CN115121335A - Positive electrode material and preparation method and application thereof - Google Patents

Positive electrode material and preparation method and application thereof Download PDF

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Publication number
CN115121335A
CN115121335A CN202110326448.2A CN202110326448A CN115121335A CN 115121335 A CN115121335 A CN 115121335A CN 202110326448 A CN202110326448 A CN 202110326448A CN 115121335 A CN115121335 A CN 115121335A
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positive electrode
equal
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battery
ltoreq
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支键
陈璞
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Ruihai Bo Changzhou Energy Technology Co ltd
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Ruihaibo Inc
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
    • B02C17/18—Details
    • B02C17/20—Disintegrating members
    • 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
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • 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

Abstract

The invention discloses a positive electrode material and a preparation method and application thereof, wherein the method comprises the following steps: the wet ball milling was performed using three kinds of grinding balls of different diameters mixed with the positive electrode active material and the solvent, so as to obtain a positive electrode material. Therefore, the anode material prepared by the method has a pseudo-capacitance phenomenon and a hierarchical structure, and can improve the capacity, rate capability and cycle performance of the battery when being applied to the battery.

Description

Positive electrode material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a positive electrode material as well as a preparation method and application thereof.
Background
A positive electrode material, particularly a spinel-type lithium manganese oxide having a three-dimensional tunnel structure for lithium ion transport, has received much attention as a potential high-power positive electrode material for an aqueous battery due to its high operating voltage, low production cost, low toxicity, excellent voltage distribution, and the like. In addition to widespread use in lithium ion batteries, in recent years, Lithium Manganese Oxide (LMO) has been used in a new secondary water system Zn/LiMn 2 O 4 A battery system, also known as a rechargeable water-based hybrid battery (ReHAB). The energy density of the ReHAB is about 50-80 Wh/kg -1 Is the energy density of a commercial lead-acid battery (about30 to 70 Wh/kg -1 ) Twice as much.
Commercial LMO generally adopts methods such as a high-temperature solid phase method, a microwave synthesis method, a hydrothermal synthesis method, a coprecipitation method and the like, and the prepared LMO is generally applied to battery production without additional treatment. Commercial LMO-based electrode materials have inherent drawbacks: poor electrical conductivity, Li + /e - The transmission dynamics is poor and the volume expansion is obvious. To date, reducing the particle size of LMO to the micro/nano scale remains the primary strategy to improve its electrochemical performance. Many LMO-based nanostructures, including nanoparticles, nanotubes, and nanoplatelets, among others, have been designed to enhance Li + /e - Transport kinetics and buffer volume expansion/contraction during discharge/charge. However, low dimensional nanostructures tend to aggregate during the reaction, resulting in poor cycle life and low capacity at high rates.
Therefore, rational design of LMO-based micro/nanostructures remains crucial for high performance batteries.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, one object of the present invention is to provide a positive electrode material, a preparation method and applications thereof, wherein the positive electrode material prepared by the method has a pseudo-capacitance phenomenon and a hierarchical structure, and when the positive electrode material is applied to a battery, the capacity, rate capability and cycle performance of the battery can be improved.
In one aspect of the invention, a method of making a positive electrode material is presented. According to an embodiment of the invention, the method comprises: the wet ball milling was performed using three kinds of grinding balls of different diameters mixed with the positive electrode active material and the solvent, so as to obtain a positive electrode material.
According to the method for preparing the cathode material, provided by the embodiment of the invention, the three grinding balls with different diameters are mixed with the cathode active material and the solvent for wet ball milling, so that the pseudo-capacitance phenomenon, namely Li, can be generated in the obtained cathode material compared with dry ball milling + Under the control of pseudo capacitance, the anode material quickly diffuses to show excellent rate propertyThe energy and the cycle performance are combined, the pseudo-capacitance contribution rate of the electrode can reach 94% at most, and the pseudo-capacitance contribution rate is close to a typical pseudo-capacitance material in a super capacitor; in addition, three grinding balls with different diameters are matched for use, wherein the large-particle-diameter ball grinding ball mainly cuts and peels off large-particle-diameter blocky positive electrode active materials, edges and corners of blocky particles are removed, and the small-particle-diameter ball grinding ball mainly crushes and peels off particles. The porous anode material consisting of micron-sized, submicron-sized and aggregated nanoparticles is obtained by wet ball milling, presents a hierarchical structure with the particle size of 100-900 nm, increases the specific surface area and pore volume of the anode material, enables the anode material to be in good contact with electrolyte, reduces the charge transfer impedance, and is beneficial to Li + The insertion/extraction reaction of (2) improves the capacity, and the hierarchical structure can also promote the above pseudocapacitance Li + And (4) diffusion. Therefore, the anode material prepared by the method has a pseudo-capacitance phenomenon and a hierarchical structure, and can improve the capacity, rate capability and cycle performance of the battery when being applied to the battery.
In addition, the method for preparing the cathode material according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the present invention, the diameter of the large ball of the grinding ball is 10 to 20mm, the diameter of the medium ball is 5 to 10mm, and the diameter of the small ball is 1 to 5 mm. Thereby, the capacity, rate capability and cycle performance of the battery can be improved.
In some embodiments of the invention, the number ratio of the large balls, the medium balls and the small balls is 1: (1-9): (1-6). Thereby, the capacity, rate capability and cycle performance of the battery can be improved.
In some embodiments of the present invention, the ball milling speed of the wet ball milling is 60 to 380 rpm, and the ball milling time is 2 to 10 hours. Thereby, the capacity, rate capability and cycle performance of the battery can be improved.
In some embodiments of the present invention, it is characterized in that the mass ratio of the positive electrode active material, the grinding balls, and the solvent is 1: (1-6): (0.1 to 3). Thereby, the capacity, rate capability and cycle performance of the battery can be improved.
In some embodiments of the present invention, a ratio of a total volume of the positive electrode active material, the grinding balls and the solvent to a container volume is (1-4): 5. thereby, the capacity, rate capability and cycle performance of the battery can be improved.
In some embodiments of the invention, the positive active material is selected from one or more of the following: corresponds to the general formula Li 1+x Mn y M z O k Wherein-1. ltoreq. x.ltoreq.0.5, 1. ltoreq. y.ltoreq.2.5, 0. ltoreq. z.ltoreq.0.5, 3. ltoreq. k.ltoreq.6, M comprises at least one of Na, Li, Co, Mg, Ti, Cr, V, Zn, Zr, Si and Al; corresponds to the general formula Li 1+x M y M' z M" c O 2+n The compound of (1), wherein<x is less than or equal to 0.5, y is less than or equal to 0 and less than or equal to 1, z is less than or equal to 0 and less than or equal to 1, c is less than or equal to 0 and less than or equal to-0.2, n is less than or equal to 0.2, and M, M 'and M' are respectively selected from at least one of Ni, Mn, Co, Mg, Ti, Cr, V, Zn, Zr, Si and Al; and corresponds to the formula Li x M 1-y M' y (XO 4 ) n A compound of (1), wherein 0<X is less than or equal to 2, y is less than or equal to 0 and less than or equal to 0.6, n is less than or equal to 1 and less than or equal to 1.5, M is selected from Fe, Mn, V or Co, M' is selected from at least one of Mg, Ti, Cr, V and Al, and X is selected from at least one of S, P and Si.
In some embodiments of the invention, it is characterized in that the positive active material includes LiMn 2 O 4 ，LiTi 2 (PO 4 ) 3 And LiNi 1/3 Co 1/3 Mn 1/3 O 2 At least one of (a).
In a second aspect of the invention, a positive electrode material is provided. According to the embodiment of the invention, the cathode material is prepared by adopting the method for preparing the cathode material. Therefore, the positive electrode material has a pseudocapacitance effect and a hierarchical structure with the particle size of 100-900 nm, so that the positive electrode material has high capacity and excellent rate capability and cycle performance.
In a third aspect of the invention, a battery is provided. According to an embodiment of the invention, the battery has the cathode material or the cathode material prepared by the method. Thus, the battery has high capacity and excellent rate performance and cycle performance.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 (a) is an SEM image of the positive electrode material of comparative example 1; fig. 1 (b) is an SEM image of the positive electrode material of example 5; fig. 1 (c) is an SEM image of the positive electrode material of example 4; fig. 1 (d) is an SEM image of the positive electrode material of example 1; fig. 1 (e) is a microstructure size of the positive electrode material of comparative example 1; fig. 1 (f) is the microstructure size of the positive electrode material of example 5; fig. 1 (g) is the microstructure size of the positive electrode material of example 4; fig. 1 (h) is a microstructure size of the positive electrode material of example 1; FIG. 1 (i) is a comparison of specific surface areas of the positive electrode materials of comparative examples 1 and 3 and examples 1, 4 to 5;
fig. 2 (a) is a cyclic voltammogram of the positive electrode of the battery of comparative example 1; fig. 2 (b) is a cyclic voltammogram of the positive electrode of the battery of example 5; fig. 2 (c) is a cyclic voltammogram of the positive electrode of the battery of example 4; FIG. 2 (d) is a cyclic voltammogram of the positive electrode of the cell of example 1 (scan rates are all 1mV/s, shaded areas show pseudocapacitance current contributions);
fig. 3 is a graph comparing the rate performance of example 1 and comparative example 1.
Detailed Description
The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
In a first aspect of the invention, a method of making a positive electrode material is presented. According to an embodiment of the invention, the method comprises: three kinds of grinding balls with different diameters are mixed with the positive electrode active material and the solvent to carry out wet ball milling.
The inventor finds that the obtained cathode material can generate pseudo capacitance phenomenon, namely Li, compared with dry ball milling by mixing three grinding balls with different diameters with cathode active materials and solvents to carry out wet ball milling + Under the control of the pseudocapacitance, the anode material is quickly diffused, so that the anode material has excellent multiplying power performance and cycle performance, the pseudocapacitance contribution rate of the electrode can reach 94% at most, and the anode material is close to a typical pseudocapacitance material in a super capacitor; in addition, three grinding balls with different diameters are matched for use, wherein the large-particle-diameter ball grinding ball mainly cuts and peels off large-particle-diameter blocky positive electrode active materials, edges and corners of blocky particles are removed, and the small-particle-diameter ball grinding ball mainly crushes and peels off particles. The porous anode material consisting of micron-sized, submicron-sized and aggregated nanoparticles is obtained by wet ball milling, and has a hierarchical structure with the particle size of 100-900 nm, the specific surface area and the pore volume of the anode material are increased, so that the anode material is in good contact with electrolyte, the charge transfer resistance is reduced, and Li is favorable for Li + The insertion/extraction reaction of (2), the capacity is improved, and the hierarchical structure can also promote the above pseudocapacitance Li + And (4) diffusion. Therefore, the anode material prepared by the method has a pseudo-capacitance phenomenon and a hierarchical structure, and can improve the capacity, rate capability and cycle performance of the battery when being applied to the battery.
Furthermore, the diameter of the large ball of the grinding ball is 10-20 mm, the diameter of the medium ball is 5-10 mm, and the diameter of the small ball is 1-5 mm. Preferably, the grinding balls have a large ball diameter of 12mm, a medium ball diameter of 6mm and a small ball diameter of 3 mm. The inventors have found that if the diameter of the large spheres is too large or too small, the micropore volume of the positive electrode material increases only to a limited extent compared to that before wet ball milling, and the electrical characteristics of the battery increase only to a limited extent. Meanwhile, if the diameter of the medium ball is too large or too small, the volume of the macropore of the anode material is greatly reduced compared with that before wet ball milling, and the performance of the battery is not favorably exerted. In addition, if the diameter of the small ball is too large or too small, the pore structure of the anode material is basically the same as that before wet ball milling, and the wet ball milling does not play a role. Therefore, by adopting the diameters of the large balls, the medium balls and the small balls, the porous anode material consisting of micron-sized, submicron-sized and aggregated nanoparticles can be obtained, and the hierarchical structure with the particle size of 100-900 nm is presented, so that the electrical property of the battery can be improved. Therefore, the grinding balls with the three diameters are beneficial to improving the capacity, rate capability and cycle performance of the battery.
Further, the number ratio of the big balls, the middle balls and the small balls is 1: (1-9): (1-6). The inventor finds that if the number of the large balls is too large, the size distribution discrete degree of the hierarchical structure of the anode material is too large, and the pseudo-capacitance phenomenon is weakened; if the number of the large balls is too small, larger particles in the anode material cannot be crushed, which is not favorable for the exertion of the electrical property; meanwhile, if the number of the medium spheres is too large or too small, the size distribution dispersion degree of the hierarchical structure of the anode material is too large, the number of particles of 300-700 nm is too large or too small, and the pseudo-capacitance phenomenon is weakened; in addition, if the number of the small balls is too large, too many particles smaller than 100nm can be generated, which is not favorable for the process performance; if the number of the small balls is too small, the size distribution of the hierarchical structure is too narrow, particles of 100-300 nm are fewer, and the pseudo-capacitance phenomenon is weakened. Therefore, the pseudocapacitance phenomenon can be enhanced by adopting the number ratio of the large balls, the middle balls and the small balls.
Furthermore, the ball milling speed of the wet ball milling is 60-380 r/min, and the ball milling time is 2-10 hours. The inventor finds that if the rotating speed of the wet ball milling is too low, the ball milling cannot be carried out sufficiently, so that the purpose of the application cannot be achieved, and if the rotating speed of the wet ball milling is too high, the size distribution of the hierarchical structure is too narrow, 700-900 nm particles are too few, the pseudo-capacitance phenomenon is weakened, and the capacity of the battery is influenced; meanwhile, if the ball milling time is too short, the size distribution of the hierarchical structure is too narrow, the battery capacity is insufficient, and the battery performance is influenced; if the ball milling time is too long, the size distribution of the hierarchical structure is too narrow, particles of 700-900 nm are too few, the pseudo-capacitance phenomenon is weakened, the capacity of the battery is obviously reduced after being increased, and the performance of the battery is also influenced. Thus, a battery having a high capacity and excellent rate capability and cycle performance can be obtained using the wet ball milling conditions described above.
Further, the mass ratio of the positive electrode active material, the grinding ball and the solvent is 1: (1-6): (0.1 to 3). The inventor finds that too much or too little grinding balls can cause the size distribution of the anode material hierarchical structure to be too narrow, so that the exertion of pseudo-capacitance capacity is not facilitated, and the battery capacity is influenced; too much or too little solvent can cause the size distribution dispersion degree of the anode material hierarchical structure to be too large, and the pseudo-capacitance phenomenon is influenced. Therefore, the mass ratio of the battery can enhance the pseudo capacitance phenomenon, and is beneficial to the exertion of pseudo capacitance capacity, thereby improving the electrical property of the battery.
Further, the ratio of the total volume of the positive electrode active material, the grinding balls and the solvent to the volume of the container is (1-4): 5. the inventor finds that when the ratio of the total volume of the positive electrode active material, the grinding ball and the solvent to the volume of the container is too small, part of large particles cannot be broken, and the electric performance is not good; the ratio of the total volume of the anode active material, the grinding ball and the solvent to the volume of the container is too large, so that the size distribution dispersion degree of the anode material hierarchical structure is too large, and the pseudo capacitance phenomenon is influenced. From this, adopt the positive pole active material of this application, the total volume of ball and solvent and the volumetric ratio of container can strengthen pseudocapacitance phenomenon, be favorable to the performance of pseudocapacitance capacity simultaneously to can promote the electrical property of battery.
It should be noted that the specific type of the positive electrode active material is not particularly limited, and may be selected by those skilled in the art according to actual needs, for example, the positive electrode active material is selected from one or more of the following: corresponds to the general formula Li 1+ x Mn y M z O k Wherein-1. ltoreq. x.ltoreq.0.5, 1. ltoreq. y.ltoreq.2.5, 0. ltoreq. z.ltoreq.0.5, 3. ltoreq. k.ltoreq.6, M comprises at least one of Na, Li, Co, Mg, Ti, Cr, V, Zn, Zr, Si and Al; corresponds to the general formula Li 1+x M y M' z M" c O 2+n The compound of (1), wherein<x is less than or equal to 0.5, y is less than or equal to 0 and less than or equal to 1, z is less than or equal to 0 and less than or equal to 1, c is less than or equal to 0 and less than or equal to 1, n is less than or equal to 0.2 and less than or equal to 0.2, and M, M 'and M' are respectively selected from at least one of Ni, Mn, Co, Mg, Ti, Cr, V, Zn, Zr, Si and Al; and corresponds to the formula Li x M 1-y M' y (XO 4 ) n A compound of (1), wherein 0<x is less than or equal to 2, y is less than or equal to 0 and less than or equal to 0.6, n is less than or equal to 1 and less than or equal to 1.5, M is selected from Fe, Mn, V or Co, and M' is selected from at least one of Mg, Ti, Cr, V and AlAnd one, X is selected from at least one of S, P and Si. Preferably, the positive electrode active material includes LiMn 2 O 4 ，LiTi 2 (PO 4 ) 3 And LiNi 1/3 Co 1/3 Mn 1/3 O 2 At least one of (a).
It should be noted that, the solvent, the grinding balls and the type of the device for performing wet ball milling can be selected by those skilled in the art according to actual needs, for example, the solvent may be water; the grinding balls comprise at least one of zirconia grinding balls, alumina grinding balls, steel balls, agate beads and polyurethane beads; the device for performing wet ball milling may be a planetary ball mill, a tubular ball mill, a horizontal ball mill or an attritor.
In a second aspect of the invention, a positive electrode material is provided. According to the embodiment of the invention, the cathode material is prepared by adopting the method for preparing the cathode material. Therefore, the positive electrode material has a pseudocapacitance effect and a hierarchical structure with the particle size of 100-900 nm, so that the positive electrode material has high capacity and excellent rate capability and cycle performance. It should be noted that the features and advantages described above for the method of preparing the cathode material are also applicable to the cathode material, and are not described herein again.
In a third aspect of the invention, a battery is provided. According to an embodiment of the present invention, the battery has the above-described cathode material or the cathode material prepared by the above-described method. Thus, the battery has high capacity and excellent rate performance and cycle performance. It should be noted that the features and advantages described above for the positive electrode material and the preparation method thereof are also applicable to the positive electrode material, and are not described herein again.
The following embodiments of the present invention are described in detail, and it should be noted that the following embodiments are exemplary only, and are not to be construed as limiting the present invention. In addition, all reagents used in the following examples are commercially available or can be synthesized according to methods herein or known, and are readily available to one skilled in the art for reaction conditions not listed, if not explicitly stated.
Example 1
Step 1: using three ZrO of different diameters 2 Mixing the balls with LMO and water for wet ball milling, wherein the number ratio of the grinding balls with different diameters is 1: 2.5: 1.5, the rotating speed of the planetary ball mill is 120 r/min, and the mass ratio of LMO to grinding balls to water is 1: 2.2: 0.45, wherein the total volume of LMO, grinding balls and water accounts for 3/5 of the volume of the ball mill, and the positive electrode material is obtained after wet ball milling for 8h, wherein the particle size of the positive electrode material is distributed in a 100-900 nm level (see (h) in the attached figure 1), and the specific surface area is 57m 2 g -1 (see (i) in FIG. 1), mesopore/micropore volume of 0.54/0.27cm 3 g -1 The SEM picture is shown in (d) of the attached figure 1. By calculation, at a scanning rate of 1mV/s, the pseudo-capacitance current contribution was 82.1% (see (d) in FIG. 2), the charge transfer resistance was 29 Ω, and the lithium ion diffusion coefficient was 15.42X 10 -15 cm 2 ·s -1 ；
Step 2: taking the positive electrode material obtained in the step (1) as a positive electrode active material, taking metal Zn as a negative electrode, and taking 1M Li 2 SO 4 +1.8M ZnSO 4 The mixed aqueous solution is used as electrolyte, AGM is used as a diaphragm, the battery is assembled in a room temperature environment, the electrical property of the battery is tested, and the test conditions are as follows: the voltage range is 1.4-2.1V, the multiplying power is 0.2C-10C, the test result is shown in table 1 when the temperature is 25 ℃, the gram capacity is as high as 127.2 mA.h.g at 0.2C -1 (see FIG. 3), retained about 124.1 mA. h. g after 100 cycles -1 The capacity retention rate after 150 cycles is 97.6 percent; can provide 100.7mA · h · g under 10 DEG C -1 The capacity retention rate after 600 cycles is 90.6%.
Example 2
The positive electrode active material LMO in example 1 was replaced with LiTi 2( PO 4 ) 3 Otherwise, the same procedure as in example 1 was repeated. The particle size distribution of the obtained anode material is between 100nm and 900 nm. By calculation, the pseudocapacitance current contribution was 78.4% at a scan rate of 1 mV/s.
Example 3
The positive electrode active material LMO in example 1 was replaced with LiNi 1/3 Co 1/3 Mn 1/3 O 2 Otherwise, the same procedure as in example 1 was repeated. The obtained anode material has the particle size distribution of 100-900 nm. By calculation, the pseudocapacitance current contribution accounted for 76.2% at a scan rate of 1 mV/s.
Example 4
The ball milling time in example 1 was changed to 6 hours, and the rest was the same as in example 1. The obtained cathode material has SEM image (c) in figure 1, size distribution (g) in figure 1, and specific surface area (i) in figure 1; by calculation, the pseudocapacitance current contribution accounted for 53.6% at a scan rate of 1mV/s (see (c) in FIG. 2).
Example 5
The ball milling time in example 1 was changed to 4 hours, and the rest of the procedure was the same as in example 1. The obtained positive electrode material has SEM image (b) in figure 1, size distribution (f) in figure 1, and specific surface area (i) in figure 1; by calculation, the pseudocapacitance current contribution was 34.7% at a scan rate of 1mV/s (see (b) in FIG. 2).
Example 6
The mass ratio of LMO to grinding balls and water in example 1 was changed to 1:1.8:0.5, as in example 1. The specific surface area and the mesopore/micropore volume of the material are both reduced and the pseudocapacitance effect is affected, thereby affecting the electrical performance.
Example 7
The ratio of the total volume of LMO to grinding balls and water to the volume of the ball mill in example 1 was changed to 4/5. The size distribution of the material is reduced and the pseudocapacitance, and thus the electrical performance, is affected.
Comparative example 1
The same as example 1 was repeated except that LMO, which was not originally wet ball-milled, was used as a positive electrode active material. The particle size thereof is distributed at the 500-900nm level (see (e) in FIG. 1), and the specific surface area thereof is 13m 2 g -1 (see (i) in FIG. 1), mesopore/micropore volume of 0.11/0.02cm 3 g -1 The SEM picture is shown in (a) of the attached figure 1. Through calculation, under the scanning rate of 1mV/s, the pseudocapacitance current contribution accounts for 23.2 percent, the charge transfer resistance is 86 omega, and the lithium ion diffusion coefficient is 2.47 multiplied by 10 < -15 > cm 2 ·s -1 Cyclic voltammogram of the battery positive electrodeSee (a) in fig. 2, and the rate capability is shown in fig. 3.
Comparative example 2
Step 1: using three ZrO of different diameters 2 Mixing the balls with LMO for dry ball milling, wherein the number ratio of the grinding balls with different diameters is 1: 2.5: 1.5, performing ball milling for 8 hours at the rotating speed of the planetary ball mill of 120 revolutions per minute to obtain a positive electrode material;
and 2, step: taking the positive electrode material obtained in the step (1) as a positive electrode active material, taking metal Zn as a negative electrode, and taking 1M Li 2 SO 4 +1.8M ZnSO 4 The mixed aqueous solution is used as electrolyte, AGM is used as a diaphragm, the battery is assembled in a room temperature environment, the electrical property of the battery is tested, and the test conditions are as follows: the voltage range is 1.4-2.1V, the multiplying power is 0.2-10C, and the test results are shown in table 1 in a 25 ℃ test.
Comparative example 3
The ball milling time in example 1 was changed to 12 hours, and the rest was the same as in example 1. Due to ZrO 2 Under the strong friction of the pellets, the LMO microporous structure collapses, resulting in a large number of fine LMO particles blocking the micropores, resulting in a sharp decrease in the material surface area and pore volume (see (i) in FIG. 1).
Comparative example 4
The rotation speed of the ball mill in example 1 was changed to 400 rpm, and the operation was otherwise the same as in example 1. The high-energy ball milling destroys the crystallinity of LMO, and the material does not have a hierarchical structure, thereby affecting the electrical property.
The results of the battery performance tests in examples 1-7 and comparative examples 1-4 are shown in Table 1:
TABLE 1 results of cell performance test in examples 1 to 7 and comparative examples 1 to 4
Figure BDA0002994859360000071
Figure BDA0002994859360000081
In the description of the specification, reference to the description of "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" or the like means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (10)

1. A method of making a positive electrode material, comprising: the wet ball milling was performed using three kinds of grinding balls of different diameters mixed with the positive electrode active material and the solvent, so as to obtain a positive electrode material.
2. The method as claimed in claim 1, wherein the grinding balls have a large ball diameter of 10 to 20mm, a medium ball diameter of 5 to 10mm and a small ball diameter of 1 to 5 mm.
3. The method of claim 2, wherein the number ratio of the large balls, the medium balls and the small balls is 1: (1-9): (1-6).
4. The method according to claim 1, wherein the wet ball milling has a ball milling rotation speed of 60-380 r/min and a ball milling time of 2-10 hours.
5. The method according to claim 1, wherein the mass ratio of the positive electrode active material, the grinding balls, and the solvent is 1: (1-6): (0.1 to 3).
6. The method according to claim 5, wherein the ratio of the total volume of the positive electrode active material, the grinding balls and the solvent to the volume of the container is (1-4): 5.
7. the method according to claim 1, wherein the positive electrode active material is selected from one or more of the following:
corresponds to the general formula Li 1+x Mn y M z O k Wherein-1. ltoreq. x.ltoreq.0.5, 1. ltoreq. y.ltoreq.2.5, 0. ltoreq. z.ltoreq.0.5, 3. ltoreq. k.ltoreq.6, M comprises at least one of Na, Li, Co, Mg, Ti, Cr, V, Zn, Zr, Si and Al;
corresponds to the general formula Li 1+x M y M' Z M" c O 2+n The compound of (1), wherein<x is less than or equal to 0.5, y is less than or equal to 0 and less than or equal to 1, z is less than or equal to 0 and less than or equal to 1, c is less than or equal to 0 and less than or equal to-0.2, n is less than or equal to 0.2, and M, M 'and M' are respectively selected from at least one of Ni, Mn, Co, Mg, Ti, Cr, V, Zn, Zr, Si and Al; and
corresponds to the general formula Li x M 1-y M' y (XO 4 ) n A compound of (1), wherein 0<X is less than or equal to 2, y is less than or equal to 0 and less than or equal to 0.6, n is less than or equal to 1 and less than or equal to 1.5, M is selected from Fe, Mn, V or Co, M' is selected from at least one of Mg, Ti, Cr, V and Al, and X is selected from at least one of S, P and Si.
8. The method according to claim 7, wherein the positive electrode active material comprises LiMn 2 O 4 ，LiTi 2 (PO 4 ) 3 And LiNi 1/3 Co 1/3 Mn 1/3 O 2 At least one of (a).
9. A positive electrode material, characterized in that the positive electrode material is prepared by the method according to any one of claims 1 to 8.
10. A battery, characterized in that the positive electrode of the battery comprises the positive electrode material of claim 9 or the positive electrode material prepared by the method of any one of claims 1 to 8.
CN202110326448.2A 2021-03-26 2021-03-26 Positive electrode material and preparation method and application thereof Pending CN115121335A (en)

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