CN114105209A - Doped modified lithium manganate lithium ion battery positive electrode material and preparation method thereof - Google Patents
Doped modified lithium manganate lithium ion battery positive electrode material and preparation method thereof Download PDFInfo
- Publication number
- CN114105209A CN114105209A CN202111385554.4A CN202111385554A CN114105209A CN 114105209 A CN114105209 A CN 114105209A CN 202111385554 A CN202111385554 A CN 202111385554A CN 114105209 A CN114105209 A CN 114105209A
- Authority
- CN
- China
- Prior art keywords
- lithium
- salt
- ion battery
- lithium ion
- positive electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 27
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical class [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 title claims abstract description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 24
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000001354 calcination Methods 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 8
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 8
- 150000002696 manganese Chemical class 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 150000003754 zirconium Chemical class 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 3
- 229910015645 LiMn Inorganic materials 0.000 claims description 18
- 239000010405 anode material Substances 0.000 claims description 14
- 150000002500 ions Chemical class 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 239000011240 wet gel Substances 0.000 claims description 9
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 8
- 239000000499 gel Substances 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 229910014158 LiMn2-x Inorganic materials 0.000 claims description 5
- 229910014412 LiMn2−x Inorganic materials 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229940071125 manganese acetate Drugs 0.000 claims description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 11
- 239000010406 cathode material Substances 0.000 abstract description 8
- 238000003980 solgel method Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229910052596 spinel Inorganic materials 0.000 description 5
- 239000011029 spinel Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910012820 LiCoO Inorganic materials 0.000 description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 description 2
- 229910003005 LiNiO2 Inorganic materials 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012982 microporous membrane Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Complex oxides containing manganese and at least one other metal element
- C01G45/1221—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof
- C01G45/1242—Manganates or manganites with trivalent manganese, tetravalent manganese or mixtures thereof of the type (Mn2O4)-, e.g. LiMn2O4 or Li(MxMn2-x)O4
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
- C01P2002/32—Three-dimensional structures spinel-type (AB2O4)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a doped modified lithium manganate positive electrode material of a lithium ion battery and a preparation method thereof, belonging to the technical field of lithium ion batteries. The chemical general formula of the cathode material is LiMn2‑ xZrxO4Wherein x is 0.01,0.03,0.05,0.07, 0.1; according to a molar ratio of 1.03: 2-x: x: 1 respectively dissolving lithium salt, manganese salt, zirconium salt and citric acid in a solvent under the stirring condition, and preparing by a sol-gel method. And drying the obtained gel, calcining twice, and cooling to room temperature to obtain the Zr-doped lithium manganate material. The material prepared by the invention has excellent cycle performance and rate capability, particularly has excellent high-temperature cycle performance and high-rate cycle performance, and has high rate capacity. The preparation method is simple to operate and suitable for industrial production。
Description
Technical Field
The invention relates to a doped modified lithium manganate positive electrode material of a lithium ion battery and a preparation method thereof, belonging to the technical field of lithium ion batteries.
Background
As a green, environment-friendly and renewable energy source, the lithium ion battery always has unique advantages, such as: the energy density is large, the cycle performance is good, the environment is friendly, and the like, and the energy density is widely used in the field of novel electric automobile production.
The development of electrode materials, particularly positive electrode materials, for lithium ion batteries is of great importance. LiCoO is the main positive electrode material for lithium battery2、LiNiO2And LiMn2O4Although LiCoO is currently available2The industrialized production is realized, but the price is high, the resources are in short supply, and most importantly, the toxicity exists, and the factors always restrict the development of the method. As for LiNiO2Although with extremely high capacity and lower price, it becomes possible to replace LiCoO2The positive electrode material of (2), it is very difficult to prepare, thereby limiting its development. And spinel LiMn2O4Not only has great advantage in price, but also has the characteristics of good safety, no environmental pollution, high working voltage, low cost and the like, and the three-dimensional tunnel structure is more favorable for the intercalation and deintercalation of lithium ions than a layered compound, so that the compound is considered as the most promising substitute for LiCoO2One of the positive electrode materials of (1).
Although the spinel lithium manganate material has many advantages, the spinel lithium manganate material has unstable structure and serious capacity attenuation problem during the cycle in the charging and discharging process, and can be recycled at high temperature, and the capacity attenuation problem can be well solved by replacing a part of manganese ions with other ions. The preparation method mainly comprises a high-temperature solid phase method, a sol-gel method, a coprecipitation method and the like. The high-temperature solid phase method is simple to operate, but the mechanical mixing easily causes the uneven mixing of raw materials; the sol-gel method can realize the nanoscale mixing of ions, but cannot control the morphology of the material; although the coprecipitation method can obtain particles with higher sphericity, the prepared material has wider particle size distribution and the experimental method is complicated.
Disclosure of Invention
The invention aims to solve the problem of capacity attenuation, particularly high-temperature attenuation, of a lithium manganate material and improve rate capacity and cycle performance. Therefore, the invention provides a Zr ion doped modified lithium ion battery anode material lithium manganate and a preparation method thereof. The anode material prepared by the invention has the advantages of high specific capacity, good cycle performance, excellent high-temperature cycle performance and excellent high-rate cycle performance.
Specifically, the invention firstly provides a preparation method of Zr ion doped modified lithium ion battery anode material lithium manganate, and the chemical general formula of the anode material is LiMn2-xZrxO4Wherein x is 0.01,0.03,0.05,0.07, 0.1; the method comprises the following steps:
(1) respectively dissolving lithium salt, manganese salt, zirconium salt and citric acid in a solvent according to a molar ratio, mixing the solution, and then adjusting the pH of the solution to 6.5-7.5;
(2) evaporating the mixed solution obtained in the step (1) for 6-9 hours under stirring at 75-85 ℃ to obtain wet gel;
(3) drying the wet gel obtained in the step (2) for 10-12 hours at the temperature of 80-120 ℃ to obtain dry gel;
(4) calcining the dried gel obtained in the step (3), heating to 350-650 ℃ at the heating speed of 3-8 ℃/min, and preserving heat for 3-10 hours to obtain a precursor;
(5) grinding the precursor obtained in the step (4) in a ball mill for 1-3 hours, calcining under an oxygen-enriched condition or in an air atmosphere at the temperature rise speed of 3-8 ℃/min and the calcination temperature of 700-800 ℃ for 12-24 hours, cooling, and grinding to obtain the Zr ion doped modified lithium ion battery anode material LiMn2-xZrxO4。
In one embodiment of the present invention, in the step (1), the molar ratio of the lithium salt, the manganese salt, the zirconium salt and the citric acid is 1.03: 2-x: x: the lithium salt excess is to prevent the loss of lithium element due to the small amount of volatilization of lithium during high-temperature calcination.
In one embodiment of the present invention, the solvent in step (1) is one or both of absolute ethyl alcohol and deionized water.
In one embodiment of the present invention, in the step (1), the lithium salt is one or more of lithium carbonate, lithium nitrate, lithium acetate, and lithium hydroxide.
In one embodiment of the present invention, in step (1), the manganese salt is one or more of manganese nitrate and manganese acetate.
In one embodiment of the present invention, in step (1), the zirconium salt is one or more of zirconium nitrate and zirconium acetate.
In one embodiment of the present invention, in the step (2), the stirring speed is 200 to 500 rpm.
In one embodiment of the present invention, in the step (3), the drying is performed in a forced air drier.
In one embodiment of the present invention, the oxygen-rich condition in step (5) is that the calcination is performed in an atmosphere having an oxygen content of more than 21%.
The invention also provides the Zr ion doped modified lithium ion battery anode material LiMn prepared by the preparation method2-xZrxO4。
The invention also provides the Zr ion doped modified lithium ion battery anode material LiMn2-xZrxO4The lithium ion battery of (1).
The invention has the following beneficial effects:
(1) the preparation method is simple and easy to operate, and the prepared anode material is uniform in particle and high in crystallinity.
(2) The lithium ion battery anode material prepared by the invention has the advantages of high specific capacity, good cycle performance, low cost, high safety and the like.
(3) The lithium ion battery anode material prepared by the invention has excellent high-temperature cycle performance and high-rate cycle performance, and has high rate capacity.
Drawings
FIG. 1 shows LiMn as a positive electrode material obtained in example 11.97Zr0.03O4XRD pattern (characterizing the structure of the material).
FIG. 2 shows LiMn as a positive electrode material obtained in example 11.97Zr0.03O4SEM picture (characterizing the morphology of the material).
FIG. 3 shows LiMn as a positive electrode material obtained in example 11.97Zr0.03O4The first charge-discharge curve (3.0-4.5V, 0.2C, room temperature (25 ℃ C.)).
FIG. 4 shows LiMn as a positive electrode material obtained in example 11.93Zr0.03O4The cycle performance curve (3.0-4.5V, 0.2C, room temperature (25 ℃).
FIG. 5 shows LiMn as a positive electrode material obtained in example 11.93Zr0.03O4(3.0-4.5V, 0.2C, 0.5C, 1C, 5C,10C, room temperature (at 25 ℃).
FIG. 6 shows LiMn as a positive electrode material obtained in example 21.95Zr0.05O4XRD pattern (characterizing the structure of the material).
FIG. 7 shows LiMn as a positive electrode material obtained in example 21.95Zr0.05O4SEM picture (characterizing the morphology of the material).
FIG. 8 shows LiMn as a positive electrode material obtained in example 21.95Zr0.05O4The first charge-discharge curve (3.0-4.5V, 0.2C, room temperature (25 ℃ C.)).
FIG. 9 shows LiMn as a positive electrode material obtained in example 21.95Zr0.05O4The cycle performance curve (3.0-4.5V, 0.2C, room temperature (25 ℃).
FIG. 10 shows LiMn as a positive electrode material obtained in example 11.95Zr0.05O4(3.0-4.5V, 0.2C, 0.5C, 1C, 5C,10C, room temperature (at 25 ℃).
Detailed Description
The present invention is further described below with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
(1) Dissolving lithium nitrate, manganese acetate, zirconium nitrate and citric acid in deionized water under stirring conditions according to a molar ratio of 1.03:1.97:0.03:1 (the deionized water volume only needs to completely dissolve the salts), mixing the solutions, and then adjusting the pH of the solution to be neutral;
(2) under the condition of 80 ℃, evaporating the mixed solution obtained in the step (1) for 8 hours at a constant temperature under the condition of a stirring speed of 300 revolutions per minute to obtain wet gel;
(3) drying the wet gel in a forced air drying oven at 120 ℃ for 12 hours to evaporate the water in the wet gel to obtain dry gel;
(4) placing the xerogel in a muffle furnace for calcining, wherein the heating rate is 5 ℃/min, heating to 500 ℃, and preserving heat for 6 hours to obtain a precursor;
(5) grinding the precursor in a ball mill for 2 hours, calcining in air atmosphere at the temperature rise speed of 6 ℃/min, the calcining temperature of 800 ℃ and the calcining time of 21 hours, cooling and grinding to obtain the Zr ion doped modified lithium ion battery anode material LiMn1.97Zr0.03O4。
FIGS. 1 and 2 are each a positive electrode material LiMn obtained in example 11.97Zr0.03O4From the XRD and SEM images, it is clear that the positive electrode material LiMn was prepared1.97Zr0.03O4Still having a spinel structure with LiMn2O4And the consistent results show that the structure and the appearance of the cathode material are not changed by doping Zr.
The cathode material obtained in example 1 was assembled into a CR2032 type coin cell and subjected to a charge-discharge cycle test. Preparing an electrode by adopting a coating method, taking N-methyl-2-pyrrolidone (NMP) as a solvent, respectively weighing the positive electrode material, acetylene black and polyvinylidene fluoride (PVDF) according to the mass ratio of 80:12:8, grinding and mixing uniformly, coating on an aluminum foil paved on glass, and drying in a vacuum drying oven at 80 ℃ to obtain the positive electrode plate. A pure metal lithium sheet is taken as a negative electrode, a polypropylene microporous membrane Celgard 2325 is taken as a diaphragm, a mixed solution of LB315 (conventional solution) is taken as an electrolyte, and the electrolyte is filled in an argon-filled glove box (H)2Content of O<1ppm) were assembled into button cells.
Performing constant current circulation charge and discharge test on the button cell by using a LAND cell test system; under the charging and discharging conditions of the test voltage of 3.0-4.5V and 0.2C, the initial discharge specific capacity at room temperature (25 ℃) is 124.9 mAh.g-1The first charge-discharge curve is shown in fig. 3, and the capacity retention rate after 50 cycles of charge-discharge at 0.2C is 81.0% (see fig. 4). The specific discharge capacities under different multiplying powers of 0.2C, 0.5C, 1C, 5C and 10C are respectively 124.9 mAh.g-1、116.9mAh·g-1、104.5mAh·g-1、85.4mAh·g-1And 57.2mAh · g-1When the current density returns to 0.2C again, the discharge specific capacity still remains 122.0mAh g-1As shown in fig. 5, it can be seen that the cathode material prepared by the invention has excellent rate performance.
Example 2
(1) According to a molar ratio of 1.03: 1.95:0.05:1 dissolving lithium nitrate, manganese acetate, zirconium nitrate and citric acid in deionized water under stirring (the volume of deionized water is only needed to completely dissolve the salts), mixing the solutions, and then adjusting the pH of the solution to be neutral;
(2) placing the mixture obtained in the step (1) in a water bath kettle with the constant temperature of 80 ℃, and continuously stirring at the speed of 300 revolutions per minute until the absolute ethyl alcohol is completely volatilized to obtain wet gel;
(3) drying the wet gel obtained in the step (2) in a forced air drying oven at 120 ℃ for 12 hours to remove residual solvent to obtain dry gel;
(4) placing the obtained dry gel in a muffle furnace for calcining at the temperature rise speed of 5 ℃/min to 500 ℃ for 6 hours to obtain a precursor;
(5) grinding the precursor in a ball mill for 2 hours, then calcining in a muffle furnace at 800 ℃ for 21 hours, cooling and grinding to obtain the lithium ion battery cathode material LiMn with low cost and high safety1.95Zr0.05O4。
FIGS. 6 and 7 show the positive electrode materials LiMn obtained in example 11.95Zr0.05O4From the XRD and SEM images, it is clear that the positive electrode material LiMn was prepared1.95Zr0.05O4Still having a spinel structure with LiMn2O4And the consistent results show that the structure and the appearance of the cathode material are not changed by doping Zr.
The cathode material obtained in example 2 was assembled into a CR2032 type coin cell for charge-discharge cycle testing. Preparing an electrode by adopting a coating method, taking N-methyl-2-pyrrolidone (NMP) as a solvent, and respectively weighing the positive electrode material and acetylene black according to a mass ratio of 80:12:8And polyvinylidene fluoride (PVDF), grinding and mixing uniformly, coating on the pretreated aluminum foil, and drying in a vacuum drying oven at 80 ℃ to obtain the positive plate. A pure metal lithium sheet is taken as a negative electrode, a polypropylene microporous membrane Celgard 2325 is taken as a diaphragm, a mixed solution of LB315 (conventional solution) is taken as an electrolyte, and the electrolyte is filled in an argon-filled glove box (H)2Content of O<1ppm) were assembled into a simulated cell.
Performing constant current circulation charge and discharge test on the button cell by using a LAND cell test system; under the charging and discharging conditions of the test voltage of 3.0-4.5V and 0.2C, the initial discharge specific capacity at room temperature (25 ℃) is 116.3 mAh.g-1The first charge-discharge curve is shown in figure 8, the capacity retention rate after 50 cycles of charge-discharge at 0.2C is 88.8% (shown in figure 9), and the specific discharge capacities at different multiplying factors of 0.2C, 0.5C, 1C, 5C and 10C are respectively 116.2mAh g-1、107.7mAh·g-1、98.8mAh·g-1、84.2mAh·g-1And 71.2mAh · g-1When the current density returns to 0.2C again, the discharge specific capacity still remains 112.6mAh g-1Referring to fig. 10, it can be seen that the cathode material prepared by the present invention has excellent rate performance.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. The preparation method of Zr ion doped modified lithium ion battery anode material lithium manganate is characterized in that the anode material has a chemical general formula of LiMn2-xZrxO4Wherein x is 0.01,0.03,0.05,0.07, 0.1; the method comprises the following steps:
(1) respectively dissolving lithium salt, manganese salt, zirconium salt and citric acid in a solvent according to a molar ratio, mixing the solution, and then adjusting the pH of the solution to 6.5-7.5;
(2) evaporating the mixed solution obtained in the step (1) for 6-9 hours under stirring at 75-85 ℃ to obtain wet gel;
(3) drying the wet gel obtained in the step (2) for 10-12 hours at the temperature of 80-120 ℃ to obtain dry gel;
(4) calcining the dried gel obtained in the step (3), heating to 350-650 ℃ at the heating speed of 3-8 ℃/min, and preserving heat for 3-10 hours to obtain a precursor;
(5) grinding the precursor obtained in the step (4) in a ball mill for 1-3 hours, calcining under an oxygen-enriched condition or in an air atmosphere at the temperature rise speed of 3-8 ℃/min and the calcination temperature of 700-800 ℃ for 12-24 hours, cooling, and grinding to obtain the Zr ion doped modified lithium ion battery anode material LiMn2-xZrxO4。
2. The method according to claim 1, wherein in the step (1), the molar ratio of the lithium salt to the manganese salt to the zirconium salt to the citric acid is 1.03: 2-x: x: 1.
3. the preparation method according to claim 1, wherein the solvent in step (1) is one or both of absolute ethyl alcohol and deionized water.
4. The method according to any one of claims 1 to 3, wherein in the step (1), the lithium salt is one or more of lithium carbonate, lithium nitrate, lithium acetate and lithium hydroxide.
5. The preparation method according to any one of claims 1 to 4, wherein in the step (1), the manganese salt is one or more of manganese nitrate and manganese acetate.
6. The method according to any one of claims 1 to 5, wherein in the step (1), the zirconium salt is one or more of zirconium nitrate and zirconium acetate.
7. The method according to any one of claims 1 to 6, wherein the stirring speed in the step (2) is 200 to 500 rpm.
8. The method according to any one of claims 1 to 7, wherein the oxygen-rich condition in the step (5) is calcination in an atmosphere having an oxygen content of more than 21%.
9. The Zr ion doped modified lithium ion battery positive electrode material LiMn prepared by the preparation method according to any one of claims 1 to 82-xZrxO4。
10. The Zr-doped modified lithium ion battery positive electrode material LiMn comprising the Zr-doped modified lithium ion battery positive electrode material of claim 92-xZrxO4The lithium ion battery of (1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111385554.4A CN114105209A (en) | 2021-11-22 | 2021-11-22 | Doped modified lithium manganate lithium ion battery positive electrode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111385554.4A CN114105209A (en) | 2021-11-22 | 2021-11-22 | Doped modified lithium manganate lithium ion battery positive electrode material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114105209A true CN114105209A (en) | 2022-03-01 |
Family
ID=80439297
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111385554.4A Pending CN114105209A (en) | 2021-11-22 | 2021-11-22 | Doped modified lithium manganate lithium ion battery positive electrode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114105209A (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102730764A (en) * | 2012-06-27 | 2012-10-17 | 江南大学 | Modified spinel lithium manganate material and preparation method thereof |
| JP2012201539A (en) * | 2011-03-24 | 2012-10-22 | Agc Seimi Chemical Co Ltd | Method for producing lithium-containing compound oxide |
| CN103579613A (en) * | 2013-11-28 | 2014-02-12 | 福建师范大学 | Method for preparing spinel-doped lithium-enriched lithium manganate anode material through doping zirconium |
| CN104253265A (en) * | 2013-06-28 | 2014-12-31 | 江南大学 | Cation-doped and modified lithium ion battery (4:4:2)type ternary cathode material and preparation method thereof |
| CN104319393A (en) * | 2014-11-12 | 2015-01-28 | 安徽工业大学 | Doping modification method of spinel lithium manganate anode material |
| CN105576231A (en) * | 2016-02-25 | 2016-05-11 | 江南大学 | High-voltage lithium oil battery positive electrode material with spinel structure and preparation method of high-voltage lithium oil battery positive electrode material |
| JP2016076369A (en) * | 2014-10-06 | 2016-05-12 | 旭化成株式会社 | Lithium ion secondary battery |
| CN108091854A (en) * | 2017-12-13 | 2018-05-29 | 江南大学 | A kind of high-voltage spinel type anode material for lithium-ion batteries of Anion-cation multiple dope and preparation method thereof |
| WO2018148833A1 (en) * | 2017-02-15 | 2018-08-23 | HYDRO-QUéBEC | Electrode materials and processes for their preparation |
| CN108899524A (en) * | 2018-07-09 | 2018-11-27 | 河南科技学院 | A kind of lithium ion battery mangaic acid lithium anode material and preparation method thereof |
| CN113644274A (en) * | 2021-09-15 | 2021-11-12 | 广州大学 | O2 type lithium ion battery anode material and preparation method and application thereof |
-
2021
- 2021-11-22 CN CN202111385554.4A patent/CN114105209A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012201539A (en) * | 2011-03-24 | 2012-10-22 | Agc Seimi Chemical Co Ltd | Method for producing lithium-containing compound oxide |
| CN102730764A (en) * | 2012-06-27 | 2012-10-17 | 江南大学 | Modified spinel lithium manganate material and preparation method thereof |
| CN104253265A (en) * | 2013-06-28 | 2014-12-31 | 江南大学 | Cation-doped and modified lithium ion battery (4:4:2)type ternary cathode material and preparation method thereof |
| CN103579613A (en) * | 2013-11-28 | 2014-02-12 | 福建师范大学 | Method for preparing spinel-doped lithium-enriched lithium manganate anode material through doping zirconium |
| JP2016076369A (en) * | 2014-10-06 | 2016-05-12 | 旭化成株式会社 | Lithium ion secondary battery |
| CN104319393A (en) * | 2014-11-12 | 2015-01-28 | 安徽工业大学 | Doping modification method of spinel lithium manganate anode material |
| CN105576231A (en) * | 2016-02-25 | 2016-05-11 | 江南大学 | High-voltage lithium oil battery positive electrode material with spinel structure and preparation method of high-voltage lithium oil battery positive electrode material |
| WO2018148833A1 (en) * | 2017-02-15 | 2018-08-23 | HYDRO-QUéBEC | Electrode materials and processes for their preparation |
| CN108091854A (en) * | 2017-12-13 | 2018-05-29 | 江南大学 | A kind of high-voltage spinel type anode material for lithium-ion batteries of Anion-cation multiple dope and preparation method thereof |
| CN108899524A (en) * | 2018-07-09 | 2018-11-27 | 河南科技学院 | A kind of lithium ion battery mangaic acid lithium anode material and preparation method thereof |
| CN113644274A (en) * | 2021-09-15 | 2021-11-12 | 广州大学 | O2 type lithium ion battery anode material and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| HAO ZHENG ET AL.: "Synthesis and Electrochemical Performance of Zn-Doped LiMn2O4 as Cathode Material for Lithium Ion Batteries", 《IOP CONFERENCE SERIES:MATERIALS SCIENCE AND ENGINEERING》 * |
| XIAOHONG LIU ET AL.: "Fabrication and characterization of Zr and Co co-doped LiMn2O4 nanowires using sol–gel–AAO template process", 《JOURNAL OF MATERIALS SCIENCE：MATERIALS IN ELECTRONICS》 * |
| ZHIGUO WANG ET AL.: "An improved solid-state reaction to synthesize Zr-doped Li4Ti5O12 anode material and its application in LiMn2O4/Li4Ti5O12 full-cell", 《CERAMICS INTERNATIONAL》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tang et al. | Synthesis and electrochemical performance of lithium-rich cathode material Li [Li0. 2Ni0. 15Mn0. 55Co0. 1-xAlx] O2 | |
| CN102437323B (en) | Anode material of lithium ion battery and preparation method thereof | |
| CN107403913B (en) | Surface-modified nickel-cobalt lithium aluminate cathode material and preparation method thereof | |
| CN110931797A (en) | High-nickel positive electrode material with composite coating layer and preparation method thereof | |
| CN102956883B (en) | AnodePositive electrode material of lithium ion battery with porous laminated structure and preparation method thereof | |
| CN105185954A (en) | LiAlO2 coated LiNi1-xCoxO2 lithium-ion battery positive electrode material and preparation method thereof | |
| CN107591529A (en) | A kind of titanium phosphate lithium cladding nickel-cobalt-manganternary ternary anode material and preparation method thereof | |
| CN111463428A (en) | Sodium ion doped ternary cathode material and preparation method thereof | |
| CN105576231A (en) | High-voltage lithium oil battery positive electrode material with spinel structure and preparation method of high-voltage lithium oil battery positive electrode material | |
| CN108448109A (en) | A kind of stratiform lithium-rich manganese-based anode material and preparation method thereof | |
| CN108091854A (en) | A kind of high-voltage spinel type anode material for lithium-ion batteries of Anion-cation multiple dope and preparation method thereof | |
| CN113629219A (en) | Sodium-ion battery positive electrode material, sodium-ion battery and preparation method and application thereof | |
| CN105236486A (en) | High-performance lithium ion batteries cathode material vanadic pentoxide hollow microballoon and preparation method | |
| CN112340786A (en) | Modification method of positive electrode material, modified positive electrode material and lithium ion battery | |
| CN106654255A (en) | Aluminum-doped and modified cathode material for high-capacity lithium ion batteries | |
| CN113644274A (en) | O2 type lithium ion battery anode material and preparation method and application thereof | |
| CN107994220A (en) | LiMn2O4 composite material, its preparation method and the lithium ion battery that a kind of molybdenum doping is modified | |
| CN110190277A (en) | A kind of anode material for lithium-ion batteries LiMnO2@C and preparation method thereof | |
| CN104577101A (en) | Preparation method for surface-modified lithium-manganese-rich cathode material of lithium ion battery | |
| CN114906880A (en) | Preparation method of positive electrode material of sodium-ion battery and sodium-ion battery | |
| CN110776007B (en) | Preparation method of ping-pong chrysanthemum-shaped lithium vanadate material | |
| CN114105209A (en) | Doped modified lithium manganate lithium ion battery positive electrode material and preparation method thereof | |
| CN115579506A (en) | Lithium ion battery | |
| CN109461897B (en) | Preparation method of spindle-shaped carbon-coated vanadium-based positive electrode material | |
| CN108011096B (en) | Porous cubic lithium battery cathode material lithium nickel manganese oxide and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220301 |