Complementary X-ray and neutron radiography study of the initial lithiation process in lithium-ion batteries containing silicon electrodes

Sun, Fu; Markötter, Henning; Manke, Ingo; Hilger, André; Alrwashdeh, Saad S.; Kardjilov, Nikolay; Banhart, John

doi:10.1016/j.apsusc.2016.12.093

Cited by 51 publications

(25 citation statements)

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“…Studies range inter alia from electrolyte filling to lithiation processes and active material synthesis. [26][27][28] In the present study, we provide a direct and detailed comparison of LFP/graphite and LFMP/graphite full-cells in order to determine the influence of manganese on the initial gas evolution by means of neutron imaging (NI). Additionally, we use Prompt Gamma Activation Analysis (PGAA) to understand the long-term development of Mn dissolution and its relation to capacity retention.…”

mentioning

confidence: 99%

Gas Evolution and Capacity Fading in LiFe_xMn_1-xPO₄/Graphite Cells Studied by Neutron Imaging and Neutron Induced Prompt Gamma Activation Analysis

Starke

Seidlmayer

Schulz

et al. 2017

J. Electrochem. Soc.

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The gas evolution in LFP/graphite and LFMP/graphite cells during the formation has been analyzed via neutron imaging (NI). The results show that in LFMP/graphite cells approximately 30% more gas is generated in comparison to LFP/graphite and stronger gas evolution is associated with the presence of Mn. For the LFP/graphite cell two different linear phases in gas evolution rate can be detected while LFMP/graphite cells reveal an additional phase. In both full-cells a distinct relation between gas evolution and electrode potentials has been determined. Additional neutron induced Prompt Gamma Activation Analysis (PGAA) measurements were carried out in order to correlate long-term Mn dissolution and capacity retention. Long-term cycling showed higher capacity retention for the LFMP/graphite cells. The results of PGAA prove that Mn dissolution decreases rapidly with increased cycle number and the Mn dissolution rate of LFMP is far below values observed for oxide-type cathode materials. Long-term cycling showed that the negative effects of higher irreversible capacity loss in the formation step and more gas evolution of LFMP/graphite cells in comparison to LFP/graphite cells is compensated after several cycles due to higher capacity retention. Due to their high energy density and operating voltage lithiumion batteries are a key technology for mobile applications such as communication devices and electric vehicles.1-3 But also stationary energy storage systems are increasingly developed under usage of lithium-ion technology. Those stationary storage systems range from small (e. g. home storage for photovoltaic plants) to large scale applications (grid stabilization). [4][5][6] Especially in cases of high capital expenditures, consumers and operators expect a long battery lifetime in terms of capacity and charge and discharge characteristics.Applications like home energy storage require high operational safety standards. These requirements are met by the cathode active material LiFePO 4 (LFP), which has first been described in 1997. Phospho-olivines such as LFP provide good operational characteristics in terms of thermal runaways and are furthermore environmentally friendly and cost-efficient. The dissolution of Mn from LFMP as such has recently been investigated and a strong correlation between dissolved Mn and traces of H 2 O contamination in the electrolyte has been stated. It has also been found that in case of LFMP there is no selective dissolution of Mn since Fe is dissolved as well and the Mn/Fe ratio in the electrolyte and the active material is equal. 18Another study has shown that transition metal dissolution also occurs in oxide-type active materials such as layered Nickel-ManganeseCobalt oxide based active materials (NMC). 19 In case of NMC all z E-mail: benjamin.starke@haw-landshut.de present transition metals Ni, Mn and Co dissolve in the electrolyte and migrate to the anodic graphite. But while Ni and Co remain in the oxidation state +II, Mn is reduced to Mn 0 and subsequently reoxidized to Mn 2+ under co...

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mentioning

confidence: 99%

Gas Evolution and Capacity Fading in LiFe_xMn_1-xPO₄/Graphite Cells Studied by Neutron Imaging and Neutron Induced Prompt Gamma Activation Analysis

Starke

Seidlmayer

Schulz

et al. 2017

J. Electrochem. Soc.

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“…With in situ configurations, the radiography methods directly probe the working anode. Recently, by combining in situ X‐ray and neutron radiography measurements, Sun et al directly visualized the initial lithiation inside Si‐based LIBs. Many Si particles underwent no lithiation, which is in agreement with previous compositional studies .…”

Section: Applications Of Advanced Characterization Methods To Siliconmentioning

confidence: 99%

“…Earlier studies have been conducted in ex situ configurations that detected specific changes in electrode materials dissembled at different states of charge (SOCs) during the first cycle, demonstrating the buffering effect of fabricated Si–carbon (Si–C) composites on first charge/discharge capacities . Recently, by means of various advanced techniques, comparative studies of the surface properties of Si‐based materials have also been realized, and they clarified the role of the native oxides during cycling by determining a lithiation/delithiation mechanism …”

Section: Fundamental Understanding Of Fading Mechanism In Silicon‐basmentioning

confidence: 99%

Recent Progress in Advanced Characterization Methods for Silicon‐Based Lithium‐Ion Batteries

Ma²,

Liu

et al. 2019

Small Methods

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With the remarkably large theoretical specific capacity of silicon (Si), Si‐based rechargeable lithium‐ion batteries (LIBs) have attracted great interest, as they are expected to meet the growing demand for large‐scale energy storage devices, electric vehicles, and portable electronic devices with high energy density. However, the Si‐based LIB faces great challenges due to the cyclic volume changes induced by Si, which lead to considerable capacity fading. To facilitate the use of high‐performance LIBs enabled by Si‐based anodes, understanding the fading mechanism is necessary. In this regard, various advanced characterization methods have been developed to reveal the fading mechanism and to develop a modification strategy associated with compositional and structural evolution. In this review, the general understanding of the fading mechanism and the technical specifications of Si‐based LIBs are discussed. The recent progress in advanced characterization methods for Si‐based LIBs is summarized with respect to the achievements in compositional and structural interpretation. Several possible future research directions for Si‐based LIBs and the expected development trends in relevant characterization methods are also discussed.

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“…It is a desirable idea to correlate X‐ray imaging with neutron imaging in one experiment. The conduction of X‐ray radiography and neutron radiography in battery research was firstly attempted by Sun et al [ 92 ] In their experiments, X‐ray and neutron results were used together to visualize the initial lithiation in silicon anode. Through combining the silicon morphology information provided by X‐ray imaging with the lithium distribution obtained by neutron imaging, the process was revealed that Li ions were alloyed with Si to cause the volume expansion of the Si electrode.…”

Section: Neutron Imagingmentioning

confidence: 99%

Recent Progress on Advanced Imaging Techniques for Lithium‐Ion Batteries

Deng

Xing

Huang³

et al. 2020

Advanced Energy Materials

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Lithium‐ion batteries are the most commercially successful electrochemical devices, extensively used in intelligent electronics, electric vehicles, grid energy storages, etc. However, there still needs to be further improvement of their performance such as in energy density, cyclability, rate capability, and safety. To do so, it is necessary to understand the detailed structural evolution progress inside the battery. Many advanced imaging techniques have been developed to directly monitor the status and get some key information inside the battery. For advanced imaging techniques, superhigh resolution, fully informative function, nondestruction of the sample, and in situ observation are required. This review introduces and discusses some recent important progress on a variety of advanced imaging techniques for battery research. These imaging techniques have enabled the visualization of sub‐micrometer level chemical valence distribution, evolution of solid‐electrolyte interface, Li dendrite growth, and trace amount of gassing, etc., which greatly promote the development of rechargeable batteries. Of particular note, a new ultrasonic imaging technique has been recently developed to monitor gas generation, the electrolyte wetting process, and the state of charge in the battery. Finally, a perspective is given on some future developments in the imaging techniques for Li‐ion batteries and other rechargeable batteries.

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Complementary X-ray and neutron radiography study of the initial lithiation process in lithium-ion batteries containing silicon electrodes

Abstract: A radiography cell for in operando X-ray radiography was designed and built. 2 A self-assembled CR2032 coin cell was built for in operando neutron radiography. 3 In operando X-ray and neuron radiography were conducted by using Si electrode half cells.

Cited by 51 publications

References 35 publications

Gas Evolution and Capacity Fading in LiFe_xMn_1-xPO₄/Graphite Cells Studied by Neutron Imaging and Neutron Induced Prompt Gamma Activation Analysis

Gas Evolution and Capacity Fading in LiFe_xMn_1-xPO₄/Graphite Cells Studied by Neutron Imaging and Neutron Induced Prompt Gamma Activation Analysis

Recent Progress in Advanced Characterization Methods for Silicon‐Based Lithium‐Ion Batteries

Recent Progress on Advanced Imaging Techniques for Lithium‐Ion Batteries

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Complementary X-ray and neutron radiography study of the initial lithiation process in lithium-ion batteries containing silicon electrodes

Abstract: A radiography cell for in operando X-ray radiography was designed and built. 2 A self-assembled CR2032 coin cell was built for in operando neutron radiography. 3 In operando X-ray and neuron radiography were conducted by using Si electrode half cells.

Cited by 51 publications

References 35 publications

Gas Evolution and Capacity Fading in LiFexMn1-xPO4/Graphite Cells Studied by Neutron Imaging and Neutron Induced Prompt Gamma Activation Analysis

Gas Evolution and Capacity Fading in LiFexMn1-xPO4/Graphite Cells Studied by Neutron Imaging and Neutron Induced Prompt Gamma Activation Analysis

Recent Progress in Advanced Characterization Methods for Silicon‐Based Lithium‐Ion Batteries

Recent Progress on Advanced Imaging Techniques for Lithium‐Ion Batteries

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Gas Evolution and Capacity Fading in LiFe_xMn_1-xPO₄/Graphite Cells Studied by Neutron Imaging and Neutron Induced Prompt Gamma Activation Analysis

Gas Evolution and Capacity Fading in LiFe_xMn_1-xPO₄/Graphite Cells Studied by Neutron Imaging and Neutron Induced Prompt Gamma Activation Analysis