CN103426498B - A kind of carbon nanotube conducting slurry and preparation method thereof - Google Patents
A kind of carbon nanotube conducting slurry and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to electrochemical material technical field, be specifically related to this carbon nanotube conducting slurry of a kind of carbon nanotube conducting slurry and preparation method thereof primarily of carbon nano-tube, other conductive fillers, dispersing aid and solvent composition, its mass percent consists of: carbon nano-tube: 0.5 ~ 15%, other conductive materials 0.1 ~ 2%, dispersing aid: 0.1 ~ 5%, all the other are solvent.This carbon nanotube conducting slurry preparation method is: first dissolved in a solvent by dispersing aid, then carbon nano-tube and other conductive fillers are added under agitation, after carbon nano-tube and other conductive fillers fully infiltrate, adopt sand mill to grind slurry, the carbon nanotube conducting slurry of stable dispersion after several hours, can be obtained.The inventive method is simple, not destroying carbon nanometer tube structure and conductivity, and obtained carbon nanotube conducting slurry has excellent conductivity, and stable in properties is homogeneous, leaves standstill after 3 months, Stability of Slurry & gt; 90%.
Description
Technical field
The invention belongs to electrochemical material technical field, be specifically related to a kind of carbon nanotube conducting slurry and preparation method thereof, this material can be used as the negative or positive electrode that conductive agent is applied to lithium rechargeable battery, capacitor.
Background technology
In the preparation process of lithium rechargeable battery and capacitor, often need to add a certain amount of conductive agent in both positive and negative polarity batching.Conductive agent effectively can contact with both positive and negative polarity active material, forms good conductive network, thus improves the high rate performance of battery.But add conductive agent too much, electrode active material content certainly will be reduced, reduce capacity and the energy density of battery.For high performance electronic equipment, select suitable conductive agent particularly important.
Carbon nano-tube is in recent years emerging conductive agent, its general diameter is at 5 ~ 60 ran, length reaches 10 ~ 20 microns, it can not only serve as the effect of " wire " in conductive network, and it also has electric double layer effect simultaneously, plays the high-rate characteristics of ultracapacitor, its good heat conductivility also helps heat radiation during battery charging and discharging, reduce the polarization of battery, improve the high temperature performance of battery, extend the life of a cell.
The people such as Liu (JournalofPowerSources2008,184,522-526.) have reported multi-walled carbon nano-tubes (MWNTs) and carbon black is the C-LiFePO of conductive agent
4/ graphite cell performance.Compared with carbon black, be that the battery of additive has more excellent chemical property with MWNTs: 50 circulation volume conservation rates reach that 99.2%, 1C discharge capacity is 0.1C 94.6%.Polarizing voltage has been reduced to 0.2V from 0.3V, and impedance has been reduced to 36.88 Ω from 423.2 Ω.Positive electrode LiFePO after circulation
4crystal formation keep also better.The people such as Jin (JournalofSolidStateElectrochemistry2008,12,1549-1554.) have studied and adopt acetylene black and MWNTs as positive conductive agent to LiFePO
4the impact of-C positive electrode material chemical property.Add the LiFePO of 5wt%MWNTs
4-C/Li battery performance is the most excellent, and under room temperature, 0.25C can reach the reversible capacity of 142mAh/g.
But because carbon nano-tube has stronger Van der Waals force each other, the mutual entanglement aggregate of meeting together (Fig. 1), is difficult to be dispersed in positive and negative electrode material, thus have impact on the performance of carbon nano-tube conductive energy.Therefore, how preparing homodisperse carbon nanotube conducting slurry is the major obstacle limiting its commercial application.At present, solve carbon nanotube dispersed problem and mainly contain chemistry and physics two kinds of methods.Although chemical method such as acid with strong oxidizing property processing method can obtain the good carbon nano-tube of dispersive property, strong acid also can the structure of destroying carbon nanometer tube, shortening carbon nano-tube, thus affects the conductivity of carbon nano-tube and be used as the performance of conductive agent.More ultrasonic processing method efficiency is low, dispersion effect is poor, stability as adopted for physical method, and the carbon nano tube dispersion liquid concentration obtained is lower than 5mg/mL, is difficult to the dispersed paste preparing carbon nano-tube on a large scale.
In the present invention, we have proposed a kind of simple new method preparing carbon nanotube conducting slurry, preparation process is reproducible, obtained carbon nanotube conducting slurry solid content is high, stable in properties is homogeneous, leaves standstill after 3 months, Stability of Slurry >90%.
Summary of the invention
The object of the present invention is to provide a kind of carbon nanotube conducting slurry.
Another object of the present invention is the preparation method providing a kind of carbon nanotube conducting slurry.
Carbon nanotube conducting slurry proposed by the invention, its feature is that this electrocondution slurry is by carbon nano-tube, other conductive fillers, dispersing aid and solvent composition, its mass percent consists of: carbon nano-tube: 0.5 ~ 15%, other conductive fillers 0.1 ~ 2%, dispersing aid: 0.1 ~ 5%, all the other are solvent.
Described carbon nano-tube is one or both mixing in Single Walled Carbon Nanotube or multi-walled carbon nano-tubes.
Other described conductive fillers are one or more in carbon black, acetylene black, carbon fiber or electrically conductive graphite.
Described dispersing aid is one or more in PVP (PVP), polyvinyl alcohol (PVA) or CMC (CMC).
Described solvent is 1-METHYLPYRROLIDONE (NMP) or water.
The preparation method of carbon nanotube conducting slurry proposed by the invention, its feature is that step is as follows: first dissolved in a solvent by dispersing aid, then carbon nano-tube and other conductive fillers are added under agitation, after carbon nano-tube and other conductive fillers fully infiltrate, adopt sand mill to grind slurry, the carbon nanotube conducting slurry of stable dispersion after several hours, can be obtained.Be specially,
(1) take a certain amount of dispersing aid, dissolve in a solvent, be configured to the solution that percentage by weight is 0.1 ~ 5%; Under mechanical agitation, add percentage by weight be 0.5 ~ 15% carbon nano-tube or carbon nano-tube and percentage by weight be the mixture of other conductive fillers of 0.1 ~ 2%, fully stir, make pressed powder complete wetting, obtained carbon nano-tube pre-dispersed liquid.
(2) by carbon nano-tube pre-dispersed liquid sand mill grinding distribution 0.5 ~ 8 hour, the carbon nanotube conducting slurry of stable dispersion can be obtained.
The diameter of described sand mill zirconia ball used is 0.1 ~ 3mm.
The inventive method is simple, not destroying carbon nanometer tube structure and conductivity, and obtained carbon nanotube conducting slurry has excellent conductivity, and stable in properties is homogeneous, leaves standstill after 3 months, Stability of Slurry >90%.
Compare the strong acid oxidation or ultrasonic wave added process for dispersing that adopt at present both at home and abroad, the present invention has following characteristics: (1) is destroying carbon nanometer tube structure not, effectively can open the aggregation (Fig. 2) of carbon nano-tube; (2) the carbon nanotube conducting size performance obtained stable (leaving standstill after 3 months, stability >90%), has higher solid content (0.5 ~ 15%).
Accompanying drawing explanation
Fig. 1. carbon nanotube agglomerate SEM photo.This result shows that carbon nano-tube is easily reunited together, forms the aggregation that diameter is 10-1000 μm.
Fig. 2. carbon nanotube conducting slurry SEM photo.This result shows that in prepared carbon nano tube paste, carbon nanotube agglomerate is fully opened, and forms the carbon nanotube conducting network be closely connected.
Fig. 3 .(A-F) carbon nano-tube premix slurry and 1-5 hour ground slurry coating post-drying photo.Premix pulp surface is coarse, has obvious caking phenomenon, and along with milling time increases, slurry coating surface is tending towards smooth, homogeneous.This result shows the growth along with milling time, and the dispersion of carbon nanotube conducting slurry is more even.
Fig. 4. carbon nano-tube upper strata slurry solid content variation diagram.Inactive slurry 40 days or adopt 3000 respectively, 6000,12000rpm centrifugal treating slurry, the solid content and the original solids content that measure upper strata slurry change not quite.This result shows that prepared carbon nano tube paste has good stability.
Fig. 5. based lithium-ion battery positive plate SEM photo.See from photo, even carbon nanotube is dispersed between iron phosphate serving as positive active material particle, defines three-dimensional conductive network.
Embodiment
Embodiment 1: add 9.25kgN-methyl pyrrolidone as solvent carrier in the container of 20 liters, add 0.15kg PVP wherein as auxiliary agent.Under 6000rpm mechanical agitation, PVP is fully dissolved in 1-METHYLPYRROLIDONE.Then in solution, add 0.6kg multi-walled carbon nano-tubes in batches, after added pressed powder is fully wetting by solvent, adds remainder carbon nano-tube again.After all adding, continue mechanical agitation 15min, obtain pre-dispersed slurry.Be transferred in nanometer sand mill by pre-dispersed for carbon nano-tube slurry, adopt diameter to be the zirconia ball of 1mm, under 2400rpm, namely grinding obtains carbon nano tube paste in 2 hours.
The pre-dispersed slurry of carbon nano-tube and ground slurry per hour coat slide dries rear photo as shown in Figure 3.Centrifugal and standing survey upper strata slurry solid content method is adopted to characterize carbon nano tube paste stability respectively, as shown in Figure 4.
Embodiment 2: add 9.4kg water as solvent carrier in the container of 20 liters, add 0.1kg CMC wherein as auxiliary agent.Under 5000rpm mechanical agitation, CMC is fully dissolved in the water.Then in solution, add 0.17kgSuper-p nanometer acetylene black conductor and 0.33kg Single Walled Carbon Nanotube in batches, after added pressed powder is fully wetting by solvent, adds remainder combined conductive agent again.After all adding, continue mechanical agitation 15min, obtain pre-dispersed slurry.Be transferred in sand mill by pre-dispersed for carbon nano-tube slurry, adopt diameter to be the zirconia ball of 0.3mm, under 1800rpm, namely grinding obtains carbon nano-tube composite conducting slurry for 5 hours.
Embodiment 3: take 9.4kg deionized water as solvent carrier in the container of 20 liters, add 0.1kg PVP wherein as auxiliary agent.Under 3000rpm mechanical agitation, PVP is fully dissolved in the water.Then in solution, add 0.5kg multi-walled carbon nano-tubes in batches, after added pressed powder is fully wetting by solvent, adds remainder carbon nano-tube again.After all adding, continue mechanical agitation 15min, obtain pre-dispersed slurry.Be transferred in sand mill by pre-dispersed for carbon nano-tube slurry, adopt diameter to be the zirconia ball of 0.6mm, under 1500rpm, namely grinding obtains carbon nano-tube composite conducting slurry for 0.5 hour.
Embodiment 4: take 9.4kgN-methyl pyrrolidone as solvent carrier in the container of 20 liters, add 0.1kg polyvinyl alcohol wherein as auxiliary agent.Under 4000rpm mechanical agitation, polyvinyl alcohol is fully dissolved in 1-METHYLPYRROLIDONE.Then in solution, add 0.17kgSuper-p nanometer acetylene black conductor and 0.33kg multi-walled carbon nano-tubes in batches, after added pressed powder is fully wetting by solvent, adds remainder combined conductive agent again.After all adding, continue mechanical agitation 30min, obtain pre-dispersed slurry.Be transferred in sand mill by pre-dispersed for carbon nano-tube slurry, adopt diameter to be the zirconia ball of 0.8mm, under 1200rpm, namely grinding obtains carbon nano-tube composite conducting slurry for 6 hours.
Embodiment 5: take 9.4kg water as solvent carrier in the container of 20 liters, adds 0.05kg polyvinyl alcohol and 0.05kg PVP wherein as auxiliary agent.Under 4000rpm mechanical agitation, polyvinyl alcohol and PVP are fully dissolved in the water.Then in solution, add 0.17kgSuper-p nanometer acetylene black conductor and 0.33kg multi-walled carbon nano-tubes in batches, after added pressed powder is fully wetting by solvent, adds remainder combined conductive agent again.After all adding, continue mechanical agitation 5min, obtain pre-dispersed slurry.Be transferred in sand mill by pre-dispersed for carbon nano-tube slurry, adopt diameter to be the zirconia ball of 0.2mm, under 1900rpm, namely grinding obtains carbon nano-tube composite conducting slurry for 4.5 hours.
Claims (1)
1. a carbon nanotube conducting slurry, it is characterized in that, this electrocondution slurry is by carbon nano-tube, other conductive fillers, dispersing aid and solvent composition, its mass percent consists of: carbon nano-tube: 0.5 ~ 15%, other conductive fillers 0.1 ~ 2%, dispersing aid: 0.1 ~ 5%, all the other are solvent, described carbon nano-tube can stably be disperseed in a solvent, sedimentation rate <10% in 3 months;
Prepared by following method:
A) take a certain amount of dispersing aid, dissolve in a solvent, be configured to the solution containing dispersing aid; Under mechanical agitation, add carbon nano-tube or carbon nano-tube and other conductive fillers, fully stir, make pressed powder complete wetting, obtained carbon nano-tube pre-dispersed liquid;
B) by carbon nano-tube pre-dispersed liquid sand mill grinding distribution 0.5 ~ 8 hour, the carbon nanotube conducting slurry of obtained stable dispersion; Wherein the diameter of sand mill zirconia ball used is 0.1 ~ 3mm;
Wherein, described carbon nano-tube is one or both mixing in Single Walled Carbon Nanotube or multi-walled carbon nano-tubes;
Other described conductive fillers are one or more in carbon black, acetylene black, carbon fiber or electrically conductive graphite;
Described dispersing aid is one or more in PVP, polyvinyl alcohol or CMC;
Described solvent is 1-METHYLPYRROLIDONE or water.
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| CN1770515B (en) * | 2005-08-22 | 2010-05-12 | 中国科学院成都有机化学有限公司 | Anode, cathode material conductive agent for lithium-ion secondary battery and preparation method thereof |
| CN101081696B (en) * | 2007-05-15 | 2010-08-25 | 深圳市贝特瑞电子材料有限公司 | Ferric phosphate lithium material for lithium ion powder cell and preparation method thereof |
| DE102008008837A1 (en) * | 2008-02-13 | 2009-08-27 | Bayer Materialscience Ag | Printable composition for producing electrically conductive coatings and process for their preparation |
| FR2943261B1 (en) * | 2009-03-20 | 2011-08-26 | Arkema France | METHOD FOR DISPERSION OF CARBON NANOTUBES, SYSTEM FOR IMPLEMENTATION AND UNIFORM DISPERSION THUS OBTAINED |
| CN102044661A (en) * | 2009-10-23 | 2011-05-04 | 比克国际(天津)有限公司 | Method for preparing lithium ion battery slurry |
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