Preparation method of LLZO solid electrolyte with long cycle life and solid lithium battery

A technology of solid electrolyte and solid electrolyte membrane, applied in the direction of non-aqueous electrolyte batteries, electrolytes, lithium batteries, etc., can solve the problems of limited improvement of interface contact, deterioration of interface conductivity, and reduced battery cycle life, so as to improve the structure and electricity. Effects of chemical stability, prolonging cycle life, and improving interfacial compatibility

Pending Publication Date: 2022-05-27
WANXIANG 123 CO LTD
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] Chinese patent CN201910797734.X discloses "an improved method for garnet-type solid electrolyte". The surface of garnet-type solid electrolyte is coated with acidic substances or ammonium salt substances. After high-temperature reaction, pollutants are removed and even converted into Uniformly deposit useful substances on lithium metal to improve the electrochemical performance of the battery, but only by removing pollutants through surface treatment to improve the affinity between lithium metal and LLZO, the degree of improvement in interface contact is limited; disclosed in Chinese patent CN112490445A "Preparation and Application of Modified Lithium Composite Anode Materials for Improving the Interface of Solid State Batteries", using molten metal lithium to improve its surface wettability to LLZO, improving the interface contact between lithium metal and LLZO, and also realizing the interface between the negative electrode and the electrolyte Tightly combined, but under continuous charge and discharge, especially at high current density, the volume change during the cycle may cause interfacial gaps in the coating, and even cause the separation of lithium metal and LLZO, deteriorating the interface conductivity and reducing the cycle life of the battery

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0036] Preparation of LLZO Solid Electrolytes Doped with Lithium Substitutes: La(NO 3 ) 3 , ZrOCl 2 , Al(NO 3 ) 3 , LiNO 3 According to the stoichiometric ratio of 3:2:7:0.07, it was added to isopropanol (IPA), the mass ratio of IPA in the mixed solution was 50%, and the mixture was stirred and fully mixed at room temperature for 10 hours, and then the LiNO used was added. 3 Molar ratio of 12% LiOH·H 2O to compensate for the loss of lithium volatilization, the above mixed materials were dried and calcined in air at 1000 °C and kept for 12 h. Naturally cooled to room temperature, the obtained powder was mixed with a small amount of IPA and then ball-milled in a high-energy vibration self-ball mill for 5 hours. The mass ratio of powder to IPA was 30:8. Finally, the powder was calcined at 1100 °C for 9 hours. After cooling to room temperature, 200 MPa was used. The particles were pressed into sheets by pressure, and the Al-doped LLZO solid electrolyte membrane Al-LLZO was o...

Embodiment 2

[0038] Preparation of LLZO Solid Electrolytes Doped with Lithium Substitutes: La(NO 3 ) 3 , ZrOCl 2 , Al(NO 3 ) 3 , LiNO 3 According to the stoichiometric ratio of 3:2:7:0.05, it was added to isopropanol (IPA), the mass ratio of IPA in the mixed solution was 65%, and the mixture was stirred and mixed at room temperature for 11 hours, and then the LiNO used was added. 3 Molar ratio of 10% LiOH·H 2 O to compensate for the loss of lithium volatilization, the above mixed materials were dried and calcined in air at 1000 °C and kept for 10 hours. Naturally cooled to room temperature, the obtained powder was mixed with a small amount of IPA and then ball-milled in a high-energy vibration self-ball mill for 5 hours. The mass ratio of powder to IPA was 35:10. Finally, the powder was calcined at 1100 °C for 9 hours. After cooling to room temperature, 200 MPa was used. The particles were pressed into sheets by pressure, and the Al-doped LLZO solid electrolyte membrane Al-LLZO was o...

Embodiment 3

[0040] Preparation of LLZO Solid Electrolytes Doped with Lithium Substitutes: La(NO 3 ) 3 , ZrOCl 2 , Al(NO 3 ) 3 , LiNO 3 According to the stoichiometric ratio of 3:2:7:0.09, it was added to isopropanol (IPA), the mass ratio of IPA in the mixed solution was 57.5%, and the mixture was stirred and fully mixed at room temperature for 12 hours, and then the LiNO used was added. 3 Molar ratio of 11% LiOH·H 2 O to compensate for the loss of lithium volatilization, the above mixed materials were dried and calcined in air at 1000 °C and kept for 12 h. Naturally cooled to room temperature, the obtained powder was mixed with a small amount of IPA and then ball-milled in a high-energy vibration self-ball mill for 6 hours. The mass ratio of powder to IPA was 35:6. Finally, the powder was calcined at 1000 °C for 9 hours. After cooling to room temperature, 200 MPa was used. The particles were pressed into sheets by pressure, and the Al-doped LLZO solid electrolyte membrane Al-LLZO wa...

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Abstract

The invention relates to the technical field of solid lithium batteries, in particular to an LLZO solid electrolyte with long cycle life and a preparation method of a solid lithium battery. The preparation method of the LLZO solid electrolyte with the long cycle life is characterized by comprising the following steps: (1) adding La (NO3) 3, ZrOCl2, lithium ions and a lithium atom substitution agent into an organic solvent, and stirring and mixing to obtain a mixed solution; (2) adding lithium ions accounting for 10-12% of the molar weight of the lithium ions in the step (1) into the mixed solution, drying and calcining, naturally cooling to room temperature to obtain powder, mixing the powder with an organic solvent, and performing ball milling to obtain a ball-milled material; and (3) cooling the ball-milled powder, and then pressing the ball-milled powder into sheets to obtain a doped LLZO solid electrolyte membrane, namely the LLZO solid electrolyte with long cycle life. The LLZO solid electrolyte and a three-dimensional lithium composite negative plate are used for preparing a lithium battery, so that the effects of improving the ionic conductivity, reducing the internal resistance of the solid lithium battery and prolonging the cycle life can be achieved.

Description

technical field [0001] The invention relates to the technical field of solid lithium batteries, in particular to an LLZO solid electrolyte with long cycle life and a method for preparing a solid lithium battery. Background technique [0002] Solid lithium batteries have become the main energy storage devices in the existing energy field due to their high safety and high energy density. People have higher and higher requirements for the safety and conductivity of solid lithium batteries. 7 La 3 Zr 2 O 12 (LLZO) has received extensive attention due to its high ionic conductivity, wide electrochemical stability window, and good chemical stability, but poor interfacial contact between solid electrolyte and electrodes used in solid lithium batteries is a bottleneck in the development of solid-state batteries. Lithium-phobic surface, lithium dendrite precipitation, especially residual pollutants such as lithium hydroxide or lithium carbonate on the surface will hinder the conta...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M10/0562H01M10/052
CPCH01M10/0562H01M10/052H01M2300/0071Y02P70/50
Inventor 宫娇娇陈军黄建根郑利峰
Owner WANXIANG 123 CO LTD
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