Online electrochemical mass spectrometry on large-format Li-ion cells

Misiewicz, Casimir; Lundström, Robin; Ahmed, Istaq; Lacey, Matthew J.; Brant, William R.; Berg, Erik J.

doi:10.1016/j.jpowsour.2022.232318

Cited by 23 publications

(17 citation statements)

References 33 publications

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“…Strong differences in the CO 2 evolution of the materials are evident and will be discussed in the following. However, while a slightly delayed CO 2 evolution for PC-LNO in the initial cycle is in accordance with previous reports, 27,54,55 the low overall amount and the unusual evolution curve require further considerations. The gas evolution profiles are affected by the use of a rather large volume of electrolyte, which is unfortunately sometimes required for the reliable cycling of DEMS cells in an open-headspace configuration.…”

Section: Chemistry Of Materialssupporting

confidence: 91%

Seesaw Effect of Substitutional Point Defects on the Electrochemical Performance of Single-Crystal LiNiO₂ Cathodes

Karger,

Korneychuk,

van den Bergh

et al. 2023

Chem. Mater.

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Layered oxide cathode materials, such as Li-Ni a Co b Mn c O 2 or LiNi a Co b Al c O 2 , are sought after mainly because of their high theoretical specific capacity. Especially those with a high nickel content are being pursued to increase capacity and lower costs. In these materials, substitutional defects are a common feature and are typically associated with poor overall quality. Herein, we employ a sodium-to-lithium ion exchange to produce LiNiO 2 (LNO) without such characteristic defects. Three different methods are used to tailor the primary particle (grain) size over a broad range, and each material is subjected to electrochemical testing. By analyzing the initial charge/discharge profiles, we separate kinetic hindrance and structural degradation as two independent contributions to the first-cycle capacity loss. We find that the Ni Li• point defects stabilize LNO at high potentials and help mitigate material degradation while leading to incomplete discharge. The kinetic hindrance at the end of discharge vanishes upon their removal, but the degradation at high states of charge becomes more pronounced. We examine the cause of material degradation and corroborate the results by artificially introducing pillaring Mg 2+ ions through a novel dual-ion exchange as a model system for nickel substitutional defects. This methodology may be exploited to identify an optimal concentration of pillar ions, especially in a range of defect densities that are inaccessible by conventional solid-state synthesis.

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Section: Chemistry Of Materialssupporting

confidence: 91%

Seesaw Effect of Substitutional Point Defects on the Electrochemical Performance of Single-Crystal LiNiO₂ Cathodes

Karger,

Korneychuk,

van den Bergh

et al. 2023

Chem. Mater.

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“…Note that delayed gas evolution during discharge in the initial cycle is common for layered Ni-rich oxides. [98][99][100] Second-cycle gas evolution could not be quantified for all materials because of the low overall gassing of clean and dry-processed CAM at a regular cut-off potential of 4.3 vs Li + /Li. Similarly, no molecular O 2 is detected, as it immediately reacts with the electrolyte upon release forming CO 2 .…”

Section: Resultsmentioning

confidence: 99%

The Effect of Doping Process Route on LiNiO₂ Cathode Material Properties

Dreyer

Kurzhals

Seiffert

et al. 2023

J. Electrochem. Soc.

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The pursuit of higher energy density in lithium-ion batteries has driven the increase of the nickel content in lithium nickel cobalt manganese oxide cathode active materials (CAMs), ultimately approaching LiNiO2 (LNO). The downside of the high specific capacity of LNO is more severe degradation of the CAM during battery operation. A common approach to increase structural stability is the introduction of dopants. Various dopants are discussed and compared with each other when integrated into the CAM and tested against undoped materials in the literature, but little attention is given to the role of the process route of their introduction. In this work, we demonstrate with a series of nominally equally Zr-doped LNO samples that effects on various physico- and electrochemical properties are due not to the dopant itself, as one would assume in comparison to an undoped sample, but to the process route and the resulting particle morphology. Dopant, concentration and process routes (co-precipitation, impregnation and co-calcination) were chosen based on their significance for industrial application.

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“…[12,[23][24][25] These processes are highly interlinked but poorly understood. Notably, oxygen evolution is not usually observed in most gassing measurements [8,26] so it is often assumed that a highly reactive oxygen species is formed [12] and chemically reacts with the electrolyte solvent to form CO 2 and CO. Østergaard et al proposed a surface reaction of the organic electrolyte that leads to the removal of oxygen and the formation of CO 2 and CO, in contrast to the mechanism that forms an oxygen molecule. [24] Identifying and quantifying gas evolution during the operation of an electrochemical system provides valuable insight into a variety of important processes.…”

Section: Introductionmentioning

confidence: 99%

Probing Degradation in Lithium Ion Batteries with On‐Chip Electrochemistry Mass Spectrometry**

Thornton,

Davies,

Scott

et al. 2023

Angew Chem Int Ed

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The rapid uptake of lithium ion batteries (LIBs) for large scale electric vehicle and energy storage applications requires a deeper understanding of the degradation mechanisms. Capacity fade is due to the complex interplay between phase transitions, electrolyte decomposition and transition metal dissolution; many of these poorly understood parasitic reactions evolve gases as a side product. Here we present an on‐chip electrochemistry mass spectrometry method that enables ultra‐sensitive, fully quantified and time resolved detection of volatile species evolving from an operating LIB. The technique's electrochemical performance and mass transport is described by a finite element model and then experimentally used to demonstrate the variety of new insights into LIB performance. We show the versatility of the technique, including (a) observation of oxygen evolving from a LiNiMnCoO2 cathode and (b) the solid electrolyte interphase formation reaction on graphite in a variety of electrolytes, enabling the deconvolution of lithium inventory loss (c) the first direct evidence, by virtue of the improved time resolution of our technique, that carbon dioxide reduction to ethylene takes place in a lithium ion battery. The emerging insight will guide and validate battery lifetime models, as well as inform the design of longer lasting batteries.

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Online electrochemical mass spectrometry on large-format Li-ion cells

Cited by 23 publications

References 33 publications

Seesaw Effect of Substitutional Point Defects on the Electrochemical Performance of Single-Crystal LiNiO₂ Cathodes

Seesaw Effect of Substitutional Point Defects on the Electrochemical Performance of Single-Crystal LiNiO₂ Cathodes

The Effect of Doping Process Route on LiNiO₂ Cathode Material Properties

Probing Degradation in Lithium Ion Batteries with On‐Chip Electrochemistry Mass Spectrometry**

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Online electrochemical mass spectrometry on large-format Li-ion cells

Cited by 23 publications

References 33 publications

Seesaw Effect of Substitutional Point Defects on the Electrochemical Performance of Single-Crystal LiNiO2 Cathodes

Seesaw Effect of Substitutional Point Defects on the Electrochemical Performance of Single-Crystal LiNiO2 Cathodes

The Effect of Doping Process Route on LiNiO2 Cathode Material Properties

Probing Degradation in Lithium Ion Batteries with On‐Chip Electrochemistry Mass Spectrometry**

Contact Info

Product

Resources

About

Seesaw Effect of Substitutional Point Defects on the Electrochemical Performance of Single-Crystal LiNiO₂ Cathodes

Seesaw Effect of Substitutional Point Defects on the Electrochemical Performance of Single-Crystal LiNiO₂ Cathodes

The Effect of Doping Process Route on LiNiO₂ Cathode Material Properties