Battery case and secondary battery

Abstract

The present invention relates to a battery case and a secondary battery, and more particularly to a battery case including a battery case cover and a gas adsorption unit housed inside the case, the gas adsorption unit being a gas adsorption pack that opens when the internal pressure of the case increases, and a secondary battery including the same. According to the present invention, gas generated inside a battery due to abnormal operation or degradation due to the battery's lifespan is quickly adsorbed by opening a gas adsorption pack filled with a gas adsorbent housed inside the case, without the need for an additional system or sensing device, thereby ensuring the stability of the battery, preventing deformation of the battery case, reducing the resistance of the battery, and allowing the secondary battery to operate even after the gas adsorption pack is opened.

Description

Technical Field

[0001] [Cross - reference to Related Applications] This application claims the benefit of priority based on Korean Patent Application No. 10 - 2022 - 0040252 filed on Mar. 31, 2022, and all the contents disclosed in the Korean Patent Application are incorporated herein by reference in their entirety.

[0002] The present invention relates to a battery case and a secondary battery. More particularly, the present invention relates to a battery case and a secondary battery that can quickly adsorb gas generated by activation or degradation of a secondary battery by opening a gas adsorption pack accommodated inside the case without an additional system or sensing device, thereby ensuring battery stability, and further driving the secondary battery even after the gas adsorption pack is opened.

Background Art

[0003] A secondary battery is a rechargeable battery manufactured using a material in which an oxidation and reduction process between current and a substance can be repeated multiple times. That is, when a reduction reaction with respect to the material is performed by current, the battery is charged, and when an oxidation reaction with respect to the material is performed, electricity is discharged from the battery.

[0004] Generally, types of secondary batteries include nickel - cadmium batteries, nickel - metal hydride batteries, lithium secondary batteries, and lithium - ion polymer batteries. Such secondary batteries are used not only in small products such as digital cameras, P - DVDs, MP3Ps, mobile phones, PDAs, portable game devices, power tools, and E - bikes, but also in large products that require high power such as electric vehicles and hybrid vehicles, as well as in power storage devices for storing surplus generated power or renewable energy, or backup power storage devices.

[0005] The lithium secondary battery, for example, is formed by laminating a cathode, a separator, and an anode, and charging and discharging are performed while the process of lithium ions being inserted (intercalated) from the lithium metal oxide of the cathode into the graphite electrode of the anode and being removed (deintercalated) is repeated. And these materials are selected in consideration of the battery life, charge and discharge capacity, temperature characteristics, stability, etc.

[0006] The lithium secondary battery is classified into a can-type secondary battery in which the electrode assembly is built into a metal can and a pouch-type secondary battery in which the electrode assembly is built into a pouch of an aluminum laminate sheet according to the shape of the battery case. The can-type secondary battery is classified into a cylindrical battery and a prismatic battery.

[0007] When the lithium secondary battery rises to a voltage equal to or higher than the operating voltage, the constituent materials are decomposed to generate flammable gas, or the battery deteriorates and gas is generated due to the collapse of the cathode structure. The gas generated in this way increases the resistance of the battery and raises the internal pressure of the battery. If left unattended, the battery may explode.

[0008] Generally, for square and cylindrical secondary batteries, in order to ensure safety when gas is generated, a method of joining a safety vent to the cap plate, which is the upper plate of the battery, is mainly used. This safety device prevents the battery from exploding by safely discharging the internal gas to the outside when the internal pressure of the battery rises abnormally.

[0009] However, in the case of a pouch-type secondary battery, since the gas discharge is determined by the seal strength of the pouch without a separate safety device, there is a problem that it is difficult to open the pouch and discharge the gas accurately when a specific pressure is reached. Furthermore, even if the risk of explosion can be reduced by opening the pouch and discharging the gas, there still remains a problem that the secondary battery cannot be driven any further after the pouch is opened.

[0010] Therefore, there is a need to develop a means to improve the resistance and internal pressure increase due to gas generation in lithium secondary batteries, as well as battery explosion, ignition, and inoperability phenomena caused thereby, and to ensure battery stability without degrading various battery performances.

Prior Art Documents

Patent Documents

[0011]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0012] In order to solve the problems of the prior art as described above, the present invention aims to provide a battery case that can ensure the stability of the battery by delaying the time when the battery case explodes due to gas by automatically opening and adsorbing the gas generated in the battery with a gas adsorption pack accommodated inside the battery case without the need for recognition work through an additional system or sensing device.

[0013] Further, the present invention aims to provide a secondary battery including the battery case, an electrode assembly accommodated inside the battery case, and an electrolyte filled inside the battery case.

[0014] The above object and other objects of the present invention can all be achieved by the present invention described below.

Means for Solving the Problems

[0015] To achieve the above object, the present invention provides a battery case including a battery case cover and a gas adsorption part accommodated inside the case, wherein the gas adsorption part is characterized in that a gas adsorption pack is opened when the internal pressure of the case increases.

[0016] The gas adsorption part can preferably include a gas adsorption pack filled with a gas adsorbent and a piezoelectric element that bends when the internal pressure increases and pierces through the gas adsorption pack.

[0017] The piezoelectric element can preferably include a pressure conversion part containing a piezoelectric substance and an electroactive part containing an electroactive substance.

[0018] The electroactive substance may preferably be an electroactive polymer (Electro Active Polymer).

[0019] The piezoelectric element can preferably include one or more perforations in the edge.

[0020] The gas adsorption part may preferably be attached to the inner wall of the case.

[0021] The gas adsorbent can preferably include one or more selected from the group consisting of a gas adsorbent molecular sieve, a gas adsorbent metal, and a gas adsorbing substance.

[0022] The gas adsorbent molecular sieve may preferably be one or more selected from the group consisting of silica gel, carbon fiber, a porous carbon material, a porous metal oxide, a porous gel, and zeolite.

[0023] The gas adsorbent metal may preferably be one or more selected from the group consisting of nickel (Ni), platinum (Pt), palladium (Pd), calcium (Ca), strontium (Sr), barium (Ba), thallium (Tl), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), and tungsten (W).

[0024] The gas adsorbing substance may preferably be BaTiO3, PB(Mg3Nb 2 / 3)It may be at least one selected from the group consisting of O3-PbTiO3 (PMN-PT), hafnium oxide (HfO2), SrTiO3, SnO2, CeO2, MgO, NiO, CaO, ZnO, ZrO2, Y2O3, Al2O3, TiO2, sodium hydroxide (NaOH), calcium hydroxide (Ca(OH)2), and potassium hydroxide (KOH).

[0025] The gas adsorption pack may preferably comprise at least one selected from the group consisting of an olefin resin, a fluororesin, and a polyamide resin.

[0026] The piezoelectric element may preferably include a connection circuit that starts from the pressure conversion part and leads to the electroactive part.

[0027] The gas adsorption part may preferably be installed such that a piezoelectric element is positioned between the inner wall of the case and the gas adsorption pack.

[0028] The present invention also provides a secondary battery including the battery case, an electrode assembly housed inside the battery case, and an electrolyte filled inside the battery case.

[0029] In the secondary battery, preferably, the gas adsorption pack may be blocked from the outside air or may be in an opened state.

[0030] The secondary battery may preferably be a pouch-type battery.

Advantages of the Invention

[0031] According to the present invention, when the structure of the positive electrode collapses due to degradation due to the battery life and gas is generated, or when an abnormal operating state such as overcharging or high-temperature exposure occurs and the internal electrolyte is decomposed while generating gas, resulting in an increase in the internal pressure of the battery, the gas adsorption pack housed inside the battery case is automatically opened to quickly adsorb the gas, ensuring the stability of the battery, reducing the resistance of the battery, and preventing deformation of the battery case.

[0032] In addition, since the battery case according to the present invention does not require an additional sensing device for checking the temperature, voltage, etc. of the battery, the manufacturing process is simple, and there is an effect that malfunction due to an error of the sensing device does not occur.

[0033] In addition, by reacting sensitively to changes in the internal pressure of the battery case, the stability of the battery is further improved, and the battery case is not damaged, so that the battery can be driven even after the gas adsorption pack is opened.

Brief Description of the Drawings

[0034] The following drawings attached to this specification illustrate embodiments of the present invention and serve to further understand the technical idea of the present invention together with the detailed description to be described later. Therefore, the present invention should not be construed as being limited to the matters described in such drawings.

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Modes for Carrying Out the Invention

[0035] When the inventors were researching a method for removing gas generated inside a secondary battery, they found that when a gas adsorption pack filled with a gas adsorbent and a piezoelectric element that bends when the internal pressure increases due to gas generation and can pierce through the gas adsorption pack are provided inside the battery case, the internal pressure increases due to the gas generated inside the battery, causing the battery case to deform. However, before it leads to an explosion, the gas can be removed. Therefore, the stability of the battery is ensured, the resistance of the battery is reduced, and the battery case is not damaged. After the gas adsorption pack is opened, the battery cell can still be driven, ensuring the performance of the battery. Based on this, the inventors further advanced their research and completed the present invention.

[0036] Hereinafter, with reference to the accompanying drawings, embodiments that can be easily implemented by those with ordinary knowledge in the technical field to which the present invention pertains will be described in detail. However, when explaining the operating principle of the preferred embodiments of the present invention in detail, if it is determined that a specific explanation of related known functions or configurations may unnecessarily obscure the gist of the present invention, the detailed explanation thereof will be omitted.

[0037] Also, the same reference numerals are used for parts having similar functions and actions throughout the drawings. Throughout the specification, when a part is said to be "connected" to another part, this includes not only the case where they are "directly connected" but also the case where they are "indirectly connected" with other elements intervening therebetween. Further, when a component is said to "include" something, it means that, unless otherwise stated to the contrary, it does not exclude other components and can further include other components.

[0038] The description of specifying components by limitation or addition is applicable to all inventions without particular limitation and is not limited to a specific invention.

[0039] A battery case according to an embodiment of the present invention includes a battery case cover 10 and a gas adsorption part 20 accommodated inside the case. The gas adsorption part 20 is characterized in that when the internal pressure of the case increases, a gas adsorption pack 21 filled with a gas adsorbent is opened. In this case, by quickly adsorbing and removing the gas that caused the pressure increase, the stability of the battery can be ensured and the resistance of the battery can be reduced.

[0040] The gas adsorption part 20 may preferably include a gas adsorption pack 21 filled with a gas adsorbent and a piezoelectric element 22 that bends and pierces the gas adsorption pack when the internal pressure increases.

[0041] The terms "secondary battery", "battery" and / or "battery cell" used in the present invention refer to those in which an electrode assembly is enclosed inside a battery case together with an electrolyte, unless otherwise specified. Furthermore, secondary batteries, batteries and battery cells can be connected in series to form a battery module, and depending on the required charge and discharge capacity, a number of battery modules can be connected in parallel and / or in series to form a battery pack.

[0042] In the present invention, the battery case cover has an empty space inside and can be formed to accommodate an electrode assembly and an electrolyte in such an internal space.

[0043] Hereinafter, the gas adsorption part 20 will be specifically described.

[0044] As an example, the gas adsorption part 20 may be attached to the inner wall of the battery case cover 10. In such a case, it can have no influence on the charge and discharge of the secondary battery.

[0045] Based on the position of the accommodated electrode assembly 110, the gas adsorption part 20 may preferably be installed on the inner wall of the upper or lower cover, or both of them. In such a case, by more quickly adsorbing the generated gas and rapidly reducing the internal pressure, the stability of the battery is ensured, deformation of the case is prevented, and the resistance of the battery is reduced.

[0046] The gas adsorption part 20 may, for example, adhere to the upper part of the electrode assembly 110. In such a case, it can have no influence on the charge and discharge of the secondary battery.

[0047] The gas adsorption part 20 may, for example, be fixed to the inner wall of the battery case cover 10 or the upper part of the electrode assembly 110 with a PET tape. In such a case, there is an advantage that it has no influence on the charge and discharge of the secondary battery and is not affected by the electrolyte.

[0048] The PET tape may, for example, be a tape in which a silicon-based adhesive is applied to a polyester film.

[0049] The gas adsorption pack 21 may, for example, be similar to the outer shape of the case, preferably rectangular, but may also be amorphous with free shape changes.

[0050] Inside the gas adsorption pack 21, a gas adsorbent capable of adsorbing gas is incorporated.

[0051] The gas generated inside the secondary battery may, for example, be gas generated by the decomposition of the electrolyte or gas generated by the collapse of the positive electrode structure during degradation due to the battery life.

[0052] The gas generated by the decomposition of the electrolyte may, for example, be oxygen, carbon monoxide (CO) and / or carbon dioxide (CO2), and the gas generated by the collapse of the positive electrode structure during degradation due to the battery life may, for example, be oxygen.

[0053] The gas adsorbent is not greatly limited in type as long as it is a substance capable of easily adsorbing the gas generated inside the secondary battery, and preferably, it may contain one or more selected from the group consisting of a gas-adsorbing molecular sieve, a gas-adsorbing metal, and a gas-adsorbing substance. In such a case, the gas inside the battery can be efficiently adsorbed, ensuring the stability of the battery, reducing the resistance of the battery, and preventing the deformation and explosion of the case.

[0054] The gas-adsorbing molecular sieve may be, for example, one or more selected from the group consisting of silica gel, carbon fiber, a porous carbon material, a porous metal oxide, a porous gel, and zeolite.

[0055] The porous carbon material may be, for example, one or more selected from the group consisting of carbon molecular sieve and activated carbon.

[0056] The activated carbon may preferably be one or more selected from the group consisting of granular carbon, powdered carbon, formed carbon, and activated fiber.

[0057] The porous metal oxide may be, for example, one or more selected from the group consisting of silica gel, alumina, and molecular sieve.

[0058] The zeolite can be classified by crystal structure and may be, for example, one or more selected from the group consisting of A-type zeolite, L-type zeolite, β-type zeolite, MFI-type zeolite, and faujasite-type zeolite.

[0059] The gas-adsorbing metal may be, for example, one or more selected from the group consisting of nickel (Ni), platinum (Pt), palladium (Pd), calcium (Ca), strontium (Sr), barium (Ba), thallium (Tl), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), and tungsten (W).

[0060] The gas adsorption material is, for example, one or more selected from the group consisting of BaTiO3, PB(Mg3Nb 2 / 3 )O3-PbTiO3 (PMN-PT), hafnium oxide (HfO2), SrTiO3, SnO2, CeO2, MgO, NiO, CaO, ZnO, ZrO2, Y2O3, Al2O3, TiO2, sodium hydroxide (NaOH), calcium hydroxide (Ca(OH)2), and potassium hydroxide (KOH).

[0061] The gas adsorption pack 21 is, for example, provided with a space portion so as to be able to store a gas adsorbent, and can be made of a material having a predetermined thickness that can be perforated or torn by a piezoelectric element.

[0062] The gas adsorption pack 21 can, for example, include one or more selected from the group consisting of an olefin resin, a fluororesin, and a polyamide resin. In such a case, it can have no adverse effect on the electrolyte.

[0063] The olefin resin can, for example, include one or more selected from the group consisting of polypropylene, polyethylene, polyethylene acrylic acid, and polybutylene.

[0064] The polyamide resin can, for example, be one or more selected from the group consisting of polyamide 4.6, polyamide 6, polyamide 6.6, polyamide 6.10, polyamide 7, polyamide 8, polyamide 9, polyamide 11, polyamide 12, and MXD6.

[0065] The fluororesin may preferably be polytetrafluoroethylene (PTFE).

[0066] Generally, in order to remove the gas generated by overcharging or degradation due to the lifespan of a secondary battery, a separate gas removal process is performed, and for this purpose, a separate sensing device is required. However, as shown in FIGS. 2 to 3, the present invention includes a gas adsorption part inside the case, and the gas adsorption part includes a gas adsorption pack filled with a gas adsorbent and a piezoelectric element that bends when the internal pressure increases and penetrates the gas adsorption pack, so that it can quickly remove the gas by sensitively reacting to the change in internal pressure caused by gas generation and opening the gas adsorption pack. Therefore, the stability of the battery is greatly ensured, and the resistance of the battery can be reduced to improve the performance of the battery.

[0067] In addition, when gas is generated due to battery degradation, the battery bulges and there is a risk of explosion. However, by opening and removing such gas from the gas adsorption pack, it is possible to significantly reduce the load applied to the secondary battery.

[0068] Also, if the case is partially damaged or opened to remove the gas, the stability of the battery is ensured, but the battery can no longer perform its functions. However, the present invention has the advantage that the battery can be driven even after the gas adsorption pack is opened by adsorbing and removing the gas without damaging the case.

[0069] The piezoelectric element 22 can include, for example, a pressure conversion part 221 containing a piezoelectric material and an electroactive part 222 containing an electroactive material.

[0070] The pressure conversion part 221 generates a voltage and transmits it to the electroactive part 222 when the internal pressure increases due to the gas generated inside the case. The electroactive part 222 deforms at a predetermined angle by the transmitted voltage to penetrate the gas adsorption pack and release the gas adsorbent, so as to adsorb and remove the internal gas.

[0071] In this description, the release of the gas adsorbent means that a fluid containing a gas comes into contact with the gas adsorbent, and the gas adsorbent is discharged into the fluid or the fluid flows into the gas adsorbent. The fluid may be, for example, an electrolyte, an inert gas (e.g., N2, Ar, etc.), or steam.

[0072] The pressure conversion unit 221 is an element that exhibits the piezoelectric phenomenon and is also called a piezoelectric battery element.

[0073] In this description, the piezoelectric phenomenon is a phenomenon that converts mechanical energy into electrical energy. When an external stress or vibration is applied, positive and negative charges proportional to the external force appear at both ends from the pressure conversion unit, and an electrical signal is generated, which means a reversible phenomenon.

[0074] When gas is generated inside the battery and the volume of the case expands, the pressure conversion unit 221 receives an applied pressure. As a result, a voltage is generated in the pressure conversion unit 221, and power can be supplied to the outside.

[0075] In particular, according to an embodiment of the present invention, the gas adsorption unit 20 may be attached to the inner wall of the case cover. Thereby, it can react sensitively to a change in the internal pressure due to gas generation inside the battery 1. That is, even if the internal pressure of the battery 1 increases slightly, a voltage can be immediately generated and power can be supplied to the outside.

[0076] Here, the pressure conversion unit 221 is preferably located near the middle of the battery case cover 10 as an example. This is because when the swelling phenomenon occurs in which the battery 1 swells due to an increase in internal pressure, the volume expands most quickly near the middle, and there is an advantage that it can react more quickly.

[0077] The pressure conversion unit 221 may be, for example, a thin film type.

[0078] The pressure conversion unit 221 may contain a piezoelectric material as an example.

[0079] The piezoelectric material may be, for example, one or more selected from the group consisting of quartz, tourmaline, Rochelle salt, Barium Titanate, ammonium dihydrogen phosphate, and ethylenediamine tartrate. However, as long as it conforms to the definition of the present invention, it is not particularly limited, and commercially available products may be used.

[0080]

[0081] The electroactive part 222 may include, for example, an electroactive substance.

[0082]

[0083]

[0084] The electroactive electroactive polymer includes, for example, a liquid crystal elastomer, an electro-viscoelastic elastomer, electrostrictive paper, an electrostrictive graft elastomer, a dielectric elastomer, a ferroelectric polymer, etc., and has the advantages of fast response speed and precise displacement adjustment.

[0085] The electroactive part 222 can have an elongated shape, for example, and when a voltage is applied from the pressure conversion part 221, it bends to pierce the gas adsorption pack 21 so that the gas adsorbent is released.

[0086] Specifically, when the internal pressure increases due to gas generation and the volume expands in the pressure conversion part 221 of the piezoelectric element 22, a voltage is generated in the pressure conversion part 221 and transmitted to the electroactive part 222. The electroactive part 222 deforms at a predetermined angle toward the gas adsorption pack 21 by the generated voltage to pierce or tear the gas adsorption pack 21, thereby releasing the gas adsorbent to adsorb and remove the gas, controlling overheating and explosion of the battery, preventing deformation of the case, and reducing the resistance of the battery.

[0087] The piezoelectric element 22 can include one or more perforations 223 on the edge, for example, and preferably can be located at the end of the electroactive part 222.

[0088] The perforation 223 may preferably be made of the same material as the electroactive substance, and its shape can change due to the voltage generated in the pressure conversion part 221 to pierce the gas adsorption pack 21.

[0089] The perforation 223 can have a pointed tip shape, for example, and in such a case, the gas adsorption pack 21 can be pierced more easily.

[0090] The perforation 223 can include one or more, preferably two or more, on the edge of the piezoelectric element 22.

[0091] The drilling portion 223 can preferably include one or more, preferably two or more, at the edge of the electroactive portion 222.

[0092] As an example, the drilling portion 223 may extend with the same thickness as the electroactive portion 222 or may gradually become thinner. Preferably, when the thickness gradually becomes thinner, the gas adsorption pack 21 can be more easily drilled or torn.

[0093] As an example, a groove portion 224 may be formed in a portion where the drilling portion 223 is connected to the electroactive portion 222. In such a case, it can react sensitively to the voltage applied from the pressure conversion portion 221 and drill or tear the gas adsorption pack 21.

[0094] As an example, the piezoelectric element 22 can include a connection circuit 225 that starts from the pressure conversion portion 221 and extends to the electroactive portion 222. In such a case, by additionally transmitting the voltage generated in the pressure conversion portion 221 to the electroactive portion 222 to cause a shape change in the electroactive portion 222, the stability of the battery can be further improved.

[0095] The connection circuit 225 is not particularly limited as long as it can transmit current. As an example, it may be a substance with high electrical conductivity, and preferably, it may be silver, copper, gold, or nickel.

[0096] As an example, the gas adsorption portion 20 may be installed such that the piezoelectric element 22 is located between the inner wall of the case and the gas adsorption pack 21. In such a case, while not affecting the charge and discharge of the secondary battery, it has the advantage of providing higher stability because it can immediately remove the rising gas even if the density is low.

[0097] As an example, the gas adsorption portion 20 may be attached to the upper surface of the electrode assembly 110. In such a case, it can be prevented from affecting the charge and discharge of the secondary battery.

[0098] The gas adsorption pack 21 and the piezoelectric element 22 can be fixed with, for example, a PET tape, but are not limited thereto.

[0099] In the piezoelectric element 22, the pressure conversion part 221 and the electroactive part 222 can be fixed with, for example, a PET tape, but are not limited thereto.

[0100] The present invention can include the battery case, the electrode assembly housed inside the battery case, and the electrolyte filled inside the battery case.

[0101] The electrode assembly can be a jelly roll type electrode assembly having a structure in which a separator is interposed between a long sheet-like positive electrode and a negative electrode and then wound up, a stack type electrode assembly composed of unit cells having a structure in which rectangular positive and negative electrodes are laminated with a separator therebetween, a stack-folding type electrode assembly in which unit cells are wound up by a long separation film, or a lamination-stack type electrode assembly in which unit cells are laminated with a separator therebetween and adhered to each other, etc., but is not limited thereto.

[0102] Further, the electrode assembly has electrode tabs (not shown) extending therefrom. As an example, the positive electrode tab extends from the positive electrode and the negative electrode tab extends from the negative electrode. Here, when the electrode assembly is configured in a state where a large number of positive electrodes and a large number of negative electrodes are laminated, the electrode tabs extend from the respective positive and negative electrodes. At this time, the electrode tabs are not directly exposed outside the case and can be connected to other components such as the electrode lead 130.

[0103] The electrode lead 130 is electrically connected in part to electrode tabs extending from the positive electrode or the negative electrode, respectively. One end of such an electrode lead is connected to the electrode tab, and the other end is exposed outside the case, and the other end exposed outside can function as an electrode terminal. Therefore, when a charger, a load, or the like is connected to the other end of such an electrode lead 130, the secondary battery can be charged and discharged. Further, an insulating film can be attached to a part of the upper and lower surfaces of the electrode lead to enhance the sealing degree with the battery case and at the same time ensure an electrically insulating state.

[0104] The positive electrode is, for example, manufactured by applying a positive electrode mixture containing a positive electrode active material onto a positive electrode current collector and then drying it. The positive electrode mixture may further selectively contain a binder, a conductive material, a filler, etc. as required.

[0105] The positive electrode current collector is manufactured, for example, with a thickness of 3 to 500 μm. Such a positive electrode current collector is not particularly limited as long as it does not induce a chemical change in the battery and has high conductivity. For example, it may be one or more selected from the group consisting of stainless steel, aluminum, nickel, titanium, fired carbon, surface-treated aluminum, and surface-treated stainless steel. The surface treatment may be, for example, surface treatment with one or more selected from the group consisting of carbon, nickel, titanium, and silver.

[0106] Also, the positive electrode current collector can, for example, form fine irregularities on its surface to enhance the adhesive force of the positive electrode active material, and various forms such as a film, a sheet, a foil, a net, a porous body, a foam body, and a non-woven fabric body are possible.

[0107] The positive electrode active material is a substance capable of causing an electrochemical reaction, and as a lithium transition metal oxide, it contains two or more transition metals. For example, lithium cobalt oxide (LiCoO2), lithium nickel oxide (LiNiO2), etc. which are substituted with one or two or more transition metals; lithium manganese oxide substituted with one or two or more transition metals; chemical formula LiNi1-y M y O₂ (where M = Co, Mn, Al, Cu, Fe, Mg, B, Cr, Zn or Ca, containing one or more of the above elements, 0.01 ≦ y ≦ 0.7); Li 1+z Ni 1 / 3 Co 1 / 3 Mn 1 / 3 O₂, Li 1+z Ni 0.4 Mn 0.4 Co 0.2 O₂, such as Li 1+z Ni b Co 1-(b+c+d) M d O (2-e) A e (where -0.5 ≦ z ≦ 0.5, 0.1 ≦ b ≦ 0.8, 0.1 ≦ c ≦ 0.8, 0 ≦ d ≦ 0.2, 0 ≦ e ≦ 0.2, b + c + d < 1, M = Al, Mg, Cr, Ti, Si or Y, A = F, P or Cl) lithium nickel cobalt manganese composite oxide; chemical formula Li 1+x M 1-y M y PO 4-z X z (where M = transition metal, preferably Fe, Mn, Co or Ni, M = Al, Mg or Ti, X = F, S or N, -0.5 ≦ x ≦ +0.5, 0 ≦ y ≦ 0.5, 0 ≦ z ≦ 0.1) olivine-type lithium metal phosphate, etc. are included, but not limited thereto.

[0108] The conductive material is added at 1 to 30% by weight based on the total weight of the mixture containing the positive electrode active material, the conductive material, and the binder, for example. Such a conductive material is not particularly limited as long as it has conductivity without inducing chemical changes in the battery. For example, graphite such as natural graphite and artificial graphite; carbon black such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black; conductive fibers such as carbon fibers and metal fibers; metal powders such as aluminum powder and nickel powder; conductive whiskers such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; and conductive materials such as polyphenylene derivatives and carbon fluoride; One or more selected from the group consisting of may be used.

[0109] The binder is a component that assists in binding the active material and the conductive material, etc. and binding to the current collector, and is added at 1 to 30% by weight based on the total weight of the mixture containing the positive electrode active material, the conductive material, and the binder, for example.

[0110] The binder may be, for example, one or more selected from the group consisting of polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinyl pyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene butadiene rubber, and fluorine rubber.

[0111] The filler is selectively used as a component for suppressing the expansion of the electrode, does not induce chemical changes in the battery, and is not particularly limited as long as it is a fibrous material. For example, olefin polymers such as polyethylene and polypropylene; and / or fibrous substances such as glass fibers and carbon fibers; are used.

[0112] The negative electrode is manufactured, for example, by applying a negative electrode mixture containing a negative electrode active material onto a negative electrode current collector and then drying it. The negative electrode mixture may contain components such as a conductive material, a binder, and a filler as described above, if necessary.

[0113] The negative electrode current collector is manufactured, for example, with a thickness of 3 to 500 μm. Such a negative electrode current collector is not particularly limited as long as it does not induce chemical changes in the battery and has high conductivity. For example, one or more selected from the group consisting of copper, stainless steel, aluminum, nickel, titanium, fired carbon, surface-treated copper, surface-treated stainless steel, and an aluminum-cadmium alloy may be used. The surface treatment may be, for example, surface-treated with one or more selected from the group consisting of carbon, nickel, titanium, and silver.

[0114] Also, similar to the positive electrode current collector, the negative electrode current collector can also form fine irregularities on its surface to strengthen the binding force of the negative electrode active material, and may be used in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a non-woven fabric.

[0115] The negative electrode active material is, for example, carbon such as graphitizable carbon and graphite-based carbon; Li x Fe2O3(0≦x≦1), Li x WO2(0≦x≦1), Sn x Me 1-x Me y O z (Me: Mn, Fe, Pb, Ge; Me: Al, B, P, Si, Group 1, Group 2, Group 3 elements of the periodic table, halogen; 0≦x≦1; 1≦y≦3; 1≦z≦8) and other metal composite oxides; lithium metal; lithium alloy; silicon-based alloy; tin-based alloy; metal oxides such as SnO, SnO2, PbO, PbO2, Pb2O3, Pb3O4, Sb2O3, Sb2O4, Sb2O5, Sb2O6, GeO, GeO2, Bi2O3, Bi2O4, Bi2O5; conductive polymers such as polyacetylene; and one or more selected from the group consisting of Li-Co-Ni-based materials may also be used.

[0116] The binder, conductive material, and components added as necessary are the same as those described for the positive electrode. In some cases, a filler may be selectively added as a component for suppressing the expansion of the negative electrode. Such a filler does not induce chemical changes in the battery, and if it is a fibrous material, it is not particularly limited. As an example, olefin polymers such as polyethylene and polypropylene; and / or fibrous substances such as glass fiber and carbon fiber are used.

[0117] In addition, the negative electrode mixture may further contain other components such as a viscosity regulator and an adhesion promoter, either selectively or in combination of two or more.

[0118] The viscosity regulator is a component that adjusts the viscosity of the electrode mixture so that the mixing process of the electrode mixture and the coating process on the current collector are facilitated. As an example, it may be added at 1 to 30% by weight based on the total weight of the negative electrode active material, conductive material, binder, and filler. Examples of such viscosity regulators include, but are not limited to, carboxymethyl cellulose and / or polyvinylidene fluoride. In some cases, the above-mentioned solvent can also serve as a viscosity regulator.

[0119] The adhesion promoter is an auxiliary component added to improve the adhesion of the active material to the current collector, and may be added at 10% by weight or less with respect to the binder, or at more than 0% by weight and up to 10% by weight. Examples include oxalic acid, adipic acid, formic acid, acrylic acid derivatives, itaconic acid derivatives, and the like.

[0120] The separator is located between the positive electrode and the negative electrode, and can be formed in the form of a porous membrane so as to electrically insulate the positive electrode and the negative electrode from each other and allow lithium ions and the like to pass through each other between the positive electrode and the negative electrode. Such a separator can be composed of, for example, a porous membrane using polyethylene, polypropylene, or a composite film thereof.

[0121] The electrolyte is for moving lithium ions generated by the electrochemical reaction of the electrodes during charging and discharging of the secondary battery, and may be an electrolytic solution, a solid electrolyte, and / or a semi-solid electrolyte.

[0122] As an example, the electrolytic solution may be a non-aqueous electrolytic solution containing a lithium salt.

[0123] As an example, the non-aqueous electrolytic solution containing a lithium salt consists of an electrolytic solution and a lithium salt, and the electrolytic solution can include, as an example, a non-aqueous organic solvent, an organic solid electrolyte, an inorganic solid electrolyte, etc.

[0124] As an example, the non-aqueous organic solvent may be an aprotic organic solvent. Specifically, it may be one or more selected from the group consisting of N-methyl-2-pyrrolidinone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, γ-butyrolactone, 1,2-dimethoxyethane, tetrahydroxyfuran (franc), 2-methyltetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolane, formamide, dimethylformamide, dioxolane, acetonitrile, nitromethane, methyl formate, methyl acetate, triphosphate ester, trimethoxymethane, dioxolane derivative, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, propylene carbonate derivative, tetrahydrofuran derivative, ether, methyl propionate, and ethyl propionate.

[0125] As an example, for the organic solid electrolyte, one or more selected from the group consisting of a polyethylene derivative, a polyethylene oxide derivative, a polypropylene oxide derivative, a phosphate ester polymer, a polyaditation lysine, a polyester sulfide, a polyvinyl alcohol, a polyvinylidene fluoride, and a polymer containing an ionic dissociation group may be used.

[0126] The inorganic solid electrolyte may be, for example, one or more selected from the group consisting of Li nitrides, halides, and sulfates. Specifically, it may be one or more selected from Li3N, LiI, Li5NI2, Li3N-LiI-LiOH, LiSiO4, LiSiO4-LiI-LiOH, Li2SiS3, Li4SiO4, Li4SiO4-LiI-LiOH, and Li3PO4-Li2S-SiS2.

[0127] The lithium salt is a substance that is easily soluble in the non-aqueous electrolyte. For example, one or more selected from the group consisting of LiCl, LiBr, LiI, LiClO4, LiBF4, LiB 10 Cl 10 , LiPF6, LiCF3SO3, LiCF3CO2, LiAsF6, LiSbF6, LiAlCl4, CH3SO3Li, (CF3SO6)2NLi, lithium chloroborane, lithium lower aliphatic carboxylate, lithium 4-phenylborate, and imide may be used.

[0128] In addition, for the purpose of improving charge-discharge characteristics, flame retardancy, etc., one or more selected from the group consisting of pyridine, triethyl phosphite, triethanolamine, cyclic ether, ethylenediamine, n-glyme, triamide hexalinic acid, nitrobenzene derivative, sulfur, quinoneimine dye, N-substituted oxazolidinone, N,N-substituted imidazolidine, ethylene glycol dialkyl ether, ammonium salt, pyrrole, 2-methoxyethanol, and aluminum trichloride may be added to the non-aqueous electrolyte.

[0129] In addition, in order to impart non-flammability to the non-aqueous electrolyte, as an example, halogen-containing solvents such as carbon tetrachloride and vinylidene fluoride can also be further included. In order to improve the high-temperature storage characteristics, carbon dioxide gas can also be further included, and FEC (Fluoro-Ethylene Carbonate), PRS (Propene sultone), etc. can also be further included. Preferably, a lithium salt such as LiPF6, LiClO4, LiBF4, LiN(SO2CF3)2, etc. is added to a mixed solvent of a cyclic carbonate of EC or PC which is a high-dielectric constant solvent and a linear carbonate of DEC, DMC or EMC which is a low-viscosity solvent to produce a lithium salt-containing non-aqueous electrolyte.

[0130] The solid electrolyte may be, for example, one or more selected from the group consisting of organic solid electrolytes, inorganic solid electrolytes having ion-conductive activity, and composite solid electrolytes.

[0131] The semi-solid electrolyte may be, for example, a gel-like electrolyte obtained by adding a polymer additive to an electrolyte composed of a lithium salt, an additive, and an organic solvent.

[0132] The polymer additive may be, for example, one or more selected from the group consisting of POE (Polyethyleneoxide) and PTFE (Polytetrafluoroethylene).

[0133] The electrode assembly includes electrode tabs. The electrode tabs are respectively connected to the positive electrode and the negative electrode of the electrode assembly, protrude to the outside on one side from the electrode assembly, and serve as a path through which electrons can move between the inside and the outside of the electrode assembly.

[0134] An electrode lead is connected to the electrode tab of the electrode assembly by spot welding or the like. A part of the electrode lead is surrounded by an insulating portion. The insulating portion is located limited to the sealing portion where the upper case and the lower case of the battery case are heat-sealed, and adheres the electrode lead to the battery case. And it prevents the electricity generated from the electrode assembly from flowing to the battery case through the electrode lead, and maintains the sealing of the battery case. Therefore, such an insulating portion is manufactured from a non-conductive insulator having poor electrical conductivity.

[0135] As the insulating portion, an insulating tape that easily adheres to the electrode lead and has a relatively thin thickness is often used, but it is not limited to this, and various members can be used as long as they can insulate the electrode lead.

[0136] One end of the electrode lead is connected to the electrode tab, and the other end protrudes outside the electric case respectively. That is, the electrode lead includes a positive electrode lead having one end connected to the positive electrode tab and extending in the direction in which the positive electrode tab protrudes, and a negative electrode lead having one end connected to the negative electrode tab and extending in the direction in which the negative electrode tab protrudes. On the other hand, both the positive electrode lead and the negative electrode lead have the other end protruding outside the battery case. Thereby, the electricity generated inside the electrode assembly can be supplied to the outside. In addition, since the positive electrode tab and the negative electrode tab are respectively formed to protrude in various directions, the positive electrode lead and the negative electrode lead can also extend in various directions respectively.

[0137] As an example, the battery case can be composed of a structure of an inner layer / metal layer / outer layer laminate sheet.

[0138] Since the inner layer is in direct contact with the electrode assembly, it must have insulation and electrolyte resistance. Also, for sealing with the outside, that is, the sealing part where the inner layers are thermally bonded to each other must have excellent thermal bonding strength. As a material for such an inner layer, as an example, one or more selected from the group consisting of polyolefin resins such as polypropylene, polyethylene, polyethylene acrylic acid, and polybutylene, which are excellent in chemical resistance and have good sealing properties, polyurethane resins, and polyamide resins may be used, but are not limited thereto. Polypropylene, which is excellent in mechanical physical properties such as tensile strength, rigidity, surface hardness, and impact resistance and chemical resistance, is preferred.

[0139] The metal layer is in contact with the inner layer and corresponds to a barrier layer that prevents moisture and various gases from penetrating into the battery from the outside. Such a metal layer can use, as an example, one or more selected from the group consisting of aluminum, aluminum alloys, copper, and iron alloys such as stainless steel, which are light and have excellent formability.

[0140] Also, an outer layer is provided on the other side of the metal layer. The outer layer can use a heat-resistant polymer that is excellent in tensile strength, moisture permeability prevention, and air permeability prevention so as to protect the electrode assembly and ensure heat resistance and chemical resistance. As an example, polyamide and / or polyethylene terephthalate can be used, but are not limited thereto.

[0141] The secondary battery may preferably be a pouch-type battery. In this case, the gas generated inside the battery can be adsorbed to prevent the risk of gas explosion or fire, and various sizes and shapes can be realized, and it has the advantage of having a high energy density.

[0142] As an example, in the secondary battery, the gas adsorption pack may be blocked from the outside air or may be opened. That is, before the battery operates normally or deteriorates due to its lifespan, the gas adsorption pack is in a state of being blocked from the outside air. When the battery deteriorates due to its lifespan or abnormal operation generates gas, the gas adsorption pack is opened and the gas adsorbent is released, thereby absorbing and removing the gas to ensure the stability of the battery, improving the performance of the battery by reducing the resistance of the battery, and having the advantage that the battery can be driven even after the gas adsorption pack is opened. Conventionally, when gas is generated inside the battery, a hole is made in the battery case to discharge and remove the gas. In such a case, there is a problem that the electrolyte or the like flows out from the battery case with the hole, and the battery cannot be driven any further.

[0143] A plurality of secondary batteries according to the present invention can be stacked in the vertical direction or the horizontal direction to form a battery module. In this case, the gas generated inside the battery due to abnormal operation or deterioration due to lifespan can be easily removed, and the battery can be driven even after the gas is removed.

[0144] Further, a plurality of the battery modules can be stacked in the vertical direction or the horizontal direction to form a battery pack. In this case, the gas generated inside the battery case due to abnormal operation of the battery can be easily removed, and the battery can be driven even after the gas is removed.

[0145] In the present invention, as an example, the manufacturing method of the secondary battery includes steps of applying a positive electrode active material slurry obtained by dissolving a positive electrode active material in a solvent to a positive electrode current collector, and applying a negative electrode active material slurry obtained by dissolving a negative electrode active material in a solvent to a negative electrode current collector to manufacture a positive electrode and a negative electrode; interposing a separator between the manufactured positive electrode and negative electrode and laminating them to form a unit cell; laminating the formed unit cells with each other to form an electrode assembly; and accommodating the formed electrode assembly in a case having a gas adsorption portion attached to the inner wall of a case cover and injecting an electrolyte.

[0146] As another example, a method for manufacturing a secondary battery includes steps of: applying a positive electrode active material slurry obtained by dissolving a positive electrode active material in a solvent onto a positive electrode current collector, and applying a negative electrode active material slurry obtained by dissolving a negative electrode active material in a solvent onto a negative electrode current collector to manufacture a positive electrode and a negative electrode; interposing a separator between the manufactured positive electrode and negative electrode and laminating them to form a unit cell; laminating the formed unit cells to each other to form an electrode assembly; installing the electrode assembly such that a gas adsorption part is positioned on the upper part of the formed electrode assembly; and housing the electrode assembly provided with the gas adsorption part in a case and injecting an electrolyte.

[0147] Embodiments of the present invention will be described in detail based on the drawings.

[0148] FIG. 2 is a side view showing a gas adsorption part 20 housed inside a battery case cover 10 filled with an electrode assembly 110 and an electrolyte 120 in a battery 1 according to an embodiment of the present invention.

[0149] The gas adsorption part 20 is attached to the inner wall of the battery case cover 10, and the gas adsorption part 20 includes a piezoelectric element 22 including a pressure conversion part 221 and an electroactive part 222, and a gas adsorption pack 21, which are installed from the inner wall of the case cover toward the central part.

[0150] FIG. 3 is a top view showing a gas adsorption part 20 housed inside a battery case cover 10 according to an embodiment of the present invention. Specifically, a piezoelectric element 22 including a pressure conversion part 221 and an electroactive part 222, and a gas adsorption pack 21 are positioned from the inside of the case cover toward the central part. Further, there is a connection circuit 225 that starts from the pressure conversion part 221 and connects to the electroactive part 222.

[0151] FIG. 4 is a diagram for explaining a change in the gas adsorption part 20 due to an increase in internal pressure caused by gas generation in a secondary battery 1 according to a preferred embodiment of the present invention.

[0152] Referring to FIG. 4 and explaining as described above, the pressure conversion section 221 of the piezoelectric element 22 generates a voltage at the pressure conversion section 221 and transmits it to the electroactive section 222 when the internal pressure increases due to gas generation and the volume expands.

[0153] That is, when normal charge and discharge are repeated in the secondary battery, the gas adsorption pack and the piezoelectric element are simply in close contact within the case. However, as shown in FIG. 4, when volume expansion occurs due to gas generation caused by overcharging or degradation due to battery life, a voltage is generated at the pressure conversion section 221 of the piezoelectric element 22, and the generated voltage is transmitted to the electroactive section 222. The transmitted voltage causes the electroactive section 222 to deform at a predetermined angle toward the gas adsorption pack 21. Then, the deformation of the electroactive section 222 makes a hole in the gas adsorption pack 21 or tears it, and as a result, the contained gas adsorbent is released to adsorb and remove the gas, thereby controlling overheating and fire of the battery and preventing deformation of the case.

[0154] FIG. 5 is a diagram showing the electroactive section 222 and the perforating section 223 located at its end. As an example, the perforating section 223 may extend with the same thickness as the electroactive section 222 or may gradually become thinner. Preferably, when the thickness gradually becomes thinner, it can more easily make a hole in or tear the gas adsorption pack 21. Referring to FIG. 5 and explaining, the thickness of the perforating section 223 is in a shape that gradually becomes thinner than the thickness of the electroactive section 222.

[0155] FIG. 6 is an enlarged view showing the cross section of the A-A section in FIG. 5.

[0156] The cross section of the electroactive section 222 can have various shapes as shown in FIG. 6.

[0157] Figure 6(a) shows a plate-shaped cross-sectional shape, Figure 6(b) shows a circular cross-sectional shape, Figure 6(c) shows a rectangular cross-sectional shape, and Figure 6(d) shows a triangular cross-sectional shape. In addition, the cross-sectional shape of the electroactive part 222 may be changed to various shapes for implementation.

[0158] Figure 7 is an enlarged view of part B in Figure 5 and is a cross-sectional view for explaining the drilling part 223 according to a preferred embodiment of the present invention.

[0159] Referring to Figure 7 for explanation, as shown in Figure 7(a), the drilling part 223 may have a shape in which the electroactive part 222 and the drilling part 223 are extended with the same thickness. In this case, there is an advantage that the manufacturing is easy.

[0160] In addition, the drilling part 223 shown in Figure 7(b) has a shape in which the drilling part 223 extended from the flat electroactive part 222 gradually decreases in thickness as it moves away from the edge of the electroactive part 222. Since the tip of the drilling part 223 is sharper, there is an advantage that it is easy to drill or tear the gas adsorption pack 21.

[0161] In addition, the drilling part 223 in Figure 7(c) is the same as in Figure 7(a) in that the electroactive part 222 and the drilling part 223 are extended with the same thickness, but a groove part 224 with a predetermined depth is further formed at the connecting part between the electroactive part 222 and the drilling part 223. Therefore, there is an advantage that the drilling part 223 can be deformed more sensitively when a voltage is generated due to an increase in the internal pressure of the battery.

[0162] In addition, the drilling part 223 in Figure 7(d) has a shape in which the drilling part 223 extended from the flat electroactive part 222 gradually decreases in thickness as it moves away from the edge of the electroactive part 222, and a groove part 224 with a predetermined depth is further formed at the connecting part between the electroactive part 222 and the drilling part 223. As explained in Figure 7(c), this makes it easy for the drilling part 223 to deform.

Explanation of reference numerals

[0163] 1 Secondary battery 10 Battery case cover 20 Gas adsorption part 21 Gas adsorption pack 22 Piezoelectric element 221 Pressure conversion part 222 Electroactive part 223 Drilled part 224 Groove part 225 Connection circuit 110 Electrode assembly 120 Electrolyte 130 Electrode lead

Claims

1. A battery case cover and a gas adsorption part accommodated inside the case, when the internal pressure of the case increases, the gas adsorption part opens the gas adsorption pack, The gas adsorption part includes a gas adsorption pack filled with a gas adsorbent and a piezoelectric element that bends when the internal pressure increases and the volume of the case expands, piercing the gas adsorption pack, and is characterized by a battery case.

2. The piezoelectric element includes a pressure conversion part containing a piezoelectric substance and an electroactive part containing an electroactive substance, and is characterized by the battery case according to Claim 1.

3. The electroactive substance is an electroactive polymer (Electro Active Polymer), and is characterized by the battery case according to Claim 2.

4. The piezoelectric element includes one or more perforations at the edge, and is characterized by the battery case according to Claim 1.

5. The gas adsorption part is attached to the inner wall of the battery case cover, and is characterized by the battery case according to Claim 1.

6. The gas adsorbent includes one or more selected from the group consisting of a gas adsorbent molecular sieve, a gas adsorbent metal, and a gas adsorbing substance, and is characterized by the battery case according to Claim 1.

7. The gas adsorbent molecular sieve is one or more selected from the group consisting of silica gel, carbon fiber, a porous carbon material, a porous metal oxide, a porous gel, and zeolite, and is characterized by the battery case according to Claim 6.

8. The gas adsorbent metal is one or more selected from the group consisting of nickel (Ni), platinum (Pt), palladium (Pd), calcium (Ca), strontium (Sr), barium (Ba), thallium (Tl), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), and tungsten (W), and is characterized by the battery case according to Claim 6.

9. The gas adsorbent is BaTiO ３ , PB(Mg ３ Nb ２／３ )O ３ -PbTiO ３ (PMN-PT), hafnia (HfO ２ ), SrTiO ３ , SnO ２ , CeO ２ , MgO, NiO, CaO, ZnO, ZrO ２ , Y ２ O ３ , Al ２ O ３ , TiO ２ , sodium hydroxide (NaOH), calcium hydroxide (Ca(OH) ２ ) and potassium hydroxide (KOH), and is characterized in that it is at least one selected from the group consisting of, the battery case according to claim 6.

10. The gas adsorption pack includes one or more selected from the group consisting of an olefin resin, a fluororesin, and a polyamide resin, and is characterized by the battery case according to Claim 1.

11. The piezoelectric element includes a connection circuit connecting from the pressure conversion part to the electroactive part, and is characterized by the battery case according to Claim 2.

12. The battery case according to claim 1, wherein the gas adsorption part is installed such that a piezoelectric element is positioned between an inner wall of the battery case cover and the gas adsorption pack.

13. A secondary battery, comprising: the battery case according to any one of claims 1 to 12; an electrode assembly housed inside the battery case; and an electrolyte filled inside the battery case.

14. The secondary battery according to claim 13, wherein in the secondary battery, the gas adsorption pack is blocked from the outside air or is in an opened state.

15. The secondary battery according to claim 13, wherein the secondary battery is a pouch-type battery.

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