KR101750203B1 - Method and apparatus for manufacturing of high density electrodes for reserve battery - Google Patents

Abstract

The present invention relates to a method and apparatus for manufacturing an electrode for producing a high-density thermocouple, comprising the steps of uniformly filling a space formed by a mold and a lower punch with a powder (100) containing a eutectic salt, And heating the powder 100 containing the eutectic salt filled in the space formed by the punch 130 and pressing the powder 100 by the upper punch to form the pellets P. [
The present invention can produce stable pellets having high density, high strength and reduced deformation after molding by heat molding, and thus an advantage of manufacturing a high-density, high-energy non-battery using the positive electrode, negative electrode and electrolyte made of the pellet have.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method and apparatus for manufacturing a high-density thermocouple,

The present invention relates to a method and apparatus for manufacturing an electrode for manufacturing a high-density thermocouple, and more particularly, to a method and apparatus for manufacturing an electrode for manufacturing a high-density thermocouple for improving the density and strength of a non-accumulator (thermal battery).

A thermal activated non-storage battery (thermal battery) is a single cell that can not be charged. It is a self-discharge battery that can be stored for 10 years or longer because there is no electric capacity loss at room temperature.

More specifically, when an electrical signal is applied to an igniter in a battery, the non-accumulator ignites a heat source between the electrodes to generate a solid state (300 to 500 ° C) inserted between the positive and negative electrodes Which activates ionic conductivity and generates an electromotive force. The battery is excellent in structural stability and reliability.

Generally, as shown in FIG. 1, a non-accumulator is formed by stacking a positive electrode, a negative electrode, an electrolyte, and a current collector in the form of pellets or disks, and the electrode and the electrolyte are formed by a uniaxial pressing molding method .

The positive electrode and the negative electrode act as a binder by adding the same or similar salt to the raw material powder as the anode active material and the anode active material of the lithium alloy, thereby improving the pellet formability and performance.

Such non-storage batteries must be formed to have a thin thickness at the same weight for high density of the anode, cathode, and electrolyte as the demand for high output power for the battery increases. However, in this case, due to the reduction in the ratio to the thickness / diameter, the room temperature molding for the thin pellets may not be sufficient in strength, or may cause some scratches on the side of the pellet molding or may cause spring- It has a drawback that it is broken.

Therefore, it is necessary to increase the density and strength of the pellets so that the basic unit of the battery is stacked in a given space, and to minimize the deformation after molding in order for the non-battery to have high density and high output.

An object of the present invention is to provide an electrode manufacturing method and apparatus for fabricating a high-density thermocapacitor that improves the density and strength of a battery and minimizes deformation after molding by mounting a heating device on the electrode manufacturing apparatus and raising the temperature to a temperature suitable for eutectic salt heating of the electrode .

According to an aspect of the present invention for accomplishing the above object, the present invention provides a method for manufacturing a metal mold, comprising: filling a powder containing eutectic salt uniformly in a space formed by a mold and a lower punch; And heating the powder containing the eutectic salt filled in the space for forming the pellet by pressurizing with the upper punch.

And heating the mold and the upper and lower punches to a temperature higher than the sintering temperature of the eutectic salt before filling the space formed by the mold and the lower punch with powder containing the eutectic salt.

The sintering temperature or higher of the eutectic salt is in the range of 150 to 300 占 폚.

The eutectic salt-containing powder includes a positive electrode powder containing a LiCl-KCl salt, a negative electrode powder containing a LiCl-KCl salt, an electrolyte powder containing a LiCl-KCl salt, a positive electrode containing a LiCl-LiBr- A negative electrode powder containing a LiCl-LiBr-LiF salt, and an electrolyte powder containing a LiCl-LiBr-LiF salt.

In the step of heating the powder containing the eutectic salt and pressurizing with the upper punch to produce pellets, the pressing force is 60 to 70 tons, and the heating and pressing time is 30 to 50 seconds.

A mold and a lower punch forming a space in which powder can be filled with each other and a powder poured into a space formed by the mold and the lower punch, the punch being raised and lowered from the upper portion of the lower punch, A lower punch, and a lower punch; and heating means for heating the powder filled in the space defined by the mold and the lower punch, respectively, and a temperature sensing unit for sensing the temperature of the mold, the upper punch and the lower punch, And a temperature control device for receiving the signal of the temperature sensing means and controlling the temperature of the heating means.

A core pin protrudes from the center of the lower punch.

The pressing force of the upper punch is adjusted by hydraulic or electric pressing means.

The present invention relates to a method for producing a metal mold by heating a mold and upper and lower punches at a temperature higher than the sintering temperature of the eutectic salt and uniformly filling the space containing the eutectic salt by a mold and a lower punch, The pellet is formed by continuing the heating, and stable pellets having high density and high strength and reduced deformation after molding can be produced.

Accordingly, there is an effect that a high-density, high-energy non-battery can be manufactured using the positive electrode made of pellet, the negative electrode and the electrolyte.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram showing an internal configuration of a conventional thermal battery. FIG.
2 is a process diagram showing an electrode manufacturing method for manufacturing a high-density thermocapacitor of the present invention.
FIG. 3 is a view showing an electrode manufacturing apparatus for manufacturing a high-density thermocouple according to the present invention, in which the upper punch is elevated. FIG.
FIG. 4 is a view showing an apparatus for manufacturing an electrode for manufacturing a high-density thermocapacitor according to the present invention, in which the upper punch is lowered to press a powder containing a eutectic salt. FIG.
FIG. 5 is a graph showing the results of heat molding of an electrolyte powder containing a LiCl-KCl salt. FIG.
6 is a graph showing the results of heat molding of an electrolyte powder containing LiCl-LiBr-LiF salt.
FIG. 7 is a graph showing the results of heat molding of a positive electrode powder containing a LiCl-KCl salt. FIG.
8 is a process chart showing a conventional method for manufacturing a non-battery electrode.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

The electrode manufacturing method for manufacturing a high-density thermocapacitor of the present invention is a pellet forming method in which the density and strength are increased and the pore diameter after molding is minimized.

The pellet is in the form of a disk and can be an anode, a cathode or an electrolyte of a non-accumulator depending on the kind of powder for forming the pellet.

A method of manufacturing an electrode for manufacturing a high-density thermocouple includes the steps of uniformly filling a space formed by a mold and a lower punch with a powder containing a eutectic salt, and a eutectic salt filled in a space formed by a mold and a lower punch And simultaneously pressurizing the powder with an upper punch to form the pellet.

The space formed by the mold and the lower punch is formed into a cylindrical shape with an open upper part to form a disc-shaped pellet, and a core pin protrudes in the center to form an inner diameter of the disc. The upper punch is lowered on the upper part of the space formed by the mold and the lower punch to press the powder containing the eutectic salt.

In order to manufacture high density and high energy non-accumulators, the pellets must have high density and high strength characteristics that are thinner than the conventional thickness. The positive and negative electrodes, which are non-battery components, add an electrolyte-like LiCl-KCl salt or LiCl-LiBr-LiF salt as a eutectic salt to improve moldability and ion conduction performance.

Accordingly, the powder containing the eutectic salt can be obtained by mixing a positive electrode powder containing a LiCl-KCl salt, a negative electrode powder containing a LiCl-KCl salt, an electrolyte powder containing a LiCl-KCl salt, and a LiCl-LiBr- An anode powder, a cathode powder containing a LiCl-LiBr-LiF salt, and an electrolyte powder containing a LiCl-LiBr-LiF salt.

The heating of the powder containing the eutectic salt is carried out by heating the mold and the upper and lower punches.

The method further comprises heating the mold and the upper and lower punches to a sintering temperature of the eutectic salt before filling the space formed by the mold and the lower punch with the powder containing the eutectic salt.

When the eutectic salt is heated to a temperature higher than the sintering temperature, the plastic deformation is facilitated and a viscosity is generated. If the eutectic salt is pressurized at the same time as heating, the reorientation is performed in a form that is uniformly applied to the periphery of the electrode active material constituting the powder, It increases the strength by the bonding force and acts to reduce the deformation after molding, thereby improving the pellet formability.

Specifically, as shown in FIG. 2, a powder containing a eutectic salt is prepared (S10), the mold and the upper and lower punches are heated (S20), the upper punch is elevated (S30) Is uniformly filled in the space formed by the mold and the lower punch (S40). Next, the upper punch is lowered (S50), and the powder containing the eutectic salt filled in the space formed by the mold and the lower punch is pressed while molding is continued to form the pellet (S60). After the pellet is formed, the pellet is discharged (S70).

The heating of the mold and the upper and lower punches is carried out at a temperature in the range of 150 to 300 ° C which is higher than the sintering temperature of the eutectic salt. When the temperature is stabilized by the heating of the mold and the upper and lower punches, the powder containing the eutectic salt is heated while being pressurized to form the pellets.

The pre-pressurization of the powder containing the eutectic salt and the heating of the upper and lower punches are carried out for maintaining a uniform heating temperature.

If the heating of the mold and the lower and upper punches is performed at a temperature lower than the sintering temperature of the eutectic salt, it is difficult to increase the density and the strength because the effect of reducing the pores after heating and molding the pellets is insufficient. Above the sintering temperature and above 300 캜, the eutectic salt may undergo pyrolysis to lose its function.

When the pellets are continuously heated while pressurizing the powder containing the eutectic salt, the pressing force is preferably in the range of 60 to 70 tons of molding load, and the heating and pressing time is preferably in the range of 30 to 50 seconds.

If the molding load is less than 60 tons, the molding force is insufficient and the effect of reducing the pore can not be expected. If the molding pressure is over 70 tons, excessive pressure may cause some defects on the side of the pellet molding.

If the heating time and the pressing time are less than 30 seconds, the formability may be insufficient. If the heating time and the pressing time are more than 50 seconds, the effect is saturated.

As shown in FIG. 3, the apparatus for manufacturing the high-density thermocouple includes a mold 110, upper and lower punches 120 and 130, a heating means 200, a temperature sensing means 300, And a control device 340.

The mold 110 and the lower punch 130 cooperate to form a space in which the powder 100 can be filled. The powder 100 is a powder containing a eutectic salt. The space in which the powder (100) containing the eutectic salt can be filled is formed into a cylindrical shape having an open upper part to form a disc-shaped pellet (P).

The lower punch 130 has a core pin 140 protruding from the center thereof. The core pin 140 is for forming an inner diameter of the pellet P, which is manufactured in the form of a disk. The core pin 140 is disposed at the center of the lower punch 130 and the lower end of the core pin 140 is supported by the spring 145 so as to be movable downward by the urging force of the upper punch 120.

The mold 110 and the lower punch 130 are supported by a lower portion of the mold support bed 150.

3 and 4, the upper punch 120 includes a powder packed in a space formed by the mold 110 and the lower punch 130 so as to be raised and lowered from the upper portion of the lower punch 130, (100) is pressed to mold the pellet (P). That is, the mold 110 and the upper and lower punches 120 and 130 cooperate to form the pellets P.

The heating means 200 is provided in the mold 110, the lower punch 130 and the upper punch 120 for uniform heating and is provided in the space formed by the mold 110 and the lower punch 130 The powder 100 is heated. The heating means 200 includes a mold heating heater 210, a lower punch heating heater 230 and an upper punch heating heater 220 embedded in the mold 110, the lower punch 130 and the upper punch 120, have.

The temperature sensing means 300 senses temperatures of the mold 110, the upper punch 120 and the lower punch 130. The temperature sensing means 300 includes a mold temperature sensor 310 provided in the mold 110, a lower punch temperature sensor 330 provided in the lower punch 130, an upper punch temperature sensor 330 provided in the upper punch 120, And a sensing sensor 320.

The heating means 200 and the temperature sensing means 300 provided in the mold 110, the upper punch 120 and the lower punch 130 independently control the temperature to be controlled at the same temperature. This is for uniform heating of the powder 100 containing the eutectic salt.

The uniform heating of the powder 100 including the eutectic salt over the sintering temperature serves to uniformly distribute the eutectic salt around the electrode active material constituting the powder and to re-arrange the powder so as to reduce the pores of the molded product, To increase the strength and to reduce deformation after molding.

The temperature control unit 340 receives the signal of the temperature sensing unit 300 and controls the temperature of the heating unit 200.

The upper punch 120 is pressurized by hydraulic or electric pressing means 160. Further comprises a pressure control device (350) for controlling the operation of the hydraulic or electric pressure means (160) to control the pressing force of the upper punch (120).

Hereinafter, embodiments of the present invention will be described in comparison with Comparative Examples. It is to be understood that the following examples are illustrative of the present invention and that the following examples do not limit the present invention.

[Example 1]

In Example 1, an electrolyte powder containing a LiCl-KCl salt was prepared, the mold and the upper and lower punches were heated, the upper punch was elevated, and the electrolyte powder containing the LiCl-KCl salt was placed in a mold and a lower punch The pellet was then formed by continuously heating the electrolyte powder including the LiCl-KCl salt filled in the space formed by the mold and the lower punch while pressurizing the upper punch.

The electrolytic powder containing LiCl-KCl salt was used in which the LiCl-KCl salt was 55% and the electrolyte powder (MgO) was 45% by mass ratio.

The sintering temperature for the LiCl-KCl salt was 150 ° C or higher, and the mold and the upper and lower punches were heated to 170 ° C to form pellets.

FIG. 5 shows the result of heat molding according to the heating temperature of the electrolyte powder containing LiCl-KCl salt.

According to FIG. 5, when heat molded at 170 ° C, it is uniformly distributed around MgO, which acts as a separator due to the deformation of particles of comparative salt when heated at room temperature (20 ° C) Or more, the strength is increased by 62% or more, and the springback to the diameter is reduced to 30% or less, resulting in a pellet having high density and high strength and little deformation after molding.

[Example 2]

In Example 2, an electrolyte powder containing a LiCl-LiBr-LiF salt was prepared, the mold and upper and lower punches were heated, the upper punch was elevated, and then an electrolyte powder containing a LiCl-LiBr- And the lower punch. Then, the upper punch is lowered, and the electrolyte powder containing the LiCl-LiBr-LiF salt filled in the space formed by the mold and the lower punch is continuously heated while being pressurized The pellets were allowed to form.

The electrolyte powder containing LiCl-LiBr-LiF salt had a mass ratio of LiCl-LiBr-LiF salt of 55% and electrolyte powder (MgO) of 45%.

The sintering temperature for the LiCl-LiBr-LiF salt was 200 DEG C or higher, and the mold and the upper and lower punches were heated to 230 DEG C to form pellets.

FIG. 6 shows the result of heat molding according to the heating temperature of the electrolyte powder containing LiCl-LiBr-LiF salt.

As shown in FIG. 6, in the case of heat molding at 230 ° C., the powder is uniformly distributed around MgO, which acts as a separator due to particle deformation of the comparative salt when heated at room temperature (20 ° C.) , The strength increased by more than 72%, and the springback to the diameter was reduced to within 30%, resulting in a pellet having a high density and high strength while having little deformation after molding.

[Example 3]

In Example 3, a positive electrode powder containing a LiCl-KCl salt was prepared, the mold and upper and lower punches were heated, the upper punch was elevated, and a positive electrode powder containing a LiCl-KCl salt was placed in a mold and a lower punch The pellet was formed by continuously heating the positive electrode powder containing the LiCl-KCl salt filled in the space formed by the mold and the lower punch while pressurizing the upper punch.

The positive electrode powder containing LiCl-KCl salt had a mass ratio of LiCl-KCl salt of 16.25%, FeS _{2 of} 73.5%, MgO of 8.75% and Li ₂ O of 1.5%.

The sintering temperature for the LiCl-KCl salt was 150 ° C or higher, and the mold and the upper and lower punches were heated to 150 ° C or higher to form pellets.

FIG. 7 shows the result of heat molding according to the heating temperature of the positive electrode powder containing LiCl-KCl salt.

As shown in FIG. 7, when the particles are heat-molded at 150 ° C or higher, the particles of the salt are converted into FeS ₂ The density is 20% or more at 250 ° C, the strength is increased more than 2 times, and the springback to the diameter is reduced to 80% or less Resulting in the production of a cathode having high density and high strength.

[Comparative Example 1]

In Comparative Example 1, an electrolyte powder containing a LiCl-KCl salt was prepared, the upper punch was elevated, and an electrolyte powder containing a LiCl-KCl salt was uniformly filled in a space formed by a mold and a lower punch And the electrolyte pellet is formed by pressurizing the electrolyte powder containing the LiCl-KCl salt filled in the space formed by the mold and the lower punch.

The pressing force was 60 ton of forming pressure, the forming temperature was room temperature (20 ℃) and 100 ℃, and pressurization and heating duration at 100 ℃ was 40 seconds.

The electrolytic powder containing LiCl-KCl salt was used in which the LiCl-KCl salt was 55% and the electrolyte powder (MgO) was 45% by mass ratio.

The results of Comparative Example 1 are confirmed from the strength, relative density, and drooping back results of the pellets molded at 20 캜 and 100 캜 shown in Fig.

As shown in FIG. 5, in the case of heat molding at 100 ° C or less, pores were slightly decreased due to compressive deformation of the salt particles, and the density and the strength were increased by half as compared with the room temperature.

[Comparative Example 2]

In Comparative Example 2, an electrolyte powder containing a LiCl-LiBr-LiF salt was prepared, and after the upper punch was elevated, an electrolyte powder containing a LiCl-LiBr-LiF salt was uniformly dispersed in a space formed by a mold and a lower punch And then the upper punch is lowered to form a pellet by pressurizing the electrolyte powder containing LiCl-LiBr-LiF salt filled in the space formed by the mold and the lower punch.

The pressing force was 60 ton of forming pressure, the forming temperature was room temperature (20 ℃) and 100 ℃, and pressurization and heating duration at 100 ℃ was 40 seconds.

The electrolyte powder containing LiCl-LiBr-LiF salt had a mass ratio of LiCl-LiBr-LiF salt of 55% and electrolyte powder (MgO) of 45%.

The results of Comparative Example 2 are confirmed from the strength, relative density, and drooping-back results of the pellets molded at 20 ° C and 100 ° C in Fig.

6, the pores are compressed and deformed by compressive deformation of the salt particles when heated to a temperature of 150 ° C or less. The density is increased by 1.5%, the strength is increased by 34%, and the springback is reduced by about 40% Respectively.

From the results of the examples and the comparative example, the mold, the upper and lower punches were heated to 150 to 250 ° C, and then the positive electrode, the negative electrode and the electrolyte powder containing the LiCl-KCl salt were uniformly dispersed in the space formed by the mold and the lower punch The density and the springback of the pellet are increased by 20% and 2 times or more, respectively, compared with the conventional pellets.

Further, the mold, the upper and lower punches were heated to 150 to 250 ° C., and the positive electrode, the negative electrode and the electrolyte powder containing the LiCl-LiBr-LiF salt were uniformly filled in the space formed by the mold and the lower punch, Compared with conventional pellets, pellets subjected to pressurization and heat molding have a density of 8%, a strength of more than 2 times, and a springback to a diameter (outer diameter) of less than half.

Therefore, it can be confirmed that stable pellets having high density and high strength, reduced deformation after molding, and improved moldability can be produced.

As described above, this embodiment fully utilizes the fluidity and coating characteristics of the eutectic salt contained in the powder. It is preferable that the mold and the upper and lower punches are heated to a temperature not lower than the sintering start temperature of the eutectic salt during molding, It is possible to form pellets uniformly coated with a eutectic salt in the positive and negative active materials, thereby forming a pellet having a high density and a high strength, It is possible to produce stabilized pellets with reduced post-strain.

As a result, it is possible to manufacture a high-density high-energy non-battery using a positive electrode made of pellets, a negative electrode, and an electrolyte by the heat molding method, and the specific power of the non-battery can be increased.

The scope of the present invention is not limited to the embodiments described above, but may be defined by the scope of the claims, and those skilled in the art may make various modifications and alterations within the scope of the claims It is self-evident.

100: powder (including eutectic salt) 110: mold
120: upper punch 130: lower punch
140: core pin 145: spring
150: mold supporting bed 160: hydraulic or electric pressing means
200: heating means 210: mold heating heater
220: upper punch heating heater 230: lower punch heating heater
300: Temperature sensing means 310: Mold temperature sensing sensor
320: Upper punch temperature sensor 330: Lower punch temperature sensor
340: Temperature control device 350: Pressure control device
P: Pellet

Claims (8)

Uniformly filling the powder containing the eutectic salt in a space formed by a mold and a lower punch; And
Heating the powder containing the eutectic salt filled in the space formed by the mold and the lower punch and pressing the powder with an upper punch to mold the pellet,
Before filling the space formed by the mold and the lower punch with the powder containing the eutectic salt,
Further comprising the step of heating the mold and the upper and lower punches to a sintering temperature of the eutectic salt or higher,
The sintering temperature or more of the eutectic salt is in the range of 150 to 300 占 폚,
The eutectic salt-
An anode containing LiCl-KCl salt, a cathode containing LiCl-KCl salt, an electrolyte powder containing LiCl-KCl salt, a cathode containing LiCl-LiBr-LiF salt, a cathode containing LiCl-LiBr- And LiCl-LiBr-LiF salt. 2. A method for manufacturing a high-density thermocouple according to claim 1, delete delete delete The method according to claim 1,
In the step of heating the powder containing the eutectic salt and pressurizing with the upper punch to produce pellets,
Wherein the pressing force is 60 to 70 tons, and the heating and pressing time is 30 to 50 seconds. A mold and a lower punch for mutually cooperating to form a space in which powder containing eutectic salt can be filled;
An upper punch which is installed upward and downward from the lower punch and presses a powder containing eutectic salt filled in a space formed by the mold and the lower punch to form a pellet;
Heating means provided in the mold, the lower punch and the upper punch to heat the powder containing the eutectic salt filled in the space defined by the mold and the lower punch;
Temperature sensing means for sensing temperatures of the mold, the upper punch and the lower punch; And
The temperature of the heating means provided in each of the mold, the lower punch and the upper punch is independently controlled to uniformly heat the sintering temperature of the powder containing the eutectic salt filled in the space by the signal of the temperature sensing means And a temperature control device for controlling the temperature of the high-density thermocouple. The method of claim 6,
And a core pin protrudes from the center of the lower punch. The method of claim 6,
Wherein the pressing force of the upper punch is controlled by hydraulic or electric pressing means.

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