Negative plate, positive plate, diaphragm, battery, battery device and electric equipment

Abstract

The invention provides a negative plate, a positive plate, a diaphragm, a battery, a battery device and electric equipment, the negative plate comprises a negative current collector and a negative active layer arranged on the surface of the negative current collector, and the negative active layer comprises a negative active material and a first metal organic framework material; in the thickness direction of the negative electrode plate, the particle size Dv50 of the first metal organic framework material on one side, far away from the negative electrode current collector, of the negative electrode active layer is greater than the particle size Dv50 of the first metal organic framework material on one side, close to the negative electrode current collector, of the negative electrode active layer; and the first metal organic framework material is suitable for absorbing gas produced by the battery. The negative plate provided by the invention comprises the first metal organic framework material, and the first metal organic framework material is suitable for absorbing gas produced by the battery, so that the cycle performance and the safety performance of the battery can be improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of batteries, and in particular relates to a negative electrode sheet, a positive electrode sheet, a separator, a battery, a battery device and electrical equipment. Background Art

[0002] Currently, batteries produce a high amount of gas during use. Large amounts of gas production will deteriorate the interface bonding effect and affect the battery's cycle performance.

[0003] Therefore, there is an urgent need to solve the problem of poor battery cycle performance caused by large gas production during battery storage. Summary of the Invention

[0004] The main purpose of the present invention is to provide a negative electrode sheet, which can reduce the storage gas production of the battery, thereby improving the cycle performance of the battery.

[0005] The present invention also provides a positive electrode sheet, which can reduce the storage gas production of the battery, thereby improving the cycle performance and safety performance of the battery.

[0006] The present invention also provides a diaphragm, which can reduce the storage gas production of the battery, thereby improving the cycle performance and safety performance of the battery.

[0007] The present invention also provides a battery comprising the above-mentioned negative electrode sheet and / or the above-mentioned positive electrode sheet and / or the above-mentioned separator. Therefore, the battery has low storage gas production and has good cycle performance and safety performance.

[0008] The present invention also provides a battery device comprising a plurality of the above batteries. Therefore, the battery device has a low storage gas production volume and has good cycle performance and safety performance.

[0009] The present invention also provides an electrical device comprising the above-mentioned negative electrode sheet, or the above-mentioned positive electrode sheet, or the above-mentioned diaphragm, or the above-mentioned battery, or the above-mentioned battery device. Therefore, the battery performance related to the electrical device is relatively excellent.

[0010] In a first aspect, the present invention provides a negative electrode sheet comprising a negative electrode current collector and a negative electrode active layer disposed on a surface of the negative electrode current collector, wherein the negative electrode active layer comprises a negative electrode active material and a first metal-organic framework material;

[0011] In the thickness direction of the negative electrode sheet, the particle size Dv50 of the first metal-organic framework material located on the side of the negative electrode active layer away from the negative electrode current collector is larger than the particle size Dv50 of the first metal-organic framework material located on the side of the negative electrode active layer close to the negative electrode current collector, and the first metal-organic framework material is suitable for absorbing battery gas.

[0012] For the negative electrode sheet as described above, in the thickness direction of the negative electrode sheet, the particle size Dv50 of the first metal organic framework material tends to increase along the direction from the negative electrode active layer to the negative electrode current collector.

[0013] The negative electrode sheet as described above, wherein the particle size Dv50 of the first metal organic framework material is 0.2%-12% of the particle size Dv50 of the negative electrode active material;

[0014] And / or, the particle size Dv50 of the negative electrode active material is 7.5 μm-20 μm.

[0015] In the negative electrode sheet as described above, the particle size Dv50 of the first metal organic framework material is 50 nm-1 μm.

[0016] In the negative electrode sheet as described above, the mass percentage of the first metal organic framework material in the negative electrode active layer is 0.1%-2%, preferably 0.3%-1%.

[0017] As described above, the negative electrode sheet, the negative electrode active layer includes a first region located on the surface of the negative electrode current collector and a second region located on the surface of the first region facing away from the negative electrode current collector; the first metal organic framework material includes a first region metal organic framework material and a second region metal organic framework material, the first region metal organic framework material is located in the first region, the second region metal organic framework material is located in the second region, and the particle size Dv50 of the first region metal organic framework material is smaller than the particle size Dv50 of the second region metal organic framework material.

[0018] The negative electrode sheet as described above, wherein the porosity of the first region is 35%-50%;

[0019] And / or, the porosity of the second region is 40%-60%.

[0020] The negative electrode sheet as described above, wherein the negative electrode active material includes a first negative electrode active material located in the first region and a second negative electrode active material located in the second region;

[0021] The particle size Dv50 of the first region metal organic framework material is 0.3%-4% of the particle size Dv50 of the first negative electrode active material;

[0022] And / or, the particle size Dv50 of the metal-organic framework material in the first region is 50 nm-200 nm;

[0023] and / or, the particle size Dv50 of the first negative electrode active material is 5 μm-15 μm;

[0024] And / or, the mass percentage of the first region metal-organic framework material in the first region is 0.1%-2%, preferably 0.3%-1%.

[0025] The negative electrode sheet as described above, wherein the particle size Dv50 of the metal-organic framework material in the second region is 0.4%-15% of the particle size Dv50 of the second negative electrode active material;

[0026] And / or, the particle size Dv50 of the metal-organic framework material in the second region is 100 nm-1.5 μm;

[0027] and / or, the particle size Dv50 of the second negative electrode active material is 10 μm-25 μm;

[0028] And / or, the mass percentage of the second-region metal-organic framework material in the second region is 0.1%-2%, preferably 0.5%-1.5%.

[0029] In the negative electrode sheet as described above, the thickness ratio of the first region to the second region is 1:(0.8-1.2).

[0030] The negative electrode sheet as described above, wherein the first metal organic framework material includes at least one of MOF-303, MOF-199, MOF-177, MIL-101, ZIF-67, ZIF-8, MOF-801, and UiO-66;

[0031] And / or, the pore size of the first metal organic framework material is 0.1nm-5nm, and the specific surface area of ​​the first metal organic framework material is greater than or equal to 1000m 2 / g.

[0032] The negative electrode sheet as described above, wherein the thickness of the negative electrode active layer is 100 μm-300 μm;

[0033] And / or, the porosity of the negative electrode sheet is 38%-55%;

[0034] And / or, the specific surface area of ​​the negative electrode sheet is 2.5m 2 / g-45m 2 / g.

[0035] In a second aspect, the present invention provides a positive electrode sheet comprising a positive electrode current collector and a positive electrode active layer disposed on a surface of the positive electrode current collector, wherein the positive electrode active layer comprises a positive electrode active material and a second metal organic framework material;

[0036] In the thickness direction of the positive electrode sheet, the particle size Dv50 of the second metal-organic framework material located on the side of the positive electrode active layer away from the positive electrode current collector is larger than the particle size Dv50 of the second metal-organic framework material located on the side of the positive electrode active layer close to the positive electrode current collector, and the second metal-organic framework material is suitable for absorbing battery gas.

[0037] In a third aspect, the present invention provides a diaphragm, comprising a diaphragm body and a protective layer provided on a surface of the diaphragm body, wherein the protective layer comprises a third metal-organic framework material;

[0038] In the thickness direction of the diaphragm, the particle size Dv50 of the third metal-organic framework material located on the side of the protective layer away from the diaphragm body is larger than the particle size Dv50 of the third metal-organic framework material located on the side of the protective layer close to the diaphragm body, and the third metal-organic framework material is suitable for absorbing battery gas.

[0039] In a fourth aspect, the present invention provides a battery comprising a negative electrode, a positive electrode and an isolating member, wherein the negative electrode comprises the negative electrode sheet as described above, and / or the positive electrode comprises the positive electrode sheet as described above, and / or the isolating member comprises the diaphragm as described above.

[0040] In a fifth aspect, the present invention provides a battery device comprising a plurality of batteries as described above.

[0041] In a sixth aspect, the present invention provides an electrical device comprising the negative electrode sheet as described above, or the positive electrode sheet as described above, or the separator as described above, or the battery as described above, or the battery device as described above.

[0042] The negative electrode sheet provided by the present invention includes a first metal-organic framework material, and the particle size Dv50 of the first metal-organic framework material in the negative electrode active layer away from the negative electrode current collector is larger than the particle size Dv50 of the first metal-organic framework material in the negative electrode active layer near the negative electrode current collector. The first metal-organic framework material can effectively absorb a large amount of gas generated during battery storage and use, and the area away from the negative electrode current collector contains more macromolecular gases, while the area near the negative electrode current collector contains more small molecule gases. MOF particles with a larger particle size Dv50 can more effectively absorb macromolecular gases generated at the interface; while MOF particles with a smaller particle size Dv50 near the current collector interface can better absorb small molecule gases. The combination of large and small particles can reduce the internal pressure of the battery, reduce the occurrence of side reactions, and improve the battery's cycle performance and safety performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] To more clearly illustrate the technical solutions in the embodiments of the present invention or related technologies, the following briefly introduces the drawings required for use in the embodiments of the present invention or related technologies. Obviously, the drawings described below are only some embodiments of the present invention. Those skilled in the art can also derive other drawings based on these drawings without inventive effort.

[0044] Figure 1 A schematic structural diagram of a negative electrode sheet provided by the present invention;

[0045] Figure 2 This is a schematic structural diagram of another negative electrode sheet provided by the present invention.

[0046] Description of reference numerals:

[0047] 10 - negative electrode current collector; 20 - negative electrode active layer; 21 - first region; 22 - second region. DETAILED DESCRIPTION

[0048] To make the objectives, technical solutions, and advantages of the present invention more clear, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts shall fall within the scope of protection of the present invention.

[0049] During battery use, especially under high-temperature storage conditions, batteries often produce high levels of gas. The composition of the gas produced varies at different battery states (such as 0% SOC and 100% SOC), primarily including H2, CO2, CO, and CH4. The production of these gases increases internal battery pressure, affecting interfacial bonding and reducing the battery's capacity and charge / discharge capabilities. Furthermore, excessive gas can cause the explosion-proof valve to open, leading to battery failure, leakage, and even safety hazards.

[0050] Therefore, how to effectively solve the problems of poor cycle performance and low safety performance of lithium-ion batteries caused by large gas production during high-temperature storage has become a technical problem that needs to be solved urgently.

[0051] Based on this, in the first aspect, the present invention provides a negative electrode sheet, such as Figure 1As shown, the negative electrode sheet includes a negative electrode current collector 10 and a negative electrode active layer 20 disposed on the surface of the negative electrode current collector 10. The negative electrode active layer 20 includes a negative electrode active material and a first metal organic framework (MOF) material. In the thickness direction of the negative electrode sheet, the particle size Dv50 of the first MOF material located on the side of the negative electrode active layer 20 away from the negative electrode current collector 10 is larger than the particle size Dv50 of the first MOF material located on the side of the negative electrode active layer 20 closer to the negative electrode current collector 10. The first MOF material is suitable for absorbing battery gas. The negative electrode active layer 20 can be disposed on either side of the negative electrode current collector 10, or on both sides of the negative electrode current collector 10.

[0052] The negative electrode sheet provided by the present invention includes a first metal-organic framework material, and the particle size Dv50 of the first metal-organic framework material in the negative electrode active layer 20 away from the side of the negative electrode current collector 10 is larger than the particle size Dv50 of the first metal-organic framework material in the negative electrode active layer 20 close to the negative electrode current collector 10. When applied to a battery, it can effectively reduce the storage gas production of the battery, thereby improving the cycle performance and safety performance of the battery.

[0053] This is because the first metal-organic framework material has a high specific surface area and an adjustable pore structure, which can improve the wetting effect of the material and absorb a large amount of gas generated during the use of the battery, including H2, CO2, CO, CH4, etc. Because the decomposition of the SEI film on the collector side is mainly H2, the first metal-organic framework material can reversibly store H2 gas. After the gas is absorbed by the first metal-organic framework material, it can avoid interface problems such as bubbles between the pole pieces that reduce the capacity and cycle performance of the battery, and can inhibit the rapid rise in air pressure inside the battery, avoid the explosion-proof valve from opening, causing battery failure or even causing safety hazards. In addition, the material itself can also be used as a negative electrode active material. Without affecting the battery capacity, it can reduce the expansion of the negative electrode active material and the gas generated by absorption, greatly improving the cycle performance and safety performance of the battery.

[0054] At the same time, the particle size Dv50 of the first metal-organic framework material in the negative electrode active layer 20 farther from the negative electrode current collector 10 is larger than the particle size Dv50 of the first metal-organic framework material in the negative electrode active layer 20 closer to the negative electrode current collector 10. This results in a higher concentration of macromolecular gases in the region farther from the negative electrode current collector, and a higher concentration of small molecule gases closer to the negative electrode current collector. MOF particles with a larger particle size Dv50 are more effective at absorbing macromolecular gases generated at the interface; whereas MOF particles with a smaller particle size Dv50 near the current collector interface are better at absorbing small molecule gases. The combination of large and small particles can reduce internal battery pressure, minimize side reactions, and improve battery cycle performance and safety.

[0055] In the present invention, the first metal organic framework material is dispersed together with the negative electrode active material, the binder and the conductive agent during the slurrying of the negative electrode sheet, and the required electrode is manufactured through a coating process.

[0056] The present invention does not limit the testing method of the particle size Dv50 of the first metal-organic framework material. For example, the battery cell is disassembled to obtain the negative electrode sheet, and then the dressing is scraped off the current collector with a scraper, and an ethanol solvent is added and dispersed by an ultrasonic instrument to obtain a test sample, and the particle size Dv50 of the first metal-organic framework material is tested by a scanning electron microscope (SEM) / transmission electron microscope (TEM) (morphology difference) or a sedimentation particle size analyzer (density difference).

[0057] The particle size Dv50 in the present invention refers to the particle size corresponding to when the volume cumulative distribution percentage reaches 50%.

[0058] The present invention is not limited to the type of the negative electrode current collector 10 . For example, copper foil or nickel foil may be used.

[0059] The present invention is not limited to the type of negative electrode active material. For example, graphite, hard carbon, silicon-containing materials, etc. can be used.

[0060] The negative electrode sheet provided by the present invention includes a first metal-organic framework material, and the particle size Dv50 of the first metal-organic framework material in the negative electrode active layer 20 away from the side of the negative electrode current collector 10 is larger than the particle size Dv50 of the first metal-organic framework material in the negative electrode active layer 20 close to the negative electrode current collector 10. The first metal-organic framework material can effectively absorb a large amount of gas generated during the storage and use of the battery, reduce the internal pressure of the battery, reduce the occurrence of side reactions, and improve the cycle performance and safety performance of the battery.

[0061] In some embodiments of the present invention, in the thickness direction of the negative electrode sheet, the particle size Dv50 of the first metal organic framework material tends to increase along the direction from the negative electrode active layer 20 away from the negative electrode current collector 10 .

[0062] In the present invention, the particle size Dv50 of the first metal-organic framework material increases as it moves away from the negative electrode current collector 10 from the negative electrode active layer 20, forming a particle size gradient within the negative electrode active layer 20. The region away from the negative electrode current collector contains more macromolecular gases, while the region closer to the negative electrode current collector contains more small molecule gases. MOF particles with a larger particle size Dv50 are more effective at absorbing macromolecular gases generated at the interface; whereas MOF particles with a smaller particle size Dv50 near the current collector interface are better at absorbing small molecule gases. This combination of large and small particles further reduces internal battery pressure, minimizes side reactions, and improves battery cycle performance and safety.

[0063] In some embodiments of the present invention, the particle size Dv50 of the first metal organic framework material is 0.2%-12% of the particle size Dv50 of the negative electrode active material, for example, it can be 0.2%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 10%, 12% or a range of any two thereof.

[0064] In some embodiments, the particle size Dv50 of the negative electrode active material is 7.5 μm-20 μm, for example, 7.5 μm, 10 μm, 12 μm, 14 μm, 16 μm, 18 μm, 19 μm, 20 μm, or a range consisting of any two thereof.

[0065] In the present invention, the relationship between the particle size Dv50 of the first metal organic framework material and the particle size Dv50 of the negative electrode active material, as well as the particle size Dv50 of the negative electrode active material being within the above range, the first metal organic framework material can be more effectively filled between the larger negative electrode active material particles, and can more effectively absorb and buffer the gas generated during the battery reaction, helping to reduce the accumulation of gas inside the battery, thereby reducing the gas pressure inside the battery and the occurrence of side reactions, and improving the battery's cycle performance and safety performance. In addition, the first metal organic framework material can form a continuous ion conduction path between the negative electrode active materials, which helps to improve the ion conductivity of the electrode, thereby improving the battery's charge and discharge efficiency and rate performance. And the appropriate size of the first metal organic framework material can reduce the difficulty of manufacturing, which is more conducive to commercial mass production, and the pore size and specific surface area of ​​the material have a better effect on gas absorption.

[0066] Furthermore, the particle size Dv50 of the first metal organic framework material is 50 nm-1 μm, for example, it can be 50 nm, 100 nm, 200 nm, 300 nm, 400 nm, 800 nm, 900 nm, 1 μm or a range consisting of any two thereof, thereby further ensuring the gas absorption effect and ion conductivity.

[0067] In some embodiments of the present invention, the mass percentage of the first metal organic framework material in the negative electrode active layer 20 is 0.1%-2%, for example, it can be 0.1%, 0.2%, 0.3%, 0.5%, 0.7%, 0.9%, 1%, 1.3%, 1.5%, 1.7%, 2% or any two thereof, preferably 0.3%-1%.

[0068] The mass percentage of the first metal-organic framework material in the present invention within the aforementioned range does not affect the conductive network of the negative electrode active material, that is, the electronic conductivity of the negative electrode sheet is not affected, thereby maintaining the battery's efficient charge and discharge performance. The high specific surface area and porous structure of the first metal-organic framework material can also be utilized to effectively absorb and buffer gases generated during the battery reaction, helping to reduce gas accumulation within the battery, thereby reducing internal battery pressure and the occurrence of side reactions, and improving the battery's cycle performance and safety.

[0069] In some embodiments of the present invention, Figure 2 As shown, the negative electrode active layer 20 includes a first region 21 located on the surface of the negative electrode current collector 10 and a second region 22 located on the surface of the first region 21 facing away from the negative electrode current collector 10; the first metal organic framework material includes a first region metal organic framework material and a second region metal organic framework material, the first region metal organic framework material is located in the first region 21, the second region metal organic framework material is located in the second region 22, and the particle size Dv50 of the first region metal organic framework material is smaller than the particle size Dv50 of the second region metal organic framework material.

[0070] The negative electrode active layer 20 can be formed by coating twice or multiple times.

[0071] In the present invention, the first region metal-organic framework material with a smaller particle size Dv50, located in the first region 21 near the negative electrode current collector 10, effectively absorbs small gas molecules and more densely packs the negative electrode active material, reducing interfacial resistance and improving electron conduction efficiency. This helps optimize the electrode's electrical conductivity and ensures efficient electron transport. It also forms a denser structure, providing better mechanical support and reducing material breakage due to volume changes during charge and discharge.

[0072] The second region metal-organic framework material with a larger particle size Dv50 can more effectively absorb the macromolecular gas generated during the battery reaction in the second region 22 away from the negative electrode current collector 10, reduce the accumulation of gas inside the battery, reduce the internal pressure of the battery and the occurrence of side reactions, and improve the cycle performance and safety performance of the battery.

[0073] In some embodiments of the present invention, the porosity of the first region 21 is 35%-50%, for example, it can be 35%, 37%, 40%, 42%, 45%, 48%, 50% or any two thereof.

[0074] In some embodiments, the porosity of the second region 22 is 40%-60%, and may be 40%, 43%, 47%, 50%, 53%, 57%, 60%, or a range consisting of any two thereof.

[0075] The lower porosity in the first region 21 of the present invention can provide a denser structure, helping to improve the mechanical strength and stability of the material, reduce excessive electrolyte penetration, and protect the negative electrode current collector 10 from direct electrolyte erosion. It can also provide better mechanical support and reduce material breakage caused by volume changes during charge and discharge.

[0076] The higher porosity in the second region 22 allows more electrolyte to penetrate into the interior of the electrode, providing sufficient ion conduction paths, increasing the ion diffusion rate, and thus improving the charge and discharge efficiency of the battery. It also provides a larger space to absorb the gas generated during the battery reaction, reducing the accumulation of gas inside the battery, reducing the pressure inside the battery and the occurrence of side reactions, and improving the cycle performance and safety performance of the battery.

[0077] In some embodiments of the present invention, the negative electrode active material includes a first negative electrode active material located in the first region 21 and a second negative electrode active material located in the second region 22; the particle size Dv50 of the metal-organic framework material in the first region is 0.3%-4% of the particle size Dv50 of the first negative electrode active material, for example, it can be 0.3%, 0.5%, 0.8%, 1%, 1.5%, 1.8%, 2%, 2.5%, 3%, 3.5%, 4% or a range consisting of any two of them.

[0078] In some embodiments, the particle size Dv50 of the first region metal-organic framework material is 50 nm-200 nm, for example, 50 nm, 60 nm, 80 nm, 100 nm, 120 nm, 150 nm, 200 nm, or a range consisting of any two thereof.

[0079] In some embodiments, the particle size Dv50 of the first negative electrode active material is 5 μm-15 μm, for example, 5 μm, 7 μm, 9 μm, 10 μm, 12 μm, 14 μm, 15 μm, or a range consisting of any two thereof.

[0080] In some embodiments, the mass percentage of the first region metal-organic framework material in the first region 21 is 0.1%-2%, for example, it can be 0.1%, 0.2%, 0.3%, 0.5%, 0.7%, 0.9%, 1%, 1.3%, 1.5%, 1.7%, 2% or any two thereof, preferably 0.3%-1%.

[0081] In the present invention, the particle size Dv50 of the first region metal-organic framework material and the particle size Dv50 of the first negative electrode active material are within the above-mentioned ranges. The first region metal-organic framework material can effectively absorb small molecule gases and can also more effectively fill the gaps between larger first negative electrode active material particles. This can more effectively absorb and buffer gases generated during battery reactions, helping to reduce gas accumulation within the battery, thereby reducing internal battery pressure and the occurrence of side reactions, and improving the battery's cycle performance and safety. In addition, the mass percentage of the first region metal-organic framework material within the above-mentioned range will not affect the conductive network of the first negative electrode active material, that is, the electronic conductivity of the negative electrode sheet will not be affected, and the battery's efficient charge and discharge performance can be maintained.

[0082] In some embodiments of the present invention, the particle size Dv50 of the second region metal-organic framework material is 0.4%-15% of the particle size Dv50 of the second negative electrode active material. For example, it can be 0.4%, 0.8%, 1%, 3%, 5%, 8%, 10%, 12%, 13%, 14%, 15% or a range of any two thereof.

[0083] In some embodiments, the particle size Dv50 of the second region metal-organic framework material is 100 nm-1.5 μm, for example, 100 nm, 500 nm, 800 nm, 1 μm, 1.5 μm, or a range consisting of any two thereof.

[0084] In some embodiments, the particle size Dv50 of the second negative electrode active material is 10 μm-25 μm, for example, 10 μm, 12 μm, 14 μm, 15 μm, 17 μm, 20 μm, 22 μm, 25 μm, or a range consisting of any two thereof.

[0085] In some embodiments, the mass percentage of the second region metal-organic framework material in the second region 22 is 0.1%-2%, for example, it can be 0.1%, 0.2%, 0.3%, 0.5%, 0.7%, 0.9%, 1%, 1.3%, 1.5%, 1.7%, 2% or any two thereof, preferably 0.5%-1.5%.

[0086] In the present invention, the particle size Dv50 of the second region metal-organic framework material and the particle size Dv50 of the second negative electrode active material are within the above ranges. The second region metal-organic framework material can more effectively absorb the macromolecular gas generated at the interface, reduce the accumulation of gas inside the battery, reduce the internal pressure of the battery and the occurrence of side reactions, and improve the cycle performance and safety performance of the battery. Moreover, the matching relationship between the particle size Dv50 of the second region metal-organic framework material and the particle size Dv50 of the second negative electrode active material is conducive to maintaining the mechanical stability of the electrode during the charge and discharge process and reducing the material fracture caused by volume change. In addition, the mass proportion of the second region metal-organic framework material is within the above range, which will not affect the conductive network of the second negative electrode active material, that is, the electronic conductivity performance of the negative electrode sheet will not be affected, and the efficient charge and discharge performance of the battery can be maintained.

[0087] In some embodiments of the present invention, the thickness ratio of the first region 21 to the second region 22 is 1:(0.8-1.2), for example, it can be 1:0.8, 1:0.9, 1:0.95, 1:1, 1:1.1, 1:1.15, 1:1.2 or a range consisting of any two thereof.

[0088] In the present invention, the thickness ratio of the first region 21 to the second region 22 is within the above range, which can enable the first region 21 to provide higher conductivity and the second region 22 to provide better ion conduction and gas absorption capabilities, thereby improving the cycle performance and safety performance of the battery.

[0089] In some embodiments of the present invention, the first metal organic framework material includes at least one of MOF-303, MOF-199, MOF-177, MIL-101, ZIF-67, ZIF-8, MOF-801, and UiO-66.

[0090] In some embodiments, the pore size of the first metal organic framework material is 0.1 nm to 5 nm, for example, 0.1 nm, 0.3 nm, 0.5 nm, 0.7 nm, 1 nm, 2 nm, 3 nm, 4 nm, 5 nm, or any two thereof. The specific surface area of ​​the first metal organic framework material is greater than or equal to 1000 m 2 / g, for example, it can be 1000m 2 / g、1100m 2 / g、1200m 2 / g、1300m 2 / g、1500m 2 / g、1800m 2 / g、2000m 2 / g or a range consisting of any two thereof.

[0091] The type, pore size and specific surface area of ​​the first metal-organic framework material in the present invention are within the above-mentioned ranges, which can further improve the gas absorption ability of the first metal-organic framework material, reduce the accumulation of gas inside the battery, reduce the internal pressure of the battery and the occurrence of side reactions, and improve the cycle performance and safety performance of the battery.

[0092] In some embodiments of the present invention, the thickness of the negative electrode active layer 20 is 100 μm-300 μm, for example, 100 μm, 130 μm, 150 μm, 180 μm, 200 μm, 250 μm, 300 μm or any two thereof.

[0093] In some embodiments, the porosity of the negative electrode sheet is 38%-55%, for example, it can be 38%, 40%, 43%, 45%, 50%, 52%, 55% or any two thereof.

[0094] In some embodiments, the specific surface area of ​​the negative electrode sheet is 2.5 m 2 / g-45m 2 / g, for example, it can be 2.5m 2 / g、5m 2 / g、10m 2 / g、15m 2 / g, 20m 2 / g、30m 2 / g、45m 2 / g, or a range consisting of any two thereof.

[0095] The thickness of the negative electrode active layer 20 in the present invention is within the above range, which can provide sufficient active material, thereby improving the energy density of the battery, avoiding the problem of excessively long ion conduction paths due to excessive thickness, and is also beneficial to maintaining the mechanical integrity of the electrode, reducing material cracking or peeling caused by volume changes during charging and discharging.

[0096] The porosity and specific surface area of ​​the negative electrode sheet in the present invention are within the above ranges, which can provide sufficient electrolyte penetration and ion conduction paths, improve the charge and discharge efficiency of the battery, and are also beneficial for absorbing the gas generated during the battery reaction, reducing the accumulation of gas inside the battery, and improving the cycle performance and safety performance of the battery.

[0097] In a second aspect, the present invention provides a positive electrode sheet comprising a positive electrode current collector and a positive electrode active layer disposed on the surface of the positive electrode current collector, wherein the positive electrode active layer comprises a positive electrode active material and a second metal organic framework material.

[0098] In the thickness direction of the positive electrode sheet, the particle size Dv50 of the second metal organic framework material located on the side of the positive electrode active layer away from the positive electrode current collector is larger than the particle size Dv50 of the second metal organic framework material located on the side of the positive electrode active layer close to the positive electrode current collector, and the second metal organic framework material is suitable for absorbing battery gas.

[0099] Similar to the mechanism of action of the negative electrode sheet, the positive electrode sheet of the present invention can also reduce the internal pressure of the battery, reduce the occurrence of side reactions, and improve the cycle performance and safety performance of the battery.

[0100] In a third aspect, the present invention provides a diaphragm, comprising a diaphragm body and a protective layer disposed on a surface of the diaphragm body, wherein the protective layer comprises a third metal-organic framework material.

[0101] In the thickness direction of the diaphragm, the particle size Dv50 of the third metal organic framework material located on the side of the protective layer away from the diaphragm body is larger than the particle size Dv50 of the third metal organic framework material located on the side of the protective layer close to the diaphragm body, and the third metal organic framework material is suitable for absorbing battery gas.

[0102] Similar to the mechanism of action of the negative electrode sheet, the separator of the present invention can also reduce the internal pressure of the battery, reduce the occurrence of side reactions, and improve the cycle performance and safety performance of the battery.

[0103] In a fourth aspect, the present invention provides a battery comprising a negative electrode, a positive electrode, and a separator, wherein the negative electrode comprises the negative electrode sheet described above, and / or the positive electrode comprises the positive electrode sheet described above, and / or the separator comprises the separator described above. This battery has the same advantages as the negative electrode sheet, and / or the positive electrode sheet, and / or the separator described above, and will not be further elaborated.

[0104] The battery of the present invention includes, in addition to the negative electrode sheet, the separator, and the positive electrode sheet, an electrolyte, wherein the electrolyte can be any electrolyte conventionally used in the art.

[0105] The battery of the present invention can be prepared by conventional methods in the field. Specifically, the positive electrode sheet, the separator and the negative electrode sheet can be stacked in sequence, and then the battery core can be obtained through a lamination or winding process, and then through baking, liquid injection, formation, packaging and other processes to obtain the above-mentioned battery.

[0106] The batteries of the present application may include battery cells, battery modules, and battery packs. In some embodiments, battery cells may be assembled into a battery module, which may contain one or more battery cells, with the specific number selected by those skilled in the art based on the application and capacity of the battery module. In some embodiments, battery modules may also be assembled into a battery pack, which may contain one or more battery modules, with the specific number selected by those skilled in the art based on the application and capacity of the battery pack.

[0107] There is no special restriction on the specific type of battery in this application. For example, from the perspective of shape, the battery includes but is not limited to square shell batteries, soft pack batteries and cylindrical batteries, etc., and this application does not impose any special restrictions. From the perspective of the pole core structure, the pole core of the battery can be a wound pole core (that is, the positive electrode sheet, the negative electrode sheet and the separator are stacked and arranged, and then the pole core is made by a winding process), or it can be a laminated pole core (that is, multiple positive electrode sheets, negative electrode sheets and separators are stacked to form a pole core). The outer shell can be a hard shell (such as a steel shell, a hard plastic shell, etc.), or a soft shell (such as an aluminum-plastic film, a bag-type soft shell, etc.). This application does not impose any special restrictions.

[0108] In a fifth aspect, the present invention provides a battery device comprising a plurality of batteries as described above.

[0109] The battery device of the present invention may include one battery or multiple battery cells, and the multiple battery cells are connected in series, parallel or mixed connection, wherein mixed connection is a combination of series and parallel connection.

[0110] In a sixth aspect, the present invention provides an electrical device comprising the negative electrode sheet as described above, or the positive electrode sheet as described above, or the diaphragm as described above, or the battery as described above, or the battery device as described above. The electrical device has advantages corresponding to the above-mentioned negative electrode sheet, or the above-mentioned positive electrode sheet, or the above-mentioned diaphragm, or the above-mentioned battery, or the above-mentioned battery device, which will not be repeated.

[0111] The electrical equipment of the present invention can be conventional electrical equipment in the field, such as power equipment (such as electric vehicles), electronic equipment (such as computers, mobile phones, digital cameras, printers, fax machines, etc.), wearable devices (such as watches, bracelets, VR glasses, etc.), household appliances (such as air conditioners, refrigerators, washing machines, microwave ovens, etc.), etc., without special restrictions.

[0112] The technical solution of the present invention is further described below with reference to specific embodiments.

[0113] Example 1

[0114] The preparation method of the battery of this embodiment includes the following steps:

[0115] 1) Preparation of positive electrode sheet: The positive electrode conductive coating is evenly applied to the surface of the aluminum foil. The thickness of the conductive coating is 1.5 μm. The positive electrode active material lithium iron phosphate, lithium supplement (Li5FeO4), conductive agent (carbon black), and binder (SR45-M08) are dispersed in N-methylpyrrolidone (NMP) solvent according to the mass percentage ratio of 95:1.5:1.5:2 to obtain a uniformly mixed positive electrode slurry; the positive electrode slurry is evenly applied to the surface of the aluminum foil coated with the conductive coating. The electrode sheet is baked and cut to obtain the positive electrode sheet; the coating amount is 440 g / m 2, the electrode thickness is 182μm.

[0116] 2) Preparation of the Negative Electrode: Disperse the first negative electrode active material, graphite, a conductive agent (carbon black), a thickener (CMC760B), a binder (SR45-M08), and the first region metal-organic framework material, MOF (ZIF-8), in deionized water at a mass ratio of 96:1:1.2:1.5:0.3. Stir and mix thoroughly to obtain a first negative electrode slurry. Apply the first negative electrode slurry evenly to the surface of the negative electrode current collector copper foil. Disperse the second negative electrode active material, graphite, a conductive agent (carbon black), a thickener (CMC760B), a binder (SR45-M08), and the second region metal-organic framework material, MOF (UiO-66), in deionized water at a mass ratio of 96:1:1.2:1.5:0.3. Stir and mix thoroughly to obtain a second negative electrode slurry. Apply the second negative electrode slurry evenly to the surface of the first negative electrode slurry facing away from the negative electrode current collector copper foil. After the electrode is baked and cut, the negative electrode is obtained; the dressing amount is 208g / m 2 The thickness of the electrode sheet is 140μm, the Dv50 of the first negative electrode active material graphite in the negative electrode sheet is 12.5μm, the Dv50 of the first region metal organic framework material is 100nm, the Dv50 of the second negative electrode active material graphite is 12.5μm, and the Dv50 of the second region metal organic framework material is 500nm.

[0117] 3) Diaphragm: PP diaphragm with a porosity of 40% and a thickness of 10 μm.

[0118] 4) Battery Assembly: The negative electrode sheet, separator, and positive electrode sheet are stacked in sequence to form an aluminum-cased battery. Electrolyte is injected, activated, and then tested.

[0119] The preparation method of the batteries of Examples 2 to 22 is similar to that of Example 1, but the particle size and amount of each component are adjusted. The parameters of the prepared batteries are shown in Table 1.

[0120] Example 23

[0121] The preparation method of the battery of Example 23 is basically the same as that of Example 1, except that, in step 1), preparation of the positive electrode sheet: the positive electrode conductive coating is evenly applied to the surface of the aluminum foil, and the thickness of the conductive coating is 1.5 μm. The first positive electrode active material lithium iron phosphate, the conductive agent (carbon black), the binder (SR45-M08), and the third region metal organic framework material MOF (ZIF-8) are dispersed in N-methylpyrrolidone (NMP) solvent according to a mass percentage ratio of 96.5:1.2:2:0.3 to obtain a uniformly mixed first positive electrode slurry, and the first positive electrode slurry is evenly applied to the surface of the positive electrode current collector aluminum foil. The second cathode active material, lithium iron phosphate, conductive agent (carbon black), binder (SR45-M08), and fourth region metal organic framework material MOF (UiO-66) are dispersed in N-methylpyrrolidone (NMP) solvent according to a mass percentage ratio of 96.5:1.2:2:0.3 to obtain a uniformly mixed second cathode slurry. The second cathode slurry is evenly coated on the surface of the aluminum foil facing away from the cathode current collector. After the electrode is baked and cut, the positive electrode sheet is obtained; the coating amount is 440g / m 2 , the thickness of the electrode sheet is 182μm. Step 2), preparation of the negative electrode sheet: disperse the negative electrode active material graphite, conductive agent (carbon black), thickener (CMC760B), and binder (SR45-M08) in deionized water according to the mass percentage ratio of 96:1:1.5:1.5, and stir and mix evenly to obtain the negative electrode slurry. The negative electrode slurry is evenly coated on the surface of the negative electrode current collector copper foil. After the electrode sheet is baked and cut, the negative electrode sheet is obtained; the dressing amount is 208g / m 2 , the electrode thickness is 140μm.

[0122] Example 24

[0123] The preparation method of the battery of Example 24 is basically the same as that of Example 1, except that, in step 2), the preparation of the negative electrode sheet is as follows: the negative electrode active material graphite, the conductive agent (carbon black), the thickener (CMC760B), and the binder (SR45-M08) are dispersed in deionized water according to a mass percentage ratio of 96:1:1.5:1.5, and stirred and mixed to obtain a negative electrode slurry. The negative electrode slurry is evenly coated on the surface of the negative electrode current collector copper foil. After the electrode sheet is baked and cut, the negative electrode sheet is obtained; the coating amount is 208g / m 2 , the electrode thickness is 140μm. Step 3), preparation of the diaphragm: the fifth region metal organic framework material MOF (ZIF-8) is coated on the surface of the PP diaphragm at a mass percentage ratio of 0.3:99.7 (double-sided coating), and the sixth region metal organic framework material MOF (UiO-66) is coated on the surface away from the PP diaphragm at a mass percentage ratio of 0.3:99.7 (double-sided coating). After baking, the diaphragm is prepared to obtain a composite diaphragm with a thickness of 14μm.

[0124] Comparative Example 1

[0125] The preparation method of the battery of Comparative Example 1 is basically the same as that of Example 1, except that, in step 2), the preparation of the negative electrode sheet: the negative electrode active material graphite (Dv50 is 12.5μm), conductive agent (carbon black), thickener (CMC760B), binder (SR45-M08), MOF (UiO-66, Dv50 is 500nm) are dispersed in deionized water according to the mass percentage ratio of 96:1:1.2:1.5:0.3, and stirred and mixed to obtain the negative electrode slurry. The negative electrode slurry is evenly coated on the surface of the negative electrode current collector copper foil. After the electrode sheet is baked and cut, the negative electrode sheet is obtained; the coating amount is 208g / m 2 The electrode sheet is 140 μm thick. The negative electrode sheet includes a negative current collector and a negative active layer disposed on the surface of the negative current collector. The negative active layer comprises graphite, a negative electrode active material, and a metal-organic framework (MOF). The MOF particle size is uniformly distributed along the negative active layer away from the negative current collector.

[0126] Comparative Example 2

[0127] The preparation method of the battery of Comparative Example 2 is basically the same as that of Example 1, except that, in step 2), the preparation of the negative electrode sheet: the negative electrode active material graphite (Dv50 is 12.5μm), conductive agent (carbon black), thickener (CMC760B), binder (SR45-M08), MOF (ZIF-8, Dv50 is 100nm) are dispersed in deionized water according to the mass percentage ratio of 96:1:1.2:1.5:0.3, and stirred and mixed to obtain the negative electrode slurry. The negative electrode slurry is evenly coated on the surface of the negative electrode current collector copper foil. After the electrode sheet is baked and cut, the negative electrode sheet is obtained; the coating amount is 208g / m 2 The electrode sheet is 140 μm thick. The negative electrode sheet includes a negative current collector and a negative active layer disposed on the surface of the negative current collector. The negative active layer comprises graphite, a negative electrode active material, and a metal-organic framework (MOF). The MOF particle size is uniformly distributed along the negative active layer away from the negative current collector.

[0128] Comparative Example 3

[0129] The preparation method of the battery of Comparative Example 3 is basically the same as that of Example 1, except that, in step 2), the preparation of the negative electrode sheet is as follows: the negative electrode active material graphite (Dv50 is 12.5μm), the conductive agent (carbon black), the thickener (CMC760B), and the binder (SR45-M08) are dispersed in deionized water according to a mass percentage ratio of 96.3:1:1.2:1.5, and stirred and mixed to obtain a negative electrode slurry. The negative electrode slurry is evenly coated on the surface of the negative electrode current collector copper foil. After the electrode sheet is baked and cut, the negative electrode sheet is obtained; the coating amount is 208g / m 2The thickness of the electrode sheet is 140 μm. The negative electrode sheet includes a negative electrode current collector and a negative electrode active layer provided on the surface of the negative electrode current collector. The negative electrode active layer includes a negative electrode active material, graphite.

[0130] Test example

[0131] 1. Dv50: A laser particle size analyzer is used to test the particle size Dv50 of the negative electrode active material and the metal organic framework material. The instrument calculates the volume distribution data by analyzing the scattering pattern of the particles to the laser.

[0132] 2. Pore size of metal organic framework materials: The pore size of the material is measured by nitrogen adsorption method (BET method), which is the same as the pore and specific surface area test method below.

[0133] 3. Porosity and specific surface area: The porosity of the material is tested using a porosity tester, and the specific surface area of ​​the metal-organic framework material is tested using the BET static method. The metal-organic framework material is first placed in a special adsorption instrument sample tube and subjected to high-temperature pretreatment (200°C nitrogen blowing and baking for 2 hours) to remove impurities and moisture on the surface. Subsequently, an inert gas (usually nitrogen or other adsorbents) is brought into contact with the metal-organic framework material under a series of known relative pressures and reaches adsorption equilibrium. The instrument measures the adsorption amount at different relative pressures, and based on these data and the BET theory, the specific surface area is calculated.

[0134] 4. Thickness of the negative electrode active layer: The thickness of the negative electrode active layer is tested using a transmission electron microscope (TEM). In a high vacuum environment, an electron beam generated by an electron gun penetrates the sample and focuses on the image. The thickness of the negative electrode active layer is measured by observing the image on the display screen using the built-in calibration tool. After measuring multiple areas, the average value is calculated to obtain the thickness of the negative electrode active layer.

[0135] 5. Storage gas production performance: The initial internal pressure P0 of the aluminum shell battery before storage is tested with an air pressure sensor, and the temperature is controlled at 60°C. After storage for 60 days, the internal pressure P1 of the aluminum shell battery is tested again with an air pressure sensor, and the internal pressure change (P1-P0) is calculated to obtain the high-temperature storage gas production situation.

[0136] 6. Cycle performance: At 45°C, charge the battery to 4.5V at a constant current of 1C, then charge it to 4.5V at a constant voltage of 0.5C, and then discharge it to 2.5V at a discharge rate of 1C. Repeat this charge and discharge cycle 600 times. Measure the discharge capacity Q1 at the first cycle and the discharge capacity Q at the 600th cycle. 600 The capacity retention rate after 600 cycles is Q = Q 600 / Q1*100%.

[0137] Table 1

[0138]

[0139]

[0140] Table 2

[0141]

[0142]

[0143] It can be seen from Table 1-2 that, compared with the comparative example, the negative electrode sheet provided by the present invention includes a metal organic framework material, and the particle size of the metal organic framework material in the negative electrode active layer away from the negative electrode current collector side is larger than the particle size of the metal organic framework material in the negative electrode active layer close to the negative electrode current collector side. The metal organic framework material can effectively absorb a large amount of gas generated during the storage and use of the battery, and in the area close to the electrolyte interface, the MOF particles with larger particle size have stronger adsorption capacity, which can quickly absorb the generated gas, thereby reducing the internal pressure of the battery, reducing the occurrence of side reactions, and improving the cycle performance and safety performance of the battery.

[0144] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the above embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A negative electrode sheet, characterized in that: It includes a negative electrode current collector and a negative electrode active layer provided on the surface of the negative electrode current collector, wherein the negative electrode active layer includes a negative electrode active material and a first metal organic framework material; In the thickness direction of the negative electrode sheet, the particle size Dv50 of the first metal-organic framework material located on the side of the negative electrode active layer away from the negative electrode current collector is larger than the particle size Dv50 of the first metal-organic framework material located on the side of the negative electrode active layer close to the negative electrode current collector, and the first metal-organic framework material is suitable for absorbing battery gas.

2. The negative electrode sheet according to claim 1, characterized in that: In the thickness direction of the negative electrode sheet, the particle size Dv50 of the first metal organic framework material tends to increase along the direction from the negative electrode active layer to the negative electrode current collector.

3. The negative electrode sheet according to claim 1 or 2, characterized in that: The particle size Dv50 of the first metal organic framework material is 0.2%-12% of the particle size Dv50 of the negative electrode active material; And / or, the particle size Dv50 of the negative electrode active material is 7.5 μm-20 μm.

4. The negative electrode sheet according to any one of claims 1 to 3, characterized in that: The particle size Dv50 of the first metal organic framework material is 50 nm-1 μm.

5. The negative electrode sheet according to any one of claims 1 to 4, characterized in that: The mass percentage of the first metal organic framework material in the negative electrode active layer is 0.1%-2%, preferably 0.3%-1%.

6. The negative electrode sheet according to any one of claims 1 to 5, characterized in that: The negative electrode active layer includes a first region located on the surface of the negative electrode current collector and a second region located on the surface of the first region facing away from the negative electrode current collector; the first metal-organic framework material includes a first-region metal-organic framework material and a second-region metal-organic framework material, the first-region metal-organic framework material is located in the first region, the second-region metal-organic framework material is located in the second region, and the particle size Dv50 of the first-region metal-organic framework material is smaller than the particle size Dv50 of the second-region metal-organic framework material.

7. The negative electrode sheet according to claim 6, characterized in that: The porosity of the first region is 35%-50%; And / or, the porosity of the second region is 40%-60%.

8. The negative electrode sheet according to claim 6 or 7, characterized in that: The negative electrode active material includes a first negative electrode active material located in the first region and a second negative electrode active material located in the second region; The particle size Dv50 of the first region metal organic framework material is 0.3%-4% of the particle size Dv50 of the first negative electrode active material; And / or, the particle size Dv50 of the metal-organic framework material in the first region is 50 nm-200 nm; and / or, the particle size Dv50 of the first negative electrode active material is 5 μm-15 μm; And / or, the mass percentage of the first region metal-organic framework material in the first region is 0.1%-2%, preferably 0.3%-1%.

9. The negative electrode sheet according to claim 8, characterized in that: The particle size Dv50 of the second region metal-organic framework material is 0.4%-15% of the particle size Dv50 of the second negative electrode active material; And / or, the particle size Dv50 of the metal-organic framework material in the second region is 100 nm-1.5 μm; and / or, the particle size Dv50 of the second negative electrode active material is 10 μm-25 μm; And / or, the mass percentage of the second-region metal-organic framework material in the second region is 0.1%-2%, preferably 0.5%-1.5%.

10. The negative electrode sheet according to any one of claims 6 to 9, characterized in that: The thickness ratio of the first region to the second region is 1:(0.8-1.2).

11. The negative electrode sheet according to any one of claims 1 to 10, characterized in that: The first metal organic framework material includes at least one of MOF-303, MOF-199, MOF-177, MIL-101, ZIF-67, ZIF-8, MOF-801, and UiO-66; And / or, the pore size of the first metal organic framework material is 0.1nm-5nm, and the specific surface area of ​​the first metal organic framework material is greater than or equal to 1000m 2 / g.

12. The negative electrode sheet according to any one of claims 1 to 11, characterized in that: The thickness of the negative electrode active layer is 100 μm-300 μm; And / or, the porosity of the negative electrode sheet is 38%-55%; And / or, the specific surface area of ​​the negative electrode sheet is 2.5m 2 / g-45m 2 / g.

13. A positive electrode sheet, characterized in that: It includes a positive electrode current collector and a positive electrode active layer provided on the surface of the positive electrode current collector, wherein the positive electrode active layer includes a positive electrode active material and a second metal organic framework material; In the thickness direction of the positive electrode sheet, the particle size Dv50 of the second metal-organic framework material located on the side of the positive electrode active layer away from the positive electrode current collector is larger than the particle size Dv50 of the second metal-organic framework material located on the side of the positive electrode active layer close to the positive electrode current collector, and the second metal-organic framework material is suitable for absorbing battery gas.

14. A diaphragm, characterized in that: It comprises a diaphragm body and a protective layer provided on the surface of the diaphragm body, wherein the protective layer comprises a third metal organic framework material; In the thickness direction of the diaphragm, the particle size Dv50 of the third metal-organic framework material located on the side of the protective layer away from the diaphragm body is larger than the particle size Dv50 of the third metal-organic framework material located on the side of the protective layer close to the diaphragm body, and the third metal-organic framework material is suitable for absorbing battery gas.

15. A battery, characterized in that: The battery comprises a negative electrode, a positive electrode and a separator, wherein the negative electrode comprises the negative electrode sheet according to any one of claims 1 to 12, and / or the positive electrode comprises the positive electrode sheet according to claim 13, and / or the separator comprises the diaphragm according to claim 14.

16. A battery device, characterized in that: Comprising a plurality of batteries as claimed in claim 15.

17. An electrical device, characterized in that: The invention comprises the negative electrode sheet according to any one of claims 1 to 12, or the positive electrode sheet according to claim 13, or the separator according to claim 14, or the battery according to claim 15, or the battery device according to claim 16.

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