Charge Storage and Aging Phenomena in Electrochemical Double Layer Capacitors (eBook, PDF)
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The storage of electrical charge in electrochemical double layer capacitors (EDLCs) is ideal for short-term energy storage in stationary and mobile or portable applications in which intermittent power demands and reliability are of prime importance. A significant limitation of the currently employed EDLC technology is the low energy density, whereby a promising approach towards increasing the energy content of present EDLC systems is a widening of the operational voltage window. However, a significant reduction of the device lifetime is observed under elevated voltage conditions.
In the p...
The storage of electrical charge in electrochemical double layer capacitors (EDLCs) is ideal for short-term energy storage in stationary and mobile or portable applications in which intermittent power demands and reliability are of prime importance. A significant limitation of the currently employed EDLC technology is the low energy density, whereby a promising approach towards increasing the energy content of present EDLC systems is a widening of the operational voltage window. However, a significant reduction of the device lifetime is observed under elevated voltage conditions.
In the present work, the contribution of interfacial charge transfer towards charge storage in and aging of EDLCs based on non-aqueous electrolyte solutions at elevated voltages is considered. The possible charge transfer mechanisms are thus conveniently classified as ionic or electronic. Through an improved understanding of these processes, possible routes for optimizing charge storage and avoiding aging at elevated voltages may be developed.
A coconut shell derived activated carbon was selected as electrode material in non-aqueous solutions of 1 M Et4NBF4 in acetonitrile (AN) and in propylene carbonate (PC). Through an electrochemical characterization of these systems via cyclic voltammetry, the potential regions of essentially ideal polarizability could be identified and separated from the regions in which irreversible charge transfer took place.
The region of ideal polarizability was characterized by in situ Raman spectroscopy, electrical resistance measurements and electrochemical dilatometry. The results are discussed in the context of those obtained on single-walled carbon nanotubes (SWCNTs) in order to establish a comparison with a high surface area electrode material of well-defined geometric and electronic structure. Fundamental differences in the reversible doping behavior of the two materials were observed, indicating that a conceptual representation of the carbonaceous framework of the activated carbon must take into account the presence of significant disorder and deviations from the idealized assembly of graphene fragments. Differences in the capacitive charging behavior could be attributed to the different electronic density of states of the materials, thus highlighting the importance of the electronic structure of carbonaceous electrodes for the storage of charge in EDLCs.
In order to investigate the possibility of ionic charge transfer in EDLC systems, the contribution of ion insertion processes to the charge storage and electrode degradation of both graphitic and activated carbon electrodes was studied using in situ electrochemical dilatometry, X-ray diffraction and small-angle X-ray scattering. It was found that the insertion of ions into graphite proceeds via well-defined intercalation sites, with the electrochemical intercalation of BF4– leading to staging and solvent cointercalation for both AN- and PC-based electrolytes. Further, the crystallinity of the graphitic electrodes was found to degrade markedly in the direction perpendicular to the graphene sheets, which could largely be attributed to the electrochemical decomposition of intercalated electrolyte species, i.e. a combination of ionic and electronic charge transfer.
On the the other hand, ion insertion processes in activated carbon could be attributed to the accumulation of ions within the confined insertion sites offered by micropores during charging. The steric requirements of these ions result in a macroscopically observable, reversible electrode expansion. A comparison with the expansion of entangled SWCNT electrodes and an expanded graphite electrode proved that the occupation of insertion sites depends directly on the electrode potential and the accessibility of the insertion site. As a particular example of this behavior, it was shown that the interstitial porosity of SWCNT bundles can be made accessible by electrochemical polarization, leading to an intrinsic capacitance enhancement. As an important conclusion, the accessibility of such sites must be evaluated in situ in order to determine their possible contribution to charge storage within the stability limits of the electrolyte solution.
Studies of the electronic charge transfer contribution towards the aging of EDLCs in the present work emphasized the possible formation of insoluble solid electrolyte degradation products. Systematic aging experiments using laboratory-scale test cells at elevated voltages enabled to distinguish between the loss of electrochemical performance and physicochemical modification of the activated carbon electrodes on the single electrode level. The rapid rate of aging at elevated voltages was found to depend notably on the solvent. In the AN-based electrolyte solution, the performance loss at a cell voltage of 3.5 V could be primarily attributed to the blockage of porosity at the positive electrode by the formation of solid degradation products within the porous structure of the activated carbon, most likely due to the oxidation of AN. This aging mechanism is promoted by the defluorination of the polymeric binder at the negative electrode, which results in unfavorable potential window shifts during aging. Preliminary studies regarding aging in the PC-based electrolyte indicated a different primary aging mechanism, likely due to reductive processes involving PC at the negative electrode. Notably, the detrimental effects of electrolyte degradation on the EDLC performance appeared to be significantly more pronounced than the contribution of ion insertion processes to aging.
Finally, suggestions for future research are made in order to deepen and exploit the insights gained regarding the insertion of ions in carbonaceous electrodes as well as the aging of EDLCs at elevated voltages.
Patrick Ruch was born in Atlanta, USA, in 1981 and studied Materials Science at the Swiss Federal Institute of Technology (ETH) in Zurich, Switzerland, followed by a dissertation at the Paul Scherrer Institut in the field of electrochemical energy storage. His academic and scientific efforts have been rewarded with the Willi Studer Prize of the ETH Zurich (2005), the Empa Research Award (2005), the Alu-Award of the Swiss Aluminium Association (2006) and the Young Author Award of the Oronzio and Niccolò De Nora Foundation (2008). The research interests of Dr. Ruch include materials engineering, renewable energy as well as energy conversion and storage.
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