CN102601383A - Method for preparing ultrafine copper powder at room temperature - Google Patents
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 35
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 42
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 41
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 20
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 20
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 20
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 18
- 239000007791 liquid phase Substances 0.000 claims abstract description 17
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims abstract description 16
- 239000003223 protective agent Substances 0.000 claims abstract description 11
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 7
- 238000006722 reduction reaction Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 14
- 150000001879 copper Chemical class 0.000 claims description 12
- 239000012266 salt solution Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 230000000694 effects Effects 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000012429 reaction media Substances 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 231100000331 toxic Toxicity 0.000 abstract description 3
- 230000002588 toxic effect Effects 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 238000009826 distribution Methods 0.000 abstract description 2
- 239000000376 reactant Substances 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 abstract 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 15
- 229910052802 copper Inorganic materials 0.000 description 14
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 9
- 229910001431 copper ion Inorganic materials 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- JRBNTSDEPVFFNT-UHFFFAOYSA-L C(CO)O.C(C)(=O)[O-].[Cu+2].C(C)(=O)[O-] Chemical compound C(CO)O.C(C)(=O)[O-].[Cu+2].C(C)(=O)[O-] JRBNTSDEPVFFNT-UHFFFAOYSA-L 0.000 description 1
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 1
- SBJKKFFYIZUCET-JLAZNSOCSA-N Dehydro-L-ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(=O)C1=O SBJKKFFYIZUCET-JLAZNSOCSA-N 0.000 description 1
- SBJKKFFYIZUCET-UHFFFAOYSA-N Dehydroascorbic acid Natural products OCC(O)C1OC(=O)C(=O)C1=O SBJKKFFYIZUCET-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229930003268 Vitamin C Natural products 0.000 description 1
- CIMUUFUVEIMCEI-UHFFFAOYSA-J [Cu+2].[Cu+2].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O Chemical compound [Cu+2].[Cu+2].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O CIMUUFUVEIMCEI-UHFFFAOYSA-J 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- -1 copper salt Chemical class 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 235000020960 dehydroascorbic acid Nutrition 0.000 description 1
- 239000011615 dehydroascorbic acid Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
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- 239000012847 fine chemical Substances 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
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- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
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- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
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- 239000011882 ultra-fine particle Substances 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
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Abstract
Description
技术领域 technical field
本发明属于材料技术领域，涉及功能材料，尤其是室温条件下超细铜粉的制备方法。The invention belongs to the technical field of materials and relates to functional materials, especially a method for preparing ultrafine copper powder at room temperature.
背景技术 Background technique
超细金属颗粒的表面效应、小尺寸效应、量子效应和宏观隧道效应使其在集成电路、催化、润滑、抗菌、电磁屏蔽等领域具有极其重要的应用价值。目前一些贵金属的超细微粒如金、铂、银都已得到了广泛的研究，而金属铜微粒易被氧化、颗粒分散性较差且形貌不易控制，所以相关研究较少。相比于贵金属微粒，金属铜的价格相对低廉，并且具有良好的导电性，这使其具有广泛的应用前景。The surface effect, small size effect, quantum effect and macroscopic tunnel effect of ultrafine metal particles make them have extremely important application value in the fields of integrated circuits, catalysis, lubrication, antibacterial, electromagnetic shielding and so on. At present, ultrafine particles of some noble metals such as gold, platinum, and silver have been extensively studied, while metal copper particles are easily oxidized, have poor particle dispersibility, and are not easy to control the shape, so there are few related studies. Compared with noble metal particles, metal copper is relatively cheap and has good electrical conductivity, which makes it have a wide range of application prospects.
目前制备超细铜粉的方法主要有球磨法、气相蒸发法、微乳液法、电解法、γ射线辐照法、溶胶-凝胶法、超临界流体干燥法、液相还原法等。其中液相还原法由于其制备成本低、设备简单易得、反应容易控制等优点而具有重要研究价值。然而通常液相还原法制备超细铜粉的关键步骤，即铜离子被还原剂还原成金属铜这一反应步骤通常需要提供较高的反应温度。较高的反应温度造成了成本的增加、升温的环节消耗了时间，这限制了液相还原法制备超细铜粉的发展。At present, the methods for preparing ultrafine copper powder mainly include ball milling method, gas phase evaporation method, microemulsion method, electrolysis method, gamma ray irradiation method, sol-gel method, supercritical fluid drying method, liquid phase reduction method, etc. Among them, the liquid-phase reduction method has important research value because of its advantages such as low preparation cost, simple and easy-to-obtain equipment, and easy control of the reaction. However, the key step in the preparation of ultrafine copper powder by the liquid phase reduction method, that is, the reaction step of reducing copper ions to metallic copper by a reducing agent, usually requires a higher reaction temperature. The higher reaction temperature increases the cost and consumes time in the heating process, which limits the development of liquid phase reduction method to prepare ultrafine copper powder.
Kyoohee Woo[参考文献Kyoohee Woo，Kongjo Kim，Jang Sub Kim，Soonkwon Lim，JoohoMoon.Ink-Jet Printing of Cu-Ag-Based Highly Conductive Tracks on a TransparentSubstrate[J].Langmuir，2009，Vol25(1)：429～433.]等人以聚乙烯吡咯烷酮为分散剂，以次亚磷酸钠为还原剂在一缩二乙二醇体系中还原硫酸铜，制得了超细铜粉，但是该反应需要140℃的反应温度。Kyoohee Woo[References Kyoohee Woo, Kongjo Kim, Jang Sub Kim, Soonkwon Lim, JoohoMoon. Ink-Jet Printing of Cu-Ag-Based Highly Conductive Tracks on a Transparent Substrate[J]. Langmuir, 2009, Vol25(1): 429 ~433.] and others used polyvinylpyrrolidone as a dispersant and sodium hypophosphite as a reducing agent to reduce copper sulfate in a diethylene glycol system to obtain ultra-fine copper powder, but this reaction requires a reaction at 140 ° C temperature.
公开号为CN 1188700A的中国专利申请提供了一种在液相中用连二亚硫酸钠还原二价铜离子制备超细铜粉的方法，但是该方法在铜离子被还原成金属铜微粒的步骤中需要40～100℃的反应温度。Publication number is that the Chinese patent application of CN 1188700A provides a kind of method in liquid phase with divalent copper ion reduction divalent copper ions to prepare superfine copper powder, but this method needs to be reduced to the step of metal copper particle in
公开号为CN 101195170A的中国专利申请提供了一种采用两步还原将二价铜离子还原为超细铜粉的方法，但是该方法在第一步和第二步还原时都需要提供60～80℃的环境温度。Publication number is that the Chinese patent application of CN 101195170A provides a kind of method that adopts two-step reduction that divalent copper ion is reduced into superfine copper powder, but this method all needs to provide 60～80 °C ambient temperature.
以上方法得到的超细铜粉都需要在铜离子被还原成金属铜的这一步骤中提供较高的反应温度，并且液相还原法制备超细铜粉过程中使用的还原剂大都为甲醛、水合肼等有毒试剂。这在很大程度上制约了液相还原法制备超细铜粉的工业生产和实际应用。The ultra-fine copper powder obtained by the above methods needs to provide a higher reaction temperature in the step where copper ions are reduced to metallic copper, and the reducing agent used in the preparation of ultra-fine copper powder by the liquid phase reduction method is mostly formaldehyde, Toxic reagents such as hydrazine hydrate. This largely restricts the industrial production and practical application of liquid-phase reduction method to prepare ultra-fine copper powder.
发明内容 Contents of the invention
本发明旨在提供一种室温下制备超细铜粉的方法，以解决反应温度对液相还原法制备超细铜粉的限制，该方法设备简单、不需热源、工艺流程短、成本低、制备出的超细铜粉纯度高、分散性好，且制备过程中采用的原料对人体无害，对环境友好。The present invention aims to provide a method for preparing ultrafine copper powder at room temperature to solve the limitation of reaction temperature on the preparation of ultrafine copper powder by liquid phase reduction method. The method has simple equipment, no heat source, short process flow, low cost, The prepared ultrafine copper powder has high purity and good dispersibility, and the raw materials used in the preparation process are harmless to human body and friendly to the environment.
本发明详细技术方案为：Detailed technical scheme of the present invention is:
一种室温下制备超细铜粉的方法，如图1所示，包括以下步骤：A method for preparing ultrafine copper powder at room temperature, as shown in Figure 1, comprises the following steps:
步骤1：配制铜盐溶液。以乙酸铜为溶质，乙二醇为溶剂，配制乙酸铜的乙二醇溶液作为铜盐溶液，其中乙酸铜的质量浓度控制在2.9g/L～20g/L之间。Step 1: Prepare copper salt solution. With copper acetate as the solute and ethylene glycol as the solvent, prepare the ethylene glycol solution of copper acetate as the copper salt solution, wherein the mass concentration of copper acetate is controlled between 2.9g/L and 20g/L.
步骤2：配制还原性保护溶液。以抗坏血酸为还原剂，聚乙烯吡咯烷酮为保护剂，将所述还原剂和保护剂溶于乙二醇中，得到还原性保护溶液；其中所述还原剂的质量浓度控制在11g/L～50g/L之间，所述保护剂的质量浓度控制在2.5g/L～100g/L之间。Step 2: Prepare a reducing protection solution. Ascorbic acid is used as a reducing agent, polyvinylpyrrolidone is used as a protecting agent, and the reducing agent and protecting agent are dissolved in ethylene glycol to obtain a reducing protective solution; wherein the mass concentration of the reducing agent is controlled at 11g/L～50g/L L, the mass concentration of the protective agent is controlled between 2.5g/L-100g/L.
步骤3：液相还原反应。在室温条件下将步骤1配制的铜盐溶液和步骤2配制的还原性保护溶液按照乙酸铜∶抗坏血酸＝1∶(2～10)的摩尔比进行混合，同时进行搅拌。Step 3: Liquid phase reduction reaction. At room temperature, the copper salt solution prepared in step 1 and the reducing protection solution prepared in step 2 are mixed according to the molar ratio of copper acetate:ascorbic acid=1:(2-10), while stirring.
步骤4：收集步骤3液相还原反应所得固体物，经无水乙醇洗涤、真空干燥，得到最终的超细铜粉。Step 4: Collect the solid obtained in the liquid-phase reduction reaction in Step 3, wash with absolute ethanol, and dry in vacuum to obtain the final ultrafine copper powder.
本发明的实质是采用乙酸铜和抗坏血酸为反应物，在乙二醇为溶剂的无水体系下反应生成金属铜，反应式为C6H8O6+Cu(CH3COO)2→Cu+C6H6O6+2CH3COOH。在原料选取方面，采用对人体无毒副作用且对环境友好、无污染的抗坏血酸(即维生素C)和弱酸性铜盐乙酸铜。在乙二醇介质中，抗坏血酸可以脱去两个羟基上的氢与铜离子在室温下反应，还原出金属铜，而抗坏血酸的氧化产物脱氢抗坏血酸易被还原回抗坏血酸，便于回收再利用。若改用硫酸铜、硝酸铜或氯化铜等强酸性金属铜盐，则在室温下不能与抗坏血酸反应得到金属铜。以乙二醇作为反应介质，是应为乙二醇的粘度适中，有利于还原出的铜粉分散，同时也对铜粉起保护作用，若改用其它多元醇作为反应介质，会不利于反应物的分散从而无法得到超细铜粉。聚乙烯吡咯烷酮是精细化工产业中常用的一种表面活性剂，对人体伤害很小，在该反应中既是保护剂，也是表面活性剂，同时还起到加快金属铜晶核形成的作用。The essence of the present invention is to use copper acetate and ascorbic acid as reactants to react in an anhydrous system with ethylene glycol as a solvent to generate metal copper, and the reaction formula is C 6 H 8 O 6 +Cu(CH 3 COO) 2 →Cu+ C 6 H 6 O 6 +2CH 3 COOH. In terms of raw material selection, ascorbic acid (that is, vitamin C) and weakly acidic copper salt copper acetate are used, which have no toxic and side effects on the human body, are environmentally friendly, and have no pollution. In ethylene glycol medium, ascorbic acid can remove the hydrogen on the two hydroxyl groups and react with copper ions at room temperature to reduce metallic copper, while the oxidation product of ascorbic acid, dehydroascorbic acid, is easily reduced back to ascorbic acid, which is convenient for recycling. If strong acid metal copper salts such as copper sulfate, copper nitrate or copper chloride are used instead, metal copper cannot be obtained by reacting with ascorbic acid at room temperature. The use of ethylene glycol as the reaction medium should be due to the moderate viscosity of ethylene glycol, which is conducive to the dispersion of the reduced copper powder and also protects the copper powder. If other polyols are used as the reaction medium, it will not be conducive to the reaction The dispersion of the material makes it impossible to obtain ultra-fine copper powder. Polyvinylpyrrolidone is a surfactant commonly used in the fine chemical industry. It has little harm to the human body. In this reaction, it is not only a protective agent but also a surfactant, and it also plays a role in accelerating the formation of metal copper crystal nuclei.
需要说明的是：1、本发明制备的超细铜粉，其平均粒径在200纳米左右，反应过程中需要采用过量的还原剂(实际还原剂的摩尔用量是铜盐的2至10倍)，如还原剂的量较少，则反应过程中生成的金属铜会与溶液中的二价铜离子反应生成一价铜离子，不利于金属铜的生成，如还原剂的量过多，则反应生成铜粉的速率增加，即金属铜的晶核成核速率加快，导致晶核聚集，使反应所得铜粉的粒径变大；2、步骤4收集液相还原反应所得固体物的具体方式可以是离心分离的方式；3、步骤4中所述真空干燥的真空度为2～5Pa，干燥温度为50～70℃；4：、步骤3和步骤4的具体液相反应和固体物收集过程，不仅可以待反应全部反应完成之后再进行固体物收集，还可以边反应边收集，从而达到连续生产、提高生产效率的目的。It should be noted that: 1, the ultrafine copper powder prepared by the present invention has an average particle diameter of about 200 nanometers, and excessive reducing agent needs to be used in the reaction process (the molar consumption of the actual reducing agent is 2 to 10 times that of copper salt) , if the amount of reducing agent is small, the metal copper generated in the reaction process will react with the divalent copper ions in the solution to form monovalent copper ions, which is not conducive to the generation of metallic copper. If the amount of reducing agent is too much, the reaction The rate of generating copper powder increases, that is, the nucleation rate of metal copper nucleation speeds up, causing the crystal nuclei to gather, and the particle size of the copper powder obtained by the reaction becomes larger; It is the way of centrifugal separation; 3. The vacuum degree of vacuum drying described in step 4 is 2-5Pa, and the drying temperature is 50-70°C; 4:, the specific liquid phase reaction and solid matter collection process of step 3 and step 4, Not only can the solid matter be collected after all the reactions are completed, but also can be collected while reacting, so as to achieve the purpose of continuous production and improve production efficiency.
综上，本发明的有益效果是：In sum, the beneficial effects of the present invention are:
本发明所述一种室温制备超细铜粉的方法可直接在常温常压下进行，不需要外加热源，便于实施且成本较低；采用对人体无毒副作用、对环境无污染、绿色环保的抗坏血酸作为还原剂，利于回收再利用；制备的超细铜粉尺寸分布均匀，无团聚，分散性良好；该方法工艺流程简单，反应所需时间较短，便于进行工业生产。A method for preparing superfine copper powder at room temperature according to the present invention can be carried out directly at normal temperature and pressure, without the need for an external heating source, and is easy to implement and low in cost; it adopts a non-toxic and side effect to human body, no pollution to the environment, and is environmentally friendly. Ascorbic acid is used as a reducing agent, which is beneficial to recycling and reuse; the prepared ultrafine copper powder has uniform size distribution, no agglomeration, and good dispersibility; the process of the method is simple, the reaction time is short, and it is convenient for industrial production.
附图说明 Description of drawings
图1为本发明流程示意图。Fig. 1 is a schematic flow chart of the present invention.
图2为本发明所制得的超细铜粉的扫描电镜图像。Fig. 2 is the scanning electron microscope image of the ultrafine copper powder that the present invention makes.
图3为本发明所制得的超细铜粉的能谱成分分析图。Figure 3 is an energy spectrum component analysis diagram of the ultrafine copper powder prepared by the present invention.
图4为本发明所制得的超细铜粉的X射线衍射图。Fig. 4 is the X-ray diffraction figure of the ultrafine copper powder that the present invention makes.
具体实施方式 Detailed ways
一种室温下制备超细铜粉的方法，包括以下步骤：A method for preparing superfine copper powder at room temperature, comprising the following steps:
步骤1：配制铜盐溶液；以乙酸铜为溶质，乙二醇为溶剂，配制乙酸铜的乙二醇溶液作为铜盐溶液，其中乙酸铜的质量浓度控制在2.9g/L～20g/L之间；Step 1: Prepare copper salt solution; use copper acetate as solute and ethylene glycol as solvent, prepare copper acetate ethylene glycol solution as copper salt solution, wherein the mass concentration of copper acetate is controlled between 2.9g/L～20g/L between;
步骤2：配制还原性保护溶液；以抗坏血酸为还原剂，聚乙烯吡咯烷酮为保护剂，将所述还原剂和保护剂溶于乙二醇中，得到还原性保护溶液；其中所述还原剂的质量浓度控制在11g/L～50g/L之间，所述保护剂的质量浓度控制在2.5g/L～100g/L之间；Step 2: preparing a reducing protection solution; using ascorbic acid as a reducing agent and polyvinylpyrrolidone as a protecting agent, dissolving the reducing agent and the protecting agent in ethylene glycol to obtain a reducing protection solution; the mass of the reducing agent The concentration is controlled between 11g/L～50g/L, and the mass concentration of the protective agent is controlled between 2.5g/L～100g/L;
步骤3：液相还原反应；在室温条件下将步骤1配制的铜盐溶液和步骤2配制的还原性保护溶液按照乙酸铜∶抗坏血酸＝1∶(2～10)的摩尔比进行混合，同时进行搅拌；Step 3: liquid phase reduction reaction; under room temperature, the copper salt solution prepared in step 1 and the reducing protection solution prepared in step 2 are mixed according to the molar ratio of copper acetate: ascorbic acid=1: (2～10), and carry out simultaneously stir;
步骤4：对步骤3液相还原反应所得固体物进行离心分离，并经无水乙醇洗涤、真空干燥，得到最终的超细铜粉。其中真空干燥的真空度为2～5Pa，干燥温度为50～70℃。Step 4: Centrifuge the solid obtained in the liquid-phase reduction reaction in Step 3, wash with absolute ethanol, and dry in vacuum to obtain the final ultrafine copper powder. Wherein the vacuum degree of vacuum drying is 2-5Pa, and the drying temperature is 50-70°C.
按照上述方案并按下表所述不同铜盐溶液浓度、不同抗坏血酸还原性保护溶液浓度和不同铜盐与抗坏血酸摩尔比制备出多种超细铜粉样品。其中样品1的扫描电镜测试结果如图2所示，其能谱成分分析和X射线衍射分析结果分别如图3和图4所示。能谱成分分析和X射线衍射分析结果表明制得的样品为金属铜，扫描电镜测试结果表明所得铜粉平均粒径为200nm。其余样品分析测试方法与样品1相同、测试结果类似。A variety of ultrafine copper powder samples were prepared according to the above scheme and with different copper salt solution concentrations, different ascorbic acid reducing protection solution concentrations and different copper salt to ascorbic acid molar ratios as described in the table below. The scanning electron microscope test results of sample 1 are shown in Figure 2, and the energy spectrum component analysis and X-ray diffraction analysis results are shown in Figure 3 and Figure 4, respectively. The results of energy spectrum component analysis and X-ray diffraction analysis showed that the prepared sample was metallic copper, and the scanning electron microscope test results showed that the average particle size of the obtained copper powder was 200nm. The rest of the samples were analyzed and tested in the same way as sample 1, and the test results were similar.
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