Anode/electrolyte interface

Fig. 12 Methane reforming reaction at the anode of a molten carbonate fuel cell. The reaction between fuel and water takes place in the outer part of the anode, the produced hydrogen reacts at the interface anode-electrolyte.

It is now well established that in lithium batteries (including lithium-ion batteries) containing either liquid or polymer electrolytes, the anode is always covered by a passivating layer called the SEI. However, the chemical and electrochemical formation reactions and properties of this layer are as yet not well understood. In this section we discuss the electrode surface and SEI characterizations, film formation reactions (chemical and electrochemical), and other phenomena taking place at the lithium or lithium-alloy anode, and at the Li. C6 anode/electrolyte interface in both liquid and polymer-electrolyte batteries. We focus on the lithium anode but the theoretical considerations are common to all alkali-metal anodes. We address also the initial electrochemical formation steps of the SEI, the role of the solvated-electron rate constant in the selection of SEI-building materials (precursors), and the correlation between SEI properties and battery quality and performance. 

Sol-gel technique has also been applied to modify the anode/electrolyte interface for SOFC running on hydrocarbon fuel [16]. ANiA SZ cermet anode was modified by coating with SDC sol within the pores of the anode. The surface modification of Ni/YSZ anode resulted in an increase of structural stability and enlargement of the TPB area, which can serve as a catalytic reaction site for oxidation of carbon or carbon monoxide. Consequently, the SDC coating on the pores of anode leads to higher stability of the cell in long-term operation due to the reduction of carbon deposition and nickel sintering. 

FIGURE 2.24 Change of impedance spectra for the anode/electrolyte interface with respect to change in H2S concentration at (a) 900°C, and (b) 750°C. (From Matsuzaki, Y. and Yasuda, I., Solid State Ionics, 132 261-269, 2000. Copyright by Elsevier, reproduced with permission.)... 

But drawing is laborious, so we generally employ a more sensible alternative we write a cell schematic, which is a convenient abbreviation of a cell. It can be read as though it was a cross-section, showing each interface and phase. It is, therefore, simply a shorthand way of saying which components are incorporated in the cell as cathode, anode, electrolyte, etc., and where they reside. 

Peled s Model Anode/Electrolyte Interface Film. In their proposal of SEI formation on a carbonaceous electrode in nonaqueous electrolytes, Dahn actually adopted Peled s model for lithium s surface and extended it to carbonaceous electrodes. By this model, a two-dimensional passivation film is established via a surface reaction. 

Due to the core importance of the SEI formation on carbonaceous anodes, the majority of the research activities on additives thus far aim at controlling the chemistry of the anode/electrolyte interface, although the number of publications related to this topic is rather limited as compared with the actual scale of interest by the industry. Table 9 summarizes the additives that have been described in the open literature. In most cases, the concentration of these interface-targeted additives is expected to be kept at a minimum so that the bulk properties of the electrolytes such as ion conduction and liquid ranges would not be discernibly affected. In other words, for an ideal anode additive, its trace presence should be sufficient to decouple the interfacial from bulk properties. Since there is no official standard available concerning the upper limit on the additive concentration, the current review will use an arbitrary criterion of 10% by weight or volume, above which the added component will be treated as a cosolvent instead of an additive. 

This sharp decline in cell output at subzero temperatures is the combined consequence of the decreased capacity utilization and depressed cell potential at a given drain rate, and the possible causes have been attributed so far, under various conditions, to the retarded ion transport in bulk electrolyte solutions, ° ° - ° ° the increased resistance of the surface films at either the cathode/electrolyte inter-face506,507 Qj. anode/electrolyte interface, the resistance associated with charge-transfer processes at both cathode and anode interfaces, and the retarded diffusion coefficients of lithium ion in lithiated graphite anodes. - The efforts by different research teams have targeted those individual electrolyte-related properties to widen the temperature range of service for lithium ion cells. 

The latter authors used anode and cathode symmetrical cells in EIS analysis in order to simplify the complication that often arises from asymmetrical half-cells so that the contributions from anode/ electrolyte and cathode/electrolyte interfaces could be isolated, and consequently, the temperature-dependences of these components could be established. This is an extension of their earlier work, in which the overall impedances of full lithium ion cells were studied and Ret was identified as the controlling factor. As Figure 68 shows, for each of the two interfaces, Ra dominates the overall impedance in the symmetrical cells as in a full lithium ion cell, indicating that, even at room temperature, the electrodic reaction kinetics at both the cathode and anode surfaces dictate the overall lithium ion chemistry. At lower temperature, this determining role of Ra becomes more pronounced, as Figure 69c shows, in which relative resistance , defined as the ratio of a certain resistance at a specific temperature to that at 20 °C, is used to compare the temperature-dependences of bulk resistance (i b), surface layer resistance Rsi), and i ct- For the convenience of comparison, the temperature-dependence of the ion conductivity measured for the bulk electrolyte is also included in Figure 69 as a benchmark. Apparently, both and Rsi vary with temperature at a similar pace to what ion conductivity adopts, as expected, but a significant deviation was observed in the temperature dependence of R below —10 °C. Thus, one... 

As has been shown in Eigure 68, since the time constants for these two electrochemical components, Rsei and Ra, are comparable at anode/electrolyte and cathode/electrolyte interfaces, respectively, the impedance spectra of a full lithium ion could have similar features in which the higher frequency semicircle corresponds to the surface films on both the anode and the cathode, and the other at lower frequency corresponds to the charge-transfer processes occurring at both the anode and the cathode. ... 

For example, Bieberle and Gauckler [7] developed an electrochemical model for the Ni, H2-H2O-YSZ system (i.e. the anodic triple phase boundary). As a result they identify possible reaction mechanisms and calculate some kinetic parameters, thus providing valuable inputs and information for simulating the entire fuel cell. Moreover a better understanding of atomistic phenomena acting at the anode-electrolyte interface is provided. 

Fig. 3.8 Schematic showing both ohmic and activation losses, and the modeled discretized potential jump at the anode-electrolyte interface.

Figure 3.8 depicts a qualitative description of the resulting potential jump taking place at the anode-electrolyte interface. 

Since electrons are produced at the anode-electrolyte interface, they proceed from this interface toward the current collector above the anode as shown in Figure 3.8. (The readeris reminded that it is a common convention to considerthe electric current direction as opposite to that of electron flow.) Due to ohmic losses, a potential decrease takes place as the current flows within the anode. At the cathode-electrolyte interface, a mass flux occurs, due to reaction (3.16). 

Fig. 4.10 (a) H2 concentration at anode/electrolyte interface (b) O2 concentration at cath-ode/electrolyte interface. The operating conditions are oxygen flow rate 12 N1 h 1, hydrogen flow rate 24 N1 h 1, cell voltage 0.8 V at 360 mA cm-1. 

Here subscripts a and c denote anode and cathode respectively, iref is the reference exchange current density, y is the concentration dependence exponent, [ ] and [ ]ref represent the local species concentration and its reference concentration, respectively. Anode transfer current, Ra, is the source in the electric potential equations at the anode/electrolyte interface with positive sign on membrane (electrolyte) side and negative sign on solid (anode) side. Similarly, near the cathode interface, the source on membrane (electrolyte) side is negative of the cathode transfer current, Rc and that on solid (cathode) side is positive of Rc. The activation over-potentials, in Equations (5.35) and (5.36) are given by... 

Fig. 5.14 Prediction of Temperature (K) distribution for five cell co-flow SOFC stack obtained using DREAM-SOFC. (a) Contours at anode/electrolyte interface of each cell, (b) Profiles along the direction of channels at the center of each cell.

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