Mehmet Karakaya

Defect-Engineered Graphene for High-Energy- and High-Power-Density Supercapacitor Devices

Defects are often written off as performance limiters. Contrary to this notion, it is shown that controlling the defect configuration in graphene is critical to overcome a fundamental limitation posed by quantum capacitance and opens new channels for ion diffusion. Defect-engineered graphene flexible pouch capacitors with energy densities of 500% higher than the state-of-the-art supercapacitors are demonstrated.The development of high-energy and high-power density supercapacitors (SCs) is critical for enabling next-generation energy storage applications. Nanocarbons are excellent SC electrode materials due to their economic viability, high-surface area, and high stability. Although nanocarbons have high theoretical surface area and hence high double layer capacitance, the net amount of energy stored in nanocarbon-SCs is much below theoretical limits due to two inherent bottlenecks: i) their low quantum capacitance and ii) limited ion-accessible surface area. Here, we demonstrate that defects in graphene could be effectively used to mitigate these bottlenecks by drastically increasing the quantum capacitance and opening new channels to facilitate ion diffusion in otherwise closed interlayer spaces. Our results support the emergence of a new energy paradigm in SCs with 250% enhancement in double layer capacitance beyond the theoretical limit. Furthermore, we demonstrate prototype defect engineered bulk SC devices with energy densities 500% higher than state-of-the-art commercial SCs without compromising the power density.

Preferential Scattering by Interfacial Charged Defects for Enhanced Thermoelectric Performance in Few-layered n-type Bi2Te3

Over the past two decades several nano-structuring methods have helped improve the figure of merit (ZT) in the state-of-the art bulk thermoelectric materials. While these methods could enhance the thermoelectric performance of p-type Bi2Te3, it was frustrating to researchers that they proved ineffective for n-type Bi2Te3 due to the inevitable deterioration of its thermoelectric properties in the basal plane. Here, we describe a novel chemical-exfoliation spark-plasma-sintering (CE-SPS) nano-structuring process, which transforms the microstructure of n-type Bi2Te3 in an extraordinary manner without compromising its basal plane properties. The CE-SPS processing leads to preferential scattering of electrons at charged grain boundaries, and thereby increases the electrical conductivity despite the presence of numerous grain boundaries, and mitigates the bipolar effect via band occupancy optimization leading to an upshift (by ~ 100 K) and stabilization of the ZT peak over a broad temperature range of ~ 150 K.

Roll-to-roll production of spray coated N-doped carbon nanotube electrodes for supercapacitors

Although carbon nanomaterials are being increasingly used in energy storage, there has been a lack of inexpensive, continuous, and scalable synthesis methods. Here, we present a scalable roll-to-roll (R2R) spray coating process for synthesizing randomly oriented multi-walled carbon nanotubes electrodes on Al foils. The coin and jellyroll type supercapacitors comprised such electrodes yield high power densities (∼700 mW/cm3) and energy densities (1 mW h/cm3) on par with Li-ion thin film batteries. These devices exhibit excellent cycle stability with no loss in performance over more than a thousand cycles. Our cost analysis shows that the R2R spray coating process can produce supercapacitors with 10 times the energy density of conventional activated carbon devices at ∼17% lower cost.

Dopant-configuration controlled carrier scattering in graphene

Controlling optical and electronic properties of graphene via substitutional doping is central to many fascinating applications. Doping graphene with boron (B) or nitrogen (N) has led to p- or n-type graphene; however, the electron mobility in doped-graphene is severely compromised due to increased electron-defect scattering. Here, we demonstrate through Raman spectroscopy, nonlinear optical and ultrafast spectroscopy, and density functional theory that the graphitic dopant configuration is stable in graphene and does not significantly alter electron–electron or electron–phonon scattering, that is otherwise present in doped graphene, by preserving the crystal coherence length (La).

Influence of carbon nanomaterial defects on the formation of protein corona

In any physiological media, carbon nanomaterials (CNM) strongly interact with biomolecules leading to the formation of biocorona, which subsequently dictate the physiological response and the fate of CNMs. Defects in CNMs play an important role not only in material properties but also in the determination of how materials interact at the nano-bio interface. In this article, we probed the influence of defect-induced hydrophilicity on the biocorona formation using micro-Raman, photoluminescence, infrared spectroscopy, electrochemistry, and molecular dynamics simulations. Our results show that the interaction of proteins (albumin and fibrinogen) with CNMs is strongly influenced by charge-transfer between them, inducing protein unfolding which enhances conformational entropy and higher protein adsorption.

Anomalous impact and strain responses in helical carbon nanotube foams

We describe the quasistatic and dynamic response of helical carbon nanotube (HCNT) foams in compression. Similarly to other CNT foams, HCNT foams exhibit preconditioning effects in response to cyclic loading; however, their fundamental deformation mechanisms are unique. In quasistatic compression, HCNT foams exhibit strain localization and collective structural buckling, nucleating at different weak sections throughout their thickness. In dynamic compression, they undergo progressive crushing, governed by the intrinsic density gradient along the thickness of the sample. HCNT micro-bundles often undergo brittle fracture that originates from nanoscale defects. Regardless of this microstructural damage, bulk HCNT foams exhibit super-compressibility and recover more than 90% of large compressive strains (up to 80%). When subjected to striker impacts, HCNT foams mitigate impact stresses more effectively compared to other CNT foams comprised of non-helical CNTs (∼50% improvement). The unique mechanical properties we revealed demonstrate that the HCNT foams are ideally suited for applications in packaging, impact protection, and vibration mitigation.

Tuning the electronic structure of graphene through nitrogen doping: experiment and theory

Tuning the electronic properties of graphene by doping atoms into its lattice makes it more applicable for electronic devices. We present a study of nitrogen doped graphene samples grown using chemical vapor deposition with a variety of synthesis conditions. Soft X-ray absorption and emission spectroscopy, which are techniques sensitive to the unoccupied and occupied partial electronic density of states, respectively, were used to study the electronic structure of N-doped graphene. Complementary full-potential, all-electron density functional theory calculations of the measured spectra reveal the existence of graphitic, pyridinic and nitrilic-like sites in the samples studied. Although our study shows that the defect type is sensitively related to the synthesis conditions, the graphitic configuration is found to be the most dominant one in each system studied. The dependence of the defect type on the sample growth conditions and the corresponding shifts in the Fermi energy level from the Dirac point, result in n- or p-type material being obtained.

Impact absorption properties of carbon fiber reinforced bucky sponges

We describe the super compressible and highly recoverable response of bucky sponges as they are struck by a heavy flat-punch striker. The bucky sponges studied here are structurally stable, self-assembled mixtures of multiwalled carbon nanotubes (MWCNTs) and carbon fibers (CFs). We engineered the microstructure of the sponges by controlling their porosity using different CF contents. Their mechanical properties and energy dissipation characteristics during impact loading are presented as a function of their composition. The inclusion of CFs improves the impact force damping by up to 50% and the specific damping capacity by up to 7% compared to bucky sponges without CFs. The sponges also exhibit significantly better stress mitigation characteristics compared to vertically aligned CNT foams of similar densities. We show that delamination occurs at the MWCNT-CF interfaces during unloading, and it arises from the heterogeneous fibrous microstructure of the bucky sponges.

Polymer-Derived Silicon Oxycarbide Ceramics as Promising Next-Generation Sustainable Thermoelectrics

We demonstrate the potential of polymer-derived ceramics (PDC) as next-generation sustainable thermoelectrics. Thermoelectric behavior of polymer-derived silicon oxycarbide (SiOC) ceramics (containing hexagonal boron nitride (h-BN) as filler) was studied as a function of measurement temperature. SiOC, sintered at 1300 °C exhibited invariant low thermal conductivity (∼1.5 W/(m·K)) over 30-600 °C, coupled with a small increase in both Seebeck coefficient and electrical conductivity, with increase in measurement temperature (30-150 °C). SiOC ceramics containing 1 wt % h-BN showed the highest Seebeck coefficient (-33 μV/K) for any PDC thus far.

A micro-Raman study of exfoliated few-layered n -type Bi 2 Te 2.7 Se 0.3

Previously we showed that the thermoelectric (TE) performance of bulk n-type Bi2Te2.7Se0.3 can be enhanced by subjecting it to a combined process of chemical or mechanical exfoliation (C/ME) followed by a rapid densification and restacking of the exfoliated layers via the spark-plasma-sintering technique (SPS). Here, we present a systematic micro-Raman study of two-dimensional flakes of n-type Bi2Te2.7Se0.3 produced by the C/ME process, as a function of the flake thickness. We found Raman evidence for flakes with: (i) integer number of quintuples which exhibited a strong electron-phonon coupling, and (ii) non-integer number of quintuples, or sub-quintuples which exhibited the forbidden IR active mode due to symmetry lowering. Detailed atomic force microscopy was used to confirm the number of quintuples in all flakes examined in this study. The restacking and densification of these flakes by SPS promoted the formation of charged grain boundaries, which led to the enhanced TE properties via the energy filtering process.