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COFs (Covalent Organic Frameworks) solid electrolyte containing lithium carboxylate group as well as preparation method and application of COFs solid electrolyte

A solid electrolyte, lithium carboxylate technology, applied in circuits, electrical components, secondary batteries, etc., can solve problems such as hindering the movement and migration of lithium ions, adverse effects of lithium metal batteries, limiting lithium ion content, etc., to promote lithium ions. Effects of migration, elimination of interface side reactions, and shortening of transition distances

Pending Publication Date: 2022-04-29
YUNNAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

At present, 2D-COFS lithium-ion batteries introduce lithium salts or organic solvents into the 2D-COFs framework for lithium ion transport, and the contact between the electrolyte and the electrode interface is improved by introducing organic solvents, but the free-moving anions and organic solvents in lithium salts The presence of solvent inevitably leads to unnecessary interfacial side reactions of multiple components (solvent, anions in lithium salt, lithium ions, and components at the electrode interface), hindering the movement and migration of lithium ions, and limiting the lithium ion content. , causing adverse effects on the actual use of lithium metal batteries

Method used

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  • COFs (Covalent Organic Frameworks) solid electrolyte containing lithium carboxylate group as well as preparation method and application of COFs solid electrolyte
  • COFs (Covalent Organic Frameworks) solid electrolyte containing lithium carboxylate group as well as preparation method and application of COFs solid electrolyte
  • COFs (Covalent Organic Frameworks) solid electrolyte containing lithium carboxylate group as well as preparation method and application of COFs solid electrolyte

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preparation example Construction

[0032] The invention provides a method for preparing a COFs solid-state electrolyte containing a lithium carboxylate group, comprising the following steps:

[0033] Mixing aldehyde-containing monomers, amino-containing organic carboxylic acid monomers, acid catalysts and organic solvents, and performing amine-aldehyde condensation reactions to obtain carboxyl-containing products;

[0034] The carboxyl group-containing product is mixed with a lithium salt solution for ion exchange to obtain a COFs solid state electrolyte containing lithium carboxylate groups.

[0035] In the present invention, unless otherwise specified, the required preparation materials are commercially available products well known to those skilled in the art.

[0036] The invention mixes aldehyde group-containing monomers, amino group-containing organic carboxylic acid monomers, acid catalysts and organic solvents to carry out amine-aldehyde condensation reaction to obtain carboxyl group-containing products...

Embodiment 1

[0060] Tritylaldehyde (Tf) (48.0 mg, 0.3 mmol), 2,5-diaminobenzoic acid (DAA) (68.5 mg, 0.45 mmol) and 4.0 mL of mesitylene / 1,4-dioxane ( 3:1, v / v) mixed solution into the ampoule, ultrasonic 10.0min, the CH 3 COOH (0.4mL, 6.0M) was added to the mixture obtained by ultrasound, the ampoule was frozen in liquid nitrogen, vacuum-sealed, sealed and placed in an oven at 120°C for 3 days. After cooling to room temperature, the resulting solid was collected by filtration and used separately After washing with tetrahydrofuran (THF) and acetone for 4 times, the obtained solid was soaked in anhydrous THF for 1 d, and the solvent was changed 4 times a day, and the obtained solid was vacuum-dried at 100 °C for 12 h to obtain a yellow powdery COF, which was designated as HOOC-COF1 ;

[0061] Incorporation of HOOC-COF1 into Li 2 CO 3 (20mL, 1.0M) aqueous solution, make HOOC-COF1 and Li 2 CO 3 The molar ratio is 1:100, stirred in a round-bottomed flask for 2 d, and the resulting solid w...

Embodiment 2

[0063] 1,3,5-Triformylphloroglucinol (Tp) (63.0 mg, 0.3 mmol), 2,5-diaminobenzoic acid (DAA) (68.5 mg, 0.45 mmol) and 3.0 mL of 1,4-dioxo The mixed solution of hexacyclic was added to the ampoule, ultrasonicated for 10.0min, and the CH 3 COOH (0.4mL, 6.0M) was added to the mixture obtained by ultrasound, the ampoule was frozen in liquid nitrogen, vacuum-sealed, sealed and placed in an oven at 120°C for 3 days. After cooling to room temperature, the resulting solid was collected by filtration and used separately After washing with tetrahydrofuran (THF) and acetone for 4 times, the obtained solid was soaked in anhydrous acetone for 1 d, and the solvent was changed 4 times a day, and the obtained solid was vacuum-dried at 100 °C for 12 h to obtain a red powdery COF, which was designated as HOOC-COF2 ;

[0064] Incorporation of HOOC-COF2 into Li 2 CO 3 (20.0mL, 1.0M) in aqueous solution, make HOOC-COF2 and Li 2 CO 3 The molar ratio is 1:100, stirred in a round-bottomed flask ...

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Abstract

The invention provides COFs (Covalent Organic Frameworks) solid electrolyte containing a lithium carboxylate group as well as a preparation method and application of the COFs solid electrolyte, and belongs to the technical field of electrochemical energy materials. The preparation method comprises the following steps: by adopting a solvothermal method, firstly, carrying out amine-aldehyde condensation reaction on a monomer to obtain a HOOC-COFs intermediate material containing carboxyl groups; and then carrying out ion exchange with lithium salt to obtain the lithium carboxylate group-containing LiOOC-COFs material, wherein the material can be used as a single-ion conductor solid electrolyte. The LiOOC-COF is assembled into the all-solid-state organic lithium ion battery, the electrochemical performance of the battery can be improved, and the lithium ion battery has huge application potential in a safe energy storage system.

Description

technical field [0001] The invention relates to the technical field of electrochemical energy materials, in particular to a COFs solid electrolyte containing lithium carboxylate groups and a preparation method and application thereof. Background technique [0002] Rechargeable lithium-ion batteries play an important role in electrochemical energy storage systems and bring enormous benefits in portable energy as well as other fields. However, organic liquid electrolytes are used in Li-ion batteries, causing safety hazards such as limited electrochemical window, short circuit, flammability, explosion, and dendrites. As an energy storage device, the all-solid-state lithium-ion battery has the advantages of high safety, high energy density and high power, and is a promising energy storage device in the future. The safety hazards of liquid lithium-ion batteries can be eliminated in solid-state lithium-ion batteries. However, the poor chemical stability of positive and negative ...

Claims

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Application Information

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IPC IPC(8): H01M10/0565H01M10/0525
CPCH01M10/0565H01M10/0525Y02E60/10
Inventor 郭洪赵根福孙勇疆安琪
Owner YUNNAN UNIV
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