Separator for electrochemical device and electrochemical device including the separator

Abstract

Disclosed is a method for manufacturing a separator. The method includes (S1) preparing a porous planar substrate having a plurality of pores, (S2) preparing a slurry containing inorganic particles dispersed therein and a polymer solution including a first binder polymer and a second binder polymer in a solvent, and coating the slurry on at least one surface of the porous substrate, (S3) spraying a non-solvent incapable of dissolving the second binder polymer on the slurry, and (S4) simultaneously removing the solvent and the non-solvent by drying. According to the method, a separator with good bindability to electrodes can be manufactured in an easy manner. In addition, problems associated with the separation of inorganic particles in the course of manufacturing an electrochemical device can be avoided.

Claims

1. A separator, comprising: (A) a planar porous polymer substrate having a plurality of pores; and (B) a porous coating layer disposed on at least one surface of the porous polymer substrate, wherein the porous coating layer has a surface disposed away from the porous polymer substrate, and an underlying portion disposed between the surface and the porous polymer substrate, wherein the porous coating layer comprises inorganic particles, and a binder polymer, wherein the binder polymer comprises a first binder polymer and a second binder polymer, wherein the second binder polymer of the binder polymer is present in a larger amount on the surface of the porous coating layer than in the underlying portion of the porous coating layer, wherein the first binder polymer is selected from the group consisting of cyanoethylpullulan, cyanoethyl polyvinyl alcohol, cyanoethyl cellulose, polycyanoacrylate, cyanoethyl sucrose, polyacrylamide-co-acrylate, and mixtures thereof, wherein the second binder polymer is selected from the group consisting of polyvinylidene fluoride-co-hexafluoropropylene, polyvinylidene fluoride-co-trichloroethylene, polymethyl methacrylate and mixtures thereof, and wherein the inorganic particles are selected from the group consisting of inorganic particles having a dielectric constant of at least 5, inorganic particles having the ability to transport lithium ions without storing the lithium, and mixtures thereof.

2. The separator according to claim 1, wherein the porous polymer substrate is selected from the group consisting of porous polyolefin membranes, porous polyethylene terephthalate membranes and non-woven fabrics.

3. The separator according to claim 1, wherein the porous polymer substrate has a thickness of 1 to 100 m.

4. The separator according to claim 1, wherein the inorganic particles have an average particle diameter of 0.001 to 10 m.

5. The separator according to claim 1, wherein the inorganic particles having a dielectric constant of at least 5 are selected from the group consisting of BaTiO.sub.3, Pb(Zr,Ti)O.sub.3 (PZT), Pb.sub.1-xLa.sub.xZr.sub.1-yTi.sub.yO.sub.3 (PLZT, 0<x<1, 0<y<1), Pb(Mg.sub.1/3Nb.sub.2/3)O.sub.3PbTiO.sub.3 (PMN-PT), hafnia (HfO.sub.2), SrTiO.sub.3, SnO.sub.2, CeO.sub.2, MgO, NiO, CaO, ZnO, ZrO.sub.2, Y.sub.2O.sub.3, Al.sub.2O.sub.3, SiC, TiO.sub.2 particles, and mixtures thereof.

6. The separator according to claim 1, wherein the inorganic particles having the ability to transport lithium ions are selected from the group consisting of lithium phosphate (Li.sub.3PO.sub.4), lithium titanium phosphate (Li.sub.xTi.sub.y(PO.sub.4).sub.3, 0<x<2, 0<y<3), lithium aluminum titanium phosphate (Li.sub.xAl.sub.yTi.sub.z(PO.sub.4).sub.3, 0<x<2, 0<y<1, 0<z<3), (LiAlTiP).sub.xO.sub.y type glass (0<x<4, 0<y<13), lithium lanthanum titanate (Li.sub.xLa.sub.yTiO.sub.3, 0<x<2, 0<y<3), lithium germanium thiophosphate (Li.sub.xGe.sub.yP.sub.zS.sub.w, 0<x<4, 0<y<1, 0<z<1, 0<w<5), lithium nitride (Li.sub.xN.sub.y, 0<x<4, 0<y<2), SiS.sub.2 type glass (Li.sub.xSi.sub.yS.sub.z, 0<x<3, 0<y<2, 0<z<4), P.sub.2S.sub.5 type glass (Li.sub.xP.sub.yS.sub.z, 0<x<3, 0<y<3, 0<z<7) particles, and mixtures thereof.

7. The separator according to claim 1, wherein the first binder polymer is polyacrylamide-co-acrylate.

8. The separator according to claim 1, wherein the inorganic particles in the porous coating layer are bound to each other by at least one of the first polymer binder and the second polymer binder in the state that the inorganic particles are fixed in contact with each other, from which interstitial volumes are formed between the inorganic particles, and the interstitial volumes between the inorganic particles become empty spaces to form pores.

9. The separator according to claim 1, wherein the first binder polymer and the second binder polymer are present in a weight ratio of 75:25 to 10:90.

10. The separator according to claim 1, wherein the inorganic particles and the binder polymers are present in a weight ratio of 50:50 to 99:1.

11. An electrochemical device, comprising a cathode, an anode, and the separator of claim 1 interposed between the cathode and the anode.

12. The electrochemical device according to claim 11, which is a lithium secondary battery.

13. The separator according to claim 1 wherein the inorganic particles are in contact with one another and interstitial volumes present between the inorganic particles comprise pores of the porous coating layer.

14. The separator according to claim 13 wherein the size of the interstitial volumes is equal to or smaller than the average particle diameter of the inorganic particles.

15. The separator according to claim 1, wherein the second binder polymer is selected from the group consisting of polyvinylidene fluoride-co-hexafluoropropylene, polyvinylidene fluoride-co-trichloroethylene, and mixtures thereof.

16. The electrochemical device according to claim 11, where the anode comprises an anode active material layer and an anode current collector, wherein the anode active material layer is interposed between the separator and the anode current collector, and wherein the cathode comprises a cathode active material layer and a cathode current collector, wherein the cathode active material layer is interposed between the separator and the cathode current collector.

17. A separator, comprising: (A) a planar porous polymer substrate having a plurality of pores; and (B) a porous coating layer disposed on at least one surface of the porous polymer substrate, wherein the porous coating layer has a surface disposed away from the porous polymer substrate, and an underlying portion disposed between the surface and the porous polymer substrate, wherein the porous coating layer comprises inorganic particles, and a binder polymer, wherein the binder polymer comprises a first binder polymer and a second binder polymer, wherein the second binder polymer of the binder polymer is present in a larger amount on the surface of the porous coating layer than in the underlying portion of the porous coating layer, wherein the first binder polymer comprises one or more of cyanoethylpullulan, cyanoethyl polyvinyl alcohol, cyanoethyl cellulose, polycyanoacrylate, cyanoethyl sucrose, and polyacrylamide-co-acrylate, wherein the second binder polymer comprises one or more of polyvinylidene fluoride-co-hexafluoropropylene, polyvinylidene fluoride-co-trichloroethylene, and polymethyl methacrylate, and wherein the inorganic particles are selected from the group consisting of inorganic particles having a dielectric constant of at least 5, inorganic particles having the ability to transport lithium ions without storing the lithium, and mixtures thereof.

Description

DESCRIPTION OF DRAWINGS

(1) Other objects and aspects of the present invention will become apparent from the following descriptions of the embodiments with reference to the accompanying drawings in which:

(2) FIG. 1 is a scanning electron microscope (SEM) image showing a porous coating layer of a separator manufactured in Example 1;

(3) FIG. 2 is a SEM image showing a porous coating layer of a separator manufactured in Example 2; and

(4) FIG. 3 is a SEM image showing a porous coating layer of a separator manufactured in Comparative Example 1.

BEST MODE

(5) Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. Prior to the description, it should be understood that the terms used in the specification and the appended claims should not be construed as limited to general and dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present invention on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation. Therefore, the description proposed herein is just a preferable example for the purpose of illustrations only, not intended to limit the scope of the invention, so it should be understood that other equivalents and modifications could be made thereto without departing from the spirit and scope of the invention.

(6) The present invention provides a method for manufacturing a separator. The method of the present invention will now be described in detail.

(7) First, a porous planar substrate having a plurality of pores is prepared (S1).

(8) The porous substrate may be any porous planar substrate commonly used in electrochemical devices. Examples of such porous planar substrates include various porous polymer membranes and non-woven fabrics. As the porous polymer membranes, there can be used, for example, porous polyolefin membranes used in separators for electrochemical devices, particularly, lithium secondary batteries. The non-woven fabrics may be, for example, those composed of polyethylene phthalate fibers. The material or shape of the porous substrate may vary according to intended purposes. Examples of materials suitable for the porous polyolefin membranes include polyethylene polymers, such as high density polyethylene, linear low density polyethylene, low density polyethylene and ultrahigh molecular weight polyethylene, polypropylene, polybutylene and polypentene. These polyolefins may be used alone or as a mixture thereof. Examples of materials suitable for the non-woven fabrics include polyolefins and polymers having higher heat resistance than polyolefins. The thickness of the porous substrate is preferably from 1 to 100 m, more preferably from 5 to 50 m, but is not particularly limited to this range. The pore size and porosity of the porous substrate are preferably from 0.001 to 50 m and 10 to 95%, respectively, but are not particularly limited to these ranges.

(9) Subsequently, a slurry containing inorganic particles dispersed therein and a polymer solution including a first binder polymer and a second binder polymer in a solvent is coated on at least one surface of the porous substrate (S2).

(10) Hereinafter, an explanation will be given of the constituent components of the slurry used in this step.

(11) The inorganic particles are not specifically limited so long as they are electrochemically stable. In other words, the inorganic particles can be used without particular limitation in the present invention if they do not undergo oxidation and/or reduction in an operating voltage range applied to an electrochemical device (for example, 0-5 V for Li/Li.sup.+). In particular, a high dielectric constant of the inorganic particles can contribute to an increase in the degree of dissociation of a salt (e.g., a lithium salt) in a liquid electrolyte to improve the ionic conductivity of the electrolyte.

(12) For these reasons, it is preferred that the inorganic particles have a high dielectric constant of at least 5, preferably at least 10. Non-limiting examples of inorganic particles having a dielectric constant of at least 5 include BaTiO.sub.3, Pb(Zr,Ti)O.sub.3 (PZT), Pb.sub.1-xLa.sub.xZr.sub.1-yTi.sub.yO.sub.3 (PLZT), Pb(Mg.sub.1/3Nb.sub.2/3O.sub.3PbTiO.sub.3 (PMN-PT), hafnia (HfO.sub.2), SrTiO.sub.3, SnO.sub.2, CeO.sub.2, MgO, NiO, CaO, ZnO, ZrO.sub.2, Y.sub.2O.sub.3, Al.sub.2O.sub.3, TiO.sub.2 and SiC particles. These inorganic particles may be used alone or as a mixture of two or more kinds thereof.

(13) The inorganic particles may be those having the ability to transport lithium ions, that is, those containing lithium atoms and having the ability to transfer lithium ions without storing the lithium. Non-limiting examples of inorganic particles having the ability to transport lithium ions include lithium phosphate (Li.sub.3PO.sub.4) particles, lithium titanium phosphate (Li.sub.xTi.sub.y(PO.sub.4).sub.3, 0<x<2, 0<y<3) particles, lithium aluminum titanium phosphate (Li.sub.xAl.sub.yTi.sub.z(PO.sub.4).sub.3, 0<x<2, 0<y<1, 0<z<3) particles, (LiAlTiP).sub.xO.sub.y type glass (0<x<4, 0<y<13) particles such as 14Li.sub.2O-9Al.sub.2O.sub.3-38TiO.sub.2-39P.sub.2O.sub.5 particles, lithium lanthanum titanate (Li.sub.xLa.sub.yTiO.sub.3, 0<x<2, 0<y<3) particles, lithium germanium thiophosphate (Li.sub.xGe.sub.yP.sub.zS.sub.w, 0<x<4, 0<y<1, 0<z<1, 0<w<5) particles such as Li.sub.3.25Ge.sub.0.25P.sub.0.75S.sub.4 particles, lithium nitride (Li.sub.xN.sub.y, 0<x<4, 0<y<2) particles such as Li.sub.3N particles, SiS.sub.2 type glass (Li.sub.xSi.sub.yS.sub.z, 0<x<3, 0<y<2, 0<z<4) particles such as Li.sub.3PO.sub.4Li.sub.2SSiS.sub.2 particles, and P.sub.2S.sub.5 type glass (Li.sub.xP.sub.yS.sub.z, 0<x<3, 0<y<3, 0<z<7) particles such as LiILi.sub.2SP.sub.2S.sub.5 particles. These inorganic particles may be used alone or as a mixture of two or more kinds thereof.

(14) There is no particular restriction on the average particle diameter of the inorganic particles. The average particle diameter of the inorganic particles is preferably limited to the range of 0.001 to 10 m. Within this range, a uniform thickness and an optimal porosity of the coating layer can be obtained. An average particle diameter of less than 0.001 m may cause deterioration of dispersibility. Meanwhile, an average particle diameter exceeding 10 m may increase the thickness of the coating layer.

(15) The first binder polymer is not specifically limited but is preferably a polymer having cyano groups. Examples of such polymers having cyano groups include cyanoethylpullulan, cyanoethyl polyvinyl alcohol, cyanoethyl cellulose, polycyanoacrylate and cyanoethyl sucrose. These polymers having cyano groups may be used alone or as a mixture of two or more thereof. Polyacrylamide-co-acrylate is preferably used as the first binder polymer.

(16) The second binder polymer may be selected from the group consisting of polyvinylidene fluoride-co-hexafluoropropylene, polyvinylidene fluoride-co-trichloroethylene, polymethyl methacrylate and mixtures thereof.

(17) The weight ratio of the first binder polymer to the second binder polymer is in the range of 75:25 to 10:90. Within this range, the objects of the present invention can be suitably achieved. The ratio of the weight of the inorganic particles to the weight of the binder polymers (i.e. the sum of the weights of the first and second binder polymers) is preferably in the range of 50:50 to 99:1 and more preferably 70:30 to 95:5. If the inorganic particles are present in an amount of less than 50% by weight (i.e. the binder polymers are present in a relatively large amount), the pore size and porosity of the porous coating layer may be reduced. Meanwhile, if the inorganic particles are present in an amount exceeding 99% by weight, the peeling resistance of the porous coating layer may be deteriorated.

(18) The solvent used in the preparation of the slurry dissolves both the first binder polymer and the second binder polymer. The solvent is preferably one whose solubility parameter has a difference of 5.0 Mpa.sup.0.5 or less from those of the first binder polymer and the second binder polymer. Examples of solvents suitable for use in the preparation of the slurry may include acetone, N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone and methyl ethyl ketone. These solvents may be used alone or as a mixture thereof.

(19) The slurry may be prepared by dissolving the first binder polymer and the second binder polymer in the solvent, adding the inorganic particles to the solution, and dispersing the inorganic particles in the solution. The inorganic particles may be crushed to a proper size before addition to the solution of the binder polymers. Preferably, the inorganic particles are added to the solution of the binder polymers and are then dispersed in the solution while being crushed by a suitable technique such as ball milling.

(20) The slurry thus prepared can be coated on at least one surface of the porous substrate by a technique well-known in the art, for example, dip coating, roll coating or die coating. Taking into consideration the functions of the coating layer and the suitability of the coating layer for a high-capacity battery, it is preferred to adjust the amount of the slurry loaded on the porous substrate such that the porous coating layer has a basis weight ranging from 5 to 20 g/m.sup.2.

(21) Then, a non-solvent incapable of dissolving the second binder polymer is sprayed on the slurry coated on the porous substrate (S3). As a result of the spraying, a non-solvent coating layer is formed on the slurry coating layer. The term non-solvent as used herein refers to a solvent that does not dissolve the second binder polymer. The non-solvent is preferably one whose solubility parameter has a difference of 8.0 Mpa.sup.0.5 or more from that of the second binder polymer. Particularly, water, methanol or ethanol is more preferred as the non-solvent.

(22) The non-solvent sprayed on the slurry coating layer promotes phase separation of the second binder polymer in the slurry to allow a larger amount of the second binder polymer to be distributed on the surface of the slurry coating layer. This distribution enhances the bindability of a separator to be manufactured after subsequent drying (S4) to electrodes, thus facilitating lamination between the separator and the electrodes and avoiding problems associated with the separation of the inorganic particles. In addition, a sufficiently high bonding strength between the separator and electrodes is ensured, so that the content of the inorganic particles in the porous coating layer can be increased, resulting in a further improvement in the stability of the separator.

(23) Finally, the solvent of the slurry coated on the porous substrate and the non-solvent are simultaneously removed by drying (S4). This simultaneous removal allows a larger amount of the second binder polymer to be present on the outermost surface of the porous coating layer. That is, the surface portion of the porous coating layer contains a larger number of the second binder polymer molecules than the underlying portion thereof. This distribution enhances the bonding strength between the separator and electrodes.

(24) The slurry coating layer may be dried before spraying with the non-solvent, unlike in the method of the present invention. In this case, however, the function of the non-solvent on the second binder polymer cannot be expected.

(25) The present invention also provides a separator manufactured by the method. The separator includes a porous substrate and a porous coating layer formed on the porous substrate. The porous substrate and the porous coating layer are the same as those explained earlier. In the porous coating layer, the binder polymers attach (that is, fixedly connect) the inorganic particles to each other so as to maintain a state in which the inorganic particles are bound to each other. It is preferred to maintain a state in which the porous coating layer is bound to the porous substrate by the binder polymers. Thus, the inorganic particles are in contact with each other in the porous coating layer. It is preferred that interstitial volumes created between the inorganic particles in contact with each other become pores of the porous coating layer. At this time, the size of the interstitial volumes is equal to or smaller than the average particle diameter of the inorganic particles.

(26) The present invention also provides a method for manufacturing an electrochemical device by interposing the separator between a cathode and an anode, followed by lamination. An electrochemical device manufactured by the method may be any device in which electrochemical reactions occur, and specific examples thereof include all kinds of primary batteries, secondary batteries, fuel cells, solar cells, and capacitors such as supercapacitor devices. Particularly preferred are lithium secondary batteries, including lithium metal secondary batteries, lithium ion secondary batteries, lithium polymer secondary batteries and lithium ion polymer secondary batteries.

(27) There is no particular restriction on the production method of a cathode and an anode to be applied together with the separator of the present invention. Each of the electrodes can be produced by binding an electrode active material to an electrode current collector by suitable methods known in the art. The cathode active material may be any of those that are commonly used in cathodes of conventional electrochemical devices. Non-limiting examples of particularly preferred cathode active materials include lithium manganese oxides, lithium cobalt oxides, lithium nickel oxides, lithium iron oxides and lithium composite oxides thereof. The anode active material may be any of those that are commonly used in anodes of conventional electrochemical devices. Non-limiting examples of particularly preferred anode active materials include lithium, lithium alloys, and lithium intercalation materials such as carbon, petroleum coke, activated carbon, graphite and other carbonaceous materials. Non-limiting examples of cathode current collectors suitable for use in the electrochemical device of the present invention include aluminum foils, nickel foils and combinations thereof. Non-limiting examples of anode current collectors suitable for use in the electrochemical device of the present invention include copper foils, gold foils, nickel foils, copper alloy foils and combinations thereof.

(28) The electrochemical device of the present invention can use an electrolyte consisting of a salt and an organic solvent capable of dissolving or dissociating the salt. The salt has a structure represented by A.sup.+B.sup. wherein A.sup.+ is an alkali metal cation such as Li.sup.+, Na.sup.+, K.sup.+ or a combination thereof and B.sup. is an anion such as PF.sub.6.sup., BF.sub.4.sup., Cl.sup., Br.sup., I.sup., ClO.sub.4.sup., AsF.sub.6.sup., CH.sub.3CO.sub.2.sup., CF.sub.3SO.sub.3.sup., N(CF.sub.3SO.sub.2).sub.2.sup., C(CF.sub.2SO.sub.2).sub.3.sup. or a combination thereof. Examples of organic solvents suitable for dissolving or dissociating the salt include, but are not limited to, propylene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), dimethyl sulfoxide, acetonitrile, dimethoxyethane, diethoxyethane, tetrahydrofuran, N-methyl-2-pyrrolidone (NMP), ethyl methyl carbonate (EMC) and -butyrolactone. These organic solvents may be used alone or as a mixture thereof.

(29) The electrolyte may be injected in any suitable step during manufacturing of the electrochemical device depending on the manufacturing processes and desired physical properties of a final product. Specifically, the electrolyte may be injected before battery assembly or in the final step of battery assembly.

MODE FOR INVENTION

(30) Hereinafter, the present invention will be explained in detail with reference to embodiments. The embodiments of the present invention, however, may take several other forms, and the scope of the invention should not be construed as being limited to the following examples. The embodiments of the present invention are provided to more fully explain the present invention to those having ordinary knowledge in the art to which the present invention pertains.

Example 1

(31) A polymer mixture of cyanoethylpullulan as a first binder polymer and polyvinylidene fluoride-co-hexafluoropropylene (PVdF-HFP) as a second binder polymer in a weight ratio of 2:10 was dissolved in acetone at 50 C. for at least about 12 hours to prepare a polymer solution. A barium titanate (BaTiO.sub.3) powder was added to the polymer solution until the weight ratio of the polymer mixture to the inorganic powder reached 10:90. The inorganic particles were crushed and dispersed using a ball mill for at least 12 hours to prepare a slurry. The inorganic particles of the slurry had an average particle diameter of 600 nm.

(32) The slurry thus prepared was dip-coated on a 12 m thick porous polyethylene terephthalate membrane (porosity 45%). The amount of the slurry loaded was adjusted to 12.5 g/m.sup.2.

(33) Subsequently, distilled water as a non-solvent for the second binder polymer was sprayed on both surfaces of the slurry. The spray rate of the non-solvent was adjusted to 9 mL/min.

(34) Then, the coated substrate was passed through a dryer to remove the solvent and the non-solvent, completing the manufacture of a separator. The separator was found to have a Gurley value of 373.9 sec/100 mL.

(35) FIG. 1 is a SEM image showing the porous coating layer of the separator. From the image of FIG. 1, it can be confirmed that a large number of the second binder polymer molecules were exposed to the surface of the porous coating layer.

(36) Another separator was manufactured as described above. The two separators were laminated to each other at 100 C. The laminate was found to have a bonding strength of 11.21 gf/cm, implying good bindability to electrodes.

Example 2

(37) A separator was manufactured in the same manner as in Example 1, except that the kind of the non-solvent was changed to a mixture of distilled water and methanol (6:4 (v/v)).

(38) FIG. 2 is a SEM image showing the porous coating layer of the separator. From the image of FIG. 2, it can be confirmed that a large number of the second binder polymer molecules were exposed to the surface of the porous coating layer.

(39) The separator was found to have a Gurley value of 371.1 sec/100 mL and a bonding strength of 9.42 gf/cm.

Example 3

(40) A separator was manufactured in the same manner as in Example 1, except that the kind of the first binder polymer was changed to polycyanoacrylate. The separator was found to have a Gurley value of 364.9 sec/100 mL and a bonding strength of 13.10 gf/cm.

Example 4

(41) A separator was manufactured in the same manner as in Example 1, except that the kind of the first binder polymer was changed to polyacrylamide-co-acrylate. The separator was found to have a Gurley value of 361.8 sec/100 mL and a bonding strength of 11.07 gf/cm.

Comparative Example 1

(42) A separator was manufactured in the same manner as in Example 1, except that the non-solvent was not sprayed.

(43) FIG. 3 is a SEM image showing the porous coating layer of the separator. Referring to FIG. 3, a much smaller number of the binder polymer molecules were exposed to the surface of the porous coating layer than those observed in the separators of Examples 1 and 2.

(44) Although the Gurley value of the separator was in a good level (382.5 sec/100 mL), the bonding strength of the separator was much lower (2.61 gf/cm) than the bonding strengths of the separators manufactured in Examples 1-4.

(45) The present invention has been described in detail. However, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.