Ceramic composite separator and manufacturing method thereof

Abstract

A ceramic composite separator and a method for preparing the ceramic composite separator are provided. The ceramic composite separator includes a polymer scaffold and a coating including a plurality of ceramic particles, a portion of the plurality of ceramic particles disposed within the polymer scaffold. The method for preparing the ceramic composite separator includes providing a polymer scaffold, forming a coating including the plurality of ceramic particles on the polymer scaffold, and solidifying the coating on the polymer scaffold to form a ceramic composite separator including the solidified coating on the polymer scaffold.

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to and the benefit of U.S. patent application Ser. No. 63 / 418,840, filed October 24, 2022, the contents of which are incorporated herein by reference in their entirety.

[0002] FIELD OF THE INVENTION

[0002] This disclosure relates to electrochemical energy storage devices and materials and designs for polymer / ceramic composite electrode separators for rechargeable lithium-based batteries. This disclosure also relates to methods for making lithium-conducting composite ceramic separators. [Background technology]

[0003] background

[0003] Demand for lithium battery technology with improved capacity, cycle life, and charge rates continues to grow with commercial interest in passenger and commercial electric vehicles. Of all available technologies, solid-state lithium-based batteries have the potential to significantly increase energy density while enabling correspondingly advanced chemistries. However, one of the challenges to achieving commercial-scale production of these advanced batteries is that some advancement must be made in one or more key components, particularly with regard to the design, manufacturing, and, more importantly, performance of such components. Among these key components, there is a need for improved separators that can provide improved performance while alleviating the design and manufacturing concerns that plague current lithium-based battery technology.

[0004] BRIEF DESCRIPTION OF THE DRAWINGS For a more complete understanding of the principles disclosed herein and their advantages, reference is now made to the following description, which should be read in conjunction with the accompanying drawings. [Brief explanation of the drawings]

[0005] [Figure 1A] 5 illustrates an exemplary embodiment of a ceramic composite separator according to various embodiments. [Figure 1B]

[0006] 1 illustrates an exemplary embodiment of a ceramic composite separator according to various embodiments. [Figure 1C]

[0007] 1 illustrates an exemplary embodiment of a ceramic composite separator according to various embodiments. [Figure 2A]

[0008] 1 illustrates an exemplary embodiment of an electrochemical cell according to various embodiments. [Figure 2B]

[0009] 1 illustrates an exemplary embodiment of a bipolar electrochemical cell according to various embodiments. [Figure 3]

[0010] 1 illustrates a method for preparing a ceramic composite separator according to various embodiments. DETAILED DESCRIPTION OF THE INVENTION

[0006]

[0011] It should be understood that the drawings are not necessarily drawn to scale, and that objects in the drawings are not drawn to scale relative to each other. The drawings are depictions intended to clarify and provide an understanding of various embodiments of the devices, systems, and methods disclosed herein. Wherever possible, the same reference numerals will be used throughout the drawings to refer to the same or like parts. Further, it should be understood that the drawings are not intended to limit the scope of the present teachings in any way.

[0007] Detailed Description

[0012] The technology disclosed herein relates to a ceramic composite separator (also referred to herein as a lithium-conducting ceramic composite separator) and a method for preparing the same. As described herein, the disclosed ceramic composite separator can be used in lithium-based rechargeable batteries and can improve performance while mitigating the aforementioned shortcomings of currently available separators. According to various embodiments, the ceramic composite separator can comprise a polymer scaffold and a coating of ceramic particles. In various embodiments, a portion of the ceramic particles of the coating can be disposed within the polymer scaffold. In various embodiments, the disclosed ceramic composite separator can be prepared by the disclosed method. The method can include providing a polymer scaffold, forming a coating on the polymer scaffold including a plurality of ceramic particles, and solidifying the coating to form a ceramic composite separator comprising the solidified coating on the polymer scaffold.

[0008]

[0013] Currently, composite coatings are often fabricated using solution-based casting methods, for example, by casting a mixture of ceramic material, binder, and solvent onto a temporary carrier substrate (after which the solvent may be removed to form a free-standing composite film). While this casting method is suitable for small-scale production of composite separators, it is less suitable for high-throughput applications. In contrast, the technology disclosed herein describes methods for forming ceramic composite separators on polymer scaffold materials. As disclosed, the use of polymer scaffold materials allows for at least partial or complete coating and impregnation of ceramic particles in the polymer scaffold, and can be utilized to form lithium-conducting solid composite separators, also referred to herein as ceramic composite separators.

[0009]

[0014] 1A, 1B, and 1C illustrate embodiments of ceramic composite separators according to various embodiments. FIG. 1A illustrates an exemplary embodiment of a ceramic composite separator 100a according to an exemplary embodiment. As shown in FIG. 1A, the ceramic composite separator 100a comprises a polymer scaffold 110 and a coating 120 including ceramic particles 130. In some embodiments, a portion of the ceramic particles 130 may be disposed within a portion of the polymer scaffold 110, as shown in FIG. 1A.

[0010]

[0015] In various embodiments, the polymer scaffold 110 can have a thickness 110t of about 5 microns to about 25 microns, about 5 microns to about 20 microns, about 5 microns to about 15 microns, or about 5 microns to about 10 microns, including any range of thickness values ​​therebetween.

[0011]

[0016] In various embodiments, the polymer scaffold 110 may comprise at least one polymer selected from the group consisting of polyolefins, polyethylene terephthalate, polyacrylonitrile, polyesters, polyamides, aromatic polyamides, polystyrene, polycarbonates, polytetrafluoroethylene, boron nitride, and cellulosic materials.

[0012]

[0017] In various embodiments, the polymer scaffold 110 can have a pore size of about 5 microns to about 50 microns, about 5 microns to about 40 microns, about 5 microns to about 30 microns, about 5 microns to about 25 microns, about 5 microns to about 20 microns, about 5 microns to about 15 microns, about 5 microns to about 10 microns, including any pore size range therebetween.

[0013]

[0018] In various embodiments, the polymer scaffold 110 can have a porosity ranging from about 20% to about 80%, about 25% to about 80%, about 30% to about 80%, about 35% to about 80%, about 40% to about 80%, about 45% to about 80%, about 50% to about 80%, about 55% to about 80%, about 60% to about 80%, about 20% to about 75%, about 20% to about 70%, about 20% to about 65%, about 20% to about 60%, about 20% to about 55%, about 20% to about 50%, about 20% to about 45%, about 20% to about 40%, about 20% to about 35%, about 20% to about 30%, including any porosity range therebetween.

[0014]

[0019] In various embodiments, coating 120 (also referred to herein as solidified coating 120) can have a thickness 120t ranging from about 1 micron to about 20 microns, from about 1 micron to about 15 microns, from about 1 micron to about 10 microns, from about 1 micron to about 5 microns, from about 1 micron to about 4 microns, from about 1 micron to about 3 microns, or from about 1 micron to about 3 microns, including any range of thickness values ​​therebetween.

[0015]

[0020] In various embodiments, the ceramic particles 130 may comprise a material selected from the group consisting of lithium perovskite (LLTO), lithium garnet (LLZO), lithium sulfide (LGPS, LPS), and NASICON-type (LAGP, LATP) ceramics.

[0016]

[0021] In various embodiments, the ceramic particles 130 can have a particle size distribution ranging from about 0.01 microns to about 10 microns, from about 0.01 microns to about 5 microns, from about 0.01 microns to about 1 micron, from about 0.05 microns to about 10 microns, from about 0.05 microns to about 5 microns, from about 0.05 microns to about 1 micron, from about 0.1 microns to about 10 microns, from about 0.1 microns to about 5 microns, or from about 0.1 microns to about 1 micron, including any particle size distribution range therebetween.

[0017]

[0022] In various embodiments, the ceramic particles 130 can have an average particle size ranging from about 0.1 microns to about 5 microns, from about 0.1 microns to about 3 microns, from about 0.1 microns to about 2 microns, from about 0.1 microns to about 1 micron, from about 0.2 microns to about 5 microns, from about 0.2 microns to about 3 microns, from about 0.2 microns to about 2 microns, from about 0.2 microns to about 1 micron, from about 0.3 microns to about 5 microns, from about 0.3 microns to about 3 microns, from about 0.3 microns to about 2 microns, from about 0.3 microns to about 1 micron, from about 0.4 microns to about 5 microns, from about 0.4 microns to about 3 microns, from about 0.4 microns to about 2 microns, from about 0.4 microns to about 1 micron, from about 0.5 microns to about 5 microns, from about 0.5 microns to about 3 microns, from about 0.5 microns to about 2 microns, or from about 0.5 microns to about 1 micron, including any average particle size range therebetween.

[0018]

[0023] In various embodiments, an organic binder 140 can be used to hold the ceramic particles 130 in place within the coating 120. In various embodiments, the organic binder 140 can bind the individual ceramic particles 130 to one another within the coating 120. In various embodiments, the organic binder 140 can bind the individual ceramic particles 130 of the coating 120 to the polymer scaffold 110.

[0019]

[0024] In various embodiments, the organic binder 140 can include a fluorinated polymer. In various embodiments, the organic binder 140 can include polyvinylidene fluoride or polyvinylidene hexafluoropropylene fluoride. In various embodiments, the organic binder 140 can include a curable resin.

[0020]

[0025] FIG. 1B illustrates an exemplary embodiment of a ceramic composite separator 100b according to various embodiments. In various embodiments, coating 120 can be a first coating 120a disposed on a first side of polymer scaffold 110, and another coating 120, referred to as second coating 120b, can be disposed on a second side of polymer scaffold 120, as shown in FIG. 1B. In other words, coating 120 is formed on both sides of polymer scaffold 110 (as coatings 120a and 120b). In various embodiments, second coating 120b can include a second plurality of ceramic particles 130 disposed on the second side of polymer scaffold 110. In some embodiments, a portion of ceramic particles 130 can be disposed on a second portion of polymer scaffold 110, as shown in FIG. 1B.

[0021]

[0026] In various embodiments, coatings 120a and 120b (also referred to herein as solidified coatings 120a and 120b) can have thicknesses 120t1 and 120t2, respectively, ranging from about 1 micron to about 20 microns, from about 1 micron to about 15 microns, from about 1 micron to about 10 microns, from about 1 micron to about 5 microns, from about 1 micron to about 4 microns, from about 1 micron to about 3 microns, or from about 1 micron to about 3 microns, including any thickness 120t1 and 120t2 range therebetween.

[0022]

[0027] Other features of ceramic composite separator 100b are similar or identical to those of ceramic composite separator 100a, as indicated by their reference numerals, and will not be described in further detail.

[0023]

[0028] 1C shows an exemplary embodiment of a ceramic composite separator 100c according to various embodiments. As shown in FIG. 1C, the ceramic particles 130 of the coating 120 are disposed completely or substantially throughout the polymer scaffold 110. In various embodiments, the ceramic composite separator 100c has a thickness 100t or 120t3 that is a combination of the thickness 110t of the polymer scaffold 110 and the thicknesses 120t1 and 120t2 of the coatings, as shown in FIG. 1C.

[0024]

[0029] Other features of ceramic composite separator 100c are similar or identical to those of ceramic composite separators 100a and 100b, as indicated by their respective reference numerals, and will not be described in further detail.

[0025]

[0030] 2A illustrates an exemplary embodiment of an electrochemical cell 200 according to various embodiments. According to various embodiments, the electrochemical cell 200 may include a battery, a lithium-based battery, a lithium battery, a lithium-ion battery, a solid-state lithium battery, a solid-state lithium-ion battery, a lithium polymer battery, or any other device that utilizes electrochemistry of chemical materials.

[0026]

[0031] As shown in FIG. 2A, electrochemical cell 200 can include a cathode 210, an anode 220, and a ceramic composite separator 100 (e.g., 100a, 100b, or 100c described with respect to FIGS. 1A, 1B, and 1C) disposed therebetween.

[0027]

[0032] 2B illustrates an exemplary embodiment of a bipolar electrochemical cell 201 according to various embodiments. As shown in FIG. 2B, the bipolar electrochemical cell 201 may be constructed by stacking two or more of the electrochemical cells 200 of FIG. 2A back-to-back on one another. According to various embodiments, the bipolar electrochemical cell 201 may be constructed by stacking two or more of the electrochemical cells 200 in a bipolar cell configuration, such that any and all components of the bipolar electrochemical cell 201 may comprise the respective components of the electrochemical cell 200 described with respect to FIG. 2A, and thus the various components of the bipolar electrochemical cell 201 are identical to, similar to, or substantially similar to the components of the electrochemical cell 200.

[0028]

[0033] As shown in FIG. 2B , bipolar electrochemical cell 201 can include first cell 201 a, second cell 201 b, third cell 201 b, and so on up to cell 201 n. Each of cells 201 a...201 n can include a cathode 210, an anode 220, and a ceramic composite separator 100 (e.g., 100 a, 100 b, or 100 c described with respect to FIGS. 1A, 1B, and 1C) disposed therebetween. In various embodiments, bipolar electrochemical cell 201 can be constructed into a high-voltage bipolar lithium-based battery having the components disclosed herein with respect to FIGS. 1A, 1B, 1C, 2A, and 2B. In various embodiments, the voltage of this battery can be varied by changing the number of cells in the stack.

[0029]

[0034] 3 illustrates a method S100 for preparing a ceramic composite separator according to various embodiments. According to various embodiments, the method S100 can be used to prepare any of the ceramic composite separators 100a, 100b, or 100c described with respect to FIGS. 1A, 1B, and 1C.

[0030]

[0035] As shown in FIG. 3, method S100 includes, in step S110, providing a polymer scaffold; in step S120, forming a coating on the polymer scaffold including a plurality of ceramic particles; and in step S130, solidifying the coating on the polymer scaffold, thereby forming a ceramic composite separator including the solidified coating on the polymer scaffold.

[0031]

[0036] According to various embodiments, the polymer scaffold of Figure 3 is similar to or identical to the polymer scaffold 110 described with respect to Figures 1A, 1B, and 1C and will not be described in further detail. According to various embodiments, the coating of Figure 3 is similar to or identical to the coating 120, 120a, or 120b described with respect to Figures 1A, 1B, and 1C and will not be described in further detail. According to various embodiments, the ceramic particles of Figure 3 are similar to or identical to the ceramic particles 130 described with respect to Figures 1A, 1B, and 1C and will not be described in further detail.

[0032]

[0037] In various embodiments, forming a coating on the polymer scaffold can be performed by applying a suspension of ceramic particles in a solution to the polymer scaffold, the suspension of ceramic particles including an organic binder dissolved in an organic solvent. In various embodiments, forming a coating on the polymer scaffold can be performed by impregnating a portion of the plurality of ceramic particles into the polymer scaffold. In various embodiments, forming a coating on the polymer scaffold can be performed via dip-coating, blade-coating, spray-coating, rolling, or painting the polymer scaffold with the suspension of ceramic particles.

[0033]

[0038] In various embodiments, the ceramic particle suspension has, by weight of the ceramic particles, about 10% to about 50%, about 15% to about 50%, about 20% to about 50%, about 25% to about 50%, about 30% to about 50%, about 35% to about 50%, about 40% to about 50%, about 10% to about 45%, about 10% to about 40%, about 10% to about 35%, about 10% to about 30%, about 10% to about 25%, or about 10% to about 20% ceramic particles.

[0034]

[0039] In various embodiments, the ceramic particle suspension is, based on the weight of the organic binder, about 0.5% to about 25% by weight, about 1% to about 25% by weight, about 1.5% to about 25% by weight, about 2% to about 25% by weight, about 2.5% to about 25% by weight, about 3% to about 25% by weight, about 3.5% to about 25% by weight, about 4% to about 25% by weight, about 4.5% to about 25% by weight, about 5% to about 25% by weight, about 7% to about 25% by weight, about 10% to about 25% by weight, or mass%, about 15 mass% to about 25 mass%, about 20 mass% to about 25 mass%, about 0.5 mass% to about 20 mass%, about 0.5 mass% to about 15 mass%, about 0.5 mass% to about 10 mass%, about 0.5 mass% to about 8 mass%, about 0.5 mass% to about 7 % by mass, about 0.5% by mass to about 6% by mass, about 0.5% by mass to about 5% by mass, about 0.5% by mass to about 4% by mass, about 0.5% by mass to about 3% by mass, about 0.5% by mass to about 2% by mass, or about 0.5% by mass to about 1% by mass.

[0035]

[0040] In various embodiments, the organic solvent comprises at least one organic compound selected from the group consisting of acetone, ethanol, 1-propanol, 2-propanol, acetonitrile, diethyl ether, dimethylformamide, tetrahydrofuran, dimethyl sulfoxide, toluene, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate.

[0036]

[0041] In various embodiments, solidifying the coating on the polymer scaffold is performed by removing the organic solvent under high temperature and / or vacuum. In other words, solidifying the coating involves drying by heating or evaporating the solvent. In various embodiments, solidifying the coating on the polymer scaffold is performed by curing the organic binder by exposure to UV light, where the organic binder is sensitive to UV light. In various embodiments, calendering can be performed after the coating is formed, for example, by pressing the coated polymer scaffold.

[0037]

[0042] Generally, the following describes one method for making a composite separator: a) creating a suspension of a lithium-conducting ceramic material in a solution containing an organic solvent and an organic binder, b) coating the suspension onto a porous polymer scaffold, and c) solidifying the film onto the polymer scaffold.

[0038]

[0043] In various embodiments, the polymer scaffold can include materials suitable for use as battery separators, such as, but not limited to, polyolefins, polyethylene terephthalate, polyacrylonitrile, polyesters, polyamides, aromatic polyamides, polystyrene, polycarbonate, polytetrafluoroethylene, boron nitride, and cellulosic materials. In some embodiments, the polymer scaffold can have a thickness of less than 25 microns, preferably between about 10 microns and about 20 microns, so that the thickness of the coated separator is less than 25 microns. The polymer scaffold preferably has an average pore size greater than 5 microns and a porosity of 20-80% so that ceramic particles can be impregnated within the scaffold material.

[0039]

[0044] In various embodiments, the ceramic particles comprising the lithium conductive ceramic material can be selected from the group consisting of lithium perovskite (LLTO), lithium garnet (LLZO), lithium sulfide (LGPS, LPS), and NASICON-type (LAGP, LATP) ceramics. The ceramic can comprise about 10% to about 50% by weight of the suspension. The ceramic particles preferably have a maximum particle size of 10 microns and an average particle size of 0.1 to 5 microns so that the ceramic particles can be impregnated within the scaffold material.

[0040]

[0045] In various embodiments, the composite suspension may contain a dissociable lithium salt at a concentration of about 0.1 M to about 1 M to increase the lithium content of the resulting composite separator, such as, but not limited to, LiPF, LiFSI, LiTFSI, or LiTDI.

[0041]

[0046] In various embodiments, an organic solvent may be used to dissolve the binder material and disperse the ceramic material. The solvent should have high solubility for the binder material so that the binder material can be completely dissolved. The organic solvent may be, for example, but not limited to, acetone, ethanol, 1-propanol, 2-propanol, acetonitrile, diethyl ether, dimethylformamide, tetrahydrofuran, dimethyl sulfoxide, toluene, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, or some combination thereof.

[0042]

[0047] In various embodiments, the binder material is an organic polymer, including but not limited to polyvinylidene fluoride or polyvinylidene hexafluoropropylene fluoride. Films utilizing polymer binders may be solidified by removing the organic solvent under application of elevated temperature and / or vacuum.

[0043]

[0048] In various embodiments, the binder material includes a monomer and / or oligomer having reactive alkene groups and a photoinitiator that is sensitive to ultraviolet light. Films using the curable binder can be solidified by exposure to ultraviolet light.

[0044]

[0049] In various embodiments, the composite suspension is dispersed by ultrasonic agitation. The composite suspension may be maintained under constant agitation to prevent agglomeration or settling of the ceramic particles.

[0045]

[0050] In various embodiments, the composite suspension is deposited onto the polymer scaffold by a coating technique, such as dip coating, blade coating, spray coating, rolling, or painting. The composite suspension may be deposited on one or both sides of the polymer scaffold. The suspension is preferentially deposited on both sides of the scaffold using dip coating.

[0046]

[0051] In various embodiments, the composite separator is a composite of a lithium metal anode and a lithiated metal cathode (e.g., LiCoO, LiFePO, LiMnO, LiNiO, LiFePOF, Li(Li a Ni x Mn y Co z ), or Li(Li a Ni x Al y Co z )), which when combined with appropriate current collectors and packaging may form a rechargeable solid-state lithium ion battery.

[0047] Enumeration of Embodiments

[0052] Embodiment 1. A ceramic composite separator comprising: a polymer scaffold; and a coating comprising a plurality of ceramic particles, a portion of the plurality of ceramic particles disposed within the polymer scaffold.

[0048]

[0053] Embodiment 2. The ceramic composite separator of embodiment 1, further comprising: a first coating disposed on a first side of the polymer scaffold, the plurality of ceramic particles being a first plurality of ceramic particles; and a second coating comprising a second plurality of ceramic particles disposed on a second side of the polymer scaffold, a portion of the second plurality of ceramic particles disposed within the polymer scaffold.

[0049]

[0054] Embodiment 3. The ceramic composite separator of embodiment 1, wherein the coating is formed on both sides of the polymer scaffold.

[0050]

[0055] Embodiment 4. The ceramic composite separator of any one of embodiments 1-3, further comprising an organic binder, wherein the organic binder binds individual ceramic particles to one another within the coating, and the organic binder binds the individual ceramic particles of the coating to the polymer scaffold.

[0051]

[0056] Embodiment 5. The ceramic composite separator of embodiment 4, wherein the organic binder comprises a fluorinated polymer.

[0052]

[0057] Embodiment 6. The ceramic composite separator of embodiment 5, wherein the organic binder is polyvinylidene fluoride or polyvinylidene hexafluoropropylene fluoride.

[0053]

[0058] Embodiment 7. The ceramic composite separator according to any one of embodiments 4 to 6, wherein the organic binder contains a curable resin.

[0054]

[0059] Embodiment 8. A ceramic composite separator according to any one of embodiments 1 to 7, wherein the polymer scaffold comprises at least one polymer selected from the group consisting of polyolefins, polyethylene terephthalate, polyacrylonitrile, polyesters, polyamides, aromatic polyamides, polystyrene, polycarbonates, polytetrafluoroethylene, boron nitride, and cellulosic materials.

[0055]

[0060] Embodiment 9. The ceramic composite separator of any one of embodiments 1 to 8, wherein the polymer scaffold has a thickness of about 5 microns to about 25 microns.

[0056]

[0061] Embodiment 10. The ceramic composite separator according to any one of embodiments 1 to 9, wherein the polymer scaffold has a pore size of about 5 microns to about 50 microns.

[0057]

[0062] Embodiment 11. The ceramic composite separator of any one of embodiments 1 to 10, wherein the polymer scaffold has a porosity ranging from about 20% to about 80%.

[0058]

[0063] Embodiment 12. The ceramic composite separator of any one of embodiments 1 to 11, wherein the plurality of ceramic particles comprises a material selected from the group consisting of lithium perovskite (LLTO), lithium garnet (LLZO), lithium sulfide (LGPS, LPS), and NASICON-type (LAGP, LATP) ceramics.

[0059]

[0064] Embodiment 13. The ceramic composite separator according to any one of embodiments 1 to 12, wherein the plurality of ceramic particles have a particle size distribution ranging from about 0.01 microns to about 10 microns.

[0060]

[0065] Embodiment 14. The ceramic composite separator according to any one of embodiments 1 to 13, wherein the plurality of ceramic particles have an average particle size ranging from about 0.1 microns to about 5 microns.

[0061]

[0066] Embodiment 15. An electrochemical cell comprising a cathode, an anode, and the ceramic composite separator according to any one of embodiments 1 to 14.

[0062]

[0067] Embodiment 16. A bipolar electrochemical cell comprising the ceramic composite separator according to any one of embodiments 1 to 14.

[0063]

[0068] Embodiment 17. A method of preparing a ceramic composite separator comprising: providing a polymer scaffold; forming a coating on the polymer scaffold comprising a plurality of ceramic particles; and solidifying the coating on the polymer scaffold, thereby forming a ceramic composite separator comprising the solidified coating on the polymer scaffold.

[0064]

[0069] Embodiment 18. The method of embodiment 17, wherein forming a coating on the polymer scaffold comprises applying a suspension of ceramic particles in a solution to the polymer scaffold, the suspension of ceramic particles comprising an organic binder dissolved in an organic solvent.

[0065]

[0070] Embodiment 19. The method of embodiment 17 or 18, wherein forming a coating on the polymer scaffold comprises impregnating a portion of the plurality of ceramic particles into the polymer scaffold.

[0066]

[0071] Embodiment 20. The method of embodiment 18 or 19, wherein forming the coating on the polymer scaffold is carried out via application of dip coating, blade coating, spray coating, rolling, or painting of the polymer scaffold with a suspension of ceramic particles.

[0067]

[0072] Embodiment 21 The method of any one of embodiments 17 to 20, wherein the coating is formed on both sides of the polymer scaffold.

[0068]

[0073] Embodiment 22. The method of any one of embodiments 18-21, wherein the suspension of ceramic particles has about 10% to about 50% by weight of ceramic particles, based on the weight of the ceramic particles.

[0069]

[0074] Embodiment 23. The method of any one of embodiments 18-22, wherein the suspension of ceramic particles has about 0.5% to about 25% by weight of the organic binder, based on the weight of the organic binder.

[0070]

[0075] Embodiment 24. The method of any one of embodiments 18-23, wherein the organic solvent comprises at least one organic compound selected from the group consisting of acetone, ethanol, 1-propanol, 2-propanol, acetonitrile, diethyl ether, dimethylformamide, tetrahydrofuran, dimethyl sulfoxide, toluene, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate.

[0071]

[0076] Embodiment 25. The method of any one of embodiments 18 to 24, wherein solidifying the coating on the polymer scaffold is carried out by removal of the organic solvent under application of elevated temperature and / or vacuum.

[0072]

[0077] Embodiment 26. The method of any one of embodiments 18-24, wherein solidifying the coating on the polymer scaffold is carried out by curing the organic binder by exposure to UV light, and the organic binder is photosensitive to UV light.

[0073]

[0078] Embodiment 27. The method of any one of embodiments 17 to 26, wherein the solidified coating has a thickness of about 1 micron to about 20 microns.

[0074]

[0079] Embodiment 28. The method of any one of embodiments 18-27, wherein the organic binder comprises a fluorinated polymer.

[0075]

[0080] Embodiment 29. The method of any one of embodiments 18 to 28, wherein the organic binder is polyvinylidene fluoride or polyvinylidene hexafluoropropylene fluoride.

[0076]

[0081] Embodiment 30. The method of any one of embodiments 18-29, wherein the organic binder comprises a curable resin.

[0077]

[0082] Embodiment 31. The method of any one of embodiments 17 to 30, wherein the polymer scaffold comprises at least one polymer selected from the group consisting of polyolefins, polyethylene terephthalate, polyacrylonitrile, polyesters, polyamides, aromatic polyamides, polystyrene, polycarbonates, polytetrafluoroethylene, boron nitride, and cellulosic materials.

[0078]

[0083] Embodiment 32. The method of any one of embodiments 17 to 31, wherein the polymer scaffold has a thickness of about 5 microns to about 25 microns.

[0079]

[0084] Embodiment 33. The method of any one of embodiments 17 to 32, wherein the polymer scaffold has a pore size of about 5 microns to about 50 microns.

[0080]

[0085] Embodiment 34. The method of any one of embodiments 17 to 33, wherein the polymer scaffold has a porosity ranging from about 20% to about 80%.

[0081]

[0086] Embodiment 35. The method of any one of embodiments 17-34, wherein the plurality of ceramic particles comprises a material selected from the group consisting of lithium perovskite (LLTO), lithium garnet (LLZO), lithium sulfide (LGPS, LPS), and NASICON-type (LAGP, LATP) ceramics.

[0082]

[0087] Embodiment 36. The method of any one of embodiments 17-35, wherein the plurality of ceramic particles has a particle size distribution ranging from about 0.01 microns to about 10 microns.

[0083]

[0088] Embodiment 37. The method of any one of embodiments 17-36, wherein the plurality of ceramic particles has an average particle size in the range of about 0.1 microns to about 5 microns.

[0084]

[0089] Embodiment 38. An electrochemical cell comprising a cathode, an anode, and a ceramic composite separator made by the method of any one of embodiments 17-37.

[0085]

[0090] Embodiment 39. A bipolar electrochemical cell comprising a ceramic composite separator made according to any one of embodiments 17-37.

Claims

1. a polymer scaffold; a coating comprising a plurality of ceramic particles, a portion of the plurality of ceramic particles disposed within the polymer scaffold; and A ceramic composite separator comprising:

2. the coating is a first coating disposed on a first side of the polymer scaffold and the plurality of ceramic particles is a first plurality of ceramic particles; a second coating including a second plurality of ceramic particles disposed on a second side of the polymer scaffold, a portion of the second plurality of ceramic particles disposed within the polymer scaffold. The ceramic composite separator of claim 1 further comprising:

3. The ceramic composite separator of claim 1 , wherein the coating is formed on both sides of the polymer scaffold.

4. An organic binder, the organic binder binds the individual ceramic particles together within the coating; the organic binder binding the individual ceramic particles of the coating to the polymer scaffold; The ceramic composite separator according to any one of claims 1 to 3, further comprising:

5. The ceramic composite separator of claim 4 , wherein the organic binder comprises a fluorinated polymer.

6. The ceramic composite separator according to claim 5 , wherein the organic binder is polyvinylidene fluoride or polyvinylidene hexafluoropropylene fluoride.

7. The ceramic composite separator according to any one of claims 4 to 6, wherein the organic binder contains a curable resin.

8. 8. The ceramic composite separator according to claim 1, wherein the polymer scaffold comprises at least one polymer selected from the group consisting of polyolefin, polyethylene terephthalate, polyacrylonitrile, polyester, polyamide, aromatic polyamide, polystyrene, polycarbonate, polytetrafluoroethylene, boron nitride, and cellulosic materials.

9. The ceramic composite separator of any one of claims 1 to 8, wherein the polymer scaffold has a thickness of from about 5 microns to about 25 microns.

10. The ceramic composite separator of any one of claims 1 to 9, wherein the polymer scaffold has a pore size of about 5 microns to about 50 microns.

11. The ceramic composite separator of any one of claims 1 to 10, wherein the polymer scaffold has a porosity ranging from about 20% to about 80%.

12. 12. The ceramic composite separator according to claim 1, wherein the plurality of ceramic particles comprises a material selected from the group consisting of lithium perovskite (LLTO), lithium garnet (LLZO), lithium sulfide (LGPS, LPS), and NASICON-type (LAGP, LATP) ceramics.

13. 13. The ceramic composite material of any one of claims 1 to 12, wherein the plurality of ceramic particles have a particle size distribution ranging from about 0.01 microns to about 10 microns.

14. The ceramic composite separator of any one of claims 1 to 13, wherein the plurality of ceramic particles have an average particle size ranging from about 0.1 microns to about 5 microns.

15. An electrochemical cell comprising a cathode, an anode, and the ceramic composite separator of any one of claims 1 to 14.

16. A bipolar electrochemical cell comprising the ceramic composite separator according to any one of claims 1 to 14.

17. providing a polymer scaffold; forming a coating on the polymer scaffold comprising a plurality of ceramic particles; solidifying the coating on the polymer scaffold, thereby forming the ceramic composite separator including the solidified coating on the polymer scaffold; A method for preparing a ceramic composite separator, comprising:

18. 18. The method of claim 17, wherein forming the coating on the polymer scaffold comprises applying a suspension of ceramic particles in a solution to the polymer scaffold, the suspension of ceramic particles comprising an organic binder dissolved in an organic solvent.

19. 19. The method of claim 17 or 18, wherein forming the coating on the polymer scaffold comprises impregnating the polymer scaffold with a portion of the plurality of ceramic particles.

20. 20. The method of claim 18 or 19, wherein forming the coating on the polymer scaffold is carried out via dip coating, blade coating, spray coating, rolling, or painting of the polymer scaffold with a suspension of the ceramic particles.

21. The method of any one of claims 17 to 20, wherein the coating is formed on both sides of the polymer scaffold.

22. 22. The method of any one of claims 18 to 21, wherein the suspension of ceramic particles has about 10% to about 50% by weight of the ceramic particles, based on the weight of the ceramic particles.

23. 23. The method of any one of claims 18 to 22, wherein the suspension of ceramic particles has from about 0.5% to about 25% by weight of the organic binder, based on the weight of the organic binder.

24. The method according to any one of claims 18 to 23, wherein the organic solvent comprises at least one organic compound selected from the group consisting of acetone, ethanol, 1-propanol, 2-propanol, acetonitrile, diethyl ether, dimethylformamide, tetrahydrofuran, dimethyl sulfoxide, toluene, dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate.

25. 25. The method of any one of claims 18 to 24, wherein solidifying the coating on the polymer scaffold is carried out by removal of the organic solvent under application of elevated temperature and / or vacuum.

26. 25. The method of any one of claims 18 to 24, wherein solidifying the coating on the polymer scaffold is carried out by curing the organic binder by exposure to UV light, the organic binder being sensitive to the UV light.

27. The method of any one of claims 17 to 26, wherein the hardened coating has a thickness of from about 1 micron to about 20 microns.

28. The method of any one of claims 18 to 27, wherein the organic binder comprises a fluorinated polymer.

29. The method according to any one of claims 18 to 28, wherein the organic binder is polyvinylidene fluoride or polyvinylidene hexafluoropropylene fluoride.

30. The method of any one of claims 18 to 29, wherein the organic binder comprises a curable resin.

31. 31. The method of any one of claims 17 to 30, wherein the polymer scaffold comprises at least one polymer selected from the group consisting of polyolefins, polyethylene terephthalate, polyacrylonitrile, polyesters, polyamides, aromatic polyamides, polystyrene, polycarbonates, polytetrafluoroethylene, boron nitride, and cellulosic materials.

32. 32. The method of any one of claims 17 to 31, wherein the polymer scaffold has a thickness of from about 5 microns to about 25 microns.

33. 33. The method of any one of claims 17 to 32, wherein the polymer scaffold has a pore size of about 5 microns to about 50 microns.

34. 34. The method of any one of claims 17 to 33, wherein the polymer scaffold has a porosity ranging from about 20% to about 80%.

35. 35. The method of any one of claims 17 to 34, wherein the plurality of ceramic particles comprises a material selected from the group consisting of lithium perovskite (LLTO), lithium garnet (LLZO), lithium sulfide (LGPS, LPS), and NASICON-type (LAGP, LATP) ceramics.

36. 36. The method of any one of claims 17 to 35, wherein the plurality of ceramic particles has a particle size distribution ranging from about 0.01 microns to about 10 microns.

37. 37. The method of any one of claims 17 to 36, wherein the plurality of ceramic particles has an average particle size ranging from about 0.1 microns to about 5 microns.

38. An electrochemical cell comprising a cathode, an anode, and a ceramic composite separator produced by the method of any one of claims 17 to 37.

39. A bipolar electrochemical cell comprising a ceramic composite separator made according to any one of claims 17 to 37.

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