Positive electrode piece and lithium-ion secondary battery containing the same

Abstract

The present invention discloses a positive electrode piece and a lithium ion secondary battery including the same. The positive electrode piece according to the present invention includes a positive electrode current collector and a positive electrode active material layer provided on at least one surface of the positive electrode current collector. The positive electrode active material layer is a first positive electrode active material, Li 1+x Mn y M 2-y O 4-t A t , and the second positive electrode lithium supplement material Li 1+r Mn 1-p N p O 2-s B s wherein the positive electrode pieces satisfy 1.5≦R P / Q≦30, R is the resistance of the positive electrode pieces, R in Ω, and P is the compressed density of the positive electrode pieces, P in g / cm 3 Q is the surface density of one side of the positive electrode piece, and the unit of Q is g / 1540.25 mm 2 In the positive electrode piece of the present invention, the free lithium content on the surface of the second positive electrode lithium supplementary material is very low, and the processing characteristics are good. The lithium ion secondary battery manufactured by the positive electrode piece of the present invention has high energy density, rate characteristics and cycle life.

Description

[Technical Field]

[0001] The present invention belongs to the field of battery technology and relates to a positive electrode piece and a lithium-ion secondary battery containing the same. [Background technology]

[0002] During the initial charge-discharge cycle of lithium-ion secondary batteries, a solid electrolyte interface (SEI) forms on the negative electrode surface, causing irreversible capacity loss and reducing the energy density of the lithium-ion energy storage device. In devices using graphite negative electrodes, approximately 10% of the active lithium source is consumed during the first cycle. Using negative electrode materials with high specific capacity, such as alloys (silicon, tin, etc.), oxides (silicon oxide, tin oxide), and amorphous carbon, further increases the consumption of the active lithium source. Therefore, appropriate lithium replenishment methods are crucial for further improving the energy density of lithium-ion secondary batteries.

[0003] Patent Document 1 describes a method for replenishing lithium at the negative electrode. Specifically, metallic lithium powder, a negative electrode material, and a non-aqueous liquid are mixed to form a slurry, which is then applied to the current collector. While such a method can improve the energy density of the battery, controlling moisture content during the production process is extremely difficult, making the process challenging. FMC Corporation in the United States has performed some improvement treatments on lithium powder, and the resulting stabilized metallic lithium powder (SLMP) has better stability. However, it can only remain stable for a few hours even in dry air, posing a significant potential risk. Similarly, employing wet operations presents problems with selecting non-aqueous solvents and controlling moisture content.

[0004] Because methods of replenishing lithium at the negative electrode face significant challenges, methods of replenishing lithium at the positive electrode, which are safer and easier to operate, are attracting increasing attention from the industry. Patent Document 2 discloses lithium-oxygen compounds, lithium sources, and positive electrode replenishing lithium materials based on alkyllithium. However, lithium-containing compounds have a high decomposition potential, and oxygen and other by-products are generated during the decomposition process, affecting battery life. Patent Document 3 discloses lithium replenishing materials of the Li2NiO2 type. The free lithium content on the surface of this type of material is extremely high, and the slurry has a very strong tendency to form a gel during the slurry preparation process, which greatly affects processing performance, leads to a sustained increase in impedance, and affects cycle characteristics. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Chinese Patent CN1427490A [Patent Document 2] China patent CN104037418A [Patent Document 3] China patent CN101877417A [Patent Document 4] China patent CN110265627A [Overview of the Initiative]

[0006] The present invention aims to overcome the shortcomings of the prior art and provides a positive electrode piece and a lithium-ion secondary battery containing the same. The objectives are to stabilize the positive electrode piece, simplify the manufacturing method, and enable the lithium-ion secondary battery to have high energy density, rate characteristics, and cycle life.

[0007] To achieve the above object, in a first aspect, the present invention provides a positive electrode sheet, the positive electrode sheet including a positive electrode current collector and a positive electrode active material layer provided on at least one surface of the positive electrode current collector, the positive electrode active material layer including a first positive electrode active material and a second positive electrode lithium supplement material, the positive electrode sheet satisfying 1.5 ≦ R·P / Q ≦ 30, where R is the resistance of the positive electrode sheet, the unit of R being Ω, P is the compression density of the positive electrode sheet, the unit of P being g / cm y and Q is the areal density of one side of the positive electrode sheet, the unit of Q being g / 1540.25 mm 2 .

[0008] Preferably, the first positive electrode active material is Li 1+x Mn y M 2-y O 4-t A t , where x, y, and t satisfy -0.1 < x < 0.2, 1 < y ≦ 2, 0 ≦ t < 0.5, M is at least one of Ni, Fe, Zn, Mg, Al, Ti, and Zr, and A is at least one of S, N, F, Cl, and Br.

[0009] Preferably, the second positive electrode lithium supplement material is Li 1+r Mn 1-p N p O 2-s B s , where r, p, and s satisfy -0.1 < r < 0.2, 0 ≦ p < 0.2, 0 ≦ s < 0.2, N is at least one of Fe, Co, Ni, Ti, Zn, Mg, Al, V, Cr, and Zr, and B is at least one of S, N, F, Cl, and Br.

[0010] Preferably, the positive electrode sheet satisfies at least one of the following characteristics (a) to (d): (a) The positive electrode sheet satisfies 3.0 ≦ R·P / Q ≦ 15. (b) R satisfies R ≦ 5 Ω, preferably R ≦ 2 Ω. (c) P is 2.5 g / cm 3<P<3.2g / cm 3 Satisfying the conditions, (d) The above Q is 0.3g / 1540.25mm 2 <Q<0.55g / 1540.25mm 2 It satisfies the condition.

[0011] Preferably, the ratio of the weight of the first positive electrode active material to the weight of the second positive electrode lithium replenishment material is first positive electrode active material:second positive electrode lithium replenishment material = 5:1 to 99:1. More preferably, the ratio of the weight of the first positive electrode active material to the weight of the second positive electrode lithium replenishment material is first positive electrode active material:second positive electrode lithium replenishment material = 9:1 to 99:1.

[0012] Preferably, the weight content of the first positive electrode active material in the positive electrode active material layer is 80% to 98%. More preferably, the weight content of the first positive electrode active material in the positive electrode active material layer is 85% to 98%.

[0013] In a second embodiment, the present invention provides a lithium-ion secondary battery comprising the positive electrode piece, the negative electrode piece, a separator, and an electrolyte.

[0014] Preferably, the electrolyte contains 0.001% to 5% vinylene carbonate and / or 0.001% to 5% 1,3-propanesultone by weight.

[0015] Compared to prior art, the beneficial effects of the present invention are as follows: The second positive electrode lithium replenishment material in the positive electrode piece of the present invention has a very low surface free lithium content, good slurry stability, and good processing characteristics. Furthermore, due to the synergistic effect of the first positive electrode active material and the second positive electrode lithium replenishment material, and by specifying the positive electrode piece to satisfy 1.5 ≤ R·P / Q ≤ 30, the resulting lithium-ion secondary battery has high energy density, rate characteristics, and cycle life. [Brief explanation of the drawing]

[0016] [Figure 1]These are the XRD spectra of the second cathode lithium replenishment material in Example 1 before and after the initial charge, with Figure 1(b) being a magnified portion of Figure 1(a). [Figure 2] This is the initial charge-discharge curve of the lithium replenishment material for the second positive electrode in Example 1. [Modes for carrying out the invention]

[0017] To better illustrate the object, technical concept and advantages of the present invention, the present invention will be further described below with reference to specific examples. It will be understood by those skilled in the art that the specific examples described herein are for illustrative purposes only and do not limit the present invention.

[0018] In the examples, unless otherwise specified, all test methods used are conventional methods, and unless otherwise specified, all materials, reagents, etc. used are commercially available.

[0019] positive electrode piece The positive electrode piece according to the present invention includes a positive electrode current collector and a positive electrode active material layer provided on at least one surface of the positive electrode current collector. As one example, the positive electrode current collector includes two opposing surfaces in the thickness direction, and the positive electrode active material layer is provided on one or both of these two surfaces.

[0020] In the positive electrode piece according to the present invention, the positive electrode active material layer comprises a first positive electrode active material and a second positive electrode lithium replenishment material, and the positive electrode piece satisfies 1.5 ≤ R·P / Q ≤ 30, where R is the resistance of the positive electrode piece, the unit of R is Ω, and P is the compressed density of the positive electrode piece, the unit of P is g / cm³. 3 Q is the surface density of one side of the positive electrode piece, and its unit is g / 1540.25mm 2 That is the case.

[0021] The first positive electrode active material is Li 1+x Mn y M 2-y O 4-t A twhere x, y, and t satisfy -0.1 < x < 0.2, 1 < y ≤ 2, and 0 ≤ t < 0.5, M is at least one of Ni, Fe, Zn, Mg, Al, Ti, and Zr, and A is at least one of S, N, F, Cl, and Br.

[0022] The second positive electrode lithium replenishing material is Li 1+r Mn 1-p N p O 2-s B s where r, p, and s satisfy -0.1 < r < 0.2, 0 ≤ p < 0.2, and 0 ≤ s < 0.2, N is at least one of Fe, Co, Ni, Ti, Zn, Mg, Al, V, Cr, and Zr, and B is at least one of S, N, F, Cl, and Br.

[0023] The positive electrode piece according to the present invention uses a first positive electrode active material and a second positive electrode lithium replenishment material of a specific composition. Of these, the first positive electrode active material has a stable structure, good cycle stability and high initial Coulomb efficiency. The second positive electrode lithium replenishment material has a low surface free lithium content and good processing characteristics, and compared to the first positive electrode active material, the second positive electrode lithium replenishment material has a higher initial charge ratio capacity and a lower initial discharge ratio capacity. That is, the initial Coulomb efficiency is low, and during the initial charge, a large amount of lithium ions are released from the second positive electrode lithium replenishment material to replenish the loss of active lithium due to SEI formation, and during the initial discharge, sufficient lithium ions are returned to and absorbed in the first positive electrode active material, improving the energy density of the battery. The synergistic effect of the first positive electrode active material and the second positive electrode lithium replenishment material effectively improves the energy density, rate characteristics and cycle life of the lithium-ion secondary battery. Compared to the combination of first and second positive electrode active materials in the previously filed Patent Document 4, the combination of first positive electrode active material and second positive electrode lithium replenishment material used in the present invention can more significantly improve the energy density, rate characteristics, and cycle life of the lithium-ion secondary battery. At the same time, the present invention has made specific designs for the resistance R, compressive density P, and single-sided surface density Q of the positive electrode piece, further improving the energy density, rate characteristics, and cycle life of the lithium-ion secondary battery, achieving an organic unification of high energy density, good rate characteristics, and long cycle life.

[0024] To achieve the lithium replenishment function, the second cathode lithium replenishment material in the present invention satisfies 1-p > 0.8 (i.e., 0 ≤ p < 0.2). Specifically, the second cathode lithium replenishment material in the present invention has two phase structures, which belong to the Pmmn space group and the C2 / m space group, respectively. The Pmmn space group corresponds to a characteristic diffraction peak A appearing at 15°~16° of the linear diffraction spectrum, and the C2 / m space group corresponds to a characteristic diffraction peak B appearing at 18°~19° of the linear diffraction spectrum, with the intensity I of the characteristic diffraction peak B being... B The intensity of characteristic diffraction peak A for I A Ratio I A / I B is, 0 A ​ / I B The condition ≤0.2 is satisfied. After the initial charge, both characteristic diffraction peak A and characteristic diffraction peak B are shifted in the lower angle direction, and the shift magnitude for both is <0.5°.

[0025] In the present invention, in order to ensure that the lithium-ion secondary battery has high energy density, rate characteristics, and cycle life, the positive electrode piece must satisfy 1.5 ≤ R·P / Q ≤ 30. In some embodiments of the present invention, R·P / Q is one of the values ​​among 1.5, 3, 6, 9, 12, 15, 18, 21, 24, 27, and 30. In some preferred embodiments of the present invention, by satisfying R·P / Q 3.0 ≤ R·P / Q ≤ 15, the resulting lithium-ion secondary battery has a longer cycle life and rate characteristics. For example, R·P / Q is one of the values ​​among 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, and 15.

[0026] In this specification, the calculation of R·P / Q is limited to numerical calculations. For example, the resistance R of the positive electrode piece is 1.0Ω, and the compressed density P is 3.0g / cm³. 3 The surface density Q on one side of the positive electrode piece is 0.35 g / 1540.25 mm². 2 Therefore, R·P / Q = 8.57.

[0027] The resistance R of the positive electrode piece is the resistance value measured by the DC two-probe method, of which the contact area between the probe and the positive electrode piece is 49π mm². 2 In this invention, during research, the resistance R of the positive electrode piece was measured using a HIOKI BT23562 internal resistance measuring device, and the specific procedure was as follows: The upper and lower sides of the positive electrode piece were sandwiched between the two conductive terminals of the measuring device, and pressure was applied to fix it in place. The diameter of the conductive terminals was 14 mm, and the applied pressure was 15 MPa to 27 MPa, thereby measuring the resistance R of the positive electrode piece.

[0028] The compressive density P of the positive electrode piece can be calculated from the formula P = m / v, where m is the weight of the positive electrode active material layer (unit: g), and v is the volume of the positive electrode active material layer (unit: cm). 3Therefore, the volume v of the positive electrode active material layer is equal to the area A of the positive electrode active material layer. r It may also be the product of the thickness of the positive electrode active material layer.

[0029] The surface density Q on one side of the positive electrode piece is given by the formula Q = 1540.25 m / A r It can be calculated from this formula, where m is the weight of the positive electrode active material layer, and the unit of m is g, A r This is the area of ​​the positive electrode active material layer, and A r The unit is mm 2 That is the case.

[0030] The film resistance R, compressive density P, and single-sided areal density Q of the positive electrode are important parameters in the design and manufacture of lithium-ion secondary batteries. If the film resistance R of the positive electrode is too high, the cycle characteristics and rate characteristics of the lithium-ion secondary battery will deteriorate. If the compressive density P is too high or too low, the cycle characteristics and rate characteristics of the lithium-ion secondary battery will also deteriorate. If the single-sided areal density Q of the positive electrode is too high, the cycle life of the lithium-ion secondary battery will decrease, affect the penetration of the electrolyte, and further affect the rate characteristics of the battery, in particular reducing the high-rate discharge capacity of the battery. If the single-sided areal density Q of the positive electrode is too low, the length of the current collector and separator will increase to maintain the same battery capacity, and the internal resistance of the electrochemical apparatus will increase. Therefore, in order for the electrochemical characteristics of the lithium-ion secondary battery to yield the expected results, these parameters must be comprehensively designed during battery manufacturing so that the positive electrode reaches the expected design values.

[0031] It is preferable that the film resistance R of the positive electrode piece satisfies R ≤ 5Ω, as this is advantageous for improving the cycle characteristics and rate characteristics of the lithium-ion secondary battery. Furthermore, to further improve the cycle characteristics and rate characteristics of the lithium-ion secondary battery, it is even more preferable that the film resistance R of the positive electrode piece satisfies R ≤ 2Ω.

[0032] Preferably, the compressed density P of the positive electrode piece is 2.5 g / cm³. 3 <P<3.2g / cm 3This satisfies the conditions, which are favorable for the movement of electrons and ions in the positive electrode piece, thereby improving the cycle characteristics of the lithium-ion secondary battery.

[0033] Preferably, the surface density Q on one side of the positive electrode piece is 0.3 g / 1540.25 mm². 2 <Q<0.55g / 1540.25mm 2 This satisfies the requirements, and while ensuring charge and discharge capacity, it can improve the cycle characteristics and rate characteristics of lithium-ion secondary batteries.

[0034] Preferably, the weight ratio of the first positive electrode active material to the weight of the second positive electrode lithium replenishment material is 5:1 to 99:1. In such a positive electrode piece, the first positive electrode active material is the majority, which has higher structural stability, reduces capacity loss and increased resistance due to structural breakdown of the positive electrode active material, and maintains cycle stability and dynamic characteristics. Preferably, the weight ratio of the first positive electrode active material to the weight of the second positive electrode lithium replenishment material is 9:1 to 99:1, which further improves cycle stability and dynamic characteristics.

[0035] positive electrode active material layer The weight content of the first positive electrode active material is 80% to 98%, more preferably 85% to 98%.

[0036] In the positive electrode piece of the embodiment of the present invention, the positive electrode active material layer further comprises a conductive agent and a binder. The present invention does not particularly limit the types of conductive agent and binder, and they may be selected according to actual needs.

[0037] For example, the conductive agent may be at least one of graphite, superconducting carbon, acetylene black, carbon black, Ketjenblack, carbon dots, carbon nanotubes, graphene, carbon nanofibers, etc., and the binder may be at least one of styrene-butadiene rubber (SBR), water-based acrylic resin, carboxymethylcellulose (CMC), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl butyral (PVB), ethylene-vinyl acetate copolymer (EVA), polyvinyl alcohol (PVA), etc.

[0038] In some arbitrary embodiments, the weight content of the conductive agent in the positive electrode active material layer is ≥0.5%, which is advantageous for obtaining a low positive electrode film resistance.

[0039] In some alternative embodiments, the weight content of the binder in the positive electrode active material layer is ≤2.0%, which is advantageous for obtaining a low positive electrode film resistance.

[0040] The positive electrode current collector may be made of a metal foil material or a porous metal plate, for example, a foil material or porous plate formed using a metal such as aluminum, copper, nickel, titanium, or silver, or an alloy thereof, such as aluminum foil.

[0041] The thickness of the positive electrode current collector is preferably 5 μm to 20 μm, more preferably 6 μm to 18 μm, and even more preferably 8 μm to 16 μm.

[0042] Lithium-ion rechargeable battery The positive electrode piece of the present invention can be used as the positive electrode of a lithium-ion secondary battery. A lithium-ion secondary battery comprises a positive electrode piece, a negative electrode piece, a separator, and an electrolyte, of which the positive electrode piece is the positive electrode piece of the present invention. By using the positive electrode piece of the present invention, the lithium-ion secondary battery of the present invention simultaneously has high energy density, cycle characteristics, and rate characteristics.

[0043] The negative electrode piece may be a metallic lithium piece, and may include a negative electrode current collector and a negative electrode active material layer provided on at least one surface of the negative electrode current collector.

[0044] The negative electrode active material layer typically contains a negative electrode active material, a conductive agent, a binder, and a thickener. Examples of negative electrode active materials include natural graphite, artificial graphite, mesocarbon microbeads (MCMB), hard carbon, soft carbon, silicon, silicon-carbon composite, SiO, Li-Sn alloy, Li-Sn-O alloy, Sn, SnO, SnO2, and lithium titanate Li4Ti5O with a spinel structure. 12 The active material may be at least one of Li-Al alloy and metallic lithium, the conductive agent may be at least one of graphite, superconducting carbon, acetylene black, carbon black, Ketjenblack, carbon dots, carbon nanotubes, graphene, carbon nanofibers, etc., the binder may be at least one of styrene-butadiene rubber (SBR), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl butyral (PVB), water-based acrylic resin, carboxymethylcellulose (CMC), etc., and the thickener may be carboxymethylcellulose (CMC), etc. However, the present invention is not limited to these materials, and other materials that can be used as negative electrode active material, conductive agent, binder and thickener for lithium-ion secondary batteries can also be used.

[0045] The negative electrode current collector may be a metal foil material or a porous metal plate, for example, a foil material or porous plate formed using a metal such as copper, nickel, titanium, or iron, or an alloy thereof, for example, copper foil.

[0046] Negative electrode pieces can be manufactured according to conventional methods in the art. Typically, a negative electrode active material and any conductive agent, binder, and thickener are dispersed in a solvent to form a uniform negative electrode slurry. The solvent may be N-methylpyrrolidone (NMP) or deionized water. The negative electrode slurry is applied to a negative electrode current collector, and negative electrode pieces are obtained through processes such as drying and cold pressing.

[0047] The above-mentioned separator is not particularly limited, and any known porous separator with electrochemical and chemical stability may be selected and used, for example, a single-layer or multi-layer film of at least one of the following: glass fiber, nonwoven fabric, polyethylene (PE), polypropylene (PP), or polyvinylidene fluoride (PVDF).

[0048] The electrolyte described above comprises an organic solvent, a lithium electrolyte salt, and additives. The present invention is not particularly limited in terms of the type of organic solvent and lithium electrolyte salt, and may be selected according to actual needs.

[0049] For example, the above organic solvent may be at least one of the following: ethylene carbonate (EC), propylene carbonate (PC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), methyl propyl carbonate (MPC), ethyl propyl carbonate (EPC), butylene carbonate (BC), fluoroethylene carbonate (FEC), methyl formate (MF), methyl acetate (MA), ethyl acetate (EA), propyl acetate (PA), methyl propionate (MP), ethyl propionate (EP), propyl propionate (PP), methyl butyrate (MB), ethyl butyrate (EB), 1,4-butyrolactone (GBL), sulfolane (SF), dimethyl sulfone (MSM), ethyl methyl sulfone (EMS), and diethyl sulfone (ESE), preferably two or more.

[0050] The lithium electrolyte salts listed above may be one or more of the following: LiPF6 (lithium hexafluorophosphate), LiBF4 (lithium tetrafluoroborate), LiClO4 (lithium perchlorate), LiAsF6 (lithium hexafluoroarsenate), LiFSI (lithium bis(fluorosulfonyl)imide), LiTFSI (lithium bis(trifluoromethanesulfonyl)imide), LiTFS (lithium trifluoromethanesulfonate), LiDFOB (lithium difluoro(oxalato)borate), LiBOB (lithium bis(oxalate)borate), LiPO2F2 (lithium difluorophosphate), LiDFOP (lithium difluoro(oxalato)phosphate), LiTFOP (lithium tetrafluoro(oxalato)phosphate), etc.

[0051] The additive in the electrolyte described above contains vinylene carbonate (VC), and the weight content of vinylene carbonate relative to the total weight of the electrolyte is 0-5% and not 0%. By adding vinylene carbonate as an additive to the electrolyte, a uniform and dense SEI film is formed at the negative electrode, suppressing the continuous loss of active lithium.

[0052] The electrolyte additive described above contains 1,3-propanesultone (PS), and the weight percentage content of 1,3-propanesultone relative to the total weight of the electrolyte is 0-5% and not 0%. By adding 1,3-propanesultone to the electrolyte, an interfacial protective layer is formed on the positive electrode side, which can further improve the cycle life of the lithium-ion secondary battery.

[0053] The electrolyte described above may optionally contain other additives, which may be any additives usable in lithium-ion batteries. The present invention is not particularly limited and should be selected according to actual needs. For example, the additive may further include one of the following: vinyl ethylene carbonate (VEC), succinonitrile (SN), adiponitrile (AND), 1,3-propensultone (PST), cyclic quaternary ammonium sulfonic acid esters, tris(trimethylsilyl) phosphate (TMSP), or tris(trimethylsilyl) borate (TMSB).

[0054] The above electrolyte can be prepared according to the conventional methods of the art. An electrolyte is obtained by homogeneously mixing an organic solvent, a lithium electrolyte salt, vinylene carbonate, 1,3-propanesultone, and any other additives, and the order in which the materials are added is not particularly limited. For example, an electrolyte is obtained by adding a lithium electrolyte salt, vinylene carbonate, 1,3-propanesultone, and any other additives to an organic solvent and mixing them homogeneously. In this case, the lithium electrolyte salt may be added to the organic solvent first, and then the vinylene carbonate, 1,3-propanesultone, and any other additives may be added to the organic solvent separately or simultaneously.

[0055] The positive electrode piece, separator, and negative electrode piece are stacked in order, with the separator positioned between the positive and negative electrodes to act as an isolation, thereby obtaining a cell. Alternatively, a cell can be obtained by winding. The cell is placed in an outer casing, electrolyte is injected, and the casing is sealed to obtain a lithium-ion secondary battery.

[0056] During the research of this invention, the charge-discharge curve, high-temperature cycle characteristics, and rate characteristics of a lithium-ion secondary battery are measured by the following method.

[0057] Measurement of charge and discharge curves: At 45°C, lithium-ion secondary batteries were charged with a constant current at a rate of 0.1C up to 4.3V, then charged with a constant voltage until the current became 0.025C or less than 0.025C, and finally discharged with a constant current at a rate of 0.1C up to 3.0V. The charge and discharge curves of the lithium-ion secondary batteries were recorded.

[0058] High-temperature cycle characteristic measurement: At 45°C, a lithium-ion secondary battery was charged with a constant current at a rate of 1.5C up to 4.3V, then charged with a constant voltage until the current became 0.05C or less than 0.05C, and finally discharged with a constant current at a rate of 1C up to 3.0V. This constituted one charge-discharge cycle. The discharge capacity of the lithium-ion secondary battery after the first cycle was recorded. Charge-discharge cycles were performed on the lithium-ion secondary battery according to the above method, and the discharge capacity of each cycle was recorded. The cycle was terminated when the discharge capacity of the lithium-ion secondary battery decreased to 80% of the discharge capacity of the first cycle, and the number of charge-discharge cycles was recorded.

[0059] Rate characteristic measurement: At 25°C, lithium-ion secondary batteries were charged with a constant current at a rate of 0.2C up to 4.3V, then charged with a constant voltage until the current became 0.05C or less than 0.05C, and then discharged with a constant current at a rate of 0.2C up to 3.0V, and the discharge capacity at the 0.2C rate was recorded. At 25°C, lithium-ion secondary batteries were charged with a constant current at a rate of 0.2C up to 4.3V, then charged with a constant voltage until the current became 0.05C or less than 0.05C, and then discharged with a constant current at a rate of 2C up to 3.0V, and the discharge capacity at the 2C rate was recorded. The discharge capacity retention rate (%) of the lithium-ion secondary battery at the 2C rate = discharge capacity at the 2C rate / discharge capacity at the 0.2C rate × 100%.

[0060] Example 1 Preparation of positive electrode pieces: LiMn2O4, the first positive electrode active material, LiMnO2, the second positive electrode lithium replenishment material, PVDF, and conductive carbon black were mixed. The weight ratio of LiMn2O4, LiMnO2, PVDF, and conductive carbon black was 92.5:4.0:1.5:2.0. NMP, the solvent, was added in a material-to-liquid ratio of 7:3, and the mixture was stirred under vacuum until a uniform and transparent system was obtained, yielding a positive electrode slurry. The positive electrode slurry was uniformly applied to the aluminum foil of the positive electrode current collector, then transferred to an oven to dry at a drying temperature of 120°C. The positive electrode was obtained by cold pressing and slitting. The weight content of LiMn2O4, the first positive electrode active material, in the positive electrode active material layer was 92.5%, and the weight content of LiMnO2, the second positive electrode lithium replenishment material, in the positive electrode active material layer was 4.0%.

[0061] Preparation of negative electrode pieces: Artificial graphite, the negative electrode active material, sodium carboxymethylcellulose (CMC), the thickener, a binder (SBR), and conductive carbon black were mixed in a mass ratio of 95.7:1.0:1.8:1.5. Deionized water, the solvent, was added in a material-to-liquid ratio of 4:6, and the mixture was stirred using a vacuum stirrer to obtain a negative electrode slurry. The negative electrode slurry was uniformly applied to the copper foil of the negative electrode current collector, then transferred to an oven to dry at a drying temperature of 120°C. The mixture was then cold-pressed and slit to obtain negative electrode pieces.

[0062] Preparation of electrolyte: Ethylene carbonate (EC), ethyl methyl carbonate (EMC), and diethyl carbonate (DEC) were uniformly mixed in a volume ratio of 1:1:1 to obtain an organic solvent. LiPF6 was dissolved in the above organic solvent, and the concentration of LiPF6 was 1 mol / L. 3% by weight of vinylene carbonate and 3% by weight of 1,3-propanesultone were further added to the total mass of the electrolyte and uniformly mixed to obtain the electrolyte.

[0063] Preparation of the lithium-ion secondary battery: A positive electrode, a separator, and a negative electrode were stacked in sequence. The separator was a 14 μm thick polypropylene (PP) film (provided by Celgard), positioned between the positive and negative electrode pieces, and served as an isolation. The film was then wound around the electrode assembly, tabs were welded, the electrode assembly was placed in an outer case, the electrolyte was injected and sealed, and then the lithium-ion secondary battery was obtained through processes such as standing, formation, and shaping.

[0064] Examples 2-27 The difference from Example 1 is that the material components in the positive electrode and the correlation parameters in the manufacturing steps were adjusted. See Table 1 for details (in this table, the weight content of the first positive electrode active material refers to the positive electrode active material layer This is the weight content of the first positive electrode active material, and the weight content of the second positive electrode lithium replenishment material is the weight content of the positive electrode active material layer This is shown as the weight content of the lithium replenishment material for the second positive electrode.

[0065] Comparative Example 1 The difference from Example 1 was that the positive electrode contained only LiMn2O4.

[0066] Comparative Example 2 The difference from Example 1 was that the positive electrode contained only LiMnO2.

[0067] Comparative Examples 3-4 The difference from Example 1 was that the ratio of the weight of the first positive electrode active material to the weight of the second positive electrode lithium replenishment material in the positive electrode was different.

[0068] Comparative Examples 5-6 The difference from Example 1 was that the film resistance, compression density, and surface density of one side of the positive electrode piece were different.

[0069] Comparative Examples 7-8 The difference from Example 1 was the weight content of vinylene carbonate and 1,3-propanesultone in the electrolyte.

[0070] Comparative Examples 9-10 The difference from Example 26 was that the electrolyte contained only vinylene carbonate or only 1,3-propanesultone.

[0071] In each example and comparative example, in Example 18, the positive electrode active material layer Except for the fact that the content of conductive carbon black and the binder PVDF in this example is 0.5 wt%, in other examples and comparative examples the positive electrode active material layer The conductive carbon black content was 2.0 wt%, and the PVDF binder content was 1.5 wt%.

[0072] According to the method described above, the high-temperature cycle characteristics and rate characteristics of the lithium-ion secondary batteries obtained in each example and comparative example were measured, and the results are shown in Table 2.

[0073] [Table 1-1] [Table 1-2]

[0074] [Table 2-1] [Table 2-2] [Table 2-3]

[0075] As can be seen from the above examples and comparative examples, (1) in the present invention, a synergistic effect is obtained by using the first positive electrode active material and the second positive electrode lithium replenishment material together. Firstly, the second positive electrode lithium replenishment material used in the present invention has a low content of surface free lithium, and when it is added to the positive electrode, the resulting slurry has good stability and good processing characteristics. Secondly, the second positive electrode lithium replenishment material used in the present invention has a high initial charge ratio capacity and a low initial Coulomb efficiency, better replenishing the loss of active lithium due to SEI formation, and during discharge, more lithium ions are absorbed back into the crystal lattice of the first positive electrode active material, effectively improving the energy density of the lithium-ion secondary battery. Thirdly, the first positive electrode active material has a stable structure and good cycle stability, and by controlling the film resistance R, compressive density P, and single-sided surface density Q of the positive electrode piece within the range of the present invention, the lithium-ion secondary battery can have good cycle characteristics and rate characteristics. (2) The lithium replenishment method using vinylene carbonate added to the electrolyte, the first positive electrode active material, and the second lithium replenishment active material can exhibit synergistic effects. During the initial charge, a large amount of active lithium released from the second positive electrode lithium replenishment material is absorbed into the negative electrode, further lowering the true potential of the negative electrode, causing the solvent in the electrolyte to continue undergoing reduction reactions and affecting the cycle characteristics. Using an additive such as vinylene carbonate within the scope of the present invention induces the formation of a denser and thinner SEI layer, preventing the sustained consumption of the electrolyte. In addition, by adding an additive such as 1,3-propanesultone to the electrolyte, an interfacial protective layer can be formed on the surface of the positive electrode active material, further improving the cycle characteristics.

[0076] Finally, it should be noted that the above embodiments are used solely to illustrate the technical aspects of the present invention and do not limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that they can modify or replace the technical aspects of the present invention with equivalents without departing from the spirit and scope of the invention.

Claims

1. Lithium-ion secondary battery, It comprises a positive electrode piece, a negative electrode piece, a separator, and an electrolyte, The positive electrode piece includes a positive electrode current collector and a positive electrode active material layer provided on at least one surface of the positive electrode current collector. The positive electrode active material layer comprises a first positive electrode active material and a second positive electrode lithium replenishment material. The ratio of the weight of the first positive electrode active material to the weight of the second positive electrode lithium replenishment material is 5:1 to 99:

1. The positive electrode piece satisfies 1.5 ≤ R・P / Q < 30, R is the resistance of the positive electrode piece, and the unit of R is Ω. P is the compressed density of the positive electrode piece, and its unit is g / cm³. ３ And, Q is the surface density of one side of the positive electrode piece, and the unit of Q is g / 1540.25 mm ２ And, The above R satisfies R ≤ 2Ω, The aforementioned P is 2.5 g / cm³ ３ <P<3.2g / cm ３ Satisfying the conditions, The electrolyte contains, by weight, 0.001% to 5% vinylene carbonate and 0.001% to 5% 1,3-propanesultone. The first positive electrode active material is Li 1+x Mn y M 2-y O 4-t At, x, y, and t satisfy -0.1 < x < 0.2, 1 < y ≤ 2, 0 ≤ t < 0.

5. M is at least one of Ni, Fe, Zn, Mg, Al, Ti, and Zr. A is at least one of S, N, F, Cl, and Br. The second cathode lithium replenishment material is Li 1+r Mn 1-p N p O 2-s B s, r, p, and s satisfy -0.1 < r < 0.2, 0 ≤ p < 0.2, and 0 ≤ s < 0.

2. N is at least one of Fe, Co, Ni, Ti, Zn, Mg, Al, V, Cr, and Zr. B is characterized by being at least one of S, N, F, Cl, and Br. Lithium-ion rechargeable battery.

2. The lithium-ion secondary battery according to claim 1, characterized in that the positive electrode piece satisfies 3.0 ≤ R・P / Q ≤ 15.

3. The aforementioned Q is 0.3 g / 1540.25 mm ２ <Q<0.55g / 1540.25mm ２ A lithium-ion secondary battery according to claim 1, characterized in that it satisfies the following conditions.

4. The lithium-ion secondary battery according to claim 1, characterized in that the weight of the first positive electrode active material : the weight of the second positive electrode lithium replenishment material is 9:1 to 99:

1.

5. The lithium-ion secondary battery according to claim 1, characterized in that the weight content of the first positive electrode active material in the positive electrode active material layer is 80% to 98%.

6. The lithium-ion secondary battery according to claim 5, characterized in that the weight content of the first positive electrode active material in the positive electrode active material layer is 85% to 98%.

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