Acidity-Aided Surface Modification Strategy to Enhance In Situ MnO2 Deposition for High Performance Zn-MnO2 Battery Prototypes.

Zn-MnO2 batteries offer cost-effective, eco-friendly, and efficient solutions for large-scale energy storage applications. However, challenges, like irreversible cathode reactions, prolonged cyclability, and electrolyte stability during high-voltage operations limit their broader application. This study provides insight into the charge-discharge process through in situ deposition of active ß-MnO2 nanoflakes on a carbon-based current collector. The study elucidates the effect of pH and electrolyte concentration on chemical conversion reactions with Zn, in particular focus on their impact on the two-electron MnO2/Mn2+ reaction crucial for high voltage operation. The electrolyte, characterized by being relatively lean in Mn2+ and with a targeted low pH, enables extended cycling. This research achieves greater cycling durability by integrating a carbon-based cathode current collector with high density of structural defects in combination with cell architectures suitable for large-scale energy storage. A flooded stack-type Zn-MnO2 battery prototype employing the optimized electrolyte demonstrates a high discharge voltage (≈2 V) at a substantial discharge current rate of 10 mA cm-2. The battery exhibits an impressive areal capacity of ≈2 mAh cm-2, maintaining ≈100% capacity retention over 400 cycles. This research establishes a promising practical, and cost-effective cathode-free design for Zn-MnO2 batteries, that minimizes additional processing and assembly costs.

New Class of High-Energy, High-Power Capacitive Devices Enabled by Stabilized Lithium Metal Anodes.

Lithium-ion capacitors (LIC) combine the energy storage mechanisms of lithium-ion batteries and electric double layer capacitors (EDLC) and are supposed to promise the best of both worlds: high energy and power density combined with a long life. However, the lack of lithium cation sources in the carbon cathode demands the cumbersome step of prelithiation of the graphite anode, mainly by using sacrificial lithium metal, hindering the mass adoption of LICs. Here, in a conceptually new class of devices termed lithium metal capacitors (LMC), we replace the graphite anode with a lithium metal anode stabilized by a complex yet stable solid-electrolyte interface (SEI). Via a specialized formation process, the well-explored synergetic reaction between the LiNO3 additive and controlled amounts of polysulfides in an ether-based electrolyte stabilizes the SEI on the lithium metal electrode. Optimized devices at the coin cell level deliver 55 mAh g-1 at a fast 30C discharge rate and maintain 95% capacity after 8000 cycles. At the pouch-cell level, energy densities of 13 Wh kg-1 are readily achieved, indicating the transferability of the technology to practical scales. The LMC, a new class of capacitive device, eliminates the prelithiation process of the conventional LIC, allowing practical production at scale and offering exciting avenues for exploring versatile cathode chemistries on account of using a lithium metal anode.

A saccharide-based binder for efficient polysulfide regulations in Li-S batteries.

The viability of lithium-sulfur batteries as an energy storage technology depends on unlocking long-term cycle stability. Most instability stems from the release and transport of polysulfides from the cathode, which causes mossy growth on the lithium anode, leading to continuous consumption of electrolyte. Therefore, development of a durable cathode with minimal polysulfide escape is critical. Here, we present a saccharide-based binder system that has a capacity for the regulation of polysulfides due to its reducing properties. Furthermore, the binder promotes the formation of viscoelastic filaments during casting which endows the sulfur cathode with a desirable web-like microstructure. Taken together this leads to 97% sulfur utilisation with a cycle life of 1000 cycles (9 months) and capacity retention (around 700 mAh g-1 after 1000 cycles). A pouch cell prototype with a specific energy of up to 206 Wh kg-1 is produced, demonstrating the promising potential for practical applications.

A High Throughput and Unbiased Machine Learning Approach for Classification of Graphene Dispersions.

Significant research to define and standardize terminologies for describing stacks of atomic layers in bulk graphene materials has been undertaken. Most methods to measure the stacking characteristics are time consuming and are not suited for obtaining information by directly imaging dispersions. Conventional optical microscopy has difficulty in identifying the size and thickness of a few layers of graphene stacks due to their low photon absorption capacity. Utilizing a contrast based on anisotropic refractive index in 2D materials, it is shown that localized thickness-specific information can be captured in birefringence images of graphene dispersions. Coupling pixel-by-pixel information from brightfield and birefringence images and using unsupervised statistical learning algorithms, three unique data clusters representing flakes (unexfoliated), nanoplatelets (partially exfoliated), and 2D sheets (well-exfoliated) species in various laboratory-based and commercial dispersions of graphene and graphene oxide are identified. The high-throughput, multitasking capability of the approach to classify stacking at sub-nanometer to micrometer scale and measure the size, thickness, and concentration of exfoliated-species in generic dispersions of graphene/graphene oxide are demonstrated. The method, at its current stage, requires less than half an hour to quantitatively assess one sample of graphene/graphene oxide dispersion.

Expansion-tolerant architectures for stable cycling of ultrahigh-loading sulfur cathodes in lithium-sulfur batteries.

Lithium-sulfur batteries can displace lithium-ion by delivering higher specific energy. Presently, however, the superior energy performance fades rapidly when the sulfur electrode is loaded to the required levels-5 to 10 mg cm-2- due to substantial volume change of lithiation/delithiation and the resultant stresses. Inspired by the classical approaches in particle agglomeration theories, we found an approach that places minimum amounts of a high-modulus binder between neighboring particles, leaving increased space for material expansion and ion diffusion. These expansion-tolerant electrodes with loadings up to 15 mg cm-2 yield high gravimetric (>1200 mA·hour g-1) and areal (19 mA·hour cm-2) capacities. The cells are stable for more than 200 cycles, unprecedented in such thick cathodes, with Coulombic efficiency above 99%.

Large-area graphene-based nanofiltration membranes by shear alignment of discotic nematic liquid crystals of graphene oxide.

Graphene-based membranes demonstrating ultrafast water transport, precise molecular sieving of gas and solvated molecules shows great promise as novel separation platforms; however, scale-up of these membranes to large-areas remains an unresolved problem. Here we demonstrate that the discotic nematic phase of graphene oxide (GO) can be shear aligned to form highly ordered, continuous, thin films of multi-layered GO on a support membrane by an industrially adaptable method to produce large-area membranes (13 × 14 cm(2)) in <5 s. Pressure driven transport data demonstrate high retention (>90%) for charged and uncharged organic probe molecules with a hydrated radius above 5 Å as well as modest (30-40%) retention of monovalent and divalent salts. The highly ordered graphene sheets in the plane of the membrane make organized channels and enhance the permeability (71 ± 5 l m(-2) hr(-1) bar(-1) for 150 ± 15 nm thick membranes).

Electrochemical capacitance of Ni-doped metal organic framework and reduced graphene oxide composites: more than the sum of its parts.

Composites of a Ni-doped metal organic framework (MOF) with reduced graphene oxide (rGO) are synthesized in bulk (gram scale) quantities. The composites are composed of rGO sheets, which avoid restacking from the physical presence of MOF crystals. At larger concentration of rGO, the MOF crystals are distributed on the overlapping and continuous rGO sheets. Ni in Ni-doped MOF is found to engage in a two-electron, reversible, efficient, redox reaction shuttling between Ni and Ni(OH)2 in aqueous potassium hydroxide (KOH) electrolyte. The reaction is rather unique as Ni-based supercapacitors use a one-electron transfer Faradaic redox reaction between Ni(OH)2 and NiO(OH). Employing electrochemical impedance spectroscopy, we determined the charge transfer resistance to be 184 mΩ for MOF, 74 mΩ for a Ni-doped MOF and 6 mΩ for a rGO-Ni-doped MOF composite, but these modifications do not affect the mass transfer resistance. This novel redox reaction in conjunction with the lowered charge transfer resistance from the introduction of rGO underpins the synergy that dramatically increases the capacitance to 758 F/g in the rGO-Ni-doped MOF composite, when the parent MOF could store only 100 F/g and a physical composite of rGO and Ni-doped MOF could algebraically achieve about 240 F/g. A generic approach of doping MOFs with a redox active metal and forming a composite with rGO transforms an electro-inactive MOF to high capacity energy storage material with energy density of 37.8 Wh/kg at a power density of 227 W/kg. These results can promote the development of high-performance energy storage materials from the wide family of MOFs available.