Plasma printing process for fabricating and producing battery electrodes and for strengthening current collectors

Abstract

Embodiments of the present invention provide a binder-free electrode for an electrochemical device manufactured using a plasma printing process. Process (100) includes depositing an electroactive material across a current collector in a continuous electrolytic plasma process to form an electrode. Because the electroactive material is mechanically bonded to the surface of the current collector, the process of the present invention is chemically independent and can deposit a wide variety of materials on the current collector. A solid-state battery manufactured using the above process is also disclosed.

Description

Technical Field

[0001] Various embodiments of the present disclosure generally relate to bind-free electrodes for electrochemical devices. More specifically, various embodiments of the present disclosure relate to plasma printing of bind-free electrodes and solid-state batteries using a continuous electrolytic plasma process.

Background Art

[0002] The demand for efficient and reliable energy storage devices is increasing. Electrochemical devices such as batteries and supercapacitors play an essential role in our daily life in a wide range of applications from mobile phones to electric vehicles. Electrodes are the center of electrochemical devices as they function as the interface where electrochemical reactions occur, enabling energy storage and / or conversion.

[0003] Electrodes of electrochemical devices are typically formed by applying an active material on a current collector. The active material can be applied by a dry process, i.e., in the absence of any solvent, by dry jet and mortar or dry powder coating methods. Applying the active material by a dry process is very complex and requires sophisticated machinery and techniques. Alternatively, a wet slurry technique may be used to make the electrodes. In the wet slurry technique, the active material is mixed with a binder and dispersed in an organic solvent or an aqueous medium to form a wet slurry. Then, the wet slurry is applied to the current collector to form an electrode. However, due to the presence of the binder, it is a challenge to achieve a high electrode density of the electrode and thus an improved energy density of the battery. Furthermore, drying of the electrodes may take 12 to 24 hours, thus affecting the production cost.

Summary of the Invention

Problems to be Solved by the Invention

[0004] A manufacturing process is needed that is cost-effective, economical, and addresses some of the shortcomings of existing processes.

[0005] The limitations and disadvantages of conventional and traditional methods will become apparent to those skilled in the art through a comparison of the described system with some aspects of this disclosure, as described with reference to the drawings in the remainder of this application. [Means for solving the problem]

[0006] Embodiments of the present invention provide electrodes for an electrochemical device manufactured using a process. The process includes providing a chamber filled with a liquid electrolyte and comprising at least one plasma anode. The liquid electrolyte comprises an electroactive material. The process further includes providing a current collector in the chamber, the current collector and at least one plasma anode moving relative to each other at a certain translational velocity, and the current collector, or at least one plasma anode, or both, being operable to move continuously in and out of the chamber. The process further includes applying a voltage between at least one plasma anode and the current collector to generate a plasma, the plasma being generated in an initial plasma zone between a portion of the current collector and at least one plasma anode, the plasma inducing the electroactive material to mechanically bond to a portion of the current collector, forming a layer. The process further includes positioning and repeating along the dimensions of the current collector to obtain an electrode by moving at least one plasma anode, current collector, or both, thereby positioning the next portion of the current collector relative to the next plasma zone, extending a layer of electroactive material over the next portion of the current collector, and repeating this step along the dimensions of the current collector, wherein the temperature of the bulk liquid electrolyte in the chamber is 100°C or less during the process.

[0007] According to embodiments of the present invention, a continuous process for manufacturing electrodes for electrochemical devices is provided. The process includes providing a chamber filled with a liquid electrolyte and comprising at least one plasma anode, the liquid electrolyte being continuously supplied at a certain flow rate and discharged from the chamber. The liquid electrolyte comprises an electroactive material. The process further includes providing a current collector in the chamber, the current collector and at least one plasma anode moving relative to each other at a certain translational velocity, and the current collector, or at least one plasma anode, or both, being operable to continuously move in and out of the chamber. The process further includes applying a voltage between at least one plasma anode and the current collector to generate a plasma, the plasma being generated in an initial plasma zone between a portion of the current collector and at least one plasma anode, the plasma inducing the electroactive material to mechanically bond to a portion of the current collector, forming a layer. The process further includes positioning and repeating along the dimensions of the current collector to obtain an electrode by moving at least one plasma anode, current collector, or both, thereby positioning the next portion of the current collector relative to the next plasma zone, extending a layer of electroactive material over the next portion of the current collector, and repeating this step along the dimensions of the current collector, wherein the temperature of the bulk liquid electrolyte in the chamber is 100°C or less during the process.

[0008] In another embodiment, a continuous process for processing a battery current collector is provided. This process includes the step of providing a chamber filled with a liquid electrolyte and comprising at least one plasma anode, the liquid electrolyte being continuously supplied at a certain flow rate and discharged from the chamber. The process further includes providing a current collector into the chamber, the current collector and at least one plasma anode moving relative to each other at a certain translational velocity, and the current collector, or at least one plasma anode, or both, being operable to continuously move in and out of the chamber. The process further includes applying a voltage between at least one plasma anode and the current collector to generate a plasma, the plasma being generated in an initial plasma zone between a portion of the current collector and at least one plasma anode, and the plasma modifying the surface of the portion of the current collector in the initial plasma zone. The process further includes positioning and repeating, by moving at least one plasma anode, current collector, or both, to position the next portion of the current collector relative to the next plasma zone, modifying the surface of the next portion of the current collector, and repeating this step along the dimensions of the current collector to obtain a processed current collector, wherein the temperature of the bulk liquid electrolyte in the chamber is 100°C or less during the process.

[0009] Another embodiment provides a method for manufacturing a battery. The method includes (i) providing a chamber filled with a first electrolyte and comprising at least one plasma anode, wherein the first electrolyte is continuously supplied at a certain flow rate and discharged from the chamber, and the first electrolyte comprises a first electroactive material. The method includes (ii) providing a current collector in the chamber, wherein the current collector and at least one plasma anode are in relative motion to each other at a certain translational velocity, and the current collector, or at least one plasma anode, or both, are operable to continuously move in and out of the chamber. The method further includes (iii) applying a voltage between at least one plasma anode and the current collector to generate a plasma, wherein the plasma is generated in an initial plasma zone between a portion of the current collector and at least one plasma anode, and the plasma induces mechanical bonding of the first electroactive material across the portion of the current collector to form a layer. The method further includes step (iv) moving at least one plasma anode, a current collector, or both to position the next portion of the current collector relative to the next plasma zone, extending a layer of a first electroactive material over the next portion of the current collector, and repeating this step along the dimensions of the current collector to form a continuous layer on the current collector and obtain a first electrode. The method further includes step (v) repeating steps (i) to (iv) using the first electrode and a second electrolyte, wherein the second electrolyte comprises a solid electrolyte material. The solid electrolyte material is deposited on the surface of the first electrode, and the solid electrolyte material is mechanically bonded to the surface of the first electrode to form a solid electrolyte bonded electrode. The method further includes step (vi) repeating steps (i) to (iv) using a solid electrolyte bonded electrode and a third electrolyte, wherein the third electrolyte comprises a second electroactive material. The second electroactive material is deposited on the surface of the solid electrolyte bonded electrode, and the second electroactive material is mechanically bonded to the surface of the solid electrolyte bonded electrode to form a battery. The battery includes a first electrode, a solid electrolyte, and a second electrode.The temperature of the bulk primary electrolyte or the bulk secondary electrolyte in the chamber is 100°C or lower.

[0010] In another embodiment, a plasma apparatus is provided for continuously manufacturing electrodes for electrochemical devices. The plasma apparatus comprises a chamber having an inlet and an outlet for circulating a liquid electrolyte at a certain flow rate. The chamber is filled with the liquid electrolyte, which comprises an electroactive material. The plasma apparatus further comprises at least one plasma anode disposed within the chamber and operable to optionally move in and out of the chamber. The plasma apparatus further comprises a current collector disposed within the chamber at a distance from the at least one plasma anode, the current collector moving relative to the at least one plasma anode at a certain translational velocity, and the current collector operable to optionally move in and out of the chamber. The plasma apparatus further comprises a DC power supply for generating a plasma by applying a voltage between the current collector and the at least one plasma anode, the generated plasma inducing mechanical bonding of the electroactive material on the surface of the current collector to form electrodes, and the plasma is controlled by adjusting the composition of the electrolyte, the composition of the current collector, the translational velocity, the flow rate, the voltage, or a combination thereof.

[0011] These and other features and advantages of this disclosure can be understood by considering the following detailed description of this disclosure, together with the attached drawings, in which similar reference numbers throughout refer to similar parts. [Brief explanation of the drawing]

[0012] [Figure 1] This is a flowchart of a continuous process for processing a current collector of an electrochemical device according to one embodiment of the present disclosure.

[0013] [Figure 2] This is a schematic diagram of a plasma apparatus for the continuous manufacturing of electrodes for electrochemical devices.

[0014] [Figure 3] This is a scanning electron microscopy (SEM-EDX) image of an electrode manufactured according to an embodiment of the present disclosure, with energy-dispersive X-ray spectroscopy. [Modes for carrying out the invention]

[0015] Further areas of application of this disclosure will become apparent from the detailed description provided below. The detailed description of embodiments is for illustrative purposes only and should be understood as not necessarily limiting the scope of this disclosure.

[0016] The following description illustrates in detail several embodiments of the disclosed disclosure. Those skilled in the art will recognize that there are numerous variations and modifications of the disclosure that are included within the scope of this disclosure. Therefore, the description of specific embodiments should not be considered to limit the scope of this disclosure.

[0017] As used herein, the term “comprising” is synonymous with “including” or “containing,” and is comprehensive or open-ended, not excluding any additional unlisted elements or method steps.

[0018] All figures used herein to represent quantities, characteristic measurements, etc., of components should be understood to be modified in all cases by the term "approximately." Therefore, unless otherwise indicated, the numerical parameters described herein are approximations that may vary depending on the desired characteristics to be obtained.

[0019] As used herein, the term “plasma printing” refers to a high-speed, continuous process, similar to traditional printing methods. Plasma printing technology utilizes plasma to modify a surface or deposit a material onto the surface of a substrate. In this disclosure, a reducing atmosphere plasma is generated by a plasma printer or a plasma apparatus using an electrolytic plasma process in which a liquid electrolyte contains the desired material(s) for deposition. The material can be deposited regardless of its properties, particle size, and form (e.g., gas, liquid, or solid), as described in detail below. In the context of this disclosure, the substrate refers to a current collector, and the material to be deposited is an electroactive material, an additive, or both. As used herein, the term “process” refers to “plasma printing” or “continuous electrolytic plasma deposition process.” The term “process” also refers to a continuous electrolytic plasma process for processing a current collector.

[0020] As used herein, the term "electrode density" is defined as the volume mass density of the electrode material, including the active material, binder, and any residual solvent within the electrode.

[0021] As used herein, the term “electrochemical device” refers to a device that generates electricity from a chemical reaction, and includes batteries, solid-state batteries, electrolytic capacitors, and supercapacitors.

[0022] The term "battery," as used herein, includes both rechargeable and non-rechargeable batteries. A typical battery consists of an anode, a cathode, an electrolyte, a separator, and two current collectors corresponding to the anode and cathode. The anode and cathode are collectively referred to as electrodes. The electrolyte may be liquid or solid. A battery containing a solid electrolyte is called a solid-state battery.

[0023] "Electrolytic capacitor", as used herein, refers to a type of capacitor that uses an electrolyte as one of its electrodes. An electrolytic capacitor consists of two plates, an anode and a cathode. The anode is typically made of a metal that forms an insulating oxide layer that acts as the dielectric of the capacitor. A solid, liquid, or gel electrolyte covers the surface of the oxide layer that acts as the cathode. The three main electrolytic capacitor series are based on aluminum, tantalum, and niobium. A "supercapacitor" is a high-capacity electrolytic capacitor that can store 10 to 100 times more energy than a typical electrolytic capacitor.

[0024] As used herein, the term "cathode", when used in the context of a battery, refers to the electrode that supplies electrons during charging of the battery and is part of the redox reaction. As used herein, the term "anode", when used in the context of a battery, refers to the electrode that receives electrons during charging and is part of the redox reaction. The terms "cathode" and "anode", as used herein, can refer to the cathode and anode of an electrolytic capacitor or a supercapacitor, respectively.

[0025] As used herein, the term "electrolyte" can refer to a material that allows ions to move through it but does not allow electrons to conduct through it, and is used in the context of an electrochemical device. The term "liquid electrolyte" refers to the electrolyte used in a plasma chamber.

[0026] As used herein, the term "current collector" refers to a bridging component that collects the current generated at an electrode via an external circuit.

[0027] Rechargeable metal-ion batteries function through the reversible intercalation and deintercalation of metal ions between the anode and cathode of the battery. During the discharge cycle, oxidation half-reactions at the anode form metal ions and electrons. The anode releases metal ions to the cathode through the electrolyte, while electrons flow from the anode through the external circuit and to the cathode via the current collector. During the charge cycle, current is applied through the external circuit, and metal ions are released from the cathode to the anode through the electrolyte.

[0028] Commercially, the electrodes of a metal-ion battery are formed by coating a current collector with a slurry containing an electroactive material. As used herein, the terms “electroactive material” or “active material” may refer to a material that generates electrical energy from a chemical reaction during battery discharge. The cathode is formed by coating a cathode current collector with a slurry containing a cathode active material. The anode current collector is coated with a slurry containing an anode active material to obtain the anode. The slurry may further contain a binder. A binder refers to a compound that can hold the active materials together and also strengthen the bond between the active materials and the current collector.

[0029] The most commonly used metal-ion batteries are based on alkali metal ions such as lithium, potassium, and sodium. Alkali metal ions are monovalent, and the amount of electrical energy that can be stored and recovered from a given weight of electroactive material, typically a metal salt, is limited because it results in only one electron / ion transfer per unit weight of metal. Divalent alkaline earth ions such as calcium, magnesium, and strontium, polyvalent transition metals such as yttrium, niobium, molybdenum, titanium, and tungsten, and lanthanide compound sources such as lanthanum, europium, and samarium are known. For the purposes of this invention, the term “battery” includes batteries that utilize the metal ions described above.

[0030] Metal-air batteries are another type of battery consisting of a metal anode, a porous air cathode, and an electrolyte. A typical air cathode comprises a current collector, a catalyst layer, and a hydrophobic diffusion layer facing the air side of the air cathode. Non-limiting examples of metal-air batteries include zinc-air, iron-air, aluminum-air, magnesium-air, lithium-air, sodium-air, potassium-air, and silicon-air batteries. For the purposes of this invention, the term "battery" includes the metal-air batteries described above.

[0031] Organic batteries are another type of battery in which organic compounds, such as small organic molecules or polymers, are responsible for charge storage. For the purposes of this invention, the term "battery" includes organic batteries.

[0032] Embodiments of the present invention provide electrodes for an electrochemical device manufactured using a process. The process includes providing a chamber filled with a liquid electrolyte and comprising at least one plasma anode, the liquid electrolyte being continuously supplied at a certain flow rate and discharged from the chamber. The liquid electrolyte comprises an electroactive material. The process further includes providing a current collector in the chamber, the current collector and at least one plasma anode moving relative to each other at a certain translational velocity, and the current collector, or at least one plasma anode, or both, being operable to continuously move in and out of the chamber. The process further includes applying a voltage between at least one plasma anode and the current collector to generate a plasma, the plasma being generated in an initial plasma zone between a portion of the current collector and at least one plasma anode, the plasma inducing the electroactive material to mechanically bond to a portion of the current collector, forming a layer. The process further includes positioning and repeating along the dimensions of the current collector to obtain an electrode by moving at least one plasma anode, current collector, or both, thereby positioning the next portion of the current collector relative to the next plasma zone, extending a layer of electroactive material over the next portion of the current collector, and repeating this step along the dimensions of the current collector, wherein the temperature of the bulk liquid electrolyte in the chamber is 100°C or less during the process.

[0033] The current collector of this disclosure corresponds to a current collector of a battery, on which an electroactive material is deposited to form electrodes. In another embodiment, the current collector corresponds to a material that forms part of the anode of an electrolytic capacitor.

[0034] In one embodiment, the current collector is a metal, a nonmetal, a metal oxide, a polymer, or a combination thereof. The suitability of a material as a current collector for a particular electrode, capacitor, and / or battery depends on the conductivity and potential stability of the material. For example, the cathode of a lithium-ion battery has a higher potential of 3 to 4.5 V relative to lithium / lithium ions, while the anode has a lower potential of 0.01 to 1.5 V relative to lithium / lithium ions. Aluminum (Al) metal is a good conductor with 61% conductivity compared to copper. However, Al is not suitable for use as an anode current collector in lithium-ion batteries because it is stable at higher potentials. Aluminum can be used as a cathode current collector because it is stable at higher potentials. Theoretically, any metal, nonmetal, metal oxide, conductive polymer, and combination thereof may be used as a current collector if the electrode potential of the battery matches the potential of the material and the material has appropriate conductivity. Current collectors can be in the form of sheets, foils, meshes, porous materials, or nonwoven fabrics. In one embodiment, the current collector has a three-dimensional structure such as a foam.

[0035] Non-limiting examples of metals include aluminum, manganese, cobalt, copper, nickel, titanium, stainless steel, platinum, zinc, tin, lithium, tungsten, molybdenum, tantalum, sodium, potassium, chromium, or alloys thereof. Non-limiting examples of metal oxides include indium tin oxide, fluorine-doped indium tin oxide, nickel oxide, cobalt oxide, manganese oxide, iron oxide, lithium oxide, titanium oxide, or combinations thereof. Non-limiting examples of non-metals include semiconductor materials such as carbon, carbon fiber, carbon black, graphene, graphite, carbon nanotubes, fullerenes, hard carbon, soft carbon, porous carbon, graphene oxide, silicon, silicon oxide, and germanium, or combinations thereof. Non-limiting examples of polymers include thermoplastic polymers such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), or combinations thereof. Polymers may be made conductive by doping them with a conductive agent such as graphite.

[0036] Electroactive materials include anode active materials and cathode active materials. Electroactive materials include metals, metal salts, nonmetals, nonmetal salts, polymers, donor-acceptor organic molecules, or combinations thereof. Exemplary electroactive materials include, but are not limited to, single metals, mixed metals, or nonmetal oxides, nitrides, oxynitrides, sulfates, phosphates, and sulfide salts. Metals include lithium, sodium, titanium, aluminum, tin, zirconium, yttrium, magnesium, sodium, copper, niobium, nickel, manganese, cobalt, and iron. Nonmetals include carbonaceous materials, sulfur, boron, and silicon. As used herein, the term “carbonaceous material” includes carbon-based materials such as graphite, carbon black, graphene oxide, reduced graphene oxide, carbon fibers, porous carbon, carbon nanotubes, fullerenes, graphene, activated carbon, amorphous carbon, soft carbon, hard carbon, or combinations thereof. Non-limiting examples of active materials include lithium metal oxides, lithium mixed metal oxides, lithium phosphate, lithium oxynitride, lithium titanate, lithium mixed metal phosphates, lithium nitride, lithium sulfide, sodium metal oxides, sodium mixed metal oxides, sodium phosphate, sodium mixed metal phosphates, silica, silicon, metal alloys, chalcogenides, transition metal oxides, metal sulfides, metal nitrides, carbon nanotubes, graphite, graphene, or combinations thereof. Exemplary electroactive materials for lithium-ion batteries include lithium metal oxides such as lithium manganese oxide (LMO), lithium nickel cobalt aluminum oxide (Li-NCA), lithium nickel manganese cobalt oxide (Li-NMC), lithium cobalt oxide (LCO), lithium nickel oxide (LNO), lithium nickel manganese oxide (LNMO), lithium nickel cobalt manganese oxide (LNCM), lithium iron phosphate (LFP), lithium manganese phosphate (LMP), and lithium cobalt phosphate (LCP).Non-limiting examples of polymers include polyvinylidene fluoride (PVDF), polyacrylic acid (PAA), perfluoroalkoxyalkanes (PFA), polythiophene, polypyrrole, polyacetylene, poly(tetramethylpiperidinyl oxymethacrylate) (PTMA), or combinations thereof.

[0037] Electroactive materials can exist in gaseous, solid, or liquid form. They can be dissolved in a liquid electrolyte, as in a typical electrolytic process. In another embodiment, the electroactive material is dispersed in a liquid electrolyte. Yet another embodiment, the electroactive material is nanostructured or microstructured. The particle size of the electroactive material can vary from a few micrometers to as small as nanometers. Furthermore, the electroactive material may be porous or non-porous.

[0038] Plasma is generated when a voltage is applied between two electrodes, namely a current collector and at least one plasma anode in a liquid electrolyte. The applied voltage is about 1000 volts (V) or less than about 1000 V. According to embodiments of the present disclosure, the plasma is generated over very short timescales of picoseconds to nanoseconds, assisting in the formation of mechanical bonds between particles and / or molecules of the electroactive material, as well as between the electroactive material and the surface of the current collector, thereby assisting in the deposition of the electroactive material. This process ensures the formation of a continuous layer on the current collector to obtain electrodes, the continuous layer containing the electroactive material. Since only mechanical bonds are formed during electrolytic plasma formation, the process of the present invention is chemistry-independent and therefore any material can be deposited using the process of the disclosure.

[0039] The continuous layer formed across the current collector using the process is a conformal layer. The conformal layer is a uniform, continuous coating or deposition on the surface of the current collector, regardless of the surface morphology or surface roughness or material type of the current collector. In one embodiment, the continuous layer of electroactive material on the current collector has a thickness ranging from 0.05 microns to 20 microns in a single pass of the current collector through the chamber.

[0040] In one embodiment, the continuous layer is multilayer and comprises a single electroactive material or two or more electroactive materials. In one embodiment, the multilayer structure may be obtained by arranging two or more plasma anodes in a chamber to form layers across layers. In another embodiment, the current collector may be capable of depositing layers across layers by passing through the chamber two or more times. In one embodiment, a multilayer structure having a single electroactive material may be obtained by providing a single electroactive material in a liquid electrolyte. In yet another embodiment, the liquid electrolyte may contain two or more electroactive materials to form a multilayer structure containing two or more electroactive materials. In another embodiment, after forming layers across a current collector using a liquid electrolyte having a first electroactive material, a second electroactive material is supplied to the liquid electrolyte to form a multilayer electrode containing the first and second electroactive materials through multiple passes of the current collector through the chamber.

[0041] In some embodiments, the multilayer continuous layer includes a first layer extending over the current collector and a second layer extending over the first layer. The current collector includes copper, steel, nickel, or aluminum. The first layer includes graphene, and the second layer includes silicon, tin, lithium, or a combination thereof. In one embodiment, the first layer is an interface layer, and the electroactive material is deposited over the interface layer to form an electrode. The interface layer may be used in electrode fabrication to enhance adhesion between the electroactive material and the current collector.

[0042] In another embodiment, the continuous layer is a stepped layer, and the concentration of the electroactive material varies across the cross-section of the continuous layer, i.e., transversely to the deposition direction. In one embodiment, the stepped layer can be formed by changing the concentration of the electroactive material in the liquid electrolyte during the process. In another embodiment, the stepped layer may be formed by including two different electroactive materials in the liquid electrolyte, and the concentrations of the two electroactive materials vary across the layer. In yet another embodiment, a pore-forming agent may be included in the electrolyte together with the electroactive material to vary the concentration of the electroactive material across the cross-section of the continuous layer. Plasma parameters as discussed above may also be used to form multilayer and stepped layers, for example by changing the voltage, which changes the plasma composition, and this can change the composition of the layer containing the electroactive material.

[0043] In one embodiment, the current collector of the electrode is aluminum, the electroactive material is graphene combined with silicon or tin, and the additive is polyvinylidene fluoride.

[0044] In some embodiments, the current collector of the electrode includes copper, aluminum, or nickel, and the electroactive material includes graphite, porous carbon, carbon nanotubes, fullerene, graphene, activated carbon, carbon black, amorphous carbon, soft carbon, hard carbon, or a combination thereof.

[0045] In some embodiments, the current collector of the electrode contains carbon, and the electroactive material includes boron-doped carbon, boron nitride, boron carbide, graphite, porous carbon, carbon nanotubes, fullerene, graphene, activated carbon, carbon black, amorphous carbon, soft carbon, hard carbon, or a combination thereof.

[0046] Figure 1 is a flowchart 100 illustrating a continuous process for processing a current collector of an electrochemical device by exemplary steps 102 to 108 according to an embodiment of the present disclosure. In step 102, a chamber is provided. The chamber is filled with a liquid electrolyte, which is continuously supplied at a certain flow rate and discharged from the chamber.

[0047] As used herein, the chamber refers to any enclosed wall system for preventing contamination and retaining liquid electrolytes. In preferred embodiments, the chamber is maintained at room temperature and atmospheric pressure. In some embodiments, the chamber may operate at high temperatures depending on process requirements. Optionally, a heater may be provided inside or outside the chamber to heat the chamber and / or its contents. In some embodiments, the chamber may be pressurized depending on process requirements. The chamber may be of any size and shape, but is not limited to these, and is customizable according to process requirements. In one example, the chamber is rectangular in shape.

[0048] The liquid electrolyte can be aqueous, solvent-based, or ionic liquid. An aqueous electrolyte is preferred. When an electric current or voltage is applied, the liquid electrolyte dissociates into its respective ions. The dissociation of ions in the liquid electrolyte should be a continuous process for stable plasma formation and persistence. Non-limiting examples of solvents that can be used in solvent-based liquid electrolytes include alcohols, ethanol, methanol, acetonitrile, dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), ethylene carbonate, propylene carbonate, or combinations thereof. Examples of ionic liquids include, but are not limited to, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-hexyl-3-methylimidazolium bath(trifluoromethylsulfonyl)imide, pyridinium-based ionic liquids, or combinations thereof. The composition and concentration of the liquid electrolyte can be controlled to control various plasma parameters, such as temperature and plasma composition. As used herein, the term “plasma composition” refers to the ions, radicals, or gases that make up the plasma, and their concentrations in the plasma.

[0049] The liquid electrolyte further comprises additives, electroactive materials, or both. Additives are in gaseous, solid, or liquid form. In one embodiment, additives include metals, metal oxides, nonmetals, nonmetallic salts, salts, binders, pore-forming agents, polymers, electroactivation-enhancing materials, or combinations thereof. In one embodiment, metals include platinum, palladium, gold, silver, cobalt, copper, nickel, iron, manganese, or any alloy thereof, which are used as catalytic materials in metal-air batteries. In another embodiment, additives include transition metal oxides and nonmetals, such as carbonaceous materials. As used herein, the term “electroactivation-enhancing material” refers to a material that functions as an electroactive material when deposited on a current collector using the electrolytic plasma of the present invention. Non-limiting examples of salts include alkali metal halides, sulfates, and carbonates, such as sodium chloride, potassium chloride, lithium chloride, potassium carbonate, sodium sulfate, or combinations thereof. Salts increase the conductivity of the liquid electrolyte by releasing the respective ions in the liquid electrolyte necessary for plasma formation. The choice of salt is based on the conductivity of the salt ions in the liquid electrolyte required for plasma generation and process requirements. For example, in sodium-free processes, non-sodium salts are preferred because sodium salts can contaminate the resulting electrodes.

[0050] A binder is added to the liquid electrolyte when the current collector is pretreated with a slurry containing an electroactive material to bond the wet slurry to the current collector. However, the binder is removed during the electrolytic plasma treatment process. Non-limiting examples of binders include polyacrylic acid, carboxymethylcellulose, styrene-butadiene rubber, sodium alginate, polyvinylidene fluoride, or combinations thereof.

[0051] Pore-forming agents may be contained in the liquid electrolyte. Exemplary pore-forming agents include polymers or surfactants that can alter the surface tension and viscosity of the liquid electrolyte, resulting in changes to the morphology and porosity of the surface of the deposited layer or current collector. The porosity of the deposited layer may be influenced by the presence of nanoparticles in the liquid electrolyte. The presence of gases in the liquid electrolyte can affect the porosity of the deposited layer. In some embodiments, the porosity of the deposited layer can be controlled by modulating processing parameters such as the voltage, current, or frequency of the power supply.

[0052] The liquid electrolyte is continuously supplied at a certain flow rate and discharged from the chamber. The circulation of the liquid electrolyte helps maintain the temperature of the bulk liquid electrolyte below, in one example, 100°C.

[0053] The chamber further comprises at least one plasma anode. The plasma anode forms half of a pair of electrodes necessary for plasma generation within the chamber. At least one plasma anode may be positioned along the vertical or horizontal axis of the chamber. At least one plasma anode may be stationary. In some embodiments, at least one plasma anode is movable.

[0054] In step 104, a current collector is provided in the chamber. The current collector corresponds to a current collector of a battery, on which an electroactive material is deposited to form electrodes. In another embodiment, the current collector corresponds to a metal forming part of the anode of an electrolytic capacitor or supercapacitor. In one embodiment, the current collector is a metal, a nonmetal, a metal oxide, a polymer, or a combination thereof.

[0055] The current collector and at least one plasma anode move relative to each other at a certain translational velocity. In one embodiment, the current collector is operable to move continuously in and out of the chamber. In some embodiments, at least one plasma anode is operable to move in and out of the chamber and moves relative to the current collector. In yet another embodiment, the relative motion between at least one plasma anode and the current collector is achieved by moving both continuously in and out of the chamber. In one example, at least one plasma anode, the current collector, or both may be mounted on rollers for continuous motion.

[0056] The current collector functions as the cathode, which is the other half of a pair of electrodes necessary for plasma generation. In one embodiment, the translational velocity can be controlled to control the plasma.

[0057] In some embodiments, providing a current collector in a chamber includes providing a current collector that is pre-coated with a slurry containing an electroactive material.

[0058] In step 106, a voltage is applied between at least one plasma anode and a current collector to generate plasma, which is generated in an initial plasma zone between a portion of the current collector and at least one plasma anode, and the plasma modifies the surface of the portion of the current collector within the initial plasma zone. The voltage is applied using a DC (direct current) power supply. A constant steady voltage is required for stable and continuous plasma generation. Inherent frequency variations of the DC power supply are minimized by modulating the frequency to achieve a steady voltage.

[0059] The relative motion of at least one plasma anode and current collector, combined with the frequency of the DC power supply, results in high-frequency on and off plasma on short timescales of picoseconds to nanoseconds. When generated on short timescales, the plasma results in surface activation of the current collector, electroactive material, and / or additives. The plasma can penetrate the surface of the current collector, additive, and / or electroactive material to a depth ranging from 5 to 10 nanometers to modify this surface. Surface activation increases the surface roughness or morphology of the surface, which can, in one example, facilitate the formation of adhesion or mechanical bonding. The plasma facilitates the generation of ions and / or radicals in the liquid electrolyte containing additives and / or electroactive material, which can help mechanically bond or adhere ions and / or radicals on the surface of the current collector.

[0060] A portion of the current collector's surface within the initial plasma zone is exposed to the plasma for a very short timescale. In one example, surface modification removes impurities from the current collector's surface. In another embodiment, surface modification includes removing undesirable oxides, sulfides, or nitrides from the surface of a metal current collector. In yet another embodiment, surface modification includes modifying the morphology of the current collector's surface.

[0061] In embodiments in which the liquid electrolyte includes an electroactive material, the electrolyte plasma induces mechanical bonding between the particles and / or molecules of the electroactive material, as well as between the particles and / or molecules of the electroactive material and a portion of the current collector, thereby forming layers.

[0062] In embodiments where the current collector is pre-coated with a slurry containing an electroactive material, a layer is formed on the current collector by surface modification, and this layer does not contain any binders present in the slurry. The pre-coated current collector may be dried before plasma treatment. In one embodiment, the current collector is dried by providing an infrared source.

[0063] The plasma can be controlled by adjusting plasma parameters. These plasma parameters include, but are not limited to, the composition of the liquid electrolyte, the flow rate, the applied voltage, the composition of the current collector, and the translational velocity. The plasma parameters are controlled during the process because these parameters are interdependent and dynamic. For example, as layers are deposited across a current collector, the composition of the current collector changes, and consequently, the conductivity of the resulting current collector changes, so the voltage that must be applied must be adjusted. As can be understood, the present disclosure by controlling plasma parameters ensures that the plasma brings about only mechanical bonding without destroying the structure or chemical properties of the particles and / or molecules of the electroactive material. Since only mechanical bonding is formed in electrolytic plasma deposition, the process of the present invention is chemistry-independent and therefore any material can be deposited using the process of the disclosure.

[0064] In step 108, by moving at least one plasma anode, current collector, or both, the next portion of the current collector is positioned relative to the next plasma zone and the surface of the next portion of the current collector is modified. Step 108 is repeated along the dimensions of the current collector to obtain the treated current collector, and the temperature of the bulk liquid electrolyte in the chamber is 100°C or less during the process.

[0065] To obtain a continuous process, the current collector, at least one anode, or both are moved, which moves the initial plasma zone to the next plasma zone, thereby moving to the next portion of the current collector and modifying the surface of the next portion. Step 108 is repeated along the dimensions of the current collector. In one embodiment, the dimensions correspond to the length of the current collector. By placing at least one plasma anode on each side of the current collector, the surfaces on both sides of the current collector can be modified during a single pass through the chamber.

[0066] During the process, the temperature of the bulk liquid electrolyte in the chamber remains below 100°C.

[0067] In one embodiment, the treated current collector includes a cleaned current collector that can be used to deposit an electroactive material over it to form electrodes. In another embodiment, the treated current collector is a current collector having a modified surface morphology.

[0068] In the embodiment, if the liquid electrolyte contains an electroactive material, step 108 is performed to form a continuous layer across the current collector by mechanically bonding the electroactive material to the surface of the current collector. The treated current collector is an electrode on which the electroactive material has been deposited as a continuous layer using the process.

[0069] The continuous layer has a thickness ranging from 0.05 microns to 20 microns in a single pass of the current collector through the chamber.

[0070] The continuous layer has a porosity ranging from 0.1% to 80%.

[0071] A specific advantage of the process is that, unlike commercial processes, the processing of current collectors or the manufacture of electrodes does not require energy-intensive or expensive equipment such as cleanrooms, or vacuum conditions. The process is carried out in a closed liquid electrolyte system at atmospheric pressure and room temperature.

[0072] Commercial slurry-based deposition requires binders, which are heavy for batteries and significantly affect their specific capacity. As used herein, the term "specific capacity" corresponds to the amount of charge (milliampere-hours (mAh)) that a material can deliver per gram of material, and is expressed as mAh per gram (mAh / g). By eliminating binders in electrodes, higher electroactive material loading can be achieved, which can lead to a higher specific capacity compared to electrodes with binders. The mechanical bonding of electroactive material to a current collector according to this disclosure provides a more mechanically stable electrode than electrodes with binders. The improved mechanical stability minimizes the breakdown and delamination of the electroactive material during operation, and therefore extends the life of the device.

[0073] This process substantially reduces or eliminates the solvents typically associated with solvent-based wet slurry methods. Furthermore, this process requires no drying time whatsoever.

[0074] A particular advantage of the process is that electroactive materials or additives can be dispersed in a liquid electrolyte, thus broadening the selection of materials that can be used in the process. Nanostructured or microstructured materials can be used without losing their morphology.

[0075] In another embodiment, a method for manufacturing a battery is provided. This method includes providing a chamber filled with a first electrolyte and containing at least one plasma anode. In step (i), the first electrolyte is continuously supplied at a certain flow rate and discharged from the chamber, and the first electrolyte comprises a first electroactive material. In step (ii), a current collector is provided into the chamber, and the current collector and at least one plasma anode move relative to each other at a certain translational velocity, and the current collector, or at least one plasma anode, or both, are operable to move continuously in and out of the chamber. In step (iii), a voltage is applied between at least one plasma anode and the current collector to generate plasma, the plasma is generated in an initial plasma zone between a portion of the current collector and at least one plasma anode, the plasma induces mechanical bonding of the first electroactive material across the portion of the current collector and forms a layer. In step (iv), by moving at least one plasma anode, current collector, or both, the next portion of the current collector is positioned relative to the next plasma zone, extending a layer of the first electroactive material onto the next portion of the current collector, and this step is repeated along the dimensions of the current collector to form a continuous layer on the current collector and obtain a first electrode. In step (v), steps (i) to (iv) are repeated using the first electrode and a second electrolyte, the second electrolyte comprising a solid electrolyte material for depositing a solid electrolyte material on the surface of the first electrode. The solid electrolyte material is mechanically bonded to the surface of the first electrode to form a solid electrolyte bonded electrode. In step (vi), steps (i) to (iv) are repeated using the solid electrolyte bonded electrode and a third electrolyte. The third electrolyte comprises a second electroactive material mechanically bonded to the surface of the solid electrolyte bonded electrode to form a battery. The battery comprises a first electrode, a solid electrolyte, and a second electrode. The "first electrode" and the "second electrode" correspond to the anode or cathode of the battery.

[0076] The temperature of the bulk primary electrolyte or the bulk secondary electrolyte in the chamber is 100°C or lower.

[0077] Current collectors are made of metal, nonmetal, metal oxide, polymer, or a combination thereof.

[0078] The first and second electrolytes are, independently of each other, aqueous, solvent, or ionic liquid systems. Non-limiting examples of solvents that can be used in solvent-based electrolytes include alcohols, ethanol, methanol, acetonitrile, dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), ethylene carbonate, propylene carbonate, or combinations thereof. Examples of ionic liquids include, but are not limited to, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-hexyl-3-methylimidazolium bath(trifluoromethylsulfonyl)imide, pyridinium-based ionic liquids, or combinations thereof.

[0079] The first electroactive material and the second electroactive material independently comprise metals, metal salts, nonmetals, nonmetal salts, polymers, donor-acceptor organic molecules, or combinations thereof. Exemplary electroactive materials include, but are not limited to, single metals, mixed metals, or nonmetal oxides, nitrides, oxynitrides, sulfates, phosphates, and sulfide salts. Metals include lithium, sodium, titanium, aluminum, tin, zirconium, yttrium, magnesium, sodium, copper, niobium, nickel, manganese, cobalt, and iron. Nonmetals include carbonaceous materials, sulfur, boron, and silicon. As used herein, the term “carbonaceous material” includes carbon-based materials such as graphite, carbon black, graphene oxide, reduced graphene oxide, carbon fibers, porous carbon, carbon nanotubes, fullerenes, graphene, activated carbon, amorphous carbon, soft carbon, hard carbon, or combinations thereof. Non-limiting examples of active materials include lithium metal oxides, lithium mixed metal oxides, lithium phosphate, lithium oxynitride, lithium titanate, lithium mixed metal phosphates, lithium nitride, lithium sulfide, sodium metal oxides, sodium mixed metal oxides, sodium phosphate, sodium mixed metal phosphates, silica, silicon, metal alloys, chalcogenides, transition metal oxides, metal sulfides, metal nitrides, carbon nanotubes, graphite, graphene, or combinations thereof. Exemplary electroactive materials for lithium-ion batteries include lithium metal oxides such as lithium manganese oxide (LMO), lithium nickel cobalt aluminum oxide (Li-NCA), lithium nickel manganese cobalt oxide (Li-NMC), lithium cobalt oxide (LCO), lithium nickel oxide (LNO), lithium nickel manganese oxide (LNMO), lithium nickel cobalt manganese oxide (LNCM), lithium iron phosphate (LFP), lithium manganese phosphate (LMP), and lithium cobalt phosphate (LCP).Non-limiting examples of polymers include polyvinylidene fluoride (PVDF), polyacrylic acid (PAA), perfluoroalkoxyalkanes (PFA), polythiophene, polypyrrole, polyacetylene, poly(tetramethylpiperidinyl oxymethacrylate) (PTMA), or combinations thereof.

[0080] The battery may further include a separator disposed between a first electrode and a second electrode. The separator separates the first electrode and the second electrode to avoid short-circuiting the electrodes. In one embodiment, the separator is deposited over the first electrode or a solid electrolyte-bonded electrode according to the process shown in Figure 1. In another embodiment, a standalone separator, plasma-treated to mechanically bond to the surface of the first electrode, the second electrode, or the surface of the solid electrolyte, may be provided in the chamber.

[0081] Examples of separators include, but are not limited to, glass, ceramics, polymers, or combinations thereof.

[0082] Exemplary solid electrolyte materials include lithium phosphate nitride, lithium garnet ceramic, sulfide-based lithium compounds, polymer-based electrolytes, polyethylene oxide-based electrolytes, poly(diallyldimethylammonium) (PDADMA), or combinations thereof. In some embodiments, the solid electrolyte separates the anode and cathode, and in such battery designs, no separator is present.

[0083] Figure 2 is a schematic diagram of a plasma apparatus 200 for continuous manufacturing of electrodes for electrochemical devices according to one embodiment of the present disclosure. The plasma apparatus 200 comprises a chamber 202 and a DC power supply 204. The plasma apparatus 200 is also called a "plasma printer".

[0084] Chamber 202 is filled with an electrolyte 206. The electrolyte is circulated within Chamber 202, supplied through an inlet 208 at a certain flow rate and discharged through an outlet 210. A set of at least one plasma anode 212 is disposed within Chamber 202. At least one plasma anode 212 is optionally operable to move in and out of Chamber 202. In the illustrated embodiment, the set of at least one plasma anode 212 is arranged parallel to each other. A current collector 214 is disposed within Chamber 202 at a distance from at least one plasma anode 212, and the current collector moves relative to at least one plasma anode at a certain translational velocity. The distance between the current collector (214) and at least one anode (212) is adjusted for stable plasma generation. The current collector 214 is optionally operable to move in and out of Chamber 202. In the roll-to-roll process illustrated in Figure 2, the current collector 214 is introduced into the chamber 202 via the roller 220, and after electrolytic plasma treatment, the treated current collector 216, i.e., the electrode (216), is removed via the roller 220. In this embodiment, the current collector 214 is sandwiched between at least one set of plasma anodes 212 so that both sides of the current collector 214 are treated.

[0085] A DC power supply 204 applies a voltage between at least one plasma anode 212 and the current collector 214. When a voltage is applied, plasma is generated, which induces mechanical bonding of the electroactive material on the surface of the current collector 214, forming a layer. The apparatus can be used for surface modification of the current collector 214, as described above. Surface modification includes cleaning the surface, removing impurities, or changing the morphology of the surface of the current collector (214).

[0086] By moving the current collector 214 on the roller 220, the next portion of the current collector falls into the next plasma zone, and the process is repeated until both sides of the current collector 214 are completely coated, forming a continuous layer on the current collector 214 and creating a coated current collector 216. The coated current collector 216, i.e., the electrode 216, is removed from the chamber 202 in a single pass. In one embodiment, the coated current collector 216 may be carried to the coating chamber 202 to complete a second pass, and this process can be repeated many times to obtain a thicker coating. Alternatively, a set of apparatus 200 may be installed in series, and the coated current collector 216 is fed through the second apparatus to form a thicker layer. In another embodiment, the second apparatus may have a different electrolyte to form a coating of a second electroactive material over the coated current collector 216, in which case the current collector is coated with the second electroactive material to form a stepped multilayer.

[0087] Plasma parameters include, but are not limited to, the composition of the liquid electrolyte, flow rate, applied voltage, composition of the current collector, translational velocity, or a combination thereof.

[0088] The plasma apparatus 200 is customizable and can be adjusted from a laboratory benchtop system to a large-scale system for fabrication. A series of plasma apparatuses 200 may be combined to manufacture processed current collectors, electrodes, or solid-state batteries.

[0089] Commercially, electrolytic plasma has been used for metal cleaning or for depositing oxide layers across metals. However, the use of electrolytic plasma is quite limited. This is because controlling the plasma and achieving precise control over the electrolytic process is extremely difficult, as variations in temperature, pressure, or plasma composition can significantly affect the results and lead to inconsistent outcomes. Furthermore, plasma processing involves complex processes and esoteric setups.

[0090] A continuous process for manufacturing binder-free electrodes and solid-state batteries is disclosed for the first time. As described in Figure 1, the relative motion of at least one plasma anode and current collector, combined with the frequency of the DC power supply, results in high-frequency on and off plasma on short timescales of picosecond to nanoseconds. When plasma is generated on short timescales, it results in surface activation of the current collector, electroactive material, and / or additives.

[0091] The coated current collector of this disclosure comprises a layer containing a desired material that is chemically independent. The morphology, thickness, or porosity of the layer can be varied as desired by adjusting the plasma parameters. [Examples]

[0092] The following examples are provided for the preparation of electrodes. Electrode samples were fabricated by electrolytic plasma deposition of electroactive materials containing graphene, tin, and silicon onto various current collectors. Sample 1 was formed using a steel substrate as the current collector. Sample 2 used copper foil as the current collector. Sample 3 used aluminum foil as the current collector.

[0093] For electrolytic plasma deposition using an aqueous liquid electrolyte, a plasma apparatus as shown in Figure 2 was used. The liquid electrolyte contained metal salts and conductive carbon to increase its conductivity. Solid electroactive materials were introduced into the liquid electrolyte as dispersions of graphene, silicon, and tin at concentrations of 45%, 45%, and 10% by weight, respectively.

[0094] When a voltage was applied between the anode of the plasma device and the current collector, plasma was generated, depositing electroactive materials onto the current collectors, namely steel, copper, and aluminum. As a result of the electroactive material deposition, a continuous layer or coating was formed across the current collector, forming Sample 1, Sample 2, and Sample 3, respectively. It was found that the electroactive layer was mechanically bonded to the surface of the current collector.

[0095] The conductivity of samples 1-3 was found to be very similar to that of a current collector exhibiting a well-formed layer with low resistance to current conduction.

[0096] The continuous layers of Sample 1, Sample 2, and Sample 3 were characterized using atomic force microscopy (AFM) to evaluate the surface smoothness of the layers. AFM revealed a surface roughness of less than 50 nanometers over an area of ​​20 square microns for Samples 1-3.

[0097] Raman spectroscopy studies were performed on samples 1-3. Sample 1 had a thicker coating, ranging from 80 to 150 microns, compared to samples 2 and 3, while the graphene feature was approximately 2 microns smaller. Although the process parameters were similar, changes in the composition of the current collector, such as the current collector material, may have contributed to the difference in coating thickness between samples 1-3.

[0098] Scanning electron microscopy (SEM-EDX) analysis with energy-dispersive X-ray spectroscopy was performed on sample 1 to analyze the layer composition at various locations within the layer. Figure 3 shows SEM-EDX images 300 at various locations, where 302 corresponds to the bulk layer, 304 to the steel substrate, 306 to the interface between the bulk layer and the layer, and 308 to the interface between the steel substrate and the layer. The compositions of carbon, oxygen, iron, and manganese detected at these locations are shown in Table 1. The presence of detected iron and manganese is most likely from the steel substrate. Within the layer, the concentrations of iron and manganese vary from the maximum value in the steel substrate to the minimum value in the bulk layer within a distance of less than 100 microns. This confirms that the plasma printing process of the present invention is a surface phenomenon without changing the material or electroactive material constituting the current collector. [Table 1]

[0099] The compositions shown in Figure 300 and Table 1 revealed close contact between graphene and the steel current collector due to mechanical bonding during electrolytic plasma deposition. The anode of a lithium battery is often coated with a primer coating (such as an interface layer) to enhance the bonding between the electroactive material and the current collector. As shown in this embodiment, electrolytic plasma deposition eliminates the need for such a primer coating. Using the method of the present invention, graphene can be coated over a metal onto which an electroactive material can be deposited.

[0100] Samples 1–3 were incorporated as anodes into lithium hemispherical cells, and battery performance was evaluated. These samples exhibited high Coulomb efficiencies in the range of 65%–98%. As used herein, the term “Coulomb efficiency” is defined as the ratio of the discharge capacity of the anode material to the theoretical discharge capacity derived from electrochemical calculations, including Faraday’s law. The lithium hemispherical cells formed using samples 1–3 exhibited the expected cell cycle patterns for the new materials. The terms “cycle life” or “cycle” refer to the number of discharge-charge cycles a battery can undergo before it no longer meets certain performance criteria. For example, electric vehicle (EV) batteries have a cycle life of over 2000 cycles.

[0101] It should be understood that the above description is intended to be illustrative and not limiting. Furthermore, many other embodiments will be apparent to those skilled in the art upon reading and understanding the above description. Although this disclosure has been described with reference to specific embodiments, it should be recognized that this disclosure is not limited to the embodiments described and can be carried out with modifications and changes within the scope of the appended claims.

Claims

1. An electrode for an electrochemical device manufactured using a process, wherein the process is A step of providing a chamber filled with a liquid electrolyte and comprising at least one plasma anode, wherein the liquid electrolyte includes an electroactive material; A step of providing a current collector in the chamber, wherein the current collector and the at least one plasma anode move relative to each other at a certain translational velocity, and the current collector, the at least one plasma anode, or both, are operable to move continuously in and out of the chamber. A step of applying a voltage between the at least one plasma anode and the current collector to generate plasma, wherein the plasma is generated in an initial plasma zone between a portion of the current collector and the at least one plasma anode, and the plasma induces mechanical bonding of the electroactive material to the portion of the current collector to form a layer; A step of obtaining the electrode by moving at least one plasma anode, the current collector, or both, to position the next portion of the current collector relative to the next plasma zone, extending the layer of the electroactive material to the next portion of the current collector, and repeating this step along the dimensions of the current collector to form a continuous layer on the current collector, wherein the temperature of the bulk liquid electrolyte in the chamber is 100°C or less during the process, Electrodes, including

2. The electrode according to claim 1, wherein the electroactive material comprises a metal, a metal salt, a nonmetal, a nonmetal salt, a polymer, a donor-acceptor organic molecule, or a combination thereof.

3. The electrode according to claim 2, wherein the electroactive material includes lithium metal oxides, lithium mixed metal oxides, lithium phosphate, lithium mixed metal phosphates, sodium metal oxides, sodium mixed metal oxides, sodium phosphate, sodium mixed metal phosphates, silica, silicon, metals, metal oxides, metal sulfates, metal oxides, alloys, chalcogenides, transition metal oxides, metal sulfides, metal nitrides, carbon nanotubes, graphite, graphene, carbon black, fullerenes, all kinds of carbon and its composites or combinations thereof.

4. The electrode according to claim 1, wherein the current collector is a metal, a nonmetal, a metal oxide, a polymer, or a combination thereof.

5. The electrode according to claim 1, wherein the continuous layer has a thickness in the range of 0.05 micrometers to 20 microns in a single pass of the current collector through the chamber.

6. The electrode according to claim 1, wherein the continuous layer has a porosity in the range of 0.1% to 80%.

7. The electrode according to claim 1, wherein the continuous layer is multilayer, and the continuous layer comprises a single electroactive material or two or more electroactive materials.

8. The electrode according to claim 1, wherein the continuous layer is a stepped layer, and the concentration of the electroactive material changes across the cross-section of the continuous layer.

9. The electrode according to claim 1, wherein the current collector comprises copper, aluminum, or nickel, and the electroactive material comprises graphite, porous carbon, carbon nanotubes, fullerene, graphene, activated carbon, carbon black, amorphous carbon, soft carbon, hard carbon, or a combination thereof.

10. The electrode according to claim 1, wherein the current collector contains aluminum, and the electroactive material contains additives including graphene combined with silicon or tin, and polyvinylidene fluoride.

11. The electrode according to claim 1, wherein the current collector contains carbon, and the electroactive material includes boron-doped carbon, boron nitride, boron carbide graphite, porous carbon, carbon nanotubes, fullerene, graphene, activated carbon, carbon black, amorphous carbon, soft carbon, hard carbon, or a combination thereof.

12. The electrode according to claim 7, wherein the multilayer continuous layer comprises a first layer extending over the current collector and a second layer extending over the first layer, the current collector comprises copper, steel, nickel, or aluminum, the first layer comprises graphene, and the second layer comprises silicon, tin, lithium, or a combination thereof.

13. The electrode according to claim 1, wherein the electrochemical device includes a battery, a solid-state battery, an electrolytic capacitor, or a supercapacitor.

14. The electrode according to claim 1, wherein the electrode does not contain a binder.

15. A continuous process for manufacturing electrodes for electrochemical devices, Step (102) of providing a chamber filled with a liquid electrolyte and comprising at least one plasma anode, wherein the liquid electrolyte is continuously supplied at a certain flow rate and discharged from the chamber, and the liquid electrolyte comprises an electroactive material, Step (104) of providing a current collector in the chamber, wherein the current collector and the at least one plasma anode move relative to each other at a certain translational velocity, and the current collector, or the at least one plasma anode, or both, are operable to move in and out of the chamber. Step (106) of applying a voltage between the at least one plasma anode and the current collector to generate plasma, wherein the plasma is generated in an initial plasma zone between a portion of the current collector and the at least one plasma anode, and the plasma induces mechanical bonding of the electroactive material over the portion of the current collector to form a layer, A step of obtaining the electrode by moving at least one plasma anode, the current collector, or both, to position the next portion of the current collector relative to the next plasma zone (108), extending the layer of the electroactive material onto the next portion of the current collector, and repeating this step along the dimensions of the current collector to form a continuous layer on the current collector, wherein the temperature of the bulk liquid electrolyte in the chamber is 100°C or less during the process, and a step of positioning and repeating (108), A continuous process that includes this.

16. The continuous process according to claim 15, wherein the liquid electrolyte comprises an additive, the additive comprising a metal, a metal oxide, a metal salt, a nonmetal, a nonmetal salt, an electroactivating material, a binder, a polymer, a pore-forming agent, or a combination thereof.

17. The continuous process according to claim 15, wherein the electroactive material comprises a metal, a metal salt, a nonmetal, a nonmetal salt, a polymer, a donor-acceptor organic molecule, or a combination thereof.

18. The continuous process according to claim 15, wherein the current collector is a metal, a metal oxide, a nonmetal, a polymer, or a combination thereof.

19. The continuous process according to claim 15, wherein the step of providing the current collector into the chamber includes providing a current collector that has been pre-coated with an electroactive slurry.

20. The continuous process according to claim 15, wherein the continuous layer has a thickness in the range of 0.05 to 20 microns in a single pass of the current collector through the chamber.

21. The continuous process according to claim 15, wherein the continuous layer has a porosity in the range of 0.1% to 80%.

22. The continuous process according to claim 15, wherein the plasma is controlled by adjusting the composition of the electrolyte, the composition of the current collector, the translational velocity, the flow rate, the voltage, or a combination thereof.

23. The continuous process according to claim 15, wherein the process is a roll-to-roll process, and the current collector enters and exits the chamber at a speed in the range of 1 to 400 meters per minute (m / min).

24. A method for manufacturing batteries, i) Providing a chamber filled with a first electrolyte and comprising at least one plasma anode, wherein the first electrolyte is continuously supplied at a certain flow rate and discharged from the chamber, and the first electrolyte comprises a first electroactive material; ii) Providing a current collector in the chamber, wherein the current collector and the at least one plasma anode move relative to each other at a certain translational velocity, and the current collector, or the at least one plasma anode, or both, are operable to move in and out of the chamber. iii) A step of applying a voltage between the at least one plasma anode and the current collector to generate a plasma, wherein the plasma is generated in an initial plasma zone between a portion of the current collector and the at least one plasma anode, and the plasma induces mechanical bonding of the first electroactive material across the portion of the current collector to form a layer; iv) Moving the at least one plasma anode, the current collector, or both to position the next portion of the current collector relative to the next plasma zone, extending the layer of the first electroactive material onto the next portion of the current collector, and repeating this step along the dimensions of the current collector to form a continuous layer on the current collector and obtain a first electrode; v) A step of repeating steps (i) to (iv) using the first electrode and the second electrolyte, wherein the second electrolyte includes a solid electrolyte material, the solid electrolyte material is deposited on the surface of the first electrode, and the solid electrolyte material is mechanically bonded to the surface of the first electrode to form a solid electrolyte bonded electrode, and the step is repeated. vi) A step of repeating steps (i) to (iv) using the solid electrolyte bonded electrode and the third electrolyte, wherein the third electrolyte includes a second electroactive material, the second electroactive material is deposited on the surface of the solid electrolyte bonded electrode, the second electroactive material is mechanically bonded to the surface of the solid electrolyte bonded electrode to form a battery, the battery includes the first electrode, the solid electrolyte, and the second electrode, and the temperature of the bulk first electrolyte or bulk second electrolyte in the chamber is 100°C or less, and repeating this step. Methods that include...

25. The method according to claim 24, wherein a separator is provided between the first electrode and the second electrode, and the separator comprises glass, ceramic, polymer, or a combination thereof.

26. The method according to claim 24, wherein the current collector comprises a metal, a nonmetal, a metal oxide, a polymer, or a combination thereof.

27. The method according to claim 24, wherein the first electroactive material and the second electroactive material independently comprise a metal, a metal salt, a nonmetal, a nonmetal salt, a polymer, a donor-acceptor organic molecule, or a combination thereof.

28. The method according to claim 24, wherein the solid electrolyte material includes lithium phosphate nitride, lithium garnet ceramic, sulfide-based lithium compound, polymer-based electrolyte, polyethylene oxide-based electrolyte, or a combination thereof.

29. The method according to claim 24, wherein the first electrode and the second electrode do not contain a binder.

30. A continuous process for processing the current collector of a battery, To provide a chamber filled with a liquid electrolyte and comprising at least one plasma anode, wherein the liquid electrolyte is continuously supplied at a certain flow rate and discharged from the chamber. To provide the current collector within the chamber, wherein the current collector and the at least one plasma anode move relative to each other at a certain translational velocity, and the current collector, or the at least one plasma anode, or both, are operable to move continuously in and out of the chamber. Applying a voltage between the at least one plasma anode and the current collector to generate plasma, wherein the plasma is generated in an initial plasma zone between a portion of the current collector and the at least one plasma anode, and the plasma modifies the surface of the portion of the current collector in the initial plasma zone. The process involves moving at least one plasma anode, the current collector, or both to position the next portion of the current collector relative to the next plasma zone, modifying the surface of the next portion of the current collector, and repeating this step along the dimensions of the current collector to obtain a current collector that has been processed, wherein the temperature of the bulk liquid electrolyte in the chamber is 100°C or less during the process, and the step of positioning and repeating is performed. A continuous process that includes this.

31. The continuous process according to claim 30, wherein the liquid electrolyte is an aqueous system, a solvent system, or an ionic liquid system.

32. The continuous process according to claim 30, wherein the liquid electrolyte comprises an additive, an electroactive material, or both.

33. The continuous process according to claim 32, wherein the additive comprises a metal, a metal oxide, a metal salt, a nonmetal, a nonmetal salt, an electroactivating material, a binder, a polymer, or a pore-forming agent, or a combination thereof.

34. The continuous process according to claim 32, wherein the additive or electroactive material is a gas, solid, liquid, or a combination thereof.

35. The continuous process according to claim 32, wherein the liquid electrolyte contains the electroactive material, and modifying the surface of the current collector includes forming a layer of the electroactive material mechanically bonded to the surface of the current collector.

36. The continuous process according to claim 30, wherein the current collector is a metal, a metal oxide, a polymer, or a combination thereof.

37. The continuous process according to claim 30, wherein providing the current collector in the chamber includes providing a current collector that has been pre-coated with an electroactive slurry.

38. The continuous process according to claim 30, wherein modifying the surface includes cleaning the surface of the current collector or modifying the morphology of the surface of the current collector using plasma generated in the liquid electrolyte.

39. The continuous process according to claim 30, wherein the modification of the surface of the current collector is controlled by adjusting the composition of the electrolyte, the composition of the current collector, the translational speed, the voltage, the flow rate, or a combination thereof.

40. The continuous process according to claim 30, wherein the process is a roll-to-roll process, and the current collector enters and exits the chamber at a speed in the range of 1 to 400 meters per minute (m / min).

41. A processed current collector prepared according to the continuous process described in claim 30.

42. A plasma apparatus for the continuous manufacture of electrodes for electrochemical devices, A chamber (202) having an inlet (208) and an outlet (210) for circulating a liquid electrolyte (206) at a certain flow rate, wherein the chamber (202) is filled with the liquid electrolyte (206) and the liquid electrolyte (206) contains an electroactive material, Displaced within the chamber (202), at least one plasma anode (212) is capable of operating to selectively enter and exit the chamber (202), A current collector (214) disposed within the chamber (202) at a distance from the at least one plasma anode (212), wherein the current collector (214) moves relative to the at least one plasma anode (212) at a certain translational velocity, and the current collector (214) is operable to move in and out of the chamber (202) at will. A DC power supply (204) for generating plasma by applying a voltage between the current collector (214) and the at least one plasma anode (212), wherein the generated plasma induces mechanical bonding of the electroactive material on the surface of the current collector (214) to form the electrode (216), and the plasma is controlled by adjusting the composition of the liquid electrolyte (206), the composition of the current collector (214), the translational velocity, the flow rate, the voltage, or a combination thereof. A plasma device equipped with the following features.

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