Cylindrical Anode-Free Solid-State Battery with a Suspected Solid Lithium Gel Layer

Abstract

Various configurations are presented for making a cylindrical dendrite-preventing anode-free solid-state battery. An anti-dendrite layer may be laminated between an anode current collector layer and a cathode layer. A laminate stack may be made including a dry separator layer, a cathode layer laminated with a cathode current collector layer, and an anti-dendrite layer laminated with an anode current collector layer. The laminate stack may be rolled into a cylindrical jelly roll shape. The rolled laminate stack may be inserted into a pouch. A liquid electrolyte mixture may be added into the pouch. The liquid electrolyte mixture may permeate the dry separator layer. Heat may be applied to the pouch to gel the liquid electrolyte mixture. The rolled laminate stack may then be removed from the pouch and inserted into a cylindrical battery cell canister.

Description

Background Art

[0001]

[0001] During the charging of a lithium-ion battery, lithium ions move from the cathode of the battery to the anode of the battery through a separator located between the cathode and the anode. Through a process called intercalation, the lithium ions come to be inserted into the material functioning as the anode. Also, during this charging process, lithium ions can be plated on the surface of the anode facing the separator. The nucleation energy associated with the anode can encourage the lithium ions to be plated on other lithium already plated on the anode (rather than being plated into a film that is substantially uniform across the surface of the anode). These accumulations of lithium can form dendrites. A dendrite can be a protrusion of lithium metal that extends away from the surface of the anode toward the separator. Over time (e.g., through multiple charge and discharge cycles), the dendrite can grow to a length such that the dendrite penetrates the separator and makes a direct electrical connection between the cathode and the anode (i.e., a short circuit). Such an electrical connection can result in the destruction of the battery and, in some cases, serious unintended consequences such as overheating and fire.

Summary of the Invention

Means for Solving the Problems

[0002]

[0002] Described are various embodiments related to a method of making a cylindrical dendrite - preventing anode - free solid - state battery. In some embodiments, a method of making a cylindrical dendrite - preventing anode - free solid - state battery is described. The method may include attaching a cathode layer to a cathode current collector layer. The method may include laminating a dendrite - preventing layer between the anode current collector layer and the cathode layer. The method may include creating a laminated stack including a dry separator layer, a cathode layer laminated with the cathode current collector layer, and a dendrite - preventing layer laminated with the anode current collector layer. The dry separator layer may be positioned between the cathode layer and the dendrite - preventing layer. The method may include winding the laminated stack into a cylindrical jelly - roll shape. The method may include inserting the wound laminated stack into a pouch. The method may include permeating a liquid electrolyte mixture into the pouch. The liquid electrolyte mixture may permeate the dry separator layer, and the liquid electrolyte mixture may include a salt and a solvent. The method may include applying pressure to the pouch after permeating the liquid electrolyte mixture. The method may include applying heat to the pouch while pressure is being applied to the pouch. The heat may at least partially gel the liquid electrolyte mixture permeating the dry separator layer. The method may include removing the wound laminated stack from the pouch after applying pressure and heat. The method may include inserting the wound laminated stack removed from the pouch into a cylindrical battery cell canister.

[0003]

[0003] Embodiments of such a method may include one or more of the following features. The liquid electrolyte mixture may further include a polymer additive and a crosslinking additive that can gel the liquid electrolyte mixture when heat is applied. A first adhesive layer may be attached to the dry separator layer such that the first adhesive layer can be positioned between the dry separator layer and the cathode layer. A second adhesive layer may be attached to the dry separator layer such that the second adhesive layer can be positioned between the dry separator layer and the dendrite prevention layer. The method may further include inserting the pouch into a cylindrical press module, the cylindrical press module including a compressible material wrapped around the curved edge of the pouch. The method may further include inserting a temperature probe for monitoring the temperature between the pouch and the cylindrical press module. The heat may be applied through the compressible material wrapped around the curved edge of the pouch. The heat applied may be between 150°C and 250°C. The presence of the dendrite prevention layer can reduce the nucleation barrier in the energy for lithium ions to deposit on the anode current collector layer. The thickness of the dendrite prevention layer may be between 0.05 micrometers and 10 micrometers. The dendrite prevention layer may include one or more materials selected from the group consisting of carbon black, acetylene black, ketjen black, silver, zinc, gold, bismuth, tin, polyvinylidene fluoride (PVDF), polyimide (PI), polyacrylic acid (PAA), and carboxymethylcellulose styrene butadiene rubber (CMC-SBR). The method may further include depositing an interfacial bonding layer on the anode current collector layer.

[0004]

[0004] In some embodiments, a cylindrical dendrite-preventing anode-free solid-state battery is described. The battery may include a cathode layer. The battery may include a cathode current collector layer attached to the cathode layer. The battery may include an anode current collector layer. The battery may include a dendrite-preventing layer positioned between the anode current collector layer and the cathode layer. The battery may include a lithium gel separator layer positioned between the cathode layer and the dendrite-preventing layer. The battery may include a canister into which the cathode layer, the cathode current collector layer, the anode current collector layer, the dendrite-preventing layer, and the lithium gel separator layer may be inserted.

[0005]

[0005] Embodiments of such a device may include one or more of the following features. The lithium gel separator layer may include a skeletal material, a lithium salt, a solvent, and two or more additives. The two or more additives may include a polymer additive and a cross-linking additive. The polymer additive and the cross-linking additive may be capable of forming a gel in the solvent and the lithium salt when exposed to heat. The device may further include an interfacial bonding layer deposited on the anode current collector layer. The first adhesion amount between the interfacial bonding layer and the anode current collector layer may be greater than the second adhesion amount between the interfacial layer and the dendrite-preventing layer. The dendrite-preventing layer may include one or more materials selected from the group consisting of carbon black, acetylene black, ketjen black, silver, zinc, gold, bismuth, tin, polyvinylidene fluoride (PVDF), polyimide (PI), polyacrylic acid (PAA), and carboxymethyl cellulose styrene butadiene rubber (CMC-SBR). The thickness of the dendrite-preventing layer may be from 0.05 micrometers to 10 micrometers. The presence of the dendrite-preventing layer may be able to reduce the nucleation barrier in the energy for lithium ions to deposit on the anode current collector layer.

Brief Description of the Drawings

[0006]

Figure 1

[0006] Shows an embodiment of a layer stack of an anode-free solid-state battery having a lithium gel separator layer and a dendrite prevention layer.

Figure 2

[0007] Shows another embodiment of a layer stack of an anode-free solid-state battery having a plurality of lithium gel separator layers and a plurality of dendrite prevention layers.

Figure 3A

[0008] Shows an embodiment of a lithium gel separator layer formed using heat.

Figure 3B

[0009] Shows an embodiment of a method for making a lithium gel separator layer.

Figure 4

[0010] Shows an embodiment of a method for manufacturing a pouch-type battery cell including an anode-free solid-state battery having a lithium gel separator layer and a dendrite prevention layer.

Figure 5

[0011] Shows an embodiment of a cylindrical battery press system.

Figure 6A

[0012] Shows an embodiment of a method for making a cylindrical dendrite-preventing anode-free solid-state battery.

Figure 6B

[0012] Shows an embodiment of a method for making a cylindrical dendrite-preventing anode-free solid-state battery.

Figure 7

[0013] Shows an embodiment of a layer stack of an anode-free solid-state battery having a lithium gel separator layer, a dendrite prevention layer, and an interfacial bonding layer.

Figure 8

[0014] Shows an embodiment of a layer stack of an anode-free solid-state battery showing the relative adhesion amounts between various layers.

Figure 9

[0015] Shows an embodiment of a layer stack of a charging anode-free solid-state battery in which lithium is deposited on the interfacial bonding layer.

Figure 10

[0016] Shows an embodiment of a method for manufacturing a pouch-type battery cell including a solid-state battery having a lithium gel separator layer, a dendrite prevention layer, and an interfacial bonding layer.

Mode for Carrying Out the Invention

[0007]

[0017] By introducing a dendrite prevention layer combined with a lithium gel separator layer, the growth of dendrites can be suppressed without significantly increasing the thickness of the battery cell. The dendrite prevention layer may be directly coated on the anode current collector of the anode-free solid-state battery (SSB). In an anode-free SSB, the anode current collector, which may be a copper foil, can effectively function as both the anode and the anode current collector. The dendrite prevention layer can reduce the nucleation energy required for lithium ions to deposit as lithium metal on the surface of the anode current collector in contact with the dendrite prevention layer. Instead of lithium ions having a tendency to deposit on top of the lithium metal already plated on the surface of the anode current collector (thus creating accumulations that can cause dendrites), lithium may tend to deposit in a substantially uniform film across the surface of the anode current collector.

[0008]

[0018] The dendrite prevention layer may be in direct contact with the lithium gel separator layer. The lithium gel separator layer can perform multiple functions. First, the lithium gel separator layer can function as a solid electrolyte that promotes the movement of lithium ions between the cathode and the anode. The lithium gel separator layer can also act as a separator to prevent direct electrical connection between the cathode and the anode. The lithium gel separator layer may further have characteristics that further suppress the growth of dendrites.

[0009]

[0019] In connection with the drawings, further details regarding such embodiments and further embodiments are provided. FIG. 1 shows an embodiment of a layer stack 100 of an anode-free solid-state battery having a lithium gel separator layer and a dendrite prevention layer. The layer stack 100 may include a cathode current collector 110, a cathode 120, a lithium gel separator layer 130, a dendrite prevention layer 140, and an anode current collector 150.

[0010]

[0020] The cathode current collector 110 may be a conductive film laminated with the cathode 120. The cathode current collector 110 may be, for example, an aluminum foil. Other forms of conductor foil are also possible. The cathode 120 may be, for example, NCA (nickel-cobalt-aluminum oxide) or NCM (nickel-manganese-cobalt).

[0011]

[0021] The cathode 120 may have a first surface in direct contact with the cathode current collector 110, and the opposite surface of the cathode 120 may be in direct contact with the lithium gel separator layer 130. The lithium gel separator layer 130 may function as a (gel-like) solid electrolyte for promoting the movement of lithium ions between the cathode 120 and the anode current collector 150. The lithium gel separator layer 130 also serves as a separator for preventing direct electrical connection between the cathode 120 and the anode current collector 150. The lithium gel separator layer 130 may have features for further suppressing the growth of dendrites. The lithium gel separator layer 130 may initially be at least partially liquid. After assembly, a process for converting the liquid to a gel state may be applied. Such a process may include pressure, heating, or both. In connection with FIG. 3A, further details regarding the lithium gel separator layer 130 are provided.

[0012]

[0022] The lithium gel separator layer 130 may have a first surface in direct contact with the cathode 120. The second surface of the lithium gel separator layer 130 opposite the first surface may be in direct contact with the dendrite prevention layer 140. The dendrite prevention layer 140 may have several key features. First, the dendrite prevention layer 140 may reduce the nucleation energy required for lithium ions to plate as lithium metal on the surface of the anode current collector 150 in direct contact with the dendrite prevention layer 140. By reducing the nucleation energy, lithium ions are more likely to deposit directly on the anode current collector 150 rather than "accumulating" or depositing on the lithium metal already plated on the anode current collector 150.

[0013]

[0023] The second key feature of the dendrite prevention layer 140 is that the amount of adhesion between the dendrite prevention layer 140 and the anode current collector 150 is less than the amount of adhesion between the dendrite prevention layer 140 and the lithium gel separator layer 130. The low adhesion between the surfaces of the dendrite prevention layer 140 and the anode current collector 150 promotes lithium plating between the dendrite prevention layer 140 and the anode current collector 150, as opposed to between the lithium gel separator layer 130 and the dendrite prevention layer 140.

[0014]

[0024] The dendrite prevention layer 140 may be relatively thin. For example, the dendrite prevention layer 140 may be from 0.05 μm to 10 μm. In some embodiments, the dendrite prevention layer 140 may be deposited as a film on the surface of the anode current collector 150. The dendrite prevention layer 140 may be made of one or more of the following materials: carbon black, acetylene black, silver, zinc, gold, bismuth, tin, polyvinylidene fluoride (PvDF), polyimide (PI), polyacrylic acid (PAA), and carboxymethyl cellulose styrene butadiene rubber (CMC-SBR). The dendrite prevention layer 140 can also be formed using an alloy of silver, zinc, gold, bismuth, and tin. The dendrite prevention layer 140 may be formed from a single type of material, but the dendrite prevention layer 140 may be formed using the plurality of materials shown.

[0015]

[0025] The anode current collector 150 may have a first surface in contact with the dendrite prevention layer 140. The anode current collector 150 may function as both an anode and an anode current collector. In some embodiments, the anode current collector 150 is a conductor foil such as a copper foil. In the absence of the dendrite prevention layer 140, the anode current collector 150 may exhibit a higher nucleation energy that tends to cause lithium accumulation rather than depositing as a film during charging of the battery cell.

[0016]

[0026] Figure 2 shows another embodiment of a layer stack 200 of an anode-free solid-state battery having a plurality of lithium gel separator layers and a plurality of dendrite prevention layers. In some embodiments, multiple sets of layers may be stacked together to increase the charge capacity of the battery cell. In the illustrated embodiment of Figure 2, the layers up to 110 - 150 are as detailed in connection with Figure 1. Additionally, a dendrite prevention layer 210 is stacked on the opposite side of the dendrite prevention layer 140 of the anode current collector 150. A second lithium gel separator layer 202 is in direct contact with the dendrite prevention layer 210. Further, a cathode 230 and a cathode current collector 240 are stacked with respect to the lithium gel separator layer 202. Additional layers may be added in the same manner as detailed in connection with Figure 2. For example, there may be another cathode under the cathode current collector 240, followed by another lithium gel separator layer, etc. For example, multiple sets of layers may be added to increase the charge capacity of the battery cell. Figure 1 shows a single stack set, and Figure 2 shows a double stack set, but other embodiments may include more stacks, such as 16 or more. Such layers, once combined, may be sealed as part of a pouch-type battery cell.

[0017]

[0027] Figure 3A shows an embodiment of a lithium gel separator layer formed using heat. Figure 3B, which is detailed herein in parallel with Figure 3A, shows an embodiment of a method for making a lithium gel separator layer. The lithium gel separator layer can function as a phase change electrolyte that can be used in a solid battery. A lithium gel separator layer, such as lithium gel separator layer 130, may include a plurality of sub-layers and may be made using heat. Pressure can also be used to increase the surface area of the interfaces between the layers of the lithium gel separator layer. First, in block 350, a non-reactive skeleton may be formed. For example, the skeleton material 305 may be polyethylene (PE) or polyethylene oxide (PEO). The skeleton material 305 may be permeable such that a liquid, such as an electrolyte solution, can penetrate, be injected into, or otherwise be introduced into the skeleton material 305. The physical structure of the skeleton material 305 can create gaps that can be filled with a liquid. For example, the skeleton material 305 may have a porosity of between 10% and 90% into which a liquid can be introduced. The specific physical structure may be a honeycomb structure, a spider web structure, or other pattern or random porous physical structure that allows a liquid to fill the empty spaces within the skeleton material 305. The skeleton layer may have a thickness of from 1 μm to 100 μm. In some embodiments, the skeleton layer has a thickness of 15 μm.

[0018]

[0028] In block 355, the first adhesive layer may be attached to the non-reactive backbone. In block 360, the second adhesive layer may be attached to the opposite side of the non-reactive backbone. Thus, the backbone material 305 may be positioned between the two adhesive layers 310. Together, these three layers may form a dry separator layer 300 into which the electrolyte has not yet been introduced. Each of the adhesive layers 310 may include PvDF, PI, PAA, or CMC-SBR. Such materials may function as an adhesive bond. Thus, the adhesive layer 310 may serve to increase the amount of adhesion between the backbone material 305, the cathode 120, and the dendrite prevention layer 140. The amount of adhesion between the lithium gel separator layer 130 and the dendrite prevention layer 140, at least partially due to the adhesive layer, may be greater than the amount of adhesion between the dendrite prevention layer 140 and the anode current collector 150.

[0019]

[0029] In some embodiments, a ceramic that can improve the transport of lithium ions and help prevent the formation of dendrites may be added to one or both of the adhesive layers. Such ceramics may include MgO, PZT, BaTiO3, SBT, BFO, LATSPO, LISICON, LICGC, LAGP, LLZO, LZO, LAGTP, LiBETI, LiBOB, LiTf, LiTF, LLTO, LLZP, LTASP, and LTZP. Each of the adhesive layers 310 may have a thickness of 1 to 500 μm. By using ceramics within the adhesive layer, the ionic conductivity may be reduced. The use of lithium ion conductor ceramics can still reduce the ionic conductivity (compared to liquids), but can ensure a higher ionic conductivity compared to other ceramics. However, the advantages of the ceramics, which can prevent short circuits and reduce the overall cell failure rate, may outweigh the disadvantage of the reduction in ionic conductivity.

[0020]

[0030] In block 365, a liquid electrolyte mixture may be made. The liquid electrolyte mixture may include a lithium salt, a solvent, and an additive. The salt may be LIFSI, LITFSI, or LiPF6. The concentration of the salt may be 1.0 to 4.0 moles per liter. The lithium salt may enable the lithium solution to function as an electrolyte. The solvent may be dimethyl carbonate (DMC), dimethoxyethane (DME), diethyl carbonate (DEC), dioxolane (DOL), bistrifluoroethyl ether (BTFE), ethyl methyl carbonate (EMC), or ethylene carbonate (EC). The solvent may function to dissolve the salt.

[0021]

[0031] The additive may include a compound in the lithium solution that causes a transition from a liquid to a gel upon heating. Generally, the additive includes a polymer and a cross-linking agent. For example, when heat of 60°C to 150°C is applied to the additive, the cross-linking agent ignites, causing further polymerization of the polymer and the solvent. Since the lithium salt is uniformly distributed throughout the solvent, when the gel is formed, the lithium salt is uniformly distributed throughout the gel. One or more additives may include CsPF6, FEC (fluoroethylene carbonate), polycarbonate (PC), or LiNO3. The additive may have a concentration of 0.01 to 4.0 moles per liter. The additive including the polymer additive and the cross-linking additive may be mixed into the lithium solution before the lithium solution penetrates throughout the non-reactive skeleton.

[0022]

[0032] One possible combination of the lithium salt and the solvent may be 4M LiFSI dissolved in DME, to which an additive may be added. Table 1 shows combinations of polymer additives, cross-linking additives, and relative concentrations at which they may be used.

[0023]

Table 1

[0024]

[0033] In some embodiments, one or more additional additives may function to reduce side reactions. The purpose of adding the additives may also be to help form LiF, i.e., the solid electrolyte interphase (SEI), which can prevent Li metal from having various side reactions.

[0025]

[0034] The lithium gel separator layer takes the form of the dry separator layer 300, but the dry separator layer 300 may be laminated with other battery cell layers instead of the lithium gel separator layer 130. When the assembly of the layers of the battery cell is completed and the battery cell is inserted into a housing (e.g., a pouch), a liquid electrolyte may be added, and then heat and pressure may be applied.

[0026]

[0035] In block 370, a liquid electrolyte mixture may be infiltrated into a non-reactive skeleton. Arrow 315 indicates that as the lithium liquid penetrates throughout the skeleton material 305, a lithium liquid-infiltrated skeleton material 320 is created. The lithium liquid can penetrate the skeleton material submerged under atmospheric pressure for a period of time such as 6 to 24 hours. This step may be performed after the dry separator layer is assembled as part of the battery cell. The liquid electrolyte, which may be a lithium liquid, penetrates into the voids within the skeleton material and may then be composed of a material that, after being exposed to heat, causes the lithium liquid to solidify at least partially into a gel or the like. Such an arrangement allows the lithium gel separator layer to be initially made as a dry separator layer and then, after the battery cell is housed in a housing (e.g., a pouch cell), the lithium liquid to penetrate throughout the skeleton material and transition to a gel. In some embodiments, pressure is also applied, and the purpose of this pressure may be to increase the amount of contact at various interfaces within the laminated stack.

[0027]

[0036] When the lithium solution penetrates the entire skeleton material 305 to create the lithium solution-penetrated skeleton material 320, a block 375 where pressure, heat, or both can be applied, as indicated by arrow 325, may be performed. For example, in some embodiments, first, pressure may be applied at room temperature with a force of 100 N / cm for a duration of 60 to 120 seconds. 2 Next, a heat press process may be performed at a temperature of 100°C to 110°C with a force of 100 to 500 N / cm for a duration of 60 to 120 seconds. The heat applied to the lithium gel separator layer 301 can transition the lithium solution-penetrated skeleton material 320 into a pseudo-solid lithium gel layer 330. In some embodiments, pressure can assist this process or help increase the surface area of the interface between the layers of the lithium gel separator layer and / or other layers of the battery cell. Next, the lithium gel separator layer 302 may be finally formed. 2

[0028]

[0037] To fabricate such a battery cell, various methods can be employed. FIG. 4 shows one embodiment of a method 400 for manufacturing a pouch-type battery cell including an anode-free solid battery having a lithium gel separator layer and a dendrite prevention layer. In block 405, the dendrite prevention layer may be laminated on the anode current collector. The dendrite prevention layer may be as detailed in connection with the dendrite prevention layer 140 of FIG. 1. The anode current collector may be as detailed in connection with the anode current collector 150 of FIG. 1.

[0029]

[0038] ​In block 410, a three-component lithium gel separator layer may be formed. First, the lithium gel separator layer may take the form of a dry separator layer. That is, as detailed in connection with FIG. 3A, a liquid electrolyte such as a lithium solution has not yet been injected into the backbone layer. In other embodiments, the backbone material in block 410 is permeated with liquid. The lithium gel separator layer, which may or may not have a lithium solution present, may be laminated on the dendrite prevention layer in block 415. The amount of adhesion between the lithium gel separator layer and the dendrite prevention layer may be greater than the amount of adhesion between the dendrite prevention layer and the anode current collector. In some cases, the amount of adhesion between the lithium gel separator layer and the dendrite prevention layer may be greater than the amount of adhesion between the dendrite prevention layer and the anode current collector after heating and pressing in block 430.

[0030]

[0039] In block 420, a cathode layer may be laminated on the lithium gel separator layer (wherein the gel is still in liquid form or has not yet been introduced into the backbone material). In block 425, a cathode collector layer may be laminated on the cathode layer. In some embodiments, block 425 may be performed, and then the integrated cathode layer and cathode current collector layer may be laminated in block 420 on the lithium gel separator layer (wherein the gel is still in liquid form or has not yet been introduced into the backbone material).

[0031]

[0040] It should be understood that blocks 405-425 may be repeated multiple times to create a multi-layer stack of solid-state battery cells. For example, in a stack set similar to that detailed in connection with FIG. 2, 16 layer sets may be created. Such an arrangement allows the anode current collector and the cathode current collector to contact the dendrite prevention layer and the cathode, respectively, on both sides.

[0032]

[0041] In block 430, one or more layer stacks may be packaged into a pouch cell. In this block, assuming that the lithium liquid (or other forms of liquid electrolyte) was introduced in block 410, it may still be in liquid form. The layer stack may be vacuum packaged within the pouch cell to remove excess air. The pouch cell may be made of a flexible material such as plastic that allows the pouch to expand and be compressed. If the lithium liquid did not penetrate the entire skeleton layer in block 410, the lithium liquid may be introduced into the pouch cell in block 432 during (or before or after) the packaging process. Thereafter, the lithium liquid may penetrate into the skeleton layer of the dry separator layer.

[0033]

[0042] In block 435, one or more processes of heat, pressure, or both may be applied to the packaged pouch cell. This process can perform multiple functions: 1) Block 435 can increase the amount of physical contact between adjacent layers of the battery cell, 2) Block 435 can change the lithium liquid into a lithium gel, and 3) Block 435 can cause adhesion between the dendrite prevention layer and the lithium gel layer that is greater than the adhesion between the dendrite prevention layer and the anode current collector. For example, in some embodiments, first, pressure may be applied at room temperature with a force of 80 - 120 N / cm for a duration of 60 - 120 seconds. Then, a heat press process may be performed at a temperature of 80°C - 130°C with a force of 100 - 500 N / cm for a duration of 60 - 120 seconds. 2 of force may be applied at room temperature for a duration of 60 - 120 seconds. Then, a heat press process may be performed at a temperature of 80°C - 130°C with a force of 100 - 500 N / cm 2 for a duration of 60 - 120 seconds.

[0034]

[0043] In block 440, the pouch cell may be installed within a jig press (or other mechanical device that applies pressure to the pouch cell). The jig press may be used to apply long-term pressure to the SSB pouch cell. In some embodiments, multiple SSB pouch cells are stacked and then compressed using a jig press. While within the jig press, the SSB pouch cell may be repeatedly charged and discharged. The SSB pouch cell can be used to supply power to a vehicle or other form of electric device.

[0035]

[0044] According to FIG. 2, and as an example of an SSB that can be manufactured by method 400, an SSB pouch cell may be made that includes 16 layer sets and is approximately 65 mm × 65 mm. For a given layer, at 0% state of charge (SOC), there is a thickness of 3.3 mm. At 100% SOC, there is a thickness of 3.64 mm, which represents an approximately 10% increase due to swelling. The overall cell performance can be 4520 mAh with an average voltage of 3.79 V. At 100% SOC, the energy density (by volume) can be 1122 Wh / L and the energy density (by weight) can be 432 Wh / Kg.

[0036]

[0045] The above embodiments are directed to creating planar layers of battery cells. Such layers can be used in pouch-type battery cells. In other embodiments, cylindrical battery cells such as those detailed in connection with FIGS. 5 and 6 may be made. Such cylindrical battery cells may have the same stacking as detailed in connection with FIGS. 1 - 3, but the process for making the cylindrical cells may be different. In connection with FIGS. 5 and 6, further details regarding such embodiments are provided.

[0037]

[0046] FIG. 5 shows an embodiment of a cylindrical battery press system 500. The cylindrical battery press system 500 may include a compression mechanism 510, a heating element 520, a buffer 530, a cylindrical pouch battery cell (also referred to as a “battery cell”) 540, a temperature sensor 550, a support structure 560, and a platform 570. Embodiments of the cylindrical battery press system and related systems are detailed in U.S. Patent Application No. 16 / 412,338, entitled “Isostatic Press Devices and Processes for Cylindrical Solid-State Batteries,” filed on May 14, 2019, which is hereby incorporated by reference in its entirety for all purposes. Other embodiments related to systems for isotropically pressing cylindrical battery cells are detailed in U.S. Patent Application No. 16 / 217,010, entitled “Hydraulic Isostatic Press Processes for Solid-State Batteries,” filed on December 11, 2018, which is hereby incorporated by reference in its entirety for all purposes.

[0038]

[0047] The compression mechanism 510 may be generally cylindrical in shape and may have a cross-section similar to a halo. There may be a gap along the curved sidewall of the compression mechanism 510. On both sides of this gap are edges 511 and 512. By moving edge 511 towards edge 512, the volume within the compression mechanism 510 can be decreased. Thus, when edge 511 moves away from edge 512, the volume within the compression mechanism becomes larger, allowing the buffer and / or battery cell 540 to be installed. When edge 511 moves towards edge 512, the volume within the compression mechanism 510 becomes smaller, and thus pressure is applied to the buffer 530 and through the buffer 530 to the battery cell 540.

[0039]

[0048] The battery cell 540 may be a cylindrical jelly roll type battery cell similar to the embodiments of FIGS. 1-3. The cylindrical jelly roll type battery cell may be stored inside a pouch that can be compressed using a cylindrical battery press system 500 (initially). As detailed in the method 600 of FIG. 6, after being compressed and heated using the cylindrical battery press system 500, the cylindrical jelly roll type battery cell may be removed from the pouch and installed in a cylindrical canister.

[0040]

[0049] The compression mechanism 510 may be formed from a semi-rigid material such as a hard rubber, plastic, or metal layer. The compression mechanism 510 may be partially deformed by the edge 511 being pushed or pulled towards the edge 512. In some embodiments, the edge 512 may be fixed to the support structure 560. The edge 511 may be connected to an extension such as a metal bar that allows a user to manually push or pull the metal bar to move the edge 511 towards the edge 512. In other embodiments, a hydraulic pump or an electric motor may be used to move the edge 511 towards the edge 512.

[0041]

[0050] The buffer material 530 may be wound around the battery cell 540. The buffer material 530 may be a semi-rigid material such as heat-resistant rubber. In some embodiments, the buffer material 530 may be a rubber filled with a liquid or other form of flexible skin. When viewed in cross-section, the buffer material 530 may generally have a halo shape. This halo shape defines a void at its center where the battery cell can be disposed inside. The buffer material 530 can serve to transmit the pressure applied by the compression mechanism 510 to the battery cell 540. The buffer material 530 can help disperse the pressure applied by the compression mechanism 510 so that the pressure applied to the curved sidewall of the battery cell 540 becomes uniform or substantially uniform. In some embodiments, the buffer material 530 is first wound around the battery cell 540. In some embodiments, the buffer material 530 may be a sheet of buffer material around which the battery cell is wound. Thus, next, the jelly roll type battery cell may be present within the jelly roll of the buffer material. The buffer material 530 may be installed together with the compression mechanism 510.

[0042]

[0051] A heating element 520 may be present between the buffer material 530 and the compression mechanism 510. The heating element 520 may generally be cylindrical in shape and may have a gap along a curved sidewall that matches the gap of the compression mechanism 510. The heating element 520 may be a resistive heater such that heat is generated when an electric current is applied to the heating element 520. In some embodiments, the heating element 520 can be heated up to 250°C. The amount of heat output by the heating element 520 may be controlled based on the output of the temperature sensor 550. The temperature sensor 550 may be located between the battery cell 540 and the buffer material 530. Thus, the temperature sensor 550 may indicate the temperature on the outer surface of the battery cell 540. In some embodiments, it may be desirable for the battery cell 540 to be heated to 80°C to 120°C. By applying a higher temperature using the heating element 520, the battery cell 540 can be heated to 80°C to 120°C more quickly at its surface. An external heating controller (not shown) may receive temperature measurements from the temperature sensor 550 and control the amount of heat generated by the heating element 520.

[0043]

[0052] The edge 512 is fixed to the support structure 560, and then the support structure 560 is fixed to the platform 570, but the edge 511 may remain free. By keeping the edge 511 free from the support structure 560 and the platform 570, the edge 511 can be moved towards the edge 512, as a result of which the compression mechanism 510 is slightly deformed. When the application of force to the edge 511 is stopped, the compression mechanism 510 can expand to return to its natural shape and can stop the application of pressure to the battery cell 540. It should be understood that the force applied to the edge 511 may be applied near the edge 511 and does not necessarily have to be applied exactly on the edge 511. However, the closer such a force is applied to the edge 511, the more uniformly the pressure applied to the buffer 530 can be distributed. Similarly, it should be understood that the edge 512 can be directly fixed to the support structure 560, or more precisely, a part of the compression mechanism 510 near the edge 512 may be fixed to the support structure 560. Here too, the closer the above-mentioned part of the compression mechanism 510 is fixed to the edge 512 of the support structure 560, the more uniformly the pressure applied to the buffer 530 can be distributed.

[0044]

[0053] Various methods can be employed to fabricate a cylindrical battery cell. FIGS. 6A and 6B illustrate one embodiment of a method for fabricating a cylindrical dendrite-free anode-free solid-state battery. In blocks 605-620, various steps may be performed to create a laminated stack similar to that presented in and described in relation to FIG. 1. In other embodiments, blocks 605-620 may be performed to create a stack set as detailed in relation to FIG. 2. That is, blocks 605-620 may be performed multiple times to create two or more (e.g., 3-20) layer sets.

[0045]

[0054] Blocks 605-620 illustrate a possible embodiment of how multiple layers can be stacked together. In other embodiments, the ordering of blocks 605-620 may be different. In block 605, the cathode layer may be attached to the cathode current collector layer. The cathode current collector layer may be an aluminum foil, and the cathode may be, for example, NCA (nickel-cobalt-aluminum oxide) or NCM (nickel-manganese-cobalt). The cathode layer may be deposited on the cathode current collector layer, or the cathode current collector layer may be deposited on the cathode layer.

[0046]

[0055] In block 610, the dendrite prevention layer may be deposited on the anode current collector layer or attached to the anode current collector layer in other ways. The anode current collector layer may be copper, and the dendrite prevention layer may be carbon black, acetylene black, silver, zinc, gold, bismuth, tin, polyvinylidene fluoride (PvDF), polyimide (PI), polyacrylic acid (PAA), and carboxymethyl cellulose styrene butadiene rubber (CMC-SBR). The dendrite prevention layer can also be formed using an alloy of silver, zinc, gold, bismuth, and tin. The dendrite prevention layer may function to reduce the nucleation energy for lithium ions to deposit on the surface of the anode current collector layer.

[0047]

[0056] In block 615, a dry separator layer such as dry separator layer 300 may be attached to the cathode layer or the dendrite prevention layer, or positioned between them. The dry separator layer may include two adhesive layers and a backbone material as detailed in connection with dry separator layer 300. In block 620, a stacked stack including a dry separator layer laminated between the cathode and the dendrite prevention layer may be made. The stacked stack may include at least a dry separator layer, a dendrite prevention layer, an anode current collector layer, a cathode layer, and a cathode current collector layer, as shown in FIG. 1 having a dry separator layer instead of a lithium gel separator layer.

[0048]

[0057] In block 625, the stacked stack may be wound around itself multiple times to create a jelly roll type battery cell. Winding these layers together can create a generally cylindrical wound stacked stack. In block 630, the wound stacked stack may be inserted into a compressible flexible pouch. The pouch can serve as a temporary housing for the battery cell during part of the manufacturing process. Before sealing the pouch, a liquid electrolyte mixture may be injected, permeated into the pouch, or otherwise added. The liquid electrolyte mixture may be a lithium solution as detailed in connection with FIG. 3A. Injection of the lithium solution can cause the backbone material of the dry separator layer to be permeated by the lithium solution and to become a lithium solution permeated backbone material such as lithium solution permeated backbone material 320. As part of block 635, the pouch may be evacuated of any air present and sealed.

[0049]

[0058] In block 640, pressure may be applied to the pouch. A system similar to the cylindrical battery press system 500 may be used to apply the pressure. Before the pressure is applied, a temperature probe may be inserted such that it is adjacent to the outer surface of the pouch within the cylindrical battery press system. The pressure may then be applied by the cylindrical battery press system manually, or using an electric or hydraulic embodiment. The pressure applied may be between 100 kPa and 100 MPa. In some embodiments, the pressure is applied for between 30 seconds and 1 hour.

[0050]

[0059] In block 645, which can be performed simultaneously with or at least partially overlap in time with block 640, heat may be applied. The amount of heat applied may be between 150°C and 250°C. The temperature of the pouch may be monitored using a temperature probe. Heat may be applied to the battery cell until it reaches a temperature between 60°C and 150°C for a certain period, such as 30 seconds to 1 hour. Pressure, heat, or both can cause the lithium solution that penetrates the skeleton layer to transition into a pseudo-solid lithium gel layer. Therefore, the liquid does not remain in the pouch. Thus, the battery cell is a solid battery cell (including the gel).

[0051]

[0060] The heat and pressure applied in blocks 640 and 645 can additionally or alternatively increase the surface area contact amount between one or more of the layers of the battery cell. Additionally or alternatively, heat and pressure can increase the adhesion between two or more of the layers of the battery cell.

[0052]

[0061] In block 650, the cylindrical jelly roll exposed to heat and pressure may be removed from the pouch. Since the liquid has transitioned to a gel within the skeleton layer, there may be no liquid present. The cylindrical jelly roll may be inserted into a cylindrical battery cell canister. The cylindrical battery cell canister may be rigid or semi-rigid. In some embodiments, the cylindrical battery cell canister may be made of metal. The cylindrical battery cell canister can apply pressure to the cylindrical jelly roll when it expands. For example, when the battery cell is charged in block 660, the lithium deposition on the anode current collector can cause the battery to expand by 0.5% to 3% in diameter. The pressure applied by the side wall of the cylindrical battery cell canister can help control the amount of expansion and help maintain contact between the layers of the battery cell. In block 660, the battery cell may be repeatedly charged and discharged to supply power to an electrical device such as an electric vehicle (EV). The cylindrical battery manufactured according to method 600 can be charged up to 7559 Ah and discharged up to 6229 Ah, and thus exhibits an initial Coulomb efficiency of 82.4%.

[0053]

[0062] When lithium deposits on the anode current collector during charging, it may tend to deposit in aggregates rather than in a generally flat film. The amount of contact existing between the deposited lithium and the anode current collector can be small, so the electrical connection between the deposited lithium and the anode current collector can be small. Having a small or weak electrical connection between the deposited lithium and the anode current collector can cause the impedance of the battery cell to increase. High impedance can result in a degradation of the battery cell's performance: that is, a battery with a low internal resistance can deliver a large amount of current as required. Depending on the application, such as use in an electric vehicle (EV), the ability to deliver current quickly can significantly affect performance such as the EV's ability to accelerate. When the battery cell has a high internal resistance, heating of the battery can be caused by the current flowing through the battery cell, which can damage the battery cell.

[0054]

[0063] In some embodiments, additional layers may be present within the layer stack of the anode-free solid battery. The additional layer may be located between the dendrite prevention layer and the anode current collector. This layer can be referred to as an interface bonding layer. The interface bonding layer can promote the formation of lithium deposits with a high state of surface contact between the interface bonding layer and the lithium deposits. Since the interface bonding layer has a large amount of contact with both the anode current collector and the deposited lithium, it can reduce the internal resistance of the battery cell. Such an interface bonding layer may be added to any of the embodiments detailed in connection with FIGS. 1-6 or FIGS. 7-10.

[0055]

[0064] The interface layer may be made of a conductive agent and a binder. In some embodiments, the interface layer may be 30% - 99% conductive agent, and the remainder of the interface bonding layer may be a binder (1% - 70%). FIG. 7 shows one embodiment of a layer stack 700 of an anode-free solid-state battery having a lithium gel separator layer, a dendrite prevention layer, and an interface bonding layer. The layer stack 700 may be as detailed in connection with FIG. 1, but the interface bonding layer 710 may be between the anode current collector 150 and the dendrite prevention layer 140. The interface bonding layer 710 may be in direct contact with the dendrite prevention layer 140 on the first surface side and in direct contact with the anode current collector 150 on the second opposite surface side.

[0056]

[0065] To promote the deposition of lithium metal on the interface bonding layer 710, the interface bonding layer 710 may have a first adhesion amount with the anode current collector 150 that is greater than a second adhesion amount between the dendrite prevention layer 140 and the interface bonding layer 710, or a third adhesion amount between the dendrite prevention layer 140 and the lithium gel separator layer 130. The thickness of the interface bonding layer 710 may be 0.05 μm - 5 μm. The density of the interface bonding layer may be 0.1 - 2.0 grams per cubic centimeter.

[0057]

[0066] The interface bonding layer 710 may use carbon as a conductive agent mixed with a binder (PvDF, SBR-CMC, PAA) and metal particles such as Bi, Sn, Ag, Au, Pt. More specifically, acetylene black or carbon black may be used as the conductive agent. The individual carbon particles may be spherical particles of 3 nm - 20 nm. Possible types of binders include PvDF, SBR-CMC, and PAA.

[0058]

[0067] The impedance or resistance of the battery cell of FIG. 7 measured between terminal 720 and terminal 730 can be significantly reduced due to the presence of the interfacial bonding layer 710 as compared to embodiments such as FIG. 1 where the interfacial bonding layer 710 is absent. As an example, one embodiment of a battery cell without an interfacial bonding layer may have an impedance of 0.85 ohms, but when an interfacial bonding layer is present between the anode current collector and the dendrite prevention layer, the impedance can be 0.05 ohms.

[0059]

[0068] FIG. 8 shows an embodiment of a layer stack 800 of an anode-free solid battery that shows the relative amount of adhesion between various layers. One of the main aspects of the layer stack 800 of FIG. 8 is that the relative amount of adhesion between the layers may also promote the plating of lithium metal between the dendrite prevention layer 140 and the interfacial bonding layer 710 during the charging process.

[0060]

[0069] The interface 801 between the lithium gel separator layer 130 and the dendrite prevention layer 140 may have a first amount of adhesion. The interface 802 between the dendrite prevention layer 140 and the interfacial bonding layer 710 may have a second amount of adhesion. The interface 803 between the interfacial bonding layer 710 and the anode current collector 150 may have a third amount of adhesion. By having the interface 802 have less adhesion than the interface 801 or the interface 803, the plating of lithium at the interface 802 can be promoted. In other words, the second amount of adhesion may be greater than the first amount of adhesion or the third amount of adhesion.

[0061]

[0070] Figure 9 shows an embodiment 900 of a layer stack of a lithium-ion moving and deposited on an interfacial bonding layer of a lithium metal-free solid-state battery. In embodiment 900, the battery cell is being charged. During charging, as indicated by arrow 905, lithium ions move from cathode 120 through lithium gel separator layer 130, through dendrite prevention layer 140, and are caused to be plated as lithium metal layer 910 between dendrite prevention layer 140 and interfacial bonding layer 710. Dendrite prevention layer 140 can help suppress the growth of dendrites that can penetrate lithium gel separator layer 130. Thus, interfacial bonding layer 710 may be used in conjunction with dendrite prevention layer 140.

[0062]

[0071] The presence of lithium metal layer 910 can cause the battery cell to expand. During the discharge cycle, lithium ions can move from lithium metal layer 910 to cathode 120. As the battery cell is discharged and lithium ions move to cathode layer 120, the expansion within the battery cell can decrease.

[0063]

[0072] Figure 10 shows an embodiment of a method 1000 for manufacturing a pouch-type battery cell including a solid-state battery having a lithium gel separator layer, a dendrite prevention layer, and an interfacial bonding layer. It should be understood that method 1000 can be adapted such that an interfacial bonding layer can be manufactured as part of a cylindrical battery cell according to the blocks of method 600 of FIGS. 6A and 6B.

[0064]

[0073] In block 1005, an interfacial bonding layer may be deposited on the anode current collector. The anode current collector may be as detailed in connection with anode current collector 150 of FIG. 1. Block 1005 may include that a conductive material such as acetylene black is mixed with a binder and deposited on the anode current collector.

[0065]

[0074] In block 1015, a three-component lithium gel separator layer may be formed. First, the lithium gel separator layer may take the form of a dry separator layer. That is, as detailed in connection with FIG. 3A, a liquid electrolyte such as a lithium solution has not yet been injected into the skeleton layer or has not yet penetrated the entire skeleton layer. In other embodiments, the skeleton material has liquid penetrating it. In block 1020, a dendrite prevention layer may be laminated on the lithium gel separator layer where a lithium solution (or another liquid electrolyte) may be present or has not yet been introduced. The dendrite prevention layer may be as detailed in connection with the dendrite prevention layer 140 of FIG. 1. In some cases, the amount of adhesion between the lithium gel separator layer and the dendrite prevention layer may be greater than the amount of adhesion between the dendrite prevention layer and the interface bonding layer.

[0066]

[0075] In block 1025, a cathode layer may be laminated on the lithium gel separator layer (wherein the gel is still liquid or does not yet exist). In block 1030, a cathode collector layer may be laminated on the cathode layer. In some embodiments, block 1030 may be performed, and then the integrated cathode layer and cathode current collector layer may be laminated on the lithium gel separator layer in block 1025.

[0067]

[0076] In block 1032, the dendrite prevention layer previously laminated on the lithium gel separator layer may have an opposite layer laminated on the interface bonding layer. The lamination of the dendrite prevention layer and the interface bonding layer may result in relatively little adhesion existing between those layers. The dendrite prevention layer may create an interface having less adhesion with the interface bonding layer than the interface bonding layer forms with the anode current collector. The amount of adhesion can be controlled by adjusting the ratio of the binder to the active conductive material of the interface bonding layer. For example, PvDF may be used as the binder and Ketjenblack as the active material at a ratio of 3% PvDF to 97% Ketjenblack. In other embodiments, the equivalent proportion of Ketjenblack is 95% - 98%.

[0068]

[0077] It should be understood that blocks 1005 - 1030 may be repeated multiple times to create a plurality of layer stacks of the solid battery cell. For example, in a stack set similar to that detailed in relation to FIG. 2 with an additional interface bonding layer, 16 layer sets may be created. Such an arrangement enables the anode current collector and the cathode current collector to contact the dendrite prevention layer and the cathode respectively on both sides.

[0069]

[0078] In block 1035, one or more layer stacks may be packaged into a pouch cell. In this block, assuming the lithium liquid (or other form of liquid electrolyte) was introduced in block 1015, it may still be in a liquid state. The layer stack may be vacuum - packaged within the pouch cell to remove excess air. The pouch cell may be made of a flexible material such as plastic that allows the pouch to expand and be compressed. If the liquid electrolyte such as lithium liquid did not penetrate the entire skeleton layer in block 1015, the liquid electrolyte may be introduced into the pouch cell when (or before or after) the packaging is being done in block 1040. Thereafter, the lithium liquid may penetrate into the skeleton layer of the dry separator layer.

[0070]

[0079] In block 1045, one or more processes of heat, pressure, or both may be applied to the packaged pouch cell. This process can perform multiple functions: 1) Block 1045 can increase the amount of physical contact between adjacent layers of the battery cell, 2) Block 1045 can change a liquid electrolyte (e.g., a lithium solution) to a lithium gel, and 3) Block 1045 can help create an adhesion between the interface bonding layer and the anode current collector that is greater than the amount of adhesion between the dendrite prevention layer and the interface bonding layer. For example, in some embodiments, first, a pressure may be applied at room temperature with a force of 80 - 120 N / cm for a duration of 60 - 120 seconds. This part of the process can increase the amount of contact present at one or more interfaces of the layers of the battery cell. Then, a heat press process may be performed at a temperature of 50°C - 130°C with a force of 100 - 1000 N / cm for a duration of 60 - 2400 seconds. 2 of force. 2

[0071]

[0080] In block 1050, the pouch cell may be placed within a jig press (or other mechanical device that applies pressure to the pouch cell). The jig press may be used to apply long - term pressure to the SSB pouch cell. In some embodiments, multiple SSB pouch cells are stacked and then compressed using a jig press. While inside the jig press, the SSB pouch cell may be repeatedly charged and discharged. The SSB pouch cell can be used to supply power to a vehicle or other form of electric device.

[0072]

[0081] The above methods, systems, and devices are examples. Various configurations may, as necessary, omit, substitute, or add various procedures or components. For example, in alternative configurations, the methods may be performed in an order different from that described, and / or various steps may be added, omitted, and / or combined. Also, the features described with respect to a particular configuration may be combined in various other configurations. Different aspects and elements of the configurations may be combined in a similar manner. Also, since technology evolves, many of the elements are examples and do not limit the scope of the disclosure or claims.

[0073]

[0082] In the above description, specific details are provided to give a complete understanding of the exemplary configurations (including embodiments). However, the configurations can be implemented without these specific details. For example, well-known processes, structures, and techniques are shown without unnecessary detail to avoid obscuring the configurations. This description merely provides exemplary configurations and does not limit the scope, applicability, or configurations of the claims. More precisely, the foregoing description of the configurations provides those skilled in the art with an explanation of the implementable requirements for carrying out the described technology. Various changes can be made regarding the functions and arrangements of the elements without departing from the spirit or scope of the present disclosure.

[0074]

[0083] Also, the configurations can be described as processes depicted as flowcharts or block diagrams. Although each may describe operations as sequential processes, many of these operations can be performed in parallel or simultaneously. Further, the order of the operations may be rearranged. The processes may have additional steps not included in the figures.

[0075]

[0084] Although several exemplary configurations have been described, various modifications, alternative configurations, and equivalents may be used without departing from the spirit of the present disclosure. For example, the above elements may be components of a larger system where other rules may take precedence over or modify the application of the present invention. Also, some steps may be initiated before, during, or after the above elements are considered.

Claims

1. A method for making a cylindrical dendrite-preventing anode-free solid-state battery, comprising: attaching a cathode layer to a cathode current collector layer; laminating a dendrite-preventing layer between an anode current collector layer and the cathode layer; forming a stacked stack including a dry separator layer located between the cathode layer and the dendrite-preventing layer, the cathode layer laminated with the cathode current collector layer, and the dendrite-preventing layer laminated with the anode current collector layer; wrapping the stacked stack into a cylindrical jelly roll shape; inserting the wrapped stacked stack into a pouch; penetrating a liquid electrolyte mixture containing a salt and a solvent into the dry separator layer within the pouch; applying pressure to the pouch after the liquid electrolyte mixture has penetrated; applying heat to the pouch to at least partially gel the liquid electrolyte mixture that penetrates into the dry separator layer while pressure is being applied to the pouch; removing the wrapped stacked stack from the pouch after applying the pressure and the heat; inserting the wrapped stacked stack removed from the pouch into a cylindrical battery cell canister; A method comprising the above steps.

2. The method for making a cylindrical dendrite-preventing anode-free solid-state battery according to claim 1, wherein the liquid electrolyte mixture further comprises a polymer additive and a cross-linking additive that gel the liquid electrolyte mixture when the heat is applied.

3. The method for making a cylindrical dendrite-preventing anode-free solid-state battery according to claim 1, wherein a first adhesive layer is attached to the dry separator layer such that the first adhesive layer is located between the dry separator layer and the cathode layer.

4. The method for making a cylindrical dendrite-preventing anode-free solid-state battery according to claim 3, wherein a second adhesive layer is attached to the dry separator layer such that the second adhesive layer is located between the dry separator layer and the dendrite-preventing layer.

5. The method for making a cylindrical dendrite-preventing anode-free solid-state battery according to claim 1, further comprising inserting the pouch into a cylindrical pressing module, wherein the cylindrical pressing module is a cushioning material wrapped around the pouch.

6. Inserting a temperature probe for monitoring the temperature between the pouch and the cylindrical pressing module The method of manufacturing a cylindrical dendrite-preventing anode-free solid battery according to claim 5, further comprising **Claim 7** The method of manufacturing a cylindrical dendrite-preventing anode-free solid battery according to claim 6, wherein the heat is applied through a compressible material wound around the curved edge of the pouch. **Claim 8** The method of manufacturing a cylindrical dendrite-preventing anode-free solid battery according to claim 7, wherein the applied heat is 150°C to 250°C. **Claim 9** The method of manufacturing a cylindrical dendrite-preventing anode-free solid battery according to claim 1, wherein the presence of the dendrite-preventing layer reduces the nucleation barrier in the energy for lithium ions to deposit on the anode current collector layer. **Claim 10** The method of manufacturing a cylindrical dendrite-preventing anode-free solid battery according to claim 9, wherein the thickness of the dendrite-preventing layer is 0.05 micrometers to 10 micrometers. **Claim 11** The method of manufacturing a cylindrical dendrite-preventing anode-free solid battery according to claim 10, wherein the dendrite-preventing layer comprises one or more materials selected from the group consisting of carbon black, acetylene black, ketjen black, silver, zinc, gold, bismuth, tin, polyvinylidene fluoride (PVDF), polyimide (PI), polyacrylic acid (PAA), and carboxymethyl cellulose styrene butadiene rubber (CMC-SBR). **Claim 12** The method of manufacturing a cylindrical dendrite-preventing anode-free solid battery according to claim 9, further comprising depositing an interfacial bonding layer on the anode current collector layer. **Claim 13** A cathode layer, A cathode current collector layer attached to the cathode layer, An anode current collector layer, A dendrite-preventing layer positioned between the anode current collector layer and the cathode layer, A lithium gel separator layer positioned between the cathode layer and the dendrite-preventing layer, A canister into which the cathode layer, the cathode current collector layer, the anode current collector layer, the dendrite-preventing layer, and the lithium gel separator layer are inserted, comprising further comprising an interfacial bonding layer deposited on the anode current collector layer, The first adhesion amount between the interface bonding layer and the anode current collector layer is greater than the second adhesion amount between the interface bonding layer and the dendrite prevention layer. Cylindrical dendrite-preventing anode-free solid battery.

14. The cylindrical dendrite-preventing anode-free solid battery according to claim 13, wherein the lithium gel separator layer contains a skeleton material, a lithium salt, a solvent, and two or more additives.

15. The cylindrical dendrite-preventing anode-free solid battery according to claim 14, wherein the two or more additives include a polymer additive and a cross-linking additive, and the polymer additive and the cross-linking additive form a gel in the solvent and the lithium salt when exposed to heat.

16. The cylindrical dendrite-preventing anode-free solid battery according to claim 13, wherein the dendrite prevention layer contains one or more materials selected from the group consisting of carbon black, acetylene black, ketjen black, silver, zinc, gold, bismuth, tin, polyvinylidene fluoride (PVDF), polyimide (PI), polyacrylic acid (PAA), and carboxymethylcellulose styrene butadiene rubber (CMC-SBR).

17. The cylindrical dendrite-preventing anode-free solid battery according to claim 13, wherein the thickness of the dendrite prevention layer is 0.05 micrometers to 10 micrometers.

18. The cylindrical dendrite-preventing anode-free solid battery according to claim 13, wherein the presence of the dendrite prevention layer reduces the nucleation barrier in the energy for lithium ions to deposit on the anode current collector layer.

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