Hard carbons

Formation of a Tr-allylpalladium complex 29 takes place by the oxidative addition of allylic compounds, typically allylic esters, to Pd(0). The rr-allylpal-ladium complex is a resonance form of ir-allylpalladium and a coordinated tt-bond. TT-Allylpalladium complex formation involves inversion of stereochemistry, and the attack of the soft carbon nucleophile on the 7r-allylpalladium complex is also inversion, resulting in overall retention of the stereochemistry. On the other hand, the attack of hard carbon nucleophiles is retention, and hence Overall inversion takes place by the reaction of the hard carbon nucleophiles. 

The phenylation of styrene with phenyl Grignard reagents as a hard carbon nucleophile proceeds in 75% yield in the presence of PdCl2, LiCl, and K2CO3 at room temperature to give stilbene (207). Selection of the solvent is crucial and the best results are obtained in MeCN. The reaction can be made catalytic by the use of CuCl2[197]. Methyllithium reacts with styrene in the presence of Pd(acac)2 or Pd(OAc)2 to give /3-methylstyrene (208) in 90% yield[198]. 

Hard carbon nucleophiles of organometallic compounds react with 7r-allyl-palladium complexes. A steroidal side-chain is introduced regio- and stereo-selectively by the reaction of the steroidal 7T-allylpalladium complex 319 with the alkenylzirconium compound 320[283]. 

In addition, a catalytic version of Tt-allylpalladium chemistry has been devel-oped[6,7]. Formation of the Tr-allylpalladium complexes by the oxidative addition of various allylic compounds to Pd(0) and subsequent reaction of the complex with soft carbon nucleophiles are the basis of catalytic allylation. After the reaction, Pd(0) is reformed, and undergoes oxidative addition to the allylic compounds again, making the reaction catalytic.-In addition to the soft carbon nucleophiles, hard carbon nucleophiles of organometallic compounds of main group metals are allylated with 7r-allylpalladium complexes. The reaction proceeds via transmetallation. These catalytic reactions are treated in this chapter. 

The stereochemistry of the Pd-catalyzed allylation of nucleophiles has been studied extensively[5,l8-20]. In the first step, 7r-allylpalladium complex formation by the attack of Pd(0) on an allylic part proceeds by inversion (anti attack). Then subsequent reaction of soft carbon nucleophiles, N- and 0-nucleophiles proceeds by inversion to give 1. Thus overall retention is observed. On the other hand, the reaction of hard carbon nucleophiles of organometallic compounds proceeds via transmetallation, which affords 2 by retention, and reductive elimination affords the final product 3. Thus the overall inversion is observed in this case[21,22]. 

Cross-Couplinf of Allylic Groups with Hard Carbon Nucleophiles... 

Dienes and allylarcncs can be prepared by the Pd-catalyzcd coupling of allylic compounds with hard carbon nucleophiles derived from alkenyl and aryl compounds of main group metals. Allylic compounds with various leaving groups can be used. Some of them are unreactive with soft nucleophiles, but... 

The reaction of 2,3-butadienyl acetate (843) with soft carbon nucleophiles such as dimethyl malonate gives dimethyl 2,3-butadienylmalonate (844)[520]. On the other hand, the reaction of the 2,3-butadienyl phosphate 845 with hard carbon nucleophiles such as Mg and Zn reagents affords the 2-allcyl-1,3-butadiene 846[520,521]. The 3-methoxy-1,3-butadiene 848 is obtained by the reaction of the 2-methoxy-2,3-butadienyl carbonate 847 with organozinc reagent. 

Among several propargylic derivatives, the propargylic carbonates 3 were found to be the most reactive and they have been used most extensively because of their high reactivity[2,2a]. The allenylpalladium methoxide 4, formed as an intermediate in catalytic reactions of the methyl propargylic carbonate 3, undergoes two types of transformations. One is substitution of cr-bonded Pd. which proceeds by either insertion or transmetallation. The insertion of an alkene, for example, into the Pd—C cr-bond and elimination of/i-hydrogen affords the allenyl compound 5 (1.2,4-triene). Alkene and CO insertions are typical. The substitution of Pd methoxide with hard carbon nucleophiles or terminal alkynes in the presence of Cul takes place via transmetallation to yield the allenyl compound 6. By these reactions, various allenyl derivatives can be prepared. 

Hydrochloric Rubber Hard Carbon Steel Rubber or Ring Rubber Rubber ... 

Fig. 2. The master graph of reversible capacity for lithium plotted versus heat treatment temperature for a variety of carbon samples. The three regions of commereial relevance are marked. Solid symbols are data for soft carbons, open symbols are data for hard carbons.

Lithium insertion in microporous hard carbons (region 3 in Fig. 2) is described in section 6. High capacity hard carbons can be made from many precursors, such as coal, wood, sugar, and different types of resins. Hard carbons made from resole and novolac resins at temperatures near 1000°C have a reversible capacity of about 550 mAh/g, show little hyteresis and have a large low voltage plateau on both discharge and charge. The analysis of powder X-ray diffraction. 

The single-point BET surface area measurement was used to check for open pores. The results for some soft and hard carbon samples heated at 700°C and 1000°C are presented in Table 2 for comparison. The hard carbon samples studied here have about ten times more open porosity than the soft carbons. 

F igure 21 compares the voltage-capacity profiles for the second cycle of lithium/carbon electrochemical cells made from OXY, a representative hard carbon, and those for samples made from CRO, a representative soft carbon. 

Microporous Carbons from Pyrolyzed Hard-Carbon Precursors... 

Fig. 24. Adsorption of lithium on the internal surfaces of micropores formed by single, bi, and trilayers of graphene sheets in hard carbon.

In lithium-ion battery applications, it is important to reduce the cost of electrode materials as much as possible. In this section, we will discuss hard carbons with high capacity for lithium, prepared from phenolic resins. It is also our goal, to collect further evidence supporting the model in Fig. 24. 

A hard carbon with high capacity can be made from epoxy novolac resin [12]. The epoxy resins used cost about US 2.50 per pound and give pyrolysis yields between 20 and 30%. However, it is well known that phenolic (or phenol-formaldehyde) resins can be pyrolyzed to give hard carbons with a yield of over 50% [42]. In addition, these resins cost about USSl.OO per pound. Phenolic resins therefore offer significant cost advantages over epoxy resins, so we... 

Powder X-ray diffraction and SAXS were employed here to explore the microstructure of hard carbon samples with high capacities. Powder X-ray diffraction measurements were made on all the samples listed in Table 4. We concentrate here on sample BrlOOO, shown in Fig. 27. A weak and broad (002) Bragg peak (near 22°) is observed. Well formed (100) (at about 43.3°) and (110) (near 80°) peaks are also seen. The sample is predominantly made up of graphene sheets with a lateral extension of about 20-30A (referring to Table 2, applying the Scherrer equation to the (100) peaks). These layers are not stacked in a parallel fashion, and therefore, there must be small pores or voids between them. We used SAXS to probe these pores. 

F ig. 29. Schematic graph showing the definition of the parameter, R, used to empirically estimate the fraction of single graphene layers in hard carbon samples. 

Sony Energytec uses a disordered hard carbon of the type described in region 3 of Fig. 2. These carbons have been produced by a number of Japanese manufacturers including Kureha [41] and Mitsubishi Gas [40], Our recent work [44], and other work in the patent literature shows how such carbons can be produced from natural precursors like sugar and wood. This suggests that it should ultimately be possible to prepare such carbons very cheaply. The specific capacity of region-3 carbons which are in commercial production are around 500 mAh/g. 

There are many kinds of carbon materials, with different crystallinity. Their crystallinity generally develops due to heat-treatment in a gas atmosphere ("soft" carbon). However, there are some kinds of carbon ("hard" carbon) in which it is difficult to develop this cristallinity by the heat-treatment method. Both kinds of carbon materials are used as the negative electrode for lithium-ion batteries. 

Both hard and soft carbons are used as negative electrode materials for lithium-ion batteries. Hard carbon is made by heat-treating organic polymer materials such as phenol resin. The heat-treatment tempera-... 

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