Behavior of Lithium Metal Anodes under Various Capacity Utilization and High Current Density in Lithium Metal Batteries

Summary Lithium (Li) metal batteries (LMBs) have recently attracted extensive interest in the energy-storage field after silence from the public view for several decades. However, many challenges still need to be overcome before their practical application, especially those that are related to the interfacial instability of Li metal anodes. Here, we reveal for the first time that the thickness of the degradation layer on the metallic Li anode surface shows a linear relationship with Li areal capacity utilization up to 4.0 mAh cm −2 in a practical LMB system. The increase in Li capacity utilization in each cycle causes variations in the morphology and composition of the degradation layer on the Li anode. Under high Li capacity utilization, the current density for charge (i.e., Li deposition) is identified to be a key factor controlling the corrosion of the Li metal anode. These fundamental findings provide new perspectives for the development of rechargeable LMBs.

[1]  Guangyuan Zheng,et al.  Interconnected hollow carbon nanospheres for stable lithium metal anodes. , 2014, Nature nanotechnology.

[2]  Doron Aurbach,et al.  The Application of Atomic Force Microscopy for the Study of Li Deposition Processes , 1996 .

[3]  Ya‐Xia Yin,et al.  Accommodating lithium into 3D current collectors with a submicron skeleton towards long-life lithium metal anodes , 2015, Nature Communications.

[4]  Kang Xu,et al.  The Role of Cesium Cation in Controlling Interphasial Chemistry on Graphite Anode in Propylene Carbonate-Rich Electrolytes. , 2015, ACS applied materials & interfaces.

[5]  Xin-Bing Cheng,et al.  Conductive Nanostructured Scaffolds Render Low Local Current Density to Inhibit Lithium Dendrite Growth , 2016, Advanced materials.

[6]  Yuki Yamada,et al.  Review—Superconcentrated Electrolytes for Lithium Batteries , 2015 .

[7]  S. Passerini,et al.  Separators for Li-Ion and Li-Metal Battery Including Ionic Liquid Based Electrolytes Based on the TFSI− and FSI− Anions , 2014, International journal of molecular sciences.

[8]  Jianming Zheng,et al.  Electrolyte additive enabled fast charging and stable cycling lithium metal batteries , 2017, Nature Energy.

[9]  Ji‐Guang Zhang,et al.  Lithium metal anodes for rechargeable batteries , 2014 .

[10]  Yi Cui,et al.  Reviving the lithium metal anode for high-energy batteries. , 2017, Nature nanotechnology.

[11]  B. Dunn,et al.  Electrical Energy Storage for the Grid: A Battery of Choices , 2011, Science.

[12]  John B Goodenough,et al.  The Li-ion rechargeable battery: a perspective. , 2013, Journal of the American Chemical Society.

[13]  B. Polzin,et al.  Effects of Propylene Carbonate Content in CsPF₆-Containing Electrolytes on the Enhanced Performances of Graphite Electrode for Lithium-Ion Batteries. , 2016, ACS applied materials & interfaces.

[14]  Daniel Sharon,et al.  Review—Development of Advanced Rechargeable Batteries: A Continuous Challenge in the Choice of Suitable Electrolyte Solutions , 2015 .

[15]  Rotraut Merkle,et al.  Electron and Ion Transport In Li2O2 , 2013, Advanced materials.

[16]  P. Bruce,et al.  Nanostructured materials for advanced energy conversion and storage devices , 2005, Nature materials.

[17]  S. Skaarup,et al.  Ionic conductivity of pure and doped Li3N , 1983 .

[18]  Ji‐Guang Zhang,et al.  Enhanced charging capability of lithium metal batteries based on lithium bis(trifluoromethanesulfonyl)imide-lithium bis(oxalato)borate dual-salt electrolytes , 2016 .

[19]  J. Eckert,et al.  Role of 1,3-Dioxolane and LiNO3 Addition on the Long Term Stability of Nanostructured Silicon/Carbon Anodes for Rechargeable Lithium Batteries , 2016 .

[20]  T. Ohzuku,et al.  Layered Lithium Insertion Material of LiCo1/3Ni1/3Mn1/3O2 for Lithium-Ion Batteries , 2001 .

[21]  Yuki Yamada,et al.  Superconcentrated electrolytes for a high-voltage lithium-ion battery , 2016, Nature Communications.

[22]  Tsutomu Ohzuku,et al.  Solid-State Chemistry and Electrochemistry of LiCo1 ∕ 3Ni1 ∕ 3Mn1 ∕ 3O2 for Advanced Lithium-Ion Batteries III. Rechargeable Capacity and Cycleability , 2007 .

[23]  Kang Xu,et al.  Nonaqueous liquid electrolytes for lithium-based rechargeable batteries. , 2004, Chemical reviews.

[24]  Rui Zhang,et al.  A Review of Solid Electrolyte Interphases on Lithium Metal Anode , 2015, Advanced science.

[25]  Yi Cui,et al.  Promises and challenges of nanomaterials for lithium-based rechargeable batteries , 2016, Nature Energy.

[26]  O. Borodin,et al.  High rate and stable cycling of lithium metal anode , 2015, Nature Communications.

[27]  M. Stanley Whittingham,et al.  History, Evolution, and Future Status of Energy Storage , 2012, Proceedings of the IEEE.

[28]  Terence J. Lozano,et al.  Failure Mechanism for Fast‐Charged Lithium Metal Batteries with Liquid Electrolytes , 2015 .

[29]  Hyun-Wook Lee,et al.  Selective deposition and stable encapsulation of lithium through heterogeneous seeded growth , 2016, Nature Energy.