CN1918727A - Organic/inorganic composite porous layer-coated electrode and electrochemical device comprising the same - Google Patents
Organic/inorganic composite porous layer-coated electrode and electrochemical device comprising the same Download PDFInfo
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- CN1918727A CN1918727A CNA2005800042357A CN200580004235A CN1918727A CN 1918727 A CN1918727 A CN 1918727A CN A2005800042357 A CNA2005800042357 A CN A2005800042357A CN 200580004235 A CN200580004235 A CN 200580004235A CN 1918727 A CN1918727 A CN 1918727A
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Abstract
Disclosed is an electrode comprising a first organic/inorganic composite porous coating layer formed on its surface, wherein the first coating layer includes inorganic particles and a binder polymer for interconnecting and fixing the inorganic particles, and has micropores formed by interstitial volumes among the inorganic particles. An electrochemical device including the same electrode is also disclosed. Further, disclosed is a method for manufacturing an electrode having an organic/inorganic composite porous coating layer on the surface thereof, comprising the steps of: (a) coating a current collector with slurry containing an electrode active material and drying it to provide an electrode; and (b) coating the surface of electrode obtained from step (a) with a mixture of inorganic particles with a binder polymer. A lithium secondary battery including the electrode shows improved safety and minimized degradation in battery performance.
Description
Technical field
The present invention relates to a kind of electrode, it can improve the performance and the fail safe of electrochemical appliance.More specifically, relate to a kind of electrode, make the method for this electrode with coating, and the electrochemical appliance that contains this electrode, described coating can replace barrier film.
Background technology
Recently, people increase the interest of energy storage technology.Battery has been widely used in the power supply of portable phone, video camera, notebook computer, PC and Electric power car, causes people to strengthen research and development to them.For this reason, electrochemical appliance has caused very big interest.More specifically, chargeable secondary cell is the focus of paying close attention to.Recently, a large amount of research and development of the novel electrode and the battery of capacity density and specific energy have been carried out to improve in the secondary cell field.
In the secondary cell that uses at present, at operating voltage and battery that energy density is higher than traditional employing aqueous electrolyte (for example Ni-MH battery, Ni-Cd battery and the H of the early stage lithium secondary battery that the occurs nineties in 20th century
2SO
4-Pb battery etc.).Therefore, use lithium secondary battery very favourable.Yet the defective that this lithium secondary battery exists is the organic bath of its use, and it can cause because the fail safe relevant issues that battery is on fire or blast causes; And the process of making this battery is very complicated.
Assessment also guarantees that the fail safe of battery is very important.Most important consideration is that battery can not damage misoperation battery user.Because this purpose, should be limited in the battery security of the on fire and burning aspect of battery according to the safety standard strictness.Therefore, made the trial of a lot of solution battery associated safety problems.
In order to prevent the battery heating, several different methods has been proposed, comprise and adopt protective circuit and come thermal insulation etc. by dividing plate.Yet, adopt protective circuit can cause battery pack on reducing size and reducing cost, to be restricted.When heating produces rapidly, come adiabatic mechanism usually to lose efficacy by dividing plate.
Recently, also mention employing organic bath additive and solve the problems referred to above.Yet have defective based on the release mechanism of additive agent electrolyte: variation and selection of time (timing) are inhomogeneous along with the internal resistance variation of charging current and battery for its calorific value (J).In addition, the device that cuts off electric current with the battery pressure inside needs the space of inside battery to hold it, is not preferred aspect high power capacity therefore.And above-mentioned traditional safety method often follows other performance decrease of battery to descend.
Korean Patent Publication No. is that the method for 0326455,0326457 and 0374010 patent disclosure is that inorganic particle is coated on the cathode active material.Yet even this method can be improved the fail safe of battery, owing to do not have lithium-ion-conducting as the inorganic particle that applies agent, there is the defective that battery performance is descended in therefore this method.
Simultaneously, except above-mentioned safety problem, electrochemical appliance, for example lithium ion battery also exists and the present used relevant problem of barrier film.For example, lithium ion battery that uses at present and lithium ion polymer battery adopt polyolefin-based separator to prevent short circuit between negative electrode and the anode.Yet there is defective in this polyolefin-based separator, because the character of diaphragm material, for example polyolefin-based materials is being less than or equal to 200 ℃ of fusings down, and processing characteristics, the expanded material in order to control aperture and porosity for example is so barrier film can be retracted to original size when heat.Therefore when battery was heated to high temperature owing to the inner/outer factor, the contraction of barrier film or fusing probably caused the short circuit between negative electrode and anode.Therefore be necessary to provide a kind of barrier film that at high temperature can not produce thermal contraction.
In order to solve the above-mentioned problem relevant with polyolefin-based separator, existing many trial exploitation electrolyte wherein use inorganic material to replace traditional barrier film.This electrolyte broadly can be divided into two classes.The first kind is a composite solid electrolyte, and it obtains by inorganic particle that will not have lithium-ion-conducting and the polymer mixed with lithium-ion-conducting.Yet, well-known is to replace conventional membrane and liquid electrolyte is worthless with this composite electrolyte, reason is that the lithium-ion-conducting of this composite electrolyte is lower than liquid electrolyte, the interface resistance height when inorganic material and polymer mixed between them; When introducing excessive inorganic material, this composite electrolyte is because its fragility is not easy processing; And assembled battery is very difficult when adopting this composite electrolyte.Referring to Japan special permission publication No.2003-022707, [" Solid StateIonics "-vol.158, n.3, p.275, (2003)], [" Journal of Power Sources "-vol.112, n.1, p.209, and [" Electrochimica Acta "-vol.48 (2002)], n.14, p.2003, (2003)] etc.
Second class is that inorganic particle is mixed the electrolyte that obtains with gel polymer electrolyte, and this gelatin polymer is formed by polymer and liquid electrolyte.Referring to U.S. Patent No. 6544689, Japan special permission publication No.2002-008724 and No.1993-314995, international monopoly open No.WO02/092638 and WO00/038263, [" Journal ofElectrochemical Society " v.147, p.1251, (2000)], [" Solid StateIonics "-v.159, n.1, p.111, (2003)], [" Journal of Power Sources "-v.110, n.1, p.38, and [" Electrochimica Acta "-v.48 (2002)], n.3, p.227 (2002)] etc.Yet, because it is poor to be used for the cementitiousness of this electrolytical polymer, so can not adopt a large amount of inorganic material.Therefore, compare with liquid electrolyte with polymer, the amount of the inorganic material of introducing is relatively little, thereby only plays the booster action of the lithium-ion-conducting of assisting liquid electrolyte.And the ionic conductivity of this gel-type polymer electrolyte is lower than liquid electrolyte, has therefore reduced battery performance.
Particularly, the composite electrolyte that contains organic and/or inorganic materials of attempting being developed of major part up to now all is the form of independent (free standing) film.Yet because this electrolytical bad mechanical property, for example in fact the high fragility of film be difficult to it is applied to battery.
In addition, U.S. Patent No. 6432586 discloses the composite membrane that contains polyolefin-based separator, is coated with silicon dioxide on this barrier film, with mechanical performance such as the fragility of improving the organic/inorganic composite membrane.Yet because this film has still adopted polyolefin-based separator, its shortcoming is to improve fail safe significantly, prevents thermal contraction when comprising high temperature.In addition, Creavis Gesellschaft has developed a kind of organic/inorganic composite diaphragm, and this barrier film comprises the nonwoven polyester carrier, is coated with silicon dioxide (SiO on it
2) or aluminium oxide (Al
2O
3) etc.Yet the composite diaphragm of Creavis can not provide good mechanical performance owing to the fundamental characteristics of its nonwoven web.And because the chemical constitution of polyester is destroyed easily in the electrochemical reaction, the Creavis composite diaphragm has a lot of difficulties [" Desalination "-vol.146, p.23 (2002)] when being applied to battery.
Therefore, the technical research and development to the barrier film of the performance that can improve electrochemical appliance and fail safe are need to continue.
Description of drawings
In conjunction with the detailed description and the following accompanying drawing of back, aforesaid purpose, characteristics and advantage with other of the present invention can be more obvious:
Fig. 1 has electrode according to the first organic/inorganic composite porous coating of the present invention schematic diagram when being applied in the battery;
Fig. 2 is the schematic diagram that forms the step of second coating in the process of electrode constructed in accordance on the surface of electrode active material;
Fig. 3 shows scanning electron microscopy (SEM) photo that has according to the section structure of the electrode of the first organic/inorganic composite porous coating of the present invention;
Fig. 4 a and 4b are scanning electron microscopy (SEM) photos, respectively show the section structure of electrode with first organic/inorganic composite porous coating, wherein Fig. 4 a is the photo with electrode of coating formed according to the present invention, and Fig. 4 b is the photo with electrode of the coating that forms according to prior art (the plasticizer extraction is used to apply gel-type polymer electrolyte to electrode);
Fig. 5 is according to embodiment 1 (PVdF-CTFE/Al
2O
3) the first organic/inorganic composite porous coating and according to the polyalkene diaphragm of comparative example 1 150 ℃ place 1 hour down after, shrink the photo of contrast;
Fig. 6 comprises the figure that has according to the charge/discharge performance of the lithium secondary battery of the electrode of the first organic/inorganic composite porous coating of embodiment 1;
Fig. 7 comprises the figure that has according to the charge/discharge performance of the lithium secondary battery of the electrode of the first organic/inorganic composite porous coating of embodiment 6 and polyolefin-based separator;
Fig. 8 is the figure according to the high rate discharge performance of the lithium secondary battery of embodiment 1 and comparative example 1 (C-speed);
Fig. 9 is the figure according to the cycle performance of the lithium secondary battery of embodiment 1 and comparative example 1;
Figure 10 is to use the figure that overcharges the result of test (10V/1A) according to the lithium secondary battery of comparative example 1;
Figure 11 is to use the figure that overcharges the result of test (10V/1A) according to the lithium secondary battery of embodiment 1; And
Figure 12 is to use according to the lithium secondary battery of embodiment 1 and photo according to the result contrast of lithium secondary battery after overcharging test (10V/1A) under the identical condition of comparative example 1.
Summary of the invention
We have found that, organic/inorganic composite porous coating can be as the substitute of conventional membrane, and described compound porous coating is by at the direct coating inorganic particle of electrode surface and can form with the polymer of liquid electrolyte swelling (swellable).And, above-mentioned organic/inorganic composite porous coating combines (bonded) securely on the interface with electrode, can not cause thermal contraction, thereby can solve the problems referred to above relevant, and can improve the performance and the fail safe of the electrochemical appliance that comprises the electrode that scribbles this coating with conventional membrane.
Therefore, a target of the present invention provides a kind of electrode with organic/inorganic composite porous coating, and it can improve the performance and the fail safe of electrochemical appliance, the electrochemical appliance of making the method for this electrode and comprising this electrode.
According to an aspect of the present invention, a kind of electrode is provided, this electrode has the first organic/inorganic composite porous coating that forms on its surface, wherein first coating comprises inorganic particle and adhesive polymer, this polymer is used to make inorganic particle to interconnect and is fixing, and the interstitial volume between the inorganic particle forms micropore.A kind of electrochemical appliance that contains this electrode also is provided.
According to another aspect of the present invention, provide a kind of method of making electrode, this electrode has the organic/inorganic composite porous coating that forms on its surface.This method comprises the steps: that slurry that (a) will contain electrode active material is coated to that current-collector (current collector) is gone up and is dry, to obtain electrode; (b) mixture of inorganic particle and adhesive polymer is coated to the surface of the electrode that obtains by step (a).
Below, will illustrate in greater detail the present invention.
The invention is characterized in provides a kind of novel integral type barrier film and electrode, and the function that it has barrier film can be used as dividing plate and prevents electrically contacting and allow ion to pass through between negative electrode and the anode; The function that also has electrode realizes the embedding of reversible lithium/deviate from.
Electrode according to the present invention is integral type barrier film and electrode, and it is that mixture by coating inorganic particle and adhesive polymer on the surface of prefabricated electrode forms organic/inorganic composite porous coating and obtains.The coating of Xing Chenging is owing to the interstitial volume between the inorganic particle has uniform loose structure as mentioned above, its with electrode in the loose structure that forms of electrode active material be the same.
The concrete feature of organic/inorganic composite porous coating is as follows:
(1) the organic/inorganic composite porous coating that is formed on the electrode according to the present invention can replace traditional barrier film, because it can prevent the short circuit between negative electrode and the anode, and because its loose structure, but its conductive electrolyte.
Thermal contraction at high temperature can take place in (2) traditional polyolefin-based separator, because their fusing point is 120-140 ℃.Yet organic/inorganic composite porous coating is not because thermal contraction can take place in the thermal endurance of inorganic particle.Therefore, adopted the electrochemical appliance of electrode with above-mentioned coating that contains inorganic particle and adhesive polymer, even under extreme condition, for example high temperature, overcharge etc., can not cause fail safe to descend owing to the short circuit between negative electrode and the anode yet.Therefore, this electrochemical appliance is compared with conventional batteries and is had the excellent safety energy.
(3) traditional barrier film or polyeletrolyte form the independent film shape and assemble with electrode then.On the contrary, the organic/inorganic composite coating is by forming on the surface that it directly is coated to electrode, so it can fix (anchor) in the hole of electrode surface, thereby the firm physical bond between coating and the electrode is provided.Therefore, can improve the problem relevant with mechanical performance such as fragility.In addition, the bonding interface of this enhancing can reduce interface resistance (interfacial resistance) between electrode and the coating.In fact, electrode according to the present invention comprises the organic/inorganic composite coating, and itself and electrode active material organically combine.In addition, coating can not influence existing pore structure in the electrode, therefore can keep this structure.And coating itself has the uniform pore structure (referring to Fig. 3 and Fig. 4) that is formed by inorganic particle.
(4) depend on the mixed proportion of diameter or the inorganic particle and the polymer of inorganic particle, organic/inorganic composite porous coating has controlled aperture and porosity.Liquid electrolyte that above-mentioned hole can be injected is subsequently filled, and therefore can reduce inorganic particle significantly each other or the interface resistance that produces between inorganic particle and the adhesive polymer.
(5) when the adhesive polymer that is used for organic/inorganic composite porous coating be when having the polymer of electrolyte function, this polymer can be by liquid electrolyte swelling and/or dissolving, the electrolyte porous that injects after assembled battery is to polymer, and the electrolyte osmosis of gained polymer wherein possesses the ability of conductive electrolyte ion.Therefore, compare, can improve the performance of electrochemical appliance according to coating of the present invention with traditional organic/inorganic composite electrolyte.In addition, can be had good affinity to electrolyte by electrolyte swelling and/or dissolved polymers, the electrode pair electrolyte that is coated with this polymer also has the affinity of raising, therefore is expected to improve battery performance.And, when this polymer applications during, can reduce the irreversible capacity of anode in the carbon anode active material, the total capacity of battery is increased.
(6) although according to prior art, adopted traditional electrode and barrier film during the assembling electrochemical appliance, only adopted electrode with organic/inorganic composite porous coating according to the present invention, this coating can replace barrier film.Therefore, simplified the method for making electrochemical appliance.In addition, the thickness of the coating that obtains with traditional painting method is controlled the coating that can obtain having the coating of the form of film that is less than or equal to 10 μ m like this or obtain the thick film form easily.
A kind of component in the organic/inorganic composite porous coating is this area inorganic material of the particle form of employing at present, and this coating is formed on the surface of electrode.This inorganic particle prevents short circuit between anode and the negative electrode, so it can replace barrier film.Therefore, the selection of inorganic particle is had no particular limits, as long as it is an electrochemical stability.In other words, the selection of inorganic particle is had no particular limits, if they in the operating voltage range of the battery that has used them (for example, based on Li/Li
+0-5V) oxidation and/or reduction can not take place.Especially, preferably the inorganic particle of Cai Yonging has high as far as possible ionic conductivity, because this inorganic particle can improve the ionic conductivity and the performance of electrochemical appliance.In addition, when the inorganic particle that adopts had high density, they were difficult to disperse in coating step, can increase the weight of the battery of manufacturing.Therefore, the density of the inorganic particle that preferably adopts is low as far as possible.And when the inorganic particle that adopts had high dielectric constant, they helped improving in the liquid electrolyte for example degree of dissociation of lithium salts of electrolytic salt, thereby have improved electrolytical ionic conductivity.
Owing to these reasons, preferably adopt the inorganic particle have more than or equal to 10 high-k, have conductive inorganic particle of lithium or their mixture.
Dielectric constant is more than or equal to the concrete of 10 inorganic particle but nonrestrictive example comprises BaTiO
3, Pb (Zr, Ti) O
3(PZT), Pb
1-xLa
xZr
1-yTi
yO
3(PLZT), PB (Mg
3Nb
2/3) O
3-PbTiO
3(PMN-PT), hafnium oxide (HfO
2), SrTiO
3, SnO
2, CeO
2, MgO, NiO, CaO, ZnO, ZrO
2, Y
2O
3, Al
2O
3, TiO
2Or their mixture.
" inorganic particle with lithium-ion-conducting " used herein is meant and contains elemental lithium and need not store the just inorganic particle of energy conductive lithium ion of lithium.Inorganic particle with lithium-ion-conducting is because the defective that exists and conducting and mobile lithium ion in its structure, so can improve lithium-ion-conducting and promote the improvement of battery performance.This non-limitative example with inorganic particle of lithium-ion-conducting comprises: lithium phosphate (Li
3PO
4), titanium phosphate lithium (Li
xTi
y(PO
4)
3, 0＜x＜2,0＜y＜3), titanium phosphate aluminium lithium (Li
xAl
yTi
z(PO
4)
3, 0＜x＜2,0＜y＜1,0＜z＜3), (LiAlTiP)
xO
yType glass (0＜x＜4,0＜y＜13) is as 14Li
2O-9Al
2O
3-38TiO
2-39P
2O
5, lanthanium titanate lithium (Li
xLa
yTiO
3, 0＜x＜2,0＜y＜3), D2EHDTPA germanium lithium (Li
xGe
yP
zS
w, 0＜x＜4,0＜y＜1,0＜z＜1,0＜w＜5) and as Li
3.25Ge
0.25P
0.75S
4, lithium nitride (Li
xN
y, 0＜x＜4,0＜y＜2) and as Li
3N, SiS
2Type glass (Li
xSi
yS
z, 0＜x＜3,0＜y＜2,0＜z＜4) and as Li
3PO
4-Li
2S-SiS
2, P
2S
5Type glass (Li
xP
yS
z, 0＜x＜3,0＜y＜3,0＜z＜7) and as LiI-Li
2S-P
2S
5Or their mixture.
According to the present invention, use the high relatively inorganic particle of dielectric constant, and do not use the inorganic particle that does not have reactivity or dielectric constant low relatively.And the present invention also provides the new purposes of inorganic particle, and this purposes never was used.Above-mentioned inorganic particle, for example Pb (Zr, Ti) O
3(PZT), Pb
1-xLa
xZr
1-yTi
yO
3(PLZT), PB (Mg
3Nb
2/3) O
3-PbTiO
3(PMN-PT), hafnium oxide (HfO
2) etc., have high-k more than or equal to 100.Inorganic particle also has piezoelectricity, when they are drawn (drawn) or compression in specific force applications, can produce voltage between two surfaces by forming electric charge.Therefore, inorganic particle can prevent two internal short-circuits between the electrode, thereby helps improving the security performance of battery.In addition, when with this inorganic particle with high-k and inorganic particle with lithium-ion-conducting in conjunction with the time, the effect that can obtain working in coordination with.
Although the size to inorganic particle has no particular limits, preferably inorganic particle is of a size of 0.001-10 μ m, is in order to form the coating with uniform thickness and suitable porosity to be provided like this.When its size during less than 0.001 μ m, the physical property of the bad dispersibility of inorganic particle so that organic/inorganic composite porous coating is wayward.When its size during greater than 10 μ m, the thickness of the organic/inorganic composite porous coating that identical solid content forms down increases, and causes mechanical performance to descend.And when charge repeatedly, this excessive hole can increase the possibility of internal short-circuit.
Another kind of component in the organic/inorganic composite porous coating is a present used adhesive polymer in this area, and this coating is formed on the surface of electrode.Preferably adhesive polymer has alap glass transition temperature (Tg), and more preferably Tg is between-200 ℃ and 200 ℃.The low adhesive polymer of preferred above-mentioned Tg is because they can improve the mechanical performance of final coating, for example pliability and elasticity.This polymer is as binding agent, makes inorganic particle each other, between the surface of inorganic particle and electrode active material and a part of hole in the electrode interconnects and held stationary, prevent the mechanical performance decline of the final electrode that forms like this.
It is optional that employing has the adhesive polymer of ionic conductivity.Yet when adhesive polymer had ionic conductivity, it can further improve the performance of electrochemical appliance.Therefore, preferably adhesive polymer has high as far as possible dielectric constant, because the degree of dissociation of salt depends on the dielectric constant of solvent for use in the electrolyte in the electrolyte, the polymer with higher dielectric constant can increase the degree of dissociation of salt in the used electrolyte of the present invention.The dielectric constant range of this polymer is 1.0-100 (measuring under the 1kHz frequency), preferably more than or equal to 10.
According to the present invention, adhesive polymer can be the polymer of solubilized or swellable, the polymer that perhaps has mixed characteristic, and this depends on the kind of used liquid electrolyte.Can absorb the electrolyte that injects after the assembled battery with the polymer of electrolyte swelling and have the electrolyte ion conductibility, thereby improve the performance of battery.In addition, be dissolvable in water electrolytical micro polymer and be dissolved in the liquid electrolyte that injects after the assembled battery, therefore can suppress the side reaction between electrode active material and electrolyte to form the high viscosity electrolyte, thereby the fail safe that has improved battery.Especially, preferred adopt swellable that electrolyte is had a good affinity in electrolytical polymer be dissolvable in water electrolytical mixture of polymers.When adopt this form of mixtures, can by electrolyte swelling and/or dissolving have the adhesive polymer of electrolyte function the time, combine to above-mentioned effect concertedness, both improved the fail safe of battery, prevented battery performance decline again.
And, to compare with hydrophobic polymer such as polyolefin polymer, the hydrophilic polymer with many polar groups is more suitable for as adhesive polymer.Therefore, be preferred for the solubility parameter of polymer of the present invention more than or equal to 17.0[J
1/2/ cm
3/2], more preferably be 17.0-30[J
1/2/ cm
3/2].When the solubility parameter of polymer is less than or equal to 17[J
1/2/ cm
3/2] time, polymer swelling fully in traditional electrolyte of battery.
Except that above-mentioned effect, according to adhesive polymer of the present invention, its feature also is, it thereby is shown high degree of swelling by gelation when it swells in liquid electrolyte.Therefore, based on total polymer weight, the consumption of this polymer is preferably 1wt% at least, more preferably 1-1000wt%,
The non-limitative example that can be used for adhesive polymer of the present invention comprises poly(ethylene oxide), polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polyvinylidene fluoride-trichloroethylene, polymethyl methacrylate, polyacrylonitrile, polyacrylonitrile-styrol copolymer, polyvinyl chloride (PVC), polyvinylpyrrolidone, polyvinyl acetate, polyethylene-vinyl acetate copolymer, gelatin, the cyanoethyl amylopectin, the cyanoethyl polyvinyl alcohol, cyanethyl cellulose, cyanoethyl sucrose, amylopectin (pullulan), cellulose acetate, cellulose acetate-butyrate, cellulose-acetate propionate, polyethylene glycol, glyme, Polyethylene glycol dimethyl ether, carboxymethyl cellulose or their mixture.
Mixed proportion according to inorganic particle in the organic/inorganic composite porous coating of the present invention and polymer does not have special restriction.Thickness and structure according to the coating of final formation are controlled mixed proportion.More specifically, the ratio preferred weight ratio of inorganic particle and polymer is 10: 90 to 99: 1, more preferably 50: 50 to 99: 1.When mixed proportion during less than 10: 90, the amount of polymer is excessive to cause reducing the interstitial volume that forms between the inorganic particle, has therefore reduced the aperture and the porosity of coating, causes battery performance to descend.When mixed proportion greater than 99: 1, the too small cohesive force that causes weakening between the inorganic particle of the amount of polymer descends the mechanical performance of the organic/inorganic composite porous coating of gained.
The organic/inorganic composite porous coating that mixture by coating inorganic particle and adhesive polymer forms also has no particular limits on thickness.Can come control thickness according to the performance of battery.Can control the thickness that is formed on each coating on anode and the negative electrode respectively.According to the present invention, in order to reduce the internal resistance of battery, the thickness of coating is 1-100 μ m preferably, more preferably 1-30 μ m.
In addition, the aperture of organic/inorganic composite porous coating and porosity depend primarily on the size of inorganic particle.For example, when adopting particle diameter to be less than or equal to the inorganic particle of 1 μ m, the aperture in formed hole also is less than or equal to 1 μ m.Electrolyte that pore structure is injected is subsequently filled, and this electrolyte is used for conducting ion.Therefore, aperture and porosity are the key factors of the ionic conductivity of control coating.Preferably, aperture and the porosity according to organic/inorganic composite porous coating of the present invention is respectively 0.001-10 μ m and 10-95%.
The organic/inorganic composite porous coating that is formed on the electrode according to the present invention also can comprise other additive.
In another embodiment of electrode, this electrode has the organic/inorganic composite porous coating that can replace barrier film, this electrode not necessarily also comprises second coating, and this coating is by forming with polymer moieties or whole surface that applies the electrode active material that forms electrode.
In the electrode manufacture process, obtain second polymer coatedly with the surface of the electrode active material in the electrode of conventional method preparation with polymer-coated, this polymer is preferably the polymer with electrolyte function, its useful electrolytes swelling and/or dissolving.When surface-coated had solution, this solution contains can be by electrolyte swelling and/or dissolved polymers, and this solution can be penetrated into electrode interior by the hole of electrode self.Therefore, under the situation of the basic structure of keeping electrode, it is possible polymer being coated to equably on the active material of electrode interior.In addition, owing to kept pore structure between the electrode active material particles, electrolysis mass-energy promptly is penetrated in the electrode, and the thickness of the gained polymer thin film that is less than or equal to 1 μ m can make the reduced minimum of lithium ion rate travel simultaneously.
Below, will illustrate in greater detail above-mentioned second polymer coated.
(1) the lip-deep second polymer coated fail safe that can improve electrochemical appliance of the electrode active material in electrode formed according to the present invention.More specifically, when the electrode active material of routine since external impact as overcharging or high temperature storage and when unstable, can reacting with the electrolyte of high reaction activity.Yet according to the present invention, the surface of the active material in the electrode is aggregated thing parcel, preferably, and by can swelling and/or be dissolved in the polymer parcel of liquid electrolyte.Therefore, after the electrochemical appliance assembling and injecting conventional electrolyte then, electrode active material does not directly contact with electrolyte and contacts with polymer, thereby the reactivity of electrode active material is significantly descended.Therefore, can reduce the calorific value that the side reaction between electrode and the electrolyte produces, thereby the fail safe that can improve electrochemical appliance.
(2) the electrode active material lip-deep second polymer coated electrochemical appliance performance decrease that can make that is formed on according to the present invention minimizes.
According to the present invention, at first prepare electrode, then at the electrode surface coated polymer.On the contrary,, before the preparation electrode, electrode active material is coated with conducting polymer or inorganic particle, forms electrode with the electrode active material after the above-mentioned coating then according to prior art.Therefore, according to the present invention, the gathering of electrode active material can not occur or be coated in the separation of the polymer on the electrode active material.In addition, because can keep structure and distribution between each composition of electrode fully, therefore also can keep performance and the fundamental characteristics such as the capacity of electrochemical appliance.
(3) polymer in polymer coated can be by electrolyte swelling and/or dissolving according to of the present invention second.As mentioned above, in the preparation process of battery, in the time of in electrolyte is injected into battery, polymer can have the electrolyte ion conductibility, therefore makes the reduced minimum of battery performance.
(4) owing to can be had good electrolyte affinity by liquid electrolyte swelling and/or dissolved polymers, the electrode that is coated with this polymer has also improved electrolytical wetability.Therefore the total capacity that reduces the irreversible capacity of anode and obtain increasing is possible.
(5) according to prior art, barrier film and electrode can be coated with polymer.Yet this barrier film that is coated with polymer can become the barrier layer of lithium ion conduction, therefore produces battery performance, as the problem of ionic conductivity decline.On the contrary, according to the present invention, can be existed only in the surface of electrode active material by liquid electrolyte swelling and/or dissolved polymers.Therefore, with on the barrier film there is not polymer and the battery performance that the causes relevant problem that descends.
The selection that can be used for the second polymer coated polymer is had no particular limits, on this second polymer coated surface that is formed on the electrode active material of electrode interconnection.Preferably adopt polymer with physical property similar to the adhesive polymer in the first organic/inorganic composite porous coating.Any material as long as they have above-mentioned character, can be used alone or as a mixture.
The electrode active material that is coated with the polymer of second coating must be kept the pore structure between the active material particle of interconnection.Preferably polymer coated conduct is independent to be existed mutually, does not mix with binding agent (binder), and this binding agent not necessarily is used for traditional electrode slurry.
Although the second polymer coated polymer can adopt the hole that makes in the electrode to be aggregated the volume that thing is filled fully, consider the performance of battery and the amount that concerns may command use polymer between the fail safe.In addition, the consumption of polymer can be controlled independently in negative electrode and the anode.The amount that is present in the polymer of second in the electrode in polymer coated is a benchmark with the weight of electrode active material, is 0.01wt% at least, preferred 0.01-50wt%.
Be coated in the lip-deep second polymer coated of the electrode active material that interconnects in the electrode mutually as independent, its thickness is preferably 0.001 μ m (1nm)-10 μ m, more preferably 10nm-100nm.When thickness during less than 1nm, can not prevent side reaction and exothermic reaction between electrode active material and the electrolyte effectively, these reactions mainly occur in overcharge or the high temperature storage condition under.Therefore, can not improve the fail safe of battery.When thickness during greater than 10 μ m, electrolyte swelling that polymer is permeated or dissolving need the long time, have reduced lithium-ion-conducting like this, and the overall performance of battery is descended.
Comprise as the independent polymer coated electrode of electrode active material lip-deep second that is coated in mutually littler than the porosity of the electrode that does not comprise second coating.The porosity that comprises the electrode of second coating preferably is controlled in the scope of 1%-50%.The bore portion of electrode is filled with electrolyte.When the porosity of electrode less than 1% the time, the ratio of electrolyte (E) and electrode active material (M), promptly E/M is too low, therefore because the lithium-ion-conducting deficiency descends battery performance.When the porosity of electrode greater than 50% the time, overcharge or the condition of high temperature storage under, exceedingly carry out the side reaction between electrolyte and electrode active material, therefore cause battery security to descend.
And the polymer of second coating has high affinity to electrolyte, as mentioned above, therefore comprises that the electrode pair electrolyte of second coating also has high affinity.Therefore, compare, comprise that the electrode of second coating and the contact angle between electrolyte reduce, be preferably and reduced 1 ° or more perspective with the electrode that does not comprise second coating.
Preferably, electrode according to the present invention has such structure, and it comprises the lip-deep second polymer coated of the electrode active material particles that is formed on interconnection, and is formed on the electrode surface, can replaces the first organic/inorganic composite porous coating of barrier film.Therefore, performance and the fail safe that improves battery synergistically is possible.
The mixture of coating inorganic particle and adhesive polymer can be finished by well known to a person skilled in the art method on the surface of electrode.
The preparation method's of an electrode of the present invention embodiment comprises the following steps: that (a) adopts conventional method will contain the slurry of electrode active material, and nonessential binding agent and/or conductive agent be administered on the current-collector, so that electrode to be provided; (b) the dissolving adhesive polymer adds inorganic particle and with they mixing, applies the electrode that is obtained by step (a) with the mixture that obtains, the dry then electrode through applying so that adhesive polymer solution to be provided in solution in suitable organic solvent.
Preferably, used solvent has and solubility parameter like the polymer phase, and boiling point is low.This solvent can mix equably with polymer, and is easy to behind the coated polymer remove.Adoptable solvent comprises: acetone, oxolane, carrene, chloroform, dimethyl formamide, N-N-methyl-2-2-pyrrolidone N-(NMP), cyclohexylamine, water and their mixture, but be not limited thereto.
In addition, preferably inorganic particle is added in the adhesive polymer solution after, carry out the step of abrasive inorganic particle.It is suitable grinding required time and be 1-20 hour.The particle size range of the particle after the grinding is preferably 0.01-10 μ m.Can adopt conventional Ginding process, preferably adopt the method for ball milling.
For the mixture with inorganic particle and adhesive polymer is coated on the prefabricated electrode, can adopt any method that well known to a person skilled in the art.Can adopt diverse ways, comprise that immersion coating, mouthful pattern apply the associating of (die coating), roller coat, spot printing (comma coating) or said method.
The conventional electrodes that is coated with the gel-type polymer that has added inorganic particle can form loose structure (referring to Fig. 4 b) by adding wittingly and extracting plasticizer.Yet in this case, the aperture in hole is several dusts (), and porosity is low.Therefore, adopt the battery of this conventional electrodes to show poor performance.On the contrary, Zhi Bei electrode has such structure as mentioned above, wherein electrode active material layer and the compound porous coating of organic/inorganic particle closely and organically combine mutually, have kept unique pore structure that exists in each layer simultaneously, shown in Fig. 3 and Fig. 4 a.And the microcellular structure that is present in each layer allows lithium ion successfully to conduct.Therefore, be expected reduced minimum (referring to Fig. 1) with electrode performance.
In another embodiment of the preparation method of electrode of the present invention, polymer-coated forms second coating on the surface of electrode active material particles.Increase step (c) in step (a) with (b), on the surface of electrode active material particles, apply the polymer that is used for second coating by this step and form second coating.
For example, in step (c), the polymer dissolution that is used for second coating, is impregnated into prefabricated electrode in the solution, so that polymer solution to be provided then in appropriate solvent as shown in Figure 2.In addition, the polymer that is used for second coating can add the conventional slurry of electrode to and mix with it.
When the polymer dissolution that is used for second coating during, should control the content of polymer in the solvent, the amount that the hole that makes it not be higher than the complete filling electrode surface is required in solvent.When polymer content was too high, the viscosity of solution increased, so polymer may not be penetrated in the hole of electrode but can be present on the surface of electrode, thereby formed extra polymer layer on the surface of electrode.In this case, be difficult to control electrode and electrolytical reaction.And this polymer layer that additionally is formed on the electrode surface causes battery performance to descend.On the other hand, cross when low when polymer content, the amount of polymer that is present in the electrode active material surface is also low, thus can not control electrode and electrolyte between reaction.Although the content of polymer can change according to the viscosity of employed polymer, solvent types, solution and the porosity of electrode in the solvent, preferably be controlled in the scope of 0.1-20wt%.
In addition, electrochemical appliance provided by the invention comprises negative electrode, anode and electrolyte, one of them or two electrodes all comprise the organic/inorganic composite porous coating that contains inorganic particle and adhesive polymer, and this coating is formed on the surface of electrode, and can replace barrier film.
This electrochemical appliance comprises any device that electrochemical reaction takes place, and its concrete example comprises all types of primary cells, secondary cell, fuel cell, solar cell or capacitor.
Adopted in the embodiment of method of electrochemical appliance of above-mentioned electrode in manufacturing, do not need conventional polyolefin-based micro-pore septum, and adopt electrode, by reeling or lamination process with above-mentioned coating, inject electrolyte then, assemble electrochemical appliance.
According to electrode of the present invention, it is coated with organic/inorganic composite porous coating, can electrode active material be applied (apply) according to the method that well known to a person skilled in the art and form to current-collector.Particularly, cathode active material can comprise any conventional cathode active material of the negative electrode that is used for conventional electrochemical appliance at present.The nonrestrictive object lesson of cathode active material comprises the lithium insert material, as lithium manganese oxide, lithium and cobalt oxides, lithium nickel oxide, oxide/lithium ferrite or their composite oxides.In addition, anode active material can comprise any conventional anode active material of the anode that is used for conventional electrochemical appliance at present.The nonrestrictive object lesson of anode active material comprises the lithium insert material, for example lithium metal, lithium alloy, carbon, petroleum coke, activated carbon, graphite or other carbonaceous material.The non-limitative example of cathode collector comprises the paper tinsel that aluminium, nickel or their composition form.The non-limitative example of anode collector comprises the paper tinsel that copper, gold, nickel, copper alloy or their composition form.
Can be used for electrolyte of the present invention and comprise formula A
+B
-The salt of expression, wherein A
+Represent alkali-metal cation, it is selected from by Li
+, Na
+, K
+With their group of composition of combination; B
-The expression anion, it is selected from by PF
6 -, BF
4 -, Cl
-, Br
-, I
-, ClO
4 -, AsF
6 -, CH
3CO
2 -, CF
3SO
3 -, N (CF
3SO
2)
2 -, C (CF
2SO
2)
3 -With their group of composition of combination; This salt dissolves in organic solvent or dissociates, this organic solvent be selected from by propylene carbonate (propylenecarbonate) (PC), the group formed of ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), dimethyl sulfoxide (DMSO), acetonitrile, dimethoxy-ethane, diethoxyethane, oxolane, N-N-methyl-2-2-pyrrolidone N-(NMP), methyl ethyl carbonate, gamma-butyrolacton and their mixture.Yet, can be used for electrode of the present invention and be not limited to above-mentioned example.
More specifically, according to the manufacture method and the desired properties of final products, can in the appropriate step of electrochemical appliance manufacturing process, inject electrolyte.In other words, can before the electrochemical appliance assembling, inject electrolyte, or in the final step of assembling electrochemical appliance, inject electrolyte.
And, because electrode is integral type barrier film and electrode, therefore do not need extra barrier film.Yet according to the purposes and the performance of final electrochemical appliance, the electrode that is coated with coating of the present invention can use with polyolefin-based micro-pore septum.
Preferably, the electrochemical appliance that obtains from said method is a lithium secondary battery, and this lithium secondary battery comprises lithium metal secondary batteries, lithium rechargeable battery, lighium polymer secondary battery and lithium ion polymer secondary cell etc.
Implement optimal mode of the present invention
Now will be in detail with reference to the preferred embodiments of the invention.Be to be understood that following example only is exemplary, the present invention is not limited to this.
[embodiment 1-9]
Electrode that embodiment 1. organic/inorganic composite porous coatings apply and the preparation that comprises the lithium secondary battery of this electrode
1-1. have the electrode (PVdF-CTFE/Al of organic/inorganic composite porous coating
2O
3)
(preparation of anode)
As solvent, add 96wt% carbon dust, with N-N-methyl-2-2-pyrrolidone N-(NMP), form the anode mixture slurry as the 3wt%PVDF (polyvinylidene fluoride) of binding agent with as the 1wt% carbon black of conductive agent as anode active material.Slurry is coated in as on the thick Copper Foil of 10 μ m of anode collector the dry then anode that forms.Then anode is carried out roll-in.
(preparation of negative electrode)
As solvent, add 92wt% lithium cobalt composite oxide (LiCoO with N-N-methyl-2-2-pyrrolidone N-(NMP) as cathode active material
2), as the 4wt% carbon black of conductive agent with as the 4wt%PVDF (polyvinylidene fluoride) of binding agent, form cathode slurry.Slurry is coated in as on the thick aluminium foil of 20 μ m of cathode collector the dry then negative electrode that forms.Then negative electrode is carried out roll-in.
(coating of electrode surface)
The PVdF-CTFE polymer (polyvinylidene fluoride-chlorotrifluoroethylcopolymer copolymer) of 5wt% is joined in the acetone, and therein in 50 ℃ of following dissolvings 12 hours or for more time to form polymer solution.Aluminium oxide (the Al that in the above-mentioned polymer solution that obtains, adds 20wt% concentration
2O
3) powder.Then, grind and about 12 hours of dispersed alumina powder or longer time with ball grinding method, to form slurry.The particle diameter of aluminium oxide can be by being used for ball grinding method the size (particle diameter) and ball milling time of globule control.In the present embodiment alumina lap to particle diameter for about 500nm so that slurry to be provided.This slurry is coated in by the immersion coating method on each surface of negative electrode and anode then, is approximately 15 μ m to thickness.
1-2. lithium secondary battery
Do not adopt conventional polyolefin-based separator, will be by negative electrode after the above-mentioned coating that obtains and the stacked formation assembly of anode.Then, (ethylene carbonate (EC)/propylene carbonate (PC)/diethyl carbonate (DEC)=30/20/50 (wt%), it contains the lithium hexafluoro phosphate (LiPF of 1M with liquid electrolyte
6)) inject wherein so that battery to be provided.
Embodiment 2
Except replacing aluminium oxide (Al with the BaTiO3 powder
2O
3) powder is as outside the inorganic particle in the coating material of electrode surface, repetition embodiment 1 has organic/inorganic composite porous coating (PVdF-CTFE/BaTiO to provide
3) electrode and lithium secondary battery.
Embodiment 3
Except replacing aluminium oxide (Al with PMN-PT (niobic acid magnesium lead-lead titanates) powder
2O
3) powder is as outside the inorganic particle in the coating material of electrode surface, embodiment 1 is to provide electrode and the lithium secondary battery with organic/inorganic composite porous coating (PVdF-CTFE/PMN-PT) in repetition.
Embodiment 4
Except using TiO
2Powder replaces aluminium oxide (Al
2O
3) powder is as outside the inorganic particle in the coating material of electrode surface, repetition embodiment 1 has organic/inorganic composite porous coating (PVdF-CTFE/TiO to provide
2) electrode and lithium secondary battery.
Embodiment 5
Except using titanium phosphate lithium (LiTi
2(PO
4)
3) powder replacement aluminium oxide (Al
2O
3) powder is as outside the inorganic particle in the coating material of electrode surface, repetition embodiment 1 has organic/inorganic composite porous coating (PVdF-CTFE/LiTi to provide
2(PO
4)
3) electrode and lithium secondary battery.
Embodiment 6
Except also having adopted the thick polyethylene barrier film of 20 μ m when the assembled battery, repeat embodiment 1 and have organic/inorganic composite porous coating (PVdF-CTFE/Al to provide
2O
3) electrode and lithium secondary battery.
Embodiment 7
7.1 on the cathode active material surface, form and comprise the polymer coated of cyanoethyl amylopectin
Under about 30 ℃, cyanoethyl amylopectin (degree of polymerization is about 600) is dissolved about 1 hour so that solution to be provided in acetone.The concentration of polymer solution is 1wt%.On according to the described negative electrode that obtains of top embodiment 1-1, apply the cyanoethyl amylopectin solution by immersion coating.Especially, cathode dipping is in polymer solution and kept about 1 to 3 minute, up to drive portal in all bubbles, the negative electrode after vacuumize at room temperature applies then.
7.2 on negative electrode and anode, form organic/inorganic composite porous coating ((CTFE/Al
2O
3)
The CTFE polymer of 5wt% is joined in the acetone, and 50 ℃ of following dissolvings 12 hours or for more time to form polymer solution.With aluminium oxide (Al
2O
3) powder joins in this polymer solution with the solid content of 20wt% and disperse therein to form mixed solution.Above-mentioned slurry is coated in by the immersion coating method on each surface of negative electrode and anode, forms the coating that thickness is approximately 15 μ m.
7.3 the assembling of lithium secondary battery
Will be by negative electrode after the above-mentioned coating that obtains and the stacked formation assembly of anode.Then, (ethylene carbonate (EC)/propylene carbonate (PC)/diethyl carbonate (DEC)=30/20/50 (wt%), it contains the lithium hexafluoro phosphate (LiPF of 1M with liquid electrolyte
6)) inject wherein so that battery to be provided.
Except replace with the cyanoethyl polyvinyl alcohol cyanoethyl amylopectin as the polymerization coating agent of cathode active material, use BaTiO
3(particle diameter=100nm) replaces Al
2O
3Outside the inorganic particle as the organic/inorganic composite porous coating on negative electrode and the anode, repeat embodiment 7 so that battery to be provided.
Embodiment 9
Except replace with polymethyl methacrylate (mean molecule quantity=120000) the cyanoethyl amylopectin as the polymerization coating agent of cathode active material, use TiO
2(particle diameter=100nm) replaces Al
2O
3Outside the inorganic particle as the organic/inorganic composite porous coating on negative electrode and the anode, repeat embodiment 7 so that battery to be provided.
[comparative example 1-2]
Comparative example 1
Except not adopting the organic/inorganic composite porous coating on electrode to form electrode, and adopt conventional three layers of barrier film of polypropylene, polyethylene/polypropylene (PP/PE/PP) to prepare outside the battery, repeat embodiment 1 so that electrode and battery to be provided.
Comparative example 2
Battery, it comprise anode, polyolefin-based separator and be coated with the negative electrode of polymer coated (cyanoethyl amylopectin),
Except on cathode active material, forming polymer coated with the cyanoethyl amylopectin and adopting polyolefin-based (PP/PE/PP) barrier film of conventional anode and routine, repeat embodiment 7 so that electrode and battery to be provided.
The evaluation of experimental example 1. electrode surfaces
Carrying out following test is the surface that has according to the electrode of organic/inorganic porous coating of the present invention in order to analyze.
The sample that is used for this test is to have an organic/inorganic composite porous coating (Al according to what embodiment 1 obtained
2O
3/ PVdF-CTFE) electrode.
When adopting electronic scanner microscope to analyze, electrode according to the present invention has shown such structure, and (referring to Fig. 3) wherein interfixes between electrode active material particles and the organic/inorganic composite porous coating.More specifically, in electrode according to the present invention, kept the pore structure that formed by electrode active material particles, and because the interstitial volume between the inorganic particle, the organic/inorganic composite bed that is formed by inorganic particle and adhesive polymer has shown that uniform pore structure (referring to Fig. 3 and Fig. 4 a).
The evaluation of experimental example 2. electrode porositys and amount of contraction
The porosity of the electrode that obtains according to the present invention and amount of contraction (shrinkage) have been estimated at high temperature.
Adopted the electrode that has according to the organic/inorganic composite porous coating of embodiment 1-6.Adopt comparative example 1 used barrier film to compare.
After measuring the porosity of each electrode and barrier film, has the porosity that shows according to the electrode of organic/inorganic composite porous coating of the present invention height (referring to table 1) than conventional barrier film with porosimeter.
In addition, will have according to each electrode of the organic/inorganic composite porous coating of embodiment 1-6 with according to the barrier film of comparative example 1 and under 150 ℃ high temperature, store 1 hour, to detect its heat-shrinkable.The thermal shrinking quantity that conventional polyolefin-based separator shows is about 60%, and applies in preparation barrier film process on the direction of tension force and shown too high thermal shrinking quantity (referring to Fig. 5).On the other hand, even after at high temperature storing according to the organic/inorganic composite porous coating of embodiment 1-6, also show and shrink.And coating has shown the anti-flammability of such degree, also can be not on fire when using the alcolhol burner heating.This shows that the organic/inorganic composite porous coating according to embodiment 1-6 has good thermal stability (referring to table 1).
[table 1]
| Porosity (%) | Amount of contraction (%) (150 ℃ were stored 1 hour) | |
| Embodiment 1 | 60 | 0 |
| Embodiment 2 | 64 | 0 |
| Embodiment 3 | 60 | 0 |
| Embodiment 4 | 59 | 0 |
| Embodiment 5 | 51 | 0 |
| Embodiment 6 | 53 | 0 |
| Comp.Ex.1 | 41 | 60 |
The evaluation of experimental example 3. lithium secondary battery performances
For the performance of evaluate root, measured the capacity and the C-speed (C-rate) of each battery according to the lithium secondary battery of embodiment 1-6 and comparative example 1.
Each battery with 760mAh stands the circulation that discharge rate is 0.2C, 0.5C, 1C and 2C.Table 2 shows the discharge capacity of each battery, and this capacity is based on the C-rate representation.
Shown and C-speed characteristic [referring to table 2, Fig. 6 (embodiment 1), Fig. 7 (embodiment 6) and Fig. 8 (embodiment 1 and comparative example 1)] according to each lithium secondary battery of embodiment 1-6 according to the battery of comparative example 1 comparable (comparable).As shown in table 2, equal capacity under 0.5C being up to capacity under the speed of 1C.Capacity under 2C has also shown good high rate discharge (high-rate discharge) characteristic (C-speed), and it is more than or equal to 90% of the discharge capacity under 0.5C.
In addition, measure the cycle characteristics of each battery.Shown long life characteristic according to the lithium secondary battery with organic/inorganic composite porous coating of embodiment 1, it equates (referring to Fig. 9) with life-span according to the battery with conventional barrier film of comparative example 1 at least.
[table 2]
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example 1 | |
| 0.2C | 756 | 758 | 757 | 755 | 758 | 755 | 759 |
| 0.5C | 753 | 756 | 756 | 754 | 755 | 755 | 757 |
| 1C | 741 | 740 | 738 | 740 | 739 | 741 | 745 |
| 2C | 689 | 690 | 681 | 688 | 691 | 690 | 695 |
The evaluation of experimental example 4. safety of lithium secondary battery
Carrying out following test is for the fail safe of evaluate root according to each lithium secondary battery of embodiment 1-9 and comparative example 1-2.
4-1. overcharge test
Each battery charges under the condition of 6V/1A, 6V/2A, 10V/1A and 12V/1A, then test.
After the test, adopted the battery of existing P P/PE/PP barrier film blast (referring to table 3, Figure 10 and Figure 12) according to comparative example 1.This shows that polyolefin-based separator owing to over-charging of battery shrinks, causes inter-electrode short-circuit, and battery security is reduced.On the contrary, each battery with organic/inorganic composite porous coating according to the present invention has all shown excellent safety (referring to table 3, Figure 11 and Figure 12) under the condition of overcharging.
[table 3]
| Overcharge test condition | ||||
| 6V/1A | 6V/2A | 10V/1A | 12V/1A | |
| Embodiment 1 | By | By | By | By |
| Embodiment 2 | By | By | By | By |
| Embodiment 3 | By | By | By | By |
| Embodiment 4 | By | By | By | By |
| Embodiment 5 | By | By | By | By |
| Embodiment 6 | By | By | By | By |
| Embodiment 7 | By | By | | By |
| Embodiment | ||||
| 8 | By | By | By | By |
| Embodiment 9 | By | By | By | By |
| Comparative example 1 | By | Failure | Failure | Failure |
| Comparative example 2 | By | By | By | Failure |
4-2. hot case test
Under the high temperature of 150 ℃, 160 ℃ and 170 ℃, deposited each battery 1 hour, detect then.The result is presented in the table 4.
After at high temperature storing, shown safe condition, can prevent on fire and burning according to each battery of the embodiment of the invention, and according to the battery with conventional barrier film of comparative example 1 (referring to table 4) on fire under the same conditions.
As a result, the electrode that has organic/inorganic composite porous coating according to the present invention can replace the conventional membrane of thermal safety difference, therefore can improve the fail safe of battery.
[table 4]
| Hot case (℃/1 hour) | |||
| 150 | 160℃ | 170℃ | |
| Embodiment 1 | By | By | By |
| Embodiment 2 | By | By | By |
| Embodiment 3 | By | By | By |
| Embodiment 4 | By | By | By |
| Embodiment 5 | By | By | By |
| Embodiment 6 | By | By | By |
| Embodiment 7 | By | | By |
| Embodiment | |||
| 8 | By | By | By |
| Embodiment 9 | By | By | By |
| Comparative example 1 | Failure | Failure | Failure |
| Comparative example 2 | By | By | Failure |
Industrial applicibility
Find out that from aforementioned organic/inorganic composite porous coating on electrode surface formed according to the present invention can replace conventional membrane, and at high temperature thermal contraction can not take place in storage.Therefore, even at high temperature store, coating also can prevent the internal short-circuit between negative electrode and anode, therefore the fail safe that can improve electrochemical appliance.In addition, coating according to the present invention has good physical property and ionic conductivity, therefore helps improving the performance of electrochemical appliance.
Though combination is considered to the most practical at present and the most preferred embodiment has been described the present invention, is to be understood that the present invention is not limited to the content of disclosed embodiment and Tu.On the contrary, the present invention is intended to cover the interior various modifications and variations schemes of spirit and scope of appended claim.
Claims (24)
1. electrode, comprise and be formed on its lip-deep first organic/inorganic composite porous coating, wherein this first coating comprises inorganic particle and adhesive polymer, this adhesive polymer interconnects inorganic particle and is fixing, and this first coating has the micropore that is formed by the interstitial volume between the inorganic particle.
2. according to the electrode of claim 1, it comprises that also second is polymer coated, this coating layer portion or be formed on fully on the surface of the electrode active material particles in the electrode.
3. according to the electrode of claim 1, wherein electrode active material is combined on the current-collector when forming loose structure, and the surface of the first organic/inorganic composite porous coating and electrode interfixes.
4. according to the electrode of claim 1 or 2, wherein, depend on used electrolyte, the polymer in the adhesive polymer in first coating and second coating has separately between 17.0 and 30[J
1/2/ cm
3/2] between solubility parameter.
5. according to the electrode of claim 1 or 2, wherein adhesive polymer in this first coating and the polymer in second coating have separately between the dielectric constant between 1 and 100 (testing under the frequency at 1KHz).
6. according to the electrode of claim 1 or 2, wherein adhesive polymer in this first coating and the polymer in second coating come swelling with the ratio based on the 1%-1000% of polymer weight with liquid electrolyte separately.
7. according to the electrode of claim 1 or 2, wherein adhesive polymer in this first coating and the polymer in second coating are respectively separately and are selected from least a in the group of being made up of following material: poly(ethylene oxide), polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polyvinylidene fluoride-trichloroethylene, polymethyl methacrylate, polyacrylonitrile, polyacrylonitrile-styrol copolymer, polyvinyl chloride (PVC), polyvinylpyrrolidone, polyvinyl acetate, polyethylene-vinyl acetate copolymer, gelatin, the cyanoethyl amylopectin, the cyanoethyl polyvinyl alcohol, cyanethyl cellulose, cyanoethyl sucrose, amylopectin, cellulose acetate, cellulose acetate-butyrate, cellulose-acetate propionate, polyethylene glycol, glyme, Polyethylene glycol dimethyl ether and carboxymethyl cellulose.
8. according to the electrode of claim 2, wherein second coating comprises polymer, and based on the electrode active material of 100wt%, the content of this polymer is 0.01wt%-50wt%.
9. according to the electrode of claim 2, the polymer coated thickness that wherein forms second coating is 0.001 μ m-10 μ m.
10. according to the electrode of claim 1, wherein inorganic particle is to be selected from least a in the group that following particle forms: (a) dielectric constant is equal to or greater than 10 inorganic particle; (b) has the inorganic particle of lithium-ion-conducting.
11. according to the electrode of claim 10, it is to be selected from least a in the group of being made up of following material that its medium dielectric constant microwave medium is equal to or greater than 10 inorganic particle: BaTiO
3, Pb (Zr, Ti) O
3(PZT), Pb
1-xLa
xZr
1-yTi
yO
3(PLZT), PB (Mg
3Nb
2/3) O
3-PbTiO
3(PMN-PT), hafnium oxide (HfO
2), SrTiO
3, SnO
2, CeO
2, MgO, NiO, CaO, ZnO, ZrO
2, Y
2O
3, Al
2O
3And TiO
2
12. according to the electrode of claim 10, the inorganic particle that wherein has lithium-ion-conducting is to be selected from least a in the group of being made up of following material: lithium phosphate (Li
3PO
4), titanium phosphate lithium (Li
xTi
y(PO
4)
3, 0＜x＜2,0＜y＜3), titanium phosphate aluminium lithium (Li
xAl
yTi
z(PO
4)
3, 0＜x＜2,0＜y＜1,0＜z＜3), (LiAlTiP)
xO
yType glass (0＜x＜4,0＜y＜13), lanthanium titanate lithium (Li
xLa
yTiO
3, 0＜x＜2,0＜y＜3), D2EHDTPA germanium lithium (Li
xGe
yP
zS
w, 0＜x＜4,0＜y＜1,0＜z＜1,0＜w＜5), lithium nitride (Li
xN
y, 0＜x＜4,0＜y＜2), SiS
2Type glass (Li
xSi
yS
z, 0＜x＜3,0＜y＜2,0＜z＜4) and P
2S
5Type glass (Li
xP
yS
z, 0＜x＜3,0＜y＜3,0＜z＜7).
13. according to the electrode of claim 1, wherein the particle diameter of inorganic particle is 0.001 μ m-10 μ m.
14. according to the electrode of claim 1, wherein the thickness of first coating is 1 μ m-100 μ m.
15. according to the electrode of claim 1, wherein the aperture that forms in first coating is 0.001 μ m-10 μ m.
16. according to the electrode of claim 1, wherein the porosity of first coating is 10%-95%.
17. according to the electrode of claim 1, wherein, be benchmark with the percentage by weight, the mixed proportion that is present in inorganic particle in first coating and adhesive polymer is between 10: 90 and 99: 1.
18. electrode according to claim 1, it comprises anode active material or the cathode active material that is incorporated into current-collector, wherein cathode active material is to be selected from least a in the group of being made up of lithium manganese oxide, lithium and cobalt oxides, lithium nickel oxide and oxide/lithium ferrite, and anode active material is to be selected from least a in the group of being made up of lithium metal, lithium alloy, carbon, petroleum coke, activated carbon, graphite and metal oxide.
19. electrochemical appliance comprises negative electrode, anode and electrolyte, wherein in negative electrode and the anode or both are defined electrode in claim 1 or 2.
20. according to the electrochemical appliance of claim 19, it is a lithium secondary battery.
21. according to the electrochemical appliance of claim 19, it also comprises the microporous polymer barrier film.
22. make the method for the electrode of definition in the claim 1 or 2, it comprises the following steps:
(a) apply current-collector and dry with the slurry that contains electrode active material so that electrode to be provided; And
(b) apply the surface of the electrode that obtains by step (a) with the mixture of inorganic particle and adhesive polymer.
23. method according to claim 22, it also comprises the step (c) between step (a) and step (b), this step (c) is the surface of the electrode active material in the electrode that is obtained by step (a) with polymer-coated, and this polymer can come swelling and/or dissolving with electrolyte.
24. method according to claim 22 or 23, coating step (b) and (c) undertaken wherein: can dissolve respectively with the mixture of electrolyte swelling and/or dissolved polymers and inorganic particle and adhesive polymer or be dispersed in the solvent so that solution to be provided by following steps, apply this solution, then solvent is removed from solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410244437.XA CN104124427B (en) | 2004-02-07 | 2005-02-05 | Electrode, electrochemical device comprising electrode, and manufacture method of electrode |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020040008136 | 2004-02-07 | ||
| KR20040008136 | 2004-02-07 | ||
| KR1020040008585 | 2004-02-10 |
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| CN201410244437.XA Division CN104124427B (en) | 2004-02-07 | 2005-02-05 | Electrode, electrochemical device comprising electrode, and manufacture method of electrode |
| CN2012101072686A Division CN102646811A (en) | 2004-02-07 | 2005-02-05 | Organic/inorganic composite porous layer-coated electrode and electrochemical device comprising the same |
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| CN1918727A true CN1918727A (en) | 2007-02-21 |
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