Concerted Effect of Ion- and Electron-Conductive Additives on the Electrochemical and Thermal Performances of the LiNi0.8Co0.1Mn0.1O2 Cathode Material Synthesized by a Taylor-Flow Reactor for Lithium-Ion Batteries.

To address the issue that a single coating agent cannot simultaneously enhance Li+-ion transport and electronic conductivity of Ni-rich cathode materials with surface modification, in the present study, we first successfully synthesized a LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode material by a Taylor-flow reactor followed by surface coating with Li-BTJ and dispersion of vapor-grown carbon fibers treated with polydopamine (PDA-VGCF) filler in the composite slurry. The Li-BTJ hybrid oligomer coating can suppress side reactions and enhance ionic conductivity, and the PDA-VGCFs filler can increase electronic conductivity. As a result of the synergistic effect of the dual conducting agents, the cells based on the modified NCM811 electrodes deliver superior cycling stability and rate capability, as compared to the bare NCM811 electrode. The CR2032 coin-type cells with the NCM811@Li-BTJ + PDA-VGCF electrode retain a discharge specific capacity of ∼92.2% at 1C after 200 cycles between 2.8 and 4.3 V (vs Li/Li+), while bare NCM811 retains only 84.0%. Moreover, the NCM811@Li-BTJ + PDA-VGCF electrode-based cells reduced the total heat (Qt) by ca. 7.0% at 35 °C over the bare electrode. Remarkably, the Li-BTJ hybrid oligomer coating on the surface of the NCM811 active particles acts as an artificial cathode electrolyte interphase (ACEI) layer, mitigating irreversible surface phase transformation of the layered NCM811 cathode and facilitating Li+ ion transport. Meanwhile, the fiber-shaped PDA-VGCF filler significantly reduced microcrack propagation during cycling and promoted the electronic conductance of the NCM811-based electrode. Generally, enlightened with the current experimental findings, the concerted ion and electron conductive agents significantly enhanced the Ni-rich cathode-based cell performance, which is a promising strategy to apply to other Ni-rich cathode materials for lithium-ion batteries.

Solid-State Lithium Metal Battery of Low Capacity Fade Enabled by a Composite Electrolyte with Sulfur-Containing Oligomers.

A solid-state lithium metal battery of low capacity fade is acquired using the electrolyte membrane of a polyurethane-acrylate-thiocarbonate (PUAT) oligomer, macromolecules, lithium salt, and an oxide additive. Two types of composite electrolytes have been prepared: the free-standing electrolyte (PUAT-FS) and the electrode-coated electrolyte (PUAT-EC). Featuring a less PUAT content and a finer granular size, PUAT-FS is less ion-conductive than PUAT-EC; 0.44 mS cm-1 in contrast to 0.51 mS cm-1 at room temperature. Nonetheless, the lithium iron phosphate battery of PUAT-FS is far superior to that of PUAT-EC in terms of cycling stability. When cycled at 0.1C and room temperature, the PUAT-FS battery reaches a maximum discharge capacity of 169.7 mAh g-1 at its 20th cycle and decreases to 141.0 mAh g-1 at the 500th cycle, 83.1% retention. The capacity fading rate of the PUAT-FS battery is 0.034% per cycle at 0.1C, significantly less than that of the PUAT-EC battery, 0.138% per cycle. Other maximum capacities and fading rates of the PUAT-FS battery are 152.5 mAh g-1 and 0.050% per cycle at 0.2C in 800 cycles and 126.1 mAh g-1 and 0.051% per cycle at 0.5C in 1000 cycles. These features of a low fading rate and high capacity are attributed to a balanced ratio of oligomer to macromolecule (1:1 w/w) in the free-standing electrolyte and the sulfur-containing oligomer.

Interface Interaction Behavior of Self-Terminated Oligomer Electrode Additives for a Ni-Rich Layer Cathode in Lithium-Ion Batteries: Voltage and Temperature Effects.

Self-terminated oligomer additives synthesized from bismaleimide and barbituric acid derivatives improve the safety and performance of lithium-ion batteries (LIBs). This study investigates the interface interaction of these additives and the cathode material. Two additives were synthesized by Michael addition (additive A) and aza-Michael addition (additive B). The electrochemical performances of bare and modified LiNi0.6Mn0.2Co0.2O2 (NMC622) materials are studied. The cycling stability and rate capability of NMC622 considerably improve on surface modification with additive B. According to the differential scanning calorimetry results, the exothermic heat of fully deliathiated NMC622 is dramatically decreased through surface modification with both additives. The electrode surface kinetics and interface interaction phenomena of the additives are determined through surface plasma resonance measurements in operando gas chromatography-mass spectroscopy (GCMS) and in situ soft X-ray absorption spectroscopy (XAS). The binding rate constant of additive B onto NMC622 particles is 1.2-2.3 × 104 M-1 s-1 in the temperature range of 299-311 K, which is ascribed to the strong binding affinity toward the electrode surface. This affinity enhances Li+ diffusion, which allows the electrode modified by additive B to provide high electrochemical performance with superior thermal stability. In operando GCMS reveals that gas evolution due to the electrolyte degradation at the NMC622 surface contributes to safety hazards in the bare NMC622 material. In situ soft XAS indicates the occurrence of structural transformation in the bare NMC622 material after it is fully charged and at elevated temperatures. The NMC622 material is stabilized by incorporating additives. The unique performance of additive B can be attributed to its linear structure that allows superior electrode surface adhesion compared with that of additive A. Therefore, this study presents an optimized working principle of self-terminated oligomers, which can be developed and applied to improve the safety and performance of LIBs.

Synthesis and characterization of poly(N-isopropylacrylamide-co-acrylamide) mesoglobule core-silica shell nanoparticles.

HYPOTHESIS: How to encapsulate poly(N-isopropylacrylamide) (PNIPAM) mesoglobule cores by silica shells greatly affects the resultant nanoparticle structures. Incorporation of acrylamide (AM) unit into PNIPAM in combination with 3-glycidyloxypropyltrimethoxysilane (GLYMO, as a coupling agent) effectively induces nucleation and growth of silica on PNIPAM core surfaces, where the -NH2 of acrylamide reacts with the epoxide of GLYMO while GLYMO further participates in subsequent sol-gel reaction of tetraethyl orthosilicate (TEOS), thereby leading to desirable particle morphology. EXPERIMENTS: PNIPAM-based core-silica shell nanoparticles were prepared by sol-gel reaction of TEOS and GLYMO in the presence of polymeric core particles. The major parameters investigated in a systematic fashion include acrylamide concentration and weight ratio of polymer:GLYMO:TEOS. GPC, DLS, DSC, FE-SEM, TEM, FTIR and TGA were then used to characterize polymeric cores and hybrid nanoparticles. FINDINGS: The particle morphology was governed primarily by the acrylamide content and the weight ratio of PNIPAM/AM:GLYMO:TEOS, and desirable hybrid nanoparticles with narrow particle size distribution were achieved. The LCST of PNIPAM-based mesoglobules increases with increasing acrylamide content. Encapsulation of PNIPAM-based mesoglobules with silica also reduces their thermo-sensitivity. This is the first report of developing a novel approach to prepare PNIPAM-based mesoglobule core-silica shell nanoparticles with controllable particle morphologies.

Preparing cuprous oxide nanomaterials by electrochemical method for non-enzymatic glucose biosensor.

Cuprous oxide (Cu2O) nanostructure has been synthesized using an electrochemical method with a two-electrode system. Cu foils were used as electrodes and NH2(OH) was utilized as the reducing agent. The effects of pH and applied voltages on the morphology of the product were investigated. The morphology and optical properties of Cu2O particles were characterized using scanning electron microscopy, x-ray diffraction, and diffuse reflectance spectra. The synthesized Cu2O nanostructures that formed in the vicinity of the anode at 2 V and pH = 11 showed high uniform distribution, small size, and good electrochemical sensing. These Cu2O nanoparticles were coated on an Indium tin oxide substrate and applied to detect non-enzyme glucose as excellent biosensors. The non-enzyme glucose biosensors exhibited good performance with high response, good selectivity, wide linear detection range, and a low detection limit at 0.4 µM. Synthesized Cu2O nanostructures are potential materials for a non-enzyme glucose biosensor.

Quantitative determination of uric acid using CdTe nanoparticles as fluorescence probes.

A convenient enzymatic optical method for uric acid detection was developed based on the fluorescence quenching of ligand-capped CdTe nanoparticles by H2O2 which was generated from the enzymatic reaction of uric acid. The interactions between the CdTe nanoparticles capped with different ligands (glutathione, 3-mercaptopropionic acid, and thioglycerol) and H2O2 were investigated. The fluorescence quenching studies of GSH-capped CdTe nanoparticles demonstrated an excellent sensitivity to H2O2. The effects of uric acid, uricase and H2O2 on the fluorescence intensity of CdTe nanoparticles were also explored. The detection conditions, reaction time, pH value, incubation period and the concentration of uricase and uric acid were optimized. The detection limit of uric acid was found to be 0.10 µM and the linear range was 0.22-6 µM under the optimized experimental conditions. These results typify that CdTe nanoparticles could be used as a fluorescent probe for uric acid detection.