CN114920909A - Aryl boron-anthraquinone based conjugated polymer and preparation method and application thereof - Google Patents
Aryl boron-anthraquinone based conjugated polymer and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of organic polymer lithium ion batteries, in particular to an aryl boron-anthraquinone based conjugated polymer and a preparation method and application thereof. A very stable conjugated porous polymer is constructed by taking triaryl boron as a center and anthraquinone as a connecting unit. The polymer can retain 95% of mass at 430 ℃ in a thermogravimetric test, and shows excellent thermal stability. Can be used as the anode material of a lithium ion battery, wherein the current density is 0.5A g ‑1 The battery capacity is 131.8mAh/g, and the high-current working performance is better; the capacity of 500 cycles of circulation under the current density of 1A/g can be kept at 86.3 percent, and the better electrochemical circulation stability is shown; the battery is stored for 27 days in the normal temperature environmentThe voltage of the material is only reduced by 0.28V, and the voltage holding ratio is 88.8%, which shows that the material has good self-discharge resistance. Meanwhile, the lithium ion battery can also be used as a positive electrode material of recyclable polymer batteries or sodium, potassium, zinc, magnesium, aluminum and calcium ion batteries.
Description
Technical Field
The invention relates to the technical field of organic polymer lithium ion batteries, in particular to an aryl boron-anthraquinone based conjugated polymer and a preparation method and application thereof.
Background
Lithium ion batteries have been one of the indispensable renewable energy storage devices, and are now widely used in portable digital devices and electric vehicles. The traditional lithium-containing transition metal oxide anode cannot meet the use requirements of high multiplying power, long cycle and the like, and the research on the lithium ion battery electrode material is in bottleneck. As a substitute for conventional inorganic materials, organic materials are considered promising electrodes for lithium ion batteries due to their attractive advantages of light weight elements, molecular-scale structural design, rapid ion transport, good environmental impact, flexible properties, and the like.
Among them, small organic carbonyl compounds and carbonyl group-containing polymers have been widely studied as electrode materials due to their high theoretical capacity, rapid redox kinetics, and structural diversity. However, the bottleneck in the commercialization of organic carbonyl electrodes is poor cyclability, mainly due to side reactions of dissolved organic materials with electrolytes.
Therefore, designing a practical organic carbonyl polymer with good thermodynamic stability and excellent cycling stability is a main research direction in the field of electrodes of organic lithium ion batteries.
Disclosure of Invention
In order to solve the technical problems, the invention constructs an extremely stable conjugated porous polymer by taking triarylboron as a center and anthraquinone as a connecting unit, and aims to provide an arylboron-anthraquinone-based conjugated polymer, and a preparation method and application thereof.
The invention protects an aryl boron-anthraquinone-based conjugated polymer, which takes triaryl boron as the center and anthraquinone as a connecting unit, and has a molecular structural formula as follows:
The invention also provides a preparation method of the aryl boron-anthraquinone-based conjugated polymer, which comprises the following steps:
under the protection of nitrogen, heating and refluxing a mixed solution of a monomer M1, a monomer M2, cuprous iodide, triethylamine of a palladium catalyst and tetrahydrofuran at 75 ℃ for 72 hours, then cooling a reaction system to room temperature, filtering, collecting precipitates, washing with chloroform, water, ethanol and acetone in sequence to remove unreacted monomers or catalyst residues, and performing Soxhlet extraction in methanol for 24 hours for further purification; finally, vacuum drying the product at 60 ℃ for 24h to obtain brown powdery aryl boron-anthraquinone-based conjugated polymer; wherein, the molecular structural formulas of the monomer M1 and the monomer M2 are respectively:
further, the preparation method of the monomer M1 comprises the following steps:
under the protection of nitrogen, dissolving the intermediate 1 in newly distilled ether solution, standing at-78 ℃ for 0.5h, dropwise adding n-butyllithium solution, heating the reaction system to 0 ℃, stirring for 1h, and slowly dropwise adding BF at-78 DEG 3 ·OEt 2 Gradually raising the reaction system to room temperature after the dropwise addition, stirring overnight, quenching the reaction with water after the reaction is finished, extracting with diethyl ether, combining organic phases, washing with brine, drying with magnesium sulfate, distilling under reduced pressure to remove the solvent, and ultrasonically suspending the crude product in Et 2 O/MeOH, and the crude white product was collected by filtration and washed with methanol to give monomer M1 as a white solid;
the preparation method of the intermediate 1 comprises the following steps:
dissolving 1,2,4, 5-tetramethylbenzene and iodine in dichloromethane, dropwise adding a dichloromethane solution in liquid bromine into the solution under stirring, heating and refluxing at 40 ℃ for 1.5h, cooling the system to room temperature, adding a sodium hydroxide solution, filtering to obtain a white crude product, washing with water and methanol, and drying under reduced pressure in a vacuum drying oven overnight to obtain a white target product, namely an intermediate 1.
Further, the preparation method of the monomer M2 comprises the following steps:
dissolving the intermediate 3 in trichloromethane, heating and refluxing, dropwise adding a trichloromethane solution of tetra-n-butylammonium fluoride into a reaction system within 1h, continuing the reaction for 2h, adding water to quench the reaction, and washing an organic phase with brine and water; removing the solvent by reduced pressure distillation, carrying out ultrasonic treatment on the obtained solid in methanol for 30min, filtering and drying to obtain brown monomer M2;
the preparation method of the intermediate 3 comprises the following steps:
under the protection of nitrogen, adding trimethylacetylene silicon into the intermediate 2, cuprous iodide, a palladium catalyst and a mixed solution of triethylamine and toluene, heating and refluxing for 3h at 100 ℃, filtering the cooled solution through diatomite, washing with toluene, washing the filtrate with brine and water respectively, removing the solvent by reduced pressure distillation, carrying out ultrasonic treatment on the obtained solid in methanol for 30min, filtering and drying to obtain a yellow target product intermediate 3;
the preparation method of the intermediate 2 comprises the following steps:
mixing 2, 6-diaminoanthraquinone, acetonitrile and hydrochloric acid, and slowly dripping a sodium nitrite aqueous solution into the mixed solution in an ice bath; stirring for 30min, and adding potassium iodide aqueous solution; stirring for 1h at room temperature, heating to 60 ℃ for reaction for 1h, cooling the system to room temperature, filtering to obtain a crude product, washing with water and methanol, stirring the crude product in dichloromethane for 1h, filtering again, washing with dichloromethane, and drying in vacuum to obtain a light brown target product intermediate 2.
The invention also discloses application of the aryl boron-anthraquinone based conjugated polymer, and the polymer can be used as a positive electrode material of a lithium ion battery.
Furthermore, the polymer can be used as a positive electrode material of a high-power lithium ion battery.
Further, the polymer can be used as a positive electrode material of a recyclable polymer battery.
Further, the polymer can be used as a positive electrode material of sodium, potassium, zinc, magnesium, aluminum and calcium ion batteries.
Compared with the prior art, the invention has the following beneficial effects:
in a thermogravimetric test, the prepared arylboron-anthraquinone-based conjugated polymer can retain 95% of mass at 430 ℃, and shows excellent thermal stability. Can be used as the anode material of a lithium ion battery, wherein the current density is 0.5A g -1 The battery capacity is 131.8mAh/g, and the high-current working performance is better; the capacity of 500 cycles of circulation under the current density of 1A/g can be kept at 86.3 percent, and the better electrochemical circulation stability is shown; when the battery is stored for 27 days in a normal-temperature environment, the voltage of the battery is only reduced by 0.28V, and the voltage retention rate is 88.8%, which shows that the material has good self-discharge resistance.
Drawings
FIG. 1 shows the NMR spectra of the polymer of the present invention;
FIG. 2 is an infrared spectrum of the polymer of the present invention;
FIG. 3 is a 10,000-fold image of a polymer of the present invention under a scanning electron microscope;
FIG. 4 is a 80,000-fold image of a polymer of the present invention under a scanning electron microscope;
FIG. 5 is a thermogravimetric plot of the polymer of the present invention measured experimentally;
FIG. 6 is a cyclic voltammogram of a half-cell assembled from a polymer of the present invention and a lithium plate; in the figure, the sweep rate is 0.2-1.0 mV/s;
FIG. 7 is a graph of rate performance of a half cell assembled from a polymer lithium plate of the present invention; in the figure, the current densities are 0.5, 1.0 and 1.5A/g respectively;
FIG. 8 is a graph showing the voltage decay with time of a half-cell assembled with a lithium plate under normal temperature regulation according to the present invention;
FIG. 9 shows a half-cell of the present invention assembled with a lithium plate at a current density of 1A g -1 A time-of-flight cycle curve;
FIG. 10 is a chemical structure of a polymer of the present invention;
FIG. 11 is a synthetic route of arylboron-anthraquinone-based conjugated polymers of the present invention.
Detailed Description
The technical solutions of the present invention will be described below clearly and completely in conjunction with the embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
An arylboron-anthraquinone-based conjugated polymer takes triarylboron as a center, anthraquinone as a connecting unit, and the molecular structural formula of the polymer is shown in figure 10, wherein n is 6-10. Such a molecular structural formula has an extremely stable conjugated structure.
The aryl boron-anthraquinone-based conjugated polymer is synthesized by a monomer M1 and a monomer M2, the synthetic route is shown as the attached figure 11, and the specific synthetic steps are as follows:
a mixed solution of monomer M1(0.50g,0.770mmol), monomer M2(0.445g,1.74mmol), cuprous iodide (0.034g,0.174mmol), tetrakis (triphenylphosphine) palladium (0.20g,0.174mmol) in triethylamine (10.0mL) and tetrahydrofuran (15.0mL) was heated under reflux at 75 ℃ for 72h under nitrogen protection, then the reaction was cooled to room temperature, the precipitate was collected by filtration and washed with chloroform, water, ethanol and acetone in order to remove unreacted monomer or catalyst residue, and further purified by soxhlet extraction in methanol for 24 h; finally, the product was vacuum dried at 60 ℃ for 24h to give a brown powdered arylboron-anthraquinone based conjugated polymer, yield: 0.523g, yield: 57.6%, IR (KBr, cm) -1 ):3036,2194,1678,1586,1312,1089. 13 C CP/MAS NMR(400MHz,ppm,293K):δ178.71,110-150,70-88,18.76。
The monomer M1 has the following synthetic route:
first step, synthesis of intermediate 1:
in a 250mL three- mouth bottleDissolving 1,2,4, 5-tetramethylbenzene (12.5g,90.0mmol) and iodine (0.50g,2.0mmol) in 70.0mL of dichloromethane, adding 50.0mL of dichloromethane solution in liquid bromine (12.0mL,233mmol) dropwise to a three-necked flask of the above solution under stirring, heating under reflux at 40 ℃ for 1.5h, cooling the system to room temperature, adding 5.0M sodium hydroxide solution (25.0mL), filtering to give a white crude product, washing with water and methanol, and drying under reduced pressure in a vacuum oven overnight to give a white target product, intermediate 1; yield: 21.2g, yield: 80.2 percent; 1 H NMR(400MHz,CDCl 3 ,ppm,293K)：δ2.49(s,12H,Ar-CH 3 )；
second step, synthesis of monomer M1:
under the protection of nitrogen, intermediate 1(3.50g,12.0mmol) was dissolved in freshly distilled ether solution (100mL) and left to stand at-78 ℃ for 0.5h, n-butyllithium solution (7.50mL,12.0mmol,1.60M in hexanes) was added dropwise, the reaction was raised to 0 ℃ and stirred for 1h, and BF was slowly added dropwise at-78 ℃ 3 ·OEt 2 (0.50mL,3.95mmol), gradually raising the reaction system to room temperature after the dropwise addition, stirring overnight, quenching the reaction with water after the reaction is finished, extracting with diethyl ether, combining organic phases, washing with brine, drying over magnesium sulfate, distilling under reduced pressure to remove the solvent, ultrasonically suspending the crude product in Et 2 O/MeOH (v: v, 5mL/5mL) in a solvent, and the crude white product was collected by filtration and washed with methanol to give a white solid as monomer M1; yield: 1.95g, yield: 76.2 percent; 1 H NMR(400MHz,CDCl 3 ,ppm,293K):δ2.35(s,18H,Ar-CH 3 ),2.01(s,18H,Ar-CH 3 )。
wherein, the monomer M2 has the following synthetic route:
first step, synthesis of intermediate 2:
a250 mL round-bottom flask was charged with 2, 6-diaminoanthraquinone (1.01g,4.22mmol), acetonitrile (30.0mL), and hydrochloric acid (10.0mL,2.40M), mixed, and then a solution of sodium nitrite (0.694mg,10.1mmol) in water (2.00mL) was added under ice bathSlowly dripping into the mixed solution; after stirring for 30min, an aqueous solution (5.0mL) of potassium iodide (3.55g,21.4mmol) was added; stirring for 1h at room temperature, heating to 60 ℃ for reaction for 1h, cooling the system to room temperature, filtering to obtain a crude product, washing with water and methanol, stirring the crude product in dichloromethane (40.0mL) for 1h, filtering again, washing with dichloromethane, and vacuum drying to obtain a light brown target product intermediate 2; yield: 1.12g, yield: 57.6 percent; 1 HNMR(400MHz,CDCl 3 ,ppm,293K):δ8.64(s,2H,Ar-H),8.18(d,2H,Ar-H),7.99(d,2H,Ar-H)；
second step, synthesis of intermediate 3:
adding trimethylethynylsilicon to a mixed solution of intermediate 2(0.46g,1.0mmol), cuprous iodide (3.80mg, 20.0. mu. mol), bis (triphenylphosphine) palladium dichloride (14.0mg, 20.0. mu. mol), and triethylamine (4.0mL) and toluene (10.0mL) under nitrogen protection, heating and refluxing at 100 ℃ for 3h, filtering the cooled solution through celite, washing with 10.0mL of toluene, washing the filtrate with brine and water, respectively, distilling off the solvent under reduced pressure, sonicating the resulting solid in methanol (75.0mL) for 30min, filtering, and drying to give intermediate 3, a yellow target product; yield: 0.250g, yield: 62.5 percent; 1 H NMR(400MHz,CDCl 3 ,ppm,293K):δ8.36(d,2H,Ar-H),8.25(d,2H,Ar-H),7.83(dd,2H,Ar-H)；
thirdly, synthesizing a monomer M2:
dissolving the intermediate 3(0.20g,0.50mmol) in chloroform (10.0mL), heating and refluxing, dropwise adding a chloroform (5.0mL) solution of tetra-n-butylammonium fluoride (1.50mL,1.50mmol,1.60M in THF) into the reaction system within 1h, continuing the reaction for 2h, adding 10.0mL of water to quench the reaction, and washing the organic phase with brine and water; after removal of the solvent by distillation under reduced pressure, the resulting solid was sonicated in methanol (20.0mL) for 30min, filtered and dried to give brown monomer M2; yield: 98.0mg, yield: 76.6 percent; 1 HNMR(400MHz,CDCl 3 ,ppm,293K):δ8.41(s,2H,Ar-H),8.29(d,2H,Ar-H),7.88(d,2H,Ar-H),3.38(s,2H,-C≡CH)。
as shown in the accompanying FIGS. 6 to 9, the arylboron-anthraquinone-based conjugated polymer acts as a lithium ionAt a current density of 0.5A g for the positive electrode of the subcell -1 The battery capacity is 131.8mAh/g, and the high-current working performance is better; the capacity of 500 cycles of circulation under the current density of 1A/g can be kept at 86.3 percent, and the better electrochemical circulation stability is shown; when the battery is stored for 27 days in a normal-temperature environment, the voltage of the battery is only reduced by 0.28V, and the voltage retention rate is 88.8%, which shows that the material has good self-discharge resistance. Meanwhile, in a thermogravimetric test, the mass can be kept at 95% at 430 ℃, and excellent thermal stability is shown. Based on the advantages, the polymer can be used as the anode material of high-power lithium ion batteries, recyclable polymer batteries and sodium, potassium, zinc, magnesium, aluminum and calcium ion batteries.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. The aryl boron-anthraquinone-based conjugated polymer is characterized in that the aryl boron-anthraquinone-based conjugated polymer takes triaryl boron as a center and anthraquinone as a connecting unit, and the molecular structural formula of the aryl boron-anthraquinone-based conjugated polymer is as follows:
2. The method for preparing an arylboron-anthraquinone-based conjugated polymer according to claim 1, which is characterized by comprising the following steps:
under the protection of nitrogen, heating and refluxing a mixed solution of a monomer M1, a monomer M2, cuprous iodide, triethylamine of a palladium catalyst and tetrahydrofuran at 75 ℃ for 72 hours, then cooling a reaction system to room temperature, filtering, collecting precipitates, washing with chloroform, water, ethanol and acetone in sequence to remove unreacted monomers or catalyst residues, and performing Soxhlet extraction in methanol for 24 hours for further purification; finally, vacuum drying the product at 60 ℃ for 24h to obtain brown powdery aryl boron-anthraquinone-based conjugated polymer; wherein, the molecular structural formulas of the monomer M1 and the monomer M2 are respectively:
3. the method for preparing arylboron-anthraquinone-based conjugated polymer according to claim 2, wherein the method for preparing monomer M1 comprises:
under the protection of nitrogen, dissolving the intermediate 1 in newly distilled ether solution, standing at-78 ℃ for 0.5h, dropwise adding n-butyllithium solution, heating the reaction system to 0 ℃, stirring for 1h, and slowly dropwise adding BF at-78 DEG 3 ·OEt 2 Gradually raising the reaction system to room temperature after the dropwise addition, stirring overnight, quenching the reaction with water after the reaction is finished, extracting with diethyl ether, combining organic phases, washing with brine, drying with magnesium sulfate, distilling under reduced pressure to remove the solvent, and ultrasonically suspending the crude product in Et 2 The crude white product was collected by filtration in a solvent of O/MeOH and washed with methanol to give monomer M1 as a white solid;
the preparation method of the intermediate 1 comprises the following steps:
dissolving 1,2,4, 5-tetramethylbenzene and iodine in dichloromethane, dropwise adding a dichloromethane solution in liquid bromine into the solution under stirring, heating and refluxing at 40 ℃ for 1.5h, cooling the system to room temperature, adding a sodium hydroxide solution, filtering to obtain a white crude product, washing with water and methanol, and drying under reduced pressure in a vacuum drying oven overnight to obtain a white target product, namely an intermediate 1.
4. The method for preparing arylboron-anthraquinone-based conjugated polymer according to claim 2, wherein the method for preparing monomer M2 comprises:
dissolving the intermediate 3 in trichloromethane, heating and refluxing, dropwise adding a trichloromethane solution of tetra-n-butylammonium fluoride into a reaction system within 1h, continuing the reaction for 2h, adding water to quench the reaction, and washing an organic phase with brine and water; removing the solvent by reduced pressure distillation, carrying out ultrasonic treatment on the obtained solid in methanol for 30min, filtering and drying to obtain brown monomer M2;
the preparation method of the intermediate 3 comprises the following steps:
under the protection of nitrogen, adding trimethylacetylene silicon into the intermediate 2, cuprous iodide, a palladium catalyst and a mixed solution of triethylamine and toluene, heating and refluxing for 3h at 100 ℃, filtering the cooled solution through diatomite, washing with toluene, washing the filtrate with brine and water respectively, removing the solvent by reduced pressure distillation, carrying out ultrasonic treatment on the obtained solid in methanol for 30min, filtering and drying to obtain a yellow target product intermediate 3;
the preparation method of the intermediate 2 comprises the following steps:
mixing 2, 6-diaminoanthraquinone, acetonitrile and hydrochloric acid, and slowly dripping the aqueous solution of sodium nitrite into the mixed solution in an ice bath; stirring for 30min, and adding potassium iodide aqueous solution; stirring for 1h at room temperature, heating to 60 ℃ for reaction for 1h, cooling the system to room temperature, filtering to obtain a crude product, washing with water and methanol, stirring the crude product in dichloromethane for 1h, filtering again, washing with dichloromethane, and drying in vacuum to obtain a light brown target product intermediate 2.
5. The use of an arylboron-anthraquinone-based conjugated polymer according to claim 1, wherein the polymer can be used as a positive electrode material of a lithium ion battery.
6. The use of the arylboron-anthraquinone-based conjugated polymer according to claim 1, wherein the polymer can be used as a positive electrode material of a high-power lithium ion battery.
7. The use of an arylboron-anthraquinone-based conjugated polymer according to claim 1, which is used as a positive electrode material for recyclable polymer batteries.
8. The use of an arylboron-anthraquinone-based conjugated polymer according to claim 1, which is used as a positive electrode material for sodium, potassium, zinc, magnesium, aluminum and calcium ion batteries.
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