Stage Transformation of Lithium‐Graphite Intercalation Compounds Caused by Electrochemical Lithium Intercalation

Funabiki, Atsushi; Inaba, Masaaki; Abe, Takeshi; Ogumi, Zempachi

doi:10.1149/1.1391953

Cited by 139 publications

(134 citation statements)

References 31 publications

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“…4 SEI is the key factor which determines the safety, power capability, morphology of lithium deposits, shelf life, and cycle life of the battery. 1,[5][6][7] To eliminate concentration polarization and to facilitate the metallic anode dissolution/deposition processes, the cation transport number should be close to unity. The SEI must be both mechanically stable and flexible.…”

Section: The Present Lithium-metal and Lithium-ion Batteriesmentioning

confidence: 99%

Review—SEI: Past, Present and Future

Peled

Menkin

2017

J. Electrochem. Soc.

1,607

1,474

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The Solid-Electrolyte-Interphase (SEI) model for non-aqueous alkali-metal batteries constitutes a paradigm change in the understanding of lithium batteries and has thus enabled the development of safer, durable, higher-power and lower-cost lithium batteries for portable and EV applications. Prior to the publication of the SEI model (1979), researchers used the Butler-Volmer equation, in which a direct electron transfer from the electrode to lithium cations in the solution is assumed. The SEI model proved that this is a mistaken concept and that, in practice, the transfer of electrons from the electrode to the solution in a lithium battery, must be prevented, since it will result in fast self-discharge of the active materials and poor battery performance. This model provides [E. Peled, in "Lithium Batteries," J.P. Gabano (ed), Academic Press, (1983), E. Peled, J. Electrochem. Soc., 126, 2047Soc., 126, (1979.] new equations for: electrode kinetics (i o and b), anode corrosion, SEI resistivity and growth rate and irreversible capacity loss of lithium-ion batteries. This model became a cornerstone in the science and technology of lithium batteries. This paper reviews the past, present and the future of SEI batteries. The PastPrior to the publication of the SEI model (1979), 1,4 researchers used the Butler-Volmer equation, in which direct electron transfer from the electrode to lithium cations in the solution is assumed. It was generally assumed that the rate-determining step (RDS) is the transfer of electrons from the metal to the cations in the solution. Researchers found that the lithium anode is covered by a passivating layer which interferes with the deposition/dissolution process of the anode. Brummer and Newman 2,3 concluded that a passivating anode can offer only a limited cycle life and in order to obtain a deep-discharge high-cycle-life secondary battery, the lithium anode must be free of a passivating layer and kinetically stable with respect to the electrolyte. The SEI model proved that this is a mistaken concept and that, in practice, the transfer of electrons from the electrode to the solution in a lithium battery, except when forming a SEI, must be prevented. The Present, Lithium-Metal and Lithium-Ion BatteriesIntroduction.-It is now generally accepted that the solidelectrolyte interphase (SEI) is essentially for the existence and successful operation of lithium-and sodium-battery systems, as primary and secondary power sources. 4 In 1979, it was proposed by Peled,

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Section: The Present Lithium-metal and Lithium-ion Batteriesmentioning

confidence: 99%

Review—SEI: Past, Present and Future

Peled

Menkin

2017

J. Electrochem. Soc.

1,607

1,474

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“…It is also known as ad ilute stage if s > IV. [79,81,82] Stage formation can be easily observed in ac harge/discharge profile in the form of ap lateau by constantc urrent measurements for ag raphite anode.T he plateausi ndicatet he coexistence of two phases. The formation of stages II, IIL (a transition stage between stage II and stage III), III, and IV were identified from experimental electrochemical curves [80,81] and were confirmed by X-ray diffraction and Ramans pectroscopy.…”

mentioning

confidence: 99%

“…[79,81,82] Stage formation can be easily observed in ac harge/discharge profile in the form of ap lateau by constantc urrent measurements for ag raphite anode.T he plateausi ndicatet he coexistence of two phases. The formation of stages II, IIL (a transition stage between stage II and stage III), III, and IV were identified from experimental electrochemical curves [80,81] and were confirmed by X-ray diffraction and Ramans pectroscopy. [79,[83][84][85] Twof actors determine the formation of stages during Li intercalation into graphite:o ne, the energy required to expandt he van der Waals gap between two graphene layers; two, the repulsive interactions between the guest species.…”

mentioning

confidence: 99%

Carbon‐Based Materials for Lithium‐Ion Batteries, Electrochemical Capacitors, and Their Hybrid Devices

2015

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A rapidly developing market for portable electronic devices and hybrid electrical vehicles requires an urgent supply of mature energy-storage systems. As a result, lithium-ion batteries and electrochemical capacitors have lately attracted broad attention. Nevertheless, it is well known that both devices have their own drawbacks. With the fast development of nanoscience and nanotechnology, various structures and materials have been proposed to overcome the deficiencies of both devices to improve their electrochemical performance further. In this Review, electrochemical storage mechanisms based on carbon materials for both lithium-ion batteries and electrochemical capacitors are introduced. Non-faradic processes (electric double-layer capacitance) and faradic reactions (pseudocapacitance and intercalation) are generally explained. Electrochemical performance based on different types of electrolytes is briefly reviewed. Furthermore, impedance behavior based on Nyquist plots is discussed. We demonstrate the influence of cell conductivity, electrode/electrolyte interface, and ion diffusion on impedance performance. We illustrate that relaxation time, which is closely related to ion diffusion, can be extracted from Nyquist plots and compared between lithium-ion batteries and electrochemical capacitors. Finally, recent progress in the design of anodes for lithium-ion batteries, electrochemical capacitors, and their hybrid devices based on carbonaceous materials are reviewed. Challenges and future perspectives are further discussed.

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“…The SEI is a passivating film that is formed on the anode surface by electrolyte decomposition in a lithium ion battery. This film protects the electrolyte solution from further decomposition, and also affects the safety, power capacity, shelf life, cycle life and performance of a lithium-ion battery (10)(11)(12). However, the SEI film also limits the capacity and dynamic response of Li-ion batteries by limiting lithium ion transport, and the resistance across the film also restricts the current flow.…”

Section: Introductionmentioning

confidence: 99%

Fundamental investigation of Si anode in Li-Ion cells

Bennett

2012

2012 IEEE Energytech

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Abstract-Silicon is a promising and attractive anode material to replace graphite for high capacity lithium ion cells since its theoretical capacity is ~10 times of graphite and it is an abundant element on earth. However, there are challenges associated with using silicon as Li-ion anode due to the significant first cycle irreversible capacity loss and subsequent rapid capacity fade during cycling. In this paper, cyclic voltammetry and electrochemical impedance spectroscopy are used to build a fundamental understanding of silicon anodes. The results show that it is difficult to form the SEI film on the surface of Si anode during the first cycle, the lithium ion insertion and deinsertion kinetics for Si are sluggish, and the cell internal resistance changes with the state of lithiation after electrochemical cycling. These results are compared with those for extensively studied graphite anodes. The understanding gained from this study will help to design better Si anodes. NASA is developing ultra-high energy Li-ion cells and batteries for future exploration missions. These cells will utilize advanced anode materials to replace graphite. Silicon is a promising candidate since its theoretical capacity is ~10 times that of graphite (1, 2), and it is an abundant element on earth. However, the use of Si anodes in Li-ion batteries is challenging due to its significantly lower conductivity and much higher (~400%) volume expansion during lithiation and delithiation that occur during the cycling processes (3). Much research has been conducted on Si anodes aimed at addressing these limitations. Approaches include the addition of carbon fibers or carbon black for improvement of Si conductivity (4, 5), the development of Si/C composite electrodes (6) and the use of nano Si wires for reduction of expansion (7-9). Much progress has been made on these fields. This study focuses on developing an understanding of the solid electrolyte interphase (SEI) and Li-ion insertion/deinsertion kinetics in cells with silicon anodes. The SEI is a passivating film that is formed on the anode surface by electrolyte decomposition in a lithium ion battery. This film protects the electrolyte solution from further decomposition, and also affects the safety, power capacity, shelf life, cycle life and performance of a lithium-ion battery (10-12). However, the SEI film also limits the capacity and dynamic response of Li-ion batteries by limiting lithium ion transport, and the resistance across the film also restricts the current flow. For optimal performance, the SEI should be highly permeable to lithium ions to minimize the concentration polarization and must be an electronic resistor to prevent SEI thickening that leads to high internal resistance, self-discharge and low faradaic efficiency. The SEI should also be highly ionconductive to reduce overvoltage, and have uniform chemical composition and morphology to ensure homogeneous current distribution. Gaining a fundamental understanding of the phenomena that control the formation of the SEI is ess...

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Stage Transformation of Lithium‐Graphite Intercalation Compounds Caused by Electrochemical Lithium Intercalation

Cited by 139 publications

References 31 publications

Review—SEI: Past, Present and Future

Review—SEI: Past, Present and Future

Carbon‐Based Materials for Lithium‐Ion Batteries, Electrochemical Capacitors, and Their Hybrid Devices

Fundamental investigation of Si anode in Li-Ion cells

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