WO2019104460A1 - 一种复合导电浆料的制备方法 - Google Patents

一种复合导电浆料的制备方法 Download PDF

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WO2019104460A1
WO2019104460A1 PCT/CN2017/113289 CN2017113289W WO2019104460A1 WO 2019104460 A1 WO2019104460 A1 WO 2019104460A1 CN 2017113289 W CN2017113289 W CN 2017113289W WO 2019104460 A1 WO2019104460 A1 WO 2019104460A1
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conductive paste
stabilizer
composite conductive
reaction
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桑胜伟
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桑胜伟
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Priority to CN201780097247.1A priority Critical patent/CN111492529B/zh
Priority to PCT/CN2017/113289 priority patent/WO2019104460A1/zh
Publication of WO2019104460A1 publication Critical patent/WO2019104460A1/zh

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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
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • 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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  • the invention belongs to the field of electrode materials, and in particular relates to a preparation method of a composite conductive paste.
  • Conductive paste has been used in many fields such as IT display, electrical enclosure, gas sensor, solar photovoltaic conversion, etc. Broad application.
  • the conductive phase of the electronic paste is mainly composed of precious metal powders such as platinum, palladium, gold, and silver, and the price of silver is relatively low, so the commercialization degree of the silver paste is the highest. In recent years, the price of silver has become higher and higher, and the production cost of silver paste has also increased, coupled with the problem of silver ion migration in the silver paste itself.
  • Porous Si is a novel one-dimensional nanophotonic crystal material with a "quantum sponge"-like microstructure with a nano-silicon cluster as a skeleton, which can be formed by electrochemical anodic corrosion or chemical etching of single crystal silicon.
  • Uhlir of Bell Labs, USA first discovered and reported that porous silicon films can be formed by electrochemical etching. Uhlir found that in the case of a small anodic current density, electrochemical etching of single crystal silicon in a concentrated hydrofluoric acid electrolyte resulted in a film of porous structure different from that of a bright polished surface, namely porous silicon. Then in 1958, D.
  • the size of silicon in nanoporous silicon is smaller than the Bohr radius of the exciton, which has a significant quantum confinement effect, causing its band to split and its bandwidth to increase.
  • the band gap energy is a function of the size of the silicon column.
  • porous silicon is an indirect bandgap semiconductor, the emission spectrum is wide, and the wavelength range is from the ultraviolet region to the near-infrared region, and the quantum efficiency of photoluminescence is between 1% and 10%.
  • the peak position and intensity of porous silicon photoluminescence are related to porosity. Porosity is the percentage of the pore volume in the porous silicon layer to the total volume of the etched silicon layer. When the porosity is greater than 80%, the photoluminescence ability is strong.
  • porous layer having a large porosity has a fast decay of light and is not stable enough.
  • the band gap structure can be inferred by the study of photoluminescence spectroscopy And electron-phonon coupling.
  • Porous silicon also has good reflective properties, and its reflectance spectrum can be as high as 99% in a certain wavelength range.
  • Porous silicon has good electroluminescence properties, and can generate electrons and holes under the excitation of light or electricity. These carriers can be combined to emit light, and can be directionally moved under the action of an electric field to generate electrical signals and also store energy.
  • porous silicon The optical and electrical properties of porous silicon have opened up new avenues for the integration and development of all-silicon-based optoelectronics, and have rapidly led to a research boom in porous silicon at home and abroad.
  • the conductivity of porous silicon is inferior to that of metal ions, and there is a problem of dispersion type.
  • the present invention provides a method for preparing a composite conductive paste.
  • the composite conductive paste prepared by the invention has high conductivity, high stability, and is not easy to agglomerate, and has simple process, low cost and convenient industrial production. .
  • a method for preparing a composite conductive paste comprising the steps of:
  • the composite powder, the binder and the deionized water are uniformly mixed to obtain a mixed solution, and the mixture is ultrasonicated for 0.5 to 1 hour to obtain a composite conductive paste.
  • the weight ratio of the porous silicon to the carbon source in the step (1) is 1 - 5:1.
  • the stabilizer in the step (1) is an organotin stabilizer or an organic hydrazine stabilizer.
  • the zinc oxide in the step (2) is prepared by slowly adding a NaOH ethanol solution having a concentration of 0.01 mol/L to a concentration of 0.01 mol/L of ZnNO 3 ethanol to obtain a mixed solution, and mixing the solution.
  • the reaction is carried out in a reaction vessel, the reaction time is 10-11 hours, the reaction temperature is 120-135 ° C, and the reaction product is obtained after the reaction, and the reaction product is washed and dried to obtain zinc oxide.
  • the inert gas in the step (3) is helium, neon or argon.
  • the invention has the following beneficial effects:
  • the invention reacts at a high temperature by a porous silicon source and a carbon source to form a silicon-bonded carbon bond to form a silicon oxycarbon polymer, and a part of the porous silicon undergoes a redox reaction to form a silica, and most of the carbon source reacts with the carbon source to form a silicon oxide polymer.
  • the surface has a variety of composites coated with in-situ carbon to increase conductivity.
  • the slurry can be made more stable, and tin and antimony are metal ions, and also have a conductive effect.
  • the composite conductive paste prepared by the invention has high conductivity, high stability, and is not easy to agglomerate, and has the advantages of simple process, low cost and convenient industrial production.
  • a method for preparing a composite conductive paste comprising the steps of:
  • the weight ratio of the porous silicon to the carbon source in the step (1) is 1:1.
  • the stabilizer in the step (1) is an organotin stabilizer.
  • the zinc oxide in the step (2) is prepared by slowly adding a NaOH ethanol solution having a concentration of 0.01 mol/L to a concentration of 0.01 mol/L of ZnNO 3 ethanol to obtain a mixed solution, and placing the mixed solution in the reaction.
  • the reaction in the kettle was carried out for 10 hours, the reaction temperature was 120 ° C, and the reaction product was obtained after the reaction.
  • the reaction product was washed and dried to obtain zinc oxide.
  • the inert gas in the step (3) is helium.
  • a method for preparing a composite conductive paste comprising the steps of:
  • the weight ratio of the porous silicon to the carbon source in the step (1) is 5:1.
  • the stabilizer in the step (1) is an organotin stabilizer.
  • the zinc oxide in the step (2) is prepared by slowly adding a NaOH ethanol solution having a concentration of 0.01 mol/L to a concentration of 0.01 mol/L of ZnNO 3 ethanol to obtain a mixed solution, and placing the mixed solution in the reaction.
  • the reaction in the kettle was carried out for 11 hours, the reaction temperature was 135 ° C, and the reaction product was obtained after the reaction.
  • the reaction product was washed and dried to obtain zinc oxide.
  • the inert gas in the step (3) is helium.
  • a method for preparing a composite conductive paste comprising the steps of:
  • the nano powder a and the nano powder b are uniformly mixed, placed in a tube furnace with an inert gas reflux, and heated to 1000 ° C at a heating rate of 8 ° C / minute, and after cooling for 2.5 hours, the mixture is cooled to room temperature to obtain a composite. powder;
  • the weight ratio of the porous silicon to the carbon source in the step (1) is 3:1.
  • the stabilizer in the step (1) is an organotin stabilizer or an organic hydrazine stabilizer.
  • the zinc oxide in the step (2) is prepared by slowly adding a NaOH ethanol solution having a concentration of 0.01 mol/L to a concentration of 0.01 mol/L of ZnNO 3 ethanol to obtain a mixed solution, and placing the mixed solution in the reaction.
  • the reaction in the kettle was carried out for 10.5 hours, the reaction temperature was 130 ° C, and the reaction product was obtained after the reaction.
  • the reaction product was washed and dried to obtain zinc oxide.
  • the inert gas in the step (3) is argon.
  • a method for preparing a composite conductive paste comprising the steps of:
  • the weight ratio of the porous silicon to the carbon source in the step (1) is 5:1.
  • the stabilizer in the step (1) is an organotin stabilizer.
  • the zinc oxide in the step (2) is prepared by slowly adding a NaOH ethanol solution having a concentration of 0.01 mol/L to a concentration of 0.01 mol/L of ZnNO 3 ethanol to obtain a mixed solution, and placing the mixed solution in the reaction.
  • the reaction in the kettle was carried out for 11 hours, the reaction temperature was 135 ° C, and the reaction product was obtained after the reaction.
  • the reaction product was washed and dried to obtain zinc oxide.
  • the inert gas in the step (3) is helium.
  • Example 2 The procedure was the same as in Example 2 except that the nanopowder b was not added.
  • a method for preparing a composite conductive paste comprising the steps of:
  • the weight ratio of the porous silicon to the carbon source in the step (1) is 5:1.
  • the stabilizer in the step (1) is an organotin stabilizer.
  • the inert gas in the step (2) is helium.
  • a method for preparing a composite conductive paste comprising the steps of:
  • the weight ratio of the porous silicon to the carbon source in the step (1) is 3:1.
  • the stabilizer in the step (1) is an organotin stabilizer or an organic hydrazine stabilizer.
  • the zinc oxide in the step (2) is prepared by slowly adding a NaOH ethanol solution having a concentration of 0.01 mol/L to a concentration of 0.01 mol/L of ZnNO 3 ethanol to obtain a mixed solution, and placing the mixed solution in the reaction.
  • the reaction in the kettle was carried out for 10.5 hours, the reaction temperature was 130 ° C, and the reaction product was obtained after the reaction.
  • the reaction product was washed and dried to obtain zinc oxide.
  • Example 1-3 The composite conductive paste prepared in Example 1-3 and Comparative Example 1-3 was allowed to stand for 3 days, observed and tested for performance. The results are shown in Table 1:
  • Example 1-3 The composite conductive paste obtained in Example 1-3 and Comparative Example 1-3 was applied to both sides of a conventional aluminum foil of a 16 u lithium battery by a spray coating technique, and the thickness of the single-sided coating was 1 u-1.5 u, and the double-sided coating material was dried.
  • the thickness is 2u ⁇ 3u, and the performance test, the results are shown in Table 2:
  • the composite conductive paste obtained by the preparation method of the present invention has excellent properties.

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  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Adhesives Or Adhesive Processes (AREA)
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Abstract

一种复合导电浆料的制备方法；通过将多孔硅、碳源和碳酸盐混合均匀放入研磨装置，加入直径为1-2mm的玻璃珠，关闭研磨装置口，研磨处理3-4小时，加入稳定剂，继续研磨处理2-3小时，得到纳米粉末a；将氧化锌和稳定剂加入球磨罐，以100-300转/分钟球磨8-12小时，得到纳米粉末b；将纳米粉末a和纳米粉末b混合均匀，反应得到复合粉末；将复合粉末、粘合剂和去离子水混合均匀得到混合液，将混合液超声处理0.5-1小时，得到复合导电浆料。所制备的复合导电浆料导电性能、稳定性高、不易发生团聚，且工艺简单、成本低、便于工业化生产。

Description

一种复合导电浆料的制备方法 技术领域
本发明属于电极材料领域，具体涉及一种复合导电浆料的制备方法。
背景技术
自从1997年富士胶卷公司在Science杂志上首次报道了复合金属氧化物可作为二次锂电池负极材料以来，导电浆料在IT领域显示器、电器机壳、气敏传感器、太阳能光电转换等众多领域有着广阔的应用。电子浆料的导电相大多以铂、钯、金和银等贵金属粉末为主,银的价格相对较低,所以银浆的商品化程度最高。近几年银的价格越来越高,银浆料的生产成本也随之增加,加之银浆料本身存在的银离子迁移问题。
多孔硅(porous Si)，是一种新型的一维纳米光子晶体材料，具有纳米硅原子簇为骨架的“量子海绵”状微结构，可以通过电化学阳极腐蚀或化学腐蚀单晶硅而形成。早在1956年时，美国贝尔实验室Uhlir首次发现并报道了通过电化学腐蚀法可以形成多孔硅薄膜。Uhlir发现在阳极电流密度较小的情况下，在浓的氢氟酸电解液中对单晶硅进行电化学腐蚀可以得到一层与明亮抛光面不同的多孔结构的薄膜，即多孔硅。随后1958年，D.Turner对阳极氧化法成膜的机理进行了研究，并详细论述了多孔硅薄膜的刻蚀条件及其相关性质。在电化学阳极氧化过程中存在两种情况，当电流密度大于某个临界点时(此临界点与硅片的类型，电阻率，腐蚀液的浓度和成分等因素相关)，发生电化学抛光现象，多孔硅薄膜会从硅基底上被剥落下来。当电流密度低于此临界点时，就会形成具有无数纳米量级的硅柱的多孔硅薄膜。1990年英国科学家Canham用紫外光和氩离子激光室温下照射多孔硅表面时，发现其具有强烈的可见光致发光(Photoluminescence，简称PL)现象。纳米多孔硅中硅的尺寸小于激子的波尔半径，具有明显的量子限制效应，使其能带发生分裂导致其带宽增大，带隙能量是硅柱尺寸的函数。但是由于多孔硅是间接带隙半导体，发射光谱较宽，波长范围从紫外区到近红外区，光致发光的量子效率在1％～10％之间。多孔硅光致发光的峰位置和强度与孔隙率有关。孔隙率即是多孔硅层中孔隙体积占被腐蚀硅层总体积的百分数。当孔隙率大于80％时光致发光的能力很强。但是孔隙率大的多孔层其发光衰减较快，不够稳定。通过光致发光谱的研究可以推知其电子带隙结构 和电子-声子耦合等。多孔硅还具有良好的反射性能，其反射光谱在一定的波长范围内的反射率可高至99％。多孔硅具有良好电致发光特性，在光或电的激发下可产生电子和空穴，这些载流子可以复合发光，在电场的作用下进行定向移动，产生电信号，也可以储能。多孔硅在光学和电学方面的特性为全硅基光电子集成和开发开创了新道路，并迅速引起了国内外对多孔硅的研究热潮。然而多孔硅的导电性不如金属离子，且存在分散型性的问题。
发明内容
针对现有技术中的不足，本发明提供一种复合导电浆料的制备方法，本发明制备的复合导电浆料导电性能、稳定性高、不易发生团聚，且工艺简单、成本低、便于工业化生产。
为了实现上述发明目的，本发明采用了以下技术方案：
一种复合导电浆料的制备方法，包括以下步骤：
(1)将多孔硅、碳源和碳酸盐混合均匀放入研磨装置，加入直径为1-2mm的玻璃珠，关闭研磨装置口，研磨处理3-4小时，加入稳定剂，继续研磨处理2-3小时，得到纳米粉末a；
(2)将氧化锌和稳定剂加入球磨罐，以100-300转/分钟球磨8-12小时，得到纳米粉末b；
(3)将纳米粉末a和纳米粉末b混合均匀，置于惰性气体回流的管式炉中，以6-9℃/分钟升温速率升温至800-1400℃，保温2-3小时后，随炉冷却至室温，得到复合粉末；
(4)将复合粉末、粘合剂和去离子水混合均匀得到混合液，将混合液超声处理0.5-1小时，得到复合导电浆料。
优选地，所述步骤(1)中多孔硅和碳源的重量比为1‐5：1。
优选地，所述步骤(1)中稳定剂为有机锡稳定剂或有机锑稳定剂。
优选地，所述步骤(2)中氧化锌的制备方法为：将浓度为0.01mol/L的NaOH乙醇溶液缓慢滴加到浓度为0.01mol/L的ZnNO3乙醇中得到混合溶液，将混合溶液置于反应釜中反应，反应时间为10-11小时，反应温度为120-135℃，反应后得到反应产物，将反应产物洗涤、干燥后得到氧化锌。
优选地，所述步骤(3)中惰性气体为氦气、氖气或氩气。
本发明与现有技术相比，具有如下有益效果：
1.本发明通过原料多孔硅和碳源在高温下发生反应成为部分硅键连接碳键形成硅碳氧聚合物，部分多孔硅发生氧化还原反应生成二氧化硅，而大部分和碳源反应生成表面有原位碳包覆的多种复合物，增加导电性能。
2.通过在研磨时添加有机锡稳定剂或有机锑稳定剂，能够使得浆料更稳定，且锡和锑为金属离子，也具有导电作用。
3.本发明制备的复合导电浆料导电性能、稳定性高、不易发生团聚，且工艺简单、成本低、便于工业化生产。
具体实施方式
下面通过具体实施方式对本发明作进一步详细说明。但本领域技术人员将会理解，下列实施例仅用于说明本发明，而不应视为限定本发明的范围。实施例中未注明具体技术或条件者，按照本领域内的文献所描述的技术或条件按照说明书进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规产品。
实施例1
一种复合导电浆料的制备方法，包括以下步骤：
(1)将多孔硅、碳源和碳酸盐混合均匀放入研磨装置，加入直径为1mm的玻璃珠，关闭研磨装置口，研磨处理3小时，加入稳定剂，继续研磨处理2小时，得到纳米粉末a；
(2)将氧化锌和稳定剂加入球磨罐，以100转/分钟球磨8小时，得到纳米粉末b；
(3)将纳米粉末a和纳米粉末b混合均匀，置于惰性气体回流的管式炉中，以6℃/分钟升温速率升温至800℃，保温2小时后，随炉冷却至室温，得到复合粉末；
(4)将复合粉末、粘合剂和去离子水混合均匀得到混合液，将混合液超声处理0.5小时，得到复合导电浆料。
所述步骤(1)中多孔硅和碳源的重量比为1：1。
所述步骤(1)中稳定剂为有机锡稳定剂。
所述步骤(2)中氧化锌的制备方法为：将浓度为0.01mol/L的NaOH乙醇溶液缓慢滴加到浓度为0.01mol/L的ZnNO3乙醇中得到混合溶液，将混合溶液置于 反应釜中反应，反应时间为10小时，反应温度为120℃，反应后得到反应产物，将反应产物洗涤、干燥后得到氧化锌。
所述步骤(3)中惰性气体为氦气。
实施例2
一种复合导电浆料的制备方法，包括以下步骤：
(1)将多孔硅、碳源和碳酸盐混合均匀放入研磨装置，加入直径为2mm的玻璃珠，关闭研磨装置口，研磨处理4小时，加入稳定剂，继续研磨处理3小时，得到纳米粉末a；
(2)将氧化锌和稳定剂加入球磨罐，以300转/分钟球磨12小时，得到纳米粉末b；
(3)将纳米粉末a和纳米粉末b混合均匀，置于惰性气体回流的管式炉中，以9℃/分钟升温速率升温至1400℃，保温3小时后，随炉冷却至室温，得到复合粉末；
(4)将复合粉末、粘合剂和去离子水混合均匀得到混合液，将混合液超声处理1小时，得到复合导电浆料。
所述步骤(1)中多孔硅和碳源的重量比为5：1。
所述步骤(1)中稳定剂为有机锡稳定剂。
所述步骤(2)中氧化锌的制备方法为：将浓度为0.01mol/L的NaOH乙醇溶液缓慢滴加到浓度为0.01mol/L的ZnNO3乙醇中得到混合溶液，将混合溶液置于反应釜中反应，反应时间为11小时，反应温度为135℃，反应后得到反应产物，将反应产物洗涤、干燥后得到氧化锌。
所述步骤(3)中惰性气体为氖气。
实施例3
一种复合导电浆料的制备方法，包括以下步骤：
(1)将多孔硅、碳源和碳酸盐混合均匀放入研磨装置，加入直径为1mm的玻璃珠，关闭研磨装置口，研磨处理3.5小时，加入稳定剂，继续研磨处理2.5小时，得到纳米粉末a；
(2)将氧化锌和稳定剂加入球磨罐，以200转/分钟球磨10小时，得到纳米粉末b；
(3)将纳米粉末a和纳米粉末b混合均匀，置于惰性气体回流的管式炉中，以8℃/分钟升温速率升温至1000℃，保温2.5小时后，随炉冷却至室温，得到复合粉末；
(4)将复合粉末、粘合剂和去离子水混合均匀得到混合液，将混合液超声处理1小时，得到复合导电浆料。
所述步骤(1)中多孔硅和碳源的重量比为3：1。
所述步骤(1)中稳定剂为有机锡稳定剂或有机锑稳定剂。
所述步骤(2)中氧化锌的制备方法为：将浓度为0.01mol/L的NaOH乙醇溶液缓慢滴加到浓度为0.01mol/L的ZnNO3乙醇中得到混合溶液，将混合溶液置于反应釜中反应，反应时间为10.5小时，反应温度为130℃，反应后得到反应产物，将反应产物洗涤、干燥后得到氧化锌。
优选地，所述步骤(3)中惰性气体为氩气。
对比例1
步骤同实施例1，不同之处在于步骤(1)中未加入稳定剂。
一种复合导电浆料的制备方法，包括以下步骤：
(1)将多孔硅、碳源和碳酸盐混合均匀放入研磨装置，加入直径为2mm的玻璃珠，关闭研磨装置口，研磨处理7小时，得到纳米粉末a；
(2)将氧化锌和稳定剂加入球磨罐，以300转/分钟球磨12小时，得到纳米粉末b；
(3)将纳米粉末a和纳米粉末b混合均匀，置于惰性气体回流的管式炉中，以9℃/分钟升温速率升温至1400℃，保温3小时后，随炉冷却至室温，得到复合粉末；
(4)将复合粉末、粘合剂和去离子水混合均匀得到混合液，将混合液超声处理1小时，得到复合导电浆料。
所述步骤(1)中多孔硅和碳源的重量比为5：1。
所述步骤(1)中稳定剂为有机锡稳定剂。
所述步骤(2)中氧化锌的制备方法为：将浓度为0.01mol/L的NaOH乙醇溶液缓慢滴加到浓度为0.01mol/L的ZnNO3乙醇中得到混合溶液，将混合溶液置于反应釜中反应，反应时间为11小时，反应温度为135℃，反应后得到反应产物， 将反应产物洗涤、干燥后得到氧化锌。
所述步骤(3)中惰性气体为氖气。
对比例2
步骤同实施例2，不同之处在于未添加纳米粉末b。
一种复合导电浆料的制备方法，包括以下步骤：
(1)将多孔硅、碳源和碳酸盐混合均匀放入研磨装置，加入直径为2mm的玻璃珠，关闭研磨装置口，研磨处理4小时，加入稳定剂，继续研磨处理3小时，得到纳米粉末a；
(2)将纳米粉末a置于惰性气体回流的管式炉中，以9℃/分钟升温速率升温至1400℃，保温3小时后，随炉冷却至室温；将纳米粉末a、粘合剂和去离子水混合均匀得到混合液，将混合液超声处理1小时，得到导电浆料。
所述步骤(1)中多孔硅和碳源的重量比为5：1。
所述步骤(1)中稳定剂为有机锡稳定剂。
所述步骤(2)中惰性气体为氖气。
对比例3
步骤同实施例3，不同之处在于步骤(3)。
一种复合导电浆料的制备方法，包括以下步骤：
(1)将多孔硅、碳源和碳酸盐混合均匀放入研磨装置，加入直径为1mm的玻璃珠，关闭研磨装置口，研磨处理3.5小时，加入稳定剂，继续研磨处理2.5小时，得到纳米粉末a；
(2)将氧化锌和稳定剂加入球磨罐，以200转/分钟球磨10小时，得到纳米粉末b；
(3)将纳米粉末a和纳米粉末b混合均匀，加热反应，加热温度为1000℃，加热时间为2.5小时，得到复合粉末；
(4)将复合粉末、粘合剂和去离子水混合均匀得到混合液，将混合液超声处理1小时，得到复合导电浆料。
所述步骤(1)中多孔硅和碳源的重量比为3：1。
所述步骤(1)中稳定剂为有机锡稳定剂或有机锑稳定剂。
所述步骤(2)中氧化锌的制备方法为：将浓度为0.01mol/L的NaOH乙醇溶 液缓慢滴加到浓度为0.01mol/L的ZnNO3乙醇中得到混合溶液，将混合溶液置于反应釜中反应，反应时间为10.5小时，反应温度为130℃，反应后得到反应产物，将反应产物洗涤、干燥后得到氧化锌。
将实施例1‐3和对比例1‐3制备得到的复合导电浆料静置3天，观察并进行性能测试，所得结果如表1所示：
表1
  肉眼观察有无团聚现象 细度(nm) 流动性(2.5rpm/10.0rpm)
实施例1 无 8 1.7
实施例2 无 10 1.9
实施例3 无 9 1.9
对比例1 轻微 17 1.2
对比例2 轻微 17 1.2
对比例3 轻微 15 1.3
将实施例1‐3和对比例1‐3所得的复合导电浆料用喷涂技术涂于16u锂电池常规铝箔两面，烘干测量使得单面涂层厚度在1u‐1.5u，双面涂层材料厚度在2u‐3u，并性能测试，所得结果如表2所示：
表2
Figure PCTCN2017113289-appb-000001
如表1和表2可见：本发明制备方法所得的复合导电浆料具有优良的性能。
以上所述，仅是本发明较佳的实施例而已，并非对本发明的技术范围作任何限制，故凡是依据本发明的技术实质对以上实施例所做的任何细微修改、等同变化和修饰，均属于本发明技术方案的范围内。

Claims (5)

  1. 一种复合导电浆料的制备方法，其特征在于，包括以下步骤：
    (1)将多孔硅、碳源和碳酸盐混合均匀放入研磨装置，加入直径为1-2mm的玻璃珠，关闭研磨装置口，研磨处理3-4小时，加入稳定剂，继续研磨处理2-3小时，得到纳米粉末a；
    (2)将氧化锌和稳定剂加入球磨罐，以100-300转/分钟球磨8-12小时，得到纳米粉末b；
    (3)将纳米粉末a和纳米粉末b混合均匀，置于惰性气体回流的管式炉中，以6-9℃/分钟升温速率升温至800-1400℃，保温2-3小时后，随炉冷却至室温，得到复合粉末；
    (4)将复合粉末、粘合剂和去离子水混合均匀得到混合液，将混合液超声处理0.5-1小时，得到复合导电浆料。
  2. 根据权利要求1所述的一种复合导电浆料的制备方法，其特征在于，所述步骤(1)中多孔硅和碳源的重量比为1‐5：1。
  3. 根据权利要求1所述的一种复合导电浆料的制备方法，其特征在于，所述步骤(1)中稳定剂为有机锡稳定剂或有机锑稳定剂。
  4. 根据权利要求1所述的一种复合导电浆料的制备方法，其特征在于，所述步骤(2)中氧化锌的制备方法为：将浓度为0.01mol/L的NaOH乙醇溶液缓慢滴加到浓度为0.01mol/L的ZnNO3乙醇中得到混合溶液，将混合溶液置于反应釜中反应，反应时间为10-11小时，反应温度为120-135℃，反应后得到反应产物，将反应产物洗涤、干燥后得到氧化锌。
  5. 根据权利要求1所述的一种复合导电浆料的制备方法，其特征在于，所述步骤(3)中惰性气体为氦气、氖气或氩气。
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