CN118525386A - Composite positive electrode material, preparation method thereof, secondary battery, battery module, battery pack and power utilization device - Google Patents
Composite positive electrode material, preparation method thereof, secondary battery, battery module, battery pack and power utilization device Download PDFInfo
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- CN118525386A CN118525386A CN202280085899.4A CN202280085899A CN118525386A CN 118525386 A CN118525386 A CN 118525386A CN 202280085899 A CN202280085899 A CN 202280085899A CN 118525386 A CN118525386 A CN 118525386A
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- lithium
- positive electrode
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
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- 229910052744 lithium Inorganic materials 0.000 claims abstract description 79
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 76
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- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 7
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 83
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- 238000005245 sintering Methods 0.000 claims description 59
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Classifications
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application provides a composite positive electrode material, a preparation method thereof, a secondary battery, a battery module, a battery pack and an electric device. The composite positive electrode material comprises a lithium-containing metal oxide and a coating layer arranged on at least one part of the lithium-containing metal oxide, wherein the coating layer is a carbon-composite ferric manganese vanadium lithium phosphate material, the general formula of the ferric manganese vanadium lithium phosphate material is shown as a formula I, and LiFe a1Mnb1Vc1M2d1PO4, the formula I is that a1 is more than or equal to 0.1 and less than or equal to 0.8,0.1, b1 is more than or equal to 0.45,0.07, c1 is more than or equal to 0.3, d1 is more than or equal to 0 and less than or equal to 0.01, and M2 is one or more of Ni, co, ti, al. The carbon-composite ferric manganese vanadium lithium phosphate material at least partially coats the composite anode material of the lithium-containing metal oxide, so that the cycle performance, the storage performance and the safety performance of the battery can be improved.
Description
The application relates to the technical field of secondary batteries, in particular to a composite positive electrode material, a preparation method thereof, a secondary battery, a battery module, a battery pack and an electric device.
In recent years, the application range of secondary batteries is becoming wider and wider, and in particular, secondary batteries have been widely used in energy storage power supply systems such as hydraulic power, thermal power, wind power and solar power stations, and in various fields such as electric tools, electric bicycles, electric motorcycles, electric automobiles, military equipment, aerospace and the like.
With the increase in the demands of the market for the endurance and safety of electric devices, secondary batteries are required to have more excellent overall performance including capacity performance, safety performance, and cycle performance. The cathode material has an important influence on the electrochemical properties of the battery, such as gram capacity. However, the new generation of positive electrode materials brings about an increase in battery capacity with a concomitant decrease in cycle performance and safety performance. Accordingly, the existing positive electrode materials remain to be improved.
Disclosure of Invention
The present application aims to solve at least one of the technical problems existing in the prior art. Therefore, it is an object of the present application to provide a composite positive electrode material to further improve cycle performance, storage performance, and safety performance of a battery.
A first aspect of the present application provides a composite positive electrode material comprising: a lithium-containing metal oxide and a coating layer arranged on at least one part of the lithium-containing metal oxide, wherein the coating layer is a carbon composite ferric manganese vanadium lithium phosphate material, the general formula of the ferric manganese vanadium lithium phosphate material is shown as formula I,
LiFe a1Mn b1V c1M2 d1PO 4, formula I
Wherein a1 is more than or equal to 0.1 and less than or equal to 0.8,0.1, b1 is more than or equal to 0.45,0.07, c1 is more than or equal to 0.3, d1 is more than or equal to 0 and less than or equal to 0.01, and M2 is one or more selected from Ni, co, ti, al.
The composite positive electrode material prepared by coating the lithium-containing metal oxide with the carbon composite ferric manganese vanadium lithium phosphate material can improve the cycle capacity retention rate of the battery at normal temperature and high temperature, reduce the unit capacity gas production volume of the battery at high temperature, namely improve the cycle performance, the storage performance and the safety performance of the battery, and meanwhile, the capacity performance of the battery can not be obviously reduced by the coating layer, and the battery taking the composite positive electrode material as the positive electrode still has excellent capacity performance and initial electricity buckling effect.
In any embodiment, the mass content of the coating layer is 0.1% to 10% based on the total mass of the composite positive electrode material. The composite positive electrode material with proper coating amount can obtain a battery with high capacity performance, excellent cycle performance, storage performance and safety performance.
In any embodiment, the mass fraction of carbon in the coating is 0.01% to 25% based on the total mass of the coating. The carbon of suitable quality allows the coating to have low powder resistivity, high material stability and conductivity, which is beneficial to maintaining high capacity performance of the battery.
In any embodiment, the powder resistivity of the composite positive electrode material is 1000 to 5500 Ω·cm. When the powder resistivity of the composite positive electrode material is within the range, the composite positive electrode material has better stability and better conductivity, and is beneficial to maintaining and improving the capacity performance of the battery.
In any embodiment, the average particle diameter Dv50 of the composite positive electrode material is 8 to 12 μm. The particle size of the composite positive electrode material is too large to be beneficial to the intercalation and deintercalation of lithium ions, the particle size of the composite positive electrode material is too small, the material is easy to aggregate, and the average particle size of the composite positive electrode material is in a proper range, so that the battery can exert excellent electrochemical performance and cycle performance.
In any embodiment, the general formula of the lithium-containing metal oxide is shown in formula II,
Li 1.05-a2M1 a2(Ni b2Co c2Mn d2) 1-e2Q e2O 2, formula II
In the method, in the process of the invention, a2 is more than or equal to 0 and less than or equal to 0.1,0.7 is more than or equal to b 0.96,0.03 c22 is less than or equal to 0.96,0.03 c2 is less than or equal to; wherein M1 is selected from one or more of alkali metal elements Na, K, rb, cs, and Q is selected from one or more of Al, mg, zr, ti, W, Y, B, co, nb, mo, sb, sr.
The lithium-containing metal oxide is a high nickel metal oxide having a high energy density, which enables the battery to have high capacity and power performance.
The second aspect of the present application provides a method for preparing a composite positive electrode material, comprising the steps of:
Performing first sintering treatment on a first mixture containing a lithium source, an iron source, a manganese source, a vanadium source, a phosphorus source and a carbon source to prepare a carbon composite ferric manganese vanadium lithium phosphate material,
Performing second sintering treatment on a second mixture containing a lithium source and a nickel cobalt manganese precursor, wherein the molar ratio of lithium element in the lithium source to the sum of nickel element, cobalt element and manganese element in the nickel cobalt manganese precursor is 0.95-1.05, so as to prepare a lithium-containing metal oxide;
Performing third sintering treatment on the carbon-compounded ferric manganese vanadium lithium phosphate material and the lithium-containing metal oxide to obtain a compound anode material,
The composite positive electrode material comprises lithium-containing metal oxide and a coating layer arranged on at least one part of the lithium-containing metal oxide, wherein the coating layer is the carbon composite ferric manganese vanadium lithium phosphate material, the general formula of the ferric manganese vanadium lithium phosphate material is shown as formula I,
LiFe a1Mn b1V c1M2 d1PO 4, formula I
Wherein a1 is more than or equal to 0.1 and less than or equal to 0.8,0.1, b1 is more than or equal to 0.45,0.07, c1 is more than or equal to 0.3, d1 is more than or equal to 0 and less than or equal to 0.01, and M2 is one or more selected from Ni, co, ti, al.
According to the composite positive electrode material prepared by the method, the carbon composite ferric manganese vanadium lithium phosphate material is at least partially coated with the lithium-containing metal oxide, so that the cycle performance, the storage performance and the safety performance of the battery can be improved, and the capacity performance of the battery has higher retention rate and even can be further improved.
In any embodiment, in the third sintering process, the mass ratio of the lithium-containing metal oxide to the carbon-composited iron-manganese-vanadium-lithium phosphate material to the carbon is 9:1 to 999:1. The proper coating amount can give consideration to the high capacity performance of the battery and excellent cycle performance, storage performance and safety performance.
In any embodiment, in the first sintering treatment, the molar ratio of the vanadium element in the vanadium source to the iron element in the iron source is 0.5:8 to 4:1. The molar ratio of vanadium element to iron element is controlled, so that the cycle performance, the storage performance and the safety performance of the battery can be improved while the high rate performance of the battery is maintained.
In any embodiment, the mass ratio of the carbon element in the carbon source to the lithium iron manganese vanadium phosphate material is 1:9999-1:4. The carbon with proper quality enables the carbon-compounded ferric manganese vanadium lithium phosphate material to have low powder resistivity, and is beneficial to maintaining high capacity performance of the positive electrode material.
In any embodiment, the sintering temperature of the first sintering treatment is 650 ℃ to 800 ℃ and the sintering time of the first sintering treatment is 10 to 20 hours. The temperature and time of the first sintering treatment are controlled within a proper range, so that the preparation of the low-powder-resistivity and proper-average-particle-diameter Dv50 carbon composite ferric manganese vanadium lithium phosphate material is facilitated, and the lithium-containing metal oxide can be effectively coated, so that the cycle performance, the storage performance and the safety performance of the battery are improved.
In any embodiment, the first mixture further comprises one or more of a nickel source, a cobalt source, a titanium source, and an aluminum source, wherein the nickel source, the cobalt source, the titanium source, and the aluminum source are respectively selected from one or more of oxides, hydroxides, carbonates, and phosphates of nickel element, cobalt element, titanium element, and aluminum element. The stability of the coating layer can be improved by doping the elements, so that the cycle performance, the storage performance and the safety performance of the battery are optimized.
In any embodiment, the iron source is selected from one or more of ferric oxide and ferric oxide; the manganese source is selected from one or more of manganese dioxide and manganous-manganic oxide; the vanadium source is selected from one or more of vanadium trioxide and vanadium pentoxide; the phosphorus source is selected from one or more of ammonium phosphate, monoammonium phosphate and lithium phosphate; the carbon source is selected from one or more of carbon black, citric acid, polyethylene glycol, sucrose and glucose.
In any embodiment, the second mixture further comprises an alkali metal compound in an amount of 0 to 5.5% by mass, based on the total mass of the second mixture. The lithium-containing metal oxide is doped with alkali metal, so that the diffusion efficiency of lithium ions can be optimized, and the rate performance, the cycle performance, the storage performance and the first-time electricity buckling effect of the battery are improved.
A third aspect of the present application provides a secondary battery comprising a positive electrode sheet, a separator, a negative electrode sheet, and an electrolyte, the positive electrode sheet comprising the composite positive electrode material of any of the embodiments of the first aspect. The battery has good cycle performance, storage performance and safety performance.
A fourth aspect of the application provides a battery module comprising the secondary battery of the third aspect. The battery module has good cycle performance, storage performance and safety performance.
A fifth aspect of the present application provides a battery pack including the battery module of the fourth aspect. The battery pack has good cycle performance, storage performance and safety performance.
A sixth aspect of the present application provides an electric device including at least one of the secondary battery of the third aspect, the battery module of the fourth aspect, and the battery pack of the fifth aspect. The electric device has good endurance and safety.
The foregoing description is only an overview of the present application, and is intended to be implemented in accordance with the teachings of the present application in order that the same may be more clearly understood and to make the same and other objects, features and advantages of the present application more readily apparent.
Fig. 1 is an SEM image of the composite positive electrode material prepared in example 1 of the present invention.
Fig. 2 is a graph for testing 25 ℃ cycle performance of a secondary battery made of the composite cathode material prepared in example 1 of the present invention.
Fig. 3 is a schematic view of a secondary battery according to an embodiment of the present application.
Fig. 4 is an exploded view of the secondary battery according to an embodiment of the present application shown in fig. 3.
Fig. 5 is a schematic view of a battery module according to an embodiment of the present application.
Fig. 6 is a schematic view of a battery pack according to an embodiment of the present application.
Fig. 7 is an exploded view of the battery pack of the embodiment of the present application shown in fig. 6.
Fig. 8 is a schematic view of an electric device in which a secondary battery according to an embodiment of the present application is used as a power source.
Reference numerals illustrate:
1, a battery pack; 2, upper box body; 3, lower box body; 4, a battery module; 5 a secondary battery; 51 a housing; 52 electrode assembly; 53 top cap assembly.
Hereinafter, embodiments of the binder, the method of producing the binder, the electrode, the battery, and the electric device according to the present application are specifically disclosed with reference to the accompanying drawings. However, unnecessary detailed description may be omitted. For example, detailed descriptions of well-known matters and repeated descriptions of the actual same structure may be omitted. This is to avoid that the following description becomes unnecessarily lengthy, facilitating the understanding of those skilled in the art. Furthermore, the drawings and the following description are provided for a full understanding of the present application by those skilled in the art, and are not intended to limit the subject matter recited in the claims.
The "range" disclosed herein is defined in terms of lower and upper limits, with the given range being defined by the selection of a lower and an upper limit, the selected lower and upper limits defining the boundaries of the particular range. Ranges that are defined in this way can be inclusive or exclusive of the endpoints, and any combination can be made, i.e., any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are also contemplated. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3,4 and 5 are listed, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In the present application, unless otherwise indicated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" have been listed throughout, and "0-5" is simply a shorthand representation of a combination of these values. When a certain parameter is expressed as an integer of 2 or more, it is disclosed that the parameter is, for example, an integer of 2,3, 4,5, 6,7,8, 9, 10, 11, 12 or the like.
All embodiments of the application and alternative embodiments may be combined with each other to form new solutions, unless otherwise specified.
All technical features and optional technical features of the application may be combined with each other to form new technical solutions, unless specified otherwise.
All the steps of the present application may be performed sequentially or randomly, preferably sequentially, unless otherwise specified. For example, the method comprises steps (a) and (b), meaning that the method may comprise steps (a) and (b) performed sequentially, or may comprise steps (b) and (a) performed sequentially. For example, the method may further include step (c), which means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), may include steps (a), (c) and (b), may include steps (c), (a) and (b), and the like.
The terms "comprising" and "including" as used herein mean open ended or closed ended, unless otherwise noted. For example, the terms "comprising" and "comprises" may mean that other components not listed may be included or included, or that only listed components may be included or included.
The term "or" is inclusive in this application, unless otherwise specified. For example, the phrase "a or B" means "a, B, or both a and B. More specifically, either of the following conditions satisfies the condition "a or B": a is true (or present) and B is false (or absent); a is false (or absent) and B is true (or present); or both A and B are true (or present).
High nickel lithium-containing metal oxides are commonly used in the prior art as positive electrode materials to increase battery capacity. However, since the surface of the high-nickel lithium-containing metal oxide is rich in defects and has high content of highly oxidative transition metal elements Ni, co, mn, etc., side reactions with the electrolyte are serious, so that the contact interface structure is easily damaged, the transition metal elements Ni, mn, co, etc., are easily dissolved out and deposited to the anode, resulting in an increase in the internal resistance of the battery, thereby causing serious cycle capacity failure of the battery and reducing the cycle performance of the battery. In addition, the high-nickel lithium-containing metal oxide has an unstable surface structure under the catalysis of electrolyte, is easy to release oxygen and is accompanied with heat release phenomenon when being extruded or at high temperature, is easy to cause thermal runaway of a battery core, and can cause safety accidents seriously. Although the conventional coating layer treatment can improve the cycle performance and the safety performance to some extent, the improvement range is limited, and it is difficult to meet the market demand for a new generation of battery.
[ Composite cathode Material ]
Based on this, the application proposes a composite positive electrode material comprising: a lithium-containing metal oxide and a coating layer arranged on at least one part of the lithium-containing metal oxide, wherein the coating layer is a carbon composite ferric manganese vanadium lithium phosphate material, the general formula of the ferric manganese vanadium lithium phosphate material is shown as formula I,
LiFe a1Mn b1V c1M2 d1PO 4, formula I
Wherein a1 is more than or equal to 0.1 and less than or equal to 0.8,0.1, b1 is more than or equal to 0.45,0.07, c1 is more than or equal to 0.3, d1 is more than or equal to 0 and less than or equal to 0.01, and M2 is one or more selected from Ni, co, ti, al.
In some embodiments, the carbon-composited lithium iron manganese vanadium phosphate material is a composite material comprising carbon and a lithium iron manganese vanadium phosphate material. It will be appreciated that the carbon and lithium iron manganese vanadium phosphate material may be composited in any manner, such as physical mixing, chemical compositing, and the like. Specifically, the carbon and the lithium iron manganese vanadium phosphate material can be compounded in the modes of stirring, grinding, ultrasonic treatment, in-situ growth, grafting, coating and the like.
In some embodiments, 0< d2.ltoreq.0.01, one or more of Ni, co, ti, al are included in the carbon-composited iron-manganese-vanadium-lithium phosphate material.
The lithium iron manganese vanadium phosphate material has the advantages of good stability, high potential and high multiplying power. The surface of the lithium-containing metal oxide can be protected by using the lithium-containing metal oxide as a coating layer, and the stability of the surface of the lithium-containing metal oxide and the interface between the lithium-containing metal oxide and the electrolyte can be improved. The composite positive electrode material prepared by coating the lithium-containing metal oxide with the carbon composite ferric manganese vanadium lithium phosphate material can improve the cycle capacity retention rate of the battery at normal temperature and high temperature, reduce the unit capacity gas production volume of the battery at high temperature, namely improve the cycle performance, the storage performance and the safety performance of the battery, and meanwhile, the capacity performance of the battery can not be greatly reduced by the coating layer, and the battery taking the composite positive electrode material as the positive electrode still has excellent capacity performance and initial electricity buckling effect.
In some embodiments, the mass content of the coating layer is 0.1% to 10% based on the total mass of the composite positive electrode material. In some embodiments, the coating is 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% by mass.
Too high a mass content of the coating layer may result in too low a mass content of the lithium-containing metal oxide, and a decrease in battery capacity. The mass content of the coating layer is too low, and the carbon composite ferric manganese vanadium lithium phosphate material cannot realize effective coating, so that the effect of improving the cycle performance and the storage performance of the battery is achieved. The proper coating amount can give consideration to the capacity performance, the cycle performance and the storage performance of the battery, and can keep and even improve the capacity performance and the first-effect of the power buckling of the battery while further improving the cycle performance, the storage performance and the safety performance of the battery.
In some embodiments, the mass fraction of carbon in the coating is 0.01% to 25% based on the total mass of the coating. In some embodiments, the mass fraction of carbon in the coating may be selected from 0.1%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%.
In some embodiments, a carbon content analyzer is used to test the mass content of carbon elements in the carbon-composite iron-manganese-vanadium-lithium phosphate material. Herein, the mass content of the carbon element in the carbon-composite iron-manganese-vanadium-lithium phosphate material may be adjusted by changing the mass of the added carbon source during the preparation of the carbon-composite iron-manganese-vanadium-lithium phosphate material.
The high mass content of carbon element in the coating layer easily causes the reduction of the ratio of the ferric manganese vanadium lithium phosphate in the ferric manganese vanadium lithium phosphate material compounded by carbon, and the characteristics of good stability and high voltage platform of the ferric manganese vanadium lithium phosphate can not be exerted. The mass content of the carbon element in the coating layer is too low, and the conductivity of the coating layer is too low, so that effective transmission of electrons cannot be realized. The mass content of the carbon element in the carbon composite oxide particle ferric manganese vanadium lithium phosphate material is controlled within a proper range, the carbon composite ferric manganese vanadium lithium phosphate material with uniform particle size distribution and high carbon element dispersibility can be obtained through uniform carbon composite, the coating layer has proper powder resistivity, the deintercalation of lithium ions is easy to realize, and even under the condition that the coating layer is added, the capacity performance and initial performance of the battery can be further maintained or improved, and the battery performance cannot be deteriorated due to the addition of the coating layer.
In some embodiments, the composite positive electrode material has a powder resistivity of 1000 to 5500 Ω -cm. In some embodiments, the powder resistivity of the composite positive electrode material is 1100Ω·cm, 1500Ω·cm, 2000 Ω·cm, 2500Ω·cm, 200Ω·cm, 4000 Ω·cm, 4500Ω·cm, 5000 Ω·cm, 5500 Ω·cm.
In this context, the term "powder resistivity" refers to a parameter used to characterize the electrical conductivity of the material itself, which is different from the resistivity of the pole piece. Typically, the powder resistivity is measured using a tester such as a four-probe tester, in accordance with GB/T30835-2014, lithium ion battery carbon composite lithium iron phosphate cathode material.
When the powder resistivity of the composite positive electrode material is within the range, the composite positive electrode material has better stability and better conductivity, and is beneficial to maintaining and improving the capacity performance of the battery.
In some embodiments, the average particle diameter Dv50 of the composite positive electrode material is 8 to 12 μm. In some embodiments, the average particle size Dv50 of the composite positive electrode material is 8.5 μm, 9 μm, 9.5 μm,10 μm, 10.5 μm, 11 μm, 11.5 μm, 12 μm.
In this context, the average particle diameter Dv50 is a meaning known in the art and means the particle diameter corresponding to a cumulative volume distribution percentage of the material of up to 50%. The determination may be performed using methods and instruments known in the art. For example, the particle size distribution can be measured by a laser particle size analyzer by referring to GB/T19077-2016 particle size distribution laser diffraction method.
The particle size of the composite positive electrode material is too large to be beneficial to the intercalation and deintercalation of lithium ions, the particle size of the composite positive electrode material is too small, the material is easy to aggregate, and the average particle size of the composite positive electrode material is in a proper range, so that the battery can exert excellent electrochemical performance and cycle performance.
In some embodiments, the lithium-containing metal oxide has the general formula of formula II,
Li 1.05-a2M1 a2(Ni b2Co c2Mn d2) 1-e2Q e2O 2, formula II
In the method, in the process of the invention, a2 is more than or equal to 0 and less than or equal to 0.1,0.7 is more than or equal to b 0.96,0.03 c22 is less than or equal to 0.96,0.03 c2 is less than or equal to; wherein M1 is selected from one or more of alkali metal elements Na, K, rb, cs, and Q is selected from one or more of Al, mg, zr, ti, W, Y, B, co, nb, mo, sb, sr.
In some embodiments, 0< a1.ltoreq.0.1. In the preparation process of the metal oxide containing lithium, na, K, rb, cs of carbonate, sulfate, chloride or oxide is added for co-sintering to realize the doping of alkali metal elements. The lithium-containing metal oxide is doped with alkali metal, so that the diffusion efficiency of lithium ions can be improved, and the high capacity and high rate performance of the battery can be further maintained.
In some embodiments, 0< e1+.0.05. In the preparation process of the metal oxide containing lithium, al, mg, zr, ti, W, Y, B, co, nb, mo, sb, sr of oxide, hydroxide, carbonate or phosphate is added for co-sintering to realize the doping of the transition metal element. The doping of the transition metal element can improve the structural stability of the lithium-containing metal oxide, stabilize the structural framework, and further improve the cycle performance and high rate performance of the battery.
The lithium-containing metal oxide has high nickel content and high energy density, and can enable the battery to have high capacity performance and power performance.
In one embodiment of the present application, there is provided a method for preparing a composite positive electrode material, including the steps of:
Performing first sintering treatment on a first mixture containing a lithium source, an iron source, a manganese source, a vanadium source, a phosphorus source and a carbon source to prepare a carbon composite ferric manganese vanadium lithium phosphate material,
Performing second sintering treatment on a second mixture containing a lithium source and a nickel cobalt manganese precursor, wherein the molar ratio of lithium element in the lithium source to the sum of nickel element, cobalt element and manganese element in the nickel cobalt manganese precursor is 0.95-1.05, so as to prepare a lithium-containing metal oxide;
performing third sintering treatment on the carbon composite ferric manganese vanadium lithium phosphate material and the lithium-containing metal oxide to obtain a composite anode material,
The composite positive electrode material comprises lithium-containing metal oxide and a coating layer arranged on at least one part of the lithium-containing metal oxide, wherein the coating layer is a carbon composite ferric manganese vanadium lithium phosphate material, the general formula of the ferric manganese vanadium lithium phosphate material is shown as formula I,
LiFe a1Mn b1V c1M2 d1PO 4, formula I
Wherein a1 is more than or equal to 0.1 and less than or equal to 0.8,0.1, b1 is more than or equal to 0.45,0.07, c1 is more than or equal to 0.3, d1 is more than or equal to 0 and less than or equal to 0.01, and M2 is one or more selected from Ni, co, ti, al.
In some embodiments, the sintering temperature of the third sintering process is 100 to 400 ℃.
In some embodiments, the sintering time of the third sintering process is 2 to 8 hours.
In some embodiments, the third sintering process is performed under a reducing atmosphere, which is nitrogen or argon.
According to the composite positive electrode material prepared by the method, the carbon composite ferric manganese vanadium lithium phosphate material is at least partially coated with the lithium-containing metal oxide, so that the cycle performance, the storage performance and the safety performance of the battery can be improved, and the capacity performance of the battery has excellent retention rate and even can be further improved.
In some embodiments, in the third sintering process, the mass ratio of lithium-containing metal oxide to carbon-composited iron-manganese-vanadium-lithium phosphate material to the material is 9:1 to 999:1.
The content of the lithium-containing metal oxide is too low, the high capacity performance of the battery is difficult to maintain, the content of the carbon-compounded ferric manganese vanadium lithium phosphate material is too low, effective coating cannot be formed on the lithium-containing metal oxide, and the improvement of the cycle performance, the storage performance and the safety performance is limited.
The proper coating amount can give consideration to the high capacity performance of the battery and excellent cycle performance, storage performance and safety performance.
In some embodiments, the lithium source is one or more of lithium carbonate, lithium hydroxide, lithium phosphate, lithium nitrate, lithium acetate. In some embodiments, the iron source is one or both of ferric oxide and ferric oxide. In some embodiments, the manganese source is one or both of manganese dioxide, manganomanganic oxide. In some embodiments, the vanadium source is one or both of vanadium trioxide and vanadium pentoxide. In some embodiments, the phosphorus source is one or more of ammonium phosphate, monoammonium phosphate, lithium phosphate. In some embodiments, the carbon source is one or more of carbon black, citric acid, polyethylene glycol, sucrose, glucose.
In some embodiments, a lithium source, an iron source, a manganese source, a vanadium source, a phosphorus source, and a carbon source are mixed, wherein the molar mass ratio of the lithium metal element in the lithium source to the total molar mass of the iron element, the manganese element, and the vanadium element in the iron source, the manganese source, and the vanadium source is 0.95 to 1.05.
In some embodiments, the first mixture comprising the lithium source, the iron source, the manganese source, the vanadium source, the phosphorus source, and the carbon source is subjected to a first sintering process after being refined by a sand mill and spray dried.
The carbon composite ferric manganese vanadium lithium phosphate material can improve the cycle performance, the storage performance and the safety performance of the battery. The carbon element is compounded in the carbon-compounded ferric manganese vanadium lithium phosphate material, so that the composite positive electrode material taking the carbon element as a coating layer does not need carbon doping post-treatment, the adverse effect brought by conventional carbon coating post-treatment is solved, the stability of the positive electrode composite material can be further improved, and the manufacturing cost is reduced.
In some embodiments, the molar ratio of elemental vanadium in the vanadium source to elemental iron in the iron source is from 0.5:8 to 4:1. In some embodiments, the molar ratio of elemental vanadium in the vanadium source to elemental iron in the iron source is 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, 1:1, 2:1, 3:1.
The molar ratio of vanadium element to iron element is excessively large, and the battery has excellent rate performance, however, the stability of the battery is lowered. The molar ratio of vanadium element to iron element is too small, the stability performance of the battery is improved, however, the rate performance of the battery is reduced. The molar ratio of vanadium element to iron element is controlled, and the multiplying power performance, the cycle performance and the storage performance of the battery can be considered.
In some embodiments, the mass ratio of carbon element in the carbon source to the iron manganese vanadium lithium phosphate material is 1:9999 to 1:4. In some embodiments, the mass content of carbon element in the carbon-composited iron-manganese-vanadium-lithium phosphate material may be selected from 1:999, 1:99, 1:9, 1:8, 1:7, 1:6, 1:5.
In some embodiments, the sintering temperature of the first sintering process is 650 ℃ to 800 ℃ and the sintering time of the first sintering process is 10 to 20 hours.
In some embodiments, the first sintering process is performed under a reducing atmosphere. In some embodiments, the first sintering process is performed under a nitrogen or argon atmosphere.
Controlling the sintering time of the first sintering treatment can control the nucleation growth process of the carbon-composited iron-manganese-vanadium-lithium phosphate material. Too short reaction time or too low reaction temperature can easily cause incomplete nucleation growth of the carbon-compounded iron-manganese-vanadium-lithium phosphate material and poor material crystallinity. The overlength of reaction time or the overhigh reaction temperature easily causes continuous growth of the carbon-compounded ferric manganese vanadium lithium phosphate material after the nucleation is completed, and causes the overlarge grain size of the carbon-compounded ferric manganese vanadium lithium phosphate material.
Controlling the temperature and time of the first sintering treatment within a proper range is beneficial to preparing the carbon composite ferric manganese vanadium lithium phosphate material with low powder resistivity, proper average particle size Dv50 and proper coating layer.
In some embodiments, the first mixture further comprises one or more of a nickel source, a cobalt source, a titanium source, and an aluminum source, wherein the nickel source, the cobalt source, the titanium source, and the aluminum source are each selected from one or more of oxides, hydroxides, carbonates, and phosphates comprising elemental nickel, elemental cobalt, elemental titanium, elemental aluminum. The stability of the carbon-composite ferric manganese vanadium lithium phosphate material is improved by doping nickel element, cobalt element, titanium element and aluminum element, and the cycle performance, storage performance and safety performance of the battery are further improved.
In some embodiments, the second sintering process is performed at a sintering temperature of 600 to 900 ℃ for a sintering time of 10 to 20 hours.
In some embodiments, the second mixture further comprises an alkali metal compound in an amount of 0 to 5.5% by mass, based on the total mass of the second mixture.
In some embodiments, the alkali metal compound is a carbonate, sulfate, chloride, or oxide of Na, K, rb, cs.
The second mixture comprises an alkali metal compound, so that alkali metal doping of lithium-containing metal oxide is realized, and therefore, the lithium ion diffusion efficiency of the positive electrode material is improved, the rate capability of the battery is further optimized, and the first electricity buckling effect of the battery can also be improved.
In one embodiment of the present application, a secondary battery is provided.
In general, a secondary battery includes a positive electrode tab, a negative electrode tab, an electrolyte, and a separator. During the charge and discharge of the battery, active ions are inserted and extracted back and forth between the positive electrode plate and the negative electrode plate. The electrolyte plays a role in ion conduction between the positive electrode plate and the negative electrode plate. The isolating film is arranged between the positive pole piece and the negative pole piece, and mainly plays a role in preventing the positive pole piece and the negative pole piece from being short-circuited, and meanwhile ions can pass through the isolating film.
[ Positive electrode sheet ]
The positive electrode plate comprises a positive electrode current collector and a positive electrode film layer arranged on at least one surface of the positive electrode current collector, and the positive electrode film layer comprises the composite positive electrode material of the first aspect of the application.
As an example, the positive electrode current collector has two surfaces opposing in its own thickness direction, and the positive electrode film layer is provided on either one or both of the two surfaces opposing the positive electrode current collector.
In some embodiments, the positive current collector may employ a metal foil or a composite current collector. For example, as the metal foil, aluminum foil may be used. The composite current collector may include a polymeric material base layer and a metal layer formed on at least one surface of the polymeric material base layer. The composite current collector may be formed by forming a metal material (aluminum, aluminum alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a polymer material substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In some embodiments, the positive electrode film layer further optionally includes a binder. As an example, the binder may include at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), a vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, a vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, a tetrafluoroethylene-hexafluoropropylene copolymer, and a fluoroacrylate resin.
In some embodiments, the positive electrode film layer further optionally includes a conductive agent. As an example, the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
In some embodiments, the positive electrode sheet may be prepared by: dispersing the components for preparing the positive electrode plate, such as the composite positive electrode material, the conductive agent, the binder and any other components, in a solvent (such as N-methyl pyrrolidone) to form positive electrode slurry; and (3) coating the positive electrode slurry on a positive electrode current collector, and obtaining a positive electrode plate after the procedures of drying, cold pressing and the like.
[ Negative electrode sheet ]
As an example, the anode current collector has two surfaces opposing in its own thickness direction, and the anode film layer is provided on either one or both of the two surfaces opposing the anode current collector.
In some embodiments, the negative electrode current collector may employ a metal foil or a composite current collector. For example, as the metal foil, copper foil may be used. The composite current collector may include a polymeric material base layer and a metal layer formed on at least one surface of the polymeric material base material. The composite current collector may be formed by forming a metal material (copper, copper alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a polymer material substrate (such as a substrate of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In some embodiments, the anode active material may employ an anode active material for a battery, which is well known in the art. As an example, the anode active material may include at least one of the following materials: artificial graphite, natural graphite, soft carbon, hard carbon, silicon-based materials, tin-based materials, lithium titanate, and the like. The silicon-based material may be at least one selected from elemental silicon, silicon oxygen compounds, silicon carbon composites, silicon nitrogen composites, and silicon alloys. The tin-based material may be at least one selected from elemental tin, tin oxide, and tin alloys. However, the present application is not limited to these materials, and other conventional materials that can be used as a battery anode active material may be used. These negative electrode active materials may be used alone or in combination of two or more.
In some embodiments, the negative electrode film layer further optionally includes a binder. The binder may be at least one selected from Styrene Butadiene Rubber (SBR), polyacrylic acid (PAA), sodium Polyacrylate (PAAs), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium Alginate (SA), polymethacrylic acid (PMAA), and carboxymethyl chitosan (CMCS).
In some embodiments, the negative electrode film layer further optionally includes a conductive agent. The conductive agent is at least one selected from superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
In some embodiments, the negative electrode film layer may optionally further include other adjuvants, such as thickening agents (e.g., sodium carboxymethyl cellulose (CMC-Na)), and the like.
In some embodiments, the negative electrode tab of a full cell may be prepared by: dispersing the above components for preparing the negative electrode sheet, such as a negative electrode active material, a conductive agent, a binder and any other components, in a solvent (e.g., deionized water) to form a negative electrode slurry; and coating the negative electrode slurry on a negative electrode current collector, and drying, cold pressing and the like to obtain the negative electrode plate of the full battery.
[ Electrolyte ]
The electrolyte plays a role in ion conduction between the positive electrode plate and the negative electrode plate. The application is not particularly limited in the kind of electrolyte, and may be selected according to the need. For example, the electrolyte may be liquid, gel, or all solid.
In some embodiments, the electrolyte is an electrolyte. The electrolyte includes an electrolyte salt and a solvent.
In some embodiments, the electrolyte salt may be selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bis-fluorosulfonyl imide, lithium bis-trifluoromethanesulfonyl imide, lithium trifluoromethanesulfonate, lithium difluorophosphate, lithium difluorooxalato borate, lithium difluorodioxaato phosphate, and lithium tetrafluorooxalato phosphate.
In some embodiments, the solvent may be selected from at least one of ethylene carbonate, propylene carbonate, methylethyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methylpropyl carbonate, ethylpropyl carbonate, butylene carbonate, fluoroethylene carbonate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate, 1, 4-butyrolactone, sulfolane, dimethyl sulfone, methyl sulfone, and diethyl sulfone.
In some embodiments, the electrolyte further optionally includes an additive. For example, the additives may include negative electrode film-forming additives, positive electrode film-forming additives, and may also include additives capable of improving certain properties of the battery, such as additives that improve the overcharge performance of the battery, additives that improve the high or low temperature performance of the battery, and the like.
[ Isolation Membrane ]
In some embodiments, a separator is further included in the secondary battery. The type of the separator is not particularly limited, and any known porous separator having good chemical stability and mechanical stability can be used.
In some embodiments, the material of the isolating film may be at least one selected from glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride. The separator may be a single-layer film or a multilayer composite film, and is not particularly limited. When the separator is a multilayer composite film, the materials of the respective layers may be the same or different, and are not particularly limited.
In some embodiments, the positive electrode tab, the negative electrode tab, and the separator may be manufactured into an electrode assembly through a winding process or a lamination process.
In some embodiments, the secondary battery may include an outer package. The outer package may be used to encapsulate the electrode assembly and electrolyte described above.
In some embodiments, the outer package of the secondary battery may be a hard case, such as a hard plastic case, an aluminum case, a steel case, or the like. The exterior package of the secondary battery may also be a pouch type pouch, for example. The material of the flexible bag may be plastic, and examples of the plastic include polypropylene, polybutylene terephthalate, and polybutylene succinate.
The shape of the secondary battery is not particularly limited in the present application, and may be cylindrical, square, or any other shape. For example, fig. 3 is a secondary battery 5 of a square structure as one example.
In some embodiments, referring to fig. 4, the outer package may include a housing 51 and a cover 53. The housing 51 may include a bottom plate and a side plate connected to the bottom plate, where the bottom plate and the side plate enclose a receiving chamber. The housing 51 has an opening communicating with the accommodation chamber, and the cover plate 53 can be provided to cover the opening to close the accommodation chamber. The positive electrode tab, the negative electrode tab, and the separator may be formed into the electrode assembly 52 through a winding process or a lamination process. The electrode assembly 52 is enclosed in the accommodating chamber. The electrolyte is impregnated in the electrode assembly 52. The number of electrode assemblies 52 included in the secondary battery 5 may be one or more, and those skilled in the art may select according to specific practical requirements.
In some embodiments, the secondary batteries may be assembled into a battery module, and the number of secondary batteries included in the battery module may be one or more, and the specific number may be selected by one skilled in the art according to the application and capacity of the battery module.
Fig. 5 is a battery module 4 as an example. Referring to fig. 5, in the battery module 4, a plurality of secondary batteries 5 may be sequentially arranged in the longitudinal direction of the battery module 4. Of course, the arrangement may be performed in any other way. The plurality of secondary batteries 5 may be further fixed by fasteners.
Alternatively, the battery module 4 may further include a case having an accommodating space in which the plurality of secondary batteries 5 are accommodated.
In some embodiments, the above battery modules may be further assembled into a battery pack, and the number of battery modules included in the battery pack may be one or more, and a specific number may be selected by those skilled in the art according to the application and capacity of the battery pack.
Fig. 6 and 7 are battery packs 1 as an example. Referring to fig. 6 and 7, a battery case and a plurality of battery modules 4 disposed in the battery case may be included in the battery pack 1. The battery box includes an upper box body 2 and a lower box body 3, and the upper box body 2 can be covered on the lower box body 3 and forms a closed space for accommodating the battery module 4. The plurality of battery modules 4 may be arranged in the battery box in any manner.
In addition, the application also provides an electric device which comprises at least one of the secondary battery, the battery module or the battery pack. The secondary battery, the battery module, or the battery pack may be used as a power source of the power consumption device, and may also be used as an energy storage unit of the power consumption device. The power utilization device may include mobile devices (e.g., cell phones, notebook computers, etc.), electric vehicles (e.g., electric-only vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric trucks, etc.), electric trains, ships and satellites, energy storage systems, etc., but is not limited thereto.
As the electricity consumption device, a secondary battery, a battery module, or a battery pack may be selected according to the use requirements thereof.
Fig. 8 is an electrical device as an example. The electric device is a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle or the like. In order to meet the high power and high energy density requirements of the secondary battery by the power consumption device, a battery pack or a battery module may be employed.
As another example, the device may be a cell phone, tablet computer, notebook computer, or the like. The device is generally required to be light and thin, and a secondary battery can be used as a power source.
Examples
Hereinafter, embodiments of the present application are described. The following examples are illustrative only and are not to be construed as limiting the application. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
Preparation of a composite positive electrode material:
1) Preparation of carbon-compounded lithium iron manganese vanadium phosphate material
And (3) performing first sintering treatment: mixing lithium carbonate, ferric oxide, manganese dioxide, vanadium trioxide and ammonium dihydrogen phosphate according to the molar ratio of 1:0.5:0.4:0.2, adding sucrose according to 5% of the mass of the mixture, adding a certain amount of water to ensure that the solid content is 40%, grinding and refining by a sand mill, putting into a stirring tank, uniformly mixing, then spraying and drying the uniformly mixed slurry to obtain mixed powder, putting the material into a kiln for sintering at the temperature of 700 ℃ for 10 hours, wherein the sintering atmosphere is nitrogen, and sintering to obtain the carbon composite ferric manganese vanadium lithium phosphate material.
2) Preparation of lithium-containing metal oxides
And (3) second sintering treatment: lithium hydroxide, a positive electrode material precursor Ni 0.8Co 0.1Mn 0.1(OH) 2 and aluminum oxide are placed in a coulter mixer according to the mol ratio of 1.05:0.99:0.01 to be uniformly mixed, then the mixed materials are placed in a kiln to be sintered, the sintering temperature is 750 ℃, the sintering time is 15 hours, the sintering atmosphere is oxygen, and after cooling, the metal oxide containing lithium is obtained through mechanical crushing.
3) Preparation of composite cathode material
And (3) third sintering treatment: and uniformly mixing the lithium-containing metal oxide and the carbon-compounded lithium iron manganese vanadium phosphate material according to the mass ratio of 95:5, and sintering for 5 hours at 300 ℃ in a nitrogen atmosphere to obtain the composite anode material.
Preparation of button cell:
1) Preparation of positive electrode plate
Mixing a composite positive electrode material, polyvinylidene fluoride (PVDF) and acetylene black in a ratio of 90:5:5 weight ratio to solvent N-methyl pyrrolidone (NMP) and stirring in a drying room to prepare slurry. And (3) coating the slurry on an aluminum foil, drying and cold pressing to obtain the positive pole piece. The coating amount was 0.01g/cm 2 and the compacted density was 3.5g/cm 3.
2) Preparation of negative electrode plate
A0.5 mm lithium metal sheet was used as the negative electrode sheet.
3) Preparation of electrolyte
Ethylene Carbonate (EC), ethylmethyl carbonate (EMC) and diethyl carbonate (DEC) are mixed according to a volume ratio of 1:1:1, and then LiPF 6 is uniformly dissolved in the mixed solution to obtain an electrolyte, wherein the concentration of LiPF 6 is 1mol/L.
4) Preparation of a separator film
The isolation film was purchased from Cellgard corporation under model Cellgard 2400.
5) Assembly of button cell
And assembling the prepared positive pole piece, negative pole piece, isolating film and electrolyte into the CR2032 type button cell in the button cell box.
Preparation of a full cell:
1) Preparation of positive electrode plate
Mixing a composite positive electrode material, polyvinylidene fluoride (PVDF) and acetylene black in a ratio of 90:5:5 weight ratio to solvent N-methyl pyrrolidone (NMP) and stirring in a drying room to prepare slurry. And (3) coating the slurry on an aluminum foil, drying and cold pressing to obtain the positive pole piece. The coating amount was 0.01g/cm 2 and the compacted density was 3.5g/cm 3.
2) Preparation of negative electrode plate
Uniformly mixing negative electrode active material artificial graphite, hard carbon, conductive agent acetylene black, binder Styrene Butadiene Rubber (SBR) and thickener sodium carboxymethylcellulose (CMC) in deionized water according to the weight ratio of 90:5:2:2:1, coating the mixture on a copper foil, drying and cold pressing to obtain a negative electrode plate. The coating amount was 0.015g/cm 2 and the compacted density was 1.6g/cm 3.
3) Preparation of electrolyte
Mixing Ethylene Carbonate (EC), ethylmethyl carbonate (EMC) and diethyl carbonate (DEC) in a volume ratio of 1:1:1, and uniformly dissolving LiPF 6 in the mixed solution to obtain an electrolyte, wherein the concentration of LiPF 6 is 1mol/L.
4) Preparation of a separator film
PE porous polymeric film is used as a isolating film.
5) Preparation of full cell
And sequentially stacking the positive pole piece, the isolating film and the negative pole piece, so that the isolating film is positioned in the middle of the positive pole and the negative pole to play a role in isolation, and winding to obtain the bare cell. The bare cell is placed in an outer package, and an electrolyte is injected and packaged to obtain a full cell (hereinafter also referred to as "full cell"). Length×width×height=90 mm×30mm×60mm of the whole battery, and the group margin of the battery is 91.0%. The batteries of examples 2 to 24 were similar to the battery preparation method of example 1,
The mass fraction of carbon in the carbon-composite iron-manganese-vanadium-lithium phosphate material was adjusted by changing the mass fraction of sucrose added in the first sintering treatment in examples 2 to 5, the temperature of the first sintering treatment was adjusted in examples 6 to 9, the time of the first sintering treatment was adjusted in examples 10 to 13, the mass fraction of the coating layer was adjusted in examples 14 to 17, and the molar ratio of the vanadium element in the vanadium source to the iron element in the iron source in the first sintering treatment was adjusted in examples 18 to 21, with specific parameters shown in fig. 1.
In example 22, sodium carbonate was added to the second sintering treatment, and the molar ratio of lithium hydroxide, sodium carbonate, the precursor of the positive electrode material Ni 0.8Co 0.1Mn 0.1(OH) 2, and alumina was 1.03:0.02:0.99:0.01.
In example 23, alumina, lithium carbonate, alumina, ferric oxide, manganese dioxide, vanadium trioxide, and ammonium dihydrogen phosphate were added at a molar ratio of 1:0.002:0.5:0.4:0.2:1.
The positive electrode material precursor added in the second sintering treatment in example 24 was Ni 0.92Co 0.06Mn 0.02(OH) 2.
The positive electrode material in comparative example 1 was a lithium-containing metal oxide, and there was no coating layer;
the coating material in comparative example 2 is a carbon-composite lithium iron manganese phosphate material, and specific parameters are shown in table 1.
The carbon-composite iron-manganese-vanadium phosphate materials and batteries obtained in examples 1 to 24 and comparative examples 1 and 2 were subjected to performance test, and the test results are shown in table 1.
The test method is as follows:
1. Performance test of carbon composite ferric manganese vanadium phosphate material
1) Particle size test of carbon composite ferric manganese vanadium phosphate material
The particle size distribution was measured by a laser particle size analyzer, malvern Mastersizer 2000E, in the United kingdom, with reference to GB/T19077-2016 laser diffraction method.
2) Powder resistivity of carbon-composited iron-manganese-vanadium phosphate material
And (3) drying the powder of the carbon composite ferric manganese vanadium phosphate material, weighing a proper amount of powder, and then using a powder resistivity tester, a digital four-probe instrument of equipment model ST2722, and measuring the powder resistivity of the sample according to GB/T30835-2014 of carbon composite lithium iron phosphate cathode material for lithium ion batteries.
3) Carbon content test of carbon-compounded iron-manganese-vanadium phosphate material
The carbon content of the powder was measured by using a carbon content analyzer C content analyzer, equipment model HCS-140, and a high frequency induction furnace post combustion infrared absorption method (conventional method) GBT20123-2006 according to the measurement of the total carbon sulfur content of steel.
2. Morphology characterization of composite positive electrode materials
The surface morphology of the composite positive electrode material was characterized using a field emission scanning electron microscope (Sigma 300) from ZEISS, germany.
3. Performance test of a battery
1) Initial gram capacity and initial efficiency test of button cell
The button cell was charged to 4.3V at 0.1C under 2.8-4.3V, then charged to 0.05mA at constant voltage under 4.3V, left standing for 2min, the charge capacity at this time was noted as C0, then discharged to 2.8V at 0.1C, and the discharge capacity at this time was noted as D0 as the initial gram capacity. The first effect is calculated according to D0/C0 x 100%.
2) Full cell capacity retention at 25 deg.c
Charging to 4.25V at 25 ℃ with a constant current of 1C, then charging to 0.05C with a constant voltage of 4.25V, and then discharging to 2.8V with a constant current of 1C to obtain a first-week discharge specific capacity (Cd 1); and repeatedly charging and discharging until 300 weeks, and recording the specific discharge capacity of the lithium ion battery after n weeks of cycle as Cdn. Capacity retention = specific discharge capacity after n weeks of cycling (Cdn)/specific discharge capacity at first week (Cd 1).
3) Full cell capacity retention at 45 DEG C
Charging to 4.25V at 45 ℃ with a constant current of 1C, then charging to 0.05C with a constant voltage of 4.25V, and then discharging to 2.8V with a constant current of 1C to obtain a first-week discharge specific capacity (Cd 1); and repeatedly charging and discharging until 300 weeks, and recording the specific discharge capacity of the lithium ion battery after n weeks of cycle as Cdn. Capacity retention = specific discharge capacity after n weeks of cycling (Cdn)/specific discharge capacity at first week (Cd 1).
4) Full cell 70 ℃ gas production test
At 70 ℃, a full battery of 100% state of charge (SOC) is stored. Open Circuit Voltage (OCV) and internal ac resistance (IMP) of the cells were measured before, after and during storage to monitor SOC and measure cell volume. Wherein the full cells were taken out after 48h of each storage, were left to stand for 1h, were tested for OCV, IMP, and were measured for cell volume by drainage after cooling to room temperature. The drainage method is to automatically measure the gravity F1 of the battery cell by using a balance for unit conversion by dial data, then completely placing the battery cell in deionized water (the density is known as 1g/cm 3), measuring the gravity F 2 of the battery cell at the moment, floating the battery cell by buoyancy F 1-F 2, and calculating according to Archimedes principle F float=ρgV Row of rows to obtain the volume V= (F 1-F 2)/ρg of the battery cell.
After the volume is tested, the battery cell is charged with 1C constant current to 4.25V, then is charged with 4.25V constant voltage until the current is reduced to 0.05C, and the battery cell is charged into the furnace for continuous test after the charging is finished.
After 30 days of storage, the cell volume is measured, and the increase of the stored cell volume relative to the cell volume before storage, namely the gas production amount, is calculated, and the gas production amount per cell volume is obtained.
The present application is not limited to the above embodiment. The above embodiments are merely examples, and embodiments having substantially the same configuration and the same effects as those of the technical idea within the scope of the present application are included in the technical scope of the present application. Further, various modifications that can be made to the embodiments and other modes of combining some of the constituent elements in the embodiments, which are conceivable to those skilled in the art, are also included in the scope of the present application within the scope not departing from the gist of the present application.
The morphology test of the composite positive electrode material is carried out by adopting a scanning electron microscope SEM, the test result is shown in figure 1, the composite positive electrode material prepared in the embodiment 1 and taking Li 2FeMn 0.4V 0.4PO 4 @C as a coating layer has uniform particle size in micron level, uniform particle distribution and no agglomeration, and the cycle performance test curve at 25 ℃ of the battery assembled by taking the composite positive electrode material as the positive electrode material is shown in figure 2, so that the cycle capacity retention rate of the battery is calculated.
As can be seen from the comparison of examples 1 to 24 and comparative example 1, the composite positive electrode material provided by the present application includes: a lithium-containing metal oxide and a coating layer arranged on at least one part of the lithium-containing metal oxide, wherein the coating layer is a carbon composite ferric manganese vanadium lithium phosphate material, the general formula of the ferric manganese vanadium lithium phosphate material is shown as formula I,
LiFe a1Mn b1V c1M2 d1PO 4, formula I
Wherein a1 is more than or equal to 0.1 and less than or equal to 0.8,0.1, b1 is more than or equal to 0.45,0.07, c1 is more than or equal to 0.3, d1 is more than or equal to 0 and less than or equal to 0.01, and M2 is one or more selected from Ni, co, ti, al.
The composite positive electrode material prepared by coating the lithium-containing metal oxide with the carbon composite ferric manganese vanadium lithium phosphate material can improve the cycle capacity retention rate of the battery at normal temperature and high temperature, reduce the unit capacity gas production volume of the battery at high temperature, namely improve the cycle performance, the storage performance and the safety performance of the battery, and meanwhile, the capacity performance of the battery can not be greatly reduced by the coating layer, so that the battery taking the composite positive electrode material as the positive electrode still has excellent capacity performance and the first effect of electricity buckling.
As can be seen from the comparison of example 1 and comparative examples 1 to 2, the coating layer of the present application can further improve the ring performance, storage performance and safety performance of the battery, and the coating layer can also improve the gram capacity of the battery, compared with the conventional lithium iron manganese phosphate coating layer.
It can be seen from examples 1 and 14 to 17 that the mass content of the coating layer is 0.1 to 10 percent, and the composite positive electrode material can further improve the cycle performance, the storage performance and the safety performance of the battery and can maintain and even improve the capacity performance and the first effect of the power buckling of the battery based on the total mass timing of the composite positive electrode material.
As can be seen from examples 1 to 5, the mass fraction of carbon in the coating layer was 0.01% to 25%, and the coating layer had a suitable powder resistivity based on the total mass timing of the coating layer, and deintercalation of lithium ions was easily achieved, and even in the case of the addition of the coating layer, the capacity performance and initial efficiency of the battery could be further maintained or improved, and the battery performance was not deteriorated by the addition of the coating layer.
As can be seen from the comparison of examples 1 to 5 and comparative example 3, the powder resistivity of the composite positive electrode material is 1000 to 5500 Ω·cm, the powder resistivity of the composite positive electrode material is low, the material stability and conductivity are higher, and the retention and improvement of the battery capacity are facilitated.
As can be seen from examples 1 and 6 to 13, the composite positive electrode material exhibits excellent electrochemical performance and cycle performance when the average particle diameter D50 of the composite positive electrode material is 8 to 12. Mu.m, alternatively 8 to 10. Mu.m.
It can be seen from examples 1 and 18 to 21 that when the molar ratio of the vanadium element in the vanadium source to the iron element in the iron source is 0.5:8 to 4:1, the composite positive electrode material can further improve the cycle performance, the storage performance and the safety performance of the battery, and simultaneously can maintain, even improve the capacity performance and the first-effect of the battery.
As can be seen from examples 1 and 23, doping aluminum element in the carbon-composite iron-manganese-vanadium-lithium phosphate material can further improve the stability of the coating layer, thereby improving the cycle performance of the battery at high temperature.
As can be seen from examples 1 and 22, the lithium-containing metal oxide was doped with alkali metal, and the battery had improved initial power efficiency, cycle performance and storage performance.
As can be seen from examples 1 and 24, the carbon-composite lithium iron manganese vanadium phosphate material is used as a coating layer for lithium-containing metal oxides with different nickel-cobalt-manganese contents, and the adjustment of the proportion of nickel-cobalt-manganese is helpful for adjusting the capacity performance and the first-effect of electricity buckling of the battery.
Claims (18)
- A composite positive electrode material, characterized in that the composite positive electrode material comprises: a lithium-containing metal oxide and a coating layer arranged on at least one part of the lithium-containing metal oxide, wherein the coating layer is a carbon-composite ferric manganese vanadium lithium phosphate material, the general formula of the ferric manganese vanadium lithium phosphate material is shown as formula I,LiFe a1Mn b1V c1M2 d1PO 4, formula IWherein a1 is more than or equal to 0.1 and less than or equal to 0.8,0.1, b1 is more than or equal to 0.45,0.07, c1 is more than or equal to 0.3, d1 is more than or equal to 0 and less than or equal to 0.01, and M2 is one or more selected from Ni, co, ti, al.
- The composite positive electrode material according to claim 1, wherein the mass content of the coating layer is 0.1 to 10% based on the total mass of the composite positive electrode material.
- The composite positive electrode material according to claim 1 or 2, wherein the mass fraction of carbon in the coating layer is 0.01 to 25% based on the total mass of the coating layer.
- The composite positive electrode material according to any one of claims 1 to 3, wherein the powder resistivity of the composite positive electrode material is 1000 to 5500 Ω -cm.
- The composite positive electrode material according to any one of claims 1 to 4, wherein the average particle diameter Dv50 of the composite positive electrode material is 8 to 12 μm.
- The composite positive electrode material according to any one of claims 1 to 5, wherein the general formula of the lithium-containing metal oxide is represented by formula II,Li 1.05-a2M1 a2(Ni b2Co c2Mn d2) 1-e2Q e2O 2, formula IIIn the method, in the process of the invention, a2 is more than or equal to 0 and less than or equal to 0.1,0.7 is more than or equal to b 0.96,0.03 c22 is less than or equal to 0.96,0.03 c2 is less than or equal to; wherein M1 is selected from one or more of alkali metal elements Na, K, rb, cs, and Q is selected from one or more of Al, mg, zr, ti, W, Y, B, co, nb, mo, sb, sr.
- The preparation method of the composite positive electrode material is characterized by comprising the following steps of:Performing first sintering treatment on a first mixture containing a lithium source, an iron source, a manganese source, a vanadium source, a phosphorus source and a carbon source to prepare a carbon composite ferric manganese vanadium lithium phosphate material,Performing second sintering treatment on a second mixture containing a lithium source and a nickel cobalt manganese precursor, wherein the molar ratio of lithium element in the lithium source to the sum of nickel element, cobalt element and manganese element in the nickel cobalt manganese precursor is 0.95-1.05, so as to prepare a lithium-containing metal oxide;Performing third sintering treatment on the carbon-compounded ferric manganese vanadium lithium phosphate material and the lithium-containing metal oxide to obtain a compound anode material,The composite positive electrode material comprises lithium-containing metal oxide and a coating layer arranged on at least one part of the lithium-containing metal oxide, wherein the coating layer is the carbon composite ferric manganese vanadium lithium phosphate material, the general formula of the ferric manganese vanadium lithium phosphate material is shown as formula I,LiFe a1Mn b1V c1M2 d1PO 4, formula IWherein a1 is more than or equal to 0.1 and less than or equal to 0.8,0.1, b1 is more than or equal to 0.45,0.07, c1 is more than or equal to 0.3, d1 is more than or equal to 0 and less than or equal to 0.01, and M2 is one or more selected from Ni, co, ti, al.
- The method according to claim 7, wherein in the third sintering treatment, a mass ratio of the lithium-containing metal oxide to the carbon-composited lithium iron manganese vanadium phosphate material is 9:1 to 999:1.
- The method according to claim 7 or 8, characterized in that in the first sintering treatment, a molar ratio of vanadium element in the vanadium source to iron element in the iron source is 0.5:8 to 4:1.
- The method for producing a composite positive electrode material according to any one of claims 7 to 9, characterized in that a mass ratio of carbon element in the carbon source to the iron-manganese-vanadium-lithium phosphate material is 1:9999 to 1:4.
- The method for producing a composite positive electrode material according to any one of claims 7 to 10, wherein the sintering temperature of the first sintering treatment is 650 to 800 ℃, or the sintering time of the first sintering treatment is 10 to 20 hours.
- The method for producing a composite positive electrode material according to any one of claims 7 to 11, wherein one or more of a nickel source, a cobalt source, a titanium source, and an aluminum source is further contained in the first mixture, the nickel source, the cobalt source, the titanium source, and the aluminum source are each selected from one or more of oxides, hydroxides, carbonates, and phosphates containing nickel element, cobalt element, titanium element, and aluminum element.
- The method for producing a composite positive electrode material according to any one of claims 7 to 12, wherein the iron source is selected from one or more of ferric oxide and ferroferric oxide; the manganese source is selected from one or more of manganese dioxide and manganous-manganic oxide; the vanadium source is selected from one or more of vanadium trioxide and vanadium pentoxide; the phosphorus source is selected from one or more of ammonium phosphate, monoammonium phosphate and lithium phosphate; the carbon source is one or more selected from carbon black, citric acid, polyethylene glycol, sucrose and glucose.
- The method for producing a composite positive electrode material according to any one of claims 7 to 13, characterized by further comprising the steps of:The second mixture further comprises an alkali metal compound, wherein the mass content of the alkali metal compound is 0-5.5% based on the total mass of the second mixture.
- A secondary battery comprising a positive electrode sheet comprising the composite positive electrode material according to any one of claims 1 to 6, a separator, a negative electrode sheet, and an electrolyte.
- A battery module comprising the secondary battery according to claim 15.
- A battery pack comprising the battery module of claim 16.
- An electric device comprising at least one selected from the secondary battery according to claim 15, the battery module according to claim 16, and the battery pack according to claim 17.
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