CN105118996A - Dispersion method for nanometer silicon - Google Patents
Dispersion method for nanometer silicon Download PDFInfo
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- CN105118996A CN105118996A CN201510557635.6A CN201510557635A CN105118996A CN 105118996 A CN105118996 A CN 105118996A CN 201510557635 A CN201510557635 A CN 201510557635A CN 105118996 A CN105118996 A CN 105118996A
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Abstract
The invention discloses a dispersion method for nanometer silicon. The dispersion method comprises the following steps: (1) dissolving nano silicon powder into a polar solvent, and stirring to prepare a nano silicon solution with the solid content of 1-20 percent; (2) pre-dispersing the nano silicon solution by physical dispersion; (3) adding a multi-anchoring-group polyether type super dispersant into the pre-dispersing solution, and uniformly stirring to obtain a uniformly stirred nano silicon dispersing solution. By adoption of a mechanical dispersion and chemical dispersion combining method and selection of the multi-anchoring-group polyether type super dispersant matched with the surface of the nano silicon and the property of the solvent, the nano silicon pre-dispersing solution with higher dispersion property and stability is obtained, and the severe agglomeration problem in application of the nano silicon powder in a silicon carbon negative electrode material is solved.
Description
Technical field
The present invention relates to a kind of process for dispersing of nano-silicon, particularly relate to a kind of method using the polymeric hyperdispersants dispersing nanometer silicon of many anchorings base.
Background technology
Silicon is the focus material of lithium ion battery negative material research in recent years, silicon has very high theoretical capacity (up to 4200mAh/g), it is the excellent substitute of graphite material, much larger than the theoretical capacity of graphite, and have solvation unlike graphite, but there is huge bulk effect in its charge and discharge process, up to 400%.Pure silicon material in cyclic process due to its huge bulk effect, SEI film can be concatenated to form on its surface in the process of Swelling and contraction repeatedly in charge and discharge process, consume electrolyte, cause the rapid decay of capacity, and the conductive network of material can be destroyed in dilation process, its conductivity is worsened rapidly, to such an extent as to capacity decay to rapidly almost nil.
In order to avoid alleviating the harm that its volumetric expansion brings electrode material, many solutions are emerged in large numbers, nanometer silicon materials, porous silica material, silicon metallic composite, Si-C composite material.Its design original intention is all the harm that the huge system effect in order to alleviate silicon materials is brought, and main design idea is mainly based on following a few class: 1) silicon materials nanometer is the degree in order to reduce volumetric expansion; 2) " rivet effect " restrains bulk effect with external stress, has derived the various coated of silicon face thus; 3) preparation of volume padded coaming, this type of design philosophy is around silicon grain, there are some flexible materials, can suppress the destruction that silicon expands to electrode.
And silicon carbon material is the focus of a research of present stage, the advantages such as be the commercial product of future generation being expected to replace on a large scale graphite cathode material, it has excellent conductivity, and synthetic method is various, advantage of lower cost.In the preparation process of the silicon-carbon cathode material of function admirable, one of them key point is exactly the scattering problem of nano silicon material, being prepared in the preparation process of silicon carbon material of dispersed and stable silicon pre-dispersed liquid is significant, if silicon pre-dispersed liquid can not deposit with material synthesis processes in be in stable dispersity, the reunion that silicon can be caused serious in so ensuing material preparation, there is larger silicon agglomerated particle, even if local still can show huge bulk effect after synthesis silicon-carbon cathode material, battery material circulation is caused to keep the consequences such as rate variance.
Chinese patent CN102702796A, publication date on October 3rd, 2012, improve the method for nano-silicon lapping liquid dispersive property, disclose and utilize ball milling that micron silicon particle is worn into silicon nanoparticle, anionic dispersing agents is added, the silicon lapping liquid dispersive property that made dispersant adsorption at silicon nanoparticle surface modification in process of lapping.Chinese patent CN1544335A, publication date on November 10th, 2004, discloses and add different anionic dispersing agents in titanium oxide dispersion, all achieve certain dispersion effect.But said method is all directly employ dispersant common on market, fail to do further research to the screening of the solute surface nature that will disperse and dispersant, institute reach dispersion and stablizing effect also not satisfactory.At present, designed many hyper-dispersants for nano material, but the unreasonable effect that causes of the Molecular Design of most hyper-dispersant is also not satisfactory.
Therefore, consider to select under the surface nature of decentralized medium and the prerequisite of residing dicyandiamide solution comprehensively a kind of suitable process for dispersing and suitable dispersant most important to the nano-silicon dispersion liquid that preparation is stable.
Summary of the invention
The technical problem to be solved in the present invention overcomes the deficiencies in the prior art, provides a kind of process for dispersing of nano-silicon.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is:
A process for dispersing for nano-silicon, comprises the following steps:
(1) nano silica fume is dissolved in polar solvent and stirs and be made into the nanometer silicon liquid that solid content is 1% ~ 20%;
(2) utilize physical dispersion to carry out pre-dispersed to described nanometer silicon liquid, open the soft-agglomerated of nano-silicon;
(3) add many anchoring groups polyethers hyper-dispersant in the solution after step (2) is pre-dispersed, and stir, namely obtain finely dispersed nano-silicon dispersion liquid.
Above-mentioned process for dispersing, preferably, the anchoring group effect group of described many anchoring groups polyethers hyper-dispersant is carboxyl, and solvent chain is polyether chain.
Above-mentioned process for dispersing, preferably, described many anchoring groups polyethers hyper-dispersant anchoring group be polyolefin acid chain, monomer whose structure is RCH=CH-COOH, and wherein R is alkyl; Solvent chain is polyvinyl methyl ether chain, and monomer whose structure is CH
2=CH-OCH
3.
Above-mentioned process for dispersing, preferably, described many anchoring groups polyethers hyper-dispersant structural formula is as follows:
in formula, R is alkyl.
Above-mentioned process for dispersing, preferably, anchoring group degree of polymerization 10<n<30, the degree of polymerization 15<m<40 of solvent chain.Suitable degree of polymerization guarantee dispersion effect is good.
Above-mentioned process for dispersing, preferably, in described step (2), the method for physical dispersion is dispersion machine process and/or ultrasonic wave dispersion treatment; Wherein during dispersion machine process, spinner velocity is 5000 ~ 50000r/min, and the processing time is 0.1 ~ 300min; During ultrasonic disperse process, instrument power is 300 ~ 2000w, and temperature controls at 5 ~ 50 DEG C, and the processing time is 0.1 ~ 300min.
Above-mentioned process for dispersing, preferably, in described step (1), polar solvent is water, glycerine or methyl-sulfoxide.
Above-mentioned process for dispersing, preferably, in described step (3), the addition of many anchoring groups ethers hyper-dispersant is 1% ~ 50% of nano silica fume quality; The time of stirring is 0.5 ~ 24h.
The present invention investigated nano-silicon surface electrically and surface with group, particle surface Zeta potential measurement result is carried out in table 1 to several nano silica fumes common on market, can see that nano silica fume surface prepared by various different manufacturers distinct methods is electronegative.
Theoretical according to DLOV, if use cation dispersing agent for the dispersion of this type of particle, will in and surface charge cause Van der Waals force to be greater than repulsive force causing rapid reunion; And if use anionic dispersing agents, effective absorption can not be there is because like charges repels mutually.Infrared spectrum analysis is carried out as shown in Figure 1 by the nano silica fume produced Guilin Minerals & Geologic Academy, can know that nano-silicon molecular surface is rich in a large amount of oh groups, therefore select to select carboxylic group at the anchoring group of dispersant, consider that the hydrogen bond action that carboxyl and hydroxyl occur is weak force, single anchoring group can not be formed with silicon nanoparticle and firmly be combined, therefore anchoring group section must have the structure of multiple hydroxyl.In the selection of solvent chain: will have in aqueous systems and water-solublely preferably must play again good sterically hindered effect, here we have selected polyether chain as solvent chain, and its strong polar functional group had can ensure that backbone is fully unfolded in polar solvent and form sufficient steric hindrance.Therefore select to possess the anchor chain of multiple carboxylic group composition and the solvent chain of polyethers composition, meet the demand that nano-silicon disperses at polar system completely.As shown in Figure 2, the anchoring group of hyper-dispersant and the hydroxyl generation hydrogen bond action on nano-silicon surface, the solvent chain of polyethers stretches in solvent and serves inhibition for many anchoring groups hyper-dispersant and silicon nanoparticle effect schematic diagram.
The zeta current potential of the nano-silicon of table 1 different manufacturers
Compared with prior art, the invention has the advantages that:
(1) the present invention adopts many anchoring groups polyethers hyper-dispersant molecular structure succinctly effective, and the monomer of anchoring group is olefin(e) acid class, and structure is simply easy to synthesis; Solvent chain selects polyvinyl methyl ether, and its structure is simple, by force water-soluble.
(2) present invention employs the method that mechanical dispersion combines with chemical dispersion, and have selected the many anchoring groups ethers hyper-dispersant mutually mated with nano-silicon surface and solvent property, obtain dispersed and stability nano-silicon pre-dispersed liquid all preferably, improve the serious agglomeration traits that nano silica fume runs in silicon-carbon cathode material application.
(3) whole operation of the present invention is carried out in polar solvent, for the process of the follow-up low cost of silicon-carbon cathode material, more options creates condition.
(4) the present invention adopts many anchoring groups ethers hyper-dispersant dispersing nanometer silicon, far better relative to traditional nano-silicon process for dispersing dispersion effect, process for dispersing technique of the present invention is simple simultaneously, only needs mechanical dispersion and add hyper-dispersant just can reach good effect.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of Guilin Minerals & Geologic Academy's nano-silicon.
Fig. 2 is the effect schematic diagram that the present invention adopts many anchoring groups ethers hyper-dispersant dispersing nanometer silicon grain.
Fig. 3 is the SEM figure of nano-silicon dispersion liquid prepared by the embodiment of the present invention 1.
Fig. 4 is that the nano-silicon SEM do not disperseed in the embodiment of the present invention 1 schemes.
Embodiment
For the ease of understanding the present invention, hereafter will do to describe more comprehensively, meticulously to the present invention in conjunction with Figure of description and preferred embodiment, but protection scope of the present invention is not limited to following specific embodiment.
Unless otherwise defined, hereinafter used all technical terms are identical with the implication that those skilled in the art understand usually.The object of technical term used herein just in order to describe specific embodiment is not be intended to limit the scope of the invention.
Apart from special instruction, the various reagent used in the present invention, raw material are can commodity commercially or can by the obtained product of known method.
Embodiment 1:
A kind of process for dispersing of nano-silicon of the present invention, comprise the following steps: nano silica fume Guilin Minerals & Geologic Academy produced (is reunited serious, average grain is about 80nm) join in pure water to stir and be made into the nanometer silicon liquid that solid content is 1%, being placed in ultrasonic cleaning instrument, to control water temperature be 20 ~ 30 DEG C, ultrasonic power is disperse 20min under the condition of 300w, then many anchoring groups polyethers hyper-dispersant (molecular weight is 2000) of silica flour quality 5% is added, utilize mechanical agitation 6h, obtain finely dispersed nano-silicon dispersion liquid.Recording nano-silicon dispersion liquid granularity is 191nm; Its electron-microscope scanning figure as shown in Figure 3,
The nano-silicon dispersion liquid sealing and standing prepared by the present embodiment records its granularity after 15 days be 207nm, and recording granularity after being then placed in the water bath with thermostatic control 40h of 80 DEG C is 201nm.
Without the SEM figure before dispersant process as shown in Figure 4, particle agglomeration is serious, does not substantially have primary particle for the silicon nanoparticle that the present embodiment adopts.From Fig. 3 and Fig. 4 relatively, process for dispersing of the present invention be nano-silicon degree of scatter improve huge.
Comparative example 1:
The nano-silicon dispersion detailed process of this comparative example is: be that the nano-silicon powder of 80nm joins pure water solution and stirs and be made into the nanometer silicon liquid that solid content is 1% by granularity, being placed in ultrasonic cleaning instrument, to control water temperature be disperse 20min under the condition of 20 ~ 30 DEG C, then add the softex kw of silica flour weight 5%, utilize mechanical agitation oar to stir 6h.Leaving standstill the thick granularity recording nano-silicon dispersion liquid of 30min is 723nm, leaves standstill and within 4 days, has occurred that the layering of comparatively obvious turbid clear liquid and a large amount of settle are in beaker bottom.
Embodiment 2:
A kind of process for dispersing of nano-silicon of the present invention, comprise the following steps: nano silica fume Guilin Minerals & Geologic Academy produced (is reunited serious, average grain is about 80nm) join in pure water to stir and be made into the nanometer silicon liquid that solid content is 1%, use high speed dispersor with 30000r/min rotating speed dispersion 20min, then many anchoring groups polyethers hyper-dispersant (molecular weight is 2000) of silica flour quality 10% is added, utilize mechanical agitation 6h, obtain finely dispersed nano-silicon dispersion liquid.Recording nano-silicon dispersion liquid granularity is 233nm; Sealing and standing records nano-silicon dispersion liquid granularity after 15 days is 231nm.
Comparative example 2:
The nano-silicon dispersion detailed process of this comparative example is: nano silica fume Guilin Minerals & Geologic Academy produced (is reunited serious, average grain is 80nm) join in pure water to stir and be made into the silicon pre-dispersed liquid that solid content is 1%, use high speed dispersor with 30000r/min rotating speed dispersion 20min, then add the lauryl sodium sulfate of silica flour weight 10%, utilize mechanical agitation oar to stir 6h.The granularity that standing 30min records nano-silicon dispersion liquid is 521nm, leaves standstill 4 days visible major parts substantially and falls to beaker bottom, occurred the layering of comparatively obvious turbid clear liquid.
Embodiment 3:
A kind of process for dispersing of nano-silicon of the present invention, comprise the following steps: nano silica fume Guilin Minerals & Geologic Academy produced (is reunited serious, average grain is about 80nm) join in pure water to stir and be made into the nanometer silicon liquid that solid content is 5%, be placed in ultrasonic cleaning instrument and control that water temperature is 20 ~ 30 DEG C, ultrasonic power is disperse 20min under the condition of 300w, then many anchoring groups polyethers hyper-dispersant (molecular weight is 2000) of silica flour quality 20% is added, utilize mechanical agitation 6h, obtain finely dispersed nano-silicon dispersion liquid.Recording nano-silicon dispersion liquid granularity is 223nm.Sealing and standing records granularity after 15 days be 231nm, then to record granularity after the water bath with thermostatic control 40h being placed in 80 DEG C be 229nm.
Comparative example 3:
The nano-silicon dispersion detailed process of this comparative example is: nano silica fume Guilin Minerals & Geologic Academy produced (is reunited serious, average grain is 80nm) join in pure water to stir and be made into the silicon pre-dispersed liquid that solid content is 5%, be placed in ultrasonic cleaning instrument and control that water temperature is 20 ~ 30 DEG C, ultrasonic power is disperse 20min under the condition of 300w, then add the polyvinylpyrrolidone (molecular weight is 5000) of silica flour weight 20%, utilize mechanical agitation oar to stir 6h.It is 221nm that standing 30min records granularity, leaves standstill 15 days visible parts substantially and falls to beaker bottom, occurred the layering of visible turbid clear liquid.
As can be seen from above-mentioned specific embodiment and comparative example, method that the present invention utilizes physical dispersion and chemical dispersion to combine and selected the polymeric hyperdispersants of many anchorings base of coupling, obtain the silicon dispersion liquid of dispersiveness, good stability, show the effect more excellent than traditional process for dispersing, solve the agglomeration traits in the use of nano-silicon in silicon-carbon cathode preferably.
Claims (8)
1. a process for dispersing for nano-silicon, is characterized in that, comprises the following steps:
(1) nano silica fume is dissolved in polar solvent and stirs and be made into the nanometer silicon liquid that solid content is 1% ~ 20%;
(2) physical dispersion is utilized to carry out pre-dispersed to described nanometer silicon liquid;
(3) add many anchoring groups polyethers hyper-dispersant in the solution after step (2) is pre-dispersed, and stir, namely obtain finely dispersed nano-silicon dispersion liquid.
2. as claimed in claim 1 point of scattering method, is characterized in that, described many anchoring groups polyethers hyper-dispersant its effect group of anchoring group be carboxyl; Solvent chain is polyether chain.
3. process for dispersing as claimed in claim 1, is characterized in that, described many anchoring groups polyethers hyper-dispersant anchoring group be polyolefin acid chain, monomer whose structure is RCH=CH-COOH, and wherein R is alkyl; Solvent chain is polyvinyl methyl ether chain, and monomer whose structure is CH
2=CH-OCH
3.
4. process for dispersing as claimed in claim 1, it is characterized in that, described many anchoring groups polyethers hyper-dispersant structural formula is as follows:
in formula, R is alkyl.
5. process for dispersing as claimed in claim 4, is characterized in that, the degree of polymerization 10<n<30 of anchoring group, the degree of polymerization 15<m<40 of solvent chain.
6. the process for dispersing as described in any one of Claims 1 to 5, is characterized in that, in described step (2), the method for physical dispersion is dispersion machine process and/or ultrasonic wave dispersion treatment; Wherein during dispersion machine process, spinner velocity is 5000 ~ 50000r/min, and the processing time is 0.1 ~ 300min; During ultrasonic disperse process, instrument power is 300 ~ 2000w, and temperature controls at 5 ~ 50 DEG C, and the processing time is 0.1 ~ 300min.
7. the process for dispersing as described in any one of Claims 1 to 5, is characterized in that, in described step (1), polar solvent is water, glycerine or methyl-sulfoxide.
8. the process for dispersing as described in any one of Claims 1 to 5, is characterized in that, in described step (3), the addition of many anchoring groups ethers hyper-dispersant is 1% ~ 50% of nano silica fume quality; The time of stirring is 0.5 ~ 24h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108199046A (en) * | 2017-12-26 | 2018-06-22 | 欣旺达电子股份有限公司 | Binding agent and lithium ion battery |
| CN110247046A (en) * | 2019-07-19 | 2019-09-17 | 深圳职业技术学院 | A kind of preparation method of lithium ion battery CA/ nano Si/graphene composite negative pole |
| CN110890537A (en) * | 2018-09-11 | 2020-03-17 | 江苏中能硅业科技发展有限公司 | Production method of high-purity nanocrystalline silicon |
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| CN102702796A (en) * | 2012-05-28 | 2012-10-03 | 深圳市贝特瑞新能源材料股份有限公司 | Method for improving dispersion property of nanosilicon grinding fluid |
| JP2014007120A (en) * | 2012-06-27 | 2014-01-16 | Sanyo Electric Co Ltd | Negative electrode for lithium secondary battery, manufacturing method thereof, and lithium secondary battery |
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