scholarly journals Dendrite-Free Lithium Electrodeposition Enabled by 3D Porous Lithiophilic Host toward Stable Lithium Metal Anodes

Author(s):  
Linghong Xu ◽  
Zhihao Yu ◽  
Junrong Zheng

Abstract Lithium metal is a promising anode utilized in cutting-edge high-energy batteries owing to the low density, low electrochemical potential, and super high theoretical capacity. Unfortunately, continuous uncontrollable lithium dendrite growth and ‘dead’ lithium result in capacity decay, low coulombic efficiency, and short circuit, severely hindering the practical utilization of lithium anode. Herein, we propose a three-dimensional porous lithiophilic current collector for lithium storage. The conductive 3D structure constructed by carbon fiber (CF) can well accommodate the deposited lithium, eliminating volume change between the lithium depositing/stripping process. Moreover, the polydopamine (PDA) coating on the CF surface possesses a large number of polar groups, which can homogenize Li+ ions distribution and apply as the sites for lithium deposition, decreasing nucleation overpotential. As a result, under the 1 mA cm−2 current density, the PDA coated CF (PDA@CF) electrode exhibits high CE (∼98%) for 1000 cycles. Galvanostatic measurements demonstrate that the Li anode using PDA@CF achieves 1000 h cycling life under 1 mA cm−2 with a low overpotential (<15 mV). The LiFePO4 full cell shows enhanced rate performance and stable long-term cycling.

NANO ◽  
2020 ◽  
Vol 15 (03) ◽  
pp. 2050033
Author(s):  
Wenyang Zhang ◽  
Jialin Li ◽  
Haixia Chen ◽  
Huixin Jin ◽  
Pan Li ◽  
...  

Metallic lithium (Li) is an outstanding anode for high-energy storage devices, but dendrite growth impedes its practical application. Herein, similar to molding process of mooncake, a facile strategy of templated etching has been developed to manufacture three dimensional (3D) current collectors with hierarchical pore structures and biomimetic surfaces derived from natural templates. By using polydimethylsiloxane (PDMS) as duplicate templates, 3D surface morphologies of natural surfaces can be printed on Cu foil, and the resuable templates facilitate mass production. By comparison, the 3D porous current collectors largely improve Li deposition behavior and suppress dendrite growth. They exhibit excellent electrochemical performances: high Coulombic efficiency (CE), long life spans of more than 1000[Formula: see text]h and good cycling performance. The templated etching method overcomes the energy/time-consuming disadvantages of past pore-creating methods and will boost the commercialization of lithium metal batteries.


2020 ◽  
Author(s):  
Urbi Pal ◽  
Fangfang Chen ◽  
Derick Gyabang ◽  
Thushan Pathirana ◽  
Binayak Roy ◽  
...  

We explore a novel ether aided superconcentrated ionic liquid electrolyte; a combination of ionic liquid, <i>N</i>-propyl-<i>N</i>-methylpyrrolidinium bis(fluorosulfonyl)imide (C<sub>3</sub>mpyrFSI) and ether solvent, <i>1,2</i> dimethoxy ethane (DME) with 3.2 mol/kg LiFSI salt, which offers an alternative ion-transport mechanism and improves the overall fluidity of the electrolyte. The molecular dynamics (MD) study reveals that the coordination environment of lithium in the ether aided ionic liquid system offers a coexistence of both the ether DME and FSI anion simultaneously and the absence of ‘free’, uncoordinated DME solvent. These structures lead to very fast kinetics and improved current density for lithium deposition-dissolution processes. Hence the electrolyte is used in a lithium metal battery against a high mass loading (~12 mg/cm<sup>2</sup>) LFP cathode which was cycled at a relatively high current rate of 1mA/cm<sup>2</sup> for 350 cycles without capacity fading and offered an overall coulombic efficiency of >99.8 %. Additionally, the rate performance demonstrated that this electrolyte is capable of passing current density as high as 7mA/cm<sup>2</sup> without any electrolytic decomposition and offers a superior capacity retention. We have also demonstrated an ‘anode free’ LFP-Cu cell which was cycled over 50 cycles and achieved an average coulombic efficiency of 98.74%. The coordination chemistry and (electro)chemical understanding as well as the excellent cycling stability collectively leads toward a breakthrough in realizing the practical applicability of this ether aided ionic liquid electrolytes in lithium metal battery applications, while delivering high energy density in a prototype cell.


2021 ◽  
Vol 13 (1) ◽  
Author(s):  
Lei Zheng ◽  
Feng Guo ◽  
Tuo Kang ◽  
Yingzhu Fan ◽  
Wei Gu ◽  
...  

AbstractLithium metal is regarded as the ultimate negative electrode material for secondary batteries due to its high energy density. However, it suffers from poor cycling stability because of its high reactivity with liquid electrolytes. Therefore, continuous efforts have been put into improving the cycling Coulombic efficiency (CE) to extend the lifespan of the lithium metal negative electrode. Herein, we report that using dual-salt additives of LiPF6 and LiNO3 in an ether solvent-based electrolyte can significantly improve the cycling stability and rate capability of a Li-carbon (Li-CNT) composite. As a result, an average cycling CE as high as 99.30% was obtained for the Li-CNT at a current density of 2.5 mA cm–2 and an negative electrode to positive electrode capacity (N/P) ratio of 2. The cycling stability and rate capability enhancement of the Li-CNT negative electrode could be attributed to the formation of a better solid electrolyte interphase layer that contains both inorganic components and organic polyether. The former component mainly originates from the decomposition of the LiNO3 additive, while the latter comes from the LiPF6-induced ring-opening polymerization of the ether solvent. This novel surface chemistry significantly improves the CE of Li negative electrode, revealing its importance for the practical application of lithium metal batteries.


Author(s):  
Naiqing Zhang ◽  
Xiaojie Shen ◽  
Guangyu Zhao ◽  
Xianbo Yu ◽  
Huihuang Huang ◽  
...  

Undesirable lithium dendrite growth limits the application of lithium metal anode in high-energy storage batteries. Here, multifunctional SnSe-C composite modified 3D scaffolds is constructed to achieve dendrite-free lithium deposition. During...


2020 ◽  
Vol 10 (12) ◽  
pp. 4185 ◽  
Author(s):  
Rajesh Pathak ◽  
Yue Zhou ◽  
Qiquan Qiao

Rechargeable lithium metal anode (LMA) based batteries have attracted great attention as next-generation high-energy-density storage systems to fuel the extensive practical applications in portable electronics and electric vehicles. However, the formation of unstable solid-electrolyte- interphase (SEI) and growth of lithium dendrite during plating/stripping cycles stimulate safety concern, poor coulombic efficiency (CE), and short lifespan of the lithium metal batteries (LMBs). To address these issues, the rational design of micro/nanostructured Li hosts are widely adopted in LMBs. The high surface area of the interconnected conductive framework can homogenize the Li-ion flux distribution, lower the effective current density, and provides sufficient space for Li accommodation. However, the poor lithiophilicity of the micro/nanostructure host cannot govern the initial lithium nucleation, which leads to the non-uniform/dendritic Li deposition and unstable SEI formation. As a result, the nucleation overpotential and voltage hysteresis increases, which eventually leads to poor battery cycling performance. Thus, it is imperative to decorate a micro/nanostructured Li host with lithiophilic coatings or seeds for serving as a homogeneous nucleation site to guide the uniform lithium deposition. In this review, we summarize research progress on porous metal and non-metal based lithiophilic micro/nanostructured Li hosts. We present the synthesis, structural properties, and the significance of lithiophilic decorated micro/nanostructured Li host in the LMBs. Finally, the perspectives and critical challenges needed to address for the further improvement of LMBs are concluded.


2019 ◽  
Vol 10 ◽  
pp. 514-521 ◽  
Author(s):  
Yongguang Zhang ◽  
Jun Ren ◽  
Yan Zhao ◽  
Taizhe Tan ◽  
Fuxing Yin ◽  
...  

In this work, a unique three-dimensional (3D) structured carbon-based composite was synthesized. In the composite, multiwalled carbon nanotubes (MWCNT) form a lattice matrix in which porous spherical reduced graphene oxide (RGO) completes the 3D structure. When used in Li–S batteries, the 3D porous lattice matrix not only accommodates a high content of sulfur, but also induces a confinement effect towards polysulfide, and thereby reduces the “shuttle effect”. The as-prepared S-3D-RGO@MWCNT composite delivers an initial specific capacity of 1102 mAh·g−1. After 200 charging/discharge cycles, a capacity of 805 mAh·g−1 and a coulombic efficiency of 98% were maintained, implying the shuttle effect was greatly suppressed by the composite matrix. In addition, the S-3D-RGO@MWCNT composite also exhibits an excellent rate capability.


2020 ◽  
Vol 6 (10) ◽  
pp. eaaz3112 ◽  
Author(s):  
Huadong Yuan ◽  
Jianwei Nai ◽  
He Tian ◽  
Zhijin Ju ◽  
Wenkui Zhang ◽  
...  

The lithium metal anode (LMA) is considered as a promising star for next-generation high-energy density batteries but is still hampered by the severe growth of uncontrollable lithium dendrites. Here, we design “spansules” made of NaMg(Mn)F3@C core@shell microstructures as the matrix for the LMA, which can offer a long-lasting release of functional ions into the electrolyte. By the assistance of cryogenic transmission electron microscopy, we reveal that an in situ–formed metal layer and a unique LiF-involved bilayer structure on the Li/electrolyte interface would be beneficial for effectively suppressing the growth of lithium dendrites. As a result, the spansule-modified anode affords a high Coulombic efficiency of 98% for over 1000 cycles at a current density of 2 mA cm−2, which is the most stable LMA reported so far. When coupling this anode with the Li[Ni0.8Co0.1Mn0.1]O2 cathode, the practical full cell further exhibits highly improved capacity retention after 500 cycles.


2010 ◽  
Vol 25 (8) ◽  
pp. 1485-1491 ◽  
Author(s):  
Emilie Perre ◽  
Pierre Louis Taberna ◽  
Driss Mazouzi ◽  
Philippe Poizot ◽  
Torbjörn Gustafsson ◽  
...  

An increasing demand on high energy and power systems has arisen not only with the development of electric vehicle (EV), hybrid electric vehicle (HEV), telecom, and mobile technologies, but also for specific applications such as powering of microelectronic systems. To power those microdevices, an extra variable is added to the equation: a limited footprint area. Three-dimensional (3D) microbatteries are a solution to combine high-density energy and power. In this work, we present the formation of Cu2Sb onto three-dimensionally architectured arrays of Cu current collectors. Sb electrodeposition conditions and annealing post treatment are discussed in light of their influence on the morphology and battery performances. An increase of cycling stability was observed when Sb was fully alloyed with the Cu current collector. A subsequent separator layer was added to the 3D electrode when optimized. Equivalent capacity values are measured for at least 20 cycles. Work is currently devoted to the identification of the causes of capacity fading.


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