Solid electrolyte interphase thickness

The rate of this process in aprotic electrolytes is rather high the exchange current density is fractions to several mA/cm. As pointed out already, the first contact of metallic lithium with electrolyte results in practically the instantaneous formation of a passive film on its surface conventionally denoted as solid electrolyte interphase (SEI). The SEI concept was formulated yet in 1979 and this film still forms the subject of intensive research. The SEI composition and structure depend on the composition of electrolyte, prehistory of the lithium electrode (presence of a passive film formed on it even before contact with electrode), time of contact between lithium and electrolyte. On the whole, SEI consists of the products of reduction of the components of electrolyte. In lithium thionyl chloride cells, the major part of SEI consists of lithium chloride. In cells with organic electrolyte, SEI represents a heterogeneous (mosaic) composition of polymer and salt components lithium carbonates and alkyl carbonates. It is essential that SEI features conductivity by lithium ions, that is, it is solid electrolyte. The SEI thickness is several to tens of nanometers and its composition is often nonuniform a relatively thin compact primary film consisting of mineral material is directly adjacent to the lithium surface and a thicker loose secondary film containing organic components is turned to electrolyte. It is the ohmic resistance of SEI that often determines polarization of the lithium electrode. 

Although reports following the initial marketing of Sony Corporation s batteries focused not only on metallic lithium anodes and graphite anodes but also on the solid electrolyte interphase (SEI), which forms on the anode as a result of electrolyte decomposition, intentional control of SEI was not considered in sufficient depth. The concept of SEI was advocated by Peled from Tel-Aviv University and Aurbach from Bar-Ilan University [8-10]. Nevertheless, upon entering the industry in 1997, Ube Industries, Ltd. started adding small amounts of additives to the electrolyte, which allowed for the undesirable thick SEI to be controlled by deliberately causing additive decomposition in order to form a controlled thin layer (CTL). 

The layer formed instantaneously upon contact of the metal with the solution, consists of insoluble and partially soluble reduction products of electrolyte components. The thickness of the freshly formed layer is determined by the electron-tunneling range. The layer acts as an interphase between the metal and the solution and has the properties of a solid electrolyte with high electronic resistivity. For this reason it was called a solid-electrolyte interphase SEI. The batteries, consisting of SEI electrode, were called SEI batteries. ... 

The surface films discussed in this section reach a steady state when they are thick enough to stop electron transport. Hence, as the surface films become electrically insulating, the active electrodes reach passivation. In the case of monovalent ions such as lithium, the surface films formed in Li salt solutions (or on Li metal) can conduct Li-ions, and hence, behave in general as a solid electrolyte interphase (the SEI model ). See the basic equations 1-7 related to ion transport through surface films in section la above. The potentiodynamics of SEI electrodes such as Li or Li-C may be characterized by a Tafel-like behavior at a high electrical field and by an Ohmic behavior at the low electrical field. The non-uniform structure of the surface films leads to a non-uniform current distribution, and thereby, Li dissolution from Li electrodes may be characterized by cracks, and Li deposition may be dendritic. The morphology of these processes, directed by the surface films, is dealt with later in this chapter. When bivalent active metals are involved, their surface films cannot conduct the bivalent ions. Thereby, Mg or Ca deposition is impossible in most of the commonly used polar aprotic electrolyte solutions. Mg or Ca dissolution occurs at very high over potentials in which the surface films are broken. Hence, dissolution of multivalent active metals occurs via a breakdown and repair of the surface films. 

We can assume that as the surface films formed on active surfaces in solutions reach a certain thickness, they become electronic insulators. Hence, any possible electrical conductance can be due to ionic migration through the films under the electrical field. The active surfaces are thus covered with a solid electrolyte interphase (the SEI model [5]), which can be either anionic or cationic conducting, or both. 

It has been suggested that in practical non-aqueous lithium battery systems the anode (Li or graphite) is always covered by a surface layer named the solid electrolyte interphase (SEI), 1-3 run thick, which is instantly formed by the reaction of the metal with the electrolyte. This film, which acts as an interphase between the metal and the solution, has the properties of a solid electrolyte. This layer has a corrosive effect and grows with the cycling life of the battery [52], Thermodynamic stability of a lithium cell requires the electrochemical potentials of electrodes a and Ec located within the energetic window of the electrolyte, which contrains the cell voltage Eq of th electrochemical ceU to ... 

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