KR101920850B1 - The machine manufacturing lithium electrode for thermal batteries - Google Patents

Abstract

A method for manufacturing a lithium electrode according to the present invention comprises the following steps: supplying argon gas to a first chamber including a lithium (Li) supply device, an iron (Fe) supply device, and a mixing container; supplying lithium from a lithium supplying apparatus to the mixing container; melting the supplied lithium using a heater; supplying an iron powder from an iron supply unit to the mixing container; mixing the melted lithium and the supplied iron powder in the mixing container to produce a lithium-iron mixture; and transferring the lithium-iron mixture to a second chamber to produce an electrode.

Description

TECHNICAL FIELD [0001] The present invention relates to a lithium ion battery,

The present invention relates to an apparatus for manufacturing a lithium electrode for a thermal battery, and more particularly, to an apparatus for manufacturing a lithium electrode for a thermal battery having a high output / large capacity.

A structure in which a unit cell composed of a pellet type positive electrode (FeS2), an electrolyte (LiCl-KCl or LiF-LiCl-LiBr), a negative electrode (LiSi or LiAl) and a heat source (Fe / KClO4) . Since such a thermal battery is operated at a high temperature (500 ° C), the ionic conductivity of the electrolyte is high and the electrochemical reaction speed is fast, and thus the output characteristic is excellent. In addition, since the electrolyte is kept in an inactive state at room temperature and then melted by ignition of a heat source, the battery is operated only with little self-discharge, and is excellent in structural stability, reliability, and long-term storage. Because of these characteristics, thermoelectric is mainly used as a power source for guided weapons and space launch vehicles. As the speed of the guided weapon system increases, there is a growing demand for high output, high reliability and longevity of the energy source for the propulsion unit and the drive power source installed thereon. Accordingly, studies on high output and large capacity of thermocells have been conducted, but the pellet type electrode (10-2014-0144427, 10-1750230), which is fundamentally manufactured by powder molding, has a limitation in meeting these requirements. Pellet-type electrodes using expensive high-capacity presses have limited production for thin electrodes (<0.25 mm) and large diameter electrodes (<150 mm). In addition, for the pellet molding, a molten salt of an electrode is mixed and manufactured. In this manufacturing method, the moldability of the pellets is improved due to the molten salt, but the amount of the electrode active material is reduced, thereby decreasing the thermal conductivity. In addition to the limitation of the thickness and the area, There is a problem that this can not be done. In addition, the pellet type electrode has a disadvantage in that it has a wide operating temperature range and excellent output characteristics but is fragile. In order to solve such problems, US Pat. No. 3,980,888 and US Pat. No. 4,221,849 disclose the preparation of a thermocatalytic cathode by mixing 15-30% of liquid lithium and 70-85% of iron powder. In US Pat. No. 4,675,257, contents of US 3,980,888 and US 4,221,849 were registered for a nickel mesh for fixing lithium on the cathode. US 7,354,678 reports on a thermocathode cathode mixed with lithium-aluminum-iron powder have. Therefore, new electrodes should be studied in order to improve not only high output and large capacity but also electrode strength and high temperature operation stability in Korea. And a manufacturing condition and apparatus for a new electrode production.

Korea Patent: 10-2014-0144427 Korea Patent: 10-1750203 US Patent: US 3,930,888 United States Patent: US 4,221,849 US Patent: US 4,675,257 US Patent: US 7,354,678

The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a process for mixing and cooling lithium used as an electrode active material with iron powder as a binder and a process apparatus for rolling and pressing the mixture, The purpose of this paper is to fabricate a large area (> 150 ㎜) electrode which is inexpensive to manufacture compared to the conventional pellet electrode manufactured by powder molding using a large press, and which can not produce pellet electrodes.

It is another object of the present invention to improve the performance of a thermocouple by manufacturing a high output / large capacity electrode through a large area.

In addition, since the present invention does not add a molten salt, it is an object of the present invention to prepare an electrode by adjusting the amount of the active material according to the intended use.

The technical problem to be solved by this embodiment is not limited to the above-mentioned technical problems, and other technical problems can be deduced from the following embodiments.

As a technical means for achieving the above-mentioned technical object, a first aspect of the present disclosure provides a method of manufacturing a semiconductor device, comprising: supplying argon gas to a first chamber including a lithium (Li) supply device, an iron (Fe) supply device and a mixing container; Supplying lithium from the lithium supplying apparatus to the mixing vessel; Melting the supplied lithium using a heater; Supplying iron powder from the iron supply unit to the mixing vessel; Mixing the molten lithium and the supplied iron powder in the mixing vessel to produce a lithium-iron mixture; And transferring the lithium-iron mixture to a second chamber to produce an electrode.

In addition, the second chamber includes a roller, a rudder and a press, rolling the transferred lithium-iron mixture to the roller to produce a lithium-iron sheet; Cutting the lithium-iron sheet to a predetermined size using the rubbing machine; And removing the cut lithium-iron sheet, and applying pressure to the pressed sheet to produce an electrode.

The second chamber may further include a case for a seat and a mesh, the method comprising: disposing the mesh in the case; And removing the cut lithium-iron sheet on the mesh.

In addition, an argon gas may be supplied to the second chamber.

Also, it is possible to provide a method of manufacturing a lithium electrode, wherein the roller, the rudder, and the press are made of the same material.

Further, the press may provide a method of manufacturing a lithium electrode including an upper press and a lower press.

In addition, the second chamber may further include a jig, wherein the second chamber is provided with the jig and cooling the lithium-iron mixture to cool the jig; And forming an electrode by applying pressure to the cooled lithium-iron mixture with the phase press.

Also, it is possible to provide a method of manufacturing a lithium electrode, wherein the devices included in the first chamber and the second chamber are made of the same material.

As a technical means for achieving the above-mentioned technical object, the first aspect of the present disclosure can provide a lithium electrode, which is produced through the above-described electrode manufacturing method.

As a technical means for achieving the above-mentioned technical object, a first aspect of the present disclosure provides a system for manufacturing an electrode, comprising: a first chamber including a lithium supply device, an iron supply device, and a mixing container; And a second chamber including a roller, a rudder, a press, a case for a sheet, a mesh and a jig, wherein the lithium-iron mixture produced in the first chamber is supplied to the second chamber through a transfer passage, The lithium electrode production system according to the present invention can provide a lithium electrode production system.

According to the present invention, it is possible to improve the performance of the thermocouple by manufacturing a high-output / high-capacity electrode through the enlargement of the size of the electrode as well as the manufacturing cost as compared with the conventional pellet electrode manufactured by the powder molding method using an expensive large- There is an effect.

Further, since the electrode can be manufactured by adjusting the amount of the electrode active material to the similar thickness and the same area, the weight and the volume of the thermal battery can be reduced.

In addition, even if no molten salt is added, it is possible to manufacture the electrode according to the intended use, thereby reducing the cost and mass production.

FIG. 1 is a flowchart illustrating a method of mixing a high-power / high-capacity electrode according to an embodiment.
FIG. 2 is a flowchart illustrating a method of mixing a high-power / high-capacity electrode according to an embodiment.
FIG. 3 is a view illustrating a high-power / high-capacity electrode mixing apparatus according to an embodiment.
4A is a diagram illustrating a high-power / high-capacity electrode mixing apparatus according to an embodiment of the present invention.
FIG. 4B is a view illustrating a high-power / high-capacity electrode mixing apparatus according to an embodiment.

While the present invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not limited to the disclosed embodiments. Also, in certain cases, there may be a term selected arbitrarily by the applicant, in which case the meaning thereof will be described in detail in the description of the corresponding invention. Therefore, the term used in the present invention should be defined based on the meaning of the term, not on the name of a simple term, but on the entire contents of the present invention.

 Whenever a part includes an element throughout the specification, it means that the element can include other elements, not excluding other elements, unless specifically stated otherwise.

Also, the connection lines or connection members between the components shown in the figures are merely illustrative of functional connections and / or physical or circuit connections. In practical devices, connections between components can be represented by various functional connections, physical connections, or circuit connections that can be replaced or added.

Conventional powder forming processes are made by mixing electrode active materials with molten salts (such as LiCl-KCl or LiF-LiCl-LiBr) in order to improve the molding and strength of pellets. If the molten salt is not added, the pellet can not be formed. If the molten salt is added, the thickness and the area of the molten salt are limited, and a thin electrode and a large area (> 150 mm) electrode can not be manufactured.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will now be described in detail with reference to the accompanying drawings, which illustrate an apparatus for manufacturing a high power, high capacity and high capacity electrode for a thermal battery (ADLIE, ADD Developed Lithium-impregnated Electrode) according to the present invention.

FIG. 1 is a flowchart illustrating a method of mixing a high-power / high-capacity electrode according to an embodiment. 2 is a flowchart illustrating a method of mixing a high-power / high-capacity electrode according to an embodiment.

The electrode mixing method shown in Figs. 1 and 2 will be described with reference to Fig. 3 and subsequent figures.

FIG. 3 is a view illustrating a high-power / high-capacity electrode mixing apparatus according to an embodiment.

Referring to FIG. 3, when a high power / high capacity electrode mixing apparatus is referred to, a mixer machine used for mixing the electrodes is constructed as follows. The inert atmosphere holding case S100, the argon gas S200, the lithium supplying device S300, the lithium S310, the lithium moving path S320, the iron powder feeder S400, the iron powder S410, The mixing chamber S600, the lithium / iron mixing vessel S700, the heater S800 and the lithium / iron mixture moving passage S900 as the moving passage S420, the stirrer S500, the lithium / iron mixture S510, .

The inert atmosphere holding case S100 may be referred to as a first chamber as compared with the inert atmosphere holding glove box A10 described below. The first chamber is supplied with argon gas (S200), and an atmosphere of 50 ppm or less oxygen and 10 ppm or less of water should be maintained (S110). The oxidation of lithium (Formula 1) may occur in a high-temperature environment in which the concentration of oxygen and water present in the first chamber does not satisfy the above conditions, which is not preferable.

Further, Ni, Al, Ti, Zr, graphite and the like among the materials of the case (S100) are not preferable due to their reactivity with lithium at high temperature (300 deg. Therefore, pure stainless steel, ferritic stainless steel and austenitic stainless steel, which are less reactive with lithium (S310), should be used as the material of the case S100.

The lithium supply device S300 serves to supply and store lithium metal or lithium granule or lithium powder S310 and the like as an electrode active material and may be connected to the lithium transfer path S320 and the lithium / iron mixed container case S600 To the lithium / iron mixing vessel S700 (S120). The transferred lithium (S310) is melted (S130) in a lithium / iron mixing vessel (S700) using a heater (S800) at 310 to 350 占 폚. The iron powder feeder (S400) supplies and stores an iron powder (S410) that serves to hold lithium so that lithium does not flow down at a high temperature. In order to mix it with lithium (S310) (S420) and the lithium / iron mixing container case (S600) to the lithium / iron mixing container (S700) to mix with the melted lithium (S140). The melted lithium and iron powder S410 is heated at a temperature of 300 to 350 ° C, a stirring speed of 100 to 500 rpm / min and a stirring time of 5 to 60 minutes using a heater S800 and a stirrer S500. ) To prepare a molten lithium / iron mixture (S510). The produced molten lithium / iron mixture (S510) may be moved to the lithium / iron mixture transfer passage (S900) and then processed as a next step of cooling, rolling and pressing, and then formed into an electrode.

The materials of the lithium supplying device S300 and the lithium transfer path S320 are made of pure iron, ferritic stainless steel or chromium coating having low reactivity and wettability with lithium S310 which is the same material as the inert atmosphere holding case S100, Should be used. The material of the iron powder feeder (S400) and the iron powder transfer passage (S420) should be the same material as the inert atmosphere holding case (S100).

Since the iron powder S410 has poor wettability with the lithium (S310), it can be supplied in three, five, ten, etc. in consideration of the weight of the lithium (S310). As the weight of lithium S310 is increased and the weight ratio of iron powder S410 is decreased when 10 to 30 wt.% Of lithium S310 and 70 to 90 wt.% Of iron powder S410 are mixed, the volume of lithium S310 The mixing amount of the iron powder S410 can be supplied in small amounts, but it is preferable to determine the amount of the iron powder S410 considering the wettability of the iron powder S410. The apparent density of the iron powder (S410) is preferably 0.3 to 2.0 g / cc, and the particle size is preferably 1 to 20 mu m or less.

The material of the stirrer (S500) should also be pure iron, ferritic stainless steel and austenitic stainless steel which have low reactivity and wettability with lithium (S310).

The lithium / iron mixing container case S600 may be formed in a double structure in consideration of the reactivity between lithium (S310) and oxygen or nitrogen, and may heat the lithium / iron mixing container S700 applied through the heater S800 It is used to prevent leakage to the outside. In addition, the material of the lithium / iron mixed container case (S600) is the same as the above-mentioned material.

It is preferable to use the aforementioned pure iron, ferritic stainless steel, and austenitic stainless steel as the material of the lithium / iron mixing vessel S700. In the lithium / iron mixing vessel S700, It can be coated with high tensile tantalum, molybdenum, chromium, etc.

The temperature of the heater S800 is preferably maintained in the range of 310 to 350 ° C. This is not preferable because the nitride (Formula 2) is formed due to the reaction of lithium (S310) with nitrogen at a temperature of 300 ° C. or less , There is a risk of explosion due to the reaction of lithium (S310) with nitrogen at a temperature of 400 占 폚 or more, which is not preferable.

4A is a diagram illustrating a high-power / high-capacity electrode mixing apparatus according to an embodiment of the present invention. FIG. 4B is a view illustrating a high-power / high-capacity electrode mixing apparatus according to an embodiment of the present invention.

4A and 4B are equipment for manufacturing a high output / large capacity electrode using a lithium / iron mixture (S510) completed in the process of FIG. 1 as a high output / large capacity electrode mixture cooling, rolling and pressing apparatus.

Referring to FIG. 4A, a glove box A10 for maintaining an inert atmosphere, argon gas (S200), a lithium / iron mixture transfer passage S900, a lithium / iron mixture S510 The lithium / iron sheet A300, and the lithium / iron sheet A300 after rolling of the substrate A100, the roller A200, the lithium / iron mixture S510, And a vacuum suction and desorption device A500 for transferring the lithium / iron sheet A300 after punching. The upper press (A600), the lower press (A700), and the heater (A) are integrally formed to integrally form the lithium / iron sheet A300, the case A320 for containing the lithium / iron sheet A300, (A800).

The inert atmosphere holding glove box A10 may be referred to as a second chamber in contrast to the first chamber described above. The second chamber is supplied with argon gas (S200), and a nitrogen atmosphere should be maintained at a concentration of 50 ppm oxygen and 10 ppm water or less. If the above conditions are not satisfied, it is not preferable due to the reaction with lithium (S310) (equations (1) and (2)).

The material of the substrate A100 used for rolling the lithium / iron mixture S510 is preferably the same material as the above-mentioned material. In addition, after the rolling, the substrate A100 may be coated so as not to be adhered on the substrate A100 according to the intended use. Further, a separate carrier may be provided on the substrate A100 so that the lithium / iron mixture S510 does not flow down.

The lithium / iron mixture A 500 is manufactured using the same material as the substrate A 100 by using the lithium / iron mixture S510 as the roller A200 (S210) (A200) so as not to be adhered to the surface of the substrate (A200). In addition, the lithium / iron mixture S510 is inserted into a polymer-based film having no adhesion to lithium at room temperature, such as polyester and polypropylene, and is rolled, thereby preventing adhesion to the roller A200. Further, in order to smooth the production of the lithium / iron sheet A300, a heater may be installed on the roller A200.

The lithium / iron sheet A300 manufactured in the above manner is cut to a desired size using a rubbing machine A400 (S220), and then the lithium / iron sheet A300 is cut by using a vacuum suction / A300 is separated from the substrate A100 on the substrate A100 and then a mesh A310 is laid in a case A320 for containing the lithium / iron sheet A300 and the lithium / iron sheet A300 is detached therefrom (S240) . Then, the pressure is applied to the upper press A 600 and the lower press A 700, and a certain pressure is applied to the upper press A 600 and then a high output / large capacity electrode (ADLIE, ADD Developed Lithium-impregnated Electrode, Lithium occlusion electrode) The ADLIE is composed of a lithium / iron sheet (A300), a mesh (A310) and a case (A320), and a hole (A330) A heater A800 may be installed in the lower press A 700 for easy manufacture of the electrode of ADLIE.

The case A320 for containing the lithium / iron sheet A300 is used to prevent the molten lithium S310 from flowing into the battery during a thermal cell operation (500 deg. C). The case A320 has good electrical conductivity, It is preferable to use less pure iron, stainless steel, nickel or the like.

The mesh A 310 is also used to prevent the molten lithium S310 from flowing into the thermal battery, and it is preferable to use pure iron, stainless steel, nickel or the like having good electrical conductivity.

It is preferable that the same material as the substrate A100 and the roller A200 is used for the material of the rubbing machine A400, the vacuum suction and desorption apparatus A500, the upper press A 600 and the lower press A 700.

The high-power / high-capacity electrode mixture cooling and press apparatus in FIG. 4B can be used in connection with the high-output / high-capacity electrode mixing apparatus of FIG. 2B, a glove box for inert atmosphere A10, a lithium / iron mixture transfer passage S900, a lithium / iron mixture S510, a lithium / iron sheet A300, and a lithium / iron sheet A300 And includes a case A320 for containing the material, a mesh A 310, an upper press A 600, a lower press A 700, and a heater A 800. It also includes a separate electrode-carrying fixture A710 for accommodating lithium / iron sheet A300, case A320, and mesh A310.

4B, the electrode supporting fixture A710 is mounted on a lower press A700 including a heater S800 and the lithium / iron sheet A300 is inserted into the electrode supporting fixture A710. Thereby fixing the case A320 and the mesh A310. Thereafter, the lithium / iron mixture S510 is transferred and cooled in the electrode supporting fixture A710 through the lithium / iron mixture transfer passage S900. When the cooling is completed, an appropriate pressure is applied using an upper press (A600) to produce an electrode.

The material of the apparatus included in the apparatus of FIG. 4B may be the same as that of the material of FIG. 4A, and the electrode supporting fixture A710 may use a stable material at a high temperature (for example, MgO, Graphite, etc.).

It will be understood by those skilled in the art that the foregoing description of the specification is for illustrative purposes only and that those skilled in the art will readily understand that various changes in form and details may be made therein without departing from the spirit and scope of the invention. It will be possible. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.

The scope of the present invention is defined by the appended claims rather than the foregoing detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be interpreted as including the claims.

S100: Case for maintaining an inert atmosphere
S200: argon
S300: Lithium supply
S310: lithium
S320: Lithium moving passage
S400: Iron powder feeder
S410: iron powder
S420:
S500:
S510: Lithium / iron mixture
S600: Lithium / iron mixing container case
S700: Lithium / iron mixing vessel
S800: Heater
S900: Lithium / iron mixture passage
S200: argon
S510: Lithium / iron mixture
S900: Lithium / iron mixture passage
A10: Glove box
A100: Substrate
A200: Roller
A300: Lithium / iron sheet
A310: Lithium / iron carrying case
A320: Mesh
A400: rudder
A500: Vacuum suction and desorption device
A600: Saw press
A700: Low press
A800: Heater
S510: Lithium / iron mixture
S900: Lithium / iron mixture passage
A10: Glove box
A300: Lithium / iron sheet
A310: Lithium / iron carrying case
A320: Mesh
A600: Saw press
A700: Low press
A710: Electrode holding fixture
A800: Heater

Claims (10)

1. A lithium electrode manufacturing system comprising a first chamber and a second chamber for maintaining an inert atmosphere,
A method for producing a lithium secondary battery, comprising: a mixing vessel; a lithium supplying unit for supplying lithium (Li) to the mixing vessel; an iron supplying unit for supplying iron (Fe) powder to the mixing vessel; And a transfer passage for providing a passage for transferring the lithium-iron mixture in which the molten lithium and the iron powder supplied to the mixing vessel are mixed, from the first chamber to the second chamber, chamber; And
A roller for rolling the lithium-iron mixture to produce a lithium-iron sheet; a rudder for cutting the lithium-iron sheet to a predetermined size; a vacuum suction and separation device for separating the cut lithium-iron sheet from the substrate; A lithium ion secondary battery comprising: a case for a sheet, in which a mesh is installed in the inside of the mesh, and the cut lithium-iron sheet is disposed on the mesh; and a press for generating an electrode by applying pressure to the cut lithium- A second chamber including a first chamber; And a lithium electrode. The method according to claim 1,
Wherein the roller, the rudder, and the press are made of the same material. The method according to claim 1,
And the second chamber further comprises a jig that receives the sheet case and cools the lithium-iron mixture contained in the sheet case. The method of claim 3,
Wherein the press comprises a upper press and a lower press,
Wherein the upper press presses the cooled lithium-iron sheet contained in the case for a sheet to generate an electrode. 5. The method of claim 4,
Wherein the devices included in the first chamber and the second chamber are made of the same material. delete delete delete delete delete

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