CN113594447B - Ternary positive electrode material, positive electrode plate, preparation method and application - Google Patents

Ternary positive electrode material, positive electrode plate, preparation method and application Download PDF

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CN113594447B
CN113594447B CN202110896425.5A CN202110896425A CN113594447B CN 113594447 B CN113594447 B CN 113594447B CN 202110896425 A CN202110896425 A CN 202110896425A CN 113594447 B CN113594447 B CN 113594447B
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ternary
positive electrode
equal
carbon material
polycrystalline
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CN113594447A (en
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曹俊琪
张小细
闫传苗
余洋
黄海宁
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Contemporary Amperex Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The application relates to a ternary positive electrode material, a positive electrode plate, a preparation method and application, wherein the ternary positive electrode material comprises a polycrystalline ternary material and/or a monocrystalline ternary material; the polycrystalline ternary material has a polycrystalline structure; the single crystal ternary material has a single crystal structure or a single crystal-like structure. The ternary monocrystal material and the high-nickel material are mixed, and particularly when the ternary monocrystal material and the high-nickel material meet a certain mass ratio, the gas production problem of the high-nickel material can be effectively improved. The polycrystalline material has higher impurity lithium content on the surface, and after being mixed into a single crystal material with a certain proportion, the total impurity lithium content is reduced, so that the gas production source is effectively reduced, meanwhile, the size particle grading is utilized, the compaction density of the pole piece can be obviously improved, the residual space inside the battery cell can be amplified to the greatest extent on the design of the battery cell, the gas produced by the battery cell can be rapidly transferred, the gas pressure of the gas production is reduced, the influence of the gas pressure of the gas production on the battery cell is reduced, and the service life of the battery cell is prolonged.

Description

Ternary positive electrode material, positive electrode plate, preparation method and application
The application is a divisional application which is proposed for the application of the application of 'a secondary battery' aiming at the application date of 2018, 02, 13 and 201810150341.5.
Technical Field
The application relates to the field of secondary batteries, in particular to a ternary positive electrode material, a positive electrode plate, a preparation method and application.
Background
Along with the popularization of electric vehicles in the global scope, the requirements of the electric vehicles on the endurance mileage are also higher and higher, and the energy density of the power battery is correspondingly required to be improved. In face of these demands, a layered ternary cathode material NCM (Li (Ni x Mn y Co z )O 2 Where x+y+z=1) should be generated. Compared with LCO positive electrode material, mn and Ni elements are introduced into NCM material, wherein Mn element has no chemical activity, but can improve the safety and stability of the material, and can reduce the material cost. The Ni element can improve the activity of the material and the gram capacity of the material. However, the thickness of the pole piece of the ternary material can be changed in the charging and discharging process, and the expansion rate of the thickness of the pole piece of the monocrystal ternary material is obviously higher than that of the polycrystal material. In the later stage of secondary battery, especially lithium ion power battery application, the thickness expansion of the positive pole piece in the circulation process can lead to circulation water jump, which is manifested by obviously reduced cycle life of the battery core.
In a high capacity battery system, since the ternary positive electrode material has a high gram capacity, in order to fully develop the capacity characteristics of the battery, the negative electrode gram capacity needs to be correspondingly increased. However, higher gram volumes of graphite generally have smaller interlayer spacing and higher graphitization. When graphite with higher gram capacity is adopted as the negative electrode plate, the compression resistance of the negative electrode plate is deteriorated. For ternary positive electrode material systems, particularly cathode systems or mixed cathode systems containing monocrystalline materials or high-nickel polycrystal, the expansion of the positive electrode plate is obvious, so that the cyclic expansion force of the battery cell is linearly increased, and the negative electrode plate is extruded. Along with the continuous progress of lithium ion intercalation and deintercalation at the negative pole, the extrusion force of positive pole and negative pole increases simultaneously, leads to electrolyte to extrude from between the positive and negative pole piece, and the negative pole dynamics reduces to reduce the lithium window of electricity core, and then arouse circulation and decay sharply, jump.
In view of this, the present application has been made.
Disclosure of Invention
The application aims to provide a ternary positive electrode material, a positive electrode plate, a preparation method and application.
In order to achieve the above purpose, the technical scheme of the application is as follows:
the first aspect of the application provides a ternary positive electrode material, which comprises a polycrystalline ternary material and/or a monocrystalline ternary material; the polycrystalline ternary material has a polycrystalline structure; the single crystal ternary material has a single crystal structure or a single crystal-like structure.
In any embodiment, the ternary positive electrode material has the formula Li a Ni x Co y M z O 2-b N b Wherein a is more than or equal to 0.95 and less than or equal to 1.2, x is more than or equal to 0, y is more than or equal to 0, z is more than or equal to 0, x+y+z=1, b is more than or equal to 0 and less than or equal to 1, M is one or more of Mn, al, cr, cd, ti, mg, ag, and N is one or more of F, P, S.
In any embodiment, the polycrystalline ternary material has the formula Li a1 (Ni x1 Co y1 Mn z1 )O 2-b1 N b1 Wherein a1 is more than or equal to 0.95 and less than or equal to 1.2,0.5, x1 is more than or equal to 0 and less than 1, y1 is more than or equal to 0 and less than 1, x1+y1+z1=1, b1 is more than or equal to 0 and less than or equal to 1, N b1 One or more selected from F, P, S.
In any embodiment, the single crystal ternary material has the formula Li a2 (Ni x2 Co y2 Mn z2 )O 2-b2 N b2 Wherein a2 is more than or equal to 0.95 and less than or equal to 1.2, x2 is more than 0 and less than 1, y2 is more than 0 and less than 1, x2+y2+z2=1, b2 is more than or equal to 0 and less than or equal to 1, N b2 One or more selected from F, P, S.
In any embodiment, the content of Ni element in the molecular formula of the single crystal ternary material is more than 0 and less than or equal to 0.5.
In any embodiment, the ternary positive electrode material comprises a polycrystalline ternary material and a single crystal ternary material, wherein the mass percentage of the polycrystalline ternary material to the single crystal ternary material is (50-85): (15-50).
In any embodiment, the mass percentage of the polycrystalline ternary material to the single crystal ternary material is (60-70): (30-40).
The second aspect of the application provides a positive electrode sheet comprising the ternary positive electrode material according to the first aspect of the application.
The third aspect of the application provides a preparation method of the positive electrode plate according to the second aspect of the application, wherein the positive electrode slurry comprising ternary positive electrode material, conductive agent and binder is coated on the surface of a positive electrode current collector, and a positive electrode active material layer is formed after drying, so that the positive electrode plate is obtained.
A fourth aspect of the application provides a use of a positive electrode sheet according to the second aspect of the application in a secondary battery.
The technical scheme of the application has at least the following beneficial effects:
the ternary monocrystal material and the high-nickel material are mixed, and particularly when the ternary monocrystal material and the high-nickel material meet a certain mass ratio, the gas production problem of the high-nickel material can be effectively improved. The polycrystalline material has higher impurity lithium content on the surface, and after being mixed into a single crystal material with a certain proportion, the total impurity lithium content is reduced, so that the gas production source is effectively reduced, meanwhile, the size particle grading is utilized, the compaction density of the pole piece can be obviously improved, the residual space inside the battery cell can be amplified to the greatest extent on the design of the battery cell, the gas produced by the battery cell can be rapidly transferred, the gas pressure of the gas production is reduced, the influence of the gas pressure of the gas production on the battery cell is reduced, and the service life of the battery cell is prolonged.
Detailed Description
The application will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application.
The embodiment of the application provides a secondary battery, which comprises a positive pole piece, a negative pole piece, an isolating film and electrolyte. The positive electrode plate comprises a positive electrode active material layer, and the positive electrode active material layer contains ternary positive electrode materials; the negative electrode plate comprises a negative electrode active material layer, wherein the active material of the negative electrode active material layer is a mixed carbon material, and the mixed carbon material comprises a carbon material A and a carbon material B.
In the application, the chemical formula of the ternary positive electrode material is Li a Ni x Co y M z O 2-b N b Wherein a is more than or equal to 0.95 and less than or equal to 1.2, x is more than or equal to 0, y is more than or equal to 0, z is more than or equal to 0, x+y+z=1, and b is more than or equal to 0 and less than or equal to 1M is selected from one or more of Mn, al, cr, cd, ti, mg, ag, and N is selected from one or more of F, P, S. As described in the background art, the material has the characteristic of high gram capacity, but the problems of large gas production and volume expansion of the battery cells exist in the circulation process. In order to exert the capacity characteristic of the battery, when graphite with high gram capacity is adopted as the negative electrode, the compression resistance of the negative electrode plate is deteriorated, and the battery cell is expanded to generate the problem of lithium precipitation.
[ carbon Material ]
The application can solve the problems by simultaneously using the carbon material A with compression resistance and quick charge functions and the carbon material B with high graphitization degree in the negative electrode plate.
In the present application, the reversible capacity C of the carbon material B B Not lower than 355mAh/g, can be matched with a ternary positive electrode material, and realizes high gram capacity of the battery. However, the mechanical strength of the carbon material B is low, resulting in poor compression resistance, and therefore the carbon material a is also added to the anode active material layer. The ratio PD (A)/PD (B) of the powder compaction density of the carbon material A to the carbon material B is 0.8-1, preferably 0.9-0.98. Compared with the carbon material B, the carbon material A has lower graphitization degree, relatively larger interlayer spacing and good compression resistance, and can effectively improve the mechanical strength of the anode mixed system.
The application has no specific requirement on the reversible capacity of the carbon material A. In order to avoid excessive decrease of the battery capacity, the reversible capacity of the carbon material A is more than or equal to 345mAh/g. In an embodiment of the application, the reversible capacity C of the carbon material B B Reversible capacity C with carbon Material A A The ratio of (2) is 1 < C B /C A ＜1.1。
The powder compaction density of the material is obtained by applying a certain pressure to the material in the powder state and measuring the volume of the compressed material in unit mass, and the parameter is closely related to the compression resistance of the powder material. For carbon materials, for example, the compaction density of the powder of the carbon material is too low, and the carbon material still has a large volume after compression, which indicates that the compression resistance of the material is too high. At the moment, the content of active substances in the pole piece is too low, which is not beneficial to manufacturing the high-capacity pole piece; if the powder compaction density is too large, the volume of the powder particles is strongly compressed under the pressure, and the material has poor compression resistance and dynamics performance, which is unfavorable for the deintercalation and intercalation of lithium ions in the subsequent cycle process.
As an improvement of the mixed carbon material, the powder compaction density of the carbon material A under 20MPa is 1.45g/cm 3 ～1.7g/cm 3 The powder compaction density of the carbon material B under 20MPa is 1.5g/cm 3 ～1.75g/cm 3 . Compared with the carbon material B, the powder compaction density of the carbon material A is relatively low, and the carbon material A has good compression resistance. When the carbon material A and the carbon material B with the powder compaction density are mixed for use, the difference of mechanical strength of the two carbon material particles can be prevented from being too large, and the particles with lower mechanical strength are prevented from being crushed by the particles with higher mechanical strength, so that the whole mixed carbon material has higher compression resistance. Therefore, the negative electrode active material provided by the application has high reversible capacity and good structural stability, so that the structural stability of a high-capacity ternary battery system is improved, the cycle performance and the dynamic performance of the high-capacity battery system are effectively improved, and the lithium precipitation problem of a battery core caused by expansion is avoided.
Since the graphite crystal has a hexagonal layered structure, the graphitization degree means the degree to which carbon atoms approach the structure of the hexagonal close-packed graphite crystal. For a carbon material, the closer the lattice size is to the lattice parameter of ideal graphite, the higher the graphitization degree. The graphitization degree can be calculated by an X-ray diffraction pattern of the carbon material. The calculation formula of graphitization degree by taking polysilicon as an internal standard reference substance is as follows: g= [ (3.44-d 002)/0.086 ]. Times.100%. Where d002 is the interplanar spacing of the carbon material in the 002 direction.
In the present application, since the reversible capacity of the carbon material B is higher than that of the carbon material a, it is preferable that the graphitization degree of the carbon material B is higher than that of the carbon material a. Specifically, the graphitization degree of the carbon material A can be 90% -96%, and the graphitization degree of the carbon material B can be 95% -99%, so that the carbon material B can be ensured to have higher reversible capacity, and the high gram capacity of the battery can be realized by matching with the ternary positive electrode material.
As an improvement of the mixed carbon material, the particle diameter of the carbon material A is 11-13.5 μm, and the particle diameter of the carbon material B is 12-14.5 μm.
Further, the powder OI value C of the carbon material A 004 /C 110 Namely, the intensity ratio of the X-ray diffraction peak of the carbon material A on the 004 crystal face to the X-ray diffraction peak of the 110 crystal face is 2-10. The strength ratio shows that the isotropy of the carbon material A is better, the structural stability and the compressive resistance are good, and the co-directional transportation of lithium ions in the carbon material A can be realized.
Correspondingly, the powder OI value C of the carbon material B 004 /C 110 35 to 70. At present, graphite is used as a negative electrode material for most commercial lithium ion batteries. The carbon material B is used as a conventional graphite anode active material, and has higher graphitization degree and reversible capacity. However, graphite materials with high graphitization degree generally have larger anisotropism, i.e. fewer inlets for lithium ion intercalation and deintercalation on the surfaces of graphite particles. Therefore, if the carbon material B is used only in the negative electrode tab, the rate performance of the battery is poor. In addition, in the lithium intercalation process, the graphite material with high anisotropy tends to undergo lattice expansion in the same direction (the C-axis direction of graphite crystals), resulting in a larger volume expansion of the battery.
According to the application, the carbon material A and the carbon material B are mixed for use, and as the isotropy of the carbon material A is good, the space for lithium ion intercalation and deintercalation is larger, and the inlet is more, so that the structural stability of graphite serving as a negative electrode active material is ensured, the compression resistance of high-capacity graphite is effectively improved, and the structural stability of the high-capacity ternary battery is improved; meanwhile, the problems of low electrolyte content between the pole pieces and lithium precipitation caused by untimely lithium ion transmission due to volume expansion of the battery core can be avoided, and the excellent dynamic performance of the battery core is ensured.
In the present application, the carbon material a may be artificial graphite, and the carbon material B may be artificial graphite or natural graphite.
As a modification of the carbon material a, the surface of the carbon material a may have a coating layer. Preferably, the coating layer material is at least one selected from soft carbon, amorphous carbon and hard carbon, and more preferably, the mass of the coating layer is 0.5wt% to 10wt% of the mass of the carbon material A. The graphitization degree of the coating layer material is lower, the hardness is higher, and the hardness and the compression resistance of the carbon material A can be further improved after the surface of the carbon material A is coated with the substances.
Further, the mass ratio of the carbon material a to the carbon material B is preferably (5 to 50) based on 100 mass sum of the carbon material a and the carbon material B: (50-95). The quality of the carbon material A is overlarge, so that the reversible capacity of the negative electrode plate and even the battery cell can be reduced; the quality of the carbon material A is too small, the improvement of the compression resistance and the quick charge performance of the negative electrode plate is not obvious, and the problem of lithium precipitation cannot be effectively solved.
In the application, the carbon material A and the carbon material B can be mixed by simple physical mixing, such as ball milling, and the like, and then the conductive agent, the binder, the solvent, and the like are added to prepare the anode slurry. Or adding the carbon material A and the carbon material B in the stirring process during the preparation of the anode slurry, and mixing to obtain the anode slurry.
[ Secondary Battery ]
The secondary battery of the present application is described in detail below.
In the above secondary battery, the positive electrode sheet includes a positive electrode current collector and a positive electrode active material layer; the negative electrode sheet comprises a negative electrode current collector and a negative electrode active material layer, and the electrolyte comprises an organic solvent and electrolyte salt dissolved in the organic solvent.
Further, the secondary battery according to the embodiment of the present application is preferably a lithium ion battery, which may be a wound or stacked lithium ion battery.
When the secondary battery is a lithium ion battery, a conventional lithium ion battery preparation method may be employed, and the method at least includes the steps of:
coating positive electrode slurry comprising a positive electrode active material, a conductive agent and a binder on the surface of a positive electrode current collector, and drying to form a positive electrode active material layer to obtain a positive electrode plate;
coating the negative electrode slurry comprising a negative electrode active material and a binder on the surface of a negative electrode current collector, and drying to form a negative electrode active material layer to obtain a negative electrode plate;
and thirdly, sequentially stacking the positive electrode plate, the isolating film and the negative electrode plate, then winding or tabletting to obtain a bare cell, then injecting electrolyte, and packaging to obtain the secondary battery.
[ Positive electrode active material layer ]
The positive electrode active material layer of the present application contains a ternary positive electrode material. As an improvement of the ternary positive electrode material, the ternary positive electrode material includes a ternary material C and/or a ternary material D.
Wherein the chemical formula of the ternary material C is Li a1 (Ni x1 Co y1 Mn z1 )O 2-b1 N b1 Wherein a1 is more than or equal to 0.95 and less than or equal to 1.2,0.5, x1 is more than or equal to 0 and less than 1, y1 is more than or equal to 0 and less than 1, x1+y1+z1=1, b1 is more than or equal to 0 and less than or equal to 1, N b1 One or more selected from F, P, S, ternary material C has a polycrystalline structure. Since x1 is greater than 0.5, ternary material C is also referred to as a high nickel material. Commercially available high nickel materials include NCM622, NCA811, NCM811.
The chemical formula of the ternary material D is Li a2 (Ni x2 Co y2 Mn z2 )O 2-b2 N b2 Wherein a2 is more than or equal to 0.95 and less than or equal to 1.2, x2 is more than 0 and less than 1, y2 is more than 0 and less than 1, x2+y2+z2=1, b2 is more than or equal to 0 and less than or equal to 1, N b2 One or more selected from F, P, S, the ternary material D has a monocrystalline structure or a monocrystalline-like structure.
As an improvement of the ternary positive electrode material, the ternary positive electrode material contains a ternary material C and a ternary material D, and the content of Ni element in the molecular formula of the ternary material D is more than 0 and less than or equal to 0.5.
As an improvement of the ternary positive electrode material, the positive electrode material contains a ternary material C and a ternary material D at the same time, and the mass percentage of the ternary material C and the ternary material D is preferably (50-85): (15-50).
At present, a report on the use of a mixed ternary material in a lithium ion battery to improve the compaction density and the safety performance of a positive electrode plate is made. However, the applicant researches find that the gas production problem of the high-nickel material can be effectively improved by mixing the ternary single crystal material with the high-nickel material, particularly when the ternary single crystal material and the high-nickel material are mixed in a certain mass ratio. The polycrystalline material has higher impurity lithium content on the surface, and after being mixed into a single crystal material with a certain proportion, the total impurity lithium content is reduced, so that the gas production source is effectively reduced, meanwhile, the size particle grading is utilized, the compaction density of the pole piece can be obviously improved, the residual space inside the battery cell can be amplified to the greatest extent on the design of the battery cell, the gas produced by the battery cell can be rapidly transferred, the gas pressure of the gas production is reduced, the influence of the gas pressure of the gas production on the battery cell is reduced, and the service life of the battery cell is prolonged.
However, as the mixed ternary material is a monocrystal material introduced into the high-nickel material, the expansion force of the battery core in the circulation process is controlled by the positive electrode plate, so that the circulation expansion force is linearly increased, and the negative electrode plate is extruded. Along with the intercalation and deintercalation of lithium ions in the negative electrode plate, the extrusion force of the positive electrode plate and the negative electrode plate synchronously increases, so that electrolyte is extruded out from between the positive electrode plate and the negative electrode plate, and the negative electrode dynamics is reduced, thereby reducing the lithium precipitation window of the battery cell, causing the problem that the battery cell precipitates lithium within 1000 cycles and causes water jump.
[ negative electrode active material layer ]
In the anode active material layer of the embodiment of the present application, it includes an anode active material, a conductive agent, and a binder.
The negative electrode active material layer is obtained by mixing and pressing a mixed carbon material with a conductive agent and a binder. Further, the negative electrode plate has a compacted density of 1.45g/cm 3 ～1.75g/cm 3 The OI value (intensity ratio of X-ray diffraction peak of the negative electrode sheet in 004 crystal face to 110 crystal face) of the negative electrode sheet containing the mixed carbon material is preferably 24 to 32. The pole piece OI value is an important parameter for representing the orientation of active substances on the negative pole piece from a macroscopic level, and the smaller the pole piece OI value is, the better the orientation of negative active substance particles in the pole piece is, and the lithium ions are more favorably embedded into the negative pole piece. According to the application, a certain amount of carbon material A with better isotropy is added into the carbon material B, so that the OI value of the negative electrode plate can be effectively improved; however, when the OI value of the negative electrode plate is lower than 24, the addition amount of the carbon material A is too large, so that the loading amount of active substances of the negative electrode plate is too low, and the capacity of a battery system is too low; when the OI value of the negative electrode plate is higher than 32, the dynamic performance of the battery is obviously reduced.
As an improvement of the negative electrode active material layer, the conductive agent may be at least one selected from carbon materials, graphite, carbon black, graphene, and carbon nanotube conductive fibers. Common conductive agents include Ketjen black (ultrafine conductive carbon black with a particle size of 30-40 nm), SP (Super P, small particle conductive carbon black with a particle size of 30-40 μm), S-O (ultrafine graphite powder with a particle size of 3-4 μm), KS-6 (large particle graphite powder with a particle size of 6.5 μm), acetylene black, VGCF (vapor grown carbon fiber with a particle size of 3-20 μm). The optional conductive agent also comprises metal powder, conductive whisker, conductive metal compound, conductive polymer, etc.
As an improvement of the negative electrode active material layer, the binder may be at least one selected from the group consisting of polyvinyl alcohol, polytetrafluoroethylene, polyvinylidene fluoride, sodium carboxymethyl cellulose, aqueous acrylic resin, ethylene-vinyl acetate copolymer, styrene-butadiene rubber, fluorinated rubber, and polyurethane.
As an improvement of the anode active material layer, it is preferable that a dispersant is further contained therein. It is further preferred that the conductive agent is one or a combination of several of amorphous carbon Super P, carbon nanotube CNT or small particle graphite with D50<0.5mm, the dispersing agent is sodium carboxymethyl cellulose (CMC), and the binder is Styrene Butadiene Rubber (SBR).
As an improvement of the anode active material layer, the anode active material layer contains 94 to 99 mass percent of the sum of the mass percent of the carbon material A and the mass percent of the carbon material B, and 1 to 5 mass percent of the binder.
[ isolation film ]
In the embodiment of the application, the material of the isolation film is not particularly limited, and may be a polymer isolation film. The polymer separator may be one selected from the group consisting of polyethylene, polypropylene and ethylene-propylene copolymer.
[ electrolyte ]
In an embodiment of the application, the electrolyte comprises an organic solvent and an electrolyte salt dissolved in the organic solvent.
Further, the organic solvent according to the embodiment of the present application may contain one or more of cyclic carbonates, linear carbonates, chain carboxylic acid esters and sulfones organic solvents. The organic solvents which can be specifically selected from the following are not limited thereto: ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl ethyl carbonate, methyl formate, ethyl formate, propyl formate, butyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, pentyl propionate, methyl butyrate, methyl valerate, methyl acrylate, sulfolane, dimethyl sulfone.
In an embodiment of the present application, when the secondary battery is a lithium ion battery, the electrolyte is a lithium salt selected from at least one of an inorganic lithium salt and an organic lithium salt.
Wherein the inorganic lithium salt is selected from lithium hexafluorophosphate (LiPF) 6 ) Lithium tetrafluoroborate (LiBF) 4 ) Lithium hexafluoroarsenate (LiAsF) 6 ) Lithium perchlorate (LiClO) 4 ) At least one of them. The organolithium salt may be selected from lithium bis (oxalato) borate (LiB (C) 2 O 4 ) 2 Abbreviated as LiBOB), lithium bis (fluorosulfonyl) imide (LiFSI), and lithium bis (trifluoromethanesulfonyl) imide (LiTFSI).
The electrolyte of the embodiment of the application can also contain additives.
The additive may be one or more selected from fluorine-containing compounds, sulfur-containing compounds, and unsaturated double bond-containing compounds. The following substances may be selected in particular without being limited thereto: fluoroethylene carbonate, ethylene sulfite, propane sultone, N-methylpyrrolidone, N-methylformamide, N-methylacetamide, acetonitrile, acrylonitrile, gamma-butyrolactone, and dimethylsulfide.
In the following specific embodiments of the present application, only the embodiments of the lithium ion battery are shown, but the embodiments of the present application are not limited thereto. The application is further illustrated below in connection with examples of lithium ion batteries. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. In the following examples and comparative examples, the positive electrode active material NCM811 (Li (Ni 0.8 Co 0.1 Mn 0.1 )O 2 )、NCM622(Li(Ni 0.6 Co 0.2 Mn 0.2 )O 2 ) And NCM211 (Li (Ni) 0.5 Co 0.25 Mn 0.25 )O 2 ) Is commercially available. Other reagents, materials, and apparatus used are commercially available unless otherwise specified.
Examples
Preparation of negative electrode plate
The carbon material A and the carbon material B are mixed with conductive agent carbon black Super P and binder Styrene Butadiene Rubber (SBR) according to the weight ratio of 92:3:5, mixing, adding solvent N-methyl pyrrolidone, and stirring and mixing uniformly to obtain the cathode slurry. And uniformly coating the anode slurry on a coating layer of an anode current collector, drying at 80-90 ℃ after coating, carrying out cold pressing, slitting and cutting, and drying for 4 hours at 110 ℃ under vacuum condition to obtain anode pieces 1-12. The preparation method of the negative electrode pieces D1-D5 is similar to that of the negative electrode pieces 1-12, except that the carbon material is changed. Wherein the carbon material A comprises carbon materials A1-A4, and the carbon material B comprises carbon materials B1-B4. The physicochemical parameters of the carbon material A and the carbon material B are shown in table 1, and the types and parameters of the carbon materials in the negative electrode plate are shown in table 2:
TABLE 1
TABLE 2
In the table "/" indicates the absence of
Preparation of positive pole piece
The polycrystalline ternary material C (NCM 622, NCM 811) and/or the single crystal ternary material D (NCM 211) are mixed according to a certain weight ratio to obtain the mixed positive electrode active material. Continuously mixing the mixed positive electrode active material with conductive agent carbon black and binder polyvinylidene fluoride (PVDF), wherein the mixing weight ratio of the three is 96:2:2. adding solvent N-methyl pyrrolidone, mixing and stirring uniformly to obtain the positive electrode slurry. And uniformly coating the positive electrode slurry on two sides of an aluminum foil of a positive electrode current collector, then drying at 85 ℃, then carrying out cold pressing, slitting and cutting, then drying at 85 ℃ under vacuum for 4 hours, and welding positive electrode lugs to obtain a positive electrode plate.
Electrolyte preparation
Preparing a basic electrolyte, wherein the basic electrolyte comprises dimethyl carbonate (DMC), methyl ethyl carbonate (EMC) and Ethylene Carbonate (EC) in a mass ratio of 2:1:1. Then adding electrolyte salt to make the concentration of lithium hexafluorophosphate in the electrolyte solution be 1mol/L.
Lithium ion battery preparation
The positive pole piece, the negative pole piece and the isolating film are wound into a battery core and injected with electrolyte, and the battery is prepared into lithium ion batteries S1-S17 and DS 1-DS 6 through procedures of packaging, molding, formation and the like. The performance parameters of the negative electrode plate, the positive electrode active material and the positive electrode active material of the lithium ion battery are shown in table 3.
TABLE 3 Table 3
In the table "-" represents absence of
Test case
Cycle performance test
The batteries in the examples were taken 3 pieces each, and the batteries were repeatedly charged and discharged by the following steps, and the discharge capacity retention rate of the batteries was calculated.
First, in an environment of 25 ℃, first charge and discharge were performed, constant current charge was performed at a charge current of 1C (i.e., a current value at which a theoretical capacity was completely discharged in 1 h), then constant voltage charge was performed until an upper limit voltage was 4.2V, then constant current discharge was performed at a discharge current of 1C until a final voltage was 2.8V, and the discharge capacity of the first cycle was recorded. Then, charge and discharge cycles were repeated, and the discharge capacity at the 1000 th cycle was recorded.
According to the formula: cycle capacity retention= (discharge capacity of 1000 th cycle/discharge capacity of first cycle) ×100%, capacity retention before and after battery cycle was calculated. When the cycle capacity retention rate was 80%, the cycle test was stopped. The average capacity retention after cycling of each of the obtained groups of cells is shown in table 4.
Capacity testing
In a constant temperature oven at 25 ℃, constant current charging is carried out at 1C rate until the voltage is 4.2V, constant voltage charging is carried out at 4.2V until the current is 0.05C, and then constant current discharging is carried out at 1C rate until the voltage is 2.8V, wherein the obtained discharge capacity is the battery capacity.
TABLE 4 Table 4
As can be seen from table 4, the negative electrode active materials in the batteries S1 to S12 are mixed carbon materials, and the positive electrode active material is a single ternary material, in accordance with the limitations of the present application. The cycling of the batteries S1 to S12 is kept well attenuated compared to DS1 to DS4 using a single negative electrode active material and DS5, DS6 in which the mixed carbon material does not conform to the definition of the present application.
Because the DS1 and the DS2 adopt the high-compression-resistance quick-charging carbon material A, the resistance to expansion force is strong, and the cycle performance is good, but the gram capacity and the compaction density of the carbon material A are lower, so that the overall design capacity of the battery cell is lower, and the battery cell design requirement is not met. While DS3 and DS4 have been hopped at the later stage of the cycle because the carbon material B has a high capacity but weak withstand voltage, and in the case that the expansion force of the battery cell gradually increases at the later stage of the cycle, the space of the pole piece thereof is continuously compressed, the pores are continuously reduced, and the electrolyte is extruded, thereby generating lithium precipitation and causing the hopping. DS5 and DS6 have also jumped, probably due to the fact that the ratio Pb/Pa <0.8 of the powder compaction densities of carbon material a and carbon material B, their compressive capacities differ too much. Materials with similar characteristics generally have large gram capacity difference, strong polarization exists on the surfaces between particles of the carbon materials A and B when lithium ions are intercalated and deintercalated, and a water jump phenomenon is generated after accumulation.
The negative electrode active material in the batteries S13 to S17 is a mixed carbon material, and the positive electrode active material is a mixed ternary material containing single-crystal low nickel and polycrystalline high nickel. Compared with S6 using a single positive electrode active material, the cyclic capacity retention rate and the battery capacity are both improved, which shows that the mixed carbon material can further improve the reversible capacity and the compression resistance of the negative electrode plate and prolong the cycle life of the battery when being used in a battery system of mixed ternary materials.
While the preferred embodiments of the application have been described above, it is not intended that the application be limited thereto. Any person skilled in the art can make several possible variations and modifications without departing from the inventive concept, and therefore the scope of the application shall be defined by the claims.

Claims (7)

1. A secondary battery comprises a positive electrode plate, a negative electrode plate, a separation film and electrolyte, and is characterized in that,
the positive electrode plate comprises a positive electrode active material layer, wherein the positive electrode active material layer contains a ternary positive electrode material; the ternary positive electrode material comprises a polycrystalline ternary material and/or a monocrystalline ternary material; the polycrystalline ternary material has a polycrystalline structure; the monocrystal ternary material has a monocrystal structure or a monocrystal-like structure;
the negative electrode plate comprises a negative electrode active material layer, wherein the active material of the negative electrode active material layer is a mixed carbon material, the mixed carbon material comprises a carbon material A and a carbon material B, and the carbon material B has a reversible capacity C B Not lower than 355mAh/g, wherein the powder compaction density of the carbon material A under 20MPa is 1.45g/cm 3 ～1.7g/cm 3 The powder compaction density of the carbon material B under 20MPa is 1.5g/cm 3 ～1.75g/cm 3 The ratio of the powder compaction density of the carbon material A to the powder compaction density of the carbon material B is 0.9-0.98; reversible capacity C of the carbon material B B Reversible capacity C with the carbon material A A The ratio of (2) is 1 < C B /C A < 1.1; the graphitization degree of the carbon material A is 90% -96%, the graphitization degree of the carbon material B is 95% -99%, and the graphitization degree of the carbon material A is lower than that of the carbon material B.
2. The secondary battery according to claim 1, wherein the ternary positive electrode material has a chemical formula of Li a Ni x Co y M z O 2-b N b Wherein a is more than or equal to 0.95 and less than or equal to 1.2, x is more than or equal to 0, y is more than or equal to 0, z is more than or equal to 0, x+y+z=1, b is more than or equal to 0 and less than or equal to 1, M is one or more of Mn, al, cr, cd, ti, mg, ag, and N is one or more of F, P, S.
3. The secondary battery according to claim 1, wherein the polycrystalline ternary material has a chemical formula of Li a1 (Ni x1 Co y1 Mn z1 )O 2-b1 N b1 Wherein a1 is more than or equal to 0.95 and less than or equal to 1.2,0.5, x1 is more than or equal to 0 and less than 1, y1 is more than or equal to 0 and less than 1, x1+y1+z1=1, b1 is more than or equal to 0 and less than or equal to 1, N b1 One or more selected from F, P, S.
4. The secondary battery according to claim 1, wherein the single crystal ternary material has a chemical formula of Li a2 (Ni x2 Co y2 Mn z2 )O 2-b2 N b2 Wherein a2 is more than or equal to 0.95 and less than or equal to 1.2, x2 is more than 0 and less than 1, y2 is more than 0 and less than 1, x2+y2+z2=1, b2 is more than or equal to 0 and less than or equal to 1, N b2 One or more selected from F, P, S.
5. The secondary battery according to claim 4, wherein the content of Ni element in the molecular formula of the single crystal ternary material is 0< x 2.ltoreq.0.5.
6. The secondary battery according to claim 1, wherein the ternary positive electrode material includes a polycrystalline ternary material and a single crystal ternary material, and the mass percentage of the polycrystalline ternary material to the single crystal ternary material is (50 to 85): (15-50).
7. The secondary battery according to claim 6, wherein the mass percentage of the polycrystalline ternary material to the single crystal ternary material is (60 to 70): (30-40).
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