CN107834007A - Barrier film and lithium ion battery - Google Patents
Barrier film and lithium ion battery Download PDFInfo
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- CN107834007A CN107834007A CN201711125086.0A CN201711125086A CN107834007A CN 107834007 A CN107834007 A CN 107834007A CN 201711125086 A CN201711125086 A CN 201711125086A CN 107834007 A CN107834007 A CN 107834007A
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- base material
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- ion battery
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/463—Separators, membranes or diaphragms characterised by their shape
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
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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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Abstract
Present invention is disclosed a kind of barrier film and lithium ion battery, wherein, barrier film includes barrier film base material and organic coating, and the single or double that the organic coating is distributed in the barrier film base material by the organic polymer with caking property with the appointed thickness strip of the scattered coating in gap is formed.The present invention is by the way of the scattered coating strip organic coating of Multiple level, equally distributed concavo-convex intervallum is showed in membrane surface, certain cushion space is left in positive and negative interpolar, be advantageous to discharge both positive and negative polarity pole piece in charge and discharge process because of stress caused by expansion, be greatly reduced the probability of lithium ion battery torsional deformation in cyclic process；The internal resistance of battery is reduced while adhesive effect preferable with both positive and negative polarity is ensured；Infiltration for electrolyte simultaneously and circulation provide passage, extend the cycle life of lithium ion battery.
Description
Technical field
The present invention relates to new energy field, especially relates to barrier film and lithium ion battery.
Background technology
Countries in the world are grown to even greater heights to the cry for improving environmental protection, and various electric automobiles are shown one's talent.But due to electricity
The energy density in pond poor hundreds of times compared with gasoline, reach the numerical value required by electric automobile far away, expert's estimation will be in future 10
Electric automobile can not also substitute fuel engines automobile completely in year, and battery technology seriously hinders the universal general of electric automobile
And.
Current those skilled in the art develop a kind of mixed power plant (Hybrid-Electric Vehicle, abbreviation
HEV automobile).Motor is exactly combined and driven on an automobile by so-called mixed power plant with auxiliary power unit
Power, auxiliary power unit are actually a small fuel engine or dynamic power unit.This mixed power plant was both sent out
Wave engine continuous longevity of service, the advantages of good dynamic property, can play that motor is pollution-free, benefit of low noise again,
The two " fighting side by side ", learns from other's strong points to offset one's weaknesses, and the thermal efficiency of automobile can improve more than 10%, and waste gas discharge can reduce by more than 30%.But
Power resources of the battery as automobile start and stop in HEV are right when starting automobile, it is necessary to which sufficiently large electric current starts up the car
The super high power performance requirement of HEV battery is higher by much than common battery, it is necessary to meets that the ultra high power of short time is put
The requirement of electricity.
The coating method of existing septate organic coating influences the performance of the short time ultra high power electric discharge of HEV battery.
Organic coating is excessively intensive in membrane surface, can be in barrier film base material table after organic coating is by nonaqueous electrolytic solution immersion or hot pressing
Face part or large area film forming, cause the aperture of barrier film to be blocked, and increase battery core internal resistance, battery is in high power discharge and recharge, lithium
Ion can not be migrated quickly, and energy can not be reclaimed or discharged in a short time, and power of battery characteristic can not meet HEV vapour
The start and stop requirement of car.And larger resistance benefit existing for inside existing HEV battery cores, in transient high-current high-power operation
When, the temperature on battery core inside and surface rapidly rises.By experiment test, its surface is local in use for common HEV battery core
Temperature has reached 70 DEG C, and the temperature at battery core inner pole piece barrier film may be between 80-90 DEG C, and this is just needed inside battery core
Component has the function of quick conduction heat, local too high temperature spot is quickly disperseed heat and is transmitted to battery core table
Face, with battery thermal runaway risk caused by reducing hot-spot.
Therefore, prior art could be improved.
The content of the invention
The main object of the present invention is a kind of barrier film of offer, it is intended to which the new energy of lithium ion battery can not be met by solving existing barrier film
The technical requirements of the ultra high power electric discharge needed during the automobile start and stop of source.
The present invention proposes a kind of barrier film, including barrier film base material and organic coating, and the organic coating is by with caking property
Organic polymer the single or double of the barrier film base material be distributed in the appointed thickness strip of the scattered coating in gap formed.
Preferably, in addition to ceramic coating, the ceramic coating are located at the coplanar and/or different of barrier film with the organic coating
Face.
Preferably, the ceramic coating is located at the coplanar of barrier film with the organic coating, and the ceramic coating is located at institute
State between barrier film base material and the organic coating.
Preferably, the ceramic coating is by the way that the aluminium nitride for being scattered in organic solvent to be coated on to the table of the barrier film base material
Face is formed.
Preferably, the particle size range of the aluminium nitride includes 0.1um to 1um；The thickness range of the ceramic coating includes：
2um to 4um.
Preferably, the organic polymer includes Kynoar, butadiene-styrene rubber, methyl acrylate, carboxymethyl cellulose
One or more in sodium, polyacrylic acid；The thickness range of the organic coating includes 1um to 10um.
Preferably, the barrier film base material include polypropylene, polyethylene, polypropylene, polyethylene/polypropylene sandwich diaphragm,
It is a kind of in polyimide film, cellulose non-woven cloth diaphragm；The thickness range of the barrier film base material includes 7um to 25um；It is described every
The porosity ranges 40% to 60% of film base material；The air permeability scope of the barrier film base material includes 100s/100ml to 300s/
100ml。
Present invention also offers a kind of lithium rechargeable battery, including above-mentioned barrier film, in addition to positive plate, negative plate with
And electrolyte；For the barrier film between the positive plate and the negative plate, the electrolyte infiltrates the positive plate, negative pole
Whole interfaces of piece and barrier film.
Preferably, the positive plate include aluminium foil and coated on the nickel-cobalt lithium manganate cathode material on the aluminium foil, lead
Electric agent and binding agent；The mass ratio of the nickel-cobalt lithium manganate cathode material, conductive agent and binding agent is：90~96：2~5：2~
5。
Preferably, the negative plate includes copper foil and graphite coated on the copper foil, conductive agent, thickener and water-based
Binding agent；The graphite, conductive agent, the mass ratio of thickener and aqueous binders are 91~96：1~4：1~2：2~3.
Advantageous effects of the present invention：The present invention is using the scattered coating strip organic coating mode of Multiple level, in barrier film table
Face shows equally distributed concavo-convex intervallum, and certain cushion space is left in positive and negative interpolar, is advantageous to discharge both positive and negative polarity
Pole piece, because of stress caused by expansion, is greatly reduced lithium ion battery torsional deformation in cyclic process in charge and discharge process
Probability；The internal resistance of battery is reduced while adhesive effect preferable with both positive and negative polarity is ensured；Infiltration for electrolyte and stream simultaneously
It is logical that passage is provided, extend the cycle life of lithium ion battery.The present invention is barrier film is applied to high-power put simultaneously
In the battery core of electricity, barrier film is coated using oiliness AlN ceramic, is normal due to the thermal conductivity about 180-300W/mK of aluminium nitride (AlN)
5-10 times of ceramic alumina is advised, under the operating mode of big multiplying power (30C-40C) discharge and recharge, AlN ceramic layer can accelerate pair battery core
Conducted and disperseed inside battery part high heat, improved the heat dispersion of high-power H EV batteries, advantageously reduce battery
Internal temperature, ensure the security performance of battery in use；AlN is also equipped with excellent electrical property such as simultaneously：Dielectric constant,
The constants such as dielectric loss, body resistivity, dielectric strength all compare the transport element for being suitable as inside battery, to reducing in battery
Resistance also has certain effect.The battery assembled using the barrier film of the present invention, in high power discharge HPPC tests at normal temperatures,
50%SOC (electricity) discharge energy density reaches 5600W/kg, meets the ultra high power electric discharge of needs during the start and stop of HEV automobiles
Technical requirements.
Brief description of the drawings
The organic coating SEM figures of Fig. 1 one embodiment of the invention septations；
Battery core cross section structure schematic diagram in Fig. 2 one embodiment of the invention；
Fig. 3 embodiment of the present invention 1 is compared with the lithium ion battery high-multiplying power discharge battery core surface temperature change of comparative example 1
Figure；
Fig. 4 embodiment of the present invention 1 becomes with battery core thickness in the lithium ion battery high rate cyclic charge and discharge process of comparative example 1
Figure is compared in change.
The realization, functional characteristics and advantage of the object of the invention will be described further referring to the drawings in conjunction with the embodiments.
Embodiment
It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not intended to limit the present invention.
Reference picture 1, the barrier film of one embodiment of the invention, including barrier film base material and organic coating, the organic coating by
Organic polymer with caking property with the appointed thickness strip of the scattered coating in gap be distributed in the barrier film base material one side or
Two-sided formation.
Use with the organic coating of the scattered coating appointed thickness strip in gap, showed in membrane surface equally distributed recessed
Convex intervallum, certain space is left in positive and negative interpolar, be advantageous to discharge both positive and negative polarity pole piece in charge and discharge process because of expansion
Caused stress, it is greatly reduced the probability of lithium ion battery torsional deformation in cyclic process；Guarantee and both positive and negative polarity simultaneously
Pole piece is preferably bonded contact effect, avoids conventional full coat and covers organic coating under state by nonaqueous electrolytic solution immersion or hot pressing
Afterwards, large area film forming causes membrane pore size to block, and the situation of caused internal resistance of cell increase, uses disperseing with gap for the present invention
The barrier film of the organic coating of the appointed thickness strip of coating, on the internal resistance of cell without influence；The scattered coating appointed thickness in gap simultaneously
On the one hand the barrier film of the organic coating of strip infiltrates pole piece for electrolyte and provides passage, promote the wellability of electrolyte, have
Beneficial to giving full play to for battery performance；On the other hand it is the expansion headspace of graphite cathode, reduces swelling stress to battery core knot
The destructive power of structure.The scattered coating in gap refers to by setting the coated panel with specific interval groove on coating machine, in barrier film table
After vertical or horizontal formation of the face along barrier film is at interval of the uncoated region of the first specified width, which width, the organic of the second specified width, which width is coated with
Coating.The present embodiment is preferably after barrier film longitudinal direction is at interval of the uncoated regions of 200um to 300um, and 200um is to 300um's for coating
Organic coating, uncoated region and the organic coating region of coating is set to be evenly spaced distribution with strip.
Further, in addition to ceramic coating, the ceramic coating and the organic coating be located at the coplanar of barrier film and/or
Antarafacial.
For the battery of high power discharge, internal temperature of battery can rapidly rise to 80-90 DEG C in a short time, if hot
Amount is in inside battery local accumulation, it is impossible to which quick conduction is scattered and disappeared, and the security presence of battery is great during by high power discharge
Hidden danger.Ceramic coating can accelerate to be conducted and disperseed at the high heat local to inside battery, reduce battery entirety
Temperature, the heat dispersion of high-power lithium ion battery is improved, ensure the security performance of battery in use.
Further, the ceramic coating is located at the coplanar of barrier film with the organic coating, and the ceramic coating is located at
Between the barrier film base material and the organic coating.
The organic coating of the present embodiment is located on ceramic coating, on the one hand reduces organic coating to diaphragm matrix aperture
Influence, and then reduce the influence to the internal resistance of cell；On the other hand more efficiently solve structure of the battery in cyclic process
Problem on deformation, improve cycle performance of battery.
Further, the ceramic coating by the aluminium nitride for being scattered in organic solvent by being coated on the barrier film base material
Surface is formed.
It it is 5-10 times of conventional ceramic aluminum oxide, battery core exists due to the thermal conductivity about 180-300W/mK of aluminium nitride (AlN)
Under the operating mode of big multiplying power (30C-40C) discharge and recharge, AlN ceramic layer can be further speeded up to being carried out inside battery part high heat
Conduct and scattered, further improve the heat dispersion of high-power lithium ion battery, reduce internal temperature of battery, guarantee battery makes
Security performance during；AlN is also equipped with excellent electrical property such as simultaneously：Dielectric constant, dielectric loss, body resistivity, it is situated between
The constants such as electric strength all compare the transport element for being suitable as inside battery, are also had certain effect to reducing the internal resistance of cell.
Further, the particle size range of the aluminium nitride includes 0.1um to 1um；The thickness range bag of the ceramic coating
Include：2um to 4um.
Further, the organic polymer includes Kynoar, butadiene-styrene rubber, methyl acrylate, carboxymethyl cellulose
One or more in plain sodium, polyacrylic acid；The thickness range of the organic coating includes 1um to 10um.
Further, it is compound to include polypropylene, polyethylene, three layers of polypropylene, polyethylene/polypropylene for the barrier film base material
It is a kind of in film, polyimide film, cellulose non-woven cloth diaphragm；The thickness range of the barrier film base material includes 7um to 25um；It is described
The porosity ranges 40% to 60% of barrier film base material；The air permeability scope of the barrier film base material includes 100s/100ml to 300s/
100ml。
The porosity and air permeability scope of barrier film base material directly affect in lithium ion battery the migration rate of lithium ion and
Internal resistance performance, and then influence the power-performance of lithium ion battery.
Reference picture 2, the embodiment of the present invention additionally provide a kind of lithium ion battery, including above-mentioned barrier film 3, in addition to positive pole
Piece 1, negative plate 2 and electrolyte；The barrier film 3 is between the positive plate 1 and the negative plate 2, the electrolyte leaching
Moisten whole interfaces of the positive plate 1, negative plate 2 and barrier film 3, barrier film 3 includes barrier film base material 30, coated on barrier film base material 30
On the scattered coating appointed thickness strip of ceramic coating 31 and gap organic coating 32.
Further, the positive plate include aluminium foil and coated on the nickel-cobalt lithium manganate cathode material on the aluminium foil,
Conductive agent and binding agent；The mass ratio of the nickel-cobalt lithium manganate cathode material, conductive agent and binding agent is：90~96：2~5：2
~5.
Further, the negative plate includes copper foil and graphite, conductive agent, thickener and water coated on the copper foil
Property binding agent；The graphite, conductive agent, the mass ratio of thickener and aqueous binders are 91~96：1~4：1~2：2~3.
The preparation method flow of septation of the embodiment of the present invention is as follows：
S1：Choose the barrier film base material of appointed thickness scope.
For example it is polypropylene to choose isolation film base material, polyethylene, polypropylene, polyethylene/polypropylene sandwich diaphragm, polyamides
The one of which such as imines film, cellulose non-woven cloth diaphragm is as barrier film base material.Its thickness is 7-25um, and basement membrane porosity is 40-
60%, air permeability is in 100-300s/100ml.
S2：After specified ceramic powder slurry is dispersed with stirring with certain process conditions in a solvent, ceramic powder mixing slurry is formed
Material.
For example aluminium nitride of the particle size range including 0.1um to 1um is scattered in ethanol, 1-METHYLPYRROLIDONE (NMP) etc.
In organic solvent, stirring vacuum degree is normal pressure；Whipping temp is 25 DEG C；Mixing speed：25 revs/min of revolution, 1000 turns of rotation/
Minute；Mixing time 60 minutes, obtain the mixed slurry A with ceramic powder.A certain amount of poly- inclined fluorine is added in mixed slurry A
After the binding agents such as ethene (PVDF), continue to stir 3 hours under vacuum conditions, mixing speed：25 revs/min of revolution, rotation
2500 revs/min, mixed slurry B is obtained, measures mixed slurry B viscosity in ＜ 500mPas, you can discharging.
S3：By organic coating stock dispersion in designated solvent, it is mixing uniformly to form with the organic of specified solid content
Coating suspension dispersion liquid.
Such as：Organic polymer is included into Kynoar, butadiene-styrene rubber, methyl acrylate, sodium carboxymethylcellulose, poly-
One or more in acrylic acid are added in agitator tank with esters solvent with certain mass ratio, in 25 DEG C of ± 5 DEG C of stirring 4h, are stirred
Mix speed：25 revs/min of revolution, 2500 revs/min of rotation, the suspended dispersed liquid of bulky grain is agglomerated into, and solid content control exists
10% or so, viscosity ＜ 500mPas.
S4：The above-mentioned designated mode of ceramic powder mixed slurry is coated in the surface of barrier film base material, after drying, formation has
Specify the ceramic diaphragm of coating layer thickness.
For example above-mentioned ceramic powder mixed slurry in the one side coated in barrier film base material, is done by way of intaglio plate coating
The oiliness aluminium nitride ceramics coating that coating layer thickness is 2um to 4um is obtained after dry.
S5：By above-mentioned organic coating suspended dispersed liquid coated in above-mentioned ceramic diaphragm ceramic coating face on, formed with
The organic coating of the appointed thickness strip of the scattered coating of gap.
For example Kynoar PVDF, styrene butadiene rubber sbr, methyl acrylate PMMA, sodium carboxymethylcellulose will be included
The organic coating of the organic polymer with high-adhesion of the one or more of which such as CMC, polyacrylic acid PAA mixing, which suspends, to be divided
Dispersion liquid, barrier film single or double is coated in by way of nick version, is formed with the appointed thickness strip-like-shaped of the scattered coating in gap
Looks, coating layer thickness is in 1-10um.The barrier film of the present embodiment has a multiple combinations form, ceramic coating and the organic coating be located at every
The coplanar and/or antarafacial of film, such as the face organic coating of barrier film base material one and another side ceramic coating, the organic painting of barrier film base material one side
Layer and ceramic coating, the two-sided organic coating of barrier film base material and ceramic coating etc., but ceramic coating is located at barrier film with organic coating
When coplanar, ceramic coating is between barrier film base material and organic coating.
The lithium ion battery made using barrier film of the present invention and positive plate, negative plate assembling, high power at normal temperatures
Discharge in HPPC tests, 50%SOC (electricity) discharge energy density reaches 5600W/kg, is suitable for the new energy of lithium ion battery HEV
High power discharge application when source car starts.
The lithium ion battery preparation flow of the embodiment of the present invention is as follows：
S6：Positive electrode, conductive agent and binding agent are carried out after stirring in advance in certain mass ratio, add organic solvent point
Positive pole coating slurry is formed after dissipating uniformly, positive pole coating slurry is coated on aluminium foil and prepares based lithium-ion battery positive plate.
It is by nickle cobalt lithium manganate, conductive agent and binding agent example in mass ratio：90~96：2~5：2~5 are stirred in advance.Stir
It is normal pressure to mix vacuum；Whipping temp is 20-30 DEG C；Mixing speed：15-30 revs/min of revolution, 500-1200 revs/min of rotation
Clock；Mixing time 30-60 minutes, obtain mixed powder material A.It is the organic of 40-80% that mass ratio is added in mixed powder material A
Solvent N-methyl pyrilidone (NMP), continue to stir 3-5 hours, mixing speed in a vacuum：20-30 revs/min of revolution, from
Turn 1000-3000 revs/min, obtain mixed slurry B, measuring mixed slurry B viscosity can discharge in 4000-6000mPa.s,
If unqualified, addition NMP can be continued and be adjusted, untill qualified.Then mixed slurry B is coated with to drying on aluminium foil,
Roll-in, cutting, make positive plate.
S7：Negative material, conductive agent and thickener are carried out after stirring in advance in certain mass ratio, add aqueous binders
Negative pole coating slurry is formed after being uniformly dispersed, negative pole coating slurry is coated on copper foil and prepares anode plate for lithium ionic cell.
It is 91~96 by the mass ratio of graphite, conductive agent, thickener and aqueous binders：1~4：1~2：2~3 weigh respectively
Material, three kinds of graphite, conductive agent and thickener dry powder are stirred in advance.Stirring vacuum degree is normal pressure；Whipping temp is 20-30
℃；Mixing speed：15-30 revs/min of revolution, 500-1200 revs/min of rotation；Mixing time 30-60 minutes, it is dry to obtain mixing
Powder C.The aqueous binders polyacrylonitrile that mass ratio is 40-60% is added in mixed powder material C, continuation is stirred in a vacuum
2-4 hours, mixing speed：20-30 revs/min of revolution, 1000-3000 revs/min of rotation, obtains mixed slurry D, measures mixing
Slurry D viscosity can discharge in 2000-4000mPa., if unqualified, can continue deionized water and be adjusted, be until qualified
Only.Then mixed slurry D is coated with to drying on copper foil, roll-in, cutting, make negative plate.
S8：Above-mentioned positive plate, barrier film, negative plate are wound into battery core, are packaged into lithium ion battery.
By above-mentioned positive plate, barrier film, and negative plate are wound into battery core, barrier film be located at adjacent positive plate and negative plate it
Between.Aluminium pole ears and nickel lug are respectively welded at reserved aluminium foil and copper foil, respectively as the external interface of discharge and recharge, then will
Battery core is placed in laminated aluminum film bag, injects electrolyte, encapsulated, chemical conversion, the process such as partial volume, lithium ion battery is made.
It is specific embodiment below：
Embodiment 1：
Thickness 16um polypropylene is chosen as barrier film base material, porosity 50%, air permeability is in 200s/100ml；By grain
Spend the AlN ceramic powder and 1-METHYLPYRROLIDONE (NMP) example 1 in mass ratio that scope is 0.5um:2 are stirred in advance.Stirring vacuum
Spend for normal pressure；Whipping temp is 25 DEG C；Mixing speed：25 revs/min of revolution, 1000 revs/min of rotation；Mixing time 60 is divided
Clock, obtain premixed slurries.Kynoar (PVDF) solution that mass ratio is 20% is added in above-mentioned premixed slurries, after
It is continuous to stir 3 hours in a vacuum, mixing speed：25 revs/min of revolution, 2500 revs/min of rotation, obtains ceramic coating sizing-agent,
Measuring the viscosity of ceramic coating sizing-agent can discharge in ＜ 500mPas..By organic polymer polymethyl methacrylate and esters
Solvent quality ratio is 10:90 are added in agitator tank, in 25 DEG C of ± 5 DEG C of stirring 4h, mixing speed：25 revs/min of revolution, rotation
2500 revs/min, it is agglomerated into the suspended dispersed liquid of bulky grain, solid content control is 10% or so, viscosity ＜ 500mPas.Will be upper
Ceramic coating sizing-agent is stated by way of intaglio plate coating in the one side coated in barrier film base material, obtaining coating layer thickness after drying is
4um oiliness AlN ceramic barrier film.Above-mentioned suspended dispersed slurry material is made pottery by way of nick version coated in above-mentioned AlN
Porcelain facing, form the strip pattern with the scattered coating in gap that coating layer thickness is 5um.
The preferred nickel-cobalt lithium manganate material of the present embodiment positive electrode, the preferred graphite of negative material, electrolyte preferably pass through six
Lithium fluophosphate is dissolved in mass ratio as 1:2:The combined system that 1 EC+DMC+EMC in the mixed solvent is formed.
By nickle cobalt lithium manganate, conductive agent, the dry powder example 93 in mass ratio of three kinds of materials of binding agent:4:3 are stirred in advance.Stir
It is normal pressure to mix vacuum；Whipping temp is 25 DEG C；Mixing speed：25 revs/min of revolution, 1000 revs/min of rotation；Mixing time
60 minutes, obtain positive pole mixed powder material.The organic solvent N- that mass ratio is 45% will be added in above-mentioned positive pole mixed powder material
Methyl pyrrolidone (NMP), continue to stir 4 hours in a vacuum, mixing speed：25 revs/min of revolution, 2500 revs/min of rotation
Clock, obtains positive pole mixed slurry, and viscosity is that 4000-6000mPa. can discharge.Positive pole mixed slurry is coated with to baking on aluminium foil
It is dry, roll-in, cutting, make positive plate.
By graphite, conductive agent, the dry powder example 94 in mass ratio of three kinds of materials of thickener:3:3 are stirred in advance.Stirring vacuum
Spend for normal pressure；Whipping temp is 25 DEG C；Mixing speed：25 revs/min of revolution, 1000 revs/min of rotation；Mixing time 60 is divided
Clock, obtain negative pole mixed powder material.The aqueous binders polyacrylonitrile that mass ratio is 50% is added in negative pole mixed powder material,
Continue to stir 3 hours in a vacuum, mixing speed：25 revs/min of revolution, 2500 revs/min of rotation, obtains negative pole mixing slurry
Material, viscosity can discharge in 2000-4000mPa..Negative pole mixed slurry is coated with to drying on copper foil, roll-in, cut, is made
Negative plate.
By above-mentioned positive plate, barrier film, and negative plate are wound into battery core, barrier film be located at adjacent positive plate and negative plate it
Between.Aluminium pole ears and nickel lug are respectively welded in reserved aluminium foil and copper foil, as the external interface of discharge and recharge, then put battery core
In laminated aluminum film bag, the processes such as electrolyte, footpath encapsulation, chemical conversion, partial volume are injected, lithium ion battery 1 is made.Its battery size
For：Thickness 4.0mm, width 6.0, length 130mm, capacity 1.8Ah, charging/discharging voltage scope 2.8-4.1V.
Embodiment 2
It is that coated side of the organic coating on barrier film is different from the difference of embodiment 1, embodiment 2 passes through binding agent micro-
Rotogravure application forms Multiple level strip distributing pattern, i.e. barrier film one side coated ceramic coating to the film surface of barrier film base material, another
Face coats organic coating.Remaining is assembled into lithium ion battery 2 with embodiment 1.
Embodiment 3
It is that coated side of the organic coating on barrier film is different from the difference of embodiment 1, embodiment 3 will have by nick version
Organic coating is coated to the two-sided of barrier film, i.e. barrier film one side coated ceramic coating and organic coating, another side only coats organic coating.
Remaining is assembled into lithium ion battery 3, the battery core cross section structure of lithium ion battery 3 is as shown in Figure 2 with embodiment 1.
Embodiment 4
Difference with embodiment 1 is
4um oiliness AlN ceramic slurry, organic coating is coated by nick version respectively on two-sided AlN ceramic barrier film after drying.Remaining
With embodiment 1, lithium ion battery 4 is assembled into.
Embodiment 5
Difference with embodiment 4 is：Thickness 7um polyethylene is as barrier film base material, and porosity 40%, air permeability exists
180s/100ml；The particle size range of AlN ceramic powder is 0.1um, and AlN ceramic coating layer thickness is 3um；Organic polymer is to gather inclined fluorine
Ethene, organic coating thickness are 5um；The mass ratio of nickle cobalt lithium manganate, conductive agent and binding agent is 90:5:5；Graphite, conduction
The mass ratio of agent, thickener and aqueous binders is 91:4:2:3.Remaining is assembled into lithium ion battery 5 with embodiment 1.
Embodiment 6
Difference with embodiment 4 is：Thickness 16um polypropylene, polyethylene/polypropylene sandwich diaphragm is as barrier film
Base material, porosity 45%, air permeability is in 300s/100ml；The particle size range of AlN ceramic powder is 1um, AlN ceramic coating layer thickness
For 2um；Organic polymer is methyl acrylate, and organic coating thickness is 1um；The matter of nickle cobalt lithium manganate, conductive agent and binding agent
Amount ratio is 96:2:2；Graphite, conductive agent, the mass ratio of thickener and aqueous binders are 96:1:1:2.Remaining same embodiment
1, it is assembled into lithium ion battery 6.
Embodiment 7
Difference with embodiment 4 is：Thickness 20um polyimide film is as barrier film base material, porosity 60%, thoroughly
Manner is in 150s/100ml；The particle size range of AlN ceramic powder is 0.8um, and AlN ceramic coating layer thickness is 2.5um；Organic polymer
For butadiene-styrene rubber, organic coating thickness is 3um；The mass ratio of nickle cobalt lithium manganate, conductive agent and binding agent is 95：3：2；Stone
Ink, conductive agent, the mass ratio of thickener and aqueous binders are 95:2:1:2.Remaining is assembled into lithium ion battery with embodiment 1
7。
Embodiment 8
Difference with embodiment 4 is：Thickness 25um cellulose non-woven cloth diaphragm is as barrier film base material, porosity
55%, air permeability is in 100s/100ml；The particle size range of AlN ceramic powder is 0.3um, and AlN ceramic coating layer thickness is 3.5um；Have
Machine polymer is sodium carboxymethylcellulose, and organic coating thickness is 8um；The mass ratio of nickle cobalt lithium manganate, conductive agent and binding agent
Example is 92:3:5；Graphite, conductive agent, the mass ratio of thickener and aqueous binders are 92:4:1:3.Remaining is the same as embodiment 1, group
Dress up lithium ion battery 8.
Comparative example 1
Difference with embodiment 1 is：Barrier film is without any coating 16um polypropylene.Remaining is assembled into lithium with embodiment 1
Ion battery 9.
Comparative example 2
Difference with embodiment 1 is, AlN ceramic slurry is applied by the coating method of intaglio plate in the one side of barrier film
Cover, obtain the barrier film that a face coating layer thickness is 4um after drying, no longer coat organic coating.Remaining is assembled into embodiment 1
Lithium ion battery 10.
The test result of the lithium ion battery 1-10 different multiplyings electric discharge of above-described embodiment is as shown in table 1, by lithium-ion electric
Pond 1-10 carries out discharge energy density HPPC tests (50%SOC, 15C constant-current discharge 10 seconds), as shown in table 2.
When high-power 30C discharges, its lithium ion battery 1,2 is higher than the electric discharge of the lithium ion battery 9,10 in comparative example
Efficiency, and the surface temperature peak value of lithium ion battery reduces, security performance gets a promotion.
Table 1
Lithium ion battery 1-10 is subjected to discharge energy density HPPC tests (50%SOC, 15C constant-current discharge 10 seconds), such as
Shown in table 2, the power-performance of embodiment 1-2 lithium ion battery is significantly improved.
Table 2
Reference picture 3 and Fig. 4, by the lithium ion battery 1 of embodiment 1 and the lithium ion battery 9 of comparative example 1 in 3C/3C charge and discharges
In electric cyclic process, lithium ion battery thickness was tested and recorded in every 500 weeks, as illustrated, the thickness of lithium ion battery 1
Change is smaller, and effectively improves battery electricity in high-power cyclic process using the scattered coating strip organic coating in gap
The problem of core dilatancy, cycle performance is guaranteed.
The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the scope of the invention, every utilization
The equivalent structure or equivalent flow conversion that description of the invention and accompanying drawing content are made, or directly or indirectly it is used in other correlations
Technical field, be included within the scope of the present invention.
Claims (10)
1. a kind of barrier film, it is characterised in that including barrier film base material and organic coating, the organic coating is by with caking property
The single or double that organic polymer is distributed in the barrier film base material with the appointed thickness strip of the scattered coating in gap is formed.
2. barrier film according to claim 1, it is characterised in that also have including ceramic coating, the ceramic coating with described
Organic coating is located at the coplanar and/or antarafacial of barrier film.
3. barrier film according to claim 2, it is characterised in that the ceramic coating is located at barrier film with the organic coating
It is coplanar, and the ceramic coating is between the barrier film base material and the organic coating.
4. the barrier film according to Claims 2 or 3, it is characterised in that the ceramic coating will be by that will be scattered in organic solvent
Aluminium nitride be coated on the surface of the barrier film base material and formed.
5. barrier film according to claim 4, it is characterised in that the particle size range of the aluminium nitride includes 0.1um to 1um；
The thickness range of the ceramic coating includes：2um to 4um.
6. barrier film according to claim 1, it is characterised in that the organic polymer includes Kynoar, butylbenzene rubber
One or more in glue, methyl acrylate, sodium carboxymethylcellulose, polyacrylic acid；The thickness range bag of the organic coating
1um is included to 10um.
7. barrier film according to claim 1, it is characterised in that the barrier film base material includes polypropylene, polyethylene, poly- third
It is a kind of in alkene/polyethylene/polypropylene sandwich diaphragm, polyimide film, cellulose non-woven cloth diaphragm；The thickness of the barrier film base material
Degree scope includes 7um to 25um；The porosity ranges 40% to 60% of the barrier film base material；The air permeability model of the barrier film base material
Enclose including 100s/100ml to 300s/100ml.
8. a kind of lithium ion battery, it is characterised in that including the barrier film any one of claim 1-7, in addition to positive pole
Piece, negative plate and electrolyte；The barrier film is between the positive plate and the negative plate, described in the electrolyte infiltration
Whole interfaces of positive plate, negative plate and barrier film.
9. lithium ion battery according to claim 8, it is characterised in that the positive plate includes aluminium foil and coated on institute
State nickel-cobalt lithium manganate cathode material, conductive agent and the binding agent on aluminium foil；The nickel-cobalt lithium manganate cathode material, conductive agent and viscous
Knot agent mass ratio be：90~96：2~5：2~5.
10. lithium ion battery according to claim 8, it is characterised in that the negative plate includes copper foil and is coated on
Graphite, conductive agent, thickener and the aqueous binders of the copper foil；The graphite, conductive agent, thickener and aqueous binders
Mass ratio is 91~96：1~4：1~2：2~3.
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| CN201711125086.0A CN107834007A (en) | 2017-11-14 | 2017-11-14 | Barrier film and lithium ion battery |
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Application publication date: 20180323 |