Anode Material For Sodium-ion Batteries Research Articles

Recent advances in alloying anode materials for sodium-ion batteries: material design and prospects

Recent advances in alloying anode materials for sodium-ion batteries: material design and prospects

Unlocking the potential of a chemically modified blue phosphorene as anode materials for high-performance sodium-ion batteries

Blue phosphorene (Blu-Pn) has recently been identified as a new two-dimensional (2D) form of black phosphorus via the epitaxial growth method and has shown the ability to host a substantial amount of Na while serving as an anode in sodium-ion batteries (NIBs). However, its structural instability is an issue that hinders its further exploitability in NIBs. In this paper, we propose to chemically modify the Blu-Pn network by substituting six phosphorus atoms with a carbon source in the form of a C6 ring, constructing a new and robust CP2 nanosheet. Based on the state-of-the-art non-local van der Waals corrected density functional theory and ab initio molecular dynamic (AIMD) simulations, we systematically explore the feasibility of the designed CP2 as a potential anode material for NIBs. Adding a C6 ring in the Blu-Pn lattice reduces its energy gap from 2 eV to 1.3 eV, which disappears after Na adsorption, indicating a conductive character. Attributed to the synergistic effect, the adsorption energy of Na on CP2 nanosheet (−2.22 eV) is greatly decreased in comparison to the pristine carbon source (e.g., graphene with −0.78 eV) and pristine Blu-Pn (−1.85 eV). The Na diffusivity on CP2 at 300 K is predicted to be 4.90 × 10−11 m2/s by AIMD. The specific capacity is up to 604.1 mAh/g, which exceeds that of the commercialized graphite anode (372 mA h/g). Ultimately, the designed electrode provides a small open circuit potential of 0.66 V that falls within a desirable voltage range. This work paves the way for exploring Blu-Pn 2D anode materials for NIBs technology and provides valuable insights into surface chemical modification towards the long-term stability of Blu-Pn.

Fabrication of a Stable and Highly Effective Anode Material for Li-Ion/Na-Ion Batteries Utilizing ZIF-12.

Transition metal selenides (TMSs) are receiving considerable interest as improved anode materials for sodium-ion batteries (SIBs) and lithium-ion batteries (LIBs) due to their considerable theoretical capacity and excellent redox reversibility. Herein, ZIF-12 (zeolitic imidazolate framework) structure is used for the synthesis of Cu2Se/Co3Se4@NPC anode material by pyrolysis of ZIF-12/Se mixture. When Cu2Se/Co3Se4@NPC composite is utilized as an anode electrode material in LIB and SIB half cells, the material demonstrates excellent electrochemical performance and remarkable cycle stability with retaining high capacities. In LIB and SIB half cells, the Cu2Se/Co3Se4@NPC anode material shows the ultralong lifespan at 2000 mAg-1, retaining a capacity of 543 mAhg-1 after 750 cycles, and retaining a capacity of 251 mAhg-1 after 200 cycles at 100 mAg-1, respectively. The porous structure of the Cu2Se/Co3Se4@NPC anode material can not only effectively tolerate the volume expansion of the electrode during discharging and charging, but also facilitate the penetration of electrolyte and efficiently prevents the clustering of active particles. In situ X-ray difraction (XRD) analysis results reveal the high potential of Cu2Se/Co3Se4@NPC composite in building efficient LIBs and SIBs due to reversible conversion reactions of Cu2Se/Co3Se4@NPC for lithium-ion and sodium-ion storage.

Insight into the configuration of hard-soft carbon composites for high performance sodium-ion batteries

Hard carbon materials are considered suitable anode materials for sodium-ion batteries due to their abundant defect sites and large interlayer distance, which are respectively beneficial to the adsorption/desorption and insertion/extraction behaviors of Na+ during the electrochemical process. However, the poor electrical conductivity resulting from the intrinsic short-range ordered structure in the carbon skeleton and limited active sites significantly hinders their electrochemical performance. Herein, hard and soft carbon composites with various configurations are developed using a layer-by-layer coating method with SiO2 nanospheres as templates. These composites, including the hard carbon coated soft carbon composite structure (SC@HC), soft carbon coated hard carbon composite structure (HC@SC), and uniformly mixed soft and hard carbon composites (HSC), are prepared through confined-carbonization under the outermost SiO2 layer. The resulting hollow nanospheres possess ultra-small diameters (approximately 50 nm), ultra-thin wall thicknesses (5-6 nm), and different hard/soft carbon layer arrangements. Evaluation of sodium storage properties showed that the combination of soft and hard carbon outperformed pure soft or hard carbon, with HC@SC configuration offering materials with larger interlayer spacing, higher defect concentration, and a more complete conductive network. This enhances sodium storage capacity (293 mAh g-1@1 A g-1) and rate performance (242 mAh g-1@5 A g-1). The findings of this study present a novel approach to designing soft and hard carbon composites for high-performance sodium-ion batteries.

Novel in-situ encapsulation of tin phosphide particles in MXene conductive networks as anode materials of the durable sodium-ion battery

Sodium-ion battery (SIB) is one of potential alternatives to lithium-ion battery, because of abundant resources and lower price of sodium. High electrical conductivity and long-term durability of MXene are advantageous as the anode material of SIB, but low energy density restricts applications. Tin phosphide possesses high theoretical capacity, low redox potential, and large energy density, but volume expansion reduces its cycling stability. In this study, tin phosphide particles are in-situ encapsulated into MXene conductive networks (SnxPy/MXene) by hydrothermal and phosphorization processes as novel anode materials of SIB. MXene amounts and hydrothermal durations are investigated to evenly distribute SnxPy in MXene. After 100 cycles, SnxPy/MXene reaches high specific capacities of 438.8 and 314.1 mAh/g at 0.2 and 1.0 A/g, respectively. The capacity retentions of 6.0% and 73.6% at 0.2 A/g are respectively obtained by SnxPy and SnxPy/MXene. The better specific capacity and cycling stability of SnxPy/MXene are attributed to less volume expansion of SnxPy during charge/discharge processes and relieved self-stacking of MXene by encapsulating SnxPy particles between MXene layers. Electrochemical impedance spectroscopy and Galvanostatic intermittent titration technique are also applied to analyze the charge storage mechanism in SIB. Higher sodium ion diffusion coefficient and smaller charge-transfer resistance are obtained by SnxPy/MXene.

In Situ Lattice-Resolution Revelation of the Origins of Unexplored Anisotropic Sodiation Kinetics and Phase Transition in the Niobium Sulfide Anode.

Layered transition metal dichalcogenides (TMDs) have exhibited huge potential as anode materials for sodium-ion batteries. Most of them usually store sodium via an intercalation-conversion mechanism, but niobium sulfide (NbS2) may be an exception. Herein, through in situ transmission electron microscopy, we carefully investigated the insertion behaviors of Na ions in NbS2 and directly visualized anisotropic sodiation kinetics. Lattice-resolution imaging coupled with density functional theory calculations reveals the preferential diffusion of Na ions within layers of NbS2, accompanied by observable interlayer lattice expansion. Impressively, the Na-inserted layers can still withstand in situ mechanical testing. Further in situ observation vertical to the a/b plane of NbS2 tracked the illusive conversion reaction, which could result from interlayer gliding or wrinkling associated with stress accumulation. In situ electron diffraction measurements ruled out the possibility of such a conversion mechanism and identified a phase transition from pristine 3R-NbS2 to 2H-NaNbS2. Therefore, the NbS2 anode stores Na ions via only the intercalation mechanism, which conceptually differs from the well-known intercalation-conversion mechanism of typical TMDs. These findings not only decipher the whole sodiation process of the NbS2 anode but also provide valuable reference for unraveling the precise sodium storage mechanism in other TMDs.

Tuning the microstructure of biomass-derived hard carbons by controlling the impurity removal process for enhanced Na ion storage performance

Biomass-derived hard carbons are promising anode materials of sodium-ion batteries (SIBs) due to their low cost, renewability and high specific capacity. However, there are inevitably some impurities in biomasses that may not only affect the purity, but microstructure and electrochemical performance of hard carbons. Although the impurities can be removed by appropriate treatments after carbonization, the microstructure of hard carbons can hardly be changed. In this work, taking ficus macrophylla leaves (FMLs) as the model biomass, the effects of impurities and their removing process on the microstructure and Na ion storage performance of hard carbons are investigated. It is found that the presence of Ca and Si-bearing impurities in FMLs results in more graphite-like structure in hard carbons because of their catalytic graphitization effect. The acid and base washing processes after carbonization can mostly get rid of the inorganic impurities is unable to increase the plateau region capacities associating to Na ion insertion in the interlayer of graphitic microcrystals and Na metal filling in micropores. By contrast, by stepwisely removing the Ca and Si-bearing impurities from raw materials before carbonization, hard carbons with high purity, larger interlayer space and more micropores are produced, which exhibit a high reversible specific capacity of 336 mAh g−1 at 20 mA g−1, a high initial Coulombic efficiency of 93 %, excellent rate capability (245 mAh g−1 at 2 A g−1) and robust cycle stability. This study implies that controlling the impurity removal process can simultaneously tune the microstructure of hard carbon anodes derived from biomasses towards high performance Na ion storage.

Fast-Charging Anode Materials for Sodium-Ion Batteries.

Sodium-ion batteries (SIBs) have undergone rapid development as a complementary technology to lithium-ion batteries due to abundant sodium resources. However, the extended charging time and low energy density pose a significant challenge to the widespread use of SIBs in electric vehicles. To overcome this hurdle, there is considerable focus on developing fast-charging anode materials with rapid Na⁺ diffusion and superior reaction kinetics. Here, the key factors that limit the fast charging of anode materials are examined, which provides a comprehensive overview of the major advances and fast-charging characteristics across various anode materials. Specifically, it systematically dissects considerations to enhance the rate performance of anode materials, encompassing aspects such as porous engineering, electrolyte desolvation strategies, electrode/electrolyte interphase, electronic conductivity/ion diffusivity, and pseudocapacitive ion storage. Finally, the direction and prospects for developing fast-charging anode materials of SIBs are also proposed, aiming to provide a valuable reference for the further advancement of high-power SIBs.

Binderless Electrodeposited NiCo2S4-MWCNT as a Potential Anode Material for Sodium-Ion Batteries

Conversion type ternary NiCo2S4, exhibiting high electrical conductivity (∼1.25 × 106 S m−1) and high theoretical capacity (703 mAh g−1), has gained interest as an anode material for sodium-ion batteries (SIBs). Despite its potential, NiCo2S4 (NCS) has extensive volume expansion during cycling. This study introduces the NCS-multi-walled carbon nanotube (MWCNT) onto a carbon fiber (CF) electrode (NCS and NCS-MWCNT@CF), developed through electrodeposition, which addresses these limitations. The unique sheet-like morphology of NCS, featuring abundant pores, ensures good access to the electrolyte. Incorporating a three-dimensional conductive CF framework that acts as a free-standing current collector helps prevent the agglomeration of NCS particles and mitigates volume expansion by providing enough buffer space in the layers of the CF matrix. Our findings reveal that NCS on CF electrodes deliver a second cycle capacity of 620 mA g−1 at 30 mA g−1 and retain 72% capacity after 200 cycles. At 200 mA g−1, the NCS@CF electrodes deliver 378 mAh g−1 in the second cycle with 68% capacity retention in the 200th cycle, whereas NCS-MWCNT@CF delivers 538 mAh g−1 at 200 mA g−1, maintaining 86 % capacity after 100 cycles, making it a potential anode for SIBs.

3D printing of porous hollow nanosphere MoS2@NiS/rGO scaffolds empowering long-cycle sodium-ion batteries

Sodium-ion batteries (SIB), as one of the most appealing electrochemical energy storage devices in the field of energy storage, consistently require optimization for both capacity and long-term cycling performance. The amalgamation of diverse material modification techniques with up-and-coming 3D printing technology presents a promising yet relatively underexplored avenue. Herein, we report a composite material, MoS2@NiS/rGO, as the anode material for SIB, achieving high reversible capacity and outstanding long-term cycling performance, surpassing current reported levels. Through carefully designed anode electrode structure and component interface engineering, the material rate capability (with a capacity of 289.5 mAh g−1 at 0.1 A g−1 and 66.8 mAh g−1 at 5 A g−1) and cycling stability (maintaining a capacity of 131.3 mAh g−1 after 800 cycles at 1 A g−1) are significantly enhanced. The reasons for the improvement in electrochemical performance are elucidated through detailed electrochemical analysis. Encouragingly, we showcase the fabrication of a sodium-ion full battery entirely through 3D printing (3DP), achieving an area loading capacity as high as 8.23 mg cm−2 and retaining a capacity of 82.1 mAh g−1 after 240 cycles at 0.1 A g−1. This work underscores the pivotal significance of 3D-printed sodium-ion batteries in advancing the frontier of energy storage technology.

High-entropy selenides derived from Prussian blue analogues as electrode materials for sodium-ion batteries

Transition metal selenides (TMS) have received much attention as anode materials for sodium-ion batteries (SIBs) because of their high theoretical capacity and excellent redox reversibility. However, their further development is constrained by the dissolution of transition metal ions and substantial volume changes experienced during cycling. Herein, the high-entropy Prussian blue analogues were selenized by the vapor infiltration method, resulting in the formation of a core–shell structured high-entropy selenides (HESe-6). The core–shell structure with voids and abundant selenium vacancies on the surface effectively mitigates bulk expansion and enhances electronic conductivity. Furthermore, the high-entropy property endows an ultra-stable crystal structure and inhibits the dissolution of metal ions. The ex-situ EIS and in-situ XRD results show that HESe-6 is able to be reversibly transformed into highly conductive ultrafine metal particles upon Na+ embedding, providing more Na+ reactive active sites. In addition, despite the incorporation of up to seven different elements, it exhibits minimal phase transitions during discharge/charge cycles, effectively mitigating stress accumulation. HESe-6 could retain an ultralong-term stability of 765.83 mAh g−1 after 1000 loops even at 1 A g−1. Furthermore, when coupled with the Na3V2(PO4)2O2F cathode, it maintains a satisfactory charge energy density of 303 Wh kg−1 after 300 cycles, which shows promising application prospect in the future.

Soft template-induced self-assembly strategy for sustainable production of porous carbon spheres as anode towards advanced sodium-ion batteries

Doped porous carbon is a prominent sodium anode material with high specific surface area (SSA) and abundant pore structure. Compared with the traditional “hard template” technique for the synthesis of porous carbon, the “soft template” method offers a more efficient synthesis process and simplified template removal. In response to the urgent need for eco-friendly synthesis methods for functional doping, our research introduces an innovative method using biomass-derived tannic acid as a precursor. We have successfully synthesized N/S double-doped porous spherical carbon materials (DF-N/S) through a self-assembly process driven by hydrogen bonding and solvent evaporation. As an anode material for sodium-ion batteries (SIBs), DF-N/S demonstrates superior electrochemical performance, achieving a specific capacity of 327.04 mAh g−1 at a current density of 0.05 Ag-1 in ether-based electrolytes. The remarkable sodium storage efficiency of DF-N/S has been thoroughly examined through kinetic analyses and ex-situ characterization methods. This study aims to provide a sustainable and widely adaptable method for the soft template production of doped carbon, while also shedding light on the intricacies of energy storage mechanisms in both ether/ester-based electrolytes.

In situ synthesis of SnPS3/Ti3C2Tx hybrid anode via molten salt etching method for superior sodium-ion batteries

Recently, SnPS3 has gained attention as an impressive sodium-ion battery anode material because of its significant theoretical specific capacity derived from the conversion-alloying reaction mechanism. Nevertheless, its practical applicability is restricted by insufficient rate ability, and severe capacity loss due to inadequate electrical conductivity and dramatic volume expansion. Inspired by the electrochemical enhancement effect of MXene substrates and the innovative Lewis acidic etching for MXene preparation, SnPS3/Ti3C2Tx MXene (T = Cl and O) is constructed by synchronously phospho-sulfurizing Sn/Ti3C2Tx precursor. Benefiting from the boosted Na+ diffusion and electron transfer rates, as well as the mitigated stress expansion, the synthesized SnPS3/Ti3C2Tx composite demonstrates enhanced rate capability (647 mA h g−1 at 10 A g−1) alongside satisfactory long-term cycling stability (capacity retention of 94.6% after 2000 cycles at 5 A g−1). Importantly, the assembled sodium-ion full cell delivers an impressive capacity retention of 97.7% after undergoing 1500 cycles at 2 A g−1. Moreover, the sodium storage mechanism of the SnPS3/Ti3C2Tx electrode is elucidated through in-situ and ex-situ characterizations. This work proposes a novel approach to ameliorate the energy storage performance of thiophosphites by facile in-situ construction of composites with MXene.

Boosting sodium storage performance of biomass-derived porous carbon anodes by surface functionalized strategy

In order to enhance the sodium ion storage performance of biomass-derived carbon anode materials, a surface functionalization strategy was employed through a simple acid etching method on porous carbon. The resulting functionalized carbon exhibits a hierarchically porous structure, expanded interlayer spacing, and oxygen-containing functional groups. The redox reactions occurring at the surface between Na ions and carbonyl groups provide additional sites for sodium ion storage, thereby improving cycling capacity and rate capability. Theoretical calculations and electrochemical tests further demonstrate that the functionalized carbon can increase the surface-controlled sodium storage capacity by modifying the transport and adsorption processes of sodium ions. After 200 cycles at a current density of 100 mA g−1, the carbon anode, which was surface-functionalized with an etching time of 6 h, achieve a high reversible capacity of 273 mA h g−1. Furthermore, it displays improved rate performance with a capacity of 194 mA h g−1 at a high current density of 2 A g−1 for sodium-ion batteries. This study introduces an effective and general strategy for the cost-effective and large-scale synthesis of carbon anode materials for sodium-ion batteries.

Pseudocapacitive TiNb0.8O4 microspheres for fast-charging and durable sodium storage

Titanium niobium oxides are promising anode materials for sodium-ion batteries (SIBs) due to their efficient ion diffusion channels. However, their poor electronic conductivity impedes the longevity of SIBs. To address these issues, core@shell TiNb0.8O4/C@C microspheres (TNO/C@C) have been developed to enhance electron conduction. The TNO/C@C, featuring a bulk and surface dual conductive configuration, outperforms pure TNO and other control samples such as TNO/C and TNO@C that rely solely on either bulk or surface electronic conductors. Thus, the TNO/C@C achieves a fast-charging rate of 200 C, allowing full charging in 2 s, and demonstrates long-term stability over 10,000 cycles. In-situ Raman analysis reveals a zero-strain feature during sodiation/desodiation, which minimizes structural degradation over repeated cycles. In-situ electrochemical impedance spectroscopy test indicates low electron resistance, enhancing both the rate capability and stability. Therefore, the bulk and surface dual conducting strategy offers new insights into robust and fast-charging SIBs.

Construction of High-Performance Anode of Potassium-Ion Batteries by Stripping Covalent Triazine Frameworks with Molten Salt.

Covalent triazine frameworks (CTFs) are promising battery electrodes owing to their designable functional groups, tunable pore sizes, and exceptional stability. However, their practical use is limited because of the difficulty in establishing stable ion adsorption/desorption sites. In this study, a melt-salt-stripping process utilizing molten trichloro iron (FeCl3) is used to delaminate the layer-stacked structure of fluorinated covalent triazine framework (FCTF) and generate iron-based ion storage active sites. This process increases the interlayer spacing and uniformly deposits iron-containing materials, enhancing electron and ion transport. The resultant melt-FeCl3-stripped FCTF (Fe@FCTF) shows excellent performance as a potassium ion battery with a high capacity of 447 mAh g-1 at 0.1 A g-1 and 257 mAh g-1 at 1.6 A g-1 and good cycling stability. Notably, molten-salt stripping is also effective in improving the CTF's Na+ and Li+ storage properties. A stepwise reaction mechanism of K/Na/Li chelation with C═N functional groups is proposed and verified by in situ X-ray diffraction testing (XRD), ex-situ X-ray photoelectron spectroscopy (XPS), and theoretical calculations, illustrating that pyrazines and iron coordination groups play the main roles in reacting with K+/Na+/Li+ cations. These results conclude that the Fe@FCTF is a suitable anode material for potassium-ion batteries (PIBs), sodium-ion batteries (SIBs), and lithium-ion batteries (LIBs).

Synthesized nanosphere ZnSe and reduced graphene oxide as anode materials for sodium-ion batteries: Analysis on phase transition and storage mechanism

Zinc selenide (ZnSe), a metal chalcogenide, is an attractive anode material for sodium-ion batteries, exhibiting high theoretical capacity (371.4 mAhg−1) and numerous redox sites. However, volume expansion and low stability during the charge/discharge processes present challenges. This study aimed to solve these inherent problems and synthesize a high-performance anode material by growing nano sized ZnSe on surface of reduced graphene oxide (rGO). ZnSe has two crystal structures, namely zinc-blende and wurtzite, and undergoes a transformation from wurtzite to the zinc-blende phase during sodium ion storage. This study conducted X-ray diffraction analysis of the electrode after the galvanostatic charge/discharge test and performed cyclic voltammetry analysis to investigate the transformation process. In addition, real-time monitoring of Nyquist plot and phase transition was performed to investigate the mechanisms of sodium ion storage. The ZnSe-rGO, exhibiting conversion reactions, shows cycle performance of 316.14 mAhg−1 at a current density of 0.5 Ag−1 after 1000 cycles. The evaluation of anode materials and analysis of their storage mechanism can facilitate sodium-ion batteries research.

Thermal vapor sulfurization modified micro-sized red phosphorus/activated carbon composite anode for sodium-ion batteries

High-capacity red phosphorus/activated carbon (P/C) composites are promising anode materials for next-generation sodium-ion batteries. However, the poor conductivity and significant volume effect of red phosphorus inevitably deposited on the outer surface of P/C composites may incur significant capacity decay and structural degradation. This work reports a method for preparing surface-modified micro-sized P/C composites with built-in nanoscale features. Through thermal vapor sulfurization, the obtained micron-sized sulfur-modified P/C (S-P/C) composites not only fulfill the requirements of the battery manufacture but also maintain their nano-in-micro structure. It can eliminate the detrimental red phosphorus on the outer surface of P/C composites and convert it into the ion conductive layer of Na3PS4, limiting its volume effect and significantly promoting ion conduction. As a result, S-P/C composites exhibit excellent cyclic stability in a half cell (610 mAh/g at 0.2 A/g and capacity retention of 94.2 % after 100 cycles) and reach a high areal capacity level (1.99 mAh cm−2) in a full cell.

Industrial-Scale Hard Carbon Designed to Regulate Electrochemical Polarization for Fast Sodium Storage.

Given the merits of abundant resource, low cost and high electrochemical activity, hard carbons have been regarded as one of the most commercializable anode material for sodium-ion batteries (SIBs). However, poor rate capability is one of the main obstacles that severely hinder its further development. In addition, the relationships between preparation method, material structure and electrochemical performance have not been clearly elaborated. Herein, a simple but effective strategy is proposed to accurately construct the multiple structural features in hard carbon via adjusting the components of precursors. Through detailed physical characterization of the hard carbons derived from different regulation steps, and further combined with in-situ Raman and galvanostatic intermittent titration technique (GITT) analysis, the network of multiple relationships between preparation method, microstructure, sodium storage behavior and electrochemical performance have been successfully established. Simultaneously, exceptional rate capability about 108.8 mAh g-1 at 8 A g-1 have been achieved from RHC sample with high reversible capacity and desirable initial Coulombic efficiency (ICE). Additionally, the practical applications can be extended to cylindrical battery with excellent cycle behaviors. Such facile approach can provide guidance for large-scale production of high-performance hard carbons and provides the possibility of building practical SIBs with high energy density and durability.

Biomass-Derived Hard Carbon for Sodium-Ion Batteries: Basic Research and Industrial Application.

Sodium-ion batteries (SIBs) have significant potential for applications in portable electric vehicles and intermittent renewable energy storage due to their relatively low cost. Currently, hard carbon (HC) materials are considered commercially viable anode materials for SIBs due to their advantages, including larger capacity, low cost, low operating voltage, and inimitable microstructure. Among these materials, renewable biomass-derived hard carbon anodes are commonly used in SIBs. However, the reports about biomass hard carbon from basic research to industrial applications are very rare. In this paper, we focus on the research progress of biomass-derived hard carbon materials from the following perspectives: (1) sodium storage mechanisms in hard carbon; (2) optimization strategies for hard carbon materials encompassing design, synthesis, heteroatom doping, material compounding, electrolyte modulation, and presodiation; (3) classification of different biomass-derived hard carbon materials based on precursor source, a comparison of their properties, and a discussion on the effects of different biomass sources on hard carbon material properties; (4) challenges and strategies for practical of biomass-derived hard carbon anode in SIBs; and (5) an overview of the current industrialization of biomass-derived hard carbon anodes. Finally, we present the challenges, strategies, and prospects for the future development of biomass-derived hard carbon materials.