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Eliciting Specific Electrochemical Reaction Behavior by Rational Design of a Red Phosphorus Electrode for Sodium-Ion Batteries.

ABSTRACT: Due to the demand to upgrade from lithium-ion batteries (LIB), sodium-ion batteries (SIB) have been paid considerable attention for their high-energy, cost-effective, and sustainable battery system. Red phosphorus is one of the most promising anode candidates for SIBs, with a high theoretical specific capacity of 2596 mAh g^-1 and in the discharge potential range of 0.01-0.8 V; however, it suffers from a low electrical conductivity, a substantial expansion of volume (~300%), and sluggish electron/ion kinetics. Herein, we have designed a well-defined electrode, which consists of red phosphorus, nanowire arrays encapsulated in the vertically aligned carbon nanotubes (P@C NWs), which were fabricated via a two-step, anodized-aluminum oxide template. The designed anode achieved a high specific capacity of 2250 mAh g^-1 (87% of the theoretical capacity), and a stepwise analysis of the reaction behavior between sodium and red phosphorus was demonstrated, both of which have not been navigated in previous studies. We believe that our rational design of the red phosphorus electrode elicited the specific reaction mechanism revealed by the charge-discharge profiles, rendered excellent electrical conductivity, and accommodated volume expansion through the effective nano-architecture, thereby suggesting an efficient structure for the phosphorus anode to advance in the future.

SUBMITTER: Yun JH

PROVIDER: S-EPMC8625586 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Red-phosphorus-impregnated carbon nanofibers for sodium-ion batteries and liquefaction of red phosphorus.

Project description:Red phosphorus offers a high theoretical sodium capacity and has been considered as a candidate anode for sodium-ion batteries. Similar to silicon anodes for lithium-ion batteries, the electrochemical performance of red phosphorus is plagued by the large volume variation upon sodiation. Here we perform in situ transmission electron microscopy analysis of the synthesized red-phosphorus-impregnated carbon nanofibers with the corresponding chemo-mechanical simulation, revealing that, the sodiated red phosphorus becomes softened with a "liquid-like" mechanical behaviour and gains superior malleability and deformability against pulverization. The encapsulation strategy of the synthesized red-phosphorus-impregnated carbon nanofibers has been proven to be an effective method to minimize the side reactions of red phosphorus in sodium-ion batteries, demonstrating stable electrochemical cycling. Our study provides a valid guide towards high-performance red-phosphorus-based anodes for sodium-ion batteries.

| S-EPMC7239945 | biostudies-literature

Effect of the Particle-Size Distribution on the Electrochemical Performance of a Red Phosphorus-Carbon Composite Anode for Sodium-Ion Batteries.

Project description:Red phosphorus (RP) is a promising candidate as an anode for sodium-ion batteries because of its low potential and high specific capacity. It has two main disadvantages. First, it experiences 490% volumetric expansion during sodiation, which leads to particle pulverization and substantial reduction of the cycle life. Second, it has an extremely low electronic conductivity of 10-14 S cm-1. Both issues can be addressed by ball milling RP with a carbon matrix to form a composite of electronically conductive carbon and small RP particles, less susceptible to pulverization. Through this procedure, however, the resulting particle-size distribution of the RP particles is difficult to determine because of the presence of the carbon particles. Here, we quantify the relationship between the RP particle-size distribution and its cycle life for the first time by separating the ball-milling process into two steps. The RP is first wet-milled to reduce the particle size, and then the particle-size distribution is measured via dynamic light scattering. This is followed by a dry-milling step to produce RP-graphite composites. We found that wet milling breaks apart the largest RP particles in the range of 2-10 ?m, decreases the Dv90 from 1.85 to 1.26 ?m, and significantly increases the cycle life of the RP. Photoelectron spectroscopy and transmission electron microscopy confirm the successful formation of a carbon coating, with longer milling times leading to more uniform carbon coatings. The RP with a Dv90 of 0.79 ?m mixed with graphite for 48 h delivered 1354 mA h g-1 with high coulombic efficiency (>99%) and cyclability (88% capacity retention after 100 cycles). These results are an important step in the development of cyclable, high-capacity anodes for sodium-ion batteries.

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Electrode Materials for High-Performance Sodium-Ion Batteries.

Project description:Sodium ion batteries (SIBs) are being billed as an economical and environmental alternative to lithium ion batteries (LIBs), especially for medium and large-scale stationery and grid storage. However, SIBs suffer from lower capacities, energy density and cycle life performance. Therefore, in order to be more efficient and feasible, novel high-performance electrodes for SIBs need to be developed and researched. This review aims to provide an exhaustive discussion about the state-of-the-art in novel high-performance anodes and cathodes being currently analyzed, and the variety of advantages they demonstrate in various critically important parameters, such as electronic conductivity, structural stability, cycle life, and reversibility.

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Electrochemical Atomic Force Microscopy of Black Phosphorus Composite Anodes: Electrode Destabilization and Degradation Mechanisms in Alkali-Ion Batteries.

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Electrochemical Response of 3D-Printed Free-Standing Reduced Graphene Oxide Electrode for Sodium Ion Batteries Using a Three-Electrode Glass Cell.

Project description:Graphene and its derivatives have been widely used to develop novel materials with applications in energy storage. Among them, reduced graphene oxide has shown great potential for more efficient storage of Na ions and is a current target in the design of electrodes for environmentally friendly Na ion batteries. The search for more sustainable and versatile manufacturing processes also motivates research into additive manufacturing electrodes. Here, the electrochemical responses of porous 3D-printed free-standing log-type structures fabricated using direct ink writing (DIW) with a graphene oxide (GO) gel ink are investigated after thermal reduction in a three-electrode cell configuration. The structures delivered capacities in the range of 50-80 mAh g-1 and showed high stability for more than 100 cycles. The reaction with the electrolyte/solvent system, which caused an initial capacity drop, was evidenced by the nucleation of various Na carbonates and Na2O. The incorporation of Na into the filaments of the structure was verified with transmission electron microscopy and Raman spectroscopy. This work is a proof of concept that structured reduced GO electrodes for Na ion batteries can be achieved from a simple, aqueous GO ink through DIW and that there is scope for improving their performance and capacity.

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Strategies for Alleviating Electrode Expansion of Graphite Electrodes in Sodium-Ion Batteries Followed by In Situ Electrochemical Dilatometry.

Project description:The electrochemical intercalation/deintercalation of solvated sodium ions into graphite is a highly reversible process, but leads to large, undesired electrode expansion/shrinkage ("breathing"). Herein, two strategies to mitigate the electrode expansion are studied. Starting with the standard configuration (-) sodium | diglyme (2G) electrolyte | graphite (poly(vinylidene difluoride) (PVDF) binder) (+), the PVDF binder is first replaced with a binder made of the sodium salt of carboxymethyl cellulose (CMC). Second, ethylenediamine (EN) is added to the electrolyte solution as a co-solvent. The electrode breathing is followed in situ (operando) through electrochemical dilatometry (ECD). It is found that replacing PVDF with CMC is only effective in reducing the electrode expansion during initial sodiation. During cycling, the electrode breathing for both binders is comparable. Much more effective is the addition of EN. The addition of 10 v/v EN to the diglyme electrolyte strongly reduces the electrode expansion during the initial sodiation (+100% with EN versus +175% without EN) as well as the breathing during cycling. A more detailed analysis of the ECD signals reveals that solvent co-intercalation temporarily leads to pillaring of the graphite lattice and that the addition of EN to 2G leads to a change in the sodium storage mechanism.

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Manganese oxide electrode with excellent electrochemical performance for sodium ion batteries by pre-intercalation of K and Na ions.

Project description:Materials with a layered structure have attracted tremendous attention because of their unique properties. The ultrathin nanosheet structure can result in extremely rapid intercalation/de-intercalation of Na ions in the charge-discharge progress. Herein, we report a manganese oxide with pre-intercalated K and Na ions and having flower-like ultrathin layered structure, which was synthesized by a facile but efficient hydrothermal method under mild condition. The pre-intercalation of Na and K ions facilitates the access of electrolyte ions and shortens the ion diffusion pathways. The layered manganese oxide shows ultrahigh specific capacity when it is used as cathode material for sodium-ion batteries. It also exhibits excellent stability and reversibility. It was found that the amount of intercalated Na ions is approximately 71% of the total charge. The prominent electrochemical performance of the manganese oxide demonstrates the importance of design and synthesis of pre-intercalated ultrathin layered materials.

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Sodium-Vanadium Bronze Na9V14O35: An Electrode Material for Na-Ion Batteries.

Project description:Na9V14O35 (η-NaxV2O5) has been synthesized via solid-state reaction in an evacuated sealed silica ampoule and tested as electroactive material for Na-ion batteries. According to powder X-ray diffraction, electron diffraction and atomic resolution scanning transmission electron microscopy, Na9V14O35 adopts a monoclinic structure consisting of layers of corner- and edge-sharing VO5 tetragonal pyramids and VO4 tetrahedra with Na cations positioned between the layers, and can be considered as sodium vanadium(IV,V) oxovanadate Na9V104.1+O19(V5+O4)4. Behavior of Na9V14O35 as a positive and negative electrode in Na half-cells was investigated by galvanostatic cycling against metallic Na, synchrotron powder X-ray diffraction and electron energy loss spectroscopy. Being charged to 4.6 V vs. Na+/Na, almost 3 Na can be extracted per Na9V14O35 formula, resulting in electrochemical capacity of ~60 mAh g-1. Upon discharge below 1 V, Na9V14O35 uptakes sodium up to Na:V = 1:1 ratio that is accompanied by drastic elongation of the separation between the layers of the VO4 tetrahedra and VO5 tetragonal pyramids and volume increase of about 31%. Below 0.25 V, the ordered layered Na9V14O35 structure transforms into a rock-salt type disordered structure and ultimately into amorphous products of a conversion reaction at 0.1 V. The discharge capacity of 490 mAh g-1 delivered at first cycle due to the conversion reaction fades with the number of charge-discharge cycles.

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Sodium vanadium titanium phosphate electrode for symmetric sodium-ion batteries with high power and long lifespan.

Project description:Sodium-ion batteries operating at ambient temperature hold great promise for use in grid energy storage owing to their significant cost advantages. However, challenges remain in the development of suitable electrode materials to enable long lifespan and high rate capability. Here we report a sodium super-ionic conductor structured electrode, sodium vanadium titanium phosphate, which delivers a high specific capacity of 147 mA h g-1 at a rate of 0.1 C and excellent capacity retentions at high rates. A symmetric sodium-ion full cell demonstrates a superior rate capability with a specific capacity of about 49 mA h g-1 at 20 C rate and ultralong lifetime over 10,000 cycles. Furthermore, in situ synchrotron diffraction and X-ray absorption spectroscopy measurement are carried out to unravel the underlying sodium storage mechanism and charge compensation behaviour. Our results suggest the potential application of symmetric batteries for electrochemical energy storage given the superior rate capability and long cycle life.

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Lanthanide doping induced electrochemical enhancement of Na2Ti3O7 anodes for sodium-ion batteries.

Project description:Na2Ti3O7 is considered as a promising anode material for sodium ion batteries (SIBs) due to its excellent high-rate performance compared with hard carbons. However, the electrochemical performance of Na2Ti3O7 is heavily limited by its low electrical conductivity. In this study, we synthesized a series of lanthanide (Ln = La, Ce, Nd, Sm, Gd, Er, and Yb) doped microsized Na2Ti3O7 anode materials and systematically studied the electrochemical performance. Compared with pristine Na2Ti3O7, all the doped samples show superior electrochemical performance. Especially, the Yb3+ doped sample not only delivers a high reversible capacity of 89.4 mA h g-1 at 30C, but also maintains 71.6 mA h g-1 at 5C after 1600 cycles, nearly twice that of pristine Na2Ti3O7. It is found for the first time that the enhancement in doped samples is attributed to the introduction of lanthanides which induces lattice distortion and oxygen vacancies.

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