Modified NASICON type oxide ceramic electrolyte as well as preparation method and application thereof

An oxide ceramic and electrolyte technology, applied in circuits, electrical components, secondary batteries, etc., can solve the problems of poor cycle performance of solid-state metal batteries, complex interface contact states, and large interface contact resistance, and improve interface compatibility. The effect of improving the carrier transport ability and suppressing the crack extension

Pending Publication Date: 2022-04-15
BEIJING INSTITUTE OF TECHNOLOGYGY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Among them, the ceramic electrolyte with NASICON structure (Li 1+x Al x Ti 2-x (PO 4 ) 3 , Li 1+x Al x Ge 2-x (PO 4 ) 3 , Na 1+x Zr 2 Si x P 3-x o 12 ) has stable chemical properties, wide electrochemical window and relatively high ionic conductivity (up to 10 at ro

Method used

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  • Modified NASICON type oxide ceramic electrolyte as well as preparation method and application thereof
  • Modified NASICON type oxide ceramic electrolyte as well as preparation method and application thereof
  • Modified NASICON type oxide ceramic electrolyte as well as preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0069] Prepare NASICON type oxide ceramic electrolyte, the NASICON type ceramic electrolyte is Na 1+x Zr 2 Si x P 3- x o 12 , where x=2:

[0070] (1) Weigh 0.03molNa 2 CO 3 , 0.02molZrN 2 o 7 (zirconyl nitrate), 0.02molSiO 2 with 0.01molNH 4 h 2 PO 4 , add ethanol ball mill for 12h, rotating speed 300r·min -1 , after uniform ball milling, discharging and drying;

[0071] (2) Put the mixture described in step (1) in a muffle furnace, raise the temperature to 1000°C, keep it warm for 6h, and the heating rate is 3°C·min -1 , cooled to room temperature to obtain a pre-sintered block;

[0072] (3) The pre-sintered block obtained in step (2) is subjected to secondary ball milling, discharging, and after drying, the pre-sintered powder is placed in an agate mortar and the mass fraction is 5% PVA aqueous solution, after fully grinding dry;

[0073] (4) Compressing the powder obtained in step (3) into tablets under a pressure of 10MPa, wherein the holding time is 10s; ...

Embodiment 2

[0077] Prepare modified NASICON type oxide ceramic electrolyte, the NASICON type ceramic matrix is ​​Na 1+x Zr 2 Si x P 3- x o 12 , where x=2; add BaTiO with a mass ratio of 3% 3 modified:

[0078] (1) Weigh 0.03molNa 2 CO 3 , 0.02molZrN 2 o 7 (zirconyl nitrate), 0.02molSiO 2 with 0.01molNH 4 h 2 PO 4 , add ethanol ball mill for 12h, rotating speed 300r·min -1 , after uniform ball milling, discharging and drying;

[0079] (2) Put the mixture described in step (1) in a muffle furnace, raise the temperature to 1000°C, keep it warm for 6h, and the heating rate is 3°C·min -1 , cooled to room temperature to obtain a pre-sintered block;

[0080] (3) The pre-sintered powder obtained in step (2) and its mass ratio are 3% commercially obtained BaTiO 3 The powder is evenly mixed for ball milling, discharged, and after drying, put in an agate mortar and add an aqueous solution of PVA with a mass fraction of 5%, fully grind and then dry;

[0081] (4) Compressing the powd...

Embodiment 3

[0085] Preparation of modified NASICON-type oxide ceramic electrolyte, the NASICON-type ceramic matrix is ​​Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 ; Add mass ratio of 3% (K,Na)NbO 3 modified:

[0086] (1) Weigh 0.013molLi 2 CO 3 , 0.003molAl(NO 3 ) 3 , 0.017molTiO 2 with 0.03molNH 4 h 2 PO 4 , add ethanol ball mill for 12h, rotating speed 300r·min -1 , after uniform ball milling, discharging and drying;

[0087] (2) Put the mixture described in step (1) in a muffle furnace, raise the temperature to 800°C, keep it warm for 6h, and the heating rate is 3°C·min -1 , cooled to room temperature;

[0088] (3) The pre-sintered powder obtained in step (2) and its mass ratio are 3% (K, Na) NbO 3 The inorganic ferroelectric phase material is ball milled, discharged, dried, placed in an agate mortar and added with a 5% PVA aqueous solution, fully ground and dried;

[0089] (4) Compressing the powder obtained in step (3) into tablets under a pressure of 10MPa, wherein the holding ...

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Abstract

The invention provides a modified NASICON type oxide ceramic electrolyte. The modified NASICON type oxide ceramic electrolyte takes NASICON type oxide ceramic as a matrix; wherein an inorganic ferroelectric material is uniformly distributed at the grain boundary of the NASICON type oxide ceramic matrix, and the mass ratio of the inorganic ferroelectric material to the NASICON type oxide ceramic matrix is (0-5): 100. The modified NASICON type oxide ceramic electrolyte is prepared by uniformly distributing the inorganic ferroelectric material at the grain boundary of the NASICON type oxide ceramic matrix, the ferroelectric effect shown by the inorganic ferroelectric material improves the carrier transport characteristic between the ceramic electrolyte and a metal electrode, the nucleation growth and extension of metal dendrites are inhibited, and the performance of the NASICON type oxide ceramic electrolyte is improved. The problems of low ionic conductivity and poor battery cycling stability of the solid electrolyte are effectively solved; the modified NASICON type oxide ceramic electrolyte provided by the invention is mainly applied to all-solid-state batteries, semi-solid-state batteries or quasi-solid-state batteries.

Description

technical field [0001] The invention relates to the technical field of solid metal batteries, in particular to a modified NASICON oxide ceramic electrolyte and its preparation method and application. Background technique [0002] The depletion of fossil energy has prompted the continuous development of renewable clean energy such as solar energy, wind energy, and geothermal energy. Therefore, it is urgent to develop a matching energy storage system. Due to the advantages of high conversion efficiency and convenient maintenance, the electrochemical energy storage system has the greatest potential for application and promotion. Since the commercial application of lithium-ion batteries in 1991, it has dominated the field of small consumer electronics such as notebook computers, mobile phones, and smart wearables. ) also show impressive potential. [0003] Traditional metal-ion batteries mostly use organic liquid electrolytes, which are prone to problems such as electrode mate...

Claims

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Application Information

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IPC IPC(8): H01M10/0562
CPCY02E60/10
Inventor 赵永杰
Owner BEIJING INSTITUTE OF TECHNOLOGYGY
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