Hard carbon possesses the ability to store Li, Na, and K ions between stacked sp 2 carbon layers and voids (micropores). We have explored hard carbon as a candidate for negative electrode materials for Li-ion, Na-ion, and K-ion batteries. Hard carbon samples have been prepared by carbonizing sucrose at different heat treatment temperatures (HTTs) in the range of 700−2000 °C to make them structurally suitable for reversible Li, Na, and K insertion. Structures and particle morphology of the hard carbon samples synthesized at different HTTs were systematically characterized using X-ray diffraction, small-angle X-ray scattering, pair distribution function analysis, electron microscopy, Raman spectroscopy, and electron spin resonance spectroscopy. All these characterizations of hard carbon samples have revealed advanced ordering of carbons and reduction of carbon defects with increasing HTT. Thus, the average stacked carbon interlayer distance decreases, the number of the stacking layers increases, the layered domains grow in the in-plane direction, and interstitial voids enlarge. Electrochemical properties of the hard carbons were examined in nonaqueous Li, Na, and K cells. Potential profiles and reversible capacities upon galvanostatic charge/discharge processes in nonaqueous cells are significantly different depending on HTTs and different alkali metal ions. On the basis of these findings, strategies to design high-capacity hard carbon negative electrodes for high-energy-density Li-ion, Na-ion, and K-ion batteries are discussed.
For a nonaqueous sodium-ion battery (NIB), phosphorus materials have been studied as the highest-capacity negative electrodes. However, the large volume change of phosphorus upon cycling at low voltage causes the formation of new active surfaces and potentially results in electrolyte decomposition at the active surface, which remains one of the major limiting factors for the long cycling life of batteries. In this present study, powerful surface characterization techniques are combined for investigation on the electrode/electrolyte interface of the black phosphorus electrodes with polyacrylate binder to understand the formation of a solid electrolyte interphase (SEI) in alkyl carbonate ester and its evolution during cycling. The hard X-ray photoelectron spectroscopy (HAXPES) analysis suggests that SEI (passive film) consists of mainly inorganic species, which originate from decomposition of electrolyte solvents and additives. The thicker surface layer is formed during cycling in the additive-free electrolyte, compared to that in the electrolyte with fluoroethylene carbonate (FEC) or vinylene carbonate (VC) additive. The HAXPES and time-of-flight secondary ion mass spectroscopy (TOF-SIMS) studies further reveal accumulation of organic carbonate species near the surface and inorganic salt decomposition species. These findings open paths for further improvement for the cyclability of phosphorus electrodes for high-energy NIBs.
Hard Optimal carbonization of glucose, sucrose, maltose, cellulose, glycogen, and amylopectin is studied for Na-ion application.
Anatase TiO 2 is a potential negative electrode for sodium-ion batteries. The sodium storage mechanism is, however, still under debate, yet its comprehension is required to optimize the electrochemical properties. To clarify the sodium storage mechanism occurring in anatase, we have used both electrochemical and chemical routes from which we obtained similar trends. During the first discharge, an irreversible plateau region is observed which corresponds to the insertion of Na + within the interstitial sites of anatase and is accompanied by a drastic loss of the long-range order as revealed by X-ray diffraction, high resolution of high angle annular dark-field scanning transmission electron microscope (HAADF-STEM), and pair distribution function (PDF) analysis. Further structural analysis of the total scattering data indicates that the sodiated phase displays a layered-like rhombohedral R3̅ m structure built from the stacking of Ti and Na slabs. Because of the initial 3D network of anatase, the reduced phase shows strong disorder due to cationic intermixing between the Ti and Na slabs and the refined chemical formula is (Na 0.43 Ti 0.57 ) 3a □ 0.22 Na 0.39 Ti 0.39 ) 3b O 2 , where □ refers to vacancy. The presence of high valence Ti ions in the Na layers induces a contraction of the c-parameter as compared to the ordered phase. Upon desodiation, the structure further amorphized and the local structure probed by PDF is shown to be similar to the anatase TiO 2 , suggesting that the 3D network is recovered. The reversible sodium insertion/deinsertion is thus attributed to the rhombohedral active phase formed during the first discharge, and an oxidized phase featuring the local structure of anatase. Due to the amorphous nature of the two phases, the potential-composition curves are characterized by a sloping curve. Finally, a comparison between the intercalation of lithium and sodium into anatase TiO 2 performed by DFT calculations confirmed that, for the sodiated phase, the rhombohedral structure is more stable than the tetragonal phase observed during the lithiation of nanoparticles.
We examined the state of sodium electrochemically inserted in HC prepared at 700-2000 C using solid state Na magic angle spinning (MAS) NMR and multiple quantum (MQ) MAS NMR. The 23 Na MAS NMR spectra of Na-inserted HC samples showed signals only in the range between +30 and À60 ppm. Each observed spectrum was ascribed to combinations of Na + ions from the electrolyte, reversible ionic Na components, irreversible Na components assigned to solid electrolyte interphase (SEI) or nonextractable sodium ions in HC, and decomposed Na compounds such as Na 2 CO 3 . No quasi-metallic sodium component was observed to be dissimilar to the case of Li inserted in HC. MQMAS NMR implies that heat treatment of HC higher than 1600 C decreases defect sites in the carbon structure. To elucidate the difference in cluster formation between Na and Li in HC, the condensation mechanism and stability of Na and Li atoms on a carbon layer were also studied using DFT calculation. Na 3 triangle clusters standing perpendicular to the carbon surface were obtained as a stable structure of Na, whereas Li 2 linear and Li 4 square clusters, all with Li atoms being attached directly to the surface, were estimated by optimization. Models of Na and Li storage in HC, based on the calculated cluster structures were proposed, which elucidate why the adequate heat treatment temperature of HC for high-capacity sodium storage is higher than the temperature for lithium storage. † Electronic supplementary information (ESI) available: XRD patterns of HC samples, wide range 23 Na NMR spectra, Na NMR spectra of some inorganic sodium compounds and NaPF 6 /PC solutions, charge/discharge curves of reassembled cells, and DFT optimizations of an alkali atom (Li or Na) set at the center of C 150 H 30 . See
Reversibility of electrochemical sodiation for Sn-based electrodes consisting of Sn powder, graphite, and sodium polyacrylate was examined at different upper cutoff voltages of 0.65 and 0.70 V in nonaqueous Na cells. The upper cutoff voltage is one of the key factors to improve the electrochemical reversibility. In case of a cutoff voltage of 0.70 V, the sodiation/desodiation cycle performance was not stable and accompanied by capacity decay, indicating that the anodic decomposition of passivation layer is led to the dissolution and reformation at 0.68 and 0.40 V, respectively, on Sn particles that were catalyzed by pure Sn metal. The repeated dissolution and reformation brought a thicker and resistive surface layer, resulting from the accumulation of electrolyte decomposition products, which was clarified by X-ray photoelectron spectroscopy. In contrast, the capacity retention and stability were improved by simply changing the upper cutoff voltage to 0.65 V due to exclusion of the SEI decomposition at 0.68 V. The results of time-of-flight secondary ion mass spectroscopy measurements suggests that the surface passivation layer containing polymer/oligomer on the Sn electrode was successfully formed and enhanced the SEI functionality for 0.65 V cutoff. The Sn-based electrode delivered ∼700 mAh g–1 reversible capacity over 100 cycles.
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