Cross Talk between Transition Metal Cathode and Li Metal Anode: Unraveling Its Influence on the Deposition/Dissolution Behavior and Morphology of Lithium

Lithium metal batteries (LMBs) combining a Li metal anode with a transition metal (TM) cathode can achieve higher practical energy densities (Wh L−1) than Li/S or Li/O2 cells. Research for improving the electrochemical behavior of the Li metal anode by, for example, modifying the liquid electrolyte is often conducted in symmetrical Li/Li or Li/Cu cells. This study now demonstrates the influence of the TM cathode on the Li metal anode, thus full cell behavior is analyzed in a way not considered so far in research with LMBs. Therefore, the deposition/dissolution behavior of Li metal and the resulting morphology is investigated with three different cathode materials (LiNi0.5Mn1.5O4, LiNi0.6Mn0.2Co0.2O2, and LiFePO4) by post mortem analysis with a scanning electron microscope. The observed large differences of the Li metal morphology are ascribed to the dissolution and crossover of TMs found deposited on Li metal and in the electrolyte by X‐ray photoelectron spectroscopy, energy‐dispersive X‐ray spectroscopy, and total reflection X‐ray fluorescence analysis. To support this correlation, the TM dissolution is simulated by adding Mn salt to the electrolyte. This study offers new insights into the cross talk between the Li metal anodes and TM cathodes, which is essential, when investigating Li metal electrodes for LMB full cells.

[1]  Kang Xu,et al.  Bisalt ether electrolytes: a pathway towards lithium metal batteries with Ni-rich cathodes , 2019, Energy & Environmental Science.

[2]  Federico Bella,et al.  Room temperature ionic liquid (RTIL)-based electrolyte cocktails for safe, high working potential Li-based polymer batteries , 2019, Journal of Power Sources.

[3]  Jinbao Zhao,et al.  Vinyl Ethylene Carbonate as an Effective SEI-Forming Additive in Carbonate-Based Electrolyte for Lithium-Metal Anodes. , 2019, ACS applied materials & interfaces.

[4]  H. Gasteiger,et al.  Nickel, Manganese, and Cobalt Dissolution from Ni-Rich NMC and Their Effects on NMC622-Graphite Cells , 2019, Journal of The Electrochemical Society.

[5]  Martin Winter,et al.  Theoretical versus Practical Energy: A Plea for More Transparency in the Energy Calculation of Different Rechargeable Battery Systems , 2018, Advanced Energy Materials.

[6]  M. Winter,et al.  Before Li Ion Batteries. , 2018, Chemical reviews.

[7]  Heng Zhang,et al.  Electrolyte Additives for Lithium Metal Anodes and Rechargeable Lithium Metal Batteries: Progress and Perspectives. , 2018, Angewandte Chemie.

[8]  Hongkyung Lee,et al.  Detrimental Effects of Chemical Crossover from the Lithium Anode to Cathode in Rechargeable Lithium Metal Batteries , 2018, ACS Energy Letters.

[9]  M. Winter,et al.  Total reflection X-ray fluorescence in the field of lithium ion batteries – Elemental detection in Lithium containing electrolytes using nanoliter droplets , 2018, Spectrochimica Acta Part B: Atomic Spectroscopy.

[10]  M. Winter,et al.  Investigation of various layered lithium ion battery cathode materials by plasma- and X-ray-based element analytical techniques , 2018, Analytical and Bioanalytical Chemistry.

[11]  H. Gasteiger,et al.  Electrolyte and SEI Decomposition Reactions of Transition Metal Ions Investigated by On-Line Electrochemical Mass Spectrometry , 2018 .

[12]  Heng Zhang,et al.  Elektrolytadditive für Lithiummetallanoden und wiederaufladbare Lithiummetallbatterien: Fortschritte und Perspektiven , 2018, Angewandte Chemie.

[13]  Daniel A. Steingart,et al.  Understanding Full-Cell Evolution and Non-chemical Electrode Crosstalk of Li-Ion Batteries , 2018, Joule.

[14]  Ji‐Guang Zhang,et al.  Dendrite‐Free and Performance‐Enhanced Lithium Metal Batteries through Optimizing Solvent Compositions and Adding Combinational Additives , 2018 .

[15]  Ji‐Guang Zhang,et al.  High‐Voltage Lithium‐Metal Batteries Enabled by Localized High‐Concentration Electrolytes , 2018, Advanced materials.

[16]  M. Winter,et al.  Interfaces and Materials in Lithium Ion Batteries: Challenges for Theoretical Electrochemistry , 2018, Topics in Current Chemistry.

[17]  M. Winter,et al.  Performance and cost of materials for lithium-based rechargeable automotive batteries , 2018 .

[18]  Shengbo Zhang.  Problem, Status, and Possible Solutions for Lithium Metal Anode of Rechargeable Batteries , 2018 .

[19]  Ji‐Guang Zhang,et al.  Guided Lithium Metal Deposition and Improved Lithium Coulombic Efficiency through Synergistic Effects of LiAsF6 and Cyclic Carbonate Additives , 2018 .

[20]  N. Wu,et al.  High Polarity Poly(vinylidene difluoride) Thin Coating for Dendrite‐Free and High‐Performance Lithium Metal Anodes , 2018 .

[21]  Hongkyung Lee,et al.  Suppressing Lithium Dendrite Growth by Metallic Coating on a Separator , 2017 .

[22]  Xiaodong Li,et al.  New Insights into Mossy Li Induced Anode Degradation and Its Formation Mechanism in Li–S Batteries , 2017 .

[23]  Jianming Zheng,et al.  Behavior of Lithium Metal Anodes under Various Capacity Utilization and High Current Density in Lithium Metal Batteries , 2017 .

[24]  Martin Winter,et al.  Lithium ion battery cells under abusive discharge conditions: Electrode potential development and interactions between positive and negative electrode , 2017 .

[25]  M. Winter,et al.  Learning from Electrochemical Data: Simple Evaluation and Classification of LiMO2‐type‐based Positive Electrodes for Li‐Ion Batteries , 2017 .

[26]  M. Winter,et al.  Improving cycle life of layered lithium transition metal oxide (LiMO2) based positive electrodes for Li ion batteries by smart selection of the electrochemical charge conditions , 2017 .

[27]  M. Winter,et al.  Lithium‐Metal Foil Surface Modification: An Effective Method to Improve the Cycling Performance of Lithium‐Metal Batteries , 2017 .

[28]  M. Winter,et al.  Determining oxidative stability of battery electrolytes: validity of common electrochemical stability window (ESW) data and alternative strategies. , 2017, Physical chemistry chemical physics : PCCP.

[29]  J. Connell,et al.  Lithium metal protected by atomic layer deposition metal oxide for high performance anodes , 2017 .

[30]  Kevin N. Wood,et al.  Dead lithium: Mass transport effects on voltage, capacity, and failure of lithium metal anodes , 2017 .

[31]  Martin Winter,et al.  Lithium ion, lithium metal, and alternative rechargeable battery technologies: the odyssey for high energy density , 2017, Journal of Solid State Electrochemistry.

[32]  Wangda Li,et al.  Formation and Inhibition of Metallic Lithium Microstructures in Lithium Batteries Driven by Chemical Crossover. , 2017, ACS nano.

[33]  Zhenan Bao,et al.  Lithium Metal Anodes with an Adaptive "Solid-Liquid" Interfacial Protective Layer. , 2017, Journal of the American Chemical Society.

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

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

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

[37]  Xuanxuan Bi,et al.  Kinetics Tuning the Electrochemistry of Lithium Dendrites Formation in Lithium Batteries through Electrolytes. , 2017, ACS applied materials & interfaces.

[38]  D. Aurbach,et al.  On the Oxidation State of Manganese Ions in Li-Ion Battery Electrolyte Solutions. , 2017, Journal of the American Chemical Society.

[39]  Guangyuan Zheng,et al.  Nanoscale Nucleation and Growth of Electrodeposited Lithium Metal. , 2017, Nano letters.

[40]  H. Althues,et al.  Intrinsic Shuttle Suppression in Lithium-Sulfur Batteries for Pouch Cell Application , 2017 .

[41]  E. Peled,et al.  Review—SEI: Past, Present and Future , 2017 .

[42]  J. Binder,et al.  Influence of Synthesis, Dopants and Cycling Conditions on the Cycling Stability of Doped LiNi0.5Mn1.5O4 Spinels , 2017 .

[43]  H. Gasteiger,et al.  Transition metal dissolution and deposition in Li-ion batteries investigated by operando X-ray absorption spectroscopy , 2016 .

[44]  Martin Winter,et al.  Unraveling transition metal dissolution of Li 1.04 Ni 1/3 Co 1/3 Mn 1/3 O 2 (NCM 111) in lithium ion full cells by using the total reflection X-ray fluorescence technique , 2016 .

[45]  Kevin N. Wood,et al.  Dendrites and Pits: Untangling the Complex Behavior of Lithium Metal Anodes through Operando Video Microscopy , 2016, ACS central science.

[46]  Jürgen Janek,et al.  A solid future for battery development , 2016, Nature Energy.

[47]  R. Zengerle,et al.  Morphological Evolution of Electrochemically Plated/Stripped Lithium Microstructures Investigated by Synchrotron X-ray Phase Contrast Tomography. , 2016, ACS nano.

[48]  A. Bhatt,et al.  Stabilizing lithium metal using ionic liquids for long-lived batteries , 2016, Nature Communications.

[49]  Myung-Hyun Ryou,et al.  Micro‐Patterned Lithium Metal Anodes with Suppressed Dendrite Formation for Post Lithium‐Ion Batteries , 2016 .

[50]  Zonghai Chen,et al.  Role of Manganese Deposition on Graphite in the Capacity Fading of Lithium Ion Batteries. , 2016, ACS applied materials & interfaces.

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

[52]  H. Hahn,et al.  The truth about the 1st cycle Coulombic efficiency of LiNi1/3Co1/3Mn1/3O2 (NCM) cathodes. , 2016, Physical chemistry chemical physics : PCCP.

[53]  M. Winter,et al.  Learning from Overpotentials in Lithium Ion Batteries: A Case Study on the LiNi1/3Co1/3Mn1/3O2 (NCM) Cathode , 2016 .

[54]  M. Winter,et al.  Investigations on the C-Rate and Temperature Dependence of Manganese Dissolution/Deposition in LiMn2O4/Li4Ti5O12 Lithium Ion Batteries , 2016 .

[55]  M. Winter,et al.  Development of a method for direct elemental analysis of lithium ion battery degradation products by means of total reflection X-ray fluorescence , 2015 .

[56]  Guangyuan Zheng,et al.  The synergetic effect of lithium polysulfide and lithium nitrate to prevent lithium dendrite growth , 2015, Nature Communications.

[57]  Martin Winter,et al.  Electrochemical in situ investigations of SEI and dendrite formation on the lithium metal anode. , 2015, Physical chemistry chemical physics : PCCP.

[58]  Peter Lamp,et al.  Future generations of cathode materials: an automotive industry perspective , 2015 .

[59]  Young-Sang Yu,et al.  The formation mechanism of fluorescent metal complexes at the Li(x)Ni(0.5)Mn(1.5)O(4-δ)/carbonate ester electrolyte interface. , 2015, Journal of the American Chemical Society.

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

[61]  Myung-Hyun Ryou,et al.  Mechanical Surface Modification of Lithium Metal: Towards Improved Li Metal Anode Performance by Directed Li Plating , 2015 .

[62]  M. Winter,et al.  Fluoroethylene Carbonate as Electrolyte Additive in Tetraethylene Glycol Dimethyl Ether Based Electrolytes for Application in Lithium Ion and Lithium Metal Batteries , 2015 .

[63]  Selena M. Russell,et al.  Dendrite-free lithium deposition with self-aligned nanorod structure. , 2014, Nano letters.

[64]  D. Abraham,et al.  Manganese in Graphite Anode and Capacity Fade in Li Ion Batteries , 2014 .

[65]  J. Steiger,et al.  Mechanisms of dendritic growth investigated by in situ light microscopy during electrodeposition and dissolution of lithium , 2014 .

[66]  Klaus Leitner,et al.  Systematical electrochemical study on the parasitic shuttle-effect in lithium-sulfur-cells at different temperatures and different rates , 2014 .

[67]  Reiner Mönig,et al.  Microscopic observations of the formation, growth and shrinkage of lithium moss during electrodeposition and dissolution , 2014 .

[68]  M. Winter,et al.  The influence of different conducting salts on the metal dissolution and capacity fading of NCM cathode material , 2014 .

[69]  B. Liaw,et al.  A review of lithium deposition in lithium-ion and lithium metal secondary batteries , 2014 .

[70]  M. Winter,et al.  Coated Lithium Powder (CLiP) Electrodes for Lithium‐Metal Batteries , 2014 .

[71]  Arumugam Manthiram,et al.  A perspective on the high-voltage LiMn1.5Ni0.5O4 spinel cathode for lithium-ion batteries , 2014 .

[72]  T. Ishihara,et al.  Surface Coating Layer on Li Metal for Increased Cycle Stability of Li–O2 Batteries , 2014 .

[73]  A. MacDowell,et al.  Detection of subsurface structures underneath dendrites formed on cycled lithium metal electrodes. , 2014, Nature materials.

[74]  Jung-Hyun Kim,et al.  Understanding Transition-Metal Dissolution Behavior in LiNi0.5Mn1.5O4 High-Voltage Spinel for Lithium Ion Batteries , 2013 .

[75]  Jun Liu,et al.  Dendrite-free lithium deposition via self-healing electrostatic shield mechanism. , 2013, Journal of the American Chemical Society.

[76]  Jens Leker,et al.  Current research trends and prospects among the various materials and designs used in lithium-based batteries , 2013, Journal of Applied Electrochemistry.

[77]  C. Delacourt,et al.  Effect of Manganese Contamination on the Solid-Electrolyte-Interphase Properties in Li-Ion Batteries , 2013 .

[78]  Martin Winter,et al.  How Do Reactions at the Anode/Electrolyte Interface Determine the Cathode Performance in Lithium-Ion Batteries? , 2013 .

[79]  G. Stucky,et al.  Spatially heterogeneous carbon-fiber papers as surface dendrite-free current collectors for lithium deposition , 2012 .

[80]  Doron Aurbach,et al.  Challenges in the development of advanced Li-ion batteries: a review , 2011 .

[81]  B. Dunn,et al.  Protection of lithium metal surfaces using tetraethoxysilane , 2011 .

[82]  Martin Winter,et al.  The Solid Electrolyte Interphase – The Most Important and the Least Understood Solid Electrolyte in Rechargeable Li Batteries , 2009 .

[83]  Glenn G. Amatucci,et al.  The effect of particle size and morphology on the rate capability of 4.7 V LiMn1.5+δNi0.5−δO4 spinel lithium-ion battery cathodes , 2008 .

[84]  J. Besenhard,et al.  Chapter 17. Lithiated Carbons , 2007 .

[85]  Kristina Edström,et al.  Recent findings and prospects in the field of pure metals as negative electrodes for Li-ion batteries , 2007 .

[86]  R. Benedek,et al.  Reaction Energy for LiMn2O4 Spinel Dissolution in Acid , 2006 .

[87]  P. Bruce,et al.  Rechargeable LI2O2 electrode for lithium batteries. , 2006, Journal of the American Chemical Society.

[88]  J. Newman,et al.  The Effect of Interfacial Deformation on Electrodeposition Kinetics , 2004 .

[89]  D. Sadoway.  Block and graft copolymer electrolytes for high-performance, solid-state, lithium batteries , 2004 .

[90]  Martin Winter,et al.  Inorganic film-forming electrolyte additives improving the cycling behaviour of metallic lithium electrodes and the self-discharge of carbon—lithium electrodes , 1993 .