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Surface coated and modified lithium lanthanum zirconium oxygen-based solid electrolyte material and preparation method and application thereof

A technology of solid electrolyte, lithium lanthanum zirconium oxide, which is applied in the field of lithium lanthanum zirconium oxide solid electrolyte material and its preparation, can solve the problems of safety restrictions on lithium ion batteries, increased charge and discharge polarization, and poor interface contact. Achieve the effects of broadening the application range, alleviating volume deformation, and improving surface chemical stability

Active Publication Date: 2019-09-20
济宁克莱泰格新能源科技有限公司
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, safety issues have always been a major bottleneck restricting the application of lithium-ion batteries in large-scale energy storage fields such as power batteries and smart grids.
Due to the high hardness and brittleness of LLZTO, it is difficult to form a good contact interface with inorganic cathode materials
During the battery cycle, both the positive electrode material and the metal lithium negative electrode will undergo a large volume change, and the resulting stress will lead to poor interface contact, increased internal resistance of the battery, and increased charge-discharge polarization.

Method used

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  • Surface coated and modified lithium lanthanum zirconium oxygen-based solid electrolyte material and preparation method and application thereof
  • Surface coated and modified lithium lanthanum zirconium oxygen-based solid electrolyte material and preparation method and application thereof
  • Surface coated and modified lithium lanthanum zirconium oxygen-based solid electrolyte material and preparation method and application thereof

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preparation example Construction

[0035] The preparation method of the surface-coated modified lithium-lanthanum-zirconium-based solid electrolyte material comprises:

[0036] (1) Preparation of the lithium lanthanum zirconium oxide solid electrolyte (LLZO);

[0037] The preparation method of lithium lanthanum zirconium oxide solid electrolyte (LLZO) is a sol-gel method, and the preparation steps include: the precursors of lithium Li, lanthanum La, zirconium Zr and doping element M are prepared according to the formula of Li, La, Zr, M The molar ratio is (5+x): 3:x:(2-x) mixing, adding a solvent to dissolve, adding a precipitating agent to form a sol-gel, heating and evaporating the solvent to obtain a mixed powder; grinding the mixed powder, first in Sintering at 250-600° C. for 2-48 hours, grinding again, and sintering at 500-1000° C. for 2-48 hours to obtain the lithium lanthanum zirconium oxide solid electrolyte (LLZO).

[0038] Alternatively, the preparation method of the lithium lanthanum zirconium oxid...

Embodiment 1

[0043] (1) The chemical formula is Li prepared by solid-state reaction method 6.75 La 3 Zr 1.75 Ta 0.25 o 12 Lithium-lanthanum-zirconium-based solid electrolyte powder, the preparation steps of which include: selecting LiOH, La 2 o 3 , ZrO 2 and Ta 2 o 5 LiOH is used as a raw material with an excess of 10 wt% LiOH, which is ball-milled in alcohol for 24 hours and then dried; then calcined at 900°C for 10 hours with a heating rate of 4°C / min, and after the sintering is completed, the powder is crushed and sieved to obtain Li 6.75 La 3 Zr 1.75 Ta 0.25 o 12 Powder (LLZTO).

[0044] (2) Dry and sieve the LLZTO powder for pretreatment, then place the pretreated LLZTO powder in the chemical vapor deposition reaction chamber, evacuate the reaction chamber to 5Pa, and preheat to the coating temperature of 800°C; The cladding material is oxide glass solid electrolyte 0.5Li 2 CO 3 0.5 Li 3 BO 3 (LCBO), heat its precursor to 100°C, the reaction chamber starts to rotate, ...

Embodiment 2

[0050] (1) The chemical formula is Li prepared by solid-state reaction method 6.75 La 3 Zr 1.75 Ta 0.25 o 12 Lithium-lanthanum-zirconium-based solid electrolyte powder, the preparation steps of which include: selecting LiOH, La 2 o 3 , ZrO 2 and Ta 2 o 5 LiOH is used as a raw material with an excess of 10 wt% LiOH, which is ball milled in alcohol for 24 hours and then dried; then calcined at 900 °C for 10 hours with a heating rate of 4 °C / min, and after the sintering is completed, the powder is crushed and sieved to obtain Li 6.75 La 3 Zr 1.75 Ta 0.25 o 12 Powder (LLZTO), which is sieved to obtain LLZTO powder with uniform particle size.

[0051] (2) Dry and sieve the LLZTO powder for pretreatment, then place the pretreated LLZTO powder in the chemical vapor deposition reaction chamber, evacuate the reaction chamber to 5 Pa, and preheat to the coating temperature of 700 °C ; The precursor of the cladding layer material is a sulfide glass solid electrolyte Li 2 S-...

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Abstract

The invention discloses a surface coated and modified lithium lanthanum zirconium oxygen-based solid electrolyte material and preparation method and application thereof. The electrolyte material comprises a core and a coating layer, wherein the coating layer is coated on a surface of the core, the core is a lithium lanthanum zirconium oxygen-based solid electrolyte (LLZO), and the coating layer material is at least one of amorphous-state glass solid electrolyte materials with lithium ion conductivity. The involved coating layer material is relatively high in flexibility, the coated and modified lithium lanthanum zirconium oxygen can form favorable interface contact with an electrode material in a solid-state lithium battery composite electrode, the volume deformation of the composite electrode during the circulation process is reduced, and the energy density and the cycle stability of the lithium lanthanum zirconium oxygen-based solid-state lithium battery are further improved.

Description

technical field [0001] The invention relates to the technical field of batteries, in particular to a surface-coated modified lithium-lanthanum-zirconium-based solid electrolyte material and a preparation method and application thereof. Background technique [0002] The development of high-efficiency secondary battery energy storage devices is of great strategic significance for improving power balance, developing wind and solar sustainable energy, and promoting the development of new energy vehicles. Lithium-ion batteries have the advantages of high specific energy, high specific power, small self-discharge, and no memory effect, and have gradually entered the fields of electric vehicles, rail transit, and large-scale energy storage. However, safety issues have always been a major bottleneck restricting the application of lithium-ion batteries in large-scale energy storage fields such as power batteries and smart grids. Currently widely used lithium-ion batteries use volati...

Claims

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Application Information

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IPC IPC(8): H01M10/0562H01M10/42H01M10/052H01M10/0525
CPCH01M10/0562H01M10/052H01M10/0525H01M10/4235H01M2300/0068H01M2300/0071Y02E60/10
Inventor 郭向欣郭新赵宁
Owner 济宁克莱泰格新能源科技有限公司
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