Sulfide solid electrolytes, preparation method thereof and all-solid lithium secondary battery

A solid electrolyte and sulfide technology, applied in the field of lithium ion batteries, can solve problems such as performance degradation, change, and air instability, and achieve the effects of improving air stability, improving ionic conductivity, and increasing content

Active Publication Date: 2014-01-22
ZHEJIANG FUNLITHIUM NEW ENERGY TECH CO LTD
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] At present, a variety of sulfide solid electrolyte materials have been developed. For example, the Chinese patent with the publication number CN102959646A discloses a sulfide electrolyte for all-solid-state lithium secondary batteries. The solid electrolyte material is composed of Li 2 S and P 2 S 5 Composition, ionic conductivity up to 10 -4 S cm -1 , although the ionic conductivity of the sulfide electrolyte material disclosed in this patent is high, it is unstable to the air, which seriously affects the low-cost and large-scale production of the sulfide electrolyte material. At the same time, it will greatly increase the solid-state battery engineering preparation process. the complexity of
In order to

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  • Sulfide solid electrolytes, preparation method thereof and all-solid lithium secondary battery
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  • Sulfide solid electrolytes, preparation method thereof and all-solid lithium secondary battery

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preparation example Construction

[0050] Due to the different preparation methods of the sulfide solid electrolyte, the present application also provides a sulfide solid electrolyte as shown in formula (II),

[0051] (100-y)[(100-x)Li 2 S·xP 2 S 5 ] · yM (Ⅱ);

[0052] Among them, 0

[0053] 0

[0054] M is one or more of oxides of lanthanide elements, oxides of transition metals of the fourth period or fifth period of the periodic table, oxides of main group metals and silicon dioxide.

[0055] According to the present invention, oxides are also introduced into the sulfide solid electrolyte represented by formula (II), M in formula (I) and M in formula (II) can be the same or different, and this application does not special restrictions. M in formula (II) can be expressed as Q c o d , where c / d is preferably 0.32 O, SiO 2 , Fe 2 o 3 , ZrO 2 、TiO 2 , La 2 o 3 , Nb 2 o 5 or GeO 2 , more preferably Fe 2 o 3 , La 2 o 3 , Nb 2 o 5 or GeO 2 , x is preferably 10≤x≤30, and y is pre...

Embodiment 1

[0085] Under the protection of argon atmosphere, Li with a purity of more than 99% 2 S, P 2 S 5 with Li 2 O After weighing according to the molar ratio of 75:24:1, manually grind and mix evenly under the condition that the water content is less than 100ppm, then high-energy ball milling under the condition of 500rpm speed and 20:1 ball-to-material ratio for 10h to obtain the initial powder material, take out the powder After the raw material is ground finely and evenly, it is pressed into tablets with a pressure of 10 MPa to obtain a flaky raw material, and the flaky 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 obtain Powder all-solid-state lithium secondary battery sulfide electr...

Embodiment 2

[0091] 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 80:20, manually grind it evenly under the condition that the water content is less than 100ppm, and then use a high-energy ball mill for 10h to obtain 80%Li 2 S·20%P 2 S 5 Primary material of amorphous powder. at 80% Li 2 S·20%P 2 S 5 According to (80% Li 2 S·20%P 2 S 5 ): ZrO 2 =99:1 molar ratio to add ZrO 2 , and then continue ball milling for 20h to get 99% (80%Li 2 S·20%P 2 S 5 )·1%ZrO 2 Primary material of glass powder. Take out the above-mentioned glass powder primary material and grind it evenly, then use 10MPa pressure to press the tablet to obtain the flake primary material, put the flake primary material into the sintering mold, then put the sintering mold with the above-mentioned flaky primary material into the muffle furnace and Heat up to 380°C at a heating rate of 1°C / min, hold for 4 hours, then lower to 2...

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Abstract

The invention provides sulfide solid electrolytes shown by a formula (I) and sulfide solid electrolytes shown by a formula (II). The invention further provides a design thought and a preparation method of the sulfide solid electrolytes. A certain amount of oxide is doped and added to or compounded to the sulfide solid electrolytes, the air stability of the sulfide solid electrolytes is improved, and the ionic conductivity of the sulfide solid electrolytes is kept.

Description

technical field [0001] The invention relates to the technical field of lithium ion batteries, in particular to a sulfide solid electrolyte, a preparation method thereof, and an all-solid lithium secondary battery. Background technique [0002] Currently, lithium secondary batteries are widely used in daily life and become an inseparable part of society. Lithium secondary batteries have the advantages of large output power, high energy density, long service life, high average output voltage, small self-discharge, no memory effect, fast charge and discharge, excellent cycle performance and no environmental pollution. The preferred object of rechargeable power supply for electronic products is also considered to be the most competitive vehicle power battery. Lithium secondary batteries are classified into liquid lithium secondary batteries and solid lithium secondary batteries. Among them, a solid-state lithium secondary battery refers to a lithium secondary battery in which ...

Claims

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Application Information

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IPC IPC(8): H01M10/052H01M10/0562H01B1/10H01B1/06H01B13/00H01M4/62
CPCH01M10/0525H01M10/0562H01M2300/0068Y02E60/10
Inventor 许晓雄邱志军黄祯陈万超陈晓添
Owner ZHEJIANG FUNLITHIUM NEW ENERGY TECH CO LTD
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