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A kind of ion conductor ceramic fiber composite diaphragm and its preparation method and application

An ion conductor and ceramic fiber technology, applied in the field of ion conductor ceramic fiber composite diaphragm and its preparation, can solve the problems of reducing the lithium ion conductivity of the diaphragm, reducing the porosity of the polymer diaphragm, increasing the internal resistance of the lithium ion battery, etc. The effect of improving Li-ion conductivity, improving puncture resistance and thermal stability, optimal battery capacity and cycle performance

Active Publication Date: 2020-12-08
QINGTAO KUNSHAN ENERGY DEV CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] At present, simple oxide ceramics are often used to coat traditional diaphragms to enhance the heat resistance and puncture resistance of the diaphragm; however, ceramic coating may block the pores of the polymer diaphragm, reduce the porosity of the polymer diaphragm, and The ionic conductivity of the selected ceramics is extremely low, which reduces the lithium ion conductivity of the diaphragm, increases the resistance of the diaphragm and increases the internal resistance of the lithium ion battery

Method used

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  • A kind of ion conductor ceramic fiber composite diaphragm and its preparation method and application
  • A kind of ion conductor ceramic fiber composite diaphragm and its preparation method and application
  • A kind of ion conductor ceramic fiber composite diaphragm and its preparation method and application

Examples

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Effect test

Embodiment 1

[0083] Li 7 La 3 Zr 2 o 12 Ionic Conductor Ceramic Fiber Composite Diaphragm S1

[0084] 1) Preparation of Li 7 La 3 Zr 2 o 12 Ceramic fiber

[0085] Weigh 5.69gLi according to the stoichiometric ratio 2 CO 3 (Li excess 10%) and 9.77gLa 2 o 3 Dissolved in 80g dilute nitric acid, 9.25g zirconium oxynitrate (ZrO(NO 3 ) 2 ) was dissolved in 20 g of absolute ethanol. The above two solutions were mixed and stirred in a constant temperature water bath environment at 50°C, then 53.80 g of citric acid and 8.69 g of ethylene glycol were added, and then stirred at a constant temperature for 12 hours to obtain a transparent sol. Add 50 g of 10% PVP aqueous solution, and fully stir for 24 hours, and use the above sol for air spinning. The fibers obtained by air spinning were calcined at 1000 °C for 60 minutes to obtain Li 7 La 3 Zr 2 o 12 Ceramic fiber, its conductivity was measured to be 6.7×10 -4 S / cm, the average length of the ceramic fiber is 2 μm, and the average ...

Embodiment 2

[0089] Li 0.35 La 0.55 TiO 3 Preparation of Ionic Conductor Ceramic Fiber Composite Separator S2

[0090] 1) Preparation of Li 0.35 La 0.55 TiO 3 ion conductor ceramic fiber

[0091] Weigh 1.59gLiNO 3 (Lithium excess 10%), 14.29gLa(NO 3 ) 3 ·6H 2 0, 20.40g tetrabutyl titanate and 12.01g acetylacetone are added in 300ml ethylene glycol methyl ether as raw materials, then adding 40g mass fraction is 10% polyvinyl alcohol aqueous solution and after fully stirring, obtain precursor solution; Then The above precursor was injected into the syringe of the electrospinning equipment, and the fiber precursor was obtained by electrospinning; then the fiber precursor was kept at 900°C for 3 hours to prepare Li 0.35 La 0.55 TiO 3 Ionic conductor ceramic fiber, the measured conductivity is 3.7×10 -4 S / cm, the average length of the ceramic fiber is 2 μm, and the average diameter is 300 nm.

[0092] 2) Preparation of composite diaphragm

[0093] With step 1) prepared Li 0.35 L...

Embodiment 3

[0095] Li 7-3y Al y La 3 Zr 2 o 12 (y=0.05) Preparation of Ion Conductor Ceramic Fiber Composite Diaphragm S3

[0096] 1) Preparation of Li 7-3y Al y La 3 Zr 2 o 12 (y=0.05) ion conductor ceramic fiber

[0097] Weigh 5.56gLi according to the stoichiometric ratio 2 CO 3 (Li excess 10%), 0.38g Al(NO 3 ) 3 9H 2 O with 9.77gLa 2 o 3 Dissolved in 80g dilute nitric acid, 9.25g zirconium oxynitrate (ZrO(NO 3 ) 2 ) was dissolved in 20 g of absolute ethanol. The above two solutions were mixed and stirred in a constant temperature water bath environment at 50°C, then 53.80 g of citric acid and 8.69 g of ethylene glycol were added, and then stirred at a constant temperature for 12 hours to obtain a transparent sol. Add 50 g of 10% PVP aqueous solution, and fully stir for 24 hours, and use the above sol for air spinning. The fibers obtained by air spinning were calcined at 1000°C for 60 minutes to obtain Li 6.85 Al 0.05 La 3 Zr 2 o 12 Ionic conductor ceramic fiber...

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Abstract

The invention provides an ionic conductor ceramic fiber composite diaphragm and a preparation method and an application thereof. The composite diaphragm provided by the invention comprises an organic polymer layer and an ionic conductor ceramic fiber layer glued on the surface of the organic polymer layer, wherein the chemical composition of the ionic conductor ceramic fiber layer is selected from one or more of ionic conductor fibers of Li<7>La<3>Zr<2>O<12>, Li<3x>La<2 / 3-x>TiO<3>, or Li<7-3y>Al<y>La<3>Zr<2>O<12>, wherein x is greater than 0 and less than 0.167, and y is greater than 0 and less than 0.15. The heat resistance and anti-puncture strength of the diaphragm are reinforced while relatively high ionic conduction performance is achieved; and when the composite diaphragm is used as the diaphragm of a lithium ion secondary battery, the safety performance can be reinforced and the high ionic conductivity of the composite diaphragm is improved.

Description

technical field [0001] The invention belongs to the technical field of lithium-ion battery diaphragms, and in particular relates to an ion conductor porcelain fiber composite diaphragm, a preparation method thereof and its application in lithium-ion batteries. Background technique [0002] The oil crisis in the 1960s and 1970s forced people to look for new alternative energy sources, and lithium batteries became one of the alternative energy sources due to their high mass and energy density; as the population increased and the earth's resources were limited, it forced people to think about it. Ways to improve the utilization of resources, and the use of rechargeable batteries is one of the effective ways, thus promoting the research and development of secondary batteries. Lithium-ion secondary batteries are currently widely used in the fields of electronic equipment mobile power supplies due to their high energy density, long life, and environmentally friendly components. Th...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): H01M2/14H01M2/16H01M10/0525C04B35/48C04B35/462C04B35/622
CPCC04B35/462C04B35/48C04B35/62227C04B2235/3203C04B2235/3217C04B2235/3227C04B2235/94C04B2235/95C04B2235/96H01M10/0525H01M50/403H01M50/431H01M50/44H01M50/449Y02E60/10
Inventor 冯玉川李峥何泓材何朝凌杨帆南策文
Owner QINGTAO KUNSHAN ENERGY DEV CO LTD