Phosphate-based Materials Research Articles

Effects of inorganic phosphate on stem cells isolated from human exfoliated deciduous teeth

Calcium phosphate-based materials (CaP) are introduced as potential dental pulp capping materials for deciduous teeth. The present study investigated the influence of inorganic phosphate (Pi) on regulating stem cells isolated from human exfoliated deciduous teeth (SHED). SHEDs were treated with Pi. Cell cycle progression and apoptosis were examined using flow cytometry analysis. Osteo/odontogenic and adipogenic differentiation were analyzed using alizarin red S and oil red O staining, respectively. The mRNA expression profile was investigated using a high-throughput RNA sequencing technique. Pi increased the late apoptotic cell population while cell cycle progression was not altered. Pi upregulated osteo/odontoblastic gene expression and enhanced calcium deposition. Pi-induced mineralization was reversed by pretreatment of cells with Foscarnet, or p38 inhibitor. Pi treatment inhibited adipogenic differentiation as determined by decreased PPARγ expression and reduced intracellular lipid accumulation. Bioinformatic analysis of gene expression profiles demonstrated several involved pathways, including PI3K/AKT, MAPK, EGFR, and VEGF signaling. In conclusion, Pi enhanced osteo/odontogenic but inhibited adipogenic differentiation in SHED.

Nanostructured bismuth phosphate-based asymmetric supercapacitor: electrochemical evaluation and oscillator application

Phosphate-based materials have received significant attention for various applications. In supercapacitors, metal phosphates exhibit high capacitance and superior rate performance. In this work, a wet chemical route was applied for the fabrication of aniline stabilized monoclinic bismuth phosphate (BPO) particles within the size range of 4–10 nm. The synthesized material was utilized as an active component for the application of a supercapacitor. The performances of the material were examined on a nickel foam for a three-electrode electrochemical cell. The material showed the maximum specific capacitance (CSP\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${C}_{SP}$$\\end{document}) value of 255 F.g−1 at the current density (CD) of 2 A.g−1. Further, an asymmetric supercapacitor (ASC) device was fabricated with BPO and single wall carbon nanotube (SWCNT) as negative and positive electrodes, respectively, which delivered a specific capacity (Qs)\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$(Qs)$$\\end{document} value of 1462 mAh.g−1 under the CD of 0.4 A.g−1 with the energy density (ED) and power density (PD) values of 2.2 Wh.kg−1 and 0.68 kW.kg−1, respectively. The device exhibited capacity retention and coulombic efficiency (CE) values of 84 and 95% at 0.9 A.g−1 for 10,000 galvanostatic charge–discharge (GCD) cycles. The ASC device generated a low-frequency waveform and has the potential to function as an oscillator.

Ion-intercalation mechanism and structural relaxation in layered iron phosphate Na3Fe3(PO4)4 cathodes

Layered Na3Fe3(PO4)4 can function as a positive electrode for both Li- and Na-ion batteries and may hold advantages from both classical layered and phosphate-based electrode materials. Using a combination of ex-situ and operando synchrotron radiation powder X-ray diffraction, void space analysis, and Mössbauer spectroscopy, we herein investigate the structural evolution of the Na3Fe3(PO4)4 framework during Li- and Na-ion intercalation. We show that during discharge, Li- and Na-intercalation into Na3Fe3(PO4)4 occurs via a solid solution reaction wherein Na-ions appear to be preferentially intercalated into the intralayer sites. The intercalation causes an expansion of the unit cell volume, however at open circuit conditions after ion-intercalation (i.e., after battery discharge), Na3+xFe3(PO4)4 and LixNa3Fe3(PO4)4 undergo a structural relaxation, wherein the unit volume contracts below that of the pristine material. Rietveld refinement suggests that the ions intercalated into the intra-layer sites diffuse to the sites in the inter-layer space during the relaxation. This behavior brings new perspectives to understanding structural relaxation and deviations between structural evolution observed under dynamic and static conditions.

Are we approaching the development of a novel calcium phosphate-based bioceramic dental material?

ObjectivesDevelop a sustainable bovine hydroxyapatite dental ceramic with the addition of titanium dioxide (TiO2) nanoparticles (5 % and 8 % by weight), analyzing the outcome of this addition to the microstructure, as well as its mechanical and chemical properties, in order to evaluate whether they satisfy the International Organization for Standardization (ISO) 6872:2015 for dental ceramics or not. MethodsDisks were obtained through uniaxial followed by isostatic pressing from bovine hydroxyapatite powder and TiO2 nanoparticles and sintered at 1300ºC for 2 h. Three experimental groups were developed (HA, HA+5 %TiO2 and HA+8 %TiO2) and subjected to X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), indentation fracture (IF), biaxial flexural strength (BFS) and chemical solubility test. ResultsXRD revealed, for HA group, the appearance of a peak corresponding to b-tricalcium phosphate (ß-TCP). For HA+ 5 %TiO2 and HA+ 8 %TiO2, the entire composition was converted into ß-TCP and calcium titanate (CaTiO3). The SEM images showed a dense ceramic matrix and a uniform distribution of another phase in groups with TiO2 nanoparticles. HA+ 5 %TiO2 (1.40 ± 0.18 MPa.m1/2) and HA+ 8 %TiO2 (1.32 ± 0.18 MPa.m1/2) showed significantly higher fracture toughness values than HA (0.67 ± 0.09 MPa.m1/2). HA showed significantly higher characteristic stress (295.8 MPa) in comparison to groups with 5 % (235.1 MPa) and 8 % (214.4 MPa) TiO2 nanoparticles. Differences were not observed between the Weibull modulus values. The solubility results indicated that all experimental ceramics were above the 2000 ug/cm2 limit set by the ISO 6872:2015. SignificanceThis study proposed the development and characterization of a new ceramic for dental prosthesis made from HA extracted from bovine bones, with the intention of reusing these solids waste and transforming them into a sustainable and low-cost material. Although the experimental calcium phosphate ceramic with additions of 5 % and 8 % of TiO2 achieved desirable mechanical properties, the chemical solubility values were very high.

An effective cascade strategy over a Sn-enriched phosphate material: Upcycling a reductive adsorbent into an environmental catalyst

A calcium phosphate-based material enriched with Sn (8.3 at.%, as revealed by X-ray photoelectron spectroscopy) was successfully used in the reductive adsorption of Cr(VI) to Cr(III) for water remediation and, after use, repurposed into a catalyst for NO oxidation into NO2.The use of multiple characterization techniques (Mӧssbauer spectroscopy, synchrotron X-ray diffraction, TEM, and HAADF-STEM/EDS) provided information on Sn-speciation (Sn(II)/Sn(IV) = 1.2), structural composition, and morphological features. Cassiterite (rutile-type SnO2) and hydroromarchite (tin oxide-hydroxide Sn6O4(OH)4) crystalline phases characterized the material, along with the presence of an amorphous Ca3(PO4)2 phase.Notably, about 15 mgCr(VI)∙g−1 could be effectively reduced over a broad pH range (2–11), even in the simultaneous presence of various anions and cations, with concurrent adsorption of the resulting Cr(III), thanks to the adsorption properties of the phosphate phase. The kinetic constant of Cr(VI) removal was as high as 0.0058 g∙mg−1∙min−1 and increased in the presence of a pool of cations (0.0147 g∙mg−1∙min−1). The catalytic performances of the adsorbent after use in Cr(VI) reductive adsorption were studied in the 150–450 °C interval at 15,000–80,000 h−1 space velocity. About 90 % of NO conversion at 350 °C was observed.This study highlights the adaptability and efficiency of the developed material across different environmental remediation processes.

Ti3C2Tx MXene-Decorated 3D-Printed Ceramic Scaffolds for Enhancing Osteogenesis by Spatiotemporally Orchestrating Inflammatory and Bone Repair Responses.

Inflammatory responses play a central role in coordinating biomaterial-mediated tissue regeneration. However, precise modulation of dynamic variations in microenvironmental inflammation post-implantation remains challenging. In this study, the traditional β-tricalcium phosphate-based scaffold is remodeled via ultrathin MXene-Ti3C2 decoration and Zn2+/Sr2+ ion-substitution, endowing the scaffold with excellent reactive oxygen species-scavenging ability, near-infrared responsivity, and enhanced mechanical properties. The induction of mild hyperthermia around the implant via periodic near-infrared irradiation facilitates spatiotemporal regulation of inflammatory cytokines secreted by a spectrum of macrophage phenotypes. The process initially amplifies the pro-inflammatory response, then accelerates M1-to-M2 macrophage polarization transition, yielding a satisfactory pattern of osteo-immunomodulation during the natural bone healing process. Later, sustained release of Zn2+/Sr2+ ions with gradual degradation of the 3D scaffold maintains the favorable reparative M2-dominated immunological microenvironment that supports new bone mineralization. Precise temporal immunoregulation of the bone healing process by the intelligent 3D scaffold enhances bone regeneration in a rat cranial defect model. This strategy paves the way for the application of β-tricalcium phosphate-based materials to guide the dynamic inflammatory and bone tissue responses toward a favorable outcome, making clinical treatment more predictable and durable. The findings also demonstrate that near-infrared irradiation-derived mild hyperthermia is a promising method of immunomodulation.

Rational design of copper phosphate based polyanionic framework for high performance supercapacitor

The key to high-performing supercapacitors is their abundance, low cost, and ability to deliver high capacitance in a wide electrochemical window. A new class of phosphate-based polyanion material has been developed to deliver high capacitance via the effective utilization of their oxidation states. Cu3(PO4)2 was synthesized by the facile hydrothermal technique and delivers an ultra high specific capacitance of about 814 F/g with multiple discharge plateaus at a current density of 1 A/g within a voltage window ranging from 0.4 v to -1.2 V. This intriguing behavior is mainly due to the multi functional Cu while interacts with the electrolytic ions and also the inductive effect of a phosphate group (PO4)2− contributes to a high discharge voltage of -1.2 V during charging and discharging process. It shows exceptional cyclic stability of 100 % over 10,000 cycles without sacrificing its coulombic efficiency and it is pertinent the structural stability of the system. The symmetric device was fabricated and delivered power density and energy density of 4.5 kW/kg and 31.5 Wh/kg, and also maintained excellent cyclic stability at 92 % with high reversibility of charged ions. This offers new insights into the high potential of using polyanion-type compounds as high-capacity materials for advanced energy storage systems.

Investigations on Microstructure and Mechanical Properties of HAp Nanocomposites reinforced with ZrO2 and TiO2

In the contemporary context, approximately 15 million individuals in India grapple with bone-related issues stemming from accidents, fractures, bone mass depletion, and the natural aging process. To address this challenge, a diverse array of biomaterials has been innovated to rectify or enhance bone deficiencies within the human body. Nevertheless, over the past decade, calcium phosphate-based bioceramic materials have gained significant prominence as synthetic alternatives for bone and dental applications in the fields of orthopaedics and dentistry. One such bioactive ceramic, Hydroxyapatite (HAp), boasts exceptional versatility and can find utility in both dental and orthopaedic contexts. In the current research, exhaustive research was conducted to explore the impact of HAp/(ZrO2+TiO2) hybrid nano-composites synthesized through a mechanical synthesis process employing high-energy ball milling (HEBM), incorporating varying weight proportions. The resulting “HAp/(ZrO2+TiO2) nano-composites” were subjected to characterization through scanning electron microscopy combined with energy-dispersive X-ray spectroscopy (SEM-EDX) and X-ray diffraction (XRD). Furthermore, the study assessed the influence of these nano-composites regarding the HAp nano-composites’ mechanical characteristics.

Boosting the capacity and stability of Na3V2(PO4)2F3-2xO2x microspheres, using atomic layer deposition of artificial CEI

Phosphate-based materials [e.g. Na3V2(PO4)2F3-2xO2x; (NVPFO2x;0 < x < 1)] are regarded as a promising intercalation cathodes for Sodium-ion batteries (SIBs) due to their high reversible specific capacity and stability. However, so far only 2 Na ion were demonstrated to be active in these polyanionic cathodes, which limit their capacity. Herein we provide a strategic approach towards electrochemical activation of a 3rd Na ion, which leads to higher capacity, and preserves structural integrity. We synthesize and study a series of NVPFO2x (0 < x < 1) with well-controlled surface morphology and vanadium oxidation state, and study the dependence of the electrochemical behavior on the various composition and morphology. The optimized NVPFO cathode exhibited highest initial specific discharge capacity (131 mA h g−1) indicating the activation of 3rd Na ion. Nevertheless, the material suffers rapid capacity fading within ~50 cycles. We demonstrate how this instability is suppressed profoundly through the formation of a thin artificial cathode electrolyte interface (CEI) layer of TiO2 (ca. 2 nm) on the surface of NVPFO by atomic layer deposition (ALD). This TiO2 coating enabled even further extraction of sodium through higher voltage domain, but more importantly, it facilitated excellent long-term stability over 200 cycles. The structural stability of the cathode material was revealed by post cycling HRSEM, XPS, and XRD study. All these studies demonstrate that the thin TiO2 layer effectively contributes to formation of a robust CEI layer, diminishes the parasitic reaction on the electrode surface, reduces carbonate formation, and restricts the electrolyte decomposition.

Downsizing and coating effects on the electrochemical performance of Mn-doped iron fluorophosphate as cathode material for sodium-ion batteries

Sodium Mn-doped iron fluorophosphate Na2Fe0·5Mn0·5PO4F is a potential positive electrode material for lithium-ion and sodium-ion batteries. This study outlines the synthesis of Na2Fe0·5Mn0·5PO4F powder through a simplified and more accessible production method. The X-rays diffraction (XRD) technique showed a pure phase with monoclinic symmetry (S.G. P21/n). The resulting uncoated material (labeled as NFeMPF) was ball-milled with dopamine hydrochloride (mentioned as dopamine hereafter) as a carbon source to enhance the specific surface and improve its electronic conductivity. Raman spectra confirmed the presence of residual carbon after the pyrolysis process. Thermogravimetric analysis (TGA) demonstrated the stability of Mn-doped iron fluorophosphate up to 1000 °C. Additionally, Mössbauer spectroscopy disclosed structural improvements in the material, indicating the reduction of all Fe(III) when coated with dopamine. The uncoated material discharge capacity when cycled against sodium exhibits reversible capacities of only 80, 67, and 38 mAh/g during the first cycle at C/20, C/16, and C/5, respectively. The coated NFeMPF@D delivered improved capacities of 272 and 202 mAh/g at C/20 and C/16, respectively. This highlights the considerable promise of the investigated phosphate-based electrode material as a cathode composite for the next generation of sodium-ion batteries.

Boosting sodium-ion battery performance using Na3(VO)2(PO4)2F microrods self-embedded in a 3D conductive interpenetrated framework

Na3(VO)2(PO4)2F (NVPOF) is considered as a promising cathode candidate for sodium-ion batteries (SIBs) owing to the high theoretical capacity and operating voltage. However, the challenges of its rate capability and cyclability limit its widespread application. Herein, the reduced graphene oxide decorated NVPOF microrods (NVPOF@G) are successfully synthesized by a facile hydrothermal-induced self-assembly procedure. It is found that the graphene oxides added act as a crystal nucleation growth regulator and provide rapid Na+ and electron transport in the electrodes. The prepared NVPOF@G microrods exhibit a superior rate capability of 82.2 mAh g−1 at 50 C (fast discharge in 72 s) as well as considerable long-term cycle stability with a capacity retention of 87.6% over 1000 cycles at 0.5 C. Even at 50 °C, the NVPOF@G still achieves a high reversible capacity of 109.4 mAh g−1 with a capacity retention of 87.7% after 1000 cycles. This microrod structure shows superior structural stability, even at high temperatures (50 °C). Such a cathode incorporates the benefits of batteries and supercapacitors. This work gives a way to fabricate microrod-structure phosphate-based materials for commercial applications in high-performance SIBs.

Magnesium-Substituted Brushite Cement: Physical and Mechanical Properties

Brushite cements (BrCs) are calcium phosphate-based materials that are being widely used in hard tissue engineering applications due to their osteoconductivity, injectability, and bioresorbability. Therefore, the goal was to evaluate the effects of Mg concentration on the phase composition, setting time, and strength of BrC. Mg, which plays a vital role in bodily functions and bone health, was added to BrC at concentrations of 0.25, 0.50, 1.00, 1.50, 2.00, and 2.50 wt.%. The results showed that Mg stabilizes the TCP structure and increases the TCP content in final BrC. The initial and final setting times of BrCs increase with higher concentrations of Mg. Although 0.25 wt.% Mg did not change the setting of BrCs significantly, a higher concentration of 1.00 wt.% increased the initial setting time from 4.87 ± 0.38 min to 15.14 ± 0.88 min. Cements with Mg concentrations of 1.5 wt.% and above did not set after 4 h. Mg addition up to 0.5 wt.% did not change the compressive strength; however, higher concentrations decreased it significantly and 2.5 Mg-BrC had the lowest strength of 0.45 ± 0.09 MPs. Together, our results show that Mg can be added up to 1.00 wt.% without any adverse effect on the physical and mechanical properties of BrC.

Metal Coatings Derived from Modified Silica as Anti-Corrosion

Metal is widely used in various industrial fields such as transportation because of its physical and mechanical strength. However, during its utilization, metal materials are often damaged by corrosion due to chemical reactions between the metal surface and the surrounding environment. Coating is one way to prevent corrosion by isolating metal surfaces from the environment. Conventional anti-corrosion coatings generally use chromate and phosphate-based materials. However, this material has been banned in some countries because it is toxic to the environment. Meanwhile, other methods with the addition of more active metals such as magnesium are considered unaffordable. Therefore, the researchers developed alternative materials that are environmentally friendly and reduce costs by using metal oxide-based materials such as Silicon dioxide (SiO2). The advantage of SiO2 is that it is chemically stable and harmless. SiO2 modification produces hydrophobic properties which increase corrosion resistance. One of the methods to make SiO2 is sol-gel method. The advantages of sol-gel method are simple, affordable, capable of forming a film for attaching chemical properties, flexible for incorporation with other compounds and the coating can be applied in several ways, such as dip coating, spray coating, electrophoretic deposition (EPD), etc. As an anti-corrosion coating, products can be tested for their resistance by analyzing the corrosion rate. This paper reviews silica-based metal coatings as anti-corrosion. The scope of the discussion in this paper is the mechanism, fabrication route, application technique, characterization, and analysis of anti-corrosion ability by studying the corrosion rate of anti-corrosion silica-based coating products for metal substrates.

A phytic acid-based CoMn bimetallic metal-organic aerogel (PA-CoMn-1 : x : 2 - x) as a modifier for electrochemical detection of non-steroidal anti-inflammatory drug 4-acetaminophenol.

Metal phosphides and phosphate-based materials have received significant attention due to their high electrocatalytic activity, adjustable structure composition and stability. Herein, we introduce a phytic acid-based CoMn bimetallic metal-organic (PA-CoMn) aerogel as an electrode modifier, derived from PA and mixed transition metal ions (Co2+, Mn2+). We explored its performance in the sensitive sensing of non-steroidal anti-inflammatory drug 4-acetaminophenol (4-AP) for the first time. We investigated the electrochemical behavior of the modified screen-printed carbon electrode (SPCE) by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The PA-CoMn-1 : 1.5 : 0.5 aerogel/Nafion/SPCE proved to be highly sensitive and selective towards the detection of 4-AP. A double linear response was recorded for 4-AP over the range of 1 μM to 0.1 mM and lower detection limits (LOD) of 0.2133 μM. The applicability of the PA-CoMn-1 : 1.5 : 0.5 aerogel/Nafion/SPCE in the detection of 4-AP in commercial drug samples with good recoveries was investigated, confirming the great potential of PA-CoMn-1 : 1.5 : 0.5 aerogel/SPCE in clinical applications.

Insights into structure, morphology and conductivity of the earth-abundant NASICON phosphate, Na4MnFe(PO4)3.

Phosphate-based NASICON materials are an excellent candidate for both electrode and solid electrolyte materials in sodium-ion batteries (SIBs). The development of new NASICON materials with higher ionic and electronic conductivities based on low cost and abundant elements is necessary for advancement of SIBs. In this study, we report the structure, morphology and conductivity of the earth-abundant Mn/Fe-based NASICON phosphate Na4MnFe(PO4)3. Pure phase powders were synthesized by solution-assisted solid-state reaction, sol-gel and Pechini methods. From refined X-ray diffraction data, the prepared phosphate was found to crystallize in trigonal symmetry with space group R3̄c. The effect of synthesis method on microstructure and conductivity was investigated using scanning electron microscopy (SEM), atomic force microscopy (AFM) and impedance measurements. Smaller particle size and regular distribution of the powder was designed using a Pechini route. Impedance measurement showed a notable enhancement in conductivity, from 0.543 × 10-7 to 1.52 × 10-7 S cm-1 at 30 °C, when the powder synthesis method was altered from a solution-assisted solid-state reaction to the Pechini route, highlighting the remarkable effect of the synthesis method on conductivity.

Phosphate-based polyanionic insertion materials for oxygen electrocatalysis

Electrocatalyst-based technologies: alkali metal–air batteries, fuel cells, and water splitting devices are the new holy grail in the next-generation energy storage landscape as they deliver higher energy densities than Li+/Na+ batteries (LIBs/SIBs).

Advances in the application of first principles calculations to phosphate-based NASICON battery materials

NASICON potential unlocked: first-principles calculations guide doping for sodium ion battery advancement.

Employing a Thin Artificial CEI Layer on Na3V2 (PO4)2F3-2xO2x (0 < x < 1) by Atomic Layer Deposition; Structure Stabilization and Capacity Enhancement

Sodium ion battery (SIB), still facing the limit in functionality due to lower energy density; arises from either low capacity or narrow potential window. The capacity improvement within material sustainability is one major challenge which needs to be addressed to satisfy the present demand for SIB. Of late phosphate-based materials [Na3V2(PO4)2F3-2xO2x; (NVPFO2x;0 < x < 1)] are established as prospective cathodes for Sodium-ion battery (SIB) due to high reversible capacity and stability. However, the reversible extraction and insertion of only 2 Na ion per formula unit in these polyanionic cathodes limit their capacity. Herein we demonstrate a strategic approach towards electrochemical activation of 3rd Na ion which leads to higher capacity and preserves structural stability. We synthesized a series of NVPFO2x (0 < x < 1) with well-controlled surface morphology and vanadium oxidation state and studied the electrochemical behavior on the various composition and morphology. Cycling within the potential window of 1.2V to 4.3V vs Na/Na+ to trigger extra Na ion in the electrochemical activity have shown their explicit behavior depending on morphology. The optimized NVPFO2x shows specific capacity >130 mA h g-1, implies 3rd Na ion activation. However, the material suffers rapid capacity fading within ~ 65 cycles which is tremendously improved through formation of a thin artificial cathode electrolyte interface (CEI) layer of TiO2 on the surface of NVPFO2x by atomic layer deposition (ALD) technique. This TiO2 coating enabled even further extraction of sodium through higher voltage domain, but more importantly, it facilitated excellent long-term stability over 200 cycles. The thin coating explicitly restores the structural and morphological integrity during prolonged electrochemical cycling which established by post cycling XRD, HRSEM and XPS study. The study demonstrated that the thin TiO2 layer on electrode material is effectively diminishes the parasitic reaction, reduces carbonate formation, and increase the stability of the formed CEI and lowers electrolyte decomposition within wide-range potential window.

On Synthesis and Electrochemical Performance of Na4Fe3(PO4)2(P2O7) Cathode for Sodium-Ion Batteries

Developing cost-effective and large-scale energy storage systems (ESSs) has been an important topic over the past years in order to implement efficient utilization of renewable electricity generated from sources like solar, wind, geothermal and tidal energy (1). Since the commercialization in 1991, lithium-ion batteries (LIBs) have been widely used in portable electronics, electric vehicles (EVs), and energy storage devices (2). However, there is an increase in demand for alternative energy sources based on abundant and low-cost materials due to the limited reserves and high costs of lithium compounds. In this context, sodium-ion batteries (SIBs) have received great attention because of their similarities to LIBs and the large abundance (2.3%) on earth, and low cost of sodium compounds (3). However, the energy density of most SIBs are lower that of LIBs, primarily due to the larger ionic radius and higher mass of Na+ ion compared to Li+ ions, as well as the lower electrochemical potential of sodium cells relative to lithium cells (4). Many efforts have been devoted to the development of high-performance cathode materials, including layered transition metal oxides, Prussian blue analogues (PBAs), sulfates, phosphates and pyrophosphates. Polyanionic compounds, in particular, are considered as promising cathode materials with regard to their high working voltage, structural stability, thermal stability and small volume change upon cycling (5). For example, iron phosphate-based materials have gained attention inspired by LiFePO4 for LIBs. However, the olivine NaFePO4 is predominantly produced through an ion exchange process (6). The maricite NaFePO4 is electrochemically inactive due to the lack of Na migration channels within its structure. On the other hand, Na2FeP2O7 shows long cycle life and structural stability with a low capacity because of its single electron diffusion process. Na4Fe3(PO4)2(P2O7) (NFPP) combines the benefits of both phosphate and pyrophosphate, offering potential advantages such as low-cost, environmental friendliness, high average working voltage (~ 3.1 V vs. Na+/Na), favorable theoretical capacity (129 mAh g-1), low volume change (< 4%) due to its open framework composed of [Fe3P2O13] layers connected by (P2O7)4- groups with 3D ion channels and low activation barriers for Na+ transport as well as structural and thermal stability. However, NFPP is susceptible to the formation of impurities such as NaFePO4 and Na2FeP2O7, which can arise from the synthesis temperature and adopted reaction materials, potentially restricting the electrochemical performance of NFPP. Additionally, the inherent insulating characteristics of the (PO4)3- group in NFPP may result in reduced electronic conductivity and slow ion diffusion, which hinders its practical application (7, 8). Therefore, various strategies have been developed to enhance conductivity such as nanosizing, carbon coating and metal ion doping.NFPP can be synthesized by various methods like solid-state, sol-gel, spray drying and combustion. In this study, we present our results on employing both sol–gel and combustion methods with distinct synthesis parameters. The structure, morphology and particle size of NFPP are characterized by X-ray powder diffraction (XRPD) and scanning electron microscopy (SEM) techniques. The electrochemical performance of NFPP cathodes is investigated in both half- and full-cells via galvanostatic charge-discharge cycling tests. Keywords: sodium-ion batteries, cathode material, iron-based mixed phosphate, sol-gel synthesis, large scale M. Armand and J. M. Tarascon, Nature, 451, 652 (2008).J. B. Goodenough and K.-S. Park, Journal of the American Chemical Society, 135, 1167 (2013).B. Dunn, H. Kamath and J.-M. Tarascon, Science, 334, 928 (2011).M. H. Han, E. Gonzalo, G. Singh and T. Rojo, Energy & Environmental Science, 8, 81 (2015).P. Barpanda, L. Lander, S.-i. Nishimura and A. Yamada, Advanced Energy Materials, 8, 1703055 (2018).K. T. Lee, T. N. Ramesh, F. Nan, G. Botton and L. F. Nazar, Chemistry of Materials, 23, 3593 (2011).X. Wu, G. Zhong and Y. Yang, Journal of Power Sources, 327, 666 (2016).H. Kim, I. Park, S. Lee, H. Kim, K.-Y. Park, Y.-U. Park, H. Kim, J. Kim, H.-D. Lim, W.-S. Yoon and K. Kang, Chemistry of Materials, 25, 3614 (2013).

On the Diversity of Phosphate Minerals for Potential Applications

Abstract This article describes the development of applications of phosphate-based materials and characterizes five non-apatite phosphate minerals using 3D optical profilometry. The results reveal the suitability of these materials for new uses in energy storage and conversion as well as medical applications.