Adhesive and paste compositions and solid-state batteries made from adhesive and paste compositions

Abstract

Various embodiments of adhesive and slurry compositions and methods of making solid-state batteries from the adhesive and slurry compositions are described herein. A solid-state electrochemical cell can include a first electrode substrate with a separator layer continuously interleaved in an alternating fashion with a second electrode substrate. A method of making a solid-state electrochemical cell can include applying a separator layer to a first electrode substrate, and continuously interleaving folded portions of the first electrode substrate with alternating folded portions of a second electrode substrate to form an electrochemical cell.

Description

[0001] Cross-reference to related applications

[0002] This application claims priority to U.S. Provisional Application No. 62 / 144,616, filed April 8, 2015, which is incorporated herein by reference.

[0003] Government rights

[0004] This invention was made with government support under Contract SOCOM Phase ISBIR, awarded by the U.S. Department of Defense with designation H92222-14-P-0030. The government holds certain rights to this invention. Technical Field

[0005] The various embodiments described herein relate to the fields of primary and secondary electrochemical cells, electrodes and electrode materials, binder and slurry compositions, and corresponding methods for manufacturing and using primary and secondary electrochemical cells, electrodes and electrode materials, binder and slurry compositions. Summary of the Invention

[0006] In one embodiment, a solid-state electrochemical cell is provided. The electrochemical cell includes a first electrode substrate with a separator layer and a second electrode substrate that is continuously interleaved with the first electrode substrate in an alternating manner to form the electrochemical cell.

[0007] In another embodiment, a method for manufacturing a solid-state electrochemical cell is provided. The method includes applying a separator layer to a first electrode substrate and continuously interleaving folded portions of the first electrode substrate with alternating folded portions of a second electrode substrate to form an electrochemical cell.

[0008] In another embodiment, a solid-state electrochemical cell is provided. The electrochemical cell includes a first electrode substrate coated with a first lithium polysulfide-based binder composition to form at least one of an anode, a cathode, and a separator; a second electrode substrate coated with a second lithium polysulfide-based binder composition; and a continuous, staggered stacking of the first and second electrodes to form an electrochemical cell having alternating first and second electrode layers.

[0009] In another embodiment, a method for manufacturing a solid-state electrochemical cell is provided. The method includes modifying a lithium polysulfide-based binder to provide at least one of an anode, a cathode, and a separator; applying the modified lithium polysulfide binder to a first electrode substrate; drying the modified lithium polysulfide binder; and forming the electrochemical cell by folding the first electrode substrate in a Z-shape and continuously interleaving the first electrode substrate with a Z-shaped folded second electrode substrate.

[0010] Other embodiments are disclosed herein, or will become apparent to those skilled in the art after reading and understanding the specification and drawings of this application. Attached Figure Description

[0011] This disclosure can be understood by referring to the brief description of the following figures in conjunction with the detailed description below. It should be noted that, for purposes of clarity, some elements in the figures may not be drawn to scale.

[0012] Figure 1 This is a flowchart of a process for manufacturing a polysulfide binder for sulfide ceramics that is useful for the construction of electrochemical cells, according to an embodiment.

[0013] Figure 2 This is a flowchart illustrating the process of using a polysulfide binder for sulfide ceramics in the construction of an electrochemical cell, according to an embodiment.

[0014] Figures 3A to 3D It is used according to the implementation method. Figure 1 and Figure 2 A set of cross-sectional views of the stacked layers of an exemplary electrochemical cell produced by a defined process.

[0015] Figure 4 This is an illustrative diagram illustrating the process of manufacturing an electrochemical cell using a double Z-shaped folded strip having the polysulfide adhesive described herein, according to an embodiment.

[0016] Figure 5 It is used according to the implementation method. Figure 1 , Figure 2 and Figure 4 A cross-sectional view of a portion of an exemplary electrochemical cell produced by a defined process.

[0017] Figure 6 It is used in accordance with the implementation method for manufacturing such as Figures 7A to 7D The flowchart shown illustrates the process of an electrochemical cell.

[0018] Figures 7A to 7D It is a set of views according to an embodiment, which details a series of steps for constructing one or more electrochemical cells and the resulting solid-state battery.

[0019] Figures 8A and 8B are examples of prior art shown here for comparison with the present invention. Detailed Implementation

[0020] In the following description, specific details are provided to provide a thorough understanding of the various embodiments of the invention. However, upon reading and understanding the specification, claims, and drawings of this invention, those skilled in the art will understand that some embodiments of the invention may be practiced without adhering to some of the specific details set forth herein. Furthermore, to avoid obscuring the invention, some known methods, processes, apparatuses, and systems applied in the various embodiments described herein are not disclosed in detail.

[0021] Advances in solid-state batteries have provided improvements in safety, packaging efficiency, and enabled new high-energy chemistry. Solid-state electrodes and electrolyte layers have traditionally been processed using thin-film deposition techniques (chemical vapor deposition (“CVD”), sputtering, thermal evaporation, etc.), powder granulation, and / or casting. Any of these methods can be combined with high-temperature sintering. Coating processes for lithium-ion electrodes are tunable and low-cost; however, one problem preventing the application of these existing technologies to solid-state electrochemical batteries is the compatibility of binders, slurries, and solvents used to process the desired layers. Promising lithium-sulfur-phosphorus (“Li-SP”) electrolyte materials for solid-state electrochemical batteries are incompatible with many conventional solvents, but conventional binders rely on such solvents, thus limiting the use of cost-effective coating processes in advanced Li-SP solid-state electrochemical batteries.

[0022] This invention includes lithium polysulfides (Li₂S₃) compatible with suitable solvents and Li-SP electrolyte materials. x S y This invention provides an adhesive composition that supports the integration of existing coating processes and current solid-state electrochemical battery materials and compositions. Most notably, the adhesive composition of this invention improves the adhesion of solid-state glass or ceramic particle layers used in electrochemical batteries. Exemplary adhesive compositions may be lithium polysulfides (e.g., Li₂) associated with one or more of the various solvents described herein. x S y *zTHF、Li2S 10 *2THF or Li2S 10*6THF, where THF is tetrahydrofuran. Adhesive compositions such as those disclosed herein allow a slurry formed from the adhesive to be coated and dried after a precursor of an additional electrolyte material or electrode material or each material of a solid-state electrochemical battery, resulting in a layer with excellent interlayer and intralayer adhesion. Intralayer adhesion includes particle-to-particle adhesion within any layer, and interlayer adhesion includes layer-to-layer adhesion or layer-to-substrate adhesion. The adhesive compositions of the present invention can be used in any or all layers of a solid-state lithium-ion electrochemical battery forming the cathode (positive electrode), anode (negative electrode), and / or separator. The adhesive and associated slurry compositions allow for the coating of solid-state electrochemical battery layers using low-cost and adaptable methods, such as conventional wet casting and coating methods.

[0023] While the content described herein applies to lithium-based electrochemical batteries, it is evident that it also applies to sodium polysulfide analogues (Na... x S y This provides potential cost advantages and compatibility with sodium battery materials. In other applications, polyselenide compositions can replace polysulfide compositions. Furthermore, the binders described herein can be used in non-lithium electrochemical batteries, sulfide film applications, solid-state electrochemical capacitors, and in liquid electrolyte batteries where the binder composition is insoluble in the electrolyte (e.g., ionic liquid).

[0024] Current solid-state electrode and separator coatings suffer from performance limitations due to the unsuitability or incompatibility of existing adhesives with the solvents in the coating slurry. A significant improvement of this invention is that the polysulfide adhesives described herein provide improved processability and compatibility for solid sulfide materials in batteries compared to conventional polymer adhesives such as polyvinylidene fluoride (“PVDF”), polytetrafluoroethylene (“PTFE”), and polyolefins commonly used in battery elements in liquid electrolytes and solid-state batteries. Examples of these applications can be found in PCT application WO2013179120A1 by Hasegawa et al., which is incorporated herein by reference. While polysulfides are considered for use as electrochemically active materials, such as cathodes in lithium polymer batteries (see, for example, U.S. Patent 6017651, incorporated herein by reference); these compounds are not described as adhesives in solid-state lithium batteries. Specifically, for example, U.S. Patent 6017651 also teaches the use of conventional adhesives for polysulfide active materials. Similarly, U.S. Patent 6,569,573, which is included herein by reference, mentions polysulfides in lithium-ion batteries but does not use them as adhesives. Furthermore, U.S. Patent 6,569,573 also teaches the use of conventional adhesives: "Examples of effective adhesives include, but are not limited to, materials such as polytetrafluoroethylene." Polyvinylidene fluoride (PVF2 or PVDF), ethylene propylene diene monomer (EPDM) rubber, polyethylene oxide (PEO), UV-curable acrylates, UV-curable methacrylates, and thermosetting divinyl ethers, etc. If an adhesive is present, its content is preferably in the range of 2% to 30% by weight. In another example, in U.S. Patent Application 2012 / 0135318, which is incorporated herein by reference, lithium polysulfide is used as an electrochemical cathode additive to compensate for irreversible capacity loss in the battery. Similarly, this application claims the use of conventional adhesives for the electrode coating.

[0025] The adhesive composition of the present invention is compatible with electrolyte-friendly solvents while achieving sufficient adhesion, conductivity, and electrochemical performance in solid-state batteries. Specifically, the adhesive composition is stable in proton-inert solvents, which are also suitable for sulfide electrolyte materials.

[0026] Figure 1 This is a flowchart of process 100 for manufacturing lithium polysulfide binders and / or slurries, wherein the lithium polysulfide binders and / or slurries are used in sulfide glasses and ceramics useful for the construction of secondary electrochemical cells. Details of the processing of lithium polysulfides and the suitability of their compositions for novel uses as binders and / or slurries are further described in detail below.

[0027] Process 100 begins with preparation step 110, where any preparatory activities such as precursor synthesis, purification, and substrate surface treatment may be performed. After all initial preparations, process 100 proceeds to step 120, where the sulfur compound and lithium compound may be combined with a suitable solvent. Exemplary sulfur compounds may include, for example, elemental sulfur powder. Exemplary lithium compounds may include, for example, metallic lithium (Li), lithium sulfide (Li₂S), and / or lithium nitride (Li₃N), typically in powder form. Exemplary solvents may include, for example, tetrahydrofuran (“THF”), dimethyl sulfoxide, γ-butyrolactone, dimethylacetamide, dimethylformamide, dimethyl sulfite, dimethyl sulfoxide, methyl acetate, methyl formate, nitromethane, propylene carbonate, chloropentafluorobenzene, methyl THF, thiophene, dimethyl carbonate, pyridine, and sulfolane, but are not limited thereto. Many solvents may be mixed with the lithium compound and sulfur compound. Additional materials such as co-solvents or polymers may also be added in this step. For example, a co-solvent may be added to the adhesive composition to control the drying properties of the resulting adhesive composition. The adhesive composition may also be modified or blended with a second polymer (such as polyvinyl chloride, polyaniline, polymethyl methacrylate (“PMMA”), nitrile rubber (“BR”), PVDF, or polystyrene) to increase or decrease the elastic modulus and processability of the coating formed from the slurry including the adhesive composition. Next, in step 130, the adhesive composition may be mixed at a predetermined time and temperature. For example, the adhesive composition may be mixed and heated at a temperature of 20 to 60 degrees Celsius for several hours to ensure sufficient homogenization. Furthermore, for steps 120 and 130, the solid lithium compound and the sulfur compound may be mixed together before the addition of the solvent. Subsequently, the composition of the solid compounds and the solvent may be stirred, stirred, or otherwise mixed until the solids dissolve. Regardless of the order of mixing, the solids in the mixture may be completely dissolved, or the lithium polysulfide adhesive composition may be prepared by partially dissolving the solid portion of the composition. Next, in step 140, the binder composition may be directly combined with ceramic or glass sulfide powder and other materials (such as electrode materials, non-sulfide electrolytes, and additional solvents) to form a slurry composition useful for the construction of solid-state electrochemical battery components. In step 150, these slurry compositions may be cast into a film using methods such as, but not limited to, blade coating, roller coating, screen printing, inkjet printing, aerosol printing, or slot die coating. In step 160, the slurry composition may be heated or allowed to air dry after coating. In the final step 170, the performance or encapsulation of the completed coated component and / or battery may be evaluated.

[0028] As an alternative to the various steps of process 100, solid lithium compounds and / or solid sulfur compounds may be introduced into a solution or solvent to form a lithium polysulfide binder composition via a potentiostatic electrochemical process. The solid lithium compounds and solid sulfur compounds may form one or more electrodes, or other materials such as carbon or platinum may be used as working electrodes in solution. Furthermore, the binder composition may be prepared and heated to remove any preparation solvents. In step 140, the dried binder composition may be added to a solvent and ceramic or glass powder to perform the same function as a wholly or partially dissolved binder composition. Other binder composition synthesis processes may be present.

[0029] More details about the formation of solid-state battery modules can be found through Figure 2 To understand the comments, Figure 2 This is a flowchart of process 200 using a polysulfide slurry composition obtained from the adhesive composition described in process 100, wherein the polysulfide slurry composition is used in the construction of secondary solid-state electrochemical cells for sulfide glass and ceramics. Process 200 begins with preparation step 210, where steps such as selecting any desired substrate and / or... Figure 1 Process 100 involves any preparatory activities related to the steps described in the description. After all initial preparations, process 200 proceeds to step 220, where a modified binder slurry composition for use in layers such as diaphragms, anodes, and / or cathodes can be prepared. It should be noted that by adding suitable materials to the binder composition to form the desired slurry composition, a suitably synthesized binder can be used to cast all sorts of desired layers. For example, for ionic and electronically conductive films, the slurry composition may include mixtures of electrochemically active ceramic or glass powders such as metal oxides, metal phosphates, elemental sulfur, or metal sulfides. The slurry composition may also include, but is not limited to, carbonaceous solids such as graphite and carbon black.

[0030] After the preparation of any desired slurry composition, during step 230, each slurry composition may be coated or cast onto a suitable substrate (as described below). Figures 3A to 3D (See related description). The slurry can be applied directly to the substrate or coated onto a carrier and then laminated to the substrate. Next, in step 240, the membrane can be heated and / or sintered to densify and / or solidify the membrane for the currently cast layer. Subsequently, process 200 can return to step 220 or step 230 to perform further slurry preparation and / or membrane casting multiple times as needed to produce the desired layer stack. For an exemplary membrane stack, see [link to example]. Figures 3A to 3D After all desired film layers have been formed, process 200 proceeds to step 250, where the stacked layers can be integrated into the solid-state battery. During the final step 260, the performance or encapsulation of the completed component and / or battery can be evaluated.

[0031] Figures 3A to 3D Is using Figure 1 and Figure 2 A set of cross-sectional views of a portion of a stacked layer of an exemplary electrochemical cell produced by a process defined herein. In each configuration of the stacked layer, a suitable substrate is provided ( Figure 3A Current collector 325, Figure 3B 340 aluminum layer Figure 3C Copper layer 355 and Figure 3D A lithium layer (365) is formed on the substrate. One or more layers may be formed on the substrate layer. Although not shown, layers may be formed on both sides of the substrate, as well as at any edges covering the substrate and / or previously deposited layers. It should also be understood that known techniques for additive or subtractive patterning of any single or multiple layers may also be used in conjunction with coating processes.

[0032] for Figure 3A The structure includes a slurry composition comprising a mixture of a binder composition and electrode particles, which can be coated onto a current collector 325, dried, and optionally densified to form a first electrode layer 320. Then, a diaphragm slurry composition comprising a mixture of a binder composition and electrolyte particles can be coated onto layer 320, dried, and again optionally densified to form a diaphragm / electrolyte layer 315. A second electrode / current collector 310 can be placed against the diaphragm / electrolyte layer 315. Figure 3A The structure forms a basically complete electrochemical cell.

[0033] for Figure 3B The structure includes a slurry composition comprising a mixture of a binder composition and cathode electrode particles, which can be coated onto an aluminum substrate 340, dried, and optionally densified to form a cathode 335. Then, a diaphragm slurry composition comprising a mixture of a binder composition and electrolyte particles can be coated onto layer 335, dried, and again optionally densified to form a diaphragm / electrolyte layer 330. Figure 3B The structure forms the cathode portion of the electrochemical cell.

[0034] for Figure 3C The structure includes a slurry composition comprising a mixture of a binder composition and anode electrode particles, which can be coated onto a copper substrate 355, dried, and optionally densified to form an anode 350. Then, a diaphragm slurry composition comprising a mixture of a binder composition and electrolyte particles can be coated onto layer 350, dried, and again optionally densified to form a diaphragm / electrolyte layer 345. Figure 3C The structure forms the anode portion of the electrochemical cell.

[0035] for Figure 3DThe structure, comprising a diaphragm slurry composition including a mixture of an adhesive composition and electrolyte particles, can be coated onto lithium foil 365, dried, and optionally densified again to form a diaphragm / electrolyte layer 360. Figure 3D The structure forms the anode portion of the electrochemical cell.

[0036] Figure 4 This is an illustrative diagram illustrating the process of fabricating a secondary electrochemical cell using the adhesive and slurry composition of the present invention, by alternatingly interlacing two separate, continuous, long, thin strips of material folded in a Z-shape onto one another. In one embodiment, as... Figure 5 Shown and with Figure 5 According to the relevant description, material strips 410 and 420 can be a double-sided coated electrode structure and a lithium foil, respectively. Furthermore, such as Figures 3A to 3D Shown and with Figures 3A to 3D According to the related description, material strips 410 and 420 can be single-striped. In another embodiment, the continuous staggered alternation includes alternating overlaps of material strips forming a Z-shaped fold of one electrode substrate with a second electrode substrate also folded into a Z-shape. For example, as... Figure 4 As shown, alternating material strips can be orthogonally oriented to each other.

[0037] By forming an electrochemical cell from continuous strips of material, the resulting cell is an interlaced electrochemical cell that is easy to form, integrate, and encapsulate, featuring integrated electrode connections. Although shown and described herein in the form of rectangular layers, the resulting electrochemical cell can be formed in a variety of different forms and shapes. Rectangles are the simplest shape for production; however, many shapes are possible, provided that these shapes can be formed from strips of material before or after continuous interlacing. For example, an L-shaped cell can be formed by constructing a rectangular cell and then removing the corners. Similarly, a cell with a central aperture can be formed by removing cylindrical portions from an interlaced rectangular cell structure.

[0038] Figure 5 It shows the use Figure 1 , Figure 2 Figure 3 and Figure 4 A portion of the electrochemical cells produced by the process specified in the middle are produced along the Figure 4A simplified cross-sectional view of the section projected by line AA. This electrochemical cell can be advantageously formed using the improved binder composition, slurry composition, coating process, and materials described above. For example, when material strip 410 is used as a cathode, it can be a double-coated electrode formed from a separator layer 411 and a cathode layer 413 coated or laminated on both surfaces of an aluminum substrate 415 serving as a current collector. Material strip 410 can be, for example, 315 cm long × 14.3 cm wide and 150 micrometers thick. In this example, material strip 420 can simply be a lithium metal foil having dimensions, for example, 485 cm long × 9.2 cm wide and 35 micrometers thick. Other material strip sizes may be used as appropriate for the cell to be constructed.

[0039] Figure 6 Is it used as Figure 4 , Figure 5 and Figures 7A to 7D A flowchart of a process 600 for fabricating a secondary electrochemical cell using double Z-shaped folded electrode strips is shown and described. Process 600 begins with a preparation step 610, where any necessary or optional setup and preparation steps may be performed. Setup and preparation operations may include, for example, cutting the anode and cathode strips (one of which may contain a separator layer) to suitable widths and lengths. Furthermore, the current collector may be exposed over a distance one cell length via area coating that can be used to create exposed areas, or by removing the electrode and separator material from suitable areas. Once all preparation operations are completed, process 600 proceeds to step 620, as described above herein, where the desired coating of the material strips (such as material strip 410) is performed. Next, in step 630, the material strips may be oriented such that the planes of the electrodes are parallel to each other and the long axes of the material strips are perpendicular to each other, and then Z-folds may be performed alternately. Figure 7A The results of two-layer Z-folding of a multilayer battery structure with two continuously interlaced material strips 410 and 420 are shown. It can be observed that the weaving of the double Z-folded electrodes allows longer, continuous electrodes to be woven together, minimizing the interconnect volume by electrically isolating the anode from the cathode through a separator encapsulated within the double-sided cathode. The folding is repeated, alternating each material strip until the desired electrochemical cell thickness or number of layers is achieved.

[0040] Following the folding operation, during step 640, the electrochemical cell can be pressed and / or heated to a temperature of 60 to 170 degrees Celsius for up to 300 minutes. After achieving the required number of Z-folds to form the desired cell, the structure of the cell 700 with two long, continuously interlaced electrodes can be as follows: Figure 7B The structure is shown. After pressing and / or heating the electrochemical cell, in step 650, the electrochemical cell can be encapsulated. Figure 7CAs shown, encapsulating one or more cells may include adding a metal sheet 710 that contacts the material layer 410 (e.g., lithium anode) and serves as a current bus. The metal sheet 710 may be made of copper, stainless steel, or other metals. For electrical interconnection of multiple cells, the last fold of the cathode material strip 410 may be designed, configured, or modified to expose the aluminum current collector 720 to allow surface-to-surface electrical contact for stacked cells. In the final step 660, process 600 ends and any further actions may be performed. Further actions may include encapsulating one or more individual cells in a parallel or series configuration and evaluating the performance of the electrochemical cells. Figure 7D As shown, multiple batteries can be stacked and encapsulated within a housing 730, which contains the batteries and applies stacking pressure (such as by means of a spring array 740 or other tools). Any and all steps of process 600 can be replicated, reordered, and / or modified to suit the specific requirements of the precise battery structure and / or materials being processed.

[0041] The resulting electrochemical cell maintains electrical contact along the functional surfaces and eliminates the need for tabs to interconnect the layers. This arrangement optimizes the effective volume of the electrochemical cell within the package and also reduces its weight and complexity because additional connectors and tabs between layers are not required. Electrical insulation between the two electrodes formed by the material strips is maintained by an insulating coating on one of the material strips. This coating (e.g., separator layer 411) prevents short circuits but has sufficient ionic conductivity to function as an electrolyte. Alternatively or optionally, to prevent short circuits at the edges, a separator layer (e.g., layer 411) may be coated onto the electrode layers such that the separator material extends beyond the edges of the electrodes, thereby covering the edges. Furthermore, after the electrode and separator coatings are applied, the electrode edges may be coated with an additional insulating material layer.

[0042] The described solid-state electrochemical cell configuration includes two interlaced Z-shaped folds, one for the cathode-separator composition and the other for lithium foil (or other anode material). This structure eliminates the need for butt tabs and interconnects, maximizing the energy density of the prismatic cell. The structure also allows for the application of uniform stacking pressure over most of the solid-state cell area. In an exemplary configuration, one surface of the resulting stack is lithium metal or a bare anode current collector, and the opposite surface is a bare cathode current collector. This configuration of the current collectors allows current to leave the cell stack while minimizing the required electrical connectors. Electrical contact is achieved through physical contact with the top and bottom of the stack, one providing a positive connection and the other a negative connection. Electrical connections can also be formed at the edges of the folds of the two electrodes, which reduces the resistance of the cell in high-power applications.

[0043] As described herein, the present invention also allows for the fabrication of bipolar batteries from solid-state batteries connected in series. Conductive sheets compatible with both electrode layers (e.g., nickel, if necessary to avoid side reactions) are placed between each battery, and the battery voltage that can be transferred is a multiple of the voltage of a single battery. Such configurability is difficult, or even impossible, in liquid electrolyte batteries because the free-flowing liquid would cause short circuits (due to the ionic conductive paths it creates between batteries). This is a significant advantage of solid-state electrochemical batteries constructed using the technology of the present invention.

[0044] Figures 8A and 8B are examples of prior art for comparison with the present invention. Various implementations of the Z-folding process for forming elements of an electrochemical cell exist in the prior art. In a common implementation for producing stacked electrochemical cells, separate continuous strips of separator layers are folded, and anode and cathode sheets are alternately placed between each separator layer. More specifically, details of past Z-folding processes are provided by reference in U.S. Patent Application Publication 2014 / 0272537A1 by Kretschmar et al., published herein. In the electrochemical cell described in this application by some embodiments represented by Figure 8A, an electrode 830 and separator 820 are staggered in a double Z-fold configuration, and a second electrode 810 is applied as a separate sheet between the layers of separator 820. This structure differs significantly from the present invention, requiring greater complexity and more manufacturing steps, at least due to the inserted electrode sheets and separate separator sheets. Furthermore, the prior art structure requires electrical contacts on each of these inserted electrode sheets and a method for connecting these contacts to an electrical bus. When the technology of this invention is used, these additional independent layers and contacts are directly integrated.

[0045] In another example in the prior art (represented by Figure 8B), Japanese patent application JP H0917441A by Kitaoka Kazuhiro, incorporated herein by reference, describes a configuration comprising two electrode layers interwoven in a double Z-shaped fold (one of which is coated with a separator material). Costly, this design relies on comb-shaped current collectors with a conductor inserted into each fold to maintain layer alignment and prevent slippage. The described battery is also not entirely solid-state, as it utilizes a liquid electrolyte. These current collectors increase manufacturing complexity and also add undesirable weight and volume to the battery. In contrast, the solid-state design of the present invention allows for lamination of the layers while the stack is being produced or when the stack folding is complete. This can be accomplished by individual mechanical pressure or by thermal assistance. In the electrochemical battery of the present invention, a polymer electrolyte with adhesive properties can also be used for lamination of the layers.

[0046] The features described above and the claims can be combined in various ways without departing from the scope of this application. The following examples illustrate some possible, non-limiting combinations:

[0047] (A1) A solid-state electrochemical cell may include a first electrode substrate having a separator layer and a second electrode substrate that is continuously interleaved with the first electrode substrate in an alternating manner to form an electrochemical cell.

[0048] (A2) An electrochemical cell as represented in (A1) may further include an anode layer coated on one of a first electrode substrate and a second electrode substrate.

[0049] (A3) An electrochemical cell represented as (A1) or (A2) may further include a cathode layer coated on one of a first electrode substrate and a second electrode substrate.

[0050] (A4) In the electrochemical cells represented as (A1) to (A3), the first electrode substrate and the second electrode substrate may be selected from the group consisting of lithium metal, copper, nickel, stainless steel and aluminum.

[0051] (A5) In the electrochemical cells represented as (A1) to (A4), the membrane layer may further include a lithium polysulfide-based binder composition.

[0052] (A6) In an electrochemical cell as shown in (A1) to (A5), the current bus may be electrically connected to at least one of the first electrode substrate and the second electrode substrate.

[0053] (A7) In the electrochemical cells represented as (A1) to (A6), a casing may be provided to house the electrochemical cell and apply pressure to the electrochemical cell.

[0054] (A8) In an electrochemical cell as shown in (A1) to (A7), the alternation may include overlapping alternating folds of a first electrode substrate folded in a z-shape and a second electrode substrate folded in a z-shape.

[0055] (B1) A method of manufacturing a solid-state electrochemical cell may include applying a separator layer to a first electrode substrate and continuously interleaving folded portions of the first electrode substrate with alternating folded portions of a second electrode substrate to form an electrochemical cell.

[0056] (B2) The method represented by (B1) may include coating an anode layer on one of the first electrode substrate and the second electrode substrate.

[0057] (B3) The method represented by (B1) or (B2) may include coating a cathode layer on one of the first electrode substrate and the second electrode substrate.

[0058] (B4) The method represented by (B1) to (B3) may include patterning the diaphragm layer to expose at least a portion of the first electrode substrate.

[0059] (B5) The methods represented by (B1) to (B4) may include heating the electrochemical cell to a temperature range of 60 to 170 degrees.

[0060] (B6) In the methods shown in (B1) to (B5), the continuously alternating steps may include repeatedly folding the first electrode substrate and the second electrode substrate to overlap each other orthogonally to form a z-shaped stack of alternating layers.

[0061] (C1) A solid-state electrochemical cell may include a first electrode substrate coated with a first lithium polysulfide-based binder composition to form at least one of an anode, a cathode, and a separator, a second electrode substrate coated with a second lithium polysulfide-based binder composition, and a continuous staggered stack of the first electrode and the second electrode to form an electrochemical cell having alternating first electrode layers and second electrode layers.

[0062] (C2) In the electrochemical cell represented as (C1), each of the first lithium polysulfide binder composition and the second lithium polysulfide binder composition may further include a lithium compound, a sulfur compound, and a solvent.

[0063] (C3) In an electrochemical cell represented as (C1) or (C2), the lithium compound may be selected from the group consisting of lithium metal, lithium sulfide and lithium nitride.

[0064] (C4) In the electrochemical cells represented as (C1) to (C3), the solvent may be selected from the group consisting of tetrahydrofuran, dimethyl sulfoxide, γ-butyrolactone, dimethylacetamide, dimethylformamide, dimethyl sulfite, dimethyl sulfoxide, methyl acetate, methyl formate, nitromethane, propylene carbonate, chloropentafluorobenzene, methyl THF, thiophene, dimethyl carbonate, pyridine, and sulfolane.

[0065] (C5) Electrochemical cells represented as (C1) to (C3) may include at least one of a cosolvent and a polymer.

[0066] (D1) A method for manufacturing a solid-state electrochemical cell may include modifying a lithium polysulfide-based binder to provide at least one of an anode, a cathode, and a separator, applying the modified lithium polysulfide binder to a first electrode substrate, drying the modified lithium polysulfide binder, and forming an electrochemical cell by folding the first electrode substrate in a Z-shape and continuously interleaving the first electrode substrate with a second electrode substrate folded in a Z-shape.

[0067] Therefore, it should be noted that the content contained in the above description or shown in the accompanying drawings should be interpreted as illustrative and not limiting. The embodiments described above should be considered as examples of the invention and not as limiting the scope of the invention. In addition to the above-described embodiments of the invention, the detailed description and commentary on the drawings will show other embodiments of such an invention. Therefore, many combinations, arrangements, variations, and modifications of the above-described embodiments of the invention not expressly set forth herein will still fall within the scope of such an invention. The claims are intended to cover all general and specific features described herein, as well as all statements of the scope of the method and system, which are linguistically considered to fall within the scope of the claims.

Claims

1. A method for manufacturing a component in a solid-state electrochemical cell, said component being an anode, a cathode, or a separator / electrolyte layer, said method comprising: Forming a lithium polysulfide adhesive composition includes: mixing a solid sulfur compound and a solid lithium compound to obtain a mixture; dissolving the solid in the mixture using a solvent to obtain the lithium polysulfide adhesive composition, wherein the lithium compound includes at least one of lithium metal, lithium sulfide, and lithium nitride; wherein the solvent includes tetrahydrofuran, dimethyl sulfoxide, γ-butyrolactone, dimethylacetamide, dimethylformamide, dimethyl sulfite, methyl acetate, methyl formate, nitromethane, propylene carbonate, chloropentafluorobenzene, methyltetrahydrofuran, thiophene, dimethyl carbonate, pyridine, and sulfolane, or mixtures thereof. Adding anode particles, cathode particles, or electrolyte particles to the lithium polysulfide binder composition to prepare an anode slurry composition, a cathode slurry composition, or a diaphragm slurry composition; The anode slurry composition, the cathode slurry composition, or the diaphragm slurry composition are cast into a film on a substrate; and The membrane is heated and / or sintered.

2. The method according to claim 1, wherein, The lithium polysulfide adhesive composition also includes one or more of a cosolvent and a polymer.

3. The method according to claim 2, wherein, The polymers include polyvinyl chloride, polyaniline, polymethyl methacrylate, nitrile rubber, polyvinylidene fluoride, or polystyrene.

4. The method according to claim 1, wherein the anode slurry composition, the cathode slurry composition, or the diaphragm slurry composition further comprises: Ceramic or glass powders containing metal oxides, metal phosphates, or electrochemically active metal sulfides; non-sulfide electrolytes; carbon-containing solids containing graphite or carbon black; Or a mixture thereof.

5. The method of claim 1, wherein the lithium polysulfide binder composition comprises Li₂S 10 2-Tetrahydrofuran or Li2S 10 6. Tetrahydrofuran.

6. The anode, cathode, or separator / electrolyte layer in a solid-state electrochemical cell obtained by the method according to any one of claims 1-5.

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