CN104966830A - 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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- CN104966830A CN104966830A CN201510269269.4A CN201510269269A CN104966830A CN 104966830 A CN104966830 A CN 104966830A CN 201510269269 A CN201510269269 A CN 201510269269A CN 104966830 A CN104966830 A CN 104966830A
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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
- 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, relate to a kind of preparation method and application of bar-shaped nickel ion doped material.
Background technology
Current battery is close to and reaches its theoretical performance, develop limited, can not meet the demands, therefore development of new lithium ion battery is the necessity of social development.The development of battery depends primarily on the development and application of battery material, for the raising then depending mainly on positive electrode performance lithium ion battery.
Since with LiCoO
2since positive electrode, graphite is the lithium ion battery commercialization of negative material, lithium ion battery is widely used in the various portable electric appts such as mobile phone, notebook computer because of its high power capacity, high voltage and advantages of environment protection.In recent years, along with the minimizing day by day of fossil fuel and the increasingly serious of environmental problem, the application of lithium ion battery in electric automobile and energy storage more and more receives the concern of people.But the energy density of existing lithium ion battery and power density are still on the low side, its fail safe and cycle life not yet reach the requirement of following electric automobile and energy-storage system application, and the energy density of lithium ion battery and fail safe need to continue to improve.The output voltage improving monocell is the effective way improving battery energy density and power density.Automaker wishes that battery material scientist is high for a kind of discharge platform of electric automobile application and development, the positive electrode of cycle performance and high rate performance excellence.
At present, conventional anode material for lithium-ion batteries comprises LiCoO
2, LiMn
2o
4, LiNi
1/3co
1/3mn
1/3o
2and LiFePO
4deng, there is the Li (Li of many lithiums structure
aco
xni
ymn
z) O
2specific capacity and energy density have advantage, and spinel-type LiNi
0.5mn
1.5o
4positive electrode has the highest average charge and discharge platform, and its average working voltage reaches 4.7 V, can provide higher operating voltage and energy and power density, be only second to Li (Li
aco
xni
ymn
z) O
2material.
Spinel-type LiNi simultaneously
0.5mn
1.5o
4material has three-dimensional ion diffuse passage, excellent structural stability, rich in natural resources, cheap cost and advantages of environment protection, one of alternative positive electrode becoming lithium ion battery of new generation, thus enjoys the concern of various countries' researcher.
Summary of the invention
The object of the present invention is to provide a kind of preparation method and application of bar-shaped nickel ion doped material, the method is simple, environmental protection, and process stabilizing is reliable, favorable reproducibility.
The object of the invention is to be achieved through the following technical solutions:
A preparation method for bar-shaped nickel ion doped material, with nano bar-shape manganese dioxide for template, the mode mixed by liquid phase is by manganese source, nickel source, lithium source Homogeneous phase mixing, and obtain the nickel ion doped material with Rod-like shape after high temperature sintering, concrete steps are as follows:
(1) with bar-shaped manganese dioxide, nickel source, lithium source for raw material, be that Li:Ni:Mn=1 ~ 1.1:0.5:1.5 adopts magneton to be uniformly mixed in ethanolic solution with mol ratio, and in 50 ~ 80 DEG C of oil baths stirring and drying, by dry powder mull;
(2) repeat step (1) three ~ five time, obtain the powder of three kinds of uniform composition mixing;
(3) put in corundum magnetic boat by the mixture of powders of above-mentioned acquisition, sinter in air atmosphere, sintering temperature is 700 ~ 800 DEG C, and sintering time is 12 ~ 20 hours, terminates rear Temperature fall.
Bar-shaped nickel ion doped material prepared by said method can be applied to the positive electrode of lithium ion battery.
In the present invention, described bar-shaped manganese dioxide adopts hydro thermal method preparation to have the manganese dioxide of club shaped structure, concrete steps are as follows: weighing 1.2726g seven hydrated manganese sulfate and 1.7176g ammonium persulfate join in 50ml distilled water, stir 30min, acquisition manganese sulfate and ammonium persulfate concentrations are all 0.15mol/L.Solution is joined in water heating kettle, be put in homogeneous reactor and be raised to 180 DEG C with the heating rate of 10 DEG C/min, react 12 hours at 180 DEG C, the precipitation suction filtration obtained is dried, obtains bar-shaped manganese bioxide material.
In the present invention, the nickel source of employing is four hydration nickel acetates, and lithium source is two hydration lithium acetates.
Advantage of the present invention is as follows:
(1) lithium source in the process of bar-shaped nickel ion doped material prepared of the present invention, manganese source, nickel source hybrid mode are simple, convenient operation.
(2) preparation method of bar-shaped nickel ion doped material of the present invention is simple to operate, and process stabilizing is reliable, favorable reproducibility.
(3) the present invention is with the bar-shaped nickel ion doped high-voltage positive electrode material of bar-shaped manganese dioxide to be templated synthesis have certain pattern.
(4) this kind of synthesis mode is using acetate as raw material, cheap.
Accompanying drawing explanation
Fig. 1 is the SEM figure of bar-shaped nickel ion doped;
Fig. 2 is the XRD collection of illustrative plates of bar-shaped nickel ion doped;
Fig. 3 is that figure swept by the Mn unit vegetarian noodles of bar-shaped nickel ion doped;
Fig. 4 is that figure swept by the Ni unit vegetarian noodles of bar-shaped nickel ion doped;
Fig. 5 is the 0.5C cycle performance of bar-shaped nickel ion doped material.
Embodiment
Below in conjunction with accompanying drawing, technical scheme of the present invention is further described; but do not limit to so; everyly technical solution of the present invention modified or equivalent to replace, and not departing from the spirit and scope of technical solution of the present invention, all should be encompassed in protection scope of the present invention.
Embodiment 1:
(1) preparation of nano bar-shape manganese dioxide
Weighing 1.2726g seven hydrated manganese sulfate and 1.7176g ammonium persulfate join in 50ml distilled water, stir 30min, and acquisition manganese sulfate and ammonium persulfate concentrations are all 0.15mol/L.Solution is joined in water heating kettle, be put in homogeneous reactor and be raised to 180 DEG C with the heating rate of 10 DEG C/min, react 12 hours at 180 DEG C, the precipitation suction filtration obtained is dried, obtains bar-shaped manganese bioxide material.
(2) with bar-shaped manganese dioxide for manganese source, nickel source and lithium source mixing
With the manganese dioxide nickel acetate of above-mentioned acquisition and lithium acetate for raw material, with Li:Ni:Mn mol ratio for after 1.1:0.5:1.5 weighing, in ethanolic solution, adopted by raw material magneton to be uniformly mixed, and in 80 DEG C of oil baths stirring and drying, by the powder mull of drying.
(3) step (2) in triplicate, can obtain the powder of three kinds of uniform composition mixing.
(4) high temperature sintering prepares nickel ion doped material
Put in corundum magnetic boat by the powder of three of above-mentioned acquisition kinds of uniform composition mixing, sinter 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 is that photo is swept in the SEM photo of bar-shaped nickel ion doped material and the face of nickel manganese element, can see, club-shaped material distribution is comparatively even, and the distribution of nickel manganese element is very even.
From electrochemistry cycle performance in Fig. 5, bar-shaped nickel ion doped material prepared by the present invention can be applied to the positive electrode of lithium ion battery, because this kind of material has higher voltage platform, lithium-ion-power cell can be applied to, there is good cycle performance, initial charge capacity 181.2139 mAh/g of material, discharge capacity is 122.705 first charge-discharge efficiencies is first that after circulating for 67.71%, 50 times, charging capacity is 106.86 mAh/g.
Embodiment 2:
(1) preparation of nano bar-shape manganese dioxide
Weighing 1.2726g seven hydrated manganese sulfate and 1.7176g ammonium persulfate join in 50ml distilled water, stir 30min, and acquisition manganese sulfate and ammonium persulfate concentrations are all 0.15mol/L.Solution is joined in water heating kettle, be put in homogeneous reactor and be raised to 180 DEG C with the heating rate of 10 DEG C/min, react 12 hours at 180 DEG C, the precipitation suction filtration obtained is dried, obtains bar-shaped manganese bioxide material.
(2) with bar-shaped manganese dioxide for manganese source, nickel source and lithium source mixing
With the manganese dioxide nickel acetate of above-mentioned acquisition and lithium acetate for raw material, with Li:Ni:Mn mol ratio for after 1:0.5:1.5 weighing, in ethanolic solution, adopt magneton to be uniformly mixed, and in 80 DEG C of oil baths stirring and drying, by the powder mull of drying.
(3) step (2) repeats four times, can obtain the powder of three kinds of uniform composition mixing.
(4) high temperature sintering prepares nickel ion doped material
Put in corundum magnetic boat by the powder of three of above-mentioned acquisition kinds of uniform composition mixing, sinter 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 (5)
1. a preparation method for bar-shaped nickel ion doped material, is characterized in that described method step is as follows:
(1) be that Li:Ni:Mn=1 ~ 1.1:0.5:1.5 adopts magneton to be uniformly mixed in ethanolic solution by bar-shaped manganese dioxide and nickel source and lithium source with mol ratio, and in 50 ~ 80 DEG C of oil baths stirring and drying, by the powder mull of drying;
(2) repeat step (1) three ~ five time, obtain the powder of three kinds of uniform composition mixing;
(3) put in corundum magnetic boat by the mixture of powders of above-mentioned acquisition, sinter in air atmosphere, sintering temperature is 700 ~ 800 DEG C, and sintering time is 12 ~ 20 hours, terminates rear Temperature fall.
2. the preparation method of bar-shaped nickel ion doped material according to claim 1, is characterized in that described bar-shaped manganese dioxide adopts hydro thermal method to be prepared from.
3. the preparation method of bar-shaped nickel ion doped material according to claim 1, is characterized in that described nickel source is four hydration nickel acetates.
4. the preparation method of bar-shaped nickel ion doped material according to claim 1, is characterized in that described lithium source is two hydration lithium acetates.
5. the bar-shaped nickel ion doped material that prepared by method described in the arbitrary claim of claim 1-4 can be applied to 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 true CN104966830A (en) | 2015-10-07 |
| CN104966830B CN104966830B (en) | 2017-05-17 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108417830A (en) * | 2018-03-21 | 2018-08-17 | 湖北大学 | A kind of nickel lithium manganate cathode 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 |
-
2015
- 2015-05-25 CN CN201510269269.4A patent/CN104966830B/en not_active Expired - Fee Related
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 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108417830A (en) * | 2018-03-21 | 2018-08-17 | 湖北大学 | A kind of nickel lithium manganate cathode material and preparation method thereof |
| 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 |
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Granted publication date: 20170517 Termination date: 20180525 |