CN107689452A - A kind of graphene composite conductive slurry, its preparation method and application - Google Patents
A kind of graphene composite conductive slurry, its preparation method and application Download PDFInfo
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- CN107689452A CN107689452A CN201710787332.2A CN201710787332A CN107689452A CN 107689452 A CN107689452 A CN 107689452A CN 201710787332 A CN201710787332 A CN 201710787332A CN 107689452 A CN107689452 A CN 107689452A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a kind of graphene composite conductive slurry, its preparation method and application.The graphene composite conductive slurry includes graphene, non-sheet conductive agent, dispersant, solvent and viscosity modifier, and between at least partially embedded graphene film lamella of non-sheet conductive agent.Described preparation method includes：Expanded graphite, dispersant and solvent are well mixed, and carry out shearing stripping, the first slurry is made；Non- sheet conductive agent is added in the first slurry, part intercalation processing is carried out at least through lapping mode, makes non-sheet conductive agent and graphene film dispersed, the second slurry is made.The graphene composite conductive slurry of the present invention has excellent dispersion stabilization, and active material is shown excellent chemical property in lithium ion battery, can improve electrode capacity, reduce the internal resistance of cell, improves cycle performance；The preparation method has the advantages such as technique is simple, workable, raw material sources are wide, cost is low simultaneously.
Description
Technical field
The present invention relates to a kind of graphene composite conductive slurry, more particularly to a kind of graphene composite conductive slurry and its system
Preparation Method and the application in lithium ion battery, belong to lithium ion battery conductive agent technical field.
Background technology
The positive electrode active materials of lithium ion battery are the transition metal oxide containing lithium, and discharge and recharge is at this by lithium ion
Shuttle and realize in a little oxides.But the electrical conductivity of these transition metal oxides is generally very low, this is greatly limited
The charge-discharge performance under the high magnification of lithium ion battery is made.Therefore, generally needed when preparing electrode by these active materials
Conductive agent is added to improve its electric conductivity.Although the electric conductivity of negative pole graphite is fine, stone after multiple discharge and recharge is undergone
Contact between the dilation effect of ink experience will make graphite particle is reduced, therefore, it is also desirable to add amount of conductive agent to tie up
Hold its structural stability.
In order to realize the chemical property under higher energy density and high magnification, it is excellent and in activity to find electric conductivity
The conductive agent that perfect conductive network can be built in material is particularly important.Graphene due to excellent electric conductivity,
And specific surface area is larger, a kind of conductive agent of great application prospect is would is that after it disperses in active material.But graphite
There is stronger π-π interaction forces in alkene interlayer, the graphene peeled away can usually reunite during storage and use,
Therefore the scattered of graphene is always a great problem for hindering it to apply.It in summary it can be seen, the complete graphene of preparation structure
And using its stable dispersion it is key point of the graphene as lithium ion battery conductive agent in the slurry.
The content of the invention
It is a primary object of the present invention to provide a kind of graphene composite conductive slurry and preparation method and application, with gram
Take deficiency of the prior art.
To realize aforementioned invention purpose, the technical solution adopted by the present invention includes：
The embodiments of the invention provide a kind of graphene composite conductive slurry, it include calculating in parts by weight such as the following group
Point：90~95 parts of 1~6 part of graphene, 1~6 part of non-sheet conductive agent, 0~1 part of dispersant and solvent, and in the graphite
In alkene composite conducting slurry between the non-at least partially embedded graphene sheet layer of sheet conductive agent.
One of preferably, it is fine that the non-sheet conductive agent includes conductive black, electrically conductive graphite, CNT and carbon
Any one in dimension or two or more combinations.
One of preferably, the dispersant includes nonionic surface active agent.
One of preferably, the solvent includes 1-METHYLPYRROLIDONE and/or deionized water.
One of preferably, the graphene composite conductive slurry also includes viscosity modifier, the viscosity regulation
Agent includes any one in Kynoar, sodium carboxymethylcellulose, polytetrafluoroethylene (PTFE) and polyvinyl alcohol or two or more
Combination.
One of preferably, the graphene is that expanded graphite is dispersed through being made after peeling off.
Further, the expanded graphite includes expanding 100~400 times of worm graphite formed, grain by expansible graphite
Footpath is 30~800 mesh.
The embodiment of the present invention additionally provides a kind of preparation method of graphene composite conductive slurry, and it includes：
(1) expanded graphite, dispersant and solvent are well mixed, and carry out shearing stripping, the first slurry is made；
(2) non-sheet conductive agent is added in first slurry, carries out part intercalation at least through lapping mode afterwards
Processing, between making non-sheet conductive agent insertion graphene, and disperse with graphene uniform, the second slurry is made.Wherein non-sheet
Conductive agent is dispersed with graphene progress in worm graphite shears stripping process, and steric hindrance is formed between graphene, can be had
Effect avoids the graphitization of graphene.
One of preferably, step (1) specifically includes：Expanded graphite, dispersant and solvent are well mixed, and with
500~1000r/min rotating speed carries out shearing decentralized processing 5~60 minutes in homogenizer, afterwards in sand mill with
1000~3000r/min rotating speed carries out shearing lift-off processing 5~60 minutes, and first slurry is made.
Preferably, described shearing lift-off processing is carried out with grinder, wherein the grinder use the particle diameter of zirconium pearl for
0.3~3.0mm.
One of preferably, step (2) specifically includes：Non- sheet conductive agent is added in first slurry, it
Use grinder to be ground intercalation processing 30~60 minutes with 800~3000r/min rotating speed afterwards, second slurry is made
Material.
One of preferably, the preparation method also includes：Viscosity with viscosity modifier to second slurry
It is adjusted, obtains the graphene composite conductive slurry.
Preferably, the viscosity of the graphene composite conductive slurry is 500~5000mPas.
The embodiment of the present invention is additionally provided by the graphene composite conductive slurry of foregoing method preparation.
Preferably, the graphene composite conductive slurry includes the following component calculated in parts by weight：Graphene 1~6
Part, 1~6 part of non-sheet conductive agent, 0~1 part of dispersant and 90~95 parts of solvent, and in the graphene composite conductive slurry
In between the non-at least partially embedded graphene sheet layer of sheet conductive agent.Wherein non-sheet conductive agent was peeled off in the shearing of worm graphite
It is dispersed with graphene progress in journey, steric hindrance is formed between graphene, can effectively avoid the graphitization of graphene.
The embodiment of the present invention additionally provides application of the foregoing graphene composite conductive slurry in lithium ion battery.
For example, the application includes：The graphene composite conductive slurry is used for anode active material of lithium ion battery
Or the conductive agent of lithium ion cell positive negative material.
Preferably, the anode active material of lithium ion battery includes LiFePO4, cobalt acid lithium, nickle cobalt lithium manganate and nickel cobalt
Any one in lithium aluminate or two or more combinations.
Preferably, the lithium ion battery anode active material include graphite, carbonaceous mesophase spherules, metal oxide, silicon,
Any one in silicon/carbon or two or more combinations.
Compared with prior art, advantages of the present invention includes：
1) graphene in graphene composite conductive slurry provided by the invention passes through the part intercalation of non-sheet conductive agent,
The graphene graphitization, therefore there is excellent dispersion stabilization again peeled away can be prevented；And use it for lithium-ion electric
Dosage can be substantially reduced during the conductive agent in pond, reduces cost, and active material is shown excellent electricity in lithium ion battery
Chemical property, illustrate that both graphene and non-sheet conductive agent have cooperative effect, electrode capacity can be improved, reduced in battery
Resistance, improve cycle performance.
2) preparation method of graphene composite conductive slurry provided by the invention is embedded in non-sheet conductive agent means of abrasion
Further stable graphene is carried out between graphene sheet layer, the graphene peeled away graphitization again is prevented, there is preparation technology
Simply, the workable, advantage such as raw material sources are wide, cost is low.
Brief description of the drawings
Fig. 1 is the SEM pictures that the embodiment of the present invention 1 obtains graphene composite mortar；
Fig. 2 is that the embodiment of the present invention 1 is obtained to acetylene black in graphene composite conductive slurry, comparative example 1, contrast respectively
Graphene in example 2, the CNT in comparative example 3, the direct hybrid conductive agent in comparative example 4 are used in tertiary cathode material
The cycle performance contrast schematic diagram of the buckle type lithium-ion half-cell of acquisition.
Embodiment
The problem of scattered, is difficult to based on graphene conductive agent present in prior art, inventor through studying for a long period of time and
A large amount of practices, it is able to propose technical scheme.The technical scheme, its implementation process and principle etc. will be made as follows into one
The explanation of step.
The one side of the embodiment of the present invention provides a kind of graphene composite conductive slurry, and it is included in parts by weight
The following component calculated：90~95 parts of 1~6 part of graphene, 1~6 part of non-sheet conductive agent, 0~1 part of dispersant and solvent, and
In the graphene composite conductive slurry between the non-at least partially embedded graphene sheet layer of sheet conductive agent.Wherein non-sheet is led
Electric agent carries out dispersed, the further stable graphene of progress, in graphite in expanded graphite shears stripping process with graphene
Steric hindrance is formed between alkene, can effectively avoid the graphitization again of graphene peeled away.Pass through graphene and non-flaky structure
The synergy of conductive agent, for dosage can be substantially reduced in lithium ion battery, cost is reduced, while improve electrode capacity, drop
The low internal resistance of cell, improve cycle performance.
One of preferably, it is fine that the non-sheet conductive agent includes conductive black, electrically conductive graphite, CNT and carbon
Any one in dimension etc. or two or more combinations, but not limited to this.
One of preferably, the dispersant is polyvinylpyrrolidone, polyethylene glycol and other nonionic tables
Any one in the activating agent of face or two or more combinations, but not limited to this.
One of preferably, the solvent is that 1-METHYLPYRROLIDONE, deionized water and other batteries are available molten
Any one in agent.
One of preferably, the graphene composite conductive slurry also includes appropriate viscosity modifier, described viscous
Spending conditioning agent includes any one in Kynoar, sodium carboxymethylcellulose, polytetrafluoroethylene (PTFE) and polyvinyl alcohol etc. or two
The combination of the kind above, but not limited to this.
One of preferably, the graphene is that expanded graphite is dispersed through being made after peeling off.
Further, the expanded graphite includes expanding 100~400 times of worm graphite formed by expansible graphite, its
Particle diameter is 30~800 mesh.
The embodiment of the present invention another aspect provides a kind of preparation method of graphene composite conductive slurry, it is wrapped
Include：
(1) expanded graphite, dispersant and solvent are well mixed, and carry out shearing stripping, the first slurry is made；
(2) non-sheet conductive agent is added in first slurry, carries out part intercalation at least through lapping mode afterwards
Processing, between making non-sheet conductive agent insertion graphene sheet layer, the second slurry is made, obtains graphene composite conductive slurry.
One of preferably, step (1) specifically includes：Expanded graphite, dispersant and solvent are well mixed, and with
500~1000r/min rotating speed carries out shearing decentralized processing 5~60 minutes in homogenizer, afterwards in sand mill with
1000~3000r/min rotating speed carries out shearing lift-off processing 5~60 minutes, and first slurry is made.
Wherein, the graphene is that expanded graphite is dispersed through being made after peeling off.Further, the expanded graphite is can be swollen
The worm graphite that swollen 100~400 times of graphite expansion obtains, its particle diameter are 30~800 mesh.The dispersant is polyvinylpyrrolidine
Any one in ketone, polyethylene glycol and other nonionic surface active agent or two or more combinations, but not limited to this.Institute
Solvent is stated as any one in 1-METHYLPYRROLIDONE, deionized water and the available solvent of other batteries.
Preferably, described shearing lift-off processing is carried out with grinder, wherein the grinder use the particle diameter of zirconium pearl for
0.3~3.0mm.
One of preferably, step (2) specifically includes：Non- sheet conductive agent is added in first slurry, it
Use grinder to be ground intercalation processing 30~60 minutes with 800~3000r/min rotating speed afterwards, second slurry is made
Material.
Wherein, the non-sheet conductive agent includes any in conductive black, electrically conductive graphite, CNT and carbon fiber etc.
One or more kinds of combinations, but not limited to this.
The present invention, which is peeled off expanded graphite into graphene, and with dispersant using sand mill in preparation process, to be divided
Dissipate.And then embedded graphene sheet layer is ground with non-lamella conductive agent and carries out further stable graphene, prevent the graphite peeled away
Alkene graphitization again.Therefore, the graphene composite conductive slurry has excellent dispersion stabilization.
One of preferably, the preparation method also includes：Viscosity with viscosity modifier to second slurry
It is adjusted, obtains the graphene composite conductive slurry.
Preferably, the viscosity of the graphene composite conductive slurry is 500~5000mPas.
Wherein, the case study on implementation being more highly preferred to as the present invention one, the preparation method of the graphene composite conductive slurry
It may include steps of：
(1) by worm graphite, dispersant into solvent, premixing processing, Ran Houyong are first carried out with homogenizer
Sand mill carries out high speed shear to expanded graphite and peels off the first slurry of preparation；
(2) other non-sheet conductive agents are added in first slurry and further ground using sand mill progress part intercalation
Mill, prepare the second slurry；
(3) it is compound that the graphene is made after the second slurry is adjusted to suitable viscosity with appropriate viscosity modifier
Electrocondution slurry.
The embodiment of the present invention is additionally provided by the graphene composite conductive slurry of foregoing method preparation.
Preferably, the graphene composite conductive slurry includes the following component calculated in parts by weight：Graphene 1~6
Part, 1~6 part of non-sheet conductive agent, 0~1 part of dispersant and 90~95 parts of solvent, and in the graphene composite conductive slurry
In between the non-at least partially embedded graphene sheet layer of sheet conductive agent.Wherein non-sheet conductive agent was peeled off in the shearing of worm graphite
It is dispersed with graphene progress in journey, steric hindrance is formed between graphene, can effectively avoid the graphitization of graphene.
The other side of the embodiment of the present invention additionally provides foregoing graphene composite conductive slurry in lithium ion battery
In application.
For example, the application includes：The graphene composite conductive slurry is used for anode active material of lithium ion battery
Or the conductive agent of lithium ion cell positive negative material.
Preferably, the anode active material of lithium ion battery includes LiFePO4, cobalt acid lithium, nickle cobalt lithium manganate and nickel cobalt
Any one in the ternary materials such as lithium aluminate or two or more combinations, but not limited to this.
Preferably, the lithium ion battery anode active material include graphite, carbonaceous mesophase spherules, metal oxide, silicon,
Any one in silicon/carbon or two or more combinations, but not limited to this.
By above-mentioned technical proposal, graphene composite conductive slurry of the invention has an excellent dispersion stabilization, and
Active material is shown excellent chemical property in lithium ion battery, electrode capacity can be improved, the internal resistance of cell is reduced, improve
Cycle performance；The preparation method has the advantages such as preparation technology is simple, workable, raw material sources are wide, cost is low simultaneously.
Technical scheme is further described below by way of some embodiments and with reference to accompanying drawing.It is however, selected
Embodiment be merely to illustrate the present invention, and do not limit the scope of the invention.
Embodiment 1
A kind of preparation method of graphene composite conductive slurry comprises the following steps in the present embodiment：
1) 80g is expanded to 400 times of worm graphite (100 mesh), 10g polyvinylpyrrolidones and 1850g N- methylpyrroles
Alkanone mixes, and is ground after being stirred scattered 30 minutes using homogenizer with 500r/min rotating speed using sand mill
Mill, rotating speed 2800r/min, milling time are 60 minutes；
2) take 60g multi-walled carbon nanotubes to add further to be ground into above-mentioned slurry, rotating speed 800r/min, grind
Time is 30 minutes；
3) viscosity of above-mentioned gained slurry is adjusted with Kynoar, adjustment viscosity to 5000mPas.
4) the graphene composite mortar is used in ternary cathode material of lithium ion battery, according to ternary active material, gathered
Vinylidene, the mass fraction of graphene composite conductive agent are configured to electrode for the ratio of 90%, 6%, 4% (in terms of solid content)
Slurry, coated on aluminium foil after stirring, anode pole piece is obtained after dry, roll-in.
Comparative example 1
Conductive agent using conventional conductive agent acetylene black as tertiary cathode material, according to ternary active material, Kynoar,
The mass fraction of acetylene black is configured to electrode slurry for the ratio of 84%, 6%, 10% (in terms of solid content), is coated on after stirring
On aluminium foil, dry, obtain anode pole piece after roll-in.
Comparative example 2
Graphene slurry is prepared by the step 1) of embodiment 1.Using the graphene contained by the graphene slurry as tertiary cathode material
The conductive agent of material, according to the mass fraction of ternary active material, Kynoar, graphene for 90%, 6%, 4% (to contain admittedly
Gauge) ratio be configured to electrode slurry, coated on aluminium foil, drying, obtain anode pole piece after roll-in after stirring.
Comparative example 3
Conductive agent using CNT as tertiary cathode material, according to ternary active material, Kynoar, CNT
Mass fraction be configured to electrode slurry for the ratio of 90%, 6%, 4% (in terms of solid content), coated on aluminium foil after stirring,
Dry, obtain anode pole piece after roll-in.
Comparative example 4
Graphene slurry is prepared by the step 1) of embodiment 1.Graphene using CNT and contained by the graphene slurry as
The conductive agent of tertiary cathode material, the mass fraction according to ternary active material, Kynoar, graphene, CNT are
90%th, the ratio of 6%, 2.3%, 1.7% (in terms of solid content), by graphene slurry, CNT, ternary active material and gather
Vinylidene is directly hybridly prepared into electrode slurry, and coated on aluminium foil after stirring, anode pole piece is obtained after dry, roll-in.
Conductive agent in graphene composite conductive slurry made from embodiment 1 and comparative example 1-4 is used for buckle type lithium-ion
Cycle performance test is carried out in half-cell, as a result as shown in Fig. 2 wherein specific capacity is with active substances.It can be sent out through Fig. 2 contrasts
Graphene composite conductive slurry prepared by the existing present invention compared to traditional acetylene black conductor for, while dosage is reduced
Performance to the coulombic efficiency of tertiary cathode material, cyclical stability and gram specific capacity is respectively provided with certain improvement result, and
And the composite conducting slurry prepared by peeling off the method for intercalation can preferably play both synergies.
Embodiment 2
A kind of preparation method of graphene composite conductive slurry comprises the following steps in the present embodiment：
1) 20g is expanded to 100 times of worm graphite (800 mesh) to mix with 1860g 1-METHYLPYRROLIDONEs, using at a high speed
Mixer is ground after being stirred scattered 30 minutes with 1000r/min rotating speed using sand mill, rotating speed 3000r/min,
Milling time is 5 minutes；
2) take 120g acetylene blacks to add further to be ground into above-mentioned slurry, rotating speed 3000r/min, milling time
For 30 minutes；
3) viscosity of above-mentioned gained slurry is adjusted with polyvinyl alcohol, the viscosity after adjustment to 4000mPas.
4) the graphene composite conductive slurry is used in lithium-ion battery lithium iron phosphate positive electrode, finds this after tested
Embodiment prepare graphene composite conductive slurry compared to conventional conductive agent for, to LiFePO4 while dosage is reduced
The performance of the coulombic efficiency of positive electrode, cycle performance and gram specific capacity is respectively provided with certain improvement result.
Embodiment 3
A kind of preparation method of graphene composite conductive slurry comprises the following steps in the present embodiment：
1) 100g is expanded to 100 times of worm graphite (500 mesh), 10g polyvinylpyrrolidones and 1870g N- methyl pyrroles
Pyrrolidone mixes, and is ground after being stirred scattered 30 minutes using homogenizer with 800r/min rotating speed using sand mill
Mill, rotating speed 2500r/min, milling time are 30 minutes；
2) take 20g Super P to add further to be ground into above-mentioned slurry, rotating speed 2500r/min, during grinding
Between be 60 minutes；
3) viscosity of above-mentioned gained slurry is adjusted with Kynoar, the viscosity after adjustment to 3000mPas.
4) the graphene composite conductive slurry is used in lithium ion battery ZnO negative materials, finds this implementation after tested
Example prepare graphene composite conductive slurry compared to conventional conductive agent for, to ZnO negative materials while dosage is reduced
The performance of coulombic efficiency, cyclical stability and gram specific capacity be respectively provided with certain improvement result.
Embodiment 4
A kind of preparation method of graphene composite conductive slurry comprises the following steps in the present embodiment：
1) by 20g expand 100 times worm graphite (200 mesh), 5g sodium taurocholates mixed with 1900g 1-METHYLPYRROLIDONEs,
It is ground after being stirred scattered 5 minutes using homogenizer with 1000r/min rotating speed using sand mill, rotating speed
3000r/min, milling time are 20 minutes；
2) take 75g acetylene blacks to add further to be ground into above-mentioned slurry, rotating speed 2500r/min, milling time
For 60 minutes；
3) viscosity of above-mentioned gained slurry is adjusted with polyvinyl alcohol, the viscosity after adjustment to 500mPas.
4) the graphene composite conductive slurry is used in lithium cobalt oxide cathode material for lithium ion battery, finds this reality after tested
Apply example preparation graphene composite conductive slurry compared to conventional conductive agent for, to lithium cobaltate cathode while dosage is reduced
The performance of the coulombic efficiency of material, cyclical stability and gram specific capacity is respectively provided with certain improvement result.
Embodiment 5
A kind of preparation method of graphene composite conductive slurry comprises the following steps in the present embodiment：
1) by 60g expand 200 times worm graphite, 5g polyethylene glycol mixed with 1875g deionized waters, use high-speed stirred
Machine is ground after being stirred scattered 30 minutes with 800r/min rotating speed using sand mill, rotating speed 1000r/min, during grinding
Between be 60 minutes；
2) take 60g carbon fibers to add further to be ground into above-mentioned slurry, rotating speed 2000r/min, milling time
For 30 minutes；
3) viscosity of above-mentioned gained slurry is adjusted with sodium carboxymethylcellulose, the viscosity after adjustment is extremely
5000mPa.s。
4) the graphene composite conductive slurry is used in lithium ion battery silicon/carbon negative pole material, finds this reality after tested
Apply example preparation graphene composite conductive slurry compared to conventional conductive agent for, to negative electrode active material while dosage is reduced
The performance of the coulombic efficiency of material, cyclical stability and gram specific capacity is respectively provided with certain improvement result.
In summary, by above-mentioned technical proposal, the graphene that the present invention is prepared for stable dispersion by worm graphite is compound
Electrocondution slurry, by the synergy of graphene and the conductive agent of non-flaky structure, for that can be substantially reduced in lithium ion battery
Dosage, cost is reduced, while improve electrode capacity, reduce the internal resistance of cell, improve cycle performance；The preparation method has system simultaneously
The standby advantage such as technique is simple, workable, raw material sources are wide, cost is low.
In addition, mode of the inventor referring also to 1~embodiment of embodiment 5, with the other originals listed in this specification
Material and condition etc. are tested, and the graphene composite conductive slurry with excellent dispersion stabilization has equally been made.
It should be appreciated that the technical concepts and features of above-described embodiment only to illustrate the invention, ripe its object is to allow
Present disclosure can be understood and implement according to this by knowing the personage of technique, and the protection model of the present invention can not be limited with this
Enclose.Any equivalent change or modification in accordance with the spirit of the invention, it should all be included within the scope of the present invention.
Claims (10)
1. a kind of graphene composite conductive slurry, it is characterised in that including the following component calculated in parts by weight：Graphene 1~
90~95 parts of 6 parts, 1~6 part of non-sheet conductive agent, 0~1 part of dispersant and solvent, and starched in the graphene composite conductive
In material between the non-at least partially embedded graphene sheet layer of sheet conductive agent.
2. graphene composite conductive slurry according to claim 1, it is characterised in that：The non-sheet conductive agent includes leading
Any one in electric carbon black, electrically conductive graphite, CNT and carbon fiber or two or more combinations；And/or the dispersant
Including nonionic surface active agent；Preferably, the dispersant includes polyvinylpyrrolidone and/or polyethylene glycol；With/
Or, the solvent includes 1-METHYLPYRROLIDONE and/or deionized water.
3. graphene composite conductive slurry according to claim 1 or 2, it is characterised in that also including viscosity modifier；It is excellent
Choosing, the viscosity modifier includes any in Kynoar, sodium carboxymethylcellulose, polytetrafluoroethylene (PTFE) and polyvinyl alcohol
One or more kinds of combinations.
4. graphene composite conductive slurry according to claim 1, it is characterised in that：The graphene passes through for expanded graphite
It is made after scattered stripping；Preferably, the expanded graphite includes expanding 100~400 times of myrmekites formed by expansible graphite
Ink, particle diameter are 30~800 mesh.
A kind of 5. preparation method of graphene composite conductive slurry, it is characterised in that including：
(1) expanded graphite, dispersant and solvent are well mixed, and carry out shearing stripping, the first slurry is made；
(2) non-sheet conductive agent is added in first slurry, carries out part intercalation processing at least through lapping mode afterwards,
Between making the non-at least partially embedded graphene of sheet conductive agent, and disperse with graphene uniform, the second slurry is made.
6. preparation method according to claim 5, it is characterised in that step (1) specifically includes：By expanded graphite, disperse
Agent and solvent are well mixed, and carry out shearing decentralized processing 5~60 minutes with 500~1000r/min rotating speed, afterwards with 1000
~3000r/min rotating speed carries out shearing lift-off processing 5~60 minutes in sand mill, and first slurry is made；Preferably,
Described shearing lift-off processing is carried out with sand mill, wherein the grinder uses the particle diameter of zirconium pearl as 0.3~3.0mm；It is preferred that
, the expanded graphite is that expansible graphite expands 100~400 times of obtained worm graphite, and particle diameter is 30~800 mesh；It is preferred that
, the dispersant includes nonionic surface active agent；Especially preferred, the dispersant includes polyvinylpyrrolidone
And/or polyethylene glycol；Preferably, the solvent includes 1-METHYLPYRROLIDONE and/or deionized water.
7. preparation method according to claim 5, it is characterised in that step (2) specifically includes：Non- sheet conductive agent is added
Enter in first slurry, use sand mill to be ground 30~60 points of intercalation processing with 800~3000r/min rotating speed afterwards
Clock, second slurry is made；Preferably, the non-sheet conductive agent includes conductive black, electrically conductive graphite, CNT and carbon
Any one in fiber or two or more combinations.
8. according to the preparation method any one of claim 5-7, it is characterised in that also include：With viscosity modifier to institute
The viscosity for stating the second slurry is adjusted, and obtains the graphene composite conductive slurry；Preferably, the graphene composite conductive
The viscosity of slurry is 500~5000mPas；Preferably, the viscosity modifier includes Kynoar, carboxymethyl cellulose
Any one in sodium, polytetrafluoroethylene (PTFE) and polyvinyl alcohol or two or more combinations.
9. the graphene composite conductive slurry prepared as the method any one of claim 5-8；Preferably, the graphite
Alkene composite conducting slurry includes the following component calculated in parts by weight：1~6 part of graphene, non-sheet conductive agent 1~6 part, point
90~95 parts of 0~1 part of powder and solvent, and non-sheet conductive agent is at least partly embedding in the graphene composite conductive slurry
Enter between graphene sheet layer.
10. the application of claim 1-4, the graphene composite conductive slurry any one of 9 in lithium ion battery；It is preferred that
, the application includes：The graphene composite conductive slurry is used for anode active material of lithium ion battery or lithium-ion electric
The conductive agent of pond positive pole negative material；Preferably, the anode active material of lithium ion battery include LiFePO4, cobalt acid lithium,
Any one in nickle cobalt lithium manganate and nickel cobalt lithium aluminate or two or more combinations；Preferably, the negative electrode of lithium ion battery
Active material includes any one or two or more groups in graphite, carbonaceous mesophase spherules, metal oxide, silicon, silicon/carbon
Close.
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| CN108470914A (en) * | 2018-06-05 | 2018-08-31 | 中国科学院苏州纳米技术与纳米仿生研究所南昌研究院 | A kind of preparation method of graphene complex lithium electricity electrocondution slurry |
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| CN110808375A (en) * | 2019-11-07 | 2020-02-18 | 深圳市德方纳米科技股份有限公司 | Preparation method and device of graphene carbon nanotube composite conductive liquid and conductive liquid |
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| CN111303586A (en) * | 2018-12-12 | 2020-06-19 | 新奥石墨烯技术有限公司 | Thermosetting resin composition based on graphene three-dimensional heat conduction network chain and preparation method thereof |
| CN111326274A (en) * | 2018-12-13 | 2020-06-23 | 山东欧铂新材料有限公司 | Modified graphene composite slurry with high dispersion stability and preparation method thereof |
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| CN111933949A (en) * | 2020-08-18 | 2020-11-13 | 东莞市海洲新材料科技有限公司 | Graphene conductive agent with adjustable sheet diameter distribution ratio, preparation method thereof, negative electrode and lithium ion battery |
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| CN108822610A (en) * | 2018-04-11 | 2018-11-16 | 杭州牛墨科技有限公司 | A kind of graphene carbon nanotube is manufactured to be electromagnetically shielded heat generating pastes and preparation method thereof |
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| CN109161110A (en) * | 2018-08-17 | 2019-01-08 | 厦门凯纳石墨烯技术股份有限公司 | A kind of addition graphene/carbon black composite material tyre airtight layer glue and preparation method thereof |
| CN110890544A (en) * | 2018-09-11 | 2020-03-17 | 深圳格林德能源有限公司 | Graphene composite conductive slurry and preparation method thereof |
| CN109461936A (en) * | 2018-09-25 | 2019-03-12 | 中国科学院苏州纳米技术与纳米仿生研究所南昌研究院 | A kind of environment-friendly preparation method thereof of the aqueous composite mortar of graphene |
| CN110970620A (en) * | 2018-09-30 | 2020-04-07 | 山东欧铂新材料有限公司 | Preparation method of high-stability graphene/carbon nanotube composite conductive slurry |
| CN110970620B (en) * | 2018-09-30 | 2021-09-14 | 山东欧铂新材料有限公司 | Preparation method of high-stability graphene/carbon nanotube composite conductive slurry |
| CN111303586A (en) * | 2018-12-12 | 2020-06-19 | 新奥石墨烯技术有限公司 | Thermosetting resin composition based on graphene three-dimensional heat conduction network chain and preparation method thereof |
| CN111326274A (en) * | 2018-12-13 | 2020-06-23 | 山东欧铂新材料有限公司 | Modified graphene composite slurry with high dispersion stability and preparation method thereof |
| CN109671952A (en) * | 2018-12-21 | 2019-04-23 | 福建翔丰华新能源材料有限公司 | Microcrystalline graphene-based composite conductive slurry for lithium battery and preparation method thereof |
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| CN109728301B (en) * | 2018-12-27 | 2020-12-25 | 宁波杉元石墨烯科技有限公司 | Graphene-containing lithium battery conductive slurry and preparation method thereof |
| CN109728301A (en) * | 2018-12-27 | 2019-05-07 | 宁波杉元石墨烯科技有限公司 | A kind of lithium battery electrocondution slurry of containing graphene and preparation method thereof |
| CN109830685A (en) * | 2019-04-03 | 2019-05-31 | 哈尔滨万鑫石墨谷科技有限公司 | A kind of composite conducting slurry, preparation method and the usage |
| CN110120498A (en) * | 2019-04-26 | 2019-08-13 | 中国航发北京航空材料研究院 | A kind of graphene flexible electrical pole piece and the preparation method and application thereof |
| CN110311132A (en) * | 2019-04-29 | 2019-10-08 | 黑龙江黑大生物质新材料科技有限公司 | A kind of graphene battery conductive agent and preparation method and application, a kind of electrode material |
| CN110048123A (en) * | 2019-04-29 | 2019-07-23 | 苏州聚龙能源科技有限公司 | Silicon/carbon/graphite in lithium ion batteries alkene few-wall carbon nanotube waterborne conductive agent and preparation method thereof |
| CN110808375A (en) * | 2019-11-07 | 2020-02-18 | 深圳市德方纳米科技股份有限公司 | Preparation method and device of graphene carbon nanotube composite conductive liquid and conductive liquid |
| CN113120887B (en) * | 2019-12-30 | 2023-06-30 | 山东欧铂新材料有限公司 | Graphene oily dispersion liquid for conductive ink, and preparation method and application thereof |
| CN113122072A (en) * | 2019-12-30 | 2021-07-16 | 山东欧铂新材料有限公司 | Graphene conductive ink for heating film and preparation method thereof |
| CN113120887A (en) * | 2019-12-30 | 2021-07-16 | 山东欧铂新材料有限公司 | Graphene oily dispersion liquid for conductive ink, and preparation method and application thereof |
| CN113555229B (en) * | 2020-04-26 | 2023-04-21 | 中天超容科技有限公司 | Graphene paper current collector, preparation method and supercapacitor |
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| CN111710863A (en) * | 2020-06-28 | 2020-09-25 | 东莞市海洲新材料科技有限公司 | Graphene conductive agent, preparation method thereof, lithium ion battery cathode and lithium ion battery |
| CN111933949A (en) * | 2020-08-18 | 2020-11-13 | 东莞市海洲新材料科技有限公司 | Graphene conductive agent with adjustable sheet diameter distribution ratio, preparation method thereof, negative electrode and lithium ion battery |
| CN114078609A (en) * | 2020-08-19 | 2022-02-22 | 山东欧铂新材料有限公司 | Graphene aqueous conductive slurry for lithium ion battery, and preparation method and application thereof |
| CN112299485A (en) * | 2020-10-23 | 2021-02-02 | 青岛昊鑫新能源科技有限公司 | Method for simply peeling off multiple two-dimensional layered materials in large quantity by means of superfine carbon tubes |
| CN112382760A (en) * | 2020-10-29 | 2021-02-19 | 厦门大学 | Preparation method of aqueous conductive binder for positive electrode of lithium-sulfur battery |
| CN112349448A (en) * | 2020-11-02 | 2021-02-09 | 山东华冠智能卡有限公司 | Graphene conductive slurry, preparation method and RFID electronic tag |
| CN113745517A (en) * | 2021-08-25 | 2021-12-03 | 金川集团股份有限公司 | Preparation method of conductive paste |
| CN113912046A (en) * | 2021-09-30 | 2022-01-11 | 赣州市康达新能源材料有限公司 | Preparation method of artificial graphene super conductive agent |
| CN114783653A (en) * | 2022-04-07 | 2022-07-22 | 江苏博纳科技有限公司 | Water-based graphene composite conductive slurry, preparation method of slurry and graphene heating film |
| CN115069364A (en) * | 2022-06-18 | 2022-09-20 | 湖北冠毓新材料科技有限公司 | Method for improving grinding efficiency of carbon nanotube slurry |
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