WO2022198815A1 - Carbonyl polymer, synthesis method therefor and use thereof - Google Patents
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- WO2022198815A1 WO2022198815A1 PCT/CN2021/101669 CN2021101669W WO2022198815A1 WO 2022198815 A1 WO2022198815 A1 WO 2022198815A1 CN 2021101669 W CN2021101669 W CN 2021101669W WO 2022198815 A1 WO2022198815 A1 WO 2022198815A1
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- 229920000642 polymer Polymers 0.000 title claims abstract description 58
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 title claims abstract description 49
- 238000001308 synthesis method Methods 0.000 title abstract description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 25
- 239000007772 electrode material Substances 0.000 claims abstract description 13
- 239000007774 positive electrode material Substances 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 12
- 230000002194 synthesizing effect Effects 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 claims description 9
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 claims description 9
- 235000012141 vanillin Nutrition 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 229920000768 polyamine Polymers 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 238000005576 amination reaction Methods 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 claims 1
- 238000000746 purification Methods 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 15
- 230000015572 biosynthetic process Effects 0.000 abstract description 11
- 238000011161 development Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000011368 organic material Substances 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OPHFPFFVGABYTB-UHFFFAOYSA-N 2H-oxazine piperazine Chemical compound O1NC=CC=C1.N1CCNCC1 OPHFPFFVGABYTB-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- -1 LiCoO 2 Chemical class 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007728 cost analysis Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- KVKFRMCSXWQSNT-UHFFFAOYSA-N n,n'-dimethylethane-1,2-diamine Chemical compound CNCCNC KVKFRMCSXWQSNT-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Electrochemistry (AREA)
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Abstract
Disclosed are a carbonyl polymer, a synthesis method therefor and the use thereof. The structure of the carbonyl polymer is as represented by formula 1, wherein R, R' and R'' are H, C1-50 alkyl straight or branched chains, and n is equal to 1-10000. The carbonyl polymer of the present invention has the advantages of low synthesis costs, a good redox activity, a high specific capacity, a high energy density, etc., and when the carbonyl polymer is used as a lithium battery positive electrode material, the specific capacity can reach 255 mAh/g, and the working voltage interval is 2.5-2.7 V. The present invention achieves the development of a class of low-cost carbonyl polymers with a theoretical production cost as low as 0.48 US dollars/g. The polymer shows a price-to-performance ratio as low as 0.0017 cents per 100 mAh, representing the best level among currently reported materials, and has good application prospects in the field of lithium battery electrode materials.
Description
本发明属于锂电池材料技术领域，具体涉及一种羰基聚合物及其合成方法与应用。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.
由于全球对于能源的需求逐年增加，石油、煤炭等传统能源日益枯竭，而且出于保护地球生态环境的需要，“碳中和”发展理念在全球持续推进，因此越来越多的科学家将研究集中在新能源材料与器件相关的方面。As the global demand for energy increases year by year, traditional energy sources such as oil and coal are increasingly depleted, and in order to protect the earth's ecological environment, the "carbon neutral" development concept continues to advance around the world, so more and more scientists focus their research on In new energy materials and devices related aspects.
近年来，随着便携式智能可穿戴电子设备、电动新能源汽车等产业的加速发展，以锂离子电池(LIBs)为代表的新能源器件得到了研究人员的持续关注。目前，商业化锂离子电池电极材料主要为无机金属氧化物，例如LiCoO
2，LiMn
2O
4和LiFePO
4等，它们通常具有低的实际使用容量，并且这类材料为稀缺不可再生资源，不利于产业的长远可持续发展。有机材料被认为是非常有希望的替代品。有机电极材料具有多方面的性能优势：有机材料可以实现单位重量上的多活性位点，因而有机电极材料具有高容量；有机材料由地壳中储量丰富的有机元素(如C、H、O、N和S)组成，可以从生物质资源或通过温和的化学合成反应获得，廉价、环保，符合可持续发展的要求；与无机化合物相比，有机材料的分子结构可灵活调节以满足不同的电化学性能要求，完全放电时更安全，并且具有较高的环境相容性。有机材料还具有质轻、柔性、机械性能优良等特点，将有助于开发储能电池在便携式、可穿戴电子设备中的前沿应用。
In recent years, with the accelerated development of industries such as portable smart wearable electronic devices and electric new energy vehicles, new energy devices represented by lithium-ion batteries (LIBs) have received continuous attention from researchers. Currently, commercial lithium-ion battery electrode materials are mainly inorganic metal oxides, such as LiCoO 2 , LiMn 2 O 4 and LiFePO 4 , etc., which usually have low practical use capacity, and such materials are scarce and non-renewable resources, which are not conducive to long-term sustainable development of the industry. Organic materials are considered very promising alternatives. Organic electrode materials have many performance advantages: organic materials can achieve multiple active sites per unit weight, so organic electrode materials have high capacity; organic materials are composed of abundant organic elements (such as C, H, O, N) in the earth's crust. and S), which can be obtained from biomass resources or through mild chemical synthesis reactions, are inexpensive, environmentally friendly, and meet the requirements of sustainable development; compared with inorganic compounds, the molecular structure of organic materials can be flexibly adjusted to meet different electrochemical performance requirements, are safer when fully discharged, and have high environmental compatibility. Organic materials also have the characteristics of light weight, flexibility, and excellent mechanical properties, which will contribute to the development of cutting-edge applications of energy storage batteries in portable and wearable electronic devices.
发明内容SUMMARY OF THE INVENTION
为解决上述现有技术中存在的不足之处，本发明的目的在于提供一种羰基聚合物及其合成方法。本发明的羰基聚合物可应用于锂电池电极材料领域，作为锂电池正极材料，具有合成成本低廉，氧化还原活性好，高比容量，高能量密度等优点。In order to solve the deficiencies existing in the above-mentioned prior art, the object of the present invention is to provide a carbonyl polymer and a synthesis method thereof. The carbonyl polymer of the invention can be applied to the field of lithium battery electrode materials, and as a lithium battery positive electrode material, it has the advantages of low synthesis cost, good redox activity, high specific capacity, high energy density and the like.
为达到其目的，本发明所采用的技术方案为：In order to achieve its purpose, the technical scheme adopted in the present invention is:
一种羰基聚合物，其具有如下结构式：A carbonyl polymer having the following structural formula:
其中，R、R′和R″为H、C
1～50烷基直链或支化链，n＝1～10000。
Wherein, R, R' and R" are H, C 1-50 alkyl straight chain or branched chain, n=1-10000.
本发明还提供了一种所述羰基聚合物的合成方法，其包括：由香草醛和多胺基单体进行胺化氧化聚合反应制得。The present invention also provides a method for synthesizing the carbonyl polymer, which comprises the following steps: preparing from vanillin and a polyamine-based monomer through amination-oxidative polymerization.
优选地，所述多胺基单体具有如下结构式中的至少一种：Preferably, the polyamine-based monomer has at least one of the following structural formulas:
优选地，所述述羰基聚合物的合成方法中，香草醛与多胺基的摩尔比为x，且0<x<100。Preferably, in the method for synthesizing the carbonyl polymer, the molar ratio of vanillin to polyamine group is x, and 0<x<100.
优选地，所述羰基聚合物的合成方法，包括如下步骤：在空气气氛下，将香草醛和多胺基单体加入溶剂中进行胺化氧化聚合反应，反应完成后纯化，即得所述羰基聚合物。Preferably, the method for synthesizing the carbonyl polymer includes the following steps: in an air atmosphere, adding vanillin and a polyamine-based monomer into a solvent to carry out amination-oxidative polymerization reaction, and purifying after the reaction is completed to obtain the carbonyl group polymer.
优选地，所述溶剂为醇溶剂；更优选为乙醇溶剂。Preferably, the solvent is an alcohol solvent; more preferably, an ethanol solvent.
本发明还提供了所述羰基聚合物在锂电池电极材料中的应用。The present invention also provides the application of the carbonyl polymer in the lithium battery electrode material.
优选地，所述羰基聚合物在制备锂电池正极材料中的应用。Preferably, the carbonyl polymer is used in the preparation of positive electrode materials for lithium batteries.
本发明还提供了一种锂电池电极材料，其包括所述羰基聚合物。The present invention also provides a lithium battery electrode material comprising the carbonyl polymer.
与现有技术相比，本发明的有益效果为：本发明的羰基聚合物具有合成成本低廉、氧化还原活性好、高比容量和高能量密度等优点，用作锂电池正极材料时，比容量可达到255mAh/g，工作电压区间为2.5～2.7V。本发明实现了研制一类理论生产成本低至0.48美元/g的低成本羰基聚合物，该聚合物展现出低至0.0017美分/100mAh的价格性能比，是目前所报道材料的最好水平，在锂电池电极材料领域具有良好的应用前景。Compared with the prior art, the beneficial effects of the present invention are as follows: the carbonyl polymer of the present invention has the advantages of low synthesis cost, good redox activity, high specific capacity and high energy density, etc. It can reach 255mAh/g, and the working voltage range is 2.5~2.7V. The invention realizes the development of a kind of low-cost carbonyl polymer with a theoretical production cost as low as 0.48 US dollars/g, the polymer exhibits a price-performance ratio as low as 0.0017 cents/100mAh, which is the best level of materials reported so far, It has good application prospects in the field of lithium battery electrode materials.
图1为本发明所述羰基聚合物的化学结构；Fig. 1 is the chemical structure of the carbonyl polymer of the present invention;
图2为实施例1的羰基聚合物1(简称NP1)的合成路线图；Fig. 2 is the synthetic route diagram of the carbonyl polymer 1 (abbreviated as NP1) of embodiment 1;
图3为实施例2的羰基聚合物2(简称NP2)的合成路线图；Fig. 3 is the synthetic route diagram of the carbonyl polymer 2 (abbreviated as NP2) of embodiment 2;
图4为羰基聚合物NP1和NP2的红外光谱图；Fig. 4 is the infrared spectrogram of carbonyl polymers NP1 and NP2;
图5为聚合物NP2应用于锂电池正极材料及相应锂电池结构示意图；FIG. 5 is a schematic diagram of the application of polymer NP2 to the positive electrode material of lithium battery and the structure of the corresponding lithium battery;
图6为基于聚合物NP2的锂电池充放电性能曲线(电压-比容量曲线)；Figure 6 is a charge-discharge performance curve (voltage-specific capacity curve) of a lithium battery based on polymer NP2;
图7为聚合物NP2与目前文献报道的有机羰基聚合物及小分子成本分析对比图。Figure 7 is a comparison diagram of the cost analysis of polymer NP2 and organic carbonyl polymers and small molecules reported in the literature.
下面通过具体实施例对本发明作进一步的说明，其目的在于帮助更好地理解本发明的内容，具体包括羰基聚合物的合成和电池的制备方法。但所描述的实施例仅仅是本发明的部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The present invention will be further described below through specific examples, the purpose of which is to help better understand the content of the present invention, specifically including the synthesis of carbonyl polymers and the preparation methods of batteries. However, the described embodiments are only some, but not all, embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative efforts shall fall within the protection scope of the present invention.
本发明的实践可采用本技术领域内的聚合物化学的常规技术。在以下实施例中，努力确保所用数字(包括量、温度、反应时间等)的准确性，但应考虑一些实验误差和偏差。在以下实施例中所用的温度以℃表示，压力为大气压或 接近大气压。所用溶剂为分析纯或色谱纯购买。除非另外指出，否则所有试剂都是商业获得的。The practice of the present invention may employ conventional techniques of polymer chemistry in the art. In the following examples, efforts have been made to ensure accuracy with respect to numbers used (including amounts, temperatures, reaction times, etc.) but some experimental errors and deviations should be accounted for. The temperatures used in the following examples are expressed in °C and the pressures are at or near atmospheric. The solvents used were of analytical grade or chromatographic grade. All reagents were obtained commercially unless otherwise noted.
实施例1Example 1
羰基聚合物1(简称NP1)的合成，其合成反应式如图2所示，具体合成步骤如下：The synthesis of carbonyl polymer 1 (abbreviated as NP1), its synthesis reaction formula is shown in Figure 2, and the specific synthesis steps are as follows:
在空气气氛下，将香草醛(10毫摩尔)和N,N′-二甲基乙二胺(10毫摩尔)溶解于15毫升乙醇中，室温(25℃)下搅拌反应48小时。反应结束后，在甲醇中沉淀出聚合物，再依次经甲醇、丙酮、正己烷抽提，最后用氯仿抽提出最终聚合物，然后再次用甲醇沉淀，最后烘干得到产物NP1，产量为1克，产率为70％。Under air atmosphere, vanillin (10 mmol) and N,N'-dimethylethylenediamine (10 mmol) were dissolved in 15 mL of ethanol, and the reaction was stirred at room temperature (25° C.) for 48 hours. After the reaction, the polymer was precipitated in methanol, then extracted with methanol, acetone and n-hexane in turn, and finally the final polymer was extracted with chloroform, then precipitated with methanol again, and finally dried to obtain the product NP1, and the yield was 1 gram. , the yield is 70%.
通过红外光谱实验，NP1的结构如图4所示，图中的红外特征峰表明NP1聚合物中的羰基特征官能团顺利合成，即成功制备得到羰基聚合物NP1。Through infrared spectroscopy experiments, the structure of NP1 is shown in Figure 4. The infrared characteristic peaks in the figure indicate that the carbonyl characteristic functional groups in the NP1 polymer are successfully synthesized, that is, the carbonyl polymer NP1 is successfully prepared.
实施例2Example 2
羰基聚合物2(简称NP2)的合成，其合成反应式如图3所示，具体合成步骤如下：The synthesis of carbonyl polymer 2 (abbreviated as NP2), its synthesis reaction formula is shown in Figure 3, and the concrete synthesis steps are as follows:
在空气气氛下，将香草醛(10毫摩尔)和哌嗪(10毫摩尔)溶解于15毫升乙醇中，室温(25℃)下搅拌反应48小时。反应结束后，在甲醇中沉淀出聚合物，再依次经甲醇、丙酮、正己烷抽提，最后用氯仿抽提出最终聚合物，然后再次用甲醇沉淀，最后烘干得到产物NP2，产量为1克，产率为70％。Under air atmosphere, vanillin (10 mmol) and piperazine (10 mmol) were dissolved in 15 mL of ethanol, and the reaction was stirred at room temperature (25° C.) for 48 hours. After the reaction, the polymer was precipitated in methanol, then extracted with methanol, acetone, n-hexane in turn, and finally the final polymer was extracted with chloroform, then precipitated with methanol again, and finally dried to obtain the product NP2, and the yield was 1 g , the yield is 70%.
通过红外光谱实验，NP2的结构如图4所示，图中的红外特征峰表明NP2聚合物中的羰基特征官能团顺利合成，即成功制备得到羰基聚合物NP2。Through infrared spectroscopy experiments, the structure of NP2 is shown in Figure 4. The infrared characteristic peaks in the figure indicate that the carbonyl characteristic functional groups in the NP2 polymer are successfully synthesized, that is, the carbonyl polymer NP2 is successfully prepared.
实施例3Example 3
以实施例2所得聚合物材料NP2为例，说明此类聚合物材料作为电极材料在锂电池中的应用：Take the polymer material NP2 obtained in Example 2 as an example to illustrate the application of this type of polymer material as an electrode material in lithium batteries:
锂电池的具体制备过程如下：The specific preparation process of the lithium battery is as follows:
(1)电极片的制备(1) Preparation of electrode sheets
将NP2、炭黑和聚偏氟乙烯(PVDF)按3:6:1的重量比称量并混合，经研磨后压片即得到基于NP2的电极片，并经过80℃真空烘箱12小时烘干后备用；NP2, carbon black and polyvinylidene fluoride (PVDF) were weighed and mixed in a weight ratio of 3:6:1, and the NP2-based electrode sheet was obtained by pressing after grinding, and dried in a vacuum oven at 80°C for 12 hours. backup;
(2)锂电池的组装(2) Assembly of lithium battery
在氩气手套箱中，按照图5所示锂电池结构依次组装制备得到的NP2电极片、隔膜(并在隔膜上滴加0.2毫升电解液)和锂片，经压力封装后，即完成锂电池的制备。In an argon gas glove box, the prepared NP2 electrode sheet, separator (with 0.2 ml of electrolyte on the separator) and lithium sheet are assembled in sequence according to the lithium battery structure shown in Figure 5. After pressure packaging, the lithium battery is completed. preparation.
在蓝电电池测试系统中进行锂电池充放电曲线测试，得到电池的电压-比容量曲线，如图6所示。从图6可以看出，基于NP2的锂电池的比容量达到255mAh/g，其工作电压区间为2.5～2.7V。因此可以看出，这类羰基聚合物是一类性能优异的锂电池电极材料。The lithium battery charge-discharge curve test is carried out in the blue battery test system, and the voltage-specific capacity curve of the battery is obtained, as shown in Figure 6. It can be seen from Figure 6 that the specific capacity of the NP2-based lithium battery reaches 255mAh/g, and its operating voltage range is 2.5-2.7V. Therefore, it can be seen that this type of carbonyl polymer is a kind of lithium battery electrode material with excellent performance.
实施例4Example 4
以实施例3所制备的锂电池性能及NP2的合成成本为例，说明此类羰基聚合物的合成方法具备低合成成本优点。Taking the performance of the lithium battery prepared in Example 3 and the synthesis cost of NP2 as an example, it is illustrated that the synthesis method of this type of carbonyl polymer has the advantage of low synthesis cost.
如图7所示，考虑商业化原料价格的基础上结合反应产率计算，由于实施例2中所合成的羰基聚合物NP2只需要1步化学合成，且原料为廉价易得的香草醛和哌嗪，因此NP2具有低至0.48美元/g的低理论生产成本，并且该聚合物NP2展现出低至0.0017美分每100mAh的价格性能比，这一成本及成本价格比是目前所报道材料的最好水平。As shown in Figure 7, considering the price of commercial raw materials and the calculation of the reaction yield, since the carbonyl polymer NP2 synthesized in Example 2 only needs one-step chemical synthesis, and the raw materials are cheap and readily available vanillin and piperazine oxazine, NP2 has a low theoretical production cost as low as $0.48/g, and the polymer NP2 exhibits a price-performance ratio as low as 0.0017 cents per 100mAh, which is the best cost-to-cost ratio for materials reported so far good level.
总体表明，这类羰基聚合物材料是一类性能优异的锂电池电极材料，并且具有低廉的合成成本，是一类非常具有商业化前景的低成本羰基聚合物材料。Overall, this type of carbonyl polymer material is a class of lithium battery electrode materials with excellent performance and low synthesis cost, which is a very promising low-cost carbonyl polymer material for commercialization.
最后所应当说明的是，以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制，尽管参照较佳实施例对本发明作了详细说明，本领域技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的实质和范围。Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit the protection scope of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the The technical solutions of the invention can be modified or equivalently replaced without departing from the spirit and scope of the technical solutions of the invention.
Claims (10)
- 一种羰基聚合物，其特征在于，具有如下结构式：A carbonyl polymer is characterized in that, has following structural formula:
其中，R、R′和R″为H、C 1～50烷基直链或支化链，n＝1～10000。 Wherein, R, R' and R" are H, C 1-50 alkyl straight chain or branched chain, n=1-10000. - 一种如权利要求1所述的羰基聚合物的合成方法，其特征在于，由香草醛和多胺基单体进行胺化氧化聚合反应制得。A method for synthesizing a carbonyl polymer as claimed in claim 1, characterized in that, it is prepared by amination oxidative polymerization of vanillin and polyamine-based monomers.
- 如权利要求2所述的羰基聚合物的合成方法，其特征在于，所述多胺基单体具有如下结构式中的至少一种：The method for synthesizing carbonyl polymers according to claim 2, wherein the polyamine-based monomer has at least one of the following structural formulas:
- 如权利要求2所述的羰基聚合物的合成方法，其特征在于，所述羰基聚合物的合成方法中，香草醛与多胺基的摩尔比为x，且0<x<100。The method for synthesizing a carbonyl polymer according to claim 2, wherein in the method for synthesizing a carbonyl polymer, the molar ratio of vanillin to polyamine group is x, and 0<x<100.
- 如权利要求2～4任一项所述的羰基聚合物的合成方法，其特征在于，所述羰基聚合物的合成方法包括如下步骤：在空气气氛下，将香草醛和多胺基单体加入溶剂中进行胺化氧化聚合反应，反应完成后纯化，即得所述羰基聚合物。The method for synthesizing a carbonyl polymer according to any one of claims 2 to 4, wherein the method for synthesizing a carbonyl polymer comprises the steps of: adding vanillin and a polyamine-based monomer into an air atmosphere The amination-oxidative polymerization reaction is carried out in a solvent, and after the reaction is completed, the carbonyl polymer is obtained by purification.
- 如权利要求5所述的羰基聚合物的合成方法，其特征在于，所述溶剂为醇溶剂。The method for synthesizing a carbonyl polymer according to claim 5, wherein the solvent is an alcohol solvent.
- 如权利要求5所述的羰基聚合物的合成方法，其特征在于，所述溶剂为乙醇溶剂。The method for synthesizing a carbonyl polymer according to claim 5, wherein the solvent is an ethanol solvent.
- 如权利要求1所述的羰基聚合物在锂电池电极材料中的应用。The application of the carbonyl polymer according to claim 1 in the electrode material of lithium battery.
- 如权利要求1所述的羰基聚合物在制备锂电池正极材料中的应用。The application of the carbonyl polymer according to claim 1 in the preparation of a positive electrode material for a lithium battery.
- 一种锂电池电极材料，其特征在于，包括如权利要求1所述的羰基聚合物。A lithium battery electrode material, characterized by comprising the carbonyl polymer according to claim 1.
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