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F<->, Zn<2+>, and B<3+> co-doped NASICON type solid lithium-ion electrolyte

A solid electrolyte, lithium ion technology, applied in circuits, electrical components, secondary batteries, etc., can solve the problem that the conductivity of non-thin-film lithium ion batteries cannot be well satisfied with the electrolyte, and increase the Li+ migration ability and weaken the bonding force. , the effect of reducing steric hindrance

Inactive Publication Date: 2012-05-16
NINGBO UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the room temperature lithium ion conductivity of these systems is usually in the range of 10 -4 S / cm-10 -6 Between S / cm, it still cannot meet the requirements of electrolyte conductivity for non-thin film lithium-ion batteries

Method used

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  • F&lt;-&gt;, Zn&lt;2+&gt;, and B&lt;3+&gt; co-doped NASICON type solid lithium-ion electrolyte
  • F&lt;-&gt;, Zn&lt;2+&gt;, and B&lt;3+&gt; co-doped NASICON type solid lithium-ion electrolyte

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0010] Embodiment 1: ZnO: LiF: B 2 o 3 :TiO 2 : NH 4 h 2 PO 4 : Li 2 CO 3 Mix evenly in a ratio of 0.1:0.1:0.05:1.9:2.9:0.6 (molar ratio), add 3% of 95% ethanol, and ball mill in a ball mill at a speed of 100 rpm for 15 hours, and vacuum at 60°C after ball milling Dry in an oven (vacuum degree 20 Pa) for 3 hours, take it out and re-grind in an agate mortar for 30 minutes, and the ground powder is heated to 700°C at a rate of 6°C / min and kept for 6 hours to make a solid electrolyte powder. The powder is mixed with 2wt% binder (PVC) and kept under a pressure of 250MPa for 2 minutes under a press to form a thin sheet, which is heated to 800°C at a rate of 10°C / min and kept for 10 hours under a nitrogen atmosphere to make lithium Ionic solid electrolyte sheets.

Embodiment 2

[0011] Embodiment 2: ZnO: LiF: B 2 o 3 :GeO 2 : NH 4 h 2 PO 4 : Li 2 CO 3 Mix evenly in a ratio of 0.3: 0.15: 0.1: 1.7: 2.8: 0.85 (molar ratio), add 9% 95% ethanol, and ball mill for 45 hours at a speed of 450 rpm in a ball mill. Dry in an oven (vacuum degree 95 Pa) for 9 hours, take it out and re-grind in an agate mortar for 30 minutes, and the ground powder is heated at a rate of 25°C / min to 950°C for 15 hours to make a solid electrolyte powder. The powder is mixed with 5wt% binder (PVC) and kept under a pressure of 450MPa for 6 minutes under a press to form a thin sheet, which is heated to 1000°C at a rate of 25°C / min and kept for 10 hours under a nitrogen atmosphere to make lithium Ionic solid electrolyte sheets.

Embodiment 3

[0012] Embodiment 3: ZnO: LiF: B 2 o 3 : ZrO 2 : NH 4 h 2 PO 4 : Li 2 CO 3 Mix evenly in a ratio of 0.5:0.2:0.15:1.5:2.7:1.1 (molar ratio), add 5% 95% ethanol, and ball mill in a ball mill at a speed of 300 rpm for 30 hours, and vacuum at 75°C after ball milling Dry in an oven (vacuum degree 50 Pa) for 6 hours, take it out and re-grind in an agate mortar for 20 minutes, and the ground powder is heated at a rate of 10°C / min to 850°C for 12 hours to make a solid electrolyte powder. The powder is mixed with 2.6wt% binder (PVA) and kept under a pressure of 400 MPa under a press for 4 minutes to form a thin sheet. The thin sheet is heated to 900°C at a rate of 15°C / min and kept for 7 hours under a nitrogen atmosphere. Lithium ion solid electrolyte sheet.

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Abstract

The invention relates to an F<->, Zn<2+>, and B<3+> co-doped NASICON type solid lithium-ion electrolyte, which is characterized by having a stoichiometric equation of Li1+2x+2z-yZnxBzM2-xP3-zO12-yFy, wherein, x=0.1-0.5; y=0.1-0.2; z=0.1-0.3; M is one of Ti, Ge and Zr. According to the invention, ZnO, LiF, B2O3, MO2 (M=Ti, Ge, Zr), NH4H2PO4, and Li2CO3 are mixed uniformly in a mole ratio of 0.1-0.5:0.1-0.2:0.05-0.15:1.5-1.9:2.7-2.9:0.5-1.2, then the obtained mixture is subjected to ball milling, pressing and sintering, thus obtaining a solid lithium-ion electrolyte with room temperature lithium ion conductivity higher than 9.10<-4>S / cm.

Description

technical field [0001] The invention relates to the field of manufacturing a solid lithium ion electrolyte. Background technique [0002] Lithium-ion batteries have absolute advantages such as high volume, high weight-to-energy ratio, high voltage, low self-discharge rate, no memory effect, long cycle life, and high power density. They have an annual share of more than 30 billion US dollars in the global mobile power market and far exceed other The market share of batteries is the most promising chemical power source [Wu Yuping, Wan Chunrong, Jiang Changyin, Lithium-ion Secondary Batteries, Beijing: Chemical Industry Press, 2002.]. At present, most of the lithium-ion secondary batteries at home and abroad use liquid electrolytes. Liquid lithium-ion batteries have some disadvantages, such as: liquid organic electrolytes may leak, and may explode at too high a temperature, causing safety accidents, and cannot be used in some applications. Occasions with high safety requiremen...

Claims

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Application Information

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IPC IPC(8): H01M10/0562
CPCY02E60/12Y02E60/10
Inventor 水淼舒杰任元龙徐丹郑卫东任政娟王青春黄峰涛
Owner NINGBO UNIV
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