Special Issue "Advanced Nanomaterials for Li- and Na-Ion Batteries"

A special issue of Energies (ISSN 1996-1073). This special issue belongs to the section "Advanced Energy Materials".

Deadline for manuscript submissions: 22 March 2021.

Special Issue Editor

Prof. Dr. Nina V. Kosova
Website
Guest Editor
Institute of Solid State Chemistry and Mechanochemistry, Siberian Branch of the Russian Academy of Sciences, 18 Kutateladze, 630128 Novosibirsk, Russia
Interests: nanostructured electrode materials for lithium- and sodium-ion batteries; mechanical activation; mechanochemically assisted solid-state synthesis; structural and electrochemical characterization
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Special Issue Information

Dear Colleagues,

Among known systems, lithium-ion batteries are recognized as the most appropriate energy storage systems because of their high energy density and thus space saving in applications. Nanotechnology has opened up new frontiers in materials science and engineering in the past several decades. Considerable efforts on nanostructured electrode materials have been made to fulfill the future requirements of electrochemical energy storage. Compared to bulk materials, most nanostructured electrode materials improve the thermodynamic and kinetic properties of electrochemical reactions for achieving higher energy and power densities. These enhancements are achieved by shortening ion diffusion paths through the solid state, reducing intercalation stress, increasing the utilization of the active materials to improve capacity, and reducing polarization to enhance working voltage.

However, their small size and large specific surface area may have adverse impacts on some applications of nanomaterials. A large electrolyte/electrode surface area may lead to more significant side reactions with electrolytes. Another potential disadvantage is the less dense packing density leading to lower volumetric energy density. A hierarchical micro–nano structure becomes an effective strategy to solve these problems. Choosing between nanostructured electrodes and those with dense architectures creates both opportunities and challenges for enhanced energy storage. In order to enhance stability and reduce the agglomeration of nanoparticles, the nanostructured core-shell approach becomes a very plausible approach to maximize the effect of nanosizing.

When using Na-ion batteries, it is hard to reach the same energy density because the Na atom is three times heavier than the Li atom and the standard electrochemical potential of Na is higher than that of Li. However, they show great potential applications in large-scale stationary energy storage systems because sodium is much more abundant, ecologically sound, and cheaper than lithium. In this context, many efforts have been made to give the electrode materials of Na-ion batteries a higher capacity, better rate capability, and a longer cycle life (including the nanosize approach). It is anticipated that totally new materials with unexpected properties will be discovered through nanotechnologies.

Prof. Dr. Nina V. Kosova
Guest Editor

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Keywords

  • nanoscale electrode materials for lithium- and sodium-ion batteries
  • nanosized electrode materials for lithium- and sodium-ion batteries
  • nanostructured electrode materials for lithium- and sodium-ion batteries
  • synthesis methods for nanosized and nanostructured electrode materials

Published Papers (10 papers)

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Research

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Open AccessArticle
Modified Activated Graphene-Based Carbon Electrodes from Rice Husk for Supercapacitor Applications
Energies 2020, 13(18), 4943; https://doi.org/10.3390/en13184943 - 21 Sep 2020
Abstract
The renewable biomass material obtained from rice husk, a low-cost agricultural waste, was used as a precursor to synthesize a highly porous graphene-based carbon as electrode material for supercapacitors. Activated graphene-based carbon (AGC) was obtained by a two-step chemical procedure and exhibited a [...] Read more.
The renewable biomass material obtained from rice husk, a low-cost agricultural waste, was used as a precursor to synthesize a highly porous graphene-based carbon as electrode material for supercapacitors. Activated graphene-based carbon (AGC) was obtained by a two-step chemical procedure and exhibited a very high specific surface area (SSA) of 3292 m2 g−1. The surface morphology of the synthesized materials was studied using scanning and transmission electron microscopy (SEM, TEM). Furthermore, the AGC was modified with nickel hydroxide Ni(OH)2 through a simple chemical precipitation method. It was found that the most significant increase in capacitance could be reached with Ni(OH)2 loadings of around 9 wt.%. The measured specific capacitance of the pure AGC supercapacitor electrodes was 236 F g−1, whereas electrodes from the material modified with 9 wt.% Ni(OH)2 showed a specific capacitance of up to 300 F g−1 at a current density of 50 mA g−1. The increase in specific capacitance achieved due to chemical modification was, therefore 27%. Full article
(This article belongs to the Special Issue Advanced Nanomaterials for Li- and Na-Ion Batteries)
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Open AccessFeature PaperArticle
Effect of Carbon Additives on the Electrochemical Performance of Li4Ti5O12/C Anodes
Energies 2020, 13(15), 3941; https://doi.org/10.3390/en13153941 - 01 Aug 2020
Abstract
The Li4Ti5O12/C composites were prepared by a hydrothermal method with in situ carbon addition. The influence of the morphology and content of various carbon materials (conductive carbon black, mesoporous carbon G_157M, and carbon replicas) on the electrochemical [...] Read more.
The Li4Ti5O12/C composites were prepared by a hydrothermal method with in situ carbon addition. The influence of the morphology and content of various carbon materials (conductive carbon black, mesoporous carbon G_157M, and carbon replicas) on the electrochemical performance of the Li4Ti5O12/C composites was investigated. The obtained composites were characterized using X-ray diffraction, scanning electron microsopy, high-resolution transmission electron microscopy, thermogravimetric analysis, Raman spectroscopy, and N2 sorption-desorption isotherms. Morphology of the Li4Ti5O12/C composites depends on the carbon matrix used, while both morphology and the amount of carbon material have a great impact on the rate capability and cycling stability of the obtained composites. At low current densities, the Li4Ti5O12/C composite with 5 wt.% G_157M exhibits the highest discharge capacity, while at high charge-discharge rates, the Li4Ti5O12/carbon black composites show the best electrochemical performance. Thus, at ~0.1C, 5C, and 18C rates, the discharge capacities of the obtained Li4Ti5O12/C composites are 175, 120, and 70 mAh/g for G_157M, 165, 126, and 78 mAh/g for carbon replicas, and 173, 128, and 93 mAh/g for carbon black. After 100 cycles, their capacity retention is no less than 95%, suggesting their promising application perspective. Full article
(This article belongs to the Special Issue Advanced Nanomaterials for Li- and Na-Ion Batteries)
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Open AccessCommunication
Nickel Salicylaldoxime-Based Coordination Polymer as a Cathode for Lithium-Ion Batteries
Energies 2020, 13(10), 2480; https://doi.org/10.3390/en13102480 - 14 May 2020
Abstract
Conjugated coordination polymers attract attention as materials for electrochemical energy storage, mostly as cathode materials for supercapacitors. Faradaic capacity may be introduced to such materials using redox-active building blocks, metals, or ligands. Using this strategy, a novel hybrid cathode material was developed based [...] Read more.
Conjugated coordination polymers attract attention as materials for electrochemical energy storage, mostly as cathode materials for supercapacitors. Faradaic capacity may be introduced to such materials using redox-active building blocks, metals, or ligands. Using this strategy, a novel hybrid cathode material was developed based on a Ni2+ metal-organic polymer. The proposed material, in addition to double-layer capacitance, shows high pseudocapacitance, which arises from the contributions of both the metal center and ligand. A tailoring strategy in the ligand design allows us to minimize the molecular weight of the ligand, which increases its gravimetric energy. According to computational results, the ligand makes the prevailing contribution to the pseudocapacitance of the material. Different approaches to metal–organic polymer (MOP) synthesis were implemented, and the obtained materials were examined by FTIR, Raman spectroscopy, powder XRD, SEM/EDX (energy-dispersive X-ray spectroscopy), TEM, and thermal analysis. Energy-storage performance was comparatively studied with cyclic voltammetry (CV) and galvanostatic charge–discharge (GCD). As a result, materials with an excellent discharge capacity were obtained, reaching the gravimetric energy density of common inorganic cathode materials. Full article
(This article belongs to the Special Issue Advanced Nanomaterials for Li- and Na-Ion Batteries)
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Open AccessArticle
Atomic Layer Deposition of Lithium–Nickel–Silicon Oxide Cathode Material for Thin-Film Lithium-Ion Batteries
Energies 2020, 13(9), 2345; https://doi.org/10.3390/en13092345 - 08 May 2020
Abstract
Lithium nickelate (LiNiO2) and materials based on it are attractive positive electrode materials for lithium-ion batteries, owing to their large capacity. In this paper, the results of atomic layer deposition (ALD) of lithium–nickel–silicon oxide thin films using lithium hexamethyldisilazide (LiHMDS) and [...] Read more.
Lithium nickelate (LiNiO2) and materials based on it are attractive positive electrode materials for lithium-ion batteries, owing to their large capacity. In this paper, the results of atomic layer deposition (ALD) of lithium–nickel–silicon oxide thin films using lithium hexamethyldisilazide (LiHMDS) and bis(cyclopentadienyl) nickel (II) (NiCp2) as precursors and remote oxygen plasma as a counter-reagent are reported. Two approaches were studied: ALD using supercycles and ALD of the multilayered structure of lithium oxide, lithium nickel oxide, and nickel oxides followed by annealing. The prepared films were studied by scanning electron microscopy, spectral ellipsometry, X-ray diffraction, X-ray reflectivity, X-ray photoelectron spectroscopy, time-of-flight secondary ion mass spectrometry, energy-dispersive X-ray spectroscopy, transmission electron microscopy, and selected-area electron diffraction. The pulse ratio of LiHMDS/Ni(Cp)2 precursors in one supercycle ranged from 1/1 to 1/10. Silicon was observed in the deposited films, and after annealing, crystalline Li2SiO3 and Li2Si2O5 were formed at 800 °C. Annealing of the multilayered sample caused the partial formation of LiNiO2. The obtained cathode materials possessed electrochemical activity comparable with the results for other thin-film cathodes. Full article
(This article belongs to the Special Issue Advanced Nanomaterials for Li- and Na-Ion Batteries)
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Open AccessFeature PaperArticle
Long-Term Cycling Behavior of Electrospun Separators for Lithium-Ion Batteries: A Comparison with Conventional Separators
Energies 2020, 13(9), 2183; https://doi.org/10.3390/en13092183 - 01 May 2020
Abstract
This paper considered the electrochemical behavior of new electrospun separators for lithium-ion batteries on the basis of nano- and microfibers of polyvinylidene fluoride (PVDF) and its polymer composition, with polytetrafluoroethylene (PTFE) having advanced electroconductive properties over conventionally used separators based on polypropylene (PP) [...] Read more.
This paper considered the electrochemical behavior of new electrospun separators for lithium-ion batteries on the basis of nano- and microfibers of polyvinylidene fluoride (PVDF) and its polymer composition, with polytetrafluoroethylene (PTFE) having advanced electroconductive properties over conventionally used separators based on polypropylene (PP) and glass-fibers (GF). Such advancement is associated with the low density of electrospun material leading to lower mechanical strengths. However, its use in the electrochemical systems with middle-voltage anode materials where dendrite growth is excluded is very prospective. The performance at the operation of the separators were investigated in the three-electrode-containing laboratory half-cells having Li4Ti5O12 as the electrode under investigation. Galvanostatic charge and discharge tests of cells were conducted under variation of the experimental conditions: the current varied in the range 0.1 C–1 C, and 1C cycling was conducted over 100 cycles. The working electrode and separator characteristics at cycling were monitored by the electrochemical impedance spectroscopy (EIS) method. The gradual decrease of Li4Ti5O12 transport characteristics at cycling was noticed for all the types of separators. However, the least degradation rate was associated with the PVDF and the PTFE-based separator. This fact is explained by the better conductivity of an electrospun separator compared to others, with therefore a better current distribution on the electrode surface and a lower concentration perturbation in the electrode. Full article
(This article belongs to the Special Issue Advanced Nanomaterials for Li- and Na-Ion Batteries)
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Open AccessArticle
The Influence of Porous Structure on the Electrochemical Properties of LiFe0.5Mn0.5PO4 Cathode Material Prepared by Mechanochemically Assisted Solid-State Synthesis
Energies 2020, 13(3), 542; https://doi.org/10.3390/en13030542 - 22 Jan 2020
Cited by 1
Abstract
Carbon-free LiFe0.5Mn0.5PO4 and carbon-coated LiFe0.5Mn0.5PO4/C cathode materials were prepared by the mechanochemically assisted solid-state synthesis. The influence of the carbon coating on the porous structure, morphology, conductivity, and electrochemical characteristics of the [...] Read more.
Carbon-free LiFe0.5Mn0.5PO4 and carbon-coated LiFe0.5Mn0.5PO4/C cathode materials were prepared by the mechanochemically assisted solid-state synthesis. The influence of the carbon coating on the porous structure, morphology, conductivity, and electrochemical characteristics of the cathode materials was analyzed using scanning electron microscopy (SEM), standard contact porosimetry (MSCP), electrochemical impedance spectroscopy (EIS), galvanostatic cycling, and galvanostatic intermittent titration technique (GITT). It has been shown that the specific surface area of LiFe0.5Mn0.5PO4/C is twice as high as that of LiFe0.5Mn0.5PO4 despite the very low content of carbon (3%). This was explained by a non-additive contribution of carbon and the active cathode material to the total specific surface area of the composite due to an introduction of carbon in the pores of the cathode material. Among the two key characteristics of a porous structure—specific surface area and volumetric porosity—specific surface area has the greatest impact on electrochemistry of LiFe0.5Mn0.5PO4/C. Mathematical modeling of the discharge profiles of LiFe0.5Mn0.5PO4/C was carried out and compared with the experiment. The cathode heating at high currents was evidenced. The temperatures and coefficients of solid-state diffusion were estimated at different currents. The calculated diffusion coefficient corresponds to the experimental one obtained by GITT at room temperature. Full article
(This article belongs to the Special Issue Advanced Nanomaterials for Li- and Na-Ion Batteries)
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Open AccessArticle
Electrochemical Properties of Nitrogen and Oxygen Doped Reduced Graphene Oxide
Energies 2020, 13(2), 312; https://doi.org/10.3390/en13020312 - 08 Jan 2020
Cited by 1
Abstract
Carbon nanostructures are promising electrode materials for energy storage devices because of their unique physical and chemical properties. Modification of the surface improves the electrochemical properties of those materials because of the changes in morphology, diffusion properties, and inclusion of additional contributions to [...] Read more.
Carbon nanostructures are promising electrode materials for energy storage devices because of their unique physical and chemical properties. Modification of the surface improves the electrochemical properties of those materials because of the changes in morphology, diffusion properties, and inclusion of additional contributions to redox processes. Oxygen-containing functional groups and nitrogen doped into the carbon matrix significantly contribute to the electrochemical behavior of reduced graphite oxide (RGO). In this work, RGO was synthesized during hydrothermal treatment of graphite oxide with a hydrazine sulfate aqueous solution. Different amounts of hydrazine sulfate were used to synthesize RGO with different nitrogen contents in the structure, and the same synthesis conditions made it possible to obtain a material with a similar composition of oxygen-containing functional groups. The materials with different nitrogen concentrations and similar amounts of oxygen were compared as electrode materials for a supercapacitor and as a negative electrode material for a Li-ion battery. It was shown that the presence of oxygen-containing functional groups has the greatest influence on the behavior and efficiency of supercapacitor electrode materials, while nitrogen atoms embedded in the graphene lattice play the largest role in lithium intercalation. Full article
(This article belongs to the Special Issue Advanced Nanomaterials for Li- and Na-Ion Batteries)
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Open AccessArticle
Electrospun Separation Material for Lithium-Ion Batteries: Synthesis and Study of Physical and Electrochemical Properties
Energies 2020, 13(1), 18; https://doi.org/10.3390/en13010018 - 19 Dec 2019
Cited by 1
Abstract
The paper presents a comprehensive study of the physicochemical and electrochemical properties of a new nano-microporous non-woven composite separation material for a lithium-ion battery based on nano- and microfibers of polyvinylidene fluoride (PVDF) and its copolymer with polytetrafluoroethylene (PTFE), obtained by capillary-less electrospinning. [...] Read more.
The paper presents a comprehensive study of the physicochemical and electrochemical properties of a new nano-microporous non-woven composite separation material for a lithium-ion battery based on nano- and microfibers of polyvinylidene fluoride (PVDF) and its copolymer with polytetrafluoroethylene (PTFE), obtained by capillary-less electrospinning. A technique for the synthesis of separation material was developed, and the composition of the polymeric solution and the electrospinning conditions were optimized to produce polymer nano-microfibers with the required physicochemical characteristics. The optimal synthesis conditions for the separation material were determined. Higher porosity of the separation material and increased wettability in the most common electrolyte compositions contribute to the higher conductivity of the obtained separation material in comparison with the widely used commercial separation materials based on polypropylene (PP). The working characteristics of the separation material were studied in laboratory half-cells with a working electrode based on Li4Ti5O12, as well as a lithium metal counter electrode and a reference electrode. Charge-discharge tests of cells were performed in a wide range of variation of currents: From 0.1 to 25 C. A decrease in the total polarization of the working electrode and an increase in the cycled capacity at comparable currents in comparison with a cell with a PP-based separator were noted. The state of the electrodes and the separator in the cell was monitored using electrochemical impedance spectroscopy: The polarization resistances of the electrodes in different frequency ranges were determined, and the diffusion coefficient of lithium ions in the Li4Ti5O12 electrode was estimated in various lithiation states and at different stages of electrochemical tests, which were in the interval of 10−10 to 10−9 cm2·s−1. Full article
(This article belongs to the Special Issue Advanced Nanomaterials for Li- and Na-Ion Batteries)
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Open AccessArticle
Electrospun Core-Shell Nanofiber as Separator for Lithium-Ion Batteries with High Performance and Improved Safety
Energies 2019, 12(17), 3391; https://doi.org/10.3390/en12173391 - 03 Sep 2019
Cited by 9
Abstract
Though the energy density of lithium-ion batteries continues to increase, safety issues related to the internal short circuit and the resulting combustion of highly flammable electrolytes impede the further development of lithium-ion batteries. It has been well-accepted that a thermal stable separator is [...] Read more.
Though the energy density of lithium-ion batteries continues to increase, safety issues related to the internal short circuit and the resulting combustion of highly flammable electrolytes impede the further development of lithium-ion batteries. It has been well-accepted that a thermal stable separator is important to postpone the entire battery short circuit and thermal runaway. Traditional methods to improve the thermal stability of separators include surface modification and/or developing alternate material systems for separators, which may affect the battery performance negatively. Herein, a thermostable and shrink-free separator with little compromise in battery performance was prepared by coaxial electrospinning and tested. The separator consisted of core-shell fiber networks where poly (vinylidene fluoride-hexafluoropropylene) (PVDF-HFP) layer served as shell and polyacrylonitrile (PAN) as the core. This core-shell fiber network exhibited little or even no shrinking/melting at elevated temperature over 250 °C. Meanwhile, it showed excellent electrolyte wettability and could take large amounts of liquid electrolyte, three times more than that of conventional Celgard 2400 separator. In addition, the half-cell using LiNi1/3Co1/3Mn1/3O2 as cathode and the aforementioned electrospun core-shell fiber network as separator demonstrated superior electrochemical behavior, stably cycling for 200 cycles at 1 C with a reversible capacity of 130 mA·h·g−1 and little capacity decay. Full article
(This article belongs to the Special Issue Advanced Nanomaterials for Li- and Na-Ion Batteries)
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Review

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Open AccessReview
Effect of Combined Conductive Polymer Binder on the Electrochemical Performance of Electrode Materials for Lithium-Ion Batteries
Energies 2020, 13(9), 2163; https://doi.org/10.3390/en13092163 - 01 May 2020
Cited by 1
Abstract
The electrodes of lithium-ion batteries (LIBs) are multicomponent systems and their electrochemical properties are influenced by each component, therefore the composition of electrodes should be properly balanced. At the beginning of lithium-ion battery research, most attention was paid to the nature, size, and [...] Read more.
The electrodes of lithium-ion batteries (LIBs) are multicomponent systems and their electrochemical properties are influenced by each component, therefore the composition of electrodes should be properly balanced. At the beginning of lithium-ion battery research, most attention was paid to the nature, size, and morphology peculiarities of inorganic active components as the main components which determine the functional properties of electrode materials. Over the past decade, considerable attention has been paid to development of new binders, as the binders have shown great effect on the electrochemical performance of electrodes in LIBs. The study of new conductive binders, in particular water-based binders with enhanced electronic and ionic conductivity, has become a trend in the development of new electrode materials, especially the conversion/alloying-type anodes. This mini-review provides a summary on the progress of current research of the effects of binders on the electrochemical properties of intercalation electrodes, with particular attention to the mechanisms of binder effects. The comparative analysis of effects of three different binders (PEDOT:PSS/CMC, CMC, and PVDF) for a number of oxide-based and phosphate-based positive and negative electrodes for lithium-ion batteries was performed based on literature and our own published research data. It reveals that the combined PEDOT:PSS/CMC binder can be considered as a versatile component of lithium-ion battery electrode materials (for both positive and negative electrodes), effective in the wide range of electrode potentials. Full article
(This article belongs to the Special Issue Advanced Nanomaterials for Li- and Na-Ion Batteries)
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