Open framework fluorine-based solid-state electrolyte material and preparation method of open framework fluorine-based solid-state electrolyte material

A technology of solid electrolytes and electrolyte materials, applied in the field of open-frame lithium-rich or sodium-rich fluorine-based solid electrolyte materials and their preparation, can solve the problems of limited electrochemical stability window, instability, complex phase diagram, etc. The effect of improving ionic conductivity, inhibiting battery performance attenuation, and simple process flow

Active Publication Date: 2017-06-23
SHANGHAI INST OF CERAMIC CHEM & TECH CHINESE ACAD OF SCI
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  • Application Information

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Problems solved by technology

Although oxide electrolytes have good stability in air, their overall conductivity is greatly reduced due to the large particle boundary resistance, and the rare earth metals contained are expensive; and the electronegativity of S is smaller than that of oxygen, making the ions of sulfide electrolytes The conductivity is often greater than that of oxides, and sulfides are easier to densify, and their interface conductivity can even be ignored. The disadvantage is air sensitivity (easy to generate H 2 S), the phase diagram is more complex, and the component deviation has a greater influence on the conductivity
Many inorganic glass-ceramic electrolytes contain redox elements (e.g., Ti, Ge, etc.), whose interfaces may be unstable when in contact with lithium, which limits their electrochemical stability window
[0004] Although lithium salt LiPF 6 Has been widely used in lithium batteries, but fluoride as a solid electrolyte is still rarely reported
In the early 1980s, Hitachi reported the amorphous LiF-AlF 3 and NaF-AlF 3 In the thin film system, it is found that the conductivity varies with the stoichiometric ratio of the compound, but the optimal room temperature conductivity is still only 10 -7 -10 -6 S / cm; Li was proposed by Tohoku University in 2012 3 AlF 6 Mixing ball milling with LiCl is beneficial to the significant improvement of lithium ion conductivity, especially the high lithium ion conductivity at the particle boundary, but its room temperature conductivity is only 2×10 -6 S / cm

Method used

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  • Open framework fluorine-based solid-state electrolyte material and preparation method of open framework fluorine-based solid-state electrolyte material
  • Open framework fluorine-based solid-state electrolyte material and preparation method of open framework fluorine-based solid-state electrolyte material
  • Open framework fluorine-based solid-state electrolyte material and preparation method of open framework fluorine-based solid-state electrolyte material

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Experimental program
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Effect test

Embodiment 1

[0054] 1) Li 3 AlF 6 Ionic Liquid-Based Preparation of Solid Electrolyte Nanoparticles:

[0055] Weigh 0.3g of Li 2 CO 3 Added to 10 mL of 1-butyl-3-methylimidazolium tetrafluoroborate (BmimBF 4 ) in the ionic liquid, stirred at room temperature for 6 hours to obtain a uniform cloudy solution. Then, while stirring, slowly add 1 g of Al(NO 3 ) 3 9H 2 O, stirring continued for 12 hours to obtain a cloudy solution from which a precipitate could precipitate. The reaction precipitate was repeatedly centrifuged and washed with anhydrous acetone, and vacuum-dried at 80° C. to obtain the solid electrolyte material. Li 3 AlF 6 SEM of solid electrolyte nanoparticles as attached figure 1 Shown, illustrate that embodiment (1) can successfully prepare the nanoscale solid electrolyte material of 20-50nm scale, and because potential surface modification (being the conformal coating of ionic liquid positive group), can reduce particle surface energy, It is conducive to uniform dis...

Embodiment 2

[0057] 1)Na 3 AlF 6 Ionic Liquid-Based Preparation of Solid Electrolytes:

[0058] Weigh 0.424g of Na 2 CO 3 Added to 10 mL of 1-butyl-3-methylimidazolium tetrafluoroborate (BmimBF 4 ) in the ionic liquid, stirred at room temperature for 6 hours to obtain a uniform cloudy solution. Then, while stirring, slowly add 1 g of Al(NO 3 ) 3 9H 2 O, stirring continued for 12 hours to obtain a cloudy solution from which a precipitate could precipitate. Wash the reaction precipitate by repeated centrifugation with anhydrous acetone, and dry it in vacuum at 80°C to obtain Na 3 AlF 6 A solid electrolyte material for the main phase. XRD attached image 3 As shown, a sharper main phase Na can be found 3 AlF 6 The diffraction peak pattern is doped with a broad heterophase Na 5 Al 3 f 14 diffraction peaks.

[0059] 2) Conductivity test of solid electrolyte sheet:

[0060] Na prepared by embodiment 2 3 AlF 6 The solid electrolyte powder is pressed into a disk with a thickness ...

Embodiment 3

[0062] 1)Na 3 Li 3 Al 2 f 12 High-temperature solid-state reaction preparation of solid electrolytes:

[0063] Weigh 0.5g of NaF, 0.31g of LiF and 0.67g of AlF 3 , grind uniformly in the agate grinding body, press the mixture into a disc with a diameter of 10mm under a pressure of 15MPa, and then seal it in a stainless steel reaction kettle filled with an Ar atmosphere, and perform a solid-state reaction at 700°C for 10 hours, and the pressed tablet Crush and grind evenly again to get the desired product. Its XRD is attached Figure 5 As shown, the sharp Na 3 Li 3 Al 2 f 12 Diffraction peaks confirm the phase-pure nature of the material.

[0064] 2) Conductivity test of solid electrolyte sheet:

[0065] Na prepared by embodiment 3 3 Li 3 Al 2 f 12 The solid electrolyte powder is pressed into a disk with a thickness of 1mm and a diameter of 10mm, and the pressure of the tablet is 15MPa. Au electrodes with a diameter of 8mm were vapor-deposited on both sides of t...

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Abstract

The invention relates to an open framework fluorine-based solid-state electrolyte material and a preparation method of the open framework fluorine-based solid-state electrolyte material. A chemical formula of the electrolyte material is as follows: AxMyFx+3y, wherein x is more than 0 and less than or equal to 6, y is more than 0 and less than or equal to 3, A is Na and/or Li and M is Al and/or Ga. The open framework fluorine-based solid-state electrolyte material AxMyFx+3y provided by the invention is lithium-enriched or sodium-enriched phase aluminum-based or gallium-based fluoride; the invention provides application of a novel open framework structural prototype to fluoride solid-state electrolyte for the first time; meanwhile, lithium enriching or sodium enriching is realized; the concentration of transferable alkali metal ions is increased so that the intrinsic ionic conductivity is easy to improve; the electrical conductivity of a bulk phase and a particle boundary can be improved through means of nanocrystallization, disordering, surface modification and the like.

Description

technical field [0001] The invention belongs to the technical field of new energy, and in particular relates to an open-frame fluorine-based solid electrolyte material for an all-solid-state lithium battery or a sodium battery, especially an open-frame lithium-rich or sodium-rich fluorine-based solid electrolyte material and a preparation method thereof. Background technique [0002] In recent years, with the increase in the price of fossil fuels and the increasing environmental pollution, the demand for clean energy is particularly strong, especially in the fields of electric vehicles and energy storage systems based on green grids. The use and promotion of secondary batteries It is making the industry and academia invest more energy in the research of its new structure and key materials. At present, lithium-ion batteries based on organic electrolyte systems have two major problems that cannot be overcome, namely (1) the high volatility and corrosiveness of the electrolyte ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M10/0562H01M10/058H01M10/0525H01M10/054
CPCH01M10/0525H01M10/054H01M10/0562H01M10/058H01M2300/0085Y02E60/10Y02P70/50
Inventor 李驰麟曹敦平韩延林章也谢俊杰
Owner SHANGHAI INST OF CERAMIC CHEM & TECH CHINESE ACAD OF SCI
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