CN108417839A - A method of cathode of lithium battery electrode high rate performance is improved by magnetic effect - Google Patents
A method of cathode of lithium battery electrode high rate performance is improved by magnetic effect Download PDFInfo
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- 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 present invention proposes a kind of method improving cathode of lithium battery electrode high rate performance by magnetic effect,Ferrofluid and Ferrite Material are loaded using 1-dimention nano negative material,Oriented structure is formed under magnetic field,It is vertical with copper current collector to be combined,Form the negative electrode of three-dimensional dense array structures,The internal resistance caused by the anisotropic growth of cathode that the present invention overcomes traditional lithium cell cathode materials during lithium ion deintercalation is excessive,The difficult problem of lithium ion insertion,It is combined by Van der Waals force with cathode by Ferrite Material and ferrofluid,Make negative material that there is the vertical of orientation to combine on copper current collector surface under magnetic fields,Form three-dimensional closely spaced array,The active point of material is set to expose more abundant,Form lithium ion transport channel,Effectively improve deintercalation and transfer ability of the lithium ion in negative material,Improve the high rate performance of battery,Achieve the purpose that reach raising negative material electrical property by controlling negative pole structure rather than ingredient.
Description
Technical field
The present invention relates to technical field of lithium ion, and in particular to a kind of to improve cathode of lithium battery electricity by magnetic effect
The method of pole high rate performance.
Background technology
Along with economic globalization process and energy demand it is continuous surging, find new energy storage device and have become newly
The focus of attention of energy related field.Compared with ni-Cd, Ni-MH battery, lithium ion battery is high, bigger than energy with voltage, recycles
Long lifespan, have a safety feature, self discharge is small, memory-less effect, can fast charging and discharging, many advantages, such as operating temperature range is wide,
It is widely used in every field.
One of critical material of lithium ion battery is negative material, and the Nomenclature Composition and Structure of Complexes of negative material is to lithium ion battery
Chemical property has decisive impact.Initial lithium battery is negative material using lithium metal, but lithium metal is filling
Li dendrite is easy tod produce when electric discharge and leads to the safety issues such as on fire or explosion.And the safeties such as on fire or explosion is caused to be asked
Topic.Then it develops Zinc-lithium alloy material and solves above-mentioned safety issue, but alloy material is easy hair in embedding and removing
Raw volume expansion, causes cycle performance to decline.Later by further studying and comparing, select graphited carbon as lithium
The commercialization negative material of ion battery.There is graphite layer structure, material to be easy preferred orientation, and graphite flake is usually put down when film
Row is accumulated in collector direction, and lithium ion is perpendicular to collector direction insertion graphite cathode.So this preferred orientation
Property can influence the diffusion and conduction of lithium ion to a certain extent.The compatibility of graphite and organic solvent is poor, and solvent easily occurs
It is embedded altogether, make graphite cathode structure collapses, loses embedding lithium activity.Compared with carbons negative material, silica-base material is because of its high power capacity
（3580 mAh/g of room temperature theoretical capacity）, low de- lithium current potential, the advantages such as low cost be considered as next-generation lithium ion cell electrode
Has the negative material of potentiality.However silicon, during charge and discharge, violent variation can occur for volume, the structure of material can be broken
It is bad, lead to the capacity attenuation of clang ion battery, electrode cycle is unstable, or even causes battery failure.
Thus the negative material exploitation of lithium ion battery is still current scientific research hot spot.The silicon-carbon composite wood of special tectonic
Material has excellent mechanical property and chemical property, causes researcher's extensive concern.Nano structural material is as lithium ion
It is interlaced between Guan Yuguan (or crystal grain and crystal grain) since caliber (or crystal grain) is nano-grade size when cell negative electrode material
Gap be also nanometer scale, make it have superior embedding lithium characteristic, lithium ion can not only be embedded into pipe between each caliber, manage
Core, and among the gap that can be embedded between pipe, a large amount of embedded space position is provided for lithium ion, to be conducive to improve
Charge/discharge capacity, cycle life and the current density of lithium ion battery.
Chinese invention patent application number 201210473878.8, which discloses, a kind of preparing carbon fiber-silicon nanowire negative electrode material
Method, first in the golden film of the golden one layer of 5-10 nanometer thickness of silicon chip surface vacuum evaporation；Argon/hydrogen mixed gas is passed through in tube furnace
It is placed in afterwards on the silicon chip after gold-plated film and one layer of silicon nanowires is prepared, carbon fiber-silicon nanowire is prepared followed by ball-milling method
Composite material, the silicon nanowires that step 1 is obtained and carbon nano-fiber by 1: 1 molar ratio, then together with polyurethane ball
It is placed in three-dimensional hybrid tank and mixes, obtain carbon fiber-silicon nanowire composite material.Chinese invention patent application number
CN201611222583.8 discloses a kind of carbon nano tube/graphene/silicon composite lithium ion battery negative material and preparation method thereof, adopts
The multilayered structure for replacing silicon/carbon nanotube composite layer with graphene layer, using graphene and the high-mechanical property of carbon nanotube with
High conductivity jointly carries out silica flour three-dimensional compound, raising cathode multiplying power and cycle performance.
Although the above method improves the chemical property of negative material to some extent, however nanofiber has
Larger draw ratio will lead to poor dispersion of the nanofiber in active material if it is not chopped effectively,
To influence its improvement to electrode material chemical property.In addition, preparation process is more complicated, it is excellent to prepare resulting materials performance
The equal unobvious of point.Traditional modified technique is mostly the high electrical-conductive nanometer material such as doped carbon nanometer pipe, graphene and then improves electricity
Chemical property, but the rare research being improved for negative pole structure.Therefore, by designing a kind of novel controllable negative pole structure,
Embedded to the lithium ion inside cathode and transfer ability raising has highly important practical significance.
Invention content
For traditional lithium cell cathode material during lithium ion deintercalation caused by the anisotropic growth of cathode
Internal resistance is excessive, the difficult problem of lithium ion insertion, and the present invention proposes a kind of by magnetic effect raising cathode of lithium battery electrode times
The method of rate performance makes negative material is vertical with electrode current collecting body to be combined, and the active point exposure of material is more abundant, reduces lithium
The diffusion path of ion, to improve the carrier mobility of material internal.
To solve the above problems, the present invention uses following technical scheme：
A method of cathode of lithium battery electrode high rate performance is improved by magnetic effect, is loaded using 1-dimention nano negative material
Ferrofluid and Ferrite Material form oriented structure under magnetic field, vertical with copper current collector to be combined, and form three-dimensional closely spaced array
The negative material of structure, specific preparation flow are as follows：
（1）1-dimention nano negative material, binder, dispersant and solvent are mixed, high-speed stirred is disperseed after 5-20 minutes
Uniform suspension, the wherein mass ratio of 1-dimention nano negative material, binder, dispersant and solvent are 1：2-5：0.1-
0.8：30-50；
（2）A small amount of Ferrite Material is added into suspension, is positioned over above neodymium magnet and is ultrasonically treated, obtain ferrite point
Dispersion liquid；
（3）A small amount of ferrofluid is added in the ferrite dispersion liquid, continues ultrasonic agitation processing 2 hours, until the magnetic
Fluid is adsorbed in completely on the 1-dimention nano negative material, and bottom suspension is passed through filtration and washing, obtains magnetic cathode slurry
Material；
（4）The magnetic negative electrode slurry is poured into bottom to be laid in the plastic mould of copper current collector, after grease sealing, is done
Dry processing, finally removes plastic mould, obtains the negative material with three-dimensional dense array structures.
Preferably, the 1-dimention nano negative material is one-dimensional nano line/nanotube of carbon, silicon, the nano wire/nanometer
Pipe draw ratio 50-200:1.
Preferably, the binder is the ethylene-vinyl acetate of polyvinyl alcohol and polyacrylic acid, solid content 40-55%
One kind in copolymer emulsion, LA132；The dispersant is neopelex, dodecyl sodium sulfate, polyethylene pyrrole
One kind in pyrrolidone, sodium taurocholate, polystyrene；The solvent is ethyl alcohol.
Preferably, the Ferrite Material is spinel type ferrite or magneto-plumbite type ferrite, the ferritic body
Product content is the 0.5-1.0% of the 1-dimention nano negative material.
Preferably, the magnetic-particle Fe that grain size is 5-12nm is included in the ferrofluid3O4、Fe2O3, in Ni, Co one
Kind or two or more combinations, the ferrofluid are 1 with the ferrite dispersion liquid volume ratio:30-55.
Preferably, step（1）High speed mixing speed is 600-1500rpm.
Preferably, step（3）It is middle to be rinsed using ethyl alcohol and/or deionized water.
Preferably, the seal thickness of the lubricating grease is 1-3mm.
Preferably, described be dried is that low pressure is dried, and environmental pressure control is 0.2-3 kPa, and drying temperature is
50-80℃。
Anisotropy in being grown due to negative material, the high warp architecture of existing porous negative material are normally resulted in
Carrier is reduced in the diffusion rate of electrode interior, and insertion of the lithium ion in negative material is also anisotropic, and
By making cathode crystal whisker materials and electrode current collecting body are vertical to be combined, so that the active point of material is exposed more abundant, reduce lithium from
The diffusion path of son, to improve the carrier mobility of material internal.In consideration of it, the present invention proposes that one kind passing through magnetic effect
The method for improving cathode of lithium battery electrode high rate performance, by auxiliary agents such as carbon, one-dimensional nano line/nanotube of silicon and binders in second
It is configured to suspension in alcoholic solution, after a small amount of Ferrite Material is added, is positioned over above neodymium magnet and carries out ultrasonic agitation processing,
Volume content is the 0.5-1% of nanometer anode material, is finally configured in a small amount of ferrofluid suspension addition system, and ultrasound is continued
2h, through the transparency of observation supernatant liquor, after magnetic fluid is adsorbed completely, by bottom suspension by being fallen after filtration and washing
Enter in plastic mould, being obtained using pole drying after grease sealing, after finally removing plastic mould has three-dimensional Phalanx
The negative electrode of array structure.It is combined by Van der Waals force with cathode whisker by Ferrite Material and ferrofluid, is made in magnetic field
Make negative material that there is the vertical of orientation to combine on copper current collector surface under, three-dimensional closely spaced array is formed, to form lithium
Ion transmission channel effectively improves deintercalation and transfer ability of the lithium ion in negative material, and then improves lithium ion battery
High rate performance is realized and achievees the purpose that improve negative material electrical property by controlling negative pole structure rather than ingredient.
A kind of method that cathode of lithium battery electrode high rate performance is improved by magnetic effect of the present invention, with prior art phase
Than the feature and excellent effect protruded is：
1, the present invention is using 1-dimention nano negative material load ferrofluid and Ferrite Material, by Ferrite Material and ferromagnetic
Fluid is combined with cathode whisker by Van der Waals force, makes negative material that there is the vertical of orientation to combine in copper under magnetic fields
Collection liquid surface forms three-dimensional closely spaced array and effectively improves lithium ion in negative material to form lithium ion transport channel
Deintercalation and transfer ability.Traditional lithium cell cathode material is overcome during lithium ion deintercalation due to the anisotropy of cathode
Internal resistance caused by growth is excessive, and the difficult problem of lithium ion insertion improves high rate performance.
2, cathode crystal whisker materials of the present invention are vertical with electrode current collecting body is combined, and so that the active point of material is exposed and is more filled
Point, the diffusion path of lithium ion is reduced, to improve the carrier mobility of material internal.
3, the method for the present invention achievees the purpose that improve negative material electrical property using control negative pole structure rather than control composition,
It is easy to implement that negative material performance is regulated and controled, facilitate environmental protection, new way is provided for negative material modification.
Specific implementation mode
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
（1）By draw ratio 120:1 carbon nanotube, polyvinyl alcohol, neopelex and ethyl alcohol mixes, and mixing speed is
1500rpm high-speed stirreds after five minutes, obtain finely dispersed suspension, carbon nanotube, polyvinyl alcohol, dodecyl benzene sulfonic acid
The mass ratio of sodium and ethyl alcohol is 1:2:0.8:30；
（2）Spinel type ferrite NiZnOFe is added into suspension2O3, ferritic volume content is carbon nanotube
0.8%, it is positioned over above neodymium magnet and carries out ultrasonic agitation processing, obtain ferrite dispersion liquid；
（3）The magnetic-particle Fe that grain size is 10nm will be included3O4、Fe2O3, Ni, Co ferrofluid ferrite dispersion is added
In liquid, ferrofluid is 1 with the ferrite dispersion liquid volume ratio:55, continue ultrasound 2 hours, until dispersion liquid supernatant liquor
Bleach, magnetic fluid are adsorbed in carbon nanotube completely, and bottom suspension is passed through ethyl alcohol washing and filtering, obtain magnetic cathode slurry
Material；
（4）The magnetic negative electrode slurry is poured into bottom to be laid in the plastic mould of copper current collector, after grease sealing, profit
The seal thickness of consistent lubricant is 3mm, and control environmental pressure is 0.2kPa, and drying temperature is 55 DEG C of progress low pressure drying process, finally
Plastic mould is removed, the negative electrode with three-dimensional dense array structures is obtained.
Using the negative electrode of three-dimensional dense array structures provided in this embodiment as battery cathode, nickle cobalt lithium manganate
（NCM）Pulping is anode pole piece coated in collector, and polyethylene porous film is diaphragm, 1M LiPF6 solution（Solvent is volume
Than 1:1 EC/EMC）For electrolyte, cylindrical battery is assembled into argon gas atmosphere glove box.It is tested in LAND battery charging and dischargings
Above to carry out charge-discharge test, after test is recycled 100 times with 1C rate charge-discharges, reversible capacity, performance test is shown in Table 1.
Embodiment 2
（1）By draw ratio 50:1 silicon nanowires, polyacrylic acid, polystyrene and ethyl alcohol mixing, mixing speed is 600rpm high
Speed stirring after five minutes, obtains finely dispersed suspension, silicon nanowires, polyacrylic acid, polystyrene and ethyl alcohol mass ratio
It is 1:2:0.8:30；
（2）Magneto-plumbite type ferrite Ba is added into suspension3Ni2Fe24O41, ferritic volume content is carbon nanotube
0.5%, it is positioned over above neodymium magnet and carries out ultrasonic agitation processing, obtain ferrite dispersion liquid；
（3）The magnetic-particle Fe that grain size is 5nm will be included3O4、Fe2O3Ferrofluid be added in the ferrite dispersion liquid, iron
Magnetic fluid is 1 with the ferrite dispersion liquid volume ratio:55, continue ultrasound 2 hours, until dispersion liquid supernatant liquor bleach,
Magnetic fluid is adsorbed in carbon nanotube completely, and bottom suspension is passed through ethyl alcohol washing and filtering, obtains magnetic negative electrode slurry；
（4）The magnetic negative electrode slurry is poured into bottom to be laid in the plastic mould of copper current collector, after grease sealing, profit
The seal thickness of consistent lubricant is 1.8mm, and control environmental pressure is 2kPa, and drying temperature is 75 DEG C of progress low pressure drying process, finally
Plastic mould is removed, the negative electrode with three-dimensional dense array structures is obtained.
Using the negative electrode of three-dimensional dense array structures provided in this embodiment as battery cathode, nickle cobalt lithium manganate
（NCM）Pulping is anode pole piece coated in collector, and polyethylene porous film is diaphragm, 1M LiPF6 solution（Solvent is volume
Than 1:1 EC/EMC）For electrolyte, cylindrical battery is assembled into argon gas atmosphere glove box.It is tested in LAND battery charging and dischargings
Above to carry out charge-discharge test, after test is recycled 100 times with 1C rate charge-discharges, reversible capacity, performance test is shown in Table 1.
Embodiment 3
（1）By draw ratio 200:1 silicon nanowires and the mixture of carbon nanotube, polyvinyl alcohol, sodium taurocholate and ethyl alcohol mixing, are stirred
Mix speed be 900rpm high-speed stirreds after five minutes, obtain finely dispersed suspension, the mixing of silicon nanowires and carbon nanotube
Object, polyvinyl alcohol, sodium taurocholate and ethyl alcohol mass ratio be 1:2:0.8:30；
（2）Magneto-plumbite type ferrite Ba is added into suspension3Co2Fe24O41, ferritic volume content is carbon nanotube
0.6%, it is positioned over above neodymium magnet and carries out ultrasonic agitation processing, obtain ferrite dispersion liquid；
（3）Ferrofluid comprising magnetic-particle Ni, Co that grain size is 8nm is added in the ferrite dispersion liquid, ferromagnetic stream
Body is 1 with the ferrite dispersion liquid volume ratio:55, continue ultrasound 2 hours, until dispersion liquid supernatant liquor bleach, magnetic current
Body is adsorbed in carbon nanotube completely, and bottom suspension is passed through ethyl alcohol washing and filtering, obtains magnetic negative electrode slurry；
（4）The magnetic negative electrode slurry is poured into bottom to be laid in the plastic mould of copper current collector, after grease sealing, profit
The seal thickness of consistent lubricant is 1.2mm, and control environmental pressure is 22kPa, and drying temperature is 65 DEG C of progress low pressure drying process, finally
Plastic mould is removed, the negative electrode with three-dimensional dense array structures is obtained.
Using the negative electrode of three-dimensional dense array structures provided in this embodiment as battery cathode, nickle cobalt lithium manganate
（NCM）Pulping is anode pole piece coated in collector, and polyethylene porous film is diaphragm, 1M LiPF6 solution（Solvent is volume
Than 1:1 EC/EMC）For electrolyte, cylindrical battery is assembled into argon gas atmosphere glove box.It is tested in LAND battery charging and dischargings
Above to carry out charge-discharge test, after test is recycled 100 times with 1C rate charge-discharges, reversible capacity, performance test is shown in Table 1.
Embodiment 4
（1）By draw ratio 180:1 carbon nanocoils, the ethylene-vinyl acetate copolymer lotion of solid content 40-55%, poly- second
Alkene pyrrolidone and ethyl alcohol mixing, mixing speed after five minutes, obtain finely dispersed suspension, carbon for 1200rpm high-speed stirreds
The mass ratio of nano wire, the ethylene-vinyl acetate copolymer lotion of solid content 40-55%, polyvinylpyrrolidone and ethyl alcohol
Example is 1:2:0.8:30；
（2）Spinel type ferrite NiZnOFe is added into suspension2O3, ferritic volume content is carbon nanotube
0.8%, it is positioned over above neodymium magnet and carries out ultrasonic agitation processing, obtain ferrite dispersion liquid；
（3）The magnetic-particle Fe that grain size is 7nm will be included3O4、Fe2O3, Co ferrofluid the ferrite dispersion liquid is added
In, ferrofluid is 1 with the ferrite dispersion liquid volume ratio:55, continue ultrasound 2 hours, until dispersion liquid supernatant liquor becomes
Transparent, magnetic fluid is adsorbed in carbon nanotube completely, and bottom suspension is passed through ethyl alcohol and deionized water washing and filtering, obtains magnetic
Property negative electrode slurry；
（4）The magnetic negative electrode slurry is poured into bottom to be laid in the plastic mould of copper current collector, after grease sealing, profit
The seal thickness of consistent lubricant is 1mm, and control environmental pressure is 1.8kPa, and drying temperature is 75 DEG C of progress low pressure drying process, finally
Plastic mould is removed, the negative electrode with three-dimensional dense array structures is obtained.
Using the negative electrode of three-dimensional dense array structures provided in this embodiment as battery cathode, nickle cobalt lithium manganate
（NCM）Pulping is anode pole piece coated in collector, and polyethylene porous film is diaphragm, 1M LiPF6 solution（Solvent is volume
Than 1:1 EC/EMC）For electrolyte, cylindrical battery is assembled into argon gas atmosphere glove box.It is tested in LAND battery charging and dischargings
Above to carry out charge-discharge test, after test is recycled 100 times with 1C rate charge-discharges, reversible capacity, performance test is shown in Table 1.
Embodiment 5
（1）By draw ratio 160:1 carbon nanotube and the mixture of silicon nanowires, LA132, dodecyl sodium sulfate and ethyl alcohol are mixed
Close, mixing speed be 800rpm high-speed stirreds after five minutes, obtain finely dispersed suspension, carbon nanotube and silicon nanowires
Mixture, LA132, dodecyl sodium sulfate and ethyl alcohol mass ratio be 1:2:0.8:30；
（2）Spinel type ferrite NiMnZnFe is added into suspension2O3, ferritic volume content is carbon nanotube
1.0%, it is positioned over above neodymium magnet and carries out ultrasonic agitation processing, obtain ferrite dispersion liquid；
（3）The magnetic-particle Fe that grain size is 12nm will be included3O4、Fe2O3, Ni ferrofluid the ferrite dispersion liquid is added
In, ferrofluid is 1 with the ferrite dispersion liquid volume ratio:55, continue ultrasound 2 hours, until dispersion liquid supernatant liquor becomes
Transparent, magnetic fluid is adsorbed in carbon nanotube completely, and bottom suspension is passed through deionized water washing and filtering, obtains magnetic cathode
Slurry；
（4）The magnetic negative electrode slurry is poured into bottom to be laid in the plastic mould of copper current collector, after grease sealing, profit
The seal thickness of consistent lubricant is 2mm, and control environmental pressure is 3kPa, and drying temperature is 80 DEG C of progress low pressure drying process, finally will
Plastic mould removes, and obtains the negative electrode with three-dimensional dense array structures.
Using the negative electrode of three-dimensional dense array structures provided in this embodiment as battery cathode, nickle cobalt lithium manganate
（NCM）Pulping is anode pole piece coated in collector, and polyethylene porous film is diaphragm, 1M LiPF6 solution（Solvent is volume
Than 1:1 EC/EMC）For electrolyte, cylindrical battery is assembled into argon gas atmosphere glove box.It is tested in LAND battery charging and dischargings
Above to carry out charge-discharge test, after test is recycled 100 times with 1C rate charge-discharges, reversible capacity, performance test is shown in Table 1.
Comparative example 1
（1）By draw ratio 120:1 carbon nanotube, polyvinyl alcohol, neopelex and ethyl alcohol mixes, and mixing speed is
1500rpm high-speed stirreds after five minutes, obtain finely dispersed suspension, carbon nanotube, polyvinyl alcohol, dodecyl benzene sulfonic acid
The mass ratio of sodium and ethyl alcohol is 1:2:0.8:30；
（2）By negative electrode slurry pour into bottom be laid with copper current collector plastic mould in, after grease sealing, lubricating grease it is close
Envelope thickness is 3mm, and control environmental pressure is 0.2kPa, and drying temperature is 55 DEG C of progress low pressure drying process, finally by the modern designs of plastics
Tool removal, obtains negative electrode.
The electrode obtained with comparative example 1 makees cathode, nickle cobalt lithium manganate（NCM）Pulping is anode pole piece coated in collector,
Polyethylene porous film is diaphragm, 1M LiPF6 solution（Solvent is volume ratio 1:1 EC/EMC）For electrolyte, in argon gas atmosphere
Cylindrical battery is assembled into glove box.Charge-discharge test is carried out more than the test of LAND battery charging and dischargings, test is filled with 1C multiplying powers
After discharge cycles 100 times, reversible capacity, performance test is shown in Table 1.
Comparative example 2
Using the carbon nanotube that 30% is added into artificial graphite collector, nickle cobalt lithium manganate are coated in as negative material pulping
（NCM）Pulping is anode pole piece coated in collector, and polyethylene porous film is diaphragm, 1M LiPF6 solution（Solvent is volume
Than 1:1 EC/EMC）For electrolyte, cylindrical battery is assembled into argon gas atmosphere glove box.It is tested in LAND battery charging and dischargings
Above to carry out charge-discharge test, after test is recycled 100 times with 1C rate charge-discharges, reversible capacity, performance test is shown in Table 1.
Embodiment 1-5 comparative example 1-2 using same positive plate, diaphragm, electrolyte equipment battery tested, performance
Such as table 1.
Table 1:
| Sample | Reversible capacity mAhg for the first time-1 | 1C recycles 100 capacity mAhg-1 |
| Embodiment 1 | 467.3 | 291.4 |
| Embodiment 2 | 456.4 | 275.1 |
| Embodiment 3 | 469.3 | 2912 |
| Embodiment 4 | 459.5 | 277.8 |
| Embodiment 5 | 403.4 | 288.4 |
| Comparative example 1 | 326.1 | 140.6 |
| Comparative example 2 | 215.9 | 84.9 |
It follows that loading ferrofluid and Ferrite Material using 1-dimention nano negative material, orientation knot is formed under magnetic field
Structure, it is vertical with copper current collector to be combined, the negative electrode of three-dimensional dense array structures is formed, compared with electrographite electrode and doped graphite
Electrode material has good high rate performance, specific capacity and conservation rate, it is shown that excellent chemical property.
Claims (9)
1. a kind of method improving cathode of lithium battery electrode high rate performance by magnetic effect, which is characterized in that use a wiener
Rice negative material load ferrofluid and Ferrite Material, form oriented structure, vertical with copper current collector to be combined, shape under magnetic field
At the negative material of three-dimensional dense array structures, specific preparation flow is as follows：
（1）1-dimention nano negative material, binder, dispersant and solvent are mixed, high-speed stirred is disperseed after 5-20 minutes
Uniform suspension, the wherein mass ratio of 1-dimention nano negative material, binder, dispersant and solvent are 1：2-5：0.1-
0.8：30-50；
（2）A small amount of Ferrite Material is added into suspension, is positioned over above neodymium magnet and is ultrasonically treated, obtain ferrite point
Dispersion liquid；
（3）A small amount of ferrofluid is added in the ferrite dispersion liquid, continues ultrasonic agitation processing 2 hours, until the magnetic
Fluid is adsorbed in completely on the 1-dimention nano negative material, and bottom suspension is passed through filtration and washing, obtains magnetic cathode slurry
Material；
（4）The magnetic negative electrode slurry is poured into bottom to be laid in the plastic mould of copper current collector, after grease sealing, is done
Dry processing, finally removes plastic mould, obtains the negative electrode with three-dimensional dense array structures.
2. a kind of method that cathode of lithium battery electrode high rate performance is improved by magnetic effect according to claim 1,
It is characterized in that, the 1-dimention nano negative material is one-dimensional nano line/nanotube of carbon, silicon, the nanowires/nanotubes major diameter
Compare 50-200:1.
3. a kind of method that cathode of lithium battery electrode high rate performance is improved by magnetic effect according to claim 1,
It is characterized in that, the binder is the ethylene-vinyl acetate copolymer of polyvinyl alcohol and polyacrylic acid, solid content 40-55%
One kind in lotion, LA132；The dispersant is neopelex, dodecyl sodium sulfate, polyvinylpyrrolidine
One kind in ketone, sodium taurocholate, polystyrene；The solvent is ethyl alcohol.
4. a kind of method that cathode of lithium battery electrode high rate performance is improved by magnetic effect according to claim 1,
It is characterized in that, the Ferrite Material is spinel type ferrite or magneto-plumbite type ferrite, the ferritic volume content
For the 0.5-1.0% of the 1-dimention nano negative material.
5. a kind of method that cathode of lithium battery electrode high rate performance is improved by magnetic effect according to claim 1,
It is characterized in that, the magnetic-particle Fe that grain size is 5-12nm is included in the ferrofluid3O4、Fe2O3, one kind or two in Ni, Co
Kind or more combination, the ferrofluid and the ferrite dispersion liquid volume ratio are 1:30-55.
6. a kind of method that cathode of lithium battery electrode high rate performance is improved by magnetic effect according to claim 1,
It is characterized in that, step（1）High speed mixing speed is 600-1500rpm.
7. a kind of method that cathode of lithium battery electrode high rate performance is improved by magnetic effect according to claim 1,
It is characterized in that, step（3）It is middle to be rinsed using ethyl alcohol and/or deionized water.
8. a kind of method that cathode of lithium battery electrode high rate performance is improved by magnetic effect according to claim 1,
It is characterized in that, the seal thickness of the lubricating grease is 1-3mm.
9. a kind of method that cathode of lithium battery electrode high rate performance is improved by magnetic effect according to claim 1,
It is characterized in that, described be dried is that low pressure is dried, and environmental pressure control is 0.2-3 kPa, drying temperature 50-80
℃。
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| CN201810224877.7A Withdrawn CN108417839A (en) | 2018-03-19 | 2018-03-19 | A method of cathode of lithium battery electrode high rate performance is improved by magnetic effect |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109192930A (en) * | 2018-09-10 | 2019-01-11 | 深圳技术大学（筹） | The preparation method of graphene complex electrode |
| CN110880582A (en) * | 2019-11-26 | 2020-03-13 | 陕西科技大学 | Ferroferric oxide three-dimensional network electrode based on magnetic adsorption and preparation method thereof |
| CN111653773A (en) * | 2019-03-19 | 2020-09-11 | 重庆金康新能源汽车有限公司 | Isotropic self-assembly of graphite particles for lithium ion anodes |
| CN113793939A (en) * | 2021-09-24 | 2021-12-14 | 鹤壁市诺信电子有限公司 | Ultralow-temperature high-rate lithium ion battery and preparation method thereof |
| CN114203956A (en) * | 2021-12-10 | 2022-03-18 | 湖南宸宇富基新能源科技有限公司 | Sandwich-structure negative pole piece, precursor pole piece, preparation and application thereof |
| CN114744160A (en) * | 2022-06-13 | 2022-07-12 | 新乡市中天新能源科技股份有限公司 | Preparation method of lithium ion battery positive plate |
| CN114759164A (en) * | 2022-06-13 | 2022-07-15 | 新乡市中天新能源科技股份有限公司 | Preparation method and application of lithium battery negative plate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109192930A (en) * | 2018-09-10 | 2019-01-11 | 深圳技术大学（筹） | The preparation method of graphene complex electrode |
| CN111653773A (en) * | 2019-03-19 | 2020-09-11 | 重庆金康新能源汽车有限公司 | Isotropic self-assembly of graphite particles for lithium ion anodes |
| CN110880582A (en) * | 2019-11-26 | 2020-03-13 | 陕西科技大学 | Ferroferric oxide three-dimensional network electrode based on magnetic adsorption and preparation method thereof |
| CN110880582B (en) * | 2019-11-26 | 2020-10-23 | 陕西科技大学 | Ferroferric oxide three-dimensional network electrode based on magnetic adsorption and preparation method thereof |
| CN113793939A (en) * | 2021-09-24 | 2021-12-14 | 鹤壁市诺信电子有限公司 | Ultralow-temperature high-rate lithium ion battery and preparation method thereof |
| CN114203956A (en) * | 2021-12-10 | 2022-03-18 | 湖南宸宇富基新能源科技有限公司 | Sandwich-structure negative pole piece, precursor pole piece, preparation and application thereof |
| CN114744160A (en) * | 2022-06-13 | 2022-07-12 | 新乡市中天新能源科技股份有限公司 | Preparation method of lithium ion battery positive plate |
| CN114759164A (en) * | 2022-06-13 | 2022-07-15 | 新乡市中天新能源科技股份有限公司 | Preparation method and application of lithium battery negative plate |
| CN114759164B (en) * | 2022-06-13 | 2022-09-02 | 新乡市中天新能源科技股份有限公司 | Preparation method and application of lithium battery negative plate |
| CN115224242A (en) * | 2022-06-13 | 2022-10-21 | 河南师范大学 | Preparation method and application of lithium battery positive plate |
| CN115224242B (en) * | 2022-06-13 | 2024-03-05 | 河南师范大学 | Preparation method and application of lithium battery positive plate |
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