The crystalline structure of di-lithium phthalocyanine (Li2Pc) is analyzed via a sequence of theoretical methods starting with ab-initio optimizations of a single molecule and dimers, followed by a series of classical molecular dynamics simulations that emulate four alternative crystalline structures. Calculated X-ray spectra are compared with those from experiments, and the results suggest that the features correspond to a dominant β-phase, although similarities in the calculated spectrum of alternative phases may imply the possible existence of polymorphism in this material. Since Li2Pc has been proposed as a solid electrolyte for lithium-ion batteries, the existence of ion-conducting channels is examined through the analyses of the simulated structures. Dynamical properties such as the lithium-ionic diffusion coefficient are determined through the velocity autocorrelation function and compared to experimental values.

Computational chemistry calculations performed with Gaussian 98 were used to develop an experimental method that facilitates ionic connection between the solid-state electrolyte dilithium phthalocyanine (Li 2 Pc) and manganese dioxide (MnO 2 ). The planar configuration of the phthalocyanine ring and the fact that the lithium ions are very close to the ring may sterically hinder effective ionic coupling between Li 2 Pc and any potential cathode. This same argument has been used for understanding the insertion and removal of magnesium from water solutions of deuteroporphyrins. Calculated results show that lithium ions are drawn closer to the phthalocyanine ring upon formation of (Li 2 Pc) 2 via molecular self-assembly when compared to the single-molecule Li 2 Pc. However, extension of lithium ions above the planar phthalocyanine ring in (Li 2 Pc) 2 can be enhanced through formation of a complex at the axial position above lithium. Calculations show that corannulene at the axial position above lithium forms an asymmetric structure with (Li 2 Pc) 2 and extends lithium further above the ring. To test the theoretical results, an electrically conducting carbon with a curved lattice was used in the fabrication of an all solid-state electrochemical cell with a lithium metal foil anode, Li 2 Pc electrolyte, and a MnO 2 cathode. Slow-scan-rate cyclic voltammograms of a Li x MnO 2 cathode demonstrate the charging and discharging of cells.During the last several years, we have been trying to develop a solid-state electrolyte that is a single-ion conductor for lithium ions where the transference number for lithium is equal to unity. We have referred to this solid-state electrolyte as a lithium-ion conducting channel. 1 The purpose of the channel is to provide a continuous negative electrostatic potential field for the lithium ion throughout the solid-state electrolyte. If there is a discontinuity of the negative electrostatic potential field within the channel, it is then reasoned that lithium-ion conduction would be terminated. The possibility exists for forming a continuous negative electrostatic potential field for lithium-ion conduction through molecular self-assembly of dilithium phthalocyanine (Li 2 Pc). Ab initio calculations discussed in this paper show that there are attractive forces between molecules of Li 2 Pc that favor formation of an assembled structure. Electrostatic potential calculations for a section of the assembled self-assembled structure suggest that one could have a continuous negative electrostatic potential field between individual molecules of Li 2 Pc throughout the molecular system for lithium-ion transport. Although these theoretical results were encouraging for using Li 2 Pc as a solid-state electrolyte, attempts at preparing functioning full electrochemical cells were not successful. In this regard, a potential problem area was the lack of electrical connection between the solid-state electrolyte and the solid-state cathode. Specifically, a lack of lithium-ion transfer between the electrolyte and...

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