CN104319400A - Preparation method of nano spinel-type lithium manganate - Google Patents
Preparation method of nano spinel-type lithium manganate Download PDFInfo
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- CN104319400A CN104319400A CN201410532016.7A CN201410532016A CN104319400A CN 104319400 A CN104319400 A CN 104319400A CN 201410532016 A CN201410532016 A CN 201410532016A CN 104319400 A CN104319400 A CN 104319400A
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- preparation
- presintering
- resorcinol
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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 relates to a preparation method of a lithium ion anode material, in particular to a preparation method of nano spinel-type lithium manganate. The preparation method comprises the steps of preparing a mixed solution of lithium acetate and manganese acetate, adding resorcinol in the mixed solution, stirring, and adding formaldehyde solution after resorcinol is completely dissolved; placing the solution in a constant-temperature water bath to react so as to form gel; placing the gel in a drying oven to be dried, and then pre-sintering the gel; grinding and secondarily sintering the pre-sintered product; and finally grinding the secondarily-sintered product to obtain nano spinel-type lithium manganate. The nano spinel-type lithium manganate is prepared by adopting lithium acetate, manganese acetate, resorcinol and formaldehyde as raw materials, the phase purity of the product can be improved by adopting the pre-sintering, the crystallization performance, the discharging specific capacity and the coulombic efficiency of the material can be improved by virtue of the secondary sintering; and the electrochemical performance of the material can be improved by virtue of reasonable proportioning of the raw materials.
Description
Technical field
The present invention relates to the preparation field of lithium ion anode material, is the preparation method of nanometer spinel type LiMn2O4 specifically.
Background technology
The advantages such as lithium manganate having spinel structure enriches with its promoter manganese, cost is low, fail safe good, non-environmental-pollution, easily preparation become the first-selection of power lithium-ion battery positive electrode, but the main cause hindering electrokinetic cell type LiMn2O4 capability of industrialization to be formed is that its performance is stable not, namely it is in charge and discharge cycles process, capacity attenuation is very fast, especially obvious under high temperature.The factor affecting its cycle performance is mainly: 1, the purity of phase structure and stability, microscopic appearance are irregular; 2, the Jahn-Teller effect of material itself; 3, the dissolving etc. of manganese in lithium manganate material.And the major measure of current suppression Jahn-Teller deformation is bulk phase-doped, after metal cation replaces Manganic ion, lattice constant reduces, structure cell shrinks, the stability of spinel structure strengthens and makes the oxidation state of manganese more than 3.55, thus reaches the object suppressing Jahn-Teller deformation.
At present, the main method of synthetic spinel type LiMn2O4 can be divided into solid phase method and liquid phase method two kinds.Liquid phase method is as sol-gal process, and the method is widely used in the preparation of nano-ceramic powder, film and fiber coat.Because the method can the atom level Homogeneous phase mixing of realization response thing, and synthesis temperature is low, and the particle diameter thus preparing product mostly is nanoscale, and homogeneity is good, specific area large, form and composition are easy to control.Existing sol-gal process principle is that various metals cation can form chelate with organic acid, this chelate can be polymerized with polyhydroxy-acid, thus form the equally distributed solid polymer precursor of cation, under vacuum precursor is heat-treated and can be obtained end product; But the method preparation time is long, complex process, vacuum heat treatment process is difficult to control, and cost is higher.
Summary of the invention
For above-mentioned technical problem, the invention provides a kind of preparation method with the nanometer spinel type LiMn2O4 of higher specific discharge capacity and coulombic efficiency.
The present invention solves the problems of the technologies described above adopted technical scheme: the preparation method of nanometer spinel type LiMn2O4, and it comprises the following steps:
(1) prepare lithium acetate and manganese acetate mixed solution, in this mixed solution, add resorcinol, and stir, after resorcinol dissolves completely, add formalin;
(2) more above-mentioned solution is placed in water bath with thermostatic control reaction and forms gel;
(3) presintering is carried out after gel being placed in baking oven drying;
(4) double sintering is carried out after being ground by the product of presintering again;
(5) finally the product of double sintering is ground, obtain nano spinel LiMn2O4.
As preferably, described lithium acetate: manganese acetate: resorcinol: the mol ratio of formaldehyde is 1:2:(3--7): (7-8).
As preferably, the temperature of described water bath with thermostatic control is 50-70 DEG C, and the reaction time is 10--14h.
As preferably, it is fully dry that described gel is placed in the baking oven of 70--90 DEG C.
As preferably, described presintering, double sintering are all carry out in air atmosphere, adopt the sintering processing of constant temperature after at the uniform velocity heating up, are then naturally down to room temperature and obtain product.
As preferably, constant temperature 8-12h after presintering adopts the at the uniform velocity heating rate of 8--10 DEG C/min to rise to 300--400 DEG C.
As preferably, after described presintering product grinding evenly, then carry out double sintering, constant temperature 8-12h after double sintering adopts the at the uniform velocity heating rate of 4--6 DEG C/min to rise to 550--800 DEG C.
As can be known from the above technical solutions, the present invention prepares nanometer spinel type LiMn2O4 with lithium acetate, manganese acetate, resorcinol, formaldehyde for raw material, adopt presintering can improve the phase purity of product therebetween, improve the crystal property of material, specific discharge capacity and coulombic efficiency through double sintering; And by rational pulp furnish, improve the chemical property of material.
Embodiment
Preparation method of the present invention is introduced in detail below in conjunction with embodiment:
This preparation method adopts the sol-gal process of improvement, and it comprises the following steps:
(1) prepare lithium acetate and manganese acetate mixed solution, in this mixed solution, add resorcinol, and stir, after resorcinol dissolves completely, add formalin; Because the pairing of raw material has larger impact to the structure of material and electrical property, the present invention adopts lithium acetate: manganese acetate: resorcinol: the mol ratio of formaldehyde is 1:2:(3--7): (7-8), this proportioning can ensure that lithium manganate material crystal property, phase purity, particle diameter, dispersiveness and homogeneity reach preferred.
(2) more above-mentioned solution is placed in water bath with thermostatic control reaction and forms gel; The temperature of described water bath with thermostatic control is 50-70 DEG C, and the reaction time is 10--14h, thus raw material is fully reacted.
(3) presintering is carried out after gel being placed in baking oven drying; It is fully dry that described gel should be placed in the constant temperature oven of 70--90 DEG C, then in air atmosphere, by gel precursor with 8--10 DEG C/min rise to 300--400 DEG C after constant temperature 8-12h carry out presintering, be then naturally down to room temperature and obtain presintering product.
(4) again constant temperature 8-12h after rising to 550--800 DEG C with the at the uniform velocity heating rate of 4--6 DEG C/min after the grinding evenly of the product of presintering is carried out double sintering, be naturally down to room temperature and obtain double sintering product.
(5) finally the product of double sintering is fully ground, obtain nanometer spinel type LiMn2O4.
Embodiment 1
First, 1mol lithium acetate and 2mol manganese acetate are mixed with mixed solution, then 3mol resorcinol is added in mixed solution and also constantly stir, 7mol formalin is added after it dissolves completely, be placed in 50 DEG C of waters bath with thermostatic control again and react 10h formation gel, then baking oven gel being placed in 70 DEG C is fully dry, in electric furnace, by the speed of 8 DEG C/min, temperature is risen to 300 DEG C subsequently, in constant temperature 8h presintering, temperature is risen to 550 DEG C by the speed of 4 DEG C/min after entering grinding evenly by presintering product in electric furnace, constant temperature 8h carries out double sintering again, finally the product of double sintering is fully ground, obtain nanometer spinel type LiMn2O4.Analyze after testing, the crystal grain average grain diameter preparing nanometer spinel type lithium manganate material under above-mentioned condition is that under 63nm, 0.2C, first discharge specific capacity and coulombic efficiency are respectively 109mAh/g and 93.2%, and the capability retention after 100 times that circulates is 81%.
Embodiment 2
First, 1mol lithium acetate and 2mol manganese acetate are mixed with mixed solution, then 5mol resorcinol is added in mixed solution and also constantly stir, 7.5mol formalin is added after it dissolves completely, be placed in 60 DEG C of waters bath with thermostatic control again and react 12h formation gel, then baking oven gel being placed in 80 DEG C is fully dry, in electric furnace, by the speed of 10 DEG C/min, temperature is risen to 360 DEG C subsequently, in constant temperature 10h presintering, temperature is risen to 650 DEG C by the speed of 5 DEG C/min after entering grinding evenly by presintering product in electric furnace, constant temperature 10h carries out double sintering again, finally the product of double sintering is fully ground, obtain nanometer spinel type LiMn2O4.Analyze after testing, the crystal grain average grain diameter preparing nanometer spinel type lithium manganate material under above-mentioned condition is that under 47nm, 0.2C, first discharge specific capacity and coulombic efficiency are respectively 137mAh/g and 96.3%, and the capability retention after 100 times that circulates is 85%.
Embodiment 3
First, 1mol lithium acetate and 2mol manganese acetate are mixed with mixed solution, then 7mol resorcinol is added in mixed solution and also constantly stir, 8mol formalin is added after it dissolves completely, be placed in 70 DEG C of waters bath with thermostatic control again and react 14h formation gel, then baking oven gel being placed in 90 DEG C is fully dry, in electric furnace, by the speed of 10 DEG C/min, temperature is risen to 400 DEG C subsequently, in constant temperature 12h presintering, temperature is risen to 800 DEG C by the speed of 6 DEG C/min after entering grinding evenly by presintering product in electric furnace, constant temperature 12h carries out double sintering again, finally the product of double sintering is fully ground, obtain nanometer spinel type LiMn2O4.Analyze after testing, the crystal grain average grain diameter preparing nanometer spinel type lithium manganate material under above-mentioned condition is that under 56nm, 0.2C, first discharge specific capacity and coulombic efficiency are respectively 113mAh/g and 94.1%, and the capability retention after 100 times that circulates is 83%.
Visible, adopt this method can prepare the LiMn2O4 of optimum performance in the condition of embodiment 2.
Above-mentioned execution mode is used for illustrative purposes only, and be not limitation of the present invention, the those of ordinary skill of relevant technical field, without departing from the spirit and scope of the present invention, can also make various change and modification, therefore all equivalent technical schemes also should belong to category of the present invention.
Claims (7)
1. the preparation method of nanometer spinel type LiMn2O4, it comprises the following steps:
(1) prepare lithium acetate and manganese acetate mixed solution, in this mixed solution, add resorcinol, and stir, after resorcinol dissolves completely, add formalin;
(2) more above-mentioned solution is placed in water bath with thermostatic control reaction and forms gel;
(3) presintering is carried out after gel being placed in baking oven drying;
(4) double sintering is carried out after being ground by the product of presintering again;
(5) finally the product of double sintering is ground, obtain nano spinel LiMn2O4.
2. preparation method according to claim 1, is characterized in that: described lithium acetate: manganese acetate: resorcinol: the mol ratio of formaldehyde is 1:2:(3--7): (7-8).
3. preparation method according to claim 1, is characterized in that: the temperature of described water bath with thermostatic control is 50-70 DEG C, and the reaction time is 10--14h.
4. preparation method according to claim 1, is characterized in that: described gel is placed in the baking oven fully drying of 70--90 DEG C.
5. preparation method according to claim 4, is characterized in that: described presintering, double sintering are all carry out in air atmosphere, adopts the sintering processing of constant temperature after at the uniform velocity heating up, is then naturally down to room temperature and obtains product.
6. preparation method according to claim 5, is characterized in that: constant temperature 8-12h after presintering adopts the at the uniform velocity heating rate of 8--10 DEG C/min to rise to 300--400 DEG C.
7. preparation method according to claim 6, is characterized in that: after described presintering product grinding evenly, then carry out double sintering, constant temperature 8-12h after double sintering adopts the at the uniform velocity heating rate of 4--6 DEG C/min to rise to 550--800 DEG C.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106830090A (en) * | 2017-03-27 | 2017-06-13 | 洛阳理工学院 | LiMn with porous laminated structure2O4The preparation method of positive electrode |
| CN107673408A (en) * | 2017-10-19 | 2018-02-09 | 柳州凯通新材料科技有限公司 | A kind of preparation method of modified lithium manganate cathode material |
| CN107697953A (en) * | 2017-10-19 | 2018-02-16 | 柳州凯通新材料科技有限公司 | A kind of preparation technology of modified lithium manganate |
| CN107792886A (en) * | 2017-11-06 | 2018-03-13 | 柳州光华科技有限公司 | A kind of production method of lithium manganate battery material |
| CN112897585A (en) * | 2021-02-01 | 2021-06-04 | 山东海科创新研究院有限公司 | Spinel lithium manganate, preparation method thereof and lithium ion battery |
| CN113353986A (en) * | 2021-07-08 | 2021-09-07 | 天津大学 | Rapid preparation method and application of lithium manganate cathode material |
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| CN101937987A (en) * | 2010-07-30 | 2011-01-05 | 合肥工业大学 | Method for preparing composite anode material LiFePO4/C for lithium ion battery |
| CN102569777A (en) * | 2012-01-02 | 2012-07-11 | 株洲泰和高科技有限公司 | New method for synthesizing porous layered LNMCO (333 material for short) |
| CN102916169A (en) * | 2012-10-26 | 2013-02-06 | 中国科学院宁波材料技术与工程研究所 | Lithium-rich manganese-based anode material and method for manufacturing same |
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Patent Citations (4)
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| CN101937987A (en) * | 2010-07-30 | 2011-01-05 | 合肥工业大学 | Method for preparing composite anode material LiFePO4/C for lithium ion battery |
| CN102569777A (en) * | 2012-01-02 | 2012-07-11 | 株洲泰和高科技有限公司 | New method for synthesizing porous layered LNMCO (333 material for short) |
| CN102916169A (en) * | 2012-10-26 | 2013-02-06 | 中国科学院宁波材料技术与工程研究所 | Lithium-rich manganese-based anode material and method for manufacturing same |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106830090A (en) * | 2017-03-27 | 2017-06-13 | 洛阳理工学院 | LiMn with porous laminated structure2O4The preparation method of positive electrode |
| CN107673408A (en) * | 2017-10-19 | 2018-02-09 | 柳州凯通新材料科技有限公司 | A kind of preparation method of modified lithium manganate cathode material |
| CN107697953A (en) * | 2017-10-19 | 2018-02-16 | 柳州凯通新材料科技有限公司 | A kind of preparation technology of modified lithium manganate |
| CN107792886A (en) * | 2017-11-06 | 2018-03-13 | 柳州光华科技有限公司 | A kind of production method of lithium manganate battery material |
| CN112897585A (en) * | 2021-02-01 | 2021-06-04 | 山东海科创新研究院有限公司 | Spinel lithium manganate, preparation method thereof and lithium ion battery |
| CN113353986A (en) * | 2021-07-08 | 2021-09-07 | 天津大学 | Rapid preparation method and application of lithium manganate cathode material |
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