FEM modelling of a coaxial three-electrode test cell for electrochemical impedance spectroscopy in lithium ion batteries

Klink, Stefan; Höche, Daniel; Mantia, Fabio La; Schuhmann, Wolfgang

doi:10.1016/j.jpowsour.2013.03.186

Cited by 46 publications

(42 citation statements)

References 16 publications

(9 reference statements)

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“…The modified equivalent circuit model of the system is provided in Figure 5b. [41][42][43] The parameter Rs is the electrolyte resistance; CPE1 and R f are the capacitance and resistance, respectively, of the passivation SEI film formed on the electrode surface; CPE2 and R ct are the double-layer capacitance and charge transfer resistance, respectively; and Zw is the Warburg impedance related to the diffusion of lithium ions into the bulk of the electrode. For the NiCo 2 S 4 NSA/carbon cloth electrode, the fitted impedance parameters were R f = 17.42 Ω, and R ct = 81.75 Ω; for the NiCo 2 S 4 flower electrode, R f = 54.11 Ω and R ct = 96.79 Ω.…”

Section: D-networked Nico 2 S 4 Nsas As Anodes In Libsmentioning

confidence: 99%

Three-dimensional-networked NiCo2S4 nanosheet array/carbon cloth anodes for high-performance lithium-ion batteries

et al. 2015

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We present the design and synthesis of three-dimensional (3D)-networked NiCo 2 S 4 nanosheet arrays (NSAs) grown on carbon cloth along with their novel application as anodes in lithium-ion batteries. The relatively small (~60%) volumetric expansion of NiCo 2 S 4 nanosheets during the lithiation process was confirmed by in situ transmission electron microscopy and is attributed to their mesoporous nature. The 3D network structure of NiCo 2 S 4 nanosheets offers the additional advantages of large surface area, efficient electron and ion transport capability, easy access of electrolyte to the electrode surface, sufficient void space and mechanical robustness. The fabricated electrodes exhibited outstanding lithium-storage performance including high specific capacity, excellent cycling stability and high rate of performance. A reversible capacity of~1275 mAh g − 1 was obtained at a current density of 1000 mA g − 1 , and the devices retained~1137 mAh g − 1 after 100 cycles, which is the highest value reported to date for electrodes made of metal sulfide nanostructures or their composites. Our results suggest that 3D-networked NiCo 2 S 4 NSA/carbon cloth composites are a promising material for electrodes in high-performance lithium-ion batteries. INTRODUCTIONRechargeable lithium-ion batteries (LIBs) are the most widely used electrochemical energy storage devices because of their inherent advantages including high energy density, long life span, lack of memory effect and environmental nontoxicity. 1-3 The increasing applications of LIBs in daily electronic devices-along with industry demands for further improvement in energy density, durability, rate capability and safety-have driven the development of new electrode materials and new electrode structures. [4][5][6][7] Among the great variety of anode materials studied, metal oxides (MOs) and metal sulfides ( 21 have been synthesized and offer superior electrochemical energy storage capacity compared with bulk MSs. However, the large volumetric change of MS nanostructures during electrochemical reactions leads to reduced capacity and poor cycling stability. Moreover, the necessary addition of conductive additives and binders inevitably lessens overall energy

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Section: D-networked Nico 2 S 4 Nsas As Anodes In Libsmentioning

confidence: 99%

Three-dimensional-networked NiCo2S4 nanosheet array/carbon cloth anodes for high-performance lithium-ion batteries

et al. 2015

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“…13 Yet, experiments and numerical simulations by Ender et al 14 showed that the impedance measurements with the latter reference electrode placement can display significant distortions caused by small in-plane offsets between anode and cathode (referred to as geometrical asymmetry) and/or by large differences in the impedance response of anode and cathode (referred to as electrical asymmetry), consistent with earlier work by Dees et al 15 This is also the case for coaxially located reference electrodes, for which the measured anode or cathode impedance is shown to be highly sensitive toward misplacements of the electrodes. 10,12,16 * Electrochemical Society Student Member. * * Electrochemical Society Fellow.…”

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A Gold Micro-Reference Electrode for Impedance and Potential Measurements in Lithium Ion Batteries

Solchenbach

Pritzl

Kong

et al. 2016

J. Electrochem. Soc.

141

227

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Impedance measurements of lithium-ion batteries are a powerful tool to investigate the electrolyte/electrode interface. To separate the contributions of anode and cathode to the full-cell impedance, a reference electrode is required. However, if the reference electrode is placed inappropriately, the impedance response can easily be biased and lead to erroneous conclusions. In this study, we present a novel micro-reference electrode for Swagelok-type T-cells which is suitable for long-term impedance and reference potential measurements. The reference electrode consists of a thin insulated gold wire, which is placed centrally between cathode and anode and is in-situ electrochemically alloyed with lithium. The resulting lithium-gold alloy reference electrode shows remarkable stability (>500 h) even during cycling or at elevated temperatures (40 • C). The accuracy of impedance measurements with this novel reference electrode is carefully validated. Further, we investigate the effect of different vinylene carbonate (VC) contents in the electrolyte on the charge transfer resistance of LFP/graphite full cells and demonstrate that the ratio of VC to active material, rather than the VC concentration, determines the impedance of the anode SEI.

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“…REs are commonly used in various areas of electrochemistry, but the close proximity of lithium-ion cell electrodes and the low conductivity of electrolytes (compared to aqueous systems) make it difficult to introduce a reliable third electrode. Several three-electrode configurations [1][2][3][4][5][6][7] have been employed for lithium-ion studies, including the following: i) T-cell set-up where the RE is positioned at the edge of the electrode sandwich ii) a Swagelok-cell design, where a coaxial micro-RE is position at each side of the cell sandwich with holes in both the working electrode (WE) and CE; (iii) a coin-cell * Electrochemical Society Member.…”

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Electrode Behavior RE-Visited: Monitoring Potential Windows, Capacity Loss, and Impedance Changes in Li_1.03(Ni_0.5Co_0.2Mn_0.3)_0.97O₂/Silicon-Graphite Full Cells

Klett

Gilbert

Trask

et al. 2016

J. Electrochem. Soc.

120

110

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The capacity and power performance of lithium-ion battery cells evolve over time. The mechanisms leading to these changes can often be identified through knowledge of electrode potentials, which contain information about electrochemical processes at the electrodeelectrolyte interfaces. In this study we monitor electrode potentials within full cells containing a Li 1.03 (Ni 0.5 Co 0.2 Mn 0.3 ) 0.97 O 2 -based (NCM523) positive electrode, a silicon-graphite negative electrode, and an LiPF 6 -bearing electrolyte, with and without fluoroethylene carbonate (FEC) or vinylene carbonate (VC) additives. The electrode potentials are monitored with a Li-metal reference electrode (RE) positioned besides the electrode stack; changes in these potentials are used to examine electrode state-of-charge (SOC) shifts, material utilization, and loss of electrochemically active material. Electrode impedances are obtained with a Li x Sn RE located within the stack; the data display the effect of cell voltage and electrode SOC changes on the measured values after formation cycling and after aging. Our measurements confirm the beneficial effect of FEC and VC electrolyte additives in reducing full cell capacity loss and impedance rise after cycling in a 3.0-4.2 V range. Comparisons with data from a full cell containing a graphite-based negative highlight the consequences of including silicon in the electrode. Our observations on electrode potentials, capacity, and impedance changes on cycling are crucial to designing long-lasting, silicon-bearing, lithium-ion cells. As applications of lithium-ion systems expand beyond consumer electronics to the transportation and electricity storage markets, battery-cell longevity has become a primary barrier to widespread commercialization. While cells in smart phones are expected to function for about two years, energy storage units in electric vehicles are expected to maintain performance over a 10-15 year period. This performance is primarily defined by cell capacity and impedance characteristics, which change as electrode potentials and electrodeelectrolyte interfaces evolve over time. The knowledge of electrode potentials is very important for battery aging investigations because it can point to sources of performance degradation and, hence, lead to solutions that improve cell life. Such improvements are urgently needed for high-energy density cells, with silicon-containing-negative and layered-oxide-positive electrodes, being developed at Argonne National Laboratory as part of the U.S. DOE's Applied Battery Research (ABR) for Transportation program.The potentials of individual electrodes, such as that of a layeredoxide electrode, can be monitored in two-electrode cells by using a Li-metal counter electrode (CE) at low currents, or by using a CE with high surface areas, which reduce current densities and maintains a relatively stable potential. However, electrode potentials cannot be measured independently in commercial lithium-ion cells, which do not contain Li-metal. Yet aging investigations of ...

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FEM modelling of a coaxial three-electrode test cell for electrochemical impedance spectroscopy in lithium ion batteries

Cited by 46 publications

References 16 publications

Three-dimensional-networked NiCo2S4 nanosheet array/carbon cloth anodes for high-performance lithium-ion batteries

Three-dimensional-networked NiCo2S4 nanosheet array/carbon cloth anodes for high-performance lithium-ion batteries

A Gold Micro-Reference Electrode for Impedance and Potential Measurements in Lithium Ion Batteries

Electrode Behavior RE-Visited: Monitoring Potential Windows, Capacity Loss, and Impedance Changes in Li_1.03(Ni_0.5Co_0.2Mn_0.3)_0.97O₂/Silicon-Graphite Full Cells

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FEM modelling of a coaxial three-electrode test cell for electrochemical impedance spectroscopy in lithium ion batteries

Cited by 46 publications

References 16 publications

Three-dimensional-networked NiCo2S4 nanosheet array/carbon cloth anodes for high-performance lithium-ion batteries

Three-dimensional-networked NiCo2S4 nanosheet array/carbon cloth anodes for high-performance lithium-ion batteries

A Gold Micro-Reference Electrode for Impedance and Potential Measurements in Lithium Ion Batteries

Electrode Behavior RE-Visited: Monitoring Potential Windows, Capacity Loss, and Impedance Changes in Li1.03(Ni0.5Co0.2Mn0.3)0.97O2/Silicon-Graphite Full Cells

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Product

Resources

About

Electrode Behavior RE-Visited: Monitoring Potential Windows, Capacity Loss, and Impedance Changes in Li_1.03(Ni_0.5Co_0.2Mn_0.3)_0.97O₂/Silicon-Graphite Full Cells