Hydrogen storage properties of lithium silicon alloy synthesized by mechanical alloying

Doi, Koichi; Hino, Satoshi; Miyaoka, Hiroki; Ichikawa, Takayuki; Kojima, Yoshitsugu

doi:10.1016/j.jpowsour.2010.05.070

Cited by 29 publications

(27 citation statements)

References 15 publications

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“…Search for new materials -capable for storing hydrogen has been very attractive field of research for material scientists. The standard requirements as practical storage material are: (1) high storage capacity, (2) high charging discharging rate, (3) ambient working temperature and pressure condition. Light hydrides like MgH 2 [1] and LiH [2] with high storage capacities of 7.6 wt.% and 12.7 wt.% respectively fulfils the first requirement but lacks on other two due to their high thermodynamic stability.…”

Section: Introductionmentioning

confidence: 99%

Catalytic modification in dehydrogenation properties of KSiH₃

Jain

Ichikawa

Yamaguchi

et al. 2014

Phys. Chem. Chem. Phys.

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A number of known catalysts, which have been proven to be very effective for several hydrogen species, were studied in order to determine their effects on the hydrogen ab/desorption properties of KSiH3. Among all the catalysts used in this work, mesoporous Nb2O5 is found to be quite effective, with a reduction in activation energy from 142 kJ mol(-1) for pristine KSi to 63 kJ mol(-1) for mesoporous-Nb2O5-added KSi, thus allowing desorption to start at 100-120 °C. Any disproportionation is not observed in the controlled hydrogenation process. The mechanism for this improvement is also proposed in detail. The kinetic modifications on the ab/desorption properties of KSiH3 provide an alternative to the well-known family of heavy BCC alloys which are capable of working in the same temperature range but with a lower gravimetric hydrogen content, almost half of the KSi system.

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Section: Introductionmentioning

confidence: 99%

Catalytic modification in dehydrogenation properties of KSiH₃

Jain

Ichikawa

Yamaguchi

et al. 2014

Phys. Chem. Chem. Phys.

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“…[8] The exothermic formation of Li x Si or Mg 2 Si silicides reduces the large endothermic character of hydrogen desorption and thus decreases the reaction enthalpy. However, the destabilized LiH/Si system still operates at too high a temperature (573-673 K) [8][9] and the MgH 2 /Si system is not reversible; [10] the Mg 2 Si compound formed upon release of hydrogen cannot be hydrogenated back to MgH 2 and Si. [8] In contrast to the present work on KSiH 3 hydrides, Si does not form a M-Si-H ternary hydride in these destabilized systems but stays as an element or intermetallic.…”

Section: Introductionmentioning

confidence: 99%

Potassium Silanide (KSiH₃): A Reversible Hydrogen Storage Material

Chotard

Tang

Raybaud

et al. 2011

Chemistry A European J

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KSi silicide can absorb hydrogen to directly form the ternary KSiH(3) hydride. The full structure of α-KSiD(3), which has been solved by using neutron powder diffraction (NPD), shows an unusually short Si-D lengths of 1.47 Å. Through a combination of density functional theory (DFT) calculations and experimental methods, the thermodynamic and structural properties of the KSi/α-KSiH(3) system are determined. This system is able to store 4.3 wt% of hydrogen reversibly within a good P-T window; a 0.1 MPa hydrogen equilibrium pressure can be obtained at around 414 K. The DFT calculations and the measurements of hydrogen equilibrium pressures at different temperatures give similar values for the dehydrogenation enthalpy (≈23 kJ mol(-1) H(2)) and entropy (≈54 J K(-1) mol(-1) H(2)). Owing to its relatively high hydrogen storage capacity and its good thermodynamic values, this KSi/α-KSiH(3) system is a promising candidate for reversible hydrogen storage.

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“…8,10 The degree of pre-lithiation was controlled by changing the contact time. While a crystalline Li-Si alloy phase was synthesized by a mechanical alloying (MA) method 11 and studied based on density functional theory, 13,17 This is the Li-Si alloy phase without Si-Si bond; all Si atoms is surrounded by Li atoms.…”

mentioning

confidence: 99%

Effect of Mechanical Pre-Lithiation on Electrochemical Performance of Silicon Negative Electrode for Lithium-Ion Batteries

Domi

Usui

Daichi

et al. 2017

J. Electrochem. Soc.

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The effect of pre-lithiation on the electrochemical performance of Si negative electrodes for lithium-ion batteries was studied. A pre-volume-expansion of Si induced by the pre-lithiation is expected to decrease the relative change in volume of Si during chargedischarge reactions. Suppression of change in volume of Si should improve the cycle performance, the Coulombic efficiency, and so on. When the mechanically pre-doped Li was extracted from Li-Si alloy during the first cycle, an alloy electrode exhibited the poor cycle performance just like a Si-alone electrode. On the other hand, the Li 1.00 Si electrode exhibited the improved cycle performance and higher Coulombic efficiency under the discharge cut-off potential of 0.7 and 0.5 V, respectively. The electrode also showed 1.5 times longer cycle life compared to the Si-alone electrode when the charge capacity and the cut-off potential were limited. These results demonstrated that the appropriate mechanical pre-lithiation helps to improve the poor electrochemical performance of the Si negative electrodes. Silicon (Si) is a potential candidate as an active material for the negative electrode in lithium-ion batteries (LIBs) due to its high theoretical capacity of 3580 mA h g -1 (Li 3.75 Si). 1,2 However, a significant change in volume of Si occur during charge (lithiation) and discharge (delithiation) reactions. 3 The expansion ratio per Si atom from Si to Li 3.75 Si corresponds to 380%, which generates high stresses and large strains in the active material. 4 The strains that accumulate under repeated charge-discharge cycling result in cracking and pulverization of the active material, which causes a loss of electric contact with the current collector. Hence, the Si negative electrode disintegrates and shows a rapid capacity fading and a poor cycle performance. In addition, the cracking and pulverization of the active material cause a decrease in the Coulombic efficiency because the reductive decomposition of the electrolyte on the newly formed Si surface.5 High Coulombic efficiency is required to achieve the practical use of LIBs with new active materials.To improve the Coulombic efficiency of Si-based electrodes, researchers have proposed various approaches, including the synthesis of three-dimensional hyperporous silicon flakes, 6 a preparation of Si nanowire with interconnected structure, 7 and a pre-lithiation of Si, 8 In addition to compensate an irreversible capacity, the pre-lithiation has been previously reported to make a full battery with active materials of lithium-free positive and negative electrodes (e.g. Silicon-Sulfur). 9,10The pre-lithiation of Si was carried out mainly by an electrochemical and a chemical methods. In the electrochemical pre-lithiation, Si electrodes were galvanostatically charged and discharged for 10 cycles between 0.1 and 0.7 V vs. Li + /Li. 9 The Si electrodes were charged without any potential limitation to obtain a pre-lithiated Si in the final discharge step. In the chemical pre-lithiation, on the other hand, the Si elec...

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Hydrogen storage properties of lithium silicon alloy synthesized by mechanical alloying

Cited by 29 publications

References 15 publications

Catalytic modification in dehydrogenation properties of KSiH₃

Catalytic modification in dehydrogenation properties of KSiH₃

Potassium Silanide (KSiH₃): A Reversible Hydrogen Storage Material

Effect of Mechanical Pre-Lithiation on Electrochemical Performance of Silicon Negative Electrode for Lithium-Ion Batteries

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Hydrogen storage properties of lithium silicon alloy synthesized by mechanical alloying

Cited by 29 publications

References 15 publications

Catalytic modification in dehydrogenation properties of KSiH3

Catalytic modification in dehydrogenation properties of KSiH3

Potassium Silanide (KSiH3): A Reversible Hydrogen Storage Material

Effect of Mechanical Pre-Lithiation on Electrochemical Performance of Silicon Negative Electrode for Lithium-Ion Batteries

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Product

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Catalytic modification in dehydrogenation properties of KSiH₃

Catalytic modification in dehydrogenation properties of KSiH₃

Potassium Silanide (KSiH₃): A Reversible Hydrogen Storage Material