CN117577822A - Oxide electrode material with partially disordered structure and preparation method and application thereof - Google Patents

Oxide electrode material with partially disordered structure and preparation method and application thereof Download PDF

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CN117577822A
CN117577822A CN202410051809.0A CN202410051809A CN117577822A CN 117577822 A CN117577822 A CN 117577822A CN 202410051809 A CN202410051809 A CN 202410051809A CN 117577822 A CN117577822 A CN 117577822A
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electrode material
oxide electrode
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oxide
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纪效波
梅雨
侯红帅
邹国强
邓文韬
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Central South University
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Central South University
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    • 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
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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Abstract

The invention relates to an oxide electrode material with a partially disordered structure, which has the structural formula: li (Li) a‑m Mn b Ti c O d F 2‑d Wherein a-m is more than or equal to 1 and less than or equal to 1.5, b is more than or equal to 0 and less than or equal to 1, c is more than or equal to 0 and less than or equal to 1, d is more than or equal to 0 and less than or equal to 2, m is more than 0 and less than 0.3, and a+b+c is less than 2; the oxide electrode material crystal has a disordered rock salt structure and an ordered spinel structure; the composite material has the advantages of high capacity of a rock salt structure and high multiplying power of a spinel structure, and is used as an anode active material of an electrochemical energy storage device, and the composite material has ultrahigh specific capacity, high multiplying power performance, high first coulombic efficiency and good cycle performance.

Description

Oxide electrode material with partially disordered structure and preparation method and application thereof
Technical Field
The invention relates to the technical field of electrode materials, in particular to an oxide electrode material with a partially disordered structure, and a preparation method and application thereof.
Background
As a key support technology of energy revolution, the lithium ion battery has huge application potential in the fields of large-scale intervention, multi-energy complementary coupling utilization, energy network construction only, traffic electric drive and the like of renewable energy in the future by virtue of the characteristics of high energy density, long service life, no memory effect and the like, but also has higher requirements on the energy density. Current lithium ion batteries are primarily limited in energy density by the cathode material. The positive electrode of the lithium-rich cation disordered rock salt structure has high specific capacity (250 mAh/g) based on a charge compensation mechanism of cation-anion redox coupling. However, in disordered rock salt structural materials, lithium ions rely on 0-TM channel seepage, so that the rate performance of the disordered rock salt structural materials is poor, and the commercialized application of the disordered rock salt structural materials is limited. The spinel-structure positive electrode material with the same anion framework has three-dimensional lithium permeation channels, and the unique ion diffusion channels enable the spinel-structure positive electrode to have faster charge and discharge characteristics. However, the spinel-structured positive electrode material has a low theoretical capacity, and is difficult to cope with the requirement of future application scenes on a high-capacity positive electrode.
The conventional technical means such as doping, coating and the like can be used for modifying a certain aspect of problems of the positive electrode material with the disordered rock salt structure of the lithium-rich cations and the positive electrode material with the spinel structure, but the conventional technical means are deficient in improving the comprehensive performance, and the limitation of composition and structural conditions is the root. The two structural oxide positive electrode materials have respective advantages and disadvantages, and the partial disordered structural oxide is obtained by integrating the two structural oxide composition spaces so as to break through the structural limitation of the oxide, thereby achieving the effect of taking advantage of the shortness and being significant for obtaining the oxide positive electrode material with excellent comprehensive performance.
Disclosure of Invention
Based on the technical problems in the prior art, the invention provides an oxide electrode material with a partially disordered structure, wherein the crystal structure of the oxide electrode material has a disordered rock salt structure (Fm-3 m space point group) and an ordered spinel structure (Fd-3 m space point group), has the advantages of high capacity of the rock salt structure and high multiplying power of the spinel structure, and is used as an anode active material of an electrochemical energy storage device, and the oxide electrode material has ultrahigh specific capacity and multiplying power performance, high first coulomb efficiency and good cycle performance.
In order to achieve the above object, the technical scheme of the present invention is as follows:
an oxide electrode material with a partially disordered structure, which has the structural formula: li (Li) a-m Mn b Ti c O d F 2-d Wherein a-m is more than or equal to 1 and less than or equal to 1.5, b is more than or equal to 0 and less than or equal to 1, c is more than or equal to 0 and less than or equal to 1, d is more than or equal to 0 and less than or equal to 2, m is more than 0 and less than 0.3, and a+b+c is less than 2; the oxide electrode material crystal has both disordered rock salt structure and ordered spinel structure.
The invention also provides a preparation method of the oxide electrode material with the partially disordered structure, which comprises the following steps:
s1, uniformly mixing stoichiometric manganese sources, stoichiometric titanium sources, stoichiometric lithium sources and stoichiometric fluorine sources to obtain a material A;
s2, calcining the material A in an inert atmosphere, and cooling to room temperature to obtain a product A;
s3, mixing the product A with an acid solution, washing, separating and drying to obtain a material B;
and S4, calcining the material B for the second time in an inert atmosphere, and cooling to room temperature to obtain the oxide electrode material.
In some embodiments, in step S1, after mixing the raw materials, adding a proper amount of volatile organic solvent to prepare slurry, ball milling uniformly, and the ball-to-material ratio is 10-20:1, a step of; the ball milling rotating speed is 500-800r/min.
In some embodiments, the organic solvent includes, but is not limited to, ethanol, acetone, isopropanol, and the like.
In some embodiments, in step S1, the ball milling time is 8-12 hours.
In some embodiments, in step S1, after ball milling, the mixture is dried at 60-80 ℃.
In some embodiments, in step S2, the calcination temperature is 900-1100 ℃ and the calcination time is 12-18 hours.
In some embodiments, in step S2, the rate of temperature increase is 3-5 ℃/min.
In some embodiments, in step S2, the rate of cooling is 1-20 ℃/min.
In some embodiments, in step S3, the acid solution has a concentration of 0.01-1mol/L; the acid solution comprises an organic acid and/or an inorganic acid, specifically including but not limited to at least one of nitric acid, sulfuric acid, hydrochloric acid, acetic acid; the acid solution treatment time is 0-8h (treatment time > 0).
In some embodiments, in step S4, the secondary calcination temperature is 500-700 ℃; the calcination time is 1-6h.
In some embodiments, in step S4, the rate of temperature increase for the secondary calcination is 3-5 ℃/min.
In some embodiments, the inert atmosphere in step S2 and step S4 each independently comprises a nitrogen atmosphere or an argon atmosphere with a purity of 99.99% or more.
In some embodiments, the lithium source includes, but is not limited to, oxides and/or compounds of lithium such as lithium carbonate, lithium oxide, lithium hydroxide, lithium chloride, lithium nitrate, lithium acetate, and the like.
In some embodiments, the manganese source comprises at least one of oxides, chlorides, sulfates, nitrates, phosphates, acetates, etc. of manganese; specifically, including but not limited to manganese sesquioxide and the like.
In some embodiments, the titanium source comprises at least one of an oxide, chloride, sulfate, nitrate, phosphate, acetate, etc. of titanium; specifically, including but not limited to titanium dioxide, and the like.
In some embodiments, the fluorine source comprises at least one of manganese fluoride, titanium fluoride, lithium fluoride, and an organic fluorine source, among others; specifically, including but not limited to lithium fluoride and the like.
The invention also provides a positive electrode active material, which comprises the oxide electrode material or the oxide electrode material prepared by the preparation method of any embodiment.
The invention also provides a positive electrode material comprising the positive electrode active material.
The invention also provides an electrode which comprises the positive electrode material.
The invention also provides an electrochemical energy storage device comprising the electrode.
In particular, the energy storage device includes, but is not limited to, lithium ion batteries, lithium ion capacitors, and the like.
Compared with the prior art, the invention has the following beneficial effects:
the oxide electrode material has a crystal structure with a disordered rock salt structure (Fm-3 m space point group) and an ordered spinel structure (Fd-3 m space point group), combines the advantages of the disordered rock salt structure and the ordered spinel structure oxide, has rich heterostructures, can show ultrahigh specific capacity and rate capability, higher first coulombic efficiency and good cycle performance, and has excellent electrochemical performance. Through detection, the oxide electrode material provided by the invention has a first discharge specific capacity of 292mAh/g and a first coulomb efficiency of 107.83%.
The method of the invention adopts a partial unordered structure construction strategy of vacancy construction-ion rearrangement, can continuously adjust unordered degree, is simple and convenient, and provides favorable conditions for the application of oxide electrode materials.
Drawings
FIG. 1 is a partially disordered oxide material Li prepared in example 1 1.25-x Mn 0.45 Ti 0.3 O 1.8 F 0.2 The preparation process is as follows;
FIG. 2 is a partially disordered oxide material Li prepared in example 1 1.25-x Mn 0.45 Ti 0.3 O 1.8 F 0.2 An XRD pattern of (b);
FIG. 3 is a partially disordered oxide material Li prepared in example 1 1.25-x Mn 0.45 Ti 0.3 O 1.8 F 0.2 STEM diagram of (a);
FIG. 4 is a partially disordered oxide material Li prepared in example 1 1.25-x Mn 0.45 Ti 0.3 O 1.8 F 0.2 A charge-discharge plot for the first 5 turns at a current density of 20 mA/g;
FIG. 5 is a partially disordered oxide material Li prepared in example 1 1.25-x Mn 0.45 Ti 0.3 O 1.8 F 0.2 A cycle chart for the first 100 turns at a current density of 1000 mA/g;
FIG. 6 is a partially disordered oxide material Li prepared in example 2 1.25-y Mn 0.45 Ti 0.3 O 1.8 F 0.2 An XRD pattern of (b);
FIG. 7 is a partially disordered oxide material Li prepared in example 2 1.25-y Mn 0.45 Ti 0.3 O 1.8 F 0.2 A charge-discharge plot for the first 5 turns at a current density of 20 mA/g;
FIG. 8 is a partially disordered oxide material Li prepared in example 2 1.25-y Mn 0.45 Ti 0.3 O 1.8 F 0.2 A cycle chart for the first 100 turns at a current density of 1000 mA/g;
FIG. 9 is a partially disordered oxide material Li prepared in example 3 1.25-z Mn 0.45 Ti 0.3 O 1.8 F 0.2 An XRD pattern of (b);
FIG. 10 is a partially disordered oxide material Li prepared in example 3 1.25-z Mn 0.45 Ti 0.3 O 1.8 F 0.2 A charge-discharge plot for the first 5 turns at a current density of 20 mA/g;
FIG. 11 is a partially disordered oxide material Li prepared in example 3 1.25-z Mn 0.45 Ti 0.3 O 1.8 F 0.2 A cycle chart for the first 100 turns at a current density of 1000 mA/g;
FIG. 12 is a partially disordered oxide material Li prepared in example 4 1.2-x Mn 0.6 Ti 0.2 O 1.8 F 0.2 An XRD pattern of (b);
FIG. 13 is a partially disordered oxide material Li prepared in example 4 1.2-x Mn 0.6 Ti 0.2 O 1.8 F 0.2 A charge-discharge plot for the first 5 turns at a current density of 20 mA/g;
FIG. 14 is a partially disordered oxide material Li prepared in example 4 1.2-x Mn 0.6 Ti 0.2 O 1.8 F 0.2 A cycle chart for the first 100 turns at a current density of 1000 mA/g;
FIG. 15 is a disordered rock salt structure oxide material Li prepared in comparative example 1 1.25 Mn 0.45 Ti 0.3 O 1.8 F 0.2 An XRD pattern of (b);
FIG. 16 is a disordered rock salt structure oxide material Li prepared in comparative example 1 1.25 Mn 0.45 Ti 0.3 O 1.8 F 0.2 STEM diagram of (a);
FIG. 17 is a disordered structure oxide material Li prepared in comparative example 1 1.25 Mn 0.45 Ti 0.3 O 1.8 F 0.2 A charge-discharge plot for the first 5 turns at a current density of 20 mA/g;
FIG. 18 is a disordered rock salt structure oxide material Li prepared in comparative example 1 1.25 Mn 0.45 Ti 0.3 O 1.8 F 0.2 Cycling chart for the first 100 turns at a current density of 1000 mA/g.
FIG. 19 is a disordered rock salt structure oxide material Li prepared in comparative example 2 1.2 Mn 0.6 Ti 0.2 O 1.8 F 0.2 An XRD pattern of (b);
FIG. 20 is a disordered structure oxide material Li prepared in comparative example 2 1.2 Mn 0.6 Ti 0.2 O 1.8 F 0.2 At a current density of 20 mA/gCharge-discharge curve graph of 5 circles;
FIG. 21 is a disordered rock salt structure oxide material Li prepared in accordance with comparative example 2 1.2 Mn 0.6 Ti 0.2 O 1.8 F 0.2 Cycling chart for the first 100 turns at a current density of 1000 mA/g.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit or scope of the invention, which is therefore not limited to the specific embodiments disclosed below.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Example 1
Oxide Li with partially disordered structure 1.25-x Mn 0.45 Ti 0.3 O 1.8 F 0.2 The preparation method of (2) is shown in figure 1, and the preparation flow chart comprises the following steps:
step 1, stoichiometric ratio is 0.225:0.3:1.05:0.2 weighing Mn 2 O 3 、TiO 2 LiOH, liF, wherein the molar excess of LiOH is 5% to compensate for losses during high temperatures; adding a proper amount of ethanol to prepare precursor slurry, and uniformly mixing the precursor slurry by using a ball milling method, wherein the ball-material ratio is 10:1, the ball milling time is 12h, and the rotating speed is 500 r/min; then drying at 80 ℃ for 8 hours to obtain a material A;
step 2, calcining the material A under high-purity argon, heating to 1000 ℃ at 3 ℃ per min, preserving heat for 12h, and cooling to room temperature at 2 ℃ per min to obtain a product A;
step 3, uniformly mixing the product A with 0.1M nitric acid solution for 1h, washing with deionized water for three times, washing with absolute ethyl alcohol for three times, vacuum filtering and separating, and drying at 80 ℃ to obtain a material B;
step 4,The material B is subjected to secondary calcination under high-purity argon, the temperature rising rate is raised to 500 ℃ at 3 ℃ per minute, the calcination time is 3 hours, and the material B is cooled to room temperature along with a furnace to obtain the oxide material Li with a partially disordered structure 1.25-x Mn 0.45 Ti 0.3 O 1.8 F 0.2 ，x=0.05。
The oxide material obtained was characterized, its XRD pattern is shown in FIG. 2, and stem pattern is shown in FIG. 3. As shown in FIGS. 2 to 3, XRD patterns and STEM patterns indicate that the metal oxide of the obtained cation disordered salt rock structure has both Fm-3m type structure and Fd-3m type structure.
Li prepared as described above 1.25-x Mn 0.45 Ti 0.3 O 1.8 F 0.2 The material is used as an anode active material of a lithium ion secondary battery to prepare an anode plate, and the specific mode is as follows: li to be prepared 1.25-x Mn 0.45 Ti 0.3 O 1.8 F 0.2 Mixing the powder with acetylene black and polyvinylidene fluoride (PVDF, adhesive) according to the mass ratio of 80:10:10, dropwise adding a proper amount of N-methylpyrrolidone (NMP) solution as a dispersing agent, and magnetically stirring for 3 hours to prepare slurry; the slurry was then coated on an aluminum foil current collector, dried in vacuo at 120 ℃ for 8h, and transferred to an Ar atmosphere glove box for use.
The half cell was assembled in an Ar atmosphere glove box with metallic lithium as the counter electrode and LiPF 6/ethylene carbonate (EC: DMC: dec=1:1:1) solution as the electrolyte to assemble a CR2016 type coin cell.
The charge and discharge test was performed at a current density of C/10 (20 mA/g) using a constant current charge and discharge mode, with a charge cut-off voltage set to 4.8V and a discharge cut-off voltage set to 1.5V, with the first five cycles of charge and discharge curves shown in FIG. 4.
The charge and discharge test was performed at a current density of 5C (1000 mA/g), the charge cut-off voltage was set to 4.8V, the discharge cut-off voltage was set to 1.5V, and the first 100 cycles of cycle performance was as shown in FIG. 5.
Example 2
Oxide material Li with partially disordered structure 1.25-y Mn 0.45 Ti 0.3 O 1.8 F 0.2 The preparation method of (2) comprises the following steps:
step 1, byThe stoichiometric ratio was 0.225:0.3:1.05:0.2 weighing Mn 2 O 3 、TiO 2 LiOH, liF, wherein the molar excess of LiOH is 5% to compensate for losses during high temperatures; adding a proper amount of ethanol to prepare precursor slurry, and uniformly mixing the precursor slurry by using a ball milling method, wherein the ball-material ratio is 10:1, the ball milling time is 12h, and the rotating speed is 500 r/min; then drying at 80 ℃ for 8 hours to obtain a material A;
step 2, calcining the material A under high-purity argon, heating to 1000 ℃ at 3 ℃ per min, preserving heat for 12h, and cooling to room temperature at 2 ℃ per min to obtain a product A;
step 3, uniformly mixing the product A with 0.1M nitric acid solution for 2 hours, washing with deionized water for three times, washing with absolute ethyl alcohol for three times, vacuum filtering and separating, and drying at 80 ℃ to obtain a material B;
step 4, the material B is subjected to secondary calcination under high-purity argon, the temperature rising rate of 3 ℃ per minute is raised to 500 ℃, the calcination time is 3 hours, and the material B is cooled to room temperature along with a furnace, so that the oxide material Li with a partially disordered structure is obtained 1.25-y Mn 0.45 Ti 0.3 O 1.8 F 0.2 ，y=0.09。
The oxide material obtained was characterized and its XRD pattern was shown in fig. 6.XRD patterns show that the metal oxide with the obtained cation disorder salt rock structure has both Fm-3m type structure and Fd-3m type structure.
Li prepared as described above 1.25-y Mn 0.45 Ti 0.3 O 1.8 F 0.2 The material is used as an anode active material of a lithium ion secondary battery to prepare an anode plate, and the specific mode is as follows: li to be prepared 1.25-y Mn 0.45 Ti 0.3 O 1.8 F 0.2 Mixing the powder with acetylene black and polyvinylidene fluoride (PVDF, adhesive) according to the mass ratio of 80:10:10, dropwise adding a proper amount of N-methylpyrrolidone (NMP) solution as a dispersing agent, and magnetically stirring for 3 hours to prepare slurry; the slurry was then coated on an aluminum foil current collector, dried in vacuo at 120 ℃ for 8h, and transferred to an Ar atmosphere glove box for use.
The half cell was assembled in an Ar atmosphere glove box with metallic lithium as the counter electrode and LiPF 6 Ethylene carbonate (EC: DMC: dec=1:1:1) solution as electricityAnd (5) dissolving the solution, and assembling the solution into the CR2016 type button battery.
The charge and discharge test was performed at a current density of C/10 (20 mA/g) using a constant current charge and discharge mode, with a charge cut-off voltage set to 4.8V and a discharge cut-off voltage set to 1.5V, with the top five cycles of charge and discharge curves shown in FIG. 7.
The charge and discharge test was performed at a current density of 5C (1000 mA/g), the charge cut-off voltage was set to 4.8V, the discharge cut-off voltage was set to 1.5V, and the first 100 cycles of cycle performance was as shown in FIG. 8.
Example 3
Oxide material Li with partially disordered structure 1.25-z Mn 0.45 Ti 0.3 O 1.8 F 0.2 The preparation method of (2) comprises the following steps:
step 1, stoichiometric ratio is 0.225:0.3:1.05:0.2 weighing Mn 2 O 3 、TiO 2 LiOH, liF, wherein the molar excess of LiOH is 5% to compensate for losses during high temperatures; adding a proper amount of ethanol to prepare precursor slurry, and uniformly mixing the precursor slurry by using a ball milling method, wherein the ball-material ratio is 10:1, the ball milling time is 12h, and the rotating speed is 500 r/min; then drying at 80 ℃ for 8 hours to obtain a material A;
step 2, calcining the material A under high-purity argon, heating to 1000 ℃ at 3 ℃ per min, preserving heat for 12h, and cooling to room temperature at 2 ℃ per min to obtain a product A;
step 3, uniformly mixing the product A with 0.1M nitric acid solution for 4 hours, washing with deionized water for three times, washing with absolute ethyl alcohol for three times, vacuum filtering and separating, and drying at 80 ℃ to obtain a material B;
step 4, the material B is subjected to secondary calcination under high-purity argon, the temperature rising rate of 3 ℃ per minute is raised to 500 ℃, the calcination time is 3 hours, and the material B is cooled to room temperature along with a furnace, so that the oxide material Li with a partially disordered structure is obtained 1.25-x Mn 0.45 Ti 0.3 O 1.8 F 0.2 ，z=0.15；
The resulting oxide material was characterized and its XRD pattern is shown in figure 9.XRD patterns show that the metal oxide with the obtained cation disorder salt rock structure has both Fm-3m type structure and Fd-3m type structure.
Li prepared as described above 1.25-x Mn 0.45 Ti 0.3 O 1.8 F 0.2 The material is used as an anode active material of a lithium ion secondary battery to prepare an anode plate, and the specific mode is as follows: li to be prepared 1.25-x Mn 0.45 Ti 0.3 O 1.8 F 0.2 Mixing the powder with acetylene black and polyvinylidene fluoride (PVDF, adhesive) according to the mass ratio of 80:10:10, dropwise adding a proper amount of N-methylpyrrolidone (NMP) solution as a dispersing agent, and magnetically stirring for 3 hours to prepare slurry; the slurry was then coated on an aluminum foil current collector, dried in vacuo at 120 ℃ for 8h, and transferred to an Ar atmosphere glove box for use.
The half cell was assembled in an Ar atmosphere glove box with metallic lithium as the counter electrode and LiPF 6 A vinyl carbonate (EC: DMC: dec=1:1:1) solution was used as an electrolyte to assemble a CR2016 type coin cell.
The charge and discharge test was performed at a current density of C/10 (20 mA/g) using a constant current charge and discharge mode, with a charge cut-off voltage set to 4.8V and a discharge cut-off voltage set to 1.5V, with the first five cycles of charge and discharge curves shown in FIG. 10.
The charge and discharge test was performed at a current density of 5C (1000 mA/g), the charge cut-off voltage was set to 4.8V, the discharge cut-off voltage was set to 1.5V, and the first 100 cycles of cycle performance was as shown in FIG. 11.
Example 4
Oxide material Li with partially disordered structure 1.2-x Mn 0.6 Ti 0.2 O 1.8 F 0.2 The preparation method of (2) comprises the following steps:
step 1, the stoichiometric ratio is 0.3:0.2:1:0.2 weighing Mn 2 O 3 、TiO 2 LiOH, liF, wherein the molar excess of LiOH is 5% to compensate for losses during high temperatures; adding a proper amount of ethanol to prepare precursor slurry, and uniformly mixing the precursor slurry by using a ball milling method, wherein the ball-material ratio is 10:1, the ball milling time is 12h, and the rotating speed is 500 r/min; then drying at 80 ℃ for 8 hours to obtain a material A;
step 2, calcining the material A under high-purity argon, heating to 1000 ℃ at 3 ℃ per min, preserving heat for 12h, and cooling to room temperature at 2 ℃ per min to obtain a product A;
step 3, uniformly mixing the product A with 0.1M nitric acid solution for 2 hours, washing with deionized water for three times, washing with absolute ethyl alcohol for three times, vacuum filtering and separating, and drying at 80 ℃ to obtain a material B;
step 4, the material B is subjected to secondary calcination under high-purity argon, the temperature rising rate of 3 ℃ per minute is raised to 500 ℃, the calcination time is 3 hours, and the material B is cooled to room temperature along with a furnace, so that the oxide material Li with a partially disordered structure is obtained 1.2-x Mn 0.6 Ti 0.2 O 1.8 F 0.2 ，x=0.1；
The resulting oxide material was characterized and its XRD pattern is shown in figure 12.XRD patterns show that the metal oxide with the obtained cation disorder salt rock structure has both Fm-3m type structure and Fd-3m type structure.
Li prepared as described above 1.2-x Mn 0.6 Ti 0.2 O 1.8 F 0.2 The material is used as an anode active material of a lithium ion secondary battery to prepare an anode plate, and the specific mode is as follows: li to be prepared 1.2-x Mn 0.6 Ti 0.2 O 1.8 F 0.2 Mixing the powder with acetylene black and polyvinylidene fluoride (PVDF, adhesive) according to the mass ratio of 80:10:10, dropwise adding a proper amount of N-methylpyrrolidone (NMP) solution as a dispersing agent, and magnetically stirring for 3 hours to prepare slurry; the slurry was then coated on an aluminum foil current collector, dried in vacuo at 120 ℃ for 8h, and transferred to an Ar atmosphere glove box for use.
The half cell was assembled in an Ar atmosphere glove box with metallic lithium as the counter electrode and LiPF 6 A vinyl carbonate (EC: DMC: dec=1:1:1) solution was used as an electrolyte to assemble a CR2016 type coin cell.
The charge and discharge test was performed at a current density of C/10 (20 mA/g) using a constant current charge and discharge mode, with a charge cut-off voltage set to 4.8V and a discharge cut-off voltage set to 1.5V, with the first five cycles of charge and discharge curves shown in FIG. 13.
The charge and discharge test was performed at a current density of 5C (1000 mA/g), the charge cut-off voltage was set to 4.8V, the discharge cut-off voltage was set to 1.5V, and the first 100 cycles of cycle performance was as shown in FIG. 14.
Comparative example 1
Preparing disordered salt rock structure oxide material Li by adopting solid phase reaction 1.25 Mn 0.45 Ti 0.3 O 1.8 F 0.2 The preparation method comprises the following specific steps:
step 1, weighing the materials with the stoichiometric ratio of 0.225:0.3:1.05:0.2 weighing Mn 2 O 3 、TiO 2 LiOH, liF, wherein the molar excess of lithium source is 5% to compensate for losses during high temperature; adding a proper amount of ethanol to prepare precursor slurry, and uniformly mixing the precursor slurry by using a ball milling method, wherein the ball-material ratio is 10:1, the ball milling time is 12h, and the rotating speed is 500 r/min; then drying at 80 ℃ for 8 hours to obtain a material A;
step 2, calcining the material A under high-purity argon, heating to 1000 ℃ at 3 ℃ per min, preserving heat for 12 hours, and cooling along with a furnace to obtain a product Li 1.25 Mn 0.45 Ti 0.3 O 1.8 F 0.2 。
The resulting product was characterized with an XRD pattern as shown in FIG. 15 and a STEM pattern as shown in FIG. 16. As shown in FIGS. 15-16, XRD patterns and STEM patterns indicate that the metal oxide of the obtained cation disorder salt rock structure is of Fm-3m type structure.
And using the prepared material as a positive electrode active substance of the lithium ion secondary battery, preparing a positive electrode plate and assembling the lithium ion half battery.
Using a constant current charge-discharge mode, a charge-discharge test was performed at a current density of 20 mA/g, the charge cut-off voltage was set to 4.8V, the discharge cut-off voltage was set to 1.5V, and the first-turn charge-discharge curve was shown in fig. 17.
The charge and discharge test was performed at a current density of 5C (1000 mA/g), the charge cut-off voltage was set to 4.8V, the discharge cut-off voltage was set to 1.5V, and the first 100 cycles of cycle performance was as shown in FIG. 18.
Comparative example 2
Preparing disordered salt rock structure oxide material Li by adopting solid phase reaction 1.2 Mn 0.6 Ti 0.2 O 1.8 F 0.2 The preparation method comprises the following specific steps:
step 1, weighing the materials with the stoichiometric ratio of 0.3:0.2:1.00:0.2 weighing Mn 2 O 3 、TiO 2 LiOH, liF, wherein the molar amount of lithium source5% excess to compensate for losses during high temperature; adding a proper amount of ethanol to prepare precursor slurry, and uniformly mixing the precursor slurry by using a ball milling method, wherein the ball-material ratio is 10:1, the ball milling time is 12h, and the rotating speed is 500 r/min; then drying at 80 ℃ for 8 hours to obtain a material A;
step 2, calcining the material A under high-purity argon, heating to 1000 ℃ at 3 ℃ per min, preserving heat for 12 hours, and cooling along with a furnace to obtain a product Li 1.2 Mn 0.6 Ti 0. O 1.8 F 0.2 。
The resulting product was characterized and its XRD pattern was seen in figure 19. As shown in fig. 19, the xrd pattern indicates that the metal oxide material of the resulting cationic disordered salt rock structure is of Fm-3m type structure.
And using the prepared material as a positive electrode active substance of the lithium ion secondary battery, preparing a positive electrode plate and assembling the lithium ion half battery.
Using a constant current charge-discharge mode, a charge-discharge test was performed at a current density of 20 mA/g, the charge cut-off voltage was set to 4.8V, the discharge cut-off voltage was set to 1.5V, and the first-turn charge-discharge curve was shown in fig. 20.
The charge and discharge test was performed at a current density of 5C (1000 mA/g), the charge cut-off voltage was set to 4.8V, the discharge cut-off voltage was set to 1.5V, and the first 100 cycles of cycle performance was as shown in FIG. 21.
As can be seen from fig. 4, 7 and 10, the oxide materials with partially disordered rock salt structures prepared by adopting different nitric acid treatment times in examples 1, 2 and 3 have specific capacities of 292mAh/g and 285 mAh/g for the first discharge, and the initial coulomb efficiencies of 117%,126% and 144% respectively. In contrast, the oxide material of disordered rock salt structure prepared in comparative example 1, as shown in fig. 17, has a specific capacity of 157 mAh/g for the first discharge and has a coulombic efficiency of only 69%. The oxide materials with partial disordered structures prepared in examples 1, 2 and 3 have specific capacities of 158 mAh/g,188 mAh/g and 204 mAh/g for the first time under high current density, and the specific capacities remain at 121 mAh/g,134 mAh/g and 133 mAh/g after 100 circles (shown in figures 5,8 and 11). In contrast, the specific discharge capacity of the oxide with the disordered structure at the high current density is only 37 mAh/g (as shown in FIG. 18).
By changing the composition of disordered rock salt phase, as can be seen from fig. 13, the oxide material with partially disordered rock salt structure prepared in example 4 has a first discharge specific capacity of 311 mAh/g and a first coulomb efficiency of 140% respectively. In contrast, the oxide material of disordered rock salt structure prepared in comparative example 2, as shown in fig. 20, has a specific capacity of 183 mAh/g for the first discharge and a coulombic efficiency of only 83%. Under high current density, the oxide material with a partially disordered structure prepared in example 4 has a specific capacity of 251 mAh/g after first discharge and a specific capacity retention rate of 184 mAh/g after 100 circles (as shown in FIG. 14). In contrast, the specific discharge capacity of the oxide with the disordered structure at the high current density is only 83mAh/g (as shown in FIG. 21).
The electrochemical data show that the oxide material with the partially disordered structure provided by the invention has obvious performance advantages compared with the oxide material with the completely disordered rock salt structure. The invention is illustrated that the partial unordered structure oxide material obtained by adjusting the cation occupation of the unordered rock salt structure breaks through the condition limitation of the oxide material with a complete unordered structure, and the structure of the unordered rock salt structure and the ordered spinel structure interweaved with each other has rich heterostructures, is favorable for carrier storage and transportation, and therefore has ultrahigh specific capacity. Meanwhile, the spinel structure enhances the structural stability of the disordered oxide material, thereby improving the first coulombic efficiency and the cycle performance.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (10)

1. An oxide electrode material with a partially disordered structure, which is characterized by having the structural formula: li (Li) a-m Mn b Ti c O d F 2-d Wherein a-m is more than or equal to 1 and less than or equal to 1.5, b is more than or equal to 0 and less than or equal to 1, c is more than or equal to 0 and less than or equal to 1, d is more than or equal to 0 and less than or equal to 2, m is more than 0 and less than 0.3, and a+b+c is less than 2; the oxide electrode material crystal has a disordered rock salt structure and an ordered spinel structure;
the preparation method comprises the following steps:
s1, uniformly mixing stoichiometric manganese sources, stoichiometric titanium sources and stoichiometric lithium sources to obtain a material A;
s2, calcining the material A in an inert atmosphere, and cooling to room temperature to obtain a product A;
s3, mixing the product A with an acid solution, washing, separating and drying to obtain a material B;
and S4, calcining the material B for the second time in an inert atmosphere, and cooling to room temperature to obtain the oxide electrode material.
2. The method for preparing an oxide electrode material of a partially disordered structure according to claim 1, comprising the steps of:
s1, uniformly mixing stoichiometric manganese sources, stoichiometric titanium sources and stoichiometric lithium sources to obtain a material A;
s2, calcining the material A in an inert atmosphere, and cooling to room temperature to obtain a product A;
s3, mixing the product A with an acid solution, washing, separating and drying to obtain a material B;
and S4, calcining the material B for the second time in an inert atmosphere, and cooling to room temperature to obtain the oxide electrode material.
3. The method for preparing a partially disordered structured oxide electrode material in accordance with claim 2, wherein in step S2, the calcination temperature is 900-1100 ℃; the cooling rate is 1-20 ℃/min.
4. The method for producing a partially disordered oxide electrode material according to claim 2, wherein in step S4, the temperature of the secondary calcination is 500-700 ℃, and after the calcination is completed, the material is cooled to room temperature with a furnace.
5. The method for producing a partially disordered structured oxide electrode material according to claim 2, wherein in step S3, said acid solution includes an organic acid and/or an inorganic acid at a concentration of 0.01-1mol/L.
6. The method for preparing oxide electrode material with partially disordered structure according to claim 2, wherein in step S1, after mixing the raw materials, ball milling is uniform, and the ball-to-material ratio is 10-20:1, a step of; the ball milling rotating speed is 500-800r/min.
7. A positive electrode active material comprising the oxide electrode material according to claim 1 or the oxide electrode material obtained by the production method according to any one of claims 2 to 6.
8. A positive electrode material comprising the positive electrode active material according to claim 7.
9. An electrode comprising the positive electrode material of claim 8.
10. An electrochemical energy storage device comprising the electrode of claim 9.
CN202410051809.0A 2024-01-15 2024-01-15 Oxide electrode material with partially disordered structure and preparation method and application thereof Pending CN117577822A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105742616A (en) * 2016-02-29 2016-07-06 江苏大学 Disordered rock salt structured lithium ion battery cathode material and preparation method thereof
CN113321244A (en) * 2021-05-19 2021-08-31 上海大学 Preparation method and application of surface-modified layered oxide positive electrode material
WO2023034137A1 (en) * 2021-08-31 2023-03-09 Wildcat Discovery Technologies, Inc. Cathode with coated disordered rocksalt material
CN116856058A (en) * 2023-07-05 2023-10-10 中国科学院物理研究所 Single crystal lithium-rich material, preparation method thereof and energy storage device

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105742616A (en) * 2016-02-29 2016-07-06 江苏大学 Disordered rock salt structured lithium ion battery cathode material and preparation method thereof
CN113321244A (en) * 2021-05-19 2021-08-31 上海大学 Preparation method and application of surface-modified layered oxide positive electrode material
WO2023034137A1 (en) * 2021-08-31 2023-03-09 Wildcat Discovery Technologies, Inc. Cathode with coated disordered rocksalt material
CN116856058A (en) * 2023-07-05 2023-10-10 中国科学院物理研究所 Single crystal lithium-rich material, preparation method thereof and energy storage device

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