Tin‐Containing Graphite for Sodium‐Ion Batteries and Hybrid Capacitors (original) (raw)
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Tin and graphite based nanocomposites: Potential anode for sodium ion batteries
Pure tin (Sn) and a homogeneous nanocomposite of tin and graphite (C), denoted as Sn/C, have been studied as a suitable anode for sodium ion batteries. The Sn/C nanocomposites have been synthesized by high energy mechanical milling (HEMM) of pure Sn and graphite of nominal composition C-70 wt.% Sn. Pure microcrystalline Sn (≤44 μm) exhibits a 1st discharge capacity ∼856 mAh g−1 which is close to the expected theoretical capacity, however, it shows a large 1st cycle irreversible loss (∼67%) and the anticipated inevitable rapid fade in capacity expectedly due to structural failure of the electrode. On the other hand, the resultant Sn/C based nanocomposite, synthesized by HEMM after 1h of milling, exhibits a 1st cycle discharge capacity ∼584 mAh g−1 with a 1st cycle irreversible loss ∼30%. The Sn/C nanocomposite shows a 1st cycle charge capacity of ∼410 mAh g−1 with improved capacity retention in comparison to pure Sn displaying 0.7% fade in capacity per cycle up to 20 cycles when cycled at a rate of ∼C/8. Scanning electron microscopy (SEM) analysis indicates that the structural integrity and microstructural stability of the Sn/C nanocomposite during the alloying/dealloying processes appear to be the primary factors contributing to the good cyclability observed in the above HEMM derived nanocomposite suggesting its promise as a potential anode for Na-ion systems.► Tin and graphite mixture and nanocomposites have been synthesized by high energy mechanical milling (HEMM). ► Mechanically milling results in nanocrystalline nanocomposites. ► The mechanically milled nanocomposites exhibit stable capacities of ∼410 mAh g−1. ► Electrochemical response varies with duration of mechanical milling. ► Good electrochemical response of the nanocomposite is due to structural stability.
Materials, 2019
A tin-decorated reduced graphene oxide, originally developed for lithium-ion batteries, has been investigated as an anode in sodium-ion batteries. The composite has been synthetized through microwave reduction of poly acrylic acid functionalized graphene oxide and a tin oxide organic precursor. The final product morphology reveals a composite in which Sn and SnO 2 nanoparticles are homogenously distributed into the reduced graphene oxide matrix. The XRD confirms the initial simultaneous presence of Sn and SnO 2 particles. SnRGO electrodes, prepared using Super-P carbon as conducting additive and Pattex PL50 as aqueous binder, were investigated in a sodium metal cell. The Sn-RGO showed a high irreversible first cycle capacity: only 52% of the first cycle discharge capacity was recovered in the following charge cycle. After three cycles, a stable SEI layer was developed and the cell began to work reversibly: the practical reversible capability of the material was 170 mA·h·g −1. Subsequently, a material of formula NaLi 0.2 Ni 0.25 Mn 0.75 O δ was synthesized by solid-state chemistry. It was found that the cathode showed a high degree of crystallization with hexagonal P2-structure, space group P6 3 /mmc. The material was electrochemically characterized in sodium cell: the discharge-specific capacity increased with cycling, reaching at the end of the fifth cycle a capacity of 82 mA·h·g −1. After testing as a secondary cathode in a sodium metal cell, NaLi 0.2 Ni 0.25 Mn 0.75 O δ was coupled with SnRGO anode to form a sodium-ion cell. The electrochemical characterization allowed confirmation that the battery was able to reversibly cycle sodium ions. The cell's power response was evaluated by discharging the SIB at different rates. At the lower discharge rate, the anode capacity approached the rated value (170 mA·h·g −1). By increasing the discharge current, the capacity decreased but the decline was not so pronounced: the anode discharged about 80% of the rated capacity at 1 C rate and more than 50% at 5 C rate.
Expanded graphite as superior anode for sodium-ion batteries
Nature communications, 2014
Graphite, as the most common anode for commercial Li-ion batteries, has been reported to have a very low capacity when used as a Na-ion battery anode. It is well known that electrochemical insertion of Na(+) into graphite is significantly hindered by the insufficient interlayer spacing. Here we report expanded graphite as a Na-ion battery anode. Prepared through a process of oxidation and partial reduction on graphite, expanded graphite has an enlarged interlayer lattice distance of 4.3 Å yet retains an analogous long-range-ordered layered structure to graphite. In situ transmission electron microscopy has demonstrated that the Na-ion can be reversibly inserted into and extracted from expanded graphite. Galvanostatic studies show that expanded graphite can deliver a high reversible capacity of 284 mAh g(-1) at a current density of 20 mA g(-1), maintain a capacity of 184 mAh g(-1) at 100 mA g(-1), and retain 73.92% of its capacity after 2,000 cycles.
Materials
A tin-decorated reduced graphene oxide, originally developed for lithium-ion batteries, has been investigated as an anode in sodium-ion batteries. The composite has been synthetized through microwave reduction of poly acrylic acid functionalized graphene oxide and a tin oxide organic precursor. The final product morphology reveals a composite in which Sn and SnO2 nanoparticles are homogenously distributed into the reduced graphene oxide matrix. The XRD confirms the initial simultaneous presence of Sn and SnO2 particles. SnRGO electrodes, prepared using Super-P carbon as conducting additive and Pattex PL50 as aqueous binder, were investigated in a sodium metal cell. The Sn-RGO showed a high irreversible first cycle capacity: only 52% of the first cycle discharge capacity was recovered in the following charge cycle. After three cycles, a stable SEI layer was developed and the cell began to work reversibly: the practical reversible capability of the material was 170 mA·h·g−1. Subsequen...
Sodium-ion batteries (SIBs) have attracted remarkable attention since they are considered a low-cost alternative for lithium-ion batteries (LIBs) for large scale energy storage system applications. Tin selenides such as SnSe and SnSe 2 are earth-abundant, environmentally friendly, chemically stable, and capable candidates as the negative electrode for SIBs, in which the capacity is provided by a conversion reaction together with the alloying mechanism. However, these materials suffer from low conductivity, drastic volume changes, and aggregation of particles during the electrochemical reaction, which lead to poor cycling performance, hindering their practical application. The combination of tin selenide with conductive carbon is an effective strategy to overcome the issues mentioned above. Herein, we report tin selenide/N-doped carbon composite as an anode material for SIBs fabricated by solvothermal synthesis followed by a dry solid state method and calcination. The as-prepared tin selenide/N-doped carbon composite electrode delivers an initial discharge capacity of 460 mAh g À1 and maintained a discharge capacity of 348 mAh g À1 at the end of the 100th cycle at a current density of 200 mA g À1 , which is almost 3.5 times higher in discharge capacity than the pristine electrodes. Moreover, the composite electrode exhibits outstanding rate capability compared to pristine tin selenide with a discharge capacity of 234 mAh g À1 even at a high current density of 1600 mA g À1. N-doped carbon provides improved conductivity as well as buffering the volume change during sodiation/desodiation, resulting in an overall enhancement of electrochemical performance.
Carbon, 2006
Electrochemical lithium insertion was carried out in tin-graphite composites obtained by two different preparation processes. In the first graphite was mixed with the products obtained by reduction of SnCl 4 with Na tert-Butanoate (t-BuONa)-activated NaH (two-step synthesis). The second used materials synthesized by reducing SnCl 4 with a graphite and (t-BuONa)-activated NaH suspension in THF (one-pot synthesis). Both composites were characterized by X-ray diffraction and transmission electron microscopy. It appeared that the tin particle size was controlled by the reduction time of SnCl 4. The stability of the electrochemical capacity of composites prepared by the two-step synthesis is dependent on the tin particle size: a stable capacity upon cycling was shown with subnanometer particles while a capacity fade was observed with larger nanoparticles. In materials prepared by the one pot synthesis, tin was present either as nanopartcles supported on graphite or as free aggregates. An initial reversible capacity of 630 mA hg À1 decayed to a constant value of 415 mA hg À1 after 12 charge/discharge cycles. It was hypothesized that the fraction of tin bound to graphite contributed to the stable reversible capacity while free tin aggregates were responsible for its decay.
Reduced graphene oxide as a stable and high-capacity cathode material for Na-ion batteries
We report the feasibility of using reduced graphene oxide (RGO) as a cost-effective and high performance cathode material for sodium-ion batteries (SIBs). Graphene oxide is synthesized by a modified Hummers' method and reduced using a solid-state microwave irradiation method. The RGO electrode delivers an exceptionally stable discharge capacity of 240 mAh g −1 with a stable long cycling up to 1000 cycles. A discharge capacity of 134 mAh g −1 is obtained at a high current density of 600 mA g −1 , and the electrode recovers a capacity of 230 mAh g −1 when the current density is reset to 15 mA g −1 after deep cycling, thus demonstrating the excellent stability of the electrode with sodium de/intercalation. The successful use of the RGO electrode demonstrated in this study is expected to facilitate the emergence of low-cost and sustainable carbon-based materials for SIB cathode applications. The development of advanced energy storage systems has become an important research area because of their vast usage in applications ranging from portable electronic devices to grid-level energy storage. Intermittent energy sources such as geothermal, solar, and wind require large-scale energy storage systems 1. Lithium-ion batteries (LIBs) are dominant amongst the energy storage technologies for small-to medium-scale electronic devices. The use of electrical energy storage is expanding to large-scale applications, such as transportation and stationary storage systems. However, LIBs are not suitable for large-scale applications because of their high production cost and limited lithium resources. Sodium-ion batteries (SIBs) have emerged as a potential candidate for large-scale energy storage systems (ESS) because of their advantages of a low production cost and evenly distributed global sodium reserves compared to lithium 2–5. For the successful application of SIBs, the electrodes should deliver high round-trip efficiency, a long cycle life and flexible power. In recent years, several cathode materials such as layered oxides (NaMO 2 (M = 3d transition metals) and their solid solutions) 6–10 , sulfates (e.(CN) 6 ·H 2 O and KMFe(CN) 6 where M = transition metal, Na 2 Mn[Mn(CN) 6 ]) 21–23 , have been reported for SIBs. However, most of these materials either have a low sodium storage capacity (< 200 mAh g −1) or undergo rapid capacity degradation over cycling. The composition of most of the cathodes used in SIBs include transition metals, which are not environmentally benign and are often costly. Furthermore, the difficult synthesis procedure, low electronic conductivity and complex structural arrangements during sodium de/intercalation process make layered transition metal oxides unsuitable for use in high-performance SIBs at their present stage of development 24,25. In that regard, inexpensive, environmentally friendly and highly conductive carbonaceous materials are of great interest as electrode materials for electrochemical energy storage devices such as SIBs, LIBs and superca-pacitors 26–28. Among them, graphene, due to its ultrathin two-dimensional structure, has unique properties such as high electrical conductivity, large surface area, and high chemical and mechanical stabilities, and has been used widely in various applications such as electrodes for energy storage systems, field effect transistors, sensors , and catalyst support 29–32. Graphene has been extensively investigated for its use in electrochemical energy
Study of Sn-Coated Graphite as Anode Material for Secondary Lithium-Ion Batteries
Journal of The Electrochemical Society, 2002
Tin-graphite composites have been developed as an alternate anode material for Li-ion batteries using an autocatalytic deposition technique. The specific discharge capacity, coulombic efficiency, rate capability behavior, and cycle life of Sn-C composites has been studied using a variety of electrochemical methods. The amount of tin loading and the heating temperature have a significant effect on the composite performance. The synthesis conditions and Sn loading on graphite have been optimized to obtain the maximum reversible capacity for the composite electrode. Heating the composite converts it from amorphous to crystalline form. Apart from higher capacity, Sn-graphite composites possesses higher coulombic efficiency, better rate capability, and longer cycle life than the bare synthetic graphite. Current studies are focused on reducing the first cycle irreversible capacity loss of this material.