CN115215337B - A method for synthesizing phenolic resin and preparing carbon material - Google Patents

A method for synthesizing phenolic resin and preparing carbon material Download PDF

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CN115215337B
CN115215337B CN202210568232.1A CN202210568232A CN115215337B CN 115215337 B CN115215337 B CN 115215337B CN 202210568232 A CN202210568232 A CN 202210568232A CN 115215337 B CN115215337 B CN 115215337B
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CN115215337A (en
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胡勋
周舒心
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Lanzhou Institute of Chemical Physics LICP of CAS
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    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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Abstract

The invention relates to a synthetic phenolic resin and a method for preparing a carbon material by using the phenolic resin, wherein the specific preparation method of the phenolic resin comprises the following steps: (a) Fully grinding and mixing tannic acid, pentahydroxymethyl furfural and nano magnesium oxide by using a mortar according to a mass ratio, adding a small amount of dilute sulfuric acid in the grinding process for catalysis, and continuously grinding until the materials are uniform; (b) And collecting the uniformly ground sample into a polytetrafluoroethylene lining, transferring the sample into a hydrothermal kettle, and reacting to obtain the phenolic resin-based material. The invention replaces common raw materials phenol and formaldehyde with tannic acid and pentahydroxymethyl furfural. The tannic acid and the pentahydroxymethyl furfural are used as raw materials for producing the phenolic resin, so that pollution and harm to human bodies caused by the preparation process can be effectively reduced. The phenolic resin carbon material prepared by the invention has larger specific surface area, reasonable pore distribution and good morphology distribution, and the specific surface area of the material can reach 950.40m 2/g.

Description

一种合成酚醛树脂且制备碳材料的方法A method for synthesizing phenolic resin and preparing carbon material

技术领域Technical Field

本发明涉及酚醛树脂领域,具体涉及一种合成酚醛树脂,以及用该酚醛树脂制备碳材料的方法。The invention relates to the field of phenolic resins, and in particular to a synthetic phenolic resin and a method for preparing a carbon material by using the phenolic resin.

技术背景technical background

酚醛树脂具有良好的耐酸性能、力学性能、耐热性能,广泛应用于防腐蚀、胶粘剂、阻燃材料等;并且酚醛树脂具有高残炭率,酚醛树脂在1000℃的惰性气体条件下会产生很高的残碳,产生的碳材料可以用于锌离子超级电容器的阴极材料。Phenolic resin has good acid resistance, mechanical properties, and heat resistance, and is widely used in anti-corrosion, adhesives, flame retardant materials, etc.; and phenolic resin has a high residual carbon rate. Phenolic resin will produce very high residual carbon under inert gas conditions at 1000°C. The produced carbon material can be used as the cathode material of zinc ion supercapacitors.

目前酚醛树脂的制备原理是酚类和醛类在酸性或者碱性的催化剂作用下,通过缩聚反应生成酚醛树脂。酚醛树脂使用的原料一般为苯酚和甲醛等。但苯酚有毒,它的浓溶液对皮肤有强烈的腐蚀性,使用时有很大的风险存在;并且甲醛对人体也有危害。At present, the preparation principle of phenolic resin is that phenols and aldehydes are reacted under the action of acidic or alkaline catalysts to generate phenolic resin through polycondensation reaction. The raw materials used for phenolic resin are generally phenol and formaldehyde. However, phenol is toxic, and its concentrated solution is highly corrosive to the skin, which poses a great risk when used; and formaldehyde is also harmful to the human body.

发明内容Summary of the invention

为了解决上述问题,本发明将常用原料苯酚和甲醛使用丹宁酸和五羟甲基糠醛代替,其中丹宁酸是一种生物质原料,普遍存在于葡萄、茶叶等植物中,并且含有大量的酚羟基;五羟甲基糠醛是由葡萄糖或者果糖脱水生成的化学物质,它的分子中含有高活性的醛基。使用丹宁酸和五羟甲基糠醛作为生产酚醛树脂的原料,可以有效地减少制备过程带来的污染和对人体的危害。制备得到的酚醛树脂基碳材料可用作锌离子超级电容器的碳阴极,并且表现出较好的性能。本发明碳材料用作碳阴极的锌离子混合超级电容器的电极测试表明,当功率密度达到731 W/kg时,比电容达到90.7 mAh/g,能量密度达到79 Wh /kg。In order to solve the above problems, the present invention replaces the commonly used raw materials phenol and formaldehyde with tannic acid and pentahydroxymethylfurfural, wherein tannic acid is a biomass raw material, which is commonly found in plants such as grapes and tea leaves and contains a large amount of phenolic hydroxyl groups; pentahydroxymethylfurfural is a chemical substance generated by dehydration of glucose or fructose, and its molecules contain highly active aldehyde groups. Using tannic acid and pentahydroxymethylfurfural as raw materials for producing phenolic resin can effectively reduce the pollution caused by the preparation process and the harm to the human body. The prepared phenolic resin-based carbon material can be used as a carbon cathode of a zinc ion supercapacitor and exhibits good performance. The electrode test of the zinc ion hybrid supercapacitor using the carbon material of the present invention as a carbon cathode shows that when the power density reaches 731 W/kg, the specific capacitance reaches 90.7 mAh/g and the energy density reaches 79 Wh/kg.

本发明酚醛树脂的制备方法如下:The preparation method of phenolic resin of the present invention is as follows:

(a)将丹宁酸、五羟甲基糠醛和纳米氧化镁按照质量比使用研钵充分研磨混合,研磨过程中加入少量稀硫酸催化后继续研磨至均匀。(a) Grind and mix tannic acid, pentahydroxymethylfurfural and nano-magnesium oxide in a mortar according to the mass ratio. Add a small amount of dilute sulfuric acid as a catalyst during the grinding process and continue grinding until the mixture is uniform.

(b)将研磨均匀后的样品收集到聚四氟乙烯内衬中,移入水热釜,反应,得到酚醛树脂基材料。(b) The uniformly ground sample is collected into a polytetrafluoroethylene liner and transferred into a hydrothermal autoclave for reaction to obtain a phenolic resin-based material.

进一步的,丹宁酸:五羟甲基糠醛:纳米氧化镁质量比为1:1:2。Furthermore, the mass ratio of tannic acid: pentahydroxymethylfurfural: nano-magnesium oxide is 1:1:2.

进一步的,稀硫酸用量为0.5mol/L。Furthermore, the amount of dilute sulfuric acid used is 0.5 mol/L.

进一步的,步骤(b)中的反应条件为:在180℃下反应12小时。Furthermore, the reaction conditions in step (b) are: reacting at 180° C. for 12 hours.

用本发明酚醛树脂基材料制备酚醛树脂碳材料的方法,具体制备步骤如下:The method for preparing a phenolic resin carbon material using the phenolic resin-based material of the present invention comprises the following specific preparation steps:

①将酚醛树脂基材料移入石墨舟,氮气气氛下,升温直至900℃,保温1小时后,得到样品。① Move the phenolic resin-based material into a graphite boat, raise the temperature to 900°C under a nitrogen atmosphere, and keep it for 1 hour to obtain a sample.

②使用盐酸清洗样品,抽滤后置于烘箱中烘干,得到酚醛树脂碳材料。② The sample was washed with hydrochloric acid, filtered and dried in an oven to obtain a phenolic resin carbon material.

进一步的,步骤①升温速度为:2℃/min。Furthermore, the heating rate in step ① is 2°C/min.

进一步的,步骤②使用盐酸清洗样品时,使用的盐酸为:1mol/L。Furthermore, when hydrochloric acid is used to clean the sample in step ②, the hydrochloric acid used is: 1 mol/L.

进一步的,步骤②烘干条件为:置于60℃烘箱中烘6h。Furthermore, the drying condition of step ② is: placing in an oven at 60° C. for 6 hours.

本发明的有益效果:Beneficial effects of the present invention:

本发明使用丹宁酸代替苯酚,其中丹宁酸中含有大量的酚羟基,满足基本反应,并且作为生物质原料,丹宁酸来源丰富,分布广泛;五羟甲基糠醛作为糖类脱水的产物,在生物质能源领域具有重要地位。使用丹宁酸和五羟甲基糠醛作为生产酚醛树脂的原料,可以大大降低生产过程中带来的对人体的危害,以及对环境带来的污染。The present invention uses tannic acid instead of phenol, wherein tannic acid contains a large amount of phenolic hydroxyl groups, which satisfies the basic reaction, and as a biomass raw material, tannic acid is rich in source and widely distributed; pentahydroxymethylfurfural, as a product of sugar dehydration, plays an important role in the field of biomass energy. Using tannic acid and pentahydroxymethylfurfural as raw materials for producing phenolic resin can greatly reduce the harm to human body and the pollution to the environment in the production process.

本发明制备得到的活化的酚醛树脂碳材料具有较大的比表面积,合理的孔分布以及良好的形貌分布,活化后的材料比表面积可达1603.40m2/g。该活化的酚醛树脂碳材料作为锌离子超级电容器的碳阴极具有高的比电容和相匹配的能量密度和功率密度,锌离子超级电容器的电极测试表明,当功率密度达到731 W/kg时,比电容达到90.7 mAh/g,能量密度达到79 Wh /kg。The activated phenolic resin carbon material prepared by the present invention has a large specific surface area, reasonable pore distribution and good morphology distribution, and the specific surface area of the activated material can reach 1603.40m2 /g. The activated phenolic resin carbon material has a high specific capacitance and a matching energy density and power density as a carbon cathode of a zinc ion supercapacitor. Electrode tests of zinc ion supercapacitors show that when the power density reaches 731 W/kg, the specific capacitance reaches 90.7 mAh/g and the energy density reaches 79 Wh/kg.

附图说明BRIEF DESCRIPTION OF THE DRAWINGS

图1实施例1酚醛树脂基材料的TGA和DTA曲线图;a)TGA曲线, b)DTA曲线Figure 1 TGA and DTA curves of phenolic resin-based materials in Example 1; a) TGA curve, b) DTA curve

图2实施例1酚醛树脂基材料的红外谱图FIG. 2 Infrared spectrum of phenolic resin-based material of Example 1

图3实施例1和实施例2的酚醛树脂碳材料电镜照片;实施例2的电镜照片a) SEM图,b) TEM 图;实施例1的电镜照片c)SEM图,d)TEM图。FIG3 is electron microscope photographs of phenolic resin carbon materials of Example 1 and Example 2; electron microscope photographs of Example 2 a) SEM image, b) TEM image; electron microscope photographs of Example 1 c) SEM image, d) TEM image.

图4对照组1和对照组2的TGA曲线;a)对照组1, b)对照组2Figure 4 TGA curves of control group 1 and control group 2; a) control group 1, b) control group 2

图5实施例1样品的a)CV曲线, b)GCD曲线。Figure 5 a) CV curve, b) GCD curve of the sample in Example 1.

具体实施方式Detailed ways

下面通过具体的实施例对本发明做进一步的阐述和说明:The present invention will be further described and illustrated by specific embodiments below:

实施例1:本发明酚醛树脂基碳材料的制备Example 1: Preparation of phenolic resin-based carbon material of the present invention

(1)将丹宁酸1g、五羟甲基糠醛1g和纳米氧化镁2g按照质量比1:1:2的比例使用研钵充分研磨混合,研磨过程中加入5ml0.5mol/L的硫酸催化后继续研磨30min;(1) 1 g of tannic acid, 1 g of pentahydroxymethylfurfural and 2 g of nano magnesium oxide were fully ground and mixed in a mortar in a mass ratio of 1:1:2. During the grinding process, 5 ml of 0.5 mol/L sulfuric acid was added as a catalyst and the grinding was continued for 30 min.

(2)将研磨均匀后的样品中收集到聚四氟乙烯内衬中,移入水热釜,在180℃下反应12小时,得到酚醛树脂基材料;(2) collecting the uniformly ground sample into a polytetrafluoroethylene liner, transferring it into a hydrothermal autoclave, and reacting it at 180° C. for 12 hours to obtain a phenolic resin-based material;

(3)将酚醛树脂基材料移入石墨舟,氮气气氛下,以2℃/min升温速度进行升温,直至900℃,保温1小时后,得到样品;(3) The phenolic resin-based material was transferred into a graphite boat, and the temperature was increased at a rate of 2°C/min to 900°C under a nitrogen atmosphere. After keeping the temperature for 1 hour, a sample was obtained.

(4)使用1mol盐酸清洗样品,抽滤后置于60℃烘箱中烘干6h后,得到酚醛树脂碳材料。(4) The sample was washed with 1 mol hydrochloric acid, filtered, and dried in an oven at 60 °C for 6 h to obtain a phenolic resin carbon material.

实施例1酚醛树脂基材料的TGA和DTA曲线图见图1;图1中,a)TGA曲线, b)DTA曲线。酚醛树脂基材料的红外谱图见图2。The TGA and DTA curves of the phenolic resin-based material of Example 1 are shown in FIG1 ; in FIG1 , a) TGA curve, b) DTA curve. The infrared spectrum of the phenolic resin-based material is shown in FIG2 .

实施例1步骤(1)材料指未进行热聚合样品,实施例1步骤(2)材料指已经过热聚合样品。从图1和图2可以看出,聚合之后材料的碳收率发生明显变化,说明在聚合温度下单宁酸和五羟甲基糠醛发生交联反应,生成酚醛树脂材料。The material in step (1) of Example 1 refers to a sample that has not been subjected to thermal polymerization, and the material in step (2) of Example 1 refers to a sample that has been subjected to thermal polymerization. As can be seen from Figures 1 and 2, the carbon yield of the material changes significantly after polymerization, indicating that tannic acid and pentahydroxymethylfurfural undergo a cross-linking reaction at the polymerization temperature to generate a phenolic resin material.

实施例2:Embodiment 2:

(1)将丹宁酸1g和五羟甲基糠醛1g按照质量比1:1的比例使用研钵充分研磨混合,研磨过程中加入5ml 0.5mol/L的硫酸催化后继续研磨30min;(1) 1 g of tannic acid and 1 g of pentahydroxymethylfurfural were thoroughly ground and mixed in a mortar at a mass ratio of 1:1. During the grinding process, 5 ml of 0.5 mol/L sulfuric acid was added as a catalyst and the grinding was continued for 30 min.

(2)将研磨均匀后的样品中收集到聚四氟乙烯内衬中,移入水热釜,在180℃下反应12小时,得到酚醛树脂基材料;(2) collecting the uniformly ground sample into a polytetrafluoroethylene liner, transferring it into a hydrothermal autoclave, and reacting it at 180° C. for 12 hours to obtain a phenolic resin-based material;

(3)将酚醛树脂基材料移入石墨舟,氮气气氛下,以2℃/min升温速度进行升温,直至900℃,保温1小时后,得到样品。(3) The phenolic resin-based material was transferred into a graphite boat and heated at a rate of 2°C/min to 900°C under a nitrogen atmosphere. After keeping the temperature for 1 hour, a sample was obtained.

对实施例1和实施例2酚醛树脂碳材料进行扫描电镜图测试,扫描电镜照片见图3。从图3a)和c)的对比可以看出,纳米氧化镁用作模板提高了碳材料孔隙率,增加吸附位点,促进后续电化学中的氧化还原反应。The phenolic resin carbon materials of Example 1 and Example 2 were tested by scanning electron microscopy, and the scanning electron microscopy photos are shown in Figure 3. From the comparison of Figure 3a) and c), it can be seen that the use of nano-magnesium oxide as a template increases the porosity of the carbon material, increases the adsorption sites, and promotes the redox reaction in the subsequent electrochemical process.

实施例3:Embodiment 3:

(1)将丹宁酸1g、五羟甲基糠醛1g和纳米氧化镁4g按照质量比1:1:4的比例使用研钵充分研磨混合,研磨过程中加入5 ml 0.5mol/L的硫酸催化后继续研磨30min;(1) 1 g of tannic acid, 1 g of pentahydroxymethylfurfural and 4 g of nano-magnesium oxide were thoroughly ground and mixed in a mortar in a mass ratio of 1:1:4. During the grinding process, 5 ml of 0.5 mol/L sulfuric acid was added as a catalyst and the grinding was continued for 30 min.

(2)将研磨均匀后的样品中收集到聚四氟乙烯内衬中,移入水热釜,在180℃下反应12小时,得到酚醛树脂基材料;(2) collecting the uniformly ground sample into a polytetrafluoroethylene liner, transferring it into a hydrothermal autoclave, and reacting it at 180° C. for 12 hours to obtain a phenolic resin-based material;

(3)将酚醛树脂基材料移入石墨舟,氮气气氛下,以2℃/min升温速度进行升温,直至900℃,保温1小时后,得到样品;(3) The phenolic resin-based material was transferred into a graphite boat, and the temperature was increased at a rate of 2°C/min to 900°C under a nitrogen atmosphere. After keeping the temperature for 1 hour, a sample was obtained.

(4)使用1mol盐酸清洗样品,抽滤后置于60℃烘箱中烘干6h后,得到酚醛树脂碳材料。(4) The sample was washed with 1 mol hydrochloric acid, filtered, and dried in an oven at 60 °C for 6 h to obtain a phenolic resin carbon material.

实施例4:Embodiment 4:

(1)将丹宁酸1g、五羟甲基糠醛1g和纳米氧化镁6g按照质量比1:1:6的比例使用研钵充分研磨混合,研磨过程中加入5 ml 0.5mol/L的硫酸催化后继续研磨30min;(1) 1 g of tannic acid, 1 g of pentahydroxymethylfurfural and 6 g of nano-magnesium oxide were thoroughly ground and mixed in a mortar in a mass ratio of 1:1:6. During the grinding process, 5 ml of 0.5 mol/L sulfuric acid was added as a catalyst and the grinding was continued for 30 min.

(2)将研磨均匀后的样品中收集到聚四氟乙烯内衬中,移入水热釜,在180 ℃下反应12小时,得到酚醛树脂基材料;(2) The uniformly ground sample was collected into a polytetrafluoroethylene liner, transferred into a hydrothermal autoclave, and reacted at 180 °C for 12 hours to obtain a phenolic resin-based material;

(3)将酚醛树脂基材料移入石墨舟,氮气气氛下,以2℃/min升温速度进行升温,直至900℃,保温1小时后,得到样品;(3) The phenolic resin-based material was transferred into a graphite boat, and the temperature was increased at a rate of 2°C/min to 900°C under a nitrogen atmosphere. After keeping the temperature for 1 hour, a sample was obtained.

(4)使用1mol盐酸清洗样品,抽滤后置于60℃烘箱中烘干6h后,得到酚醛树脂碳材料。(4) The sample was washed with 1 mol hydrochloric acid, filtered, and dried in an oven at 60 °C for 6 h to obtain a phenolic resin carbon material.

对照组1:(用苯甲醛1g替换实施例1中的五羟甲基糠醛1g)Control group 1: (1 g of pentahydroxymethylfurfural in Example 1 was replaced with 1 g of benzaldehyde)

(1)将丹宁酸1g、苯甲醛1g和纳米氧化镁2g按照质量比1:1:2的比例使用研钵充分研磨混合,研磨过程中加入5ml 0.5mol/L的硫酸催化后继续研磨30min;(1) 1 g of tannic acid, 1 g of benzaldehyde and 2 g of nano magnesium oxide were thoroughly ground and mixed in a mortar in a mass ratio of 1:1:2. During the grinding process, 5 ml of 0.5 mol/L sulfuric acid was added as a catalyst and the grinding was continued for 30 min.

(2)将研磨均匀后的样品中收集到聚四氟乙烯内衬中,移入水热釜,在180℃下反应12小时,得到酚醛树脂基材料;(2) collecting the uniformly ground sample into a polytetrafluoroethylene liner, transferring it into a hydrothermal autoclave, and reacting it at 180° C. for 12 hours to obtain a phenolic resin-based material;

(3)将酚醛树脂基材料移入石墨舟,氮气气氛下,以2℃/min升温速度进行升温,直至900℃,保温1小时后,得到样品;(3) The phenolic resin-based material was transferred into a graphite boat, and the temperature was increased at a rate of 2°C/min to 900°C under a nitrogen atmosphere. After keeping the temperature for 1 hour, a sample was obtained.

(4)使用1mol盐酸清洗样品,抽滤后置于60℃烘箱中烘干6h后,得到酚醛树脂碳材料。(4) The sample was washed with 1 mol hydrochloric acid, filtered, and dried in an oven at 60 °C for 6 h to obtain a phenolic resin carbon material.

对照组2:(用对苯二甲醛1g替换实施例1中的五羟甲基糠醛1g)Control group 2: (1 g of pentahydroxymethylfurfural in Example 1 was replaced with 1 g of terephthalaldehyde)

(1)将丹宁酸1g、对苯二甲醛1g和纳米氧化镁2g按照质量比1:1:2的比例使用研钵充分研磨混合,研磨过程中加入5ml 0.5mol/L的硫酸催化后继续研磨30min;(1) 1 g of tannic acid, 1 g of terephthalaldehyde and 2 g of nano magnesium oxide were thoroughly ground and mixed in a mortar in a mass ratio of 1:1:2. During the grinding process, 5 ml of 0.5 mol/L sulfuric acid was added as a catalyst and the grinding was continued for 30 min.

(2)将研磨均匀后的样品中收集到聚四氟乙烯内衬中,移入水热釜,在180℃下反应12小时,得到酚醛树脂基材料;(2) collecting the uniformly ground sample into a polytetrafluoroethylene liner, transferring it into a hydrothermal autoclave, and reacting it at 180° C. for 12 hours to obtain a phenolic resin-based material;

(3)将酚醛树脂基材料移入石墨舟,氮气气氛下,以2℃/min升温速度进行升温,直至900℃,保温1小时后,得到样品;(3) The phenolic resin-based material was transferred into a graphite boat, and the temperature was increased at a rate of 2°C/min to 900°C under a nitrogen atmosphere. After keeping the temperature for 1 hour, a sample was obtained.

(4)使用1mol盐酸清洗样品,抽滤后置于60℃烘箱中烘干6h后,得到酚醛树脂碳材料。(4) The sample was washed with 1 mol hydrochloric acid, filtered, and dried in an oven at 60 °C for 6 h to obtain a phenolic resin carbon material.

从本发明实施例1、3、4可以看出,本发明经过酸催化和热处理后的丹宁酸和五羟甲基糠醛可以成功制备得到酚醛树脂基材料。对照组1和对照组2更换醛类物质依旧可以制备得到酚醛树脂。It can be seen from Examples 1, 3 and 4 of the present invention that the tannic acid and pentahydroxymethylfurfural after acid catalysis and heat treatment can be successfully used to prepare phenolic resin-based materials. Control group 1 and control group 2 can still prepare phenolic resin by replacing aldehyde substances.

本发明使用丹宁酸和五羟甲基糠醛作为生产酚醛树脂的原料,可以大大降低生产过程中带来的对人体的危害,以及对环境带来的污染。The present invention uses tannic acid and pentahydroxymethylfurfural as raw materials for producing phenolic resin, which can greatly reduce the harm to human body and the pollution to the environment brought about in the production process.

本发明制备得到的酚醛树脂碳材料具有较大的比表面积,合理的孔分布以及良好的形貌分布,材料比表面积可达950.40m2/g。该酚醛树脂碳材料作为锌离子超级电容器的碳阴极具有高的比电容和相匹配的能量密度和功率密度,锌离子超级电容器的电极测试表明,当功率密度达到731 W/kg时,比电容达到90.7 mAh/g,能量密度达到79 Wh /kg。The phenolic resin carbon material prepared by the present invention has a large specific surface area, reasonable pore distribution and good morphology distribution, and the specific surface area of the material can reach 950.40m2 /g. The phenolic resin carbon material has a high specific capacitance and a matching energy density and power density as a carbon cathode of a zinc ion supercapacitor. Electrode tests of zinc ion supercapacitors show that when the power density reaches 731 W/kg, the specific capacitance reaches 90.7 mAh/g and the energy density reaches 79 Wh/kg.

以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (5)

1. The preparation method of the phenolic resin-based material is characterized by comprising the following specific preparation steps:
(a) Fully grinding and mixing tannic acid, pentahydroxymethyl furfural and nano magnesium oxide by using a mortar according to a mass ratio, adding a small amount of dilute sulfuric acid in the grinding process for catalysis, and continuously grinding until the materials are uniform;
(b) Collecting a uniformly ground sample into a polytetrafluoroethylene lining, transferring the sample into a hydrothermal kettle, and reacting to obtain a phenolic resin-based material;
Tannic acid: pentahydroxymethyl furfural: the mass ratio of the nano magnesium oxide is 1:1:2;
The dosage of the dilute sulfuric acid is 0.5 mol/L;
the reaction conditions in step (b) are: the reaction was carried out at 180℃for 12 hours.
2. A method for preparing a phenolic resin carbon material by using the phenolic resin-based material as claimed in claim 1, which is characterized by comprising the following specific preparation steps:
① Transferring the phenolic resin-based material into a graphite boat, heating to 900 ℃ under nitrogen atmosphere, and preserving heat for 1 hour to obtain a sample;
② And cleaning the sample by using hydrochloric acid, and placing the sample in an oven for drying after suction filtration to obtain the phenolic resin carbon material.
3. The method of preparing a phenolic resin carbon material of claim 2 wherein step ① is performed at a rate of temperature rise of: 2 ℃/min.
4. The method of preparing a phenolic carbon material of claim 2 wherein in step ②, hydrochloric acid is used to clean the sample by: 1mol/L.
5. The method of preparing a phenolic resin carbon material as claimed in claim 2, wherein the drying conditions of step ② are: and placing the mixture in a baking oven at 60 ℃ for baking for 6 hours.
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