Wire-type tri-electrode secondary battery

Abstract

A wire-type tri-electrode secondary battery according to some embodiments may comprise: a support in the form of a hollow cylinder provided with a plurality of holes on the surface; a reference electrode inserted into the support; and an electrode assembly wound around the support. Accordingly, some embodiments allow measurements of the tri-electrodes to be taken stably even in the presence of physical movement.

Description

Wire-type three-electrode secondary battery

[0001] The present invention relates to a wire-type three-electrode secondary battery.

[0002] This disclosure claims the benefit of priority to Republic of Korea Patent Application No. 10-2024-0115029, filed August 27, 2024, the entire contents of which are incorporated by reference herein.

[0003]

[0004] To reduce dependence on fossil fuels and carbon emissions, interest in rechargeable secondary batteries, which can be recharged for extended periods of time, is growing. Secondary batteries are used in a wide range of applications, including vehicles, portable electronic devices, and energy storage systems (ESS), as well as wearable and flexible devices.

[0005] Secondary batteries are generally classified into cylindrical, prismatic, or pouch-shaped types based on their external appearance. However, secondary batteries with these external shapes may not be suitable for wearable and flexible devices. Accordingly, flexible wire-type secondary batteries can be used in wearable and flexible devices.

[0006] Meanwhile, in order to confirm the performance of a secondary battery, the electrode potential of the secondary battery must be measured. Measuring the electrode potential requires a three-electrode system including a reference electrode, a working electrode, and a counter electrode (or auxiliary electrode). The performance of a wire-type secondary battery can also be confirmed through a three-electrode system. In the case of a wire-type secondary battery, the performance needs to be confirmed while there is physical movement. In the past, three-electrode measurements were performed by placing the reference electrode outside the wire-type secondary battery, but this method had the problem that the three-electrode measurements were unstable when there was physical movement in the wire-type secondary battery.

[0007] Accordingly, a technology is needed to enable stable three-electrode measurement even when there is physical movement in a wire-type secondary battery.

[0008]

[0009] The technical idea of ​​the present invention aims to solve a problem by providing a wire-type three-electrode secondary battery capable of stably performing three-electrode measurement even when there is physical movement.

[0010]

[0011] Some embodiments of the present invention that can solve the above problem are as follows.

[0012] According to some embodiments, a wire-type three-electrode secondary battery comprises a support having a hollow cylinder structure and including a plurality of holes on a surface;

[0013] a reference electrode inserted into the interior of the support; and

[0014] An electrode assembly wound on the above support;

[0015] may include.

[0016] In some embodiments, the reference electrode comprises a reference electrode active material layer on one side,

[0017] The above reference electrode active material layer is located inside the support.

[0018] The other side of the reference electrode, which is the opposite side of one side of the reference electrode, may be located outside the support.

[0019] In some embodiments, the reference electrode active material layer may include one or more of lithium metal and lithium titanium oxide.

[0020] In some embodiments, the electrode assembly comprises a first electrode, a first separator, and a second electrode,

[0021] The first electrode, the first separator, and the second electrode are sequentially stacked based on the support,

[0022] The electrical polarities of the first electrode and the second electrode may be opposite to each other.

[0023] In some embodiments, the electrode assembly may include a second separator covering the electrode assembly.

[0024] In some embodiments, the second separator may also cover the support.

[0025] In some embodiments, the second separator may include packaging covering the second separator.

[0026] In some embodiments, the electrode assembly may be sheet-shaped.

[0027] In some embodiments, the electrode assembly may be wound so as not to overlap in a spiral manner.

[0028] In some embodiments, the electrode assembly may be wound in a spiral manner with an overlap of 0.1 to 0.5 times the width of the electrode assembly.

[0029]

[0030] Some embodiments of the present invention can stably perform three-electrode measurements even when there is physical movement.

[0031] The effects of the embodiments of the present invention are not limited to the effects mentioned above, and other effects not mentioned can be clearly derived and understood by those skilled in the art to which the embodiments of the present invention pertain from the following description. In other words, unintended effects resulting from practicing the embodiments of the present invention can also be clearly derived and understood by those skilled in the art to which the embodiments of the present invention pertain.

[0032]

[0033] FIG. 1 is a schematic diagram illustrating a wire-type three-electrode secondary battery according to some embodiments.

[0034] Fig. 2 is a cross-sectional view taken along the cutting line I-I' of Fig. 1.

[0035] FIG. 3 is a schematic drawing of an electrode assembly included in a wire-type three-electrode secondary battery according to some embodiments.

[0036] FIG. 4 is a schematic drawing showing a support included in a wire-type three-electrode secondary battery according to some embodiments.

[0037] FIG. 5 is a schematic diagram illustrating a reference electrode included in a wire-type three-electrode secondary battery according to some embodiments.

[0038] FIG. 6 is a schematic drawing showing, in some embodiments, an electrode assembly wound around a support.

[0039] FIG. 7 is a schematic drawing showing an electrode assembly wound around a support in some other embodiments.

[0040] FIG. 8 is a schematic drawing of a portion of an electrode assembly wound to overlap a support in some other embodiments.

[0041] FIG. 9 is a schematic drawing showing, in some embodiments, a second separator covering an electrode assembly.

[0042] FIG. 10 is a schematic drawing showing, in some other embodiments, a second separator covering an electrode assembly.

[0043]

[0044] The terms or words used in this specification should not be interpreted as limited to their usual or dictionary meanings, but should be interpreted in a meaning that conforms to the technical idea of ​​the present invention based on the principle that the inventor can appropriately define the meaning of the terms or words to explain his or her own invention in the best way.

[0045] In this specification, it should be understood that terms such as "include" or "have" are intended to specify the presence of a feature, number, step, operation, component, part or combination thereof described in the specification, but do not preclude the possibility of the presence or addition of one or more other features, numbers, steps, operations, components, parts or combinations thereof. In addition, when it is said that a part such as a layer, film, region or plate is "on" another part, this includes not only the case where it is "directly above" the other part, but also the case where there is another part in between. Conversely, when it is said that a part such as a layer, film, region or plate is "under" another part, this includes not only the case where it is "directly below" the other part, but also the case where there is another part in between.

[0046] It should be understood that the examples and drawings are merely examples of the present invention and do not represent all of the technical ideas of the present invention, and that various equivalents and modifications may be substituted for them.

[0047] When describing the present invention, if it is determined that a detailed description of a known configuration or function may obscure the gist of the present invention, the detailed description will be omitted.

[0048] Since the drawings are provided to more completely explain the present invention to those skilled in the art, the shape, size, and number of components in the drawings may be exaggerated, omitted, or schematically illustrated for clearer explanation. The shape, size, ratio, and number of each component in the drawings do not entirely reflect the actual shape, size, ratio, and number of each component.

[0049]

[0050] (Example 1)

[0051] FIG. 1 is a schematic diagram illustrating a wire-type three-electrode secondary battery according to some embodiments.

[0052] Fig. 2 is a cross-sectional view taken along the cutting line I-I' of Fig. 1.

[0053] FIG. 3 is a schematic drawing of an electrode assembly included in a wire-type three-electrode secondary battery according to some embodiments.

[0054] FIG. 4 is a schematic drawing showing a support included in a wire-type three-electrode secondary battery according to some embodiments.

[0055] FIG. 5 is a schematic diagram illustrating a reference electrode included in a wire-type three-electrode secondary battery according to some embodiments.

[0056] FIG. 6 is a schematic drawing showing, in some embodiments, an electrode assembly wound around a support.

[0057] FIG. 9 is a schematic drawing showing, in some embodiments, a second separator covering an electrode assembly.

[0058] Referring to FIGS. 1 to 6 and 9, a wire-type three-electrode secondary battery (1000) according to some embodiments may include a support (1200), a reference electrode (1100), an electrode assembly (1300), a second separator (1400), and packaging (1500).

[0059] Referring to FIG. 4, in some embodiments, the support (1200) may have a hollow tubular structure and include a plurality of holes (1200H2) on the surface. The support (1200) may include an internal space (1200H1) into which a reference electrode (1100) may be inserted.

[0060] Since the support (1200) provides an internal space (1200H1), the reference electrode (1100) can be integrated with the electrode assembly (1300) into the wire-type three-electrode secondary battery (1000). Accordingly, the wire-type three-electrode secondary battery (1000) can stably perform three-electrode measurements even when there is physical movement. Consequently, the wire-type three-electrode secondary battery (1000) can be advantageous in predicting and analyzing the electrochemical behavior of the positive and negative electrodes in situations where it is applied to wearable devices, flexible devices, etc.

[0061] Since the support (1200) includes a plurality of holes (1200H2) on the surface, the electrolyte injected into the internal space (1200H1) of the support (1200) during the manufacturing step of the wire-type three-electrode secondary battery (1000) can freely enter and exit through the plurality of holes (1200H2).

[0062] The support (1200) can be the basis of the wire-shaped shape of the wire-shaped three-electrode secondary battery (1000). The support (1200) can prevent deformation, collapse, destruction, etc. of the wire-shaped three-electrode secondary battery (1000) even when physical movement occurs in the wire-shaped three-electrode secondary battery (1000). The support (1200) can provide flexibility and / or resilience to the wire-shaped three-electrode secondary battery (1000). The higher the flexibility and / or resilience of the support (1200), the more desirable it may be. The support (1200) may be an insulator.

[0063] In some embodiments, the material of the support (1200) may be one or more of polyethylene, polypropylene, polytetrafluoroethylene, polyvinylidene fluoride, polyacrylonitrile, polyimide, polyethylene terephthalate, polyamide imide, polyester imide, polyether sulfone, and polysulfone.

[0064] Referring to FIG. 2, in some embodiments, the reference electrode (1100) may be inserted into the interior of the support (1200). Referring to FIG. 5, in some embodiments, the reference electrode (1100) may include a reference electrode active material layer (1110) and a metal wire (1120).

[0065] The reference electrode active material layer (1110) may surround one side of the metal wire (1120). In some embodiments, the reference electrode active material layer (1110) may include one or more of lithium metal and lithium titanium oxide.

[0066] Although FIG. 5 illustrates one metal wire (1120), this is merely exemplary and the number of metal wires (1120) may be plural. As a non-limiting example, the number of metal wires (1120) may be two, and the two metal wires (1120) may be twisted with each other. The material of the metal wire (1120) may be a metal with excellent conductivity. As a non-limiting example, the material of the metal wire (1120) may be copper or nickel-coated copper.

[0067] Referring to FIGS. 1, 6, and 9, in some embodiments, a portion of the reference electrode (1100) may be located inside the support (1200) and the remainder may be located outside the support (1200). In some embodiments, an insulating layer may surround a portion of the reference electrode (1100) located inside the support (1200). The reference electrode active material layer (1110) may be located inside the support (1200). A portion of the metal wire (1120) may be located inside the support (1200) and the remainder may be located outside the support (1200). A portion of the metal wire (1120) located outside the support (1200) may become a reference electrode tab that is electrically connected to the reference electrode (1200) during three-electrode measurement.

[0068] Referring to FIG. 2, in some embodiments, the electrode assembly (1300) may be wound around the support (1200). In some embodiments, the electrode assembly (1300) may be in a sheet shape. Referring to FIGS. 2 and 3, in some embodiments, the electrode assembly (1300) may include a first electrode (1310), a first separator (1330), and a second electrode (1320). The first electrode (1310), the first separator (1330), and the second electrode (1320) may be sequentially stacked with respect to the support (1200). The electrical polarities of the first electrode (1310) and the second electrode (1320) may be opposite to each other.

[0069] The first electrode (1310) may include a first electrode current collector (1310CC). The first electrode current collector (1310CC) may be positioned on a support (1200). The first electrode current collector (1310CC) may include a material that is conductive without causing a chemical change in the electrode that is ultimately manufactured. As a non-limiting example, the first electrode current collector (1310CC) may include aluminum, copper, stainless steel, nickel, titanium, or calcined carbon. As a non-limiting example, the first electrode current collector (1310CC) may include aluminum, copper, and stainless steel that are surface-treated with carbon, nickel, titanium, silver, or the like. A micro-roughened structure may be formed on the surface of the first electrode current collector (1310CC) to increase adhesion with the first electrode active material layer (1310AML). The first electrode current collector (1310CC) may be in a sheet shape. The thickness of the first electrode current collector (1310CC) may be in the range of about 3 μm to about 500 μm.

[0070] The first electrode (1310) may include a first electrode active material layer (1310AML). The first electrode (1310) may be a positive electrode or a negative electrode. The first electrode active material layer (1310AML) may be positioned on a first current collector (1310CC). The first electrode active material layer (1310AML) may include an electrode active material, a binder, and a conductive material. The first electrode active material layer (1310AML) may be in a sheet form.

[0071] If the first electrode (1310) is a positive electrode, the first electrode active material layer (1310AML) may include a positive electrode active material. As a non-limiting example, the positive electrode active material may be a lithium-iron oxide (e.g., LiFePO4, etc.), a lithium-manganese oxide (e.g., LiMnO2, LiMn2O4, etc.), a lithium-cobalt oxide (e.g., LiCoO2, etc.), a lithium-nickel oxide (e.g., LiNiO2, etc.), a lithium-nickel-manganese oxide (e.g., LiNi 1-y1 Mny1 O2 (here, 0 <y1<1) 및 LiMn 2-z1 Ni z1 O4 (where 0<z1<2), etc.), lithium-nickel-cobalt oxides (e.g., LiNi 1-y2 Co y2 O2 (here, 0 <y2<1) 등), 리튬-망간-코발트계 산화물(예를 들면, LiCo 1-y3 Mn y3 O2 (here, 0 <y3<1) 및 LiMn 2-z2 Co z2 O4 (where 0<z2<2) etc.), lithium-nickel-manganese-cobalt oxides (e.g., Li(Ni p1 Co q1 Mn r1 )O2(where, 0<p1<1, 0<q1<1, 0<r1<1, p1+q1+r1=1), Li(Ni p2 Co q2 Mn r2 )O4 (wherein, 0<p2<2, 0<q2<2, 0<r2<2, p2+q2+r2=2) etc.) and lithium-nickel-cobalt-manganese-metal (M) oxides (e.g., Li(Ni p3 Co q3 Mn r3 M s1 )O2 (wherein, M is selected from the group consisting of Al, Cu, Fe, V, Cr, Ti, Zr, Zn, Ta, Nb, Mg, B, W and Mo, and 0<p3<1, 0<q3<1, 0<r3<1, 0<s1<1, p3+q3+r3+s1=1), etc.) may include one or more of the following.

[0072] If the first electrode (1310) is a negative electrode, the first electrode active material layer (1310AML) may include a negative electrode active material. As a non-limiting example, the negative electrode active material may include lithium metal; graphite-based carbon materials such as natural graphite or artificial graphite in an amorphous, plate-like, flaky, spherical or fibrous form; amorphous carbon materials such as soft carbon and hard carbon; metals such as Cu, Ni, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al and Sn or alloys of the metals and lithium; PbO, PbO2, Pb2O3, Pb3O4, Sb2O3, Sb2O4, Sb2O5, GeO, GeO2, Bi2O3, Bi2O4, Bi2O5, Li x Fe2O3(0≤x≤1), Li x WO2(0≤x≤1), Sn x Me 1-x Me' y O z (Me: Mn, Fe, Pb, Ge; Me': Al, B, P, Si, elements of group 1, 2, and 3 of the periodic table, halogens; 0 <x≤1; 1≤y≤3; 1≤z≤8); Si, SiO x (0 <x≤2), Si-Y 합금(상기 Y는 알칼리 금속, 알칼리 토금속, 13족 원소, 14족 원소, 전이금속, 희토류 원소 및 이들의 조합으로 이루어진 군에서 선택되는 원소이며, Si은 아님), Sn, SnO2, Sn-Y(상기 Y는 알칼리 금속, 알칼리 토금속, 13족 원소, 14족 원소, 전이금속, 희토류 원소 및 이들의 조합으로 이루어진 군에서 선택되는 원소이며, Sn은 아님) 중 하나 이상을 포함할 수 있다.

[0073] As non-limiting examples, the binder may include one or more of polyvinylidene fluoride, polyvinyl alcohol, carboxymethylcellulose, starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene terpolymer, sulfonated ethylene-propylene-diene terpolymer, styrene-butadiene rubber, and styrene-butadiene rubber-carboxymethylcellulose fluoroelastomer.

[0074] As non-limiting examples, the conductive material may include one or more of carbon nanotubes; graphite; carbon-based materials such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, and thermal black; conductive fibers such as carbon fibers or metal fibers; metal powders such as carbon fluoride, aluminum, and nickel powders; conductive whiskies such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; and polyphenylene.

[0075] The first separator (1330) may be positioned between the first electrode active material layer (1310AML) and the second electrode active material layer (1320AML). The first separator (1330) may be in a sheet shape. As a non-limiting example, the first separator (1330) may include a porous polymer substrate made of a polyolefin polymer selected from the group consisting of ethylene homopolymer, propylene homopolymer, ethylene-butene copolymer, ethylene-hexene copolymer, and ethylene-methacrylate copolymer; a porous polymer substrate made of a polymer selected from the group consisting of polyester, polyacetal, polyamide, polycarbonate, polyimide, polyetheretherketone, polyethersulfone, polyphenylene oxide, polyphenylene sulfide, and polyethylene naphthalate; It may be a porous coating layer formed of a mixture of inorganic particles and a binder polymer on at least one surface of the porous polymer substrate; or a porous substrate formed of a mixture of inorganic particles and a binder polymer.

[0076] The second electrode (1320) may include a second electrode active material layer (1320AML). The second electrode (1320) may be a positive electrode or a negative electrode. If the first electrode (1310) is a positive electrode, the second electrode (1320) may be a negative electrode, and if the first electrode (1310) is a negative electrode, the second electrode (1320) may be a positive electrode. The second electrode active material layer (1320AML) may be positioned on the first separator (1330). The second electrode active material layer (1320AML) may include an electrode active material, a binder, and a conductive material. The electrode active material, binder, and conductive material that the second electrode active material layer (1320AML) may include are the same as those described above for the first electrode active material layer (1310AML). The second electrode active material layer (1320AML) may be in a sheet form.

[0077] The second electrode (1320) may include a second electrode current collector (1320CC). The second electrode current collector (1320CC) may be positioned on a second electrode active material layer (1320AML). The materials that the second electrode current collector (1320CC) may include and the structure of the second electrode current collector (1320CC) are the same as those described above for the first electrode current collector (13200CC).

[0078] Referring to FIGS. 1, 6, and 9, the first electrode tab (1310T) and the second electrode tab (1320T) may protrude from both ends of the wire-type three-electrode secondary battery (1000). One of the first electrode tab (1310T) and the second electrode tab (1320T) may be located on the same side as the reference electrode tab. However, alternatively, the first electrode tab (1310T) and the second electrode tab (1320T) may protrude from one end of the wire-type three-electrode secondary battery (1000). In addition, both the first electrode tab (1310T) and the second electrode tab (1320T) may be located on the same side as the reference electrode tab.

[0079] The first electrode tab (1310T) may be connected to the first electrode current collector (1310CC) by welding or the like. The second electrode tab (1320T) may be connected to the second electrode current collector (1320CC) by welding or the like. In the case of three-electrode measurement, an electrical connection to the first electrode (1310) may be made through the first electrode tab (1310T). In the case of three-electrode measurement, an electrical connection to the second electrode (1320) may be made through the second electrode tab (1320T).

[0080] Referring to FIG. 6, the electrode assembly (1300) may be wound around the support (1200) so as not to overlap in a spiral manner. In general, the electrode assembly (1300) may have lower flexibility and / or resilience than the support (1200). Therefore, the electrode assembly (1300) may be wound around the support (1200) so as not to overlap in a spiral manner to increase the flexibility and / or resilience of the wire-type three-electrode secondary battery (1000). The gap between the electrode assemblies (1300) wound around the support (1200) so as not to overlap in a spiral manner may be in a range of twice the width (W) of the electrode assembly (1300). If the gap is too large, the performance, such as the capacity, of the wire-type three-electrode secondary battery (1000) may be reduced.

[0081] Referring to FIG. 9, in some embodiments, the second separator (1400) may cover the electrode assembly (1300). The second separator (1400) may not cover the support (1200). In the present specification, "A covers B" means that A directly contacts B and covers B so that B is not visible from the outside. The second separator (1400) may be wound around the support (1200) along the electrode assembly (1300) so as not to overlap in a spiral manner.

[0082] As a non-limiting example, in the manufacturing process of a wire-type three-electrode secondary battery (1000), the second separator (1400) may be wound around the support (1200) along the electrode assembly (1300) after the electrode assembly (1300) is wound around the support (1200).

[0083] As a non-limiting example, the second separator (1400) may be a part of the electrode assembly (1300). That is, the electrode assembly (1300) may be a laminate in which a first electrode (1310), a first separator (1300), a second electrode (1320), and a second separator (1400) are sequentially laminated. In this case, in the manufacturing process of the wire-type three-electrode secondary battery (1000), the second separator (1400) may be wound on the support (1200) when the electrode assembly (1300) is wound on the support (1200). The second separator (1400) may be positioned on the second electrode current collector (1320CC).

[0084] The material and structure of the second separator (1400) are the same as those described above for the first separator (1330).

[0085] Referring to FIGS. 1 and 2, the packaging (1500) can cover the second separator (1400). The packaging (1500) can protect all components except the first electrode tab (1310T), the second electrode tab (1320T), and the reference electrode tab from the external environment.

[0086] In some embodiments, the packaging (1500) may include a pouch made of a polymeric material. As a non-limiting example, the pouch made of the polymeric material may include one or more of PET, PVC, HDPE, and epoxy resin.

[0087] In some embodiments, the packaging (1500) may additionally include a moisture barrier layer, an insulation layer, and a thermal bonding layer. As a non-limiting example, the moisture barrier layer may include a metal such as aluminum. As a non-limiting example, the insulation layer may include polyester or polyamide. As a non-limiting example, the thermal bonding layer may include polypropylene, polycarbonate, polyethylene, or the like.

[0088]

[0089] (Example 2)

[0090] For the second embodiment, only the parts that differ from the first embodiment will be described.

[0091] FIG. 7 is a schematic drawing showing an electrode assembly wound around a support in some other embodiments.

[0092] FIG. 8 is a schematic drawing of a portion of an electrode assembly wound to overlap a support in some other embodiments.

[0093] Referring to FIGS. 7 and 8, the electrode assembly (1300) may be wound around the support (1200) in a spiral shape. However, as described above, the electrode assembly (1300) may generally have lower flexibility and / or resilience than the support (1200), and thus, if the electrode assemblies (1300) overlap too much, the flexibility and / or resilience of the wire-type three-electrode secondary battery (1000) may be significantly reduced. In some embodiments, the electrode assemblies (1300) may overlap in a range of 0.1 to 0.5 times the width (W) of the electrode assemblies (1300). Referring to FIG. 8, the length of the overlapping width (OL) may be in a range of 0.1 to 0.5 times the width (W) of the assembly (1300).

[0094] The second embodiment may have lower flexibility and / or resilience than the first embodiment, but may have higher performance, such as capacity, than the first embodiment.

[0095]

[0096] (Example 3)

[0097] For the third embodiment, only the parts that differ from the first embodiment will be described.

[0098] FIG. 10 is a schematic drawing showing, in some other embodiments, a second separator covering an electrode assembly.

[0099] Referring to FIG. 10, in some embodiments, the second separator (1400) may cover not only the electrode assembly (1300) but also the support (1200).

[0100] The third embodiment may be safer than the first embodiment.

[0101]

[0102] The above description is intended solely to illustrate the present invention. The scope of the present invention should be interpreted in accordance with the claims, and all technical ideas within the scope equivalent or equivalent thereto should be construed as being included within the scope of the present invention.

[0103]

[0104] [Explanation of symbols]

[0105] 1000: Wire-type three-electrode secondary battery

[0106] 1100: Reference electrode

[0107] 1110: Reference electrode active material layer

[0108] 1120: Metal wire

[0109] 1200: Support

[0110] 1200H1: Interior space

[0111] 1200H2: Hall

[0112] 1300: Electrode assembly

[0113] 1310: First electrode

[0114] 1310CC: First electrode current collector

[0115] 1310AML: First electrode active material layer

[0116] 1320: Second electrode

[0117] 1320CC: Second electrode current collector

[0118] 1320AML: Second electrode active material layer

[0119] 1330: First membrane

[0120] 1400: Second membrane

[0121] 1500: Packaging

Claims

1. A support having a hollow cylinder structure and including a plurality of holes on the surface; a reference electrode inserted into the interior of the support; and An electrode assembly wound on the above support; A wire-type three-electrode secondary battery comprising:

2. In claim 1, The above reference electrode includes a reference electrode active material layer on one side, The above reference electrode active material layer is located inside the support. A wire-type three-electrode secondary battery, wherein the other side of the reference electrode, which is the opposite side of one side of the reference electrode, is located outside the support.

3. In claim 2, A wire-type three-electrode secondary battery, wherein the reference electrode active material layer comprises at least one of lithium metal and lithium titanium oxide.

4. In claim 1, The electrode assembly comprises a first electrode, a first separator, and a second electrode, The first electrode, the first separator, and the second electrode are sequentially stacked based on the support, A wire-type three-electrode secondary battery in which the electrical polarities of the first electrode and the second electrode are opposite to each other.

5. In claim 1, A wire-type three-electrode secondary battery including a second separator covering the electrode assembly.

6. In claim 5, The above second separator is a wire-type three-electrode secondary battery that also covers the support.

7. In claim 5, A wire-type three-electrode secondary battery including a packaging covering the second separator.

8. In claim 1, The above electrode assembly is a sheet-shaped wire-type three-electrode secondary battery.

9. In claim 8, The above electrode assembly is a wire-type three-electrode secondary battery wound so as not to overlap in a spiral shape.

10. In claim 8, A wire-type three-electrode secondary battery in which the electrode assembly is wound in a spiral manner so as to overlap by a range of 0.1 to 0.5 times the width of the electrode assembly.

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