Surface groups, carbons

Biniak, S. et al.. The characterization of activated carbons with oxygen and nitrogen surface groups. Carbon, 35, 1799, 1997. 

In addition, carbon-hydrogen bonds are present, particularly in carbonaceous materials obtained by carbonizing polymers at low temperatures, typically <1000 °C. Detailed discussions on the types of surface groups and their surface concentrations are presented by Boehm (14] and Rivin [15],... 

The surface oxide groups on carbon play a major role in its surface properties for example, the wettability in aqueous electrolytes, work function, and pH in water are strongly affected by the presence of surface groups on the carbonaceous material. Typically, the wettability of carbon... 

The physicochemical properties of carbon are highly dependent on its surface structure and chemical composition [66—68], The type and content of surface species, particle shape and size, pore-size distribution, BET surface area and pore-opening are of critical importance in the use of carbons as anode material. These properties have a major influence on (9IR, reversible capacity <2R, and the rate capability and safety of the battery. The surface chemical composition depends on the raw materials (carbon precursors), the production process, and the history of the carbon. Surface groups containing H, O, S, N, P, halogens, and other elements have been identified on carbon blacks [66, 67]. There is also ash on the surface of carbon and this typically contains Ca, Si, Fe, Al, and V. Ash and acidic oxides enhance the adsorption of the more polar compounds and electrolytes [66]. 

It has been suggested that the active sites for tiie ODE reaction over carbon catalysts are the basic surface groups [4]. As the air-treated composite possesses the greatest amount of CO-forming surface groups based on the sample wei t, while the HN03-treated composite... 

Due to their moderate specific surface area, carbon nanotubes alone demonstrate small capacitance values. However, the presence of heteroatoms can be a source of pseudocapacitance effects. It has been already proven that oxygenated functional groups can significantly enhance the capacitance values through redox reactions [11]. Lately, it was discovered that nitrogen, which is present in carbon affects also the capacitance properties [12]. 

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. 

There are various possibilities for functional groups on the surface of carbonates, sulfides, phosphates etc. Using a very simple approach similar to the one in Fig. 2.1 for hydrous oxides one could postulate surface groups for carbonates (e.g., FeC03) and sulfides (e.g., ZnS), as follows ... 

Abstracting from the complexity of the real systems, there is one common property of all natural particles. Their surfaces contain functional groups which can interact with H+, OH and metal ions and - if Lewis acid sites, e.g., =AI and =Fe, are available on the surface - with ligands. Many inorganic solids (oxidesQand silicates) contain hydroxo groups carbonates and sulfides expose -C-oh,-c oh, MeOH and -SH groups, respectively. While the interaction of alkaline and earth-alkaline ions... 

The hydrothermal carbons obtained in the end from soluble, non-structural carbohydrates are micrometer sized, spherically shaped particle dispersions, containing a sp2 hybridized backbone (also responsible for the brown to black color) decorated with a dense layer of polar oxygenated functionalities still remaining from the original carbohydrate. The presence of these surface groups offers the possibility of further functionalization and makes the materials more hydrophilic and well-dispersible in water. The size of the final particles depends mainly on the carbonization time and precursor concentration inside the autoclave, as well as additives and stabilizers potentially added to the primary reaction recipe. An SEM image of a model reaction illustrating this dispersion state is shown in Fig. 7.1. 

Fig. 15.5 Oxygen and nitrogen surface groups on carbon, (a) lactone, (b) carboxylic anhydride,...

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