KR101132957B1 - electrode of battery - Google Patents

Abstract

An electrode of a battery is disclosed. The electrode of the battery includes a current collector including a plurality of trench structures disposed on the first surface side by side, and an active material is bonded inside the plurality of trench structures, so that the upper surface of the bonded active material and the plurality of trench structures are formed. The formed first surface is exposed together. Accordingly, since the active material is inserted into the trench structure, volume expansion of the active material can be suppressed and the charge / discharge cycle characteristics can be improved.

Description

Electrode of Battery

The present invention relates to an electrode of a battery, and more particularly, to an electrode of a battery that performs charge and discharge using lithium ions.

Recently, with the rapid development of communication technology, multifunctionalization of mobile devices such as cellular phones is being made, and accordingly, interest in the development of high capacity batteries is increasing.

In particular, research into high-capacity batteries has been actively conducted for application to storage devices for renewable energy such as wind, solar, and solar power or power supply for electric vehicles.

A battery is a device that converts chemical energy into electrical energy. It is composed of a positive electrode, a negative electrode, and an electrolyte, and a positive electrode (high potential material) and a negative electrode (low potential material) are caused by a relative potential difference with the ionic substance exchanged. Are distinguished. The positive electrode and the negative electrode are collectively called an electrode, and the electrode is composed of an active material causing an electrochemical reaction, and a current collector used as a movement path of electrons.

For example, in the case of a lithium battery, charge and discharge are performed through lithium ion exchange between a cathode and an anode disposed with an electrolyte therebetween, and alkali ions such as Mg, Na, Ca, and Li, depending on the type of exchange ion. This can be used.

An electrode is charged and discharged through intercalation or deintercalation of the ions, and the high capacity electrode in the present invention refers to an electrode made of a material having a theoretical capacity of about 300 mAh / g or more.

In the case of a high-capacity positive electrode, a change in the volume of the active material and a phase change of the active material may cause weakening of the binding force between the active material and the current collector and dissolution into the electrolyte.

In addition, in the case of a high capacity negative electrode, a relatively large volume change occurs due to the bonding and decomposition of a large amount of exchange ions during the charge and discharge process, and separation of the active material and the current collector occurs.

Such a structural problem in the electrode reduces the electrical conductivity in the electrode, and eventually causes the performance of the battery to deteriorate.

Such a lithium battery repeats an operation of intercalation / deintercalation or alloying / dealloying lithium ions in an active material during a charging process or a discharging process.

As a result of this repetitive operation, when the structural stability of the electrode is deteriorated, the electrical conductivity of the electrode is lowered, and thus the function is not properly performed.

Therefore, in the battery, even if the exchange of ions is performed according to the charging and discharging, there is a need for a method for improving the performance of the electrode, such that the active material is immobilized on the current collector, the high-capacity electrode can operate properly.

The present invention has been made to solve the above-described problems, by inserting the active material in a plurality of trench structures, by fixing the active material inside the current collector during the charge and discharge process, to improve the binding force of the current collector-active material in the electrode and to change the volume It is an object of the present invention to provide an electrode of a battery capable of suppressing the problem.

An electrode of a battery according to an embodiment of the present disclosure includes a current collector having a plurality of trench structures disposed on a first surface in parallel with each other, and an active material is bonded to the plurality of trench structures to form the active material. An upper surface of and a first surface on which the plurality of trench structures are formed are exposed together.

The current collector may further include a plurality of trench structures arranged in parallel with each other that are orthogonal to the plurality of trench structures arranged in parallel with each other on the first surface.

The current collector may further include a plurality of trench structures disposed in parallel with each other on a second surface that is a rear surface of the first surface.

The active material may be in powder form, and the active material in powder form may be mixed with a conductive material and a binder to be combined into the plurality of trench structures.

The active material may be formed of a single thin film.

The active material may include an interlayer formed on a bottom surface of the trench structure, and an electrode material formed on the interlayer.

The active material may further include a bonding layer formed on a boundary region of the interlayer and the electrode material.

The electrode is a negative electrode, and the active material may include at least one of Si, Sn, Pb, Ge, and Al.

The electrode is a positive electrode, and the active material may include at least one of S (sulfur) and sulfide.

The electrode may be a cathode, and the electrode material may include at least one of Si, Sn, Pb, Ge, and Al, and the interlayer may include at least one of a metal, an oxide of the metal, and a nitride of the metal. .

The electrode is an anode, and the electrode material may include at least one of S (sulfur) and sulfide, and the interlayer may include at least one of a metal, an oxide of the metal, and a nitride of the metal.

The active material may include a bonding layer formed by heat treating the intermediate layer and the electrode material.

In the current collector, when the trench structure is formed on the first surface, a roughness structure may be formed on a bottom surface of the trench structure.

The current collector may be selected from the group consisting of copper, nickel, iron, molybdenum, tungsten, cobalt, stainless steel, titanium, and aluminum, or an alloy thereof or a compound thereof.

The active material and the current collector can form a compound by heat treatment.

The active material may include at least one of Si, Sn, Pb, Ge, and Al and a carbon-based material.

According to various embodiments of the present disclosure, since the active material is inserted into the trench structure on the surface of the current collector, the volume expansion caused by the phase change of the active material may be suppressed and the semi-solid active material may be fixed by the surface tension. Accordingly, the charge and discharge cycle characteristics can be improved.

1 is a view showing an electrode according to an embodiment of the present invention.
2A to 3B are views showing various examples of the current collector.
4 to 7 illustrate examples of electrodes according to various forms of active materials.
8 is a view showing the form of the active material according to the insertion or alloying of lithium ions.
9 illustrates an example of an electrode on which a roughness structure is formed.
10A to 10D are views illustrating an electrode manufacturing method according to an embodiment of the present invention.
11A to 11D are views illustrating an electrode manufacturing method according to another embodiment of the present invention.
12 is a diagram for explaining the operation of the electrolytic etching.
13A-13C illustrate various examples of trench structures in which elastic materials are formed.
14 is a flowchart illustrating a method of manufacturing an electrode according to an exemplary embodiment.

Hereinafter, various embodiments of the present disclosure will be described with reference to the accompanying drawings.

1 is a view showing an electrode according to an embodiment of the present invention.

Referring to FIG. 1, the electrode 100 may be, for example, an electrode of a lithium battery (not shown) that may be charged or discharged according to exchange of lithium ions.

The electrode 100 may be any one of a cathode and an anode.

The electrode 100 includes a current collector having a plurality of trench structures 120: 120-1, 120-2, 120-3, 120-4, and 120-5 arranged on the first surface in parallel with each other. 110.

The current collector 110 is made of a metal foil, preferably copper foil. As an example, the current collector 110 is coated with copper, nickel, iron, molybdenum, tungsten, cobalt, stainless steel, titanium, aluminum, carbon-coated aluminum, nickel foam, copper foam, conductive metal It can be used selected from the group consisting of a polymer substrate, and combinations thereof, and in some cases, the above-described material may be processed into a foam, a mesh, a conductive material coating, a perforation, etc., but not limited thereto. It doesn't happen. Alternatively, a material obtained by coating at least one surface of the above materials with another material may be used.

In the plurality of trench structures 120, active materials may be inserted into each of the plurality of trench structures 120. Preferably, the plurality of trench structures 120 have the same shape, and the amount of the active materials 130 inserted into each of the plurality of trench structures 120 is also the same. Do.

In addition, the plurality of trench structures 120 may be formed by various methods such as dry etching, wet etching, and lithography. Preferably, the plurality of trench structures 120 may be formed on at least one surface of the current collector 110 by an electrolytic etching method. Accordingly, the electrode 100 can be mass-produced at low cost.

Lithium ions may bind to the active material 130, and thus, the active material 130 may have volume expansion inside the plurality of trench structures 120.

However, since the active material 130 is inserted into the trench structure, volume expansion may be limited (ie, suppressed) by the trench structure 120.

In addition, since the plurality of trench structures 120 are arranged in parallel with each other, and the shapes thereof are all the same, the plurality of trench structures 120 may generate stresses (ie, deformation forces) generated by volume expansion of the active material 130. It may be distributed evenly to each.

In addition, the active material 130 is inserted into the trench structure, the plurality of trench structures 120 are each disposed in parallel to each other, the shape of the same according to the same structural characteristics, the lithium ion bonded to the active material 130 The minute cracks of the active material 130 generated by being separated from the active material 130 may also be alleviated.

On the other hand, the electrode 100 has a first surface in which the active material 130 is coupled to the inside of the plurality of trench structures 120, and the upper surfaces T1, T2, T3, T4, and T5 of the active material are formed. (140: 140-1, 140-2, 140-3, 140-4, 140-5, 140-6) may be exposed together.

Here, since the first surface (not shown) represents the entire upper surface of the current collector before the plurality of trench structures are formed, it is different from the first surface 140 on which the plurality of trench structures 120 are formed.

According to the present electrode 100, unlike the conventional general electrode, in which the active material is bonded to the entire upper surface of the current collector to improve the coating force of the current collector, the upper surface (T1, T2, T3, T4, T5) of the active material and a plurality of The first surface 140 with the two trench structures already formed may be exposed together. As a result, according to the present invention, since the volume expansion by the active material 130 can be suppressed, it is possible to provide the electrode 100 excellent in charge and discharge cycle characteristics.

2A to 3C are diagrams illustrating various examples of the current collector.

Referring to FIG. 2A, an example of the current collector 210 of the present electrode 200 is illustrated. It has the same shape as the current collector 210 shown in FIG. 1 shown in FIG. 2A.

Preferably, the total height H of the current collector 210 is 25 μm, the depth C of the plurality of trenches is 10 μm, and the width A of the plurality of trenches and the first trench structure in which the plurality of trench structures are formed. The width B of the surface is preferably the same and may be 10 μm.

In addition, the ratio of the total height H of the current collector 210 to the depth C of the plurality of trenches is preferably 40% or more.

The number of trench structures of the main electrode 200, the number of the heights of the main electrode 200, the depth of the trench, the width of the trench, and the like are not limited thereto.

Referring to FIG. 2B, another example of the structure of the current collector 210 of the present electrode 200 is illustrated.

The current collector 210 may further include a plurality of trench structures arranged side by side, orthogonal to each other, orthogonal to the plurality of trench structures arranged side by side on the first surface.

Specifically, as shown in FIG. 2B, a plurality of trench structures are arranged side by side in the + X axis (or -X axis) direction on the first surface of the current collector 210, and the + Y axis (or − A plurality of trench structures arranged side by side in the (Y-axis) direction may be formed together.

On the other hand, in this case, after the plurality of trench structures orthogonal to each other are formed in the current collector 210, the remaining pillars J1, J2, J3, and J4 have a square in which their cross sections (cross sections in the XY plane direction) are shown. In addition, it may be in various forms such as regular hexagon, regular octagon, circle.

In FIG. 2B, only some of the remaining pillars J1, J2, J3, and J4 are shown for convenience of description.

As described above, an example in which a plurality of trench structures are formed in the first plane of the electrode 200 in FIGS. 2A and 2B has been described. Hereinafter, in FIGS. 3A and 3B, the back surface of the first plane of the electrode 200 is described. An example in which a plurality of trench structures are also formed in the second plane disposed in the will be described.

Referring to FIG. 3A, a plurality of trench structures are formed on a first surface (upper surface shown) of the electrode 300, and a plurality of trench structures are formed on a second surface (lower surface shown) of the electrode 300. Can be.

For convenience of description, the current collector 310 may be divided into a first current collector 310a having a plurality of trench structures formed on a first surface and a second current collector 310b having a plurality of trench structures formed on a second surface. .

In FIG. 3A, the plurality of trench structures formed in the first current collector 310a and the plurality of trench structures formed in the second current collector 310b may be the same. In detail, each of the plurality of trench structures formed in the first current collector 310a may have a form facing each of the plurality of trench structures formed in the second current collector 310b.

 Referring to FIG. 3B, the first current collector 310a formed on the first surface may be different from the second current collector 310b formed on the second surface. In detail, each of the plurality of trench structures formed in the first current collector 310a may have a shape facing the second surface of the second current collector 310b.

Referring to FIG. 3C, the first current collector 310a may further include a plurality of trench structures disposed in parallel with each other that are orthogonal to the plurality of trench structures arranged in parallel with each other on the first surface. In addition, a plurality of trench structures may be formed on the second surface of the second current collector 310b.

Accordingly, according to the present exemplary embodiment, an electrode 300 having a relatively high volume (volume) energy density may be provided as compared to the electrode 200 illustrated in FIGS. 2A and 2B.

Since the structure of the current collector 310 illustrated in FIGS. 3A to 3C is merely an example, the structure of the current collector 310 is not limited to the illustrated current collector 310.

4 to 7 are views illustrating examples of electrodes according to various forms of the present active material.

Referring to FIG. 4, the electrode 400 according to the first embodiment of the present invention may include active materials 430-1, 430-2, 430-3, 430-4, and 430-5 in powder form. . For convenience of description, it will be described based on the active material 430-1 inserted into the single trench structure.

The active material 430-1 may be mixed with the conductive material and the binder together with a powdered active material to be coupled to the plurality of trench structures.

If the electrode 400 is a negative electrode, the active material 430-1 may include at least one of Sn, Pb, Ge, Al, and Si. In this case, the active material 430-1 is preferably Si.

If the electrode 400 is a cathode, a carbon-based material may be mixed with at least one of Sn, Pb, Ge, Al, and Si to be used as the active material 430-1. Preferably, a carbon-based material may be mixed with Si to be used as the active material 430-1. Carbon-based materials include high crystalline soft carbon and low crystalline hard carbon. Soft carbon may comprise graphite (graphite).

If the electrode 400 is a positive electrode, the active material 430-1 may include at least one of S (sulfur) and sulfide. In this case, the active material 430-1 is preferably S.

The conductive material is a material for improving electrical conductivity, and may be, for example, carbon. The binder is a material for bonding the active material 430-1 with the conductive material. For example, the binder may be a resin.

As an example, when the electrode 400 is a negative electrode, a conventional electrode is used as the active material in powder form, but graphite having a low theoretical capacity of about 372 mAh / g, but used in the present electrode 400. Preferably, the active material 430-1 is Si having a high theoretical capacity of about 4200 mAh / g. Here, the theoretical capacity refers to, for example, the degree to which the active material can bond with lithium ions transferred from the positive electrode in a lithium battery (not shown).

Accordingly, even if the entire surface of the upper part of the current collector 410 is not coated with the active material, and the active material is inserted only inside the trench structure, the electrode 400 having better performance than the conventional electrode can be provided.

Meanwhile, when heat treatment is performed on the main electrode 400 (specifically, the active material 430-1), the current collector 410 and the active material 430 may form a compound. Accordingly, the bonding force between the current collector 410 and the active material 430-1 may be increased. As a result, according to the present invention, since the volume expansion of the active material can be further suppressed, it is possible to provide the electrode 400 having more excellent charge / discharge characteristics.

Here, the heat treatment is preferably performed in an inert atmosphere or a vacuum atmosphere, but in some cases, heat treatment in the air may also be performed. The heat treatment temperature may vary depending on the formation temperature and composition of the compound.

As an example, when the binder for bonding the active material 430-1 and the conductive material is made of a thermosetting resin, the active material 430-1 is heat treated at a low temperature to improve the bonding strength between the active material 430-1 and the conductive material. Alternatively, the binder may be removed by heat treating the active material 430-1 to a high temperature. As such, the heat treatment temperature may vary depending on the application.

 Referring to FIG. 5, the electrode 500 according to the second embodiment of the present invention may include active materials 530-1, 530-2, 530-2, 530-3, 530-4, and 530-5 in the form of a thin film. It may include. For convenience of description, the active material 530-1 inserted into the single trench structure will be described.

The active material 530-1 included in the trench structure of the current collector 510 may be a material having a relatively high theoretical capacity.

If the electrode 500 is a cathode, the active material 530-1 may include at least one of Sn, Pb, Ge, Al, and Si. In this case, the active material 530-1 is preferably Si.

If the electrode 500 is a positive electrode, the active material 530-1 may include at least one of S (sulfur) and sulfide. In this case, the active material 530-1 is preferably S.

Accordingly, when the electrode 500 is a negative electrode, the electrode 500 uses a relatively thin film inside the trench structure of the current collector 510, compared with a conventional electrode in the form of powder, which uses graphite as the active material. -1) can be formed.

As a result, even if the entire surface of the current collector 510 is not coated with the active material 530-1, and the active material 530-1 is inserted only inside the trench structure, the electrode 500 having better performance than the conventional electrode can be obtained. Can provide.

Meanwhile, when heat treatment is performed on the electrode 500 (specifically, the active material 530-1), the current collector 510 and the active material 530 may form a compound. Accordingly, the bonding force between the current collector 510 and the active material 530 may be increased. As a result, according to the present invention, it is possible to further suppress the volume expansion of the active material, it is possible to provide an electrode 500 having more excellent charge and discharge characteristics.

As in FIG. 4, the heat treatment is preferably performed in an inert atmosphere or a vacuum atmosphere, but in some cases, heat treatment in the air may also be performed. The heat treatment temperature may vary depending on the formation temperature and composition of the compound.

Referring to FIG. 6, the electrode 600 according to the third exemplary embodiment of the present invention may be an active material 630-1, 630-2, 630-3, 630-4, and 630-5 in the form of a thin film. It may include. For convenience of description, the active material 630-1 inserted into the single trench structure will be described.

The active material 630-1 included in the trench structure of the current collector 610 may include an interlayer film L1 formed on the bottom surface of the trench structure and an electrode material L2 formed on the interlayer film L1.

The interlayer L1 may be a material having a high bonding force with the electrode material L2, and the interlayer L1 may be a material having a negative value of the formation mixing enthalpy with the electrode material L2. . As an example, the interlayer L1 may include a general metal, an oxide of a general metal, and a nitride of a general metal.

If the electrode 600 is a cathode, the intermediate film L1 may be Ti, and the electrode material L2 may include at least one of Sn, Pb, Ge, Al, and Si. In this case, the electrode material L2 is preferably Si.

If the electrode 600 is an anode, the interlayer L1 is preferably Ni, and the electrode material L2 may include at least one of S (sulfur) and sulfide. In this case, the electrode material L2 is preferably S.

The active material 630-1 is inserted into the trench structure, and each of the plurality of trench structures is disposed in parallel with each other, and the shape of the active material 630-1 overlaps the volume expansion by the active material 630-1 according to the same structural characteristics. Since this can be suppressed, the present electrode 600 can provide an electrode having excellent charge / discharge cycle characteristics.

In addition, the electrode 600 may further mitigate fine cracks of the active material 630-1, which are generated when lithium ions bonded to the active material 630-1 are separated from the active material 630-1.

Referring to FIG. 7, the electrode 700 according to the fourth embodiment of the present invention includes an active material 730-1, 730-2, 730-3, 730-4, and 730-5 that are formed of a plurality of films and a bonding layer. It may include. For convenience of description, the active material 730-1 inserted in the single trench structure will be described.

The bonding layer C may be formed on the boundary area between the intermediate layer L1 and the electrode material L2 by heat treatment.

After the intermediate film L1 and the electrode material L2 are sequentially formed on the current collector 710, and then heat treatment is performed on the active material 730-1, the intermediate film L1 reacts with the electrode material L2 to form a compound, That is, since the bonding layer C can be formed, and the interlayer L1 has better bonding strength with the electrode material L2 due to mutual diffusion, the amount of bonding of the electrode material L2 with lithium ions can be reduced. It becomes possible. Accordingly, the interlayer film L1 can suppress the volume expansion of the active material 630-1.

The interlayer L1 and the electrode material L2 may be made of the same material as the embodiment described above with reference to FIG. 6. However, when the electrode 700 is a cathode, it is preferable that a bonding layer C having Ti and Si bonded thereto is formed. When the electrode 700 is an anode, a bonding layer C having Ni and S bonded thereto is formed. It is preferable.

That is, the active material 730-1 may have a form in which the intermediate layer L1, the bonding layer C, and the electrode material L2 are sequentially disposed.

Meanwhile, the active material 730-1 in various forms may be generated by changing various factors of the heat treatment such as heat treatment temperature, heat treatment intensity, heat treatment time, and the like.

As an example, the active material 730-1 of the present electrode 700 is, for example, a single compound of NiS when the electrode 700 is a positive electrode, or Ni, NiS, and S are from the bottom of the trench to the top surface. It may be a plurality of compounds formed sequentially.

Accordingly, the volume expansion of the electrode material L2 is suppressed by the bonding layer C, and the active material 730-1 is included in the trench structure, thereby overlapping the volume expansion by the active material 730-1. Since the present invention 700 can be suppressed, the present electrode 700 can provide an electrode having excellent charge / discharge cycle characteristics.

8 is a view showing the form of the active material according to the negative electrode charge.

Referring to FIG. 8, the active materials 830-1, 830-2, 830-3, 830-4, and 830-5 in which lithium ions are combined with an active material (lithium insertion or alloying), that is, in a charged state are shown. .

Even though lithium ions are bonded to the active material, the main electrode 800 is preferably formed to have a lower upper surface than the first surface of the active materials 830-1, 830-2, 830-3, 830-4, and 830-5. .

Accordingly, even when charging or discharging is repeatedly performed, the electrode 800 having excellent charge / discharge cycle characteristics may be provided by minimizing cracking of the electrode 800.

9 is a diagram illustrating an example of an electrode on which a roughness structure is formed.

Referring to FIG. 9, when the trench structure is formed on the first surface of the current collector 910 by the electrolytic etching method, the electrode 900 may have roughness on the lower surface of the trench structure. Roughness structure R, that is, roughness structure may be naturally formed.

The roughness structure R formed on the bottom of the trench structure may be adjusted by at least one of a current, a voltage, an etching time, an etching temperature, and a concentration of an etching solution applied to the current collector 910 to perform an electrolytic etching. have.

Accordingly, as long as the trench structure is formed on the first surface of the current collector 910 by the electrolytic etching method, the roughness structure R may be naturally formed on the bottom surface of the trench structure. The application force of the whole 910 can be improved.

Meanwhile, an electrode according to various embodiments of the present disclosure is a combination of one of various types of current collectors shown in FIGS. 2A to 3C and 9 and one of various types of active materials shown in FIGS. 4 to 7. It may have a structure of.

In addition, the present electrode, if it is possible to suppress the volume expansion caused by the phase change of the active material, and to fix the semi-solid active material by the surface tension, it is obvious that it can have a variety of forms without being limited to the illustrated form.

Meanwhile, an electrode according to various embodiments of the present disclosure may be applied to at least one of a cathode and an anode. In this case, when the negative electrode and the positive electrode are disposed to face each other with an electrolyte (separation membrane) interposed therebetween, a battery can be formed.

In order to use a battery as a battery of a mobile device, such as a battery of a cellular phone, the negative electrode, the electrolyte, and the positive electrode are arranged side by side, which is rolled up, and then the cells which are dried in a circular shape are compressed into thin plates. Let's go. According to various embodiments of the present disclosure, the electrode may have a relatively low dropout of the active material from the current collector even under such a deformation, and thus may provide an electrode having excellent charge / discharge cycle characteristics.

On the other hand, the battery (not shown) according to an embodiment of the present invention, at least one of the negative electrode and the positive electrode, one of the various types of current collector (200, 300) shown in Figures 2a to 3c, and Figures 4 to It can be made in the form of a combination of one of the various types of active material shown in FIG.

As an example, a battery (not shown) may have a negative electrode as the electrode described above with reference to FIG. 4 and a positive electrode as the electrode described above with reference to FIG. 5.

As another example, a battery (not shown) may have a current collector illustrated in FIG. 3C, an active material inserted into the current collector, illustrated in FIG. 7, and the anode may be an electrode illustrated in FIG. 6.

However, a battery (not shown) according to an embodiment of the present invention is not limited thereto.

10A to 10D are views illustrating an electrode manufacturing method according to an embodiment of the present invention. In FIGS. 10A to 10D, reference numerals are shown only for the single resist 1020, the single metal material 1025, and the single active material 1030 for convenience of description.

Referring to FIG. 10A, the electrode manufacturing method forms a resist 1020 having a predetermined pattern on the metal thin film 1010.

The metal thin film 1010 may be formed of various materials of the above-described current collector, and may be preferably a copper foil.

The resist 1020 may be ink or toner applied to the metal thin film 1010.

The resist 1020 may be formed on the metal thin film 1010 by applying a method of forming an image on a printing paper of an image forming apparatus such as a printer, a scanner, a copying machine, and a multifunction printer in which they are integrated.

Alternatively, the resist 1020 may be formed on the metal thin film 1010 by a screen method using spraying or pasting.

Alternatively, the resist 1020 may be formed on the metal thin film 1010 using a lithography process of patterning the photoresist, exposing, developing, and etching to remove the photoresist.

The resist 1020 may be formed on the metal thin film 1010 by using the above-described various methods. In this case, the resist 1020 may be in the form of a plurality of line patterns spaced apart at predetermined intervals. The resist 1020 may be expressed in various terms, such as an etching resist and a photo resist, according to an embodiment.

10B and 10C, the electrode manufacturing method may form a plurality of trench structures disposed side by side on the metal thin film 1010 using the resist 1020.

Referring to FIG. 10B, the metal material 1025 may be formed on the surface of the metal thin film 1010 between the plurality of line patterns, that is, the surface of the metal thin film 1010 in which the resist 1020 is not formed and thus the metal thin film 1010 is exposed. Can grow.

Specifically, the metal thin film exposed by at least one of chemical vapor deposition (CVD), physical vapor deposition (PVD), powder filling (coating), electrolytic plating, and electroless plating ( The metal material 1025 may be grown on the surface of the 1010.

Referring to FIG. 10C, the electrode manufacturing method may then remove the resist 1020 to form a plurality of trench structures made of the metal material 1025. Accordingly, a current collector having a trench structure including the metal thin film 1010 and the metal material 1020 may be manufactured.

Since the resist 1020 may be formed of an ink or toner having a resin component, the resist 1020 may be removed (or cleaned) using an organic solvent such as ethanol or the like.

Here, the metal material 1025 may be made of a material different from the metal thin film 1010 and may be a material elastomer. As an example, when the metal thin film 1010 is copper, the metal material 1025 may be a material of any one of Fi, Ni, Fe, and W having high elasticity. However, the present invention is not limited thereto.

Accordingly, the volume expansion caused by the active material 1030 can be alleviated to some extent by the above-described elastic metal material 1025. According to the present electrode manufacturing method, an electrode having excellent charge / discharge cycle characteristics can be provided. .

Meanwhile, after the plurality of trench structures are formed on the surface of the metal thin film 1010, as illustrated in FIG. 10C, an elastic material may be further formed on the inner side surfaces of each of the plurality of trench structures. This will be described in more detail with reference to the drawings to be described later.

Referring to FIG. 10D, the electrode manufacturing method may fill the active material 1030 in the plurality of trench structures.

When the active material 1030 is applied inside the plurality of trench structures, the active material 1030 may be applied to an upper surface of the metal material 1025 and an upper surface of the metal thin film 1010 on which the metal material 1025 is not formed. In addition, by removing the active material 1030 through a planarization process, as illustrated in FIG. 10D, an electrode having an active material 1030 inserted into the plurality of trench structures may be manufactured.

For example, when the active material 1030 is filled in the plurality of trench structures, the active material 1030 may be formed in a thin film form on the bottom surface of each of the plurality of trenches.

As another example, when the active material 1030 is filled in the plurality of trench structures, a slurry is prepared by mixing an active material in a powder form with a conductive material and a binder, and then applying the active material into the plurality of trench structures by blinding. It can be filled.

As another example, when the active material 1030 is filled in the plurality of trench structures, an intermediate film made of the first active material is formed on the bottom surface of the trench structure, and then an electrode material made of the second active material is formed on the intermediate film. Can be.

As another example, when the active material 1030 is filled in the plurality of trench structures, the interlayer and the electrode material may be heat-treated to form a bonding layer in the boundary region of the interlayer and the electrode material.

In various examples, as described above with reference to FIGS. 4 to 7, the active material 1030 may be filled in the plurality of trench structures.

In FIG. 10D, the upper surface of the active material 1030 is shown to have the same height as the upper surface of the metal material 1025, but the upper surface of the active material 1030 is formed of the metal material 1025 through the planarization operation described above. It may be lower than the upper surface of).

Accordingly, in the electrode manufactured by the method of manufacturing the electrode for growing a metal material, the upper surface of the active material 1030 and the upper surface of the plurality of trench structures may be exposed together.

On the other hand, the electrode manufacturing method can be implemented with a resist ink, the ink will be described in detail with reference to Table 1 below.

Printing ink Color Pigment Organic Pigments
Inorganic pigments dyes Vehicle Oil Vegetable oil Processed oil Mineral oil Suzy Natural resin
Processing resin
Synthetic resin solvent Aliphatic hydrocarbon system
Aromatic hydrocarbons
Alcohol
Ester
A geton system
Glycol system, glycol induction system additive Dryness regulator Dryer, Inhibitor Viscosity Adjuster Reducers, Corpp Pounds, Thickeners, Gelling Agents, etc. Other adjustments Backing prevention agent, mold prevention agent, antifoaming agent, plasticizer, etc.

Colorants are materials for giving ink color and are classified into dyes and pigments. Dyes are colorants that dissolve in water, oil, alcohol, etc., and pigments do not dissolve in these. Since the ink in the print must not dissolve, most pigments are used except in special cases. The properties of the pigment affect the ink's fluidity, dryness, gloss, discoloration, fading, elution of color, and migration.

Pigments can be divided into inorganic pigments and organic pigments.

The inorganic pigment may be colored powder mainly composed of metal. Since metal is the main ingredient, its specific gravity is high and its coloring power is weak. Therefore, it is inferior to organic pigments in printability and printing effect. However, indispensable inorganic pigments are achromatic ones such as white and black. Titanium bag, calcium carbonate, carbon black and the like.

Organic pigments have many advantages, such as rich colors, vivid colors, small specific gravity, and transparent colors. Although it is currently the main agent of ink pigments, there are also disadvantages such as light resistance, heat resistance, solvent resistance, and the like. Representative examples include Dis Azo yellow, Lake Red C, Phthalocyanine Blue, and fluorescent pigments.

Dye is limited to a specific ink and is not used for the most part. Examples used include acid dyes, basic dyes (aqueous anti-counterfeit ink, flexo ink), oil-soluble dyes (gravure ink, flexo ink, double tone ink, stamp ink), disperse dyes (sublimation transfer printing ink) Can be.

A vehicle is a carrier for moving an object, and has a role of transferring a colorant to the ground and fixing it. As the components of the vehicle, oils, solvents and resins are generally used, and there are inks in which plasticizers are blended as necessary. The vehicle has several effects such as fluidity, dryness of the ink, interfacial property, gloss, and adhesion of printing materials.

Oil is insoluble in water at room temperature and in liquid. The vegetable oils used are vegetable oils, processed oils and mineral oils.

The solvent is mainly dried by evaporation as a main component of the vehicle for liquid ink. The degree of properties, evaporation rate, dissolving power, etc., are different from each other, and may be used in combination with the ink and used as a vehicle. The chemical structures include aliphatic hydrocarbons, alcohols, ketones, and the like.

The resin is insoluble in water, but is heated or dissolved in oil or dissolved in a solvent to serve as a printing ink vehicle, and plays an important role as a delivery agent for the surface of the printed material and as a fixing agent. Natural resins, synthetic resins (phenolic resins, alkyd resins, vinyl resins, polyamide resins).

The plasticizer is a nonvolatile solvent component and serves to give flexibility to the dry film. Suitable plasticizers are used according to the use and the type of printed material, and typical examples thereof include dioctyl phthalate and octyl adipic acid.

Wax is used as a main component of cold set ink, copy carbon ink and the like by using a low melting point and soft property, and a small amount is added in printing ink to improve the film strength such as friction resistance.

Additives include catalysts that promote oxidative drying, increase the viscosity of the ink, impart gel structure and thixotropy of the ink, midpoints that prevent pigment settling, gerohaze, thixotropy-imparting agents, defoamers, mold removers, Drying inhibitors, ultraviolet absorbers, antistatic agents and the like.

On the other hand, in the electrode manufacturing method according to an embodiment of the present invention, since the resist may be implemented as a toner, the toner will be described in detail below.

Toner is fine particles having a size on the order of several micrometers for forming a print image on a print medium. The toner may include fine plastic particles, lubricants, iron, wax, carbon, and other materials. That is, the toner composition generally includes a colorant, a binder resin, a charge control agent, and other functional additives.

Colorants can be broadly classified into dye-based colorants and pigment-based colorants. Among them, pigment-based colorants are more commonly used as colorants for toners because they are advantageous in thermal stability and light resistance than dye-based colorants.

The binder resin accounts for about 90% of the toner as a whole and serves to fix the toner particles onto the recording medium. There are many polymer materials that can be used as the binder resin, and in particular, a latex form of a colloidal gel in which two components are dispersed in a particulate form can be used as the binder resin.

The charge control agent is used to control the amount of charge charged to the toner particles, and a metal azo compound, a salicylic acid metal complex, nigrosine, a quaternary ammonium salt, and the like can be used.

Among the functional additives added to the toner, there is a releasing agent as an additive for improving the release property. The release agent improves releasability between the roller and the toner when the toner image is transferred to and fixed to the recording medium to prevent toner offset, and the toner causes the recording medium to stick to the roller, causing the recording medium to jam. It is added to the toner composition to prevent it.

As the release agent, low molecular weight polyolefins, silicones having a softening point by heating, fatty acid amides, waxes and the like can be used.

11A to 11D are views illustrating an electrode manufacturing method according to another exemplary embodiment of the present invention. 11A through 11D, reference numerals are shown only for the single resist 1120, the single metal material 1125, and the single active materials 1130a and 1130b for convenience of description.

Referring to FIG. 11A, the electrode manufacturing method forms a resist 1120 having a predetermined pattern on the metal thin film 1110. Since the method of forming the resist 1120 having a predetermined pattern on the metal thin film 1110 is the same as that described with reference to FIG. 10A, a description of overlapping portions will be omitted.

Referring to FIG. 11B, the electrode manufacturing method may form a plurality of trench structures by etching the surface of the metal thin film 1110 between the plurality of line patterns.

The plurality of trench structures may be formed according to at least one of electrolytic etching, dry etching, and wet etching. The electrolytic etching will be described in more detail with reference to the drawings to be described later.

When the plurality of trench structures are formed in the metal thin film 1110, an elastic material may be formed on the side surface of each of the plurality of trench structures. This will be described in more detail with reference to the drawings to be described later.

11C and 11D, the electrode manufacturing method may apply active materials 1130a and 1130b to an upper surface of the resist 1120 and an upper surface of the etched metal thin film 1110.

In this electrode manufacturing method, the resist 1120 filled with the active materials 1130a and 1130b can then be removed using an organic solvent such as ethanol. Accordingly, an electrode in which the active material 1130a is inserted may be manufactured in the plurality of trench structures of the metal thin film 1110.

However, one example of inserting the active material in the electrode shown in FIG. 4 is different from that shown in FIG. 11C. After removing the resist 1120 first, the active material 1130 in powder form is mixed with a conductive material and a binder to form a slurry. After forming, the active material 1130 may be filled into the plurality of trench structures by blinding. Accordingly, it may be different from an example of inserting the active material 1130 in the electrode illustrated in FIGS. 5 to 7.

As described above with reference to FIG. 10D, the active material 1030 may be filled in the plurality of trench structures by the method described above with reference to FIGS. 4 to 7.

Accordingly, the electrode manufactured by the present electrode manufacturing method of forming the trench structure in the metal thin film 1110 by etching may expose the upper surface of the active material 1130 and the upper surface of the plurality of trench structures together.

10 and 11 illustrate a method of manufacturing a current collector (or an electrode) having trench structures arranged side by side in one direction, but having trench structures orthogonal to each other as shown in FIG. 3C. The method of manufacturing the current collector (or the electrode) may also be manufactured in the same manner as described above.

In addition, according to the manufacturing method in FIGS. 10 and 11, various current collectors or electrodes described above in the previous drawings may be manufactured.

12 is a diagram for explaining the operation of the electrolytic etching.

Referring to FIG. 12, an electrolytic cell 1210 filled with an etching solution 1220 includes a positive electrode plate 1230 and a negative electrode plate 1240.

The positive electrode plate 1230 and the negative electrode plate 1240 are immersed in the etching solution 1220, and the positive electrode plate 1230 and the negative electrode plate 1240 may be connected to the power source A through wires. Here, the positive electrode plate 1230 may be a first electrode, and the negative electrode plate 1240 may be a second electrode.

When the power A is supplied, electrons may move from the illustrated arrow direction, that is, the negative electrode plate to the positive electrode plate, and thus ions constituting the negative electrode plate 1240 may be separated and attached to the positive electrode plate 1230. Accordingly, the negative electrode plate 1240 may be electrolytically etched.

Here, the etching solution 1220 may include a liquid acid or a liquid base and an electrolytic solution of acids, bases and salts. Specifically, the etching solution 1220 may include Lewis acid, Lewis base, or a solution thereof, and may include sodium chloride, potassium chloride, aluminum chloride, zinc chloride, tin chloride, ferric chloride sodium nitrite, and potassium nitrite. And an aqueous solution of hydrochloric acid, nitric acid, sulfuric acid and the like, and various liquids including an aqueous solution of these acids diluted with water.

On the other hand, since the etching solution 1220 itself has an etching force, the etching solution 1220 may be physically or chemically etched even when there is no power source A for applying a current.

As illustrated in FIG. 11A, when the resist 1120 is formed in the metal thin film 1110 in a plurality of line patterns, the metal thin film 1110 on which the resist 1120 is formed may be used as the negative electrode plate 1240.

According to the above-described electrolytic etching, the surface of the metal thin film 1110 between the plurality of line patterns may be etched, and as a result, a plurality of trench structures may be formed.

13A to 13C illustrate various examples of trench structures in which an elastic material is formed.

13A to 13C may form an elastic material in the trench structure using the trench structure illustrated in FIG. 10C. Also, after the resist 1120 is removed from the trench structure illustrated in FIG. 11B, an elastic material may be formed inside the trench structure.

Referring to FIG. 13A, the electrode manufacturing method may form elastic materials 1340: 1340a and 1340b on side surfaces of each of the plurality of trench structures.

The elastic material 1340 may be a metal material having a relatively higher elasticity than the metal thin film 1310.

The electrode manufacturing method uses a method such as chemical vapor deposition (CVD) or physical vapor deposition (PVD) to deposit (stack) an elastic material 1340 inside each of the plurality of trench structures, and then to the side of the trench structure. By removing the remaining elastic material except the formed elastic material 1340 by an etching method, the elastic material 1340 may be formed on the side surface of each of the plurality of trench structures.

In this case, in a state where the metal thin film 1310 is inclined at a predetermined angle, when a gas (particle) for depositing an elastic material is injected from the nozzle into the trench structure of the metal thin film 1310, each of the plurality of trench structures An elastic material 1340 having a structure as shown in FIG. 13B may be formed on the inner side of the.

Here, when the inclination angle and injection time of the metal thin film 1310 are adjusted, an elastic material 1340 having a structure as shown in FIG. 13C may be formed on the inner side surface of each of the plurality of trench structures.

In addition, when the metal thin film 1310 rotates in a state inclined at a predetermined angle, each of the plurality of trench structures may have various shapes, such as a cone and a cylinder.

14 is a flowchart illustrating an electrode manufacturing method according to an exemplary embodiment.

Referring to FIG. 14, in the method of manufacturing an electrode, a resist having a predetermined pattern is formed on a metal thin film (S1410).

Thereafter, a plurality of trench structures arranged side by side on the metal thin film are formed using the resist (S1420).

Then, the active material may be filled in the plurality of trench structures (S1430).

Accordingly, in the electrode manufactured by the electrode manufacturing method, the upper surface of the active material and the upper surface of the plurality of trench structures may be exposed together. In addition, since the active material is inserted into the trench structure of the surface of the current collector, the electrode manufactured by the present electrode manufacturing method can suppress the volume expansion caused by the phase change of the active material and fix the semi-solid active material due to the surface tension. . Accordingly, the charge and discharge cycle characteristics can be improved.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is clearly understood that the same is by way of illustration and example only and is not to be taken by way of illustration, It goes without saying that the example can be variously changed. Therefore, various modifications may be made without departing from the spirit of the invention as claimed in the claims, and such modifications should not be individually understood from the technical spirit or outlook of the invention.

100, 200, 300, 400, 500, 600, 700, 800, 900: electrode
110, 210, 310, 410, 510, 610, 710, 810, 910: current collector
120: multiple trench structures
130, 430, 530, 630, 730, 830: active material
140: first surface with a plurality of trench structures
310a: first current collector 310b: second current collector
1010, 1110, 1310: metal thin film 1020, 1120: resist
1030, 1130: active material 1210: electrolytic cell
1220 etching solution 1230 positive electrode plate
1240: negative electrode plate 1340: elastic material

Claims (16)

And a current collector having a plurality of trench structures disposed on the first surface side by side.
An active material is bonded to the plurality of trench structures, and the upper surface of the bonded active material and the first surface on which the plurality of trench structures are formed are exposed together. The method of claim 1,
The current collector further includes a plurality of trench structures arranged next to each other that are orthogonal to the plurality of trench structures arranged next to each other on the first surface. The method of claim 1,
The current collector further includes a plurality of trench structures disposed in parallel with each other on a second surface that is a rear surface of the first surface. The method of claim 1,
The active material is in powder form, wherein the active material in powder form is mixed with a conductive material and a binder and bonded to the plurality of trench structures inside. The method of claim 1,
The active material is a battery electrode, characterized in that formed in a single thin film. The method of claim 1,
The active material may include an interlayer film formed on the bottom surface of the trench structure, and an electrode material formed on the interlayer film. The method of claim 6,
The active material is a battery electrode, characterized in that further comprising a bonding layer formed in the boundary region of the interlayer and the electrode material. The method according to claim 4 or 5,
The electrode is a cathode,
The active material includes at least one of Si, Sn, Pb, Ge, and Al. The method according to claim 4 or 5,
The electrode is an anode,
The active material is a battery electrode, characterized in that it comprises at least one of S (sulfur) and sulfide. The method according to claim 6 or 7,
The electrode is a cathode,
The electrode material comprises at least one of Si, Sn, Pb, Ge, and Al,
And the interlayer includes at least one of a metal, an oxide of the metal, and a nitride of the metal. The method according to claim 6 or 7,
The electrode is an anode,
The electrode material comprises at least one of S (sulfur) and sulfide,
The interlayer film includes at least one of a metal, an oxide of the metal, and a nitride of the metal. The method according to claim 6 or 7,
The active material is a battery electrode, characterized in that it comprises a bonding layer formed by heat treatment of the interlayer and the electrode material. The method of claim 1,
The current collector,
And when the trench structure is formed on the first surface, a roughness structure is formed on a bottom surface of the trench structure. The method of claim 1,
The current collector is selected from the group consisting of copper, nickel, iron, molybdenum, tungsten, cobalt, stainless steel, titanium, aluminum, and carbon-coated aluminum, or an alloy thereof or a compound thereof. The electrode of the battery made into. The method according to claim 4 or 5,
The said active material and the said electrical power collector form a compound by heat processing, The electrode of the battery characterized by the above-mentioned. The method of claim 8,
The active material,
At least one of the Si, the Sn, the Pb, the Ge, and the Al and a carbon-based material are mixed.

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