Sodiation energetics in pore size controlled hard carbons determined <i>via</i> entropy profiling

Mercer, Michael; Nagarathinam, Mangayarkarasi; Arriazu, Edgardo Maximiliano Gavilán; Binjrajka, Anshika; Panda, Swoyam; Au, Heather; Crespo‐Ribadeneyra, Maria; Titirici, Maria‐Magdalena; Leiva, E.P.M.; Hoster, Harry E.

doi:10.1039/d2ta09406a

Cited by 15 publications

(6 citation statements)

References 55 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Quantitative evaluation of the data yielded approximately 80 J mol −1 K −1 at t =400 ms, which comes close to the value for Na metal‐deposition from NaClO 4 /PC solution (83 J mol −1 K −1 ) [93] . This is in agreement with results from entropy profiling of half‐cells reported in the literature, [94] where only small differences between metal‐deposition and sodiation entropies at high SoC were reported. The positive reaction entropy upon Na insertion or deposition is readily explained by the entropy gain upon the release of solvent molecules from the solvation shell, which overcompensates entropy losses due to fixation of Na + ions and which was similarly observed for Li deposition [44,92] .…”

Section: Resultssupporting

confidence: 93%

Spray‐coated Hard Carbon Composite Anodes for Sodium‐Ion Insertion

Palanisamy,

Daboss,

Schäfer

et al. 2023

Batteries & Supercaps

View full text Add to dashboard Cite

Sodium‐ion batteries are among the most promising alternatives to lithium‐ion batteries. Hard carbon (HC) electrodes have been recognized as suitable active anode material for mono‐valent ion batteries. Here, we present a simple and cost‐effective spray‐coating process to prepare HC composite electrodes on copper current collectors with different binder (sodium carboxy methyl cellulose, CMC) content and different HC particle sizes. The spray‐coated electrodes were evaluated and tested in 1 M sodium perchlorate (NaClO4) in propylene carbonate (PC) in dependence of the CMC content with and without fluoroethylene carbonate (FEC) as additive and the performance was also compared to doctor bladed HC electrodes. Spray‐coated anodes in Na half‐cells revealed improved capacity during the first cycles compared with doctor bladed anodes with similar thicknesses. Time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) studies were performed, which revealed a significant increase of inorganic fluoro‐compounds in the formed solid electrolyte interface (SEI) when FEC was present as additive. In addition, first single electrode microcalorimetry studies on spray‐coated thin HC composite electrodes yielded an entropy of the sodiation process of 80 J mol‐1 K‐1 at high state of charge (SoC), comparable to that of bulk Na deposition.

show abstract

Section: Resultssupporting

confidence: 93%

Spray‐coated Hard Carbon Composite Anodes for Sodium‐Ion Insertion

Palanisamy,

Daboss,

Schäfer

et al. 2023

Batteries & Supercaps

View full text Add to dashboard Cite

show abstract

“…Excessive micropores can increase the adsorption capacity, [107] but also lead to an increase in the probability of side reactions, thus affecting the initial coulomb efficiency. [108] However, it is worth noting that pore and specific side reactions are not positively correlated. Therefore, more research and characterization methods are needed to further analyze pore structure.…”

Section: Constructed Porous Structure Of Plant-based Hard Carbonmentioning

confidence: 99%

“…The pore structure is a contradictory structure in PBHC. Excessive micropores can increase the adsorption capacity, [107] but also lead to an increase in the probability of side reactions, thus affecting the initial coulomb efficiency [108] . However, it is worth noting that pore and specific side reactions are not positively correlated.…”

Section: Designing Preferred Structures Of Plant‐based Hard Carbon Vi...mentioning

confidence: 99%

Pretreatment Process Before Heat Pyrolysis of Plant‐based Precursors Paving Way for Fabricating High‐Performance Hard Carbon for Sodium‐Ion Batteries

Zhang,

Wang

et al. 2023

ChemElectroChem

View full text Add to dashboard Cite

The increasing demand for sodium‐ion batteries has risen due to sodium resources that are inexpensive and abundant compared with its counterpart of lithium‐ion batteries. Development of anode materials with high performance is central issue for sodium‐ion batteries. Plant‐based hard carbon material is a promising anode material for sodium ion batteries due to its green preparation process, favorable ions transport channel, and special porous structure. Previous studies have not systematically correlated the material's inherent structure limitation with its electrochemical properties, resulting in a complex classification and a lack selection of pretreatment methods. In this review, the intrinsic limitations in the structure of plant‐based precursors are divided into four parts, including impure components, single chemical structure, uncontrollable crystalline texture, and irregular porous structure. The previous pretreatment methods are reclassified, including purification component aiming at plant‐based precursors, optimized structure, and precabornized process aiming at intermediate products. Furthermore, the pretreatment strategies are discussed according to the preferred structures of plant‐based hard carbon and the relationship between structure and performance is systematically expounded. This review provides deep understanding of the mechanism of pretreatment and a guide for selecting appropriate pretreatment strategies to optimize the structure of plant‐based hard carbon for sodium ion batteries.

show abstract

“…Scientists have made many efforts to solve the controversial problems in developing sodium-ion batteries, and enormous achievements have been made during this period [ 74 , 75 , 76 ]. This review summarizes four different sodium-storage models for hard carbon anodes [ 77 , 78 ] ( Figure 1 ), including the “embedding-adsorption” model [ 79 , 80 ], the “adsorption-embedding” model [ 3 , 81 , 82 ], the “three-stage model” [ 83 ], and the “adsorption-filling” model [ 84 ]. The following section describes the storage of sodium ions in hard carbon.…”

Section: Mechanism Of Sodium Storage By Hard Carbonmentioning

confidence: 99%

The Progress of Hard Carbon as an Anode Material in Sodium-Ion Batteries

et al. 2023

View full text Add to dashboard Cite

When compared to expensive lithium metal, the metal sodium resources on Earth are abundant and evenly distributed. Therefore, low-cost sodium-ion batteries are expected to replace lithium-ion batteries and become the most likely energy storage system for large-scale applications. Among the many anode materials for sodium-ion batteries, hard carbon has obvious advantages and great commercial potential. In this review, the adsorption behavior of sodium ions at the active sites on the surface of hard carbon, the process of entering the graphite lamellar, and their sequence in the discharge process are analyzed. The controversial storage mechanism of sodium ions is discussed, and four storage mechanisms for sodium ions are summarized. Not only is the storage mechanism of sodium ions (in hard carbon) analyzed in depth, but also the relationships between their morphology and structure regulation and between heteroatom doping and electrolyte optimization are further discussed, as well as the electrochemical performance of hard carbon anodes in sodium-ion batteries. It is expected that the sodium-ion batteries with hard carbon anodes will have excellent electrochemical performance, and lower costs will be required for large-scale energy storage systems.

show abstract

Sodiation energetics in pore size controlled hard carbons determined via entropy profiling

Abstract: Hard carbons show considerable potential as anode materials in emerging sodium-ion battery technologies. Recent work suggests sodiation of hard carbon proceeds by insertion of sodium at defects, within the interlayers...

Cited by 15 publications

References 55 publications

Spray‐coated Hard Carbon Composite Anodes for Sodium‐Ion Insertion

Spray‐coated Hard Carbon Composite Anodes for Sodium‐Ion Insertion

Pretreatment Process Before Heat Pyrolysis of Plant‐based Precursors Paving Way for Fabricating High‐Performance Hard Carbon for Sodium‐Ion Batteries

The Progress of Hard Carbon as an Anode Material in Sodium-Ion Batteries

Contact Info

Product

Resources

About