Electrolyte materials liquid/polymer gels

The electrochemically active electrode materials in Li-ion batteries are a lithium metal oxide for the positive electrode and lithiated carbon for the negative electrode. These materials are adhered to a metal foil current collector with a binder, typically polyvinylidene fluoride (PVDF) or the copolymer polyvinylidene fluoride-hexafluroropropylene (PVDF-HFP), and a conductive diluent, typically a high-surface-area carbon black or graphite. The positive and negative electrodes are electrically isolated by a microporous polyethylene or polypropylene separator film in products that employ a liquid electrolyte, a layer of gel-polymer electrolyte in gel-polymer batteries, or a layer of solid electrolyte in solid-state batteries. 

Various workers have studied electrol5des made by blending ionic liquids with solvents [3536,43,51,61-63], polymer electrolytes [26,48303538,64-68], polymers as electrode binders [21,4833,69] and ionomers whereby elements of the ionic liquids are incorporated into the pol)rmer backbone [70-75]. Such work has opened up new fields for these materials and simultaneously blurred the distinctions among ionic liquids, and rubber, glassy, gel, ionomer and polymer electrolytes. This is exemplified by a complex scheme in a review by AngeU [26]. hi this chapter, we have included such materials only when the salt forms the major component of the electrolyte, such as polymer-in-a-salt electrolytes or PISE [76,77]. 

The solidity of gel electrolytes results from chain entanglements. At high temperatures they flow like liquids, but on cooling they show a small increase in the shear modulus at temperatures well above T. This is the liquid-to-rubber transition. The values of shear modulus and viscosity for rubbery solids are considerably lower than those for glass forming liquids at an equivalent structural relaxation time. The local or microscopic viscosity relaxation time of the rubbery material, which is reflected in the 7], obeys a VTF equation with a pre-exponential factor equivalent to that for small-molecule liquids. Above the liquid-to-rubber transition, the VTF equation is also obeyed but the pre-exponential term for viscosity is much larger than is typical for small-molecule liquids and is dependent on the polymer molecular weight. 

Solid polymer and gel polymer electrolytes could be viewed as the special variation of the solution-type electrolyte. In the former, the solvents are polar macromolecules that dissolve salts, while, in the latter, only a small portion of high polymer is employed as the mechanical matrix, which is either soaked with or swollen by essentially the same liquid electrolytes. One exception exists molten salt (ionic liquid) electrolytes where no solvent is present and the dissociation of opposite ions is solely achieved by the thermal disintegration of the salt lattice (melting). Polymer electrolyte will be reviewed in section 8 ( Novel Electrolyte Systems ), although lithium ion technology based on gel polymer electrolytes has in fact entered the market and accounted for 4% of lithium ion cells manufactured in 2000. On the other hand, ionic liquid electrolytes will be omitted, due to both the limited literature concerning this topic and the fact that the application of ionic liquid electrolytes in lithium ion devices remains dubious. Since most of the ionic liquid systems are still in a supercooled state at ambient temperature, it is unlikely that the metastable liquid state could be maintained in an actual electrochemical device, wherein electrode materials would serve as effective nucleation sites for crystallization. 

Figure 17.14 Steady-state voltammetry of a liquid and polymer (PVDF-HFP) gel electrolyte at a Pt ultramicroelectrode. Scan speed lOmV/s. Reprinted by permission from Mac Millan Publishers Ltd Nature Materials, 2003, 2, 402.

Both the anode and the cathode are composed of a coating of the electrochemically active material onto a current collector (copper or aluminum). Another key component of the battery is the separator that physically separates the two electrodes and prevents contact between them. In the case of a liquid technology battery, a polyolefin separator is typically used and a liquid electrolyte is used to transport the Li ions from one side of the porous separator to the other. In the case of a polymer Li ion battery, a polymer, such as PVDF, is used to form a porous structure, which is then swollen with a Li" " conducting liquid electro-lyte. " This results in a gel-type electrolyte, which plays the dual role of electrolyte and separator, with no free liquid present. 

Pandey, G. P, and S. A. Hashmi. 2013. Ionic liquid l-ethyl-3-methylimidazolium tetracyanoborate-based gel polymer electrolyte for electrochemical capacitors. Journal of Materials Chemistry A 1 3372-3378. 

Hashmi and Upadhyaya compared the electrochemical properties of the electrochemically synthesized MnO /PPy composite electrodes, fabricated with different electrolytes, namely polymer electrolyte film (polyvinyl alcohol [PVA]-HjPO aqueous blend), aprotic liquid electrolyte (LiClO -propylene carbonate [PC]), and polymeric gel electrolyte (poly methyl methacrylate [PMMA]-ethylene carbonate [EC]-PC-NaClO ) [60]. The cell with aqueous PVA-H PO showed non-capacitive behavior owing to some reversible chemical reaction of MnO with water, while the MnO / PPy composite was found to be a suitable electrode material for redox supercapacitors with aprotic (non-aqueous) electrolytes. The solid-state supercapacitor based on the MnO /PPy composite electrodes with gel... 

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