| 1. |
- Abbasi, M., et al.
(författare)
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Fabrication of Spin-Coated Ti/TiHx/Ni-Sb-SnO2 Electrode : Stability and Electrocatalytic Activity
- 2018
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Ingår i: Journal of the Electrochemical Society. - : ELECTROCHEMICAL SOC INC. - 0013-4651 .- 1945-7111. ; 165:9, s. H568-H574
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Tidskriftsartikel (refereegranskat)abstract
- A novel three-layer anode having the composition Ti/TiHx/Ni-Sb-SnO2 (Ti/TiHx/NATO) was successfully prepared by a spin-coating and pyrolysis process aiming at a long service lifetime and good electrocatalytic properties for ozone formation. The TiHx as an interlayer was produced by electrochemical cathodic reduction of a coated layer of the TiOx on the titanium substrate. Spin coating and thermal decomposition were used to deposit the Sn-Sb-Ni precursor on the surface of the prepared Ti/TiHx electrode. Cyclic and linear scanning voltammetry, Raman spectroscopy, scanning electron microscopy (SEM) and X-ray diffraction (XRD) were used to reveal the electrode performance and morphology. Results show that the onset potential for the oxygen evolution reaction (OER) of Ti/TiHx /NATO is higher than for Ti/NATO. They also indicate that the service lifetime of the Ti/TiHx/NATO is twice as long as the Ti/NATO at a current density of 50 mA.cm(-2) at room temperature. Electrochemical ozone generation and degradation of the methylene blue were investigated to confirm selectivity and activity of the electrodes. After 5 min electrolysis, a current efficiency for ozone generation of 56% was obtained the electrode with TiHx while 38% was obtained on Ti/NATO under same conditions. The results also confirm that the Ti/TiH x /NATO has a higher kinetic rate constant and decolorization efficiency for removal of the methylene blue compare to the Ti/NATO. The rate constant for the pseudo-first ordered reaction of methylene blue degradation showed high values of 350 x 10(-3) min(-1) for Ti/NATO and 440 x 10(-3) min(-1) for Ti/TiHx/NATO.
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| 2. |
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| 3. |
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| 4. |
- Endrodi, Balazs, et al.
(författare)
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A review of chromium(VI) use in chlorate electrolysis : Functions, challenges and suggested alternatives
- 2017
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Ingår i: Electrochimica Acta. - : PERGAMON-ELSEVIER SCIENCE LTD. - 0013-4686 .- 1873-3859. ; 234, s. 108-122
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Forskningsöversikt (refereegranskat)abstract
- Sodium chlorate is industrially produced by electrolysis of an aqueous salt solution, in which chromium ( VI) constitutes an important excipient component. It is added to a concentration of a few grams Na2Cr2O7/ liter to the electrolyte and has several functions in the process, the most important being to increase the Faradaic efficiency for hydrogen evolution in the undivided electrochemical cells. A thin film of Cr(OH)(3) x nH(2)O formed by reductive deposition on the cathodes decreases the rate of unwanted side reactions, while still enabling hydrogen evolution to occur. In addition chromium(VI) buffers the electrolyte at the optimum pH for operation and promotes the desired homogeneous reactions in the electrolyte bulk. Chromium species also affect the rates of hydrogen and oxygen evolution at the electrodes and are said to protect the steel cathodes from corrosion. Although chromium(VI) stays in a closed loop during chlorate production, chromate is a highly toxic compound and new REACH legislation therefore intends to phase out its use in Europe from 2017. A production without chromium(VI), with no other process modifications is not possible, and today there are no commercially available alternatives to its addition. Thus, there is an urgent need for European chlorate producers to find solutions to this problem. It is expected that chromium-free production will be a requirement also in other parts of the world, following the European example. As the chromium(VI) addition affects the chlorate process in many ways its replacement might require a combination of solutions targeting each function separately. The aim of this paper is to explain the role and importance of chromium(VI) in the chlorate manufacturing process. Previous achievements in its replacement are summarized and critically evaluated to expose the current state of the field, and to highlight the most promising avenues to be followed. An attempt is also made to reveal connections with other research fields (e.g. photochemical water splitting, corrosion science) facing similar problems. Allied effort of these different communities is expected to open up research avenues to the mutual benefit of these fields.
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| 5. |
- Endrodi, Balazs, et al.
(författare)
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In situ formed vanadium-oxide cathode coatings for selective hydrogen production
- 2019
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Ingår i: Applied Catalysis B. - : Elsevier. - 0926-3373 .- 1873-3883. ; 244, s. 233-239
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Tidskriftsartikel (refereegranskat)abstract
- Electrode selectivity towards hydrogen production is essential in various conversion technologies for renewable energy, as well as in different industrial processes, such as the electrochemical production of sodium chlorate. In this study we present sodium metavanadate as a solution additive, inducing selective cathodic formation of hydrogen in the presence of various other reducible species such as hypochlorite, chlorate, oxygen, nitrate, hydrogen-peroxide and ferricyanide. During electrolysis a vanadium-oxide coating forms from the reduction of sodium metavanadate, explaining the observed enhanced selectivity. The hydrogen evolution reaction proceeds without significantly altered kinetics on such in situ modified electrode surfaces. This suggests that the reaction takes place at the interface between the electrode surface and the protective film, which acts as a diffusion barrier preventing the unwanted species to reach the electrode surface.
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| 6. |
- Endrodi, Balazs, et al.
(författare)
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Selective Hydrogen Evolution on Manganese Oxide Coated Electrodes : New Cathodes for Sodium Chlorate Production
- 2019
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Ingår i: ACS Sustainable Chemistry and Engineering. - : American Chemical Society (ACS). - 2168-0485. ; 7:14, s. 12170-12178
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Tidskriftsartikel (refereegranskat)abstract
- The safety and feasibility of industrial electrochemical production of sodium chlorate, an important chemical in the pulp and paper industry, depend on the selectivity of the electrode processes. The cathodic reduction of anodic products is sufficiently suppressed in the current technology by the addition of chromium(VI) to the electrolyte, but due to the high toxicity of these compounds, alternative pathways are required to maintain high process efficiency. In this paper, we evaluate the electrochemical hydrogen evolution reaction kinetics and selectivity on thermally formed manganese oxide-coated titanium electrodes in hypochlorite and chlorate solutions. The morphology and phase composition of manganese oxide layers were varied via alteration of the annealing temperature during synthesis, as confirmed by scanning electron microscopy, X-ray diffraction, synchrotron radiation X-ray photoelectron spectroscopy, and near-edge X-ray absorption fine structure spectroscopy measurements. As shown in mass spectroscopy coupled electrochemical measurements, the hydrogen evolution selectivity in hypochlorite and chlorate solutions is dictated by the phase composition of the coating. Importantly, a hydrogen evolution efficiency of above 95% was achieved with electrodes of optimized composition (annealing temperature, thickness) in hypochlorite solutions. Further, these electrode coatings are nontoxic and Earth-abundant, offering the possibility of a more sustainable chlorate production.
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| 7. |
- Endrodi, Balázs, et al.
(författare)
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Suppressed oxygen evolution during chlorateformation from hypochlorite in the presenceof chromium(VI)
- 2019
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Ingår i: Journal of chemical technology and biotechnology (1986). - : Wiley. - 0268-2575 .- 1097-4660. ; 94:5, s. 1520-1527
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Tidskriftsartikel (refereegranskat)abstract
- BACKGROUND: Chromium(VI) is a crucial electrolyte component in industrial chlorate production. Due to its toxicity, iturgently needs to be abandoned and its functions fulfilled by new solutions. In the industrial production of sodium chlorate,homogeneous decomposition of the hypochlorite intermediate to chlorate is a key step. As a competing loss reaction,hypochlorite can decompose to oxygen. How chromium(VI) affects these reactions is not well understood.RESULTS: This work shows, for the first time, that chromium(VI) selectively accelerates the chlorate formation from hypochloriteboth in dilute and concentrated, industrially relevant solutions. The effect of the ionic strength and the specific contributionof different electrolyte components were systematically studied. By simultaneously measuring the concentration decayof hypochlorite (UV–vis spectroscopy) and the oxygen formation (mass spectrometry), both the rate and the selectivity of thereactions were evaluated.CONCLUSION: In the presence of chromium(VI) the hypochlorite decomposition is described by the sum of an uncatalyzedand a parallel catalyzed reaction, where oxygen only forms in the uncatalyzed reaction. When removing chromium(VI),the homogeneous oxygen formation increases, causing economic and safety concerns. The need for a catalyst selectivefor chlorate formation is emphasized.
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| 8. |
- Endrődi, Balázs, et al.
(författare)
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Towards sustainable chlorate production : The effect of permanganate addition on current efficiency
- 2018
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Ingår i: Journal of Cleaner Production. - : Elsevier. - 0959-6526 .- 1879-1786. ; 182, s. 529-537
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Tidskriftsartikel (refereegranskat)abstract
- Sodium dichromate is an essential solution additive for the electrocatalytic production of sodium chlorate, assuring selective hydrogen evolution. Unfortunately, the serious environmental and health concerns related to hexavalent chromium mean there is an urgent need to find an alternative solution to achieve the required selectivity. In this study sodium permanganate is evaluated as a possible alternative to chromate, with positive results. The permanganate additive is stable in hypochlorite-containing solutions, and during electrolysis a thin film is reductively deposited on the cathode. The deposit is identified as amorphous manganese oxide by Raman spectroscopic and X-ray diffraction studies. Using different electrochemical techniques (potentiodynamic measurements, galvanostatic polarization curves) we demonstrate that the reduction of hypochlorite is suppressed, while the hydrogen evolution reaction can still proceed. In addition, the formed manganese oxide film acts as a barrier for the reduction of dissolved oxygen. The extent of hydrogen evolution selectivity in hypochlorite solutions was quantified in an undivided electrochemical cell using mass spectrometry. The cathodic current efficiency is significantly enhanced after the addition of permanganate, while the effect on the anodic selectivity and the decomposition of hypochlorite in solution is negligible. Importantly, similar results were obtained using electrodes with manganese oxide films formed ex situ. In conclusion, manganese oxides show great promise in inducing selective hydrogen evolution, and may open new research avenues to the rational design of selective cathodes, both for the chlorate process and for related processes such as photocatalytic water splitting.
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| 9. |
- Huiran, Lu, 1989-
(författare)
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Wood-based Materials for Lithium-ion Batteries
- 2017
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Lithium-ion batteries (LIB) have become very important recently as power sources for portable electronics and electric vehicles. Today non-renewable petroleum-based polymers are used as binders in state-of-the-art LIB. Therefore, it is essential to investigate alternative binders, which are environmentally friendly and inexpensive. Using wood-based materials, such as cellulose and lignin, could make the batteries more environmentally benign, cheaper and easier to produce.Lignin, a byproduct from the pulping industry and the second most abundant bio-polymer in wood, has been investigated for the first time as binder material for eco-friendly LIB. Both LiFePO4 (LFP) positive and graphite negative electrodes using pretreated lignin as binder exhibited good electrochemical performance. The drawback of lignin as binder is that its poor mechanical properties limit the preparation of a thick electrode, constraining the energy density for LIB.In order to meet the demands of flexible and bendable electronic devices, cellulose nanofibrils (CNF) as binder materials have been successfully fabricated for flexible batteries by a water-based paper making process. It showed excellent binding properties for different kinds of electrode materials, which were homogenously dispersed in its visible network. The flexible electrodes obtained good mechanical and electrochemical properties. A study of different CNF shows that the manufacturing process affects the performance of the electrodes.Another innovative LIB concept in this thesis was to build both lightweight and bendable LIB. Chopped carbon fibers (CF), bound by CNF, were demonstrated as both current collector and as a current collector-free negative electrode, produced by an easy filtration process. The gravimetric energy density was increased compared to cells with metallic current collectors. The CF-based lightweight and flexible electrode achieved a good cycling stability, rate capability, even after 4000 times of bending.
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| 10. |
- Karlsson, Rasmus K. B., et al.
(författare)
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Selectivity between Oxygen and Chlorine Evolution in the Chlor-Alkali and Chlorate Processes
- 2016
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Ingår i: Chemical Reviews. - : American Chemical Society (ACS). - 0009-2665 .- 1520-6890. ; 116:5, s. 2982-3028
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Forskningsöversikt (refereegranskat)abstract
- Chlorine gas and sodium chlorate are two base chemicals produced through electrolysis of sodium chloride brine which find uses, in many areas of industrial chemistry. Although the industrial production of these chemicals started over 100 years ago, there are still factors that limit the energy efficiencies of the processes. This review focuses on the unwanted production of oxygen gas, which decreases the charge yield by up to 5%. Understanding the factors that control the rate of oxygen production requires understanding of both chemical reactions occurring in the electrolyte, as well as surface reactions occurring on the anodes. The dominant anode material used in chlorate and chlor-alkali production is the dimensionally stable anode (DSA), Ti coated by a mixed oxide of RuO2 and TiO2. Although the selectivity for chlorine evolution on DSA is high, the fundamental reasons for this high selectivity are just now becoming elucidated. This review summarizes the research, since the early 1900s until today, concerning the selectivity between chlorine and oxygen evolution in chlorate and chlor-alkali production. It covers experimental as well as theoretical studies and highlights the relationships between process conditions, electrolyte composition, the material properties of the anode, and the selectivity for oxygen formation.
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| 11. |
- Karlsson, Rasmus K. B., et al.
(författare)
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Structural Changes in RuO2 during Electrochemical Hydrogen Evolution
- 2016
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Ingår i: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 120:13, s. 7094-7102
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Tidskriftsartikel (refereegranskat)abstract
- A comprehensive theoretical study of the X-ray photoelectron shifts for RuO2 during hydrogen evolution has been performed. The shifts have been calculated using first-principles density functional theory and are compared with previous theoretical and experimental results to reconsider the proposed structural changes occurring during hydrogen evolution on RuO2. We find that during hydrogen evolution hydrogen enters the rutile RuO2 lattice and converts oxygen groups into hydroxyl groups and that this process explains the experimentally observed increase in unit cell dimensions as well as observed chemical shifts. Furthermore, carbon contamination is the most likely explanation for a set of peaks previously identified as caused by a new RuO(OH)2 phase. We find that formation of metallic Ru is just one possible explanation for another peak in the X-ray photoelectron spectrum and that explanations including conversion of RuO2 into Ru(OH)3, or removal of oxygen from Ru active surface sites, also can explain the observed shifts. (Figure Presented)
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| 12. |
- Karlsson, Rasmus K. B., et al.
(författare)
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The electrocatalytic properties of doped TiO2
- 2015
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Ingår i: Electrochimica Acta. - : PERGAMON-ELSEVIER SCIENCE LTD. - 0013-4686 .- 1873-3859. ; 180, s. 514-527
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Tidskriftsartikel (refereegranskat)abstract
- To rationally control the catalytic properties of heterogeneous catalysts is the goal in heterogeneous (electro)catalysis research. Recent developments of theoretical methods based on density functional theory have enabled computational screening of catalysts, to achieve fundamental understanding of which catalyst is optimal for a certain reaction. In the present work, such screening is employed to elucidate the electrocatalytic properties of doped rutile TiO2. Electrodes based on this material are widely used in industrial production of, e.g., chlorine and sodium chlorate. The screening covers 38 different dopants, including all fourth, fifth and sixth row transition metals. Several dopants are predicted to activate TiO2, resulting in a material optimal either for the oxygen evolution reaction, or for selective chlorine evolution. The results can serve as a map for the rational design of electrocatalysts based on TiO2.
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| 13. |
- Karlsson, Rasmus, 1987-
(författare)
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Theoretical and Experimental Studies of Electrode and Electrolyte Processes in Industrial Electrosynthesis
- 2015
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Heterogeneous electrocatalysis is the usage of solid materials to decrease the amount of energy needed to produce chemicals using electricity. It is of core importance for modern life, as it enables production of chemicals, such as chlorine gas and sodium chlorate, needed for e.g. materials and pharmaceuticals production. Furthermore, as the need to make a transition to usage of renewable energy sources is growing, the importance for electrocatalysis used for electrolytic production of clean fuels, such as hydrogen, is rising. In this thesis, work aimed at understanding and improving electrocatalysts used for these purposes is presented.A main part of the work has been focused on the selectivity between chlorine gas, or sodium chlorate formation, and parasitic oxygen evolution. An activation of anode surface Ti cations by nearby Ru cations is suggested as a reason for the high chlorine selectivity of the “dimensionally stable anode” (DSA), the standard anode used in industrial chlorine and sodium chlorate production. Furthermore, theoretical methods have been used to screen for dopants that can be used to improve the activity and selectivity of DSA, and several promising candidates have been found. Moreover, the connection between the rate of chlorate formation and the rate of parasitic oxygen evolution, as well as the possible catalytic effects of electrolyte contaminants on parasitic oxygen evolution in the chlorate process, have been studied experimentally.Additionally, the properties of a Co-doped DSA have been studied, and it is found that the doping makes the electrode more active for hydrogen evolution. Finally, the hydrogen evolution reaction on both RuO2 and the noble-metal-free electrocatalyst material MoS2 has been studied using a combination of experimental and theoretically calculated X-ray photoelectron chemical shifts. In this way, insight into structural changes accompanying hydrogen evolution on these materials is obtained.
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| 14. |
- Kim, Hyeyun, et al.
(författare)
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Lithium Ion Battery Separators Based On Carboxylated Cellulose Nanofibers From Wood
- 2019
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Ingår i: ACS Applied Energy Materials. - : American Chemical Society (ACS). - 2574-0962. ; 2:2, s. 1241-1250
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Tidskriftsartikel (refereegranskat)abstract
- Carboxylated cellulose nanofibers, prepared by TEMPO-mediated oxidation (TOCN), were processed into asymmetric mesoporous membranes using a facile paper-making approach and investigated as lithium ion battery separators. Membranes made of TOCN with sodium carboxylate groups (TOCN-COO-Na+) showed capacity fading after a few cycles of charging and discharging. On the other hand, its protonated counterpart (TOCN-COOH) showed highly improved electrochemical and cycling stability, displaying 94.5% of discharge capacity maintained after 100 cycles at 1 C rate of charging and discharging. The asymmetric surface porosity of the membranes must be considered when assembling a battery cell as it influences the rate capabilities of the battery. The wood-based TOCN-membranes have a good potential as an ecofriendly alternative to conventional fossil fuel-derived separators without adverse side effects.
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| 15. |
- Kim, Hyeyun, 1986-, et al.
(författare)
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One-step electro-precipitation of nanocellulose hydrogels on conducting substrates and its possible applications : coatings, composites, and energy devices
- 2019
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Ingår i: ACS Sustainable Chemistry and Engineering. - : American Chemical Society (ACS). - 2168-0485. ; 7:24, s. 19415-19425
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Tidskriftsartikel (refereegranskat)abstract
- TEMPO-oxidized cellulose nanofibrils (TOCN) are pH-responsive biopolymers which undergo sol–gel transition at acidic conditions (pH < 4) due to charge neutralization. Electronically conducting materials can be coated by such gels during aqueous electrolysis, when an electrochemical reaction generates a local pH decrease at the electrode surface. In this work, electro-precipitation of different TOCN gels has been performed on oxygen evolving anodes. We demonstrate that TOCN hydrogels can be electrochemically coated on the surface of any conductive material with even complex 3D shape. Further, not only TOCN but also micro- or nanosized particles containing TOCN composites can be coated on the electrode surface, and coatings containing multiple layers of different composites can be also produced. We demonstrate that this simple and facile electrocoating technique can be subject to various applications, such as coatings making electrodes selective for the hydrogen evolution reaction, as well as a new eco-friendly aqueous-based synthesis of Li-ion battery electrodes.
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| 16. |
- Lindberg, Jonas, 1988-
(författare)
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Electrochemical Investigation of the Reaction Mechanism in Lithium-Oxygen Batteries
- 2017
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Lithium-oxygen batteries, also known as Lithium-air batteries, could possibly revolutionize energy storage as we know. By letting lithium react with ambient oxygen gas very large theoretical energy densities are possible. However, there are several challenges remaining to be solved, such as finding suitable materials and understanding the reaction, before the lithium-oxygen battery could be commercialized. The scope of this thesis is focusing on the latter of these challenges.Efficient ion transport between the electrodes is imperative for all batteries that need high power density and energy efficiency. Here the mass transport properties of lithium ions in several different solvents was evaluated. The results showed that the lithium mass transport in electrolytes based on the commonly used lithium-oxygen battery solvent dimethyl sulfoxide (DMSO) was very similar to that of conventional lithium-ion battery electrolytes. However, when room temperature ionic liquids were used the performance severely decreased.Addition of Li salt will effect the oxygen concentration in DMSO-based electrolytes. The choice of lithium salt influenced whether the oxygen concentration increased or decreased. At one molar salt concentration the highest oxygen solubility was 68 % larger than the lowest one.Two model systems was used to study the electrochemical reaction: A quartz crystal microbalance and a cylindrical ultramicroelectrode. The combined usage of these systems showed that during discharge soluble lithium superoxide was produced. A consequence of this was that not all discharge product ended up on the electrode surface.During discharge the cylindrical ultramicroelectrodes displayed signs of passivation that previous theory could not adequately describe. Here the passivation was explained in terms of depletion of active sites. A mechanism was also proposed.The O2 and Li+ concentration dependencies of the discharge process were evaluated by determining the reactant reaction order under kinetic and mass transport control. Under kinetic control the system showed non-integer reaction orders with that of oxygen close to 0.5 suggesting that the current determining step involves adsorption of oxygen. At higher overpotentials, at mass transport control, the reaction order of lithium and oxygen was zero and one, respectively. These results suggest that changes in oxygen concentration will influence the current more than that of lithium.During charging not all of the reaction product was removed. This caused an accumulation when several cycles was examined. The charge reaction pathway involved de-lithiation and bulk oxidation, it also showed an oxygen concentration dependence.
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| 17. |
- Lindberg, Jonas, et al.
(författare)
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Li Salt Anion Effect on O-2 Solubility in an Li-O-2 Battery
- 2018
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Ingår i: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 122:4, s. 1913-1920
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Tidskriftsartikel (refereegranskat)abstract
- For the promising Li-O-2 battery to be commercialized, further understanding of its constituents is needed. This study deals with the role of O-2 in Li-O-2 batteries, both its influence on electrochemical performance and its solubility in lithium-salt-containing dimethyl sulfoxide (DMSO) electrolytes. Experimentally, the electrochemical performance was evaluated using cylindrical ultramicroelectrodes. Two independent techniques, using a mass spectrometer and an optical sensor, were used to evaluate the O-2 solubility, expressed as Henry's constant. Furthermore, the ionic conductivity, dynamic viscosity, and density were also measured. Density functional theory calculations were made of the interaction energy between O-2 and the different species in the electrolytes. When varying O-2 partial pressure, the current was larger at high pressures confirming that the O-2 concentration is of key importance when studying the kinetics of this system. Compared with neat DMSO, the O-2 solubility increased with addition of LiTFSI and decreased with addition of LiClO4, indicating that the salt influences the solubility. This solubility trend is best explained in terms of apparent molar volume and interaction energy between O-2 and the salt anion. In conclusion, this study shows the importance of O-2 concentration, not just its partial pressure, and that the choice of Li salt can make this concentration increase or decrease.
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| 18. |
- Lindberg, Jonas, et al.
(författare)
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The effect of O2 concentration on the reaction mechanism in Li-O2 batteries
- 2017
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Ingår i: Journal of Electroanalytical Chemistry. - : Elsevier BV. - 1572-6657 .- 0022-0728 .- 1873-2569. ; 797, s. 1-7
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Tidskriftsartikel (refereegranskat)abstract
- The promising lithium-oxygen battery chemistry presents a set of challenges that need to be solved if commercialization is ever to be realized. This study focuses on how the O2 reaction path is effected by the O2 concentration in the electrolyte. An electrochemical quartz crystal microbalance system was used to measure current, potential, and change in electrode mass simultaneously. It is concluded that the mass reversibility is O2 concentration dependent while the coulombic efficiency is not. The mass reversibility is higher at low O2 concentration meaning that more of the deposited Li2O2 is removed during oxidation in relation to the amount deposited during reduction. The first step of the reduction is the formation of soluble LiO2, which is then either reacting further at the electrode or being transported away from the electrode resulting in low current efficiency and low deposited mass per electrons transferred. During the oxidation, the first step involves de-lithiation of Li2O2 at low potential followed by bulk oxidation. The oxidation behavior is O2 concentration dependent, and this dependence is likely indirect as the O2 concentration effects the amount of discharge product formed during the reduction. The O2 concentration at different saturation pressures was determined using a mass spectrometer. It was found that the electrolyte follows Henry's law at the pressures used in the study. In conclusion, this study provides insight to the O2 concentration dependence and the preferred path of the O2 electrochemical reactions in lithium-oxygen batteries.
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| 19. |
- Lu, Huiran, et al.
(författare)
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Effects of Different Manufacturing Processes on TEMPO-Oxidized Carboxylated Cellulose Nanofiber Performance as Binder for Flexible Lithium-Ion Batteries
- 2017
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Ingår i: ACS Applied Materials and Interfaces. - : American Chemical Society (ACS). - 1944-8244 .- 1944-8252. ; 9:43, s. 37712-37720
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Tidskriftsartikel (refereegranskat)abstract
- Carboxylated cellulose nanofibers (CNF) prepared using the TEMPO-route are good binders of electrode components in flexible lithium-ion batteries (LIB). However, the different parameters employed for the defibrillation of CNF such as charge density and degree of homogenization affect its properties when used as binder. This work presents a systematic study of CNF prepared with different surface charge densities and varying degrees of homogenization and their performance as binder for flexible LiFePO4 electrodes. The results show that the CNF with high charge density had shorter fiber lengths compared with those of CNF with low charge density, as observed with atomic force microscopy. Also, CNF processed with a large number of passes in the homogenizer showed a better fiber dispersibility, as observed from rheological measurements. The electrodes fabricated with highly charged CNF exhibited the best mechanical and electrochemical properties. The CNF at the highest charge density (ISSO mu mol g(-1)) and lowest degree of homogenization (3 + 3 passes in the homogenizer) achieved the overall best performance, including a high Young's modulus of approximately 311 MPa and a good rate capability with a stable specific capacity of 116 mAh g(-1) even up to 1 C. This work allows a better understanding of the influence of the processing parameters of CNF on their performance as binder for flexible electrodes. The results also contribute to the understanding of the optimal processing parameters of CNF to fabricate other materials, e.g., membranes or separators.
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| 20. |
- Lu, Huiran, et al.
(författare)
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Flexible and Lightweight Lithium-Ion Batteries Based on Cellulose Nanofibrils and Carbon Fibers
- 2018
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Ingår i: BATTERIES-BASEL. - : MDPI. - 2313-0105. ; 4:2
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Tidskriftsartikel (refereegranskat)abstract
- Flexible, low-weight electrodes with integrated current collectors based on chopped polyacrylonitrile carbon fibers (CF) were produced using an easy, aqueous fabrication process, where only 4 wt% of TEMPO-oxidized cellulose nanofibrils (CNF) were used as the binder. A flexible full cell was assembled based on a LiFePO4 (LFP) positive electrode with a CF current collector and a current collector-free CF negative electrode. The cell exhibited a stable specific capacity of 121 mAh g(-1) based on the LFP weight. The CF in the negative electrode acted simultaneously as active material and current collector, which has a significant positive impact on energy density. Stable specific capacities of the CF/CNF negative electrode of 267 mAh g(-1) at 0.1 C and 150 mAh g(-1) at 1 C are demonstrated. The LFP/CNF with CF/CNF, as the current collector positive electrode (LFP-CF), exhibited a good rate performance with a capacity of -150 mAh g(-1) at 0.1 C and 133 mAh g(-1) at 1 C. The polarization of the LFP-CF electrode was similar to that of a commercial Quallion LFP electrode, while much lower compared to a flexible LFP/CNF electrode with Al foil as the current collector. This is ascribed to good contact between the CF and the active material.
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| 21. |
- Lu, Huiran, et al.
(författare)
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Flexible Paper Electrodes for Li-Ion Batteries Using Low Amount of TEMPO-Oxidized Cellulose Nanofibrils as Binder
- 2016
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Ingår i: ACS Applied Materials and Interfaces. - : American Chemical Society. - 1944-8244 .- 1944-8252. ; 8:28, s. 18097-18106
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Tidskriftsartikel (refereegranskat)abstract
- Flexible Li-ion batteries attract increasing interest for applications in bendable and wearable electronic devices. TEMPO-oxidized cellulose nanofibrils (TOCNF), a renewable material, is a promising candidate as binder for flexible Li-ion batteries with good mechanical properties. Paper batteries can be produced using a water-based paper making process, avoiding the use of toxic solvents. In this work, finely dispersed TOCNF was used and showed good binding properties at concentrations as low as 4 wt %. The TOCNF was characterized using atomic force microscopy and found to be well dispersed with fibrils of average widths of about 2.7 nm and lengths of approximately 0.1-1 μm. Traces of moisture, trapped in the hygroscopic cellulose, is a concern when the material is used in Li-ion batteries. The low amount of binder reduces possible moisture and also increases the capacity of the electrodes, based on total weight. Effects of moisture on electrochemical battery performance were studied on electrodes dried at 110 °C in a vacuum for varying periods. It was found that increased drying time slightly increased the specific capacities of the LiFePO4 electrodes, whereas the capacities of the graphite electrodes decreased. The Coulombic efficiencies of the electrodes were not much affected by the varying drying times. Drying the electrodes for 1 h was enough to achieve good electrochemical performance. Addition of vinylene carbonate to the electrolyte had a positive effect on cycling for both graphite and LiFePO4. A failure mechanism observed at high TOCNF concentrations is the formation of compact films in the electrodes.
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| 22. |
- Lu, Huiran, et al.
(författare)
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Li4Ti5O12 flexible, lightweight electrodes based on cellulose nanofibrils as binder and carbon fibers as current collectors for Li-ion batteries
- 2017
-
Ingår i: Nano Energy. - : Elsevier. - 2211-2855 .- 2211-3282. ; 39, s. 140-150
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Tidskriftsartikel (refereegranskat)abstract
- TEMPO oxidized cellulose nanofibrils (TOCNF) were used as binder material to prepare bendable Li4Ti5O12 (LTO) electrodes. Carbon fiber (CF) layers were integrated as current collectors to enhance the mechanical properties and to increase the specific energy of the electrodes. These electrodes combined with CF current collectors (LTO/CF) show good electrochemical properties and are flexible, sustainable, mechanical and chemical stable, lightweight and produced by a water-based easy filtration process. An increase of the active material weight (LTO) from around 19% to 71% of the electrode and current collector combined weight is demonstrated with CF compared with a copper current collector. Additionally, preparation of the current collector material is non-expensive, quick and easy compared to that of carbon nanotube or graphene. To test the flexible battery application, 4000 times repeated bending was carried out on both the LTO electrodes and the LTO/CF electrodes. This had no significant effect on the morphology, mechanical and electrochemical properties of neither the LTO nor the LTO/CF electrodes. Addition of the CF layer improves the mechanical properties and specific capacity of the LTO-electrode. A thicker LTO electrode with only 2 wt% TOCNF is demonstrated which is promising for thicker electrodes with high energy density. A full cell was assembled with the LTO/CF as negative electrode and LiFePO4 (LFP)/CF as positive, which exhibited a stable cycling performance and good energy density.
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| 23. |
- Lu, Huiran, et al.
(författare)
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Lignin as a Binder Material for Eco-Friendly Li-Ion Batteries
- 2016
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Ingår i: Materials. - : MDPI AG. - 1996-1944. ; 9:3
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Tidskriftsartikel (refereegranskat)abstract
- The industrial lignin used here is a byproduct from Kraft pulp mills, extracted from black liquor. Since lignin is inexpensive, abundant and renewable, its utilization has attracted more and more attention. In this work, lignin was used for the first time as binder material for LiFePO4 positive and graphite negative electrodes in Li-ion batteries. A procedure for pretreatment of lignin, where low-molecular fractions were removed by leaching, was necessary to obtain good battery performance. The lignin was analyzed for molecular mass distribution and thermal behavior prior to and after the pretreatment. Electrodes containing active material, conductive particles and lignin were cast on metal foils, acting as current collectors and characterized using scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS) and galvanostatic charge-discharge cycles. Good reversible capacities were obtained, 148 mAhg(-1) for the positive electrode and 305 mAhg(-1) for the negative electrode. Fairly good rate capabilities were found for both the positive electrode with 117 mAhg(-1) and the negative electrode with 160 mAhg(-1) at 1C. Low ohmic resistance also indicated good binder functionality. The results show that lignin is a promising candidate as binder material for electrodes in eco-friendly Li-ion batteries.
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| 24. |
- Martín-Yerga, Daniel, et al.
(författare)
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Effects of Incorporated Iron or Cobalt on the Ethanol Oxidation Activity of Nickel (Oxy)Hydroxides in Alkaline Media
- 2019
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Ingår i: Electrocatalysis. - : Springer Science and Business Media LLC. - 1868-2529 .- 1868-5994.
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Tidskriftsartikel (refereegranskat)abstract
- Nickel (oxy)hydroxides (NiOxHy) are promising cost-effective materials that exhibit a fair catalytic activity for the ethanol oxidation reaction (EOR) and could be used for sustainable energy conversion. Doping the NiOxHy structure with other metals could lead to enhanced catalytic properties but more research needs to be done to understand the role of the doping metal on the EOR. We prepared NiOxHy films doped with Fe or Co with different metallic ratios by electrodeposition and evaluated the EOR. We found a positive and negative effect on the catalytic activity after the incorporation of Co and Fe, respectively. Our results suggest that Ni atoms are the active sites for the EOR since Tafel slopes were similar on the binary and pristine nickel (oxy)hydroxides and that the formal potential of the Ni(II)/Ni(III) redox couple is a good descriptor for the EOR activity. This work also highlights the importance of controlled metal doping on catalysts and may help in the design and development of improved materials for the EOR.
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| 25. |
- Sandin, Staffan, et al.
(författare)
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Catalyzed and uncatalyzed decomposition of hypochlorite in dilute solutions
- 2015
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Ingår i: Industrial & Engineering Chemistry Research. - : American Chemical Society (ACS). - 0888-5885 .- 1520-5045. ; 54:15, s. 3767-3774
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Tidskriftsartikel (refereegranskat)abstract
- Hypochlorite decomposition has been investigated by the combined measurement of aqueous concentrations of total hypochlorite, chlorate, and chloride, as well as that of evolved oxygen. In all experiments, the initial concentrations of NaOCl and NaCl were 80 mM, and the temperature was 80°C. The pH was kept constant in the range 5-10.5. The uncatalyzed decomposition of hypochlorite and the formation of chlorate and oxygen were all found to be third order of the form ri = ki[HOCl]2[OCl-], and kO2 was determined to be 0.046 M-2 s-1. A reaction mechanism in which oxygen and chlorate formation share an intermediate is proposed. Several compounds were tested for catalytic effects. The addition of chloride salts of cobalt and iridium showed catalytic effects on oxygen formation. The addition of iridium chloride also catalyzed the formation of chlorate with increasing selectivity for chlorate with increasing pH.
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| 26. |
- Sandin, Staffan, et al.
(författare)
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Deposition efficiency in the preparation of ozone-producing nickel and antimony doped tin oxide anodes
- 2017
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Ingår i: Journal of Electrochemical Science and Engineering. - : INT ASSOC PHYSICAL CHEMISTS-IAPC. - 1847-9286. ; 7:1, s. 51-64
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Tidskriftsartikel (refereegranskat)abstract
- The influence of precursor salts in the synthesis of nickel and antimony doped tin oxide (NATO) electrodes using thermal decomposition from dissolved chloride salts was investigated. The salts investigated were SnCl4 center dot 5H(2)O, SnCl2 center dot 2H(2)O, SbCl3 and NiCl2 center dot 6H(2)O. It was shown that the use of SnCl4 center dot 5H(2)0 in the preparation process leads to a tin loss of more than 85 %. The loss of Sb can be as high as 90 % while no indications of Ni loss was observed. As a consequence, the concentration of Ni in the NATO coating will be much higher than in the precursor solution. This high and uncontrolled loss of precursors during the preparation process will lead to an unpredictable composition in the NATO coating and will have negative economic and environmental effects. It was found that using SnCl2 center dot 2H(2)0 instead of SnCl4 center dot 5H(2)O can reduce the tin loss to less than 50 %. This tin loss occurs at higher temperatures than when using SnCl4 center dot 5H(2)O where the tin loss occurs from 56 - 147 degrees C causing the composition to change both during the drying (80 - 110 degrees C) and calcination (460 - 550 degrees C) steps of the preparation process. Electrodes coated with NATO based on the two different tin salts were investigated for morphology, composition, structure, and ozone electrocatalytic properties.
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| 27. |
- Sandin, Staffan, 1984-
(författare)
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Oxygen formation in the chlorate process and preparation and deactivation of ozone selective anodes
- 2019
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- This thesis presents experimental studies concerning two differ-ent electrolytic processes. One part deals with the electrochemicalformation of ozone and focuses on the preparation and deactiva-tion of a highly ozone-selective metal oxide anode (NATO - nickeland antimony doped tin oxide). The preparation of this anode bythermal decomposition of metal chloride salts was investigated anddifficulties and complications of common procedures were identi-fied. The same anodes were also studied regarding the deactivationof their ozone selective properties, identifying possible underlyingmechanisms for this as well as providing indications of the ozoneformation mechanism on the anode. When preparing these anodesby thermal decomposition, the volatility of the precursor salt usedfor the different components needs to be considered. For instanceextensive evaporation of the precursors of tin and antimony canlead to an unreliable preparation process resulting in the difficultyof controlling the properties of the prepared electrodes and a poorreproducibility of the process. The deactivation of the NATOelectrodes was investigated using the ozone current efficiency as amain indicator. The electrodes and the electrolyte were examinedusing electrochemical as well as physical techniques after differentperiods of galvanostatic polarization. The main mechanism behindthe deactivation was identified as the dissolution of antimony fromthe electrode surface. Also contributing, but not as detrimental,seems to be the dissolution of nickel. Both dopants, Ni and Sb, arepresent at the surface of the oxide anode and both seem equallyimportant for enabling the electrochemical ozone formation.The second part of this thesis concerns the decomposition ofhypochlorite, an important intermediate in the industrial chlorateprocess. A connection was found between the formation of chlorateand oxygen, both occurring according to 3rd order kinetics withregard to hypochlorite and both having their highest rates atpH 6 - 7. In the presence of chromium(VI) the hypochloritedecomposition can be modelled as the sum of two parallel reactions:one catalyzed by chromium(VI) and one uncatalyzed reaction.The byproduct oxygen seems to be formed only in the latter. Thusvaddition of chromium(VI) in the electrolyte increases both therate and the selectivity of chlorate formation. These findings areimportant as chromium(VI) needs to be removed from the processdue to its toxicity and in its absence the uncatalyzed decompositionpath would lead to an increase in oxygen formation, resultingin efficiency losses as well as potentially explosive gas mixtures.There is a need for a catalyst that can replace chromium(VI) inthis function.
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