CN111440179A - Conjugated organic lithium ion battery electrode material and preparation method and application thereof - Google Patents
Conjugated organic lithium ion battery electrode material and preparation method and application thereof Download PDFInfo
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- CN111440179A CN111440179A CN202010264736.5A CN202010264736A CN111440179A CN 111440179 A CN111440179 A CN 111440179A CN 202010264736 A CN202010264736 A CN 202010264736A CN 111440179 A CN111440179 A CN 111440179A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains three hetero rings
- C07D487/14—Ortho-condensed systems
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a conjugated organic lithium ion battery electrode material and a preparation method and application thereof, belonging to the technical field of lithium ion batteries. First, compound 1 is hydrolyzed by acid to synthesize compound 2, compound 2 and TFA, NaNO2，NaHCO3Reacting with NaOH, and then reacting with HCl to obtain H6HAT, adding excess lithium hydroxide to react to obtain L i, a derivative of 1,4,5,8,9, 12-Hexaazatriphenylene (HAT)6HAT the conjugated organic electrode material L i6HAT is used for lithium ion battery electrodes, and the first discharge specific capacity reaches 1126mAh/g under the current density of 100mA/g and 0.01V-3V; the discharge capacity after 50 cycles was 588.0 mAh/g. The conjugated organic electrode material synthesized by the invention has novel and stable structure, and is a novel lithium ion battery electrode material.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a conjugated organic lithium ion battery electrode material and a preparation method and application thereof.
Background
Lithium ion batteries play an important role in the development of portable electronic devices, and are considered to be the most promising energy technology for the next generation of electric vehicles. However, the widespread use of lithium ion batteries also presents environmental challenges such as metal contamination and greenhouse effect, which means that the development of environmentally friendly and sustainable electrode materials to replace conventional graphite anodes and inorganic metal oxide anodes is imminent.
Organic materials have excellent charge storage capacity due to the presence of appropriate functional groups, which are electrochemically active against lithium ions, and their HOMO/L UMO high energy can be easily designed at the molecular level.
However, the dissolution of organic compounds in L i-based electrolytes can lead to rapid capacity fade during charge/discharge.thus, in order to enhance stability in electrolytes, it is important to explore novel organic compounds with high energy density and excellent cycling stability by (1) covalently attaching electroactive organic molecules to a conductive backbone, such as carbon black, (2) polymerizing redox active compounds to reduce dissolution, (2) forming salts with organic carboxylic acid compounds, such as terephthalate.
Disclosure of Invention
The invention aims to provide a conjugated organic lithium ion battery electrode material, a preparation method and application thereof, which are used for solving the problems in the prior art.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides a conjugated organic lithium ion battery electrode material, which is a 1,4,5,8,9, 12-hexaazatriphenylene derivative, and has the following molecular structure:
the invention also provides a preparation method of the conjugated organic lithium ion battery electrode material, which comprises the following steps:
1) taking the compound 1 as a raw material, and synthesizing a compound 2 by acid hydrolysis;
2) compound 2 with TFA and NaNO in the presence of AcOH2Reacting, adding EtOH solvent, and continuing with NaHCO3Reacting with NaOH, and adding HCl to react at 90 deg.C to obtain H6-HAT；
3) The obtained H6Dissolving HAT in an ethanol solution, adding an excess of lithium hydroxide solution, and reacting to obtain L i6-a HAT compound.
Further, in the step 1), the acid involved in the acid hydrolysis of the compound 1 is concentrated sulfuric acid, the hydrolysis temperature is room temperature, and the hydrolysis time is 72 hours.
Further, in step 2), the compound 2 is mixed with TFA and NaNO2The reaction temperature of (A) is room temperature, the reaction time is 72h, and NaHCO is used3The reaction temperature of NaOH and the reaction time is 12h, the added amount of HCl is 6N, and the reaction time is 1 h.
Further, in the step 2), the mass ratio of TFA to the compound 2 is 50:1, and the compound 2 and NaNO are mixed2In a molar ratio of 1: 9.
Further, in step 3), H6The reaction temperature of HAT and lithium hydroxide solution is room temperature, and the reaction time is 48 h.
The invention also provides an application of the conjugated organic lithium ion battery electrode material or the conjugated organic lithium ion battery electrode material prepared by the preparation method in a lithium ion battery electrode.
The invention discloses the following technical effects:
it has been particularly inspired by the design of extended pi-conjugated organic semiconductor molecules in the field of organic electronics, which can stabilize the-1 and +1 valence charge states and promote charge transport, nitrogen-containing heteroaromatics (e.g., azo compounds), pteridine and indigo carmine have proven to be promising cathodes for lithium ion batteries.
The conjugated organic lithium ion battery electrode material is pi-conjugated N-containing heteroaromatic hexacarboxylate (L i)6HAT) molecule, is a derivative of 1,4,5,8,9, 12-Hexaazatriphenylene (HAT). the conjugated organic lithium ion battery electrode material L i6The HAT is used for the lithium ion battery electrode, and the result of an electrochemical performance test proves that the first discharge specific capacity reaches 1126mAh/g and the discharge capacity after 50 cycles is 588.0mAh/g under the current density of 0.01V-3V and 100 mA/g. The preparation method has low requirements on synthesis equipment, and the synthesized conjugated organic electrode material has high energy density, excellent cycle stability, novel structure and stable performance, and is a novel lithium ion battery electrode material.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 shows a conjugated organic lithium ion battery electrode material L i6-a map of the structure of the HAT and a surface electrostatic potential map;
FIG. 2 shows a conjugated organic lithium ion battery electrode material L i6-structural and XRD patterns of HAT;
FIG. 3 shows a conjugated organic lithium ion battery electrode material L i6-an infrared spectrum of HAT;
FIG. 4 shows a conjugated organic lithium ion battery electrode material L i6-XPS elemental gross spectrum of HAT;
FIG. 5 shows a conjugated organic lithium ion battery electrode material L i6-XPS-C1 s spectrum of HAT;
FIG. 6 shows a conjugated organic lithium ion battery electrode material L i6-XPS-Ns spectra of HAT;
FIG. 7 shows a conjugated organic lithium ion battery electrode material L i6-XPS-O1 s spectrum of HAT;
FIG. 8 shows a conjugated organic lithium ion battery electrode material L i6-SEM picture of HAT;
FIG. 9 shows a conjugated organic lithium ion battery electrode material L i6-TEM images of HAT;
FIG. 10 shows a conjugated organic lithium ion battery electrode material L i6HRTEM of HAT;
FIG. 11 shows a conjugated organic lithium ion battery electrode material L i6-first charge-discharge curve of HAT;
FIG. 12 shows a conjugated organic lithium ion battery electrode material L i6-50 th charge-discharge curve of HAT;
FIG. 13 shows a conjugated organic lithium ion battery electrode material L i6-50 cycles curve of HAT;
FIG. 14 shows a conjugated organic lithium ion battery electrode material L i6500 cycles of HAT curve.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
The invention provides a conjugated organic lithium ion battery electrode material, which is a 1,4,5,8,9, 12-hexaazatriphenylene derivative, and has the following molecular structure:
the preparation method of the conjugated organic lithium ion battery electrode material comprises the following steps:
1) taking a compound 1 as a raw material, and hydrolyzing in the presence of concentrated sulfuric acid at room temperature for 72 hours to synthesize a compound 2;
2) compound 2 with TFA and NaNO in the presence of AcOH2Reacting for 72h at room temperature, wherein the mass ratio of TFA to compound 2 is 50:1, and the mass ratio of compound 2 to NaNO2In a molar ratio of 1:9, then adding EtOH solvent, and continuing with NaHCO3Reacting with NaOH at room temperature for 12H, and adding 6N HCl to react at 90 deg.C for 1H to obtain H6-HAT；
3) The obtained H6Dissolving HAT in ethanol solution, adding excess lithium hydroxide solution, and reacting at room temperature for 48h to obtain L i6-a HAT compound.
Example 1
Conjugated organic lithium ion battery electrode material L i6The synthetic route for HAT is as follows:
the method comprises the following steps:
1) adding 400g of concentrated sulfuric acid into 10g of the compound 1, stirring at room temperature for reaction for 72h, filtering after the reaction is finished, washing the filtered solid for 3 times by using deionized water, then washing for 3 times by using acetone, and then drying for 14h at 100 ℃ in vacuum to obtain a compound 2, wherein the product yield can be more than 87%;
2) 4.92g of Compound 2 are added to 150m L trifluoroacetic acid (TFA) and stirred at room temperature, and 7.0g of sodium nitrite NaNO are added2Reacting at room temperature, wherein the mass ratio of TFA to compound 2 is 50:1, and the mass ratio of compound 2 to NaNO2The molar ratio of the components is 1:9, a brown suspension is obtained after the reaction is finished, 150m of L acetic acid is added, the mixture is stirred for 12 hours, the mixture is poured into 300m of L ice water, and a solid product is obtained by filtration, and the solid product is dissolved into 150m of L NaHCO3Stirring the solution, filtering to remove insoluble solid to obtain filtrate, adding 30m of L EtOH solvent, treating the filtrate with active carbon, heating to boil, filtering to obtain clear yellow solution, and treating the solution with cold sodium hydroxide(20.0 g in 100 ml water) to give HAT, suspending HAT in water at a solid-to-liquid ratio of HAT to water (2.52g/40mmol) of 100m L, heating to 50 ℃, acidifying by addition of 6N concentrated HCl, reacting the resulting mixture at 90 ℃ for 1H, filtering to give the crude product, washing with 10% HCl (3X 25m L), washing with deionized water (2X 25m L), and drying under vacuum at 120 ℃ to give H6-HAT
3) H is to be6Dissolving HAT in ethanol solution, adding excessive lithium hydroxide aqueous solution, stirring at room temperature for reaction for 48h, filtering after the reaction is finished, washing with deionized water for 3 times, washing with ethanol for 3 times, and drying at 50 ℃ to balance weight to obtain the electrode material L i of the conjugated organic lithium ion battery6-HAT。
FIG. 1 shows a conjugated organic lithium ion battery electrode material L i6The structural diagram of HAT and the surface electrostatic potential diagram.
For the obtained electrode material L i of the conjugated organic lithium ion battery6HAT for morphological analysis, XRD analysis, infrared spectroscopy and XPS elemental analysis.
Conjugated organic lithium ion battery electrode material L i6The structural diagram and XRD pattern of HAT are shown in FIG. 2.
Conjugated organic lithium ion battery electrode material L i6The IR spectrum of the HAT is shown in FIG. 3.
Conjugated organic lithium ion battery electrode material L i6XPS spectra of HAT are shown in FIGS. 4-7.
Conjugated organic lithium ion battery electrode material L i6The profile analysis of HAT is shown in FIGS. 8-10.
Conjugated organic lithium ion battery electrode material L i6-performance detection of HAT:
according to L i6Preparing a mixture of HAT, PVDF and KS6 in a mass ratio of 60:10:30, adding NMP as a solvent, and stirring for 2 hours to prepare the lithium ion battery electrode slurry. And (3) coating the electrode viscous slurry on a copper foil with the thickness of 12 microns, wherein the coating thickness is 50 microns, and drying at 100 ℃ for 12 hours to obtain the lithium ion battery electrode.
The lithium ion battery negative pole piece is cut into a circular pole piece with the diameter of 14mm, and the lithium ion battery counter electrode adopts a metal lithium piece with the diameter of 15 mm. ElectrolysisThe liquid is 1 mol/L L iPF6The button cell was assembled in a 2032 type glove box filled with argon gas, dissolved in a solvent of Ethylene Carbonate (EC) and dimethyl carbonate (DMC) (molar ratio EC: DMC 1: 1).
The prepared button cell is tested for charge and discharge, and the electrode material L i of the conjugated organic lithium ion battery is obtained under the current density of 100mA/g6The first charge-discharge curve of HAT is shown in FIG. 11, and it can be seen from FIG. 11 that L i is measured at a current density of 100mA/g from 0.01V to 3V6The specific first discharge capacity of HAT reaches 1126 mAh/g.
FIG. 12 shows L i at a current density of 100mA/g6-50 th charge-discharge curve of HAT.
It can be seen that L i at a current density of 100mA/g from 0.01V to 3V6The 50 th discharge specific capacity of HAT can still be as high as 588 mAh/g.
FIG. 13 shows L i at a current density of 100mA/g 650 cycles of HAT, capacity retention after 50 cycles calculated from the second discharge capacity being 72%.
FIG. 14 shows L i at a current density of 800mA/g 6500 cycles of HAT curve.
As can be seen in FIG. 14, L i6After 500 cycles of HAT, the capacity retention rate is 87.2%, and the HAT has excellent cycle stability.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (7)
1. The electrode material of the conjugated organic lithium ion battery is characterized in that the electrode material is a 1,4,5,8,9, 12-hexaazatriphenylene derivative, and the molecular structure of the electrode material is as follows:
2. the method for preparing the electrode material of the conjugated organic lithium ion battery according to claim 1, comprising the steps of:
1) taking the compound 1 as a raw material, and synthesizing a compound 2 by acid hydrolysis;
2) compound 2 with TFA and NaNO in the presence of AcOH2Reacting, adding EtOH solvent, and continuing with NaHCO3Reacting with NaOH, and adding HCl to react at 90 deg.C to obtain H6-HAT；
3) The obtained H6Dissolving HAT in an ethanol solution, adding an excess of lithium hydroxide solution, and reacting to obtain L i6-a HAT compound.
3. The method for preparing the electrode material of the conjugated organic lithium ion battery according to claim 2, wherein in the step 1), the acid involved in the acid hydrolysis of the compound 1 is concentrated sulfuric acid, the hydrolysis temperature is room temperature, and the hydrolysis time is 72 hours.
4. The method for preparing an electrode material of a conjugated organolithium-ion battery according to claim 2, wherein in step 2), the compound 2 is reacted with TFA or NaNO2The reaction temperature of (A) is room temperature, the reaction time is 72h, and NaHCO is used3The reaction temperature of NaOH and the reaction time is 12h, the added amount of HCl is 6N, and the reaction time is 1 h.
5. The method for preparing an electrode material of a conjugated organolithium-ion battery according to claim 2, wherein the mass ratio of TFA to compound 2 in step 2) is 50:1, and the mass ratio of compound 2 to NaNO2In a molar ratio of 1: 9.
6. The method for preparing an electrode material for a conjugated organic lithium ion battery according to claim 2, wherein the step 3) is performed by，H6The reaction temperature of HAT and lithium hydroxide solution is room temperature, and the reaction time is 48 h.
7. The use of the conjugated organic lithium ion battery electrode material of claim 1 or the conjugated organic lithium ion battery electrode material prepared by the method of any one of claims 2 to 6 in an electrode of a lithium ion battery.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113410451A (en) * | 2021-06-10 | 2021-09-17 | 宁波大学 | Lithium metal negative electrode flexible protection material and preparation method thereof |
| CN114373992A (en) * | 2022-01-25 | 2022-04-19 | 宁德新能源科技有限公司 | Electrolyte solution, electrochemical device, and electronic device |
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| US20060052509A1 (en) * | 2002-11-01 | 2006-03-09 | Mitsubishi Rayon Co., Ltd. | Composition containing carbon nanotubes having coating thereof and process for producing them |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113410451A (en) * | 2021-06-10 | 2021-09-17 | 宁波大学 | Lithium metal negative electrode flexible protection material and preparation method thereof |
| CN114373992A (en) * | 2022-01-25 | 2022-04-19 | 宁德新能源科技有限公司 | Electrolyte solution, electrochemical device, and electronic device |
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