Mårten Behm

Influence of structure and composition upon performance of tin phosphate based negative electrodes for lithium batteries

Tin oxide and amorphous tin borophosphates have recently received significant attention as possible new negative electrode materials for lithium batteries. In this study, we have carefully investigated a number of different well-characterised tin phosphates as electrodes in Li-ion cells, in order to better understand the mode of operation of these materials and how their performance is related to structure and composition. The materials that were investigated were crystalline cubic and layered SnP2O7, LiSn2(PO4)3, Sn2P2O7, and Sn3(PO4)2, and amorphous Sn2BPO6. Cubic SnP2O7 showed the best performance with a reversible specific charge capacity of >360 mA h g−1 and a capacity retention of 96% over 50 cycles when cycled between 0.02 and 1.2 V versus Lim. The three Sn(IV) materials showed lower initial reversible capacity but better capacity retention than the three Sn(II) materials in the study. Their higher proportion of inert matrix material can partly explain this. However, cubic SnP2O7 cycled significantly better than its layered polymorph, which shows that the structure of the starting material is also of great importance. Another important conclusion drawn from the results is that it is not necessary for the starting material to be amorphous, or if crystalline, to have small grain size, to cycle well. The three pyrophosphates all show an initial reduction capacity that corresponds to around 2 Li per P2O74− unit more than is predicted by theory. This might be explained by reductive break-up of the POP bond.

Electrochemical production of polysulfides and sodium hydroxide from white liquor: Part I: Experiments with rotating disc and ring-disc electrodes

Electrochemical oxidation of white liquor in a membrane cell is a process of great potential for the pulp and paper industry. The process produces polysulfide-containing white liquor in the anode chamber, and pure sodium hydroxide solution in the cathode chamber. The anode reaction has been investigated using cyclic voltammetry at temperatures between 25 and 90°C on rotating disc and ring-disc electrodes. It was further investigated using chronoamperometry on rotating disc electrodes at 90°C. The experiments, which were mainly run in dilute alkaline sulfide solutions, using platinum electrodes, show that the electrochemical production of polysulfide ions, at lower anode potentials (−0.1 to+0.1V vs SCE), proceeds via formation of elemental sulfur on the electrode surface. The sulfur is dissolved by hydrosulfide and polysulfide ions producing (longer-chain) polysulfide ions. The rate of dissolution, and thus the overall reaction rate, increases strongly with temperature. Polysulfide ions have an autocatalytic effect on the anode reaction due to their ability to dissolve adsorbed sulfur. At higher anode potentials (≥0.2V vs SCE), a change of reaction mechanism is observed. In this region the reaction rate depends on electrode potential and is not catalysed by polysulfide ions.

How amorphous are the tin alloys in li-inserted tin oxides?

Several different metal oxides based anode systems are compared to give insight into their cycling behaviour. The simple electrochemical model for these systems does not usefully predict the ability for a battery to cycle. Pb and Zn oxides cycle less well than Sn oxides, and show more initial crystallinity. SnF2 and PbF2 cycle less well than SnO and PbO. Cubic SnP2O7 cycles better than the layered polymorph. The nature and structure of the supporting matrix is therefore important in the ability of the tin oxides to cycle. Any material with observable crystallinity in first cycle, will not cycle well.

Flexible Paper Electrodes for Li-Ion Batteries Using Low Amount of TEMPO-Oxidized Cellulose Nanofibrils as Binder

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.

A Theoretical and Experimental Study of the Mass Transport in Gel Electrolytes II. Experimental Characterization of LiPF6-EC-PC-P(VdF-HFP)

The mass transport in a gel consisting of LiPF6 dissolved in ethylene carbonate (EC), propylene carbonate (PC) and poly(vinylide-nefluoride-hexafluoropropylene) (P(VdF-HFP)) was characterized at 25 ...

Lignin as a Binder Material for Eco-Friendly Li-Ion Batteries

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 mAh·g−1 for the positive electrode and 305 mAh·g−1 for the negative electrode. Fairly good rate capabilities were found for both the positive electrode with 117 mAh·g−1 and the negative electrode with 160 mAh·g−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.

Graphite as anode material for the electrochemical production of polysulfide ions in white liquor

Graphite as anode material for the electrochemical production of polysulfide ions in white liquor

Nitrate Removal by Continuous Electropermutation Using Ion-Exchange Textile II. Experimental Investigation

Increased levels of nitrate in ground water have made many wells unsuitable as sources for drinking water. In this thesis an ion-exchang eassisted electromembrane process, suitable for nitrate removal, is investigated both theoretically and experimentally. An ion-exchange textile material is introduced as a conducting spacer in the feed compartment of an electropermutation cell. The sheet shaped structure of the textile makes it easy to incorporate into the cell. High permeability and fast ion-exchange kinetics, compared to ion-exchange resins, are other attractive features of the ion-exchange textile. A steady-state model based on the conservation of the ionic species is developed. The governing equations on the microscopic level are volume averaged to give macro-homogeneous equations. The model equations are analyzed and relevant simplifications are motivated and introduced. Dimensionless parameters governing the continuous electropermutation process are identified and their influence on the process are discussed. The mathematical model can be used as a tool when optimising the process parameters and designing equipment. An experimental study that aimed to show the positive influence of using the ion-exchange textile in the feed compartment of an continuous electropermutation process is presented. The incorporation of the ion-exchange textile significantly improves the nitrate removal rate at the same time as the power consumption is decreased. A superficial solution of sodium nitrate with a initial nitrate concentration of 105 ppm was treated. A product stream with less than 20 ppm nitrate could be obtained, in a single pass mode of operation. Its concluded from these experiments that continuous electropermutation using ion-exchange textile provides an interesting alternative for nitrate removal, in drinking water production. The predictions of the mathematical model are compared with experimental results and a good agreement is obtained. Enhanced water dissociation is known to take place at the surface of ion-exchange membranes in electromembrane processes operated above the limiting current density. A model for this enhanced water dissociation in presented in the thesis. The model makes it possible to incorporate the effect of water dissociation as a heterogeneous surface reaction. Results from simulations of electropermutation with and without ion-exchange textile incorporated are presented. The influence of the water dissociation is investigated with the developed model.

Electrochemical production of polysulfides and sodium hydroxide from white liquor. Part II : Electrolysis in a laboratory scale flow cell

Electrochemical production of polysulfide-containing white liquor and pure sodium hydroxide solution was investigated at 90°C in a laboratory scale flow cell. A mixed iridium–tantalum oxide coated titanium electrode was used as the anode and the two electrolyte compartments were separated by a cation-exchange membrane. The process was demonstrated at current densities up to 5kAm−2, resulting in high current efficiencies for both products. The previously reported autocatalytic effect of polysulfide ions was confirmed, and its technical implications on the use of three-dimensional electrodes were demonstrated and discussed. The current efficiency was found to depend strongly on the degree of conversion of sulfur(–ii) to sulfur(0). The anode material showed favourable properties, with respect to activity and selectivity, but suffered from limited durability.

Model-Based Lithium-Ion Battery Resistance Estimation From Electric Vehicle Operating Data

State-of-health estimates of batteries are essential for onboard electric vehicles in order to provide safe, reliable, and cost-effective battery operation. This paper suggests a method to estimate the 10-s discharge resistance, which is an established battery figure of merit from laboratory testing, without performing the laboratory test. Instead, a state-of-health estimate of batteries is obtained using data directly from their operational use, e.g., onboard electric vehicles. It is shown that simple dynamical battery models, based on a current input and a voltage output, with model parameters dependent on temperature and state of charge, can be derived using AutoRegressive with eXogenous input models, whose order can be adjusted to describe the complex battery behavior. Then, the 10-s discharge resistance can be conveniently computed from the identified model parameters. Moreover, the uncertainty of the estimated resistance values is provided by the method. The suggested method is validated with usage data from emulated electric vehicle operation of an automotive lithium-ion battery cell. The resistance values are estimated accurately for a state-of-charge and temperature range spanning typical electric vehicle operating conditions. The identification of the model parameters and the resistance computation are very fast, rendering the method suitable for onboard application.