KR20200010069A - Forming method for battery using for light sintering and battery manufactured by the same - Google Patents

Abstract

Disclosed is a method for producing a battery using a photosintering process. The method for producing a battery using a photosintering process according to an embodiment of the present invention comprises the following steps: applying a paste for a positive electrode on a substrate and then sintering the same to form a positive electrode; applying a paste for a solid electrolyte on the positive electrode and then sintering the to form a solid electrolyte; and applying a paste for a negative electrode on the solid electrolyte, and sintering the same to form a negative electrode. At least one of forming the positive electrode, forming the solid electrolyte, and forming the negative electrode is conducted by the photosintering process.

Description

TECHNICAL FIELD OF THE INVENTION A battery manufacturing method using a light sintering process and a battery manufactured therefrom {FORMING METHOD FOR BATTERY USING FOR LIGHT SINTERING AND BATTERY MANUFACTURED BY THE SAME}

The present invention relates to a method for manufacturing a battery using a photosintering process and a battery manufactured therefrom. More particularly, the photosintering process includes a solid state electrode or a solid electrolyte effectively prepared in a short time using a photosintering process. It relates to a method for producing a battery using the process and a battery produced therefrom.

Lithium-ion secondary battery has the advantages of high operating voltage, light weight, small size, non-memory effect, low self-discharge rate, long cycle life, high energy density, etc., widely used in mobile phones, notebook computers, tablet computers and other mobile terminals do. In recent years, in view of environmental protection, electric vehicles have been rapidly developed under the promotion of government and automobile manufacturers, and lithium ion batteries have become an ideal power source for next generation electric vehicles due to their excellent performance.

Lithium ion secondary batteries include a positive electrode, an electrolyte and a negative electrode, and electrodes (anode and / or negative electrode) or solid electrolytes used in the lithium ion secondary battery are manufactured by a sintering process, and generally, electrodes (anode and / or negative electrode) Or solid electrolytes were prepared using a heat sintering process, a laser sintering process and a microwave sintering process.

However, the heat treatment process has a disadvantage in that the process time is very long because various processes such as temperature raising, heat treatment, and cooling proceed, and the substrate selection is limited because the process proceeds in a high temperature environment.

However, rapid thermal annealing (RTA) speeds up the temperature in a very short time, resulting in a shorter process time compared to the general heat treatment process. There is a problem such as material destruction for forming a lithium ion secondary battery by thermal stress.

Furthermore, in the case of a material containing lithium among the components of the lithium ion secondary battery, there is a problem that lithium is evaporated when exposed to a high temperature environment for a long time.

In addition, the laser sintering process has a disadvantage in that the application area is narrow, and the microwave sintering process has a disadvantage in that the sintering depth is shallow and the selection of the substrate is limited.

Therefore, a study on the sintering process for manufacturing a lithium-ion secondary battery is required.

Republic of Korea Patent Publication No. 10-2017-0090449, "Materials and methods for lithium ion battery anode" Korean Patent Publication No. 10-2018-0029254, "Cathode Material for Rechargeable Solid Lithium Ion Battery"

It is an object of embodiments of the present invention to effectively produce a solid state electrode (anode or cathode) or a solid electrolyte in a short time using a photosintering process.

More specifically, an object of an embodiment of the present invention is to prepare an electrode or a solid electrolyte through a photo sintering process, to prepare in a very short time compared to the electrode or a solid electrolyte produced through a heat sintering process, to prepare an electrode or a solid electrolyte It is intended to improve various problems that may occur when the material is exposed to a high temperature environment for a long time (eg substrate breakdown, reduction of durability due to residual thermal stress).

An embodiment of the present invention is to provide a method for manufacturing a battery using a light sintering process that can effectively reduce material loss because the lithium sintering process is very short photochemical sintering time is not vaporized.

According to an embodiment of the present invention is to provide a method for manufacturing a battery using a light sintering process that can prevent the element diffusion between the electrode and the solid electrolyte due to the very short time of the light sintering process.

Method of manufacturing a battery using a photo sintering process according to an embodiment of the present invention comprises the steps of applying a paste for the positive electrode on the substrate, followed by sintering to form a positive electrode; Applying a paste for a solid electrolyte on the anode and then sintering to form a solid electrolyte; And applying a paste for a negative electrode on the solid electrolyte, followed by sintering to form a negative electrode, forming the positive electrode, forming the solid electrolyte, and forming the negative electrode. The step of is characterized in that sintered by the photosintering process.

According to the method of manufacturing a battery using a photosintering process according to an embodiment of the present invention, the photosintering process may be performed for 0.1 second to 10 seconds.

According to the method of manufacturing a battery using a photosintering process according to an embodiment of the present invention, the photosintering process for the positive electrode paste and the negative electrode paste may be performed at 300 ° C to 600 ° C.

According to the method of manufacturing a battery using the photosintering process according to the embodiment of the present invention, the photosintering process for the solid electrolyte paste may be performed at 500 ° C to 600 ° C.

According to the method of manufacturing the battery using the photosintering process according to the embodiment of the present invention, the light energy of the photosintering process for the positive electrode paste and the negative electrode paste may be 70J to 100J.

According to the manufacturing method of the battery using the photosintering process according to an embodiment of the present invention, the light energy of the photosintering process for the solid electrolyte paste may be 90J to 130J.

A battery manufactured using a photosintering process according to an embodiment of the present invention comprises a positive electrode formed on the substrate using a paste for the positive electrode; A solid electrolyte formed on the anode using a paste for solid electrolyte; And a negative electrode formed on the solid electrolyte using a paste for negative electrode, wherein at least one of the positive electrode, the solid electrolyte, and the negative electrode is sintered by a photosintering process.

According to a battery manufactured using the photosintering process according to an embodiment of the present invention, the positive electrode paste is LiCoO ₂ , LiNiO ₂ , LiNi _1-x CoxO ₂ , LiMnO ₂ , LiMn ₂ O ₄ , LiV ₃ O ₈ , It may include a cathode active material including at least one of LiFePO ₄ , LiMnPO ₄ , LiCoPO ₄ and Li ₃ V ₂ (PO ₄ ) ₃ .

According to the battery manufactured using the photosintering process according to an embodiment of the present invention, the solid electrolyte paste may include at least one of an oxide-based material and a sulfide-based material. It may include a lithium-conductive material.

According to the battery manufactured using the photosintering process according to the embodiment of the present invention, the oxide-based material may include Li-La-Ti-O or Li-La-Zr-O.

According to the battery manufactured using the photosintering process according to the embodiment of the present invention, the sulfide-based material may include Li ₂ SP ₂ S ₅ .

According to a battery manufactured using a photosintering process according to an embodiment of the present invention, the negative electrode paste is an intercalation / deintercalation type material including a carbon-based material or a titanium oxide-based material. ; An alloy / de-alloy type material comprising at least one of Si, Ge, Sn, Sb and SnO ₂ ; And an anode active material including at least one of a conversion type material including at least one metal oxide-based material of Fe ₂ O ₃ , Co ₃ O ₄ , MnxOy, and NiO.

According to the exemplary embodiment of the present invention, the electrode or the solid electrolyte in the solid state may be effectively manufactured in a short time by using the photosintering process.

More specifically, according to an embodiment of the present invention by preparing an electrode or a solid electrolyte through a photo sintering process, compared to the electrode or a solid electrolyte produced through a heat sintering process in a very short time, for producing an electrode or a solid electrolyte Various problems that may occur when the material is exposed to a high temperature environment for a long time (eg, substrate breakdown, reduction in durability due to residual thermal stress, etc.) may be improved.

According to the exemplary embodiment of the present invention, since the photosintering process time is very short in lithium ion batteries, lithium is hardly vaporized, thereby effectively reducing material loss.

According to an embodiment of the present invention, the photosintering process time is very short to prevent elemental diffusion between the electrode and the solid electrolyte.

1 is a flowchart illustrating a method of manufacturing a battery using a light sintering process according to an embodiment of the present invention.
2 is a cross-sectional view illustrating a structure of a battery manufactured using a photosintering process according to an embodiment of the present invention.
3 is a schematic diagram illustrating a photosintering process apparatus.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings and the contents described in the accompanying drawings, but the present invention is not limited or limited to the embodiments.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In this specification, the singular also includes the plural unless specifically stated otherwise in the phrase. As used herein, “comprises” and / or “comprising” refers to the presence of one or more other components, steps, operations and / or elements. Or does not exclude additions.

As used herein, “an embodiment”, “an example”, “side”, “an example”, etc., should be construed that any aspect or design described is better or advantageous than other aspects or designs. It is not.

In addition, the term 'or' refers to an inclusive or 'inclusive or' rather than an exclusive or 'exclusive or'. In other words, unless stated otherwise or unclear from the context, the expression 'x uses a or b' means any one of natural inclusive permutations.

Also, the singular forms “a” or “an”, as used in this specification and in the claims, generally refer to “one or more” unless the context clearly dictates otherwise or in reference to a singular form. Should be interpreted as.

The terminology used in the following description has been chosen to be general and universal in the art to which it relates, although other terms may vary depending on the development and / or change in technology, conventions, and preferences of those skilled in the art. Therefore, the terms used in the following description should not be understood as limiting the technical idea, but should be understood as exemplary terms for describing the embodiments.

In addition, in certain cases, there is also a term arbitrarily selected by the applicant, in which case the meaning will be described in detail in the corresponding description. Therefore, the terms used in the following description should be understood based on the meanings of the terms and the contents throughout the specification, rather than simply the names of the terms.

Meanwhile, terms such as first and second may be used to describe various components, but the components are not limited by the terms. The terms are used only to distinguish one component from another.

In addition, when a part such as a film, layer, area, or configuration request is said to be "on" or "on" another part, not only when it is directly above another part, but also another film, layer, area, or component in between. It also includes the case where it is interposed.

Unless otherwise defined, all terms used in the present specification (including technical and scientific terms) may be used in a sense that can be commonly understood by those skilled in the art. In addition, terms that are defined in a commonly used dictionary are not ideally or excessively interpreted unless they are specifically defined clearly.

On the other hand, in describing the present invention, when it is determined that the detailed description of the related known function or configuration may unnecessarily obscure the subject matter of the present invention, the detailed description thereof will be omitted. Terminology used herein is a term used to properly express an embodiment of the present invention, which may vary according to a user, an operator's intention, or a custom in the field to which the present invention belongs. Therefore, the definitions of the terms should be made based on the contents throughout the specification.

The battery manufactured by the method of manufacturing a battery using a photosintering process according to an embodiment of the present invention is at least one of a secondary battery, such as a lithium ion battery, a lithium-sulfur battery or a lithium-air battery, a primary battery and a solid oxide fuel cell (SOFC) It may be any one, but is not limited thereto.

In particular, the method of manufacturing a battery using a photosintering process according to an embodiment of the present invention may be applied to at least one of an electrode, a solid electrolyte, a lithium ion conductive solid electrolyte, a solid electrode containing lithium, and a solid electrolyte containing lithium. And, moreover, can be applied to various secondary battery component fields.

Therefore, the battery manufacturing method using the light sintering process according to an embodiment of the present invention can produce a high efficiency battery (battery) through an ultra-short sintering process.

In addition, when a method of manufacturing a battery using a photosintering process according to an embodiment of the present invention is applied to various component fields of a battery, a method of sintering a positive electrode, a solid electrolyte, and a negative electrode may be used in the same way. The materials of the positive electrode, solid electrolyte and negative electrode may vary.

Preferably, a lithium ion battery may be manufactured by a method of manufacturing a battery using a photosintering process according to an embodiment of the present invention. Hereinafter, a method of manufacturing a battery using a photosintering process according to an embodiment of the present invention using a lithium ion battery, but is not limited thereto.

1 is a flowchart illustrating a method of manufacturing a battery using a light sintering process according to an embodiment of the present invention.

Referring to FIG. 1, in the method of manufacturing a battery using a photosintering process according to an embodiment of the present invention, after applying a paste for a positive electrode on a substrate, sintering to form a positive electrode (S110), a solid electrolyte on the positive electrode After applying the paste, the step of sintering to prepare a solid electrolyte (S120) and after applying the paste for the negative electrode on the solid electrolyte, and sintering to prepare a negative electrode (S130).

In addition, at least one of forming a positive electrode (S110), manufacturing a solid electrolyte (S120), and manufacturing a negative electrode (S130) may be performed by a sintering process by a photosintering process.

Before describing the steps S110 to S130, a description of the light sintering process performed in the battery manufacturing method using the light sintering process according to the embodiment of the present invention will be described.

In the method of manufacturing a battery using the light sintering process according to an embodiment of the present invention, a strong light is instantaneously generated by applying a strong voltage to a lamp that generates light, and the light is an electrode (anode or cathode) or a solid. Reaching the electrolyte to supply the energy can be achieved through the photosintering process.

In addition, since the light sintering process is made very instantaneously, the time required for the process is very short, and the process cost can be reduced because the process can be performed in a general environment of normal temperature and pressure.

In addition, the light sintering process can easily adjust the application area so that it can be sintered locally or over a large area (wide area), and because it uses strong light energy, it can control energy from thin samples to thick thickness through energy control. It can show the overall sintering capacity up to the sample.

The method of manufacturing a battery using a photosintering process according to an embodiment of the present invention effectively suppresses problems that may occur when applying a high temperature sintering environment and other sintering techniques, particularly by introducing a photosintering process in manufacturing a lithium ion battery component. At the same time, as the sintering time is greatly shortened, not only the performance of the battery but also the productivity can be greatly increased.

More specifically, the method for manufacturing a battery using the photosintering process according to the embodiment of the present invention may produce a solid electrode (anode or cathode) and a solid electrolyte of a lithium ion battery using the photosintering process.

For example, electrodes of lithium ion batteries such as LiCoO ₂ and lithium ion conductive solid electrolytes such as Li-La-Ti-O, Li-La-Zr-O or Li-Ge-PS may contain Li. In many cases, Li is a very unstable material and has a very low melting point, resulting in a lot of material loss due to vaporization after prolonged exposure to a high temperature environment.

However, in the method for manufacturing a battery using the photosintering process according to the embodiment of the present invention, a process using the photosintering process under normal temperature and atmospheric pressure is performed, and the processing time is very short, which can drastically reduce the loss of Li. .

In addition, in the conventional case, due to the diffusion of elements between the electrodes (anode and cathode) and the process of producing a solid electrolyte, problems such as La-Co interdiffusion (co-diffusion) between the LLZO solid electrolyte and LiCoO ₂ electrode Interface and resistance increase), but the method of manufacturing a battery using a photosintering process according to an embodiment of the present invention by introducing a photosintering process, shortening the process time to solve the problem of diffusion of elements Can be solved.

In addition, the synthesis method using a conventional sintering method, such as a heat sintering process has a long manufacturing time and a high process temperature, there is an uneconomic problem, the method of manufacturing a battery using a light sintering process according to an embodiment of the present invention is a photo sintering process The process time can be shortened by introducing a process, and the process proceeds under normal temperature and normal pressure, thereby eliminating the problem caused by heat sintering.

Hereinafter, a method of manufacturing a battery using a light sintering process according to an embodiment of the present invention will be described in detail.

First, in step S110 after applying the paste for the positive electrode on the substrate, it is sintered to form the positive electrode.

According to an embodiment, the substrate may include at least one of a silicon substrate, a glass substrate, a ceramic substrate, a polymer substrate, or a metal substrate.

According to an embodiment, the polymer substrate may be polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polypropylene (PP), polyimide (polyimide, PI). ) And triacetylcellulose (TAC).

The metal substrate is silver (Ag), gold (Au), platinum (Pt), palladium (Pd), aluminum (Al), nickel (Ni), copper (Cu), titanium (Ti), vanadium (V), chromium At least one of (Cr), iron (Fe), cobalt (Co), manganese (Mn), molybdenum (Mo), niobium (Nb), thallium (Ta), tungsten (W) and stainless steel It may include.

According to an embodiment, the substrate may be a conductive substrate or a non-conductive substrate.

When the substrate is a conductive substrate such as a metal substrate, the substrate can be used as an anode since it exhibits conductivity.

In some embodiments, the substrate may be flexible, such as a polymer substrate, or may be substantially non-flexible.

The positive electrode paste may include a positive electrode active material, a binder, and an organic solvent.

According to an embodiment, the cathode active material included in the cathode paste may include a cathode active material including Li, and specifically, the cathode active material is LiCoO ₂ , LiNiO ₂ , LiNi _1-x CoxO ₂ , LiMnO ₂ , LiMn It may include at least one of ₂ O ₄ , LiV ₃ O ₈ , LiFePO ₄ , LiMnPO ₄ , LiCoPO ₄ and Li ₃ V ₂ (PO ₄ ) ₃ .

In some embodiments, the cathode active material may include a transition metal, and may be, for example, a compound including transition metal elements such as lanthanum (La), strontium (Sr), cobalt (Co), and manganese (Mn). have.

In step S110, the paste for the cathode may be applied onto the substrate by a vacuum process or a non-vacuum process.

The non-vacuum process is dip coating, spin coating, screen printing, laser blade coating, spray coating and electrostatic spray deposition. It may be any one of.

The vacuum process may be at least one of evaporation, sputtering, pulsed laser deposition, chemical vapor deposition, and atomic layer deposition.

Step S110 may be sintered by a photosintering process or a heat sintering process, but preferably, may be sintered by a photosintering process.

The light sintering process may be performed using a light sintering process apparatus, and the light sintering process apparatus will be described with reference to FIG. 2.

The photosintering process for the cathode paste may be performed at room temperature, but may be performed at 400 ° C. according to an embodiment.

The photosintering process for the positive electrode paste may be performed at 300 ° C. to 600 ° C. when the positive electrode active material including a transition metal is included in the positive electrode paste.

If the light sintering process is carried out at less than 300 ℃ there is a problem that does not show a significant difference with the progress at room temperature.

When the light sintering process is in excess of 600 ° C., when the light sintering is performed, a phenomenon such as failure of the strong energy and the destruction of the film (anode) may occur, or excessive sintering may occur.

The photosintering process may be carried out under an air atmosphere or atmospheric pressure by exposure to a general laboratory environment.

The light sintering process may be controlled by at least one of a capacitor, a controller, and a power supply to vary (adjust) the light energy.

In some embodiments, the optical sintering process may control at least one of a capacitor, a controller, and a power supply to vary (adjust) the number of pulses.

In some embodiments, the optical sintering process may control at least one of a capacitor, a controller, and a power supply to vary (adjust) the pulse interval.

For example, when sintering a positive electrode paste containing a positive electrode active material containing a transition metal, the light energy 70J to 100J, the number of pulses 5 to 6, the light irradiation time (on-time) 10ms per pulse, the pulse interval (off -time) 10ms can be used to proceed with the light sintering process.

According to the embodiment, since the high energy is required depending on the kind of the material to be sintered or the method of applying the paste for the anode in the light sintering process, the pulse interval may be extended to 200 ms.

The method of manufacturing a battery using the photosintering process according to the embodiment of the present invention may reduce the photosintering process time of the cathode paste to a level of 0.1 seconds to 10 seconds.

The photosintering process time may be calculated by [pulse on time (s) + pulse off time (s)] × pulse number.

When the pulse off time is long in the light sintering process time, the interval at which the light energy is transmitted is widened, so that sufficient energy is hardly transmitted.

In addition, when the light sintering process time increases as the number of pulses in the light sintering process time increases, it is difficult to construct a very large number of pulses in the light sintering equipment structure.

The pulse start time is typically very short compared to the pulse off time.

However, in the increase of the photosintering process time according to the increase of the pulse start time, when the pulse start time is excessively increased, it is not suitable for the light sintering of instantaneous energy irradiation.

Therefore, the photosintering process may be performed for 0.1 seconds to 10 seconds, in particular, the photosintering process time of 0.1 seconds is the shortest time of the photosintering process that can be performed in the laboratory.

Therefore, the method of manufacturing a battery using the photosintering process according to the embodiment of the present invention introduces a photosintering process to manufacture a positive electrode, thereby greatly reducing the sintering time and effectively suppressing the loss due to vaporization of Li element. can do.

In addition, the method for manufacturing a battery using the photosintering process according to the embodiment of the present invention can effectively improve the crystallinity of the material for forming the positive electrode by introducing a photosintering process to manufacture the positive electrode.

In addition, the method of manufacturing a battery using a photosintering process according to an embodiment of the present invention can effectively suppress the formation and development of grain boundaries that hinder the conduction of lithium ions by introducing a photosintering process to manufacture a positive electrode. have.

In addition, the battery manufacturing method using a photosintering process according to an embodiment of the present invention by introducing a photosintering process to produce a positive electrode, very short sintering time, to suppress the formation of secondary phases that interfere with the conduction of lithium ions can do.

Step S120 is a paste for applying a solid electrolyte on the positive electrode, and then sintered to form a solid electrolyte.

The solid electrolyte paste may include a solid electrolyte material, a binder, and an organic solvent.

In some embodiments, the solid electrolyte material included in the solid electrolyte paste may include a solid lithium-conductive material including at least one of an oxide-based material and a sulfide-based material. It may include.

According to an embodiment, the oxide-based material included in the solid electrolyte paste may include perovskite such as Li-La-Ti-O and NASICON, LISICON or Li-La-Zr-O. It may include at least one of the same garnet (garnet).

According to an embodiment, the sulfide-based material included in the solid electrolyte paste may include Li ₂ SP ₂ S ₅ .

In step S120, the solid electrolyte paste may be applied onto the anode by a vacuum process or a non-vacuum process.

The non-vacuum process is dip coating, spin coating, screen printing, laser blade coating, spray coating and electrostatic spray deposition. It may be any one of.

The vacuum process may be at least one of evaporation, sputtering, pulsed laser deposition, chemical vapor deposition, and atomic layer deposition.

The step S120 may be sintered by a photosintering process or a heat sintering process, but preferably, may be sintered by a photosintering process.

The light sintering process may be performed using a light sintering process apparatus, and the same apparatus as the light sintering process apparatus for sintering the paste for the cathode may be used.

The photosintering process for the solid electrolyte paste may be performed at room temperature, and in some embodiments, the photosintering process for the solid electrolyte paste may be performed at 400 ° C.

According to an embodiment, the photosintering process for the solid electrolyte paste may be performed at 500 ° C to 600 ° C.

In the case of the solid electrolyte paste, densification is required, and therefore, the photosintering process may be performed at a temperature of 500 ° C. to 600 ° C., which is a relatively high temperature environment, than that of the cathode paste.

That is, in the step S120, the instantaneous energy irradiation and the photosintering process in a relatively high temperature environment are advantageous for removing voids, suppressing crack generation, and increasing density of the solid electrolyte.

The photosintering process may be carried out under an air atmosphere or atmospheric pressure by exposure to a general laboratory environment.

The light sintering process may be controlled by at least one of a capacitor, a controller, and a power supply to vary (adjust) the light energy.

In some embodiments, the optical sintering process may control at least one of a capacitor, a controller, and a power supply to vary (adjust) the number of pulses.

In some embodiments, the optical sintering process may control at least one of a capacitor, a controller, and a power supply to vary (adjust) the pulse interval.

At this time, the photosintering process of the solid electrolyte paste requires higher light energy than in the photosintering process of the positive electrode paste.

Specifically, when the solid electrolyte paste is photosintered, light energy 90J to 130J, pulse number 5 to 6, light irradiation time per pulse (on-time) 10ms, pulse interval (off-time) to 150ms to 200ms Photosintering process can proceed.

This is because conditions such as sintering temperature and melting point of materials constituting the positive electrode paste and the solid electrolyte paste are different, so that the conditions of the photosintering process are different.

According to the embodiment, since the high energy is required depending on the kind of the material to be sintered or the method of applying the paste for the anode in the light sintering process, the pulse interval may be extended to 200 ms.

The method of manufacturing a battery using the photosintering process according to the embodiment of the present invention may reduce the photosintering process time of the solid electrolyte paste to a level of 0.1 second to 10 seconds.

Detailed description thereof is the same as the description of the photosintering process time of the positive electrode paste, and thus redundant description thereof will be omitted.

Therefore, the method of manufacturing a battery using the photosintering process according to the embodiment of the present invention introduces a photosintering process to prepare a solid electrolyte, thereby greatly reducing the sintering time and effectively suppressing the loss due to vaporization of Li element. can do.

In addition, the method for manufacturing a battery using the photosintering process according to the embodiment of the present invention can effectively improve the crystallinity of the material for forming the solid electrolyte by introducing the photosintering process to produce a solid electrolyte.

In addition, the method of manufacturing a battery using a photosintering process according to an embodiment of the present invention can effectively suppress the formation and development of grain boundaries that hinder the conduction of lithium ions by introducing the photosintering process to prepare a solid electrolyte. Can be.

In addition, the battery manufacturing method using the photosintering process according to the embodiment of the present invention can suppress the formation of a secondary phase that interferes with the conduction of lithium ions by introducing a photosintering process to produce a solid electrolyte.

Step S130 after applying the negative electrode paste on the solid electrolyte, and then sintered to form a negative electrode.

The negative electrode paste may include a negative electrode active material, a binder, and an organic solvent.

According to an embodiment, the negative electrode active material included in the negative electrode paste may be an intercalation / de-intercalation type material or an alloy / de-alloy type. At least one of a material and a conversion type material may be included.

The intercalation / deintercalation type material may include at least one of a carbon-based material such as graphene and a titanium oxide-based material such as TiO ₂ or LiTi ₄ O ₅ . It is not limited to the above materials.

The alloy / de-alloy type material may include at least one of Si, Ge, Sn, Sb, and SnO ₂ , but is not limited thereto.

The conversion type material may include at least one metal oxide-based material of Fe ₂ O ₃ , Co ₃ O ₄ , MnxOy, and NiO, but is not limited thereto.

According to an embodiment, the negative electrode active material may include a transition metal, and for example, may be a compound including a transition metal element such as lanthanum (La), strontium (Sr), cobalt (Co), and manganese (Mn). have.

In step S130, the negative electrode paste may be applied onto the solid electrolyte by a vacuum process or a non-vacuum process.

The non-vacuum process is dip coating, spin coating, screen printing, laser blade coating, spray coating and electrostatic spray deposition. It may be any one of.

The vacuum process may be at least one of evaporation, sputtering, pulsed laser deposition, chemical vapor deposition, and atomic layer deposition.

The step S130 may be sintered by a photosintering process or a heat sintering process, but preferably, may be sintered by a photosintering process.

The light sintering process may be performed using a light sintering process apparatus, and the same apparatus as the light sintering process apparatus for sintering the positive electrode paste or the solid electrolyte paste may be used.

The photosintering process for the anode paste may be performed at room temperature, and may be performed at 400 ° C. according to an embodiment.

The photosintering process for the negative electrode paste may be performed at 300 ° C. to 600 ° C. when the negative electrode active material including the transition metal is included in the negative electrode paste.

The reason why the photosintering process temperature of the anode paste is limited to the above numerical range has been dealt with above in the description of the photosintering process temperature of the cathode paste, and thus redundant description thereof will be omitted.

The photosintering process may be carried out under an air atmosphere or atmospheric pressure by exposure to a general laboratory environment.

The light sintering process may be controlled by at least one of a capacitor, a controller, and a power supply to vary (adjust) the light energy.

In some embodiments, the optical sintering process may control at least one of a capacitor, a controller, and a power supply to vary (adjust) the number of pulses.

In some embodiments, the optical sintering process may control at least one of a capacitor, a controller, and a power supply to vary (adjust) the pulse interval.

For example, when sintering a negative electrode paste containing a negative electrode active material including a transition metal, light energy 70J to 100J, the number of pulses 5 to 6, light irradiation time (on-time) 10ms per pulse, pulse interval (off -time) 10ms can be used to proceed with the light sintering process.

According to the embodiment, since the high energy is required depending on the kind of the material to be sintered or the method of applying the paste for the negative electrode in the light sintering process, the pulse interval may be extended to 200 ms.

The method of manufacturing a battery using the photosintering process according to the embodiment of the present invention may reduce the photosintering process time of the negative electrode paste to a level of 0.1 seconds to 10 seconds.

The reason why the photosintering process time of the negative electrode paste is limited to the numerical range has been dealt with in the above description of the photosintering process time of the positive electrode paste, and thus redundant description thereof will be omitted.

Therefore, the method of manufacturing a battery using the photosintering process according to the embodiment of the present invention introduces a photosintering process for manufacturing a negative electrode, thereby greatly reducing the sintering time and effectively suppressing the loss due to vaporization of Li element. can do.

In addition, the method of manufacturing a battery using the photosintering process according to the embodiment of the present invention can effectively improve the crystallinity of the material for forming the negative electrode by introducing a photosintering process to produce a negative electrode.

In addition, the method of manufacturing a battery using a photosintering process according to an embodiment of the present invention can effectively suppress the formation and development of grain boundaries that hinder the conduction of lithium ions by introducing the photosintering process to manufacture a negative electrode. have.

In addition, the method of manufacturing a battery using a photosintering process according to an embodiment of the present invention by introducing a photosintering process to produce a negative electrode, thereby greatly shortening the sintering time, to suppress the diffusion between the negative electrode and the solid electrolyte material, Secondary phase formation that inhibits conduction of lithium ions can be suppressed.

Through a method of manufacturing a battery using a photosintering process according to an embodiment of the present invention, a battery such as a lithium ion battery in which a positive electrode, a solid electrolyte, and a negative electrode are sequentially stacked may be manufactured.

According to an embodiment, the method of manufacturing a battery using the light sintering process according to the embodiment of the present invention may further include forming a current collector on the lower part of the positive electrode and the upper part of the negative electrode.

The current collector may collect electrons generated by the electrochemical reaction of the positive electrode active material or the negative electrode active material or supply electrons required for the electrochemical reaction.

According to an embodiment, the current collector may include stainless steel, aluminum, nickel, titanium, calcined carbon, or copper; Stainless steel surface-treated with carbon, nickel, titanium or silver; Aluminum-cadmium alloys; Non-conductive polymer surface-treated with a conductive material; Conductive polymers; Metal pastes comprising metal powders of Ni, Al, Au, Ag, Pd / Ag, Cr, Ta, Cu, Ba, or ITO; Or a carbon paste including carbon powder which is graphite, carbon black or carbon nanotubes; It may include at least one of, but is not limited to the material.

Therefore, a battery such as a lithium ion battery manufactured according to a method of manufacturing a battery using a photosintering process according to an embodiment of the present invention may further include a current collector at a lower portion of the positive electrode and an upper portion of the negative electrode.

2 is a cross-sectional view illustrating a structure of a battery manufactured using a photosintering process according to an embodiment of the present invention.

Referring to FIG. 2, the battery 100 manufactured using the light sintering process according to the embodiment of the present invention is manufactured through the method of manufacturing the battery 100 using the light sintering process described with reference to FIG. 1.

The battery 100 manufactured using the light sintering process according to the embodiment of the present invention uses the anode 120 formed by using the anode paste on the substrate 110 and the solid electrolyte paste on the anode 120. And a cathode 140 formed on the solid electrolyte 130 and the cathode paste on the solid electrolyte 130.

In this case, at least one of the anode 120, the solid electrolyte 130, and the cathode 140 may be formed by sintering by a photosintering process.

Since the configuration and the light sintering process of the battery 100 manufactured using the light sintering process according to the exemplary embodiment of the present invention are specifically mentioned in the above description of FIG. 1, redundant descriptions thereof will be omitted.

3 is a schematic diagram illustrating a photosintering process apparatus.

Referring to FIG. 3, the photosintering apparatus includes a support part 5 supporting a sample 6, a Xenon lamp 1 for irradiating white light, a reflector 2 for intensively irradiating white light, and a xenon It may include, but is not limited to, a power supply 4 for powering the lamp 1 and a capacitor 3 for supplying instantaneous high power to the white light.

The power supply 4 supplies electric power to the xenon lamp 1 and generates voltage and current and transmits the generated voltage and current to the xenon lamp 1.

According to an embodiment, the photosintering process apparatus may comprise at least one power supply 4.

The capacitor 3 is connected to the power supply 4 to supply instantaneous high power to the xenon lamp 1, which can deliver instantaneously high power in a very short time to form a pulse.

Accordingly, when voltage and current are input from the power supply 4 to the xenon lamp 1, the integrated charge from the capacitor 3 is applied to generate an arc plasma in the xenon lamp 1.

Then, the microwave white light may be output from the xenon lamp 1 to the surface of the sample 6 in which any one of the positive electrode paste, the solid electrolyte paste, and the negative electrode paste according to the embodiment of the present invention is formed.

According to an embodiment, the photosintering process apparatus may comprise at least one or more capacitors 3.

The photosintering process apparatus may include a controller (not shown) for controlling the white light emitted from the xenon lamp 1 to be irradiated at least two or more pulse cycles.

The controller applies power to the xenon lamp 1 to perform the photosintering process.

The controller may apply power to the xenon lamp 1 in the form of a pulse, and the controller may apply pulses having different heights according to time changes, or mix two or more pulses to change more various heights. The pulse having a can be applied.

More specifically, at least two pulse cycles have different pulse parameters, and the pulse parameter may be at least one of pulse intensity, pulse gap, pulse width, and pulse number.

According to an embodiment, the photosintering process apparatus may further include at least one of a controller for controlling the pulse of the light energy of the white light and a cooler for controlling the temperature of the xenon lamp 1.

Further, according to the embodiment, a heater for applying heat to the sample 6 may be used as the support 5 included in the photosintering process apparatus.

Further, according to the embodiment, when the light sintering process apparatus includes a heater 5, the xenon lamp 1 and the heater 5 are properly adjusted to proceed with the light sintering process or the heat sintering process, or the light sintering process and The heat sintering process can also be carried out simultaneously.

On the other hand, the embodiments of the present invention disclosed in the specification and drawings are merely presented specific examples to aid understanding, and are not intended to limit the scope of the present invention. It is apparent to those skilled in the art that other modifications based on the technical spirit of the present invention can be carried out in addition to the embodiments disclosed herein.

1: xenon lamp 2: reflector
3: capacitor 4: power supply
5: support or heater 6: sample
100: battery 110: substrate
120: anode 130: solid electrolyte
140: cathode

Claims (12)

Applying a paste for a cathode on a substrate and then sintering to form a cathode;
Applying a paste for a solid electrolyte on the anode and then sintering to form a solid electrolyte; And
Applying a paste for a negative electrode on the solid electrolyte, and then sintering to form a negative electrode
Including,
At least one of forming the positive electrode, forming the solid electrolyte, and forming the negative electrode is sintered by a photosintering process.
The method of claim 1,
The photo sintering process is a manufacturing method of a battery using a photo sintering process, characterized in that for about 0.1 to 10 seconds.
The method of claim 1,
The photosintering process for the cathode paste and the anode paste is carried out at 300 ° C to 600 ° C.
The method of claim 1,
The photo sintering process for the paste for the solid electrolyte is a manufacturing method of a battery using a photo sintering process, characterized in that proceeds at 500 ℃ to 600 ℃.
The method of claim 1,
The light energy of the photosintering process for the positive electrode paste and the negative electrode paste is 70J to 100J.
The method of claim 1,
The light energy of the photosintering process for the solid electrolyte paste is 90J to 130J, the manufacturing method of a battery using a photosintering process.
An anode formed on the substrate using an anode paste;
A solid electrolyte formed on the anode using a paste for solid electrolyte; And
A negative electrode formed on the solid electrolyte using a paste for the negative electrode
Including,
At least one of the positive electrode, the solid electrolyte and the negative electrode is a battery produced using a photo sintering process, characterized in that sintered by a photo sintering process.
The method of claim 7, wherein
The positive electrode paste is of _{LiCoO 2, LiNiO 2, LiNi 1} -x CoxO 2, LiMnO 2, LiMn 2 O 4, LiV 3 O 8, LiFePO 4, LiMnPO 4, LiCoPO 4 and _{Li 3 V 2 (PO 4)} 3 A battery manufactured using a photosintering process comprising a positive electrode active material including at least one.
The method of claim 7, wherein
The solid electrolyte paste may include a solid lithium-conductive material including at least one of an oxide-based material and a sulfide-based material. Battery prepared by.
The method of claim 9,
The oxide-based material is a battery produced using a photo-sintering process characterized in that it comprises Li-La-Ti-O or Li-La-Zr-O.
The method of claim 9,
The sulfide-based material is a battery manufactured using a photosintering process characterized in that it comprises Li ₂ SP ₂ S ₅ .
The method of claim 7, wherein
The negative electrode paste may include an intercalation / deintercalation type material including a carbon-based material or a titanium oxide-based material; An alloy / de-alloy type material comprising at least one of Si, Ge, Sn, Sb and SnO ₂ ; And a negative electrode active material including at least one of a conversion type material including at least one metal oxide-based material of Fe ₂ O ₃ , Co ₃ O ₄ , MnxOy, and NiO. Battery prepared by.

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