CN109192987A - Graphene composite conductive agent for lithium battery and preparation method thereof - Google Patents
Graphene composite conductive agent for lithium battery and preparation method thereof Download PDFInfo
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- CN109192987A CN109192987A CN201811190580.XA CN201811190580A CN109192987A CN 109192987 A CN109192987 A CN 109192987A CN 201811190580 A CN201811190580 A CN 201811190580A CN 109192987 A CN109192987 A CN 109192987A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 193
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 76
- 239000006258 conductive agent Substances 0.000 title claims abstract description 69
- 239000002131 composite material Substances 0.000 title claims abstract description 63
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 53
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 53
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 44
- 239000010439 graphite Substances 0.000 claims abstract description 44
- 239000000243 solution Substances 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 22
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 239000002270 dispersing agent Substances 0.000 claims abstract description 11
- 239000003381 stabilizer Substances 0.000 claims abstract description 8
- 239000006185 dispersion Substances 0.000 claims description 41
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000010813 municipal solid waste Substances 0.000 claims description 9
- 239000004576 sand Substances 0.000 claims description 9
- 238000003801 milling Methods 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002048 multi walled nanotube Substances 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000010008 shearing Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 238000012546 transfer Methods 0.000 description 12
- 239000011149 active material Substances 0.000 description 10
- 238000003860 storage Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 238000005411 Van der Waals force Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- -1 graphite Alkene Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000002969 artificial stone Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a graphene composite conductive agent for a lithium battery and a preparation method thereof, wherein the graphene composite conductive agent comprises the following components in parts by weight: 2-4 parts of powder graphite, 1-3 parts of carbon nano tube, 1.0-1.5 parts of dispersant, 0.2-0.8 part of stabilizer, 90-95 parts of solvent and 0-0.3 part of viscosity reducer; the preparation method comprises the steps of taking carbon nanotubes and graphite powder as raw materials, dispersing the graphite powder by using ultrasonic waves, dispersing and depolymerizing the carbon nanotubes by using shearing force generated by mechanical high-speed rotation, mixing a graphite powder solution and a carbon nanotube solution, then mechanically dispersing again, then carrying out sanding treatment on the mixed solution, and stripping graphene to obtain the battery-grade graphene composite conductive agent; the battery prepared by using the graphene composite conductive agent has the advantages of low internal resistance and good rate capability, and can remarkably improve the energy density of the lithium battery and enhance the market competitiveness of lithium battery products.
Description
Technical field
The present invention relates to lithium ion battery, photoelectricity information material technical field, in particular to a kind of lithium battery graphene
Combined conductive agent and preparation method thereof.
Background technique
Active material in lithium ion cell positive is the core material of lithium ion battery, promotes active material and matches in anode
Accounting in side can effectively improve the energy density of lithium ion battery；Anode formula includes by that can provide the activity of lithium ion source
Substance, conductive agent and binder；And with the raising of active material accounting in anode formula, the accounting of binder, conductive agent
It can accordingly reduce, scientific research personnel wishes that ideal conductive agent can be evenly dispersed in active material and establishes good conductive mesh
Network reduces electrode ohmic internal resistance, increases electrode interior imbibition ability, and then improve active material utilization.
Conductive agent used at present is usually carbon material, such as conductive carbon black, electrically conductive graphite and carbon nanotube；Due to
These carbon materials density for active material is lower, and the usage amount for reducing conductive agent can significantly improve the volume of battery
Energy density；But carbon nanotube/carbon black composite material conductive agent is since its electronic conduction ability is limited, the cycle life of battery,
The major parameters such as energy density are difficult have room for promotion, and the conduction of its heat is uneven, and then influences the overall thermal of battery
Amount distribution, and finally have an adverse effect to battery.
Graphene is a kind of two-dimensional material that carbon atom is constituted, and has very big excellent performance, and thermal coefficient is
5300W/m.K, room temperature electron mobility are more than 15000cm2/ V.s, resistivity only have 10-6Ω .cm, be current resistivity most
Small material has boundless application prospect in terms of lithium battery conductive agent.
Carbon nanotube in axial direction electron mobility with higher, and large specific surface area, high-tensile and elasticity
Modulus；But electron-transport mode between by the defect and pipe of self structure, and the factors such as introducing of impurity during the preparation process,
Electric conductivity is also somewhat limited.In view of the difference on graphene and carbon nano tube structure, complementarity in performance,
It is be combined with each other with carbon nanotube by graphite is dilute, can not only efficiently use the one-dimensional tubular structure of carbon nanotube, but also dilute using graphite
Two-dimensional layered structure plug the gap, mutually learn from other's strong points to offset one's weaknesses, the advantage both given full play to.
There are many carbon nano tube/graphene composite preparation process at present, such as in patent CN103779097A, disclose by
Graphite oxide and carbon nanotube are added to the water ultrasonic treatment, then dry high-temperature process and obtain graphene/carbon nano-tube composite wood
Material；The patent since the graphite that uses is graphite oxide, the oxidation with oxygen-containing group obtained after ultrasonic treatment
Graphene will lead to electric property and have a greatly reduced quality, and folded situation is returned there may be graphene after drying；Additionally, due to removing
Graphene size reaches nanoscale, and intergranular Van der Waals force causes to reunite, and makes it be difficult to effectively disperse in active material, leads
Causing the good electric conductivity of graphene can not play；There is an urgent need to one kind to disperse graphene and carbon nanotube effectively at present, stablize
The method of preservation to improve active material efficiency for charge-discharge, and then improves the performance of lithium battery.
Summary of the invention
The purpose of the present invention is to provide a kind of graphene composite conductive agent and preparation method thereof of lithium battery, improve graphite
Alkene/carbon nanotube composite conductive agent dispersion stabilization, and improve the efficiency for charge-discharge of active material in combined conductive agent.
To achieve the above object, the invention adopts the following technical scheme:
A kind of lithium battery graphene composite conductive agent is made of following components by respective parts by weight:
2-4 parts of powder graphite；
1-3 parts of carbon nanotube；
1.0-1.5 parts of dispersing agent；
0.2-0.8 parts of stabilizer；
90-95 parts of solvent；
0-0.3 parts of thinner.
Preferably, the powder graphite is crystalline flake graphite powder, expansible graphite powder, expanded graphite powder, artificial stone
One of ink powder body, highly oriented graphite composite powder or multiple combinations.
Preferably, the carbon nanotube is the multi-walled carbon nanotube of caliber 5-80nm, length 5-60nm.
A kind of preparation method of above-mentioned lithium battery graphene composite conductive agent, comprising the following steps:
Powder graphite is added in solvent by S1, the solvent for weighing powder graphite and half amount, and through ultrasonic disperse, it is equal to obtain dispersion
Even graphite solution；
S2, the solvent for weighing carbon nanotube, dispersing agent and the other half amount carbon nanotube and dispersing agent are added in solvent, through machine
Tool dispersion, obtains finely dispersed carbon nano-tube solution；
S3, finely dispersed carbon nano-tube solution and graphite solution are mixed, and adds stabilizer and viscosity reduction in mixed solution
Agent carries out mechanical dispersion again, obtains finely dispersed mixed solution；
S4, mixed solution is delivered to sanding apparatus, lithium battery graphene composite conductive agent is obtained after sanded treatment.
Preferably, it further comprises the steps of: S5, by resulting graphene composite conductive agent, is removed by magnetic force trash separator or electromagnetism
Miscellaneous device processing removes metal impurities, obtains lithium battery graphene composite conductive agent finished product.
Preferably, the frequency of the ultrasonic disperse is 40-60KHz, and the time of ultrasonic disperse is 30-90min.
Preferably, for 500-1300r/min, the time of mechanical dispersion is the blade revolving speed that mechanical dispersion uses in the S2
30-120min。
Preferably, the blade revolving speed that mechanical dispersion uses in the S3 is 1000-1500r/min, the time of mechanical dispersion
For 60-90min.
Preferably, the time of the frosted processing is 5-8h, and the temperature of frosted processing is 5-60 DEG C, the linear speed of sand milling device
Degree is 10-13m/s.
Preferably, the lithium battery is less than 10ppm with the iron content in graphene composite conductive agent finished product.
Beneficial effects of the present invention are as follows:
The present invention is using carbon nanotube and graphite composite powder as raw material, revolves using ultrasonic disperse graphite composite powder, while using mechanical high-speed
The shearing force dispersion of changing the line of production raw, depolymerization carbon nanotube, mechanical point again after graphite composite powder solution and carbon nano-tube solution are mixed
It dissipates, mixed solution is then subjected to sanded treatment, the shearing force of generation is run at high speed by sand milling device and frictional force acts on
Graphite crystal overcomes the Van der Waals force between graphite crystal, nanoscale graphene or graphene sheet layer from graphite crystal
In separate, i.e., removing graphene, obtain the graphene composite conductive agent of LITHIUM BATTERY；Simple production process of the invention is easily grasped
Make, is conducive to automatic management, the production equipment of required investment is at low cost, and production process is environment friendly and pollution-free.
Formula and preparation method through the invention, can successfully solve carbon nanotube and graphene is difficult to disperse and depolymerization
Problem, the present invention be combined with each other graphite is dilute with carbon nanotube, makes full use of the one-dimensional tubular structure of carbon nanotube, adopt simultaneously
It is plugged the gap with the dilute two-dimensional layered structure of graphite, forms dimensional network structure, give full play to the advantage of the two；Utilize the present invention
Graphene composite conductive agent prepared by battery, have the advantages that internal resistance is low, good rate capability, lithium battery can be significantly improved
Energy density, enhance the lithium battery competitiveness of product in market.
Detailed description of the invention
Fig. 1 is the SEM figure for the graphene composite conductive agent that in the present invention prepared by embodiment 1；
Fig. 2 is the SEM figure for the graphene composite conductive agent that in the present invention prepared by embodiment 2；
Fig. 3 is the SEM figure for the graphene composite conductive agent that in the present invention prepared by embodiment 3；
Fig. 4 is battery and the preparation of routine SP conductive agent of the graphene composite conductive agent preparation of the embodiment 1,2,3 in the present invention
Battery DCR data comparison figure；
Fig. 5 is battery and the preparation of routine SP conductive agent of the graphene composite conductive agent preparation of the embodiment 1,2,3 in the present invention
Battery put again capacity keep contrast curve chart.
Specific embodiment
The invention will be further described with reference to embodiments, and purpose, which is only that, is best understood from the object of the invention, and
Unrestricted protection scope of the present invention.
Embodiment 1
The preparation method of the lithium battery of the present embodiment graphene composite conductive agent, comprising the following steps:
1, the electrographite powder of 2.0kg, the 1- methyl pyrrolidone (solvent) of highly oriented graphite composite powder and 46.5kg are weighed, it will
Electrographite powder, highly oriented graphite composite powder are added in solvent, deliver into and carry out ultrasonic disperse, supersonic frequency in ultrasonic disperse tank
Rate is set as 50HZ, disperses 60min, obtains finely dispersed graphite solution；Graphite solution is delivered in transfer tank.
2, the carbon nanotube of 3.0kg, the polyethylene glycol adipate (dispersing agent) of 1.2kg and other 46.5kg are weighed
1- methyl pyrrolidone (solvent), carbon nanotube select the multi-walled carbon nanotube of caliber 5nm, length 5nm；By carbon nanotube and divide
Powder is added in solvent, delivers into and carries out mechanical dispersion in dispersion tank, and dispersion blade revolving speed is 1000r/min, dispersion
60min obtains finely dispersed carbon nano-tube solution.
3, finely dispersed carbon nano-tube solution is delivered in the transfer tank for having graphite solution；In storage carbon nanometer
The acetylacetone,2,4-pentanedione of 0.5kg is added in pipe/graphite mixed solution transfer tank according to the hydroxyethyl cellulose of (stabilizer) and 0.3kg
(thinner) carries out mechanical dispersion again；Dispersion blade revolving speed is 1200r/min, disperses 70min, viscosity is in 5000- after dispersion
20000mpa.s obtains finely dispersed mixed solution.
4, the mixed solution in transfer tank is delivered to sand milling device, carries out sanded treatment, setting sand mill linear velocity is
11m/s carries out that removing graphene, depolymerization carbon nanotube is sanded, time 6h is sanded, is sanded 30 DEG C of temperature；After depolymerization, dispersion
To lithium battery graphene composite conductive agent.
5, obtained combined conductive agent is delivered in storage tank, then is handled through magnetic force trash separator or electromagnetism trash separator,
The metal impurities such as Fe, Cr, Co, Ni, Cu, Zn in graphene composite conductive agent are removed, wherein Fe content requirement is less than 10ppm,
Obtain lithium battery graphene composite conductive agent finished product 1.
It is scanned Electronic Speculum test to lithium battery graphene composite conductive agent finished product 1, for details, reference can be made to shown in Fig. 1,
Graphene sheet layer after removing is relatively thin, and carbon nanotube dispersion is more uniform, and is attached on graphene sheet layer, and the two forms solid
Conductive network.
Embodiment 2
The preparation method of the lithium battery of the present embodiment graphene composite conductive agent, comprising the following steps:
1, the crystalline flake graphite powder of 3.0kg and the N-Methyl pyrrolidone (solvent) of 47.5kg are weighed, crystalline flake graphite powder is added
Enter in solvent, deliver into and carry out ultrasonic disperse in ultrasonic disperse tank, supersonic frequency is set as 40HZ, disperses 90min, is divided
Dissipate uniform graphite solution；Graphite solution is delivered in transfer tank.
2, carbon nanotube, the polyvinylpyrrolidone (dispersing agent) of 1kg and the N- first of other 47.5kg of 2.0kg are weighed
Base pyrrolidones (solvent), carbon nanotube select the multi-walled carbon nanotube of caliber 40nm, length 30nm；By carbon nanotube and dispersion
Agent is added in solvent, delivers into and carries out mechanical dispersion in dispersion tank, and dispersion blade revolving speed is 500r/min, disperses 120min,
Obtain finely dispersed carbon nano-tube solution.
3, finely dispersed carbon nano-tube solution is delivered in the transfer tank for having graphite solution；In storage carbon nanometer
The guar gum (stabilizer) of addition 0.2kg, carries out mechanical dispersion again in pipe/graphite mixed solution transfer tank；Disperse paddle
Leaf revolving speed is 1000r/min, disperses 90min, and it is molten to obtain finely dispersed mixing in 5000-20000mpa.s for viscosity after dispersion
Liquid.
4, the mixed solution in transfer tank is delivered to sand milling device, carries out sanded treatment, setting sand mill linear velocity is
13m/s carries out that removing graphene, depolymerization carbon nanotube is sanded, time 5h is sanded, temperature 60 C is sanded；After depolymerization, dispersion
To lithium battery graphene composite conductive agent.
5, obtained combined conductive agent is delivered in storage tank, then is handled through magnetic force trash separator or electromagnetism trash separator,
The metal impurities such as Fe, Cr, Co, Ni, Cu, Zn in graphene composite conductive agent are removed, wherein Fe content requirement is less than 10ppm,
Obtain lithium battery graphene composite conductive agent finished product 2.
It is scanned Electronic Speculum test to lithium battery graphene composite conductive agent finished product 2, for details, reference can be made to shown in Fig. 1,
Graphene sheet layer after removing is relatively thin, and carbon nanotube dispersion is more uniform, and is attached on graphene sheet layer, and the two forms solid
Conductive network.
Embodiment 3
The preparation method of the lithium battery of the present embodiment graphene composite conductive agent, comprising the following steps:
1, the expansible graphite powder of 4.0kg, the butyl acetate (solvent) of expanded graphite powder and 45kg are weighed, by inflatable stone
Ink powder body, expanded graphite powder are added in solvent, deliver into and carry out ultrasonic disperse in ultrasonic disperse tank, and supersonic frequency is set as
60HZ disperses 30min, obtains finely dispersed graphite solution；Graphite solution is delivered in transfer tank.
2, the carbon nanotube of 1.0kg, the acetic acid of the lauryl sodium sulfate of 1.5kg (dispersing agent) and other 45kg are weighed
Butyl ester (solvent), carbon nanotube select the multi-walled carbon nanotube of caliber 80nm, length 60nm；Carbon nanotube and dispersing agent are added
It in solvent, delivers into and carries out mechanical dispersion in dispersion tank, dispersion blade revolving speed is 1300r/min, disperses 30min, is divided
Dissipate uniform carbon nano-tube solution.
3, finely dispersed carbon nano-tube solution is delivered in the transfer tank for having graphite solution；In storage carbon nanometer
The polyethylene maleimide (stabilizer) of addition 0.8kg and the carboxymethyl of 0.1kg are fine in pipe/graphite mixed solution transfer tank
Plain (thinner) is tieed up, carries out mechanical dispersion again；Dispersion blade revolving speed is 1500r/min, disperses 60min, viscosity exists after dispersion
5000-20000mpa.s obtaining finely dispersed mixed solution.
4, the mixed solution in transfer tank is delivered to sand milling device, carries out sanded treatment, setting sand mill linear velocity is
10m/s carries out that removing graphene, depolymerization carbon nanotube is sanded, time 8h is sanded, is sanded 5 DEG C of temperature；After depolymerization, dispersion
To lithium battery graphene composite conductive agent.
5, obtained combined conductive agent is delivered in storage tank, then is handled through magnetic force trash separator or electromagnetism trash separator,
The metal impurities such as Fe, Cr, Co, Ni, Cu, Zn in graphene composite conductive agent are removed, wherein Fe content requirement is less than 10ppm,
Obtain lithium battery graphene composite conductive agent finished product 3.
It is scanned Electronic Speculum test to lithium battery graphene composite conductive agent finished product 3, for details, reference can be made to shown in Fig. 1,
Graphene sheet layer after removing is relatively thin, and carbon nanotube dispersion is more uniform, and is attached on graphene sheet layer, and the two forms solid
Conductive network.
By the graphene composite conductive agent finished product 1-3 of lithium battery in above-described embodiment and the SP conductive agent of routine difference
It is added in lithium-iron phosphate active material, lithium battery anode electrocondution slurry is made, is coated on foil and forms positive plate；Again with cathode
Battery is prepared in piece, diaphragm, electrolyte, shell together, tests the performance of battery, and performance evaluation is as shown in Figure 4, Figure 5.
As Fig. 4 and Fig. 5 it is found that lithium battery of the present invention battery prepared by graphene composite conductive agent is utilized, and in phase
Compared under the conditions of using battery prepared by SP conductive agent, the present invention reduces the effect of the internal resistance of cell clearly, while multiplying power
Capacity retention ratio is greatly improved in discharge process, therefore lithium battery graphene composite conductive agent of the invention is conducive to mention
The energy density of high battery improves the cycle performance of battery, enhances the market competitiveness of lithium battery.
This hair can be understood and applied the above description of the embodiments is intended to facilitate those skilled in the art
It is bright.Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein
General Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to implementations here
Example, those skilled in the art's announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be
Within protection scope of the present invention.
Claims (10)
1. a kind of graphene composite conductive agent of lithium battery, which is characterized in that be made of following components by respective parts by weight:
2-4 parts of powder graphite；
1-3 parts of carbon nanotube；
1.0-1.5 parts of dispersing agent；
0.2-0.8 parts of stabilizer；
90-95 parts of solvent；
0-0.3 parts of thinner.
2. a kind of lithium battery graphene composite conductive agent according to claim 1, which is characterized in that the powder graphite
For one in crystalline flake graphite powder, expansible graphite powder, expanded graphite powder, electrographite powder, highly oriented graphite composite powder
Kind or multiple combinations.
3. a kind of lithium battery graphene composite conductive agent according to claim 1, which is characterized in that the carbon nanotube
For the multi-walled carbon nanotube of caliber 5-80nm, length 5-60nm.
4. a kind of preparation method of lithium battery graphene composite conductive agent according to claim 1, which is characterized in that packet
Include following steps:
Powder graphite is added in solvent by S1, the solvent for weighing powder graphite and half amount, and through ultrasonic disperse, it is equal to obtain dispersion
Even graphite solution；
S2, the solvent for weighing carbon nanotube, dispersing agent and the other half amount carbon nanotube and dispersing agent are added in solvent, through machine
Tool dispersion, obtains finely dispersed carbon nano-tube solution；
S3, finely dispersed carbon nano-tube solution and graphite solution are mixed, and adds stabilizer and viscosity reduction in mixed solution
Agent carries out mechanical dispersion again, obtains finely dispersed mixed solution；
S4, mixed solution is delivered to sanding apparatus, lithium battery graphene composite conductive agent is obtained after sanded treatment.
5. a kind of preparation method of lithium battery graphene composite conductive agent according to claim 1, which is characterized in that also
Comprising steps of S5, by resulting graphene composite conductive agent, it is miscellaneous that metal is removed by magnetic force trash separator or the processing of electromagnetism trash separator
Matter obtains lithium battery graphene composite conductive agent finished product.
6. a kind of preparation method of lithium battery graphene composite conductive agent according to claim 1, which is characterized in that institute
The frequency for stating ultrasonic disperse is 40-60KHz, and the time of ultrasonic disperse is 30-90min.
7. a kind of preparation method of lithium battery graphene composite conductive agent according to claim 1, which is characterized in that institute
Blade revolving speed that mechanical dispersion in S2 uses is stated as 500-1300r/min, the time of mechanical dispersion is 30-120min.
8. a kind of preparation method of lithium battery graphene composite conductive agent according to claim 1, which is characterized in that institute
Blade revolving speed that mechanical dispersion in S3 uses is stated as 1000-1500r/min, the time of mechanical dispersion is 60-90min.
9. a kind of preparation method of lithium battery graphene composite conductive agent according to claim 1, which is characterized in that institute
The time for stating frosted processing is 5-8h, and the temperature of frosted processing is 5-60 DEG C, and the linear velocity of sand milling device is 10-13m/s.
10. a kind of preparation method of lithium battery graphene composite conductive agent according to claim 5, which is characterized in that
The lithium battery is less than 10ppm with the iron content in graphene composite conductive agent finished product.
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