CN113097480B

CN113097480B - Carbonyl polymer and synthesis method and application thereof

Info

Publication number: CN113097480B
Application number: CN202110307563.5A
Authority: CN
Inventors: 刘熙; 李彩婷; 汪达; 何芷灵; 张誉元
Original assignee: Wuyi University
Current assignee: Wuyi University
Priority date: 2021-03-23
Filing date: 2021-03-23
Publication date: 2022-04-05
Anticipated expiration: 2041-03-23
Also published as: WO2022198815A1; CN113097480A

Abstract

The invention discloses a carbonyl polymer and a synthesis method and application thereof, wherein the structure of the carbonyl polymer is shown in figure 1, wherein R' is C_1～50Alkyl, straight or branched, R and R' are H, C_1～50Alkyl is straight chain or branched chain, and n is 1-10000. The carbonyl polymer has the advantages of low synthesis cost, good redox activity, high specific capacity, high energy density and the like, and when the carbonyl polymer is used as a lithium battery anode material, the specific capacity can reach 255mAh/g, and the working voltage interval is 2.5-2.7V. The invention realizes the development of a low-cost carbonyl polymer with theoretical production cost as low as $ 0.48/g, the polymer shows the price-to-performance ratio as low as 0.0017 cents per 100mAh, is the best level of the reported materials at present, and has good application prospect in the field of lithium battery electrode materials.

Description

Carbonyl polymer and synthesis method and application thereof

Technical Field

The invention belongs to the technical field of lithium battery materials, and particularly relates to a carbonyl polymer and a synthesis method and application thereof.

Background

As global demand for energy has increased year by year, traditional energy sources such as petroleum and coal have been increasingly exhausted, and the development concept of "carbon neutralization" has been continuously promoted globally due to the need of protecting the global ecological environment, more and more scientists have focused on the aspects related to new energy materials and devices.

In recent years, with the accelerated development of industries such as portable intelligent wearable electronic devices and electric new energy vehicles, new energy devices represented by Lithium Ion Batteries (LIBs) have been drawing attention. Currently, the electrode materials of commercial lithium ion batteries are mainly inorganic metal oxides, such as LiCoO₂，LiMn₂O₄And LiFePO₄Etc. they are generally lowThe capacity is practically used, and the materials are scarce and non-renewable resources, which is not beneficial to the long-term sustainable development of the industry. Organic materials are considered to be very promising alternatives. Organic electrode materials have many performance advantages: the organic material can realize multiple active sites per unit weight, so that the organic electrode material has high capacity; the organic material is composed of organic elements (such as C, H, O, N and S) rich in earth crust, can be obtained from biomass resources or through mild chemical synthesis reaction, is cheap and environment-friendly, and meets the requirement of sustainable development; compared with inorganic compounds, the molecular structure of the organic material can be flexibly adjusted to meet different electrochemical performance requirements, is safer when completely discharged, and has higher environmental compatibility. The organic material also has the characteristics of light weight, flexibility, excellent mechanical property and the like, and is favorable for developing the leading-edge application of the energy storage battery in portable and wearable electronic equipment.

Disclosure of Invention

In order to solve the defects in the prior art, the invention aims to provide a carbonyl polymer and a synthesis method thereof. The carbonyl polymer can be applied to the field of lithium battery electrode materials, can be used as a lithium battery anode material, and has the advantages of low synthesis cost, good redox activity, high specific capacity, high energy density and the like.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

a carbonyl polymer having the formula:

wherein R' is C_1～50Alkyl, straight or branched, R and R' are H, C_1～50Alkyl is straight chain or branched chain, and n is 1-10000.

The invention also provides a synthesis method of the carbonyl polymer, which comprises the following steps: prepared by amination, oxidation and polymerization of vanillin and polyamine monomer.

Preferably, the polyamine-based monomer has at least one of the following structural formulae:

preferably, in the method for synthesizing the carbonyl polymer, the molar ratio of the vanillin to the polyamine is x, and 0< x < 100.

Preferably, the synthesis method of the carbonyl polymer comprises the following steps: adding vanillin and a polyamine monomer into a solvent in an air atmosphere to carry out amination oxidation polymerization reaction, and purifying after the reaction is finished to obtain the carbonyl polymer.

Preferably, the solvent is an alcohol solvent; more preferably an ethanol solvent.

The invention also provides application of the carbonyl polymer in lithium battery electrode materials.

Preferably, the carbonyl polymer is used for preparing the lithium battery cathode material.

The invention also provides a lithium battery electrode material which comprises the carbonyl polymer.

Compared with the prior art, the invention has the beneficial effects that: the carbonyl polymer has the advantages of low synthesis cost, good redox activity, high specific capacity, high energy density and the like, and when the carbonyl polymer is used as a lithium battery anode material, the specific capacity can reach 255mAh/g, and the working voltage interval is 2.5-2.7V. The invention realizes the development of a low-cost carbonyl polymer with theoretical production cost as low as $ 0.48/g, the polymer shows the price-performance ratio as low as 0.0017 cents/100 mAh, is the best level of the reported materials at present, and has good application prospect in the field of lithium battery electrode materials.

Drawings

FIG. 1 is a chemical structure of a carbonyl polymer according to the invention;

FIG. 2 is a schematic diagram showing the synthesis scheme of carbonyl polymer 1 (abbreviated as NP1) of example 1;

FIG. 3 is a schematic diagram showing the synthesis scheme of carbonyl polymer 2 (abbreviated as NP2) of example 2;

FIG. 4 is a chart of the infrared spectra of carbonyl polymers NP1 and NP 2;

FIG. 5 is a schematic structural diagram of a lithium battery positive electrode material and a corresponding lithium battery using the polymer NP 2;

fig. 6 is a lithium battery charge and discharge performance curve (voltage-specific capacity curve) based on polymer NP 2;

FIG. 7 is a comparison of cost analysis of NP2 polymer with current organic carbonyl polymers and small molecules reported in the literature.

Detailed Description

The invention is further illustrated by the following specific examples, which are intended to aid in a better understanding of the present invention, including in particular the synthesis of carbonyl polymers and the preparation of batteries. The described embodiments are only some, and not all, embodiments of the invention. 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.

The practice of the present invention may employ conventional techniques of polymer chemistry within the skill of the art. In the following examples, efforts are made to ensure accuracy with respect to numbers used (including amounts, temperature, reaction time, etc.) but some experimental errors and deviations should be accounted for. The temperatures used in the following examples are expressed in degrees Celsius and the pressures are at or near atmospheric. The solvents used were purchased analytically or chromatographically pure. All reagents were obtained commercially unless otherwise indicated.

Example 1

The synthesis reaction formula of the carbonyl polymer 1 (NP 1 for short) is shown in figure 2, and the specific synthesis steps are as follows:

vanillin (10 mmol) and N, N' -dimethylethylenediamine (10 mmol) were dissolved in 15 ml ethanol under an air atmosphere, and the reaction was stirred at room temperature (25 ℃) for 48 hours. After the reaction is finished, a polymer is precipitated in methanol, then the polymer is sequentially extracted by the methanol, the acetone and the normal hexane, finally the final polymer is extracted by chloroform, then the methanol is used for precipitation again, and finally the product NP1 is obtained by drying, wherein the yield is 1 g, and the yield is 70%.

Through infrared spectrum experiments, the structure of NP1 is shown in figure 4, and the infrared characteristic peak in the figure shows that the carbonyl characteristic functional group in NP1 polymer is successfully synthesized, i.e. carbonyl polymer NP1 is successfully prepared.

Example 2

The synthesis reaction formula of the carbonyl polymer 2 (NP 2 for short) is shown in figure 3, and the specific synthesis steps are as follows:

vanillin (10 mmol) and piperazine (10 mmol) were dissolved in 15 ml ethanol under an air atmosphere, and the reaction was stirred at room temperature (25 ℃) for 48 hours. After the reaction is finished, a polymer is precipitated in methanol, then the polymer is sequentially extracted by the methanol, the acetone and the normal hexane, finally the final polymer is extracted by chloroform, then the methanol is used for precipitation again, and finally the product NP2 is obtained by drying, wherein the yield is 1 g, and the yield is 70%.

Through infrared spectrum experiments, the structure of NP2 is shown in figure 4, and the infrared characteristic peak in the figure shows that the carbonyl characteristic functional group in NP2 polymer is successfully synthesized, i.e. carbonyl polymer NP2 is successfully prepared.

Example 3

The application of the polymer material NP2 obtained in example 2 as an electrode material in a lithium battery is illustrated by taking the polymer material as an example:

the specific preparation process of the lithium battery is as follows:

(1) preparation of electrode sheet

Weighing and mixing NP2, carbon black and polyvinylidene fluoride (PVDF) according to the weight ratio of 3:6:1, grinding and tabletting to obtain an electrode slice based on NP2, and drying for later use in a vacuum oven at 80 ℃ for 12 hours;

(2) lithium battery assembly

In an argon glove box, the prepared NP2 electrode plate, the diaphragm (0.2 ml of electrolyte is dripped on the diaphragm) and the lithium plate are sequentially assembled according to the lithium battery structure shown in fig. 5, and the lithium battery is prepared after pressure packaging.

A lithium battery charging and discharging curve test is performed in a blue battery test system to obtain a voltage-specific capacity curve of the battery, as shown in fig. 6. As can be seen from FIG. 6, the specific capacity of the lithium battery based on NP2 reaches 255mAh/g, and the working voltage range is 2.5-2.7V. Therefore, the carbonyl polymer is a lithium battery electrode material with excellent performance.

Example 4

Taking the performance of the lithium battery prepared in example 3 and the synthesis cost of NP2 as an example, the synthesis method of the carbonyl polymer has the advantage of low synthesis cost.

As shown in fig. 7, in combination with the reaction yield calculation on the basis of the commercial raw material price, since the carbonyl polymer NP2 synthesized in example 2 requires only 1-step chemical synthesis, and the raw materials are vanillin and piperazine which are cheap and readily available, NP2 has a low theoretical production cost as low as $ 0.48/g, and the polymer NP2 exhibits a price to performance ratio as low as 0.0017 cents per 100mAh, which is the best level of the currently reported material.

The carbonyl polymer material is a lithium battery electrode material with excellent performance, has low synthesis cost, and is a low-cost carbonyl polymer material with great commercial prospect.

Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims

1. A carbonyl polymer having the formula:

wherein R' is C_1~50Alkyl, linear or branched, R and R '' are H, C_1~50Alkyl is straight chain or branched chain, and n = 1-10000.

2. A method for synthesizing a carbonyl polymer as claimed in claim 1, characterized in that, the carbonyl polymer is prepared by amination, oxidation and polymerization of vanillin and polyamine monomers.

3. The method of claim 2, wherein the polyamine-based monomer has at least one of the following structural formulas:

。

4. the method for synthesizing a carbonyl polymer according to claim 2, characterized in that, in the method for synthesizing a carbonyl polymer, the molar ratio of vanillin to the polyamino monomers is x, and 0< x < 100.

5. A process for the synthesis of a carbonyl polymer as claimed in any one of claims 2 to 4, characterized in that, the process for the synthesis of a carbonyl polymer comprises the following steps: adding vanillin and a polyamine monomer into a solvent in an air atmosphere to carry out amination oxidation polymerization reaction, and purifying after the reaction is finished to obtain the carbonyl polymer.

6. A process for the synthesis of a carbonyl polymer as claimed in claim 5, characterized in that, the solvent is an alcoholic solvent.

7. The method for synthesizing a carbonyl polymer as claimed in claim 5, characterized in that, the solvent is ethanol solvent.

8. Use of the carbonyl polymer as defined in claim 1 in an electrode material for lithium batteries.

9. Use of the carbonyl polymer as defined in claim 1 for the preparation of a positive electrode material for lithium batteries.

10. A lithium battery electrode material comprising the carbonyl polymer of claim 1.