Batteries containing solid ionically conductive membranes

Abstract

A battery comprising: an anode and a cathode defining an electric field therebetween; and a solid, ionically conductive membrane between the anode and the cathode, the solid, ionically conductive membrane comprising a polycrystalline microstructure, the polycrystalline microstructure defining grain boundaries between adjacent grains of the polycrystalline microstructure, a majority of the grain boundary regions of the polycrystalline microstructure being oriented substantially perpendicular to the direction of the electric field defined by the anode and the cathode.

Description

[Technical Field]

[0001] This application relates to the field of batteries that include solid ionically conductive membranes. [Background technology]

[0002] Solid ionically conductive membranes offer a safe alternative to liquid electrolytes in battery technology, but they are susceptible to the formation, growth, and penetration of metallic dendrites, which can cause short circuits and limit the cycle life of batteries.

[0003] Accordingly, those skilled in the art continue to conduct research and development in the field of batteries that include solid ionically conductive membranes. Summary of the Invention [Means for solving the problem]

[0004] In one embodiment, a battery includes an anode and a cathode defining an electric field therebetween, and a solid, ionically conductive membrane between the anode and the cathode, the solid, ionically conductive membrane including a polycrystalline microstructure defining grain boundaries between adjacent grains of the polycrystalline microstructure, the majority of the grain boundary regions of the polycrystalline microstructure being oriented substantially perpendicular to the direction of the electric field defined by the anode and the cathode.

[0005] In another embodiment, a method of fabricating a solid ionically conductive membrane for a battery includes melting and spraying an ionically conductive material onto a substrate to form a solid ionically conductive membrane having a polycrystalline microstructure, the polycrystalline microstructure defining grain boundaries between adjacent grains of the polycrystalline microstructure, and disposing the solid ionically conductive membrane between an anode and a cathode, wherein a majority of the grain boundary regions of the polycrystalline microstructure are oriented substantially perpendicular to the direction of an electric field defined by the anode and cathode.

[0006] Other embodiments will become apparent from the following detailed description, the accompanying drawings, and the appended claims. [Brief explanation of the drawings]

[0007]

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[0008] Figure 1 shows an exploded perspective cross-sectional view of a comparative battery 2, where battery 2 includes an anode 4 and a cathode 6 defining an electric field 8 therebetween, and a conventionally sintered solid ionically conductive membrane 10 between anode 4 and cathode 6. Figure 2 is a vertical cross-sectional view of the conventionally sintered solid ionically conductive membrane 10 of Figure 1. Conventionally sintered solid electrolyte membranes 10 are susceptible to the formation and growth of metallic dendrites that cause short circuits leading to battery failure.

[0009] The inventors believe that the formation and growth of metallic dendrites in a solid ion conductive membrane sintered by a conventional method are driven by the presence of electrons at grain boundaries. As shown in FIGS. 1 and 2, a solid ion conductive membrane sintered by a conventional method typically has grain boundaries in the form of close-packed hexagons oriented substantially randomly, and many of the grain boundary regions are oriented substantially parallel to the direction of the electric field of the battery. As shown in FIG. 2, during use of the battery, the electric field drives electrons to pass through grain boundaries that are substantially parallel to the direction of the electric field. These grain boundaries then become charged with electrons or function as highly conductive channels. When ions (e.g., lithium ions) pass through these same grain boundaries, these ions are reduced by the electrons to form and / or grow metallic dendrites along these grain boundaries, thereby causing or contributing to a short circuit that leads to battery failure. This description addresses the aforementioned problems of batteries that include solid ion conductive membranes sintered by conventional methods.

[0010] According to the present disclosure, a battery according to this description includes an anode and a cathode that define an electric field therebetween, and a solid ion conductive membrane between the anode and the cathode. The solid ion conductive membrane includes a polycrystalline microstructure that defines grain boundaries between adjacent particles of the polycrystalline microstructure, and most of the grain boundary regions of the polycrystalline microstructure are oriented substantially perpendicular to the direction of the electric field defined by the anode and the cathode.

[0011] FIG. 3 shows an exploded perspective cross-sectional view of a battery 2 according to this description, where the battery 2 includes an anode 4 and a cathode 6 that define an electric field 8 therebetween, and a solid ion conductive membrane 10 according to this description between the anode 4 and the cathode 6. FIG. 4 is a cross-sectional view perpendicular to the solid ion conductive membrane 10 of FIG. 3. As shown in FIGS. 3 and 4, the solid ion conductive membrane 10 includes a polycrystalline microstructure 12 that defines grain boundaries 14 between adjacent particles 16 of the polycrystalline microstructure 12, and most of the grain boundary regions of the polycrystalline microstructure 12 are oriented substantially perpendicular to the direction of the electric field 8 defined by the anode 6 and the cathode 8.

[0012] The electric field of the battery does not tend to drive electrons through grain boundaries that are substantially perpendicular to the direction of the electric field. By orienting the majority of the grain boundary regions of the polycrystalline microstructure to be substantially perpendicular to the direction of the electric field, the electric field does not tend to drive electrons through those grain boundaries, and the aforementioned problems with the formation and / or growth of metallic dendrites are minimized. The polycrystalline microstructure can be provided with the desired grain boundary orientation of the present disclosure by the manufacturing method used to form the solid ionically conductive membrane, for example, by forming the solid ionically conductive membrane by a spraying process, as further described below.

[0013] The term "major portion" of the grain boundary region of the polycrystalline microstructure refers to at least 50% of the grain boundary region being oriented substantially perpendicular to the direction of the electric field. Preferably, at least 55% of the grain boundary region is oriented substantially perpendicular to the direction of the electric field. More preferably, at least 60% of the grain boundary region is oriented substantially perpendicular to the direction of the electric field. More preferably, at least 65% of the grain boundary region is oriented substantially perpendicular to the direction of the electric field. A more preferred embodiment is that at least 70% of the grain boundary region is oriented substantially perpendicular to the direction of the electric field. More preferably, at least 75% of the grain boundary region is oriented substantially perpendicular to the direction of the electric field. More preferably, at least 80% of the grain boundary region is oriented substantially perpendicular to the direction of the electric field. More preferably, at least 85% of the grain boundary region is oriented substantially perpendicular to the direction of the electric field. More preferably, at least 90% of the grain boundary region is oriented substantially perpendicular to the direction of the electric field. The amount of the grain boundary region oriented substantially perpendicular to the direction of the electric field can be controlled by the selection of parameters during the manufacturing method of the solid ion conductive membrane. In one example, the parameters of the spraying process can be controlled to reduce the amount of the completely melted raw material, thereby achieving a reduction in the amount of the grain boundary region oriented substantially perpendicular to the direction of the electric field, or the parameters of the spraying process can be controlled to increase the amount of the completely melted raw material, thereby achieving an increase in the amount of the grain boundary region oriented substantially perpendicular to the direction of the electric field. In another example, a raw material with lower ductility can be selected to achieve a reduction in the amount of the grain boundary region oriented substantially perpendicular to the direction of the electric field, or a raw material with higher ductility can be selected to achieve an increase in the amount of the grain boundary region oriented substantially perpendicular to the direction of the electric field. By increasing the amount of the grain boundary region oriented substantially perpendicular to the direction of the electric field, the tendency of the electric field to drive electrons and cause the electrons to pass through the grain boundaries will decrease.

[0014] Regarding the fact that the grain boundary region of the polycrystalline microstructure is substantially perpendicular to the direction of the electric field, the term "substantially perpendicular" means that the orthogonal vector to the grain boundary plane in the vertical cross-section of the polycrystalline microstructure is within an angle A of 40 degrees from the direction of the electric field. More preferably, the orthogonal vector to the grain boundary plane is within 35 degrees from the direction of the electric field. More preferably, the orthogonal vector to the grain boundary plane is within 30 degrees from the direction of the electric field. More preferably, the orthogonal vector to the grain boundary plane is within 25 degrees from the direction of the electric field. More preferably, the orthogonal vector to the grain boundary plane is within 20 degrees from the direction of the electric field. More preferably, the orthogonal vector to the grain boundary plane is within 15 degrees from the direction of the electric field. The perpendicularity of the grain boundaries can be controlled by the selection of parameters during the manufacturing method of the solid ion conductive film. In one example, the parameters of the spraying process can be controlled to achieve flatter particles and higher perpendicularity of the grain boundaries, or the parameters of the spraying process can be controlled to achieve less flat particles and lower perpendicularity of the grain boundaries. By increasing the degree of perpendicularity of the grain boundary region with respect to the direction of the electric field, the tendency of electrons to pass through the grain boundaries due to the electric field will be reduced.

[0015] Therefore, according to the present disclosure, the grain boundary region of the polycrystalline microstructure is oriented such that at least 50% (or at least 55%, 60%, 65%, 70%, 75%, 80%, 85%, or 90%) of the grain boundary region has an orthogonal direction within 40 degrees (or within 35 degrees, 30 degrees, 25 degrees, 20 degrees, 15 degrees) from the direction of the electric field defined by the anode and the cathode.

[0016] The percentage of grain boundary regions oriented substantially perpendicular to the direction of the electric field can be determined from a vertical cross-section of the polycrystalline microstructure. Referring to the vertical cross-section of FIG. 4, an orthogonal vector 20 can be determined for each portion of the grain boundary 14. In FIG. 4, the orthogonal vectors are shown as vertical cross-sections perpendicular to the respective portions of the grain boundary 14. A majority of the grain boundary regions of the polycrystalline microstructure of a solid ionically conductive membrane are substantially perpendicular to the direction of the electric field when at least 50% (or preferably at least 55%, 60%, 65%, 70%, 75%, 80%, 85%, or 90%) of the grain boundary regions have an orthogonal orientation with angle A within 40 degrees (or within 35 degrees, 30 degrees, 25 degrees, 20 degrees, 15 degrees) of the direction of the electric field. It is visually apparent in FIG. 4 that a majority of the grain boundary regions of the illustrated polycrystalline microstructure of a solid ionically conductive membrane are substantially perpendicular to the direction of the electric field.

[0017] In a further aspect, the polycrystalline microstructure can include a plurality of high aspect ratio particles having a high length-to-thickness ratio. The average length-to-thickness ratio of the high aspect ratio particles can be at least 2:1, more preferably at least 3:1, more preferably at least 4:1, more preferably at least 5:1, more preferably at least 6:1, more preferably at least 7:1, more preferably at least 8:1, more preferably at least 9:1, more preferably at least 10:1. The average length of the particles can be determined as the length of the particles in the vertical cross-section of the polycrystalline microstructure. The thickness of the particles can be determined as the length of the particles in the vertical cross-section of the polycrystalline microstructure. By increasing the length-to-thickness ratio of the plurality of high aspect ratio particles, the polycrystalline microstructure of the solid ion conductive membrane can comprise a large number of grain boundary regions oriented substantially perpendicular to the direction of the electric field, providing a high degree of perpendicularity of the grain boundary regions and reducing the tendency of the electric field to drive electrons to pass through the grain boundaries to the electrons. The aspect ratio can be controlled by the selection of parameters during the manufacturing method of the solid ion conductive membrane. In one example, the parameters of the spraying process can be controlled to achieve flatter particles and a higher aspect ratio, or the parameters of the spraying process can be controlled to achieve less flat particles and a lower aspect ratio.

[0018] In a further embodiment, the polycrystalline microstructure can include a large amount of high aspect ratio grains. The amount of high aspect ratio grains can be at least 10 percent, more preferably at least 20 percent, more preferably at least 30 percent, more preferably at least 40 percent, more preferably at least 50 percent, more preferably at least 60 percent, more preferably at least 70 percent, and more preferably at least 80 percent. The percentage of high aspect ratio grains can be determined as an area percentage relative to a vertical cross-section of the polycrystalline microstructure. By increasing the percentage of high aspect ratio grains, the polycrystalline microstructure of the solid ionically conductive membrane can comprise a large amount of grain boundary regions that are oriented substantially perpendicular to the direction of the electric field, providing a high degree of verticality of the grain boundary regions and reducing the tendency of the electric field to drive electrons through the grain boundaries. The amount of high aspect ratio grains can be controlled by selection of parameters during the fabrication method of the solid ionically conductive membrane. In one example, the parameters of the atomization process can be controlled to reduce the amount of fully melted raw material, thereby achieving a reduced amount of high aspect ratio particles, or the parameters of the atomization process can be controlled to increase the amount of fully melted raw material, thereby achieving an increased amount of high aspect ratio particles.

[0019] Thus, according to the present disclosure, the polycrystalline microstructure can include at least 10 percent (or at least 20 percent, 30 percent, 40 percent, 50 percent, 60 percent, 70 percent, 80 percent) high aspect ratio grains having an average length to thickness of at least 2:1 (or at least 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1). The average grain length can be determined as the length of the grain in a vertical cross section of the polycrystalline microstructure.

[0020] In a further aspect, the high aspect ratio particles of the polycrystalline microstructure can have an average length of at least 1 micron, more preferably at least 2 microns, more preferably at least 5 microns, more preferably at least 10 microns, more preferably at least 15 microns, more preferably at least 20 microns. By increasing the average length of the high aspect ratio particles, the polycrystalline microstructure of the solid ion conductive membrane can comprise a large number of grain boundary regions oriented substantially perpendicular to the direction of the electric field and a smaller amount of grain boundary regions oriented substantially parallel to the direction of the electric field. The average length of the high aspect ratio particles of the polycrystalline microstructure can be controlled by the selection of parameters during the manufacturing method of the solid ion conductive membrane. In one example, the parameters of the spray process can be controlled to reduce the amount of flatter particles and make the average length of the high aspect ratio particles shorter, or the parameters of the spray process can be controlled to increase the amount of flatter particles and make the average length of the high aspect ratio particles longer.

[0021] In one embodiment, the high aspect ratio grains of the polycrystalline microstructure can have an average thickness of less than 100 microns. In another embodiment, the high aspect ratio grains of the polycrystalline microstructure can have an average thickness of less than 50 microns. In another embodiment, the high aspect ratio grains of the polycrystalline microstructure can have an average thickness of less than 20 microns. In another embodiment, the high aspect ratio grains of the polycrystalline microstructure can have an average thickness of less than 10 microns. In another embodiment, the high aspect ratio grains of the polycrystalline microstructure can have an average thickness of less than 5 microns. In another embodiment, the high aspect ratio grains of the polycrystalline microstructure can have an average thickness of less than 1 micron. In another embodiment, the high aspect ratio grains of the polycrystalline microstructure can have an average thickness of less than 500 nm. By reducing the average thickness of the high aspect ratio grains, the polycrystalline microstructure of the solid ionically conductive membrane can have an increased density of high aspect ratio grains with respect to the thickness direction, which can inhibit the formation and / or growth of metallic dendrites along the grain boundaries. The average thickness of the high aspect ratio grains of the polycrystalline microstructure can be controlled by selection of parameters during the manufacturing method of the solid ion conducting membrane. In one example, the parameters of the spraying process can be controlled to decrease the droplet size and decrease the thickness of the high aspect ratio grains, or the parameters of the spraying process can be controlled to increase the droplet size and increase the thickness of the high aspect ratio grains.

[0022] In a further aspect, the polycrystalline microstructure of the solid ionically conductive membrane may be partially amorphous. The presence of an amorphous phase (i.e., a glassy phase) can be confirmed by X-ray diffraction. It is believed that the amorphous phase may form between the grains of the polycrystalline microstructure and thus further reduce grain boundary effects, in which grain boundaries may become charged with electrons or act as fast conductive channels. The amorphous phase may be formed in the polycrystalline microstructure of the solid ionically conductive membrane, for example, by rapidly cooling the solid ionically conductive membrane from a molten phase.

[0023] The solid ionically conductive membranes of the present disclosure comprised solid ionically conductive materials. Solid ionically conductive materials are a type of material that can selectively pass certain charged elements in the presence of a chemical potential, such as an electric field or a concentration difference. The solid ionically conductive material allows the movement of ions but may not readily allow electrons to pass through. Ions can carry one, two, three, four or more positive charges. Examples of charged ions include H + , Li + , Na + , K. + , Ag + , Mg 2+ , Zn 2+ , Al 3+ , etc. The ionic conductivity of the corresponding ions is preferably >10 -7 S / cm, more preferably >10 -4 S / cm. Lower conductivities (e.g., <10 -7 It is preferable that the viscosity of the film has a viscosity of 1000 MPa (S / cm).

[0024] Examples of solid ionically conductive materials include those having the general formula: Li n [A( 3-a’-a’’) A'( a’ )A''( a’’ )][B( 2-b’-b’’ )B'( b’ )B''( b’’ )][C'( c’ )C''( c’’ )]O 12 , Examples of oxide materials include, but are not limited to, garnet-like structure oxide materials having a. wherein A, A', and A'' represent octahedral positions in a crystal structure; i. wherein A represents one or more trivalent rare earth elements; ii. wherein A' represents one or more alkaline earth elements; iii. wherein A'' represents one or more alkali metal elements other than Li; iv. wherein 0≦a'≦2 and 0≦a''≦1; b. Wherein, B, B', and B'' represent octahedral positions in the crystal structure, i. Wherein, B represents one or more tetravalent elements, ii. Wherein, B' represents one or more pentavalent elements, iii. Wherein, B'' represents one or more hexavalent elements, iv. Wherein, 0 ≤ b', 0 ≤ b'', and b' + b'' ≤ 2; c. Wherein, C' and C'' represent tetrahedral positions in the crystal structure, i. Wherein, C' represents one or more of Al, Ga, and boron, ii. Wherein, C'' represents one or more of Si and Ge, iii. Wherein, 0 ≤ c' ≤ 0.5 and 0 ≤ c'' ≤ 0.4; d. Wherein, n = 7 + a' + 2·a'' - b' - 2·b'' - 3·c' - 4·c'', and 4.5 ≤ n ≤ 7.5.

[0025] In another example, the solid ion conductive material includes perovskite-type oxides such as (Li,La)TiO3, or doped or substituted compounds. In yet another example, the solid ion conductive material includes lithium films with a NASICON structure, such as LAGP (Li1-xAl x Ge 2-x (PO4)3), LATP (Li1+xAl x Ti 2-x (PO4)3), and these materials doped with other elements are included. In yet another example, the solid ion conductive material includes anti-perovskite structure materials and their derivatives, such as compositions of Li3OCl, Li3OBr, and Li3OI. In yet another example, the solid ion conductive material includes materials of the Li3YH6 (H = F, Cl, Br, I) group, and Y can be replaced by other rare earth elements. In yet another example, the solid ion conductive material includes Li 2x S x+w+5z M y P 2z is included, wherein x is 8 to 16, y is 0.1 to 6, w is 0.1 to 15, z is 0.1 to 3, and M is selected from the group consisting of atoms of lanthanides, Group 3, Group 4, Group 5, Group 6, Group 7, Group 8, Group 9, Group 12, Group 13, and Group 14, and combinations thereof. In yet another example, the solid ion conductive material includes the general formula: Li12-m-x (M m Y4 2- )Y 2-x 2- X x - contains an al-dirodite material, where M m+ =B 3+ , Ga 3+ , Sb 3+ , Si 4+ , Ge 4+ , P 5+ , As 5+ , or a combination thereof; Y 2- =O 2- , S 2- , Se 2- , Te 2- , or a combination thereof; X - =F - , Cl - , Br - , I - , or a combination thereof; and x is in the range of 0 ≦ x ≦ 2. In yet another example, the solid ion-conductive material contains a general formula: Li 18-2m-x (M2 m+ Y7 2- )Y 2-x 2- X x - contains an al-dirodite material, where M m+ =B 3+ , Ga 3+ , Sb 3+ , Si 4+ , Ge 4+ , P 5+ , As 5+ , or a combination thereof; Y 2- =O 2- , S 2- , Se 2- , Te 2- , or a combination thereof; X - =F - , Cl - , Br - , I - , or a combination thereof; and x is in the range of 0 ≦ x ≦ 2. The ion-conductive material may be a single crystal or a polycrystal. Alternatively, two or more ion-conductive materials may be premixed to form a composite of two or more ion-conductive materials.

[0026] The shape of the solid ion conductive membrane is not limited. In one example, the shape of the solid ion conductive membrane may be planar. In another example, the shape of the solid ion conductive membrane may be tubular. In yet another example, the shape of the solid ion conductive membrane may be an irregular shape. In still another example, the shape of the solid ion conductive membrane may match the shapes of the anode and the cathode.

[0027] The thickness of the solid ion conductive membrane is not limited. In one example, the thickness of the solid ion conductive membrane may be in the range of 0 < t < 400 μm. In another example, the thickness of the solid ion conductive membrane may be in the range of 100 < t < 200 μm. Reducing the thickness of the membrane may increase the ionic conductivity of the target ions, and thus the performance of the membrane may be improved.

[0028] In one aspect, the solid ion conductive membrane can be formed as a free-standing solid ion conductive membrane. In another aspect, the solid ion conductive membrane can be directly formed on the final substrate as a non-free-standing solid ion conductive membrane.

[0029] The main concept of the present disclosure is that in the case of a battery including a solid ion conductive membrane, when most of the grain boundary regions of the polycrystalline microstructure of the solid ion conductive membrane are oriented substantially perpendicular to the direction of the electric field, the formation and / or growth of metal dendritic crystals along these grain boundaries may be suppressed. This description is not limited to any specific method of forming the solid ion conductive membrane. The solid ion conductive membrane can be manufactured using any method capable of achieving the grain boundary orientation.

[0030] In another embodiment, a method of making a solid ionically conductive membrane includes melting and spraying an ionically conductive material to form a solid ionically conductive membrane. Spraying the molten ionically conductive material can include tapping the ionically conductive material onto a substrate to form the shape of a plate that is affixed to the surface of the substrate. The melting and spraying of the ionically conductive material continues to build up layers of the ionically conductive material on top of previously applied layers, resulting in a structure of randomly stacked interlocking layers (i.e., sheets) of ionically conductive material. Rapid cooling of the molten ionically conductive material can then form an amorphous phase in the polycrystalline microstructure of the solid ionically conductive membrane.

[0031] In one aspect, a method for making a solid ionically conductive membrane comprises a thermal spray process. Thermal spraying can be defined as a coating or spraying technique in which a feedstock or powder (i.e., a solid ionically conductive ceramic) is fed into a thermal zone where it is rapidly heated to a surface-molten state or a plastically deformable state, accelerated toward a structure, and impinged upon the structure to form a film or coating. The feedstock or powder can be defined as a solid ionically conductive material in powder form that is used to form an interlocking layered structure. Thermal spraying includes, but is not limited to, variants such as plasma spraying, flame spraying, wire arc spraying, high velocity oxy-fuel spraying, laser-assisted, and induction-assisted spraying processes. Thermal spraying may also include any other thermal spraying process that uses high temperatures to melt a solid ionically conductive powder to form a solid ionically conductive membrane.

[0032] Thermal spraying parameters are well known to those skilled in the art, and methods for varying the thermal spraying parameters to modify the resulting microstructure are well known, and the parameters may vary depending on the feedstock used. The following is a general description of the thermal spraying parameters for achieving the polycrystalline microstructure of the solid ionically conductive membranes described herein.

[0033] In the spraying process, a current can be applied to the cathode of the spraying gun. The range of the applied current can be from 100 to 1000 amperes, and the preferred range is from 250 to 750 amperes. A voltage can be applied between the anode and the cathode of the spraying gun. The range of the applied voltage can be from 10 to 200 volts, and the preferred range is from 50 to 120 volts. The operating power of the spraying gun can be in the range of 1 to 200 kilowatts, and the preferred range is from 5 to 90 kilowatts. The distance between the nozzle tip of the spraying gun and the substrate on which the solid ion conductive film is formed can be in the range of 5 to 100 cm, and the preferred range is from 10 to 25 cm. The angle of the spraying gun with respect to the substrate on which the solid ion conductive film is formed can be in the range of 10° to 170°, and the preferred range is from 45° to 135°. A primary arc gas can be supplied to the spraying gun to form a plasma between the cathode and the anode. The primary arc gas may include an inert gas such as argon, helium, or nitrogen. A pressure in the range of 10 to 200 psi may be applied to the primary arc gas. The normal liter per minute flow rate of the primary arc gas can be in the range of 25 to 300 NLPM. A secondary arc gas can be supplied to the spraying gun to form a plasma between the cathode and the anode. The secondary arc gas may include, for example, hydrogen. A pressure in the range of 10 to 200 psi may be applied to the secondary arc gas. The normal liter per minute flow rate of the secondary arc gas can be in the range of 25 to 300 NLPM. A carrier gas can be used to deliver the ion conductive material from the feedstock to the powder injector port at the tip of the spraying gun, where the ion conductive material is introduced into the plasma plume and softened or melted during the process. The carrier gas may include an inert gas such as argon, helium, or nitrogen. A pressure in the range of 10 to 150 psi may be applied to the carrier gas. The carrier gas can have a flow rate in the range of 1 to 25 standard cubic feet per hour (SCFH). The ion conductive material can have a flow rate in the range of 1 to 100 grams per minute. The ion conductive material may have a particle size in the range of 1 to 250 μm, and the preferred range is from 5 to 45 μm. The ion conductive material may be single crystal or polycrystalline.Two or more different types of ion conductive materials may be used to form a composite of two or more ion conductive materials. When powders are premixed and sprayed, a uniformly mixed composite is formed, and when two or more ion conductive materials are sprayed continuously, a layered composite is formed.

[0034] It should be understood that the spraying can be carried out in an atmospheric environment or an inert environment. The inert environment may include, but is not limited to, nitrogen, helium, argon, etc. Alternatively, the spraying may be carried out under vacuum conditions. In yet another alternative, the spraying can be performed in a reactive environment such as oxygen, H2S, ozone, S vapor, LiOH vapor, or any other necessary reactive gas that can enhance the performance of the material. In yet another alternative, the spraying may be carried out in a dry atmosphere. The spraying can be carried out manually or using a robotic system. The target or surface to be sprayed may be kept at room temperature, heated, or cooled. When the target or surface to be sprayed is rapidly cooled, an amorphous phase can then be formed in the polycrystalline microstructure of the solid ion conductive film.

[0035] In another aspect, the solid electrolyte membrane can be sprayed without a heat assist source. The solid electrolyte particles can be accelerated by a carrier gas to a speed of at least 200 meters per second until they reach the substrate, and when the particles collide with the substrate, the particles deform into a grain boundary structure with a specified high aspect ratio. This deformation may be formed by the ductility of the material or the heat generated by the kinetic energy. Helium, argon, or nitrogen gas can be used as the carrier gas.

[0036] Thus, the present description relates to a system and method for constructing interlocking layered structures (e.g., membranes) as solid ionically conductive structures (e.g., membranes) for use in electrochemical systems using thermal spraying or similar fabrication processes. The present description addresses the problems of conventional sintered ceramic solid electrolytes. The present description describes an interlocking layered structure formed by melting and spraying ionically conductive materials. The structure uses an interlocking layered grain structure that can effectively block partial grain boundary vectors parallel to the electric field. Electrons crossing the membrane can be suppressed due to the lack of a driving force perpendicular to the electric field. This, in turn, suppresses the formation of membrane-penetrating metallic dendrites in the battery, improving battery performance.

[0037] The lack of high-throughput processing and the penetration and propagation of metal dendrites through solid ionically conductive membranes present challenges to their integration in electrochemical systems. Thermal spraying and other similar fabrication processes offer the ability to fabricate solid ionically conductive membranes on a large scale. In addition to lithium batteries, the processed membranes can be incorporated into a variety of different electrical energy storage technologies. Additionally, thermal spraying and other similar manufacturing processes can provide advantageous interlocking layered structures to avoid or minimize the penetration and propagation of metal dendrites. Interlocking layered structures are structures formed by melting and spraying an ionically conductive material onto a substrate. In spraying the molten ionically conductive material, the ionically conductive material is slammed onto the substrate to form the shape of a plate attached to the surface of the substrate. The melting and spraying of the ionically conductive material continues to build up layers of the ionically conductive material on top of previously applied layers, resulting in a structure of interlocking layers (i.e., sheets) of randomly stacked ionically conductive material. By forming an interlocking layered structure, grain boundaries parallel to the electric field through the sheet are minimized. If there are electrons that migrate through the grain boundaries to form dendrites, they will be inhibited because there is no in-plane potential to drive them perpendicular to the applied electric field.

[0038] According to one aspect of the present disclosure, a thermal spray process can be used to process the solid ionically conducting electrolyte. According to another aspect of the present disclosure, the resulting solid electrolyte can have an intralayer grain structure. The solid ionically conducting membrane can be, for example, free-standing, supported on a porous structure, or coated on a substrate.

[0039] Ion conducting solid ion conducting membranes can be used in a variety of electrochemical technologies or systems, including, but not limited to, lithium ion batteries, sodium ion batteries, magnesium ion batteries, aluminum ion batteries, potassium ion batteries, zinc ion batteries, lithium metal batteries, sodium metal batteries, magnesium metal batteries, aluminum metal batteries, potassium metal batteries, zinc metal batteries, lithium-air batteries, sodium-air batteries, magnesium-air batteries, aluminum-air batteries, potassium-air batteries, and zinc-air batteries, nickel cadmium batteries, nickel-metal hydride batteries, glass batteries, lithium lithium-ion polymer batteries, lead acid batteries, silver-zinc batteries, lithium-sulfur batteries, sodium sulfide batteries, zinc bromide batteries, zinc-cerium batteries, redox flow batteries, vanadium-redox batteries, hybrid-flow batteries, nickel-iron batteries, nickel-zinc batteries, silicon-air batteries, lithium titanate batteries, organic radical batteries, alkaline rechargeable batteries, alkaline batteries, aluminum-air batteries, dry cell batteries, lithium batteries, lithium-air batteries, magnesium batteries, nickel oxyhydroxide batteries, paper batteries, silver oxide batteries, sugar batteries, air-zinc batteries, zinc-carbon batteries, solid oxide fuel cells, molten batteries, and water or seawater batteries.

[0040] Electrochemical technologies can be primary or secondary in nature, where primary refers to a single electrochemical cycle and secondary refers to a rechargeable system.

[0041] The present disclosure relates to the microstructure of a solid ion conductive membrane structure having an interlocking layered structure as described and illustrated. The interlocking layered structure can be formed from the melting and spraying of an ion conductive material. The layers in the interlocking layered structure can be formed by continuous or raster spraying of the molten ion conductive material. In contrast to the irregular hexagonal-like grain boundary structure of conventional solid electrolytes prepared by thermal sintering, the interlocking layered structure can have an in-plane grain structure. When an electric field is applied across the interlocking layered structure, the direction of the grain boundary vector parallel to the electric field can be blocked by subsequent interlocking layers perpendicular to the electric field, which may prevent electrons from crossing the membrane. When the movement of electrons across the interlocking layered structure is hindered, the penetration and propagation of metal dendrites, particularly lithium dendrites, across the membrane can be blocked. The interlocking layered structure may be partially amorphous and can further reduce the grain boundary effect by forming a glassy phase between particles.

[0042] The present disclosure relates to the fabrication of free-standing solid ion-conducting membranes. The solid ion-conducting membranes can be formed on a removable substrate. After spraying, the removable substrate can be removed, leaving a free-standing solid ion-conducting membrane. The solid ion-conducting membrane may or may not have an epitaxial relationship with the removable substrate. The solid ion-conducting membrane can generally be planar, with some exceptions, such as when the removable substrate happens to be non-planar. Examples of removable substrate removal processes are listed below. In one example, the solid ion-conducting membrane can be built on a removable substrate. The relationship between the membrane and the removable substrate may allow for direct removal of the removable substrate. In another example, the solid ion-conducting membrane can be built on the surface of a dissolvable crystalline salt substrate, which serves as a removable support substrate. The single-crystal salt substrate can then be dissolved in water or other solvent, leaving a free-standing layered membrane. Examples of dissolvable salt substrates include, but are not limited to, halides, sulfates, nitrates, hydroxides, oxides, sulfides, carbonates, nitrites, acetates, citrates, cyanides, phosphates, etc. In yet another example, a salt film can be deposited on the surface of a removable support substrate. A solid, ionically conductive membrane can be constructed on top of the salt film. The salt film can be removed by placing the removable substrate in a solvent such as water to dissolve the salt film, leaving a free-standing layered membrane. Examples of salt films include, but are not limited to, halides, sulfates, nitrates, hydroxides, oxides, sulfides, carbonates, nitrites, acetates, citrates, cyanides, phosphates, etc. Examples of removable support substrates include, but are not limited to, glass, silicon wafers, copper foils, titanium foils, polymer sheets, carbon tapes, composite sheets, etc. In yet another example, a resin can be disposed on the surface of a removable support substrate. After the resin is cured, a solid, ionically conductive membrane can be constructed on top of the resin layer. The resin can then be chemically removed by placing the resin layer in a suitable aqueous or non-aqueous solvent, leaving a free-standing layered film, or heat treatment can be used to remove or decompose the resin.Examples of removable support substrates include, but are not limited to, glass or silicon wafers. Examples of resins include, but are not limited to, polyester, epoxy, polyurethane, and silicone. In yet another example, a low-melting-point metal film can serve as the removable substrate. A solid ion-conducting membrane can be constructed on the surface of the metal film. The metal can then be softened or dehydrated at high temperatures to remove the layered film. Examples of low-melting-point metals include, but are not limited to, tin, tellurium, gallium, or indium. The metals used preferably have low to moderate toxicity levels. In yet another example, a metal film can be used as the removable substrate. A solid ion-conducting membrane can be constructed on the film surface. The metal film can then be dissolved by placing the solid ion-conducting membrane in a dilute aqueous or non-aqueous solution. An example includes constructing a solid ion-conducting membrane on a copper film. A dilute solution of hydrogen peroxide and hydrochloric acid can dissolve the copper, leaving a free-standing membrane. In yet another example, the substrate can be removed using laser lift-off (LLO) techniques, and gallium nitride, sapphire, or glass can be used as the removable substrate. A solid, ionically conductive membrane can be constructed on the surface of a supporting substrate. When an Nd:YAG or KrF laser is passed over the substrate, the membrane is peeled off, leaving a free-standing membrane.

[0043] The present disclosure relates to the fabrication of a solid ion conductive membrane on a porous support substrate. The solid ion conductive membrane can be sprayed onto the supporting porous substrate. The supporting porous substrate may be essentially described as a nanoporous support or a macroporous support. The nanoporous substrate can be defined as a porous support having an average pore diameter in the range of 1 ≦ d ≦ 1000 nm, and the preferred range is 10 ≦ d ≦ 100 nm. The macroporous substrate can be defined as a porous support having an average pore diameter in the range of 1 ≦ d ≦ 5000 μm, and the preferred range is 10 ≦ d ≦ 500 μm. Examples of the porous substrate include, but are not limited to, nickel foam, copper foam, carbon foam, graphene foam, silicon foam, silicon carbide, silicon nitride, aluminum nitride, alumina foam, zirconia foam, silver foam, cobalt foam, graphite, stainless steel foam, etc.

[0044] The following description relates to porous substrates that support solid ionically conductive membranes. Porous substrates can generally be planar, with some exceptions where the porous substrate happens to be non-planar. Non-planar porous substrates can be in shapes such as, but not limited to, cubes, tubes, cones, pyramids, hollow-centered tubes, and the like. Porous substrates can be conductive, semi-conductive, or non-conductive. A conductive or semi-conductive porous substrate can be conformally coated with a thin non-conductive layer. The non-conductive layer can include, but is not limited to, oxides, polymers, ceramics, and the like. The non-conductive layer can have a thickness in the range of 1≦t≦10,000 nm, with a preferred range being 10≦t≦1,000 nm. A non-conductive or semi-conductive porous substrate can be conformally coated with a thin conductive layer. The conductive layer can include, but is not limited to, aluminum, copper, titanium, stainless steel, iron, iron oxide, carbon, nickel, and the like. Alternatively, the conductive layer may comprise a conductive polymer such as polyaniline, polypyrrole, poly(3,4-ethylenedioxythiophene (PEDOT)), polyphenylene vinylene, etc. The conductive layer may have a thickness in the range of 1≦t≦10,000 nm, with a preferred range of 10≦t≦1,000 nm. Deposition methods for the non-conductive or conductive layer may include, but are not limited to, sputtering, RF sputtering, magnetron sputtering, pulsed laser deposition, atomic layer deposition, electrochemical plating, thermal spraying, plasma spraying, flame spraying, immersion, pulsed electrochemical deposition, chemical vapor deposition, physical vapor deposition, evaporation, etc. Alternatively, the conductive and non-conductive coatings may be deposited following the formation of the solid ionically conductive membrane.

[0045] The following description relates to the thermal spraying of a solid ion conductive membrane onto a porous substrate. In one embodiment, the solid ion conductive membrane can be thermally sprayed onto a bare porous substrate using a thermal gun perpendicular to the porous substrate surface. In another embodiment, the solid ion conductive membrane can be thermally sprayed onto a bare porous substrate using a thermal gun set at an angle less than 90 degrees relative to the porous substrate surface. In yet another embodiment, the solid ion conductive membrane can be thermally sprayed onto a porous substrate pre-filled with a temporary filler material. After spraying the membrane, the temporary filler material is removed. The thermal gun can be set perpendicular to the porous substrate surface or at an angle less than 90 degrees. In yet another embodiment, the solid ion conductive membrane can be thermally sprayed onto a porous substrate pre-filled with a secondary battery electrode active material. The thermal gun can be set perpendicular to the porous substrate surface or at an angle less than 90 degrees. In yet another embodiment, the solid ion conductive membrane can be thermally sprayed onto a green body of the porous substrate. After spraying the membrane, the green body can be converted into a porous substrate.

[0046] The following is an example of a temporary filler material process or green body support. In one example, a porous substrate is placed in a saturated salt solution. The water is removed by evaporation, leaving a porous structure filled with solid salt. Once a solid, ionically conductive membrane is formed, the porous substrate can then be placed in fresh water to dissolve and remove the salt filler. Examples of solid salts can include, but are not limited to, halides, sulfates, nitrates, hydroxides, oxides, sulfides, carbonates, nitrites, acetates, citrates, cyanides, phosphates, etc.

[0047] In another example, the porous substrate can be filled with a thermosetting polymer, resin, or thermoplastic, and then cured. After a solid ion conductive membrane is constructed on top of it, the resin can be removed by chemical etching or thermal decomposition. Examples of resins include, but are not limited to, acrylic, polyester, epoxy, polypropylene, nylon, polytetrafluoroethylene, polyurethane, phenol, and silicone. The thermosetting polymer or resin can be deposited on the porous substrate by means such as, but not limited to, spraying, spin coating, drop casting, dipping, etc. In yet another example, the porous substrate can be filled with polydimethylsiloxane and then cured. After a solid ion conductive membrane is constructed on top, the porous substrate is removed by etching, dissolving, or decomposing it. Next, the polydimethylsiloxane functions as a new porous substrate. One example includes, but is not limited to, filling the voids of copper foam with polydimethylsiloxane and then curing it. After forming the solid ion conductive membrane, a mixture of hydrogen peroxide and hydrochloric acid is used to dissolve and remove the copper foam. Another example includes, but is not limited to, filling the voids of carbon foam with polydimethylsiloxane and then curing it. After the membrane is constructed on top, the carbon foam can be removed by thermal decomposition. In yet another example, the solid ion conductive membrane can be constructed on a porous support to form a green body, and then a co-thermal decomposition treatment can be performed. One example includes, but is not limited to, the use of a highly cross-linked hybrid organic-inorganic polymer resin matrix composed of polycarbosilane, diisocyanate, and epoxy resin to prepare foamed silicon carbide. Typically, the resulting hybrid matrix is heated, and then foamed silicon carbide with continuous bubbles is obtained by subsequent thermal decomposition. Before the thermal decomposition process, a solid ion conductive membrane can be constructed on the surface of the hybrid matrix. After the membrane is constructed, foamed silicon carbide with continuous bubbles is obtained by thermal decomposition. In this example, the foamed silicon carbide is the new porous support scaffold.

[0048] The present disclosure relates to the fabrication of solid ionically conductive films on permanent substrates. The solid ionically conductive films can be thermally sprayed onto permanent substrates. The permanent substrates can be defined as metals, semiconducting materials, or non-conducting materials, but are not limited to these. Metallic substrates may include, but are not limited to, copper, aluminum, titanium, stainless steel, tantalum, chromium, cobalt, gold, silver, indium, magnesium, molybdenum, niobium, nickel, lead, palladium, vanadium, tungsten, zirconium, zinc, iron, gold, sodium, platinum, tin, beryllium, rhodium, bismuth, iridium, cadmium, uranium, osmium, tantalum, potassium, ruthenium, rhenium, calcium, plutonium, scandium, cerium, hafnium, dysprosium, thorium, yttrium, radium, lanthanum, samarium, gadolinium, thallium, neodymium, and the like.Examples of the semiconductive substrate include, but are not limited to, diamond, silicon wafer, germanium wafer, gray tin, silicon carbide, gray selenium, red selenium, tellurium, boron nitride, boron phosphide, boron arsenide, aluminum nitride, aluminum phosphide, aluminum arsenide, aluminum antimonide, gallium nitride, gallium phosphide, gallium arsenide, gallium antimonide, indium nitride, indium phosphide, indium arsenide, indium antimonide, cadmium selenide, cadmium sulfide, cadmium telluride, zinc oxide, zinc selenide, zinc sulfide, zinc telluride, cuprous chloride, copper sulfide, lead selenide, lead(II) sulfide, lead telluride, tin(II) sulfide, tin ten telluride, lead tin telluride, thallium tin telluride, thallium germanium telluride, bismuth telluride, cadmium phosphide, cadmium arsenide, cadmium antimonide, zinc phosphide, zinc arsenide, zinc antimonide, titanium dioxide, copper oxide, uranium dioxide, uranium trioxide, bismuth trioxide, tin dioxide, barium titanate, strontium titanate, lithium niobate, lanthanum copper oxide, monoclinic vanadium oxide, lead iodide, molybdenum disulfide, gallium selenide, tin sulfide, bismuth sulfide, gallium manganese arsenide, indium manganese arsenide, cadmium manganese telluride, manganese lead telluride, lanthanum calcium manganate, iron(II) oxide, nickel(II) oxide, europium(II) oxide, chromium(III) bromide, copper indium selenide, gallium silver sulfide, zinc silicon phosphide, arsenic trisulfide, platinum silicide, mercury(II) iodide, thallium bromide, silver sulfide, iron disulfide, copper zinc tin sulfide, copper zinc antimony sulfide, copper tin sulfide, etc.

[0049] A secondary battery electrode may be formed on a substrate, and an interlocking layer may be sprayed on the secondary battery electrode. Such a spraying process environment (i.e., inert) is assumed to be suitable with respect to not destroying the electrode material. The electrode may be coated on a current collector such as, but not limited to, aluminum, copper, carbon, titanium, stainless steel, nickel, a mesh-like structure, etc. A solid ion conductive membrane may be sprayed to cover the whole or only a part of the substrate surface. The substrate can be coated on one or a plurality of its sides with a solid ion conductive membrane. For example, both sides of the current collector can be coated with an electrode active material, and the solid ion conductive membrane can be coated on both surfaces of the electrode active material. The solid ion conductive membrane can be sprayed on a tape cast and sintered second ionic conducting solid-state ionic conductive membrane. For example, a solid ion conductive membrane composed of LLZO having a garnet oxide structure can be formed on a self-supporting tape cast LLZO membrane, or vice versa.

[0050] The present disclosure relates to secondary batteries containing solid ionically conductive membranes. A secondary battery can be defined as a battery that can be recharged and is not limited to a single discharge cycle. The secondary battery may be in the form of, but is not limited to, an ion-based battery or a metal battery. The secondary battery may be in the shape or orientation of, but is not limited to, a pouch-type, cylindrical, coin-type, button-type, or prismatic cell. Secondary battery types include, but are not limited to, lithium-ion batteries, sodium-ion batteries, magnesium-ion batteries, aluminum-ion batteries, potassium-ion batteries, zinc-ion batteries, lithium metal batteries, sodium metal batteries, magnesium metal batteries, aluminum metal batteries, potassium metal batteries, zinc metal batteries, nickel-cadmium batteries, nickel-metal hydride batteries, glass batteries, lithium-ion polymer batteries, lithium-sulfur batteries, sodium sulfide batteries, zinc bromide batteries, lithium titanate batteries, and water or seawater batteries. The secondary battery may be a solid-state secondary battery comprising a composite cathode, a composite anode or a metal / metal alloy anode, and a solid ionically conductive membrane. Alternatively, the secondary battery may be a liquid, polymer, or semi-solid secondary battery comprising a cathode or composite cathode, an anode or composite anode or metal / metal alloy anode, a solid ionically conductive membrane, and a liquid-based or gel polymer-based electrolyte.

[0051] This description relates to a cathode for a secondary battery. The cathode or composite cathode for a secondary battery can be coated with a thin protective layer on the surface to increase stability and reduce interfacial resistance with the solid ion-conducting membrane. The cathode can have the following characteristics: The cathode can be composed of an intercalation active material, a binder, and a conductive additive, but is not limited to these. The cathode can also contain an intercalation active material, for example, but not limited to, layered YMO2, Y-enriched layered Y 1+x M 1-xThe cathode can include O2, spinel YM2O4, olivine YMPO4, silicate Y2MSiO4, borate YMBO3, tavorite YMPO4F (where M is Fe, Co, Ni, Mn, Cu, Cr, etc.), (where Y is Li, Na, K, etc.), vanadium oxide, iron sulfide FeF3, LiSe. The cathode can interact with the ions through a non-intercalation mechanism. Examples of cathodes can include, but are not limited to, oxygen, air, water, or sulfur. For lithium intercalation, the cathode can be lithium iron phosphate (LiFePO4), lithium cobalt oxide (LiCoO2), lithium manganese oxide (LiMn2O4), lithium nickel oxide (LiNiO2), lithium nickel manganese cobalt oxide (LiNi x Co y Mn z O2, 0.95≧x≧0.5, 0.3≧y≧0.025, 0.2≧z≧0.025), lithium nickel cobalt aluminum oxide (LiNi x Co y Al z O2, 0.95≧x≧0.5, 0.3≧y≧0.025, 0.2≧z≧0.025), lithium nickel manganese spinel (LiNi 0.5 Mn 1.5 The cathode may include, but is not limited to, polyvinylidene fluoride, polyacrylic acid, lotader, carboxymethyl cellulose, styrene butadiene rubber, sodium alginate, etc. The cathode may include, but is not limited to, a conductive additive, such as, but not limited to, graphene, reduced graphene oxide, carbon nanotubes, carbon black, Super P, acetylene black, carbon nanofibers, or a conductive polymer, such as polyaniline, polypyrrole, poly(3,4-ethylenedioxythiophene (PEDOT), polyphenylene vinylene, etc.

[0052] The composite cathode can have the following characteristics. The composite cathode can be composed of, but is not limited to, an intercalation active material, a binder, a conductive additive, and an ion conduction medium. The composite cathode may include an intercalation active material, for example, but not limited to, layered YMO2, Y-enriched layered Y 1+x M 1-x O2, spinel YM2O4, olivine YMPO4, silicate Y2MSiO4, borate YMBO3, tabularite YMPO4F (where M is Fe, Co, Ni, Mn, Cu, Cr, etc.), (where Y is Li, Na, K, etc.), vanadium oxide, sulfur, lithium sulfide FeF3, LiSe, etc. In the case of lithium intercalation, the composite cathode may include lithium iron phosphate (LiFePO4), lithium cobalt oxide (LiCoO2), lithium manganese oxide (LiMn2O4), lithium nickel oxide (LiNiO2), lithium nickel manganese cobalt oxide (LiNi x Co y Mn z O2, 0.95 ≧ x ≧ 0.5, 0.3 ≧ y ≧ 0.025, 0.2 ≧ z ≧ 0.025), lithium nickel cobalt aluminum oxide (LiNi x Co y Al z O2, 0.95 ≧ x ≧ 0.5, 0.3 ≧ y ≧ 0.025, 0.2 ≧ z ≧ 0.025), lithium nickel manganese spinel (LiNi 0.5 Mn 1.5 O4), etc., but is not limited to these. The composite cathode may include a binder, for example, but not limited to, polyvinylidene fluoride, polyacrylic acid, carboxymethyl cellulose, styrene-butadiene rubber, sodium alginate, etc. The composite cathode may include a conductive additive, for example, but not limited to, graphene, reduced graphene oxide, carbon nanotube, carbon black, Super P, acetylene black, carbon nanofiber, or a conductive polymer, for example, polyaniline, polypyrrole, poly(3,4-ethylenedioxythiophene) (PEDOT), polyphenylene vinylene, etc.

[0053] Examples of the ion conductive medium in the composite cathode include, but are not limited to, polymers, ion conductive ceramics, or polymer-ceramic composites. The polymer in the composite cathode may include ion conductive polymers or non-ion conductive polymers. Examples of polymers include, but are not limited to, polyethylene glycol, polyisobutene (e.g., OPPANOL (trademark)), polyvinylidene fluoride, polyvinyl alcohol. Additional examples of suitable polymers include polyolefins (e.g., polyethylene, poly(butene-1), poly(n-pentene-2), polypropylene, polytetrafluoroethylene), polyamines (e.g., poly(ethyleneimine) and polypropyleneimine (PPI)); polyamides (e.g., polyamide (nylon), poly(ε-caprolactam) (nylon 6), poly(hexamethylene adipamide) (nylon 66)), polyimides (e.g., polyimide, polynitrile, and poly(pyromellitic diimide-1,4-diphenylether)) (Kapton (registered trademark)) (NOMEX (registered trademark)) (KEVLAR (registered trademark)); polyetheretherketone (PEEK); vinyl polymers (e.g., polyacrylamide, poly(2-vinylpyridine), poly(N-vinylpyrrolidone), poly(methyl cyanoacrylate), poly(ethyl cyanoacrylate), poly(butyl cyanoacrylate), poly(isobutyl cyanoacrylate), poly(vinyl acetate), poly(vinyl alcohol), poly(vinyl chloride), poly(vinyl fluoride), poly(2-vinylpyridine), vinyl polymer, polychlorotrifluoroethylene, and poly(isoohexyl cyanoacrylate)); polyacetal; polyesters (e.g., polycarbonate, polybutylene terephthalate, polyhydroxybutyrate); polyethers (poly(ethylene oxide) (PEO), poly(propylene oxide) (PPO), poly(tetramethylene oxide) (PTMO)); vinylidene polymers (e.g., polyisobutylene, poly(methylstyrene), poly(methyl methacrylate) (PMMA), poly(vinylidene chloride), and poly(vinylidene fluoride)); polyaramides (e.g.,Poly(imino-1,3-phenyleneiminoisophthaloyl) and poly(imino-1,4-phenyleneiminoterephthaloyl)); polyheteroaromatic compounds (e.g., polybenzimidazole (PBI), polybenzobisoxazole (PBO), and polybenzobisthiazole (PBT)); polyheterocyclic compounds (e.g., polypyrrole); polyurethanes; phenolic polymers (e.g., phenol formaldehyde); polyalkynes (e.g., polyacetylene); polydienes (e.g., 1,2-polybutadiene, cis or trans-1,4-polybutadiene); polysiloxanes (e.g., poly(dimethylsiloxane) (PDMS), poly(diethylsiloxane) (PDES), polydiphenylsiloxane (PDPS), and polymethylphenylsiloxane (PMPS)); inorganic polymers (e.g., polyphosphazenes, polyphosphonates, polysilanes, polysilazanes). In some embodiments, the polymer can be selected from poly(n-pentene-2), polypropylene, polytetrafluoroethylene, polyamides (e.g., polyamide (nylon), poly(ε-caprolactam) (nylon 6), poly(hexamethylene adipamide) (nylon 66)), polyimides (e.g., polynitrile, and poly(pyromellitimide-1,4-diphenyl ether)) (Kapton®), (NOMEX®), (KEVLAR®), polyetheretherketone (PEEK). In the case of non-ionic polymers, an ionically conductive salt may be added. Examples of ionically conductive salts include lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(oxalato)borate (LiBOB), lithium difluoro(oxalato)borate (LiDFOB), LiSCN, LiBr, LiI, LiClO4, LiAsF6, LiSO3CF3, LiSO3CH3, LiBF4, LiB(Ph)4, LiPF6, LiC(SO2CF3)3, LiN(SO2CF3)2), LiNO3, sodium bis(trifluoromethanesulfonyl)imide (NaTFSI) and sodium bis(fluorosulfonyl)imide (NaFSI),Sodium bis(oxalato)borate (NaBOB), sodium difluoro(oxalato)borate (NaDFOB), NaSCN, NaBr, NaI, NaAsF6, NaSO3CF3, NaSO3CH3, NaBF4, NaPF6, NaN(SO2F)2, NaClO4, NaN(SO2CF3)2, NaNO3, magnesium bis(trifluoromethanesulfonyl)imide (Mg(TFSI)2) and magnesium bis(fluorosulfonyl)imide (Mg(FSI)2), magnesium bis(oxalato)borate (Mg(BOB)2), magnesium difluoro(oxalato)borate (Mg)(DFOB)2), Mg(SCN)2, MgBr2, MgI2, Mg(ClO4)2, Mg(AsF6)2, Mg(SO3CF 3)2, Mg(SO3CH3)2, Mg(BF4)2, Mg(PF6)2, Mg(NO3)2, Mg(CH3COOH)2, potassium bis(trifluoromethanesulfonyl)imide (KTFSI) and potassium bis(fluorosulfonyl)imide (KFSI), potassium bis(oxalato)borate (KBOB), potassium difluoro(oxalato)borate (KDFOB), KSCN, KBr, KI, KClO4, KAsF6, KSO3CF3, KSO3CH3, KBF4, KB(Ph)4, KPF6, KC(SO2CF3)3, KN(SO2CF3)2), KNO3, Al(NO3)2, AlCl3, Al2(SO4)3, AlBr3, AlI3, AlN, AlSCN, and Al(ClO4)3.

[0054] Ion-conducting ceramics used in composite cathodes can have the following characteristics: Ion-conducting ceramics include or are formed from solid ion-conducting materials. Solid ion-conducting materials can be described as materials that can have the following characteristics: A solid ion-conducting material is a type of material that can selectively pass certain charged elements in the presence of a chemical potential, such as an electric field or a concentration difference. The solid ion-conducting material allows the movement of ions but may not readily allow electrons to pass through. Ions can carry one, two, three, four or more positive charges. Examples of charged ions include H +, Li + , Na + , K + , Ag + , Mg 2+ , Zn 2+ , Al 3+ and the like, but not limited thereto. The ionic conductivity of the corresponding ions can preferably be > 10 -7 S / cm. It is preferable to have a lower conductivity (< 10 -7 S / cm). The composite cathode may include a mixture of two or more solid ionic conductive materials. Examples of solid ionic conductive materials include the general formula: Li n [A( 3-a’-a’’) A’( a’ )A’’( a’’ )][B( 2-b’-b’’ )B’( b’ )B’’( b’’ )][C’( c’ )C’’( c’’ )]O 12 , and garnet-like structured oxide materials having a. Wherein, A, A', and A'' represent octahedral positions in the crystal structure, i. Wherein, A represents one or more trivalent rare earth elements, ii. Wherein, A' represents one or more alkaline earth elements, iii. Wherein, A'' represents one or more alkali metal elements other than Li, iv. Wherein, 0 ≦ a' ≦ 2 and 0 ≦ a'' ≦ 1; b. Wherein, B, B', and B'' represent octahedral positions in the crystal structure, i. Wherein, B represents one or more tetravalent elements, ii. Wherein, B' represents one or more pentavalent elements, iii. Wherein, B'' represents one or more hexavalent elements, iv. Wherein, 0 ≦ b', 0 ≦ b'', and b' + b'' ≦ 2; c. Wherein, C' and C'' represent tetrahedral positions in the crystal structure, i. Wherein, C' represents one or more of Al, Ga, and boron, ii. Wherein, C'' represents one or more of Si and Ge, iii. Wherein, 0 ≦ c' ≦ 0.5 and 0 ≦ c'' ≦ 0.4; d. Wherein, n = 7 + a' + 2·a'' - b' - 2·b'' - 3·c' - 4·c'', and 4.5 ≤ n ≤ 7.5.

[0055] In another example, the solid ion conductive material includes perovskite-type oxides such as (Li,La)TiO3, or doped or substituted compounds. In yet another example, the solid ion conductive material includes a lithium film having a NASICON structure, for example, LAGP (Li1-xAl x Ge 2-x (PO4)3), LATP (Li1+xAl x Ti 2-x (PO4)3), and these materials doped with other elements are included. In yet another example, the solid ion conductive material includes anti-perovskite structure materials and their derivatives, for example, compositions of Li3OCl, Li3OBr, and Li3OI. In yet another example, the solid ion conductive material includes materials of the Li3YH6 (H = F, Cl, Br, I) group, and Y can be replaced with other rare earth elements. In yet another example, the solid ion conductive material includes Li 2x S x+w+5z M y P 2z is included, wherein x is 8 to 16, y is 0.1 to 6, w is 0.1 to 15, z is 0.1 to 3, and M is selected from the group consisting of atoms of lanthanide, Group 3, Group 4, Group 5, Group 6, Group 7, Group 8, Group 9, Group 12, Group 13, and Group 14, and combinations thereof. In yet another example, the solid ion conductive material includes a general formula: Li 12-m-x (M m Y4 2- )Y 2-x 2- X x - of the aludidite material is included, wherein M m+ = B 3+ , Ga 3+ , Sb 3+ , Si 4+ , Ge 4+ , P 5+ , As 5+ , or combinations thereof; Y 2- = O 2- , S2- , Se 2- , Te 2- , or a combination thereof; X - =F - , Cl - , Br - , I - or a combination thereof; and x is in the range of 0≦x≦2. In yet another example, the solid ionically conductive material may have a structure having the general formula: Li 18-2m-x (M2 m+ Y7 2- )Y 2-x 2- X x - The argyrodite material includes an argyrodite material of the formula M m+ =B 3+ , Ga 3+ , Sb 3+ , Si 4+ , Ge 4+ , P 5+ , As 5+ , or a combination thereof; Y 2- =O 2- , S 2- , Se 2- , Te 2- , or a combination thereof; X - =F - , Cl - , Br - , I - or a combination thereof; and x is in the range of 0≦x≦2.

[0056] This description relates to the anode of a secondary battery. The anode of a secondary battery, a metal / metal alloy anode, or a composite anode can be coated with a thin layer on its surface to enhance stability and reduce interfacial resistance with a solid ion conductive membrane. The anode can have the following characteristics. In the case of an ion-based secondary battery, the anode can also be composed of, but not limited to, an active material, a binder, and a conductive additive. The active material may interact with ions through various mechanisms such as intercalation, alloying, and conversion, among others. Examples of active material anode materials include titanium oxide, silicon, tin oxide, germanium, antimony, silicon oxide, iron oxide, cobalt oxide, ruthenium oxide, molybdenum oxide, molybdenum sulfide, chromium oxide, nickel oxide, manganese oxide, carbon-based materials (hard carbon, soft carbon, graphene, graphite’s, reduced graphene oxide, carbon nanofiber, carbon nanotube, etc.), but are not limited thereto.

[0057] The anode may include a binder, such as, but not limited to, polyvinylidene fluoride, polyacrylic acid, carboxymethyl cellulose, styrene butadiene rubber, sodium alginate, etc. The anode may include a conductive additive, such as, but not limited to, graphene, reduced graphene oxide, carbon nanotube, carbon black, Super P, acetylene black, carbon nanofiber, or a conductive polymer, such as polyaniline, polypyrrole, poly(3,4-ethylenedioxythiophene (PEDOT), polyphenylene vinylene, etc.

[0058] The metal / metal alloy anode can have the following characteristics. In the case of a metal-based secondary battery, the anode can be composed of a metal or a metal alloy. The metal / metal alloy anode may interact with ions through a plating and stripping mechanism. Such anodes are composed of, but not limited to, lithium metal, lithium metal alloy, sodium metal, sodium metal alloy, magnesium metal, magnesium metal alloy, aluminum metal, aluminum metal alloy, potassium metal, potassium metal alloy, zinc metal, zinc metal alloy. Examples of the alloy include, but are not limited to, materials such as indium, tin, manganese, etc.

[0059] The composite anode can have the following characteristics. Generally, a composite anode is used in a solid secondary battery. The composite anode is composed of an active material, a binder, a conductive additive, and an ion conductive medium. The active material may interact with ions through various mechanisms such as intercalation, alloying, and conversion, although not limited thereto. Examples of the active material anode material include titanium oxide, silicon, tin oxide, germanium, antimony, silicon oxide, iron oxide, cobalt oxide, ruthenium oxide, molybdenum oxide, molybdenum sulfide, chromium oxide, nickel oxide, manganese oxide, carbon-based materials (hard carbon, soft carbon, graphene, graphite’s, reduced graphene oxide, carbon nanofiber, carbon nanotube, etc.), but are not limited thereto. The composite anode may include a binder, for example, but not limited to, polyvinylidene fluoride, polyacrylic acid, carboxymethyl cellulose, styrene butadiene rubber, sodium alginate, etc. The composite anode may include a conductive additive, for example, but not limited to, graphene, reduced graphene oxide, carbon nanotube, carbon black, Super P, acetylene black, carbon nanofiber, or a conductive polymer, for example, polyaniline, polypyrrole, poly(3,4-ethylenedioxythiophene (PEDOT), polyphenylene vinylene, etc. Examples of the ion conductive medium in the composite anode include, but are not limited to, a polymer, an ion conductive ceramic, or a polymer ceramic composite. The polymer used in the composite anode can be an ion conductive polymer or a non-ion conductive polymer. Examples of the polymer include polyethylene glycol, polyisobutene (e.g., OPPANOL (trademark)), polyvinylidene fluoride, polyvinyl alcohol, but are not limited thereto. Additional examples of suitable polymers include polyolefins (e.g., polyethylene, poly(butene-1), poly(n-pentene-2), polypropylene, polytetrafluoroethylene), polyamines (e.g., poly(ethyleneimine) and polypropyleneimine (PPI));Polyamides (e.g., polyamide (nylon), poly(ε-caprolactam) (nylon 6), poly(hexamethylene adipamide) (nylon 66)), polyimides (e.g., polyimide, polynitrile, and poly(pyromellitimide-1,4-diphenyl ether)) (Kapton®) (NOMEX®) (KEVLAR®); polyetheretherketone (PEEK); vinyl polymers (e.g., polyacrylamide, poly(2-vinylpyridine), poly(N-vinylpyrrolidone), poly(methyl cyanoacrylate), poly(ethyl cyanoacrylate), poly(butyl cyanoacrylate), poly(isobutyl cyanoacrylate), poly(vinyl acetate), poly(vinyl alcohol), poly(vinyl chloride), poly(vinyl fluoride), poly(2-vinylpyridine), vinyl polymer, polychlorotrifluoroethylene, and poly(isobutyl cyanoacrylate)); polyacetal; polyesters (e.g., polycarbonate, polybutylene terephthalate, polyhydroxybutyrate); polyethers (poly(ethylene oxide) (PEO), poly(propylene oxide) (PPO), poly(tetramethylene oxide) (PTMO)); vinylidene polymers (e.g., polyisobutylene, poly(methylstyrene), poly(methyl methacrylate) (PMMA), poly(vinylidene chloride), and poly(vinylidene fluoride)); polyaramides (e.g., poly(imino-1,3-phenylene iminoisophthaloyl) and poly(imino-1,4-phenylene iminoterephthaloyl)); polyheteroaromatic compounds (e.g., polybenzimidazole (PBI), polybenzobisoxazole (PBO) and polybenzobisthiazole (PBT)); polyheterocyclic compounds (e.g., polypyrrole); polyurethanes; phenolic polymers (e.g., phenol formaldehyde); polyalkynes (e.g., polyacetylene); polydienes (e.g., 1,2-polybutadiene, cis or trans-1,4-polybutadiene); polysiloxanes (e.g., poly(dimethylsiloxane) (PDMS), poly(diethylsiloxane) (PDES), polydiphenylsiloxane (PDPS), and polymethylphenylsiloxane (PMPS));Examples of inorganic polymers include, but are not limited to, polyphosphazenes, polyphosphonates, polysilanes, and polysilazanes. In some embodiments, the polymer can be selected from poly(n-pentene-2), polypropylene, polytetrafluoroethylene, polyamides (e.g., polyamide (nylon), poly(ε-caprolactam) (nylon 6), poly(hexamethylene adipamide) (nylon 66)), polyimides (e.g., polynitrile, and poly(pyromellitimide-1,4-diphenyl ether)) (Kapton®) (NOMEX®) (KEVLAR®), polyetheretherketone (PEEK).;

[0060] In the case of non-ionic polymers, an ionically conductive salt may be added. Examples of the ionically conductive salt include lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(oxalato)borate (LiBOB), lithium difluoro(oxalato)borate (LiDFOB), LiSCN, LiBr, LiI, LiClO4, LiAsF6, LiSO3CF3, LiSO3CH3, LiBF4, LiB(Ph)4, LiPF6, LiC(SO2CF3)3, LiN(SO2CF3)2), LiNO3, sodium bis( (trifluoromethanesulfonyl)imide (NaTFSI) and sodium bis(fluorosulfonyl)imide (NaFSI), sodium bis(oxalato)borate (NaBOB), sodium difluoro(oxalato)borate (NaDFOB), NaSCN, NaBr, NaI, NaAsF6, NaSO3CF3, NaSO3CH3, NaBF4, NaPF6, NaN(SO2F)2, NaClO4, NaN(SO2CF3)2, NaNO3, magnesium bis(trifluoromethanesulfonyl)imide (Mg(TFSI)2) and magnesium bis(fluorosulfonyl)imide (Mg(FSI)2), magnesium bis(oxalato)borate (Mg(BOB)2), magnesium difluoro(oxalato)borate (Mg)(DFOB)2), Mg(SCN)2, MgBr2, MgI2, Mg(ClO4)2, Mg(AsF6)2, Mg(SO3CF3)2, Mg(SO3CH3)2, Mg(BF4)2, Mg(PF6)2, Mg(NO3)2, Mg(CH3COOH)2, potassium bis(trifluoromethanesulfonyl)imide (KTFSI), and potassium Examples of suitable fluorocarbons include, but are not limited to, potassium bis(fluorosulfonyl)imide (KFSI), potassium bis(oxalato)borate (KBOB), potassium difluoro(oxalato)borate (KDFOB), KSCN, KBr, KI, KClO4, KAsF6, KSO3CF3, KSO3CH3, KBF4, KB(Ph)4, KPF6, KC(SO2CF3)3, KN(SO2CF3)2), KNO3, Al(NO3)2, AlCl3, Al2(SO4)3, AlBr3, AlI3, AlN, AlSCN, and Al(ClO4)3.

[0061] Ion-conducting ceramics used in composite anodes can have the following characteristics: Ion-conducting ceramics include or are formed from solid ion-conducting materials. Solid ion-conducting materials can be described as materials that can have the following characteristics: A solid ion-conducting material is a type of material that can selectively pass certain charged elements in the presence of a chemical potential, such as an electric field or a concentration difference. The solid ion-conducting material allows the movement of ions but may not readily allow electrons to pass through. Ions can carry one, two, three, four or more positive charges. Examples of charged ions include H + , Li + , Na + , K. + , Ag + , Mg 2+ , Zn 2+ , Al 3+ The ionic conductivity of the corresponding ions is preferably >10 -7 S / cm. Lower conductivity (<10 -7 Preferably, the composite cathode has a conductivity of 0.15 S / cm. The composite cathode may comprise a mixture of one or more solid, ionically conductive materials. Examples of solid, ionically conductive materials include those having the general formula: Li n [A( 3-a’-a’’) A'( a’ )A''( a’’ )][B( 2-b’-b’’ )B'( b’ )B''( b’’ )][C'( c’ )C''( c’’ )]O 12 , Examples of oxide materials include, but are not limited to, garnet-like structure oxide materials having a. wherein A, A', and A'' represent octahedral positions in a crystal structure; i. wherein A represents one or more trivalent rare earth elements; ii. wherein A' represents one or more alkaline earth elements; iii. wherein A'' represents one or more alkali metal elements other than Li; iv. wherein 0≦a'≦2 and 0≦a''≦1; b. In the formula, B, B', and B'' represent octahedral positions in the crystal structure, where: i. In the formula, B represents one or more tetravalent elements; ii. In the formula, B' represents one or more pentavalent elements; iii. In the formula, B'' represents one or more hexavalent elements; iv. In the formula, 0 ≤ b', 0 ≤ b'', and b' + b'' ≤ 2; c. In the formula, C' and C'' represent tetrahedral positions in the crystal structure, where: i. In the formula, C' represents one or more of Al, Ga, and boron; ii. In the formula, C'' represents one or more of Si and Ge; iii. In the formula, 0 ≤ c' ≤ 0.5 and 0 ≤ c'' ≤ 0.4; d. In the formula, n = 7 + a' + 2·a'' - b' - 2·b'' - 3·c' - 4·c'', and 4.5 ≤ n ≤ 7.5.

[0062] In another example, the solid ion conductive material includes perovskite-type oxides such as (Li,La)TiO3, or doped or substituted compounds. In yet another example, the solid ion conductive material includes lithium films with a NASICON structure, such as LAGP (Li1-xAl x Ge 2-x (PO4)3), LATP (Li1+xAl x Ti 2-x (PO4)3), and these materials doped with other elements. In yet another example, the solid ion conductive material includes anti-perovskite structure materials and their derivatives, such as compositions of Li3OCl, Li3OBr, and Li3OI. In yet another example, the solid ion conductive material includes materials of the Li3YH6 (H = F, Cl, Br, I) group, where Y can be replaced by other rare earth elements. In yet another example, the solid ion conductive material includes Li 2x S x+w+5z M y P 2z is included, where x is 8 - 16, y is 0.1 - 6, w is 0.1 - 15, z is 0.1 - 3, and M is selected from the group consisting of atoms of lanthanides, Group 3, Group 4, Group 5, Group 6, Group 7, Group 8, Group 9, Group 12, Group 13, and Group 14, and combinations thereof. In yet another example, the solid ion conductive material has the general formula: Li12-m-x (M m Y4 2- )Y 2-x 2- X x - contains an argyrodite material of the formula, where M m+ = B 3+ , Ga 3+ , Sb 3+ , Si 4+ , Ge 4+ , P 5+ , As 5+ , or a combination thereof; Y 2- = O 2- , S 2- , Se 2- , Te 2- , or a combination thereof; X - = F - , Cl - , Br - , I - , or a combination thereof; and x is in the range of 0 ≦ x ≦ 2. In yet another example, the solid ion conductive material includes a general formula: Li 18-2m-x (M2 m+ Y7 2- )Y 2-x 2- X x - contains an argyrodite material of the formula, where M m+ = B 3+ , Ga 3+ , Sb 3+ , Si 4+ , Ge 4+ , P 5+ , As 5+ , or a combination thereof; Y 2- = O 2- , S 2- , Se 2- , Te 2- , or a combination thereof; X - = F - , Cl - , Br - , I - , or a combination thereof; and x is in the range of 0 ≦ x ≦ 2.

[0063] This description relates to liquid-based electrolytes in liquid or semi-solid secondary batteries. Liquid-based electrolytes include, but are not limited to, organic-based liquid electrolytes or room-temperature ionic liquid electrolytes. Examples of organic-based liquid electrolytes include, but are not limited to, ethylene carbonate (EC), fluoroethylene carbonate (FEC), propylene carbonate (PC), ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), diethyl carbonate (DEC), dimethyl ether (DME), diethylene glycol dimethyl ether (DEGDME), tetraethylene glycol dimethyl ether (TEGDME), 1,3-dioxolane (DOL), and 1-ethyl-3-methylimidazolium chloride, as well as mixtures of two or more thereof. Examples of room temperature ionic liquid electrolytes include, but are not limited to, imidazolium, pyrrolidinium, piperidinium, ammonium, hexafluorophosphate, dicyanamide, tetrachloroaluminate, sulfonium, phosphonium, pyridinium, parazonium, and thiazolium. Organic-based liquid electrolytes and room temperature ionic liquid electrolytes can include ionically conducting salts.Examples of ionic conductive salts include, but are not limited to, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(oxalato)borate (LiBOB), lithium difluoro(oxalato)borate (LiDFOB), LiSCN, LiBr, LiI, LiClO4, LiAsF6, LiSO3CF3, LiSO3CH3, LiBF4, LiB(Ph)4, LiPF6, LiC(SO2CF3)3, LiN(SO2CF3)2), LiNO3, sodium bis(trifluoromethanesulfonyl)imide (NaTFSI), sodium bis(fluorosulfonyl)imide (NaFSI), sodium bis(oxalato)borate (NaBOB), sodium difluoro(oxalato)borate (NaDFOB), NaSCN, NaBr, NaI, NaAsF6, NaSO3CF3, NaSO3CH3, NaBF4, NaPF6, NaN(SO2F)2, NaClO4, NaN(SO2CF3)2, NaNO3, magnesium bis(trifluoromethanesulfonyl)imide (Mg(TFSI)2), magnesium bis(fluorosulfonyl)imide (Mg(FSI)2), magnesium bis(oxalato)borate (Mg(BOB)2), magnesium difluoro(oxalato)borate (Mg)(DFOB)2), Mg(SCN)2, MgBr2, MgI2, Mg(ClO4)2, Mg(AsF6)2, Mg(SO3CF3)2, Mg(SO3CH3)2, Mg(BF4)2, Mg(PF6)2, Mg(NO3)2, Mg(CH3COOH)2, potassium bis(trifluoromethanesulfonyl)imide (KTFSI), potassium bis(fluorosulfonyl)imide (KFSI), potassium bis(oxalato)borate (KBOB), potassium difluoro(oxalato)borate (KDFOB), KSCN, KBr, KI, KClO4, KAsF6, KSO3CF3, KSO3CH3, KBF4, KB(Ph)4, KPF6, KC(SO2CF3)3, KN(SO2CF3)2), KNO3, Al(NO3)2, AlCl3, Al2(SO4)3, AlBr3, AlI3, AlN, AlSCN, Al(ClO4)3.

[0064] The present disclosure relates to other electrochemical systems using solid ion conductive membranes. Other electrochemical cells include, but are not limited to, flow batteries, lithium-sulfur batteries, sodium-sulfur batteries, molten salt batteries, air batteries, and primary lithium batteries.

[0065] This description relates to flow batteries. Flow batteries, also known as redox flow batteries in the art, are a type of electrochemical system that stores and supplies electrochemical energy by two electrochemically active components dissolved in liquids called catholyte and anolyte, which are separated by a solid ion conductive membrane contained within the system. The solid ion conductive membrane can be used both to conduct ions and to prevent crossover between the catholyte and anolyte. Flow batteries may sometimes be referred to as regenerative fuel cells or secondary fuel cells. The energy stored in a flow battery is determined by the size of the storage tanks for the anolyte and / or catholyte. Types of flow batteries include, but are not limited to, redox batteries, hybrid batteries, organic batteries, metal hydrides, nanonetworks, or semi-solids. Other types of flow batteries include, but are not limited to, organic batteries, both aqueous and non-aqueous types, metal hydrides, and nanostructures; where the flow battery has a design similar to either a redox system or a hybrid system and uses an ion exchange membrane, an ion selective membrane, or a ceramic ion conductive membrane. The electrodes, catholyte, and anolyte (analytes) are specific to each system and are described elsewhere in the art.

[0066] This description relates to lithium-sulfur batteries and sodium-sulfur batteries. Lithium-sulfur batteries can be characterized as secondary batteries containing metallic lithium as the anode and sulfur as the cathode, where a liquid organic solution composed of a lithium salt and an ether, such as a cyclic ether, a short-chain ether, or a glycol ether, or a combination thereof, serves as the electrolyte. A solid, ionically conductive membrane is used to separate the lithium anode from the sulfide cathode. Alternatively, the anode may be composed of carbon, lithiated carbon, or silicon. Sodium-sulfur batteries can be characterized as secondary batteries containing metallic sodium as the anode and sulfur as the cathode, where a liquid organic solution composed of a sodium salt and an ether, such as a cyclic ether, a short-chain ether, or a glycol ether, or a combination thereof, serves as the electrolyte. Alternatively, the anode may be composed of carbon, lithiated carbon, or silicon. In some cases, the sulfur cathode can be encapsulated in a carbon structure or similar design, or coated with a polymer to reduce or prevent the polysulfide shuttle effect.

[0067] This description relates to molten salt batteries. Molten salt batteries include, but are not limited to, sodium-sulfur batteries or sodium-nickel chloride (Zebra) batteries. Sodium-sulfur (NaS) batteries can be characterized as secondary molten salt batteries containing metallic sodium as the negative electrode and sulfur as the positive electrode, with both electrodes typically in a liquid state during battery operation. The electrolyte for NaS batteries may include, but is not limited to, an interlocking beta-alumina layered membrane as a ceramic solid electrolyte, typically in tubular form. Sodium-nickel chloride (Na-NiCl) or Zebra batteries can be characterized as secondary molten salt batteries containing metallic sodium as the negative electrode and nickel as the positive electrode, with the sodium being in a liquid state during battery operation. The electrolyte for Na-NiCl batteries may include, but is not limited to, molten sodium tetrachloroaluminate (NaAlCl), with an interlocking beta-alumina layered membrane acting as a separator between the NaAlCl and the molten sodium. This disclosure relates to air batteries. Air batteries include primary air batteries and secondary air batteries. Primary air batteries include, but are not limited to, aluminum-air batteries and zinc-air batteries. Secondary air batteries include, but are not limited to, lithium-air batteries, sodium-air batteries, potassium-air batteries, aluminum-air batteries, iron-air batteries, and silicon-air batteries. Secondary air batteries can contain metals, metal alloys, or metal oxides as the negative electrode or anode. For example, lithium-air batteries can contain lithium metal or lithium metal alloys. Sodium-air batteries can contain sodium metal or sodium metal alloys. Potassium-air batteries can contain potassium metal or potassium metal alloys. Silicon-air batteries can contain silicon metal, silicon wafers, or silicon alloys. Iron-air batteries can contain iron metal or iron oxide anodes. Secondary air battery anodes can be coated with a thin layer that acts as an artificial solid electrolyte interfacial layer, including, but not limited to, a protective layer or layer to reduce the resistance at the electrode / solid ionically conductive membrane interface.Secondary air batteries can contain a porous cathode structure to allow atmospheric oxygen to enter the system. The porous cathode can be composed of carbon, such as mesoporous carbon. Alternatively, the porous cathode can be a screen, grid, or foam material, such as nickel foam, coated with a carbon layer. Secondary air batteries can contain catalysts, such as, but not limited to, manganese, cobalt, ruthenium, platinum, silver, or combinations thereof. The catalyst can be deposited on the carbon in the case of catalytic particles, or oriented within the carbon structure as a dopant. Alternatively, secondary air batteries can lack a cathode structure, and atmospheric oxygen functions as the cathode, as in silicon-air batteries. Secondary air batteries can contain liquid electrolytes, including, but not limited to, aprotic, aqueous, mixed aqueous / aprotic, or solid-state properties or compositions.

[0068] This description relates to lithium primary batteries. Primary batteries, particularly lithium primary batteries, can use a solid ionically conductive membrane as a separator. Lithium primary batteries may include, but are not limited to, lithium carbon monofluoride, lithium manganese dioxide, lithium copper oxide, and lithium thionyl chloride. Other primary lithium batteries may be specialized with cathodes composed of, but not limited to, lithium silver chromate, lithium silver vanadium oxide, lithium lead bismuthate, lithium bismuth trioxide, lithium copper sulfide, lithium copper lead sulfide, lithium iodide, lithium sulfur dioxide, lithium sulfuryl chloride, and the like.

[0069] Further examples of electrochemical cells using thermally sprayed solid ionically conductive membranes are referenced in the following figures.

[0070] Figure 1 is a schematic diagram of a solid ion-conducting electrolyte membrane prepared by conventional means such as pressing or tape casting, followed by heat treatment, showing a randomly distributed irregular hexagonal-like high-angle grain boundary structure. Figure 2 is a schematic diagram of the grain boundary vector orientation in an applied electric field for a conventional solid conductor with randomly distributed irregular hexagonal high-angle grain boundaries.

[0071] Figure 3 is a schematic diagram of the presently described solid ionically conductive membrane prepared by thermal spraying, showing an in-plane layered grain structure. Figure 4 is a schematic diagram of the grain boundary vector direction perpendicular to the direction of the applied electric field, with subsequent layers blocking electron crossing. This diagram illustrates the ability of the interlocking layered structure to block the penetration and propagation of metal dendrites, such as lithium dendrites. The diagram in Figure 4 shows additional inventive features of the presently described interlocking layered structure microstructure. The present description may include any illustrated embodiment of the disclosed microstructure.

[0072] Figure 5 is a schematic diagram of the process for fabricating an interlocking layer structure in which an ion-conducting membrane (104) is thermally sprayed onto a removable substrate (102). The removable substrate is removed from the solid ion-conducting membrane to form a free-standing solid ion-conducting membrane (106).

[0073] 6 is a schematic diagram of a solid ion-conducting membrane supported on a porous support substrate (110). In a first example, the ion-conducting membrane (108) supported on the porous support substrate is sprayed onto a bare porous substrate as the porous support substrate (108). In a second example, the ion-conducting membrane (108) supported on the porous support substrate is sprayed onto a porous support substrate (108) pre-loaded with a temporary filler material. In a third example, the ion-conducting membrane supported on the porous support substrate (108) is sprayed onto a porous support substrate (108) pre-loaded with a secondary battery electrode active material.

[0074] Figure 7 is a schematic view of a solid ion conductive film formed on a flat surface (108). In a first example, an ion conductive film (116) is formed on a non-conductive substrate as the flat surface (108). In a second example, an ion conductive film (116) is formed on a conductive substrate as the flat surface (108).

[0075] Figure 8 is a schematic view of a solid ion conductive film formed on a secondary battery electrode, and the ion conductive film (122) is sprayed on a secondary battery electrode (124) preformed on a current collector (126).

[0076] Figure 9 is a schematic view of a secondary battery including a solid ion conductive film, and the ion conductive film is a self-supporting solid ion conductive film (106) assembled between a secondary battery negative electrode (130) coated on a negative electrode current collector (128) and a secondary battery positive electrode (132) coated on a positive electrode current collector (134).

[0077] Figure 10 is a schematic view of a secondary battery including a solid ion conductive film, and the ion conductive film is supported on a porous support substrate (108), and the porous support substrate is a conductive porous support substrate (136) pre-filled with an embedded secondary battery positive electrode (138). The conductive porous support substrate may be conductive itself or may be conformally coated with a conformally coated conductive material. After spraying, the secondary battery is assembled with a secondary battery negative electrode (130) coated on a negative current collector (128).

[0078] Figure 11 is a schematic view of a secondary battery including a solid ion conductive film, and the ion conductive film is supported on a porous support substrate (108), and the porous support substrate is a conductive porous support substrate (136) pre-filled with an embedded secondary battery negative electrode (140). The conductive porous support substrate may be conductive itself or may be conformally coated with a conformally coated conductive material. After spraying, the secondary battery is assembled with a secondary battery positive electrode (132) coated on a positive current collector (134).

[0079] Figure 12 is a schematic diagram of a secondary battery including a solid ion conductive membrane. The ion conductive membrane is formed on a secondary battery electrode (122), and the secondary battery electrode is a secondary battery positive electrode (132) coated on a positive current collector (134). After spraying, the secondary battery is assembled (142) with the secondary battery negative electrode (130) coated on the negative current collector (128).

[0080] Figure 13 is a schematic diagram of a secondary battery including a solid ion conductive membrane. The ion conductive membrane is formed on a secondary battery electrode (122), and the secondary battery electrode is a secondary battery negative electrode (130) coated on a negative current collector (128). After spraying, the secondary battery is assembled (142) with the secondary battery positive electrode (132) coated on the positive current collector (134).

[0081] Figure 14 is a schematic diagram of an air battery including a solid ion conductive membrane. The ion conductive membrane is an independent solid ion conductive membrane (106) assembled between a negative electrode (130) coated on a negative current collector (128) of the air battery or the secondary battery, and a porous positive electrode (144) containing a catalyst by which oxygen gas or atmosphere (146) may enter the system and react accordingly. Alternatively, the ion conductive membrane may be formed on the negative electrode of the air battery.

[0082] Figure 15 is a schematic diagram of an air battery including a solid ion conductive membrane. The ion conductive membrane is supported on a porous support substrate (108), and the porous support substrate is a conductive porous support substrate (136) pre-filled with an embedded air battery or secondary battery negative electrode (140). The conductive porous support substrate may be conductive itself, or may be conformally coated with a conformally coated conductive material. After spraying, the air battery is assembled using a porous positive electrode (144) containing a catalyst by which oxygen gas or atmosphere (146) may enter the system and react accordingly.

[0083] Figure 16 is a schematic diagram of an air battery including a solid ion conductive membrane. The ion conductive membrane is supported on a porous support substrate (108), and the porous support substrate is a conductive porous support substrate (148) coated with a catalyst by which oxygen gas or atmosphere (146) can enter the system and react accordingly. After spraying, an air battery is assembled using an air battery or secondary battery negative electrode (130) coated on a negative current collector (128).

[0084] Figure 17 is a schematic diagram of a cathode-less secondary battery composed of a solid ion conductive membrane. The solid ion conductive membrane is formed on a flat substrate (116), and the flat substrate is a negative current collector (128). After spraying, a cathode-less battery is assembled with a secondary cathode (132) coated on a positive current collector (134). A bias (150) is applied to the assembled cathode-less battery to form a metal anode layer (152) between the solid ion conductive membrane (116) and the negative current collector (128).

[0085] Figure 18 is a schematic diagram of a flow-type secondary battery including a solid ion conductive membrane. The ion conductive membrane is a self-supporting solid ion conductive membrane (106) that separates an anode liquid (158) and a cathode liquid (160). On the anode liquid side opposite to the self-supporting membrane, there is a flow-type secondary battery negative electrode (154) coated on a negative current collector (128). On the cathode liquid side opposite to the self-supporting membrane, there is a flow-type secondary battery positive electrode (156) coated on a positive current collector (134).

[0086] FIG. 19 is a schematic diagram of a flow-type secondary battery including a solid ion conductive membrane. The ion conductive membrane is supported on a porous support substrate (108). The porous support substrate (110) is pre-filled with a flow-type secondary battery negative electrode (154) embedded therein and a negative current collector (128) on the opposite side of the support substrate. Alternatively, the porous support substrate is a conductive porous substrate (136) or has a conductive layer that is conformal although insulating, and the flow-type secondary battery negative electrode is conformally coated on the support porous substrate. The anode liquid (158) is preferably added after spraying and the assembly of the flow-type secondary battery. On the opposite side of the ion conductive membrane, there are a cathode liquid (160) and a flow-type secondary battery positive electrode (156) coated on a positive current collector (134).

[0087] FIG. 20 is a schematic diagram of a flow-type secondary battery including a solid ion conductive membrane. The ion conductive membrane is supported on a porous support substrate (108). The porous support substrate (110) is pre-filled with a flow-type secondary battery positive electrode (156) embedded therein and a positive current collector (134) on the opposite side of the support substrate. Alternatively, the porous support substrate is a conductive porous substrate (136) or has a conductive layer that is conformal although insulating, and the flow-type secondary battery positive electrode is conformally coated on the support porous substrate. The cathode liquid (160) is preferably added after spraying and the assembly of the flow-type secondary battery. On the opposite side of the ion conductive membrane, there are an anode liquid (158) and a flow-type secondary battery negative electrode (154) coated on a negative current collector (128).

[0088] FIG. 21 is a schematic diagram of a flow-type secondary battery including a solid ion conductive membrane. The ion conductive membrane is formed on a preformed battery electrode (122), and the preformed battery electrode is a metal or metal alloy anode (162) formed on a negative current collector (128). On the opposite side of the ion conductive membrane, there are a cathode liquid (160) and a flow-type secondary battery positive electrode (156) coated on a negative current collector (134).

[0089] Figure 22 is a cross-sectional scanning electron microscope image of a solid ion conductive electrolyte membrane prepared by conventional means such as pressure molding or tape casting and then heat-treated.

[0090] Figure 23 is a plan-view scanning electron microscope image of a solid ion conductive membrane prepared by spraying, showing the melting / hardening structure of the ion conductive ceramic membrane. The scanning electron microscope image of Figure 23 shows the additional inventive features of the microstructure of the interlocking layered structure described herein. This description includes any of the illustrated aspects of the disclosed microstructure.

[0091] Figure 24 is a cross-sectional scanning electron microscope image of a solid ion conductive membrane with a thickness of about 170 μm prepared by spraying, showing the in-plane layered nature of the structure. The scanning electron microscope image of Figure 24 shows the additional inventive features of the microstructure of the interlocking layered structure described herein. This description includes any of the illustrated aspects of the disclosed microstructure.

[0092] Figure 25 is a top-view digital image of a sprayed self-supporting solid ion conductive membrane with a diameter of 2.5 cm.

[0093] Figure 26 is a side-view digital image of a sprayed self-supporting solid ion conductive membrane with a thickness of about 250 μm.

[0094] Figure 27 is a cross-sectional scanning electron microscope image of an interlocking layered structure sprayed on a porous substrate.

[0095] Figure 28 is a digital image of an inclined plan view of a solid ion conductive membrane supported on a porous support structure.

[0096] Figure 29 is an X-ray diffraction spectrum of a sprayed lithium lanthanum zirconium oxide (LLZO) solid ion conductive membrane, compared with the standard LLZO PDF card number 7215448. The sprayed membrane shows an amorphous phase in the material.

[0097] In connection with the drawings, the examples may include one or more of the following.

Example

[0098] Fabrication of a self-supporting solid ion conductive membrane In one example, the self-supporting solid ion conductive membrane can be formed using thermal spraying, and the ion conductive material is sprayed onto a removable substrate.

[0099] In one aspect, the thermal spraying technique may also be called plasma spraying.

[0100] In one aspect, the ion conductive material may be lithium lanthanum zirconia oxide or LLZO, and LLZO is doped with a stabilizing element such as aluminum (Al-LLZO) and has a D50 particle size in the range of 1 to 100 μm.

[0101] In one aspect, the removable substrate is composed of a salt such as sodium chloride that can be dissolved in water after the spraying is completed.

[0102] In one aspect, the spraying distance between the plasma gun and the salt substrate may be in the range of 5 to 25 cm.

[0103] In one aspect, the carrier gas may be an inert gas such as helium or argon.

[0104] In one aspect, the plasma energy and flow rate are determined by external parameters such as tank pressure, regulator, gun type, etc., and can therefore be adjusted during spraying to achieve optimal spraying conditions.

[0105] In one aspect, the plasma spraying can be performed in a raster pattern on the salt substrate with a number of passes or repetitions between 2 and 50.

[0106] A cross-sectional scanning electron microscope image of the self-supporting LLZO (Al-doped) solid ion conductive membrane is shown in FIG. 24.

[0107] Digital images of the self-supporting LLZO (Al-doped) solid ion conductive film are shown in FIGS. 25 and 26.

[0108] The X-ray diffraction pattern of the plasma-sprayed LLZO (Al-doped) is shown in FIG. 29, and the LLZO composition is confirmed.

Example

[0109] Fabrication of a solid ion conductive film on a porous substrate In one example, the solid ion conductive film can be formed on the substrate using spraying, and the ion conductive material is sprayed onto the porous support substrate.

[0110] In one aspect, the spraying technique may also be called plasma spraying.

[0111] In one aspect, the ion conductive material may be lithium lanthanum zirconia oxide or LLZO, and the LLZO is doped with a stabilizing element such as tantalum and has a D50 particle size in the range of 1 to 100 μm.

[0112] In one aspect, the porous support substrate may be bare nickel foam.

[0113] In one aspect, the spraying distance between the plasma gun and the porous substrate may be in the range of 10 to 30 cm.

[0114] In one aspect, the spraying angle with respect to the surface of the porous substrate may be in the range of 5 to 45°.

[0115] In one aspect, the carrier gas may be an inert gas such as helium or argon.

[0116] In one aspect, the plasma energy and flow rate are determined by external parameters and can therefore be adjusted during spraying to achieve optimal spraying conditions.

[0117] In one aspect, plasma spraying can be performed in a raster pattern on a salt substrate with a number of passes or repetitions between 2 and 50.

[0118] A cross-sectional scanning electron microscope image of an LLZO (Ta-doped) solid ion conductive film supported on foamed nickel is shown in FIG. 27.

[0119] Digital images of an LLZO (Ta-doped) solid ion conductive film supported on foamed nickel are shown in FIGS. 27 and 28.

Examples

[0120] Solid Ion Conductive Films in Gel Polymer Secondary Batteries In one aspect, the solid ion conductive film can be used in a gel polymer secondary battery, and the secondary battery contains an ion conductive gel polymer in addition to the ion conductive layer film.

[0121] In one example, the solid ion conductive film can be formed on a porous positive current collector. After the formation of the layer film, the porous positive current collector can be filled with a cathode and an ion conductive gel polymer. The lithium metal anode can be formed on the opposite side of the solid ion conductive film. A schematic diagram of the example is shown in FIG. 10.

[0122] In one aspect, the solid ion conductive film can be composed of argyrodite (Li6PS5Cl).

[0123] In one aspect, the porous positive current collector may be porous foamed aluminum.

[0124] In one aspect, the cathode can be composed of lithium cobalt oxide (LiCoO2) as an electrode active material, carbon black as a conductive medium, and polyvinylidene fluoride as a binder.

[0125] In one aspect, the ion conductive gel polymer can be composed of polyethylene glycol (PEO) and a lithium salt.

[0126] In one aspect, the lithium metal anode can be deposited on the layered film using vapor deposition. Alternatively, the lithium metal anode coated on the negative current collector can be compression molded onto the layered film.

[0127] In one aspect, before the formation of the lithium layer, argyrodite can be coated with a protective layer to enhance cycle performance. Alternatively, before compression molding argyrodite, the lithium metal anode can be coated with a protective layer.

[0128] In the scenario of compression molding lithium metal onto argyrodite, a liquid electrolyte can be applied at the interface between the lithium anode and argyrodite.

[0129] In another example, a solid ion-conductive film can be formed on a porous negative current collector. After the formation of the layered film, the porous negative current collector can be filled with an anode and an ion-conductive gel polymer. The cathode can be formed on the opposite side of the solid ion-conductive film containing the gel polymer at the interface. A schematic diagram of the example is shown in FIG. 11.

[0130] In one aspect, the solid ion-conductive film can be composed of LAGP (Li1-xAl x Ge 2-x (PO4)3) having a NASICON structure.

[0131] In one aspect, the porous negative current collector may be porous foamed copper.

[0132] In one aspect, the anode can be composed of silicon as the electrode active material, carbon black as the conductive medium, and styrene-butadiene rubber as the binder. The voids in the foamed copper may enable the volume expansion of silicon. In addition, silicon may be coated with a protective layer.

[0133] In one aspect, the ion-conducting gel polymer can be composed of poly(vinylidene fluoride)-co-hexafluoropropylene (PVDF-HFP), a lithium salt, and an organic-based liquid electrolyte.

[0134] In one aspect, the cathode can be composed of lithium manganate (LiMnO4) as the electrode active material, carbon black as the conductive medium, and styrene-butadiene rubber as the binder, coated on an aluminum foil current collector.

[0135] In one aspect, the ion-conducting gel polymer can be composed of poly(vinylidene fluoride)-co-hexafluoropropylene (PVDF-HFP) and a lithium salt, and an organic-based liquid electrolyte can be used at the cathode / layered film interface.

[0136] In yet another example, the solid ion-conducting membrane can be made self-standing and assembled into a gel polymer battery, and the ion-conducting gel polymer is coated on both sides of the layered film at the interfaces of both the anode and the cathode. A schematic diagram of the example is shown in FIG. 9.

[0137] In one aspect, the solid ion-conducting membrane can be composed of niobium-doped lithium lanthanum zirconate oxide (Nb-LLZO).

[0138] In one aspect, the anode can be composed of graphite as the electrode active material, carbon black as the conductive medium, and polyvinylidene fluoride as the binder, coated on a copper current collector.

[0139] In one aspect, the cathode can be composed of lithium iron phosphate (LiFePO4) as the electrode active material, carbon black as the conductive medium, and polyvinylidene fluoride as the binder, coated on an aluminum current collector.

[0140] In one aspect, the ion-conducting gel polymer can be composed of polyacrylonitrile (PAN), a lithium salt, and an organic-based liquid electrolyte.

[0141] In yet another example, a solid ion-conducting membrane can be formed directly on the lithium metal surface, and the ion-conducting gel polymer is applied on the opposite side of the cathode / laminated film interface. A schematic diagram of the example is shown in FIG. 12.

[0142] In one aspect, the solid ion-conducting membrane can be composed of thiophosphate glass ceramic or LPS (Li3PS4) sputtered on the lithium metal.

[0143] In one aspect, a lithium metal or a lithium metal alloy can be coated on a stainless-steel foil so as not to react with the sulfide in the LPS.

[0144] In one aspect, the lithium metal or the lithium metal alloy may be coated with a protective layer before sputtering the LPS.

[0145] In one aspect, the cathode can be coated on an aluminum current collector and composed of lithium nickel cobalt manganese oxide (NCM-811) as an electrode active material, and can be coated with a protective layer, carbon black as a conductive medium, and polyvinylidene fluoride as a binder.

[0146] In one aspect, the ion-conducting gel polymer can be composed of polyethylene glycol (PEO), a lithium salt, and an organic-based liquid electrolyte.

Examples

[0147] Solid Ion-Conducting Membrane in Hybrid / Semi-Solid Secondary Batteries In one aspect, the solid ion-conducting membrane can be used in a hybrid or semi-solid secondary battery, and the secondary battery contains an ion-conducting liquid electrolyte in addition to the ion-conducting laminated film.

[0148] In one example, a solid ion conductive membrane can be formed on a porous positive current collector. After the formation of the layered membrane, the porous positive current collector can be filled with a cathode and a liquid electrolyte. The lithium metal anode can be formed on the opposite side of the solid ion conductive membrane. A schematic diagram of the example is shown in FIG. 10.

[0149] In one aspect, the solid ion conductive membrane can be composed of thiophosphate glass ceramic or LPS (Li3PS4).

[0150] In one aspect, the porous positive current collector may be porous foamed aluminum.

[0151] In one aspect, the cathode can be composed of lithium cobalt oxide (LiCoO2) as an electrode active material, and can be coated with a protective layer, carbon black as a conductive medium, and polyvinylidene fluoride as a binder.

[0152] In one aspect, the liquid electrolyte may be a complex salt organic-based liquid electrolyte system such as 2M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) + lithium difluoro(oxalato)borate (LiDFOB) in dimethyl ether (DME).

[0153] In one aspect, the lithium metal or lithium metal alloy anode can be deposited on the layered membrane using vapor deposition. Alternatively, the lithium metal anode or lithium metal alloy coated on the negative current collector can be pressure-molded on the layered membrane.

[0154] In one aspect, before the formation of the lithium layer, LPS can be coated with a protective layer to enhance the cyclability. Alternatively, before pressure-molding onto LPS, the lithium metal anode may be coated with a protective layer.

[0155] In the scenario of pressure-molding lithium metal onto LPS, a liquid electrolyte can be added to the interface between the lithium anode and LPS.

[0156] In another example, a solid ion conductive membrane can be formed on a porous negative current collector. After the formation of the layered membrane, the porous negative current collector can be filled with an anode and a liquid electrolyte. The cathode can be formed on the opposite side of the solid ion conductive membrane containing the liquid electrolyte at the interface. A schematic diagram of the example is shown in FIG. 11.

[0157] In one aspect, the solid ion conductive membrane can be composed of a sulfide solid electrolyte Thio-LISICON LGPS (Li 10 GeP2S 12 ).

[0158] In one aspect, the porous negative current collector may be porous foamed copper.

[0159] In one aspect, the anode can be composed of silicon as an electrode active material, carbon black as a conductive medium, and styrene-butadiene rubber as a binder. The voids in the foamed copper may enable the volume expansion of silicon. In addition, silicon may be coated with a protective layer.

[0160] In one aspect, the liquid electrolyte may be a complex salt organic-based liquid electrolyte system such as 2M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) + lithium difluoro(oxalato)borate (LiDFOB) in dimethyl ether (DME).

[0161] In one aspect, the cathode can be coated on an aluminum foil current collector and composed of lithium manganate (LiMnO4) as an electrode active material, and can be coated with a protective layer, carbon black as a conductive medium, and styrene-butadiene rubber as a binder.

[0162] In one aspect, the liquid electrolyte may be a complex salt organic-based liquid electrolyte system such as 2M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) + lithium difluoro(oxalato)borate (LiDFOB) in dimethyl ether (DME), and can be used at the interface of the cathode / layered film.

[0163] In yet another example, the solid ion-conductive membrane can be self-standing and assembled into a hybrid or semi-solid secondary battery, and the ion-conductive liquid electrolyte is applied to both sides of the layered film at the interfaces of both the anode and the cathode. A schematic diagram of the example is shown in FIG. 9.

[0164] In one aspect, the solid ion-conductive membrane can be composed of argyrodite (Li6PS5Cl x Br y [X + Y = 1]) having a mixed halogen formulation.

[0165] In one aspect, the anode can be composed of graphite as the electrode active material, carbon black as the conductive medium, and polyvinylidene fluoride as the binder, coated on a copper current collector.

[0166] In one aspect, the cathode can be coated on an aluminum current collector and composed of lithium iron phosphate (LiFePO4) as the electrode active material, and can be coated with a protective layer, carbon black as the conductive medium, and polyvinylidene fluoride as the binder.

[0167] In one aspect, the liquid electrolyte may also be a complex salt organic-based liquid electrolyte system such as 2M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) + lithium difluoro(oxalato)borate (LiDFOB) in tetraethylene glycol dimethyl ether (TEGDME).

[0168] In yet another example, a solid ion conductive membrane can be formed directly on the surface of a lithium metal or a lithium metal alloy, and the ion conductive liquid is applied on the side opposite to the cathode / laminar film interface. A schematic diagram of the example is shown in FIG. 13.

[0169] In one aspect, the solid ion conductive membrane can be composed of aluminum-doped lithium lanthanum zirconate oxide (Al-LLZO) sprayed on a lithium metal.

[0170] In one aspect, a lithium metal or a lithium metal alloy can be coated on a copper or stainless steel foil.

[0171] In one aspect, before spraying Al-LLZO, the lithium metal or the lithium metal alloy may be coated with a protective layer.

[0172] In one aspect, the cathode can be composed of lithium nickel cobalt manganese oxide (NCM-622) as an electrode active material, carbon black as a conductive medium, and polyvinylidene fluoride as a binder, coated on an aluminum current collector.

[0173] In one aspect, the liquid electrolyte may contain bis(trifluoromethanesulfonyl)imide (LiTFSI) in a mixture of ethylene carbonate, dimethyl carbonate, and diethyl carbonate (EC / DMC / DEC 1 / 1 / 1 ratio) and 2% vinylene carbonate (VC).

Examples

[0174] Solid Ion Conductive Membrane in a Solid Secondary Battery In one aspect, the solid ion conductive membrane can be used in a solid secondary battery, and the secondary battery contains only a solid ion conductive material as the sole ion conductive medium.

[0175] In one example, the solid ion conductive membrane is self - supporting and can be assembled into a solid - state secondary battery, and the secondary battery is composed of a composite cathode, a composite anode or a lithium metal anode, and a layered membrane. A schematic diagram of the example is shown in FIG. 9.

[0176] In one aspect, the solid ion conductive membrane can be composed of tantalum - doped lithium lanthanum zirconium oxide (Ta - LLZO).

[0177] In one aspect, the composite cathode can be composed of lithium nickel oxide (LiNiO2) as an electrode active material, carbon black as a conductive medium, polyvinylidene fluoride as a binder, and polyethylene oxide (PEO) mixed with a lithium salt as an ion conductive medium, which is coated on an aluminum current collector.

[0178] In one aspect, the composite anode can be composed of graphite as an electrode active material, carbon black as a conductive medium, polyvinylidene fluoride as a binder, and polyethylene oxide (PEO) mixed with a lithium salt as an ion conductive medium, which is coated on a copper current collector.

[0179] In one aspect, an alternative to the composite anode, a lithium metal or lithium metal alloy anode, can be coated with a protective layer to improve the cycle life.

[0180] In another example, the solid ion conductive membrane can be sprayed or directly formed on the surface of a lithium metal or lithium metal alloy, and the composite cathode is assembled on the surface opposite to the layered membrane. A schematic diagram of the example is shown in FIG. 13.

[0181] In one aspect, the solid ion conductive membrane can be composed of argyrodite (Li6PS5Cl).

[0182] In one aspect, the composite cathode can be coated on an aluminum current collector and composed of lithium nickel cobalt aluminum oxide (NCA) as an electrode active material, carbon black as a conductive medium, polyvinylidene fluoride as a binder, and polyacrylonitrile (PAN) mixed with a lithium salt as an ion conductive medium.

[0183] In one aspect, to prevent the formation of copper sulfide, a lithium metal or lithium metal alloy anode can be coated on a stainless steel or aluminum foil current collector.

[0184] In one aspect, the lithium metal or lithium metal alloy anode can be coated with a protective layer to enhance cyclability before the formation of an interlocking layered structure.

[0185] In yet another example, a solid ion conductive membrane can be sprayed or directly formed on the composite cathode, and a lithium metal, lithium metal alloy, or composite anode is assembled on the surface opposite to the side of the layered membrane. A schematic diagram of the example is shown in FIG. 12.

[0186] In one aspect, the solid ion conductive membrane can be composed of LAGP (Li1-xAl x Ge 2-x (PO4)3) having a NASICON structure.

[0187] In one aspect, the composite cathode can be composed of lithium nickel cobalt manganese oxide (NCM-811) as an electrode active material, carbon black as a conductive medium, polyvinylidene fluoride as a binder, and LAGP as an ion conductive medium, which are coated on an aluminum current collector.

[0188] Alternatively, a thin-layer cathode may be used in contrast to the composite cathode. The thin-layer cathode is a thin layer of an active material such as NCM-811 coated on an aluminum current collector.

[0189] In one aspect, the composite anode can be composed of graphite as an electrode active material, carbon black as a conductive medium, polyvinylidene fluoride as a binder, and polyethylene oxide (PEO) mixed with a lithium salt as an ion conductive medium, which is coated on a copper current collector.

[0190] In one aspect, a lithium metal or lithium metal alloy anode, which is an alternative to the composite anode, can be coated with a protective layer to improve the cycle life.

[0191] In yet another example, a solid ion conductive film can be sprayed or directly formed on the composite anode, and the composite cathode is assembled on the surface opposite to that of the layer film. A schematic diagram of the example is shown in FIG. 13.

[0192] In one aspect, the interlocking film can be composed of thiophosphate glass ceramic or LPS (Li3PS4).

[0193] In one aspect, the composite anode can be composed of graphite as an electrode active material, carbon black as a conductive medium, styrene-butadiene rubber as a binder, and LPS as an ion conductive medium, which is coated on a stainless steel or aluminum current collector.

[0194] Alternatively, a thin-layer anode may be used in contrast to the composite anode. The thin-layer anode is a thin layer of an active material such as titanium oxide coated on a copper current collector.

[0195] In one aspect, the composite cathode can be composed of lithium nickel cobalt manganese oxide (NCM-622) as an electrode active material by coating on an aluminum current collector, and can be coated with a protective layer, carbon black as a conductive medium, styrene-butadiene rubber as a binder, and LPS as an ion conductive medium.

Examples

[0196] Solid Ion Conductive Membrane in Metal-Sulfur Secondary Battery In one aspect, the solid ion conductive membrane can be used in a metal-sulfur secondary battery, and the secondary battery includes a metal anode, a sulfur anode, and a layered membrane.

[0197] In one example, the solid ion conductive membrane can be sprayed onto an anode of lithium metal or a lithium metal alloy, and the secondary battery is a lithium-sulfur secondary battery. A schematic diagram of the example is shown in FIG. 13.

[0198] In one aspect, the solid ion conductive membrane can be composed of argyrodite (Li6PS5Cl) or argyrodite with a halogen mixing ratio.

[0199] In one aspect, the lithium metal or lithium metal alloy anode can be coated with a protective layer to increase the number of cycles.

[0200] In one aspect, a sulfur-based cathode can be assembled on the opposite side of the layered membrane. Also, sulfur may be encapsulated in an open material such as carbon nanotubes.

[0201] In one aspect, the sulfur-based cathode may be a composite-based cathode in the case of a solid sulfur battery, and argyrodite functions as a lithium ion conduction medium.

[0202] In one aspect, a lithium-metal sulfur battery can use a gel polymer or a liquid electrolyte to further promote lithium transport in the cathode.

[0203] In one example, the solid ion conductive membrane can be sprayed onto an anode of sodium metal or a sodium metal alloy, and the secondary battery is a sodium-sulfur secondary battery. A schematic diagram of the example is shown in FIG. 13.

[0204] In one aspect, the solid ion conductive membrane can be composed of sodium-based argyrodite (Na6PS5Cl) or argyrodite with a halogen mixing ratio.

[0205] In one aspect, the sodium metal or sodium metal alloy anode can be coated with a protective layer to increase the cycle.

[0206] In one aspect, a sulfur-based cathode can be assembled on the opposite side of the layered membrane. Also, sulfur may be encapsulated in an open material such as carbon nanotubes.

[0207] In one aspect, the sulfur-based cathode may be a composite-based cathode in the case of a solid sulfur battery, and the sodium-based argyrodite functions as an ion conduction medium.

[0208] In one aspect, a sodium-metal sulfur battery can use a gel polymer or a liquid electrolyte to further promote sodium transport at the cathode.

[0209] In one example, the solid ion conductive membrane can be sprayed onto a porous positive current collector, and sulfur is encapsulated after the formation of the layered membrane. A schematic diagram of the example is shown in FIG. 10.

[0210] In one aspect, the solid ion conductive membrane can be composed of a sulfide solid electrolyte Thio-LISICON LGPS (Li 10 GeP2S 12 )

[0211] In one aspect, the positive current collector may be composed of foamed aluminum.

[0212] In one aspect, the positive current collector encapsulated with sulfur may be further encapsulated with a conductive polymer such as poly(3,4-ethylenedioxythiophene (PEDOT)).

[0213] In one aspect, the metal or metal alloy anode can be deposited onto a layered film using vapor deposition. Alternatively, a metal or metal alloy anode coated on a negative current collector can be compression molded onto a layered film.

[0214] In one aspect, before the formation of the metal layer, LGPS can be coated with a protective layer to enhance cyclability. Alternatively, the metal anode may be coated with a protective layer before compression molding onto LGPS.

[0215] In the scenario of compression molding the metal anode onto LGPS, a liquid electrolyte can be added to the interface between the metal anode and LPS.

[0216] In one example, the solid ion conductive film may be self - supporting and assembled between a metal anode and a sulfur - based cathode. A schematic diagram of the example is shown in FIG. 9.

[0217] In one aspect, the self - supporting solid ion conductive film can be composed of thiophosphate glass ceramic or LPS (Li3PS4).

[0218] In one aspect, a sulfur - based cathode coated on an aluminum foil can be assembled into a metal - sulfur battery. Also, sulfur may be encapsulated in an open material such as carbon nanotubes.

[0219] In one aspect, the sulfur - based cathode may be a composite - based cathode in the case of a solid sulfur battery, and LPS functions as an ion - conducting medium.

[0220] In one aspect, the metal - sulfur battery can use a gel polymer or a liquid electrolyte to further promote sodium transport at the cathode.

[0221] In one aspect, to avoid the formation of copper sulfide, the metal or metal alloy anode can be coated onto a stainless - steel or aluminum foil current collector.

[0222] In one aspect, the metal or metal alloy anode can be coated with a protective layer to enhance cyclability.

Examples

[0223] Solid Ion Conductive Membrane in an Air-Type Battery In one aspect, the solid ion conductive membrane can be used in an air-type battery such as a lithium-air secondary battery, and the secondary battery contains an anode, a layered membrane, and a porous cathode containing a catalyst.

[0224] In one example, the solid ion conductive membrane may be self-supporting, and the layered membrane is assembled between a lithium metal anode and a porous cathode. A schematic diagram of the example is shown in FIG. 14.

[0225] In one aspect, the solid ion conductive membrane can be composed of niobium-doped lithium lanthanum aluminum oxide (Nb-LLZO).

[0226] In one aspect, the porous cathode can be composed of a carbon material coated on a mesh-like structure such as an aluminum mesh.

[0227] In one aspect, a catalyst such as platinum can be coated on the carbon material or mixed into the carbon material.

[0228] In one aspect, the lithium metal or lithium metal alloy anode can be coated with a protective layer to enhance the cycle.

[0229] In one aspect, an ionic conductive liquid or a gel polymer can be disposed at the interface between the electrode and the Nb-LLZO.

[0230] In another example, the solid ion conductive membrane can be formed on a porous negative current collector containing an embedded anode material, and a porous cathode containing a catalyst is assembled on the surface on the opposite side of the layered membrane. A schematic diagram of the example is shown in FIG. 15.

[0231] In one aspect, the solid ion conductive membrane can be composed of LAGP (Li1-xAl x Ge 2-x (PO4)3) having a NASICON structure.

[0232] In one aspect, the negative porous current collector may include foamed copper.

[0233] In one aspect, the anode material can include silicon as an electrode active material, a binder, and a conductive additive such as carbon nanotubes.

[0234] In one aspect, an ionic conductive liquid or a gel polymer can be disposed at the interface between the porous cathode and the LAGP.

[0235] In one aspect, the porous cathode assembled on the surface opposite to the LAGP can be composed of a carbon material coated on a mesh-like structure such as a steel mesh.

[0236] In one aspect, a catalyst such as cobalt oxide can be coated on or mixed into the carbon material.

[0237] In one aspect, an ionic conductive gel polymer can be disposed at the interface between the porous cathode and the LAGP.

[0238] In yet another example, a solid ion conductive membrane can be formed on the porous cathode, and the anode can be assembled on the surface opposite to the surface of the layered membrane. A schematic diagram of the example is shown in FIG. 16.

[0239] In one aspect, the solid ion conductive membrane can be composed of a perovskite-type oxide such as (Li,La)TiO3.

[0240] In one aspect, first, a porous cathode can be formed on a porous support substrate, and the porous support substrate can be composed of foamed aluminum.

[0241] In one aspect, a catalyst such as manganese can be coated on the carbon material or mixed into the carbon material.

[0242] In one aspect, the anode can be composed of graphite as an electrode active material by mixing with a binder and an electron additive.

[0243] In one aspect, the anode can be coated on a layered film or on a current collector such as copper and assembled into an air battery.

[0244] In the scenario where the anode is coated on a current collector, an ion-conductive liquid or a gel polymer can be disposed at the interface between the layered film and the anode.

[0245] In one aspect, an alternative to graphite may be a lithium metal or a lithium metal alloy anode.

[0246] In one aspect, the lithium metal or lithium metal alloy anode can be deposited on a layered film using vapor deposition. In this scenario, the layered film can be coated with a protective layer to increase the cycle.

[0247] In one aspect, a lithium metal or lithium metal alloy anode coated on a current collector such as a copper foil can be assembled into an air battery. In this scenario, the metal surface can be coated with a protective layer to increase the cycle.

[0248] In the scenario where a lithium metal or lithium metal alloy is coated on a current collector, an ion-conductive liquid or a gel polymer can be disposed at the interface between the layered film and the metal anode.

[0249] In yet another example, a solid ion-conductive membrane can be formed on the lithium metal anode, and a porous cathode containing a catalyst is assembled on the surface opposite to the layered film. A schematic diagram of the example is shown in FIG. 14.

[0250] In one aspect, the solid ion conductive membrane can be composed of aluminum-doped lithium lanthanum aluminum oxide (Al-LLZO).

[0251] In one aspect, the lithium metal or lithium metal alloy anode can be coated with a protective layer to increase the cycle.

[0252] In one aspect, an ionic conductive liquid or gel polymer can be disposed at the interface between the electrode and Nb-LLZO.

[0253] In one aspect, the porous cathode can be composed of a carbon material coated on a mesh-like structure such as an aluminum mesh.

[0254] In one aspect, a catalyst such as platinum can be coated on the carbon material or mixed in the carbon material.

[0255] In one aspect, an ionic conductive gel polymer can be disposed at the interface between the porous cathode and Al-LLZO.

Examples

[0256] Solid ion conductive membrane in aqueous or seawater batteries In one aspect, the solid ion conductive membrane can be used in a seawater secondary battery, and the secondary battery contains an anode, a layered membrane, and a cathode or seawater as a sodium ion source.

[0257] In one example, a solid ion conductive membrane is formed on the surface of an anode of sodium metal or a sodium metal alloy, and the layered membrane protects the metal from seawater. A schematic diagram of the example is shown in FIG. 13.

[0258] In one aspect, the solid ion conductive membrane is composed of sodium ion conductive NASICON

[0259] In one aspect, sodium metal or a sodium metal alloy can be coated on a current collector such as a copper foil.

[0260] In one aspect, the NASICON structure can protect sodium metal from seawater.

[0261] In one aspect, the seawater battery can be further protected by coating a polymer or resinous substance around the copper and on the sides of the metal and the NASICON structure.

[0262] In one aspect, the NASICON structure may be coated with a thin protective layer that allows the conduction of sodium ions but prevents the intrusion of water.

[0263] In another example, a solid ion-conductive membrane is formed on a porous negative current collector, and a hard carbon anode is embedded in the current collector. A schematic diagram of the example is shown in FIG. 11.

[0264] In one aspect, the solid ion-conductive membrane is composed of a sodium ion-conductive garnet structure.

[0265] In one aspect, the porous negative current collector can be composed of foamed copper.

[0266] In one aspect, the hard carbon anode as the active material can be mixed with a binder and a conductive additive.

[0267] In one aspect, the seawater battery can be further protected by coating a polymer or resin on the outer periphery of the foamed copper and on the sides of the garnet structure.

[0268] In one aspect, an ionic conductive liquid or a gel polymer can be added to the hard carbon mixture to further promote the transport of sodium ions.

[0269] In one aspect, the garnet structure may be coated with a thin protective layer that allows the conduction of sodium ions but prevents the intrusion of water.

Example

[0270] Solid ion conductive film in an anode-less battery In one aspect, the solid ion conductive film can be used in an anode-less secondary battery. When a bias is applied, a metal such as lithium metal is formed between the negative current collector and the layered film.

[0271] In one example, the solid ion conductive film can be sprayed onto a flat current collector or a pre-treated current collector, and a cathode coated on the current collector is assembled into a battery to form an anode-less battery. A schematic diagram of the example is shown in FIG. 17.

[0272] In one aspect, the solid ion conductive film can be composed of argyrodite (Li6PS5Cl) or argyrodite with a halogen mixing ratio.

[0273] In one aspect, the current collector may include a copper foil.

[0274] In one aspect, the anode-less film may be all-solid, and the cathode coated on the aluminum foil is a composite cathode composed of an active material, a binder, a conductive additive, and argyrodite as an ion conductive medium.

[0275] In one aspect, the anode-less film may not be all-solid, and the cathode coated on the aluminum foil is a conventional cathode composed of an active material, a binder, and a conductive additive.

[0276] In one aspect, the non-all-solid anode-less battery can contain an ion conductive liquid or a gel polymer at one or both interfaces of the argyrodite.

[0277] In another example, the solid ion conductive film can be sprayed onto the cathode, and the negative current collector is assembled on the surface opposite to the surface of the layered film to form an anode-less structure. A schematic diagram of the example is shown in FIG. 17.

[0278] In one aspect, the solid ion conductive membrane can be composed of niobium-doped lithium lanthanum zirconium oxide (Nb-LLZO).

[0279] In one aspect, the anode-less membrane may be all-solid, and the cathode coated on the aluminum foil is a composite cathode composed of an active material, a binder, a conductive additive, and aludidite as an ion conductive medium.

[0280] Alternatively, the cathode can be composed of a thin active material layer such as lithium cobalt oxide (LiCoO2) coated on the aluminum foil.

[0281] In one aspect, the anode-less membrane may not be all-solid, and the cathode coated on the aluminum foil is a conventional cathode composed of an active material, a binder, and a conductive additive.

[0282] In one aspect, the non-all-solid anode-less battery can contain an ion conductive liquid or a gel polymer at one or both interfaces of Nb-LLZO.

Example

[0283] Solid ion conductive membrane in a flow-type secondary battery In one aspect, the solid ion conductive membrane can be used as an ion conductive separator in a lithium flow-type or redox flow-type secondary battery, and the layered membrane is used to separate the anode liquid and the cathode liquid to prevent crossover.

[0284] In one example, the solid ion conductive membrane may be self-supporting. The solid ion conductive membrane is directly assembled into a flow battery to separate the anode liquid and the cathode liquid and prevent crossover. A schematic diagram of the example is shown in FIG. 18.

[0285] In one aspect, the solid ion conductive membrane can be composed of doped lithium lanthanum zirconium oxide.

[0286] In one aspect, the LLZO film can be coated with a thin protective layer that enables lithium ion conduction, rather than a solvent that forms the anode liquid and / or the cathode liquid.

[0287] In another example, a solid ion conductive film can be formed on a porous negative current collector, which contains an anode material and an anode liquid. A schematic diagram of the example is shown in FIG. 19.

[0288] In one aspect, the solid ion conductive film can be composed of argyrodite (Li6PS5Cl) or a mixed halogen composition.

[0289] In one aspect, the porous negative current collector can be composed of foamed copper.

[0290] Alternatively, the porous negative current collector can be composed of foamed aluminum oxide conformally coated with a conductive metal layer.

[0291] In one aspect, the negative electrode active material can be conformally coated on a conductive porous substrate.

[0292] In one aspect, the porous negative current collector can be planar, or non-planar such as tubular or cylindrical.

[0293] In yet another example, a solid ion conductive film can be formed on a porous positive current collector, which contains a cathode material and a cathode liquid. A schematic diagram of the example is shown in FIG. 20.

[0294] In one aspect, the solid ion conductive film can be composed of LAGP (Li1-xAl x Ge 2-x (PO4)3) having a NASICON structure.

[0295] In one aspect, the porous positive current collector may be composed of foamed aluminum.

[0296] Alternatively, the porous positive current collector can be composed of foamed aluminum oxide conformally coated with a conductive polymer layer.

[0297] In one aspect, the positive electrode active material can be conformally coated on a conductive porous substrate.

[0298] In one aspect, the porous positive current collector may be planar or non-planar in the shape of a tube or a cylinder.

[0299] In yet another example, a solid ion conductive membrane can be formed on the surface of a lithium metal or lithium metal alloy anode, and the flow battery can more precisely be described as a hybrid flow battery without an anode liquid. A schematic diagram of the example is shown in FIG. 19.

[0300] In one aspect, the solid ion conductive membrane can be composed of a sulfide solid electrolyte Thio-LISICON LGPS (Li 10 GeP2S 12 ).

[0301] In one aspect, the lithium metal or lithium metal alloy anode can be coated on a current collector such as stainless steel.

[0302] In one aspect, to enhance the cycle of the flow battery, the lithium metal or lithium metal alloy anode may be coated with a protective layer.

[0303] Alternatively, the lithium metal or lithium metal alloy anode may be coated on a porous conductive current collector, and the voids of the porous current collector are filled with an anode liquid.

[0304] The above-described systems and methods can be attributed to lithium-based secondary batteries, including but not limited to, for example, lithium-ion batteries, lithium metal batteries, all-solid-state lithium batteries, aqueous batteries, lithium polymer batteries, etc.

[0305] The above-described systems and methods can be attributed to secondary batteries having chemical properties beyond lithium, which may include sodium ions, aluminum ions, magnesium ions, iron ions, potassium ions, etc.

[0306] The above-described systems and methods can be attributed to various secondary battery designs, including but not limited to pouch cells, coil cells, button cells, cylindrical cells, prismatic cells, etc.

[0307] The above-described systems and methods can be attributed to secondary batteries with end uses including but not limited to electric vehicles, hybrid electric vehicles, mobile devices, handheld electronic devices, household appliances, medical, medical wearables, and wearable for portable energy storage.

[0308] The above-described systems and methods can be attributed to secondary batteries for grid-scale energy storage backup systems.

[0309] The above-described systems and methods can be attributed to secondary batteries with long life, high energy density and output density, and improved safety.

[0310] The above-described systems and methods can be attributed to alternative energy storage technologies such as primary batteries, flow batteries, air batteries, and molten salt batteries, and the solid ion conductive membrane is the main ion conductive separator.

[0311] The various aspects described herein are represented below by the following clauses. This application is not limited to the aspects represented by these clauses. Rather, this description includes these aspects in combination with any one or more additional features described above or shown in the drawings. For example, the present disclosure includes the following:

[0312] 1. A battery comprising an anode and a cathode that define an electric field therebetween, and a solid ion conductive membrane between the anode and the cathode, wherein the solid ion conductive membrane comprises a polycrystalline microstructure that defines grain boundaries between adjacent particles of the polycrystalline microstructure, and most of the grain boundary regions of the polycrystalline microstructure are oriented substantially perpendicular to the direction of the electric field defined by the anode and the cathode.

[0313] 2. The battery according to clause 1, wherein at least 55% of the grain boundary region is oriented substantially perpendicular to the direction of the electric field.

[0314] 3. The battery according to clause 1, wherein at least 60% of the grain boundary region is oriented substantially perpendicular to the direction of the electric field.

[0315] 4. The battery according to clause 1, wherein at least 65% of the grain boundary region is oriented substantially perpendicular to the direction of the electric field.

[0316] 5. The battery according to clause 1, wherein at least 70% of the grain boundary region is oriented substantially perpendicular to the direction of the electric field.

[0317] 6. The battery according to clause 1, wherein at least 75% of the grain boundary region is oriented substantially perpendicular to the direction of the electric field.

[0318] 7. The battery according to clause 1, wherein at least 80% of the grain boundary region is oriented substantially perpendicular to the direction of the electric field.

[0319] 8. The battery according to clause 1, wherein at least 85% of the grain boundary region is oriented substantially perpendicular to the direction of the electric field.

[0320] 9. The battery according to clause 1, wherein at least 90% of the grain boundary region is oriented substantially perpendicular to the direction of the electric field.

[0321] 10. The battery according to any one of clauses 1 to 9, wherein the percentage of the grain boundary region has an orthogonal direction within 35 degrees from the direction of the defined electric field.

[0322] 11. The battery according to any one of claims 1 to 9, wherein the percentage of the grain boundary region has an orthogonal direction within 30 degrees from the direction of the defined electric field.

[0323] 12. The battery according to any one of claims 1 to 9, wherein the percentage of the grain boundary region has an orthogonal direction within 25 degrees from the direction of the defined electric field.

[0324] 13. The battery according to any one of claims 1 to 9, wherein the percentage of the grain boundary region has an orthogonal direction within 20 degrees from the direction of the defined electric field.

[0325] 14. The battery according to any one of claims 1 to 9, wherein the percentage of the grain boundary region has an orthogonal direction within 15 degrees from the direction of the defined electric field.

[0326] 15. The battery according to any one of claims 1 to 14, wherein the polycrystalline microstructure includes a plurality of high aspect ratio particles having an average ratio of length to thickness of at least 2:1.

[0327] 16. The battery according to any one of claims 1 to 14, wherein the polycrystalline microstructure includes a plurality of high aspect ratio particles having an average ratio of length to thickness of at least 3:1.

[0328] 17. The battery according to any one of claims 1 to 14, wherein the polycrystalline microstructure includes a plurality of high aspect ratio particles having an average ratio of length to thickness of at least 4:1.

[0329] 18. The battery according to any one of claims 1 to 14, wherein the polycrystalline microstructure includes a plurality of high aspect ratio particles having an average ratio of length to thickness of at least 5:1.

[0330] 19. The battery according to any one of claims 1 to 14, wherein the polycrystalline microstructure includes a plurality of high aspect ratio particles having an average ratio of length to thickness of at least 6:1.

[0331] 20. The battery according to any one of clauses 1 to 14, wherein the polycrystalline microstructure comprises a plurality of high aspect ratio particles having an average length-to-thickness ratio of at least 7:1.

[0332] 21. The battery according to any one of clauses 1 to 14, wherein the polycrystalline microstructure comprises a plurality of high aspect ratio particles having an average length-to-thickness ratio of at least 8:1.

[0333] 22. The battery according to any one of clauses 1 to 14, wherein the polycrystalline microstructure comprises a plurality of high aspect ratio particles having an average length-to-thickness ratio of at least 9:1.

[0334] 23. The battery according to any one of clauses 1 to 14, wherein the polycrystalline microstructure comprises a plurality of high aspect ratio particles having an average length-to-thickness ratio of at least 10:1.

[0335] 24. The battery according to any one of clauses 15 to 23, wherein the amount of the high aspect ratio particles is at least 10 percent.

[0336] 25. The battery according to any one of clauses 15 to 23, wherein the amount of the high aspect ratio particles is at least 20 percent.

[0337] 26. The battery according to any one of clauses 15 to 23, wherein the amount of the high aspect ratio particles is at least 30 percent.

[0338] 27. The battery according to any one of clauses 15 to 23, wherein the amount of the high aspect ratio particles is at least 40 percent.

[0339] 28. The battery according to any one of clauses 15 to 23, wherein the amount of the high aspect ratio particles is at least 50 percent.

[0340] 29. The battery according to any one of clauses 15 to 23, wherein the amount of the high aspect ratio particles is at least 60 percent.

[0341] 30. The battery according to any one of clauses 15 to 23, wherein the amount of the high aspect ratio particles is at least 70 percent.

[0342] 31. The battery according to any one of clauses 15 to 23, wherein the amount of the high aspect ratio particles is at least 80 percent.

[0343] 32. The battery according to any one of clauses 15 to 31, wherein the high aspect ratio particles have an average length of at least 1 micron.

[0344] 33. The battery according to any one of clauses 15 to 31, wherein the high aspect ratio particles have an average length of at least 2 microns.

[0345] 34. The battery according to any one of clauses 15 to 31, wherein the high aspect ratio particles have an average length of at least 5 microns.

[0346] 35. The battery according to any one of clauses 15 to 31, wherein the high aspect ratio particles have an average length of at least 10 microns.

[0347] 36. The battery according to any one of clauses 15 to 31, wherein the high aspect ratio particles have an average length of at least 20 microns.

[0348] 37. The battery according to any one of clauses 15 to 36, wherein the high aspect ratio particles have an average thickness of less than 100 microns.

[0349] 38. The battery according to any one of clauses 15 to 36, wherein the high aspect ratio particles have an average thickness of less than 50 microns.

[0350] 39. The battery according to any one of clauses 15 to 36, wherein the high aspect ratio particles have an average thickness of less than 20 microns.

[0351] 40. The battery according to any one of clauses 15 to 36, wherein the high aspect ratio particles have an average thickness of less than 10 microns.

[0352] 41. The battery according to any one of clauses 15 to 36, wherein the high aspect ratio particles have an average thickness of less than 5 microns.

[0353] 42. The battery according to any one of clauses 15 to 36, wherein the high aspect ratio particles have an average thickness of less than 1 micron.

[0354] 43. The battery according to any one of clauses 15 to 36, wherein the high aspect ratio particles have an average thickness of less than 500 nm.

[0355] 44. The battery according to any one of clauses 1 to 43, wherein the polycrystalline microstructure of the solid ion conductive membrane is partially amorphous.

[0356] 45. A method for manufacturing a solid ion conductive membrane for a battery, comprising the steps of melting an ion conductive material and spraying it onto a substrate to form a solid ion conductive membrane having a polycrystalline microstructure, the polycrystalline microstructure defining grain boundaries between adjacent particles of the polycrystalline microstructure, and disposing the solid ion conductive membrane between an anode and a cathode, wherein most of the grain boundary regions of the polycrystalline microstructure are oriented substantially perpendicular to the direction of the electric field defined by the anode and the cathode.

[0357] 46. The method according to clause 45, wherein the solid ion conductive membrane is rapidly cooled from a molten phase so that the polycrystalline microstructure of the solid ion conductive membrane is partially amorphous.

[0358] Although various embodiments have been shown and described, those skilled in the art will conceive of modifications upon reading this specification. This application includes such modifications and is limited only by the claims.

Explanation of Reference Numerals

[0359] 2 Battery 4 Anode 6 Cathode 8 Electric field 10 Solid ion conductive membrane 12 Polycrystalline microstructure 14 Grain boundary 16 Particle 102 Removable substrate 104 Ion conductive membrane 106 Self-supporting solid ion conductive membrane 108 Ion conductive membrane supported on a porous support substrate 110 Porous support substrate 116 Solid ion conductive membrane / Ion conductive membrane 118 Flat surface 122 Ion conductive membrane 124 Preformed secondary battery electrode 126 Current collector 128 Negative current collector / Negative collector 130 Secondary battery negative electrode 132 Secondary battery positive electrode 134 Positive current collector / Positive collector 136 Conductive porous support substrate 138 Embedded secondary battery positive electrode 140 Embedded secondary battery negative electrode 142 Assembling a secondary battery 144 Porous positive electrode 146 Oxygen gas or atmosphere 148 Conductive porous support substrate 150 Bias 152 Metal anode layer 154 Flow-type secondary battery negative electrode 156 Flow-type secondary battery positive electrode 158 Anode liquid 160 Cathode liquid 162 Metal or metal alloy anode

Claims

1. An anode and a cathode that define an electric field therebetween; A battery including a solid ion conductive membrane between the anode and the cathode, The solid ion conductive membrane includes a polycrystalline microstructure that defines grain boundaries between adjacent particles of the polycrystalline microstructure, and most of the grain boundary regions between adjacent particles of the polycrystalline microstructure are oriented substantially perpendicular to the direction of the electric field defined by the anode and the cathode. Battery.

2. The battery according to claim 1, wherein most of the grain boundary regions between adjacent particles of the polycrystalline microstructure have an orthogonal direction within 35 degrees from the direction of the electric field defined by the anode and the cathode.

3. The battery according to claim 1, wherein most of the grain boundary regions between adjacent particles of the polycrystalline microstructure have an orthogonal direction within 25 degrees from the direction of the electric field defined by the anode and the cathode.

4. The battery according to claim 1, wherein most of the grain boundary regions between adjacent particles of the polycrystalline microstructure have an orthogonal direction within 15 degrees from the direction of the electric field defined by the anode and the cathode.

5. The battery according to claim 1, wherein the polycrystalline microstructure of the solid ion conductive membrane is partially amorphous.

6. The battery according to claim 1, wherein the anode interacts with ions through an intercalation mechanism, a non-intercalation mechanism, or a combination thereof.

7. The battery according to claim 1, wherein the cathode interacts with ions through an intercalation mechanism, a non-intercalation mechanism, or a combination thereof.

8. The battery according to claim 1, wherein the polycrystalline microstructure includes at least one of a garnet structure oxide material, a NASICON structure material, a perovskite type oxide material, an anti-perovskite type oxide material, a thiophosphate material, and an argyrodite structure sulfide.

9. A liquid system, a gel polymer system, an all-solid system, a semi-solid system, a hybrid system, or a combination thereof, the battery according to claim 1.

10. A primary battery or a secondary battery including the solid ion conductive membrane as an ion conductive separator, the battery according to claim 1.

11. A flow type secondary battery, wherein the solid ion conductive membrane is used as an ion conductive membrane, the battery according to claim 1.

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