Active ion supplement material, secondary battery, and electric device

Abstract

The invention discloses an active ion supplementing material, a secondary battery and a power utilization device, and belongs to the technical field of batteries, the active ion supplementing material comprises a metal organic framework and an active ion supplementing agent located in pores of the metal organic framework, the active ion supplementing agent can supplement active ions for the secondary battery, and the active ion supplementing agent can supplement active ions for the secondary battery. The active ion supplement is located in pores of the metal organic framework, can achieve the effect of slowly releasing and supplementing active ions, supplements the active ions in the circulation and / or storage process of the secondary battery, achieves long-period supplementation of the active ions, avoids performance reduction of the secondary battery caused by excessive consumption of the active ions, and improves the service life of the secondary battery. And the cycle life and the storage stability of the secondary battery are effectively improved.

Description

Technical Field

[0001] The present application relates to the field of battery technology, and in particular to an active ion supplement material, a secondary battery, and an electrical device. Background Art

[0002] The warranty life of secondary batteries directly determines the value of new energy vehicles. Currently, the short warranty life of secondary batteries is one of the problems that plague new energy vehicle end users.

[0003] In commercial secondary batteries, the number of active ions (lithium or sodium ions) directly determines the battery capacity. However, during the cycling and storage of secondary batteries, the instability of the active materials or the solid electrolyte interphase (SEI and CEI) causes the electrode / electrolyte interface to continuously repair, which in turn consumes active ions, resulting in a decrease in secondary battery capacity.

[0004] In view of this, this application is filed. Summary of the Invention

[0005] The purpose of this application is to overcome the shortcomings of the existing technology and provide an active ion supplement material, a secondary battery and an electrical device. The active ion supplement material described in this application can effectively improve the cycle life and storage stability of the secondary battery.

[0006] To achieve the above-mentioned object, the first aspect of the present application provides an active ion supplement material, comprising a metal organic framework and an active ion supplement located in the pores of the metal organic framework;

[0007] The active ion supplement includes at least one of a lithium supplement and a sodium supplement.

[0008] As an embodiment of the present application, the lithium supplement comprises lithium trifluoromethanesulfinate.

[0009] As an embodiment of the present application, the sodium supplement comprises sodium trifluoromethanesulfinate.

[0010] As an embodiment of the present application, the mass ratio of the metal organic framework to the active ion supplement is (5-50):1.

[0011] As an embodiment of the present application, the pore diameter of the metal organic framework is 1.0 to 4.0 nm.

[0012] As an embodiment of the present application, the metal organic framework D V50 The particle size is 1 to 10 μm.

[0013] As an embodiment of the present application, the metal organic framework includes metal ions and organic ligands;

[0014] The metal ions include Zn 2+ 、Co 3+ 、Co 2+ 、Cu 2+ 、Fe 3+ 、Fe 2+ 、Mn 3+ 、Mn 2+ 、Al 3 +、Ni 2+ 、Ni + Mg 2+ 、Ti 4+ 、Na + , K + , Rb + , Ca 2+ 、Sr 2+ Sc 3+ 、Y 3+ 、Zr 4+ 、V 4+ 、V 3+ 、V 2+ 、Nb 3+ Cr 3+ 、Ru 3+ 、Ru 2+ , Pt 2+ , Pt + 、Ag + 、Au + 、Cd 2+ 、Sn 4+ 、Sn 2+ At least one of;

[0015] The organic ligand includes at least one of a carboxylic acid ligand, an ester ligand, a pyridine ligand, an azole ligand, an aminocarboxylic acid ligand, a urea ligand, and a porphyrin ligand.

[0016] A second aspect of the present application provides a secondary battery, which includes an active ion supplement material, and the active ion supplement material includes the active ion supplement material described above.

[0017] As an embodiment of the present application, the ratio of the mass of the active ion supplement material in the secondary battery to the capacity of the secondary battery is in the range of 50 to 500 mg / Ah.

[0018] As an embodiment of the present application, the secondary battery includes an electrolyte, and the electrolyte includes at least one of a first additive and a second additive.

[0019] As an embodiment of the present application, the first additive includes at least one of vinylene carbonate and fluoroethylene carbonate.

[0020] As an embodiment of the present application, the second additive includes at least one of vinyl sulfate, 1,3-propane sultone, propenyl-1,3-sultone, ethylene sulfite, methylene methanedisulfonate, 1,4-butane sultone, and tripropynyl phosphate.

[0021] As an embodiment of the present application, the mass percentage of the first additive in the electrolyte is 0.5% to 4.2%.

[0022] As an embodiment of the present application, the mass percentage of the second additive in the electrolyte is 0.1% to 1.4%.

[0023] A third aspect of the present application provides an electrical device, comprising the secondary battery described above, wherein the secondary battery is used as a power supply for the electrical device.

[0024] The beneficial effects of the present application are as follows: the active ion supplement material of the present application includes a metal-organic framework and an active ion supplement located in the pores of the metal-organic framework, the active ion supplement can supplement active ions (lithium ions and / or sodium ions) for the secondary battery, the active ion supplement is stored in the pores of the metal-organic framework, and can achieve the effect of sustained-release supplementation of active ions, supplement active ions during the circulation and / or storage process of the secondary battery, achieve long-term supplementation of active ions, avoid the performance degradation of the secondary battery caused by excessive consumption of active ions, and effectively improve the cycle life and storage stability of the secondary battery. DETAILED DESCRIPTION

[0025] To make the purpose, technical solutions, and advantages of the embodiments of this application more clear, the technical solutions in the embodiments of this application will be clearly and completely described below. Obviously, the described embodiments are part of the embodiments of this application, not all of them. Based on the embodiments of this application, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of this application.

[0026] In this application, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0027] In this application, when referring to numerical ranges, unless otherwise specified, the numerical ranges are considered continuous and include the minimum and maximum values ​​of the range, as well as every value between such minimum and maximum values. Further, when a range refers to an integer, every integer between the minimum and maximum values ​​of the range is included. In addition, when multiple ranges are provided to describe a feature or characteristic, the ranges can be combined. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges subsumed therein.

[0028] The inventors of this application have found that replenishing active ions (lithium ions and / or sodium ions) is a feasible solution to improve the service life of secondary batteries. The current mainstream solution for replenishing active ions in secondary batteries is: adding lithium-rich compounds (such as lithium ferrite, lithium nickelate, etc.) and / or sodium-rich compounds (sodium oxalate, sodium cobaltate, etc.) to the positive electrode active material layer of the positive electrode plate, thereby improving the cycle stability of the secondary battery. However, these lithium-rich compounds and / or sodium-rich compounds will remain in the positive electrode plate, which will hinder the electron conduction path between the particles inside the positive electrode, affecting the energy density and kinetic performance of the secondary battery; at the same time, the prior art discloses directly adding lithium replenishers and / or sodium replenishers to the electrolyte, and then adding the electrolyte to the battery to achieve pre-embedding of lithium / sodium in the battery, which can effectively replenish the active lithium / sodium consumed during the formation process, but it cannot replenish lithium and / or sodium during the circulation and / or storage of the secondary battery.

[0029] The term "metal-organic framework" used in this article is also referred to as MOF (Metal-Organic Frameworks), which is an organic-inorganic hybrid material with intramolecular pores formed by self-assembly of organic ligands and metal ions or clusters through coordination bonds.

[0030] Therefore, based on the above problems, the embodiments of the present application provide an active ion supplement material, comprising a metal organic framework and an active ion supplement located in the pores of the metal organic framework;

[0031] The active ion supplement includes at least one of a lithium supplement and a sodium supplement.

[0032] The active ion supplement material of the present application includes a metal-organic framework and an active ion supplement located in the pores of the metal-organic framework. The active ion supplement can supplement active ions (lithium ions and / or sodium ions) for the secondary battery. The active ion supplement is located in the pores of the metal-organic framework and can achieve the effect of sustained-release supplementation of active ions. It supplements active ions during the circulation and / or storage process of the secondary battery, realizes long-term supplementation of active ions, avoids the performance degradation of the secondary battery caused by excessive consumption of active ions, and effectively improves the cycle life and storage stability of the secondary battery.

[0033] In some embodiments, the lithium supplement comprises lithium trifluoromethanesulfinate.

[0034] In some embodiments, the sodium supplement comprises sodium trifluoromethanesulfinate.

[0035] In particular, when the active ion supplement includes lithium trifluoromethanesulfinate and / or sodium trifluoromethanesulfinate, the active ion supplement can effectively supplement the active ions of the secondary battery, and supplement the active ions consumed by continuous film formation and repair of the interface during formation, circulation and storage. At the same time, the reaction products of the lithium / sodium supplementation electrochemical reaction are all gases, which can be completely discharged during the formation process, without adversely affecting the secondary battery, and can more effectively improve the cycle life and storage stability of the secondary battery.

[0036] In some embodiments, the mass ratio of the metal organic framework to the active ion supplement is (5-50):1, for example, it can be 5:1, 10:1, 20:1, 30:1, 40:1, 50:1 or a range consisting of any two values ​​therein. By controlling the mass ratio of the metal organic framework to the active ion supplement within this range, the energy density of the secondary battery can be improved, and the cycle life and storage stability of the secondary battery can be improved.

[0037] In some embodiments, the pore size of the metal organic framework is 1.0 to 4.0 nm, for example, it can be 1.0 nm, 1.2 nm, 1.5 nm, 1.8 nm, 2.0 nm, 2.5 nm, 3.0 nm, 3.5 nm, 4.0 nm or a range consisting of any two values ​​therein. By controlling the pore size of the metal organic framework within this range, the distribution uniformity of the active ion supplement inside the metal organic framework can be improved, the stability of the active ion supplement in the pores of the metal organic framework can be improved, and the sustained release that is too fast or too slow can be avoided, thereby achieving long-term and stable supplementation of active ions, which can more effectively improve the cycle life and storage stability of the secondary battery.

[0038] The pore size test method of the metal organic framework is nitrogen elution desorption test, referring to GB / T21650.3-2011.

[0039] In some embodiments, the metal organic framework D V50 The particle size is 1 to 10 μm, for example, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm or a range consisting of any two values ​​thereof. V50 The particle size within this range can ensure the replenishment efficiency of the MOF material to the active ion supplement, while reducing the catalytic effect of the MOF material on the side reactions of the electrolyte.

[0040] Wherein, the D of the metal organic framework V50 The particle size refers to the particle size corresponding to 50% of the volume distribution of the metal organic framework, which can be obtained by laser particle size analysis test, referring to GB / T19077-2016 laser particle size analyzer diffraction method.

[0041] In some embodiments, the metal organic framework comprises a metal ion and an organic ligand;

[0042] The metal ions include Zn 2+ 、Co 3+ 、Co 2+ 、Cu 2+ 、Fe 3+ 、Fe 2+ 、Mn 3+ 、Mn 2+ 、Al 3 +、Ni 2+ 、Ni + Mg 2+ 、Ti 4+ 、Na + , K + , Rb + , Ca 2+ 、Sr 2+ Sc 3+ 、Y 3+ 、Zr 4+ 、V 4+ 、V 3+ 、V 2+ 、Nb 3+ Cr 3+ 、Ru 3+ 、Ru 2+ , Pt 2+ , Pt + 、Ag + 、Au + 、Cd 2+ 、Sn 4+ 、Sn 2+ At least one of;

[0043] The organic ligand includes at least one of a carboxylic acid ligand, an ester ligand, a pyridine ligand, an azole ligand, an aminocarboxylic acid ligand, a urea ligand, and a porphyrin ligand.

[0044] In some embodiments, the carboxylic acid ligand includes at least one of terephthalic acid, trimesic acid, naphthalene dicarboxylic acid, 2,5-dihydroxyterephthalic acid, 4,4'-biphenyl dicarboxylic acid, 2-aminoterephthalic acid, and adamantane tetracarboxylic acid.

[0045] In some embodiments, the ester ligand includes at least one of terephthalate, trimesic acid ester, naphthalene dicarboxylic acid ester, and 4,4',4'-(benzene-1,3,5-trialkyltris(benzene-4,1-diyl))tribenzoate.

[0046] In some embodiments, the azole ligand includes at least one of dimethylimidazole, diethyltetramethylimidazole, imidazole cyanoethylide, and 1H-1,2,3-triazole.

[0047] In some embodiments, the pyridine ratio includes 4,4-bipyridine.

[0048] In some embodiments, the aminocarboxylic acid ligand includes 2-aminoterephthalic acid,

[0049] In some embodiments, the urea ligand comprises urea.

[0050] In some embodiments, the porphyrin ligand includes 4-carboxyphenylporphyrin.

[0051] In some embodiments, the metal organic framework includes at least one of MOF-808, MOF-74, MOF-77, MOF-177, MOF-180, MIL-101, ZIF-68, UiO-67, IRMOF-1, IRMOF-3, IRMOF-8, IRMOF-9, IRMOF-10, IRMOF-11, IRMOF-12, PCN-224, and PCN-222.

[0052] The present application does not limit the source of the metal organic framework, and the metal organic framework can be obtained through conventional commercial purchase, or the corresponding metal organic framework can be prepared by a public method.

[0053] In some embodiments, the preparation method of the active ion supplement material is: adding a metal organic framework to an active ion supplement solution, stirring, washing, and drying to obtain the CF3SO2Li@MOF or CF3SO2Na@MOF composite material (hereinafter referred to as "composite material").

[0054] The mass ratio of the active ion supplement to the metal organic framework is controlled by controlling the stirring time, the amount of the active ion supplement solution, and the mass ratio of the metal organic framework to the active ion supplement solution.

[0055] In some embodiments, the mass ratio of the metal organic framework to the active ion supplement solution is 5:1, 10:1, 20:1, 30:1, 40:1, 50:1, or a range consisting of any two values ​​thereof, and the mass ratio is changed by the selection of the MOF carrier.

[0056] In some embodiments, the molar concentration of the active ion supplement solution is 0.2-1.5 mol / L, for example, 0.2 mol / L, 0.5 mol / L, 0.7 mol / L, 1 mol / L, 1.5 mol / L, or a range consisting of any two values ​​therein.

[0057] In some embodiments, the solvent in the active ion supplement solution is at least one of methanol, ethanol, water, acetone, propanol, N,N-dimethylformamide, acetonitrile, dimethyl sulfoxide, sulfolane, tetrahydrofuran, 2-methyltetrahydrofuran, ethylene nitrate, ethylene carbonate, acetone and dimethylacetamide.

[0058] One embodiment of the present application provides a secondary battery, including an active ion supplement material, wherein the active ion supplement material includes the active ion supplement material described above. The present application adds the above-mentioned active ion supplement material to the electrolyte, and the active ion supplement can supplement the active ions (lithium ions and / or sodium ions) for the secondary battery. The active ion supplement is located in the pores of the metal-organic framework, and can achieve the effect of sustained-release supplementation of active ions. The active ions are supplemented during the cycle and / or storage process of the secondary battery, and the active ions are supplemented throughout the life cycle, thereby avoiding performance degradation of the secondary battery caused by excessive consumption of active ions. At the same time, the reaction product of the active ion supplement is mainly gas, which can be completely discharged through the secondary sealing process after formation, and has little adverse effect on the secondary battery. It can avoid the negative impact of the addition to the positive active material layer on the positive electrode plate, and effectively improve the cycle life and storage stability of the secondary battery.

[0059] Among them, the present application can observe whether the active ion supplement material (MOF has a regular crystal morphology) is present in the secondary battery (for example, electrolyte, positive electrode, negative electrode, separator, etc.) by scanning electron microscopy, and then determine the MOF type and content by combining characterization methods such as X-ray diffractometer (XRD), inductively coupled plasma mass spectrometer (ICP-MS) / X-ray photoelectron spectroscopy (XPS) and infrared spectroscopy (IR).

[0060] The active ion supplement material can be detected by the following method: the positive electrode, negative electrode, and separator of the secondary battery are rinsed three times in EMC (ethyl methyl carbonate) to remove any residual active ion supplement material, electrolyte residue, and SEI on the positive, negative, and separator. The S element on the positive, negative, and separator is characterized by EDS (energy dispersive spectrometer) to ensure that no residue is present. The cleaned positive, negative, and separator are then thoroughly soaked in a methanol solution to extract the active ion supplement material from the MOF pores. The extract sample is qualitatively analyzed by IR (infrared spectroscopy) and GC (gas chromatography). The mass ratio of the metal organic framework (MOF) to the active ion supplement material is then determined by comparing the ratio of the MOF central ion to the S element using inductively coupled plasma optical emission spectrometry (ICP-OES). In some embodiments, the secondary battery includes a positive electrode sheet, a negative electrode sheet, and a separator.

[0061] In some embodiments, at least one of the positive electrode sheet, the negative electrode sheet, and the separator includes the active ion supplement material.

[0062] In some embodiments, the ratio of the mass of the active ion supplement material in the secondary battery to the capacity of the secondary battery is in the range of 50 to 500 mg / Ah, for example, it can be 50 mg / Ah, 100 mg / Ah, 200 mg / Ah, 250 mg / Ah, 300 mg / Ah, 350 mg / Ah, 400 mg / Ah, 450 mg / Ah, 500 mg / Ah, or a range consisting of any two values ​​therein. By controlling the ratio of the mass of the active ion supplement material in the secondary battery to the capacity of the secondary battery within this range, the cycle stability can be improved while reducing the risk of gas production. In some embodiments, the ratio of the mass of the active ion supplement material in the secondary battery to the capacity of the secondary battery is in the range of 125 to 375 mg / Ah.

[0063] In some embodiments, the secondary battery includes an electrolyte, the electrolyte includes at least one of a first additive and a second additive, the first additive includes at least one of vinylene carbonate and fluoroethylene carbonate, and by adding the first additive to the electrolyte, the first additive preferentially reduces and decomposes the solvent in the electrolyte at the electrode / electrolyte interface to form a passivation layer, forming a dense SEI film that is ion-conductive and electronically insulating to improve interface stability and inhibit interface side reactions, which can significantly improve electrochemical performance. The reaction products of the first additive during the film formation process include organic salts and inorganic salts, which inevitably consume active ions (Li2O3) in the electrochemical system. + / Na + ), resulting in capacity loss, the active ion supplement material can effectively supplement the active ions consumed by the film-forming reaction, thereby further improving the cycle and storage performance of the secondary battery.

[0064] In some embodiments, the second additive includes at least one of vinyl sulfate, 1,3-propane sultone, propenyl-1,3-sultone, ethylene sulfite, methylene methanedisulfonate, 1,4-butane sultone, and tripropynyl phosphate. The second additive can participate in the formation of the SEI film and inhibit interfacial side reactions, thereby reducing the risk of high-temperature gas production of the active ion supplement material.

[0065] In some embodiments, the mass percentage of the first additive in the electrolyte is 0.5% to 4.2%, for example, it can be 0.5%, 1%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5% or a range consisting of any two of these values.

[0066] In some embodiments, the mass percentage of the second additive in the electrolyte is 0.1% to 1.4%, for example, it can be 0.1%, 0.2%, 0.4%, 0.5%, 1.0%, 1.2%, 1.4% or a range consisting of any two of these values, which can effectively inhibit gas production of the secondary battery and improve cycle stability.

[0067] The content of the first and second additives in the electrolyte was determined using the following method: The content of each component in the electrolyte was monitored by combining electrolyte quantification, organic matter qualitative analysis, and ion composition analysis. The reference standard for electrolyte quantification was GB / T 9722-2006, "General Rules for Gas Chromatography of Chemical Reagents." Specific testing conditions included: FID detector, detector temperature 300°C, inlet temperature 250°C, split ratio 100:1, injection volume 0.2 μL, chromatographic column: KB-200, 60 m x 0.32 mm x 0.50 μm. The reference standard for organic matter qualitative analysis was GB / T 9722-2006, "General Rules for Mass Spectrometry Methods," MS ion source temperature 230°C, inlet temperature 240°C, split ratio 150:1, injection volume 0.2 μL, chromatographic column: HP-5MS, 30 m x 0.32 mm x 0.25 μm. The reference standards for the ion composition analysis method are GB / T 19282-2014 "Analysis Method for Lithium Hexafluorophosphate Products" and GB / T 34672-2017 "General Rules for Determination by Ion Chromatography". Electrolyte sample pretreatment: take 1g and dilute 100 times (conventional), eluent concentration: 4.1mmol / L Na2CO3 and 2.7mmol / L NaHCO3 and 20% acetonitrile, methanesulfonic acid concentration: 0.05mol / L, test time: 65min.

[0068] In some embodiments, the second additive includes vinyl sulfate and methylene methanedisulfonate in a mass ratio of (0.5 to 4):1. In particular, when vinyl sulfate and methylene methanedisulfonate in a mass ratio of (0.5 to 4):1 are used as the second additive, it can more effectively inhibit the gas production of the secondary battery, reduce the volume expansion rate of the secondary battery, and improve the safety of the secondary battery.

[0069] In one embodiment, the electrolyte further includes a solvent, and the solvent includes at least one of ethylene carbonate (EC), propylene carbonate (PC), γ-butyrolactone, dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), methyl propyl carbonate (MPC), methyl isopropyl carbonate (MIPC), methyl butyl carbonate, ethyl propyl carbonate, dipropyl carbonate, dibutyl carbonate, diphenyl carbonate, methyl propionate (MP), ethyl propionate (EP), propyl propionate (PP), ethyl butyrate (EB), methyl acetate (MA), ethyl acetate (EA), propyl acetate (PA), dioxolane (DOL), tetrahydrofuran (THF), 2-methyltetrahydrofuran (2Me-THF), tetrahydropyran (THP), 1,2-dimethoxyethane (DME), diethylene glycol dimethyl ether (G2), 1,2-diethoxyethane and 1,2-dibutoxyethane.

[0070] In one embodiment, the electrolyte includes a first solvent and a second solvent;

[0071] The first solvent comprises at least one of ethylene carbonate, propylene carbonate, butylene carbonate and gamma-butyrolactone;

[0072] The second solvent includes at least one of dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methylpropyl carbonate, diphenyl carbonate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, and ethyl butyrate.

[0073] In some embodiments, the mass ratio of the first solvent to the second solvent is (20-50):(50-80).

[0074] In some embodiments, the electrolyte further comprises a lithium salt or a sodium salt.

[0075] In some embodiments, the lithium salt includes at least one of lithium hexafluorophosphate (LiPF6), lithium tetrafluoroborate (LiBF4), lithium bis(oxalatoborate) (LiBOB), lithium difluorooxalatoborate (LiDFOB), lithium difluorobis(oxalatophosphate) (LiDFOP), lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethylsulfonyl)imide (LiTFSI), and lithium perchlorate (LiClO4).

[0076] In some embodiments, the mass percentage of the lithium salt in the electrolyte is 10.0% to 18.44%, for example, it can be 10.0%, 12.50%, 13.07%, 13.65%, 14.22%, 14.80%, 15.37%, or 18.44%. By controlling the concentration of the lithium salt within this range, the conductivity of the electrolyte can be improved and the stability of the electrolyte can be improved.

[0077] In some embodiments, the lithium salt includes lithium hexafluorophosphate and lithium bis(fluorosulfonyl)imide.

[0078] In some embodiments, the mass percentage of the lithium bis(fluorosulfonyl)imide in the electrolyte is 0 to 18.44%, for example, it can be 0, 3.07%, 6.15%, 9.22%, 12.30%, 15.37%, 18.44% or a range consisting of any two values ​​therein, which can improve the stability of the electrolyte and the lithium ion migration number.

[0079] The present application adopts a combination of lithium hexafluorophosphate and lithium bis(fluorosulfonyl)imide as the lithium salt, which can improve the lithium ion migration number and antioxidant performance, and has good aluminum foil passivation ability. It has good compatibility with the additive system and diaphragm of the electrolyte of the present application, improves stability, repairs the electrode / electrolyte interface, improves ionic conductivity, and promotes the conduction of lithium ions in the bulk phase.

[0080] In some embodiments, the electrolyte includes a sodium salt, and the sodium salt includes one or more of sodium perchlorate, sodium tetrafluoroborate, sodium hexafluorophosphate, sodium hexafluoroarsenate, sodium trifluoromethylsulfonate, sodium bis(fluorosulfonyl)imide, and sodium bis(trifluoromethylsulfonyl)imide.

[0081] In some embodiments, the mass percentage of the sodium salt in the electrolyte is 10.8% to 21.0%, for example, it can be 10.8%, 13.5%, 14.3%, 15.1%, 16.2%, 16.7%, 21.0% or a range consisting of any two values ​​therein, which can improve the stability of the electrolyte and the sodium ion migration number.

[0082] In one embodiment, the positive electrode sheet includes a positive electrode current collector and a positive electrode active material layer disposed on at least one surface of the positive electrode current collector, and the positive electrode active material layer includes a positive electrode active material.

[0083] In one embodiment, the positive electrode active material may be a positive electrode active material for secondary batteries known in the art.

[0084] As a non-limiting example, when the secondary battery is a lithium-ion battery, the positive electrode active material may include lithium-containing phosphates, lithium transition metal oxides, and their respective modified compounds. However, the present application is not limited to these materials or substances, and other traditional materials or substances that can be used as secondary battery positive electrode active materials may also be used. These positive electrode active materials may be used alone or in combination of two or more. Among them, non-limiting examples of lithium transition metal oxides may include, but are not limited to, one or more of lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, and their modified compounds.

[0085] As a non-limiting example, when the secondary battery is a sodium ion battery, the positive electrode active material can be selected from at least one of sodium iron composite oxide, sodium cobalt composite oxide, sodium manganese composite oxide, sodium nickel composite oxide, sodium nickel titanium composite oxide, sodium nickel manganese composite oxide, sodium iron manganese composite oxide, sodium nickel cobalt manganese composite oxide, sodium iron phosphate compound, sodium manganese phosphate compound, and sodium cobalt phosphate compound.

[0086] In one embodiment, the positive electrode active material includes lithium iron phosphate, and the lithium iron phosphate includes a compound with the general chemical formula LiFePO4.

[0087] In one embodiment, the positive electrode active material layer further includes a binder and a conductive agent.

[0088] In some embodiments, the type of the positive electrode current collector is not particularly limited, and the positive electrode current collector can be any material known to be suitable for use as a positive electrode current collector.

[0089] In some embodiments, the positive electrode current collector includes metal materials such as aluminum, stainless steel, nickel plating, titanium, tantalum, and carbon materials such as carbon cloth and carbon paper.

[0090] The form of the positive electrode current collector is not particularly limited. When the positive electrode current collector is a metal material, the positive electrode current collector may be in the form of metal foil, metal cylinder, metal strip coil, metal plate, metal foil, metal mesh, stamped metal, foamed metal, etc. When the positive electrode current collector is a carbon material, the positive electrode current collector may be in the form of, but not limited to, carbon plate, carbon film, carbon cylinder, etc.

[0091] In some embodiments, the negative electrode sheet includes a negative electrode current collector and a negative electrode active material layer disposed on at least one surface of the negative electrode current collector, and the negative electrode active material layer includes a negative electrode active material.

[0092] In the present application, there is no particular limitation on the negative electrode current collector, as long as it can achieve the purpose of the present application. For example, it can be copper foil, copper alloy foil, aluminum foil, nickel foil, stainless steel foil, titanium foil, foam nickel, foam copper or a composite current collector.

[0093] In some embodiments, the negative electrode active material includes graphite, silicon-based materials, mesophase microcarbon beads (MCMB), hard carbon, soft carbon, Li-Sn alloy, Li-Sn-O alloy, Sn, SnO, SnO2, spinel structure lithium titanate Li4Ti5O 12 , at least one of Li-Al alloy and metallic lithium.

[0094] In some embodiments, the negative electrode active material includes graphite or silicon-based materials.

[0095] In some embodiments, the silicon-based material includes at least one of silicon, a silicon-carbon alloy, a silicon-oxygen compound, or a silicon-containing metal compound.

[0096] In some embodiments, the mass of the silicon-based material accounts for 3% to 20% of the total mass of the negative electrode active material, for example, 3%, 5%, 10%, 12%, 15%, 18%, 20%, or any combination thereof.

[0097] In some embodiments, the negative electrode active material layer further includes a conductive agent and a binder.

[0098] In some embodiments, the type of the conductive agent mentioned in the present application is not limited, and known conductive agents can be used.

[0099] In some embodiments, the conductive agent includes at least one of carbon materials such as acetylene black, needle coke, carbon nanotubes, and graphene.

[0100] In some embodiments, the type of the binder mentioned in this application is not limited, and known binders can be used.

[0101] In some embodiments, the binder mentioned includes at least one of polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, polyimide, aromatic polyamide, cellulose, nitrocellulose, styrene-butadiene rubber, nitrile rubber, fluororubber, isoprene rubber, polybutadiene rubber, ethylene-propylene rubber, styrene-butadiene-styrene block copolymer or its hydride, ethylene-propylene-diene terpolymer, styrene-ethylene-butadiene-ethylene copolymer, styrene-isoprene-styrene block copolymer, syndiotactic-1,2-polybutadiene, polyvinyl acetate, ethylene-vinyl acetate copolymer, polyvinylidene fluoride, polytetrafluoroethylene, fluorinated polyvinylidene fluoride, and polytetrafluoroethylene-ethylene copolymer.

[0102] In one embodiment, the separator comprises a porous sheet or non-woven fabric having excellent liquid retention. Materials for the resin or glass fiber separator include, but are not limited to, polyolefin, aromatic polyamide, polytetrafluoroethylene, polyethersulfone, and the like.

[0103] In one embodiment, the polyolefin is polyethylene or polypropylene. In some embodiments, the polyolefin is polypropylene. The materials of the above-mentioned diaphragm can be used alone or in any combination.

[0104] In some embodiments, the secondary battery may include an outer packaging, which may be used to encapsulate the electrode assembly and the electrolyte.

[0105] In some embodiments, the outer packaging of the secondary battery can be a hard shell, such as a hard plastic shell, an aluminum shell, or a steel shell. Alternatively, the outer packaging of the secondary battery can be a soft shell, such as a pouch-type soft shell. The soft shell can be made of plastic, such as polypropylene, polybutylene terephthalate, and polybutylene succinate.

[0106] The present application has no particular limitation on the shape of the secondary battery, which may be cylindrical, square, or any other shape.

[0107] An embodiment of the present application provides an electric device, comprising the secondary battery described above, wherein the secondary battery serves as a power supply for the electric device.

[0108] Exemplarily, the above-mentioned electrical devices may include mobile devices (such as mobile phones, laptops, etc.), electric vehicles (such as pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc., but are not limited to these.

[0109] The present application is further described below with specific examples:

[0110] Example 1

[0111] A method for preparing a secondary battery comprises the following steps:

[0112] (1) Preparation of active ion supplement materials:

[0113] Zirconium oxychloride octahydrate (ZrOCl2·8H2O, 0.97 mg, 3.0 mmol) and 1,3,5-benzenetricarboxylic acid (H3BTC, 0.21 mg, 1 mmol) were dissolved in a 30 mL / 30 mL N,N-dimethylformamide (DMF) / formic acid mixture and transferred to a 100 mL polytetrafluoroethylene-lined autoclave. The mixture was heated at 130°C for two days. After cooling to room temperature, the MOF-808 powder was collected by filtration and washed three times with DMF. The sample was then immersed in methanol for solvent exchange for three days, with the methanol replaced three times daily. Finally, the MOF-808 was vacuum-dried at room temperature and then at 150°C for 10 hours to obtain MOF-808 nanoparticles.

[0114] 8g of MOF-808 nanoparticles were immersed in 10mL of a 1mol / L CF3SO2Li methanol solution and stirred for 24 hours to allow the CF3SO2Li to fully enter the pores of MOF-808 and ensure that the CF3SO2Li in the MOF support was saturated (the concentration of the CF3SO2Li methanol solution no longer changed as determined by UV-visible absorption spectroscopy). Then, the particles were washed three times with methanol to remove the CF3SO2Li remaining on the outside of the MOF-808 particles and vacuum dried at 100°C for 10h to obtain a lithium-supplementing material.

[0115] Among them, the obtained active ion supplement material includes a metal organic framework (MOF-808) and an active ion supplement (CF3SO2Li) located in the pores of the metal organic framework, abbreviated as CF3SO2Li@MOF808.

[0116] (2) Preparation of electrolyte:

[0117] Ethylene carbonate (EC) and ethyl methyl carbonate (EMC) were mixed in a mass ratio of 35:65 to obtain a mixed solvent. The molecular sieve was used to remove water and set aside; lithium hexafluorophosphate (LiPF6) was added to the mixed solvent in an argon-filled glove box at room temperature, and the mixture was continuously stirred and cooled to obtain a transparent liquid; active ion supplement material, vinylene carbonate (VC), vinyl sulfate (DTD), and methylene methanedisulfonate (MMDS) were added to the transparent liquid and stirred evenly to obtain an electrolyte;

[0118] Among them, the mass percentage of LiPF6 in the electrolyte is 12.8%, the content of active ion supplement material is 20 mg / mL, the mass percentage of the first additive VC is 3%, and the second additives are DTD and MMDS, among which the mass percentage of DTD is 0.5% and the mass percentage of MMDS is 0.3%.

[0119] (2) Preparation of positive electrode sheet:

[0120] The positive electrode active material LiFePO4, the conductive agent acetylene black (Super P) and the binder polyvinylidene fluoride (PVDF) were mixed uniformly in a mass ratio of LiFePO4:Super P:PVDF=94:3:3, and evenly dispersed in 1-methyl-2-pyrrolidone (NMP) to prepare a uniform black slurry. The mixed slurry was coated on both sides of the aluminum foil, and then baked and roller pressed (the compaction density was 2.6g / cm 3 ), and then cut into strips and pieces to obtain the positive electrode sheet.

[0121] (3) Preparation of negative electrode sheet:

[0122] The negative electrode active material artificial graphite (AG), conductive agent acetylene black (Super P) and binder SBR were mixed uniformly at a mass ratio of AG:Super P:SBR = 94:3:3, and evenly dispersed in deionized water to form a uniform black slurry. The mixed slurry was coated on both sides of the copper foil and then baked and roller pressed (the compaction density was 1.65g / cm 3 ), and then cut into strips and pieces to obtain the negative electrode sheet.

[0123] (4) Production of secondary batteries

[0124] The prepared positive electrode sheet, separator (PE film with a thickness of 7 μm), and negative electrode sheet are stacked in order with the separator placed between the positive and negative electrode sheets. The bare battery cell is obtained by winding, hot pressing, Hi-pot testing, and tab welding. The bare battery cell is encapsulated in an outer packaging aluminum-plastic film and baked in an oven at 100±5°C for 48 hours. The prepared electrolyte (injection coefficient is 4.0 g / Ah) is injected into the dried battery, allowed to stand for 5 minutes, formed (0.05C constant current charging to 4.0V), allowed to stand for 5 minutes, and capacity divided to obtain a secondary battery.

[0125] The parameters of the active ion supplement material of this embodiment are shown in Table 1 and Table 2.

[0126] Examples 2 to 5

[0127] The difference between Examples 2 to 5 and Example 1 is that Examples 2 to 5 change the amount of active ion supplement material added to the electrolyte, thereby changing the ratio range of the mass of the active ion supplement material in the secondary battery to the capacity of the secondary battery, as shown in Tables 1 and 2.

[0128] Example 21, Example 22

[0129] The difference between Example 21 and Example 2 is that the first additive is not added in Example 21, as shown in Table 1.

[0130] The difference between Example 22 and Example 2 is that the second additive is not added in Example 22, as shown in Table 1.

[0131] Examples 6 to 8

[0132] The difference between Examples 6 to 8 and Example 2 is that Examples 6 to 8 change the type of metal organic framework, as shown in Table 1.

[0133] Examples 9 to 12

[0134] The difference between Examples 9 to 12 and Example 2 is that Examples 9 to 12 change the amount of vinylene carbonate (VC) added to the electrolyte, thereby changing the mass percentage of vinylene carbonate (VC) in the electrolyte, as shown in Tables 1 and 2.

[0135] Example 13

[0136] The difference between Example 13 and Example 2 is that Example 13 uses an equal amount of fluoroethylene carbonate (FEC) to replace vinylene carbonate (VC), as shown in Table 1.

[0137] Examples 14 to 19

[0138] The difference between Examples 14 to 15 and 17 to 19 and Example 2 is that Examples 14 to 15 and 17 to 19 change the amount of vinyl sulfate (DTD) and / or methylene methanedisulfonate (MMDS) added to the electrolyte, thereby changing the mass percentage of vinyl sulfate (DTD) and / or methylene methanedisulfonate (MMDS) in the electrolyte, as shown in Tables 1 and 2.

[0139] In Example 16, 1,3-propane sultone (PS) was used to replace methylene methanedisulfonate (MMDS).

[0140] Example 20

[0141] A method for preparing a secondary battery comprises the following steps:

[0142] (1) Preparation of active ion supplement materials:

[0143] 8g of MOF-808 nanoparticles were immersed in 10mL of a 1mol / L methanol solution of CF3SO2Na and stirred for 24 hours to allow the CF3SO2Na to fully penetrate the pores of the MOF-808. The composite was then washed three times with methanol to remove any residual CF3SO2Na on the outside of the MOF-808 particles and dried under vacuum at 100°C for 10 hours to obtain the active ion supplement material.

[0144] The obtained active ion supplement material includes a metal organic framework (MOF-808) and an active ion supplement (CF3SO2Na) located in the pores of MOF-808, referred to as CF3SO2Na@MOF-808.

[0145] (2) Preparation of electrolyte:

[0146] Propylene carbonate (PC) and ethyl methyl carbonate (EMC) were mixed in a mass ratio of 30:70 to obtain a mixed solvent. Molecular sieves were used to remove water and set aside; sodium hexafluorophosphate (NaPF6) was added to the mixed solvent in an argon-filled glove box at room temperature, and the mixture was stirred continuously and cooled to obtain a transparent liquid; active ion supplement material, fluoroethylene carbonate (FEC), and diethylene sulfate (DTD) were added to the transparent liquid and stirred evenly to obtain an electrolyte;

[0147] The mass percentage of NaPF6 in the electrolyte is 13.5%, the content of the active ion supplement material is 50 mg / mL, the mass percentage of FEC is 2.0%, and the mass percentage of DTD is 1.0%.

[0148] (2) Preparation of positive electrode sheet:

[0149] The positive electrode active material NaNi 1 / 3 Mn 1 / 3 Fe 1 / 3 O2, conductive agent acetylene black (Super P) and binder polyvinylidene fluoride (PVDF) are NaNi 1 / 3 Mn 1 / 3 Fe 1 / 3 O2:Super P:PVDF=95:3:2 were mixed evenly and dispersed evenly in 1-methyl-2-pyrrolidone (NMP) to make a uniform black slurry. The mixed slurry was coated on both sides of aluminum foil and then baked and rolled (the compaction density was 3.0g / cm 3 ), and then cut into strips and pieces to obtain the positive electrode sheet.

[0150] (3) Preparation of negative electrode sheet:

[0151] The negative electrode active material hard carbon (HC), conductive agent acetylene black (Super P) and binder SBR, CMC were mixed uniformly at a mass ratio of HC:Super P:SBR:CMC=94:2.5:2.5:1, and evenly dispersed in deionized water to form a uniform black slurry. The mixed slurry was coated on both sides of the copper foil, and then baked and roller pressed (the compaction density was 0.9g / cm 3 ), and then cut into strips and pieces to obtain the negative electrode sheet.

[0152] (4) Production of secondary batteries

[0153] The prepared positive electrode sheet, diaphragm (PE film with a thickness of 7 μm), and negative electrode sheet are stacked in order with the diaphragm placed between the positive and negative electrode sheets. The bare battery cell is obtained by winding, hot pressing, Hi-pot testing, and tab welding. The bare battery cell is encapsulated in an outer packaging aluminum-plastic film and baked in an oven at 90±5°C for 48 hours. The prepared electrolyte (injection coefficient is 6.0 g / Ah) is injected into the dried battery, allowed to stand for 5 minutes, formed (0.05C constant current charging to 4.3V), allowed to stand for 5 minutes, and capacity divided to obtain a secondary battery.

[0154] The parameters of the active ion supplement material of this embodiment are shown in Table 1, and the parameters of the electrolyte are shown in Table 2.

[0155] Testing method for the capacity of secondary batteries: Place the secondary batteries obtained in the examples and comparative examples at 25±1°C, and charge and discharge them at a charge and discharge rate of 0.33C / 0.33C in the range of 2.5~3.65V (voltage range of lithium battery) / 1.5~4.0V (voltage range of sodium battery) for 3 weeks, and record the average discharge capacity of the secondary batteries over the 3 weeks, and use this capacity as the nominal capacity.

[0156] Comparative Example 1

[0157] The difference between Comparative Example 1 and Example 2 is that no active ion supplement material is added in Comparative Example 1.

[0158] Comparative Example 1-1

[0159] The difference between Comparative Example 1 and Example 2 is that the active ion supplement material, the first additive and the second additive are not added in Comparative Example 1.

[0160] Comparative Example 2

[0161] The difference between Comparative Example 2 and Example 19 is that an equal amount of CF3SO2Li is added to Comparative Example 2, that is, this comparative example uses an equal amount of CF3SO2Li to replace the active ion supplement material.

[0162] Table 1 Active ion supplement materials and electrolyte design parameters

[0163]

[0164]

[0165] Table 2 Ratio of active ions to capacity and electrolyte composition after fractionation and capacity

[0166]

[0167] Lithium-ion battery performance test methods

[0168] Normal temperature cycle performance test: The secondary batteries obtained from the examples and comparative examples were placed at 25±1°C, and charged and discharged at a charge and discharge rate of 0.33C / 0.33C in the range of 2.5 to 3.65V for 3 weeks, and the average discharge capacity of the secondary battery over 3 weeks was recorded as the nominal capacity. The secondary battery was then charged to 4.0V at 0.1C for lithium replenishment reaction. The secondary batteries obtained from the examples and comparative examples were subjected to charge and discharge cycle tests at a charge and discharge rate of 1C / 1C in the range of 2.5 to 3.65V, and the discharge capacity of the secondary battery in the first week and the discharge capacity after 2000 cycles were recorded. During this period, the secondary battery was charged to 4.0V at a rate of 0.1C every 200 cycles for lithium replenishment reaction. The capacity retention rate for 2000 weeks = discharge capacity for 2000 weeks / discharge capacity for the first week * 100%. The recorded data is shown in Table 3.

[0169] 60°C Storage Performance: The secondary batteries obtained from the Examples and Comparative Examples were placed at 25±1°C and charged and discharged at a charge and discharge rate of 0.33C / 0.33C within a range of 2.5 to 3.65V for three weeks. The average discharge capacity of the secondary batteries over the three weeks was recorded as the nominal capacity. The secondary batteries were then charged to 4.0V at a rate of 0.1C for lithium replenishment, discharged to 2.5V at 0.33C, and then charged to 3.65V at a constant current of 0.33C. The batteries were then maintained at a constant voltage of 3.65V until the current was below 0.05C. The batteries were then stored at 60±1°C. Every 30 days, the secondary batteries were charged to 4.0V at room temperature for lithium replenishment. After 120 days, the charge and discharge tests were repeated and the discharge capacity was recorded. 60°C Storage Capacity Retention = Discharge Specific Capacity after 120 Days / Discharge Specific Capacity in the First Week * 100%. The recorded data is shown in Table 3.

[0170] High-temperature storage gas production test: The secondary batteries obtained from the examples and comparative examples were placed at 25±1°C and charged and discharged at a charge and discharge rate of 0.33C / 0.33C within the range of 2.5 to 3.65V for 3 weeks, and the average discharge capacity of the secondary batteries over the 3 weeks was recorded as the nominal capacity. The secondary batteries were then charged to 4.0V at 0.1C for lithium replenishment, discharged to 2.5V at a rate of 0.33C, and then charged to 3.65V at a constant current of 0.33C. The batteries were then kept at a constant voltage of 3.65V until the current was below 0.05C, bringing the batteries to a fully charged state of 3.65V. The batteries were then stored at 70±1°C. During this period, the secondary batteries were charged to 4.0V at room temperature every 10 days for lithium replenishment. The volume of the fully charged secondary batteries before storage was measured and recorded as V0. The fully charged secondary batteries were then placed in an oven at 70±1°C. After 70 days, the batteries were removed and their volume after storage was immediately measured and recorded as V1. Volume expansion ratio = (V1-V0) / V0*100%. The results are shown in Table 3.

[0171] Sodium ion battery performance test method

[0172] Normal temperature cycle performance test: The secondary batteries obtained from the examples and comparative examples were placed at 25±1°C, and charged and discharged at a charge and discharge rate of 0.33C / 0.33C within the range of 1.5 to 4.0V for 3 weeks, and the average discharge capacity of the secondary batteries over the 3 weeks was recorded, and this capacity was used as the nominal capacity. The secondary batteries were then charged to 4.3V at a rate of 0.1C for sodium replenishment reaction. The secondary batteries obtained from the examples and comparative examples were subjected to charge and discharge cycle tests at a charge and discharge rate of 1C / 1C within the range of 1.5 to 4.0V, and the discharge capacity in the first week and the discharge capacity after 2000 cycles were recorded. During this period, the secondary batteries were charged to 4.3V at a rate of 0.1C every 200 cycles for sodium replenishment reaction. The capacity retention rate for 2000 weeks = discharge capacity in 2000 weeks / discharge capacity in the first week * 100%. The recorded data are shown in Table 3.

[0173] 60°C Storage Performance: The secondary batteries obtained from the examples and comparative examples were placed at 25±1°C and charged and discharged at a charge and discharge rate of 0.33C / 0.33C within the range of 1.5-4.0V for 3 weeks. The average discharge capacity of the secondary batteries over the 3 weeks was recorded as the nominal capacity. The secondary batteries were then charged at a rate of 0.1C until a sodium replenishment reaction occurred, discharged at a rate of 0.33C to 2.5V, and then charged at a constant current rate of 0.33C to 4.0V. The batteries were then charged at a constant voltage of 4.0V until the current was less than 0.05C. The batteries were then stored at 60±1°C. During this period, the secondary batteries were charged to 4.3V at room temperature every 30 days for a sodium replenishment reaction. After 120 days, the charge and discharge tests were performed again and the discharge capacity was recorded. 60°C Storage Capacity Retention Rate = Discharge Specific Capacity after 120 Days / Discharge Specific Capacity in the First Week * 100%. The recorded data is shown in Table 3.

[0174] High-temperature storage gas production test: The secondary batteries obtained from the examples and comparative examples were placed at 25±1°C and charged and discharged at a charge and discharge rate of 0.33C / 0.33C within the range of 1.5 to 4.0V for 3 weeks, and the average discharge capacity of the secondary battery over 3 weeks was recorded as the nominal capacity. The secondary battery was then charged to 4.3V at a rate of 0.1C for sodium replenishment reaction, discharged to 2.5V at a rate of 0.33C, and then charged to 4.0V at a constant current rate of 0.33C. The battery was then kept at a constant voltage of 4.0V until the current was lower than 0.05C, making it fully charged at 4.0V. The battery was then stored at 70±1°C. During this period, the secondary battery was charged to 4.3V at room temperature every 10 days for sodium replenishment reaction. The volume of the fully charged secondary battery before storage was tested and recorded as V0. The fully charged secondary battery was then placed in an oven at 70±1°C. After 70 days, the battery was taken out and its volume after storage was immediately tested and recorded as V1. Volume expansion ratio = (V1-V0) / V0*100%. The results are shown in Table 3.

[0175] Table 3 Electrochemical performance test results

[0176]

[0177]

[0178] As can be seen from Table 3, the active ion supplement material of the present application includes a metal-organic framework and an active ion supplement located in the pores of the metal-organic framework. The active ion supplement can supplement active ions for the secondary battery. The active ion supplement is located in the pores of the metal-organic framework and can achieve the effect of sustained-release supplementation of active ions. Active ions are supplemented during the cycle and / or storage process of the secondary battery, thereby achieving full life cycle supplementation of active ions, avoiding performance degradation of the secondary battery caused by excessive consumption of active ions, and effectively improving the cycle life and storage stability of the secondary battery.

[0179] Specifically, by comparing Example 19 with Comparative Example 2, and by comparing Example 2 with Comparative Example 1, the performance of the secondary battery to which the active ion supplement material of the present application is added is significantly improved; by comparing Example 2 with Example 21 and Example 22, the performance of the secondary battery to which the active ion supplement material of the present application is added and the first additive and the second additive are added at the same time is further improved.

[0180] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application and are not intended to limit the scope of protection of the present application. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application may be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the present application.

Claims

1. An active ion supplement material, characterized in that: including a metal organic framework and an active ion supplement located within the pores of the metal organic framework; The active ion supplement includes at least one of a lithium supplement and a sodium supplement.

2. The active ion supplement material according to claim 1, characterized in that The lithium supplement comprises lithium trifluoromethanesulfinate; and / or The sodium supplement includes sodium trifluoromethanesulfinate.

3. The active ion supplement material according to claim 1, characterized in that The mass ratio of the metal organic framework to the active ion supplement is (5-50):

1.

4. The active ion supplement material according to claim 1, characterized in that The pore diameter of the metal organic framework is 1.0 to 4.0 nm.

5. The active ion supplement material according to claim 1, characterized in that The metal organic framework comprises metal ions and organic ligands; The metal ions include Zn 2+ 、Co 3+ 、Co 2+ 、Cu 2+ 、Fe 3+ 、Fe 2+ 、Mn 3+ 、Mn 2+ 、Al 3 +、Ni 2+ 、Ni + Mg 2+ 、Ti 4+ 、Na + , K + , Rb + , Ca 2+ 、Sr 2+ Sc 3+ 、Y 3+ 、Zr 4+ 、V 4+ 、V 3+ 、V 2+ 、Nb 3+ Cr 3+ 、Ru 3+ 、Ru 2+ , Pt 2+ , Pt + 、Ag + 、Au + 、Cd 2 + 、Sn 4+ 、Sn 2+ At least one of; The organic ligand includes at least one of a carboxylic acid ligand, an ester ligand, a pyridine ligand, an azole ligand, an aminocarboxylic acid ligand, a urea ligand, and a porphyrin ligand.

6. A secondary battery, characterized in that: The invention comprises an active ion supplement material, wherein the active ion supplement material comprises the active ion supplement material according to any one of claims 1 to 5.

7. The secondary battery according to claim 6, characterized in that: The ratio of the mass of the active ion supplement material in the secondary battery to the capacity of the secondary battery is in the range of 50 to 500 mg / Ah.

8. The secondary battery according to claim 6, wherein The secondary battery includes an electrolyte, the electrolyte includes at least one of a first additive and a second additive, the first additive includes at least one of vinylene carbonate and fluoroethylene carbonate; the second additive includes at least one of vinyl sulfate, 1,3-propane sultone, propenyl-1,3-sultone, ethylene sulfite, methylene methanedisulfonate, 1,4-butane sultone, and tripropynyl phosphate.

9. The secondary battery according to claim 8, characterized in that The mass percentage of the first additive in the electrolyte is 0.5% to 4.2%; and / or The mass percentage of the second additive in the electrolyte is 0.1% to 1.4%.

10. An electrical device, characterized in that: The secondary battery comprises the secondary battery according to any one of claims 6 to 9, wherein the secondary battery is used as a power supply for the electrical device.

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