CN112919546B - Positive electrode material of monoclinic/tetragonal spinel heterostructure and preparation method thereof - Google Patents
Positive electrode material of monoclinic/tetragonal spinel heterostructure and preparation method thereof Download PDFInfo
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- CN112919546B CN112919546B CN201911241469.3A CN201911241469A CN112919546B CN 112919546 B CN112919546 B CN 112919546B CN 201911241469 A CN201911241469 A CN 201911241469A CN 112919546 B CN112919546 B CN 112919546B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
- C01G45/1228—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [MnO2]n-, e.g. LiMnO2, Li[MxMn1-x]O2
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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
- 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
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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
- H01M4/48—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
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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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- 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 of a monoclinic/tetragonal spinel heterostructure and a preparation method thereof. The method comprises the steps of taking a manganese oxide material as a positive electrode and a lithium metal sheet as a negative electrode to assemble a half-cell, and based on the mass of the manganese-containing oxide material, adopting a constant current of 0.02-0.2A/g to carry out charge and discharge within a voltage range of 2.0-4.5V to prepare the LiMnO with a monoclinic/tetragonal spinel heterostructure2And (3) a positive electrode material. The preparation method disclosed by the invention is simple in preparation process and low in energy consumption, and the prepared lithium ion anode material has excellent electrochemical properties such as specific capacity, rate capability and cycling stability.
Description
Technical Field
The invention belongs to the technical field of battery materials, and relates to a monoclinic/tetragonal spinel heterostructure cathode material and a preparation method thereof.
Background
Compared with the anode material of the lithium ion battery such as LiFePO4、LiCoO2And LiNi0.8Mn0.1Co0.1O2Etc. LiMnO2The material has higher theoretical specific capacity, and the manganese element has the advantages of low price, wide source and the like. Monoclinic LiMnO reported at present2Although having a large theoretical capacity (approximately 286mAh/g), part of the Mn of the transition metal layer migrates to the Li layer during charging to form cubic spinel LiMn2O4And causing capacity fade, to form cubic spinel LiMn2O4And can not be completely converted into tetragonal spinel Li2Mn2O4The capacity of the final material decreases dramatically (Okubo, m.et al. acs Nano,2010,4, 741). Monoclinic LiMnO2And tetragonal spinel Li2Mn2O4The crystal structure is easy to generate irreversible transformation and capacity attenuation due to the influence of Jahn-Teller in the charge-discharge process, so that novel LiMnO needs to be developed2. If LiMnO could be suppressed2Jahn-Teller distortion of the material is reduced, and irreversible change of a crystal structure in the charge-discharge process is reduced, so that LiMnO is expected to be greatly improved2The commercial application value of the material.
Disclosure of Invention
The invention aims to provide a monoclinic/tetragonal spinel heterostructure cathode material with higher capacity and better cycling stability and a preparation method thereof.
The technical solution for realizing the purpose of the invention is as follows:
the positive electrode material of the monoclinic/tetragonal spinel heterostructure is LiMnO with monoclinic and tetragonal spinel heterostructures2The structural formula is as follows:
wherein, two Mn-O bonds (1 and 2) forming the included angle alpha are [ MnO ]6]Octahedral long bonds, and the included angle alpha is 60-90 deg.
The invention also provides a preparation method of the monoclinic/tetragonal spinel heterostructure cathode material, which comprises the following steps:
the method comprises the steps of taking a manganese oxide material as a positive electrode material, taking a lithium metal sheet as a negative electrode, assembling a half cell in a glove box in an argon atmosphere, based on the mass of the manganese-containing oxide material, carrying out charge and discharge by adopting a constant current of 0.02-0.2A/g within a voltage range of 2.0-4.5V, and carrying out charge and discharge for 10-50 times to obtain the LiMnO with a monoclinic/tetragonal spinel heterostructure2And (3) a positive electrode material.
In the present invention, the manganese oxide material may be a powder material or a thin film material.
When the manganese oxide powder material is used as a positive electrode material, the manganese oxide powder material, a conductive agent and a binder are dissolved in N-methylpyrrolidone (NMP), coated on the surface of a conductive substrate, and dried to obtain the manganese oxide positive electrode sheet. In the specific embodiment of the invention, the adopted conductive agent is superconducting carbon black, and the adopted binder is polyvinylidene fluoride.
In the invention, the manganese oxide thin film material refers to a manganese oxide thin film or a nano array grown on a conductive substrate, and the conductive substrate material can be stainless steel, Ti, Ni, Au, Pt or a carbon material.
In the present invention, the manganese oxide is selected from Mn3O4MnO and MnO2One or more combinations thereof.
Preferably, the charging and discharging are performed 10 times with a constant current of 0.05A/g.
Compared with the prior art, the invention has the following advantages:
(1) the method forms monoclinic/tetragonal spinel heterostructure LiMnO in situ through charge-discharge reaction2The electrode material has the advantages of low reaction energy consumption and the like; (2) the monoclinic/tetragonal spinel heterostructure LiMnO of the invention2The electrode material has excellent electrochemical properties such as capacity, rate capability, cycling stability and the like, has excellent charge and discharge properties, and can be used as a positive electrode material of a lithium ion battery.
Detailed Description
The invention is further illustrated, but is not limited, by the following examples.
References in the preparation of manganese oxide thin film materials [ Xia H, nanosci.nanotechnol.lett.2012,4, 559-:
putting a conductive substrate into a mixed aqueous solution of manganese acetate and sodium sulfate, and depositing Mn (OH) on the surface of the conductive substrate in a constant potential mode in situ2Naturally drying the mixture in the air at normal temperature for 12-18 h, washing and then drying the mixture in vacuum to obtain Mn growing on a current collector3O4The nano-sheet array has a constant potential deposition potential of-1.30 to-1.85V, an electrodeposition time of 5 to 15min, and a ratio of the molar quantity of manganese to the molar quantity of sodium is 1:1 to 3. And taking a current collector as a working electrode, an Ag/AgCl electrode as a reference electrode, a Pt electrode as a counter electrode, and a mixed aqueous solution of manganese acetate and sodium sulfate as an electrolyte. Or preparing the manganese oxide thin film material by adopting a magnetron sputtering method (Xia H, et al.Small,2018,14, 1804149).
The monoclinic/tetragonal spinel heterostructure LiMnO of the invention2The preparation of the electrode material comprises the following two modes according to the difference of the raw materials of the manganese oxide:
oxide powder of manganese, superconducting carbon black (Super P) and polyvinylidene fluoride (PVDF) are mixed according to the mass ratio of 8: 1:1, uniformly mixing, dissolving in N-methyl pyrrolidone (NMP), coating on the surface of an aluminum foil, drying in a vacuum oven at 120 ℃ for 12 hours to obtain a manganese oxide positive plate, taking the manganese oxide positive plate as a positive electrode material and a lithium metal plate as a negative electrode, assembling into a half cell in a glove box in an argon atmosphere, and charging and discharging for 10-80 times by adopting a constant current of 0.02-0.2A/g within a voltage range of 2.0-4.5V to obtain the monoclinic/tetragonal spinel heterostructure LiMnO2A powder electrode material.
Secondly, manganese oxide film material is used as anode material, lithium metal sheet is used as cathode, half cell is assembled in a glove box in argon atmosphere, and monoclinic/tetragonal spinel heterostructure LiMnO can be obtained after charging and discharging for 10-80 times by adopting 0.02-0.2A/g constant current within the voltage range of 2.0-4.5V2A thin film electrode material.
Monoclinic/tetragonal spinel heterostructure LiMnO prepared by the invention2Film material as positive electrode, lithium metal sheet as negative electrode, 1.0mol/L LiPF6Propylene carbonate is used as electrolyte to detect monoclinic/tetragonal spinel heterostructure LiMnO2The capacity, rate capability, cycling stability and first coulombic efficiency of the electrode material are shown, and the test voltage range is 2.0-4.5V.
Example 1
Adding Mn3O4The powder, superconducting carbon black (Super P) and polyvinylidene fluoride (PVDF) are mixed according to the mass ratio of 8: 1:1, uniformly mixing, dissolving in N-methyl pyrrolidone (NMP), coating on the surface of an aluminum foil, drying in a vacuum oven at 120 ℃ for 12 hours to obtain a manganese oxide positive plate, taking the manganese oxide positive plate as a positive electrode material and a lithium metal plate as a negative electrode, assembling into a half cell in a glove box in an argon atmosphere, and charging and discharging for 50 times by adopting a constant current of 0.02A/g within a voltage range of 2.0-4.5V to obtain monoclinic/tetragonal spinelLiMnO of stone heterostructure2And (3) a positive electrode material.
Example 2
Dissolving 0.02mol of manganese acetate and 0.02mol of sodium sulfate in 50mL of deionized water, quickly and uniformly stirring, and mixing the water solution for later use. Gold foil is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a Pt electrode is used as a counter electrode, a mixed aqueous solution is used as an electrolyte, constant potential deposition is carried out for 15min under the condition of-1.4V, natural drying is carried out for 12h in the air at normal temperature, and vacuum drying is carried out after washing to obtain Mn3O4/Au thin film material. Then adding Mn3O4The Au thin film material is directly used as a positive electrode, the lithium metal sheet is used as a negative electrode, the half cell is assembled in a glove box in an argon atmosphere, and the half cell is charged and discharged for 10 times in a voltage range of 2.0-4.5V by adopting a constant current of 0.2A/g to obtain the LiMnO with the monoclinic/tetragonal spinel heterostructure2A thin film positive electrode material.
Example 3
Dissolving 0.02mol of manganese acetate and 0.02mol of sodium sulfate in 50mL of deionized water, quickly and uniformly stirring, and mixing the water solution for later use. Carbon cloth is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a Pt electrode is used as a counter electrode, a mixed aqueous solution is used as an electrolyte, constant potential deposition is carried out for 5min under the condition of-1.8V, natural drying is carried out for 14h in the air at normal temperature, and vacuum drying is carried out after washing to obtain Mn3O4A carbon cloth film material. Then adding Mn3O4The/carbon cloth film material is directly used as a positive electrode, the lithium metal sheet is used as a negative electrode, the lithium metal sheet is assembled into a half cell in a glove box in an argon atmosphere, and the half cell is charged and discharged for 10 times within the voltage range of 2.0-4.5V by adopting a constant current of 0.05A/g to obtain the LiMnO with the monoclinic/tetragonal spinel heterostructure2A thin film positive electrode material.
Monoclinic/tetragonal spinel heterostructures of LiMnO prepared in examples 1-32Electrode material as positive electrode, lithium metal sheet as negative electrode, 1.0mol/L LiPF6Propylene carbonate as electrolyte, half cell in argon glove box, testing monoclinic/tetragonal spinel heterostructures of LiMnO2The capacity, rate capability, cycling stability and first coulombic efficiency of the electrode material are shown, and the test voltage range is 2.0-4.5V.
Table 1 shows the LiMnO of monoclinic/tetragonal spinel heterostructures prepared in examples 1-32Electrical property data of the electrode material.
Comparative example 1
This comparative example is substantially the same as example 3, except that after 10 charges and discharges with a constant current of 0.01A/g, the capacity of the resulting product was only 3mAh/g at 0.05A/g.
Comparative example 2
This comparative example is substantially the same as example 3, except that after 10 charges and discharges with a constant current of 0.25A/g, the product obtained has a capacity of only 5mAh/g at 0.05A/g.
TABLE 1
Table 2 shows the LiMnO of monoclinic/tetragonal spinel heterostructures prepared in examples 1-32The molar ratio of lithium element to manganese element in the electrode material.
TABLE 2
As can be seen from Table 2, the monoclinic/tetragonal spinel heterostructures of LiMnO prepared in examples 1-32Li of the electrode material: the higher the Mn ratio, the larger the capacity presented in Table 1.
Claims (9)
1. The positive electrode material of the monoclinic/tetragonal spinel heterostructure is characterized in that the positive electrode material is LiMnO with monoclinic and tetragonal spinel heterostructures2The structural formula is as follows:
wherein, the two Mn-O bonds forming the included angle alpha are [ MnO ]6]Octahedral long bonds, and the included angle alpha is 60-90 deg.
2. The preparation method of the positive electrode material of the monoclinic/tetragonal spinel heterostructure according to claim 1, characterized by comprising the following steps:
the method comprises the steps of taking a manganese oxide material as a positive electrode material, taking a lithium metal sheet as a negative electrode, assembling a half cell in a glove box in an argon atmosphere, based on the mass of the manganese-containing oxide material, carrying out charge and discharge by adopting a constant current of 0.02-0.2A/g within a voltage range of 2.0-4.5V, and carrying out charge and discharge for 10-50 times to obtain the LiMnO with a monoclinic/tetragonal spinel heterostructure2And (3) a positive electrode material.
3. The method according to claim 2, wherein the manganese oxide material is a powder material or a thin film material.
4. The preparation method according to claim 3, wherein when the manganese oxide powder material is used as a positive electrode material, the manganese oxide powder material, a conductive agent and a binder are dissolved in N-methylpyrrolidone, coated on the surface of a conductive substrate, and dried to obtain the manganese oxide positive electrode sheet.
5. The method according to claim 4, wherein the conductive agent is superconducting carbon black, and the binder is polyvinylidene fluoride.
6. The method according to claim 3, wherein the thin film material of manganese oxide is a thin film or nanoarray of manganese oxide grown on a conductive substrate.
7. The method according to claim 6, wherein the conductive substrate is stainless steel, Ti, Ni, Au, Pt or carbon material.
8. The method of claim 2The preparation method is characterized in that the manganese oxide is selected from Mn3O4MnO and MnO2One or more combinations thereof.
9. The method according to claim 2, wherein the charging and discharging are performed 10 times with a constant current of 0.05A/g.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1817800A (en) * | 2006-01-26 | 2006-08-16 | 合肥工业大学 | Synthesis of series nanometer lithium and manganese oxide for lithium ion battery |
| CN102569797A (en) * | 2012-01-20 | 2012-07-11 | 中国科学院宁波材料技术与工程研究所 | Novel phosphate based composite cathode material, its preparation method and application thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1817800A (en) * | 2006-01-26 | 2006-08-16 | 合肥工业大学 | Synthesis of series nanometer lithium and manganese oxide for lithium ion battery |
| CN102569797A (en) * | 2012-01-20 | 2012-07-11 | 中国科学院宁波材料技术与工程研究所 | Novel phosphate based composite cathode material, its preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| Origin of Cycling Stability in Monoclinic and orthorhombic phase lithium manganese oxide cathodes;Haifeng Wang et al.;《Electrochemical and solid state Letters》;19991231;第490-493页 * |
| 尖晶石型锰酸锂在锂离子二次电池中的研究分析;朱律忠;《广东化工》;20171231;第98,111页 * |
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