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CN114256448A - Lithium iron manganese phosphate composite material, preparation method thereof and lithium ion battery - Google Patents

Lithium iron manganese phosphate composite material, preparation method thereof and lithium ion battery Download PDF

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Publication number
CN114256448A
CN114256448A CN202011026080.XA CN202011026080A CN114256448A CN 114256448 A CN114256448 A CN 114256448A CN 202011026080 A CN202011026080 A CN 202011026080A CN 114256448 A CN114256448 A CN 114256448A
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layer
lithium iron
lithium
manganese phosphate
composite material
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陈娜
郝嵘
潘仪
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BYD Co Ltd
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BYD Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

The application provides a lithium iron manganese phosphate composite material, including kernel and cladding the coating of kernel, the coating includes at least one deck barrier material layer and at least one deck lithium iron manganese phosphate layer, the barrier material layer with the lithium iron manganese phosphate layer is in turn in proper order range upon range of setting up the surface of kernel, the material of kernel includes LiMnxFe1‑xPO4The material of the lithium iron manganese phosphate layer comprises LiMnyFe1‑yPO4Wherein y < x. The wrapping layer is arranged to wrap the lithium manganese iron phosphate core, so that the phenomenon that manganese in the lithium manganese iron phosphate composite material is dissolved out is effectively improved, the structural stability and the electrochemical stability of the lithium manganese iron phosphate composite material are ensured, the application in a lithium ion battery is facilitated, and the performance of the lithium ion battery is improved. The application also provides a preparation method of the lithium iron manganese phosphate composite material and a lithium ion battery.

Description

Lithium iron manganese phosphate composite material, preparation method thereof and lithium ion battery
Technical Field
The application relates to the technical field of lithium ion batteries, in particular to a lithium iron manganese phosphate composite material, a preparation method thereof and a lithium ion battery.
Background
Compared with the traditional battery, the lithium ion battery has the advantages of high energy density, high voltage, long service life, environmental friendliness and the like, and is widely applied to the fields of electronic equipment, automobiles, aerospace and the like. As an important component of lithium ion batteries, the selection of the positive electrode material directly affects the performance of the lithium ion battery. The lithium iron manganese phosphate has the advantages of high capacity, high safety, good cycle performance, safety and no toxicity, and is an important lithium ion battery anode material. However, in actual use, manganese dissolution occurs in the lithium manganese iron phosphate, which results in capacity fading, influences the stability of the lithium manganese iron phosphate structure, and influences other composition structures of the lithium ion battery, which results in performance degradation of the lithium ion battery.
Disclosure of Invention
In view of this, the application provides a lithium iron manganese phosphate composite material and a preparation method thereof, and by arranging a lithium iron manganese phosphate core wrapped by a wrapping layer, the occurrence of a manganese dissolution phenomenon in the lithium iron manganese phosphate composite material is effectively improved, the structural stability and the electrochemical stability of the lithium iron manganese phosphate composite material are ensured, the application in a lithium ion battery is facilitated, and the performance of the lithium ion battery is improved.
In a first aspect, the application provides a lithium iron manganese phosphate composite material, including kernel and cladding the coating of kernel, the coating includes at least one deck barrier material layer and at least one deck lithium iron manganese phosphate layer, the barrier material layer with the lithium iron manganese phosphate layer is in turn range upon range of the setting on the surface of kernel, the material of kernel includes LiMnxFe1-xPO4The material of the lithium iron manganese phosphate layer comprises LiMnyFe1-yPO4Wherein y < x.
According to the application, the core wrapped by the wrapping layer is arranged, so that the manganese dissolution phenomenon in the high-manganese-content lithium manganese iron phosphate core is effectively improved; the energy density of the lithium manganese iron phosphate composite material is improved by the high manganese content lithium manganese iron phosphate core; the barrier material layer blocks the dissolution of manganese in the core, so that the structural stability and the electrochemical stability of the lithium iron manganese phosphate composite material are ensured; the manganese content in the lithium iron manganese phosphate layer is low, so that the phenomenon that a large amount of manganese is dissolved out is avoided, and meanwhile, the performance of the lithium iron manganese phosphate layer with low manganese content is closer to the performance of lithium iron phosphate, so that the high-rate charging and discharging of the lithium iron manganese phosphate composite material is improved.
Optionally, the value range of x is as follows: x is more than or equal to 0.6 and less than 1.
Optionally, the material of the lithium iron manganese phosphate layer on the outermost layer in the coating layer comprises LiMnyFe1-yPO4Wherein y is more than 0 and less than or equal to 0.65.
Optionally, when the coating layer has a plurality of lithium iron manganese phosphate layers, the material LiMn of the lithium iron manganese phosphate layer is in a direction from the core to the coating layeryFe1-yPO4The manganese content in the steel is gradually reduced.
Optionally, the lithium iron manganese phosphate composite material further comprises a carbon coating layer, the carbon coating layer coats the coating layer, and the mass content of the carbon coating layer in the lithium iron manganese phosphate composite material is 0.5% -5%.
Optionally, the material of the barrier material layer includes at least one of metal oxide, metaphosphate and pyrophosphate, and the thickness of the barrier material layer is 100nm to 500 nm.
Optionally, the mass of the core accounts for 80% -95% of the total mass of the lithium manganese iron phosphate in the lithium manganese iron phosphate composite material.
In a second aspect, the present application provides a preparation method of a lithium iron manganese phosphate composite material, including:
forming a coating layer on the surface of the inner core through solid-phase sintering to obtain the lithium iron manganese phosphate composite material, wherein the coating layer comprises at least one layer of barrier material layer and at least one layer of lithium iron manganese phosphate layer, the barrier material layer and the lithium iron manganese phosphate layer are sequentially and alternately stacked on the surface of the inner core, and the material of the inner core comprises LiMnxFe1-xPO4The material of the lithium iron manganese phosphate layer comprises LiMnyFe1-yPO4Wherein y < x.
Optionally, the forming of the coating layer on the surface of the inner core through solid phase sintering to obtain the lithium iron manganese phosphate composite material includes:
providing a core material comprising LiMnxFe1-xPO4；
Mixing the core material and the barrier material, and performing solid-phase sintering to obtain an intermediate;
and mixing the intermediate, the manganese iron phosphate and a lithium source, and performing solid-phase sintering to obtain the lithium iron manganese phosphate composite material.
The preparation method of the lithium iron manganese phosphate composite material is simple, the raw material source is rich and easy to obtain, the lithium iron manganese phosphate composite material is suitable for large-scale production, and the lithium iron manganese phosphate composite material with excellent performance is prepared.
In a third aspect, the present application provides a lithium ion battery, which includes a positive electrode, a negative electrode and an electrolyte, wherein the positive electrode includes the lithium iron manganese phosphate composite material prepared by the preparation method of the first aspect or the second aspect.
The lithium ion battery provided by the application has excellent structural stability and electrochemical performance, and is beneficial to wide application.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. The specific embodiments described herein are merely illustrative of the invention and do not delimit the invention.
Fig. 1 is a schematic structural diagram of a lithium iron manganese phosphate composite material according to an embodiment of the present disclosure.
Fig. 2 is a schematic structural diagram of a lithium iron manganese phosphate composite material according to another embodiment of the present application.
Fig. 3 is a schematic structural diagram of a lithium iron manganese phosphate composite material according to another embodiment of the present application.
Fig. 4 is a flowchart of a method for preparing a lithium iron manganese phosphate composite material according to an embodiment of the present disclosure.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Referring to fig. 1, a schematic structural diagram of a lithium iron manganese phosphate composite material according to an embodiment of the present disclosure is shown, the lithium iron manganese phosphate composite material includes a core 10 and a coating layer 20 coating the core 10, the coating layer 20 includes at least one barrier material layer 21 and at least one lithium iron manganese phosphate layer 22, the barrier material layer 21 and the lithium iron manganese phosphate layer 22 are sequentially and alternately stacked on a surface of the core 10, and a material of the core 10 includes LiMnxFe1-xPO4The material of the lithium iron manganese phosphate layer 22 includes LiMnyFe1-yPO4Wherein y < x.
After manganese in the high-manganese-content lithium manganese iron phosphate is dissolved out, the structure of the lithium manganese iron phosphate can be damaged, and the performance of the lithium manganese iron phosphate is influenced; in the application, the barrier material layer blocks the manganese in the high-manganese-content lithium manganese iron phosphate core from dissolving out, so that the manganese dissolving-out amount of the lithium manganese iron phosphate composite material in the use process is reduced, and the structural stability and excellent performance of the lithium manganese iron phosphate composite material are ensured.
In the present application, the material of the core includes LiMnxFe1-xPO4The material of the lithium iron manganese phosphate layer comprises LiMnyFe1- yPO4Y is less than x; that is to say, in the direction from inside to outside of the lithium manganese iron phosphate composite material, the manganese content of the lithium manganese iron phosphate material is gradually reduced, so that the core can maintain the original high-voltage platform and high capacity, and meanwhile, the performance of the outer lithium manganese iron phosphate layer is closer to that of the lithium iron phosphate layer, so that the lithium manganese iron phosphate composite material has better cycle performance, and the electrochemical performance of the lithium manganese iron phosphate composite material is improved。
In this application, through the coating that the setting has at least one deck separation material layer and at least one deck manganese iron lithium phosphate layer, can show that the manganese dissolves out in the manganese iron lithium phosphate kernel that reduces high manganese content, has promoted the performance of manganese iron lithium phosphate composite.
It can be understood that the lithium iron manganese phosphate composite material is in a core-shell structure, the direction from the core to the coating layer is from inside to outside in the application, the innermost layer is a layer structure closest to the core in the multilayer structure, and the outermost layer is a layer structure farthest from the core in the multilayer structure.
In the embodiment of the present application, the value range of x is: x is more than or equal to 0.6 and less than 1. Further, LiMnxFe1-xPO4X is more than or equal to 0.6 and less than 0.95, the manganese content in the core is further reduced, the manganese elution amount is reduced, and the performance of the lithium iron manganese phosphate composite material is ensured. Further, LiMnxFe1-xPO4X is more than or equal to 0.65 and less than or equal to 0.85. Specifically, x may be, but is not limited to, 0.65, 0.7, 0.75, 0.8, or 0.85. The inventor of the application finds that the lithium iron manganese phosphate material LiMnxFe1-xPO4X is more than or equal to 0.6 and less than 1, and the lithium iron manganese phosphate material LiMn is prepared at the momentxFe1-xPO4Manganese dissolves more in the in-service use, consequently wraps above-mentioned lithium iron manganese phosphate material with the coating to effectively having slowed down the manganese and having dissolved the phenomenon, greatly having promoted lithium iron manganese phosphate composite material structural stability, above-mentioned lithium iron manganese phosphate material can show the energy density who promotes lithium iron manganese phosphate material composite material simultaneously, more is favorable to its application.
In the embodiment of the application, the mass of the core accounts for 80-95% of the total mass of the lithium manganese iron phosphate in the lithium manganese iron phosphate composite material. That is, LiMnxFe1-xPO4Accounting for 80-95% of the total mass of the lithium manganese iron phosphate in the lithium manganese iron phosphate composite material. The high manganese content lithium manganese iron phosphate core ensures that the lithium manganese iron phosphate composite material has high voltage and high energy density. Furthermore, the mass of the core accounts for 85% -90% of the total mass of the lithium manganese iron phosphate in the lithium manganese iron phosphate composite material. In particular, the quality of the kernel may be, but is not limited toIs limited to 82%, 83%, 86%, 87%, 90%, 92% or 93% of the total mass of the lithium manganese iron phosphate in the lithium manganese iron phosphate composite material.
In the present embodiment, the radius of the inner core is 5 μm to 13 μm. The inner core with the radius of 5-13 mu m accounts for more in the lithium manganese iron phosphate composite material, and the lithium manganese iron phosphate composite material is endowed with high energy density. Furthermore, the radius of the inner core is 6-12 μm. Specifically, the radius of the inner core may be, but is not limited to, 5 μm, 7 μm, 8 μm, 10 μm, 11.5 μm, or 13 μm.
In the application, the coating layer comprises at least one barrier material layer and at least one lithium iron manganese phosphate layer, and the barrier material layer and the lithium iron manganese phosphate layer are sequentially and alternately stacked on the surface of the core; that is, the innermost layer of the coating layer is a barrier material layer, and the outermost layer is a lithium iron manganese phosphate layer. In one embodiment of the present application, the coating layer includes a barrier material layer coating the core, and a lithium iron manganese phosphate layer coating the barrier material layer. In another embodiment of the present application, the coating layer includes a plurality of barrier material layers and a plurality of lithium iron manganese phosphate layers, and the barrier material layers and the lithium iron manganese phosphate layers are sequentially and alternately stacked on the surface of the core.
Referring to fig. 1, the coating layer 20 includes a barrier material layer 21 and a lithium iron manganese phosphate layer 22. Referring to fig. 2, a schematic structural diagram of a lithium iron manganese phosphate composite material according to another embodiment of the present disclosure is shown, the lithium iron manganese phosphate composite material includes a core 10 and a coating layer 20 coating the core 10, the coating layer 20 includes two barrier material layers 21 and two lithium iron manganese phosphate layers 22, and the barrier material layers 21 and the lithium iron manganese phosphate layers 22 are sequentially and alternately stacked on a surface of the core 10. It is understood that the coating layer may further include more than two barrier material layers and more than two lithium iron manganese phosphate layers, which are not described herein again. In the embodiment of the application, the number of the barrier material layers in the coating layer is not more than 5, and the number of the lithium iron manganese phosphate layers in the coating layer is not more than 5. Therefore, the manganese dissolution is avoided as much as possible, and the excellent electrochemical performance of the lithium iron manganese phosphate composite material can be ensured. Furthermore, the number of the barrier material layers in the coating layer is 1-3, and the number of the lithium iron manganese phosphate layers in the coating layer is 1-3.
In the present application, the coating layer may completely coat the core or partially coat the core; the barrier material layer can completely cover the inner core or can cover part of the inner core; the lithium iron manganese phosphate layer can completely cover the barrier material layer, and can also cover part of the barrier material layer. In one embodiment of the present application, the coating layer completely covers the core, and prevents elution of manganese as much as possible.
In this application, barrier material layer can play the barrier effect to the kernel, avoids manganese to dissolve out, promotes the bulk property of lithium iron manganese phosphate composite. Compared with the setting of the lithium iron manganese phosphate with the gradient change of manganese content, the barrier material layer can block the occurrence of the condition of uniform distribution caused by the free diffusion of manganese in the inner core and the lithium iron manganese phosphate layer, so that the dissolution of manganese is fundamentally avoided, and the lithium iron manganese phosphate composite material with the manganese molar mass reduced from inside to outside is formed.
In the embodiments, the material of the barrier material layer includes at least one of metal oxide, metaphosphate, and pyrophosphate. The barrier material layer can block manganese self-diffusion caused by the difference of the manganese content of the inner layer and the outer layer, so that the manganese is distributed differentially, and meanwhile, the direct contact between the electrolyte and the manganese is avoided, and the manganese is prevented from dissolving out. Optionally, the metal oxide comprises at least one of titanium oxide, yttrium oxide, niobium oxide, and aluminum oxide. The metal oxide has good stability, and is beneficial to stably coating the kernel for a long time, so that the lithium iron manganese phosphate composite material has long-term and efficient performance and long service life. In one embodiment, the metaphosphate comprises a metal-containing metaphosphate. Optionally, the metaphosphate comprises at least one of aluminum metaphosphate, barium metaphosphate, calcium metaphosphate, magnesium metaphosphate, and zinc metaphosphate. In one embodiment, the pyrophosphate salt comprises a metal element-containing pyrophosphate salt. Optionally, the pyrophosphate salt comprises at least one of yttrium pyrophosphate, potassium pyrophosphate, sodium pyrophosphate, and calcium pyrophosphate. In an embodiment, when the lithium iron manganese phosphate composite material has multiple barrier material layers, the materials of the multiple barrier material layers may be the same or different.
In the present embodiment, the thickness of the barrier material layer is 100nm to 500 nm. Can effectively prevent manganese from dissolving out. Further, the thickness of the barrier material layer is 150nm-480 nm. Further, the thickness of the barrier material layer is 180nm-430 nm. In particular, the thickness of the layer of barrier material may be, but is not limited to, 130nm, 190nm, 200nm, 240nm, 300nm, 360nm, or 450 nm. In this application, when the lithium iron manganese phosphate composite material has multiple barrier material layers, the thickness of each barrier material layer may be the same or different. In one embodiment, when the lithium iron manganese phosphate composite material has multiple barrier material layers, the thickness of each barrier material layer is 100nm to 500 nm.
In the present application, the material of the lithium iron manganese phosphate layer includes LiMnyFe1-yPO4And y is less than x. That is, when the lithium iron manganese phosphate layer has a multilayer or single-layer structure, y is smaller than x. In the embodiment of the present application, the material of the lithium iron manganese phosphate layer of the outermost layer of the coating layer includes LiMnyFe1-yPO4Wherein y is more than 0 and less than or equal to 0.65. It will be appreciated that y is still less than x at this time. Further, the material of the manganese iron lithium phosphate layer at the outermost layer in the coating layer comprises LiMnyFe1-yPO4Y is more than or equal to 0.3 and less than or equal to 0.6. Furthermore, the material of the outermost lithium iron manganese phosphate layer in the coating layer comprises LiMnyFe1-yPO4Y is more than or equal to 0.5 and less than or equal to 0.6. The manganese dissolution of the low-manganese-content lithium manganese iron phosphate is less, the structural stability and the electrochemical stability of the composite material cannot be influenced too much, and meanwhile, the manganese content is lower, so that the performance of the lithium manganese iron phosphate is closer to that of the lithium iron phosphate, and the rate capability of the composite material is improved. In one embodiment, when the coating layer has a lithium iron manganese phosphate layer, the material of the lithium iron manganese phosphate layer includes LiMnyFe1-yPO4Wherein y is more than 0 and less than or equal to 0.65. In another embodiment, when the coating layer has multiple lithium iron manganese phosphate layers, the material of the outermost lithium iron manganese phosphate layer in the coating layer includes LiMnyFe1-yPO4Wherein y is more than 0 and less than or equal to 0.65.
In the embodiment of the present application, when the coating layer has a plurality of lithium iron manganese phosphate layers,LiMn material of multiple lithium iron manganese phosphate layers from inside to outsideyFe1-yPO4The content of the medium manganese is gradually reduced or unchanged. In one embodiment, the inside-out multiple lithium iron manganese phosphate layers are LiMnyFe1-yPO4The medium manganese content gradually decreases. That is, the value of y gradually decreases from the inside to the outside. Therefore, the manganese content of the outmost lithium iron manganese phosphate layer in the lithium iron manganese phosphate composite material is low, the occurrence of manganese dissolution is greatly reduced, and the structural stability of the lithium iron manganese phosphate composite material is improved.
In the embodiment of the application, the mass of the lithium iron manganese phosphate layer accounts for 5% -20% of the total mass of the lithium iron manganese phosphate in the lithium iron manganese phosphate composite material. It can be understood that the lithium manganese iron phosphate composite material provided by the application can include one or more lithium manganese iron phosphate layers, and the mass of all the lithium manganese iron phosphate layers in the lithium manganese iron phosphate composite material accounts for 5% -20% of the total mass of the lithium manganese iron phosphate in the lithium manganese iron phosphate composite material. The lithium iron manganese phosphate layer occupies a small area, so that the occurrence of manganese dissolution in the lithium iron manganese phosphate layer is reduced, and the performance of the lithium iron manganese phosphate composite material is ensured. Furthermore, the mass of the lithium iron manganese phosphate layer accounts for 10% -15% of the total mass of the lithium iron manganese phosphate in the lithium iron manganese phosphate composite material. Specifically, the mass of the lithium iron manganese phosphate layer may be, but is not limited to, 7%, 8%, 10%, 13%, 14%, 17%, or 18% of the total mass of the lithium iron manganese phosphate in the lithium iron manganese phosphate composite material. In an embodiment of the present application, when the coating layer has multiple lithium iron manganese phosphate layers, the mass of each lithium iron manganese phosphate layer is gradually increased, gradually decreased, or unchanged in the ratio of the total mass of lithium iron manganese phosphate in the lithium iron manganese phosphate composite material from inside to outside. It can be understood that, when the coating layer has multiple lithium iron manganese phosphate layers, the proportion of each lithium iron manganese phosphate layer in the total mass of the lithium iron manganese phosphate in the lithium iron manganese phosphate composite material is influenced by the surface area and the thickness of each layer, and can be specifically selected according to needs.
In the embodiment of the application, the thickness of the lithium iron manganese phosphate layer is 300nm-1000nm, so that the phenomenon that manganese is dissolved out more due to over-thickness is avoided. Further, the thickness of the lithium iron manganese phosphate layer is 400nm-800 nm. Specifically, the thickness of the lithium iron manganese phosphate layer may be, but is not limited to, 350nm, 500nm, 600nm, 700nm, or 900 nm.
In the embodiment of the present application, the particle size of the lithium manganese iron phosphate primary particles in the lithium manganese iron phosphate layer is 30nm to 100 nm. Specifically, the particle size of the lithium manganese iron phosphate primary particles in the lithium manganese iron phosphate layer is 30nm, 35nm, 50nm, 60nm, 75nm, 80nm or 95 nm.
In the embodiment of the application, the inner core in the lithium iron manganese phosphate composite material accounts for 70-95 parts by weight. The core is used as a main component of the lithium manganese iron phosphate composite material, so that the lithium manganese iron phosphate composite material can be endowed with higher platform voltage and energy density, and the performance of the lithium manganese iron phosphate composite material is improved. Furthermore, the proportion of the inner core in the lithium iron manganese phosphate composite material is less than 95 parts by weight, so that the influence caused by excessive manganese dissolution when the content of manganese in the inner core is too high is further avoided. In one embodiment, the lithium iron manganese phosphate composite material has an inner core accounting for 80-90 parts. Furthermore, the inner core of the lithium iron manganese phosphate composite material accounts for 85-90 parts by weight. Specifically, the inner core of the lithium iron manganese phosphate composite material can be, but is not limited to, 75 parts, 85 parts, 87 parts, 88 parts, 92 parts or 94 parts by weight.
In the embodiment of the application, the barrier material layer in the lithium iron manganese phosphate composite material accounts for 0.24-0.6 part by weight. The barrier material layer is used as a component of the lithium iron manganese phosphate composite material, so that the structural stability of the lithium iron manganese phosphate composite material is improved. Furthermore, the barrier material layer in the lithium iron manganese phosphate composite material accounts for 0.3-0.6 part. Specifically, the barrier material layer in the lithium iron manganese phosphate composite material may be, but is not limited to, 0.3 part, 0.4 part, 0.5 part or 0.6 part by weight. In the application, when the lithium iron manganese phosphate composite material has multiple barrier material layers, each barrier material layer accounts for 0.24 to 0.6 parts by weight. The mass ratio of each barrier material layer in the lithium iron manganese phosphate composite material can be the same or different.
In the embodiment of the application, the lithium iron manganese phosphate layer in the lithium iron manganese phosphate composite material accounts for 5-20 parts by weight. The lithium iron manganese phosphate layer is used as a component of the lithium iron manganese phosphate composite material, so that the problem that the structure of the lithium iron manganese phosphate composite material is damaged due to the fact that more manganese is dissolved out can be solved, the lithium iron manganese phosphate composite material can be endowed with higher energy density, meanwhile, the manganese content in the lithium iron manganese phosphate layer is relatively small and is close to the performance of lithium iron manganese phosphate, and the cycle performance of the lithium iron manganese phosphate composite material is improved. Further, the lithium iron manganese phosphate layer in the lithium iron manganese phosphate composite material accounts for 10-15 parts by weight. Specifically, the lithium iron manganese phosphate layer in the lithium iron manganese phosphate composite material is 6 parts, 7 parts, 9 parts, 12 parts, 15 parts or 18 parts by weight. In the present application, when the lithium iron manganese phosphate composite material has a plurality of lithium iron manganese phosphate layers, each lithium iron manganese phosphate layer accounts for 5 to 20 parts by weight. The mass ratio of each lithium iron manganese phosphate layer in the lithium iron manganese phosphate composite material can be the same or different.
In an embodiment of the present application, the lithium iron manganese phosphate composite material further includes a carbon coating layer, and the carbon coating layer coats the coating layer. Referring to fig. 3, a schematic structural diagram of a lithium iron manganese phosphate composite material according to another embodiment of the present disclosure is shown, where the lithium iron manganese phosphate composite material includes a core 10, a coating layer 20 coating the core 10, and a carbon coating layer 30 coating the coating layer 20. Through the arrangement of the carbon coating layer, the conductivity of the lithium iron manganese phosphate composite material is improved, and the charge and discharge performance of the lithium iron manganese phosphate composite material is ensured. In one embodiment, the mass content of the carbon coating layer in the lithium iron manganese phosphate composite material is 0.5% -5%. The conductivity of the lithium iron manganese phosphate composite material can be improved, and the cycle rate and the high energy density of the lithium iron manganese phosphate composite material cannot be influenced too much. Further, the mass content of the carbon coating layer in the lithium iron manganese phosphate composite material is 1-4%.
In one embodiment of the present application, the primary particles of the lithium iron manganese phosphate composite material have a particle size of 30nm to 100 nm. Specifically, the particle size of the primary particle of the lithium iron manganese phosphate composite material is 30nm, 40nm, 50nm, 65nm, 80nm, 90nm or 95 nm. In another embodiment of the present application, the lithium iron manganese phosphate composite further comprises agglomerated primary particles of the lithium iron manganese phosphate composite.
The application also provides a preparation method of the lithium iron manganese phosphate composite material, and the lithium iron manganese phosphate composite material in any one of the above embodiments is prepared by the method, which comprises the following steps: forming a coating layer on the surface of the inner core through solid-phase sintering to obtain the lithium iron manganese phosphate composite material, wherein the coating layer comprises at least one barrier material layer and at least one lithium iron manganese phosphate layer, the barrier material layer and the lithium iron manganese phosphate layer are sequentially and alternately stacked on the surface of the inner core, and the material of the inner core comprises LiMnxFe1-xPO4The material of the lithium iron manganese phosphate layer comprises LiMnyFe1-yPO4Wherein y < x.
Referring to fig. 4, a flow chart of a preparation method of a lithium iron manganese phosphate composite material according to an embodiment of the present application includes:
operation 101: providing a core material comprising LiMnxFe1-xPO4。
Operation 102: and mixing the core material and the barrier material, and performing solid-phase sintering to obtain an intermediate.
Operation 103: the intermediate, the manganese iron phosphate and the lithium source are mixed, and the manganese iron phosphate composite material is obtained through solid phase sintering, the manganese iron phosphate composite material comprises a core formed by a core material and a coating layer for coating the core, the coating layer comprises a barrier material layer and a manganese iron phosphate lithium layer, the barrier material layer and the manganese iron phosphate lithium layer are sequentially arranged on the surface of the core, and the manganese iron phosphate lithium layer is made of LiMnyFe1-yPO4Wherein y < x.
The coating layer with the barrier material layer and the lithium iron manganese phosphate layer can be prepared by the preparation method.
In another embodiment of the present application, a method for preparing a lithium iron manganese phosphate composite material includes: mixing the core material and the barrier material, performing solid-phase sintering, mixing with ferric manganese phosphate and a lithium source, and performing solid-phase sintering to obtain a transition material; and repeating the steps on the transition material to obtain the lithium iron manganese phosphate composite material.
The coating layer with multiple layers of barrier material layers and multiple layers of lithium iron manganese phosphate layers can be prepared by the preparation method. In one embodiment, the number of repetitions is greater than or equal to 1, and two or more layers of barrier material and two or more layers of lithium iron manganese phosphate can be formed.
In an embodiment of the present application, providing a core material includes: uniformly mixing ferric manganese phosphate and a lithium source, and adding water for grinding; after spray drying, sintering and air crushing are carried out to obtain the core material. In one embodiment, the mixing time is 0.5h to 1.5 h. Further, the mixing time is 0.75h-1.2 h. Thereby allowing the ferromanganese phosphate and the lithium source to be thoroughly mixed. In another embodiment, milling comprises milling to a particle size of less than 25 μm in grinding media having a diameter of 0.6mm to 0.8mm followed by milling to a particle size of 20nm to 30nm in grinding media having a diameter of 0.1mm to 0.3 mm. In yet another embodiment, sintering comprises performing in an atmosphere having an oxygen concentration of less than 150 ppm. Further, the sintering curve comprises a temperature rising section, a constant temperature section and a temperature reduction section. In a specific embodiment, the first temperature raising section comprises raising the temperature to 400 ℃ for 2.5h-3.5 h; the constant temperature of the first constant temperature section is 400 ℃, and the first constant temperature time is 3.5h-5.5 h; the second temperature rise section is to heat up to 400-700 ℃, and the temperature rise time is 3-4 h; the constant temperature of the second constant temperature section is 700 ℃, and the constant temperature time is 2.5h-4.5 h; the temperature of the cooling section is reduced to 50 ℃, and the cooling time is 5.5h-7.5 h. In yet another embodiment, the particles having a median particle diameter D50 of 6 μm to 12 μm are obtained by classification after gas milling.
In the embodiment of the application, the mass of the barrier material accounts for 0.3-0.6% of the mass of the core material. Therefore, the barrier material is favorable for completely coating the core formed by the core material in the solid-phase sintering process, and the overall performance of the lithium iron manganese phosphate composite material is favorably improved.
In an embodiment of the present application, solid phase sintering comprises sintering at 500 ℃ to 1000 ℃ for 3h to 20 h. The coating layer is formed by high-temperature solid-phase sintering. In one embodiment, solid phase sintering comprises sintering at 500 ℃ to 800 ℃ for 3h to 5 h. Thereby being beneficial to the barrier material to completely coat the inner core, further reducing the possibility of manganese dissolution and improving the overall performance of the lithium iron manganese phosphate composite material.
In the embodiment of the application, the core material and the barrier material are mixed, and after solid-phase sintering, the mixture is also subjected to gas crushing to obtain particles with the median particle diameter D50 of 5-8 μm. Thereby obtaining an intermediate material with proper grain size, and being beneficial to the subsequent coating of the lithium iron manganese phosphate layer and the carbon coating layer.
In the present application, the intermediate body includes an inner core formed of an inner core material, and a barrier layer formed of a barrier material, and the barrier layer covers the inner core.
In an embodiment of the present application, the lithium source includes at least one of lithium hydroxide, lithium carbonate, lithium nitrate, lithium oxalate, lithium dihydrogen phosphate, lithium citrate, and lithium acetate.
In an embodiment of the present application, the intermediate, the manganese iron phosphate, and the lithium source are mixed, and the solid-phase sintering is performed to obtain the lithium iron manganese phosphate composite material, including: and mixing the intermediate, the manganese iron phosphate and a lithium source, performing solid-phase sintering, performing mechanical fusion, performing spray drying, performing secondary solid-phase sintering, performing gas crushing, and removing iron to obtain the lithium iron manganese phosphate composite material.
In one embodiment of the present application, the spray drying comprises performing at a temperature of 150 ℃ to 200 ℃. Further, the spray drying comprises performing at 160 ℃ to 180 ℃. In one embodiment of the present application, gas milling comprises a gas milling treatment at 3MPa to 5MPa for 2h to 3h to obtain a material with a suitable particle size.
In the application, the intermediate, the ferromanganese phosphate and the lithium source are mixed and subjected to solid-phase sintering to obtain the lithium iron manganese phosphate composite material, wherein the ferromanganese phosphate and the lithium source form a lithium iron manganese phosphate layer in the process. The content of manganese element in the manganese-iron phosphate is controlled, so that the material LiMn of the formed lithium iron manganese phosphate layeryFe1-yPO4The content of medium manganese is less than that of the LiMn core materialxFe1- xPO4The content of medium manganese.
In an embodiment of the present application, the intermediate, the manganese iron phosphate, and the lithium source are mixed, and the solid-phase sintering is performed to obtain the lithium iron manganese phosphate composite material, including: and mixing the intermediate, the ferromanganese phosphate, a lithium source and a carbon source, and performing solid-phase sintering to obtain the lithium iron manganese phosphate composite material. Thereby obtaining the lithium iron manganese phosphate composite material with the carbon coating layer and improving the conductivity of the lithium iron manganese phosphate composite material. In one embodiment, the carbon source comprises at least one of glucose, sucrose, starch, fructose, citric acid, ascorbic acid, and polyethylene glycol.
The preparation method of the lithium iron manganese phosphate composite material is simple, the raw material source is rich and easy to obtain, the lithium iron manganese phosphate composite material is suitable for large-scale production, and the lithium iron manganese phosphate composite material with excellent performance is prepared.
The application also provides a positive electrode, and the positive electrode comprises the lithium iron manganese phosphate composite material in any one of the above embodiments.
The application also provides a lithium ion battery which comprises a positive electrode, a negative electrode and electrolyte, wherein the positive electrode comprises the lithium iron manganese phosphate composite material in any one of the above embodiments.
In a lithium ion battery, manganese in high-manganese-content lithium manganese iron phosphate is dissolved out and then reduced at a negative electrode, the manganese is deposited on a solid electrolyte interface film to damage the structure of the lithium manganese iron phosphate, and lithium ions are consumed when the damaged solid electrolyte interface film is repaired, so that the structural stability and the performance of the lithium manganese iron phosphate are greatly reduced; in the application, the barrier material layer blocks the direct contact between the core and the electrolyte, and effectively reduces the dissolution of manganese in the high-manganese-content lithium manganese iron phosphate core, so that the dissolution of manganese in the use process of the lithium manganese iron phosphate composite material is reduced, the damage to other structures of the lithium ion battery is also avoided, and the structural stability and excellent performance of the lithium ion battery are ensured. The lithium ion battery provided by the application has excellent structural stability and electrochemical performance, and is beneficial to wide application.
Example 1
A lithium iron manganese phosphate composite material comprises LiMn0.75Fe0.25PO4The formed inner core, a titanium oxide layer wrapping the inner core and LiMn wrapping the titanium oxide layer0.55Fe0.45PO4Layer and coating LiMn0.55Fe0.45PO4A carbon coating layer, wherein the manganese iron lithium phosphate composite material comprises 70 parts of inner core and LiMn by weight0.55Fe0.45PO430 parts of layer, 0.4 part of titanium oxide layer and carbon coatingThe layer accounts for 2 parts, and the thickness of the titanium oxide layer is 200 nm. Wherein, the manganese content in the lithium manganese iron phosphate is measured and added with hydrochloric acid and nitric acid for heating and digestion (l mL (V) according to GB/T9723-2007 general rules of chemical reagent flame atomic absorption Spectroscopy)HCl:VH2O＝1:1)+3mL HNO3) Filtering with filter paper, and washing the filter paper with deionized water for more than three times to ensure that ions fully enter the filtrate and the volume is 100 mL; and detecting the metal content by adopting ICP-OES.
Example 2
A lithium iron manganese phosphate composite material comprises LiMn0.75Fe0.25PO4The formed inner core, a titanium oxide layer wrapping the inner core and LiMn wrapping the titanium oxide layer0.55Fe0.45PO4Layer and coating LiMn0.55Fe0.45PO4A carbon coating layer, wherein the inner core of the lithium iron manganese phosphate composite material accounts for 80 parts by weight, and LiMn0.55Fe0.45PO420 parts of layer, 0.4 part of titanium oxide layer and 2 parts of carbon coating layer.
Example 3
A lithium iron manganese phosphate composite material comprises LiMn0.75Fe0.25PO4The formed inner core, a titanium oxide layer wrapping the inner core and LiMn wrapping the titanium oxide layer0.55Fe0.45PO4Layer and coating LiMn0.55Fe0.45PO4A carbon coating layer, wherein the manganese iron lithium phosphate composite material comprises 85 parts of inner core and LiMn by weight0.55Fe0.45PO415 parts of layer, 0.4 part of titanium oxide layer and 2 parts of carbon coating layer.
Example 4
A lithium iron manganese phosphate composite material comprises LiMn0.75Fe0.25PO4The formed inner core, a titanium oxide layer wrapping the inner core and LiMn wrapping the titanium oxide layer0.55Fe0.45PO4Layer and coating LiMn0.55Fe0.45PO4A carbon coating layer, wherein the lithium iron manganese phosphate composite material comprises 90 parts of inner core and LiMn by weight0.55Fe0.45PO410 parts of layer, 0.4 part of titanium oxide layer and 2 parts of carbon coating layer.
Example 5
A lithium iron manganese phosphate composite material comprises LiMn0.75Fe0.25PO4The formed inner core, a titanium oxide layer wrapping the inner core and LiMn wrapping the titanium oxide layer0.55Fe0.45PO4Layer and coating LiMn0.55Fe0.45PO4A carbon coating layer, wherein the manganese iron lithium phosphate composite material comprises 95 parts of inner core and LiMn by weight0.55Fe0.45PO45 parts of layer, 0.4 part of titanium oxide layer and 2 parts of carbon coating layer.
Example 6
A lithium iron manganese phosphate composite material comprises LiMn0.75Fe0.25PO4The formed inner core, a titanium oxide layer wrapping the inner core and LiMn wrapping the titanium oxide layer0.55Fe0.45PO4Layer and coating LiMn0.55Fe0.45PO4A carbon coating layer, wherein the inner core of the lithium iron manganese phosphate composite material accounts for 98 parts by weight, and LiMn0.55Fe0.45PO42 parts of layer, 0.4 part of titanium oxide layer and 2 parts of carbon coating layer.
Example 7
A lithium iron manganese phosphate composite material comprises LiMn0.65Fe0.35PO4The formed inner core, a titanium oxide layer wrapping the inner core and LiMn wrapping the titanium oxide layer0.5Fe0.5PO4Layer and coating LiMn0.5Fe0.5PO4A carbon coating layer, wherein the manganese iron lithium phosphate composite material comprises 85 parts of inner core and LiMn by weight0.5Fe0.5PO415 parts of layer, 0.4 part of titanium oxide layer and 2 parts of carbon coating layer.
Example 8
A lithium iron manganese phosphate composite material comprises LiMn0.8Fe0.2PO4The formed inner core, a titanium oxide layer wrapping the inner core and LiMn wrapping the titanium oxide layer0.6Fe0.4PO4Layer and coating LiMn0.6Fe0.4PO4A carbon coating layer, wherein the manganese iron lithium phosphate composite material comprises 85 parts of inner core and LiMn by weight0.6Fe0.4PO415 parts of layer, 0.4 part of titanium oxide layer and 2 parts of carbon coating layer.
Example 9
A lithium iron manganese phosphate composite material comprises LiMn0.85Fe0.15PO4The formed inner core, a titanium oxide layer wrapping the inner core and LiMn wrapping the titanium oxide layer0.65Fe0.35PO4Layer and coating LiMn0.65Fe0.35PO4A carbon coating layer, wherein the manganese iron lithium phosphate composite material comprises 85 parts of inner core and LiMn by weight0.65Fe0.35PO415 parts of layer, 0.4 part of titanium oxide layer and 2 parts of carbon coating layer.
Example 10
A lithium iron manganese phosphate composite material comprises LiMn0.95Fe0.05PO4The formed inner core, a titanium oxide layer wrapping the inner core and LiMn wrapping the titanium oxide layer0.4Fe0.6PO4Layer and coating LiMn0.4Fe0.6PO4A carbon coating layer, wherein the manganese iron lithium phosphate composite material comprises 85 parts of inner core and LiMn by weight0.4Fe0.6PO415 parts of layer, 0.4 part of titanium oxide layer and 2 parts of carbon coating layer.
Example 11
A lithium iron manganese phosphate composite material comprises LiMn0.75Fe0.25PO4The formed inner core, a titanium oxide layer wrapping the inner core and LiMn wrapping the titanium oxide layer0.55Fe0.45PO4A layer, wherein, according to the weight portion, the manganese iron phosphate lithium composite material has 70 portions of inner core and LiMn0.55Fe0.45PO4The layer accounts for 30 parts, and the titanium oxide layer accounts for 0.4 part.
Example 12
A lithium iron manganese phosphate composite material comprises LiMn0.75Fe0.25PO4Formed ofInner core, aluminum oxide layer wrapping the inner core and LiMn wrapping the aluminum oxide layer0.55Fe0.45PO4Layer and coating LiMn0.55Fe0.45PO4A carbon coating layer, wherein the manganese iron lithium phosphate composite material comprises 70 parts of inner core and LiMn by weight0.55Fe0.45PO4The layer accounts for 30 parts, the alumina layer accounts for 0.5 part, the carbon coating layer accounts for 2 parts, and the thickness of the alumina layer is 400 nm.
Example 13
A lithium iron manganese phosphate composite material comprises LiMn0.75Fe0.25PO4The formed inner core, a titanium oxide layer wrapping the inner core and LiMn wrapping the titanium oxide layer0.55Fe0.45PO4Layer and coating LiMn0.55Fe0.45PO4A carbon coating layer, wherein the manganese iron lithium phosphate composite material comprises 70 parts of inner core and LiMn by weight0.55Fe0.45PO4The carbon coating layer accounts for 30 parts of the titanium layer, the titanium oxide layer accounts for 0.4 part of the titanium layer, the carbon coating layer accounts for 2 parts of the titanium layer, and the thickness of the titanium oxide layer is 50 nm.
Example 14
A lithium iron manganese phosphate composite material comprises LiMn0.75Fe0.25PO4The formed inner core, a titanium oxide layer wrapping the inner core and LiMn wrapping the titanium oxide layer0.55Fe0.45PO4Layer and coating LiMn0.55Fe0.45PO4A carbon coating layer, wherein the manganese iron lithium phosphate composite material comprises 70 parts of inner core and LiMn by weight0.55Fe0.45PO4The titanium oxide layer accounts for 30 parts, the titanium oxide layer accounts for 0.4 part, the carbon coating layer accounts for 2 parts, and the thickness of the titanium oxide layer is 600 nm.
Example 15
A lithium iron manganese phosphate composite material comprises LiMn0.75Fe0.25PO4The formed kernel, the aluminum metaphosphate layer wrapping the kernel and the LiMn wrapping the aluminum metaphosphate layer0.55Fe0.45PO4Layer and coating LiMn0.55Fe0.45PO4A carbon coating layer of the layer, wherein, calculated by weight portion, the lithium iron manganese phosphate composite material85 parts of middle core and LiMn0.55Fe0.45PO415 parts of layer, 0.4 part of aluminum metaphosphate layer and 2 parts of carbon coating layer.
Example 16
A lithium iron manganese phosphate composite material comprises LiMn0.75Fe0.25PO4An inner core formed, a yttrium pyrophosphate layer wrapping the inner core, and LiMn wrapping the yttrium pyrophosphate layer0.55Fe0.45PO4Layer and coating LiMn0.55Fe0.45PO4A carbon coating layer, wherein the manganese iron lithium phosphate composite material comprises 85 parts of inner core and LiMn by weight0.55Fe0.45PO415 parts of layer, 0.4 part of yttrium pyrophosphate layer and 2 parts of carbon coating layer.
Example 17
A lithium iron manganese phosphate composite material comprises LiMn0.75Fe0.25PO4The formed kernel is a titanium oxide layer and LiMn which wrap the kernel in sequence0.6Fe0.4PO4Layer, titanium oxide layer, LiMn0.55Fe0.45PO4The lithium iron manganese phosphate composite material comprises a layer and a carbon coating layer, wherein the lithium iron manganese phosphate composite material comprises 70 parts of inner core and LiMn by weight0.6Fe0.4PO4Layer 10 parts, LiMn0.55Fe0.45PO4The layer accounts for 20 parts, the titanium oxide layer accounts for 0.4 part totally, and the carbon coating layer accounts for 2 parts.
Comparative example 1
A lithium iron manganese phosphate composite material comprises LiMn0.55Fe0.45PO4The formed inner core, a titanium oxide layer wrapping the inner core and LiMn wrapping the titanium oxide layer0.7Fe0.3PO4Layer and coating LiMn0.7Fe0.3PO4A carbon coating layer, wherein the manganese iron lithium phosphate composite material comprises 85 parts of inner core and LiMn by weight0.7Fe0.3PO415 parts of layer, 0.4 part of titanium oxide layer and 2 parts of carbon coating layer.
Comparative example 2
A lithium iron manganese phosphate composite material comprises LiMn0.75Fe0.25PO4The core and the carbon coating layer wrap the core are formed, wherein the core in the lithium iron manganese phosphate composite material accounts for 100 parts by weight, and the carbon coating layer accounts for 2 parts by weight.
Comparative example 3
A lithium iron manganese phosphate composite material comprises LiMn0.75Fe0.25PO4Formed kernel, LiMn wrapping the kernel0.55Fe0.45PO4Layer and coating LiMn0.55Fe0.45PO4A carbon coating layer, wherein the manganese iron lithium phosphate composite material comprises 85 parts of inner core and LiMn by weight0.55Fe0.45PO415 parts of layer and 2 parts of carbon coating layer.
Comparative example 4
A lithium iron manganese phosphate composite material comprises LiMn0.75Fe0.25PO4The core, the titanium oxide layer wrapping the core and the carbon coating layer wrapping the titanium oxide layer are formed, wherein the core, the titanium oxide layer and the carbon coating layer are respectively 100 parts, 0.4 part and 2 parts of the manganese lithium iron phosphate composite material in parts by weight.
Effects of the embodiment
Taking the carbon tube, the carbon black and the graphene according to the mass ratio of 0.6:0.5:0.2, and stirring the carbon tube, the carbon black and the graphene in a stirrer for 30min to obtain the conductive agent. And stirring the N-methyl pyrrolidone (NMP) and polyvinylidene fluoride (PVDF) in a stirrer for 1h to obtain the bonding slurry. And mixing the lithium iron manganese phosphate composite materials prepared in the embodiments and the comparative examples with a conductive agent and a bonding slurry, stirring for 1.5 hours, and sieving to obtain a positive electrode material, wherein the mass ratio of the lithium iron manganese phosphate composite material to the conductive agent to the bonding slurry is 100:2:2: 30. Coating the prepared anode material on an aluminum foil, and compacting to obtain an anode; combining the positive electrode, the graphite negative electrode, the diaphragm and the electrolyte to obtain the lithium ion battery, and carrying out the following detection:
specific capacity detection: the prepared surface density is 2g/dm2The single-sided positive plate of (1) is compacted to 2.65g/cm3And making the button cell 2025. The button cell is charged and discharged under 0.1C, CC-CV, 4.3V, 0.1C and 2.5V for three cycles, and the discharge capacity of the third cycle is takenAnd (4) calculating the specific capacity by combining the auxiliary material amount of the positive plate.
Detecting a median voltage: the median voltage was detected by the lithium ion cell 1/3C discharge curve.
And (3) testing rate performance: the lithium ion battery was charged at 25 ℃: charging to 4.2V at 0.2C constant current; discharging: constant current discharge is carried out to 2.5V at 0.2C and 5C under different multiplying factors. The ratio of 0.2C to 5C discharge capacity was calculated.
And (3) detecting the manganese content of the negative electrode: circulating the lithium ion battery at 45 ℃ and 2.5-4.3V for 500 times, disassembling the battery, and testing the manganese content in the negative electrode material in the negative electrode plate, wherein the manganese content adopts an ICP (inductively coupled plasma) testing method; the results of the above measurements are shown in Table 1.
TABLE 1 test results
Figure BDA0002702160110000171
It can be seen that through the arrangement of the barrier material layer, the manganese dissolution of the manganese-iron-lithium phosphate with high manganese content in the core is effectively improved, the structural stability of the manganese-iron-lithium phosphate composite material is further improved, meanwhile, the manganese-iron-lithium phosphate composite material has excellent electrochemical performance and is beneficial to the application of the manganese-iron-lithium phosphate composite material in a lithium ion battery, and the conductivity of the manganese-iron-lithium phosphate composite material can be further improved through the arrangement of the carbon coating layer, so that the application requirement can be further met.
The above-mentioned embodiments only express several embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present application. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the concept of the present application, which falls within the scope of protection of the present application. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. The lithium iron manganese phosphate composite material is characterized by comprising a core and a coating layer coating the core, wherein the coating layer comprises at least one barrier material layer andat least one lithium iron manganese phosphate layer, the barrier material layer with the lithium iron manganese phosphate layer is in the alternative range upon range of setting in proper order on the surface of kernel, the material of kernel includes LiMnxFe1-xPO4The material of the lithium iron manganese phosphate layer comprises LiMnyFe1-yPO4Wherein y < x.
2. The lithium iron manganese phosphate composite material of claim 1, wherein x has a value in a range of: x is more than or equal to 0.6 and less than 1.
3. The lithium iron manganese phosphate composite material according to claim 1, wherein a material of the lithium iron manganese phosphate layer at the outermost layer of the coating layers includes LiMnyFe1-yPO4Wherein y is more than 0 and less than or equal to 0.65.
4. The lithium iron manganese phosphate composite material according to claim 1, wherein when the coating layer has a plurality of the lithium iron manganese phosphate layers, the lithium iron manganese phosphate layer is made of LiMn in a direction from the core to the coating layeryFe1-yPO4The manganese content in the steel is gradually reduced.
5. The lithium iron manganese phosphate composite material of claim 1, further comprising a carbon coating layer, wherein the carbon coating layer coats the coating layer, and the mass content of the carbon coating layer in the lithium iron manganese phosphate composite material is 0.5% -5%.
6. The lithium iron manganese phosphate composite material of claim 1, wherein the material of the barrier material layer comprises at least one of a metal oxide, a metaphosphate and a pyrophosphate, and the thickness of the barrier material layer is 100nm to 500 nm.
7. The lithium iron manganese phosphate composite material of claim 1, wherein the mass of the core is 80% -95% of the total mass of lithium iron manganese phosphate in the lithium iron manganese phosphate composite material.
8. The preparation method of the lithium iron manganese phosphate composite material is characterized by comprising the following steps of:
forming a coating layer on the surface of the inner core through solid-phase sintering to obtain the lithium iron manganese phosphate composite material, wherein the coating layer comprises at least one layer of barrier material layer and at least one layer of lithium iron manganese phosphate layer, the barrier material layer and the lithium iron manganese phosphate layer are sequentially and alternately stacked on the surface of the inner core, and the material of the inner core comprises LiMnxFe1-xPO4The material of the lithium iron manganese phosphate layer comprises LiMnyFe1-yPO4Wherein y < x.
9. The preparation method according to claim 8, wherein the step of forming the coating layer on the surface of the inner core by solid-phase sintering to obtain the lithium iron manganese phosphate composite material comprises the following steps:
providing a core material comprising LiMnxFe1-xPO4；
Mixing the core material and the barrier material, and performing solid-phase sintering to obtain an intermediate;
and mixing the intermediate, the manganese iron phosphate and a lithium source, and performing solid-phase sintering to obtain the lithium iron manganese phosphate composite material.
10. A lithium ion battery comprises a positive electrode, a negative electrode and an electrolyte, wherein the positive electrode comprises the lithium iron manganese phosphate composite material prepared by the preparation method of any one of claims 1 to 7 or any one of claims 8 to 9.
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