Solid battery and method for forming the same

Abstract

Methods for forming electrochemical cells using non-inert gases are disclosed. Exemplary methods include providing a first gas prior to applying one or more of a current and a voltage to the cell. The first (e.g., non-inert) gas can facilitate the formation of a solid electrolyte interphase interface (SEI). A further embodiment of the present disclosure relates to a method for forming an electrochemical cell, or a portion thereof, by electrospraying a solution including a polymeric material. Such a method potentially eliminates the step of compressing the cell at pressures exceeding 100 MPa and extends cycle life while reducing fire hazards.

Description

Technical Field

[0001] (Cross - Reference to Related Applications) This application is a continuation - in - part of U.S. Non - Provisional Patent Application No. 17 / 122,462, entitled “SOLID - STATE BATTERY AND METHOD OF FORMING SAME,” filed on Dec. 15, 2020, and claims priority to U.S. Non - Provisional Patent Application No. 17 / 242,284, entitled “SOLID - STATE BATTERY AND METHOD OF FORMING SAME,” filed on Apr. 27, 2021, which claims priority to the above - mentioned application. The contents of each of the above - mentioned applications are hereby incorporated by reference into this specification to the extent not inconsistent with the present disclosure.

[0002] The present disclosure generally relates to solid - state batteries and methods of forming such batteries. More specifically, embodiments of the present disclosure relate to methods of forming solid - state batteries using a first gas or a non - inert gas. Further embodiments of the present disclosure relate to methods of forming a battery or a component of a battery using an electrospray process to create a polymer thin film that can advantageously suppress dendritic growth during the lifetime of the battery.

Background Art

[0003] Batteries are in high demand for a wide range of applications, from small batteries for industrial and medical devices to larger batteries for electric vehicles and power grid energy storage systems. Well - known and widely used batteries include lithium - ion batteries.

[0004] A lithium-ion battery generally includes one or more electrochemical cells, each electrochemical cell including an anode, a cathode, and an electrolyte (e.g., liquid), and often including a separator between the anode and the cathode. During discharge of the battery, lithium ions flow from the anode to the cathode through the electrolyte of the electrochemical cell to provide current. To recharge the battery, a sufficiently biased external current source is applied to the battery to flow the lithium ions in the reverse direction, i.e., from the cathode to the anode, for reattachment to the anode or substrate. A typical lithium-ion electrochemical cell includes at least one electrode that utilizes intercalation to add lithium.

[0005] Typical lithium-ion batteries work well for some applications, but there is a need for batteries with high energy density, increased charging rates, lower cost materials, and reduced safety issues, such as reduced flammability. Accordingly, improved lithium-ion cells, components of such cells, batteries including such cells, and methods of forming and using such cells and batteries are desired.

[0006] Any discussion, including the discussion of problems and solutions, described in this chapter is included in this disclosure solely for the purpose of providing a background for the disclosure. Such discussion should not be construed as an admission that any or all of this information was known at the time the invention was made or otherwise constitutes prior art. SUMMARY OF THE INVENTION

[0007] The present disclosure generally relates to solid electrochemical cells and batteries, and to methods of forming such cells and batteries. Embodiments of the present disclosure provide solid batteries having solid electrolytes that advantageously have a low interfacial resistance similar to that of a lithium-ion battery formed using a conventional liquid electrolyte. Utilization of a solid rather than a liquid electrolyte can reduce safety issues such as the potential fire hazard associated with use or storage of the battery. Additionally or alternatively, utilization of a solid electrolyte can extend the cycle life of the battery.

[0008] According to various embodiments of the present disclosure, a method of forming an electrochemical cell and / or a battery includes supplying a first (e.g., non-inert) gas. The first / non-inert gas can include at least one oxygen atom. The first gas can be supplied to move all or a portion of the gas that may be present, for example, within the housing of the battery, during the formation of the battery and / or within the battery. Advantageously, a solid-state battery manufactured according to an exemplary embodiment exhibits an improvement in interfacial ion conductivity that can result in an improvement in specific capacity, rate capability, cycle life, energy density, power density, self-discharge rate, charge rate, and low and high temperature performance.

[0009] According to embodiments of the present disclosure, a method of forming an electrochemical cell is provided. According to an exemplary aspect of these embodiments, the cell does not generate a significant amount of gas during operation. In this context, not generating a significant amount of gas means that gas generation is not a significant form of the electrochemical reaction. For example, the above method is not used to form a gas (e.g., air) cathode electrochemical cell. According to a further aspect, the above method includes providing a housing, providing a first electrode within the housing, providing a solid electrolyte in contact with the first electrode and within the housing, supplying a first gas (e.g., a non-inert gas) to the housing so as to move the ambient gas within the housing, wherein the ambient gas is not an electrode, sealing the housing, applying one or more of voltage and current to the electrochemical cell under the influence of the first gas, and after the applying step, removing at least 90% by mass, preferably at least 95% by mass, more preferably at least 99% by mass of the gas present within the housing, wherein the mass% removed is based on the original mass within the housing prior to the removing step. The existing gas can be removed, for example, using a vacuum source (e.g., a vacuum pump) coupled to a port through the housing. According to a further aspect, the above method includes forming a solid layer on the surface of the electrolyte and on one or more of the first and second electrodes during the applying step. Further, or alternatively, the above method includes forming a solid layer between the electrodes. The solid layer may have a thickness in the range of about 1 nm to about 1 μm, or preferably, a diameter in the range of about 2 nm to about 500 nm, more preferably about 5 nm to about 200 nm. When present, the solid layer may contain oxygen or sulfur. When present, the solid layer, which is part of the solid electrolyte, may be ion-conductive and electrically insulating. The first gas is not generated during the applying step or during operation of the cell. The above method may further include supplying a second gas to the housing in order to move at least a portion of the first gas within the housing and to remove at least a portion of the gas formed during the applying step prior to the removing step.The above method can additionally include performing at least one additional step of applying one or more of a voltage and a current to the electrochemical cell to form a solid layer between the solid electrolyte and one or more of the first electrode and the second electrode before the removing step. The second gas is different from the first gas. The first gas contains at least one oxygen atom. Exemplary first gases can be selected from one or more of the group consisting of CO2, CO, O2, N2O, NO2, and SO2. The solid electrolyte contains at least one oxygen atom or at least one sulfur atom. Optionally, the first gas can contain at least one sulfur atom. For example, the first gas can contain one or more of S8, COS, CS2, SF6, H2S, SO2, CH4S, and C2H6S. The above method can include the step of electrospraying a solution to form one or more of the first electrode, the electrolyte, and the second electrode. Further, or alternatively, the above method can include the step of compressing a cell component including the first electrode and the solid electrolyte at a reduced stack pressure lower than 100 MPa, preferably lower than 50 MPa, more preferably lower than 10 MPa.

[0010] According to a further embodiment of the present disclosure, a method of forming an electrochemical cell includes providing a housing, providing a first electrode within the housing, providing a solid electrolyte in contact with the first electrode and within the housing, providing a substrate within the housing, supplying a first non-inert gas to the housing to move ambient gas within the housing, and sealing the housing. The exemplary method can further include forming a solid electrolyte interphase (SEI) between the solid electrolyte and one or more of the first electrode and the second electrode. For example, the non-inert gas can be used during one or more of the steps of charging the electrochemical cell and discharging the electrochemical cell. Gas formed during one or more of the steps of charging the electrochemical cell and discharging the electrochemical cell can be removed using a non-inert gas, another (e.g., second) non-inert gas, and / or an inert gas. The method can further include one or more second and / or additional steps of discharging the electrochemical cell, which can be performed after the discharging step and the removing step.

[0011] According to an additional embodiment of the present disclosure, an electrochemical cell is provided. The electrochemical cell can be formed, for example, using the methods described herein. The first electrode can include a first current collector, and the second electrode can include a second current collector, and one or more of the first and second current collectors includes an alloy having at least one material selected from the group consisting of molybdenum, titanium, zirconium, and combinations thereof. The electrochemical cell can substantially eliminate a liquid electrolyte.

[0012] According to yet further embodiments of the present disclosure, a battery is provided. The battery can include an electrochemical cell as described herein and / or can be formed according to a method as described herein. By way of example, the battery can include a first (e.g., non-inert gas), e.g., a gas containing at least one oxygen atom. According to various aspects of these embodiments, the first / non-inert gas is not intended to be used as an active material. The non-inert gas can be consumed or dissolved to less than 0.01 mg per mAh on average during the entire life cycle of the battery. The term "entire life cycle of the battery" as used herein is intended to mean that the life of the battery is considered to have exceeded its normal service life, which can be the case when the battery first exhibits 80% of its original capacity. Also, the battery can include a cathode that can include a compound containing an organic moiety or a halogen atom. The first / non-inert gas can be brought into contact with the cathode and the electrolyte. The battery can also include a plasticizer as part of the electrode and electrolyte materials. Additionally, or alternatively, the battery can include an electrosprayed polymer material as described herein.

[0013] According to further embodiments of the present disclosure, a method of forming a solid electrochemical cell or a part thereof includes providing a substrate such as a current collector, generating a solution containing a polymer material, and electrospraying the solution onto the substrate.

[0014] According to further embodiments of the present disclosure, a method of forming a solid electrochemical cell or a portion thereof includes generating a solution comprising a polymeric material and a solid electrolyte material, electrospraying the solution onto a substrate, and forming an independent solid electrolyte, wherein the independent solid electrolyte comprises more than 70 wt% of the solid electrolyte material, preferably more than 80 wt%, more preferably more than 90 wt%, and compressing a cell component comprising the independent solid electrolyte and an electrode at a stack pressure lower than 100 MPa, preferably lower than 50 MPa, more preferably lower than 10 MPa. The method can further include supplying a first gas to form a solid layer on the surface of the electrolyte and on one or more of the first and second electrodes.

[0015] According to still other embodiments, a battery includes an electrolyte comprising an electrosprayed polymeric material. The polymeric material can have an ionic conductivity lower than 10 -6 S / cm or lower than 10 -7 S / cm. The weight percent of the polymeric material on the electrolyte can be greater than 0% and less than 5%. Further, or alternatively, the cathode can include an electrosprayed polymeric material. Also, the battery can include a plasticizer as part of the electrode (e.g., cathode) and / or the electrolyte material.

[0016] According to another exemplary embodiment, a method of manufacturing a battery includes forming a battery stack comprising a cathode comprising a cathode active material incorporated on a conductive material and an electrolyte disposed within and on the cathode. The method also includes introducing a non-inert gas into the battery stack. The electrolyte is in contact with the cathode and the gas. The battery can perform at least one charge and / or discharge operation at a current density greater than 0 mA / cm 2 and less than 0.1 mA / cm 2 under the influence of the gas.

[0017] According to another exemplary embodiment, a method of manufacturing a battery includes forming a battery stack in an atmosphere filled with a non-inert gas. The battery includes a cathode including a cathode active material incorporated on a conductive material, and an electrolyte disposed in and on the cathode. The electrolyte is in contact with the cathode and the gas. The battery can perform at least one charge and / or discharge operation at a current density greater than 0 mA / cm 2 and less than 0.1 mA / cm 2 under the influence of the gas.

[0018] In other embodiments and aspects, the battery can include an anode comprising a material selected from the group consisting of lithium, sodium, potassium, magnesium, calcium, vanadium, aluminum, zinc, silicon, graphite, graphene, porous carbon, activated carbon, a form of silicon, metal oxides, and combinations thereof.

[0019] In other embodiments and aspects, the conductive material includes a porous carbon material selected from the group consisting of carbon black, carbon nanotubes, carbon nanofibers, carbon dots, activated carbon, amorphous carbon, mesoporous carbon, porous carbon, graphite, graphene, graphene oxide, graphene nanoribbons, nitrogen-doped carbon, nitrogen-doped graphene, nitrogen-doped graphene oxide, and combinations thereof.

[0020] In further aspects and embodiments, the porous carbon is in the form of particles, powders, paper, foams, fibers, sheets, disks, rods, and / or foils.

[0021] These and other embodiments will be readily apparent to those skilled in the art from the following detailed description of the specific embodiments with reference to the accompanying drawings, and the present invention is not limited to any specific embodiment disclosed.

Brief Description of the Drawings

[0022] A more complete understanding of the exemplary embodiments of the present disclosure can be obtained by referring to the detailed description and claims when considered in conjunction with the following exemplary drawings.

[0023] FIG. 1 shows a battery according to at least one exemplary embodiment of the present disclosure.

[0024] FIG. 2 shows a method according to at least one embodiment of the present disclosure.

[0025] FIGS. 3 to 7 show exemplary methods of manufacturing a battery according to exemplary embodiments of the present disclosure.

[0026] FIG. 8 shows a solid electrolyte according to an exemplary embodiment of the present disclosure.

[0027] FIG. 9 shows a structure including a solid electrolyte interphase electrochemically generated by a non-inert gas according to an exemplary embodiment of the present disclosure.

[0028] FIG. 10 is a graph showing the stable cycle performance of a symmetric cell including a pre-formed solid electrolyte under the influence of a non-inert gas compared to the cell performance under the influence of an inert gas.

[0029] FIG. 11 is a graph showing the improvement of the ionic conductivity of a pre-formed electrolyte under different partial pressures of various non-inert gases.

[0030] FIG. 12 is a graph showing the ionic conductivity of a battery according to an example of the present disclosure.

[0031] FIG. 13 shows the formation of a solid electrolyte interface under the influence of a non-inert gas according to an example of the present disclosure.

[0032] FIG. 14 shows another method according to an example of the present disclosure.

[0033] It will be recognized that the elements in the drawings are shown for simplicity and clarity and are not necessarily drawn to scale. For example, some of the dimensions of the elements in the drawings may be exaggerated compared to other elements to assist in the understanding of the exemplary embodiments of the present disclosure.

Best Mode for Carrying Out the Invention

[0034] Although specific embodiments and examples are disclosed below, those skilled in the art will understand that the present invention extends beyond the specifically disclosed embodiments and / or the uses of the present invention and its obvious modifications and equivalents. Accordingly, it is intended that the scope of the disclosed invention should not be limited by the specifically disclosed embodiments described below.

[0035] The present disclosure relates to batteries and methods of manufacturing batteries that address various drawbacks of conventional lithium-ion batteries. The batteries described according to various exemplary (and non-limiting) embodiments herein provide several advantages. For example, the exemplary batteries exhibit one or more of higher energy density, higher power density, longer cycle life, improved safety, and improved low-temperature performance compared to other lithium-ion batteries and particularly other solid lithium-ion batteries.

[0036] In this disclosure, "gas" can include materials that are gases, vaporized solids, and / or vaporized liquids at normal temperature and pressure (NTP), and can be composed of a single gas or a mixture of gases depending on the situation.

[0037] The term "non-inert gas", as used in the present specification, refers to a gaseous substance excluding inert gases. Optionally, the first gas is a non-inert gas. An inert gas is a gas that does not participate in chemical reactions to a significant or measurable extent. Inert gases can include, for example, nitrogen, helium, neon, argon, krypton, xenon, radon, or any combination thereof.

[0038] The term "plasticizer", as used in the present specification, refers to a material that is added to an organic or polymeric material to make it softer, more flexible, and / or to enhance its plasticity. Exemplary plasticizers include, by way of non-limiting example, succinonitrile, glutaronitrile, adiponitrile, ethylene carbonate, propylene carbonate, dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, sulfolane, 3-methyl-2-oxazolidinone, butylene carbonate, phthalic acid derivatives, trimellitic acid, adipates, sebacates, maleates, or any combination thereof.

[0039] The term "cathode", as used in the present specification, refers to the electrode of a battery cell that receives electrons from an external circuit and is reduced during discharge, and transfers electrons to the external circuit by oxidation during charging. The cathode can also be referred to as the positive electrode.

[0040] The term "anode", as used in the present specification, refers to the electrode of a battery cell that transfers electrons to the external circuit by oxidation during discharge, and receives electrons from the external circuit and is reduced during charging. The anode can also be referred to as the negative electrode.

[0041] The term "electrolyte", as used in the present specification, refers to a material that enables ion transport in a battery cell. The electrolyte acts as a conduit for ion transport through interaction with the anode and cathode. During charging of the battery, the electrolyte facilitates the movement of ions from the cathode to the anode, while during discharge, the electrolyte facilitates the movement of ions from the anode to the cathode. In a rechargeable battery, the electrolyte promotes ion cycling between the anode and the cathode.

[0042] The term "current collector", as used in the present specification, is typically used to refer to a component adjacent to the positive or negative electrode. In some embodiments, the current collector includes a conductive material. In some embodiments, the current collector includes an alloy having at least one material selected from the group consisting of molybdenum, titanium, zirconium, and combinations thereof.

[0043] The term "electrospray", also known as electrospinning, as used in the present specification, is used to refer to a thin-film manufacturing method that utilizes an electric force to draw in charged threads of an organic solution or organic melt. The electrospray method described in the present specification can advantageously enable the stretching and thinning of the organic material coated on the substrate.

[0044] The term "substrate", as used in the present specification, can refer to some underlying material, or a material on which another material can be deposited. The substrate can include, for example, a current collector, a current collector and an electrode material, and / or a current collector and an electrolyte.

[0045] Furthermore, any value of the variables shown (regardless of whether it is indicated with "about") can refer to an exact value or an approximate value, and includes equivalents, and can refer to an average value, a median value, a representative value, a mode value, etc. Furthermore, in this disclosure, the terms "comprising", "consisting of", and "having" can, in some embodiments, independently refer to "typically or extensively provided with", "equipped with", "essentially consisting of", or "consisting of". Substantially none or substantially zero can mean less than 1, less than 0.5, or less than 0.001 in terms of volume or weight percentage conversion. In this disclosure, any defined meaning does not necessarily exclude the ordinary and customary meanings in some embodiments.

[0046] Next, referring to the drawings, a battery 100 according to various embodiments of the present disclosure is illustrated in FIG. 1. The battery 100 includes a housing 102, a cathode current collector 104, a cathode material 106, an electrolyte 108, an anode material 110, an anode current collector 112, and a gas 114. The battery 100 can be a solid lithium ion battery or can include a solid lithium ion battery. Although not separately illustrated, the battery 100 can also include terminals and leads from the current collectors 104, 112 to the respective terminals. The battery 100 is illustrated as a single cell battery, but the same principle can be applied to an assembly including two or more cells in one battery and / or two or more batteries (e.g., a battery pack, etc.). Such a multi-battery assembly should be understood to fall within the scope of the present disclosure.

[0047] The housing 102 can include any suitable material. Generally, the housing 102 seals the battery components 104-114 from the environment. By way of example, the housing can include metals, foil pouches, polymer thin films, and the like.

[0048] Suitable current collectors for the cathode current collector 104 and the anode current collector 112 include conductive materials. By way of example, the cathode current collector can be aluminum, a form of aluminum, an aluminum alloy, nickel, a form of nickel, a nickel alloy, duplex steel, stainless steel, titanium, a form of titanium, a titanium alloy, or can include these, and the anode current collector can be copper, copper oxide, a copper alloy, nickel, nickel oxide, a nickel alloy, duplex steel, stainless steel, silver, a silver alloy, or can include these. Further, or alternatively, any current collector can be at least one material selected from the group consisting of molybdenum, titanium, zirconium, and combinations thereof, or can include the one material. The current collector is a compound containing at least one halogen atom such as Li6PS5Cl, and / or Li 10 GeP2S 12It can be brought into contact with a compound containing one sulfur atom such as this. The compound can be used as an electrolyte and / or an electrode (anode and / or cathode) material. The current collector can be perforated, the pore size can be about 500 nm or more (for example, about 500 nm to about 5 mm), and the distance between pores can be about 10 μm or more (for example, about 10 μm to about 10 mm).

[0049] The cathode material 106 is a cathode active material, for example, sulfur, a form of sulfur, a sulfide (for example, lithium titanium disulfide: LTS), an oxide (for example, M´´ 1-x M´´O2, M´ 1-w (M´´ x M´´´ y )O2, M 1-w (Mn x Ni y Co z )O2, M 1-w (Mn x Ni y Co z Al w )O2, M 1-w (Ni x Co y Al z )O2, M´ 1-w (Ni x Co y M´´ z )O2, M´ 1-w (Ni x Mn y M´´ z )O2, M´M´´M´´´2O4, M x V y O z 、M´M´´PO4, M´M´´ x M´´´ 1-xMaterials in the form of PO4 (where M′, M″, and M‴ are different metals), lithium iron phosphate, (LFP), lithium nickel manganese cobalt oxides (NMC), lithium nickel cobalt aluminum oxides (NCA), lithium cobalt oxides (LCO), lithium nickel oxides (LNO), lithium manganese oxides (LMO)), organic materials (e.g., torquxenone, torquxenone derivatives, phenoxazine, phenoxazine derivatives, phenothiazine, phenothiazine derivatives, quinone, quinone derivatives, diamine derivatives, phenazine, phenazine derivatives, quinoxaline, quinoxaline derivatives, pyrazine, pyrazine derivatives, cyclohexane, cyclohexane derivatives, triazine, triazine derivatives, melanin, melanin derivatives, dimethoxybenzene, dimethoxybenzene derivatives, cyclopropenium derivatives, amide derivatives), a form of halogen, a halide, or any combination thereof. The cathode active material can accumulate and release ions. Examples of ions include alkali metal ions (e.g., lithium ions, sodium ions, potassium ions), alkaline earth metal ions (e.g., magnesium ions, calcium ions), or amphoteric metal ions (e.g., aluminum ions, zinc ions). Among them, alkali metal ions are preferred, and lithium ions are particularly suitable for providing a high energy density. The cathode active material can be mixed with an electrolyte material and applied to a cathode current collector. The cathode contains the cathode active material.

[0050] The anode material 110 is an anode active material, e.g., lithium, sodium, potassium, magnesium, calcium, vanadium, aluminum, zinc, silicon, graphite, graphene, porous carbon, activated carbon, silicon compounds, metal sulfides (e.g., MV 0.5 Ti 0.5 S2), metal oxides (e.g., M x Ti5O12 , TiO2, TiNb2O7, Nb2O5, M x VO4, H2Ti6O 13 , M x MnBO3, M x V2O5, M x MoO4, M x Materials in the form of W2O7 (where M is a metal), lithium titanate (LTO), or any combination thereof can be included. The anode active material is not particularly limited as long as it can accumulate and release ions. Examples of ions include alkali metal ions (e.g., lithium, sodium, potassium), alkaline earth metal ions (e.g., magnesium, calcium), or amphoteric metal ions (e.g., aluminum, zinc). Among them, alkali metal ions are preferred, and lithium ions are particularly preferred for providing a high energy density. The anode active material can be mixed with the electrolyte material and can be disposed on or covering the anode current collector. Optionally, the battery can include a substrate (e.g., a current collector) that initially contains no anode active material. The anode active material can be attached to the substrate or intercalated into the substrate during the first charge of the battery. The anode material can further include an electrolyte material as described herein. The anode includes the anode material. Optionally, the battery according to an embodiment of the present disclosure does not include an anode. In those cases, the electrolyte can be disposed within the cathode and between the anode current collector and the cathode.

[0051] The electrolyte 108 is a solid electrolyte. According to an embodiment of the present disclosure, the electrolyte 108 is a polymer, glass, phosphate, fluorophosphate, carbonate, amine, borate, fluoroborate, halide, halate, oxohalide, oxides such as SiO2, TiO2, Al2O3, Y2O3, Mg2B2O5, Li2O, LiOH, Li2O2, Li2CO3, P2O5, GeO2, AlPO4, Li2Ti3O7, perovskite, antiperovskite such as Li3OBr, Li3OCl, Li2OHBr, Li2OHCl, Li1+x Al x Ti 2-x (PO4)3, Li 2+2x Zn 1-x GeO4, Li (3+x) Ge x V (1-x) O4, Li (4-x) Si (1-x) P x O4, Li 1+x+y Al x Ti 2-x Si y P 3-y O 12 , Li 1+x Al x Ge y Ti 2-x-y P3O 12 , Li 1+x+3y Al x (Ge, Ti) 2-x (Si y PO4)3, Li 14 ZnGe4O 16 , Li 4-x V x Ge x O4 and other LISICON-type electrolytes, Li7La3Zr2O 12 , Li 7-x La3Zr 2-x Nb x O 12 , L i7 La 3-x Ca x Zr 2-x Nb x O 12 , Li 6+x La3Zr 1+x Ta 1-x O 12 and other garnets, Li6PS5Cl, Li 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 , Li 10 GeP2S 12 , Li7PS6, Li7P3S 11 , Li 3.25 P 0.95 S4, Li 3+x Ge x P 1-x S4 and other sulfides, Li (4-x)Ge (1-x) P x It includes one or more of thio-LISICON type electrolytes such as S4, oxynitrides, nitrides, etc. The electrolyte can have its width and length larger than those of the current collector in order to avoid contact between the cathode and the anode.

[0052] As described in more detail below, according to an embodiment of the present disclosure, one or more electrodes and / or electrolytes include an electrosprayed organic material or polymer material. The organic / polymer (sometimes simply referred to as polymer) material has an ionic conductivity greater than 0 S / cm and less than 10 -6 S / cm or 10 -7 S / cm, and a weight percentage of the polymer material with respect to the electrolyte greater than 0 wt% and less than 5 wt% of the total weight of the polymer material and the electrolyte.

[0053] The cathode and the anode can also include an electrosprayed organic / polymer material. The battery may include a plasticizer, for example, the plasticizer described in the present specification, as part of the electrode and / or electrolyte.

[0054] The gas 114 can include an inert gas or a first gas (e.g., a non-inert gas) and / or the gas in the housing 102 after applying one or more of voltage and current to the electrochemical cell under the influence of the first gas. According to an embodiment of the present disclosure, the first or non-inert gas is not used as an active material. The first or non-inert gas can be consumed or dissolved to less than 0.01 mg per 1 mAh on average during the entire life cycle of the battery. The term "the entire life cycle of the battery" as used in the present specification is intended to mean that the life of the battery can be considered to exceed its normal service life when the battery first shows 80% of its original capacity. The gas 114 can be brought into contact with the anode active material, the cathode active material, and / or the electrolyte.

[0055] The battery 100 can be formed in the form of a button battery, a pouch cell, an alternating plate, a cylindrical battery, a jelly roll, a prismatic cell, a flow battery, etc. The battery 100 can be formed using the method described in the present specification. The electrochemical cells in the battery 200 and / or the battery 100 can substantially eliminate the liquid electrolyte. For example, the liquid electrolyte in the battery and / or the cell can be less than 1 wt%, 0.5 wt% or 0.001 wt%.

[0056] Figure 2 shows a method 200 according to an additional embodiment of the present disclosure. The method 200 includes a step of providing a housing (202), a step of providing a first electrode in the housing (204), a step of providing a solid electrolyte in contact with the first electrode and in the housing (206), a step of providing a substrate in the housing (208), a step of supplying a first non-inert gas to the housing to move the ambient gas in the housing (step 210), a step of sealing the housing (step 212), and a step of performing at least one charge and / or discharge cycle (step 214). Unless otherwise specified, the steps of the method 200 do not necessarily have to be performed in the order shown in the figure. For example, step 212 can be performed before step 210, and / or the order of step 204 and step 208 can be reversed. Other orders are also possible. Further, the exemplary method does not necessarily have to include all of the steps shown in the figure and / or can include additional steps.

[0057] During step 202, a housing, for example, housing 102, is provided.

[0058] During step 204, a first electrode (for example, a cathode) is provided. The first electrode can be an anode or a cathode. The first electrode can include an electrode active material. The first electrode can include an electrolyte material. Optionally, step 204 can also include providing a current collector.

[0059] During step 206, a solid electrolyte is provided. The solid electrolyte can be, for example, electrolyte 108.

[0060] During step 208, a substrate, for example, a current collector is provided. Optionally, step 208 can also include an electroactive electrode (e.g., anode) material. Optionally, step 208 does not include initially providing an electroactive electrode material.

[0061] During step 210, a non-inert gas (e.g., a first one) is supplied to the housing to move the ambient gas within the housing. The non-inert gas can contain at least one oxygen. By way of example, the non-inert gas can contain one or more of CO2, CO, O2, N2O, NO2, and SO2. The non-inert gas can be brought into contact with the electrodes and the electrolyte.

[0062] During step 212, the battery components (e.g., electrodes, electrolyte, current collector, etc.) are sealed. Once sealed, gas can be added, for example, via one or more ports 116, 118 shown in FIG. 1, or gas can be evacuated from within the housing.

[0063] During step 214, at least one discharge step and / or at least one charge step is / are performed. Step 214 can be performed in the presence of the non-inert gas and / or inert gas supplied during step 210. The charge and / or discharge current density can be greater than 0 mA / cm 2 and less than 0.1 mA / cm 2 during step 214.

[0064] Figures 3 to 7 show various methods 300 to 700 which are variations of method 200. Each of methods 300 to 700 includes at least one step of supplying a non-inert gas. In addition to the other advantages shown in the present specification, the use of the non-inert gas can extend the cycle life of the cell while reducing any fire accidents associated with the use.

[0065] Figure 3 shows method 300, which includes a step of providing cell components (step 302), a step of compressing the cell components (step 304), a step of supplying a non-inert gas (step 306), a step of performing at least one charge / discharge cycle (step 308), and a step of moving the generated gas using the non-inert gas (step 310).

[0066] During step 302, cell components such as a housing, an anode, a cathode, and an electrolyte as described in the present specification are provided.

[0067] During step 304, the cell components are compressed. The cell components can be compressed, for example, using a press at a stack pressure of about 10 MPa (for example, about 1 MPa to about 100 MPa). Step 304 can be used to facilitate the desired contact between the electrolyte, the anode material, and the cathode material. During step 304, the amount of stack pressure applied to the cell can be controlled to define the anode and the cathode. Advantageously, the stack pressure applied during step 304 and during similar steps described in the present specification can be made lower than the stack pressure typically applied to an electrochemical cell during the manufacture of the cell. The typical stack pressure is greater than 100 MPa. Figure 13 shows the formation of SEI between the electrolyte material and the electrode material. The formation of SEI using a non-inert gas is considered to reduce the contact loss between the electrolyte material and the electrode material without using a higher stack pressure (for example, higher than about 10 MPa) as described in the present specification.

[0068] During step 306, a (for example, first) non-inert gas is supplied into the housing provided during step 302. The non-inert gas can be a non-inert gas as described in the present specification. The non-inert gas can be used to displace the ambient gas contained or sealed within the housing. The use of the non-inert gas can add electroactive functional groups to the surface of the electrode material and / or change the chemical structure of the electrode material that may contribute to storing more energy per unit mass or area of the electrode, and / or can be used to form a solid electrolyte interface (SEI) layer during step 308.

[0069] The housing can be sealed before or after step 306. In the former case, a non-inert gas can be introduced and the ambient gas can be discharged through a port within the housing, for example, a port as described in the present specification.

[0070] During step 308, at least one discharge cycle and / or at least one charge cycle is performed. During step 308, an SEI can be formed between at least one electrode and the electrolyte. For example, the SEI can be formed between the cathode and the solid electrolyte and / or between the anode and the solid electrolyte on one or more of, for example, the anode, cathode, and electrolyte. The SEI layer is considered to reduce the interfacial resistance and / or the charge transfer resistance. The charging and / or discharging of the battery can be performed at a current density greater than 0 mA / cm 2 and less than 0.1 mA / cm 2 .

[0071] The number of charge steps and / or discharge steps can be varied depending on the anode material, non-inert gas, etc. By way of example, about 1 to about 10, or about 2 to about 50, or about 3 to about 100 charge and / or discharge cycles are performed during step 308. A similar number of charge / discharge steps can be performed during other methods described in the present specification.

[0072] During step 310, the pressure inside the housing can be reduced (e.g., up to 1 bar of approximately standard atmospheric pressure), and the gas formed during step 208 can be removed using a non-inert gas. It should be understood that not all the gas inside the housing needs to be removed during this step, or it is not necessary to remove it. The non-inert gas used during step 310 can be the same as or different from the non-inert gas used during step 306. After step 310, the battery is in a usable state.

[0073] Method 400 includes a step of providing cell components (step 402), a step of compressing the cell components (step 404), a step of supplying an inert gas (step 406), a step of performing at least one charge / discharge cycle (step 408), and a step of moving the generated gas using a non-inert gas (step 410).

[0074] Steps 402, 404, 408, and 410 can be the same as or similar to steps 302, 204, 308, and 310 described above. Method 400 is different from method 300 in steps 306 / 406. In method 400, an inert gas is supplied into the housing during step 406. Then, the cell is cycled during step 408, and the housing is purged using a non-inert gas during step 410.

[0075] Method 500 is also similar to method 300. Method 500 includes a step of providing cell components (step 502), a step of compressing the cell components (step 504), a step of supplying a non-inert gas (step 506), a step of performing at least one charge / discharge cycle (step 508), and a step of moving the generated gas using a gas (step 510).

[0076] Steps 502 to 508 can be the same as or similar to steps 302 to 308 described above. Method 500 differs from method 300 in steps 510 / 310. In method 500, an inert gas is supplied into the housing during step 510 to purge the housing. In contrast, in method 300, a non-inert gas is used to purge the housing.

[0077] Method 600 is similar to method 300, except that it includes additional steps 612 and 614, and steps 610 and 614 can include supplying an inert gas and / or a non-inert gas. As shown, method 600 can include a step of providing a cell component (step 602), a step of compressing the cell component (step 604), a step of supplying a non-inert gas (step 606), a step of performing at least one charge / discharge cycle (step 608), a step of moving the generated gas using a gas (step 610), a step of performing at least one additional charge / discharge cycle (612), and a step of moving the generated gas using a gas (step 614) during step 612. In an alternative method, step 606 can include supplying an inert gas.

[0078] Steps 602 to 608 can be the same as or similar to steps 302 to 308 described above. During step 610, an inert gas and / or a non-inert gas can be supplied to the housing to move the gas generated during step 608. The inert gas and / or the non-inert gas can be as described in the present specification.

[0079] Step 612 can be the same as or similar to step 608. For example, step 612 can be greater than 0 mA / cm 2 and less than 0.1 mA / cm 2It can include at least one discharge cycle and / or at least one charge cycle at a current density smaller than. Charging / discharging can be repeated as described in the present specification.

[0080] Finally, during step 614, the housing can be purged with a gas containing a non-inert gas or an inert gas as described in the present specification. Step 614 can be the same as or similar to, for example, step 310 or step 510. The gases used in step 610 and step 614 can be the same or can be made different. As an example, the gas used during step 610 can be a non-inert gas, and the gas used during step 614 can be an inert gas.

[0081] FIG. 14 shows another method 1400 according to an embodiment of the present disclosure. Method 1400 includes a step of providing a housing (step 1402), a step of providing a first electrode in the housing (step 1404), a step of providing a solid electrolyte in contact with the first electrode and within the housing (step 1406), a step of supplying a first gas to the housing (step 1408), a step of sealing the housing (step 1410), a step of applying one or more of a voltage and a current to the electrochemical cell under the influence of the first gas (step 1412), and a step of removing at least 90% by mass (based on the original mass) of the gas existing within the housing after the applying step (step 1414).

[0082] Steps 1402 to 1406 can be the same as or similar to steps 202 to 206 described above.

[0083] Step 1408 includes supplying a first gas to the housing to move ambient gas within the housing. According to an embodiment of the present disclosure, the gas supplied during step 1408 does not substantially form a portion of the electrodes. According to an embodiment of the method, the cell does not generate a significant amount of gas during operation. If the first gas includes a non-inert gas, step 1408 can be the same as or similar to step 210 described above.

[0084] Step 1410 can be the same as or similar to step 212.

[0085] During step 1412, one or more of a current and a voltage are applied to an electrochemical cell (e.g., across an electrode or respective current collectors) under the influence of the first gas. A portion of the gas within the housing after step 1412 (e.g., greater than 90 wt%, greater than 95 wt%, greater than 97 wt%, greater than 99 wt%) can be removed from the housing during step 1414. Similar to above, the mass percent of the gas removed can be based on the mass of the gas prior to the step of removing the gas. For example, the gas existing within the housing after step 1412 can be removed using a second gas and / or a vacuum source. According to an embodiment of the present disclosure, the battery or cell does not generate a significant amount of gas during operation. Thus, the battery can be maintained at a reduced stack pressure. The second gas can be different from the first gas and can be, for example, an inert gas or another non-inert gas. The first gas can include oxygen atoms and / or sulfur atoms as described herein in relation to the first gas and / or non-inert gas.

[0086] According to an embodiment of the present disclosure, method 1400 can additionally include forming a solid layer on the surface of the electrolyte, on one or more of the first and second electrodes, and / or between the two electrodes and / or between the electrolytes during the applying step. An exemplary method can include at least one additional step of applying a voltage and / or current to an electrochemical cell to form a solid layer before the removing step. Further, method 1400 can include spraying a solution by electrospraying to form one or more of the first electrode, the electrolyte, and the second electrode using techniques as described herein. Method 1400 can additionally include compressing cell components including the first electrode and the solid electrolyte at a reduced stack pressure lower than 100 MPa, preferably lower than 50 MPa, more preferably lower than 10 MPa.

[0087] Figure 7 is a flowchart of a method of manufacturing an electrochemical cell according to another exemplary embodiment. Method 700 includes providing a substrate (step 702), generating a solution (step 703), electrospraying the solution onto the substrate (step 706), drying the solution (step 708), providing cell components (step 710), and compressing the cell components (step 712). Method 700 can be used to form a cell including an independent electrolyte.

[0088] Step 702 includes providing a substrate onto which the solution is electrosprayed. Exemplary substrates can include a current collector, an electrode, an electrolyte, or any combination thereof. By way of example, the substrate can include an electrolyte and optionally an electrode and / or a current collector.

[0089] During step 704, a solution containing a polymer material is generated. The solution can include the polymer material and a suitable solvent. Exemplary solvents include one or more of methanol, ethanol, chloroform, toluene, ethyl acetate, acetonitrile, n-propanol, acetone, N,N-dimethylformamide, isopropanol, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylacetamide, tetrahydrofuran, 1,1,1,3,3,3-hexafluoro-2-propanol, 1,2-dimethoxyethane, N-methyl-2-pyrrolidone, N-methylimidazole, carbon disulfide, ethyl formate, 3-methoxypropionitrile, oxalic acid, trichloroacetic acid, trifluoroacetic acid, acetic acid, cyclohexane, diethyl ether, nitromethane, pyridine, water in any combination. The polymer material can be non-ion conductive or have low ion conductivity (e.g., conductivity higher than 0 S / cm and lower than 10 -7 S / cm), and can form part of an electrolyte and / or an electrode. The polymer material can include, for example, one or more of polycaprolactone, polyacrylic acid, polymethyl methacrylate, polytetrafluoroethylene, polyvinylidene fluoride, polyacrylonitrile, polyethylene terephthalate, polyvinyl pyrrolidone, and poly(4-vinylpyridine) in any combination. The concentration of the polymer material in the solution can be from about 0.01 wt% to about 10 wt%, or from about 0.1 wt% to about 5 wt%.

[0090] During step 706, the solution generated during step 704 can be electrosprayed onto the substrate formed during step 702.

[0091] During step 706, one or more electrospray parameters can be adjusted, such as flow rate, applied voltage, applied current, nozzle dimensions, nozzle type, distance between the tip of the nozzle and the current collector, etc. The electrospray process advantageously enables the stretching and thinning of a polymer material (e.g., non-ion conductive or low ion conductive), which not only allows for manufacturing micron-thick independent films (e.g., thicker than 5 μm) without cracking by strongly bonding the electrolyte material, but also enables coating the surface of the electrolyte material with a relatively small amount of non-ion conductive or low ion conductive polymer material compared to conventional application techniques. The benefit of having a thin (e.g., nanolayer) non-ion conductive or low ion conductive polymer material on the surface of the electrolyte material is that it serves to chemically suppress dendritic growth from the anode while maintaining the ionic conductivity of the electrolyte. The independent electrolyte can contain more than 70 wt% of the solid electrolyte, preferably more than 80 wt%, more preferably more than 90 wt%.

[0092] During step 708, the solution applied during step 706 is dried. Step 708 can be carried out at a low pressure (e.g., about 0.1 MPa to about 10 MPa) and / or in an inert gas atmosphere.

[0093] During step 710, cell components, such as a current collector, one or more electrodes, and an electrolyte, are provided within the housing. Step 710 can be the same as or similar to step 302.

[0094] During step 712, the cell components are compressed. Step 712 can be the same as or similar to step 304. Thereafter, the method of forming a battery can include additional steps, such as steps 306 - 310, steps 406 - 410, steps 506 - 510 or steps 606 - 614. The use of the electrospray process can be used with any of the methods described in connection with any of methods 300 - 600.

[0095] FIG. 8 shows a solid (also referred to herein as a solid state) electrolyte 800 according to an exemplary embodiment. The solid electrolyte 800 can include solid electrolyte particles 802 at least partially coated with a polymer material 804. The solid electrolyte can be disposed within the anode and cathode and between the anode and cathode. The solid electrolyte 800 can also be contacted, for example, with a non-inert gas 806 containing at least one oxygen atom. The thickness of the polymer material on the surface of the solid electrolyte can be greater than 0 nm and less than 100 nm, or about 1 - about 50 nm. The polymer material may not be present when the solid electrolyte is in contact with the electrode material.

[0096] FIG. 9 is a schematic diagram of a structure 900 including an electrode (e.g., an anode or a cathode) 902, a protective solid electrolyte interphase (SEI) layer 904 (e.g., electrochemically formed by a non-inert gas as described above), and a solid electrolyte 906 according to an exemplary embodiment. The SEI layer can be formed between the solid electrolyte 906 and the electrode 902 when a battery composed of the electrolyte, the electrode, and the non-inert gas is charged and / or discharged. The SEI layer can include a compound containing at least one oxygen atom. The thickness of the SEI layer can be greater than 0 nm and less than 100 nm. The SEI layer can reduce the ionic resistance and the interfacial resistance between the electrode 902 and the electrolyte 906.

[0097] Figure 10 is a graph showing the stable cycle performance of a symmetric cell containing a solid electrolyte, executed under the influence of a non-inert gas (e.g., carbon dioxide), compared to under the influence of an inert gas (e.g., argon). A battery formed according to an embodiment of the present disclosure (e.g., including a lithium metal foil, a solid electrolyte, and carbon dioxide gas) exhibits excellent cycle performance at a current density of 5 mA / cm 2 for 2,000 cycles and 500 hours, whereas a battery including a lithium metal foil, a solid electrolyte, and an inert / argon gas showed interruption at about 100 cycles within 24 hours. The solid electrolyte membrane was disposed between two lithium metal foils. Li 1.3 Al 0.3 Ti 1.7 (PO4)3 (LATP), that is, a lithium superionic conductor (LiSICON) structure was selected as the solid electrolyte material. The solid electrolyte membrane was manufactured by electrospraying an independent and solid electrolyte, polycaprolactone, and poly(ethylene oxide). The weight ratio of the electrolyte membrane including the solid electrolyte, polycaprolactone, and poly(ethylene oxide) was 95:1:4. The thickness of the electrolyte membrane was about 35 μm. The cell stack pressure was measured to be about 9 MPa. Polycaprolactone was selected as a non-ion-conductive or low-ion-conductive polymer material. Polycaprolactone was electrosprayed in the outer region of the coaxial nozzle, and a mixture of the solid electrolyte and poly(ethylene oxide) was electrosprayed in the core region in order to coat the mixture of the solid electrolyte and poly(ethylene oxide) with an ultrathin nanomembrane containing polycaprolactone.

[0098] Figure 11 is a graph showing the improvement of the interfacial ion conductivity of a battery containing a lithium metal foil and a solid electrolyte pre-formed under different partial pressures of a non-inert gas. The conductivity was measured after 10 cycles of charging and discharging at a current density of 0.01 mA / cm 2 . The solid electrolyte membrane was disposed between two lithium metal foils. Li 1.3 Al 0.3 Ti 1.7(PO4)3(LATP), that is, a lithium superionic conductor (LiSICON) structure was selected as the solid electrolyte material. The solid electrolyte membrane was manufactured by electrospraying an independent and solid electrolyte, polycaprolactone, and poly(ethylene oxide). The weight ratio of the electrolyte membrane containing the solid electrolyte, polycaprolactone, and poly(ethylene oxide) was 95:1:4. The electrolyte or electrolyte membrane according to the present disclosure can include at least 70 wt% of an electrolyte material, 10 wt% or less of a non-conductive or low-conductive polymer material, such as polycaprolactone, and 10 wt% or less of a conductive polymer material, such as poly(ethylene oxide). The thickness of the electrolyte membrane was about 35 μm. The cell stack pressure was measured to be about 9 MPa. Polycaprolactone was selected as a non-ion conductive or low-ion conductive polymer material. Polycaprolactone was electrosprayed into the outer region of the coaxial nozzle, and a mixture of the solid electrolyte and poly(ethylene oxide) was electrosprayed into the core region. Nitrous oxide and carbon dioxide were selected as non-inert gases. The high partial pressure of the non-inert gas showed a high conductivity of the electrolyte at 25°C. The conductivity at 25°C reached higher than about 10 -3 S / cm. The conductivity at 25°C under argon gas was measured to be about 7×10 -6 S / cm.

[0099] Figure 12 is a graph showing the improvement of the interfacial ion conductivity of a battery containing a lithium metal foil and a solid electrolyte under a carbon dioxide partial pressure of 0.2 bar with respect to the number of cycles. The conductivity of the battery was measured after each cycle was operated at a current density of 0.01 mA / cm 2 . The solid electrolyte membrane was placed between two lithium metal foils. Li 1.3 Al 0.3 Ti 1.7(PO4)3(LATP), that is, a lithium superionic conductor (LiSICON) structure was selected as the solid electrolyte material. The solid electrolyte membrane was fabricated by electrospraying an independent and solid electrolyte, polycaprolactone, and poly(ethylene oxide). The weight ratio of the electrolyte membrane containing the solid electrolyte, polycaprolactone, and poly(ethylene oxide) was 95:1:4. The thickness of the electrolyte membrane was approximately 35 μm. The cell stack pressure was measured to be approximately 9 MPa. Polycaprolactone was selected as a non-ion conductive or low-ion conductive polymer material. Polycaprolactone was electrosprayed into the outer region of the coaxial nozzle, and a mixture of the solid electrolyte and poly(ethylene oxide) was electrosprayed into the core region. Carbon dioxide was selected as the non-inert gas. The conductivity at 25 °C reached approximately 10 -3 S / cm after the 100th cycle under a carbon dioxide partial pressure of 0.2 bar. The conductivity at 25 °C under argon gas was measured to be approximately 7×10 -6 S / cm.

[0100] This disclosure has described the use of various features and methods for manufacturing batteries and cells. It should be understood that any combination of such features and methods is within the scope of this disclosure. For example, the embodiments described regarding the use of organic materials for cathode active materials may be modified to be manufactured under a non-inert gas atmosphere, and such modifications are intended to be within the scope of this disclosure. Other substitutions and combinations that utilize one or more of the features / methods described herein are also possible, and such substitutions and combinations are also considered to be part of this disclosure without specifically listing them.

[0101] Despite the embodiments described above and shown in the accompanying drawings, various changes and incorporations to those embodiments are intended and considered to be within the scope of this disclosure.

[0102] As used in this specification with respect to numerical ranges, the terms "substantially", "about", "approximately" and similar terms, unless otherwise specified, generally mean ±10% of the disclosed value. When used in this specification with respect to structural features (e.g., to describe shape, size, orientation, direction, relative position, etc.), the terms "substantially", "about", "approximately" and similar terms are intended to cover minor variations in the structure that may result from, for example, the manufacturing or assembly process, and are intended to have a broad meaning consistent with the syntax generally recognized by those of ordinary skill in the art relevant to this disclosure. Accordingly, those terms should be construed to indicate that minor or insignificant changes or modifications to the subject matter of the invention as described and claimed are within the scope of this disclosure as set forth in the appended claims.

[0103] The term "exemplary" and variations thereof, as used in this specification to describe various embodiments, are intended to indicate that such embodiments are intended to be examples of possible embodiments, representative examples, or illustrations of possible embodiments (and such terms are not intended to imply that such embodiments are necessarily special or the best examples).

[0104] References in this specification to the position of elements (e.g., "top", "bottom", "above", "below") are used merely to describe the orientation of the various elements in the figures. It should be noted that the orientation of the various elements may vary according to other exemplary embodiments, and such variations are intended to be encompassed by this disclosure.

[0105] As described above, the figures and the description can illustrate the specific order of method steps, but such an order of steps may be different from that shown and described, unless specified otherwise. Also, two or more steps may be performed simultaneously or partially simultaneously, unless specified otherwise. Further, one or more steps can be repeated before the next step.

[0106] It is important to note that any element disclosed in one embodiment can be incorporated into any other embodiment described in this specification or used in conjunction with any other embodiment. Although only one example of an element from one embodiment that can be incorporated into another embodiment or used in another embodiment has been described above, it should be understood that other elements of the various embodiments may be incorporated into any of the other embodiments disclosed in this specification or used in conjunction with any of such embodiments.

Claims

1. A method of forming an electrochemical cell, wherein the electrochemical cell does not generate a significant amount of gas during operation, comprising the steps of providing a housing, providing a first electrode within the housing, providing a solid electrolyte in contact with the first electrode and within the housing, supplying a first gas to the housing to move the ambient gas within the housing, wherein the gas is not an electrode, sealing the housing, applying one or more of voltage and current to the electrochemical cell under the influence of the first gas, forming a solid layer on the surface of the solid electrolyte, and on one or more of the first electrode and the second electrode, and / or between the two electrodes, and / or between the solid electrolytes, during the applying step under the influence of the first gas, removing at least 90% by mass of the gas present within the housing after the applying step, The first gas is CO ２ , CO, O ２ , N ２ O, NO ２ and SO ２ or one or more of S ８ , COS, CS ２ , SF ６ , H ２ S, SO ２ , CH ４ S and C ２ H ６ S, or a method comprising one or more of them.

2. The method according to claim 1, further comprising the step of supplying a second gas to the housing to move at least a portion of the first gas within the housing and to remove at least a portion of the gas generated during the applying step, prior to the removing step.

3. The method according to claim 2, further comprising performing at least one additional step of applying one or more of voltage and current to the electrochemical cell under the influence of the first gas to form the solid layer between the solid electrolyte and one or more of the first electrode and the second electrode, prior to the removing step.

4. The method according to claim 2, wherein the second gas is different from the first gas.

5. The method according to claim 1, wherein the solid electrolyte contains at least one oxygen atom or at least one sulfur atom.

6. The method according to claim 1, wherein the solid layer contains at least one oxygen atom or at least one sulfur atom.

7. The method according to claim 1, further comprising the step of electrospraying a solution to form one or more of the first electrode, the solid electrolyte, and the second electrode.

8. The method according to claim 1, further comprising the step of compressing the cell component including the first electrode and the solid electrolyte at a stack pressure lower than 100 MPa.

9. An electrochemical cell formed according to the method of claim 1.

10. The first electrode includes a first current collector, the second electrode includes a second current collector, and one or more of the first and second current collectors include an alloy having at least one material selected from the group consisting of molybdenum, titanium, zirconium, and combinations thereof. The electrochemical cell according to claim 9.

11. The electrochemical cell according to claim 9, substantially free of a liquid electrolyte.

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