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Nanomaterials for Lithium(-ion) Batteries
Published in Sam Zhang, Materials for Devices, 2023
Lithium hexafluorophosphate (LiPF6) is currently the most widely used lithium salt in commercial LIBs. The success of LiPF6 does not only lie in its single outstanding performance in all aspects, but it also owns the majority of the fundamental and mutually exclusive properties that are required for durable cells. It exhibits characteristics such as moderate ion migration number, dissociation constant, and aluminum foil passivation ability. Despite all its virtues, it is unstable when heating; even worse, it would decompose into LiF(s) and PF5(g) at room temperature [90]. PF5 is a strong Lewis acid, which can easily attack lone pair electrons on oxygen atoms in organic solvents, resulting in cationic polymerization of organic solvents and ether bond cracking. Yet, the P-F bond is labile toward hydrolysis by even trace amounts of moisture in nonaqueous solvents, producing HF and LiF. The presence of LiF will increase the interface resistance and affect the cycle life of LIBs.
Li -ion Batteries for Electric Vehicles
Published in Subhas K. Sikdar, Frank Princiotta, Advances in Carbon Management Technologies, 2021
Nowadays, most of the commercialized LIBs use organic liquid electrolytes with lithium hexafluorophosphate ( LiPF6 ) as the conducting salt dissolved in various mixtures of carbonate solvents. The most commonly-used carbonate solvents are ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC) and ethylmethyl carbonate (EMC). These carbonates have large electrolyte voltage windows, possess low viscosities that enable better Li+ diffusion, and are oxidatively stable enough to be used for high voltage cathode materials (Aurbach, 2000).
Solid-State Materials for Batteries
Published in Elaine A. Moore, Lesley E. Smart, Solid State Chemistry, 2020
Elaine A. Moore, Lesley E. Smart
In current batteries, the anode is made of lithium embedded in graphite, forming an intercalation compound, typically C6Li; in discharge mode, this easily releases Li+. The lithium ions travel through a Li+-containing electrolyte to a cathode, where it intercalates. The cathode can be made of mixed metal oxides, e.g. NixMnyCozO2 or other materials that intercalate lithium, notably FePO4, NiO2, and TiS2. The battery used in the second-generation Nissan Leaf electric car, for example, has a layered cathode consisting of layers of oxide ions, lithium ions, and mixed Mn/Co/Ni ions. The structure of a layered cathode, LiMO2, is shown in Figure 6.15. The electrolyte is a nonaqueous solvent, such as ethylene carbonate, mixed with a lithium complex salt; lithium hexafluorophosphate (LiPF6), lithium tetrafluoroborate (LiBF4), and lithium triflate (LiCF3SO3), being commonly used. The Li+ ions ‘rock’ between the two intercalation compounds and no lithium metal is ever present, eliminating many of the hazards associated with lithium batteries.The structure of LiMO2. Li, small purple spheres. O, small red spheres attached to blue octahedra (M).
Lithium iron phosphate batteries recycling: An assessment of current status
Published in Critical Reviews in Environmental Science and Technology, 2021
Federica Forte, Massimiliana Pietrantonio, Stefano Pucciarmati, Massimo Puzone, Danilo Fontana
As a general rule, LIBs are made of an anode, a cathode, current collectors, a separator, liquid electrolyte, container and sealing parts (Gratz et al., 2014). The anode is usually a copper foil coated with a mixture of graphite, a conductor, polyvinylidene fluoride (PVDF) binder and the electrolyte. The electrolyte is normally lithium hexafluorophosphate (LiPF6) dissolved in an organic solvent (commonly ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC) or their mixture). Similarly, the cathode is an aluminum foil coated with cathode materials, a conductor, a PVDF binder and fluoride salt. In order to prevent a short circuit between two electrodes, a separator made of polypropylene (PP) or polyethylene (PE) is placed between the anode and cathode as a barrier (Zhang et al., 2014). The structure of a Li-ion cell is shown in Figure 1 (Mancini, 2008). Li ions move from the anode to the cathode during discharge and are intercalated into open spaces in the voids in the cathode. The Li ions make the reverse journey during charging. Numerous designs are possible for assembling cells into a battery pack for an electric or hybrid vehicle (Gaines & Cuenca, 2000). A modular design is used in most cases, with a number of cells (typically between 6 and 12) packaged together into a unit called a “module.” The modules can then be combined into a battery pack sized to match the requirements of the vehicle (Figure 2). The same modules could be used in a variety of different battery packs. The shapes and sizes of a LIB cell vary greatly and the number of individual cells in battery packs or modules may vary from tens to thousands depending on the applications (Huang et al., 2018).
Detailed characterization of particle emissions from battery fires
Published in Aerosol Science and Technology, 2022
Vinay Premnath, Yanyu Wang, Nolan Wright, Imad Khalek, Steven Uribe
Battery failure can be categorized into four failure stages. The first stage is when batteries are subjected to an abuse factor such as thermal (over-heating), electrical (over-charging) or mechanical (Lamb et al. 2015; Larsson and Mellander 2014; Ohsaki et al. 2005). Typically, electrolytes used in Li-ion batteries are composed of a Li salt such as lithium hexafluorophosphate (LiPF6) and a solvent. Commonly used solvents include ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), and ethyl methyl carbonate (EMC). These solvents are traditionally stable chemicals, however, the presence of lithium salt catalyzes their breakdown to volatile species in the presence of abuse factors that enhance thermal exposure (Larsson et al. 2017; Zinigrad et al. 2005). As electrical or thermal abuse continues, liquid electrolyte starts transforming to gas. Gases that include solvent vapors, carbon dioxide (CO2), carbon monoxide (CO), water vapor, hydroflouric acid (HF), lithium fluoride (LiF) among others eventually vent from the cell. This is referred to as Stage 2 of failure where the escaping gases may be susceptible to ignition. At this stage, early detection of leakage gases from electrolyte could help prevent thermal runaway if certain measures are implemented to stop abuse from continuing (Cai et al. 2020, 2021; Cai, Stefanopoulou, and Siegel 2019; Essl et al. 2021). If the battery cell continues to get subjected to the abuse factor, gas generation will continue to the point where pressure generated from these gases will eventually result in breaching the separator. This is classified as Stage 3 of failure and there is onset of smoke generation, and thermal runaway is imminent. The significant release of energy that follows separator breakdown results in a fire, and often, explosion (Stage 4). This results in the emissions of various species that include electrolyte solvent vapors, hydrogen, carbon monoxide (CO), volatile organic compounds (such as alkanes), water vapor, carbon dioxide, elemental carbon compounds, in addition to fluorine compounds stemming from electrolyte and electrode materials such as hydrogen fluoride, phosphorus pentafluoride, phosphoryl fluoride among others (Golubkov et al. 2014; Larsson et al. 2014; Larsson, Andersson, and Mellander 2016; Larsson and Mellander 2014; Nedjalkov et al. 2016). Other compounds are also released depending on the battery chemistry. While the above stages are more applicable for thermal and electrical abuse factors that lead to cell heating, mechanical abuse factors may directly result in failure stages 3 and 4 (Aiello et al. 2021; Doose, Haselrieder, and Kwade 2021; Essl, Golubkov, and Fuchs 2020; Feng et al. 2018; Huang et al. 2020; Yokoshima et al. 2019). After onset of thermal runaway, fire and gases could contribute toward heating adjacent cells thereby leading to propagation of thermal runaway (Larsson, Andersson, and Mellander 2016; Liu et al. 2016; Lopez, Jeevarajan, and Mukherjee 2015). Furthermore, these stages may also be influenced by the state-of-charge (SOC) of the cells (Golubkov et al. 2015).