Lithium Anode Properties in a Nonaqueous Cell

Jackson, G. W.; Blomgren, G. E.

doi:10.1149/1.2411577

Cited by 13 publications

(11 citation statements)

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“…One important concept developed during this period, the solid-electrolyte interphase (SEI), will have long-lasting influence that goes beyond Li metal to virtually any advanced battery systems, as long as their electrodes operate at potentials away from the thermodynamic stability limits of electrolytes. Almost as soon as Li metal was found to be stable in nonaqueous electrolytes, people suspected that a passivation process was responsible, − because the reduction potentials of almost any nonaqueous solvent are far above the potential of Li 0 /Li + . Dey even proposed that Li 2 CO 3 is the composition of such film and that Li + will possess a transference number of 1.0 across this film .…”

Section: Quest For the “Holy Grail”mentioning

confidence: 99%

Before Li Ion Batteries

2018

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This Review covers a sequence of key discoveries and technical achievements that eventually led to the birth of the lithium-ion battery. In doing so, it not only sheds light on the history with the advantage of contemporary hindsight but also provides insight and inspiration to aid in the ongoing quest for better batteries of the future. A detailed retrospective on ingenious designs, accidental discoveries, intentional breakthroughs, and deceiving misconceptions is given: from the discovery of the element lithium to its electrochemical synthesis; from intercalation host material development to the concept of dual-intercalation electrodes; and from the misunderstanding of intercalation behavior into graphite to the comprehension of interphases. The onerous demands of bringing all critical components (anode, cathode, electrolyte, solid-electrolyte interphases), each of which possess unique chemistries, into a sophisticated electrochemical device reveal that the challenge of interfacing these originally incongruent components often outweighs the individual merits and limits in their own properties. These important lessons are likely to remain true for the more aggressive battery chemistries of future generations, ranging from a revisited Li-metal anode, to conversion-reaction type chemistries such as Li/sulfur, Li/oxygen, and metal fluorides, and to bivalent cation intercalations.

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Section: Quest For the “Holy Grail”mentioning

confidence: 99%

Before Li Ion Batteries

2018

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“…The solution to Eq. [7][8][9][10][11][12] will first be examined for small ~ by expressing A and 0 as a power series in T.…”

Section: Mathematical Formulationmentioning

confidence: 99%

“…[7][8][9][10][11][12], the unknown coefficients can be determined. The result is given by A = ~ --~2/2 -5 5"~3/6 --17z4/8 -5 827z5/120 + 0(T s) [15] o Let us now determine if -% --~1/2 at long times, which would be characteristic of unrestricted semiinfinite diffusion from an electrode.…”

Section: + D(x)z 4 + O(t 5) [14]mentioning

confidence: 99%

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Growing Porous Layers

Tiedemann¹,

Newman²

1972

J. Electrochem. Soc.

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The precipitation of ions generated at an electrode, operating at a constant current, with ions of the adjacent electrolytic solution has been modeled as a growing porous layer. The thickness of the layer as a function of time for short times is given by a power series expansion of time. The long-time solution was determined by a numerical calculation on a digital computer. A criterion for linear growth rate as a function of time is given.Moving boundary problems, such as melting-freezing, evaporation-condensation, and purification of materials, involving heat and mass transfer have been treated in depth (1-7). A moving boundary problem is encountered in the field of electrochemistry when ions being generated at an electrode, operating at a constant current, form a precipitate with ions of the adjacent electrolytic solution. The resulting precipitate forms a growing porous layer on the electrode. Studies of anodic dissolution of various metals which form porous coatings (8) can be considered examples of growing porous layers. In the case of silver, a porous layer occurs only after a nonporous layer has been formed or when large currents are employed (9, 10). Jackson and Blomgren (11) studied the anodic dissolution of lithium in a 1M solution of A1C13 in propylene carbonate and observed a growing porous layer of LiC1. Other examples of growing porous layers are the oxidation of tungsten (12) and the scaling of metals (13). In the following analysis, the thickness of a growing porous layer as a function of time is determined, and a criterion for linear growth rate as a function of time is given.

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“…These cells often have higher internal resistances or polarization due to the metal counter electrode, and hence a larger ohmic drop upon cycling is observed. 39 Lithium also reacts to form an interface layer on the electrode, which needs to reform upon every redeposition. Therefore the coulombic efficiencies of the half cells are marginally lower than that observed without a lithium metal counter electrode (full cell), which leads to shorter cell lifetimes.…”

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confidence: 99%

Development of Experimental Techniques for Parameterization of Multi-scale Lithium-ion Battery Models

Chen

Planella

O’Regan

et al. 2020

J. Electrochem. Soc.

347

339

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Presented here, is an extensive 35 parameter experimental data set of a cylindrical 21700 commercial cell (LGM50), for an electrochemical pseudo-two-dimensional (P2D) model. The experimental methodologies for tear-down and subsequent chemical, physical, electrochemical kinetics and thermodynamic analysis, and their accuracy and validity are discussed. Chemical analysis of the LGM50 cell shows that it is comprised of a NMC 811 positive electrode and bi-component Graphite-SiOx negative electrode. The thermodynamic open circuit voltages (OCV) and lithium stoichiometry in the electrode are obtained using galvanostatic intermittent titration technique (GITT) in half cell and three-electrode full cell configurations. The activation energy and exchange current coefficient through electrochemical impedance spectroscopy (EIS) measurements. Apparent diffusion coefficients are estimated using the Sand equation on the voltage transient during the current pulse; an expansion factor was applied to the bi-component negative electrode data to reflect the average change in effective surface area during lithiation. The 35 parameters are applied within a P2D model to show the fit to experimental validation LGM50 cell discharge and relaxation voltage profiles at room temperature. The accuracy and validity of the processes and the techniques in the determination of these parameters are discussed, including opportunities for further modelling and data analysis improvements.

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Lithium Anode Properties in a Nonaqueous Cell

Cited by 13 publications

References 0 publications

Before Li Ion Batteries

Before Li Ion Batteries

Growing Porous Layers

Development of Experimental Techniques for Parameterization of Multi-scale Lithium-ion Battery Models

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