CN109859951A - A kind of carbon-based composite negative pole material and preparation method thereof and a kind of electrochmical power source and preparation method thereof - Google Patents
A kind of carbon-based composite negative pole material and preparation method thereof and a kind of electrochmical power source and preparation method thereof Download PDFInfo
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- CN109859951A CN109859951A CN201910088946.0A CN201910088946A CN109859951A CN 109859951 A CN109859951 A CN 109859951A CN 201910088946 A CN201910088946 A CN 201910088946A CN 109859951 A CN109859951 A CN 109859951A
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The present invention provides a kind of carbon-based composite negative pole material and preparation method thereof and a kind of electrochmical power sources and preparation method thereof.The negative electrode material is mainly made of graphite and hard carbon, and the graphite and hard carbon independently are spherical or spherical, and the ratio between partial size D50 of the graphite and hard carbon isThe electrochmical power source includes the carbon-based composite negative pole material.The preparation method of the electrochmical power source includes: (1) preparation negative electrode tab；(2) positive plate is prepared；(3) battery core is made in negative electrode tab, positive plate and diaphragm, be put into shell, be inserted into lithium source pole after injecting electrolyte, carry out lithium ion pre-doping, be melted into later, remove lithium source pole, sealing obtains the electrochmical power source.Negative electrode material compacted density provided by the invention is high, and electrochmical power source first charge discharge efficiency provided by the invention is high, and chemical property is good.
Description
Technical field
The invention belongs to technical field of chemical power, it is related to a kind of carbon-based composite negative pole material, more particularly to a kind of carbon-based
Composite negative pole material and preparation method thereof and a kind of electrochmical power source and preparation method thereof.
Background technique
As economic development, the consumption of fossil resource and environmental crisis problem come out one after another, people increasingly pay attention to development can
Duration and safety.Therefore electrochmical power source is as energy storage in converting system is high with its resource utilization, environmental pollution is small
Plurality of advantages receives significant attention.Lithium ion battery has many advantages, such as that high output voltage, high-energy density, memory-less effect are mesh
Preceding secondary cell that is most widely used, most having development potentiality, however its power-performance, cycle life are poor.Supercapacitor conduct
A kind of model electrochemical energy storage device has many advantages, such as that high magnification, extra long life, high security, high power density compensate for lithium
The deficiency of ion battery.High-specific-power and specific energy appropriate are then required with the electrical source of power that hybrid electric vehicle (HEV) is representative.
Lithium ion mixed capacitor and high power lithium ion cell can have both biggish ratio under the premise of guaranteeing high-power output
Energy is the first choice of the dynamic power supply of the hybrid electricallies such as public transport, the rail friendship of line operation and pure electric automobile.
Graphite cathode material has good layer structure, and first charge discharge efficiency is high, the high advantage of compacted density, but interlamellar spacing compared with
It is small, it is unfavorable for fast charge.Hard carbon cathode material interlamellar spacing is larger, is conducive to fast charge, but the material has first charge discharge efficiency low, is compacted close
Spend the performance that low disadvantage is unfavorable for device specific energy.The shortcomings that in order to overcome above two material, many researchers are by two
Kind material is used in mixed way.But be used in mixed way by hard carbon influenced negative electrode tab density and anode first charge discharge efficiency it is all impacted, one
Determine in degree or can lose the specific energy of device.
CN102339988A discloses a kind of lithium ion battery cathode graphite material of high compacted density and preparation method thereof, packet
It includes following steps: being 1. uniformly mixed spherical natural graphite and amorphous carbon；2. in 800~1500 DEG C of progress superficial charring processing
2~6 hours；3. being sufficiently mixed with additive, the additive is the carbide or their oxide of silicon, iron, tin or boron
One of or it is a variety of；4. carry out catalyzed graphitization processing to get.Although compacting that the program improves carbon based negative electrodes material is close
Degree, but structure is complicated for negative electrode material, preparation process is cumbersome, higher cost.
CN104108699A discloses a kind of preparation side of high capacity high compacted density graphite negative material of lithium ion battery
Method the steps include: 1. 2. the natural graphite nodularization of fixed carbon content 80-99% to be carried out purification of graphite to it, needed for obtaining
Graphite cathode material.Although the program can also improve the compacted density of carbon based negative electrodes material, and the side of preparation to a certain extent
Method is simple, but obtained negative electrode material chemical property is poor.
CN102290572A discloses a kind of lithium ion secondary battery cathode active material and cathode, the lithium ion
Negative-electrode active material for secondary battery is with spherical or torispherical graphite, the engineered stone ink that particle aspect ratios are 1.0~3.0
The mixture for the needle-shaped artificial graphite for being 1.0~4.0 with particle aspect ratios is matrix, and mixed matrix is coated with non-graphite carbon
Material, covering amount are the 1~20% of mixed matrix quality；The non-graphite carbon material is pitch or resin.The present embodiment
Although improving the compacted density of carbon based negative electrodes material, structure is complicated for negative electrode material, and preparation process is cumbersome, higher cost.
Therefore, a kind of negative electrode material that compacted density is high is developed, and carries out process optimization, so that including the negative electrode material
Electrochmical power source first charge discharge efficiency it is high, have important research value for this field.
Summary of the invention
Aiming at the above shortcomings existing in the prior art, the purpose of the present invention is to provide a kind of carbon-based composite negative pole materials
And preparation method thereof and a kind of electrochmical power source and preparation method thereof.Carbon-based composite negative pole material compacted density provided by the invention
Height, electrochmical power source provided by the invention solve the problems, such as that first charge discharge efficiency is lower by the pre-doping of lithium ion.
To achieve this purpose, the present invention adopts the following technical scheme:
In a first aspect, the present invention provides a kind of carbon-based composite negative pole material, the negative electrode material is mainly by graphite and hard carbon
Composition, the graphite and hard carbon independently are spherical or spherical, and the ratio between the graphite and the D50 of hard carbon are
In carbon-based composite negative pole material provided by the invention, the ratio between the graphite and the D50 of hard carbon areSuch as1∶0.375、1∶0.38、1∶0.385、1∶0.39、1∶0.395、
1: 0.40,1: 0.405,1: 0.41 orDeng, it is not limited to cited numerical value, in the numberical range other
Unlisted numerical value is equally applicable.
In the present invention, because graphite and hard carbon independently are spherical or spherical, when the diameter of graphite and hard carbon is formed
Circle, the latter it is tangent with the former when, the ratio between partial size of the two isIn the grain of graphite and hard carbon that the present invention limits
The ratio between diameter D50 isIn the range of, the two mixes the compacted density for not reducing pole piece not only, instead
And promote the compacted density of the two.
Heretofore described hard carbon refers to difficult graphitized carbon, generally have specific capacity high (reaching 300-700mAh/g), times
The good feature of rate performance, while insertion of the lithium ion in this kind of material will not cause structure significantly to expand, and have and fill well
Discharge cycle performance.
It is used as currently preferred technical solution below, but not as the limitation to technical solution provided by the invention, leads to
Following preferred technical solution is crossed, can preferably reach and realize technical purpose and beneficial effect of the invention.
As currently preferred technical solution, the mass ratio of the graphite and hard carbon is Such as Or Deng it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable, wherein ρGraphite
For the density of graphite, ρHard carbonFor the density of hard carbon.In the application, using the mass ratio of above-mentioned graphite and hard carbon, it is ensured that energy
Enough guarantee in obtained C-base composte material, hard carbon is tangential on graphite, so that the compacted density of C-base composte material gets a promotion.
Preferably, the graphite include in artificial graphite, natural graphite or carbonaceous mesophase spherules any one or at least
Two kinds of combination, typical but unrestricted combination have: the combination of artificial graphite and natural graphite, artificial graphite and mesocarbon
The combination etc. of the combination of microballoon, natural graphite and carbonaceous mesophase spherules.
Preferably, the hard carbon includes resin carbon and/or organic polymer pyrolytic carbon.
Preferably, the resin carbon includes in phenolic resin carbon, epoxy resin carbon, poly furfuryl alcohol resin carbon or furfural resin carbon
Any one or at least two combination.
Preferably, the organic polymer pyrolytic carbon includes benzene carbon, poly furfuryl alcohol pyrolytic carbon, polyvinyl chloride pyrolytic carbon or phenolic aldehyde
In pyrolytic carbon any one or at least two combination.
Second aspect, the present invention provides a kind of preparation method of composite negative pole material carbon-based as described in relation to the first aspect, described
Method includes: to mix graphite and hard carbon, obtains the carbon-based composite negative pole material.
The third aspect, the present invention provide a kind of electrochmical power source, and the electrochmical power source includes as described in relation to the first aspect carbon-based
Composite negative pole material.
As currently preferred technical solution, the electrochmical power source includes positive plate, negative electrode tab, is located at positive plate and bears
Diaphragm, electrolyte and shell between pole piece；The negative electrode tab includes negative current collector and is coated on negative on negative current collector
Pole coating, the cathode coating include the lithium of negative electrode active material, conductive agent, binder and pre-doping；The positive plate includes
Plus plate current-collecting body and the positive coating being coated on plus plate current-collecting body, the anode coating includes positive active material, conductive agent
And binder；The negative electrode active material includes carbon-based composite negative pole material as described in relation to the first aspect.
By the pre-doping lithium on cathode coating, the lower problem of hard carbon first charge discharge efficiency can solve.
Preferably, in the cathode coating, conductive agent include in graphite powder, carbon black or acetylene black any one or at least
Two kinds of combination.
Preferably, in the cathode coating, binder includes polytetrafluoroethylene (PTFE) (PTFE), Kynoar (PVDF), hydroxyl
Any one in propyl methocel (HPMC), sodium carboxymethylcellulose (CMC) or butadiene-styrene rubber (SBR) or at least two
Combination.
Preferably, in the cathode coating, the mass ratio of negative electrode active material, conductive agent and binder is 95: 2: 3.
Preferably, in the cathode coating, the lithium of pre-doping is lithium ion.
Preferably, the negative current collector is non-Kong Jiliu, preferably non-porous copper foil, non-porous stainless steel foil or non-porous
Titanium foil in any one or at least two combination.
As currently preferred technical solution, the positive active material includes porous carbon and/or lithium transition-metal acid
Salt.
Preferably, the porous carbon include in active carbon, carbon nanotube, fold graphene or mesoporous carbon any one or
At least two combination.
Preferably, the lithium-transition metal mixtures include LiCoO2、LiMn2O4、LiNiO2、LiFePO4、
LiNi0.8Co0.2O2、LiNi1/3Co1/3Mn1/3O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2、
LiNi0.8Co0.1Mn0.1O2、LiNi0.8Co0.1Al0.1O2In any one or at least two combination.
Preferably, in the positive coating, conductive agent include in graphite powder, carbon black or acetylene black any one or at least
Two kinds of combination.
Preferably, in the positive coating, binder includes polytetrafluoroethylene (PTFE) (PTFE), Kynoar (PVDF), hydroxyl
Any one in propyl methocel (HPMC), sodium carboxymethylcellulose (CMC) or butadiene-styrene rubber (SBR) or at least two
Combination.
In the anode coating, the mass ratio of positive active material, conductive agent and binder is 90: (2-5): (5-8), example
Such as 90: 2: 8,90: 3: 7,90: 4: 6 or 90: 5: 5, it is not limited to cited numerical value, in the numberical range, other are not
The numerical value enumerated is equally applicable.
Preferably, the plus plate current-collecting body is non-hole collector, preferably non-porous aluminium foil, non-porous stainless steel foil or nothing
In the titanium foil in hole any one or at least two combination.
As currently preferred technical solution, the electrolyte includes organic solvent and the solute containing lithium ion.
Preferably, the solute containing lithium ion includes LiClO4、LiBF4、LiPF6、LiCF3SO3、LiN(CF3SO2)、
LiBOB or LiAsF6In any one or at least two combination.Lithium ion insertion-deintercalation invertibity in this kind of material
Well, diffusion velocity is fast, and the volume change with reaction is small, they all have good cycle characteristics and large current characteristic in this way.
Preferably, the organic solvent includes ethylene carbonate, propene carbonate, gamma-butyrolacton, dimethyl carbonate, carbon
Diethyl phthalate, butylene, methyl ethyl carbonate, methyl propyl carbonate, ethylene sulfite, propylene sulfite, ethyl acetate
In acetonitrile any one or at least two combination.
In the present invention, it can be charge and discharge that electrolyte, which uses above-mentioned preferably solute and organic solvent containing lithium ion,
The migration of lithium ion provides quick channel in journey, increases the rate of reaction；Have electrochemically stable potential range wide simultaneously
(being stable between 0-5V), the features such as thermal stability is good, use temperature range is wide, so that electrochmical power source discharge and recharge reaction
Stability greatly improves, and is conducive to the promotion of electrochmical power source cycle life.
Preferably, the diaphragm includes polyethene microporous membrane (PE), microporous polypropylene membrane (PP), composite membrane (PP+PE+
PP), any one in inorganic ceramic membrane or paper diaphragm or at least two combination.Above-mentioned its thickness of preferred diaphragm is general
At 10-30 μm, aperture is at 0.03-0.05 μm, ability and high-temperature stability with good absorption electrolyte.
Preferably, the shell includes any one in aluminum plastic film, steel shell or aluminum hull.
Preferably, the electrochmical power source includes supercapacitor and/or lithium ion battery.
In the present invention, the electrochmical power source can be square electrochmical power source device, or cylindrical type electrochmical power source device
Part.
Fourth aspect, the present invention provide a kind of preparation method of electrochmical power source as described in the third aspect, the method includes
Following steps:
(1) negative electrode active material, conductive agent and binder are mixed, is tuned into slurry with solvent, is coated on negative current collector
On, it is post-processed, obtains negative electrode tab；
(2) positive active material, conductive agent and binder are mixed, is tuned into slurry with solvent, is coated on plus plate current-collecting body
On, it is post-processed, obtains positive plate；
(3) battery core is made in step (1) negative electrode tab, step (2) positive plate and diaphragm, be put into shell, infused
It is inserted into lithium source pole after entering electrolyte, lithium ion pre-doping is carried out, is melted into later, removes lithium source pole, sealing obtains describedization
Learn power supply.
In the present invention, non-porous collector can be used using the method that insertion lithium source pole carries out lithium ion pre-doping, get rid of
Dependence to there is hole collector, avoid because perforation copper foil and aluminium foil technology it is immature caused by it is tired in industrialization production
It is difficult.
In the present invention, the battery core of step (3) can be lamination or winding-structure, and the battery core can be flexible package device
Part.
As currently preferred technical solution, step (1) described solvent includes N-Methyl pyrrolidone (NMP).
Preferably, step (1) post-processing include dry, roll, cut-parts and vacuum drying.
Preferably, the temperature of the drying is 80-90 DEG C, such as 80 DEG C, 82 DEG C, 84 DEG C, 86 DEG C, 88 DEG C or 90 DEG C etc.,
It is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.
Preferably, the vacuum drying temperature is 120-130 DEG C, such as 120 DEG C, 122 DEG C, 124 DEG C, 126 DEG C, 128
DEG C or 130 DEG C etc., it is not limited to cited numerical value, other unlisted numerical value are equally applicable in the numberical range, very
The sky dry time is for 24 hours.
Preferably, step (2) described solvent includes N-Methyl pyrrolidone (NMP).
Preferably, step (2) post-processing include dry, roll, cut-parts and vacuum drying.
Preferably, the temperature of the drying is 80-90 DEG C, such as 80 DEG C, 82 DEG C, 84 DEG C, 86 DEG C, 88 DEG C or 90 DEG C etc.,
It is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.
Preferably, the vacuum drying temperature is 120-130 DEG C, such as 120 DEG C, 122 DEG C, 124 DEG C, 126 DEG C, 128
DEG C or 130 DEG C etc., it is not limited to cited numerical value, other unlisted numerical value are equally applicable in the numberical range, very
The sky dry time is for 24 hours.
Preferably, in step (3), first shell is dried before injecting electrolyte.
Preferably, in step (3), the lithium source pole includes lithium piece and/or active material containing lithium.It is heretofore described to contain lithium
Active material refers to the electrode active material containing lithium, such as LiCoO2、LiMn2O4、LiNiO2、LiFePO4、LiNi0.8Co0.2O2、
LiNi1/3Co1/3Mn1/3O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.8Co0.1Al0.1O2Or LiNi0.6Co0.2Mn0.2O2Deng.
Preferably, in step (3), the lithium source pole not with anode and cathode contact.
Preferably, in step (3), the method for the lithium ion pre-doping applies constant current to battery core.By making battery core
Generate electric current, lithium ion in electrolyte can be made mobile to cathode, pre-doping on cathode, and lithium source extremely in lithium then enter electricity
Solve the lithium ion in liquid supplement electrolyte.During pre-doping, lithium ion of the pre-doping on cathode some will form SEI
Film, another part, which is stored on cathode, participates in discharge and recharge reaction.
Preferably, the 0.05C of the size of constant current negative electrode tab theoretical capacity in battery core is hereinafter, for example
0.05C, 0.04C, 0.03C or 0.02C etc., only sufficiently small electric current just can guarantee going on smoothly for pre-doping lithium technique, and
And keep doping more uniform, if electric current is excessive, it will lead to and adulterate the consequences such as uneven.
Preferably, the electricity size in the lithium ion pre-doping is the 15-30% of negative electrode tab theoretical capacity in battery core, example
Such as 15%, 18%, 19%, 20%, 21%, 23%, 26%, 28% or 30%, it is not limited to cited numerical value, it should
Other unlisted numerical value are equally applicable in numberical range.Size of current when electricity described here is by lithium ion pre-doping
With the product of electric current duration.In the present invention, if the electricity in lithium ion pre-doping is excessive, it will lead to positive excessive existing
As repeated charge can generate Li dendrite, cause monomer failure or free safety hazards；If in lithium ion pre-doping
Electricity is too small, and hard carbon will affect first charge discharge efficiency, reduces the capacity of device.
Preferably, in step (3), the removal lithium source pole carries out in dry atmosphere.
As the further preferred technical solution of electrochmical power source preparation method of the present invention, the method includes following steps
It is rapid:
(1) negative electrode active material, conductive agent and binder are mixed, is tuned into slurry with N-Methyl pyrrolidone, is coated on
On negative current collector, carries out 80-90 DEG C of drying, rolls and cut-parts, 120-130 DEG C of vacuum drying for 24 hours, obtains negative electrode tab；
(2) positive active material, conductive agent and binder are mixed, is tuned into slurry with N-Methyl pyrrolidone, is coated on
On plus plate current-collecting body, carries out 80-90 DEG C of drying, rolls and cut-parts, 120-130 DEG C of vacuum drying for 24 hours, obtains positive plate；
(3) battery core is made in step (1) negative electrode tab, step (2) positive plate and diaphragm, be put into shell, into
Row drying is inserted into lithium source pole after injecting electrolyte, carries out lithium ion pre-doping by applying constant generation electric current to battery core, described
The 0.05C of the size of electric current negative electrode tab theoretical capacity in battery core is hereinafter, the electricity size in the lithium ion pre-doping is
The 15-30% of negative electrode tab theoretical capacity, is melted into later in battery core, and lithium source pole is removed in dry atmosphere, and sealing obtains institute
State electrochmical power source.
Compared with prior art, the invention has the following advantages:
(1) carbon-based composite negative pole material provided by the invention by the ratio between partial size and quality of optimization graphite and hard carbon it
Than being obviously improved the compacted density of carbon-based composite negative pole material, compacted density is up to 1.45g/cm3。
(2) electrochmical power source provided by the invention by under reduced-current using lithium source pole carry out cathode lithium pre-doping,
The disadvantage that hard carbon first charge discharge efficiency is low in cathode is compensated for, the chemical property of electrochmical power source, electrification provided by the invention are improved
The specific energy of power supply is learned up to 180Wh/kg, maximum specific power is protected up to 18000Wh/kg, 5C charge and discharge time 10000 energy of circulation
There is rate up to 98%.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the carbon-based composite negative pole material prepared in the embodiment of the present invention 1, wherein 1- graphite, 2-
Hard carbon；
Fig. 2 carries out schematic diagram of cell structure when lithium ion pre-doping for step (3) in the embodiment of the present invention 10, wherein 3-
Positive plate, 4- negative electrode tab, 5- lithium source pole.
Specific embodiment
In order to better illustrate the present invention, it is easy to understand technical solution of the present invention, below further specifically to the present invention
It is bright.But following embodiments is only simple example of the invention, does not represent or limit the scope of the present invention, this
Invention protection scope is subject to claims.
The following are typical but non-limiting embodiments of the invention:
Embodiment 1
The present embodiment provides a kind of carbon-based composite negative pole material, the preparation method of the C-base composte material is by partial size
Spherical artificial graphite (the real density 2.25g/cm that D50 is 10 μm3) and partial size D50 be 4 μm spherical hard carbon (real density is
1.8g/cm3), it is mixed according to 19.5 mass ratioObtain the carbon-based composite negative pole material.
The structural schematic diagram of carbon-based composite negative pole material manufactured in the present embodiment is as shown in Figure 1, spherical hard carbon 2 is distributed in
In the gap of spherical graphite 1, and it is tangent with adjacent multiple graphite 1.
The present embodiment also provides a kind of preparation method of negative electrode tab:
Carbon-based composite negative pole material manufactured in the present embodiment is mixed with SuperP, PVDF according to 95: 2: 3 and is tuned into NMP
Then slurry is coated on 9 μm of copper foil (surface density are as follows: 100g/m2) on, drying (85 DEG C), roll, cut-parts, vacuum is dry for 24 hours
Dry (125 DEG C) are fabricated to negative electrode tab.
It is 1.45g/cm with the negative electrode tab compacted density that carbon-based composite negative pole material manufactured in the present embodiment obtains3。
Embodiment 2
The present embodiment provides a kind of carbon-based composite negative pole material, the preparation method of the C-base composte material is by partial size
Spherical artificial graphite's (identical as the artificial graphite density of embodiment 1) that D50 is 10 μm and the spherical hard carbon that partial size D50 is 4 μm
(identical as the hard carbon density of embodiment 1) mixes according to 22.5: 1 mass ratioIt obtains
The carbon-based composite negative pole material.
The present embodiment also provides a kind of preparation method of negative electrode tab:
Carbon-based composite negative pole material manufactured in the present embodiment is mixed with SuperP, PVDF according to 95: 2: 3, is tuned into NMP
Then slurry is coated on 9 μm of copper foil (surface density are as follows: 100g/m2) on, drying (85 DEG C), roll, cut-parts, vacuum is dry for 24 hours
Dry (125 DEG C) are fabricated to negative electrode tab.
It is 1.42g/cm with the negative electrode tab compacted density that carbon-based composite negative pole material manufactured in the present embodiment obtains3。
Embodiment 3
The present embodiment provides a kind of carbon-based composite negative pole material, the preparation method of the C-base composte material is by partial size
Spherical artificial graphite's (identical as the artificial graphite density of embodiment 1) that D50 is 10 μm and the spherical hard carbon that partial size D50 is 4 μm
(identical as the hard carbon density of embodiment 1) mixes according to 23: 1 mass ratioObtain institute
State carbon-based composite negative pole material.
The present embodiment also provides a kind of preparation method of negative electrode tab:
Carbon-based composite negative pole material manufactured in the present embodiment is mixed with SuperP, PVDF according to 95: 2: 3, is tuned into NMP
Then slurry is coated on 9 μm of copper foil (surface density are as follows: 100g/m2) on, drying (85 DEG C), roll, cut-parts, vacuum is dry for 24 hours
Dry (125 DEG C) are fabricated to negative electrode tab.
It is 1.40g/cm with the negative electrode tab compacted density that carbon-based composite negative pole material manufactured in the present embodiment obtains3。
Embodiment 4
The present embodiment provides a kind of carbon-based composite negative pole material, the preparation method of the C-base composte material is by partial size
Spherical artificial graphite's (identical as the artificial graphite density of embodiment 1) that D50 is 10 μm and the spherical hard carbon that partial size D50 is 4 μm
(identical as the hard carbon density of embodiment 1) mixes according to 24.3: 1 mass ratio?
To the carbon-based composite negative pole material.
The present embodiment also provides a kind of preparation method of negative electrode tab:
Carbon-based composite negative pole material manufactured in the present embodiment is mixed with SuperP, PVDF according to 95: 2: 3, is tuned into NMP
Then slurry is coated on 9 μm of copper foil (surface density are as follows: 100g/m2) on, drying (85 DEG C), roll, cut-parts, vacuum is dry for 24 hours
Dry (125 DEG C) are fabricated to negative electrode tab.
It is 1.38g/cm with the negative electrode tab compacted density that carbon-based composite negative pole material manufactured in the present embodiment obtains3。
Embodiment 5
The present embodiment provides a kind of carbon-based composite negative pole material, the preparation method of the C-base composte material is by partial size
Spherical natural graphite (the real density 2.25g/cm that D50 is 10 μm3) and partial size D50 be 3.7 μm of spherical hard carbon (phenolic aldehyde
Resin carbon, real density 1.75g/cm3), it is mixed according to 24.3: 1 mass ratioMatter
Amount obtains the carbon-based composite negative pole material than mixing.
Carbon-based composite negative pole material manufactured in the present embodiment is mixed with SuperP, PVDF according to 95: 2: 3, is tuned into NMP
Then slurry is coated on 9 μm of copper foil (surface density are as follows: 100g/m2) on, drying (90 DEG C), roll, cut-parts, vacuum is dry for 24 hours
Dry (130 DEG C) are fabricated to negative electrode tab.
It is 1.36g/cm with the negative electrode tab compacted density that carbon-based composite negative pole material manufactured in the present embodiment obtains3。
Embodiment 6
The present embodiment provides a kind of carbon-based composite negative pole material, the preparation method of the C-base composte material is by partial size
Spherical carbonaceous mesophase spherules (the real density 2.25g/cm that D50 is 10 μm3) and partial size D50 be 3.9 μm of spherical hard carbon
(poly furfuryl alcohol pyrolytic carbon, real density 1.85g/cm3)), it is mixed according to 19: 1 mass ratioMatter
Amount obtains the carbon-based composite negative pole material than mixing.
Carbon-based composite negative pole material manufactured in the present embodiment is mixed with SuperP, PVDF according to 95: 2: 3, is tuned into NMP
Then slurry is coated on 9 μm of copper foil (surface density are as follows: 100g/m2) on, drying (80 DEG C), roll, cut-parts, vacuum is dry for 24 hours
Dry (120 DEG C) are fabricated to negative electrode tab.
It is 1.43g/cm with the negative electrode tab compacted density that carbon-based composite negative pole material manufactured in the present embodiment obtains3。
Comparative example 1
The spherical artificial graphite that the partial size in embodiment 1 is 10 μm is used only in this comparative example.
Spherical artificial graphite's cathode that the partial size applied in example 1 is 10 μm is mixed with SuperP, PVDF according to 95: 2: 3, is used
NMP is tuned into slurry, is then coated on 9 μm of copper foil (surface density are as follows: 100g/m2) on, drying (85 DEG C), roll, cut-parts,
Vacuum drying (125 DEG C) is fabricated to negative electrode tab for 24 hours.
The compacted density for the negative electrode tab that this comparative example provides is 1.35g/cm3。
Comparative example 2
The spherical hard carbon that the partial size in embodiment 1 is 4 μm is used only in this comparative example.
The spherical hard carbon cathode that the partial size applied in example 1 is 4 μm is mixed with SuperP, PVDF according to 95: 2: 3, with NMP tune
At slurry, it is then coated on 9 μm of copper foil (surface density are as follows: 100g/m2) on, drying (85 DEG C) rolls, cut-parts, for 24 hours vacuum
Dry (125 DEG C) are fabricated to negative electrode tab.
The compacted density for the negative electrode tab that this comparative example provides is 1.0g/cm3。
Comparative example 3
This comparative example provides a kind of carbon-based composite negative pole material, and the preparation method of the C-base composte material is by partial size
Spherical artificial graphite's (identical as the artificial graphite density of embodiment 1) that D50 is 10 μm and the spherical hard carbon that partial size D50 is 5 μm
(real density 1.78g/cm3), it is mixed according to 20: 1 mass ratio It obtains described carbon-based
Composite negative pole material.
Carbon-based composite negative pole material prepared by this comparative example is mixed with SuperP, PVDF according to 95: 2: 3, is tuned into NMP
Then slurry is coated on 9 μm of copper foil (surface density are as follows: 100g/m2) on, drying (85 DEG C), roll, cut-parts, vacuum is dry for 24 hours
Dry (125 DEG C) are fabricated to negative electrode tab.
It is 1.25g/cm with the negative electrode tab compacted density that carbon-based composite negative pole material prepared by this comparative example obtains3。
Embodiment 7
The present embodiment provides a kind of preparation methods of positive plate:
A certain amount of active carbon, SuperP, CMC are weighed, SBR is slurred according to 90: 2: 3: 5 ratio with deionized water
Material, is coated on the aluminium foil of 20um (surface density are as follows: 100g/m2) on, drying (85 DEG C) is rolled, cut-parts, is dried in vacuo for 24 hours
(125 DEG C) are fabricated to anode pole piece.Compacted density is 0.60g/cm3。
Embodiment 8
The present embodiment provides a kind of preparation methods of positive plate:
Weigh a certain amount of LiFePO4, active carbon, SuperP, PVDF be in mass ratio 45: 45: 5: 5 mixing, with NMP tune
At slurry, it is then coated on 20 μm of aluminium foil (surface density are as follows: 160g/m2) on, drying (80 DEG C) rolls, is cut-parts, true for 24 hours
Sky dry (120 DEG C) is fabricated to positive plate, compacted density 1.8g/cm3。
Embodiment 9
The present embodiment provides a kind of preparation methods of positive plate:
Weigh a certain amount of LiNi1/3Co1/3Mn1/3O2, SuperP, PVDF be in mass ratio 90: 5: 5 mixing, with NMP tune
At slurry, it is then coated on 20 μm of aluminium foil (surface density are as follows: 160g/m2) on, drying (90 DEG C) rolls, is cut-parts, true for 24 hours
Sky dry (130 DEG C) is fabricated to positive plate, compacted density 3.2g/cm3。
Embodiment 10
The present embodiment provides a kind of preparation methods of electrochmical power source:
(1) carbon-based composite negative pole material prepared by embodiment 1 is mixed according to 95: 2: 3 with NMP tune with SuperP, PVDF
At slurry, it is then coated on 9 μm of copper foil (surface density are as follows: 100g/m2) on, drying (85 DEG C) rolls, cut-parts, for 24 hours vacuum
Dry (125 DEG C) are fabricated to negative electrode tab, and being cut into effective area is 94*198mm；
(2) positive plate is prepared according to the method for embodiment 7, and being cut into effective area is 91*195mm；
(3) by step (1) negative electrode tab, step (2) positive plate and diaphragm, (width is the NKK4030 paper of 203mm
Diaphragm) battery core is made in lamination, is put into shell, is dried, it is inserted into lithium source pole (lithium piece) after injecting electrolyte, by battery core
Apply constant current and carry out lithium ion pre-doping, the size of the electric current is the 0.05C of negative electrode tab theoretical capacity in battery core, institute
Stating the electricity size in lithium ion pre-doping is 22% of negative electrode tab theoretical capacity in battery core, is melted into later, in dry gas
Lithium source pole is removed in atmosphere, sealing obtains the electrochmical power source.
Schematic diagram of cell structure when Fig. 2 is step (3) progress lithium ion pre-doping in the present embodiment, this laminated cell
Lithium source pole 5 neither contacted with negative electrode tab 4, also do not contact, but negative electrode tab carried out by the effect of electric current pre- with positive plate 3
Mix lithium.
The electrochemical property test of electrochmical power source manufactured in the present embodiment the results are shown in Table 1.
Embodiment 11
The electrochmical power source preparation method of the present embodiment is referring to embodiment 10, and difference is: step (1) directlys adopt embodiment
1 negative electrode tab, step (2) directly adopt the positive plate of embodiment 8, and the electricity size in step (3) lithium ion pre-doping is electricity
The 15% of negative electrode tab theoretical capacity in core.
The electrochemical property test of electrochmical power source manufactured in the present embodiment the results are shown in Table 1.
Embodiment 12
The electrochmical power source preparation method of the present embodiment is referring to embodiment 10, and difference is: step (1) directlys adopt embodiment
2 negative electrode tab, step (2) directly adopt the positive plate of embodiment 8, and the electricity size in step (3) lithium ion pre-doping is electricity
The 15% of negative electrode tab theoretical capacity in core.
The electrochemical property test of electrochmical power source manufactured in the present embodiment the results are shown in Table 1.
Embodiment 13
The electrochmical power source preparation method of the present embodiment is referring to embodiment 10, and difference is: step (1) directlys adopt embodiment
3 negative electrode tab, step (2) directly adopt the positive plate of embodiment 8, and the electricity size in step (3) lithium ion pre-doping is electricity
The 15% of negative electrode tab theoretical capacity in core.
The electrochemical property test of electrochmical power source manufactured in the present embodiment the results are shown in Table 1.
Embodiment 14
The electrochmical power source preparation method of the present embodiment is referring to embodiment 10, and difference is: step (1) directlys adopt embodiment
4 negative electrode tab, step (2) directly adopt the positive plate of embodiment 8, and the electricity size in step (3) lithium ion pre-doping is electricity
The 15% of negative electrode tab theoretical capacity in core.
The electrochemical property test of electrochmical power source manufactured in the present embodiment the results are shown in Table 1.
Embodiment 15
The electrochmical power source preparation method of the present embodiment is referring to embodiment 10, and difference is: step (2) directlys adopt embodiment
9 positive plate, the material that step (3) lithium source pole uses are LiNi1/3Co1/3Mn1/3O2, electricity size in lithium ion pre-doping
It is 15% of negative electrode tab theoretical capacity in battery core.
The electrochemical property test of electrochmical power source manufactured in the present embodiment the results are shown in Table 1.
Embodiment 16
The electrochmical power source preparation method of the present embodiment is referring to embodiment 10, and difference is, step (1) directlys adopt embodiment
5 negative electrode tab, the size of the electric current of step (3) lithium ion pre-doping are the 0.04C of negative electrode tab theoretical capacity in battery core, lithium from
Electricity size in sub- pre-doping is 25% of negative electrode tab theoretical capacity in battery core.
The electrochemical property test of electrochmical power source manufactured in the present embodiment the results are shown in Table 1.
Embodiment 17
The electrochmical power source preparation method of the present embodiment is referring to embodiment 10, and difference is, step (1) directlys adopt embodiment
6 negative electrode tab, the size of the electric current of step (3) lithium ion pre-doping are the 0.03C of negative electrode tab theoretical capacity in battery core, lithium from
Electricity size in sub- pre-doping is 25% of negative electrode tab theoretical capacity in battery core.
The electrochemical property test of electrochmical power source manufactured in the present embodiment the results are shown in Table 1.
Comparative example 3
The electrochmical power source preparation method of this comparative example is referring to embodiment 10, and difference is: step is not inserted into lithium source in (3)
Pole is melted into after injecting electrolyte without lithium ion pre-doping.
The electrochemical property test of the electrochmical power source of this comparative example preparation the results are shown in Table 1.
Comparative example 4
The electrochmical power source preparation method of this comparative example is referring to embodiment 10, and difference is: step (2) directlys adopt embodiment
8 positive plate, step are not inserted into lithium source pole in (3), without lithium ion pre-doping, are melted into after injecting electrolyte.
The electrochemical property test of the electrochmical power source of this comparative example preparation the results are shown in Table 1.
Comparative example 5
The electrochmical power source preparation method of this comparative example is referring to embodiment 15, and difference is: step is not inserted into lithium source in (3)
Pole is melted into after injecting electrolyte without lithium ion pre-doping.
The electrochemical property test of the electrochmical power source of this comparative example preparation the results are shown in Table 1.
Comparative example 6
The electrochmical power source preparation method of this comparative example is referring to embodiment 15, and difference is: lithium ion pre-doping in step (3)
In electricity size be battery core in negative electrode tab theoretical capacity 40%.
The electrochemical property test of the electrochmical power source of this comparative example preparation the results are shown in Table 1.
Comparative example 7
The electrochmical power source preparation method of this comparative example is referring to embodiment 10, and difference is: step (1) directlys adopt comparative example
1 negative electrode tab, step (2) directly adopt the positive plate of embodiment 8.
The electrochemical property test of the electrochmical power source of this comparative example preparation the results are shown in Table 1.
Comparative example 8
The electrochmical power source preparation method of this comparative example is referring to embodiment 10, and difference is: step (1) directlys adopt comparative example
2 negative electrode tab, step (2) directly adopt the positive plate of embodiment 8.
The electrochemical property test of the electrochmical power source of this comparative example preparation the results are shown in Table 1.
Comparative example 9
The electrochmical power source preparation method of this comparative example is referring to embodiment 10, and difference is: step (1) directlys adopt comparative example
3 negative electrode tab, step (2) directly adopt the positive plate of embodiment 8.
The electrochemical property test of the electrochmical power source of this comparative example preparation the results are shown in Table 1.
Test method
For the electrochmical power source in embodiment and comparative example, with Arbin (SCTS 5V 100A) test equipment, in 25 DEG C of items
Part, 100%DOD test its 5C electric discharge specific energy；Its maximum specific power is tested according to method as defined in QC/T-2014, uses Arbin
(SCTS 5V 100A) test equipment is tested 5C charge and discharge time 10000 energy of circulation under 25 DEG C of conditions, 100%DOD and is possessed
Rate.
The compacting of negative electrode tab used in electrochmical power source in the result and embodiment and comparative example of above-mentioned electro-chemical test
Density is as shown in the table.
Table 1
Based on the above embodiments with comparative example it is found that carbon-based composite negative pole material provided by the invention needs graphite and hard carbon
The ratio between partial size and mass ratio be just able to achieve the purpose for improving compacted density in a specific range.Do not make in comparative example 1
With hard carbon, without using artificial graphite in comparative example 2, the partial size of artificial graphite and hard carbon is than improper in comparative example 3, therefore nothing
Method obtains the excellent compacted density of the present invention.
Electrochmical power source provided by the invention is because used the carbon-based composite negative pole material of function admirable provided by the invention
And it is subject to lithium ion pre-doping means, specific power and cycle life are very good, and in 5C electric discharge specific energy, by positive electrode
With the joint effect of cathode, there is some difference between each embodiment.Comparative example 3-5 does not carry out lithium ion pre-doping, therefore
Chemical property is integrally poor.Electricity in 6 lithium ion pre-doping of comparative example is excessive, and cycle performance is caused to be decreased obviously.Comparison
Example 7-9 does not use carbon-based composite negative pole material provided by the invention as negative electrode active material, therefore compared to other conditions
Identical but negative electrode active material uses the embodiment 11-13 of carbon-based composite negative pole material provided by the invention with comparative example 7-9,
The 5C electric discharge specific energy and maximum specific power of comparative example 7-9 declines.
The Applicant declares that the present invention is explained by the above embodiments detailed features and method detailed of the invention, but
The invention is not limited to above-mentioned detailed features and method detaileds, that is, do not mean that the present invention must rely on above-mentioned detailed features
And method detailed could be implemented.It should be clear to those skilled in the art, any improvement in the present invention, to this hair
The bright equivalence replacement for selecting component and addition, the selection of concrete mode of auxiliary element etc., all fall within protection scope of the present invention
Within the open scope.
Claims (10)
1. a kind of carbon-based composite negative pole material, which is characterized in that the negative electrode material is mainly made of graphite and hard carbon, the stone
Ink and hard carbon independently are spherical or spherical, and the ratio between partial size D50 of the graphite and hard carbon is
2. carbon-based composite negative pole material according to claim 1, which is characterized in that the mass ratio of the graphite and hard carbon isWherein, ρGraphiteFor the density of graphite, ρHard carbonFor the close of hard carbon
Degree；
Preferably, the graphite includes any one in artificial graphite, natural graphite or carbonaceous mesophase spherules or at least two
Combination；
Preferably, the hard carbon includes resin carbon and/or organic polymer pyrolytic carbon；
Preferably, the resin carbon includes appointing in phenolic resin carbon, epoxy resin carbon, poly furfuryl alcohol resin carbon or furfural resin carbon
It anticipates a kind of or at least two combinations；
Preferably, the organic polymer pyrolytic carbon includes benzene carbon, poly furfuryl alcohol pyrolytic carbon, polyvinyl chloride pyrolytic carbon or phenolic aldehyde pyrolysis
In carbon any one or at least two combination.
3. a kind of preparation method of carbon-based composite negative pole material as claimed in claim 1 or 2, which is characterized in that the method packet
It includes: graphite and hard carbon being mixed, the carbon-based composite negative pole material is obtained.
4. a kind of electrochmical power source, which is characterized in that the electrochmical power source includes carbon-based Compound Negative as claimed in claim 1 or 2
Pole material.
5. electrochmical power source according to claim 4, which is characterized in that the electrochmical power source includes positive plate, negative electrode tab, position
Diaphragm, electrolyte and shell between positive plate and negative electrode tab；The negative electrode tab includes negative current collector and is coated on cathode
Cathode coating on collector, the cathode coating include the lithium of negative electrode active material, conductive agent, binder and pre-doping；Institute
The positive coating that positive plate includes plus plate current-collecting body He is coated on plus plate current-collecting body is stated, the anode coating includes positive-active
Substance, conductive agent and binder；The negative electrode active material includes carbon-based composite negative pole material as claimed in claim 1 or 2；
Preferably, in the cathode coating, conductive agent includes any one or at least two in graphite powder, carbon black or acetylene black
Combination；
Preferably, in the cathode coating, binder includes polytetrafluoroethylene (PTFE), Kynoar, hydroxypropyl methyl cellulose, carboxylic
In sodium carboxymethylcellulose pyce or butadiene-styrene rubber any one or at least two combination；
Preferably, in the cathode coating, the mass ratio of negative electrode active material, conductive agent and binder is 95: 2: 3；
Preferably, in the cathode coating, the lithium of pre-doping is lithium ion；
Preferably, the negative current collector is non-hole collector, preferably non-porous copper foil, non-porous stainless steel foil or non-porous
In titanium foil any one or at least two combination.
6. electrochmical power source according to claim 5, which is characterized in that the positive active material include porous carbon and/or
Lithium-transition metal mixtures；
Preferably, the porous carbon include in active carbon, carbon nanotube, fold graphene or mesoporous carbon any one or at least
Two kinds of combination；
Preferably, the lithium-transition metal mixtures include LiCoO2、LiMn2O4、LiNiO2、LiFePO4、LiNi0.8Co0.2O2、
LiNi1/3Co1/3Mn1/3O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2、
LiNi0.8Co0.1Al0.1O2In any one or at least two combination；
Preferably, in the positive coating, conductive agent includes any one or at least two in graphite powder, carbon black or acetylene black
Combination；
Preferably, in the positive coating, binder includes polytetrafluoroethylene (PTFE), Kynoar, hydroxypropyl methyl cellulose, carboxylic
In sodium carboxymethylcellulose pyce or butadiene-styrene rubber any one or at least two combination；
In the anode coating, the mass ratio of positive active material, conductive agent and binder is 90: (2-5): (5-8)；
Preferably, the plus plate current-collecting body is non-hole collector, preferably non-porous aluminium foil, non-porous stainless steel foil or non-porous
In titanium foil any one or at least two combination.
7. electrochmical power source according to claim 5 or 6, which is characterized in that the electrolyte includes organic solvent and contains
The solute of lithium ion；
Preferably, the solute containing lithium ion includes LiClO4、LiBF4、LiPF6、LiCF3SO3、LiN(CF3SO2)、LiBOB
Or LiAsF6In any one or at least two combination；
Preferably, the organic solvent includes ethylene carbonate, propene carbonate, gamma-butyrolacton, dimethyl carbonate, carbonic acid two
Ethyl ester, butylene, methyl ethyl carbonate, methyl propyl carbonate, ethylene sulfite, propylene sulfite, ethyl acetate or second
In nitrile any one or at least two combination；
Preferably, the diaphragm includes in polyethene microporous membrane, microporous polypropylene membrane, composite membrane, inorganic ceramic membrane or paper diaphragm
Any one or at least two combination；
Preferably, the shell includes any one in aluminum plastic film, steel shell or aluminum hull；
Preferably, the electrochmical power source includes supercapacitor and/or lithium ion battery.
8. a kind of preparation method of the electrochmical power source as described in claim any one of 4-7, which is characterized in that the method includes with
Lower step:
(1) negative electrode active material, conductive agent and binder are mixed, is tuned into slurry with solvent, is coated on negative current collector, into
Row post-processing, obtains negative electrode tab；
(2) positive active material, conductive agent and binder are mixed, is tuned into slurry with solvent, is coated on plus plate current-collecting body, into
Row post-processing, obtains positive plate；
(3) battery core is made in step (1) negative electrode tab, step (2) positive plate and diaphragm, be put into shell, injection electricity
It is inserted into lithium source pole after solving liquid, lithium ion pre-doping is carried out, is melted into later, removes lithium source pole, sealing obtains the chemical-electrical
Source.
9. the preparation method of electrochmical power source according to claim 8, which is characterized in that step (1) described solvent includes N- first
Base pyrrolidones；
Preferably, step (1) post-processing include dry, roll, cut-parts and vacuum drying；
Preferably, the temperature of the drying is 80-90 DEG C；
Preferably, the vacuum drying temperature is 120-130 DEG C, and the vacuum drying time is for 24 hours；
Preferably, step (2) described solvent includes N-Methyl pyrrolidone；
Preferably, step (2) post-processing include dry, roll, cut-parts and vacuum drying；
Preferably, the temperature of the drying is 80-90 DEG C；
Preferably, the vacuum drying temperature is 120-130 DEG C, and the vacuum drying time is for 24 hours；
Preferably, in step (3), first shell is dried before injecting electrolyte；
Preferably, in step (3), the lithium source pole includes lithium piece and/or active material containing lithium；
Preferably, in step (3), the lithium source pole not with anode and cathode contact；
Preferably, in step (3), the method for the lithium ion pre-doping is to apply constant current to battery core；
Preferably, the 0.05C or less of the size of constant current negative electrode tab theoretical capacity in battery core；
Preferably, the electricity size in the lithium ion pre-doping is the 15-30% of negative electrode tab theoretical capacity in battery core；
Preferably, in step (3), the removal lithium source pole carries out in dry atmosphere.
10. the preparation method of electrochmical power source according to claim 8 or claim 9, which is characterized in that the method includes following steps
It is rapid:
(1) negative electrode active material, conductive agent and binder are mixed, is tuned into slurry with N-Methyl pyrrolidone, is coated on cathode
On collector, carries out 80-90 DEG C of drying, rolls and cut-parts, 120-130 DEG C of vacuum drying for 24 hours, obtains negative electrode tab；
(2) positive active material, conductive agent and binder are mixed, is tuned into slurry with N-Methyl pyrrolidone, is coated on anode
On collector, carries out 80-90 DEG C of drying, rolls and cut-parts, 120-130 DEG C of vacuum drying for 24 hours, obtains positive plate；
(3) battery core is made in step (1) negative electrode tab, step (2) positive plate and diaphragm, is put into shell, is done
It is dry, it is inserted into lithium source pole after injecting electrolyte, carries out lithium ion pre-doping, the constant current by applying constant current to battery core
Size negative electrode tab theoretical capacity in battery core 0.05C hereinafter, electricity size in the lithium ion pre-doping is battery core
The 15-30% of middle negative electrode tab theoretical capacity, is melted into later, and lithium source pole is removed in dry atmosphere, and sealing obtains describedization
Learn power supply.
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| CN112735836A (en) * | 2020-12-25 | 2021-04-30 | 上海奥威科技开发有限公司 | Lithium ion capacitor negative pole piece, lithium ion capacitor and preparation method thereof |
| WO2023134340A1 (en) * | 2022-01-13 | 2023-07-20 | 宁德时代新能源科技股份有限公司 | Negative electrode active material, negative electrode plate, secondary battery, battery module, battery pack, and electric device thereof |
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Application publication date: 20190607 |