In Situ Neutron Depth Profiling: A Powerful Method to Probe Lithium Transport in Micro‐Batteries

Oudenhoven, Jfm Jos; Labohm, F.; Mulder, Martijn; Niessen, Rah Rogier; Mulder, Fokko M.; Notten, Phl Peter

doi:10.1002/adma.201101819

Cited by 90 publications

(66 citation statements)

References 27 publications

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“…However, as typical for the low Li-density insertion hosts, the time resolution is poor, 10-60 min for operando (dis)charging (Zhang et al, 2015;. Enriching samples with Li-6 provides the opportunity to improve this, however it adds the complication of relaxation and homogenization effects if not all components are enriched (Oudenhoven et al, 2011). As shown recently,Li-metal plating is a process where full enrichment is achieved relatively easy (Lv et al, 2018).…”

Section: Introductionmentioning

confidence: 99%

“…As a result, high resolution set-ups employ multiple detectors to improve counting statistics (Parikh et al, 1990;Mulligan et al, 2012). Another strategy to increase the count rate is to enrich the 6 Li contents of the materials under investigation (Downing et al, 1987;Oudenhoven et al, 2011) as the natural abundancy of the 6 Li isotope is only 7.5% (Hutchison, 1954). Hence replacing all 7 Li with 6 Li would increase count rates by a factor of 13.…”

Section: Introductionmentioning

confidence: 99%

“…Whitney et al (2009), first suggested using the 6 Li capture reaction for NDP on lithium ion battery systems. The technique offers the unique ability to quantitatively measure lithium concentrations, as function of depth, independent of oxidation state, during battery cycling (Oudenhoven et al, 2011;Wang et al, 2014;Harks et al, 2015;Liu and Co, 2016). Techniques allowing direct, non-invasive lithium detection operando are limited, as a result NDP was quickly adopted by a number of research groups in to order to study problems such as degradation (Nagpure et al, 2011) and charge transport limitations (Zhang et al, 2015).…”

Section: Introductionmentioning

confidence: 99%

“…An important implication of the geometrical resolution is that the detector is typically positioned at several centimeteres from the sample. This requires the setup to be operated under vacuum conditions to avoid parasitic energy absorption of the 3 H and He particles by the air (Hutchison, 1954;Downing et al, 1987;Oudenhoven et al, 2011). The vacuum conditions of the setup is one of the major obstacles for batteries containing liquid electrolytes, (Nagpure et al, 2014;Zhang et al, 2015) as most electrolytes contain solvents with a large vapor pressure, the evaporation of which leads to contact loss between the electrodes and the electrolyte, severely hindering battery performance (Zhang et al, 2015;.…”

Section: Introductionmentioning

confidence: 99%

“…Oudenhoven et al (2011)who were one of the first groups to perform operando NDP on a lithium ion cell, performed in situ lithium metal plating from a LiCoO 2 cathode through a lipon solid electrolyte in a thin film system using the increased depth resolution of the 4 He 2+ spectrum. Moreover by using different isotopes the authors demonstrated that lithium ion exchange between cathode and electrolyte is almost nonexistent in the pristine cell, due lack of lithium vacancies (Oudenhoven et al, 2011). It is noteworthy that the change in stopping power are marginal for Li-ion insertion hosts, making quantitative analysis straightforward.…”

Section: Introductionmentioning

confidence: 99%

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Operando Neutron Depth Profiling to Determine the Spatial Distribution of Li in Li-ion Batteries

Verhallen

Wagemaker

2018

Front. Energy Res.

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Neutron Depth Profiling (NDP) allows determination of the spatial distribution of specific isotopes, via neutron capture reactions. In a capture reaction charged particles with fixed kinetic energy are formed, where their energy loss through the material of interest can be used to provide the depth of the original isotope. As lithium-6 has a relatively large probability for such a capture reaction, it can be used by battery scientists to study the lithium concentration in the electrodes even during battery operation. The selective measurement of the 6 Li isotope makes it a direct and sensitive technique, whereas the penetrative character of the neutrons allows practical battery pouch cells to be studied. Using NDP lithium diffusion and reaction rates can be studied operando as a function of depth, opening a large range of opportunities including the study of alloying reactions, metal plating, and (de) intercalation in insertion hosts. In the study of high rate cycling of intercalation materials the relatively low Li density challenges counting statistics while the limited change in electrode density due to the Li-ion insertion and extraction allows straightforward determination of the Li density as a function of electrode depth. If an electrode can be (dis)charged reversibly, data can be acquired and accumulated over multiple cycles to increase the time resolution. For Li metal plating and alloying reactions, the large lithium density allows good time resolution, however the large change of the electrode composition and density makes extracting the Li-density as a function of depth more challenging. Here an effective method is presented, using calibration measurements of the individual components, based on which the ratio of the components as a function of depth can be determined as well as the total Li-density. The same principles can be applied to insertion host materials, where the differences in density due to electrolyte infiltration yield the electrode porosity as a function of depth. This is of particular importance for battery electrodes where porosity has a direct influence on the energy density and charge transport.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Operando Neutron Depth Profiling to Determine the Spatial Distribution of Li in Li-ion Batteries

Verhallen

Wagemaker

2018

Front. Energy Res.

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Combining In Situ Synchrotron X‐Ray Diffraction and Absorption Techniques with Transmission Electron Microscopy to Study the Origin of Thermal Instability in Overcharged Cathode Materials for Lithium‐Ion Batteries

Nam

Bak

et al. 2012

Adv Funct Materials

491

429

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The thermal instability of the cathode materials in lithium‐ion batteries is an important safety issue, requiring the incorporation of several approaches to prevent thermal runaway and combustion. Systematic studies, using combined well‐defined in situ techniques, are crucial to obtaining in‐depth understanding of the structural origin of this thermal instability in overcharged cathode materials. Here time‐resolved X‐ray diffraction, X‐ray absorption, mass spectroscopy, and high‐resolution transmission electron microscopy during heating are combined to detail the structural changes in overcharged LixNi0.8Co0.15Al0.05O2 and LixNi1/3Co1/3Mn1/3O2 cathode materials. By employing these several techniques in concert, various aspects of the structural changes are investigated in these two materials at an overcharged state; these include differences in phase‐distribution after overcharge, phase nucleation and propagation during heating, the preferred atomic sites and migration paths of Ni, Co, and Mn, and their individual contributions to thermal stability, together with measuring the oxygen release that accompanies these structural changes. These results provide valuable guidance for developing new cathode materials with improved safety characteristics.

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Interface Engineering for Garnet‐Based Solid‐State Lithium‐Metal Batteries: Materials, Structures, and Characterization

et al. 2018

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Lithium‐metal batteries are considered one of the most promising energy‐storage systems owing to their high energy density, but their practical applications have long been hindered by significant safety concerns and poor cycle stability. Solid‐state electrolytes (SSEs) are expected to improve not only the safety but also the energy density of Li‐metal batteries. The key challenge for solid‐state Li‐metal batteries lies in the low ionic conductivity of the SSEs and moreover the interface contact between the electrode and SSE. To achieve feasible solid‐state Li‐metal batteries, it is imperative that the ionic conductivity is improved, especially at the electrode–SSE interface. Herein, recent advances in interface engineering for solid‐state Li‐metal batteries are reported, mainly focusing on garnet‐type SSEs. Various materials to modify the cathode–garnet and Li–garnet interfaces by intermediate layers, alloys, and polymer electrolytes are analyzed. Structural innovations for SSEs including composite electrolytes and multilayer SSE frameworks are reviewed, along with advanced characterization approaches to probe the interfaces, which will provide further insights for garnet‐based solid‐state batteries. Future challenges and the great promise of garnet‐based Li‐metal batteries are discussed to close.

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In Situ Neutron Depth Profiling: A Powerful Method to Probe Lithium Transport in Micro‐Batteries

Cited by 90 publications

References 27 publications

Operando Neutron Depth Profiling to Determine the Spatial Distribution of Li in Li-ion Batteries

Operando Neutron Depth Profiling to Determine the Spatial Distribution of Li in Li-ion Batteries

Combining In Situ Synchrotron X‐Ray Diffraction and Absorption Techniques with Transmission Electron Microscopy to Study the Origin of Thermal Instability in Overcharged Cathode Materials for Lithium‐Ion Batteries

Interface Engineering for Garnet‐Based Solid‐State Lithium‐Metal Batteries: Materials, Structures, and Characterization

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