CN114230789B - Hyperbranched polymer and preparation method and application thereof - Google Patents
Hyperbranched polymer and preparation method and application thereof Download PDFInfo
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Abstract
The application relates to the technical field of electrode active substances, in particular to a hyperbranched polymer and a preparation method and application thereof. A hyperbranched polymer is synthesized by a connection monomer and an active group monomer through click chemistry reaction; the linking monomer contains at least two ethynyl groups or at least two azide groups, and the reactive group monomer contains at least two azide groups or at least two ethynyl groups. According to the technical scheme, the high-efficiency click chemical reaction is adopted, the technical problem that the two-dimensional (three-dimensional) polymer active electrode material is easy to generate defects is solved, and the theoretical capacity and the actual capacity/theoretical capacity percentage of the lithium battery prepared by the lithium battery active electrode material are further improved. The material of the scheme has a more complete conjugated structure, is beneficial to promoting the efficient transmission of charges in a plane, improves the effectiveness and reversibility of oxidation-reduction reaction, and improves the mechanical property of the material, thereby effectively improving the performance of the corresponding lithium ion battery and having wide application prospect.
Description
Technical Field
The application relates to the technical field of electrode active substances, in particular to a hyperbranched polymer and a preparation method and application thereof.
Background
The lithium ion battery has the advantages of high energy density, excellent charge and discharge characteristics and the like, so that the lithium ion battery is one of the most widely used battery types in the current society. With the continuous emergence of various new application scenes, new challenges are presented to traditional battery technologies, for example, lithium batteries which are light and thin and have certain flexibility are required in application scenes such as smart tags and wearable devices. The new application scenario puts forward new demands on lithium ion battery technology, and lithium batteries are required to have flexibility, contain no toxic or harmful metals, be rapidly charged, have excellent cycle life, and be processed by efficient low-cost technologies (such as printing, reel-to-reel technology, etc.). For electrode materials of lithium ion batteries, the anode materials of the traditional lithium ion batteries generally contain toxic and harmful metal elements such as cobalt and nickel, and the exploitation and refinement of the cobalt and the nickel have high energy consumption, so that the application potential of the lithium ion batteries in novel application scenes is restricted.
At present, organic electrode active materials are being utilized to replace traditional electrode materials so as to meet the requirements of new application scenes. The organic active material of the common lithium ion battery is usually a polymer electrode active material, has flexibility, can be manufactured and processed at low cost through a film production process, has low solubility in electrolyte, and is beneficial to prolonging the cycle life. Over decades of development, various battery indexes of lithium ion batteries using polymer electrode active materials have advanced. Currently, lithium battery polymer active electrode materials can be divided into two main categories according to chemical structures: linear polymers and two-dimensional (three-dimensional) polymers. Of the two-dimensional (three-dimensional) polymers, the most important class is the conjugated organic framework class of polymers (covalent organic framework). The synthesis of this class of polymers is mainly produced by polycondensation of amino groups with aldehyde groups. The prior art reports a negative electrode material named COF-300 and COF-301 (Chinese j. Polym. Sci.2020,38, 550-557) prepared by polycondensation of amino groups with aldehyde groups. The literature also reports a negative electrode material (Energy, 2020,199,117372) named DMTA-COF, which is produced by polycondensation of amino groups with aldehyde groups. However, the performance of lithium batteries prepared from conjugated organic framework-type polymers of the prior art still cannot meet the demands of practical applications, for which reason further studies are required to improve the capacity of batteries prepared with such electrode active materials and the cycling stability thereof.
Disclosure of Invention
The application aims to provide a hyperbranched polymer to solve the technical problems of non-ideal battery capacity and cycle performance of a lithium battery prepared from the existing organic electrode active material.
In order to achieve the above purpose, the application adopts the following technical scheme:
a hyperbranched polymer is synthesized by a connection monomer and an active group monomer through click chemistry reaction; the linking monomer contains at least two ethynyl groups or at least two azide groups, and the reactive group monomer contains at least two azide groups or at least two ethynyl groups.
The principle of the technical scheme and the beneficial effects are as follows:
according to the technical scheme, the click chemistry reaction is used for polymerizing the connecting monomer and the active group monomer into the hyperbranched polymer, so that the defects of the polymer are reduced, and the regularity of the material structure is improved. If the hyperbranched polymer of the scheme is used for preparing the electrode active material, and then the lithium ion battery is prepared, the performance of the corresponding lithium ion battery can be improved. The advantage of this solution over existing two-dimensional (three-dimensional) polymeric materials is: through efficient click chemistry reaction, structural defects in the material are effectively inhibited, so that the material has a more complete conjugated structure, efficient transmission of charges in a plane is facilitated, effectiveness and reversibility of oxidation-reduction reaction are improved, mechanical properties of the material are improved, and performance of a corresponding lithium ion battery is effectively improved.
The lithium battery polymer active electrode materials can be divided into two major classes of linear polymers and two-dimensional (three-dimensional) polymers according to chemical structures. The conjugated organic framework polymer is one of two-dimensional (three-dimensional) polymers, and the method for preparing the polymer in the prior art generally comprises the steps that active groups form hyperbranched structures through polycondensation reaction of amino groups and aldehyde groups, so that the active electrode material of the lithium battery polymer is prepared. However, the performance of lithium batteries prepared from existing organic electrode materials has been problematic: the theoretical capacity of the lithium battery needs to be further improved, and the ratio of the actual battery capacity to the theoretical battery capacity is low, so that the cycle performance of the battery is poor. The inventors have conducted extensive studies on the problems existing in the prior art, and found that the reason for the problems is that the polycondensation reaction efficiency of amino groups and aldehyde groups is low, and the obtained conjugated organic frame polymer has certain defects, which ultimately results in the non-ideal performance of lithium batteries prepared from the existing organic electrode materials. The inventor adopts a click chemistry reaction mode to polymerize the connecting monomer and the active group monomer into the hyperbranched polymer. Due to the high efficiency of click chemistry reaction, the defects are avoided, the regularity of the material structure is further improved, and the performance of a lithium battery prepared from the material is also improved.
Further, the general formula of the connecting monomer is shown as a formula (A) or a formula (B) or a formula (C);
wherein R is 1 Represents any straight-chain hydrocarbon, non-aromatic ring or aromatic ring.
By adopting the technical scheme, the connecting monomer contains ethynyl required by click reaction, and active groups which can contain azido react to form hyperbranched polymer.
Further, the structural formula of the connecting monomer is shown as a formula (3) or a formula (3-1) or a formula (3-2) or a formula (3-3) or a formula (3-4);
wherein m is an integer of 1 to 10.
The coupling of the coupling monomer with the ethynyl group to the active group monomer can be realized by adopting the coupling monomer with the ethynyl group, so that the hyperbranched polymer is formed.
Further, the structural formula of the active group monomer is shown as a formula (D).
Pyrene-4, 5,9, 10-tetraketone is a common positive electrode active material in the prior art, and the technical scheme adds azido based on pyrene-4, 5,9, 10-tetraketone, so that the pyrene-4, 5,9, 10-tetraketone has the performance of click reaction with ethynyl.
Further, a hyperbranched polymer has a general formula shown in formula (E) or formula (F) or formula (G);
wherein A represents an active group represented by the formula (H), R 1 Represents any straight-chain hydrocarbon, non-aromatic ring or aromatic ring; n is an integer of 10 to 300.
The hyperbranched polymer shown in the formula (E), the formula (F) or the formula (G) has good electrochemical performance, and the three polymers are used as positive electrode materials to prepare the lithium ion battery.
Although the efficiency of click chemistry reaction can be utilized to reduce defects and improve the regularity of the polymer, the selection of the linking monomer still has a certain influence on the advantages and disadvantages of the parameters such as the actual first discharge capacity and the 20 th discharge capacity/first discharge capacity. The number of linking groups linking the monomers and the specific choice of their R1 groups can have a significant impact on the performance of the electrode active material and the performance of the lithium battery made therefrom.
The battery prepared using the polymer shown in formula (F) has a higher initial discharge practical capacity, but has a slightly poorer cycle performance than the other two. The inventors analyzed the reason for: the connecting monomer contains 3 or more ethynyl groups (or azido groups), and the obtained polymer can form a three-dimensional structure, but is in a nonlinear structure, so that partial electrode materials in the charge and discharge process are restrained from being dissolved, and the cycle performance is good.
In addition to R 1 The choice of groups will also have an effect on the performance of the cell made from the polymer of this embodiment. If R is 1 The group is straight-chain hydrocarbon or non-aromatic ring, and the initial discharge practical capacity of the battery prepared by using the polymer is ideal. And fruit R 1 The group is aromatic ring, and the initial discharge actual capacity of the battery prepared by using the polymer is relatively low. The inventors also analyzed the generation of the above-mentioned findingsThe reason for this is: due to R 1 R is a straight-chain hydrocarbon or a non-aromatic ring 1 Is R of aromatic ring 1 The flexibility of the material is higher, so that active groups of the material can be fully utilized. Especially straight chain hydrocarbons, which give the material a higher flexibility, facilitate the adequate reaction of lithium ions with active groups and thus have optimal properties.
The scheme also provides a preparation method of the hyperbranched polymer, and the hyperbranched polymer is obtained by carrying out click chemical reaction on the connection monomer and the active group monomer in a sodium ascorbate/copper sulfate system.
In the technical scheme, a sodium ascorbate/copper sulfate system can provide monovalent copper as a catalyst, so that a catalytic active group monomer and a connecting monomer are polymerized to form the hyperbranched polymer.
Further, adding a connecting monomer and an active group monomer into an ethanol water solution, adding a sodium ascorbate solution under the stirring condition, and then adding copper sulfate pentahydrate to perform click chemistry reaction; then ethanol precipitation and vacuum drying are carried out to obtain the hyperbranched polymer; the ratio of the number of ethynyl or azido groups of the linking monomer to the number of azido or ethynyl groups of the reactive group monomer is from 0.8 to 1.2.
In the actual operation process, the ratio of the number of ethynyl groups or azido groups of the connection monomer and the azido groups of the active group monomer to obtain the ethynyl groups is maintained at 0.8-1.2, hyperbranched polymers shown in the formulas (E) - (G) can be successfully obtained, and the hyperbranched polymers have ideal performances, and can obtain ideal actual initial discharge capacity and cycle performance when the hyperbranched polymers are applied to the preparation of lithium batteries.
Further, the synthesis method of the connecting monomer comprises the following steps: containing R 1 The halide of the group is subjected to substitution reaction with 2-methyl-3-butyn-2-ol, and then the linking monomer shown as the formula (A) or the formula (B) or the formula (C) is obtained through alkaline hydrolysis.
The reaction can introduce ethynyl more efficiently, the reaction conditions are easy to control, and the raw materials are easy to obtain. By 2-methyl-3-butyn-2-ol, R can be contained 1 Radicals (C)An ethynyl group is introduced into the halide of (a) through a substitution reaction to prepare for the subsequent click reaction.
Further, the use of a hyperbranched polymer as an electrode material.
Further, an application of the hyperbranched polymer in preparing lithium batteries.
The hyperbranched polymer synthesized by the technical scheme is rich in active groups, is obtained through efficient click reaction, has fewer structural defects, has a more complete conjugated structure, is favorable for promoting efficient transmission of charges in a plane, improves the effectiveness and reversibility of redox reaction, and has better mechanical properties. The hyperbranched polymer can be used as an electrode material in the preparation of lithium batteries, so that the performance of the corresponding lithium ion batteries is effectively improved.
Drawings
FIG. 1 is a schematic diagram of the synthesis scheme of Polymer 1 of example 3 of the present application.
FIG. 2 is an infrared absorption spectrum of the polymer 1 of example 3 of the present application.
FIG. 3 is a schematic diagram of the synthesis scheme of Polymer 2 of example 4 of the present application.
Detailed Description
The present application will be described in further detail with reference to examples, but embodiments of the present application are not limited thereto. The technical means used in the following examples are conventional means well known to those skilled in the art unless otherwise indicated; the experimental methods used are all conventional methods; the materials, reagents, and the like used are all commercially available.
The hyperbranched polymer and the key monomers in the technical scheme are as follows:
the technical scheme adopts a connecting monomer (the structural formula of the general formula is shown as formula (A) or formula (B) or formula (C)) and an active group monomer, and the hyperbranched polymer is synthesized by click chemistry reaction. The linking monomer contains at least two ethynyl groups, or at least two azide groups, R 1 Is any straight-chain hydrocarbon, non-aromatic ring or aromatic ring. Reactive groupThe monomer contains active groups, and the active groups are connected with at least two azido groups or at least two ethynyl groups. The electroactive group monomer is exemplified by pyrene-4, 5,9, 10-tetraketone, and the electroactive group monomer is shown as formula (D). The reactive group may also be a sulfide containing an S-S bond reactive group; carbonyl and polycarbonyl containing compounds (including benzoquinones); imine group-containing compounds (including phenazine structure-containing compounds); containing compounds capable of forming stable free radicals, including tetramethyl piperidine oxide (TEMPO) class. The process of polymerizing the linking monomer (exemplified by formula (A)) and the active group monomer to form the hyperbranched polymer is shown in figure 1, the general formula of the polymer obtained by synthesis is shown in formula (E), wherein A represents the active group (the active group shown in formula (H)) and R 1 Is any straight-chain hydrocarbon, non-aromatic ring or aromatic ring. If a linking monomer represented by the formula (B) is used, the polymer obtained by synthesis has the formula (E), wherein A represents an active group (an active group represented by the formula (H)) and R 1 Is any straight-chain hydrocarbon, non-aromatic ring or aromatic ring, n is an integer of 10-300. If a linking monomer represented by the formula (C) is used, the polymer obtained by synthesis has the formula (G), wherein A represents an active group (an active group represented by the formula (H)) and R 1 Is any straight-chain hydrocarbon, non-aromatic ring or aromatic ring, n is an integer of 10-300.
Example 1: synthesis of connection monomer (backbone)
In this example, the synthetic process of the linking monomer is described using R1 as a benzene ring. Compound 1 (namely tribromobenzene, structural formula is shown as formula (1)) is used as a raw material to synthesize compound 2 (structural formula is shown as formula (2)), and the synthesis method and process are shown as formula (I), specifically: in a 50mL three-necked flask under nitrogen protection, compound 1 (4.5 g,14.4 mmol) and Pd (PPh 3 ) 4 (250 mg,0.216 mmol), cuI (49 mg,0.216 mmol) and triethylamine (50 mL), heating to 75deg.C and dropping a solution of 2-methyl-3-butyn-2-ol (4.85 g,60.0 mmol) in triethylamine (10 mL)Into a three-necked flask, and reacted for 3 hours. After cooling, the reaction mixture was suction-filtered, dried, and purified by silica gel column chromatography to give the product as a pale yellow solid (3.4 g, yield 71%). The spectral data for compound 2 were: 1 H NMR(400MHz,CDCl 3 )δ:7.37(s,3H)，1.60(s,18H)。
a method for synthesizing compound 3 (structural formula see formula (3), synthetic process see formula (I)): a50 mL three-necked flask was charged with compound 2 (3.00 g,9.5 mmol) and sodium hydroxide (3.2 g,29.0 mmol) in 30mL toluene. Reflux is performed for 6 hours. Suction filtration and drying. Silica gel column chromatography gave the product as a white solid (0.98 g,70% yield). The spectral data for compound 3 were: 1 H NMR(400MHz,CDCl 3 )δ:7.57(s,3H)，3.11(s,3H)。
in addition to the compound 3 shown in the formula (3), the connecting monomer can be a compound shown in the formula (3-1), the formula (3-2), the formula (3-3) or the formula (3-4), and can be prepared by adopting a preparation method of the compound 3. Wherein m is an integer of 1 to 4.
Example 2: synthesis of reactive monomers
Taking pyrene-4, 5,9, 10-tetraketone as a raw material monomer as an example, describing the process of adding azido groups on active groups, and adding azido groups on other active groups according to actual needs, wherein the other active groups comprise: sulfide containing S-S bond active group; carbonyl and polycarbonyl containing compounds such as benzoquinones; imine group-containing compounds, such as phenazine structure-containing compounds; containing compounds which form stable free radicals, such as tetramethylpiperidine oxide (TEMPO). The inventor has proved through experimental study that the active groups can be connected to the connecting monomer through click reaction in a mode of adding azido or alkynyl, so as to form the electrode material with accurately controllable group number.
The side group synthesis procedure of this example is shown in formula (J), and is as follows:
a synthetic method of compound 5 (structural formula see formula (5)): 1.0g (3.8 mmol) of starting compound 4 (structural formula: see formula (4), i.e., pyrene-4, 5,9, 10-tetraketone) was added to a mixture of fuming nitric acid and fuming sulfuric acid (10mL+10mL), heated to 100℃with stirring, reacted for 2 hours, cooled to room temperature, and the reaction mixture was slowly poured into deionized water (150 mL), and the precipitate was collected and dried in vacuo at 80℃for 2 hours to give the product compound 5 (0.89 g, 70%). The spectral data for compound 5 were: 1 H NMR(400MHz，DMSO-d 6 )：9.07(s，4H)。
a synthetic method of compound 6 (structural formula see formula (6)): 0.5g (1.63 mmol) of Compound 5 was added to an aqueous sodium hydroxide solution (2.0M, 15 mL) of sodium thiosulfate (1.3 g,8.2 mmol), heated to 50℃with stirring, reacted for 6 hours, cooled to room temperature, the reaction mixture was poured into deionized water (200 mL), the precipitate was collected, and dried under vacuum at 80℃for 2 hours to give the product compound 6 (0.29 g, 65%). The spectrum data are: 1 H NMR(400MHz，DMSO-d 6 )：8.41(s，4H)，4.27(s，4H)。
a synthetic method of compound 7 (structural formula see formula (7)): 0.5g (1.63 mmol) of Compound 6 was dissolved in tetrahydrofuran (30 mL), cooled to 0℃with stirring, and then t-BuONO (0.26 g,2.5 mmol) and TMSN were added sequentially 3 (0.22 g,2.0 mmol) for 3 hours, and after spin-drying, the silica gel column was separated (toluene as a eluent) to give the product compound 7 (0.39 g, 72%). The spectral data for compound 7 were: 1 H NMR(400MHz，DMSO-d 6 )：8.29(s，4H)。
example 3: polymerization (Polymer 1 was obtained)
The polymerization process will be described by taking the polymerization of compound 3 and compound 7 as an example, and the specific process is as follows (see fig. 1):
synthesis of Polymer 1The method comprises the following steps: compound 3 (0.50 g,3.33 mmol) and compound 7 (1.72 g,4.99 mmol) were added to a mixed solution of ethanol and deionized water (15 mL, v: v=9:1), a freshly prepared sodium ascorbate solution (1.0 m,64 μl,0.064 mmol) was added with vigorous stirring, then copper sulfate pentahydrate (3.2 mg,0.013 mmol) was added, heated to 30 ℃, reacted for 24 hours, cooled to room temperature, the reaction mixture was poured into methanol (150 mL), the precipitate was collected and dried under vacuum for 3 hours to give polymer 1 (1.68 g, 76%). Insoluble in common organic solvents. The synthetic process of this example is schematically shown in FIG. 1, and the structural formula of the polymer 1 is shown in formula (E), wherein R 1 Is benzene ring. The infrared absorption spectrum of the polymer 1 is shown in FIG. 2. In the actual operation process, the ratio of the ethynyl group of the compound 3 to the number of the azido groups of the compound 7 is maintained to be 0.8-1.2, and the obtained polymer 1 has ideal performance, and can obtain ideal initial discharge actual capacity and cycle performance when being applied to the preparation of lithium batteries.
The present example uses a sodium ascorbate/copper sulfate system to provide monovalent copper as a catalyst, and other copper-containing compounds (e.g., cuprous bromide, cuprous triphenylphosphine bromide, etc.) can be used as long as monovalent copper is provided to the reaction system.
Example 4: polymerization (Polymer 2 was obtained)
This comparative example was conducted to synthesize polymer 2 by polymerization using compound 8 (structural formula see formula (3-4)) and compound 7. The synthesis method and principle of the compound 8 are the same as those of the example 1, and are not described in detail here. The polymerization parameters were the same as in example 3 except for the amounts of compound 8 and compound 7. Polymer 2 (1.35 g, 82%) was obtained from compound 8 (0.42 g,3.33 mmol) and compound 7 (1.15 g,3.33 mmol). The synthesis of Polymer 2 is shown in FIG. 3, and the structural formula of Polymer 2 is shown in formula (F), wherein R 1 Is a pyridine ring. In the actual operation process, the ratio of the ethynyl group of the compound 8 to the number of the azido groups of the compound 7 is maintained to be 0.8-1.2, and the obtained polymer 2 has ideal performance, and can obtain ideal actual initial discharge capacity and cycle performance when being applied to the preparation of lithium batteries.
Example 5: polymerization (Polymer 3 was obtained)
Compound 9 (formula (3-3), m=2) 3 (0.79 g,3.33 mmol) and compound 7 (2.29 g,6.66 mmol) were added to a mixed solution of ethanol and deionized water (15 mL, v: v=9:1), a freshly prepared sodium ascorbate solution (1.0 m,64 μl,0.064 mmol) was added with vigorous stirring, then copper sulfate pentahydrate (3.2 mg,0.013 mmol) was added, heated to 30 ℃ for 24 hours, cooled to room temperature, the reaction mixture was poured into methanol (150 mL), the precipitate was collected, and dried in vacuo for 3 hours to give polymer 3 (2.39 g, 79%). Insoluble in common organic solvents. The structural formula of the polymer 3 is shown as a formula (G), wherein R 1 Is n-octyl (in the actual preparation of polymer 3, alkanes having m of 1 to 10 may be used). In the actual operation process, the ratio of the ethynyl group of the compound 9 to the number of the azido groups of the compound 7 is maintained to be 0.8-1.2, and the obtained polymer 3 has ideal performance, and can obtain ideal initial discharge actual capacity and cycle performance when being applied to the preparation of lithium batteries.
Example 6: polymerization (Polymer 4 was obtained)
Compound 10 (formula (3-1), 0.52g,3.33 mmol) and monomer compound 7 (1.72 g,4.99 mmol) were added to a mixed solution of ethanol and deionized water (15 mL, v: v=9:1), a freshly prepared sodium ascorbate solution (1.0 m,64 μl,0.064 mmol) was added with vigorous stirring, then copper sulfate pentahydrate (3.2 mg,0.013 mmol) was added, heated to 30 ℃, reacted for 24 hours, cooled to room temperature, the reaction mixture was poured into methanol (150 mL), the precipitate was collected, and dried in vacuo for 3 hours to give polymer 4 (1.77 g, 80%). Insoluble in common organic solvents. The synthetic process of this example is schematically shown in FIG. 1, and the structural formula of Polymer 4 is shown in formula (E), wherein R 1 Is a cyclohexyl group. In the actual operation process, the ratio of the ethynyl group of the compound 10 to the number of the azido groups of the compound 7 is maintained between 0.8 and 1.2, and the obtained polymer 4 has ideal performance, and can obtain ideal initial discharge actual capacity and cycle performance when being applied to the preparation of lithium batteries.
Experimental example 1: button type lithium ion battery prepared by using novel electrode material
Preparation of a battery: polymer 1 (100 mg) was ground to a fine powder, acetylene black (80 mg) was added thereto, grinding was continued to a uniform fine powder, and an NMP solution of polyvinylidene fluoride (10 wt%,20 mL) was added thereto, and grinding was performed until complete mixing was performed, to thereby prepare a slurry for producing a positive electrode active layer. The slurry was knife coated on an aluminum foil (thickness 40 μm), vacuum-dried at 60℃for 2 hours, and then at 120℃for 6 hours, to obtain a positive electrode sheet. The pole pieces were punched into small pole pieces (14 mm diameter) by a punch. Assembling the battery in a glove box: the method comprises the steps of placing a negative electrode shell on an insulating table top horizontally, then placing a metal lithium sheet and flattening, then placing a diaphragm (polyethylene film), dripping electrolyte (EC: DEC=1:2, lithium hexafluorophosphate concentration is 1.0M, about 200 microliters) into the negative electrode shell, then placing the positive electrode sheet, the gasket, the spring piece and the positive electrode shell sequentially, and then pressing and sealing by using a pressing machine to obtain the button type lithium ion test battery.
Button-type lithium ion test cells were prepared in the same manner using polymers 2-4.
And (3) carrying out charge and discharge test on the battery, wherein the multiplying power is 1C, and the test voltage is 1.0V-4.0V. Discharge-charge was repeated 20 times at 10 minute intervals between charges and discharges for one cycle, and the test results are shown in table 1.
Table 1: charge and discharge test results
The test results of this experimental example include the actual capacity of the first discharge, the 20 th discharge capacity/the first discharge capacity. From the data in Table 1, polymers 1-4 all exhibited excellent capacities. The battery using the polymer 2 as the electrode material has a higher actual capacity for first discharge, but has poor cycle performance. The inventors analyzed that the reason is that polymer 2 is a linear structure, and stability to an electrolyte is not as good as polymer 1 of a three-dimensional structure. The battery using the polymer 1 as the electrode material has lower actual capacity of first discharge, but better cycle performance. Containing 3 or more ethynyl groups (or azides) on the linking monomerBased), the obtained polymer can form a three-dimensional structure, but not a linear structure, which is favorable for inhibiting partial electrode material dissolution during charge and discharge. The actual discharge capacity of the batteries prepared from polymers 3 and 4 was improved relative to polymer 1, and the 20 th discharge capacity/first discharge capacity values were maintained at a desirable level. The inventors analyzed the reason for the increase in the actual capacity of the first discharge due to R 1 R of polymers 3 and 4 1 The flexibility of the polymer is higher than that of benzene rings in the polymer 1, so that active groups of the material can be fully utilized. In particular, the polymer 3, the flexible n-octyl, enables the material to have higher flexibility, is beneficial to promoting the full reaction of lithium ions and active groups, and therefore has the best performance.
The above results show that the novel material in the scheme has excellent performance as an electrode material, and important indexes such as capacity, stability and the like can be realized through the selection and optimization of the structure of the monomer according to practical application requirements.
The foregoing is merely exemplary of the present application, and specific technical solutions and/or features that are well known in the art have not been described in detail herein. It should be noted that, for those skilled in the art, several variations and modifications can be made without departing from the technical solution of the present application, and these should also be regarded as the protection scope of the present application, which does not affect the effect of the implementation of the present application and the practical applicability of the patent. The protection scope of the present application is subject to the content of the claims, and the description of the specific embodiments and the like in the specification can be used for explaining the content of the claims.
Claims (7)
1. A hyperbranched polymer characterized in that: the method is synthesized by a connection monomer and an active group monomer through click chemistry reaction; the linking monomer contains at least two ethynyl groups or at least two azide groups, and the active group monomer contains at least two azide groups or at least two ethynyl groups;
the general formula of the connecting monomer is shown as a formula (A) or a formula (C); wherein R is 1 Represents any straight-chain hydrocarbon, non-aromatic or aromatic ring；
Formula (A);
formula (C);
the structural formula of the connecting monomer is shown as formula (3) or formula (3-1) or formula (3-3); wherein m is an integer of 1 to 10;
formula (3);
formula (3-1);
formula (3-3);
the structural formula of the active group monomer is shown as a formula (D):
formula (D).
2. The hyperbranched polymer according to claim 1 wherein: the general formula is shown as a formula (E) or a formula (G); wherein A represents an active group represented by the formula (H), R 1 Represents any straight-chain hydrocarbon, non-aromatic ring or aromatic ring; n is an integer of 10 to 300,
formula (E);
formula (G);
formula (H).
3. The method for preparing a hyperbranched polymer according to claim 1 or 2, characterized in that: and carrying out click chemistry reaction on the connecting monomer and the active group monomer in a sodium ascorbate/copper sulfate system to obtain the hyperbranched polymer.
4. A process for the preparation of a hyperbranched polymer according to claim 3 characterised in that: adding a connecting monomer and an active group monomer into an ethanol water solution, adding a sodium ascorbate solution under the stirring condition, and then adding copper sulfate pentahydrate to perform click chemistry reaction; then ethanol precipitation and vacuum drying are carried out to obtain the hyperbranched polymer; the ratio of the number of ethynyl or azido groups of the linking monomer to the number of azido or ethynyl groups of the reactive group monomer is from 0.8 to 1.2.
5. The method for producing a hyperbranched polymer according to claim 4, wherein: the synthesis method of the connecting monomer comprises the following steps: containing R 1 The halide of the group is subjected to substitution reaction with 2-methyl-3-butyn-2-ol, and then the linking monomer shown as the formula (A) or the formula (C) is obtained through alkaline hydrolysis.
6. Use of a hyperbranched polymer according to claim 1 or 2 as electrode material.
7. Use of a hyperbranched polymer according to claim 1 or 2 for the preparation of lithium batteries.
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