Accelerating rate calorimetry studies of the reactions between ionic liquids and charged lithium ion battery electrode materials

Using accelerating rate calorimetry (ARC), the reactivity between six ionic liquids (with and without added LiPF₆) and charged electrode materials is compared to the reactivity of standard carbonate-based solvents and electrolytes with the same electrode materials. The charged electrode materials used were Li₁Si, Li₇Ti₄O₁₂ and Li_0.45CoO₂. The experiments showed that not all ionic liquids are safer than conventional electrolytes/solvents. Of the six ionic liquids tested, 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide (EMI-FSI) shows the worst safety properties, and is much worse than conventional electrolyte. 1-Ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMI-TFSI) and 1-propyl-1-methylpyrrolidinium bis(fluorosulfonyl)imide (Py13-FSI) show similar reactivity to carbonate-based electrolyte. The three ionic liquids 1-butyl-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide (BMMI-TFSI), 1-butyl-1-methylpiperidinium bis(trifluoromethanesulfonyl)imide (Pp14-TFSI) and N-trimethyl-N-butylammonium bis(trifluoromethanesulfonyl)imide (TMBA-TFSI) show similar reactivity and are much safer than the conventional carbonate-based electrolyte. A comparison of the reactivity of ionic liquids with common anions and cations shows that ionic liquids with TFSI⁻ are safer than those with FSI⁻, and liquids with EMI⁺ are worse than those with BMMI⁺, Py13⁺, Pp14⁺ and TMBA⁺.     

LiFePO4 cathode in N-methyl-N-propylpiperidinium and N-methyl-N-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide

Ternary [Li⁺][MePrPip⁺][NTf₂⁻] and [Li⁺][MePrPyrr⁺][NTf₂⁻] room temperature ionic liquids (ILs) were obtained by dissolution of solid lithium bis(trifluoromethanesulfonyl)imide (LiNTf₂) in liquid N-methyl-N-propylpiperidinium bis(trifluoromethanesulfonyl)imide and N-methyl-N-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide, respectively, and studied as electrolytes for the use in Li/LiFePO₄ or C(Li)/LiFePO₄ batteries. The cell worked properly in the presence of 10 wt% of vinylene carbonate (VC). Impedance-spectroscopy studies showed that the additive (VC) forms a protective coating on the anode. The LiFePO₄ cathode shows good efficiency (135 mAh g⁻¹) working together with [Li⁺][MePrPip⁺][NTf₂⁻] + VC and [Li⁺][MePrPyrr⁺][NTf₂⁻] + VC ionic liquid electrolytes. The flash point of ionic liquid electrolytes containing 10 wt% of VC is above 300 °C, which makes them practically non-flammable.     

The effects of LiBOB additive for stable SEI formation of PP13TFSI-organic mixed electrolyte in lithium ion batteries

A safe electrolyte system is prepared from N-methyl-N-propylpiperidinium bis (trifluoromethanesulfonyl) imide (PP13TFSI), organic electrolyte (1 mol L⁻¹ LiPF₆/EC-DEC) and lithium bis (oxalato) borate (LiBOB). The additive of LiBOB enhances the stability of interface between electrolyte and anode. The LiBOB-containing mixed electrolytes show non-flammability and good compatibility with active materials. The performance of anode for lithium ion battery is successfully improved by LiBOB-containing mixed electrolytes, which shows 200 mA h g⁻¹ reversible capacities at 0.3 C rate. The ionic conductivity and the lithium ion transference number in LiBOB-containing mixed electrolytes system also suits to application for lithium ion battery.     

Impact of electrolyte additives (alkali metal salts) on the capacitive behavior of NiO-based capacitors

To improve the specific capacitance and energy density of electrochemical capacitor, nanostructured NiO was prepared by high temperature solid-state method as electrode material. The crystal structure and morphology of as-parepared NiO samples were investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Cyclic voltammetry (CV) measurement was applied to investigate the specific capacitance of the NiO electrode. Furthermore, a novel mixed electrolyte consisting of NaOH, KOH, LiOH and Li₂CO₃ was prepared for the NiO capacitor, and the component and concentration of the four different electrolytes was examined by orthogonal test. The results showed that the NiO sample has cubic structure with nano-size particles, and the optimal composition of the electrolyte was: NaOH 2 mol L⁻¹, KOH 3 mol L⁻¹, LiOH 0.05 mol L⁻¹, and Li₂CO₃ 0.05 mol L⁻¹. At a scan rate of 10 mV s⁻¹, the fabricated capacitor exhibits excellent electrochemical capacitive performance, while the specific capacitance and the energy density were 239 F g⁻¹ and 85 Wh kg⁻¹, which was higher than one-component electrolyte.     

Polymer Electrolytes Based on Polymeric Ionic Liquid Poly(methyl 2-(3-vinylimidazolidin-1-yl)acetate bis(trifluoromethane sulfonyl)imide)

A new kind of ionic liquid monomer methyl 2-(3-vinylimidazolidin-1-yl)acetate bromide (MVIm-Br) and polymeric ionic liquid (PIL), poly(methyl 2-(3-vinylimidazolidin-1-yl)acetate bis(trifluoromethanesulfonyl)imide) (PMVIm-TFSI), were synthesized and characterized. Different compositions of polymer electrolytes were prepared by blending PMVIm-TFSI and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) with poly(methylmethacrylate-co-vinyl acetate) (P(MMA-VAc)). The thermal stability and ionic conductivity improved significantly when PMVIm-TFSI was added into P(MMA-VAc)/LiTFSI polymer. For the polymer electrolytes obtained, the highest ionic conductivity at 30 °C is 4.71 × 10⁻⁴ S cm⁻¹ and the corresponding decomposition temperature is ca. 308 °C. Moreover, P(MMA-VAc)/PMVIm-TFSI/LiTFSI electrolyte membrane (transmittance ≥90%) can be used as the ion-conductive layer material for electrochromic devices, which reveal excellent electrochromic performance.     

Effects of surface area on electrochemical performance of Li[Ni<Subscript>0.2</Subscript>Li<Subscript>0.2</Subscript>Mn<Subscript>0.6</Subscript>]O<Subscript>2</Subscript> cathode material

The effect of surface area on the electrochemical properties and thermal stability of Li[Ni_0.2Li_0.2Mn_0.6]O₂ powders was characterized using a charge/discharge cycler and DSC (Differential Scanning Calorimeter). The surface area of the samples was successfully controlled from ~4.0 to ~11.7 m² g⁻¹ by changing the molar ratio of the nitrate/acetate sources and adding an organic solvent such as acetic acid or glucose. The discharge capacity and rate capability was almost linearly increased with increase in surface area of the sample powder. A sample with a large surface area of 9.6–11.7 m² g⁻¹ delivered a high discharge capacity of ~250 mAh g⁻¹ at a 0.2 C rate and maintained 62–63% of its capacity at a 6 C rate versus a 0.2 C rate. According to the DSC analysis, heat generation by thermal reaction between the charged electrode and electrolyte was not critically dependent on the surface area. Instead, it was closely related to the type of organic solvent employed in the fabrication process of the powder.     

Polymeric ionic liquid membranes as electrolytes for lithium battery applications

A new kind of polymeric ionic liquid (PIL) membrane based on guanidinium ionic liquid (IL) with ester and alkyl groups was synthesized. On addition of guanidinium IL, lithium salt, and nano silica in the PIL, a gel PIL electrolyte was prepared. The chemical structure of the PIL and the properties of gel electrolytes were characterized. The ionic conductivity of the gel electrolyte was 5.07 × 10⁻⁶ and 1.92 × 10⁻⁴ S cm⁻¹ at 30 and 80 °C, respectively. The gel electrolyte had a low glass transition temperature (T _g ) under −60 °C and a high decomposition temperature of 310 °C. When the gel polymer electrolyte was used in the Li/LiFePO₄ cell, the cell delivered 142 mAh g⁻¹ after 40 cycles at the current rates of 0.1 C and 80 °C.     

Polydopamine-Assisted Bi-Functional Modification of NiO Anode for Enhanced Lithium-Ion Storage Performance

The blooming requirement of high-performance energy storage systems has aroused the thirst for advanced energy storage materials. As a high capacity anode, however, the application of NiO nanoparticles (NiO NPs) is hindered by intractable issues of dramatic volume change, intrinsic low electronic conductivity, and severe aggregation tendency during lithiation/delithiation. Herein, a polydopamine (PDA) assisted bi-functionalization strategy for fabricating of PDA@NiO-CNT composites for fast and durable lithium storage is reported. In this composite, CNTs intertwine to form a network to ensure sufficient electrolyte infiltration and act as a highly conductive system to motivate fast charge transmission. The strong binding affinity of PDA facilitates bonding between NiO NPs and CNTs, which not only forms uniform and flexible PDA coating but also ensures homogeneous distribution of NiO NPs on CNTs network. Therefore, the bi-functional modified PDA@NiO-CNT electrode possesses high conductivity, alleviates volume change and aggregation of NiO NPs during cycling, achieves a reversible capacity of 1326 mAh g⁻¹ at 100 mA g⁻¹, a rate capability of 215 mAh g⁻¹ at 2000 mA g⁻¹ and a cycling stability with 78% capacity retention after 250 cycles. This bi-functional modification approach manifests its prospective potential for architecting other electrode materials toward high-performance electrochemical devices.     

Solar hydrogen generation from organic substance using earth abundant CuS–NiO heterojunction semiconductor photocatalyst

This work explores the critical role of NiO co-catalyst assembled on the surface of a CuS primary photocatalyst which effectively improves interface properties and enhances solar-to-hydrogen production by prolonging lifetime of photo-excitons generated at the CuS surface. The nanoscale CuS/NiO heterojunction is formulated using hydrothermal and wet impregnation methods. The resultant CuS/NiO composite shows optical absorbance between 380 and 780 nm region. The type-II energetic structure formed at CuS/NiO heterojunction facilitates rapid charge separation and as a result, the CuS/NiO composite exhibits 13 folds higher photocatalytic water splitting performance than CuO and NiO. The champion CuO/NiO photocatalyst is first identified by screening the catalysts using a preliminary water splitting test reaction under natural Sunlight irradiation. After the optimization of the catalyst, it was further explored for enhanced photocatalytic hydrogen production using different organic substances dispersed in water (alcohols, amine and organic acids). The champion CuS/NiO catalyst (CPN-2) exhibited the photocatalytic hydrogen production rate of 52.3 mmol h^?1.g^?1_cat in the presence of lactic acid-based aqueous electrolyte and, it is superior than hydrogen production rate obtained in the presence of other organic substances (triethanolamine, glycerol, ethylene glycol, methanol) tested under identical experimental conditions. These results indicate that the energetic structure of CuS/NiO photocatalyst is favorable for photocatalytic oxidation or reforming of lactic acid. The oxidation of lactic acid contributes both protons and electrons for enhanced hydrogen generation as well as protects CuS from photocorrosion. The modification of surface property and energetic structure of CuS photocatalyst by the NiO co-catalyst improves photogenerated charge carrier separation and in turn enhances the solar-to-hydrogen generation efficiency. The recyclability tests showed the potential of CPN-2 photocatalyst for prolonged photocatalytic hydrogen production while continuous supply of lactic acid feedstock is available.     

Preparation of solid-state composite electrolytes based on organic/inorganic hybrid star-shaped polymer and PEG-functionalized POSS for all-solid-state lithium battery applications

A series of composite electrolytes (CEs) consisting of organic/inorganic hybrid star-shaped polymer (SPP13), plasticizer (PEG-functionalized POSS derivatives), and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) were prepared to investigate the effects of the composite compositions and PEG chain length of PEs on the properties of CEs. SPP13 was prepared via ATRP from poly(ethylene glycol) methyl ether methacrylate (PEGMA) and methacryl-cyclohexyl-POSS (MA-POSS) using an octafunctional initiator, and the PEG-functionalized POSS derivatives were synthesized by the hydrosilylation reaction of octakis(dimethylsilyloxy)silsesquioxane (OHPS) and allyl-PEG. The CEs were found to be dimensionally-stable enough to separate the electrodes in batteries, but they still possessed high mobility of ion-conducting P(PEGMA) segments, as estimated by the low glass transition temperatures (T_g). The CEs having solid-state show quite high ionic conductivity (4.5 × 10⁻⁵ S cm⁻¹ at 30 °C) which is about three times of magnitude larger than that of the matrix polymer (SPP13) electrolyte (1.5 × 10⁻⁵ S cm⁻¹ at 30 °C). The CEs were electrochemically stable up to +4.2 V without the decomposition of electrolytes. An all-solid-state lithium battery prepared from the CEs exhibited larger discharge capacity than that prepared from the SPP13 electrolyte at 60 °C.     

Highly porous metal organic framework derived NiO hollow spheres and flowers for oxygen evolution reaction and supercapacitors

In this study, metal-organic-framework (MOF) derived porous NiO hollow spheres and flowers were obtained using facile solvothermal synthesis and heat treatment. After pyrolyzing, the flower like and hollow spherical like morphology of NiO nanoparticles was successfully inherited from the initial MOF-based templates. The electrochemical studies demonstrated that the porous NiO hallow spheres unveiled a better supercapacitive performance (specific capacitance (C_s) = 1058 F g^?1 at current density (j) = 2 A g^?1) and oxygen evolution reaction (OER) catalytic activity (overpotential (?) = 323 mV) compared to porous NiO flowers (C_s = 857 F g^?1 at j = 2 A g^?1 and ? = 346 mV). Moreover, excellent capacity retention of over 93% was obtained in porous NiO-hs nanoparticles even after 5000 cycles. The fabricated NiO//Fe₂O₃ asymmetric supercapacitor delivered an energy density (E) of 35.75 W h Kg^?1 under power density (P) of 780 W kg^?1 and showed promising stability over 3000 cycles. Considering the ease of preparation and high catalytic activity and supercapacitive performance, these prous NiO hallow structures can be considered as a potential electrode material for next generation energy storage devices and OER catalysts.     

Ag nanoparticles anchored NiO/GO composites for enhanced capacitive performance

Hierarchical nickel oxide/graphene oxide (NiO/GO) and nickel oxide/graphene oxide/silver (NiO/GO/Ag) heterostructures were sucessfully fabricated as high-performance supercapacitors electrode materials by using a hydrothermal process and a photoreduction process. The experimental results showed that the NiO/GO/Ag heterostructure electrodes showed better electrochemical performance than those of NiO/GO and bare NiO nanosheets. The NiO/GO/Ag electrode exhibited a higher specific capacitance of 229 F g⁻¹ at a current density of 1 A g⁻¹, higher than that of 161 F g⁻¹ for NiO/GO composites. Furthermore, NiO/GO/Ag electrode also showed good rate capability (still 200 F g⁻¹ at 6 A g⁻¹) and cycling stability (24% loss after 2000 repetitive cycles at a scan rate of 20 mV s⁻¹). The enhanced capacitive performance of the NiO/GO/Ag composites was mainly attributed to the introduction of Ag nanoparticles, which increased the electrical conductivities of the composites, and promoted the electron transfer between the active components. This study suggested that NiO/GO/Ag composites were a promising class of electrode materials for high performance energy storage applications.     

Preparation and formation mechanism of Cr-free spinel-structured high entropy oxide (MnFeCoNiCu)3O4

In this work, two Cr-free high entropy oxides (HEOs), an equimolar (MnFeCoNiCu)₃O₄ and a non-equimolar (Mn_0.272Fe_0.272Co_0.272Ni_0.092Cu_0.092)₃O₄ have been synthesized by a solid-state reaction method. The reaction sequence and electrical conductivity were also studied for these two HEOs. It is demonstrated that a rock-salt phase containing a solid solution of NiO and CuO appears in the synthesizing process of (MnFeCoNiCu)₃O₄, which is ascribed to the incomplete solubilization of rock-salt phase in the spinel phase. For (Mn_0.272Fe_0.272Co_0.272Ni_0.092Cu_0.092)₃O₄, a single spinel phase (Fd-3m) is obtained at 750 °C, which is much lower than that of the (MnFeCoNiCu)₃O₄ sample. Furthermore, Mn, Fe, Co, Ni elements exist in the chemical states of +2 and + 3, and Cu exists in Cu²⁺ state. The electrical conductivity of (Mn_0.272Fe_0.272Co_0.272Ni_0.092Cu_0.092)₃O₄ is approximately 15.77 S cm^-1 at 800 °C, which is nearly three times higher than that of the (MnFeCoNiCu)₃O₄ sample.     

In-situ generation Cu2O/CuO core-shell heterostructure based on copper oxide nanowires with enhanced visible-light photocatalytic antibacterial activity

As visible light-driven photocatalysts in wastewater treatment, Cu₂O/CuO composites have garnered considerable attention. Herein, Cu₂O/CuO core–shell nanowires were fabricated directly on a Cu mesh using a simple two-step synthesis process involving a wet chemical method and rapid annealing. Unlike conventional composite nanowires, controllable core–shell nanowires exhibit high photoelectrochemical properties and overcome the problems associated with the recovery of powder-based photocatalysts. The presence and structural distribution of the Cu₂O/CuO core–shell nanowires were confirmed using X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. Among the samples subjected to different rapid annealing temperatures for 180 s, the sample exposed to rapid annealing at 350 °C achieved the highest photocurrent density of ?6.96 mA cm^?2. In the core–shell nanowires fabricated on the samples, the ratio of Cu₂O/CuO was 1:1. The photocatalytic activity of the Cu₂O/CuO nanowire samples was also determined by measuring methyl blue degradation to determine their applicability in wastewater treatment. A remarkable photocatalytic degradation rate of 91.6% was achieved at a loading bias voltage of ?0.5 V. The Cu₂O/CuO heterojunction enhanced the photodegradation of the samples because the different bandgaps improved the dissociation of the photogenerated electron–hole pairs. Furthermore, the antibacterial activity of the Cu₂O/CuO nanowires exhibited considerable resistance against Escherichia coli and photocatalytic antibacterial treatment for only 20 min under visible light killed 10⁶ CFU/mL of E. coli. Therefore, the Cu₂O/CuO controllable core–shell nanowires with a high photodegradation performance and excellent antibacterial activity under general illumination show diverse applications in water treatment.     

Pseudo-capacitance properties of porous metal oxide nanoplatelets derived from hydrotalcite-like compounds

Nanoplatelets of metal oxides with interesting porous structure were obtained by thermal treatment of Ni/Al hydrotalcite. Structural and surface properties of the porous oxides were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM and HRTEM), and N₂ adsorption–desorption. The electrochemical performance of the electrodes was investigated by cyclic voltammetry, electrochemical impedance spectroscopy and constant current charge–discharge measurements. Ni/Al hydrotalcite calcined at 450 °C (NA-450) displayed a maximum specific capacitance (419.0 F g⁻¹) due to the porous structure with the highest specific surface area (142.3 m² g⁻¹) and small pore size (4.4 nm). The present study shows the potential of NiO nanoplatelets composite material for electrochemical pseudo-capacitors.     

Growth of yolk-shell CuCo2S4 on NiO nanosheets for high-performance flexible supercapacitors

A poor electrical conductivity and short cycle life limits the wide application of transition metal oxides in energy storage applications. In this study, yolk-shell structured CuCo₂S₄ was grown on NiO nanosheets (NiO@CuCo₂S₄) via a hydrothermal method and vulcanization, which combined the synergistic interactions between Ni, Co, and Cu. The effect of varying the amount of the vulcanizing agent (thiourea) on the electrochemical performance of NiO@CuCo₂S₄ was also investigated. Moreover, the amount of thiourea not only tuned the morphology of the composite, but significantly influenced its electrochemical performance. When the Cu²⁺: Co²⁺: thiourea molar ratio in the precursor solution was 1:2:6, the obtained NiO@CuCo₂S₄ exhibited the best electrochemical performance of the various systems examined, with a specific capacitance of 1658 F g^?1 being achieved at 1 A g^?1. Density functional theory calculations further confirmed the excellent synergistic effect between NiO and CuCo₂S₄. In addition, the asymmetric supercapacitor composed of a NiO@CuCo₂S₄ positive electrode reached an ultrahigh energy density of 73 Wh kg^?1 at a power density of 802 W kg^?1, as well as excellent cycling stability (i.e., 91% capacitance retention after 5000 cycles). These results suggest that NiO@CuCo₂S₄ is a promising candidate for use in energy storage applications.     

NiO/C nanocapsules with onion-like carbon shell as anode material for lithium ion batteries

The synthesis of NiO/C nanocapsules with NiO nanoparticles as the core and onion-like carbon layers as the shell is reported. The NiO/C nanocapsules deliver an initial discharge capacity of 1689.4 mAh g⁻¹ at 0.5 C and maintain a high reversible capacity of 1157.7 mAh g⁻¹ after 50 cycles compared to the NiO nanoparticles of 383.5 mAh g⁻¹. As an anode material for lithium ion batteries, the NiO/C nanocapsules exhibit a remarkable discharge capacity, a high rate charge–discharge capability and an excellent cycling stability. The improvements are ascribed to the fact that the onion-like carbon shells not only can provide enough voids to accommodate the volume change of NiO nanoparticles but also can prevent the formation of solid electrolyte interface (SEI) films on the surface of the NiO nanoparticles and hence the direct contact of Ni and SEI films upon lithium extraction.     

Promising electrode material of Fe3O4 nanoparticles decorated on V2O5 nanobelts for high-performance symmetric supercapacitors

Bundled V₂O₅ nanobelts decorated with Fe₃O₄ nanoparticles (F3V nanostructures) were successfully synthesized to develop a low-cost electrode material for energy storage applications. The synthesized samples were subjected to structural, morphological and electrochemical studies. The Fe₃O₄ nanoparticles decorated over bundled V₂O₅ nanobelts exhibited better electrochemical properties than the pristine Fe₃O₄ nanoparticles and V₂O₅ nanobelts. The electrochemical behavior of the fabricated electrodes was investigated in an electrolyte of 3 M KOH, demonstrated an exceptional specific capacity values of 750.1, 660.3, and 1519 F g^–1 for V₂O₅, Fe₃O₄, and F3V respectively at a current density of 15 A g^–1. The assembled F3V symmetric supercapacitor (SSC) device exhibited an excellent specific capacitance of 93 F g^–1 at a current density of 0.5 A g^–1, delivering energy and power densities of 13 Wh.kg^–1 and 1530 W kg^–1, respectively, and superior long-term cycling stability of ～84% capacity retention over 5000 galvanostatic charge–discharge cycles. These findings demonstrate the extraordinary electrochemical characteristics of the F3V nanostructures, indicating their potential use in energy storage applications.     

Electropolymerization of poly(3-methylthiophene) in pyrrolidinium-based ionic liquids for hybrid supercapacitors

The ionic liquids (ILs) N-butyl-N-methyl-pyrrolidinium trifluoromethanesulfonate (PYR₁₄Tf) and N-methyl-N-propyl-pyrrolidinium bis(fluorosulfonyl)imide (PYR₁₃FSI) are investigated as electropolymerization media for poly(3-methylthiophene) (pMeT) in view of their use in carbon/IL/pMeT hybrid supercapacitors. Data on the viscosity, solvent polarity, conductivity and electrochemical stability of PYR₁₄Tf and PYR₁₃FSI as well as the effect of their properties on the electropolymerization and electrochemical performance of pMeT, which features >200 Fg⁻¹ at 60 °C when prepared and tested in such ILs, are reported and discussed; the results of the electrochemical characterization in N-butyl-N-methyl-pyrrolidinium bis(trifluoromethanesulfonyl)imide of the so-obtained pMeT are also given, for comparison.     

Improving electrochemical performance of NiO films by electrodeposition on foam nickel substrates

NiO films for lithium-ion batteries were deposited on copper plates and foam nickel substrates by electrodeposition and subsequent heat treatment at 300 °C. At a discharge/charge rate of 0.1 C, foam NiO films delivered reversible capacity larger than 650 mAh g⁻¹ and capacity retention over 93% after 50 cycles. NiO films deposited on foam nickel exhibited higher reversible capacity, better cyclability, as well as higher rate capability than those on copper plates. The unique three-dimensionally porous morphologies of foam NiO films were responsible for the better electrochemical performance, which provided not only high electrode/electrolyte contact area but also a good electronic conduction matrix. The present finding offers a new pathway for the large scale fabrication of high-energy-density electrodes for lithium-ion batteries.