Kinetics of Na|CF x and Li|CF x systems

Lewandowski, Andrzej; Jakóbczyk, Paweł

doi:10.1007/s10008-016-3305-5

Cited by 16 publications

(10 citation statements)

References 64 publications

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“…Powder X‐ray diffraction patterns were obtained using a Bruker AXS D8 Advance X‐ray diffractometer (Germany) with Cu Kα radiation in a step size of 0.02 o at a dwell time of 1 s. The conductivity of CF x is relatively low. [ 3,5a,26 ] To improve the conductivity of the electrode, the CF 0.88 materials were mixed with conductive acetylene black and poly(vinylidene fluoride) binder at a weight ratio of 7:2:1 and then dissolved completely in N ‐methyl‐2‐pyrrolidone. After stirring for 1 h, the obtained slurry was homogeneously pasted onto Al foil and dried at 110 °C for 12 h in a vacuum oven.…”

Section: Methodsmentioning

confidence: 99%

Reaction Mechanism and Structural Evolution of Fluorographite Cathodes in Solid‐State K/Na/Li Batteries

et al. 2020

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Fluorographites (CFx) are ultrahigh‐energy‐density cathode materials for alkaline‐metal primary batteries. However, they are generally not rechargeable. To elucidate the reaction mechanism of CFx cathodes, in situ transmission electron microscopy characterizations and ab initio calculations are employed. It is found that it is a two‐phase mechanism upon K/Na/Li ion insertion; crystalline KF (crystalline NaF nanoparticles and amorphous LiF) is generated uniformly within the amorphous carbon matrix, retaining an unchanged volume during the discharge process. The diffusivity for K/Na/Li ion migration within the CFx is ≈2.2–2.5 × 10–12, 3.4–5.3 × 10–12 , and 1.8–2.5 × 10–11 cm2 s–1, respectively, which is comparable to the diffusivity of K/Na/Li ions in liquid‐state cells. Encouraged by the in situ transmission electron microscopy (TEM) results, a new rechargeable all‐solid‐state Li/CFx battery is further designed that shows a part of the reversible specific discharge capacity at the 2nd cycle. These findings demonstrate that a solid‐state electrolyte provides a different reaction process compared with a conventional liquid electrolyte, and enables CFx to be partly rechargeable in solid‐state Li batteries.

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Section: Methodsmentioning

confidence: 99%

Reaction Mechanism and Structural Evolution of Fluorographite Cathodes in Solid‐State K/Na/Li Batteries

et al. 2020

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“…Both electrodes include an active material, a conductive agent, a current collector, and a polymeric binder. Although the content of the binder in electrodes is small (0.5-12 wt%), it is a key component of electrodes [5][6][7][8]. Binder materials have an influence on the physical structure and the whole electrical network integrity of electrodes [9].…”

Section: Introductionmentioning

confidence: 99%

Locust bean gum as green and water-soluble binder for LiFePO4 and Li4Ti5O12 electrodes

2020

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Locust Bean Gum (LBG, carob bean gum) was investigated as an environmentally friendly, natural, and water-soluble binder for cathode (LFP) and anode (LTO) in lithium-ion batteries (Li-ion). For the first time, we show LBG as an electrode binder and compare to those of the most popular aqueous (CMC) and conventional (PVDF) binders. The electrodes were characterized using TGA/DSC, the galvanostatic charge–discharge cycle test, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). Thermal decomposition of LBG is seen to begin above 250 °C with a weight loss of about 60 wt% observed at 300 °C, which is sufficient to ensure stable performance of the electrode in a Li-ion battery. For CMC, weight loss at the same temperature is about 45%. Scanning electron microscopy (SEM) shows that the LFP–LBG system has a similar distribution of conductive carbon black particles to PVDF electrodes. The LTO–LBG electrode has a homogeneous dispersion of the electrode elements and maintains the electrical integrity of the network even after cycling, which leads to fast electron migration between LTO and carbon black particles, as well as ion conductivity between LTO active material and electrolyte, better than in systems with CMC and PVDF. The exchange current density, obtained from impedance spectroscopy fell within a broad range between 10−4 and 10−2 mA cm−2 for the LTO|Li and LFP|Li systems, respectively. The results presented in this paper indicate that LBG is a new promising material to serve as a binder. Graphic abstract

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“…To enhance the performance of the Li/CF x battery, many efforts have been devoted to overcoming these drawbacks. These efforts may be divided into three categories: (1) the improvement of the CF x cathode conductivity, which includes a new material, hybrid cathode, preparation method, conductive additive, and surface modification; − (2) the exploration of a novel electrolyte, which includes a low-temperature electrolyte, a high-temperature electrolyte, and a solid-state electrolyte; − and (3) the geometry modification of the discharge product layer, which comprises the electrolyte additive and a selection of different CF x materials. − …”

Section: Introductionmentioning

confidence: 99%

Study on Crystal Growth Kinetics and Preferred Orientation for LiF Crystal in Dimethyl Sulfoxide/1,3-Dioxolane-based Electrolyte

et al. 2019

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The Li/CF x primary battery with the highest energy density has been widely applied in many fields. However, the Li/CF x battery has been suffering from some problems for large-scale applications, such as low energy density, which needs to be overcome urgently. Among the technical solutions, the modification of the discharge product layer is an effective approach to solve the problem. To adjust the pore structure of the discharge product layer, it is necessary to explore both the growth and the orientation kinetics of LiF crystals as the main discharge product of Li/ CF x batteries. In this work, the growth kinetics of the LiF crystal during discharge in dimethyl sulfoxide/1,3-dioxolane (DMSO/1,3-DO)-based electrolytes is first explored by kinetic models of crystal growth. The calculated results show that the nucleation and nuclei growth mechanism is best suited for the growth kinetics of the LiF crystal in the DMSO/1,3-DO (5:5 v/v)-based electrolyte, which is different from the 2D diffusion mechanism of the LiF crystal in the PC/DME (5:5 v/v). Then, the orientation kinetics of LiF crystals is investigated by using quantum-chemical calculations. The simulation results reveal that the total chemical adsorption energies of both DMSO and 1,3-DO solvent molecules on the crystal planes of LiF could change with the ratio variation of DMSO/1,3-DO. The preferred crystal orientation growth of the LiF grain during discharge mainly depends on the total chemical adsorption energy on each crystal plane of LiF, which is caused by the selective adsorption of both DMSO and 1,3-DO on different crystal planes. The study of the growth kinetics of LiF grains and the preferred orientation growth can help our understanding of the structure control mechanism of discharge products of LiF. In general, this work may pave the way for the future development of a novel electrolyte of the large-capacity Li/CF x battery with high power density.

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Kinetics of Na|CF x and Li|CF x systems

Cited by 16 publications

References 64 publications

Reaction Mechanism and Structural Evolution of Fluorographite Cathodes in Solid‐State K/Na/Li Batteries

Reaction Mechanism and Structural Evolution of Fluorographite Cathodes in Solid‐State K/Na/Li Batteries

Locust bean gum as green and water-soluble binder for LiFePO4 and Li4Ti5O12 electrodes

Study on Crystal Growth Kinetics and Preferred Orientation for LiF Crystal in Dimethyl Sulfoxide/1,3-Dioxolane-based Electrolyte

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