On the Structure of Porous Poly(vinylidene fluoride) Membrane Prepared by Phase Inversion from Water-NMP-PVDF System
A PVDF membrane was prepared by isothermal immersion precipitation of a PVDF/NMP solution from pure water bath. FESEM imaging of the formed membrane revealed its porous structure, featuring tight skin, macrovoids, and cellular pores. These structural characteristics were common to membranes that were formed by precipitation of amorphous polymers from harsh nonsolvents. Evidence of crystallization in the present PVDF membrane could be observed on the surfaces of the various pores in the form of branching dendrites.
UNDERSTANDING AND IMPROVING MANUFACTURING PROCESSES FOR MAKING LITHIUM-ION BATTERY ELECTRODES
OF DISSERTATION UNDERSTANDING AND IMPROVING MANUFACTURING PROCESSES FOR MAKING LITHIUM-ION BATTERY ELECTRODES Lithium-ion batteries (LIBs) have been widely used as the most popular rechargeable energy storage and power sources in today’s portable electronics, electric vehicles, and plug-in hybrid electric vehicles. LIBs have gained much interest worldwide in the last three decades because of their high energy density, voltage, rate of charge and discharge, reliability, and design flexibility. I am exploring the possibility of developing battery manufacturing technologies that would lower the cost, reduce the environmental impact, and increase cell performance and durability. This dissertation is focused firstly on understanding the effect of mixing sequence (the order of introducing materials) and optimizing the electrode fabrication for the best electrochemical performance, durability, lower cost, and improve the existing manufacturing processes. The electrode system consists of active material, polymer binder, conductive agent, and solvent. I have investigated four different mixing sequences to prepare the slurries for making the positive electrode. The key sequencerelated factor appears to be whether the active material and conductive agent are mixed in the presence of or prior to the introduction of the binder solution. The mixing sequences 1, 2, 3, and 4 were optimized, and the rheological behavior of the slurries, morphology, conductivity, and mechanical and electrochemical properties of electrodes were investigated. Slurries from sequences 1 and 4 show different rheological properties from 2 and 3. The amount of NMP required to achieve a comparable final slurry viscosity differed significantly for the sequences under study. The sequence 1 shows better long-term cycling behavior than sequences 2, 3 and 4. This study quantifies the link between electrode slurry mix parameters and electrode quality. Secondly, a new method of making lithium-ion battery electrodes by adapting an immersion precipitation (IP) technology commonly used in membrane manufacturing was developed and demonstrated. The composition, structure, and electrochemical performance of the electrode made by the IP method were compared favorably with that made by the conventional method. The toxic and expensive organic solvent (NMP) was captured in coagulation bath instead of being released to the atmosphere. The IP electrodes show an excellent performance and durability at potentially lower cost and less environmental impact. Thirdly, I have developed and demonstrated a solvent-free dry-powder coating process for making LiNi1/3Mn1/3Co1/3O2 (NMC) positive electrodes in lithium-ion batteries, and compared the performance and durability of electrodes made by the drypowder coating processes with that by wet-slurry coating processes. The technology that has been used is the electrostatic spray deposition (ESD) process. This process eliminates volatile organic compound emission, reduces thermal curing time from hours to minutes, and offers high deposition rates onto large surfaces. The long-term cycling shows that the dry-powder coated electrodes have similar performance and durability as the conventional wet-slurry made electrodes.
The transport properties of polyimide isomers containing hexafluoroisopropylidene in the diamine residue
The effect of modification of the central moiety of the dianhydride residue and isomerism on the gas transport and physical properties were compared for six polyimides containing the hexafluoroisopropylidene group in the diamine residue. Substitution of bulkier groups within the dianhydride residue resulted in disruption of chain packing and slight increases in resistance to chain motions which led to an increase in permeability with little loss in selectivity. The permeabilities and diffusivities in the meta connected polyimide isomers were considerably lower than in the para connected polyimide isomers. Similarly, the permselectivities in the meta connected isomers were consistently higher than in the para connected isomers. These lower permeabilities and higher permselectivities were a result of the more dense packing and a significant suppression of small scale motions in the meta connected isomers. The suppression of segmental mobility in the meta connected isomers was indicated by an increase in the sub Tg transition temperatures in these materials relative to the para connected isomers. The differences in transport properties for these polyimides were attributed to contributions by several factors, including: (1) total free volume (2) distribution of free volume (3) intersegmental resistance to chain motions, and (4) intrasegmental resistance to chain motions. © 1994 John Wiley & Sons, Inc.