Current collector

Abstract

Disclosed in the present specification are a current collector and uses thereof. The current collector comprises a polymer layer which exhibits a so-called positive temperature coefficient (PTC) effect at a required level when needed, and thus can be appropriately applied in applications where stability due to abnormally high heat and / or flames is problematic. The polymer layer of the current collector can quickly exhibit the PTC effect when the PTC effect is needed. The present specification also discloses uses of the current collector.

Description

Whole house

[0001] This application claims the benefit of priority to Korean Patent Application No. 10-2024-0012285, dated January 26, 2024, and Korean Patent Application Nos. 10-2024-0126162, 10-2024-0126161, and 10-2024-0126164, dated September 13, 2024, the entire contents of which are incorporated herein by reference.

[0002] This specification discloses a collector and its uses.

[0003] Energy storage technology is expanding its application areas to include mobile phones, tablets, laptops, and even electric vehicles.

[0004] As the data processing speed of mobile devices such as cell phones and tablets increases and their usage time increases, development of secondary batteries with high energy density and operating potential, long cycle life, and low self-discharge rate is underway.

[0005] As major developed countries curb the production of vehicles powered by internal combustion engines to address global warming and air pollution, major automakers are also developing various electric vehicles. As such, the importance of secondary batteries with high energy density, high discharge voltage, and output stability as power sources is increasing.

[0006] In line with the above trend, the frequency of fire or explosion accidents caused by overcharging, exposure to high temperatures, or external impact in devices or automobiles that use secondary batteries as an energy source is also increasing.

[0007] A major cause of these accidents is known to be a short circuit, which occurs when the positive and negative electrodes within the electrode assembly come into direct contact, primarily due to external stimuli. This short circuit can occur when a secondary battery is overcharged, exposed to high temperatures, or exposed to external stimuli, resulting in shrinkage of the separator due to an increase in the battery's internal temperature, or destruction of the battery's internal structure due to external impact.

[0008] When a short circuit occurs, the movement of lithium ions and electrons is concentrated at the point where the positive and negative electrodes are in direct contact, potentially accelerating internal heat generation. This is known to generate gases and other substances within the battery, causing its volume to expand and increasing the risk of fire.

[0009] The present specification discloses a current collector and its uses. The purpose of the present specification is to disclose a current collector with a polymer layer that can rapidly exhibit the so-called PTC (Positive Temperature Coefficient) effect at a required level at a required time, thereby ensuring stability in applications where stability due to abnormally high temperatures and / or flames is a concern. Another purpose of the present specification is to disclose uses of the current collector.

[0010] In this specification, the term room temperature means a natural temperature that is not artificially heated or cooled, and may mean, for example, any temperature within the range of 10°C to 30°C, or a temperature of about 23°C, about 25°C, or about 27°C.

[0011] Among the properties mentioned in this specification, properties that are affected by the measurement temperature are properties measured at room temperature, unless otherwise specified.

[0012] The unit of temperature referred to in this specification is Celsius (℃) unless otherwise specified.

[0013] In this specification, the term atmospheric pressure means a natural pressure that has not been artificially pressurized or depressurized, and can typically mean a pressure of about 730 mmHg to 790 mmHg.

[0014] Among the properties mentioned in this specification, the properties affected by the measurement pressure are properties measured at the atmospheric pressure, unless otherwise specified.

[0015] Among the properties mentioned in this specification, properties affected by measured humidity are properties measured at room temperature and pressure and at humidity that is not artificially controlled, unless otherwise specified.

[0016] In this specification, the term normal state means the normal operating state (e.g., normal charging or discharging state of a secondary battery) and / or storage state of an electrical / electronic device such as a secondary battery.

[0017] The term "abnormal state" as used herein refers to a state in which abnormal heat generation, ignition, and / or explosion occurs in an electrical / electronic device such as a secondary battery, or a state in which the risk of such abnormal heat generation, ignition, and / or explosion increases. For example, a state in which abnormal heat generation, ignition, or explosion occurs in a secondary battery due to a short circuit phenomenon, or a dangerous state in which the risk of such heat generation, ignition, or explosion increases may be considered an abnormal state.

[0018] This specification discloses a whole house.

[0019] The current collector may include a current collector body and a polymer layer formed on the current collector body. The current collector may be, for example, a current collector for an electrode used in forming an electrode. For example, an electrode formed using the current collector may include the current collector body and an active material layer formed on the polymer layer of the current collector body. Fig. 1 is a cross-sectional view of a current collector including a current collector body (100) and a polymer layer (200), and Fig. 2 is a cross-sectional schematic diagram showing an electrode in which an active material layer (1003) is formed on a polymer layer (1002) of the current collector body (1001).

[0020] As shown in the drawing, the current collector body (100) and the polymer layer (200), and the polymer layer (200) and the active material layer (300) in the current collector or electrode may be in contact with each other. In some cases, other elements may exist between the current collector body (100) and the polymer layer (200) or between the polymer layer (200) and the active material layer (300). In addition, although the drawing shows a case where the active material layer (300) exists only on one side of the current collector body (100), the active material layer (300) may exist on both sides of the current collector body (100). In this case, the polymer layer (200) may exist in two layers between each of the active material layers (300) present on both sides of the current collector body (100) and the current collector body (100), or may exist in one layer between any one of the active material layers (300) present on both sides and the current collector body (100).

[0021] The electrode formed by the above-mentioned collector may be an anode or a cathode applied to a secondary battery.

[0022] The polymer layer exhibits the so-called PTC (positive temperature coefficient) effect. Therefore, the polymer layer can variably control the movement of charges through the electrode depending on the temperature.

[0023] By applying such a polymer layer, the electrode having the current collector exhibits excellent electrical characteristics including low resistance in a normal state, and can secure stability through an increase in resistance in an abnormal state.

[0024] In order for a polymer layer to be applied to an electrode and exhibit the above-described effect, the tendency of the PTC effect exhibited by the polymer layer must be controlled. The PTC effect is an effect in which resistance increases in response to changes in temperature and / or voltage. In order for an electrode to which a polymer layer having the PTC effect is applied to operate stably and ensure stability under abnormal conditions, the electrical characteristics before the resistance increases due to the PTC effect and the point in time when the resistance increases due to the PTC effect must be adjusted.

[0025] For example, if the resistance of the polymer layer is excessively high under normal conditions, it can adversely affect the operation of the secondary battery. Furthermore, if the temperature at which the PTC effect manifests falls within the normal temperature range, the secondary battery's performance cannot be properly realized.

[0026] The above polymer layer has a PTC effect, the timing of the PTC effect's occurrence is controlled, and stable electrical characteristics are maintained before the PTC effect's occurrence.

[0027] To achieve this PTC effect, a specific conductive polymer can be introduced into the polymer layer. Furthermore, by introducing a conductive material into the polymer layer and uniformly dispersing it, oxidation potential and electrical properties can be appropriately maintained. Furthermore, through the appropriate application and dispersion of the conductive material, coatability can be secured and a uniform polymer layer can be formed.

[0028] For example, the above-described collector or an electrode including the collector may exhibit a predetermined result in an ARC (Accelerated Rate Calorimeter) test. The ARC test may be performed in the manner described in “Test Example 5” of the present specification.

[0029] For example, the current collector or an electrode including the current collector can be adjusted to determine the time point at which the TR generation temperature is determined in the ARC test. The TR generation temperature is the time required until the temperature change rate reaches 1°C / minute in the ARC test performed in the manner described in "Test Example 5" of this specification.

[0030] In one example, the lower limit of the time point at which the TR occurrence temperature is confirmed may be approximately 30 hours, 31 hours, 32 hours, 33 hours, 34 hours, 35 hours, 36 hours, or 37 hours, and the upper limit may be approximately 50 hours, 45 hours, 40 hours, or 38 hours. The time point may be within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above; or within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above and equal to or less than any upper limit arbitrarily selected from the upper limits listed above. The longer the time point at which the TR occurrence temperature is confirmed, the more effectively the collector or the electrode including the collector has dealt with an abnormality in an abnormal state.

[0031] In one example, the current collector or the electrode including the current collector may be controlled such that the TR generation temperature in the ARC test is controlled to a certain level. For example, the lower limit of the TR generation temperature may be approximately 60°C, 80°C, 100°C, 120°C, 140°C, 160°C, or 170°C, and the upper limit may be approximately 250°C, 200°C, or 180°C. The temperature may be within a range that is lower than or lower than any upper limit arbitrarily selected from the upper limits listed above; or within a range that is higher than or higher than any lower limit arbitrarily selected from the lower limits listed above and lower than or lower than any upper limit arbitrarily selected from the upper limits listed above. The lower the TR generation temperature, the more effectively the current collector or the electrode including the current collector has dealt with an abnormality in an abnormal state.

[0032] In one example, the current collector or the electrode including the current collector may be controlled to a certain level in the maximum temperature confirmed in the ARC test. For example, the lower limit of the TR generation temperature may be approximately 200°C, 250°C, 300°C, or 350°C, and the upper limit may be approximately 410°C, 400°C, 390°C, 380°C, 370°C, or 360°C. The temperature may be within a range that is lower than or lower than any upper limit arbitrarily selected from the upper limits listed above; or within a range that is higher than or higher than any lower limit arbitrarily selected from the lower limits listed above and lower than or lower than any upper limit arbitrarily selected from the upper limits listed above. The lower the TR generation temperature, the more effectively the current collector or the electrode including the current collector has dealt with an abnormality in an abnormal state.

[0033] In one example, the current collector or the electrode including the current collector can have a metal migration ratio in an impact test adjusted within a predetermined range. The metal migration ratio is the ratio of metal (e.g., metal of the current collector of the counter electrode) migrating to the current collector or electrode via the separator in the impact test described in the "Test Example 6" section of the present specification, and is expressed as a unit area of ​​1 cm of the surface of the current collector or electrode. 2 This refers to the ratio of the metal transferred to the current collector present in the present invention. In the above "Test Example 6", the electrode to which the current collector disclosed in this specification is applied is used as the positive electrode, and the positive electrode is laminated with the negative electrode via a separator and subjected to the impact test, and then the area of ​​the negative electrode current collector (Cu foil) to which the metal has transferred is evaluated. In this case, the metal is Cu.

[0034] In one example, the lower limit of the ratio of the above metal transition rate is 1 cm per unit area. 2 The content may be about 0 wt%, 0.0001 wt%, 0.0005 wt%, 0.001 wt%, 0.005 wt% or 0.01 wt%, and the upper limit may be about 0.35 wt%, 0.3 wt%, 0.25 wt%, 0.2 wt%, 0.15 wt%, 0.1 wt%, 0.09 wt%, 0.08 wt%, 0.07 wt%, 0.06 wt%, 0.05 wt%, 0.04 wt%, 0.03 wt%, 0.02 wt% or 0.015 wt%. The ratio is within a range that is equal to or less than any one upper limit arbitrarily selected from the upper limits listed above; Or, it may be within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above, and equal to or less than any upper limit arbitrarily selected from the upper limits listed above. The lower the ratio, the more effectively the collector or the electrode including the collector effectively copes with abnormalities in an abnormal state.

[0035] In one example, the current collector or an electrode including the current collector may exhibit a certain level of PTC onset temperature (Positive Temperature Coefficient on set temperature). The PTC onset temperature (Positive Temperature Coefficient on set temperature) is measured in the manner described in "Test Example 3" of the present specification, and is the temperature at which a significant increase in resistance occurs in the current collector or an electrode including the current collector.

[0036] In one example, the lower limit of the PTC start temperature may be about 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, or 100°C, and the upper limit may be about 200°C, 180°C, 160°C, 140°C, 120°C, 110°C, or 100°C. The PTC start temperature may be in a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above, and equal to or less than any upper limit arbitrarily selected from the upper limits listed above. The PTC start temperature is a suitable temperature range when the current collector or the like is applied to a secondary battery, for example, and this can be adjusted by controlling the composition of the polymer layer (e.g., whether a conductive material is included) and / or the composition of the conductive polymer included in the polymer layer (e.g., monomer composition).

[0037] In one example, the above-described collector or an electrode including the collector may exhibit a rapid resistance increase rate at a point where the PTC start temperature (Positive Temperature Coefficient on set temperature) is exceeded. The resistance increase rate is measured by the method described in “Test Example 3” of the present specification.

[0038] In one example, the lower limit of the resistance rising rate may be about 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1,000, or 1,100, and the upper limit may be about 5,000, 4,500, 4,000, 3,500, 3,000, 2,500, 2,000, 1,500, 1,000, 800, or 600. The upper limit of the resistance rising rate is ohms / sec. The resistance rising rate is within a range that is equal to or greater than any one lower limit arbitrarily selected from the lower limits listed above; Or, it may be within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above, and equal to or less than any upper limit arbitrarily selected from the upper limits listed above. The speed is a range that can effectively respond to the occurrence of an abnormal state, and this can be adjusted by controlling the composition of the polymer layer (e.g., whether a conductive material is included) and / or the composition of the conductive polymer included in the polymer layer (e.g., monomer composition).

[0039] The above characteristics can be achieved by introducing a polymer layer.

[0040] In one example, a polymer layer exhibiting the above characteristics can have a 2θ peak confirmed within an appropriate range in XRD (X-ray diffraction) analysis. The XRD analysis can be performed as described in the “Test Example 1” section of this specification.

[0041] For example, the lower limit of the range in which the 2θ peak appears may be about 3.4 degrees, 3.6 degrees, or 3.8 degrees, and the upper limit may be about 5 degrees, 4.8 degrees, 4.6 degrees, 4.4 degrees, 4.2 degrees, 4.0 degrees, or 3.9 degrees. The range may be a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above, and equal to or less than any upper limit arbitrarily selected from the upper limits listed above.

[0042] For example, the polymer layer may have a d-spacing of the (100) plane within a predetermined range in the XRD (X-ray diffraction) analysis. For example, the lower limit of the d-spacing may be about 1.8 nm, 1.9 nm, 2.0 nm, 2.1 nm, 2.2 nm, or 2.3 nm, and the upper limit may be about 2.6 nm, 2.5 nm, 2.4 nm, or 2.3 nm. The range may be a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above, and is equal to or less than any upper limit arbitrarily selected from the upper limits listed above.

[0043] The position and / or d-spacing of the 2θ peak in the above XRD analysis represent the intermolecular distance of the polymer (conductive polymer) within the polymer layer. As the intermolecular distance becomes closer, the electrical properties improve, but the effect of the PTC effect expression decreases, and as the intermolecular distance becomes farther away, the temperature at the start of the PTC decreases. Therefore, the desired effect can be achieved by controlling the intermolecular distance so that the above characteristics appear. This intermolecular distance can be achieved by controlling the composition of the conductive polymer.

[0044] As the above-mentioned current collector body, one that is commonly used as a current collector body for a positive or negative electrode can be used without any special restrictions.

[0045] As for the current collector body, as long as it is conductive and does not cause chemical changes in an application device such as a secondary battery, its type, size, shape, etc. are not particularly limited. Examples of materials that can be used as the current collector body include copper, aluminum, stainless steel, nickel, titanium, or sintered carbon, or materials whose surfaces are copper, aluminum, or stainless steel and are surface-treated with carbon, nickel, titanium, or silver, etc. The current collector body may be in the form of a film, sheet, foil, net, porous body, foam, or non-woven body containing the above material. In some cases, a known surface treatment may be performed on the surface of the current collector body to improve adhesion to other layers such as a polymer layer or an active material layer.

[0046] The entire body of the collector may have a thickness typically within a range of 3 μm to 500 μm, but is not limited thereto.

[0047] The polymer layer is present on one or both sides of the above-mentioned main body.

[0048] The term polymer layer refers to a layer containing a polymer. The lower limit of the content of the polymer in the polymer layer may be about 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 or 95, and the upper limit may be about 100, 95, 90, 85, 80, 75, 70, 65, 60, 55 or 50. The content is the content of the polymer based on the total weight of the polymer layer, and the unit is weight%. The content may be within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above; or may be within a range that is equal to or less than any upper limit arbitrarily selected from the upper limits listed above, and equal to or greater than any lower limit arbitrarily selected from the lower limits listed above.

[0049] The polymer layer may not be a so-called electrode active material layer. The content of the electrode active material within the polymer layer may be controlled. For example, the upper limit of the content of the electrode active material within the polymer layer may be about 10, 9, 8, 7, 6, 5, 4, 3, 2, 1, 0.5, 0.1, 0.05, 0.01, 0.005, or 0.001, and the lower limit may be 0. The content is the content of the electrode active material based on the total weight of the polymer layer, and the unit is weight%. The content may be within a range that is less than or equal to any upper limit arbitrarily selected from the upper limits listed above; or may be within a range that is less than or equal to any upper limit arbitrarily selected from the upper limits listed above, but greater than or equal to the lower limit described above.

[0050] The polymer layer may include a conductive polymer. As is well known, a conductive polymer is a polymer that exhibits conductivity due to a conjugated system and / or doping of a polymer chain. For example, the conductive polymer may be a polymer that exhibits low resistance in a doped state and high resistance in a de-doped state, and may be a polymer designed so that the transition between the doped and de-doped states can occur quickly at a necessary point in time in response to temperature and / or voltage.

[0051] The lower limit of the content of the conductive polymer in the polymer layer may be about 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 or 95, and the upper limit may be about 100, 95, 90, 85, 80, 75, 70, 65, 60, 55 or 50. The content is the content of the conductive polymer based on the total weight of the polymer layer, and the unit is weight%. The content may be within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above; or may be within a range that is equal to or less than any upper limit arbitrarily selected from the upper limits listed above, and equal to or greater than any lower limit arbitrarily selected from the lower limits listed above.

[0052] The thickness of the polymer layer can be appropriately controlled depending on the purpose. For example, the lower limit of the thickness of the polymer layer can be about 10 nm, 50 nm, 100 nm, 150 nm, 200 nm, 250 nm, 300 nm, 350 nm, 400 nm, 450 nm, 500 nm, 550 nm or 600 nm, and the upper limit can be about 2 μm, 1.5 μm, 1 μm, 950 nm, 900 nm, 850 nm, 800 nm, 750 nm, 700 nm, 650 nm, 600 nm, 550 nm, 500 nm, 450 nm or 400 nm. The above thickness may be within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above and equal to or less than any upper limit arbitrarily selected from the upper limits listed above.

[0053] The conductive polymer included in the above polymer layer may be a thiophene polymer (or polythiophene).

[0054] The term thiophene polymer or polythiophene refers to a polymer containing a certain level or more of thiophene monomer units.

[0055] For example, the lower limit of the ratio of the number of moles of thiophene monomer units in the thiophene polymer may be about 50 mol%, 55 mol%, 60 mol%, 65 mol%, 70 mol%, 75 mol%, 80 mol%, 85 mol%, 90 mol% or 95 mol%, and the upper limit may be about 100 mol%, 95 mol%, 90 mol%, 80 mol%, 75 mol%, 70 mol%, 65 mol%, 60 mol%, 55 mol% or 50 mol%. The ratio of the number of moles of the thiophene monomer units is the number of moles (M) of all monomer units present in the thiophene polymer or the number of moles (M) of all monomers applied to prepare the thiophene polymer. T ) or the ratio of the mole number (MT) of all thiophene monomers applied to prepare the above thiophene polymer (100×M T / M). The ratio of the above thiophene monomer unit (100×M T / M) may be within a range that is greater than or equal to any lower limit arbitrarily selected from the lower limits listed above; or within a range that is greater than or equal to any lower limit arbitrarily selected from the lower limits listed above and less than or equal to any upper limit arbitrarily selected from the upper limits listed above.

[0056] The term monomer unit refers to the form in which a monomer is polymerized and incorporated into a polymer. The term thiophene monomer refers to a monomer of the thiophene series, and includes a thiophene skeleton.

[0057] The above conductive polymer may include a long-chain hydrocarbon functional group or a monomer unit having the long-chain hydrocarbon functional group (hereinafter referred to as unit A). The unit A may be a thiophene monomer unit.

[0058] The term long-chain hydrocarbon functional group means a monovalent hydrocarbon group having a certain number of carbon atoms or a monovalent functional group containing the monovalent hydrocarbon group.

[0059] For example, the lower limit of the number of carbon atoms present in the long-chain hydrocarbon functional group (i.e., the number of carbon atoms of the monovalent hydrocarbon group) may be about 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and the upper limit may be about 30, 29, 28, 27, 26, 25, 24, 23, 22, 21, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, or 4. The above carbon number may be within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above; or within a range that is equal to or less than any upper limit arbitrarily selected from the upper limits listed above and equal to or greater than any lower limit arbitrarily selected from the lower limits listed above.

[0060] The above carbon number may be the total number of carbons present in the long-chain hydrocarbon functional group, or the carbon number of the hydrocarbon chain of the straight-chain structure of the functional group. That is, the monovalent hydrocarbon group present in the long-chain hydrocarbon functional group may have a straight-chain or branched-chain structure. When the monovalent hydrocarbon group has a straight-chain structure, the carbon number of the straight-chain structure may be within the above range. When the monovalent hydrocarbon group has a branched-chain structure, the carbon number constituting the longest straight-chain chain in the branched-chain structure may be within the above range. For example, if the branched-chain structure is a 2-ethylhexyl group, the carbon number constituting the longest straight-chain chain is 6.

[0061] Examples of the long-chain hydrocarbon functional group include at least one selected from the group consisting of an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkylcarbonyl group, and an alkylcarbonyloxy group. In a suitable example, the long-chain hydrocarbon functional group may be an alkyl group and / or an alkoxy group.

[0062] The number of carbon atoms present in the alkyl group, alkenyl group, alkynyl group, alkoxy group, alkyl group of the alkylcarbonyl group and alkyl group of the alkylcarbonyloxy group may be in the range of the number of carbon atoms present in the long-chain hydrocarbon functional group (i.e., the number of carbon atoms in the monovalent hydrocarbon group).

[0063] The above alkyl group, alkenyl group, alkynyl group, the above alkoxy group, the alkyl group of the alkylcarbonyl group, and the alkyl group of the alkylcarbonyloxy group may have a straight-chain or branched-chain structure. In the case of a branched chain, the number of carbon atoms constituting the longest straight chain in the branched chain structure may be within the above range.

[0064] The above long-chain hydrocarbon functional group, such as an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkylcarbonyl group or an alkylcarbonyloxy group, may be optionally substituted with one or more substituents.

[0065] Long-chain hydrocarbon functional groups can exhibit enhanced vibrational energy at elevated temperatures. This enhanced vibrational energy can affect the doping and dedoping states of conductive polymers. The degree of the vibrational energy and the temperature at which the vibrational energy appears are affected by the carbon number and arrangement state of the long-chain hydrocarbon functional group. Therefore, by adjusting the carbon number and amount of the long-chain hydrocarbon functional group and adjusting its arrangement state using the manufacturing method described below, the desired properties of the polymer layer can be secured. For example, at the same temperature, the vibrational energy of a relatively long chain is greater than that of a relatively short chain. Therefore, by appropriately employing long and short chains as long-chain hydrocarbon functional groups, a conductive polymer that satisfies the desired effect can be provided.

[0066] In addition, by appropriately adjusting the type and ratio of the long-chain hydrocarbon functional group, the intermolecular distance described above can be adjusted to a desired level.

[0067] Additionally, the long-chain hydrocarbon functional group can provide appropriate mobility to a monomer or polymer during the polymerization process of a conductive polymer, thereby improving polymerization efficiency and coating efficiency.

[0068] For example, the number of moles (M) of the long-chain hydrocarbon functional group relative to the number of moles (M) of the total monomer units of the conductive polymer L ) or the number of moles (M) of monomer units (unit A) having the above functional group L ) can be adjusted. For example, the lower limit of the ratio can be about 20 mol%, 25 mol%, 30 mol%, 35 mol%, 40 mol%, 45 mol%, 50 mol%, 55 mol%, 60 mol%, 65 mol%, 70 mol%, 75 mol%, 80 mol%, 85 mol% or 95 mol%, and the upper limit can be about 100 mol%, 97 mol%, 95 mol%, 90 mol%, 85 mol%, 80 mol%, 75 mol%, 70 mol%, 65 mol% or 60 mol%. The ratio is the number of moles (M) of all long-chain hydrocarbon functional groups present in the conductive polymer relative to the number of moles (M) of all monomer units present in the conductive polymer or the number of moles (M) of all monomers applied to prepare the conductive polymer. L ) or the number of moles of monomer units having the long-chain hydrocarbon functional group (M L ) or the ratio of the mole number (ML) of monomers having all long-chain hydrocarbon functional groups applied to prepare the above thiophene polymer (100×M L / M). The ratio may be within a range that is greater than or equal to any lower limit arbitrarily selected from the lower limits listed above; or within a range that is less than or equal to any upper limit arbitrarily selected from the upper limits listed above and greater than or equal to any lower limit arbitrarily selected from the lower limits listed above.

[0069] The conductive polymer may include a first hydrocarbon functional group and a second hydrocarbon functional group.

[0070] The first hydrocarbon functional group is a functional group having a relatively large number of carbon atoms among the long-chain hydrocarbon functional groups. The lower limit of the carbon atoms of the first hydrocarbon functional group may be about 10, 11, or 12, and the upper limit may be about 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, or 10. The carbon atoms of the first hydrocarbon functional group may be within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above; or may be within a range that is equal to or less than any upper limit arbitrarily selected from the upper limits listed above and equal to or greater than any lower limit arbitrarily selected from the lower limits listed above.

[0071] The second hydrocarbon functional group is a functional group having a relatively small number of carbon atoms among the long-chain hydrocarbon functional groups. The lower limit of the carbon atoms of the second hydrocarbon functional group may be about 3, 4, 5, 6, 7, or 8, and the upper limit may be about 9, 8, 7, or 6. The carbon atoms of the second hydrocarbon functional group may be within a range that is less than or equal to any upper limit arbitrarily selected from the upper limits listed above; or within a range that is less than or equal to any upper limit arbitrarily selected from the upper limits listed above and greater than or equal to any lower limit arbitrarily selected from the lower limits listed above.

[0072] The number of carbon atoms in each of the first and second hydrocarbon functional groups may be the number of carbon atoms in a straight-chain hydrocarbon chain present in the hydrocarbon functional group. For example, the first and second hydrocarbon functional groups may each independently be at least one selected from the group consisting of an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkylcarbonyl group, and an alkylcarbonyloxy group, and may be an alkyl group and / or an alkoxy group in an appropriate example, and the number of carbon atoms may be the number of carbon atoms in the alkyl group, the alkenyl group, the alkynyl group, the alkoxy group, the alkyl group of the alkylcarbonyl group, and the alkyl group of the alkylcarbonyloxy group.

[0073] The above alkyl group, alkenyl group, alkynyl group, the above alkoxy group, the alkyl group of the alkylcarbonyl group and the alkyl group of the alkylcarbonyloxy group may have a straight-chain or branched-chain structure. In the case of a straight-chain structure, the total number of carbon atoms may be within the above range, and in the case of a branched-chain structure, the number of carbon atoms constituting the longest straight-chain chain in the branched-chain structure may be within the above range.

[0074] The carbon number of the long-chain hydrocarbon functional group is a functional group that exhibits enhanced vibrational energy at increased temperature, and the greater the carbon number at the same temperature, the higher the vibrational energy is exhibited. That is, the first hydrocarbon functional group exhibits higher vibrational energy than the second hydrocarbon functional group at the same temperature, and the sum of the vibrational energies of these two functional groups can optimize the properties of the conductive polymer, which are difficult to precisely control with a single functional group.

[0075] For example, the first hydrocarbon functional group exhibits enhanced vibrational energy at an increased temperature, and the second hydrocarbon functional group dilutes the vibrational energy of the first hydrocarbon functional group at the same temperature, thereby allowing the onset point of dedoping of the conductive polymer to be precisely controlled according to the purpose.

[0076] Additionally, the desired intermolecular distance can be achieved by adjusting the ratio of the first and second hydrocarbon functional groups.

[0077] The ratio of the total mole number of the first and second hydrocarbon functional groups to the mole number (M) of the total monomer units of the conductive polymer or the total mole number of monomer units having the first hydrocarbon functional group and monomer units having the second hydrocarbon functional group is the ratio described above 100×M L / Can be adjusted within the same range as M.

[0078] The lower limit of the ratio (M2 / M1) of the number of moles (M2) of the second hydrocarbon functional group or the number of moles (M2) of the monomer unit having the second hydrocarbon functional group to the number of moles (M1) of the first hydrocarbon functional group or the number of moles (M1) of the monomer unit having the first hydrocarbon functional group may be about 0.01, 0.05, 0.1, 0.5, 0.6, 0.7, 0.8, 0.9, 0.95, 1.0, 1.1 or 1.15, and the upper limit may be about 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, It can be about 15, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1.5, 1.3, 1 or 0.7. The ratio can be within a range that is less than or equal to any upper limit arbitrarily selected from the upper limits listed above and greater than or equal to any lower limit arbitrarily selected from the lower limits listed above. The ratio M2 / M1 can be changed in consideration of the level of the desired vibrational energy and the design value of the polymer layer.

[0079] The conductive polymer may include a polar functional group together with the long-chain hydrocarbon functional group. The monomer having the polar functional group may be a thiophene monomer.

[0080] The term polar functional group refers to a functional group containing one or more polar atoms, such as oxygen and / or nitrogen. Examples of such functional groups include, but are not limited to, a carboxyl group, a hydroxyl group, an amino group, a cyano group, a nitro group, an ether group, an alkoxy group, and / or a functional group represented by the following formula (1).

[0081] The alkoxy group may be, in one example, an alkoxy group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms. The alkoxy group may be linear, branched, or cyclic, and may be linear or branched, as appropriate. The alkoxy group may be optionally substituted with one or more substituents.

[0082] In one example, the functional group of the following chemical formula 1 can be applied as the polar functional group.

[0083] [Chemical Formula 1]

[0084]

[0085] In chemical formula 1, L1 is a single bond, an alkylene group, or an alkylidene group, L2 is an alkylene group or an alkylidene group, R1 is hydrogen or an alkyl group, and n is any number.

[0086] In chemical formula 1, L1 being a single bond means that L1 does not exist and the oxygen atom between L1 and L2 is directly connected to the monomer.

[0087] The alkyl group of R1 in Chemical Formula 1 may be, in one example, an alkyl group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms, or a methyl group or an ethyl group. The alkyl group may be linear, branched, or cyclic, and may be linear or branched, as appropriate. The alkyl group may be optionally substituted with one or more substituents.

[0088] The term alkylene group refers to a divalent functional group formed by the removal of one hydrogen atom from each of two different carbon atoms of an alkane, and the term alkylidene group refers to a divalent functional group formed by the removal of two hydrogen atoms from one carbon atom of an alkane.

[0089] The alkylene groups of L1 and L2 in Chemical Formula 1 may each be, in one example, an alkylene group having 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms, or an ethylene group or a propylene group. The alkylene group may be linear, branched, or cyclic, and may be linear or branched, as appropriate. The alkylene group may be optionally substituted with one or more substituents.

[0090] The alkylidene groups of L1 and L2 in the chemical formula 1 may each be, in one example, an alkylidene group having 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms, or a methylidene group, an ethylylene group, or a propylidene group. The alkylidene group may be linear, branched, or cyclic, and may be linear or branched, as appropriate. The alkylidene group may be optionally substituted with one or more substituents.

[0091] In chemical formula 1, the lower limit of n may be 1, 2, 3, or 4, and the upper limit may be about 10, 9, 8, 7, 6, 5, 4, or 3. The m may be within a range that is less than or equal to any upper limit arbitrarily selected from the upper limits listed above, and greater than or equal to any lower limit arbitrarily selected from the lower limits listed above.

[0092] The polar functional group can bind the polymer layer to another layer with appropriate bonding strength, and in combination with the long-chain hydrocarbon functional group, can significantly improve the dispersibility of the conductive material described below within the polymer layer. In addition, the polar functional group can also play a role in suppressing the PTC effect from appearing at relatively low temperatures.

[0093] The mole numbers of the polar functional groups and long-chain hydrocarbon functional groups within the conductive polymer can be controlled to ensure an appropriate effect.

[0094] For example, the number of moles (M) of the long-chain hydrocarbon functional groups in the conductive polymer L ) or the number of moles (M) of monomer units having the long-chain hydrocarbon functional group L ) and the number of moles of the polar functional group (M P ) or the number of moles (M) of monomer units having the polar functional group P ) ratio (M L / M P ) may be about 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6 6.5, 7, 7.5, 8, 8.5, 9, 10, 13, 15, 17 or 19, and its upper limit may be about 500, 450, 400, 350, 300, 250, 200, 150, 100, 90, 80, 70, 60, 50, 40, 30, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10 or 9.5. The above ratio M L / M P It may be within a range that is less than or equal to an upper limit arbitrarily selected from the upper limits listed above; or within a range that is greater than or equal to an lower limit arbitrarily selected from the lower limits listed above; or within a range that is less than or equal to an upper limit arbitrarily selected from the upper limits listed above and greater than or equal to an lower limit arbitrarily selected from the lower limits listed above. In the above, the ratio M L / M P If is the ratio between monomer units, the ratio is the number of moles M of monomer units having all long-chain hydrocarbon functional groups present in the conductive polymer. L and the number of moles M of monomer units having all polar functional groups P The ratio of; or the number of moles M of monomers having all long-chain hydrocarbon functional groups applied to prepare the conductive polymer L and the number of moles M of monomers having all polar functional groups P It can be a ratio of .

[0095] The total number of moles M of monomer units having the long-chain hydrocarbon functional group and monomer units having the polar functional group relative to the number of moles M of all monomer units in the conductive polymer S The ratio is 100×M as described above T / can be adjusted within the same range as M. At this time, the number of confiscations M T Instead, confiscate M S is substituted.

[0096] For example, the conductive polymer may include a unit of the following chemical formula 2 as the thiophene monomer unit.

[0097] [Chemical Formula 2]

[0098]

[0099] In Chemical Formula 2, R2 and R3 can each independently be hydrogen, the polar functional group, or the long-chain hydrocarbon functional group. In another example, R2 and R3 in Chemical Formula 2 can be linked to each other to form a divalent functional group of Chemical Formula 3 below.

[0100] [Chemical Formula 3]

[0101]

[0102] In chemical formula 3, L3 and L4 can each independently be a single bond, an alkylene group, or an alkylidene group, and R4 and R5 can each independently be hydrogen, the polar functional group, or the long-chain hydrocarbon functional group.

[0103] In the chemical formula 2, when R2 and R3 are each independently hydrogen, a polar functional group or a long-chain hydrocarbon functional group, at least one of R2 and R3 may be the polar functional group or the long-chain hydrocarbon functional group.

[0104] In the case where R2 and R3 in the chemical formula 2 form a divalent functional group of the chemical formula 3, at least one of R4 and R5 may be the polar functional group or long-chain hydrocarbon functional group.

[0105] In Chemical Formula 3, the meanings and specific examples of the single bond, alkylene group, and alkylidene group are the same as in Chemical Formula 1. In Chemical Formulas 2 and 3, the technical significance and specific examples of the long-chain hydrocarbon functional group and the polar functional group are as described above.

[0106] The number of moles M of the unit of the above chemical formula 2 compared to the number of moles M of the total monomer units of the conductive polymer C2 The ratio is 100×M above. T / M can be adjusted to the same extent, where M T Go M C2 is replaced by

[0107] In one example, the conductive polymer may include a monomer unit represented by the following chemical formula 4. The monomer unit of the chemical formula 4 may be an example of a monomer unit having the first hydrocarbon functional group.

[0108] [Chemical Formula 4]

[0109]

[0110] In chemical formula 4, R6 and R7 can each independently be hydrogen or the first hydrocarbon functional group. In this case, at least one of R6 and R7 can be the first hydrocarbon functional group.

[0111] In another example, R6 and R7 can be linked to each other to form a divalent functional group of the following chemical formula 5.

[0112] [Chemical Formula 5]

[0113]

[0114] In chemical formula 5, L5 and L6 are each independently a single bond, an alkylene group, or an alkylidene group, and R8 and R9 are each independently hydrogen or the first hydrocarbon functional group, but at least one of R8 and R9 may be the first hydrocarbon functional group.

[0115] The specific details of the first hydrocarbon functional group are as described above, and the specific details of the single bond, alkylene group or alkylidene group are as described in the chemical formula 1.

[0116] The conductive polymer may also include a monomer unit represented by the following chemical formula 6. The monomer unit of the chemical formula 6 may be an example of a monomer unit having the second hydrocarbon functional group.

[0117] [Chemical Formula 6]

[0118]

[0119] R in chemical formula 6 10 and R 11 Each of which may independently be hydrogen or the second hydrocarbon functional group, in which case R 10 and R 11 At least one of the above may be a second hydrocarbon functional group.

[0120] In another example, the above R 10 and R 11can be linked to each other to form a divalent functional group of the following chemical formula 7.

[0121] [Chemical Formula 7]

[0122]

[0123] In chemical formula 7, L7 and L8 are each independently a single bond, an alkylene group or an alkylidene group, and R 12 and R 13 are each independently hydrogen or the second hydrocarbon functional group, R 12 and R 13 At least one of the above is a second hydrocarbon functional group.

[0124] The specific details of the second hydrocarbon functional group are as described above, and the specific details of the single bond, alkylene group, and alkylidene group are as described in Chemical Formula 1.

[0125] The conductive polymer may also include a monomer unit represented by the following chemical formula 8. The monomer unit of the chemical formula 8 may be an example of a monomer unit having the polar functional group.

[0126] [Chemical Formula 8]

[0127]

[0128] R in chemical formula 8 14 and R 15 Each of which can independently be hydrogen or the polar functional group. In the above case, the R 14 and R 15 At least one of the above polar functional groups.

[0129] In another example, R of the above chemical formula 8 14 and R 15 can be linked to each other to form a divalent functional group of the following chemical formula 9.

[0130] [Chemical Formula 9]

[0131]

[0132] In chemical formula 9, L9 and L 10 are each independently a single bond, an alkylene group or an alkylidene group, and R 16 and R 17 are each independently hydrogen or a polar functional group, R 16 and R 17 At least one of the above polar functional groups.

[0133] The specific details of the above polar functional group are as described above, and the specific details of the single bond, alkylene group, and alkylidene group are as described in Chemical Formula 1.

[0134] In the case where the conductive polymer simultaneously contains the monomer unit of the above chemical formula 4 and the monomer unit of the chemical formula 6, the total mole number M of the monomer unit of the above chemical formula 4 and the monomer unit of the chemical formula 6 is compared to the mole number M of the total monomer unit contained in the conductive polymer. 4+6 The ratio is 100×M as mentioned above. L / M can be adjusted within the same range, where M L This M 4+6 is replaced by

[0135] The ratio of the mole number M4 of the monomer unit of the above chemical formula 4 and the mole number M6 of the monomer unit of the above chemical formula 6 can be adjusted within the same range as the above ratio M2 / M1. At this time, the mole number M1 can be the mole number of the monomer unit of the above chemical formula 4, and the mole number M2 can be the mole number of the monomer unit of the above chemical formula 6.

[0136] When the conductive polymer contains monomer units of the above chemical formula 8, the units have a molar ratio M L / M P It can be included so that it is satisfied. At this time, the mole number of the monomer unit of the above chemical formula 8 is mole number M P becomes. In addition, the above confiscation M Lmay be the number of moles of the monomer unit of the above chemical formula 4, the number of moles of the monomer unit of the above chemical formula 6, or the total number of moles of the monomer unit of the above chemical formula 4 and the monomer unit of the above chemical formula 6.

[0137] When the monomer units of the chemical formulae 4, 6 and 8 are present in the conductive polymer, the total mole number M of the monomer units of the chemical formulae 4, 6 and 8 4+6+8 The ratio of the total mole number M of all monomer units in the above conductive polymer is 100×M T / can be adjusted within the same range as M. At this time, the number of confiscations M 4+6+8 This confiscation M T It becomes.

[0138] The conductive polymer comprises the above monomer units and may additionally comprise other monomer units.

[0139] The above conductive polymer may have a weight average molecular weight within a predetermined range. The lower limit of the weight average molecular weight of the above conductive polymer may be about 10,000, 15,000, 20,000, 25,000, 30,000, 35,000, 40,000, 45,000, 50,000, 55,000, 60,000, 65,000, 70,000, 75,000, 80,000, 85,000, 90,000, 95,000, 100,000, 110,000, 120,000, 130,000 or 135,000, and the upper limit may be about 1,000,000, 950,000, 900,000, It may be about 850,000, 800,000, 750,000, 700,000, 650,000, 600,000, 550,000, 500,000, 450,000, 400,000, 350,000, 300,000, 250,000, 200,000, 150,000, 130,000, 110,000 or 100,000. The weight average molecular weight may be within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above, and equal to or less than any upper limit arbitrarily selected from the upper limits listed above. The unit of the above weight average molecular weight is g / mol, and can be confirmed according to the description of “2. GPC (Gel Permeation Chromatograph) Analysis” in the Examples section of this specification.

[0140] The molecular weight distribution of the conductive polymer, i.e., the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw / Mn), may be within a predetermined range. The lower limit of the molecular weight distribution may be about 2, 2.5, 3, 3.5, 4, 4.5, or 5, and the upper limit may be about 8, 7.5, 7, 6.5, 6, 5.5, 5, 4.5, 4, or 3.7. The molecular weight distribution may have a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above, and equal to or less than any upper limit arbitrarily selected from the upper limits listed above. The molecular weight distribution can be confirmed according to the description of "2. GPC (Gel Permeation Chromatograph) Analysis" in the Examples section of the present specification.

[0141] The polymer layer includes the conductive polymer and can thus exhibit the above-described properties. As long as the polymer layer includes the conductive polymer, it can also include any additional components.

[0142] For example, the polymer layer may additionally include a conductive material along with the conductive polymer. By adding such a material, the properties of the polymer layer can be further adjusted according to the purpose. As the conductive material, a material having appropriate conductivity can be used. For example, the conductive material may be one or more selected from carbon particles, carbon fibers, graphene, graphite, carbon black, and carbon nanotubes.

[0143] As the above-mentioned challenging material, an appropriate type may be selected and used from the types described above, and the form of the material may be, but is not limited to, a particle shape (spherical, irregular or other shape), a plate shape or a fiber shape.

[0144] The size of the above challenge material can also be appropriately adjusted as needed. For example, the lower limit of the size of the above-mentioned challenging material may be about 10 nm, 50 nm, 100 nm, 150 nm, 200 nm, 250 nm, 300 nm, 350 nm, 400 nm, 450 nm, 500 nm, 550 nm, 600 nm, 650 nm, 700 nm, 750 nm, 800 nm, 850 nm, 900 nm, 950 nm, 1000 nm, 5000 nm or 10000 nm, and the upper limit may be about 100000 nm, 90000 nm, 80000 nm, 70000 nm, 60000 nm, 50000 nm, 40000 nm, 30000 nm, 20000 nm, 10000 nm, It may be about 5000 nm, 1000 nm, 950 nm, 900 nm, 850 nm, 800 nm, 750 nm, 700 nm, 650 nm, 600 nm, 550 nm, 500 nm, 450 nm, 400 nm, 350 nm, 300 nm, 250 nm, 200 nm, 200 nm, 150 nm, 100 nm, 90 nm, 80 nm or 70 nm. The size may be within a range that is less than or equal to any upper limit arbitrarily selected from the above-listed upper limits; or within a range that is greater than or equal to any lower limit arbitrarily selected from the above-listed lower limits; or within a range that is less than or equal to any upper limit arbitrarily selected from the above-listed upper limits and greater than or equal to any lower limit arbitrarily selected from the above-listed lower limits.

[0145] The above size is the average diameter (so-called D50 particle diameter) measured according to the “4. Average particle diameter measurement” section described in the Examples section of this specification.

[0146] If necessary, the above-mentioned challenging material may be surface-treated to take into account dispersibility and coatability. In particular, such surface treatment can secure stable coatability and form a uniform polymer layer.

[0147] In this case, a surface treatment agent having appropriate compatibility with the conductive polymer can be used as a surface treatment agent. For example, the conductive material may be surface-treated with a polyphenol-based compound as a surface treatment agent. A polyphenol-based compound refers to a compound having a structure containing two or more linked hydroxyl groups substituted on benzene. Examples of such compounds include so-called catechol-based compounds (i.e., catechol or compounds containing the structure), and examples thereof include, but are not limited to, dopamine, polydopamine, 3,4-dihydroxy phenyl alanine, norephinephrine, tannic acid, humic acid, and / or lignin.

[0148] There is no limitation on the method for surface treating a conductive material with the above surface treating agent, and for example, a method of mixing the conductive material and the surface treating agent in an appropriate solvent, etc., or a method of synthesizing or polymerizing the surface treating agent on the surface of the conductive material can be applied.

[0149] The content of the above-described conductive material can be adjusted in consideration of the desired oxidation potential. Generally, as the content of the conductive material in the polymer layer increases, the oxidation potential of the polymer layer decreases. Therefore, the content of the conductive material can be adjusted in consideration of the oxidation potential of the electrode active material and the corresponding oxidation potential of the polymer layer. For example, the lower limit of the content of the conductive material in the polymer layer relative to 100 parts by weight of the conductive polymer may be about 0.5 parts by weight, 1 part by weight, 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight, 80 parts by weight, 90 parts by weight or 100 parts by weight, and the upper limit may be about 1,000 parts by weight, 900 parts by weight, 800 parts by weight, 700 parts by weight, 600 parts by weight, 500 parts by weight, 400 parts by weight, 300 parts by weight, 200 parts by weight, 150 parts by weight, 100 parts by weight, 50 parts by weight, 48 parts by weight, 46 parts by weight, 44 parts by weight, 42 parts by weight, 40 parts by weight, 38 The content may be about 36 parts by weight, 34 parts by weight, 32 parts by weight, 30 parts by weight, 28 parts by weight, 26 parts by weight, 24 parts by weight, 22 parts by weight, 20 parts by weight, 18 parts by weight, 16 parts by weight, 14 parts by weight, 12 parts by weight, or 10 parts by weight. The content may be within a range that is less than or equal to any upper limit arbitrarily selected from the upper limits listed above; or within a range that is greater than or equal to any lower limit arbitrarily selected from the lower limits listed above; or within a range that is less than or equal to any upper limit arbitrarily selected from the upper limits listed above and greater than or equal to any lower limit arbitrarily selected from the lower limits listed above.

[0150] Under such a ratio, the above-mentioned challenging material can appropriately interact with the above-mentioned conductive polymer to effectively form a polymer layer of the desired shape.

[0151] The present specification also discloses a method for preparing the polymer layer.

[0152] As described above, in order for the polymer layer to exhibit the desired effect, selection of long-chain hydrocarbon functional groups and / or conductive materials is important, and furthermore, control of the arrangement state of the long-chain hydrocarbon functional groups and / or the dispersion state of the conductive material is important. The desired arrangement and / or dispersion state can be secured by the manufacturing method described below. In addition, the desired intermolecular distance can also be effectively secured by the manufacturing method described below.

[0153] The above manufacturing method may include, for example, a step of forming a polymer layer precursor including the conductive polymer and a step of heat-treating the polymer layer precursor.

[0154] The conductive polymers described above can be manufactured using known methods. For example, methods for manufacturing polythiophene include oxidative polymerization and radical reactions, and these methods can also be applied to the process of forming the conductive polymer. Furthermore, commercially available conductive materials can be used, and their surface treatment can be performed using known methods.

[0155] The above polymer layer precursor refers to a layer that is converted into the polymer layer, for example, a layer that includes the conductive polymer and, if necessary, additional components such as a conductive material. Such a precursor can be formed by a known method, for example, by coating a polymer solution in which the conductive polymer or the like is dispersed in an appropriate solvent.

[0156] When the polymer solution is coated on the main body of the current collector and the process is performed, the above manufacturing method becomes the manufacturing method of the current collector described above.

[0157] As the solvent, an appropriate solvent capable of dispersing the conductive polymer and conductive material may be selected, and examples thereof include, but are not limited to, ether solvents such as diethyl ether, tetrahydrofuran, dioxane, trioxane, dimethoxyethane, or toluene; aromatic hydrocarbon solvents such as ethyl benzene or alicyclic hydrocarbon solvents such as cyclohexane; tertiary amine solvents such as tetramethylethylenediamine (TMEDA) or hexamethylphosphorictriamide (HMPA), or mixed solvents containing two or more of the above.

[0158] The polymer solution described above is used to form a polymer layer precursor. This process can typically be performed by coating the polymer solution onto an appropriate process substrate. There are no specific restrictions on the coating method.

[0159] The above manufacturing method further includes a step of heat-treating the precursor of the polymer layer. By adjusting the conditions during this process, the orientation state of the conductive polymer (e.g., the orientation state of the long-chain hydrocarbon functional group and / or polar functional group) and / or the dispersion state of the conductive material can be adjusted, thereby forming a polymer layer exhibiting the desired effect.

[0160] The heat treatment step may be performed in two stages. For example, the heat treatment step may include a first stage of performing a primary heat treatment on the polymer layer precursor; and a second stage of performing a secondary heat treatment on the polymer layer precursor that has undergone the first stage.

[0161] The conditions of the first and second steps can be adjusted to achieve the desired orientation or alignment of the functional groups and the dispersion state of the challenging material.

[0162] For example, the temperature T1 of the first heat treatment and the temperature T2 of the second heat treatment can be adjusted. For example, the lower limit of the ratio (T1 / T2) of the temperatures T1 and T2 can be about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, or 1.2, and the upper limit can be about 10, 5, 4.5, 4, 3.5, 3, 2.5, 2, 1.9, 1.8, 1.7, 1.6, 1.5, 1.4, 1.3, or 1.2. The ratio is within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above; or within a range that is equal to or less than any upper limit arbitrarily selected from the upper limits listed above; Or, it may be within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above, and equal to or less than any upper limit arbitrarily selected from the upper limits listed above.

[0163] For example, the temperature T1 of the first heat treatment can be adjusted within a predetermined range. For example, the lower limit of the temperature T1 may be about 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C or 140°C, and the upper limit may be about 300°C, 290°C, 280°C, 270°C, 260°C, 250°C, 240°C, 230°C, 220°C, 210°C, 200°C, 190°C, 180°C, 170°C, 160°C, 150°C or 140°C. The above temperature T1 may be within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above; or within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above and equal to or less than any upper limit arbitrarily selected from the upper limits listed above.

[0164] In order to form the desired polymer layer, the first heat treatment temperature can be achieved by increasing the temperature at a specific heating rate.

[0165] The ratio of the heat treatment time S1 in the first heat treatment and the heat treatment time S2 in the second heat treatment can be additionally adjusted. For example, the lower limit of the above ratio S2 / S1 may be about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 50, 70, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260 or 270, and the upper limit may be about 1,000, 950, 900, 850, 800, 750, 700, 650, 600, 550, 500, 450, It can be about 400, 350, 300, 290, 280, 270, 250, 200, 150, 100, 90, 80, 70, 60, 50, 40, 30 or 20. The ratio S2 / S1 can be within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above; or within a range that is equal to or less than any upper limit arbitrarily selected from the upper limits listed above; or within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above and equal to or less than any upper limit arbitrarily selected from the upper limits listed above.

[0166] The lower limit of the above secondary heat treatment time S2 may be about 0.1 hours, 0.2 hours, 0.3 hours, 0.4 hours, 0.5 hours, 0.6 hours, 0.7 hours, 0.8 hours, 0.9 hours, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours or 18 hours, and the upper limit may be about 50 hours, 48 ​​hours, 46 hours, 44 hours, 42 hours, 40 hours, 38 hours, 36 hours, 34 hours, 32 hours, 30 hours, 28 hours, 26 hours, 24 hours, 22 hours, 20 hours, 18 hours. It can be about 16 hours, 14 hours, 12 hours or 10 hours. The secondary heat treatment time S2 can be within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above; or within a range that is equal to or less than any upper limit arbitrarily selected from the upper limits listed above; or within a range that is equal to or greater than any lower limit arbitrarily selected from the lower limits listed above and equal to or less than any upper limit arbitrarily selected from the upper limits listed above.

[0167] The polymer layer can be formed through the above process.

[0168] The present specification also discloses an electrode comprising the above-described collector.

[0169] As described above, the electrode may sequentially include the current collector body; the polymer layer and the active material layer.

[0170] The above polymer layer may be a polymer layer formed on the current collector body by being included in the current collector as specifically described above.

[0171] A layer that is commonly applied can also be used as the above active material layer.

[0172] Typically, the above active material layer includes an electrode active material. There is no particular limitation on the specific type of the electrode active material, and typically, a material forming a positive or negative electrode can be used.

[0173] For example, when the active material layer is a positive electrode active material layer, the electrode active material may be a layered compound such as lithium nickel oxide (LiNiO2) or a compound substituted with one or more transition metals; lithium iron oxide such as LiFe3O4; or a compound having the chemical formula Li. 1+c1 Mn 2-c1 Lithium manganese oxides such as O4(0≤c1≤0.33), LiMnO3, LiMn2O3, or LiMnO2; lithium copper oxide (Li2CuO2); vanadium oxides such as LiV3O8, V2O5, or Cu2V2O7; chemical formula LiNi 1-c2 M c2 Ni-site type lithium nickel oxide represented by O2 (wherein, M is at least one selected from the group consisting of Co, Mn, Al, Cu, Fe, Mg, B, and Ga, and satisfies 0.01≤c2≤0.3); chemical formula LiMn 2-c3 M c3 Lithium manganese composite oxide represented by O2 (wherein, M is at least one selected from the group consisting of Co, Ni, Fe, Cr, Zn, and Ta, and satisfies 0.01≤c3≤0.1) or Li2Mn3MO8 (wherein, M is at least one selected from the group consisting of Fe, Co, Ni, Cu, and Zn); lithium nickel cobalt manganese (NCM) composite oxide, lithium nickel cobalt manganese aluminum (NCMA) composite oxide, and LiMn2O4 in which a part of Li in the chemical formula is replaced with an alkaline earth metal ion, but is not limited thereto.

[0174] When the above-mentioned active material layer is a negative electrode active material layer, a compound capable of reversible intercalation and deintercalation of lithium may be used as the electrode active material. Specific examples thereof include carbonaceous materials such as artificial graphite, natural graphite, graphitized carbon fiber, and amorphous carbon; metallic compounds capable of alloying with lithium such as Si, Al, Sn, Pb, Zn, Bi, In, Mg, Ga, Cd, Si alloys, Sn alloys, and Al alloys; metallic oxides capable of doping and dedoping lithium such as SiOa (0 < a < 2), SnO2, vanadium oxide, and lithium vanadium oxide; or composites comprising the above-mentioned metallic compounds and carbonaceous materials such as Si-C composites or Sn-C composites, and any one or a mixture of two or more thereof may be used.

[0175] As the above negative active material, a lithium thin film may be used, and low-crystalline carbon and high-crystalline carbon may be used as carbon materials. Soft carbon and hard carbon are representative examples of low-crystalline carbon, and high-crystalline carbon is representative examples of amorphous, plate-like, flaky, spherical or fibrous natural or artificial graphite, Kish graphite, pyrolytic carbon, mesophase pitch-based carbon fiber, mesocarbon microbeads, mesophase pitches, and high-temperature calcined carbon such as petroleum or coal tar pitch derived cokes.

[0176] The above electrode active material may be included in the active material layer in a range of about 80 wt% to 99.5 wt% or 88 wt% to 99 wt% relative to the total weight of the active material layer, but the ratio may be changed depending on the purpose or design of the electrode.

[0177] The above active material layer may additionally include a binder. The binder serves to improve adhesion between active materials and adhesive strength between the active material layer and the current collector body. Examples of the above binder are not particularly limited, and include, for example, PVDF (Poly(vinylidene fluoride)), PVA (poly(vinyl alcohol)), SBR (styrene butadiene rubber), PEO (poly(ethylene oxide)), CMC (carboxyl methyl cellulose), cellulose acetate, cellulose acetate butylate, cellulose acetate propionate, cyanoethylpullulan, cyanoethyl polyvinylalcohol, cyanoethyl cellulose, cyanoethyl sucrose, pullulan, polymethylmethacrylate, polybutylacrylate, polyacrylonitrile, At least one selected from the group consisting of polyvinylpyrrolidone, polyvinylacetate, polyethylene-co-vinyl acetate, and polyarylate may be used.

[0178] In one example, the binder may be included in the active material layer in an amount of 0.1 to 10 parts by weight or 0.5 to 5 parts by weight relative to 100 parts by weight of the electrode active material, but is not limited thereto.

[0179] The above active material layer may additionally include a conductive material, if necessary. As the conductive material, any known material may be used without particular limitation as long as it is conductive and does not cause chemical changes in the secondary battery. For example, graphite such as natural graphite or artificial graphite; carbon black such as carbon black, acetylene black, Ketjen black, channel black, paneth black, lamp black, thermal black, etc.; conductive fibers such as carbon fiber or metal fiber; conductive tubes such as carbon nanotubes (CNTs); metal powders such as fluorocarbon, aluminum, and nickel powder; conductive whiskers such as zinc oxide or potassium titanate; conductive metal oxides such as titanium oxide, and / or conductive materials such as polyphenylene derivatives, etc. may be used.

[0180] The above-mentioned conductive material may be included in the active material layer in an amount of 0.1 to 20 parts by weight or 0.3 to 10 parts by weight relative to 100 parts by weight of the electrode active material, but is not limited thereto.

[0181] In addition to the components described above, the active material layer may additionally include any known components required.

[0182] The present specification discloses a method for manufacturing the electrode.

[0183] This manufacturing method may include a step of forming the active material layer on the polymer layer on the current collector body.

[0184] There is no particular limitation on the method for forming the active material layer on the polymer layer. Typically, the active material layer is formed by coating a slurry containing the electrode active material, a binder, a conductive agent, etc. on the current collector body (polymer layer), drying it, and then rolling it. This known method can be applied in the same manner. Accordingly, the manufacturing method may include a step of rolling the active material layer of the above-mentioned electrode (i.e., an electrode having no protrusions in the sliding region of the active material layer).

[0185] The present specification also discloses an electrode assembly or electrochemical device comprising the above electrode, for example, a secondary battery.

[0186] The above-mentioned electrochemical device may include the electrode as an anode and / or cathode. As long as the electrode is used as an anode and / or cathode, other configurations or manufacturing methods of the electrochemical device are not particularly limited, and known methods may be applied.

[0187] The present specification discloses a current collector and its uses. The current collector comprises a polymer layer that exhibits a so-called positive temperature coefficient (PTC) effect at a required level at a required time, making it suitable for use in applications where stability under abnormally high temperatures and / or flames is a concern. The polymer layer of the current collector can rapidly exhibit the PTC effect at a required time. The present specification also discloses uses of the current collector.

[0188] Figure 1 is a cross-sectional view of an exemplary collector.

[0189] Figure 2 is a cross-sectional view of an exemplary electrode.

[0190] Figure 3 shows the NMR analysis results for the monomer of Manufacturing Example 1.

[0191] Figure 4 shows the NMR analysis results for the conductive polymer of Manufacturing Example 2.

[0192] Figure 5 shows the results of XRD (X-ray diffraction) analysis performed on the polymer layer.

[0193] Figure 6 shows the results of XRD (X-ray diffraction) analysis performed on the polymer layer.

[0194] Figure 7 is a photograph of a conductive polymer dispersed in toluene at a concentration of 3 wt%.

[0195] Figure 8 is a diagram showing the EIS impedance plot results according to the temperature of the polymer layer.

[0196] Figure 9 is a diagram showing the change in EIS impedance versus potential within the range of 3 V to 4.5 V.

[0197] Figure 10 is a diagram showing the change in EIS impedance versus potential within the range of 3 V to 4.5 V.

[0198] Figure 11 is an EIS nyquist plot at different applied voltages.

[0199] Figure 12 is a CV (Cyclic voltammetry) curve confirmed for an example at a scan rate (sweep rate) of 0.4 mV / s.

[0200] Figure 13 is a CV (Cyclic voltammetry) curve of Example 1 according to a scan rate (sweep rate) in the range of 0.15 mV / s to 0.8 mV / s.

[0201] Figure 14 is a CV (Cyclic voltammetry) curve of Example 2 according to a scan rate in the range of 0.15 mV / s to 0.8 mV / s.

[0202] Figure 15 is a CV curve of Examples 1 and 3 according to the cycle.

[0203] Fig. 16 is a drawing showing the results of a galvanostatic cycling test for an example.

[0204] Figure 17 is a charge / discharge profile in a cycle test.

[0205] Figure 18 shows the energy density retention results (140 cycles) in a cycle test.

[0206] Figure 19 shows the rate test results for a 3-Ah pouch cell.

[0207] Figure 20 shows the results of a cycle test for a 3-Ah pouch cell.

[0208] Figure 21 is a drawing showing the results of the ARC test of the test example.

[0209] Figure 22 shows the XRF observation results for the electrodes of the examples and comparative examples.

[0210] Figure 23 is a drawing showing the process of performing a needle test.

[0211] Figure 24 is a drawing showing the results of a needle test.

[0212] Figure 25 is a drawing showing a method for performing an impact test and the results thereof.

[0213] The above-described collector and the like are specifically described through the following examples and comparative examples, but the scope of the above-described collector and the like is not limited by the following examples.

[0214]

[0215] 1. NMR analysis

[0216] 1 H-NMR analysis was performed at room temperature (approximately 25°C) using an NMR spectrometer (including a Bruker UltraShield spectrometer (300 MHz)) equipped with a triple resonance 5 mm probe. Samples were diluted in NMR measuring solvent (CDCl3) to a concentration of approximately 10 mg / ml, and chemical shifts were expressed in ppm.

[0217]

[0218] 2. GPC (Gel Permeation Chromatograph) analysis

[0219] Molecular weight characteristics were measured using gel permeation chromatography (GPC). The sample was placed in a 5 mL vial and diluted with chloroform to a concentration of approximately 1 mg / mL. The standard sample for calibration and the sample to be analyzed were filtered through a syringe filter (pore size: 0.45 μm), and then the molecular weight characteristics were measured. The analysis program used Waters' Empower 3, and the weight-average molecular weight (Mw) and number-average molecular weight (Mn) were obtained by comparing the elution time of the sample with the calibration curve, and the molecular weight distribution (PDI) was calculated as the ratio (Mw / Mn).

[0220] The measurement conditions of GPC are as follows.

[0221] <GPC 측정 조건>

[0222] Device: Waters 2414

[0223] Column: Using 3 Styragel from Waters

[0224] Solvent: THF (Tetrahydrofuran)

[0225] Column temperature: 35℃

[0226] Sample concentration: 1 mg / mL, 1 μL injection

[0227] Standard samples: polystyrene (Mp: 3900000, 723000, 316500, 52200, 31400, 7200, 3940, 485)

[0228]

[0229] 3. Thickness measurement

[0230] After exposing the cross-section of the thickness measurement target using an ion milling device (Hitachi, IM5000), an SEM (Scanning Electron Microscope) (JEOL, JSM-7200F) image of the cross-section was taken, and the thickness was obtained from the image. The exposure of the cross-section was performed under the conditions of the ion milling device (Hitachi, IM5000) in cross-section milling mode, speed (reciprocation / min) 3, acceleration voltage 6 kD, discharge voltage 15 kV, and current 150 μA, and the time was set to 4 hours. The SEM (Scanning Electron Microscope) (JEOL, JSM-7200F) image was taken under the condition of a voltage of 5 kV, with the magnification adjusted within the range of 500 to 20,000 times.

[0231]

[0232] 4. Measurement of average particle size

[0233] The average particle size (D50 particle size) was measured using a MASTERSIZER3000 from Marvern in accordance with the ISO-13320 standard. Toluene was used as the solvent during the measurement. When a sample (particle) is dispersed in the solvent and a laser is irradiated, the laser is scattered by the sample dispersed in the solvent. Since the intensity and directionality of the scattered laser vary depending on the size of the particles, this can be analyzed using Mie theory to obtain the average particle size. Through the above analysis, the measurement results were converted into the particle size of a sphere having the same volume as the dispersed sample, and a volume-based cumulative graph of the particle size distribution was obtained, and the particle diameter at 50% of the cumulative point of the graph (median particle size) was designated as the average particle size (D50 particle size).

[0234]

[0235] 5. EIS measurement

[0236] Coin cells were used for evaluation through EIS (Electrochemical Impedance Spectroscopy). A separator and a lithium film (thickness: about 300 μm) were laminated on a current collector (Example: Al foil / polymer layer, Comparative Example: Al foil) of an example or a comparative example, to manufacture a laminate (Example: Al foil / polymer layer / separator / lithium film, Comparative Example: Al foil / separator / lithium film), and the laminate was punched into a circle with a diameter of about 1.4 cm. Coin cells were manufactured using a CR2032 coin cell kit from Wellcos, the punched laminate, and the electrolyte. As the above separator, the WL20C model separator of W-SCOPE KOREA was used, and as the electrolyte, the electrolyte of GTHR KOREA (1 M LiPF6 solution, solvent = EC:DMC:DEC (3:3:4, volume ratio) (EC: Ethylene Carbonate, DMC: dimethyl carbonate, EMC: ethylmethyl carbonate)) (3 μL mAh- 1 ) was used.

[0237] A voltage of 4.3 V was applied to the coin cell at room temperature (25°C) for 10 minutes, and the impedance obtained in the high frequency region of the Nyquist plot obtained by the EIS measurement method from 50,000 Hz to 0.1 Hz was measured. A potentiostat (Princeton Applied Research, PARASTAT-MC) was used as the EIS measurement device.

[0238] When measuring impedance according to temperature change, the coin cell was placed in the center of a convection oven (Jeotech, OF3-05W), and the impedance was measured while increasing the oven temperature from 25°C to 130°C at a rate of 2°C / min.

[0239]

[0240] Manufacturing Example 1. Synthesis of monomer (A)

[0241] The monomer of the following chemical formula A was synthesized in the following manner.

[0242] [Chemical Formula A]

[0243]

[0244] 3-Methoxythiophene 3 g (26.28 mmol, 1 eq) and triethylene glycol monomethyl ether 7.03 g (39.42 mmol, 1.5 eq) were dissolved in 150 ml of toluene and mixed with 500 mg of p-toluenesulfonic acid (p-TsOH) (2.63 mmol, 0.1 eq). The mixture was refluxed at 120°C under a nitrogen atmosphere, and the methanol produced by the reaction (transetherification) was removed with a 4A type molecular sieve packed in a soxhlet extractor. After refluxing for 24 h, the reaction mixture was cooled to room temperature, quenched with water, extracted with ethyl acetate, washed with brine, and dried over magnesium sulfate (MgSO4). The solvent was removed using a rotary evaporator, and the residue was purified by column chromatography using methylene chloride / hexane (2:1) elution to obtain the target compound (monomer (A)). The NMR analysis results for the monomer (A) are shown in Figure 3.

[0245]

[0246] Manufacturing Example 2. Synthesis of polythiophene (A)

[0247] A solution prepared by dispersing 215 g of iron (III) chloride in 700 mL of hexane was stirred vigorously at 30°C for about 30 minutes. A solution of 53.3 g (approximately 0.21 mol) of 3-dodecylthiophene, 41.5 g (approximately 0.25 mol) of 3-hexylthiophene, and 6.1 g (0.024 mol) of the monomer (A) of Preparation Example 1 was added to the hexane in which the iron chloride was dissolved at a rate of about 5 mL / min to prepare a mixture. The mixture was stirred at about 150 rpm for about 1 hour. The temperature was set to about 10°C, and 2.4 L of methanol was added to obtain a precipitate. The obtained precipitate was redissolved in 2 L of THF (Tetrahydrofuran) at 60°C for 5 hours. After redissolution, an additional 2.5 L of methanol was added to obtain a precipitate through a reprecipitation process, and the precipitate was washed three times with 1.5 L of methanol to remove impurities. After removing impurities, the precipitate was dried at 60°C for 12 hours to produce polythiophene (A). The weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the polythiophene (A) were approximately 138,000 g / mol and 26,000 g / mol, respectively. The NMR analysis results for the polythiophene (A) are as shown in Fig. 4.

[0248]

[0249] Example 1.

[0250] Polythiophene (A) of Manufacturing Example 2 was dispersed in toluene at a concentration of about 3 wt% to prepare a polymer solution. Then, the polymer solution was completely filled in the pan of a coating equipment to perform micro gravure coating. As the current collector body, an Al foil (SAMA) having a thickness of about 15 μm was used. The polymer solution was coated on the current collector body using the coating equipment (coating speed: 15 meters per minute). Then, the coated polymer solution was dried at 140°C for about 4 minutes. Then, the current collector body coated with the polymer solution was additionally maintained at 110°C for 10 hours to form a polymer layer (thickness: 600 nm), thereby preparing a current collector.

[0251] Next, an active material layer was formed on the polymer layer to manufacture an electrode. The active material layer was formed by applying a slurry containing lithium cobalt oxide (LiCoO2) (XTC), a carbon-based conductive material (ECP (Ketjen Black) 0.5%, SFG (Trimrex graphite) 0.4%, DB (Denka Black) 0.4%), PVDF (polyvinylidene fluoride) (Kureha), and NMP (N-Methyl-2-pyrrolidone) in a weight ratio of 75:1:1:23 (LiCoO2:conductive material:PVDF:NMP) using a doctor blade to a thickness of about 90 μm on the polymer layer, drying at room temperature (about 25°C), and then further drying under vacuum conditions at 120°C. Subsequently, the electrode was manufactured by rolling to have a porosity of about 25%.

[0252]

[0253] Example 2.

[0254] Polythiophene (A) of Manufacturing Example 2 was dispersed in toluene at a concentration of about 3 wt%. Then, conductive particles (Super C, Imerys) were mixed with the toluene so that the weight ratio of the polythiophene (A) and the conductive particles (B) was about 8:2 to prepare a polymer solution. Using the polymer solution, a polymer layer was formed on the current collector body in the same manner as in Example 1, thereby preparing a current collector and an electrode.

[0255]

[0256] Example 3.

[0257] Polythiophene (A) of Manufacturing Example 2 was dispersed in toluene at a concentration of about 3 wt%. Then, conductive particles (Super C, Imerys) were mixed with the toluene so that the weight ratio of the polythiophene (A) and the conductive particles (B) was about 6:4 to prepare a polymer solution. Using the polymer solution, a polymer layer was formed on the current collector body in the same manner as in Example 1, thereby preparing a current collector and an electrode.

[0258]

[0259] Comparative Example 1.

[0260] An electrode was manufactured by forming an active material layer directly on Al foil in the same manner as described in Example 1 without forming a polymer layer.

[0261]

[0262] Test Example 1.

[0263] Figures 5 and 6 show the results of XRD (X-ray diffraction) analysis performed on the polymer layer. The XRD analysis was performed using XRD equipment (Bruker D8 Discover instrument featuring a Cu-K alpha source operating at 40 kV and 40 mA).

[0264] In Fig. 5, P3HT is the result for a polymer layer formed using polythiophene synthesized in the same manner as in Manufacturing Example 2 using only 3-hexylthiophene as a monomer, P3DDT is the result for a polymer layer formed using polythiophene synthesized in the same manner as in Manufacturing Example 2 using only 3-dodecylthiophene as a monomer, and PDDHEO is the result for the polymer layer of Example 1. The method for forming the polymer layers P3HT and P3DDT was the same as in Example 1.

[0265] In Fig. 6, SC0 is the result for the polymer layer of Example 1, SC20 is the result for the polymer layer of Example 2, and SC40 is the result for the polymer layer of Example 3.

[0266] In the results of Fig. 5, the position of the 2θ peak of P3HT was about 5.23 degrees, the position of the 2θ peak of P3DDT was about 3.31 degrees, and the position of the 2θ peak of PDDHEO was about 3.85 degrees. According to these results, the d-spacing of the (100) plane of P3HT was about 1.7 nm, the d-spacing of the (100) plane of P3DDT was about 2.7 nm, and the d-spacing of the (100) plane of PDDHEO was about 2.3 nm.

[0267] These results demonstrate that the intermolecular distance can be controlled by selecting the long-chain hydrocarbon functional group introduced into polythiophene. Furthermore, the results in Figure 6 demonstrate that once polythiophene is established, the addition of conductive particles does not significantly change the intermolecular distance.

[0268]

[0269] Test Example 2.

[0270] Figure 7 is a photograph of a case where polythiophene was dispersed in toluene at a concentration of 3 wt%. In Figure 7, P3HT is a polythiophene synthesized in the same manner as in Manufacturing Example 2, and is the result for polythiophene using only 3-hexylthiophene as a monomer; P3DDT is a polythiophene synthesized in the same manner as in Manufacturing Example 2, and is the result for polythiophene using only 3-dodecylthiophene as a monomer; and PDDHEO is the result for polythiophene (A) manufactured in Manufacturing Example 2. From the figure, it can be confirmed that the solution for PDDHEO is relatively transparent, but that P3DDT and P3HT are relatively opaque. In addition, for the P3HT solution, the viscosity was approximately 15.1 cps (solubility in toluene: 1.04 wt%), for the P3DDT solution, the viscosity was approximately 401 cps (solubility in toluene: 0.76 wt%), and for the PDDHEO solution, the viscosity was approximately 4.5 cps (solubility in toluene: 9.0 wt%). From these results, it can be confirmed that when the conductive polymer disclosed in the present specification is applied, appropriate coating efficiency is secured, providing properties suitable for mass production, etc.

[0271]

[0272] Test Example 3.

[0273] Figure 8 shows the results of an EIS impedance plot according to temperature for a polymer layer. In Figure 8, SC0 is the result for the polymer layer of Example 1, and SC40 is the result for the polymer layer of Example 3. The solid line in Figure 8 represents the change in EIS impedance for each case, and the dotted line represents the change in OCV (Open Circuit Voltage) for each case.

[0274] From the drawing, it can be seen that for SC0, the PTC onset temperature is approximately 95°C, and for SC40, the PTC onset temperature is approximately 105°C. Through this, it can be confirmed that the PTC onset temperature can be adjusted by introducing conductive particles. In addition, looking at the resistance increase speed, for SC0, the speed is approximately 561 ohms·sec- 1 And for SC40, the speed is about 1135 ohms·sec- about 561 ohms·sec- 1 It was about that level.

[0275] Figures 9 to 11 show the impedance results according to the applied voltage.

[0276] Figures 9 and 10 show the change in EIS impedance versus potential in the range of 3 V to 4.5 V. Figure 9 simulates the charging process of a battery, and Figure 10 simulates the discharging process of a battery. In Figures 9 and 10, LCO indicates the charge / discharge curve of a typical LCO cathode material. Figure 11 is an EIS Nyquist plot at different applied voltages, showing that as the voltage decreases, the resistance increases in the order of SC0 (Example 1), SC20 (Example 2), and SC40 (Example 3). In the case of SC40 (Example 3), the minimum resistance was maintained at 3.3 V.

[0277] From the drawing, it can be seen that the resistance of SC40 decreases rapidly as the applied voltage increases during charging, and in the case of SC0, it maintains insulating properties up to 3.6 V. Similarly, during discharging, the resistance of SC0 (Example 1) begins to increase around 3.6 V, and that of SC40 (Example 3) remains almost constant above 3.2 V. These results indicate that the presence of conductive particles causes a more significant increase in resistance, which can more effectively block the flow of current in an abnormal state.

[0278] Figure 12 is a CV (cyclic voltammetry) curve of SC0 (Example 1), SC20 (Example 2), and SC40 (Example 3) at a scan rate (sweep rate) of 0.4 mV / s. Typically, polythiophene exhibits two oxidation peaks. Polythiophene in a neutral state is converted into a polaron state and a bipolaron state when oxidized by anion doping. The first oxidation peak of SC0 at 3.75 V shifted to 3.56 V or 3.41 V as the content of conductive particles increased, and the second oxidation peak was maintained at about 3.83 V. In addition, the reversibility of the first oxidation was improved by the addition of conductive particles.

[0279] Fig. 13 is a cyclic voltammetry (CV) curve of SC0 (Example 1) according to a scan rate (sweep rate) in the range of 0.15 mV / s to 0.8 mV / s, and Fig. 14 is a cyclic voltammetry (CV) curve of SC20 (Example 2) according to a scan rate in the range of 0.15 mV / s to 0.8 mV / s. The reversibility of the first oxidation was improved by the addition of the conductive particles, which is distinguished from the gradual increase in the corresponding reduction peak current. At a low scan rate (0.15 mV / s, corresponding to 0.33 C in galvanostatic cycling), oxidation by anion doping occurred above 3.65 V, and in contrast to the corresponding CV curve of SC40 (Fig. 14), the corresponding reduction peak was barely observed (Fig. 13).

[0280] Figure 15 shows CV curves of SC0 (Example 1) and SC40 (Example 3) according to cycle, and the CV curves between the 2nd and 10th cycles are almost identical. From Figure 15, it can be confirmed that the redox peak for multiple CV cycles is almost constant, which indicates high electrochemical stability.

[0281] These results imply that the challenge particles not only simply increase conductivity, but also promote p-doping and ensure reversible dedoping through combination with specific conductive polymers.

[0282]

[0283] Test Example 4.

[0284] The capability of the electrodes of the comparative examples or examples was compared through a galvanostatic cycling test that increased the C-rate from 0.1C to 2C. This test was performed by manufacturing coin half cells using the electrodes. A separator and a lithium film were laminated on the electrodes of the examples or comparative examples (Example: Al foil / polymer layer / active material layer, Comparative example: Al foil / active material layer), thereby manufacturing a laminate (Example: Al foil / polymer layer / active material layer / separator / lithium film, Comparative example: Al foil / active material layer / separator / lithium film). The laminate was then punched into a circle with a diameter of about 1.4 cm. A Wellcos CR2032 coin cell kit was used, and a coin cell was manufactured using the laminate and the electrolyte punched into the circle. As the separator in the above, the WL20C model of W-SCOPE KOREA was used, and as the electrolyte, the electrolyte of GTHR KOREA (1 M LiPF6 solution, solvent = EC:DMC:DEC (3:3:4, volume ratio) (EC: Ethylene Carbonate, DMC: dimethyl carbonate, EMC: ethylmethyl carbonate)) (3 μL mAh- 1 ) was used, and a film with a thickness of approximately 300 μm was used as the lithium film.

[0285] Figure 16 shows the results of the test performed on the coin half-cell. In Figure 16, the colored squares, circles, and triangles represent capacity, and the uncolored squares, circles, and triangles represent Coulombic efficiency. In the case of Example 3 (SC40), although the introduction of the polymer layer increased the resistance of the electrode, the initial discharge capacity was measured to be approximately 179.5 mAh / g, which means that the loss due to the introduction of the polymer layer was less than 1.2%. Even at 2C, the difference in capacity was less than 2.2%.

[0286] Fig. 17 is a charge / discharge profile of a cycle test, and Fig. 18 is an energy density retention (140 cycles). Compared to Comparative Example 1 (Ref), the energy density retention for Examples 2 and 3 was 92% and 95%, respectively.

[0287] A 3-Ah pouch cell was manufactured using the electrodes of the examples or comparative examples, and its electrochemical performance was evaluated.

[0288] A 3-Ah pouch cell using the electrode of the example as the anode and a 3-Ah pouch cell using the reference electrode as the anode were each assembled.

[0289] The above positive electrodes were each manufactured in the following manner.

[0290] <Electrode of the embodiment>

[0291] The electrode of the example was manufactured by forming polymer layers on both sides of the same current collector as used in Example 3 in the same manner as in Example 3, and forming a positive electrode active material layer on each of the polymer layers. The positive electrode active material layer was formed so that the loading density was approximately 24.29 mg / cm and the porosity was approximately 3.99 g / cc.

[0292] A slurry containing lithium cobalt oxide (LiCoO2) (XTC), carbon-based conductive material (ECP (Ketjen Black) 0.5%, SFG (Trimrex graphite) 0.4%, DB (Denka Black) 0.4%), PVDF (polyvinylidene fluoride) (Kureha), and NMP (N-Methyl-2-pyrrolidone) in a weight ratio of 75:1:1:23 (LiCoO2:conductive material:PVDF:NMP) was applied to a polymer layer with a doctor blade to a thickness of about 90 μm, dried at room temperature (about 25°C), and then further dried under vacuum conditions at 120°C, and then rolled to manufacture the active material layer.

[0293] <Reference electrode>

[0294] The positive electrode, which is the reference electrode, was manufactured in the same manner as the electrode of the above example, but without forming a polymer layer, it was manufactured by forming a positive electrode active material layer on each side of the current collector.

[0295] The cathode for the 3-Ah pouch cell was manufactured in the following manner.

[0296] <Cathode>

[0297] The negative electrode was manufactured by forming a negative electrode active material layer on both sides of a copper foil (thickness: approximately 8 μm). The negative electrode active material layer was formed to have a loading density of approximately 13.88 mg / cm and a porosity of approximately 1.75 g / cc. Water (I), SBR (Styrene-Butadiene rubber) (average particle diameter (D50 particle diameter): 150 nm) (II), a thickener (CMC, carboxymethyl cellulose) (III), electrode active material (1) (IV) (artificial graphite (GT), average particle diameter (D50 particle diameter): 20 μm), and electrode active material (2) (V) (natural graphite (PAS), average particle diameter (D50 particle diameter): 15 μm) were mixed in a weight ratio of 48.5:1:0.5:45:5 (I:II:III:IV:V) to prepare a slurry. The above slurry was applied to the surface of the Cu foil to a thickness of about 280 μm by gap coating, dried at about 75°C for about 10 minutes, and then rolled to form the active material layer.

[0298] A stack cell was manufactured by stacking 14 of the above-mentioned cathodes and 13 of the above-mentioned anodes (electrodes of the embodiment or reference electrodes). A separator was placed between the cathodes and the anodes. As the separator, a separator of the WL20C model from W-SCOPE KOREA was used. A 3-Ah pouch cell was manufactured using the stack cell and electrolyte. As the electrolyte, an electrolyte (1 M LiPF6 solution, solvent = EC:DMC:DEC (3:3:4, volume ratio) (EC: Ethylene Carbonate, DMC: dimethyl carbonate, EMC: ethylmethyl carbonate)) (3 μL mAh-) from GTHR KOREA was used. 1 ) was used, and an envelope-type pouch (DNP, D-EL408PH(3)) was used as a case. The pouch cell was manufactured to have a width and height of 50 mm and 90 mm, respectively.

[0299] Fig. 19 shows the results of the rate test of the 3-Ah pouch cell, and Fig. 20 shows the results of the cycle test of the 3-Ah pouch cell (in the drawings, SFL represents the case of applying the electrode of the example, and Ref represents the case of applying the reference electrode). The difference in capacity between Example 3 and Comparative Example 1 in the cycle from 0.1 C to 2.5 C was less than 1.5% from 0.1 C to 2.5 C. In addition, the capacity retention of the Example in the recovery cycle after 300 cycles was 97%, which was equivalent to that of the reference electrode. Looking at these results, it can be confirmed that stability in an abnormal state can be secured without adversely affecting the operation of the battery in a normal state through the application of the polymer layer disclosed in the present specification.

[0300]

[0301] Test Example 5.

[0302] The ARC (Accelerated Rate Calorimeter) test was performed in the following manner. The ARC test was performed on a 1-Ah pouch cell. The 1-Ah pouch cell was manufactured to have a width and length of 30 mm and 42 mm, respectively.

[0303] As the positive electrode of the above 1-Ah pouch cell, an electrode in which an active material layer was formed on a polymer layer of a current collector manufactured in the example was used. The active material layer was formed so that the loading density was approximately 24.29 mg / cm and the porosity was approximately 3.99 g / cc. Specifically, a slurry containing lithium cobalt oxide (LiCoO2) (XTC), a carbon-based conductive agent (ECP (Ketjen Black) 0.5%, SFG (Trimrex graphite) 0.4%, DB (Denka Black) 0.4%), PVDF (polyvinylidene fluoride) (Kureha), and NMP (N-Methyl-2-pyrrolidone) in a weight ratio of 75:1:1:23 (LiCoO2:conductive agent:PVDF:NMP) was applied to a thickness of about 90 μm on the polymer layer of a current collector using a doctor blade, dried at room temperature (about 25°C), and then further dried under vacuum conditions at 120°C, and then rolled to manufacture an electrode. In the manufacture of the electrode, a polymer layer was formed on both sides of the current collector body, and an active material layer was formed on each polymer layer.

[0304] The negative electrode of the above 1-Ah pouch cell was used by forming a negative electrode active material layer on a current collector, Cu foil (thickness: approximately 8 μm), so that the loading density was approximately 13.88 mg / cm and the porosity was approximately 1.75 g / cc. Water, SBR (Styrene-Butadiene rubber) binder (average particle size (D50 particle size): 150 nm), thickener (CMC, carboxymethyl cellulose), and electrode active material (1) (artificial graphite (GT), average particle size (D50 particle size): 20 μm), electrode active material (2) (natural graphite (PAS), average particle size (D50 particle size): 15 μm) were mixed in a weight ratio of 48.5:1:0.5:45:5 (water:SBR:CMC:active material (1):active material (2)), and the slurry was applied to the surface of the current collector to a thickness of about 280 μm by gap coating, and then dried at about 75°C for about 10 minutes and rolled to form the active material layer. During the manufacture of the electrode, the active material layer was formed on both sides of the current collector.

[0305] The 1100 mAh stack cell was manufactured by stacking the above 6 negative electrodes and 7 positive electrodes. A separator was placed between the negative electrode and the positive electrode. As the separator, the WL20C model separator of W-SCOPE KOREA was used. The 1-Ah pouch cell was manufactured using the stack cell and electrolyte. The electrolyte was GTHR KOREA's electrolyte (1 M LiPF6 solution, solvent = EC:DMC:DEC (3:3:4, volume ratio) (EC: Ethylene Carbonate, DMC: dimethyl carbonate, EMC: ethylmethyl carbonate))(3 μL mAh- 1 ) was used, and an envelope-type pouch (DNP, D-EL408PH(3)) was used as a case.

[0306] After charging the 1-Ah pouch cell to 4.5 V at a rate of 0.1 C, a thermocouple capable of measuring the temperature of the cell was attached to the 1-Ah pouch cell using insulating Kapton tape. The 1-Ah pouch cell equipped with the thermocouple was placed in an ARC chamber (Yeonjin S-Tech Co., Ltd., EV+ ARC), and an ARC test was performed using the standard Heat-Wait-Seek (HWS) method with an initial temperature of 50 °C. The temperature was increased at an exothermic limit of 0.02 °C / min, and heating was stopped when self-heating was confirmed in the 1-Ah pouch cell. The temperature change in this state was monitored and the TR (thermal runaway) occurrence temperature and the maximum temperature were measured. The terminal temperature was set to 300 °C for appropriate cooling of the ARC chamber. The TR occurrence temperature was set to the temperature at which the temperature change rate became 1 °C / min.

[0307] Fig. 21 shows the results of the ARC test performed on a 1-Ah pouch cell (SRL) using the current collector of the embodiment and a 1-Ah pouch cell (Bare) of the comparative example. The comparative example is a 1-Ah pouch cell manufactured in the same manner as described above, except that an Al foil without a polymer layer formed thereon is used as the current collector for manufacturing the positive electrode. In Fig. 21(a), the solid line represents the temperature change, and the dotted line represents the voltage change. Fig. 21(b) is a graph of temperature vs. temperature change rate, in which T1 is the temperature at which self-heating is confirmed in the ARC test, T2 is the TR generation temperature, and T3 is the maximum temperature. As shown in the figure, the self-heating temperature and the TR generation temperature of the 1-Ah pouch cell of the embodiment and the comparative example were the same, but in the case of the embodiment, it could be confirmed that the TR generation was significantly delayed, and the maximum temperature was also confirmed to be lower in the case of the embodiment. Similar results to Example 3 were confirmed in the case of Examples 1 and 2.

[0308]

[0309] Test Example 6.

[0310] The impact test was performed on a 3500 mAh pouch cell when the cell had a SOC (state of charge) of 100%. The 3500 mAh pouch cell was manufactured using the same method and materials as the 3-Ah pouch cell of Test Example 4, except that the number of stacks of the positive and negative electrodes was changed.

[0311] As shown in Fig. 25, the 3500 mAh pouch cell (1000) was placed on a flat floor, and a stainless steel rod (2000) having a circular cross-section with a diameter of about 2 cm was placed at the center of the pouch cell (1000). Next, a cylindrical tube with an inner diameter of about 18.5 cm was fixed on the rod, and an iron impact weight (4000) having a diameter of about 18 cm and a mass of about 9.1 kg was freely dropped from a height (H) 61 cm away from the pouch cell (1000) to the center of the cell (1000), thereby performing an impact test. The impact weight was freely dropped once for each pouch cell (1000).

[0312] In the case of introducing the electrode of the comparative example, 12 out of 19 cells exploded, whereas in the case of the cell with the current collector of the example, 17 out of 19 cells remained intact. These results emphasize the important role of the polymer layer in improving the stability of the battery. The non-explosive cells were disassembled and the condition of each component was examined. Among the non-explosive cells, the cathode and anode from the cell with the electrode of the comparative example were significantly burnt, and the separator was severely deformed. In contrast, in the cell with the electrode of the example that did not explode, each component remained intact even after an external impact.

[0313] In situ temperature changes were measured using a temperature controller (TC) attached to the external surface of the cell. Upon ignition, the temperature rose very rapidly, up to 59°C / sec, due to cascaded exothermic reactions between battery components. Even in the absence of explosion, cells incorporating the comparative electrode experienced localized heating, which was attributed to structural deformation from the impact-induced intense current flow. In cells incorporating the comparative electrode and not exploding, the temperature rise occurred 1.7 times faster than in cells incorporating the corresponding polymer layer-incorporated electrode. This result is consistent with the contrasting temperature responses observed in the impact test, with the apparent structural deformations dependent on the inclusion of the polymer layer. These contrasting results are attributed to the effective de-doping of the conducting polymer within the polymer layer under conditions of increased voltage and temperature induced by internal shorting, providing a mechanism for instantaneous shutdown of localized current flow.

[0314] After the above impact test, the pouch cell was disassembled, the positive electrode was removed, and XRF (X-ray fluorescence) analysis was performed on the positive electrode surface (active material layer surface). The analysis was performed using a Bruker Micro-XRF spectrometer, the X-ray tube was set to 5 kV and 600 mA, and a Rh target was applied.

[0315] Figure 22 shows the XRF observation results for the positive electrode surface (active material layer surface) when the electrode of Example 3 was used (SRL, SRL XRF) and the XRF observation results for the positive electrode surface (active material layer surface) when the comparative example (Bare, Bare XRF) was used. The comparative example is a 3500 mAh pouch cell manufactured in the same manner as described above, except that Al foil without a polymer layer formed thereon was used as a current collector for manufacturing the positive electrode.

[0316] In the case of the comparative example as shown in the drawing, a large amount of Cu migration from the current collector of the negative electrode was observed, but in the case of the example, almost no migration of Cu was observed.

[0317] As a result of observing a 5 cm x 5 cm square area of ​​each active material layer through the above XRF device, in the case of the example, the Cu content was approximately 0.33 wt% (unit area 1 cm 2 In the comparative example, the content of Cu was about 10.15 wt% (unit area 1 cm 2 The sugar content was approximately 0.406 wt%.

[0318]

[0319] Test Example 7.

[0320] A needle test was performed to measure the temperature surge within the battery by inserting a temperature controller (TC) inside the needle.

[0321] A TC-integrated needle was manufactured with reference to the needle design reported in the literature (Huang, S. et al. Understanding Li-Ion Cell Internal Short Circuit and Thermal Runaway through Small, Slow and In Situ Sensing Nail Penetration. J. Electrochem. Soc. 167, 090526 (2020)).

[0322] As shown in Fig. 23, the temperature change was measured while inserting the needle into a monocell (electrode area: 30 mm × 42 mm) using the positive electrode and graphite-based negative electrode of the above example. Fig. 24 shows the results of the test.

[0323] In Fig. 24, Bare is the result for the pouch cell to which the electrode of Comparative Example 1 was applied, and SRL is the result for the pouch cell to which the electrode of Example 3 was applied. The solid line in the figure indicates the temperature change during the needle test, and the dotted line indicates the voltage change during the needle test. As shown in Fig. 24 a), when the needle was inserted, the internal temperature of the cell in the case of the Comparative Example (Bare) rose to 92°C, but in the case of the Example (SRL), the internal temperature of the cell was maintained below 57°C. In the case of the Comparative Example (Bare), the temperature increase rate of the cell was 154°C / sec, and in the case of the Example (SRL), the temperature increase rate of the cell was 42°C / sec.

Claims

1. The entire body of the house; and Including a polymer layer formed on one or both sides of the above-mentioned main body, The above polymer layer includes a conductive polymer, A current collector showing a 2θ peak within a range of 3.4 to 5 degrees in the XRD (X-ray diffraction) graph of the polymer layer above.

2. A current collector in which the d-spacing of the (100) plane of XRD (X-ray diffraction) analysis in the first paragraph is within the range of 1.8 to 2.6 nm.

3. A current collector in which the ARC (Accelerated Rate Calorimeter) temperature change rate of 1℃ / min is confirmed for 30 hours or more in the first paragraph.

4. In the third paragraph, a current collector having a temperature of 200°C or less at the time of confirming the ARC (Accelerated Rate Calorimeter) temperature change rate of 1°C / min.

5. A current collector having an ARC (Accelerated Rate Calorimeter) maximum temperature of 410°C or less in the third paragraph.

6. In paragraph 1, the metal migration rate in the impact test is 1 cm per unit area. 2 A collector having a sugar content of 0.35 wt% or less.

7. A current collector in accordance with claim 1, wherein the PTC starting temperature of the polymer layer is within a range of 70°C to 200°C.

8. A current collector having a resistance increase rate of 400 ohms / sec or more after the PTC start temperature in the 7th paragraph.

9. In the first paragraph, the conductive polymer is a current collector having a long-chain hydrocarbon functional group.

10. In the 9th paragraph, the conductive polymer is a current collector including a first hydrocarbon functional group having 10 or more carbon atoms and a second hydrocarbon functional group having 9 or less carbon atoms as long-chain hydrocarbon functional groups.

11. A current collector in the 10th paragraph, wherein the ratio M2 / M1 of the number of moles of the second hydrocarbon functional group to the number of moles of the first hydrocarbon functional group M1 is within a range of 0.01 to 100.

12. In the 9th paragraph, the conductive polymer further comprises a functional group of the following chemical formula 1: [Chemical Formula 1] In chemical formula 1, L1 is a single bond, an alkylene group, or an alkylidene group, L2 is an alkylene group or an alkylidene group, R1 is hydrogen or an alkyl group, and m is a number in the range of 1 to 10.

13. In paragraph 12, the number of moles of long-chain hydrocarbon functional groups M L and the number of moles M of functional groups in chemical formula 1 P The ratio of M L / M P The entire house is within the range of 1 to 500.

14. In the first paragraph, a current collector further comprising a conductive material.

15. In the 14th paragraph, the current collector is a carbon particle, carbon fiber, graphene, graphite, carbon black or carbon nanotube.

16. The entire body of any one of paragraphs 1 to 15; and An electrode comprising an active material layer formed on a polymer layer of the above-mentioned collector.

17. In the 16th paragraph, the active material layer is an electrode including a positive electrode active material.

18. An electrode assembly comprising the electrode of clause 16.

19. A secondary battery comprising the electrode of clause 16.

20. A secondary battery comprising the electrode assembly of claim 18.

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