John B. Kerr

Design of an Electrochemical Cell Making Syngas (CO + H2) from CO2 and H2O Reduction at Room Temperature

An electrolysis-cell design for simultaneous electrochemical reduction of CO 2 and H 2 O to make syngas (CO + H 2 ) at room temperature (25°C) was developed, based on a technology very close to that of proton-exchange-membrane fuel cells (PEMFC), i.e., based on the use of gas-diffusion electrodes so as to achieve high current densities. While a configuration involving a proton-exchange membrane (Nafion) as electrolyte was shown to be unfavorable for CO 2 reduction, a modified configuration based on the insertion of a pH-buffer layer (aqueous KHCO 3 ) between the silver-based cathode catalyst layer and the Nafion membrane allows for a great enhancement of the cathode selectivity for CO 2 reduction to CO [ca. 30 mA/cm 2 at a potential of -1.7 to -1.75 V vs SCE (saturated-calomel reference electrode)]. A CO/H 2 ratio of 1/2, suitable for methanol synthesis, is obtained at a potential of ca. -2 V vs SCE and a total current density of ca. 80 mA/cm 2 . An issue that has been identified is the change in product selectivity upon long-term electrolysis. Results obtained with two other cell designs are also presented and compared.

Diagnostic Characterization of High Power Lithium-Ion Batteries for Use in Hybrid Electric Vehicles

A baseline cell chemistry was identified as a carbon anode, LiNi 0.8 Co 0.2 O 2 cathode, and diethyl carbonate-ethylene carbonate LiPF 6 electrolyte, and designed for high power applications. Nine 18650-size advanced technology development cells were tested under a variety of conditions. Selected diagnostic techniques such as synchrotron infrared microscopy, Raman spectroscopy, scanning electronic microscopy, atomic force microscopy, gas chromatography, etc., were used to characterize the anode, cathode, current collectors and electrolyte taken from these cells. The diagnostic results suggest that the four factors that contribute to the cell power loss are solid electrolyte interphase deterioration and nonuniformity on the anode; morphology changes, increase of impedance, and phase separation on the cathode; pitting corrosion on the cathode current collector; and decomposition of the LiPF 6 salt in the electrolyte at elevated temperature.

Comparison of lithium-polymer cell performance with unity and nonunity transference numbers

Abstract This work compares the performance of lithium batteries with polymer electrolytes with unity (“ionomer”) and nonunity (“polymer electrolyte”) transference numbers. The study is performed with respect to a particular cell chemistry, Li metal∣polymer∣LiV 6 O 13 -composite electrode, which is currently a top candidate for use in electric vehicles. Cell performance was modeled to determine the best possible performance of cells containing four different electrolytes: “ideal” polymer membrane and ionomer with properties defined by USABC goals, and the presently best available polymer electrolyte and ionomer. Positive electrode thickness, porosity, and current density were varied to find the cell geometry with the highest combined energy density and peak power performance for cells with each electrolyte, and concentration and potential profiles are examined to determine the limitations of the electrolytes. The results show that at 40°C, the “ideal” polymer electrolyte can provide 104 W h/kg and 99 W p /kg, the “ideal” ionomer can provide 94 W h/kg and 58 W p /kg, and the currently available electrolytes can provide about one-fifth of these values.

The Formation Mechanism of Fluorescent Metal Complexes at the LixNi0.5Mn1.5O4−δ/Carbonate Ester Electrolyte Interface

Electrochemical oxidation of carbonate esters at the Li(x)Ni(0.5)Mn(1.5)O(4-δ)/electrolyte interface results in Ni/Mn dissolution and surface film formation, which negatively affect the electrochemical performance of Li-ion batteries. Ex situ X-ray absorption (XRF/XANES), Raman, and fluorescence spectroscopy, along with imaging of Li(x)Ni(0.5)Mn(1.5)O(4-δ) positive and graphite negative electrodes from tested Li-ion batteries, reveal the formation of a variety of Mn(II/III) and Ni(II) complexes with β-diketonate ligands. These metal complexes, which are generated upon anodic oxidation of ethyl and diethyl carbonates at Li(x)Ni(0.5)Mn(1.5)O(4-δ), form a surface film that partially dissolves in the electrolyte. The dissolved Mn(III) complexes are reduced to their Mn(II) analogues, which are incorporated into the solid electrolyte interphase surface layer at the graphite negative electrode. This work elucidates possible reaction pathways and evaluates their implications for Li(+) transport kinetics in Li-ion batteries.

Nonprecious Metal Catalysts for Fuel Cell Applications: Electrochemical Dioxygen Activation by a Series of First Row Transition Metal Tris(2-pyridylmethyl)amine Complexes

A series of divalent first row triflate complexes supported by the ligand tris(2-pyridylmethyl)amine (TPA) have been investigated as oxygen reduction catalysts for fuel cell applications. [(TPA)M(2+)](n+) (M = Mn, Fe, Co, Ni, and Cu) derivatives were synthesized and characterized by X-ray crystallography, cyclic voltammetry, NMR spectroscopy, magnetic susceptibility, IR spectroscopy, and conductance measurements. The stoichiometric and electrochemical O(2) reactivities of the series were examined. Rotating-ring disk electrode (RRDE) voltammetry was used to examine the catalytic activity of the complexes on a carbon support in acidic media, emulating fuel cell performance. The iron complex displayed a selectivity of 89% for four-electron conversion and demonstrated the fastest reaction kinetics, as determined by a kinetic current of 7.6 mA. Additionally, the Mn, Co, and Cu complexes all showed selective four-electron oxygen reduction (<28% H(2)O(2)) at onset potentials (~0.44 V vs RHE) comparable to state of the art molecular catalysts, while being straightforward to access synthetically and derived from nonprecious metals.

Performance limitations of polymer electrolytes based on ethylene oxide polymers

Abstract Studies of polymer electrolyte solutions for lithium-polymer batteries are described. Two different salts, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium trifluoromethanesulfonate (LiTf), were dissolved in a variety of polymers. The structures were all based upon the ethylene oxide unit for lithium ion solvation, and both linear and comb-branch polymer architectures have been examined. Conductivity, salt diffusion coefficient and transference number measurements demonstrate the superior transport properties of the LiTFSI salt over LiTf. Data obtained on all of these polymers combined with LiTFSI salts suggest that there is a limit to the conductivity achievable at room temperature, at least for hosts containing ethylene oxide units. The apparent conductivity limit is 5×10 −5 S/cm at 25°C. Providing that the polymer chain segment containing the ethylene oxide units is at least 5–6 units long, there appears to be little influence of the polymer framework to which the solvating groups are attached. To provide adequate separator function, the mechanical properties may be disconnected from the transport properties by selection of an appropriate architecture combined with an adequately long ethylene oxide chain. For both bulk and interfacial transport of the lithium ions, conductivity data alone is insufficient to understand the processes that occur. Lithium ion transference numbers and salt diffusion coefficients also play a major role in the observed behavior and the transport properties of these polymer electrolyte solutions appear to be quite inadequate for ambient temperature performance. At present, this restricts the use of such systems to high temperature applications. Several suggestions are given to overcome these obstacles.

Compatibility of Li x Ti y Mn1 − y O2 ( y = 0 , 0.11 ) Electrode Materials with Pyrrolidinium-Based Ionic Liquid Electrolyte Systems

The possibility of using electrolyte systems based on room-temperature ionic liquids (RTILs) in lithium-battery configurations is discussed. The nonflammability and wide potential windows of RTIL-based systems are attractive potential advantages, which may ultimately lead to the development of safer, higher energy density devices than those that are currently available. An evaluation of the compatibility of these electrolyte systems with candidate electrodes is critical for further progress. A comparison of the electrochemical behavior of Li/RTIL/Li x MnO 2 and Li x Ti 0.11 Mn 0.89 O 2 cells with those containing conventional carbonate solutions is presented and discussed in terms of the physical properties of two RTIL systems and their interactions with the cathodes. Strategies to improve performance and minimize cathode dissolution are presented.

An Investigation of the Effect of Graphite Degradation on the Irreversible Capacity in Lithium-ion Cells

An Investigation of the Effect of Graphite Degradation on the Irreversible Capacity in Lithium-ion Cells Laurence J. Hardwick * , Marek Marcinek a* , Leanne Beer, John B. Kerr*, Robert Kostecki b,* Environmental Energy Technologies Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA a Electrochemical Society Active Member Present address: The Warsaw University of Technology, Noakowskiego 3, 00-664, Warsaw, Poland b Corresponding author: r_kostecki@lbl.gov, tel: (1) 510 486 6002, fax: (1) 510 486 7303

Transport properties of a high molecular weight poly(propylene oxide)-LiCF{sub 3}SO{sub 3} system

Conductivities ({sigma}), salt diffusion coefficients (D{sub s}), and cationic transference numbers (t{sub +}{sup 0}) are reported for a high molecular weight polypropylene oxide (Parel{trademark})-LiCF{sub 3}SO{sub 3} polymer electrolyte system at 85 C. Transference numbers were determined as a function of salt concentration using a recently described electrochemical method based on concentrated solution theory. For the Parel-LiCF{sub 3}SO{sub 3} system, t{sub +}{sup 0} is slightly positive for electrolytes with O:Li ratios of 15 or 12:1 but decreases to negative values for more concentrated solutions. This implies that negatively charged ionic aggregates such as triplets are more mobile than free cations in this concentration range. Such behavior is commonly seen in binary salt/polymer electrolytes, which typically exhibit a high degree of nonideality. The nonunity transference numbers and microphase separation in the Parel-LiCF{sub 3}SO{sub 3} system strongly suggest that salt precipitation or phase separation in operating cells containing these electrolytes due to the development of large concentration gradients during passage of current.

From molecular models to system analysis for lithium battery electrolytes

The behavior of polymer electrolytes in lithium batteries is reviewed in the context of molecular scale models as well as on the system scale. It is shown how the molecular structure of the electrolyte strongly influences ion transport through the polymer as well as across the interfaces and determines the values of a number of parameters needed for system models that can predict the performance of the battery (e.g. κ, D, t0+ and i0). The interaction of the electrolyte with the electrodes not only leads to transfer of the lithium ion across the interface but also to side reactions that profoundly influence the calendar and life cycle of the battery. Typically these electrochemically induced side reactions generate the SEI layer, but inherent instability of the bulk electrolyte may also play a role in the formation of surface layers. These various reactions can lead to changes in the mechanical properties of the separator and electrode structure that promote life-limiting phenomena such as dendrite growth, passivation and morphology changes. The rheological model of Eisenberg is drawn upon to show how the interactions of the electrolyte with surfaces can lead to distinct changes in mechanical and transport properties that may limit the battery performance and lead to diminished performance with time. The molecular level models may be combined with the rheological models to provide workable models of the interfaces and bulk electrolyte dynamics that in turn can be used to provide a more accurate level of performance prediction from the system models. This connects molecular structure with battery performance and guides the design and synthesis of new and better materials.