117 research outputs found
Porous Graphene-like Carbon from Fast Catalytic Decomposition of Biomass for Energy Storage Applications
A novel carbon material made of porous graphene-like nanosheets was synthesized from biomass resources by a simple catalytic graphitization process using nickel as a catalyst for applications in electrodes for energy storage devices. A recycled fiberboard precursor was impregnated with saturated nickel nitrate followed by high-temperature pyrolysis. The highly exothermic combustion of in situ formed nitrocellulose produces the expansion of the cellulose fibers and the reorganization of the carbon structure into a three-dimensional (3D) porous assembly of thin carbon nanosheets. After acid washing, nickel particles are fully removed, leaving nanosized holes in the wrinkled graphene-like sheets. These nanoholes confer the resulting carbon material with ≈75% capacitance retention, when applied as a supercapacitor electrode in aqueous media at a specific current of 100 A·g–1 compared to the capacitance reached at 20 mA·g–1, and ≈35% capacity retention, when applied as a negative electrode for lithium-ion battery cells at a specific current of 3720 mA·g–1 compared to the specific capacity at 37.2 mA·g–1. These findings suggest a novel way for synthesizing 3D nanocarbon networks from a cellulosic precursor requiring low temperatures and being amenable to large-scale production while using a sustainable starting precursor such as recycled fiberwood.Spanish Government Agency Ministerio de Economí a y Competitividad (MINECO) (grant number MAT2016-76526-R)
Regularization of the big bang singularity with random perturbations
We show how to regularize the big bang singularity in the presence of random
perturbations modeled by Brownian motion using stochastic methods. We prove
that the physical variables in a contracting universe dominated by a scalar
field can be continuously and uniquely extended through the big bang as a
function of time to an expanding universe only for a discrete set of values of
the equation of state satisfying special co-prime number conditions. This
result significantly generalizes a previous result \cite{Xue:2014} that did not
model random perturbations. This result implies that the extension from a
contracting to an expanding universe for the discrete set of co-prime equation
of state is robust, which is a surprising result. Implications for a purely
expanding universe are discussed, such as a non-smooth, randomly varying scale
factor near the big bang.Comment: 21 pages, 4 figure
Enabling Aqueous Processing of Ni‐Rich Layered Oxide Cathode Materials by Addition of Lithium Sulfate
Aqueous processing of Ni-rich layered oxide cathode materials is a promising approach to simultaneously decrease electrode manufacturing costs, while bringing environmental benefits by substituting the state-of-the-art (often toxic and costly) organic processing solvents. However, an aqueous environment remains challenging due to the high reactivity of Ni-rich layered oxides towards moisture, leading to lithium leaching and Al current collector corrosion because of the resulting high pH value of the aqueous electrode paste. Herein, a facile method was developed to enable aqueous processing of LiNi0.8Co0.1Mn0.1O2 (NCM811) by the addition of lithium sulfate (Li2SO4) during electrode paste dispersion. The aqueously processed electrodes retained 80 % of their initial capacity after 400 cycles in NCM811||graphite full cells, while electrodes processed without the addition of Li2SO4 reached 80 % of their capacity after only 200 cycles. Furthermore, with regard to electrochemical performance, aqueously processed electrodes using carbon-coated Al current collector outperformed reference electrodes based on state-of-the-art production processes involving N-methyl-2-pyrrolidone as processing solvent and fluorinated binders. The positive impact on cycle life by the addition of Li2SO4 stemmed from a formed sulfate coating as well as different surface species, protecting the NCM811 surface against degradation. Results reported herein open a new avenue for the processing of Ni-rich NCM electrodes using more sustainable aqueous routes.European Union
http://dx.doi.org/10.13039/501100000780European Union's Horizon 2020 research and innovation programPeer Reviewe
Synthesis and Comparative Investigation of Silicon Transition Metal Silicide Composite Anodes for Lithium Ion Batteries
A significant increase in energy density of lithium ion batteries (LIBs) can be achieved by using high‐capacity, silicon (Si)‐based negative electrode materials. Several challenges arise from the enormous volumetric changes of Si during lithiation/delithiation, such as disintegration/pulverization of the active material and the electrode as well as ongoing electrolyte decomposition, leading to rapid capacity fading. Here, we synthesize and comparatively investigate three different porous transition metal‐Si‐carbon composite materials that are composed of an active Si phase and the corresponding inactive metal‐silicide phases. In this material design, the inactive phases, as well as the pores serve as a buffer to attenuate the previously mentioned detrimental effects. The synthesized materials are studied with respect to their structural and surface properties and are characterized electrochemically regarding their rate performance, and long‐term charge/discharge cycling stability. Thereby, the composite materials show a promising rate capability and a high specific capacity. Their low initial Coulombic efficiency, due to the porous structure, can be partially compensated by pre‐lithiation. This is demonstrated by the application of the synthesized materials in a LIB full‐cell set‐up vs. NMC‐111 cathodes, where the amount of lithium is confined due to anode/cathode capacity balancing
New insights into the uptake/release of FTFSI − anions into graphite by means of in situ powder X-ray diffraction
The redox-amphoteric character of graphite enables its utilization as intercalation host for various types of cations and anions to form either donor-type or acceptor-type graphite intercalation compounds (GICs), respectively. While the donor-type GIC LiC6 is commonly used in the field of lithium ion batteries, acceptor-type GICs were suggested for application in dual-ion cells. In this contribution, the electrochemical intercalation/de-intercalation of fluorosulfonyl-(trifluoromethanesulfonyl) imide (FTFSI−) anions into graphite was studied for dual-ion cells during a cyclic voltammetry experiment using in situ powder X-ray diffraction. For the GICs, a series of most dominant stages could be assigned and the periodic repeat distance as well as the FTFSI− gallery height/gallery expansion were determined. The obtained dominant stage numbers of the formed GICs were correlated to cell voltage ranges. Upon charge, a transition of the different stages was observed, while upon discharge stage 1 was still preserved for a broad voltage range. These novel findings indicate different mechanisms for the uptake and release of the anions
Lithium ion, lithium metal, and alternative rechargeable battery technologies: the odyssey for high energy density
Since their market introduction in 1991, lithium ion batteries (LIBs) have developed evolutionary in terms of their specific energies (Wh/kg) and energy densities (Wh/L). Currently, they do not only dominate the small format battery market for portable electronic devices, but have also been successfully implemented as the technology of choice for electromobility as well as for stationary energy storage. Besides LIBs, a variety of different technologically promising battery concepts exists that, depending on the respective technology, might also be suitable for various application purposes. These systems of the “next generation,” the so-called post-lithium ion batteries (PLIBs), such as metal/sulfur, metal/air or metal/oxygen, or “post-lithium technologies” (systems without Li), which are based on alternative single (Na+, K+) or multivalent ions (Mg2+, Ca2+), are currently being studied intensively. From today’s point of view, it seems quite clear that there will not only be a single technology for all applications (technology monopoly), but different battery systems, which can be especially suitable or combined for a particular application (technology diversity). In this review, we place the lithium ion technology in a historical context and give insights into the battery technology diversity that evolved during the past decades and which will, in turn, influence future research and development
Running out of lithium? A route to differentiate between capacity losses and active lithium losses in lithium-ion batteries
Active lithium loss (ALL) resulting in a capacity loss (QALL), which is caused by lithium consuming parasitic reactions like SEI formation, is a major reason for capacity fading and, thus, for a reduction of the usable energy density of lithium-ion batteries (LIBs). QALL is often equated with the accumulated irreversible capacity (QAIC). However, QAIC is also influenced by non-lithium consuming parasitic reactions, which do not reduce the active lithium content of the cell, but induce a parasitic current. In this work, a novel approach is proposed in order to differentiate between QAIC and QALL. The determination of QALL is based on the remaining active lithium content of a given cell, which can be determined by de-lithiation of the cathode with the help of the reference electrode of a three-electrode set-up. Lithium non-consuming parasitic reactions, which do not influence the active lithium content have no influence on this determination. In order to evaluate this novel approach, three different anode materials (graphite, carbon spheres and a silicon/graphite composite) were investigated. It is shown that during the first charge/discharge cycles QALL is described moderately well by QAIC. However, the difference between QAIC and QALL rises with increasing cycle number. With this approach, a differentiation between “simple” irreversible capacities and truly detrimental “active Li losses” is possible and, thus, Coulombic efficiency can be directly related to the remaining useable cell capacity for the first time. Overall, the exact determination of the remaining active lithium content of the cell is of great importance, because it allows a statement on whether the reduction in lithium content is crucial for capacity fading or whether the fading is related to other degradation mechanisms such as material or electrode failure
Toward High Power Batteries: Pre-lithiated Carbon Nanospheres as High Rate Anode Material for Lithium Ion Batteries
In this work, carbon nanospheres (CS) are prepared by hydrothermal synthesis using glucose as precursor, followed by a subsequent carbonization step. By variation of the synthesis parameters, CS particles with different particle sizes are obtained. With particular focus on the fast charging capability, the electrochemical performance of CS as anode material in lithium ion batteries (LIBs) is investigated, including the influence of particle size and carbonization temperature. It is shown that CS possess an extraordinary good long-term cycling stability and a very good rate capability (up to 20C charge/discharge rate) at operating temperatures of 20 and 0 °C compared to graphitic carbon and Li4Ti5O12 (LTO)-based anodes. One major disadvantage of CS is the very low first cycle Coulombic efficiency (Ceff) and the related high active lithium loss, which prevents usage of CS within LIB full cells. Nevertheless, in order to overcome this problem, we performed electrochemical pre-lithiation, which significantly improves the first cycle Ceff and enables usage of CS within LIB full cells (vs NMC-111), which is shown here for the first time. The improved rate capability of CS is also verified in electrochemically pre-lithiated NMC-based LIB full cells, in comparison to graphite and LTO anodes. Further, CS also display an improved specific energy (at ≥5C), energy efficiency (at ≥2C), and energy retention (at ≥2C) compared to graphite and LTO-based LIB full cells
Enabling bis(fluorosulfonyl)imide-based ionic liquid electrolytes for application in dual-ion batteries
In this work, we present a comprehensive study on the effect of adding different conductive salt additives including LiPF6, LiBF4 and LiDFOB, as well as the fluorinated solvent additive methyl difluoroacetate (MDFA) to a bis(fluorosulfonyl)imide (FSI)-based ionic liquid (IL) electrolyte, i.e. Pyr14FSI/LiFSI, to protect the Al current collector (ACC) from anodic dissolution and, thus, enable reversible charge/discharge cycling in a high performance dual-ion cell. Chronocoulometry and scanning electron microscopy measurements were conducted to evaluate the specific ACC passivation ability of each electrolyte. Furthermore, the influence of these additives on anion intercalation behavior into the graphite positive electrode with special emphasis on the Coulombic efficiency (CE), reversible capacity, as well as capacity retention is presented. Overall, we can show that the addition of small amounts of LiPF6, LiBF4 and MDFA (0.5 wt%) into the FSI-based IL electrolyte significantly increases the overall cell performance, whereas LiDFOB as electrolyte additive deteriorates the dual-ion cell performance. In addition, an excellent cycling performance for 1000 cycles is obtained for the Pyr14FSI electrolyte having 5 wt% LiPF6, displaying an average reversible capacity of 40 mAh g−1, a CE exceeding 98% and a capacity retention of 91%, which has not been reported so far
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