Anode For Lithium-ion Batteries Research Articles

Estimating price elasticity of demand for mineral commodities used in Lithium-ion batteries in the face of surging demand

The accelerating adoption of clean energy technologies is driving demand for certain mineral commodities like lithium, essential for electric vehicle batteries. Understanding the influence of the energy transition on each market requires examining their supply and demand price elasticities. However, there have only been a limited number of studies that have estimated mineral demand price elasticities in emerging technologies. We empirically estimate the price elasticity demand (PEDs) for mineral commodities used in lithium-ion battery cathodes and anodes—cobalt, graphite, lithium, manganese, and nickel. We also test whether the price elasticities of these mineral commodities have changed due to any structural changes in recent years, given the recent expansion in the sales of electric vehicles. Using Two Stage Least Squared (2SLS) econometric techniques, we find that demand has become less elastic for lithium (-0.11), cobalt (-0.45), nickel (-0.09), and manganese (-0.04) after structural breaks in 2020, 2013, 2009, and 2014, respectively. In contrast, demand for natural amorphous graphite (-0.36), and natural flake graphite (-0.58) remains relatively stable over the time period assessed.

One-step chemical vapor deposition synthesis of Si NWs@C core/shell anodes without additional catalysts by the oxide-assisted growth mechanism for lithium-ion batteries.

Si NWs@C core/shell anodes for lithium-ion batteries were synthesized via a one-step environmental-pressure chemical vapor deposition (CVD) process utilizing nano-silicon and methane as raw materials. In this structure, the silicon nanowire core is obtained by controlling the temperature above 900 °C to catalyze the growth of nano-silicon particles coated with a natural oxide layer according to the oxide-assisted growth (OAG) mechanism, while the carbon as a protective coating shell is derived from methane cracking. In contrast to the conventional nanowire catalytic approach, this method obviates the addition of metal catalysts while ensuring a straightforward and scalable process. This Si NWs@C electrode displayed excellent electrochemical performance, exhibiting high reversible capacity (745.8 mA h g-1) and excellent cycling stability (91.3% after 100 cycles at 0.5 A g-1).

First principles investigation of Li[formula omitted]Si and Li[formula omitted]Sn alloys: Unraveling atomic-scale influences on material properties

Commercial batteries have currently reached their peak specific capacity, which proves insufficient for the ongoing global energy transition. Consequently, there has been a surge of interest in developing new materials over the last decade, especially those based on silicon (Si) and tin (Sn), known for their high capacity. Despite numerous publications highlighting the advantages of these materials, crucial questions remain regarding volume expansion that must be addressed to propose effective solutions and facilitate their widespread commercial application. In this study, density functional theory was employed to investigate the formation of LixM (M = Si, Sn). Our analysis delves into crystal (c-LixM), amorphous (a-LixM), and amorphous slab (s-LixM) configurations during structural optimization calculations, with the aim of comparing and contrasting relevant findings. The exploration encompasses energetic aspects, volume expansion, and electronic properties. The obtained data enables the simulation of lithiation potential curves for each structural type, directly comparable with experimental results of these materials functioning as anodes in lithium-ion batteries. Notably, the volume expansion of a-LixM exhibits non-linear behavior, correlating with characteristic plateaus in the voltage profile curves.

Multilayer boron doped Si@SiOx/C from Si-Ca alloy for lithium-ion battery anodes

SiOx has been considered as a promising anode for next-generation lithium-ion batteries. However, the poor rate performance caused by the low electrical conductivity is a bottleneck of its application. Approaches involving carbon composites, boron doping and two-dimensional structure have been pursued to improve the electrical conductivity. In this work, through the combination of these strategies, a multilayer boron doped Si@SiOx/C composites are fabricated by a chemical exfoliation of CaSi2 with B2O3 and CaCO3. The production exhibits favorable properties for lithium-ion battery anodes, such as proper specific surface area, complete multilayer structure, boron doped and carbon composite structure. The as-obtained B-Si@SiOx/C-700 delivers a capacity of 659.3 mAh g−1 after 500 cycles at 1 A g−1. Especially, at 4 A g−1, the capacity retention of the B-Si@SiOx/C-700 anode is still 40.9 % of its average discharge capacity at 0.2 A g−1. The capacitive contribution to the total Li+ storage capacity for the B-Si@SiOx/C-700 electrode is 83.6 % at 1.0 mV s−1. This work presents a simple and efficient strategy to construct a multilayer doped structure to improve electrochemical properties.

Enhancing the electrochemical properties of TiNb2O7 anodes with SP-CNT binary conductive agents for both liquid and solid state lithium ion batteries.

A high performance oxide composite electrode is obtained with a two-step solid state calcined titanium niobium oxide TiNb2O7 (TNO) anode and super P-carbon nanotube (SP-CNT) binary conductive agents. The solid state synthesized TNO-0.2C (the proportion of CNTs in the binary conductive agent is 20% wt) anode exhibits a high reversible discharge capacity of 278.6 mA h g-1 at 0.5C, a competitive rate capability with reported works that employed wet chemical methods at moderate rates (178.1 mA h g-1 at 10C), and an excellent capacity retention of 92.2% after 200 cycles at 1.5C/1.5C. The enhancement in electrochemical properties of the TNO-0.2C anode is mainly attributed to the combination of the short range and long range conductive agents in the SP-CNT binary conductive system, which guarantees an efficient electronic conductive network. The Li|Li1.3Al0.3Ti1.7(PO4)3 composite polymer electrolyte (LATPCPEs)|TNO-0.2C solid state batteries are also assembled, which deliver a high initial reversible discharge capacity of 241.3 mA h g-1 at 1C and a good capacity retention rate of 93% after 50 cycles. This work provides an efficient way to improve the electrochemical properties of TNO anodes in lithium ion batteries, especially for solid state batteries.

Novel binary regulated silicon-carbon materials as high-performance anodes for lithium-ion batteries.

The massive volume dilation, unsteady solid electrolyte interphase, and weak conductivity about Si have failed to bring it to practical applications, although its potential capacity is up to 4200 mAh g-1. For solving these problems, novel binary regulated silicon-carbon materials (Si/BPC) were done by a sol-gel procedure combined with single carbonization. Analytical techniques were systematically utilized to examine the effects of element doping at several gradients on morphology, structure and electrochemical properties of composites, thus the optimal content was identified. Si/BPC preserves a discharge specific capacity of 1021.6 mAh g-1with a coulomb efficiency of 99.27% after 180 cycles at 1000 mA g-1, within the upgrade than single-doped and undoped. In rate test, it has a specific capacity of 1003.2 mAh g-1at a high current density of 5000 mA g-1, quickly back towards 2838.6 mAh g-1at 200 mA g-1. The inclusion of B and P elements is linked to the electrochemical characteristics. In the co-doped carbon layers, the synergistic impact of doping B and P accelerates the diffusion kinetics of lithium ions, boosts diffusion rate of Li+, offers low electrochemical impedance (45.75 Ω). This brings more defects to provide transport carriers and induces a substantial amount of electrochemically active sites, which fosters the storage of Li+, thus making silicon material electrochemically more active and potential.

Superparticle of multidirectional graphitic nanospheres derived from metal–organic mesocrystal for fast-chargeable lithium-ion battery anode

Superparticle of multidirectional graphitic nanospheres derived from metal–organic mesocrystal for fast-chargeable lithium-ion battery anode

Incorporating ZIF-8-derived ZnSe into hollow carbon nanospheres as anodes for lithium-ion batteries

Transition metal selenides (TMSs) show great potential as anode materials for lithium-ion batteries (LIBs), boasting a high theoretical capacity. Nevertheless, their practical utility faces challenges, mainly stemming from significant volume changes that lead to rapid capacity decay during charge and discharge cycles. To overcome this challenge, we present a systematic approach involving the growth of uniformly dispersed ultrafine ZnSe nanoparticles derived from ZIF-8 on the surface of hollow carbon nanospheres (ZnSe@N-HCS/700). When utilized as an anode material for LIBs, the ZnSe@N-HCS/700 electrode demonstrates exceptional electrochemical performance. Specifically, it achieves a capacity of 1299 mAh g−1 after 100 cycles at a current density of 100 mA g−1 and maintains a capacity of 614 mAh g−1 even after 1800 cycles at 2500 mA g−1. The hollow structure of the composite alleviates the volume variation of ZnSe nanoparticles during charge and discharge processes, and provides a large reactive surface area, thereby significantly enhancing lithium storage capacity. In conclusion, our strategy presents an innovative approach to synthesize negative electrode materials with unique structures for LIBs.

Using Sandwiched Silicon/Reduced Graphene Oxide Composites with Dual Hybridization for Their Stable Lithium Storage Properties

Using silicon/reduced graphene oxide (Si/rGO) composites as lithium-ion battery (LIB) anodes can effectively buffer the volumetric expansion and shrinkage of Si. Herein, we designed and prepared Si/rGO-b with a sandwiched structure, formed by a duple combination of ammonia-modified silicon (m-Si) nanoparticles (NP) with graphene oxide (GO). In the first composite process of m-Si and GO, a core–shell structure of primal Si/rGO-b (p-Si/rGO-b) was formed. The amino groups on the m-Si surface can not only hybridize with the GO surface to fix the Si particles, but also form covalent chemical bonds with the remaining carboxyl groups of rGO to enhance the stability of the composite. During the electrochemical reaction, the oxygen on the m-Si surface reacts with lithium ions (Li+) to form Li2O, which is a component of the solid–electrolyte interphase (SEI) and is beneficial to buffering the volume expansion of Si. Then, the p-Si/rGO-b recombines with GO again to finally form a sandwiched structure of Si/rGO-b. Covalent chemical bonds are formed between the rGO layers to tightly fix the p-Si/rGO-b, and the conductive network formed by the reintroduced rGO improves the conductivity of the Si/rGO-b composite. When used as an electrode, the Si/rGO-b composite exhibits excellent cycling performance (operated stably for more than 800 cycles at a high-capacity retention rate of 82.4%) and a superior rate capability (300 mA h/g at 5 A/g). After cycling, tiny cracks formed in some areas of the electrode surface, with an expansion rate of only 27.4%. The duple combination of rGO and the unique sandwiched structure presented here demonstrate great effectiveness in improving the electrochemical performance of alloy-type anodes.

A graphene-like hollow sphere anode for lithium-ion batteries.

We report a flash Joule heating method for the rapid preparation of graphene-like materials. The L-GHS exhibited a uniform diameter of 200 nm and an ideal specific surface area of 670 m2 g-1. Meanwhile, the specific capacity of L-GHS remained at 942 mA h g-1 after 600 cycles (1 A g-1), which shows excellent electrochemical performance.

A Solid-State Reaction in a Vapor Chamber: Synthesis of Bi2(MoO4)3 Nanorods as High-Capacity Anode for Lithium-Ion Batteries

Abstract Conversion- and alloying-type materials have been investigated as alternatives to intercalating graphite anodes of lithium-ion batteries for recent decades. However, the electrochemical pulverization and limitations in large-scale production of metal oxides prohibit them from practical applications. This work provided an ambient solid-state reaction accelerated by water vapor for synthesizing Bi2(MoO4)3 nanorods combined with carbon under mild-condition ball-milling for composite fabrication. The obtained composite performs superior electrochemical performance: a delivered capacity of 802.2 mAh·g-1 after 300 cycles at a specific current of 500 mA·g-1 with a retention of 82.3%. This improvement was ascribed to the better accommodation to volume variation and reinforced physical contact raised by one-dimensional morphology and ball-milling treatment. The complex conversion-intercalation-alloying mechanism of the lithium-ion storage in Bi2(MoO4)3 anode was also clarified using cyclic voltammetry and ex-situ X-ray photoelectron spectroscopy results.

Effect of precursor solution temperature on the morphology and electrochemical performance of electrodeposited MnO2 nanofilms for lithium-ion batteries

ABSTRACT This study investigated the impact of precursor solution temperature on the electrodeposition of MnO2 material, which were prepared on a nickel substrate using the electrodeposition method under varying precursor solution temperatures of 25°C, 40°C, 50°C, and 60°C, respectively. These materials were subsequently employed as anodes in lithium-ion batteries to study their electrochemical performance. The results indicate that an increase in temperature induces preferential aggregation and growth of MnO2 nanosheets towards specific orientations, which is advantageous for enhancing the electrochemical performance of MnO2 electrode materials. Notably, the electrode material prepared at a solution temperature of 50°C exhibited optimal performance. Additionally, the charge transfer impedance was lower, which could be attributed to the growth of the highly conductive β-MnO2 main phase under 50°C. This study presents a novel approach for effectively improving electrodeposited nanomaterials, offering insights into the optimisation of electrochemical performance.

BC cone-shaped anodes for lithium-ion batteries

The efficiency of lithium-ion batteries (LIBs) depends upon anode materials possessing high capacity. In present study, we investigate boron carbide cone anode (BCC) for LIBs. The first-principles density functional theory (DFT) method is used to design anode materials based on BCC for application in LIBs. We found that the BCC shows negative Li adsorption energies. Our results also revealed the fast diffusions of Li ion on the BCC with the small energy barrier of 0.34 eV. The storage capacity of BCC system rank among the highest capacity of anodes for LIBs, with value of 785 mAh/g. The low average open-circuit voltage (OCV) value of BCC system indicates that this anode can handle a large operating voltage in LIBs.

Phase Evolution of Multi-Metal Dichalcogenides With Conversion-Alloying Hybrid Mechanism for Superior Lithium Storage.

Traditional lithium-ion battery (LIB) anodes, whether intercalation-type like graphite or alloying-type like silicon, employing a single lithium storage mechanism, are often limited by modest capacity or substantial volume changes. Here, the kesterite multi-metal dichalcogenide (CZTSSe) is introduced as an anode material that harnesses a conversion-alloying hybrid lithium storage mechanism. Results unveil that during the charge-discharge processes, the CZTSSe undergoes a comprehensive phase evolution, transitioning from kesterite structure to multiple dominant phases of sulfides, selenides, metals, and alloys. The involvement of multi-components facilitates electron transport and mitigates swelling stress; meanwhile, it results in formation of abundant defects and heterojunctions, allowing for increased lithium storage active sites and reduced lithium diffusion barrier. The CZTSSe delivers a high specific capacity of up to 2266mA h g-1 at 0.1 A g-1; while, maintaining a stable output of 116mA h g-1 after 10000 cycles at 20 A g-1. It also demonstrates remarkable low-temperature performance, retaining 987mA h g-1 even after 600 cycles at -40°C. When employed in full cells, a high specific energy of 562Wh kg-1 is achieved, rivalling many state-of-the-art LIBs. This research offers valuable insights into the design of LIB electrodes leveraging multiple lithium storage mechanisms.

Boron–Silicon Alloy Nanoparticles as a Promising New Material in Lithium-Ion Battery Anodes

Boron–Silicon Alloy Nanoparticles as a Promising New Material in Lithium-Ion Battery Anodes

Synthesis of core–shell silicon–carbon nanocomposites via in-situ molten salt-based reduction of rice husks: A promising approach for the manufacture of lithium-ion battery anodes

Silicon (Si) has gained substantial interest as a potential component of lithium-ion battery (LIB) anodes due to its high theoretical specific capacity. However, conventional methods for producing Si for anodes involve expensive metal reductants and stringent reducing environments. This paper describes the development of a calcium hydride (CaH2)–aluminum chloride (AlCl3) reduction system that was used for the in-situ low-temperature synthesis of a core–shell structured silicon–carbon (Si–C) material from rice husks (RHs), and the material was denoted RHs-Si@C. Moreover, as an LIB anode, RHs-Si@C exhibited exceptional cycling performance, exemplified by 90.63 % capacity retention at 5 A g−1 over 2000 cycles. Furthermore, the CaH2–AlCl3 reduction system was employed to produce Si nanoparticles (Si NPs) from RHs (R-SiO2, where SiO2 is silica) and from commercial silica (C-SiO2). The R-SiO2-derived Si NPs exhibited a higher residual silicon oxides (SiOx) content than the C-SiO2-derived Si NPs. This was advantageous, as there was sufficient SiOx in the R-SiO2-derived Si NPs to mitigate the volumetric expansion typically associated with Si NPs, resulting in enhanced cycling performance. Impressively, Si NPs were fabricated on a kilogram scale from C-SiO2 in a yield of 82 %, underscoring the scalability of the low-temperature reduction technique.

Sealing porous carbon via surface-initiated polymerization achieves low-surface-area Si-C microparticles for Li-ion batteries

Porous Si-carbon composite architecture represents an effective design for lithium-ion batteries (LIBs) anodes. However, the high specific surface area (SSA) greatly negates cell initial Coulombic efficiency (ICE), and the function of porous carbon is challenged by practical conditions such as calendaring and high-mass-loading cycling. Here, we report a crosslinked conductive polymer layer as sealing layer for porous Si-C particles to enable high ICE and stable cycling of densified Si-anodes. A surface-initiated polymerization was adopted to form a conformal polymeric skin that can greatly lower the SSA and improve ICE of porous Si-C particles (94.8 vs. 5.7 m2/g, and 77.3% vs. 84.4%). The “sealed” Si-C particle maintains desirable intraparticle porosity to digest the volume changes during Li insertion, while the polymeric skin is key to shield off electrolyte penetration into the particles interior and to mechanically package the porous secondary particles throughout calendaring and cycling. The Si-C graphite mixtures anode (650mAh/g) retains 70.8% capacity after 500 cycles. Adopting high-mass-loading NCM622, the full cell with stringent electrode metrics (anode at 1.2g/cm3, NCM622 at 3.1g/cm3, 3.4 mAh/cm2) demonstrates 65.9% capacity retention after 100 cycles. This study opens up a pathway to produce low-SSA porous anodes for practical LIBs.

3D porous structure Fe3O4@SnO2/MXene composites with enhanced electrochemical performance for lithium ion battery anode

The low theoretical capacity of the commercial graphite electrodes used in lithium-ion batteries (LIBs) necessitates the development of novel anode materials with higher rate performance, reversible specific capacities, long cycle lives, and low costs. In this work, three-dimensional porous structure Fe3O4 nanosphere with extremely thin SnO2 coatings are prepared by a method of getting twice the result with half the effort. And it was uniformly dispersed in an MXene flexible conductive matrix to fabricate a 3D porous heterogeneous Fe3O4@SnO2/MXene composite to act as an anode material for LIBs. The 3D porous heterojunction structure integrates the advantages of Fe3O4@SnO2 and MXene, achieving rapid electron and ion transport at the interface and the effective release of structural stress. The introduction of MXene markedly enhances the conductibility of the materials, limits the expansion of Fe3O4 during the Li+ insertion/removal process, and inhibits its aggregation. The Fe3O4@SnO2/MXene anode exhibits excellent electrochemical performance (1609 mAh g−1 over 200 cycles at 100 mA g−1 and 626.1 mAh g−1 over 900 cycles at 1000 mA g−1). These findings demonstrate that the Fe3O4@SnO2/MXene composite is a promising anode material for LIBs.

Flexible and crosslinking electrospun porous carbon nanofiber membranes as freestanding binder-free anodes for lithium-ion batteries

Electrospinning carbon nanofibers with one-dimensional nanostructures have enormous potential for electronic applications owing to their flexibility, electrical conductivity, high surface area and attractive structure. In this paper, porous nitrogen-doped carbon nanofiber membranes with chemical crosslinking structure (PNCNMs-CC) were prepared for lithium-ion batteries anodes by crosslinking treatment and carbonization process using polyimide as precursor, melamine as nitrogen source and ethyl orthosilicate as pore-forming agent. The heightened nitrogen content synergizes with the augmented specific surface area, engendering a striking electrochemical enhancement. Rich pore structure provides more active sites. When utilized as a binder-free, current collector-free anode, PNCNMs-CC shows an excellent rate performance and long cycle stability. The first discharge specific capacity of PNCNMs-CC delivered 710 mAh g−1 at 50 mA g−1. After 1000 cycles at a high current density of 1 A g−1, PNCNMs-CC shows 88 % capacity retention, demonstrating a promising candidate as the flexible anodes for high-performance energy storage devices.

A Tripartite Composite Incorporating Nitrogen-Doped Graphene Oxide, Polypyrrole, and Silica for Lithium-Ion Battery Anodes

In this study, N-doped graphene oxide-polypyrrole-silica (NGO-PPy-SiO2) composite was employed as a possible anode in Li-ion batteries. The chronoamperometric technique was employed to synthesize NGO, and within this study two samples were produced, one characterized by a high polypyrrle content (N1) and the other by a low polypyrrle content (N2). N2 has the maximum initial discharge capacity of 785 mAh g−1 at 0.1 C, which is greater than N1’s capacity of 501 mAh g−1. The initial coulombic efficiency of the first cycle is around 72%, whereas the ICE of N2 is approximately 60%. N1 demonstrates outstanding cycling performance for 100 cycles at high rate (10 C) with maintain capacity as 100% and coulombic efficiency of 100%, as well as extremely stable capacity during the cycling. N2 has a maintain capacity of ≈79% and excellent coulombic efficiency, however the capacity during cycling is not as stable as N1.