Lithium ion solid conductor stable on metal lithium, preparation method of lithium ion solid conductor, and full-solid lithium secondary battery

A lithium ion and metal lithium technology, applied in the field of all-solid lithium secondary batteries, can solve problems such as the instability of metal lithium restricting development and application, loss of safe electrode active materials, low charge-discharge cycle efficiency, etc., and achieve lithium ion conductivity Improve, improve stability, improve the effect of ion conductivity

Active Publication Date: 2015-12-09
ZHEJIANG FUNLITHIUM NEW ENERGY TECH CO LTD
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Fundamentally speaking, when lithium metal is used as the negative electrode of secondary batteries, the main problems are: (1) the low charge-discharge cycle efficiency and the continuous increase of interface impedance caused by complex interfacial reactions; (2) "dendrites" and The production of "dead lithium", the safety problems and the loss of electrode active materials
However, the instability of sulfide solid electrolytes to lithium metal greatly limits their development and application in all-solid-state lithium secondary batteries.

Method used

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  • Lithium ion solid conductor stable on metal lithium, preparation method of lithium ion solid conductor, and full-solid lithium secondary battery
  • Lithium ion solid conductor stable on metal lithium, preparation method of lithium ion solid conductor, and full-solid lithium secondary battery
  • Lithium ion solid conductor stable on metal lithium, preparation method of lithium ion solid conductor, and full-solid lithium secondary battery

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preparation example Construction

[0048] The present invention also provides a kind of preparation method of lithium ion solid conductor material as shown in formula (I), comprises the following steps:

[0049] A) will Li 2 S, P 2 S 5 Mix and grind with M to obtain the initial material;

[0050] B) under the condition of inert gas, heat treatment is carried out to described initial material, obtain the lithium ion solid conductor material as shown in formula (I);

[0051] (100-x)(yLi2 S·zP 2 S 5 )·xM formula (I)

[0052] In formula (I): 0

[0053] M is lithium halide.

[0054] In the present invention, Li 2 S, P 2 S 5 Mix and grind with M to get the initial material. In the present invention, preferably carry out Li under the condition of inert gas 2 S, P 2 S 5 For weighing and mixing grinding with M, the inert gas is preferably nitrogen or argon. Among them, the Li 2 S and P 2 S 5 The molar ratio of Li is preferably 3:1, Li 2 S and P 2 S 5 The molar ratio of the mixed sulfi...

Embodiment 1

[0066] Under the protection of argon atmosphere, Li with a purity of more than 99% 2 S, P 2 S 5 After weighing according to the molar ratio of 75:25, press (75Li 2 S·25P 2 S 5 ): LiI=90:10 molar ratio is added LiI, under the condition of water content less than 10ppm with 500rpm rotating speed grinds and mixes evenly, under the condition of 45:1 ball-to-material ratio condition, after high-energy ball milling 12h, obtain powder primary material, take out powder primary material After the material is ground finely and evenly, it is pressed into tablets with a pressure of 10 MPa to obtain a flake-like raw material, and the flake-like raw material is loaded into a sintering mold. Heat the sintering mold equipped with the above flake raw material to 250°C at a heating rate of 2°C / min, keep it warm for 2h, cool down to room temperature with the furnace, take out the flake sintered product under the condition that the water content is less than 100ppm, and grind it evenly to obt...

Embodiment 2

[0071] Under the protection of argon atmosphere, Li with a purity of more than 99% 2 S, P 2 S 5 After weighing according to the molar ratio of 75:25, press (75Li 2 S·25P 2 S 5 ): LiI=95:5 in molar ratio, add LiI, grind and mix uniformly at 200rpm under the condition of water content less than 10ppm, and obtain the primary powder after high-energy ball milling under the condition of 40:1 ball-to-material ratio for 18h, take out the primary powder After the material is ground finely and evenly, it is pressed into tablets with a pressure of 10 MPa to obtain a flake-like raw material, and the flake-like raw material is loaded into a sintering mold. Heat the sintering mold equipped with the above-mentioned flaky raw material to 300°C at a heating rate of 1°C / min, keep it warm for 4h, cool down to room temperature with the furnace, take out the flaky sintered product under the condition that the water content is less than 100ppm, and grind it evenly to obtain Powder all-solid l...

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Abstract

The invention provides a lithium ion solid conductor material shown as a formula (I): (100-x)(yLi2S.zP2S5).xM. In the formula (I), the x is greater than 0 but smaller than or equal to 40, a ratio of the y to the z is 3:1; the M is lithium halide. According to a lithium ion solid conductor, lithium halide compounds are introduced into sulphide electrolyte, so that halogen atoms and metal lithium mutually act to form a buffer layer, like an SEI film in a liquid lithium battery; the further reaction between the electrolyte material ingredient and the metal lithium is effectively relieved; the stability of the electrolyte and the metal lithium electrode is improved. In addition, the lithium halide compounds are introduced into the sulphide electrolyte; a multi-dimensional passage for lithium ion transmission is provided; the activity space is increased; the lithium ion conductivity improvement is caused. Therefore the ion conductivity of the sulphide electrolyte can also be improved through the introduction of lithium halide.

Description

technical field [0001] The invention belongs to the technical field of lithium batteries, and in particular relates to a lithium ion solid conductor material stable to metal lithium, a preparation method thereof, and an all-solid lithium secondary battery. Background technique [0002] The all-solid lithium secondary battery refers to a lithium secondary battery in which each unit of the battery, including the positive electrode, negative electrode and electrolyte, is made of solid materials. Lithium secondary batteries are widely used in daily life with many advantages such as large output power, high energy density, excellent cycle performance, no memory effect and no environmental pollution. The most competitive vehicle power battery. Since all-solid-state lithium secondary batteries have incomparable safety than liquid lithium secondary batteries, and are expected to completely eliminate safety hazards during use, they are more in line with the needs of future developme...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M10/0562H01M10/058H01M10/0525
CPCH01M10/0525H01M10/0562H01M10/058Y02E60/10Y02P70/50
Inventor 许晓雄陈少杰陶益成彭刚姚霞银
Owner ZHEJIANG FUNLITHIUM NEW ENERGY TECH CO LTD
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