DISCUSSION SECTION 1271tion of the amount of stored electrostatic charges (E = q/C, for a linear capacitor).P. J. Nigrey, 23 D. MacInnes, Jr.,23 D. P Nairns, 23 A. G. MacDiarmid, 23 and A. J. Heeger:24 The suggestion by Dr. Schuldiner that partially oxidized polyacetylene, (CH)x, e.g., , when used as the cathode in a (rechargeable) battery is actually a positively charged electrolytic capacitor plate was based on the assumption that the potential (E) of the polyacetylene cathode would be a simple function of the amount of stored electrostatic charge (E : q/c for a linear capacitor, where q --the magnitude of the stored electrostatic charge and c --the capacitance of the polyacetylene electrode). This assumption is incorrect.We have found during work carried out subsequently to submission of our paner discussed above that when the open-circuit voltage, Voc, of a (CH)~/1M LiC104 in propylene carbonate/Li cell is plotted as a function of the charge stored in the polyacetylene, the potential shows only a relatively small dependence on the magnitude of the stored charge above a doping level of ca. 1%, the semiconductor-metal transition. 25 Voc values were recorded at intervals during charging together with the amount of charge stored in the polyacetylene. In order to allow for some equilibration of the (C104)-ions in the (CH)x fibrils, the Voc values were measured, in each case, 5 min after the d-c power supply was disconnected. Charging was then immediately restarted to obtain further data points. The potential of parent, nonoxidized (CH)~ vs. a standard lithium electrode in this electrolyte is ca. 2.5V. The potential of the polyacetylene cathode increases by ca. 1.0V (to ca. 3.5V) on oxidizing it to 1% and increases an additional 0.3V (to 3.8V) on oxidation from 1 to 6%. Contrary to a conventional electrode, the potential of the polyacetylene cathode is not expected to be independent of the total quantity of stored electroactive species, since unlike a conventional cathode, the chemical composition (oxidation state) of the polyacetylene is constantly changing during the charging process from (CH~ to (CH+a)z to (CH+a+b)x to

No abstract

No abstract

Polyacetylene, false(CH)x can be controllably doped electrochemically through the semiconducting to the metallic regime using a solution of LiClCO4 in propylene carbonate and a lithium cathode. Flexible, golden, free‐standing films of false[CH+yfalse(ClO4)y−]x false(y=0 normalto 0.06false) having conductivities up to ∼103Ω−1 cm−1 are readily obtained. Electrochemical “undoping” of the false[CH+yfalse(ClO4)y−]x allows this doped film to be used as the cathode‐active material in lightweight rechargeable storage batteries. The overall complete discharge reaction isCH+0.06)(ClO40.06−x+0.06xnormalLi→CHx+0.06xLiClO4A 0.5 cm2 piece of the 6% doped film ( 1.0×0.5×0.01 normalcm ; ∼3 mg) exhibited an open‐circuit voltage of 3.7V and an initial short‐circuit current of 25 mA. No change in the open‐circuit voltage characteristics of a battery could be detected even after 326 successive constant current partial charge/discharge cycles. No degradation of the polyacetylene electrode was observed. Experimental energy densities of ∼176 W‐hr/Kg were obtained based on the weight of the false[CH+0.06false(ClO4−)0.06]x initially employed and the weight of Li consumed (exclusive of weights of electrolyte, solvent, and packaging material) during partial discharge when false[CH+0.06false(ClO4)0.06−]x was converted to false[CH+0.024false(ClO4)0.024−]x .

Aluminum I 2100Facile Synthesis of the Tridecameric Al13 Nanocluster Al 13 (μ 3 -OH) 6 (μ 2 -OH) 18 (H 2 O) 24 (NO 3 ) 15 . -The structures of title compound (II) and the strongly related compound (III) which contains extra ammonium and nitrate counterions are determined by single crystal XRD. Both compounds crystallize in the triclinic space group P1 with Z = 1 and contain nearly identical [Al13(OH)24(H2O)24] 15+ cluster cations consisting of planar centrosymmetric Anderson-Type Al(μ 3 -OH) 6 Al 6 (μ 2 -OH) 6 core fragments surrounded by six Al atoms. -(GATLIN, J. T.; MENSINGER, Z. L.; ZAKHAROV, L. N.; MACINNES, D.; JOHNSON*, D.; Inorg.