1000 Wh L−1 lithium-ion batteries enabled by crosslink-shrunk tough carbon encapsulated silicon microparticle anodes

Abstract Microparticulate Si, normally shelled with carbons, features higher tap density and less interfacial side reactions compared to its nanosized counterpart, showing great potential to be applied as high energy lithium-ion battery anodes. However, localized high stress generated during fabrication and particularly, under operating, could induce cracking of carbon shells and release pulverized nanoparticles, significantly deteriorating its electrochemical performance. Here we design a strong yet ductile carbon cage from an easily processing capillary shrinkage of graphene hydrogel followed by precise tailoring of inner voids. Such a structure, analog to the stable structure of plant cells, presents “imperfection-tolerance” to volume variation of irregular Si microparticles, maintaining the electrode integrity over 1000 cycles with Coulombic efficiency over 99.5%. This design enables the use of a dense and thick (3 mAh cm–2) microparticulate Si anode with an ultrahigh volumetric energy density of 1048 Wh L–1 achieved at pouch full-cell level coupled with a LiNi0.8Co0.1Mn0.1O2 cathode.

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Micron-Sized Monodisperse Particle LiNi0.6Co0.2Mn0.2O2 Derived by Oxalate Solvothermal Process Combined with Calcination as Cathode Material for Lithium-Ion Batteries

Materials ◽

10.3390/ma14102576 ◽

2021 ◽

Vol 14 (10) ◽

pp. 2576

Author(s):

Zhuo Chen ◽

Fangya Guo ◽

Youxiang Zhang

Keyword(s):

Lithium Ion Batteries ◽

Discharge Capacity ◽

Coulombic Efficiency ◽

Lithium Ion ◽

High Energy ◽

High Energy Density ◽

Commercial Application ◽

Side Reactions ◽

Monodisperse Particles ◽

Voltage Range

Ni-rich cathode LiNixCoyMn1-x-yO2 (NCM, x ≥ 0.5) materials are promising cathodes for lithium-ion batteries due to their high energy density and low cost. However, several issues, such as their complex preparation and electrochemical instability have hindered their commercial application. Herein, a simple solvothermal method combined with calcination was employed to synthesize LiNi0.6Co0.2Mn0.2O2 with micron-sized monodisperse particles, and the influence of the sintering temperature on the structures, morphologies, and electrochemical properties was investigated. The material sintered at 800 °C formed micron-sized particles with monodisperse characteristics, and a well-order layered structure. When charged–discharged in the voltage range of 2.8–4.3 V, it delivered an initial discharge capacity of 175.5 mAh g−1 with a Coulombic efficiency of 80.3% at 0.1 C, and a superior discharge capacity of 135.4 mAh g−1 with a capacity retention of 84.4% after 100 cycles at 1 C. The reliable electrochemical performance is probably attributable to the micron-sized monodisperse particles, which ensured stable crystal structure and fewer side reactions. This work is expected to provide a facile approach to preparing monodisperse particles of different scales, and improve the performance of Ni-rich NCM or other cathode materials for lithium-ion batteries.

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Nanocomposite of Si/C Anode Material Prepared by Hybrid Process of High-Energy Mechanical Milling and Carbonization for Li-Ion Secondary Batteries

Applied Sciences ◽

10.3390/app8112140 ◽

2018 ◽

Vol 8 (11) ◽

pp. 2140 ◽

Cited By ~ 6

Author(s):

Reddyprakash Maddipatla ◽

Chadrasekhar Loka ◽

Woo Choi ◽

Kee-Sun Lee

Keyword(s):

Electron Microscopy ◽

Anode Material ◽

Mechanical Milling ◽

Coulombic Efficiency ◽

Electronic Conductivity ◽

High Capacity ◽

Lithium Ion ◽

High Energy ◽

Particle Size Reduction ◽

Milled Powders

Si/C nanocomposite was successfully prepared by a scalable approach through high-energy mechanical milling and carbonization process. The crystalline structure of the milled powders was studied using X-ray diffraction (XRD) and transmission electron microscopy (TEM). Morphology of the milled powders was investigated by Field-emission scanning electron microscopy (FE-SEM). The effects of milling time on crystalline size, crystal structure and microstructure, and the electrochemical properties of the nanocomposite powders were studied. The nanocomposite showed high reversible capacity of ~1658 mAh/g with an initial cycle coulombic efficiency of ~77.5%. The significant improvement in cyclability and the discharge capacity was mainly ascribed to the silicon particle size reduction and carbon layer formation over silicon for good electronic conductivity. As the prepared nanocomposite Si/C electrode exhibits remarkable electrochemical performance, it is potentially applied as a high capacity anode material in the lithium-ion secondary batteries.

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Theoretical and Experimental Sets of Choice Anode/Cathode Architectonics for High-Performance Full-Scale LIB Built-up Models

Nano-Micro Letters ◽

10.1007/s40820-019-0315-8 ◽

2019 ◽

Vol 11 (1) ◽

Cited By ~ 15

Author(s):

H. Khalifa ◽

S. A. El-Safty ◽

A. Reda ◽

M. A. Shenashen ◽

M. M. Selim ◽

...

Keyword(s):

High Performance ◽

Density Functional ◽

Coulombic Efficiency ◽

Density Functional Theory Calculation ◽

Scale Up ◽

Lithium Ion ◽

Building Blocks ◽

High Energy ◽

Full Scale ◽

High Energy Density

Abstract To control the power hierarchy design of lithium-ion battery (LIB) built-up sets for electric vehicles (EVs), we offer intensive theoretical and experimental sets of choice anode/cathode architectonics that can be modulated in full-scale LIB built-up models. As primary structural tectonics, heterogeneous composite superstructures of full-cell-LIB (anode//cathode) electrodes were designed in closely packed flower agave rosettes TiO2@C (FRTO@C anode) and vertical-star-tower LiFePO4@C (VST@C cathode) building blocks to regulate the electron/ion movement in the three-dimensional axes and orientation pathways. The superpower hierarchy surfaces and multi-directional orientation components may create isosurface potential electrodes with mobile electron movements, in-to-out interplay electron dominances, and electron/charge cloud distributions. This study is the first to evaluate the hotkeys of choice anode/cathode architectonics to assemble different LIB–electrode platforms with high-mobility electron/ion flows and high-performance capacity functionalities. Density functional theory calculation revealed that the FRTO@C anode and VST-(i)@C cathode architectonics are a superior choice for the configuration of full-scale LIB built-up models. The integrated FRTO@C//VST-(i)@C full-scale LIB retains a huge discharge capacity (~ 94.2%), an average Coulombic efficiency of 99.85% after 2000 cycles at 1 C, and a high energy density of 127 Wh kg−1, thereby satisfying scale-up commercial EV requirements.

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Gaussian Process Based Crack Initiation Modeling for Design of Battery Anode Materials

Volume 2A: 45th Design Automation Conference ◽

10.1115/detc2019-97547 ◽

2019 ◽

Author(s):

Zhuoyuan Zheng ◽

Yanwen Xu ◽

Bo Chen ◽

Pingfeng Wang

Keyword(s):

Crack Initiation ◽

Surrogate Model ◽

High Stress ◽

Lithium Ion ◽

Electrochemical Process ◽

Fe Model ◽

Model Framework ◽

Major Drawback ◽

Cracking Behavior ◽

Si Anode

Abstract Silicon-based anode is one of the promising candidates for the next generation lithium ion batteries (LIBs) to achieve high power/energy density. However, the major drawback limiting the practical application of Si anode is that Si experiences significant volume change during its lithiation/de-lithiation cycles, which induces high stress and causes degradation and pulverization of the anode. This study focuses on the crack initiation performances of Si anode during the de-lithiation process. A multi-physics based finite element (FE) model is built to simulate the electrochemical process and crack generation during de-lithiation. On top of that, a Gaussian Processes (GP) based surrogate model is developed to assist the exploration of the crack initiation performances within the anode design space. It is found that, the thickness of the Si coating layer TSi, the yield strength σFc of Si material, the cohesive strength between Si and substrate σFs, and the curvature of the substrate ρ have large impacts on the cracking behavior of Si. This coupled FE simulation-GP surrogate model framework is also applicable to other types of LIB electrodes.

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A flexible high-energy lithium-ion battery with a carbon black-sandwiched Si anode

Electrochimica Acta ◽

10.1016/j.electacta.2016.12.105 ◽

2017 ◽

Vol 225 ◽

pp. 11-18 ◽

Cited By ~ 8

Author(s):

Chao Li ◽

Tongfei Shi ◽

Hideya Yoshitake ◽

Hongyu Wang

Keyword(s):

Carbon Black ◽

Lithium Ion Battery ◽

Lithium Ion ◽

High Energy ◽

Si Anode

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Zn Metal Anodes for Zn-Ion Batteries in Mild Aqueous Electrolytes: Challenges and Strategies

Nanomaterials ◽

10.3390/nano11102746 ◽

2021 ◽

Vol 11 (10) ◽

pp. 2746

Author(s):

Vo Pham Hoang Huy ◽

Luong Trung Hieu ◽

Jaehyun Hur

Keyword(s):

Coulombic Efficiency ◽

Low Cost ◽

Lithium Ion ◽

Uniform Electric Field ◽

Side Reactions ◽

Aqueous Electrolytes ◽

Design Strategies ◽

Practical Applications ◽

High Theoretical Capacity ◽

Metal Anodes

Over the past few years, rechargeable aqueous Zn-ion batteries have garnered significant interest as potential alternatives for lithium-ion batteries because of their low cost, high theoretical capacity, low redox potential, and environmentally friendliness. However, several constraints associated with Zn metal anodes, such as the growth of Zn dendrites, occurrence of side reactions, and hydrogen evolution during repeated stripping/plating processes result in poor cycling life and low Coulombic efficiency, which severely impede further advancements in this technology. Despite recent efforts and impressive breakthroughs, the origin of these fundamental obstacles remains unclear and no successful strategy that can address these issues has been developed yet to realize the practical applications of rechargeable aqueous Zn-ion batteries. In this review, we have discussed various issues associated with the use of Zn metal anodes in mildly acidic aqueous electrolytes. Various strategies, including the shielding of the Zn surface, regulating the Zn deposition behavior, creating a uniform electric field, and controlling the surface energy of Zn metal anodes to repress the growth of Zn dendrites and the occurrence of side reactions, proposed to overcome the limitations of Zn metal anodes have also been discussed. Finally, the future perspectives of Zn anodes and possible design strategies for developing highly stable Zn anodes in mildly acidic aqueous environments have been discussed.

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Nanostructured Si-C Composites As High-Capacity Anode Material For All-Solid-State Lithium-Ion Batteries

10.26434/chemrxiv.14096049.v1 ◽

2021 ◽

Author(s):

Stephanie Poetke ◽

Felix Hippauf ◽

Anne Baasner ◽

Susanne Dörfler ◽

Holger Althues ◽

...

Keyword(s):

Solid State ◽

Lithium Ion Batteries ◽

Silicon Nanoparticles ◽

Coulombic Efficiency ◽

High Capacity ◽

Lithium Ion ◽

Carbon Matrix ◽

Liquid Electrolyte ◽

Side Reactions ◽

Silicon Carbon

Silicon carbon void structures (Si-C) are attractive anode materials for Lithium-ion batteries to cope with the volume changes of silicon during cycling. In this study, Si-C with varying Si contents (28 ‑ 37 %) are evaluated in all-solid-state batteries (ASSBs) for the first time. The carbon matrix enables enhanced performance and lifetime of the Si-C composites compared to bare silicon nanoparticles in half-cells even at high loadings of up to 7.4 mAh cm-2. In full cells with nickel-rich NCM (LiNi0.9Co0.05Mn0.05O2, 210 mAh g-1), kinetic limitations in the anode lead to a lowered voltage plateau compared to NCM half-cells. The solid electrolyte (Li6PS5Cl, 3 mS cm-1) does not penetrate the Si-C void structure resulting in less side reactions and higher initial coulombic efficiency compared to a liquid electrolyte (72.7 % vs. 31.0 %). Investigating the influence of balancing of full cells using 3-electrode ASSB cells revealed a higher delithiation of the cathode as a result of the higher cut-off voltage of the anode at high n/p ratios. During galvanostatic cycling, full cells with either a low or rather high overbalancing of the anode showed the highest capacity retention of up to 87.7 % after 50 cycles.

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An ultrathin ionomer interphase for high efficiency lithium anode in carbonate based electrolyte

Nature Communications ◽

10.1038/s41467-019-13783-1 ◽

2019 ◽

Vol 10 (1) ◽

Cited By ~ 11

Author(s):

Yu-Ting Weng ◽

Hao-Wen Liu ◽

Allen Pei ◽

FeiFei Shi ◽

Hansen Wang ◽

...

Keyword(s):

High Efficiency ◽

Coulombic Efficiency ◽

Solid Electrolyte Interphase ◽

Lithium Ion ◽

Current Collector ◽

High Energy ◽

Theoretical Simulation ◽

Polyhedral Oligosilsesquioxane ◽

Polyether Ether Ketone ◽

Lithium Metal Anodes

AbstractHigh coulombic efficiency and dendrite suppression in carbonate electrolytes remain challenges to the development of high-energy lithium ion batteries containing lithium metal anodes. Here we demonstrate an ultrathin (≤100 nm) lithium-ion ionomer membrane consisting of lithium-exchanged sulfonated polyether ether ketone embedded with polyhedral oligosilsesquioxane as a coating layer on copper or lithium for achieving efficient and stable lithium plating-stripping cycles in a carbonate-based electrolyte. Operando analyses and theoretical simulation reveal the remarkable ability of the ionomer coating to enable electric field homogenization over a considerably large lithium-plating surface. The membrane coating, serving as an artificial solid-electrolyte interphase filter in minimizing parasitic reactions at the electrolyte-electrode interface, enables dendrite-free lithium plating on copper with outstanding coulombic efficiencies at room and elevated (50 °C) temperatures. The membrane coated copper demonstrates itself as a promising current collector for manufacturing high-quality pre-plated lithium thin-film anode.

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Carbon-rich Conjugated Framework PTEB Modified Cu Nanowires for Stabilizing Lithium Metal Anode

Chemical Communications ◽

10.1039/d1cc04822h ◽

2021 ◽

Author(s):

Shan Yang ◽

Ru Xiao ◽

Tongwei Zhang ◽

Yuan Li ◽

Benhe Zhong ◽

...

Keyword(s):

Energy Density ◽

Dendritic Growth ◽

Coulombic Efficiency ◽

Lithium Ion ◽

High Energy ◽

High Energy Density ◽

Lithium Metal ◽

Metal Anode ◽

Cu Nanowires ◽

Lithium Metal Anode

Lithium metal anode provides a direction for the development of high-energy-density lithium ion batteries. In order to solve lithium dendritic growth and low Coulombic efficiency in lithium plating/stripping process, designing...

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