CN106784653A - Electrokinetic cell negative pole and the electrokinetic cell comprising the negative pole - Google Patents
Electrokinetic cell negative pole and the electrokinetic cell comprising the negative pole Download PDFInfo
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- CN106784653A CN106784653A CN201611052174.8A CN201611052174A CN106784653A CN 106784653 A CN106784653 A CN 106784653A CN 201611052174 A CN201611052174 A CN 201611052174A CN 106784653 A CN106784653 A CN 106784653A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/387—Tin or alloys based on tin
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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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
Abstract
The invention belongs to power battery technology field, more particularly to a kind of electrokinetic cell negative pole, including negative current collector and the negative electrode active material layer for being coated on the negative current collector surface, the negative electrode active material layer includes graphite and the composite being scattered in the gap of the graphite, the composite is silicon carbon material and/or carbon tin material, and the proportion of the graphite is 10% 100%；The surface of the negative electrode active material layer is provided with based solid electrolyte interfacial film（SEI films）Coat.Relative to prior art, the setting of class SEI film coats can reduce electrolyte contact with silicon grain/tin particles, the protection carried out to negative pole in the present invention, while the initial coulomb efficiency of composite negative pole can be improved.I.e. the present invention proposes to carry out negative pole modifying interface, and bionical structure SEI films improve material coulombic efficiency and the interface compatibility with electrolyte, promotes the application in the battery of silicon carbon material and carbon tin material.
Description
Technical field
The invention belongs to power battery technology field, more particularly to a kind of electrokinetic cell negative pole and moving comprising the negative pole
Power battery.
Background technology
Urban climate constantly deteriorates, and haze is seriously polluted, the health of serious harm people, development New-energy electric vehicle into
To reduce the inevitable choice of municipal pollution.The scale application of electric automobile is to security of lithium-ion-power cell and energy density
Propose requirement very high.Lithium ion battery has the characteristic that energy density is high, have extended cycle life and is widely used in all kinds of
In electronic product and electric automobile.But, current lithium-ion-power cell still use liquid electrolyte, liquid electrolyte with it is positive and negative
Have very strong thermal response activity, easily cause cells burst and blast；In addition, electrokinetic cell energy density is still relatively low.
Electrokinetic cell generally comprises the building blocks such as positive pole, negative pole, electrolyte and barrier film, wherein, all of at present negative
In the material of pole, the theoretical specific capacity of silicon is maximum, and its capacity is up to 4200mAh/g.But, silicon is used as negative material
During also encounter obviously difficult, it fails to be used widely in the industry.Influence its apply it is main because
Two are have, is first that irreversible capacity is excessive first in the middle of battery charge and discharge process, secondly, during circulating battery, silicon
Alternately, violent Volume Changes will cause the destruction of electrode surface structures, cycle performance of battery urgency for volume contraction and expansion
Play deteriorates.As described above, graphite cathode material is compared with silicon, its coulombic efficiency and cycle performance have greater advantage.But its
Theoretical specific capacity 372mAh/g and silicon have compared sizable gap.Therefore in lithium ion battery negative material preparation process, it is past
Toward graphite and silicon are prepared into composite, both advantages are fully combined, the composite cycle performance is than simple silicon material
Expect, while its specific capacity is again higher than graphite.Common practice is that silicon is wrapped up by various method carbon materials, makes it
It is well dispersed in formation Si/C negative materials in carbon material.Either for traditional graphite cathode material, or most have at present
The silicon-carbon cathode material of energy-density lithium ion battery, or carbon tin negative pole material are desirably used for, process is used in electrokinetic cell
In, cubical expansivity higher is easily caused, so that the cyclical stability of electrokinetic cell is poor, and electrode is compatible with electrolyte
Property is poor, causes the LiPF in electrolyte6Decompose and produce micro hydrofluoric acid corrosion silicon materials, and then cause can not on its surface
Form the SEI films of stabilization, so as to cause the decay of capacity even big potential safety hazard the problems such as.
Negative material can generate solid electrolyte interface film (SEI films) in cyclic process first in electrode surface.It is this
The composition of passivating film mainly includes inorganic layer and organic layer, and inorganic layer mainly includes Li2CO3、LiF、Li2O, LiOH etc., organic layer
Mainly include ROCO2Li、ROLi、(ROCO2Li)2Deng.SEI films have organic solvent insoluble, and solvent molecule can not pass through
This layer of passivating film, can effectively hinder the directly contact of electrolyte and electrode material, prevent the generation of side reaction, while effectively anti-
The only common insertion of solvent molecule, it is to avoid the destruction caused by solvent molecule is embedded in electrode material altogether；SEI films also have good
Ionic conductivity, the charge and discharge process of battery is not influenceed, thus substantially increase the cycle performance and service life of electrode.To the greatest extent
Pipe is in this way, the formation of SEI films is but can be with the lithium ion of deintercalation as cost to consume part so that first charge-discharge is irreversible
Capacity increases, coulombic efficiency reduction, if the SEI films that electrode surface is formed are unstable, it also occur that SEI films in cyclic process
The process of " formed-ruptured-re-formed ", will reduce battery.
The present invention is intended to provide a kind of electrokinetic cell negative pole and the electrokinetic cell comprising the negative pole, it passes through negative electrode active
The reasonable disposition of material, and by the surface of negative electrode active material layer set class SEI film coats, this SEI films be not with
It is cost to sacrifice recyclable active lithium, and can reduce the contact of electrolyte and silicon grain/tin particles, and negative pole is protected,
The initial coulomb efficiency of composite negative pole can be improved simultaneously.I.e. the present invention proposes to carry out negative pole modifying interface, bionical structure SEI
Film, improves material coulombic efficiency and the interface compatibility with electrolyte, extends the service life of battery, promotes silicon carbon material and carbon
Tin material application in the battery.
The content of the invention
An object of the present invention is：In view of the shortcomings of the prior art, a kind of electrokinetic cell negative pole is provided, it leads to
The reasonable disposition of negative active core-shell material is crossed, and class SEI film coats are set by the surface of negative electrode active material layer, it is this
It to sacrifice recyclable active lithium is cost that SEI films are not, the contact of electrolyte and silicon grain/tin particles can be reduced, to negative pole
The protection for carrying out, while the initial coulomb efficiency of composite negative pole can be improved.I.e. the present invention proposes to carry out modifying interface to negative pole,
Bionical structure SEI films, improve material coulombic efficiency and the interface compatibility with electrolyte, extend the service life of battery, promote
The application in the battery of silicon carbon material and carbon tin material.
In order to achieve the above object, the present invention is adopted the following technical scheme that：
Electrokinetic cell negative pole, including negative current collector and the negative electrode active material for being coated on the negative current collector surface
Layer, the negative electrode active material layer includes graphite and the composite being scattered in the gap of the graphite, the composite
It is silicon carbon material and/or carbon tin material, the proportion of the graphite is 10%-100%；Negative electrode active material i.e. of the invention be with
Used as the framework material in electrode, skeleton gap is silicon carbon material and/or carbon tin material to graphite, silicon carbon material and/or carbon tin material
Material provides filling and cushion space, and while improving electrode energy density, macroscopic view is without the compound of expansion in obtaining charge and discharge process
Electrode.It is zero thermal expansion or microdilatancy that is, the expansion rate of the negative electrode active material layer of this composition is very low, meanwhile, this is answered
The characteristics of negative pole is closed also with high power capacity and high-energy-density.
The surface of the negative electrode active material layer is provided with class SEI film coats.The setting of class SEI film coats can drop
The contact of low electrolyte and silicon grain/tin particles, the protection carried out to negative pole, while the coulomb first of composite negative pole can be improved
Efficiency, extends the service life of battery.I.e. the present invention proposes to carry out negative pole modifying interface, bionical structure SEI films, this SEI
It to sacrifice recyclable active lithium is cost that film is not, improves material coulombic efficiency and the interface compatibility with electrolyte, extension electricity
Pond service life, promotes the application in the battery of silicon carbon material and carbon tin material.
Improved as one kind of electrokinetic cell negative pole of the present invention, by mass percentage, the class SEI film coats
Constitute and be：The bonding agent of the amorphous carbon of 8%-96.5%, the lithium compound of 3%-90% and 0.5%-2%.
As electrokinetic cell negative pole of the present invention one kind improve, the lithium compound be lithium carbonate, alkyl lithium carbonates and
At least one in lithium fluoride.
Improved as one kind of electrokinetic cell negative pole of the present invention, the thickness of the class SEI film coats is 1 μm -50 μm.
Improved as one kind of electrokinetic cell negative pole of the present invention, the particle diameter of the graphite is 0.5 μm -100 μm.
Improved as one kind of electrokinetic cell negative pole of the present invention, the silicon carbon material is the silicon material of porous carbon layer cladding
Material, the carbon tin material is the tin material of porous carbon layer cladding.
Improved as one kind of electrokinetic cell negative pole of the present invention, the thickness of porous carbon layer is 5 μm -90 μm, porous carbon layer
It is 10%-50% to account for the mass ratio of the silicon carbon material or carbon tin material, and the porosity of porous carbon layer is 1%-90%.Porous carbon
The silicon materials and the tin material of porous carbon layer cladding of layer cladding can fully be combined porous carbon and silicon materials/tin with the compound of graphite
The advantage of both materials, its cycle performance is better than simple silicon/tin material, while its specific capacity is again higher than graphite.Porous carbon layer
The expansion of silicon materials/tin material can also to a certain extent be suppressed, while not influenceing its ion, electronic transmission performance again.
Improved as one kind of electrokinetic cell negative pole of the present invention, the preparation method of the class SEI film coats is：By nothing
Setting carbon, lithium compound and bonding agent are proportionally added into being modulated into slurry in solvent, then spray or be needed on negative pole work by slurry
Property material layer surface, be then heat-treated at 70 DEG C -100 DEG C, formed class SEI film coats.By polymer and lithiumation
Compound is proportionally added into being modulated into the mixture that slurry can be disperseed, is well mixed in solvent, so that the class for being formed
The distributed components of SEI film coats, it is ensured that the uniformity of its performance.
As electrokinetic cell negative pole of the present invention one kind improve, the bonding agent be polytetrafluoroethylene (PTFE), butadiene-styrene rubber and
At least one in sodium alginate, the solvent is at least one in water, ethanol and acetone.
It is another object of the present invention to provide a kind of electrokinetic cell, including positive pole, negative pole, electrolyte and barrier film, institute
Negative pole is stated for electrokinetic cell negative pole of the present invention.
Specific embodiment
Embodiment 1
Present embodiments provide a kind of electrokinetic cell negative pole, including negative current collector and be coated on the negative current collector
The negative electrode active material layer on surface, negative electrode active material layer includes graphite and the silicon carbon material being scattered in the gap of graphite, stone
The proportion of ink is 50%, and the particle diameter of graphite is 0.5 μm -100 μm；Silicon carbon material is the silicon materials of porous carbon layer cladding, porous carbon
The thickness of layer is 5 μm -90 μm, and the mass ratio that porous carbon layer accounts for silicon carbon material is 30%, and the porosity of porous carbon layer is 45%.
The surface of negative electrode active material layer is provided with class SEI film coats, and by mass percentage, the class SEI films are applied
The composition of coating is：80% amorphous carbon, 3% lithium carbonate, 5% alkyl lithium carbonates and 11% lithium fluoride and 1%
Bonding agent polytetrafluoroethylene (PTFE), the thickness of the class SEI film coats is 20 μm.The preparation method of class SEI film coats is：Will
Amorphous carbon, polytetrafluoroethylene (PTFE), lithium carbonate, alkyl lithium carbonates and lithium fluoride are proportionally added into being modulated into slurry in deionized water,
Slurry is sprayed at the surface of negative electrode active material layer again, is then heat-treated at 75 DEG C, form the class that thickness is 20 μm
SEI film coats.
Embodiment 2
As different from Example 1：
Negative electrode active material layer includes graphite and the silicon carbon material being scattered in the gap of graphite, and the proportion of graphite is
60%；Silicon carbon material is the silicon materials of porous carbon layer cladding, and the thickness of porous carbon layer is 5 μm -90 μm, and porous carbon layer accounts for silicon-carbon material
The mass ratio of material is 20%, and the porosity of porous carbon layer is 60%.
The composition of class SEI film coats is：70% amorphous carbon, 10% lithium carbonate, 10% alkyl lithium carbonates,
9.3% lithium fluoride and 0.7% bonding agent butadiene-styrene rubber, the thickness of class SEI film coats is 10 μm.
Remaining is repeated no more here with embodiment 1.
Embodiment 3
As different from Example 1：
Negative electrode active material layer includes graphite and the silicon carbon material being scattered in the gap of graphite, and the proportion of graphite is
80%；Silicon carbon material is the silicon materials of porous carbon layer cladding, and the thickness of porous carbon layer is 5 μm -90 μm, and porous carbon layer accounts for silicon-carbon material
The mass ratio of material is 25%, and the porosity of porous carbon layer is 30%.
The composition of class SEI film coats is：50% amorphous carbon, 20% lithium carbonate, 18.5% alkyl lithium carbonates,
10% lithium fluoride and 1.5% bonding agent sodium alginate, the thickness of class SEI film coats is 25 μm.
In the preparation method of class SEI film coats, deionized water is replaced by ethanol, and spraying is replaced by transfer, at heat
The temperature of reason is 80 DEG C.
Remaining is repeated no more here with embodiment 1.
Embodiment 4
As different from Example 1：
Negative electrode active material layer includes graphite and the silicon carbon material being scattered in the gap of graphite, and the proportion of graphite is
90%；Silicon carbon material is the silicon materials of porous carbon layer cladding, and the thickness of porous carbon layer is 5 μm -90 μm, and porous carbon layer accounts for silicon-carbon material
The mass ratio of material is 15%, and the porosity of porous carbon layer is 35%.
The composition of class SEI film coats is：88.8% amorphous carbon, 3% lithium carbonate, 2% alkyl lithium carbonates,
5% lithium fluoride and 1.2% bonding agent polytetrafluoroethylene (PTFE), the thickness of class SEI film coats is 28 μm.
In the preparation method of class SEI film coats, deionized water is replaced by acetone, and the temperature of heat treatment is 75 DEG C.
Remaining is repeated no more here with embodiment 1.
Embodiment 5
As different from Example 1：
Negative electrode active material layer includes graphite and the carbon tin material being scattered in the gap of graphite, and the proportion of graphite is
85%；Carbon tin material is the tin material of porous carbon layer cladding, and the thickness of porous carbon layer is 5 μm -90 μm, and porous carbon layer accounts for carbon tin material
The mass ratio of material is 18%, and the porosity of porous carbon layer is 45%.
The composition of class SEI film coats is：65% amorphous carbon, 10% lithium carbonate, 8.2% alkyl lithium carbonates,
15% lithium fluoride and 1.8% butadiene-styrene rubber, the thickness of class SEI film coats is 18 μm.
In the preparation method of class SEI film coats, the temperature of heat treatment is 85 DEG C.
Remaining is repeated no more here with embodiment 1.
Embodiment 6
As different from Example 1：
Negative electrode active material layer includes graphite and the carbon tin material being scattered in the gap of graphite, and the proportion of graphite is
55%；Carbon tin material is the tin material of porous carbon layer cladding, and the thickness of porous carbon layer is 5 μm -90 μm, and porous carbon layer accounts for carbon tin material
The mass ratio of material is 35%, and the porosity of porous carbon layer is 65%.
The composition of class SEI film coats is：75% amorphous carbon, 7.2% lithium carbonate, 8% alkyl lithium carbonates,
9% lithium fluoride and 0.8% bonding agent sodium alginate, the thickness of class SEI film coats is 16 μm.
In the preparation method of class SEI film coats, deionized water is replaced by ethanol, and spraying is replaced by transfer, at heat
The temperature of reason is 90 DEG C.
Remaining is repeated no more here with embodiment 1.
Embodiment 7
As different from Example 1：
Negative electrode active material layer includes graphite and the carbon tin material being scattered in the gap of graphite, and the proportion of graphite is
75%；Carbon tin material is the tin material of porous carbon layer cladding, and the thickness of porous carbon layer is 5 μm -90 μm, and porous carbon layer accounts for carbon tin material
The mass ratio of material is 28%, and the porosity of porous carbon layer is 80%.
The composition of class SEI film coats is：83.7% amorphous carbon, 4% lithium carbonate, 5% alkyl lithium carbonates,
6% lithium fluoride and 1.3% bonding agent butadiene-styrene rubber, the thickness of class SEI film coats is 22 μm.
In the preparation method of class SEI film coats, deionized water is replaced by acetone.
Remaining is repeated no more here with embodiment 1.
Embodiment 8
As different from Example 1：
Negative electrode active material layer includes graphite and the silicon carbon material being scattered in the gap of graphite, and the proportion of graphite is
75%；Silicon carbon material is the silicon materials of porous carbon layer cladding, and the thickness of porous carbon layer is 5 μm -90 μm, and porous carbon layer accounts for silicon-carbon material
The mass ratio of material is 25%, and the porosity of porous carbon layer is 55%.
The composition of class SEI film coats is：80.4% amorphous carbon, 8% lithium carbonate, 7% alkyl lithium carbonates,
3% lithium fluoride and 1.6% bonding agent sodium alginate, the thickness of class SEI film coats is 32 μm.
In the preparation method of class SEI film coats, the temperature of heat treatment is 95 DEG C.
Remaining is repeated no more here with embodiment 1.
Embodiment 9
As different from Example 1：
Negative electrode active material layer includes graphite and the silicon carbon material being scattered in the gap of graphite, and the proportion of graphite is
82%；Silicon carbon material is the silicon materials of porous carbon layer cladding, and the thickness of porous carbon layer is 5 μm -90 μm, and porous carbon layer accounts for silicon-carbon material
The mass ratio of material is 16%, and the porosity of porous carbon layer is 53%.
The composition of class SEI film coats is：35% amorphous carbon, 23.3% lithium carbonate, 20% alkyl lithium carbonates,
20% lithium fluoride and 1.7% bonding agent butadiene-styrene rubber, the thickness of class SEI film coats is 27 μm.
In the preparation method of class SEI film coats, the temperature of heat treatment is 85 DEG C.
Remaining is repeated no more here with embodiment 1.
Embodiment 10
As different from Example 1：
Negative electrode active material layer includes graphite and the carbon tin material being scattered in the gap of graphite, and the proportion of graphite is
95%；Carbon tin material is the tin material of porous carbon layer cladding, and the thickness of porous carbon layer is 5 μm -90 μm, and porous carbon layer accounts for carbon tin material
The mass ratio of material is 15%, and the porosity of porous carbon layer is 35%.
The composition of class SEI film coats is：40% amorphous carbon, 15% lithium carbonate, 15% alkyl lithium carbonates,
29% lithium fluoride and 1% bonding agent polytetrafluoroethylene (PTFE), the thickness of class SEI film coats is 9 μm.
In the preparation method of class SEI film coats, spraying is replaced by transfer, and the temperature of heat treatment is 95 DEG C.
Remaining is repeated no more here with embodiment 1.
Comparative example 1
This comparative example provides a kind of power battery cathode, including negative current collector and is coated on negative current collector surface
Negative electrode active material layer, negative electrode active material layer includes graphite, and the particle diameter of graphite is 0.5 μm -100 μm.
Embodiment 11-20
Present invention also offers a kind of electrokinetic cell, including positive pole, negative pole, electrolyte and barrier film, wherein negative pole is respectively
The negative pole of embodiment 1-10.
The preparation method of the battery is comprised the following steps：
S1, the preparation of negative pole：By the negative electrode active material (graphite and silicon carbon material/tin carbon material) of embodiment 1-10, glue
Agent SBR and conductive agent CNT are connect according to mass ratio 96：2：It is well mixed to obtain cathode size in 2 addition deionized waters, will
Cathode size is coated on Copper Foil, and negative pole coating surface density is 7.37mg/cm3, negative electrode active material layer is obtained, in negative electrode active
Class SEI coat films are arranged on material layer；
S2, the preparation of positive pole：By cobalt acid lithium, bonding agent PVDF and conductive agent conductive black according to mass ratio 96：2：2 add
It is well mixed to obtain anode sizing agent in NMP, anode sizing agent is coated on aluminium foil, positive pole is obtained, positive pole coating surface density is
13.5mg/cm3；
S3, battery core is prepared into by negative pole and positive pole, barrier film by winding process；
S4, is 1 by volume ratio:1:1 ethylene carbonate (EC), diethyl carbonate (DEC) and methyl ethyl carbonate (EMC)
Mixed solvent is mixed into, the ethylene carbonate of 1wt.% and the fluorinated ethylene carbonate of 2wt.% is subsequently adding, hexafluoro is added
Lithium phosphate (LiPF6), make its concentration for 1mol/L, liquid electrolyte is obtained, then liquid electrolyte is injected in battery core, take out true
Sky simultaneously stands 1h, and then battery is evacuated, and forms battery.
Comparative example 2
This comparative example provides a kind of preparation method of battery, comprises the following steps：
S1, the preparation of negative pole：By graphite, bonding agent SBR and conductive agent CNT according to mass ratio 96：2：2 additions are gone
It is well mixed to obtain cathode size in ionized water, cathode size is coated on Copper Foil, negative pole coating surface density is 7.37mg/
cm3, obtain negative electrode active material layer；
S2, the preparation of positive pole：By cobalt acid lithium, bonding agent PVDF and conductive agent conductive black according to mass ratio 96：2：2 add
It is well mixed to obtain anode sizing agent in NMP, anode sizing agent is coated on aluminium foil, positive pole coating surface density is 13.5mg/cm3,
Obtain positive pole；
S3, battery core is prepared into by negative pole and positive pole, barrier film by winding process；
S4, is 1 by volume ratio:1:1 ethylene carbonate (EC), diethyl carbonate (DEC) and methyl ethyl carbonate (EMC)
Mixed solvent is mixed into, the ethylene carbonate of 1wt.% and the fluorinated ethylene carbonate of 2wt.% is subsequently adding, hexafluoro is added
Lithium phosphate (LiPF6), make its concentration for 1mol/L, liquid electrolyte is obtained, then liquid electrolyte is injected in battery core, take out true
Sky simultaneously stands 1h, and then battery is evacuated, and forms battery.
Battery to embodiment 11 to 20 and comparative example 1 is circulated performance test (25 DEG C, 0.5C/1C) and first coulomb
Efficiency test, acquired results are shown in Table 1.
Table 1：The cycle performance test of the battery of embodiment 11 to 20 and comparative example 2 and first coulombic efficiency test result.
As can be seen from Table 1, battery of the invention has the coulomb first of more excellent normal-temperature circulating performance and Geng Gao
Efficiency.
The announcement and teaching of book according to the above description, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula is changed and changed.Therefore, the invention is not limited in specific embodiment disclosed and described above, to of the invention
Some modifications and changes should also be as falling into scope of the claims of the invention.Although additionally, being used in this specification
Some specific terms, but these terms are merely for convenience of description, do not constitute any limitation to the present invention.
Claims (10)
1. electrokinetic cell negative pole, including negative current collector and the negative electrode active material for being coated on the negative current collector surface
Layer, it is characterised in that：
The negative electrode active material layer includes graphite and the composite being scattered in the gap of the graphite, the composite
It is silicon carbon material and/or carbon tin material, the proportion of the graphite is 10%-100%；
The surface of the negative electrode active material layer is provided with class SEI film coats.
2. electrokinetic cell negative pole according to claim 1, it is characterised in that：By mass percentage, the class SEI films
The composition of coat is：The bonding agent of the amorphous carbon of 8%-96.5%, the lithium compound of 3%-90% and 0.5%-2%.
3. electrokinetic cell negative pole according to claim 2, it is characterised in that：The lithium compound is lithium carbonate, alkyl
At least one in lithium carbonate and lithium fluoride.
4. electrokinetic cell negative pole according to claim 1, it is characterised in that：The thickness of the class SEI film coats is 1
μm-50μm。
5. electrokinetic cell negative pole according to claim 1, it is characterised in that：The particle diameter of the graphite is 0.5 μm of -100 μ
m。
6. electrokinetic cell negative pole according to claim 1, it is characterised in that：The silicon carbon material is coated for porous carbon layer
Silicon materials, the carbon tin material be porous carbon layer cladding tin material.
7. electrokinetic cell negative pole according to claim 6, it is characterised in that：The thickness of porous carbon layer is 5 μm -90 μm,
It is 10%-50% that porous carbon layer accounts for the mass ratio of the silicon carbon material or carbon tin material, and the porosity of porous carbon layer is 1%-
90%.
8. electrokinetic cell negative pole according to claim 2, it is characterised in that：The preparation side of the class SEI film coats
Method is：Amorphous carbon, lithium compound and bonding agent are proportionally added into be modulated into slurry in solvent, then slurry is sprayed or transferred
In the surface of negative electrode active material layer, then it is heat-treated at 70 DEG C -100 DEG C, is formed class SEI film coats.
9. electrokinetic cell negative pole according to claim 8, it is characterised in that：The bonding agent is polytetrafluoroethylene (PTFE), fourth
At least one in benzene rubber and sodium alginate, the solvent is at least one in water, ethanol and acetone.
10. a kind of electrokinetic cell, including positive pole, negative pole, electrolyte and barrier film, it is characterised in that：The negative pole is claim 1
Electrokinetic cell negative pole described in 9 any one.
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| CN108365168A (en) * | 2018-01-10 | 2018-08-03 | 山东奥冠新能源科技有限公司 | Lithium battery cathode plate and its preparation method and application prepared by carbon material containing film |
| CN108365167A (en) * | 2017-12-19 | 2018-08-03 | 成都亦道科技合伙企业（有限合伙） | A kind of graphite cathode structure combination and preparation method thereof, lithium battery electric core |
| CN110176634A (en) * | 2019-05-16 | 2019-08-27 | 湖北锂诺新能源科技有限公司 | A kind of preparation process of low bulk lithium ion battery |
| CN111540886A (en) * | 2020-04-20 | 2020-08-14 | 欣旺达电动汽车电池有限公司 | Negative electrode material, preparation method thereof and multilayer electrode |
| CN112310347A (en) * | 2020-11-03 | 2021-02-02 | 珠海冠宇电池股份有限公司 | Lithium ion battery with high energy density and charging capacity |
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| CN112640182A (en) * | 2018-09-14 | 2021-04-09 | 旭化成株式会社 | Nonaqueous electrolyte solution and nonaqueous secondary battery |
| CN112635744A (en) * | 2021-03-09 | 2021-04-09 | 河南电池研究院有限公司 | Carbon-silicon-tin composite cathode material and preparation method thereof |
| CN114447330A (en) * | 2021-11-19 | 2022-05-06 | 惠州市豪鹏科技有限公司 | Electrode, electrode material and preparation method thereof |
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| CN108365168A (en) * | 2018-01-10 | 2018-08-03 | 山东奥冠新能源科技有限公司 | Lithium battery cathode plate and its preparation method and application prepared by carbon material containing film |
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| CN112640182A (en) * | 2018-09-14 | 2021-04-09 | 旭化成株式会社 | Nonaqueous electrolyte solution and nonaqueous secondary battery |
| CN110176634A (en) * | 2019-05-16 | 2019-08-27 | 湖北锂诺新能源科技有限公司 | A kind of preparation process of low bulk lithium ion battery |
| CN111540886A (en) * | 2020-04-20 | 2020-08-14 | 欣旺达电动汽车电池有限公司 | Negative electrode material, preparation method thereof and multilayer electrode |
| CN111540886B (en) * | 2020-04-20 | 2023-09-12 | 欣旺达电动汽车电池有限公司 | Negative electrode material, preparation method thereof and multilayer electrode |
| CN112310347A (en) * | 2020-11-03 | 2021-02-02 | 珠海冠宇电池股份有限公司 | Lithium ion battery with high energy density and charging capacity |
| CN112310347B (en) * | 2020-11-03 | 2022-03-18 | 珠海冠宇电池股份有限公司 | Lithium ion battery with high energy density and charging capacity |
| CN112635744A (en) * | 2021-03-09 | 2021-04-09 | 河南电池研究院有限公司 | Carbon-silicon-tin composite cathode material and preparation method thereof |
| CN114447330A (en) * | 2021-11-19 | 2022-05-06 | 惠州市豪鹏科技有限公司 | Electrode, electrode material and preparation method thereof |
| CN115632105A (en) * | 2022-12-19 | 2023-01-20 | 四川新能源汽车创新中心有限公司 | Porous negative pole piece, preparation method thereof and lithium ion battery |
| CN115632105B (en) * | 2022-12-19 | 2023-03-21 | 四川新能源汽车创新中心有限公司 | Porous negative pole piece, preparation method thereof and lithium ion battery |
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