CN106981653B - Preparation method of nano spinel type nickel-doped lithium manganate material - Google Patents
Preparation method of nano spinel type nickel-doped lithium manganate material Download PDFInfo
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- CN106981653B CN106981653B CN201710330440.7A CN201710330440A CN106981653B CN 106981653 B CN106981653 B CN 106981653B CN 201710330440 A CN201710330440 A CN 201710330440A CN 106981653 B CN106981653 B CN 106981653B
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- H—ELECTRICITY
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- 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
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- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- 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
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Abstract
The invention discloses a nano spinel type nickel-doped lithium manganate materialA method for preparing the material. The method comprises the following steps: according to the formula LiNi0.08Mn1.82O4Accurately weighing lithium salt, manganese salt and nickel salt in a beaker according to the molar ratio of the lithium ions to the manganese ions to the nickel ions of 1:1.92:0.08, stirring and dissolving the lithium salt, the manganese salt and the nickel salt in a proper amount of distilled water at 50 ℃ to form a uniform mixed solution, then dropwise adding an oxidant while stirring, and keeping the temperature for 5-15 min. The solution was heated at 100 ℃ to evaporate a volume of water and transferred to a porcelain crucible. Placing the porcelain crucible containing the solution in a temperature programming box type resistance furnace at 150 ℃ for heat preservation and heating for 5min, then performing combustion reaction for 30-60min at 400 ℃ in air atmosphere, finally preserving heat for 1-2h at 500 ℃, cooling and grinding. And (4) roasting the ground powder at the temperature of 600-700 ℃ for 3-6h, and grinding again to obtain the final product. The anode material prepared by the invention has excellent cycling stability.
Description
Technical Field
The invention relates to a preparation method of a lithium ion battery anode material, in particular to a nano spinel type nickel-doped lithium manganate material and a preparation method thereof, belonging to the technical field of inorganic non-metallic functional materials.
Background
The lithium ion battery has the advantages of high energy, high power density, no memory effect, good safety performance and the like, and is widely applied to electric vehicles, hybrid electric vehicles and portable electronic equipment, so that the energy supply market is led.
The spinel type lithium manganate has a unique three-dimensional space structure for rapid migration of lithium ions, has the advantages of low toxicity, low consumption, high safety, environmental friendliness and the like, and can replace commercial lithium cobaltate to become a new generation of promising positive electrode material.
However, the lithium manganate has unstable structure and poor cycle performance in the cycle process, and particularly under the high-temperature condition, the capacity is rapidly attenuated, which restricts the large-scale commercial use of spinel type lithium manganate in the field of lithium ion batteries. Currently, the main methods to ameliorate this disadvantage are bulk doping and surface modification of the material.
It is reported that nickel-doped spinel-type lithium manganate can significantly improve structural stability and thermal stability during cycling, and thus has attracted extensive attention of many researchers.
The Chinese patent publication No. CN103887490B discloses a preparation method of lithium nickel manganese oxide powder, which comprises the following steps: firstly, dissolving monomer acrylamide and bifunctional group monomer N, N' -methylene bisacrylamide in deionized water to obtain a mixed solution, then mixing the mixed solution with a solution of soluble lithium salt, nickel salt and manganese salt, and uniformly stirring ammonium persulfate serving as an initiator in the mixed solution. Placing the foamed ceramic in the mixed solution, soaking, heating with medium fire to evaporate water, forming gel, and combusting to obtain high-activity powder. Finally, the powder is insulated for 2-5h at 500 ℃ and then insulated for 3-10h at 750-900 ℃.
The Chinese patent application publication No. CN 103943849A relates to a preparation method of a nickel-doped lithium manganate anode material for a lithium ion battery, which comprises the following steps: (1) firstly, preparing a mixed solution of manganese acetate and polyvinylpyrrolidone: dropwise adding a sodium nickel-hydrogen carbonate aqueous solution into the mixed solution of manganese acetate and polyvinylpyrrolidone, controlling the dropwise adding amount to enable the molar ratio of nickel ions to manganese ions to be 1:1, after dropwise adding, magnetically stirring, standing, performing centrifugal separation to obtain manganese nickel-hydrogen carbonate nanoparticles, and adding the manganese nickel-hydrogen carbonate nanoparticles into a precursor manganese nitrate; (2) mixing lithium hydroxide, a precursor and manganese hydroxide, adding deionized water, stirring to form thick slurry, and reacting at the constant temperature of 150-250 ℃ to obtain the nickel-doped lithium manganate.
The main literature for preparing nickel-doped lithium-rich spinel lithium manganate is as follows:
(1) Raju K, Nkosi F P, Viswanathan E, et al. Microwave-enhancedelectrochemical cycling performance of the LiNi0.2Mn1.8O4spinel cathodematerial at elevated temperature[J]. Physical Chemistry Chemical Physics,2016, 18(18):13074.
(2) Kunjuzwa N, Kebede M, Ozoemena K I, et al. Stable nickel-substituted spinel cathode material (LiMn1.9Ni0.1O4) for lithium-ion batteryobtained by low temperature aqueous reduction technique[J]. Rsc Advances,2016.
（3）Gu Y J, Li Y, Fu Y, et al. LiNi0.5Mn1.5O4, synthesized throughammonia-mediated carbonate precipitation[J]. Electrochimica Acta, 2015, 176:1029-1035.
（4）Wu W W. Preparation and electrochemical performance of spinelLiNi0.5−xMn1.5+xO4(x = 0, 0.05, 0.1) hollow microspheres as cathode materialsfor lithium-ion batteries[J]. Ionics, 2015, 21(7):1843-1849.
（5）Zhou H, Ding X, Liu G, et al. Characterization of cathode fromLiNixMn2−xO4nanofibers by electrospinning for Li-ion batteries[J]. RscAdvances, 2015, 5(130):108007-108014.
(6)Xue Y, Wang Z B, Zheng L L, et al. Synthesis and performance ofhollow LiNi0.5Mn1.5O4with different particle sizes for lithium-ion batteries[J]. Rsc Advances, 2015, 5(122):100730-100735.
the method has the advantages of complex process steps, over-harsh sintering temperature and over-long heat preservation time, and restricts the large-scale production of the lithium manganate. Or, although the method has simple process steps, the specific capacity, rate capability, cycling stability and other aspects of the product cannot meet the requirements of the power battery.
According to the method for preparing the nano-scale nickel-doped spinel type lithium manganate cathode material in the air atmosphere, the reaction rate between the reactant raw material and the oxidant is controlled by controlling the concentration of the reactant raw material and the oxidant. The nickel-doped lithium spinel lithium manganate anode material is rapidly obtained by controlling the combustion reaction, the roasting temperature, the heat preservation time and the heating mode. The product synthesized by the method has excellent cycle stability.
Disclosure of Invention
The invention aims to provide a nickel-doped spinel lithium manganate positive electrode material and a preparation method thereof aiming at the defects of the spinel lithium manganate in the circulating process. The invention comprises the following steps:
according to the molecular formula LiNi0.08Mn1.92O4Accurately weighing solid lithium salt, manganese salt and nickel salt in a beaker according to the molar ratio of lithium ions to manganese ions to nickel ions of 1:1.92:0.08, adding a proper amount of distilled water into the beaker, heating and stirring at a constant temperature of 50 ℃ to form a uniform mixed solution, continuously dropwise adding an oxidant with the concentration of 5-9mol/L under the condition of stirring at the constant temperature of 50 ℃, keeping the temperature for 5-15min, then heating and stirring at the constant temperature of 100 ℃ to evaporate a certain volume of water from the solution, and finally transferring the mixed solution into a ceramic crucible. Placing the ceramic crucible containing the mixed solution in a temperature programming box type resistance furnace at the temperature of 150 ℃, carrying out heat preservation and heating for 5min under the air atmosphere, then heating to 400 ℃ to carry out combustion reaction for 30-60min, finally carrying out heat preservation for 1-2h at the temperature of 500 ℃, taking out and cooling to room temperature after heat preservation is finished, obtaining a black flaky powder product with fluffy appearance, and grinding by using a mortar to obtain powder. And roasting the ground powder in an air atmosphere of 600-700 ℃, preserving heat for 3-6h, taking out the powder after heat preservation, and cooling the powder to room temperature to obtain a nano-scale spinel type nickel-doped lithium manganate product.
The lithium salt is one or two of lithium nitrate and lithium acetate; the manganese salt is manganese acetate; the nickel salt is one or two of nickel nitrate and nickel acetate; the oxidant is nitric acid, the preferred concentration is 6mol/L, and the heat preservation time is 5-15min, preferably 10 min; the volume of the evaporated water was one fifth of the total volume.
The temperature programming is respectively raised to 400 ℃ and 500 ℃ at the speed of 20 ℃/min; the heating combustion reaction at 400 ℃ is carried out for 30-60min, and the preferable time is 30 min; the temperature is kept at 500 ℃ for 1-2h, and the preferable time is 1 h.
The roasting temperature is 600-700 ℃, and the preferred temperature is 700 ℃; and (3) keeping the temperature for 3-6h, preferably for 6 h.
Drawings
Fig. 1 is an XRD analysis result of the nickel-doped spinel-type lithium manganate prepared in example 1 according to the present invention.
Fig. 2 is a TEM image of nickel-doped spinel-type lithium manganate prepared in example 1 according to the present invention.
Fig. 3 is a high-resolution TEM image of nickel-doped spinel-type lithium manganate prepared in example 1 according to the present invention.
Fig. 4 is a cycle performance curve (1C rate) of nickel-doped spinel-type lithium manganate prepared according to the present invention in example 1.
Detailed Description
Example 1
Accurately weighing 1.1427 g of solid salt lithium nitrate, 7.9215 g of manganese acetate and 0.2062 g of nickel acetate in a beaker according to the molar ratio of lithium ions to manganese ions to nickel ions of 1:1.92:0.08 of 3g of target products, adding 10mL of distilled water into the beaker, heating and stirring at a constant temperature of 50 ℃ to form a uniform mixed solution, dropwise adding 5mL of 6mol/L nitric acid solution under constant temperature stirring to form a light red mixed solution, and keeping the temperature for 10 min. The solution was heated and stirred at a constant temperature of 100 ℃ to evaporate water in a volume of one fifth of the total volume of the solution, and then the mixed solution was transferred to a porcelain crucible. And (3) moving the ceramic crucible to a temperature programming box type resistance furnace at 150 ℃, carrying out heat preservation and heating for 5min in the air atmosphere, then heating to 400 ℃ at the speed of 20 ℃/min, carrying out heating combustion reaction for 30min in the air atmosphere, finally heating to 500 ℃ at the speed of 20 ℃/min, carrying out heat preservation for 1h, taking out and cooling to room temperature after heat preservation, and grinding the product into powder. And roasting the ground powder at 700 ℃ in an air atmosphere, preserving heat for 6 hours, and grinding again to obtain a nano-grade final product.
Claims (4)
1. A preparation method of a nickel-doped spinel lithium manganate positive electrode material is provided, wherein the molecular formula of the nickel-doped spinel lithium manganate positive electrode material is LiNi0.08Mn1.82O4The method is characterized by comprising the following steps:
(1) accurately weighing lithium salt, manganese salt and nickel salt in a beaker according to the molar ratio of lithium ions to manganese ions to nickel ions of 1:1.92:0.08, adding a proper amount of distilled water into the beaker, heating and stirring at a constant temperature of 50 ℃ to form a uniform mixed solution, continuously dropwise adding an oxidant with the concentration of 5-9mol/L under the condition of stirring at the constant temperature of 50 ℃, keeping the temperature for 5-15min, then heating and stirring at the constant temperature of 100 ℃ to evaporate a certain volume of water from the solution, and finally transferring the mixed solution into a ceramic crucible;
(2) placing the ceramic crucible containing the mixed solution in an air atmosphere temperature programmed box type resistance furnace at the temperature of 150 ℃ for heating for 5min, then heating to 400 ℃ for combustion reaction for 30-60min, finally preserving heat at 500 ℃ for 1-2h, taking out after heat preservation, cooling to room temperature to obtain a black powder product with fluffy appearance, and grinding the black powder product into powder;
(3) and roasting the ground powder in an air atmosphere of 600-700 ℃, preserving heat for 3-6h, taking out the powder after heat preservation, and cooling the powder to room temperature to obtain a nano-scale spinel type nickel-doped lithium manganate product.
2. The method for preparing the nickel-doped spinel lithium manganate cathode material as claimed in claim 1, wherein in said step (1), the lithium salt is one or two of lithium nitrate and lithium acetate; the manganese salt is manganese acetate; the nickel salt is one or two of nickel nitrate and nickel acetate; the oxidant is nitric acid with the concentration of 6mol/L, and the heat preservation time is 10 min; the volume of the evaporated water was one fifth of the total volume.
3. The method for preparing the nickel-doped spinel lithium manganate cathode material as claimed in claim 1, wherein in said step (2), the temperature is raised to 400 ℃ and 500 ℃ at a rate of 20 ℃/min; the time for combustion reaction by heating at 400 ℃ is 30 min; the heat preservation time at 500 ℃ is 1 h.
4. The method for preparing the nickel-doped spinel lithium manganate cathode material as claimed in claim 1, wherein in said step (3), the ground powder is baked in 700 ℃ air atmosphere and kept warm for 6 h.
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| CN107732212A (en) * | 2017-10-25 | 2018-02-23 | 广东邦普循环科技有限公司 | A kind of porous nickel cobalt manganese composite hydroxide and preparation method thereof and the application in lithium ion anode material |
| CN108400295B (en) * | 2018-02-02 | 2020-04-24 | 云南民族大学 | Silver-coated spinel-type LiMn2O4Material and method for the production thereof |
| CN109244453A (en) * | 2018-10-31 | 2019-01-18 | 云南民族大学 | A kind of method of nickel doping preparation High-performance lithium manganate anode material |
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| CN1288774C (en) * | 2004-03-31 | 2006-12-06 | 北京科技大学 | Method of synthetizing lithium ion cell positive electrode material through solution burning |
| CN104393236A (en) * | 2014-12-15 | 2015-03-04 | 中信大锰矿业有限责任公司大新锰矿分公司 | Doped lithium manganate anode material for lithium ion batteries and preparation method of doped lithium manganate anode material |
| CN104538625A (en) * | 2014-12-23 | 2015-04-22 | 云南民族大学 | One-step method for preparing high-magnification copper-doped lithium manganese dioxide lithium ion battery positive electrode material |
| CN104752711A (en) * | 2015-03-11 | 2015-07-01 | 云南民族大学 | Preparation method of high-performance nickel doped LiMn2O4 cathode material |
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