Tin Phosphide Research Articles

Synthesis of hollow spherical tin phosphides (Sn4P3) and their high adsorptive and electrochemical performance

Sn4P3 hollow spherical microstructures are successfully synthesized by a facile Solvothermal approach with the help of ethylenediamine tetraacetic acid (EDTA). Further study show that EDTA plays an important role as chelating and capping reagent in the formation of Sn4P3 hollow microspheres at room temperature. The research displays that the as-prepared Sn4P3 catalysts could absorb some typical organic dyes such as Methylene Blue, Safranine T and Methyl Orange, especially the adsorption ratio for some could reach to 99%. Meanwhile, as anode materials for lithium ion batteries, the initial discharge capacity of the as-prepared Sn4P3 hollow microspheres exceed 1478mAhg−1 at 100mAg−1 and it still keeps at 261mAhg−1 after 20 cycles. Even the current density is increased to 500mAg−1, the second discharge capacity still can attain to 689mAhg−1.

Solvothermal preparation of tin phosphide as a long-life anode for advanced lithium and sodium ion batteries

Tin phosphide (Sn4P3) nanoparticles with different sizes are synthesized via a facile solvothermal method at 180 °C for 10 h. The as-prepared Sn4P3 nanoparticles have an average size of about 15 nm. Meanwhile, their size could be easily controlled by the solvent ratio. The long cycle stability and rate performance of the as-obtained Sn4P3 nanoparticles have been tested as an anode material for lithium ion batteries for the first time. Electrochemical measurements show that the Sn4P3 nanoparticles with a smallest size give the best cycling and rate performances. They deliver a discharge capacity of 612 mAh g−1 after 10 cycles and could still maintain 442 mAh g−1 after 320 cycles at the current density of 100 mA g−1 within voltage limit of 0.01–3.0 V. Even after 200 cycles at a current density of 200 mA g−1, the specific capacity still could be remained at 315 mAh g−1. The improved electrochemical performances of Sn4P3 electrode might be largely attributed to their small-size. Furthermore, the as-prepared Sn4P3 nanoparticles have also been tested as an anode material for Na-ion batteries, this Sn4P3 anode can deliver a reversible capacity of 305 mAh g−1 after 10 cycles at the current density of 50 mA g−1.

Tin and Tin Compounds for Sodium Ion Battery Anodes: Phase Transformations and Performance.

Sodium ion batteries (NIB, NAB, SIB) are attracting interest as a potentially lower cost alternative to lithium ion batteries (LIB), with readily available and geographically democratic reserves of the metal. Tin is one of most promising SIB anode materials, which alloys with up to 3.75 Na, leading to a charge storage capacity of 847 mAh g(-1). In this Account, we outline the state-of-the-art understanding regarding the sodiation-induced phase transformations and the associated performance in a range of Sn-based systems, treating metallic Sn and its alloys, tin oxide (SnO2), tin sulfide (SnS2/SnS), and tin phosphide (Sn4P3). We first detail what is known about the sodiation sequence in metallic Sn, highlighting the most recent insight into the reactions prior to the terminal equilibrium Na15Sn4 intermetallic. We explain why researchers argue that the equilibrium (phase diagram) series of phase transitions does not occur in this system, and rather why sodiation/desodiation proceeds through a series of metastable crystalline and amorphous structures. We also outline the recent modeling-based insight regarding how this phase transition profoundly influences the mechanical properties of the alloy, progressively changing the bonding and the near neighbor arrangement from "Sn-like" to "Na-like" in the process. We then go on to discuss the sodiation reactions in SnO2. We argue that while a substantial amount of experimental work already exists where the focus is on synthesis and testing of tin oxide-based nanocomposites, the exact sodiation sequence is just beginning to be understood. Unlike in Sn and Sn alloys, where capacities near the theoretical are reached at least early during cycling, SnO2 never quite achieves anything close to the 1398 mAh g(-1) that would be possible with a combination of fully reversible conversion and alloying reactions. We highlight recent work demonstrating that contrary to general expectations, it is the Sn to Na15Sn4 alloying reaction that is incomplete and hence limits the capacity of the electrode. We also describe how the oxide conversion reaction goes through an intermediate SnO phase, and how its reversibility in a half-cell is highly dependent on the terminal anodic voltage. We then present what is known about sodiation of tin sulfide and of tin phosphide phases, including emerging microstructural evidence that may explain why both the sulfides and the phosphides are unable to achieve their highly promising theoretical capacities under conventional electrode testing conditions. Finally, we provide a broad comparison of the capacity (cycling and rate) performance for a range of Sn based anode materials, and show that there may be indeed an optimum microstructural architecture.

Investigation of Graphite/Tin Phosphide Composites As the Potential Anode in Li-Ion Batteries

Driven by the rapidly-growing of hybrid and electric vehicles, there is an increasing demand on lithium ion batteries (LIBs) with high energy density, long cycle life, and low cost. One of the most widely used anode materials in LIBs, graphite, only possesses a theoretical specific capacity of about 370 mAh/g, limiting the specific energy of LIBs.1 Recently, conversion-type of electrode materials, i.e. metal oxide and metal sulfide, has been regarded as one of the most promising anode materials for high performance LIBs, due to the low cost and exceptionally high specific capacity (>1000 mAh/g).2 However, these conversion-type electrode materials suffers from several issues, i.e. relatively low conductivity and rapid capacity fade due to irreversible phase change and particle pulverization during cycling. For example, the poor performance of tin oxide is mainly caused by its low intrinsic conductivity, formation of irreversible insulating Li2O phase during discharging, and large volume change.3 To overcome these disadvantages, various methods have been developed, like carbon/tin oxide composites, tin phosphide (Sn4P3). Tin phosphide has a layered structure and can be prepared by a mechanochemical or hydrothermal method. It has shown promising electrochemical performance as the anode in Li-ion batteries.4,5 As the lithium was inserted, Sn4P3 was first converted into lithium phosphides and Sn, followed by lithium-tin alloy formation. The advantage of Sn4P3 is its high capacity and Li+ conductivity of the Li3P. However, it suffers from similar drawbacks as tin oxide, i.e. large volume change and irreversible Li3P phase formation. In this work, we prepared Sn4P3 nanowires by hydrothermal reaction of red phosphorus and tin in ethylenediamine at 200 °C for 40 h. Then, graphite/Sn4P3 composites were prepared by high-energy ball milling for 2 h under Ar atmosphere. Graphite and Sn4P3 were uniformly distributed in the composites, shown in Figure 1a. When tested as the anode materials, the composites showed superior performance compared to Sn4P3 alone. The capacity of Sn4P3 rapidly decreased to around 200 mAh/g after 15 cycles. In comparison, graphite/Sn4P3 composites showed an initial specific capacity of about 1014 mAh/g and maintained a capacity of 782 mAh/g after 50 cycles. In addition, the coulombic efficiency was also much higher in the graphite/Sn4P3 composites, indicating a reversible Li insertion/deinsertion behavior and more stable SEI layer. The rate performance of graphite/Sn4P3 composites was also much better than pure Sn4P3. In conclusion, we report a facile preparation of graphite/Sn4P3 composites with excellent electrochemical performance as anode material in Li-ion batteries. Figure 1

Electrochemical Na-insertion/Extraction Properties of Sn–P Anodes

Thick-film electrodes of tin phosphides, Sn4P3 and SnP3, were prepared using a mechanical alloying method followed by a gas-deposition method, and were evaluated as Na-ion battery anodes in an organic electrolyte and ionic liquid electrolytes. The Sn4P3 electrode showed a better cycling performance in the organic electrolyte compared with the SnP3 electrode and an Sn electrode. The performance of the Sn4P3 electrode was further improved by using ionic liquid electrolytes because of a uniformly formed surface layer and resulting uniform sodiation/desodiation reactions on the electrode.

Solution-based synthesis and purification of zinc tin phosphide nanowires.

The solution-based synthesis of nanoscale earth-abundant semiconductors has the potential to unlock simple, scalable, and tunable material processes which currently constrain development of novel compounds for alternative energy devices. One such promising semiconductor is zinc tin phosphide (ZnSnP2). We report the synthesis of ZnSnP2 nanowires via a solution-liquid-solid mechanism utilizing metallic zinc and tin in decomposing trioctylphosphine (TOP). Dried films of the reaction product are purified of binary phosphide phases by annealing at 345 °C. Tin is removed using a 0.1 M nitric acid treatment leaving pure ZnSnP2 nanowires. Diffuse reflectance spectroscopy indicates ZnSnP2 has a direct bandgap energy of 1.24 eV which is optimal for solar cell applications. Using a photoelectrochemical cell, we demonstrate cathodic photocurrent generation at open circuit conditions from the ZnSnP2 nanowires upon solar simulated illumination confirming p-type conductivity.

ChemInform Abstract: Tin Phosphide as a Promising Anode Material for Na‐Ion Batteries.

AbstractSn4P3 is prepared by ball milling of Sn and red phosphorus powders (Ar atmosphere, 1 h) and characterized by powder XRD, FESEM, TEM, and electrochemical measurements.

Phosphorus-Based Negative Electrode Materials for Na-Ion Batteries

Introduction Na-ion batteries have recently received a lot of attention as a next-generation battery, because Na resources are inexhaustible and cheaper than Li resources. However, although Na-ion batteries have shown promising electrochemical performance including stable cycle performance and good rate performance, it should be mentioned that it is not easy for Na-ion batteries to replace Li-ion batteries owing to the critical issue of Na-ion batteries having slightly lower energy density than Li-ion batteries. Therefore, in order to successfully replace Li-ion batteries by Na-ion batteries, new anode materials having a high reversible capacity should be introduced. In this presentation, phosphorus-based negative electrode materials are introduced for Na-ion batteries. Phosphorus-based electrodes showed excellent electrochemical performance including a high reversible capacity (>700 mAh/g), excellent cycle performance, and an ideal redox potential (< 0.4 V vs. Na/Na+), thus making it a promising candidate for Na ion batteries. Experimental Two types of phosphorus-based active materials were prepared as follows. For red phosphorus/carbon composites, phosphorus powder and Super P carbon were mixed in a 7:3 weight ratio using a high energy mechanical ball-milling method. For the synthesis of tin phosphide, phosphorus and Sn powders were mixed using the same ball-milling method.Samples of active materials were mixed with carbon black (Super P) and polyacrylic acid (PAA) in a 7:1:2 weight ratio. The electrochemical performance was evaluated using 2032 coin cells with a Na metal anode and 1 M NaClO4in ethylene carbonate and diethyl carbonate (1:1 v/v) with or without the addition of 5% fluoroethylene carbonate (FEC).For the analysis of the reaction mechanism, ex-situ X-ray diffraction (ex-situXRD), high resolution transmission electron microscope (HR-TEM) and X-ray absorption spectroscopy (XAS) analysis were performed. Results and Discussion The amorphous red phosphorus/carbon composite exhibited promising electrochemical performance including i) high reversible capacity of 1890 mA h g-1 (equivalent to 2.18 mol of Na alloyed with one mole of P); ii) good cycle performance over 30 cycles; and iii) appropriate redox potential of ca.0.4 V vs. Na/Na+.Also, tin phosphide electrode showed excellent electrochemical performance including i) high reversible capacity of about 718 mA h g-1; ii) negligible capacity fading over 100 cycles in spite of the large particle size (> a few micrometer).Finally, the reaction and failure mechanisms of both electrodes were studied using ex situ instrumental analysis.

Tin Phosphide as a Promising Anode Material for Na‐Ion Batteries

Sn4 P3 is introduced for the first time as an anode material for Na-ion batteries. Sn4 P3 delivers a high reversible capacity of 718 mA h g(-1), and shows very stable cycle performance with negligible capa-city fading over 100 cycles, which is attributed to the confinement effect of Sn nanocrystallites in the amorphous phosphorus matrix during cycling.

VASP Calculation on Lithium Reaction to Tin Phosphides

Studies on electrochemical reaction of SnPx materials were carried out by VASP ab initio calculation, where. SnPx having four different crystalline compositions, SnP0.75(Sn4P3), SnP0.94(SnP17/18), SnP and SnP3. The reaction potential of the lithiation of SnP0.94(SnP17/18) material was compared between intercalation and conversion reaction. The total-energy calculation and full structural optimization of SnPx, SnPx related materials and Li materials were performed using the Vienna ab initio Simulation Package (VASP)[1]. The possibility of intercalation of lithium to SnP0.94 was analyzed to obtain reaction potential of 1.853 V (Li/Li+) accommodating lithium to 6i site. 6i site is a vacant site in Sn18P17 (SnP0.94). Through further intercalation of lithium, reaction potential of Li0.5SnP0.94, Li1.5SnP1.56 and Li6.06SnP0.94 can also be calculated as 0.9026, 0.705 and -1.5 V(Li/Li+), respectively.Considering conversion reaction, SnP0.94 can react to produce 2 kinds of products such as LiP and Li3P as shown in Eq. 1. SnP0.94 + (0.94z+y) = 0.94LizP + LiySn ---------(1) At LiySn formation, y of zero means that only conversion reaction takes place without the formation of LiySn. Reaction potential of y=0 were 1.35 V and 0.948 V for the formation of LiP and Li3P. Reaction potential of the hole reaction [SnP0.94 + xLi = products], including intercalation and conversion, was plotted against reacted lithium extent of x in Fig. 1. It is observed that the reaction potential of conversion is higher than that of the lithium intercalation. In case of conversion reaction to form LiP with reacted lithium extent of 0.94 was 1.35 V which was higher than 0.937 V of lithium intercalation to form Li0.56SnP0.94 . Therefore, conversion reaction is labile compared to intercalation. Moreover, the reaction potential of conversion to form Li3P with reacted lithium extent of 2.833 was 0.948 V which is higher than that of the conversion reaction potential of 0.704 V to form LiP with reacted lithium extent of 3.28. Therefore conversion reaction to form Li3P is easier than to form LiP. We will discuss VASP calculation on lithium reaction to Tin Phosphides in details[1] Kresse,G.; Hafner, J. Phys. Rev. B , 47 (1993) 558; 49(1994) 14251.

A Novel Solvothermal Route to Nanocrystalline Sn&lt;sub&gt;4&lt;/sub&gt;P&lt;sub&gt;3&lt;/sub&gt; with Red Phosphorous as Raw Material

Nanocrystalline tin phosphide Sn4P3 was synthesized from red phosphorus and tin chloride SnCl22H2O by a low temperature (200°C) solvothermal reaction in ethanolamine for only 10 hours. The important parameters of solvothermal processmolar ratio of initial components (P/Sn), temperature and duration were investigated. The phase, composition and morphology of the products were characterized by X-ray diffraction (XRD), energy dispersive spectroscopy (EDS) and transmission electron microscopy (TEM). The ideal solvothermal conditions to synthesize pure and nanocrystallined Sn4P3 were summarized in this work.

Electrochemical performance of all-solid-state lithium batteries with Sn4P3 negative electrode

All-solid-state lithium secondary batteries have been studied as new energy storage devices with safety and reliability. To enhance the energy density of the batteries, negative electrode materials with high capacity have been actively studied. Tin phosphide Sn4P3 has a high theoretical capacity and forms Li3P with Li ion conductivity in the initial lithium insertion. Li3P would act as a matrix suppressing the volume change and giving lithium ion conduction paths. In this study, Sn4P3 was prepared by mechanical milling and electrochemical performance of all-solid-state cells with the Sn4P3 was evaluated. The working electrode of all-solid-state cell consist of Sn4P3, solid electrolyte (SE) and acetylene black (AB) for smooth conduction of lithium ion and electron. The cell with the Sn4P3 composite electrode showed the first discharge capacity of 1080 mA h g−1 and the initial columbic efficiency of 88%. Moreover, Sn4P3 was applied to the working electrode without SE and AB and its cell performance was evaluated. The cell discharged and charged, and showed the first discharge capacity of 670 mA h g−1. Sn4P3 is thus a favorable negative electrode material to improve energy density of all-solid-state cells.

Synthesis of tin phosphides (Sn4P3) and their high photocatalytic activities

Tin phosphides (Sn4P3) with different shapes were successfully synthesized via a solvothermal method, using N,N-dimethylformamide (DMF) as solvent in the presence of NaBH4. The phases and morphologies of the products were characterized by means of X-ray powder diffraction (XRD) and scanning electron microscopy (SEM). It was found that the sodium dodecyl sulphate (SDS) played an important role in the formation of Sn4P3 with different shapes. Furthermore, research also showed that both of the as-prepared Sn4P3 catalysts could photocatalytically degrade some typical organic dyes such as Safranine T, Methylene Blue, Methyl Orange and Pyronine B. In order to investigate the correlation between properties and shapes, the photocatalytic degradation abilities and selectivities of two different phosphides for organic dyes were discussed.

SnP0.94 active material synthesized in high-boiling solvents for all-solid-state lithium batteries

Tin phosphide (SnP0.94) particles were synthesized by thermal decomposition of tin acetate in a mixed solution of trioctylphosphine and a high-boiling solvent. Teardrop-shaped SnP0.94 particles with the size of about 500 nm were obtained by using trioctylphosphine oxide as a coordinating solvent. In the case using oleylamine as a solvent, the shape of SnP0.94 particles was not uniform. Formation mechanism of teardrop-shaped SnP0.94 was discussed. SnP0.94 particles prepared by using the trioctylphosphine oxide as a coordinating solvent were applied as an active material to all-solid-state lithium cells. The cell Li–In/80Li2S·19P2S5·1P2O5/SnP0.94 exhibited the initial discharge capacity of 1000 mAh g−1 at a current density of 1.3 mA cm−2.

Highly Disordered Crystal Structure and Thermoelectric Properties of Sn3P4

The crystal structure of Sn3P4, a long-known tin phosphide, has been determined. It crystallizes in the trigonal space group R3m with unit-cell parameters a = 4.4315(1) A and c = 28.393(1) A (Z = 3). The crystal structure of Sn3P4 is disordered. It consists of alternating layers of phosphorus and tin atoms that are combined into five-layer blocks and propagate along the c-axis. The major structural feature is the disordered orientation of the P24– dumbbells, which link the tin atoms. The latter possess two types of coordination. One third of the tin atoms reside inside the block and are octahedrally coordinated by phosphorus atoms. The rest of the tin atoms confine the block and possess a [3 + 3] environment made up of three close phosphorus neighbors and three rather distant (3.4 A) tin atoms of the adjacent block. The coordination of the tin atoms is confirmed by 119Sn Mossbauer spectroscopy. The electron diffraction and high-resolution electron microscopy data reveal ordered regions at the microscopic...

A Facile High‐Yield Solvothermal Route to Tin Phosphide Sn4P3.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.

Reversible Lithium Intercalation in Teardrop‐Shaped Ultrafine SnP0.94 Particles: An Anode Material for Lithium‐Ion Batteries

Uniformly dispersed teardrop-shaped tin phosphide particles for lithium-ion batteries are synthesized by the reaction of tin acetate in a mixed solution of trioctyl phosphine (TOP) and trioctylphosphine oxide (TOPO). Reversible intercalation/deintercalation of lithium ions into/from the tin phosphide is found, giving LixSnP0.94 with x up to 3.91 (740 mA h g–1), and little capacity fading between 0 and 1.2 V.

A facile high-yield solvothermal route to tin phosphide Sn 4P 3

An effective method of synthesis of tin phosphide Sn 4P 3 starting from metallic tin and amorphous red phosphorus by a low-temperature (200 °C) solvothermal reaction in ethylenediamine is offered. The key parameters of this process – duration, temperature, and the ratio of initial components (Sn/P) are studied. The structure, phase composition, and morphology of the products are investigated using powder X-ray diffraction and scanning electron microscopy. Different synthetic ways for tin phosphide are discussed and compared with the proposed one. The mechanism of solvothermal preparation of tin phosphide in ethylenediamine is discussed. It is shown that the proposed solvothermal method opens up the possibility of preparing other metal-rich phosphides.

On the Mechanism of the Electrochemical Reaction of Tin Phosphide with Lithium

With a view to the possible application of tin phosphide as the negative electrode in advanced lithium-ion battery test cells, and magic angle spinning nuclear magnetic resonance and Mössbauer spectroscopy techniques were used to reveal the mechanism of the electrochemical reactions in lithium test cells. The formation of and Sn through a conversion reaction was observed. This process was followed by the successive formation of intermetallics up to stoichiometry. Reversibility was restricted to the formation of lithium–tin intermetallics thus limiting the maximum allowed reversible capacity.

Superior high rate capability of tin phosphide used as high capacity anode for aqueous primary batteries

Tin phosphide (Sn 4P 3) with a layered structure was synthesized by direct ball-milling method and tested for possible use as an electroactive anode material in alkaline aqueous solution. The experimental results demonstrated that the Sn 4P 3 electrode could deliver a discharge capacity of 775 mAh/g at the constant current of 200 mA/g, 716 mAh/g at 2000 mA/g and 511 mAh/g at 5000 mA/g respectively, showing a superiorly high rate capability in alkaline aqueous solution. The excellent electrochemical activity of the Sn 4P 3 material is found to arise from the cooperative interaction of the P and Sn atoms in the layered crystalline structure, in which the Sn atom layers serve as a conductive framework providing an electronic passage for the 5-electron oxidation of the P atoms.