Delocalized Lithium Ion Flux by Solid-State Electrolyte Composites Coupled with 3D Porous Nanostructures for Highly Stable Lithium Metal Batteries.

This work investigates the root cause of failure with the ultimate anode, Li metal, when employing conventional/composite separators and/or porous anodes. Then a feasible route of utilizing Li metal is presented. Our operando and microscopy studies have unveiled that Li+ flux passing through the conventional separator is not uniform, resulting in preferential Li plating/stripping. Porous anodes alone are subject to clogging with moderate- or high-loading cathodes. Here we discovered it is necessary to seek synergy from our separator and anode pair to deliver delocalized Li+ to the anode and then uniformly plate Li metal over the large surface areas of the porous anode. Our polymer composite separator containing a solid-state electrolyte (SE) can provide numerous Li+ passages through the percolated SE and pore networks. Our finite element analysis and comparative tests disclosed the synergy between the homogeneous Li+ flux and current density reduction on the anode. Our composite separators have induced compact and uniform Li plating with robust inorganic-rich solid electrolyte interphase layers. The porous anode decreased the nucleation overpotential and interfacial contact impedance during Li plating. Full cell tests with LiFePO4 and Li[Ni0.8Mn0.1Co0.1]O2 (NMC811) exhibited remarkable cycling behaviors: ∼80% capacity retention at the 750th and 235th cycle, respectively. A high-loading NMC811 (4 mAh cm-2) full cell displayed maximum cell-level energy densities of 334 Wh kg-1 and 783 Wh L-1. This work proposes a solution for raising energy density by adopting Li metal, which could be a viable option considering only incremental advancement in conventional cathodes lately.

Printing Composites with Salt Hydrate Phase Change Materials for Thermal Energy Storage.

Salt hydrate phase change materials are important in advancing thermal energy storage technologies for the development of renewable energies. At present, their widespread use is limited by undesired undercooling and phase separation, as well as their tendency to corrode container materials. Herein, we report a direct ink writing (DIW) additive manufacturing technique to print noncorrosive salt hydrate composites with thoroughly integrated nucleating agents and thermally conductive additives. First, salt hydrate particles are prepared from nonaqueous Pickering emulsions and then employed as rheological modifiers to formulate thixotropic inks with polymer dispersions in toluene serving as the matrix. These inks are successfully printed at room temperature and cured by solvent evaporation under ambient conditions. The resulting printed and cured composites, containing up to 70 wt % of the salt hydrate, exhibit reliable thermal cyclability for 10 cycles and suppressed undercooling compared to the bulk salt hydrate. Remarkably, the composites consistently maintain their structural integrity and thermal performance throughout the entirety of both the melting and solidification processes. We demonstrate the versatility of this approach by utilizing two salt hydrates, magnesium nitrate hexahydrate (MNH, Tm = 89 °C) and zinc nitrate hexahydrate (ZNH, Tm = 36 °C), to achieve desired thermal characteristics across a wide range of temperatures. Further, we establish that the incorporation of carbon black in these inks enhances the thermal conductivity by at least 33%. This approach consolidates the strengths of additive manufacturing and salt hydrate phase change materials to harness customizable thermal properties, well suited for targeted thermal energy management applications.

Sustainable power generation via hydro-electrochemical effects.

Recent efforts towards energy scavenging with eco-friendly methods and abundant water look very promising for powering wearables and distributed electronics. However, the time duration of electricity generation is typically too short, and the current level is not sufficient to meet the required threshold for the proper operation of electronics despite the relatively large voltage. This work newly introduced an electrochemical method in combination with hydro-effects in order to extend the energy scavenging time and boost the current. Our device consists of corroded porous steel electrodes whose corrosion overpotential was lowered when the water concentration was increased and vice versa. Then a potential difference was created between two electrodes, generating electricity via the hydro-electrochemical method up to an open-circuit voltage of 750 mV and a short-circuit current of 90 µA cm-2. Furthermore, electricity was continuously generated for more than 1500 minutes by slow water diffusion against gravity from the bottom electrode. Lastly, we demonstrated that our hydro-electrochemical power generators successfully operated electronics, showing the feasibility of offering electrical power for sufficiently long time periods in practice.

Revamping Lithium-Sulfur Batteries for High Cell-Level Energy Density by Synergistic Utilization of Polysulfide Additives and Artificial Solid-Electrolyte Interphase Layers.

Despite the high theoretical capacity of lithium-sulfur (Li-S) batteries, a high cell-level energy density and a long cycling life are barely achieved, mainly due to the large electrolyte-to-sulfur ratio, polysulfide (PS) shuttle causing the loss of active sulfur, and the formation of passivation layers on the Li anode. To raise the energy density, holding PS in the cathode has been the most popular approach. Still, it has failed, particularly, when the sulfur loading is high enough to have energy densities similar to those of commercial Li-ion batteries. Here, a practical approach of achieving high "cell-level" energy densities is attempted using lithium PS (LPS)-containing electrolytes instead of a pure electrolyte, reducing the electrolyte-to-sulfur ratio and PS diffusion out of the cathode due to concentration differences. Meanwhile, the persistent problems including PS passivation and Li dendrites are suppressed using Li2 S-phobic artificial solid-electrolyte interphase (A-SEI) layers on Li metal. The synergistic effects from the LPS additives and A-SEI result in a superior cell-level volumetric energy density of 650 Wh L-1 as well as large cumulative energy densities considering cycling life. This approach provides an important stepping stone to realize commercial Li-S batteries rivaling the current Li-ion batteries.

Colossal thermo-hydro-electrochemical voltage generation for self-sustainable operation of electronics.

Thermoelectrics are suited to converting dissipated heat into electricity for operating electronics, but the small voltage (~0.1 mV K-1) from the Seebeck effect has been one of the major hurdles in practical implementation. Here an approach with thermo-hydro-electrochemical effects can generate a large thermal-to-electrical energy conversion factor (TtoE factor), -87 mV K-1 with low-cost carbon steel electrodes and a solid-state polyelectrolyte made of polyaniline and polystyrene sulfonate (PANI:PSS). We discovered that the thermo-diffusion of water in PANI:PSS under a temperature gradient induced less (or more) water on the hotter (or colder) side, raising (or lowering) the corrosion overpotential in the hotter (or colder) side and thereby generating output power between the electrodes. Our findings are expected to facilitate subsequent research for further increasing the TtoE factor and utilizing dissipated thermal energy.

Thermal treatment using microwave irradiation for the phytosanitation of Xylella fastidiosa in pecan graftwood.

Pecan bacterial leaf scorch caused by Xylella fastidiosa is an emerging disease for the U.S. and international pecan industries and can be transmitted from scion to rootstock via grafting. With the expanse of global transportation and trade networks, phytosanitation is critical for reducing the spread of economically significant pathogens, such as X. fastidiosa. We developed and evaluated thermal treatments using microwave irradiation and microwave absorbers [sterile deionized water (dH2O) and carbon nanotubes (CNTs)] as novel disinfectant methods for remediating X. fastidiosa in pecan scions. Partial submergence of scions in dH2O or CNT dispersions resulted in the transport of microwave absorbers in the xylem tissue via transpiration but did not compromise plant health. The microwave absorbers effectively transferred heat to the scion wood to reach an average temperature range of 55-65°C. Microwave radiation exposure for 6 sec (3 sec for two iterations) of CNT- or dH2O-treated scions reduced the frequency of X. fastidiosa-positive in pecan scions without negatively affecting plant viability when compared to the control group (dH2O-treated with no microwave). The efficacy of the new thermal treatments based on microwave irradiation was comparable to the conventional hot-water treatment (HWT) method, in which scions were submerged in 46°C water for 30 min. Microwave irradiation can be employed to treat X. fastidiosa-infected scions where the conventional HWT treatment is not feasible. This study is the first report to demonstrate novel thermal treatment methods based on the microwave irradiation and microwave absorbers of dH2O and CNT as an application for the phytosanitation of xylem-inhabiting bacteria in graftwood.

Understanding of Lithium Insertion into 3D Porous Carbon Scaffolds with Hybridized Lithiophobic and Lithiophilic Surfaces by In-Operando Study.

In-operando study coupled with voltage/current profiles are presented in order to unveil lithium insertion processes into 3D porous carbon nanotube (CNT) structures whose surfaces were altered to have lithiophobic, lithiophilic, and hybridized lithiophobic/philic characteristics using graphitic surfaces with/without carboxyl/hydroxyl groups. We found the lithiophobic graphitic surfaces hindered lithium insertion into the scaffold despite the high conductivity of CNT. The lithiophilic surface caused another problem of lithium deposition on the outer surface of the electrode, clogging pores and engendering dendrites. Conversely, in the hybridized CNT, lithiophilic trenches partially created on the pristine CNT allowed for uniform lithium deposition into the pores by simultaneously improved lithium attraction and charge transfer, reaching a high areal capacity of 16 mAh cm-2 even with a current density of 8 mA cm-2 without noticeable dendrite formation and volume expansion. Our hybridization approach provides valuable insight to realize a high-energy-density anode by uniformly impregnating lithium into porous media.

Promoting Dual Electronic and Ionic Transport in PEDOT by Embedding Carbon Nanotubes for Large Thermoelectric Responses.

Thermoelectric (TE) energy conversion with nontraditional organic materials is promising in wearable electronics and roll-to-roll manufacturing because of mechanical flexibility, lightweight, and easy processing. Although typical organic materials have a benefit of low thermal conductivity that creates a large temperature gradient, relatively small thermopower (or Seebeck coefficient) often requires copious number of TE legs to fabricate practical TE devices. Here, we show that hybrids of poly(3,4-ethylenedioxythiophene)-tosylate (PEDOT-Tos) and carbon nanotubes (CNTs) can produce extremely large thermopower, ∼14 mV/K at room temperature by a chemical reduction. With decent electrical conductivity, an extraordinary power factor of ∼1200 µW/m K2 at room temperature was observed. The large power factor could be attributed to prominent dual electronic and ionic conduction, which is likely to be promoted by embedding the CNTs in PEDOT  due to the improvement in the carrier mobility, in comparison with the inferior and widely varying  TE properties of PEDOT-only samples in the literature. While a higher CNT concentration gave a larger electronic contribution, a longer reduction or a lower CNT concentration provided a larger ionic contribution. Meanwhile, well-separated CNTs created CNT junctions intervened by PEDOT-Tos, suppressing the thermal transport. Further research utilizing the high TE responses could greatly help to develop practical wearable and/or mass-producible thermal energy harvesting and storage devices.

Clay-Facilitated Aqueous Dispersion of Graphite and Poly(vinyl alcohol) Aerogels Filled with Binary Nanofillers.

Dispersion of graphite in water was achieved using clay as dispersing aid. In the absence of polymer, the clay/graphite suspensions were sufficiently stable to produce aerogels composed of very thin layers of uniformly dispersed nanoparticles. Poly(vinyl alcohol) (PVOH) aerogels containing binary nanofillers (clay plus graphite) were then fabricated and tested. These composites were found to maintain low thermal and electrical conductivities even with high loading of graphite. A unique compressive stress-strain behavior was observed for the aerogel, exhibiting a plateau in the densification region, likely due to sliding between clay and graphite layers within the PVOH matrix. The aerogels containing only graphite exhibited higher compressive modulus, yield stress and toughness values than the samples filled with binary nanofillers. X-ray diffraction (XRD) spectra for the same composite aerogel before and after compression testing illustrated the compression-induced dispersion changes of nanofillers. Composites containing 50 wt % graphite demonstrated a downshift of its 2D Raman peak implying graphite exfoliation to graphene with less than 5 layers.

Novel Organic Schottky Barrier Diode Created in a Single Planar Polymer Film.

An organic Schottky barrier diode is created in a single planar PEDOT:Tos film by treating a half of the PEDOT:Tos film with TDAE vapor. Current is rectified in one direction by the Schottky barrier at the junction. The unique planar structure made of a single film greatly reduces defects, resulting in a remarkably high current density with a high rectification ratio, as well as making it suitable for ink-jet-type or roll-to-roll printing techniques.

Thermal Transport Driven by Extraneous Nanoparticles and Phase Segregation in Nanostructured Mg2(Si,Sn) and Estimation of Optimum Thermoelectric Performance.

Solid solutions of magnesium silicide and magnesium stannide were recently reported to have high thermoelectric figure-of-merits (ZT) due to remarkably low thermal conductivity, which was conjectured to come from phonon scattering by segregated Mg2Si and Mg2Sn phases without detailed study. However, it is essential to identify the main cause for further improving ZT as well as estimating its upper bound. Here we synthesized Mg2(Si,Sn) with nanoparticles and segregated phases, and theoretically analyzed and estimated the thermal conductivity upon segregated fraction and extraneous nanoparticle addition by fitting experimentally obtained thermal conductivity, electrical conductivity, and thermopower. In opposition to the previous speculation that segregated phases intensify phonon scattering, we found that lattice thermal conductivity was increased by the phase segregation, which is difficult to avoid due to the miscibility gap. We selected extraneous TiO2 nanoparticles dissimilar to the host materials as additives to reduce lattice thermal conductivity. Our experimental results showed the maximum ZT was improved from ∼0.9 without the nanoparticles to ∼1.1 with 2 and 5 vol % TiO2 nanoparticles at 550 °C. According to our theoretical analysis, this ZT increase by the nanoparticle addition mainly comes from suppressed lattice thermal conductivity in addition to lower bipolar thermal conductivity at high temperatures. The upper bound of ZT was predicted to be ∼1.8 for the ideal case of no phase segregation and addition of 5 vol % TiO2 nanoparticles. We believe this study offers a new direction toward improved thermoelectric performance of Mg2(Si,Sn).

Thermally Driven Large N-Type Voltage Responses from Hybrids of Carbon Nanotubes and Poly(3,4-ethylenedioxythiophene) with Tetrakis(dimethylamino)ethylene.

Hybrids of carbon nanotubes (CNTs) and poly(3,4-ethylenedioxythiophene) (PEDOT) treated by tetrakis(dimethylamino)ethylene (TDAE) have large n-type voltages in response to temperature differences. The reduced carrier concentration by TDAE reduction and partially percolated CNT networks embedded in the PEDOT matrix result in high thermopower and low thermal conductivity. The high electron mobility in the CNTs helps to minimally reduce the electrical conductivity of the hybrid, resulting in a large figure-of-merit.

Simultaneously improving electrical conductivity and thermopower of polyaniline composites by utilizing carbon nanotubes as high mobility conduits.

Electrical conductivity and thermopower of isotropic materials typically have inversely proportional correlation because both are strongly affected in the opposite way by the electronic carrier concentration. This behavior has been one of the major hurdles in developing high-performance thermoelectrics whose figure-of-merit enhances with large thermopower and high electrical conductivity. Here we report a promising method of simultaneously improving both properties with polyaniline (PANI) composites filled by carbon nanotubes (CNTs). With addition of double-wall CNTs (DWCNTs), the electronic mobility of PANI doped with camphorsulfonic acid (PANI-CSA) was raised from ∼0.15 to ∼7.3 cm(2)/(V s) (∼50 time improvement) while the carrier concentration was decreased from ∼2.1 × 10(21) to ∼5.6 × 10(20) cm(-3) (∼4 time reduction). The larger increase of mobility increased electrical conductivity despite the carrier concentration reduction that enlarges thermopower. The improvement in the carrier mobility could be attributed to the band alignment that attracts hole carriers to CNTs whose mobility is much higher than that of PANI-CSA. The electrical conductivity of the PANI-CSA composites with 30-wt % DWCNTs was measured to be ∼610 S/cm with a thermopower value of ∼61 µV/K at room temperature, resulting in a power factor value of ∼220 µW/(m K(2)), which is more than two orders higher than that of PANI-CSA as well as the highest among those of the previously reported PANI composites. Further study may result in high performance thermoelectric organic composites uniquely offering mechanical flexibility, light weight, low toxicity, and easy manufacturing. unlike conventional inorganic semiconductors.

Completely organic multilayer thin film with thermoelectric power factor rivaling inorganic tellurides.

Composed exclusively of organic components, polyaniline (PANi), graphene, and double-walled nanotubes (DWNTs) are alternately deposited from aqueous solutions using a layer-by-layer assembly. The 40 quadlayer thin film (470 nm thick) exhibits electrical conductivity of 1.08 × 10(5) S m(-1) and a Seebeck coefficient of 130 µV K(-1) , producing a thermoelectric power factor of 1825 µW m(-1) K(-2) .

Liquid-type cathode enabled by 3D sponge-like carbon nanotubes for high energy density and long cycling life of Li-S batteries.

High energy density and long-term stability of Li-S batteries are achieved by employing a 3D sponge-like carbon nanotube cathode and a liquid-type polysulfide catholyte. Carbon nanotubes not only provide excellent electron pathways and polysulfide reservoirs, but they can also be used as a standalone cathode without current collectors, which greatly alleviates problems arising from insulating sulfur and polysulfide shuttles as well as remarkably increasing the energy density.

Flexible power fabrics made of carbon nanotubes for harvesting thermoelectricity.

Thermoelectric energy conversion is very effective in capturing low-grade waste heat to supply electricity particularly to small devices such as sensors, wireless communication units, and wearable electronics. Conventional thermoelectric materials, however, are often inadequately brittle, expensive, toxic, and heavy. We developed both p- and n-type fabric-like flexible lightweight materials by functionalizing the large surfaces and junctions in carbon nanotube (CNT) mats. The poor thermopower and only p-type characteristics of typical CNTs have been converted into both p- and n-type with high thermopower. The changes in the electronic band diagrams of the CNTs were experimentally investigated, elucidating the carrier type and relatively large thermopower values. With our optimized device design to maximally utilize temperature gradients, an electrochromic glucose sensor was successfully operated without batteries or external power supplies, demonstrating self-powering capability. While our fundamental study provides a method of tailoring electronic transport properties, our device-level integration shows the feasibility of harvesting electrical energy by attaching the device to even curved surfaces like human bodies.

Lossless hybridization between photovoltaic and thermoelectric devices.

The optimal hybridization of photovoltaic (PV) and thermoelectric (TE) devices has long been considered ideal for the efficient harnessing solar energy. Our hybrid approach uses full spectrum solar energy via lossless coupling between PV and TE devices while collecting waste energy from thermalization and transmission losses from PV devices. Achieving lossless coupling makes the power output from the hybrid device equal to the sum of the maximum power outputs produced separately from individual PV and TE devices. TE devices need to have low internal resistances enough to convey photo-generated currents without sacrificing the PV fill factor. Concomitantly, a large number of p-n legs are preferred to drive a high Seebeck voltage in TE. Our simple method of attaching a TE device to a PV device has greatly improved the conversion efficiency and power output of the PV device (~30% at a 15°C temperature gradient across a TE device).

N-type thermoelectric performance of functionalized carbon nanotube-filled polymer composites.

Carbon nanotubes (CNTs) were functionalized with polyethyleneimine (PEI) and made into composites with polyvinyl acetate (PVAc). CNTs were dispersed with different amounts of sodium dodecylbenzenesulfonate (SDBS) prior to the PEI functionalization. The resulting samples exhibit air-stable n-type characteristics with electrical conductivities as great as 1500 S/m and thermopowers as large as -100 µV/K. Electrical conductivity and thermopower were strongly affected by CNT dispersion, improving the properties with better dispersion with high concentrations of SDBS. This improvement is believed to be due to the increase in the number of tubes that are evenly coated with PEI in a better-dispersed sample. Increasing the amount of PEI relative to the other constituents positively affects thermopower but not conductivity. Air exposure reduces both thermopower and conductivity presumably due to oxygen doping (which makes CNTs p-type), but stable values were reached within seven days following sample fabrication.

Highly doped carbon nanotubes with gold nanoparticles and their influence on electrical conductivity and thermopower of nanocomposites.

Carbon nanotubes (CNTs) are often used as conductive fillers in composite materials, but electrical conductivity is limited by the maximum filler concentration that is necessary to maintain composite structures. This paper presents further improvement in electrical conductivity by precipitating gold nanoparticles onto CNTs. In our composites, the concentrations of CNTs and poly (vinyl acetate) were respectively 60 and 10 vol%. Four different gold concentrations, 0, 10, 15, or 20 vol% were used to compare the influence of the gold precipitation on electrical conductivity and thermopower of the composites. The remaining portion was occupied by poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate), which de-bundled and stabilized CNTs in water during synthesis processes. The concentrations of gold nanoparticles are below the percolation threshold of similar composites. However, with 15-vol% gold, the electrical conductivity of our composites was as high as ∼6×10(5) S/m, which is at least ∼500% higher than those of similar composites as well as orders of magnitude higher than those of other polymer composites containing CNTs and gold particles. According to our analysis with a variable range hopping model, the high conductivity can be attributed to gold doping on CNT networks. Additionally, the electrical properties of composites made of different types of CNTs were also compared.

Enhanced overcharge performance of nano-LiCoO2 by novel Li3VO4 surface coatings.

LiCoO(2) nanoparticles were coated with 3.4 and 5.5 wt% of lithium vanadate (Li(3)VO(4)) by a wet-chemical and sintering method. When the electrode containing 5.5-wt% Li(3)VO(4)-coated LiCoO(2) was overcharged to 4.5 V at a current of 30 mA g(-1) (∼0.2 C), ∼85% of the initial discharge capacity after 100 charge-discharge cycles was maintained, compared to only ∼67% for the electrode with bare LiCoO(2) nanoparticles. The electrode with 5.5 wt% coating can also deliver 115 mA h g(-1) discharge capacity at a current of 1200 mA g(-1) (∼8 C) and a discharge-charge voltage of 4.5 V, which is twice the capacity of the bare LiCoO(2) sample. The improvement of overcharge cyclability and high-rate capability was believed to be due to the structurally protective Li(3)VO(4) surface coating with good Li-ion conductivity.