discharge capacity of 215 mAh g –1 at 0.1 C with an initial Coulombic efficiency of 97.5%, and capacity retention of 82.2% after 1200 cycles at 1 C. Importantly, this work offers a viable lattice engineering to address the stability and low initial Coulombic efficiency of the Ni-rich layered oxides, and facilitates the implementation of Li-ion batteries with high-energy density and long durability.
Ether solvents are suitable for formulating solid-electrolyte interphase (SEI)-less ion-solvent cointercalation electrolytes in graphite for Na-ion and K-ion batteries. However, ether-based electrolytes have been historically perceived to cause exfoliation of graphite and cell failure in Li-ion batteries. In this study, we develop strategies to achieve reversible Li–solvent cointercalation in graphite through combining appropriate Li salts and ether solvents. Specifically, we design 1M LiBF 4 1,2-dimethoxyethane (G1), which enables natural graphite to deliver ~91% initial Coulombic efficiency and >88% capacity retention after 400 cycles. We captured the spatial distribution of LiF at various length scales and quantified its heterogeneity. The electrolyte shows self-terminated reactivity on graphite edge planes and results in a grainy, fluorinated pseudo-SEI. The molecular origin of the pseudo-SEI is elucidated by ab initio molecular dynamics (AIMD) simulations. The operando synchrotron analyses further demonstrate the reversible and monotonous phase transformation of cointercalated graphite. Our findings demonstrate the feasibility of Li cointercalation chemistry in graphite for extreme-condition batteries. The work also paves the foundation for understanding and modulating the interphase generated by ether electrolytes in a broad range of electrodes and batteries.
Lithium-ion batteries (LIBs) feature structural and chemical complexities across a broad range of length scales. It is the hierarchy of the battery structure that determines its functionality. An in-depth understanding of the battery function, degradation, and failure mechanisms requires a thorough and systematic investigation from structural, chemical, mechanical, and dynamic perspectives. Here we present a macro-to-nano zoom through the hierarchy of a commercial 18650 type LIB using a suite of state-of-the-art X-ray microscopy techniques. Damage, deformation, and heterogeneity at different length scales are visualized and are associated with different degradation phenomena and mechanisms. Our results highlight the importance of the mechanical properties of the cathode material, which could impact both the immediate and the long-term cell behaviors significantly. While this study focuses on a commercial lithium cell with a standard configuration, our findings can be extrapolated and are applicable to the development of next-generation energy storage technology, e.g. solid-state batteries.
In 2019 the International Space Station (ISS) experienced an on on-orbit failure that affected 1 of 28 Battery Charge Discharge Units (BCDUs). Telemetry pointed to a short circuit failure of a Power Rectifier Quad Diode Module. Astronauts removed the failed unit from service which was then returned to Earth for failure analysis. The failure analysis confirmed that the quad diode module had failed short circuit. The investigation identified silver dendrites had grown on the insulated, sloped edge of the mesa semiconductor die of the failed diode and also a 2nd diode in the same quad diode module. Voids between the diode’s protective encapsulating ring and the die provided space within which dendrites were able to form and cause catastrophic failure. The NASA Engineering & Safety Center (NESC) convened a EEE Parts Sub-Team to investigate root cause and to assist with risk assessment for all of the flight diode modules (4 distinct production lots) and the flight spares (from a 5th lot). Analysis of the original diode manufacturer’s read and record screening test data identified some lots which contained diodes with parametric instabilities that could signal conditions suited for silver dendrite formation. Computed Tomography (CT) X-ray screening inspection was performed on flight spare modules to identify diodes that do not exhibit voids between the edge of die and encapsulating ring as a mitigation against dendrite formation.
Test program, employing empirical, statistical and physical methods, determines service life and failure probabilities of electrochemical cells and batteries, and is applicable to testing mechanical, electrical, and chemical devices. Data obtained aids long-term performance prediction of battery or cell.
Aluminum foils are an appealing anode for lithium-ion batteries due to high capacity and low-cost, but their viability has been limited due to poor cyclability arising from pulverization and solid-electrolyte interphase growth. Here, we show that significant capacity degradation of aluminum foil anodes during electrochemical cycling also occurs due to diffusional lithium trapping. Scanning electron microscopy of cross-sectioned, cycled foils in the delithiated state reveals large regions of β-LiAl that are passivated by a surface layer of α-Al, which has poor Li + diffusivity. It is found that lithium diffusion occurs preferentially along the β-LiAl grain boundaries, so the grain structure after initial lithiation significantly affects the trapping behavior. Diffusional lithium trapping is exacerbated by both higher delithiation rates and higher areal capacity, presenting a challenge towards commercialization of aluminum foil anodes. We further demonstrate that diffusional trapping in aluminum foil anodes can be mitigated through alloy design, with the addition of 2–3 wt% Li yielding improved first cycle efficiency, and the addition of 1 wt% Si yielding improved cycle life. These results provide a mechanistic understanding of diffusional lithium trapping in aluminum foil anodes and highlight compositional design of alloys as a promising strategy to overcome it.
Internal short-circuit in a lithium-ion cell causes an abrupt increase in cell temperature and triggers subsequent thermal runaway. In this work, we present a detailed electrochemical-thermal model to investigate the physical behavior during an internal short-circuit. Simulations at wide range of heat transfer coefficients and short-circuit resistances are conducted to illustrate electrochemical and thermal behavior under a wide range of conditions. The Joule heating at the shorted region promotes electrochemical reactions nearby, causing in-plane non-uniformity of electrolyte and active material transport. Furthermore, it is found that diffusion in solid active materials plays a significant role at very high shorting currents (~20 C), as electrochemical reactions rate are being controlled progressively more by availability of Li + at the interface, due to limitations in diffusion through the active material with increasing discharge rates. This diffusion limitation causes a drop in available energy, and subsequently a decrease in cell equilibrium potential and the heat generation rate at the location of the short. On the other hand, rapid depletion of lithium concentration in the electrolyte and accumulation on the electrode surface results in highly non-uniform transport properties resulting in higher heat generation rates. Hence, the heating regime shifts from "local heating" to "global heating". Based on the findings, important design parameters for battery safety are discussed.
Rollup solar array, thermoelectric failure mode testing, sterilizable battery, and surface potential of silver electrodes - spacecraft power
A large scale test of 6.0 Ah Nickel-Cadmium Cells conducted at the Naval Weapons Support Center, Crane, Indiana has demonstrated a methodology for predicting battery life based on failure data from cells cycled in an accelerated mode. After examining eight variables used to accelerate failure, it was determined that temperature and depth of discharge were the most reliable and efficient parameters for use in accelerating failure and for predicting life.
India's first experimental communication satellite, APPLE, carried a 12 AH Ni-Cd battery for supplying power during eclipse. Failure to deploy one of the two solar panels resulted in the battery operating in a high temperature environment, around 40 C. This also resulted in the battery being used in diurnal cycles rather than just half yearly eclipse seasons. The management and performance of the battery during its life of two years are described. An attempt to identify the probable degradation mechanisms is also made.