CN113611841B - Secondary battery and method for manufacturing the same - Google Patents
Secondary battery and method for manufacturing the same Download PDFInfo
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- CN113611841B CN113611841B CN202110897511.8A CN202110897511A CN113611841B CN 113611841 B CN113611841 B CN 113611841B CN 202110897511 A CN202110897511 A CN 202110897511A CN 113611841 B CN113611841 B CN 113611841B
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- 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
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- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
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- 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
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract
The present application relates to a secondary battery and a method of manufacturing the sameThe preparation method comprises a positive pole piece, a negative pole piece, a separation film and electrolyte, and is characterized in that the negative pole piece comprises a negative active material layer, an active material of the negative active material layer is a mixed carbon material, the mixed carbon material comprises a carbon material A and a carbon material B, and the ratio of the powder compaction density of the carbon material A to the powder compaction density of the carbon material B is 0.8-1; reversible capacity C of the carbon material B B A reversible capacity C larger than that of the carbon material A A (ii) a The carbon material A and the graphitization degree are lower than the graphitization degree of the carbon material B. The carbon material B has higher reversible capacity, and is matched with a ternary cathode material to realize the high gram capacity of the battery. Carbon material a has a lower graphitization degree, a relatively large interlayer distance, and a higher mechanical strength than carbon material B. The two carbon materials are mixed for use, so that the negative pole piece can be ensured to have high reversible capacity and good pressure resistance, and the cycle life of the battery is prolonged.
Description
The application is a divisional application which is provided for the application with the application date of 2018, 13.02 and the application number of 201810150341.5 and the name of 'a secondary battery'.
Technical Field
The present disclosure relates to the field of secondary batteries, and more particularly, to a secondary battery and a method for manufacturing the same.
Background
With the popularization of electric vehicles in the global range, the requirement of the electric vehicles on the endurance mileage is higher and higher, and the energy density of power batteries is correspondingly required to be improved. In response to these demands, a layered ternary cathode material NCM (Li (Ni) x Mn y Co z )O 2 Where x + y + z is 1) occurs at the same time. Compared with an LCO anode material, Mn and Ni elements are introduced into the NCM material, wherein the Mn element has no chemical activity, but can improve the safety and stability of the material and simultaneously reduce the material cost. Ni element may beThe activity of the material is improved, and the gram volume of the material is improved. However, the thickness of the pole piece of the ternary material can change in the charging and discharging processes, and the expansion rate of the thickness of the pole piece of the single crystal ternary material is obviously higher than that of the polycrystalline material. In the later period of application of a secondary battery, particularly a lithium ion power battery, because the thickness of the positive pole piece expands in the circulating process, circulating water can be caused, and the circulating service life of the battery cell is obviously shortened.
In a high capacity battery system, since the ternary positive electrode material has a high gram-capacity, in order to sufficiently exert the capacity characteristics of the battery, it is necessary to increase the gram-capacity of the negative electrode accordingly. However, higher gram-capacity graphites generally have smaller interlayer spacing and higher graphitization degree. When the negative electrode plate is made of graphite with a high gram capacity, the compressive resistance of the negative electrode plate is deteriorated. For a ternary positive electrode material system, particularly a cathode system or a mixed cathode system containing a single crystal material or high-nickel polycrystal, the expansion of a positive electrode plate is obvious, so that the cyclic expansion force of a battery cell is increased linearly, and a negative electrode plate is extruded. Along with the continuous process of the insertion and the extraction of lithium ions in the negative electrode, the extrusion force of the positive electrode and the negative electrode is increased simultaneously, so that the electrolyte is extruded out from the space between the positive electrode piece and the negative electrode piece, the dynamics of the negative electrode is reduced, the lithium precipitation window of the battery cell is reduced, and the rapid cycle attenuation and water jump are further caused.
In view of this, the present application is specifically proposed.
Disclosure of Invention
An object of the present application is to provide a secondary battery and a method of manufacturing the same.
In order to achieve the purpose, the technical scheme of the application is as follows:
the secondary battery comprises a positive pole piece, a negative pole piece, a separation film and electrolyte, and is characterized in that the negative pole piece comprises a negative active material layer, the active material of the negative active material layer is a mixed carbon material, the mixed carbon material comprises a carbon material A and a carbon material B, and the ratio of the powder compaction density of the carbon material A to the powder compaction density of the carbon material B is 0.8-1; reversible capacity C of the carbon material B B A reversible capacity C larger than that of the carbon material A A (ii) a The carbon isThe degree of graphitization of the material a and the carbon material B is lower than the degree of graphitization of the carbon material B.
In any embodiment, the reversible capacity C of the carbon material B B Reversible capacity C with the carbon material A A The ratio of (1) to (C) B /C A ＜1.1。
In any embodiment, the reversible capacity C of the carbon material B B Not less than 355 mAh/g.
In any embodiment, the carbon material A has a reversible capacity of 345mAh/g or more.
In any embodiment, the powder compaction density ratio of the carbon material a to the carbon material B is 0.9 to 0.98.
In any embodiment, the carbon material A has a powder compacted density of 1.45g/cm at 20MPa 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 。
In any embodiment, the degree of graphitization of carbon material a is 90% to 96%, and the degree of graphitization of carbon material B is 95% to 99%.
In any embodiment, the carbon material a has a D50 particle size of 11 to 13.5 μm, and the carbon material B has a D50 particle size of 12 to 14.5 μm.
In any embodiment, the powder OI value C of the carbon material A 004 /C 110 Is 2 to 10.
In any embodiment, the mass ratio of the carbon material a to the carbon material B is (5 to 50): (50-95).
In any embodiment, the mixed carbon material is mixed with a conductive agent and a binder and pressed to a compacted density of 1.45g/cm 3 ～1.75g/cm 3 When the negative electrode plate is used, the OI value C of the negative electrode plate 004 /C 110 Is 24 to 32.
In any embodiment, the carbon material a has a coating layer on the surface thereof.
In any embodiment, the coating material is selected from at least one of soft carbon, amorphous carbon, and hard carbon.
In any embodiment, the mass of the coating layer is 0.5 to 10 wt% of the mass of the carbon material a.
In any embodiment, the positive electrode sheet includes a positive electrode active material layer containing a ternary positive electrode material; the ternary positive electrode material comprises a polycrystalline ternary material and/or a single crystal 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 cathode material comprises 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 (50-85): (15-50).
In any embodiment, the ternary cathode material has the chemical 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 is 1, b is more than or equal to 0 and less than or equal to 1, M is selected from one or more of Mn, Al, Cr, Cd, Ti, Mg and Ag, and N is selected from one or more of F, P, S.
In any embodiment, the polycrystalline ternary material has the chemical 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, x1 is more than 0.5 and less than 1, y1 is more than 0 and less than 1, x1+ y1+ z1 is 1, b1 is more than or equal to 0 and less than or equal to 1, and N is b1 One or more selected from F, P, S.
In any embodiment, 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 is 1, b2 is more than or equal to 0 and less than or equal to 1, and N is b2 One or more selected from F, P, S.
In any embodiment mode, 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 x2 and less than or equal to 0.5.
The application also provides a preparation method of the secondary battery, wherein the positive pole piece, the isolating membrane and the negative pole piece are sequentially stacked and then wound or pressed to obtain a bare cell, then the electrolyte is injected, and the secondary battery is obtained after packaging.
In any embodiment, the electrolyte contains an additive, and the additive is selected from one or more of fluorine-containing compounds, sulfur-containing compounds and unsaturated double bond-containing compounds.
In any embodiment, the additive is selected from one or more of fluoroethylene carbonate, ethylene sulfite, propane sultone, N-methyl pyrrolidone, N-methyl formamide, N-methyl acetamide, acetonitrile, acrylonitrile, gamma-butyrolactone and methyl sulfide.
The technical scheme of the application has at least the following beneficial effects:
the ternary material is used in a positive electrode plate of a secondary battery, and a mixed carbon material comprising a carbon material A and a carbon material B is used in a negative electrode plate. The carbon material B has high reversible capacity, and can be matched with a ternary cathode material to realize the high gram capacity of the battery. However, carbon material B has low mechanical strength, resulting in poor compression resistance, and therefore carbon material a is also added to the negative electrode active material layer. Compared with the carbon material B, the carbon material A has lower graphitization degree, relatively larger interlayer spacing and good pressure resistance, and can effectively improve the mechanical strength of a negative electrode mixed system. The two carbon materials are mixed for use, so that the negative pole piece can be ensured to have high reversible capacity and good structural stability. Particularly when the positive active substance contains a single crystal structure or a high-nickel ternary material with high volume expansion rate, the mixed negative active substance can effectively improve the structural stability of a high-capacity ternary battery system, improve the cycle life and the dynamic performance of the battery, and avoid the problem of lithium precipitation caused by local dynamic performance reduction due to the fact that the negative active substance collapses under high pressure due to the expansion of a pole piece in a battery cell.
In a preferred embodiment of the present invention, the intensity ratio (C) of the X-ray diffraction peak of carbon material A in the 004 crystal plane to the X-ray diffraction peak of the 110 crystal plane is 004 /C 110 ) Is 2 to 10. The strength ratio can ensure that the carbon material A has better isotropy, good structural stability and pressure resistance, and is favorable for improving the dynamic performance of the battery, such as rate capability。
Detailed Description
The present application is further illustrated with reference to specific examples. It should be understood that these examples are for illustrative purposes only 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 membrane and electrolyte. The positive pole piece comprises a positive active material layer, and the positive active material layer contains a ternary positive material; the negative electrode plate comprises a negative electrode active material layer, wherein an 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 present application, the chemical formula of the ternary cathode 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 is 1, b is more than or equal to 0 and less than or equal to 1, M is selected from one or more of Mn, Al, Cr, Cd, Ti, Mg and 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 expansion of the volume of a battery core exist in the circulation process. In order to exert the capacity characteristics of the battery, when the negative electrode adopts graphite with high gram capacity, the pressure resistance of a negative electrode plate is deteriorated, and the lithium precipitation problem is caused by the expansion of a battery core.
[ carbon Material ]
The carbon material A with the compression resistance and the quick charging function and the carbon material B with the high graphitization degree are simultaneously used in the negative pole piece, and the problems can be solved.
In the present application, the reversible capacity C of the carbon material B B Not less than 355mAh/g, can be matched with a ternary cathode material to realize the high gram capacity of the battery. However, carbon material B has low mechanical strength and poor pressure resistance, and therefore carbon material a is also added to the negative electrode 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 pressure resistance, and can effectively improve the machinery of a negative electrode mixed systemAnd (4) strength.
The reversible capacity of carbon material a is not particularly required. In order to avoid excessive reduction in battery capacity, the reversible capacity of carbon material A was 345mAh/g or more. In the examples of the present application, the reversible capacity C of the carbon material B B Reversible capacity C with carbon material A A The ratio of (1) to (C) B /C A ＜1.1。
The powder compacted density of the material is obtained by applying a certain pressure to the material in a powder state and measuring the volume of the material after compression per unit mass, and the parameter is closely related to the compression resistance of the powder material. For carbon materials, for example, the powder compaction density of the carbon material is too low and the carbon material still has a large volume after compression, which indicates that the material has too high compression resistance. At the moment, the content of active substances in the pole piece is too low, so that the pole piece is not beneficial to manufacturing a high-capacity pole piece; if the powder compaction density is too high, the volume of the powder particles is strongly compressed under pressure, and the material has poor compression resistance and dynamic performance and is not favorable 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 at 20MPa is 1.45g/cm 3 ～1.7g/cm 3 The powder compacted density of the carbon material B under 20MPa is 1.5g/cm 3 ～1.75g/cm 3 . Compared with the carbon material B, the carbon material A has relatively low powder compaction density and good pressure resistance. When the carbon material A with the powder compacted density and the carbon material B are mixed for use, the difference of the mechanical strength of two carbon material particles can be ensured not to be overlarge, and the particles with lower mechanical strength are prevented from being crushed by another particles with higher mechanical strength, so that the whole mixed carbon material has higher compressive resistance. Therefore, the cathode active material can have 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 ternary battery system are effectively improved, and the problem of lithium precipitation of a battery core due to expansion is avoided.
Since the graphite crystal has a hexagonal layered structure, the graphitization degree means a degree that carbon atoms approach a close-packed hexagonal graphite crystal structure. For a carbon material, the closer the lattice size is to the lattice parameter of an ideal graphite, the higher the degree of graphitization. The graphitization degree can be obtained by calculating an X-ray diffraction pattern of the carbon material. Taking polycrystalline silicon as an internal standard reference substance, and the calculation formula of the graphitization degree is as follows: g ═ 100% of [ (3.44-d002)/0.086 ]. Wherein 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, the graphitization degree of the carbon material B is preferably higher than that of the carbon material a. Specifically, the graphitization degree of the carbon material A can be 90-96%, the graphitization degree of the carbon material B can be 95-99%, the carbon material B can be ensured to have higher reversible capacity, and the carbon material B is matched with a ternary cathode material to realize the high gram capacity of the battery.
As an improvement of the mixed carbon material, the particle size of the carbon material A is 11 to 13.5 μm, and the particle size of the carbon material B is 12 to 14.5 μm.
Further, the powder OI value C of the carbon material A 004 /C 110 That is, the intensity ratio of the X-ray diffraction peak of carbon material A on the 004 crystal plane to the X-ray diffraction peak of the 110 crystal plane is 2 to 10. This strength ratio indicates that carbon material a has good isotropy, good structural stability and compressive resistance, and is capable of realizing the homodromous transport of lithium ions in carbon material a.
Accordingly, the powder OI value C of the carbon material B 004 /C 110 Is 35 to 70. At present, most commercial lithium ion batteries use graphite as a negative electrode material. The carbon material B is used as a conventional graphite negative electrode active material and has high graphitization degree and reversible capacity. However, graphite materials with high graphitization degree generally have larger anisotropy, that is, the surface of graphite particles has less entrance for lithium ion intercalation and deintercalation. Therefore, if carbon material B is used only in the negative electrode tab, the rate performance of the battery is poor. Also, during lithium intercalation, highly anisotropic graphite materials tend to undergo lattice expansion in the same direction (the C-axis direction of the graphite crystal), resulting in a large volume expansion of the battery.
According to the preparation method, the carbon material A and the carbon material B are mixed for use, and the carbon material A has good isotropy, so that the space for lithium ion insertion and extraction is larger, and more inlets are provided, so that the structural stability of graphite serving as a negative electrode active material is ensured, the pressure resistance of high-capacity graphite is effectively improved, and the structural stability of a high-capacity ternary battery is improved; meanwhile, the problems of low electrolyte content between pole pieces and lithium precipitation caused by untimely lithium ion transmission due to the volume expansion of the battery cell can be avoided, and the excellent dynamic performance of the battery cell 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. The coating material is preferably at least one selected from soft carbon, amorphous carbon and hard carbon, and more preferably the mass of the coating layer is 0.5 wt% to 10 wt% of the mass of the carbon material a. Since the coating material has a low graphitization degree and a high hardness, the hardness and compressive resistance of the carbon material a can be further improved after the carbon material a is coated with the coating material.
Further, the mass ratio of the carbon material A to the carbon material B is preferably (5 to 50): (50-95). The mass of the carbon material A is too large, so that the reversible capacity of the negative pole piece and even the battery cell can be reduced; the carbon material A is too small in mass, so that the improvement on the compression resistance and the quick charge performance of the negative pole piece 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 a conductive agent, a binder, a solvent and the like are added to prepare the negative electrode slurry. Or when the negative electrode slurry is prepared, adding the carbon material A and the carbon material B in the stirring process, and mixing to obtain the negative electrode slurry.
[ Secondary Battery ]
The secondary battery of the present application is explained 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 plate 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 of the embodiment of the present application is preferably a lithium ion battery, and the lithium ion battery 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 can be adopted, and the method at least comprises the following steps:
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 piece;
coating 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 step three, sequentially stacking the positive pole piece, the isolating membrane and the negative pole piece, then winding or pressing 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 contains a ternary positive electrode material. As an improvement of the ternary cathode material, the ternary cathode material comprises a ternary material C and/or a ternary material D.
Wherein the ternary material C 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, x1 is more than 0.5 and less than 1, y1 is more than 0 and less than 1, x1+ y1+ z1 is 1, b1 is more than or equal to 0 and less than or equal to 1, and N is b1 F, P, S, and the ternary material C has a polycrystalline structure. Since x1 is greater than 0.5, ternary material C is also referred to as a nickelic material. Commercially available nickel-rich materials include NCM622, NCA811, and NCM 811.
The ternary material D has the 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 is 1, b2 is more than or equal to 0 and less than or equal to 1, and N is b2 F, P, S, the ternary material D has a single crystal structure or a quasi-single crystal structure.
As an improvement of the ternary cathode material, the ternary cathode material simultaneously 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 and x 2.
As an improvement of the ternary cathode material, the cathode material simultaneously contains a ternary material C and a ternary material D, and the mass percentage of the ternary material C to the ternary material D is preferably (50-85): (15-50).
At present, reports on the use of mixed ternary materials in lithium ion batteries to improve the compaction density and safety performance of positive electrode plates have been reported. However, the applicant researches and discovers that the gas generation problem of the high nickel material can be effectively improved by mixing the ternary single crystal material and the high nickel material, particularly when the ternary single crystal material and the high nickel material are mixed according to a certain mass ratio. The content of the impure lithium on the surface of the polycrystalline material is high, and after the polycrystalline material is mixed with the single crystal material in a certain proportion, the content of the overall impure lithium is reduced, so that the gas production source is effectively reduced, meanwhile, the size grain composition is utilized, the compaction density of a pole piece can be obviously improved, the residual space in the battery cell can be enlarged to the greatest extent in the design of the battery cell, the gas production of 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, because the single crystal material is introduced into the high-nickel material, the expansion force of the battery cell in the circulation process is controlled by the positive pole piece, so that the circulation expansion force is linearly increased, and the negative pole piece is extruded. Along with the embedding and the releasing of lithium ions in the negative pole piece, the extrusion force of the positive pole piece and the negative pole piece is synchronously increased, so that the electrolyte is extruded out from the positive pole piece and the negative pole piece, the negative pole dynamics is reduced, the lithium precipitation window of the battery cell is reduced, and the problems of lithium precipitation and water jump of the battery cell within 1000 cycles are caused.
[ 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, a conductive agent, and a binder. Further, the negative pole pieceHas a compacted density of 1.45g/cm 3 ～1.75g/cm 3 The negative electrode sheet containing the mixed carbon material preferably has an OI value (intensity ratio of X-ray diffraction peaks of the negative electrode sheet in the 004 and 110 crystal planes) of 24 to 32. The pole piece OI value is an important parameter for representing the orientation of the active material on the negative pole piece from a macroscopic level, and the smaller the pole piece OI value is, the better the orientation of the negative active material particles in the pole piece is, and the more the lithium ions can be embedded into the negative pole piece. According to the method, a certain amount of carbon material A with good isotropy is added into the carbon material B, so that the OI value of the negative pole piece can be effectively improved; however, when the OI value of the negative electrode tab is less than 24, the addition amount of the carbon material a is too large, which easily causes the active material loading capacity of the negative electrode tab to be too low and the capacity of the battery system to be too low; when the OI value of the negative pole piece 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 a carbon material, graphite, carbon black, graphene, and carbon nanotube conductive fiber. Commonly used conductive agents include Ketjen black (ultra fine conductive carbon black, particle size 30-40nm), SP (Super P, small particle conductive carbon black, particle size 30-40 μm), S-O (ultra fine graphite powder, particle size 3-4 μm), KS-6 (large particle graphite powder, particle size 6.5 μm), acetylene black, VGCF (vapor grown carbon fiber, particle size 3-20 μm). The optional conductive agent also includes 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 carboxymethylcellulose, an aqueous acrylic resin, an ethylene-vinyl acetate copolymer, styrene-butadiene rubber, fluorinated rubber, and polyurethane.
As an improvement of the negative electrode active material layer, it is preferable to further contain a dispersant. Further preferably, the conductive agent is one or a combination of more of amorphous carbon Super P, carbon nanotube CNT or small-particle graphite with D50<0.5mm, the dispersant is sodium carboxymethyl cellulose (CMC), and the binder is poly Styrene Butadiene Rubber (SBR).
As an improvement of the negative electrode active material layer, in the negative electrode active material layer, the sum of the mass percentages of negative electrode active materials, namely the carbon material A and the carbon material B, is 94-99%, and the mass percentage of a binder is 1-5%.
[ isolating film ]
In the embodiment of the present application, the material of the isolation film is not particularly limited, and may be a polymer isolation film. The polymeric barrier film may be selected from one of polyethylene, polypropylene and ethylene-propylene copolymer.
[ electrolyte ]
In the embodiment of the present application, the electrolytic solution includes an organic solvent and an electrolyte salt dissolved in the organic solvent.
Further, the organic solvent in the embodiment of the present application may contain one or more of cyclic carbonate, linear carbonate, chain carboxylate, and sulfone organic solvents. The organic solvent which can be specifically selected from the following is not limited thereto: ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, ethyl methyl carbonate, methyl formate, ethyl formate, propyl formate, butyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, pentyl propionate, methyl butyrate, methyl valerate, methyl acrylate, sulfolane, dimethyl sulfone.
In the 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 inorganic lithium salts and organic lithium salts.
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 (a). The organic lithium 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 can be selected in particular and are not limited thereto: fluoroethylene carbonate, ethylene sulfite, propane sultone, N-methyl pyrrolidone, N-methyl formamide, N-methyl acetamide, acetonitrile, acrylonitrile, gamma-butyrolactone and methyl sulfide.
In the following specific examples of the embodiments of the present application, only examples of the lithium ion battery are shown, but the embodiments of the present application are not limited thereto. The present application is further illustrated below with reference to examples of lithium ion batteries. It should be understood that these examples are for illustrative purposes only 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 ) Are commercially available. Other reagents, materials and equipment used are commercially available unless otherwise specified.
Examples
Preparation of negative pole piece
Mixing carbon material A and carbon material B with conductive agent carbon black Super P and binder Styrene Butadiene Rubber (SBR) according to different proportions, wherein the weight ratio of carbon material A to carbon material B is 92: 3: and 5, mixing, adding N-methyl pyrrolidone serving as a solvent, and stirring and uniformly mixing to obtain the cathode slurry. And uniformly coating the negative electrode slurry on a coating layer of a negative electrode current collector, drying at 80-90 ℃ after coating, cold pressing, slitting and cutting, and drying for 4 hours at 110 ℃ under a vacuum condition to obtain a negative electrode plate 1-12. The preparation method of the negative pole pieces D1-D5 is similar to that of the negative pole pieces 1-12, and only 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 physical and chemical parameters of the carbon material a and the carbon material B are shown in table 1, and the types and parameters of the carbon material in the negative electrode sheet are shown in table 2:
TABLE 1
TABLE 2
In the table "/" represents absence
Preparation of positive pole piece
And mixing the polycrystalline ternary material C (NCM622 and NCM811) and/or the single crystal ternary material D (NCM211) according to a certain weight ratio to obtain the mixed positive electrode active material. Continuously mixing the mixed positive electrode active material, a conductive agent carbon black and a binder polyvinylidene fluoride (PVDF) in a mixing weight ratio of 96: 2: 2. adding solvent N-methyl pyrrolidone, and mixing and stirring uniformly to obtain the anode slurry. And uniformly coating the positive electrode slurry on two sides of the positive electrode current collector aluminum foil, drying at 85 ℃, cold pressing, slitting and cutting into pieces, drying at 85 ℃ for 4 hours under a vacuum condition, and welding a positive electrode tab to obtain a positive electrode piece.
Preparation of electrolyte
Preparing a basic electrolyte, wherein the basic electrolyte comprises dimethyl carbonate (DMC), Ethyl Methyl Carbonate (EMC) and Ethylene Carbonate (EC), and the mass ratio of the dimethyl carbonate to the ethyl methyl carbonate to the ethylene carbonate is 2:1: 1. Then, an electrolyte salt was added so that the concentration of lithium hexafluorophosphate in the electrolyte solution was 1 mol/L.
Lithium ion battery preparation
The positive pole piece, the negative pole piece and the isolating film are wound into a battery cell and injected with electrolyte, and the lithium ion batteries S1-S17 and DS 1-DS 6 are prepared through the procedures of packaging, molding, formation and the like. The performance parameters of the negative electrode plate, the positive active material and the positive active material of the lithium ion battery are shown in table 3.
TABLE 3
In the table "-" stands for absence
Test example
Cycle performance test
3 batteries were taken out from each group of the batteries in the examples, and the batteries were repeatedly charged and discharged through the following steps, and the discharge capacity retention rate of the batteries was calculated.
First, in an environment of 25 ℃, first charging and discharging are performed, constant current charging is performed at a charging current of 1C (i.e., a current value at which a theoretical capacity is completely discharged within 1 h), then constant voltage charging is performed until an upper limit voltage is 4.2V, then constant current discharging is performed at a discharging current of 1C until a final voltage is 2.8V, and a discharge capacity of a first cycle is recorded. The charge and discharge cycles were then repeated and the discharge capacity was recorded for the 1000 th cycle.
According to the formula: the cycle capacity retention rate (discharge capacity at 1000 th cycle/discharge capacity at first cycle) × 100%, and the capacity retention rates before and after the battery cycle were calculated. When the cycle capacity retention rate was 80%, the cycle test was stopped. The average capacity retention after cycling of each battery group is shown in table 4.
Capacity testing
In a 25 ℃ constant temperature box, charging at a constant current of 1C multiplying power until the voltage is 4.2V, then charging at a constant voltage of 4.2V until the current is 0.05C, and then discharging at a constant current of 1C multiplying power until the voltage is 2.8V, wherein the obtained discharge capacity is the battery capacity.
TABLE 4
As can be seen from table 4, the negative electrode active material in the batteries S1 to S12 is a mixed carbon material, and the positive electrode active material is a single ternary material, in conformity with the limitation of the present application. Compared with DS 1-DS 4 using a single negative active material and DS5 and DS6 not conforming to the definition of the present application, the cycles of the batteries S1-S12 maintain benign attenuation.
The DS1 and DS2 adopt the high-pressure-resistant quick-charging carbon material A, and have strong resistance to expansion force, so 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 does not meet the design requirement of the battery cell. And the DS3 and DS4 have been subjected to water jumping at the later stage of the cycle, because the carbon material B has high capacity but weak pressure resistance, and under the condition that the expansion force of the battery core is gradually increased at the later stage of the cycle, the space of the pole piece is continuously compressed, the pores are continuously reduced, the electrolyte is extruded out, and lithium precipitation is caused and the water jumping is initiated. DS5 and DS6 have also jumped water, probably because the ratio Pb/Pa of the powder compaction density of carbon material A and carbon material B is less than 0.8, and the pressure resistance is too different. In general, materials with similar characteristics have large difference in gram capacity, and strong polarization exists on the surfaces between carbon material A and carbon material B particles when lithium ions are inserted and extracted, so that a water jumping phenomenon is generated after accumulation.
The negative active material in the cells S13 to S17 is a mixed carbon material, and the positive active material is a mixed ternary material containing single-crystal low nickel and polycrystalline high nickel, in conformity with the definition of the present application. Compared with S6 using a single positive active material, the cycle capacity retention rate and the battery capacity are both increased, and the mixed carbon material can further improve the reversible capacity and the pressure resistance of the negative pole piece and prolong the cycle life of the battery when used in a battery system of a mixed ternary material.
The preferred embodiments disclosed above are not intended to limit the scope of the claims. A number of possible variations and modifications can be made by anyone skilled in the art without departing from the concept of the present application, and the scope of protection of the present application shall therefore be subject to the ambit defined by the claims.
Claims (13)
1. A secondary battery comprises a positive electrode plate, a negative electrode plate, a separation film and electrolyte, and is characterized in that the negative electrode plate comprises a negative electrode active substance layer, the active substance of the negative electrode active substance layer is a mixed carbon material, the mixed carbon material comprises a carbon material A and a carbon material B, and the powder compaction density ratio of the carbon material A to the carbon material B is 0.8-1; 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 ；
Reversible capacity C of the carbon material B B Reversible capacity C with the carbon material A A The ratio of (1) to (C) B /C A Less than 1.1; reversible capacity C of the carbon material B B Not less than 355 mAh/g; the reversible capacity of the carbon material A is more than or equal to 345 mAh/g;
the carbon material A and the graphitization degree are lower than the graphitization degree of the carbon material B; the graphitization degree of the carbon material A is 90-96%, and the graphitization degree of the carbon material B is 95-99%.
2. The secondary battery according to claim 1,
the powder compaction density ratio of the carbon material A to the carbon material B is 0.9-0.98.
3. The secondary battery according to claim 1,
the D50 particle size of the carbon material A is 11-13.5 μm, and the D50 particle size of the carbon material B is 12-14.5 μm;
and/or the powder OI value C of the carbon material A 004 /C 110 Is 2 to 10;
and/or the mass ratio of the carbon material A to the carbon material B is (5-50): (50-95).
4. The secondary battery according to claim 1, wherein the mixed carbon material is mixed with a conductive agent and a binder and pressed to a compacted densityIs 1.45g/cm 3 ～1.75g/cm 3 When the negative electrode plate is used, the OI value C of the negative electrode plate 004 /C 110 Is 24 to 32.
5. The secondary battery according to claim 1, wherein the carbon material A has a coating layer on the surface thereof.
6. The secondary battery according to claim 5, wherein the coating material is selected from at least one of soft carbon, amorphous carbon, and hard carbon.
7. The secondary battery according to claim 5, wherein the mass of the coating layer is 0.5 to 10 wt% of the mass of the carbon material A.
8. The secondary battery according to claim 1, wherein the positive electrode sheet includes a positive electrode active material layer containing a ternary positive electrode material; the ternary positive electrode material comprises a polycrystalline ternary material and/or a single crystal 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.
9. The secondary battery according to claim 8, wherein the ternary positive electrode material comprises a polycrystalline ternary material and a single crystal ternary material, and the mass percentages of the polycrystalline ternary material and the single crystal ternary material are (50-85): (15-50).
10. The secondary battery according to claim 8, wherein the chemical formula of the polycrystalline ternary material 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, x1 is more than 0.5 and less than 1, y1 is more than 0 and less than 1, x1+ y1+ z1 is 1, b1 is more than or equal to 0 and less than or equal to 1, and N is b1 One or more selected from F, P, S.
11. According to claimThe secondary battery according to claim 8, 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 is 1, b2 is more than or equal to 0 and less than or equal to 1, and N b2 One or more selected from F, P, S.
12. The secondary battery according to claim 11, wherein the content of Ni element in the molecular formula of the single crystal ternary material is 0< x2 ≤ 0.5.
13. A method for preparing a secondary battery according to any one of claims 1 to 12, wherein the positive electrode sheet, the separator and the negative electrode sheet are stacked in sequence and then wound or pressed to obtain a bare cell, and then the electrolyte is injected and encapsulated to obtain the secondary battery.
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| CN114243089B (en) * | 2021-12-13 | 2023-10-13 | 上海瑞浦青创新能源有限公司 | Lithium iron phosphate secondary battery |
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| EP2696408B1 (en) * | 2011-05-23 | 2016-04-06 | LG Chem, Ltd. | High output lithium secondary battery having enhanced output density characteristic |
| CN102368549A (en) * | 2011-09-20 | 2012-03-07 | 山东沃特森新能源科技有限公司 | Lithium ion battery positive electrode material and lithium ion battery using it |
| CN102637859B (en) * | 2012-04-06 | 2014-08-27 | 宁德新能源科技有限公司 | Lithium ion battery, graphite cathode material of lithium ion battery, and preparation method of graphite anode material |
| EP2945209B1 (en) * | 2013-01-11 | 2018-04-11 | Nec Corporation | Lithium ion secondary battery |
| CN103811744B (en) * | 2014-02-13 | 2016-09-21 | 北大先行科技产业有限公司 | A kind of preparation method of ternary cathode material of lithium ion battery |
| CN104134791B (en) * | 2014-07-10 | 2017-01-25 | 宁波金和锂电材料有限公司 | High-voltage mono-crystal lithium nickel cobalt manganese oxide anode material and preparation method thereof |
| CN105185982A (en) * | 2015-08-31 | 2015-12-23 | 宁波金和锂电材料有限公司 | Cathode material and preparation method thereof and lithium-ion battery |
| JP2017142997A (en) * | 2016-02-10 | 2017-08-17 | 戸田工業株式会社 | Lithium nickelate-carbon composite positive electrode active material particle powder, and manufacturing method thereof, and nonaqueous electrolyte secondary battery |
| CN107293744A (en) * | 2016-04-12 | 2017-10-24 | 河南科隆新能源股份有限公司 | High-voltage monocrystal-like ternary cathode material and preparation method thereof |
| CN106229489B (en) * | 2016-08-29 | 2019-09-06 | 青海泰丰先行锂能科技有限公司 | A kind of high voltage ternary lithium ion anode material of monocrystalline pattern and preparation method thereof |
| CN106450155B (en) * | 2016-09-18 | 2019-11-29 | 贵州振华新材料股份有限公司 | Spherical or spherical anode material for lithium-ion batteries and preparation method and application |
| CN107437616B (en) * | 2017-07-11 | 2020-03-10 | 贵州振华新材料股份有限公司 | Lithium ion battery anode material and lithium ion battery |
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