Simultaneous Stabilization of LiNi0.76 Mn0.14 Co0.10 O2 Cathode and Lithium Metal Anode by Lithium Bis(oxalato)borate as Additive.

The long-term cycling performance, rate capability, and voltage stability of lithium (Li) metal batteries with LiNi0.76 Mn0.14 Co0.10 O2 (NMC76) cathodes is greatly enhanced by lithium bis(oxalato)borate (LiBOB) additive in the LiPF6 -based electrolyte. With 2 % LiBOB in the electrolyte, a Li∥NMC76 cell is able to achieve a high capacity retention of 96.8 % after 200 cycles at C/3 rate (1 C=200 mA g-1 ), which is the best result reported for a Ni-rich NMC cathode coupled with Li metal anode. The significantly enhanced electrochemical performance can be ascribed to the stabilization of both the NMC76 cathode/electrolyte and Li-metal-anode/electrolyte interfaces. The LiBOB-containing electrolyte not only facilitates the formation of a more compact solid-electrolyte interphase on the Li metal surface, it also forms a enhanced cathode electrolyte interface layer, which efficiently prevents the corrosion of the cathode interface and mitigates the formation of the disordered rock-salt phase after cycling. The fundamental findings of this work highlight the importance of recognizing the dual effects of electrolyte additives in simultaneously stabilizing both cathode and anode interfaces, so as to enhance the long-term cycle life of high-energy-density battery systems.

[1]  Ji‐Guang Zhang,et al.  High Voltage Operation of Ni‐Rich NMC Cathodes Enabled by Stable Electrode/Electrolyte Interphases , 2018 .

[2]  Yuyan Shao,et al.  Addressing Passivation in Lithium–Sulfur Battery Under Lean Electrolyte Condition , 2018 .

[3]  Xin-bo Zhang,et al.  Hybrid electrolyte with robust garnet-ceramic electrolyte for lithium anode protection in lithium-oxygen batteries , 2018, Nano Research.

[4]  C. Yoon,et al.  High-Energy Ni-Rich Li[NixCoyMn1–x–y]O2 Cathodes via Compositional Partitioning for Next-Generation Electric Vehicles , 2017 .

[5]  Shiyou Li,et al.  Synthesis and properties of nanostructured LiNi1/3Co1/3Mn1/3O2 as cathode with lithium bis(oxalate)borate-based electrolyte to improve cycle performance in Li-ion battery , 2017 .

[6]  B. McCloskey,et al.  Promising Routes to a High Li+ Transference Number Electrolyte for Lithium Ion Batteries , 2017 .

[7]  G. Veith,et al.  Lithium malonatoborate additives enabled stable cycling of 5 V lithium metal and lithium ion batteries , 2017 .

[8]  Quan-hong Yang,et al.  Processable and Moldable Sodium-Metal Anodes. , 2017, Angewandte Chemie.

[9]  A. Trifonova,et al.  The effect of electrolyte additives on electrochemical performance of silicon/mesoporous carbon (Si/MC) for anode materials for lithium-ion batteries , 2017 .

[10]  Zhengcheng Zhang,et al.  Functionality Selection Principle for High Voltage Lithium-ion Battery Electrolyte Additives. , 2017, ACS applied materials & interfaces.

[11]  T. Kyu,et al.  Chemical and electrochemical stability enhancement of lithium bis(oxalato)borate (LiBOB)-modified solid polymer electrolyte membrane in lithium ion half-cells , 2017 .

[12]  Wei Liu,et al.  Atomic Layer Deposition of Stable LiAlF4 Lithium Ion Conductive Interfacial Layer for Stable Cathode Cycling. , 2017, ACS nano.

[13]  Yue Yu,et al.  In Situ Construction of Stable Tissue‐Directed/Reinforced Bifunctional Separator/Protection Film on Lithium Anode for Lithium–Oxygen Batteries , 2017, Advanced materials.

[14]  Benjamin T. Young,et al.  Effect of Lithium Borate Additives on Cathode Film Formation in LiNi0.5Mn1.5O4/Li Cells. , 2017, ACS applied materials & interfaces.

[15]  Ji‐Guang Zhang,et al.  Li‐ and Mn‐Rich Cathode Materials: Challenges to Commercialization , 2017 .

[16]  Chong Yan,et al.  Fluoroethylene Carbonate Additives to Render Uniform Li Deposits in Lithium Metal Batteries , 2017 .

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

[18]  Weishan Li,et al.  Insight into the interaction between layered lithium-rich oxide and additive-containing electrolyte , 2017 .

[19]  G. Veith,et al.  A Novel Electrolyte Salt Additive for Lithium‐Ion Batteries with Voltages Greater than 4.7 V , 2017 .

[20]  Ji‐Guang Zhang,et al.  The roles of oxygen non-stoichiometry on the electrochemical properties of oxide-based cathode materials , 2016 .

[21]  T. Rojo,et al.  Towards High‐Safe Lithium Metal Anodes: Suppressing Lithium Dendrites via Tuning Surface Energy , 2016, Advanced science.

[22]  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 .

[23]  Fabio Albano,et al.  Modification of Ni-Rich FCG NMC and NCA Cathodes by Atomic Layer Deposition: Preventing Surface Phase Transitions for High-Voltage Lithium-Ion Batteries , 2016, Scientific Reports.

[24]  Liu Zhou,et al.  Development of novel lithium borate additives for designed surface modification of high voltage LiNi0.5Mn1.5O4 cathodes , 2016 .

[25]  Samuel S. Cartmell,et al.  Highly Stable Operation of Lithium Metal Batteries Enabled by the Formation of a Transient High‐Concentration Electrolyte Layer , 2016 .

[26]  Hui Li,et al.  Enhanced electrochemical performance of LiNi0.5Co0.2Mn0.3O2 cathode material by ultrathin ZrO2 coating , 2016 .

[27]  K. Amine,et al.  Atomic to Nanoscale Investigation of Functionalities of an Al2O3 Coating Layer on a Cathode for Enhanced Battery Performance , 2016 .

[28]  Kang Xu,et al.  “Water-in-salt” electrolyte enables high-voltage aqueous lithium-ion chemistries , 2015, Science.

[29]  Xin-bo Zhang,et al.  Artificial Protection Film on Lithium Metal Anode toward Long‐Cycle‐Life Lithium–Oxygen Batteries , 2015, Advanced materials.

[30]  M. J. McDonald,et al.  Copper Phosphate as a Cathode Material for Rechargeable Li Batteries and Its Electrochemical Reaction Mechanism , 2015 .

[31]  J. E. Lee,et al.  Lithium difluoro(oxalate)borate for robust passivation of LiNi0.5Mn1.5O4 in lithium-ion batteries , 2015 .

[32]  W. Liu,et al.  Nickel‐reiche Lithium‐Übergangsmetall‐Schichtverbindungen für Hochenergie‐Lithiumionenakkumulatoren , 2015 .

[33]  Min-Joon Lee,et al.  Nickel-rich layered lithium transition-metal oxide for high-energy lithium-ion batteries. , 2015, Angewandte Chemie.

[34]  A. Manthiram,et al.  Role of Mn content on the electrochemical properties of nickel-rich layered LiNi(0.8-x)Co(0.1)Mn(0.1+x)O₂ (0.0 ≤ x ≤ 0.08) cathodes for lithium-ion batteries. , 2015, ACS applied materials & interfaces.

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

[36]  J. Dahn,et al.  Effect of Sulfate Electrolyte Additives on LiNi1/3Mn1/3Co1/3O2/Graphite Pouch Cell Lifetime: Correlation between XPS Surface Studies and Electrochemical Test Results , 2014 .

[37]  Kang Xu,et al.  Electrolytes and interphases in Li-ion batteries and beyond. , 2014, Chemical reviews.

[38]  D. Abraham,et al.  Electrolyte additive combinations that enhance performance of high-capacity Li1.2Ni0.15Mn0.55Co0.1O2–graphite cells , 2013 .

[39]  Yong Yang,et al.  Improved electrochemical performance of Li[Li0.2Mn0.54Ni0.13Co0.13]O2 cathode material by fluorine incorporation , 2013 .

[40]  Chong Seung Yoon,et al.  Improvement of long-term cycling performance of Li[Ni0.8Co0.15Al0.05]O2 by AlF3 coating , 2013 .

[41]  Shengbo Zhang,et al.  Liquid electrolyte lithium/sulfur battery: Fundamental chemistry, problems, and solutions , 2013 .

[42]  Chong Seung Yoon,et al.  Nanostructured high-energy cathode materials for advanced lithium batteries. , 2012, Nature materials.

[43]  Yang-Kook Sun,et al.  High-voltage performance of concentration-gradient Li[Ni0.67Co0.15Mn0.18]O2 cathode material for lithium-ion batteries , 2010 .

[44]  M. Armand,et al.  Issues and challenges facing rechargeable lithium batteries , 2001, Nature.

[45]  Yang-Kook Sun,et al.  Nickel‐Rich and Lithium‐Rich Layered Oxide Cathodes: Progress and Perspectives , 2016 .

[46]  Vanchiappan Aravindan,et al.  Effect of LiBOB Additive on the Electrochemical Performance of LiCoPO4 , 2012 .

[47]  B. Lucht,et al.  Effect of Added LiBOB on High Voltage (LiNi0.5Mn1.5O4) Spinel Cathodes , 2011 .