Method of depositing a layer of an electrochemical half-cell or cell, an electrochemical half-cell or cell comprising such a layer and method of producing an electrochemical half-cell or cell

Abstract

The invention relates to a method of depositing a layer of an electrochemical half-cell or cell, the layer being selected from a group comprising a layer of an electrode, a layer of a solid electrolyte or a protective layer, wherein the method comprises the following steps: (a) producing a mixture comprising: - at least one material which constitutes the solid electrolyte or at least one material which constitutes the electrode or a material which constitutes the protective layer or a mixture of at least one material which constitutes the electrode and at least one material which constitutes the solid electrolyte, - at least one binding agent, and - at least one volatile solvent which is chemically inert with respect to components used; and (b) spraying the mixture produced in step (a) on a solid substrate by means of a spraying device, using an inert gas under a pressure falling within the range of 0.1 to 2 bar, to deposit the layer of an electrochemical half-cell or cell. The invention further relates to a method of producing an electrochemical half-cell or cell wherein at least one layer is deposited by the above-defined method, and to an electrochemical half-cell or cell comprising at least one layer deposited by the above-defined method.

Description

[0001] Method of depositing a layer of an electrochemical half-cell or cell, an electrochemical half-cell or cell comprising such a layer and method of producing an electrochemical half-cell or cell

[0002] The invention relates to a method of depositing a layer of an electrochemical half-cell or cell, such as an electrode layer, a solid electrolyte layer or a protective layer. The invention also relates to an electrochemical half-cell or cell comprising at least one layer deposited by the method according to the invention. The invention further relates to a method of producing an electrochemical half-cell or cell, wherein at least one layer is deposited by the method of depositing a layer according to the invention.

[0003] From the publication Printable, high-performance solid-state electrolyte films WEIWEI PING et al. SCIENCE ADVANCES 6, 47 (2020) (US provisional patent application 62 / 849578) there is known a method for depositing solid-state electrolyte films in which a step of high-temperature (800°C) annealing is used to crystallize appropriate compounds. The authors suggest using their technique for the production of many layers, with intermediate steps of annealing each layer. In the described method, precursors of individual cell elements are used instead of ready-made materials.

[0004] The publications C.-W. Ahn et al. “Microstructure and Ionic Conductivity in LivLasZriOii Film Prepared by Aerosol Deposition Method”, J. Electrochem. Soc., vol. 162, no. 1, p. A60, Nov. 2014, Icpyo Kim et al. “Electrochemical properties of an as-deposited LiFePCU thin film electrode prepared by aerosol deposition”, Journal of Power Sources 244 (2013) 646- 651 and Jong-Jin Choi et al. “Microstructural evolution of YSZ electrolyte aerosol -deposited on porous NiO-YSZ”, Journal of the European Ceramic Society, Vol. 32, no. 12, September 2012, pp. 3249-3254 describe the use of aerosol deposition (AD) technique for applying an electrode material film (LFP) as well as a solid electrolyte film (LLZ) on a solid metallic surface (and NiO-YSZ). The carrier gas used in the methods described in the cited publications is air or oxygen. The process of depositing is carried out in a chamber under reduced pressure (1 Torr). The half-cell produced is subjected to the process of vacuum drying in order to remove water. In the methods described, neither an additional binding polymer nor a liquid medium is used.

[0005] The publications R. Inada et al. “Properties of garnet-type LisLasZrTaOn solid electrolyte fdms fabricated by aerosol deposition method”, Progress in Natural Science: Materials International, vol. 27, no. 3, pp. 350-355, June 2017 and R. Inada et al. “Characterization of as-deposited LUTisOii thin fdm electrode prepared by aerosol deposition method”, Journal of Power Sources, vol. 253, pp. 181-186, May 2014, describe a method of powder deposition of electrode or solid electrolyte material on a solid surface (glass or metal), which can be used for the production of multilayer systems. In this method, compressed carrier gas N2 is used, which collects dry powder (active material or electrolyte) and transports it to a spraying chamber where it is deposited on a given surface. Multilayer systems obtained by means of this technique do not have however appropriate mechanical resistance.

[0006] The purpose of the invention was to develop a simple and universal method of depositing electrode, solid electrolyte and protective layers, which would make it possible to obtain multilayer systems characterized by elasticity and mechanical resistance suitable for use in electrochemical half-cells and cells.

[0007] The invention relates to a method of depositing a layer of an electrochemical half-cell or cell, the layer being selected from a group comprising a layer of an electrode, a layer of a solid electrolyte or a protective layer, wherein the method comprises the following steps:

[0008] (a) producing a mixture containing:

[0009] - at least one material which constitutes the solid electrolyte or at least one material which constitutes the electrode or a material which constitutes the protective layer or a mixture of at least one material which constitutes the electrode and at least one material which constitutes the solid electrolyte,

[0010] - at least one binding agent, and

[0011] - at least one volatile solvent which is chemically inert with respect to components used; and

[0012] (b) spraying the mixture produced in step (a) on a solid substrate by means of a spraying device, using an inert gas under a pressure falling within the range of 0.1 to 2 bar, to deposit the layer of an electrochemical half-cell or cell.

[0013] Preferably, the mixture produced in step (a) is stirred before step (b).

[0014] Preferably, the method additionally comprises step (c) of drying or annealing the layer deposited in step (b).

[0015] Preferably, steps (a) and (b), and optionally (c), are repeated in order to deposit another layer on the layer deposited previously.

[0016] Preferably, steps (a) and (b), and optionally (c), are repeated from 1 to 6 times. Preferably, the method additionally comprises step (d) of pressing the deposited layer before depositing another layer, and / or pressing all layers together.

[0017] Preferably, a material selected from a group comprising the following is used as the material which constitutes the electrode:

[0018] (a) intercalation compounds, such as layered compounds, olivines, spinels and carbon compounds;

[0019] (b) conversion compounds;

[0020] (c) dopants of the intercalation compounds with other ions; and

[0021] (d) a composite of any compound indicated in point (a), (b) and (c) with another compound indicated in point (a), (b) and (c) and / or with another organic or inorganic compound.

[0022] Preferably, a spinel or a composite thereof with the material which constitutes the solid electrolyte, and more preferably LUTisOii or its composite with lithium argyrodite, is used as the material which constitutes the electrode.

[0023] Preferably, the material which constitutes the electrode is or the materials which constitute the electrode are or the mixture of at least one material which constitutes the electrode and at least one material which constitutes the solid electrolyte is used in an amount in the range of 70% to 99% by weight relative to the total mass of the mixture produced in step (a).

[0024] Preferably, at least one electrical conductor, and more preferably conductive carbon, is added to the material which constitutes the electrode.

[0025] Preferably, the electrical conductor is or the electrical conductors are added in an amount of 25% by weight or less relative to the total mass of the mixture produced in step (a).

[0026] Preferably, a chemical compound selected from a group of compounds comprising argyrodites, phosphates, thiophosphates, titanates, garnets, perovskites, sulphides, NASICON, antiperovskites, oxides, chlorides, ion-conducting polymers, and analogs of the above-indicated compounds, and dopants of the above-indicated compounds with other elements, and composites of the above-indicated compounds, is used as the material which constitutes the solid electrolyte.

[0027] Preferably, the argyrodites or the thiophosphates are used as the chemical compound.

[0028] Preferably, LiePSsX wherein X is an atom or atoms of halides such as Cl, Br or I is used as the argyrodites, and LisPS4 is preferably used as the thiophosphates. Preferably, the material which constitutes the solid electrolyte is or the materials which constitute the solid electrolyte are used in an amount in the range of 70% to 99% by weight relative to the total mass of the mixture produced in step (a).

[0029] Preferably, a conductive or non-conductive polymer soluble in the used solvent, and more preferably acrylonitrile-butadiene rubber, is used as the binding agent.

[0030] Preferably, the binding agent is or the binding agents are used in an amount in the range of 1% to 15% by weight relative to the total mass of the mixture produced in step (a).

[0031] Preferably, non-polar and polar solvent, and more preferably xylene, toluene, benzene, hexane, ethanol, isopropanol, methanol, iV-methylpyrrolidone or their mixture, is used as the volatile solvent which is chemically inert with respect to components used.

[0032] Preferably, in step (b), the spraying device having a nozzle with an orifice width falling within the range of 0.1 mm to 3 mm is used.

[0033] Preferably, the solid substrate is a current collector, an / the layer of an electrode, a / the layer of a solid electrolyte or a / the protective layer.

[0034] Preferably, the material which constitutes the solid electrolyte or the material which constitutes the electrode is used as the material which constitutes the protective layer.

[0035] Furthermore, the invention relates to a method of producing an electrochemical half-cell or cell that comprises deposition of subsequent layers of the electrochemical half-cell or cell on a current collector, wherein at least one layer from one or more electrode layers, one or more solid electrolyte layers and one or more protective layers is deposited by the abovedefined method.

[0036] Preferably, the method of producing an electrochemical half-cell or cell additionally comprises a step of pressing the deposited layer before depositing another layer.

[0037] Preferably, the method of producing an electrochemical half-cell or cell additionally comprises a step of pressing the produced electrochemical half-cell or cell.

[0038] The invention also relates to an electrochemical half-cell or cell comprising at least one layer deposited by the above-defined method of depositing layers.

[0039] Preferably, the electrochemical half-cell or cell further comprises an additive of a liquid electrolyte. The developed method of depositing a layer of an electrochemical half-cell or cell is simple, quick and effective. It consists in depositing thin layers from suspensions or solutions by means of a spraying nozzle using any carrier gas which is chemically inert with respect to the deposited layers (materials, compounds). The use of a binding agent makes it possible to obtain layers that are resistant to mechanical bending and that have good adhesion. The method according to the invention is universal in terms of materials used. It can use any known electrode material from which the suspension or the solution in a liquid medium can be made, and any known electrolytes (ion-conducting membranes, e.g. ceramic, polymeric, composite) and binding agents (e.g. polymers). With the development of technologies related to lithium-ion cells and other ion-conducting metals (Na+, Mg2+, Al3+etc.) for use in energy storage devices, the developed technique may bring benefits wherever, technologically, the deposition of subsequent thin layers by the tape casting technique (doctor blade casting) would be difficult. The method according to the invention avoids the necessity of using high temperatures, and commonly available current collectors (copper and aluminium ones) can be used. The method according to the invention is suitable for depositing layers of various thickness. It is possible to deposit intermediate layers (e.g. a double layer of different solid electrolytes or protective layers on electrodes). It is also possible to use pressing between depositing each layer or after depositing all layers.

[0040] A schematic diagram of the method of depositing layers according to the invention and the results of tests of the properties of layers deposited by the method according to the invention are presented in the drawing, wherein:

[0041] Fig. 1 shows the schematic diagram of the method according to the invention.

[0042] Fig. 2 A) shows a photograph of an electrode layer based on LTO, sprayed by the method according to the invention, and Fig. 2 B) shows a photograph of an LTO|LPSC half-cell with partially exposed electrode layer based on LTO, wherein both layers have been produced by the method according to the invention.

[0043] Fig. 3 A) shows a comparison of cycles of a cell with an electrode layer based on LTO, deposited by a classical method and of cells with an electrode layer based on LTO, deposited by the method according to the invention, Fig. 3 B) shows a graph illustrating the capacity drop of the tested cells after 50 cycles, and Fig. 3 C) shows a graph illustrating the cycling stability of the tested cells. Fig. 4 shows a graph of specific conductivity as the function of temperature for a layer of a solid electrolyte based on LPSC, obtained by the method according to the invention and for a LPSC pellet obtained by a classical method, and a schematic diagram of a measurement cell for the tests of ionic conductivity: A) in the case of a solid electrolyte (SE) pressed into a pellet and B) in the case of a solid electrolyte (SE) layer sprayed on a measurement collector by the method according to the invention.

[0044] Fig. 5 shows SEM images of an LTO-LPSC (1: 1) / LPSC half-cell after pressing (magnification lOOOx): A) top view and B) a cross-section of the cell.

[0045] Fig. 6 shows potentiometric curves of the first cycle of cells with a solid electrolyte in comparison with a standard LTO cell with LP30 liquid electrolyte.

[0046] Fig. 7. shows potentiometric curves of the first cycle of hybrid cells in comparison with a standard LTO cell with LP30 liquid electrolyte.

[0047] Below is presented a detailed description of the invention and examples illustrating it.

[0048] The first step of the method (step (a)) consists generally in producing a mixture (a suspension or solution, preferably a suspension) comprising components that form a layer of an electrochemical half-cell or cell and a volatile solvent which is chemically inert with respect to components used. The type of components depends on the type of layer to be deposited. In the case of depositing a layer of an electrode, the first component is a material which constitutes the electrode (positive or negative) or a mixture of such a material with a material which constitutes a solid electrolyte, in the case of depositing a layer of a solid electrolyte - a material which constitutes the solid electrolyte, whereas in the case of depositing a protective layer - a material which constitutes the protective layer. In the case of depositing the protective layer, the material which constitutes the electrode or the material which constitutes the solid electrolyte can be used as the material for such a layer. Considering the fact that the method according to the invention has been successfully used for depositing various layers (a layer of both positive and negative electrodes and a layer of a solid electrolyte), the inventors have established that the method is suitable for depositing layers of any electrode materials and any solid electrolytes known in the art and commonly used in electrochemical half-cells and cells due to their similar physical and chemical properties.

[0049] Therefore, in the case of depositing the layer of an electrode, in the method according to the invention, the following are used as the materials which constitute the electrode (positive or negative): 1) intercalation compounds selected from a group comprising the following compounds:

[0050] (a) layered compounds selected from a group comprising compounds such as: LixNi(a)Mn(b)Co(c)O2, wherein x > 1 and a+b+c is in the range of 0.9 to 1 (NMC), LixNi(a)Co(b)Al(c)O2 wherein x > 1 and a+b+c is in the range of 0.9 to 1 (NCA), LiMcC . wherein Me is a transition metal (e.g. LiCoCL, LiNiCh, LiMnCL),

[0051] (b) olivines selected from a group comprising compounds such as: LiFcPCL (LFP), LMnPCU, mixed LFcaMribPCU (LFMP, wherein a + b = 1),

[0052] (c) spinels selected from a group comprising compounds such as: LUTisO^ (LTO), LiM CU (LMO), mixed LiMnaNibO4 (LMNO) wherein a + b = 2;

[0053] (d) carbon compounds; and

[0054] 2) conversion compounds, such as sulphur, silicon, tin, silver.

[0055] Dopants of the intercalation compounds with other ions, for example metal ions, can also be used as the material which constitutes the electrode.

[0056] Moreover, the material which constitutes the electrode may be a composite of any compound indicated above (a compound from the intercalation compounds or a compound from the conversion compounds or a dopant from the dopants of the intercalation compounds) with another compound which constitutes the electrode (a compound from the intercalation compounds or a compound from the conversion compounds or a dopant from the dopants of the intercalation compounds) and / or with another organic or inorganic compound, e.g. a composite of various materials which constitute the electrode, a composite of the material which constitutes the electrode and the material which constitutes the solid electrolyte, a composite of the material which constitutes the electrode and carbon, or a composite of the material which constitutes the electrode and a conductive polymer. In this field, commonly used are, for example, composites of carbon and Si (or another conversion compound), composites of carbon and LiFePCU, a composite of NMC and LiNbOs (which forms a protective layer), a composite of LMO and ceramic oxides (also forming a protective layer), a composite of NMC and Li2MnOs, a composite of LiMnPO4 and LiFePO4 and carbon, and a composite of NMC and LiFePO4 (which is an electroactive composite having better operating parameters).

[0057] Preferably, the material which constitutes the electrode is a compound selected from a group of the spinels or their composites with the material which constitutes the solid electrolyte, more preferably LUTisOii or its composite with lithium argyrodite, such as LiyPSe or LiePSsX, wherein X is an atom or atoms of halides, such as Cl, Br or I.

[0058] In the case of depositing the layer of the electrode, more than one material which constitutes the electrode can be used, e.g. two or three different materials in a mixture. However, preferably one type of material which constitutes the electrode is used.

[0059] It is also possible to use a mixture of at least one material which constitutes the electrode with at least one material which constitutes the solid electrolyte, which is produced by the simple mixing of the indicated materials. According to literature, it is preferably a two- component or three-component mixture.

[0060] In the case of depositing the layer of a solid electrolyte, the material which constitutes the solid electrolyte is a chemical compound selected from a group of compounds comprising: argyrodites (e.g. LiyPSe, LiePSsX, wherein X is an atom or atoms of halides, such as Cl, Br or I), phosphates (e.g. LLPCh. Lii+xAlxTi2-x(PO4)3X(LATP), wherein x is the number of moles per mole of the entire compound and amounts to 0.3 < x < 0.5 ), thiophosphates (e.g. LisPS4, U7P3S11), titanates, garnets (e.g. LasLivZnO (LLZO)), perovskites (e.g. La2 / 3-xLi3XTiO3 (LLTO), wherein x is the number of moles per mole of the entire compound and amounts to 0 to 0.17), sulphides (e.g. LiiS-PiSs, Li IOGCPIS 12 (LGPS)), NAS ICON ((Na) Super Ionic CONductor) (e.g. Lii+xAlxGe2-x(PO4)3 (LAGP), wherein x is the number of moles per mole of the entire compound and amounts to 0 < x < 0.65), antiperovskites (e.g. LLOX, wherein X is one or more halides), oxides, chlorides, ion-conductive polymers (e.g. polyethylene oxide) with LiTFSI), and analogs of the above- specified compounds, and dopants of the above- specified compounds with other elements, and composites of the above- specified compounds.

[0061] Preferably, the argyrodites and the thiophosphates are used as the chemical compound, and preferably LiePSsX (wherein X is an atom or atoms of halides, such as Cl, Br or I) is used as the argyrodites, and Li3PS4 - as the thiophosphates.

[0062] In the case of depositing the layer of a solid electrolyte, more than one material which constitutes the solid electrolyte can be used, e.g. two or three different materials in a mixture. However, preferably one type of material which constitutes the solid electrolyte is used.

[0063] The necessary condition when selecting layer components is inertness of a solvent with respect to components used, and in the case of components forming a solid electrolyte layer, additionally, low grain boundary resistance and stability with respect to electrode materials. Additionally, in the case of depositing a layer of a solid electrolyte on a layer of an electrode, i.e. when producing an electrochemical half-cell or cell, the electrochemical stability of materials in the same electrochemical window should be considered.

[0064] In the case of depositing the layer of an electrode, the material which constitutes the electrode is or the materials which constitute the electrode are or the mixture of at least one material which constitutes the electrode and at least one material which constitutes the solid electrolyte is used in an amount of 70% to 99% by weight relative to the total mass of the mixture produced in step (a).

[0065] In the case of depositing the layer of a solid electrolyte, the material which constitutes the solid electrolyte is or the materials which constitute the solid electrolyte are also used in an amount of 70% to 99% by weight relative to the total mass of the mixture produced in step (a).

[0066] Regardless of the type of deposited layer, the second important component of the mixture produced in step (a) is a binding agent. During tests, the criteria for the assessment of suitability of biding agents included chemical inertness with respect to the remaining components, chemical stability in the assumed electrochemical window, mechanical resistance of the produced layer, adhesion to a substrate, solubility in a solvent used and formation of a stable suspension with the solvent. It results from the tests carried out that conductive or non-conductive polymers soluble in the solvent used are suitable as the binding agents, namely acrylonitrile -butadiene rubber (NBR), poly(styrene-co-butadiene- co-styrene) copolymer (SBS), poly(methyl methacrylate) (PMMA), poly(acrylonitrile-co- butadiene) copolymer (PAB), poly(acrylic acid) (PAA), poly(ethylene-co-vinyl acetate) copolymer (PEcVA), poly(styrene-co-ethylene-co-butadiene-co-styrene) copolymer (SEBS), poly(ethylene-co-(acrylic acid)) copolymer (PEAA), poly(tetrafluoroethylene) (PTFE), poly(vinylidene fluoride) (PVDF), poly(vinylidene fluoride-co- hexafluoropropylene) copolymer (PVDF-HFP), poly(ethylene oxide) copolymer (PEO), lithium carboxymethyl cellulose (CMC), polyaniline (PANI) and others. The preferred binding agent is acrylonitrile-butadiene rubber (NBR). A mixture including two or more of the above-mentioned agents can be used. However, preferably one type of binding agent is used.

[0067] The binding agent is or the binding agents are used in an amount of 1% to 15% by weight relative to the total mass of the mixture produced in step (a). The content of the binding agent depends on the desired mechanical properties and on the nature of the solid material and on the effect of the binding agent on the electrochemical results (too small amount results in a poor adhesion of a layer, too large amount has a negative effect on ion and / or electron conductivity).

[0068] Another component of the mixture produced in step (a) is a solvent. When selecting a suitable solvent, the basic condition is its chemical inertness with respect to the remaining components, easy evaporation at a reasonable temperature and ability to dissolve or form a stable suspension with the binding agent. In the case of a solid electrolyte, it is optionally possible to use a solvent in which the electrolyte recrystallizes after spraying on the desired surface. In the method according to the invention, both polar and non-polar solvents proved to be suitable for use, such as:

[0069] - polar protic: ethanol, methanol, isopropanol, n-propanol, n-butanol, ammonia, formic acid, water;

[0070] - polar aprotic: acetone, acetonitrile, dichloromethane (DCM), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), ethyl acetate, tetrahydrofuran (THF), dimethyl carbonate, propylene carbonate, ethyl propionate, N-methylpyrrolidone, furan, furfural, N- methylformamide, 1,2-dimethoxyethane (DME), dimethylacetamide (DMA);

[0071] - non-polar: xylene, hexane, cyclohexane, benzene, toluene, diethyl ether, dioxane, chloroform, tetrachloromethane, pentane, cyclopentane.

[0072] A mixture of the above-indicated compounds can also be used as the solvent.

[0073] Preferably, xylene, toluene, benzene, hexane, ethanol, isopropanol, methanol or N- methylpyrrolidone or their mixture is used.

[0074] In the case of producing the layer of an electrode, when a non-conductive polymer is used as the biding agent, an electrical conductor, such as conductive carbon (e.g. conductive black carbon, carbon black, carbon nanotubes, carbon fibres, graphene, graphene oxide, etc.) is additionally added to components forming the electrode layer. A mixture containing two or more of the above-specified electrical conductors can also be used. However, preferably one type of conductor is used.

[0075] The electrical conductor is or the electrical conductors are added to the components forming electrode layer in an amount of 25% by weight or less relative to the total mass of the mixture produced in step (a). When selecting individual components of the mixture to be sprayed, one should remember that it is necessary, first of all, to ensure that individual components are chemically inert with respect to each other.

[0076] After step (a), the mixture is preferably stirred before step (b).

[0077] Stirring is carried out, after adding the solvent, for a time in the range from a few minutes to even several dozen hours until an even dispersion of all components is obtained. The time of stirring depends on the used stirring apparatus and its efficiency. It is possible to use e.g. an ultrasonic stirrer, a magnetic stirrer, a mechanical stirrer, a mixer. The decisive parameters that determine the time of stirring are porosity, morphology, wettability and the mass of the used components of the mixture. For example, in the case of using the mechanical stirrer, the time of stirring is about 8-12 hours.

[0078] The next step (step (b)) is depositing (spraying) an appropriate layer of an electrochemical half-cell or cell on a solid substrate by spraying the mixture produced in step (a) by means of a spraying device. The spraying device to be used can be an aerograph or a larger device for spraying (painting) (e.g. used for painting walls or covering car parts with lacquer). Depending on the scale of the process, pressure and grain size of the sprayed material, the spraying device having a nozzle with an orifice width falling within the range of 0.1 to 3 mm is used. An inert gas under a pressure in the range of 0.1 to 2 bar is used for spraying. The minimum and maximum pressure of the used gas depends on such parameters as the density and viscosity of a suspension and grain size of the sprayed substance. The lower the pressure, the more liquid carrier phase reaches the surface subjected to deposition and the evaporation process takes place after deposition. With the increase of the deposition pressure, the content of the liquid phase in the deposited layer decreases. As mentioned above, any carrier gas that is chemically inert with respect to the deposited layers (materials and compounds), e.g. argon, can be used. Selection of the nozzle shape, orifice size and distance from the substrate depends on the used materials and the size and shape of the surface to be sprayed. In the case of small laboratory samples (layers not exceeding 10 x 10 cm) a round nozzle is used.

[0079] A schematic diagram of spraying layers by the method according to the invention is presented in Fig. 1, wherein the arrow marked with number 1 indicates the supply of an inert gas, and the arrow marked with number 2 - supply of a suspension of a material which constitutes an electrode or a material which constitutes a solid electrolyte or a material which constitutes a protective layer. After step (b) the obtained layer can be subjected to drying or annealing (step (c)) in order to accelerate the process.

[0080] The drying temperature depends on the used components, mainly on the used binding polymer and on the solvent volatility. Its minimum value is determined by the evaporation temperature of the solvent (in the case of vacuum drying, it can be lower). The maximum value of the drying temperature depends on the thermal stability of the components used (the most sensitive is the binding polymer). The used materials also determine the drying conditions. If one of the components is unstable in contact with the air components, vacuum drying or drying in a protective atmosphere is necessary.

[0081] The drying step consists of two or more steps:

[0082] 1. Evaporating the solvent - for example, in the case of xylene and NBR (binding polymer), this step is carried out at the temperature of 80-90°C;

[0083] 2. In the case layers are prepared in air atmosphere, subsequently the solvent is additionally evaporated in a vacuum dryer (the temperature depends on the used binding polymer) for a determined time (e.g. about 12 hours) in order to remove of trace amounts of water before the process of assembling an electrochemical cell. In the case a layer of an electrode is produced from a suspension of LTO in xylene with NBR, drying is carried out at the temperature of 80°C for about 12 hours. Vacuum evaporation is also recommended in the case of the recrystallization of a material is, e.g. during spraying LPSC from ethanol. In the case of materials that are stable in oxygen it is also possible to carry out drying in an anhydrous atmosphere without using vacuum, and using e.g. the so-called “clean” room with reduced humidity, used in industry.

[0084] Steps (a) and (b) and optionally (c) can be repeated from 1 to 6 times in order to produce subsequent layer / layers on the layer produced previously (Fig. 2). Each produced layer is optionally pressed before depositing the subsequent layer, and / or all layers are pressed together. Pressing is carried out, for example, in a hydraulic press under a pressure of 0 to 900 MPa, preferably from 50 to 400 MPa. Selection of appropriate pressure depends on the properties of materials used, e.g. on their hardness and morphology.

[0085] The solid substrate is a current collector, a layer of an electrode, a layer of a solid electrolyte or a protective layer, depending on the type of system to be produced and type of layer to be deposited. This is related to the fact that the method according to the invention is used for both depositing the first layer on the current collector and depositing one or more layers on another layer produced by the method according to the invention or by another method known in this field.

[0086] Therefore, the method according to the invention is suitable for depositing:

[0087] - a single layer (e.g. a layer of an electrode, a protective layer or a layer of a solid electrolyte),

[0088] - many layers of an electrochemical cell or half-cell, or

[0089] - a layer in which a dissolved compound recrystallizes from the evaporated solvent after deposition on a surface.

[0090] Moreover, the method according to the invention can be used to produce an electrochemical half-cell or cell comprising, for example, the following layers:

[0091] - a layer of a positive electrode / a layer of type A solid electrolyte / a layer of type B solid electrolyte / a layer of a negative electrode, or

[0092] - a layer of a positive electrode / a layer of a solid electrolyte / a layer of a negative electrode, or

[0093] - a layer of an electrode / a layer of a solid electrolyte, and the method according to the invention can be used to deposit one or more or all layers of the above- specified systems.

[0094] Furthermore, a protective layer can be deposited onto a layer of an electrode or a layer of a solid electrolyte, if necessary. The protective layer can be a layer of a solid electrolyte having different chemical stability than a layer of the main electrolyte and corresponding to the stability of the electrochemical window of the “protected” electrode. In such case, the protective layer should be ion-conductive. The protective layer can be a layer of a material other than an electrode material to ensure the chemical or mechanical stability of the “protected” layer. The protective layer can also be a layer of another material which constitutes an electrode with a different potential than the protected” electrode to maintain better chemical stability and cycling stability. Furthermore, in the case of depositing the protective layer, an electrical conductor can be added to the components of the mixture produced in step (a), as specified in the case of depositing the layer of an electrode.

[0095] The invention also relates to a method of producing an electrochemical half-cell or cell which comprises depositing subsequent layers of the electrochemical half-cell or cell on a current collector i.e. a layer of an electrode / a layer of a solid electrolyte and optionally a protective layer on the layer of an electrode and / or on the layer of a solid electrolyte (in the case of the half-cell), or a layer of an electrode / one or more layers of a solid electrolyte / a layer of an electrode and, optionally, a protective layer on the layer of an electrode and / or on one or more layers of the solid electrolyte (in the case of the cell), wherein at least one layer from the above-mentioned layers is deposited by the above-described method of spraying a mixture of appropriate components. Each deposited layer can be pressed before depositing another layer thereon, and / or all deposited layers can be pressed together.

[0096] In view of the above, the invention also relates to an electrochemical half-cell or cell comprising at least one layer deposited by the method according to the invention and a hybrid cell in which, apart from solid layers, an additive of a liquid electrolyte is also used.

[0097] The invention is illustrated by means of examples below, which however do not limit the invention.

[0098] In the following part of the description, the method of depositing layers according to the invention is also described as TLAD (Thin Layer Aerosol Deposition) technique.

[0099] In the examples below and in the figures, the following abbreviations are used:

[0100] LTO - LUTisOii

[0101] C - active carbon

[0102] CF - carbon fibres

[0103] PVdF - poly (vinylidene fluoride)

[0104] NMP - N-Methylpyrrolidone

[0105] NBR (or NBR 346) - acrylonitrile-butadiene rubber

[0106] LPSC - Li6PS5Cl

[0107] LPS - Li3PS4

[0108] LiTFSI - lithium bis(trifluoromethanesulfonyl)imide, LiNCSOiCFsL

[0109] LP30 - I M solution of lithium hexafluorophosphate in ethylene carbonate and dimethyl carbonate, 1.0 M LiPFe in EC:DMC=50:50 (vol.:vol.), battery quality

[0110] LiPFe - lithium hexafluorophosphate

[0111] EC:DMC - ethylene carbonate: dimethyl carbonate Example 1

[0112] Producing an electrode layer

[0113] In order to determine how spraying of a layer would affect its electrochemical results, three types of samples were prepared. The first sample was a reference sample prepared by spreading a suspension on aluminium foil by means of a doctor blade. The second and third samples were layers produced by the method according to the invention i.e. by spraying a suspension on aluminium foil.

[0114] The first suspension was prepared classically by grinding an LTO electrode material with active carbon (Vulcan Carbon Black - C), then 5% solution of PVdF polymer in NMP was added. The weight ratio of LTO:C:PVdF was 82.5%: 12.5%:5%. The second and third suspensions were prepared by dry grinding LTO with carbon fibres (Sigma Aldrich) in a mortar. Then, 5% solution of NBR 346 polymer (trade name PERBUNAN 2846 F OS, product code: 06449999) dissolved in anhydrous xylene (Sigma Aldrich) was added. The mass was supplemented with xylene to obtain a thick suspension which was stirred for 24 hours before spraying. The content of LTO, CF, NBR 346 in the second suspension was 82.5, 12.5 and 5% by weight, respectively, and in the third suspension: 80%, 10% and 10% by weight.

[0115] Suspension 1 was spread on a tarnished aluminium foil by the tape casting method (a classic method used in the battery industry) using a doctor blade. The orifice size was 100 pm, and the speed was 10 mm s’1.

[0116] Suspensions 2 and 3 were sprayed on a tarnished (prepared) aluminium foil by the method according to the invention, i.e. by means of an aerograph (Harder & Steenbeck Evolution) having 0.4 mm orifice, using compressed argon under the pressure of 1 bar, thus forming electrode layers. A round nozzle was used. The obtained layers were characterized by moderate mechanical resistance. The layer with 10% content of NBR 346 showed better adhesion due to a larger content of polymer (binding agent). The photograph of this layer is presented in Fig. 2A. A sprayed area may have any predetermined shape. For this purpose, an appropriate mould should be used (in the described example, it was a rectangular mould).

[0117] The electrode layers were dried in a vacuum dryer overnight at 80°C. Electrodes cut out from the layers (by an El-Cut cutting tool with 9 mm diameter, El-Cell company) were dried in a vacuum drier at 80°C overnight. Cells were assembled in a glove box in argon atmosphere (O2 and H2O content below 10 ppm) in a Swagelok-type system with a counter electrode and a reference electrode of lithium (Sigma Aldrich) in the standard liquid electrolyte, i.e. 1 M LiPFe in EC:DMC (1: 1) (BASF). Measurements were performed after 24 hours from the assembly of the cells, by applying current C / 5 (50 cycles).

[0118] Fig. 3A shows charge specific capacities of the FTO material (current value C / 5) for the layers prepared by two different techniques and with different contents of NBR (squares - the layer based on FTO with 5% PVDF and C, deposited using a doctor blade, triangles - the layer based on LTO with 5% NBR and 12.5% CF, deposited using TLAD technique, and circles - the layer based on LTO with 10% NBR and 10% CF, deposited using TLAD technique). No great differences between the results obtained for the cells produced by TLAD and doctor blade techniques were observed. A slightly greater theoretical discharge capacity compared to that in the literature may result from errors in determining active mass in the course of preparing laboratory measurement systems (small scale). The smallest capacity drop after 50 cycles was observed for the sample sprayed by TLAD technique, containing 5% NBR (Fig. 3B). The cells prepared by this technique (TLAD, 5% NBR) were characterized by the best cycling stability (Fig. 3C).

[0119] The above data confirmed that the method of depositing layers by TLAD technique can be an alternative for the commonly used spreading of layers.

[0120] Example 2

[0121] Producing a solid electrolyte layer

[0122] In order to determine how spraying of a solid electrolyte layer would affect its ion conductivity, two types of samples were prepared. The first sample was a pellet prepared by weighing out about 100 mg of an LPSC material (annealed at 500°C). The material was placed in a pelleting machine between current collectors (the pelleting machine pistons made of stainless steel) having 10 mm in diameter and were compressed in a hydraulic press under the pressure of 340 MPa.

[0123] The second sample was prepared from the same LPSC material (annealed at 500°C). For this purpose, an analytical sample was weighed to constitute 95% by weight of dry components in a suspension. The powder was ground in an agate mortar, and then it was transferred to a vial with a magnetic stirrer. Then, 5% by weight of NBR 346 binder from 5% solution in anhydrous xylene (Sigma Aldrich) was added. The suspension was left under magnetic stirring at the stirring speed of 250 rpm for 24 hours. The suspension was sprayed on the prepared current collector (the pelleting machine pistons made of stainless steel) by means of an aerograph (Harder & Steenbeck Evolution) with a round nozzle having 0.4 mm orifice, using compressed argon under the pressure of 1 bar, thus forming a layer on the surface of the current collector. Then, like in the case of the pellet, the prepared layer was compressed in a hydraulic press under the pressure of 340 MPa.

[0124] Both samples were tested in the same measurement system by means of electrochemical impedance spectroscopy (Fig. 4). Specific conductivity was registered as the function of temperature in order to determine activation energy for the LPSC material. The sprayed layer of electrolyte is characterized by a much lower resistance than the pellet of the same material. The value of the activation energy of the sprayed layer (0.27 eV) is much lower than that of the sample prepared in the form of pellet (0.4 eV).

[0125] The data confirm that the critical point for the results of ion conductivity in solid electrolytes is grain boundary resistance. Fig. 4 also shows the schematic diagram of a measurement cell for ion conductivity tests A) - in the case of a pressed solid electrolyte (SE) pellet and B) - a sprayed solid electrolyte (SE) layer, to illustrate that the layer sprayed by TLAD technique is thinner and there are fewer contacts between grains therein (Fig. 4B). Additionally, a polymer present in a sprayed suspension may facilitate the mutual arrangement of grains and fitting to a substrate after pressing.

[0126] The obtained data clearly indicate that the problem of poor mechanical resistance of the pellets has been eliminated, and the sprayed material has better adhesion to the substrate.

[0127] The TLAD technique made it possible to both perform basic characterization of the tested compounds and produce semiconductor cells.

[0128] An LTO|LPSC half-cell was also produced, in which both layers were deposited by the method according to the invention, using suitable suspensions described in Example 1 and 2. The photograph of that cell with partially exposed (by means of a mould) electrode layer is shown in Fig. 2 B.

[0129] Example 3

[0130] Production of a semiconductor half-cell

[0131] 3a) Depositing electrode layers

[0132] A suspension was prepared from a dry powder of an LTO-LPSC (1: 1) composite. An appropriate mass of the dry powder was measured out, assuming that it would constitute 80% by weight of dry components of the electrode mass. To the measured-out portion, 15% by weight of carbon fibres (Sigma Aldrich) was added as a conductor to facilitate the exchange of electrons in the active mass. The dry powders were ground in an agate mortar and were transferred to vials with a magnetic stirrer. 5% by weight based on the dry components, from 5% solution of NBR 346 polymer (commercial acrylonitrile -butadiene rubber from Silspek Rubber Sp. z o.o.) in anhydrous xylene was added to the sample. Xylene was added to the vial so that, after mixing, the powder materials would form a suspension having the consistency of paint.

[0133] NBR 346 was chosen as the polymer due to its electrochemical stability in the tested system and the best mechanical properties among the tested xylene- soluble polymers. Moreover, NBR 346 shows good solubility in anhydrous xylene. Xylene, on the other hand, was chosen for preparing the suspension due to its chemical inertness with respect to the other components and its favourable properties for preparing suspensions. The suspension was left under magnetic stirring at the stirring speed of 250 rpm for 24 hours. After that time, the suspension was spread on aluminium foil by the tape casting method using a doctor blade. The thickness of the orifice was 100 pm. An electrode layer of the LTO-LPSC (1: 1) composite was dried in a glove box overnight. Electrodes having 9 mm in diameter were cut out from the dried layer by an El-Cut cutting tool (El-Cell company) and then they were weighed. Before depositing layers of solid electrolytes, an average mass of the active material on the electrode (mg cm-2) was determined relative to the mass of pure current collector (aluminium foil) based on the measurement of 6 subsequent electrodes cut out from the electrode layer.

[0134] 3b) Depositing layers of solid electrolytes

[0135] Layers of solid electrolytes for assembling semiconductor cells were deposited by the method according to the invention (TLAD technique). An appropriate mass of LPSC powder (annealed at 500°C) was measured so that it constituted 95% by weight of dry components in a suspension. The powder was ground in an agate mortar, and then it was transferred to a vial with a magnetic stirrer - (in the case of powder materials from which a suspension will be made it is necessary to homogenize the size of grains. Homogenization of solid material ensures the stable suspension and does not disturb the process of flow and spraying of the suspension). Then, 5% by weight of NBR 346 binding agent from 5% solution in anhydrous xylene (Sigma Aldrich) was added. The suspension was left under magnetic stirring at the stirring speed of 250 rpm for 24 hours. A suspension of LPS (annealed at 200°C) was made in an analogous way. The individual suspensions were sprayed onto spread electrode layer based on the LTO-LPSC (1: 1) composite by means of an aerograph (Harder & Steenbeck Evolution) having 0.4 mm orifice, using compressed argon under the pressure of about 1 bar, thus making a half-cell. In the same way, two layers of a material which constitutes a solid electrolyte were sprayed onto the electrode layer, namely, first LPSC and then LPS, thus also forming a half-cell. In this case, the LPS layer was a protective layer. The layers of the half-cells were dried in a glove box overnight. Half-cells having the diameter of 9 mm were cut out from the dried layers by an El-Cut cutting tool (from El-Cell company). Halfcells with the following configuration LTO-LPSC (1: 1) / LPSC, LTO-LPSC (1: 1) / LPS and LTO-LPSC (1: 1) / LPSC / LPS were obtained.

[0136] 3c) Testing the properties of semiconductor cells containing the half-cells produced by the above-described method.

[0137] First, imagining of the LTO-LPSC (1: 1) / LPSC half-cell (Fig. 5) was performed using scanning electron microscopy (SEM). It can be seen that, after pressing (Fig. 5A), the surface is even and homogenized. The cross-sectional view of the half-cell (Fig. 5B) shows that both layers (~10 pm thick each) are pressed together and fit each other (the white arrow -cathode, the black arrow - the solid electrolyte layer). Mapping by means of EDS detector confirmed that the electrolyte layer deposited by the TLAD technique is tight and evenly covers the electrode. This aspect was particularly important because uneven covering or penetration of the electrode layer from under the electrolyte would lead to a short circuit of the electrodes. The EDS analysis confirmed that pressing the LPSC layer does not interfere with its integrity and homogeneity.

[0138] The half-cells (prepared by the method described above) were tested in a Swagelok-type system with a spring current collector on the side of the positive electrode (for a better pressure) and metallic lithium (Sigma Aldrich) on a current collector with perforated surface as the counter electrode. Thus, cells with the following configurations were tested: LTO- LPSC (l: l) / LPSC / Li, LTO-LPSC (l: l) / LPS / Li and LTO-LPSC (l: l) / LPSC / LPS / Li. To assess the efficiency of the cells, measurements using cyclic potentiometry were performed in a climatic chamber at the temperature of 60°C. During the first hours, an increase in the cell potential from the value of 2.2 V to about 2.5 V was observed. After stabilizing the voltage, the cells were cyclically discharged and charged with current C / 20. Discharging was carried out to 1.2 V whereas charging to 2.1 V.

[0139] Fig. 6 shows the first cycles of the tested cells in relation to the cell with the liquid electrolyte (LP30). For simplicity, the material which constitutes the electrode, which was the LTO and LPSC composite, is marked simply as LTO on the graph. The LTO-LPSC(1 : l) / LPSC / Li cell showed the first discharge capacity of 39.4 mAh g1, and the charge capacity - 24.7 mAh g1. The LTO-LPSC (l:l) / LPS / Li cell showed more than twofold increase in the capacity relative to the previous one, during the first discharging. The LTO- LPSC(l: l) / LPSC / LPS / Li cell was assembled by spraying two layers of different electrolytes. First, on the side of the composite electrode, LPSC layer was deposited, and then LPS layer forming a protective layer was deposited thereon. This approach yielded the best results among all tested entirely semiconductive cells. In the first cycle, during discharging, the value of 181 mAhg1was obtained. The increased capacity relative to the theoretical capacity of LTO may result from additional chemical reactions taking place on the phase boundary. Analogously to the remaining cells, the charging curve here also has more than half smaller capacity, but it is nevertheless worth emphasizing that a considerable capacity was obtained using only spring pressure during the electrochemical tests.

[0140] The tests carried out have shown that the solid electrolyte layer deposited on the composite electrode layer, both before and after pressing, was characterized by high mechanical resistance, including resistance to bending, compression and falls from a small height. Ceramic pellets are totally non-resistant to bending and compression tests and falls from a small height. It is of colossal importance for cells in which all solid-state systems would be used for mobile applications. It is worth noting that the standard Swagelok system equipped only with an additional compression spring, and not a hydraulic press with a pressure force between 50 and 360 MPa as indicated in the literature, was used for the measurements.

[0141] Example 4

[0142] Hybrid cells

[0143] When designing a hybrid cell, the key aspect was using the smallest possible amount of a liquid electrolyte and its compatibility with other components. IM solution of LiTFSI in propylene carbonate (LiTFSLPC) was prepared. A drop of the liquid electrolyte was deposited on metallic lithium and was spread to form a thin film. Then, two complete hybrid cells were assembled from half-cells based on LTO-LPSC (4: 1) / LPSC and LTO-LPSC (1: 1) / LPSC composite materials, obtained by the method described in Example 3 and were tested by means of cyclic potentiometry with current C / 20 at room temperature.

[0144] CP curves (Fig. 7) show a change in the charging / discharging profiles of the hybrid cells (i.e. LTO-LPSC (4: l) / LPSC / LiTFSI-PC / Li and LTO-LPSC (l:l) / LPSC / LiTFSI-PC / Li) as compared with the standard cell based on LTO in liquid electrolyte (LP30). In both hybrid cells, a significant change in the curve profiles can be noticed compared to the cells with solid electrolyte (ASS) (Example 3). A decrease in internal resistance of the cell and an increase in the specific capacity can be observed. For the LTO-LPSC (1: 1) electrode material, the first discharging shows the capacity of 103,56 mAh g1, whereas for LTO-LPSC (4: 1) - 146 mAh g’1.

[0145] The use of an additive of a liquid electrolyte made it possible to eliminate insufficient contact between the solid electrolyte and lithium electrode (SE / Li) and improve the total efficiency of the cells. Information was also provided about another aspect, which is the oxidation of the solid electrolyte. It should be noted here that the effect of adding liquid electrolyte to

[0146] ASS cell, as described in scientific papers, is wrongly downplayed or even omitted in discussions. The differences in the capacities of the composites 4: 1 and 1 : 1 clearly show that liquid penetrates the entire volume of the cell. The TLAD technique can be used for covering electrodes with ion-conducting layers in order to provide mechanical and / or chemical protection.

Claims

Claims1. A method of depositing a layer of an electrochemical half-cell or cell, the layer being selected from a group comprising a layer of an electrode, a layer of a solid electrolyte or a protective layer, characterized in that the method comprises the following steps:(a) producing a mixture containing:- at least one material which constitutes the solid electrolyte or at least one material which constitutes the electrode or a material which constitutes the protective layer or a mixture of at least one material which constitutes the electrode and at least one material which constitutes the solid electrolyte,- at least one binding agent, and- at least one volatile solvent which is chemically inert with respect to components used; and(b) spraying the mixture produced in step (a) on a solid substrate by means of a spraying device, using an inert gas under a pressure falling within the range of 0.1 to 2 bar, to deposit the layer of an electrochemical half-cell or cell.

2. The method according to claim 1, characterized in that the mixture produced in step (a) is stirred before step (b).

3. The method according to claim 1 or claim 2, characterized in that the method additionally comprises step (c) of drying or annealing the layer deposited in step (b).

4. The method according to any one of claims 1-3, characterized in that steps (a) and (b), and optionally (c), are repeated in order to deposit another layer on the layer deposited previously.

5. The method according to claim 4, characterized in that steps (a) and (b), and optionally(c), are repeated from 1 to 6 times.

6. The method according to any one of claims 1-5, characterized in that the method additionally comprises step (d) of pressing the deposited layer before depositing another layer, and / or pressing all layers together.

7. The method according to any one of claims 1-6, characterized in that a material selected from a group comprising the following is used as the material which constitutes the electrode:(a) intercalation compounds, such as layered compounds, olivines, spinels and carbon compounds;(b) conversion compounds;(c) dopants of the intercalation compounds with other ions; and(d) a composite of any compound indicated in point (a), (b) and (c) with another compound indicated in point (a), (b) and (c) and / or with another organic or inorganic compound.

8. The method according to claim 7, characterized in that a spinel or a composite thereof with the material which constitutes the solid electrolyte is used as the material which constitutes the electrode.

9. The method according to claim 8, characterized in that Li^isOn or its composite with lithium argyrodite is used as the material which constitutes the electrode.

10. The method according to any one of claims 1-9, characterized in that the material which constitutes the electrode is or the materials which constitute the electrode are or the mixture of at least one material which constitutes the electrode and at least one material which constitutes the solid electrolyte is used in an amount in the range of 70% to 99% by weight relative to the total mass of the mixture produced in step (a).

11. The method according to any one of claims 1-10, characterized in that at least one electrical conductor is added to the material which constitutes the electrode.

12. The method according to claim 11, characterized in that conductive carbon is added as at least one electrical conductor.

13. The method according to claim 11 or claim 12, characterized in that the electrical conductor is or the electrical conductors are added in an amount of 25% by weight or less relative to the total mass of the mixture produced in step (a).

14. The method according to any one of claims 1-6, characterized in that a chemical compound selected from a group of compounds comprising argyrodites, phosphates, thiophosphates, titanates, garnets, perovskites, sulphides, NASICON, antiperovskites, oxides, chlorides, ion-conducting polymers, and analogs of the above-indicated compounds and dopants of the above-indicated compounds with other elements, and composites of the above-indicated compounds is used as the material which constitutes the solid electrolyte.

15. The method according to claim 14, characterized in that the argyrodites or the thiophosphates are used as the chemical compound.

16. The method according to claim 15, characterized in that LiePSsX is used as the argyrodites wherein X is an atom or atoms of halides, such as Cl, Br or I.

17. The method according to claim 15, characterized in that LisPS4 is used as the thiophosphates.

18. The method according to any one of claims 1-6 and claims 14-17, characterized in that the material which constitutes the solid electrolyte is or the materials which constitute the solid electrolyte are used in an amount in the range of 70% to 99% by weight relative to the total mass of the mixture produced in step (a).

19. The method according to any one of claims 1-18, characterized in that a conductive or non-conductive polymer soluble in the used solvent is used as the binding agent.

20. The method according to claim 19, characterized in that acrylonitrile-butadiene rubber is used as the polymer.

21. The method according to any one of claims 1-20, characterized in that the binding agent is or the binding agents are used in an amount in the range of 1% to 15% by weight relative to the total mass of the mixture produced in step (a).

22. The method according to any one of claims 1-21, characterized in that non-polar and polar solvents are used as the volatile solvent which is chemically inert with respect to components used.

23. The method according to claim 22, characterized in that xylene, toluene, benzene, hexane, ethanol, isopropanol, methanol, iV-methylpyrrolidone or their mixture is used as the solvent.

24. The method according to any one of claims 1-23, characterized in that in step (b), the spraying device having a nozzle with an orifice width falling within the range of 0.1 mm to 3 mm is used.

25. The method according to any one of claims 1-24, characterized in that the solid substrate is a current collector, an / the electrode layer, a / the solid electrolyte layer or a / the protective layer.

26. The method according to any one of claims 1-25, characterized in that the material which constitutes the solid electrolyte or the material which constitutes the electrode is used as the material which constitutes the protective layer.

27. A method of producing an electrochemical half-cell or cell that comprises deposition of subsequent layers of the electrochemical half-cell or cell on a current collector, characterized in that at least one layer from one or more electrode layers, one or more solid electrolyte layers and one or more protective layers is deposited by the method defined in claims 1-26.

28. The method of producing according to claim 27, characterized in that said method additionally comprises a step of pressing the deposited layer before depositing another layer.

29. The method of producing according to claim 27 or claim 28, characterized in that said method additionally comprises a step of pressing the produced electrochemical half-cell or cell.

30. An electrochemical half-cell or cell, characterized in that it comprises at least one layer deposited by the method defined in claims 1-26.

31. The electrochemical half-cell or cell according to claim 30, characterized in that it further comprises an additive of a liquid electrolyte.

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