CN104966830B - Preparation method and application of rod-shaped lithium nickel manganese oxide material - Google Patents
Preparation method and application of rod-shaped lithium nickel manganese oxide material Download PDFInfo
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- CN104966830B CN104966830B CN201510269269.4A CN201510269269A CN104966830B CN 104966830 B CN104966830 B CN 104966830B CN 201510269269 A CN201510269269 A CN 201510269269A CN 104966830 B CN104966830 B CN 104966830B
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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
-
- 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
- H01M4/52—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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- 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 preparation method and an application of a rod-shaped lithium nickel manganese oxide material. The method comprises the following steps: 1, carrying out magneton stirring mixing on rod-shaped manganese dioxide, a nickel source and a lithium source according to a molar ratio of Li:Ni:Mn of 1-1.1:0.5:1.5 in an ethanol solution, carrying out stirring drying in 50-80DEG C oil bath, and grinding the obtained dried powder; 2, repeating step 1 3-5 times to obtain a uniformly-mixed three-component mixture; and 3, putting the above obtained powder mixture in a corundum magnetic boat, sintering in air atmosphere at 700-800DEG C for 12-20h, and naturally cooling. The lithium source, a manganese source and the nickel source are simply mixed in the preparation process of the rod-shaped lithium nickel manganese oxide material, so the method is convenient to operate, and the preparation method also has the advantages of simple operation, stable and reliable process and good reappearance.
Description
Technical field
The invention belongs to technical field of lithium ion battery positive pole material preparation, is related to a kind of system of bar-shaped nickel ion doped material
Preparation Method and application.
Background technology
Current battery almost reaches its theoretical performance, develops limited, it is impossible to meets and requires, therefore exploitation new type lithium ion electricity
Pond is the necessity of social development.The development of battery depends primarily on the development and application of battery material, and for lithium ion
The raising of positive electrode performance is depended mainly on for battery then.
Since with LiCoO2Since the lithium ion battery commercialization of positive electrode, graphite for negative material, lithium-ion electric
Pond is widely used in the various portable electrics such as mobile phone, notebook computer because of its high power capacity, high voltage and advantages of environment protection
Sub- equipment.In recent years, with Fossil fuel increasingly reduce and environmental problem it is increasingly serious, lithium ion battery is in electric automobile
Increasingly paid close attention to by people with the application in energy storage.However, the energy density and power of existing lithium ion battery
Density is still low, and its safety and cycle life not yet reach the requirement of following electric automobile and energy-storage system application, lithium from
The energy density of sub- battery needs to continue to improve with safety.Improve monocell output voltage be improve battery energy density and
The effective way of power density.Automaker wishes that battery material scientist is flat for a kind of electric discharge of electric automobile application and development
Platform is high, the positive electrode that cycle performance and high rate performance are excellent.
At present, conventional anode material for lithium-ion batteries includes LiCoO2、LiMn2O4、LiNi1/3Co1/3Mn1/3O2And
LiFePO4Deng the Li (Li with many lithium structuresaCoxNiyMnz)O2There is in specific capacity and energy density advantage, and point is brilliant
Stone-type LiNi0.5Mn1.5O4Positive electrode has the average charge and discharge platform of highest, and its average working voltage, can be with up to 4.7 V
Higher running voltage and energy and power density are provided, Li (Li are only second toaCoxNiyMnz)O2Material.
While spinel-type LiNi0.5Mn1.5O4Material has three-dimensional ion diffusion admittance, excellent structural stability, rich
Rich resource, cheap cost and advantages of environment protection, become one of alternative positive electrode of lithium ion battery of new generation,
So as to enjoy the concern of various countries' researcher.
The content of the invention
It is an object of the invention to provide a kind of preparation method and application of bar-shaped nickel ion doped material, the method is simply easy
OK, environmental protection, process stabilizing reliability, favorable reproducibility.
The purpose of the present invention is achieved by the following technical solution：
A kind of preparation method of bar-shaped nickel ion doped material, with nano bar-shape manganese dioxide as template, by liquid-phase mixing
Mode manganese source, nickel source, lithium source are uniformly mixed, after high temperature sintering obtain with Rod-like shape nickel ion doped material, specifically
Step is as follows：
（1）With bar-shaped manganese dioxide, nickel source, lithium source as raw material, with mol ratio as Li:Ni:Mn=1~1.1:0.5:1.5
Using magneton stirring mixing in ethanol solution, and the stirring and drying in 50 ~ 80 DEG C of oil baths, by the powder mull of drying；
（2）Repeat step（1）Three ~ five times, the mixed uniformly powder of three kinds of compositions of acquisition；
（3）The mixture of powders of above-mentioned acquisition is put in corundum magnetic boat, is sintered in air atmosphere, sintering temperature is
700 ~ 800 DEG C, sintering time is 12 ~ 20 hours, terminates rear Temperature fall.
Bar-shaped nickel ion doped material prepared by said method can apply to the positive electrode of lithium ion battery.
In the present invention, the bar-shaped manganese dioxide prepares the manganese dioxide with club shaped structure using hydro-thermal method, concrete to walk
It is rapid as follows：Weigh seven anhydrous manganeses of 1.2726g and 1.7176g Ammonium persulfate .s be added in 50ml distilled water, stir 30min,
It is all 0.15mol/L to obtain manganese sulfate and ammonium persulfate concentrations.Solution is added in water heating kettle, be put in homogeneous reactor with
The heating rate of 10 DEG C/min is raised to 180 DEG C, and 12 hours are reacted at 180 DEG C, by the precipitation sucking filtration drying for obtaining, obtains rod
Shape manganese bioxide material.
In the present invention, the nickel source for adopting is four hydration nickel acetates, and lithium source is two hydration lithium acetate.
Advantages of the present invention is as follows：
（1）During bar-shaped nickel ion doped material prepared by the present invention, lithium source, manganese source, nickel source hybrid mode are simple, just
In operation.
（2）The preparation method of the bar-shaped nickel ion doped material of the present invention is simple to operate, process stabilizing reliability, favorable reproducibility.
（3）The present invention bar-shaped nickel ion doped high-voltage positive electrode with certain pattern with bar-shaped manganese dioxide as templated synthesis
Material.
（4）This kind of synthesis mode is using acetate as raw material, cheap.
Description of the drawings
Fig. 1 is the SEM figures of bar-shaped nickel ion doped；
Fig. 2 is the XRD spectrum of bar-shaped nickel ion doped；
Fig. 3 is that the Mn units vegetarian noodles of bar-shaped nickel ion doped sweeps figure；
Fig. 4 is that the Ni units vegetarian noodles of bar-shaped nickel ion doped sweeps figure；
Fig. 5 is the 0.5C cycle performances of bar-shaped nickel ion doped material.
Specific embodiment
Below in conjunction with the accompanying drawings technical scheme is further described, but is not limited to thus, every to this
Inventive technique scheme is modified or equivalent, without deviating from the spirit and scope of technical solution of the present invention, all should cover
In protection scope of the present invention.
Embodiment 1：
（1）The preparation of nano bar-shape manganese dioxide
Weigh seven anhydrous manganeses of 1.2726g and 1.7176g Ammonium persulfate .s be added in 50ml distilled water, stir 30min,
It is all 0.15mol/L to obtain manganese sulfate and ammonium persulfate concentrations.Solution is added in water heating kettle, be put in homogeneous reactor with
The heating rate of 10 DEG C/min is raised to 180 DEG C, and 12 hours are reacted at 180 DEG C, by the precipitation sucking filtration drying for obtaining, obtains rod
Shape manganese bioxide material.
（2）With bar-shaped manganese dioxide as manganese source, nickel source and lithium source mix
Manganese dioxide nickel acetate and lithium acetate with above-mentioned acquisition as raw material, with Li:Ni:Mn mol ratios are 1.1:0.5:
After 1.5 weighings, raw material is mixed using magneton stirring in ethanol solution, and the stirring and drying in 80 DEG C of oil baths, by drying
Powder mull.
（3）Step（2）In triplicate, you can the mixed uniformly powder of three kinds of compositions of acquisition.
（4）High temperature sintering prepares nickel ion doped material
The mixed uniformly powder of three kinds of compositions of above-mentioned acquisition is put in corundum magnetic boat, is sintered in air atmosphere,
Heating rate is 10 DEG C/min, and sintering temperature is 700 DEG C, and sintering time is 12 hours, terminates rear Temperature fall.
Fig. 1-4 sweeps photo for the face of the SEM photograph and nickel manganese element of bar-shaped nickel ion doped material, it can be seen that bar-shaped
Material distribution is more uniform, and the distribution of nickel manganese element is very uniform.
From electrochemistry cycle performance in Fig. 5, bar-shaped nickel ion doped material prepared by the present invention can apply to lithium from
The positive electrode of sub- battery, as this kind of material has higher voltage platform, can apply to lithium-ion-power cell, has
Good cycle performance, 181.2139 mAh/g of initial charge capacity of material, first discharge capacity filled for 122.705 first
Discharging efficiency is 67.71%, and after 50 circulations, charging capacity is 106.86 mAh/g.
Embodiment 2：
（1）The preparation of nano bar-shape manganese dioxide
Weigh seven anhydrous manganeses of 1.2726g and 1.7176g Ammonium persulfate .s be added in 50ml distilled water, stir 30min,
It is all 0.15mol/L to obtain manganese sulfate and ammonium persulfate concentrations.Solution is added in water heating kettle, be put in homogeneous reactor with
The heating rate of 10 DEG C/min is raised to 180 DEG C, and 12 hours are reacted at 180 DEG C, by the precipitation sucking filtration drying for obtaining, obtains rod
Shape manganese bioxide material.
（2）With bar-shaped manganese dioxide as manganese source, nickel source and lithium source mix
Manganese dioxide nickel acetate and lithium acetate with above-mentioned acquisition as raw material, with Li:Ni:Mn mol ratios are 1:0.5:1.5
After weighing, using magneton stirring mixing in ethanol solution, and the stirring and drying in 80 DEG C of oil baths, by the powder mull of drying.
（3）Step（2）It is repeated four times, you can the mixed uniformly powder of three kinds of compositions of acquisition.
（4）High temperature sintering prepares nickel ion doped material
The mixed uniformly powder of three kinds of compositions of above-mentioned acquisition is put in corundum magnetic boat, is sintered in air atmosphere,
Heating rate is 10 DEG C/min, and sintering temperature is 700 DEG C, and sintering time is 12 hours, terminates rear Temperature fall.
Claims (2)
1. a kind of preparation method of bar-shaped nickel ion doped material, it is characterised in that methods described step is as follows：
（1）Weigh seven anhydrous manganeses of 1.2726g and 1.7176g Ammonium persulfate .s be added in 50ml distilled water, stir 30min,
Acquisition manganese sulfate and ammonium persulfate concentrations are all the solution of 0.15mol/L；Solution is added in water heating kettle, homogeneous reaction is put into
180 DEG C are raised to the heating rate of 10 DEG C/min in device, 12 hours are reacted at 180 DEG C, by the precipitation sucking filtration drying for obtaining,
Obtain bar-shaped manganese bioxide material；
（2）Bar-shaped manganese dioxide and four hydration nickel acetates and two are hydrated into lithium acetate with mol ratio as Li:Ni:Mn=1~1.1:
0.5:1.5 are mixed using magneton stirring in ethanol solution, and the stirring and drying in 50 ~ 80 DEG C of oil baths, and the powder of drying is ground
Mill；
（3）Repeat step（2）Three ~ five times, the mixed uniformly powder of three kinds of compositions of acquisition；
（4）By step（3）The powder of acquisition is put in corundum magnetic boat, is sintered in air atmosphere, and sintering temperature is 700 ~ 800
DEG C, sintering time is 12 ~ 20 hours, terminates rear Temperature fall.
2. application of the bar-shaped nickel ion doped material that prepared by claim 1 methods described in the positive electrode of lithium ion battery.
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| CN201510269269.4A CN104966830B (en) | 2015-05-25 | 2015-05-25 | Preparation method and application of rod-shaped lithium nickel manganese oxide material |
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| CN201510269269.4A CN104966830B (en) | 2015-05-25 | 2015-05-25 | Preparation method and application of rod-shaped lithium nickel manganese oxide material |
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| CN104966830A CN104966830A (en) | 2015-10-07 |
| CN104966830B true CN104966830B (en) | 2017-05-17 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108417830B (en) * | 2018-03-21 | 2020-05-15 | 湖北大学 | Lithium nickel manganese oxide positive electrode material and preparation method thereof |
| CN111087030A (en) * | 2019-12-20 | 2020-05-01 | 佛山科学技术学院 | LiNi0.5Mn1.5O4Method for producing materials and use thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102120624A (en) * | 2011-01-14 | 2011-07-13 | 哈尔滨工业大学 | Method for preparing high-voltage lithium ion battery positive electrode material LiXyNi0.5-yMn1.5O4 |
| CN103762354A (en) * | 2014-01-22 | 2014-04-30 | 中南大学 | LiNi0.5Mn1.5O4 material, preparation method thereof as well as lithium ion battery |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102120624A (en) * | 2011-01-14 | 2011-07-13 | 哈尔滨工业大学 | Method for preparing high-voltage lithium ion battery positive electrode material LiXyNi0.5-yMn1.5O4 |
| CN103762354A (en) * | 2014-01-22 | 2014-04-30 | 中南大学 | LiNi0.5Mn1.5O4 material, preparation method thereof as well as lithium ion battery |
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