CN105990550A - Composite separator membrane, preparation method thereof, and application thereof in lithium ion batteries - Google Patents
Composite separator membrane, preparation method thereof, and application thereof in lithium ion batteries Download PDFInfo
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- CN105990550A CN105990550A CN201510042148.6A CN201510042148A CN105990550A CN 105990550 A CN105990550 A CN 105990550A CN 201510042148 A CN201510042148 A CN 201510042148A CN 105990550 A CN105990550 A CN 105990550A
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Abstract
The invention provides a composite separator membrane which includes a separator membrane and a conductor material coating which is composited on the surface of the separator membrane. The conductor material coating includes a garnet conductor material. The conductor material coating on the surface of the separator membrane contains the garnet conductor material, so that during charging and discharging of a lithium ion battery, the separator membrane can supply a path for transmitting lithium ions, so that damage on the charging and discharging performance of the lithium ion battery is avoided due to existence of the path in the garnet conductor material even the surface of the separator membrane is coated with the coating and the porosity of the surface of the separator membrane is reduced, and meanwhile, a long cycle life is achieved. The invention also provides a preparation method of the composite separator membrane and an application thereof in the lithium ion batteries.
Description
Technical field
The present invention relates to technical field of lithium ion, particularly relate to a kind of composite diaphragm, its system
Preparation Method and its application in lithium ion battery.
Background technology
The application of lithium ion battery is still based on the lithium ion battery of liquid electrolyte, its
The critical piece constituting includes positive pole, negative pole, electrolyte and barrier film.Its septation is lithium ion
The interior layer assembly of battery most critical and core material, the capacity of battery, security, circulation ability
All have with barrier film with key performances such as fast charging and discharging abilities and directly contact, diaphragm material enter one
Step optimization can solve lithium ion battery specific energy and security the two problem simultaneously.Tradition side
Formula uses the electrolyte of liquid to combine simple high molecular barrier film, but lithium ion battery cannot make
With lithium metal as negative pole, thus limit the raising further of battery performance.Meanwhile, high score
The heat resistanceheat resistant performance of sub-barrier film also can affect the security feature of battery.
Apple and three magnitude electronic equipments remain unchanged and select the lithium ion battery of liquid electrolyte, at present
Electric automobile tesla the most fiery use equally Panasonic make the lithium-ion electric of liquid electrolyte
Pond, but upgrading is optimized to diaphragm material, use the high score with inorganic coat
Sub-barrier film.
The polymer separators of inorganic coat can effectively prevent inside battery thermal runaway and lithium branch
Brilliant and the short circuit that occurs.But, the inorganic coat of polymer separators is mainly high-purity nano
Al2O3, it belongs to non-lithium ion conductor.Employing has inorganic particle (as aluminum oxide, zirconium aoxidize
The non-lithium ion conductor such as thing, titanium oxide) work preventing thermal contraction is played as the barrier film of filler
With, it is possible to increase the security of battery, but battery trends towards showing bad charge/discharge
Characteristic.Particularly under relatively large electric current to battery charging and discharging when, battery at low ambient temperatures
Performance significantly reduces, and this is to be filled with inorganic particle, therefore, nothing densely owing to porous is intermembranous
Machine filler particles does not only play the raising effect in front for lithium ion battery, and non-lithium
Ion conductor oxide has a possibility intercepting lithium ion fast transferring, thus lithium ion battery
Rapid charge/flash-over characteristic is impaired, and can not in low temperature environment charge/discharge.
Publication number is respectively in CN103296235A and CN103236511A patent application, all
It is to use the non-lithium ion conductor of inorganic oxide as diaphragm material, above-mentioned two patent septation
The increase of thickness and the resistance that increases composite diaphragm, simultaneously fine and close inorganic oxide nonionic is led
Know from experience the volume ratio reducing membrane surface Porous hollow gap, reduce ionic diffusion coefficient and ion-conductance
Conductance, reduces battery actual capacity, makes rapid charge/discharge performance impaired.
Content of the invention
Present invention solves the technical problem that and be to provide a kind of composite diaphragm and preparation method thereof, this
The composite diaphragm that application provides can improve high-rate charge-discharge capability and the circulation of lithium ion battery
Performance.
In view of this, this application provides a kind of composite diaphragm, comprising: barrier film, be compound in institute
State the conductor material coating of membrane surface；Described conductor material coating includes carbuncle type conductor material
Material.
Preferably, described carbuncle type conductor material is the lithium ion conductor as shown in formula (I):
LixA3B2CδO12±λ(Ⅰ)；
3≤x≤8,0≤λ≤1,0≤δ≤1；
A selected from Na, K, Mg, Ca, Sr, Ba, Sc, Y, Al, Cr, Fe, Mo,
La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu
In one or more；When A is selected from more than one elements, each Elements Atom summation is 3；
B selected from Zr, Hf, Nb, Ta, W, In, Sb, Bi, Te, Y, Al, Cr, Fe,
Mo, La, Sc, Ba, Sr, Ca, Sn and one or more in Mg；When B is selected from one
When planting above element, each Elements Atom summation is 2；
One or more in B, Ga, Al, In, Tl, Bi, Y, Cr with Fe of C.
Preferably, A selected from K, Mg, Ca, Sr, Ba, La, Ta, Nd, Gd, Er,
Tb, Y and one or more in Lu；When A is selected from more than one elements, each pantogen
Sub-summation is 3；
B is in Zr, Hf, Nb, Ta, W, Zn, Sb, Bi, Te, Y, La with Sn
One or more；When B is selected from more than one elements, each Elements Atom summation is 2；
C is selected from one or both in Ga and Al.
Preferably, described conductor material is Li5La3Ta2O12、Li7La3Zr2O12、
Li5La3Nb2O12、Li5Ln3Sb2O12、Li3Nd3Te2O12、Li3Gd3Te2O12、Li3Tb3Te2O12、
Li3Er3Te2O12、Li3Lu3Te2O12、Li3.5Nd3Te1.5Sb0.5O12、Li6BaLa2Ta2O12、
Li5La3Sb2O12、Li5La3Bi2O12、Li5Nd3Ta2O12、Li5Nd3Sb2O12、
Li5.2La3Nb1.9Y0.1O12、Li5.5La3Nb1.75In0.25O12、Li5.5La2.75K0.25Nb2O12、
Li6.25La3Zr2Ga0.25O12、Li6MgLa2Ta2O12、Li6CaLa2Nb2O12、
Li6CaLa2Ta2O12、Li6BaLa2Nb2O12、Li7BaLa2Nb2O12.5、
Li6.6La3Zr1.6Sb0.4O12、Li6.75La3Zr1.75Ta0.25O12、Li7La3Sn2O12、
Li7La3Hf2O12、Li7.16La3Zr1.84Ga0.16O12、Li3Y3Te2O12、Li7La3Zr2O12、
Li7La3Ta2O13、Li6.15La3Zr1.75Ta0.25Al0.2O12、Li6.4La3Zr1.7W0.3O12、
Li6.75La3Zr1.75Nb0.25O12Or Li7.06La3Zr1.94Y0.06O12。
Preferably, A is selected from one or both in La and Y；When A is selected from two kinds of elements,
Each Elements Atom summation is 3；
One or more in Zr, Nb, Ta, W, Te with Y of B；When B is selected from one
When planting above element, each Elements Atom summation is 2；
C is selected from one or both in Ga and Al.
Preferably, the thickness of described conductor material coating is 0.3～10 μm.
Preferably, described barrier film is polypropylene-polyethylene-polypropylene diaphragm.
Present invention also provides the preparation method of composite diaphragm described in a kind of such scheme, including with
Lower step:
Adhesive, organic solvent are mixed with carbuncle type conductor material, is suspended after dispersion
Liquid；
Described suspension is obtained composite diaphragm after membrane surface, drying.
Preferably, described adhesive is polyvinylidene fluoride, and described organic solvent is N-methyl pyrrole
Pyrrolidone.
Present invention also provides application in lithium ion battery for the described composite diaphragm.
This application provides a kind of composite diaphragm, including barrier film be compound in described membrane surface
Conductive material coating, described conductive material coating includes carbuncle type conductor material.The present invention exists
It is compounded with carbuncle type conductor material coating, when discharge and recharge, owing to carbuncle type is led on barrier film
Body material can provide Li+Passage, even if therefore the porosity on composite diaphragm surface declines, right
Extending influence of lithium ion is minimum so that it is have the ionic conductivity suitable with uncoated barrier film；
Compared with inorganic oxide coating barrier film, the high-rate characteristics of lithium ion battery will not be impacted,
And cycle life strengthens, battery trends towards showing more excellent charge/discharge characteristics.In addition,
Owing to the conductor material coating of composite diaphragm is electrophilic solution liquid status, its surface exists fine in a large number
Gap, electrolyte is possible not only to sprawl at conductor material surface, can also pass through capillarity,
Enter inside conductor material coating, good to the wellability of electrolyte, there are enough imbibition moisturizing energy
Power；The conductor material coating on composite diaphragm surface belongs to inorganic dielectric layers simultaneously, and its fusing point is high,
When membrane surface shrinks and even melts, the existence that dielectric substrate can also be stable, effectively prolong
Slow barrier film deforms upon so that it is keeps certain shape, thus alleviates the possibility of short circuit,
Reach to protect the effect of battery.
The composite diaphragm wetability that the application provides is good, electrical conductivity is high, Heat stability is good, application
In lithium ion battery, the generation that both can reduce short circuit phenomenon improves battery security, also can
The high-rate characteristics making lithium ion battery is unaffected, and cycle life strengthens, and battery trends towards table
Now more excellent charge/discharge characteristics, thus there is very wide application prospect.
Brief description
Fig. 1 is tradition inorganic material coat Li+Transmission route schematic diagram；
The conductor material coating Li that Fig. 2 provides for the application+Transmission route schematic diagram；
Fig. 3 is the composite diaphragm profile scanning photo of the embodiment of the present invention 1 preparation；
Fig. 4 is that the composite diaphragm of the embodiment of the present invention 1 drips electrolyte surface with organic battery barrier film
Infiltration photo；
Fig. 5 is composite diaphragm and the organic battery barrier film thermal contraction curve of the embodiment of the present invention 1
Figure；
The lithium ion battery of composite diaphragm with organic barrier film for using the embodiment of the present invention 1 for the Fig. 6
Discharge performance curve map；
The lithium ion of composite diaphragm with organic barrier film for using the embodiment of the present invention 1 preparation for the Fig. 7
The high rate performance curve map of battery；
Fig. 8 is composite diaphragm and the organic battery barrier film thermal contraction curve of the embodiment of the present invention 2
Figure；
Fig. 9 is composite diaphragm and the organic battery barrier film thermal contraction curve of the embodiment of the present invention 3
Figure；
Figure 10 is composite diaphragm and the organic battery barrier film thermal contraction curve of the embodiment of the present invention 4
Figure；
Figure 11 is composite diaphragm and the organic battery barrier film thermal contraction curve of the embodiment of the present invention 5
Figure；
Figure 12 is composite diaphragm and the organic battery barrier film thermal contraction curve of the embodiment of the present invention 6
Figure；
Figure 13 is composite diaphragm and the organic battery barrier film thermal contraction curve of the embodiment of the present invention 7
Figure；
Figure 14 is composite diaphragm and the organic battery barrier film thermal contraction curve of the embodiment of the present invention 8
Figure；
Figure 15 is composite diaphragm and the organic battery barrier film thermal contraction curve of the embodiment of the present invention 9
Figure；
Figure 16 is composite diaphragm and the organic battery barrier film thermal contraction curve of the embodiment of the present invention 10
Figure.
Detailed description of the invention
In order to be further appreciated by the present invention, below in conjunction with embodiment to the preferred embodiment of the invention
It is described, but it is to be understood that these describe simply as further illustrating inventive feature
And advantage, rather than limiting to the claimed invention.
The embodiment of the invention discloses a kind of composite diaphragm, comprising: barrier film, be compound in described every
The conductor material coating on film surface；Described conductor material coating includes carbuncle type conductor material,
The preferably lithium ion conductor as shown in formula (I):
LixA3B2CδO12±λ(Ⅰ)；
3≤x≤8,0≤λ≤1,0≤δ≤1；
A selected from Na, K, Mg, Ca, Sr, Ba, Sc, Y, Al, Cr, Fe, Mo,
La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu
In one or more；When A is selected from more than one elements, each Elements Atom summation is 3；
B selected from Zr, Hf, Nb, Ta, W, In, Sb, Bi, Te, Y, Al, Cr, Fe,
Mo, La, Sc, Ba, Sr, Ca, Sn and one or more in Mg；When B is selected from one
When planting above element, each Elements Atom summation is 2；
One or more in B, Ga, Al, In, Tl, Bi, Y, Cr with Fe of C.
Further, A selected from K, Mg, Ca, Sr, Ba, La, Nd, Gd, Er, Tb,
One or more in Y and Lu；When A is selected from more than one elements, each Elements Atom is total
With for 3；
B is in Zr, Hf, Nb, Ta, W, Zn, Sb, Bi, Te, Y, La with Sn
One or more；When B is selected from more than one elements, each Elements Atom summation is 2；
C is selected from one or both in Ga and Al.
Preferably, A is selected from one or both in La and Y；When A is selected from two kinds of elements,
Each Elements Atom summation is 3；
One or more in Zr, Nb, Ta, W, Te with Y of B；When B is selected from one
When planting above element, each Elements Atom summation is 2.
C is selected from one or both in Ga and Al.
Lithium Ionic Conducting Materials as described in formula (I) can include but is not limited to following compound:
Li5La3Ta2O12、Li7La3Zr2O12、Li5La3Nb2O12、Li5Ln3Sb2O12、Li3Nd3Te2O12、
Li3Gd3Te2O12、Li3Tb3Te2O12、Li3Er3Te2O12、Li3Lu3Te2O12、
Li3.5Nd3Te1.5Sb0.5O12、Li6BaLa2Ta2O12、Li5La3Sb2O12、Li5La3Bi2O12、
Li5Nd3Ta2O12、Li5Nd3Sb2O12、Li5.2La3Nb1.9Y0.1O12、
Li5.5La3Nb1.75In0.25O12、Li5.5La2.75K0.25Nb2O12、Li6.25La3Zr2Ga0.25O12、
Li6MgLa2Ta2O12、Li6CaLa2Nb2O12、Li6CaLa2Ta2O12、Li6BaLa2Nb2O12、
Li7BaLa2Nb2O12.5、Li6.6La3Zr1.6Sb0.4O12、Li6.75La3Zr1.75Ta0.25O12、
Li7La3Sn2O12、Li7La3Hf2O12、Li7.16La3Zr1.84Ga0.16O12、Li3Y3Te2O12、
Li7La3Zr2O12、Li7La3Ta2O13、Li6.15La3Zr1.75Ta0.25Al0.2O12、
Li6.4La3Zr1.7W0.3O12Or Li7.06La3Zr1.94Y0.06O12；More preferably Li3Y3Te2O12、
Li5La3Ta2O12、Li7La3Zr2O12、Li7La3Ta2O13、Li6.25La3Zr2Ga0.25O12、
Li6.15La3Zr1.75Ta0.25Al0.2O12、Li6.4La3Zr1.7W0.3O12、
Li6.75La3Zr1.75Nb0.25O12、Li5.5La3Nb1.75In0.25O12、Li6.75La3Zr1.75Nb0.25O12
Or Li7.06La3Zr1.94Y0.06O12。
(Fig. 1 is tradition inorganic material such as alundum (Al2O3) coating to herein described conductor material
Layer Li+Transmission route schematic diagram, the conductor material coating Li that Fig. 2 provides for the application+Transmission road
Line schematic diagram) Fig. 1 and 2 is understood that it has the passage of lithium ion transport, therefore lithium ion can
To be directly transmitted, it has higher lithium ion diffusion coefficient and ion than inorganic oxide
Electrical conductivity, make composite diaphragm keep good heat endurance, infiltrating while, also can make lithium
The high-rate characteristics of ion battery is unaffected, and cycle life strengthens, and battery trends towards showing more
Add excellent charge/discharge characteristics.
The material that conductor material described herein refers to that resistivity is very little and is easy to conduct electric current.
Herein described conductor material has garnet structure, and it contains the eight-coordinate of oxonium ion, six joins
Position and four-coordination, and various cation is in different valence states, is not therefore changing conductor material
On the premise of crystal phase structure, the introducing of different valence state cation can change ion transmission channel
Size, simultaneously because charge balance can introduce more transportable lithium ion, thus is conducive to
Improve the transmission route of lithium ion, and then improve the performance of lithium ion battery.The application is to described
The source of carbuncle type conductor material has no particular limits, and knows according to those skilled in the art
Mode prepare.
Herein described carbuncle type conductor material is preferably glassy state, pottery state or glass ceramics
State, when described carbuncle type conductor material is above-mentioned three kinds of states, it has as diaphragm material
Higher ionic conductivity, and be conducive to improving the performance of battery.
Barrier film described herein refers between anode and negative pole, and isolation positive and negative electrode is simultaneously
Make the electronics in battery not pass freely through, allow the ion in electrolyte between both positive and negative polarity freely
The material passing through.The species of barrier film described herein does not has concrete restriction, is selected from weaving
Film, nowoven membrane (non-woven fabrics), microporous barrier, composite membrane, diaphragm paper, laminate；It is preferably
TPO barrier film or non-woven fabrics barrier film, TPO barrier film be selected from monolayer polyethylene barrier film,
Double-layer polyethylene barrier film, single-layer polypropylene barrier film, double-deck polypropylene diaphragm, polyethylene polypropylene
Two-layer separator, ceramic coated polyethylene diagrams and the one or many in ceramic coated polypropylene diaphragm
Kind, more preferably three layers of composite diaphragm of polypropylene-polyethylene-polypropylene.Herein described conductor
The thickness of material coating does not has concrete restriction, can be 0.3～10 μm, preferably 1～3 μm,
More preferably 2 μm.Conductor material in conductor material coating described herein is conducive to
The passage of lithium ion transport, therefore has higher lithium ion diffusion coefficient and ionic conductivity,
Thus do not affect the performance of lithium ion battery.
Present invention also provides the preparation method of a kind of composite diaphragm, comprise the following steps:
Adhesive, organic solvent are mixed with carbuncle type conductor material, is suspended after dispersion
Liquid；
Described suspension is obtained composite diaphragm after membrane surface, drying.
The lithium ion that herein described carbuncle type conductor material is preferably as shown in formula (I) is led
Body:
LixA3B2CδO12±λ(Ⅰ)；
3≤x≤8,0≤λ≤1,0≤δ≤1；
A selected from Na, K, Mg, Ca, Sr, Ba, Sc, Y, Al, Cr, Fe, Mo,
La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu
In one or more；When A is selected from more than one elements, each Elements Atom summation is 3；
B selected from Zr, Hf, Nb, Ta, W, In, Sb, Bi, Te, Y, Al, Cr, Fe,
Mo, La, Sc, Ba, Sr, Ca, Sn and one or more in Mg；When B is selected from one
When planting above element, each Elements Atom summation is 2；
One or more in B, Ga, Al, In, Tl, Bi, Y, Cr with Fe of C.
During preparing composite diaphragm, the application is first by adhesive, organic solvent and stone
Garnet type conductor material mixes, and obtains suspension, then by suspension in membrane surface,
I.e. obtain composite diaphragm after drying.
Herein described adhesive refers to have sticking material, can be by two kinds points by its viscosity
From material link together.Herein described adhesive can include selected from natural glue but
It is not limited to the bioadhesives such as starch, protein, dextrin, animal glue, shellac, hide glue, rosin
Agent；Also the mineral binders such as pitch are included but is not limited to；Can include selected from artificial adhesive but
It is not limited to the inorganic bonds such as waterglass, and the organic bond such as synthetic resin, synthetic rubber.
Herein described adhesive is preferably the adhesive of electrolyte-resistant, including but not limited to fluorocarbon resin,
There is polymer or the polyacrylic acid derivative of caoutchouc elasticity, further preferably use and gather inclined difluoro
Ethene.
Herein described organic solvent be a class by the solvent that organic matter is medium, not particularly
Limiting, the organic solvent being well known to those skilled in the art, such as dimethylacetylamide
(DMAc), metacresol, cresols, dimethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO),
Chloroform (CHCl3), oxolane (THF), dichloromethane (CH2Cl2), toluene and diformazan
One or more in benzene, the application preferably employs 1-METHYLPYRROLIDONE as solvent.This Shen
Please described adhesive, organic solvent have no particular limits with the mass ratio of conductor material, preferably
For 1:(10-50): (5-30), more preferably 1:20:10.
The application, after mix adhesive, organic solvent with conductor material, disperses, makes
Conductor material can be evenly dispersed in adhesive and organic solvent, obtains suspension.This Shen
Described dispersion please refer to that conductor material is distributed in mixed system with tiny particle state, described
Scattered mode is not limited to specific mode, can for ball milling dispersion, sand milling dispersion, basket
Mill dispersion, ultrasonic disperse or dispersed with stirring.Herein described suspension refers to solid particle dispersions
In liquid, can not quickly sink because of Brownian movement and the solid dispersed phase that formed and liquid
Mixture.
According to the present invention, then described suspension is answered after membrane surface, drying
Close barrier film.The technique that described coating refers to be uniformly coated to coating on coated article surface.Institute
The mode the application stating coating does not particularly limit, and can be gravure coating process, curtain coating work
Skill, narrow slit technique, spraying coating process, silk-screen printing technique or dipping process etc., the application is preferred
Use narrow slit technique.Herein described barrier film can be TPO diaphragm material or non-woven fabrics every
Membrane material.What the application preferably employed is the polypropylene-polyethylene-polypropylene being sequentially overlapped setting
Composite diaphragm, the thickness of described barrier film does not limit, preferably 6 μm～25 μm, more preferably
9～16 μm.The application can be coated in the one side of barrier film also to carry out at the bilateral of barrier film
Coating, there is no particular limitation for the application.Barrier film after coating is finally dried by the application,
Described drying refers to remove the technical process that solvent retains solids content, described baking by some way
Dry mode does not has concrete restriction, preferably first dries in an oven, then at vacuum drying chamber
Middle drying.The temperature and time of described drying is without concrete restriction, and the temperature of described drying is preferred
Being 50～80 DEG C, the time of described drying is preferably 0.5h～24h.After drying, the application obtains
To composite diaphragm in the thickness of conductive material coating be preferably 0.3～10 μm.
The application by measure the absorbent of composite diaphragm, wettability, thermal stability with
Chemical property detects the performance of composite diaphragm, and the detection process of above-mentioned performance is as follows:
Absorbent: barrier film is soaked 15 minutes in the electrolytic solution, dried by filter paper after taking-up,
Weigh the quality before and after soaking, pick up=(m1-m0)/m0, m0For weight before imbibition, m1
For weight after imbibition；
Wettability: drop in electrolyte on barrier film, observes the infiltration at membrane surface for the electrolyte
Situation；
Heat endurance: by commodity barrier film and the prepared Ceramic Composite barrier film bought different
At a temperature of keep 30 minutes, contrast heat endurance by measuring its percent thermal shrinkage, its thermal contraction
Rate=(S0-S1)/S0, S0For the area of barrier film before heating, S1For heating the area of metacneme；
Chemical property: prepared Ceramic Composite barrier film is assembled into CR2032 buckle type lithium-ion
Battery carries out the test of chemical property, the discharge performance of test lithium ion battery and high rate performance.
This application provides a kind of composite diaphragm, including barrier film be compound in described membrane surface
Conductive material coating, described conductive material coating includes carbuncle type conductor material, preferably such as formula
(I) the conductor material shown in.The present invention is compounded with carbuncle type conductor material on barrier film and applies
Layer, when discharge and recharge, owing to carbuncle type conductor material can provide Li+Passage, be therefore
The porosity making composite diaphragm surface declines, minimum to extending influence of lithium ion so that it is to have
The ionic conductivity suitable with uncoated barrier film.With inorganic oxide coating barrier film compared with, lithium from
The high-rate characteristics of sub-battery will not be impacted, and cycle life strengthens, and battery trends towards performance
More excellent charge/discharge characteristics.Further, since the conductor material coating of composite diaphragm is parent
Electrolyte state, there is a large amount of fine gap in its surface, electrolyte is possible not only at conductor material
Surface spreading, can also pass through capillarity, enters inside conductor material coating, to electrolyte
Wellability good, have enough imbibition moisture-retaining capacity；The conductor material on composite diaphragm surface simultaneously
Coating belongs to inorganic dielectric layers, and its fusing point is high, when membrane surface shrinks and even melts,
Dielectric substrate can also be stable existence, effectively delay barrier film to deform upon so that it is to keep certain
Shape, thus alleviate the possibility of short circuit, reach to protect the effect of battery.
The composite diaphragm wetability that the application provides is good, electrical conductivity is high, Heat stability is good, application
In lithium ion battery, the generation that both can reduce short circuit phenomenon improves battery security, also can
The high-rate characteristics making lithium ion battery is unaffected, and cycle life strengthens, and battery trends towards table
Now more excellent charge/discharge characteristics, thus there is very wide application prospect.
In order to be further appreciated by the present invention, below in conjunction with embodiment the present invention is provided compound every
Film and preparation method thereof is described in detail, and protection scope of the present invention is not by following example
Limit.
Embodiment 1
It is 0.3 micron of Li with average grain diameter3Y3Te2O12For ceramic layer, adhesive, organic solvent
Mass ratio with conductor material is 1:20:10, after three's mixing after planetary ball mill dispersion 2h, uses
The AFA-II automatic film applicator of Shanghai Pu Shen chemical machinery Co., Ltd is multiple PP-PE-PP tri-layers
Close and on barrier film (celgard 2300), carry out unilateral coating, in an oven after 60 DEG C of drying 4h,
It is transferred to 60 DEG C of continuation in vacuum drying oven and dries 10h, obtain Ceramic Composite barrier film.Coating before every
Film is 25 microns, and coating and dry metacneme thickness is 27 microns, is calculated coating layer thickness
It is 2 microns.Li3Y3Te2O12-PP-PE-PP composite diaphragm profile scanning electromicroscopic photograph such as Fig. 3
Shown in, coating thickness, pick up and conductivity data contrast are shown in Table 1, organic battery barrier film and
Li3Y3Te2O12Photo such as Fig. 4 institute of upper electrolyte solvent is dripped on ceramic coating composite diaphragm
Showing, a figure is PP-PE-PP composite diaphragm, and b figure is Li3Y3Te2O12-PP-PE-PP compound every
Film；Thermal contraction Data Comparison is shown in Fig. 5, and in figure, zero curve is that organic barrier film is processed at temperature undetermined
Percent thermal shrinkage curve, ● curve is that composite diaphragm prepared by the present embodiment is located at temperature undetermined
The percent thermal shrinkage curve of reason.
Button cell CR2032 is used to carry out charge-discharge performance test to it.With cobalt acid lithium for just
Pole, lithium metal as to electricity than electrode, composite diaphragm is as barrier film, 1mol/L
LiPF6(EC:DMC=1:1 volume ratio), as electrolyte, assembles in the glove box of argon shield
Become battery CR2032 button cell.Battery is carried out on Land tester rate charge-discharge
Test, the multiplying power of discharge and recharge is 0.2C, and charging/discharging voltage interval is 3.0～4.4V.Use PP-PE-PP/
Li3Y3Te2O12The battery 0.2C initial discharge capacity 153mAh/g of composite diaphragm, through 70 times
After circulation, capacity is 143mAh/g, and conservation rate is 94%, as shown in Figure 6,7.In Fig. 6 ●
The discharge performance curve of the lithium ion battery of the composite diaphragm that curve is prepared for using the present embodiment,
Zero curve is for using the discharge performance curve of the lithium ion battery of the organic barrier film of alundum (Al2O3)；Fig. 7
In ● the high rate performance of the lithium ion battery of the composite diaphragm that curve is prepared for using the present embodiment is bent
Line, zero curve is for using the high rate performance curve of the lithium ion battery of the organic barrier film of alundum (Al2O3).
Embodiment 2
It is 0.3 micron of Li with average grain diameter5La3Ta2O12For ceramic layer, adhesive, organic solvent
Mass ratio with conductor material is 1:20:10, after three's mixing after planetary ball mill dispersion 2h, uses
The AFA-II automatic film applicator of Shanghai Pu Shen chemical machinery Co., Ltd is multiple PP-PE-PP tri-layers
Close and on barrier film (celgard 2300), carry out unilateral coating, in an oven after 60 DEG C of drying 4h,
It is transferred to 60 DEG C of continuation in vacuum drying oven and dry 10h.Obtain Li5La3Ta2O12Ceramic Composite every
Film.Coating thickness, pick up and conductivity data contrast are shown in Table 1, and thermal contraction Data Comparison is shown in
Fig. 8, in figure, zero curve is the percent thermal shrinkage curve that organic barrier film is processed at temperature undetermined, ● bent
Line is the percent thermal shrinkage curve that composite diaphragm prepared by the present embodiment is processed at temperature undetermined.
Embodiment 3
It is 0.3 micron of Li with average grain diameter7La3Zr2O12For ceramic layer, adhesive, organic solvent
Mass ratio with conductor material is 1:20:10, after three's mixing after planetary ball mill dispersion 2h, uses
The AFA-II automatic film applicator of Shanghai Pu Shen chemical machinery Co., Ltd is multiple PP-PE-PP tri-layers
Close and on barrier film (celgard 2300), carry out unilateral coating, in an oven after 60 DEG C of drying 4h,
It is transferred to 60 DEG C of continuation in vacuum drying oven and dry 10h.Obtain Li7La3Zr2O12Ceramic Composite every
Film.Coating thickness, pick up and conductivity data contrast are shown in Table 2, and thermal contraction Data Comparison is shown in
Fig. 9, in figure, zero curve is the percent thermal shrinkage curve that organic barrier film is processed at temperature undetermined, ● bent
Line is the percent thermal shrinkage curve that composite diaphragm prepared by the present embodiment is processed at temperature undetermined.
Embodiment 4
It is 0.3 micron of Li with average grain diameter7La3Ta2O13For ceramic layer, adhesive, organic solvent
Mass ratio with conductor material is 1:20:10, after three's mixing after planetary ball mill dispersion 2h, uses
The AFA-II automatic film applicator of Shanghai Pu Shen chemical machinery Co., Ltd is multiple PP-PE-PP tri-layers
Close and on barrier film (celgard 2300), carry out unilateral coating, in an oven after 60 DEG C of drying 4h,
It is transferred to 60 DEG C of continuation in vacuum drying oven and dry 10h.Obtain Li7La3Ta2O13Ceramic Composite every
Film.Coating thickness, pick up and conductivity data contrast are shown in Table 2, and thermal contraction Data Comparison is shown in
Figure 10, in figure, zero curve is the percent thermal shrinkage curve that organic barrier film is processed at temperature undetermined, ●
Curve is the percent thermal shrinkage curve that composite diaphragm prepared by the present embodiment is processed at temperature undetermined.
Embodiment 5
Identical with the method that embodiment 1 prepares composite diaphragm, difference is: the present embodiment uses
Conductor material be Li6.25La3Zr2Ga0.25O12.The coating thickness of composite diaphragm, pick up number
Being shown in Table 1 according to contrast, thermal contraction Data Comparison is shown in Figure 11, and in Figure 11, zero curve is that organic barrier film exists
The percent thermal shrinkage curve processing at temperature undetermined, ● curve is composite diaphragm prepared by the present embodiment
The percent thermal shrinkage curve processing at temperature undetermined.
Embodiment 6
Identical with the method that embodiment 1 prepares composite diaphragm, difference is: the present embodiment uses
Conductor material be Li6.15La3Zr1.75Ta0.25Al0.2O12.The coating thickness of composite diaphragm, imbibition
Rate Data Comparison is shown in Table 1, and thermal contraction Data Comparison is shown in Figure 12, in Figure 12 zero curve be organic every
The percent thermal shrinkage curve that film is processed at temperature undetermined, ● curve be the present embodiment prepare compound
The percent thermal shrinkage curve that barrier film is processed at temperature undetermined.
Embodiment 7
Identical with the method that embodiment 1 prepares composite diaphragm, difference is: the present embodiment uses
Conductor material be Li6.4La3Zr1.7W0.3O12.The coating thickness of composite diaphragm, pick up data
Contrast is shown in Table 1, and thermal contraction Data Comparison is shown in Figure 13, and in Figure 13, zero curve is that organic barrier film is being treated
The percent thermal shrinkage curve processing under fixed temperature, ● curve is that composite diaphragm prepared by the present embodiment exists
The percent thermal shrinkage curve processing at temperature undetermined.
Embodiment 8
Identical with the method that embodiment 1 prepares composite diaphragm, difference is: the present embodiment uses
Conductor material be Li6.75La3Zr1.75Nb0.25O12.The coating thickness of composite diaphragm, pick up
Data Comparison is shown in Table 1, and thermal contraction Data Comparison is shown in Figure 14, and in Figure 14, zero curve is organic barrier film
The percent thermal shrinkage curve processing at temperature undetermined, ● curve be the present embodiment prepare compound every
The percent thermal shrinkage curve that film is processed at temperature undetermined.
Embodiment 9
Identical with the method that embodiment 1 prepares composite diaphragm, difference is: the present embodiment uses
Conductor material be Li5.5La3Nb1.75In0.25O12.The coating thickness of composite diaphragm, pick up number
Being shown in Table 1 according to contrast, thermal contraction Data Comparison is shown in Figure 15, and in Figure 15, zero curve is that organic barrier film exists
The percent thermal shrinkage curve processing at temperature undetermined, ● curve is composite diaphragm prepared by the present embodiment
The percent thermal shrinkage curve processing at temperature undetermined.
Embodiment 10
Identical with the method that embodiment 1 prepares composite diaphragm, difference is: the present embodiment uses
Conductor material be Li7.06La3Zr1.94Y0.06O12.The coating thickness of composite diaphragm, pick up number
Being shown in Table 1 according to contrast, thermal contraction Data Comparison is shown in Figure 16, and in Figure 16, zero curve is that organic barrier film exists
The percent thermal shrinkage curve processing at temperature undetermined, ● curve is composite diaphragm prepared by the present embodiment
The percent thermal shrinkage curve processing at temperature undetermined.
The composite diaphragm of table 1 embodiment 1～10 preparation and the performance number of conventional composite membrane contrast
According to table
| Group | Thick deg micron | Pick up | Electrical conductivity |
| PP-PE-PP | 25 | 102 | 3.92×10-4S/cm |
| Embodiment 1 | 27 | 118 | 3.89×10-4S/cm |
| Embodiment 2 | 27 | 121 | 3.88×10-4S/cm |
| Embodiment 3 | 27 | 120 | 3.93×10-4S/cm |
| Embodiment 4 | 27 | 119 | 3.91×10-4S/cm |
| Embodiment 5 | 27 | 123 | 3.92×10-4S/cm |
| Embodiment 6 | 27 | 122 | 3.95×10-4S/cm |
| Embodiment 7 | 27 | 120 | 3.93×10-4S/cm |
| Embodiment 8 | 27 | 122 | 3.89×10-4S/cm |
| Embodiment 9 | 27 | 121 | 3.93×10-4S/cm |
| Embodiment 10 | 27 | 119 | 3.92×10-4S/cm |
The explanation of above example is only intended to help to understand that the method for the present invention and core thereof are thought
Think.It should be pointed out that, for those skilled in the art, without departing from this
On the premise of bright principle, the present invention can also be carried out some improve and modify, these improve and
Modify in the protection domain also falling into the claims in the present invention.
Described above to the disclosed embodiments, makes professional and technical personnel in the field be capable of
Or the use present invention.Those skilled in the art are come by the multiple modifications to these embodiments
Saying and will be apparent from, generic principles defined herein can be without departing from the present invention's
In the case of spirit or scope, realize in other embodiments.Therefore, the present invention will not be by
It is limited to the embodiments shown herein, and be to fit to and principles disclosed herein and new
The consistent scope the widest of grain husk feature.
Claims (10)
1. a composite diaphragm, comprising: barrier film, is compound in the conductor material of described membrane surface
Material coating；Described conductor material coating includes carbuncle type conductor material.
2. composite diaphragm according to claim 1, it is characterised in that described garnet
Type conductor material is the lithium ion conductor as shown in formula (I):
LixA3B2CδO12±λ(Ⅰ)；
3≤x≤8,0≤λ≤1,0≤δ≤1；
A selected from Na, K, Mg, Ca, Sr, Ba, Sc, Y, Al, Cr, Fe, Mo,
La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu
In one or more；When A is selected from more than one elements, each Elements Atom summation is 3；
B selected from Zr, Hf, Nb, Ta, W, In, Sb, Bi, Te, Y, Al, Cr, Fe,
Mo, La, Sc, Ba, Sr, Ca, Sn and one or more in Mg；When B is selected from one
When planting above element, each Elements Atom summation is 2；
One or more in B, Ga, Al, In, Tl, Bi, Y, Cr with Fe of C.
3. composite diaphragm according to claim 2, it is characterised in that A selected from K,
Mg, Ca, Sr, Ba, La, Nd, Gd, Er, Tb, Y and one or more in Lu；
When A is selected from more than one elements, each Elements Atom summation is 3；
B is in Zr, Hf, Nb, Ta, W, Zn, Sb, Bi, Te, Y, La with Sn
One or more；When B is selected from more than one elements, each Elements Atom summation is 2；
C is selected from one or both in Ga and Al.
4. composite diaphragm according to claim 3, it is characterised in that described conductor material
For Li5La3Ta2O12、Li7La3Zr2O12、Li5La3Nb2O12、Li5Ln3Sb2O12、
Li3Nd3Te2O12、Li3Gd3Te2O12、Li3Tb3Te2O12、Li3Er3Te2O12、Li3Lu3Te2O12、
Li3.5Nd3Te1.5Sb0.5O12、Li6BaLa2Ta2O12、Li5La3Sb2O12、Li5La3Bi2O12、
Li5Nd3Ta2O12、Li5Nd3Sb2O12、Li5.2La3Nb1.9Y0.1O12、
Li5.5La3Nb1.75In0.25O12、Li5.5La2.75K0.25Nb2O12、Li6.25La3Zr2Ga0.25O12、
Li6MgLa2Ta2O12、Li6CaLa2Nb2O12、Li6CaLa2Ta2O12、Li6BaLa2Nb2O12、
Li7BaLa2Nb2O12.5、Li6.6La3Zr1.6Sb0.4O12、Li6.75La3Zr1.75Ta0.25O12、
Li7La3Sn2O12、Li7La3Hf2O12、Li7.16La3Zr1.84Ga0.16O12、Li3Y3Te2O12、
Li7La3Zr2O12、Li7La3Ta2O13、Li6.15La3Zr1.75Ta0.25Al0.2O12、
Li6.4La3Zr1.7W0.3O12、Li6.75La3Zr1.75Nb0.25O12Or Li7.06La3Zr1.94Y0.06O12。
5. composite diaphragm according to claim 3, it is characterised in that A selected from La with
One or both in Y；When A is selected from two kinds of elements, each Elements Atom summation is 3；
One or more in Zr, Nb, Ta, W, Te with Y of B；When B is selected from one
When planting above element, each Elements Atom summation is 2；
C is selected from one or both in Ga and Al.
6. composite diaphragm according to claim 1, it is characterised in that described conductor material
The thickness of material coating is 0.3～10 μm.
7. composite diaphragm according to claim 1, it is characterised in that described barrier film is
Polypropylene-polyethylene-polypropylene diaphragm.
8. the preparation method of composite diaphragm as described in claim 1～7 any one, bag
Include following steps:
Adhesive, organic solvent are mixed with carbuncle type conductor material, is suspended after dispersion
Liquid；
Described suspension is obtained composite diaphragm after membrane surface, drying.
9. preparation method according to claim 8, it is characterised in that described adhesive
For polyvinylidene fluoride, described organic solvent is 1-METHYLPYRROLIDONE.
10. one kind as described in claim 1～7 any one composite diaphragm in lithium ion battery
Application.
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| CN106684292A (en) * | 2017-01-18 | 2017-05-17 | 清陶（昆山）能源发展有限公司 | Ionic conductor ceramic fiber composite diaphragm and preparation method and application thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101542777A (en) * | 2007-02-05 | 2009-09-23 | Lg化学株式会社 | Organic/inorganic composite separator having porous active coating layer and electrochemical device containing the same |
| CN103682216A (en) * | 2013-11-01 | 2014-03-26 | 中国第一汽车股份有限公司 | Lithium ion battery separator containing poly-dopamine and ceramic coatings |
| CN103988337A (en) * | 2011-12-16 | 2014-08-13 | 罗伯特·博世有限公司 | Separator having a polysulphide barrier layer for lithium-sulphur cells |
| CN104051688A (en) * | 2013-03-15 | 2014-09-17 | 通用汽车环球科技运作有限责任公司 | Coating for separator or cathode of lithium-sulfur or silicon-sulfur battery |
-
2015
- 2015-01-28 CN CN201510042148.6A patent/CN105990550A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101542777A (en) * | 2007-02-05 | 2009-09-23 | Lg化学株式会社 | Organic/inorganic composite separator having porous active coating layer and electrochemical device containing the same |
| CN103988337A (en) * | 2011-12-16 | 2014-08-13 | 罗伯特·博世有限公司 | Separator having a polysulphide barrier layer for lithium-sulphur cells |
| CN104051688A (en) * | 2013-03-15 | 2014-09-17 | 通用汽车环球科技运作有限责任公司 | Coating for separator or cathode of lithium-sulfur or silicon-sulfur battery |
| CN103682216A (en) * | 2013-11-01 | 2014-03-26 | 中国第一汽车股份有限公司 | Lithium ion battery separator containing poly-dopamine and ceramic coatings |
Cited By (15)
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| CN106941190A (en) * | 2017-04-14 | 2017-07-11 | 中国科学院宁波材料技术与工程研究所 | The preparation method of garnet-type solid electrolyte material |
| JP2019121464A (en) * | 2017-12-28 | 2019-07-22 | トヨタ自動車株式会社 | Separator for battery, lithium battery, and manufacturing methods thereof |
| JP2019121463A (en) * | 2017-12-28 | 2019-07-22 | トヨタ自動車株式会社 | battery |
| CN110707267A (en) * | 2018-07-10 | 2020-01-17 | 中国科学院大连化学物理研究所 | Composite diaphragm for alkali metal battery and preparation and application thereof |
| CN110707267B (en) * | 2018-07-10 | 2022-03-29 | 中国科学院大连化学物理研究所 | Composite diaphragm for alkali metal battery and preparation and application thereof |
| CN109119573A (en) * | 2018-08-02 | 2019-01-01 | 山东理工大学 | The preparation method of lithium ion battery modified diaphragm |
| CN111719183A (en) * | 2019-03-21 | 2020-09-29 | 中国科学院理化技术研究所 | Magneto-optical crystal and preparation method and application thereof |
| CN110085791A (en) * | 2019-04-11 | 2019-08-02 | 电子科技大学 | A kind of lithium ion battery separator and preparation method thereof |
| CN110128140A (en) * | 2019-04-29 | 2019-08-16 | 内蒙古工业大学 | A kind of ytterbium aluminium codope carbuncle type Li7La3Zr2O12Lithium Ionic Conducting Materials and preparation method thereof |
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| CN111900309A (en) * | 2020-08-06 | 2020-11-06 | 莱西市寰球新能源技术中心 | High-cycle high-capacity performance battery |
| CN111900309B (en) * | 2020-08-06 | 2021-09-07 | 湖南盛利高新能源科技有限公司 | High-cycle high-capacity performance battery |
| CN114552129A (en) * | 2021-07-13 | 2022-05-27 | 万向一二三股份公司 | Two-sided differentiation lithium cell diaphragm and contain lithium cell of this diaphragm |
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