Selenium Batteries Research Articles

An alkali metal–selenium battery with a wide temperature range and low self-discharge

A high performance alkali metal–selenium battery with a wide temperature range was obtained by the synergistic effect of microporous fixation and heteroatom adsorption.

Four new Zn(ii) and Cd(ii) coordination polymers using two amide-like aromatic multi-carboxylate ligands: synthesis, structures and lithium-selenium batteries application.

Four new coordination polymers, {[Zn(3-PBI)(H2O)]·2DMF}n (1), [Cd(3-PBI)(DMF)]n (2), {[Zn4(μ4-O)(4-PBI)3]·3DMF}n (3), {[Cd4(4-PBI)4(H2O)6]·13H2O}n (4), have been constructed from two isomeric flexible multi-carboxylate ligands, 3-H2PBI = 5-(3-(pyridin-3-yl)benzamido)isophthalic acid and 4-H2PBI = 5-(3-(pyridin-4-yl)benzamido)isophthalic acid. Structural analysis reveals that compound 1 is a one-dimensional (1D) ladder-like chain assembled by Zn(ii) ions and 3-PBI2− ligands, which further extend into a 3D supramolecular structure through π⋯π stacking and interlayer (O–H⋯O) hydrogen bonding interactions. In compound 2, Cd2+ metal ions are connected by carboxylate groups to form [Cd2(COO)4] secondary building units (SBUs). The whole framework possesses a quadrilateral channel and constitutes a unique 3D (3,6)-connected rutile net with the Schläfli symbol of (42·610·83)(4·62)2. As for 3, Zn(ii) ions are bridged by one μ4-O and six carboxylate groups to form a tetranuclear [Zn4(μ4-O)(COO)6] cluster, resulting in a rare (3,9)-connected 3D network. Compound 4 has an appealing 2D layered architecture involving two distinct topologies in the crystal structure, stacking in an unusual ABBABB mode (where A represents (4·82) topology and B denotes kgd topology). Moreover, compound 2 is prepared as a support for active selenium through a melt-diffusion method. The obtained Cd-CP/Se electrode can be tested for lithium–selenium batteries and shows an initial capacity of 514 mA h g−1 and a reversible capacity of 200 mA h g−1 at 1C after 500 cycles. The good storage performance of Cd-CP/Se demonstrates it to be a prospective cathode material for lithium–selenium batteries.

Poly(carbazole)-Coated Selenium@Conical Carbon Nanofibers Hybrid for Lithium–Selenium Batteries with Enhanced Lifespan

A scalable protocol enabling selenium (Se) cathodes in Lithium (Li)-Se batteries to retain a high reversible capacity with repeated cycling is demonstrated. A hybrid of Se powder with conical carbo...

Metal-Organic-Framework-Derived N-Doped Hierarchically Porous Carbon Polyhedrons Anchored on Crumpled Graphene Balls as Efficient Selenium Hosts for High-Performance Lithium-Selenium Batteries.

Developing carbon scaffolds showing rational pore structures as cathode hosts is essential for achieving superior electrochemical performances of lithium-selenium (Li-Se) batteries. Hierarchically porous N-doped carbon polyhedrons anchored on crumpled graphene balls (NPC/CGBs) are synthesized by carbonizing a zeolitic imidazolate framework-8 (ZIF-8)/CGB composite precursor, producing an unprecedented effective host matrix for high-performance Li-Se batteries. Mesoporous CGBs obtained by one-pot spray pyrolysis are used as a highly conductive matrix for uniform polyhedral ZIF-8 growth. During carbonization, ZIF-8 polyhedrons on mesoporous CGBs are converted into N-doped carbon polyhedrons showing abundant micropores, forming a high-surface-area, high-pore-volume hierarchically porous NPC/CGB composite whose small unique pores effectively confine Se during melt diffusion, thereby providing conductive electron pathways. Thus, the integrated NPC/CGB-Se composite ensures high Se utilization originating from complete electrochemical reactions between Se and Li ions. The NPC/CGB-Se composite cathode exhibits high discharge capacities (998 and 462 mA h g-1 at the 1st and 1000th cycles, respectively, at a 0.5 C current density), good capacity retention (68%, calculated from the 3rd cycle), and excellent rate capability. A discharge capacity of 409 mA h g-1 is achieved even at an extremely high (15.0 C) current density.

Optimization of Structure and Porosity of Nitrogen Containing Mesoporous Carbon Spheres for Effective Selenium Confinement in Futuristic Lithium–Selenium Batteries

A series of nitrogen containing mesoporous carbon spheres (NCS), possessing a range of hollow to nonhollow core structures to confine Se, are prepared using an easily tunable silica template and ex...

A Self-Repairing Cathode Material for Lithium-Selenium Batteries: Se-C Chemically Bonded Selenium-Graphene Composite.

Lithium-selenium batteries, employing selenium as a cathode material, exhibit some notable advantages, such as high discharge rates and good cycling performance, due to their high electrical conductivity, high output voltages, and high volumetric capacity density. However, an important problem, termed the "shuttle effect", can lead to capacity decay in Li-Se cells (and in Li-S cells), which arises from aggregation and the loss of Se or S from the cathode into the electrolyte. In this work, in order to solve this problem, a new self-repairing system has been devised, in which some Se atoms are chemically bonded to the carbon atoms of graphene and act as reclaiming points for dissociated Se atoms through the establishment of -Se-Se-Se- chains. Se-decorated graphene (Se-GE) was first constructed through a facile high-energy ball-milling process. Its formation was confirmed by XRD, SEM, HRTEM, XPS, and Raman analyses. As we anticipated, in examining cell properties, the as-prepared Se-GE composite underwent an initial capacity decay in the first 20 cycles (from 1050 mAh g-1 to 750 mAh g-1 , ca. 29 % loss), but the capacity then reverted to 970 mAh g-1 (ca. 92 % of the initial value). Other measurements were also consistent with the recapture of dissociated Se atoms.

Vacuum Calcination Induced Conversion of Selenium/Carbon Wires to Tubes for High‐Performance Sodium–Selenium Batteries

AbstractA vacuum calcination approach is developed to fabricate selenium/carbon composites, which does not require intensive mixing and durable heating such as in commonly used melt‐infusion methods of loading selenium into carbon hosts. Starting from carbon‐coated selenium wires prepared via a wet‐chemical reaction, selenium/carbon tubes are fabricated by a straightforward calcination process. The calcination is conducted in a confined space to reduce the insulating carbon shell under vacuum, and selenium melts but remains a constituting part of the composite. Paired with sodium metal anode, the resultant selenium/carbon tubes deliver a high reversible capacity of 601 and 509 mA h g−1 at 0.2 and 2 C normalized by the mass of selenium, which corresponds to energy and power densities of 860 and 667 Wh kg−1 at 193 and 1770 W kg−1, respectively. Such capacity and rate performance surpasses most typical cathode materials for lithium or sodium (ion) batteries, according to the comparative literature analysis. Moreover, the robust tubular‐like hollow structure of the selenium/carbon composites ensures for impressive capacity retention of more than 90% after 1000 cycles at 20 C.

A conductive selenized polyacrylonitrile cathode in nucleophilic Mg2+/Li+ hybrid electrolytes for magnesium–selenium batteries

Rechargeable magnesium–selenium (Mg–Se) batteries are promising electrochemical systems with higher energy density than traditional magnesium batteries. This work proposes combining of a conductive Se/PAN cathode and a compatible nucleophilic electrolyte to promote the performance of Mg–Se batteries.

Selenium embedded in MOF-derived N-doped microporous carbon polyhedrons as a high performance cathode for sodium–selenium batteries

ZIF-8 derived N-doped microporous carbon/selenium composites as cathodes for Na–Se batteries deliver a superior long-term cycling performance and rate capability.

Carbon microspheres with well-developed micro- and mesopores as excellent selenium host materials for lithium–selenium batteries with superior performances

Highly porous carbon microspheres with well-developed micro- and mesopores were fabricated as excellent host materials for selenium by applying a spray pyrolysis process.

Long Cycle Life, Low Self‐Discharge Sodium–Selenium Batteries with High Selenium Loading and Suppressed Polyselenide Shuttling

AbstractThe use of selenium as a cathode in rechargeable sodium–selenium batteries is hampered by low Se loading, inferior electrode kinetics, and polyselenide shuttling between the cathode and anode. Here a high‐performance sodium–selenium cell is presented by coupling a binder‐free, self‐interwoven carbon nanofiber–selenium cathode with a light‐weight carbon‐coated bifunctional separator. With this strategy, electrodes with a high Se mass loading (4.4 mg cm−2) render high reversible capacities of 599 mA h g−1 at 0.1C rate and 382 mA h g−1 at 5C rate. In addition, this novel cell offers good shelf‐life with a low self‐discharge, retaining 93.4% of its initial capacity even after resting for six months. As evidenced by experimental and density functional theory analysis, the remarkable dynamic (cycle life) and static (shelf‐life) stabilities originate from the high electrical conductivity, improved Na‐ion accessibility through the 3D interconnected open channels, and highly restrained polyselenide shuttle. The results demonstrate the viability of high‐performance sodium–selenium batteries with high selenium loading.

Exceptional Energy and New Insight with Sodium – Selenium Battery Based on Carbon Nanosheet Cathode and Pseudographite Anode

We created a unique sodium ion battery (NIB, SIB) cathode based on selenium in cellulose-derived carbon nanosheets (CCN), termed Se-CCN. The elastically compliant two-dimensional CCN host incorporates a high mass loading of amorphous Se (53wt.%), which is primarily impregnated into the 1 cm3g-1 of the nanopores. This results in facile sodiation kinetics due to short solid-state diffusion distances and large charge transfer area of the nanosheets. The architecture also leads to an intrinsic resistance to polyselenide shuttle and to disintegration/coarsening. As a Na half-cell, the Se-CCN cathode delivers a reversible capacity of 613 mAh g-1 with 88% retention over 500 cycles. The exceptional stability is achieved employing a standard electrolyte (1M NaClO4 EC-DMC), without secondary additives or high salt concentrations. The rate capability is also superb, achieving 300 mAhg-1 at 10C. Compared to recent state-of-the-art literature, the Se-CCN is the most cyclically stable and offers the highest rate performance. As a Se-Na battery, the system achieves 992 Wh/kg at 68 W/kg and 384 Wh/kg at 10144 W/kg (by active mass in cathode). We are the first to fabricate and test a Se-based full NIB, which is based on Se-CCN coupled to a Na intercalating pseudographitic carbon anode (PGC). It is demonstrated that the PGC anode increases its structural order in addition to dilating as a result of Na intercalation at voltages below 0.2 V vs. Na/Na+. The {110} Na reflections are distinctly absent from the XRD patterns of PGC sodiated down to 0.001 V, indicating that Na metal pore filling is not significant for pseudographitic carbons. The battery delivers highly promising Ragone chart characteristics, for example yielding 203 and 50 Wh kg-1 at 70 and 14000 W kg-1 (by total material mass in anode and cathode).

A stable lithium–selenium interface via solid/liquid hybrid electrolytes: Blocking polyselenides and suppressing lithium dendrite

Here we report a novel lithium–selenium (Li–Se) battery with hybrid electrolytes that permit fast solution-phase Li–Se redox reactions, eliminate polyselenides-shuttling and suppress the formation of lithium dendrite. The hybrid electrolytes consist of NASICON-type Li1.5Al0.5Ge1.5 (PO4)3 (LAGP) ceramics sandwiched by tetraethylene glycol dimethyl ether (TEGDME) electrolyte, enabling the use of low-cost and highly-scalable carbon, demonstrating full utilization of the Se cathode (e.g., 677mAhg−1 at 0.1C (100% of theoretical capacity)), superior cycling stability (e.g., 613mAhg−1 over 500 cycles at 0.8C, fading rate=0.008% per cycle), and promising rate capabilities (e.g., 540mAhg−1 at 1.5C). With the hybrid electrolytes, we further demonstrate a high Se loading of 5.9mgcm−2 with a stable discharge capacity of 454mAhg−1 (2.68mAhcm−2). Our work demonstrates that combining solid state electrolyte with liquid glyme electrolyte is key to achieve stable and high-performance Li–Se batteries.

The rise of lithium–selenium batteries

The lithium–selenium (Li–Se) battery is an alternative to its sulfur counterpart with some noticeable advantages, such as the significantly higher electrical conductivity of Se and better electrochemical performance.

Exceptional energy and new insight with a sodium–selenium battery based on a carbon nanosheet cathode and a pseudographite anode

We created a unique sodium ion battery (NIB, SIB) cathode based on selenium in cellulose-derived carbon nanosheets (CCNs), termed Se-CCN.

Advances and challenges of nanostructured electrodes for Li–Se batteries

In this review, the recent advances of nanostructured electrodes for lithium–selenium batteries and their characterizations and mechanisms are reviewed and discussed.

Hollow selenium encapsulated into 3D graphene hydrogels for lithium–selenium batteries with high rate performance and cycling stability

Hollow selenium nanospheres encapsulated within 3D graphene hydrogels were prepared and researched as Li–Se battery cathode materials. It was shown that the hollow Se structure and 3D graphene were beneficial to the application Li–Se batteries.

A high performance lithium–selenium battery using a microporous carbon confined selenium cathode and a compatible electrolyte

Exceptional performances are obtained for a lithium–selenium battery using a nanostructured Se/C cathode material and a compatible LiDFOB/EC-DMC-FEC carbonate electrolyte.

Porous carbon derived from Sunflower as a host matrix for ultra-stable lithium–selenium battery

A novel porous carbon material using the spongy tissue of sunflower as raw material is reported for the first time. The obtained porous carbon has an extremely high surface area of 2493.0m2g−1, which is beneficial to focus on encapsulating selenium in it and have an inhibiting effect about diffusion of polyselenides over the charge/discharge processes used as the host matrix for Li-Se battery. The porous carbon/Se composite electrode with 63wt% selenium delivers a high specific capacitance of 319mAhg−1 of the initial capacity, and maintains 290mAhg−1, representing an extremely high capacity retention of 90.9% after 840 cycles with the rate of 1C.

Confined selenium within metal-organic frameworks derived porous carbon microcubes as cathode for rechargeable lithium–selenium batteries

Unique hierarchically porous carbon microcubes (CMCs) consists of irregular bubbles derived from metal organic frameworks (MOFs) have been prepared via simple hydrothermal synthesis method and carbonization treatment. Selenium nanoparticles are uniformly dispersed in the hierarchical porous structure of CMCs by a typical melt-diffusion process, and the yielding Se/CMCs composite is enabled as a cathode material for lithium-selenium rechargeable batteries. In the carbonate-based electrolyte, with Se loading of nearly ∼50 wt%, the Se/CMCs composite exhibits an ultrahigh initial discharge specific capacity of 780.4 mAh g−1 and still retains a reversible capacity of 425.2 mAh g−1 after 100 cycles at 0.2 C. Specially, these hollow structure CMCs with high conductivity contribute to the outstanding electrochemical properties by effectively decreasing the charge transfer resistance and suppressing polyselenides dissolution in carbonate electrolyte.