Solid State Electrolytes: Nonuniform Ionic and Electronic Transport of Ceramic and Polymer/Ceramic Hybrid Electrolyte by Nanometer‐Scale Operando Imaging for Solid‐State Battery (Adv. Energy Mater. 21/2020)     

Chun‐Sheng Jiang  Nathan Dunlap  Yejing Li  Harvey Guthrey  Ping Liu  Se‐Hee Lee  Mowafak M. Al‐Jassim 《Liver Transplantation》2020,10(21)

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Anton Tokranov  Ravi Kumar  Chunzeng Li  Stephen Minne  Xingcheng Xiao  Brian W. Sheldon 《Liver Transplantation》2016,6(8)

The formation of the solid electrolyte interphase (SEI) on Si is examined in detail using several in situ techniques. The results show that employing different conditions during the first lithiation cycle produces SEI films with substantially different properties. Longer time at higher potentials produces softer SEI, whereas inorganic phases produced at lower potentials have higher elastic moduli. The SEI thickness stabilizes during the first cycle; however, the SEI resistance decreases during the first 20 cycles (in sharp contrast to typical surface passivation processes, where resistance is expected to increase with time). This behavior is consistent with the slow growth of inorganic constituents at lower potentials, inside of a mesoporous soft SEI that initially forms at higher potentials. This interpretation is based on the premise that these inorganic phases have a lower resistivity than that associated with electrolyte transport through the mesoporous organic phase. Based on this set of observations, the multiphase structure that evolves during initial cycling determines critical electrochemical and mechanical properties of the SEI. A basic model of these tradeoffs is proposed to provide guidelines for creating more stable interfacial films.  相似文献   

    

Jianwen Liang  Xiaona Li  Yang Zhao  Lyudmila V. Goncharova  Weihan Li  Keegan R. Adair  Mohammad Norouzi Banis  Yongfeng Hu  Tsun‐Kong Sham  Huan Huang  Li Zhang  Shangqian Zhao  Shigang Lu  Ruying Li  Xueliang Sun 《Liver Transplantation》2019,9(38)

Li metal is a promising anode material for all‐solid‐state batteries, owing to its high specific capacity and low electrochemical potential. However, direct contact of Li metal with most solid‐state electrolytes induces severe side reactions that can lead to dendrite formation and short circuits. Moreover, Li metal is unstable when exposed to air, leading to stringent processing requirements. Herein, it is reported that the Li₃PS₄/Li interface in all‐solid‐state batteries can be stabilized by an air‐stable Li_xSiS_y protection layer that is formed in situ on the surface of Li metal through a solution‐based method. Highly stable Li cycling for over 2000 h in symmetrical cells and a lifetime of over 100 cycles can be achieved for an all‐solid‐state LiCoO₂/Li₃PS₄/Li cell. Synchrotron‐based high energy X‐ray photoelectron spectroscopy in‐depth analysis demonstrates the distribution of different components within the protection layer. The in situ formation of an electronically insulating Li_xSiS_y protection layer with highly ionic conductivity provides an effective way to prevent Li dendrite formation in high‐energy all‐solid‐state Li metal batteries.  相似文献   

    

Yaoyu Ren  Timo Danner  Alexandra Moy  Martin Finsterbusch  Tanner Hamann  Jan Dippell  Till Fuchs  Marius Müller  Ricky Hoft  André Weber  Larry A. Curtiss  Peter Zapol  Matthew Klenk  Anh T. Ngo  Pallab Barai  Brandon C. Wood  Rongpei Shi  Liwen F. Wan  Tae Wook Heo  Martin Engels  Jagjit Nanda  Felix H. Richter  Arnulf Latz  Venkat Srinivasan  Jürgen Janek  Jeff Sakamoto  Eric D. Wachsman  Dina Fattakhova-Rohlfing 《Liver Transplantation》2023,13(1):2201939

The garnet-type phase Li₇La₃Zr₂O₁₂ (LLZO) attracts significant attention as an oxide solid electrolyte to enable safe and robust solid-state batteries (SSBs) with potentially high energy density. However, while significant progress has been made in demonstrating compatibility with Li metal, integrating LLZO into composite cathodes remains a challenge. The current perspective focuses on the critical issues that need to be addressed to achieve the ultimate goal of an all-solid-state LLZO-based battery that delivers safety, durability, and pack-level performance characteristics that are unobtainable with state-of-the-art Li-ion batteries. This perspective complements existing reviews of solid/solid interfaces with more emphasis on understanding numerous homo- and heteroionic interfaces in a pure oxide-based SSB and the various phenomena that accompany the evolution of the chemical, electrochemical, structural, morphological, and mechanical properties of those interfaces during processing and operation. Finally, the insights gained from a comprehensive literature survey of LLZO–cathode interfaces are used to guide efforts for the development of LLZO-based SSBs.  相似文献   

    

Jingyi Wu  Zhixiang Rao  Zexiao Cheng  Lixia Yuan  Zhen Li  Yunhui Huang 《Liver Transplantation》2019,9(46)

All‐solid‐state batteries are promising candidates for the next‐generation safer batteries. However, a number of obstacles have limited the practical application of all‐solid‐state Li batteries (ASSLBs), such as moderate ionic conductivity at room temperature. Here, unlike most of the previous approaches, superior performances of ASSLBs are achieved by greatly reducing the thickness of the solid‐state electrolyte (SSE), where ionic conductivity is no longer a limiting factor. The ultrathin SSE (7.5 µm) is developed by integrating the low‐cost polyethylene separator with polyethylene oxide (PEO)/Li‐salt (PPL). The ultrathin PPL shortens Li⁺ diffusion time and distance within the electrolyte, and provides sufficient Li⁺ conductance for batteries to operate at room temperature. The robust yet flexible polyethylene offers mechanical support for the soft PEO/Li‐salt, effectively preventing short‐circuits even under mechanical deformation. Various ASSLBs with PPL electrolyte show superior electrochemical performance. An initial capacity of 135 mAh g^?1 at room temperature and the high‐rate capacity up to 10 C at 60 °C can be achieved in LiFePO₄/PPL/Li batteries. The high‐energy‐density sulfur cathode and MoS₂ anode employing PPL electrolyte also realize remarkable performance. Moreover, the ASSLB can be assembled by a facile process, which can be easily scaled up to mass production.  相似文献   

    

Ah‐Young Song  Yiran Xiao  Kostiantyn Turcheniuk  Punith Upadhya  Anirudh Ramanujapuram  Jim Benson  Alexandre Magasinski  Marco Olguin  Lamartine Meda  Oleg Borodin  Gleb Yushin 《Liver Transplantation》2018,8(3)

Li‐halide hydroxides (Li₂OHX) and Li‐oxyhalides (Li₃OX) have emerged as new classes of low‐cost, lightweight solid state electrolytes (SSE) showing promising Li‐ion conductivities. The similarity in the lattice parameters between them, careless synthesis, and insufficient rigor in characterization often lead to erroneous interpretations of their compositions. Finally, moisture remaining in the synthesis or cell assembling environment and variability in the equivalent circuit models additionally contribute to significant errors in their properties. Thus, there remains a controversy about the real values of Li‐ion conductivities in such SSEs. Here an ultra‐fast synthesis and comprehensive material characterization is utilized to report on the ionic conductivities of contaminant‐free Li2+xOH_1?xCl (x=0‐0.7), and Li₂OHBr not exceeding 10^‐4 S cm^‐1 at 110 °C. Using powerful combination of experimental and numerical approaches, it is demonstrated that the presence of H in these SSEs yields significantly higher Li⁺ ‐ionic conductivity. Born‐Oppenheimer molecular dynamics simulations show excellent agreement with experimental results and reveal an unexpected mechanism for faster Li⁺ transport. It involves rotation of a short OH‐group in SSEs, which opens lower‐energy pathways for the formation of Frenkel defects and highly‐correlated Li⁺ jumps. These findings will reduce the existing confusions and show new avenues for tuning SSE compositions for further improved Li‐ion conductivities.  相似文献   

Ion Conductivities: Protons Enhance Conductivities in Lithium Halide Hydroxide/Lithium Oxyhalide Solid Electrolytes by Forming Rotating Hydroxy Groups (Adv. Energy Mater. 3/2018)          下载免费PDF全文

Ah‐Young Song  Yiran Xiao  Kostiantyn Turcheniuk  Punith Upadhya  Anirudh Ramanujapuram  Jim Benson  Alexandre Magasinski  Marco Olguin  Lamartine Meda  Oleg Borodin  Gleb Yushin 《Liver Transplantation》2018,8(3)

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Frédéric Le Cras  Brigitte Pecquenard  Vincent Dubois  Viet‐Phong Phan  Delphine Guy‐Bouyssou 《Liver Transplantation》2015,5(19)

All‐solid‐state thin film lithium batteries are promising devices to power the next generations of autonomous microsystems. Nevertheless, some industrial constraints such as the resistance to reflow soldering (260 °C) and to short‐circuiting necessitate the replacement of the lithium anode. In this study, a 2 V lithium‐ion system based on amorphous silicon nanofilm anodes (50–200 nm thick), a LiPON electrolyte, and a new lithiated titanium oxysulfide cathode Li_1.2TiO_0.5S_2.1 is prepared by sputtering. The determination of the electrochemical behavior of each active material and of whole systems with different configurations allows the highlighting of the particular behavior of the Li_xSi electrode and the understanding of its consequences on the performance of Li‐ion cells. Lithium‐ion microbatteries processed with industrial tools and embedded in microelectronic packages exhibit particularly high cycle life (?0.006% cycle^?1), ultrafast charge (80% capacity in 1 min), and tolerate both short‐circuiting and reflow soldering. Moreover, the perfect stability of the system allows the assignment of some modifications of the voltage curve and a slow and reversible capacity fade occurring in specific conditions, to the formation of Li₁₅Si₄ and to the expression of a “memory effect.” These new findings will help to optimize the design of future Li‐ion systems using nanosized silicon anodes.  相似文献   

    

Insun Yoon  Daniel P. Abraham  Brett L. Lucht  Allan F. Bower  Pradeep R. Guduru 《Liver Transplantation》2016,6(12)

In situ measurements of the growth of solid electrolyte interphase (SEI) layer on silicon and the lithiation‐induced volume changes in silicon in lithium ion half‐cells are reported. Thin film amorphous silicon electrodes are fabricated in a configuration that allows unambiguous separation of the total thickness change into contribution from SEI thickness and silicon volume change. Electrodes are assembled into a custom‐designed electrochemical cell, which is integrated with an atomic force microscope. The electrodes are subjected to constant potential lithiation/delithiation at a sequence of potential values and the thickness measurements are made at each potential after equilibrium is reached. Experiments are carried out with two electrolytes—1.2 m lithium hexafluoro‐phosphate (LiPF₆) in ethylene carbonate (EC) and 1.2 m LiPF₆ in propylene carbonate (PC)—to investigate the influence of electrolyte composition on SEI evolution. It is observed that SEI formation occurs predominantly during the first lithiation and the maximum SEI thickness is ≈17 and 10 nm respectively for EC and PC electrolytes. This study also presents the measured Si expansion ratio versus equilibrium potential and charge capacity versus equilibrium potential; both relationships display hysteresis, which is explained in terms of the stress–potential coupling in silicon.  相似文献   

    

Vanchiappan Aravindan  Yun‐Sung Lee  Srinivasan Madhavi 《Liver Transplantation》2017,7(17):1602607

Development of high performance lithium‐ion (Li‐ion) power packs is a topic receiving significant attention in research today. Future development of the Li‐ion power packs relies on the development of high capacity and high rate anodes. More specifically, materials undergo either conversion or an alloying mechanism with Li. However, irreversible capacity loss (ICL) is one of the prime issues for this type of negative electrode. Traditional insertion‐type materials also experience ICL, but it is considered negligible. Therefore, eliminating ICL is crucial before the fabrication of practical Li‐ion cells with conventional cathodes such as LiFePO₄, LiMn₂O₄, etc. There are numerous methods for eliminating ICL such as pre‐treating the electrode, usage of stabilized Li metal powder, chemical and electrochemical lithiation, sacrificial salts for both anode and cathode, etc. The research strategies that have been explored are reviewed here in regards to the elimination of ICL from the high capacity anodes as described. Additionally, mitigating ICL observed from the carbonaceous anodes is discussed and compared.  相似文献   

    

Jan van den Broek  Semih Afyon  Jennifer L. M. Rupp 《Liver Transplantation》2016,6(19)

All‐solid‐state Li‐ion batteries based on Li₇La₃Zr₂O₁₂ (LLZO) garnet structures require novel electrode assembly strategies to guarantee a proper Li⁺ transfer at the electrode–electrolyte interfaces. Here, first stable cell performances are reported for Li‐garnet, c‐Li_6.25Al_0.25La₃Zr₂O₁₂, all‐solid‐state batteries running safely with a full ceramics setup, exemplified with the anode material Li₄Ti₅O₁₂. Novel strategies to design an enhanced Li⁺ transfer at the electrode–electrolyte interface using an interface‐engineered all‐solid‐state battery cell based on a porous garnet electrolyte interface structure, in which the electrode material is intimately embedded, are presented. The results presented here show for the first time that all‐solid‐state Li‐ion batteries with LLZO electrolytes can be reversibly charge–discharge cycled also in the low potential ranges (≈1.5 V) for combinations with a ceramic anode material. Through a model experiment, the interface between the electrode and electrolyte constituents is systematically modified revealing that the interface engineering helps to improve delivered capacities and cycling properties of the all‐solid‐state Li‐ion batteries based on garnet‐type cubic LLZO structures.  相似文献   

    

William Fitzhugh  Fan Wu  Luhan Ye  Wenye Deng  Pengfei Qi  Xin Li 《Liver Transplantation》2019,9(21)

Interfacial reactions between ceramic‐sulfide solid‐electrolytes and common electrodes have remained a major impediment to the development of solid‐state lithium‐ion batteries. In practice, this means that ceramic‐sulfide batteries require a suitable coating material to isolate the electrolyte from the electrode materials. In this work, the interfacial stability of Li₁₀SiP₂S₁₂ with over 67 000 materials is computationally evaluated. Over 2000 materials that are predicted to form stable interfaces in the cathode voltage range and over 1000 materials for the anode range are reported on and cataloged. LiCoO₂ is chosen as an example cathode material to identify coating compounds that are stable with both Li₁₀SiP₂S₁₂ and a common cathode. The correlation between elemental composition and multiple instability metrics (e.g., chemical/electrochemical) is analyzed, revealing key trends in, amongst others, the role of anion selection. A new binary‐search algorithm is introduced for evaluating the pseudo‐phase with improved speed and accuracy. Computational challenges posed by high‐throughput interfacial phase‐diagram calculations are highlighted as well as pragmatic computational methods to make such calculations routinely feasible. In addition to the over 3000 materials cataloged, representative materials from the anionic classes of oxides, fluorides, and sulfides are chosen to experimentally demonstrate chemical stability when in contact with Li₁₀SiP₂S₁₂.  相似文献   

    

Ying Zhang  Yang Shi  Xin‐Cheng Hu  Wen‐Peng Wang  Rui Wen  Sen Xin  Yu‐Guo Guo 《Liver Transplantation》2020,10(3)

To reconcile the energy storage ability and operational safety of lithium metal batteries (LMBs), a transformation from a liquid to a solid‐state system is required. However, Li volume variation, poor interfacial contact, and high operation temperatures hinder its practical applications. To address the above issues, here, an integral structure design for solid‐state LMBs is shown, in which a Li‐preinfused 3D carbon fiber (Li/CF) anode is ionically connected to a cathode via an autopolymerized gel electrolyte. The gel electrolyte helps to encapsulate the liquid electrolyte within the Li/CF anode and the cathode to improve the interfacial contact. The gel also serves as a reservoir that balances the liquid electrolyte supply during repeated Li stripping/plating process. As a result, the symmetrical cells and full cells with Li/CF electrodes exhibit improved cycling stability and effective suppression of dendrites at ambient temperature. This work facilitates the realization of solid‐state LMBs with high energy and high safety.  相似文献   

    

Ah‐Young Song  Kostiantyn Turcheniuk  Johannes Leisen  Yiran Xiao  Lamartine Meda  Oleg Borodin  Gleb Yushin 《Liver Transplantation》2020,10(8)

Low‐melting‐point solid‐state electrolytes (SSE) are critically important for low‐cost manufacturing of all‐solid‐state batteries. Lithium hydroxychloride (Li₂OHCl) is a promising material within the SSE domain due to its low melting point (mp < 300 °C), cheap ingredients (Li, H, O, and Cl), and rapid synthesis. Another unique feature of this compound is the presence of Li vacancies and rotating hydroxyl groups which promote Li‐ion diffusion, yet the role of the protons in the ion transport remains poorly understood. To examine lithium and proton dynamics, a set of solid‐state NMR experiments are conducted, such as magic‐angle spinning ⁷Li NMR, static ⁷Li and ¹H NMR, and spin‐lattice T₁(⁷Li)/T₁(¹H) relaxation experiments. It is determined that only Li⁺ contributes to long‐range ion transport, while H⁺ dynamics is constrained to an incomplete isotropic rotation of the OH group. The results uncover detailed mechanistic understanding of the ion transport in Li₂OHCl. It is shown that two distinct phases of ionic motions appear at low and elevated temperatures, and that the rotation of the OH group controls Li⁺ and H⁺ dynamics in both phases. The model based on the NMR experiments is fully consistent with crystallographic information, ionic conductivity measurements, and Born–Oppenheimer molecular dynamic simulations.  相似文献   

    

Patrick J. Phillips  Javier Bareño  Yan Li  Daniel P. Abraham  Robert F. Klie 《Liver Transplantation》2015,5(23)

Although the Li‐excess layered‐oxide Li₂MnO₃ has a high theoretical capacity, structural transformations within the oxide during electrochemical cycling lead to relatively low experimental capacities, hindering its use in practical applications. Here, aberration‐corrected scanning transmission electron microscopy/electron energy loss spectroscopy and high‐resolution X‐ray diffraction are used to characterize the oxide following electrochemical cycling. Microscopy reveals the coexistence of regions with local monoclinic, spinel, and rock‐salt symmetries, indicating localized and inhomogeneous structural evolutions. Crystal structure transformations are observed both at the particle surface and in the bulk. At the surface, these transformed regions resemble spinel Mn₃O₄ or rock‐salt MnO, consistent with oxygen loss. In the bulk, the regions resemble defect spinels, such as the layered‐spinel Li_xMn_4/3O₄, which suggest a partial phase transformation consistent with oxygen retention. Both microscopy and diffraction data of the cycled sample indicate areas of pristine Li₂MnO₃; the presence of such areas, in close proximity to Li_xMn_4/3O₄ areas, suggests that the layered to spinel structure transformation is partially reversible. Spinel, disordered rock salt, and pristine areas are also observed in Li₂MnO₃ samples intentionally damaged by electron beam irradiation. This observation indicates that the dynamic processes resulting in phase transformations can be studied for a variety of oxide systems by a judicious selection of irradiation conditions.  相似文献   

    

Mrunal M. Yawalkar  G. D. Zade  K. V. Dabre  S. J. Dhoble 《Luminescence》2016,31(4):1037-1042

In this study, Li₆Y_1–xEu_x(BO₃)₃ phosphor was successfully synthesized using a modified solid‐state diffusion method. The Eu³⁺ ion concentration was varied at 0.05, 0.1, 0.2, 0.5 and 1 mol%. The phosphor was characterized for phase purity, morphology, luminescent properties and molecular transmission at room temperature. The XRD pattern suggests a result closely matching the standard JCPDS file (#80‐0843). The emission and excitation spectra were followed to discover the luminescence traits. The excitation spectra indicate that the current phosphor can be efficiently excited at 395 nm and at 466 nm (blue light) to give emission at 595 and 614 nm due to the ⁵D₀ → ⁷F_j transition of Eu³⁺ ions. Concentration quenching was observed at 0.5 mol% Eu³⁺ in the Li₆Y_1–xEu_x(BO₃)₃ host lattice. Strong red emission with CIE chromaticity coordinates of phosphor is x = 0.63 and y = 0.36 achieved with dominant red emission at 614 nm the ⁵D₀ → ⁷ F₂ electric dipole transition of Eu³⁺ ions. The novel Li₆Y_1–xEu_x(BO₃)₃ phosphor may be a suitable red‐emitting component for solid‐state lighting using double‐excited wavelengths, i.e. near‐UV at 395 nm and blue light at 466 nm. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

    

Yanming He  Chuanyang Lu  Shan Liu  Wenjian Zheng  Jiayan Luo 《Liver Transplantation》2019,9(36)

Rechargeable Li‐ion batteries (LIBs) are electrochemical storage device widely applied in electric vehicles, mobile electronic devices, etc. However, traditional LIBs containing liquid electrolytes suffer from flammability, poor electrochemical stability, and limited operational temperature range. Replacement of the liquid electrolytes with inorganic solid‐state electrolytes (SSEs) would solve this problem. However, several critical issues, such as poor interfacial compatibility, low ionic conductivity at ambient temperatures, etc., need to be surmounted before the commercialization of all‐solid‐state Li‐ion batteries (ASSLIBs). In this review, a brief historical context for the inorganic SSEs is described first. Then, two critical issues in the ASSLIBs are highlighted: interfacial incompatibility of the electrodes and SSEs and internal stresses. For the interfacial incompatibility, the discussion is focused on the dynamic characterization of the electrode/SSE interfaces, the origin and evolution of the interfacial resistance, and interface engineering to minimize the interfacial resistance. The internal stresses in the ASSLIBs are another major concern because rigid contacts are introduced. Stress generation, stress evolution during battery cycling, stress measurement/simulation, and ways to alleviate the stresses are outlined in detail. Finally, current challenges and perspectives for future development of the inorganic SSEs and ASSLIBs are outlined.  相似文献   

    

Andrea Di Cicco  Angelo Giglia  Roberto Gunnella  Stephan L. Koch  Franziska Mueller  Francesco Nobili  Marta Pasqualini  Stefano Passerini  Roberto Tossici  Agnieszka Witkowska 《Liver Transplantation》2015,5(18)

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Jongsoon Kim  Jung‐Keun Yoo  Yeon Sik Jung  Kisuk Kang 《Liver Transplantation》2013,3(8):1004-1007

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Xiaoyu Zhang  Tomas W. Verhallen  Freek Labohm  Marnix Wagemaker 《Liver Transplantation》2015,5(15)

One of the key challenges of Li‐ion electrodes is enhancement of (dis)charge rates. This is severely hindered by the absence of a technique that allows direct and nondestructive observation of lithium ions in operating batteries. Direct observation of the Li‐ion concentration profiles using operando neutron depth profiling reveals that the rate‐limiting step is depended not only on the electrode morphology but also on the cycling rate itself. In the LiFePO₄ electrodes phase nucleation limits the charge transport at the lowest cycling rates, whereas electronic conductivity is rate limiting at intermediate rates, and only at the highest rates ionic transport through the electrode is rate limiting. These novel insights into electrode kinetics are imperative for the improvement of Li‐ion batteries and show the large value of in situ NDP in Li‐ion battery research and development.  相似文献