A method for producing a layer or multilayer structure comprising lithium using laser ablation of a coating

Abstract

In the present invention, a method for manufacturing a material for electrochemical energy storage devices is introduced, such that a laser-ablation-based deposition method is used for manufacturing at least one material layer containing lithium. The method is characterized in that measurement information obtained from the spectrum of the electromagnetic radiation generated from laser ablation is used to control the process. A so-called roll-to-roll method can be used in the deposition, in which the substrate (15, 32, 44, 64, 75, 85) to be coated is guided from one roller (31a) to a second roller (31b), and the deposition takes place in the area between the rollers (31a-b). Furthermore, rotating and / or moving mirrors (21) can be used to direct the laser beam (12, 41, 71a-d, 81a-d) as a beam line array (23) to the surface of the target material (13, 42a-b, 72a-d, 82a-d, 82A-D).

Description

TECHNICAL FIELD

[0001] The present invention relates to the fabrication of electrochemical energy storage devices utilizing lithium, such as batteries and capacitors, their structure, and materials used in these devices. The invention is particularly directed to a method of fabricating at least one lithium-containing component of a lithium battery, lithium-ion battery, or lithium-ion capacitor, which method utilizes laser ablation, i.e. the removal of material by a laser. The invention is also directed to the use of lithium-containing materials produced by laser ablation deposition in batteries, capacitors, and other electrochemical devices. BACKGROUND

[0002] With the growth of mobile devices, electric vehicles, and energy storage needs, the demand for battery technology development is also increasing. Li-ion batteries have been successful in many applications, especially because they have good energy density and charging possibilities, among others, compared to traditional Ni-Cd (nickel-cadmium) and Ni-Mn (nickel-manganese) batteries.

[0003] Today, the widely adapted lithium battery technology is based on a positive electrode (cathode) made of a transition metal oxide and a carbon-based negative electrode (anode). The migration path for Li ions between the positive and negative electrodes is an electrolyte, which in contemporary solutions is liquid, but methods using solid-state electrolytes are being actively developed. Especially in the case of liquid electrolytes, a microporous polymer separator is used between the anode and the cathode as an insulator, which prevents the contact of the anode and the cathode, but allows the passage of ions through the separator.

[0004] The energy density of a Li-ion battery depends on the ability of the electrode materials to reversibly store lithium and the amount of lithium available for ion exchange in the battery. When the battery is used, meaning that energy is extracted from the battery or stored in the battery, lithium ions move between the positive and negative electrodes. During use, the electrode materials undergo chemical and structural changes that affect the materials' ability to store lithium or the amount of lithium. Some chemical reactions are irreversible and consume lithium, which means that the lithium available for ion exchange, i.e. for storing and releasing stored energy, will decrease. One example of such a reaction is the formation of a so-called SEI (Solid Electrolyte Interface) layer at the surface of the negative electrode. The formation of the SEI layer occurs to a large extent during the first charge-discharge cycle, but it is also possible that new SEI layers are continuously formed. In contemporary Li-ion battery technology, lithium is introduced into the battery structure and almost completely stored in the positive electrode material. When lithium is consumed during the formation of the SEI layer during the first charge-discharge cycle, parts of the material in the electrodes will not be utilized and will increase the volume and mass of the battery as inactive material, which decreases the energy density of the battery. It is also known that Li has a tendency to get trapped in materials that form compounds with it. This happens when the active electrode material is a Li compound forming material such as Si, Sn or Al. Furthermore, it is known that the same phenomenon occurs on current collector materials such as Cu, Ni and Ti. Taking these factors into account, and in order to optimize the performance of a Li-ion battery, it can be beneficial to fill the Li storage material to its maximum capacity before the normal use of the battery.

[0005] To compensate for the above-mentioned loss of lithium, an excess of lithium can be introduced into the battery structure before the battery is assembled, so that after the first charge-discharge cycle, the amount of active lithium available will be greater and will be more suitable for the capacity of the electrode materials to store lithium. However, the total amount of lithium should be chosen so that it does not exceed the lithium storage capacity of the electrode materials during use of the battery, so that it does not lead to the formation of metallic lithium at the surface of the negative electrode and does not affect the safe use of the battery.

[0006] A number of methods have been developed to add lithium to the battery materials. This method is called pre-lithiation. Pre-lithiation can be achieved by chemical or electrochemical means, by using Li metal or with the help of additives. Large-scale commercial development of these methods is mostly limited due to the lack of cost-effective industrial methods. In particular, in many of the proposed methods, pre-lithiation is achieved as a separate process step before battery assembly, which makes the manufacturing process of the battery more complex and slower. In the existing Li-ion battery manufacturing process, pre-lithiated powders of the electrode materials can be utilized as such, but due to their instability, a separate stabilization step and / or protective layer is required, both of which reduce the total amount of active material ja, thereby interfering with the normal operation of the battery. These methods and the state of the art are presented by Florian Holtstiege et al. in the publication: “Pre-Lithiation Strategies for Rechargeable Energy Storage Technologies: Concepts, Promises and Challenges”, Batteries, 2018, Vol. 4.

[0007] In some specific cases, pre-lithiation can enable the utilization of new materials in batteries, thereby increasing the energy density and lifetime of the battery. For example, the use of silicon as an active material in the negative electrode can be advantageous, as in theory, the energy storage capacity of silicon is 10 times that of the traditional negative electrode active material, graphite. Silicon has its limitations due to the volume change caused by charging and discharging during battery use, which also causes structural damage, contact between particles and connection to other structures. In addition, the continuous volume change of silicon particles causes the SEI layer formed on the particle surface to break, which leads to the formation of a new SEI, thereby consuming the available lithium during each charge and discharge cycle. By introducing silicon as a lithium-containing substance into the battery structure, the relative volume change, the associated regrowth of the SEI layer and the mechanical damage of the electrode can be reduced. In addition, pre-lithiation has the potential to improve the performance of the electrode material (for example, by enabling the use of higher current densities due to reduced impedance) and to improve the beneficial mechanical properties, thereby reducing the magnitude of the stresses generated in the material during battery use.

[0008] When talking about lithium batteries, one usually refers to Li metal batteries with lithium metal as anode. The advantage of a Li anode is its high energy density, but its use is limited by the uncontrolled growth of so-called Li dendrites, i.e. the formation of needle-like protrusions, which can lead to short circuits as the dendrites are able to penetrate the separator and electrically connect the anode and cathode. This is a major safety risk. Furthermore, lithium is highly reactive, which is why special provisions for its handling and use are required to avoid the detrimental effects of the reaction products. For example, this reactivity easily leads to the formation of a thick SEI layer on the lithium metal surface. Furthermore, when using lithium metal as such, without a supporting frame as anode, the volume change of the anode can be unlimited as the anode is free of lithium in the discharged state of the battery.

[0009] One of the limiting factors associated with the use of lithium metal is the difficulty to form a reliable bond with other materials. For example, it has been found challenging to bond Li metal to a metal foil current collector in such a way that its contact is able to withstand long-term use.

[0010] The use of Li metal as anode has been widely studied and solutions have been developed that enable the safe use of Li metal. Possible solutions include the creation of a more robust SEI layer on the Li surface, as well as protective coatings, solid-state electrolyte materials and supporting frames. The lithium storage frame should have chemical and mechanical stability, provide sufficient free surface area for lithium storage, be a good conductor of ions and electrons, and be light in weight.

[0011] Various protective coatings can be required to minimize detrimental electrochemical and chemical reactions at the interface between different materials, especially lithium-containing materials, and to minimize damage that occurs to the battery or capacitor materials during use. Furthermore, protective coatings can need to be lithiated in order to function as Li ion shuttles. For example at the cathode surface, inorganic materials such as ZnO, AI2O3, AIPO4, AIF3, in their lithium-containing form, allow Li ions to pass through, but prevent reactions between the cathode and the electrolyte or prevent dissolution of cathode components. Solid-state electrolytes, such as Li 2.88 PO 3.73 N 0.14 (LIPON), Li 10 GeP2S 12 (LGPS), Li 9.54 Si 1.74 P 1.44 5 11.7 Cl 0.3 , Li 9.6 P3S 12 (LPS), Li 1.3 Al 0.3 Ti 1.7(LATP), LLTO, LLMO (M = Zr, Nb, Ta) can be used as protective coatings for the electrodes. In particular, the LLMO type electrolytes described above can be used as mechanically durable protective coatings and support frames.

[0012] So-called supercapacitors are electrochemical devices for energy storage. In comparison to modern batteries, they are able to absorb and generate higher currents and, in addition, they are also able to withstand more charge and discharge cycles. These properties complement battery technology, for example, in electric cars, supercapacitors can be used for short-term energy storage, to absorb the energy generated by the drive and to provide the high currents required for acceleration. Li-ion capacitors are a special hybrid type of supercapacitors, which partially utilize the properties and functions of Li-ion battery technology. Controlling the amount of lithium and adding additional lithium in the structure of Li-ion capacitors is a method to improve the performance of the capacitor, which is the reason why prelithiation has been applied to commercial Li-ion capacitors.

[0013] For example, to utilize Li metal in energy storage applications, it should be possible to produce a Li metal layer with the following properties, among others:

[0014] - free of impurities or harmful reaction products within the layer or at the interface

[0015] - having a smooth surface

[0016] - having good adhesion to the substrate

[0017] - controlled to contain a certain precise amount of Li metal SUMMARY

[0018] The present invention discloses a method for the production of lithium containing materials and material layers for lithium batteries, Li-ion batteries and Li-ion capacitors, which utilizes the advantages of laser ablation deposition to control the composition and microstructure, the doping of the material and the production of multilayer structures. The method is suitable for the large-scale industrial production of material layers and coatings. The method enables a quantitative and qualitative precise treatment of the material in a controlled atmosphere, which enables the production of reaction sensitive materials, such as lithium and lithium containing compounds for batteries and capacitors, with the desired composition and without the presence of reaction products that can be harmful to the operation of the final product.

[0019] With regard to the manufacturing method (laser ablation deposition, pulsed laser deposition, PLD) and the manufactured product (components of Li-ion batteries), the present invention relates to existing patent applications and granted patents, in which the state of the art is presented:

[0020] - Finnish patent application FI20175056 discusses the manufacturing of anode materials and Finnish patent application FI20175057 discusses the manufacturing of cathode materials by pulsed laser ablation deposition. These applications disclose the use of laser ablation deposition in the manufacturing of layered composite structures and the possibility to achieve a combination of performance improvements in electrochemical, chemical and mechanical properties in the electrodes of Li-ion batteries by these methods. In addition, these applications mix the electrode materials with some other materials by using final hybrid target materials, separate targets or successive coating steps.

[0021] - Finnish patent application FI20175058 discusses the manufacturing of solid electrolyte materials by pulsed laser ablation deposition.

[0022] - Finnish patent application FI20145837 (WO2016046452A1) discusses the coating of porous polymer separators for Li batteries with porous materials by applying pulsed laser ablation technology.

[0023] - Finnish patent FI126659 (application WO2018087427) discusses the production of thin and dense oxide coatings on the surface of porous polymer separators or electrodes by pulsed laser ablation deposition.

[0024] - Finnish patent FI126759B (application WO2016087718A1) discusses the production of porous coatings by pulsed laser ablation deposition with composite target materials.

[0025] - Patent application US20050276931A1 discloses the manufacturing of electrochemical devices based on thin films (e.g. thickness less than 10 pm) and multilayer structures by pulsed laser ablation deposition.

[0026] In addition, the object of the present invention (the production of lithium layers or the addition of lithium to one / more components of electrochemical energy storage devices utilizing lithium, i.e. prelithiation) has been previously discussed in the following patents, patent applications and publications of prior art:

[0027] - Florian Holtstiege et al.: “Prelithiation strategies for rechargeable energy storage technologies: concepts, promises, and challenges”, Batteries, 2018, Vol. 4.

[0028] - The addition of lithium to the anode material of silicon-based Li-ion batteries by thermal evaporation has been discussed in the publication of Takezawa et al.: “Electrochemical Properties of a SiOx Film Anode Pre-lithiated by Evaporation of Metallic Li in Li-ion Batteries”, Chem. Lett., 46, 1365-1367, 2017.

[0029] - The use of a three-dimensional support structure in a composite anode containing Li metal has been proposed in the publication of Liang et al.: “Composite lithium metal anode by melt infusion of lithium into a 3D conducting scaffold with lithiophilic coating”, Proc. Natl. Acad. Sci. U. S. A., vol. 113, no. 11, 2862-2867, 2016.

[0030] - US9966598B2 “High capacity prelithiation reagents and lithium-rich anode materials”. This publication proposes pre-lithiation reagent compounds for batteries.

[0031] - The publication KR101771122B1 proposes a pre-lithiation method which makes use of a lithium battery based on silicon or silicon oxide.

[0032] - Other publications in this field are US9705154B2, WO201519205iA1 and US2017338480A1.

[0033] - The patent KR101794625B1 shows a lithium-containing coating which makes use of molten Li metal.

[0034] - The patent application US2010120179A1 proposes a Li-ion battery anode in which lithium is first added to the active anode material and then the lithium-containing active anode material is ground into particles before producing the anode layer. In particular, the application shows the use of Si as such anode material. The application mentions laser ablation as a method for adding lithium to the anode material.

[0035] - Patent application US2019386315A1 proposes a lithium electrode, wherein lithium is coated with a layer of aluminum oxide to prevent direct contact of electrolyte and lithium metal and with a layer of carbon for forming a stable interface with the electrolyte.

[0036] - Patent application WO2005013397 discloses a method of introducing lithium into electrochemical systems, in particular into electrodes for such systems.

[0037] - Patent application WO2018025036A1 discloses a method of manufacturing a lithium metal coating using a molten lithium source evaporation method.

[0038] - Patent US10476065B2 discloses the deposition of a lithium coating on a separator. Among other manufacturing methods, this patent lists PVD (Physical Vapor Deposition) as one possible method to produce a lithium layer. Furthermore, the patent description also mentions roll-to-roll manufacturing as well as the deposition of a protective layer and a current collector layer.

[0039] In the method of the present invention, a laser beam is directed at a target material to remove material from the target material in the form of atoms, ions, particles or droplets or from a combination of such choices. The material ejected from the target material is directed to the surface of the object to be coated, thereby forming a coating with the desired properties and thickness.

[0040] The quality, structure, quantity, size distribution and energy of the material ejected from the target material are controlled by the parameters used in the laser ablation, which include the wavelength, power and intensity of the laser, the temperature of the target material, the pressure of the optional background gas, etc., and in the case of pulsed lasers, the laser pulse energy, pulse length, pulse repetition rate and pulse overlap. Furthermore, the microstructure and composition of the applied target material can be adjusted together with the selected laser parameters to produce the desired process, material distribution and coating.

[0041] One significant advantage of laser ablation deposition is that it can be applied in the processing of many different materials, thereby enabling the production of different combinations of materials and microstructures. This provides the freedom to achieve material selection and structures that are primarily based on the properties of the desired end product and are less influenced by the limitations of the manufacturing method. Depending on the material or material combination and the desired properties, the process parameters of the laser ablation can be adjusted to achieve the desired microstructure and morphology.

[0042] By utilizing laser ablation, it is possible to produce both dense and porous coatings, and also to adjust the porosity, particle size, and free surface area of the layers, all of which properties are of importance in lithium batteries, Li-ion batteries, and Li-ion capacitors. For example, the porosity of the electrode layer enables the electrolyte to be distributed throughout the volume of the electrode material, the contact area between the electrolyte and the electrode material particles is large, and the diffusion length of the ions and electrons is short. Reducing the particle size in the porous structure to below 1 pm is considered a good way to improve the functionality of the lithium storage material. The large open surface area increases the contact area with the electrolyte, thereby increasing the Li atom flux through the interface between the electrode particles and the electrolyte. In addition, the smaller the particle size of the electrode material, the smaller the required diffusion length of lithium, and the faster the electron transfer speed. In some cases, small particle size and large specific surface area increase the storage capacity of Li atoms by increasing the number of storage sites for active Li atoms, thereby increasing the specific storage capacity. The aforementioned benefits achieved by controlling the structure of the electrode material can improve the overall performance of the battery.

[0043] When a Li-ion battery is charged, Li ions move from the cathode to the anode in the electrolyte, for example, in the case of graphite, lithium is stored in the anode material through intercalation between the lattice planes, or in the case of silicon, lithium is stored in the anode material through alloying. During discharge, lithium moves from the anode to the cathode as ions and is stored in the cathode material, for example, in the case of LiCoO2, lithium ions are stored in the cathode material through intercalation between the lattice planes. The storage of lithium causes changes in the structure and properties of the electrode material. Especially for lithium alloying electrode materials, when alloyed with lithium, the volume increases significantly, for example, in the case of silicon, up to 4 times its initial volume, and in the case of tin, more than 2 times its initial volume.

[0044] Controlling and reducing the size of the structural sub-units through laser ablation improves the durability of the material, preventing cracking and bond breaking due to volume changes caused by charge and discharge cycles. Smaller size of the microstructural units, such as anode material particles, can better accommodate the stresses associated with volume changes, whether these units are particles or fibrous sheets or a combination of both. For example, when using silicon as an anode material, reducing the size of the particles to below 150 nm can reduce the tendency of crystalline silicon to crack and the risk of battery performance deterioration. By selecting appropriate laser parameters and controlling the deposition temperature, the laser ablation technique can be used to produce amorphous phase silicon particles, thereby reducing the tendency to crack during charge and discharge cycles, and even increasing the crack-free particle size up to 1 pm.

[0045] Furthermore, the increase of the internal volume of the structure generated by the porosity during the manufacturing process increases the possibility to adapt to volume changes of the structure, especially during the use of the battery. Besides the total amount of porosity, it is also important to control the distribution of the porosity. It is especially advantageous to increase the homogeneity of the porosity distribution. For example, when creating a silicon doped anode material with a binder material by slurry method, the porosity distribution in the created coating is not homogeneous in terms of the volume and size distribution of the pores, which can lead to high local stresses and micro cracking. Laser ablation deposition leads to structures with a homogeneous pore distribution, which type of structure can better withstand volume changes and stresses associated with the charge and discharge cycle without breaking.

[0046] During the use of a Li-ion battery, especially in the case of a liquid electrolyte based, a reaction layer called solid electrolyte interface (SEI) is formed on the surface of the anode material. Due to the volume changes of the anode material, this reaction layer is easily cracked, which cracks lead to the reaction of the fresh anode material surface with the electrolyte. This leads to the constant formation of a new reaction layer and an increase in the layer thickness, which leads to the consumption of the electrolyte. In addition, the increase in the thickness of the reaction layer can disturb the diffusion of Li ions, thus reducing the performance of the Li-ion battery. The cracks generated in the reaction layer can also lead to the growth of needle-shaped Li dendrites through the separator, thus leading to short circuits and permanent damage to the battery. Reducing the particle size reduces the risk of cracking and forming an unstable reaction layer of the reaction layer.

[0047] Some promising electrode materials, such as the anode material Li4Ti5O 12 , whose use is limited by poor electronic conductivity, which can be improved not only by reducing the particle size of Li4Ti5O 12 , but also in the coating process by adding metal particles such as nickel or copper to the particles and the structure. This can be achieved in laser ablation technology by adding the required amount of the doping material to the target material or by performing a so-called combined coating, for example, such that, together with the ablation of Li4Ti5O 12 , a material flow of copper (or some other material capable of improving the electrical conductivity) generated by laser ablation is simultaneously directed to the coating. One possibility is to create the coating in a layer-by-layer manner, for example, such that after the creation of the electrode material coating, a coating of the material improving the electrical conductivity is created, then the electrode material layer is obtained, and this process needs to be repeated for a long enough time to create the desired structure and total layer thickness.

[0048] In addition to the particle size in the electrode coating, factors related to the specific capacity required for optimizing the particle size must also be taken into account, which are not necessarily minimized. For example, in the case of Li4Ti5O 12In some cases, particle sizes smaller than 20 nm may reduce specific capacity, but in practice, controlling the particle size within the 20-80 nm range would be beneficial. Furthermore, due to the high surface area to volume ratio, the number of storage sites for Li atoms in very small particles may be even smaller, highlighting the necessity of structural optimization. In the conventional Li₄Ti₅O₂… 12 In the manufacturing process, the particle size is greater than 1μm, which is outside the optimal size range.

[0049] In the laser ablation deposition process, in order to improve the performance of the battery, the particle size can be adjusted to the optimal range by controlling the laser parameters and background gas pressure, which has significant advantages over other physical or chemical deposition methods such as slurry coating or atomic layer deposition (ALD) or chemical vapor deposition (CVD).

[0050] If necessary, as a final coating process step after producing the so-called active electrode material coating, a thermomechanical protective layer, a coating that affects the properties of the reactive layer, or a coating that improves the chemical durability of the electrode material layer can be produced. The porosity and thickness of this final coating can be adjusted according to the desired functionality.

[0051] Composite material structures can be produced through layer-by-layer or combined processes (combining two or more simultaneous material flows generated by laser ablation), allowing for the modification of electrode material coatings in a variety of ways. For example, when another material with suitable properties (such as carbon) is ablated together with silicon particles or fibers, or sequentially layer-by-layer, the mechanical flexibility and convertibility of the structure can be improved compared to cases where the material contains only silicon. When different materials are added via laser ablation in appropriate proportions and size distributions, both combined and layer-by-layer methods can achieve an optimal combination of electrochemical, chemical, and mechanical properties.

[0052] The crystallinity of materials produced by laser ablation can be controlled, for example, by adjusting the temperature of the substrate. Pulsed laser ablation using short pulses can generate amorphous structures, such as those with different lithium diffusion properties compared to the crystalline structure of silicon. For example, lithium diffusion into silicon particles is more linear, thus reducing particle cracking.

[0053] In conclusion, it can be shown that laser ablation can impart characteristics to the final product that cannot be achieved through other methods. In particular, regardless of the material, the adhesion between the material layer deposited by laser ablation and the substrate is excellent, which is not always achievable with other coating methods. Furthermore, the purity of the coating and the precision of the selected material distribution are also outstanding.

[0054] Based on this process technology, many of the advantageous features described above can be utilized even in a single coating process step with certain prerequisites. Alternatively, the laser ablation process can also be realized in several sequences in one production line, for example, in a first stage a porous layer formed from particles of the electrode material, in the next stage a lithium layer. These stages can be carried out successively until the desired coating thickness is produced. In this process, it is also possible to supplement a stage in which some other metal layer can be doped or dispersed. Furthermore, in order to prevent harmful reactions at the interface between the different materials, different process sequences can be used to deposit protective layers between the layers. Since the coating process takes place in a vacuum chamber in which the gas pressure and composition can be controlled, harmful reactions can be minimized. This ability is crucial when working with battery materials, especially the reaction-sensitive lithium.

[0055] When composite or alloy materials are to be produced, for example a combination of lithium and silicon, the so-called combination method as described above can be used to direct the material streams from two different targets simultaneously to the object to be coated. If necessary, the parameters of the laser directed to the different targets can be adjusted individually and independently in order to optimize the ablation process of the different target materials and to produce the desired structure, composition and material distribution. This type of structure and alloying by lithium can make it possible to use, in particular, silicon and tin as negative electrode materials with less cracking due to volume changes.

[0056] In order to reduce the particle size of the electrode material and to generate the beneficial features described above, it is also possible to use a method in which the nanoparticles are first produced, for example by chemical means. In a next step, the nanoparticles are mixed with binder material and other components, for example lithium and carbon, which together with the nanoparticles form the electrode material, and the mixture is used to produce the final electrode material layer, for example by the slurry method. However, the handling of nanoparticles is very complex and the described method using nanoparticles requires several process steps, thus increasing the production time, costs and the likelihood of quality problems. In the method of the present invention, the production of nanoparticles, the coating process and the addition and mixing of other materials take place in one or both procedures of the laser ablation process, thus improving the cost-effectiveness and controllability of the process. Furthermore, no complex handling of the nanoparticles is necessary. For example, since no binder material is necessary contrary to the slurry method, the potential dissolution of the binder does not interfere with the electrochemical operation of the Li-ion battery.

[0057] In principle, some or more of the aforementioned methods can be used in combination with some other coating methods, for example, since the process steps are carried out sequentially, laser ablation should be utilized in the most suitable coating process step, and some or more other coating methods can be used to supplement the laser ablation. This can be realized as a continuous process step or as a separate process. Furthermore, it is also to be considered that different parameters can be used to generate different types of laser ablation processes, which, in combination with simultaneous events or successive stages, can create quality-related production characteristics or benefits.

[0058] The coating process can be realized by a roll-to-roll method or, for example, by means of a continuous feeding of the sheet material into the production line.

[0059] In view of the productivity of large series, the deposition process must be carried out by utilizing an array of wide laser beams (scanning lines) that can be generated, for example, by moving or rotating mirrors. The laser beam scanning lines ablate the material from the target in the desired manner over the entire coating width and direct the material flow from the target to the selected area on the surface of the substrate. The productivity can also be increased by using multiple laser sources and simultaneously ablating material from one or more targets.

[0060] The inventive concept of the present application also contains the final product manufactured using the method, i.e. a Li battery, Li-ion battery or Li-ion capacitor, which contains all the required material layers, wherein at least one layer containing lithium metal or lithium compound can be manufactured by laser ablation deposition. BRIEF DESCRIPTION OF DRAWINGS

[0061] Figure 1 The principle of the coating procedure using different physical components in the examples of the present application is illustrated,

[0062] Figure 2 The principle of forming a fan array of parallel laser beams using the device setup of the present application is illustrated,

[0063] Figure 3 The so-called roll-to-roll principle related to the coating process is illustrated by way of example,

[0064] Figure 4a The production of coating material on a substrate by the PLD method is illustrated,

[0065] Figure 4b The setup for producing a porous coating is illustrated,

[0066] Figure 4c The setup for producing a composite structure coating by using a composite structure target is illustrated,

[0067] Figure 4d The setup for producing an alloy material coating by using a composite structure target is illustrated,

[0068] Figure 5 The typical structure of a Li-ion battery is illustrated in the form of a cross-sectional view,

[0069] Figure 6 The use of continuous processing units in roll-to-roll manufacturing in connection with the method of the invention is illustrated,

[0070] Figure 7a The combined coating method for composite coatings (also including hybrid coatings) by using two synchronized material flows is illustrated,

[0071] Figure 7b The combined coating method for alloy material coatings by using two synchronized material flows is illustrated,

[0072] Figure 8a The use of continuous coating units to increase the productivity is illustrated,

[0073] Figure 8b The use of continuous coating units to increase the productivity in manufacturing composite structures is illustrated,

[0074] Figure 8c The use of continuous coating units to increase the productivity in manufacturing hybrid materials is illustrated. DETAILED DESCRIPTION

[0075] In the method of the invention, the lithium-containing material layer or multilayer structure of a lithium battery, Li-ion battery or Li-ion capacitor is manufactured by laser ablation deposition, which is used to produce material layers suitable for laser ablation deposition or to obtain relative productivity or quality advantages by the method.

[0076] In laser ablation, material is ejected from a solid or liquid surface by directing a laser beam with sufficiently high irradiance onto the surface of the solid or liquid. The laser beam can be pulsed or continuous wave. Under suitable environmental conditions, the material removed by laser ablation can be collected on the surface of a substrate, thereby forming a coating. This method is called laser ablation deposition.

[0077] In pulsed laser ablation with a pulsed laser beam, material is removed by short laser pulses, the duration of which can vary from milliseconds to femtoseconds. Pulsed laser (ablation) deposition (PLD) generally involves laser pulses with a duration of at most 100000 ps (in other words, at most 100 ns). In one embodiment, a method of ultra-short pulsed laser ablation deposition (so-called US PLD) can also be used, in which the duration of the laser pulses is at most 1000 ps. If necessary, different laser parameters are used to produce different material layers of a lithium battery, Li-ion battery or Li-ion capacitor.

[0078] When using laser pulses to remove material and to generate a material flow from one or more targets to the surface of an object to be coated, the laser energy density (J / cm 2 ) needs to be sufficiently high to remove material from the target. The threshold energy density, i.e. the ablation threshold, at which material is removed from the target, is a material-specific parameter whose value depends, inter alia, on the laser wavelength and the duration of the laser pulse.

[0079] The available laser energy typically used has an order of magnitude which requires an optical modification of the laser beam so that the area of the laser spot on the target surface is reduced in order to achieve a sufficiently high energy density. The simplest way to achieve this is to place a focusing lens in the path of the laser beam at a suitable distance from the target. However, it needs to be taken into account that the intensity of the laser beam has a characteristic spatial and temporal distribution which depends on the laser and the optics used. In practice, even if means are used to homogenize the distribution, there is no completely uniform distribution of intensity and thus of energy density in the laser spot on the target surface. This can lead to the ablation threshold being exceeded only in certain parts of the laser spot, and the size and proportion of the area in which the ablation threshold is exceeded depend on the total laser energy used.

[0080] The removal of material can occur in the form of atoms, ions, molten particles, spalled particles, particles which condense from atoms and ions after ejection, or a combination of several of the above. The removal pattern of material and the properties of the material after removal from the target, such as the condensation tendency, depend, inter alia, on the extent to which the laser energy exceeds the ablation threshold. Depending on the material and the requirements for the structure and morphology of the coating, the parameters of the laser ablation can be adjusted. Suitable parameters can be defined specifically for each material in order to produce the desired coating.

[0081] One feature of laser ablation is that the ablation process generates electromagnetic radiation whose properties depend on the material being processed by the laser ablation and the laser parameters used for the ablation, and in some cases also on the nature of the ablation environment. By analyzing the spectrum of this electromagnetic radiation generated by the ablation, it is possible to gather essential information from the ablation process which can be used to control the process. This, for example, makes it possible to stabilize the course of a long-term coating process so that the desired properties of the coating can be maintained from start to finish and a product of uniform quality can be produced. The process needs to be monitored in detail and, if necessary, adjusted, for example, because the target material is continuously worn away by the ablation and the properties of the laser beam hitting the target can additionally change. The spectrum of the electromagnetic radiation generated by the laser ablation is a kind of fingerprint of the process which also allows the process to be repeated. The spectrum can also identify elements and potential impurities in the target material.

[0082] To ensure the reliability of the measurement of the spectrum generated by laser ablation, it is very important to reliably reproduce the measurement. For the above reasons, the setup of the device for collecting electromagnetic radiation needs to ensure that the radiation path between the ablation spot and the measuring device is clear and constant. Since the laser ablation ejected material can accumulate on any surface that can see the ablation spot, it is necessary to protect the measuring device and the associated optics for collecting electromagnetic radiation. For example, the protection can be a movable window or a plastic film that can continuously expose a fresh surface to the radiation path in order to keep the path clear for the radiation from the ablation spot to the collection optics. As an alternative to this type of consumable protector, the window or film can be continuously cleaned, for example by ion bombardment or laser ablation. In addition, the reliability of the measurement can be improved by using a reference radiation source that can be used for calibration of the measurement and direct comparison of the reference spectrum with the spectrum generated by ablation.

[0083] In addition to the constant repetition rate of the laser pulses, the laser pulses can also be delivered to the target material as so-called pulse trains, which consist of a selected number of pulses at a selected repetition rate. For example, 100-μJ laser pulses at a single 1 -MHz repetition frequency, or a pulse train consisting of 10-μJ laser pulses at a 60-MHz repetition frequency with a 1 -MHz pulse train repetition frequency can produce an average laser power of 100 W. The pulse energy of the individual pulses that make up the pulse train can also be controlled.

[0084] Pulse trains or laser pulse packets, and the high pulse repetition rate achieved by pulse trains, are very important, especially in the case of short laser pulses. By using pulse trains, it is possible to change the interaction between the laser and the material and control the properties of the ejected material. For example, due to the fact that part of the laser pulses interact directly with the cloud of the ejected material, not the solid surface of the target, the high repetition rate can increase the total energy of the material ejected from the target and reduce the number or size of particles in the ejected material.

[0085] It must be noted that after ejection from the target, changes in the structure, size distribution and composition of the material can occur in the material stream before the material adheres to the substrate. This change process can be controlled, for example, by the composition and pressure of the atmosphere, i.e. the background gas, in the deposition chamber, and by adjusting the travel distance of the material (from the target to the substrate).

[0086] It is also possible to bring additional energy to the material stream by directing another laser beam into it. In addition, by a continuous wave laser beam, a pulse train of the above-mentioned laser pulses or a high repetition rate, it is possible to absorb part of the laser energy into the ejected material. The laser beam directed into the material stream can be used to make the potential particles in the material stream smaller, but also to increase the total energy and ionization degree.

[0087] In laser ablation, multiple laser beams directed to the same target can be used simultaneously. Especially when the laser beams have different properties, respectively, the simultaneous interaction on the same area on the surface of the target changes the ablation process. For example, a continuous wave laser beam can be used to heat or melt an area, while a pulsed laser beam directed to the same area is more efficiently absorbed and removes material. When the laser spots at least partially overlap and interact on the surface of the target simultaneously, combining laser beams of different wavelengths and laser pulses of different durations, in addition to making the process more efficient, it is also possible to control the material quality, such as reducing the number of particles and increasing the density of the coating.

[0088] The composition of the material can be changed by using reactive background gases (e.g. oxygen for oxides and nitrogen for nitrides) or by bringing together material streams from multiple different sources. By implementing the ablation process on multiple different targets simultaneously and directing the material streams into the same volume, a composite coating can be formed, the composition of which can be flexibly adjusted on the elemental level. One particular case of such a setup is a composite target, for example, produced by mixing two materials in powder form and pressing them into a solid block. When a laser beam with sufficiently high irradiance is directed to a target composed of two materials, the ablation affects both materials as if there were two separate sources of material, and the material streams generated from these sources are able to interact and react with each other, forming a new compound, which coagulates on the substrate to form a coating. Laser ablation deposition can be used for the above-mentioned compound formation method, or it can be used in combination with other coating methods, in which case other material streams can be generated by thermal evaporation, ion sputtering or electron beam.

[0089] The crystal structure and adhesion (between the coating and the substrate) of the produced coating can be influenced by heating the substrate or by directing ion bombardment, laser beams, light pulses or laser pulses onto the coating while the coating process is in progress or after it is completed.

[0090] Laser ablation deposition can be used to control micro- and nanostructures to achieve and optimize the functional benefits of lithium, Li-ion batteries and Li-ion capacitors. Nanostructured electrodes have a high surface-to-volume ratio, so they are able to produce high energy and power densities in electrochemical energy storage applications. Because the small particle size of the electrode material shortens the (diffusion) distance required for lithium ions to travel inside the particles, it accelerates the storage and release processes of lithium and lithium ions. On the other hand, when the amount of active surface area per unit volume increases, the number of reactions between the electrode surface and the electrolyte increases, resulting in, for example, an increase in the amount of SEI layer, which in turn leads to a decrease in the amount of active lithium. Therefore, in the case of nanostructured electrodes, the addition of lithium to the structure has a great relevance in compensating for the side effects caused by nanostructuring. Small particle size conductive coatings and dopants are ways to increase the electronic and ionic conductivity of electrode materials.

[0091] When incorporating lithium into the structure of battery materials, it is particularly important to optimize the total amount of active lithium based on the electrode storage capacity of the Li-ion battery, while also considering the amount of lithium consumed by irreversible reactions during the first charge-discharge cycle. This maximizes the utilization of the active electrode material and improves the battery's energy density. Furthermore, by selecting materials and structures, ionic and electronic conductivity can be optimized, and the battery's properties and performance can be maintained over the long term with increasing charge-discharge cycle count. Manufacturing costs, influenced by raw material selection and battery safety, also need to be considered.

[0092] Suitable materials for use as anode materials in Li-ion batteries include: for example, different forms of carbon (carbon particles, carbon nanotubes, graphene, graphite), and titanium-containing oxides (such as Li₄Ti₅O₂). 12 TiO2), lithium silicon-silicon alloy, tin, germanium, silicon oxide (SiO2) x SnO2, iron oxides, cobalt oxides, metal phosphides, and metal sulfides. Other suitable materials and compounds, alloys, composites, or material-based layered structures can also be used. For example, potentially suitable silicon compounds and alloys include Si-Sn, SiSnFe, SiSnAl, SiFeCo, SiB4, SiB6, Mg2Si, Ni2Si, TiSi2, MoSi2, CoSi2, NiSi2, CaSi2, CrSi2, Cu5Si, FeSi2, MnSi2, NbSi2, TaSi, VSi2, WSi2, ZnSi2, SiC, Si3N4, Si2N2O, and SiO2. x LiSi, LiSiO.

[0093] Lithium-ion batteries can use Li metal as the anode. The Li metal electrode structure has a three-dimensional support structure, which prevents large changes in electrode volume and reduces Li dendrite growth, which is beneficial to battery functionality. The support structure can include electron-conducting materials, such as carbon or inert metals that react with minimal amounts with Li metal, and / or Li-ion-conducting materials, such as solid-state electrolyte materials. In particular, LLMO (where M = Zr, Nb, Ta) type solid-state electrolyte materials are suitable for use as such structures.

[0094] The cathode can be any cathode material suitable for Li-ion batteries, such as transition metal oxides containing lithium, such as LiCoO2, LiMnO2, LiMn2O4, LiMnO3, LiMn2O3, and LiMn. 2-x M x O2 (M=Co, Ni, Fe, Cr, Zn, Ta, 0.01<x<0.1), LiNiO2, LiNi 1-x Mx O2 (M = Co, Ni, Fe, Mg, B, Ga, 0.01 < x < 0.3), LiNi x Mn 2-x O4 (0.01 < x < 0.6), LiNiMnCoO2, LiNiCoAlO2, Li2CuO2; LiV3O8, LiV3O4, V2O5, CU2V2O7, Li2Mn3MO8 (M = Fe, Co, Ni, Cu, Zn), various materials capable of storing lithium ions in their structure (so-called intercalation cathode materials) such as TiS3, NbSe3, LiTiS2, or some polyanionic compounds such as LiFePO4. Other cathode materials are sulfur and sulfur-based composites or sulfur-based materials: Li2S, transition metal sulfides MS2 tai MS (M = Fe, Mo, Co, Ti...). Other applicable materials and compounds, alloys, composites or layered structures based on materials can also be employed.

[0095] By adding particles of, for example, nickel, silver, copper or platinum as a dispersion on the surface of the material, the electrode material can be doped with a small amount of suitable material. The purpose of using a combined material, i.e. a composite or a doped or mixed material, is to eliminate the defects associated with certain electrode materials, which include, for example, weak ionic conductivity or electrical conductivity or microscopic damage caused by volume changes. The desired advantages and optimization of the desired microstructure vary depending on the material and the application, as all material groups have their defects in addition to their advantages, which are desired to be minimized with the aid of the coating method based on laser ablation.

[0096] When the purpose is to produce a porous material, the manufacture of a porous material can be implemented on the basis of quite diverse ablation processes and combinations of ablation processes. The choice of ablation process is influenced by the desired porosity, particle size and the open surface area resulting therefrom, the thickness of the coating layer (the particle size varies depending on the ablation mechanism), the crystallinity of the coating layer, the productivity requirements and the requirements related to stoichiometry control. For single-element materials, there are no stoichiometry problems unless the material reacts with the atmosphere inside the deposition chamber. In the case of multi-element compounds, stoichiometry control needs to be taken into account, as changes in composition can also cause changes in the structure and functionality of the material. For the robustness of the porous structure, it is crucial to produce a structure such that, in addition to the particles, a material flow also constitutes a fine, atomized or ionized material to help the binding between the particles, thus contributing to the robustness of the structure. In addition, sufficient kinetic energy of the material flow helps the binding between the particles and the binding of the particles to the substrate.

[0097] The coating method based on laser ablation differs from other thin film deposition methods, as laser ablation deposition allows a relatively precise control of the size of the particles forming the coating. If the desired coating is to be produced by first generating a substantially atomized or ionized material, the tendency of the material to form so-called clusters is particularly dependent on the velocity and size distribution of the constituent units of the material stream generated by the ablation, as well as the pressure of the background gas. For example, the condensation of a specific material stream generated by laser ablation from a target into particles can be strengthened by increasing the pressure of the background gas in the deposition chamber in a controlled manner. The increase in pressure increases the likelihood of collisions with gas atoms and molecules. In these collisions, the units of the material stream lose energy and change their direction. The deceleration and change in direction, on the one hand, increase the likelihood of collisions between the units of the material stream, thus increasing the likelihood of the formation of clusters.

[0098] In order to produce porous materials, the ablation process can also be performed such that particles are ejected from the target by peeling (spalling) material from the surface of a target made of a powder material. For example, by weakening selected microstructure regions and interfaces, the spalling and boundaries at which spalling occurs can be adjusted such that material can be more easily ejected and become fragments of a certain size. Alternatively, the laser ablation process can be adjusted such that the surface of the target is locally melted and the molten droplets are ejected from the target and directed to the surface of the base material. In the above case, the process can be defined as thermal ablation. The alternative methods described above can be selected depending on the desired microstructure of the material to be produced and the ablation process that is best suited for this material.

[0099] Due to the flexibility of the method and its suitability for different materials by selecting appropriate parameters, laser ablation processes can produce materials and coatings of different concepts even with one single method and apparatus. This greatly reduces the equipment-related investment required for battery material coating solutions, increases the manufacturing speed and reduces the amount of errors occurring in manufacturing and handling.

[0100] The method is particularly suitable for roll-to-roll manufacturing, in which the substrate, for example a copper foil, is guided from a roll as a continuous substrate to a coating station, after which a battery material coating is deposited on the substrate in the coating station, which can have one or more units. The coating stations can also be arranged in a row in such a way that the same or different materials are deposited successively in the coating stations to increase the productivity, or different materials are deposited in the coating stations to produce a composite or multilayer structure, or a dopant material, for example a material that increases the electrical conductivity, is added on the surface of the battery material. These application alternatives have their own exemplary figures. The coating stations can be separate units, enabling the properties and environment, for example the gases, pressure and temperature, of each coating station to be controlled separately and the most suitable environment to be applied for each process.

[0101] Instead of multiple inline coating stations, the coating can be manufactured by a roll-to-roll process, so that the substrate to be coated is first passed through a coating station, whereupon a layer of the desired material is deposited on the substrate. In the next step, the direction of movement of the substrate is reversed and the target material is automatically changed in the coating station, followed by deposition of another material, which can be, for example, a doped material (hybrid material), a second part of a composite material, a second layer material of a layered material, and the process is repeated until the desired structure is obtained. It is also possible that the different steps of deposition and treatment are carried out in different treatment units, one complete roll being completed in one treatment unit and transferred to the next unit under suitable conditions and the procedure is repeated until the desired level of completeness is achieved.

[0102] The coating station is also able to produce different types of protective layers on the surface of the different layers or, for example, only on the last layer of the battery material, in order to prevent, for example, the dissolution of the essential components of the material or harmful reactions with the environment or the electrolyte.

[0103] It is not necessary to deposit all material layers using laser ablation, and other deposition and manufacturing methods for the material layers and various treatment and conditioning methods can be included in the process chain if this is optimal from the overall process point of view. Such auxiliary deposition and manufacturing methods include CVD (chemical vapor deposition) techniques, ALD (atomic layer deposition) techniques and PVD (physical vapor deposition) techniques, such as sputtering. The treatment and conditioning methods of the material include, among others, various thermal treatments (oven, lamp, laser) and surface modification and texturing treatments (ion bombardment, laser ablation). For example, the good adhesion to the substrate that is typical of laser ablation deposition can be exploited by first depositing only a thin layer of the desired material on the substrate surface by laser ablation deposition, and then continuing the deposition process with another suitable method.

[0104] The composition of the material ablated by the laser must remain within the proper range of the coating functionality. In principle, pulsed laser technology, especially ultra-short pulsed laser technology, is a method suitable for minimizing adverse changes in the composition, for example, due to different types of evaporation or non-simultaneous evaporation of the dopant material. By means of ultra-short pulsed laser technology, the melting of the material and the formation of large-area molten regions, which increase the inhomogeneous material loss and impede stoichiometric control, can be minimized. In the case of many target materials, limiting the duration of the laser pulses to below 5-10 ps is sufficient to minimize the melting of the target material and the excessive loss of the dopant component in the laser ablation, if the overlap of the laser beams is minimal. At high repetition rates, the overlap of the laser pulses can also cause material melting, even if a short pulse duration is used. Changes in stoichiometry can cause a loss of the desired structure and proper functionality. In industrial manufacturing, the process must remain stable at all times, so changes in the composition or other properties of the target material over a long period of time are also detrimental.

[0105] In the manufacture of composite materials, layered structures or by doping some other material in the main material of the coating, the optimum process parameters and environment of the different materials are not necessarily the same. This must be taken into account when planning and combining the different steps in the production process. If it is desired to manufacture composite materials using a combined solution, the laser parameters can be optimized for the different materials by using different laser sources for the different materials, but in this case it must be possible to ablate all materials sufficiently in the same coating atmosphere, because it is difficult to adjust the coating atmosphere separately when performing combined ablation. If it is necessary to adjust the coating atmosphere separately for all materials, this can be done most easily in successive coating steps, so that the coating atmosphere favorable for the different materials can be controlled separately. Depending on the type of material distribution desired to be produced, several such coating steps can be established in the process solution.

[0106] In some cases, it is also possible to perform the desired doping on a single target material piece, and if the ablation thresholds of the materials in relation to each other and the condensation tendency in the selected gas atmosphere are suitable, the composite structure can be manufactured by mixing the desired materials with the target material in the desired proportions. In Figure 4c this case, this is described separately.

[0107] The basic principle of the method (laser ablation deposition) is shown in the principle view in Figure 1 , in which the structural parts of the materials included in the coating process and the direction of movement are shown on the principle level. In Figure 1In this ablation process, the energy source used is a laser source 11, from which the laser beam 12 is directed to the target 13. The laser beam 12 causes material on the surface of the target 13 to locally detach in the form of particles or other corresponding fragments, as mentioned above. This generates a material flow 14 that extends toward the object to be coated 15. The object to be coated 15 can also be referred to as the coating substrate or base. Proper alignment can be performed by appropriately setting the orientation of the plane containing the surface of the target 13 relative to the object to be coated 15, thereby directing the kinetic energy of the material flow toward the object to be coated 15. The laser source 11 can be moved relative to the target 13, or the target 13 can be moved relative to the laser source 11, and the angle of the laser beam relative to the surface of the target 13 can be changed. Optical components (e.g., mirrors and lenses) can be placed between the laser source 11 and the target 13. Furthermore, separate optical setups can be made between the laser source 11 and the target 13 for focusing and paralleling the laser beam array impacting the target 13. Figure 3 This setting is shown separately.

[0108] The electromagnetic radiation generated in laser ablation can be used... Figure 1 The setup shown is used for collecting radiation, in which the radiation collecting optics 16 is positioned to provide an unobstructed view of the material released during ablation. A protective, movable window is necessary between the collecting optics 16 and the released material to prevent material buildup on the surface of the collecting optics 16 and to attenuate the radiation to be measured. The electromagnetic radiation from the collecting optics 16 is guided to a spectrometer 18 within an optical fiber 17. Using the spectrometer 18 and a connected computer, the spectrum of the electromagnetic radiation generated during laser ablation can be measured, and meaningful information for adjusting the laser ablation process parameters can be interpreted, thereby obtaining the desired coating on the surface of the object 15 to be coated.

[0109] Figure 1 The material flow 14 can be fan-shaped, so assuming there is no lateral transfer of the material to be coated (see figures), a wider area can be coated on the surface region of the object 15 by means of an orientation angle of the target 13. In another embodiment, the material to be coated is movable, and Figure 3 This embodiment is shown separately.

[0110] Typically, in the ablation examples used in this invention, the detachment of material from the target surface, the formation of particles, and the transfer of material from the target to the substrate and to the previously formed material layer are achieved by laser pulses directed to the target, wherein the duration of a single laser pulse can be in the range of 0.1-10000 ps.

[0111] In examples of the present invention, the laser pulses can be generated with a repetition rate between 50 kHz and 100 MHz.

[0112] The coating formed by the material disengaged by laser ablation and transferred as particles from the target to the substrate has to establish a reliable bond with the substrate or the previously prepared material layer. This can be achieved by sufficient kinetic energy of the particles, thus providing sufficient energy for the generation of bonds between the different materials. Furthermore, in a particle dense material flow, there is preferably a sufficient amount of atomized and ionized material to support the generation of bonds between the particles.

[0113] In the production of porous coatings, one very important process parameter in laser ablation is the gas pressure used in the process chamber. Increasing the gas pressure can promote the formation and growth of particles during the flight of the material from the target to the surface of the material to be coated. The optimum gas pressure can differ depending on the gas or gas mixture used, the type of material to be coated, and the desired particle size distribution, porosity and adhesion between the particles, and the bonding of the particles to the rest of the material. With regard to the selection of the gas and the gas purity, potential reactions between the gas and the materials of the substrate, the object to be coated, and the target have to be considered.

[0114] In one embodiment, the laser ablation and deposition take place in a vacuum chamber, i.e. in a vacuum or in a background gas, in which a controlled pressure can be applied. One possible alternative is to set the pressure between 10 -8 - 1000 mbar. When pursuing a porous coating or wanting to increase the porosity, a background gas pressure between 10 -6 - 1 mbar is usually used. The relative use of the background gas depends on the density and total energy of the material flow and the distance of the material from the ablation point to the surface of the object to be coated. If the laser ablation is carried out by so-called thermal ablation and partial melting of the target material surface, then a porous coating with particle sizes of less than 1 pm can also be produced at low background pressures, since the particles are formed by molten droplets, not by condensation of atomized material. Further, the disengagement of particles in the target material can also be promoted by a selective energy absorption or partial cracking of the target material, thus enabling a particle-based material flow.

[0115] Controlling the composition and pressure of the gas inside the deposition chamber is of great importance, especially when handling reaction-sensitive materials such as lithium. Furthermore, before and after the actual deposition process, a treatment of the object to be coated and the target under controlled conditions and a controlled gas atmosphere is required, which includes placing the object and the target into and removing them from the volume limited by the chamber walls, in order to avoid harmful reactions and material contamination.

[0116] To improve homogeneity and productivity, it is preferred to create as wide a material flow as possible between the target material and the substrate. In examples of the present invention, this can be achieved by splitting the laser beam by means of a rotating mirror to form an array of laser beams in a plane, which results in a line on the plane of the target material surface. In Figure 2 A possible implementation of this setup is shown in Fig. 6. Instead of a target material, the laser beam 12 of the laser source 11 is first directed to a moving and / or turning mirror 21, which can be a hexagonal and rotatable polygon, for example as shown, with mirrored facets. The laser beam 12 is reflected by the mirror 21 to form a fan-shaped laser beam distribution, and the reflected beams are directed to a telecentric lens 22. By means of the telecentric lens 22, an array of laser pulses can be aligned, forming an array 23 of substantially parallel laser beams, so that the laser beams hit the target material 13 at the same angle. In the observation plane of the example of Fig. 6, the angle is 0° with respect to the normal of the surface. If the intensity distribution of the laser beams is the same at each point of incidence, the material can be detached at each point of incidence of the laser beam in the same way. Figure 2

[0117] The array of laser beams can also be generated by other means, for example a rotating single-prism, which directs the laser beam to a ring-shaped target material, for example, thereby forming a ring-shaped material flow.

[0118] In an application example, a part of a lithium battery, Li-ion battery or Li-ion capacitor is very well suited for deposition, so that the material is unwound from a roll of the desired width to be coated in the deposition chamber. Figure 3 A principle view of this application alternative is shown. The material is guided from one or more coating sources onto one or more surfaces of the object to be coated in the desired coating width, so that the material is continuously unwound from a roll for coating, and after the material has passed the deposition zone, the material is collected again on a roll. As mentioned above, this method can be referred to as a roll-to-roll method. In other words, the part to be coated 32 is initially wound in a roll 31a. As mentioned above, an ablation device comprising a laser source 11 and a target material 13 is included. The laser beam 12 causes the material to detach as a flow 14, i.e. in the form of a material flux, towards the material to be coated 32, and due to adhesion, a coated part 33 is created. The coated substrate 33 is wound around a second roll 31b, in Figure 3 ​In the case shown, the direction of movement of the substrate is from left to right. The roller structure 31a, 31b can be driven by a motor. Seen in the depth direction (cross direction) in the figure, the object to be coated can be the entire area of the surface, or only a part of the surface. Likewise, in the direction of movement of the substrate (machine direction), it is possible to select the desired part (length) of the substrate to be coated, or alternatively, it is possible to pass the entire roller from beginning to end, so that the substrate is coated over the entire length of the roller. In the case of a film material, it is possible to coat one or both sides completely in the machine direction and / or cross direction, or as mentioned above, partially.

[0119] Figure 4a is a structural view of an arrangement in which material is deposited onto a substrate by using a laser ablation deposition technique. A laser beam 41 has been marked with a thick dashed line in the lower part of the figure, and the laser beam arrives in the picture area from the lower right. The laser beam is directed onto the surface of a target material piece 42a, and preferably the direction in which the target surface meets the light beam is arranged to be in an oblique direction in relation to the direction of arrival of the light beam. As a result of this interaction, a material flow 43a consisting of particles, atoms and / or ions is formed. The material flow is shown in the figure as a linearly advancing and expanding cloud of material. A substrate 44 to be coated is located at the topmost, and an actual coating 45a is formed on its lower surface, which is shown in the figure as a rectangle. In other words, in this case the material flow hits the lower surface of the substrate and adheres to it, forming a dense coating.

[0120] Figure 4b is shown a structural view of an arrangement in which a porous coating is produced. The arrangement is otherwise the same as in Figure 4a , but here the material flow 43b consists mainly of particles, and the coating 45b formed on the substrate 44 is porous. In this example, the target material 42a used consists of one material, and one target material is used.

[0121] Figure 4c is shown a structural view of an arrangement in which a coating with a composite structure is produced. The arrangement is otherwise the same as in Figure 4a-4b , but here the target material 42b has a composite structure and consists of two different materials. The target material 42b can be manufactured, for example, by mixing two different powders and compacting them into a solid block. In this case, the materials maintain their composition in the material flow 43c, and the composite material coating 45c formed on the lower surface of the substrate 44 consists of two different materials. The structure of the coating 45c can be dense or porous.

[0122] Figure 4d is shown the production of a composite material coating using the same principles as in Figure 4c . As in Figure 4cIn contrast to the case in Fig. 1, the difference is that the materials of the target material 42b with the composite structure react with each other in the material stream 43d and form a compound. The coating 45d formed on the lower surface of the substrate 44 is a compound formed from two different materials. The structure of the coating 45d can be dense or porous.

[0123] Figure 5 A typical structure of a lithium-ion battery is shown in the form of a cross-sectional view. Of the parts, the first part from the top is an aluminum foil 51, which serves as a current collector. Looking further down, the next part is a cathode material 52. Next is a porous polymer film 53, which serves as a separator in the battery. It can be made of, for example, polyethylene, and it can also be coated with, for example, a ceramic material. The fourth film is an anode material 54. The fifth and lowermost film is a copper film 55, which serves as a current collector in a corresponding manner to the uppermost aluminum film 51.

[0124] Figure 6 A simplified diagram of an exemplary roll-to-roll manufacturing setup in one possible embodiment of the invention is shown. In the example of Fig. 2, Figure 6 In the example of Fig. 2, there are three separate process stations 61, 62, 63, which have been positioned in a row so that the untreated substrate is unwound from a roll 65 and after material deposition in the first station 61, the product 66 comprising the substrate and the first coating material is treated by, for example, heat treatment and / or by means of a laser and / or by means of mechanical means in the second station 62. The treated product 67 continues to move to the third station 63, where a second coating is deposited, after which the product 68 is wound onto a roll 69. In the same production line, between the unwinding and winding rolls, other process stations can also be included, for example, in which pretreatment and cleaning of the substrate can be carried out before deposition. On the other hand, the product can be wound onto a roll after each individual process step and then transferred to the next process station for the next process. The order can be optimized according to the materials used.

[0125] In one embodiment of the invention, Figure 6 The three process stations in Fig. 2 are the first step of depositing metallic lithium, the second step of processing the lithium layer with a laser, and the third step of producing a protective layer on the surface of the lithium.

[0126] Figure 7aAn example of a combined coating method using two simultaneous material streams to form a compound coating is shown. Here, two separate laser beams, a first laser beam 71c and a second laser beam 71d enter the setup and these beams are directed to impinge on pieces of target material, a first target 72c and a second target 72d. The material of the first target is different from the material of the second target. In these interactions, material streams 73c and 73d are formed due to laser ablation. These two material streams mainly contain components in a reactive form, but involve different materials. Before impinging on the lower surface of the substrate 75, the material streams partly advance simultaneously within the same volume, thereby forming a compound coating 74b mainly formed of two different materials. The proportion of the different substances in the compound coating 74b can be varied, for example, by independently adjusting one or both of the laser sources generating the laser beams 71c and 71d. Thus, the compound coating 74b is mainly formed in one step from the material streams 73c and 73d on the lower surface of the substrate 75 and can be immediately used as a finished coating.

[0127] Figure 7b An example of a combined coating method using two simultaneous material streams to form a compound coating is shown. Here, two separate laser beams, a first laser beam 71c and a second laser beam 71d enter the setup and these beams are directed to impinge on pieces of target material, a first target 72c and a second target 72d. The material of the first target is different from the material of the second target. In these interactions, material streams 73c and 73d are formed due to laser ablation. These two material streams mainly contain components in a reactive form, but involve different materials. Before impinging on the lower surface of the substrate 75, the material streams partly advance simultaneously within the same volume, thereby forming a compound coating 74b mainly formed of two different materials. The proportion of the different substances in the compound coating 74b can be varied, for example, by independently adjusting one or both of the laser sources generating the laser beams 71c and 71d. Thus, the compound coating 74b is mainly formed in one step from the material streams 73c and 73d on the lower surface of the substrate 75 and can be immediately used as a finished coating.

[0128] Figure 8aThe use of successive deposition stations to increase productivity is shown. In this example, four deposition stations are shown, and each incident laser beam (or pulse train) 81a-d is directed to the appropriate target 82a-d by a mirror (P, each beam has its own mirror). In this case, a roll-to-roll approach can be used, and the lower surface of the substrate 85 first encounters a first material stream 83a, which forms a first coating layer 84a. As the substrate 85 moves to the right in the figure, the first coating layer 84a again encounters a second material stream 83b, resulting in a second coating layer 84b on top of the first coating layer 84a. The process continues in the remaining two coating stations, with the end result being that the substrate 85 encounters four material streams 83a-d, and the coating has a layered structure 84a, 84b, 84c, 84d. The targets 82a-d can be made of the same material, as shown in this figure.

[0129] Figure 8b The use of successive coating stations to increase productivity in the manufacture of composite and multilayer structures is shown. This is similar to the case in Figure 8a , but now two different types of materials have been chosen as target material pieces 82A, 82B, and these materials are positioned alternately, one target to one coating station, the next target has the second material. In other words, looking from the left side, the first and third targets have the same first material “A”, while the second and fourth targets have the same second material “B” respectively. The laser beams 81a-d can still be controlled independently and directed by mirrors P onto the targets. This setup provides two different types of material streams 83A, 83B, which are alternating. When the material streams hit the moving substrate 85, another new layer is formed on top of the older layer, and the end result is a 4-layer composite structure 84A, 84B, 84A, 84B visible at the right edge of the figure. Thus, in this coating, the material layers alternate with each other.

[0130] Figure 8c The use of successive coating stations to increase productivity in the manufacture of doped materials is shown. The setup is similar to the setup in Figure 8b , but here the first and third targets 82C are made of a base material, and the second and fourth targets 82D are made of an additive (i.e. doping material) respectively. The laser beams 81a-d can still be controlled independently and directed by mirrors P onto the targets. This setup results in two different types of material streams 83C, 83D, which are alternating. By the principles described above, the doped base material now forms the coating of the substrate 85, and the relative proportion of the doping material throughout the coating can be selected by independently adjusting the laser parameters. In the coating, 84C represents a layer of base material, and 84D represents a layer of additive.

[0131] As occurs in many of the cases described above, in addition to the manufacturing method, the inventive concept of the present application also comprises the manufactured product, i.e. the foil or film type electrode (anode or cathode), as well as the basic components of the entire lithium battery, Li-ion battery or Li-ion capacitor, in which at least part of the lithium content is manufactured using laser ablation.

[0132] In summary, in the present application, a material coating is produced for a part of an electrochemical energy storage device, so that at least one of the targets used in the laser ablation deposition contains lithium as a metal or compound or alloy, so that at least one material coating containing lithium is produced by the laser ablation deposition method. Finally, the assembled device, i.e. the lithium battery, Li-ion battery or Li-ion capacitor, comprises a component having one or more material layers produced by laser ablation.

[0133] The combination deposition settings according to Figure 7a , 7b and 8a can be combined, for example, with another type of deposition setting instead of one or some of the deposition stations in Figure 8a , such as a combination deposition station consisting of two or more targets according to the principles of the examples in Figure 7a . The continuous and combination deposition settings can also be combined, so that instead of one or more material sources, some other suitable coating method is used instead of the laser ablation deposition method.

[0134] In the following, the features of the present application are further compiled in an overviewy manner by means of lists.

[0135] The present application relates to a method of manufacturing a lithium-containing material, the method comprising the steps of:

[0136] - directing a laser beam (12, 23, 41, 71a-d, 81a-d) to at least one target (13, 42a-b, 72a-b, 82a-d, 82A-D) containing lithium and / or a lithium compound;

[0137] - detaching at least one material (14, 43a-d, 73a-d, 83a-d, 83A-D) from the at least one target (13, 42a-b, 72a-d, 82a-d, 82A-D, 92) by laser ablation;

[0138] - directing the at least one detached material (14, 43-d, 73a-d, 83a-d, 83A-D) to be deposited onto at least one surface or partial surface of a substrate (15, 32, 44, 64, 75, 85);

[0139] - the energy delivered to the target material by the laser beam and / or the surface area of the laser spot on the target material surface is adjusted based on a measurement of the electromagnetic radiation generated by the laser ablation during the material detachment.

[0140] The invention is characterized in that the method further comprises the following steps:

[0141] - producing a part of a lithium battery, Li-ion battery or Li-ion capacitor, thereby producing at least one layer of a lithium containing material by laser ablation deposition.

[0142] In one embodiment of the invention, by using parts comprising an anode, a cathode and a solid or liquid electrolyte material, a lithium battery, Li-ion battery or Li-ion capacitor is further assembled in the method, so that at least one of the parts has a layer of material manufactured by using laser ablation deposition.

[0143] In one embodiment of the invention, when using laser ablation deposition, the detachment of the material, the formation of particles and the transfer of the material from the target material (13, 62, 72a-d, 82a-d, 82A-D) to the substrate (15, 32, 44, 64, 75, 85) is achieved by a laser beam (12, 23, 41, 71a-d, 81a-d) which is pulsed, directed to the target material (13, 42a-b, 72a-d, 82a-d, 82A-D), wherein the duration of a single laser pulse is between 0.5-100000 ps (0.5 ps - 100 ns).

[0144] In one embodiment of the invention, the laser pulses are generated with a repetition rate which can be selected in the range of 50 kHz - 100 MHz.

[0145] In one embodiment of the invention, at least one layer containing lithium in metallic form is produced by laser ablation deposition using a Li metal target material.

[0146] In one embodiment of the invention, a lithium layer with a thickness of less than 100 nm is produced by laser ablation deposition using a Li metal target material.

[0147] In one embodiment of the invention, the manufacturing of the material layers is carried out in at least two consecutively arranged continuous deposition stations, so that at least one of the deposition stations is in operation, so that the material flow produced thereby does not meet another material flow produced in a preceding or subsequent deposition station before the material flow forms a coating on the surface of the substrate.

[0148] In one embodiment of the invention, a lithium layer with a thickness of less than 100 nm is produced by laser ablation deposition using a Li metal target, after which in the following process steps more lithium metal is produced on top of the lithium layer by using suitable methods.

[0149] In one embodiment of the invention, a layer consisting essentially of lithium with a thickness of not more than 5 pm is first produced by laser ablation deposition using a Li metal target, then deposition is continued using another method to produce a layer consisting essentially of lithium with a thickness of not more than 100 pm.

[0150] In one embodiment of the invention, at least two laser beams with different properties are directed simultaneously to the target (13, 42a-b, 72a-d, 82a-d, 82A-D).

[0151] In one embodiment of the invention, the focal spots of at least two of the individual laser beams directed to the target (13, 42a-b, 72a-d, 82a-d, 82A-D) partially overlap on the surface of the target and interact on the surface of the target simultaneously.

[0152] In one embodiment of the invention, in the two laser beams, the first laser beam is a pulsed laser beam and the second laser beam is a continuous wave laser beam, which are directed to the target (13, 42a-b, 72a-d, 82a-d, 82A-D) simultaneously.

[0153] In one embodiment of the invention, a lithium layer is produced by laser ablation deposition using a Li metal target, so that the area hit by the laser beam has liquid lithium.

[0154] In one embodiment of the invention, after the material manufacturing is complete, the material layer is modified by directing a laser beam to it.

[0155] In one embodiment of the invention, at least one layer containing mainly lithium in the form of a metal is produced by laser ablation deposition using a composite target (42b) containing Li metal.

[0156] In one embodiment of the invention, at least one layer containing mainly lithium bound in a compound is produced by laser ablation deposition using a composite target (42b) containing Li metal.

[0157] In one embodiment of the invention, at least one layer containing mainly lithium bound in a compound is produced by laser ablation deposition using a composite target (42b) containing Li metal and an electrode material.

[0158] In one embodiment of the application, the deposition of the active electrode material is carried out by using a target material which, in addition to the electrode material and / or lithium compound, comprises a metallic material and / or carbon, wherein, in the case of a metallic material, the metallic material comprises at least 25% by weight of copper, silver, iridium, gold, tin, nickel, platinum or palladium or an alloy of at least two of the listed metals.

[0159] In one embodiment of the application, the electrode material mentioned above is one or more of the following materials:

[0160] carbon (carbon particles, carbon nanotubes, graphene, graphite), Li4Ti5O 12 , TiO2, Si, Li-Si compound, LiSiO, Sn, Ge, silicon oxide SiO x , SnO2, iron oxide, cobalt oxide, metallic phosphides and metallic sulfides, Si-Sn, SiSnFe, SiSnAl, SiFeCo, SiB4, SiB6, Mg2Si, Ni2Si, TiSi2, MoSi2, CoSi2, NiSi2, CaSi2, CrSi2, Cu5Si, FeSi2, MnSi2, NbSi2, TaSi, VSi2, WSi2, ZnSi2, SiC, Si3N4, Si2N2O, SiO x .

[0161] In one embodiment of the application, the electrode material mentioned above is one or more of the following materials: LiCoO2, LiMnO2, LiMn2O4, LiMnO3, LiMn2O3, LiMn 2-x M x O2(M = Co, Ni, Fe, Cr, Zn, Ta, 0.01 < x < 0.1), LiNiO2, LiNi 1-x M x O2(M = Co, Ni, Fe, Mg, B, Ga, 0.01 < x < 0.3), LiNi x Mn 2-x O4(0.01 < x < 0.6), LiNiMnCoO2, LiNiCoAlO2, Li2CuO2, LiV3O8, LiV3O4, V2O5, Cu2V2O7, Li2Mn3MO8(M = Fe, Co, Ni, Cu, Zn), TiS3, NbSe3, LiTiS2, LiFePO4, Li2S, MS2 or MS (M = Fe, Mo, Co, Ti).

[0162] In one embodiment of the application, lithium is produced using a Li metal target by laser ablation deposition on a three-dimensional electronically conductive structure.

[0163] In one embodiment of the present invention, lithium is deposited on the surface of a metal or metal alloy layer with a thickness of less than 100 nm, which metal layer does not consist of lithium or which metal alloy layer does not contain lithium.

[0164] In one embodiment of the present invention, lithium is deposited on the surface of a metal or metal alloy layer with a thickness of less than 100 nm, which metal or metal alloy layer contains one or more metals from the following group: copper, silver, iridium, gold, tin, nickel, platinum or palladium.

[0165] In one embodiment of the present invention, a lithium compound or lithium metal is deposited on the surface of at least one electrode material by laser ablation deposition.

[0166] In one embodiment of the present invention, a protective layer is generated on top of the layer generated by laser ablation deposition and containing lithium or a lithium compound in a subsequent deposition step by using a continuous deposition station.

[0167] In one embodiment of the present invention, the protective layer mentioned above is one or more from the following group: LLMO (with M = Zr, Nb, Ta), LPS, LGPS, LiPON, oxides (such as AI2O3, SiO2, TiO2or ZnO), nitrides (such as TiN, Si3N4or BN), fluorides (such as AIF3), phosphates (such as AIPO4).

[0168] In one embodiment of the present invention, the lithium-containing coating has up to 15 vol% of a metal generated by laser ablation or at least 20 wt% of metal-containing particles.

[0169] In one embodiment of the present invention, a layer of a material containing at least 25 wt% of lithium and another metal is generated by a combined way or using a continuous deposition station.

[0170] In one embodiment of the present invention, the metal mentioned above is one or more from the following group: copper, silver, iridium, gold, tin, nickel, platinum or palladium.

[0171] In one embodiment of the present invention, the metal-containing particles have an average size of up to 500 nm.

[0172] In one embodiment of the present invention, at least one active electrode material used for deposition has an average particle size of less than 900 nm, the volume fraction of which in the electrode material coating is at least 10 vol%.

[0173] In one embodiment of the present invention, the electrode material coating contains at least 10 wt% of lithium.

[0174] In one embodiment of the present invention, the electrode material coating contains at least 30 wt% of lithium.

[0175] In one embodiment of the application, the electrode material coating comprises at least 10 wt.% carbon.

[0176] In one embodiment of the application, the electrode material coating comprises at least 15 wt.% carbon.

[0177] In one embodiment of the application, at least two laser sources are arranged to operate simultaneously, jointly forming a combined continuous material flow (73a, 73b) from at least two target materials (72a, 72b) to the surface of the substrate (75), thereby forming a composite coating (74a) consisting of at least two different materials.

[0178] In one embodiment of the application, at least two laser sources are arranged to operate simultaneously, jointly forming a combined continuous material flow (73c, 73d) from at least two target materials (72c, 72d) to the surface of the substrate (75), thereby forming a compound coating (74a) consisting of at least two different materials.

[0179] In one embodiment of the application, the carbon-based material is deposited together with the lithium-containing material in a combined manner in at least one deposition step by pulsed laser ablation deposition.

[0180] In one embodiment of the application, the total thickness of the electrode material coating is at most 100 pm.

[0181] In one embodiment of the application, the amount of metal material in the target material is at most 15 wt.%.

[0182] In one embodiment of the application, the amount of carbon in the target material is at most 90 wt.%.

[0183] In one embodiment of the application, the porosity of the electrode material coating is at least 5 vol.%.

[0184] In one embodiment of the application, the porosity of the electrode material coating is at least 20 vol.%.

[0185] The inventive concept also comprises an electrochemical device (lithium battery, Li-ion battery or Li-ion capacitor) comprising a cathode material and an anode material. It is characterized in that the device also comprises a solid or liquid electrolyte, and wherein at least one embodiment option of the above-described method has been used to manufacture a lithium-containing coating.

[0186] In one embodiment of the application, the material layers of the electrochemical device contain active (i.e. usable for the reactions required for the basic operation of the device) lithium in an amount exceeding the storage capacity of the cathode material present in the device during the assembly phase of the device.

[0187] In one embodiment of the application, at the stage of assembly of the device, the material layers of the electrochemical device contain active lithium in an amount exceeding the storage capacity of the cathode material present in the device, so that, at the use of the device, the excess lithium is stored in the active anode material, which additionally has a free Li-ion / lithium storage capacity at least equal to the cathode capacity.

[0188] In one embodiment of the application, at the stage of assembly of the device, the material layers of the electrochemical device contain metallic lithium, which is consumed in irreversible reactions and / or is stored in the electrode material after participating in ion exchange without the formation of metallic lithium at later stages of the use of the device.

[0189] In one embodiment of the application, at the stage of assembly of the device, the material layers of the electrochemical device contain active lithium in an amount exceeding the storage capacity of the cathode material present in the device, so that, at the first operating cycle of the assembled and ready-to-use device (Li-ion transfer from one electrode to another and back), as well as at the stages preceding the first operating cycle, the Li content exceeding the cathode storage capacity, preferably 50-100%, more preferably 70-100%, even more preferably 80-100%, most preferably 90-100%, is consumed in irreversible reactions.

[0190] The method according to the application has the following advantages:

[0191] i. The material layer containing lithium or lithium compounds can be produced by simple setup without damaging or contaminating the material

[0192] ii. The material layer can be produced at low temperatures without damaging the substrate

[0193] iii. Good adhesion between different material layers is achieved without the need for special adhesion layers or adhesives

[0194] iv. The lithium content in the coating can be precisely controlled

[0195] v. New electrode materials can be manufactured and put into use, which appropriate and full utilization requires the introduction of additional lithium in the structure

[0196] vi. Electrode materials storing lithium in the form of compounds can be transferred to the electrode layer in the form containing lithium, so that the harmful effects caused by the volume changes of the electrode material generated by the charge and discharge cycles associated with the operation of the battery can be minimized

[0197] vii. Composite materials can be manufactured to produce the optimal combination of different materials

[0198] viii. Doping can be performed, for example, to add small amounts of doping substances to increase the electrical conductivity

[0199] ix. Layered structures can be manufactured to optimize properties

[0200] x. Layers of materials necessary for several different functions can be manufactured with one manufacturing method, and some even in one manufacturing step

[0201] xi. During the production of different material layers, there is no risk of material damage or contamination if one device is used to produce the layers

[0202] xii. Reaction-sensitive surfaces and materials, such as lithium, can be protected in the same process by one or more protective layers

[0203] xiii. The use of adhesives can be avoided, thus reducing contamination of battery chemicals over the long term

[0204] xiv. During the transfer from the target to the coating, the composition of the coating can be maintained correctly

[0205] xv. The open area and porosity of the active electrode material can be adjusted by adjusting the laser parameters, the background gas or its pressure, and the distance between the target and the substrate

[0206] xvi. By collecting and measuring the electromagnetic radiation generated by the laser ablation, the process can be precisely controlled, thus achieving repeatability and uniform quality in industrial manufacturing

[0207] xvii. Production investments can be reduced

[0208] xviii. Electrode materials with very small particle sizes (<1 pm) can be manufactured, thus

[0209] a. Increasing the number of active surfaces in contact with the electrolyte

[0210] b. Reducing the diffusion length of ions and electrons

[0211] c. Reducing the cracking sensitivity of the electrode material particles due to volume changes during the discharge and charge steps

[0212] xix. A fine structure is ultimately obtained, in which the optimized pore distribution better withstands the volume changes that occur during battery discharge and charging, and cracking is avoided

[0213] xx. Amorphous materials can be manufactured, which better withstand the volume changes caused by the charge / discharge cycle and do not crack or damage due to certain materials (e.g. silicon)

[0214] xxi. A uniform pore distribution reduces the stress generated by the volume changes caused by the charge / discharge cycle

[0215] xxii. Batteries with a rather high energy density can be manufactured compared to conventional material solutions

[0216] In the present application, the individual features of the application mentioned in the above and dependent claims can be combined into new combinations, wherein two or more individual features can be included in the same embodiment.

[0217] The present application is not limited to the examples shown, but many variations are possible within the scope of protection defined by the appended claims.

Claims

1. A method for manufacturing a material layer comprising lithium (Li), wherein the apparatus for carrying out the method comprises – A chamber in which the composition and pressure of a gas can be controlled, and in which material processing can be performed under controlled conditions and a controlled gas atmosphere, the processing comprising introducing material into a volume defined by the chamber walls and removing it from the volume defined by the chamber walls; -At least one laser source generates a laser beam; - At least one optical component for influencing the optical properties of the laser beam; - At least one optical component for changing the direction of the laser beam; – At least one lithium-containing target is disposed in the chamber; – A device for moving the target material located within the chamber; – Perform laser beam processing on a selected surface area of ​​the target material; –Guide at least one laser beam to strike the surface of the lithium-containing target and cause the lithium-containing material to detach from the target, thereby moving the target and / or controlling the laser beam to detach the material from the desired area on the surface of the target; – The substrate to be coated is placed in the chamber; – A device for moving the substrate located within the cavity; – Control the substrate such that lithium-containing material detached from the target by laser ablation impacts a desired surface area on the surface of the substrate; The device is characterized in that it further comprises – Measuring device used to measure electromagnetic radiation generated by laser ablation; The method includes the following steps: – A lithium-containing layer of selected thickness, less than 250 μm, is formed on the surface region of the surface of the substrate. – The formed lithium-containing layer is processed and modified by means of heat treatment, laser, or mechanical methods through an apparatus configured to process and modify the material, and also contains – Adjust the energy transmitted to the target material through the laser beam and / or adjust the surface area of ​​the laser spot on the target material surface based on the measurement results of the electromagnetic radiation generated by laser ablation during the material removal process.

2. The method of claim 1, wherein, The substrate is a current collector, a solid electrolyte, or a separator.

3. The method of claim 1, wherein, The method also includes the step of assembling a lithium battery or Li-ion capacitor by using a fabrication material layer comprising an anode, a cathode, and a solid or liquid electrolyte material, such that at least one lithium-containing layer is fabricated by pulsed laser ablation deposition.

4. The method of claim 3, wherein, The lithium battery includes a Li-ion battery.

5. The method of claim 1, wherein, The material is generated on the substrate in a layered manner during the coating process, such that at least one layer is Li metal.

6. The method of claim 1, wherein, The fabrication of the material layer is carried out in at least two consecutive deposition stations, such that at least one of the deposition stations is in operation, and the material flow generated therefrom does not encounter another material flow generated in the preceding or following deposition station before the material flow forms a coating on the surface of the substrate.

7. The method of claim 1, wherein, First, a layer of Li metal with a thickness of less than 5 μm is deposited on the surface of the substrate by laser ablation. Then, the deposition process is continued by another method to produce a layer of Li metal with a total thickness of up to 100 μm.

8. The method of claim 1, wherein, directing at least two independent laser beams with different properties simultaneously to a target comprising lithium.

9. The method of claim 8, wherein, The light spots of the at least two independent laser beams directed to the target comprising lithium partially overlap on the surface of the target and interact on the surface of the target simultaneously.

10. The method of claim 1, wherein, Providing at least two laser sources to be operated simultaneously and to produce material on the surface of the substrate simultaneously from at least two different targets in the same environment, so that the material flow from the targets to the substrate meets each other before they form a coating on the surface of the substrate.

11. The method of claim 3, wherein, At least one of the targets used in the deposition is a composite material in structure and comprises Li metal.

12. The method of claim 11, wherein, The components of the Li composite material form together at least one Li compound during the laser ablation process and when forming the material layer.

13. The method of claim 1, wherein, Depositing a lithium layer by laser ablation deposition by using a Li metal target, so that the area on the target hit by the laser beam has liquid lithium.

14. The method of claim 1, wherein, In one of the subsequent processing steps, a protective layer is deposited on top of at least one material layer comprising lithium.

15. The method of claim 1, wherein, Depositing lithium on the surface of a metal or metal alloy layer comprising one or more metals of the following group: copper, silver, iridium, gold, tin, nickel, platinum or palladium in a thickness of less than 100 nm.

16. An electrochemical energy storage device utilizing lithium, the device comprising: a. a cathode material, and b. an anode material, characterized in that the device further comprising c. a solid or liquid electrolyte, and wherein d. the method according to any one of claims 1 to 15 has been used for the manufacture of at least one material layer.

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