CN109728300A - A kind of lithium battery electrocondution slurry and preparation method thereof containing different defect graphenes - Google Patents
A kind of lithium battery electrocondution slurry and preparation method thereof containing different defect graphenes Download PDFInfo
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Abstract
The present invention provides a kind of lithium battery electrocondution slurry and preparation method thereof containing different defect graphenes, and the graphene of the difference defect includes graphene one and graphene two, and the intensity ratio ID/IG at one peak Raman D of graphene and the peak G isThe intensity ratio ID/IG at two peak Raman D of graphene and the peak G isGraphene one has defect and porous characteristic, is conducive to lithium ion conduction, and two defect of graphene is few, non-porous in face, is conducive to electronics conduction, the two works in coordination, forms the conductive network of perfect electronics and lithium ion, can effectively promote monolithic conductive performance.
Description
Technical field
The invention belongs to new energy lithium battery electrocondution slurry fields, and in particular to a kind of lithium electricity containing different defect graphenes
Pond electrocondution slurry and preparation method thereof.
Background technique
It is increasingly significant with energy and environment problem, it taps a new source of energy, promote electric tool and have become market orientation,
And the exploitation of these emerging technologies be unable to do without the development of energy storage device, lithium ion battery is as presently the most important accumulator
Part has obtained vast industrial circle and the favor of researcher.And the anode material for lithium-ion batteries being widely used at present includes ternary
The conductivity of material, LiFePO4, cobalt acid lithium, LiMn2O4 etc., positive electrode is lower, needs to add between material granule suitable
The fine and close conductive network of conductive agent building, provides express passway for electron-transport.Currently used conductive agent be mostly conductive black,
The conductive agent of carbon nanotube, graphene or a few persons compounding, is added to various dispersing agents or surfactant, reacts in battery system
Complex, if additionally adding other dispersing agents or surfactant be easy to cause security risk, and various conductive agents compound
In it is more apparent with carbon nanotube and graphene compounding effect advantage, and carbon nanotube is there are agglomeration is more serious, and its viscosity
Changing over time can become larger, and have problem in industrialization coating.Application system of the graphene in lithium ion battery is to pass through
With active material face contact, graphene has lower conductivity threshold, electrode can be increased substantially when usage amount is less
Electronic conductivity, reduce conductive agent dosage, improve the volume energy density of battery.But the meanwhile two-dimensional surface knot of graphene
Structure can generate " steric effect " to the lithium ion transport of electrode interior again, for ionic conduction, large stretch of diameter stone of liquid phase stripping method
The ionic conduction of black alkene is relatively poor, may be limited in high-multiplying-power battery application；And oxidation-reduction method preparation graphene, because
When this step of graphene oxide, a large amount of functional groups are contained on surface, and after reduction, this functional group site graphene easy to form
Defect and hole influence the formation of conductive network, and electronics conduction is relatively poor, but with liquid phase stripping method still in an order of magnitude.
Summary of the invention
The purpose of the present invention is by using containing different defects graphene one and graphene two graphene conductive slurry,
Solve the problems, such as that the transmission of graphene conductive agent intermediate ion and electronic conduction, concrete scheme are as follows:
The graphene of a kind of lithium battery electrocondution slurry containing different defect graphenes, the difference defect includes graphene one
With graphene two, the intensity ratio at one peak Raman D of graphene and the peak G is that ID/IG is preferablyThe graphene
The intensity ratio ID/IG at two peaks Raman D and the peak G is
Optionally, the intensity ratio ID/IG at one peak Raman D of graphene and the peak G is
Optionally, the intensity ratio ID/IG at two peak Raman D of graphene and the peak G is
Optionally, the mass ratio of the graphene two and graphene one existsBetween.
A kind of preparation method of above-mentioned lithium battery electrocondution slurry, includes the following steps:
(1) redox method prepares redox graphene powder, by the redox graphene powder, dispersion
Agent one and the mixed mixture of solvent one pass through dispersion milling apparatus unit one and carry out dispersion grinding, obtain the slurry of graphene one
Material；
(2) expanded graphite powder, dispersing agent two and the mixed mixture of solvent two are passed through into dispersion milling apparatus unit
Two carry out dispersion grinding removing, obtain the slurry of graphene two；
(3) slurry of graphene two made from by described in (2) is mixed with the slurry of graphene one made from (1)
Dispersion.
Optionally, the dispersing agent one and dispersing agent two are Kynoar.
Optionally, the solvent one and solvent two are N-Methyl pyrrolidone.
Optionally, the mass percent of the graphene powder isThe mass percent of the dispersing agent one
ForThe mass percent of the expanded graphite powder isThe mass percent of the dispersing agent two
For
Optionally, the graphene one is prepared as follows acquisition:It is lower that natural stone is added into the concentrated sulfuric acid
After stirring is completely dissolved, natural graphite quality multiple is added in inkTimes potassium permanganate andSodium nitrate again,
?StirringThen ultrasonic in ice-water bathIt is diluted with water reaction solution, hydrogen peroxide stirring, mistake is added
Filter is sufficiently washed to pH value extremely with acid and waterDry, airflow milling crushes, after obtaining graphene oxide powder, Gao Wenre
Reduction.
Optionally, after high temperature thermal reduction, the intensity ratio at one peak Raman D of graphene and the peak G is improved by further pore-creating.
Optionally, graphene is limited without specific surface area and the number of plies in the present invention, the redox graphene powder is logical
Under type such as is crossed to prepare:It is lower that natural graphite is added into the concentrated sulfuric acid, after stirring is completely dissolved, natural stone is added
Black quality multipleTimes potassium permanganate andSodium nitrate again,StirringNitric acid oxidation
The higher defect area of chemical activity in graphene oxide layer can be selectively removed in the process, reach the mesh of the pore-creating on lamella
's.Then ultrasonic in ice-water bathIt is diluted with water reaction solution, hydrogen peroxide stirring is added, filtering is sufficiently washed with acid and water
Extremely to pH valueDry, airflow milling crushes, and after obtaining graphene oxide powder, high temperature is sufficiently heat-treated.It is prepared
It can be activated using electronics etching method or KOH with defective and some perforations redox graphenes, further be had again
The graphene of more multiple hole.Graphene is activated by electronics etching method or KOH, can effectively be introduced on lamella a large amount of micropores with
It is mesoporous.
Compared with prior art, it is provided by the invention using the lithium battery electrocondution slurry prepared containing different defect graphenes and
Preparation method is led by the lithium battery that the graphene one and graphene two at the peak different Raman D and the intensity ratio at the peak G form graphene
Plasma-based material.The graphene one easily forms hole or broken, electrolyte large amount of adsorption on its surface, easy to disperse, though electronic conduction
Property is slightly worse, but is conducive to the transmission of lithium ion；The graphene two, does not form compared with havoc graphene itself, and defect is less,
Structural integrity, electron conduction is good, but lithium ion transport access denial.Two kinds of graphenes are worked in coordination, and lithium ion biography has both been possessed
Defeated channel, and there is good electron conduction, the two acts synergistically to form perfect conductive network, effectively improves entirety
Electric conductivity.
Detailed description of the invention
Fig. 1 is that the graphene slurry of embodiment 1-3, embodiment 5-9 ﹑ comparative example 1 and comparative example 2 scratch on utter misery aluminium foil
Pole piece test EIS effect picture.
Specific embodiment
Below by specific embodiment, the present invention is described in further detail, but the present invention is not limited to tool below
Body embodiment.
Lithium battery electrocondution slurry of the specific embodiment of the invention containing different defect graphenes, it is characterised in that, it is described not
Graphene with defect includes graphene one and graphene two, the intensity ratio i.e. ID/IG at one peak Raman D of graphene and the peak G
PreferablyThe intensity ratio ID/IG at two peak Raman D of graphene and the peak G isHair of the invention
Bright people passes through the study found that graphene one, has a more defect, and surface forms hole, in the electrocondution slurry being prepared into, lithium from
Son transmission is with the obvious advantage, and electronic conduction is poor, simultaneously because it with more defect and hole, liquid absorption amount is big, viscosity is excessively high；
And graphene two, structural integrity, size are larger, electron conduction is excellent, but since complete large stretch of diameter can make lithium ion conduction
It is obstructed, ionic conductivity is poor；After the two combines, high speed dispersion is uniform, thus both in terms of lithium ion transport, electronic conduction
It cooperates with, work in coordination, form perfect conductive network.
The mass ratio of the lithium battery electrocondution slurry of the specific embodiment of the invention, the graphene two and graphene one existsBetween, preferablyBetween, further preferablyBetween, still more preferably forBetween,
When the mass ratio of graphene two and graphene one existsBetween when, on the one hand while can obtain good electrical property, holding
The graphene one is in lower ratio, since the graphene one usually requires to prepare by redox, in the preparation
Complex process, and it is easy to produce a large amount of spent acid waste liquid, to be conducive to improve process efficiency, and reduce industrial wastewater
Processing cost.
The lithium battery electrocondution slurry of the specific embodiment of the invention, one defect of graphene and hole will affect lithium when less
Ion transmission, when excessively high, the cost increase process time extends, and comprehensively considers lithium ion transport and electron conduction and cost process etc.,
The peak Raman D and G peak intensity ratio of the graphene one, i.e. the peak ID/IG is preferablyMore preferably
The process time can be at when the lithium battery electrocondution slurry of the specific embodiment of the invention, two defect of graphene are more
Extend again, it is higher to energy consumption, equipment requirement；And defect hour, then it is that graphite flake is not peeled away with piece, still keeps stacked in multi-layers
State causes electric conductivity very poor, and sedimentation is serious, and viscosity is very low, comprehensively considers performance and cost process etc., the graphene two
The peak Raman D and G peak intensity ratio, i.e., ID/IG existsBetween, preferablyBetween.
The lithium battery electrocondution slurry of the specific embodiment of the invention, one partial size of graphene is excessive, will affect its electrical property
Can, too small grinding technics requires height, comprehensively considers its electrical property and grinding technics, the partial size D50 of the graphene one is preferablyFurther preferablyStill more preferably it isThe partial size D50 refers to accumulative grain
Degree percentile reaches partial size corresponding when 50%, and the particle greater than the partial size accounts for 50%, less than of the partial size
Grain also accounts for 50%, D50 and is also meso-position radius or median particle diameter.D50 is commonly used to indicate the average particle size of powder.
The pole piece resistivity of the lithium battery electrocondution slurry of the specific embodiment of the invention, preferably described one slurry of graphene isThe pole piece resistivity of two slurry of graphene isOne He of containing graphene
The pole piece resistivity of the slurry of graphene two is
A kind of preparation method of above-mentioned lithium battery electrocondution slurry of the specific embodiment of the invention, includes the following steps:
(1) redox method prepares redox graphene powder, by the redox graphene powder, dispersion
Agent one and the mixed mixture of solvent one pass through dispersion milling apparatus unit one and carry out dispersion grinding, obtain the slurry of graphene one
Material；
(2) expanded graphite powder, dispersing agent two and the mixed mixture of solvent two are passed through into dispersion milling apparatus unit
Two carry out dispersion grinding removing, obtain the slurry of graphene two；
(3) slurry of graphene two made from by described in (2) is mixed with the slurry of graphene one made from (1)
Dispersion.
A kind of preparation method of above-mentioned lithium battery electrocondution slurry of the specific embodiment of the invention, the solvent one and solvent
Two be independently the common solvent of graphene, for example, N-Methyl pyrrolidone, dimethyl acetamide, dimethylformamide or
Dimethyl sulfoxide, the preferably described solvent one and solvent two are N-Methyl pyrrolidone.
A kind of preparation method of above-mentioned lithium battery electrocondution slurry of the specific embodiment of the invention, the dispersing agent one and point
Powder two is independently Kynoar (PVDF), polytetrafluoroethylene (PTFE) (PTFE) etc., preferably Kynoar.
A kind of preparation method of above-mentioned lithium battery electrocondution slurry of the specific embodiment of the invention, the graphene powder
Mass percent isIt is preferred thatThe mass percent of the dispersing agent one isIt is preferred thatThe mass percent of the expanded graphite powder isIt is preferred thatThe dispersing agent two
Mass percent beIt is preferred that
A kind of preparation method of above-mentioned lithium battery electrocondution slurry of the specific embodiment of the invention, the reduction-oxidation graphite
Alkene powder is prepared as follows acquisition:The lower natural graphite that is added into the concentrated sulfuric acid adds after stirring is completely dissolved
Enter natural graphite quality multipleTimes potassium permanganate andSodium nitrate again,Stirring
The higher defect area of chemical activity in graphene oxide layer can be selectively removed during nitric acid oxidation, is reached on lamella
The purpose of pore-creating, it is then ultrasonic in ice-water bathIt is diluted with water reaction solution, hydrogen peroxide stirring, filtering, with acid and water is added
It sufficiently washs to pH value extremelyDry, airflow milling crushes, after obtaining graphene oxide powder, high temperature thermal reduction, and specific work
Skill condition can be configured according to the actual situation.Further, high temperature thermal reduction after, be prepared with defective and partial hole
The redox graphene in hole can further obtain the graphene with more multiple hole again using electronics etching or KOH activation, from
And the intensity ratio at one peak Raman D of graphene and the peak G is improved by electronics etching or KOH activation.
A kind of preparation method of above-mentioned lithium battery electrocondution slurry of the specific embodiment of the invention, the expanded graphite,
Its expansion multiplying power isTimes, mesh number is
It is described further below by way of specific embodiment.
Raw material explanation:
Natural graphite: Qingdao day Sheng Da graphite Co., Ltd
Expanded graphite: one sail graphite Co., Ltd of Shanghai
Test method:
Raman test: Raman spectrometer uses Germany color dispersion-type Confocal laser-scanning microscopy instrument Senterra R200-L.Raman
Spectrum has unique advantage, the meeting near 1350cm-1 with defective graphene in terms of the defect of characterization grapheme material
There is the peak Raman D, it is general to characterize the defect density in graphene with the intensity ratio (ID/IG) at the peak D and the peak G, studies have shown that defect
Density is proportional to ID/IG.Sample solvent is dispersed, after ultrasonic 10min, with dropper drop on silicon wafer, natural air drying, sampling is surveyed
Examination.
D50 partial size: test equipment is Dandong Bai Te laser particle analyzer S2600, and NMP does mobile phase, and refractive index is when test
Real part 1.8 and imaginary part 0.7 after scanning mobile phase background, take 1 droplet slurry sample to instill sample cell, use before testing with small dropper
Ultrasonic machine built in laser particle analyzer is ultrasonically treated 30 seconds, and follow-on test is averaged.
Pole piece resistivity: the graphene slurry is used in lithium ion battery LFP system material, according to LFP, polyvinylidene fluoride
Alkene, graphene composite mortar conductive agent mass ratio be 100:3:1 (in terms of conductive agent), by adding NMP adjustment solid containing to 49%,
Anode sizing agent is made after 2 hours in stirring, is coated on PET film, obtains anode pole piece after 90 degree of drying.Pole piece (PET film) is cut out
At 5cmx5cm square, pole piece thickness is measured using altimeter, is tested using four probe resistance rate of Suzhou lattice ST2258C type
Instrument test pole sheet resistivity.
Electrochemical impedance spectroscopy (EIS) test: first pole piece (Al foil substrate) is prepared into button electricity in glove box, used
CHI660E electrochemical workstation is electrically connected with button, and setting parameter is tested, and saves data, does figure with Origin software.
The preparation of redox graphene slurry
Preparation example 1-1
It is lower that natural graphite is added into the concentrated sulfuric acid, after stirring is completely dissolved, natural graphite quality multiple 3 is added
Potassium permanganate and 0.41 times of sodium nitrate again,3h is stirred, then ultrasound 3h in ice-water bath, is diluted with water anti-
Liquid is answered, hydrogen peroxide stirring is added, filtering is sufficiently washed to pH value extremely with acid and waterDry, airflow milling crushes, and obtains oxygen
After graphite alkene powder, 800 DEG C of high temperature sufficiently thermal reduction 0.5h.By redox graphene powder (4wt%), dispersing agent
Said mixture material is carried out pre-dispersed and grinding by (1wt%), NMP (95wt%) mixing, so that each component is sufficiently mixed, grain
Diameter D50 is ground to 1um, ID/IG 1.1.
Preparation example 1-2
It is lower that natural graphite is added into the concentrated sulfuric acid, after stirring is completely dissolved, natural graphite quality multiple 3 is added
Potassium permanganate and 0.62 times of sodium nitrate again,5h is stirred, then ultrasound 6h in ice-water bath, is diluted with water anti-
Liquid is answered, hydrogen peroxide stirring is added, filtering is sufficiently washed to pH value extremely with acid and waterDry, airflow milling crushes, and obtains oxygen
After graphite alkene powder, 800 DEG C of high temperature sufficiently thermal reduction 0.5h.By redox graphene powder (4wt%), dispersing agent
Said mixture material is carried out pre-dispersed and grinding by (1wt%), NMP (95wt%) mixing, so that each component is sufficiently mixed, grain
Diameter D50 is ground to 1um, ID/IG 1.5.
Preparation example 1-3
It is lower that natural graphite is added into the concentrated sulfuric acid, after stirring is completely dissolved, natural graphite quality multiple 3 is added
Potassium permanganate and 0.55 times of sodium nitrate again,4h is stirred, then 5h in ultrasonic ice-water bath, is diluted with water anti-
Liquid is answered, hydrogen peroxide stirring is added, filtering is sufficiently washed to pH value extremely with acid and waterDry, airflow milling crushes, and obtains oxygen
After graphite alkene powder, 800 DEG C of high temperature sufficiently thermal reduction 0.5h.By redox graphene powder (4wt%), dispersing agent
Said mixture material is carried out pre-dispersed and grinding by (1wt%), NMP (95wt%) mixing, so that each component is sufficiently mixed, grain
Diameter D50 is ground to 1um, ID/IG 1.4.
Preparation example 1-4
It is lower that natural graphite is added into the concentrated sulfuric acid, after stirring is completely dissolved, natural graphite quality multiple 3 is added
Potassium permanganate and 0.48 times of sodium nitrate again,3.5h is stirred, then ultrasound 4h in ice-water bath, is diluted with water
Reaction solution, is added hydrogen peroxide stirring, and filtering is sufficiently washed to pH value extremely with acid and waterDry, airflow milling crushes, and obtains
After graphene oxide powder, 800 DEG C of high temperature sufficiently thermal reduction 0.5h.By redox graphene powder (4wt%), dispersing agent
Said mixture material is carried out pre-dispersed and grinding by (1wt%), NMP (95wt%) mixing, so that each component is sufficiently mixed, grain
Diameter D50 is ground to 1um, ID/IG 1.3.
Preparation example 1-5
It is lower that natural graphite is added into the concentrated sulfuric acid, after stirring is completely dissolved, natural graphite quality multiple 3 is added
Potassium permanganate and 0.27 times of sodium nitrate again,2.5h is stirred, then ultrasound 2h in ice-water bath, is diluted with water
Reaction solution, is added hydrogen peroxide stirring, and filtering is sufficiently washed to pH value extremely with acid and waterDry, airflow milling crushes, and obtains
After graphene oxide powder, 800 DEG C of high temperature sufficiently thermal reduction 0.5h.By redox graphene powder (4wt%), dispersing agent
Said mixture material is carried out pre-dispersed and grinding by (1wt%), NMP (95wt%) mixing, so that each component is sufficiently mixed, grain
Diameter D50 is ground to 1um, ID/IG 0.9.
Preparation example 1-6
It is lower that natural graphite is added into the concentrated sulfuric acid, after stirring is completely dissolved, natural graphite quality multiple 3 is added
Potassium permanganate and 0.2 times of sodium nitrate again,2h is stirred, then ultrasound 1h in ice-water bath, is diluted with water reaction
Liquid, is added hydrogen peroxide stirring, and filtering is sufficiently washed to pH value extremely with acid and waterDry, airflow milling crushes, and is aoxidized
Graphene powder is last, 800 DEG C of high temperature sufficiently thermal reduction 0.5h.By redox graphene powder (4wt%), dispersing agent
Said mixture material is carried out pre-dispersed and grinding by (1wt%), NMP (95wt%) mixing, so that each component is sufficiently mixed, grain
Diameter D50 is ground to 1um, ID/IG 0.8.
Preparation example 1-7
It is lower that natural graphite is added into the concentrated sulfuric acid, after stirring is completely dissolved, natural graphite quality multiple 3 is added
Potassium permanganate and 0.2 times of sodium nitrate again,2h is stirred, then ultrasound 1h in ice-water bath, is diluted with water reaction
Liquid, is added hydrogen peroxide stirring, and filtering is sufficiently washed to pH value extremely with acid and waterDry, airflow milling crushes, and is aoxidized
Graphene powder is last, 800 DEG C of high temperature sufficiently thermal reduction 0.5h.It takes above-mentioned powder to be configured to aqueous slurry, reduced powder constitution is added
The KOH of 5 times of multiple of amount is activated, and after 2h is sufficiently stirred, 20h is placed in sealing under room temperature, is placed in 70 DEG C of baking ovens and is dried,
It is sufficiently washed to pH value extremely with acid and waterAirflow milling crushes, after obtaining graphene oxide powder, 800 DEG C of high temperature heat treatments
0.5h。
The redox graphene powder (4wt%), dispersing agent (1wt%), NMP (95wt%) of activation are mixed, it will be upper
It states mixed material and carries out pre-dispersed and grinding, so that each component is sufficiently mixed, partial size D50 is ground to 1um, ID/IG 1.1.
The preparation of liquid phase stripping method graphene slurry
Preparation example 2-1
By expanded graphite powder (4wt%, expansion multiplying power are 200 times, and mesh number is 20 mesh), dispersing agent (1wt%), NMP
Said mixture material is carried out pre-dispersed and grinding and removed by (95wt%) mixing, so that each component is sufficiently mixed, milling time
3h, ID/IG 0.35.
Preparation example 2-2
By expanded graphite powder (4wt%, expansion multiplying power are 200 times, and mesh number is 20 mesh), dispersing agent (1wt%), NMP
Said mixture material is carried out pre-dispersed and grinding and removed by (95wt%) mixing, so that each component is sufficiently mixed, milling time is
1h, ID/IG 0.2.
Preparation example 2-3
By expanded graphite powder (4wt%, expansion multiplying power are 200 times, and mesh number is 20 mesh), dispersing agent (1wt%), NMP
Said mixture material is carried out pre-dispersed and grinding and removed by (95wt%) mixing, so that each component is sufficiently mixed, milling time
1.5h, ID/IG 0.25.
Preparation example 2-4
By expanded graphite powder (4wt%, expansion multiplying power are 200 times, and mesh number is 20 mesh), dispersing agent (1wt%), NMP
Said mixture material is carried out pre-dispersed and grinding and removed by (95wt%) mixing, so that each component is sufficiently mixed, milling time
4.5h, ID/IG 0.45.
Preparation example 2-5
By expanded graphite powder (4wt%, expansion multiplying power are 200 times, and mesh number is 20 mesh), dispersing agent (1wt%), NMP
Said mixture material is carried out pre-dispersed and grinding and removed by (95wt%) mixing, so that each component is sufficiently mixed, milling time
7h, ID/IG 0.5.
Embodiment 1
The slurry of the slurry of preparation example 1-1 and preparation example 2-1 are subjected to mixing dispersion, high speed dispersion 2h in 1:4 ratio.
Embodiment 2
The slurry of the slurry of preparation example 1-2 and preparation example 2-1 are subjected to mixing dispersion, high speed dispersion 2h in 1:4 ratio.
Embodiment 3
The slurry of the slurry of preparation example 1-3 and preparation example 2-1 are subjected to mixing dispersion, high speed dispersion 2h in 1:4 ratio.
Embodiment 4
The slurry of the slurry of preparation example 1-4 and preparation example 2-1 are subjected to mixing dispersion, high speed dispersion 2h in 1:4 ratio.
Embodiment 5
The slurry of the slurry of preparation example 1-5 and preparation example 2-1 are subjected to mixing dispersion, high speed dispersion 2h in 1:4 ratio.
Embodiment 6
The slurry of the slurry of preparation example 1-6 and preparation example 2-1 are subjected to mixing dispersion, high speed dispersion 2h in 1:4 ratio.
Embodiment 7
The slurry of the slurry of preparation example 1-7 and preparation example 2-1 are subjected to mixing dispersion, high speed dispersion 2h in 1:4 ratio.
Embodiment 8
The slurry of the slurry of preparation example 1-1 and preparation example 2-1 are subjected to mixing dispersion, high speed dispersion 2h in 1:1 ratio.
Embodiment 9
The slurry of the slurry of preparation example 1-1 and preparation example 2-1 are subjected to mixing dispersion, high speed dispersion 2h in 1:10 ratio.
Embodiment 10
The slurry of the slurry of preparation example 1-1 and preparation example 2-2 are subjected to mixing dispersion, high speed dispersion 2h in 1:4 ratio.
Embodiment 11
The slurry of the slurry of preparation example 1-1 and preparation example 2-3 are subjected to mixing dispersion, high speed dispersion 2h in 1:4 ratio.
Embodiment 12
The slurry of the slurry of preparation example 1-1 and preparation example 2-4 are subjected to mixing dispersion, high speed dispersion 2h in 1:4 ratio.
Embodiment 13
The slurry of the slurry of preparation example 1-1 and preparation example 2-5 are subjected to mixing dispersion, high speed dispersion 2h in 1:4 ratio.
Comparative example 1
Prepare the redox graphene slurry of 1-1.
Comparative example 2
The liquid phase stripping method graphene slurry of preparation example 2-1.
The graphene (GN) of the slurry of embodiment and comparative example, LiFePO4 (LFP) are mixed in the following proportions with PVDF,
After being stirred under vacuum uniformly using Vacuum mixer, blade coating test pole sheet resistivity on PET, LFP:PVDF:GN=100:3:1,
As a result such as following table
As shown in Table 1, embodiment 1,2,3,4,5,6,7 is respectively that the redox graphene of different ID/IG and liquid phase are shelled
It is mixed from method graphene according to 1:4 proportion, it can be seen that when ID/IG is 0.8,0.9,1.1,1.3,1.4, pole piece electricity
Resistance rate slightly has gap but is not much different, and when ID/IG continues to become larger, and such as embodiment 2,3, pole piece resistivity becomes larger amplitude increasing
Greatly, this explanation increases with defect and hole, and pole piece electron conduction is deteriorated, and when ID/IG is 1.5, elevation amplitude compared with
Greatly.
The electrochemical impedance spectroscopy (EIS) for the pole piece test that graphene slurry is scratched on utter misery aluminium foil, effect such as attached drawing 1
Shown, embodiment 1,2,3,5 is respectively that the redox graphene of different ID/IG and liquid phase stripping method graphene are matched according to 1:4
Than what is mixed, it can be seen that when ID/IG is 0.9,1.1,1.4,1.5, EIS is not much different, this illustrates lithium ion transport
Similar performance；And the EIS of embodiment 6 is much larger than embodiment 1, illustrates that lithium ion transport is poor, i.e., as ID/IG to 0.8, lithium
Ion transmission is obstructed, degradation.
Shown in attached drawing 1,1 impedance of comparative example is minimum, and illustrating redox graphene, liquid absorption amount is larger in the battery, is conducive to
Lithium ion is transmitted, but compared with Example 1, gap is not particularly evident；2 liquid phase stripping method of comparative example it is worst and with embodiment 1
Differ larger.Embodiment 7 is to be activated on the basis of embodiment 6 by KOH, further increases graphene hole, makes ID/IG
Becoming the 1.1 of embodiment 7 from the 0.8 of embodiment 6, it can be seen that the impedance of embodiment 7 is lower, the enhancing of lithium ion transport ability,
This explanation, by KOH pore-creating, improving ID/IG may be implemented good lithium ion transport.
Slurry and liquid phase stripping method graphite under the redox graphene that embodiment 1 and embodiment 8,9 are identical ID/IG
What alkene was mixed according to 1:4,1:1 and 1:10 proportion respectively, three can be seen that simple go back compared with comparative example 1,2, by table one
Former graphene oxide and liquid phase stripping method graphene, pole piece resistivity is higher, illustrates different graphenes in terms of electron conduction
With synergistic effect；Embodiment 8,9 pole piece resistivity are higher than embodiment 1, illustrate the graphene of different proportion, play a leading role
Graphene is also different, and when redox graphene content is higher, defect is more to keep electronic conduction limited, liquid phase stripping method stone
When black alkene is too many, You Tuyi finds out, lithium ion transport is obstructed, EIS higher, only when ratio is moderate, two kinds of graphenes collaborations
Effect, lithium ion transport is also good while pole piece resistivity reduces.
Table one can obtain, the ID/IG's identical with the respectively redox graphene of embodiment 10,11,12,13 of embodiment 1
The liquid phase stripping method graphene of slurry and different ID/IG is mixed according to 1:4 proportion.It can be seen that embodiment 11,12 poles
Sheet resistivity is close, is better than embodiment 1, but 13 milling time of embodiment is too long, and energy consumption increases more；And embodiment 10 is than implementing
1 pole piece resistivity of example is much higher, and electric conductivity is poor, and embodiment 11 is by further grinding, and ID/IG increases, and lamella is also into one
Step is peeled away, and pole piece resistivity is less than embodiment 10.
Although present disclosure is as above, present invention is not limited to this.Anyone skilled in the art are not departing from this
It in the spirit and scope of invention, can make various changes or modifications, therefore protection scope of the present invention should be with claim institute
Subject to the range of restriction.
Claims (10)
1. a kind of lithium battery electrocondution slurry containing different defect graphenes, it is characterised in that, the graphene packet of the difference defect
Graphene one and graphene two are included, the intensity at one peak Raman D of graphene and the peak G is preferably than i.e. ID/IG
The intensity ratio ID/IG at two peak Raman D of graphene and the peak G is
2. lithium battery electrocondution slurry according to claim 1, which is characterized in that one peak Raman D of graphene and the peak G
Intensity ratio ID/IG is
3. lithium battery electrocondution slurry according to claim 1, which is characterized in that two peak Raman D of graphene and the peak G
Intensity ratio ID/IG is
4. lithium battery electrocondution slurry according to claim 1, which is characterized in that the matter of the graphene two and graphene one
Amount ratio existsBetween.
5. a kind of such as claimThe preparation method of lithium battery electrocondution slurry described in any one, which is characterized in that including
Following steps:
(1) redox method prepares redox graphene powder, by the redox graphene powder, dispersing agent one
Dispersion grinding is carried out by dispersing milling apparatus unit one with the mixed mixture of solvent one, obtains the slurry of graphene one；
(2) by expanded graphite powder, dispersing agent two and the mixed mixture of solvent two by dispersion milling apparatus unit two into
Row dispersion grinding removing, obtains the slurry of graphene two；
(3) slurry of graphene two made from by described in (2) and the slurry of graphene one made from (1) mix point
It dissipates.
6. the preparation method of lithium battery electrocondution slurry according to claim 5, which is characterized in that the dispersing agent one and point
Powder two is Kynoar.
7. the preparation method of lithium battery electrocondution slurry according to claim 5, which is characterized in that the solvent one and solvent
Two be N-Methyl pyrrolidone.
8. the preparation method of lithium battery electrocondution slurry according to claim 5, which is characterized in that the graphene powder
Mass percent isThe mass percent of the dispersing agent one isThe expanded graphite powder
Mass percent isThe mass percent of the dispersing agent two is
9. the preparation method of lithium battery electrocondution slurry according to claim 5, which is characterized in that the graphene one passes through
As under type prepares:It is lower that natural graphite is added into the concentrated sulfuric acid, after stirring is completely dissolved, natural graphite is added
Quality multipleTimes potassium permanganate andSodium nitrate again,StirringThen ice-water bath
Middle ultrasoundIt is diluted with water reaction solution, hydrogen peroxide stirring is added, filtering is sufficiently washed to pH value extremely with acid and waterDry, airflow milling crushes, after obtaining graphene oxide powder, high temperature thermal reduction.
10. the preparation method of lithium battery electrocondution slurry according to claim 9, which is characterized in that after high temperature thermal reduction, lead to
Cross the intensity ratio that further pore-creating improves one peak Raman D of graphene and the peak G.
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