Electrolytic decomposition

Early demand for chlorine centered on textile bleaching, and chlorine generated through the electrolytic decomposition of salt (NaCl) sufficed. Sodium hydroxide was produced by the lime—soda reaction, using sodium carbonate readily available from the Solvay process. Increased demand for chlorine for PVC manufacture led to the production of chlorine and sodium hydroxide as coproducts. Solution mining of salt and the avadabiHty of asbestos resulted in the dominance of the diaphragm process in North America, whereas soHd salt and mercury avadabiHty led to the dominance of the mercury process in Europe. Japan imported its salt in soHd form and, until the development of the membrane process, also favored the mercury ceU for production. 

Pkctrolysis of HCl Electrolytic decomposition of aqueous HCl to generate CI2 and H2 foHows the overaH reaction... 

The electrolytic decomposition of alumina yields oxygen which reacts with the carbon anode for an overall cell reaction ... 

Sir Humphry Davy first isolated metallic sodium ia 1807 by the electrolytic decomposition of sodium hydroxide. Later, the metal was produced experimentally by thermal reduction of the hydroxide with iron. In 1855, commercial production was started usiag the DeviUe process, ia which sodium carbonate was reduced with carbon at 1100°C. In 1886 a process for the thermal reduction of sodium hydroxide with carbon was developed. Later sodium was made on a commercial scale by the electrolysis of sodium hydroxide (1,2). The process for the electrolytic decomposition of fused sodium chloride, patented ia 1924 (2,3), has been the preferred process siace iastallation of the first electrolysis cells at Niagara Falls ia 1925. Sodium chloride decomposition is widely used throughout the world (see Sodium compounds). 

The charge state of the cell must be maintained in operation to have a cell voltage of 0.9 to 1.2 V [6]. Overcharging the cell is to be avoided due to electrolytic decomposition of water and evolution of gas. The cell voltage should therefore not exceed 1.4 V. Cathodic protection stations should be operated so that the cell voltage lies in the desired range. 

Besides the irreversible charge loss caused by electrolyte decomposition, several authors claim that the following reactions are also responsible for (additional) irreversible charge losses ... 

It was observed in other works that in sulfide electrolyte, decomposition of ZnSe was still obtained stable PECs could be constructed though from singlecrystal, n-type, Al-doped ZnSe electrodes and aqueous diselenide or ditelluride electrolytes [124]. Long-term experiments in these electrolytes were accompanied by little electrode weight loss, while relatively constant photocurrents and lack of surface damage were obtained, as well as competitive electrolyte oxidation. Photoluminescence and electroluminescence from the n-ZnSe Al electrodes were investigated. 

FIGURE 9.6 Cyanide reduction via electrolytic decomposition. (Adapted from U.S. EPA, Meeting Hazardous Waste Requirements for Metal Finishers, Report EPA/625/4-87/018, U.S. Environmental Protection Agency, Cincinnati, OH, 1987.)... 

Figure 9. Excerpts of the peaks due to "electrolyte decomposition " recorded by voltammetry in 1 MLiCl04 in y-butyrolactone as electrolyte without and with C02 (saturated in the electrolyte) as electrolyte additive, scan rate 0.01 mV s 1 [12, 13].

It should be noted here, that not only the (chemical and morphological) composition of the protective layers at the basal plane surfaces and prismatic surfaces is different, but that these layers also have completely different functions. At the prismatic surfaces, lithium ion transport into/ffom the graphite structure takes place by intercalation/de-intercalation. Here the formed protective layers of electrolyte decomposition products have to act as SEI, i.e., as transport medium for lithium cations. Those protective layers, which have been formed on/at the basal plane surfaces, where no lithium ion transport into/from the graphite structure takes place, have no SEI function. However, these non-SEI layers still protect these anode sites from further reduction reactions with the electrolyte. 

Figure 17. The basal plane and prismatic surfaces of graphite have different functions with respect to lithium intercalation and de-intercalation (= charge, discharge, self-discharge, etc.). As a consequence, only the electrolyte decomposition product layers at the prismatic surfaces have SEIfunction. Any processes related with electrolyte decomposition product layers at the basal plane surfaces (= non-SEI layers) therefore can not be directly related to electrochemical data such as charge, discharge, self-discharge, etc. The situation is even more complex as the SEI composition and morphology at the basal and prismatic surface...

Hence, it is clear that the irreversible capacity is not directly related with the presence of surface oxygenated groups. In the conditions used for outgassing at 900°C, the number of active sites has not been modified [33], Therefore, taking into account that the irreversible capacity is almost the same for the experiments shown in Figures 2 and 3, it might mean that only the active sites are responsible of the electrolyte decomposition, and consequently of the SEI development. 

In this paper, we presented new information, which should help in optimising disordered carbon materials for anodes of lithium-ion batteries. We clearly proved that the irreversible capacity is essentially due to the presence of active sites at the surface of carbon, which cause the electrolyte decomposition. A perfect linear relationship was shown between the irreversible capacity and the active surface area, i.e. the area corresponding to the sites located at the edge planes. It definitely proves that the BET specific surface area, which represents the surface area of the basal planes, is not a relevant parameter to explain the irreversible capacity, even if some papers showed some correlation with this parameter for rather low BET surface area carbons. The electrolyte may be decomposed by surface functional groups or by dangling bonds. Coating by a thin layer of pyrolytic carbon allows these sites to be efficiently blocked, without reducing the value of reversible capacity. 

Sodium chloride, 22 797-822. See also Salt analytical methods for, 22 811-812 applications of, 22 814-820 from brine, 5 800-801 corrosive effect on iron, 7 806 deposits of, 22 798, 799, 805 described, 22 797 in detergent formulations, 3 418 economic aspects of, 22 810-811 electrolysis of, 22 760 electrolysis of fused, 22 769-772 electrolytic decomposition, 6 175-177 environmental impact of, 22 813-814, 817... 

These include the variations of sacrificial anode, sonication, and alternating polarity cell mentioned above, different solvent/co-solvent and electrolyte systems, monomer concentration, total current passed, and temperature. Best results appear to be obtained with THF and dimethyl ether (DME) as solvent and a perchlorate supporting electrolyte in some systems using fluorides, electrolyte decomposition occurred releasing fluoride anion which formed unreactive fluorosilanes.125... 

On the fundamental front, Dahn et al. successfully accounted for the irreversible capacity that accompanies all carbonaceous anodes in the first cycling. They observed that the irreversible capacity around 1.2 V follows an almost linear relation with the surface area of the carbonaceous anodes and that this irreversible process is essentially absent in the following cycles. Therefore, they speculated that a passivation film that resembles the one formed on lithium electrode in nonaqueous electrolyte must also be formed on a carbonaceous electrode via similar electrolyte decompositions, and only because... 

According to Peled s model, the existence of an SEI constitutes the foundation on which lithium ion chemistry could operate reversibly. Therefore, an ideal SEI should meet the following requirements (1) electron transference number 4 = 0 (otherwise, electron tunneling would occur and enable continuous electrolyte decomposition), (2) high ion conductivity so that lithium ions can readily migrate to intercalate into or deintercalate from graphene layers, (3) uniform morphology and chemical composition for ho-... 

There has been considerable controversy concerning the mechanism of SEI formation on a carbonaceous anode, but it is generally agreed that the initial electrolyte decomposition is responsible and that a competition among a variety of reactions involving the solvent as well as the salt components is also present. 

On the basis of the above observation, Dahn and co-workers proposed a thermal reaction scheme for the coupling of carbonaceous anodes and electrolytes. The initial peak, which was almost identical for all of the anode samples and independent of lithiation degrees, should arise from the decomposition of the SEI because the amount of SEI chemicals was only proportional to the surface area. This could have been due to the transformation of the metastable lithium alkyl carbonate into the stable Li2C03. After the depletion of the SEI, a second process between 150 and 190 °C was caused by the reduction of electrolyte components by the lithiated carbon to form a new SEI, and the autocatalyzed reaction proceeded until all of the intercalated lithium was consumed or the thickness of this new SEI was sufficient to suppress further reductions. The corresponding decrease in SHR created the dip in the least lithiated sample in Eigure 35. Above 200 °C (beyond the ARC test range as shown in Eigure 35), electrolyte decomposition occurred, which was also an exothermic process. 

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