CN105336958B - Graphene/CNTs/Super P combined conductive agents, combined conductive agent slurry and preparation method thereof - Google Patents
Graphene/CNTs/Super P combined conductive agents, combined conductive agent slurry and preparation method thereof Download PDFInfo
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- 239000006258 conductive agent Substances 0.000 title claims abstract description 145
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 122
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 110
- 238000002360 preparation method Methods 0.000 title claims abstract description 53
- 239000002002 slurry Substances 0.000 title claims abstract description 52
- 238000007613 slurry method Methods 0.000 title abstract 2
- 239000000843 powder Substances 0.000 claims abstract description 29
- 239000012298 atmosphere Substances 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 239000004094 surface-active agent Substances 0.000 claims abstract description 18
- 230000009467 reduction Effects 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000006245 Carbon black Super-P Substances 0.000 claims description 90
- 239000007787 solid Substances 0.000 claims description 36
- 239000002245 particle Substances 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 26
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 238000013019 agitation Methods 0.000 claims description 13
- 239000011521 glass Substances 0.000 claims description 13
- 239000011268 mixed slurry Substances 0.000 claims description 13
- 239000011802 pulverized particle Substances 0.000 claims description 13
- 238000000967 suction filtration Methods 0.000 claims description 13
- 238000010792 warming Methods 0.000 claims description 13
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 17
- 229910001416 lithium ion Inorganic materials 0.000 description 17
- 239000000463 material Substances 0.000 description 17
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 description 15
- 238000006722 reduction reaction Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 238000012956 testing procedure Methods 0.000 description 11
- 239000004567 concrete Substances 0.000 description 9
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 9
- 239000003643 water by type Substances 0.000 description 7
- 238000007599 discharging Methods 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 239000002482 conductive additive Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- -1 graphene alkene Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910001305 LiMPO4 Inorganic materials 0.000 description 1
- 229910002993 LiMnO2 Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- 229910013415 LiNixCoyMn(1-x-y)O2 Inorganic materials 0.000 description 1
- 229910013424 LiNixCoyMn(1−x−y)O2 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000009955 starching Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 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
-
- 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 discloses a kind of Graphene/CNTs/Super P combined conductive agents, combined conductive agent slurry and preparation method thereof, combined conductive agent is by Graphene（Graphene）、CNTs（CNT）And Super P（Conductive black）Composition.Its preparation method is：Graphene oxide slurry, CNT, conductive black and surfactant are added in reactor and are stirred, then through sufficient ultrasonic disperse, then dried and crush；The mixture crushed is added in Muffle furnace, after expanded in air, inert atmosphere reduction treatment, normal temperature is cooled to, combined conductive agent powder is obtained；Also powder combined conductive agent can be mixed with solvent, stirring, ultrasonic disperse are obtained combined conductive agent slurry.The combined conductive agent excellent electrical property of the present invention, the conductive agent for being suitable as power ion battery are used.The preparation technology that adopted is easy, energy consumption is little, is adapted to scale industrial production.
Description
Technical field
The invention belongs to the energy and field of new, are related to a kind of power lithium-ion rechargeable battery combined conductive agent and system
Preparation Method, and in particular to a kind of Graphene/CNTs/Super-P combined conductive agents, combined conductive agent slurry and its preparation side
Method.
Background technology
Lithium ion battery, because its high power capacity, high voltage, have extended cycle life, security is good, memory-less effect the advantages of, extensively
It is general to be applied to the portable electric appts such as mobile phone, notebook computer, video camera.As people are for the ring caused by fuel-engined vehicle
The growing interest of border pollution, in recent years, application of the lithium ion battery as power source on electric automobile enjoys the concern of people.
Lithium ion battery is applied on electric automobile as power source and first has to meet the demand for being capable of fast charging and discharging.In order to improve lithium
The fast charging and discharging performance of ion battery, mainly has following approach：1. existing lithium ion battery is repaiied with positive and negative electrode material
Decorations are modified, improve conduction, the transfer ability of its electronics or lithium ion, so as to reach the purpose for improving its fast charging and discharging；2. send out
The positive and negative electrode material of existing new suitable fast charging and discharging；3. conductive additive is added in electrode slice preparation process, improve just,
The surface electronic electric conductivity of negative active core-shell material.Using graphite-like material with carbon element as negative pole more than the lithium ion battery of commercialization at present
Material, for graphite-like carbon negative pole material is with respect to positive pole, has preferable electric conductivity, in principle without adding conductive agent increasing material
The electric conductivity of material.But it is as graphite-like material with carbon element is during embedded, abjection lithium, it may occur that volumetric expansion and contraction, several
After circulation, the contact between material can be reduced, or space occur, cause polarization of electrode to be increased dramatically, it is therefore desirable to appropriate to add
Enter conductive agent.The sky that the carbon black of particle, acetylene black or fibrous conductive agent can be filled up between carbon negative pole material well
Gap, keeps the stability of electrode in cyclic process, the electric conductivity of electrode will not be caused because of the increase of cycle-index drastically to decline.
The positive electrode of lithium ion battery is generally transition-metal oxide, such as：LiCoO2、LiNiO2、LiMnO2, and
LiNixCoyMn（1-x-y）O2Deng, and the phosphate of transition metal, such as LiMPO4（M is Fe or Mn）, their electrical conductivity are low, typically
It is semiconductor or insulator, in order to ensure the normal work of lithium ion battery, therefore must adds during prepared by electrode
Enter conductive additive.
Excellent conductive agent needs to have following feature：First, electrical conductivity is higher, and the material of high conductivity can improve electricity
The migration rate of son；2nd, particle diameter is less, and the material of small particle can fill the space of lithium ion battery positive and negative electrode material, make material
Between contact it is preferable, it is easy to the migration of lithium ion；3rd, high-specific surface area, the big material of specific surface area can preferably with it is positive and negative
Pole material, is equally easy to Electolyte-absorptive；4th, it is easily dispersed, it is easily upon opening in positive and negative electrode material prepares slurry process
And dispersion, preferably can mix with positive and negative electrode material；5th, high stability, during lithium ion battery discharge and recharge
Can stable existence, will not occur with the reaction of electrolyte and affect the cycle performance of battery.Existing commercial conductive agent is with carbon
Based on material, mainly including electrically conductive graphite, conductive black and CNT etc., above-mentioned conductive agent respectively has the advantages that itself, but
Do not possess the features described above that a kind of excellent conductive agent should possess, it is impossible to meet the demand of power lithium-ion battery conductive agent,
Therefore, it is necessary to develop new conductive agent.
The content of the invention
It is an object of the invention to develop a kind of new Graphene/CNTs/Super-P of power lithium-ion battery be combined
Conductive agent and preparation method.
First, the present invention provides a kind of Graphene/CNTs/Super-P combined conductive agents, and its technical scheme is as follows：
A kind of Graphene/CNTs/Super-P combined conductive agents, described combined conductive agent by Graphene, CNTs and
Super-P is constituted；Weight/mass percentage composition shared by Graphene is 0.01% ~ 30%；Weight/mass percentage composition shared by CNTs is
0.01%~30%。
Preferably, in the combined conductive agent, Graphene sizes are more than 5 m, and the number of plies is 5 ~ 7 layers.
Preferably, 3 m ~ 5 m of CNTs length in the combined conductive agent, diameter 50nm ~ 70nm.
Secondly, the present invention also provides a kind of above-mentioned combined conductive agent slurry, and its technical scheme is as follows：
A kind of above-mentioned combined conductive agent slurry, including above-mentioned combined conductive agent and solvent；The combined conductive agent percentage
Content≤50%.
Preferably, the solvent is selected from secondary deionized water, 1-METHYLPYRROLIDONE.
Preferably, the combined conductive agent relative content is 10%.
Again, the present invention provides a kind of preparation method of Graphene/CNTs/Super-P combined conductive agents, is adopted
Technical scheme is as follows：
A kind of preparation method of Graphene/CNTs/Super-P combined conductive agents, comprises the steps：
（1）Mixing：The graphene oxide slurry of solid content≤50% is added in single-glass reactor, addition CNTs,
Super-P and surfactant, mechanical agitation 25min～35min, then ultrasonic disperse 20min～35min again so as to mix
Uniformly；
（2）Crush：By step（1）In mixed slurry suction filtration and in the drying of 90 DEG C～110 DEG C environment, be dried to water content
≤ 5%, the solid of drying is crushed with pulverizer, particle diameter≤74 μm of pulverized particles are made；
（3）It is expanded：Heating muffle stove so as to be warming up to 200 DEG C～450 DEG C, by step（2）The compound particles of middle crushing
Grain is put in Muffle furnace rapidly, takes out rapidly, be cooled to normal temperature in air after expanding treatment 3min～10min；
（4）Reduction：By step（3）In mixture be placed on 1000 DEG C, in the tube furnace of inert atmosphere, heat treatment 5
Min～15min, obtains Graphene/CNTs/Super-P combined conductive agent powders；
In the preparation method of combined conductive agent of the present invention:
Step（1）In graphene oxide slurry be the product prepared using oxidation-reduction reaction, and obtained
Washing process, in faintly acid；
Step（2）It is middle moisture control below 5%, be the burning that water decomposition may bring in order to prevent during expanding treatment
Or blast；
Step（3）Preferably 200 DEG C～300 DEG C of the temperature of middle expanding treatment, time preferably 3～5min, primarily to anti-
Only temperature is too high may be to the damage caused by raw material；
Step（4）Employed in 1000 DEG C of high temperature be to ensure that graphene oxide is reduced into Graphene, being adopted
Inert atmosphere be to ensure that Graphene, CNTs and Super-P are not burned off.
Preferably, the step（1）Middle surfactant selected from polyvinylpyrrolidone, dodecyl sodium sulfate, 16
Alkyl trimethyl ammonium chloride any one.
Preferably, the step（1）Middle surfactant adds mass percent to be graphene oxide, CNT and lead
The 0.01%～1% of electric carbon black gross mass.
Finally, the present invention provides a kind of preparation method of above-mentioned combined conductive agent slurry, and concrete scheme is as follows：
A kind of preparation method of above-mentioned combined conductive agent slurry, on the basis of above-mentioned combined conductive agent is prepared, also includes
Following steps：
By step（4）In the Graphene/CNTs/Super-P combined conductive agent powders that obtain be added in solvent, admittedly contain
Amount≤50%, ultrasonic disperse 8min～12min, are obtained Graphene/CNTs/Super-P combined conductive agent slurries.
The present invention principle be：
Using the superior electrical conductivity energy of Graphene and CNTs, while using the microcosmic of Graphene, CNTs and Super-P
Architectural characteristic, when which is used as conductive agent, Graphene, CNTs and Super-P play cooperative effect, can be in electrode slice
It is middle to build efficient conductive network, reach and farthest contact with electrode active material, electrode activity can greatly be improved
The surface electronic electric conductivity of material, so that electrode active material can carry out quick charging and discharging, therefore, it is suitable as
Conductive additive for power lithium-ion battery is used.
The present invention has advantages below：（1）Used in the present invention, graphene oxide slurry is raw material, is aoxidized in this condition
Graphene due to the solvent action on its surface, in good dispersity, be not in as powder state when as surface is strong
Van der waals force and caused agglomeration, be thus advantageous to compound with CNT；（2）The Large ratio surface of Graphene
The small particle size of product, the high length-diameter ratio of CNT and Super-P, can build efficient conductive network in electrode slice,
The effective contact with electrode active material is realized to the full extent, is improved its electronic conductivity, is especially realized high current
Fast charging and discharging performance；（3）Present invention reduction treatment in atmosphere to the expanded and high temperature inert atmosphere of raw material, mainly have with
Lower effect：A. decompose the surfactant of addition, can decompose completely when selected surfactant is heat-treated in atmosphere,
Without residue；B. the functional group at surface of graphene oxide or edge is removed, and is allowed to stone is reduced into by situ in the composite
Black alkene；C. expanding treatment in air, make product become it is fluffy, be easily dispersed, facilitate its application in actual production；（4）This
Invented technology is easy, energy consumption is little, is adapted to large-scale production.
Description of the drawings
Fig. 1 is the ESEM of Graphene/CNTs/Super-P combined conductive agents in the embodiment of the present invention 1（SEM）Figure
Picture；
Scanning electricity of the Fig. 2 for Graphene in Graphene/CNTs/Super-P combined conductive agents in the embodiment of the present invention 1
Mirror（SEM）Image；
Transmission electricity of the Fig. 3 for Graphene in Graphene/CNTs/Super-P combined conductive agents in the embodiment of the present invention 1
Mirror（TEM）Image；
ESEMs of the Fig. 4 for CNTs in Graphene/CNTs/Super-P combined conductive agents in the embodiment of the present invention 1
（SEM）Image；
Transmission electron microscopes of the Fig. 5 for CNTs in Graphene/CNTs/Super-P combined conductive agents in the embodiment of the present invention 1
（TEM）Image；
Fig. 6 is the ESEM of Graphene/CNTs combined conductive agents in comparative example of the present invention 1（SEM）Image；
Fig. 7 is the ESEM of CNTs/Super-P combined conductive agents in comparative example of the present invention 3（SEM）Image；
Fig. 8 is in Graphene/CNTs/Super-P combined conductive agents in the embodiment of the present invention 1 and comparative example 1
Graphene/Super-P combined conductive agents and comparative example 3 in Graphene/CNTs combined conductive agents, comparative example 2
Middle CNTs/Super-P combined conductive agents are improving lithium ion battery negative material（Spinel type lithium titanate-Li4Ti5O12）Times
The comparison of rate aspect of performance.
Specific embodiment
The present invention is further illustrated with reference to embodiments, and protection scope of the present invention is not limited only to following institute
State.
A kind of preparation method of 1. Graphene/CNTs/Super-P combined conductive agents of embodiment, its concrete steps is such as
Under：
（1）Mixing：The graphene oxide slurry of 100g solid contents 10% is added in single-glass reactor, 5g is added
CNTs, 5g Super-P and 0.2g surfactant polyvinylpyrrolidones, mechanical agitation 30min, then ultrasonic disperse again
30min so as to be well mixed；
（2）Crush：By step（1）In mixed slurry suction filtration and in the drying of 100 DEG C of environment, be dried to water content≤5%, will
The solid of drying is crushed with pulverizer, makes particle diameter≤74 μm of pulverized particles；
（3）It is expanded：Heating muffle stove so as to be warming up to 300 DEG C, by step（2）The compound particles of middle crushing are put rapidly
Enter in Muffle furnace, taken out after expanding treatment 5min rapidly in air, be cooled to normal temperature；
（4）Reduction：By step（3）In mixture be placed on 1000 DEG C, in the tube furnace of inert atmosphere, heat treatment
10min, obtains Graphene/CNTs/Super-P combined conductive agent powders.
The following is the preparation of combined conductive agent slurry：
On the preparation basis of above-mentioned combined conductive agent, 10g steps are taken（4）In obtained Graphene/CNTs/
Super-P combined conductive agent powders are added in 90g secondary deionized waters, and ultrasonic disperse 10min, prepared solid content are 10%
Aqueous Graphene/CNTs/Super-P combined conductive agents slurry.
A kind of ESEM of Graphene/CNTs/Super-P combined conductive agents that the present embodiment is obtained（SEM）Image
As shown in Figure 1, it can be observed that Graphene, CNTs and Super-P are more uniform to be combined with each other, while can also observe
Arrive, Graphene/CNTs/Super-P combined conductive agents are loose, porous, illustrate which will be easy to dispersion in actual applications.
The ESEM of Graphene in a kind of Graphene/CNTs/Super-P combined conductive agents that the present embodiment is obtained
（SEM）Image as shown in Fig. 2 it is observed that Graphene presents relatively bright gloss under field emission microscope,
Illustrate that prepared Graphene has more excellent electronic conductivity.Further, it is also possible to it was observed that, the size of Graphene
More than 5 m.
The transmission electron microscope of Graphene in a kind of Graphene/CNTs/Super-P combined conductive agents that the present embodiment is obtained
（TEM）Image as shown in figure 3, it is observed that prepared Graphene be form the few-layer graphene alkene, the number of plies is at 7 layers or so.
The ESEM of CNTs in a kind of Graphene/CNTs/Super-P combined conductive agents that the present embodiment is obtained
（SEM）Image as shown in figure 4, it is observed that prepared CNTs have higher draw ratio, its length be 3 m ~ 5 m.
The transmission electron microscope of CNTs in a kind of Graphene/CNTs/Super-P combined conductive agents that the present embodiment is obtained
（TEM）Image is as shown in figure 5, it is observed that a diameter of 50 nm ~ 70nm of prepared CNTs.
It is below Experimental Testing Procedures：
a）, electrode slice preparation：By active material Li4Ti5O12(lithium ion battery negative material-spinel-type metatitanic acid
Lithium), conductive agent, binding agent LA132 is with weight ratio as 90:5:Uniformly grind in agate mortar after 5 ratio mixing, make electricity
Pole slurry, then on aluminium foil, in vacuum drying oven, 80 DEG C are dried 12h to even application, make electrode slice, wherein active material
Load capacity is more than 3.0 mg/cm2。
b）, button cell assembling and high rate performance test：Using CR2032 type button cell models, it is right with metal lithium sheet
Electrode, diaphragm type are Celgard2400, LiPF6/EC of the electrolyte for 1mol/L:DEC:DMC (1:1:1 volume ratio),
It is assembled into button cell.Test its high rate performance under room temperature by the way of constant current charge-discharge, test voltage scope be 3.0 V～
1.0 V, test size of current represent respectively 0.2 C, 0.5 C, 1.0 C, 3.0 C, 5.0 C and 10.0 C with multiplying power.
3）, experimental result：As shown in figure 8, Graphene/CNTs/Super-P combined conductive agents are improving Li4Ti5O12Times
Rate aspect of performance has shown the performance of optimum, Li4Ti5O12Specific discharge capacity in 0.2 C is up to 163 mAh/g, 1.0 C
When specific discharge capacity be 156 mAh/g, the specific discharge capacity of 3.0 C is 147 mAh/g, and the specific discharge capacity of 5.0 C is 138
MAh/g, even if its specific discharge capacity is still up to 130 mAh/g under 10.0 C of high magnification.Graphene/CNTs/Super-P
Combined conductive agent is improving Li4Ti5O12It is better than Graphene/CNTs combined conductive agents in terms of high rate performance（Comparative example 1）、
Better than Graphene/Super-P combined conductive agents（Comparative example 2）And it is better than CNTs/Super-P combined conductive agents（Contrast
Embodiment 3）.
A kind of preparation method of 2. Graphene/CNTs/Super-P combined conductive agents of embodiment, its concrete steps is such as
Under：
（1）Mixing：The graphene oxide slurry of 100g solid contents 20% is added in single-glass reactor, 10g is added
CNTs, 10g Super-P and 0.4g surfactant polyvinylpyrrolidones, mechanical agitation 30min, then ultrasonic disperse again
30min so as to be well mixed；
（2）Crush：By step（1）In mixed slurry suction filtration and in the drying of 100 DEG C of environment, be dried to water content≤5%, will
The solid of drying is crushed with pulverizer, makes particle diameter≤74 μm of pulverized particles；
（3）It is expanded：Heating muffle stove so as to be warming up to 300 DEG C, by step（2）The compound particles of middle crushing are put rapidly
Enter in Muffle furnace, taken out after expanding treatment 5min rapidly in air, be cooled to normal temperature；
（4）Reduction：By step（3）In mixture be placed on 1000 DEG C, in the tube furnace of inert atmosphere, heat treatment
10min, obtains Graphene/CNTs/Super-P combined conductive agent powders.
The following is the preparation of combined conductive agent slurry：
On the preparation basis of above-mentioned combined conductive agent, 5g steps are taken（4）In obtained Graphene/CNTs/
Super-P combined conductive agent powders are added in 95g 1-METHYLPYRROLIDONEs, ultrasonic disperse 10min, and it is 5% that solid content is obtained
Oiliness Graphene/CNTs/Super-P combined conductive agent slurry.
With reference to the testing procedure of embodiment 1, experimental result： Li4Ti5O12Specific discharge capacity in 0.2 C is up to 161
MAh/g, specific discharge capacity during 1.0 C is 154 mAh/g, and the specific discharge capacity of 3.0 C is 145 mAh/g, the electric discharge of 5.0 C
Specific capacity is 136 mAh/g, even if its specific discharge capacity is still up to 131 mAh/g under 10.0 C of high magnification.
A kind of preparation method of 3. Graphene/CNTs/Super-P combined conductive agents of embodiment, its concrete steps is such as
Under：
（1）Mixing：The graphene oxide slurry of 100g solid contents 5% is added in single-glass reactor, 2.5g is added
CNTs, 2.5g Super-P and 0.1g surfactant polyvinylpyrrolidones, mechanical agitation 30min, then ultrasonic disperse again
30min so as to be well mixed；
（2）Crush：By step（1）In mixed slurry suction filtration and in the drying of 100 DEG C of environment, be dried to water content≤5%, will
The solid of drying is crushed with pulverizer, makes particle diameter≤74 μm of pulverized particles；
（3）It is expanded：Heating muffle stove so as to be warming up to 300 DEG C, by step（2）The compound particles of middle crushing are put rapidly
Enter in Muffle furnace, taken out after expanding treatment 5min rapidly in air, be cooled to normal temperature；
（4）Reduction：By step（3）In mixture be placed on 1000 DEG C, in the tube furnace of inert atmosphere, heat treatment
10min, obtains Graphene/CNTs/Super-P combined conductive agent powders.
The following is the preparation of combined conductive agent slurry：
On the preparation basis of above-mentioned combined conductive agent, 1g steps are taken（4）In obtained Graphene/CNTs/
Super-P combined conductive agent powders are added in 99g 1-METHYLPYRROLIDONEs, ultrasonic disperse 10min, and it is 1% that solid content is obtained
Oiliness Graphene/CNTs/Super-P combined conductive agent slurry.
With reference to the testing procedure of embodiment 1, experimental result： Li4Ti5O12Specific discharge capacity in 0.2 C is up to 164
MAh/g, specific discharge capacity during 1.0 C is 158 mAh/g, and the specific discharge capacity of 3.0 C is 147 mAh/g, the electric discharge of 5.0 C
Specific capacity is 139 mAh/g, even if its specific discharge capacity is still up to 134 mAh/g under 10.0 C of high magnification.
A kind of preparation method of 4. Graphene/CNTs/Super-P combined conductive agents of embodiment, its concrete steps is such as
Under：
（1）Mixing：The graphene oxide slurry of 100g solid contents 10% is added in single-glass reactor, 15g is added
CNTs, 15g Super-P and 0.4g surfactant hexadecyltrimethylammonium chlorides, mechanical agitation 30min are then ultrasonic again
Dispersion 30min so as to be well mixed；
（2）Crush：By step（1）In mixed slurry suction filtration and in the drying of 100 DEG C of environment, be dried to water content≤5%, will
The solid of drying is crushed with pulverizer, makes particle diameter≤74 μm of pulverized particles；
（3）It is expanded：Heating muffle stove so as to be warming up to 300 DEG C, by step（2）The compound particles of middle crushing are put rapidly
Enter in Muffle furnace, taken out after expanding treatment 5min rapidly in air, be cooled to normal temperature；
（4）Reduction：By step（3）In mixture be placed on 1000 DEG C, in the tube furnace of inert atmosphere, heat treatment
10min, obtains Graphene/CNTs/Super-P combined conductive agent powders.
The following is the preparation of combined conductive agent slurry：
On the preparation basis of above-mentioned combined conductive agent, 20g steps are taken（4）In obtained Graphene/CNTs/
Super-P combined conductive agent powders are added in 80g secondary deionized waters, and ultrasonic disperse 10min, prepared solid content are 20%
Aqueous Graphene/CNTs/Super-P combined conductive agents slurry.
With reference to the testing procedure of embodiment 1, experimental result： Li4Ti5O12Specific discharge capacity in 0.2 C is up to 160
MAh/g, specific discharge capacity during 1.0 C is 151 mAh/g, and the specific discharge capacity of 3.0 C is 140 mAh/g, the electric discharge of 5.0 C
Specific capacity is 132 mAh/g, even if its specific discharge capacity is still up to 127 mAh/g under 10.0 C of high magnification.
A kind of preparation method of 5. Graphene/CNTs/Super-P combined conductive agents of embodiment, its concrete steps is such as
Under：
（1）Mixing：The graphene oxide slurry of 100g solid contents 5% is added in single-glass reactor, 15g is added
CNTs, 20g Super-P and 0.4g surfactant polyvinylpyrrolidones, mechanical agitation 30min, then ultrasonic disperse again
30min so as to be well mixed；
（2）Crush：By step（1）In mixed slurry suction filtration and in the drying of 100 DEG C of environment, be dried to water content≤5%, will
The solid of drying is crushed with pulverizer, makes particle diameter≤74 μm of pulverized particles；
（3）It is expanded：Heating muffle stove so as to be warming up to 300 DEG C, by step（2）The compound particles of middle crushing are put rapidly
Enter in Muffle furnace, taken out after expanding treatment 5min rapidly in air, be cooled to normal temperature；
（4）Reduction：By step（3）In mixture be placed on 1000 DEG C, in the tube furnace of inert atmosphere, heat treatment
10min, obtains Graphene/CNTs/Super-P combined conductive agent powders.
The following is the preparation of combined conductive agent slurry：
On the preparation basis of above-mentioned combined conductive agent, 5g steps are taken（4）In obtained Graphene/CNTs/
Super-P combined conductive agent powders are added in 95g secondary deionized waters, ultrasonic disperse 10min, and prepared solid content is 5% water
Property Graphene/CNTs/Super-P combined conductive agent slurries.
With reference to the testing procedure of embodiment 1, experimental result： Li4Ti5O12Specific discharge capacity in 0.2 C is up to 162
MAh/g, specific discharge capacity during 1.0 C is 152 mAh/g, and the specific discharge capacity of 3.0 C is 142 mAh/g, the electric discharge of 5.0 C
Specific capacity is 133 mAh/g, even if its specific discharge capacity is still up to 130 mAh/g under 10.0 C of high magnification.
A kind of preparation method of 6. Graphene/CNTs/Super-P combined conductive agents of embodiment, its concrete steps is such as
Under：
（1）Mixing：The graphene oxide slurry of 100g solid contents 1% is added in single-glass reactor, 9g is added
CNTs, 40g Super-P and 0.1g surfactant polyvinylpyrrolidones, mechanical agitation 30min, then ultrasonic disperse again
30min so as to be well mixed；
（2）Crush：By step（1）In mixed slurry suction filtration and in the drying of 100 DEG C of environment, be dried to water content≤5%, will
The solid of drying is crushed with pulverizer, makes particle diameter≤74 μm of pulverized particles；
（3）It is expanded：Heating muffle stove so as to be warming up to 300 DEG C, by step（2）The compound particles of middle crushing are put rapidly
Enter in Muffle furnace, taken out after expanding treatment 5min rapidly in air, be cooled to normal temperature；
（4）Reduction：By step（3）In mixture be placed on 1000 DEG C, in the tube furnace of inert atmosphere, heat treatment
10min, obtains Graphene/CNTs/Super-P combined conductive agent powders；
The following is the preparation of combined conductive agent slurry：
On the preparation basis of above-mentioned combined conductive agent, 5g steps are taken（4）In obtained Graphene/CNTs/
Super-P combined conductive agent powders are added in 45g 1-METHYLPYRROLIDONEs, ultrasonic disperse 10min, and it is 10% that solid content is obtained
Oiliness Graphene/CNTs/Super-P combined conductive agent slurry.
With reference to the testing procedure of embodiment 1, experimental result： Li4Ti5O12Specific discharge capacity in 0.2 C is up to 163
MAh/g, specific discharge capacity during 1.0 C is 152 mAh/g, and the specific discharge capacity of 3.0 C is 143 mAh/g, the electric discharge of 5.0 C
Specific capacity is 133 mAh/g, even if its specific discharge capacity is still up to 134 mAh/g under 10.0 C of high magnification.
A kind of preparation method of 7. Graphene/CNTs/Super-P combined conductive agents of embodiment, its concrete steps is such as
Under：
（1）Mixing：The graphene oxide slurry of 100g solid contents 9% is added in single-glass reactor, 1g is added
CNTs, 40g Super-P and 0.1g surfactant sodium dodecyl base sodium sulfonates, mechanical agitation 30min, then ultrasonic disperse again
30min so as to be well mixed；
（2）Crush：By step（1）In mixed slurry suction filtration and in the drying of 100 DEG C of environment, be dried to water content≤5%, will
The solid of drying is crushed with pulverizer, makes particle diameter≤74 μm of pulverized particles；
（3）It is expanded：Heating muffle stove so as to be warming up to 300 DEG C, by step（2）The compound particles of middle crushing are put rapidly
Enter in Muffle furnace, taken out after expanding treatment 5min rapidly in air, be cooled to normal temperature；
（4）Reduction：By step（3）In mixture be placed on 1000 DEG C, in the tube furnace of inert atmosphere, heat treatment
10min, obtains Graphene/CNTs/Super-P combined conductive agent powders.
The following is the preparation of combined conductive agent slurry：
On the preparation basis of above-mentioned combined conductive agent, 5g steps are taken（4）In obtained Graphene/CNTs/
Super-P combined conductive agent powders are added in 45g secondary deionized waters, and ultrasonic disperse 10min, prepared solid content are 10%
Aqueous Graphene/CNTs/Super-P combined conductive agents slurry.
With reference to the testing procedure of embodiment 1, experimental result： Li4Ti5O12Specific discharge capacity in 0.2 C is up to 163
MAh/g, specific discharge capacity during 1.0 C is 152 mAh/g, and the specific discharge capacity of 3.0 C is 141 mAh/g, the electric discharge of 5.0 C
Specific capacity is 132 mAh/g, even if its specific discharge capacity is still up to 129 mAh/g under 10.0 C of high magnification.
A kind of preparation method of 8. Graphene/CNTs/Super-P combined conductive agents of embodiment, its concrete steps is such as
Under：
（1）Mixing：The graphene oxide slurry of 100g solid contents 5% is added in single-glass reactor, 5g is added
CNTs, 1g Super-P and 0.1g surfactant polyvinylpyrrolidones, mechanical agitation 30min, then ultrasonic disperse again
30min so as to be well mixed；
（2）Crush：By step（1）In mixed slurry suction filtration and in the drying of 100 DEG C of environment, be dried to water content≤5%, will
The solid of drying is crushed with pulverizer, makes particle diameter≤74 μm of pulverized particles；
（3）It is expanded：Heating muffle stove so as to be warming up to 300 DEG C, by step（2）The compound particles of middle crushing are put rapidly
Enter in Muffle furnace, taken out after expanding treatment 5min rapidly in air, be cooled to normal temperature；
（4）Reduction：By step（3）In mixture be placed on 1000 DEG C, in the tube furnace of inert atmosphere, heat treatment
10min, obtains Graphene/CNTs/Super-P combined conductive agent powders.
The following is the preparation of combined conductive agent slurry：
On the preparation basis of above-mentioned combined conductive agent, 5g steps are taken（4）In obtained Graphene/CNTs/
Super-P combined conductive agent powders are added in 45g 1-METHYLPYRROLIDONEs, ultrasonic disperse 10min, and it is 10% that solid content is obtained
Oiliness Graphene/CNTs/Super-P combined conductive agent slurry.
With reference to the testing procedure of embodiment 1, experimental result： Li4Ti5O12Specific discharge capacity in 0.2 C is up to 163
MAh/g, specific discharge capacity during 1.0 C is 154 mAh/g, and the specific discharge capacity of 3.0 C is 144 mAh/g, the electric discharge of 5.0 C
Specific capacity is 138 mAh/g, even if its specific discharge capacity is still up to 134mAh/g under 10.0 C of high magnification.
A kind of preparation method of 1. Graphene/CNTs combined conductive agents of comparative example, which comprises the following steps that：
（1）Mixing：The graphene oxide slurry of 100g solid contents 5% is added in single-glass reactor, 5g is added
CNTs and 0.1g surfactant polyvinylpyrrolidones, mechanical agitation 30min, then ultrasonic disperse 30min again so as to mix
Uniformly；
（2）Crush：By step（1）In mixed slurry suction filtration and in the drying of 100 DEG C of environment, be dried to water content≤5%, will
The solid of drying is crushed with pulverizer, makes particle diameter≤74 μm of pulverized particles；
（3）It is expanded：Heating muffle stove so as to be warming up to 300 DEG C, by step（2）The compound particles of middle crushing are put rapidly
Enter in Muffle furnace, taken out after expanding treatment 5min rapidly in air, be cooled to normal temperature；
（4）Reduction：By step（3）In mixture be placed on 1000 DEG C, in the tube furnace of inert atmosphere, heat treatment
10min, obtains Graphene/CNTs combined conductive agent powders；
The following is the preparation of combined conductive agent slurry：
On the preparation basis of above-mentioned combined conductive agent, 5g steps are taken（4）In obtained Graphene/CNTs composite guides
Electric agent powder is added in 45g secondary deionized waters, ultrasonic disperse 10min, and prepared solid content is 10% aqueous Graphene/
CNTs combined conductive agent slurries.
A kind of ESEM of Graphene/CNTs combined conductive agents that this comparative example obtains（SEM）Image such as Fig. 6
It is shown, it can be observed that Graphene and CNTs is more uniform to be combined with each other.Even so, with embodiment 1 in
Graphene/CNTs/Super-P combined conductive agents compare, and Graphene/CNTs combined conductive agents are building high-effective conductive network
Aspect ability is poor.
With reference to the testing procedure of embodiment 1, experimental result：As shown in figure 8, Li4Ti5O12Electric discharge specific volume in 0.2 C
Measure as 159 mAh/g, specific discharge capacity during 1.0 C is 152mAh/g, the specific discharge capacity of 3.0 C is 148 mAh/g, 5.0
The specific discharge capacity of C is 138 mAh/g, even if its specific discharge capacity is still up to 126 mAh/g under 10.0 C of high magnification.
A kind of preparation method of 2. Graphene/Super-P combined conductive agents of comparative example, which comprises the following steps that：
（1）Mixing：The graphene oxide slurry of 100g solid contents 5% is added in single-glass reactor, 5g is added
Super-P and 0.05g surfactant sodium dodecyl base sodium sulfonates, mechanical agitation 30min, then ultrasonic disperse 30min again so as to
It is well mixed；
（2）Crush：By step（1）In mixed slurry suction filtration and in the drying of 100 DEG C of environment, be dried to water content≤5%, will
The solid of drying is crushed with pulverizer, makes particle diameter≤74 μm of pulverized particles；
（3）It is expanded：Heating muffle stove so as to be warming up to 300 DEG C, by step（2）The compound particles of middle crushing are put rapidly
Enter in Muffle furnace, taken out after expanding treatment 5min rapidly in air, be cooled to normal temperature；
（4）Reduction：By step（3）In mixture be placed on 1000 DEG C, in the tube furnace of inert atmosphere, heat treatment
10min, obtains Graphene/CNTs combined conductive agent powders.
The following is the preparation of combined conductive agent slurry：
On the preparation basis of above-mentioned combined conductive agent, 1g steps are taken（4）In obtained Graphene/Super-P it is multiple
Close conductive agent powder to be added in 49g 1-METHYLPYRROLIDONEs, ultrasonic disperse 10min, prepared solid content are 2% oiliness
Graphene/Super-P combined conductive agent slurries.
With reference to the testing procedure of embodiment 1, experimental result：As shown in figure 8, Li4Ti5O12Electric discharge specific volume in 0.2 C
Measure as 150 mAh/g, specific discharge capacity during 1.0 C is 137mAh/g, and the specific discharge capacity of 3.0 C is 91 mAh/g, 5.0 C
Specific discharge capacity be 80 mAh/g, even if under 10.0 C of high magnification its specific discharge capacity still be up to 71 mAh/g.
A kind of preparation method of 3. CNTs/Super-P combined conductive agents of comparative example, which comprises the following steps that：
（1）Mixing：5g CNTs are added in single-glass reactor, 95g secondary deionized waters is added, is added 5g
Super-P and 0.05g surfactant hexadecyltrimethylammonium chlorides, mechanical agitation 30min, then ultrasonic disperse again
30min so as to be well mixed；
（2）Crush：By step（1）In mixed slurry suction filtration and in the drying of 100 DEG C of environment, be dried to water content≤5%, will
The solid of drying is crushed with pulverizer, makes particle diameter≤74 μm of pulverized particles；
（3）It is expanded：Heating muffle stove so as to be warming up to 300 DEG C, by step（2）The compound particles of middle crushing are put rapidly
Enter in Muffle furnace, taken out after expanding treatment 5min rapidly in air, be cooled to normal temperature；
（4）Reduction：By step（3）In mixture be placed on 1000 DEG C, in the tube furnace of inert atmosphere, heat treatment
10min, obtains Graphene/CNTs combined conductive agent powders；
The following is the preparation of combined conductive agent slurry：
On the preparation basis of above-mentioned combined conductive agent, 1g steps are taken（4）In obtained CNTs/Super-P composite guides
Electric agent powder is added in 49g secondary deionized waters, ultrasonic disperse 10min, and prepared solid content is 2% aqueous CNTs/Super-
P combined conductive agent slurries.
A kind of ESEM of CNTs/Super-P combined conductive agents that this comparative example obtains（SEM）Image such as Fig. 8
It is shown, it can be observed that CNTs and Super-P do not have more uniform being combined with each other.Illustrate without through starching with graphene oxide
The In-situ reaction of material, is difficult to realize more uniform compound.
With reference to the testing procedure of embodiment 1, experimental result：As shown in figure 8, Li4Ti5O12Electric discharge specific volume in 0.2 C
Measure as 157 mAh/g, specific discharge capacity during 1.0 C is 145 mAh/g, the specific discharge capacity of 3.0 C is 125 mAh/g, 5.0
The specific discharge capacity of C is 117 mAh/g, even if its specific discharge capacity is still up to 105 mAh/g under 10.0 C of high magnification.
Claims (5)
1. a kind of preparation method of Graphene/CNTs/Super-P combined conductive agents, it is characterised in that comprise the steps：
（1）Mixing：The graphene oxide slurry of solid content≤50% is added in single-glass reactor, CNTs, Super- is added
P and surfactant, mechanical agitation 25min～35min, then ultrasonic disperse 20min～35min again so as to be well mixed；
（2）Crush：By step（1）In mixed slurry suction filtration and in the drying of 90 DEG C～110 DEG C environment, be dried to water content≤5%,
The solid of drying is crushed with pulverizer, particle diameter≤74 μm of pulverized particles are made；
（3）It is expanded：Heating muffle stove so as to be warming up to 200 DEG C～450 DEG C, by step（2）The compound particles of middle crushing are fast
Speed is put in Muffle furnace, takes out rapidly, be cooled to normal temperature in air after expanding treatment 3min～10min；
（4）Reduction：By step（3）In mixture be placed on 1000 DEG C, in the tube furnace of inert atmosphere, heat treatment 5min～
15min, obtains Graphene/CNTs/Super-P combined conductive agent powders.
2. the preparation method of combined conductive agent according to claim 1, it is characterised in that the step（1）Live on middle surface
Property agent selected from polyvinylpyrrolidone, dodecyl sodium sulfate, hexadecyltrimethylammonium chloride any one.
3. the preparation method of combined conductive agent according to claim 1, it is characterised in that the step（1）Live on middle surface
Property agent add mass percent for graphene oxide, CNT and conductive black gross mass 0.01%～1%.
4. a kind of preparation method of combined conductive agent slurry, it is characterised in that prepare the combined conductive agent in claim 1
On the basis of, also comprise the steps：
By the step（4）In the Graphene/CNTs/Super-P combined conductive agent powders that obtain be added in solvent, admittedly contain
Amount≤50%, ultrasonic disperse 8min～12min, are obtained Graphene/CNTs/Super-P combined conductive agent slurries.
5. the preparation method of combined conductive agent slurry according to claim 4, it is characterised in that the solvent is selected from secondary
Deionized water, 1-METHYLPYRROLIDONE.
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| CN106058264A (en) * | 2016-07-29 | 2016-10-26 | 成都新柯力化工科技有限公司 | Composite graphene conductive agent for lithium battery and preparation method |
| CN108091877A (en) * | 2016-11-23 | 2018-05-29 | 无锡格致新材料研发科技有限公司 | A kind of graphene denatured conductive agent and preparation method thereof |
| CN106711453A (en) * | 2016-12-28 | 2017-05-24 | 深圳市德方纳米科技股份有限公司 | Conductive carbon slurry, cathode material pole piece and lithium ion battery |
| CN106532059A (en) * | 2016-12-28 | 2017-03-22 | 深圳市德方纳米科技股份有限公司 | Preparation methods of conductive carbon slurry and positive electrode material plate |
| CN108269973B (en) * | 2017-01-02 | 2020-11-06 | 深圳格林德能源集团有限公司 | Carbon-based nano material based fast charging polymer lithium ion battery |
| CN106935312B (en) * | 2017-03-29 | 2018-09-28 | 浙江师范大学 | A kind of aqueous mixed type electrocondution slurry and preparation method thereof |
| CN107316751B (en) * | 2017-08-17 | 2019-01-01 | 大英聚能科技发展有限公司 | A kind of dedicated combined conductive agent of super capacitance cell and preparation method thereof |
| CN107579250B (en) * | 2017-08-28 | 2020-10-20 | 中国石油大学(北京) | Composite carbon material conductive agent |
| JP6822369B2 (en) * | 2017-10-02 | 2021-01-27 | トヨタ自動車株式会社 | Electrode plate manufacturing method |
| CN107732212A (en) * | 2017-10-25 | 2018-02-23 | 广东邦普循环科技有限公司 | A kind of porous nickel cobalt manganese composite hydroxide and preparation method thereof and the application in lithium ion anode material |
| CN107887594A (en) * | 2017-12-04 | 2018-04-06 | 中国科学院青岛生物能源与过程研究所 | A kind of compound lithium-rich manganese-based anode material and preparation method for lithium ion battery |
| CN109524667A (en) * | 2018-10-16 | 2019-03-26 | 上海力信能源科技有限责任公司 | A kind of preparation method of combined conductive agent and preparation method thereof, carbon nanotube |
| CN109768279A (en) * | 2018-12-20 | 2019-05-17 | 上海力信能源科技有限责任公司 | A kind of combined conductive agent and preparation method thereof, lithium ion cell positive |
| CN111430686A (en) * | 2020-02-27 | 2020-07-17 | 蜂巢能源科技有限公司 | Negative electrode material, battery, and vehicle |
| CN111640526B (en) * | 2020-06-08 | 2021-09-14 | 淮北市吉耐新材料科技有限公司 | Composite carbon nanotube conductive slurry and preparation process thereof |
| CN111484271B (en) * | 2020-06-28 | 2020-09-18 | 山东海科创新研究院有限公司 | Method for preparing graphene composite conductive slurry by microwave-ultrasonic and obtained product |
| CN112436146B (en) * | 2020-11-20 | 2022-06-17 | 安徽南都华拓新能源科技有限公司 | Lithium battery positive electrode material, preparation method and lithium battery |
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