CN105655542B - Negative electrode of lithium ion battery and preparation method thereof - Google Patents
Negative electrode of lithium ion battery and preparation method thereof Download PDFInfo
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- CN105655542B CN105655542B CN201410649911.7A CN201410649911A CN105655542B CN 105655542 B CN105655542 B CN 105655542B CN 201410649911 A CN201410649911 A CN 201410649911A CN 105655542 B CN105655542 B CN 105655542B
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Abstract
The present invention provides a kind of negative electrode of lithium ion battery, including the cathode coating being made of carbon material, binder and conductive agent；The carbon material includes：Carbon core is coated on the first material with carbon on carbon core surface, is coated on second carbon material on the first material with carbon surface；The carbon core is graphite or mesocarbon microspheres；The first material with carbon is hard carbon, graphene or carbon nanotube, and second carbon material is amorphous carbon or graphite；The porosity of the cathode coating be 20%~40%, the cathode coating with a thickness of 40 μm~90 μm.The application adds the carbon material of special construction by the cathode in lithium ion battery, and adjusts electrode characteristic parameter porosity and thickness, makes battery energy density with higher and power density.Present invention also provides the preparation methods of the negative electrode of lithium ion battery.
Description
Technical field
The present invention relates to technical field of lithium ion more particularly to a kind of negative electrode of lithium ion battery and preparation method thereof.
Background technique
Lithium power technology has become the important component of modern society, is all using lithium from smart phone to electric vehicle etc.
The portable energy source that electricity provides.Lithium ion battery is commercialized by Sony realization in 1991 earliest, is continued to develop later, technically
Significant progress is achieved, but the energy density of battery, power, service life and safety etc. still have defect, no
The demand of social development can be fully met, therefore becomes research staff's problem in the urgent need to address.It is known that battery performance
It is heavily dependent on material technology, the raising of battery performance is usually to realize by improving cathode and positive electrode.
The commercialized lithium ion battery overwhelming majority is using a certain or several carbon materials as cathode now.1973
Carbon material is suggested for the first time can be used as intercalation electrode, then be widely used.Using different carbon materials material precursors, system
Preparation Method and heat treatment/chemistry method can obtain having different crystallinity, chemical component and microstructure
Carbon material.
The carbon material of lithium ion intercalation mainly has graphite, coke, mesophase pitch, carbon fiber, pyrolytic carbon, carbon 60 and receives
Rice carbon pipe etc..Amorphous carbon (such as soft carbon and hard carbon) is relative to crystalloid carbon material (such as artificial graphite and natural graphite)
For, advantage is had more in terms of service life, power and security performance, but graphite material is then in energy density and advantage in price
Obviously.Based on this, in order to improve service life, power and the security performance of battery, soft carbon or hard carbon are often blended into stone by people
It is made into cathode in ink material, but the step of increasing blending while also increasing production cost.Therefore, how low cost is manufactured
High performance cathode is always a major challenge of lithium electrician's industry.
Summary of the invention
Present invention solves the technical problem that being to provide a kind of negative electrode of lithium ion battery, lithium ion battery provided by the present application
Cathode makes lithium ion battery energy density with higher, power density and cost is relatively low.
In view of this, this application provides a kind of negative electrode of lithium ion battery, including by carbon material, binder and conductive agent group
At cathode coating；
The carbon material includes：Carbon core is coated on the first material with carbon on carbon core surface, is coated on first carbon materials
Expect second carbon material on surface；The carbon core is graphite or mesocarbon microspheres；The first material with carbon be hard carbon, graphene or
Carbon nanotube, second carbon material are amorphous carbon or graphite；
The porosity of the cathode coating be 20%~40%, the cathode coating with a thickness of 40 μm~90 μm.
Preferably, the content of the carbon core is 59wt%~99.8wt%, and the content of the first material with carbon is 0.1wt%
~40wt%, second carbon material are 0.1wt%~10wt%.
Preferably, the content of the binder be the carbon material, binder and conductive agent total amount 0.5wt%~
10wt%；The content of the conductive agent is 0.5wt%~10wt% of the carbon material, binder and conductive agent total amount.
Preferably, the porosity of the cathode coating be 25%~35%, the cathode coating with a thickness of 50 μm~75 μ
m。
Present invention also provides a kind of preparation methods of negative electrode of lithium ion battery, include the following steps：
Carbon material, conductive agent are mixed with binder, obtain slurry；
The slurry is applied on a current collector, obtains negative electrode of lithium ion battery；
The carbon material includes：Carbon core is coated on the first material with carbon on carbon core surface, is coated on first material with carbon surface
Second carbon material；
The carbon nuclear material is graphite or mesocarbon microspheres, and the first material with carbon is graphene, carbon nanotube or heat
Solution generates the carbon materials material precursor of hard carbon, and second carbon material is the carbon material forerunner that graphite or pyrolysis generate amorphous carbon
Body；
The porosity of the negative electrode of lithium ion battery be 20%~40%, the negative electrode of lithium ion battery with a thickness of 40 μm
~90 μm.
Preferably, the preparation method of the carbon material includes the following steps：
Carbon nuclear material, first material with carbon are mixed in a solvent with the second carbon material, obtain mixed liquor；
The mixed liquor is evaporated, it is subsequently heat-treated, obtain carbon material；
The carbon nuclear material is graphite or mesocarbon microspheres, and the first material with carbon is graphene, carbon nanotube or heat
Solution generates the carbon materials material precursor of hard carbon, and second carbon material is the carbon material forerunner that graphite or pyrolysis generate amorphous carbon
Body.
Preferably, the partial size of the carbon nuclear material is 10 μm~30 μm, and the partial size of the first material with carbon is 0.1 μm~10
μm, the partial size of second carbon material is 0.1~10 μm.
Preferably, the preparation method of the carbon material, includes the following steps：
Carbon nuclear material, first material with carbon are mixed with solvent, obtain the first mixed liquor, the second carbon material is mixed with solvent
It closes, obtains the second mixed liquor；
It will be heat-treated after first mixed liquor evaporation, obtain the first cladding carbon material；
The first cladding carbon material is mixed with second mixed liquor, is heat-treated after evaporation, obtains carbon material；
The carbon nuclear material is graphite or mesocarbon microspheres, and the first material with carbon is graphene, carbon nanotube or heat
Solution generates the carbon materials material precursor of hard carbon, and second carbon material is the carbon material forerunner that graphite or pyrolysis generate amorphous carbon
Body.
Preferably, it is petroleum base resin that the pyrolysis, which generates the carbon materials material precursor of hard carbon, and the pyrolysis generates amorphous
The carbon materials material precursor of carbon is coal tar asphalt.
Preferably, the process for obtaining slurry is specially：
It is mixed again with binder after carbon material is mixed with conductive agent, obtains slurry.
This application provides a kind of negative electrode of lithium ion battery comprising is made of carbon material, conductive agent and binder negative
Pole coating, wherein the carbon material includes carbon core, first material with carbon and the second carbon material, the first material with carbon is coated on carbon core
Surface, second carbon material are coated on the first material with carbon surface, wherein the carbon core be graphite or mesocarbon microspheres,
The first material with carbon is hard carbon, graphene or carbon nanotube, and second carbon material is amorphous carbon or graphite；The cathode
The porosity of coating is 20%~40%, with a thickness of 40 μm~90 μm.
The coating of negative electrode of lithium ion battery provided by the present application is made of carbon material, binder and conductive agent, wherein carbon materials
The carbon core of material is to provide the component of energy density, and first material with carbon is to improve cell power density, the component in service life and safety,
And the second carbon material have lower specific surface area, be easy to electrolyte interface formed solid phase electrode interface, with protect carbon core with
First material with carbon, therefore carbon material provided by the present application makes carbon material by setting carbon core, first material with carbon and the second carbon material
Cathode energy density with higher and power density applied to lithium ion battery；The carbon material that the application uses simultaneously
To be obtained by simple approach, then cost is relatively low for the carbon material of the application；The application, which also passes through, adjusts negative electrode of lithium ion battery
The porosity and thickness of electrode characteristic parameter cathode coating, further make lithium ion battery energy density with higher and power
Density.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still
It should be appreciated that these descriptions are only further explanation the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
The embodiment of the invention discloses a kind of negative electrode of lithium ion battery, which is characterized in that including by carbon material, binder with
The cathode coating of conductive agent composition；
The carbon material includes：Carbon core is coated on the first material with carbon on carbon core surface, is coated on first carbon materials
Expect second carbon material on surface；The carbon core is graphite or mesocarbon microspheres；The first material with carbon be hard carbon, graphene or
Carbon nanotube, second carbon material are amorphous carbon or graphite；
The porosity of the cathode coating be 20%~40%, the cathode coating with a thickness of 40 μm~90 μm.
This application provides a kind of negative electrode of lithium ion battery, the cathode of the lithium ion battery includes collector and collector
The cathode coating on surface.The coating of herein described negative electrode of lithium ion battery is made of carbon material, binder and conductive agent.This
Application adjusts the electrode characteristic parameter of negative electrode material by introducing the carbon material of special construction in cathode：Cathode coating
Thickness and porosity make the lithium ion battery of the application energy density with higher and power density.
Carbon material in the application cathode coating has double-coating structure, and wherein carbon core is the group for contributing energy density
Point, it is coated by first material with carbon, first material with carbon is the material with high power, long-life and high security, is entire material
Improve power, the component in service life and safety in material, first material with carbon is coated by the second carbon material, and the second carbon material has low
Specific surface area easily forms Solid phase electrolysis interface with electrolyte interface, as a result, the carbon core and the first carbon of the carbon material setting of the application
Material makes carbon electrode material energy density with higher, power density, service life and safety, and is coated on the second carbon material
It can guarantee that carbon electrode material and electrolyte interface form solid phase electrode interface, therefore the carbon material of the application is as lithium-ion electric
The negative electrode material in pond makes lithium ion battery energy density with higher, power density, safety and service life.
Herein described carbon core is graphite or mesocarbon microspheres, and the graphite can be natural graphite, is also possible to people
Graphite is made, the carbon core is to provide the component of energy density in carbon electrode material.The content of the carbon core be 59wt%~
99.8wt%, more preferably 70wt%~90wt%.If the content of carbon core is too low, the energy density of carbon electrode material can be made too
It is low, if the too high levels of carbon core, it will affect the promotion of carbon material power density.For coming for graphite or carbonaceous mesophase spherules
Source, the application are not particularly limited.
According to the application, the first material with carbon for being coated on carbon core surface is hard carbon, graphene or carbon nanotube, described second
Carbon material is characterized in high efficiency, long-life and high security, is improvement power, service life in entire carbon electrode material
With the component of safety.The hard carbon refers to the carbon for being difficult to be graphitized, and is the thermal decomposition product of high molecular polymer, described hard
Carbon can be resin carbon, carbon black etc..The hard carbon material all has very high reversible specific capacity.The graphene is that one kind has carbon
The material of the individual layer laminated structure of atomic building.The content of the first material with carbon is 0.1wt%~40wt%, preferably
The content of 5wt%~35wt%, the first material with carbon are too low, then will affect the promotion of power density, and too high levels can then be led
The decline of enable metric density.The application is not particularly limited the source of the hard carbon, graphene or carbon nanotube.The application
The middle material as carbon core can not be exchanged with the first material with carbon for being coated on carbon core surface, this is because having high-power the
One carbon material is conducive to the quick charge electric discharge of lithium ion as clad.
It is coated on second carbon material on first material with carbon surface in the application as external coating, itself and electrolyte can be made
Interface forms solid phase electrode interface.Second carbon material is amorphous carbon or graphite.The content of second carbon material is
0.1wt%~10wt%, preferably 3wt%~8wt%.The content of second carbon material is too low, then cannot be with electrolyte shape
At interface is effectively protected, too high levels then can make specific surface area cause energy density to decline greatly very much.
The application, which also passes through adjusting electrode characteristic, makes lithium ion battery energy density with higher and power density, wherein
Electrode characteristic includes the porosity and thickness of cathode coating.The porosity of herein described cathode coating is 20%~40%, thick
Degree is 40 μm~90 μm.The porosity, which is greater than 40%, increases the power of electrode, but energy density can be decreased obviously, described
Porosity is preferably 25%~35%.The thickness of the cathode coating is preferably 50 μm~75 μm, and more preferably 55 μm~70 μm,
The thickness of the cathode coating is greater than 90 μm, then the energy density of electrode increases but power density is decreased obviously, and less than 40 μ
The power density of m electrode increases but energy density is decreased obviously.
According to the present invention, the type and additive amount of the conductive agent and binder, also can be to electricity as electrode characteristic parameter
The performance in pond impacts.The conductive agent is preferably one or both of carbon black and graphite, and the binder is preferably poly-
Vinylidene (PVDF) and carboxylic styrene butadiene latex (Letax).The content of the conductive agent is the carbon material, conductive agent and bonding
0.5wt%~10wt% of agent total amount, preferably 2wt%~8wt%, if content increase will lead to conductivity and increase still energy
Density is decreased obviously, if content reduces the energy density increase that can make electrode but conductivity is decreased obviously.The binder
Content is 0.5wt%~10wt%, the preferably 2wt%~8wt% of the carbon material, conductive agent and binder total amount, bonding
The content of agent is excessive or the too small energy density that can make electrode declines.
Negative electrode of lithium ion battery provided by the present application adjusts the porosity of electrode by selecting the carbon material of special construction
With thickness, make lithium ion battery power density with higher and energy density.
Present invention also provides the preparation methods of negative electrode of lithium ion battery, include the following steps：
Carbon material, conductive agent are mixed with binder, obtain slurry；
The slurry is applied on a current collector, obtains negative electrode of lithium ion battery；
The carbon material includes：Carbon core is coated on the first material with carbon on carbon core surface, is coated on first material with carbon surface
Second carbon material；
The carbon nuclear material is graphite or mesocarbon microspheres, and the first material with carbon is graphene, carbon nanotube or heat
Solution generates the carbon materials material precursor of hard carbon, and second carbon material is the carbon material forerunner that graphite or pyrolysis generate amorphous carbon
Body；
The porosity of the coating of the negative electrode of lithium ion battery is 20%~40%, the coating of the negative electrode of lithium ion battery
With a thickness of 40 μm~90 μm.
The present invention provides the preparation methods of negative electrode of lithium ion battery, are prepared for carbon material, conductive agent and bonding first
The slurry of agent, then slurry is coated on a current collector to get negative electrode of lithium ion battery is arrived.
The preparation method of herein described carbon material is preferably prepared according to following processes：
Carbon nuclear material, first material with carbon are mixed in a solvent with the second carbon material, obtain mixed liquor；
The mixed liquor is evaporated, it is subsequently heat-treated, obtain carbon electrode material；
The carbon nuclear material is graphite or mesocarbon microspheres, and the first material with carbon is graphene, carbon nanotube or heat
Solution generates the carbon materials material precursor of hard carbon, and second carbon material is the carbon material forerunner that graphite or pyrolysis generate amorphous carbon
Body.
During preparing carbon material, the carbon nuclear material of the application, first material with carbon with the second carbon material by mixing,
The process of evaporation and heat treatment has obtained the structure of the double-deck carbon material cladding.
The application during preparing carbon material, first by carbon nuclear material, first material with carbon with the second carbon material molten
It is mixed in agent, has obtained mixed liquor.During the mixing, the solvent is preferably paraxylene, is conducive to above-mentioned
The dissolution of three kinds of carbon materials, while being also easy to separate in subsequent processes.The carbon nuclear material is graphite or intermediate-phase carbon
Microballoon, partial size are preferably 10~30 μm, and the carbon nuclear material within the scope of this makes the energy density highest of carbon material, the carbon core material
The partial size of material is more preferably 15~20 μm.The first material with carbon is the carbon materials that graphene, carbon nanotube or pyrolysis generate hard carbon
Material precursor, preferably petroleum base resin, epoxy resin, natural plant fibre, lignin or carbon liquefied residue, more preferably stone
Oil-based resin；The partial size of the first material with carbon is preferably 0.1~10 μm, and the first material with carbon within the scope of this makes carbon electrode material
Power density highest, the partial size of the first material with carbon is more preferably 2~7 μm.Second carbon material is graphene, carbon is received
Mitron or pyrolysis generate the carbon materials material precursor of amorphous carbon, and preferably coal tar asphalt, the partial size of second carbon material is excellent
It is selected as 0.1~10 μm, the second carbon material within the scope of this keeps the outer layer formed after cladding most uniform, the solid phase formed with electrolyte
Interface is most stable, and the partial size of second carbon material is more preferably 3~8 μm.
According to the present invention, after being prepared for mixed liquor, then the mixed liquor is evaporated, is then heat-treated,
To obtain carbon material.In order to make the organic solvent in mixed liquor be easy to steam, the application preferably uses Rotary Evaporators to institute
Mixed liquor is stated to be evaporated.The Rotary Evaporators are to make container under most suitable speed, with constant speed rotary by electronic control
Increase disengagement area, and so that container for evaporation is in negative pressure state by vacuum pump, container for evaporation is in rotation while being placed in oil bath pan
Middle heated at constant temperature, solution carries out heating diffusive evaporation in rotary flask in bottle.The process that the application is evaporated in mixed liquor
In first material with carbon made and the second carbon material is constantly precipitated and is coated on the surface of carbon nuclear material due to the evaporation of solution.The evaporation
Temperature be preferably 100 DEG C~150 DEG C, the evaporating temperature is too low, causes the operating time too long, and in the mixed liquor
Solution cannot volatilize completely, influence the covered effect of carbon electrode material；Evaporating temperature is excessively high, then it is uneven to will lead to cladding.?
It after the mixed liquor is evaporated, is then heat-treated, makes the material after pervaporation by dehydration, dehydrogenation polymerization and carbon
Change, ultimately forms the effectively double-deck carbon material clad.In order to avoid carbon electrode material introduces other impurities during the preparation process
And covered effect is influenced, the application preferably carries out under nitrogen atmosphere protection.In order to guarantee the covered effect of the double-deck carbon material, institute
The heating rate for stating heat treatment is preferably 2 DEG C/min~6 DEG C/min, and the temperature of the heat treatment is preferably 800 DEG C~1200 DEG C,
The time of the heat treatment is preferably 1.5h~3h.
The preparation method of herein described carbon material can also carry out in the following manner：
Carbon nuclear material, first material with carbon are mixed with solvent, obtain the first mixed liquor, the second carbon material is mixed with solvent
It closes, obtains the second mixed liquor；
It will be heat-treated after first mixed liquor evaporation, obtain the first cladding carbon material；
The first cladding carbon material is mixed with second mixed liquor, is heat-treated after evaporation, obtains carbon material；
The carbon nuclear material is graphite or mesocarbon microspheres, and the first material with carbon is graphene, carbon nanotube or heat
Solution generates the carbon materials material precursor of hard carbon, and second carbon material is the carbon material forerunner that graphite or pyrolysis generate amorphous carbon
Body.
The above-mentioned process for preparing carbon material is first to coat first material with carbon on the surface of carbon nuclear material, then by the first carbon coated
Material is mixed with the solution of the second carbon material, after pervaporation and heat treatment, is finally coated in the first cladding carbon material surface
Second carbon material, has obtained carbon material.By the above process it is found that the process that the above process prepares carbon material is first to be prepared for first
Then the material of carbon material carbon coated core is prepared for the double-coating material of cladding second layer carbon material again.
It is above-mentioned to prepare the selection of related parameter and preferred embodiment and the first preparation carbon materials during carbon material
The method of material is identical, is no longer repeated herein.
According to the present invention, after the completion of the carbon material preparation, then the carbon material, conductive agent is mixed with binder, obtained
To slurry.The carbon material and conductive agent are solid powders, are easier to realize uniform mixing, and binder is as full-bodied
The uniform mixing of liquid and solid powder, which is compared, to be difficult to realize, and therefore, the preparation process of the slurry is preferably：By carbon material
It is mixed again with binder after being mixed with conductive agent, obtains slurry.
After obtaining slurry, the application then applies the slurry on a current collector, obtains lithium-ion electric after dry
Pond cathode.Wherein the collector is well known to those skilled in the art, and the application does not limit particularly, and the application is preferable
For copper foil.During coating, the application makes the porosity 20% of cathode coating by adjusting the roller spacing of roll squeezer
~40%, the roller spacing is 30 μm~70 μm.
This application provides a kind of negative electrode of lithium ion battery comprising is made of carbon material, conductive agent and binder negative
Pole coating, wherein the carbon material includes carbon core, first material with carbon and the second carbon material, the first material with carbon is coated on carbon core
Surface, second carbon material are coated on the first material with carbon surface, wherein the carbon core be graphite or mesocarbon microspheres,
The first material with carbon is hard carbon, graphene or carbon nanotube, and second carbon material is amorphous carbon or graphite；The cathode
The porosity of coating is 20%~40%, with a thickness of 40 μm~90 μm.
The coating of negative electrode of lithium ion battery provided by the present application is made of carbon material, binder and conductive agent, wherein carbon materials
The carbon core of material is to provide the component of energy density, and first material with carbon is to improve cell power density, the component in service life and safety,
And the second carbon material have lower specific surface area, be easy to electrolyte interface formed solid phase electrode interface, with protect carbon core with
First material with carbon, therefore carbon material provided by the present application makes carbon material by setting carbon core, first material with carbon and the second carbon material
Cathode energy density with higher and power density applied to lithium ion battery；The carbon material that the application uses simultaneously
To be obtained by simple approach, then cost is relatively low for the carbon material of the application；The application also passes through the electrode for adjusting lithium ion battery
The porosity and thickness of characterisitic parameter cathode coating further make lithium ion battery energy density with higher and power close
Degree.
For a further understanding of the present invention, carbon electrode material provided by the invention is carried out specifically below with reference to embodiment
Bright, protection scope of the present invention is not limited by the following examples.
Embodiment 1
Use 17 microns of average grain diameter of spherical natural graphite as the core of negative electrode material, that is, carbon material A, using flat
The petroleum base resin of equal 7 microns of partial size uses 3 microns of coal tar of average grain diameter as internal layer covering material, that is, carbon material B
Oil asphalt is as external sheath material.
Weigh 800 grams of spherical natural graphites, 200 grams of coal tar asphaltes, 200 grams of petroleum base resins respectively first.Spherical day
Right graphite and solvent paraxylene are mixed to form the suspension that concentration is 0.5M；Petroleum base resin and coal tar asphalt are separately added into
The solution that concentration is 1.0M is formed into solvent paraxylene.Three kinds of solution are stirred at room temperature it is uniformly mixed, using rotation
Evaporimeter makes solvent gradually volatilize in 125 DEG C of dryings, is finally heat-treated in tube furnace under nitrogen atmosphere protection, nitrogen
Flow 30ml/min, 5 DEG C/min of heating rate, stop 2h, have obtained the advanced carbon materials of double-coating by 1000 DEG C of final temperature
Material.
Prepared carbon material 900g is mixed into 20min in Dry powder mixing apparatus with 50g carbon black, is added
The PVDF/NMP solution of 500g10%, mixes 30min in planetary-type mixer, obtained slurry coating on copper foil, dry,
And negative electrode of lithium ion battery is obtained to roller using roll squeezer；Roller spacing to roll squeezer during roller is 50 μm, lithium-ion electric
The porosity of pond cathode coating is 31%, with a thickness of 79 μm.Using cathode manufactured in the present embodiment as the cathode of half-cell, half electricity
The test result of pond performance is as shown in table 1.
Embodiment 2
Use 17 microns of average grain diameter of spherical natural graphite as the core of negative electrode material, that is, carbon material A, using flat
The lignin of equal 7 microns of partial size is dripped as internal layer covering material, that is, carbon material B using 3 microns of average grain diameter of coal tar
Blueness is used as external sheath material.
Weigh 800 grams of spherical natural graphites, 200 grams of coal tar asphaltes, 200 grams of lignin respectively first.Spherical natural stone
Ink and solvent paraxylene are mixed to form the suspension that concentration is 0.5M.Lignin and coal tar asphalt are added separately to solvent pair
The solution that concentration is 1.0M is formed in dimethylbenzene.First lignin liquor and graphite suspension are stirred at room temperature it is uniformly mixed,
So that solvent is gradually volatilized in 125 DEG C of dryings using Rotary Evaporators, finally carries out heat in tube furnace under nitrogen atmosphere protection
Processing, nitrogen flow 30ml/min, 5 DEG C/min of heating rate, stop 2h by 1000 DEG C of final temperature, have obtained one layer of cladding
Material；Then this layer of covering material is added to be uniformly mixed in cold primer-oil and forms suspension, using Rotary Evaporators
So that solvent is gradually volatilized in 125 DEG C of dryings, is finally heat-treated in tube furnace under nitrogen atmosphere protection, nitrogen flow
30ml/min, 5 DEG C/min of heating rate, stop 2h, have obtained the advanced carbon material of double-coating by 1000 DEG C of final temperature.
Prepared carbon material 895g is mixed into 20min in Dry powder mixing apparatus with 52.5g carbon black, is added
The PVDF/NMP solution of 525g10%, mixes 30min in planetary-type mixer, obtained slurry coating on copper foil, dry,
And negative electrode of lithium ion battery is obtained to roller using roll squeezer；Roller spacing to roll squeezer during roller is 70 μm, lithium-ion electric
The porosity of pond cathode coating is 40%, with a thickness of 90 μm.Using cathode manufactured in the present embodiment as the cathode of half-cell, half electricity
The test result of pond performance is as shown in table 1.
Embodiment 3
Use 17 microns of average grain diameter of spherical natural graphite as the core of negative electrode material, that is, carbon material A, using flat
The petroleum base resin of equal 7 microns of partial size uses 3 microns of coal tar of average grain diameter as internal layer covering material, that is, carbon material B
Oil asphalt is as external sheath material.
Weigh 500 grams of spherical natural graphites, 200 grams of coal tar asphaltes, 800 grams of petroleum base resins respectively first.Spherical day
Right graphite and solvent paraxylene are mixed to form the suspension that concentration is 0.5M, and resin and pitch are added separately to solvent to diformazan
The solution that concentration is 1.0M is formed in benzene.Three kinds of solution are stirred at room temperature it is uniformly mixed, using Rotary Evaporators at 125 DEG C
Drying makes solvent gradually volatilize, and is finally heat-treated in tube furnace under nitrogen atmosphere protection, nitrogen flow 30ml/min,
5 DEG C/min of heating rate, stops 2h, has obtained the advanced carbon material of double-coating by 1000 DEG C of final temperature.
Prepared carbon material 980g is mixed into 20min in Dry powder mixing apparatus with 10g carbon black, is added
The PVDF/NMP solution of 100g10%, mixes 30min in planetary-type mixer, obtained slurry coating on copper foil, dry,
And negative electrode of lithium ion battery is obtained to roller using roll squeezer；Roller spacing to roll squeezer during roller is 30 μm, lithium-ion electric
The porosity of pond cathode coating is 20%, with a thickness of 40 μm.Using cathode manufactured in the present embodiment as the cathode of half-cell, half electricity
The test result of pond performance is as shown in table 1.
Performance data table of the carbon material of 1 Examples 1 to 3 of table preparation as electrode material half-cell
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (9)
1. a kind of negative electrode of lithium ion battery, which is characterized in that the cathode including being made of carbon material, binder and conductive agent applies
Layer；
The carbon material includes：Carbon core is coated on the first material with carbon on carbon core surface, is coated on the first material with carbon table
Second carbon material in face；The carbon core is graphite or mesocarbon microspheres；The first material with carbon is that hard carbon, graphene or carbon are received
Mitron, second carbon material are amorphous carbon or graphite；
The porosity of the cathode coating be 20%~40%, the cathode coating with a thickness of 40 μm~90 μm；
The content of the carbon core is 70wt%~90wt%, and the content of the first material with carbon is 5wt%~35wt%, described the
Two carbon materials are 0.1wt%~10wt%.
2. negative electrode of lithium ion battery according to claim 1, which is characterized in that the content of the binder is the carbon materials
0.5wt%~10wt% of material, binder and conductive agent total amount；The content of the conductive agent be the carbon material, binder with
0.5wt%~10wt% of conductive agent total amount.
3. negative electrode of lithium ion battery according to claim 1, which is characterized in that the porosity of the cathode coating is 25%
~35%, the cathode coating with a thickness of 50 μm~75 μm.
4. a kind of preparation method of negative electrode of lithium ion battery, includes the following steps：
Carbon material, conductive agent are mixed with binder, obtain slurry；
The slurry is applied on a current collector, obtains negative electrode of lithium ion battery；
The carbon material includes：Carbon core is coated on the first material with carbon on carbon core surface, is coated on the second of first material with carbon surface
Carbon material；
The carbon nuclear material is graphite or mesocarbon microspheres, and the first material with carbon is that graphene, carbon nanotube or pyrolysis produce
The carbon materials material precursor of stiff carbon, second carbon material are the carbon materials material precursor that graphite or pyrolysis generate amorphous carbon；
The porosity of the negative electrode of lithium ion battery be 20%~40%, the negative electrode of lithium ion battery with a thickness of 40 μm~90
μm；
The content of the carbon core is 70wt%~90wt%, and the content of the first material with carbon is 5wt%~35wt%, described the
Two carbon materials are 0.1wt%~10wt%.
5. the preparation method according to claim 4, which is characterized in that the preparation method of the carbon material includes following step
Suddenly：
Carbon nuclear material, first material with carbon are mixed in a solvent with the second carbon material, obtain mixed liquor；
The mixed liquor is evaporated, it is subsequently heat-treated, obtain carbon material；
The carbon nuclear material is graphite or mesocarbon microspheres, and the first material with carbon is that graphene, carbon nanotube or pyrolysis produce
The carbon materials material precursor of stiff carbon, second carbon material are the carbon materials material precursor that graphite or pyrolysis generate amorphous carbon.
6. preparation method according to claim 4 or 5, which is characterized in that the partial size of the carbon nuclear material is 10 μm~30 μ
M, the partial size of the first material with carbon are 0.1 μm~10 μm, and the partial size of second carbon material is 0.1~10 μm.
7. the preparation method according to claim 4, which is characterized in that the preparation method of the carbon material, including following step
Suddenly：
Carbon nuclear material, first material with carbon are mixed with solvent, obtain the first mixed liquor, the second carbon material is mixed with solvent, is obtained
To the second mixed liquor；
It will be heat-treated after first mixed liquor evaporation, obtain the first cladding carbon material；
The first cladding carbon material is mixed with second mixed liquor, is heat-treated after evaporation, obtains carbon material；
The carbon nuclear material is graphite or mesocarbon microspheres, and the first material with carbon is that graphene, carbon nanotube or pyrolysis produce
The carbon materials material precursor of stiff carbon, second carbon material are the carbon materials material precursor that graphite or pyrolysis generate amorphous carbon.
8. preparation method according to claim 7, which is characterized in that it is described pyrolysis generate hard carbon carbon materials material precursor be
Petroleum base resin, the carbon materials material precursor that the pyrolysis generates amorphous carbon is coal tar asphalt.
9. the preparation method according to claim 4, which is characterized in that the process for obtaining slurry is specially：
It is mixed again with binder after carbon material is mixed with conductive agent, obtains slurry.
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| CN106898740B (en) * | 2017-02-22 | 2020-09-01 | 深圳市金润能源材料有限公司 | Graphite negative electrode material and lithium ion battery |
| CN109461964B (en) * | 2017-09-06 | 2021-06-08 | 宁德时代新能源科技股份有限公司 | Lithium ion secondary battery |
| CN109713237A (en) * | 2017-10-26 | 2019-05-03 | 宁德时代新能源科技股份有限公司 | Lithium ion secondary battery |
| CN109713225A (en) * | 2017-10-26 | 2019-05-03 | 宁德时代新能源科技股份有限公司 | Lithium ion secondary battery |
| KR102519441B1 (en) * | 2017-12-22 | 2023-04-07 | 삼성에스디아이 주식회사 | Composite negative electrode active material for lithium secondary battery, an anode comprising the same, and the lithium secondary battery comprising the anode |
| US10468674B2 (en) | 2018-01-09 | 2019-11-05 | South Dakota Board Of Regents | Layered high capacity electrodes |
| JP7049004B2 (en) * | 2018-01-09 | 2022-04-06 | サウス ダコタ ボード オブ リージェンツ | Layered high capacity electrode |
| CN110165195A (en) * | 2019-06-13 | 2019-08-23 | 广东凯金新能源科技股份有限公司 | A kind of secondary lithium battery composite graphite particles and preparation method thereof |
| CN113451575B (en) * | 2020-03-24 | 2022-09-09 | 比亚迪股份有限公司 | Lithium ion battery cathode material, preparation method thereof, cathode and lithium ion battery |
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| CN102299308B (en) * | 2011-09-03 | 2014-05-07 | 深圳市贝特瑞新能源材料股份有限公司 | Lithium ion battery cathode material, and preparation method and lithium ion battery thereof |
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