WO2018048002A1 - Liquid metal battery - Google Patents

Abstract

A liquid metal battery is provided. Specifically, a liquid metal battery comprises: a liquid anode; a solid electrolyte disposed on the liquid anode; a liquid cathode disposed on the solid electrolyte; an anode current collector in contact with the liquid anode; and a cathode current collector of a spring shape which passes through the liquid cathode to be connected to the solid electrolyte.

Description

Liquid metal battery

The present invention relates to a liquid metal battery, and more particularly to a liquid metal battery that can improve the electrochemical stability.

Liquid metal batteries (liquid metal battery) is a battery that can provide a high energy density and power density, attracting attention as a next-generation battery for storing a large amount of electrical energy, such as in the energy storage system (ESS). When the liquid metal battery is operated at a high temperature of about 450 ° C., the liquid metal battery uses high density electricity by ion exchange through the active material and electrolyte in the liquid by using the difference in density of the liquid anode, the liquid electrolyte and the liquid cathode and the immiscible property. Capacity can be implemented.

However, in the high temperature environment in which the liquid metal battery is driven, as the ions from the liquid negative electrode are infiltrated into the liquid electrolyte, the liquid negative electrode and the liquid positive electrode are not completely separated by the liquid electrolyte, and therefore, infiltrate during the charging operation. There is a problem of self-discharging in which the negative ions react with the liquid anode, and self-discharge occurs even when the amount of ions contained in the liquid negative electrode is higher than a predetermined level.

When the thickness of the liquid electrolyte is increased in order to prevent such self discharge, there is a disadvantage in that the resistance inside the battery is increased and the capacitance is decreased. There is a problem that it is difficult to find an appropriate thickness range of the liquid metal battery.

In addition, as the liquid metal battery is driven at a high temperature of about 450 ° C., a small amount of gases such as Ar, O ₂ , H ₂ O remaining in the vacuum reacts with the highly reactive high temperature liquid electrode, and the liquid electrode is oxidized, thereby causing the capacitance. And a high level of sealing required at high temperature, which is a battery driving environment, is substantially difficult.

The problem to be solved by the present invention is to provide a liquid metal battery with improved electrochemical stability and electrical properties.

In order to solve the above problems, an aspect of the present invention provides a liquid metal battery. The liquid metal cell is connected to the solid electrolyte through a liquid anode, a solid electrolyte disposed on the liquid anode, a liquid cathode disposed on the solid electrolyte, a positive electrode current collector in contact with the liquid anode, and the liquid cathode. And a negative electrode current collector having a spring shape.

The negative electrode current collector may be configured to maintain contact between the solid electrolyte and the liquid positive electrode when the liquid positive electrode expands or contracts in a depth direction.

The negative electrode current collector may include a plurality of springs connected to the solid electrolyte to provide an elastic force against a volume change of the liquid positive electrode.

The solid electrolyte may have a curved shape between the liquid anode and the liquid cathode.

The solid electrolyte may include a flat portion parallel to the surface of the liquid cathode, and a plurality of recesses bent upward or downward from the flat portion.

The thickness of the recess may be less than or equal to the thickness of the flat portion.

The positive electrode current collector may accommodate the liquid positive electrode, the solid electrolyte and the liquid negative electrode.

The solid electrolyte may extend upwardly to surround the liquid negative electrode between the liquid negative electrode and the positive electrode current collector.

One of the inner side of the positive electrode current collector and the outer side of the solid electrolyte is provided with a protrusion for limiting the volume change of the liquid positive electrode, the other of the inner side of the positive electrode current collector and the outer side of the solid electrolyte A recess may be formed in the protrusion to accommodate the protrusion.

The liquid positive electrode may be further disposed between the solid electrolyte and the positive electrode current collector.

The liquid positive electrode may be sealed by the solid electrolyte and the positive electrode current collector.

The positive electrode current collector may have a spring shape passing through the liquid positive electrode and connected to the solid electrolyte.

The negative electrode current collector and the positive electrode current collector may each have a plurality of spring shapes.

The elastic modulus of the spring of the positive electrode current collector may be the same as the elastic modulus of the spring of the negative electrode current collector.

According to the present invention, instead of driving all of the positive electrode, the electrolyte and the negative electrode of the liquid metal battery into an all-liquid, by using a thin solid electrolyte as the electrolyte, the liquid negative electrode and the liquid positive electrode can be sufficiently separated, As a result, self-discharge can be reduced.

In addition, as the negative electrode current collector is connected to the solid electrolyte in a spring shape, the solid electrolyte can be moved in close contact with the liquid positive electrode and the liquid negative electrode according to the change in the depth direction due to the volume expansion and contraction of the liquid positive electrode. And it is possible to improve the electrochemical stability at the time of driving while sealing the cathode.

In addition, since the solid electrolyte has a curved shape between the liquid anode and the liquid cathode, the surface area of the solid electrolyte capable of ion migration can be increased, thereby increasing the charge / discharge rate of the liquid metal battery.

In addition, as the negative electrode current collector having a plurality of spring shapes is connected to the solid electrolyte, the elastic movement of the solid electrolyte may be smoothed according to the volume change of the liquid positive electrode and the negative electrode, and the surface area collected in the liquid negative electrode may be increased. In addition, the electric capacity of the liquid metal battery can be improved.

In addition, the spring-shaped positive electrode current collector is further connected to the solid electrolyte through the liquid positive electrode, thereby increasing the positive electrode current collecting area and maintaining contact between the liquid positive electrode and the solid electrolyte according to the volume change of the liquid positive electrode. .

However, the effects of the invention are not limited to the above-mentioned effects, and other effects not mentioned will be clearly understood by those skilled in the art from the following description.

1 is a cross-sectional view showing a liquid metal battery in one embodiment of the present invention.

FIG. 2 is a partial perspective view illustrating the liquid metal battery of FIG. 1.

3A and 3B are cross-sectional views illustrating movement of a solid electrolyte when driving a liquid metal battery according to an embodiment of the present invention.

4 is a cross-sectional view showing a solid electrolyte of a liquid metal battery according to an embodiment of the present invention.

5 is a cross-sectional view illustrating a liquid metal battery according to an embodiment of the present invention.

6 is a cross-sectional view illustrating a liquid metal battery according to an embodiment of the present invention.

7 is a cross-sectional view showing a liquid metal battery according to an embodiment of the present invention.

8 is a cross-sectional view illustrating a liquid metal battery according to an embodiment of the present invention.

9 is a cross-sectional view showing a liquid metal battery according to an embodiment of the present invention.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings in order to describe the present invention in more detail. However, the present invention is not limited to the embodiments described herein and may be embodied in other forms.

In the drawings, the thicknesses of layers and regions may be exaggerated or reduced for clarity. Like reference numerals denote like elements throughout the specification.

1 is a cross-sectional view showing a liquid metal battery in one embodiment of the present invention. FIG. 2 is a partial perspective view illustrating the liquid metal battery of FIG. 1.

1 and 2, the liquid metal battery according to the present embodiment includes a positive electrode 100, an electrolyte 200, a negative electrode 300, a positive electrode current collector 150, and a negative electrode current collector 350. The liquid metal battery may further include a vacuum valve 400 and a current collector protection part 370.

When the liquid metal battery is driven, i.e., charged or discharged, the positive electrode 100 and the negative electrode 300 have a liquid state, and the electrolyte 200 is kept in a solid state. At this time, the solid electrolyte 200 may have a density greater than that of the liquid anode 100, but the solid electrolyte 200 is supported by the negative electrode current collector 350 connected thereto, such that the liquid anode 100 and The liquid cathode 300 may be separated and positioned on the liquid anode 100.

The liquid anode 100 may include a metal of Group II-VI. For example, the liquid anode 100 may include at least one selected from the group consisting of Al, Zn, Ga, Cd, In, Sn, Sb, Te, Hg, Ti, Pb, Bi, and alloys thereof. . The liquid anode 100 has a greater density than the liquid cathode 300 and may have a melting point of 1000 ° C. or less. For example, when the liquid anode 100 includes an alloy of Sb-Pb, the melting point of the liquid anode 100 may be about 253 ° C. Accordingly, the liquid metal battery can be driven even in a low temperature (300 ° C or less) environment.

The liquid cathode 300 may include an alkali metal or an alkaline earth metal. For example, the liquid cathode 300 may include at least one selected from the group consisting of Li, Na, Mg, K, Ca, Rb, Sr, Cs, Ba, and alloys thereof. The liquid cathode 300 has a smaller density than the liquid anode 100 and may have a melting point of 1000 ° C. or less. For example, when the liquid cathode 300 includes Li, the liquid metal battery may be driven at a melting point of about 180 ° C. even in a low temperature (300 ° C. or less) environment.

The solid electrolyte 200 may separate the liquid anode 100 and the liquid cathode 300. The solid electrolyte 200 is disposed between the liquid anode 100 and the liquid cathode 300. The solid electrolyte 200 is connected to the negative electrode current collector 350 having a spring shape and supported by the negative electrode current collector 350 so as to be held on the liquid positive electrode 100. The solid electrolyte 200 may seal the liquid positive electrode 100 together with the positive electrode current collector 150. As described below, the position of the solid electrolyte 200 may be moved up and down as the liquid anode 100 is expanded or contracted in the depth direction according to the driving of the liquid metal battery. In this case, as the position of the solid electrolyte 200 is moved up and down by the negative electrode current collector 350 which is connected to the solid electrolyte 200 and provides an elastic force, the contact between the liquid anode 100 and the solid electrolyte 200 is increased. Can be maintained.

The melting point of the solid electrolyte 200 may be much higher than the driving temperature of the liquid metal cell. For example, the solid electrolyte 200 may include a material having an ion conductivity while melting point exceeds 1000 ° C., such as beta-alumina, CaF _2, or the like.

The solid electrolyte 200 may have a predetermined thickness such that metal ions from the liquid cathode 300 are not transferred to the liquid anode 100 when charging the liquid metal battery. For example, the solid electrolyte 200 may have a thickness of 0.1 mm to 10 mm. When the thickness of the solid electrolyte 200 is less than 0.1 mm, metal ions from the liquid cathode 300 may be transferred to the liquid anode 100 to cause self-discharging, and the solid electrolyte 200 If the thickness is greater than 10 mm, the ion migration distance between the liquid anode 100 and the liquid cathode 300 is increased, thereby reducing the capacitance of the liquid metal battery.

On the other hand, the thickness of the solid electrolyte 200 may be thinner than the thickness set so as not to self-discharging when the liquid metal battery has a liquid electrolyte. When the liquid metal battery has a liquid electrolyte, when the thickness of the liquid electrolyte is thin, the metal ions from the liquid cathode are infiltrated into the liquid electrolyte and then moved to the liquid anode, so that self discharge is generated. However, in the liquid metal battery according to the present embodiment, since the electrolyte 200 in the solid state is used during operation, the amount of the metal ions that are infiltrated from the liquid cathode 300 is greatly reduced, so that the metal ions by the solid electrolyte 200 Movement of the liquid metal battery may be prevented even if the solid electrolyte 200 has a thin thickness.

In this embodiment, the solid electrolyte 200 not only separates the liquid anode 100 and the liquid cathode 300, but also surrounds the liquid cathode 300 between the liquid cathode 300 and the liquid current collector 150. May be further extended upwards. When the liquid metal cell is driven, the volume of the liquid cathode 300 may also expand or contract. A portion extending upward of the solid electrolyte 200 may be expanded in the solid electrolyte 200 even if the volume of the liquid cathode 300 expands. The accommodated liquid negative electrode 300 may have an appropriate height so as not to overflow the outside of the receiving space of the solid electrolyte 200. Also, when the liquid metal battery is driven, the liquid anode 100 leaks through a gap between the liquid anode 100 and the cathode current collector 150 when the volume of the liquid anode 100 is expanded, thereby causing the liquid metal to leak. The risk of shorting the battery can be prevented, and the liquid positive electrode 100 can be more tightly sealed.

The positive electrode current collector 150 may accommodate the liquid positive electrode 100, the solid electrolyte 200, and the liquid negative electrode 300, and may at least partially accommodate the negative electrode current collector 350. In some embodiments, the liquid positive electrode 100, the solid electrolyte 200, and the liquid negative electrode 300 may be sealed in the positive electrode current collector 150. In this case, an empty space 410 may be positioned on the liquid cathode 300 to accommodate a volume change of the liquid anode 100 and / or the liquid cathode 300. The empty space 410 may be maintained in a vacuum state by removing the gas remaining through the vacuum valve 400. As a result, a small amount of gases such as Ar, O ₂ , and H ₂ O remaining in the empty space 410 may be prevented from being reduced as the battery is reacted with the liquid cathode 300 and oxidized.

The negative electrode current collector 350 may have a spring shape, at least a part of which is immersed in the liquid negative electrode 300 and connected to the solid electrolyte 200. The negative electrode current collector 350 supports the solid electrolyte 200 to be disposed on the liquid positive electrode 100, while maintaining the contact between the liquid positive electrode 100 and the solid electrolyte 200 when the volume of the liquid positive electrode expands. It may be elastically contracted to raise 200, and may be elastically stretched to lower the solid electrolyte 200 while maintaining contact between the liquid anode 100 and the solid electrolyte 200 when the volume of the liquid anode is contracted. have. In this case, since the liquid cathode 300 is disposed in the receiving space of the solid electrolyte 200, the contact with the solid electrolyte 200 is always maintained regardless of the volume expansion and contraction of the liquid anode 100.

As such, when the liquid metal battery is driven, the contact between the solid electrolyte 200 and the liquid anode 100 is maintained even when the volume of the liquid anode 100 expands or contracts, such that the ion movement distance through the solid electrolyte 200 is increased. It can be kept constant, and thus the electrical characteristics of the liquid metal battery can be maintained.

On the other hand, the current collector protection unit 370 may include an insulating material, and may partially wrap the outer surface of the negative electrode current collector 350 to prevent a short circuit with the positive electrode current collector 100.

3A and 3B are cross-sectional views illustrating movement of a solid electrolyte when driving a liquid metal battery according to an embodiment of the present invention. 3A and 3B, only the liquid anode 100, the solid electrolyte 200, and the liquid cathode 300 are briefly illustrated for convenience of description.

In FIG. 3A, the state just before the liquid metal battery is discharged is shown. Referring to Figure 3a, when the liquid metal battery is being discharged (discharging), the molten metal constituting the liquid cathode 300, a metal cation (50) and an electron (e ^-) is dissociated by, e (e ^-) is The negative electrode current collector 350 is transferred to an external circuit terminal, and the metal cation 50 may move to the liquid positive electrode 100 through the solid electrolyte 200. Accordingly, the composition of the liquid anode 100 may be changed to a liquid alloy containing the metal cation 50 from the liquid cathode 300. At this time, as the metal cation 50 is transferred to the liquid anode 100 and an alloy reaction occurs, the volume of the liquid anode 100 starts to increase. As the volume of the liquid anode 100 increases, the liquid anode 100 may expand in the depth direction, and the solid electrolyte 200 may move upward. At this time, the solid electrolyte 200 is moved upward by the elastic contraction of the negative electrode current collector 350, so that the contact with the liquid positive electrode 100 can be maintained well.

In FIG. 3B, the state just before the liquid metal battery is charged is illustrated. Referring to FIG. 3B, when the liquid metal cell is charged, electrons provided through the negative electrode current collector 350 from an external circuit terminal are dissociated from the liquid alloy included in the liquid anode 100 to be solid electrolyte ( As combined with the metal cation 50 moved through the 200, the volume of the liquid cathode 300 is increased, the volume of the liquid anode 100 is reduced. As the volume of the liquid anode 100 decreases, the liquid anode 100 may shrink in the depth direction, and the solid electrolyte 200 may move downward. At this time, the solid electrolyte 200 is moved downward by its own density and elastic extension of the negative electrode current collector 350, so that the contact with the liquid positive electrode 100 can be maintained well.

4 is a cross-sectional view showing a solid electrolyte of a liquid metal battery according to an embodiment of the present invention.

Referring to FIG. 4, the solid electrolyte 200 of the liquid metal battery according to the present exemplary embodiment may have a curved shape between the liquid anode 100 and the liquid cathode 300. For example, the solid electrolyte 200 may include a flat portion 201 parallel to the surface of the liquid cathode 300, and a plurality of recesses 203 bent upward or downward from the flat portion 201. . The depression 203 is formed to increase the ion transport area of the liquid anode 100 and the liquid cathode 300 sandwiching the solid electrolyte 200, and the thickness of the depression 203 is the flat portion 201. It may be less than or equal to the thickness of. This is because when the thickness of the recessed portion 203 is thicker than the flat portion 201, the effect of increasing the ion transport area of the liquid anode 100 and the liquid cathode 300 with the solid electrolyte 200 therebetween becomes small.

As such, since the solid electrolyte 200 includes the depression 203 that is bent upward or downward, an area in which the ions 50 may move between the liquid anode 100 and the liquid cathode 300 may be increased. In addition, electrical characteristics such as charge and discharge rates of the liquid metal battery including the solid electrolyte 200 may be improved. In this case, the negative electrode current collector 350 in which the electrons 70 are collected may be connected to the flat portion 350 to stably provide an elastic force with respect to the vertical movement of the solid electrolyte 200. When the negative electrode current collector 350 is connected to the recessed portion 203, stress is concentrated on the recessed portion to which the negative electrode current collector 350 is connected, and the recessed portion may be formed by repeated vertical movement of the solid electrolyte 200. This is because self-discharge may be caused by damage to 203).

In FIG. 4, the depressions 203 that are bent downward from the flat portion 201 of the solid electrolyte 200 to a predetermined height H are shown. However, this is exemplary and in other embodiments, the depressions 203 are illustrated. Both may be bent to the top where the liquid cathode 300 is located, or some may be bent to the top and some may be bent to the bottom. Alternatively, the solid electrolyte 200 may be formed to have a plurality of depressions 203 arranged entirely without the flat portion 201, or one U-shaped curved portion 201 of the solid electrolyte 200 may be curved. The depression 203 may be formed.

5 is a cross-sectional view illustrating a liquid metal battery according to an embodiment of the present invention.

Referring to FIG. 5, in the liquid metal battery according to the present embodiment, a predetermined space may be defined between a vertically extending side of the positive electrode current collector 150 and a vertically extending side of the solid electrolyte 200. Accordingly, during volume expansion and contraction of the liquid anode 100, the liquid anode 100 may contact the side of the solid electrolyte 200 as well as the lower portion of the solid electrolyte 200. However, the height A in which the expanded liquid anode 100 is in contact with the side of the solid electrolyte 200 may not exceed the height of the side of the solid electrolyte 200. In this embodiment, by contacting the liquid anode 100 and the liquid cathode 300 with the lower and side portions of the solid electrolyte 200 interposed therebetween, the ion transport area can be increased, and the electrical characteristics of the liquid metal battery are improved. Can be.

6 is a cross-sectional view illustrating a liquid metal battery according to an embodiment of the present invention.

Referring to FIG. 6, the liquid metal battery according to the present embodiment is the same as the embodiment shown in FIG. 1 except that the negative electrode current collector has a plurality of spring shapes 350a, 350b, and 350c, and therefore, the same component may be used. The description is omitted.

In the present embodiment, since the negative electrode current collector 350 has a plurality of springs 350a, 350b, and 350c shapes, a current collecting area through which electrons dissociated in the liquid negative electrode 300 can be greatly increased. . In detail, since the negative electrode current collector 350 has a plurality of spring shapes, the surface area of the portion immersed in the liquid negative electrode 300 may be increased, thereby improving electrical characteristics such as capacitance of the liquid metal battery. Can be.

In addition, as the spring shape of the negative electrode current collector 350 is increased to a plurality, the vertical movement of the solid electrolyte 200 may be more smoothly performed due to elastic elongation and elastic contraction. The contact with the solid electrolyte 200 according to the volume change of may be better maintained.

7 is a cross-sectional view showing a liquid metal battery according to an embodiment of the present invention.

Referring to FIG. 7, the liquid metal battery according to the present embodiment is the same as the embodiment shown in FIG. 1 except that the cathode current collector 150 further has a spring shape 170 connected to the solid electrolyte 200. Do.

In the present embodiment, the positive electrode current collector 150 has a spring shape 170 connected to the solid electrolyte, thereby increasing the current collecting area of the positive electrode current collector 150 in contact with the liquid positive electrode 100, as well as the solid electrolyte. Elastic elongation and contraction with respect to 200 can be made more gentle. For example, when it is difficult to support the solid electrolyte 200 only by the spring of the negative electrode current collector 350, the spring 170 of the positive electrode current collector 150 connected to the lower portion of the solid electrolyte 200 is elastically stretched. By further supporting the solid electrolyte 200, the vertical movement of the solid electrolyte 200 may be smoother. According to an embodiment, the spring 170 of the positive electrode current collector 150 and the spring 350 of the negative electrode current collector have substantially the same elastic modulus, so that the elastic movement of the solid electrolyte 200 may be more smoothly performed. .

8 is a cross-sectional view illustrating a liquid metal battery according to an embodiment of the present invention.

Referring to FIG. 8, in the liquid metal battery according to the present embodiment, except that the spring shapes 170a, 170b and 170c of the positive electrode current collector 150 and the spring shapes 350a and 350b of the negative electrode current collector are plural. , The same as the embodiment shown in FIG.

In the present embodiment, as the spring is increased in plural, the current collecting area of the negative electrode current collector 350 and the current collecting area of the positive electrode current collector 170 may respectively increase, and accordingly, the electrical capacity such as the capacitance of the liquid metal battery is increased. Properties can be improved.

In addition, the upper and lower portions of the solid electrolyte 200, respectively, by supporting a plurality of springs by elastic expansion and elastic contraction, the vertical movement of the solid electrolyte 200 can be smoothed.

9 is a cross-sectional view showing a liquid metal battery according to an embodiment of the present invention.

Referring to FIG. 9, in the liquid metal battery according to the present exemplary embodiment, the protrusion 210 is formed on the outer surface of the solid electrolyte 200, and the protrusion 210 is accommodated on the inner surface of the positive electrode current collector 150. Except that the recess 151 is formed, it is the same as the embodiment shown in FIG.

In the embodiment of FIG. 1, the liquid positive electrode 100 of the liquid metal cell may partially leak into a gap between the side of the solid electrolyte 200 and the positive electrode current collector 150 according to volume expansion and contraction. In the example, the liquid leaks along the side of the solid electrolyte 200 by the protrusion 210 formed on the outer surface of the solid electrolyte 200 and the recess 151 formed on the inner surface of the positive electrode current collector 150. By increasing the length that the anode must move, leakage of the liquid anode 100 can be more reliably prevented. In addition, since the protrusion 210 moves up and down in the space R of the recess 151 and is caught by the top or bottom of the recess 151, the volume expansion of the liquid anode 100 is within a predetermined range. Can be adjusted. By the protrusion 210 of the solid electrolyte 200 and the recess 151 of the positive electrode current collector 150, the liquid anode 100 surrounded by the solid electrolyte 200 and the positive electrode current collector 150 is more visible. It can be securely sealed.

In addition, when the volume expansion and contraction of the liquid anode 100, the protrusion 210 is caught on the top or bottom of the recess 151, thereby supporting elasticity by the negative electrode current collector 350 connected to the solid electrolyte 200 In addition, the support force by the locking may be further provided so that the solid electrolyte 200 may be raised or lowered more stably on the liquid anode 100.

Meanwhile, in FIG. 9, the protrusion 210 is formed on the outer surface of the solid electrolyte 200, and the recess 151 is formed on the inner surface of the positive electrode current collector 150. On the contrary, a recessed portion may be formed on the outer side of the solid electrolyte 200, and a protrusion may be formed on the inner side of the positive electrode current collector. In addition, an insulation protection part (not shown) may be further disposed between the outer side of the solid electrolyte 200 and the inner side of the positive electrode current collector 150. In this case, the outer side of the solid electrolyte 200, the positive electrode current collector ( A protrusion may be formed on at least one of the inner side of the 150 and the insulation protection unit, and a recessed portion may be formed on at least the other.

As described above, according to the present invention, the liquid metal cell includes a solid electrolyte, thereby reducing the metal ions of the liquid negative electrode infiltrated into the electrolyte to sufficiently separate the liquid negative electrode and the liquid positive electrode, thereby reducing self-discharge. You can.

In addition, as the negative electrode current collector is connected to the solid electrolyte in a spring shape, the solid electrolyte can be moved in close contact with the liquid positive electrode and the liquid negative electrode according to the change in the depth direction due to the volume expansion and contraction of the liquid positive electrode. And it is possible to improve the electrochemical stability at the time of driving while sealing the cathode.

In addition, since the solid electrolyte has a curved shape between the liquid anode and the liquid cathode, the surface area of the solid electrolyte capable of ion migration can be increased, thereby increasing the charge / discharge rate of the liquid metal battery.

In addition, as the negative electrode current collector having a plurality of spring shapes is connected to the solid electrolyte, the elastic movement of the solid electrolyte may be smoothed according to the volume change of the liquid positive electrode and the negative electrode, and the surface area collected in the liquid negative electrode may be increased. In addition, the capacitance of the liquid metal battery can be improved.

In addition, the spring-shaped positive electrode current collector is further connected to the solid electrolyte through the liquid positive electrode, thereby increasing the positive electrode current collecting area and maintaining contact between the liquid positive electrode and the solid electrolyte according to the volume change of the liquid positive electrode. .

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 idea of the present invention can be carried out in addition to the embodiments disclosed herein.

Claims (15)

Liquid anode; A solid electrolyte disposed on the liquid anode; A liquid negative electrode disposed on the solid electrolyte; A positive electrode current collector in contact with the liquid positive electrode; And And a negative electrode current collector having a spring shape passing through the liquid negative electrode and connected to the solid electrolyte. The method of claim 1, The negative electrode current collector is configured to maintain the contact between the solid electrolyte and the liquid positive electrode when the liquid positive electrode expands or contracts in the depth direction. The method of claim 2, The negative electrode current collector includes a plurality of springs connected to the solid electrolyte to provide an elastic force against the volume change of the liquid positive electrode. The method of claim 1, Wherein said solid electrolyte has a curved shape between said liquid anode and said liquid cathode. The method of claim 4, wherein The solid electrolyte is A flat portion parallel to the surface of the liquid cathode; And Liquid metal battery comprising a plurality of depressions bent to the top or bottom from the flat portion. The method of claim 5, The thickness of the recess portion is a liquid metal battery, characterized in that less than or equal to the thickness of the flat portion. The method of claim 5, The negative electrode current collector is a liquid metal battery, characterized in that connected to the flat portion. The method of claim 1, And the cathode current collector accommodates the liquid anode, the solid electrolyte, and the liquid cathode. The method of claim 8, And the solid electrolyte extends upwardly to surround the liquid cathode between the liquid cathode and the cathode current collector. The method of claim 9, One of the inner side of the positive electrode current collector and the outer side of the solid electrolyte is provided with a protrusion for limiting the volume change of the liquid positive electrode, the other of the inner side of the positive electrode current collector and the outer side of the solid electrolyte Liquid metal battery, characterized in that the recess for receiving the protrusion is formed. The method of claim 9, And the liquid anode is further disposed between the solid electrolyte and the cathode current collector. The method of claim 1, The liquid anode is sealed by the solid electrolyte and the cathode current collector. The method of claim 1, The positive electrode current collector has a spring shape connected to the solid electrolyte through the liquid positive electrode. The method of claim 13, The negative electrode current collector and the positive electrode current collector, respectively, characterized in that it has a plurality of spring shape. The method of claim 13, The elastic modulus of the spring of the positive electrode current collector is the same as the elastic modulus of the spring of the negative electrode current collector.

Images