CN118266096A

CN118266096A - Dry method for manufacturing electrode for solid-state energy storage device

Info

Publication number: CN118266096A
Application number: CN202280076726.6A
Authority: CN
Inventors: 钟琳达
Original assignee: Lirong Technology Co ltd
Current assignee: Lirong Technology Co ltd
Priority date: 2021-10-01
Filing date: 2022-09-22
Publication date: 2024-06-28

Abstract

A method of manufacturing an electrode block for a solid state battery, comprising: providing an electrode film having a current collector on a first side of the electrode film, coating a dry electrolyte powder layer on a second side of the electrode film opposite the first side, and pressing the dry electrolyte powder coated on the electrode film to make a solid electrolyte layer on the electrode film. A method of manufacturing an electrolyte membrane for a solid state battery, comprising: preparing a powder mixture comprising at least one fiberizable binder and at least one dry electrolyte powder, the at least one dry electrolyte powder comprising a majority by weight of the powder mixture, fiberizing at least one fiberizable binder in the powder mixture by subjecting the powder mixture to shear forces, and pressing the powder mixture into a self-supporting film.

Description

Dry method for manufacturing electrode for solid-state energy storage device

Cross Reference to Related Applications

The present application is a continuation-in-part application of U.S. patent application Ser. No.17/492,458, entitled "DRY ELECTRODEMANUFACTURE FOR SOLID STATE ENERGY STORAGEDEVICES," filed on 1 at 10/2021, the entire disclosure of which is incorporated herein by reference.

Statement: federally sponsored research/development

Is not suitable for

Background

Technical Field

The present disclosure relates generally to manufacturing energy storage devices such as lithium ion batteries, and more particularly to dry processes for manufacturing solid state batteries.

2. Related art

In view of the safety issues associated with the use of flammable liquid electrolytes in lithium ion batteries and other energy storage devices, and in order to take advantage of the high energy density that can be achieved by the use of lithium metal anodes, there is great interest in developing solid state batteries and other energy storage devices. In solid state batteries, conventional liquid electrolytes and separators are replaced with ceramic or solid polymer electrolytes. Unfortunately, electrolyte materials tend to be sensitive to N-methyl pyrrolidone (NMP) or other solvents used to form solid electrolyte membranes by wet coating, resulting in reduced cell performance. In addition, current solid state battery assembly techniques result in a significant boundary layer between the solid electrolyte and the electrodes, making it difficult for electrolyte ions to pass through, thereby increasing battery resistance.

Summary of The Invention

The present disclosure contemplates various methods and apparatus for overcoming the aforementioned drawbacks attendant with the related art. One aspect of the embodiments of the present disclosure is a method of manufacturing an electrode block for a solid-state battery. The method may comprise: providing an electrode film having a current collector on a first side of the electrode film; coating a layer of dry electrolyte powder on a second side of the electrode film opposite the first side; and pressing the dry electrolyte powder coated on the electrode film to make a solid electrolyte layer on the electrode film.

Providing an electrode film having a current collector may include: preparing a powder mixture comprising at least one electrode active material and at least one fiberizable binder, fiberizing at least one fiberizable binder in the powder mixture by subjecting the powder mixture to a shear force, pressing the powder mixture into a self-supporting film, and laminating the self-supporting film on a current collector. The powder mixture may also comprise at least one dry electrolyte powder.

Another aspect of an embodiment of the present disclosure is a method of manufacturing a solid-state battery. The method may comprise: providing a first electrode film having a first side and a second side opposite the first side; providing a second electrode film having a first side and a second side opposite the first side; coating a second side of the first electrode film with a layer of dry electrolyte powder; placing a second side of a second electrode film on the dry electrolyte powder layer; and pressing the first electrode film coated with the dry electrolyte powder layer thereon together with the second electrode film to produce a solid-state battery including the first electrode film, the second electrode film, and the solid electrolyte layer therebetween.

Providing one or both of the first electrode film and the second electrode film may include: preparing a powder mixture comprising at least one electrode active material and at least one fiberizable binder, fiberizing at least one fiberizable binder of the powder mixture by subjecting the powder mixture to shear forces, and pressing the powder mixture into a self-supporting film. The powder mixture may also comprise at least one dry electrolyte powder.

The method may comprise: the first electrode film is laminated on the first current collector such that the first current collector is located on the first side of the first electrode film, and the second electrode film is laminated on the second current collector such that the second current collector is located on the first side of the second electrode film. Lamination of the first electrode film and lamination of the second electrode film may be performed before coating or after pressing.

Another aspect of an embodiment of the present disclosure is a method of manufacturing an electrode film for a solid state battery. The method may comprise: preparing a powder mixture comprising at least one electrode active material, at least one fiberizable binder, and at least one dry electrolyte powder, the at least one dry electrolyte powder being 5 to 30 weight percent of the powder mixture; fiberizable binder of at least one of the powder mixtures by subjecting the powder mixture to shear forces; and pressing the powder mixture into a self-supporting film.

The method may comprise: a solvent is added to the powder mixture prior to fiberization to activate the at least one fiberizable binder.

The method may comprise: prior to fiberization, the powder mixture is heated to a temperature above 70 ℃ to activate the at least one fiberizable binder.

The powder mixture may comprise an additive solution comprising the polymer additive and the liquid carrier, the additive solution being less than 5% by weight of the powder mixture.

The powder mixture may comprise a conductive paste comprising a polymer additive, a liquid carrier, and a conductive material, the conductive paste being less than 5% by weight of the powder mixture.

Another aspect of an embodiment of the present disclosure is a self-supporting electrode film. The self-supporting electrode film may comprise at least one electrode active material, at least one fiberizable binder, and at least one dry electrolyte powder in an amount of 5 to 30 weight percent of the self-supporting electrode film.

Another aspect of the embodiments of the present disclosure is a method of manufacturing an electrolyte membrane for a solid state battery. The method may comprise: preparing a powder mixture comprising at least one fiberizable binder and at least one dry electrolyte powder, the at least one dry electrolyte powder comprising a majority (e.g., more than 80% by weight, such as from 80% to 97% by weight or from 80% to 99% by weight, preferably from 95% to 99% by weight) of the powder mixture; fiberizable binder of at least one of the powder mixtures by subjecting the powder mixture to shear forces; and pressing the powder mixture into a self-supporting film.

The method may comprise: the powder mixture is heated to a temperature above 70 ℃ to activate the at least one fiberizable binder prior to fiberization.

Another aspect of an embodiment of the present disclosure is a method of manufacturing an electrode block for a solid state battery. The method may comprise: the above method of manufacturing an electrolyte membrane is carried out, an electrode membrane (with or without a current collector) is provided, and a self-supporting electrolyte membrane is laminated on the electrode membrane.

Another aspect of an embodiment of the present disclosure is a self-supporting electrolyte membrane. The self-supporting electrolyte membrane may include at least one fiberizable binder and at least one dry electrolyte powder. The at least one dry electrolyte powder may account for a majority of the weight of the self-supporting electrolyte membrane. For example, the dry electrolyte powder may constitute 80 wt% or more of the self-supporting electrolyte membrane, such as 80 wt% to 97 wt% or 80 wt% to 99 wt%, preferably 95 wt%

To 99% by weight.

Another aspect of an embodiment of the present disclosure is a method of manufacturing an electrode block for a solid state battery. The method may include laminating the above-described self-supporting electrolyte membrane on an electrode membrane.

Brief description of the drawings

These and other features and advantages of the various embodiments disclosed herein will be better understood with reference to the following description and drawings in which like numbers refer to like parts throughout, and in which:

Fig. 1 shows an apparatus for manufacturing an electrode block of a solid-state battery;

FIG. 1A is a close-up view showing an electrode block;

fig. 2 shows an apparatus for manufacturing a solid-state battery;

Fig. 2A is a close-up view showing a solid-state battery;

FIG. 3 is an operational flow for manufacturing an electrode block;

Fig. 4 is an operation flow for manufacturing a solid-state battery;

Fig. 5 is an operational flow for manufacturing an electrode film, which is an exemplary sub-operational flow of step 310 in fig. 3, step 410 in fig. 4, or step 420 in fig. 4; and

Fig. 6 is an operation flow for manufacturing an electrolyte membrane.

Detailed Description

The present disclosure encompasses various embodiments of solid state batteries and electrodes, and methods of making and intermediates thereof. The detailed description set forth below in connection with the appended drawings is intended as a description of several embodiments presently contemplated and is not intended to represent the only forms in which the disclosed invention may be developed or utilized. The description sets forth the functions and features associated with the illustrated embodiments. However, it is to be understood that the same or equivalent functions may be accomplished by different embodiments that are also intended to be encompassed within the scope of the disclosure. It is further understood that the use of relational terms such as first and second, and the like are used solely to distinguish one entity from another entity without necessarily requiring or implying any actual such relationship or order between such entities.

Fig. 1 shows an apparatus 10 for manufacturing an electrode block 100 of a solid-state battery. Fig. 1A is a close-up view illustrating an electrode block 100, and the electrode block 100 may include an electrode film 110 and a solid electrolyte layer 120 laminated thereon. The electrode block 100 may be stacked and/or rolled with additional electrode blocks 100 to manufacture a multi-layer battery, such as a cylindrical or prismatic battery. As shown, the apparatus 10 may include one or more pieces of roll-to-roll processing equipment, and may include: for example, the first reel 12, the electrode film 110 may be initially wound into a roll on the first reel 12; a second reel 14 on which the finished electrode block 100 may be wound on the second reel 14; and one or more rollers 16 (e.g., drive and/or driven rollers) for transporting the electrode film 110 through the apparatus 10 from the first spool 12 toward the second spool 14. Unlike conventional solid state battery manufacturing equipment, the apparatus 10 of fig. 1 may include a dispersion coater 11 or other device for coating a layer of dry electrolyte powder 119 on one side 114 of the electrode film 110, and then the dry electrolyte powder 119 may be pressed by a roll press or calender 18 to make a solid electrolyte layer 120 on the electrode film 110. In this way, the solid electrolyte layer 120 can be formed in a dry process, avoiding the large amounts of NMP or other solvents used in conventional slurry-based processes, which might otherwise degrade the performance of the solid electrolyte. Further, since the solid electrolyte layer 120 is directly formed on the electrode film 110, rather than being stacked later on the electrode film 110, the boundary between the resulting electrode film 110 and the solid electrolyte layer 120 may be easier to pass electrolyte ions, thereby reducing the battery resistance.

The electrode film 110 may be a cathode film or an anode film, and may include an active material layer suitable for a cathode or an anode, respectively. To assemble a multi-layered battery, the electrode block 100 having the cathode electrode film 110 and the electrode block 100 having the anode electrode film 110 may be generally stacked in an alternating manner such that the solid electrolyte layer 120 separates each cathode from adjacent anodes and separates each anode from adjacent cathodes. For ease of illustration, the electrode film 110 is shown with only a single layer, i.e., an active material layer (which may be, for example, 50 μm to 350 μm), and the dry electrolyte powder 119 is coated on one side 114 thereof. However, a current collector (which may be, for example, 8 μm to 30 μm), such as an aluminum metal sheet in the case of the cathode electrode film 110, or a copper metal sheet in the case of the anode electrode film 110, may be laminated on the back side 112. Although not separately shown, the current collector may be present in the process shown in fig. 1 as well as in the finished electrode block 100 shown in fig. 1A, and may help provide stability during pressing of the dry electrolyte powder 119 into the solid electrolyte layer 120. It is also contemplated that the current collector may be laminated to the electrode block 100 after, rather than before, the process of fig. 1, although generally less practical.

Fig. 2 shows an apparatus 20 for manufacturing a solid-state battery 200. Fig. 2A is a close-up view showing the solid-state battery 200, and the solid-state battery 200 may include a first electrode film 210, a solid electrolyte layer 220, and a second electrode film 230 in the order shown in the drawing. The device 20 may be substantially identical to the device 10 of fig. 1 and may similarly include: a first reel 12 on which the first electrode film 210 may be initially wound into a roll; a second reel 14, on which a finished product (in this case, the solid-state battery 200) may be wound on the second reel 14; one or more rollers 16; a roll press or calender 18; and a dispersion applicator 11 or other device. The apparatus 20 may differ from the apparatus 10 in that a third spool 22 is added, and the second electrode film 230 is initially wound into a roll on the third spool 22. In the apparatus 20, the dispersion applicator 11 may apply a layer of dry electrolyte powder 119 on one side 214 of the first electrode film 210, after which one side 234 of the second electrode film 230 may be placed on the layer of dry electrolyte powder 119. Then, the first electrode film 210 having the layer of dry electrolyte powder 119 coated thereon may be pressed together with the second electrode film 230 using a roll press or calender 18 to make the solid-state battery 200 including the first electrode film 210, the second electrode film 230, and the solid electrolyte layer 220 therebetween.

The apparatus 10 shown in fig. 1 and 1A may manufacture a single electrode block 100 for use in a multi-layer battery, while the apparatus 20 of fig. 2 and 2A may manufacture a finished single layer solid state battery 200 having only one cathode and one anode. For example, such a single-layer solid-state battery 200 may be packaged as a pouch battery or a button battery. It should be noted that either one of the first electrode layer 210 and the second electrode layer 230 may be a cathode, and the other one may be an anode. That is, the dry electrolyte powder 119 may be coated on the cathode or anode, and then the dry electrolyte powder 119 may be sandwiched and pressed by the other to form the solid electrolyte layer 220.

Also, for ease of illustration, the electrode film 210 is shown with only a single layer, i.e., an active material layer, and the dry electrolyte powder 119 is coated on one side 214 thereof. Similarly, electrode film 230 is shown with only an active material layer and one side 234 is disposed on dry electrolyte powder 119. It should be understood that, as described above, a current collector, such as an aluminum metal sheet in the case of the cathode electrode films 210, 230 or a copper metal sheet in the case of the anode electrode films 210, 230, may be laminated on the back side 212, 232, and the current collector may be present in the process shown in fig. 2 as well as in the finished solid-state battery 200 shown in fig. 2A. However, since some single cells 200 may not have a current collector, such as button cells that utilize a housing metal for this purpose, it is contemplated that the process of fig. 2 may actually be performed without a current collector on the electrode films 210, 230. In this regard, the actual demand on the metal current collector layer by the process of fig. 2 may be lower, as the additional electrode film 230 may bring about some stability during pressing relative to the process of fig. 1. Thus, in the case where current collectors are to be employed in the finished solid-state battery 200, the electrode films 210, 230 may be laminated onto the respective current collectors either before coating with the dry electrolyte powder 119 (and thus before pressing) or after pressing.

Fig. 3 is an operational flow for manufacturing an electrode block, such as electrode block 100 shown in fig. 1A. The operational flow may begin with the provision of electrode film 110, as explained above, electrode film 110 may generally be laminated on a current collector (step 310). The electrode film 110 may be manufactured by any method including, for example, a slurry coating method, an extrusion method, and a dry method. Advantageously, a dry process may be used, such as any of the methods described in the inventors' own prior patents and patent applications, including U.S. Pat. No.10,069,131 entitled "Electrode for Energy Storage DEVICES AND Method of MAKING SAME", U.S. patent application publication No. 2020/0388022 entitled "Dry Electrode Manufacture by Temperature Activation Method", U.S. Pat. No.17/014,862 entitled "Dry Electrode Manufacture with Lubricated ACTIVE MATERIAL Mixture", and U.S. Pat. No.17/097,200 entitled "Dry Electrode Manufacture with Composite Binder", the disclosures of each of which are incorporated herein by reference in their entirety. In particular, as described in more detail below, the electrode film 110 may be manufactured by: preparing a powder mixture comprising at least one electrode active material (e.g., lithium metal oxide in the case of a cathode, or graphite in the case of an anode) and at least one fiberizable binder (e.g., polytetrafluoroethylene (PTFE), polyvinylpyrrolidone (PVP), polyvinylidene fluoride (PVDF), polyethylene oxide (PEO), or carboxymethyl cellulose (CMC)), fiberizing the binder by subjecting the powder mixture to a shear force, and pressing the powder mixture into a self-supporting film, which may then be laminated on a current collector.

Where electrode film 110 has been fabricated or otherwise provided (preferably including a current collector on first side 112 thereof), the operational flow of fig. 3 may continue with the coating of dry electrolyte powder 119 layer on second side 114 of electrode film 110 opposite first side 112 (step 320). As shown in fig. 1, the application of the dry electrolyte powder 119 to the electrode film 110 may be part of a roll-to-roll process as illustrated by the apparatus 10, wherein the dispersion applicator 11 applies the dry electrolyte powder 119 to the electrode film 110 as the electrode film 110 is transferred from the first reel 12 to the second reel 14 by one or more rollers 16. The operation flow may end by pressing the dry electrolyte powder 119 coated on the electrode film 110 to make the solid electrolyte layer 120 on the electrode film 110 (step 330). As shown in fig. 1, for example, a roll press or calender 18 may compress dry electrolyte powder 119 on electrode film 110 as the electrode film 110 passes from first reel 12 to second reel 14 through apparatus 10 to form solid electrolyte layer 120. The electrode block 100 (which may be used to fabricate a multi-layer battery as described above) may be fabricated as shown in fig. 1A (current collectors are omitted for ease of illustration).

Fig. 4 is an operation flow for manufacturing a solid-state battery such as the solid-state battery 200 shown in fig. 2A. The operational flow may begin with providing the first electrode film 210 and the second electrode film 230 (steps 410 and 420). Similar to electrode film 110 described above, electrode films 210, 230 may be fabricated by any method, including slurry coating, extrusion, and dry methods, including, for example, any of the methods described in the inventors' own prior patents and patent applications (e.g., those incorporated by reference above). In particular, as described in more detail below, each electrode film 210, 230 may be manufactured by: a powder mixture comprising at least one electrode active material (e.g., lithium metal oxide in the case of a cathode, or graphite in the case of an anode) and at least one fiberizable binder (e.g., PTFE, PVP, PVDF, PEO or CMC) is prepared, the binder is fibrillated by subjecting the powder mixture to shear forces, and the powder mixture is pressed into a self-supporting film, which can then be laminated on a current collector. In the case where the first electrode film 210 is made of a cathode active material, the second electrode film 230 may be made of an anode active material. In the case where the first electrode film 210 is made of an anode active material, the second electrode film 230 may be made of a cathode active material.

Where electrode films 210, 230 have been fabricated or otherwise provided (optionally including respective current collectors on first sides 212, 232 thereof), the operational flow of fig. 4 may continue with the coating of dry electrolyte powder 119 layer on second side 214 of first electrode film 310 opposite first side 212 (step 430). As shown in fig. 2, coating the dry electrolyte powder 119 on the electrode film 210 may be part of a roll-to-roll process as exemplified by the apparatus 20, wherein the dispersion coater 11 coats the dry electrolyte powder 119 on the first electrode film 210 (which may be a cathode or an anode) as the first electrode film 210 is transferred from the first reel 12 to the second reel 14 by the one or more rollers 16. After the dry electrolyte powder 119 is coated on the first electrode film 210, the operational flow may continue with the placement of the second electrode film 230 on the layer of dry electrolyte powder 119. Specifically, as shown in fig. 2, the second side 234 of the second electrode film 230 (i.e., the side opposite the first side 232 with the optional current collector) may be brought into proximity with the layer of dry electrolyte powder 119 such that the first electrode film 210 and the second electrode film 230 sandwich the layer of dry electrolyte powder 119 therebetween. The operational flow may continue to press (e.g., using a roll press or calender 18) the first electrode film 210 with the second electrode film 230 coated with the layer of dry electrolyte powder 119 thereon to produce a solid state battery 200 comprising the first electrode film 210, the second electrode film 230, and the solid electrolyte layer 220 therebetween (step 450). The solid-state battery 200 (which may be a single-layer battery as described above) may be manufactured as shown in fig. 2A.

The operational flow of fig. 4 may end with the lamination of the first electrode film 210 on the first current collector (e.g., aluminum sheet metal in the case of a cathode, or copper sheet metal in the case of an anode), and the lamination of the second electrode film 230 on the second current collector as well (steps 460, 470). These steps may follow step 450, as shown in fig. 4, wherein the finished solid state battery 200 is then laminated to the respective current collectors on both outer sides 212, 232. Or one or both of steps 460 and 470 may precede step 430 such that electrode films 210, 230 are laminated to the respective current collectors prior to coating with dry electrolyte powder 119 as described above. In this case, fig. 2A omits such an optional current collector for convenience of illustration. Or steps 460 and 470 may be omitted entirely, which may be useful in the case of manufacturing certain button cells without current collectors.

The dry electrolyte powder 119 used in the operational flow of either of fig. 3 and 4 (and either of the devices 10, 20) may be predominantly (e.g., 80 wt% to 100 wt%): ceramics, such as garnet-structured oxides, e.g. Lithium Lanthanum Zirconium Oxide (LLZO) and various dopants (e.g. Li _6.5La₃Zr₂O₁₂ or Li ₇La₃Zr₂O₁₂), lithium Lanthanum Zirconium Tantalum Oxide (LLZTO) (e.g. Li _6.4La₃Z_1.4Ta_0.6O₁₂), Lithium lanthanum zirconium niobium oxide (LLZNbO) (e.g., li _6.5La₃Zr_1.5Nb_0.5O₁₂), lithium lanthanum zirconium tungsten oxide (LLZWO) (e.g., li _6.3La₃Zr_1.65W_0.35O₁₂), perovskite structure oxides such as Lithium Lanthanum Titanate (LLTO) (e.g., li _0.5La_0.5TiO₃、Li_0.34La_0.56TiO₃ or Li _0.29La_0.57TiO₃) or Lithium Aluminum Titanium Phosphate (LATP) (e.g., li _1.4Al_0.4Ti_1.6(PO₄)₃), lithium super-ion conductors Li _2+2xZn_1-xGeO₄ (LISICON), such as Lithium Aluminum Titanium Phosphate (LATP) (e.g., li _1.3Al_0.3Ti_1.7(PO₄)₃), lithium aluminum germanium phosphate (LAG), or sodium super-ion conductors (i.e., NASICON type LAGP) (e.g., li _1.5Al_0.5Ge_1.5(PO₄)₃ or Li _1.5Al_0.5Ge_1.5P₃O₁₂), Or a phosphate, such as Lithium Titanium Phosphate (LTPO) (e.g., liTi ₂(PO₄)₃), lithium Germanium Phosphate (LGPO) (e.g., liGe ₂(PO₄)₃), lithium Phosphate (LPO) (e.g., gamma-Li ₃PO₄ or Li ₇P₃O₁₁), or lithium phosphorus oxynitride (LiPON). As a further example, the dry electrolyte powder 119 may be mainly (e.g., 80 to 100 wt%): polymers such as PEO, PEO-PTFE, PEO-LiTFSi/LLZO, PEO-LiClO ₄、PEO-LiClO₄/LLZO, poly (3, 4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT: PSS), polyphenylene oxide (PPO), polyethylene glycol (PEG), polyether polymers, polyester polymers, nitrile polymers, polysiloxane polymers, polyurethanes, poly (bis ((methoxyethoxy) ethoxy) phosphazene) (MEEP) or polyvinyl alcohol (PVA). as a further example, the dry electrolyte powder 119 may be mainly (e.g., 80 to 100 wt%): sulfides such as Lithium Sulfide (LS) (e.g., li ₂ S), lithium phosphorous sulfide (LSPS) (e.g., li ₂S-P₂S₅), lithium boron sulfide (LSBS) (e.g., li ₂S-B₂S₃), lithium phosphorous sulfide (LSPS), Vitreous lithium sulfide silicon sulfide (LSSiS) (e.g., li ₂S-SiS₂), lithium Germanium Sulfide (LGS) (e.g., li ₄GeS₄), lithium Phosphosulfide (LPS) (e.g., li ₃PS₄ such as 75Li ₂S-25P₂S₅, Or Li ₇P₃S₁₁ such as 70Li ₂S-30P₂S₅), lithium Silicon Phosphorus Tin Sulfide (LSPTS) (e.g., li _x(SiSn)P_yS_z), sulfur silver germanium ore type Li ₆PS₅ X (x=cl), Br) (e.g., LPSBr such as Li ₆PS₅ Br, LPSCl such as Li ₆PS₅ Cl, LPSClBr such as Li ₆PS₅Cl_0.5Br_0.5, or LSiPSCl such as Li _9.54Si_1.74P_1.44S_11.7Cl_0.3), Or thio LISICON (e.g., LGPS such as Li ₁₀GePS₁₂).

Fig. 5 is an operational flow for manufacturing electrode films (e.g., electrode films 110, 210, 230 described above). Accordingly, fig. 5 may be provided as an exemplary sub-operational flow of step 310 in fig. 3, step 410 in fig. 4, or step 420 in fig. 4. Specifically, fig. 5 provides an example of a dry process for manufacturing a cathode electrode film or anode electrode film 110, 210, 230, which in turn may be used to manufacture an electrode block 100 of a multi-layer battery according to the operational flow of fig. 3, or to manufacture a single-layer battery according to the operational flow of fig. 4. As described above, manufacturing the electrode films 110, 210, 230 by dry method may generally involve: preparing a powder mixture comprising at least one electrode active material and at least one fiberizable binder, fiberizing the binder by subjecting the powder mixture to a shearing force, and pressing the powder mixture into a self-supporting film, which can then be laminated on a current collector. More specifically, the operational flow of FIG. 5 may begin with the preparation of a powder mixture for the electrode films 110, 210, 230 (step 510). The electrode active material may constitute a majority of the powder mixture, for example, from 82 wt% to 99 wt% (e.g., 94 wt%) of the powder mixture. For the cathode, the electrode active material may be lithium metal oxide, such as Lithium Manganese Oxide (LMO), lithium nickel manganese cobalt oxide (NCM), lithium nickel cobalt aluminum oxide (NCA), lithium nickel manganese oxide (LMNO), or the like. In the case of the anode, the electrode active material may be graphite, silicon dioxide (SiO ₂), a mixture of both, or the like. The conductive material may also be added to the powder mixture in an amount of, for example, 0 to 10 wt% (e.g., 4 wt%) depending on the conductivity of the active material. Exemplary conductive materials may include: activated Carbon, conductive Carbon black, e.g. acetylene black, ketjen black or SUPER P (e.g. under the trade name SUPER by IMERYS GRAPHITE & Carbon in SwitzerlandCarbon black sold), carbon Nanotubes (CNT), graphite particles, conductive polymers, or combinations thereof.

In order to form the electrode films 110, 210, 230 by dry methods (and thus avoid the long drying times associated with conventional slurry coating and extrusion processes), the powder mixture may also include at least one fiberizable binder, such as Polytetrafluoroethylene (PTFE), polyvinylpyrrolidone (PVP), polyvinylidene fluoride (PVDF), polyethylene oxide (PEO), or carboxymethyl cellulose (CMC), including composite binders, as described in U.S. patent application No.17/097,200, entitled "Dry Electrode Manufacture with Composite Binder," incorporated by reference above. The fiberizable binder may be characterized by its soft, pliable consistency, particularly its ability to stretch, which becomes longer and finer when subjected to shear forces and assumes a fibrous state. Because of the use of one or more fiberizable binders (which may be further chemically or thermally activated to increase their flexibility, as described below), the powder mixture can be pressed into a self-supporting film without cracking and without the need for excessive use of solvents such as NMP.

As described in more detail in U.S. patent application No.17/014,862 entitled "Dry Electrode Manufacture with Lubricated ACTIVE MATERIAL mix," incorporated by reference above, a powder Mixture containing an electrode active material can be lubricated by mixing an additive solution or conductive paste containing a polymer prior to the addition of a binder. For example, the powder mixture may contain, in addition to the electrode active material (and in addition to the fiberizable binder to be added later), an additive solution comprising a polymer additive and a liquid carrier. The additive solution may be less than 5% by weight of the powder mixture so that the powder mixture may remain as a dry powder despite the addition of a relatively small amount of liquid. For example, the final powder mixture comprising electrode active material, any conductive material, a fiberizable binder and additive solution, and any electrolyte powder (see below) may have a total solids content of greater than 95% by weight. The polymer additive may be 0.5 to 10 wt% of the additive solution, and the polymer additive may be a polymeric compound, a surfactant, or a high viscosity liquid (e.g., mineral oil or wax), such as those known for use as carbon nanotube dispersants or as binders. See, for example, U.S. patent No.8,540,902, which provides exemplary dispersants and polymeric binders including polyethylene, polypropylene, polyamide, polyurethane, polyvinylchloride, polyvinylidene fluoride, thermoplastic polyester resins, polyvinylpyrrolidone, polystyrene sulfonate, polyphenylacetylene, poly (polymeta-phenylene vinylene), polypyrrole, poly (p-phenylene benzobisoxazole), natural polymers, aqueous solutions of amphiphilic materials, anionic aliphatic surfactants, sodium lauryl sulfate, cyclic lipopeptides biosurfactants, water soluble polymers, sodium polyvinyl alcohol lauryl sulfate, polyoxyethylene surfactants, polyvinylidene fluoride (PVDF), carboxymethyl cellulose (CMC), hydroxyethyl cellulose, polyacrylic acid, polyvinylchloride, and combinations thereof. Another exemplary polymer additive may be Styrene Butadiene Rubber (SBR). The liquid carrier used to prepare the additive solution may be aqueous or non-aqueous and may include, for example, one or more chemical agents selected from the group consisting of n-methylpyrrolidone, hydrocarbons, acetates, alcohols, glycols, alcohols, methanol, isopropanol, acetone, diethyl carbonate, and dimethyl carbonate.

Or the powder mixture may contain, in addition to the electrode active material (and in addition to the fiberizable binder to be added later), a conductive paste containing a polymer additive, a liquid carrier, and a conductive material. Similar to the additive solution described above, the conductive paste may be less than 5% by weight of the powder mixture. For example, the final powder mixture comprising electrode active material, a fiberizable binder and a conductive paste (no separate conductive material is typically used in the powder mixture), and any electrolyte powder (see below) may have a total solids content of greater than 95% by weight. The conductive paste may differ from the additive solution in that a conductive material is added, for example, in an amount of 1 to 20 wt%, preferably 2 to 15 wt%, more preferably 5 to 10 wt% of the conductive paste. For example, the conductive paste may be a CNT paste conventionally used to enhance the conductivity of wet mixtures used in coating processes, as exemplified by U.S. patent No.8,540,902. As an example, the conductive paste may be composed of 3.08% (by weight) PVP as a polymer additive, 91.67% NMP as a liquid carrier, and 6.25% carbon nanotubes as a conductive material.

In the finished electrode block 100 or the solid-state battery 200, the powder mixture may contain at least one dry electrolyte powder in order to enable the resulting electrode films 110, 210, 230 to exchange electrolyte ions with the solid electrolyte layers 120, 220 more easily, thereby reducing the battery resistance. The amount of dry electrolyte powder in the powder mixture may be, for example, 5 to 30 wt.%. The dry electrolyte powder contained in the powder mixture may be the same as or different from the dry electrolyte powder 119 used to form the solid electrolyte layers 120, 220, and may be, for example, any of the materials listed above in relation to the dry electrolyte powder 119.

Where a powder mixture comprising the electrode active material, any additive solution or conductive paste used to lubricate the electrode active material, the fiberizable binder, any additional conductive material, and advantageously at least one dry electrolyte powder has been prepared, the operational flow of fig. 5 may continue to activate the fiberizable binder by one or more activation methods. In the solvent activation step, a solvent may be added to the powder mixture to chemically activate the fiberizable binder such that the fiberizable binder softens and becomes capable of being stretched longer and finer without breaking and improving its adhesive strength (step 520). Unlike solvents such as NMP, which can be difficult to remove and require a lengthy drying process, the solvent added in the solvent activation step 520 can have a relatively low boiling point of less than 130 ℃ or less than 100 ℃ (i.e., less than the boiling point of water). Exemplary solvents may include hydrocarbons (e.g., hexane, benzene, toluene), acetates (e.g., methyl acetate, ethyl acetate), alcohols (e.g., propanol, methanol, ethanol, isopropanol, butanol), ethylene glycol, acetone, dimethyl carbonate (DMC), ethanamine (DEC), tetrachloroethylene, and the like. Unlike slurry coating processes and extrusion processes, where the solvent may be 60 to 80 weight percent of the resulting wet mixture, the solvent added in step 520 may be less than 20% of the resulting mixture. For example, the ratio of powder mixture to added solvent may be about 100:10 or 100:5 or 100:3.

Instead of or in addition to the solvent activation step 520, the operational flow may include a temperature activation step in which the powder mixture is heated to above 70 ℃, preferably above 100 ℃, to thermally activate the fiberizable binder (step 530). Similar to the solvent activation step 520, the temperature activation step 530 may cause the fiberizable binder to soften and become capable of being stretched longer and finer without breaking, thereby improving its adhesive strength. In the temperature activation step 530, the heating temperature of the powder mixture may be below the glass transition temperature of the binder (e.g., 114.85 ℃ for PTFE) because the binder may soften before reaching the glass transition temperature. Alternatively, the mixture may be heated to a temperature at or above the glass transition temperature of the binder. In the case where both the solvent activation step 520 and the temperature activation step 530 are used, these two steps may be performed in any order.

Where the fiberizable binder has been chemically and/or thermally activated by one or both of steps 520 and 530, the operational flow of fig. 5 may continue to fiberize the binder in the powder mixture by subjecting the powder mixture to shear forces (step 540). For example, the powder mixture may be stirred in a common kitchen stirrer or an industrial stirrer. The shear force required to deform (e.g., elongate) the fiberizable binder to provide a more viscous, pliable mixture can be achieved by: the powder mixture is stirred in a mixer at about 10,000rpm for 1 to 10 minutes (e.g., 5 minutes), either using a commercial dough mixer, or using an industrial scale mortar and pestle followed by the kneading process. Preferably, a high shear mixer, such as a high shear granulator (e.g., jet mill), may be used. If a solvent is added in the solvent activation step 520 to chemically activate the binder, the solvent may be injected into the powder mixture while the powder mixture is subjected to shear force in step 540 in some cases. Thus, steps 520 and 540 may be performed in a single step.

After the mixture is subjected to shear forces, the operational flow of fig. 5 may proceed to step 550, i.e., pressing the mixture to make a self-supporting film that will serve as the electrode film 110, 210, 230. This can be done using, for example, a roll press or calender, for example, at a temperature of 150℃and a nip condition of 20. Mu.m. The resulting self-supporting electrode film 110, 210, 230 may comprise at least one electrode active material, at least one fiberizable binder, and at least one dry electrolyte powder in an amount of 5% to 30% by weight of the self-supporting electrode film. In the case where the electrode films 110, 210, 230 are to be laminated on the current collector before the dry electrolyte powder 119 is coated to form the solid electrolyte layers 120, 220 (steps 320, 430), the operation flow of fig. 5 may end with lamination of the self-supporting electrode films 110, 210, 230 on the current collector (step 560). This may be particularly advantageous, for example, when manufacturing electrode block 100 for a multi-layer battery according to the operational flow of fig. 3 (i.e., when fig. 5 is a sub-operational flow of step 310), as explained above. Step 560 may be omitted if no current collector is used, or if a current collector is to be added later (as is the case with optional steps 460 and 470 of fig. 4).

As described above, the operation flow of fig. 5 may be advantageously used to manufacture the electrode films 110, 210, 230 shown in fig. 1 and 2, and then may be assembled into the electrode block 100 of the multi-layered solid-state battery according to the operation flow of fig. 3, or may be assembled into the single-layered solid-state battery 200 according to the operation flow of fig. 4. To this end, the powder mixture prepared in step 510 of fig. 5 may preferably include at least some of the dry electrolyte powder described above, thereby making the activated dry process described herein particularly suitable for the manufacture of solid state batteries. Using the combination of the operation flow of fig. 5 and the operation flow of fig. 3 or 4, the electrode block 100 or the solid-state battery 200 is manufactured through the full dry process throughout in this manner, the problems of long drying time and degradation of battery performance associated with the conventional wet process can be completely avoided, thereby enabling more practical and efficient manufacturing of the solid-state battery.

Fig. 6 is an operation flow of manufacturing an electrolyte membrane. The operational flow of fig. 6 may be part of an alternative method of dry-manufacturing a solid-state battery. Unlike the solid electrolyte layers 120, 220 formed of the dry electrolyte powder 119 directly coated on the electrode films 110, 210 described in relation to fig. 1 to 4, the solid electrolyte layer made in fig. 6 is in the form of a self-supporting film, which may then be laminated on the electrode films. In this respect, it is noted that the electrode membrane that is to receive the electrolyte membrane of fig. 6 can still be manufactured according to the dry method of fig. 5, resulting in another completely dry process for manufacturing a solid-state battery.

The operational flow of fig. 6 may be considered to be similar to the dry process used to fabricate the electrode film (e.g., the exemplary method of fig. 5), with the primary difference: the powder mixture contains components for manufacturing a solid electrolyte, not for manufacturing a cathode or an anode. Specifically, the operational flow of fig. 6 may begin with the preparation of a powder mixture for an electrolyte membrane (step 610). In this case, the dry electrolyte powder (instead of the electrode active material) may account for a majority by weight of the powder mixture, for example, may account for 80% by weight or more of the powder mixture, for example, 80% by weight to 97% by weight or 80% by weight to 99% by weight, preferably 95% by weight to 99% by weight. Examples of the dry electrolyte powder may include any of those listed above in relation to the dry electrode powder 119. In order to form the electrolyte membrane by dry methods (and thus avoid the long drying time problems associated with conventional wet methods), the powder mixture may also include at least one fiberizable binder, such as PTFE, PVP, PVDF, PEO or CMC, including a composite binder, as described in U.S. patent application No.17/097,200, entitled "Dry Electrode Manufacture with Composite Binder," which is incorporated by reference above. As explained above, the use of one or more fiberizable binders (which may be further chemically or thermally activated to increase their flexibility) may allow the powder mixture to be pressed into a self-supporting film without cracking and without the need for excessive use of solvents such as NMP.

As in the case of the powder mixture of the electrode films 110, 210, 230, it is conceivable that the powder mixture containing the dry electrolyte powder may be lubricated by mixing in the additive solution containing the polymer before the binder is added. For example, the powder mixture may contain, in addition to the dry electrolyte powder (and in addition to the fiberizable binder to be added later), an additive solution comprising a polymer additive and a liquid carrier. The additive solution may be less than 5% by weight of the powder mixture so that the powder mixture may remain as a dry powder despite the addition of a relatively small amount of liquid. For example, the final powder mixture comprising dry electrolyte powder, a fiberizable binder, and an additive solution may have a total solids content of greater than 95 weight percent. The polymer additives may be the same as described above. It is to be noted that the above-described electroconductive paste is not generally used in preparing the powder mixture for an electrolyte membrane, because electroconductivity is not generally required in a solid electrolyte.

Where a powder mixture comprising dry electrolyte powder, any additive solution used to lubricate the dry electrolyte powder, and a fiberizable binder has been prepared, the operational flow of fig. 6 may continue to activate the fiberizable binder by one or more activation methods. That is, the operational flow of fig. 6 may include the same solvent activation step 620 as the solvent activation step 520 of fig. 5 and/or the same temperature activation step 630 as the temperature activation step 530 of fig. 5. This can chemically and/or thermally activate the fiberizable binder to soften and become capable of being stretched longer and finer without breaking, thereby improving its adhesive strength. In the case where both the solvent activation step 620 and the temperature activation step 630 are used, the two steps may be performed in any order. The operational flow of fig. 6 may continue to fiberize the binder in the powder mixture by subjecting the powder mixture to shear forces (step 640), which may be the same as step 540 of fig. 5. If a solvent is added in the solvent activation step 620 to chemically activate the binder, in some cases the solvent may be injected into the powder mixture while the powder mixture is subjected to shear forces in step 640. Thus, steps 620 and 640 may be performed in a single step.

After the mixture is subjected to shear forces, the operational flow of fig. 6 may end at step 650 of pressing the mixture to make a self-supporting film, which may be performed, for example, in the same manner as step 550 of fig. 5. The resulting self-supporting electrolyte membrane may comprise at least one fiberizable binder and at least one dry electrolyte powder, which constitutes a majority of the weight of the self-supporting electrolyte membrane, for example in an amount of 80% by weight or more, such as 80% to 97% by weight or 80% to 99% by weight, preferably 95% to 99% by weight, of the self-supporting electrolyte membrane. Such a self-supporting electrolyte membrane may then be laminated on an electrode membrane (cathode or anode) to manufacture a solid state battery or an intermediate product thereof (e.g., an electrode block of a multilayer solid state battery). Similar to the operational flows of fig. 3 and 4, the operational flow of fig. 6 may be used in combination with the operational flow of fig. 5 to manufacture a solid-state electrode block or a solid-state battery by a completely dry process throughout. In this way, the problems of long drying time and reduced battery performance associated with the conventional wet method can also be completely avoided, thereby enabling more practical and efficient manufacture of solid-state batteries.

The above description is given by way of example and not by way of limitation. From the foregoing disclosure, those skilled in the art can devise variations that are within the scope and spirit of the invention disclosed herein. Furthermore, the various features of the embodiments disclosed herein may be used alone or in various combinations with one another and are not intended to be limited to the specific combinations described herein. Accordingly, the scope of the claims is not limited by the illustrated embodiments.

Claims

1. A method of manufacturing an electrode block for a solid state battery, the method comprising:

providing an electrode film having a current collector on a first side of the electrode film;

coating a layer of dry electrolyte powder on a second side of the electrode film opposite the first side; and

Pressing the dry electrolyte powder coated on the electrode film to form a solid electrolyte layer on the electrode film.

2. The method of claim 1, wherein the providing an electrode film with a current collector comprises:

preparing a powder mixture comprising at least one electrode active material and at least one fiberizable binder;

Fiberizing said at least one fiberizable binder in said powder mixture by subjecting said powder mixture to shear forces;

Pressing the powder mixture into a self-supporting film; and

The self-supporting film is laminated on the current collector.

3. The method of claim 2, wherein the powder mixture further comprises at least one dry electrolyte powder.

4. A method of manufacturing a solid state battery, the method comprising:

providing a first electrode film having a first side and a second side opposite the first side;

providing a second electrode film having a first side and a second side opposite the first side;

Coating a second side of the first electrode film with a layer of dry electrolyte powder;

placing a second side of the second electrode film on the dry electrolyte powder layer; and

The first electrode film having the dry electrolyte powder layer coated thereon is pressed together with the second electrode film to make a solid-state battery including the first electrode film, the second electrode film, and a solid electrolyte layer therebetween.

5. The method of claim 4, wherein one or both of the providing a first electrode film and the providing a second electrode film comprises:

Fiberizing said at least one fiberizable binder in said powder mixture by subjecting said powder mixture to shear forces; and

The powder mixture is pressed into a self-supporting film.

6. The method of claim 5, wherein the powder mixture further comprises at least one dry electrolyte powder.

7. The method of claim 4, further comprising:

Laminating the first electrode film on a first current collector such that the first current collector is located on a first side of the first electrode film; and

The second electrode film is laminated on a second current collector such that the second current collector is located on a first side of the second electrode film.

8. The method of claim 7, wherein the lamination of the first electrode film and the lamination of the second electrode film are performed prior to the coating.

9. The method according to claim 7, wherein lamination of the first electrode film and lamination of the second electrode film are performed after the pressing.

10. A method of manufacturing an electrode film for a solid-state battery, the method comprising:

Preparing a powder mixture comprising at least one electrode active material, at least one fiberizable binder, and at least one dry electrolyte powder, the at least one dry electrolyte powder being 5 to 30 weight percent of the powder mixture;

The powder mixture is pressed into a self-supporting film.

11. The method of claim 10, further comprising adding a solvent to the powder mixture to activate the at least one fiberizable binder prior to the fiberizing.

12. The method of claim 10, further comprising heating the powder mixture to a temperature above 70 ℃ to activate the at least one fiberizable binder prior to the fiberizing.

13. The method of claim 10, wherein the powder mixture further comprises an additive solution comprising a polymer additive and a liquid carrier, the additive solution being less than 5% by weight of the powder mixture.

14. The method of claim 10, wherein the powder mixture further comprises a conductive paste comprising a polymer additive, a liquid carrier, and a conductive material, the conductive paste being less than 5% by weight of the powder mixture.

15. A self-supporting electrode film comprising:

At least one electrode active material;

At least one fiberizable binder; and

At least one dry electrolyte powder in an amount of 5 to 30 wt% of the self-supporting electrode film.

16. A method of manufacturing an electrolyte membrane for a solid state battery, the method comprising:

Preparing a powder mixture comprising at least one fiberizable binder and at least one dry electrolyte powder, said at least one dry electrolyte powder comprising a majority of said powder mixture;

The powder mixture is pressed into a self-supporting electrolyte membrane.

17. The method of claim 16, wherein the amount of the at least one dry electrolyte powder is 80 to 97 weight percent of the powder mixture.

18. The method of claim 16, wherein the amount of the at least one dry electrolyte powder is 80% by weight or more of the powder mixture.

19. The method of claim 18, wherein the amount of the at least one dry electrolyte powder is 80 to 99 weight percent of the powder mixture.

20. The method of claim 19, wherein the amount of the at least one dry electrolyte powder is 95 to 99 weight percent of the powder mixture.

21. The method of claim 16, further comprising adding a solvent to the powder mixture to activate the at least one fiberizable binder prior to the fiberizing.

22. The method of claim 16, further comprising heating the powder mixture to a temperature above 70 ℃ to activate the at least one fiberizable binder prior to the fiberizing.

23. The method of claim 16, wherein the powder mixture further comprises an additive solution comprising a polymer additive and a liquid carrier, the additive solution being less than 5% by weight of the powder mixture.

24. A method of manufacturing an electrode block for a solid state battery, the method comprising:

the method of claim 16;

Providing an electrode film having a current collector on a first side of the electrode film; and

The self-supporting electrolyte membrane is laminated on a second side of the electrode membrane opposite the first side.

25. The method of claim 24, wherein the providing an electrode film with a current collector comprises:

Pressing the powder mixture into a self-supporting film; and

The self-supporting film is laminated on the current collector.

26. The method of claim 25, wherein the powder mixture further comprises at least one dry electrolyte powder.

27. A method of manufacturing an electrode block for a solid state battery, the method comprising:

the method of claim 16;

Providing an electrode film; and

The self-supporting electrolyte membrane is laminated on the electrode membrane.

28. The method of claim 27, wherein the providing an electrode film comprises:

The powder mixture is pressed into a self-supporting film.

29. The method of claim 28, wherein the powder mixture further comprises at least one dry electrolyte powder.

30. A self-supporting electrolyte membrane comprising:

At least one fiberizable binder; and

At least one dry electrolyte powder in an amount of 80 to 97 wt% of the self-supporting electrolyte membrane.

31. A self-supporting electrolyte membrane comprising:

At least one fiberizable binder; and

At least one dry electrolyte powder that comprises a majority of the weight of the self-supporting electrolyte membrane.

32. The self-supporting electrolyte membrane according to claim 31, wherein the amount of the at least one dry electrolyte powder is 80% by weight or more of the self-supporting electrolyte membrane.

33. The self-supporting electrolyte membrane according to claim 32, wherein the amount of the at least one dry electrolyte powder is 80 to 99 wt% of the self-supporting electrolyte membrane.

34. The self-supporting electrolyte membrane according to claim 33, wherein the amount of the at least one dry electrolyte powder is 95 to 99 wt% of the self-supporting electrolyte membrane.

35. A method of manufacturing an electrode block for a solid state battery, the method comprising:

Providing a self-supporting electrolyte membrane according to claim 31; and

The self-supporting electrolyte membrane is laminated on an electrode membrane.