Results from a Novel Method for Corrosion Studies of Electroplated Lithium Metal Based on Measurements with an Impedance Scanning Electrochemical Quartz Crystal Microbalance

Schedlbauer, Tanja; Hoffmann, B.; Krüger, Steffen; Gores, H. J.; Winter, Martin

doi:10.3390/en6073481

Cited by 8 publications

(4 citation statements)

References 58 publications

(86 reference statements)

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“…Numerous fluorinated borate based salts have been fabricated including LiBFMB 57,127 and LiD-FOB. 50,116,128 Both of these Li salts have much higher solubility in carbonate solvents than LiBOB and Li transference numbers greater than LiPF 6 (t Li+ = 0.47 LiBFMB; 0.33 LiDFOB; 0.24 LiPF 6 ). 127 Schedlbauer et al reported a study of the cyclability of Li in LiPF 6 and LiDFOB electrolytes, 129 and found that the LiDFOB electrolytes had much higher Coulombic efficiencies compared to LiPF 6 upon cycling, 95-97% vs. 75% after 500 cycles.…”

Section: Li-salts For Li-metal Batteriesmentioning

confidence: 99%

Lithium salts for advanced lithium batteries: Li–metal, Li–O₂, and Li–S

Younesi

Veith

Johansson

et al. 2015

Energy Environ. Sci.

500

365

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Presently lithium hexafluorophosphate (LiPF 6 ) is the dominant Li-salt used in commercial rechargeable lithium-ion batteries (LIBs) based on a graphite anode and a 3-4 V cathode material. While LiPF 6 is not the ideal Li-salt for every important electrolyte property, it has a uniquely suitable combination of properties (temperature range, passivation, conductivity, etc.) rendering it the overall best Li-salt for LIBs. However, this may not necessarily be true for other types of Li-based batteries. Indeed, next generation batteries, for example lithium-metal (Limetal), lithium-oxygen (Li-O 2 ), and lithium-sulfur (Li-S), require a re-evaluation of Li-salts due to the different electrochemical and chemical reactions and conditions within such cells. This review explores the critical role Li-salts play in ensuring in these batteries viability.

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Section: Li-salts For Li-metal Batteriesmentioning

confidence: 99%

Lithium salts for advanced lithium batteries: Li–metal, Li–O₂, and Li–S

Younesi

Veith

Johansson

et al. 2015

Energy Environ. Sci.

500

365

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“…[15][16][17][18] However, corrosion of aluminum is observed in this same potential range for other electrolyte salts. [19][20][21] Many different types of carbon additives have been utilized in cathode laminates and differences in the physical properties such as surface area and porosity affect stability and performance. [22][23][24][25][26][27][28] However, studies of carbon additives at high potential (>4.6 V) are limited and typically have been investigated in the presence of active materials.…”

mentioning

confidence: 99%

Stability of Inactive Components of Cathode Laminates for Lithium Ion Batteries at High Potential

Chen

Nguyen

et al. 2014

J. Electrochem. Soc.

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The stability of inactive components in LIB (lithium ion batteries) electrodes upon exposure to high potentials can affect cell performance. A series of Li/ inactive component cells with aluminum, conductive carbon, and graphite as the inactive component were prepared and stored at high potential for one week. Electrochemical measurements and ex-situ surface analysis, including TEM (transmission electron microscopy), XPS (X-ray photoelectron spectroscopy), and FTIR (Fourier transform infrared spectroscopy), were conducted to investigate the stability of inactive components in the presence of LiPF 6 in 3:7 ethylene carbonate (EC) and ethyl methyl carbonate (EMC) electrolyte at different potentials. The results show that all components are stable upon storage at 4.3 V. Storage at 4.6 or 4.9 V results in no aluminum corrosion, but limited decomposition on conductive carbon and greater decomposition on graphite. Storage at 5.3 V results in significant electrolyte oxidation to generate poly(ethylene carbonate) on the surface of all inactive electrodes and aluminum corrosion.Lithium ion batteries (LIBs) have had great success for portable electronics applications since their initial commercialization in the 1990s. 1-3 However, the development of LIB for hybrid electric vehicles (HEVs) and electric vehicles (EVs), requires LIBs with higher energy and power density. Significant research has been conducted on the development of novel cathode active materials with a higher operating potential (> 4.5 V vs Li/Li + ) or higher capacity, such as high voltage spinel LiNi 0.5 Mn 1.5 O 4 and lithium magnesium rich NMC. [4][5][6][7][8][9][10][11] However, there are significant concerns regarding the stability of standard carbonate based electrolytes, LiPF 6 in a mixture of ethylene carbonate (EC) and dialkyl carbonates, at higher potential. 12 The cathode laminate of a typical lithium ion battery includes the active materials along with inactive components, such as carbonaceous materials (usually graphite or conductive carbon) to enhance the conductivity, polymeric binder (typically PVDF), and an aluminum current collector. While much effort has been expended on the development and investigation of active cathode materials, less attention has been given to the inactive components of the positive electrode. 13,14 The aluminum current collector is stable in LiPF 6 or LiBF 4 based electrolyte due to the formation of a passivation film at standard potential ranges (up to 4.3 V). 15-18 However, corrosion of aluminum is observed in this same potential range for other electrolyte salts. [19][20][21] Many different types of carbon additives have been utilized in cathode laminates and differences in the physical properties such as surface area and porosity affect stability and performance. [22][23][24][25][26][27][28] However, studies of carbon additives at high potential (>4.6 V) are limited and typically have been investigated in the presence of active materials. 13,14,22,29 Herein, a systematic investigation of the stability of the inac...

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“…[23][24][25] An example is the recent EQCM analysis of heavily damped systems such as metal foils adhered to an electrode mounted on a quartz crystal. 36,37 Those two publications interpreted frequency changes gravimetrically, correlating frequency increases to mass decreases and vice versa. Our nanofoam results are also interpreted gravimetrically, but we do not assign mass values because of the thickness (∼100 μm) and varying porosity of these electrodes.…”

Section: Resultsmentioning

confidence: 99%

Extending Electrochemical Quartz Crystal Microbalance Techniques to Macroscale Electrodes: Insights on Pseudocapacitance Mechanisms in MnOx-Coated Carbon Nanofoams

Beasley¹,

Sassin

Long

2015

J. Electrochem. Soc.

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Electrochemical quartz crystal microbalance studies of MnOx-coated carbon nanofoams reveal that charge-compensation mechanisms associated with MnOx pseudocapacitance in mild aqueous electrolytes are dominated by anion insertion rather than more commonly reported cation ejection. Specific charge-compensation behavior depends on such factors as electrolyte composition, nanofoam pore size, and polarization amplitude. For example, MnOx-carbon nanofoams with average pore sizes of 5-20 nm, cycled in 2.5 M LiNO 3 , reveal a kinetically-hindered, mixed anion-cation charge-compensation mechanism, whereas the same nanofoam cycled in 2.5 M NaNO 3 shows only anion association. Nanofoams with larger pores (10-200 nm) Transition metal oxides that exhibit "pseudocapacitance", capacitor-like behavior that arises from faradaic reactions, are challenging high-surface-area carbons, which rely primarily on doublelayer capacitance, as active materials in next-generation electrochemical capacitors (ECs).1-4 Because pseudocapacitance involves electrontransfer reactions, the quantity of charge-storage per mass or volume often surpasses that achieved with double-layer capacitance alone. The enhanced charge-storage capacity provided by pseudocapacitive metal oxides compensates for the voltage limitations of aqueous-electrolyte ECs, resulting in asymmetric aqueous EC designs 5-7 that provide competitive performance and safer operation compared to conventional symmetric carbon-carbon ECs that use organic electrolytes.Manganese oxides (MnOx) have emerged as one of the most important classes of pseudocapacitive materials due to their low cost, competitive specific capacitance, availability in a wide range of compositions and crystal habits, and adaptability to a variety of electrode architectures. [8][9][10][11] The electrochemical characteristics of MnOx have been extensively demonstrated, yet the underlying mechanisms responsible for pseudocapacitance are still a subject of debate. Spectroscopic methods have been used to confirm that pseudocapacitive charge storage is supported by reversible toggling of the Mn oxidation state (ranging between +3 and +4, but typically <1 e -per Mn site) during electrochemical cycling in aqueous electrolytes. [12][13][14] Changes in Mn oxidation state must be accompanied by insertion or adsorption of charge-balancing ions from the contacting electrolyte. In the case of mild aqueous electrolytes, charge compensation typically occurs via cation-insertion/association mechanisms where the cations are supplied by either the electrolyte salt (e.g., Li + , Na + , or K + ), the H 2 O solvent (in the form of H + or H 3 O + ), or combinations thereof.14-20 Because of the prospective participation of multiple types of ions (in varying degrees of solvation), deconvolution of MnOx pseudocapacitance mechanisms has proven difficult. The ability to draw broader conclusions regarding MnOx pseudocapacitance mechanisms has been further complicated by the wide range of materials that are broadly identified in the literature a...

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Results from a Novel Method for Corrosion Studies of Electroplated Lithium Metal Based on Measurements with an Impedance Scanning Electrochemical Quartz Crystal Microbalance

Cited by 8 publications

References 58 publications

Lithium salts for advanced lithium batteries: Li–metal, Li–O₂, and Li–S

Lithium salts for advanced lithium batteries: Li–metal, Li–O₂, and Li–S

Stability of Inactive Components of Cathode Laminates for Lithium Ion Batteries at High Potential

Extending Electrochemical Quartz Crystal Microbalance Techniques to Macroscale Electrodes: Insights on Pseudocapacitance Mechanisms in MnOx-Coated Carbon Nanofoams

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Results from a Novel Method for Corrosion Studies of Electroplated Lithium Metal Based on Measurements with an Impedance Scanning Electrochemical Quartz Crystal Microbalance

Cited by 8 publications

References 58 publications

Lithium salts for advanced lithium batteries: Li–metal, Li–O2, and Li–S

Lithium salts for advanced lithium batteries: Li–metal, Li–O2, and Li–S

Stability of Inactive Components of Cathode Laminates for Lithium Ion Batteries at High Potential

Extending Electrochemical Quartz Crystal Microbalance Techniques to Macroscale Electrodes: Insights on Pseudocapacitance Mechanisms in MnOx-Coated Carbon Nanofoams

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Product

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Lithium salts for advanced lithium batteries: Li–metal, Li–O₂, and Li–S

Lithium salts for advanced lithium batteries: Li–metal, Li–O₂, and Li–S