CN106450331A - Method for preparing graphene conducting agent slurry from graphite tailings - Google Patents
Method for preparing graphene conducting agent slurry from graphite tailings Download PDFInfo
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- CN106450331A CN106450331A CN201610950435.1A CN201610950435A CN106450331A CN 106450331 A CN106450331 A CN 106450331A CN 201610950435 A CN201610950435 A CN 201610950435A CN 106450331 A CN106450331 A CN 106450331A
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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
Abstract
The invention relates to graphene and provides a method for preparing a graphene conducting agent slurry from graphite tailings. The method comprises the following steps: removing all impurities from the graphite tailings; adding hydrofluoric acid, hydrochloric acid, nitric acid and water into the graphite tailings without the impurities, and reacting for 12 hours; adding water for cooling and centrifuging and washing until a product is neutral; dehydrating to obtain a graphite filter cake with the moisture content of 15%-25%; carrying out an oxidization reaction with concentrated sulfuric acid and a strong oxidant for 1-12 hours; raising the temperature to 32-38 DEG C; adding ionized water and raising the temperature to 80-100 DEG C; continuing to stir and adding hydrogen peroxide to enable materials to react sufficiently; filtering while a solution is still hot; washing until no sulfate ions exist in the solution; adding a graphite oxide filter cake obtained by centrifuging and dehydrating and a reducing agent solution into a graphene generation tank at a ratio; raising the temperature and keeping the inner temprature at 50-70 DEG C; stirring for 1-5 hours and centrifuging and filtering; washing with de-ionized water; and dehydrating to obtain the graphene slurry with the moisture content of 30%-40%. The method provided by the invention adopts the graphite tailings with low price and changes wastes into valuable things; and the cost of a lithium battery can be effectively reduced, so that the method is suitable for industrial large-batch production.
Description
Technical field
The present invention relates to Graphene, the more particularly, to preparation method of graphene conductive agent slurry.
Background technology
Natural flake graphite is widely used in lithium ion battery from the beginning of late nineteen nineties Japanese enterprises are at first, passes through
Substantial amounts of research, crystalline flake graphite is pulverized, nodularization, purification, drying, bag shoe, carbonization, etc. operation carry out surface modification after be applied to
In lithium ion battery, there is high-energy-density, high circulation stability, have extended cycle life, self discharge is little, the spy such as memory-less effect
Point, and native graphite has wide material sources, cheap, processing characteristics is excellent etc. becomes the main material of cathode of lithium battery.
Constantly expand with its application of lithium battery, not only have been widely used for various portable type electronic products, Er Qiedong
Power lithium ion battery is widely used in new-energy automobile and becomes a Main way of " 13 " New Energy Industry.Lithium
Battery is widely applied and causes negative material to be doubled and redoubled, and the spherical graphite producing negative material use now is by original 1
Enterprise development becomes an industry, and its manufacturing enterprise reaches 20-30 house, and yield reaches 100～5000 tons/month, and crystalline flake graphite adds
Work becomes negative pole its yield rate of base spherical graphite to be up to 65%, has 35% to become graphite tailing.These graphite tailings are because of particle
Carefully, meso-position radius are less than 12um, and the largest particles is less than 20um, and smallest particles is 500nm, and distribution of particles is wider, for refractory material
It is also easy to produce crack, therefore can only be used as filler or pencil stamen or graphite paint, but because yield is too big, drug on the market makes graphite
Tailing causes seriously to overstock, and its price is also to drop many times.How the finishing of graphite tailing being turned waste into wealth is to solve graphite tail
Material overstocks in a large number, it is to avoid a large amount of key issue wasting of resource.
Content of the invention
Present invention seek to address that drawbacks described above, provide a kind of method that graphene conductive agent slurry is prepared with graphite tailing.
The present invention is cheap graphite tailing using raw material, and genus is turned waste into wealth, and can effectively reduce lithium battery cost, and technical process is easily-controllable
System, suitable industrialized mass production.
For solving the above problems, a kind of method that graphene conductive agent slurry is prepared with graphite tailing of the present invention, it includes
The following step：
Step one, removal of impurities：Graphite tailing is crossed 100 eye mesh screens, removes the internal various debris more than 50 microns；
Step 2, purification：Graphite tailing after removal of impurities is put into retort, is proportionally added into hydrofluoric acid, hydrochloric acid, nitric acid and
Pure water, its mixed proportion with graphite：Graphite tailing：Hydrofluoric acid：Hydrochloric acid：Nitric acid：Pure water=1:0.1～0.5:0.3～0.9：
0.1～0.3：0.5～1.0；Stir and be warming up to 80～120 DEG C, the constant reaction of keeping temperature 12 hours, add water cooling
And centrifuge washing, to neutral, obtains the aqueous Graphite Cake for 15-25% through dehydration；
Step 3, oxidation：Above-mentioned aqueous graphite feed filter cake is added in graphite oxide retort, retort internal temperature is adjusted
Save to 0-4 DEG C, add the appropriate concentrated sulfuric acid, open the solid mixing stirring and being proportionally added into described Graphite Cake and nitrate
Thing, adds strong oxidizer while stirring, to be mixed uniformly continue to stir and adjust retort internal temperature afterwards and be less than 20 DEG C, stir
Heat up after mixing reaction 1-12 hour and control internal temperature in the range of 32-38 DEG C, be further continued for stirring 30min, be slowly added to fit
Amount deionized water, and it is warming up to 80-100 DEG C of continuation stirring 30min, add appropriate hydrogen peroxide to make material reaction fully, now
Solution is changed into glassy yellow, filters while hot, till washing sulfate radical-free ion in the solution, obtains graphite oxide through centrifugal dehydration
Filter cake；
Step 4, reduction：Described graphite oxide filter cake and reductant solution are proportionally added in Graphene generate the tank, rise
Temperature simultaneously keeps internal temperature at 50-70 DEG C, turn on agitator, and rotating speed controls in 1000-5000rpm, stirs 1-5 hour, centrifugation
Filter, be washed with deionized, through dehydration, dewatering time is less than 30 minutes, obtains the Graphene slurry of water content 30-40%；
Graphene oxide filter cake：Reducing agent=1：10-30；Reducing agent is hydrazine hydrate, ethylene glycol, ethylene glycol sodium, in sodium borohydride one
Plant or several.
The described method that graphene conductive agent slurry is prepared with graphite tailing, described step 2, in purification, described hydrogen fluorine
Acid content is 40-60%, and content of hydrochloric acid is 30%, and nitric acid content is 40-70%, and concentrated sulfuric acid content is 70-99%, deionized water
It is less than 15 μ S/cm reverse osmosis waters for electrical conductivity.
The described method that graphene conductive agent slurry is prepared with graphite tailing, described step 3, in oxidation, described graphite
Powder：Strong acid solution：Nitrate：Strong oxidizer：Hydrogen peroxide：Deionized water quality ratio：1：10～50:0.3～0.8：1～5:1
～5：30～60.
The described method preparing graphene conductive agent slurry with graphite tailing, described step 3, in oxidation, first with 5%
Hydrochloric acid solution centrifuge washing about 5-20min, then use pure water.
The described method that graphene conductive agent slurry is prepared with graphite tailing, described step 3, aoxidize used oxygen
Graphite retort can adjust retort for temperature, and its housing is to have interlayer in carbon steel, is liquid temperature control medium in interlayer, internal
Being close to inwall has the thick polytetrafluoroethylene floor of 3-8mm, prevents materials inside from tank body is corroded；Interlayer dielectric is connected with compressor,
To liquid medium cooling or heating, materials inside temperature is controlled with heat exchange pattern by liquid medium, passes through by compressor
Thermocouple sensor is temperature required to adjust material.
The described method that graphene conductive agent slurry is prepared with graphite tailing, the Graphene generate the tank in described step 4,
For one similar to kettle shape reactor, inner-wall spraying wear-resistant ceramic, kettle shape shell wall is contained within interlayer, is cast by carbon steel, interlayer
Built with liquid medium, control internal temperature for heat transfer；There are an oval agitator, agitator surface spraying carbonization inside tank
Tungsten, agitator speed 1000-6000rpm.
The described method preparing graphene conductive agent slurry with graphite tailing, described graphite tailing is that crystalline flake graphite production is negative
Tailing produced by the spherical graphite of pole, its meso-position radius is≤graphite microparticles of 12um, its carbon content is 92-95%, and density is about
0.1-0.8g/ml.
The described method that graphene conductive agent slurry is prepared with graphite tailing, preparation-obtained graphene conductive agent slurry
Particle size distribution be 10nm-15um, its color is pitchy pulpous state, is that the parallel graphene sheet layer of 1-600 layer is constituted
Carbonaceous material, its electrical conductivity is 5 × 104-9×104S/m, its specific surface area is 300-600m2/ g, under its 10mA current strength its
Charge specific capacity reaches 120-150F/g.
Graphene is a kind of new material of the individual layer laminated structure being made up of carbon atom, is that a kind of technology content is very high,
Application potential material with carbon element widely, aobvious in semiconductor industry, lithium ion battery, photovoltaic industry, space flight, military project, a new generation
Show that the traditional field such as device and emerging field all will bring revolutionary technological progress, its potential application field includes high speed crystal
Pipe, transparency electrode, printed electronic, advanced composite material (ACM), hypersensor, new catalyst, gene sequencing, energy storage device
Deng；Grapheme material is that 21st century development potentiality is maximum, purposes most commonly used high-tech new material.
And graphene conductive agent has more important and extensive purposes, graphene conductive agent is used for coating lithium battery positive and negative
Pole, can be obviously improved the electrochemical reaction rates of electrode interior, lift rate charge-discharge performance, significantly improve high current simultaneously and fill
The Decay Rate of the lower battery of electric discharge.Benefit from the superpower electric conductivity of Graphene, stability and heat dispersion, same conductive agent adds
On the premise of amount, the resistance of Graphene is 1/10th of CNT, is 1st/40th of conductive carbon black, and conductive effect shows
Write, cell decay degree is significantly better than other conductive agents simultaneously.Future comes into the market with electric automobile high-volume, graphene conductive
The demand of agent can be in explosive growth；It is 30GWh according to scholarly forecast national dynamic lithium battery consumption in 2016, according to unit
KWh positive electrode demand 0.27Kg, 80,000 tons of total positive electrode demand is it is assumed that 10% electrokinetic cell producing line with the addition of stone
Black alkene conductive agent, ratio is 0.3%, then 24 tons of graphene conductive agent demand.Graphene price is averagely in 30-50 at present
Unit/g, total market scale is 1,000,000,000 about, and the joining of the increase with supporting electrokinetic cell producing line and graphene conductive agent
The increase of ratio is indeed it is contemplated that next three years market scale is maintained at more than 100% speedup, most explosive force.
And graphite tailing has fine particles, closest with the particle requirement of graphene conductive agent, sheet easy processing, source
Extensively, the features such as low price, therefore graphite tailing is processed into graphene conductive agent and is of great significance, one is permissible
Reduce the cost of graphene conductive agent, reduce the market price of lithium battery, improve the performance of lithium ion battery.It two can be abundant
Turned waste into wealth using graphite resource, obtain bigger economic benefit.
The graphene conductive agent slurry of the present invention has less internal resistance and higher capacity, and electric conductivity is good, dispersion
Uniformly, it is applied in ultracapacitor or electrode material of lithium battery, charge/discharge rates can be improved, increase leading of electrode material
Electrically, rate charge-discharge performance can be effectively improved, reduce producing and improving its cycle life of irreversible capacity.This production method
It is cheap graphite tailing using raw material, genus is turned waste into wealth, and can effectively reduce lithium battery cost, decrease multiple in production process
Baking operation, technical process is easy to control, suitable industrialized mass production.
Brief description
Fig. 1 is the Graphene SME photo of the present invention；
Fig. 2 is Graphene/LiCoO2With conductive carbon black/LiCoO2The charging and discharging curve of battery；
Fig. 3 is Graphene/LiCoO2With conductive carbon black/LiCoO2The cyclic curve of battery；
Fig. 4 is the SEM photograph of conductive carbon black/LiCoO2 positive plate；
Fig. 5 is the SEM photograph of Graphene/LiCoO2 positive plate.
Specific embodiment
Below, in conjunction with specific embodiments, further illustrate the present invention, as shown in Figure 1：The graphene conductive agent slurry of the present invention
Material Main Ingredients and Appearance is submicron order Graphene, and particle diameter distribution is 10nm-15um, and its color is pitchy pulpous state, is put down by 1-600 layer
The carbonaceous material that the graphene sheet layer of row is constituted, its electrical conductivity is 5 × 103-9×104S/m, its specific surface area is 300-600m2/
G, under its 10mA current strength, charge specific capacity is up to 120-150F/g.
Graphene conductive agent granular size directly affects conductive effect, and the less conductive effect of particle is better, and particle is less than
Then agglomeration projects 10nm, is difficult dispersed：When particle is too big, electric conductivity weakens, and is also unfavorable for graphite granule simultaneously
Bag carry out.Product cut size of the present invention, in 10nm-15um, had both been beneficial to bag and had carried out, had stronger electric conductivity again.The Graphene number of plies is also shadow
One of electrical factor of pilot, the number of plies more at most conductive capability is weak, tends to general graphite, and the number of plies is easily reunited less, granule stability
Reduce, the present invention is controlled by process conditions and parameter, makes stratum granulosum numerical control system within less than 600.Graphene conductive agent
Specific surface area is excessive, easily generates SEI film, thus affecting the performance of battery, the graphene conductive agent specific surface area in the present invention exists
300-600m2/ g, because particle is thin, conductive agent adding proportion is little, does not result in material specific surface area and significantly increases phenomenon, it is to avoid
The generation of SEI film.The introducing of graphene conductive agent makes the charge movement speed of electrolyte intermediate ion accelerate, and improves discharge and recharge speed
Degree, graphene conductive agent electrical conductivity of the present invention is up to 5 × 103-9×104S/m.
The production method process route of the graphene conductive agent slurry of the present invention be by graphite tailing removal of impurities, pulverizing, purification,
Oxidation, reduction；Specific as follows：
Example one：
Graphite tailing 200kg is taken first to cross 100 mesh using the spin vibration sieve of the Φ 1500 of Xinxiang Gao Fu screening plant company production
Screen cloth, the largest particles is less than 15um, then tailing is put into the PP retort being produced by Anqiu Ke Hua glass steel mill, is proportionally added into
Hydrofluoric acid 80kg, hydrochloric acid 120kg, S nitric acid 40kg and pure water 240kg, open stirring, material are sufficiently mixed and stir simultaneously
It is passed through steam continuous heating 12 hours, adding substantial amounts of pure water makes material be cooled to room temperature, then mixed material is passed through pipeline
Put into the depickling of centrifuge elder generation, then be washed with deionized material to neutral, obtain the aqueous filter of the graphite for 15-25% through dehydration
Cake.
Above-mentioned aqueous graphite feed filter cake is added the oxygen of the liner tetrafluoroethene layer of Wuxi moral fluon chemical industry equipment company production
In graphite retort, retort internal temperature is adjusted to 0-4 DEG C, add the concentrated sulfuric acid of 2000kg, open and stir simultaneously
It is proportionally added into sodium nitrate 60kg, add potassium permanganate 200kg while stirring, to be mixed uniformly continue afterwards to stir and adjust reaction
Tank internal temperature is less than 20 DEG C, heats up and control internal temperature in the range of 32-38 DEG C after stirring reaction 1-12 hour, followed by
Continuous stirring 30min, is slowly added to 500kg deionized water, and is warming up to 80-100 DEG C of continuation stirring 30min, adds 1000kg's
Hydrogen peroxide makes material reaction fully, and now solution is changed into glassy yellow, filters while hot, first with 5% hydrochloric acid solution centrifuge washing about
5-20min, then with till pure water sulfate radical-free ion in the solution, obtaining graphene oxide filter cake through centrifugal dehydration.
Reduction：Above-mentioned graphene oxide filter cake and 2000kg hydrazine hydrate solution are sequentially added Wuxi moral fluon in proportion set
In the Graphene generate the tank that standby Co., Ltd produces, heat up and keep internal temperature at 50-70 DEG C, turn on agitator, rotating speed control
System, in 1000-5000rpm, stirs 5 hours, centrifugal filtration, is washed with deionized 30 minutes, without dehydration, direct discharging obtains
Graphene conductive agent slurry to water content 35%.
The graphene conductive agent slurry of present invention preparation adopts (SEM) SEM that HIT produces
Pattern is observed, to observe the microstructure of graphene particles using Hitachi transmission electron microscope HT7700, with Beijing gold angstrom spectrum
The F-Sorb2400 type N2 adsorption ratio surface area instrument that scientific ＆ technical corporation produces is long-pending to measure graphene conductive agent specific grain surface.Using
Shanghai thunder magnetic DDSJ-318 conductivity meter is measuring the electrical conductivity of graphene conductive agent.
The graphene conductive agent slurry of present invention preparation and the test of carbon black conductive agent chemical property；Graphene slurry：
PVDF：LiCoO2=3:5:93 mix in proportion, first will add after mixing according to the above ratio in graphene conductive agent slurry and PVDF
Enter a certain proportion of 1-METHYLPYRROLIDONE, ultrasonic disperse 60min, then by LiCoO2Add and stir and make slip, N-
The consumption of methyl pyrrolidone is being tuned into slip；Made battery slip coating machine is spread evenly across on aluminium foil,
It is placed in 120 DEG C of vacuum drying chamber and is dried more than 8 hours, dry and roll and make Graphene/LiCoO2 positive plate.With same
Method makes conductive carbon black/LiCoO2Positive plate, dried pole piece is transferred in glove box, using lithium piece as to electrode,
Full of being assembled into simulation button cell in the dry glove box of argon gas, barrier film adopts porous polypropylene film, and electrolyte adopts 1mol/
The LiPF6 of L, solvent is the mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC), EC：The mass ratio of DEC is 1：1；
Carry out battery performance test, discharge and recharge using the battery performance test instrument button type battery that Shenzhen Xin Wei energy science and technology company produces
Voltage range is 2.75-42V, surveys battery capacity with 0.5C charging and discharging currents, and 1C charging and discharging currents survey battery cycle life；Fig. 2
It is Graphene/LiCoO2With conductive carbon black/LiCoO2The charging and discharging curve of battery；
Graphene/LiCoO is recorded during 1C discharge and recharge2The charging capacity of simulated battery is 147.9mAh/g, its discharge capacity
For 145.9mAh/g, efficiency for charge-discharge is 98.7%；And testing conductive carbon black/LiCoO2The charging capacity of simulated battery is
144.3mAh/g；Its discharge capacity is 135.5mAh/g, and its efficiency for charge-discharge is 93.9%；Graphene/LiCoO2Simulated battery
Discharge capacity under 1C charge-discharge magnification is than conductive carbon black/LiCoO2The high 12.4mAh/g of discharge capacity of simulated battery, this fills
Bright Graphene conductive agent of defending oneself not only changes the electric conductivity of battery electrode, so that the capacity of positive active material is also obtained simultaneously
Further performance.
Cycle life compares：Fig. 3 is Graphene/LiCoO2Simulated battery and conductive carbon black/LiCoO2Simulated battery cyclicity
Energy curve, Graphene/LiCoO under 1C multiplying power2Simulated battery its discharge capacity after 150 circulations is still initial capacity
98.7%, after circulation 300 times, discharge capacity decays to 137mAh/g due to 145mAh/g, and discharge capacity can keep initial
95.1%, only reduce 4.9%；And make the conductive carbon black/LiCoO of conductive agent with conductive carbon black2Simulated battery is in similarity condition
Lower circulation 300 times, its discharge capacity decays to 121mAh/g by 135mAh/g, then discharge capacity is held only in initial capacity
89.7%, therefore its chemical property in lithium battery is used for graphene conductive agent slurry more superior than conventional carbon black conductive agent
Many.
Graphene/LiCoO2Positive plate and conductive carbon black/LiCoO2The sem analysis of positive plate：
Fig. 4 is conductive carbon black/LiCoO2The SEM figure of positive plate, Fig. 5 is Graphene/LiCoO2The SEM figure of positive plate, by scheming
4 find out that carbon black granules have significantly to reunite with having no is regularly distributed on LiCoO2Around particle, and Fig. 5 graphene particles have
Relatively large surface area, its surface folding can effectively wrap LiCoO2Particle, forms the conductive contact interface of face contact, shows
Write and improve LiCoO2The electric conductivity of particle, compared with granular conductive agent conductive carbon black, Graphene be flake thus be easy to
Build good three-dimensional conductive network in the electrodes；And conductive carbon black little particle is easily reunited it is easy to be absorbed in LiCoO2The sky of particle
Electric action is not had in gap.The thickness of Graphene in 1nm, under same quality because the specific surface area of Graphene than
Big many of conductive carbon black, can form more effectively conductive network, and this three-dimensional conductive network structure not only can improve electricity
The electric conductivity of pole, and the amount added in the electrodes is relatively fewer just can reach good conductive effect.
Example two：
Graphite tailing 500kg is taken first to cross 100 mesh using the spin vibration sieve of the Φ 1500 of Xinxiang high frequency screening plant company production
Screen cloth, then tailing is put into the PP retort being produced by Anqiu Ke Hua glass steel mill, it is proportionally added into hydrofluoric acid 200kg, hydrochloric acid
300kg, nitric acid 100kg and pure water 600kg, open stirring, and material being sufficiently mixed to stir is passed through steam simultaneously and persistently adds
Heat 12 hours, adding substantial amounts of pure water makes material be cooled to room temperature, then mixed material is put into centrifuge by pipeline first takes off
Acid, then it is washed with deionized material to neutral, obtain the aqueous Graphite Cake for 15-25% through dehydration.
Above-mentioned aqueous graphite feed filter cake is added the oxygen of the liner tetrafluoroethene layer of Wuxi moral fluon chemical industry equipment company production
In graphite retort, retort internal temperature is adjusted to 0-4 DEG C, add the concentrated sulfuric acid of 5000kg, open and stir simultaneously
Be proportionally added into sodium nitrate 150kg, add potassium permanganate 500kg while stirring, to be mixed uniformly continue afterwards to stir and adjust anti-
Answer tank internal temperature to be less than 20 DEG C, heat up after stirring reaction 1-12 hour and control internal temperature in the range of 32-38 DEG C, then
Continue stirring 30min, be slowly added to 1500kg deionized water, and be warming up to 80-100 DEG C to continue stirring 30min, add 1500kg
Hydrogen peroxide make material reaction fully, now solution is changed into glassy yellow, filters while hot, first with 5% hydrochloric acid solution centrifuge washing
About 5-20min, then with till pure water sulfate radical-free ion in the solution, obtaining graphite oxide filter cake through centrifugal dehydration.
Reduction：Above-mentioned graphite oxide filter cake and 2000kg hydrazine hydrate solution are sequentially added Wuxi moral fluon equipment in proportion
In the Graphene generate the tank that Co., Ltd produces, heat up and keep internal temperature at 50-70 DEG C, turn on agitator, rotating speed controls
In 1000-5000rpm, stir 5 hours, centrifugal filtration, be washed with deionized 30 minutes, without dehydration, direct discharging obtains
The graphene conductive agent slurry of water content 35%.
The graphene conductive agent slurry of present invention preparation adopts (SEM) SEM that HIT produces
Pattern is observed, to observe the microstructure of graphene particles using Hitachi transmission electron microscope HT7700, with Beijing gold angstrom spectrum
The F-Sorb2400 type N2 adsorption ratio surface area instrument that scientific ＆ technical corporation produces is long-pending to measure graphene conductive agent specific grain surface.Using
Shanghai thunder magnetic DDSJ-318 conductivity meter is measuring the electrical conductivity of graphene conductive agent.
The graphene conductive agent slurry of present invention preparation and the test of carbon black conductive agent chemical property；
Embodiment：
The making of graphene conductive agent anode pole piece：
Graphene slurry：PVDF：LiCoO2=3:5:93 mix in proportion, first by graphene conductive agent slurry and PVDF
A certain proportion of 1-METHYLPYRROLIDONE is added after mixing according to the above ratio, ultrasonic disperse 60min, then by LiCoO2Add and mix
Stirred 4 hours with 2000rpm in machine, make slip, made battery slip coating machine is spread evenly across on aluminium foil, is placed in
It is dried more than 8 hours in 120 DEG C of vacuum drying chamber, dry and roll and make Graphene/LiCoO2Positive plate.Again through cut-parts with
Barrier film and negative plate wind in order, fluid injection, encapsulation are obtained 18650 cylindrical batteries and carry out electrochemical property test.Cathode pole piece
Making：Graphene conductive agent slurry：Negative material MCMB：Binding agent SBR：Thickener CMC=2：94：2.5：1.5 press this matter
Amount ratio adds in mixing machine, is mixed with 1500rpm rotating speed stirring 5h using water as solvent, in mixer after mixing
Slip is coated on Copper Foil, is dried 8 hours, obtains cathode pole piece through roll-in in 120 DEG C of vacuum drying chambers.
Comparative example：Conductive carbon black is made conductive agent and is made conductive carbon black/LiCoO in same way as described above2Positive plate and conduction
Carbon black/MCMB negative plate, positive plate winds in order through cut-parts and barrier film and negative plate, fluid injection, encapsulation are obtained 18650 cylinders electricity
Pond carries out electrochemical property test.Barrier film adopts porous polypropylene film, and electrolyte adopts the LiPF of 1mol/L6, solvent is carbonic acid
Vinyl acetate (EC) and the mixed solvent of diethyl carbonate (DEC), EC：The mass ratio of DEC is 1：1；Using Shenzhen Xin Wei Energy Section
The battery performance test instrument that skill company produces carries out battery performance test to 18650 batteries, its chemical property contrast such as following table：
From table, test result be can be seen that graphene conductive agent slurry and is added in battery material with the ratio of 2-5%,
Its electric conductivity increases, and its internal resistance significantly reduces, and charge/discharge rates and rate charge-discharge performance and cycle performance are greatly improved, can not
Inverse capacity reduces, and being therefore used for its chemical property in lithium battery with graphene conductive agent slurry will than conventional carbon black conductive agent
Outstanding much.
Claims (8)
1. a kind of the method for graphene conductive agent slurry is prepared it is characterised in that it comprises the following steps with graphite tailing：
Step one, removal of impurities：Graphite tailing is crossed 100 eye mesh screens, removes the internal various debris more than 50 microns；
Step 2, purification：Graphite tailing after removal of impurities is put into retort, is proportionally added into hydrofluoric acid, hydrochloric acid, nitric acid and pure
Water, its mixed proportion with graphite：Graphite tailing：Hydrofluoric acid：Hydrochloric acid：Nitric acid：Pure water=1:0.1～0.5:0.3～0.9：0.1
～0.3：0.5～1.0；Stir and be warming up to 80～120 DEG C, the constant reaction of keeping temperature 12 hours, add water cooling simultaneously
Centrifuge washing, to neutral, obtains the aqueous Graphite Cake for 15-25% through dehydration；
Step 3, oxidation：By above-mentioned aqueous graphite feed filter cake add graphite oxide retort in, by retort internal temperature adjust to
0-4 DEG C, add the appropriate concentrated sulfuric acid, open the solid mixture stirring and being proportionally added into described Graphite Cake and nitrate,
Add strong oxidizer while stirring, to be mixed uniformly continue to stir and adjust retort internal temperature afterwards and be less than 20 DEG C, stirring
Heat up after reaction 1-12 hour and control internal temperature in the range of 32-38 DEG C, be further continued for stirring 30min, be slowly added to appropriate
Deionized water, and it is warming up to 80-100 DEG C of continuation stirring 30min, add appropriate hydrogen peroxide to make material reaction fully, now molten
Liquid is changed into glassy yellow, filters while hot, till washing sulfate radical-free ion in the solution, obtains graphite oxide filter through centrifugal dehydration
Cake；
Step 4, reduction：Described graphite oxide filter cake and reductant solution are proportionally added in Graphene generate the tank, heat up simultaneously
Keep internal temperature at 50-70 DEG C, turn on agitator, rotating speed controls in 1000-5000rpm, stirring 1-5 hour, centrifugal filtration,
It is washed with deionized, through dehydration, dewatering time is less than 30 minutes, obtains the Graphene slurry of water content 30-40%；Oxidation stone
Black filter cake：Reducing agent=1：10-30；Reducing agent is one or more of hydrazine hydrate, ethylene glycol, ethylene glycol sodium, sodium borohydride.
2. according to claim 1 the method for graphene conductive agent slurry is prepared with graphite tailing it is characterised in that described
Step 2, in purification, described fluohydric acid content is 40-60%, and content of hydrochloric acid is 30%, and nitric acid content is 40-70%, the concentrated sulfuric acid
Content is 70-99%, and deionized water is less than 15 μ S/cm reverse osmosis waters for electrical conductivity.
3. according to claim 1 the method for graphene conductive agent slurry is prepared with graphite tailing it is characterised in that described
Step 3, in oxidation, described graphite powder：Strong acid solution：Nitrate：Strong oxidizer：Hydrogen peroxide：Deionized water quality ratio：1：
10～50:0.3～0.8：1～5:1～5：30～60.
4. according to claim 1 the method for graphene conductive agent slurry is prepared with graphite tailing it is characterised in that described
Step 3, in oxidation, first with 5% hydrochloric acid solution centrifuge washing about 5-20min, then use pure water.
5. according to claim 1 the method for graphene conductive agent slurry is prepared with graphite tailing it is characterised in that described
Step 3, aoxidizes used graphite oxide retort and can adjust retort for temperature, and its housing is to have interlayer, interlayer in carbon steel
Interior inwall is close in inside the thick polytetrafluoroethylene floor of 3-8mm for liquid temperature control medium, prevents materials inside from tank body is corroded；
Interlayer dielectric is connected with compressor, by compressor, liquid medium is cooled down or heats, by liquid medium with heat exchange pattern
Control materials inside temperature, material is adjusted by thermocouple sensor temperature required.
6. according to claim 1 the method for graphene conductive agent slurry is prepared it is characterised in that described step with graphite tailing
Graphene generate the tank in rapid four, be one similar to kettle shape reactor, inner-wall spraying wear-resistant ceramic, kettle shape shell wall is contained within
Interlayer, is cast by carbon steel, and interlayer, built with liquid medium, controls internal temperature for heat transfer；There is an oval stirring inside tank
Device, agitator surface spraying tungsten carbide, agitator speed 1000-6000rpm.
7. according to claim 1 the method for graphene conductive agent slurry is prepared it is characterised in that described stone with graphite tailing
Black tailing is that crystalline flake graphite produces tailing produced by negative pole spherical graphite, the graphite microparticles of its meso-position radius≤12um, and its carbon contains
Measure as 92-95%, density is about 0.1-0.8g/ml.
8. according to claim 1 the method for graphene conductive agent slurry is prepared with graphite tailing it is characterised in that prepared
The particle size distribution of the graphene conductive agent slurry obtaining is 10nm-15um, and its color is pitchy pulpous state, is 1-600 layer
The carbonaceous material that parallel graphene sheet layer is constituted, its electrical conductivity is 5 × 104-9×104S/m, its specific surface area is 300-
600m2/ g, under its 10mA current strength, its charge specific capacity reaches 120-150F/g.
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Denomination of invention: Method for preparing Graphene conductive agent slurry with graphite tail Effective date of registration: 20230614 Granted publication date: 20190205 Pledgee: Postal Savings Bank of China Limited Hegang branch Pledgor: LUOBEI AOXING NEW MATERIALS CO.,LTD. Registration number: Y2023230000049 |