Room temperature sodium-ion batteries are of great interest for high-energy-density energy storage systems because of low-cost and natural abundance of sodium. Here, we report a novel phosphorus/graphene nanosheet hybrid as a high performance anode for sodium-ion batteries through facile ball milling of red phosphorus and graphene stacks. The graphene stacks are mechanically exfoliated to nanosheets that chemically bond with the surfaces of phosphorus particles. This chemical bonding can facilitate robust and intimate contact between phosphorus and graphene nanosheets, and the graphene at the particle surfaces can help maintain electrical contact and stabilize the solid electrolyte interphase upon the large volume change of phosphorus during cycling. As a result, the phosphorus/graphene nanosheet hybrid nanostructured anode delivers a high reversible capacity of 2077 mAh/g with excellent cycling stability (1700 mAh/g after 60 cycles) and high Coulombic efficiency (>98%). This simple synthesis approach and...

Chemically Bonded Phosphorus/Graphene Hybrid as a High Performance Anode for Sodium-Ion Batteries

In the present work, the surface of chitosan membranes was modified using a phosphorylation method carried out at room temperature. Phosphorylation may be of particular interest in materials for orthopaedic applications, due to the cation-exchange properties of phosphate functionalities. Phosphate groups chelate calcium ions, thus inducing the deposition of an apatite-like layer known to improve the osteoconduction of polymer-based implants. Additionally, the negatively charged phosphate functionalities, together with the positively charged amine groups from chitosan, are expected to provide chitosan with an amphoteric character, which may be useful as a combinatorial therapeutic strategy, by simultaneously allowing the immobilization of signalling molecules like growth factors. Phosphorylation was carried out at room temperature using the H3PO4/Et3PO4/P2O5/butanol method. Surface characterization was performed by XPS, ATR-FT-IR, and SEM. Cross-sections were analyzed by SEM fitted with EDS. The phosphate content increased with the reaction time, as shown by XPS and ATR-FT-IR, a P/N atomic ratio of 0.73 being obtained after 48 h of treatment. High-resolution XPS spectra regarding C1s, O1s, N1s and P2p are discussed. The introduction of a neutralization step led to a reduction of P content, which pointed out to the presence of phosphates ionically bound to protonated amines, in addition to phosphate esters. EDS analysis of cross-sections revealed a gradual P reduction up to 50% towards the inner part of the membrane.

Chemical modification of chitosan by phosphorylation: an XPS, FT-IR and SEM study

Maintaining structural stability is a great challenge for high-capacity conversion electrodes with large volume change but is necessary for the development of high-energy-density, long-cycling batteries. Here, we report a stable phosphorus anode for sodium ion batteries by the synergistic use of chemically bonded phosphorus–carbon nanotube (P–CNT) hybrid and cross-linked polymer binder. The P–CNT hybrid was synthesized through ball-milling of red phosphorus and carboxylic group functionalized carbon nanotubes. The P–O–C bonds formed in this process help maintain contact between phosphorus and CNTs, leading to a durable hybrid. In addition, cross-linked carboxymethyl cellulose–citric acid binder was used to form a robust electrode. As a result, this anode delivers a stable cycling capacity of 1586.2 mAh/g after 100 cycles, along with high initial Coulombic efficiency of 84.7% and subsequent cycling efficiency of ∼99%. The unique electrode framework through chemical bonding strategy reported here is potenti...

Advanced Sodium Ion Battery Anode Constructed via Chemical Bonding between Phosphorus, Carbon Nanotube, and Cross-Linked Polymer Binder

The results and detailed discussion of an extensive experimental study of infrared spectra of the x (PbO)-(1−x)P2O5 vitreous system (x=0.3–0.75) together with a brief review of infrared spectra of phosphate compounds, are presented. Theoretical models employed in the interpretation of infrared spectra of glasses have been reviewed. The frequency ranges of various infrared bands belonging to PO
 4
 3−
 and P2O
 7
 4−
 , observed in different phosphate compounds, are discussed. The glassy and quenched samples were prepared from PbO and NH4H2PO4 by the rapid quenching technique. The infrared spectra of the constituents of the system, PbO and P2O5, in their polycrystalline and glassy forms, have been discussed. The intensity and wavenumbers of the infrared bands around 1600 and 3300 cm−1, assigned to the bending and stretching modes in H2O trapped by the hygroscopic glasses, have been followed for different compositions with x<0.5. The changes observed in these infrared bands established the role of water as an additional glass modifier. The intensity and frequency variations of the infrared bands have been followed through all the compositions for characteristic phosphate group frequencies including P=O, P-O-P stretching and bending modes and P-O bending mode. The results clearly suggest that the x(PbO)-(1−x)P2O5 system undergoes gradual structural changes from metaphosphate (x=0.5), to pyrophosphate (x=0.66) and to orthophosphate (x=0.75). The continuing presence of the infrared band, in varying intensity, in the region 1200–1280 cm−1 attributed to P=O, suggests that the glass-forming ability of the binary system is extendable at least up to x=0.66 composition, and that no complete rupture of P=O bond by Pb2+ takes place. The ionic character of the phosphate groups, P-O(−), PO
 4
 3−
 is well revealed by significant changes with the PbO content in the spectral features of the infrared bands around 1120 and 980 cm−1 respectively. The maximum intensity of the P-O(−) band at 1120 cm−1 for 55 mol% PbO suggests a partial breakdown of the covalent vitreous network of the phosphates and formation of a crystalline phase consisting of ionic groups PO
 4
 3−
 , P2O
 6
 2−
 and P2O
 7
 4−
 for PbO greater than 55 mol%. The observed pattern of variation in the intensity of the infrared bands in the 940–1080 cm−1 region attributed to the v3-mode in PO
 4
 3−
 , suggests a gradual transformation of PO
 4
 3−
 units to PO
 3
 −
 groups in lead meta-phosphate glass and then their restoration to PO
 4
 3−
 groups of pyro- and ortho-phosphate quenched samples. The results indicate a gradual decrease in the number of bridging oxygens and increase in the resonance behaviour of non-bridging oxygens as the mole percentage of metal oxide (PbO) increases in the glass. The infrared spectra of several binary phosphate glasses have been reviewed in the context of the study of effect of the cation on the infrared spectra. It is found that the influence of the cation on the infrared spectra of phosphate glasses does not show any striking regularity. Theoretical calculations of these band frequencies were found to agree well only in the case of pure stretching (P=O and O-H) vibrations and pure bending (P-O-P and O-H) vibrations. The disagreement in the case of P-O(−), P-O-H and other modes of P-O-P groups, has been attributed to the mixed nature of modes occurring in glasses. The changes in the positions of the characteristic bands and their relative intensities are strongly dependent on the structural units and PbO content in the phosphate glasses and the results emphasize the role of PbO as a network modifier.

Structural investigations of phosphate glasses: a detailed infrared study of the x(PbO)-(1−x) P2O5 vitreous system

https://escholarship.org/content/qt6tp4d0gt/qt6tp4d0gt.pdf?t=p0fvnt

D.C. Smith

Papers

Infrared Spectra of Phosphorus Compounds