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  • 1
    In: Electrochemical Energetics, Saratov State University, Vol. 19, No. 1 ( 2019), p. 48-59
    Type of Medium: Online Resource
    ISSN: 1608-4039
    Uniform Title: МОДЕЛИРОВАНИЕ ХАРАКТЕРИСТИК ЛИТИЙ-СЕРНЫХ АККУМУЛЯТОРОВ НА ОСНОВЕ ЭКСПЕРИМЕНТАЛЬНОЙ ОЦЕНКИ ЭЛЕКТРОХИМИЧЕСКИХ СВОЙСТВ ЭЛЕКТРОДНЫХ МАТЕРИАЛОВ
    Language: Unknown
    Publisher: Saratov State University
    Publication Date: 2019
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  • 2
    In: Electrochemical Energetics, Saratov State University, Vol. 22, No. 3 ( 2022-11-23), p. 113-128
    Abstract: The effect of sulfur content in positive electrodes (the surface capacity of sulfur electrodes) on the characteristics (such as the depth of sulfur electrochemical reduction, changes in capacitance and Coulomb efficiency during cycle life) of lithium-sulfur cells with electrolytes based on sulfolane was studied. It was shown that the reason for the capacitance decrease of the lithium-sulfur cells at the early stage of its cycle life is the displacement of sulfur of the porous positive electrode from the rear regions into the front ones. It was established that in order to achieve the maximum possible specific energy of the lithium-sulfur batteries with the electrolytes based on sulfolane, the surface capacitance of the positive electrodes should be in the range of 2-3 mA·h/cm2.
    Type of Medium: Online Resource
    ISSN: 1608-4039 , 1680-9505
    Uniform Title: Влияние поверхностной ёмкости положительных электродов на длительность циклирования литий-серных аккумуляторов
    Language: Unknown
    Publisher: Saratov State University
    Publication Date: 2022
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  • 3
    In: Electrochemical Energetics, Saratov State University, Vol. 21, No. 2 ( 2021-06-24), p. 96-107
    Abstract: The possibility of determining the charge state of lithium-sulfur batteries using the ANFIS model was estimated. Easily measurable in practice physical quantities were used as input parameters of the model. They are the battery voltage, the rate of its change and the number of previous cycles. The analysis of ANFIS models with various parameters (the number and type of membership functions) was carried out. It was shown that ANFIS is a model that makes it possible to estimate the charge state of a lithium-sulfur battery with the accuracy of more than 95%. The proposed type of models can be used in control and monitoring systems, together with digital aggregated twins, for additional training of models based on real data and increasing the accuracy of estimating the charge state of lithium-sulfur batteries.
    Type of Medium: Online Resource
    ISSN: 1608-4039
    Uniform Title: Моделирование и оценка зарядового состояния литий-серного аккумулятора с помощью нейронно-нечёткой сети
    Language: Unknown
    Publisher: Saratov State University
    Publication Date: 2021
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  • 4
    In: ECS Meeting Abstracts, The Electrochemical Society, Vol. MA2019-01, No. 2 ( 2019-05-01), p. 238-238
    Abstract: Lithium-sulfur batteries are batteries with a liquid cathode. Electrochemical transformations of sulfur and the products of its reduction (lithium polysulfides and lithium sulfide) occur on the surface of carbon particles, forming a porous carbon conductive matrix (porous carbon electrode).The depth and rate of electrochemical transformations of sulfur and lithium polysulfides are determined by both the properties of the carbon matrix (porosity, specific surface area, electrical conductivity, sorption capacity towards sulfur and lithium polysulfides) and the properties of electrolyte systems. One of the most important parameters of a porous electrode is the characteristic length - the penetration depth of the electrochemical process into the electrode volume, the value of which is determined by the ratio of the conductivity of electrolyte and charge transfer resistance (equation). We studied the effect of the conductivity of electrolyte solutions and the surface capacity of sulfur electrodes on the depth of the electrochemical reduction of sulfur (figure). The sulfur electrodes (d=2.85 cm, A=6.38 cm 2 ) used in this study had the following composition: S (99.5%, Acros) - 70% wt., Ketjenblack ® EC-600JD (Akzo Nobel) - 10% wt., Polyethylene oxide (ММ=4x10 6 , Aldrich) - 20% wt. The negative electrodes (d=2.55 cm, A=5.10 cm 2 ) were made of lithium foil (99.9%, Russia) with a thickness of 120 micrometers. 1M solution of LiSO 3 CF 3 in sulfolane (specific conductivity is 0.87 mS/cm at 30 0 C) and 1M solution of LiClO 4 in sulfolane (specific conductivity is 2.23 mS/cm at 30 0 C) were used as electrolytes. The content of electrolytes into lithium-sulfur cells was 4 microliters per 1 mAh, which is equivalent to 6.7 microliters per 1 mg of sulfur. The electrolyte was introduced into lithium-sulfur cells using a “MICROLITER TM Syringe” (Hamilton Company, USA) with a volume of 50 microliters. The accuracy of electrolyte dosing into the cells was ±5 %. It was established that the penetration depth of the reactions of electrochemical reduction of sulfur and lithium polysulfides into volume of the sulfur electrode is higher in 1M solution of LiClO 4 in sulfolane than 1M solution of LiSO 3 CF 3 in sulfolane. The observed patterns are explained from the standpoint of the theory of a porous electrode. This work was performed as part Government Order of the Ministry of Science and Higher Education of the Russian Federation (theme No. АААА-А17-117011910031-7) and was also financially supported by Russian Science Foundation (Project No 17-73-20115) and by Russian Foundation for Basic Research (Project No 16-29-06190). Figure 1
    Type of Medium: Online Resource
    ISSN: 2151-2043
    Language: Unknown
    Publisher: The Electrochemical Society
    Publication Date: 2019
    detail.hit.zdb_id: 2438749-6
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  • 5
    In: International Journal of Quantum Chemistry, Wiley, Vol. 122, No. 22 ( 2022-11-15)
    Abstract: The structure of lithium polysulfides has been studied using density functional theory. The thermodynamic characteristics of their most probable transformations in sulfolane (Sl) have been evaluated. Various models of lithium oxidation and reduction of sulfur are studied by the PBE1PBE/6–311 +  G ( d , p ) approximation, considering the influence of the solvation environment by the IEF‐PCM. The most probable mechanism of sulfur reduction in the Li–S system is considered (Voltage vs. Li/Li + ): (I) S 8  + 2Li → Li 2 S 8 (2.6 V), (II) Li 2 S 8  + 2Li → 2Li 2 S 4 (2.3 V), (III) Li 2 S 4  + 2Li → 2Li 2 S 2 (1.6 V), (IV) Li 2 S 2  + 2Li → 2Li 2 S (1.3 V). It was shown that the potential of the reduction of sulfur compounds is substantially determined by the composition of the solvate complexes of lithium polysulfides. The solvate complex Li 2 S 8 ·2Sl is the most stable in the form of a «broken crown». The preference of the fragmentation of Li 2 S 8 into LiS 4 − and LiS 4 upon electron transfer is shown using FMO theory.
    Type of Medium: Online Resource
    ISSN: 0020-7608 , 1097-461X
    URL: Issue
    Language: English
    Publisher: Wiley
    Publication Date: 2022
    detail.hit.zdb_id: 1475014-4
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  • 6
    In: Electrochemical Energetics, Saratov State University, Vol. 13, No. 3 ( 2013), p. 150-157
    Abstract: In this paper, we investigated the possibility of determining the internal resistance of the battery by pulsed method with followed Fourier transformation in transition characteristics. The changes of internal resistance of lithium sulfur cells were studied in dependence on the discharge and charge depths during continuous cycling by proposed method. It was shown that the internal resistance of lithium sulfur cell was maximal at the point corresponding to the transition between high-voltage and low-voltage plateaus both at the charge curves and at the discharge curves. The most significant increase in the internal resistance of lithium sulfur cells occurs at the initial stages of cycling. It was found that the internal resistance of lithium sulphur cell is governed by the way the state of charge is achieved. This is due to the difference in densities of products, generated in positive electrodes by electrochemical reactions at charge (d(S)=2.07 g/cm3) and discharge (d(Li2S)=1.63 g/cm3).
    Type of Medium: Online Resource
    ISSN: 1608-4039 , 1680-9505
    Uniform Title: Исследование изменения внутреннего сопротивления литий-серных ячеек в процессе гальваностатического циклирования импульсным методом
    Language: Unknown
    Publisher: Saratov State University
    Publication Date: 2013
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  • 7
    In: New Carbon Materials, Elsevier BV, Vol. 38, No. 4 ( 2023-08), p. 641-655
    Type of Medium: Online Resource
    ISSN: 1872-5805
    Language: English
    Publisher: Elsevier BV
    Publication Date: 2023
    detail.hit.zdb_id: 2374609-9
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  • 8
    Online Resource
    Online Resource
    American Chemical Society (ACS) ; 2022
    In:  The Journal of Physical Chemistry B Vol. 126, No. 39 ( 2022-10-06), p. 7676-7685
    In: The Journal of Physical Chemistry B, American Chemical Society (ACS), Vol. 126, No. 39 ( 2022-10-06), p. 7676-7685
    Type of Medium: Online Resource
    ISSN: 1520-6106 , 1520-5207
    RVK:
    Language: English
    Publisher: American Chemical Society (ACS)
    Publication Date: 2022
    detail.hit.zdb_id: 1357799-2
    detail.hit.zdb_id: 2006039-7
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  • 9
    Online Resource
    Online Resource
    The Electrochemical Society ; 2014
    In:  ECS Meeting Abstracts Vol. MA2014-02, No. 1 ( 2014-08-05), p. 50-50
    In: ECS Meeting Abstracts, The Electrochemical Society, Vol. MA2014-02, No. 1 ( 2014-08-05), p. 50-50
    Abstract: The lithium sulphur electrochemical system has high value of theoretical specific energy – 2600 Wh/kg. However a real reached specific energy of prototypes of lithium sulphur batteries is only 6-15% (150-400 Wh/kg) against theoretical expected value. The main reason of that is great share of accessory components – 70-80%, from which an electrolyte share is 40-60%. Necessity of using a great volume of electrolyte is caused by multifunctionality of electrolyte in lithium sulphur cells: ion transport between electrodes; sulphur dissolution; lithium polysulphides solvation and dissolution; stabilization of the necessary molecular and ionic forms of lithium polysulphides. A problem of high rate of capacity fading of lithium sulphur batteries during cycling is another problem which should be solved for commercial application of these batteries. Both problems are caused by feature of lithium sulphur batteries – transformation of sulphur and lithium sulphide into lithium polysulphides readily dissolves in the electrolytes. Solubility of lithium polysulphides and the forms of their existence in electrolytes are basically determined by electrolyte salt and nature of solvent. Therefore characteristics of lithium sulphur batteries should also depend on electrolyte salt and nature of solvent. The aim of the present work is to estimate an effect of lithium salts and amount of electrolyte on the cycle life of lithium sulphur cells. A study of the electrochemical properties of lithium sulphur cells was carried out in Swagelok type cell. The sulphur (working) electrodes consisted of 70 wt.% sulphur, 10 wt.% carbon and 20 wt.% binder. The sulphur electrodes had an average loading of 1.2 mg sulphur per cm 2 . Lithium metal foil (99.9%, LE-1, Russia) with the thickness of 80 μm was used as the auxiliary electrode. 1M LiClO 4 and 1M LiSO 3 CF 3 in sulfolane were used as the electrolytes. Amount of electrolyte into cells was 1.0; 1.5; 2.0; 3.0 and 4.0 μl/mAh(S). Porous polypropylene Celgard ® 3501 was used as the separator. The lithium sulphur cells were assembled by stacking lithium electrode, separator containing electrolyte and sulphur electrode. Electrolyte preparation, lithium electrode manufacture and lithium sulphur cells assembly were all carried out in dry air filled glove box. The charge and discharge performances of the assembled cells were investigated with a PG12-100 potentiostat between 1.5 V and 2.8 V at +30 o C. The charge current density was 0.1 mA/cm 2 , the discharge current density was 0.2 mA/cm 2 . It has shown, that lithium salt has no effect on the shape of discharge curves (fig.a and fig.c), but has an effect on the rate of capacity fading and cycle life of lithium sulphur cells (fig.b and fig.d). Irrespective of amount of 1M LiClO 4 in sulfolane the discharge capacity of lithium sulphur cells primarily decreases dramatically on about 40-50 %, then rate of capacity fading decreases and capacity stabilizes. Cycle life of these cells does not practically depend on amount of electrolyte (fig.b). For 1M LiSO 3 CF 3 in sulfolane rate of discharge capacity fading of lithium sulphur cells depends on amount of electrolyte. The increase of amount of electrolyte into cells leads to reduction of rate of discharge capacity fading during cycling and to increase of cycle life (fig.d). This study was carried out under project of Russian Academy of Sciences No. 01201152192 and also partially supported by RFBR, research project No 13-00-14056.
    Type of Medium: Online Resource
    ISSN: 2151-2043
    Language: Unknown
    Publisher: The Electrochemical Society
    Publication Date: 2014
    detail.hit.zdb_id: 2438749-6
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  • 10
    Online Resource
    Online Resource
    The Electrochemical Society ; 2014
    In:  ECS Meeting Abstracts Vol. MA2014-02, No. 1 ( 2014-08-05), p. 49-49
    In: ECS Meeting Abstracts, The Electrochemical Society, Vol. MA2014-02, No. 1 ( 2014-08-05), p. 49-49
    Abstract: The efficiency of chemical energy conversion to electric is a significant characteristic of batteries and it is especially for batteries on base of high power electrochemical systems (for example Li-S). The maximal possible efficiency of energy conversion is determined by thermodynamic properties of the electrochemical systems. There are two main methods to estimate of the thermodynamic properties of the electrochemical processes: calorimetric and potentiometric. Heat generation or absorption of the electrochemical processes is possible to register direct by calorimetric methods . However registered heat generation or absorption includes both thermal effects of the electrochemical reaction and Joule heat during polarization of batteries. If some concurrent processes are going in the batteries then their thermal effects will be part of the registered heat generation or absorption by the instrument. One of the other disadvantages of the calorimetric methods is complexity and high price of instruments. Potentiometric method is much easier in instrument executions than calorimetric method and allows to more accurate estimate the thermodynamic properties of the electrochemical processes in the batteries. Therefore it is wide used to estimate the thermodynamic properties of active components of positive and negative electrodes of batteries. The main criterion of applicability of the potentiometric method to measure thermodynamic properties is reversibility of material and energy flows. Therefore this method must be used with care and especially for batteries with high self-discharge rate, for example batteries with liquid cathode (Li-S battery). The aim of present work is an assessment of applicability of the potentiometric method to determine the thermodynamic properties of the electrochemical processes in the lithium sulphur batteries. The test subjects were the lithium sulphur pouch cell. Lithium foil (99.9%, LE-1, Russia) with a thickness of 100 μm was used as negative electrodes. The working electrodes were sulphur electrodes (70% of Sulphur, 10% of Carbon and 20% of Polyethylene oxide). One layer of micro porous membrane Celgard ® 3501 was used as a separator. An electrolyte was 1M solution of LiCF 3 SO 3 in sulfolane. Electrolyte preparation, lithium electrode manufacture and lithium sulphur batteries assembly were all carried out in dry air filled glove box. Sulphur and products of its reduction (lithium polysulphides) are able to direct interact with metallic lithium and disturb the reversibility of material and energy flows. It should be noted that reactivity of sulphur and lithium polysulphides toward metallic lithium depends on them chemical composition (number of sulphur atoms per molecule). Therefore to study the effect of depth of discharge (DoD) on the reversibility of material and energy flows in the lithium sulphur batteries we measured temperature dependence of open circle voltage (OCV) of batteries at different values of DoD. Current density was 0.2 mA cm -2 . To reach equilibrium (to obtain uniform lithium polysulphide distribution in the bulk of battery) after discharging or charging at the specified DoD batteries were stored 12 hours at constant temperature (30.0 ± 0.1 °C). Then the temperature dependence of OCV was registered in the range of temperature of 10-40 °C. The equilibrium was considered to have been reached when OCV stabilized to less than 0.2 mV h -1 at a constant temperature (±0,1 °C) and OVC-T measurements were completely reproducible at heating and cooling. The thermodynamic properties were calculated by equations: ΔG = -nFE P,T (1) ΔH = -nFE P,T + nFE P,T (∂E/∂T) P (2) ΔS = nF(∂E/∂T) P (3) We estimated that thermodynamic properties of electrochemical reduction of sulphur in the lithium sulphur batteries only can be made by the potentiometric method at the first cycle. At the following cycles of lithium sulphur batteries this method can be applied only at the DoD of 33-100 %. At the depth of discharge of 0-33% (high voltage plateau of charge-discharge curves) lithium sulphur batteries cannot achieve equilibrium because of high rate of self- discharge. The OCV was constantly reducing to the value characteristic to the low voltage plateau of charge-discharge curves. Figure shows the obtained dependences of Free energy (Gibbs energy), enthalpy and entropy changes of the electrochemical reduction of sulphur and lithium polysulphides on the DoD at 1 st cycle. Thus it can be concluded that the potentiometric method of measuring thermodynamic properties of electrochemical reactions in lithium sulphur batteries can be applied at 1 st cycle in all range of DoD and at the following cycles it can be applied only in the range of DoD of 33-100 %. The reported study was partially supported by RFBR, research projects No 13-00-14056 and 4-03-31399.
    Type of Medium: Online Resource
    ISSN: 2151-2043
    Language: Unknown
    Publisher: The Electrochemical Society
    Publication Date: 2014
    detail.hit.zdb_id: 2438749-6
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