CN116404161A - Positive electrode material, preparation method thereof, positive electrode plate and secondary battery - Google Patents

Positive electrode material, preparation method thereof, positive electrode plate and secondary battery Download PDF

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Publication number
CN116404161A
CN116404161A CN202310334256.5A CN202310334256A CN116404161A CN 116404161 A CN116404161 A CN 116404161A CN 202310334256 A CN202310334256 A CN 202310334256A CN 116404161 A CN116404161 A CN 116404161A
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positive electrode
electrode material
layer
buffer layer
core
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Inventor
谭旗清
万远鑫
孔令涌
赖佳宇
张莉
裴现一男
戴浩文
骆文森
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Foshan Defang Chuangjie New Energy Technology Co ltd
Qujing Defang Chuangjie New Energy Technology Co ltd
Shenzhen Dynanonic Innovazone New Energy Technology Co Ltd
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Foshan Defang Chuangjie New Energy Technology Co ltd
Qujing Defang Chuangjie New Energy Technology Co ltd
Shenzhen Dynanonic Innovazone New Energy Technology Co Ltd
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Priority to CN202310334256.5A priority Critical patent/CN116404161A/en
Publication of CN116404161A publication Critical patent/CN116404161A/en
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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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M4/04—Processes of manufacture in general
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • 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
    • 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
    • H01M2004/028—Positive 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The positive electrode material comprises a core, a buffer layer and a coating layer; wherein the core comprises a lithium-rich compound; the coating layer is coated on the outer surface of the inner core; the buffer layer is positioned between the inner core and the cladding layer; the deformation resistance of the cladding layer is greater than the deformation resistance of the core, and the deformation resistance of the buffer layer is located between the cladding layer and the deformation resistance of the core. The structural stability of the positive electrode material can be improved by using a combination of the buffer layer and the coating layer.

Description

Positive electrode material, preparation method thereof, positive electrode plate and secondary battery
Technical Field
The application relates to the technical field of secondary batteries, in particular to a positive electrode material, a preparation method thereof, a positive electrode plate and a secondary battery.
Background
The lithium ion battery is used as a representative of high-efficiency clean energy technology, has the advantages of high voltage, high energy density, good circularity, no memory effect and the like, and has been widely applied to various fields of national economy such as portable electronic equipment, electric automobiles, large-scale energy storage and the like.
However, while lithium ion batteries are widely used, the safety of lithium ion batteries is also receiving more attention. In the process of manufacturing lithium ion batteries, it is often necessary to squeeze the positive electrode sheet so that the positive electrode sheet can have a higher energy density. But this process also causes the structure of the positive electrode material to be damaged, thereby affecting the performance of the lithium battery. In addition, the anode material with the damaged structure is deformed and expanded due to atomic lattices in the use process, so that the battery pole piece is chalked or falls off, the electrochemical performance and the service life of the lithium ion battery are reduced, and the safety of the battery is also influenced.
Therefore, the method is a key problem in the manufacturing process of the lithium ion battery, so that the structure of the positive electrode material is prevented from being damaged, and the phenomenon that the positive electrode material is pulverized or falls off in the charging and discharging processes is ensured.
Disclosure of Invention
The purpose of the application is to provide a positive electrode material, a preparation method thereof, a positive electrode plate and a secondary battery.
The application provides the following technical scheme:
in a first aspect, the present application provides a positive electrode material comprising a core, a buffer layer, and a cladding layer; wherein the core comprises a lithium-rich compound; the coating layer is coated on the outer surface of the inner core; the buffer layer is positioned between the inner core and the cladding layer; the deformation resistance of the cladding layer is greater than the deformation resistance of the core, and the deformation resistance of the buffer layer is located between the cladding layer and the core. According to the invention, the inner core is coated by the material with higher Young modulus, so that the compression deformation resistance of the inner core is improved, the residual alkalinity of the surface of the inner core is reduced, and the corrosion of harmful substances in the external environment on the positive electrode material is reduced, thereby further improving the structural stability of the positive electrode material. When the lithium battery is assembled by the positive electrode material, structural collapse can not occur on the positive electrode material under the condition of uneven stress, and the formed positive electrode plate can also have a more uniform pore structure on the premise that the positive electrode material can have a complete structure, so that the permeation of electrolyte and the transmission of active ions are more facilitated; in addition, in the charging and discharging process of the lithium battery, the buffer layer and the coating layer can also prevent the lithium-rich compound from expanding, reduce pole piece pulverization and improve the electrochemical performance of the lithium battery.
In one possible embodiment, the Young's modulus G1 of the buffer layer and the Young's modulus G2 of the cladding layer are both greater than the Young's modulus G0 of the core, and the Young's modulus G2 of the cladding layer is greater than the Young's modulus G1 of the buffer layer. Specifically, on the basis of the above mode, when the young's modulus of the coating layer is greater than that of the buffer layer, the coating layer can have more excellent deformation resistance. When the coating layer is extruded by external force, the deformation amount of the coating layer is small, so that the pressure applied to the outer surface of the buffer layer is uniform. And after the buffer layer and the coating layer are matched, the deformation degree of the anode material can be relieved step by step, so that the outer surface of each layer (from the coating layer to the inner core) is uniformly stressed on the basis of smaller deformation. Therefore, collapse can not occur on the positive electrode material under the condition of uneven stress, and the formed positive electrode plate can also have a more uniform pore structure under the condition that the positive electrode material has uniform particle size, so that the permeation of electrolyte and the transmission of active ions are more facilitated.
In one possible embodiment, the Young's modulus G2 of the cladding layer 30 and the Young's modulus G1 of the buffer layer 20 differ by 40Gpa to 350Gpa. The difference value of the Young modulus G2 of the coating layer and the Young modulus G1 of the buffer layer is controlled within the range, so that the buffer layer and the coating layer can control the deformation of the buffer layer and the coating layer by layer through the obvious difference value, and the purpose of protecting the inner core is further achieved.
In one possible embodiment, the positive electrode material satisfies the relationship: and (G2-G1)/(G1-G0) is less than or equal to 0.1 and less than or equal to 9, wherein G0 is the Young's modulus of the inner core, G1 is the Young's modulus of the buffer layer, and G2 is the Young's modulus of the coating layer. When the above relation is satisfied, the Young's modulus difference between the layers is in a similar range, so that the pressure applied to the inside and outside of the positive electrode material can be kept consistent. When the Young's modulus is lower than the above range, the Young's modulus difference between the buffer layer and the coating layer is smaller, the deformation resistance of the coating layer and the buffer layer is similar, and the effect of the coating layer is easy to be smaller; above the above range, it is indicated that the Young's modulus difference between the buffer layer and the inner core is small, the deformation resistance of the buffer layer and the inner core are similar, and the effect of the buffer layer is small.
In one possible embodiment, the thickness H1 of the buffer layer is 1nm to 200nm. The thickness of the buffer layer is controlled within the above range, which is beneficial to adjusting the particle size of the positive electrode material, and simultaneously, the specific capacity and the electron conducting environment of the positive electrode material can be ensured.
In one possible embodiment, the thickness H2 of the coating layer is 1nm to 200nm. The thickness of the coating layer is controlled within the above range, which is favorable for adjusting the particle size of the positive electrode material, and at the same time, the specific capacity and the electron conduction environment of the positive electrode material can be ensured.
In one possible embodiment, the thicknesses of the buffer layer and the coating layer satisfy the relationship: H1/H2 is more than or equal to 0.005 and less than or equal to 200. When the above relation is satisfied, the thickness of the buffer layer and the thickness of the coating layer can be controlled within a proper range, so that the buffer layer and the coating layer can realize the deformation preventing effect on the inner core through a proper thickness ratio. When the deformation resistance is lower than the range, the buffer layer is too thin relative to the coating layer, so that the buffer layer cannot provide enough deformation resistance effect under the extrusion of the coating layer, and the deformation of the buffer layer is larger to influence the inner core; above this range, the coating layer is too thin relative to the buffer layer, and after the initial stress of the coating layer, a large deformation amount may be generated, thereby affecting the buffer layer.
In one possible embodiment, the buffer layer has a conductivity of 1×10 -13 S/cm～1.84S/cm。
In one possible embodiment, the electrical conductivity of the coating is 1×10 -13 S/cm～1.84S/cm。
In one possible embodiment, the specific surface area of the positive electrode material is 0.1m 2 /g～35m 2 /g。
In one possible embodiment, the positive electrode material has a particle diameter D50 of 1 μm to 20 μm.
In one possible embodiment, the mass of the buffer layer is 0.1% to 10% of the mass of the core. The mass ratio of the buffer layer is controlled in the range, so that the coating thickness of the buffer layer is adjusted more favorably, the buffer layer can effectively protect the inner core, and the buffer layer is prevented from being too thin or too thick, so that the structural stability or performance of the inner core is influenced.
In one possible embodiment, the mass of the coating layer is 0.1% to 10% of the mass of the core. The mass ratio of the coating layer is controlled within the range, so that the coating thickness of the coating layer is adjusted more favorably, the effective protection of the coating layer on the inner core is realized, and the coating layer is prevented from being too thin or too thick, so that the structural stability or performance of the inner core and the buffer layer are influenced.
In one possible embodiment, the residual alkalinity of the positive electrode material is 0.1% -3%.
In one possible embodiment, the lithium-rich compound has the chemical formula of Li 1+x M y O z Wherein M is one or more elements in Fe, ni, mn, cu, zn, co, cr, zr, ni, sb, ti, V, mo, sn, and 0 < x is less than or equal to 1,0 < y,0 < z < 10. Specifically, the lithium-rich compound may be Li 2 NiO 2 、Li 2 CuO 2 、Li 2 CoO 2 、Li 2 MnO 2 、Li 2 Ni 0.5 Mn 1.5 O 4 One or more of the following.
In a second aspect, the present application further provides a method for preparing a positive electrode material, including: mixing a lithium-rich compound and a buffer material in proportion, and sintering under an inert atmosphere to obtain a first anode material; mixing the first anode material and the coating material in proportion, and sintering under inert atmosphere to obtain a second anode material; the second positive electrode material comprises a core, a buffer layer and a coating layer, wherein the coating layer is coated on the outer surface of the core, and the buffer layer is positioned between the core and the coating layer; the coating layer has a deformation resistance greater than that of the core, and the buffer layer is located between the coating layer and the core.
In a third aspect, the present application further provides a positive electrode sheet, where the positive electrode sheet includes a current collector and an active material layer disposed on the current collector, the active material layer includes the positive electrode material described in any one of the above, or the active material layer includes the positive electrode material obtained by the method for preparing a positive electrode material described in any one of the above.
In a fourth aspect, the present application further provides a secondary battery, including the positive electrode sheet described above, or the secondary battery includes the positive electrode material obtained by the method for preparing the positive electrode material described above.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic cross-sectional view of a positive electrode material in one embodiment;
fig. 2 is a schematic diagram of a preparation process of a positive electrode material in an embodiment.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all, of the embodiments of the present application. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present disclosure.
It will be understood that when an element is referred to as being "fixed to" another element, it can be directly on the other element or intervening elements may also be present. When a component is considered to be "connected" to another component, it can be directly connected to the other component or intervening components may also be present.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in the description of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
Some embodiments of the present application are described in detail below with reference to the accompanying drawings. The following embodiments and features of the embodiments may be combined with each other without conflict.
In a first aspect, the present application provides a positive electrode material, please refer to fig. 1, including a core 10, a buffer layer 20 and a coating layer 30; wherein the core 10 comprises a lithium-rich compound; a cladding layer 30 which is coated on the outer surface of the core 10; the buffer layer 20 is located between the core 10 and the cladding layer 30; the deformation resistance of the cladding layer 30 is greater than the deformation resistance of the core 10, and the deformation resistance of the buffer layer 20 is located between the cladding layer 30 and the core 10.
Specifically, the positive electrode material has a core-shell structure, and the inner core 10 is a lithium-rich compound. The lithium-rich compound can be positive electrode material particles, is used for being assembled into a lithium battery by being matched with a negative electrode material, and provides lithium ions for a negative electrode; the lithium-rich compound can also be lithium supplementing material particles, and can be used as a sacrificial agent for supplementing a lithium source, so that the primary charging efficiency is ensured.
Alternatively, the material of the buffer layer 20 may be organic or inorganic, and the buffer layer 20 may be an aerogel structure. When the material of the buffer layer 20 is an organic material, the material includes, but is not limited to, one or more of polyvinylidene fluoride, polyacrylic acid, polyacrylonitrile, polyamide, polyimide, polyvinylpyrrolidone, polyethylene oxide, polypyrrole, polytetrafluoroethylene, polyurethane, polyethylene dioxythiophene, and asphalt such as asphalt-based fiber. When the material of the buffer layer 20 is inorganic, the material includes, but is not limited to, artificial graphite, aluminum oxide, silicon dioxide, tungsten carbide, silicon nitride, li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 (LATP)、Li 7 La 3 Zr 2 O 12 (LLZO)、Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 And the like.
Alternatively, the material of the coating layer 30 may be an organic or inorganic material, the material of the coating layer 30 may be the same as or different from the material of the buffer layer 20, and the material of the coating layer 30 may refer to the material of the buffer layer 20. It is understood that Young's modulus is related to the structural properties of the material itself and to the processing, such as monocrystalline, polycrystalline, amorphous, structural, dimensional, processing. Therefore, when the material of the buffer layer 20 and the clad layer 30 are the same, the young's modulus difference between the buffer layer 20 and the clad layer 30 can be further controlled by controlling the above parameters.
Further, the deformation resistance of both the buffer layer 20 and the cladding layer 30 is greater than the deformation resistance of the core 10. It will be appreciated that the resistance to deformation can be reflected by the Young's modulus, with a material having a greater Young's modulus having a greater resistance to deformation and a lesser degree of deformation under the same degree of stress. Of course, in other embodiments, the resistance to deformation may also be manifested by other mechanical properties parameters, such as hardness, strength, toughness, etc. When the battery is assembled, the pole pieces are pressed, the positive electrode material is pressed from outside to inside, and the conduction process occurs from the coating layer to the inner core 10. At the same compaction density, the pressure exerted by the cladding is transmitted uniformly to the core 10 due to the lesser degree of deformation of the cladding itself. The pressure applied to the outer surface of the inner core 10 is uniform, so that structural deformation or collapse of the inner core 10 caused by uneven stress can be avoided. Meanwhile, in the process of using the cathode material, the inner core 10 may have a lattice volume expansion, so that the inner core 10 is coated by the buffer layer 20 and the coating layer 30 with stronger deformation resistance, the expansion of the lattice volume of the cathode material can be restrained, and the phenomena of pulverization and falling of the pole pieces assembled by the buffer layer and the coating layer can be prevented.
According to the invention, the inner core is coated by the material with higher Young modulus, so that the compression deformation resistance of the inner core is improved, the residual alkalinity of the surface of the inner core is reduced, and the corrosion of harmful substances in the external environment on the positive electrode material is reduced, thereby further improving the structural stability of the positive electrode material. When the lithium battery is assembled by the positive electrode material, structural collapse can not occur on the positive electrode material under the condition of uneven stress, and the formed positive electrode plate can also have a more uniform pore structure on the premise that the positive electrode material can have a complete structure, so that the permeation of electrolyte and the transmission of active ions are more facilitated; in addition, in the charging and discharging process of the lithium battery, the buffer layer and the coating layer can also prevent the lithium-rich compound from expanding, reduce pole piece pulverization and improve the electrochemical performance of the lithium battery.
In one possible embodiment, the lithium-rich compound has the formula Li 1+x M y O z Wherein M is Fe, ni, mn, cu, zn, co,Cr, zr, ni, sb, ti, V, mo, sn, wherein x is more than 0 and less than or equal to 1, y is more than 0 and less than or equal to 10. Specifically, the lithium-rich compound may be Li 2 NiO 2 、Li 2 CuO 2 、Li 2 CoO 2 、Li 2 MnO 2 、Li 2 Ni 0.5 Mn 1.5 O 4 One or more of the following.
In one possible embodiment, the buffer layer may be one or more layers; and/or the coating layer may be one or more layers.
In one possible embodiment, the Young's modulus G1 of the buffer layer and the Young's modulus G2 of the cladding layer are both greater than the Young's modulus G0 of the core, and the Young's modulus G2 of the cladding layer is greater than the Young's modulus G1 of the buffer layer. Specifically, on the basis of the above-described manner, when the young's modulus of the clad layer 30 is greater than that of the buffer layer 20, the clad layer 30 can have more excellent deformation resistance. When the coating layer 30 is pressed by an external force, the deformation amount thereof is small, so that the pressure applied to the outer surface of the buffer layer 20 is uniform. And, after the buffer layer 20 and the cladding layer 30 are matched, the deformation degree of the positive electrode material can be relieved step by step, so that the outer surface of each layer (to the cladding layer 30 to the inner core 10) is uniformly stressed on the basis of smaller deformation. Therefore, collapse can not occur on the positive electrode material under the condition of uneven stress, and the formed positive electrode plate can also have a more uniform pore structure under the condition that the positive electrode material has uniform particle size, so that the permeation of electrolyte and the transmission of active ions are more facilitated.
In addition, in order to obtain higher energy density when the battery is assembled, the pole piece is generally extruded, so that the positive electrode material inside the pole piece is more dense. The application adopts two materials with different Young modulus to coat the positive electrode material based on the process, namely an active material with low Young modulus is used as a buffer layer of the positive electrode material, and an active material with high Young modulus is used as a coating layer. So that the material with a higher Young's modulus deforms less under pressure at the same compacted density, and thus does not destroy the pore structure of the electrode surface layer region. In addition, as the deformation of the positive electrode material particles on the outer layer is smaller, more force can be transmitted to the positive electrode material particles positioned in the pole piece, so that the pressure consistency of the upper layer particles and the lower layer particles is ensured, and the pore structure of the whole electrode is more beneficial to the permeation of electrolyte and the transmission of active ions. On the other hand, the better pore structure is beneficial to the retention of electrolyte in the electrode during the circulation process, thereby improving the circulation performance of the battery.
In one possible embodiment, the Young's modulus G2 of the cladding layer 30 and the Young's modulus G1 of the buffer layer 20 differ by 40Gpa to 350Gpa. Specifically, the difference between the Young's modulus G2 of the cladding layer and the Young's modulus G1 of the buffer layer may be, but not limited to, 40GPa, 50GPa, 60GPa, 80GPa, 100GPa, 150GPa, 200GPa, 250GPa, 350GPa. Controlling the difference between the young's modulus G2 of the cladding layer 30 and the young's modulus G1 of the buffer layer 20 within the above range can ensure that the buffer layer and the cladding layer can control their own deformation layer by a remarkable difference, thereby further achieving the purpose of protecting the core.
In one possible embodiment, the positive electrode material satisfies the relationship: and (G2-G1)/(G1-G0) is less than or equal to 0.1 and less than or equal to 9, wherein G0 is the Young's modulus of the inner core 10, G1 is the Young's modulus of the buffer layer, and G2 is the Young's modulus of the coating layer. Specifically, (G2-G1)/(G1-G0) may be, but is not limited to, 0.1, 0.2, 0.3, 0.5, 0.7, 1, 1.2, 1.5, 2, 3, 5, 7, 9. When the above relation is satisfied, the Young's modulus difference between the layers is in a similar range, so that the pressure applied to the inside and outside of the positive electrode material can be kept consistent. When the Young's modulus is lower than the above range, it means that the difference in Young's modulus between the buffer layer 20 and the clad layer 30 is smaller, the deformation resistance of the clad layer 30 and the buffer layer 20 are similar, and the effect of the clad layer 30 is liable to be smaller; above the above range, it is indicated that the Young's modulus difference between the buffer layer 20 and the inner core 10 is small, the deformation resistance of the buffer layer 20 and the inner core 10 are similar, and the effect of the buffer layer 20 is small.
In one possible embodiment, the thickness H1 of the buffer layer 20 is 1nm to 200nm. Specifically, the thickness of the buffer layer 20 may be, but is not limited to, 1nm, 5nm, 10nm, 20nm, 50nm, 100nm, 150nm, 200nm. Controlling the thickness of the buffer layer 20 within the above range is advantageous in adjusting the particle size of the positive electrode material while also ensuring the specific capacity of the positive electrode material and the electron conductive environment. When the thickness of the coating layer is lower than the above range, the buffer layer 20 does not completely coat the core 10, and the deformation preventing effect on the core 10 cannot be achieved through the buffer layer 20; when the thickness of the buffer layer 20 is higher than the above range, the particle diameter of the cathode material may be excessively large, and the overall gram capacity of the cathode material may be reduced since the buffer layer 20 does not contribute lithium ions.
In one possible embodiment, the thickness H2 of the cladding layer 30 is 1nm to 200nm; specifically, the thickness of the cladding layer 30 may be, but is not limited to, 1nm, 5nm, 10nm, 20nm, 50nm, 100nm, 150nm, 200nm. The thickness of the coating layer 30 is controlled within the above range, which is advantageous in adjusting the particle size of the cathode material while also ensuring the specific capacity of the cathode material and the electron conductive environment. When the thickness of the cladding layer is lower than the above range, the cladding layer 30 does not completely clad the core 10, and the deformation preventing effect on the buffer layer 20 and the core 10 cannot be achieved by the cladding layer 30; when the thickness of the coating layer 30 is higher than the above range, the particle diameter of the cathode material may be excessively large, and the overall gram capacity of the cathode material may be reduced since the buffer layer 20 does not contribute lithium ions.
In one possible embodiment, the thicknesses of the buffer layer 20 and the cladding layer 30 satisfy the relationship: H1/H2 is more than or equal to 0.005 and less than or equal to 200. Specifically, the thickness ratio of the buffer layer 20 and the cladding layer 30 may be, but not limited to, specifically 0.005, 0.01, 0.02, 0.05, 0.1, 0.2, 0.5, 1, 5, 10, 20, 50, 100, 200. When the above relation is satisfied, the thicknesses of the buffer layer 20 and the cladding layer 30 can be controlled within a proper range, so that the buffer layer 20 and the cladding layer 30 can achieve the deformation preventing effect on the core 10 through a proper thickness ratio. When the thickness is lower than the above range, the buffer layer 20 is too thin relative to the cladding layer 30, so that the buffer layer 20 cannot provide enough deformation resistance under the extrusion of the cladding layer 30, and the deformation degree of the buffer layer 20 is larger to affect the core 10; above this range, the coating layer 30 is too thin relative to the buffer layer 20, and a large deformation amount may occur after the coating layer 30 is initially stressed, thereby affecting the buffer layer 20.
In a possible embodiment, the buffer layer 20 has a conductivity of 1X 10 -13 S/cm-1.84S/cm. Specifically, the conductivity of the buffer layer 20 may be, but is not limited to, 1×10 -13 S/cm、0.67S/cm、0.85S/cm、1.02S/cm、1.28S/cm、1.49S/cm、1.62S/cm、1.84S/cm。
In one possible embodiment, the electrical conductivity of the coating 30 is 1×10 -13 S/cm-1.84S/cm. Specifically, the electrical conductivity of the cladding layer 30 may be, but is not limited to, 1×10 -13 S/cm、0.67S/cm、0.85S/cm、1.02S/cm、1.28S/cm、1.49S/cm、1.62S/cm、1.84S/cm。
In one possible embodiment, the specific surface area of the positive electrode material is 0.1m 2 /g～35m 2 And/g. Specifically, the specific surface area of the positive electrode material may be, but is not limited to, 0.1m 2 /g、1m 2 /g、2m 2 /g、5m 2 /g、10m 2 /g、20m 2 /g、35m 2 /g。
In one possible embodiment, the particle diameter D50 of the positive electrode material is 1 μm to 20 μm. Specifically, the particle diameter D50 of the positive electrode material may be, but is not limited to, 1 μm, 2 μm, 3 μm, 5 μm, 8 μm, 10 μm, 12 μm, 13 μm, 15 μm, 20 μm.
In one possible embodiment, the mass of the buffer layer 20 is 0.1% to 10% of the mass of the core 10. Specifically, the mass ratio of the buffer layer 20 may be, but is not limited to, 0.1%, 0.3%, 0.5%, 1%, 2%, 5%, 8%, 10%. By controlling the mass ratio of the buffer layer 20 within the above range, the coating thickness of the buffer layer 20 is more favorably adjusted, so that the buffer layer 20 can effectively protect the core 10, and the buffer layer 20 is prevented from being too thin or too thick, thereby affecting the structural stability or performance of the core 10. When the thickness is less than the above range, the buffer layer 20 is too thin, and the buffer layer 20 cannot exert an anti-deformation effect; above the above range, the buffer layer 20 may be excessively thick, but since the buffer layer 20 does not contribute lithium ions, the overall gram capacity of the positive electrode material may be reduced.
In one possible embodiment, the mass of the cladding 30 is 0.1% to 10% of the mass of the core 10. Specifically, the mass ratio of the coating layer 30 may be, but is not limited to, 0.1%, 0.3%, 0.5%, 1%, 2%, 5%, 8%, 10%. By controlling the mass ratio of the cladding layer 30 within the above range, it is more advantageous to adjust the cladding thickness of the cladding layer 30, thereby realizing effective protection of the core 10 by the cladding layer 30, and avoiding the cladding layer 30 from being too thin or too thick, thereby affecting the structural stability or performance of the core 10 and the buffer layer 20. When the thickness is less than the above range, the coating layer 30 is too thin, and the coating layer 30 cannot exert an anti-deformation effect; when above the above range, the coating layer 30 may be excessively thick, but since the coating layer 30 does not contribute lithium ions, the overall gram capacity of the positive electrode material may be reduced.
In one possible embodiment, the residual alkalinity of the positive electrode material is 0.1% to 3%. Specifically, the residual alkalinity of the positive electrode material may be, but is not limited to, 0.1%, 0.5%, 1%, 1.5%, 2.5%, 3%. It can be understood that the above residual alkali mass ratio is the residual alkali mass that may remain in the positive electrode material after the residual alkali is removed by the organic acid. The residual alkali in the range has small influence on the performance of the positive electrode material, and can also show that the residual alkali content in the positive electrode material coated by the organic acid reaction is obviously reduced.
In a second aspect, the present application further provides a method for preparing a positive electrode material, please refer to fig. 2, which is specifically used for preparing the positive electrode material in the first aspect. The preparation method comprises the following steps:
step S10, mixing a lithium-rich compound and a buffer material in proportion, and sintering under an inert atmosphere to obtain a first anode material;
and step S20, mixing the first positive electrode material and the coating material in proportion, and sintering under inert atmosphere to obtain the second positive electrode material.
Specifically, the second positive electrode material comprises a core, a buffer layer and a coating layer, wherein the coating layer is coated on the outer surface of the core, and the buffer layer is positioned between the core and the coating layer; the deformation resistance of the cladding layer is greater than the deformation resistance of the core, and the deformation resistance of the buffer layer is located between the cladding layer and the core.
In one possible embodiment, the method for preparing the lithium-rich compound in step S10 is not particularly limited, as long as the lithium-rich compound can be prepared. For example, the method of preparing the lithium-rich compound may employ solid phase sintering. In one possible embodiment, the step of preparing the lithium-rich compound comprises:
step S001, uniformly mixing an M source and a lithium source according to a molar ratio to obtain a mixture; step S002, sintering the mixture under inert atmosphere, cooling and crushing to obtain the lithium-rich compound.
Wherein the M source in the step S001 is a compound composed of M element in the chemical formula of the lithium-rich compound provided in the first aspect, and the compound includes at least one of an oxide, a hydroxide, a carbonate, a sulfate, and a chloride of M. The lithium source is at least one of lithium hydroxide, lithium oxide, lithium carbonate, lithium sulfate and lithium oxalate.
In a possible embodiment, in step S002, the inert atmosphere may be an atmosphere formed by any one of a nitrogen gas, an argon gas, and a nitrogen-argon mixture gas.
In a possible embodiment, in step S002, the sintering temperature of the mixture may be 650 to 900 ℃ and the sintering time may be 2 to 10 hours. The heating rate can be 100 ℃/h to 500 ℃/h.
In a possible embodiment, in step S10, the buffer material may be one or more of the raw materials of the buffer layer provided in the first aspect.
In a possible embodiment, in step S10, the sintering temperature after mixing the lithium-rich compound and the buffer material may be 450 to 700 ℃ and the sintering time may be 1 to 4 hours.
In a possible embodiment, in step S20, the coating material may be one or more of the raw materials of the coating layer provided in the first aspect. Also, the cushioning material and the cladding material may be different.
In a possible embodiment, in step S20, the sintering temperature after the first cathode material and the coating material are mixed may be 450 to 700 ℃ and the sintering time may be 1 to 4 hours.
In a third aspect, the present application also provides a positive electrode sheet comprising a current collector and an active material layer disposed on the current collector, the active material layer comprising the positive electrode material of any one of the second aspects. The positive electrode material can be used as a lithium supplementing additive to supplement active lithium consumed by forming an SEI film when the battery is charged for the first time, can be used as a positive electrode active material to participate in circulation, and has good application prospect. In some embodiments of the present application, the current collector comprises any one of copper foil and aluminum foil. In some embodiments, the active material layer includes an electrode active material, a lithium-rich material, a binder, and a conductive agent. In some embodiments, the active material layer includes a lithium-rich material, a binder, and a conductive agent, i.e., the lithium-rich material acts directly as the active material. In an embodiment of the present application, the binder comprises one or more of polyvinylidene chloride, soluble polytetrafluoroethylene, styrene-butadiene rubber, hydroxypropyl methylcellulose, carboxymethyl cellulose, polyvinyl alcohol, acrylonitrile copolymer, sodium alginate, chitosan, and chitosan derivatives. In embodiments of the present application, the conductive agent includes one or more of graphite, carbon black, acetylene black, graphene, carbon fiber, C60, and carbon nanotubes. In an embodiment of the present application, the electrode active material includes one or more of lithium cobaltate, lithium manganate, lithium iron phosphate, lithium manganese iron phosphate, lithium vanadium phosphate, lithium vanadyl phosphate, lithium vanadium fluorophosphate, lithium titanate, lithium nickel cobalt manganate, and lithium nickel cobalt aluminate.
In a fourth aspect, the present application also provides a secondary battery comprising a positive electrode, a negative electrode, a separator and an electrolyte, wherein the positive electrode comprises the positive electrode sheet provided by the present application. The secondary battery provided by the application has better cycle performance and safety performance due to the adoption of the positive electrode material, and is beneficial to the application of the secondary battery in various fields.
The technical scheme of the invention is described in detail by specific examples.
Example 1
The present embodiment provides a positive electrode material including Li 2 NiO 2 The inner core is formed, a buffer layer and a coating layer are arranged outside the inner core, and the buffer layer and the coating layer are made of artificial graphite. Young's modulus of the core is 8Gpa, yang Shimo of the buffer layerThe amount was 50GPa, the Young's modulus of the coating layer was 100GPa, the buffer layer thickness was 3.22nm, and the coating layer thickness was 4.15nm.
The preparation method of the positive electrode material comprises the following steps:
(1) Nickel oxide and lithium hydroxide are mixed according to a mole ratio of 1:2, uniformly mixing, then sintering for 10 hours in a nitrogen atmosphere, taking materials and crushing after the tube furnace is cooled, so as to obtain the lithium-rich compound. Wherein the sintering temperature is 770 ℃.
(2) And adding artificial graphite into the lithium-rich compound, uniformly mixing, and sintering for 1h in an inert atmosphere to obtain the positive electrode material containing the buffer layer. Wherein the artificial graphite is weighed according to 0.5% of the mass of the lithium-rich compound, and the Young's modulus of the artificial graphite in this step is 50Gpa. The sintering temperature was 450 ℃.
(3) And adding artificial graphite into the positive electrode material containing the buffer layer again, uniformly mixing, and sintering for 2 hours in an inert atmosphere to obtain the positive electrode material containing the coating layer. Wherein the artificial graphite is weighed according to 0.5% of the mass of the lithium-rich compound, and the Young's modulus of the tungsten carbide in the step is 100Gpa. The sintering temperature was 450 ℃.
Example 2
The present embodiment provides a positive electrode material including Li 2 NiO 2 The inner core is formed, a buffer layer and a coating layer are arranged outside the inner core, and the buffer layer and the coating layer are made of asphalt-based fibers. The Young's modulus of the core was 8Gpa, the Young's modulus of the buffer layer was 350Gpa, the Young's modulus of the cladding layer was 560Gpa, the buffer layer thickness was 3.40nm, and the cladding layer thickness was 4.18nm.
The preparation method of the positive electrode material comprises the following steps:
(1) The same as in example 1.
(2) The same as in example 1, except that the buffer layer material was an asphalt-based fiber.
(3) The same as in example 1, except that the coating material was an asphalt-based fiber.
Example 3
This embodiment provides a positive electrode material and a method for preparing the same, the positive electrodeThe electrode material comprises Li 2 NiO 2 The inner core is formed, a buffer layer and a coating layer are arranged outside the inner core, the buffer layer is made of 3, 4-ethylenedioxythiophene (PEDOT) aerogel, and the coating layer is made of silicon carbide. The Young's modulus of the core was 8Gpa, the Young's modulus of the buffer layer was 164Gpa, the Young's modulus of the cladding layer was 450Gpa, the buffer layer thickness was 3.51nm, and the cladding layer thickness was 5.10nm.
The preparation method of the positive electrode material comprises the following steps:
(1) The same as in example 1.
(2) The same as in example 1, except that the buffer layer material was 3, 4-ethylenedioxythiophene (PEDOT) aerogel.
(3) The same as in example 1, except that the coating material was silicon carbide.
Example 4
The present embodiment provides a positive electrode material including Li 2 NiO 2 The inner core is formed, a buffer layer and a coating layer are arranged outside the inner core, the buffer layer is made of 3, 4-ethylenedioxythiophene (PEDOT) aerogel, and the coating layer is made of silicon carbide. The Young's modulus of the core was 8Gpa, the Young's modulus of the buffer layer was 164Gpa, the Young's modulus of the cladding layer was 450Gpa, the buffer layer thickness was 5.57nm, and the cladding layer thickness was 10.31nm.
The preparation method of the positive electrode material comprises the following steps:
(1) The same as in example 3.
(2) The same as in example 3, except that 3, 4-ethylenedioxythiophene (PEDOT) aerogel was 2wt% of the mass fraction of the core material.
(3) The same as in example 3, except that silicon carbide was 3wt% of the mass fraction of the core material.
Example 5
The present embodiment provides a positive electrode material including Li 2 NiO 2 The inner core is formed, a buffer layer and a coating layer are arranged outside the inner core, the buffer layer is made of 3, 4-ethylenedioxythiophene (PEDOT) aerogel, and the coating layer is made of silicon carbide. The kernelThe Young's modulus of the buffer layer is 164Gpa, the Young's modulus of the coating layer is 450Gpa, the thickness of the buffer layer is 24.10nm, and the thickness of the coating layer is 32.5nm.
The preparation method of the positive electrode material comprises the following steps:
(1) The same as in example 3.
(2) The same as in example 3, except that the 3, 4-ethylenedioxythiophene (PEDOT) aerogel was 8wt% of the mass fraction of the core material.
(3) The same as in example 3, except that silicon carbide was 9wt% of the mass fraction of the core material.
Comparative example 1
This comparative example provides a positive electrode material and a method of producing the same, which is not provided with a buffer layer and a coating layer.
The preparation method of the positive electrode material comprises the following steps:
(1) The same as in example 1.
Comparative example 2
This comparative example provides a positive electrode material comprising Li 2 NiO 2 The coating layer is arranged outside the inner core, the Young modulus of the coating layer is larger than that of the inner core, the material of the coating layer is graphene, the Young modulus of the coating layer is 15Gpa, and the thickness of the coating layer is 2.51nm.
The preparation method of the positive electrode material comprises the following steps:
(1) The same as in example 1.
(2) The same as in example 1.
The positive electrode materials provided in examples 1 to 5 and the positive electrode materials provided in comparative examples 1 to 2 were assembled into a positive electrode and a lithium ion battery, respectively, as follows:
positive electrode: mixing the anode material with lithium iron phosphate according to the mass ratio of 4:96 to obtain a mixture, mixing the mixture with polyvinylidene fluoride and SP-Li according to the mass ratio of 93:3:4, ball-milling and stirring to obtain anode slurry, coating the anode slurry on the surface of an aluminum foil, vacuum-drying at 110 ℃ for overnight, and rolling to obtain an anode plate;
and (3) a negative electrode: graphite with carboxymethylcellulose (CMC), SBR and SP according to 95.8: mixing, ball milling and stirring in a mass ratio of 1.2:2:1 to obtain negative electrode slurry, coating the negative electrode slurry on the surface of a copper foil, and vacuum drying overnight at 110 ℃ to obtain a negative electrode plate;
electrolyte solution: mixing ethylene carbonate and ethylmethyl carbonate in a volume ratio of 3:7, and adding LiPF 6 Electrolyte is formed, liPF 6 The concentration of (2) is 1mol/L;
a diaphragm: a polypropylene microporous separator;
and (3) assembling a lithium ion battery: and assembling the button type lithium ion full battery in an inert atmosphere glove box according to the assembling sequence of the graphite negative electrode plate, the diaphragm, the electrolyte and the positive electrode plate.
The electrochemical properties of each lithium ion battery assembled in the above lithium ion battery examples were respectively subjected to the performance test as in table 1, and the test conditions were as follows:
constant-current constant-voltage charging, the first-circle charging and discharging voltage is 2.5-4.3V, the current is 0.1C, the cut-off current is 0.01C, and 500 circles of circulation are carried out by the current of 2C, and the cut-off current is 0.01C.
The test results are shown in table 1 below:
TABLE 1
Figure BDA0004155886030000101
As can be seen from the test results of examples 1-5 and comparative examples 1-2 of table 1, the lithium batteries prepared by the positive electrode materials provided in the present application all have higher electrical properties. This demonstrates that the electrochemical performance of the positive electrode material can be improved by coating the lithium-rich compound with a material having a higher resistance to deformation as the buffer layer and the coating layer.
As can be seen from comparing example 1 and comparative examples 1-2, one-layer coated (coating layer) positive electrode material is superior to uncoated positive electrode material, and two-layer coated (buffer layer and coating layer) positive electrode material is superior to one-layer coated positive electrode material. Specifically, from the data of the 500-cycle capacity retention rate, the capacity retention rate in examples 1-5 is greater than 87%, and the capacity retention rate in comparative examples 1-2 is lower than 80%, so that it is demonstrated that the positive electrode material with the double-layer coating layer structure prepared by the method has stable mechanical properties, and in the high-rate charge and discharge process of the lithium battery, the coating layer can reduce the volume expansion of the positive electrode material, reduce pole piece pulverization, and improve the electrochemical performance of the lithium battery.
It can be seen from examples 1-3 that the solution provided in the present application is not limited to coating with inorganic materials, but can be used with organic materials or with a common way of organic-inorganic materials. The buffer layer and the cladding layer can be constructed more flexibly according to the type of the core or the type of the required pole piece.
As can be seen from the comparison of examples 3 to 5, the ratio and thickness of the coating layer and the buffer layer are controlled within the appropriate ranges, so that the lithium battery prepared from the positive electrode material of example 4 has a significantly higher primary charge capacity than other examples, since the lithium ion transmission rate can be improved and the heterogeneous interface of the internal resistance can be reduced.
In the description of the embodiments of the present application, it should be noted that, the terms "center," "upper," "lower," "left," "right," "vertical," "horizontal," "inner," "outer," and the like refer to the orientation or positional relationship described based on the drawings, which are merely for convenience of description and simplification of the description, and do not indicate or imply that the apparatus or element to be referred to must have a specific orientation, be configured and operated in a specific orientation, and therefore should not be construed as limiting the present application.
The foregoing disclosure is only a preferred embodiment of the present application, and it is not intended to limit the scope of the claims, and one of ordinary skill in the art will understand that all or part of the processes for implementing the embodiments described above may be performed with equivalent changes in the claims of the present application and still fall within the scope of the present application.

Claims (11)

1. A positive electrode material, characterized by comprising:
a core comprising a lithium-rich compound;
the coating layer is coated on the outer surface of the inner core; the method comprises the steps of,
a buffer layer located between the core and the cladding layer;
the deformation resistance of the cladding layer is greater than the deformation resistance of the core, and the deformation resistance of the buffer layer is located between the deformation resistance of the cladding layer and the core.
2. The positive electrode material according to claim 1, wherein the young's modulus G1 of the buffer layer and the young's modulus G2 of the coating layer are both larger than the young's modulus G0 of the core, and the young's modulus G2 of the coating layer is larger than the young's modulus G1 of the buffer layer.
3. The positive electrode material according to claim 1, wherein a difference between the young's modulus G2 of the coating layer and the young's modulus G1 of the buffer layer is 40Gpa to 350Gpa.
4. The positive electrode material according to claim 1, wherein the positive electrode material satisfies the relation: and (G2-G1)/(G1-G0) is less than or equal to 0.1 and less than or equal to 9, wherein G0 is the Young's modulus of the inner core, G1 is the Young's modulus of the buffer layer, and G2 is the Young's modulus of the coating layer.
5. The positive electrode material according to claim 1, wherein the thickness H1 of the buffer layer is 1nm to 200nm; and/or the thickness H2 of the coating layer is 1 nm-200 nm; and/or, the thicknesses of the buffer layer and the coating layer satisfy the relation: H1/H2 is more than or equal to 0.005 and less than or equal to 200.
6. The positive electrode material according to claim 1, wherein the mass of the buffer layer is 0.1% to 10% of the mass of the core; and/or the mass of the coating layer is 0.1-10% of the mass of the inner core.
7. The positive electrode material according to claim 1, wherein the buffer layer has an electrical conductivity of 1 x 10 -13 S/cm-1.84S/cm; and/or the electrical conductivity of the coating layer is 1×10 -13 S/cm～1.84S/cm。
8. The positive electrode material according to any one of claims 1 to 7, wherein the lithium-rich compound has a chemical formula of Li 1+x M y O z Wherein M is one or more elements in Fe, ni, mn, cu, zn, co, cr, zr, ni, sb, ti, V, mo, sn, x is more than 0 and less than or equal to 1, y is more than 0 and less than or equal to 10, and z is more than 0 and less than or equal to 10; and/or the number of the groups of groups,
the specific surface area of the positive electrode material is 0.1m 2 /g～35m 2 /g, and/or,
the particle diameter D50 of the positive electrode material is 1-20 mu m, and/or,
the residual alkalinity of the positive electrode material is 0.1% -3%.
9. A method for preparing a positive electrode material, comprising:
mixing a lithium-rich compound and a buffer material in proportion, and sintering under an inert atmosphere to obtain a first anode material;
mixing the first anode material and the coating material in proportion, and sintering under inert atmosphere to obtain a second anode material;
the second positive electrode material comprises a core, a buffer layer and a coating layer, wherein the coating layer is coated on the outer surface of the core, and the buffer layer is positioned between the core and the coating layer; the coating layer has a deformation resistance greater than that of the core, and the buffer layer is located between the coating layer and the core.
10. A positive electrode sheet, characterized in that the positive electrode sheet comprises a current collector and an active material layer provided on the current collector, the active material layer comprising the positive electrode material according to any one of claims 1 to 8, or the active material layer comprising the positive electrode material obtained by the method for producing a positive electrode material according to claim 9.
11. A secondary battery comprising the positive electrode sheet according to claim 10, or comprising the positive electrode material according to any one of claims 1 to 8, or comprising the positive electrode material obtained by the method for producing the positive electrode material according to claim 9.
CN202310334256.5A 2023-03-27 2023-03-27 Positive electrode material, preparation method thereof, positive electrode plate and secondary battery Pending CN116404161A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116864662A (en) * 2023-07-21 2023-10-10 深圳市德方创域新能源科技有限公司 Lithium-rich positive electrode material and preparation method and application thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116864662A (en) * 2023-07-21 2023-10-10 深圳市德方创域新能源科技有限公司 Lithium-rich positive electrode material and preparation method and application thereof

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