CN111162258A - Positive electrode material for battery, battery positive electrode, battery and preparation method of positive electrode material - Google Patents

Positive electrode material for battery, battery positive electrode, battery and preparation method of positive electrode material Download PDF

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Publication number
CN111162258A
CN111162258A CN201911412805.6A CN201911412805A CN111162258A CN 111162258 A CN111162258 A CN 111162258A CN 201911412805 A CN201911412805 A CN 201911412805A CN 111162258 A CN111162258 A CN 111162258A
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positive electrode
battery
electrode material
capacity
lithium
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骆亦琦
王岑
李喆
陆玉婷
张和宝
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Boselis Hefei Co ltd
Bosellis Nanjing Co ltd
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Amprius Nanjing 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
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present application relates to a positive electrode material for a battery, comprising: has a chemical formula of Li6+aCo1‑xFexO4‑bWherein 0 is<x is less than or equal to 0.6, a is less than or equal to 0.2, b is less than or equal to 0.2, and the median particle diameter D50 is between 5 and 30 mu m. The cathode material for the lithium ion battery is represented by Li6CoO4A uniform single homogeneous phase. By introducing a high proportion of iron element into the material synthesis process, the method is remarkableThe material cost is reduced.

Description

Positive electrode material for battery, battery positive electrode, battery and preparation method of positive electrode material
Technical Field
The application relates to the technical field of batteries, in particular to a positive electrode material for a battery, a battery positive electrode, a battery and a preparation method of the positive electrode material.
Background
With the development of society, lithium ion batteries have attracted extensive attention and are widely applied to the fields of consumer electronics and power electronics. With the progress of the downstream industrial technology, people have higher and higher requirements on lithium ion batteries. At present, lithium ion batteries widely applied in the market have low energy density, and the endurance of consumer electronic products and electric vehicles is greatly limited. As an important component of the lithium ion battery, the anode and cathode materials are the key to improve the energy density of the battery. The prior negative electrode materials mainly adopt graphite negative electrode materials such as natural graphite, artificial graphite, hard carbon, soft carbon and the like, and the capacity of the graphite negative electrode materials is very close to the upper limit of the theoretical capacity (372 mAh/g). In recent years, in the research of negative electrodes, materials of silicon carbon and silicon oxygen are pulverized and inactivated due to large expansion and contraction in the circulation process, and meanwhile, SEI is repeatedly generated due to expansion cracking, so that lithium ions are excessively consumed, and the circulation performance of the materials is poor. Therefore, it is difficult to greatly increase the energy density of the battery only by the negative electrode at this stage. Therefore, it is important to improve the energy density of the battery by using the positive electrode material.
The development history of the positive electrode material of the lithium ion battery is basically the development history of most of the lithium ion batteries, and from the earliest lithium cobaltate, the technology of the positive electrode material of the lithium battery is continuously developed from lithium iron phosphate, ternary NCM, NCA, spinel material, lithium-rich manganese and other materials at present. However, as the requirements for energy density and cycle life of lithium batteries are continuously increased, the conventional positive electrode materials cannot meet the requirements at the same time.
Prior art LiCoO2As a consumptionThe theoretical capacity of the anode material commonly used for the electronic class is 274mAh/g, and is limited by a plurality of factors even at a higher voltage (4.4Vvs+) Next, LiCoO2The exerted capacity is only about 190 mAh/g. In some disclosed methods for making lithium cobaltate positive electrodes, a controlled crystallization process is used to produce a specific cobaltosic oxide material. The lithium cobaltate product prepared by using the cobaltosic oxide material has the advantages that the powder particles are uniformly distributed, and the compaction density of the product is improved. And meanwhile, the surface of the lithium cobaltate anode is coated by adopting non-transition metal, so that the reaction activity of the lithium cobaltate anode and electrolyte is reduced, and the cycle performance of the battery is improved. However, the reversible capacity of the lithium cobaltate positive electrode material is only 175mAh/g, and the energy density of the battery is difficult to be greatly improved. The ternary materials (NCM and NCA) improve the capacity exertion to a certain extent by properly improving the doping amount of the transition metal elements, but due to the limitation of theoretical capacity, the energy density is difficult to greatly improve, and meanwhile, potential safety hazards are brought. Therefore, the energy density of the battery can be increased to some extent by means of doping coating, increasing the compaction of the positive electrode material, and the like, but this is limited.
Disclosure of Invention
In view of the above-described background art and the drawbacks of the prior art, the present application provides a positive electrode material for a battery, in view of the crystal structure and specific capacity (electron supply capacity) of the material itself. The anode material has the advantages of low cost, high specific capacity, low cost, high energy density and long cycle life in a lithium ion battery system.
According to an aspect of the present application, there is provided a positive electrode material including: has a chemical formula of Li6+aCo1-xFexO4-bWherein 0 is<x is less than or equal to 0.6, a is less than or equal to 0.2, b is less than or equal to 0.2, and the median particle diameter D50 is between 5 and 30 mu m.
According to some embodiments of the present application, the specific surface area of the cathode material is 0.11m2G to 0.92m2Between/g.
According to some embodiments of the present application, the Li6+aCo1-xFexO4-bThe width of the particle size distribution is between 1.2 and 2.4.
According to some embodiments of the present application, the positive electrode material further comprises a coating substance coating a surface of the positive electrode material.
According to some embodiments of the application, the coating substance comprises: al (Al)2O3、TiO2、SiO2、MgO、ZrO2、AlPO4、ZnO、SnO2One or more of (a).
According to some embodiments of the present application, the amount of the coating substance is between 0.1 wt% and 5 wt% based on the total weight of the positive electrode material.
According to some embodiments of the present application, the Li6+aCo1-xFexO4-bDiffraction peaks generated when the material is tested by an X-ray diffractometer comprise peak positions at which the 2 theta diffraction angles are 19.2 +/-0.2 degrees, 23.4 +/-0.2 degrees, 27.3 +/-0.2 degrees, 33.5 +/-0.2 degrees, 36.3 +/-0.2 degrees and 56.0 +/-0.2 degrees.
According to another aspect of the present application, there is also provided a battery positive electrode comprising the positive electrode material as described above.
According to another aspect of the present application, there is also provided a battery including the battery positive electrode as described above.
According to another aspect of the present application, there is also provided a method for preparing the positive electrode material, including: grinding and mixing a lithium precursor, a cobalt precursor and an iron precursor to obtain a precursor mixture of lithium, cobalt and iron; sintering the precursor mixture of lithium, cobalt and iron in an inert atmosphere to obtain a first product; and crushing, screening and demagnetizing the first product to obtain the cathode material.
According to some embodiments of the present application, crushing, screening and demagnetizing the first product to obtain the cathode material further comprises: and grinding, mixing and coating the first product and the pre-coating object, and sintering in an inert atmosphere.
According to some embodiments of the present application, the lithium precursor, the cobalt precursor, and the iron precursor are mill-mixed in a ratio of an atomic ratio Li/(Co + Fe) of 6.0 to 6.3.
According to some embodiments of the present application, the lithium precursor comprises: one or more of anhydrous lithium hydroxide, lithium hydroxide monohydrate, lithium carbonate, lithium peroxide, lithium oxide and lithium hydride.
According to some embodiments of the application, the cobalt precursor comprises: one or more of cobaltosic oxide, cobaltous oxide and cobaltous hydroxide.
According to some embodiments of the application, the iron precursor comprises: one or more of ferroferric oxide, ferric oxide and ferric hydroxide.
According to some embodiments of the present application, the conditions of the milling and mixing are: grinding and mixing in at least one of air, nitrogen, argon, helium and neon with humidity less than 20%.
According to some embodiments of the application, the abrasive mixing comprises mechanical abrasive mixing.
According to some embodiments of the application, the conditions of the sintering comprise: sintering the precursor mixture of lithium, cobalt and iron at 400-1000 deg.C for 4-24 hr.
According to some embodiments of the application, the inert atmosphere comprises: nitrogen, argon, helium, neon, or krypton.
According to some embodiments of the application, the crushing comprises mechanical grinding.
According to some embodiments of the application, the milling and mixing of the first product with the precoating is a mechanical blending or a mechanical milling and mixing.
According to some embodiments of the present application, the mechanical milling mixing conditions comprise: the mechanical milling is carried out in at least one of air, nitrogen, argon, helium, neon or krypton at a humidity of less than 20%.
According to some embodiments of the present application, in the step of performing the grinding, mixing, coating and sintering under an inert atmosphere on the first product and the pre-coating, the sintering condition is between 300 ℃ and 900 ℃ for 2-12 hours.
According to some embodiments of the application, the inert atmosphere comprises: nitrogen, argon, helium, neon or krypton.
In the positive electrode material for the lithium ion battery provided by the scheme of each embodiment of the application, the iron element with high proportion is introduced in the material synthesis process, so that the material cost is obviously reduced, and the material can be expressed as the original Li6CoO4A uniform single homogeneous phase. Because the iron element replaces the cobalt lattice site, the synergistic effect of the iron-cobalt diatoms is exerted, and the oxygen adsorption Gibbs free energy delta G of the atomic site in the lattice is improvedOThe method enhances the partial adsorption of active oxygen and reduces the generation of side reaction between solid and liquid interfaces. In addition, the coating material is uniformly coated on the surface of the material through a coating process, the coating layer has the effect of inhibiting the reaction of the anode material and water molecules in the air, and meanwhile, the side reaction of the anode material and electrolyte can be effectively reduced, and the stability of the anode material is obviously improved.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application. In the drawings:
fig. 1 is a method of preparing a positive electrode material according to an example embodiment of the present application.
Fig. 2 is a scanning electron microscope photograph of a positive electrode material according to an exemplary embodiment of the present application;
FIG. 3 is a scanning electron microscope photograph at another magnification of a positive electrode material according to an exemplary embodiment of the present application;
FIG. 4 is a scanning electron microscope photograph at another magnification of a positive electrode material according to an exemplary embodiment of the present application;
fig. 5 is an X-ray diffraction (XRD) pattern of a positive electrode material according to an exemplary embodiment of the present application;
Detailed Description
In the following, only certain exemplary embodiments are briefly described. As those skilled in the art will recognize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present application. Accordingly, the drawings and description are to be regarded as illustrative in nature, and not as restrictive.
In the description of the present disclosure, it is to be understood that the terms "first", "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, features defined as "first", "second", may explicitly or implicitly include one or more of the described features. In the description of the present disclosure, "a plurality" means two or more unless specifically limited otherwise. The specific meaning of the above terms in the present disclosure can be understood by those of ordinary skill in the art as appropriate.
In general, the specific capacity of the cathode material is closely related to the valence change capability of the transition metal, which is a main reason why the specific capacity of the conventional cathode material has been difficult to be improved. The lithium-rich material has a large amount of lithium atoms in crystal lattices, so that not only transition metals but also part of lattice oxygen participate in valence change when lithium ions are extracted, and electrons are released, thereby providing more positive electrode capacity. Li6CoO4As one of the lithium-rich materials, the lithium-rich material has the advantages of stable structure, simple synthesis method and high theoretical specific capacity. However, due to the deintercalation of lithium ions and the reduction of lattice oxygen into oxygen during charging, the almost irreversible phase transition has very poor cycle stability, and is difficult to be used as a main material of the whole lithium ion battery. Consider that part of the lithium ions in the positive electrode material are consumed in the form of sei (solid electrolyte interphase) during cycling of the lithium ion battery. Therefore, by adding part of Li of high capacity6CoO4The mixed use with the prior anode material is a very effective method for improving the energy density of the battery. In addition, when the particle size distribution and the specific charge capacity meet the requirements of the positive electrode material, the edges and corners of the particles of the positive electrode material for the lithium battery are clear, and the poor sphericity affects the compaction density of the positive electrode and the contact degree among the particles. On the other hand, the cathode material is reduced by doping other elementsThe content of cobalt is reduced, but the actual doping amount is less than 5%, the content of cobalt is not obviously reduced, and the cost advantage does not exist. In recent years, with the rapid development of lithium ion batteries, cobalt element is used as a main element in the anode material with the most cost of lithium batteries, and the price of cobalt element is rapidly increased, and the storage capacity of cobalt ore in China is very limited in the world, so that how to reduce the cost on the premise of not losing the electrochemical performance is very important.
The preferred embodiments of the present application will be described in conjunction with the accompanying drawings, and it will be understood that they are described herein only to illustrate and explain the present application and not to limit the present application.
Example 1:
fig. 1 is a method of preparing a positive electrode material according to an example embodiment of the present application.
Referring to fig. 1, according to an exemplary embodiment of the present application, a lithium precursor, a cobalt precursor, and an iron precursor are milled and mixed in S101 to obtain a precursor mixture of lithium, cobalt, and iron. The lithium precursor, the cobalt precursor and the iron precursor are ground and mixed according to the atomic ratio Li/(Co + Fe) of 6.0-6.3. According to some embodiments, the lithium precursor comprises: one or more of anhydrous lithium hydroxide, lithium hydroxide monohydrate, lithium carbonate, lithium peroxide, lithium oxide and lithium hydride. The cobalt precursor comprises: one or more of cobaltosic oxide, cobaltous oxide and cobaltous hydroxide. The iron precursor includes: one or more of ferroferric oxide, ferric oxide and ferric hydroxide.
As shown in fig. 1, according to an exemplary embodiment of the present application, the milling mixing conditions are: grinding and mixing in at least one of air, nitrogen, argon, helium and neon with humidity less than 20%. In this example, Li is weighed2CO3229.1g, Li was added by using a ball mill2CO3Grinding, crushing, then adding Co (OH)237.2g and Fe2O347.91g, continuously grinding and mixing by using a ball mill to obtain uniformly mixed Li2CO3、Co(OH)2And Fe2O3A mixture of (a).
As shown in fig. 1, according to the present inventionApplying for example embodiments, in S103, sintering a precursor mixture of lithium, cobalt, and iron under an inert atmosphere to obtain a first product, wherein the sintering conditions include: sintering the precursor mixture of lithium, cobalt and iron at 400-1000 ℃ for 4-24 hours, wherein the inert atmosphere comprises: one or more of nitrogen, argon, helium, neon and krypton. Placing the obtained material into an electric heating furnace, keeping the temperature of 1000 ℃ for 4 hours in an argon atmosphere to obtain Li6+ aCo1-xFexO4-bAccording to the test and the calculation of the theoretical error range, x is 0.6, -0.2 is not less than a and not more than 0.2, -0.2 is not less than b and not more than 0.2.
Referring to fig. 1, in S105, the first product obtained above is freely cooled to room temperature, and then taken out, and subjected to crushing, sieving, demagnetizing, and the like, wherein the crushing treatment includes mechanical grinding, and a positive electrode material for a battery of the present application is obtained.
In addition, as shown in fig. 1, according to the exemplary embodiment of the present application, a step S104 may be added between S103 and S105, and the first product and the pre-coating are subjected to grinding, mixing, coating, and sintering under an inert gas. Wherein the grinding mixed coating adopts mechanical fusion or mechanical grinding mixing, and the conditions are as follows: and mechanically grinding in at least one of air, nitrogen, argon, helium, neon and krypton with humidity of less than 20%. The sintering conditions in the sintering step are as follows: 300-900 ℃ for 2-12 hours, wherein the sintering atmosphere comprises: at least one or more of nitrogen, argon, helium, neon and krypton. In this example, the first product was ground and sieved, and then 0.1 wt% ZrO was added2And after a uniformly mixed mixture is obtained, putting the obtained material into an electric heating furnace, and keeping the temperature of 900 ℃ for 2 hours in an argon atmosphere. Then mixing by using a mechanical grinding mode, wherein equipment used for mechanical grinding comprises: high speed stirred mills, ball mills, tube mills, cone mills, rod mills, sand mills, and the like. Uniformly coating a coating substance on the surface of the material by a coating process, wherein the coating comprises: al (Al)2O3、TiO2、SiO2、MgO、ZrO2、AlPO4、ZnO、SnO2One or more of (a). According to some embodiments of the present disclosure, the content of the coating substance is between 0.1 wt% and 5 wt% of the total weight of the cathode material, which has an effect of inhibiting a water molecule reaction of the cathode material in air, and can also effectively reduce a side reaction of the cathode material with an electrolyte, thereby significantly improving the stability of the cathode material.
The positive electrode material for the battery prepared above was characterized using the following apparatus, and the same characterizing apparatus was used in the following examples.
The particle size distribution of the prepared anode material is tested by a Dandongbeit BetterSize 2000 type laser particle sizer. The median particle diameter D50 of the test sample was 29.98. mu.m, and the width of the particle size distribution (D90-D10)/D50 was 2.4 (particle size distributions D90, D50 and D10 respectively represent the particle diameters at which the percentages of the cumulative particle size distributions reached 90%, 50% and 10%).
Fig. 2 is a scanning electron microscope photograph of a cathode material according to an exemplary embodiment of the present application.
Fig. 3 is a scanning electron microscope photograph at another magnification of a cathode material according to an example embodiment of the present application.
Fig. 4 is a scanning electron microscope photograph at another magnification of a cathode material according to an example embodiment of the present application.
Referring to fig. 2, 3 and 4, according to the exemplary embodiment of the present application, the surface morphology of the prepared cathode material was observed by using a Hitachi SU8010 type scanning electron microscope. In this embodiment, as shown in the scanning electron microscope photographs of fig. 2, fig. 3, and fig. 4, due to the introduction of the iron element, the surface energy of the material is significantly improved, the morphology of the positive electrode material is effectively controlled, the particle surface is smoother and smoother, the mutual contact between the positive electrode materials is greatly improved, and the compaction density is enhanced. Meanwhile, the size distribution of the anode material is narrow, and when the anode material is mixed with other anode materials, large, medium and small particles are uniformly distributed, so that the compaction density of the mixed material is improved.
The specific surface area of the prepared material is 0.11m by adopting a Congta NOVA4200e type specific surface area tester2The smaller specific surface area is more favorable for the homogenate coating process of the anode material and reduces the occurrence of side reaction on the interface with the electrolyte.
A Rigaku MiniFlex600 type X-ray diffractometer is adopted, a diffraction angle is set to be 10-80 degrees, a step length is set to be 0.02 degrees, and a speed is set to be 1 degree/min, and the crystal structure of the prepared anode material is tested under the parameters.
Fig. 5 is an X-ray diffraction (XRD) pattern of the cathode material according to an exemplary embodiment of the present application.
As shown in FIG. 5, Li according to an exemplary embodiment of the present application6+aCo1-xFexO4-bDiffraction peaks generated when the material is tested by an X-ray diffractometer comprise peak positions at which the 2 theta diffraction angles are 19.2 +/-0.2 degrees, 23.4 +/-0.2 degrees, 27.3 +/-0.2 degrees, 33.5 +/-0.2 degrees, 36.3 +/-0.2 degrees and 56.0 +/-0.2 degrees.
Referring to fig. 5, in this example, the prepared positive electrode material crystal form and Li6CoO4 corresponds well. Meanwhile, the diffraction angles of the crystal do not have diffraction peaks at 31.3 +/-0.2 degrees, 31.8 +/-0.2 degrees, 32.5 +/-0.2 degrees, 32.7 +/-0.2 degrees, 35.0 +/-0.2 degrees, 37.4 +/-0.2 degrees and 42.4 +/-0.2 degrees, and the diffraction angles are Co3O4、Li2CO3、LiOH、Co(OH)2、Li2O2、LiCoO2And characteristic peaks corresponding to CoO show that the prepared cathode material does not contain Co, Li simple substance or compound impurities basically. Further, the 2 theta diffraction angle thereof does not correspond to Li at 16.7 + -0.2 DEG and 21.6 + -0.2 DEG5FeO4Shows that no new Li appears in the prepared cathode material after the Fe is introduced5FeO4An impurity phase.
The prepared positive electrode material, the conductive agent and the binder are uniformly mixed according to the proportion of 90:3:7, and the mixture is coated on an aluminum foil to prepare a pure electrode. And cutting, vacuum baking, winding the obtained positive pole piece, the paired negative pole piece and the diaphragm together, filling the wound positive pole piece, the paired negative pole piece and the diaphragm into an aluminum plastic shell with an air bag of a corresponding size, injecting a certain amount of electrolyte, and sealing the opening of the aluminum plastic shell to obtain the complete lithium ion full battery. The battery capacity is tested by using a Xinwei test device BTS79, and the positive electrode charging capacity is calculated to reach 901.7 mAh/g.
The obtained positive electrode material and LiCoO2The conductive agent and the adhesive are uniformly mixed according to the proportion of 2:96.2:0.6:1.2, coated on an aluminum foil to prepare a blended electrode, an all-electric cell with an air bag is assembled, the air bag is removed after formation, and the electrochemical performance is tested. According to the test result, the first charge capacity of the mixed positive electrode material in the battery is calculated to be 214.2mAh/g, the discharge capacity is 192.5mAh/g, the volume energy density of the battery is 805Wh/L, and the capacity retention rate of the battery is 84.5% after the battery is subjected to 500 charge-discharge cycles.
By introducing a high proportion of Fe element in the material synthesis process, the cost of the metal oxide is reduced by more than 50% in the aspect of cost, and obvious advantages are embodied. Tests show that the introduction of high iron content does not cause change of crystal structure or negative influence on the anode material. In addition, Fe replaces lattice sites of Co to exert a diatomic synergistic effect of Fe and Co, so that the oxygen adsorption Gibbs free energy delta G of atomic sites in the lattice is improvedOThe method enhances the partial adsorption of active oxygen and reduces the generation of solid-liquid interface load reduction reaction. In addition, the introduction of ferric ion doping enables electron orbits of atoms in crystal lattices to be coupled, so that the conduction of electrons in the crystal lattices is effectively improved, partial oxygen vacancy defects can be caused by mismatch of valence states, the electronic conductivity and the ionic conductivity are improved, further, the cycle effect and the thermal stability during high-rate discharge are improved, the capacity is improved, and the power is increased.
In the following examples, the pure-electrode full cell and the blended-electrode full cell were prepared by performing test characterization in the same manner as in example 1, and the charge and discharge capacity, energy density and cycle retention rate of the two full cells were tested on the same equipment while the cathode formulation and surface density were adjusted accordingly.
Example 2
LiH 50.4g was weighed, and crushed by grinding with a ball mill, followed by addition of Co (OH)246.5g and Fe2O339.93g, further grinding and mixing with a ball mill to obtain uniformly mixed LiH and Co (OH)2And Fe2O3A mixture of (a). Putting the obtained material into an electric heating furnaceKeeping the temperature of 900 ℃ for 8h under the nitrogen atmosphere. Freely cooling to room temperature, taking out, grinding, sieving, and adding 0.3 wt% SnO2And then, mixing by using a mechanical grinding mode to obtain a uniformly mixed mixture, and then placing the obtained material into an electric heating furnace to keep the temperature of 800 ℃ for 3 hours in a nitrogen atmosphere. Freely cooling to room temperature, taking out, grinding and sieving to obtain Li6+aCo1-xFexO4-bWherein x is 0.5, -0.2. ltoreq. a.ltoreq.0.2, -0.2. ltoreq. b.ltoreq.0.2.
The median particle diameter D50 of the sample was 24.37 μm and the width of the particle size distribution (D90-D10)/D50 was 2.27. The specific surface area of the material is 0.26m2The XRD spectrum in figure 5 shows that the prepared anode material crystal form and Li6CoO4The correspondence is good.
The prepared positive electrode material is made into a complete lithium ion full battery. The battery capacity is tested by adopting a Xinwei test device BTS79, and the charging capacity can reach 912.4 mAh/g.
The prepared cathode material was fabricated into a blended electrode and assembled into a full cell in the same manner as in example 1, including the components, formulations, and negative electrode formulation, and the electrochemical performance was tested. The first charge capacity of the battery reaches 214.5mAh/g, the discharge capacity is 193.4mAh/g, the energy density reaches 809Wh/L, and the capacity retention rate of the battery is 84.7 percent after the battery is subjected to 500 charge-discharge cycles.
Example 3
Weighing Li2O91.5 g, Li by ball mill2O grinding and crushing, then adding Co (OH)255.8g and Fe2O331.94g, and continuously grinding and mixing by using a ball mill to obtain uniformly mixed Li2O、Co(OH)2And Fe2O3A mixture of (a). Placing the obtained material into an electric heating furnace, and keeping the temperature of the electric heating furnace at 850 ℃ for 10 hours in an argon atmosphere. And (3) freely cooling to room temperature, taking out, grinding, sieving, adding 0.5 wt% of ZnO2, mixing in a mechanical grinding mode to obtain a uniformly mixed mixture, and placing the obtained material into an electric heating furnace to keep the temperature of 700 ℃ for 4 hours in an argon atmosphere. Cooling to room temperature, grinding, and sievingUntil the present application, Li was available6+aCo1-xFexO4-bWherein x is 0.4, -0.2. ltoreq. a.ltoreq.0.2, -0.2. ltoreq. b.ltoreq.0.2.
The median particle diameter D50 of the sample was 22.55 μm and the width of the particle size distribution (D90-D10)/D50 was 2.03. The specific surface area of the material is 0.37m2The XRD spectrum in figure 5 shows that the prepared anode material crystal form and Li6CoO4The correspondence is good.
The prepared positive electrode material was fabricated into a complete lithium ion full cell in the manner of example 1. The battery capacity is tested by adopting a Xinwei test device BTS79, and the charging capacity can reach 924.9 mAh/g.
The prepared anode material is made into a blended electrode and assembled into a full cell to test the electrochemical performance. The first charge capacity of the battery reaches 214.7mAh/g, the discharge capacity is 193.7mAh/g, the energy density reaches 810Wh/L, and the capacity retention rate of the battery is 85.1% after the battery is subjected to 500 charge-discharge cycles.
Example 4
Weighing Li2O93g, Li by ball milling2O grinding and crushing, then adding Co (OH)265.1g and Fe2O323.96g, further grinding and mixing by using a ball mill to obtain uniformly mixed Li2O、Co(OH)2And Fe2O3A mixture of (a). Placing the obtained material into an electric heating furnace, and keeping the temperature of 800 ℃ for 12h under the nitrogen atmosphere. Freely cooling to room temperature, taking out, grinding, sieving, and adding 1 wt% Al2O3And then, mixing by using a mechanical grinding mode to obtain a uniformly mixed mixture, and then placing the obtained material into an electric heating furnace to keep the temperature of 600 ℃ for 5 hours in a nitrogen atmosphere. The Li can be obtained after the battery is freely cooled to room temperature and then taken out, ground and sieved6+aCo1-xFexO4-bWherein x is 0.3, -0.2. ltoreq. a.ltoreq.0.2, -0.2. ltoreq. b.ltoreq.0.2.
The median particle diameter D50 of the sample was 19.79 μm and the width of the particle size distribution (D90-D10)/D50 was 1.81. The specific surface area of the material is 0.46m2The XRD pattern in figure 5 shows that the prepared positive electrode material has crystal formWith Li6CoO4The correspondence is good.
The prepared positive electrode material was fabricated into a complete lithium ion full cell in the manner of example 1. The battery capacity is tested by adopting a Xinwei test device BTS79, and the charging capacity can reach 935.2 mAh/g.
The prepared anode material is made into a blended electrode and assembled into a full cell to test the electrochemical performance. The first charge capacity of the battery reaches 214.9mAh/g, the discharge capacity is 193.9mAh/g, the energy density reaches 811Wh/L, and the capacity retention rate of the battery is 86.7 percent after 500 charge-discharge cycles.
Example 5
Weighing LiOH. H2O264.6 g, using a ball mill to mix LiOH. H2O grinding and crushing, then adding CoO 60g and Fe (OH)321.37g, further grinding and mixing by using a ball mill to obtain uniformly mixed LiOH & H2O, CoO and Fe (OH)3A mixture of (a). Placing the obtained material into an electric heating furnace, and keeping the temperature of 750 ℃ for 14h under the atmosphere of neon. Freely cooling to room temperature, taking out, grinding, sieving, and adding 2 wt% AlPO4And then, mixing by using a mechanical grinding mode to obtain a uniformly mixed mixture, and then placing the obtained material into an electric heating furnace to keep the temperature of 600 ℃ for 6 hours in a nitrogen atmosphere. The Li can be obtained after the battery is freely cooled to room temperature and then taken out, ground and sieved6+aCo1-xFexO4-bWherein x is 0.2, -0.2. ltoreq. a.ltoreq.0.2, -0.2. ltoreq. b.ltoreq.0.2.
The median particle diameter D50 of the sample was 17.86 μm and the width of the particle size distribution (D90-D10)/D50 was 1.63. The specific surface area of the material is 0.51m2The XRD spectrum in figure 5 shows that the prepared anode material crystal form and Li6CoO4The correspondence is good.
The prepared positive electrode material was fabricated into a complete lithium ion full cell in the manner of example 1. The battery capacity is tested by adopting a Xinwei test device BTS79, and the charging capacity can reach 945.1 mAh/g.
The prepared anode material is made into a blended electrode and assembled into a full cell to test the electrochemical performance. The first charge capacity of the battery reaches 215.2mAh/g, the discharge capacity is 193.5mAh/g, the energy density reaches 809Wh/L, and the capacity retention rate of the battery is 86.2 percent after the battery is subjected to 500 charge-discharge cycles.
Example 6
Weighing 151.2g of LiOH, grinding and crushing the LiOH by using a ball mill, and then adding 67.5g of CoO and Fe (OH)310.69g, further grinding and mixing by using a ball mill to obtain uniformly mixed LiOH, CoO and Fe (OH)3A mixture of (a). Placing the obtained material into an electric heating furnace, and keeping the temperature of 700 ℃ for 16h under the atmosphere of krypton. And (3) freely cooling to room temperature, taking out, grinding, sieving, adding 3 wt% of MgO, mixing in a mechanical grinding mode to obtain a uniformly mixed mixture, and placing the obtained material into an electric heating furnace to keep the temperature of 500 ℃ for 8 hours in an argon atmosphere. The Li can be obtained after the battery is freely cooled to room temperature and then taken out, ground and sieved6+aCo1-xFexO4-bWherein x is 0.1, -0.2. ltoreq. a.ltoreq.0.2, -0.2. ltoreq. b.ltoreq.0.2.
The median particle diameter D50 of the sample was 15.97 μm and the width of the particle size distribution (D90-D10)/D50 was 1.52. The specific surface area of the material is 0.62m2The XRD spectrum in figure 5 shows that the prepared anode material crystal form and Li6CoO4The correspondence is good.
The prepared positive electrode material was fabricated into a complete lithium ion full cell in the manner of example 1. The battery capacity is tested by adopting a Xinwei test device BTS79, and the charging capacity can reach 956.4 mAh/g.
The prepared anode material is made into a blended electrode and assembled into a full cell to test the electrochemical performance. The first charge capacity of the battery reaches 215.3mAh/g, the discharge capacity is 192.6mAh/g, the energy density reaches 805Wh/L, and the capacity retention rate of the battery is 85.2 percent after the battery is subjected to 500 charge-discharge cycles.
Example 7
Weighing Li2CO3221.7g, Li was added by using a ball mill2CO3Grinding, then adding CoO 74.25g and Fe (OH)31.069g, continuously grinding and mixing by using a ball mill to obtain uniformly mixed Li2CO3CoO and Fe (OH)3OfA compound (I) is provided. Placing the obtained material into an electric heating furnace, and keeping the temperature of 600 ℃ for 18h under the helium atmosphere. Freely cooling to room temperature, taking out, grinding, sieving, and adding 4 wt% SiO2And then, mixing by using a mechanical grinding mode to obtain a uniformly mixed mixture, and then placing the obtained material into an electric heating furnace to keep the temperature of 400 ℃ for 10 hours in an argon atmosphere. The Li can be obtained after the battery is freely cooled to room temperature and then taken out, ground and sieved6+aCo1-xFexO4-bWherein x is 0.01, -0.2. ltoreq. a.ltoreq.0.2, -0.2. ltoreq. b.ltoreq.0.2.
The median particle diameter D50 of the sample was 11.44 μm and the width of the particle size distribution (D90-D10)/D50 was 1.44. The specific surface area of the material is 0.76m2The XRD spectrum in figure 5 shows that the prepared anode material crystal form and Li6CoO4The correspondence is good.
The prepared positive electrode material was fabricated into a complete lithium ion full cell in the manner of example 1. The battery capacity is tested by adopting a Xinwei test device BTS79, and the charging capacity can reach 960.9 mAh/g.
The prepared anode material is made into a blended electrode and assembled into a full cell to test the electrochemical performance. The first charge capacity of the battery reaches 215.2mAh/g, the discharge capacity is 192.0mAh/g, the energy density reaches 803Wh/L, and the capacity retention rate of the battery is 84.5 percent after 500 charge-discharge cycles.
Example 8
Weighing Li2O2138g, Li by ball mill2O2Grinding and crushing, then adding Co3O479.87g and Fe3O40.386g, continuously using the ball mill to grind and mix to obtain evenly mixed Li2O2、Co3O4And Fe3O4A mixture of (a). Placing the obtained material into an electric heating furnace, and keeping the temperature of the furnace at 500 ℃ for 21h under the argon atmosphere. Freely cooling to room temperature, taking out, grinding, sieving, and adding 5 wt% of TiO2And then, mixing by using a mechanical grinding mode to obtain a uniformly mixed mixture, and then putting the obtained material into an electric heating furnace to keep the temperature of 300 ℃ for 12 hours in an argon atmosphere. Freely cooling to room temperatureThen taking out, grinding and sieving to obtain Li for the battery6+aCo1-xFexO4-bWherein x is 0.005, -0.2. ltoreq. a.ltoreq.0.2, -0.2. ltoreq. b.ltoreq.0.2.
The median particle diameter D50 of the sample is 8.058 μm, and the width of the particle size distribution (D90-D10)/D50 is 1.34. The specific surface area of the material is 0.88m2The XRD spectrum in figure 5 shows that the prepared anode material crystal form and Li6CoO4The correspondence is good.
The prepared positive electrode material was fabricated into a complete lithium ion full cell in the manner of example 1. The battery capacity is tested by adopting a Xinwei test device BTS79, and the charging capacity can reach 965.3 mAh/g.
The prepared anode material is made into a blended electrode and assembled into a full cell to test the electrochemical performance. The first charge capacity of the battery reaches 214.6mAh/g, the discharge capacity is 191.6mAh/g, the energy density reaches 801Wh/L, and the capacity retention rate of the battery is 84.2% after the battery is subjected to 500 charge-discharge cycles.
Example 9
LiH48.8g was weighed, and LiH was ground and crushed using a ball mill, after which Co was added3O480.11g and Fe3O40.154g, continuously grinding and mixing by using a ball mill to obtain uniformly mixed LiH and Co3O4And Fe3O4A mixture of (a). Placing the obtained material into an electric heating furnace, and keeping the temperature of the material at 400 ℃ for 24 hours in an argon atmosphere. The Li can be directly obtained for the battery without coating treatment after being ground and sieved6+aCo1-xFexO4-bWherein x is 0.002, -0.2. ltoreq. a.ltoreq.0.2, -0.2. ltoreq. b.ltoreq.0.2.
The median particle diameter D50 of the sample is 5.011 mu m, and the width of the particle size distribution (D90-D10)/D50 is 1.2. The specific surface area of the material is 0.92m2The XRD spectrum in figure 5 shows that the prepared anode material crystal form and Li6CoO4The correspondence is good.
The prepared positive electrode material was fabricated into a complete lithium ion full cell in the manner of example 1. The battery capacity is tested by adopting a Xinwei test device BTS79, and the charging capacity can reach 966.2 mAh/g.
The prepared anode material is made into a blended electrode and assembled into a full cell to test the electrochemical performance. The first charge capacity of the battery reaches 214.6mAh/g, the discharge capacity is 191.6mAh/g, the energy density reaches 801Wh/L, and the capacity retention rate of the battery is 84.2% after the battery is subjected to 500 charge-discharge cycles.
Comparative example 1
Weighing Li2O94.5 g, Li was added by using a ball mill2Grinding and crushing O, adding 75g of CoO, and continuously grinding and mixing by using a ball mill to obtain uniformly mixed Li2Mixtures of O and CoO. Placing the obtained material into an electric heating furnace, and keeping the temperature of 750 ℃ for 14h under the argon atmosphere. Freely cooling to room temperature, taking out, grinding, sieving, and adding 2 wt% AlPO4And then, mixing by using a mechanical grinding mode to obtain a uniformly mixed mixture, and then putting the obtained material into an electric heating furnace to keep the temperature of 600 ℃ for 6 hours in an argon atmosphere. And (4) freely cooling to room temperature, taking out, grinding and sieving to obtain the cathode material for the comparative example.
The median particle diameter D50 of the sample is 17.77 μm, and the width of the particle size distribution (D90-D10)/D50 is 1.66. The specific surface area of the material is 1.24m2(g) specific surface area of the positive electrode material in example 5: 0.51m2Compared with the specific surface area per gram, the specific surface area of the positive electrode material is obviously overlarge, and the overlarge specific surface area of the positive electrode material is easy to agglomerate and difficult to disperse and the pole piece is difficult to process.
As shown in XRD spectrum in figure 5, the prepared anode material crystal form and Li6CoO4 corresponds.
The prepared positive electrode material was fabricated into a complete lithium ion full cell in the manner of example 1. The cell capacity was tested using the novalr test equipment BTS79 and was found to have a charge capacity of 966.6mAh/g (this charge capacity is the maximum delithiation capacity of the positive electrode material and its relative size is not equivalent to the full cell reversible capacity or the relative size of the volumetric energy density). And the increase of the compaction density caused by the introduction of Fe and the reduction of side reactions between solid-liquid interfaces enable the increase of the total volume energy density of the battery to be more visual.
The prepared positive electrode material was fabricated into a blended electrode in the manner of example 1 and assembled into a full cell to test electrochemical properties. The first charge capacity of the battery reaches 214.6mAh/g, the discharge capacity is 191.2mAh/g, the energy density reaches 797Wh/L, and the capacity retention rate of the battery is 84.1% after the battery is subjected to 500 charge-discharge cycles. Compared with the comparative example 1, the positive electrode material of the embodiment 5 introduced with Fe has the advantages of higher full cell volumetric energy density, better cycle stability and lower cost.
Comparative example 2
Weighing Li2O2559.7g, Li was added by using a ball mill2O grinding and crushing, then adding CoO 148.4g, Co (OH)2184.0g、Al2O31.1g and 0.56g of elemental Si, to give uniformly mixed Li2O2、CoO、Al2O3And a mixture of Si. Placing the obtained material into an electric heating furnace, and keeping the temperature of 750 ℃ for 15h under the argon atmosphere. Freely cooling to room temperature, taking out, grinding, sieving, and adding 8.9g AlPO4And then, mixing by using a mechanical grinding mode to obtain a uniformly mixed mixture, and then placing the obtained material into an electric heating furnace to keep the temperature of 650 ℃ for 2 hours in an argon atmosphere. And (4) freely cooling to room temperature, taking out, grinding and sieving to obtain the battery positive electrode material.
The median particle diameter D50 of the sample was 10.32 μm and the width of the particle size distribution (D90-D10)/D50 was 1.77. The specific surface area of the material is 1.22m2Per g, as compared with example 5, it can be shown that there is Li incorporated by Fe6CoO4The specific surface area is lower, so that the cathode material is easier to process. And the introduction of Fe improves the compaction density of the anode material, and the total volume energy density of the battery is improved.
As shown in XRD spectrum in figure 4, the prepared anode material crystal form and Li6CoO4And correspondingly.
The prepared positive electrode material is made into a complete lithium ion full battery. The battery capacity was tested using the nova test equipment BTS79 and the charge capacity was 965 mAh/g. But the increase of the compaction density brought by the introduction of Fe enables the increase of the total volume energy density of the battery to be more visual.
The prepared positive electrode material was fabricated into a blended electrode in the manner of example 1 and assembled into a full cell to test electrochemical properties. The first charge capacity of the battery reaches 214.3mAh/g, the discharge capacity is 192.3mAh/g, the energy density reaches 801Wh/L, and the capacity retention rate of the battery is 84.0% after 500 charge-discharge cycles. Compared with the comparative example 2, the cathode material has higher volume energy density and cycle stability, and meanwhile, the cost of iron is far lower than that of cobalt, so the cathode material provided by the application has more popularization and commercial significance.
Comparative example 3
49.6g of LiH is weighed, the LiH is ground and crushed using a ball mill, and then Co is added3O416.05g and Fe (OH)385.5g, continuously using the ball mill to grind and mix to obtain evenly mixed LiH and Co3O4And Fe (OH)3A mixture of (a). Placing the obtained material into an electric heating furnace, and keeping the temperature of 800 ℃ for 12h under the argon atmosphere. Freely cooling to room temperature, taking out, grinding, sieving, and adding 1 wt% Al2O3And then, mixing by using a mechanical grinding mode to obtain a uniformly mixed mixture, and then placing the obtained material into an electric heating furnace to keep the temperature of 600 ℃ for 5 hours in an argon atmosphere. And (4) freely cooling to room temperature, taking out, grinding and sieving to obtain the anode material for the battery.
The median particle diameter D50 of the sample was 19.66 μm and the width of the particle size distribution (D90-D10)/D50 was 1.83. The specific surface area of the material is 0.98m2The XRD spectrum in figure 5 shows that the prepared cathode material crystal form fails to be combined with Li6CoO4Good correspondence, impurity Li appearing in the middle5FeO4The crystalline phase of (a). When the amount of Fe is 80%, synthesized Li6CoO4Starting to appear impurity Li5FeO4. Impurity (impurity Li)5FeO4) The capacity of the battery is generally difficult to exert, and part of impurities can influence the circulation of the battery, thereby causing the performance of the subsequent battery to be poor.
The prepared positive electrode material is made into a complete lithium ion full battery. The battery capacity was tested using the nova test equipment BTS79 and its charge capacity was 636.8 mAh/g.
The prepared positive electrode material was fabricated into a blended electrode in the manner of example 1 and assembled into a full cell to test electrochemical properties. The battery has the first charge capacity of 206.8mAh/g, the discharge capacity of 186.6mAh/g and the energy density of 776Wh/L, and after the battery is subjected to 500 charge-discharge cycles, the capacity retention rate is 77.6%, impurities obviously influence the cycle performance, and the battery is difficult to serve as a preferred anode material.
Comparative example 4
Directly using 100% LiCoO2Electrodes were fabricated and assembled into a full cell in the manner of example 1, and electrochemical performance was tested. The first charge capacity of the battery reaches 200mAh/g, the discharge capacity is 189.3mAh/g, the energy density is 780Wh/L, and the capacity retention rate of the battery is 83.9 percent after the battery is subjected to 500 charge-discharge cycles. The cathode material provided by the application is a blended electrode system which passes through a blending part (Li)6CoO4) The released high capacity compensates Li consumed by CEI and SEI on the surfaces of the positive electrode and the negative electrode, so that higher reversible capacity and higher energy density of the battery are obtained.
Li prepared by the above preferred embodiments and comparative examples, the synthesis method adopted in the present application6+aCo1- xFexO4-bThe prepared anode material is a strict homogeneous phase, segregation impurity phases of lithium oxide, cobalt oxide and iron oxide do not exist, local lithium precipitation of the cathode cannot be caused, the pH value of the material is low, and the subsequent processability of the material is ensured. The highest charge capacity can reach 966.2mAh/g, exceeding the maximum value that can be reached by the prior art charge capacity, and almost in line with the theoretical capacity. While Li6+aCo1-xFexO4-bLi at decomposition release+And then, the generated products are cobalt and iron oxide, and have no obvious negative influence on the cycle performance of the battery. In addition, element doping and surface coating are carried out on the anode material, so that the high-rate discharge of the material is improved, the cycle efficiency and the thermal stability of the anode material are improved, the cobalt atoms in the anode material are uniformly dissolved out, and the stability of the anode material provided by the application can be greatly improved.
As can be seen from SEM test results, the synthesized Li in the application6+aCo1-xFexO4-bThe particle size distribution is uniform, the particle sphericity is high, the compaction density of the electrode can be improved to the maximum extent, and when the electrode is mixed with other anode materials, the contact among particles can be greatly improved by a round and smooth surface, the internal resistance is reduced, and the compaction density is improved. In the existing lithium battery system, the energy density of the battery can be greatly improved. In addition, the preparation, doping and coating methods and processes related to the method are relatively simple, and expensive equipment support is not needed, so that industrial production is realized, and the use scale is enlarged.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Finally, it should be noted that: although the present application has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described in the foregoing embodiments, or equivalents may be substituted for elements thereof. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims (10)

1. A positive electrode material for a battery, comprising:
has a chemical formula of Li6+aCo1-xFexO4-bWherein 0 is<x is less than or equal to 0.6, a is less than or equal to 0.2, b is less than or equal to 0.2, and the median particle diameter D50 is between 5 and 30 mu m.
2. The positive electrode material according to claim 1, wherein the specific surface area of the positive electrode material is 0.11m2G to 0.92m2Between/g.
3. The positive electrode material according to claim 1, wherein the positive electrode material is characterized in thatIn the above, Li6+aCo1-xFexO4-bThe width of the particle size distribution is between 1.2 and 2.4.
4. The positive electrode material according to claim 1, further comprising a coating substance that coats a surface of the positive electrode material.
5. The positive electrode material according to claim 1, wherein the coating substance comprises: al (Al)2O3、TiO2、SiO2、MgO、ZrO2、AlPO4、ZnO、SnO2One or more of (a).
6. The positive electrode material according to claim 4, wherein the content of the covering material is between 0.1 wt% and 5 wt% based on the total weight of the positive electrode material.
7. The positive electrode material according to any one of claims 1 to 6, wherein the Li6+aCo1-xFexO4-bDiffraction peaks generated when the material is tested by an X-ray diffractometer comprise peak positions at which the 2 theta diffraction angles are 19.2 +/-0.2 degrees, 23.4 +/-0.2 degrees, 27.3 +/-0.2 degrees, 33.5 +/-0.2 degrees, 36.3 +/-0.2 degrees and 56.0 +/-0.2 degrees.
8. An electrode comprising the positive electrode material according to claims 1 to 7.
9. A battery comprising the electrode of claim 8.
10. A method for producing the positive electrode material according to claim 1, comprising:
grinding and mixing a lithium precursor, a cobalt precursor and an iron precursor to obtain a precursor mixture of lithium, cobalt and iron;
sintering the precursor mixture of lithium, cobalt and iron in an inert atmosphere to obtain a first product;
and crushing, screening and demagnetizing the first product to obtain the cathode material.
CN201911412805.6A 2019-12-31 2019-12-31 Positive electrode material for battery, battery positive electrode, battery and preparation method of positive electrode material Pending CN111162258A (en)

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