阅读说明：本技术 杯[八]醌的制备方法及其应用 (Preparation method and application of calix [ octaquinone ] ) 是由 黄苇苇 刘帅 胡攀登 孙会民 张卫生 于 2021-10-22 设计创作，主要内容包括：本发明公开了杯[八]醌的制备方法及其应用,制备方法包括：将4-苄氧基苯酚与多聚甲醛在碱性条件下缩聚反应得到4-苄氧基杯[八]芳烃,通过4-苄氧基杯[八]芳烃的去苄基反应得到杯[八]氢醌,将杯[八]氢醌氧化得到杯[八]醌。本发明通过三步法首次制备得到杯[八]醌,制备方法简单,高效,为杯芳醌化合物的制备开创思路。本发明制备得到的杯[八]醌制备的锂电子电池,电池初始放电比容量达到408mAh g～(-1),且循环稳定,拓宽了杯芳醌类化合物的应用范围。(The invention discloses a cup (eight)]The preparation method of the quinone comprises the following steps: 4-benzyloxy phenol and paraformaldehyde are subjected to polycondensation reaction under the alkaline condition to obtain 4-benzyloxy cup [ octa]Arene through 4-benzyloxy cup [ octal ]]Debenzylation of aromatic hydrocarbons to obtain calix [ octal ]]Hydroquinone, mixing cup (Ba)]Oxidation of hydroquinone to give cup]A quinone. The cup is prepared by a three-step method for the first time [ eight)]The preparation method of the quinone is simple and efficient, and opens the way for preparing the calixarene compound. Cup [ eight ] prepared by the invention]The initial discharge specific capacity of the lithium electronic battery prepared from the quinone reaches 408mAh g ‑1 And the circulation is stable, and the application range of the calixarene compound is widened.)

1. The preparation method of calix [ octaquinone is characterized by comprising the following steps:

wherein, the step i is the polycondensation reaction of 4-benzyloxy phenol and paraformaldehyde under the alkaline condition to obtain a compound 14-benzyloxy calix [ octa ] arene, the step ii is the debenzylation reaction of a compound 1 to obtain a compound 2 calix [ octa ] hydroquinone, and the step iii is the oxidation reaction of the compound 2 to obtain the calix [ octa ] quinone.

2. The method for preparing calix [ octa ] quinone according to claim 1, wherein the molar ratio of 4-benzyloxyphenol to paraformaldehyde in step i is 1: 1.7 to 1.9; the step i is carried out in an organic solvent, wherein the organic solvent is xylene; the pH value under the alkaline condition is 11-13;

preferably, the alkaline condition is constructed by dissolving an alkali metal hydroxide or an organic base in the organic solvent, the alkali metal hydroxide being selected from any one of sodium hydroxide, potassium hydroxide and rubidium hydroxide; the organic base is potassium tert-butoxide;

preferably, the molar ratio of the 4-benzyloxyphenol to the organic solvent is 1: 19 to 21 parts by weight;

preferably, the molar ratio of the 4-benzyloxyphenol to the alkali metal hydroxide or organic base is 1: 0.03 to 0.04.

3. The preparation method of calix [ octa ] quinone according to claim 1, wherein the condensation polymerization reaction of step i 4-benzyloxyphenol and paraformaldehyde under alkaline conditions is carried out under the protection of inert gas, and the heating is carried out until the reflux reaction lasts for 4-8 h.

4. The method for preparing calix [ octa ] quinone according to claim 1, wherein the step i further comprises cooling, suction filtration and organic solvent washing.

5. The preparation method of calix [ octa ] quinone according to claim 1, wherein the step ii is to add the compound 1 into chloroform or 1, 2-dichloroethane, then slowly add the iodotrimethylsilane, heat to reflux reaction for more than 10h, then cool to below 30 ℃ and then add methanol or ethanol to obtain the compound 2;

preferably, the molar ratio of the compound 1 to chloroform or 1, 2-dichloroethane is 1: 740 to 760 parts;

preferably, the molar ratio of compound 1 to iodotrimethylsilane is 1: 420 to 430;

preferably, the molar ratio of compound 1 to methanol or ethanol is 1: 1450-1470;

preferably, the addition of chloroform or 1, 2-dichloroethane to the compound 1 is carried out under the protection of inert gas;

preferably, the heating to reflux reaction of the added iodotrimethylsilane is carried out under the protection of inert gas.

6. The preparation method of calix [ octa ] quinone according to claim 1, wherein in the step iii, under the protection of inert gas, the compound 2 is dissolved in organic acid, heated to 45-55 ℃, added with ferric trichloride solution, then added into potassium dichromate solution, heated to 80-95 ℃, reacted for 10-60min, cooled and filtered to obtain a crude product;

preferably, the organic acid is at least one selected from glacial acetic acid, propionic acid, butyric acid, methanesulfonic acid, p-toluenesulfonic acid and tert-valeric acid, and the molar ratio of the compound 2 to the acid group of the organic acid is 1: 1150 to 1160;

preferably, the molar ratio of the compound 2 to the ferric chloride in the ferric chloride solution is 1: 22-24;

preferably, the molar ratio of the compound 2 to the potassium dichromate in the potassium dichromate solution is 1: 11 to 14.

7. The method for preparing calix [ octa ] quinone according to claim 5, wherein in step ii, the methanol is anhydrous methanol.

8. The method for preparing calix [ octa ] quinone according to claim 6, wherein step iii further comprises purification of said crude product.

9. The application of calix [ octa ] quinone obtained by the preparation method according to any one of claims 1 to 8 in the preparation of batteries is characterized by being applied to the preparation of lithium electronic batteries.

Technical Field

The invention relates to the technical field of materials, in particular to a preparation method and application of calix [ octa ] quinone.

Background

Calixarenes are a generic term for macrocyclic compounds composed of methylene-bridged phenol units. Calixarene has the characteristics of adjustable cavity, designable conformation, convenience for chemical modification of calixarene and the like, and is widely applied to numerous fields of liquid film transmission, complex extraction, molecular probes, molecular devices, sensors, liquid crystals, nonlinear optics and the like.

Calixarenes are currently used in electrochemistry, e.g. the calixarene derivative calix [ tetra [ ]]Quinone (Calix [4]]quinone) and cup [ six]The theoretical specific capacity of the quinone used as the anode material of the lithium ion battery is 446mAh g^-1. However, cup [ four]Quinone and cup]Quinone has the same problem that the positive electrode material is dissolved in the organic electrolyte to cause the active material (calix]Quinone or cup]Quinone) has a capacity loss during cycling. The method using physical coating of porous carbon CMK-3 also does not solve this problem well, see document 1: zheng S, Sun H, Yan B, et al, high-capacity organic electrode material Calix [4]quinone/CMK-3nanocomposite for lithium batteries.Science China Materials,2018,61(10)：1285-1290。

Cup [ eight)]Quinone as cup [ four ]]Quinone and cup]Quinone of the same series of substances having the same structure as calix [ IV ]]Quinone, cup (Liu)]Quinone-identical structural unit and theoretical specific capacity 446mAh g^-1. Cause cup (IV)]Quinone is easily dissolved in organic electrolyte, and has poor circulation stability and large molecular weight]Although the cycle stability of the quinone is improved, the quinone still has the problem of being easily dissolved in an organic electrolyte, and the application of the quinone in the electrochemical field is limited. In order to further slow down the dissolution in organic electrolytes and to increase the cycling stability of the cells, a cup of the same series of substances with a greater molecular weight is synthesized [ eight]Quinones become especially critical. The existing report about cup [ n]The quinone synthesis method mainly comprises a one-step oxidation method and a reduction-oxidation method. By one-step oxidation process using PbO₂Strong oxidizing property of (C) in 70% HClO₄Under the action of the catalyst, calixarene and para-tertiary butyl derivatives thereof are oxidized into corresponding calixarene. Through multiple experimentsAnd analysis of the detection result, the cup cannot be obtained by the one-step oxidation method [ eight]Quinones are used to reduce the difficulty of oxidation by intermediates, since the oxidation is largely incomplete. Redox oxidation, i.e. existing synthesis cups]Quinone and cup]The most commonly used method for quinones. With cup (four)]Quinone for example: cup (IV)]The target product is obtained by coupling, reducing and oxidizing aromatic hydrocarbon as a raw material, specifically refer to document 2: morita Y, Agawa T, Nomura E, et al Synthesis and NMR behavior of calix [4]quinone and Calix[4]Journal of Organic Chemistry,1992,57 (13): 3658-3662. The applicant found that in the actual operation process, the synthesis cup was not successfully synthesized by referring to the above synthesis method [ eight ]]A quinone.

Referring to FIG. 11, the synthetic route for the preparation of calix [ octa ] quinone by the above synthetic method, the reason for the failure to prepare calix [ octa ] quinone is suspected to be: the first coupling reaction did not proceed completely and there was a small fraction of incompletely coupled by-products (mass spectrometry showed peaks for by-products coupling only 6 or 7 azo groups); azo compound M1 has very poor solubility in a solution of sodium bicarbonate and sodium carbonate, resulting in difficult subsequent handling; compared with the amino compounds for synthesizing the calix [ tetra ] quinone and the calix [ hexa ] quinone, the amino compound M2 is easier to be oxidized in the air, and the reaction difficulty is greatly increased. Therefore, the exploration of the synthetic method of calix [ octa ] quinone is very critical to the application of the calix aromatic quinone.

Disclosure of Invention

In view of the above technical problems, it is an object of the present invention to provide a simple method for preparing calixarene and to provide application of the calixarene to batteries, thereby expanding the application of calixarene.

In order to achieve the purpose, the invention adopts the technical scheme that:

the invention provides a preparation method of calix [ octa ] quinone, which comprises the following steps:

wherein, the step i is the polycondensation reaction of 4-benzyloxy phenol and paraformaldehyde under the alkaline condition to obtain a compound 14-benzyloxy calix [ octa ] arene, the step ii is the debenzylation reaction of a compound 1 to obtain a compound 2 calix [ octa ] hydroquinone, and the step iii is the oxidation reaction of the compound 2 to obtain the calix [ octa ] quinone.

As a preferred embodiment, the molar ratio of 4-benzyloxyphenol to paraformaldehyde in step i is 1: 1.7 to 1.9; said step i is carried out in an organic solvent, preferably xylene; the pH value under the alkaline condition is 11-13;

preferably, the alkaline condition is constructed by dissolving an alkali metal hydroxide or an organic base in the organic solvent, wherein the alkali metal hydroxide is selected from any one of sodium hydroxide, potassium hydroxide and rubidium hydroxide; the organic base is potassium tert-butoxide;

preferably, the molar ratio of the 4-benzyloxyphenol to the organic solvent is 1: 19 to 21 parts by weight;

preferably, the molar ratio of the 4-benzyloxyphenol to the alkali metal hydroxide or organic base is 1: 0.03 to 0.04;

in a preferable embodiment, the condensation polymerization reaction of the step i 4-benzyloxy phenol and paraformaldehyde under the alkaline condition is carried out under the protection of inert gas, and the reaction is heated to reflux for 4-8 h.

As a preferred embodiment, the step i further comprises cooling, suction filtration and organic solvent washing.

Preferably, the step ii is to add the compound 1 into chloroform or 1, 2-dichloroethane, then slowly add iodotrimethylsilane, heat to reflux reaction for more than 10 hours, then cool to below 30 ℃, and then add methanol or ethanol to obtain a compound 2;

preferably, the molar ratio of the compound 1 to chloroform or 1, 2-dichloroethane is 1: 740 to 760 parts;

preferably, the molar ratio of compound 1 to iodotrimethylsilane is 1: 420 to 430;

preferably, the molar ratio of compound 1 to methanol or ethanol is 1: 1450-1470;

preferably, the addition of chloroform or 1, 2-dichloroethane to the compound 1 is carried out under the protection of inert gas;

preferably, the heating to reflux reaction of the added iodotrimethylsilane is carried out under the protection of inert gas.

As a preferable embodiment, in the step iii, under the condition of inert gas protection, dissolving the compound 2 in an organic acid, heating to 45-55 ℃, adding a ferric trichloride solution, stirring for 15-60 min, then adding into a potassium dichromate solution, heating to 80-95 ℃, reacting for 10-60min, cooling, and filtering to obtain a crude product;

preferably, the organic acid is at least one selected from glacial acetic acid, propionic acid, butyric acid, methanesulfonic acid, p-toluenesulfonic acid and tert-valeric acid, and the molar ratio of the compound 2 to the acid group of the organic acid is 1: 1150 to 1160;

preferably, the molar ratio of the compound 2 to glacial acetic acid is 1: 1150 to 1160;

preferably, the molar ratio of the compound 2 to the ferric chloride in the ferric chloride solution is 1: 22-24;

preferably, the molar ratio of the compound 2 to the potassium dichromate in the potassium dichromate solution is 1: 11 to 14;

preferably, the concentration of ferric trichloride is 1.3-1.7mol/L and the concentration of potassium dichromate is 0.05-0.09 mol/L.

As a preferred embodiment, in step ii, the methanol is anhydrous methanol.

As a preferred embodiment, the crude product in step iii is purified to afford calix [ octa ] quinone.

In certain specific embodiments, the purification is as follows: washing with glacial acetic acid, acetone, ethyl acetate and petroleum ether in sequence to obtain calix [ octa ] quinone.

The invention provides the application of the calix [ octa ] quinone obtained by the preparation method in the preparation of batteries, preferably lithium electronic batteries.

In the technical scheme of the invention, calix [ octa ] quinone is prepared by a three-step method of polycondensation, debenzylation and oxidation, 4-benzyloxy phenol and paraformaldehyde are selected as initial reaction raw materials, 8 4-benzyloxy phenol molecules are subjected to polycondensation to form rings, a calix [ octa ] quinone framework is constructed to obtain 4-benzyloxy calix [ octaarene, then benzyl on the 4-benzyloxy calix [ octaarene is removed through debenzylation reaction to obtain calix [ octa ] hydroquinone, and finally hydroquinone on the calix [ octa ] hydroquinone is oxidized into p-benzoquinone through oxidation to obtain the calix [ octa ] quinone.

The technical scheme has the following advantages or beneficial effects:

1. the calix [ octa ] quinone is synthesized for the first time by a three-step method of polycondensation, debenzylation and oxidation.

2. The preparation method provided by the invention adopts common reagents, has low toxicity and simple post-treatment. The reaction conditions are mild, no harsh conditions are needed, and the method has no other cyclic side products and high yield of the final product.

3. The prepared calix [ octa ] quinone has larger molecular weight and more electrochemical reaction active sites, so that the dissolution of the calix [ octa ] quinone in electrolyte can be reduced, and the electrochemical performance of the calix [ octa ] quinone is improved. The active sites are more, so that the lithium ion battery has high specific capacity and cycle performance, and has good application prospect when being used for green organic lithium ion secondary batteries.

4. Cup of preparation [ eight ]]Quinone is used as the anode material of lithium ion battery, and in the electrolyte system, the initial discharge specific capacity of the first ring is 408mAh g^-1After 200 weeks of circulation, the concentration is kept at 174mAh g^-1. The battery is expected to be applied to next-generation high-energy, high-power, green and sustainable energy storage batteries.

Drawings

FIG. 1 is a Fourier infrared characterization of calix [ octa ] quinone prepared in example 1 of the present invention.

FIG. 2 is a mass spectrum of calix [ octa ] quinone prepared in example 2 of the present invention.

FIG. 3 is a cup [ eight ] prepared in example 3 of the present invention]Process for preparing quinones¹H NMR test chart.

FIG. 4 is a cup [ eight ] prepared in example 3 of the present invention]Process for preparing quinones¹³C NMR test chart.

FIG. 5 is a plot of cyclic voltammetry of a lithium ion battery containing calix [ octa ] quinone prepared in example 4 of the present invention.

FIG. 6 is a graph showing the charge and discharge curves of a lithium ion battery containing calix [ octa ] quinone prepared in example 4 of the present invention.

FIG. 7 is a graph showing the charge and discharge curves of lithium ion batteries prepared from calixaquinone and calixaquinone in comparative example 1 and calixaquinone in example 4 of the present invention.

FIG. 8 is a scheme for the preparation of calix [ octa ] quinone according to the present invention.

FIG. 9 is a mass spectrum of Compound 2 prepared in example 1 of the present invention.

FIG. 10 is a photograph of Compound 1 prepared in example 1 of the present invention¹H NMR test chart.

FIG. 11 is a synthesis scheme for the preparation of calix [ octaquinone according to reference 2 of the background of the invention.

Detailed Description

The following examples are only a part of the present invention, and not all of them. Thus, the detailed description of the embodiments of the present invention provided below is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the invention without making creative efforts, belong to the protection scope of the invention.

The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.

The temperature range of room temperature in the following examples is 10 to 30 ℃.

Reagents and instrumentation:

anhydrous methanol: adding a small amount of polished bright magnesium tape into analytically pure methanol, heating and refluxing for 4h under the protection of nitrogen, distilling to remove the solvent under the condition of nitrogen, and collecting to obtain anhydrous oxygen-free methanol.

Oxygen-free water: and refluxing the deionized water for 2 hours under the nitrogen condition, and distilling and collecting to obtain oxygen-free distilled water.

EC: ethylene carbonate.

DMC: dimethyl carbonate.

TMSI: and (3) trimethyl iodosilane.

Mass spectrometry: finnigan LCQ, Finnigan Inc., USA.

Preparation of calix [ tetra ] quinone reference is made to the method described in Huang W, Zhu Z, Wang L, et al, Quasi-solid-state recoverable lithium-ion batteries with a calix [4] quinone catalyst and gel polymer electrolyte [ J ]. Angewandte Chemie,2013,52(35): 9162-.

Process for the preparation of Calix [ hexa ] quinone reference is made to the method described in Huang W, Zheng S, Zhang X, et al Synthesis and Application of Calix [6] quinone as a High-Capacity Organic catalyst for Plastic Crystal electronics [ J ] Energy Storage Materials,2019,26.

The invention provides a preparation method of calix [ octa ] quinone, wherein a preparation route and a structure of the calix [ octa ] quinone are shown in figure 8.

Example 1:

in this example, the preparation method was as follows:

(1) as 4-benzyloxyphenol: xylene: paraformaldehyde: the molar ratio of potassium hydroxide is 1: 19: 1.7: 0.03, placing 4-benzyloxy phenol, paraformaldehyde and potassium hydroxide in a xylene solvent, uniformly mixing, heating to reflux (the temperature is about 138 ℃ C. and 144 ℃ C.) after mixing under the protection of nitrogen, cooling to room temperature after reacting for 6h, and performing suction filtration to obtain an off-white crude product. Sequentially washing with xylene, acetone and petroleum ether to obtain white light powder solid 4-benzyloxy cup]Aromatic hydrocarbons in 50.6% yield¹The H NMR chart is shown in FIG. 10, 4-benzyloxy cup [ eight]Process for preparing aromatic hydrocarbons¹H NMR((CD₃)₂SO) at 3.35 and 2.50 are solvent peaks, 3.78 for the hydrogen on the methylene attached to the benzene ring, 4.82 for the hydrogen on the methylene attached to the oxygen, 6.60 for the hydrogen on the benzene ring, 7.29 for the hydrogen on the benzyl benzene ring, 8.65 for the hydrogen on the hydroxyl.¹H NMR((CD₃)₂SO)δ8.65(s，8H，-OH)，δ7.27(s，40H，-CH₂-)，δ6.60(s，16H，-CH₂-)，δ4.82(s，16H，-O-CH₂-),δ3.78(s，16H，-CH₂-)。

(2) Press 4-benzyloxy cup [ eight ]]Aromatic hydrocarbons: chloroform: iodotrimethylsilane: the molar ratio of the anhydrous methanol is 1: 740: 420: 1450 proportion of 4-benzyloxy cup [ eight ] under the protection of nitrogen]Adding aromatic hydrocarbon into a chloroform solvent, slowly adding iodotrimethylsilane (extremely volatile and highly corrosive) into the suspension, heating to reflux (the temperature is about 55-65 ℃) under the protection of nitrogen for reaction for 12 hours, cooling to room temperature, adding anhydrous methanol to obtain yellow suspension, and performing centrifugal separation to obtain a white solid. Vacuum drying to obtain bluish substance cup]Hydroquinone (substance blue in water) yield of 74.2%, mass spectrum thereof is shown in FIG. 9, cup [ octa ] of]Hydroquinone M ═ 975.00[976-H ]⁺]And cup [ eight ]]The relative molecular masses of the hydroquinones matched, demonstrating that the synthetic material was calixate [ octa ]]Hydroquinone.

(3) According to the content of cup [ eight ] hydroquinone: glacial acetic acid: ferric chloride: potassium dichromate: the molar ratio of the deionized water is 1: 1150: 22: 11: according to the 10200 proportion, calix [ octa ] hydroquinone is dissolved in glacial acetic acid, the temperature is raised to 50 ℃ under the protection of nitrogen, anhydrous ferric trichloride solution is added dropwise, the color of the solution gradually changes from gray to green, and finally changes to yellow-green. And after stirring for 15min, pouring the obtained yellow-green solution into a potassium dichromate solution, heating to 90 ℃, and reacting for 15 min. Cooling to room temperature, and filtering to obtain a yellow green solid crude product. Dissolving the obtained crude product in dimethyl sulfoxide, stirring at room temperature for 30min, performing suction filtration, and sequentially washing with glacial acetic acid, acetone, ethyl acetate and petroleum ether to obtain the yellow calix [ octa ] quinone with yield of 74.9%.

For the obtained product cup [ eight ]]Quinone characterization was performed, as shown in FIG. 1, with Fourier Infrared Spectroscopy at 1650, 1604cm^-1The positions correspond to infrared absorption peaks of 1297cm caused by stretching vibration of C ═ O and double bond C ═ C respectively^-1The infrared absorption peak of (a) is represented by-CH linked to p-benzoquinone unit₂-induced.

The resulting cup of organic material [ eight ]]Application of quinone in lithium ion secondary batteries: the positive electrode of the lithium ion secondary battery is a cup (eight)]Quinone, the cathode material is a metal lithium sheet, and the electrolyte is 1M LiPF₆/(EC：DMC＝1：1w/w)A solution; and (3) standing the assembled battery in an oven at 30 ℃ for 8-12h, and then carrying out electrochemical test.

Example 2

(1) As 4-benzyloxyphenol: xylene: paraformaldehyde: the molar ratio of potassium hydroxide is 1: 19: 1.8: 0.04, placing 4-benzyloxy phenol, paraformaldehyde and potassium hydroxide in a xylene solvent, uniformly mixing, heating to reflux (the temperature is about 138 ℃ C. and 144 ℃ C.) after mixing under the protection of nitrogen, cooling to room temperature after reacting for 8h, and performing suction filtration to obtain an off-white crude product. Washing with dimethylbenzene, acetone and petroleum ether in sequence to obtain white light powder solid 4-benzyloxy calix [ octa ] arene with the yield of 40.3%.

(2) According to the formula of 4-benzyloxy calix [ octa ] arene: chloroform: iodotrimethylsilane: the molar ratio of the anhydrous methanol is 1: 750: 420: 1460, under the protection of nitrogen, adding 4-benzyloxy calix [ octa ] arene into a chloroform solvent, slowly adding iodotrimethylsilane (extremely volatile and highly corrosive) into the suspension, heating to reflux (the temperature is about 55-65 ℃) for reaction for 14 hours under the protection of nitrogen, cooling to room temperature, adding anhydrous methanol to obtain a yellow suspension, and performing centrifugal separation to obtain a white solid. After drying under vacuum, the bluish substance calix [ octa ] hydroquinone (bluing in water) was obtained in 70.6% yield.

(3) According to the content of cup [ eight ] hydroquinone: glacial acetic acid: ferric chloride: potassium dichromate: the molar ratio of the oxygen-free water is 1: 1150: 23: 12: 10250 dissolving calix [ octa ] hydroquinone in glacial acetic acid, heating to 50 deg.C under nitrogen protection, and adding dropwise anhydrous ferric chloride solution to gradually turn from gray to green and finally to yellow-green. And after stirring for 15min, pouring the obtained yellow-green solution into a potassium dichromate solution, heating to 90 ℃, and reacting for 15 min. Cooling to room temperature, and filtering to obtain a yellow green solid crude product. Dissolving the obtained crude product in dimethyl sulfoxide, stirring at room temperature for 60min, performing suction filtration, and sequentially washing with glacial acetic acid, acetone, ethyl acetate and petroleum ether to obtain yellow calix [ octa ] quinone with yield of 66.9%.

FIG. 2 shows a cup [ eight ] made according to the present invention]The quinone adopts liquid chromatography-mass spectrometryIon Mass-to-charge ratio (Mass-to-charge ratio) measured by spectrum combination instrument (Liquid chromatography Mass Spectrometer, LC-MS for short), N-dimethylformamide as solvent, experimental result of positive ion mode test, cup [ octa ] of]Quinone M/z M ═ 959.0 (M-H)⁺) And cup [ eight ]]The relative molecular masses of the quinones are consistent.

The resulting cup of organic material [ eight ]]The application of the quinone in the lithium ion secondary battery: the positive electrode of the lithium ion secondary battery is a cup (eight)]Quinone, the cathode material is a metal lithium sheet, and the electrolyte is 1M LiPF₆V (EC: DMC ═ 1: 1w/w) solution; and (3) standing the assembled battery in an oven at 30 ℃ for 8-12h, and then carrying out electrochemical test.

Example 3

(1) As 4-benzyloxyphenol: xylene: paraformaldehyde: the molar ratio of potassium hydroxide is 1: 20: 1.8: 0.035, mixing 4-benzyloxy phenol, paraformaldehyde and potassium hydroxide in xylene solvent, heating to reflux (temperature about 138 ℃ C. and 144 ℃ C.) after mixing under the protection of nitrogen, cooling to room temperature after reacting for 6h, and filtering to obtain off-white crude product. Washing with dimethylbenzene, acetone and petroleum ether in sequence to obtain white light powder solid 4-benzyloxy calix [ octa ] arene with the yield of 45.2%.

(2) According to the formula of 4-benzyloxy calix [ octa ] arene: chloroform: iodotrimethylsilane (TMSI): the molar ratio of the anhydrous methanol is 1: 750: 430: 1470 proportion, under the protection of nitrogen, adding 4-benzyloxy calix [ octa ] arene into a chloroform solvent, slowly adding TMSI (very volatile and highly corrosive) into the suspension, heating to reflux (the temperature is about 55-65 ℃) under the protection of nitrogen, reacting for 12 hours, cooling to room temperature, adding anhydrous methanol to obtain a yellow suspension, and performing centrifugal separation to obtain a white solid. After drying under vacuum, the bluish substance calix [ octa ] hydroquinone (bluing in water) was obtained in 76.5% yield.

(3) According to the content of cup [ eight ] hydroquinone: glacial acetic acid: iron chloride: potassium dichromate: the molar ratio of water is 1: 1160: 24: 14: according to the 10200 proportion, calix [ octa ] hydroquinone is dissolved in glacial acetic acid, the temperature is raised to 50 ℃ under the protection of nitrogen, anhydrous ferric trichloride solution is added dropwise, the color of the solution gradually changes from gray to green, and finally changes to yellow-green. And after stirring for 15min, pouring the obtained yellow-green solution into a potassium dichromate solution, heating to 90 ℃, and reacting for 15 min. Cooling to room temperature, and filtering to obtain a yellow green solid crude product. Dissolving the obtained crude product in dimethyl sulfoxide, stirring at room temperature for 30min, performing suction filtration, and sequentially washing with glacial acetic acid, acetone, ethyl acetate and petroleum ether to obtain the yellow calix [ octa ] quinone with a yield of 70.2%.

Prepared cup [ octa ] using deuterated trifluoroacetic acid as solvent]Quinones are respectively subjected to nuclear magnetic resonance¹HNMR and¹³c NMR measurement:

FIG. 3 shows a cup [ eight ] prepared in this example]Process for preparing quinones¹H NMR test chart: the peak at 11.50 is the solvent peak, 6.90 and 3.74 correspond to hydrogen on the p-benzoquinone unit and hydrogen on the methylene, respectively, with an integrated ratio of 1: 1.¹H NMR(C₂DF₃O₂-d₁)δ6.90(s，16H，-CH＝C-)，δ3.74(s，16H，-CH₂-)

FIG. 4 shows a cup [ eight ] prepared in this example]Process for preparing quinones¹³C NMR test chart: two quartets between 160 and 165 and between 110 and 120 correspond to the solvent peak of deuterated trifluoroacetic acid, calix [ octa ]]Process for preparing quinones¹³C NMR(C₂DF₃O₂-d₁) Is delta 29.18(s, -CH)₂-)，δ134.47(s，-C＝CH-)，δ147.33(s，-C-CH₂-)，δ185.83(s，-C＝O)，δ190.15(s，-C＝O)。

The resulting cup of organic material [ eight ]]The application of the quinone in the lithium ion secondary battery: the positive electrode of the lithium ion secondary battery is a cup (eight)]Quinone, the cathode material is a metal lithium sheet, and the electrolyte is 1M LiPF₆V (EC: DMC ═ 1: 1w/w) solution. And (4) standing the assembled battery in an oven at 30 ℃ for 8-12h, and carrying out electrochemical test.

Example 4

(1) As 4-benzyloxyphenol: xylene: paraformaldehyde: the molar ratio of potassium hydroxide is 1: 21: 1.9: 0.04, placing 4-benzyloxy phenol, paraformaldehyde and potassium hydroxide in a xylene solvent, uniformly mixing, heating to reflux (the temperature is about 138 ℃ C. and 144 ℃ C.) after mixing under the protection of nitrogen, cooling to room temperature after reacting for 8h, and performing suction filtration to obtain an off-white crude product. Washing with xylene, acetone and petroleum ether in turn to obtain white light powder solid 4-benzyloxy calix [ octa ] arene with the yield of 45.4%.

(2) 4-benzyloxy calix [ octa ] arene: chloroform: according to the weight ratio of iodotrimethylsilane: the molar ratio of the anhydrous methanol is 1: 760: 430: 1460 adding 4-benzyloxy calix [ octa ] arene into chloroform solvent under the protection of nitrogen, slowly adding iodotrimethylsilane (extremely volatile and highly corrosive) into the suspension, heating to reflux (about 55-65 ℃) under the protection of nitrogen for reaction for 14 hours, cooling to room temperature, adding anhydrous methanol to obtain yellow suspension, and centrifuging to obtain white solid. After drying under vacuum, the bluish substance calix [ octa ] hydroquinone (bluish in water) was obtained in 60.2% yield.

(3) According to the content of cup [ eight ] hydroquinone: glacial acetic acid: ferric chloride: potassium dichromate: the molar ratio of water is 1: 1160: 23: 13: 10300 dissolving calix [ octa ] hydroquinone in glacial acetic acid, heating to 50 deg.C under the protection of nitrogen, adding dropwise anhydrous ferric chloride solution to gradually turn from gray to green, and finally to yellow-green. And after stirring for 15min, pouring the obtained yellow-green solution into a potassium dichromate solution, heating to 90 ℃, and reacting for 15 min. Cooling to room temperature, and filtering to obtain a yellow green solid crude product. Dissolving the obtained crude product in dimethyl sulfoxide, stirring at room temperature for 60min, performing suction filtration, and sequentially washing with glacial acetic acid, acetone, ethyl acetate and petroleum ether to obtain yellow calix [ octa ] quinone with a yield of 50.6%.

Cup [ eight)]Application of quinone in lithium ion secondary batteries: with cup [ eight ]]Quinone is used as a positive electrode, a metal lithium sheet is used as a negative electrode, and the electrolyte is 1M LiPF₆V (EC: DMC ═ 1: 1w/w) solution; and (3) standing the assembled battery in an oven at 30 ℃ for 8-12h, and then carrying out electrochemical test.

In this example, the cyclic voltammetry test results are shown in FIG. 5, using a cup of a common electrolyte [ eight]The cyclic voltammetry curve of the quinone lithium ion battery is within the voltage range of 1.2-3.9V and at the sweep rate of 0.2 mV/s. As can be seen from the figure, cup [ eight ]]In the charging and discharging processes, the quinone is respectively at 2.6V,3.0V and 3.5V show one reduction peak and two oxidation peaks. This description cup [ eight ]]Quinone in the discharge process, one-step reduction reaction occurs, cup [ eight]The 16 carbonyl structures of the quinone can be simultaneously combined with 16 electrons to generate corresponding radical anions, and 16 Li are inserted⁺(ii) a While in the charging process, the oxidation reaction is carried out in two steps, with loss of electrons and Li⁺Removed and reduced to carbonyl structure. As shown in fig. 6, cup [ eight ]]The initial discharge specific capacity of the quinone reaches 408mAh g^-1(theoretical specific capacity 446mAh g^-1) Teaching cup (eight)]16 carbonyl active sites in the quinone molecule participate in charge and discharge reactions.

Comparative example 1

With cup (four)]Quinone is used as a positive electrode, a metal lithium sheet is used as a negative electrode, and the electrolyte is 1M LiPF₆V (EC: DMC ═ 1: 1w/w) solution; and (3) standing the assembled battery in an oven at 30 ℃ for 8-12h, and then carrying out electrochemical test.

With cup (six)]Quinone is used as a positive electrode, a metal lithium sheet is used as a negative electrode, and the electrolyte is 1M LiPF₆V (EC: DMC ═ 1: 1w/w) solution; and (3) standing the assembled battery in an oven at 30 ℃ for 8-12h, and then carrying out electrochemical test.

To test the cycling stability of calix [ octaquinone, the cells of example 4 and comparative example 1 were subjected to a capacity cycling test, see fig. 7, where C4Q is calix [ tetra ] quinone, C6Q is calix [ hexa ] quinone, and C8Q is calix [ octaquinone.

According to the results, the initial discharge capacity of C8Q can reach 408mAh g^-1(theoretical specific capacity is 446mAh g^-1) The coulombic efficiency was substantially stabilized at 99%, indicating that C8Q has good redox reversibility. The capacity of C8Q decayed as the number of cycles increased, and the discharge capacity remained at 174mAh g after 200 cycles^-1The capacity retention rate was 49%. Compared with the similar substances C4Q and C6Q, the C6Q has 120mAh g left after 200 times of circulation^-1Whereas, C4Q only left 40mAh g of discharge capacity after 200 cycles^-1Therefore, the cycling stability of C8Q is significantly better, which indicates that C8Q, although it also has dissolution problems, has a larger molecular structure that effectively alleviates its dissolution in organic electrolytes.

The above description is only for the preferred embodiment of the present invention and is not intended to limit the scope of the present invention, and all equivalent modifications made by the contents of the present specification and the drawings, or applied directly or indirectly to other related technical fields, are included in the scope of the present invention.