CN112429728A - Preparation method of graphene material suitable for cold spraying - Google Patents
Preparation method of graphene material suitable for cold spraying Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 69
- 239000000463 material Substances 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000010288 cold spraying Methods 0.000 title claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 30
- 239000003999 initiator Substances 0.000 claims abstract description 21
- 239000000701 coagulant Substances 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 14
- 239000010439 graphite Substances 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 6
- 238000003763 carbonization Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000006185 dispersion Substances 0.000 claims description 25
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 22
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical group NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 20
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000003431 cross linking reagent Substances 0.000 claims description 13
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 11
- 239000000292 calcium oxide Substances 0.000 claims description 11
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 11
- 239000011787 zinc oxide Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000002270 dispersing agent Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical group CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000003822 epoxy resin Substances 0.000 claims description 5
- 238000005469 granulation Methods 0.000 claims description 5
- 230000003179 granulation Effects 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 5
- 229920000647 polyepoxide Polymers 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000001704 evaporation Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 4
- 229910001290 LiPF6 Inorganic materials 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 3
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000005355 Hall effect Effects 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910001867 inorganic solvent Inorganic materials 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
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Abstract
Description
技术领域technical field
本发明涉及石墨烯材料的制备方法技术领域,具体涉及一种适用于冷喷涂的石墨烯材料制备方法。The invention relates to the technical field of preparation methods of graphene materials, in particular to a preparation method of graphene materials suitable for cold spraying.
背景技术Background technique
石墨烯(Graphene)是由sp2杂化的碳原子紧密排列而成的二维蜂窝状晶体结构,属于石墨类材料。它具有优异的杨氏模量(1100GPa)、高导热率(约5000J·(m·K·s)-1)、高载流子迁移率(2×105cm2·(V·s)-1)和高比表面积(理论计算值2630m2·g-1),以及量子霍尔效应和量子遂穿效应,同时还有优异的不可渗透性等,使其在电子器件、复合材料和功能涂料等领域有着巨大的应用前景。然而,石墨烯由于其层与层之间拥有较强的π-π相互作用和范德华力,使得其极易趋于团聚,而石墨烯优异的性能与其层数有关;此外,石墨烯只能分散于少数极性极强的溶剂中,并且这些溶剂大都有毒,不利于环境和人的可持续发展,大大地限制了石墨烯的应用。因此,简单、高效地提高石墨烯在常见的有机溶剂和无机溶剂中的分散性,对石墨烯的应用有着十分重要的实际意义。Graphene is a two-dimensional honeycomb crystal structure composed of sp2-hybridized carbon atoms closely arranged, belonging to graphite materials. It has excellent Young's modulus (1100GPa), high thermal conductivity (about 5000J·(m·K·s)-1), high carrier mobility (2×105cm2·(V·s)-1) and High specific surface area (theoretical calculation value 2630m2·g-1), as well as quantum Hall effect and quantum tunneling effect, as well as excellent impermeability, etc., make it have great applications in the fields of electronic devices, composite materials and functional coatings. application prospects. However, graphene tends to agglomerate easily due to its strong π-π interaction and van der Waals forces between layers, and the excellent properties of graphene are related to the number of layers; in addition, graphene can only be dispersed In a few extremely polar solvents, most of these solvents are toxic, which is not conducive to the sustainable development of the environment and people, and greatly limits the application of graphene. Therefore, it is of great practical significance for the application of graphene to simply and efficiently improve the dispersibility of graphene in common organic and inorganic solvents.
发明内容SUMMARY OF THE INVENTION
针对现有技术存在的不足,本发明的目的在于提供一种适用于冷喷涂的石墨烯材料制备方法,其具有保证聚合物完全包覆到石墨表面且让每次的包覆量都相同优点。In view of the deficiencies in the prior art, the object of the present invention is to provide a graphene material preparation method suitable for cold spraying, which has the advantages of ensuring that the polymer is completely coated on the graphite surface and the coating amount is the same each time.
为实现上述目的,本发明提供了如下技术方案:一种适用于冷喷涂的石墨烯材料制备方法,其特征在于:包括如下步骤:In order to achieve the above object, the present invention provides the following technical solutions: a graphene material preparation method suitable for cold spraying, characterized in that: comprising the following steps:
步骤1:将石墨烯进行预氧化,即称取五氧化二磷、过硫酸钾、浓硫酸于容器中密封,水浴加热至75-85℃,在水浴中搅拌,直至原料全部溶解,少量多次缓慢的加入石墨烯,保温反应4-8h,反应结束后,使用去离子水洗至中性后,40-60℃干燥20-28h备用,上述五氧化二磷、过硫酸钾、浓硫酸、石墨粉的重量比为8:2:30:15,将预氧化后的石墨烯溶液溶于水中,得到石墨烯溶液,再加入分散剂和高分子聚合物,混合搅拌,得到石墨烯分散液,分散剂用量为石墨烯溶液质量的0.05%~0.2%;Step 1: Pre-oxidize the graphene, that is, weigh phosphorus pentoxide, potassium persulfate and concentrated sulfuric acid, seal them in a container, heat them to 75-85°C in a water bath, and stir in a water bath until all the raw materials are dissolved. Graphene was slowly added, and the reaction was kept for 4-8 hours. After the reaction was over, washed with deionized water until neutral, and dried at 40-60°C for 20-28 hours. The above-mentioned phosphorus pentoxide, potassium persulfate, concentrated sulfuric acid, graphite powder The weight ratio is 8:2:30:15, dissolving the pre-oxidized graphene solution in water to obtain a graphene solution, then adding a dispersant and a high molecular polymer, mixing and stirring to obtain a graphene dispersion liquid, a dispersant The dosage is 0.05% to 0.2% of the mass of the graphene solution;
步骤2:将丙烯酰胺单体和交联剂加入到石墨烯分散液中,混合搅拌,并进行预加热,得到预加热溶液,丙烯酰胺单体用量为石墨烯分散液质量的5%~7%;交联剂与丙烯酰胺单体的摩尔比为1:(18~22);Step 2: adding the acrylamide monomer and the crosslinking agent into the graphene dispersion, mixing and stirring, and preheating to obtain a preheated solution, and the amount of the acrylamide monomer is 5% to 7% of the mass of the graphene dispersion ; The molar ratio of crosslinking agent to acrylamide monomer is 1:(18~22);
步骤3:将步骤②所得的混合物继续升温加入引发剂、促凝剂、硅烷偶联剂,引发剂为过硫酸盐引发剂,促凝剂为四甲基乙二胺,引发剂用量为丙烯酰胺单体和交联剂总质量的1%~2%;促凝剂用量为预加热溶液体积的0.05%,其中石墨烯分散液质量与硼酸的质量比为100:2,蒸除有机溶剂后再升温使该高分子聚合物完全固化,升温过程中充分搅拌造粒,获得表面包覆高分子聚合物的石墨复合材料,冷却至室温;Step 3: Continue to heat up the mixture obtained in step ②, add initiator, coagulant and silane coupling agent, the initiator is persulfate initiator, the coagulant is tetramethylethylenediamine, and the amount of initiator is acrylamide 1% to 2% of the total mass of the monomer and crosslinking agent; the amount of the coagulant is 0.05% of the volume of the preheated solution, and the mass ratio of the graphene dispersion to the boric acid is 100:2. The high-molecular polymer is completely solidified by heating up, and during the heating process, the granulation is fully stirred to obtain a graphite composite material coated with the high-molecular polymer, and cooled to room temperature;
步骤4:将步骤③冷却后的表面包覆高分子聚合物的石墨复合材料进行常规炭化处理。Step 4: performing conventional carbonization treatment on the graphite composite material whose surface is coated with high molecular polymer after cooling in step ③.
优选的,所述高分子聚合物选取环氧树脂。Preferably, the high molecular polymer is selected from epoxy resin.
优选的,所述步骤3中还添加有氧化锌和氧化钙,其中石墨烯分散液质量与氧化锌和氧化钙的质量比为100:1:1。Preferably, zinc oxide and calcium oxide are also added in the step 3, wherein the mass ratio of the graphene dispersion liquid to zinc oxide and calcium oxide is 100:1:1.
综上所述,本发明具有以下有益效果:To sum up, the present invention has the following beneficial effects:
本发明在升温固化过程中结合了浸渍和蒸除溶剂处理,简化了工艺;所制得的改性石墨烯溶液不会结块,不需要破碎处理,减少了设备投资,有利于大规模生产;而且本发明的改性石墨、特别是改性天然石墨作为炭负极材料具有较长的循环寿命和较佳的大电流放电性能,另外加入了氧化锌和氧化钙增强整体的物理性能。In the process of heating and curing, the method combines immersion and solvent removal treatment, which simplifies the process; the prepared modified graphene solution does not agglomerate, does not require crushing treatment, reduces equipment investment, and is beneficial to large-scale production; Moreover, the modified graphite of the present invention, especially the modified natural graphite, has longer cycle life and better high current discharge performance as a carbon negative electrode material, and zinc oxide and calcium oxide are added to enhance the overall physical properties.
具体实施方式Detailed ways
对本发明做进一步说明。The present invention will be further described.
实施例1:一种适用于冷喷涂的石墨烯材料制备方法,包括如下步骤:Embodiment 1: a kind of graphene material preparation method applicable to cold spraying, comprises the steps:
步骤1:将石墨烯进行预氧化,即称取五氧化二磷、过硫酸钾、浓硫酸于容器中密封,水浴加热至75-85℃,在水浴中搅拌,直至原料全部溶解,少量多次缓慢的加入石墨烯,保温反应4-8h,反应结束后,使用去离子水洗至中性后,40-60℃干燥20-28h备用,上述五氧化二磷、过硫酸钾、浓硫酸、石墨粉的重量比为8:2:30:15,将预氧化后的石墨烯溶液溶于水中,得到石墨烯溶液,再加入分散剂和高分子聚合物,混合搅拌,得到石墨烯分散液,分散剂用量为石墨烯溶液质量的0.05%;Step 1: Pre-oxidize the graphene, that is, weigh phosphorus pentoxide, potassium persulfate and concentrated sulfuric acid, seal them in a container, heat them to 75-85°C in a water bath, and stir in a water bath until all the raw materials are dissolved. Graphene was slowly added, and the reaction was kept for 4-8 hours. After the reaction was over, washed with deionized water until neutral, and dried at 40-60°C for 20-28 hours. The above-mentioned phosphorus pentoxide, potassium persulfate, concentrated sulfuric acid, graphite powder The weight ratio is 8:2:30:15, dissolving the pre-oxidized graphene solution in water to obtain a graphene solution, then adding a dispersant and a high molecular polymer, mixing and stirring to obtain a graphene dispersion liquid, a dispersant The dosage is 0.05% of the mass of the graphene solution;
步骤2:将丙烯酰胺单体和交联剂加入到石墨烯分散液中,混合搅拌,并进行预加热,得到预加热溶液,丙烯酰胺单体用量为石墨烯分散液质量的5%%;交联剂与丙烯酰胺单体的摩尔比为1:18;Step 2: adding the acrylamide monomer and the crosslinking agent into the graphene dispersion, mixing and stirring, and preheating to obtain a preheated solution, and the amount of the acrylamide monomer is 5% of the mass of the graphene dispersion; The molar ratio of linking agent and acrylamide monomer is 1:18;
步骤3:将步骤②所得的混合物继续升温加入引发剂、促凝剂、硅烷偶联剂,引发剂为过硫酸盐引发剂,促凝剂为四甲基乙二胺,引发剂用量为丙烯酰胺单体和交联剂总质量的1%;促凝剂用量为预加热溶液体积的0.05%,其中石墨烯分散液质量与硼酸的质量比为100:2,蒸除有机溶剂后再升温使该高分子聚合物完全固化,升温过程中充分搅拌造粒,获得表面包覆高分子聚合物的石墨复合材料,冷却至室温;Step 3: Continue to heat up the mixture obtained in step ②, add initiator, coagulant and silane coupling agent, the initiator is persulfate initiator, the coagulant is tetramethylethylenediamine, and the amount of initiator is acrylamide 1% of the total mass of the monomer and crosslinking agent; the amount of the coagulant is 0.05% of the volume of the preheated solution, and the mass ratio of the graphene dispersion to the boric acid is 100:2, and the temperature is raised after the organic solvent is evaporated to make the The high-molecular polymer is completely solidified, and the granulation is fully stirred during the heating process to obtain a graphite composite material coated with the high-molecular polymer, and cooled to room temperature;
步骤4:将步骤③冷却后的表面包覆高分子聚合物的石墨复合材料进行常规炭化处理。Step 4: performing conventional carbonization treatment on the graphite composite material whose surface is coated with high molecular polymer after cooling in step ③.
所述高分子聚合物选取环氧树脂。The high molecular polymer is selected from epoxy resin.
所述步骤3中还添加有氧化锌和氧化钙,其中石墨烯分散液质量与氧化锌和氧化钙的质量比为100:1:1。Also added zinc oxide and calcium oxide in described step 3, wherein the mass ratio of graphene dispersion liquid to zinc oxide and calcium oxide is 100:1:1.
将制得的改性石墨作负极,钴酸锂作正极,1M-LiPF6 EC∶DMC∶EMC=1∶1∶1溶液作电解液装配成全电池,以3C放电的容量是0.5C放电容量的85%,以2C放电的容量是0.5C放电容量的95%,且以1C充放300周容量保持率在91%。The obtained modified graphite is used as the negative electrode, lithium cobalt oxide is used as the positive electrode, and the 1M-LiPF6 EC:DMC:EMC=1:1:1 solution is used as the electrolyte to assemble a full battery. The discharge capacity at 3C is 85% of the discharge capacity at 0.5C. %, the discharge capacity at 2C is 95% of the discharge capacity at 0.5C, and the capacity retention rate at 1C for 300 cycles is 91%.
实施例2:一种适用于冷喷涂的石墨烯材料制备方法,包括如下步骤:Embodiment 2: a kind of graphene material preparation method applicable to cold spraying, comprises the steps:
步骤1:将石墨烯进行预氧化,即称取五氧化二磷、过硫酸钾、浓硫酸于容器中密封,水浴加热至75-85℃,在水浴中搅拌,直至原料全部溶解,少量多次缓慢的加入石墨烯,保温反应4-8h,反应结束后,使用去离子水洗至中性后,40-60℃干燥20-28h备用,上述五氧化二磷、过硫酸钾、浓硫酸、石墨粉的重量比为8:2:30:15,将预氧化后的石墨烯溶液溶于水中,得到石墨烯溶液,再加入分散剂和高分子聚合物,混合搅拌,得到石墨烯分散液,分散剂用量为石墨烯溶液质量的0.1%;Step 1: Pre-oxidize the graphene, that is, weigh phosphorus pentoxide, potassium persulfate and concentrated sulfuric acid, seal them in a container, heat them to 75-85°C in a water bath, and stir in a water bath until all the raw materials are dissolved. Graphene was slowly added, and the reaction was kept for 4-8 hours. After the reaction was over, washed with deionized water until neutral, and dried at 40-60°C for 20-28 hours. The above-mentioned phosphorus pentoxide, potassium persulfate, concentrated sulfuric acid, graphite powder The weight ratio is 8:2:30:15, dissolving the pre-oxidized graphene solution in water to obtain a graphene solution, then adding a dispersant and a high molecular polymer, mixing and stirring to obtain a graphene dispersion liquid, a dispersant The dosage is 0.1% of the mass of the graphene solution;
步骤2:将丙烯酰胺单体和交联剂加入到石墨烯分散液中,混合搅拌,并进行预加热,得到预加热溶液,丙烯酰胺单体用量为石墨烯分散液质量的6%;交联剂与丙烯酰胺单体的摩尔比为1:20;Step 2: adding the acrylamide monomer and the crosslinking agent into the graphene dispersion, mixing and stirring, and preheating to obtain a preheated solution, and the amount of the acrylamide monomer is 6% of the mass of the graphene dispersion; crosslinking The molar ratio of agent to acrylamide monomer is 1:20;
步骤3:将步骤②所得的混合物继续升温加入引发剂、促凝剂、硅烷偶联剂,引发剂为过硫酸盐引发剂,促凝剂为四甲基乙二胺,引发剂用量为丙烯酰胺单体和交联剂总质量的1.5%;促凝剂用量为预加热溶液体积的0.05%,其中石墨烯分散液质量与硼酸的质量比为100:2,蒸除有机溶剂后再升温使该高分子聚合物完全固化,升温过程中充分搅拌造粒,获得表面包覆高分子聚合物的石墨复合材料,冷却至室温;Step 3: Continue to heat up the mixture obtained in step ②, add initiator, coagulant and silane coupling agent, the initiator is persulfate initiator, the coagulant is tetramethylethylenediamine, and the amount of initiator is acrylamide 1.5% of the total mass of the monomer and crosslinking agent; the amount of the coagulant is 0.05% of the volume of the preheated solution, and the mass ratio of the graphene dispersion to the boric acid is 100:2. After the organic solvent is evaporated, the temperature is raised to make the The high-molecular polymer is completely solidified, and the granulation is fully stirred during the heating process to obtain a graphite composite material coated with the high-molecular polymer, and cooled to room temperature;
步骤4:将步骤③冷却后的表面包覆高分子聚合物的石墨复合材料进行常规炭化处理。Step 4: performing conventional carbonization treatment on the graphite composite material whose surface is coated with high molecular polymer after cooling in step ③.
所述高分子聚合物选取环氧树脂。The high molecular polymer is selected from epoxy resin.
所述步骤3中还添加有氧化锌和氧化钙,其中石墨烯分散液质量与氧化锌和氧化钙的质量比为100:1:1。Also added zinc oxide and calcium oxide in described step 3, wherein the mass ratio of graphene dispersion liquid to zinc oxide and calcium oxide is 100:1:1.
将制得的改性石墨作负极,钴酸锂作正极,1M-LiPF6 EC∶DMC∶EMC=1∶1∶1溶液作电解液装配成全电池,以3C放电的容量是0.5C放电容量的85%,以2C放电的容量是0.5C放电容量的95%,且以1C充放300周容量保持率在91%。The obtained modified graphite is used as the negative electrode, lithium cobalt oxide is used as the positive electrode, and the 1M-LiPF6 EC:DMC:EMC=1:1:1 solution is used as the electrolyte to assemble a full battery. The discharge capacity at 3C is 85% of the discharge capacity at 0.5C. %, the discharge capacity at 2C is 95% of the discharge capacity at 0.5C, and the capacity retention rate at 1C for 300 cycles is 91%.
实施例3:一种适用于冷喷涂的石墨烯材料制备方法,包括如下步骤:Embodiment 3: a kind of graphene material preparation method applicable to cold spraying, comprises the steps:
步骤1:将石墨烯进行预氧化,即称取五氧化二磷、过硫酸钾、浓硫酸于容器中密封,水浴加热至75-85℃,在水浴中搅拌,直至原料全部溶解,少量多次缓慢的加入石墨烯,保温反应4-8h,反应结束后,使用去离子水洗至中性后,40-60℃干燥20-28h备用,上述五氧化二磷、过硫酸钾、浓硫酸、石墨粉的重量比为8:2:30:15,将预氧化后的石墨烯溶液溶于水中,得到石墨烯溶液,再加入分散剂和高分子聚合物,混合搅拌,得到石墨烯分散液,分散剂用量为石墨烯溶液质量的0.2%;Step 1: Pre-oxidize the graphene, that is, weigh phosphorus pentoxide, potassium persulfate and concentrated sulfuric acid, seal them in a container, heat them to 75-85°C in a water bath, and stir in a water bath until all the raw materials are dissolved. Graphene was slowly added, and the reaction was kept for 4-8 hours. After the reaction was over, washed with deionized water until neutral, and dried at 40-60°C for 20-28 hours. The above-mentioned phosphorus pentoxide, potassium persulfate, concentrated sulfuric acid, graphite powder The weight ratio is 8:2:30:15, dissolving the pre-oxidized graphene solution in water to obtain a graphene solution, then adding a dispersant and a high molecular polymer, mixing and stirring to obtain a graphene dispersion liquid, a dispersant The dosage is 0.2% of the mass of the graphene solution;
步骤2:将丙烯酰胺单体和交联剂加入到石墨烯分散液中,混合搅拌,并进行预加热,得到预加热溶液,丙烯酰胺单体用量为石墨烯分散液质量的5%~7%;交联剂与丙烯酰胺单体的摩尔比为1:22;Step 2: adding the acrylamide monomer and the crosslinking agent into the graphene dispersion, mixing and stirring, and preheating to obtain a preheated solution, and the amount of the acrylamide monomer is 5% to 7% of the mass of the graphene dispersion ; The molar ratio of crosslinking agent to acrylamide monomer is 1:22;
步骤3:将步骤②所得的混合物继续升温加入引发剂、促凝剂、硅烷偶联剂,引发剂为过硫酸盐引发剂,促凝剂为四甲基乙二胺,引发剂用量为丙烯酰胺单体和交联剂总质量的2%;促凝剂用量为预加热溶液体积的0.05%,其中石墨烯分散液质量与硼酸的质量比为100:2,蒸除有机溶剂后再升温使该高分子聚合物完全固化,升温过程中充分搅拌造粒,获得表面包覆高分子聚合物的石墨复合材料,冷却至室温;Step 3: Continue to heat up the mixture obtained in step ②, add initiator, coagulant and silane coupling agent, the initiator is persulfate initiator, the coagulant is tetramethylethylenediamine, and the amount of initiator is acrylamide 2% of the total mass of the monomer and crosslinking agent; the amount of the coagulant is 0.05% of the volume of the preheated solution, wherein the mass ratio of the graphene dispersion to the boric acid is 100:2, and the temperature is raised after the organic solvent is evaporated to make the The high-molecular polymer is completely solidified, and the granulation is fully stirred during the heating process to obtain a graphite composite material coated with the high-molecular polymer, and cooled to room temperature;
步骤4:将步骤③冷却后的表面包覆高分子聚合物的石墨复合材料进行常规炭化处理。Step 4: performing conventional carbonization treatment on the graphite composite material whose surface is coated with high molecular polymer after cooling in step ③.
所述高分子聚合物选取环氧树脂。The high molecular polymer is selected from epoxy resin.
所述步骤3中还添加有氧化锌和氧化钙,其中石墨烯分散液质量与氧化锌和氧化钙的质量比为100:1:1。Also added zinc oxide and calcium oxide in described step 3, wherein the mass ratio of graphene dispersion liquid to zinc oxide and calcium oxide is 100:1:1.
将制得的改性石墨作负极,钴酸锂作正极,1M-LiPF6 EC∶DMC∶EMC=1∶1∶1溶液作电解液装配成全电池,以3C放电的容量是0.5C放电容量的85%,以2C放电的容量是0.5C放电容量的95%,且以1C充放300周容量保持率在91%。The obtained modified graphite is used as the negative electrode, lithium cobalt oxide is used as the positive electrode, and the 1M-LiPF6 EC:DMC:EMC=1:1:1 solution is used as the electrolyte to assemble a full battery. The discharge capacity at 3C is 85% of the discharge capacity at 0.5C. %, the discharge capacity at 2C is 95% of the discharge capacity at 0.5C, and the capacity retention rate at 1C for 300 cycles is 91%.
以上所述仅为本发明的较佳实施例,并不用于限制本发明,凡在本发明的设计构思之内,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 are only preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the design concept of the present invention shall be included in the protection scope of the present invention. within.
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