Li-ion battery materials: present and future

We developed two-step solution-phase reactions to form hybrid materials of Mn3O4 nanoparticles on reduced graphene oxide (RGO) sheets for lithium ion battery applications. Mn3O4 nanoparticles grown selectively on RGO sheets over free particle growth in solution allowed for the electrically insulating Mn3O4 nanoparticles wired up to a current collector through the underlying conducting graphene network. The Mn3O4 nanoparticles formed on RGO show a high specific capacity up to ~900mAh/g near its theoretical capacity with good rate capability and cycling stability, owing to the intimate interactions between the graphene substrates and the Mn3O4 nanoparticles grown atop. The Mn3O4/RGO hybrid could be a promising candidate material for high-capacity, low-cost, and environmentally friendly anode for lithium ion batteries. Our growth-on-graphene approach should offer a new technique for design and synthesis of battery electrodes based on highly insulating materials.

Mn3O4-Graphene Hybrid as a High Capacity Anode Material for Lithium Ion Batteries

Advanced energy conversion and storage (ECS) devices (including fuel cells, photoelectrochemical water splitting cells, solar cells, Li-ion batteries and supercapacitors) are expected to play a major role in the development of sustainable technologies that alleviate the energy and environmental challenges we are currently facing. The successful utilization of ECS devices depends critically on synthesizing new nanomaterials with merits of low cost, high efficiency, and outstanding properties. Recent progress has demonstrated that nanostructured metal chalcogenides (MCs) are very promising candidates for efficient ECS systems based on their unique physical and chemical properties, such as conductivity, mechanical and thermal stability and cyclability. In this review, we aim to provide a summary on the liquid-phase synthesis, modifications, and energy-related applications of nanostructured metal chalcogenide (MC) materials. The liquid-phase syntheses of various MC nanomaterials are primarily categorized with the preparation method (mainly 15 kinds of methods). To obtain optimized, enhanced or even new properties, the nanostructured MC materials can be modified by other functional nanomaterials such as carbon-based materials, noble metals, metal oxides, or MCs themselves. Thus, this review will then be focused on the recent strategies used to realize the modifications of MC nanomaterials. After that, the ECS applications of the MC/modified-MC nanomaterials have been systematically summarized based on a great number of successful cases. Moreover, remarks on the challenges and perspectives for future MC research are proposed (403 references).

Nanostructured metal chalcogenides: synthesis, modification, and applications in energy conversion and storage devices

Commercial lithium-ion (Li-ion) batteries suffer from low energy density and do not meet the growing demands of the energy storage market. Therefore, building next-generation rechargeable Li and Li-ion batteries with higher energy densities, better safety characteristics, lower cost and longer cycle life is of outmost importance. To achieve smaller and lighter next-generation rechargeable Li and Li-ion batteries that can outperform commercial Li-ion batteries, several new energy storage chemistries are being extensively studied. In this review, we summarize the current trends and provide guidelines towards achieving this goal, by addressing batteries using high-voltage cathodes, metal fluoride electrodes, chalcogen electrodes, Li metal anodes, high-capacity anodes as well as useful electrolyte solutions. We discuss the choice of active materials, practically achievable energy densities and challenges faced by the respective battery systems. Furthermore, strategies to overcome remaining challenges for achieving energy characteristics are addressed in the hope of providing a useful and balanced assessment of current status and perspectives of rechargeable Li and Li-ion batteries.

Guidelines and trends for next-generation rechargeable lithium and lithium-ion batteries.

As new members of carbon material family, carbon and graphene quantum dots (CDs, GQDs) have attracted tremendous attentions for their potentials for biological, optoelectronic, and energy related applications. Among these applications, bio-imaging has been intensively studied, but optoelectronic and energy devices are rapidly rising. In this Feature Article, recent exciting progresses on CD- and GQD-based optoelectronic and energy devices, such as light emitting diodes (LEDs), solar cells (SCs), photodetctors (PDs), photocatalysis, batteries, and supercapacitors are highlighted. The recent understanding on their microstructure and optical properties are briefly introduced in the first part. Some important progresses on optoelectronic and energy devices are then addressed as the main part of this Feature Article. Finally, a brief outlook is given, pointing out that CDs and GQDs could play more important roles in communication- and energy-functional devices in the near future.

Carbon and Graphene Quantum Dots for Optoelectronic and Energy Devices: A Review

A metal-free ORR/OER bifunctional electrocatalyst derived from metal-organic frameworks for rechargeable Zn-Air batteries

We have developed a kind of high-yield synthesis strategy for silver nanowires by a two-step injection polyol method. Silver nanowires and polyethylene oxide (PEO) (M(w) = 900,000) were prepared in a homogeneous-coating ink. Wet composite films with different thicknesses were fabricated on a PET substrate by drawn-down rod-coating technology. Silver nanowires on PET substrates present a homogeneous distribution under the assistance of PEO. Then PEO was thermally removed in situ at a relatively low temperature attributed to its special thermal behavior under atmospheric conditions. As-prepared metallic nanowire films on PET substrates show excellent stability and a good combination of conductivity and light transmission. A layer of transparent poly(ethersulfones) (PESs) was further coated on silver nanowire networks by the same coating method to prevent the shedding and corrosion of silver nanowires. Sandwich-structured flexible transparent films were obtained and displayed excellent electromagnetic interference (EMI) shielding effectiveness.

Flexible transparent PES/silver nanowires/PET sandwich-structured film for high-efficiency electromagnetic interference shielding.

Rechargeable Zn-air batteries are under intensive studies because of their high-energy density, low cost, and safety. However, their wide application is prevented by several remaining technical issues, one of which is the lack of suitable bifunctional cathodic catalysts for oxygen reduction reaction (ORR) during discharging and oxygen evolution reaction (OER) during charging. Due to low material cost and wide distribution, carbon-based materials may serve as promising electrocatalysts, while doping heteroatoms such as nitrogen or boron can effectively enhance their catalytic activity. Herein, we pyrolyze a metal-organic framework containing Zn, N, and B as the precursor to synthesize dual-doped and metal-free porous carbon materials as efficient ORR/OER bifunctional electrocatalysts. The surface area of obtained carbon materials can be greatly enhanced by pyrolysis under H 2 -containing atmosphere. In addition, N and B are evenly distributed within the carbon materials due to the crystalline MOF precursor. The resultant carbon materials exhibit high ORR and OER catalytic activities in both half-cell and single-cell battery measurements. Our study has demonstrated for the first time that MOFs can be used as precursors to synthesize metal-free ORR/OER bifunctional cathodic electrocatalysts with great potential in rechargeable Zn-air batteries.

LiFePO4 (LFP) nanoparticles (∼50 nm in size), nanoplates (100 nm thick and 800 nm wide) and microplates (300 nm thick and 3 μm wide) have been selectively synthesized by a solvothermal method in a water–polyethylene glycol (PEG) binary solvent using H3PO4, LiOH•H2O and FeSO4•7H2O as precursors. The morphology and size of the LFP particles were strongly dependent on synthetic parameters such as volume ratio of PEG to water, temperature, concentration, and feeding sequence. The carbon coated nanoparticles and nanoplates could deliver a discharge capacity of >155 mAh g−1 at 0.1C rate (i.e. 17 mA g−1 of current density); in comparison, the carbon coated microplates had a discharge capacity as low as 110 mAh g−1 at 0.1C rate. The Li-ion diffusion coefficients of the carbon coated nanoparticles, nanoplates, and microplates were calculated to be 6.4 × 10−9, 4.2 × 10−9, and 2.2 × 10−9 cm2 s−1, respectively. When the content of conductive Super P carbon (SP) was increased to 30 wt.%, the prepared electrodes could charge–discharge at a rate as high as 20C. Over 1000 cycles at 20C, the nanoparticle electrode could maintain 89% of its initial capacity (126 mAh g−1), the nanoplate electrode showed 79% capacity retention compared to an initial capacity (129 mAh g−1), and the microplate electrode retained 80% of its initial capacity (63.5 mAh g−1).

Morphology-controlled solvothermal synthesis of LiFePO4 as a cathode material for lithium-ion batteries

Co(OH)2 in the form of hexagonal nanoplates synthesized by a simple hydrothermal reaction has shown even greater activity than cobalt oxides (CoO and Co3O4) in oxygen reduction and oxygen evolution reactions (ORR and OER) under alkaline conditions. The bifunctionality for oxygen electrocatalysis as shown by the OER–ORR potential difference (ΔE) could be reduced to as low as 0.87 V, comparable to the state-of-the-art non-noble bifunctional catalysts, when the Co(OH)2 nanoplates were compounded with nitrogen-doped reduced graphene oxide (N-rGO). The good performance was attributed to the nanosizing of Co(OH)2 and the synergistic interaction between Co(OH)2 and N-rGO. A zinc–air cell assembled with a Co(OH)2–air electrode also showed a performance comparable to that of the state-of-the-art zinc–air cells. The combination of bifunctional activity and operational stability establishes Co(OH)2 as an effective low-cost alternative to the platinum group metal catalysts.

Shiliu Yang

Papers

A metal-free ORR/OER bifunctional electrocatalyst derived from metal-organic frameworks for rechargeable Zn-Air batteries

Flexible transparent PES/silver nanowires/PET sandwich-structured film for high-efficiency electromagnetic interference shielding.

A metal-free ORR/OER bifunctional electrocatalyst derived from metal-organic frameworks for rechargeable Zn-Air batteries

Morphology-controlled solvothermal synthesis of LiFePO4 as a cathode material for lithium-ion batteries

Development of Cobalt Hydroxide as a Bifunctional Catalyst for Oxygen Electrocatalysis in Alkaline Solution.