CN104860324A - Method for controlling dispersion particle size of fumed silica - Google Patents
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- CN104860324A CN104860324A CN201510241684.9A CN201510241684A CN104860324A CN 104860324 A CN104860324 A CN 104860324A CN 201510241684 A CN201510241684 A CN 201510241684A CN 104860324 A CN104860324 A CN 104860324A
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910021485 fumed silica Inorganic materials 0.000 title claims abstract description 60
- 239000002245 particle Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 15
- 239000006185 dispersion Substances 0.000 title abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 238000010008 shearing Methods 0.000 claims abstract description 10
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 7
- 230000007423 decrease Effects 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- 239000003349 gelling agent Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Landscapes
- Silicon Compounds (AREA)
Abstract
Description
技术领域 technical field
本发明属于化学电源材料的制备领域，具体涉及一种控制气相二氧化硅分散粒径的方法。 The invention belongs to the field of preparation of chemical power source materials, and in particular relates to a method for controlling the dispersed particle size of fumed silica.
背景技术 Background technique
硫酸电解液的凝胶化是阀控式铅酸蓄电池的重要发展方向，应用气相二氧化硅作为胶凝剂是目前各蓄电池厂家的首选。气相二氧化硅具有很高的化学纯度和很强的触变性，它通过在氢氧焰中燃烧热解硅烷获得原生微粒，微粒经碰撞凝结成含104个或更大数目SiO4单元的支状初级粒子，在冷却过程中这些初级粒子形成了聚集体，聚集体表面硬化后又经范德华力结合成更大的聚集体，这即商品气相二氧化硅通常呈现的形貌。经剪切或剪切超声结合只能得到一定大小的分散粒子，分散粒径不同决定了粒子表面硅羟基种类和数量的不同，因此强烈影响了气相二氧化硅的胶凝特性以及加入蓄电池后的电池性能，控制气相二氧化硅分散粒径成为制备性能优良胶体蓄电池的第一个关键步骤。 The gelation of sulfuric acid electrolyte is an important development direction of valve-regulated lead-acid batteries, and the use of fumed silica as a gelling agent is currently the first choice for battery manufacturers. Fumed silica has high chemical purity and strong thixotropy. It obtains primary particles by burning pyrolyzed silane in an oxygen-hydrogen flame, and the particles condense into branches containing 10 4 or more SiO 4 units During the cooling process, these primary particles form aggregates, and after the surface of the aggregates hardens, they are combined into larger aggregates by van der Waals force, which is the general shape of commercial fumed silica. Only dispersed particles of a certain size can be obtained by shearing or shearing ultrasonic combination. The difference in dispersed particle size determines the difference in the type and quantity of silicon hydroxyl groups on the particle surface, thus strongly affecting the gelation characteristics of fumed silica and the gelation properties after adding the battery. Battery performance, controlling the dispersed particle size of fumed silica has become the first key step in the preparation of high-performance colloidal batteries.
关于气相二氧化硅粒径的重要性早已被意识（Gençten, M.等，J Solid State Electrochem. 2014, 18, 2469–2479；Chen, M.等，Electrochimica Acta 2015, 164, 243–251；Chen, M.等，J. Power Sources 2008, 181, 161-171；Kamiya, H.等，J. Am. Ceram. Soc. 2000, 83, 287-293），但他们都是根据电镜拍摄的原生粒子或初级粒子来考虑这些单元的尺寸（10-50nm）（Park, J.等，J. Non-Crystalline Solids 2005, 351, 2352–2357；Sun, C.等，Applied Mechanics Materials 2012, 110-116, 514-518; Chen, M.等，J. Power Sources 2008, 181, 161-171；Kamiya, H.等，J. Am. Ceram. Soc. 2000, 83, 287-293）。这与实际应用严重不相符，因为商品气相二氧化硅经机械力只能破坏彼此结合的范德华力，即分散只能得到如上所述的聚集体，这时的粒径在100-300nm之间。这种理论与实际的脱节导致对分散这一关键的前处理工艺迄今没有明确的知识指导，严重影响甚至阻碍了气相二氧化硅的实际应用。 The importance of fumed silica particle size has long been recognized (Gençten, M. et al., J Solid State Electrochem. 2014, 18, 2469–2479; Chen, M. et al., Electrochimica Acta 2015, 164, 243–251; Chen , M. et al., J. Power Sources 2008, 181, 161-171; Kamiya, H. et al., J. Am. Ceram. Soc. 2000, 83, 287-293), but they are all primary particle or primary particles to consider the size of these units (10-50nm) (Park, J. et al., J. Non-Crystalline Solids 2005, 351, 2352–2357; Sun, C. et al., Applied Mechanics Materials 2012, 110-116, 514-518; Chen, M. et al., J. Power Sources 2008, 181, 161-171; Kamiya, H. et al., J. Am. Ceram. Soc. 2000, 83, 287-293). This is seriously inconsistent with the actual application, because the commercial fumed silica can only destroy the van der Waals force combined with each other through mechanical force, that is, the dispersion can only obtain the above-mentioned aggregates, and the particle size at this time is between 100-300nm. This disconnection between theory and reality has led to no clear knowledge guidance for the key pretreatment process of dispersion, which has seriously affected or even hindered the practical application of fumed silica.
本发明经过系统深入地研究，在明确机械分散粒径是决定商品气相二氧化硅应用效果的重要因素基础上，总结了综合利用剪切力、超声力、分散时间、气相二氧化硅浓度等手段，可以实现对商品气相二氧化硅的分散以及对粒径的有效控制。 After systematic and in-depth research, on the basis of clarifying that the particle size of mechanical dispersion is an important factor determining the application effect of commercial fumed silica, the present invention summarizes the comprehensive utilization of shear force, ultrasonic force, dispersion time, concentration of fumed silica and other means , can achieve the dispersion of commercial fumed silica and the effective control of particle size.
发明内容 Contents of the invention
本发明在于针对现有技术的不足，提供一种能有效控制气相二氧化硅分散粒径的方法。该方法在商品气相二氧化硅配制成浓度为4wt%~25wt%的水溶液时，综合利用剪切力、超声力、分散时间等，能有效控制气相二氧化硅的分散粒径在130nm~240nm。 The present invention aims to provide a method capable of effectively controlling the dispersed particle size of fumed silica aiming at the deficiencies of the prior art. This method can effectively control the dispersed particle size of fumed silica at 130nm~240nm by comprehensively utilizing shear force, ultrasonic force, dispersion time, etc. when commercial fumed silica is formulated into an aqueous solution with a concentration of 4wt%~25wt%.
为实现上述目的，本发明采用如下技术方案： To achieve the above object, the present invention adopts the following technical solutions:
一种控制气相二氧化硅分散粒径的方法：将商品气相二氧化硅配制成浓度为4wt%~25wt%的水溶液，在剪切线速度为9.64 m/s~27 m/s下，剪切1分钟~15分钟；或再在超声功率为9.5W ~950W下，超声分散1分钟~15分钟；制得分散粒径控制在130nm~240nm（粒度分布仪测定并经浓度外推法处理）的气相二氧化硅。 A method for controlling the dispersed particle size of fumed silica: prepare commercial fumed silica into an aqueous solution with a concentration of 4wt%~25wt%, and shear 1 minute to 15 minutes; or ultrasonically disperse for 1 minute to 15 minutes at an ultrasonic power of 9.5W to 950W; the prepared particle size is controlled at 130nm~240nm (determined by particle size distribution analyzer and processed by concentration extrapolation method) fumed silica.
本申请采用由定子和转子构成的高速剪切机或均质机进行剪切。 This application adopts a high-speed shearing machine or a homogenizer composed of a stator and a rotor for shearing.
本申请采用由超声发生器构成的超声波粉碎机进行超声分散。 This application uses an ultrasonic pulverizer composed of an ultrasonic generator for ultrasonic dispersion.
本发明综合利用剪切力、超声力、分散时间、气相二氧化硅浓度等手段，单独使用剪切力或联合使用剪切与超声力，合理选择气相二氧化硅浓度，在所述分散时间内，可以良好地控制气相二氧化硅的分散粒径在130nm~240nm。 The present invention comprehensively utilizes shear force, ultrasonic force, dispersion time, gas phase silica concentration and other means, uses shear force alone or in combination with shear force and ultrasonic force, reasonably selects the concentration of gas phase silica, within the dispersion time , can well control the dispersed particle size of fumed silica at 130nm~240nm.
条件试验： Condition test:
1）二氧化硅浓度变化对气相二氧化硅分散粒径的影响 1) Effect of silica concentration change on dispersed particle size of fumed silica
分别称量浓度为4wt%~25wt%的二氧化硅水溶液，固定剪切线速度为15.5 m/s下，剪切3分钟。气相二氧化硅的分散粒径随气相二氧化硅浓度的变化如图1所示。随着气相二氧化硅浓度增加，分散粒径减小。 Weigh the silicon dioxide aqueous solution with a concentration of 4wt%~25wt%, respectively, and shear for 3 minutes at a fixed shear line speed of 15.5 m/s. The variation of the dispersed particle size of fumed silica with the concentration of fumed silica is shown in Figure 1. As the concentration of fumed silica increases, the dispersed particle size decreases.
2）剪切线速度的变化对气相二氧化硅的分散粒径的影响 2) The influence of the change of shear line speed on the dispersed particle size of fumed silica
称量浓度为15wt%的二氧化硅水溶液，分别固定剪切线速度为12~24 m/s下，剪切3分钟。气相二氧化硅的分散粒径随剪切线速度的变化如图2所示。随着剪切线速度增加，气相二氧化硅分散粒径减小。 Weigh the silicon dioxide aqueous solution with a concentration of 15wt%, and shear for 3 minutes at a fixed shear line speed of 12-24 m/s. The variation of the dispersed particle size of fumed silica with the shear line speed is shown in Figure 2. The dispersed particle size of fumed silica decreases with the increase of shear line velocity.
3）剪切时间的变化对气相二氧化硅的分散粒径的影响 3) The influence of the change of shear time on the dispersed particle size of fumed silica
称量浓度为15wt%的二氧化硅水溶液，固定剪切线速度为15.5 m/s下，分别剪切3~15分钟。气相二氧化硅的分散粒径随剪切时间的变化如图3所示。随着剪切时间增加，气相二氧化硅分散粒径略减小。 Weigh the silicon dioxide aqueous solution with a concentration of 15wt%, and shear at a fixed shear line speed of 15.5 m/s for 3 to 15 minutes respectively. The change of dispersed particle size of fumed silica with shear time is shown in Fig. 3. With the increase of shear time, the dispersed particle size of fumed silica decreases slightly.
4）超声时间的变化对气相二氧化硅的分散粒径的影响 4) The influence of the change of ultrasonic time on the dispersed particle size of fumed silica
称量浓度为15wt%的二氧化硅水溶液，在固定剪切线速度为15.5 m/s下，剪切3分钟后，再联合超声分散，在665W功率下分别超声1~9分钟。气相二氧化硅的分散粒径随超声时间的变化如图4所示。随着超声时间增加，气相二氧化硅分散粒径减小。超声条件下能获得比剪切更小的气相二氧化硅分散粒径。 Weigh the silica aqueous solution with a concentration of 15wt%, shear at a fixed shear line speed of 15.5 m/s for 3 minutes, and then combine with ultrasonic dispersion, and ultrasonicate for 1 to 9 minutes at a power of 665W. The change of dispersed particle size of fumed silica with ultrasonic time is shown in Figure 4. As the ultrasonic time increases, the dispersed particle size of fumed silica decreases. Under ultrasonic conditions, the particle size of fumed silica can be smaller than that of shearing.
5）超声功率的变化对气相二氧化硅的分散粒径的影响 5) The influence of the change of ultrasonic power on the dispersed particle size of fumed silica
称量浓度为15wt%的二氧化硅水溶液，在固定剪切线速度为15.5 m/s下，剪切3分钟后，再联合超声分散，分别固定超声功率为450W~900W下，超声5分钟。气相二氧化硅的分散粒径随超声功率的变化如图5所示。随着超声功率增加，气相二氧化硅分散粒径略减小。 Weigh the silicon dioxide aqueous solution with a concentration of 15wt%, cut it for 3 minutes at a fixed shear line speed of 15.5 m/s, and then combine with ultrasonic dispersion, respectively, fix the ultrasonic power at 450W~900W, and ultrasonicate for 5 minutes. The variation of dispersed particle size of fumed silica with ultrasonic power is shown in Figure 5. As the ultrasonic power increases, the dispersed particle size of fumed silica decreases slightly.
本发明的显著优点在于：Significant advantage of the present invention is:
（1）本发明有目的地改善了商品气相二氧化硅的前处理工艺，综合利用剪切力、超声力、分散时间、气相二氧化硅浓度等手段，实现了对二氧化硅的分散粒径的有效控制，从而大大影响胶凝剂性质以及胶体电池性能； (1) The present invention purposely improves the pretreatment process of commercial fumed silica, and realizes the dispersed particle size of silica by comprehensively utilizing means such as shear force, ultrasonic force, dispersion time, and concentration of fumed silica. Effective control, which greatly affects the properties of the gelling agent and the performance of the gel battery;
（2）通过加大气相二氧化硅的浓度来增加粒子间碰撞，从而获得更小的粒径，这个方法不增加生产成本，仅简单地改变浓度条件，就可以获得良好的额外分散效果，具备显著地进步。 (2) By increasing the concentration of gaseous silica to increase the collision between particles, so as to obtain a smaller particle size, this method does not increase production costs, and a good additional dispersion effect can be obtained by simply changing the concentration conditions. significantly improved.
附图说明 Description of drawings
图1为固定剪切线速度为15.5 m/s，剪切3分钟条件下，气相二氧化硅浓度对分散粒径的影响； Figure 1 shows the effect of the concentration of fumed silica on the dispersed particle size under the condition of a fixed shear line speed of 15.5 m/s and a shear rate of 3 minutes;
图2为固定气相二氧化硅浓度为15.0wt%，剪切3分钟条件下，剪切线速度对分散粒径的影响； Fig. 2 is that the concentration of fumed silica is 15.0wt%, under the condition of shearing for 3 minutes, the influence of shear line speed on the dispersed particle size;
图3为固定气相二氧化硅浓度为15.0wt%，剪切线速度为15.5 m/s条件下，剪切时间对分散粒径的影响； Figure 3 shows the effect of shear time on the dispersed particle size under the condition of a fixed fumed silica concentration of 15.0wt% and a shear line velocity of 15.5 m/s;
图4为固定气相二氧化硅浓度为15.0wt%，剪切线速度为15.5 m/s下剪切3分钟后，再固定665W功率下超声分散，超声时间对分散粒径的影响； Figure 4 shows the effect of ultrasonic dispersion at a fixed power of 665W after a fixed fumed silica concentration of 15.0wt%, a shear line speed of 15.5 m/s for 3 minutes, and ultrasonic dispersion on the dispersed particle size;
图5为固定气相二氧化硅浓度为15.0wt%，剪切线速度为15.5 m/s下剪切3分钟后，再超声分散5分钟下，超声功率对分散粒径的影响。 Figure 5 shows the effect of ultrasonic power on the dispersed particle size after 3 minutes of shearing at a fixed fumed silica concentration of 15.0wt% and a shear line speed of 15.5 m/s, followed by ultrasonic dispersion for 5 minutes.
具体实施方式 Detailed ways
本发明用下列实施例来进一步说明本发明，但本发明的保护范围并不限于下列实施例。 The present invention further illustrates the present invention with following examples, but protection scope of the present invention is not limited to following examples.
实施例Example 11
将商品气相二氧化硅配制成浓度为4wt%水溶液，在剪切线速度为9.64 m/s下，剪切1分钟，处理后的气相二氧化硅的分散粒径为240±5 nm。 The commercial fumed silica was prepared into an aqueous solution with a concentration of 4wt%, and sheared for 1 minute at a shear line speed of 9.64 m/s. The dispersed particle size of the treated fumed silica was 240±5 nm.
实施例Example 22
将商品气相二氧化硅配制成浓度为20wt%水溶液，在剪切线速度为27 m/s下，剪切10分钟，处理后的气相二氧化硅的分散粒径为150±3 nm。 The commercial fumed silica was prepared into an aqueous solution with a concentration of 20wt%, and sheared for 10 minutes at a shear line speed of 27 m/s. The dispersed particle size of the treated fumed silica was 150±3 nm.
实施例Example 33
将商品气相二氧化硅配制成浓度为15.0wt%水溶液，在剪切线速度为15.5m/s下，剪切3分钟后；再在超声功率为855W下，超声分散5分钟，处理后的气相二氧化硅的分散粒径为130±2 nm。 Commercial fumed silica was prepared into an aqueous solution with a concentration of 15.0wt%, sheared for 3 minutes at a shear line speed of 15.5m/s, and then ultrasonically dispersed for 5 minutes at an ultrasonic power of 855W, the treated gas phase The dispersed particle size of silica is 130±2 nm.
以上所述仅为本发明的一部分实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。 The above description is only a part of the embodiments of the present invention, and all equivalent changes and modifications made according to the scope of the patent application of the present invention shall fall within the scope of the present invention.
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